JP6931198B2 - Compound purification method - Google Patents

Description

The present invention relates to a method for purifying a compound (eg, a hydroxy-substituted aromatic compound).

Hydroxy-substituted aromatic compounds such as dihydroxynaphthalene are useful as raw materials for compounds or resins used as encapsulants for semiconductors, coating agents, resist materials, semiconductor underlayer film forming materials (for example, Patent Documents 1 to 1). 2). Further, a specific method is known as a method for purifying a hydroxy-substituted aromatic compound such as dihydroxynaphthalene (see, for example, Patent Document 3).

International Publication No. 2013/024778 International Publication No. 2013/024779 Chinese Patent Application Publication No. 1034627249

In the above applications, the metal content is an important performance evaluation item for improving the yield. That is, when a large amount of metal is contained in the compound or resin obtained from the hydroxy-substituted aromatic compound as a raw material, the metal remains in the semiconductor and deteriorates the electrical characteristics of the semiconductor. Therefore, the metal content as an impurity Is required to be reduced.
As a purification method for reducing the metal content of a compound or resin obtained from a hydroxy-substituted aromatic compound, recrystallization was carried out by adding ion-exchanged water or pure water to the compound or a mixture containing the resin and an organic solvent. After that, a method of performing solid-liquid separation, the compound or resin is dissolved in an organic solvent that is not arbitrarily mixed with water, and the solution is brought into contact with an aqueous solution to perform an extraction treatment to transfer the metal component to the aqueous phase. , A method of reducing the metal content by separating the organic phase and the aqueous phase can be considered.
However, in the above method, when a hydroxy-substituted aromatic compound having a high metal content is used as a raw material, there is a problem that the removing effect on a specific metal species is not sufficient.
Therefore, it is desired to establish an industrially advantageous purification method for high-purity hydroxy-substituted aromatic compounds having a reduced metal content.
Further, when the purity of the hydroxy-substituted aromatic compound is low, there is a problem that the yield of the compound or resin obtained from the hydroxy-substituted aromatic compound decreases or varies.
Furthermore, conventionally, the disclosed purification methods have not been studied to reduce the metal content, and the reduction of the metal content is insufficient.
An object of the present invention is to provide a method for industrially advantageous purification of hydroxy-substituted aromatic compounds.

As a result of diligent studies to solve the above problems, the present inventors have found that the content of various metals is significantly reduced by contacting a solution containing a hydroxy-substituted aromatic compound and a solvent with an ion exchange resin. The heading led to the present invention.

（前記式（Ａ_０）中、ｎ^０は０〜９の整数であり、ｍ^０は０〜２の整数であり、ｐ^０は０〜９の整数であり、ここで、該ｎ^０、ｍ^０及びｐ^０の少なくとも１つが１以上の整数であり、さらに、ｍ^０が１のとき、前記式（Ａ_０）はナフタレン骨格又はビフェニル骨格を有することを示し、Ｒaは各々独立して、水酸基、ハロゲン基、炭素数１〜４０の直鎖状、分岐状若しくは環状のアルキル基、置換基を有していてもよい炭素数６〜４０のアリール基、又は炭素数２〜４０のアルケニル基及びそれらの組み合わせからなる群より選択される基であり、該アルキル基、該アリール基又は該アルケニル基は、エーテル結合、ケトン結合、あるいはエステル結合を含んでいてもよい。前記式（Ｂ_０）中、ｎ^１は０〜９の整数であり、ｐ^１は０〜９の整数であり、Ｒｂは各々独立して、水素原子、水酸基、ハロゲン基、炭素数１〜４０の直鎖状、分岐状若しくは環状のアルキル基、置換基を有していてもよい炭素数６〜４０のアリール基、又は炭素数２〜４０のアルケニル基及びそれらの組み合わせからなる群より選択される基であり、該アルキル基、該アリール基又は該アルケニル基は、エーテル結合、ケトン結合、あるいはエステル結合を含んでいてもよい。）
［２］
前記ヒドロキシ置換芳香族化合物が、下記式（Ａ）及び／又は（Ｂ）で表される化合物である、［１］に記載の化合物の精製方法。

（前記式（Ａ）中、ｎ^０は０〜９の整数であり、ｍ^０は０〜２の整数であり、ｐ^０は０〜９の整数であり、ここで、該ｎ^０、ｍ^０及びｐ^０の少なくとも１つが１以上の整数であり、さらに、ｍ^０が１のとき、前記式（Ａ_０）はナフタレン骨格又はビフェニル骨格を有することを示し、Ｒ_０は各々独立して、炭素数１〜３０の直鎖状、分岐状若しくは環状のアルキル基、置換基を有していてもよい炭素数６〜１５のアリール基、又は炭素数２〜１５のアルケニル基であり、上記式（Ｂ）中、ｎ^１は０〜９の整数であり、ｐ^１は０〜９の整数であり、Ｒ_１は各々独立して、炭素数１〜３０の直鎖状、分岐状若しくは環状のアルキル基、置換基を有していてもよい炭素数６〜１５のアリール基、又は炭素数２〜１５のアルケニル基である。）
［３］
前記ヒドロキシ置換芳香族化合物が、下記式（Ａ−１）で表される化合物、下記式（Ａ−２）で表される化合物、下記式（Ａ−３）で表される化合物、下記式（Ａ−４）で表される化合物、及び下記式（Ｂ−１）で表される化合物からなる群より選ばれる１種以上である、［１］に記載の化合物の精製方法。

（前記式（Ａ−１）中、ｎ^０は１〜５の整数であり、前記式（Ａ−２）中、ｎ^０は０〜７の整数であり、前記式（Ａ−３）〜（Ａ−４）中、ｎ^０は０〜９の整数であり、上記式（Ｂ−１）中、ｎ^１は０〜９の整数である。）
［４］
前記ヒドロキシ置換芳香族化合物が、下記式（１）で表される化合物である、［１］に記載の化合物の精製方法。

［５］
前記ヒドロキシ置換芳香族化合物が、２，６−ジヒドロキシナフタレン及び２，７−ジヒドロキシナフタレンからなる群より選ばれる１種以上である、［１］に記載の化合物の精製方法。
［６］
前記工程において、前記接触吸着処理の後、さらに、ろ過により溶液（Ａ）の分離回収を行う、［１］〜［５］のいずれかに記載の化合物の精製方法。
［７］
前記接触が、酸素濃度が２０％未満の雰囲気で行われる、［１］〜［６］のいずれかに記載の化合物の精製方法。
［８］
前記溶媒が、酢酸エチル、酢酸ブチル、メチルイソブチルケトン、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、シクロペンタノン及びシクロヘキサノンからなる群より選ばれる１種以上である、［１］〜［７］のいずれかに記載の化合物の精製方法。That is, the present invention is as follows.
[1]
A method for purifying a compound, which comprises a step of contacting a solution (A) containing a hydroxy-substituted aromatic compound represented by the following formulas (A ₀ ) and / or (B _{0) and a solvent with an ion exchange resin.}

(In the above equation (A ₀ ), n ⁰ is an integer of ^{0 to 9, m 0} is an integer of 0 to 2, and p ⁰ is an integer of 0 to 9, where n ⁰ and m. ^When at least one of 0 and p ⁰ is an integer of 1 or more and m ⁰ is 1, the above formula (A ₀ ) indicates that it has a naphthalene skeleton or a biphenyl skeleton, and Ra is independently a hydroxyl group. , Halogen groups, linear, branched or cyclic alkyl groups having 1 to 40 carbon atoms, aryl groups having 6 to 40 carbon atoms which may have substituents, or alkenyl groups having 2 to 40 carbon atoms and It is a group selected from the group consisting of a combination thereof, and the alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond. In the above formula (B ₀ ). , N ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and Rb is independently a hydrogen atom, a hydroxyl group, a halogen group, and a linear or branched form having 1 to 40 carbon atoms. Alternatively, it is a group selected from the group consisting of a cyclic alkyl group, an aryl group having 6 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 40 carbon atoms and a combination thereof, and the alkyl group. The group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond.)
[2]
The method for purifying a compound according to [1], wherein the hydroxy-substituted aromatic compound is a compound represented by the following formulas (A) and / or (B).

(In the above equation (A), n ⁰ is an integer of ^{0 to 9, m 0} is an integer of 0 to 2, and p ⁰ is an integer of 0 to 9, where n ⁰ and m ^0. And p ⁰ is an integer of 1 or more, and when m ⁰ is 1, the formula (A ₀ ) indicates that it has a naphthalene skeleton or a biphenyl skeleton, and R ₀ is independently carbon. A linear, branched or cyclic alkyl group having a number of 1 to 30, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms, according to the above formula ( In B), n ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and R ₁ is an independently linear, branched or cyclic alkyl having 1 to 30 carbon atoms. An aryl group having 6 to 15 carbon atoms, which may have a group or a substituent, or an alkenyl group having 2 to 15 carbon atoms.)
[3]
The hydroxy-substituted aromatic compound is a compound represented by the following formula (A-1), a compound represented by the following formula (A-2), a compound represented by the following formula (A-3), and a compound represented by the following formula (A-3). The method for purifying a compound according to [1], which is one or more selected from the group consisting of a compound represented by A-4) and a compound represented by the following formula (B-1).

(In the formula (A-1), n ⁰ is an integer of 1 to 5, and in the formula (A-2), n ⁰ is an integer of 0 to 7, and the formulas (A-3) to ( In A-4), n ⁰ is an integer from 0 to 9, and in the above equation (B-1), n ¹ is an integer from 0 to 9.)
[4]
The method for purifying a compound according to [1], wherein the hydroxy-substituted aromatic compound is a compound represented by the following formula (1).

[5]
The method for purifying a compound according to [1], wherein the hydroxy-substituted aromatic compound is at least one selected from the group consisting of 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene.
[6]
The method for purifying a compound according to any one of [1] to [5], wherein in the step, after the contact adsorption treatment, the solution (A) is further separated and recovered by filtration.
[7]
The method for purifying a compound according to any one of [1] to [6], wherein the contact is performed in an atmosphere having an oxygen concentration of less than 20%.
[8]
[1] to [7], wherein the solvent is one or more selected from the group consisting of ethyl acetate, butyl acetate, methyl isobutyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclopentanone and cyclohexanone. The method for purifying a compound according to any one.

INDUSTRIAL APPLICABILITY According to the present invention, a hydroxy-substituted aromatic compound can be industrially advantageously purified, and the content of various metals can be adjusted.

Hereinafter, embodiments of the present invention (hereinafter, also referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and the present invention is not limited to the embodiments.

（前記式（Ａ_０）中、ｎ^０は０〜９の整数であり、ｍ^０は０〜２の整数であり、ｐ^０は０〜９の整数であり、ここで、該ｎ^０、ｍ^０及びｐ^０の少なくとも１つが１以上の整数であり、さらに、ｍ^０が１のとき、前記式（Ａ_０）はナフタレン骨格又はビフェニル骨格を有することを示し、Ｒaは各々独立して、水酸基、ハロゲン基、炭素数１〜４０の直鎖状、分岐状若しくは環状のアルキル基、置換基を有していてもよい炭素数６〜４０のアリール基、又は炭素数２〜４０のアルケニル基及びそれらの組み合わせからなる群より選択される基であり、該アルキル基、該アリール基又は該アルケニル基は、エーテル結合、ケトン結合、あるいはエステル結合を含んでいてもよい。前記式（Ｂ_０）中、ｎ^１は０〜９の整数であり、ｐ^１は０〜９の整数であり、Ｒｂは各々独立して、水素原子、水酸基、ハロゲン基、炭素数１〜４０の直鎖状、分岐状若しくは環状のアルキル基、置換基を有していてもよい炭素数６〜４０のアリール基、又は炭素数２〜４０のアルケニル基及びそれらの組み合わせからなる群より選択される基であり、該アルキル基、該アリール基又は該アルケニル基は、エーテル結合、ケトン結合、あるいはエステル結合を含んでいてもよい。）
上記のように構成されているため、本実施形態に係る化合物の精製方法により、ヒドロキシ置換芳香族化合物を工業的に有利に精製することができる。すなわち、式（Ａ上記ヒドロキシ置換芳香族化合物を溶媒に溶解させ、その溶液をイオン交換樹脂と接触させ、吸着処理が行われることにより、該溶液に含まれる不純物としての金属成分をイオン交換樹脂に移行させることができる。その後、該溶液とイオン交換樹脂とを分離して、高純度を維持しつつも金属成分量が低減されたヒドロキシ置換芳香族化合物とすることができる。
上記のとおり、本実施形態における「精製」とは、ヒドロキシ置換芳香族化合物と共存し得る金属成分を十分に低減する操作を意味し、具体的には、Ｎａ量が５０ｐｐｂ以下、Ｆｅ量が５０ｐｐｂ以下、Ｃｒ量が５０ｐｐｂ以下、及びＺｎ量が５０ｐｐｂ以下であるヒドロキシ置換芳香族化合物が得られる。これらの金属成分量は後述する実施例に記載の方法で測定することができる。
なお、本実施形態における「接触」とは、例えば、上記溶液をイオン交換樹脂の表面で接触させる態様や、上記溶液を当該表面上で接触させつつイオン交換樹脂の外部で移動させる態様等を意味し、上記溶液がイオン交換樹脂の外部から当該イオン交換樹脂の内部を通過して再度イオン交換樹脂の外部へと移動する態様（すなわち、通液する態様）は除外される。The method for purifying a compound according to the present embodiment includes a step of contacting a solution containing a hydroxy-substituted aromatic compound represented by the following _{formulas (A 0} ) and / or (B _{0) and a solvent with an ion exchange resin.} ..

(In the above equation (A ₀ ), n ⁰ is an integer of ^{0 to 9, m 0} is an integer of 0 to 2, and p ⁰ is an integer of 0 to 9, where n ⁰ and m. ^When at least one of 0 and p ⁰ is an integer of 1 or more and m ⁰ is 1, the above formula (A ₀ ) indicates that it has a naphthalene skeleton or a biphenyl skeleton, and Ra is independently a hydroxyl group. , Halogen groups, linear, branched or cyclic alkyl groups having 1 to 40 carbon atoms, aryl groups having 6 to 40 carbon atoms which may have substituents, or alkenyl groups having 2 to 40 carbon atoms and It is a group selected from the group consisting of a combination thereof, and the alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond. In the above formula (B ₀ ). , N ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and Rb is independently a hydrogen atom, a hydroxyl group, a halogen group, and a linear or branched form having 1 to 40 carbon atoms. Alternatively, it is a group selected from the group consisting of a cyclic alkyl group, an aryl group having 6 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 40 carbon atoms and a combination thereof, and the alkyl group. The group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond.)
Since it is configured as described above, the hydroxy-substituted aromatic compound can be industrially advantageously purified by the method for purifying the compound according to the present embodiment. That is, the formula (A. The hydroxy-substituted aromatic compound is dissolved in a solvent, the solution is brought into contact with an ion exchange resin, and an adsorption treatment is performed to convert a metal component as an impurity contained in the solution into an ion exchange resin. After that, the solution and the ion exchange resin can be separated to obtain a hydroxy-substituted aromatic compound in which the amount of metal components is reduced while maintaining high purity.
As described above, "purification" in the present embodiment means an operation of sufficiently reducing the metal component that can coexist with the hydroxy-substituted aromatic compound, and specifically, the Na amount is 50 ppb or less and the Fe amount is 50 ppb. Hereinafter, a hydroxy-substituted aromatic compound having a Cr amount of 50 ppb or less and a Zn amount of 50 ppb or less can be obtained. The amounts of these metal components can be measured by the method described in Examples described later.
The term "contact" in the present embodiment means, for example, a mode in which the solution is brought into contact with the surface of the ion exchange resin, a mode in which the solution is brought into contact with the surface, and the solution is moved outside the ion exchange resin. However, a mode in which the solution passes from the outside of the ion exchange resin through the inside of the ion exchange resin and moves to the outside of the ion exchange resin again (that is, a mode in which the solution is passed) is excluded.

In the method for purifying a compound according to the present embodiment, the hydroxy-substituted aromatic compound is a hydroxy-substituted aromatic compound represented by the following formulas (A) and / or (B) from the viewpoint of raw material supply. Is preferable.

（前記式（Ａ）中、ｎ^０は０〜９の整数であり、ｍ^０は０〜２の整数であり、ｐ^０は０〜９の整数であり、ここで、該ｎ^０、ｍ^０及びｐ^０の少なくとも１つが１以上の整数であり、さらに、ｍ^０が１のとき、前記式（Ａ）はナフタレン骨格又はビフェニル骨格を有することを示し、Ｒ_０は各々独立して、炭素数１〜３０の直鎖状、分岐状若しくは環状のアルキル基、置換基を有していてもよい炭素数６〜１５のアリール基、又は炭素数２〜１５のアルケニル基であり、上記式（Ｂ）中、ｎ^１は０〜９の整数であり、ｐ^１は０〜９の整数であり、Ｒ_１は各々独立して、炭素数１〜３０の直鎖状、分岐状若しくは環状のアルキル基、置換基を有していてもよい炭素数６〜１５のアリール基、又は炭素数２〜１５のアルケニル基である。）

(In the above equation (A), n ⁰ is an integer of ^{0 to 9, m 0} is an integer of 0 to 2, and p ⁰ is an integer of 0 to 9, where n ⁰ and m ^0. And p ⁰ is an integer of 1 or more, and when m ⁰ is 1, the formula (A) indicates that it has a naphthalene skeleton or a biphenyl skeleton, and R ₀ is an independent number of carbon atoms. A linear, branched or cyclic alkyl group of 1 to 30, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms, according to the above formula (B). ), N ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and R ₁ is an independently linear, branched or cyclic alkyl group having 1 to 30 carbon atoms. , An aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms.)

In the method for purifying a compound according to the present embodiment, from the viewpoint of solubility in an organic solvent, the hydroxy-substituted aromatic compound is represented by the compound represented by the following formula (A-1) and the following formula (A-2). 1 selected from the group consisting of the compounds represented by the following formula (A-3), the compounds represented by the following formula (A-4), and the compounds represented by the following formula (B-1) 1 More preferably, it is more than a seed.

（前記式（Ａ−１）中、ｎ^０は１〜５の整数であり、前記式（Ａ−２）中、ｎ^０は０〜７の整数であり、前記式（Ａ−３）〜（Ａ−４）中、ｎ^０は０〜９の整数であり、上記式（Ｂ−１）中、ｎ^１は０〜９の整数である。）

(In the formula (A-1), n ⁰ is an integer of 1 to 5, and in the formula (A-2), n ⁰ is an integer of 0 to 7, and the formulas (A-3) to ( In A-4), n ⁰ is an integer from 0 to 9, and in the above equation (B-1), n ¹ is an integer from 0 to 9.)

In the method for purifying a compound according to the present embodiment, the hydroxy-substituted aromatic compound is particularly preferably a compound represented by the following formula (1) from the viewpoint of raw material supply and purification pot efficiency.

Here, the compound represented by the above formula (1) is not particularly limited, but from the viewpoint of raw material supply, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1 , 5-Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene. One or more selected from the above is preferable.

The compound represented by the above formula (1) is not particularly limited, but from the viewpoint of heat resistance of a compound or a resin obtained by using the compound represented by the formula (1) as a raw material, 2,6-dihydroxynaphthalene and More preferably, one or more selected from the group consisting of 2,7-dihydroxynaphthalene.

The compound represented by the above formula (1) is not particularly limited, but 2,6-dihydroxynaphthalene is further added from the viewpoint of further heat resistance of the compound or resin obtained by using the compound represented by the formula (1) as a raw material. preferable.

_{Formula (A 0} ), formula (B ₀ ), formula (A), formula (B), formula (A-1), formula (A-2), formula (A-3), used in this embodiment, The compounds represented by the formulas (A-4), (B-1) and (1) can be easily obtained by known means such as manufacturers and reagent manufacturers, respectively. Further, a known method can be applied to appropriately synthesize, and the synthesis method is not particularly limited.

_{Formula (A 0} ), formula (B ₀ ), formula (A), formula (B), formula (A-1), formula (A-2), formula (A-3), formula used in this embodiment. The compounds represented by (A-4), the formula (B-1) and the formula (1) may be used alone or in combination of two or more. Further, these compounds may contain various surfactants, various cross-linking agents, various acid generators, various stabilizers and the like.

The solvent used in this embodiment is not particularly limited, but an organic solvent that can be safely applied to the semiconductor manufacturing process is preferable. The amount of the solvent used is usually 1 to 100 times by mass with respect to the compound represented by the formula (1) to be used, which is preferable from the viewpoint of improving solubility and easiness of solid recovery after purification. It is more preferably 5 to 50 times by mass, and even more preferably 10 to 50 times by mass.

Specific examples of the solvent used in this embodiment are not limited to the following, but are not limited to ethyl ether, isopropyl ether, n-butyl ether, hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4 -Methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2- Ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol dibutyl ether, propylene glycol monomethyl Ethers such as ether (PGME), dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol monopropyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpen Tanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec -Undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone Alcohol, monoalcohols such as cresol, diethylca -Bonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-acetate Pentyl, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, acetate Ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i propionate -Pentyl, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, phthalate Esters such as diethyl acid, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl-n-pentyl ketone, ethyl butyl ketone, methylhexyl ketone, diisobutyl ketone, trimethyl Ketones such as nonanone, cyclohexanone, methylcyclohexanone, 2,4-pentandione, acetonylacetone, acetophenone, N-methylpyrrolidone, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA) ), Glycol ether acetates such as propylene glycol monoethyl ether acetate, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N- Nitrogen compound solvents such as methylpropionamide and N-methylpyrrolidone, aliphatic hydrocarbons such as n-hexane and n-heptan, aromatic hydrocarbons such as toluene and xylene, halogenated carbides such as methylene chloride and chloroform. Examples include hydrogens.
The above solvents can be used alone or in combination of two or more.
Among the above, the solvents used are ethyl acetate, butyl acetate, methyl isobutyl ketone, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and cyclo, from the viewpoint of workability and ease of control of the amount charged. It is preferably one or more selected from the group consisting of pentanone and cyclohexanone.

The ion exchange resin used in the present embodiment is not particularly limited, and examples thereof include a resin having a cation exchange ability. More specifically, for example, a resin having a cation-exchangeable functional group such as a sulfonium group or a carboxyl group on the resin surface can be mentioned.

By using an ion exchange resin, Li, Na, Mg, K, Ca, Ni, Co, Fe, Cu, Al, Zn, Sn, Sr, Ti, Pb present in the solution containing the hydroxy-substituted aromatic compound , Cr, Mo, Cd, Ba and the like can be removed by ion exchange with the functional group H on the resin surface.

The amount of the ion exchange resin used is determined by the balance between the amount of metal ions to be removed and the ion exchange capacity of the ion exchange resin, and is not particularly limited, but the exchange capacity of the above ion exchange resin is removed. It is preferable to set it so as to exceed 10 times the amount of metal ions to be used.

The method of using the ion exchange resin is not particularly limited, but for example, the ion exchange resin is preferably made into a slurry with a solvent, packed in a column, and the column contains a hydroxy-substituted aromatic compound. There is a column method in which a liquid is passed, or a decantation method in which a solution containing a hydroxy-substituted aromatic compound is mixed with an ion exchange resin, dispersed for an arbitrary time, allowed to stand, and then filtered to remove the ion exchange resin. Among the above, the column method is particularly preferable.

In the above column method, the amount of the solvent used when the ion exchange resin is made into a slurry is not particularly limited, but is usually about 1 to 100 times by mass with respect to the hydroxy-substituted aromatic compound, which is preferable. Is 1 to 10 times by mass, more preferably 5 to 10 times by mass.

Further, the temperature at which the column is filled with the ion exchange resin in the form of a slurry and the solution containing the hydroxy-substituted aromatic compound is passed through the column is not particularly limited, but is usually 0 to 60 ° C. It is preferably 0 to 40 ° C, more preferably 10 to 40 ° C.

In the above decantation method, the pot for mixing the solution (A) containing the hydroxy-substituted aromatic compound and the ion exchange resin is a stainless steel material subjected to electropolishing, a stainless steel material subjected to glass lining treatment, or a fluororesin lining treatment. The stainless steel material that has been subjected to the above is preferable, and the stainless steel material that has been subjected to the fluororesin lining treatment is particularly preferable.

In the decantation method, the time for mixing and dispersing the solution (A) containing the hydroxy-substituted aromatic compound and the ion exchange resin is preferably at least 10 minutes or more, and more preferably 30 minutes or more. The time for standing still is preferably 30 minutes or more, more preferably 1 hour or more.

In the decantation method, the method for removing the ion exchange resin by filtration is not particularly limited, and known suction filtration, pressure filtration, centrifugation and the like can be used.

In addition, at least one type of packing member such as an O-ring contained in the lid, bottom portion, connecting joint, and cock of each device is made of perfluoro rubber or perfluoro elastomer, and all of these components are made of fluorine-containing resin. It is preferably composed of a material selected from perfluoro rubber and perfluoro elastomer. Further, it is particularly preferable that the packing member is made of a material selected from perfluoro rubber and perfluoro elastomer. With only members other than these, the metal compound content of the hydroxy-substituted aromatic compound may not be reduced to the ppb level.

The water mixed in the solution containing the hydroxy-substituted aromatic compound and the solvent thus obtained can be easily removed by performing an operation such as vacuum distillation. Further, if necessary, a solvent can be added to adjust the concentration of the hydroxy-substituted aromatic compound to an arbitrary concentration.

The method for obtaining only the hydroxy-substituted aromatic compound from the solution containing the hydroxy-substituted aromatic compound and the solvent is not particularly limited, and is carried out by a known method such as removal under reduced pressure, separation by reprecipitation, and a combination thereof. Can be done. If necessary, known treatments such as concentration operation, filtration operation, centrifugation operation, and drying operation can be performed.

Further, the contact between the solution and the ion exchange resin in the present embodiment is preferably performed in an atmosphere having an oxygen concentration of less than 20%. The oxygen concentration is more preferably less than 10%, even more preferably less than 5%, and particularly preferably less than 1%. By setting the oxygen concentration to less than 20%, the alteration of the hydroxy-substituted aromatic compound tends to be further suppressed, and a higher-purity hydroxy-substituted aromatic compound tends to be obtained.

The method for lowering the oxygen concentration can be carried out by a known method and is not particularly limited. For example, gas replacement can be performed by flowing nitrogen through a column or a kettle for purification, or by reducing the pressure and then introducing nitrogen. It can be carried out. It is convenient, reliable and preferable to reduce the pressure of the column or kettle to be purified and then introduce nitrogen.

The oxygen concentration can be confirmed by a known method and is not particularly limited. For example, nitrogen is flowed through a column or a kettle for purification, and the oxygen concentration of the gas discharged from the vent is measured with an oxygen concentration meter. can do. An oximeter can also be installed on the column or kettle for purification.

Hereinafter, the present embodiment will be described in more detail with reference to examples. However, this embodiment is not limited to these examples.

(Example 1) Metal reduction treatment by column method In a class 1000 clean booth, 25 g of ion exchange resin (Mitsubishi Chemical Diaion: SMT100-mix resin) is swollen with 25 mL of propylene glycol monomethyl ether (hereinafter, also referred to as PGME). After that, the column was filled with Teflon (registered trademark), and 500 mL of PGME was passed through the column to replace the solvent. Next, 500 g of a solution (2.5% by mass) in which 2,6-dihydroxynaphthalene (hereinafter, also referred to as 2,6-DHN) having a purity of 99.3% was dissolved in PGME was charged into the column, and then inside the column. PGME of 2,6-DHN having a purity of 99.3% treated with an ion exchange resin by removing air under reduced pressure, introducing nitrogen gas, adjusting the internal oxygen concentration to less than 1%, and then passing the solution through the solution. A solution was obtained. The oxygen concentration was measured with an oxygen concentration meter "OM-25MF10" manufactured by AS ONE Corporation (the following was also measured in the same manner).

(Example 2) Metal reduction treatment by decantation method In a class 1000 clean booth, 2,6-DHN with a purity of 99.4% was dissolved in PGME in a 1000 mL capacity four-necked flask (bottom punching type). 500 g of the prepared solution (2.5 mass%) was charged, then the air inside the flask was removed under reduced pressure to introduce nitrogen gas, the oxygen concentration inside was adjusted to less than 1%, and then the temperature was raised to 30 ° C. with stirring. Heated. Next, 25 g of an ion exchange resin (Mitsubishi Chemical Diaion: SMT100-mix resin) was added, and the mixture was stirred for 30 minutes and allowed to stand for 1 hour. Next, the ion exchange resin was separated from the 2,6-DHN PGME solution by suction filtration to obtain a 2,6-DHN PGME solution having a reduced metal content and a purity of 99.3%.

(Example 3) Metal reduction treatment by decantation method In a class 1000 clean booth, 2,6-DHN with a purity of 99.4% was dissolved in PGME in a 1000 mL capacity four-necked flask (bottom punching type). 500 g of the prepared solution (2.5% by mass) was charged, and then the air inside the flask was removed under reduced pressure to introduce nitrogen gas, the oxygen concentration inside was adjusted to 5.0%, and then the temperature was 30 ° C. with stirring. Heated up to. Next, 25 g of an ion exchange resin (Mitsubishi Chemical Diaion: SMT100-mix resin) was added, and the mixture was stirred for 30 minutes and allowed to stand for 1 hour. Next, the ion exchange resin was separated from the 2,6-DHN PGME solution by suction filtration to obtain a 2,6-DHN PGME solution having a reduced metal content and a purity of 97.9%.

(Example 4) Metal reduction treatment by decantation method In a class 1000 clean booth, 2,6-DHN with a purity of 99.4% was dissolved in PGME in a 1000 mL capacity four-necked flask (bottom punching type). 500 g of the prepared solution (2.5% by mass) was charged, then the air inside the flask was removed under reduced pressure to introduce nitrogen gas, the oxygen concentration inside was adjusted to 10.2%, and then the temperature was 30 ° C. with stirring. Heated up to. Next, 25 g of an ion exchange resin (Mitsubishi Chemical Diaion: SMT100-mix resin) was added, and the mixture was stirred for 30 minutes and allowed to stand for 1 hour. Next, the ion exchange resin was separated from the 2,6-DHN PGME solution by suction filtration to obtain a 2,6-DHN PGME solution having a reduced metal content and a purity of 97.8%.

(Example 5) Metal reduction treatment by decantation method In a class 1000 clean booth, 2,6-DHN having a purity of 99.4% was dissolved in PGME in a 1000 mL capacity four-necked flask (bottom punching type). 500 g of the prepared solution (2.5% by mass) was charged and heated to 30 ° C. with stirring. Next, 25 g of an ion exchange resin (Mitsubishi Chemical Diaion: SMT100-mix resin) was added, and the mixture was stirred for 30 minutes and allowed to stand for 1 hour. Next, the ion exchange resin was separated from the 2,6-DHN PGME solution by suction filtration to obtain a 2,6-DHN PGME solution having a reduced metal content and a purity of 97.8%.

(Example 6)
In a class 1000 clean booth, 25 g of ion exchange resin (Mitsubishi Chemical Diaion: SMT100-mix resin) is swollen with 25 mL of PGME, then filled in a Teflon (registered trademark) column, and solvent is replaced by passing 500 mL of PGME. bottom. Next, 500 g of a solution (2.5% by mass) in which a crude material of 4,4'-biphenol having a purity of 99.2% was dissolved in PGME was charged into the column, and then the air inside the column was removed under reduced pressure to remove nitrogen gas. Was introduced, the internal oxygen concentration was adjusted to less than 1%, and then the solution was passed through to obtain a PGME solution of 4,4'-biphenol having a purity of 99.2% treated with an ion exchange resin.

(Example 7)
In a class 1000 clean booth, 25 g of ion exchange resin (Mitsubishi Chemical Diaion: SMT100-mix resin) is swollen with 25 mL of PGME, then filled in a Teflon (registered trademark) column, and solvent is replaced by passing 500 mL of PGME. bottom. Next, 500 g of a solution (2.5% by mass) in which a crude product of 99.1% pure resorcinol (1,3-dihydroxybenzene) was dissolved in PGME was charged into the column, and then the air inside the column was removed under reduced pressure. A PGME solution of 99.0% pure resorcinol (1,3-dihydroxybenzene) treated with an ion exchange resin by introducing nitrogen gas, adjusting the internal oxygen concentration to less than 1%, and then passing the solution through. Got

(Example 8)
In a class 1000 clean booth, 25 g of ion exchange resin (Mitsubishi Chemical Diaion: SMT100-mix resin) is swollen with 25 mL of PGME, then filled in a Teflon (registered trademark) column, and solvent is replaced by passing 500 mL of PGME. bottom. Next, 500 g of a solution (2.5% by mass) in which a crude product of 9,10-dihydroxyanthracene having a purity of 98.8% was dissolved in PGME was charged into the column, and then the air inside the column was removed under reduced pressure to remove nitrogen gas. Was introduced, the internal oxygen concentration was adjusted to less than 1%, and then the solution was passed through to obtain a PGME solution of 9,10-dihydroxyanthracene having a purity of 98.8% treated with an ion exchange resin.

(Example 9)
In a class 1000 clean booth, 25 g of ion exchange resin (Mitsubishi Chemical Diaion: SMT100-mix resin) is swollen with 25 mL of PGME, then filled in a Teflon (registered trademark) column, and solvent is replaced by passing 500 mL of PGME. bottom. Next, 500 g of a solution (2.5% by mass) in which a crude material of 1-hydroxypyrene having a purity of 98.9% was dissolved in PGMEA was charged into the column, and then the air inside the column was removed under reduced pressure to introduce nitrogen gas. Then, after adjusting the internal oxygen concentration to less than 1%, the solution was passed through the solution to obtain a PGME solution of resorcinol (1,3-dihydroxybenzene) having a purity of 98.8% treated with an ion exchange resin.

(Comparative Example 1) Purification method without using an ion exchange resin A solution (2.5) in which 2,6-DHN having a purity of 98.7% was dissolved in ethyl acetate in a 1000 mL volume four-necked flask (bottom punching type). 150 g) was charged, and then the air inside the flask was removed under reduced pressure to introduce nitrogen gas, and the mixture was heated to 25 ° C. with stirring to obtain a solution. In this step, the oxygen concentration in the flask was less than 1% by volume. Next, 37.5 g of an aqueous oxalic acid solution (pH 1.3) was added to the obtained solution, and the mixture was stirred for 5 minutes and allowed to stand for 30 minutes. As a result, the oil phase and the aqueous phase were separated, and the aqueous phase was removed. After repeating this operation once, 37.5 g of ultrapure water was added to the obtained oil phase, stirred for 5 minutes, and allowed to stand for 30 minutes to remove the aqueous phase. By repeating this operation three times, an ethyl acetate solution of 2,6-DHN having a reduced metal content and a purity of 98.7% was obtained.

The various metal contents and organic purity of the hydroxy-substituted aromatic compound solutions obtained in Examples 1 to 9 and Comparative Example 1 and the hydroxy-substituted aromatic compound solutions before treatment were measured. In Examples 1 to 9, the solution immediately before the prepared solution comes into contact with the ion exchange resin is used for the above measurement as “before treatment”, and in Comparative Example 1, oxalic acid is added to the prepared solution. It was decided that the solution just before adding the aqueous solution was used for the above measurement as "before treatment". The measurement results are shown in Table 1. Each measurement was carried out under the following equipment and measurement conditions.

[Measurement of various metal contents]
Various metal contents of 2,6-DHN were measured using ICP-MS under the following measurement conditions.
Equipment: ELAN DRCII (manufactured by PerkinElmer)
Temperature: 25 ° C
Environment: Class 100 clean room

[Organic purity measurement]
The organic purity of 2,6-DHN was measured under the following measurement conditions using high performance liquid chromatography.
Equipment: GL-7400 type (manufactured by Hitachi)
Column: X-BRIDE C18
Eluent: acetonitrile / water Temperature: 40 ° C

This application is based on a Japanese patent application filed on September 4, 2015 (Japanese Patent Application No. 2015-174634), the contents of which are incorporated herein by reference.

According to the present invention, the hydroxy-substituted aromatic compound can be industrially advantageously purified, and a high-purity hydroxy-substituted aromatic compound having a reduced metal content can be obtained.

Claims (3)

A method for purifying a hydroxy-substituted aromatic compound represented by the following formulas (A ₀ ) and / or (B _0).
The step of contacting the solution (A) containing the hydroxy-substituted aromatic compound and the solvent with the ion exchange resin is included.
The contact was made in an atmosphere with an oxygen concentration of less than 5%.
The hydroxy-substituted aromatic compounds include 2,6-dihydroxynaphthalene, 4,4'-biphenol, 1,3-dihydroxybenzene, 9,10-dihydroxyanthracene and / or 1-hydroxypyrene.
A method for purifying a hydroxy-substituted aromatic compound after purification, wherein the amount of Na is 50 ppb or less, the amount of Fe is 50 ppb or less, the amount of Cr is 50 ppb or less, and the amount of Zn is 50 ppb or less.

(In the above equation (A ₀ ), n ⁰ is an integer of ^{0 to 9, m 0} is an integer of 0 to 2, and p ⁰ is an integer of 0 to 9, where n ⁰ , m. ^When at least one of 0 and p ⁰ is an integer of 1 or more, and m ⁰ is 1, the above formula (A ₀ ) indicates that it has a naphthalene skeleton or a biphenyl skeleton, and Ra is independently a hydroxyl group. , Halogen groups, linear, branched or cyclic alkyl groups having 1 to 40 carbon atoms, aryl groups having 6 to 40 carbon atoms which may have substituents, or alkenyl groups having 2 to 40 carbon atoms and It is a group selected from the group consisting of a combination thereof, and the alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond. In the above formula (B ₀ ). , N ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and Rb is independently a hydrogen atom, a hydroxyl group, a halogen group, and a linear or branched form having 1 to 40 carbon atoms. Alternatively, it is a group selected from the group consisting of a cyclic alkyl group, an aryl group having 6 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 40 carbon atoms and a combination thereof, and the alkyl group. The group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond.) The method for purifying a compound according to claim 1, wherein in the step, after the contact, the solution (A) is further separated and recovered by filtration. The solvent according to claim 1 or 2, wherein the solvent is at least one selected from the group consisting of ethyl acetate, butyl acetate, methyl isobutyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclopentanone and cyclohexanone. Method for purifying a compound.