JP4661273B2 - End-capped polybenzoxazole precursor and method for producing end-capped polybenzoxazole resin. - Google Patents

Description

  The present invention relates to a method for producing a terminal-capped polybenzoxazole precursor and a terminal-capped polybenzoxazole resin.

In the conventional method for producing an end-capped polybenzoxazole precursor by polycondensation reaction, the polybenzoxazole precursor was produced by a two-step process of synthesis and end-capping, but the first-stage resin ( In the synthesis of (polymers), it is based on a method of reacting by adding a dicarboxylic acid compound as a powder to a solution containing a diaminophenol compound, or a method of slowly dropping and reacting a solution in which the dicarboxylic acid compound is dissolved. In such a state, the two compounds described above were mixed, resulting in variations in the reaction molar ratio, which could have a significant effect on the three-dimensional structure of the resulting polymer (see, for example, Non-Patent Document 1). In the second-stage reaction, it is difficult to efficiently mix the solution containing the high-viscosity polymer obtained in the first-stage synthesis and the solution containing the low-viscosity organic compound. It is difficult to obtain an end-capped polymer structure. Further, since these reactions are reactions accompanied by a rapid exotherm, hot spots are generated in the reaction solution, and it is difficult to obtain a uniform polymer structure (see, for example, Non-Patent Document 2), and the resulting resin. The molecular weight distribution of was also wide.
Moreover, since the terminal is not completely sealed by the equivalent addition of the terminal blocking agent in the conventional polymerization method, the terminal blocking agent is excessively added. However, even if it is added in excess, the ends are not completely sealed, and the reaction probability between the ends of the polymer and the sealing agent is low in the conventional polymerization reaction system, and the molecular weight of the polymer is large. Indeed, the reaction probability between the end of the polymer and the sealant becomes smaller due to its difficulty.

Imai Itsuo and Yokota Rikio, "Latest Polyimides-Fundamentals and Applications", NTS Corporation, 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 terminal-capped polybenzoxazole precursor and a method for producing a terminal-capped polybenzoxazole resin capable of producing a uniform polymerization product in a short time with a narrow molecular weight distribution. It is.

In the present invention, the first solution containing the diaminophenol compound (A) and the second solution containing the dicarboxylic acid compound (B) are each made to have a cross-sectional area of 10 ² from the first hollow channel portion and the second hollow channel portion, respectively. And introduced into a first hollow mixer having a fine structure of 10 ⁷ μm ² and a reaction region of the dicarboxylic acid compound (B) with respect to the diaminophenol compound (A), mixed, and a polybenzoxazole precursor ( A method for producing an end-capped polybenzoxazole precursor characterized by obtaining a third solution containing C), and more preferably a third solution containing the polybenzoxazole precursor (C) obtained above. A solution and a fourth solution containing an end-capping compound (D) are added to the end-capping compound (D) with respect to the polybenzoxazole precursor (C) through a third hollow channel portion and a fourth hollow channel portion, respectively. ) And a second hollow mixer having a fine structure with a cross-sectional area of 10 ² to 10 ⁷ μm ² , which is a reaction region with the above, and a high-speed uniform mixing method. It is.

In the method for producing an end-capped polybenzoxazole precursor of the present invention, the reaction molar ratio (B / A) of the dicarboxylic acid compound (B) to the diaminophenol compound (A) in the reaction region in the first hollow mixer. ) Is adjusted more uniformly by adjusting the concentration of the first solution and the second solution and / or the linear velocity of the first solution and the second solution in the first hollow channel portion and the second hollow channel portion. Can be reacted.
The reaction molar ratio (D / C) of the end-capping compound (D) to the polybenzoxazole precursor (C) in the reaction region in the second hollow mixer is the concentration of the third solution and the fourth solution. And / or it can be made to react more uniformly by adjusting with the linear velocity of the 3rd solution and the 4th solution in the 3rd hollow channel part and the 4th hollow channel.

The reaction molar ratio (B / A) of the dicarboxylic acid compound (B) to the diaminophenol compound (A) in the reaction zone in the first hollow mixer is preferably 0.5 to 2.0, and the second hollow mixing The reaction molar ratio (D / C) of the end-capping compound (D) to the polybenzoxazole precursor (C) in the in-machine reaction region is preferably 0.01 to 0.25. The linear velocities of the first solution, the second solution, the third solution, and the fourth solution are each preferably 10 ⁻⁴ to 10 ² m / sec.
The first solution preferably contains a base because the molecular weight can be further increased.

Moreover, it is preferable to carry out by controlling the reaction temperature in the reaction region in the first hollow mixer and / or the second hollow mixer from 20 ° C to 30 ° C.
The hollow mixer can improve productivity by having a plurality of the microstructures.

  The molecular weight distribution (Mw / Mn) of the end-capped polybenzoxazole precursor obtained by the production method is preferably 3.0 or less.

  Furthermore, the present invention provides a polybenzoxazole resin characterized by obtaining a polybenzoxazole resin by further heating and condensing the end-capped polybenzoxazole precursor obtained by the above production method. This is a production method, whereby a terminal-capped polybenzoxazole resin can be obtained.

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

In the present invention, the first solution containing the diaminophenol compound (A) and the second solution containing the dicarboxylic acid compound (B) are each made to have a cross-sectional area of 10 ² from the first hollow channel portion and the second hollow channel portion, respectively. ^{to 107} wherein the [mu] m ² at which the microstructure polybenzoxazole precursor (C) and the end capping compound (D) and the diaminophenol compound reaction zone (a) and the dicarboxylic acid compound (B) and the And a first step of obtaining a third solution containing the polybenzoxazole precursor (C) by introducing the mixture into a first hollow mixer having a reaction region and mixing the end-capped polybenzoxazole It is a manufacturing method of a precursor. More preferably, in the method for producing an end-capped polybenzoxazole precursor of the present invention, the third solution containing the polybenzoxazole precursor (C) and the fourth solution containing the end-capping compound (D) are used. And a reaction of the fine structure having a cross-sectional area of 10 ² to 10 ⁷ μm ² , the polybenzoxazole precursor (C), and the end-capping compound (D) from the third hollow channel and the fourth hollow channel, respectively. And a second step of introducing into a second hollow mixer having a region and mixing at high speed uniformly.

In the method for producing an end-capped polybenzoxazole precursor of the present invention, the reaction molar ratio (B / A) of the dicarboxylic acid compound (B) to the diaminophenol compound (A) in the reaction region of the first hollow mixer. ) Adjust the concentration of the first solution and the second solution as appropriate and / or adjust the linear velocity of the first solution and the second solution as appropriate in the first hollow flow path part and the second hollow flow path part. It is preferable to do.
Further, the reaction molar ratio (D / C) of the end-capping compound (D) to the polybenzoxazole precursor (C) in the reaction region in the second hollow mixer is the concentration of the third solution and the fourth solution. It is preferable to adjust as appropriate and / or adjust the linear velocity of the third solution and the fourth solution in the third hollow channel portion and the fourth hollow flow channel portion as appropriate, and the reaction can be performed uniformly by these. .

According to the production method of the present invention, in a multistage reaction, it is possible to mix uniformly at high speed, and since the reaction is performed in a micromixing space which is a reaction region after the microstructure, the specific surface area of the reaction region is obtained. Can increase the temperature of the reaction solution due to the heat of reaction, and thus can produce a uniform end-capped polybenzoxazole precursor in a short time without causing hot spots. is there.
In addition, the polymer is stretched due to shear due to the flow in the micro space after the microstructure in the mixer, and the reaction between the end-capping agent and the high molecular weight is easily performed in the reaction region in the second mixer. Probability increases.

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.
In the production process of the end-capped polybenzoxazole precursor of the present invention, the first solution and the second solution are passed through the first hollow flow channel 01 and the second hollow flow channel 02, respectively. In the first mixing space 04 continuously supplied to the first hollow mixer 03 having a structure and provided as a flow cell type reaction region in the first hollow mixer 03, the first solution and the second solution Are mixed to obtain a third solution in which an end-capped polybenzoxazole precursor is produced.

  In the present invention, the fourth solution can be reacted further continuously, via the third solution third hollow flow path 07 obtained above, and the fourth solution via the fourth hollow flow path 06. Thus, an addition reaction occurs in the second mixing space 09 that is continuously supplied to the second hollow mixer 08 having a fine structure and is provided as a flow cell type reaction region in the second hollow mixer 08, and end-capping is performed. A stop-type polybenzoxazole precursor is produced. Here, in order to improve the mixing efficiency in the first mixing space 04 and the second mixing space 09, the first solution and the second solution in the minute space 05, which is a hollow channel, in the third solution and the second solution. The four solutions are preferably mixed in a layered structure in the minute space 10 which is a hollow channel.

  In the present invention, as the reaction region, the flow in which each reaction material is supplied from the inlet hollow portion of the fine structure is fed from the fine structure, and the flow region is in contact with each other, and after the merging where the mixing and reaction proceed. This is the space for mixing and reaction, including the region.

FIG. 2 is a cross-sectional view showing an example of a reaction apparatus composed of hollow mixers 03 and 08 having a fine structure.
As the reaction apparatus used in the present invention, first, the first solution and the second solution are supplied by a syringe pump, a plunger pump, or the like, and the first hollow channel and the second hollow channel are respectively supplied from the inlet connection portions 11 and 12. Can be used, so that it is continuously supplied to the first hollow mixer 03 having the fine structure portion 16. The first solution and the second solution react in the first mixing space 14 that is a reaction region from the fine structure portion, and the solution containing the reaction product is discharged from the outlet connection portion 13.
Next, the fourth solution supplied by a plunger pump or the like and the third solution discharged from the outlet connection portion 13 are passed through the third hollow flow channel and the fourth hollow flow channel, respectively, and the fine structure portion 22 is formed. What is comprised so that it may be continuously supplied to the 2nd hollow mixer 08 which has can be used. The third solution and the fourth solution further react in the mixed space 20 that is a reaction region from the fine structure portion to generate an end-capped polybenzoxazole precursor, which is discharged from the outlet connection portion 19.

Here, in order to improve the mixing efficiency in the mixing spaces 14 and 20, the first solution and the second solution are in the micro space 05 which is a hollow channel, and the third solution and the fourth solution are the micro space which is a hollow channel. 10, the structure is preferably layered.
Furthermore, in order to improve productivity, in the hollow mixers 03 and 08, it is preferable to provide a plurality of fine structure parts and further a plurality of mixing spaces, and specifically, it is preferable to connect a plurality of these in parallel. Moreover, as a control method of reaction temperature, it can carry out by methods, such as the method of providing and controlling a temperature control part in the vicinity of mixing space, or the method of immersing a hollow mixer and a reaction area in a temperature-controlled water bath.

FIG. 3 is a plan view showing an example of the fine structures 16 and 22 attached to the holding members 15 and 21 of FIG.
The fine structure portion will be described in more detail. The fine structure portion of the first hollow mixer and the fine structure portion of the second hollow mixing portion can use the same structure, and the fine structure portion 23 is the first solution. And inlet hollow portions 24 and 25 serving as supply ports for the second solution (third solution and fourth solution) are provided, and the first solution and the second solution (third solution and fourth solution) are respectively provided in the inlet hollow portions. Are introduced into the fine hollow flow paths (first hollow flow path, second hollow flow path, (third hollow flow path, fourth hollow flow path)) 26, 27 from the parts 24, 25, and further, the first hollow flow The channel and the second hollow flow channel (third hollow flow channel and fourth hollow flow channel) are respectively introduced in layers in a direction perpendicular to the flow of the solution from each inlet hollow portion, It is the reaction zone provided afterwards as a structure where the laminar flow contacts alternately In the small mixing space, it is preferable to mix the laminar flow, and the mixing space may be configured to be supplied to the mixing space having a rectangular shape having a horizontal section that is elongated in the width direction as the reaction region. The space may have the same cross-sectional area as that of the microstructure.

More specifically, the first and second hollow flow paths (third hollow flow path and fourth hollow flow path) 26 and 27 extend between the inlet space portions 24 and 25, respectively. It is preferable in mixing that it is formed in a zigzag shape. The first hollow flow channel 26 and the second hollow flow channel 27 (the third hollow flow channel 26 and the fourth hollow flow channel 27) are a plurality of, for example, 10 to 20 flow channels that are alternately adjacent to each other. It is preferable to be provided.
In the first and second hollow mixers, the fine structure preferably has a cross-sectional area of 10 ² to 10 ⁷ μm ² , and the first hollow channel, the second hollow channel, and the third hollow channel in the fine structure. The widths D1 and D2 of the fourth hollow channels 26 and 27 are preferably 1 to 1000 μm, more preferably 10 to 500 μm, and further preferably 25 to 50 μm. The thickness D3 of the partition wall 28 between the first hollow channel and the second hollow channel and between the third hollow channel and the fourth hollow channel is, for example, 10 to 30 μm, for example 10 μm, The depth D4 is, for example, 10 to 500 μm, for example, 300 μm.

  Examples of the diaminophenol compound (A) used in the present invention include 2,4-diaminoresorcinol, 4,6-diaminoresorcinol, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2 , 2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) Compounds having dihydroxylbenzene such as propane, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone and 4,4′-diamino-3,3′-dihydroxydiphenylsulfone, 3,3′-diamino-4 , 4′-dihydroxybiphenyl and 4,4′-diamino-3,3′-dihydroxybiphenyl Compounds having dihydroxy-biphenyl such as enyl, 9,9-bis (4-((4-amino-3-hydroxy) phenoxy) phenyl) fluorene and 9,9-bis (4-((3-amino-4- Compounds having dihydroxy-fluorene compounds such as hydroxy) phenoxy) phenyl) fluorene, dihydroxys such as 3,3′-diamino-4,4′-dihydroxydiphenyl ether and 4,4′-diamino-3,3′-dihydroxyphenyl ether -Compounds having ether, 2,2-bis (3-amino-4-hydroxy-2-trifluoromethylphenyl) propane, 2,2-bis (4-amino-3-hydroxy-2-trifluoromethylphenyl) Propane and 2,2-bis (3-amino-4-hydroxy-5-trifluoro Compounds having dihydroxy-propane, such as methylphenyl) propane, 2,2-bis (3-amino-4-hydroxy-2-trifluoromethylphenyl) hexafluoropropane and 2,2-bis (4-amino-3-) Compounds having dihydroxy-hexafluoropropane, such as hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 1,1′-binaphthyl-3,3′-diamino-2,2′-diol, bis (2-(( 4-amino-3-hydroxy) phenoxy))-1,1′-binaphthyl and bis (2-((3-amino-4-hydroxy) phenoxy))-1,1′-binaphthyl. These may be used alone or in combination of two or more.

  Examples of the dicarboxylic acid compound (B) used in the present invention include compounds having biphenyl dicarboxylic acid such as phthalic acid such as isophthalic acid and terephthalic acid, 3,4′-biphenyldicarboxylic acid and 3,3′-biphenyldicarboxylic acid. Compounds having naphthalene dicarboxylic acids such as 2,3-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid, bisbenzoic acids such as 4,4′-oxybisbenzoic acid and 3,4′-oxybisbenzoic acid, 3, Compounds having naphthalenedicarboxylic acid such as 3′-naphthalenedicarboxylic acid, carboxyphenyl-hexafluoropropane such as 2,2-bis (4-carboxyphenyl) propane and 2,2-bis (3-carboxyphenyl) hexafluoropropane 2,2 ′ compounds having Bis (trifluoromethyl) -4,4′-biphenyldicarboxylic acid, 3,3′-bis (trifluoromethyl) -4,4′-biphenyldicarboxylic acid and 2,2′-bis (trifluoromethyl) -3 , 3′-biphenyldicarboxylic acid and other compounds having trifluoromethyl-biphenyldicarboxylic acid, 9,9-bis (4- (4-carboxyphenoxy) phenyl) fluorene and 9,9-bis (4- (3-carboxyl) Compounds having carboxyphenoxy-fluorene such as phenoxy) phenyl) fluorene, 4,4′-bis (4-carboxyphenoxy) biphenyl and 4,4′-bis (3-carboxyphenoxy) biphenyl, 3,4′-bis Carboxyphenoxy-biphenyl such as (4-carboxyphenoxy) biphenyl Compounds having 4,4′-bis (4-carboxyphenoxy) -p-terphenyl, 4,4′-bis (4-carboxyphenoxy) -m-terphenyl and 3,4′-bis (4-carboxyphenoxy) ) Compounds having carboxyphenoxy-terphenyl such as -p-terphenyl, 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroterephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2, Examples include fluorophthalic acid such as 3,5,6-tetrafluoroterephthalic acid and 5-trifluoromethylisophthalic acid, and these may be used alone or in combination of two or more.

As the end-capping compound (D) used in the present invention, a carboxylic acid compound is used in the case of an aminophenol compound terminal, for example, phthalic anhydride, maleic anhydride, 2,3-naphthalenedicarboxylic anhydride, 1, 8-naphthalenedicarboxylic anhydride, cis-1,2-cyclohexyldicarboxylic acid, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, benzoic acid, 1 -Carboxylic acids such as naphthoic acid. These may be used alone or in combination of two or more.
Further, as the end-capping compound (D) used in the present invention, an aminophenol compound is used in the case of a carboxylic acid compound terminal, for example, o-aminophenol, 2,4-aminoresorcinol, 4,6-aminoresorcinol, and 4 Compounds having hydroxyl benzene such as amino-3-hydroxydiphenyl sulfone, compounds having hydroxy-biphenyl such as 3-diamino-4-hydroxybiphenyl and 4-amino-3-hydroxybiphenyl, 3-amino-4-hydroxydiphenyl ether And compounds having a hydroxy-ether such as 4-amino-3-hydroxyphenyl ether. These may be used alone or in combination of two or more.

  Examples of the base used in the present invention include pyridine, N, N-dimethylaminopyridine, 2,4,6-trimethylpyridine, 2-trimethylsilylpyridine, triethylamine and the like. These may be used alone or in combination of two or more.

As a method for producing the end-capped polybenzoxazole precursor of the present invention, first, a diaminophenol compound (A), a dicarboxylic acid compound (B), and an end-capping compound (D), and a base as necessary. , N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, etc. are dissolved in an organic solvent to prepare a first solution, a second solution, and a fourth solution, respectively.
When the second step is further performed by sequentially feeding the first solution and the second solution to the first hollow mixer with a syringe pump or a plunger pump and reacting them in a specific temperature range. In the same manner, the third solution and the fourth solution are sequentially fed to the second hollow mixer and reacted to obtain a solution of the end-capped polybenzoxazole precursor. The reaction temperature is preferably 20 to 30 ° C. and more preferably 23 to 27 ° C. in order to form a polymer structure. The reaction temperature may be the same or different in the first mixer and the second mixer.

In the method for producing a polybenzoxazole precursor of the present invention, the reaction molar ratio (B / A) of the dicarboxylic acid compound (B) to the diaminophenol compound (A) is the concentration of the first solution and the second solution, or The linear velocity immediately before mixing the first solution and the second solution in the first hollow mixer, that is, the linear velocity of the first solution and the second solution in the first hollow channel portion and the second hollow channel portion is adjusted. Among these, it is more preferable to adjust the linear velocity, and it is more preferable to adjust the concentrations of the first solution and the second solution and the linear velocity.
Further, the reaction molar ratio (D / C) of the end-capping compound (D) to the polybenzoxazole precursor (C) is the concentration of the third solution and the fourth solution, or the third in the second hollow mixer. It is preferable to adjust the linear velocity immediately before the mixing of the solution and the fourth solution, that is, the linear velocity of the third solution and the fourth solution in the third hollow channel and the fourth hollow channel. It is more preferable to adjust the speed, and it is more preferable to adjust the concentrations of the third solution and the fourth solution and the linear speed.

The reaction molar ratio (B / A) of the component (B) to the component (A) is preferably 0.5 to 1.0 when the polybenzoxazole precursor is end-capped derived from an aminophenol compound, In the case of terminal blocking derived from a carboxylic acid compound, 1.0 to 2.0 is preferable.
In addition, the reaction molar ratio (D / C) of the end-capping compound (D) to the polybenzoxazole precursor (C) is preferably 0.01 to 0.5, and preferably 0.01 to 0.25. More preferred.

The linear velocity of the diaminophenol compound (A) and the dicarboxylic acid compound (B) immediately before the mixing is preferably 10 ⁻⁴ to 10 ² m / sec in order to exhibit sufficient mixing ability and control the molecular weight. More preferably, it is 10 ⁻³ to 10 ⁻¹ m / sec. When the upper limit is exceeded, the molecular weight does not increase, and when it is less than the lower limit, the molecular weight distribution may become wide. In addition, the linear velocity of the polybenzoxazole precursor (C) and the dicarboxylic anhydride compound (D) immediately before mixing is 10 ⁻⁴ to 10 ² m in order to exhibit sufficient mixing ability and control the molecular weight. / Sec is preferable, and 10 ⁻³ to 10 ⁻¹ m / sec is more preferable. The total reaction time is preferably 1 to 60 seconds when calculated from the linear velocity.

  In addition, as described above, in terms of linear velocity, it is preferable to provide a linear velocity ratio, particularly for improving the mixing efficiency between the third solution and the fourth solution. As the linear velocity ratio between the third solution and the fourth solution (third solution / fourth solution), for example, a linear velocity ratio of 10/1 to 1/10 is preferable, and 1/1 to 1/10. A linear velocity ratio is more preferable. It is preferable to increase the linear velocity of the solution having a smaller viscosity. The linear velocity ratio can be adjusted by the cross-sectional area of the hollow channel in the microstructure.

  According to the production method of the present invention, an end-capped polybenzoxazole precursor having a narrow molecular weight distribution with a molecular weight distribution (Mw / Mn) of 3.0 or less can be obtained, and 1.0 to 3.0 A linear velocity and concentration of the component (A), the component (B), and the component (C), and the component (A), the component (B), and The end-capped polybenzoxazole precursor can be produced by controlling the molecular weight by adjusting any one or more of the reaction molar ratio with the component (C), and the end-capping obtained thereby. The type polybenzoxazole precursor also has a narrow molecular weight distribution.

  The polybenzoxazole precursor obtained by the method for producing a polybenzoxazole precursor of the present invention can be converted into a rebenzoxazole resin by heating and performing a condensation reaction. The obtained rebenzoxazole resin can be used for applications such as semiconductor interlayer insulating films and surface protective films. When producing a resin film for such an application, the polybenzoxazole precursor solution obtained by the production method of the present invention is applied to a substrate such as glass, fiber, metal, silicon wafer and ceramic substrate. A coating film is formed, and the resulting coating film is heated at about 320 ° C., preferably at a temperature stepwise changed to 100 ° C., 200 ° C., and 320 ° C., thereby causing a cyclization condensation reaction. A polybenzoxazole resin film can be used as the benzoxazole resin.

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

  Including the reaction time in Examples and Comparative Examples, and the results of the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the respective resins calculated using gel permeation chromatography, These results are summarized in Table 1.

Example 1
(1) Synthesis of polybenzoxazole precursor 1.09888 g (3.0 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane 0.4651 g (5.88 mmol) of pyridine was dissolved in 10 ml of dried N-methyl-2-pyrrolidone, and 0.8854 g (3.0 mmol) of 4,4′-oxybisbenzoyl chloride was dissolved in 10 ml of γ-butyrolactone. . Further, 0.2655 g (1.6 mmol) of 5-norbornene-2,3-dicarboxylic acid anhydride was dissolved in 8.0 ml of N-methyl-2-pyrrolidone.
These solutions are sucked into a gas tight syringe, and 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane and pyridine solutions and 4, The 4′-oxybisbenzoic acid chloride solution is fed to the first hollow mixer at a linear velocity of 6.6 × 10 ⁻² m / sec, and 0.2655 g of 5-norbornene-2,3-dicarboxylic anhydride. (1.6 mmol) was fed to the second hollow mixer at a linear velocity of 1.3 × 10 ⁻¹ m / sec and mixed and reacted (the total reaction time calculated from the linear velocity was 51.10). 2 seconds). In addition, the thing of the same structure was used for the 1st hollow mixer and the 2nd hollow mixer. The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained polybenzoxazole precursor were converted to polystyrene using gel permeation chromatography (hereinafter abbreviated as GPC) manufactured by Tosoh Corporation. Were 3.84 × 10 ⁴ and 1.61 respectively.
Note that the hollow mixer has the first hollow flow path and the second hollow flow path in the microfabricated member shown in FIG. 2 The hollow channel width D2 was 40 μm, and the cross-sectional area of the microstructure and 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 800 μmφ, outer diameter 1/16 inch, Tefzel is a resin tube product name obtained from DuPont). The first hollow mixer and the second hollow mixer are connected with a Tefzel tube 0.4 m (inner diameter 800 μmφ, outer diameter 1/16 inch), and the Tefzel tube 9.0 m is connected to the outlet of the second hollow mixer. In order to keep the reaction temperature attached with an inner diameter of 800 μmφ and an outer diameter of 1/16 inch, 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.

(2) Production of polybenzoxazole precursor The polybenzoxazole 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, and 320 degreeC / 1 hour in nitrogen atmosphere in oven, and obtained the 10-micrometer-thick polybenzoxazole resin film.

(3) Evaluation Using the polybenzoxazole resin film obtained above, the glass transition temperature and heat resistance were measured by the following methods for property evaluation. These results are summarized in Table 1.
1. Heat Resistance Using a TG / DTA220 manufactured by Seiko Instruments Inc., the temperature at a weight loss of 5% 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 DMS6100 manufactured by Seiko Instruments Inc., measured in tension mode under a flow of nitrogen gas of 300 mL / min under the conditions of a measurement frequency of 1 Hz and a heating rate of 3 ° C./min, the peak top temperature of loss tangent (tan δ) The glass transition temperature was taken.

(Example 2)
In the same manner as in Example 1, except that 5-norbornene-2,3-dicarboxylic acid anhydride was changed to 0.2025 g (1.6 mmol) of benzoyl chloride, end-capped polybenzoxazole was used. A precursor was synthesized. The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained end-capped polybenzoxazole precursor were determined using GPC in the same manner as in Synthesis Example 1, and found to be 3.44 × 10 4 respectively. ⁴ and 1.74.

(Example 3)
In Example 1, 1.02-255 g (2.8 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 4,4′- Oxybisbenzoic acid chloride 0.8854 g (3.0 mmol), 5-norbornene-2,3-dicarboxylic acid anhydride o-aminophenol 0.1091 g (1.6 mmol) amount and linear velocity of 2.65 × 10 respectively ^-2 and 8.28 × 10 ^-2 m / sec, except that the end-capped polybenzoxazole precursor was synthesized in the same manner as in Example 1 (calculated from the linear velocity of each component). The linear velocity ratio between the third solution and the fourth solution is 5/8). When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained end-capped polyamide resin were determined using GPC in the same manner as in Example 1, 3.47 × 10 ⁴ and It was 1.81.

Example 4
A terminal-capped polybenzoxazole precursor was synthesized in the same manner as in Example 3 except that in Example 3, o-aminophenol was changed to 2,4-aminoresorcinol. When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained end-capped polybenzoxazole precursor were determined using GPC in the same manner as in Example 1, they were 3.81 × 10 4 respectively. ⁴ and 1.94.

In a glass three-necked flask, 1.09888 g (3.0 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane and 0.4651 g of pyridine ( 5.88 mmol) was added and dissolved in 10.0 ml of dry N-methyl-2-pyrrolidone. Thereafter, a solution prepared by dissolving 0.8854 g (3.0 mmol) of 4,4′-oxybisbenzoyl chloride in 10.0 ml of γ-butyrolactone was added at 10 ° C. or less in a nitrogen atmosphere, and stirring was continued for 60 minutes. Next, a solution prepared by dissolving 0.0676 g (0.4 mmol) of 5-norbornene-2,3-dicarboxylic anhydride in 1.0 ml of N-methyl-2-pyrrolidone was added, and stirring was further continued for 60 minutes. All reactions were performed at room temperature. 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 end-capped polybenzoxazole precursor were determined using GPC in the same manner as in Example 1, they were 2.99 × 10 4 respectively. ⁴ and 2.11.

(Comparative Example 2)
In Comparative Example 1, 1.8313 g (4.0 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane and 0.4651 g of pyridine (5.88 mmol), 4,4′-oxybisbenzoic acid chloride 1.4756 g (5.0 mmol), and benzoyl chloride 0.0506 g (0.4 mmol) were used. An encapsulated polybenzoxazole precursor was synthesized. When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained end-capped polybenzoxazole precursor were determined using GPC in the same manner as in Example 1, each was 3.03 × 10. ⁴ and 2.30.

  From the results of Examples and Comparative Examples summarized in Table 1, the end-capped polybenzoxazole precursor synthesized by the production method of the present invention can be synthesized efficiently and in a short time compared to conventional products. In addition, since the reaction temperature can be precisely controlled within a specific temperature range, a uniform end-capped polybenzoxazole precursor is formed, and the molecular weight distribution is It turns out that it became narrow compared with the legal method.

  Since the end-capped polybenzoxazole precursor obtained by the production method of the present invention is a uniform polymerization product with a narrow molecular weight distribution, it is used for photosensitive resins and high-performance resins that require such characteristics. It is suitable for.

It is a figure which simplifies and shows the whole structure of one Embodiment of this invention. It is sectional drawing for demonstrating the reaction apparatus comprised from the hollow mixer which has a fine structure. It is a top view for demonstrating the fine structure part with which the holding member was mounted | worn.

Explanation of symbols

01 1st hollow flow path 02 2nd hollow flow path 03 1st hollow mixing machine 04 1st mixing space 05,10 micro space 06 3rd hollow flow path 07 4th hollow flow path 08 2nd hollow mixing machine 09 2nd mixing Space 11, 12, 17, 18 Inlet connection portion 13, 19 Outlet connection portion 14, 20 Mixing space 15, 21 Holding member 16, 22, 23 Fine structure portion 24, 25 Inlet hollow portion 26, 27 Hollow flow path 28 Partition

Claims (15)

The first solution containing the diaminophenol compound (A) and the second solution containing the dicarboxylic acid compound (B) are respectively cross-sectional areas of 10 ² to 10 ⁷ μm from the first hollow channel portion and the second hollow channel portion. ² is introduced into a first hollow mixer having a microstructure of ² and a reaction region of the diaminophenol compound (A) and the dicarboxylic acid compound (B), and mixed to obtain a polybenzoxazole precursor (C). A method for producing an end-capped polybenzoxazole precursor, comprising a first step of obtaining a third solution containing the first solution. The method for producing an end-capped polybenzoxazole precursor according to claim 1, wherein the first solution contains a base. The third solution containing the polybenzoxazole precursor (C) and the fourth solution containing the end-capping compound (D) are respectively cross-sectional area 10 ² from the third hollow channel portion and the fourth hollow channel portion. A second step of introducing and mixing into a second hollow mixer having a fine structure of 10 ⁷ μm ² and a reaction region of the polybenzoxazole precursor (C) and the end-capping compound (D) A method for producing an end-capped polybenzoxazole precursor according to claim 1 or 2. The method for producing an end-capped polybenzoxazole precursor according to any one of claims 1 to 3, wherein the hollow mixer has a plurality of the fine structures. The reaction molar ratio (B / A) of the dicarboxylic acid compound (B) to the diaminophenol compound (A) in the reaction zone in the first hollow mixer is the concentration of the first solution and the second solution and / or the first The end-capped polybenzoxazole precursor according to any one of claims 1 to 4, which is adjusted by the linear velocity of the first solution and the second solution in the hollow channel portion and the second hollow channel portion. Body manufacturing method. The reaction molar ratio (D / C) of the end-capping compound (D) to the polybenzoxazole precursor (C) in the reaction region in the second hollow mixer is the concentration of the third solution and the fourth solution and / or Or an end-capped polybenzo according to any one of claims 3 to 5, which is adjusted by the linear velocity of the third solution and the fourth solution in the third hollow channel portion and the fourth hollow channel. A method for producing an oxazole precursor. The end-capping type according to any one of claims 1 to 6, wherein a reaction molar ratio (B / A) of the dicarboxylic acid compound (B) to the diaminophenol compound (A) is 0.5 to 2.0. A method for producing a polybenzoxazole precursor . The terminal mole according to claim 3, wherein a reaction molar ratio (D / C) of the end-capping compound (D) to the polybenzoxazole precursor (C) is 0.01 to 0.25. A method for producing a sealed polybenzoxazole precursor. 9. The method for producing an end-capped polybenzoxazole precursor according to claim 5, wherein the linear velocities of the first solution and the second solution are 10 ⁻⁴ to 10 ² m / sec, respectively. The method for producing an end-capped polybenzoxazole precursor according to any one of claims 6 to 9, wherein the linear velocities of the third solution and the fourth solution are 10 ^-4 to 10 ² m / sec, respectively. 11. The end-capping type according to claim 6, wherein a linear velocity ratio (third solution / fourth solution) of the third solution to the fourth solution is 10/1 to 1/10. A method for producing a polybenzoxazole precursor. The method for producing an end-capped polybenzoxazole precursor according to claim 11, wherein the linear velocity ratio is adjusted by a cross-sectional area of a hollow flow path in the microstructure. The end-capped polybenzoxazole precursor according to any one of claims 1 to 12, wherein the reaction temperature in the reaction region in the first and / or second hollow mixer is controlled from 20 ° C to 30 ° C. Production method. The molecular weight distribution (Mw / Mn) of the end-capped polybenzoxazole resin obtained by the production method is 3.0 or less. Production of the end-capped polybenzoxazole resin according to any one of claims 1 to 13. Method. The polybenzoxazole precursor obtained by the manufacturing method of the polybenzoxazole precursor in any one of Claims 1-14 is further heated, and a polybenzoxazole resin is obtained by carrying out a condensation reaction. A method for producing a polybenzoxazole resin.

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