JP2019183115A - Polyamic acid manufacturing system and manufacturing method, and polyimide manufacturing system and manufacturing method - Google Patents

Abstract

To provide a polyamic acid manufacturing system and a manufacturing method, capable of providing desire polyamic acid continuously and stably.SOLUTION: A polyamic acid manufacturing system 1 has a first supply part for supplying a first solution A1 containing a first polymerizable compound, a second supply part for supplying a second solution A2 containing a second polymerizable compound, a first mixing part 20 for mixing the first solution A1 and the second solution A2 to generate a first mixed solution B, a first reaction part 30 for processing a polymerization reaction to generate a first polymerization solution C containing polyamic acid, and a first control part 200 for controlling a flow rate variation rate of the first solution A1 to be a first threshold or lower, and controlling a flow rate variation rate of the second solution A1 to be a second threshold or lower.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a polyamic acid production system and production method for producing a polyamic acid which is a polyimide precursor, and a polyimide production system and production method for producing polyimide. Specifically, the present invention relates to a polyamic acid production system and a production method capable of continuously producing polyamic acid, and a polyimide production system and a production method capable of continuously producing polyimide.

  Conventionally, for example, the following two methods are known as continuous polyamic acid synthesis methods. Patent Document 1 describes a method of producing polyamic acid (polyamic acid) and polyimide using a tube reactor, and describes that stirring is performed by ultrasonic irradiation in order to advance the reaction of the mixed solution. ing. Patent Document 2 describes a method of producing polyamic acid (polyamic acid) using an inline mixer having a special fine structure.

JP 2006-249380 A JP 2005-105079 A

However, in the technique described in Patent Document 1, it is necessary to construct a reactor having a special apparatus shape in order to perform ultrasonic irradiation, and there is a problem in that the equipment becomes expensive.
In addition, in the technique described in Patent Document 2, the pressure loss is large due to the use of the fine flow path, and the incidental equipment such as a pump becomes expensive, or the production capacity of polyamic acid necessary on an industrial scale is obtained. There was a problem that was difficult.

  An object of this invention is to provide the polyamic acid manufacturing system and manufacturing method which can obtain a desired polyamic acid continuously and stably, without using an expensive installation. Another object of the present invention is to provide a polyimide production system and a production method capable of continuously and stably obtaining a desired polyimide.

Specific means for solving the above problems include the following embodiments.
<1> A polyamic acid is produced using a first solution containing a polyadditive first polymerizable compound and a second solution containing a polyadditive second polymerizable compound polyadded to the first polymerizable compound as a raw material. A polyamic acid production system for producing,
A first supply unit for supplying the first solution;
A second supply part for supplying the second solution;
A first mixing unit that mixes the first solution and the second solution to form a first mixed solution;
A first flow rate measuring unit for measuring a flow rate of the first solution;
A second flow rate measuring unit for measuring the flow rate of the second solution;
The first that is arranged continuously downstream of the first mixing part and includes a polyamic acid by proceeding a polymerization reaction between the first polymerizable compound and the second polymerizable compound contained in the first mixed solution. A first reaction part for producing a polymerization solution;
A polyamic acid production comprising: a first control unit that controls the flow rate fluctuation rate of the first solution to be equal to or lower than a first threshold value and controls the flow rate fluctuation rate of the second solution to be equal to or lower than a second threshold value. system.

<2> a first flow rate adjustment unit capable of adjusting a flow rate of the first solution;
A second flow rate adjustment unit capable of adjusting the flow rate of the second solution,
The first control unit adjusts the flow rate with the first flow rate adjusting unit and supplies the solution with the first supply unit so that the flow rate variation rate of the first solution is equal to or less than the first threshold value. Adjusting the flow rate by the second flow rate adjustment unit and adjusting the supply pressure of the solution supplied by the second supply unit so that the flow rate fluctuation rate of the second solution is less than or equal to the second threshold value. <1> The polyamic acid production system according to <1>.

<3> The first control unit is configured so that a ratio of the first polymerizable compound contained in the first solution and the second polymerizable compound contained in the second solution is within a predetermined range. The polyamic acid production system according to <1> or <2>, which controls the first supply unit and / or the second supply unit.

<4> The flow rate variation of the first solution and / or the second solution is reduced so that the difference between the flow rate variation rate of the first solution and the flow rate variation rate of the second solution is reduced. The polyamic acid production system according to any one of <1> to <3>, wherein the rate is controlled.

<5> The polyamic acid production system according to any one of <1> to <4>, wherein the first reaction unit includes a first reaction stirring unit that stirs the first mixed solution without contacting the gas. .

<6> The polyamic acid contained in the first polymerization solution is a polyamic acid having an acid anhydride group terminal or an amino group terminal,
A third supply unit for supplying a third solution containing diamine or tetracarboxylic dianhydride to be polyadded to the acid anhydride group-terminated or amino group-terminated polyamic acid contained in the first polymerization solution;
A second mixing unit that mixes the first polymerization solution and the third solution to form a second mixed solution;
A polymerization solution flow rate measuring unit for measuring a flow rate of the first polymerization solution;
A third flow rate measuring unit for measuring the flow rate of the third solution;
An acid anhydride-terminated or amino-terminated polyamic acid from the first polymerization solution, which is continuously disposed downstream of the second mixing unit and contained in the second mixed solution, and from the third solution A second reaction section for producing a second polymerization solution containing a polyamic acid by advancing a polymerization reaction with diamine or tetracarboxylic dianhydride;
The polyamic acid production system according to any one of <1> to <5>, further comprising a second control unit that controls the flow rate variation rate of the third solution to be equal to or less than a third threshold value.

<7> A third flow rate adjustment unit capable of adjusting the flow rate of the third solution is further provided.
The second control unit adjusts the flow rate by the third flow rate adjustment unit so that the flow rate variation rate of the third solution is equal to or less than the third threshold value, and supplies the solution by the third supply unit. <6> The polyamic acid production system according to <6>.

<8> The second control unit is a ratio of an acid anhydride group-terminated or amino group-terminated polyamic acid contained in the first polymerization solution to a diamine or tetracarboxylic dianhydride contained in the third solution. <6> or <7> The polyamic acid production system according to <7>, wherein the third supply unit is controlled so that the value falls within a predetermined range.

<9> The second control unit controls the flow rate fluctuation rate of the third solution so that the difference between the flow rate fluctuation rate of the first polymerization solution and the flow rate fluctuation rate of the third solution becomes smaller <6. The polyamic acid production system according to any one of> to <8>.

<10> The polyamic acid production system according to any one of <6> to <9>, wherein the second reaction unit includes a second reaction stirring unit that stirs the second mixed solution without contacting the gas. .

<11> The polyamic acid production system according to any one of <1> to <10>,
A polyimide production system comprising: an imidization unit that imidizes the polyamic acid produced by the polyamic acid production system.

<12> Using a polyamic acid as a raw material, a first solution containing a polyadditive first polymerizable compound and a second solution containing a polyadditive second polymerizable compound polyadded with the first polymerizable compound A method for producing a polyamic acid to be produced, comprising:
A first supply step of supplying the first solution;
A second supply step of supplying the second solution;
A first mixing step of mixing the first solution and the second solution to form a first mixed solution;
A first measuring step for measuring a flow rate of the first solution;
A second measuring step for measuring a flow rate of the second solution;
A first reaction step of generating a first polymerization solution containing a polyamic acid by advancing a polymerization reaction between the first polymerizable compound and the second polymerizable compound contained in the first mixed solution;
A first control step of controlling the flow rate fluctuation rate of the first solution to be equal to or lower than a first threshold value and controlling the flow rate fluctuation rate of the second solution to be equal to or lower than a second threshold value. Production method.

<13> a first flow rate adjustment step capable of adjusting the flow rate of the first solution;
A second flow rate adjusting step capable of adjusting the flow rate of the second solution,
In the first control step, the supply pressure of the solution supplied by the first supply step and the flow rate is adjusted by the first flow rate adjustment step so that the flow rate fluctuation rate of the first solution is not more than the first threshold value. The flow rate is adjusted by the second flow rate adjustment step and the supply pressure of the solution supplied by the second supply step is adjusted so that the flow rate fluctuation rate of the second solution is less than or equal to the second threshold value. <12> The method for producing a polyamic acid according to <12>.

<14> In the first control step, the ratio of the first polymerizable compound contained in the first solution and the second polymerizable compound contained in the second solution is within a predetermined range. The method for producing a polyamic acid according to <12> or <13>, wherein the first supply step and / or the second supply step is controlled.

<15> In the first control step, the flow rate fluctuations of the first solution and / or the second solution so that the difference between the flow rate fluctuation rate of the first solution and the flow rate fluctuation rate of the second solution is reduced. The method for producing a polyamic acid according to any one of <12> to <14>, wherein the rate is controlled.

<16> The production of the polyamic acid according to any one of <12> to <15>, wherein the first reaction step includes a first reaction stirring step in which the first mixed solution is stirred without contacting the gas. Method.

<17> The polyamic acid contained in the first polymerization solution is a polyamic acid having an acid anhydride group terminal or an amino group terminal,
A third supply step of supplying a third solution containing a diamine or tetracarboxylic dianhydride to be polyadded to the acid anhydride group-terminated or amino group-terminated polyamic acid contained in the first polymerization solution;
A second mixing step of mixing the first polymerization solution and the third solution to form a second mixed solution;
A polymerization solution flow rate measuring step for measuring a flow rate of the first polymerization solution;
A third flow rate measuring step for measuring a flow rate of the third solution;
The polymerization reaction of the acid-terminated or amino-terminated polyamic acid from the first polymerization solution contained in the second mixed solution and the diamine or tetracarboxylic dianhydride from the third solution is allowed to proceed. A second reaction step for producing a second polymerization solution containing a polyamic acid;
The method for producing a polyamic acid according to any one of <12> to <16>, further comprising a second control step of controlling the flow rate variation rate of the third solution to be equal to or less than a third threshold value.

<18> The method further includes a third flow rate adjustment step capable of adjusting the flow rate of the third solution,
In the second control step, the supply pressure of the solution supplied by the third supply step and the flow rate is adjusted by the third flow rate adjustment step so that the flow rate variation rate of the third solution is not more than the third threshold value. <17> The method for producing a polyamic acid according to <17>.

<19> In the second control step, the ratio of the acid anhydride group terminal or amino group terminal polyamic acid contained in the first polymerization solution to the diamine or tetracarboxylic dianhydride contained in the third solution. The method for producing a polyamic acid according to <17> or <18>, wherein the third supply step is controlled so that is within a predetermined range.

<20> In the second control step, the flow rate fluctuation rate of the third solution is controlled so as to reduce a difference between the flow rate fluctuation rate of the first polymerization solution and the flow rate fluctuation rate of the third solution <17. The method for producing a polyamic acid according to any one of> to <19>.

<21> The production of the polyamic acid according to any one of <17> to <20>, wherein the second reaction step includes a second reaction stirring step of stirring the second mixed solution without contacting the gas. Method.

<22> A polyamic acid production process for producing a polyamic acid by the production method according to any one of <12> to <21>,
The imidization process of imidating the polyamic acid manufactured in the said polyamic acid manufacturing process, The manufacturing method of the polyimide containing.

  ADVANTAGE OF THE INVENTION According to this invention, the polyamic acid manufacturing system and manufacturing method which can obtain a desired polyamic acid continuously and stably can be provided. Moreover, according to this invention, the polyimide manufacturing system and manufacturing method which can obtain a desired polyimide continuously and stably can be provided.

It is a figure which shows the polyamic acid manufacturing system in 1st Embodiment. It is a figure which shows the flow volume waveform which controlled the 1st flow rate fluctuation rate and the 2nd flow rate fluctuation rate. It is a flowchart explaining operation | movement of the polyamic-acid manufacturing system in 1st Embodiment. It is a figure which shows the polyamic-acid manufacturing system in 2nd Embodiment. It is a flowchart explaining operation | movement of the polyamic-acid manufacturing system in 2nd Embodiment.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
The first embodiment is an example of a polyamic acid production system having one reaction section. The second embodiment is an example of a polyamic acid production system having two stages of reaction parts.

<First Embodiment>
The polyamic acid production system in the first embodiment will be described with reference to FIGS. FIG. 1 is a diagram showing a polyamic acid production system in the first embodiment. FIG. 2 is a diagram showing a flow rate waveform in which the first flow rate variation rate and the second flow rate variation rate are controlled. FIG. 3 is a flowchart for explaining the operation of the polyamic acid production system in the first embodiment.

First, the outline | summary of the polyamic-acid manufacturing system 1 in 1st Embodiment is demonstrated.
The polyamic acid production system 1 includes a first solution A1 in which a polyadditive first polymerizable compound is dissolved, and a second solution A2 in which a polyadditive second polymerizable compound to be polyadded with the first polymerizable compound is dissolved. Is a production system for producing polyamic acid using as a raw material. The first embodiment is an example of a polyamic acid production system having one reaction section.

  Hereinafter, as an example, one of the first polymerizable compound and the second polymerizable compound will be described in which one is a tetracarboxylic dianhydride and the other is a diamine. More specifically, a case where the first polymerizable compound contained in the first solution A1 is tetracarboxylic dianhydride and the second polymerizable compound contained in the second solution A2 is diamine will be described.

  The tetracarboxylic dianhydride is not particularly limited, and those similar to those used in conventional polyimide synthesis can be used. Specific examples of the tetracarboxylic dianhydride include 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2, 3,3 ′, 4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (2, 3-dicarboxyphenoxy) benzene dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2', 6,6'-biphenyltetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, Anthracene-2,3,6,7-te Lacarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic Aromatic tetracarboxylic dianhydrides such as acid dianhydrides; aliphatic tetracarboxylic dianhydrides such as butane-1,2,3,4-tetracarboxylic dianhydrides; cyclobutane-1,2,3 Alicyclic tetracarboxylic dianhydrides such as 4-tetracarboxylic dianhydride; thiophene-2,3,4,5-tetracarboxylic dianhydride, pyridine-2,3,5,6-tetracarboxylic acid Heterocyclic tetracarboxylic dianhydrides such as dianhydrides; and the like. Tetracarboxylic dianhydride may be used individually by 1 type, and may use 2 or more types together.

  As the solvent of the first solution A1, a solvent in which tetracarboxylic dianhydride and polyamic acid are dissolved is used. Specific examples of the solvent include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and acetanilide; Cyclic ester solvents such as butyrolactone; Chain ester solvents such as ethyl acetate; Ketone solvents such as 2-propanone, 3-pentanone, acetone, and methyl ethyl ketone; Ether solvents such as tetrahydrofuran and dioxolane; Methanol, ethanol, isopropanol, and the like Alcohol-based solvents; aromatic hydrocarbon solvents such as toluene and xylene; and the like. Among these, an amide solvent, a cyclic ester solvent, and an ether solvent with high solubility of polyamic acid are preferable. A solvent may be used individually by 1 type and may mix 2 or more types. For example, the solubility of polyamic acid can be improved by mixing a highly polar alcohol solvent with a relatively low solubility of polyamic acid such as acetone, ethyl acetate, methyl ethyl ketone, toluene, xylene. Is also possible.

  The first solution A1 may contain a small amount of a tertiary amine such as trimethylamine or triethylamine in order to increase the solubility of the tetracarboxylic dianhydride or increase the reactivity with the diamine.

  The diamine is not particularly limited, and those similar to those used in conventional polyimide synthesis can be used. Specific examples of the diamine include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4′-bis (4- Aminophenoxy) biphenyl, 1,4′-bis (4-aminophenoxy) benzene, 1,3′-bis (4-aminophenoxy) benzene, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-methylene-bis (2-chloroaniline), 3, 3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl sulfide, 2,6 Diaminotoluene, 2,4-diaminochlorobenzene, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 4, Aromatic diamines such as 4′-diaminobibenzyl; aliphatic diamines such as 1,2-diaminoethane, 1,4-diaminobutane, tetramethylenediamine, 1,10-diaminododecane; 1,4-diaminocyclohexane, 1 , 2-diaminocyclohexane, bis (4-aminocyclohexyl) methane, alicyclic diamines such as 4,4′-diaminodicyclohexylmethane; heterocyclic diamines such as 3,4-diaminopyridine; A diamine may be used individually by 1 type and may use 2 or more types together.

  As the solvent of the second solution A2, a solvent in which diamine and polyamic acid are dissolved is used. Specific examples of the solvent include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and acetanilide; Cyclic ester solvents such as butyrolactone; Chain ester solvents such as ethyl acetate; Ketone solvents such as 2-propanone, 3-pentanone, acetone, and methyl ethyl ketone; Ether solvents such as tetrahydrofuran and dioxolane; Methanol, ethanol, isopropanol, and the like Alcohol-based solvents; aromatic hydrocarbon solvents such as toluene and xylene; and the like. Among these, an amide solvent, a cyclic ester solvent, and an ether solvent with high solubility of polyamic acid are preferable. A solvent may be used individually by 1 type and may mix 2 or more types. For example, the solubility of polyamic acid can be improved by mixing a highly polar alcohol solvent with a relatively low solubility of polyamic acid such as acetone, ethyl acetate, methyl ethyl ketone, toluene, xylene. Is also possible.

  As shown in FIG. 1, the polyamic acid production system 1 mixes a first solution A1 and a second solution A2 that are raw materials in a first mixing unit 20 to generate a first mixed solution B, and a first reaction unit 30. The polyamic acid is produced by causing the polymerization reaction to proceed to produce the first polymerization solution C.

  Here, the polyamic acid production system 1 has a tubular liquid feed line L that connects a first tank 11 and a second tank 12 described later to the first cushion tank 40 in a sealed state. Thereby, the polyamic acid production system 1 can continuously produce polyamic acid in a state where no bubbles are generated in the first mixed solution B or the first polymerization solution C.

Then, the specific structure of the polyamic acid manufacturing system 1 is demonstrated.
As shown in FIG. 1, the polyamic acid production system 1 includes a first tank 11, a second tank 12, a first supply pump 15 (first supply unit), and a second supply pump 16 (second supply unit). A first mixing unit 20, a first reaction unit 30, a first cushion tank 40, a liquid feeding line L, and a first control unit 200. The above-mentioned liquid feeding line L has the 1st liquid feeding part L1, the 2nd liquid feeding part L2, and the 3rd liquid feeding part L3. The polyamic acid production system 1 also includes a first flow rate adjustment valve 151 (first flow rate adjustment unit), a first flow rate measurement unit 152, a second flow rate adjustment valve 161 (second flow rate adjustment unit), and a second flow rate. A measurement unit 162.

  The first tank 11 contains a first solution A1 containing a polyadditive first polymerizable compound. In the present embodiment, the first tank 11 stores the first solution A1 containing tetracarboxylic dianhydride. The first solution A1 stored in the first tank 11 is supplied to the first mixing unit 20 via the first liquid feeding unit L1.

  Between the 1st tank 11 and the 1st mixing part 20 in the 1st liquid feeding part L1, the 1st supply pump 15, the 1st flow control valve 151, and the 1st flow measurement part 152 are the downstream from the upstream. It is arranged in this order toward.

  The first supply pump 15 (first supply unit) supplies the first solution A1 stored in the first tank 11 to the first mixing unit 20. The first supply pump 15 discharges the first solution A1 so as to supply the first solution A1 with a predetermined liquid feeding amount. For example, the 1st supply pump 15 is adjusted so that the 1st solution A1 may be supplied on the conditions from which the polyamic acid of a desired property is obtained.

  In the present embodiment, the first supply pump 15 is constituted by a metering pump. The metering pump is a positive displacement pump, and is a pump that repeatedly delivers a fixed amount of solution with high accuracy. Examples of the metering pump include an extruding reciprocating pump such as a plunger pump; a rotary pump such as a gear pump including gears; and the like.

  As the first supply pump 15, it is preferable to select a pump having a small inherent pulsation rate (flow rate fluctuation rate). For example, the inherent pulsation rate (flow rate fluctuation rate) of the first supply pump 15 is preferably 3% or less, and more preferably 1% or less. The inherent pulsation rate (flow rate fluctuation rate) of the first supply pump 15 is a flow rate that is half the amplitude of the flow rate fluctuation with respect to the flow rate value at the center of the amplitude of the flow rate fluctuation, as in the case of the first flow rate fluctuation rate Ha described later. It is defined as the ratio of.

  Instead of selecting a specific pulsation rate (flow rate fluctuation rate) as the first supply pump 15, or selecting a first supply pump 15 having a low specific pulsation rate (flow rate variation rate). In addition, it is also preferable to arrange a buffer device (for example, an accumulator) for fluctuations in the flow rate in the liquid feeding line L. By arranging a shock absorber such as an accumulator, the flow rate fluctuation rate can be further reduced.

  The first flow rate adjustment valve 151 is disposed between the first supply pump 15 and the first mixing unit 20. The first flow rate adjustment valve 151 is a valve capable of adjusting the flow rate of the first solution A1 supplied by the first supply pump 15. In the present embodiment, the flow rate of the first solution A1 is adjusted by adjusting the valve opening degree of the first flow rate adjustment valve 151. The valve opening degree of the first flow rate adjusting valve 151 is controlled by a first control unit 200 described later.

  The first flow rate measuring unit 152 measures the flow rate of the first solution A1 on the downstream side of the first supply pump 15 in the first liquid feeding unit L1. In the present embodiment, the first flow rate measurement unit 152 is disposed between the first flow rate adjustment valve 151 and the first mixing unit 20. Note that the first flow rate measurement unit 152 may be disposed upstream of the first flow rate adjustment valve 151 and downstream of the first supply pump 15. The first flow rate measurement unit 152 outputs the measured flow rate of the first solution A1 to the first control unit 200 described later.

  The second tank 12 contains a second solution A2 containing a polyadditive second polymerizable compound that is polyadded with the first polymerizable compound. In the present embodiment, the second tank 12 stores the second solution A2 containing diamine. The second solution A2 stored in the second tank 12 is supplied to the first mixing unit 20 via the second liquid feeding unit L2.

  Between the second tank 12 and the first mixing unit 20 in the second liquid feeding unit L2, a second supply pump 16, a second flow rate adjusting valve 161, and a second flow rate measuring unit 162 are connected from the upstream side to the downstream side. It is arranged in this order toward.

The second supply pump 16 (second supply unit) supplies the second solution A2 stored in the second tank 12 to the first mixing unit 20. The second supply pump 16 discharges the second solution A2 so as to supply the second solution A2 with a predetermined liquid feeding amount. For example, the 2nd supply pump 16 is adjusted so that the 2nd solution A2 may be supplied on the conditions from which the polyamic acid of a desired property is obtained.
In this embodiment, the 2nd supply pump 16 is comprised with a metering pump similarly to the 1st supply pump 15 mentioned above.

  As the second supply pump 16, it is preferable to select a pump having a small inherent pulsation rate (flow rate fluctuation rate). The inherent pulsation rate (flow rate fluctuation rate) of the second supply pump 16 is, for example, preferably 3% or less, and more preferably 1% or less. The inherent pulsation rate (flow rate fluctuation rate) of the second supply pump 16 is defined as the ratio of the flow rate that is half the amplitude of the flow rate change to the flow rate value at the center of the amplitude of the flow rate change, as with the first supply pump 15. To do.

  In addition, instead of selecting a specific pulsation rate (flow rate fluctuation rate) as the second supply pump 16, or selecting a specific low pulsation rate (flow rate variation rate) as the second supply pump 16. In addition, it is also preferable to arrange a buffer device (for example, an accumulator) for fluctuations in the flow rate in the liquid feeding line L. By arranging a shock absorber such as an accumulator, the flow rate fluctuation rate can be further reduced.

  The second flow rate adjustment valve 161 is disposed between the second supply pump 16 and the first mixing unit 20. The second flow rate adjustment valve 161 is a valve capable of adjusting the flow rate of the second solution A2 supplied by the second supply pump 16. In the present embodiment, the flow rate of the second solution A2 is adjusted by adjusting the valve opening degree of the second flow rate adjustment valve 161. The valve opening degree of the second flow rate adjustment valve 161 is controlled by the first control unit 200 described later.

  The second flow rate measuring unit 162 measures the flow rate of the second solution A2 on the downstream side of the second supply pump 16 in the second liquid feeding unit L2. In the present embodiment, the second flow rate measurement unit 162 is disposed between the second flow rate adjustment valve 161 and the first mixing unit 20. Note that the second flow rate measuring unit 162 may be disposed upstream of the second flow rate adjustment valve 161 and downstream of the second supply pump 16. The second flow rate measuring unit 162 outputs the measured flow rate of the second solution A2 to the first control unit 200 described later.

  The first mixing unit 20 is disposed on the downstream side of the first supply pump 15 and the second supply pump 16. The first mixing unit 20 mixes the first solution A1 and the second solution A2 to generate the first mixed solution B. The first mixing unit 20 is configured by a merging valve that joins the first solution A1 supplied by the first supply pump 15 and the second solution A2 supplied by the second supply pump 16.

  The first control unit 200 to be described later controls the first supply pump 15 and / or the second supply pump 16 to thereby control the first polymerizable compound contained in the first solution A1 and the second solution A2 contained in the second solution A2. The molar ratio with the polymerizable compound is controlled to be within a predetermined range. The above molar ratio is set so that, for example, a polyamic acid having a desired property can be obtained.

  In this embodiment, for example, when the number of moles of diamine (second polymerizable compound) is 100 when the equivalent ratio is the number of moles of tetracarboxylic dianhydride (first polymerizable compound). The number of moles of diamine (second polymerizable compound) is preferably in the range of 95 to 105, and more preferably in the range of 97.5 to 102.5.

  Here, in this embodiment, when the molar ratio of tetracarboxylic dianhydride (first polymerizable compound) and diamine (second polymerizable compound) is an equivalent ratio, the molecular weight of the polyamic acid is maximized. The viscosity of the first polymerization solution C is also maximized. In addition, as the molar ratio of tetracarboxylic dianhydride (first polymerizable compound) and diamine (second polymerizable compound) deviates from the equivalent ratio, the molecular weight of the polyamic acid decreases significantly, and the first polymerization solution C Viscosity of the resin is greatly reduced. Therefore, due to the inherent pulsation of the first supply pump 15 and the second supply pump 16, the molar ratio of tetracarboxylic dianhydride (first polymerizable compound) and diamine (second polymerizable compound) is When it fluctuates, the molecular weight of the polyamic acid changes greatly, and the viscosity of the first polymerization solution C also changes greatly. As described above, when unevenness of viscosity occurs in the first polymerization solution C, flow rate fluctuation (pulsation) occurs in the first polymerization solution C, and accordingly, flow rate fluctuations (pulsation) also occur in the first solution A1 and the second solution A2. Occurs. This flow rate fluctuation (pulsation) becomes more significant as the viscosity increases.

  At this time, if the back pressure applied to the solution flowing through the liquid feeding line L is sufficiently high, the flow rate fluctuation (pulsation) of the first polymerization solution C due to the unevenness of the viscosity is reduced, and the first solution A1 and the first solution A The flow rate fluctuation (pulsation) of the two solutions A2 is also reduced. However, since the inherent pulsations of the first supply pump 15 and the second supply pump 16 are superimposed on the flow rate fluctuations (pulsations) of the first solution A1 and the second solution A2, the first solution A1 and the second solution A2 The flow rate of fluctuates in a complicated manner. In this embodiment, in order to obtain a desired polyamic acid continuously and stably even in such a situation, various controls are executed in the first control unit 200 described later.

  The first reaction unit 30 is continuously arranged on the downstream side of the first mixing unit 20. The first reaction unit 30 is a part that advances the polymerization reaction between the first polymerizable compound and the second polymerizable compound contained in the first mixed solution B. In the first reaction unit 30, the polymerization reaction between the first polymerizable compound and the second polymerizable compound contained in the first mixed solution B gradually proceeds to obtain the first polymerization solution C.

  The first reaction unit 30 is composed of a double tube extending in a predetermined direction, and includes a first reaction stirring unit 31 disposed on the inner side in the radial direction, and a first reaction temperature adjusting unit 32 disposed on the outer side in the radial direction. Have. The first reaction unit 30 is formed so that the first mixed solution B flows in a desired residence time.

  The 1st reaction stirring part 31 stirs the 1st mixed solution B with which 1st solution A1 and 2nd solution A2 were mixed in the state which does not contact gas. In this embodiment, the 1st reaction stirring part 31 stirs the 1st mixed solution B adjusted to the temperature suitable for the polymerization reaction by the 1st reaction temperature adjustment part 32 in the state which does not contact gas.

  The first reaction stirring unit 31 includes, for example, a static mixer, a static mixer such as a nozzle and an orifice, and a driving mixer such as a centrifugal pump, a vortex pump, and an inline mixer having stirring blades, preferably It is comprised including a static mixer, More preferably, it is comprised including a static mixer. It should be noted that a tube with a twisted tape inserted therein (see [FIG. 19] in JP-A-2003-314882) can provide an agitation promoting effect as in the case of a static mixer, but the static mixer is more effective in promoting agitation. Is preferable.

  The static mixer is not particularly limited, and for example, Kenics mixer type, Sulzer SMV type, Sulzer SMX type, Ray Hi-mixer type, Komax mixer type, Lightnin mixer type, Ross ISG type, Bran & Lub mixer type, etc. Can be mentioned. Among these, the Kenics mixer type static mixer is more preferable because of its simple structure and no dead space.

  The first reaction temperature adjustment unit 32 is a piping unit that is disposed outside the first reaction stirring unit 31 in the radial direction. The first reaction temperature adjustment unit 32 adjusts the temperature of the first mixed solution B flowing through the first reaction stirring unit 31 to a desired temperature condition (for example, cooling). In the first reaction temperature adjusting unit 32, the first mixed solution B is adjusted to a temperature suitable for the polymerization reaction and is circulated through the first reaction stirring unit 31.

  The first cushion tank 40 accommodates the first polymerization solution C from the first reaction unit 30. The first cushion tank 40 is, for example, a tank for storing a raw material solution when imidizing polyamic acid to produce polyimide.

  The polyamic acid production system 1 in the present embodiment may be part of a polyimide production system that produces polyimide. In this case, the polyimide manufacturing system further includes an imidization unit that imidizes the polyamic acid. The imidization part (not shown) imidizes the polyamic acid by, for example, a thermal imidization method that thermally dehydrates and closes a ring, a chemical imidization method that uses a dehydrating agent and an imidization accelerator, and the like.

  In addition, when the polyamic acid manufacturing system 1 in this embodiment is a part of the polyimide manufacturing system which manufactures a polyimide, the 1st cushion tank 40 is abbreviate | omitted and it sends to the imidation part from the 1st reaction part 30. You may comprise. However, as described above, it is preferable to store the polyamic acid in the first cushion tank 40 once.

  The first control unit 200 will be described. The first control unit 200 includes the first supply pump 15, the second supply pump 16, the first flow rate adjustment valve 151, the first flow rate measurement unit 152, the second flow rate adjustment valve 161, and the second flow rate measurement unit 162. Connected.

  The first control unit 200 controls the flow rate fluctuation rate of the first solution A1 (hereinafter also referred to as “first flow rate fluctuation rate”) to be equal to or lower than the first threshold, and the flow rate fluctuation rate of the second solution A2 ( Hereinafter, control is also performed so that “the second flow rate fluctuation rate” is equal to or lower than the second threshold. In the present embodiment, the first flow rate variation rate and / or the second flow rate variation rate is, for example, preferably 3% or less, and more preferably 2.5% or less. The lower limit value of the first flow rate fluctuation rate and / or the second flow rate fluctuation rate is not particularly limited, but may be 0.01%, for example.

  In the present embodiment, for example, as shown in the flow rate waveform before control in FIG. 2, the first flow rate fluctuation rate Ha is set to a flow rate Sa that is half the amplitude of the flow rate fluctuation with respect to the flow rate value Ka at the center of the amplitude of the flow rate fluctuation. It is defined as a ratio (Ha = (Sa / Ka) × 100 [%]). Further, for example, the second flow rate fluctuation rate Hb is defined as a ratio of the flow rate Sb that is half the amplitude of the flow rate variation to the flow rate value Kb at the center of the amplitude of the flow rate variation (Hb = (Sb / Kb) × 100 [%]). ).

  For example, when the first flow rate fluctuation rate Ha is larger than the first threshold value TH1, the first control unit 200 sets the first flow rate fluctuation rate Ha to the first threshold value TH1 as shown in the flow rate waveform before control in FIG. In order to make the following, while adjusting the valve opening of the first flow rate adjustment valve 151 to be small, the supply amount of the first solution A1 before the valve opening of the first flow rate adjustment valve 151 is adjusted It changes so that the supply pressure of the solution supplied with the 1st supply pump 15 may be enlarged so that it may become the same supply amount. In addition, when the second flow rate fluctuation rate Hb is larger than the second threshold value TH2, the first control unit 200 sets the second flow rate fluctuation rate Hb to be equal to or less than the second threshold value TH2, so that the valve of the second flow rate adjustment valve 161 is used. The second supply pump 16 is adjusted so that the opening degree is decreased and the supply amount of the second solution A2 is the same as the supply amount before the valve opening degree of the second flow rate adjustment valve 161 is adjusted. To change the supply pressure of the solution to be supplied. Thereby, as shown in the flow waveform after control in FIG. 2, the first flow rate fluctuation rate Ha is adjusted to be equal to or lower than the first threshold value TH1 (Ha ≦ TH1), and the second flow rate fluctuation rate Hb is set to the second threshold value TH2. The following adjustment is made (Hb ≦ TH2). In the present embodiment, the first threshold value TH1 of the first flow rate fluctuation rate Ha and the second threshold value TH2 of the second flow rate fluctuation rate Hb are preferably 3%, for example, and more preferably 2.5%. preferable.

  As described above, the supply of the solution supplied by the first supply pump 15 and / or the second supply pump 16 in accordance with the adjustment of the valve opening degree of the first flow rate adjustment valve 151 and / or the second flow rate adjustment valve 161. By adjusting the pressure, the first solution A1 and the second solution A2 are not changed without changing the ratio of the first polymerizable compound contained in the first solution A1 and the second polymerizable compound contained in the second solution A2. And can be mixed.

  Further, the first control unit 200 controls the first flow rate fluctuation rate to be equal to or lower than the first threshold value, and controls the second flow rate fluctuation rate to be lower than the second threshold value. The first flow rate variation rate and / or the second flow rate variation rate may be controlled so that the difference between the first flow rate variation and the second flow rate variation rate is small. Specifically, the first control unit 200 controls the flow rate by the first flow rate adjustment valve 151 and / or the second flow rate adjustment valve 161 so that the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate becomes small. While adjusting, the supply pressure of the solution supplied by the first supply pump 15 and / or the second supply pump 16 may be adjusted. In the present embodiment, the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate is, for example, preferably 1% or less, and more preferably 0.5% or less.

  In addition, the first control unit 200 controls the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate to be small, and the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate is a predetermined lower limit. The first flow rate fluctuation rate and / or the second flow rate fluctuation rate may be controlled so as not to be smaller than the value. In the present embodiment, the lower limit value of the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate is preferably, for example, 0.001%. Thus, by setting a lower limit value for the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate, and slightly shifting the mixing ratio of the first solution A1 and the second solution A2, the first solution A1 and It exists in the tendency which can be favorably mixed with 2nd solution A2.

Next, the operation of the polyamic acid production system 1 in the first embodiment will be described with reference to FIG.
First, in the polyamic acid production system 1, by starting the operation, the first supply pump 15 supplies the first solution A1 (first supply step), and the second supply pump 16 supplies the second solution A2 ( Second supply step). Here, the first control pump 200 controls the first supply pump 15 and the second supply pump 16 so that the first control unit 200 supplies the first solution A1 and the second solution A2 at a desired ratio. It is controlled.

  Next, as shown in FIG. 3, in step ST11, the first flow rate measuring unit 152 measures and acquires the flow rate of the first solution A1 (first measurement step). The second flow rate measuring unit 162 measures and acquires the flow rate of the second solution A2 (second measurement step).

  Next, in step ST12, the first controller 200 determines whether or not the first flow rate fluctuation rate is greater than the first threshold value and whether or not the second flow rate fluctuation rate is greater than the second threshold value. In the state before the control shown in FIG. 2, the first flow rate fluctuation rate Ha is larger than the first threshold value TH1 (Ha> TH1). Further, the second flow rate fluctuation rate Hb is larger than the second threshold value TH2 (Hb> TH2). In the present embodiment, the first threshold value and the second threshold value are set to 3%, for example. This is because the desired polyamic acid can be stably obtained when the first flow rate variation rate and the second flow rate variation rate are 3% or less.

  If the first control unit 200 determines that the first flow rate variation rate is greater than the first threshold value or the second flow rate variation rate is greater than the second threshold value (YES), the process proceeds to step ST13. . Moreover, the 1st control part 200 returns a process to step ST11, when it determines with a 1st flow rate fluctuation rate being below a 1st threshold value and a 2nd flow rate fluctuation rate being below a 2nd threshold value (NO). .

  Next, in step ST13, the first controller 200 controls the first flow rate fluctuation rate and / or the second flow rate fluctuation rate. When the first flow rate variation rate is larger than the first threshold value, the first control unit 200 reduces the valve opening degree of the first flow rate adjustment valve 151 in order to make the first flow rate variation rate equal to or less than the first threshold value. The supply pressure of the solution supplied by the first supply pump 15 is adjusted so that the supply amount of the first solution A1 is the same as the supply amount before adjusting the valve opening degree of the first flow rate adjustment valve 151. Is changed to be larger (first control step). When the second flow rate fluctuation rate is larger than the second threshold value, the first control unit 200 decreases the valve opening degree of the second flow rate adjustment valve 161 in order to make the second flow rate fluctuation rate equal to or less than the second threshold value. Of the solution supplied by the second supply pump 16 so that the supply amount of the second solution A2 is the same as the supply amount before adjusting the valve opening degree of the second flow rate adjustment valve 161. The supply pressure is changed to increase (first control step). As a result, as shown in FIG. 2, the first flow rate fluctuation rate Ha after the control is equal to or lower than the first threshold value TH1 (Ha ≦ TH1), and the second flow rate fluctuation rate Hb after the control is equal to or lower than the second threshold value TH2 ( Hb ≦ TH2).

  The first control unit 200 controls the first flow rate fluctuation rate to be equal to or lower than the first threshold value, and controls the second flow rate fluctuation rate to be lower than the second threshold value. The first flow rate fluctuation rate and / or the second flow rate fluctuation rate may be controlled so that the difference becomes small. Specifically, the first control unit 200 controls the flow rate by the first flow rate adjustment valve 151 and / or the second flow rate adjustment valve 161 so that the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate becomes small. While adjusting, the supply pressure of the solution supplied by the first supply pump 15 and / or the second supply pump 16 may be adjusted. In the present embodiment, the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate is, for example, preferably 1% or less, and more preferably 0.5% or less.

  In addition, the first control unit 200 controls the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate to be small, and the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate is a predetermined lower limit. The first flow rate fluctuation rate and / or the second flow rate fluctuation rate may be controlled so as not to be smaller than the value. In the present embodiment, the lower limit value of the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate is preferably, for example, 0.001%.

  Next, the control of the first control unit 200 enters a standby state (step ST14). Thereafter, the process returns to step ST11.

  Here, for example, the method for producing polyamic acid in the present embodiment may be a part of the method for producing polyimide. In this case, the method for producing polyimide further includes an imidization step of imidizing the polyamic acid.

According to the polyamic acid production system 1 of the present embodiment, the following effects are exhibited.
The polyamic acid production system 1 is a polyamic acid production system including a first supply pump 15 that supplies the first solution A1 and a second supply pump 16 that supplies the second solution A2. The first control unit 200 is controlled to control the second flow rate fluctuation rate to be equal to or lower than the second threshold value. According to such a polyamic acid production system 1, since the first flow rate fluctuation rate and the second flow rate fluctuation rate can be reduced, a desired polyamic acid can be obtained continuously and stably.

  In the polyamic acid production system 1, the first control unit 200 adjusts the flow rate by the first flow rate adjustment valve 151 and supplies the first supply pump 15 so that the first flow rate fluctuation rate is equal to or lower than the first threshold value. Adjust the supply pressure of the solution. In addition, the first control unit 200 adjusts the flow rate by the second flow rate adjustment valve 161 and adjusts the supply pressure of the solution supplied by the second supply pump 16 so that the second flow rate fluctuation rate is equal to or less than the second threshold value. To do. As a result, the polyamic acid production system 1 can reduce the first flow rate fluctuation rate and the second flow rate fluctuation rate and can distribute the first solution A1 and the second solution A2 without changing the flow rate. It is possible to obtain polyamic acid continuously and more stably.

  Further, in the polyamic acid production system 1, the first control unit 200 sets the first flow rate variation rate and / or the second flow rate variation rate so that the difference between the first flow rate variation rate and the second flow rate variation rate becomes small. Can be controlled. By reducing the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate, it is possible to obtain a desired polyamic acid continuously and more stably.

  In the present embodiment, one of the first polymerizable compound and the second polymerizable compound is described in which one is a tetracarboxylic dianhydride and the other is a diamine, and a polyamic acid is produced. Is not to be done. For example, among the first polymerizable compound and the second polymerizable compound, one is a polyamic acid (prepolymer) having an acid anhydride group terminal or amino group terminal, the other is a diamine or a tetracarboxylic dianhydride, and the polyamic acid is You may make it manufacture. In this case, when one of the first polymerizable compound and the second polymerizable compound is a polyamic acid having an acid anhydride group terminal, the other is a diamine. In addition, when one of the first polymerizable compound and the second polymerizable compound is an amino group-terminated polyamic acid, the other is a tetracarboxylic dianhydride.

  Moreover, although this embodiment demonstrated the case where the 1st reaction part 30 was comprised with the double tube | pipe of the 1st reaction stirring part 31 and the 1st reaction temperature adjustment part 32, it is not limited to this. . For example, the first reaction unit 30 may be constituted by a single tube having only the first reaction stirring unit 31, and the first reaction stirring unit 31 may be immersed in a temperature control liquid.

Second Embodiment
Next, the polyamic acid manufacturing system in 2nd Embodiment is demonstrated using FIG.4 and FIG.5. FIG. 4 is a diagram showing a polyamic acid production system in the second embodiment. FIG. 5 is a flowchart for explaining the operation of the polyamic acid production system in the second embodiment. The second embodiment is an example of a polyamic acid production system having two stages of processing units (reaction units).

First, the polyamic acid production system 1A in the second embodiment will be described with reference to FIG.
As illustrated in FIG. 5, the polyamic acid production system 1A includes a first processing unit K1 and a second processing unit K2.

  Since the 1st process part K1 is the structure similar to the polyamic-acid manufacturing system 1 in 1st Embodiment, detailed description in this embodiment is abbreviate | omitted. The description in the first embodiment can be used for the configuration requirements and operations in the first processing unit K1. However, the 1st polymerization solution C manufactured by the 1st treating part K1 shall contain polyamic acid (prepolymer) of an acid anhydride group end or an amino group end.

  The second processing unit K2 further proceeds the polymerization reaction using the first polymerization solution C manufactured by the first processing unit K1 (polyamic acid manufacturing system 1 in the first embodiment) and the third solution A3 as raw materials, A polyamic acid having a higher molecular weight is produced. The second processing unit K2 has the same basic configuration as the first processing unit K1, but is the first processing in that polyamic acid is manufactured using the first polymerization solution C manufactured by the first processing unit K1 as a raw material. This is different from the part K1.

  The second processing unit K2 includes a third tank 13, a third supply pump 17 (third supply unit), a second mixing unit 50, a second reaction unit 60, a second cushion tank 70, and a liquid feed line. A part of L. A part of the above-described liquid feeding line L includes a fourth liquid feeding part L4 and a fifth liquid feeding part L5. The second processing unit K2 includes a third flow rate adjustment valve 171 (third flow rate adjustment unit), a third flow rate measurement unit 172, and a fourth flow rate measurement unit 182 (polymerization solution flow rate measurement unit).

  The fourth flow rate measuring unit 182 measures the flow rate of the first polymerization solution C on the downstream side of the first reaction unit 30 in the third liquid feeding unit L3. The fourth flow rate measuring unit 182 outputs the measured flow rate of the first polymerization solution C to the second control unit 200A described later.

  The third tank 13 accommodates a third solution A3 in which a diamine or tetracarboxylic dianhydride to be polyadded to a polyamic acid having an acid anhydride group terminal or an amino group terminal contained in the first polymerization solution C is dissolved. The third solution A3 stored in the third tank 13 is supplied to the second mixing unit 50 through the fourth liquid feeding unit L4.

  Hereinafter, as an example, the case where the first polymerization solution C contains a polyamic acid at the terminal of an acid anhydride group and the third solution A3 contains a diamine will be described.

  Between the 3rd tank 13 and the 2nd mixing part 50 in the 4th liquid sending section L4, the 3rd supply pump 17, the 3rd flow control valve 171, and the 3rd flow measurement part 172 are the downstream from the upstream. It is arranged in this order toward.

The third supply pump 17 (third supply unit) supplies the third solution A3 stored in the third tank 13 to the second mixing unit 50. The third supply pump 17 discharges the third solution A3 so as to supply the third solution A3 with a predetermined liquid feeding amount. For example, the third supply pump 17 is adjusted so as to supply the third solution A3 under the condition that a polyamic acid having a desired property is obtained. The supply amount in the third supply pump 17 can be set according to the properties and composition in the first polymerization solution C. The supply amount in the third supply pump 17 can be set according to the reaction rate in the first polymerization solution C and the like. In other words, the supply amount in the third supply pump 17 can be adjusted to a supply amount that achieves the target property, composition, and reaction rate.
In this embodiment, the 3rd supply pump 17 is comprised with a metering pump similarly to the 1st supply pump 15 mentioned above.

  As the third supply pump 17, it is preferable to select a pump having a small inherent pulsation rate (flow rate fluctuation rate). The inherent pulsation rate (flow rate fluctuation rate) of the third supply pump 17 is, for example, preferably 3% or less, and more preferably 1% or less. The inherent pulsation rate (flow rate fluctuation rate) of the third supply pump 17 is half of the amplitude of the flow rate variation with respect to the flow rate value at the center of the amplitude of the flow rate variation, as in the first supply pump 15 and the second supply pump 16. It is defined as the flow rate ratio.

  Instead of selecting a specific pulsation rate (flow rate fluctuation rate) as the third supply pump 17, or selecting a low specific pulsation rate (flow rate variation rate) as the third supply pump 17. In addition, it is also preferable to arrange a buffer device (for example, an accumulator) for fluctuations in the flow rate in the liquid feeding line L. By arranging a shock absorber such as an accumulator, the flow rate fluctuation rate can be further reduced.

  The third flow rate adjustment valve 171 is disposed between the third supply pump 17 and the second mixing unit 50. The third flow rate adjustment valve 171 is a valve capable of adjusting the flow rate of the third solution A3 supplied by the third supply pump 17. In the present embodiment, the flow rate of the third solution A3 is adjusted by adjusting the valve opening degree of the third flow rate adjustment valve 171. The valve opening degree of the third flow rate adjustment valve 171 is controlled by a second control unit 200A described later.

  The third flow rate measuring unit 172 measures the flow rate of the third solution A3 on the downstream side of the third supply pump 17 in the fourth liquid feeding unit L4. In the present embodiment, the third flow rate measurement unit 172 is disposed between the third flow rate adjustment valve 171 and the second mixing unit 50. Note that the third flow rate measurement unit 172 may be disposed upstream of the third flow rate adjustment valve 171 and downstream of the third supply pump 17. The third flow rate measuring unit 172 outputs the measured flow rate of the third solution A3 to the second control unit 200A described later.

  The second mixing unit 50 is disposed on the downstream side of the first reaction unit 30 and the third supply pump 17 of the first processing unit K1. The second mixing unit 50 mixes the first polymerization solution C from the first reaction unit 30 and the third solution A3 from the third supply pump 17 to generate a second mixed solution D. The second mixing unit 50 is configured by a merging valve that merges the first polymerization solution C from the first reaction unit 30 and the third solution A3 from the third supply pump 17.

  The second control unit 200A, which will be described later, controls the third supply pump 17, so that the molar ratio between the polyamic acid at the terminal of the acid anhydride group contained in the first polymerization solution C and the diamine contained in the third solution A3 is increased. Control to be within a predetermined range. The above molar ratio is set so that, for example, a polyamic acid having a desired property can be obtained.

  In this embodiment, assuming that the number of moles of diamine when the equivalent ratio to the number of moles of polyamic acid at the terminal of the acid anhydride group is 100, the number of moles of diamine is within the range of 95 to 105. It is preferable that it falls within the range of 97.5 to 102.5.

  Here, in this embodiment, when the molar ratio of the polyamic acid and the diamine at the terminal of the acid anhydride group is an equivalent ratio, the molecular weight of the polyamic acid is maximized, and the viscosity of the second polymerization solution E is also maximized. . Further, as the molar ratio between the polyamic acid at the terminal of the acid anhydride group and the diamine deviates from the equivalent ratio, the molecular weight of the polyamic acid is greatly reduced, and the viscosity of the second polymerization solution E is also greatly reduced. For this reason, due to the inherent pulsation of the third supply pump 17 and the like, when the molar ratio of the polyamic acid to the diamine at the terminal of the acid anhydride group fluctuates, the molecular weight of the polyamic acid greatly changes, and the second polymerization solution E Viscosity also changes greatly. Thus, when the non-uniformity of viscosity occurs in the second polymerization solution E, the flow rate fluctuation (pulsation) occurs in the second polymerization solution E, and accordingly, the flow rate fluctuation (pulsation) also occurs in the third solution A3. This flow rate fluctuation (pulsation) becomes more significant as the viscosity increases.

  At this time, if the back pressure applied to the solution flowing through the liquid feeding line L is sufficiently high, the flow rate fluctuation (pulsation) of the second polymerization solution E due to the unevenness of viscosity becomes small, and the flow rate of the third solution A3 associated therewith. The fluctuation (pulsation) is also reduced. However, since the inherent pulsation of the third supply pump 17 is superimposed on the flow rate fluctuation (pulsation) of the third solution A3, the flow rate of the third solution A3 fluctuates in a complicated manner. In this embodiment, in order to obtain a desired polyamic acid continuously and stably even in such a situation, various controls are executed in the second control unit 200A described later.

  The second reaction unit 60 is continuously arranged on the downstream side of the second mixing unit 50. The 2nd reaction part 60 is a part which advances the polymerization reaction with the polyamic acid of the acid anhydride group terminal from the 1st polymerization solution C contained in the 2nd mixed solution D, and the diamine from the 3rd solution A3. In the second reaction unit 60, the polymerization reaction of the polyamic acid at the terminal of the acid anhydride group from the first polymerization solution C contained in the second mixed solution D and the diamine from the third solution A3 gradually proceeds, Bipolymerization solution E is obtained.

  The second reaction unit 60 is composed of a double tube extending in a predetermined direction, and includes a second reaction stirring unit 61 disposed inside in the radial direction, and a second reaction temperature adjusting unit 62 disposed outside in the radial direction. Have. The second reaction unit 60 is formed so that the second mixed solution D flows in a desired residence time.

  The 2nd reaction stirring part 61 stirs the 2nd mixed solution D with which the 1st polymerization solution C and the 3rd solution A3 were mixed in the state which does not contact gas. In this embodiment, the 2nd reaction stirring part 61 stirs the 2nd mixed solution D adjusted to the temperature suitable for polymerization reaction by the 2nd reaction temperature adjustment part 62 in the state which does not contact gas.

  The second reaction agitation unit 61 includes, for example, a static mixer, a static mixer such as a nozzle, an orifice, or the like, or a driving mixer such as a centrifugal pump, a vortex pump, or an in-line mixer having a stirring blade, preferably It is comprised including a static mixer, More preferably, it is comprised including a static mixer. As described above, the tube with the twist tape inserted can provide the stirring promotion effect similarly to the static mixer, but the static mixer is preferable because the stirring promotion effect can be obtained more.

  The static mixer is not particularly limited. For example, Kenics mixer type, Sulzer SMV type, Sulzer SMX type, Ray Hi-mixer type, Komax mixer type, Lightnin mixer type, Ross ISG type, Bran & Lub mixer type, etc. Can be mentioned. Among these, the Kenics mixer type static mixer is more preferable because of its simple structure and no dead space.

  The second reaction temperature adjusting unit 62 is a piping unit arranged on the outer side in the radial direction of the second reaction stirring unit 61. The second reaction temperature adjusting unit 62 adjusts the temperature of the second mixed solution D flowing through the second reaction stirring unit 61 to a desired temperature condition (for example, cooling). In the second reaction temperature adjusting unit 62, the second mixed solution D is adjusted to a temperature suitable for the polymerization reaction and is circulated through the second reaction stirring unit 61.

  The second cushion tank 70 stores the second polymerization solution E from the second reaction unit 60. For example, the second cushion tank 70 is a tank that stores a raw material solution when imidizing polyamic acid to produce polyimide.

  The polyamic acid production system 1A in the present embodiment may be a part of a polyimide production system that produces polyimide. In this case, the polyimide manufacturing system further includes an imidization unit that imidizes the polyamic acid. The imidization part (not shown) imidizes the polyamic acid by, for example, a thermal imidization method that thermally dehydrates and closes a ring, a chemical imidization method that uses a dehydrating agent and an imidization accelerator, and the like.

  In addition, when the polyamic acid manufacturing system 1A in the present embodiment is a part of a polyimide manufacturing system for manufacturing polyimide, the second cushion tank 70 is omitted, and the liquid is sent from the second reaction unit 60 to the imidization unit. You may comprise. However, it is preferable that the polyamic acid is once stored in the second cushion tank 70 as described above.

  The second controller 200A will be described. The second control unit 200A includes a first supply pump 15, a second supply pump 16, a first flow rate adjustment valve 151, a first flow rate measurement unit 152, a second flow rate adjustment valve 161, a second flow rate measurement unit 162, and a third flow rate. The flow rate adjusting valve 171, the third flow rate measuring unit 172, and the fourth flow rate measuring unit 182 are electrically connected.

  The second control unit 200A also has the function of the first control unit 200 in the first embodiment, but in the following, detailed description of portions common to the first control unit 200 is omitted.

  The second control unit 200A performs control so that the flow rate fluctuation rate of the third solution A3 (hereinafter also referred to as “third flow rate fluctuation rate”) is equal to or lower than the third threshold value. In the present embodiment, the third flow rate variation rate is, for example, preferably 3% or less, and more preferably 2.5% or less. The lower limit value of the third flow rate fluctuation rate is not particularly limited, but may be 0.01%, for example.

  In the present embodiment, based on the same concept as the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb of the first embodiment, the third flow rate fluctuation rate Hd is set to the flow rate with respect to the flow rate value Kd at the center of the amplitude of the flow rate fluctuation. It is defined as the ratio of the flow rate Sd that is half the amplitude of fluctuation (Hd = (Sd / Kd) × 100 [%]).

  For example, when the third flow rate variation rate is larger than the third threshold value, the second control unit 200A reduces the valve opening degree of the third flow rate adjustment valve 171 in order to make the third flow rate variation rate equal to or less than the third threshold value. The solution supplied by the third supply pump 17 so that the supply amount of the third solution A3 is the same as the supply amount before adjusting the valve opening degree of the third flow rate adjusting valve 171. Change to increase the supply pressure. In the present embodiment, the third threshold value of the third flow rate variation rate is preferably 3%, for example, and more preferably 2.5%.

  In this way, the acid anhydride contained in the first polymerization solution C is adjusted by adjusting the supply pressure of the solution supplied by the third supply pump 17 in accordance with the adjustment of the valve opening degree of the third flow rate adjustment valve 171. The first polymerization solution C and the third solution A3 can be mixed without changing the ratio of the polyamic acid at the end of the substance group and the diamine contained in the third solution A3.

  Further, when the second control unit 200A controls the third flow rate fluctuation rate to be equal to or lower than the third threshold, the flow rate fluctuation rate of the first polymerization solution C (hereinafter also referred to as “polymerization solution flow rate fluctuation rate”), The third flow rate fluctuation rate may be controlled so that the difference from the third flow rate fluctuation rate is small. Specifically, the second control unit 200A adjusts the flow rate of the third solution A3 by the third flow rate adjustment valve 171 so that the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate is small, The supply pressure of the solution supplied by the third supply pump 17 may be adjusted. In the present embodiment, the difference between the flow rate variation rate of the polymerization solution and the third flow rate variation rate is, for example, preferably 1% or less, and more preferably 0.5% or less.

  Further, the second control unit 200A controls the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate to be small, while the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate is a predetermined lower limit. The third flow rate fluctuation rate may be controlled so as not to be smaller than the value. In the present embodiment, the lower limit value of the difference between the polymerization solution flow rate variation rate and the third flow rate variation rate is preferably, for example, 0.001%. Thus, the first polymerization solution is obtained by providing a lower limit for the difference between the polymerization solution flow rate variation rate and the third flow rate variation rate and slightly shifting the mixing ratio of the first polymerization solution C and the third solution A3. C and the third solution A3 tend to be mixed well.

Next, the operation of the polyamic acid production system 1A in the second embodiment will be described with reference to FIG.
First, in the polyamic acid production system 1A, by starting the operation, the first supply pump 15 supplies the first solution A1 (first supply step), and the second supply pump 16 supplies the second solution A2 ( (Second supply step), the third supply pump 17 supplies the third solution A3 (third supply step). Here, the supply pressure (discharge pressure) of the first supply pump 15 and the second supply pump 16 is controlled by the second controller 200A so as to supply the first solution A1 and the second solution A2 at a desired ratio. It is controlled. In the third supply pump 17, the supply pressure (discharge pressure) is controlled by the second controller 200A so as to supply the third solution A3 at a desired ratio.

  Next, as shown in FIG. 5, in step ST21, the fourth flow rate measurement unit 182 measures and acquires the flow rate of the first polymerization solution C (polymerization solution flow rate measurement step). The third flow rate measuring unit 172 measures and acquires the flow rate of the third solution A3 (third measurement step).

  Next, in step ST22, the second controller 200A determines whether or not the third flow rate variation rate is greater than a third threshold value. In the present embodiment, the third threshold is set to 3%, for example. This is because it is possible to stably obtain a desired polyamic acid when the third flow rate fluctuation rate is 3% or less.

  If the second control unit 200A determines that the third flow rate variation rate is greater than the third threshold (YES), the process proceeds to step ST23. Further, when the second control unit 200A determines that the third flow rate fluctuation rate is equal to or less than the third threshold (NO), the process returns to step ST21.

  Next, in step ST23, the second control unit 200A adjusts the third flow rate adjusting valve 171 so as to reduce the valve opening degree so that the third flow rate fluctuation rate is equal to or less than the third threshold value, and the third solution A3. So that the supply pressure of the solution supplied by the third supply pump 17 is increased so that the supply amount becomes the same as the supply amount before adjusting the valve opening degree of the third flow rate adjustment valve 171 ( Second control step). Thereby, the 3rd flow rate fluctuation rate after control becomes below the 3rd threshold.

  The second controller 200A controls the third flow rate fluctuation rate so that the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate is small when the third flow rate fluctuation rate is controlled to be equal to or lower than the third threshold. May be. Specifically, the second control unit 200A adjusts the flow rate of the third solution A3 by the third flow rate adjustment valve 171 so that the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate is small, The supply pressure of the solution supplied by the third supply pump 17 may be adjusted. In the present embodiment, the difference between the flow rate variation rate of the polymerization solution and the third flow rate variation rate is, for example, preferably 1% or less, and more preferably 0.5% or less.

  Further, the second control unit 200A controls the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate to be small, while the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate is a predetermined lower limit. The third flow rate fluctuation rate may be controlled so as not to be smaller than the value. In the present embodiment, the lower limit value of the difference between the polymerization solution flow rate variation rate and the third flow rate variation rate is preferably, for example, 0.001%.

  Next, the control of the second control unit 200A enters a standby state (step ST24). Thereafter, the process returns to step ST21.

  Here, for example, the method for producing polyamic acid in the present embodiment may be a part of the method for producing polyimide. In this case, the method for producing polyimide further includes an imidization step of imidizing the polyamic acid.

According to the polyamic acid production system 1A of the present embodiment, the following effects can be obtained in addition to the effects in the first embodiment described above.
The polyamic acid production system 1A includes a second control unit 200A that controls the third flow rate variation rate to be equal to or less than a third threshold in the polyamic acid production system including the third supply pump 17 that supplies the third solution A3. . According to such a polyamic acid production system 1A, since the third flow rate fluctuation rate can be reduced, a desired polyamic acid can be obtained continuously and stably.

  In the polyamic acid production system 1A, the second controller 200A adjusts the flow rate with the third flow rate adjustment valve 171 and supplies it with the third supply pump 17 so that the third flow rate fluctuation rate is equal to or lower than the third threshold value. Adjust the supply pressure of the solution. As a result, the polyamic acid production system 1A can reduce the third flow rate variation rate and distribute the third solution A3 without changing the flow rate, so that the desired polyamic acid can be obtained continuously and more stably. It is possible.

  In the polyamic acid production system 1A, the second controller 200A can control the third flow rate fluctuation rate so that the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate is small. By reducing the difference between the polymerization solution flow rate variation rate and the third flow rate variation rate, it is possible to obtain a desired polyamic acid continuously and more stably.

  In addition, although this embodiment demonstrated the case where the 2nd reaction part 60 was comprised with the double tube | pipe of the 2nd reaction stirring part 61 and the 2nd reaction temperature adjustment part 62, it is not limited to this. . For example, the second reaction unit 60 may be composed of a single tube only with the second reaction stirring unit 61, and the second reaction stirring unit 61 may be immersed in a temperature control liquid.

<Modification>
Although two embodiments have been described above, the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

  For example, in the above-described embodiment, the polyamic acid production system is configured to include one or two reaction units (processing units), but is not limited thereto, and three or more reaction units (processing) Part). That is, the polyamic acid production system is not limited to a one-stage or two-stage reaction, and may be a three-stage or more reaction. For example, the polyamic acid production system may be configured to have three or more sets of mixing parts and reaction parts. The polyamic acid production system can adjust the supply amount and the like in multiple stages so as to approach the target reaction rate and quality each time it passes through each reaction section (treatment section).

  In the polyamic acid production system, the first solution A1 and / or the second solution A2 may contain a filler. By adding a filler to the first solution A1 and / or the second solution A2, it is possible to easily introduce the filler into the produced polyamic acid.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

<Example 1>
In Example 1, a polyamic acid was produced using a polyamic acid production system 1 having a structure as shown in FIG. In the first tank 11, a first solution in which a polyamic acid at the terminal end of an acid anhydride obtained by reaction of 4,4′-diaminodiphenyl ether and pyromellitic dianhydride is dissolved in N, N-dimethylformamide. A1 was housed. The second tank 12 contained a second solution A2 in which p-phenylenediamine was dissolved in N, N-dimethylformamide.

  First, in the first mixing unit 20, the first solution A1 supplied by the first supply pump 15 and the second solution A2 supplied by the second supply pump 16 are merged and mixed, and the first mixed solution B Was generated. Subsequently, the first mixed solution B was stirred without being in contact with gas by a Kenics mixer type static mixer (inner diameter: 8 mm, length: 520 mm). As a result of controlling the first flow rate fluctuation rate to be 0.25% and the second flow rate fluctuation rate to be 0.50%, 2410 Poise first polymerization solution C having no viscosity unevenness was obtained.

<Example 2>
In Example 2, a polyamic acid was produced using a polyamic acid production system 1 having a structure as shown in FIG. In the first tank 11, a first solution in which a polyamic acid at the terminal end of an acid anhydride obtained by reaction of 4,4′-diaminodiphenyl ether and pyromellitic dianhydride is dissolved in N, N-dimethylformamide. A1 was housed. The second tank 12 contained a second solution A2 in which p-phenylenediamine was dissolved in N, N-dimethylformamide.

  First, in the first mixing unit 20, the first solution A1 supplied by the first supply pump 15 and the second solution A2 supplied by the second supply pump 16 are merged and mixed, and the first mixed solution B Was generated. Subsequently, the first mixed solution B was stirred without being in contact with gas by a Kenics mixer type static mixer (inner diameter: 8 mm, length: 520 mm). As a result of controlling the first flow rate fluctuation rate to be 0.32% and the second flow rate fluctuation rate to be 0.40%, 5700 Poise first polymerization solution C having no viscosity unevenness was obtained.

<Comparative Example 1>
In Comparative Example 1, a polyamic acid was produced using a polyamic acid production system 1 having a structure as shown in FIG. In the first tank 11, a first solution in which a polyamic acid at the terminal end of an acid anhydride obtained by reaction of 4,4′-diaminodiphenyl ether and pyromellitic dianhydride is dissolved in N, N-dimethylformamide. A1 was housed. The second tank 12 contained a second solution A2 in which p-phenylenediamine was dissolved in N, N-dimethylformamide.

  First, in the first mixing unit 20, the first solution A1 supplied by the first supply pump 15 and the second solution A2 supplied by the second supply pump 16 are merged and mixed, and the first mixed solution B Was generated. Next, the first mixed solution B was stirred without being in contact with gas by a Kenics mixer type static mixer (inner diameter: 8 mm, length: 930 mm). As a result of continuing the liquid feeding at the first flow rate fluctuation rate of 0.44% and the second flow rate fluctuation rate of 8.8%, a first polymerization solution C having a large viscosity unevenness of 50 to 630 poise was obtained.

1, 1A Polyamic acid production system 15 First supply pump (first supply unit)
16 2nd supply pump (2nd supply part)
17 3rd supply pump (3rd supply part)
20 1st mixing part 30 1st reaction part 50 2nd mixing part 60 2nd reaction part 151 1st flow control valve (1st flow control part)
152 1st flow measurement part 161 2nd flow adjustment valve (2nd flow adjustment part)
162 Second flow rate measurement unit 171 Third flow rate adjustment valve (third flow rate adjustment unit)
172 Third flow rate measurement unit 182 Fourth flow rate measurement unit (polymerization solution flow rate measurement unit)
200 first control unit 200A second control unit A1 first solution A2 second solution A3 third solution B first mixed solution C first polymerization solution D second mixed solution E second polymerization solution L liquid feed line

Claims (22)

Polyamics for producing polyamic acid using as raw materials a first solution containing a polyadditive first polymerizable compound and a second solution containing a polyadditive second polymerizable compound polyadded with the first polymerizable compound An acid production system comprising:
A first supply unit for supplying the first solution;
A second supply part for supplying the second solution;
A first mixing unit that mixes the first solution and the second solution to form a first mixed solution;
A first flow rate measuring unit for measuring a flow rate of the first solution;
A second flow rate measuring unit for measuring the flow rate of the second solution;
The first that is arranged continuously downstream of the first mixing part and includes a polyamic acid by proceeding a polymerization reaction between the first polymerizable compound and the second polymerizable compound contained in the first mixed solution. A first reaction part for producing a polymerization solution;
A polyamic acid production comprising: a first control unit that controls the flow rate fluctuation rate of the first solution to be equal to or lower than a first threshold value and controls the flow rate fluctuation rate of the second solution to be equal to or lower than a second threshold value. system. A first flow rate adjustment unit capable of adjusting a flow rate of the first solution;
A second flow rate adjustment unit capable of adjusting the flow rate of the second solution,
The first control unit adjusts the flow rate with the first flow rate adjusting unit and supplies the solution with the first supply unit so that the flow rate variation rate of the first solution is equal to or less than the first threshold value. Adjusting the flow rate by the second flow rate adjustment unit and adjusting the supply pressure of the solution supplied by the second supply unit so that the flow rate fluctuation rate of the second solution is less than or equal to the second threshold value. The polyamic acid production system according to claim 1.   The first controller controls the first supply so that a ratio of the first polymerizable compound contained in the first solution and the second polymerizable compound contained in the second solution is within a predetermined range. The polyamic acid production system according to claim 1, wherein the system controls the part and / or the second supply part.   The first control unit controls the flow rate fluctuation rate of the first solution and / or the second solution so that a difference between the flow rate fluctuation rate of the first solution and the flow rate fluctuation rate of the second solution becomes small. The polyamic acid manufacturing system according to any one of claims 1 to 3.   The polyamic acid production system according to any one of claims 1 to 4, wherein the first reaction unit includes a first reaction stirring unit that stirs the first mixed solution without contacting the gas. The polyamic acid contained in the first polymerization solution is a polyamic acid having an acid anhydride group terminal or an amino group terminal,
A third supply unit for supplying a third solution containing diamine or tetracarboxylic dianhydride to be polyadded to the acid anhydride group-terminated or amino group-terminated polyamic acid contained in the first polymerization solution;
A second mixing unit that mixes the first polymerization solution and the third solution to form a second mixed solution;
A polymerization solution flow rate measuring unit for measuring a flow rate of the first polymerization solution;
A third flow rate measuring unit for measuring the flow rate of the third solution;
An acid anhydride-terminated or amino-terminated polyamic acid from the first polymerization solution, which is continuously disposed downstream of the second mixing unit and contained in the second mixed solution, and from the third solution A second reaction section for producing a second polymerization solution containing a polyamic acid by advancing a polymerization reaction with diamine or tetracarboxylic dianhydride;
The polyamic acid production system according to any one of claims 1 to 5, further comprising a second control unit that controls the flow rate variation rate of the third solution to be equal to or less than a third threshold value. A third flow rate adjusting unit capable of adjusting the flow rate of the third solution;
The second control unit adjusts the flow rate by the third flow rate adjustment unit so that the flow rate variation rate of the third solution is equal to or less than the third threshold value, and supplies the solution by the third supply unit. The polyamic acid production system according to claim 6, wherein the pH is adjusted.   The second control unit has a predetermined ratio of a polyamic acid having an acid anhydride group terminal or an amino group terminal contained in the first polymerization solution and a diamine or tetracarboxylic dianhydride contained in the third solution. The polyamic acid production system according to claim 6 or 7, wherein the third supply unit is controlled to be inside.   The second control unit controls the flow rate fluctuation rate of the third solution so that a difference between the flow rate fluctuation rate of the first polymerization solution and the flow rate fluctuation rate of the third solution becomes small. The polyamic acid manufacturing system of any one of these.   The polyamic acid production system according to any one of claims 6 to 9, wherein the second reaction unit includes a second reaction stirring unit that stirs the second mixed solution without contacting the gas. The polyamic acid production system according to any one of claims 1 to 10,
A polyimide production system comprising: an imidization unit that imidizes the polyamic acid produced by the polyamic acid production system. Polyamics for producing polyamic acid using as raw materials a first solution containing a polyadditive first polymerizable compound and a second solution containing a polyadditive second polymerizable compound polyadded with the first polymerizable compound A method for producing an acid, comprising:
A first supply step of supplying the first solution;
A second supply step of supplying the second solution;
A first mixing step of mixing the first solution and the second solution to form a first mixed solution;
A first measuring step for measuring a flow rate of the first solution;
A second measuring step for measuring a flow rate of the second solution;
A first reaction step of generating a first polymerization solution containing a polyamic acid by advancing a polymerization reaction between the first polymerizable compound and the second polymerizable compound contained in the first mixed solution;
A first control step of controlling the flow rate fluctuation rate of the first solution to be equal to or lower than a first threshold value and controlling the flow rate fluctuation rate of the second solution to be equal to or lower than a second threshold value. Production method. A first flow rate adjusting step capable of adjusting the flow rate of the first solution;
A second flow rate adjusting step capable of adjusting the flow rate of the second solution,
In the first control step, the supply pressure of the solution supplied by the first supply step and the flow rate is adjusted by the first flow rate adjustment step so that the flow rate fluctuation rate of the first solution is not more than the first threshold value. The flow rate is adjusted by the second flow rate adjustment step and the supply pressure of the solution supplied by the second supply step is adjusted so that the flow rate fluctuation rate of the second solution is less than or equal to the second threshold value. The method for producing a polyamic acid according to claim 12.   In the first control step, the first supply is performed so that a ratio between the first polymerizable compound contained in the first solution and the second polymerizable compound contained in the second solution is within a predetermined range. The method for producing a polyamic acid according to claim 12 or 13, wherein the step and / or the second supply step is controlled.   In the first control step, the flow rate fluctuation rate of the first solution and / or the second solution is controlled so that the difference between the flow rate fluctuation rate of the first solution and the flow rate fluctuation rate of the second solution is reduced. The method for producing a polyamic acid according to any one of claims 12 to 14.   The method for producing a polyamic acid according to any one of claims 12 to 15, wherein the first reaction step includes a first reaction stirring step of stirring the first mixed solution without contacting the gas. The polyamic acid contained in the first polymerization solution is a polyamic acid having an acid anhydride group terminal or an amino group terminal,
A third supply step of supplying a third solution containing a diamine or tetracarboxylic dianhydride to be polyadded to the acid anhydride group-terminated or amino group-terminated polyamic acid contained in the first polymerization solution;
A second mixing step of mixing the first polymerization solution and the third solution to form a second mixed solution;
A polymerization solution flow rate measuring step for measuring a flow rate of the first polymerization solution;
A third flow rate measuring step for measuring a flow rate of the third solution;
The polymerization reaction of the acid-terminated or amino-terminated polyamic acid from the first polymerization solution contained in the second mixed solution and the diamine or tetracarboxylic dianhydride from the third solution is allowed to proceed. A second reaction step for producing a second polymerization solution containing a polyamic acid;
The method for producing a polyamic acid according to any one of claims 12 to 16, further comprising a second control step of controlling the flow rate variation rate of the third solution to be equal to or less than a third threshold value. A third flow rate adjusting step capable of adjusting the flow rate of the third solution;
In the second control step, the supply pressure of the solution supplied by the third supply step and the flow rate is adjusted by the third flow rate adjustment step so that the flow rate variation rate of the third solution is not more than the third threshold value. The manufacturing method of the polyamic acid of Claim 17 which adjusts.   In the second control step, the ratio between the acid anhydride group-terminated or amino group-terminated polyamic acid contained in the first polymerization solution and the diamine or tetracarboxylic dianhydride contained in the third solution is within a predetermined range. The method for producing a polyamic acid according to claim 17 or 18, wherein the third supply step is controlled to be inside.   In the second control step, the flow rate fluctuation rate of the third solution is controlled so that the difference between the flow rate fluctuation rate of the first polymerization solution and the flow rate fluctuation rate of the third solution is reduced. The manufacturing method of the polyamic acid of any one of these.   The method for producing a polyamic acid according to any one of claims 17 to 20, wherein the second reaction step includes a second reaction stirring step in which the second mixed solution is stirred without being in contact with gas. The polyamic acid manufacturing process which manufactures a polyamic acid with the manufacturing method of any one of Claims 12-21,
The imidization process of imidating the polyamic acid manufactured in the said polyamic acid manufacturing process, The manufacturing method of the polyimide containing.

Images