KR101616798B1 - Solution film-forming method and solution film-forming apparatus - Google Patents

Abstract

The polymer 26 is dissolved in the solvent 27 in the dissolving tank 23 of the mixing section 15. The solution is dissolved in the dissolving section 16 by the first heater 31 and the cooler 32 and then filtered with the first filter 34. Concentrated in the concentrating section 17, and stored in the storage tank 43 as the pure dop 44. Additives necessary for each variety are combined in the additive liquid supply part 50 and mixed with the solvent 27 to prepare an additive liquid 67. [ The additive liquid 67 is added to the pure dop 44 from the additive nozzle 51 and mixed uniformly in the static mixer 52. When the variety is changed, a new varieties additive liquid (67) is added from the addition nozzle (51). The old flexible dope 54 is subjected to extrusion substitution with the new flexible dope 54 for the pipe capacity C2 smaller than the piping capacity C1 of the entire process to perform the type switching.

Solution forming equipment

Description

TECHNICAL FIELD [0001] The present invention relates to a solution film forming method,

The present invention relates to a solution casting method and apparatus for casting a dope in which a polymer is dissolved in a solvent on a support, followed by peeling and drying to obtain a polymer film.

TAC films formed of cellulose esters, particularly cellulose triacetate (hereinafter referred to as "TAC") having an average degree of acetylation of 57.5% to 62.5%, are excellent in optical isotropy, and therefore polarizers And the like.

As a method for producing a TAC film, for example, a solution casting method is well known as disclosed in JP-A-2005-104148. The solution film formation method can produce a film having excellent physical properties such as optical properties as compared with other production methods such as a melt film formation method. In the solution film-forming method, a dope is prepared by mixing a polymer and a variety of additives such as an ultraviolet absorber (UV), a matting agent, a retardation control agent and a plasticizer in a mixed solvent containing dichloromethane or methyl acetate as a main solvent. Subsequently, the dope is formed on the support from the flexible die to form a flexible film. After the flexible film has become self-supporting on the support, the flexible film is peeled off from the support as a wet film, dried, and wound in the form of a roll as a product film.

However, the polymer film needs to be produced according to the purpose. However, it is not realistic to provide a solution film-forming facility for each type of product, and it is usual to manufacture a plurality of varieties with one solution film-forming equipment. Since a plurality of varieties can not be manufactured at the same time, when a plurality of varieties are manufactured by a single solution deposition facility, one of the varieties is firstly manufactured and then the varieties are changed . There are the following two methods for changing this variety.

The first method is as follows. First, a new dope is prepared in a dissolving tank in which the kind and amount of additives are changed. Subsequently, a new dope prepared is flowed into the film formation line, and the dope is switched by replacing the old dope with this new dope.

The second method prepares another feeding device, prepares a new dope with this feeding device of another system, and switches the piping system. This switching eliminates the need to extrude the old dope into a new dope and reduces the piping capacity for replacing the old dope with the new dope, thereby enabling rapid variety switching.

In addition, in order to finely adjust the addition amount of the additive, Japanese Patent Laid-Open Nos. 2006-76280 and 2007-216674 carry out the addition immediately before the additive liquid is added immediately before the flexible die. In the addition just before the addition of the additive, the amount of the additive is measured by sampling the dope or sampling the finished product. When the amount of the additive is insufficient, the necessary amount is added just before the flexible die using an inline mixer. The addition or mixing of the additive by the inline mixer into the dope is also disclosed in, for example, Japanese Patent Application Laid-Open No. 2006-088583.

The first method and the second method are the methods for producing films by switching a plurality of kinds of films with one solution film-forming equipment. However, in the case of the first method in which the old dope is replaced with a new dope of the new prescription and the variety is switched, there is no need to provide another feeding device, so that the configuration is simplified. However, It is necessary to pass a new dope of about three times the piping capacity. For this reason, there is a problem that loss of time during extrusion or product loss becomes large.

Further, in the case of the second method of installing different feeding devices, there is no time loss or product loss as in the case of extrusion substitution of the first method, but it is necessary to install a plurality of feeding devices separately, There is a problem of becoming.

Further, the methods of Japanese Patent Application Laid-Open Nos. 2006-76280 and 2007-216674, in which the additive liquid is added to the dope immediately before the flexible die, are effective when one kind of product is manufactured by one film-forming equipment. However, when a plurality of varieties are produced by one film-forming equipment, there are cases where not only the kinds of additives used but also the timing of adding the additives and the target addition ratio are different for each type of film. Therefore, even if the methods of Japanese Patent Application Laid-Open Nos. 2006-76280 and 2007-216674 are used, it is not sufficient to merely switch the kind of additive in these methods depending on the kind of the film to be newly produced . For example, even when the additive liquid containing the additive in the liquid is changed, it is impossible to mix the additive liquid so that the dope is uniformized at all times under the same conditions. Therefore, there is a problem in that a film of a target variety can not be obtained until the addition amount of the additive liquid becomes a constant level and the properties of the dope after the addition of the additive liquid are stabilized, leading to the loss of raw materials and manufacturing time. Further, in some cases, since the objective additive is flexible in a state of being insufficient, a problem of film formation such as punching may occur during film formation, leading to a soft stop.

Particularly, when the amount of the additive liquid added immediately before the flow rate of the dope is small, the time loss and the product loss are large. This is because the piping leading to the additive nozzle is commonly used irrespective of the change of the additive liquid, and the smaller the flow rate of the new additive liquid, the longer it takes for the inside of the pipeline to fill up with the new additive. Therefore, this time becomes the loss time, and the dope flowing at this time does not have a predetermined ratio of the additive liquid, and therefore, when the film becomes a product, it can not be said to be a product.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a solution casting method and apparatus capable of suppressing the occurrence of a manufacturing time and a product loss without increasing the cost of the production facility even when a film of different kinds is produced The purpose is to provide. It is another object of the present invention to provide a solution casting method and apparatus capable of suppressing production time and product loss even when the amount of additive to be added to new varieties is small.

The solution film-forming method of the present invention comprises preparing a reference dope containing a polymer and a solvent (Step A), adding an additive peculiar to each type to the reference dope immediately before the flexible die to make a soft dope (Step B Forming a flexible film on the support by smoothing the flexible dope on the support by the flexible die (step C); applying a self-supporting property to the flexible film to peel the flexible film from the support as a wet film (Step D), drying the wet film to form a film (step E), and changing the additive in the adding step in the kind switching of the film in accordance with the kind (step F) do.

In the step B, it is preferable that the additive is contained in a liquid to prepare an additive liquid, and the additive liquid is added by an additive nozzle. (1/2) x C1} or more ({1/7) x C1} or less on the basis of the flexible die when the piping capacity from the step A to the flexible die is taken as C1, It is preferred to add the additive at the position. It is preferable that the ratio of the flow rate of the additive liquid to the flow rate of the reference dope in the step B is 1% or more and 30% or less. In the step B, it is preferable to add the additive in-line. Further, it is preferable that the additive contains a plasticizer, and the concentration of the plasticizer in the additive liquid is 10 wt% or more and 65 wt% or less. It is preferable that the reference dope contains an additive commonly required for each variety, or a pure dope comprising the polymer and the solvent.

It is preferable to circulate the additive liquid in advance before the step B, and it is more preferable to circulate the additive liquid at the same flow rate as that when the additive liquid is added to the reference dope. It is more preferable that the circulation starts more than 120 minutes before the start of the addition. In addition, it is preferable to clean the flow path of the additive liquid up to the additive nozzle with a cleaning liquid comprising the same liquid as that of the solvent before adding the additive liquid used for the new varieties to the reference dope in the kind switching of the film .

(QAE / QD) x 100} is 10% or less, when the flow rate of the reference dope is QD and the addition flow rate of the additive liquid to be added to a new variety is QAE (QAS) of 1.5 to 3.0 times the added flow rate (QAE) when the additive flow rate QAE of the additive liquid is not more than 300 × 10 ^-6 m 3 / min (= 300 cc / minute) And the initial addition flow rate (QAS) is set to the addition flow rate (QAE) after the lapse of the predetermined time. The predetermined time is preferably a time until the pressure of the additive liquid at the outlet of the additive nozzle becomes equal to the pressure of the reference dope near the outlet of the additive nozzle, , And it is more preferable to circulate the additive liquid at the same flow rate as the initial addition flow rate (QAS).

In the step B, it is preferable that the additive liquid has a buffer layer formed on the outer periphery thereof and added to the reference dope, and in step B, the reference dope added with the additive liquid is mixed and homogenized to form the soft dope.

The buffer solution constituting the buffer layer is prepared by adding the same liquid as the solvent, diluting the additive liquid with the same liquid as that of the solvent, diluting the reference dope with the same liquid as that of the solvent, And a diluent. The step B preferably sets the flow rate ratio (QB / QAE) to 0.01 or more and 0.1 or less when the buffer solution is the same as the solvent component and the flow rate of the additive solution is QAE and the flow rate of the buffer solution is QB .

It is preferable that the mixing is performed by passing through a plurality of inline mixers having different mixing methods.

Wherein the inline mixer includes a torsional mixing type static mixer in which a plurality of first elements constituted by twisted partition members are arranged in a passage of a reference dope and a second element formed by alternately crossing a plurality of elongated partition members, A through-the-mixer in which a plurality of mixers are arranged in a passage of a dope, and a dynamic mixer in which a rotating mixer body is arranged in a passage of a reference dope.

The solution deposition apparatus of the present invention comprises a reference dope preparation unit for preparing a reference dope containing a polymer and a solvent, and a reference dope preparation unit for preparing an additive peculiar to each kind, And a soft dope to which the additive is added is softened on the support by means of the flexible die to form a flexible film on the support and impart a self supporting property to the flexible film, And an additive changing unit for changing the additive to be added to the reference dope to a new prescription in the kind switching of the film. The film forming apparatus according to claim 1, .

It is preferable that the additive adding unit has an additive nozzle for adding the additive liquid contained in the liquid to the reference dope and an additive supply unit for preparing the additive liquid to be supplied to the additive nozzle, It is more preferable to have the additive circulation means for circulating upstream of the addition nozzle. It is preferable that the additive adding unit has a cleaning section for cleaning the flow path of the additive liquid up to the additive nozzle with a cleaning liquid comprising the same liquid as that of the solvent in switching the kind of the film.

It is preferable that the additive supply unit has flow rate control means for controlling the flow rate of the additive liquid.

It is preferable that the additive nozzle has a buffer layer forming means for forming a buffer layer on the outer periphery of the additive liquid and the additive adding unit has a mixing portion which mixes and homogenizes the reference dope added with the additive to make a soft doping.

According to the present invention, in the case of producing a film of a new variety having different components and amounts of various additives, it is possible to suppress the occurrence of production time loss and product loss without increasing the equipment cost. Further, switching of the additive can be performed efficiently, and it is possible to operate quickly at a predetermined addition ratio. This reduces the time from starting the addition of the additive to stabilizing the quality and suppressing the problem of film formation such as punching due to insufficient additive and waste of dope is also eliminated. According to the present invention, this effect can be obtained even when the amount of the additive used in a new variety is small. Furthermore, since gelation due to the addition of the additive and the occurrence of agglomeration of the additive are suppressed, the product loss is more reliably reduced as a result.

The above objects and advantages will be easily understood by those skilled in the art by reading the detailed description of the preferred embodiments with reference to the accompanying drawings.

The solution film-forming equipment 10 according to the first embodiment of the present invention shown in Fig. 1 comprises a pure doping unit 11, an additive adding unit 12, and a film-forming unit 13.

The pure doping unit 11 includes a mixing unit 15, a dissolution unit 16, a concentration unit 17, and a storage unit 18. The mixing section 15 has first and second tanks 21 and 22, a dissolution tank 23, a reservoir tank 24 and a pump 25. A polymer 26 is placed in the first tank 21 and a predetermined amount of the polymer 26 is metered by an attached meter to be introduced into the dissolution tank 23. A solvent 27 is placed in the second tank 22 and a predetermined amount of the solvent 27 is introduced into the dissolution tank 23 by an attached metering pump (not shown).

The dope comprising only the polymer 26 and the solvent 27 is referred to as a pure dop in the present invention. This pseudo-dope is commonly used for each variety, and a minimum amount of each of the varieties to be added may be added at the time of preparation of the Pseudo-Dope, and this is referred to as a consultation reference dope (see the second embodiment to be described later) . In addition, pure dope and reference dope of consultation are collectively referred to as reference dope only.

The polymer 26 according to the present invention is not particularly limited and may be applied to a solution casting method. Among them, the use of cellulose acylate allows obtaining a film having high transparency and excellent optical characteristics, and thus the resulting film is suitable for optical applications such as a protective film for a polarizing plate and an optical compensation film. Among them, cellulose acetate is used, and in particular, TAC having an average value of acetylation of 57.5% to 62.5% is used to obtain a film having excellent optical properties. The degree of acetylation refers to the amount of bound acetic acid per unit weight of cellulose, which can be obtained by measurement and calculation of acetylation degree in ASTM: D-817-91 (test method such as cellulose acetate). In this embodiment, granular TAC is used. When a granular polymer is used, from the viewpoint of compatibility with a solvent, it is preferable that 90 wt% or more of the granular polymer is 0.1 to 4 mm in diameter, more preferably 1 to 4 mm in diameter.

The solvent 27 is preferably a halogenated hydrocarbon, an ester, a ketone, an ether, an alcohol, or the like, but is not particularly limited and may be appropriately selected in consideration of solubility with a polymer to be used. The solvent (27) may be one kind of compound or a mixed solvent in which a plurality of compounds are mixed. Specific examples include halogenated hydrocarbons such as dichloromethane and the like, esters such as methyl acetate, methyl formate, ethyl acetate, amyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone, cyclohexanone, Etc.), ethers (e.g., dioxane, dioxolane, tetrahydrofuran, diethyl ether, methyl-t-butyl ether and the like) and alcohols (e.g. methanol and ethanol).

The dissolution tank 23 is provided with a stirring blade, and the polymer 26 and the solvent 27 in the dissolution tank 23 are agitated by the rotation of the stirring blade. By this stirring, a crude dissolution liquid in which the solute such as the polymer (26) is not completely dissolved in the solvent is obtained.

The solution to be dissolved in the dissolution tank 23 is once stored in the reservoir tank 24. As a result, the dissolution tank 23 becomes empty, and a continuous batch-forming process in which batch solutions are repeated one by one is made possible. The storage tank 24 also has a stirring blade. By rotating the stirring blades, the stirring solution is stirred and homogenized.

The crude solution in the storage tank 24 is sent to the first heater 31 of the dissolution section 16 through the pump 25. As the first heater 31, an inline mixer such as a multi-tube heat exchanger or a static mixer is used. The crude solution is heated by the first heater (31). The heating temperature, that is, the temperature of the crude solution by heating is preferably 50 to 120 ° C, and the so-called heating time for maintaining the temperature of the crude solution in this temperature range is preferably 5 to 30 minutes. By this heating, the solute such as the polymer 26, which is required for solution casting, is completely dissolved without being denatured, and the pure doping is prepared. The pure dopant thus prepared has a solid content concentration of 14 to 24% by weight of the cellulose ester.

The Pure Dope heated by the first heater 31 is sent to the cooler 32. [ Is cooled to below the boiling point of the main solvent constituting the pure dop by the cooler (32). The cooled pure dopant is sent to the first filter 34 by the pump 33. The main solvent means a single component when the solvent 27 is composed of a single component and means a liquid component having the largest mass ratio when composed of a plurality of liquid components.

Although not shown, the first filter 34 includes a plurality of filter bodies for switching use, a cleaning device for the filter bodies, and the like, and the filters are cleaned / exchanged on the other side while performing filtration on one side . This enables continuous filtration of the pure dopant. The filtration method is not particularly limited. After filtration, the pure dope is sent to the concentration section 17 by the pump 35.

After the filtration, the pure dope 44 is heated by the second heater 40 of the concentrating section 17 and then sent to the flash tank 41 where the pure dope is concentrated by the flash concentration method. The pure dope after concentration is stored in the reservoir tank 43 of the storage section 18 by the pump 42. [ Further, the thickening section 17 is provided as required and may be omitted.

The Pure dope 44 stored in the storage tank 43 is sent to the additive adding unit 12 by the pump 45. The additive adding unit 12 adds inline the additive liquid to the pure dop 44. The additive adding unit 12 includes an additive liquid supply unit 50 for making a predetermined additive liquid 67 and supplying the additive liquid 67 made to the pure dope 44 flowing through the dope pipe 46, 51, a static mixer 52, and a second filter 53. A check valve (not shown) or an open / close valve (not shown) for preventing the backflow of the additive liquid 67 is provided in the pipe for feeding the additive liquid 67 to the additive nozzle 51, if necessary.

The additive liquid supply part 50 includes a plurality of additive combination systems 61, a pump 62, and a controller 63, which contain predetermined additives and prepare an additive liquid to be used as it is or in mixture with the additive liquid 67, . The additive combination system 61 comprises an additive combination unit 64, an additive liquid tank 65, and an on-off valve 66a. The additive liquid prepared in each additive combination system 61 may be used alone as the additive liquid 67 or the additive liquid prepared in the different additive combination system 61 may be used as the additive liquid 67 67). In this manner, by providing a plurality of additive combination systems 61, it is possible to introduce a plurality of kinds of additive liquids 67 into the pure dope 44 according to the film type.

The types of the various additives in the additive liquid 67 and the amount added to the pure dope 44 are obtained in advance for each type of the film 106 to be produced (see Fig. 2), and a combination lookup table memory (combination LUT) . The controller 63 obtains the kind and amount of the additive to be added from the combination LUT 68 according to the type of the film 106. Based on the type and amount of the additive thus obtained, the additive combination of the kind and amount of the additive according to the film type is combined by the additive combination unit 64. This additive liquid is stored in each of the additive liquid tanks 65. The plurality of additive liquid tanks 65 are provided with additive liquid changing means 66 for adjusting the opening degree of the pipe to change the additive liquid 67 in accordance with the kind of the film. The additive liquid changing means 66 is constituted by a plurality of open / close valves 66a. By controlling the degree of opening and closing thereof, the additive liquid to be constituted by the additive liquid 67 is sent to the predetermined amount adding nozzle 51 do. The degree of opening and closing of the opening and closing valve 66a is controlled by the controller 63 so that the additive liquid 67 added to the pure dope 44 is changed and the additive liquid 67 And is sent to the addition nozzle 51 by the metering pump 62.

The additive nozzle 51 is a flat nozzle whose tip is flattened and extended in the radial direction of the circular section of the dope pipe 46. The addition nozzle 51 and the static mixer 52 disposed on the downstream side are described in detail in Japanese Patent Laid-Open Publication No. 2006-117904, and a detailed description thereof will be omitted. After the additive liquid 67 is uniformly added to the Pure dope 44 by the static mixer 52, the Pure dope 44 is removed by the second filter 53 to become the Smooth Dope 54. [ The flexible dope 54 is sent to the flexible die 107 (see Fig. 2) of the film forming unit 13.

In the additive adding unit 12, the flow rate of the additive liquid 67 to the reference dope, that is, the flow rate of the reference dope when the additive liquid is added to the reference dope is QD, (Unit:%) obtained by {(QAE / QD) x 100} is preferably not less than 1% and not more than 30%. In the present embodiment shown in Fig. 1, QD is the flow rate of the pure dop 44.

In addition, when the additive flow rate ratio of the additive liquid 67 to the reference dope is 0.9%, it is often the case that the additive liquid 67 has to be made as high concentration as the additive flow rate ratio is set low, Gel failure may also occur in the film 106, which is a product, but when the ratio of the added flow rate is 1% or more, occurrence of gelation is reliably suppressed.

On the other hand, when the additive flow rate ratio of the additive liquid 67 to the reference dope is 31%, the flow rate QAE of the additive liquid 67 becomes larger with respect to the flow rate QD of the reference dope, However, by setting the addition flow rate to 30% or less, the reference dope and the additive liquid 67 are mixed with each other and become uniform, and the mixing property surely improves.

The ratio (rho l / rho 2) of the viscosity (rho 1) of the pure dope (44) to the viscosity (rho 2) of the additive liquid (67) is preferably 500 or less. When the viscosity ratio exceeds 500 or the added flow rate exceeds 30%, it becomes difficult for them to be mixed. When the viscosity ratio is less than 1%, they are mixed but no efficient addition is performed.

It is preferable that the additive contains a plasticizer and the concentration of the plasticizer in the additive liquid 67 is 10 wt% or more and 65 wt% or less. The concentration of the plasticizer is a percentage (unit:%) obtained by (x / y) x 100 when the weight of the additive liquid 67 is x and the weight of the plasticizer is y. When the amount of the additive liquid 67 is less than 10 wt%, the amount of the additive liquid 67 to the pure dope 44 needs to be increased in order to make the final amount of the plasticizer necessary, The mixing ratio of the two may increase, resulting in poor mixing properties. On the other hand, when the amount of the additive exceeds 65 wt%, the amount of the additive which is insoluble in the Pseudodope 44 increases.

In the present invention, necessary additives are added to the flexible dies 107 of the film-forming unit 13 by the additive liquid feeder 50 and the additive nozzle 51 in accordance with the kind of the film to be produced, ), So it can respond quickly to new varieties. Thus, the addition is performed in the vicinity of the flexible die 107 and on the upstream side of the flexible die 107. Further, when the additive liquid 67 is supplied to the pure dop 44, the additive contained in the additive liquid 67 is required for each type of product containing a substance peculiar to each kind of additive. On the other hand, in the case where the additive liquid 67 is supplied to the reference dope obtained in the above manner by adding the additive commonly necessary for each variety to the pure dope 44 as in the case of the third embodiment described later, The additive contained in the liquid 67 becomes an additive peculiar to each variety.

Examples of additives include plasticizers, matting agents, ultraviolet absorbers (UV agents), retardation control agents, and other additives. In the additive combination unit 64, various additives required for the varieties to be produced from the combination LUT 68 are identified. These specific additives are added to the solvent 27 by a necessary amount and mixed, and the additive liquid 67 is combined. These additives are described, for example, in paragraphs [0196] to [0516] of Japanese Patent Application Laid-Open No. 2005-104148, and these substrates are also applicable to the present invention.

As described above, in the present invention, it is only necessary to change the type of the additive liquid 67 or the amount thereof to be added. Compared with the conventional methods, the section in which the former dope is replaced by the new dope can be shortened during the dope switching .

The extruded substitution portion becomes a state in which the new and the old dope are mixed. A new dope of about three times the piping capacity from the reservoir tank 24 to the flexible die of the film forming unit 13 is required if the conventional equipment in which the additive is put in the mixing section 15 until the new dope is completely replaced . Therefore, in the conventional facility, since the new dope of about three times the piping capacity from the reservoir tank 24 to the flexible die does not become a product until the extrusion replacement is completed and the additive is mixed, Can not be provided for recycling. That is, the new dope corresponding to the extrusion displacement amount is wasted. For this reason, in the conventional switching method of a new product type by the extrusion substitution, loss of the new doping becomes enormous. In contrast, in the present invention, since the additive is added to the reference dope just before the flexible die 107 (see Fig. 2) of the film-forming unit 13, the displacement replacement amount can be suppressed to a lesser extent.

In the first embodiment, the piping capacity C2 of 1/280 or more and 1/7 or less of the conventional piping capacity C1 on the downstream side, that is, the entrance of the flexible die of the film-forming unit 13, It is possible to dispose the addition nozzle 51 at a position where the nozzle 51 is located. Further, the film portion in which the old and new additives are mixed is about three times as large as the piping capacity after the addition nozzle, and the loss of the dope can be suppressed to about 1/280 to 1/7 of that of the conventional equipment.

The pure Dope 44 flowing through the dope pipe 46 has a very high viscosity as compared with the additive liquid 67. For example, the viscosity rho 2 of the additive liquid 67 is approximately 0.001 to 1.0 (unit Pa s), the viscosity rho 1 of the pure dope 44 is approximately 10 to 150 (unit Pa s) , And the viscosity (rho 2) of the additive liquid (67) is 1/150000 to 1/10 of the viscosity (rho 1) of the pure dope. As described above, when the pure dop 44 and the additive liquid 67 having different viscosities are mixed with each other, it is likely that the droplet of the additive liquid 67 is formed in the pure dop 44. That is, a minute droplet of the additive liquid 67 is likely to be dispersed in the pure dop 44, and gelation tends to occur. This tendency is greater as the flow rate of the additive liquid 67 is smaller than the flow rate of the pure dop 44 when the additive liquid 67 is supplied to the pure dop 44.

In order to proceed the mixing so that the additive is uniformly dispersed in the pure dop 44 from such a droplet dispersed state, a so-called inline mixer, for example, a static mixer, which mixes the liquid by continuously sending the liquid to be mixed to a plurality of elements (52) is valid. However, the inline mixer such as the static mixer 52 is arranged so that a plurality of elements 52a of a predetermined shape are aligned in the longitudinal direction of the dope pipe 46, as known in the art. Since the number of the elements 52a is determined such that the additive can be uniformly dispersed in the pure dop 44, the length of the inline mixer becomes longer as the number of the elements 52a increases, The viscosity is determined according to the ratio of the viscosity or the flow rate, and the viscosity and the flow rate become longer. Further, as the length of the inline mixer is lengthened by increasing the number of the elements 52a, the gelation is more reliably suppressed.

As described above, the static mixer 52 used for supplying the additive liquid 67 to the pure dope 44 to uniformly disperse the additive is provided with a certain length, that is, the additive is uniformly dispersed by shearing by the element 52a, So long as it can be dispersed to a certain extent. The upstream end of C2 is set to the upstream side as the static mixer 52 becomes longer.

Although only one dissolving tank 23 is shown in Fig. 1, a plurality of dissolving tanks 23 are usually provided, and these dissolving tanks 23 are connected to the reservoir tank 24. Fig. Each of the dissolution tanks 23 may be connected to the reservoir tank 24 by independent pipes and only the connection pipe to the predetermined dissolution tank 23 may be changed to be in the open state. There is a case where a pipe is connected to one pipe connected to the reservoir tank 24 and a switching valve for switching the solution to flow into the reservoir tank 24 from a predetermined dissolution tank 23 is provided . 1 shows the former case. The upstream end of C1 is an upstream end of the pipe connecting the downstream end of the dissolution tank 23, that is, the dissolution tank 23 and the reservoir tank 24. On the other hand, in the latter case, the connecting portion connecting the pipes extending from the respective melting tanks 23 to one pipe may be the upstream end of C1.

Among the additives to be used, there are those dissolved in the solvent (27). Therefore, conventionally, the additive liquid 67 is added upstream of the first heater 31. Further, it is considered preferable that the solvent 27 and the additive come into contact with each other at the earliest possible timing, and the additive liquid 67 is added on the upstream side as much as possible. However, the additive liquid 67 can be added to the solution tank 23 and the reservoir tank 24 at the most upstream side since the plurality of dissolution tanks 23 are switched and used as described above in forming the coagulated solution. The upstream end of the pipe to which the pipe is connected. From this point of view, the upstream end of the conventional pipe capacity C1 is shown as a downstream end of the dissolving tank 23 in Fig. On the other hand, when the additive is also mixed in the dissolving tank 23, the upstream end of the dissolving tank 23 may be the upstream end of the conventional pipe capacity C1.

As described above, the upstream end of the conventional piping capacity C1 and the upstream end of the piping capacity C2 are set. Therefore, the range of 1/280 ~ 1/7 of C2 / C1 is based on these settings.

1, the additive liquid 67 is added to the crude solution at the upstream end of the piping connecting the dissolution tank 23 and the reservoir tank 24 with respect to the conventional piping capacity C1 FIG. In this case, since the mixture of the crude solution and the additive liquid 67 flowing in the piping between the dissolution tank 23 and the reservoir tank 24 is replaced with a mixture of the crude solution and the new additive liquid 67, The upstream end of the piping capacity C1 serves as a connection portion between the dissolving tank 23 and the piping. Therefore, in the case where the mixing solution and the additive liquid 67 are mixed in the dissolving tank 23, the inside of the dissolving tank 23 is replaced with a new mixture. Therefore, the upstream end of the conventional piping capacity C1 And is the upstream end of the dissolving tank 23.

The conventional piping capacity C1 and the piping capacity C2 are not limited to the capacity of piping connecting between the equipment such as between the cooler 32 and the pump 33 or between the tanks, . That is, all capacities, including piping, are present.

If necessary, an on-line component system may be provided on the outlet side of the additive liquid tank 65 to determine whether or not the additive component of the additive liquid is within the predetermined range. In this case, the addition amount of various additives in the additive combination portion 64 is increased or decreased in accordance with the measurement result, and the addition amount of various additive components is controlled within a predetermined range. Near-infrared spectroscopy is used for on-line component measurement.

Near infrared spectroscopy is a method in which near infrared light in a short wavelength region is irradiated to an additive liquid and a light sensor measures light such as scattered reflection light, scattered transmission light or transmitted reflection light from the measured object, And calculating the absorbance of the additive liquid from the absorbance based on the previously prepared calibration curve by obtaining the absorbance of the spectral wavelength region having a correlation inherent to the component amount.

2, the film forming unit 13 includes a flexible chamber 100, a moving section 101, a tenter 102, a drying chamber 103, and a take-up machine 104, 54 is used to make the film 106. The flexible chamber 100 is provided with a flexible die 107 on which a discharge port of the flexible dope 54 is formed, a flexible drum 108 serving as a support and a peeling roller 109.

The flexible dope 54 is plied on the rotating flexible drum 108 as an infinite flexible support through the flexible die 107 and the flexible film 111 is formed on the peripheral surface. It is preferable that the surface temperature of the flexible drum 108 is kept substantially constant within the range of -10 占 폚 to 10 占 폚. If the flexible drum 108 is flexible, the gel is rapidly cooled, so that the gel film 111 is formed within a short period of time. The flexible film 111 having the self supporting property is supported by the peeling roller 109 and is transferred from the flexible drum 108 to the wet film 113 as the wet film 113 Peeled.

In the moving part 101, the wet film 113 is supported by a plurality of rollers, and the drying progresses during conveyance. In the tenter 102, both side ends of the wet film 113 are held by a retaining means such as a fin, and then dried during the conveyance to become a film 106. [ Thereafter, the film 106 is wound in a roll on the core 105 of the winder 104.

The second filter 53 of the additive adding unit 12 is provided on the upstream side of the flexible die 107 and the Pure Dope 44 in which the additive liquid 67 is mixed is filtered before being supplied to the fusing. As a result, the soft dope 54 in which impurities are further removed is obtained. In this embodiment, an apparatus equipped with a metal filter is used, but the filtration method is not particularly limited, and a filter paper is suitably used. Here, it is preferable that the hole of the filter has an average pore diameter of 100 mu m or less in order to remove even minute impurities. If the average pore diameter is too small, the filtration pressure becomes high and the internal pressure limit of the filter may be reached in a short time. On the other hand, if the average pore diameter is too large, it is difficult to capture fine impurities in the soft dopes 54. The filter may be appropriately selected in consideration of productivity and the like.

The solvent recovery from the structure of the flexible chamber 100, the flexible die 107 and the flexible drum 108, the coaming, the peeling, the drawing, the drying conditions of each process, the handling method, Method and film recovery method are described in detail in paragraph [0617] to paragraph [0889] of Japanese Patent Application Laid-Open No. 2005-104148, and the description thereof can also be applied to the present invention. In the above-described embodiment, the cooling gel is used to cool the flexible film 108 on the flexible drum 108 to have a self-supporting property. However, the present invention is also applicable to a drying method in which a flexible film is dried on a band or drum, can do.

The film obtained by the present invention has high transparency and retardation value and low humidity dependency. Therefore, in particular, it can be suitably used as a retardation film of a polarizing plate, but it can also be used as a protective film for protecting the surface of a polarizing plate. For example, Japanese Patent Application Laid-Open No. 2005-104148 discloses a specific use of the cellulose ester film of the present invention. In the paragraph [1088] to [1265], TN, STN, VA, OCB , Reflection type, and other examples are described in detail, and these descriptions can also be applied to the present invention.

In the continuous production of the film, when the kinds and amounts of the various additives are changed to carry out the kind switching, the additive adding unit 12 switches from the old additive to the new additive in a state where the softening is continued. First, the type switching information is sent from the master controller (not shown) to the controller 63 of the additive adding unit 12. The type of switching information includes the timing of switching and the type and concentration of additives used in new varieties. When the type switching information is sent, the controller 63 controls the additive combination unit 64 to make each additive liquid (not shown) constituting the additive liquid 67 corresponding to the new variety. The controller 63 controls the opening degree of each of the opening / closing valves 66a of the additive liquid changing means 66 so as to send the additive liquid made in the additive combination portion 64 from the additive liquid tank 65 to the downstream side. In this manner, the additive liquid 67 corresponding to the old cultivar type is switched to the additive liquid 67 of the new variety by inputting the kind switching timing signal to the controller 63. [ At this time, the additive liquid 67 of the old varieties is discharged and cleaned, and then the additive liquid 67 of the new variety is sent to the additive nozzle 51.

In addition, although the above-described first embodiment has been described by taking a single-layered flexible as an example, it is also possible to additionally form a shared layer in which the outer layer is flexed simultaneously or sequentially on both sides of the base layer. In this case as well, as in the above embodiment, first, a pure doping without an additive is prepared, and necessary additives in each layer for the pure doping may be added to each layer immediately before the flexible die.

In the case of the simultaneous sharing type, a plurality of flexible dopes 54 are independently guided to one flexible die 107 to be joined and flexed in the flexible die 107, There is a case where a plurality of dope pieces 54, which are provided upstream of the flexible die 107 and joined together, are fed to the flexible die 107 in a single stream in a flexible manner. In the latter case using the feed block, the internal flow path of the feed block is also included in the conventional piping capacity (C1) and piping capacity (C2).

Since the flexible dopes 54 are flexible by using the plurality of flexible dies 107 in the case of the sequential shared pipe, the upstream end of each flexible die 107 is used as the downstream end of the conventional pipe capacity C1, It may be set as a reference position at the time of determination of the capacitance C2.

In the first embodiment, the additive is added at the same addition position. However, as shown in Fig. 3, the multi-stage addition unit 70 for adding an additive at a plurality of positions may be used. The multi-stage addition unit 70 according to the second embodiment is constituted by disposing the first addition unit 71 and the second addition unit 72 in the direction of the Doped flow downward with respect to the dope pipe 73. The first and second adders 71 and 72 are composed of an additive liquid feeder 50, additive nozzles 51, and a static mixer 52. The multiple stage addition unit 70 further includes a second filter 53, which is the same as the additive addition unit 12, downstream of the second addition unit 72.

This multi-step addition is effective when the addition at the same addition position is not performed uniformly once. Further, a plurality of stages may be connected in series, and the number of stages is not particularly limited. The additives at the respective addition sites may be the same or may be added at the respective addition sites.

Next, a third embodiment of the present invention will be described with reference to Fig. In the third embodiment, for the additive to be commonly used in each kind of the pure dope composed of the polymer and the solvent, the minimum amount of the additive to be used is added in advance to the reference dope preparing unit 80, ). In the additive adding unit 82, the deficiency is added based on the amount of additive added in the reference dope 81. However, the constitution of the additive adding unit 82 is the same as that of the additive adding unit 12 in Fig. In Fig. 4, reference numeral 87 is added to the additive agent added in the additive adding unit 82. Fig.

The third embodiment differs from the first embodiment in the following points (1) to (3), and the other features are the same as those of the first embodiment. In FIG. 4, Are denoted by the same reference numerals as those in Fig. (Common additive) 83 serving as a base to the dissolving tank 23 of the mixing section 85 is added from the third tank 84, (2) adding an insufficient amount of additives to the additive adding unit 82 in the narrow reference dope 81, and (3) adding the insufficient amount of additives necessary for each film type Add new additives. Therefore, the additive liquid 87 contains at least one of the " deficient fraction " of (2) and the " new additive necessary for each kind of (3) ".

In this third embodiment, when preparing the new flexible dope 54 in which the common additive 83 added at the time of making the narrow reference dope 81 is made unnecessary, There is a disadvantage in that switching of the new prescription is troublesome because the reference dope 81 for consultation for the new prescription dope should be produced after writing. On the other hand, the common additive 83, which is commonly used, The addition amount in the additive adding unit 82 can be reduced by that much, and the addition amount in the addition unit 82 can be reduced. The method of adding the common additive 83 is not limited to the third tank 84 but may be added to the dissolving tank 23 by various adding methods.

Next, a fourth embodiment of the present invention will be described with reference to Fig. In the fourth to eighth embodiments described below, only different forms from those of the first embodiment will be described. In Fig. 5, the same devices and members as those of Figs. 1 to 4 are shown in Figs. 4, and description thereof is omitted.

The solution film-forming equipment 90 of the fourth embodiment has an additive adding unit 92 as described below instead of the additive adding unit 12 of the first embodiment.

The pure dope 44 stored in the reservoir tank 43 of the storage section 18 is sent to the additive agent adding unit 92 by the pump 45. The additive adding unit 92 is connected to the additive liquid supply unit 93, the additive nozzle 51, the static mixer 52, the second filter 53, the pipe for connecting the additive liquid supply unit 93 and the additive nozzle 51 55). A check valve 56 and an on-off valve 57 for preventing the backflow of the additive liquids 99a to 99c are provided in the piping 55 for feeding the additive liquids 99a to 99c to the additive nozzle 51. [

The additive liquid supply unit 93 includes first to third additive liquid combining systems 95 to 97 and a controller 98 of these combined systems 95 to 97. The piping 180 extending downstream independently from each additive combination unit 170 of each of the first to third additive liquid combination systems 95 to 97 is provided with a three-chamber switching valve 179b described later, And is connected to a pipe 55 connected to the addition nozzle 51 downstream of the three-way switching valve 179b. As described above, by providing a plurality of additive liquid combining systems 95 to 97, it is possible to add a plurality of kinds of additive liquids 99a to 99c to the pure dopes 44, respectively, in accordance with the film type. Although three additive liquid combining systems 95 to 97 are provided in this embodiment, two or more of them may be used.

The first additive liquid combining system 95 is for adding a plasticizer and includes an additive liquid combining unit 170, a metering pump 172 for sending the additive liquid 99a produced in the additive liquid combining unit 170 to the downstream side, And a circulation unit 173. The additive liquid combination unit 170 is connected to the pipe 55 as described above and the plasticizer and solvent supplied from the plasticizer supply unit 174, the solvent supply unit 175, and the supply units 174 and 175 are stirred and mixed A mixing tank 176, and an additive liquid tank 177. The supply units 174 and 175 are connected to respective additive tanks or solvent tanks (not shown), and additive or solvent is metered and supplied to the mixing tank 176. The mixing tank 176 prepares the additive liquid 99a by adding a plasticizer to the solvent in a predetermined amount in accordance with the type of the TAC film. The plasticizer concentration of the additive liquid 99a is, for example, 25% by weight and the viscosity is 10 MPa · s. The plasticizer concentration is preferably used in the range of 10 wt% or more and 65 wt% or less. Further, the plasticizer viscosity is preferably used in the range of 10000 MPa s or less.

The second additive liquid combining system 96 prepares an additive liquid 99b obtained by mixing a UV agent and a solvent. Further, the third additive liquid combination system 97 is prepared by adding an additive liquid 99c obtained by mixing a retardation control agent and a solvent. These second and third additive liquid combining systems 96 and 97 are configured in the same manner as the first additive liquid combining system 95.

The kind and amount of various additives such as a plasticizer, a UV agent, a retardation control agent and a matting agent to be added to the Pure dop 44 are determined in advance for each type of film to be produced, and a combination lookup table memory (combination LUT) 167 And is stored in the controller 98. The controller 98 obtains the type and amount of the additive to be added from the combination LUT 167 according to the film type. Then, the additive liquids 99a to 99c are prepared in the additive liquid combining section 170 based on the kind and amount of the obtained additive. The prepared additive liquids 99a to 99c are stored in the respective additive liquid tanks 177.

Each of the circulation units 173 is constituted by a circulation pipe 178 and three-way switching valves 179a and 179b for circulating the additive liquids 99a to 99c upstream of the connection unit of the pipe 55 and the pipe 180 . The circulation piping 178 is connected to the piping 180 connecting the additive liquid combination unit 170 and the pump 172. The connection unit is provided with a three-way switching valve (hereinafter referred to as an inlet-side three-way switching valve) 179a. That is, the inlet-side three-chamber switching valve 179a is provided in the pipe 180 between the additive liquid combination section 170 and the pump 172. [ The pipeline extending downstream from the first additive liquid mixture system 95 and provided with the pump 172 is connected to the piping 55 as described above and is connected to the circulation piping 178 Branch. The above-described three-room switching valve (hereinafter referred to as an outlet-side three-room switching valve) 179b is provided at this branching portion.

These three valves on the inlet side three-way switching valve 179a and the outlet side three-way switching valve 179b are separately opened and adjusted. This opening adjustment also includes switching of the opening and closing, and switching of the opening and closing switches the flow paths of the additive liquids 99a to 99c, respectively. For example, when the outlet-side three-chamber switching valve 179b closes only the valve on the circulation pipe 178 side, the additive liquids 99a to 99c of the additive liquid combination section 170 do not flow into the circulation pipe 178, 55 to the addition nozzle 51. When the outlet side three-chamber switching valve 179b closes only the valve on the side of the connection portion with the pipe 55, the additive liquids 99a to 99c flow into the circulation pipe 178 without being sent to the additive nozzle 51 , Flows to circulate the pipe 180 extending from the additive liquid combination section 170 to the downstream side and the circulation pipe 178 branching therefrom. When a predetermined valve of the inlet-side three-chamber switching valve 179a and the outlet-side three-chamber switching valve 179b is opened, the flow rate and pressure of each of the additive liquids 99a to 99c flowing by adjusting the opening degree Respectively.

Each of the three-chamber switching valves 179a and 179b switches the opening degree of the valve based on the switching timing signal when the next new kind of switching timing signal is inputted. By this switching, the additive liquids 99a to 99c used in the new varieties flow into the circulation piping 178 at a predetermined flow rate prior to the addition timing, and the additive liquid 99a to 99c is circulated through the circulation piping 178 and the piping 180 99a to 99c) is started. Thereafter, when the predetermined timing is reached, the opening degrees of the respective valves of the three-chamber switching valves 179a and 179b are changed again, so that the additive liquids 99a to 99c to be sent to the additive nozzle 51 are supplied at a predetermined flow rate And flows into the pipe 55. In this manner, the pre-circulation process for circulating the liquid before the addition to the pure dope 44 and the preparation of the additive liquid to be added to the pure dope 44 are carried out. The pre-circulation time is preferably in a range from 120 minutes to 1440 minutes, particularly preferably from 150 minutes to 720 minutes.

In addition, although the pre-circulation time is set to 120 minutes so as to start circulation 120 minutes before the start timing signal, and the pre-circulation process is performed before the addition, the pre-circulation time Was varied from 60 minutes to 300 minutes. As a result, it was found that when the content of the additive was less than 120 minutes, the additive did not become homogeneous, and the product had some unevenness. On the other hand, if it exceeds 240 minutes, the product phase is not particularly problematic, but it can not be said to be a desirable value from the viewpoint of the process cost and the like because it is an excessive operation time. Therefore, the pre-circulation time is preferably from 120 minutes to 1440 minutes, particularly preferably from 150 minutes to 720 minutes.

The circulation flow rate in the circulation portion 173 is equal to the flow rate of addition of the additive liquids 99a to 99c. The addition flow rate is set as a flow rate ratio to the pure dop 44. When the addition flow rate of the additive liquid having the additive concentration of 1% is set when the pure dop 44 is 20 L / 200 x 10 < ^-6 > m < 3 > / min) in the circulation unit 173. The additive liquids 99a to 99c are added to the pure dope 44 from the additive nozzle 51 at the same amount as the circulating flow rate by opening the on-off valve by the addition start timing signal to the pure dope 44. In this way, since the pre-circulation process is performed at the same flow rate as that at the time of addition, the flow rate at the time of the pre-circulation process becomes the same as the flow rate at the time of addition, so that only the valve moves during the switching process from circulation to addition. Therefore, pulsation does not occur, and the adjustment time of the additive switching for suppressing the occurrence of pulsation becomes unnecessary. On the other hand, in the case of the conventional switching process, since the flow rate is adjusted after the addition start timing signal is inputted, the pressure fluctuates and the flow rate also fluctuates. Therefore, the pulsation and the pressure fluctuation are large, and the adjustment time until stabilization is long. During this adjustment time, since the soft doping is not reached to the content of the additive necessary for the product, the film due to the soft dope between these products can not be made into a product, which is a waste. In the present invention, since the adjustment time becomes unnecessary, the loss time is reduced by that much, and the waste of the flexible dope is reduced.

Other additive liquid mixture systems 96 and 97 are similarly constructed, and the same constituent members are denoted by the same reference numerals. The circulation unit 173 constitutes the circulation unit 173 in a state in which the opening and closing valve 57 is closed until the addition of the additive liquids 99a to 99c newly added to the pure dope 44 is started, The additive liquids 65a to 65c are circulated in the liquid supply line 173 and are waiting.

The cleaning liquid supply portion 182 is connected to the circulation portion 173 through an opening / closing valve 181. [ The cleaning liquid supply unit 182 sends the solvent, which is a cleaning liquid, to the circulation unit 173 at the time of kind switching, and cleans the additive liquid supplied first. The cleaning liquid after cleaning is discharged from the addition nozzle 51, and the cleaning liquid from the additive liquid supply portion 93 to the addition nozzle 51 is cleaned. After cleaning, each of the additive liquid combination systems 95 to 97 closes the on-off valve 57, and then new additive liquids 65a to 65c for the next kind of liquid are fed and circulated in the circulation unit 173. In addition, the film obtained by soft dope during the kind switching operation in which the cleaning liquid is discharged from the addition nozzle 51 is not added with a predetermined additive amount, and is excluded from the product. As described above, in the kind switching of the film 106, the additive liquids 99a to 99c added to the film 106 before the switching and the additive liquid 99a added to the film 106 after switching To 99c) are cleaned with a cleaning liquid.

The addition nozzle 51 is the same flat nozzle as the first embodiment. After the additive liquids 99a to 99c are uniformly added to the pure dope 44 by the static mixer 52, foreign matter is removed from the pure dope 44 by the second filter 53 as in the first embodiment And becomes the soft dope 54. [ The flexible dope 54 is sent to the flexible die 107 (see Fig. 2) of the film-forming unit 13.

In the fourth embodiment, similarly to the first embodiment, necessary additives are supplied to the pure dope 44 to which the additive is not added by the additive liquid supply part 93 and the additive nozzle 51 So it can respond quickly to new varieties.

In the additive liquid combination unit 170, various additives necessary for the variety to be produced from the combination LUT 167 are specified. These specific additives are added to the solvent 27 by a necessary amount and mixed, and the additive liquids are combined.

In this way, when the flexible dope 54 containing different additives is produced by switching to one solution-depositing equipment 90, it is only necessary to change the kind of the additive liquids 99a to 99c and the addition amount thereof, , It is possible to shorten the section in which the previous dope is replaced by the new dope in the dope switching of the old and new dope.

In the fourth embodiment, the addition nozzle 51 is disposed at a position where the piping capacity C2 is 1/280 to 1/7 of the conventional piping capacity C1 on the downstream side in the type switching . Therefore, as in the first to third embodiments, the loss of the dope can be reduced to about 1/280 to 1/7 of that of the conventional equipment.

An on-line component system may be provided on the outlet side of the additive liquid tank 177 so as to be the same as the outlet side of the additive liquid tank 65 (see FIG. 1) to measure whether or not the additive component of the additive liquid is within a predetermined range good. In this case, the amount of various additives in the mixing tank 176 is increased or decreased according to the measurement result, and various additive components are controlled within a predetermined range.

The additive adding unit 92 is provided with the second filter 53 similarly to the additive adding unit 12 of the first embodiment. The second filter 53 filters the pure dope 44 added with the additive liquids 99a to 99c on the upstream side of the flexible die 107 before it is supplied to the softening. As a result, the soft dope 54 in the third embodiment is further removed from impurities.

In the continuous production of the film 106, when the types and amounts of the various additives are changed to carry out the kind switching, the additive adding unit 92 switches from the old additive to the new additive in a state in which the flexibility is continuously maintained. First, when the type switching information is sent from the master controller (not shown) to the controller 98 of the additive adding unit 92, the controller 98 prepares the additive liquids 99a to 99c corresponding to the new variety. Further, the controller 98 switches the additive liquid added to the pure dope 44 at this switching timing by inputting the kind switching timing signals of the additive liquids 99a to 99c corresponding to the old varietals among the supplied kind change information The additive liquids 65a to 65c of the old varieties are discharged and cleaned, and the additive liquids 65a to 65c of the new varietals are circulated. The three-way switching valves 179a and 179b are switched again by the type switching timing signal to stop the circulation and the switching valve 57 provided in the pipe 55 extending to the addition nozzle 51, And the additive liquid of the new variety is added from the additive nozzle 51 into the Pure dope 44. [

Further, in the fourth embodiment, various additive liquids 99a to 99c are added to the pure dope 44 by using one additive nozzle 51. Alternatively, as shown in Fig. 6, The additive adding unit 187 may be used in which the additive liquid is added at different positions to the pure dope 44 by using the four additive nozzles 185a to 185d. In the case of the fifth embodiment, the additive liquid supply units 186a to 186d are provided for each of the additive liquids. The additive liquid supply units 186a to 186d are configured similarly to the additive liquid supply unit 93 of the fourth embodiment, but the additive liquid additive system has only one system corresponding to each additive. Further, a plurality of additive liquid supply portions 93, which can supply the plural kinds of additive liquids of the fourth embodiment, may be used as the additive liquid supply portions 86a to 86d. 6, the same components as those of the first to fourth embodiments are denoted by the same reference numerals as those in Figs. 1 to 5, and redundant description is omitted.

The solution film-forming equipment 210 of the sixth embodiment shown in Fig. 7 comprises a pure doping unit 11, an additive adding unit 212, and a film-forming unit 13. In Fig. 7, the same constituent members as those of the first to fifth embodiments are denoted by the same reference numerals as those in Figs. 1 to 6, and redundant description is omitted.

The pure dope 44 stored in the stock tank 43 of the storage section 18 is sent to the additive adding unit 212 by the pump 45. The additive adding unit 212 includes the first to fourth additive liquid supply units 247 to 250, the additive nozzles 51a to 51d, the static mixer 52, the second filter 53, and the controller 258 have. A check valve 56 and an on-off valve 57 for preventing the backflow of the additive liquids 261a to 261d are provided in the piping 255 for feeding the additive liquids 261a to 261d to the additive nozzles 51a to 51d have.

The first additive liquid supply portion 247 is for adding a plasticizer and includes an additive liquid combination portion 170 and a liquid delivering portion 251 for sending the additive liquid 261a from the additive liquid combination portion 260 to the additive nozzle 51a. (Not shown). The liquid delivery section 262 is composed of a pump 263, a pipe 264, and a circulation section 265.

The additive liquid combination unit 170 is the same as that in the fourth embodiment shown in Fig. 5 and is provided with a plasticizer supply unit 174, a solvent supply unit 175, and a plasticizer and a solvent supplied from the respective supply units 174, A mixing tank 176 for mixing and an additive liquid tank 177 are provided. The plasticizer concentration of the additive liquid 261a adjusted by the mixing tank 176 is, for example, 25% by weight and the viscosity is 10 MPa · s. The plasticizer concentration is preferably used in the range of 10 wt% or more and 65 wt% or less. Further, the plasticizer viscosity is preferably used in the range of 10000 MPa s or less.

The circulation unit 265 is composed of a circulation pipe 268 and three-chamber switching valves 266 and 267. A cleaning liquid supply unit 270 is connected to the circulation pipe 268 through an on-off valve 269. [ The inlet-side three-chamber switching valve 266 is provided in a pipe 264 connecting the additive liquid combination section 170 and the pump 263. And the outlet-side three-chamber switching valve 267 is provided in the liquid delivery pipe 255 of the first additive liquid supply portion 247. Each of the three-chamber switching valves 266, 267 switches the opening degree of the valve based on this switching timing signal in the same manner as in the fourth embodiment, when the following new kinds of switching timing signals are input. By this switching, the additive liquids 261a to 261d used in the new varieties are subjected to the pre-circulation process to the predetermined flow rate prior to the addition timing. Thereafter, when the predetermined timing is reached, the opening degrees of the respective valves of the three-chamber switching valves 266 and 267 are changed again so that the additive liquids 261a to 261d to be added to the pure dope 44 are supplied to the additive nozzles 51a to 51d. In this manner, the additive liquids 261a to 261d are prepared and pre-circulated. The pre-circulation time is preferably in a range from 120 minutes to 240 minutes, particularly preferably from 150 minutes to 210 minutes.

The circulation flow rate in the circulation section 265 is equal to the addition flow rate of the additive liquid 261a. If the flow rate is added is set as the flow rate of the pure dope 44, a pure dope 44 is added to the flow rate of the additive solution of 1% is set, when 20L / min, the 200㏄ / min (= 200 × 10 ^{- 6} < RTI ID = 0.0 > m3 / min). ≪ / RTI > Then, the opening / closing valve is opened by the addition start timing signal to the pure dope 44, and the additive liquid 261a is added from the addition nozzle 51a in the same amount as the circulating flow rate. As described above, in the sixth embodiment, since the atmospheric circulation operation is performed at the same flow rate to be added, the flow rate in the atmospheric circulation operation becomes equal to the flow rate in the addition, so that only the valve do. Therefore, pulsation does not occur, and the adjustment time of the additive switching for suppressing the occurrence of pulsation becomes unnecessary. Therefore, the loss time is reduced by the extent that the adjustment time becomes unnecessary, and the waste of the flexible dope is reduced.

However, when the addition amount of the additive liquid 261a is less than the flow rate of the Pure Dope 44, it takes a long time to wait until the predetermined pressure is reached even if it is changed at a predetermined timing after the circulation as described above , The switching time becomes longer as compared with the usual addition. If switching takes a long time, efficient switching becomes impossible. Further, during the switching time, since the soft doping is not reached to the content of the additive necessary for the product, the film due to the soft dope between the films can not be a product, which is a waste. This manufacturing time loss or product loss is larger as the addition amount of the additive liquid 261a is smaller with respect to the flow rate of the pure dop 44.

Therefore, in the sixth embodiment, in order to shorten the adjustment time when a small amount is added, when the addition amount of the additive liquid in the kind switching is not more than a predetermined amount ("A" in FIG. 8) (QAE / QD) × 100} (unit%), which is the flow rate of the added flow rate (target value) (QAE) of the additive liquid to be switched to the new varieties with respect to the flow rate QD of the dope, (QAE) of not less than 1.5 times and not more than 3.0 times the added flow rate (QAE) when the added flow rate (QAE) is 300 × 10 ^-6 m 3 / min For a certain period of time. Then, after a predetermined time elapses, the flow rate is set as the target value QAE from the QAS. If the initial addition flow rate QAS is less than 1.5 times the addition flow rate QAE, the effect of shortening the time is small and if the addition flow rate QAE is more than 3.0 times, pulsation is generated when returning to the target addition flow rate It is necessary to use a pump having a large capacity of the liquid delivery pump. In this way, it is sufficient to carry out increase addition to flow the additive liquid at a flow rate larger than the target additive flow rate QAE, and to reduce the flow rate to the target additive flow rate QAE after a predetermined time has elapsed.

The predetermined time is a period of time until the pressure of the additive liquid 261a at the outlet of the additive nozzle 51a becomes equal to the pressure of the Pure dope 44 near the outlet of the additive nozzle 51a It is time. This time may be stored in the LUT memory 258a for each additive liquid in a representative value determined in advance by experiments or the like, and the increase addition may be performed based on the stored time. Instead of using a representative value stored in advance, the pressure of the additive liquid 261a is measured by a pressure gauge provided in the vicinity of the outlet of the addition nozzle 51a as in the seventh embodiment shown in Fig. 9, The predetermined time may be changed based on the measured pressure value. When the pressure value of the measured additive liquid 261a becomes equal to the pressure of the Pure dope 44 in the vicinity of the outlet of the addition nozzle 51a, the predetermined time is changed based on the measured pressure value, The increase addition is terminated irrespective of the above-mentioned predetermined time.

The "fixed time" for performing the increase addition is the time until the pressure of the additive liquid 261a at the outlet of the addition nozzle 51a becomes equal to the pressure of the pure Dope 44 . However, even if the flow rate setting of the additive liquid 261a is changed from the initial addition flow rate QAS to the addition flow rate QAE, the pressure at the outlet of the addition nozzle 51a of the additive liquid 261a immediately at the time of changing the flow rate It is difficult to make the time difference to 0 (zero) because a time difference occurs when the flow rate setting is changed and when the rising pressure becomes constant. For example, in such a case, the time difference may be taken into account to increase the amount of increase in the pressure before reaching the same pressure as the pressure of the Pure dope 44 in the vicinity of the outlet of the addition nozzle 51a, The addition may be terminated. That is, the predetermined time may be shorter than the time required for the pressure of the additive liquid 261a to reach the same pressure as the pressure of the Pure Dop 44, depending on the time difference or the like.

Since the amount of the additive liquid added for each kind is previously obtained and stored in the LUT memory 258a, there is no need for the operator to input the flow rate of the additive liquid of the various additive liquids, I will not. For this reason, in the case of the set value error, the dope of the set value miss section is unnecessary, but this waste can be eliminated.

If the added flow rate {(QAE / QD) x 100} of the additive flow rate QAE of the additive liquid to be switched to the new varieties with respect to the flow rate QD of the pure dope 44 as the reference dope exceeds 10% It is not necessary to carry out the circulation treatment or the increase addition treatment at the initial addition flow rate QAS as described above, and the circulation is performed at the addition flow rate QAE for a certain period of time. The predetermined time is obtained in advance by experiment, simulation or the like, and stored in the LUT memory 58a of the controller 258. [ By this circulation processing, as described above, it is possible to reduce the doping time (loss time) in the state where the additives are mixed during the switching in the kind switching, and the waste of the soft doping is reduced.

The LUT memory 258a stores kinds and amounts of various additives such as a plasticizer, a matting agent, a UV agent, and a retardation control agent to be added to the Pure dope 44 in addition to the predetermined time. The types and amounts of these various additives are determined in advance for each type of the film 106 to be produced. The controller 258 obtains the type and amount of the additive corresponding to the film type from the LUT memory 258a. Then, the additive liquids 261a to 261d are prepared in the additive liquid combining section 170 based on the kind and amount of the obtained additive. The prepared additive liquids 261a to 261d are stored in the respective additive liquid tanks 177. Also, the presence or absence of the incremental addition processing, the increase ratio at the time of the incremental addition processing, and the like are previously determined by experiments and stored in the LUT memory 258a.

The other second to fourth additive liquid supply units 248 to 250 are also configured similarly to the first additive liquid supply unit 247, and a detailed description thereof will be omitted. The second additive liquid supply unit 248 supplies an additive liquid 261b prepared by mixing a matting agent and a solvent. The third additive liquid supply unit 249 supplies an additive liquid 261c obtained by mixing a UV agent and a solvent. Further, the fourth additive liquid supplier 250 prepares an additive liquid 261d obtained by mixing a retardation control agent and a solvent.

Thus, by providing a plurality of additive liquid supply portions 247 to 250 for the necessary additives, it is possible to add a plurality of kinds of additive liquids 261a to 261d to the Pure Dope 44, respectively, have. In the present embodiment, four additive liquid supply units 247 to 250 are provided, but they may have as many as necessary.

The circulation unit 265 circulates and waits by the three-way switching valves 266 and 267 and the circulation pipe 268 until addition of the newly added additive liquids 261a to 261d to the Pure Dope 44 is started.

The circulation unit 265 is connected to a cleaning liquid supply unit 270 through an on-off valve 269. [ The cleaning liquid supply unit 270 sends the solvent to the circulation unit 265 at the time of type switching, and cleans the additive liquid supplied first. The cleaning liquid after cleaning is discharged from the addition nozzle 51a, and the cleaning liquid from the first additive liquid supply portion 247 to the addition nozzle 51a is cleaned. After the cleaning, the additive liquid combination unit 170 closes the on-off valve 57, and then delivers new additive liquids 261a to 261d for the next variety and circulates in the circulation unit 265. In addition, the film obtained by the soft dope during the type switching operation of the three semen discharged from the addition nozzle 51a is not made into a predetermined amount of the additive, and is excluded from the product.

The other second to fourth additive liquid supply units 248 to 250 are also configured similarly to the first additive liquid supply unit 247, and a detailed description thereof will be omitted. The second additive liquid supply unit 248 supplies an additive liquid 261b prepared by mixing a matting agent and a solvent. The third additive liquid supply unit 249 supplies an additive liquid 261c obtained by mixing a UV agent and a solvent. Further, the fourth additive liquid supplier 250 prepares an additive liquid 261d obtained by mixing a retardation control agent and a solvent.

Thus, by providing a plurality of additive liquid supply portions 247 to 250 for the necessary additives, it is possible to add a plurality of kinds of additive liquids 261a to 261d to the Pure Dope 44, respectively, have. Although four additive liquid supply units 247 to 250 are provided in the present embodiment, they may be increased or decreased as appropriate.

The addition nozzles 51a to 51d are the same flat nozzles as the addition nozzle 51 of the first embodiment in which the tip ends are flatly crushed. The additive nozzles 51a to 51d are arranged in the dope pipe 46 in such a manner that the tip end flat portion is aligned with the diameter direction of the dope pipe 46. [ The static mixer 52 disposed on the downstream side of the addition nozzles 51a to 51d is provided with a plurality of elements 52a formed by twisting the rectangular plate by 180 degrees in series in the piping so that the addition nozzles 51a to 51d ) Are dispersed and mixed. The foreign matter is removed from the Pure dope 44 via the static mixer 52 by the second filter 53 to become the flexible dope 54. [ The flexible dope 54 is sent to the flexible die 107 (see Fig. 2) of the film forming unit 13.

In the sixth embodiment, since the necessary additive is supplied by the additive liquid supply portions 47 to 50 and the additive nozzles 51a to 51d in accordance with the film type to be produced for the Pure Dope 44 to which the additive is not added, It can respond quickly.

In the additive liquid combination unit 170, various additives necessary for the variety to be produced from the LUT 258a are specified, and these specific additives are added to the solvent 27 by a necessary amount and mixed, and the additive liquids are combined.

As described above, in the sixth embodiment, it is only necessary to change the type of the additive liquid and the amount of addition thereof. As in the present embodiment, it is possible to shorten the section in which the old dope is replaced by the new dope during the dope switching.

The extruded substitution portion becomes a state in which the new and the old dope are mixed. Even in the sixth embodiment, addition nozzles 51a to 51d are disposed at positions where the piping capacity C2 is 1/280 to 1/7 of the conventional piping capacity C1 on the downstream side in the type switching . Therefore, the film portion in which the old and new additives are mixed is about three times as large as the piping capacity after the addition nozzle, and the loss of the dope can be suppressed to about 1/280 to 1/7 of that of the conventional equipment.

Also in the sixth embodiment, an on-line component system may be provided on the outlet side of the additive liquid tank 177 to determine whether the additive component of the additive liquid is within a predetermined range. Depending on the measurement result, the amount of various additives in the mixing tank 76 may be increased or decreased, and various additives may be controlled within a predetermined range.

The additive adding unit 212 is provided with the second filter 53 in the same manner as the additive adding unit 12 of the first embodiment. The Pure Dope 44 to which the additive liquids 261a to 261d are added on the upstream side of the flexible die 107 is filtered by the second filter 53 before being softened. As a result, the soft doping 54 in this embodiment is further removed from impurities.

In the continuous production of the film 106, when the kinds and amounts of the various additives are changed to carry out the kind switching, the additive adding unit 212 switches from the old additive to the new additive in a state where the flexibility is continuously maintained. First, when the type switching information is sent from the master controller (not shown) to the controller 258 of the additive adding unit 212, the controller 258 controls each unit to prepare the additive liquids 261a to 261d corresponding to the new variety . The additive liquids 261a to 261d corresponding to the old varieties are discharged and cleaned of the additive liquids 261a to 261d of the old breeds so as to be switched at the switching timing by inputting the type switching timing signal, (261a to 261d). Then, the three-way switching valves 266 and 267 are switched to stop the circulation, the open / close valve 57 is opened, and the additive liquid of the new variety is supplied from the additive nozzles 51a to 51d during the pure dope .

In the fifth embodiment, various additive liquids 261a to 261d are added to the pure dope 44 by using the additive nozzles 51a to 51d provided corresponding to the additive liquid feed units 247 to 250 However, instead of this, an additive adding unit may be used in which the additive liquid is added to the pure dop 44 at the same position, for example, by using one additive nozzle.

In the sixth embodiment, it is determined whether or not the time for adding the increase amount by the initial addition amount of flow QAS has reached a predetermined time previously determined, and after the elapse of a predetermined time, the initial addition amount QAS is changed from the addition amount QAE However, the timing of this change is the same as in the seventh embodiment shown in Fig. 9, in which the pressure near the exit of the addition nozzle is detected by the pressure sensor, and the detection pressure Pa is, for example, 90 %, It may be changed from the initial addition flow rate (QAS) to the addition flow rate (QAE).

The solution film-forming equipment 310 of the eighth embodiment shown in FIG. 10 includes a pure doping unit 11, an additive adding unit 312, and a film-forming unit 13. In Fig. 10, the same components as those in Figs. 1 to 10, which are the first to seventh embodiments, are denoted by the same reference numerals, and a description thereof will be omitted.

The pure dope (reference dope) 44 stored in the reservoir tank 43 of the reservoir portion 18 is sent to the additive adding unit 312 by the pump 45. The additive adding unit 312 includes a dope pipe 46 through which the pure dope 44 flows, first to fourth additive liquid supply units 247 to 250 as in the sixth embodiment, addition nozzles 51a to 51d, A mixer 352, a second filter 53, and a controller 358. Check valves 56 and 57 for preventing the backflow of the additive liquids 261a to 261d are installed in the respective pipes 355 for feeding the additive liquids 261a to 261d to the additive nozzles 51a to 51d .

Like the LUT memory 258a in Fig. 7, the LUT memory 358a stores the amount of additive liquid added for each type in advance.

The circulation processing time before addition of the additive liquid is obtained by experiment or simulation beforehand, and these are stored in the LUT memory 358a of the controller 358. [ By this circulation processing, as described above, it is possible to reduce the doping time (loss time) in the state where the additives are mixed during the switching in the kind switching, and the waste of the soft doping is reduced.

In addition to the predetermined time, the LUT memory 358a stores kinds and amounts of various additives such as a plasticizer, a matting agent, a UV agent, and a retardation control agent to be added to the Pure dop 44. The kinds and amounts of these various additives are determined in advance for each type of film to be produced. The controller 358 obtains the type and amount of the additive corresponding to the film type from the LUT memory 358a. Then, the additive liquids 261a to 261d are prepared in the additive liquid combining section 170 based on the kind and amount of the obtained additive. The prepared additive liquids 261a to 261d are stored in the respective additive liquid tanks 177. The presence or absence of the incremental addition processing, the increase ratio at the time of the incremental addition processing, and the like are previously determined by experiments and stored in the LUT memory 358a.

The other second to fourth additive liquid supply units 248 to 250 are also configured similarly to the first additive liquid supply unit 247, and a detailed description thereof will be omitted. The second additive liquid supply unit 48 prepares an additive liquid 61b obtained by mixing a matting agent and a solvent. The third additive liquid supply unit 49 prepares an additive liquid 61c obtained by mixing a UV agent and a solvent. Further, the fourth additive liquid supply part 50 prepares an additive liquid 61d obtained by mixing a retardation control agent and a solvent.

By providing a plurality of additive liquid supply portions 47 to 50 corresponding to the necessary additive types as described above, a plurality of kinds of additive liquids 61a to 61d are supplied from the additive nozzles 51a to 51d, respectively, Each of the four additive liquid supply units 47 to 50 is provided in the Pure Dope 44 (the dope pipe 46). In this embodiment, four additive liquid supply units 47 to 50 are provided, Line mixers 352 are provided on the downstream sides of the addition nozzles 51a to 51d, respectively.

11 and 12, the addition nozzle 51a has a double piping structure by an inner pipe 380 and an outer pipe 381, and the inner pipe 380 of the additive liquid 61a An outer passage 384 through which the buffer solution 387 flows is formed between the outer circumferential surface and the inner circumferential surface of the outer tube 381. The first additive liquid supply portion 247 is connected to the inner passage 383 of the additive nozzle 51a and the buffer liquid supply portion 385 for supplying the buffer liquid 387 to the outer passage 384 is connected to the outer passage 384, Respectively.

The buffer liquid supply unit 385 includes a solvent supply unit 375 and a liquid delivery pump 386. The liquid supply pump 386 supplies liquid equal to the components of the solvent 27 of the second tank 22 Is supplied to the outer passage 384 as a buffer solution 387. The buffer liquid 388 is supplied to the outer passage 384 to form a buffer liquid layer 389a having a buffer liquid flow 389 at the boundary between the additive liquid 388 and the purge dope 44a. Since the additive liquid 261a and the buffer liquid 387 and the buffer liquid 387 and the pure dop 44 are slightly mixed by the buffer layer 389a, the additive liquid 261a is directly supplied to the pure dop 44 The gelation and the condensation of the additive are not generated as compared with the case of contacting and mixing. Thus, the buffer solution 387 is used to form the buffer solution layer 389a for suppressing the buffer solution of the additive liquid 261a and the pure dop 44 at the time of addition. When the static mixers 392 and 393 (see Fig. 13) of the inline mixer 352 are reached, the pure dope 44, the buffer solution 387 and the additive liquid 261a ) Are mixed and dispersed, so that gelation and aggregation of additives do not occur in the same manner. The distal end portion of the inner tube 380 is formed in a tapered shape in which the diameter of the inner peripheral surface of the circular section is constant in the longitudinal direction while the outer peripheral surface is tapered so that the diameter becomes smaller toward the tip. As a result, the buffer layer 389a is formed more reliably around the additive liquid stream 388.

At this time, in the eighth embodiment, when the flow rate of the additive liquids 388, that is, the flow rate of the additive liquid 261a is QAE and the flow rate of the buffer liquid 389 is QB, the flow rate ratio QB / The flow rate of each of the liquids 388 and 389 is adjusted. This is because when the flow ratio is less than 0.01, the buffering function by the buffer layer 389a is weakened, and as described above, gelation and aggregation of the additives may occur. On the contrary, if the flow rate ratio exceeds 0.1, the concentration of the additive liquid 261a in the pure dop 44 is lowered and the flexibility suitability of the soft doping 54 may be lowered.

The other second to fourth additive liquid supply units 248 to 250 also have double structure addition nozzles 51b to 51d and a buffer liquid supply unit 385 in the same manner. Further, depending on the type of the additive liquid, gelation or condensation may be less likely to occur. In this case, the additive nozzle having a double structure or the buffer supply portion may be omitted. In this case, an additive liquid may be added using a common additive nozzle . The addition nozzles 51 and 51a used in the first to seventh embodiments are also the same as the addition nozzle 51a of the present embodiment.

As shown in Fig. 13, the inline mixer 352 includes a split mixing type static mixer 392 and a salt mixing type static mixer 393. The split mixing type static mixer 392 is installed near the front of each of the addition nozzles 51a to 51d. The split mix type static mixer 392 is provided with elements 394a and 394b which are arranged alternately in the longitudinal direction of the dope pipe 46. [ The elements 394a and 394b are formed so as to be interlaced with each other so as to alternately cross a plurality of thin and long boundary plates. The split mixed static mixer 392 mixes the pure dope 44 and additive liquids 261a to 261d flowing in the dope pipe 46 while dividing them by the elements 394a and 394b.

The tribo-type static mixer 393 is disposed on the downstream side of the split-mixing static mixer 392. The triboelectric static mixer 393 is provided with elements 395a and 395b, which are arranged alternately in the longitudinal direction of the dope pipe 46. [ The elements 395a and 395b are formed by twisting a rectangular plate by 180 °, and the directions of twisting in the elements 395a and 395b are reversed. The elements 395a and 395b are arranged in a state in which they are rotated 90 占 about the axis of the dope pipe 46 so that the side ends of the plate are perpendicular to each other. The triboelectric static mixer 393 mixes the pure dope 44 and the additive liquids 261a to 261d flowing in the dope pipe 46 while converting them by the elements 395a and 395b.

Although the four addition nozzles 51a to 51d and the four inline mixers 352 shown in Fig. 13 are shown at the most upstream addition nozzle 51a and the inline mixer 352 in Fig. 13, And the inline mixer 352 disposed downstream of each of the inline mixers 51b to 51d.

The additive adding unit 312 is also provided with the second filter 53 similarly to the additive adding unit 12 of the first embodiment. The second filter 53 filters the pure dope 44 via the inline mixer 352 on the upstream side of the flexible die 107 before it is supplied to the fusing. As a result, the flexible dope 54 in the eighth embodiment also becomes more impurities removed and is sent to the flexible die 107 (see Fig. 2) of the film-forming unit 13.

In the present embodiment as well, since the necessary additives are supplied to the pure dope 44 to which additives are not added by the additive liquid supply units 247 to 250 and the additive nozzles 51a to 51d, It can respond quickly. In this embodiment, the inline mixer 352 is provided on the downstream side of the addition nozzles 51a to 51d and mixed every time the additive liquids 261a to 261d are supplied. Therefore, the additive liquids 261a- 261d are likely to be uniformly dispersed in the pure dopes 44, respectively.

In the additive liquid combination unit 170, various additives necessary for the variety to be produced from the combination LUT 358a are specified, and these specific additives are added to the solvent 27 by a necessary amount to mix them, and the additive liquids are combined.

In the continuous production of the film 106, when the kinds and amounts of the various additives are changed to carry out the kind switching, the additive adding unit 212 switches from the old additive to the new additive in a state where the flexibility is continuously maintained. First, when the type-switching information is transmitted from the master controller (not shown) to the controller 358 of the additive adding unit 312, the controller 358 controls the respective units to prepare the additive liquids 261a to 261d corresponding to the new- do. The additive liquids 261a to 261d corresponding to the old varieties are discharged and cleaned of the additive liquids 261a to 261d of the old breeds so as to be switched at the switching timing by inputting the type switching timing signal, (261a to 261d). Then, the three-way switching valves 266 and 267 are switched to stop the circulation, the opening / closing valve 57 is opened, and a new kind of additive liquid is supplied from the adding nozzles 51a to 51d .

Also in this embodiment, the additive liquids 61a to 61d are added to the pure dopes by using the additive nozzles 51a to 51d provided in correspondence with the additive liquid supply portions, but instead of this, However, it is also possible to use, for example, an additive adding unit in which the additive liquid is added at the same position to the pure dope by using one additive nozzle. In this case as well, a mixed additive liquid in which a plurality of kinds of additive liquids are mixed in the inner passage is supplied with a double piping structure, and a buffer solution is supplied to the outer passages. Although not shown in the figure, a plurality of additive liquid passages may be formed by, for example, a quadruple piping structure, and the additive liquid may be separately supplied to each of the passages, and the buffer solution may be supplied to the outermost passages.

Further, in the case of adding at the same position, as shown in Fig. 11, an additive may be added to the reference dope (pure dope) by arranging a plurality of addition nozzles having the double pipe structure. Further, a plurality of additives may be added at the same position or at different positions in the passage of the reference dope by using a plurality of addition nozzles having a multiple piping structure.

In the eighth embodiment, the static mixers 392 and 393 are exemplified as the inline mixer 352, but the present invention is not limited thereto and may be a dynamic mixer 420 (see FIG. 14).

14, the dynamic mixer 420 includes a tubular case 421 disposed in the middle of the dope pipe 46, a mixer main body 422 housed in the case 421, a mixer main body 422, And a support member 423 for rotatably supporting the support member 423.

The mixer main body 422 is composed of a conical tip end portion 422a and a cylindrical body portion 422b and is attached to the support member 423 such that the tip end portion 422a thereof is directed upstream in the liquid flow direction. Thereby, a clearance 425 is formed between the inner wall surface of the case 421 and the outer peripheral surface of the mixer main body 422 so as to gradually decrease from the upstream side toward the downstream side in the liquid flow direction. The mixer main body 422 is operated (rotated) by an electromagnet provided at a predetermined pitch on the outer peripheral surface of the case 421 and a magnet built in the torso body 422b, do.

The support member 423 is a substantially cylindrical rotary shaft extending from the downstream side in the liquid flow direction toward the upstream side. The mixer main body 422 is attached to the tip end thereof, and the rear end thereof is fixed to the inner wall surface of the case 421 . The support member 423 is provided with a gap passage 423a communicating with the dope pipe 46 on the downstream side in the liquid flow direction.

The pure dop 44 and additive liquids 261a to 261d sent to the dynamic mixer 420 are divided by the tip end portion 422a of the mixer main body 422 and pass through the gap 425 and the gap flow path 423a, To the dope piping 46 on the side of the dope. At this time, as the mixer main body 422 rotates, the pure dope 44 and the additive liquids 261a to 261d passing through the gap 425 are stirred and mixed.

In the above embodiment, the same liquid as that of the solvent 27 of the reference dope is used as the buffer 387, but the present invention is not limited to this, and the additive liquid may be the same liquid as that of the solvent And a reference DOP diluted solution obtained by diluting the reference dope with the same solution as that of the solvent may be used as the buffer solution 387. [ The same liquid as the component is a single component when the solvent 27 is composed of a single component and at least one of plural components when the solvent 27 is composed of a plurality of components. In the above embodiment, the additive nozzle having a substantially circular sectional shape is taken as an example. However, the present invention is not limited to this. For example, a flat nozzle such as a long nozzle extending in the radial direction of the dope pipe 46 And nozzles of various shapes may be used.

Also in the fourth to eighth embodiments, the additive liquid is added to the pure dope 44 immediately before the flexible die 107. However, the dope is not limited to the pure dope 44, A flexible dope containing various additives in the dope may be used. In this case, a film of a new variety can be similarly produced by adding an additive immediately before the flexible die. Various additives are mixed in the same manner when the polymer (26) and the solvent (27) are mixed in the mixing section (15) in Fig.

It is also possible to add a common additive in mixing the polymer 26 and the solvent 27 in the mixing portion 15 in Figs. 5, 7, and 10 instead of the pure doping 44 and the conventional soft doping And may be mixed to form a reference dope for negotiation. When the polymer 26 and the solvent 27 are solubilized in advance, only the additive commonly required in the respective varieties is dispersed and prepared. In this case, the amount of the additive to be added immediately before the flexible die, that is, the amount immediately before the flexible die can be reduced by the amount of the common additive, thereby enabling efficient addition.

Although the fourth to eighth embodiments have been described by taking the single layer flexible as an example, they may be shared as in the case of the first to third embodiments.

The static mixer 52 of the first to seventh embodiments may be any one of the split mixing type static mixer 392 and the salt-mixing type static mixer 393 in the eighth embodiment, or a combination thereof. The static mixer 52 may be replaced by a dynamic mixer 420 instead.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples. However, the present invention is not limited to these examples.

[Example 1]

The following polymer 26 and solvent 27 were mixed in a dissolution tank 23 to prepare a pure dop 44. As the solvent (27), a so-called mixed solvent obtained by mixing dichloromethane, methanol and 1-butanol was used.

[Polymer]

100 parts by weight of cellulose triacetate

[Mixed solvent]

320 parts by weight of dichloromethane

Methanol 83 parts by weight

1-butanol 3 parts by weight

In the additive adding unit 12, the above-mentioned mixed solvent and the additive were mixed to constitute the additive liquid (A), and this additive liquid was added to the pure dope 44 by the additive nozzle 51.

[Additive liquid (A)]

80 parts by weight of a mixed solvent

Plasticizer A 7.6 parts by weight

Plasticizer B 3.8 parts by weight

UV a 0.7 part by weight

UV b 0.3 parts by weight

Citric acid ester mixture 0.006 part by weight

Fine particles 0.05 part by weight

The additive liquid (B) when switching film varieties is as follows.

[Additive liquid (B)]

80 parts by weight of a mixed solvent

Plasticizer C 6 parts by weight

Plasticizer D 6 parts by weight

UV a 0.7 part by weight

UV b 0.3 parts by weight

Citric acid ester mixture 0.006 part by weight

Fine particles 0.05 part by weight

The above-mentioned cellulose triacetate was a powder having a degree of substitution of 2.84, a viscosity average degree of polymerization of 306, a water content of 0.2% by weight, a viscosity of 6% by weight in a dichloromethane solution of 315 mPa.s, an average particle diameter of 1.5 mm and a standard deviation of 0.5 mm, A is triphenyl phosphate, plasticizer B is diphenyl phosphate, UV a is 2 (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, UV b is (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) -5-chlorobenzotriazole, the citric acid ester compound is a mixture of citric acid, monoethyl ester, diethyl ester and triethyl ester, The fine particles are silicon dioxide having an average particle diameter of 15 nm and a Mohs hardness of about 7. Further, at the time of preparing the pure dop 44, a retardation control agent (N-N'-di-m-tolyl-Np-methoxyphenyl-1,3,5-triazine- Amine) was added in an amount of 4.0% by weight based on the total weight of the film.

Subsequently, by using the flexible dope 54 from which the foreign substance is removed by the second filter 53 of the solution film-forming equipment 10 shown in Fig. 1, the film forming unit 13 shown in Fig. Each step was performed to obtain a TAC film 106.

The piping capacity C1 of the entire process from the dissolution tank 23 to the inlet of the flexible die 107 of the film forming unit 13 is 56000 liters and the flexible die 107 is moved from the addition position by the addition nozzle 51, The piping capacity C2 to 8000L is 8000L. The additive liquid (A) was added to the additive nozzle (51) and then mixed inline with the static mixer (52). When switching from the film of the type A using the additive liquid A to the pure dop 44 to the film of the type B using the additive liquid B from the pure dop 44 to the film of the type B using the additive liquid A, ) To the additive liquid (B). The time required for breed switching was 6 hours.

[Comparative Example 1]

Comparative Example 1 is a case where the additive liquid A is changed from the additive liquid A to the additive liquid B in the dissolving tank 23 in the same manner as in the conventional equipment in place of the addition just before the flexible die 107 in Example 1, Was the same as that in Example 1. The piping capacity C1 is 56000 L and it takes 42 hours to make the flexible dope of the product B from the flexible dope of the product A while the additive liquids A and B are mixed therewith, About three times more flexible dope could not be used as a product, resulting in product loss.

[Example 2]

In order to obtain the film 106 of the cultivar A, the solution film-forming equipment 90 shown in Fig. 5 and the film forming equipment shown in Fig. 2 were used at a dope flow rate of 20 L / min, immediately before the plasticizer addition rate of 2% The film 106 was produced by the unit 13. (= 400 x 10 < 4 > / minute (= 400 cc / min) of the additive liquid 99a in which the additive liquid 99a containing the plasticizer was added at the same rate as the additive ratio before 120 minutes before the addition was performed immediately before ^-6 m < ³ > / min). In addition, and to the atmosphere by the liquid additive (99b) UV I entered the addition rate and a tie additive solution flow rate [200㏄ / min ^{(= 200 × 10 -6 ㎥ /} min)] in circulation. The addition start timing signal is received and the additive liquid is added from the additive nozzle 51 to the Pure dope 44 by switching from circulation to addition. Was added without causing a change in flow rate after the start of the addition operation. That is, since the atmospheric circulation operation is performed at the same flow rate to be added, the flow rate in the atmospheric circulation operation becomes equal to the flow rate in the addition, so that only the valve moves during the switching process from circulation to addition. Therefore, pulsation does not occur, and the adjustment time of the additive switching for suppressing the occurrence of pulsation becomes unnecessary. In the case of the conventional switching process, since the flow rate is adjusted after the addition start timing signal is inputted, the pressure also fluctuates, and the flow rate also fluctuates. Therefore, the pulsation and the pressure fluctuation are large, and the time (adjustment time) until stabilization takes a long time to cause the loss, which can be solved. In Example 2, the time for preventing pulsation at the time of addition and the time for adjusting the additive were not necessary, and the loss time until reaching the target amount of addition which could be made into a product was 300 minutes, which was about 20% lower than in Example 4 described later.

[Example 3]

In order to obtain the film 106 of the variant B, the dope flow rate was 20 L / min, the addition rate of the plasticizer immediately before the addition was 2%, the addition rate of the UV product was 1.1%, and the addition rate of the retardation control agent was 5% A film 106 was produced. (= 400 x 10 < 4 > / minute (= 400 cc / min) in which the additive liquid 65a containing the plasticizer was added at the same rate as the additive ratio before 120 minutes before the immediately preceding addition ^-6 m < ³ > / min). Further, the additive liquid 65b containing the UV agent was circulated in the additive liquid flow rate [220 cc / min (= 220 x 10 ^-6 m < 3 > / min)] Further, the additive liquid 65c containing the retardation control agent was circulated at an additive liquid flow rate of 1,000 cc / min (= 1000 x 10 ^-6 m / min) with the addition ratio equal to the addition ratio. The addition start timing signal is received and the additive liquid is added from the additive nozzle 51 to the Pure dope 44 by switching from circulation to addition. Was added without causing a change in flow rate after the start of the addition operation. The time for preventing the pulsation and the time for adjusting the additives at the time of addition were not required, and the loss time until reaching the target addition amount that can be the product was 300 minutes, which was about 20% lower than that of Example 4 described later.

[Example 4]

In order to obtain a film of the same kind A as in Example 2, the solution film-forming equipment 90 shown in Fig. 5 and the film-forming equipment 90 shown in Fig. 2 were used at a dope flow rate of 20 L / min, immediately before the addition rate of plasticizer of 2% Film forming unit 13 shown in Fig. C2 / C1 is 1/280. The additive liquid 65a containing the plasticizer is added at an additive liquid flow rate of 200 cc / min (= 200 x 10 < ^-6 > / min / min )] And added to the pure dop 44. The additive liquid 65b containing the UV agent was added to the Pure dope 44 at an additive liquid flow rate of 100 cc / min (= 100 x 10 ^-6 m < ³ > / min) In Embodiment 4, as in Embodiments 2 and 3, the circulation process of the additive liquid is not performed immediately before the switching, and the flow rate is adjusted after the addition start timing signal is input, so that the pressure also fluctuates and the flow rate also fluctuates. Because of this, the pulsation and the pressure fluctuation are large, and the time (adjustment time) until stabilization is long. Since the dope during this adjustment time has not reached the prescribed additive addition ratio, it can not become a product and causes loss. The loss time in Example 4 was 360 minutes.

[Example 5]

In order to obtain a film of the same kind A as in Example 2, the solution film-forming equipment 90 shown in Fig. 5 and the film-forming equipment 90 shown in Fig. 2 were used at a dope flow rate of 20 L / min, immediately before the addition rate of plasticizer of 2% Film forming unit 13 shown in Fig. Just before the addition of (C2 / C1 = 1/280 in the timing of the addition) before (110 minutes ago) to the plasticizer containing the additive liquid (65a), the addition ratio and other additive solution flow rate [200㏄ / min (= 200 × 10 ^-6 Lt; 3 > / min) (about half of the flow rate of Example 2)). The additive liquid 65b containing the UV agent was circulated using the additive liquid flow rate [100 cc / min (= 100 x 10 ^-6 m 3 / min) (flow rate about half of Example 2) I waited. And the additive liquid was added to the dope from the additive nozzle 51 by switching from circulation to addition. Since the circulation process is performed up to the half of the flow rate of the first embodiment as compared with the fourth embodiment, the adjustment time can be shortened as compared with the fourth embodiment. However, since the pulsation and the pressure fluctuation are larger than those in the second embodiment, The adjustment time is slightly longer, which causes a loss as in the fourth embodiment. The loss time in Example 5 was 330 minutes.

[Example 6]

Hereinafter, the sixth to ninth embodiments will be described in detail with reference to FIG. The solution film-forming equipment 210 shown in Fig. 7 was used, and in Examples 6 to 8, the increase was added, and in Example 9, the increase was not added. In Fig. 15, the sixth embodiment is denoted by A, the seventh example is denoted by B, the eighth example is denoted by C, and the ninth example is denoted by D in FIG. 15 is a time period (unit: minute) in which the increase addition is performed, that is, a period in which the initial addition flow amount QAS continues (hereinafter referred to as an increase addition period), and "P1" Quot; P2 " is a flow rate switching time point at which the flow rate of the additive liquid 261a is switched from the initial addition flow rate QAS to the addition flow rate QAE by terminating the incremental addition and terminating the addition of the additive liquid 261a at the outlet of the addition nozzle 51a When the pressure of the additive nozzle 261a reaches the same pressure as the pressure of the pure dope 44 in the vicinity of each outlet of the addition nozzle 51a, that is, the pressure rise attainment point, "T2" (Hereinafter referred to as target flow rate addition period) (unit: minute).

In order to obtain the film 106 of the varieties B, the flow rate QD of the pure dop 44 was 5 L / min, the addition flow rate QAE was 50 cc / min (= 50 x 10 ^-6 m < ³ > / min). C2 / C1 is 1/100. In this case, the initial addition flow rate QAS was set to 150 cc / min (= 150 x 10 ^-6 m < 3 > / min) and the feed increasing period T1 was set to 15 minutes. After the increase amount addition period T1 has elapsed, the target flow amount addition period T2 is set to 10 minutes while the addition flow rate QAE is set to 50 cc / min (= 50 x 10 ^-6 m3 / min). The target outlet pressure of the addition nozzle 51a was set at 1 MPa. It took 25 minutes to raise the pressure to 1 MPa, and the time from addition of the varieties A to the varieties B when the varieties were added could be shortened by 30 minutes for Example 9, which is carried out only at the additive flow rate (QAE) described later. In this embodiment, the amount of the additive liquid 261a flowing from the start of the incremental addition to the point P2 is 150 (cc / min) x 15 min + 50 cc / min x 10 min = 2750 cc ^-6 ㎥).

[Example 7]

Except that the initial addition flow rate (QAS) was 75 cc / min (= 75 × 10 ^-6 m 3 / min), the increasing addition period (T1) was 30 minutes, and the target flow adding period (T2) 6 under the same conditions. It took 40 minutes to raise the pressure to 1 MPa, and the time from addition of the kind A to the type B at the time of kind switching could be shortened by 15 minutes for Example 9 which is carried out only at the additive flow rate (QAE) described later. Further, in this embodiment, the amount of additive liquid (261a) flows to P2 from the beginning of the increment added 75 (㏄ / min) × 30 min +50 (㏄ / min) × 10 minutes = 2750㏄ (= 2750 × 10 ^{- 6} ㎥).

[Example 8]

Except that the initial addition flow rate QAS was 150 cc / min (= 150 x 10 ^-6 m cc / min), the increasing addition period T1 was 18 minutes, and the target flow addition period T2 was 1 minute, 6 under the same conditions. It took 19 minutes to raise the pressure to 1 MPa, and the time from addition of the varieties A to the varieties B when the varieties were added could be shortened by 36 minutes for Example 9, which is carried out only at the additive flow rate QAE described later. Further, in this embodiment, the amount of additive liquid (261a) flows to P2 from the beginning of the increase was added 150 (㏄ / min) × 18 min +50 (㏄ / min) × 1 min = 2750㏄ (= 2750 × 10 ^{- 6} ㎥).

[Example 9]

The increase was not performed and the target addition flow rate QAE was set to 50 cc / min (= 50 x 10 ^-6 m < 3 > / min) and fed only in the target flow rate addition period T2 and increased. The other conditions are the same as those in the sixth embodiment. It took 55 minutes to raise the pressure to 1 MPa. In this embodiment, the amount of the additive liquid 261a flowing from the start of the incremental addition to the point P2 was 50 cc / min. × 55 min = 2750 cc (= 2750 × 10 ^-6 m 3).

[Example 10]

In Example 10, TAC was used as the polymer 26 and the mixed solvent of dichloromethane, methanol and 1-butanol was used as the organic solvent 27 using the solution film-forming equipment 310 shown in FIG. 10, 44) was prepared. The piping capacity C1 of the whole process is 56000 L, and the piping capacity C2 after adding the additive is 8000 L. Therefore, C2 / C1 is 1/7. (Additive weight / additive weight + mixed solvent weight) x 100 = 55%) was used as the additive and an organic solvent 27 for preparation of the Pseudodop 44 was used as the buffer solution 387 And a buffer layer 389a was formed between the Pure dop 44 and the additive liquid. The amount of the additive solution was 7% with respect to the flow rate of the Pure dop 44 and the addition ratio of the buffer solution 387 with respect to the Pure dop 44 was 0.07% (flow ratio = buffer flow rate / additive liquid amount = 0.07 / 7 = 0.01 ). After the addition of the additive liquid, the additive liquid and the Pseudo-Dope were mixed and dispersed by a composite mixer in which a dynamic mixer 420 and a torsional mixer type static mixer 393 were connected in series. Gelation did not occur, and the softening and peeling could be performed without any problem.

[Example 11]

The conditions were the same as those in Example 10 (flow ratio = 0.7 / 7 = 0.1) except that the addition ratio of the buffer solution 387 was changed to 0.7%. Gelation did not occur, and the softening and peeling could be performed without any problem.

[Example 12]

The same conditions as in Example 10 (flow ratio = 0.06 / 7? 0.009) were obtained, except that the addition ratio of the buffer solution 387 was 0.06%. Gelation occurred.

[Example 13]

The same conditions as in Example 10 (flow ratio = 0.8 / 7? 0.11) were obtained, except that the addition ratio of the buffer solution 387 was 0.8%. Gelation did not occur but the concentration of the soft doping was lowered, and the gel strength was lowered, so that peeling residue was generated at the time of peeling.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a solution casting facility as a first embodiment of the present invention. Fig.

2 is a schematic view showing a film-forming unit.

Fig. 3 is a schematic view showing an adding unit in which the additive is added to the dope in the second step as the second embodiment. Fig.

4 is a schematic view showing a solution film-forming equipment according to a third embodiment of the present invention.

5 is a schematic view showing a solution film-forming equipment according to a fourth embodiment.

6 is a schematic view showing an additive adding unit of the solution film-forming equipment according to the fifth embodiment.

7 is a schematic view showing a solution film-forming equipment according to a sixth embodiment.

8 is a flow chart in the sixth embodiment of the present invention in which the pre-addition treatment is performed at an initial addition flow rate at a flow rate larger than a target addition flow rate.

Fig. 9 is a flow chart in the seventh embodiment.

10 is a schematic view showing a solution film-forming equipment according to an eighth embodiment.

11 is a sectional view of the addition nozzle.

12 is a perspective view of the tip of the addition nozzle.

13 is a perspective view of an inline mixer.

14 is a sectional view of the dynamic mixer.

15 is a graph showing the relationship between the amount of the additive liquid transferred and the liquid delivery time for explaining the embodiment of the present invention.

Claims (26)

A solution casting method for producing a film from soft dope, A solution casting method comprising the steps of: (A) preparing a reference dope containing a polymer and a solvent; (B) an additive peculiar to each of the types of the reference dope is selected from the group consisting of {(1/280) xC1} or more with respect to the flexible die as a reference when the piping capacity from the reference dope- Is added at an upstream position at which the piping capacity is equal to or smaller than {(1/7) xC1}; (C) forming a flexible film on the support by softening the flexible dope on the support by the flexible die; (D) imparting self-supporting property to the flexible film to peel the flexible film from the support as a wet film; (E) drying the wet film to form the film; And (F) In the step of changing the kind of the film, the additive in step B is changed according to the kind. The solution film-forming method according to claim 1, wherein the step B includes an additive liquid adjusting step of containing the additive in a liquid to prepare an additive liquid, wherein the additive liquid is added by an additive nozzle. The method according to claim 2, wherein when the piping capacity from the step A to the flexible die is defined as C1, a ratio of {(1/280) xC1} to {(1/7) xC1} Wherein said additive liquid is added at an upstream position which is a piping capacity The solution film-forming method according to claim 2, wherein the ratio of the flow rate of the additive liquid to the flow rate of the reference dope in the step B is 1% or more and 30% or less. The solution film-forming method according to claim 2, wherein the additive is added in-line in the step (B). The solution film-forming method according to claim 2, wherein the additive contains a plasticizer, and the concentration of the plasticizer in the additive solution is 10 wt% or more and 65 wt% or less. The solution film-forming method according to claim 2, wherein the reference dope contains additives necessary in common for each variety. 3. The solution film-forming method according to claim 2, wherein the reference dope is a pure dop of the polymer and the solvent. The solution film-forming method according to claim 2, wherein the additive liquid is circulated before the step B is performed. 10. The solution casting method according to claim 9, wherein in the circulation, the additive liquid is circulated at the same flow rate as that at the time of adding the additive liquid to the reference dope. The method according to claim 9, wherein the circulation starts more than 120 minutes before the start of the step B. The method according to claim 9, wherein, in the type switching of the film, before the additive liquid used for a new variety is added to the reference dope, the flow path of the additive liquid to the additive nozzle is changed to a cleaning liquid And then cleaning the solution. The method according to claim 2, wherein when the flow rate of the reference dope is QD in the type switching of the film, and the addition flow rate of the additive liquid to be added to a new variety is QAE, When the flow rate ratio is 10% or less and the additive flow rate QAE of the additive liquid is 300 × 10 ^-6 m 3 / min or less, the initial added flow rate QAS of the additive flow rate QAE is 1.5 to 3.0 times, And the initial addition flow rate (QAS) is set to the addition flow rate (QAE) after the lapse of the predetermined time. 14. The method according to claim 13, wherein the predetermined time is a time until the pressure of the additive liquid at the outlet of the additive nozzle becomes equal to the pressure of the reference dope in the vicinity of the outlet of the additive nozzle . 14. The solution film-forming method according to claim 13, wherein the additive liquid is circulated before the step B, and the additive liquid is circulated at the same flow rate as the initial additive flow rate (QAS). The method according to claim 2, wherein in the step B, the additive liquid has a buffer layer formed on the outer periphery thereof and added to the reference dope, and in the step B, the reference dope added with the additive liquid is mixed and homogenized to form the flexible dope . The method according to claim 16, wherein the buffer solution constituting the buffer layer is prepared by adding the same liquid as the solvent, diluting the additive liquid with the same liquid as that of the solvent, And a reference Dopp dilution diluted with the same solution. 18. The method according to claim 17, wherein said step B is a step of setting the flow rate ratio (QB / QAE) to 0.01 or more and 0.1 or less when said buffer solution is the same as that of said solvent and the flow rate of said additive solution is QAE and the flow rate of said buffer solution is QB. By weight or less. 17. The solution casting method according to claim 16, wherein the mixing is performed by passing through a plurality of inline mixers having different mixing methods. 20. The inline mixer according to claim 19, wherein the inline mixer comprises: a triboelectric static mixer comprising a plurality of first elements formed of twisted partition members in a passage of the reference dope; and a second element formed by alternately crossing a plurality of elongated partition members And a dynamic mixer in which a rotating mixer main body is disposed in the passage of the reference dope. The liquid film forming method according to claim 1, As solution casting equipment for producing a film from soft dope, A solution deposition equipment comprising: A reference dope preparation unit for preparing a reference dope containing a polymer and a solvent; The additive peculiar to each grade is set as {(1/280) xC1} or more {(1/7)} or more as a reference relative to the flexible die as the reference dope, and the piping capacity from the reference dope- ) X C 1} or less at an upstream position which becomes the piping capacity to make a soft dope; Forming a flexible film on the support by softening the flexible dope on the support by the flexible die to impart self-supporting property to the flexible film, peeling the flexible film from the support as a wet film, drying the wet film A film-forming unit for obtaining a film; And Wherein the additive changing portion changes the additive to be added to the reference dope to a new prescription in the type switching of the film. The additive adding unit according to claim 21, characterized in that the additive adding unit has an additive nozzle for adding the additive liquid contained in the liquid to the reference dope and an additive supply unit for preparing the additive liquid to be supplied to the additive nozzle Solution deposition equipment. The solution film-forming equipment according to claim 22, wherein the additive supply unit has additive circulation means for circulating the additive liquid upstream of the additive nozzle. The additive adding unit according to claim 22, wherein the additive adding unit includes a cleaner for cleaning the flow path of the additive liquid to the additive nozzle in the kind switching of the film with a cleaning liquid comprising the same liquid as that of the solvent Solution deposition equipment. 23. The solution film-forming equipment according to claim 22, wherein the additive supply part has flow rate control means for controlling the flow rate of the additive solution. 23. The method of claim 22, wherein the additive nozzle has buffer layer forming means for forming a buffer layer on an outer periphery of the additive liquid, wherein the additive adding unit mixes the reference dope added with the additive liquid, And a mixing section for mixing the solution with the solution.

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