WO2016190024A1

WO2016190024A1 - Method for producing hydroxy-substituted aromatic compound and method for packaging same

Info

Publication number: WO2016190024A1
Application number: PCT/JP2016/062964
Authority: WO
Inventors: 直哉内山; 淳矢堀内; 牧野嶋　高史; 越後　雅敏; 篤大越
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2015-05-27
Filing date: 2016-04-26
Publication date: 2016-12-01
Also published as: JP7249733B2; CN107614472A; JP2020111609A; JPWO2016190024A1; JP6952954B2; TW201706237A

Abstract

This method for producing a hydroxy-substituted aromatic compound involves a step of drying a hydroxy-substituted aromatic compound in an atmosphere in which the oxygen concentration is less than 20 vol%. This method for packaging a hydroxy-substituted aromatic compound involves a step of packaging a hydroxy-substituted aromatic compound in an atmosphere in which the oxygen concentration is less than 20 vol%.

Description

Process for producing and packaging hydroxy-substituted aromatic compounds

The present invention relates to a method for producing and packaging a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene).

Hydroxy-substituted aromatic compounds such as dihydroxynaphthalene are useful as raw materials for compounds or resins used as semiconductor sealing materials, coating agents, resist materials, and semiconductor underlayer film forming materials (for example, Patent Document 1). To 2). Moreover, a specific method is known as a purification method of a hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene (see, for example, Patent Document 3).

International Publication No. 2013/024778 International Publication No. 2013/024779 Chinese Patent Application No. 1034746749

Conventionally, hydroxy-substituted aromatic compounds such as dihydroxynaphthalene (naphthalenediol) are generally used after drying. However, at the same time, problems such as simultaneous deterioration and variations in purity have become apparent, and there is a need for an improved method for drying hydroxy-substituted aromatic compounds such as dihydroxynaphthalene.
In addition, conventionally, hydroxy-substituted aromatic compounds, for example, dihydroxynaphthalene, have been packaged during storage and transportation, but at the same time, problems such as deterioration at the same time and variations in purity have become apparent. Thus, there is a need for an improved packaging method for 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) that suppresses deterioration of a hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene, and is industrially advantageous in the drying step. is there.
A second object of the present invention is to provide a packing method that suppresses deterioration during storage and transportation of a hydroxy-substituted aromatic compound such as dihydroxynaphthalene and is industrially advantageous.

As a result of intensive studies to solve the above-mentioned problems, the present inventors dried hydroxy-substituted aromatic compounds (for example, dihydroxynaphthalene) under specific conditions, so that hydroxy-substituted aromatic compounds (for example, dihydroxynaphthalene) It has been 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 intensive studies to solve the above second problem, the present inventors have determined that the hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) is deteriorated during storage and transportation by packing under specific conditions. As a result, the inventors have found that it can be stored and transported while maintaining high purity.

That is, the present invention is as follows.
[1]
The manufacturing method of a hydroxy substituted aromatic compound including the process of drying a hydroxy substituted aromatic compound in the atmosphere whose oxygen concentration is less than 20 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 formula (A ₀ ) and / or (B ₀ ).

(In the above formula (A ₀ ), n ⁰ is an integer of 0 to 9, m ⁰ is an integer of 0 to 2, p ⁰ is an integer of 0 to 9, and each Ra is independently hydrogen. An atom, a hydroxyl group, a halogen group, a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms which may have a substituent, or a group having 2 to 40 carbon atoms It is a group consisting of an alkenyl group and 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 R _b is each independently a hydrogen atom, a hydroxyl group, a halogen group, a carbon number of 1 to A group consisting of 40 linear, branched or cyclic alkyl groups, optionally substituted aryl groups having 6 to 40 carbon atoms, or alkenyl groups having 2 to 40 carbon atoms and combinations thereof. The alkyl group, aryl group or 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 formula (A) and / or (B).

(In the above formula (A), n ⁰ is an integer of 0 to 9, m ⁰ is an integer of 0 to 2, p ⁰ is an integer of 0 to 9, and R ₀ is each independently carbon. A 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 above formula (B), n ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and each R ₁ is independently a linear, branched or branched group having 1 to 30 carbon atoms. 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), The method for producing a hydroxy-substituted aromatic compound according to [1], which is at least one selected from the group consisting of a compound represented by A-4) and a compound represented by the following formula (B-1).

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

[6]
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 substance is sulfurous acid (salt), bisulfite (salt), pyrosulfurous acid (salt), dithionic acid (salt), trithionic acid (salt), tetrathionic acid (salt), thiosulfuric acid (salt) Rongalite, thioacetic acid (salt), 2,3-dimercapto-1-propanol, dimethyl sulfoxide, thiourea dioxide, monomethylamine, dimethylamine, trimethylamine, monoethanolamine, diethanolamine, triethanolamine, phosphorous acid ( Salt) and hypophosphorous acid (salt). The production method according to [6], which is one or more selected from the group consisting of:
[8]
A method for packing a hydroxy-substituted aromatic compound, the method comprising packing the hydroxy-substituted aromatic compound in an atmosphere having an oxygen concentration of less than 20% by volume.
[9]
The method for packing hydroxy-substituted aromatic compounds according to [8], wherein the hydroxy-substituted aromatic compound is a hydroxy-substituted aromatic compound represented by the following formula (A ₀ ) and / or (B ₀ ).

(In the above formula (A ₀ ), n ⁰ is an integer of 0 to 9, m ⁰ is an integer of 0 to 2, p ⁰ is an integer of 0 to 9, and each Ra is independently hydrogen. An atom, a hydroxyl group, a halogen group, a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms which may have a substituent, or a group having 2 to 40 carbon atoms It is a group consisting of an alkenyl group and 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 R _b is each independently a hydrogen atom, a hydroxyl group, a halogen group, a carbon number of 1 to A group consisting of 40 linear, branched or cyclic alkyl groups, optionally substituted aryl groups having 6 to 40 carbon atoms, or alkenyl groups having 2 to 40 carbon atoms and combinations thereof. The alkyl group, aryl group or 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 formula (A) and / or (B).

(In the above formula (A), n ⁰ is an integer of 0 to 9, m ⁰ is an integer of 0 to 2, p ⁰ is an integer of 0 to 9, and R ₀ is each independently carbon. A 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 above formula (B), n ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and each R ₁ is independently a linear, branched or branched group having 1 to 30 carbon atoms. 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), The method for packing a hydroxy-substituted aromatic compound according to [8], which is at least one selected from the group consisting of a compound represented by A-4) and a compound represented by the following formula (B-1).

(In the above formulas (A-1) to (A-4), n ⁰ is an integer from 0 to 9, and in the above formula (B-1), n ¹ is an integer from 0 to 9.)
[12]
The packaging method according to [8], wherein the hydroxy-substituted aromatic compound is a compound represented by the following formula (1).

[13]
The packaging method according to any one of [8] to [12], comprising a step of allowing the hydroxy-substituted aromatic compound and a desiccant to coexist in a packaging container.
[14]
The packaging method according to any one of [8] to [13], comprising a step of allowing the hydroxy-substituted aromatic compound and the reducing substance to coexist in a packaging container.
[15]
The packaging method according to any one of [8] to [14], comprising a step of allowing the hydroxy-substituted aromatic compound and the oxygen scavenger to coexist in a packaging container.
[16]
The reducing substance is sulfurous acid (salt), bisulfite (salt), pyrosulfurous acid (salt), dithionic acid (salt), trithionic acid (salt), tetrathionic acid (salt), thiosulfuric acid (salt) Rongalite, thioacetic acid (salt), 2,3-dimercapto-1-propanol, dimethyl sulfoxide, thiourea dioxide, monomethylamine, dimethylamine, trimethylamine, monoethanolamine, diethanolamine, triethanolamine, phosphorous acid ( Salt) and hypophosphorous acid (salt). The packaging method according to [14], which is at least one selected from the group consisting of.

According to the present invention, alteration and deterioration of a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) in the 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 suppressing deterioration during storage and transportation of a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) and stably maintaining high purity.

Hereinafter, embodiments of the present invention (hereinafter also referred to as “present embodiments”) will be described in detail. In addition, the following embodiment is an illustration for demonstrating this invention, and this invention is not limited only to the embodiment.

<Method for producing hydroxy-substituted aromatic compound>
The manufacturing method of the hydroxy substituted aromatic compound of this embodiment includes the process of drying a hydroxy substituted aromatic compound in the atmosphere whose oxygen concentration is less than 20 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. For example, the following formula (A ₀ ) and / or (B ₀ It is preferable that it is a hydroxy substituted aromatic compound represented by this.

(In the above formula (A ₀ ), n ⁰ is an integer of 0 to 9, m ⁰ is an integer of 0 to 2, p ⁰ is an integer of 0 to 9, and each Ra is independently hydrogen. An atom, a hydroxyl group, a halogen group, a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms which may have a substituent, or a group having 2 to 40 carbon atoms It is a group consisting of an alkenyl group and 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 R _b is each independently a hydrogen atom, a hydroxyl group, a halogen group, a carbon number of 1 to A group consisting of 40 linear, branched or cyclic alkyl groups, optionally substituted aryl groups having 6 to 40 carbon atoms, or alkenyl groups having 2 to 40 carbon atoms and combinations thereof. The alkyl group, aryl group or alkenyl group may contain an ether bond, a ketone bond or an ester bond. )

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 formula (A) and / or (B).

(In the above formula (A), n ⁰ is an integer of 0 to 9, m ⁰ is an integer of 0 to 2, p ⁰ is an integer of 0 to 9, and R ₀ is each independently carbon. A 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 above formula (B), n ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and each R ₁ is independently a linear, branched or branched group having 1 to 30 carbon atoms. 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. )

In the production method of the present embodiment, the hydroxy-substituted aromatic compound is a compound represented by the following formula (A-1), a compound represented by the following formula (A-2), or a compound represented by the following formula (A-3). More preferably, it is at least one selected from the group consisting of a compound represented by the following formula (A-4) and a compound represented by the following formula (B-1).

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

In the production method of the present embodiment, the hydroxy-substituted aromatic compound is particularly preferably a compound represented by the following formula (1).

Hydroxy-substituted aromatic compounds, such as dihydroxynaphthalene, have a problem that dimers are likely to be formed. However, by drying the compound in an atmosphere having an oxygen concentration of less than 20% by volume, dihydration by oxidation of the compound is caused. It is possible to suppress the production of by-products such as a monomer and stably produce the high-purity compound.

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. Although the minimum of the oxygen concentration of a drying process is not specifically limited, For example, it is 0.01 volume%.

The method for reducing the oxygen concentration can be a known method and is not particularly limited, and examples thereof include a method of supplying a gas mainly containing a gas other than oxygen into the dryer. The method of depressurizing a dryer and performing in vacuum can also be mentioned.

Confirmation of the oxygen concentration can be carried out by a known method, and is not particularly limited. For example, a method of measuring the oxygen concentration of the gas discharged from the vent by flowing nitrogen gas into a dryer with an oximeter. Can be mentioned. A method of installing an oxygen concentration meter in the dryer can also be mentioned.

The drying temperature is not particularly limited as long as the alteration of the hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene can be suppressed, but it is usually preferably in the range of 10 to 230 ° C.
If the drying temperature is 10 ° C. or higher, undried products tend not to occur. Further, when the drying temperature is lower than 230 ° C., the alteration of the hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene tends to hardly occur. A more preferable drying temperature is 50 to 100 ° C., and a further preferable drying temperature is 60 to 90 ° C.
The drying time is not particularly limited, but usually 30 minutes to 1 week is preferable. More preferably, it is 45 minutes to 1 day, and more preferably 1 hour to 12 hours. The drying pressure can be any of reduced pressure, normal pressure and increased pressure.

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).

Here, the compound represented by the above formula (1) is not particularly limited, but 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, , 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 preferred.

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

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

The compound represented by the above formula (1) can be easily obtained by known means such as a manufacturer and a reagent manufacturer. Moreover, it can synthesize | combine suitably applying a well-known method, The synthesis | combining method is not specifically limited.

In the production method of the present embodiment, the hydroxy-substituted aromatic compound may be used alone or in combination of two or more. Further, the hydroxy-substituted aromatic compound may contain various surfactants, various crosslinking agents, various acid generators, various stabilizers and the like.

In the manufacturing method of this embodiment, it is preferable that the said drying process is performed in 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. Although it does not specifically limit as a reducing substance, For example, sulfurous acid (salt), bisulfite (salt), pyrosulfurous acid (salt), dithionic acid (salt), trithionic acid (salt), tetrathionic acid (salt) ), Thiosulfuric acid (salt), Rongalite, thioacetic acid (salt), 2,3-dimercapto-1-propanol, dimethyl sulfoxide, thiourea dioxide, and other sulfur-containing atomic reducing substances; monomethylamine, dimethylamine, trimethylamine And organic amines such as monoethanolamine, diethanolamine, and triethanolamine; and phosphorus-containing atom-reducing substances such as phosphorous acid (salt) and hypophosphorous acid (salt). Among these, it is preferable to use bisulfite (salt) that is inexpensive, easily available industrially, and highly effective.
These reducing substances may be used alone or in combination of two or more.

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, it is 0.1 to 1 part by mass. In addition, 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 when manufacturing an inexpensive product.

<Packaging method of hydroxy-substituted aromatic compound>
The packaging method of the hydroxy substituted aromatic compound of this embodiment includes the process of packaging a hydroxy substituted aromatic compound in the atmosphere whose oxygen concentration is less than 20%.

In the packaging 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. For example, the following formula (A ₀ ) and / or (B ₀ It is preferable that it is a hydroxy substituted aromatic compound represented by this.

In the packaging method of the present embodiment, the hydroxy-substituted aromatic compound is more preferably a hydroxy-substituted aromatic compound represented by the following formula (A) and / or (B).

In the packaging method of the present embodiment, the hydroxy-substituted aromatic compound is a compound represented by the following formula (A-1), a compound represented by the following formula (A-2), or a compound represented by the following formula (A-3). More preferably, it is at least one selected from the group consisting of a compound represented by the following formula (A-4) and a compound represented by the following formula (B-1).

In the packaging 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).

A hydroxy-substituted aromatic compound such as 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 oxidation of the compound. It is possible to suppress the production of by-products such as a polymer, and to store and transport while maintaining high purity.

In the packaging method of this embodiment, the oxygen concentration in the packaging process is preferably less than 10% by volume, more preferably less than 5% by volume, and even more preferably less than 1% by volume. As the oxygen concentration in the packaging process is lower, the alteration of the hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene can be suppressed. Although the minimum of the oxygen concentration of a packing process is not specifically limited, For example, it is 0.01 volume%.

A known method can be applied as a method for reducing the oxygen concentration, and is not particularly limited. For example, a method of performing gas replacement by flowing nitrogen gas into a packing container or introducing nitrogen gas after reducing the pressure. Can be mentioned. Alternatively, a method in which the pressure is reduced and the reaction is performed in a vacuum can be mentioned. A method in which the packing container is decompressed and nitrogen gas is introduced thereafter is simple, reliable and preferable.

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).

In the packaging 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 crosslinking agents, various acid generators, various stabilizers and the like.

In the packing method of the present embodiment, a known form can be applied as the packing form and is not particularly limited. Examples of packaging containers include resin film bags made of polyethylene, polypropylene, nylon, polyethylene terephthalate, or the like, aluminum bags, multilayer film bags thereof, or combinations 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. However, heat sealing is preferable from the viewpoint of further suppressing deterioration.

∙ Exterior materials can also be used for product protection and content display. As the exterior material, a known form can be applied and is not particularly limited, and examples thereof include cardboard, fiber drum, pail can, metal can, glass container and the like. Also, vinyl tape, caulking, metal bands or the like are used for fixing these lids.

In the packaging method of this embodiment, it is more preferable from the viewpoint of suppressing alteration of the hydroxy-substituted aromatic compound to include a step of allowing the hydroxy-substituted aromatic compound and the desiccant to coexist in the packaging container. As a desiccant, a well-known thing can be used, Although it does not specifically limit, For example, a silica gel, aluminum oxide, etc. are mentioned.
These desiccants may be used alone or in combination of two or more.

In the packaging method of the present embodiment, it is more preferable from the viewpoint of suppressing alteration of the compound to include a step of allowing the hydroxy-substituted aromatic compound and the reducing substance to coexist in the packaging container. When a reducing substance is added to the hydroxy-substituted aromatic compound and then subjected to a drying step, deterioration may be further suppressed. In some cases, it is also effective to arrange the reducing substance in the packaging container without adding it to the hydroxy-substituted aromatic compound.

The reducing substance is not particularly limited, and examples thereof include sulfite (salt), bisulfite (salt), pyrosulfite (salt), dithionite (salt), trithionate (salt), and tetrathionate ( Salt), thiosulfuric acid (salt), Rongalite, thioacetic acid (salt), 2,3-dimercapto-1-propanol, dimethyl sulfoxide, thiourea dioxide, and other sulfur-containing atomic reducing substances; monomethylamine, dimethylamine, Examples thereof include organic amines such as trimethylamine, monoethanolamine, diethanolamine, and triethanolamine; phosphorus-containing atom-reducing substances such as phosphorous acid (salt) and hypophosphorous acid (salt). Among these, it is preferable to use bisulfurous acid (salt) that is inexpensive, easily available industrially, and highly effective.
These reducing substances may be used alone or in combination of two or more.

In the packaging 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, and 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 even more preferable.
In addition, when these reducing substances are used, it may be possible to obtain a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) having no thermal degradation even when the oxygen concentration is relatively high. This can be a particularly effective means in the case of manufacturing.

In the packaging method of this embodiment, it is more preferable from the viewpoint of suppressing alteration of the compound to include a step of allowing the hydroxy-substituted aromatic compound and the oxygen scavenger to coexist in the packaged container. The oxygen scavenger is not particularly limited, and examples thereof include inorganic oxygen scavengers mainly composed of iron, phenols, ascorbic acid, glycerin, sugar alcohols and unsaturated fatty acids. Among these, an inorganic oxygen scavenger containing iron as a main component is preferable because it is inexpensive and easily available industrially. Examples of such inorganic oxygen scavengers 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.

In the packing method of the present embodiment, the amount of these oxygen scavengers used is preferably in the range of 0.01 to 5 parts by weight, and in the range of 0.05 to 3 parts by weight, with respect to 100 parts by weight of the hydroxy-substituted aromatic compound. Is more preferable, and the range of 0.1 to 1 part by mass is even more preferable.
In addition, when these oxygen scavengers are used, even if the oxygen concentration at the time of packing is relatively high, it becomes possible to reduce the oxygen concentration immediately 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.

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

Heat loss measurement method: About 1 g of naphthalene diol was taken in each dryer, dried under predetermined drying conditions, and calculated according to the following formula.
Heat loss (%) = (A−B) / A × 100
A: Weight of naphthalenediol collected (g)
B: Weight after drying (g)

(Example 1)
1 g of 2,6-dihydroxynaphthalene crude product having a water content of 10% by mass and a purity of 89.0% was placed in an ESPEC vacuum dryer (VACUUM OVEN LCV-233) and dried at 80 ° C. for 24 hours under vacuum. It was. The oxygen concentration at that time was less than 1% by volume.
As a result, the loss on heating was 10% by mass, and 0.9 g of 2,6-dihydroxynaphthalene having a purity of 99.0% was obtained.
It was possible to dry while suppressing deterioration of 2,6-dihydroxynaphthalene.

(Example 2)
1 g of 2,6-dihydroxynaphthalene crude product having a water content of 10% by mass and a purity of 89.0% was placed in a hot air dryer (HIGH-TEMP OVEN PHH-100) manufactured by Tabai Co., for 24 hours at 80 ° C. under a nitrogen stream. Drying was performed. The oxygen concentration at that time was less than 1% by volume.
As a result, the loss on heating was 10% by mass, and 0.9 g of 2,6-dihydroxynaphthalene having a purity of 99.0% was obtained.
It was possible to dry while suppressing deterioration of 2,6-dihydroxynaphthalene.

(Example 3)
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 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 loss on heating was 10% by mass, and 0.9 g of 2,6-dihydroxynaphthalene having a purity of 99.0% was obtained.
It was possible to dry while suppressing deterioration of 2,6-dihydroxynaphthalene.

Example 4
2 g of crude 9,10-dihydroxyanthracene having a water content of 12.4% by mass and a purity of 87.2% was placed in an ESPEC vacuum dryer (VACUUM OVEN LCV-233) 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 loss on 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 dry while suppressing the deterioration of 9,10-dihydroxyanthracene.

(Example 5)
2 g of 4,4-biphenol crude product having a moisture content of 11.8% by mass and a purity of 88.0% was placed in an ESPEC vacuum dryer (VACUUM OVEN LCV-233) 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 loss on 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 dry while suppressing deterioration of 4,4-biphenol.

(Example 6)
2 g of 1-hydroxypyrene crude product having a water content of 12.2% by mass and a purity of 87.6% was placed in an ESPEC vacuum dryer (VACUUM OVEN LCV-233) and dried under vacuum at 80 ° C. for 24 hours. It was. The oxygen concentration at that time was less than 1% by volume.
As a result, the loss on heating was 11.9% by mass, and 1.7 g of 1-hydroxypyrene having a purity of 98.0% was obtained.
It was possible to dry while suppressing deterioration of 1-hydroxypyrene.

(Example 7)
2 g of a resorcinol (1,3-dihydroxybenzene) crude product having a water content of 10.2% by mass and a purity of 89.6% was placed in an ESPEC vacuum dryer (VACUUM OVEN LCV-233), and at 80 ° C. under vacuum. Drying was performed for 24 hours. The oxygen concentration at that time was less than 1% by volume.
As a result, the loss on heating was 9.9% by mass, and 1.7 g of resorcinol having a purity of 99.8% was obtained.
The resorcinol could be dried while suppressing deterioration.

(Comparative Example 1)
1 g of 2,6-dihydroxynaphthalene crude product having a water content of 10% by mass and a purity of 89.0% was placed in a hot air dryer (HIGH-TEMP OVEN PHH-100) manufactured by Tabai Co., Ltd. and dried at 80 ° C. for 24 hours in an air stream. Went. The oxygen concentration at that time was 20.8% by volume.
As a result, although loss on heating was 10% by mass, 0.9 g of 2,6-dihydroxynaphthalene having a purity of 95.1% was obtained.
Although dried, 2,6-dihydroxynaphthalene deteriorated.

(Comparative Example 2)
1 g of 2,6-dihydroxynaphthalene crude product having a water content of 10% by mass and a purity of 89.0% was dried on the hot stirrer (HOT STIRRE F-17HSD) manufactured by Tokyo Glass Instruments Co., Ltd. at 100 ° C. for 24 hours. Went. The oxygen concentration at that time was 20.8% by volume.
As a result, although loss on heating was 10% by mass, 0.9 g of 2,6-dihydroxynaphthalene having a purity of 90.0% was obtained.
Although dried, 2,6-dihydroxynaphthalene deteriorated.

Example 1-1
10 kg of 99% pure 2,6-dihydroxynaphthalene was put in an RP system aluminum bag (Mitsubishi Gas Chemical Co., 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 at 25 ° C. for 1 week, and then 2,6-dihydroxynaphthalene was taken out from the bag and the purity was measured. The purity was as good as 99%.
In addition, the said RP system aluminum bag is a bag used for the packaging made into the environment where the permeability is substantially zero and oxygen-free, and can be confirmed, for example, at the following site.
http: www.mgc.co.jp/seihin/a/rpsystem/bag.html

Example 1-2
Put RP system aluminum bag (Mitsubishi Gas Chemical Co., Ltd .; dimensions: 600 mm x 700 mm) with 10 kg of 99% pure 2,6-dihydroxynaphthalene, and use commercially available RP agent (Mitsubishi Gas Chemical Co., Ltd.) as an oxygen absorber. Ten pieces were enclosed, heat-sealed, and sealed. It was stored in an environment of 25 ° C. for 1 week, and the oxygen concentration in the RP system aluminum bag at that time was less than 1% by volume.
Thereafter, 2,6-dihydroxynaphthalene was taken out from the bag and the purity was measured. The purity was 99% and it was good without change.

(Example 1-3)
Put RP system aluminum bag (Mitsubishi Gas Chemical Co., Ltd .; dimensions: 600 mm x 700 mm) with 10 kg of 99% pure 2,6-dihydroxynaphthalene, and use commercially available RP agent (Mitsubishi Gas Chemical Co., Ltd.) as an oxygen absorber. Eight sealed and heat 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.
Thereafter, 2,6-dihydroxynaphthalene was taken out from the bag and the purity was measured. The purity was 99% and it was good without change.

(Example 1-4)
Put RP system aluminum bag (Mitsubishi Gas Chemical Co., Ltd .; dimensions: 600 mm x 700 mm) with 10 kg of 99% pure 2,6-dihydroxynaphthalene, and use commercially available RP agent (Mitsubishi Gas Chemical Co., Ltd.) as an oxygen absorber. Six were enclosed and heat 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.
Thereafter, 2,6-dihydroxynaphthalene was taken out of the bag and the purity was measured. The purity was as good as 98.4%.

(Example 1-5)
Put RP system aluminum bag (Mitsubishi Gas Chemical Co., Ltd .; dimensions: 600 mm x 700 mm) with 10 kg of 99% pure 2,6-dihydroxynaphthalene, and use commercially available RP agent (Mitsubishi Gas Chemical Co., Ltd.) as an oxygen absorber. Three were enclosed and heat sealed. It was stored in an environment of 25 ° C. for 1 week, and the oxygen concentration in the RP system aluminum bag at that time was 11% by volume.
Thereafter, 2,6-dihydroxynaphthalene was taken out of the bag and measured for purity. The purity was as good as 98%.

(Comparative Example 1-1)
10 kg of 99% pure 2,6-dihydroxynaphthalene was placed in an RP system aluminum bag (manufactured by Mitsubishi Gas Chemical Company), and the RP system aluminum bag was heat-sealed and sealed without degassing. The oxygen concentration in the RP system aluminum bag at that time was 20.8% by volume.
After storing for 1 week at 25 ° C., 2,6-dihydroxynaphthalene was taken out of the bag and the purity was measured.

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)).
Moreover, this invention can provide the method of packing a hydroxy substituted aromatic compound (for example, compound represented by Formula (1)) industrially advantageously.

Claims

A method for producing a hydroxy-substituted aromatic compound, comprising a step of drying the hydroxy-substituted aromatic compound in an atmosphere having an oxygen concentration of less than 20% by volume.
The method for producing a hydroxy-substituted aromatic compound according to claim 1, wherein the hydroxy-substituted aromatic compound is a hydroxy-substituted aromatic compound represented by the following formula (A 0 ) and / or (B 0 ).

(In the above formula (A 0 ), n 0 is an integer of 0 to 9, m 0 is an integer of 0 to 2, p 0 is an integer of 0 to 9, and each Ra is independently hydrogen. An atom, a hydroxyl group, a halogen group, a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms which may have a substituent, or a group having 2 to 40 carbon atoms It is a group consisting of an alkenyl group and 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 R b is each independently a hydrogen atom, a hydroxyl group, a halogen group, a carbon number of 1 to A group consisting of 40 linear, branched or cyclic alkyl groups, optionally substituted aryl groups having 6 to 40 carbon atoms, or alkenyl groups having 2 to 40 carbon atoms and combinations thereof. The alkyl group, aryl group or alkenyl group may contain an ether bond, a ketone bond or an ester bond. )
The method for producing a hydroxy-substituted aromatic compound according to claim 1, wherein the hydroxy-substituted aromatic compound is a hydroxy-substituted aromatic compound represented by the following formula (A) and / or (B).

(In the above formula (A), n 0 is an integer of 0 to 9, m 0 is an integer of 0 to 2, p 0 is an integer of 0 to 9, and R 0 is each independently carbon. A 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 above formula (B), n 1 is an integer of 0 to 9, p 1 is an integer of 0 to 9, and each R 1 is independently a linear, branched or branched group having 1 to 30 carbon atoms. 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. )
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), The method for producing a hydroxy-substituted aromatic compound according to claim 1, which is at least one selected from the group consisting of a compound represented by A-4) and a compound represented by the following formula (B-1).

(In the above formulas (A-1) to (A-4), n 0 is an integer from 0 to 9, and in the above formula (B-1), n 1 is an integer from 0 to 9.)
The manufacturing method of Claim 1 whose said hydroxy substituted aromatic compound is a compound represented by following formula (1).
The production method according to any one of claims 1 to 5, wherein the drying step is performed in the presence of a reducing substance.
The reducing substance is sulfurous acid (salt), bisulfite (salt), pyrosulfurous acid (salt), dithionic acid (salt), trithionic acid (salt), tetrathionic acid (salt), thiosulfuric acid (salt) Rongalite, thioacetic acid (salt), 2,3-dimercapto-1-propanol, dimethyl sulfoxide, thiourea dioxide, monomethylamine, dimethylamine, trimethylamine, monoethanolamine, diethanolamine, triethanolamine, phosphorous acid ( The manufacturing method of Claim 6 which is 1 or more types chosen from the group which consists of a salt) and hypophosphorous acid (salt).
A method for packing a hydroxy-substituted aromatic compound, including a step of packing the hydroxy-substituted aromatic compound in an atmosphere having an oxygen concentration of less than 20% by volume.
The packaging method of the hydroxy substituted aromatic compound of Claim 8 whose said hydroxy substituted aromatic compound is a hydroxy substituted aromatic compound represented by a following formula ( A0 ) and / or ( B0 ).

(In the above formula (A 0 ), n 0 is an integer of 0 to 9, m 0 is an integer of 0 to 2, p 0 is an integer of 0 to 9, and each Ra is independently hydrogen. An atom, a hydroxyl group, a halogen group, a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms which may have a substituent, or a group having 2 to 40 carbon atoms It is a group consisting of an alkenyl group and 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 R b is each independently a hydrogen atom, a hydroxyl group, a halogen group, a carbon number of 1 to A group consisting of 40 linear, branched or cyclic alkyl groups, optionally substituted aryl groups having 6 to 40 carbon atoms, or alkenyl groups having 2 to 40 carbon atoms and combinations thereof. The alkyl group, aryl group or alkenyl group may contain an ether bond, a ketone bond or an ester bond. )
The method for packing a hydroxy-substituted aromatic compound according to claim 8, wherein the hydroxy-substituted aromatic compound is a hydroxy-substituted aromatic compound represented by the following formula (A) and / or (B).

(In the above formula (A), n 0 is an integer of 0 to 9, m 0 is an integer of 0 to 2, p 0 is an integer of 0 to 9, and R 0 is each independently carbon. A 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 above formula (B), n 1 is an integer of 0 to 9, p 1 is an integer of 0 to 9, and each R 1 is independently a linear, branched or branched group having 1 to 30 carbon atoms. 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. )
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), The method for packing a hydroxy-substituted aromatic compound according to claim 8, which is at least one selected from the group consisting of a compound represented by A-4) and a compound represented by the following formula (B-1).

(In the above formulas (A-1) to (A-4), n 0 is an integer from 0 to 9, and in the above formula (B-1), n 1 is an integer from 0 to 9.)
The packaging method according to claim 8, wherein the hydroxy-substituted aromatic compound is a compound represented by the following formula (1).
The packaging method according to any one of claims 8 to 12, comprising a step of allowing the hydroxy-substituted aromatic compound and a desiccant to coexist in a packaging container.
The packaging method according to any one of claims 8 to 13, comprising a step of allowing the hydroxy-substituted aromatic compound and the reducing substance to coexist in a packaging container.
The packaging method according to any one of claims 8 to 14, comprising a step of allowing the hydroxy-substituted aromatic compound and the oxygen scavenger to coexist in a packaging container.
The reducing substance is sulfurous acid (salt), bisulfite (salt), pyrosulfurous acid (salt), dithionic acid (salt), trithionic acid (salt), tetrathionic acid (salt), thiosulfuric acid (salt) Rongalite, thioacetic acid (salt), 2,3-dimercapto-1-propanol, dimethyl sulfoxide, thiourea dioxide, monomethylamine, dimethylamine, trimethylamine, monoethanolamine, diethanolamine, triethanolamine, phosphorous acid ( The packaging method according to claim 14, which is at least one selected from the group consisting of a salt) and hypophosphorous acid (salt).