KR20100025495A - Solution film-forming method and solution film-forming apparatus - Google Patents

Abstract

PURPOSE: A solution film-forming method and device are provided to prevent waste of a dope by preventing a hole which is generated due to the shortage of addictive. CONSTITUTION: A standard dope containing polymer and solvent is manufactured. The additive is added in the standard dope before a softening die(107) in order to be a softening dope(54). A flexible film(111) is formed on a supporting body(108) by softening the softening dope on a supporter using the softening die. The flexible film is separated from the supporter as a wet film(113). The film is made by drying the wet film. The additive can be changed according to the kind of product.

Description

SOLUTION FILM-FORMING METHOD AND SOLUTION FILM-FORMING APPARATUS}

TECHNICAL FIELD This invention relates to the solution film forming method and equipment which cast dope which melt | dissolved the polymer in the solvent on the support body, and then peels and dries to obtain a polymer film.

Since TAC films formed from cellulose esters, especially cellulose triacetate (hereinafter referred to as "TAC") having an average degree of acetylation of 57.5% to 62.5%, are excellent in optical isotropy, the polarizing plate of liquid crystal display devices which have recently expanded the market. Is used for a protective film.

As a manufacturing method of a TAC film, the solution film forming method is well known, for example as described in Unexamined-Japanese-Patent No. 2005-104148. The solution film-forming method can produce the film excellent in physical properties, such as an optical property, compared with other manufacturing methods, such as a melt film-forming method. In the solution film-forming method, a dope is prepared by first mixing various additives, such as a polymer and a ultraviolet absorber (UV agent), a mat agent, a retardation control agent, a plasticizer, in the mixed solvent which uses dichloromethane and methyl acetate as a main solvent. Next, the dope is cast on the support from the casting die to form a casting film. Then, after the cast film becomes self-supporting on the support, the cast film is peeled off from the support as a wet film and dried, and then wound in a roll form as a product film.

By the way, the polymer film needs to manufacture the varieties according to a use. However, it is not practical to have a solution film production facility for each variety, and it is common to manufacture a plurality of varieties with one solution film production facility. Since the solution filmmaking facility cannot manufacture a plurality of varieties at the same time, when manufacturing a plurality of varieties with one solution filmmaking facility, a variety of varieties may be changed, such as first producing one breed and then manufacturing another variety. Do it. There are two methods for changing this variety.

The first method is as follows. First, the new dope which changed the kind and addition amount of an additive is prepared in a dissolution tank. Next, the prepared dope is flowed into a film forming line, and the dope is switched by replacing the old dope with this new dope.

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

In addition, in order to fine-tune the addition amount of an additive, Unexamined-Japanese-Patent No. 2006-76280 and 2007-216674 do not add immediately before adding an additive liquid just before a casting die. In the immediately preceding addition of this additive, the amount of the additive is measured by sampling the dope or by sampling the finished product. When the additive amount is insufficient, the necessary amount is added immediately before the casting die using an in-line mixer. In addition, addition or mixing of the dope with the additive by an inline mixer is disclosed also in Unexamined-Japanese-Patent No. 2006-088583.

As a method of switching and producing a plurality of varieties of films by one solution film forming facility, there are the first method and the second method described above. However, in the first method of switching varieties by replacing old dope with new dope in the new prescription, it is not necessary to install another feeding system and the configuration becomes simple. However, extrusion replacement is performed until the replacement is completed. New dope about three times the pipe capacity needs to be poured. For this reason, there exists a problem that the loss of time and product loss during extrusion increase.

In addition, in the case of the second method of installing another feeding device, there is no loss of time or product loss as in the extrusion replacement of the first method, but it is necessary to install a plurality of separate feeding devices, resulting in large equipment cost. There is a problem.

Moreover, the method of Unexamined-Japanese-Patent No. 2006-76280 or 2007-216674 which adds an additive liquid to dope just before a casting die is effective when manufacturing one kind with one film forming facility. However, when manufacturing a plurality of varieties with one film forming facility, not only the kind of additive to be used, but also the timing of adding the additive and the target addition ratio may be different for each kind of film. Therefore, even if the methods of JP-A-2006-76280 or JP-A-2007-216674 are used, it is not enough to simply switch according to the kind of film to be newly manufactured in these methods. . For example, even if the additive liquid contained in the liquid is changed under the same conditions, it is impossible to mix the additive liquid so that the dope is uniform. Therefore, until the addition amount of the additive liquid is at a constant level and the properties of the dope after the additive liquid is added are stabilized, a film of the target variety cannot be obtained, leading to a loss of raw materials and production time. Moreover, in some cases, in the state of being flexible in the state where the target additive is lacking, a film forming problem such as a hole is formed in the middle of the film forming, resulting in a soft stop.

In particular, when the amount of the additive liquid added immediately before the dope flow rate is small, both the time loss and the product loss are large. This is because piping to the addition nozzle is commonly used regardless of the change of the additive liquid, and the smaller the flow rate of the new additive liquid, the longer it takes to fill the inside of the pipe with new additives. Therefore, this time becomes a loss time, and since the dope which flows in this time does not become a predetermined ratio in the additive liquid, since it cannot be called a product when it became a film, it was discarded and led to raw material loss.

Accordingly, the present invention has been made to solve the above problems, and even when a film having different varieties is produced, a solution forming method and a facility which can suppress the production time and product loss without increasing the cost of the manufacturing facility. It aims to provide. It is also an object of the present invention to provide a method and equipment for forming a solution that can suppress production time or product loss even when the amount of additives to be added to the new variety is small.

In the solution film forming method of the present invention, a reference dope containing a polymer and a solvent is prepared (step A), and an additive specific to each variety is added to the casting dope immediately before the casting die with respect to the reference dope (step B). ), The flexible dope is cast on the support by the casting die to form a casting film on the support (step C), to impart self-support to the casting film, and to peel the casting 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 addition step according to the variety in the variety switching of the film (step F). do.

In said step B, it is preferable to contain the said additive in a liquid, to prepare an additive liquid, and to add this additive liquid with an addition nozzle. When the piping capacity from the step A to the flexible die is C1, an upstream side that becomes a piping capacity of {(1/280) × C1} or more and {(1/7) × C1} or less based on the flexible die. It is preferred to add the additive in position. Moreover, it is preferable that the ratio of the flow volume of the said additive liquid with respect to the flow volume of the said reference dope in the said step B is 1% or more and 30% or less. In said step B, it is preferable to add the said additive inline. Moreover, it is preferable that the said additive contains a plasticizer and the density | concentration of the said plasticizer in the said additive liquid is 10 weight% or more and 65 weight% or less. It is preferable that the said reference dope contains the additive which is common to each breed, or is a pure dope which consists of the said polymer and the said solvent.

It is preferable to circulate beforehand the said additive liquid before the said step B, and it is more preferable to circulate at the same flow volume when the said additive liquid is added to the said reference dope. As for circulation, it is more preferable to start 120 minutes or more before the said start of addition. In addition, it is preferable to wash the flow path of the additive liquid up to the addition nozzle with a cleaning liquid composed of the same liquid as the components of the solvent before adding the additive liquid used for the new varieties in the breeding of the film to the reference dope. .

In the varietal switching of the film, the addition flow rate ratio obtained by {(QAE / QD) × 100} is 10% or less when the flow rate of the additive dope added according to the QD and the new varieties is QAE. When the addition flow rate (QAE) of the additive liquid is 300 × 10 ^-6 m 3 / min (= 300 kPa / min) or less, the initial addition flow rate (QAS) of 1.5 to 3.0 times the addition flow rate (QAE) It is preferable to perform time addition, and to make the said initial addition flow volume QAS into the said addition flow volume QAE after the said fixed time passes. It is preferable that the said fixed time is time until the pressure of the additive liquid at the exit of an addition nozzle becomes equal to the pressure of the reference dope in the vicinity of the exit of an addition nozzle, and circulates an additive liquid previously before the said step B beforehand. It is more preferable that the additive liquid be circulated at the same flow rate as the initial addition flow rate QAS.

In said step B, it is preferable that the said additive liquid forms a buffer layer in the outer periphery, and is added to the said reference dope, and in step B, it is preferable to mix and equalize the reference dope to which the additive liquid was added, and to make it said casted dope.

The buffer constituting the buffer layer is a diluent liquid containing the same liquid as the component of the solvent, an additive liquid dilution obtained by diluting the additive liquid with the same liquid as the component of the solvent, and a reference dope diluted with the same liquid as the component of the solvent. It is preferable that it is either diluent. It is preferable that the said step B makes the said buffer liquid the same liquid as the component of the said solvent, and makes flow volume ratio (QB / QAE) into 0.01 or more and 0.1 or less, when the flow volume of the said additive liquid is QAE and the flow volume of the said buffer liquid is QB. .

It is preferable to perform the said mixing by letting a some inline mixer pass through different mixing methods.

The in-line mixer refers to a salt mixing-type static mixer configured by arranging a plurality of first elements made of twisted partition members in a passage of a reference dope, and a second element formed by alternately intersecting a plurality of elongated partition members. At least one of a split-mix type through the mixer configured by plurally arranged in the passage of the dope, and a dynamic mixer configured by arranging the rotating mixer main body in the passage of the reference dope.

Moreover, the solution film-forming installation of this invention is a reference dope preparation unit which prepares the reference dope containing a polymer and a solvent, and the additive specific to each variety is located just before a casting die, ie, the upstream side near a casting die with respect to a reference dope. An additive addition unit to be added to the casted dopant and the casted dope to which the additive was added, the casted die was casted on the support with the casted die to form a casted film on the support; And a film forming unit for peeling off as a wet film from the film, drying the wet film to obtain a film, and an additive changing part for changing the additive added to the reference dope in the switching of the film to a new prescription. It is.

It is preferable that the said additive addition unit has the addition nozzle which adds the additive liquid which the said additive contains in the liquid to a reference dope, and the additive supply part which prepares the additive liquid supplied to this addition nozzle, The additive supply part adds an additive liquid, It is more preferable to have the additive circulation means to circulate upstream than the addition nozzle. It is preferable that an additive addition unit has the washing | cleaning part which wash | cleans the flow path of the said additive liquid to the said addition nozzle in the kind switching of a film with the washing | cleaning liquid which consists of the same liquid as the component of the said solvent.

It is preferable that the said additive supply part has a flow volume control means which controls the flow volume of the said additive liquid.

It is preferable that the addition nozzle has a buffer layer forming means for forming a buffer layer on the outer circumference of the additive liquid, and the additive adding unit has a mixing portion for mixing and uniformizing the standard dope to which the additive is added to form a cast dope.

According to the present invention, when producing a film of a new variety having different components or amounts of various additives, it is possible to suppress production time loss and product loss without increasing equipment cost. In addition, the switching of the additive can be performed efficiently, and it is possible to operate quickly at a predetermined addition ratio. Thereby, film forming problems, such as the shortening of time from the start of the additive addition operation until the quality is stabilized, and the puncture due to the lack of additives, are suppressed, and the waste of dope is also eliminated. According to the present invention, this effect is obtained even when the amount of the additive used in the new variety is small. In addition, since the occurrence of gelation and the aggregation of the additive due to the addition of the additive is suppressed, as a result, product loss is more surely reduced.

The above objects and advantages will be readily 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 illustrated in FIG. 1 includes a pure dope preparation unit 11, an additive adding unit 12, and a film forming unit 13.

The pure dope preparation unit 11 is comprised from the mixing part 15, the dissolution part 16, the concentration part 17, and the storage part 18. As shown in FIG. The mixing section 15 has first and second tanks 21 and 22, a dissolution tank 23, a storage tank 24, and a pump 25. The polymer 26 is put in the 1st tank 21, and a predetermined amount is measured by the attached meter and the polymer 26 is injected into the dissolution tank 23. As shown in FIG. The solvent 27 is put into the 2nd tank 22, and predetermined amount of the solvent 27 is thrown into the dissolution tank 23 by the attached metering pump (not shown).

Thus, the dope which consists only of the polymer 26 and the solvent 27 is called pure dope in this invention. This pure dope is necessary in common in each variety, and the amount of addition may be added to the minimum amount of each variety at the time of preparation of pure dope in advance, and this is referred to as a consultation standard dope (see second embodiment of the following). . In addition, pure dope and negotiated reference dope are collectively called only reference dope.

The polymer 26 which concerns on this invention is not specifically limited, What is necessary is just to be applicable to the solution film forming method. When a cellulose acylate is used in this, the film which is high in transparency and excellent in an optical characteristic can be obtained, and the film obtained is suitable as optical uses, such as a protective film for polarizing plates, an optical compensation film, and the like. Especially, when a cellulose acetate is used and especially TAC whose average value of acetylation degree is 57.5%-62.5% is used, the film excellent in optical characteristics can be obtained. Said acetylation degree means the amount of bound acetic acid per unit weight of a cellulose, and can be calculated | required according to the measurement and calculation of the acetylation degree in ASTM: D-817-91 (test methods, such as cellulose acetate). In this embodiment, granular TAC is used. Moreover, when using a granular polymer, it is preferable that 90 weight% or more is a particle size of 0.1-4 mm from a compatibility viewpoint with a solvent, More preferably, it is 1-4 mm.

Halogenated hydrocarbons, esters, ketones, ethers, alcohols and the like are suitable, but the solvent 27 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. Specifically, halogenated hydrocarbons (eg, dichloromethane, etc.), esters (eg, methyl acetate, methyl formate, ethyl acetate, amyl acetate, butyl acetate, etc.), ketones (eg, acetone, methyl ethyl ketone, cyclohexanone, etc.) Etc.), ethers (for example, dioxane, dioxolane, tetrahydrofuran, diethyl ether, methyl t-butyl ether, etc.), alcohols (for example, methanol, ethanol, etc.), etc. are mentioned.

The melting tank 23 is provided with the stirring blade, and the polymer 26 and the solvent 27 in the melting tank 23 are stirred by this stirring blade rotating. This stirring yields a crude solution in which solutes such as polymer 26 are not completely dissolved in the solvent.

The crude solution in the dissolution tank 23 is once stored in the storage tank 24. Thereby, the dissolution tank 23 becomes empty, and the continuous batch type which makes the crude dissolution liquid repeat repeatedly by one batch becomes possible. The storage tank 24 also has a stirring blade. By rotating this stirring blade, the crude solution is stirred and made uniform.

The crude solution in the storage tank 24 is sent to the first heater 31 of the melting part 16 via the pump 25. As the first heater 31, an inline mixer such as a multi-tube heat exchanger or a stationary mixer is used. The crude solution is heated by this first heater 31. 50-120 degreeC is preferable, and, as for the so-called heating time which maintains the temperature of a crude solution in this temperature range, 5-30 minutes are preferable. By this heating, solutes, such as the polymer 26 required for solution film formation, are completely dissolved without being denatured to prepare pure dope. The pure dope prepared in this way becomes 14 to 24 weight% as solid content concentration of a cellulose ester.

Pure dope heated by the first heater 31 is sent to the cooler 32. By the cooler 32, it cools to below the boiling point of the main solvent which comprises pure dope. The cooled pure dope 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 the solvent 27 is composed of a plurality of liquid components.

Although not shown in the drawing, the first filter 34 includes a plurality of filter bodies for cleaning and use, a cleaning device for these filter bodies, and the like. The filter is cleaned and exchanged on the other side while filtration is performed on one side. . This enables continuous filtration of pure dope. The filtration system is not particularly limited. The pure dope after filtration is sent to the concentrating part 17 by the pump 35.

The pure dope 44 after the filtration is heated by the second heater 40 of the condenser 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 storage tank 43 of the storage part 18 by the pump 42. In addition, the concentrating part 17 is provided as needed, and you may abbreviate | omit.

The pure dope 44 stored in the storage tank 43 is sent to the additive addition unit 12 by the pump 45. The additive liquid is added inline to the pure dope 44 by the additive adding unit 12. The additive adding unit 12 makes a predetermined additive liquid 67, and adds the additive liquid 67 to the pure dope 44 flowing through the dope pipe 46 and the addition nozzle ( 51), the static mixer 52, and the second filter 53. As shown in FIG. In addition, a check valve (not shown) or an opening / closing valve (not shown) for preventing the back flow of the additive liquid 67 is provided in the piping for feeding the additive liquid 67 to the addition nozzle 51 as necessary.

The additive liquid supply unit 50 contains a predetermined additive, and includes a plurality of additive combination systems 61, a pump 62, and a controller 63 for preparing an additive liquid that is used as it is or mixed with the additive liquid 67. Equipped with. The additive combination system 61 is comprised from the additive combination part 64, the additive liquid tank 65, and the opening / closing valve 66a. The additive liquids made in each additive combination system 61 may be used alone as the additive liquid 67, or the additive liquids produced in the different additive combination systems 61 may be mixed to add the additive liquid ( 67). In this way, the plurality of additive combination systems 61 are provided so that the plural kinds of additive liquids 67 can be introduced into the pure dope 44 according to the film type.

The kind of various additives in the additive liquid 67 and the addition amount to the pure dope 44 are previously calculated | required for each kind of film 106 (refer FIG. 2) to manufacture, and the combined lookup table memory (combined LUT) 68 is carried out. Remembered. The controller 63 obtains the type and the amount of the corresponding additive from the combination LUT 68 according to the variety of the film 106. And the additive liquid of the additive kind and quantity according to film varieties is combined by the additive combination part 64 from the kind and addition amount of the calculated additive. This additive liquid is stored in each additive liquid tank 65. The plurality of additive liquid tanks 65 are provided with additive liquid changing means 66 for adjusting the opening degree of the pipe in order to change the additive liquid 67 according to the kind of the film. The additive liquid changing means 66 is composed of a plurality of opening / closing valves 66a, and the opening and closing degrees thereof are controlled so that the additive liquid, which should constitute the additive liquid 67, is sent to the predetermined amount addition nozzle 51. do. The opening / closing degree of the opening / closing valve 66a is controlled by the controller 63, whereby the additive liquid 67 added to the pure dope 44 is changed, and the additive liquid 67 according to the film variety is changed. It is sent to the addition nozzle 51 by the metering pump 62.

As the addition nozzle 51, a flat nozzle whose tip is flattened and extended in the radial direction of the circular cross section of the dope pipe 46 is used. The addition nozzle 51 and the static mixer 52 disposed downstream of this are described in detail in Japanese Patent Application Laid-Open 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 flexible dope 54. This casting dope 54 is sent to the casting die 107 (see FIG. 2) of the film forming unit 13.

In the additive addition unit 12, QD and the additive liquid 67 at the time of adding the flow volume ratio of the additive liquid 67 with respect to a reference dope, ie, the flow volume of the reference dope when adding an additive liquid to a reference dope, are added. When the flow rate of QA is QAE, the percentage (unit:%) determined by {(QAE / QD) × 100} is preferably 1% or more and 30% or less. QD in this embodiment shown in FIG. 1 is the flow volume of the pure dope 44.

In addition, when the addition flow rate ratio of the additive liquid 67 to the reference dope is 0.9%, it is often necessary to make the additive liquid 67 at a high concentration by the minute that the addition flow rate ratio is set to be low. Although a gel failure may arise also in the film 106 which is a product which generate | occur | produces, generation | occurrence | production of gelatinization is suppressed reliably when the addition flow rate ratio is 1% or more.

On the other hand, when the addition flow rate ratio of the additive liquid 67 to the reference dope is 31%, the flow rate QAE of the additive liquid 67 increases with respect to the flow rate QD of the reference dope, and a problem appears in the mixing property after the addition. In some cases, when the addition flow rate ratio is 30% or less, the reference dope and the additive liquid 67 are mixed with each other to be uniform, whereby the mixing properties are reliably improved.

Moreover, it is preferable that ratio (rho1 / rho2) of the viscosity (rho1) of the pure dope 44 which is an addition liquid, and the viscosity (rho2) of the additive liquid 67 is 500 or less. When the viscosity ratio exceeds 500 or the addition flow rate ratio exceeds 30%, both become difficult to mix and are mixed at less than 1%, but no efficient addition is performed.

Moreover, it is preferable that an additive contains a plasticizer and the density | concentration of the plasticizer in the additive liquid 67 is 10 weight% or more and 65 weight% or less. The density | concentration of this plasticizer is a percentage (unit:%) calculated | required as (y / x) x100 when the weight of the additive liquid 67 is x and the weight of a plasticizer is y. If it is less than 10% by weight, it is necessary to increase the amount of the additive liquid 67 to the pure dope 44 in order to make the concentration too small and finally to the required amount of plasticizer, and the additive liquid 67 to the pure dope 44. The mixing ratio of may increase, resulting in poor mixing of both. Moreover, when it exceeds 65 weight%, the additive which is not melt | dissolved in the pure dope 44 will increase.

In the present invention, the additive required according to the film varieties produced for the pure dope 44 to which the additive is not added is added to the flexible die 107 of the film forming unit 13 by the additive liquid supply unit 50 and the addition nozzle 51. As it is supplied just before entering), it can respond quickly to new varieties. In this way, the addition is in the vicinity of the casting die 107 and is performed upstream of the casting die 107. In addition, when supplying the additive liquid 67 to the pure dope 44, the additive contained in the additive liquid 67 becomes necessary for each breed containing the thing peculiar to each breed. On the other hand, in the same manner as in the third embodiment described later, additives commonly required for each variety are added to the pure dope 44 in advance, and when the additive liquid 67 is supplied to the narrow reference dope thus obtained, the additive is added. The additive contained in the liquid 67 becomes an additive unique to each variety.

As an additive, a plasticizer, a mat agent, a ultraviolet absorber (UV agent), a retardation control agent, another additive, etc. are mentioned. In the additive combination unit 64, various additives required for the varieties produced from the combination LUT 68 are specified, these specific additives are added to the solvent 27 as needed, and the additive liquid 67 is combined. These additives are described, for example in Paragraph-[0516] of Unexamined-Japanese-Patent No. 2005-104148, These description can also be applied to this invention.

As described above, in the present invention, it is only necessary to change the type of the additive liquid 67 and the amount of addition thereof, and the section in which the previous dope is extruded and replaced by the new dope during the dope switching of the new and old can be shortened as compared with the conventional method. .

Extrusion substitution part will be in the state which mixed old and new dope. With conventional equipment that adds additives from the mixing section 15 until it is completely replaced with new dope, a new dope of about three times the piping capacity from the storage tank 24 to the flexible die of the film forming unit 13 is required. Shall be. Therefore, in the conventional installation, since the new dope of about three times the pipe capacity from the storage tank 24 to the flexible die is not a product until the extrusion replacement is completed, and the additive is mixed, this extrusion replacement is performed. It is not possible to provide for continuous recycling a film for recycling. That is, new dope corresponding to this extrusion substitution amount is wasted. For this reason, the loss of new dope was enormous in the conventional new switching method by extrusion replacement. On the other hand, in the present invention, since the additive is added to the reference dope immediately before the casting die 107 (see FIG. 2) of the film forming unit 13, the amount of extrusion displacement can be reduced.

In the first embodiment, the piping capacity C2 of 1/280 or more and 1/7 or less with respect to the conventional piping capacity C1 on the downstream side, that is, on the basis of the inlet of the flexible die of the film forming unit 13, is changed. It becomes possible to arrange | position the addition nozzle 51 in the position to become. Moreover, the film part in which the old and new additives are mixed is about three times the piping capacity after this addition nozzle, and the loss of dope can be suppressed about 1 / 280-1 / 7 with respect to the thing of a conventional installation.

The pure dope 44 flowing through the dope pipe 46 has a very high viscosity compared with the additive liquid 67. For example, the viscosity ρ1 of the pure dope 44 is approximately 10 to 150 (unit; ㎩ · s) while the viscosity ρ2 of the additive liquid 67 is approximately 0.001 to 1.0 (unit; 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 dope 44 and the additive liquid 67 having significantly different viscosities are mixed, the droplets of the additive liquid 67 tend to remain in the pure dope 44. That is, the fine droplets of the additive liquid 67 tend to be dispersed in the pure dope 44, and gelation tends to occur. And this tendency is so large that the flow volume of the additive liquid 67 is small with respect to the flow volume of the pure dope 44 at the time of supplying the additive liquid 67 to the pure dope 44.

In order to proceed the mixing so that the additives are uniformly dispersed in the pure dope 44 from the liquid droplet dispersion state, a so-called inline mixer such as a static mixer, in which a liquid to be mixed in a plurality of elements is continuously sent to mix the liquids. (52) is valid. However, in-line mixers, such as the static mixer 52, are arrange | positioned so that the some element 52a of a predetermined shape may be aligned in the longitudinal direction of the dope piping 46 as well known. In addition, since the number of the elements 52a is determined so that the additives can be uniformly dispersed in the pure dope 44, the length of the in-line mixer, which increases as the number of the elements 52a increases, increases the length of the additive liquid 67 and the pure dope. The viscosity ratio and the flow rate ratio are determined, and the larger the viscosity ratio and the flow rate ratio, the longer. In addition, the gelation is more surely suppressed as the number of elements 52a is increased to lengthen the length of the inline mixer.

Thus, in order to supply the additive liquid 67 to the pure dope 44 and to disperse | distribute an additive uniformly, the additive is uniformly uniform by some length, ie, the shear by the element 52a, etc. in the static mixer 52 used. It needs to be long enough to be distributed. The upstream end of C2 is set to the upstream side as the static mixer 52 becomes longer.

In addition, although only one melting tank 23 is shown in FIG. 1, a plurality of melting tanks 23 are normally provided, and these several melting tanks 23 are connected to the storage tank 24. As shown in FIG. Each dissolution tank 23 is connected to the storage tank 24 by independent piping, and may be changed so that only the connection pipe with the predetermined dissolution tank 23 is in an open state. A switching valve may be provided in which the pipe is connected to one of the pipes connected to the storage tank 24, and the switching valve is switched to the storage tank 24 so that the crude solution flows from the predetermined solution tank 23. . In FIG. 1, the former case is shown and the upstream end of C1 is made into the downstream end of the dissolution tank 23, ie, the upstream end of the piping which connects the dissolution tank 23 and the storage tank 24. As shown in FIG. On the other hand, in the latter case, the connecting portion to which the pipes extending from the respective dissolution tanks 23 connect to one pipe may be an upstream end of C1.

In addition, some of the additives used are dissolved in the solvent 27. Therefore, the additive liquid 67 was added upstream from the 1st heater 31 conventionally. In addition, since it is thought that it is preferable to contact the solvent 27 and an additive as soon as possible, the additive liquid 67 was added as possible upstream. However, in forming the crude solution, the plurality of melting tanks 23 are switched and used as described above, so that the additive liquid 67 can be added, even if it is the most upstream side. ) Upstream end of the pipe to connect. From this viewpoint, the upstream end of the conventional piping capacity C1 is shown as the downstream end of the dissolution tank 23. On the other hand, when the additive is also mixed in the dissolution tank 23, the upstream end of the dissolution tank 23 may be the upstream end of the conventional piping 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.

In FIG. 1, as described above, the additive liquid 67 is added to the crude solution at the upstream end of the pipe connecting the melting tank 23 and the storage tank 24 with respect to the conventional piping capacity C1. The case is illustrated. In this case, the mixture of the crude dissolution liquid and the additive liquid 67 flowing in the piping between the dissolution tank 23 and the storage tank 24 is replaced with the mixture of the crude dissolution liquid and the new additive liquid 67. The upstream end of the piping capacity C1 serves as a connection portion between the melting tank 23 and the piping. Therefore, when the mixing of the crude solution and the additive liquid 67 is performed in the dissolution tank 23, the inside of the dissolution tank 23 is replaced with a new mixture, so that the upstream end of the conventional piping capacity C1 is It becomes the upstream end of the melting tank 23.

Conventional piping capacity (C1) and piping capacity (C2) is not only the capacity of pipes for connecting between devices such as the cooler 32 and the pump 33, and tanks, but also the capacity of each device or each tank. Included. That is, all the capacity of the old dope, including the piping.

In addition, if necessary, an online component system may be provided on the outlet side of the additive liquid tank 65 to determine whether the additive component of the additive liquid is within the predetermined range. In this case, according to the measurement result, the addition amount of the various additives in the additive combination part 64 is increased and decreased, and the addition amount of the various additive components is controlled in a predetermined range. Near-infrared spectroscopy is used as an online component measurement.

Near-infrared spectroscopy is performed by irradiating near-infrared light in a short wavelength region to the additive liquid, and measuring the absorbance spectrum of the measured object by detecting measured light such as scattered reflected light, scattered transmitted light, or transmitted reflected light from the measured product, and measuring the absorbance spectrum of the additive liquid. It is a method of calculating the component amount of an additive liquid from absorbance based on the calibration curve previously prepared by obtaining the absorbance of the spectral wavelength region which has a correlation intrinsic to the component amount.

As shown in FIG. 2, the film forming unit 13 includes a flexible chamber 100, a moving unit 101, a tenter 102, a drying chamber 103, and a winding machine 104. 54 is used to make a film 106. In the flexible chamber 100, the flexible die 107 in which the discharge opening of the flexible dope 54 was formed, the flexible drum 108 which functions as a support body, and the peeling roller 109 are arrange | positioned.

The casting dope 54 is cast through the casting die 107 on the rotating drum 108 serving as an infinite casting support, and the casting film 111 is formed on the circumferential surface thereof. It is preferable to make the surface temperature of the casting drum 108 substantially constant in the range of -10 degreeC or more and 10 degrees C or less. When the dope is cast on such a casting drum 108, the dope is cooled rapidly, and thus, a gel casting film 111 is formed within a short time. As the casting drum 108 rotates, the gelation of the casting membrane 111 proceeds, and the casting membrane 111 having self-supporting property is supported by the peeling roller 109 as the wet film 113 from the casting drum 108. Peel off.

The moving part 101 supports the wet film 113 with many rollers, and drying advances during conveyance. In the tenter 102, both ends of the wet film 113 are held by a holding means such as a pin, and then drying proceeds to convey the film 106 during conveyance. Thereafter, the film 106 is wound in a roll shape on the core 105 of the winder 104.

The upstream side of the casting die 107 is provided with the second filter 53 of the additive adding unit 12, and the pure dope 44 mixed with the additive liquid 67 is filtered before being supplied to the casting. As a result, the flexible dope 54 in which impurities are further removed is obtained. In this embodiment, although the apparatus provided with a metal filter is used, a filtration system is not specifically limited, A filter is also used suitably. Here, it is preferable that the average hole diameter is 100 micrometers or less in the hole which a filter has in removing even fine 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, when the average hole diameter is too large, it is difficult to capture fine impurities in the flexible dope 54. The filter may be appropriately selected while considering productivity and the like.

Solvent recovery from the structure of the casting chamber 100, the casting die 107, the casting drum 108, and the like, the ball flexibility, the peeling method, the stretching, the drying conditions of each process, the handling method, the curl, and the winding method after the flatness correction. The method and the film recovery method are described in detail in paragraphs [0617] to [0889] of JP 2005-104148 A, and these descriptions can also be applied to the present invention. Moreover, in the said embodiment, although the cooling gelation method made the cooling gelation of the flexible film | membrane on the casting drum 108, and made it self-supporting, the invention is similarly implemented also in the drying system which also makes a casting film dry on a band or drum, and also makes self-supporting. can do.

The film obtained by this invention has high transparency and retardation value, and its humidity dependence is low. Therefore, although it can use suitably especially as a retardation film of a polarizing plate, it can use also as a protective film for protecting the surface of a polarizing plate. Regarding the specific use of the cellulose ester film of the present invention, Japanese Patent Laid-Open No. 2005-104148 discloses, for example, paragraphs [1088] to [1265] as TN type, STN type, VA type, and OCB type as liquid crystal display devices. , Reflection, 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, in the case of carrying out variety switching by changing the type and amount of various additives, the additive addition unit 12 is switched from the old additive to the new additive in the state of continuous casting. First, the variety switching information is sent from the master controller (not shown) to the controller 63 of the additive adding unit 12. The variety switching information includes the timing of switching and the kind and concentration of the additive used in the new variety. When the variety switching information is sent, the controller 63 controls the additive combination unit 64 to produce each additive liquid (not shown) constituting the additive liquid 67 corresponding to the new variety. Moreover, the controller 63 controls the opening degree of each opening / closing valve 66a of the additive liquid changing means 66 to send the additive liquid made by the additive combination unit 64 to the downstream side from the additive liquid tank 65. In this way, the additive liquid 67 corresponding to the old variety is switched to the additive liquid 67 of the new variety by input to the controller 63 of the variety switching timing signal. At this time, the discharge | emission and washing | cleaning of the additive liquid 67 of an old type are performed, and the additive liquid 67 of a new type is sent to the addition nozzle 51 after that.

In addition, although the 1st embodiment mentioned above demonstrated single-layer softening as an example, in addition to a base layer, you may make it the shared lead which softens an outer layer simultaneously or sequentially in both surfaces of this base layer. Also in this case, like the said embodiment, first, pure dope without an additive is prepared, and the additive required in each layer with respect to this pure dope may be added at the position immediately before a casting die with respect to each layer.

In the case of simultaneous sharing, the plurality of flexible dope 54 is guided independently to one flexible die 107 and joined in the flexible die 107 to be flexible, and the plurality of flexible dope independently guided. A feed block for joining 54 in a layered shape may be provided upstream of the casting die 107 and the plurality of joined dope 54 may be sent to the casting die 107 in one layered flow to be flexible. 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.

In the case of sequential shared lead, each flexible dope 54 is flexible using a plurality of flexible dies 107, so that the upstream end of each flexible die 107 is a downstream end of the conventional piping capacity C1, and this is piped. What is necessary is just to set it as the reference position at the time of determination of the capacitance C2.

In the said 1st Embodiment, although the additive is added in the same addition position, as shown in FIG. 3, you may use the multistage addition unit 70 which adds an additive in multiple positions. This multi-stage addition unit 70 which is 2nd Embodiment is comprised so that the 1st addition part 71 and the 2nd addition part 72 may be arrange | positioned with respect to the dope piping 73 in the dope dripping direction. The first and second addition parts 71 and 72 are composed of an additive liquid supply part 50, an addition nozzle 51, and a static mixer 52. Moreover, the multistage addition unit 70 is equipped with the 2nd filter 53 same as the additive addition unit 12 downstream of the 2nd addition part 72. As shown in FIG.

This multistage addition is effective when the addition is not performed uniformly with one addition at the same addition position. Moreover, what is necessary is just to connect multiple stages in series, and the number of stages is not specifically limited. The additive at each addition position may be the same component, or may add the additive of the other component in each addition position.

Next, with reference to FIG. 4, 3rd Embodiment of this invention is described. In this 3rd Embodiment, about the additive used commonly in each breed with respect to the pure dope which consists of a polymer and a solvent, the minimum usage amount is previously added to the reference dope preparation unit 80, and the reference dope 81 of consultation is negotiated. ). Although the additive addition unit 82 adds a shortfall based on the additive addition amount in narrow reference dope 81, the structure of the additive addition unit 82 is the same as the additive addition unit 12 of FIG. In addition, in FIG. 4, the code | symbol 87 is attached | subjected to the additive liquid added by the additive addition unit 82. In addition, in FIG.

In 3rd Embodiment, the part different from 1st Embodiment is three points of the following (1)-(3), and the others are the same structure as 1st Embodiment, and the same structural member as 1st Embodiment in FIG. Is denoted by the same reference numeral as in FIG. 1. The part different from 1st Embodiment is, (1) adding the additive (common additive) 83 which becomes a base to the dissolution tank 23 of the mixing part 85 from the 3rd tank 84, and negotiates Preparing the reference dope 81, (2) adding only a shortage to the additives already added in the agreed reference dope 81 with the additive addition unit 82, and (3) the necessary film type Is to add new additives. Therefore, the additive liquid 87 contains at least either of the "lack" of (2) and the "new additive required for every kind" of (3).

In this 3rd embodiment, when the flexible prescription dope 54 of the new prescription which becomes unnecessary for the common additive 83 added at the time of preparation of the consultation reference dope 81 is produced, the consultation reference dope 81 is used. The disadvantage is that it is troublesome to switch the new prescription because it is necessary to produce a negotiated reference dope 81 for the new prescription dope after writing. On the other hand, a common additive 83 commonly used is used in the dissolution tank 23. By adding it, the addition amount in the additive addition unit 82 can be reduced by that much, and there exists an advantage that the addition amount in the addition unit 82 can be reduced. In addition, the addition method of the common additive 83 is not limited only to the 3rd tank 84, You may add to the dissolution tank 23 by various addition methods.

Next, 4th Embodiment of this invention is described, referring FIG. In addition, in 4th-8th embodiment demonstrated below, only the form different from 1st embodiment is demonstrated, and in FIG. 5, about the apparatus and member similar to FIG. 1-FIG. The same code | symbol as FIG. 4 is attached | subjected, and description is abbreviate | omitted.

The solution film forming facility 90 of the fourth embodiment includes the following additive addition unit 92 instead of the additive addition unit 12 of the first embodiment.

The pure dope 44 stored in the storage tank 43 of the storage portion 18 is sent to the additive addition unit 92 by the pump 45. The additive adding unit 92 is a pipe connecting the additive liquid supply unit 93, the addition nozzle 51, the static mixer 52, the second filter 53, the additive liquid supply unit 93, and the addition nozzle 51 ( 55). In the pipe 55 for feeding the additive liquids 99a to 99c to the addition nozzles 51, a check valve 56 and an open / close valve 57 for preventing back flow of the additive liquids 99a to 99c are provided.

The additive liquid supply part 93 is equipped with the 1st-3rd additive liquid combination systems 95-97, and the controller 98 of these combination systems 95-97. The piping 180 extended downstream from each additive combination part 170 of each of the first to third additive liquid combination systems 95 to 97 is provided with a three-way switching valve 179b to be described later, It is connected to the piping 55 connected to the addition nozzle 51 downstream of this three-way switching valve 179b. Thus, by providing the several additive liquid combination systems 95-97, several kinds of additive liquids 99a-99c can be added to the pure dope 44 by the required part according to a film variety. Although three additive liquid combination systems 95-97 are provided in this embodiment, these should just be two or more.

The first additive liquid combination system 95 is for adding a plasticizer, and the additive liquid combination unit 170, the metering pump 172 which sends the additive liquid 99a made by the additive liquid combination unit 170 to the downstream side, The circulation part 173 is provided. The additive liquid combination unit 170 is connected to the pipe 55 as described above, and stir-mixes the plasticizer supply unit 174, the solvent supply unit 175, and the plasticizer and the solvent supplied from the respective supply units 174 and 175. The mixing tank 176 and the additive liquid tank 177 are provided. Each supply part 174,175 is connected to each additive tank or solvent tank which is not shown in figure, and an additive or a solvent is measured and supplied to the mixing tank 176. FIG. The mixing tank 176 prepares the additive liquid 99a by adding a plasticizer to the solvent in a predetermined amount for each film variety in accordance with the variety of the TAC film. The plasticizer concentration of this additive liquid 99a is 25 weight%, for example, and a viscosity is 10 Mpa * s. This plasticizer concentration is preferably used in the range of 10 weight% or more and 65 weight% or less. In addition, a plasticizer viscosity is used preferably in the range of 10000 Mpa * s or less.

The second additive liquid combination system 96 prepares an additive liquid 99b obtained by mixing a UV agent and a solvent. Moreover, the 3rd additive liquid combination system 97 prepares the additive liquid 99c which mixed the retardation control agent and the solvent. These second and third additive liquid combination systems 96 and 97 are configured similarly to the first additive liquid combination system 95.

The types and amounts of various additives such as plasticizers, UV agents, retardation control agents, and matting agents added to the pure dope 44 are determined in advance for each type of film to be produced, and the combined lookup table memory (combined LUT) 167 ) Is stored in the controller 98. The controller 98 obtains the type and amount of additives from the combination LUT 167 according to the film type. The additive liquids 99a to 99c are prepared in the additive liquid combination unit 170 based on the type and the amount of the additives obtained. The prepared additive liquids 99a to 99c are stored in the respective additive liquid tanks 177.

Each circulation part 173 is composed of a circulation pipe 178 and three-way switching valves 179a and 179b for circulating additive liquids 99a to 99c upstream of the connecting portion of the pipe 55 and the pipe 180. It is. The circulating pipe 178 is connected to the pipe 180 connecting the additive liquid combination unit 170 and the pump 172, and this connection part has a three-way switching valve (hereinafter referred to as an inlet side three-way switching valve) ( 179a) is provided. That is, the inlet side three-way switching valve 179a is provided in the piping 180 between the additive liquid combination part 170 and the pump 172. The pipe extending downstream from the first additive liquid combination system 95 and the pump 172 is provided is connected to the pipe 55 as described above, and is connected to the circulation pipe 178 upstream from this connection part. Diverged. The three-way switching valve (hereinafter referred to as an outlet-side three-way switching valve) 179b described above is provided in this branch portion.

These inlet three-way switching valves 179a and outlet side three-way switching valves 179b have three valves independently adjusted. This opening degree adjustment also includes switching of opening and closing, and the flow path of each of the additive liquids 99a to 99c is switched by switching of opening and closing. For example, if the outlet three-way switching valve 179b closes only the valve on the circulation pipe 178 side, the additive liquids 99a to 99c of the additive liquid combination unit 170 do not flow to the circulation pipe 178 and the pipe ( It is sent to the addition nozzle 51 through 55. When the outlet three-way switching valve 179b closes only the valve on the connection side with the pipe 55, the additive liquids 99a to 99c flow into the circulation pipe 178 without being sent to the addition nozzle 51. It flows so that the piping 180 extended downstream from the additive liquid combination part 170 and the circulation piping 178 branching from this may circulate. When the predetermined valves of the inlet three-way switching valve 179a and the outlet three-way switching valve 179b are opened, the flow rate and pressure of each of the additive liquids 99a to 99c flowing by adjusting the opening degree are Controlled.

When each of the three-way switching valves 179a and 179b is input with the following new type of switching timing signal, the opening degree of the valve is switched based on this switching timing signal. By this switching, the additive liquids 99a to 99c used for the new varieties flow into the circulation pipe 178 at a predetermined flow rate prior to the addition timing, and the additive liquid (circuit 178 and the pipe 180 circulates). The pre-circulation process which flows 99a-99c) is started. Thereafter, when the predetermined timing is reached, the opening degrees of the respective valves of the three-way switching valves 179a and 179b are changed again, and the additive liquids 99a to 99c to be sent to the addition nozzle 51 at a predetermined flow rate. It flows into the pipe 55. In this way, the pre-circulation process to circulate before adding to the pure dope 44, and preparation of the additive liquid added to the pure dope 44 are performed. The pre-circulation time is preferably in the range of 120 minutes or more and 1440 minutes or less, and particularly preferably 150 minutes or more and 720 minutes or less.

The pre-circulation time is set to 120 minutes so as to start the circulation 120 minutes before the addition start timing signal, and the pre-circulation process is performed before the addition, but in order to obtain an appropriate value of the pre-circulation time, the pre-circulation time When various values were changed between 60 minutes and 300 minutes, when it was less than 120 minutes, an additive might not become uniform and a nonuniformity might appear in a product. In addition, when it exceeds 240 minutes, a product phase does not have a problem especially, but it is an excessive operation time, and cannot be said to be a preferable value from a viewpoint of process cost. Therefore, the pre-circulation time is preferably 120 minutes or more and 1440 minutes or less, and particularly preferably 150 minutes or more and 720 minutes or less.

The circulation flow rate in the circulation part 173 becomes the same amount as the addition flow volume of the additive liquids 99a-99c. The addition flow rate is set as the flow rate ratio with respect to the pure dope 44, and when the addition flow rate of the additive liquid whose additive concentration is 1% is set when the pure dope 44 is 20 L / min, it is 200 Pa / min (= Circulated in the circulation portion 173 at a flow rate of 200 × 10 ⁻⁶ m 3 / min. The open / close valve is opened by the addition start timing signal to the pure dope 44, and the additive liquids 99a to 99c are added to the pure dope 44 from the addition nozzle 51 at the same amount as the circulation flow rate. Thus, since the flow rate at the time of the pre-circulation process and the flow rate at the time of addition are made the same by performing the pre-circulation process at the same flow rate as at the time of addition, only a valve moves during the switching process from circulation to the addition. For this reason, neither pulsation occurs nor the adjustment time of additive switching for suppressing pulsation occurs. On the other hand, in the case of the conventional switching process, since the addition start timing signal is input and the flow rate is adjusted, the pressure also changes and the flow rate also changes. Therefore, the pulsation and pressure fluctuation are large, and it takes a long time to adjust until it stabilizes. During this adjustment time, since the flexible dope has not reached the content of the additive required for the product, the film by the flexible dope between them is not used as a product, which is wasteful. In this invention, since this adjustment time becomes unnecessary, the loss time is reduced by that much, and the waste of flexible dope is also reduced.

The other additive liquid combination systems 96 and 97 are similarly comprised, and the same code | symbol is attached | subjected to the same structural member. The circulation part 173 comprises the circulation part 173 in the state which closed the opening-closing valve 57 until the addition of the newly added additive liquid 99a-99c to the pure dope 44 starts, and this circulation part The additive liquids 65a to 65c are circulated in the atmosphere 173.

The cleaning liquid supply part 182 is connected to the circulation part 173 through the opening / closing valve 181. The cleaning liquid supply part 182 sends the solvent which is a cleaning liquid to the circulation part 173 at the time of breed switching, and wash | cleans the additive liquid previously supplied. The washing liquid after washing is discharged from the addition nozzle 51, and the additive liquid 51 is washed from the additive liquid supply part 93. After washing, each additive liquid combination system 95 to 97 supplies a new additive liquid 65a to 65c for the next variety after closing the on / off valve 57 and circulates in the circulation 173. In addition, the film by flexible dope during the varieties switching operation in which this washing | cleaning liquid is discharged | emitted from the addition nozzle 51 does not become a predetermined additive addition amount, and is excluded from a product. As described above, in the varieties switching of the film 106, the additive liquids 99a to 99c added to the film 106 before switching and the additive liquid 99a added to the film 106 after switching in the additive liquid supply unit 93. The pipe flowing in common with ˜99c) is cleaned with a cleaning liquid.

The addition nozzle 51 is the same flat nozzle as 1st Embodiment. After the additive liquids 99a to 99c are uniformly added to the pure dope 44 by the static mixer 52, the foreign substance is removed from the pure dope 44 by the second filter 53 like the first embodiment. It becomes the flexible dope 54. And the casting dope 54 is sent to the casting die 107 (refer FIG. 2) of the film forming unit 13. As shown in FIG.

Also in this 4th embodiment, like the 1st embodiment, necessary additives are supplied by the additive liquid supply part 93 and the addition nozzle 51 according to the film varieties manufactured with respect to the pure dope 44 to which the additive is not added. This makes it possible to respond quickly to new varieties.

In the additive liquid combination unit 170, various additives required for the varieties produced from the combination LUT 167 are specified, these specific additives are added to the solvent 27 as needed, and the additive liquid is combined.

As described above, when the flexible dope 54 containing different additives is switched to one solution film production facility 90 to be manufactured, it is good to change only the type of additive liquids 99a to 99c and the amount of addition thereof. As mentioned above, the section which extrudes and replaces previous dope with new dope at the time of dope switching of an old and new can be shortened.

Also in this 4th embodiment, the addition nozzle 51 is arrange | positioned in the position which becomes piping capacity C2 of 1 / 280-1 / 7 with respect to the conventional piping capacity C1 on the downstream side in breed switching. Doing. For this reason, like 1st-3rd embodiment, the loss of dope can be suppressed about 1 / 280-1 / 7 about the thing of a conventional installation.

On the outlet side of the additive liquid tank 177, an online component system may be provided as necessary to be the same as the outlet side of the additive liquid tank 65 (see FIG. 1) to measure whether the additive component of the additive liquid is within a predetermined range. good. In this case, the additive amount of the various additives in the mixing tank 176 is increased or decreased in accordance with the measurement result to control the various additive components within a predetermined range.

The additive addition unit 92 is equipped with the 2nd filter 53 similarly to the additive addition unit 12 of 1st Embodiment. The second filter 53 is filtered before the pure dope 44 to which the additive liquids 99a to 99c are added on the upstream side of the casting die 107 is provided to the casting. Thereby, the dope 54 in 3rd Embodiment also becomes that the impurity was removed further.

In the continuous manufacture of the film 106, when the variety switching is performed by changing the type or amount of various additives, the additive addition unit 92 is switched from the old additive to the new additive in the state of continuous casting. First, when the variety switching information is sent from the master controller (not shown) to the controller 98 of the additive adding unit 92, the controller 98 prepares additive liquids 99a to 99c corresponding to the new product. In addition, the controller 98 switches the additive liquid added to the pure dope 44 at this switching timing by inputting a varieties switching timing signal of the additive liquids 99a to 99c corresponding to the old product among the variety switching information sent. Discharge and washing of the additive liquids 65a to 65c of the old type are carried out so as to be possible, and circulation of the additive liquids 65a to 65c of the new type is performed. Then, the three-way switching valves 179a and 179b are switched again by the varieties switching timing signal to stop the circulation, and the on-off valve 57 provided in the pipe 55 extending to the addition nozzle 51 is provided. Is opened, and a new kind of additive liquid is added into the pure dope 44 from the addition nozzle 51.

In addition, in the said 4th Embodiment, although various additive liquids 99a-99c were added to the pure dope 44 using one addition nozzle 51, as shown in FIG. 6 instead, for example, You may use the additive addition unit 187 which added the additive liquid with respect to the pure dope 44 using four addition nozzles 185a-185d. In the case of this fifth embodiment, the additive liquid supply parts 186a to 186d are provided for each additive liquid, respectively. Although the additive liquid supply part 186a-186d is comprised similarly to the additive liquid supply part 93 of 4th Embodiment, the additive liquid combination system has only one system corresponding to each additive. Moreover, you may use plural additive liquid supply parts 93 which can supply the several types of additive liquid of 4th Embodiment as additive liquid supply parts 86a-86d. In FIG. 6, the same code | symbol as FIG. 1-FIG. 5 is attached | subjected to the structural member similar to 1st Embodiment-4th Embodiment, and the overlapping description is abbreviate | omitted.

The solution film forming equipment 210 of the sixth embodiment shown in FIG. 7 includes a pure dope preparation unit 11, an additive adding unit 212, and a film forming unit 13. In FIG. 7, the same code | symbol as FIG. 1-FIG. 6 is attached | subjected to the structural member similar to 1st Embodiment-5th Embodiment, and the overlapping description is abbreviate | omitted.

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

The 1st additive liquid supply part 247 is for adding a plasticizer, and the liquid supply part for sending the additive liquid combination part 170 and the additive liquid 261a from this additive liquid combination part 260 to the addition nozzle 51a. 262 is provided. The liquid feeding part 262 is composed of a pump 263, a pipe 264, and a circulation part 265.

The additive liquid combination part 170 is the same as that in 4th Embodiment shown in FIG. 5, The plasticizer supply part 174, the solvent supply part 175, and the plasticizer and solvent supplied from each supply part 174 and 175 are stirred. The mixing tank 176 and the additive liquid tank 177 to mix 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. This plasticizer concentration is preferably used in the range of 10 weight% or more and 65 weight% or less. In addition, a plasticizer viscosity is used preferably in the range of 10000 Mpa * s or less.

The circulation section 265 is composed of a circulation pipe 268 and three-way switching valves 266 and 267. In addition, the cleaning liquid supply part 270 is connected to the circulation pipe 268 through the opening / closing valve 269. The inlet-side three-way switching valve 266 is provided in a pipe 264 connecting the additive liquid combination unit 170 and the pump 263. The outlet 3-way switching valve 267 is provided in the liquid supply pipe 255 of the first additive liquid supply part 247. When each of the three-way switching valves 266 and 267 is input with the following new type of switching timing signal, the opening degree of the valve is switched in the same manner as in the fourth embodiment based on this switching timing signal. By this switching, the additive liquids 261a to 261d used in the new varieties are pre-circulated at a predetermined flow rate prior to the addition timing. Thereafter, when a predetermined timing is reached, the opening degree of each valve of each of the three-way switching valves 266 and 267 is changed again, and the additive liquids 261a to 261d to be added to the pure dope 44 are added at a predetermined flow rate. 51a ~ 51d). In this way, preparation and pre-circulation processing of the additive liquids 261a to 261d are performed. The pre-circulation time is preferably in the range of 120 minutes or more and 240 minutes or less, and particularly preferably 150 minutes or more and 210 minutes or less.

The circulation flow rate in the circulation portion 265 is equal to the flow rate of addition of the additive liquid 261a. The addition flow rate is set as the flow rate ratio with respect to the pure dope 44, and when the addition flow rate of the 1% additive liquid is set when the pure dope 44 is 20 L / min, it is 200 kPa / min (= 200x10 <^->). Circulation in the circulation section 265 at a flow rate of ⁶ m 3 / min. The open / close 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 at the same amount as the circulation flow rate. As described above, in the sixth embodiment, the flow rate during the atmospheric circulation operation and the flow rate during the addition become the same by performing the atmospheric circulation operation at the same flow rate to be added, so that only the valve moves during the switching process from the circulation to the addition. do. For this reason, neither pulsation occurs nor the adjustment time of additive switching for suppressing pulsation occurs. Therefore, the loss time is reduced as much as this adjustment time becomes unnecessary, and the waste of flexible dope is also reduced.

By the way, when the addition flow rate of the additive liquid 261a is smaller than the flow rate of the pure dope 44, it takes time to circulate as described above and wait for the predetermined pressure even if it is changed at a predetermined timing thereafter. In comparison with normal addition, switching time becomes long. If switching takes long, efficient switching is impossible. In addition, since the flexible dope has not reached the content of the additive required for the product during the switching time, the film by the flexible dope between them is not a product, which is wasteful. This production time loss or product loss is larger as the additive flow rate of the additive liquid 261a to the flow rate of the pure dope 44 is smaller.

Therefore, in the sixth embodiment, in order to shorten the adjustment time at the time of addition of a small amount, as shown in FIG. 8, when the addition amount of the additive liquid is below a predetermined amount ("A" in FIG. 8) in breed switching, For example, {(QAE / QD) × 100} (unit is%), which is the addition flow rate ratio of the addition flow rate (target value) (QAE) of the additive liquid switched according to the new variety with respect to the flow rate (QD) of the dope, is 10. % Or less, and when the addition flow rate QAE is 300 × 10 ⁻⁶ m 3 / min (= 300 m 3 / min) or less, the initial addition flow rate QAS equal to 1.5 times or more and 3.0 times or less of the addition flow rate QAE. The addition is carried out for a certain time. After the elapse of the predetermined time, the flow rate is set to QAE, which is a target value from QAS. When the initial addition flow rate QAS is less than 1.5 times the addition flow rate QAE, the effect of time reduction is small, and when the initial addition flow rate QAS exceeds 3.0 times the addition flow rate QAE, pulsation is generated upon returning to the target addition flow rate. In addition, it is necessary to use a large capacity of the liquid feed pump, which is disadvantageous in terms of equipment. In this manner, the addition may be performed to increase the additive liquid at a constant flow rate at a flow rate larger than the target flow rate QAE, and the flow rate may be reduced to the target flow rate QAE after a predetermined time.

The fixed time is 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 in the vicinity of the outlet of the addition nozzle 51a. It's time. This time is stored in the LUT memory 258a for each additive liquid, and the representative value obtained by experiment or the like in advance can be increased on the basis of the stored time. In addition, instead of using the representative value memorize | stored previously, the pressure of the additive liquid 261a is measured with the pressure gauge installed in the vicinity of the exit of the addition nozzle 51a like 7th embodiment shown in FIG. You may change the said fixed time based on the measured pressure value. Changing the fixed time based on the measured pressure value, that is, if the pressure value of the measured additive liquid 261a becomes equal to the pressure of the pure dope 44 near the outlet of the addition nozzle 51a, initially. The increase is terminated regardless of the predetermined time period expected.

"Scheduled time" for increasing the amount of 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 as described above. Most preferably. However, even if the setting of the flow rate 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 flow rate change point. The time difference occurs at the time when the flow rate setting is changed without changing the flow rate setting and the rising pressure becomes constant, and it is sometimes difficult to set this time difference to zero (zero). For example, in such a case, the amount is increased before reaching the same pressure as the pressure of the pure dope 44 near the outlet of the addition nozzle 51a in consideration of the time difference, that is, the pressure smaller than the pressure of the pure dope 44. The addition may be finished. That is, according to the time difference or the like, the "constant time" may be shorter than the time until the pressure of the additive liquid 261a reaches the same pressure as the pressure of the pure dope 44.

Since the amount of additive liquid for each variety is obtained and stored in the LUT memory 258a in advance, the operator does not need to input the additive liquid flow rate of the various additive liquids, and there is no error in the set value due to an input operation error. There will be no. For this reason, in the case of a set value miss, the dope of the section of this set value miss was wasteful, but such a waste can be eliminated.

In addition, the addition flow rate ratio {(QAE / QD) x 100} of the addition flow rate QAE of the additive liquid switching to new varieties with respect to the flow rate QD of the pure dope 44 which is the reference dope may exceed 10%. In this case, it is not necessary to perform the circulation treatment or the increase addition treatment at the increased initial addition flow rate QAS as described above, and the circulation is performed for a predetermined time at the addition flow rate QAE. The predetermined time is determined in advance by experiment, simulation, or the like, and is stored in the LUT memory 58a of the controller 258. By the circulation treatment, as described above, the dope addition time (loss time) in the state in which the additives during the switching are mixed in the breed switching can be reduced, and the waste of the flexible dope is reduced.

The LUT memory 258a stores kinds and addition amounts of various additives such as a plasticizer, a mat agent, a UV agent, and a retardation control agent added to the pure dope 44 in addition to the predetermined time. The kind and addition amount of these various additives are calculated | required in advance for every kind of film 106 to manufacture. The controller 258 obtains the type and amount of additives from the LUT memory 258a according to the film type. The additive liquids 261a to 261d are prepared in the additive liquid combination unit 170 based on the type and the amount of the additives obtained. The prepared additive liquids 261a to 261d are stored in the respective additive liquid tanks 177. In addition, the presence or absence of the addition process and the increase ratio during the addition process are also determined in advance by experiments and stored in the LUT memory 258a.

The other 2nd-4th additive liquid supply parts 248-250 are comprised similarly to the 1st additive liquid supply part 247, and detailed description is abbreviate | omitted. The second additive liquid supply part 248 prepares the additive liquid 261b in which the mat agent and the solvent are mixed. The third additive liquid supply unit 249 prepares the additive liquid 261c in which the UV agent and the solvent are mixed. In addition, the fourth additive liquid supply unit 250 prepares an additive liquid 261d in which a retardation control agent and a solvent are mixed.

As such, by providing the plurality of additive liquid supply parts 247 to 250 for the kinds of the additives required, the plurality of kinds of the additive liquids 261a to 261d can be introduced into the pure dope 44 as necessary, respectively. have. In this embodiment, four additive liquid supply parts 247-250 are provided, but what is necessary is just these as needed.

The circulation unit 265 is circulated by the three-way switching valves 266 and 267 and the circulation pipe 268 until the newly added additive liquids 261a to 261d are started to be added to the pure dope 44.

In addition, the circulating part 265 is connected to the cleaning liquid supply part 270 through an opening / closing valve 269. The cleaning liquid supply unit 270 sends the solvent to the circulation unit 265 at the time of breed switching, and cleans the additive liquid that has been supplied first. The washing liquid after washing is discharged from the addition nozzle 51a, and the washing liquid from the first additive liquid supply part 247 to the addition nozzle 51a is washed. After the cleaning, the additive liquid combination unit 170 closes the on / off valve 57 and sends new additive liquids 261a to 261d for the next variety to circulate in the circulation unit 265. In addition, the film by flexible dope during the varieties switching operation in which these three semens are discharged from the addition nozzle 51a is not a predetermined additive addition amount, and is excluded from a product.

The other 2nd-4th additive liquid supply parts 248-250 are comprised similarly to the 1st additive liquid supply part 247, and detailed description is abbreviate | omitted. The second additive liquid supply part 248 prepares the additive liquid 261b in which the mat agent and the solvent are mixed. The third additive liquid supply unit 249 prepares the additive liquid 261c in which the UV agent and the solvent are mixed. In addition, the fourth additive liquid supply unit 250 prepares an additive liquid 261d in which a retardation control agent and a solvent are mixed.

As such, by providing the plurality of additive liquid supply parts 247 to 250 for the kinds of the additives required, the plurality of kinds of the additive liquids 261a to 261d can be introduced into the pure dope 44 as necessary, respectively. have. In this embodiment, although four additive liquid supply parts 247-250 are provided, these may be increased or decreased suitably.

Addition nozzles 51a-51d are the same flat nozzles as the addition nozzle 51 of 1st Embodiment in which the tip was crushed flat. These addition nozzles 51a-51d are arrange | positioned in the dope piping 46 in accordance with the radial direction of the dope piping 46 at the front-end flat part. The static mixer 52 disposed on the downstream side of the addition nozzles 51a to 51d is formed by twisting a rectangular plate by 180 degrees. The plurality of elements 52a are arranged in series in the piping to add the addition nozzles 51a to 51d to the pure dope. Various additive liquids added by the dispersion are dispersed and mixed. In the pure dope 44 via the static mixer 52, foreign matter is removed from the second filter 53 to become the flexible dope 54. This casting dope 54 is sent to the casting die 107 (see FIG. 2) of the film forming unit 13.

In the sixth embodiment, since the necessary additives are supplied by the additive liquid supply parts 47-50 and the addition nozzles 51a-51d according to the film varieties produced for the pure dope 44 to which the additives are not added, You can respond quickly.

In the additive liquid combination unit 170, various additives required for varieties produced from the LUT 258a are specified, these specific additives are added to the solvent 27 as needed, and the additive liquid is combined.

Thus, also in 6th Embodiment, it is only good to change the kind of additive liquid, and the addition amount, and it can shorten the section which extrudes and replaces the previous dope with new dope at the time of dope switching of a new and old as before.

Extrusion substitution part will be in the state which mixed old and new dope. Also in the sixth embodiment, the addition nozzles 51a to 51d are positioned at a position that becomes the piping capacity C2 of 1/280 to 1/7 with respect to the conventional piping capacity C1 on the downstream side in the breed switching. To place. For this reason, the film part in which the old and new additives are mixed is about three times as much as the piping capacity after this addition nozzle, and the loss of dope can be suppressed about 1 / 280-1 / 7 with respect to the thing of a conventional installation.

Moreover, also in 6th Embodiment, you may provide an online component system in the exit side of the additive liquid tank 177, and may measure whether the additive component of an additive liquid exists in a predetermined range. And the addition amount of the various additives in the mixing tank 76 may be increased or decreased according to a measurement result, and various additive components may be controlled in a predetermined range.

The additive addition unit 212 is provided with the 2nd filter 53 similarly to the additive addition unit 12 of 1st Embodiment. The second filter 53 is filtered before the pure dope 44 to which the additive liquids 261a to 261d are added is upstream of the casting die 107. As a result, the dope 54 in the present embodiment is also one in which impurities are further removed.

In the continuous production of the film 106, in the case of performing variety switching by changing the type or amount of various additives, the additive addition unit 212 is switched from the old additive to the new additive in the state of continuous casting. First, when the variety 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 additive liquids 261a to 261d corresponding to the new varieties. . Further, the additive liquids 261a to 261d corresponding to the old varieties are discharged, washed, and added to the new varieties of the additive liquids 261a to 261d to enable switching at this switching timing by input of the varieties switching timing signal. The cycle of (261a-261d) is performed. Then, the three-way switching valves 266 and 267 are switched by the varieties switching timing signal to stop the circulation, the opening / closing valve 57 is opened, and a new kind of additive liquid is added to the pure dope from the addition nozzles 51a to 51d. Add.

In addition, in 5th Embodiment, it is made to add various additive liquids 261a-261d with respect to the pure dope 44 using each addition nozzle 51a-51d provided corresponding to each additive liquid supply part 247-250. However, instead of this, although not shown, for example, an additive addition unit may be used in which the additive liquid is added to the pure dope 44 at the same position using one addition nozzle.

In the sixth embodiment, it is judged whether or not the time of the increase addition by the initial addition flow rate QAS has reached a predetermined time determined in advance, and after the fixed time has elapsed, the flow rate is changed from the initial addition flow rate QAS to the addition flow rate QAE. Although the change is made, the timing of this change is similar to the seventh embodiment shown in FIG. 9, and the pressure in the vicinity of the outlet of the addition nozzle is detected by the pressure sensor, and the detected pressure Pa is 90, for example, of the set pressure P1. When the% is reached, the flow rate 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 dope preparation unit 11, an additive adding unit 312, and a film forming unit 13. In FIG. 10, the same code | symbol is attached | subjected to the structural member similar to FIGS. 1-10 which is 1st-7th embodiment, and description is abbreviate | omitted.

The pure dope (reference dope) 44 stored in the storage tank 43 of the storage portion 18 is sent to the additive adding unit 312 by the pump 45. The additive addition unit 312 is the dope pipe 46 through which the pure dope 44 flows, the 1st-4th additive liquid supply parts 247-250 like 6th embodiment, the addition nozzles 51a-51d, and an inline The mixer 352, the 2nd filter 53, and the controller 358 are comprised. A check valve 56 or an opening / closing valve 57 is installed in each pipe 355 to transfer the additive liquids 261a to 261d to the addition nozzles 51a to 51d to prevent the backflow of the additive liquids 261a to 261d. It is.

In the LUT memory 358a, the amount of additive liquid added for each variety is obtained in advance and stored in the same manner as the LUT memory 258a in FIG.

In addition, the circulation processing time before addition of an additive liquid is calculated | required previously by experiment, simulation, etc., These are memorize | stored in the LUT memory 358a of the controller 358. By the circulation treatment, as described above, the dope addition time (loss time) in the state in which the additives during the switching are mixed in the breed switching can be reduced, and the waste of the flexible dope is reduced.

In addition to the fixed time, the LUT memory 358a stores kinds and addition amounts of various additives such as a plasticizer, a mat agent, a UV agent, and a retardation control agent added to the pure dope 44. The kind and addition amount of these various additives are calculated | required previously for every kind of film to manufacture. The controller 358 obtains the type and amount of additives from the LUT memory 358a according to the film type. The additive liquids 261a to 261d are prepared in the additive liquid combination unit 170 based on the type and the amount of the additives obtained. The prepared additive liquids 261a to 261d are stored in the respective additive liquid tanks 177. In addition, the presence or absence of the addition process, the increase ratio during the addition process, and the like are also determined in advance by experiments and stored in the LUT memory 358a.

The other 2nd-4th additive liquid supply parts 248-250 are comprised similarly to the 1st additive liquid supply part 247, and detailed description is abbreviate | omitted. The 2nd additive liquid supply part 48 prepares the additive liquid 61b which mixed the mat agent and the solvent. The 3rd additive liquid supply part 49 prepares the additive liquid 61c which mixed the UV agent and the solvent. Moreover, the 4th additive liquid supply part 50 prepares the additive liquid 61d which mixed the retardation control agent and the solvent.

Thus, by providing the several additive liquid supply parts 47-50 for the kind of additive required, the several kinds of additive liquid 61a-61d according to a film type are added from the addition nozzle 51a-51d by the required degree, respectively. Each can be fed into the pure dope 44 (the dope piping 46. In this embodiment, although four additive liquid supply parts 47-50 are provided, these may be increased or decreased appropriately.) This embodiment In each case, the inline mixers 352 are provided on the downstream sides of the addition nozzles 51a to 51d, respectively.

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

The buffer supply part 385 is provided with the solvent supply part 375 and the liquid feed pump 386, and is the same liquid as the component of the solvent 27 of the 2nd tank 22 (refer FIG. 10) by the liquid supply pump 386. Is supplied to the outer passage 384 as a buffer 387. By supplying the buffer solution 387 to the outer passage 384, a buffer layer 389a is formed in which the boundary between the pure dope 44a and the buffer solution 389 is formed at the outer circumference of the additive solution 388. Since the additive solution 261a and the buffer 387 and the buffer 387 and the pure dope 44 are mixed little by little by this buffer layer 389a, the additive liquid 261a directly contacts the pure dope 44. Compared to contact and mixing, gelation and condensation of additives do not occur. Thus, the buffer 387 is used in order to form the buffer layer 389a which suppresses the buffer of the additive liquid 261a and the pure dope 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 solution 261a in each of the elements 394a, 394b, 395a, and 395b. ) Is dispersed and mixed, so that gelation and aggregation of the additives are not generated in the same manner. The tip portion of the inner tube 380 is formed in a tapered shape in which the diameter of the inner circumferential surface of the circular cross section is constant in the longitudinal direction, while the outer circumferential surface thereof becomes smaller in diameter toward the tip. As a result, the buffer layer 389a is more reliably formed around the additive liquid stream 388.

At this time, in 8th Embodiment, when the flow volume of the additive liquid flow 388, ie, the flow volume of the additive liquid 261a, is QAE and the flow volume of the buffer liquid 389 is QB, the flow rate ratio (QB / QAE) is 0.01 or more and 0.1. The flow rates and the like of the respective liquid flows 388 and 389 are adjusted to be below. This is because when the flow rate ratio is less than 0.01, the buffer function by the buffer layer 389a is weakened, and as mentioned above, gelation and aggregation of the additive may occur. On the contrary, when the flow rate ratio exceeds 0.1, the concentration of the additive liquid 261a in the pure dope 44 is lowered, which may lower the casting suitability of the cast dope 54.

The other 2nd-4th additive liquid supply parts 248-250 are similarly equipped with the addition nozzle 51b-51d of the dual structure, and the buffer solution supply part 385. In addition, depending on the type of the additive liquid, gelling and condensation are less likely to occur. In this case, the double nozzle addition nozzle and the buffer supply portion may be omitted, and in this case, the additive liquid may be added using a normal addition nozzle. . In addition, the addition nozzles 51 and 51a used by 1st Embodiment-7th embodiment are also the same as the addition nozzle 51a of this embodiment.

As shown in FIG. 13, the in-line mixer 352 is comprised from the split mixing type static mixer 392 and the salt mixing type static mixer 393. As shown in FIG. The split-mix type static mixer 392 is provided near the front of each addition nozzle 51a-51d. Elements 394a and 394b are provided in the split-mix type static mixer 392, and they are alternately arranged in the longitudinal direction of the dope pipe 46. The elements 394a and 394b are formed by being joined to alternately intersect a plurality of elongated boundary plates. The split-mix type static mixer 392 mixes the pure dope 44 and the additive liquids 261a to 261d flowing through the dope pipe 46 by dividing the elements by the elements 394a and 394b.

The salt mixing type static mixer 393 is disposed downstream of the split mixing type static mixer 392. The salt mixing type static mixer 393 is provided with elements 395a and 395b, and these are alternately arranged in the longitudinal direction of the dope pipe 46. The elements 395a and 395b are formed by twisting a rectangular plate 180 degrees, and the twisting directions of the elements 395a and 395b are reversed. The elements 395a and 395b are disposed in a state of being rotated 90 degrees about the axis of the dope pipe 46 so that the side ends of the plates are perpendicular to each other. The salt mixing type static mixer 393 mixes the pure dope 44 and the additive liquids 261a to 261d flowing through the dope pipe 46 while switching by the elements 395a and 395b.

In addition, although FIG. 13 shows the most upstream addition nozzle 51a and the inline mixer 352 of the four addition nozzles 51a-51d and four inline mixers 352 shown in FIG. 10, another addition nozzle is shown. The same applies to the 51b to 51d and the inline mixers 352 disposed downstream of these.

The additive addition unit 312 is also equipped with the 2nd filter 53 similarly to the additive addition unit 12 of 1st Embodiment. The second filter 53 is filtered before the pure dope 44 via the inline mixer 352 on the upstream side of the casting die 107 is provided to the casting. Thereby, also in the casting dope 54 in 8th Embodiment, an impurity is further removed, and is sent to the casting die 107 (refer FIG. 2) of the film forming unit 13. As shown in FIG.

Also in this embodiment, since the required additives are supplied by the additive liquid supply parts 247 to 250 and the addition nozzles 51a to 51d, respectively, according to the film varieties to be produced for the pure dope 44 to which the additives are not added, You can respond quickly. In addition, in this embodiment, since the inline mixer 352 is provided in each downstream of addition nozzles 51a-51d, and it mixes every time each of the additive liquids 261a-261d is supplied, each additive liquid 261a- The additive contained in 261d) is likely to be dispersed in the pure dope 44 uniformly, respectively.

In the additive liquid combination unit 170, various additives required for the varieties produced from the combination LUT 358a are specified, these specific additives are added to the solvent 27 as needed, and the additive liquid is combined.

In the continuous production of the film 106, in the case of performing variety switching by changing the type or amount of various additives, the additive addition unit 212 is switched from the old additive to the new additive in the state of continuous casting. First, when the variety switching information is sent from the master controller (not shown) to the controller 358 of the additive adding unit 312, the controller 358 controls each unit to prepare additive liquids 261a to 261d corresponding to the new varieties. do. Further, the additive liquids 261a to 261d corresponding to the old varieties are discharged, washed, and added to the new varieties of the additive liquids 261a to 261d to enable switching at this switching timing by input of the varieties switching timing signal. The cycle of (261a-261d) is performed. Then, the three-way switching valves 266 and 267 are switched by the varieties switching timing signal to stop the circulation, the opening / closing valve 57 is opened, and a new kind of additive liquid is added to the pure dope from the addition nozzles 51a to 51d. Add.

Moreover, also in this embodiment, various additive liquids 61a-61d were added to pure dope using each addition nozzle 51a-51d provided corresponding to each additive liquid supply part, However, illustration is abbreviate | omitted instead. However, you may use the additive addition unit which made the additive liquid add in the same position with respect to pure dope, for example using one addition nozzle. Also in this case, it is set as a double piping structure, the mixed additive liquid which mixed several types of additive liquids to the inner channel | path is supplied, and a buffer liquid is supplied to an outer channel | path. In addition, although illustration is abbreviate | omitted instead of the mixed addition, you may form a some additive liquid path | route, for example in a quadruple piping structure, supply an additive liquid to each channel individually, and supply a buffer liquid to the channel of an outermost layer.

In addition, when adding in the same position, as shown in FIG. 11, you may add an additive to a reference dope (pure dope) by arrange | positioning two or more addition nozzles of the said double piping structure. Moreover, you may add some additive in the same position or another position in the passage of reference dope using multiple addition nozzles of 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 the dynamic mixer 420 (see FIG. 14) may be used.

As shown in FIG. 14, the dynamic mixer 420 has the cylindrical case 421 provided in the middle of the dope piping 46, the mixer main body 422 accommodated in the case 421, and the mixer main body 422. As shown in FIG. It consists of a support member 423 for rotatably supporting the.

The mixer main body 422 consists of a conical tip 422a and a cylindrical body 422b, and is attached to the support member 423 such that the tip 422a faces the upstream of the liquid flow direction. As a result, a gap 425 is gradually formed between the inner wall surface of the case 421 and the outer peripheral surface of the mixer main body 422 from the upstream side to the downstream side in the liquid flow direction. The mixer main body 422 operates (rotates) on the same operation principle as that of a known pulse motor by, for example, an electromagnet provided at a predetermined pitch on the outer circumferential surface of the case 421 and a magnet built into the body portion 422b. do.

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

The pure dope 44 and the additive liquids 261a-261d sent to the dynamic mixer 420 are divided by the tip portion 422a of the mixer main body 422, and are passed downstream through the gap 425 and the gap flow path 423a. It flows into the dope pipe 46 of the side. At this time, as the mixer main body 422 rotates, the pure dope 44 and the additive liquids 261a to 261d that pass through the gap 425 are stirred and mixed.

In the above embodiment, the same liquid as that of the component of the solvent 27 of the pure dope or narrow reference dope is used as the buffer 387. However, the present invention is not limited thereto, and the additive liquid is the same liquid as the component of the solvent. May be used as the buffer solution 387, such as the dilution liquid of the additive liquid diluted with the dilution solution, the dilution liquid of the reference dope diluted with the same liquid as the components of the solvent. In addition, the same liquid as a component is the single component when the solvent 27 consists of a single component, and what is necessary is just at least any one of a plurality of components when the solvent 27 consists of multiple components. In addition, in the said embodiment, although demonstrated using the addition nozzle of the substantially circular cross-sectional shape as an example, this invention is not limited to this, For example, such as a flat nozzle extended in the radial direction of the dope piping 46, etc. You may use nozzles of various shapes.

In addition, in said 4th-8th embodiment, although the additive liquid was added to the pure dope 44 just before the casting die 107, the dope is not limited to the pure dope 44, As conventionally, Flexible dope may contain various additives in the dope, and even in this case, a new variety of films can be similarly produced by adding the additive immediately before the flexible die. Various additives are similarly mixed when the polymer 26 and the solvent 27 are mixed in the mixing section 15 in FIG. 5.

In addition, instead of the pure dope 44 or the conventional flexible dope, a common additive is added and mixed together when the polymer 26 and the solvent 27 are mixed in the mixing section 15 in FIGS. 5, 7 and 10. You may mix and use as a reference criterion of consultation. The standard reference dope is prepared by dispersing only the additives commonly required in each variety in dissolving the polymer 26 and the solvent 27 in advance. In this case, the amount of additives added immediately before the casting die, i.e., just before the addition, can be reduced by the amount of the common additive, thereby enabling efficient addition.

In the fourth to eighth embodiments, single-layer softening has been described as an example, but may be shared lead as in the case of the first to third embodiments.

In addition, the static mixer 52 of 1st-7th embodiment may be any of the split-mixing type static mixer 392 and the salt mixing type static mixer 393 in 8th Embodiment, and may combine these. In addition, the static mixer 52 may be replaced with the dynamic mixer 420.

Hereinafter, the Example performed about this invention is shown, and this invention is demonstrated concretely. However, this invention is not limited to these Examples.

Example 1

The following polymer 26 and solvent 27 were mixed in the dissolution tank 23 to prepare a pure dope 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 tri acetate

[Mixed solvent]

320 parts by weight of dichloromethane

83 parts by weight of methanol

3 parts by weight of 1-butanol

In the additive addition unit 12, said mixed solvent and additives were mixed, the additive liquid A was comprised, and this additive liquid was added to the pure dope 44 by the addition nozzle 51. As shown in FIG.

[Additives amount (A)]

80 parts by weight of a mixed solvent

Plasticizer A 7.6 parts by weight

Plasticizer B 3.8 parts by weight

UV agent: 0.7 parts by weight

UV agent b 0.3 parts by weight

0.006 parts by weight of citric acid ester mixture

0.05 part by weight of fine particles

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

[Additives amount (B)]

80 parts by weight of a mixed solvent

Plasticizer C 6 parts by weight

Plasticizer D 6 parts by weight

UV agent: 0.7 parts by weight

UV agent b 0.3 parts by weight

0.006 parts by weight of citric acid ester mixture

0.05 part by weight of fine particles

The cellulose triacetate has a viscosity of 315 mPa · s, a substitution degree of 2.84, a viscosity average degree of polymerization of 306, a water content of 0.2% by weight, and 6% by weight of a dichloromethane solution, a powder having 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 agent a is 2 (2'-hydroxy-3 ', 5'-di-tert-butyl phenyl) benzotriazole, UV agent b is 2 (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) -5-chlor benzotriazole, 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. In the preparation of the pure dope 44, a retardation control agent (N-N'-di-m-toluyl-Np-methoxyphenyl-1,3,5-triazine-2,4,6-tree) Amine) was added so as to be 4.0% by weight based on the total weight of the film.

Subsequently, by the film forming unit 13 shown in FIG. 2 using the casting dope 54 in which the foreign material was removed by the 2nd filter 53 among the solution film forming facilities 10 shown in FIG. Each process was performed and the TAC film 106 was obtained.

The piping capacity C1 of the whole process from the melt tank 23 to the inlet of the flexible die 107 of the film forming unit 13 is 56000 L (liter), and the flexible die 107 is from the addition position by the addition nozzle 51. The piping capacity C2 up to is 8000L. After adding the additive liquid A with the addition nozzle 51, it mixed inline with the static mixer 52. As shown in FIG. When switching from the film of the varieties A using the additive liquid (A) to the pure dope 44 to the film of the varieties B using the additive liquid (B) with respect to the pure dope 44, the additive liquid (A) does not stop continuously. ) Was switched to the additive liquid (B). The time required for breed switching was 6 hours.

Comparative Example 1

In Comparative Example 1, in the case of switching from the additive liquid (A) to the additive liquid (B) in the dissolution tank 23 in the same manner as the conventional equipment instead of the addition just before the casting die 107 in Example 1, varieties A and B Was prescribed in the same manner as in Example 1. The piping capacity (C1) is 56000L, 42 hours are required for the flexible doping of the product B from the flexible dope of the product A, and during this time, the additive liquids (A, B) are mixed, and the About 3 times of flexible dope could not be used as a product, resulting in product loss.

Example 2

In order to obtain the film 106 of the varieties A, the film forming equipment 90 shown in FIG. 5 and the film forming film shown in FIG. 2 are used as the dope flow rate 20L / min, the immediate addition rate of the plasticizer 2%, and the immediately preceding addition rate of the UV agent 1%. The film 106 was manufactured by the unit 13. Additive liquid flow rate [400 kPa / min (= 400 × 10) using the additive liquid (99a) containing the plasticizer at the same rate as before (120 minutes ago) immediately before the addition (added at the timing of C2 / C1 = 1/280). ^-6 m &lt; ³ &gt; / min)]. In addition, the additive liquid 99b containing the UV agent was circulated at an additive liquid flow rate (200 kPa / min (= 200 x 10 ^-6 m 3 / min)) at the same ratio as the addition ratio, and the atmosphere was circulated. In response to the addition start timing signal, each additive liquid was added to the pure dope 44 from the addition nozzle 51 by switching from circulation to addition. It added without generating a flow rate change after the start of addition operation. That is, since the flow rate at the time of atmospheric circulation operation and the flow rate at the time of addition become the same by performing atmospheric circulation operation at the same flow rate to add, only a valve moves during the switching process from circulation to addition. For this reason, neither pulsation occurs nor the adjustment time of additive switching for suppressing pulsation occurs. In the conventional switching process, since the addition start timing signal is input, the flow rate is adjusted, so that the pressure changes and the flow rate also changes. For this reason, although the pulsation and pressure fluctuation were large and time (adjustment time) until it stabilized was long, it was a cause of a loss, but this could be eliminated. In Example 2, the pulsation prevention and additive adjustment time at the time of addition were unnecessary, and the loss time until reaching the target addition amount which can become a product became 300 minutes, and reduced about 20% compared with Example 4 mentioned later.

Example 3

In order to obtain the film 106 of the varieties B, the dope flow rate was 20L / min, the immediate addition ratio of the plasticizer was 2%, the immediate addition ratio of the UV agent was 1.1%, and the immediate addition ratio of the retardation control agent was 5%. Film 106 was prepared. Additive liquid flow rate [400 kPa / min (= 400 × 10) using the additive liquid 65a containing the plasticizer before the last addition (added at the timing of C2 / C1 = 1/280) (120 minutes ago) ^-6 m &lt; ³ &gt; / min)]. In addition, the additive liquid 65b containing the UV agent was circulated at an additive liquid flow rate (220 kPa / min (= 220 x 10 ^-6 m &lt; 3 &gt; The additive liquid 65c containing the retardation control agent was circulated at the additive liquid flow rate [1000 Pa / min (= 1000 x 10 ^-6 m &lt; ³ &gt; In response to the addition start timing signal, each additive liquid was added to the pure dope 44 from the addition nozzle 51 by switching from circulation to addition. It added without generating a flow rate change after the start of addition operation. The pulsation prevention and additive adjustment time at the time of addition were unnecessary, and the loss time until reaching the target addition amount which can become a product became 300 minutes, and reduced about 20% compared with Example 4 mentioned later.

Example 4

In order to obtain the film of the kind A same as Example 2, the solution film forming installation 90 shown in FIG. 5 and dope flow rate 20L / min, the immediate addition ratio of a plasticizer 2%, and the immediate addition ratio of a UV agent 1%, and FIG. The film was manufactured by the film forming unit 13 shown to. C2 / C1 is 1/280. The part different from Example 2 does not carry out the circulation treatment of the additive liquid, and adds the additive liquid 65a containing the plasticizer at an additive liquid flow rate of 200% / min (= 200 x 10 ^-6 m3 / min). )] Was added to the pure dope (44). In addition, the additive liquid 65b containing the UV agent was added to the pure dope 44 as an additive liquid flow rate [100 kPa / min (= 100 x 10 ^-6 m 3 / min)] which was 1/2 of the addition ratio. In Example 4, since the addition start timing signal is input and the flow rate is adjusted without performing the circulation processing of the additive liquid just before switching as in Examples 2 and 3, the pressure also changes and the flow rate also changes. For this reason, the pulsation and pressure fluctuation are large, and it takes long time (adjustment time) to stabilize. Since the dope during this adjustment time has not reached the prescribed additive addition ratio, it cannot be a product and causes loss. The loss time in Example 4 was 360 minutes.

Example 5

In order to obtain the film of the kind A same as Example 2, the solution film forming installation 90 shown in FIG. 5 and dope flow rate 20L / min, the immediate addition ratio of a plasticizer 2%, and the immediate addition ratio of a UV agent 1%, and FIG. The film was manufactured by the film forming unit 13 shown to. The additive liquid 65a containing the plasticizer before the last addition (added at the timing of C2 / C1 = 1/280) (110 minutes before) was added to the additive liquid flow rate different from the addition ratio [200 s / min (= 200 × 10 ^-6) M 3 / min) (about half of the flow rate in Example 2)] and the atmosphere was circulated. Further, the additive liquid 65b containing the UV agent was circulated at an additive liquid flow rate [100 kPa / min (= 100x10 ^-6 m &lt; 3 &gt; Waited. In response to the addition start timing signal, each additive liquid was added to the dope from the addition nozzle 51 by switching from circulation to addition. Since the circulating process is carried out until just before switching at about half the flow rate as compared with Example 1, the adjustment time can be shortened as compared with Example 4, but the pulsation and pressure fluctuation are larger than those of Example 2 until the stability is achieved. It took a long time for adjustment, and caused the loss similarly to Example 4. The loss time in Example 5 was 330 minutes.

Example 6

Hereinafter, with reference to FIG. 15, Example 6-Example 9 are demonstrated concretely. In Example 6-8, the addition was carried out using the solution film forming installation 210 shown in FIG. 7, and in Example 9, the addition was not carried out. In FIG. 15, Example 6 is denoted by code A, Example 7 is denoted by Code B, Example 8 is denoted by Code C, and Example 9 is denoted by Code D. In FIG. In addition, "T1" shown below the graph of FIG. 15 is the period which extended the addition, ie, the period which continued the initial addition flow volume QAS (henceforth an extension addition period) (unit: minute), and "P1" Silver is the additive liquid at the outlet of the addition nozzle 51a at the flow rate switching time point at which the increase of the additive liquid is completed and the flow rate of the additive liquid 261a is switched from the initial addition flow rate QAS to the addition flow rate QAE. When the pressure of 261a reaches the same pressure as the pressure of the pure dope 44 near each outlet of the addition nozzle 51a, that is, the boosting point, "T2", is the addition flow rate QAE until the boosting point. Means a period (hereinafter, referred to as a target flow rate addition period) (unit; minute) that is continued.

In order to obtain the film 106 of the varieties B, the flow rate QD of the pure dope 44 was 5 L / min and the addition flow rate QAE was 50 kV / min (= 50 x 10) at 1% immediately before the additive liquid. ^-6 m 3 / min). C2 / C1 is 1/100. In this case, the initial flow rate QAS was 150 kPa / min (= 150 x 10 ^-6 m &lt; 3 &gt; Moreover, after passing the increase addition period T1, the addition flow volume QAE was 50 mW / min (= 50x10 <^-6> m <3> / min), and the liquid flow rate was added for 10 minutes as target flow rate addition period T2. In addition, the target outlet pressure of the addition nozzle 51a was 1 MPa. It took 25 minutes to boost the pressure to 1 MPa, and the time from the addition of the varieties A to the varieties B at the time of addition switching was shortened by 30 minutes with respect to the ninth example performed only by the addition flow rate QAE described later. In this embodiment, the amount of the additive liquid 261a that flowed from the start of the increase addition to P2 is 150 (mm / min) × 15 minutes + 50 (mm / min) × 10 minutes = 2750 mm (= 2750 × 10). ^-6 m 3).

Example 7

Example except that the initial addition flow rate QAS was 75 kPa / min (= 75 × 10 ⁻⁶ m 3 / min), the increase addition period T1 was 30 minutes, and the target flow rate addition period T2 was 10 minutes. It was set as the same conditions as 6. It took 40 minutes to boost the pressure to 1 MPa, and the time from the addition of the varieties A to the varieties B at the time of addition was reduced by 15 minutes with respect to the ninth example performed only by the addition flow rate QAE described later. In this example, the amount of the additive liquid 261a flowing from the start of the increase addition to P2 is 75 (cc / minute) x 30 minutes + 50 (cc / minute) x 10 minutes = 2750 ms (= 2750 x 10- ^{). 6} m 3).

Example 8

Except having changed initial addition flow rate QAS into 150 kPa / min (= 150x10 <^-6> m <3> / min), extending | stretching addition period T1 for 18 minutes, and target flow rate addition period T2 for 1 minute. It was set as the same conditions as 6. It took 19 minutes to boost the pressure to 1 MPa, and it was possible to reduce the time from the varieties A to the varieties B by 36 minutes with respect to the ninth example which performs only the addition flow rate (QAE) described later. In this example, the amount of the additive liquid 261a flowing from the start of the increase addition to P2 is 150 (mm / min) x 18 minutes + 50 (mm / min) x 1 minute = 2750 mm (= 2750 x 10- ^{). 6} m 3).

Example 9

The addition flow rate (QAE) was made into 50 kPa / min (= 50x10 <^-6> m <3> / min), and it conveyed and boosted only in target flow volume addition period T2, without extending | stretching addition. Other conditions are the same as those in Example 6. It took 55 minutes to step up to 1 MPa. In this example, the amount of the additive liquid 261a flowing from the start of the increase addition to P2 was 50 (cc / min) x 55 minutes = 2750 cc (= 2750 x 10 ^-6 m 3).

Example 10

In Example 10, TAC was used as the polymer 26 using the solution film forming facility 310 shown in FIG. 10, and pure dope was prepared using a mixed solvent of dichloromethane, methanol, and 1-butanol as the organic solvent 27. 44) was prepared. The piping capacity C1 of the whole process is 56000L, and the piping capacity C2 after the additive addition is 8000L. Therefore, C2 / C1 is 1/7. As an additive, a phosphate ester plasticizer solution ({additive weight / (additive weight + mixed solvent weight)} x 100 = 55%) was used, and the organic solvent 27 for preparing the pure dope 44 was used as the buffer 387. The buffer layer 389a was formed between the pure dope 44 and the additive liquid. The amount of the additive liquid was 7% with respect to the flow rate of the pure dope 44, and the addition ratio of the buffer solution 387 was 0.07% with respect to the pure dope 44 (flow rate ratio = buffer flow rate / additive liquid amount = 0.07 / 7 = 0.01). ). After the additive liquid was added, the additive liquid and the pure dope were dispersed and mixed in a composite mixer in which the dynamic mixer 420 and the salt mixture mixed static mixer 393 were connected in series. Gelation did not occur, and casting and peeling could be performed without any problem.

Example 11

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

Example 12

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

Example 13

The same conditions as in Example 10 were carried out except that the addition ratio of the buffer solution 387 was 0.8% (flow rate ratio 0.8 / 7 to 0.11). Although no gelation occurred, peeling residues were generated at the time of peeling because the gel strength was lowered by causing the concentration of the cast dope to decrease.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the solution film forming installation which is 1st Embodiment of this invention.

2 is a schematic view showing a film forming unit.

3 is a schematic view showing an addition unit for adding an additive to the dope in two stages as a second embodiment.

It is a schematic diagram which shows the solution film forming installation which is 3rd Embodiment of this invention.

It is a schematic diagram which shows the solution film forming installation which is 4th Embodiment.

It is a schematic diagram which shows the additive addition unit of the solution film forming installation which is 5th Embodiment.

It is a schematic diagram which shows the solution film forming installation which is 6th Embodiment.

8 is a flowchart in a sixth embodiment of the present invention in which addition pretreatment is performed at an initial addition flow rate at a flow rate larger than the target addition flow rate.

9 is a flowchart in the seventh embodiment.

It is a schematic diagram which shows the solution film forming installation which is 8th Embodiment.

11 is a cross-sectional view of the addition nozzle.

It is a perspective view of the front end of an addition nozzle.

13 is a perspective view of an inline mixer.

14 is a cross-sectional view of the dynamic mixer.

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

Claims (26)

The solution film-forming method which manufactures a film from casting dope characterized by including the following steps: (A) preparing a reference dope containing a polymer and a solvent; (B) adding the additive specific to each variety with respect to the reference dope immediately before the casting die to make the casting dope; (C) casting the casting dope on the support by the casting die to form a casting film on the support; (D) imparting self-support to the cast film to peel the cast film from the support as a wet film; (E) drying the wet film to form the film; And (F) Changing the additive in the step B according to the variety in the variety switching of the film. The method for forming a solution according to claim 1, wherein the step B includes an additive liquid adjustment step of preparing the additive liquid by containing the additive in a liquid, and adding the additive liquid by an addition nozzle. The method according to claim 2, wherein when the piping capacity from the step A to the flexible die is C1, {(1/280) × C1} or more and {(1/7) × C1} or less based on the flexible die as a reference. A solution film forming method, wherein the additive liquid is added at an upstream position that becomes 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 method for forming a solution according to claim 2, wherein the additive is added in-line at the step B. The solution forming method according to claim 2, wherein the additive contains a plasticizer, and the concentration of the plasticizer in the additive liquid is 10% by weight or more and 65% by weight or less. The method for forming a solution according to claim 2, wherein the reference dope contains an additive commonly required for each variety. The solution film forming method according to claim 2, wherein the reference dope is a pure dope comprising the polymer and the solvent. The solution film forming method according to claim 2, wherein the additive liquid is circulated before the step B in advance. The solution film forming method according to claim 9, wherein in the circulation, the additive liquid is circulated at the same flow rate as when the additive liquid is added to the reference dope. 10. The method of claim 9, wherein the circulation is started at least 120 minutes before the start of step B. 10. The cleaning liquid according to claim 9, wherein the flow path of the additive liquid to the addition nozzle is made of the same liquid as that of the solvent before the additive liquid used for the new variety in the variety switching of the film is added to the reference dope. The solution film-forming method characterized by washing. 3. The addition according to claim 2, wherein the flow rate of the reference dope is added to QD and the new varieties in the varieties switching of the film, where {(QAE / QD) x 100} is obtained when QAE is added. 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 flow rate (QAS) is 1.5 to 3.0 times the addition flow rate (QAE) for a predetermined time. Addition is carried out and the initial film flow rate QAS is made into the said addition flow rate QAE after the said fixed time passes, The solution film forming method characterized by the above-mentioned. The said fixed time is a time until the pressure of the said additive liquid at the exit of the said addition nozzle becomes the same as the pressure of the said reference dope in the vicinity of the exit of the said addition nozzle. Solution film forming method. The method for forming a solution 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 addition flow rate QAS. The method of claim 2, wherein in the step B, the additive liquid is added to the reference dope with a buffer layer formed on the outer circumference, and the step B is uniformized by mixing the reference dope to which the additive liquid is added to the flexible dope. Solution forming method characterized by the above-mentioned. 17. The method according to claim 16, wherein the buffer constituting the buffer layer comprises a diluent liquid containing the same liquid as the component of the solvent, an additive liquid dilution of the additive liquid with the same liquid as the component of the solvent, and the reference dope with a component of the solvent. It is any one of the reference dope dilution liquid diluted with the same liquid. 18. The flow rate ratio (QB / QAE) of claim 17, wherein the buffer B is the same liquid as that of the solvent, and the flow rate of the additive solution is QAE and the flow rate of the buffer is QB. Solution forming method characterized by the following. The method for forming a solution according to claim 16, wherein the mixing is performed by passing a plurality of inline mixers having different mixing methods. 20. The static induction mixer of claim 19, wherein the inline mixer comprises a plurality of first elements formed by twisted partition members in a passage of the reference dope, and a second element formed by alternately intersecting a plurality of elongated partition members. And at least one of a split-mix type thru-the mixer configured by plurally arranged in the passage of the reference dope, and a dynamic mixer configured by disposing the rotating mixer body in the passage of the reference dope. Solution film production facility which manufactures film from flexible dope characterized by including the following: A reference dope preparation unit for preparing a reference dope containing a polymer and a solvent; An additive addition unit which adds an additive specific to each variety to the above-mentioned reference dope immediately before the casting die to form the casting dope; The cast dope is cast on the support with the cast die to form a cast film on the support, impart self-support to the cast film, peel the cast film from the support as a wet film, and dry the wet film. A film forming unit obtaining a film; And The additive change part which changes the said additive added to the said reference dope to the thing of a new prescription in the kind switching of the said film. The said additive addition unit has an addition nozzle which adds the additive liquid which the said additive contained in the liquid to the said reference dope, and the additive supply part which prepares the said additive liquid supplied to the said addition nozzle. Solution film production facility to do. 23. The solution film forming facility according to claim 22, wherein the additive supply unit has additive circulation means for circulating the additive liquid upstream from the addition nozzle. 23. The cleaning apparatus according to claim 22, wherein said additive adding unit includes a cleaning unit for cleaning a flow path of said additive liquid to said addition nozzle with a cleaning liquid composed of the same liquid as the components of said solvent in the variety switching of said film. Solution film production equipment. The solution film forming equipment according to claim 22, wherein the additive supply unit has a flow rate control means for controlling a flow rate of the additive liquid. 23. The method according to claim 22, wherein the addition nozzle has a buffer layer forming means for forming a buffer layer on the outer circumference of the additive liquid, and the additive adding unit mixes and uniforms the reference dope to which the additive liquid is added to form a flexible dope. Solution forming equipment characterized by having a mixing section.

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