JP4273904B2 - Method for producing polyimide precursor and polyimide resin - Google Patents

Description

  The present invention relates to a polyimide precursor and a method for producing a polyimide resin.

  In the conventional method for producing a polyimide precursor by polyaddition reaction, a powder of a tetracarboxylic acid compound is slowly added to a solution containing a diamine compound, resulting in uneven mixing of the raw materials. Therefore, since the reaction molar ratio of the two compounds varies, it has a significant effect on the three-dimensional structure of the resulting polymer (see, for example, Non-Patent Document 1). In addition, since this reaction is a reaction accompanied by a rapid exotherm, a hot spot is generated in the reaction solution, and it is difficult to obtain a uniform polymer structure (see, for example, Non-Patent Document 2). The molecular weight distribution was also wide.

Imai, Ikuo, Yokota Rikio, “Latest Polyimide: Fundamentals and Applications”, NTS, January 2002 Material / Process Committee Microreactor Working Group, Microreactor WG Research Report “Research on Microreactor Technology Oriented to Chemical Synthesis”, Chemical Technology Strategy Promotion Organization, June 2000

  An object of the present invention is to provide a method for producing a polyimide precursor and a method for producing a polyimide resin, which can produce a uniform polymerization product in a short time with a narrow molecular weight distribution.

The present invention provides a first solution containing a diamine compound (A) and a second solution containing a tetracarboxylic acid compound (B), respectively, in the reaction region from the first hollow channel portion and the second hollow channel portion, respectively. The concentration of the first solution and the second solution or the first hollow channel portion and the second hollow channel so that the reaction molar ratio of the component (B) to the component (A) is 0.5 to 2.0. The linear velocity of the first solution and the second solution in the section is adjusted, and the first hollow channel and the second hollow channel are configured, and the respective mixing space opening portions are alternately provided adjacent to each other in layers and opened. and microstructure area of the surface is 10 ² to 10 ⁶ [mu] m ^2, was introduced into a hollow mixer having a mixing space, in the first solution and the second solution linear velocity of each 10 ^-3 to 10 ² m / s A method for producing a polyimide precursor characterized by high-speed uniform mixing.
In the production method of the polyimide precursor of the present invention, the reaction temperature in the reaction zone is preferably performed by controlling the 25 ℃ ± 2 ℃. The polyimide precursor obtained by the production method of the above SL are those having a molecular weight distribution 2.00~3.50 (Mw / Mn).
In the reaction apparatus used in the method for producing a polyimide precursor of the present invention, the hollow mixer may be one having a plurality of the microstructures.
Furthermore, the present invention provides a polyimide resin characterized in that a polyimide resin is obtained by further heating and condensing a polyimide precursor obtained by any of the above polyimide precursor production methods. Is the method.

  According to the present invention, a uniform polymerization product of polyimide can be generated in a short time, and a polyimide having a narrow molecular weight distribution as compared with the conventional method can be obtained.

In the present invention, the first solution containing the diamine compound (A) and the second solution containing the tetracarboxylic acid compound (B) have a reaction molar ratio of the component (B) to the component (A) of 0.5 to 0.5. In producing a polyimide precursor by reacting at 2.0, the first solution and the second hollow channel part, using a reaction apparatus having a hollow mixer having a fine structure, the first solution and the The second solution is composed of a first hollow channel and a second hollow channel, which are reaction regions, from a first hollow channel and a second hollow channel, respectively, and each mixing space opening is layered. The reaction molar ratio is 0.5 to 2.0 in the hollow mixer having the mixing structure and the fine structure which is alternately provided adjacently and has an open surface area of 10 ² to 10 ⁶ μm ^2. As described above, the concentration of the first solution and the second solution or the first hollow flow path portion and the second hollow Since the linear velocity of the first solution and the second solution in the flow path section is adjusted and introduced, and high-speed uniform mixing is performed, the temperature rise of the reaction solution due to the reaction heat can be suppressed, thereby generating a hot spot. And a uniform polyimide precursor can be generated in a short time.

A reaction apparatus having a production process in the present invention and a hollow mixer used for production will be described with reference to the drawings.
FIG. 1 is a perspective view showing a simplified overall configuration of an embodiment of the present invention.
As the manufacturing process, the first solution is supplied from the first supply source 001 and the second solution is supplied from the second supply source 002 through the first hollow channel 005 and the second hollow channel 006, respectively. It supplies continuously to the hollow mixer 003 which has a structure, and a 1st solution and a 2nd solution are mixed in the mixing space 004 of the hollow mixer 003, a polyaddition reaction occurs, and a polyimide precursor produces | generates. Here, in order to improve the mixing efficiency in the mixing space 004, it is preferable that the first solution and the second solution have a layered structure in the minute space 007 that is a hollow channel.

FIG. 2 is a cross-sectional view showing an example of a reaction apparatus composed of a hollow mixer 003 having a fine structure.
The reaction device is a supply device such as a syringe pump or a plunger pump, and the first solution and the second solution are supplied from the supply sources 001 and 002 from the inlet connection members 009 and 010, respectively. It is configured to be supplied to a microfabricated member 015 provided with a flow path and a mixing space. The microfabricated member 015 is housed in a holding member 013 and is mounted on the microfabricated member 015 of the mixing member 012 and the holding member 013. Further, the mixing space is disposed on the first hollow channel and the second hollow channel, has a narrowed shape, and further has an outlet slit 016 that is a slit-type space at the outlet portion, thereby mixing efficiency. Can be improved. In order to improve productivity, it is preferable to provide a plurality of microstructures (microfabricated members) composed of the first hollow channel and the second hollow channel in the hollow mixer 003. Examples of the method for controlling the reaction temperature include a method in which a temperature controller is provided in the vicinity of the mixing space and a method in which the hollow mixer is immersed in a temperature-controlled water bath.

FIG. 3 is a plan view of the microfabricated member 015 attached to the holding member 013 and an enlarged view thereof.
The microfabricated member 015 is provided with inlet hollow portions 017 and 018 serving as supply ports from the first supply source and the second supply source, and the first solution and the second solution are respectively provided in the inlet hollow portions 017 and 018. Are introduced into fine hollow flow channels (first hollow flow channel, second hollow flow channel) 019, 020. Further, the first solution is introduced from the first hollow flow channel and the second solution is introduced from the second hollow flow channel in a layered manner in a direction perpendicular to the flow of the solution from the inlet hollow portion to form a reaction region. It is supplied to the outlet slit part 016 having a mixing space whose rectangular horizontal section is rectangular.

In the mixing, the first and second hollow flow channels 019, 020 are preferably formed in a zigzag shape between the inlet space portions 017, 018. Moreover, it is preferable that a plurality of, for example, 10 to 20 channels, for example, the first hollow channel 019 and the second hollow channel 020 are adjacently provided alternately.
In the hollow mixer, the fine structure preferably has an area of the open surface of the mixing space of 10 ² to 10 ⁶ μm ^2. The widths D 1 and D 2 of the first and second hollow flow channels 019 and 020 in the fine structure are: 1-1000 micrometers is preferable, it is more preferable that it is 10-500 micrometers, and it is further more preferable that it is 25-50 micrometers. Further, the thickness D3 of the partition wall 021 is, for example, 10 to 30 μm, for example, 10 μm, and the depth D4 is, for example, 10 to 500 μm, for example, 300 μm.

  Examples of the diamine compound (A) used in the present invention include m-phenylenediamine, p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, bis (4-aminophenyl) ether, and 1,4-cyclohexanediamine. O-toluidinediamine, p-toluidinediamine, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethylbiphenyl, 4, , 4'-diamino-2,2'-bis (trifluoromethyl) biphenyl and the like. These may be used alone or in combination of two or more.

  Examples of the tetracarboxylic acid compound (B) used in the present invention include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3,4 ′. -Biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) ) -1,1,1,3,3,3-hexafluoropropane dianhydride, tetracarboxylic dianhydride such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride. These may be used alone or in combination of two or more.

As a method for producing the polyimide precursor of the present invention, first, the diamine compound (A) and the tetracarboxylic acid compound (B) are dissolved in an organic solvent such as N, N-dimethylacetamide or N-methyl-2-pyrrolidone. Then, the first solution and the second solution are prepared. These solutions are sent to the reaction apparatus with a syringe pump or a plunger pump, introduced into a hollow mixer having a fine structure, and reacted in a specific temperature range to obtain a polyimide precursor solution. . The reaction temperature is preferably 20 to 30 ° C. and more preferably 23 to 27 ° C. in order to form a polymer structure.
The concentration of the diamine compound (A) and the tetracarboxylic acid compound (B) is preferably 0.2 to 1.0M, and more preferably 0.3 to 0.7M in order to obtain a high viscosity polymer solution. The reaction molar ratio of the component (B) to the component (A) is preferably 0.5 to 2.0 and more preferably 0.75 to 1.25 in order to control the molecular weight.
The concentration of the first solution and the second solution or the first hollow flow so that the reaction molar ratio of the tetracarboxylic acid compound (B) to the diamine compound (A) in the reaction region is 0.5 to 2.0. It can adjust with the linear velocity of the 1st solution and the 2nd solution in a channel and the 2nd hollow channel part.
In addition, the linear velocity of the solution of the diamine compound (A) and the tetracarboxylic acid compound (B) is preferably 10 ⁻³ to 10 ² m / sec in order to exhibit sufficient mixing ability, and 10 ⁻² to 10 ^1. More preferred is m / sec. The reaction time is preferably 1 to 60 seconds when calculated from the linear velocity.

According to the production method of the present invention, a polyimide precursor having a molecular weight distribution (Mw / Mn) of 2.00 to 3.50 can be obtained.
The polyimide precursor solution obtained by the production method of the present invention is applied to, for example, glass, fiber, metal, silicon wafer, ceramic substrate, etc., and the obtained coating film is 300 ° C., preferably 100 ° C., 200 By heating at a temperature that is changed in steps of ℃ and 300 ℃, a cyclized condensation reaction occurs and a polyimide resin can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by this.

Using the films prepared in Examples and Comparative Examples, heat resistance and glass transition temperature (Tg) were measured by the following methods for property evaluation. These results are summarized in Table 1, including the reaction time, weight average molecular weight (Mw) calculated using gel permeation chromatography, and molecular weight distribution (Mw / Mn). .
1. Heat resistance Using a TG / DTA220 manufactured by Seiko Instruments Inc., weight loss at 200 to 450 ° C. was measured under a nitrogen gas flow of 200 mL / min and a temperature increase rate of 10 ° C./min.
2. Glass transition temperature (Tg)
Using a TMA / SS1200DM manufactured by Seiko Instruments Inc., the glass transition temperature was determined from the intersection of the asymptotic lines of the inflection point by measuring in a tensile mode at a temperature rising rate of 5 ° C./min.

(Example 1)
(1) Synthesis of polyimide precursor 20 ml of N, N-dimethylacetamide obtained by drying 1.6060 g (8.0 mmol) of bis (4-aminophenyl) ether and 1.752 g (8.0 mmol) of pyromellitic dianhydride, respectively. Each was dissolved. These solutions are sucked into a gas tight syringe manufactured by Hamilton, and fed to a hollow mixer at a linear velocity of 8.3 × 10 ⁻¹ m / sec using a Harvard PHD 2000 Programmable Syringe Pump. (The reaction time calculated from the linear velocity is 1.2 seconds). The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained polyimide precursor were converted to polystyrene using gel permeation chromatography (hereinafter abbreviated as GPC) manufactured by Shimadzu Corporation. When determined, they were 12,000 and 3.08, respectively.
In the hollow mixer, in the microfabricated member in FIG. 3, the first hollow flow path and the second hollow flow path are adjacently arranged to be adjacent to each other so that the first hollow flow path width D1 and the first hollow flow path 2 The hollow channel width D2 was 40 μm, and the cross-sectional area of the mixing space was 3.6 × 10 ⁵ μm ² . The gas tight syringe and the hollow mixer were connected by a Tefzel tube (inner diameter 500 μmφ, outer diameter 1/16 inch). A Tefzel tube 1.0 m (inner diameter 500 μmφ, outer diameter 1/16 inch) was attached to the outlet of the hollow mixer. In order to keep the reaction temperature constant, the hollow mixer was immersed in a 25 ° C. water bath whose temperature was controlled by a circulation tank. The reaction temperature was measured using a wide range temperature data logger TR-81 manufactured by T & D Corporation.
(2) Production of polyimide resin The polyamide precursor solution obtained above was applied onto a glass plate using a doctor blade. Then, it heated in order of 100 degreeC / 1 hour, 200 degreeC / 1 hour, 300 degreeC / 1 hour in nitrogen atmosphere in oven, and obtained the 10-micrometer-thick polyimide resin film.

(Example 2)
In the synthesis of the polyimide of Example 1, except that the amounts of bis (4-aminophenyl) ether and pyromellitic dianhydride were changed to 1.6841 g (8.4 mmol) and 1.7423 g (8.0 mmol), respectively. A polyimide precursor was synthesized in the same manner as in Example 1. When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained polyimide precursor were determined using GPC in the same manner as in Synthesis Example 1, they were 8,000 and 3.10.
The polyamide precursor solution obtained above was treated in the same manner as in Example 1 to obtain a polyimide resin film.

(Comparative Example 1)
In a 100 ml glass three-necked flask, 1.5108 g (7.5 mmol) of bis (4-aminophenyl) ether was dissolved in 32 ml of dried N, N-dimethylacetamide. Thereafter, 1.6371 g (7.5 mmol) of pyromellitic dianhydride was added at 25 ° C. under a nitrogen atmosphere, and stirring was continued for 120 minutes. In order to keep the reaction temperature constant, the three-necked flask was immersed in a 25 ° C. water bath. The reaction temperature was measured using a wide range temperature data logger TR-81 manufactured by T & D Corporation. When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained polyimide precursor were calculated | required using GPC similarly to Example 1, they were 8,200 and 3.74, respectively.
The polyamide precursor solution obtained above was treated in the same manner as in Example 1 to obtain a polyimide resin film.

(Comparative Example 2)
Comparative Example 1 except that the amounts of bis (4-aminophenyl) ether and pyromellitic dianhydride were changed to 1.5060 g (7.5 mmol) and 1.5584 g (7.1 mmol), respectively, in Comparative Example 1. In the same manner as in Example 1, a polyimide precursor was synthesized. When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained polyimide precursor were calculated | required using GPC similarly to Example 1, they were 8,000 and 3.57, respectively.
The polyamide precursor solution obtained above was treated in the same manner as in Example 1 to obtain a polyimide resin film.

  From the evaluation results of the examples and comparative examples summarized in Table 1, the polyimide precursor synthesized by the polyaddition reaction method of the present invention maintains the same resin properties (glass transition temperature, heat resistance) as conventional products, It was clarified that it was synthesized efficiently in a short time. In addition, since the reaction temperature during polymerization can be precisely controlled within a specific temperature range, a uniform polyimide precursor is generated, and the molecular weight distribution is narrower than that of conventional polymerization methods. I understand that.

  Since the polyimide obtained by the production method of the present invention is a uniform polymerization product with a narrow molecular weight distribution, it is suitable for use in photosensitive resins and high-performance resins that require such characteristics.

It is a perspective view which simplifies and shows the whole structure of one Embodiment of this invention. It is sectional drawing of the hollow mixer 003 which has a microstructure. It is the top view of the microfabricated member 015 with which the holding member 013 was mounted | worn, and its enlarged view.

Explanation of symbols

001 1st supply source 002 2nd supply source 003 Hollow mixing machine having microfabrication site 004 Mixing space 005 1st hollow flow path 006 2nd hollow flow path 007 Micro space 008 Partition wall 009,010 Inlet connection member 011 Outlet connection member 012 Mixing member 013 Holding member 014 Mounting screw part 015 Finely processed member 016 Exit slit part 017,018 Inlet hollow part 019 First hollow channel 020 Second hollow channel 021 Bulkhead

Claims (5)

The first solution containing the diamine compound (A) and the second solution containing the tetracarboxylic acid compound (B) are respectively added to the component (A) in the reaction region from the first hollow channel portion and the second hollow channel portion. The concentration of the first solution and the second solution or the first and second hollow flow path portions in the first solution and the second hollow flow path portion so that the reaction molar ratio of the component (B) to 0.5 to 2.0 is achieved. The linear velocity of 1 solution and 2nd solution is adjusted, it is comprised from the 1st hollow flow path and the 2nd hollow flow path, and each mixing space opening part is alternately provided adjacent to the layer form, and the area of an open surface is It is introduced into a hollow mixer having a fine structure of 10 ² to 10 ⁶ μm ² and a mixing space , and the linear velocity of the first solution and the second solution is uniformly mixed at 10 ⁻³ to 10 ² m / sec. The manufacturing method of the polyimide precursor characterized by the above-mentioned. The method for producing a polyimide precursor according to claim 1, wherein the hollow mixer has a plurality of the fine structures. The method for producing a polyimide precursor according to claim 1 or 2, wherein the reaction temperature in the reaction region is controlled to 25 ° C ± 2 ° C. The method for producing a polyimide precursor according to any one of claims 1 to 3 , wherein the polyimide precursor obtained by the production method has a molecular weight distribution (Mw / Mn) of 2.00 to 3.50. The polyimide precursor obtained by the manufacturing method of the polyimide precursor in any one of Claims 1 thru | or 4 is further heated and condensation-reacted, A polyimide resin is obtained, The manufacturing method of the polyimide resin characterized by the above-mentioned .