JP6952954B2 - Packing method for hydroxy-substituted aromatic compounds - Google Patents
Packing method for hydroxy-substituted aromatic compounds Download PDFInfo
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- JP6952954B2 JP6952954B2 JP2020071226A JP2020071226A JP6952954B2 JP 6952954 B2 JP6952954 B2 JP 6952954B2 JP 2020071226 A JP2020071226 A JP 2020071226A JP 2020071226 A JP2020071226 A JP 2020071226A JP 6952954 B2 JP6952954 B2 JP 6952954B2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/14—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with at least one hydroxy group on a condensed ring system containing two rings
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Description
本発明は、ヒドロキシ置換芳香族化合物（例えば、ジヒドロキシナフタレン）の製造方法及び梱包方法に関する。 The present invention relates to a method for producing a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) and a method for packing.
ヒドロキシ置換芳香族化合物、例えば、ジヒドロキシナフタレンは、半導体用の封止材、コーティング剤、レジスト用材料、半導体下層膜形成材料として使用される化合物又は樹脂の原料として有用である（例えば、特許文献１〜２参照）。また、ヒドロキシ置換芳香族化合物、例えば、ジヒドロキシナフタレンの精製方法として、特定の方法が知られている（例えば、特許文献３参照）。 Hydroxy-substituted aromatic compounds, for example, 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 Document 1). See ~ 2). Further, a specific method is known as a method for purifying a hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene (see, for example, Patent Document 3).
従来、ヒドロキシ置換芳香族化合物、例えば、ジヒドロキシナフタレン（ナフタレンジオール）は一般的に乾燥して用いられる。しかし、その際に同時に劣化を起こし、純度にばらつきが発生するといった問題が顕在化しており、ヒドロキシ置換芳香族化合物、例えば、ジヒドロキシナフタレンの乾燥方法の改善が求められている。
また、従来、一般的にヒドロキシ置換芳香族化合物、例えば、ジヒドロキシナフタレンは保管・運搬の際に梱包されているが、その際に同時に劣化を起こし、純度にばらつきが発生するといった問題が顕在化しており、ヒドロキシ置換芳香族化合物、例えば、ジヒドロキシナフタレンの梱包方法について改善が求められている。
本発明の目的は、乾燥工程におけるヒドロキシ置換芳香族化合物、例えば、ジヒドロキシナフタレンの劣化を抑制し、かつ工業的に有利なヒドロキシ置換芳香族化合物（例えば、ジヒドロキシナフタレン）の製造方法を提供することにある。
また、本発明の第二の目的は、ヒドロキシ置換芳香族化合物、例えば、ジヒドロキシナフタレンの保管・運搬の際の劣化を抑制し、かつ工業的に有利な梱包方法を提供することにある。
Conventionally, hydroxy-substituted aromatic compounds such as dihydroxynaphthalene (naphthalene diol) are generally used after drying. However, at that time, problems such as deterioration occur at the same time and variation in purity has become apparent, and improvement of the drying method of hydroxy-substituted aromatic compounds such as dihydroxynaphthalene is required.
Further, conventionally, hydroxy-substituted aromatic compounds, for example, dihydroxynaphthalene are generally packed at the time of storage and transportation, but at the same time, deterioration occurs at the same time, and a problem that the purity varies becomes apparent. Therefore, improvements are required in the packing method of hydroxy-substituted aromatic compounds such as dihydroxynaphthalene.
An object of the present invention is to provide a method for producing a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) which suppresses deterioration of a hydroxy-substituted aromatic compound in a drying step, for example, dihydroxynaphthalene and is industrially advantageous. be.
A second object of the present invention is to provide a packaging method that suppresses deterioration of a hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene, during storage and transportation, and is industrially advantageous.
本発明者らは上記課題を解決するため鋭意検討した結果、ヒドロキシ置換芳香族化合物（例えば、ジヒドロキシナフタレン）を特定の条件下で乾燥することにより、ヒドロキシ置換芳香族化合物（例えば、ジヒドロキシナフタレン）の劣化を抑制し、高純度のヒドロキシ置換芳香族化合物（例えば、ジヒドロキシナフタレン）を安定的に製造できることを見出し、本発明に至った。
また、本発明者らは上記第二の課題を解決するため鋭意検討した結果、ヒドロキシ置換芳香族化合物（例えば、ジヒドロキシナフタレン）を特定の条件下で梱包することにより、保管・運搬の際の劣化を抑制し高純度を維持したまま保管・運搬できることを見出し、本発明に至った。
As a result of diligent studies to solve the above problems, the present inventors have obtained a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) by drying the hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) under specific conditions. We have found that deterioration can be suppressed and a high-purity hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) can be stably produced, leading to the present invention.
In addition, as a result of diligent studies to solve the above-mentioned second problem, the present inventors have made that a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) is packed under specific conditions, thereby deteriorating during storage and transportation. We have found that it can be stored and transported while maintaining high purity by suppressing the above, and have reached the present invention.
すなわち、本発明はつぎの通りである。
［１］
ヒドロキシ置換芳香族化合物を、酸素濃度が２０体積％未満の雰囲気にて乾燥する工程を含む、ヒドロキシ置換芳香族化合物の製造方法。
［２］
前記ヒドロキシ置換芳香族化合物が、下記式（Ａ０）及び／又は（Ｂ０）で表されるヒドロキシ置換芳香族化合物である、［１］に記載のヒドロキシ置換芳香族化合物の製造方法。
上記式（Ｂ０）中、ｎ１は０〜９の整数であり、ｐ1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。）
［３］
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）で表されるヒドロキシ置換芳香族化合物である、［１］に記載のヒドロキシ置換芳香族化合物の製造方法。
上記式（Ｂ）中、ｎ１は０〜９の整数であり、ｐ1は０〜９の整数であり、Ｒ１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。）
［４］
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］に記載のヒドロキシ置換芳香族化合物の製造方法。
［５］
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］に記載の製造方法。
前記乾燥工程が、還元性物質の存在下で行われる、［１］〜［５］のいずれかに記載の製造方法。
［７］
前記還元性物質が、亜硫酸（塩）、重亜硫酸（塩）、ピロ亜硫酸（塩）、亜二チオン酸（塩）、三チオン酸（塩）、四チオン酸（塩）、チオ硫酸（塩）、ロンガリット、チオ酢酸（塩）、２，３−ジメルカプト−１−プロパノール、ジメチルスルホキサイド、二酸化チオ尿素、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、亜リン酸（塩）及び次亜リン酸（塩）からなる群より選ばれる１種以上である、［６］に記載の製造方法。
［８］
ヒドロキシ置換芳香族化合物を、酸素濃度が２０体積％未満の雰囲気にて梱包する工程を含む、ヒドロキシ置換芳香族化合物の梱包方法。
［９］
前記ヒドロキシ置換芳香族化合物が、下記式（Ａ０）及び／又は（Ｂ０）で表されるヒドロキシ置換芳香族化合物である、［８］に記載のヒドロキシ置換芳香族化合物の梱包方法。
上記式（Ｂ０）中、ｎ１は０〜９の整数であり、ｐ1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。）
［１０］
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）で表されるヒドロキシ置換芳香族化合物である、［８］に記載のヒドロキシ置換芳香族化合物の梱包方法。
上記式（Ｂ）中、ｎ１は０〜９の整数であり、ｐ1は０〜９の整数であり、Ｒ１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。）
［１１］
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、［８］に記載のヒドロキシ置換芳香族化合物の梱包方法。
［１２］
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、［８］に記載の梱包方法。
梱包容器内に前記ヒドロキシ置換芳香族化合物と乾燥剤とを共存させる工程を含む、［８］〜［１２］のいずれかに記載の梱包方法。
［１４］
梱包容器内に前記ヒドロキシ置換芳香族化合物と還元性物質とを共存させる工程を含む、［８］〜［１３］のいずれかに記載の梱包方法。
［１５］
梱包容器内に前記ヒドロキシ置換芳香族化合物と脱酸素剤とを共存させる工程を含む、［８］〜［１４］のいずれかに記載の梱包方法。
［１６］
前記還元性物質が、亜硫酸（塩）、重亜硫酸（塩）、ピロ亜硫酸（塩）、亜二チオン酸（塩）、三チオン酸（塩）、四チオン酸（塩）、チオ硫酸（塩）、ロンガリット、チオ酢酸（塩）、２，３−ジメルカプト−１−プロパノール、ジメチルスルホキサイド、二酸化チオ尿素、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、亜リン酸（塩）及び次亜リン酸（塩）からなる群より選ばれる１種以上である、［１４］に記載の梱包方法。
That is, the present invention is as follows.
[1]
A method for producing a hydroxy-substituted aromatic compound, which comprises a step of drying the hydroxy-substituted aromatic compound in an atmosphere having an oxygen concentration of less than 20% by volume.
[2]
The method for producing a hydroxy-substituted aromatic compound according to [1], wherein the hydroxy-substituted aromatic compound is a hydroxy-substituted aromatic compound represented by the following formulas (A 0 ) and / or (B 0).
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 R b is independently a hydrogen atom, a hydroxyl group, a halogen group, and 1 to 1 carbon atoms. A group consisting of 40 linear, branched or cyclic alkyl groups, an aryl group having 6 to 40 carbon atoms which may have a substituent, or an alkenyl group having 2 to 40 carbon atoms and a combination thereof. , The alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond. )
[3]
The method for producing a hydroxy-substituted aromatic compound according to [1], wherein the hydroxy-substituted aromatic compound is a hydroxy-substituted aromatic compound represented by the following formulas (A) and / or (B).
In 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 independently linear, branched, or having 1 to 30 carbon atoms. It is a cyclic alkyl group, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms. )
[4]
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 producing a hydroxy-substituted aromatic compound according to [1], which is one or more selected from the group consisting of the compound represented by A-4) and the compound represented by the following formula (B-1).
[5]
The production method according to [1], wherein the hydroxy-substituted aromatic compound is a compound represented by the following formula (1).
The production method according to any one of [1] to [5], wherein the drying step is performed in the presence of a reducing substance.
[7]
The reducing substances are sulfite (salt), barite sulfite (salt), pyrosulfite (salt), dithionic acid (salt), trithionic acid (salt), tetrathionic acid (salt), thiosulfate (salt). , Longarit, thioacetic acid (salt), 2,3-dimercapto-1-propanol, dimethylsulfoxide, thiourea dioxide, monomethylamine, dimethylamine, trimethylamine, monoethanolamine, diethanolamine, triethanolamine, phosphite ( The production method according to [6], which is one or more selected from the group consisting of (salt) and hypophosphite (salt).
[8]
A method for packing a hydroxy-substituted aromatic compound, which comprises a step of packing the hydroxy-substituted aromatic compound in an atmosphere having an oxygen concentration of less than 20% by volume.
[9]
The method for packing a hydroxy-substituted aromatic compound according to [8], wherein the hydroxy-substituted aromatic compound is a hydroxy-substituted aromatic compound represented by the following formulas (A 0 ) and / or (B 0).
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 R b is independently a hydrogen atom, a hydroxyl group, a halogen group, and 1 to 1 carbon atoms. A group consisting of 40 linear, branched or cyclic alkyl groups, an aryl group having 6 to 40 carbon atoms which may have a substituent, or an alkenyl group having 2 to 40 carbon atoms and a combination thereof. , The alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond. )
[10]
The method for packing a hydroxy-substituted aromatic compound according to [8], wherein the hydroxy-substituted aromatic compound is a hydroxy-substituted aromatic compound represented by the following formulas (A) and / or (B).
In 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 independently linear, branched, or having 1 to 30 carbon atoms. It is a cyclic alkyl group, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms. )
[11]
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 packing a hydroxy-substituted aromatic compound according to [8], which is one or more selected from the group consisting of the compound represented by A-4) and the compound represented by the following formula (B-1).
[12]
The packing method according to [8], wherein the hydroxy-substituted aromatic compound is a compound represented by the following formula (1).
The packing method according to any one of [8] to [12], which comprises a step of allowing the hydroxy-substituted aromatic compound and the desiccant to coexist in the packing container.
[14]
The packing method according to any one of [8] to [13], which comprises a step of allowing the hydroxy-substituted aromatic compound and the reducing substance to coexist in the packing container.
[15]
The packing method according to any one of [8] to [14], which comprises a step of allowing the hydroxy-substituted aromatic compound and the oxygen scavenger to coexist in the packing container.
[16]
The reducing substances are sulfite (salt), barite sulfite (salt), pyrosulfite (salt), dithionic acid (salt), trithionic acid (salt), tetrathionic acid (salt), thiosulfate (salt). , Longarit, thioacetic acid (salt), 2,3-dimercapto-1-propanol, dimethylsulfoxide, thiourea dioxide, monomethylamine, dimethylamine, trimethylamine, monoethanolamine, diethanolamine, triethanolamine, phosphite ( The packing method according to [14], which is one or more selected from the group consisting of (salt) and hypophosphite (salt).
本発明により、乾燥工程におけるヒドロキシ置換芳香族化合物（例えば、ジヒドロキシナフタレン）の変質や劣化を抑制し、高純度のヒドロキシ置換芳香族化合物（例えば、ジヒドロキシナフタレン）を安定的に製造できる。
また、本発明により、ヒドロキシ置換芳香族化合物（例えば、ジヒドロキシナフタレン）の保管・運搬の際の劣化を抑制し、高純度を安定的に維持可能な梱包方法を提供できる。
INDUSTRIAL APPLICABILITY According to the present invention, alteration and deterioration of a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) in a drying step can be suppressed, and a high-purity hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) can be stably produced.
Further, according to the present invention, it is possible to provide a packaging method capable of stably maintaining high purity by suppressing deterioration of a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) during storage and transportation.
以下、本発明の実施形態（以下「本実施形態」とも記す。）について詳細に説明する。なお、以下の実施形態は、本発明を説明するための例示であり、本発明はその実施形態のみに限定されない。 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.
＜ヒドロキシ置換芳香族化合物の製造方法＞
本実施形態のヒドロキシ置換芳香族化合物の製造方法は、ヒドロキシ置換芳香族化合物を、酸素濃度が２０体積％未満の雰囲気にて乾燥する工程を含む。
本実施形態の製造方法において、前記ヒドロキシ置換芳香族化合物は、フェノール性ヒドロキシ基を少なくとも１個有する芳香族化合物であれば特に限定されないが、例えば、下記式（Ａ０）及び／又は（Ｂ０）で表されるヒドロキシ置換芳香族化合物であることが好ましい。
<Method for producing hydroxy-substituted aromatic compounds>
The method for producing a hydroxy-substituted aromatic compound of the present embodiment includes a step of drying the hydroxy-substituted aromatic compound in an atmosphere having an oxygen concentration of less than 20% by volume.
In the production method of the present embodiment, the hydroxy-substituted aromatic compound is not particularly limited as long as it is an aromatic compound having at least one phenolic hydroxy group, and is, for example, the following formula (A 0 ) and / or (B 0). ) Is preferably a hydroxy-substituted aromatic compound.
上記式（Ｂ０）中、ｎ１は０〜９の整数であり、ｐ1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。）
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 R b is independently a hydrogen atom, a hydroxyl group, a halogen group, and 1 to 1 carbon atoms. A group consisting of 40 linear, branched or cyclic alkyl groups, an aryl group having 6 to 40 carbon atoms which may have a substituent, or an alkenyl group having 2 to 40 carbon atoms and a combination thereof. , The alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond. )
また、本実施形態の製造方法において、前記ヒドロキシ置換芳香族化合物は、下記式（Ａ）及び／又は（Ｂ）で表されるヒドロキシ置換芳香族化合物であることがより好ましい。 Further, in the production method of the present embodiment, the hydroxy-substituted aromatic compound is more preferably a hydroxy-substituted aromatic compound represented by the following formulas (A) and / or (B).
上記式（Ｂ）中、ｎ１は０〜９の整数であり、ｐ1は０〜９の整数であり、Ｒ１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 formula (B), n 1 is an integer of 0 to 9, p 1 is an integer of 0 to 9, and R 1 is independently linear, branched, or having 1 to 30 carbon atoms. It is a cyclic alkyl group, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms. )
本実施形態の製造方法において、前記ヒドロキシ置換芳香族化合物は、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種以上であることがさらに好ましい。 In the production method of the present embodiment, the hydroxy-substituted aromatic compound is represented by the following formula (A-1), the compound represented by the following formula (A-2), and the following formula (A-3). It is more preferable that the compound is one or more selected from the group consisting of a compound represented by the following formula, a compound represented by the following formula (A-4), and a compound represented by the following formula (B-1).
本実施形態の製造方法において、前記ヒドロキシ置換芳香族化合物は、下記式（１）で表される化合物であることが特に好ましい。 In the production method of the present embodiment, the hydroxy-substituted aromatic compound is particularly preferably a compound represented by the following formula (1).
ヒドロキシ置換芳香族化合物、例えば、ジヒドロキシナフタレンは二量体を生成し易いという問題があったが、該化合物を酸素濃度が２０体積％未満の雰囲気にて乾燥することにより、該化合物の酸化による二量体等の副生成物の生成を抑制し、安定的に高純度の該化合物を製造することが可能になる。 A hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene, has a problem that it easily forms a dimer. However, by drying the compound in an atmosphere having an oxygen concentration of less than 20% by volume, the compound is oxidized. It is possible to stably produce the compound having high purity by suppressing the formation of by-products such as a dimer.
本実施形態の製造方法において、乾燥工程の酸素濃度は１０体積％未満が好ましく、５体積％未満がより好ましく、１体積％未満がさらに好ましい。乾燥工程の酸素濃度が低いほど、ヒドロキシ置換芳香族化合物、例えば、ジヒドロキシナフタレンの変質を抑制し得る。乾燥工程の酸素濃度の下限は、特に限定されないが、例えば、０．０１体積％である。 In the production method of the present embodiment, the oxygen concentration in the drying step is preferably less than 10% by volume, more preferably less than 5% by volume, and even more preferably less than 1% by volume. The lower the oxygen concentration in the drying step, the more the alteration of the hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene, can be suppressed. The lower limit of the oxygen concentration in the drying step is not particularly limited, but is, for example, 0.01% by volume.
酸素濃度を低下させる方法は、公知の方法が適用でき、特に限定されないが、例えば、酸素以外のガスを主成分とするガスを乾燥機内に供給する方法を挙げることができる。乾燥機を減圧して真空下で行う方法も挙げることができる。 A known method can be applied as a method for lowering the oxygen concentration, and the method is not particularly limited, and examples thereof include a method of supplying a gas containing a gas other than oxygen as a main component into the dryer. A method of depressurizing the dryer and performing it under vacuum can also be mentioned.
酸素濃度の確認は、公知の方法で実施でき、特に限定されないが、例えば、乾燥機に窒素ガスをフローして、ベントから排出されるガスの酸素濃度を、酸素濃度計にて測定する方法を挙げることができる。乾燥機に酸素濃度計を設置する方法も挙げることができる。 The oxygen concentration can be confirmed by a known method and is not particularly limited. For example, a method in which nitrogen gas is flowed through a dryer and the oxygen concentration of the gas discharged from the vent is measured with an oxygen concentration meter. Can be mentioned. A method of installing an oxygen concentration meter in the dryer can also be mentioned.
乾燥温度はヒドロキシ置換芳香族化合物、例えば、ジヒドロキシナフタレンの変質を抑制できれば特に限定されないが、通常、１０〜２３０℃の範囲が好ましい。
乾燥温度が１０℃以上の温度であれば未乾燥物が生じにくい傾向にある。また、乾燥温度が２３０℃未満の温度であればヒドロキシ置換芳香族化合物、例えば、ジヒドロキシナフタレンの変質が起こりにくい傾向にある。より好ましい乾燥温度は、５０〜１００℃、さらに好ましい乾燥温度は、６０〜９０℃である。
乾燥時間は特に限定されないが、通常、３０分〜１週間が好ましい。より好ましくは、４５分〜１日、さらに好ましくは１時間〜１２時間である。また、乾燥圧力は減圧、常圧及び加圧のいずれでも適用し得る。
The drying temperature is not particularly limited as long as it can suppress the alteration of the hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene, but is usually preferably in the range of 10 to 230 ° C.
If the drying temperature is 10 ° C. or higher, undried products tend to be less likely to occur. Further, if the drying temperature is less than 230 ° C., alteration of the hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene tends to be less likely to occur. A more preferable drying temperature is 50 to 100 ° C., and a more preferable drying temperature is 60 to 90 ° C.
The drying time is not particularly limited, but is usually preferably 30 minutes to 1 week. More preferably, it is 45 minutes to 1 day, and further preferably 1 hour to 12 hours. Further, the drying pressure can be applied to any of reduced pressure, normal pressure and pressurization.
本実施形態の製造方法で使用されるヒドロキシ置換芳香族化合物は、下記式（１）で表される化合物であることが特に好ましい。 The hydroxy-substituted aromatic compound used in the production method of the present embodiment is particularly preferably a compound represented by the following formula (1).
ここで、上記式（１）で表される化合物は、特に限定されないが、原料の供給性の観点から、１，２−ジヒドロキシナフタレン、１，３−ジヒドロキシナフタレン、１，４−ジヒドロキシナフタレン、１，５−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、１，７−ジヒドロキシナフタレン、１，８−ジヒドロキシナフタレン、２，３−ジヒドロキシナフタレン、２，６−ジヒドロキシナフタレ及び２，７−ジヒドロキシナフタレンからなる群から選ばれる１種以上が好ましい。 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 group is preferable.
また、上記式（１）で表される化合物は、特に限定されないが、該化合物を原料として得られる化合物又は樹脂の耐熱性の観点から、２，６−ジヒドロキシナフタレ及び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種以上がより好ましい。 The compound represented by the above formula (1) is not particularly limited, but from the viewpoint of heat resistance of the compound or resin obtained from the compound as a raw material, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene are used. More preferably, one or more selected from the group consisting of.
上記式（１）で表される化合物は、特に限定されないが、該化合物を原料として得られる化合物又は樹脂のさらなる耐熱性の観点から、２，６−ジヒドロキシナフタレンがさらに好ましい。 The compound represented by the above formula (1) is not particularly limited, but 2,6-dihydroxynaphthalene is more preferable from the viewpoint of further heat resistance of the compound or resin obtained from the compound as a raw material.
上記式（１）で表される化合物は、製造メーカー及び試薬メーカー等公知の手段にて容易に入手できる。また、公知の手法を応用して適宜合成することができ、その合成手法は特に限定されない。 The compound represented by the above formula (1) can be easily obtained by known means such as a manufacturer and a reagent manufacturer. Further, a known method can be applied and appropriately synthesized, and the synthesis method is not particularly limited.
本実施形態の製造方法においてヒドロキシ置換芳香族化合物は単独で使用してもよいが、２種以上混合して使用することもできる。また、ヒドロキシ置換芳香族化合物は、各種界面活性剤、各種架橋剤、各種酸発生剤、各種安定剤等を含有したものであってもよい。 In the production method of the present embodiment, the hydroxy-substituted aromatic compound may be used alone, or two or more kinds may be mixed and used. Further, the hydroxy-substituted aromatic compound may contain various surfactants, various cross-linking agents, various acid generators, various stabilizers and the like.
本実施形態の製造方法では、前記乾燥工程が、還元性物質の存在下で行われることが好ましい。すなわち、ヒドロキシ置換芳香族化合物を還元性物質の存在下で乾燥することが好ましい。ヒドロキシ置換芳香族化合物に還元性物質を添加した後、乾燥工程に供すると更に劣化を抑制することができる場合がある。還元性物質としては、特に限定されないが、例えば、亜硫酸（塩）、重亜硫酸（塩）、ピロ亜硫酸（塩）、亜二チオン酸（塩）、三チオン酸（塩）、四チオン酸（塩）、チオ硫酸（塩）、ロンガリット、チオ酢酸（塩）、２，３−ジメルカプト−１−プロパノール、ジメチルスルホキサイド、二酸化チオ尿素等の含イオウ原子還元性物質；モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等の有機アミン類；亜リン酸（塩）、次亜リン酸（塩）等の含リン原子還元性物質などを挙げることができる。これらの中でも、安価且つ工業的に入手し易くしかも効果の高い重亜硫酸（塩）の使用が好ましい。
これらの還元性物質は１種単独で用いてもよく、２種以上併用してもよい。
In the production method of the present embodiment, it is preferable that the drying step is performed in the presence of a reducing substance. That is, it is preferable to dry the hydroxy-substituted aromatic compound in the presence of a reducing substance. When a reducing substance is added to the hydroxy-substituted aromatic compound and then subjected to a drying step, deterioration may be further suppressed. The reducing substance is not particularly limited, but for example, sulfite (salt), barous sulfate (salt), pyrosulfate (salt), dithionic acid (salt), trithioic acid (salt), tetrathioic acid (salt). ), Thiosulfate (salt), longalite, thioacetic acid (salt), 2,3-dimercapto-1-propanol, dimethylsulfoxide, thiourea dioxide and other sulfur-containing atomic reducing substances; monomethylamine, dimethylamine, trimethylamine , Organic amines such as monoethanolamine, diethanolamine, triethanolamine; phosphorus-containing atomic reducing substances such as phosphite (salt) and hypophosphite (salt) can be mentioned. Among these, it is preferable to use sodium bisulfite (salt), which is inexpensive, industrially easily available, and highly effective.
These reducing substances may be used alone or in combination of two or more.
本実施形態の製造方法において、これら還元性物質の使用量は、ヒドロキシ置換芳香族化合物１００質量部に対して０．０１〜５質量部の範囲が好ましく、より好ましくは０．０５〜３質量部、さらに好ましくは０．１〜１質量部である。また、これら還元性物質を使用した場合、酸素濃度が比較的高い場合でも、熱劣化の全くないヒドロキシ置換芳香族化合物（例えば、ジヒドロキシナフタレン）を得ることが可能な場合がある。そのため安価な製品を製造する場合には有効な手段となり得る。 In the production method of the present embodiment, the amount of these reducing substances used is preferably in the range of 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the hydroxy-substituted aromatic compound. , More preferably 0.1 to 1 part by mass. Further, when these reducing substances are used, it may be possible to obtain a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) having no thermal deterioration even when the oxygen concentration is relatively high. Therefore, it can be an effective means for manufacturing inexpensive products.
＜ヒドロキシ置換芳香族化合物の梱包方法＞
本実施形態のヒドロキシ置換芳香族化合物の梱包方法は、ヒドロキシ置換芳香族化合物を、酸素濃度が２０％未満の雰囲気にて梱包する工程を含む。
<Packing method of hydroxy-substituted aromatic compounds>
The packing method of the hydroxy-substituted aromatic compound of the present embodiment includes a step of packing the hydroxy-substituted aromatic compound in an atmosphere having an oxygen concentration of less than 20%.
本実施形態の梱包方法において、前記ヒドロキシ置換芳香族化合物は、フェノール性ヒドロキシ基を少なくとも１個有する芳香族化合物であれば特に限定されないが、例えば、下記式（Ａ０）及び／又は（Ｂ０）で表されるヒドロキシ置換芳香族化合物であることが好ましい。 In the packing method of the present embodiment, the hydroxy-substituted aromatic compound is not particularly limited as long as it is an aromatic compound having at least one phenolic hydroxy group, and is, for example, the following formula (A 0 ) and / or (B 0). ) Is preferably a hydroxy-substituted aromatic compound.
上記式（Ｂ０）中、ｎ１は０〜９の整数であり、ｐ1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。）
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 R b is independently a hydrogen atom, a hydroxyl group, a halogen group, and 1 to 1 carbon atoms. A group consisting of 40 linear, branched or cyclic alkyl groups, an aryl group having 6 to 40 carbon atoms which may have a substituent, or an alkenyl group having 2 to 40 carbon atoms and a combination thereof. , The alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond. )
また、本実施形態の梱包方法において、前記ヒドロキシ置換芳香族化合物は、下記式（Ａ）及び／又は（Ｂ）で表されるヒドロキシ置換芳香族化合物であることがより好ましい。 Further, in the packing method of the present embodiment, the hydroxy-substituted aromatic compound is more preferably a hydroxy-substituted aromatic compound represented by the following formulas (A) and / or (B).
上記式（Ｂ）中、ｎ１は０〜９の整数であり、ｐ1は０〜９の整数であり、Ｒ１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 formula (B), n 1 is an integer of 0 to 9, p 1 is an integer of 0 to 9, and R 1 is independently linear, branched, or having 1 to 30 carbon atoms. It is a cyclic alkyl group, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms. )
本実施形態の梱包方法において、前記ヒドロキシ置換芳香族化合物は、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種以上であることがさらに好ましい。 In the packing method of the present embodiment, the hydroxy-substituted aromatic compound is represented by the following formula (A-1), the compound represented by the following formula (A-2), and the following formula (A-3). It is more preferable that the compound is one or more selected from the group consisting of a compound represented by the following formula, a compound represented by the following formula (A-4), and a compound represented by the following formula (B-1).
また、本実施形態の梱包方法において、前記式（Ａ）で表されるヒドロキシ置換芳香族化合物は、下記式（１）で表される化合物であることが特に好ましい。 Further, in the packing method of the present embodiment, the hydroxy-substituted aromatic compound represented by the formula (A) is particularly preferably a compound represented by the following formula (1).
ヒドロキシ置換芳香族化合物、例えば、ジヒドロキシナフタレンは二量体を生成し易いという問題があったが、該化合物を酸素濃度が２０体積％未満の雰囲気にて梱包することにより、該化合物の酸化による二量体等の副生成物の生成を抑制し、高純度を維持したまま保管・輸送することが可能になる。 A hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene, has a problem that it easily forms a dimer. However, by packing the compound in an atmosphere having an oxygen concentration of less than 20% by volume, the compound is oxidized. By suppressing the formation of by-products such as dimers, it becomes possible to store and transport while maintaining high purity.
本実施形態の梱包方法において、梱包工程の酸素濃度は１０体積％未満が好ましく、５体積％未満がより好ましく、１体積％未満がさらに好ましい。梱包工程の酸素濃度が低いほど、ヒドロキシ置換芳香族化合物、例えば、ジヒドロキシナフタレンの変質を抑制することができる。梱包工程の酸素濃度の下限は、特に限定されないが、例えば、０．０１体積％である。 In the packing method of the present embodiment, the oxygen concentration in the packing step is preferably less than 10% by volume, more preferably less than 5% by volume, and even more preferably less than 1% by volume. The lower the oxygen concentration in the packing step, the more the alteration of the hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene can be suppressed. The lower limit of the oxygen concentration in the packing step is not particularly limited, but is, for example, 0.01% by volume.
酸素濃度を低下させる方法は、公知の方法が適用でき、特に限定されないが、例えば、梱包容器に窒素ガスをフローして、又は減圧してその後窒素ガスを導入することで、ガス置換を行う方法を挙げることができる。もしくは減圧して真空下で行う方法も挙げることができる。梱包容器を減圧してその後窒素ガスを導入する方法ことが簡便かつ確実で好ましい。 A known method can be applied to reduce the oxygen concentration, and the method is not particularly limited. For example, a method of performing gas replacement by flowing nitrogen gas into a packaging container or reducing the pressure and then introducing nitrogen gas. Can be mentioned. Alternatively, a method of reducing the pressure and performing under vacuum can be mentioned. A method of depressurizing the packing container and then introducing nitrogen gas is convenient, reliable and preferable.
本実施形態の梱包方法で使用されるヒドロキシ置換芳香族化合物は、下記式（１）で表される化合物であることが特に好ましい。 The hydroxy-substituted aromatic compound used in the packaging method of the present embodiment is particularly preferably a compound represented by the following formula (1).
ここで、上記式（１）で表される化合物は、特に限定されないが、原料の供給性の観点から、１，２−ジヒドロキシナフタレン、１，３−ジヒドロキシナフタレン、１，４−ジヒドロキシナフタレン、１，５−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、１，７−ジヒドロキシナフタレン、１，８−ジヒドロキシナフタレン、２，３−ジヒドロキシナフタレン、２，６−ジヒドロキシナフタレ及び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種以上が好ましい。 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 group is preferable.
また、上記式（１）で表される化合物は、特に限定されないが、該化合物を原料として得られる化合物又は樹脂の耐熱性の観点から、２，６−ジヒドロキシナフタレ及び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種以上がより好ましい。 The compound represented by the above formula (1) is not particularly limited, but from the viewpoint of heat resistance of the compound or resin obtained from the compound as a raw material, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene are used. More preferably, one or more selected from the group consisting of.
上記式（１）で表される化合物は、特に限定されないが、該化合物を原料として得られる化合物又は樹脂のさらなる耐熱性の観点から、２，６−ジヒドロキシナフタレンがさらに好ましい。 The compound represented by the above formula (1) is not particularly limited, but 2,6-dihydroxynaphthalene is more preferable from the viewpoint of further heat resistance of the compound or resin obtained from the compound as a raw material.
上記式（１）で表される化合物は、製造メーカー及び試薬メーカー等公知の手段にて容易に入手できる。また、公知の手法を応用して適宜合成することができ、その合成手法は特に限定されない。 The compound represented by the above formula (1) can be easily obtained by known means such as a manufacturer and a reagent manufacturer. Further, a known method can be applied and appropriately synthesized, and the synthesis method is not particularly limited.
本実施形態の梱包方法において、ヒドロキシ置換芳香族化合物は単独で使用してもよいが、２種以上混合して使用することもできる。また、ヒドロキシ置換芳香族化合物は、各種界面活性剤、各種架橋剤、各種酸発生剤、各種安定剤等を含有したものであってもよい。 In the packing method of the present embodiment, the hydroxy-substituted aromatic compound may be used alone, or two or more kinds may be mixed and used. Further, the hydroxy-substituted aromatic compound may contain various surfactants, various cross-linking agents, various acid generators, various stabilizers and the like.
本実施形態の梱包方法において、梱包形態は、公知の形態が適用でき、特に限定されない。例えば、梱包用の容器としては、ポリエチレン、ポリプロピレン、ナイロン若しくはポリエチレンテレフタレート等を素材とする樹脂フィルム袋、アルミ袋、それらの多層フィルム袋又はそれらの組み合わせ等が挙げられる。さらに劣化を抑制する観点から、アルミラミネートしたフィルムを使用することが好ましい。
また、封は、輪ゴム、ガムテープやビニールテープあるいはヒートシール等の方法により行うことができるが、さらに劣化を抑制する観点から、ヒートシールが好ましい。
In the packing method of the present embodiment, known forms can be applied to the packing form, and the packing form is not particularly limited. For example, examples of the packaging container include a resin film bag made of polyethylene, polypropylene, nylon, polyethylene terephthalate, or the like, an aluminum bag, a multilayer film bag thereof, or a combination thereof. Further, from the viewpoint of suppressing deterioration, it is preferable to use an aluminum-laminated film.
Further, the sealing can be performed by a method such as rubber band, gum tape, vinyl tape or heat sealing, but from the viewpoint of further suppressing deterioration, heat sealing is preferable.
製品の保護及び内容物の表示等のために外装材を用いることもできる。外装材としては、公知の形態が適用でき、特に限定されないが、例えば、段ボール、ファイバードラム、ペール缶、金属缶、ガラス容器等が挙げられる。また、それらの蓋の固定には、ビニールテープ、かしめあるいは金属バンド等が用いられる。 Exterior materials can also be used to protect the product and display the contents. As the exterior material, known forms can be applied, and the exterior material is not particularly limited, and examples thereof include corrugated cardboard, fiber drums, pail cans, metal cans, and glass containers. Further, vinyl tape, caulking, a metal band, or the like is used to fix the lids.
本実施形態の梱包方法において、梱包容器内にヒドロキシ置換芳香族化合物と乾燥剤とを共存させる工程を含むことが、ヒドロキシ置換芳香族化合物の変質抑制の観点からより好ましい。乾燥剤としては、公知のものが使用でき、特に限定されないが、例えば、シリカゲル、酸化アルミニウム等が挙げられる。
これらの乾燥剤は１種単独で用いてもよく、２種以上併用してもよい。
In the packing method of the present embodiment, it is more preferable to include a step of coexisting the hydroxy-substituted aromatic compound and the desiccant in the packing container from the viewpoint of suppressing deterioration of the hydroxy-substituted aromatic compound. As the desiccant, known ones can be used, and the desiccant is not particularly limited, and examples thereof include silica gel and aluminum oxide.
These desiccants may be used alone or in combination of two or more.
本実施形態の梱包方法において、梱包容器内にヒドロキシ置換芳香族化合物と還元性物質とを共存させる工程を含むことが、該化合物の変質抑制の観点からより好ましい。ヒドロキシ置換芳香族化合物に還元性物質を添加した後、乾燥工程に供すると更に劣化を抑制することができる場合がある。また、還元性物質をヒドロキシ置換芳香族化合物に添加せずに梱包容器内に配置することでも効果がある場合がある。 In the packing method of the present embodiment, it is more preferable to include a step of coexisting the hydroxy-substituted aromatic compound and the reducing substance in the packing container from the viewpoint of suppressing deterioration of the compound. When a reducing substance is added to the hydroxy-substituted aromatic compound and then subjected to a drying step, deterioration may be further suppressed. It may also be effective to place the reducing substance in the packaging container without adding it to the hydroxy-substituted aromatic compound.
上記還元性物質としては、特に限定されないが、例えば、亜硫酸（塩）、重亜硫酸（塩）、ピロ亜硫酸（塩）、亜二チオン酸（塩）、三チオン酸（塩）、四チオン酸（塩）、チオ硫酸（塩）、ロンガリット、チオ酢酸（塩）、２，３−ジメルカプト−１−プロパノール、ジメチルスルホキサイド、二酸化チオ尿素等の含イオウ原子還元性物質；モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等の有機アミン類；亜リン酸（塩）、次亜リン酸（塩）等の含リン原子還元性物質などを挙げることができる。これらの中でも、安価且つ工業的に入手し易く、しかも効果の高い重亜硫酸（塩）の使用が好ましい。
これらの還元性物質は１種単独で用いてもよく、２種以上併用してもよい。
The reducing substance is not particularly limited, but for example, sulfite (salt), barous sulfate (salt), pyrosulfate (salt), dithionic acid (salt), trithioic acid (salt), tetrathioic acid (salt). Sulfur-containing atomic reducing substances such as salt), thiosulfate (salt), longalite, thioacetic acid (salt), 2,3-dimercapto-1-propanol, dimethylsulfoxide, thiourea dioxide; monomethylamine, dimethylamine, Organic amines such as trimethylamine, monoethanolamine, diethanolamine and triethanolamine; phosphorus-containing atomic reducing substances such as phosphite (salt) and hypophosphite (salt) can be mentioned. Among these, it is preferable to use sodium bisulfite (salt), which is inexpensive, industrially easily available, and highly effective.
These reducing substances may be used alone or in combination of two or more.
本実施形態の梱包方法において、これら還元性物質の使用量は、ヒドロキシ置換芳香族化合物１００質量部に対して、０．０１〜５質量部の範囲が好ましく、０．０５〜３質量部の範囲がより好ましく、０．１〜１質量部の範囲がさらに好ましい。
また、これら還元性物質を使用した場合、酸素濃度が比較的高い場合でも、熱劣化の全くないヒドロキシ置換芳香族化合物（例えば、ジヒドロキシナフタレン）を得ることが可能な場合があるため、安価な製品を製造する場合には特に有効な手段となり得るものである。
In the packing method of the present embodiment, the amount of these reducing substances used is preferably in the range of 0.01 to 5 parts by mass, preferably in the range of 0.05 to 3 parts by mass with respect to 100 parts by mass of the hydroxy-substituted aromatic compound. Is more preferable, and the range of 0.1 to 1 part by mass is further preferable.
Further, when these reducing substances are used, it may be possible to obtain a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) having no thermal deterioration even when the oxygen concentration is relatively high, so that it is an inexpensive product. It can be a particularly effective means in the production of.
本実施形態の梱包方法において、梱包した容器内にヒドロキシ置換芳香族化合物と脱酸素剤とを共存させる工程を含むことが、該化合物の変質抑制の観点からより好ましい。脱酸素剤としては、特に限定されないが、鉄を主成分とする無機系脱酸素剤、フェノール類、アスコルビン酸、グリセリン、糖アルコールまたは不飽和脂肪酸を主成分とするものが挙げられる。これらの中でも、安価且つ工業的に入手し易く、しかも効果の高い鉄を主成分とする無機系脱酸素剤が好ましい。このような無機系脱酸素剤としては、例えば、三菱ガス化学（株）社製エージレス等の製品名で知られるもの挙げられる。
これらの脱酸素剤は１種単独で用いてもよく、２種以上併用してもよい。
In the packing method of the present embodiment, it is more preferable to include a step of coexisting a hydroxy-substituted aromatic compound and an oxygen scavenger in the packed container from the viewpoint of suppressing deterioration of the compound. The oxygen scavenger is not particularly limited, and examples thereof include an inorganic oxygen scavenger containing iron as a main component, phenols, ascorbic acid, glycerin, a sugar alcohol, and an unsaturated fatty acid as a main component. Among these, an inorganic oxygen scavenger containing iron as a main component, which is inexpensive, industrially easily available, and highly effective, is preferable. Examples of such an inorganic oxygen scavenger include those known by product names such as Ageless manufactured by Mitsubishi Gas Chemical Company, Inc.
These oxygen scavengers may be used alone or in combination of two or more.
本実施形態の梱包方法において、これら脱酸素剤の使用量は、ヒドロキシ置換芳香族化合物１００質量部に対して、０．０１〜５質量部の範囲が好ましく、０．０５〜３質量部の範囲がより好ましく、０．１〜１質量部の範囲がさらに好ましい。
また、これら脱酸素剤を使用した場合、梱包時の酸素濃度が比較的高い場合でも、梱包後に速やかに酸素濃度を低減することが可能となり、設備投資を行わず品質の優れた製品を製造する場合に特に有効な手段となり得るものである。
In the packaging method of the present embodiment, the amount of these oxygen scavengers used is preferably in the range of 0.01 to 5 parts by mass, preferably in the range of 0.05 to 3 parts by mass with respect to 100 parts by mass of the hydroxy-substituted aromatic compound. Is more preferable, and the range of 0.1 to 1 part by mass is further preferable.
In addition, when these oxygen scavengers are used, even if the oxygen concentration at the time of packing is relatively high, the oxygen concentration can be reduced promptly after packing, and a product with excellent quality can be manufactured without making capital investment. It can be a particularly effective means in some cases.
以下、実施例を挙げて、本実施形態をさらに具体的に説明する。但し、本実施形態は、これらの実施例に限定されない。 Hereinafter, the present embodiment will be described in more detail with reference to examples. However, this embodiment is not limited to these examples.
加熱減量測定法：各乾燥機にナフタレンジオール約１ｇを取り、所定の乾燥条件で乾燥し、次式により算出した。
加熱減量（％）＝（Ａ−Ｂ）／Ａ×１００
Ａ：採取したナフタレンジオールの重量（ｇ）
Ｂ：乾燥後の重量（ｇ）
Heat loss measurement method: About 1 g of naphthalene diol was taken in each dryer, dried under predetermined drying conditions, and calculated by the following formula.
Heat loss (%) = (AB) / A × 100
A: Weight of collected naphthalene diol (g)
B: Weight after drying (g)
（実施例１）
含水率１０質量％かつ純度８９．０％の２，６−ジヒドロキシナフタレン粗体１ｇを、ＥＳＰＥＣ社製真空乾燥機（ＶＡＣＵＵＭ ＯＶＥＮ ＬＣＶ−２３３）に入れ、真空下、８０℃で２４時間乾燥を行った。その際の酸素濃度は１体積％未満であった。
その結果、加熱減量は１０質量％であり、純度９９．０％の２，６−ジヒドロキシナフタレン０．９ｇを得た。
２，６−ジヒドロキシナフタレンの劣化を抑制して乾燥することができた。
(Example 1)
1 g of a crude 2,6-dihydroxynaphthalene having a water content of 10% by mass and a purity of 89.0% was placed in a vacuum dryer (VACUUM OVEN LCV-233) manufactured by ESPEC, and dried at 80 ° C. for 24 hours under vacuum. rice field. The oxygen concentration at that time was less than 1% by volume.
As a result, the weight loss by heating was 10% by mass, and 0.9 g of 2,6-dihydroxynaphthalene having a purity of 99.0% was obtained.
Deterioration of 2,6-dihydroxynaphthalene was suppressed and drying was possible.
（実施例２）
含水率１０質量％かつ純度８９．０％の２，６−ジヒドロキシナフタレン粗体１ｇを、ＴＡＢＡＩ社製熱風乾燥機（ＨＩＧＨ−ＴＥＭＰ ＯＶＥＮ ＰＨＨ−１００）に入れ、窒素気流下、８０℃で２４時間乾燥を行った。その際の酸素濃度は１体積％未満であった。
その結果、加熱減量は１０質量％であり、純度９９．０％の２，６−ジヒドロキシナフタレン０．９ｇを得た。
２，６−ジヒドロキシナフタレンの劣化を抑制して乾燥することができた。
(Example 2)
1 g of 2,6-dihydroxynaphthalene crude having a water content of 10% by mass and a purity of 89.0% was placed in a TABAI hot air dryer (HIGH-TEMP OVEN PHH-100) at 80 ° C. for 24 hours under a nitrogen stream. It was dried. The oxygen concentration at that time was less than 1% by volume.
As a result, the weight loss by heating was 10% by mass, and 0.9 g of 2,6-dihydroxynaphthalene having a purity of 99.0% was obtained.
Deterioration of 2,6-dihydroxynaphthalene was suppressed and drying was possible.
（実施例３）
含水率１０質量％かつ純度８９．０％の２，６−ジヒドロキシナフタレン粗体１ｇを、ＹＡＭＡＴＯ社製ロータリーエバポレーター（Ｒｏｔａｒｙ Ｅｖａｐｏｒａｔｏｒ ＲＥ２００）に入れ、真空下、バス温度１００℃で２４時間乾燥を行った。その際の酸素濃度は１体積％未満であった。
その結果、加熱減量は１０質量％であり、純度９９．０％の２，６−ジヒドロキシナフタレン０．９ｇを得た。
２，６−ジヒドロキシナフタレンの劣化を抑制して乾燥することができた。
(Example 3)
1 g of 2,6-dihydroxynaphthalene crude having a water content of 10% by mass and a purity of 89.0% was placed in a rotary evaporator (Rotary Evaporator RE200) manufactured by YAMATO, and dried under vacuum at a bath temperature of 100 ° C. for 24 hours. .. The oxygen concentration at that time was less than 1% by volume.
As a result, the weight loss by heating was 10% by mass, and 0.9 g of 2,6-dihydroxynaphthalene having a purity of 99.0% was obtained.
Deterioration of 2,6-dihydroxynaphthalene was suppressed and drying was possible.
（実施例４）
含水率１２．４質量％かつ純度８７．２％の９，１０−ジヒドロキシアントラセン粗体２ｇを、ＥＳＰＥＣ社製真空乾燥機（ＶＡＣＵＵＭ ＯＶＥＮ ＬＣＶ−２３３）に入れ、真空下、８０℃で２４時間乾燥を行った。その際の酸素濃度は１体積％未満であった。
その結果、加熱減量は１１．６質量％であり、純度９８．２％の９，１０−ジヒドロキシアントラセン１．７ｇを得た。
９，１０−ジヒドロキシアントラセンの劣化を抑制して乾燥することができた。
(Example 4)
2 g of 9,10-dihydroxyanthracene crude having a moisture content of 12.4% by mass and a purity of 87.2% is placed in a vacuum dryer (VACUUM OVEN LCV-233) manufactured by ESPEC and dried under vacuum at 80 ° C. for 24 hours. Was done. The oxygen concentration at that time was less than 1% by volume.
As a result, the weight loss by heating was 11.6% by mass, and 1.7 g of 9,10-dihydroxyanthracene having a purity of 98.2% was obtained.
It was possible to suppress the deterioration of 9,10-dihydroxyanthracene and dry it.
（実施例５）
含水率１１．８質量％かつ純度８８．０％の４，４−ビフェノール粗体２ｇを、ＥＳＰＥＣ社製真空乾燥機（ＶＡＣＵＵＭ ＯＶＥＮ ＬＣＶ−２３３）に入れ、真空下、８０℃で２４時間乾燥を行った。その際の酸素濃度は１体積％未満であった。
その結果、加熱減量は１１．６質量％であり、純度９８．０％の４，４−ビフェノール１．７ｇを得た。
４，４−ビフェノールの劣化を抑制して乾燥することができた。
(Example 5)
2 g of 4,4-biphenol crude having a moisture content of 11.8% by mass and a purity of 88.0% was placed in a vacuum dryer (VACUUM OVEN LCV-233) manufactured by ESPEC, and dried at 80 ° C. for 24 hours under vacuum. went. The oxygen concentration at that time was less than 1% by volume.
As a result, the weight loss by heating was 11.6% by mass, and 1.7 g of 4,4-biphenol having a purity of 98.0% was obtained.
It was possible to suppress the deterioration of 4,4-biphenol and dry it.
（実施例６）
含水率１２．２質量％かつ純度８７．６％の１−ヒドロキシピレン粗体２ｇを、ＥＳＰＥＣ社製真空乾燥機（ＶＡＣＵＵＭ ＯＶＥＮ ＬＣＶ−２３３）に入れ、真空下、８０℃で２４時間乾燥を行った。その際の酸素濃度は１体積％未満であった。
その結果、加熱減量は１１．９質量％であり、純度９８．０％の１−ヒドロキシピレン１．７ｇを得た。
１−ヒドロキシピレンの劣化を抑制して乾燥することができた。
(Example 6)
2 g of 1-hydroxypyrene crude having a water content of 12.2% by mass and a purity of 87.6% was placed in a vacuum dryer (VACUUM OVEN LCV-233) manufactured by ESPEC, and dried at 80 ° C. for 24 hours under vacuum. rice field. The oxygen concentration at that time was less than 1% by volume.
As a result, the weight loss by heating was 11.9% by mass, and 1.7 g of 1-hydroxypyrene having a purity of 98.0% was obtained.
Deterioration of 1-hydroxypyrene was suppressed and drying was possible.
（実施例７）
含水率１０．２質量％かつ純度８９．６％のレゾルシノール（１、３−ジヒドロキシベンゼン）粗体２ｇを、ＥＳＰＥＣ社製真空乾燥機（ＶＡＣＵＵＭ ＯＶＥＮ ＬＣＶ−２３３）に入れ、真空下、８０℃で２４時間乾燥を行った。その際の酸素濃度は１体積％未満であった。
その結果、加熱減量は９．９質量％であり、純度９９．８％のレゾルシノール１．７ｇを得た。
レゾルシノールの劣化を抑制して乾燥することができた。
(Example 7)
2 g of a crude resorcinol (1,3-dihydroxybenzene) having a water content of 10.2% by mass and a purity of 89.6% was placed in a vacuum dryer (VACUUM OVEN LCV-233) manufactured by ESPEC at 80 ° C. under vacuum. It was dried for 24 hours. The oxygen concentration at that time was less than 1% by volume.
As a result, the weight loss by heating was 9.9% by mass, and 1.7 g of resorcinol having a purity of 99.8% was obtained.
Deterioration of resorcinol was suppressed and drying was possible.
（比較例１）
含水率１０質量％かつ純度８９．０％の２，６−ジヒドロキシナフタレン粗体１ｇを、ＴＡＢＡＩ社製熱風乾燥機（ＨＩＧＨ−ＴＥＭＰ ＯＶＥＮ ＰＨＨ−１００）に入れ、大気流下、８０℃で２４時間乾燥を行った。その際の酸素濃度は２０．８体積％であった。
その結果、加熱減量は１０質量％であったが、純度９５．１％の２，６−ジヒドロキシナフタレン０．９ｇを得た。
乾燥はできたものの、２，６−ジヒドロキシナフタレンは劣化した。
(Comparative Example 1)
1 g of 2,6-dihydroxynaphthalene crude having a moisture content of 10% by mass and a purity of 89.0% was placed in a TABAI hot air dryer (HIGH-TEMP OVEN PHH-100) and dried at 80 ° C. for 24 hours under atmospheric flow. Was done. The oxygen concentration at that time was 20.8% by volume.
As a result, the weight loss by heating was 10% by mass, but 0.9 g of 2,6-dihydroxynaphthalene having a purity of 95.1% was obtained.
Although it could be dried, 2,6-dihydroxynaphthalene deteriorated.
（比較例２）
含水率１０質量％かつ純度８９．０％の２，６−ジヒドロキシナフタレン粗体１ｇを、東京硝子器械社製ホットスターラー（ＨＯＴ ＳＴＩＲＲＥＲ Ｆ−１７ＨＳＤ）上にて、大気下、１００℃で２４時間乾燥を行った。その際の酸素濃度は２０．８体積％であった。
その結果、加熱減量は１０質量％であったが、純度９０．０％の２，６−ジヒドロキシナフタレン０．９ｇを得た。
乾燥はできたものの、２，６−ジヒドロキシナフタレンは劣化した。
(Comparative Example 2)
1 g of 2,6-dihydroxynaphthalene crude having a water content of 10% by mass and a purity of 89.0% is dried on a hot stirrer (HOT STIRRER F-17HSD) manufactured by Tokyo Glass Instruments Co., Ltd. at 100 ° C. for 24 hours. Was done. The oxygen concentration at that time was 20.8% by volume.
As a result, the weight loss by heating was 10% by mass, but 0.9 g of 2,6-dihydroxynaphthalene having a purity of 90.0% was obtained.
Although it could be dried, 2,6-dihydroxynaphthalene deteriorated.
（実施例１−１）
ＲＰシステムアルミ袋（三菱ガス化学社製；寸法６００ｍｍ×７００ｍｍ）に、純度９９％の２，６−ジヒドロキシナフタレンを１０ｋｇ入れ、ＲＰシステムアルミ袋を脱気、ヒートシールを行い、封をした。その際のＲＰシステムアルミ袋内の酸素濃度は１体積％未満であった。
１週間２５℃環境下にて保管し、その後、袋から２，６−ジヒドロキシナフタレンを取り出し純度を測定したところ、純度９９％と変化無く良好であった。
なお、前記ＲＰシステムアルミ袋とは、透過度がほぼゼロで、無酸素無水分の環境とする包装に用いられる袋であり、例えば、以下のサイトにより確認することができる。
http:www.mgc.co.jp/seihin/a/rpsystem/bag.html
(Example 1-1)
10 kg of 2,6-dihydroxynaphthalene having a purity of 99% was placed in an RP system aluminum bag (manufactured by Mitsubishi Gas Chemical Company, Ltd .; dimensions 600 mm × 700 mm), and the RP system aluminum bag was degassed, heat-sealed, and sealed. At that time, the oxygen concentration in the RP system aluminum bag was less than 1% by volume.
It was stored in an environment of 25 ° C. for one week, and then 2,6-dihydroxynaphthalene was taken out from the bag and the purity was measured. As a result, the purity was 99%, which was good without any change.
The RP system aluminum bag has almost zero transmittance and is used for packaging in an oxygen-free and anhydrous environment. For example, it can be confirmed at the following site.
http: www.mgc.co.jp/seihin/a/rpsystem/bag.html
（実施例１−２）
ＲＰシステムアルミ袋（三菱ガス化学社製；寸法６００ｍｍ×７００ｍｍ）に、純度９９％の２，６−ジヒドロキシナフタレンを１０ｋｇ入れ、酸素吸収剤として市販されているＲＰ剤（三菱ガス化学社製）を１０個同封、ヒートシールを行い、封をした。１週間２５℃環境下にて保管し、その際のＲＰシステムアルミ袋内の酸素濃度は１体積％未満であった。
その後、袋から２，６−ジヒドロキシナフタレンを取り出し純度を測定したところ、純度９９％と変化無く良好であった。
(Example 1-2)
RP system Put 10 kg of 2,6-dihydroxynaphthalene with a purity of 99% in an aluminum bag (manufactured by Mitsubishi Gas Chemical Company; dimensions 600 mm x 700 mm), and put a commercially available RP agent (manufactured by Mitsubishi Gas Chemical Company) as an oxygen absorber. Ten pieces were enclosed, heat-sealed, and sealed. It was stored in an environment of 25 ° C. for one week, and the oxygen concentration in the RP system aluminum bag at that time was less than 1% by volume.
After that, 2,6-dihydroxynaphthalene was taken out from the bag and the purity was measured. As a result, the purity was 99%, which was good without any change.
（実施例１−３）
ＲＰシステムアルミ袋（三菱ガス化学社製；寸法６００ｍｍ×７００ｍｍ）に、純度９９％の２，６−ジヒドロキシナフタレンを１０ｋｇ入れ、酸素吸収剤として市販されているＲＰ剤（三菱ガス化学社製）を８個同封、ヒートシールを行い、封をした。１週間２５℃環境下にて保管し、その際のＲＰシステムアルミ袋内の酸素濃度は３体積％であった。
その後、袋から２，６−ジヒドロキシナフタレンを取り出し純度を測定したところ、純度９９％と変化無く良好であった。
(Example 1-3)
RP system Put 10 kg of 2,6-dihydroxynaphthalene with a purity of 99% in an aluminum bag (manufactured by Mitsubishi Gas Chemical Company; dimensions 600 mm x 700 mm), and put a commercially available RP agent (manufactured by Mitsubishi Gas Chemical Company) as an oxygen absorber. Eight pieces were enclosed, heat-sealed, and sealed. It was stored in an environment of 25 ° C. for one week, and the oxygen concentration in the RP system aluminum bag at that time was 3% by volume.
After that, 2,6-dihydroxynaphthalene was taken out from the bag and the purity was measured. As a result, the purity was 99%, which was good without any change.
（実施例１−４）
ＲＰシステムアルミ袋（三菱ガス化学社製；寸法６００ｍｍ×７００ｍｍ）に、純度９９％の２，６−ジヒドロキシナフタレンを１０ｋｇ入れ、酸素吸収剤として市販されているＲＰ剤（三菱ガス化学社製）を６個同封、ヒートシールを行い、封をした。１週間２５℃環境下にて保管し、その際のＲＰシステムアルミ袋内の酸素濃度は６体積％であった。
その後、袋から２，６−ジヒドロキシナフタレンを取り出し純度を測定したところ、純度９８．４％と良好であった。
(Example 1-4)
RP system Put 10 kg of 2,6-dihydroxynaphthalene with a purity of 99% in an aluminum bag (manufactured by Mitsubishi Gas Chemical Company; dimensions 600 mm x 700 mm), and put a commercially available RP agent (manufactured by Mitsubishi Gas Chemical Company) as an oxygen absorber. Six pieces were enclosed, heat-sealed, and sealed. It was stored in an environment of 25 ° C. for one week, and the oxygen concentration in the RP system aluminum bag at that time was 6% by volume.
Then, 2,6-dihydroxynaphthalene was taken out from the bag and the purity was measured. As a result, the purity was as good as 98.4%.
（実施例１−５）
ＲＰシステムアルミ袋（三菱ガス化学社製；寸法６００ｍｍ×７００ｍｍ）に、純度９９％の２，６−ジヒドロキシナフタレンを１０ｋｇ入れ、酸素吸収剤として市販されているＲＰ剤（三菱ガス化学社製）を３個同封、ヒートシールを行い、封をした。１週間２５℃環境下にて保管し、その際のＲＰシステムアルミ袋内の酸素濃度は１１体積％であった。
その後、袋から２，６−ジヒドロキシナフタレンを取り出し純度を測定したところ、純度９８％と良好であった。
(Example 1-5)
RP system Put 10 kg of 2,6-dihydroxynaphthalene with a purity of 99% in an aluminum bag (manufactured by Mitsubishi Gas Chemical Company; dimensions 600 mm x 700 mm), and put a commercially available RP agent (manufactured by Mitsubishi Gas Chemical Company) as an oxygen absorber. Three pieces were enclosed, heat-sealed, and sealed. It was stored in an environment of 25 ° C. for one week, and the oxygen concentration in the RP system aluminum bag at that time was 11% by volume.
Then, 2,6-dihydroxynaphthalene was taken out from the bag and the purity was measured. As a result, the purity was as good as 98%.
（比較例１−１）
ＲＰシステムアルミ袋（三菱ガス化学社製）に、純度９９％の２，６−ジヒドロキシナフタレンを１０ｋｇ入れ、ＲＰシステムアルミ袋を脱気せずに、ヒートシールを行い、封をした。その際のＲＰシステムアルミ袋内の酸素濃度は２０．８体積％であった。
１週間２５℃環境下にて保管し、その後、袋から２，６−ジヒドロキシナフタレンを取り出し純度を測定したところ、純度９５％と劣化が認められ不良であった。
(Comparative Example 1-1)
10 kg of 2,6-dihydroxynaphthalene having a purity of 99% was placed in an RP system aluminum bag (manufactured by Mitsubishi Gas Chemical Company, Inc.), and the RP system aluminum bag was heat-sealed and sealed without degassing. At that time, the oxygen concentration in the RP system aluminum bag was 20.8% by volume.
It was stored in an environment of 25 ° C. for one week, and then 2,6-dihydroxynaphthalene was taken out from the bag and the purity was measured. As a result, deterioration of purity of 95% was observed, which was defective.
本発明は、ヒドロキシ置換芳香族化合物（例えば、上記式（１）で表される化合物）を工業的に有利に製造する方法を提供することができる。
また、本発明は、ヒドロキシ置換芳香族化合物（例えば、式（１）で表される化合物）を工業的に有利に梱包する方法を提供することができる。
The present invention can provide a method for industrially advantageously producing a hydroxy-substituted aromatic compound (for example, a compound represented by the above formula (1)).
The present invention can also provide a method for industrially advantageous packaging of hydroxy-substituted aromatic compounds (eg, compounds represented by formula (1)).
Claims (8)
前記ヒドロキシ置換芳香族化合物が、下記式（Ａ 0 ）及び／又は（Ｂ 0 ）で表されるヒドロキシ置換芳香族化合物である、ヒドロキシ置換芳香族化合物の梱包方法。
上記式（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、Ｒ b 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。） The oxygen concentration of the hydroxy-substituted aromatic compound is 20 volumes based on 100% by volume of the gas volume obtained by subtracting the volume of the hydroxy-substituted aromatic compound from the total amount of gas components under atmospheric pressure in the packing container before packing. atmosphere of less than% (However,. except those of the pressure-reduced state) only contains the step of packing in,
A method for packing a hydroxy-substituted aromatic compound, wherein the hydroxy-substituted aromatic compound is a hydroxy-substituted aromatic compound represented by the following formulas (A 0 ) and / or (B 0 ).
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 R b is independently a hydrogen atom, a hydroxyl group, a halogen group, and 1 to 1 carbon atoms. A group consisting of 40 linear, branched or cyclic alkyl groups, an aryl group having 6 to 40 carbon atoms which may have a substituent, or an alkenyl group having 2 to 40 carbon atoms and a combination thereof. , The alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond. )
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）で表されるヒドロキシ置換芳香族化合物である、ヒドロキシ置換芳香族化合物の梱包方法。
上記式（Ｂ）中、ｎ1は０〜９の整数であり、ｐ1は０〜９の整数であり、Ｒ1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。） The oxygen concentration of the hydroxy-substituted aromatic compound is 20 volumes based on 100% by volume of the gas volume obtained by subtracting the volume of the hydroxy-substituted aromatic compound from the total amount of gas components under atmospheric pressure in the packing container before packing. Including the process of packing in an atmosphere of less than% (excluding those in a depressurized state)
The hydroxy-substituted aromatic compound is a hydroxy-substituted aromatic compound represented by the following formula (A) and / or (B), the packing method arsenide Dorokishi substituted aromatic compound.
In 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 independently linear, branched or branched with 1 to 30 carbon atoms. It is a cyclic alkyl group, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms. )
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、ヒドロキシ置換芳香族化合物の梱包方法。
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). a compound represented by a-4), and is at least one selected from the group consisting of compounds represented by the following formula (B-1), the packing method arsenide Dorokishi substituted aromatic compound.
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、ヒドロキシ置換芳香族化合物の梱包方法。
A method for packing a hydroxy-substituted aromatic compound, wherein the hydroxy-substituted aromatic compound is a compound represented by the following formula (1).
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| JPS6055491B2 (en) * | 1977-05-23 | 1985-12-05 | 三井東圧化学株式会社 | Purification method of β-naphthol |
| JPS5511513A (en) * | 1978-07-10 | 1980-01-26 | Mitsui Petrochem Ind Ltd | Purification of resorcinol |
| JPS5643228A (en) * | 1979-09-19 | 1981-04-21 | Mitsui Toatsu Chem Inc | Prevention of color development of aromatic compound having hydroxyl group |
| JPS6270333A (en) * | 1985-09-20 | 1987-03-31 | Mitsui Petrochem Ind Ltd | Production of 2,6-dihydroxynaphthalene |
| JPH0667865B2 (en) * | 1986-08-02 | 1994-08-31 | 三井石油化学工業株式会社 | Purification method of dihydroxynaphthalene |
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