WO2021065653A1

WO2021065653A1 - Powder, powder production method, and solution production method

Info

Publication number: WO2021065653A1
Application number: PCT/JP2020/035950
Authority: WO
Inventors: 健史細井; 峰男渡辺
Original assignee: セントラル硝子株式会社
Priority date: 2019-09-30
Filing date: 2020-09-24
Publication date: 2021-04-08
Also published as: JPWO2021065653A1; CN114555549A; KR20220069060A; TW202120463A

Abstract

A powder for a compound represented by general formula (A). For example, the mode diameter D_m for this powder, measured using the laser diffraction scattering method, is 75–150 μm and the Ca ion content is less than 1 ppm. In general formula (A), R¹–R⁸ each independently indicate a hydrogen atom, a C1–4 alkyl group, a halogen atom, or an amino group. This powder can be obtained by a method including, for example, a melting step (i) in which a feedstock substance is melted in the presence of an aqueous carrier fluid and an heterogeneous fluid is obtained, by the feedstock substance, which includes a compound indicated by general formula (A), and an aqueous carrier fluid (a poor solvent of the compound indicated in general formula (A)) being put into a container and heated; and a crystallization step (ii) in which the melt is crystallized by reducing the temperature of the heterogeneous fluid.

Description

Powder, powder manufacturing method and solution manufacturing method

The present invention relates to a powder, a method for producing a powder, and a method for producing a solution. More specifically, the present invention relates to a powder of a fluorinated bisphenol compound represented by the general formula (A) described later, a method for producing the powder, and a method for producing a solution using the powder.

Fluorinated bisphenol compounds typified by 2,2-bis (4-hydroxyphenyl) hexafluoropropane (hereinafter also abbreviated as "BIS-AF") are often used as raw materials for various resins.

As an example, in Patent Document 1, which is a document relating to an epoxy resin composition, as Production Example 1, BIS-AF was crystallized in a mixed solvent of ethylene glycol and pure water to obtain a white powder thereof. It is stated that.

As another example, in the examples of Patent Document 2, a solid BIS-AF in which the impurity hexafluoroacetone is reduced by neutralizing and precipitating BIS-AF dissolved in an alkaline aqueous solution with hydrochloric acid is used. It is stated that it was obtained.

As yet another example, in the claims and examples of Patent Document 3, 2,2-bis (4-hydroxyphenyl) hexafluoropropane and water are heated to room temperature or higher, and a solution (aqueous solution) is prepared. A method for purifying 2,2-bis (4-hydroxyphenyl) hexafluoropropane is described, which obtains a solid that precipitates by cooling.

Japanese Unexamined Patent Publication No. 2007-246819 Japanese Unexamined Patent Publication No. 4-054144 Japanese Unexamined Patent Publication No. 2-067239

Fluorinated bisphenol compounds typified by BIS-AF are industrially usually manufactured and sold as powders. In addition, the powder may be used as it is in various industrial processes.
According to the findings of the present inventors, there is room for improvement in the conventional powdery fluorinated bisphenol compound from the viewpoint of industrial handleability. "Industrial handleability" means, for example, one or more of the following items.
・ Good filterability ・ Short drying time when drying wet powder ・ Difficult to absorb moisture ・ Good fluidity of powder ・ Good solvent solubility, specifically, quick dissolution in solvent ・ Agglomeration Difficult to (block)

The present invention has been made in view of such circumstances. One of the objects of the present invention is to provide a powdery fluorinated bisphenol compound having excellent industrial handleability.

The present inventors have completed the following first to fourth inventions.

The first invention is as follows.

A powder of a compound represented by the general formula (A) below.
_{The mode diameter D m} measured by the laser diffraction / scattering method is 75 to 150 μm.
A powder having a Ca ion content of less than 1 ppm.

In the general formula (A), R ¹ to R ⁸ independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom or an amino group, respectively.

The second invention is as follows.

A powder of a compound represented by the general formula (A) below.
The volume-reduced cumulative 50% diameter measured by a laser diffraction scattering method and D _50, when the arithmetic volume average diameter measured by the law and the D _ave,
D ₅₀ is 50-100 μm
D ₅₀ / D _ave is a powder of 1.1 to 1.5.

The third invention is as follows.

A powder of a compound represented by the general formula (A) below.
Volume-reduced cumulative 50% diameter _{D 50} measured by a laser diffraction scattering method is 50 ~ 100 [mu] m,
A powder with an angle of repose of 35 to 49 °.

The fourth invention is as follows.

2,2-Bis (4-hydroxyphenyl) hexafluoropropane powder
The half width of the peak near 2θ = 22.3 ° in the X-ray diffraction spectrum is 0.050 ° or more and 0.180 ° or less.
The half width of the peak near 2θ = 23.7 ° in the X-ray diffraction spectrum is 0.050 ° or more and 0.120 ° or less.
A powder having a peak width of 0.040 ° or more and 0.120 ° or less in the X-ray diffraction spectrum near 2θ = 25.8 °.

In addition, the present inventors have completed the following invention of the powder manufacturing method.

Hereinafter, a method for producing a powder of a compound represented by the general formula (A).
By putting the raw material containing the compound represented by the general formula (A) and the aqueous dispersion medium in a container and heating the raw material, the raw material is melted in the presence of the aqueous dispersion medium, and the raw material is melted. A melting step of obtaining a non-uniform liquid containing a melt and the aqueous dispersion medium, and
A crystallization step of crystallizing the melt to obtain crystals by lowering the temperature of the non-uniform liquid.
Including
In the melting step, the melting temperature T ₁ of the said raw material, said aqueous dispersion medium, the solubility of the compound represented by the general formula (A), 10 [g / 100g] or less, the production of the powder Method.

In addition, the present inventors have completed the following invention of the solution manufacturing method.

A method for producing a solution containing a compound represented by the general formula (A) below.
A method for producing a solution, which comprises a step of obtaining a solution of the compound represented by the general formula (A) using a solvent and at least one of the powders of the first to fourth inventions.

The powder of the present invention is excellent in industrial handleability.

It is a figure for demonstrating the particle size distribution of the powder of 2nd Embodiment. It is a figure for demonstrating the particle size distribution of the powder of 2nd Embodiment.

Hereinafter, embodiments of the present invention will be described in detail.
In the present specification, the notation "XY" in the description of the numerical range means X or more and Y or less unless otherwise specified. For example, "1 to 5% by mass" means "1% by mass or more and 5% by mass or less".

In the notation of a group (atomic group) in the present specification, the notation that does not indicate whether it is substituted or unsubstituted includes both those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The term "electronic device" as used herein refers to an element to which electronic engineering technology is applied, such as a semiconductor chip, a semiconductor element, a printed wiring board, an electric circuit display device, an information communication terminal, a light emitting diode, a physical battery, and a chemical battery. , Devices, final products, etc.

In the present specification, the compound represented by the general formula (A) may be referred to as "compound (A)".

In the present specification, the embodiment of the first invention is the first embodiment, the embodiment of the second invention is the second embodiment, the embodiment of the third invention is the third embodiment, and the embodiment of the fourth invention. May be referred to as the fourth embodiment.
Further, in the present specification, the embodiment of the above-mentioned powder manufacturing method invention may be described as the first manufacturing method. On the other hand, a method for producing a powder that does not correspond to the above-mentioned invention of the powder production method but can produce the powder of the present invention (at least one of the first to fourth inventions) is described as a second production method. Sometimes.

<Powder>
The powders of the first to third embodiments are powders of a compound (compound (A)) represented by the following general formula (A). Further, the powder of the fourth embodiment is a powder of a compound in which all of ^{R 1} to R ^{8 are hydrogen atoms in the following general formula (A).}

In formula ^(A), the alkyl group having 1 to 4 carbon atoms R 1 ~ ^{R 8,} methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, t- butyl group And so on.
In the general formula (A), preferably, R ¹ to R ⁸ are independently hydrogen atoms or amino groups.
In the general formula (A), when ^{at least one of R 1} to R ⁸ is a group other than a hydrogen atom, the group other than the hydrogen atom is at any position of R ² , R ³ , R ⁶ , or R ^7. It is preferable to be present in. This is because of the ease of synthesizing the compound.
In the general formula (A) ^{, 0 to 4 of R 1} to R ⁸ are preferably groups other than hydrogen atoms, and 0 to 2 are more preferably groups other than hydrogen atoms.

Specifically, the compound (A) includes 2,2 bis (4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxy-3-methylphenyl) hexafluoropropane, and 2,2-bis (3). -Ethyl-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, 2,2-bis (3-fluoro-4-hydroxyphenyl) hexafluoro Propane, 2,2-bis (3-bromo-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-bis) Amino-4-hydroxyphenyl) hexafluoropropane and the like can be mentioned.

In particular, the following compounds are mentioned as preferable compounds (A).

(First Embodiment)
_{The mode diameter (mode diameter) D m} of the powder of the first embodiment measured by the laser diffraction / scattering method is 75 to 150 μm, preferably 75 to 135 μm, and more preferably 75 to 120 m.
The Ca ion content of the powder of the first embodiment is less than 1 ppm, preferably 0.7 ppm or less, and more preferably 0.5 ppm or less. As a reminder, in the present specification, the "ppm" of the Ca ion (and Na ion described later) content is one million of "mass of Ca ion in powder / mass of powder". It is a fraction. The relationship with mass% is 1 ppm = 0.0001 mass%.

The industrial handleability of the powder of the first embodiment is good. Specifically, the powder of the first embodiment has advantages such as "good filterability" and "the drying time when drying the wet powder can be shortened". It is presumed that these advantages are due to the D _m being 75 to 150 μm.
The details are unknown, but it is presumed that when the D _m is 75 μm or more, there is an appropriate “gap” between the particles, which makes it easier for the liquid to flow. Further, _{it is presumed that when D m} is 150 μm or less, the “gap” does not become too large, and it is difficult to hold a large amount of liquid between the particles in the first place.

In addition, the present inventors have tried to control the content of Ca ions in the powder to less than 1 ppm in the first embodiment.
Ca ion is a component inevitably contained in general industrial water. Therefore, if the powder of compound (A) is produced so that the content of Ca ions is less than 1 ppm using the content of Ca ions as an index, various trace impurities (industrial water) other than Ca ions in the obtained powder can be produced. The amount of origin) can also be reduced. That is, the compound (A) in which the amount of Ca ions is less than 1 ppm is considered to have a small amount of not only Ca ions but also various impurities, and is preferably applicable to various technical fields. In addition, as will be described later, since Ca ions can be measured by ion chromatography, it is possible to facilitate process control in mass production equipment.

By the way, the fact that the Ca ion content is less than 1 ppm means that the powder of the first embodiment can be directly used preferably as a material for manufacturing an electronic device that requires a small amount of metal ions. Means.

The Ca ion content is preferably 0.7 ppm or less, more preferably 0.5 ppm or less.
Basically, the smaller the amount of Ca ions, the more preferable. The Ca ion content may be zero (below the measurement limit of the device). From a practical point of view, the Ca ion content is, for example, 0.01 ppm or more.

The method and conditions for producing the powder of the first embodiment are not limited. By selecting appropriate methods and conditions, _{a powder of compound (A) having a D m} of 75 to 150 μm and a Ca ion content of less than 1 ppm can be obtained. Preferably, as in the first production method described later, it is preferable that the raw material is melted (not dissolved) in an aqueous dispersion medium and then crystallized. By appropriately selecting the conditions for melting and crystallization, a _{powder of compound (A) having a D m} of 75 to 150 μm and a Ca ion content of less than 1 ppm can be obtained. The manufacturing method and manufacturing conditions will be described in detail later.

The Na ion content of the powder of the first embodiment is less than 1 ppm, preferably 0.7 ppm or less, and more preferably 0.5 ppm or less. By setting the amount of Na ions in addition to Ca ions to less than 1 ppm, the powder of the present embodiment can be further more preferably applied to the production of electronic devices. Further, the Na ion content may be zero (below the measurement limit of the device). From a practical point of view, the Na ion content is, for example, 0.01 ppm or more.

The content of Mg ions in the powder of the first embodiment is less than 1 ppm, preferably 0.7 ppm or less, and more preferably 0.5 ppm or less. Like Ca ions, the content of Mg ions is also an index that can be used when calculating the hardness of water, and Mg ions may be unavoidably contained in industrial water. Therefore, by setting the amount of Mg ions in addition to Ca ions to less than 1 ppm, the powder of the present embodiment can be further more suitably applied to various uses such as manufacturing of electronic devices. Further, the content of Mg ions may be zero (below the measurement limit of the apparatus). From a practical point of view, the content of Mg ions is preferably 0.01 ppm or more, for example.

The content of metal ions such as Ca ions can be determined by using an ion chromatography analysis method. In ion chromatography analysis, a sample solution in which the powder of compound (A) is usually dissolved in an organic solvent such as t-butyl methyl ether is prepared. The content of metal ions in this sample liquid is measured, and "mass of Ca ions in powder / mass of powder" is calculated from the obtained measured values.

In the conventional BIS-AF purification method, particularly the reprecipitation method using water, it was often difficult to reduce the amount of metal ions because the water used itself contained metal ions. A metal such as Ca ion is formed by recrystallizing the compound (A) by a method of "not actively" dissolving "the compound (A) in water while using water as in the first manufacturing method described later. A powder having a small amount of ions can be obtained.

The powder of the first embodiment does not contain alcohol such as monool and diol, or preferably contains a small amount of alcohol. Water-soluble monools with 4 or less carbon atoms, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl, even if they contain alcohol. It is more preferable to contain a small amount of -2-propanol or the like.
The content of alcohol in the powder of the first embodiment is preferably 400 ppm or less, more preferably 200 ppm or less, still more preferably 100 ppm or less. Although it is common sense in chemistry, it should be mentioned here that "alcohol" does not include phenolic compounds (compounds having phenolic hydroxyl groups).
Since the powder does not contain alcohol, or even if it contains a small amount of alcohol, an unintended reaction is unlikely to occur when a polymer is produced using the powder of the present embodiment as a raw material, and a desired polymer can be obtained. Easy to manufacture.
Further, since the compound (A) and the alcohol can be hydrogen-bonded, it is easy to accurately weigh the amount of the pure compound (A) when the powder does not contain alcohol or even if it contains a small amount of alcohol. There are advantages. This means that, for example, the "equivalent ratio" when the compound (A) and the epoxy compound are reacted can be accurately controlled, and the physical properties of the finally obtained resin can be easily controlled.

Incidentally, in Patent Document 1, since ethylene glycol is used for purification of BIS-AF, it is considered that BIS-AF described in Patent Document 1 contains ethylene glycol of more than 400 ppm.
On the other hand, when the powder of the first embodiment is produced by the production method (first production method) described later, alcohol may be used as a part of the dispersion medium for dispersing the compound (A). However, in the first production method, the amount of alcohol in the powder is small because the compound (A) is not positively "dissolved" in alcohol. Further, when only water is used as the dispersion medium, the compound (A) does not contain alcohol in principle.

The amount of alcohol in compound (A) can be determined using, for example, a gas chromatograph.

When the volume-based cumulative 50% diameter of the powder of the first embodiment measured by the laser diffraction / scattering method is D ₅₀ , D ₅₀ is preferably 40 to 100 μm, more preferably 40 to 90 μm, and further preferably 40. It is ~ 80 μm.
The powder of the first embodiment _{can be more easily handled when D 50} is within a specific numerical range. It is considered that when D ₅₀ is relatively large, the contact area between the particles becomes smaller and the friction between the particles during flow becomes smaller. And it is considered that it leads to further improvement of filterability and dryness.

In the powder of the first embodiment, when the volume-based cumulative 90% diameter measured by the laser diffraction / scattering method is D ₉₀ , the value of (D _90- D ₅₀ ) / D ₅₀ is preferably 1.3 to 1. It is 1.7, more preferably 1.4 to 1.7.
The index (D _90- D ₅₀ ) / D ₅₀ can be said to be an index indicating the degree of spread of the "hem" on the large particle size side in the particle size distribution curve. When this value is 1.7 or less, it means that the particle size distribution on the large particle size side is relatively sharp. It is considered that the sharp particle size distribution enhances the homogeneity of the powder and further enhances the handleability.
Further, the fact that (D _90- D ₅₀ ) / D ₅₀ is 1.7 or less is considered to mean that the number of coarse particles is relatively small. With a relatively small number of coarse particles, for example, agglomeration may be suppressed.
By the way, _{1.3, which is the lower limit of the preferable range of (D 90-} D ₅₀ ) / D ₅₀ , sets a range in which the cost and labor of recrystallization when obtaining the powder of the compound (A) are not excessive. It was done.

As an index similar to the above, in the powder of the first embodiment, the _{value of (D 90-} D _m ) / D _m is preferably 0.93 or less, more preferably 0.92 or less. The lower limit of the value of (D _90- D _m ) / D _m is, for example, 0.40 or more.

Another aspect, of the powder of the first embodiment, when the average diameter measured by a laser diffraction scattering method was _{D _ave,} _{D ave} is preferably 45 ~ 80 [mu] m, more preferably 45 ~ 60 [mu] m. The powder of the first embodiment tends to have a larger average diameter than the powder of the conventional compound (A) as a major tendency.

In the first embodiment, _{various values related to the particle size such as D m} and D ₅₀ can be obtained from the volume-based particle size distribution curve measured by the laser diffraction / scattering method. As an apparatus capable of measuring by the laser diffraction / scattering method, for example, a particle size distribution meter "SALD" series manufactured by Shimadzu Corporation can be mentioned. The measurement is usually carried out in a wet manner by dispersing the powder in a solvent that is substantially insoluble (for example, n-decane).

(Second Embodiment)
When the volume-based cumulative 50% diameter of the powder of the second embodiment measured by the laser diffraction / scattering method is D ₅₀ and the arithmetic volume average diameter measured by the same method is _Dave , D ₅₀ is 50 to It is 100 μm and D ₅₀ / D _ave is 1.1 to 1.5.

The reason why the handleability of the powder of the second embodiment is good is presumed as follows.
If the particle size of the particles contained in the powder is relatively large, the contact area between the particles is relatively small, and it is presumed that the friction between the particles during flow is small.
In the second embodiment, D ₅₀ is 50 μm or more, that is, 50% or more of relatively large particles having a particle size of 50 μm or more on a volume basis are contained in the powder. It is presumed that the friction is small.
Further, in the second embodiment, the fact that D ₅₀ / D _ave is 1.1 or more means that the shape of the particle size distribution curve in which the frequency is plotted on the vertical axis and the particle size is plotted on the horizontal axis is as shown in FIG. It is not symmetrical (normal distribution), but is biased to the right side (larger particle size side) as shown in FIG. Even with the same D _50, better particle size distribution as shown in FIG. 1, the proportion of relatively large particles in the whole particles are larger, likely smaller the contact area of the particles. Therefore, it is presumed that the friction between the particles during flow is smaller.
It is presumed that these things lead to good handleability.

As another viewpoint, the solvent solubility of the powder of the second embodiment is good. That is, surprisingly, the powder of the present embodiment, despite having a relatively large D _50, soluble relatively quickly in the solvent. The inventors speculate that the reason for this is that the small number of small particle particles in the powder suppresses the swelling and aggregation of BIS-AF in the solvent (swelling). When or agglomeration occurs, the dispersibility of the powder decreases and the dissolution rate is presumed to slow down).

Incidentally, _{the upper limit value of D 50} , 100 μm, is set to a range in which the cost and labor of recrystallization when obtaining the powder of the compound (A) are not excessive. The same applies to 1.5, which is the upper limit of _{D 50} / D _ave.

The method and conditions for producing the powder of the second embodiment are not limited. However, _{in order to obtain a powder of compound (A) having a D 50} of 50 to 100 μm and a D ₅₀ / D _ave of 1.1 to 1.5, it is preferable to select appropriate methods and conditions.
In the present embodiment, for example, when the powder of the compound (A) is obtained by recrystallization, it is preferable to use a specific organic solvent, use a seed crystal, or slowly cool the powder. By selecting an appropriate production method and production conditions, a powder of compound (A) having _{a D 50} of 50 to 100 μm and a D ₅₀ / D _{ave of 1.1 to 1.5 can be obtained.} A specific manufacturing method will be described later as a "second manufacturing method". As a reminder, in producing the powder of the second embodiment, the first production method may be adopted.

As described above, in the powder of the second embodiment, D ₅₀ is 50 to 100 μm, and D ₅₀ / D _ave is 1.1 to 1.5.
D ₅₀ is preferably 50 to 90 μm, more preferably 50 to 80 μm, and even more preferably 50 to 70 μm.
D ₅₀ / D _ave is preferably 1.1 to 1.4, more preferably 1.1 to 1.3.

In the powder of the second embodiment, the fluidity can be further improved by setting the _{mode diameter (mode diameter) D m} measured by the laser diffraction / scattering method within a specific numerical range. It is considered that when D _m is relatively large, the contact area between the particles becomes smaller and the friction between the particles during flow becomes smaller. And it is considered that the handleability is further improved.
As a specific numerical value, D _m is preferably 75 to 150 μm, more preferably 80 to 120 μm.

In the powder of the second embodiment, when the volume-based cumulative 90% diameter measured by the laser diffraction / scattering method is D ₉₀ , the value of (D _90- D ₅₀ ) / D ₅₀ is preferably 1.3 to 1. It is 1.7, more preferably 1.4 to 1.7.
The index (D _90- D ₅₀ ) / D ₅₀ can be said to be an index showing the degree of spread of the "hem" on the right side (large particle size side) in the particle size distribution curve. The fact that (D _90- D ₅₀ ) / D ₅₀ is 1.7 or less means that the particle size distribution on the large particle size side is relatively sharp, and from a different point of view from _{D 50} / D _{ave, the powder} It is considered to mean that the particle size distribution deviates from the normal distribution as shown in FIG. Therefore, _{in addition to the fact that D 50} / D _ave is 1.1 to 1.5, it is considered that the handleability is further improved by the _{fact that (D 90-} D ₅₀ ) / D _{50 is 1.7 or less.} ..
Further, the fact that (D _90- D ₅₀ ) / D ₅₀ is 1.7 or less is considered to mean that the number of coarse particles is relatively small. With a relatively small number of coarse particles, for example, agglomeration may be further suppressed.
By the way, _{1.3, which is the lower limit of the preferable range of (D 90-} D ₅₀ ) / D ₅₀ , sets a range in which the cost and labor of recrystallization when obtaining the powder of the compound (A) are not excessive. It was done.

In the second embodiment, D ₅₀ , D ₉₀ , D _ave and D _m can be obtained from the volume-based particle size distribution curve measured by the laser diffraction / scattering method. As an apparatus capable of measuring by the laser diffraction / scattering method, for example, a particle size distribution meter "SALD" series manufactured by Shimadzu Corporation can be mentioned. The measurement is usually carried out in a wet manner by dispersing the powder in a solvent that is substantially insoluble (for example, n-decane). For details of the measurement method, refer to the examples below.

(Bulk density)
When the bulk density of the powder of the second embodiment is within a certain numerical range, the handleability of the powder can be further improved.
Specifically, the looseness density of the powder of the second embodiment is preferably 0.50 to 0.75 g / cm ³ , and more preferably 0.60 to 0.75 g / cm ³ . The firmness density of the powder of the present embodiment is preferably 0.76 to 0.90 g / cm ³ , and more preferably 0.80 to 0.90 g / cm ³ .
For the method of measuring the loose bulk density and the firm bulk density, refer to the examples below.

(Third Embodiment)
Powder of the third _{embodiment, D 50} is 50 ~ 100 [mu] m. D ₅₀ is preferably 50 to 90 μm, more preferably 50 to 80 μm, and even more preferably 50 to 70 μm.

In the powder of the third embodiment, the fluidity can be further improved by setting the _{mode diameter (mode diameter) D m} measured by the laser diffraction / scattering method within a specific numerical range. It is considered that when D _m is relatively large, the contact area between the particles becomes smaller and the friction between the particles during flow becomes smaller. And it is considered that the handleability is further improved.
As a specific numerical value, D _m is preferably 75 to 150 μm, more preferably 80 to 120 μm.

In the powder of the third embodiment, when the volume-based cumulative 90% diameter measured by the laser diffraction / scattering method is D ₉₀ , the value of (D _90- D ₅₀ ) / D ₅₀ is preferably 1.3 to 1. It is 1.7, more preferably 1.4 to 1.7.
The index (D _90- D ₅₀ ) / D ₅₀ can be said to be an index indicating the degree of spread of the "hem" on the large particle size side in the particle size distribution curve. When this value is 1.7 or less, it means that the particle size distribution on the large particle size side is relatively sharp. It is considered that the sharp particle size distribution enhances the homogeneity of the powder and further enhances the handleability.
Further, the fact that (D _90- D ₅₀ ) / D ₅₀ is 1.7 or less is considered to mean that the number of coarse particles is relatively small. With a relatively small number of coarse particles, for example, agglomeration may be further suppressed.
By the way, _{1.3, which is the lower limit of the preferable range of (D 90-} D ₅₀ ) / D ₅₀ , sets a range in which the cost and labor of recrystallization when obtaining the powder of the compound (A) are not excessive. It was done.

In the third embodiment, D ₅₀ , D ₉₀ and D _m can be obtained from the volume-based particle size distribution curve measured by the laser diffraction / scattering method. As an apparatus capable of measuring by the laser diffraction / scattering method, for example, a particle size distribution meter "SALD" series manufactured by Shimadzu Corporation can be mentioned. The measurement is usually carried out in a wet manner by dispersing the powder in a solvent that is substantially insoluble (for example, n-decane).

As described above, the angle of repose of the powder of the third embodiment is 35 to 49 °. The angle of repose is preferably 40 to 49 °, more preferably 40 to 47 °.
For the method of measuring the angle of repose, refer to the description of the examples below.

By appropriately designing the bulk density of the powder of the third embodiment, the handleability of the powder can be further improved.
_{Specifically, the looseness density ρ 1} of the powder of the third embodiment is preferably 0.50 to 0.75 g / cm ³ , and more preferably 0.60 to 0.75 g / cm ³ . _{The firmness density ρ 2} of the powder of the third embodiment is preferably 0.76 to 0.90 g / cm ³ , and more preferably 0.80 to 0.90 g / cm ³ .
For the method of measuring the loose bulk density and the firm bulk density, refer to the examples below.

In particular, in the third embodiment, ρ ₂ / ρ ₁ is preferably in the range of 1.01 to 1.45, and more preferably in the range of 1.10 to 1.40. When ρ ₂ / ρ ₁ is 1.45 or less, for example, when the powder of the present embodiment is weighed, the fluctuation of the mass to be weighed can be sufficiently reduced.

(Fourth Embodiment)
Powder of the fourth embodiment, 2,2 (In Formula ^(A), all of R 1 ~ ^{R 8} is as a hydrogen atom) bis (4-hydroxyphenyl) hexafluoropropane was in a powder of hand,
The half width of the peak near 2θ = 22.3 ° in the X-ray diffraction (XRD) spectrum is 0.050 ° or more and 0.180 ° or less.
The half width of the peak near 2θ = 23.7 ° in the X-ray diffraction spectrum is 0.050 ° or more and 0.120 ° or less.
It is a powder in which the half width of the peak near 2θ = 25.8 ° in the X-ray diffraction spectrum is 0.040 ° or more and 0.120 ° or less.

Specifically, the powder of the fourth embodiment has advantages such as "fast dissolution rate in a solvent, particularly a polar solvent or an alkaline solvent" and "the drying time when drying a wet powder can be shortened". Has. These advantages are that the half width of the peak near 2θ = 22.3 ° in the X-ray diffraction spectrum is 0.050 ° or more and 0.180 ° or less, and the peak near 2θ = 23.7 ° in the X-ray diffraction spectrum. The half-value width of is 0.050 ° or more and 0.120 ° or less, and the half-value width of the peak near 2θ = 25.8 ° in the X-ray diffraction spectrum is 0.040 ° or more and 0.120 ° or less. It is presumed that this is due to.
The present inventors focused on the full width at half maximum of the peaks at three specific 2θs in the X-ray diffraction spectrum of the powder.
Although the details are unknown, the half width of the peak near 2θ = 22.3 °, which is peculiar to 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and the half width of the peak near 2θ = 23.7 °, By designing the powder so that the half width of the peak near 2θ = 25.8 ° is small, the size of the crystallites of the powder is large and the size of the crystallites is adjusted over the entire powder. It is thought that it was.
As a result, it is considered that the aggregation caused by the variation in the size of the crystallites was suppressed during the dissolution in the solvent, and the dissolution rate in the solvent was increased. In addition, when the wet powder is dried, aggregation due to variation in crystallite size is suppressed, so that aggregation is suppressed.
It is presumed that the liquid component was less likely to exist between the powder particles and the drying time of the powder could be shortened.

The vicinity of 2θ = 22.3 ° in the X-ray diffraction spectrum means a range of ± 1 ° centered on 2θ = 22.3 °, and the vicinity of 2θ = 22.3 ° in the X-ray diffraction spectrum. The peak means the maximum peak within the range of ± 1 ° centered on 2θ = 22.3 °.
The vicinity of 2θ = 23.7 ° in the X-ray diffraction spectrum means a range of ± 1 ° centered on 2θ = 23.7 °, and the vicinity of 2θ = 23.7 ° in the X-ray diffraction spectrum. The peak means the maximum peak within the range of ± 1 ° centered on 2θ = 23.7 °.
The vicinity of 2θ = 25.8 ° in the X-ray diffraction spectrum means a range of ± 1 ° centered on 2θ = 25.8 °, and the vicinity of 2θ = 25.8 ° in the X-ray diffraction spectrum. The peak means the maximum peak within the range of ± 1 ° centered on 2θ = 25.8 °.

The half width of the peak near 2θ = 22.3 ° in the X-ray diffraction spectrum of the powder of 2,2-bis (4-hydroxyphenyl) hexafluoropropane is 0.050 ° or more and 0.180 ° or less.
The half width of the peak near 2θ = 22.3 ° in the X-ray diffraction spectrum is preferably 0.055 ° or more, and more preferably 0.060 ° or more.
Further, it is preferably 0.170 ° or less, and more preferably 0.165 ° or less.

The half width of the peak near 2θ = 23.7 ° in the X-ray diffraction spectrum of the powder of 2,2-bis (4-hydroxyphenyl) hexafluoropropane is 0.050 ° or more and 0.120 ° or less.
The half width of the peak near 2θ = 23.7 ° in the X-ray diffraction spectrum is preferably 0.055 ° or more, and more preferably 0.060 ° or more.
Further, it is preferably 0.100 ° or less, and more preferably 0.090 ° or less.

The half width of the peak near 2θ = 25.8 ° in the X-ray diffraction spectrum of the powder of 2,2-bis (4-hydroxyphenyl) hexafluoropropane is 0.040 ° or more and 0.120 ° or less.
The half width of the peak near 2θ = 25.8 ° in the X-ray diffraction spectrum is preferably 0.045 ° or more, and more preferably 0.050 ° or more.
Further, it is preferably 0.115 ° or less, and more preferably 0.110 ° or less.

The X-ray diffraction (XRD) spectrum of the powder can be measured using an X-ray powder diffractometer (Smart Lab; manufactured by Rigaku Co., Ltd.) using Cu—Kα (λ = 1.5418 Å) irradiation.
After grinding the sample in a mortar, the measurement sample is collected on a non-reflective sample plate (available from Rigaku Co., Ltd.) that does not have a diffraction peak within the measurement range, flattened, and set in the device together with the sample plate for measurement. To do. An example of the measurement conditions is as follows.
[Measurement conditions for X-ray diffraction]
Tube: Cu
Voltage: 40kV
Current: 50mA
Solar slit: 2.5 ° (incident side, light receiving side)
Scan range: 10-80 °
Step width: 0.01 °
Scan speed: 35 ° / min
Detector: 1-dimensional X-ray detector (D / tex Ultra250; manufactured by Rigaku Co., Ltd.)

In the X-ray diffraction spectrum obtained from the measurement, the half widths of the peaks near 2θ = 22.3 °, 23.7 °, and 25.8 ° are calculated, respectively (θ is the Bragg angle). The calculation of the half width of the peak can be performed using Smart Lab Studio II (analysis software: Power XRD).

Since the powder of the fourth embodiment is produced, the method and conditions are not limited. For example, as described in the first production method will be described later, the raw material is melted in an aqueous dispersion medium, a sufficient time at a temperature T ₂ of the subsequent later crystallization step (e.g., more than 30 minutes) while maintaining By crystallization, the half widths of the peaks near 2θ = 22.3 ° and the peaks near 2θ = 23.7 ° and the peaks near 2θ = 25.8 ° in the X-ray diffraction (XRD) spectrum are described above. A powder in the range can be preferably obtained.

The particle size of the powder of the fourth embodiment is not particularly limited, and it is sufficient that the powder has an appropriate handleability. For example, the volume-based cumulative 50% diameter (D ₅₀ ) measured by the laser diffraction / scattering method may be preferably 20 to 100 μm. Further, the lower limit may be more preferably 30 μm or more, further preferably 40 μm or more, and the upper limit may be more preferably 90 μm or less, further preferably 80 μm or less.
As an apparatus capable of measuring by the laser diffraction / scattering method, for example, a particle size distribution meter "SALD" series manufactured by Shimadzu Corporation can be mentioned. The measurement is usually carried out in a wet manner by dispersing the powder in a solvent that is substantially insoluble (for example, n-decane).

<Powder manufacturing method>
The powders of the first to fourth embodiments can be produced through an appropriate production method. In the following, two preferable production methods (first production method and second production method) for producing the powders of the first to fourth embodiments will be described.

(1st manufacturing method)
The method for producing a powder of a compound represented by the general formula (A) (first production method) is, for example,
-By putting the raw material containing the compound represented by the general formula (A) and the aqueous dispersion medium in a container and heating the raw material, the raw material is melted in the presence of the aqueous dispersion medium, and the melted product of the raw material is obtained. A melting step to obtain a heterogeneous liquid containing an aqueous dispersion medium,
・ Crystallization process to obtain crystals by crystallizing the melt by lowering the temperature of the non-uniform liquid,
Can be included.
In the melting step of the first production method, at the melting temperature _{T 1} of the raw material, the aqueous dispersion medium, the solubility of the compound represented by the general formula (A), 10 [g / 100g] or less, preferably 8 [g / 100 g] or less. The lower limit of this solubility may be zero, but the solubility is usually 0.5 [g / 100 g] or more.
"Melting temperature T _{1 of} raw material" means the lowest temperature at which all powdered (solid) raw material melts and loses its original form. The fact that all the raw material has melted is (i) a method of visually observing the state of the raw material in the container and confirming that no powdery (solid) raw material is found, (ii) from inside the container. It can be confirmed by a method of quickly visually observing the extracted aqueous layer and confirming that the raw material does not remain in the powder form (solid form).

The first manufacturing method can also be described as follows.
-In the melting step, the raw material containing the compound (A) is heated in an aqueous dispersion medium and melted (not melted) at _{a temperature T 1 to obtain a melt.} Aqueous dispersion medium, Briefly, a compound at the temperature T ₁ (A) "poor solvent" in the (unlikely liquid by dissolving the compound (A)). By heating the compound (A) in a poor solvent (aqueous) of the compound (A), a heterogeneous liquid containing a melt of the raw material and an aqueous dispersion medium can be obtained.
-In the crystallization step, the melt in the non-uniform liquid is crystallized.

In the first production method, it is considered that the amount of Ca ions and the like can be reduced by moving Ca ions and the like from the raw material material side to the aqueous dispersion liquid side at the interface between the melt of the raw material and the aqueous dispersion. This is preferable from the viewpoint of producing the powder of the first embodiment (less Ca ions).

Further, in the first production method, since the raw material is not positively "dissolved" (it does not go through a state in which the solute and the solvent are completely and uniformly mixed), Ca ions and the like, which are impurities derived from the solvent such as water, etc. However, it is considered that the raw material is suppressed from being incorporated into the recrystallized substance. Similarly, it is considered that Ca ions and the like, which are impurities once dissolved from the raw material, are suppressed from being "re-incorporated" into the crystallized raw material. These are also considered to be related to the fact that the amount of impurities such as Ca ions can be reduced.

By the way, for example, BIS-AF by itself does not melt when heated to 100 ° C. (boiling point of water), but BIS-AF in water melts when heated to 100 ° C. (or lower temperature). This is because, according to publicly known information and the findings of the present inventors, the melting point of BIS-AF is lowered by hydration. For known information, refer to, for example, the above-mentioned Patent Document 3.

The first manufacturing method also has the additional advantage of having a small environmental load. Specifically, in carrying out the first production method, an aqueous dispersion is mainly used, and an organic solvent (a good solvent of compound (A)) is unnecessary. That is, by adopting the above manufacturing method, the use of organic solvent can be reduced, so that the environmental load can be reduced.

Hereinafter, the melting process and the crystallization process will be described in more detail.

-Melting step Normally, in the melting step, the raw material containing the compound (A) and the aqueous dispersion medium are heated in a container equipped with a stirring means and a heating means. By doing so, a heterogeneous liquid containing a melt of the raw material and an aqueous dispersion medium can be obtained. By heating with stirring, the non-uniform liquid usually becomes a suspended liquid. When agitated or stopped and allowed to stand, the non-uniform liquid is usually in a two-layer separated state. By the way, it is considered that by heating while stirring, the melt of the raw material and the aqueous dispersion medium are in sufficient contact with each other, and Ca ions and the like are more easily moved from the raw material side to the aqueous dispersion side.

As an example, the aqueous dispersion can contain substantially only water. By using an aqueous dispersion containing substantially only water, the amount of alcohol in the finally obtained compound (A) can be made substantially zero. Further, since the solubility of the compound (A) in water is very small, there is an advantage that the amount of the compound (A) contained in the waste liquid can be reduced.

As another example, the aqueous dispersion can include water and alcohol. In this case, the ratio of alcohol in the aqueous dispersion medium is usually 30% by mass or less, preferably 1 to 30% by mass, and more preferably 5 to 25% by mass. If the proportion of alcohol is too high, the raw material may not be properly dispersed in the aqueous dispersion and many may "dissolve". Therefore, the ratio of alcohol in the aqueous dispersion is preferably about the above.
By using a liquid containing water and alcohol as the aqueous dispersion, there is an advantage that the _{temperature T 1 can be lowered.} According to the findings of the present inventors, when only water is used as the aqueous dispersion, T ₁ becomes 90 ° C. or higher, but since the aqueous dispersion contains 30% by mass or less of alcohol, T ₁ is higher than 90 ° C. It tends to be low (about 30 to 90 ° C). When T ₁ is lowered, delicate temperature adjustment becomes easy, and for example, crystal growth may be facilitated in a later crystallization step.

Regarding the ratio of the raw material to the aqueous dispersion, the effect of reducing impurities such as Ca ions (the more the aqueous dispersion is used, the easier it is for Ca ions in the raw material to move to the water-based dispersion) and the cost. It may be set appropriately from the balance of. The amount of the aqueous dispersion with respect to 100 parts by mass of the raw material is usually 100 to 3000 parts by mass, preferably 200 to 1500 parts by mass.

The temperature T ₁ varies depending on the specific structure of the compound (A) and the composition of the aqueous dispersion. The heating temperature and time required in the melting step may be appropriately set accordingly. In the melting step, the total amount of the compound (A) excluding the portion dissolved in the aqueous dispersion may be melted.

-Crystallization step In the crystallization step, the temperature of the non-uniform liquid obtained in the melting step is lowered to crystallize the melt in the non-uniform liquid. A compound in which Ca ions and the like are small and the particle size distribution is appropriately controlled (for example, D _m is 75 to 150 μm as in the first embodiment) by appropriately selecting specific conditions for lowering the temperature. The powder of (A) can be obtained. Further, by appropriately selecting the specific conditions for lowering the temperature, the powder of the compound (A) having a relatively small half-value width of the XRD spectrum can be obtained, probably because the size of the crystallite is controlled.

The crystallization step in the first process is different from the general crystallization step, that is, the crystallization of a substance dissolved in a uniform "solution".
In a general crystallization step, it is necessary to gradually lower the temperature of the solution as the crystals precipitate.
On the other hand, in the crystallization step in the first production method, the temperature of the non-uniform liquid may be lowered to a certain temperature or less (less than the melting temperature), and the temperature does not necessarily have to be "gradually lowered". Most of compound (A) is not "melted" but simply "melted", so as long as the temperature is kept below a certain temperature (less than the melting temperature), compound (A) Most of them crystallize (solidify). Due to such an unusual crystallization mechanism, the obtained crystal (final product) is different from the conventional product.
However, for example, when the aqueous dispersion medium contains alcohol, a certain amount of the compound (A) is "dissolved" in the dispersion medium, so that the temperature lowering operation may be performed at an appropriate rate. Further, in the crystallization step, the temperature may be lowered after the temperature is maintained at a constant temperature lower than the melting temperature.

The temperature T _{2 in the} crystallization step is preferably 1 to 10 ° C. lower than the temperature T _{1 and more preferably 1 to 8 ° C. lower.} Specifically, in the crystallization step, the system may be maintained at the above temperature T ₂ (within a range of 1 to 10 ° C. lower than the temperature T ₁ ), preferably for 30 minutes or longer, more preferably 60 minutes or longer. preferable. By maintaining the temperature T ₂ for a sufficiently long time, Ca ions and the like were sufficiently reduced, and the particle size distribution was appropriately controlled (for example, D _m is 75 to 150 μm as in the first embodiment). Easy to obtain crystals. On the other hand, from the viewpoint of production efficiency, the _{time for maintaining the temperature T 2} in the crystallization step is preferably, for example, 300 minutes or less.

The crystallization step is preferably carried out while stirring the non-uniform liquid. When stirring is performed in the melting step, it is preferable to continue stirring as it is. By doing so, it is easy to sufficiently reduce the amount of impurities such as Ca ions. Further, by constantly stirring the dispersion liquid, the crystal growth is appropriately controlled and the particle size distribution is appropriately controlled (for example, D _m is 75 to 150 μm as in the first embodiment). Easy to get. The above stirring is preferably performed at a speed of 50 to 500 rpm, and more preferably at a speed of 150 to 300 rpm.

In the crystallization step, seed crystals may or may not be used. When a seed crystal is used, the amount of the seed crystal added can be about 1/1000 to 1/100 of the compound (A) dispersed in the aqueous dispersion medium in terms of mass ratio. The seed crystal is not particularly limited as long as it is a solid compound (A).

-Treatment after the crystallization step After the crystallization step, the system is usually cooled to room temperature (about 25 ° C.).
The cooling conditions are not particularly limited. It may or may not be naturally cooled. As described above, since this embodiment is different from the prior art of crystallizing the "dissolved" compound (A), a large amount of the compound (A) is not precipitated by cooling.
However, since the aqueous dispersion medium dissolves a small amount of the compound (A), some crystals are precipitated by cooling. From the viewpoint of precise adjustment of the amount of Ca ions and the like and the particle size distribution, it is preferable that the cooling is gently performed at about 0.1 to 0.3 [° C./min].

After cooling, the obtained crystals can be recovered by, for example, vacuum filtration, washed with water, and dried under reduced pressure in an environment of about 20 to 50 ° C. to obtain the final powder.

(2nd manufacturing method)
The method for producing a powder of a compound represented by the general formula (A) (second production method) includes, for example, a series of procedures such as the following steps 1 to 4. By such a procedure, the particle size distribution was appropriately controlled (for example, D ₅₀ is 50 to 100 μm and D ₅₀ / D _ave is 1.1 to 1.5 as in the second embodiment). A powder of compound (A) can be obtained.

-Step 1: Preparation of raw material First, as a raw material, a substance containing a chemical structure represented by the general formula (A) is prepared. Such a raw material can be obtained, for example, by the method described in Patent Document 2 described above. Commercially available products may be used as raw materials.

-Step 2: Dissolution in organic solvent (heating, etc.)
The raw material prepared in step 1 is put into an organic solvent. Then, the organic solvent is heated with stirring to dissolve the raw material in the organic solvent.

At this time, it is important to select an appropriate organic solvent. Specifically, as the organic solvent, it is preferable to use a mixed solvent containing the poor solvent and the good solvent of the compound (A). As a result, in the subsequent (3) recrystallization, the crystals tend to grow slowly, and the particle size distribution is appropriately controlled (for example, as in the second embodiment, D ₅₀ and D ₅₀ / D _ave). Easy to obtain (properly controlled) powder.

Examples of the poor solvent include alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and ethylcyclohexane, and n-pentane, n-hexane, isohexane, n-heptane, n-octane, isooctane, n-decane and the like. An aliphatic hydrocarbon solvent can be mentioned.
Examples of good solvents include ester solvents such as methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, methyl lactate, ethyl lactate, and butyl lactate.
The mixing ratio of the poor solvent and the good solvent is a mass ratio, for example, poor solvent / good solvent = 99/1 to 50/50, preferably poor solvent / good solvent = 95/5 to 75/25, and more preferably poor solvent. / Good solvent = 95/5 to 80/20.

In step 2, the organic solvent is heated to, for example, about 60 to 80 ° C. This heating and stirring completely dissolves the raw material in the organic solvent. In other words, the amount of the raw material added to the organic solvent is adjusted so that the organic solvent is completely dissolved when heated to about 60 to 80 ° C., but precipitation occurs in step 3 (lowering temperature) described later. This amount may be appropriately set based on the solubility of the raw material, the organic solvent used, the heating temperature, and the like.
Although it is only an example, the amount of the raw material used (the amount input to the organic solvent) can be about 100 g per 1000 g of the organic solvent.

-Step 3: Temperature lowering / addition of seed crystals / stirring In step 2, the organic solvent heated to about 60 to 80 ° C. and completely dissolved in the raw material was slowly brought to about 55 ° C. over about 30 minutes to 3 hours. To cool down.

After the temperature is lowered, the solid compound (A) is added to the organic solvent as a seed crystal. As the findings of the present inventors, in particular, when the above-mentioned poor solvent and good solvent are used as the organic solvent, the particle size distribution is finally appropriately controlled by using the seed crystal (for example, the second). It is easy to obtain the powder of the compound (A) in which D ₅₀ and D ₅₀ / D _{ave are controlled as in the embodiment.}
The amount of the seed crystal added can be about 1/1000 to 1/100 of the raw material dissolved in the organic solvent in the step 2 in terms of mass ratio. The seed crystal is not particularly limited as long as it is a solid compound (A). For example, a seed crystal obtained according to the method described in Examples of Patent Document 2 described above can be used. Further, a commercially available solid compound (A) can also be used as a seed crystal.

After adding the seed crystal, the organic solvent is stirred for about 30 minutes to 3 hours while maintaining the temperature of about 55 ° C. to precipitate the crystal.

-Step 4: Cooling After the step 3, the organic solvent is slowly cooled to about 30 to 40 ° C. for about 1 to 5 hours while stirring. This causes the crystals to grow.
The obtained crystals are collected by vacuum filtration and dried under reduced pressure in an environment of about 20 to 50 ° C. By doing so, it is possible to obtain a powder having an appropriately controlled particle size distribution and the like.

<Method of manufacturing solution>
A solution containing the compound represented by the general formula (A) can be produced by using the solvent and at least one of the powders of the first to fourth embodiments. By using this solution, various low molecular weight compounds, oligomers, polymers and the like can be produced.

In producing the solution, (i) at least one of the powders of the first to fourth embodiments may be added as it is to the solvent, and the mixture may be stirred or dissolved. (Ii) First, the first to fourth embodiments may be added. At least one of the powders of the embodiment may be finely divided to obtain a finely divided powder, and at least the finely divided powder may be added to a solvent and stirred or dissolved.
As described above, the industrial handleability of the powders of the first to fourth embodiments is good. For example, in the first embodiment, when the mode diameter D _m is 75 to 150 μm, there are advantages such as “good filterability” and “the drying time when drying the wet powder can be shortened”. .. On the other hand, when the mode diameter D _m is relatively large, 75 to 150 μm, there is a concern that it may take some time to dissolve depending on the type of solvent. Therefore, it may be preferable to produce the solution as described in (ii) above.

The method of "miniaturization" is not particularly limited. A typical miniaturization method is pulverization. Industrially, pulverization can be performed using devices such as jet mills, roller mills, hammer mills, pin mills, rotary mills, vibration mills, planetary mills, and bead mills.
As another method of miniaturization, at least one of the powders of the first to fourth embodiments is put into a solvent, and the undissolved powder is taken out (for example, by filtration) before being completely dissolved to be finely divided. Powder may be obtained.
As yet another method for micronization, at least one of the powders of the first to fourth embodiments is put into a solvent in an amount that does not dissolve the entire amount of the powder, and after the dissolution of the powder is saturated, it is not dissolved. Fine powder may be obtained by taking out the powder of. Alternatively, the solution containing the undissolved powder may be used as it is.

When miniaturization is performed, the degree of miniaturization is not particularly limited. The degree of miniaturization may be determined by balancing the cost required for miniaturization with the merit of performing miniaturization (for example, the above-mentioned improvement in solubility). _{From one viewpoint, the Dave} may be 1/20 to 1/2, more preferably 1/15 to 1/4 before and after miniaturization (preferably pulverization). In terms of absolute value of D _ave, _{D ave} of the powder after fine (preferably crushed) is preferably 0.1 ~ 15 [mu] m, and more preferably may be such that the 0.5 ~ 10 [mu] m.

The solvent that can be used in producing the solution of compound (A) can be appropriately selected according to various purposes. The solvent that can be used is not particularly limited as long as the compound (A) is dissolved. Specifically, amide-based solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformamide, hexamethylphosphate triamide, and N-methyl-2-pyrrolidone, methanol, ethanol, and 1-propanol. , 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol and other alcohol solvents, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether , Diphenyl ether, dimethoxyethane, diethoxyethane, tetrahydrofuran, dioxane 1-methoxy-2-propanol and other ether solvents, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, propylene glycol monomethyl acetate, ethyl lactate and other ester solvents. , Niterite solvents such as acetonitrile, propanenitrile, benzonitrile, aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, cumene, dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2- Examples thereof include halogen-based solvents such as tetrachloroethane, and lactone-based solvents such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, and ε-caprolactone. The solvent may be used alone or in combination of two or more.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the range in which the object of the present invention can be achieved are included in the present invention.

Embodiments of the present invention will be described in detail based on Examples and Comparative Examples. As a reminder, the invention is not limited to examples.

[Examples 1 to 5 and Comparative Examples 1 to 6]
The following Examples 1 to 5 and Comparative Examples 1 to 6 are, in particular, Examples and Comparative Examples for explaining the first embodiment in detail.

<Example 1>
25.0 g (74.4 mmol) of BIS-AF powder manufactured by Central Glass Co., Ltd. was collected from a reagent bottle and placed in a glass container made of borosilicate glass having a volume of 500 mL equipped with a stirrer and a cooling condenser. Then, 225.0 g of pure water was added into the container. Then, the temperature inside the container was raised to 95 ° C. while stirring.
While the temperature was being raised, the BIS-AF powder began to melt, and the inside of the container became suspended. The temperature was maintained at 95 ° C. and the mixture was stirred for 1 hour.

After 1 hour, the stirring was stopped and the container was allowed to stand, and the inside of the container was observed. As a result of observation, it was confirmed that the two phases of the aqueous layer and the melt of BIS-AF were separated (not completely mixed) in the container. In addition, unmelted BIS-AF was not confirmed.
At this time, the BIS-AF concentration on the aqueous layer side was measured. The concentration was about 1% by mass, and most of BIS-AF was not "dissolved" in water even at a high temperature of about 95 ° C. That is, at the melting temperature of the raw material BIS-AF powder, the solubility of the aqueous dispersion medium BIS-AF was far below 10 [g / 100 g].

Next, the internal temperature was slightly lowered from 95 ° C., and the mixture was stirred for 1 hour while maintaining the temperature of 92 to 94 ° C. Then, crystals were precipitated. Then, the internal temperature was cooled to room temperature at a temperature lowering rate of 15 ° C./1 hour. The room temperature at this time was about 25 ° C.
After cooling, the precipitated BIS-AF was separated and recovered by vacuum filtration using a suction filter equipped with a filter paper. After recovery, it was washed with 75 mL of pure water. The washed BIS-AF was dried at 75 ° C. under reduced pressure (1 kPa or less) for 8 hours using a vacuum dryer.

The BIS-AF powder obtained after drying was 24.1 g, and the yield was 96%.

<Example 2>
25.0 g (74.4 mmol) of BIS-AF powder was collected from the same reagent bottle as in Example 1 and placed in a glass container made of borosilicate glass having a volume of 500 mL and equipped with a stirrer and a cooling condenser. Next, 202.5 g of pure water and 22.5 g of methanol were added into the container, and the temperature inside the container was raised to 66 ° C. with stirring.
While the temperature was being raised, the BIS-AF powder began to melt and the inside of the container became suspended. The temperature was maintained as it was, and the mixture was stirred for 1.5 hours.

After 1.5 hours, the stirring was stopped and the container was allowed to stand, and the inside of the container was observed. As a result of observation, it was confirmed that the two phases of the aqueous layer and the melt of BIS-AF were separated (not completely mixed) in the container. In addition, unmelted BIS-AF was not confirmed.
At this time, the BIS-AF concentration on the aqueous layer side was measured. The concentration was 2% by mass or less, and most of BIS-AF was not "dissolved" in water / methanol even at a high temperature of about 66 ° C. That is, at the temperature at which the raw material BIS-AF powder was completely "melted", the solubility of the aqueous dispersion medium BIS-AF was well below 10 [g / 100 g].

Next, the mixture was stirred for 1 hour while maintaining an internal temperature of 60 to 65 ° C. Then, crystals were precipitated. Then, the internal temperature was cooled to room temperature at a temperature lowering rate of 15 ° C./1 hour. The room temperature at this time was about 25 ° C.
After cooling, the precipitated BIS-AF was separated and recovered by vacuum filtration using a suction filter equipped with a filter paper. After recovery, it was washed with 75 mL of pure water. The washed BIS-AF was dried at 80 ° C. under reduced pressure (1 kPa or less) for 6 hours using a vacuum dryer.
The BIS-AF powder obtained after drying was 22.9 g, and the yield was 92%.

<Example 3>
25.0 g (74.4 mmol) of BIS-AF powder was collected from the same reagent bottle as in Example 1 and placed in a glass container made of borosilicate glass having a volume of 500 mL and equipped with a stirrer and a cooling condenser. Next, 112.5 g of pure water and 12.5 g of methanol were added into the container, and the temperature inside the container was raised to 66 ° C. with stirring.
While the temperature was being raised, the BIS-AF powder began to melt and the inside of the container became suspended. The temperature was maintained as it was, and the mixture was stirred for 2 hours.

After 2 hours, the stirring was stopped and the container was allowed to stand, and the inside of the container was observed. As a result of observation, it was confirmed that the two phases of the aqueous layer and the melt of BIS-AF were separated (not completely mixed) in the container. In addition, unmelted BIS-AF was not confirmed.
At this time, the BIS-AF concentration on the aqueous layer side was measured. The concentration was 2% by mass or less, and most of BIS-AF was not "dissolved" in water / methanol even at a high temperature of about 66 ° C. That is, at the temperature at which the raw material BIS-AF powder was completely "melted", the solubility of the aqueous dispersion medium BIS-AF was well below 10 [g / 100 g].

Next, the mixture was stirred for 1 hour while maintaining an internal temperature of 59 to 65 ° C. Then, crystals were precipitated. Then, the internal temperature was cooled to room temperature at a temperature lowering rate of 15 ° C./1 hour. The room temperature at this time was about 25 ° C.
After cooling, the precipitated BIS-AF was separated and recovered by vacuum filtration using a suction filter equipped with a filter paper. After recovery, it was washed with 75 mL of pure water. The washed BIS-AF was dried at 80 ° C. under reduced pressure (1 kPa or less) for 6 hours using a vacuum dryer.
The BIS-AF powder obtained after drying was 23.4 g, and the yield was 94%.

<Example 4>
25.0 g (74.4 mmol) of BIS-AF powder was collected from the same reagent bottle as in Example 1 and placed in a glass container made of borosilicate glass having a volume of 500 mL and equipped with a stirrer and a cooling condenser. Next, 100.0 g of pure water and 25.0 g of methanol were added into the container, and the temperature inside the container was raised to 40 ° C. with stirring.
While the temperature was being raised, the BIS-AF powder began to melt and the inside of the container became suspended. The temperature was maintained as it was, and the mixture was stirred for 2 hours.

After 2 hours, the stirring was stopped and the container was allowed to stand, and the inside of the container was observed. As a result of observation, it was confirmed that the two phases of the aqueous layer and the melt of BIS-AF were separated (not completely mixed) in the container. In addition, unmelted BIS-AF was not confirmed.
At this time, the BIS-AF concentration on the aqueous layer side was measured. The concentration was 2% by mass or less, and most of BIS-AF was not "dissolved" in water / methanol even at a temperature of about 40 ° C. That is, at the temperature at which the raw material BIS-AF powder was completely "melted", the solubility of the aqueous dispersion medium BIS-AF was well below 10 [g / 100 g].

Next, the mixture was stirred for 1 hour while maintaining an internal temperature of 34 to 39 ° C. Then, crystals were precipitated. Then, the internal temperature was cooled to room temperature at a temperature lowering rate of 10 ° C./1 hour. The room temperature at this time was about 25 ° C.
After cooling, the precipitated BIS-AF was separated and recovered by vacuum filtration using a suction filter equipped with a filter paper. After recovery, it was washed with 75 mL of pure water. The washed BIS-AF was dried at 80 ° C. under reduced pressure (1 kPa or less) for 6 hours using a vacuum dryer.
The BIS-AF powder obtained after drying was 23.0 g, and the yield was 92%.

<Example 5>
100.0 g (298 mmol) of BIS-AF powder manufactured by Central Glass Co., Ltd. was collected from a reagent bottle and placed in a glass container made of borosilicate glass having a volume of 2000 mL equipped with a stirrer and a cooling condenser. Then, 425.0 g of pure water and 75.0 g of methanol were added into the container. Then, the temperature inside the container was raised to 55 ° C. while stirring.
While the temperature was being raised, the BIS-AF powder began to melt, and the inside of the container became suspended. The temperature was maintained at 55 ° C. and the mixture was stirred for 1 hour.

After 1 hour, the stirring was stopped and the container was allowed to stand, and the inside of the container was observed. As a result of observation, it was confirmed that the two phases of the aqueous layer and the melt of BIS-AF were separated (not completely mixed) in the container. In addition, unmelted BIS-AF was not confirmed.
At this time, the BIS-AF concentration on the aqueous layer side was measured. The concentration was about 1% by mass, and most of BIS-AF was not "dissolved" in water. That is, at the melting temperature of the raw material BIS-AF powder, the solubility of the aqueous dispersion medium BIS-AF was far below 10 [g / 100 g].

Next, the internal temperature was slightly lowered from 55 ° C., and the mixture was stirred for 1 hour while maintaining the temperature of 49-50 ° C. Then, crystals were precipitated. Then, the internal temperature was cooled to room temperature at a temperature lowering rate of 15 ° C./1 hour. The room temperature at this time was about 25 ° C.
After cooling, the precipitated BIS-AF was separated and recovered by vacuum filtration using a suction filter equipped with a filter paper. After recovery, it was washed with 300 mL of pure water. The washed BIS-AF was dried at 75 ° C. under reduced pressure (1 kPa or less) for 8 hours using a vacuum dryer.

The BIS-AF powder obtained after drying was 95.1 g, and the yield was 95%.

<Comparative example 1>
Comparative Example 1 is an example in which an attempt is made to reduce Ca ions by simple washing with water.

25.0 g (74.4 mmol) of BIS-AF powder was collected from the same reagent bottle as in Example 1 and placed in a glass container made of borosilicate glass having a volume of 300 mL equipped with a stirrer. Next, 125.0 g of pure water was added, and the BIS-AF powder was washed while stirring at room temperature (about 20 ° C.) for 1 hour.
After the washing was completed, the mixture was separated and collected by vacuum filtration using a suction filter equipped with a filter paper.
Then, using a vacuum dryer, it was dried at 80 ° C. under reduced pressure (1 kPa or less) for 6 hours.
The BIS-AF powder obtained after drying was 24.0 g, and the yield was 96%.

<Comparative example 2>
Comparative Example 2 is an example in which the reduction of Ca ions by reprecipitation, which is often attempted to reduce the amount of metal in the crystalline compound, is attempted.

200.0 g of pure water was placed in a glass container made of borosilicate glass having a volume of 300 mL and equipped with a stirrer.
Next, a borosilicate glass container containing the pure water in a solution prepared by dissolving 25.0 g (74.4 mmol) of BIS-AF powder collected from the same reagent bottle as in Example 1 in 50.0 g of methanol. Gradually dropped into the inside while turning the stirrer. As a result, a solid BIS-AF was precipitated.
The precipitated BIS-AF was collected by vacuum filtration using a suction filter equipped with a filter paper. Then, using a vacuum dryer, it was dried at 80 ° C. under reduced pressure (1 kPa or less) for 8 hours.
The BIS-AF powder obtained after drying was 23.2 g, and the yield was 93%.

<Comparative example 3>
Comparative Example 3 is an example in which an attempt was made to reduce Ca ions using activated carbon with reference to the description in Patent Document (CN104528717A).

25.0 g (74.4 mmol) of BIS-AF powder was collected from the same reagent bottle as in Example 1 and placed in a glass container made of borosilicate glass having a volume of 300 mL equipped with a stirrer. Next, 50.0 g of methanol and 2.0 g of activated carbon (manufactured by Osaka Gas Chemical Co., Ltd., trade name Shirasagi ANOX-1) were added to the container, and the mixture was stirred at room temperature (about 20 ° C.) for 5 hours.
After the stirring was completed, the activated carbon was removed by filtration using a suction filter equipped with a filter paper, and the methanol solution of BIS-AF was recovered. When the metal ion concentration of the methanol solution was measured, Na ion was 9 ppm and Ca ion was 12 ppm.
Then, BIS-AF was reprecipitated by gradually dropping this methanol solution into 200 g of pure water. After precipitation of BIS-AF, BIS-AF was recovered by vacuum filtration using a suction filter equipped with a filter paper. Then, using a vacuum dryer, it was dried at 80 ° C. under reduced pressure (1 kPa or less) for 8 hours.
The BIS-AF powder obtained after drying was 21.9 g, and the yield was 88%.

<Comparative example 4>
Comparative Example 4 is an example in which the activated carbon is replaced with an ion exchange resin in Comparative Example 3.

25.0 g (74.4 mmol) of BIS-AF powder was collected from the same reagent bottle as in Example 1 and placed in a glass container made of borosilicate glass having a volume of 300 mL equipped with a stirrer. Next, 50.0 g of methanol and 2.0 g of an ion exchange resin (manufactured by Sumika Chemtex Co., Ltd., trade name, Duolite C255LFH) were added to the container, and the mixture was stirred at room temperature (about 20 ° C.) for 5 hours.
After the stirring was completed, the ion exchange resin was removed by filtration using a suction filter equipped with a filter paper, and the methanol solution of BIS-AF was recovered. When the metal ion concentration of the methanol solution was measured, Na ion was 3 ppm and Ca ion was 2 ppm.
Then, BIS-AF was reprecipitated by gradually dropping this methanol solution into 200 g of pure water. After precipitation of BIS-AF, BIS-AF was recovered by vacuum filtration using a suction filter equipped with a filter paper. Then, using a vacuum dryer, it was dried at 80 ° C. under reduced pressure (1 kPa or less) for 7 hours.
The BIS-AF powder obtained after drying was 22.2 g, and the yield was 89%.

<Comparative example 5>
Comparative Example 5 is an example in which activated carbon was replaced with activated clay in Comparative Example 3.

25.0 g (74.4 mmol) of BIS-AF powder was collected from the same reagent bottle as in Example 1 and placed in a glass container made of borosilicate glass having a volume of 300 mL equipped with a stirrer. Next, 50.0 g of methanol and 2.0 g of activated clay (manufactured by Mizusawa Industrial Chemicals, Inc., trade name, galleon earth) were added to the container, and the mixture was stirred at room temperature (about 20 ° C.) for 5 hours.
After the stirring was completed, the active clay was removed by filtration using a suction filter equipped with a filter paper, and the methanol solution of BIS-AF was recovered. When the metal ion concentration of the methanol solution was measured, Na ion was 18 ppm and Ca ion was 4 ppm.
(Since the metal concentration in this methanol solution was clearly higher than that of Comparative Example 4, it was presumed that the metal could not be removed even if the subsequent reprecipitation was performed, and the reprecipitation was not performed.)

<Comparative Example 6>
Comparative Example 6 is an example referring to the matters described in Japanese Patent Application Laid-Open No. 2007-246819.
In Comparative Example 6, a mixed solvent of water and alcohol (ethylene glycol) is used. However, in a series of flows, the raw material BIS-AF powder was completely dissolved in the mixed solvent (became a uniform single layer), and Comparative Example 6 was essentially different from the present embodiment. different.

150 g of BIS-AF powder was put into a 2 L volume borosilicate glass container equipped with a stirrer and a cooling condenser from the same reagent bottle as in Example 1, and 300 g of ethylene glycol and 700 g of ion-exchanged water were poured into the container. .. Then, using an oil bath, BIS-AF was dissolved while heating and stirring until the internal temperature of the flask reached 85 ° C. The temperature was maintained as it was, and the mixture was stirred for 1 hour. After 1 hour, the stirring was stopped and the container was allowed to stand, and the inside of the container was observed. Then, a uniform solution was confirmed.

Next, while continuing stirring, the flask was cooled at a temperature lowering rate of 10 ° C./hour until the internal temperature of the flask reached 25 ° C. Then, the crystals began to gradually precipitate (recrystallize) at the same time as the temperature lowering started. The precipitated crystals were collected by filtration under reduced pressure (1 kPa or less) and dried under reduced pressure at 60 ° C.
The BIS-AF powder obtained after drying was 137.0 g, and the yield was 91%. The concentration of Na ions was 0.2 ppm, and the concentration of Ca ions was 0.3 ppm.

<Measurement>
(Diameter distribution)
Using SALD-2200, a particle size distribution meter manufactured by Shimadzu Corporation, the particle size distribution of the obtained powder BIS-AF dispersed in an n-decane solvent was measured. At the time of measurement, BIS-AF and n-decane solvent were mixed in advance on a slide glass to prepare a paste-like BIS-AF. Then, paste-like BIS-AF is gradually added to n-decane, which is a dispersion solvent, and the amount of addition is adjusted so that the absorbance value is 0.1 L / (mol · cm) or less, and the particle size distribution is distributed. Was measured.
By analyzing the obtained measurement results (particle size distribution), D _{m and the} like were calculated.

(Content of Ca, Na and Mg ions)
The contents of Ca, Na and Mg ions in the powder were determined by using an ion chromatography analysis method. The details of the analysis method are as follows.

First, 0.4 g of each BIA-AF powder obtained in Example / Comparative Example was dissolved in 2.0 mL of t-butyl methyl ether to prepare a solution. This solution and 2.0 mL of ultrapure water were placed in a separatory funnel, and the separatory funnel was vigorously shaken to extract a metal ion component on the ultrapure water (aqueous layer) side. The separating funnel was allowed to stand, and the side of the separated aqueous layer was used as an analytical sample solution for analysis of metal ion components.
The metal ion content of this analytical sample solution was measured using an ion chromatography device (CS-2100) manufactured by Thermo Fisher Scientific. As the columns, a separation column (Ion Pac CS16 (inner diameter 4 mm × 250 mm)) and a guard column (Ion Pac CG16 (inner diameter 4 mm × 100 mm)) were used. As the eluent, 30 mM methanesulfonic acid was used, the eluent flow rate was 1.0 mL / min, and the temperature was 35 ° C.

Information on the particle size distribution and the content of Ca, Na and Mg ions is summarized in the table below. Incidentally, in some comparative examples, the particle size distribution was not measured because the content of metal ions was clearly large (indicated by N.D. in the table).

(Alcohol content)
In Example 2, 1.00 g of dried BIS-AF was dissolved in 1.00 g of ethyl acetate, and gas chromatography analysis was performed. The methanol content was less than 100 ppm based on the peak area excluding ethyl acetate.
In Comparative Example 6, 1.00 g of BIS-AF after drying was dissolved in 1.00 g of ethyl acetate, and gas chromatography analysis was performed. The ethylene glycol content was 500 ppm based on the peak area excluding ethyl acetate.

<Evaluation>
The dispersion liquid in which the BIS-AF powder was dispersed in water was passed through a suction filter equipped with a filter paper to separate the powder and water. The good filterability (drainage) at this time was evaluated as follows.
-Good: After the start of decompression, the dripping from the filter (funnel foot) disappears quickly.
・ Bad: After decompression starts, dripping from the filter (funnel foot) continues for a while.

In addition, the water content of the powder after suction filtration until the dripping from the filter (funnel foot) disappeared was measured by the Karl Fischer method.

The evaluation results are summarized in the table below. Incidentally, as described above, since reprecipitation was not performed in Comparative Example 5, there was no evaluation result of liquid drainage or water content (ND = No Data).

As shown in Table 2, the filterability of the BIS-AF powders of Examples 1 to 5 was good. Further, from the evaluation results of the water content, it was found that the drying time when drying the BIS-AF powders of Examples 1 to 5 was short. That is, the BIS-AF powders of Examples 1 to 5 were excellent in industrial handleability.

In addition, the Ca ion content of the BIS-AF powders of Examples 1 to 5 was less than 1 ppm. From this, it was found that the BIS-AF powders of Examples 1 to 5 are preferably used in various technical fields (for example, manufacturing of electronic devices).

[Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3]
The following Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3 are, in particular, Examples and Comparative Examples for explaining the second embodiment in detail.

<Example 2-1>
First, 200 g of BIS-AF (manufactured by Central Glass Co., Ltd.) was placed in a 3 L flask made of borosilicate glass equipped with a stirring motor, a thermometer and a cooling condenser, and 1800 g of n-hexane and 200 g of ethyl acetate were poured into the flask.
Then, using an oil bath, BIS-AF was dissolved while heating and stirring until the internal temperature of the flask reached 65 ° C.
After the internal temperature of the flask reaches 65 ° C., the temperature is slowly lowered to 55 ° C. over 1 hour, and after the temperature reduction, 1 g of BIS-AF (manufactured by Central Glass Co., Ltd.) is added as a seed crystal, and 1 g is added as it is. The target BIS-AF was precipitated by stirring for a time.
After that, the mixture was cooled over 2 hours until the internal temperature reached 35 ° C., and the precipitated crystals were collected by vacuum filtration. The recovered crystals were dried under reduced pressure at 30 ° C. to obtain 24 g of BIS-AF in powder form.

<Example 2-2>
First, 200 g of BIS-AF (manufactured by Central Glass Co., Ltd.) was placed in a 3 L flask made of borosilicate glass equipped with a stirring motor, a thermometer and a cooling condenser, and 1800 g of n-hexane and 200 g of ethyl acetate were poured into the flask.
Then, using an oil bath, BIS-AF was dissolved while heating and stirring until the internal temperature of the flask reached 65 ° C.
After the internal temperature of the flask reaches 65 ° C., the temperature is slowly lowered to 55 ° C. over 2 hours, and after the temperature reduction, 1 g of BIS-AF (manufactured by Central Glass Co., Ltd.) is added as a seed crystal, and 2 as it is. The target BIS-AF was precipitated by stirring for a time.
After that, the mixture was cooled over 4 hours until the internal temperature reached 35 ° C., and the precipitated crystals were collected by vacuum filtration. The recovered crystals were dried under reduced pressure at 30 ° C. to obtain 27 g of BIS-AF in powder form.

<Example 2-3>
First, 200 g of BIS-AF (manufactured by Central Glass Co., Ltd.) was placed in a 3 L flask made of borosilicate glass equipped with a stirring motor, a thermometer and a cooling condenser, and 1800 g of n-heptane and 200 g of ethyl acetate were poured into the flask.
Then, using an oil bath, BIS-AF was dissolved while heating and stirring until the internal temperature of the flask reached 65 ° C.
After the internal temperature of the flask reaches 65 ° C., the temperature is slowly lowered to 55 ° C. over 1 hour, and after the temperature is lowered, 1 g of BIS-AF (manufactured by Central Glass Co., Ltd.) is added as a seed crystal and stirred as it is for 1 hour. The desired BIS-AF was precipitated.
After that, the mixture was cooled over 2 hours until the internal temperature reached 35 ° C., and the precipitated crystals were collected by vacuum filtration. The recovered crystals were dried under reduced pressure at 30 ° C. to obtain 23 g of BIS-AF in powder form.

<Example 2-4>
BIS-AF powder was obtained in the same manner as in <Example 5> described above.

<Comparative Example 2-1>
Comparative Example 2-1 is an example in which powder is produced by a method according to the example of Patent Document 2 (precipitation of BIF-AF by neutralization reaction).
200 g of BIS-AF (manufactured by Central Glass Co., Ltd.) and 52 g of sodium hydroxide were placed in a 3 L flask made of borosilicate glass equipped with a stirring motor and a thermometer. Then, 1800 g of water was added while paying attention to heat generation, and the mixture was stirred to obtain a uniform solution (the salt of BIF-AF was dissolved).
Then, the mixture was cooled to an internal temperature of 10 ° C. in an ice bath, and then neutralized by dropping 136 g of 35% hydrochloric acid water to precipitate BIS-AF.
The precipitated crystals were collected by vacuum filtration and dried under reduced pressure at 60 ° C. As a result, 171 g of powdery BIS-AF was obtained.

<Comparative Example 2-2>
Comparative Example 2-2 is an example in which the powder was produced by the method and conditions according to the examples of Patent Document 1 (the main component of the solvent is water).
150 g of BIS-AF (manufactured by Central Glass Co., Ltd.) was placed in a 2 L flask made of borosilicate glass equipped with a stirring motor, a thermometer and a cooling condenser, and 300 g of ethylene glycol and 700 g of ion-exchanged water were poured into the flask.
Then, using an oil bath, BIS-AF was dissolved while heating and stirring until the internal temperature of the flask reached 65 ° C.
After the internal temperature of the flask reached 65 ° C., BIS-AF was precipitated while cooling at a temperature lowering rate of 10 ° C./hour until the internal temperature of the flask reached 25 ° C.
The precipitated crystals were collected by vacuum filtration and dried under reduced pressure at 60 ° C. As a result, 135 g of powdery BIS-AF was obtained.

<Comparative Example 2-3>
Comparative Example 2-3 is an example in which the powder was produced by the method and conditions according to the examples of Patent Document (CN104528717A) (precipitation of BIS-AF by reprecipitation).
800 g of ion-exchanged water was poured into a 1 L flask made of borosilicate glass equipped with a stirring motor and a thermometer. A solution prepared by dissolving 100 g of BIS-AF (manufactured by Central Glass Co., Ltd.) in 100 g of methanol was added dropwise thereto at an internal temperature of 20 to 23 ° C., and BIS-AF was reprecipitated while stirring the inside of the flask.
The precipitated crystals were collected by vacuum filtration and dried under reduced pressure at 60 ° C. As a result, 89 g of powdery BIS-AF was obtained.

<Various measurements / evaluations>
(Diameter distribution)
Using SALD-2200, a particle size distribution meter manufactured by Shimadzu Corporation, the particle size distribution of the obtained powder BIS-AF dispersed in an n-decane solvent was measured. At the time of measurement, BIS-AF and n-decane solvent were mixed in advance on a slide glass to prepare a paste-like BIS-AF. Then, paste-like BIS-AF is gradually added to n-decane, which is a dispersion solvent, and the amount of addition is adjusted so that the absorbance value is 0.1 L / (mol · cm) or less, and the particle size distribution is distributed. Was measured. By analyzing the obtained measurement results, D ₅₀ , D ₉₀ , D _ave and D _m were calculated.

Table 3 summarizes information on particle size.

(Handling: Evaluation of agglomeration)
50 g of BIS-AF powder was placed in a 100 mL polyethylene container with a lid and allowed to stand at room temperature for 1 month. Then, the container was opened and the entire amount of BIS-AF powder was taken out, and the presence or absence of agglomeration due to aggregation of BIS-AF was visually confirmed.
The case where no agglomeration was confirmed was evaluated as ◯ (good), and the case where agglomeration was confirmed was evaluated as × (bad).

(Handling: Liquidity evaluation (Rohto test))
A total amount of 60 g of BIS-AF powder was added to a funnel having a funnel diameter of 150 mm, a nozzle diameter of 12 mm, and a nozzle length of 22 mm, and it was confirmed whether or not the powder could be discharged naturally. At that time, the case where the entire amount of BIS-AF powder was spontaneously discharged was evaluated as 〇 (good), and the case where it was not naturally discharged was evaluated as × (bad).

(Handling: Measurement of angle of repose)
Using a funnel with a funnel diameter of 150 mm, a nozzle diameter of 12 mm, and a nozzle length of 22 mm, a shake plate with a mesh opening of 0.5 mm is placed on the funnel, and a horizontal base is placed at a position 4.5 cm away from the tip of the funnel nozzle. did. Next, 50 g of BIS-AF powder was taken on a shaker plate, and the BIS-AF powder was dropped in the direction of the funnel nozzle using a brush and deposited on a horizontal table. Next, a photograph was taken of the accumulated powder pile, and the angle of repose was measured on the photograph. The smaller the angle of repose, the easier it is for the powder to flow smoothly, that is, the better the handleability.

(Measurement of bulk density (looseness, firmness))
The bulk density was measured using a JIS bulk specific gravity measuring instrument manufactured by Tsutsui Rikagaku Kikai. The bulk specific gravity measuring instrument is provided with a funnel having a funnel diameter of 150 mm, a nozzle diameter of 12 mm, and a nozzle length of 22 mm, a shaking plate having a mesh opening of 0.5 mm on the funnel, and a cylindrical 30 mL receiver under the funnel nozzle. 50 g of BIS-AF powder was taken on a shaking plate and slowly dropped into a receiver using a brush to allow natural filling. After scraping off the BIS-AF powder overflowing from the receiver, the looseness density was calculated by measuring the weight of the receiver. Further, when the BIS-AF powder was dropped, the hardness density was calculated from the weight obtained by compressing and filling the lower part of the receiver while lightly striking it.

(Evaluation of solvent solubility / undissolved residue)
The solvent solubility of the BIS-AF powders of Example 2-1 and Comparative Examples 2-1 to 2-3 was evaluated by the following procedure.
(I) Comparison of dissolution rate in 40% aqueous methanol solution 10 g of BIS-AF powder was weighed into a 100 mL flask made of borosilicate glass equipped with a stirrer and a thermometer. While stirring the powder BIS-AF at a constant speed, 40 g of a 40% aqueous methanol solution was immediately poured. Then, stirring at a constant rate was maintained, and the BIS-AF powder was completely dissolved at 18 to 20 ° C.
In the above procedure, the time taken from immediately after the addition of the aqueous methanol solution to the complete dissolution of the BIS-AF powder was measured.

(Ii) Comparison of dissolution rate with 10% sodium hydroxide aqueous solution 40 g of 10% sodium hydroxide aqueous solution was weighed into a 100 mL flask made of borosilicate glass equipped with a stirrer and a thermometer. 10 g of BIS-AF powder was added little by little to a 10% aqueous sodium hydroxide solution being stirred at a constant speed over 30 seconds. Then, stirring at a constant speed was maintained, and the integrated time until the BIS-AF powder was completely dissolved was measured at 18 to 20 ° C.

Table 4 summarizes the results of various measurements / evaluations.

From Tables 3 and 4, the agglomeration of the powders of Examples 2-1 to 2-4 was suppressed. In addition, the results of the Rohto test of the powders of Examples 2-1 to 2-4 were good. Furthermore, the angle of repose of the powders of Examples 2-1 to 2-4 was smaller than that of the powders of Comparative Examples 2-1 and 2-2. From these results, it is understood that the powder of the compound (A) having _{a D 50} of 50 to 100 μm and a D ₅₀ / D _{ave of 1.1 to 1.5 has good handleability.}
The bulk density (looseness, firmness) of the powders of Examples 2-1 to 2-4 was larger than that of the powders of Comparative Examples 2-1 to 2-3. From this, it can be said that the handleability of the powders of Examples 2-1 to 2-3 is good.
The solvent solubility of the powder of Example 2-1 was good. From this, it can be said that the handleability of the powder of Example 2-1 is good.

[Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-3]
The following Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-3 are, in particular, Examples and Comparative Examples for explaining the third embodiment in detail.

<Example 3-1>
First, 200 g of BIS-AF (manufactured by Central Glass Co., Ltd.) was placed in a 3 L flask made of borosilicate glass equipped with a stirring motor, a thermometer and a cooling condenser, and 1800 g of n-hexane and 200 g of ethyl acetate were poured into the flask.
Then, using an oil bath, BIS-AF was dissolved while heating and stirring until the internal temperature of the flask reached 65 ° C.
After the internal temperature of the flask reaches 65 ° C., the temperature is slowly lowered to 55 ° C. over 1 hour, and after the temperature reduction, 1 g of BIS-AF (manufactured by Central Glass Co., Ltd.) is added as a seed crystal, and 1 g is added as it is. The target BIS-AF was precipitated by stirring for a time.
After that, the mixture was cooled over 2 hours until the internal temperature reached 35 ° C., and the precipitated crystals were collected by vacuum filtration. The recovered crystals were dried under reduced pressure at 30 ° C. to obtain 24 g of BIS-AF in powder form.

<Example 3-2>
First, 200 g of BIS-AF (manufactured by Central Glass Co., Ltd.) was placed in a 3 L flask made of borosilicate glass equipped with a stirring motor, a thermometer and a cooling condenser, and 1800 g of n-hexane and 200 g of ethyl acetate were poured into the flask.
Then, using an oil bath, BIS-AF was dissolved while heating and stirring until the internal temperature of the flask reached 65 ° C.
After the internal temperature of the flask reaches 65 ° C., the temperature is slowly lowered to 55 ° C. over 2 hours, and after the temperature reduction, 1 g of BIS-AF (manufactured by Central Glass Co., Ltd.) is added as a seed crystal, and 2 as it is. The target BIS-AF was precipitated by stirring for a time.
After that, the mixture was cooled over 4 hours until the internal temperature reached 35 ° C., and the precipitated crystals were collected by vacuum filtration. The recovered crystals were dried under reduced pressure at 30 ° C. to obtain 27 g of BIS-AF in powder form.

<Example 3-3>
First, 200 g of BIS-AF (manufactured by Central Glass Co., Ltd.) was placed in a 3 L flask made of borosilicate glass equipped with a stirring motor, a thermometer and a cooling condenser, and 1800 g of n-heptane and 200 g of ethyl acetate were poured into the flask.
Then, using an oil bath, BIS-AF was dissolved while heating and stirring until the internal temperature of the flask reached 65 ° C.
After the internal temperature of the flask reaches 65 ° C., the temperature is slowly lowered to 55 ° C. over 1 hour, and after the temperature is lowered, 1 g of BIS-AF (manufactured by Central Glass Co., Ltd.) is added as a seed crystal and stirred as it is for 1 hour. The desired BIS-AF was precipitated.
After that, the mixture was cooled over 2 hours until the internal temperature reached 35 ° C., and the precipitated crystals were collected by vacuum filtration. The recovered crystals were dried under reduced pressure at 30 ° C. to obtain 23 g of BIS-AF in powder form.

<Example 3-4>
BIS-AF powder was obtained in the same manner as in <Example 5> described above.

<Comparative Example 3-1>
Comparative Example 3-1 is an example in which powder is produced by a method according to the example of Patent Document 2 (precipitation of BIF-AF by neutralization reaction).
200 g of BIS-AF (manufactured by Central Glass Co., Ltd.) and 52 g of sodium hydroxide were placed in a 3 L flask made of borosilicate glass equipped with a stirring motor and a thermometer. Then, 1800 g of water was added while paying attention to heat generation, and the mixture was stirred to obtain a uniform solution (the salt of BIF-AF was dissolved).
Then, the mixture was cooled to an internal temperature of 10 ° C. in an ice bath, and then neutralized by dropping 136 g of 35% hydrochloric acid water to precipitate BIS-AF.
The precipitated crystals were collected by vacuum filtration and dried under reduced pressure at 60 ° C. As a result, 171 g of powdery BIS-AF was obtained.

<Comparative Example 3-2>
Comparative Example 3-2 is an example in which the powder was produced by the method and conditions according to the examples of Patent Document 1 (the main component of the solvent is water).
150 g of BIS-AF (manufactured by Central Glass Co., Ltd.) was placed in a 2 L flask made of borosilicate glass equipped with a stirring motor, a thermometer and a cooling condenser, and 300 g of ethylene glycol and 700 g of ion-exchanged water were poured into the flask.
Then, using an oil bath, BIS-AF was dissolved while heating and stirring until the internal temperature of the flask reached 65 ° C.
After the internal temperature of the flask reached 65 ° C., BIS-AF was precipitated while cooling at a temperature lowering rate of 10 ° C./hour until the internal temperature of the flask reached 25 ° C.
The precipitated crystals were collected by vacuum filtration and dried under reduced pressure at 60 ° C. As a result, 135 g of powdery BIS-AF was obtained.

<Comparative Example 3-3>
Comparative Example 3-3 is an example in which the powder was produced by the method and conditions according to the examples of Patent Document (CN104528717A) (precipitation of BIS-AF by reprecipitation).
800 g of ion-exchanged water was poured into a 1 L flask made of borosilicate glass equipped with a stirring motor and a thermometer. A solution prepared by dissolving 100 g of BIS-AF (manufactured by Central Glass Co., Ltd.) in 100 g of methanol was added dropwise thereto at an internal temperature of 20 to 23 ° C., and BIS-AF was reprecipitated while stirring the inside of the flask.
The precipitated crystals were collected by vacuum filtration and dried under reduced pressure at 60 ° C. As a result, 89 g of powdery BIS-AF was obtained.

(Measurement of angle of repose)
Using a funnel with a funnel diameter of 150 mm, a nozzle diameter of 12 mm, and a nozzle length of 22 mm, a shake plate with a mesh opening of 0.5 mm is placed on the funnel, and a horizontal base is placed at a position 4.5 cm away from the tip of the funnel nozzle. did. Next, 50 g of BIS-AF powder was taken on a shaker plate, and the BIS-AF powder was dropped in the direction of the funnel nozzle using a brush and deposited on a horizontal table. Next, a photograph was taken of the accumulated powder pile, and the angle of repose was measured on the photograph.

(Evaluation of agglomeration)
50 g of BIS-AF powder was placed in a 100 mL polyethylene container with a lid and allowed to stand at room temperature for 1 month. Then, the container was opened and the entire amount of BIS-AF powder was taken out, and the presence or absence of agglomeration due to aggregation of BIS-AF was visually confirmed.
The case where no agglomeration was confirmed was evaluated as ◯ (good), and the case where agglomeration was confirmed was evaluated as × (bad).

(Liquidity evaluation: Rohto test)
A total amount of 60 g of BIS-AF powder was added to a funnel having a funnel diameter of 150 mm, a nozzle diameter of 12 mm, and a nozzle length of 22 mm, and it was confirmed whether or not the powder could be discharged naturally. At that time, the case where the entire amount of BIS-AF powder was spontaneously discharged was evaluated as 〇 (good), and the case where it was not naturally discharged was evaluated as × (bad).

(Evaluation of solvent solubility / undissolved residue)
The solvent solubility of the BIS-AF powders of Example 3-1 and Comparative Examples 3-1 to 3-4 was evaluated by the following procedure.
(I) Comparison of dissolution rate in 40% aqueous methanol solution 10 g of BIS-AF powder was weighed into a 100 mL flask made of borosilicate glass equipped with a stirrer and a thermometer. While stirring the powder BIS-AF at a constant speed, 40 g of a 40% aqueous methanol solution was immediately poured. Then, stirring at a constant rate was maintained, and the BIS-AF powder was completely dissolved at 18 to 20 ° C.
In the above procedure, the time taken from immediately after the addition of the aqueous methanol solution to the complete dissolution of the BIS-AF powder was measured.

The above various information are summarized in Tables 5 and 6.

From Tables 5 and 6, the evaluation results regarding the agglomeration and the Rohto test of the powders of Examples 3-1 to 3-4 were good. Moreover, the solvent solubility of the powder of Example 3-1 was good. _{That, D 50} is 50 ~ 100 [mu] m, the powder of the compound angle of repose is 35 ~ 49 ° (A) was excellent in industrial handling property.

[Examples 4-1 to 4-5 and Comparative Examples 4-1 to 4-3]
The following Examples 4-1 to 4-5 and Comparative Examples 4-1 to 4-3 are, in particular, Examples and Comparative Examples for explaining the fourth embodiment in detail.

<Example 4-1>
25.0 g (74.4 mmol) of BIS-AF powder manufactured by Tokyo Chemical Industry Co., Ltd. was collected from a reagent bottle and placed in a glass container made of borosilicate glass having a volume of 500 mL equipped with a stirrer and a cooling condenser. Next, 202.5 g of pure water and 22.5 g of methanol were added into the container, and the temperature inside the container was raised to 65 ° C. with stirring.
While the temperature was being raised, the BIS-AF powder began to melt and the inside of the container became suspended. The temperature was maintained as it was, and the mixture was stirred for 1.5 hours.

After 1.5 hours had passed, stirring was temporarily stopped and the container was allowed to stand, and the inside of the container was visually observed. As a result of observation, it was confirmed that the two phases of the aqueous layer and the melt of BIS-AF were separated (not completely mixed) in the container. In addition, unmelted BIS-AF was not confirmed.
At this time, the BIS-AF concentration on the aqueous layer side was measured by ^{19 F-NMR using p-bis (trifluoromethyl) benzene as an internal standard.} The concentration was 2% by mass or less, and most of BIS-AF was not "dissolved" in water / methanol even at a high temperature of about 65 ° C. That is, at the temperature at which the raw material BIS-AF powder was completely "melted", the solubility of the aqueous dispersion medium BIS-AF was well below 10 [g / 100 g].
Next, when the mixture was stirred for 1 hour while maintaining the internal temperature of 60 to 65 ° C., crystals were precipitated. Then, the internal temperature was cooled to room temperature at a temperature lowering rate of 15 ° C./1 hour. The room temperature at this time was about 25 ° C.
After cooling, the precipitated BIS-AF was separated and recovered by vacuum filtration using a suction filter equipped with a filter paper. After recovery, it was washed with 75 mL of pure water. The washed BIS-AF was dried at 80 ° C. under reduced pressure (1 kPa or less) for 6 hours using a vacuum dryer.

The BIS-AF powder obtained after drying was 22.9 g, and the yield was 92%.

<Example 4-2>
BIS as in Example 4-1 except that the amount of BIS-AF powder was changed to 100.0 g (298 mmol), the amount of pure water was changed to 810.0 g, and methanol was changed to 90.0 g. -AF powder was obtained.
The BIS-AF powder obtained after drying was 94.6 g, and the yield was 95%.

In the same manner as in Example 1, after 1.5 hours had passed, stirring was temporarily stopped and the container was allowed to stand, and the inside of the container was visually observed. As a result of observation, it was confirmed that the two phases of the aqueous layer and the melt of BIS-AF were separated (not completely mixed) in the container. In addition, unmelted BIS-AF was not confirmed.
At this time, the BIS-AF concentration on the aqueous layer side was measured by ^{19 F-NMR using p-bis (trifluoromethyl) benzene as an internal standard.} The concentration was 2% by mass or less, and most of BIS-AF was not "dissolved" in water / methanol even at a high temperature of about 65 ° C. That is, at the temperature at which the raw material BIS-AF powder was completely "melted", the solubility of the aqueous dispersion medium BIS-AF was well below 10 [g / 100 g].

<Example 4-3>
25.0 g (74.4 mmol) of BIS-AF powder was collected from the same reagent bottle as in Example 4-1 and placed in a glass container made of borosilicate glass having a volume of 500 mL and equipped with a stirrer and a cooling condenser. .. Then, 225.0 g of pure water was added into the container. Then, the temperature inside the container was raised to 95 ° C. while stirring.
While the temperature was being raised, the BIS-AF powder began to melt, and the inside of the container became suspended. The temperature was maintained at 95 ° C. and the mixture was stirred for 1 hour.

After 1 hour, the stirring was stopped and the container was allowed to stand, and the inside of the container was visually observed. As a result of observation, it was confirmed that the two phases of the aqueous layer and the melt of BIS-AF were separated (not completely mixed) in the container. In addition, unmelted BIS-AF was not confirmed.
At this time, the BIS-AF concentration on the aqueous layer side was measured by ^{19 F-NMR using p-bis (trifluoromethyl) benzene as an internal standard.} The concentration was about 2% by mass, and most of BIS-AF was not "dissolved" in water even at a high temperature of about 95 ° C. That is, at the melting temperature of the raw material BIS-AF powder, the solubility of the aqueous dispersion medium BIS-AF was far below 10 [g / 100 g].

Next, when the mixture was stirred for 1 hour while maintaining the internal temperature at 92 to 94 ° C., crystals were precipitated. Then, the internal temperature was cooled to room temperature at a temperature lowering rate of 15 ° C./1 hour. The room temperature at this time was about 25 ° C.
After cooling, the precipitated BIS-AF was separated and recovered by vacuum filtration using a suction filter equipped with a filter paper. After recovery, it was washed with 75 mL of pure water. The washed BIS-AF was dried at 75 ° C. under reduced pressure (1 kPa or less) for 8 hours using a vacuum dryer.

The BIS-AF powder obtained after drying was 24.1 g, and the yield was 96%.

<Example 4-4>
25.0 g (74.4 mmol) of BIS-AF powder was collected from the same reagent bottle as in Example 4-1 and placed in a glass container made of borosilicate glass having a volume of 500 mL and equipped with a stirrer and a cooling condenser. Next, 112.5 g of pure water and 12.5 g of methanol were added into the container, and the temperature inside the container was raised to 65 ° C. with stirring.
While the temperature was being raised, the BIS-AF powder began to melt and the inside of the container became suspended. The temperature was maintained as it was, and the mixture was stirred for 1.5 hours.

After 1.5 hours had passed, stirring was temporarily stopped and the container was allowed to stand, and the inside of the container was visually observed. As a result of observation, it was confirmed that the two phases of the aqueous layer and the melt of BIS-AF were separated (not completely mixed) in the container. In addition, unmelted BIS-AF was not confirmed.
At this time, the BIS-AF concentration on the aqueous layer side was measured by ^{19 F-NMR using p-bis (trifluoromethyl) benzene as an internal standard.} The concentration was 2% by mass or less, and most of BIS-AF was not "dissolved" in water / methanol even at a high temperature of about 65 ° C. That is, at the temperature at which the raw material BIS-AF powder was completely "melted", the solubility of the aqueous dispersion medium BIS-AF was well below 10 [g / 100 g].

Next, when the mixture was stirred for 1 hour while maintaining the internal temperature of 60 to 65 ° C., crystals were precipitated. Then, the internal temperature was cooled to room temperature at a temperature lowering rate of 15 ° C./1 hour. The room temperature at this time was about 25 ° C.
After cooling, the precipitated BIS-AF was separated and recovered by vacuum filtration using a suction filter equipped with a filter paper. After recovery, it was washed with 75 mL of pure water. The washed BIS-AF was dried at 80 ° C. under reduced pressure (1 kPa or less) for 6 hours using a vacuum dryer.

The BIS-AF powder obtained after drying was 23.5 g, and the yield was 94%.

<Example 4-5>
25.0 g (74.4 mmol) of BIS-AF powder was collected from the same reagent bottle as in Example 4-1 and placed in a glass container made of borosilicate glass having a volume of 500 mL and equipped with a stirrer and a cooling condenser. Next, 100.0 g of pure water and 25.0 g of methanol were added into the container, and the temperature inside the container was raised to 45 ° C. with stirring.
While the temperature was being raised, the BIS-AF powder began to melt and the inside of the container became suspended. The temperature was maintained as it was, and the mixture was stirred for 1.5 hours.

After 1.5 hours had passed, stirring was temporarily stopped and the container was allowed to stand, and the inside of the container was visually observed. As a result of observation, it was confirmed that the two phases of the aqueous layer and the melt of BIS-AF were separated (not completely mixed) in the container. In addition, unmelted BIS-AF was not confirmed.
At this time, the BIS-AF concentration on the aqueous layer side was measured by ^{19 F-NMR using p-bis (trifluoromethyl) benzene as an internal standard.} The concentration was 2% by mass or less, and most of BIS-AF was not "dissolved" in water / methanol even at a temperature of about 45 ° C. That is, at the temperature at which the raw material BIS-AF powder was completely "melted", the solubility of the aqueous dispersion medium BIS-AF was well below 10 [g / 100 g].

Next, when the mixture was stirred for 1 hour while maintaining the internal temperature of 35 to 40 ° C., crystals were precipitated. Then, the internal temperature was cooled to room temperature at a temperature lowering rate of 10 ° C./1 hour. The room temperature at this time was about 25 ° C.

After cooling, the precipitated BIS-AF was separated and collected by vacuum filtration using a suction filter equipped with a filter paper. After recovery, it was washed with 75 mL of pure water. The washed BIS-AF was dried at 80 ° C. under reduced pressure (1 kPa or less) for 6 hours using a vacuum dryer.

The BIS-AF powder obtained after drying was 24.1 g, and the yield was 96%.

<Comparative Example 4-1>
BIS-AF (manufactured by Tokyo Chemical Industry Co., Ltd.) was collected from a reagent bottle.

<Comparative Example 4-2>
200 g of pure water was poured into a glass container made of borosilicate glass having a volume of 500 L equipped with a stirrer, and stirring was started at room temperature (about 20 ° C.). 25.0 g of BIS-AF (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 50 g of methanol was slowly added dropwise thereto using a dropping funnel to reprecipitate BIS-AF.
After precipitation of BIS-AF, BIS-AF was recovered by vacuum filtration using a suction filter equipped with a filter paper. Then, it was dried in a vacuum dryer at 80 ° C. under reduced pressure for 8 hours. The BIS-AF powder obtained after drying was 22.1 g, and the yield was 88%.

<Comparative Example 4-3>
150 g of BIS-AF (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a 2 L volume borosilicate glass container equipped with a stirrer and a cooling condenser, and 300 g of ethylene glycol and 700 g of ion-exchanged water were poured into the container. Then, using an oil bath, BIS-AF was dissolved while heating and stirring until the internal temperature of the flask reached 85 ° C. The temperature was maintained as it was, and the mixture was stirred for 1 hour. After 1 hour, the stirring was stopped and the mixture was allowed to stand, and the inside of the container was visually observed to confirm a uniform solution.
Next, when the flask was cooled at a temperature lowering rate of 10 ° C./hour with stirring until the internal temperature of the flask reached 25 ° C., precipitation of crystals was confirmed during the temperature lowering. The precipitated crystals were collected by vacuum filtration and dried under reduced pressure at 60 ° C. The BIS-AF powder obtained after drying was 137 g, and the yield was 91%.

<Measurement>
(X-ray diffraction (XRD) spectrum)
The X-ray diffraction (XRD) spectrum of the powder is based on the measurement method and measurement conditions described above.

Table 7 summarizes information on the X-ray diffraction spectrum.

<Evaluation>
(Dissolution rate)
(I) Comparison of dissolution rate in 40% aqueous methanol solution (40% MeOH water) 10 g of BIS-AF powder was weighed into a 100 mL flask made of borosilicate glass equipped with a stirrer and a thermometer. While stirring the powder BIS-AF at a constant speed (200 rpm), 40 g of a 40% aqueous methanol solution was immediately poured. Then, stirring at a constant speed (200 rpm) was maintained, and the BIS-AF powder was completely dissolved at 18 to 20 ° C.
In the above procedure, the time taken from immediately after the addition of the aqueous methanol solution to the complete dissolution of the BIS-AF powder was measured. It was confirmed by visual observation that the BIS-AF powder was completely melted.

(Ii) Comparison of dissolution rate in 10% sodium hydroxide aqueous solution (10% NaOH water) 40 g of 10% sodium hydroxide aqueous solution was weighed into a 100 mL flask made of borosilicate glass equipped with a stirrer and a thermometer. 10 g of BIS-AF powder was added little by little over 30 seconds to a 10% aqueous sodium hydroxide solution being stirred at a constant speed (200 rpm). After that, stirring was maintained at a constant speed (200 rpm), and the integrated time from immediately after the start of adding the BIS-AF powder to the complete dissolution of the BIS-AF powder was measured at 18 to 20 ° C. It was confirmed by visual observation that the BIS-AF powder was completely melted.

(Drying test)
The dispersion liquid in which the BIS-AF powder was dispersed in water was passed through a filter equipped with a filter paper and filtered to obtain a water-wet BIS-AF powder. The obtained BIS-AF powder was placed in a vacuum dryer manufactured by Yamato Scientific Co., Ltd., dried at 0.5 KPa and 60 ° C., and the water content of the powder was measured.

When 10 g of BIS-AF powder was added and dried at 0.5 kPa and 60 ° C. (0 hours), 0.5 hours and 1 hour later, the water content of the powder was measured by volumetric titration type Karl Fischer (MKV). -710B, manufactured by Kyoto Electronics Industry Co., Ltd.).

The evaluation results are summarized in the table below.

As shown in Table 8, the dissolution rates of the BIS-AF powders of Examples 4-1, 4-4 and 4-5 were good. Further, from the evaluation results of the water content, it was found that the drying time when drying the BIS-AF powders of Examples 4-1, 4-4 and 4-5 was short. That is, the BIS-AF powder of Example 4-1 and the like was excellent in industrial handleability.

Moreover, about Example 4-1, the "moisture absorption test" was performed as follows.
(Hygroscopic test)
10 g of BIS-AF powder was weighed on a charley, and the water content of the BIS-AF powder was measured with a capacitive Karl Fischer (MKV-710B, manufactured by Kyoto Denshi Kogyo Co., Ltd.).
In addition, 10 g of BIS-AF powder is weighed in a charley and allowed to stand in a constant temperature and humidity chamber at a temperature of 30 ° C. and a humidity of 98%. MKV-710B, manufactured by Kyoto Electronics Industry Co., Ltd.).

The evaluation results are shown in the table below.

As shown in Table 9, the water content of the BIS-AF powder of Example 4-1 did not change even after 24 hours, and it was found that it was difficult to absorb moisture. That is, the BIS-AF powder of Example 4-1 was excellent in industrial handleability.

This application is filed on September 30, 2019, Japanese Application Japanese Patent Application No. 2019-178923, Japanese Application Japanese Patent Application No. 2019-178924, filed on September 30, 2019, December 27, 2019. Claim priorities based on Japanese Patent Application No. 2019-238016 filed and Japanese Patent Application No. 2020-03338 filed on February 28, 2020, all of which are incorporated herein by reference.

Claims

A powder of a compound represented by the general formula (A) below.
The mode diameter D m measured by the laser diffraction / scattering method is 75 to 150 μm.
A powder having a Ca ion content of less than 1 ppm.

In the general formula (A), R 1 to R 8 independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom or an amino group, respectively.
The powder according to claim 1.
A powder having a Na ion content of less than 1 ppm.
The powder according to claim 1 or 2.
When the volume-reduced cumulative 50% diameter measured was D 50 by a laser diffraction scattering method, the powder D 50 of a 40 ~ 100 [mu] m.
The powder according to any one of claims 1 to 3.
When the volume-based cumulative 50% diameter measured by the laser diffraction / scattering method is D 50 and the volume-based cumulative 90% diameter measured by the same method is D 90 .
A powder having a value of (D 90- D 50 ) / D 50 of 1.3 to 1.7.
The powder according to any one of claims 1 to 4.
A powder having an alcohol content of 400 ppm or less.
A powder of a compound represented by the general formula (A) below.
The volume-reduced cumulative 50% diameter measured by a laser diffraction scattering method and D 50, when the arithmetic volume average diameter measured by the law and the D ave,
D 50 is 50-100 μm
D 50 / D ave is a powder of 1.1 to 1.5.

In the general formula (A), R 1 to R 8 independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom or an amino group, respectively.
The powder according to claim 6.
A powder having a mode diameter D m of 75 to 150 μm measured by a laser diffraction / scattering method.
The powder according to claim 6 or 7.
When the volume-based cumulative 90% diameter measured by the laser diffraction / scattering method is D 90 ,
A powder having a value of (D 90- D 50 ) / D 50 of 1.3 to 1.7.
The powder according to any one of claims 6 to 8.
A powder having a loose bulk density of 0.50 to 0.75 g / cm 3 and a firm bulk density of 0.76 to 0.90 g / cm 3.
A powder of a compound represented by the general formula (A) below.
Volume-reduced cumulative 50% diameter D 50 measured by a laser diffraction scattering method is 50 ~ 100 [mu] m,
A powder with an angle of repose of 35 to 49 °.

In the general formula (A), R 1 to R 8 independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom or an amino group, respectively.
The powder according to claim 10.
A powder having a mode diameter D m of 75 to 150 μm measured by a laser diffraction / scattering method.
The powder according to claim 10 or 11.
When the volume-based cumulative 90% diameter measured by the laser diffraction / scattering method is D 90 ,
A powder having a value of (D 90- D 50 ) / D 50 of 1.3 to 1.7.
The powder according to any one of claims 10 to 12.
A powder in which ρ 2 / ρ 1 is 1.01 to 1.45 when the looseness density of the powder is ρ 1 and the hardness density of the powder is ρ 2.
2,2-Bis (4-hydroxyphenyl) hexafluoropropane powder
The half width of the peak near 2θ = 22.3 ° in the X-ray diffraction spectrum is 0.050 ° or more and 0.180 ° or less.
The half width of the peak near 2θ = 23.7 ° in the X-ray diffraction spectrum is 0.050 ° or more and 0.120 ° or less.
A powder having a peak width of 0.040 ° or more and 0.120 ° or less in the X-ray diffraction spectrum near 2θ = 25.8 °.
The powder according to claim 14.
A powder having a peak width at half maximum of around 2θ = 22.3 ° in an X-ray diffraction spectrum of 0.055 ° or more and 0.170 ° or less.
The powder according to claim 14 or 15.
A powder having a peak width at half maximum of around 2θ = 22.3 ° in an X-ray diffraction spectrum of 0.060 ° or more and 0.165 ° or less.
The powder according to any one of claims 14 to 16.
A powder having a peak width at half maximum of around 2θ = 23.7 ° in an X-ray diffraction spectrum of 0.055 ° or more and 0.100 ° or less.
The powder according to any one of claims 14 to 17.
A powder having a peak width of 0.060 ° or more and 0.090 ° or less in the X-ray diffraction spectrum near 2θ = 23.7 °.
The powder according to any one of claims 14 to 18.
A powder having a peak width at half maximum of around 2θ = 25.8 ° in the X-ray diffraction spectrum of 0.045 ° or more and 0.115 ° or less.
The powder according to any one of claims 14 to 19.
A powder having a peak width at half maximum of around 2θ = 25.8 ° in the X-ray diffraction spectrum of 0.050 ° or more and 0.110 ° or less.
Hereinafter, a method for producing a powder of a compound represented by the general formula (A).
By putting the raw material containing the compound represented by the general formula (A) and the aqueous dispersion medium in a container and heating the raw material, the raw material is melted in the presence of the aqueous dispersion medium, and the raw material is melted. A melting step of obtaining a non-uniform liquid containing a melt and the aqueous dispersion medium, and
A crystallization step of crystallizing the melt to obtain crystals by lowering the temperature of the non-uniform liquid.
Including
In the melting step, the melting temperature T 1 of the said raw material, said aqueous dispersion medium, the solubility of the compound represented by the general formula (A), 10 [g / 100g] or less, the production of the powder Method.

In the general formula (A), R 1 to R 8 independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom or an amino group, respectively.
The powder manufacturing method according to claim 21.
A method for producing a powder, wherein the aqueous dispersion medium contains substantially only water.
The powder manufacturing method according to claim 21.
The aqueous dispersion medium contains water and alcohol, and contains water and alcohol.
A method for producing a powder, wherein the ratio of the alcohol in the aqueous dispersion medium is 30% by mass or less.
The method for producing a powder according to any one of claims 21 to 23.
A method for producing a powder, wherein the temperature T 2 in the crystallization step is 1 to 10 ° C. lower than the temperature T 1.
The method for producing a powder according to any one of claims 21 to 24.
The crystallization step is a method for producing a powder, which is carried out while stirring the non-uniform liquid.
A method for producing a solution containing a compound represented by the general formula (A) below.
A method for producing a solution, which comprises a step of obtaining a solution of the compound represented by the general formula (A) using a solvent and the powder according to any one of claims 1 to 20.

In the general formula (A), R 1 to R 8 independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom or an amino group, respectively.
The method for producing a solution according to claim 26.
A method for producing a solution, which comprises a step of refining the powder.