JP2000186080A - Production of high-purity hydroquinone bis(anhydrotrimellitate) - Google Patents
Production of high-purity hydroquinone bis(anhydrotrimellitate)Info
- Publication number
- JP2000186080A JP2000186080A JP36287098A JP36287098A JP2000186080A JP 2000186080 A JP2000186080 A JP 2000186080A JP 36287098 A JP36287098 A JP 36287098A JP 36287098 A JP36287098 A JP 36287098A JP 2000186080 A JP2000186080 A JP 2000186080A
- Authority
- JP
- Japan
- Prior art keywords
- anhydrotrimellitate
- purity
- group
- hydroquinone bis
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高純度ヒドロキノ
ンビス（アンヒドロトリメリテート）の製造方法に関す
る。The present invention relates to a method for producing high-purity hydroquinone bis (anhydrotrimellitate).
【０００２】[0002]
【従来の技術】一般式（２） で表されるヒドロキノンビス（アンヒドロトリメリテー
ト）（以下「ＴＭＨＱ」という）は、ポリイミド原料と
して有用である。ポリイミド原料としてＴＭＨＱを供給
する場合、高分子量のポリイミドを得るためには、ＴＭ
ＨＱの純度が９８重量％以上であり、且つポリイミドフ
ィルムを形成した際、ＴＭＨＱ由来のゲル状異物が生じ
ず、フィルムの表面が平滑であることが求められてい
る。ここで、ゲル状異物とは、倍率１００倍の光学顕微
鏡で観察される、直径１〜１００μｍの大きさを有した
粒状異物であり、該異物がポリイミドフィルム中に存在
した場合、ポリイミドフィルムの機械強度、電気的特性
等が損なわれる。2. Description of the Related Art General formula (2) The hydroquinone bis (anhydrotrimellitate) (hereinafter referred to as “TMHQ”) is useful as a polyimide raw material. When TMHQ is supplied as a polyimide raw material, in order to obtain a high molecular weight polyimide, TM
It is required that the purity of HQ is 98% by weight or more, and when a polyimide film is formed, no gel-like foreign matter derived from TMHQ occurs and the surface of the film is smooth. Here, the gel-like foreign matter is a particulate foreign matter having a size of 1 to 100 μm in diameter, which is observed with an optical microscope at a magnification of 100 times, and when the foreign matter is present in the polyimide film, the mechanical properties of the polyimide film Strength, electrical characteristics, etc. are impaired.
【０００３】一方、ＴＭＨＱを製造する方法としては以
下の方法が知られている。 （１）ベンゼンやトルエン等の溶媒中、無水トリメリッ
ト酸クロリドとフェノール類（或いはジオール類）との
反応による方法（特公昭４３−５９１１号）。 （２）無水トリメリット酸とジオール類を２００℃以上
に加熱することによる方法（特公昭４５−２９９７４
号）。 （３）無機化合物触媒の存在下、フェノール類の低級ア
ルカン酸エステルとトリメリット酸無水物とをエステル
交換する方法（特開平７−４１４７２号）。On the other hand, the following method is known as a method for producing TMHQ. (1) A method of reacting trimellitic anhydride chloride with phenols (or diols) in a solvent such as benzene or toluene (JP-B-43-5911). (2) A method by heating trimellitic anhydride and diols to 200 ° C. or higher (Japanese Patent Publication No. 45-29974)
issue). (3) A method of transesterifying a lower alkanoic acid ester of a phenol with trimellitic anhydride in the presence of an inorganic compound catalyst (JP-A-7-41472).
【０００４】しかしながら、これらの製造法においては
純度９８重量％以上の高純度ＴＭＨＱは得られない。
又、（１）で示される方法では、高価で安全衛生面で問
題のある無水トリメリット酸クロリドを使用せねばなら
ず、工業的に問題が多い。However, in these production methods, high-purity TMHQ having a purity of 98% by weight or more cannot be obtained.
Further, in the method shown in (1), it is necessary to use trimellitic anhydride chloride which is expensive and has a problem in terms of safety and hygiene, and there are many industrial problems.
【０００５】又、高純度ＴＭＨＱを製造する方法とし
て、特開平１０−３６３６４号では、ヒドロキノンの低
級アルカン酸エステルと無水トリメリット酸とからＴＭ
ＨＱ反応粗物を得、その後、反応粗物を反応容器から直
接取り出した後、該粗物を疎水性溶媒と、ケトン、エー
テル及びエステル等の溶媒との混合溶媒を用いて精製す
ることにより高純度のＴＭＨＱを得ている。この方法で
は、反応容器から固体状のＴＭＨＱ粗物を直接取り出す
必要があり、作業性が悪いという問題があった。As a method for producing high-purity TMHQ, Japanese Patent Application Laid-Open No. 10-36364 discloses a method for preparing TMHQ from a lower alkanoic acid ester of hydroquinone and trimellitic anhydride.
The HQ reaction crude is obtained, and then the reaction crude is directly taken out of the reaction vessel, and the crude is purified by using a mixed solvent of a hydrophobic solvent and a solvent such as ketone, ether and ester. Purity of TMHQ is obtained. In this method, it is necessary to directly remove the solid TMHQ crude from the reaction vessel, and there is a problem that workability is poor.
【０００６】更に、ＴＭＨＱの製造方法によっては、Ｈ
ＰＬＣでは高純度のＴＭＨＱであるが、ＨＰＬＣ等の分
析では検出できない異物を含み、ポリイミドフィルムを
形成した際のフィルムにゲル状の異物が生じ、ポリイミ
ドフィルム用に使用する場合に機械強度が低下する等の
問題が生じるＴＭＨＱもあり、より高純度化が求められ
ている。Further, depending on the method of producing TMHQ, H
Although it is a high-purity TMHQ in PLC, it contains foreign matter that cannot be detected by analysis such as HPLC, and gel-like foreign matter occurs in the film when the polyimide film is formed, and the mechanical strength decreases when used for polyimide film In some cases, such problems as TMHQ occur, and higher purification is required.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、ポリイミド
フィルムを形成した際のフィルムにＴＭＨＱ由来のゲル
状異物が生じない、ポリイミド原料として有用な高純度
ＴＭＨＱを、効率よく且つ作業性良く製造する方法を提
供することを目的とする。DISCLOSURE OF THE INVENTION The present invention is to produce a high-purity TMHQ useful as a polyimide raw material, in which no gel-like foreign matter derived from TMHQ is formed in the film when the polyimide film is formed, efficiently and with good workability. The aim is to provide a method.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、かかる課
題を達成すべく鋭意検討を行った結果、ＴＭＨＱ反応粗
物を特定溶媒を用いてスラリー化し、次いで特定の溶媒
を用いて精製するという一連の工程により所期の目的が
達成されることを見いだし、かかる知見に基づいて本発
明を完成するに至った。本発明でスラリーとは、溶媒中
にＴＭＨＱ及び／又はＴＭＨＱ反応粗物が、流動性を有
した直径１０μｍ〜５ｍｍの大きさの固体状態で析出
し、懸濁又は分散している状態をいう。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the object, and as a result, the TMHQ reaction crude product is slurried using a specific solvent and then purified using a specific solvent. It has been found that the intended purpose is achieved by the series of steps described above, and the present invention has been completed based on such knowledge. In the present invention, the slurry refers to a state in which TMHQ and / or a crude TMHQ reaction precipitate in a solvent in a solid state having a diameter of 10 μm to 5 mm having fluidity and are suspended or dispersed.
【０００９】即ち、本発明は、一般式（１） ［式中、Ｒ１、Ｒ２は、同一又は異なって、炭素数１〜
３のアルキル基を表す。］で表されるヒドロキノンの低
級アルカン酸エステルと無水トリメリット酸をエステル
交換反応しヒドロキノンビス（アンヒドロトリメリテー
ト）を製造するに際し、エステル交換反応により得たヒ
ドロキノンビス（アンヒドロトリメリテート）反応粗物
を（Ａ）群に属する溶媒を用いてスラリー状としたの
ち、（Ａ）群及び（Ｂ）群からなる混合溶媒を用いて精
製することを特徴とする。 （Ａ）群： ラクトン系溶媒の１種若しくは２種以上。 （Ｂ）群：炭素数が６〜２０の芳香族又は脂肪族の炭化
水素の１種若しくは２種以上。That is, the present invention provides a compound represented by the general formula (1) [Wherein, R 1 and R 2 are the same or different and each have 1 to 1 carbon atoms.
3 represents an alkyl group. In the production of hydroquinone bis (anhydrotrimellitate) by transesterification of a lower alkanoic acid ester of hydroquinone represented by the following formula and trimellitic anhydride, hydroquinone bis (anhydrotrimellitate) obtained by the transesterification reaction The reaction crude is made into a slurry using a solvent belonging to the group (A), and then purified using a mixed solvent consisting of the groups (A) and (B). Group (A): One or more lactone solvents. Group (B): One or more aromatic or aliphatic hydrocarbons having 6 to 20 carbon atoms.
【００１０】同時に、本発明は、一般式（１）で表され
るヒドロキノンの低級アルカン酸エステルと無水トリメ
リット酸をエステル交換反応しヒドロキノンビス（アン
ヒドロトリメリテート）を製造するに際し、エステル交
換反応により得たヒドロキノンビス（アンヒドロトリメ
リテート）反応粗物を（Ａ）群に属する溶媒を用いてス
ラリー状としたのち、（Ａ）群に属する溶媒を用いて精
製することを特徴とする高純度ヒドロキノンビス（アン
ヒドロトリメリテート）の製造方法をも提供する。At the same time, the present invention provides a method for producing a hydroquinone bis (anhydrotrimellitate) by transesterification of a lower alkanoic acid ester of hydroquinone represented by the general formula (1) with trimellitic anhydride. A hydroquinone bis (anhydrotrimellitate) reaction crude product obtained by the reaction is converted into a slurry using a solvent belonging to Group (A), and then purified using a solvent belonging to Group (A). A method for producing high-purity hydroquinone bis (anhydrotrimellitate) is also provided.
【００１１】更に、本発明は、ヒドロキノンビス（アン
ヒドロトリメリテート）の純度が９８重量％以上であ
り、且つポリイミドフィルムを形成した際の、フィルム
の表面が平滑であり且つフィルム中にゲル状異物を生じ
ない高純度ヒドロキノンビス（アンヒドロトリメリテー
ト）をも提供する。Further, the present invention relates to a hydroquinone bis (anhydrotrimellitate) having a purity of 98% by weight or more, a polyimide film formed on a smooth surface and a gel-like film in the film. Also provided is a high-purity hydroquinone bis (anhydrotrimellitate) which does not generate foreign matter.
【００１２】[0012]
【発明の実施の形態】本発明に係る一般式（１）で表さ
れるヒドロキノンの低級アルカン酸エステルとしては、
ヒドロキノンの酢酸エステル、プロピオン酸エステル及
び酪酸エステルが例示され、特に好ましくは酢酸エステ
ルが挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION The lower alkanoic acid ester of hydroquinone represented by the general formula (1) according to the present invention includes:
Examples thereof include acetate, propionate and butyrate of hydroquinone, and particularly preferably acetate.
【００１３】ヒドロキノンの低級アルカン酸エステル
は、通常のエステル化技術を用いて製造することができ
る。具体的な方法としては、無触媒下で、過剰のアルカ
ン酸無水物を用いてアルカン酸エステルとする方法や、
従来公知のエステル化触媒の存在下に、ヒドロキノンと
アルカン酸或いはアルカン酸無水物とを反応させる方法
（有機化学Ｉ、ｐ１８１〜１８９、梅沢純夫著、丸善株
式会社、１９５９年出版等を参照）等が例示される。[0013] The lower alkanoic acid esters of hydroquinone can be prepared using conventional esterification techniques. Specific methods include, in the absence of a catalyst, a method of using an excess of an alkanoic anhydride to form an alkanoic acid ester,
A method of reacting hydroquinone with an alkanoic acid or an alkanoic anhydride in the presence of a conventionally known esterification catalyst (see Organic Chemistry I, pp. 181 to 189, written by Sumio Umezawa, Maruzen Co., 1959, etc.), and the like. Is exemplified.
【００１４】本発明に係るヒドロキノンの低級アルカン
酸エステルと無水トリメリット酸（以下、「ＴＭＡ」と
いう）とのエステル交換反応に於いて、ヒドロキノンの
低級アルカン酸エステル１モルに対するＴＭＡの仕込み
量は１．８〜５．０モルが挙げられ、より好ましくは
２．０〜４．０モルが推奨される。ＴＭＡの仕込み量が
１．８モル未満であると反応粗物中にヒドロキノンモノ
アセチルモノ（アンヒドロトリメリテート）が生じやす
く、このものはヒドロキノンビス（アンヒドロトリメリ
テート）からの除去が非常に困難となり好ましくない。
一方、５．０モルを越える場合は反応粗物の純度が低く
なり、以下の精製工程で目的とする純度が得られなかっ
たり、得られても精製回数を増やす必要があり、収率が
極端に低くなり好ましくない。In the transesterification reaction between the lower alkanoic acid ester of hydroquinone and trimellitic anhydride (hereinafter referred to as "TMA") according to the present invention, the amount of TMA charged to 1 mole of the lower alkanoic acid ester of hydroquinone is 1 0.8 to 5.0 mol, more preferably 2.0 to 4.0 mol. If the charged amount of TMA is less than 1.8 mol, hydroquinone monoacetyl mono (anhydrotrimellitate) is liable to be generated in the reaction crude, which is very difficult to remove from hydroquinone bis (anhydrotrimellitate). It is not preferable because it becomes difficult.
On the other hand, if it exceeds 5.0 moles, the purity of the reaction crude will be low, and the following purification steps will not provide the desired purity, or if it is obtained, it will be necessary to increase the number of purifications. Is not preferred.
【００１５】エステル交換反応は、無触媒下でも触媒存
在下でも行うことができ、適応される触媒としては、硫
酸、ｐ−トルエンスルホン酸等の酸触媒、ゼオライト、
ベントナイト、カオリン等のシリカ・アルミナ系触媒、
酢酸ナトリウム、水酸化ナトリウム等のアルカリ金属塩
系触媒類、三級アミン類、トリフェニルフォスフィン等
が例示され、ＴＭＨＱの用途に応じて、適宜、触媒の有
無及びその種類を選択することができる。例えば、ＴＭ
ＨＱを電子部品用のポリイミド原料として使用する場合
は、無触媒或いは触媒の形態が液状である三級アミン
類、硫酸等が好ましい。The transesterification can be carried out without a catalyst or in the presence of a catalyst. Suitable catalysts include acid catalysts such as sulfuric acid and p-toluenesulfonic acid, zeolites, and the like.
Silica-alumina catalysts such as bentonite and kaolin,
Examples thereof include alkali metal salt-based catalysts such as sodium acetate and sodium hydroxide, tertiary amines, and triphenylphosphine. Depending on the use of TMHQ, the presence or absence of the catalyst and the type thereof can be appropriately selected. . For example, TM
When HQ is used as a polyimide raw material for electronic components, tertiary amines, sulfuric acid, etc., which are non-catalytic or in the form of a catalyst in a liquid form, are preferred.
【００１６】触媒の添加量としては、触媒の種類やエス
テル交換反応条件により適宜選択されるが、通常、原料
であるヒドロキノンの低級アルカン酸エステル及びＴＭ
Ａの合計量に対し０〜１０重量％が例示され、より好ま
しくは０〜５重量％が推奨される。The amount of the catalyst to be added is appropriately selected depending on the type of the catalyst and the conditions of the transesterification reaction.
0 to 10% by weight based on the total amount of A is exemplified, and more preferably 0 to 5% by weight is recommended.
【００１７】当該エステル交換反応は撹拌下で行われ、
反応温度としては、通常、１５０〜３００℃、特に２２
０〜２６０℃程度が奨励され、エステル交換反応中に生
成する低級アルカン酸を常圧または減圧下にて、逐次反
応系外に留去させることにより行う。The transesterification is carried out under stirring,
The reaction temperature is usually 150 to 300 ° C., especially 22
It is carried out by successively distilling the lower alkanoic acid generated during the transesterification reaction out of the reaction system at normal pressure or under reduced pressure.
【００１８】当該エステル交換反応をより有利に進める
には、反応時にキシレン、トルエン、アニソール等のエ
ントレーナーの使用、窒素ガス、炭酸ガス等の反応に不
活性なガスを通気させる方法が有効である。In order to promote the transesterification more advantageously, it is effective to use an entrainer such as xylene, toluene, or anisole during the reaction, or to pass a gas inert to the reaction, such as nitrogen gas or carbon dioxide gas. .
【００１９】反応圧力については、当該エステル交換反
応の後半に５００〜２０ｍｍＨｇまで徐々に減圧するこ
とで、より反応を有効に進めることができる。Regarding the reaction pressure, the reaction can be more effectively advanced by gradually reducing the pressure to 500 to 20 mmHg in the latter half of the transesterification reaction.
【００２０】当該エステル交換反応に於いて留出させる
低級アルカン酸量は、理論量の６５重量％以上が例示さ
れ、好ましくは９０重量％以上が挙げられる。その反応
時間は反応条件により異なるが、通常０．５〜２０時間
である。The amount of lower alkanoic acid distilled in the transesterification reaction is, for example, 65% by weight or more of the theoretical amount, and preferably 90% by weight or more. The reaction time varies depending on the reaction conditions, but is usually 0.5 to 20 hours.
【００２１】エステル交換反応で生成したＴＭＨＱ反応
粗物は、引き続き反応系内に（Ａ）群に属する溶媒を添
加し攪拌することにより、スラリー状とする。この際、
好ましくは温度が２００℃以上の、より好ましくは２４
０〜２２０℃のＴＭＨＱ反応粗物中に、（Ａ）群の溶媒
を添加し、徐冷しながら、０．１〜５時間、好ましくは
０．２〜１時間攪拌することによりスラリー化する。The TMHQ reaction crude product produced by the transesterification reaction is continuously converted into a slurry by adding a solvent belonging to the group (A) into the reaction system and stirring. On this occasion,
Preferably the temperature is above 200 ° C., more preferably 24
The solvent of the group (A) is added to the TMHQ reaction crude at 0 to 220 ° C., and the slurry is formed by stirring for 0.1 to 5 hours, preferably 0.2 to 1 hour while cooling slowly.
【００２２】（Ａ）群に係る溶媒としてはラクトン系溶
媒であり、１種若しくは２種以上を適宜混合して用いら
れる。The solvent according to the group (A) is a lactone-based solvent, and one kind or a mixture of two or more kinds is used as appropriate.
【００２３】具体的なラクトン系溶媒としては、γ−ブ
チロラクトン、α−メチレン−γ−ブチロラクトン等が
例示される。なかでも、スラリー化させるに際し用いる
好ましい溶媒としてγ−ブチロラクトンが挙げられる。Specific lactone solvents include γ-butyrolactone, α-methylene-γ-butyrolactone and the like. Among them, γ-butyrolactone is a preferred solvent used for slurrying.
【００２４】スラリー化する際の（Ａ）群に属する溶媒
の使用量は、ＴＭＨＱ反応粗物１００重量部に対し５０
〜３００重量部が挙げられる。溶媒使用量が５０部未満
であれば非常に高濃度スラリーとなり抜き出す場合非常
に困難であり、３００重量部を越えるとＴＭＨＱ粗物の
収量が低下し工業的な方法としては好ましくない。The amount of the solvent belonging to the group (A) at the time of slurrying is 50 to 100 parts by weight of the crude product of TMHQ reaction.
To 300 parts by weight. If the amount of the solvent used is less than 50 parts, the slurry becomes very high in concentration and it is very difficult to extract the slurry. If the amount exceeds 300 parts by weight, the yield of the TMHQ crude material decreases, which is not preferable as an industrial method.
【００２５】スラリー化したＴＭＨＱは、引き続き次の
（１）〜（３）のいずれかの方法で精製を行うことによ
り高純度のＴＭＨＱを得る。The slurried TMHQ is subsequently purified by any of the following methods (1) to (3) to obtain high-purity TMHQ.
【００２６】（１）該スラリーを濾別、乾燥して、高純
度のＴＭＨＱを得る方法。 （２）該スラリー中に（Ｂ）群の溶媒を加え、（Ａ）群
及び（Ｂ）群からなる混合溶媒とし、この混合溶媒を用
いてＴＭＨＱを精製し、引き続き濾別、乾燥して、高純
度のＴＭＨＱを得る方法。 （３）該スラリーを濾別した後、（Ａ）群及び（Ｂ）群
からなる混合溶媒を加えてＴＭＨＱを精製し、引き続き
濾別、乾燥して、高純度のＴＭＨＱを得る方法。(1) A method of filtering and drying the slurry to obtain high-purity TMHQ. (2) A solvent of group (B) is added to the slurry to form a mixed solvent consisting of group (A) and group (B). TMHQ is purified using this mixed solvent, followed by filtration and drying. A method for obtaining high purity TMHQ. (3) A method of filtering the slurry, adding a mixed solvent consisting of groups (A) and (B) to purify TMHQ, and subsequently filtering and drying to obtain high-purity TMHQ.
【００２７】上記３つの方法による精製のなかでも、よ
り高純度のＴＭＨＱを所望する場合は（３）の方法が、
単離収率を考慮した場合（１）又は（２）の方法が好ま
しい。[0027] Among the above three purification methods, when a higher purity TMHQ is desired, the method (3) is used.
In consideration of the isolation yield, the method (1) or (2) is preferable.
【００２８】（Ｂ）群に係る溶媒としては、炭素数６〜
２０の芳香族又は脂肪族の炭化水素が挙げられ、具体的
には、ベンゼン、トルエン、キシレン、エチルベンゼン
等の芳香族炭化水素、ヘキサン、オクタン、シクロヘキ
サン等の脂肪族鎖状あるいは脂肪族環状炭化水素が例示
され、なかでも好ましくはキシレン、トルエン、ベンゼ
ン、シクロヘキサン及びヘキサンが推奨される。これら
（Ｂ）群に属する溶媒はそれぞれ単独で又は２種以上を
適宜混合して用いられる。As the solvent according to the group (B), those having 6 to 6 carbon atoms are used.
20 aromatic or aliphatic hydrocarbons, specifically, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; and aliphatic chain or aliphatic cyclic hydrocarbons such as hexane, octane, and cyclohexane. Xylene, toluene, benzene, cyclohexane and hexane are particularly preferred. These solvents belonging to the group (B) may be used alone or in combination of two or more.
【００２９】以下、３つの方法について具体的に説明す
る。Hereinafter, the three methods will be specifically described.
【００３０】（１）スラリーを濾別、乾燥して、高純度
のＴＭＨＱを得る方法 該スラリーから（Ａ）群の溶媒を除去してＴＭＨＱを得
る方法であり、一般的には濾過或いは遠心分離等により
行う。(1) The slurry is filtered and dried to obtain a high purity
This is a method for obtaining TMHQ by removing the solvent of group (A) from the slurry, and is generally performed by filtration or centrifugation.
【００３１】該スラリーを４０℃程度に冷却後、濾過或
いは遠心分離により高純度ＴＭＨＱを得、続いて、常圧
下若しくは減圧下（好ましくは５〜３００ｍｍＨｇ）、
室温〜２００℃の温度で、０．１時間〜２０時間程度乾
燥することにより高純度ＴＭＨＱを得る。After cooling the slurry to about 40 ° C., high purity TMHQ is obtained by filtration or centrifugation, and subsequently under normal pressure or reduced pressure (preferably 5 to 300 mmHg).
High-purity TMHQ is obtained by drying at room temperature to 200 ° C. for about 0.1 to 20 hours.
【００３２】スラリー化する（Ａ）群の好ましい溶媒量
としてはＴＭＨＱ反応粗物１００重量部につき（Ａ）群
の溶媒を１００〜３００量部用いることが推奨される。It is recommended to use 100 to 300 parts by weight of the solvent of the group (A) per 100 parts by weight of the crude TMHQ reaction product.
【００３３】尚、必要に応じて、ＴＭＨＱ濾別結晶を、
又は溶媒を除去後のＴＭＨＱを、再度、（Ａ）群の溶媒
を用いて精製しても良い。If necessary, the TMHQ filtered crystal may be
Alternatively, the TMHQ from which the solvent has been removed may be purified again using the solvent of the group (A).
【００３４】（２）スラリーに（Ｂ）群の溶媒を加え混
合溶媒とし精製し、高純度のＴＭＨＱを得る方法 該スラリー中に（Ｂ）群の溶媒を加え、系内で（Ａ）群
及び（Ｂ）群からなる混合溶媒を調製し精製する方法で
ある。(2) The solvent of group (B) is added to the slurry and mixed.
A method of obtaining a high-purity TMHQ by purifying as a mixed solvent This is a method of adding a solvent of the group (B) to the slurry to prepare and purify a mixed solvent composed of the groups (A) and (B) in the system. .
【００３５】この場合、スラリー化する（Ａ）群の溶媒
量としてより好ましくはＴＭＨＱ反応粗物１００重量部
につき（Ａ）群の溶媒を１００〜３００量部用いること
が推奨される。In this case, it is more preferable to use 100 to 300 parts by weight of the solvent of the group (A) per 100 parts by weight of the crude TMHQ reaction product as the amount of the solvent of the group (A) to be slurried.
【００３６】該スラリーに、３０〜１５０℃の温度で
（Ｂ）群の溶媒を加えた後、３０〜２００℃の温度で、
好ましくは、３０〜１６０℃で、０．１〜１０時間加熱
攪拌し、溶解または懸濁させる。次に系を４０℃以下ま
で徐冷し、（１）の方法に準じ析出物を濾別することに
よりＴＭＨＱ濾別結晶を得る。得られた高純度ＴＭＨＱ
濾別結晶は、（１）の方法に準じて乾燥する。After adding the solvent of group (B) to the slurry at a temperature of 30 to 150 ° C.,
Preferably, the mixture is heated and stirred at 30 to 160 ° C. for 0.1 to 10 hours to dissolve or suspend. Next, the system is gradually cooled to 40 ° C. or lower, and the precipitate is filtered out according to the method (1) to obtain a TMHQ filtered crystal. High purity TMHQ obtained
The filtered crystals are dried according to the method (1).
【００３７】尚、スラリー中に（Ｂ）群の溶媒を加える
場合の（Ｂ）群の溶媒量としては、混合溶媒となった際
の（Ａ）群に属する溶媒と（Ｂ）群に属する溶媒の混合
重量比（Ａ群の溶媒／Ｂ群の溶媒）が、０．５／９．５
〜９．５／０．５となるような溶媒量が例示され、好ま
しくは混合溶媒として５／５〜９．５／０．５の範囲内
が挙げられる。In addition, when the solvent of the group (B) is added to the slurry, the amount of the solvent of the group (B) may be a solvent belonging to the group (A) and a solvent belonging to the group (B) when the mixed solvent is obtained. (Solvent of group A / solvent of group B) is 0.5 / 9.5.
The amount of the solvent is from 9.5 / 0.5 to 9.5 / 0.5, and preferably, the mixed solvent is from 5/5 to 9.5 / 0.5.
【００３８】（３）スラリーを濾別後、（Ａ）群及び
（Ｂ）群の混合溶媒により精製し高純度のＴＭＨＱを得
る方法 該スラリーから（Ａ）群の溶媒を除去してＴＭＨＱ濾別
結晶を得た後、更に、（Ａ）群及び（Ｂ）群からなる混
合溶媒を用いて精製する方法である。特に（１）又は
（２）の方法ではＴＭＨＱの純度が不十分な場合に効果
的である。(3) After the slurry is filtered off, group (A) and
Purification with a mixed solvent of group (B) to obtain high-purity TMHQ
This is a method of removing the solvent of group (A) from the slurry to obtain a TMHQ filtered crystal, and then purifying the crystal using a mixed solvent consisting of group (A) and group (B). In particular, the method (1) or (2) is effective when the purity of TMHQ is insufficient.
【００３９】この場合、スラリー化する（Ａ）群の溶媒
量としてより好ましくはＴＭＨＱ反応粗物１００重量部
につき（Ａ）群の溶媒を８０〜２５０量部用いることが
推奨される。In this case, it is more preferable to use 80 to 250 parts by weight of the solvent of the group (A) per 100 parts by weight of the crude TMHQ reaction product as the amount of the solvent of the group (A) to be slurried.
【００４０】（１）の方法に準じて、該スラリーを濾過
又は遠心分離することによりＴＭＨＱの濾別結晶を得
る。該濾別結晶を更に（Ａ）群及び（Ｂ）群からなる混
合溶媒を用いて精製する。According to the method (1), the slurry is filtered or centrifuged to obtain TMHQ filtered crystals. The separated crystals are further purified using a mixed solvent consisting of the groups (A) and (B).
【００４１】又、スラリー化させる際の（Ａ）群に属す
る溶媒は、精製に用いる混合溶媒の成分である溶媒と同
一であることが好ましい。The solvent belonging to the group (A) at the time of slurrying is preferably the same as the solvent which is a component of the mixed solvent used for purification.
【００４２】（Ａ）群及び（Ｂ）群からなる混合溶媒を
用いて精製を行う場合の（Ａ）群に属する溶媒と（Ｂ）
群に属する溶媒の混合重量比（Ａ群の溶媒／Ｂ群の溶
媒）は、通常０．５／９．５〜９．５／０．５が例示さ
れ、好ましくは０．５／９．５〜５／５の範囲内で適宜
選択される。Ｂ群に属する溶媒の比率が高くなると所定
の高純度品が得られにくく、また当該比率が極端に低い
場合には精製物の収率が低下する。When the purification is carried out using a mixed solvent consisting of groups (A) and (B), the solvent belonging to group (A) and (B)
The mixing weight ratio of the solvents belonging to the group (solvent of group A / solvent of group B) is usually 0.5 / 9.5 to 9.5 / 0.5, preferably 0.5 / 9.5. It is appropriately selected within the range of ５ to ／. When the ratio of the solvent belonging to Group B is high, it is difficult to obtain a predetermined high-purity product, and when the ratio is extremely low, the yield of the purified product is reduced.
【００４３】混合溶媒の使用量として、好ましくは、Ｔ
ＭＨＱ濾別結晶１００重量部に対し、５０〜１０００重
量部が挙げられ、特に、２００〜４００重量部の範囲内
が推奨される。溶媒使用量が５０重量部未満であれば高
純度ＴＭＨＱが得られにくく、１０００重量部を越える
と収率が低下し、工業的な方法としては好ましくない。The amount of the mixed solvent used is preferably T
The amount is 50 to 1000 parts by weight, preferably 200 to 400 parts by weight, based on 100 parts by weight of the MHQ filtered crystal. If the amount of the solvent used is less than 50 parts by weight, it is difficult to obtain high-purity TMHQ, and if it exceeds 1000 parts by weight, the yield decreases, which is not preferable as an industrial method.
【００４４】精製において、ＴＭＨＱ濾別結晶に（Ａ）
群及び（Ｂ）群からなる混合溶媒を添加した後、１００
〜２００℃程度に、好ましくは１００〜１６０℃程度で
加熱攪拌し、溶解または懸濁させる。次に系を４０℃以
下まで徐冷して得たスラリーを、（１）の方法に準じて
濾別する。得られた結晶は前述の混合溶媒で洗浄するこ
とが望ましい。次に、ＴＭＨＱ結晶中に残存する溶媒を
乾燥除去し、高純度ＴＭＨＱを得る。操作は窒素ガス等
の不活性ガス雰囲気下で行うことが安全上望ましい。In the purification, (A) was added to the TMHQ filtered crystal.
After adding the mixed solvent consisting of the group (B) and the group (B), 100
The mixture is heated and stirred at about -200 ° C, preferably about 100-160 ° C, and dissolved or suspended. Next, the slurry obtained by gradually cooling the system to 40 ° C. or lower is separated by filtration according to the method (1). The obtained crystals are desirably washed with the above-mentioned mixed solvent. Next, the solvent remaining in the TMHQ crystal is removed by drying to obtain high-purity TMHQ. The operation is desirably performed in an atmosphere of an inert gas such as nitrogen gas for safety.
【００４５】（２）又は（３）の混合溶媒による精製方
法において、（Ａ）群に属する溶媒と（Ｂ）群に属する
溶媒からなる混合溶媒の好ましい組み合わせとしては、 ＊ γ−ブチロラクトン（Ａ）：キシレン（Ｂ）、 ＊ γ−ブチロラクトン（Ａ）：ヘキサン（Ｂ）、 が例示できる。In the purification method using a mixed solvent of (2) or (3), a preferred combination of a mixed solvent comprising a solvent belonging to the group (A) and a solvent belonging to the group (B) is * γ-butyrolactone (A) : Xylene (B), * γ-butyrolactone (A): hexane (B).
【００４６】又、（１）から（３）の精製方法により得
られた、乾燥前の高純度ＴＭＨＱをより高純度化する目
的で、ＴＭＨＱ濾別結晶又は溶媒除去後のＴＭＨＱを更
に（Ａ）群及び（Ｂ）群からなる混合溶媒を用いて繰り
返し精製しても差し支えない。For the purpose of further purifying the high-purity TMHQ before drying obtained by the purification method of (1) to (3), the filtered TMHQ or the TMHQ after removing the solvent is further subjected to (A) The purification may be repeated using a mixed solvent consisting of the group (B) and the group (B).
【００４７】かくして得られた高純度ＴＭＨＱは、ポリ
イミド等の耐熱性樹脂の原料、エポキシ樹脂やウレタン
樹脂の硬化剤、その他化成品の中間原料、樹脂改質剤等
の用途に利用可能である。The high-purity TMHQ thus obtained can be used as a raw material for a heat-resistant resin such as polyimide, a curing agent for an epoxy resin or a urethane resin, an intermediate raw material for a chemical product, a resin modifier, and the like.
【００４８】[0048]
【実施例】以下、実施例を挙げて本発明を詳細に説明す
る。尚、各例における生成物の純度は高速液体クロマト
グラフィーにより測定した。The present invention will be described below in detail with reference to examples. In addition, the purity of the product in each example was measured by high performance liquid chromatography.
【００４９】ポリイミドフィルムの製造 ＴＭＨＱ（１モル）と４，４’−ジアミノジフェニルエ
ーテル（１モル）とをＮ，Ｎ−ジメチルアセトアミド中
（基質濃度１０重量％となる溶媒量）、室温で１０時間
アミド化反応を行い、ポリアミド酸とする。このポリア
ミド酸のＮ，Ｎ−ジメチルアセトアミド溶液をガラス板
上にキャストして５ｍｍＨｇの減圧下、室温から３００
℃に徐々に昇温し、３００℃に達した時点で５〜２０分
間加熱し、厚さ約２０μｍのポリイミドフィルムを調製
する。Preparation of Polyimide Film TMHQ (1 mol) and 4,4'-diaminodiphenyl ether (1 mol) were amide-bonded in N, N-dimethylacetamide (the amount of a solvent to give a substrate concentration of 10% by weight) at room temperature for 10 hours. The reaction is carried out to obtain a polyamic acid. The N, N-dimethylacetamide solution of this polyamic acid was cast on a glass plate, and was heated from room temperature to 300 mm under a reduced pressure of 5 mmHg.
C. and gradually heated to 300.degree. C., and when heated to 300.degree. C., heated for 5 to 20 minutes to prepare a polyimide film having a thickness of about 20 .mu.m.
【００５０】ポリイミドフィルムの観察 イミドフィルムを１００倍の光学顕微鏡を用いてその表
面の突起物及びゲル状異物の存在の有無を観察する。 Observation of Polyimide Film The presence or absence of protrusions and gel-like foreign matters on the surface of the imide film is observed using an optical microscope of 100 times.
【００５１】製造例１ 攪拌機、温度計、冷却管付きデカンター及び窒素ガス導
入口の付いた１Ｌの四ツ口フラスコにヒドロキノン１１
０．１ｇ（１．０モル）及び無水酢酸３０６．３ｇ
（３．０モル）を仕込み、窒素雰囲気下、１３０℃で２
時間反応させた。反応終了後、減圧下に過剰の無水酢酸
と生成した酢酸を留去し純度９９．９％のヒドロキノン
ジアセテート１９２．２ｇ（収率９９％）を得た。Production Example 1 Hydroquinone 11 was placed in a 1 L four-necked flask equipped with a stirrer, a thermometer, a decanter equipped with a cooling tube, and a nitrogen gas inlet.
0.1 g (1.0 mol) and 306.3 g of acetic anhydride
(3.0 mol) at 130 ° C. in a nitrogen atmosphere.
Allowed to react for hours. After completion of the reaction, excess acetic anhydride and generated acetic acid were distilled off under reduced pressure to obtain 192.2 g (yield: 99%) of hydroquinone diacetate having a purity of 99.9%.
【００５２】実施例１ 製造例１と同様の装置に製造例１で得たヒドロキノンジ
アセテート５８．３ｇ（０．３モル）及びＴＭＡ１８
４．４ｇ（０．９６モル）を仕込み、窒素雰囲気下、２
６０℃まで昇温した。同温度で０．５時間反応し、更に
８０ｍｍＨｇまで徐々に減圧して０．５時間反応した。
窒素にて常圧に戻し反応粗物を得た。この反応粗物を２
２５℃まで冷却後、γ−ブチロラクトン５１６．８ｇ
（理論反応粗物の２．５重量倍量）を攪拌下０．５時間
かけて滴下した。滴下終了時、温度は８５℃まで低下し
た。更に４０℃まで冷却し、ＴＭＨＱスラリーを得た。Example 1 In the same apparatus as in Production Example 1, 58.3 g (0.3 mol) of hydroquinone diacetate obtained in Production Example 1 and TMA18
In a nitrogen atmosphere, 4.4 g (0.96 mol) was charged.
The temperature was raised to 60 ° C. The reaction was carried out at the same temperature for 0.5 hour, and further, the pressure was gradually reduced to 80 mmHg, and the reaction was carried out for 0.5 hour.
The pressure was returned to normal pressure with nitrogen to obtain a crude reaction product. This reaction crude is
After cooling to 25 ° C., 516.8 g of γ-butyrolactone
(2.5 weight times the theoretical reaction crude) was added dropwise over 0.5 hour with stirring. At the end of the drop, the temperature dropped to 85 ° C. It was further cooled to 40 ° C. to obtain a TMHQ slurry.
【００５３】該ＴＭＨＱスラリーを濾過し、濾別結晶を
得た。この濾別結晶を５ｍｍＨｇの減圧下、１４０℃の
温度で１０時間乾燥し、ＴＭＨＱ純度９８．７％、ＴＭ
Ａ含有率１．０％、ヒドロキノンモノアセチルモノ（ア
ンヒドロトリメリテート）（以下「ＴＭＨＱモノ体」と
いう）０．３％のＴＭＨＱを６２ｇ得た。収率（対理論
反応粗物）は３０％であった。The TMHQ slurry was filtered to obtain a separated crystal. The separated crystals were dried at 140 ° C. for 10 hours under a reduced pressure of 5 mmHg to give a TMHQ purity of 98.7%.
62 g of TMHQ having an A content of 1.0% and hydroquinone monoacetyl mono (anhydrotrimellitate) (hereinafter referred to as "TMHQ mono-form") 0.3% was obtained. The yield (vs. the theoretical reaction crude) was 30%.
【００５４】得られたＴＭＨＱ１０ｇを、９０ｇのＮ，
Ｎ−ジメチルホルムアミド（以下「ＤＭＦ」という）に
溶解したところ、得られた溶液に濁りは見られなかっ
た。10 g of the obtained TMHQ was mixed with 90 g of N,
When dissolved in N-dimethylformamide (hereinafter referred to as "DMF"), no turbidity was observed in the obtained solution.
【００５５】更に、このＴＭＨＱ４．６４ｇ（ＴＭＨＱ
換算で１．０モル）と４，４’−ジアミノジフェニルエ
ーテル２．０ｇ（１．０モル）及びＮ，Ｎ−ジメチルア
セトアミド５９．８ｇを、攪拌機、窒素ガス導入口を取
り付けた１００ｍｌ三ツ口フラスコに窒素雰囲気下に仕
込み、室温で１０時間攪拌し、固形分濃度１０重量％の
粘稠なポリアミド酸溶液を得た。このポリアミド酸溶液
をガラス板上にキャストして５ｍｍＨｇの減圧下、室温
〜３００℃に徐々に昇温し、３００℃で１０分間加熱す
ることにより、厚さ２０μｍのポリイミドフィルムを得
た。このポリイミドフィルムをガラス板上から剥がし、
１００倍の光学顕微鏡で観察したが、ゲル状異物は観察
されず、且つフィルム表面は平滑であった。Further, 4.64 g of this TMHQ (TMHQ
1.0 mol), 2.0 g (1.0 mol) of 4,4'-diaminodiphenyl ether and 59.8 g of N, N-dimethylacetamide were placed in a 100 ml three-necked flask equipped with a stirrer and a nitrogen gas inlet. The mixture was charged in an atmosphere and stirred at room temperature for 10 hours to obtain a viscous polyamic acid solution having a solid content of 10% by weight. The polyamic acid solution was cast on a glass plate, gradually heated from room temperature to 300 ° C. under a reduced pressure of 5 mmHg, and heated at 300 ° C. for 10 minutes to obtain a polyimide film having a thickness of 20 μm. Peel this polyimide film from the glass plate,
When observed with an optical microscope of 100 times, no gel-like foreign matter was observed and the film surface was smooth.
【００５６】実施例２ 実施例１と同様にＴＭＨＱ反応粗物を合成した後、２２
５℃でγ−ブチロラクトン２５２．２ｇ（対理論反応粗
物の１．２２重量倍量）を攪拌下０．５時間かけて滴下
した。滴下終了時、温度は１２５℃まで低下した。更に
４０℃まで冷却してＴＭＨＱスラリーを得た。Example 2 After the TMHQ reaction crude was synthesized in the same manner as in Example 1,
At 5 ° C., 252.2 g of γ-butyrolactone (1.22 times the weight of the theoretical reaction crude) was added dropwise with stirring over 0.5 hours. At the end of the drop, the temperature dropped to 125 ° C. It was further cooled to 40 ° C. to obtain a TMHQ slurry.
【００５７】該ＴＭＨＱスラリーを濾過し、１１６．３
ｇの濾別結晶を得た。この濾別結晶の一部を５ｍｍＨｇ
の減圧下、１４０℃の温度で１０時間乾燥したところＴ
ＭＨＱ純度９６．２％、ＴＭＡ含有率３．０％、ＴＭＨ
Ｑモノ体０．８％であった。又、この濾別結晶中の固形
分含有率は８０重量％であり、残り２０重量％は溶媒で
あった。The TMHQ slurry was filtered to obtain 116.3.
g of filtered crystals were obtained. A part of the crystal separated by filtration is 5 mmHg.
After drying at 140 ° C. for 10 hours under reduced pressure of
MHQ purity 96.2%, TMA content 3.0%, TMH
The Q mono body was 0.8%. The solid content in the filtered crystal was 80% by weight, and the remaining 20% by weight was a solvent.
【００５８】次いで、得られた濾別結晶１００ｇ（固形
分８０ｇ）とγ−ブチロラクトン４８ｇ及びキシレン１
９２ｇを同様の装置に窒素ガス雰囲気下で仕込み、混合
溶媒の還流温度（１４２℃）で２時間攪拌した。次に４
０℃まで冷却した後濾過し、得られた濾別結晶をγ−ブ
チロラクトン６ｇ、キシレン２４ｇの混合溶媒で洗浄し
た。更にこの濾別結晶を５ｍｍＨｇの減圧下、１２０℃
の温度で１０時間乾燥し、ＴＭＨＱ純度９９．１％、Ｔ
ＭＡ含有率０．８％、ＴＭＨＱモノ体０．１％のＴＭＨ
Ｑを７１．１ｇ得た。精製収率（対理論反応粗物）は４
０％であった。Next, 100 g (solid content: 80 g) of the obtained filtered crystals, 48 g of γ-butyrolactone and xylene 1
Under a nitrogen gas atmosphere, 92 g of the mixture was charged in the same apparatus and stirred at the reflux temperature of the mixed solvent (142 ° C.) for 2 hours. Then 4
After cooling to 0 ° C., the mixture was filtered, and the obtained separated crystals were washed with a mixed solvent of 6 g of γ-butyrolactone and 24 g of xylene. Further, the filtered crystal was subjected to 120 ° C. under a reduced pressure of 5 mmHg.
, Dried at a temperature of 10 hours, TMHQ purity 99.1%, T
TMH with MA content 0.8%, TMHQ mono body 0.1%
71.1 g of Q was obtained. Purification yield (vs. theoretical crude) is 4
It was 0%.
【００５９】得られたＴＭＨＱを、実施例１と同様の操
作でＤＭＦ溶液とし、ポリイミドフィルムを作製した。
ＤＭＦ溶液に濁りは見られず、且つポリイミドフィルム
中にゲル状異物は観察されず、フィルム表面は平滑であ
った。The obtained TMHQ was used as a DMF solution in the same manner as in Example 1 to prepare a polyimide film.
No turbidity was observed in the DMF solution, no gel-like foreign matter was observed in the polyimide film, and the film surface was smooth.
【００６０】実施例３ 実施例１と同様にＴＭＨＱ反応粗物を合成した後、２２
５℃でγ−ブチロラクトン４１３．４ｇ（対理論反応粗
物の２重量倍量）を攪拌下０．５時間かけて滴下した。
滴下終了時、温度は９５℃であった。更に４０℃まで冷
却してＴＭＨＱスラリーを得た。Example 3 A TMHQ reaction crude product was synthesized in the same manner as in Example 1,
At 5 ° C., 413.4 g of γ-butyrolactone (2 times the weight of the theoretical reaction crude) was added dropwise with stirring over 0.5 hours.
At the end of the addition, the temperature was 95 ° C. It was further cooled to 40 ° C. to obtain a TMHQ slurry.
【００６１】該ＴＭＨＱスラリーを濾過し、１０３．４
ｇの濾別結晶を得た。この濾別結晶の一部を５ｍｍＨｇ
の減圧下、１４０℃の温度で１０時間乾燥したところＴ
ＭＨＱ純度９７．４％、ＴＭＡ含有率２．２％、ＴＭＨ
Ｑモノ体０．４％であり、固形分含有率は８０％であっ
た。The TMHQ slurry was filtered and 103.4
g of filtered crystals were obtained. A part of the crystal separated by filtration is 5 mmHg.
After drying at 140 ° C. for 10 hours under reduced pressure of
MHQ purity 97.4%, TMA content 2.2%, TMH
The Q mono body was 0.4%, and the solid content was 80%.
【００６２】次いで、得られた濾別結晶９０ｇ（固形分
７２ｇ）とγ−ブチロラクトン１０８ｇ及びキシレン１
０８ｇを同様の装置に窒素ガス雰囲気下で仕込み、混合
溶媒の還流温度（１４５℃）で２時間攪拌した。次に４
０℃まで冷却した後濾過し、得られた濾別結晶をγ−ブ
チロラクトン１５ｇ、キシレン１５ｇの混合溶媒で洗浄
した。更にこの濾別結晶を５ｍｍＨｇの減圧下、１２０
℃の温度で１０時間乾燥し、ＴＭＨＱ純度９９．８％、
ＴＭＡ含有率０．２％のＴＭＨＱを６６．１ｇ得た。精
製収率（対理論反応粗物）は３２％であった。Next, 90 g (solid content: 72 g) of the obtained separated crystals, 108 g of γ-butyrolactone and xylene 1
08 g was charged into a similar apparatus under a nitrogen gas atmosphere, and the mixture was stirred at the reflux temperature of the mixed solvent (145 ° C.) for 2 hours. Then 4
After cooling to 0 ° C., the mixture was filtered, and the obtained separated crystals were washed with a mixed solvent of 15 g of γ-butyrolactone and 15 g of xylene. Further, the separated crystals were filtered under reduced pressure of 5 mmHg for 120 minutes.
Dried at a temperature of 10 ° C. for 10 hours, TMHQ purity 99.8%,
66.1 g of TMHQ having a TMA content of 0.2% was obtained. Purification yield (vs. theoretical crude) was 32%.
【００６３】得られたＴＭＨＱを、実施例１と同様の操
作でＤＭＦ溶液とし、ポリイミドフィルムを作製した。
ＤＭＦ溶液に濁りは見られず、且つポリイミドフィルム
中にゲル状異物は観察されず、フィルム表面は平滑であ
った。The obtained TMHQ was used as a DMF solution in the same manner as in Example 1 to prepare a polyimide film.
No turbidity was observed in the DMF solution, no gel-like foreign matter was observed in the polyimide film, and the film surface was smooth.
【００６４】実施例４ 実施例１と同様にＴＭＨＱ反応粗物を合成した後、２２
５℃でγ−ブチロラクトン２５２．２ｇ（対理論反応粗
物の１．２２重量倍量）を攪拌下０．５時間かけて滴下
した。滴下終了時、温度は１２７℃であった。次いで１
２５℃でキシレン２８．０ｇを攪拌下５分間で滴下した
後、４０℃まで冷却してＴＭＨＱスラリーを得た。この
ＴＭＨＱスラリーを濾過し、１２６．６ｇの濾別結晶を
得た。この濾別結晶の一部を５ｍｍＨｇの減圧下、１４
０℃の温度で１０時間乾燥したところＴＭＨＱ純度９
３．５％、ＴＭＡ含有率５．５％、ＴＭＨＱモノ体１．
０％であり、固形分含有率は８０％であった。Example 4 After the TMHQ reaction crude was synthesized in the same manner as in Example 1,
At 5 ° C., 252.2 g of γ-butyrolactone (1.22 times the weight of the theoretical reaction crude) was added dropwise with stirring over 0.5 hours. At the end of the dropwise addition, the temperature was 127 ° C. Then 1
After 28.0 g of xylene was added dropwise at 25 ° C. with stirring for 5 minutes, the mixture was cooled to 40 ° C. to obtain a TMHQ slurry. The TMHQ slurry was filtered to obtain 126.6 g of crystals separated by filtration. A part of the separated crystals was filtered under reduced pressure of 5 mmHg to 14
After drying at 0 ° C. for 10 hours, TMHQ purity 9
3.5%, TMA content 5.5%, TMHQ monobody
0% and the solids content was 80%.
【００６５】次いで得られた濾別結晶１００ｇ（固形分
８０ｇ）とγ−ブチロラクトン４８ｇ及びキシレン１９
２ｇを同様の装置に窒素ガス雰囲気下で仕込み、混合溶
媒の還流温度（１４２℃）で２時間攪拌した。次に４０
℃まで冷却した後濾過し、得られた濾別結晶をγ−ブチ
ロラクトン６ｇ、キシレン２４ｇの混合溶媒で洗浄し
た。更にこの濾別結晶を５ｍｍＨｇの減圧下、１２０℃
の温度で１０時間乾燥し、ＴＭＨＱ純度９８．６％、Ｔ
ＭＡ含有率１．２％、ＴＭＨＱモノ体０．２％のＴＭＨ
Ｑを９０．９ｇ得た。精製収率（対理論反応粗物）は４
４％であった。Then, 100 g (solid content: 80 g) of the obtained filtered crystals, 48 g of γ-butyrolactone and xylene 19
2 g of the mixture was charged into a similar apparatus under a nitrogen gas atmosphere, and the mixture was stirred at the reflux temperature of the mixed solvent (142 ° C.) for 2 hours. Then 40
After cooling to 0 ° C., the mixture was filtered, and the obtained separated crystals were washed with a mixed solvent of 6 g of γ-butyrolactone and 24 g of xylene. Further, the filtered crystal was subjected to 120 ° C. under a reduced pressure of 5 mmHg.
, Dried at a temperature of 10 hours, TMHQ purity 98.6%, T
TMH with MA content 1.2% and TMHQ mono body 0.2%
90.9 g of Q was obtained. Purification yield (vs. theoretical crude) is 4
4%.
【００６６】得られたＴＭＨＱを、実施例１と同様の操
作でＤＭＦ溶液とし、ポリイミドフィルムを作製した。
ＤＭＦ溶液に濁りは見られず、且つポリイミドフィルム
中にゲル状異物は観察されず、フィルム表面は平滑であ
った。The obtained TMHQ was used as a DMF solution in the same manner as in Example 1 to prepare a polyimide film.
No turbidity was observed in the DMF solution, no gel-like foreign matter was observed in the polyimide film, and the film surface was smooth.
【００６７】実施例５ 攪拌機、温度計、冷却管付きデカンター及び窒素ガス導
入口の付いた１Ｌの四ツ口フラスコにヒドロキノン３
３．０ｇ（０．３モル）、無水酢酸９１．９ｇ（０．９
モル）及びラウリルジメチルアミン２．５ｇ（０．０１
モル）を仕込み、窒素雰囲気下、１３０℃で０．５時間
反応させた。一部を取り出し分析したところヒドロキノ
ンジアセテートの純度は９９．９％であった。Example 5 Hydroquinone 3 was placed in a 1 L four-necked flask equipped with a stirrer, a thermometer, a decanter equipped with a cooling tube, and a nitrogen gas inlet.
3.0 g (0.3 mol), acetic anhydride 91.9 g (0.9
Mol) and 2.5 g of lauryldimethylamine (0.01
Mol), and reacted at 130 ° C. for 0.5 hour in a nitrogen atmosphere. A portion was taken out and analyzed. As a result, the purity of hydroquinone diacetate was 99.9%.
【００６８】次いでＴＭＡ１８４．４ｇ（０．９６モ
ル）を仕込み、窒素雰囲気下、２２０℃まで昇温した。
同温度で０．５時間反応し、更に２２５℃まで昇温し、
８０ｍｍＨｇまで徐々に減圧して０．５時間反応した。
窒素にて常圧に戻し反応粗物を得た。この２２５℃の反
応粗物にγ−ブチロラクトン２５２．２ｇ（理論反応粗
物の１．２２重量倍量）を攪拌下０．５時間かけて滴下
した。滴下終了時、温度は１２９℃であった。更に４０
℃まで冷却してＴＭＨＱスラリーを得た。Next, 184.4 g (0.96 mol) of TMA was charged and heated to 220 ° C. under a nitrogen atmosphere.
The reaction was carried out at the same temperature for 0.5 hour, and the temperature was further raised to 225 ° C
The pressure was gradually reduced to 80 mmHg, and the reaction was performed for 0.5 hour.
The pressure was returned to normal pressure with nitrogen to obtain a crude reaction product. 252.2 g of γ-butyrolactone (1.22 times the weight of the theoretical reaction crude) was added dropwise to the reaction crude at 225 ° C. over 0.5 hour with stirring. At the end of the dropwise addition, the temperature was 129 ° C. Further 40
It cooled to ° C and obtained TMHQ slurry.
【００６９】このＴＭＨＱスラリーを濾過し、１１４．
０ｇの濾別結晶を得た。この濾別結晶の一部を５ｍｍＨ
ｇの減圧下、１４０℃の温度で１０時間乾燥したところ
ＴＭＨＱ純度９６．７％、ＴＭＡ含有率２．８％、ＴＭ
ＨＱモノ体０．５％であり、固形分含有率は８０％であ
った。The TMHQ slurry was filtered, and 114.
0 g of crystals separated by filtration were obtained. A part of the filtered crystal is 5 mmH
g at a temperature of 140 ° C. for 10 hours under a reduced pressure to give TMHQ purity of 96.7%, TMA content of 2.8%, TM
The HQ mono body was 0.5%, and the solid content was 80%.
【００７０】次いで得られた濾別結晶１００ｇ（固形分
８０ｇ）とγ−ブチロラクトン４８ｇ及びキシレン１９
２ｇを同様の装置に窒素ガス雰囲気下で仕込み、混合溶
媒の還流温度（１４２℃）で２時間攪拌した。次に４０
℃まで冷却した後濾過し、得られた濾別結晶をγ−ブチ
ロラクトン６ｇ、キシレン２４ｇの混合溶媒で洗浄し
た。更にこの濾別結晶を５ｍｍＨｇの減圧下、１２０℃
の温度で１０時間乾燥し、ＴＭＨＱ純度９９．６％、Ｔ
ＭＡ含有率０．３％、ＴＭＨＱモノ体０．１％のＴＭＨ
Ｑを６８．９ｇ得た。精製収率（対理論反応粗物）は３
８％であった。Next, 100 g (solid content: 80 g) of the obtained separated crystals, 48 g of γ-butyrolactone and xylene 19
2 g of the mixture was charged into a similar apparatus under a nitrogen gas atmosphere, and the mixture was stirred at the reflux temperature of the mixed solvent (142 ° C.) for 2 hours. Then 40
After cooling to 0 ° C., the mixture was filtered, and the obtained separated crystals were washed with a mixed solvent of 6 g of γ-butyrolactone and 24 g of xylene. Further, the filtered crystal was subjected to 120 ° C. under a reduced pressure of 5 mmHg.
, Dried at a temperature of 10 hours, TMHQ purity 99.6%, T
TMH with MA content 0.3% and TMHQ mono body 0.1%
68.9 g of Q were obtained. Purification yield (vs. theoretical reaction crude) is 3
8%.
【００７１】得られたＴＭＨＱを、実施例１と同様の操
作でＤＭＦ溶液とし、ポリイミドフィルムを作製した。
ＤＭＦ溶液に濁りは見られず、且つポリイミドフィルム
中にゲル状異物は観察されず、フィルム表面は平滑であ
った。The obtained TMHQ was used as a DMF solution in the same manner as in Example 1 to prepare a polyimide film.
No turbidity was observed in the DMF solution, no gel-like foreign matter was observed in the polyimide film, and the film surface was smooth.
【００７２】実施例６ 攪拌機、温度計、冷却管付きデカンター及び窒素ガス導
入口の付いた１Ｌの四ツ口フラスコにヒドロキノン４
４．０ｇ（０．４モル）、無水酢酸１２２．５ｇ（１．
２モル）及びラウリルジメチルアミン３．４ｇ（０．０
２モル）を仕込み、窒素雰囲気下、１３０℃で０．５時
間反応させた。一部を取り出し分析したところヒドロキ
ノンジアセテートの純度は９９．９％であった。Example 6 Hydroquinone 4 was placed in a 1-L four-necked flask equipped with a stirrer, a thermometer, a decanter equipped with a cooling tube, and a nitrogen gas inlet.
4.0 g (0.4 mol), 122.5 g of acetic anhydride (1.
2 mol) and 3.4 g of lauryldimethylamine (0.0
2 mol), and reacted at 130 ° C. for 0.5 hour under a nitrogen atmosphere. A portion was taken out and analyzed. As a result, the purity of hydroquinone diacetate was 99.9%.
【００７３】次いでＴＭＡ１５３．７ｇ（０．８モル）
を仕込み、窒素雰囲気下、２６０℃まで昇温した。同温
度で０．５時間反応し、更に８０ｍｍＨｇまで徐々に減
圧して０．５時間反応した。窒素にて常圧に戻し反応粗
物を得た。この反応粗物を２４０℃まで冷却した後、γ
−ブチロラクトン２２３．６ｇ（理論反応粗物の１．２
２重量倍量）を攪拌下０．５時間かけて滴下した。滴下
終了時、温度は１３６℃であった。更に４０℃まで冷却
してＴＭＨＱスラリーを得た。Next, 153.7 g (0.8 mol) of TMA
And heated to 260 ° C. in a nitrogen atmosphere. The reaction was carried out at the same temperature for 0.5 hour, and further, the pressure was gradually reduced to 80 mmHg, and the reaction was carried out for 0.5 hour. The pressure was returned to normal pressure with nitrogen to obtain a crude reaction product. After cooling the reaction crude to 240 ° C., γ
223.6 g of butyrolactone (1.2% of the theoretical reaction crude)
(2 weight times) was added dropwise over 0.5 hour with stirring. At the end of the addition, the temperature was 136 ° C. It was further cooled to 40 ° C. to obtain a TMHQ slurry.
【００７４】該ＴＭＨＱスラリーを濾過し、１４５．２
ｇの濾別結晶を得た。この濾別結晶の一部を５ｍｍＨｇ
の減圧下、１４０℃の温度で１０時間乾燥したところＴ
ＭＨＱ純度９７．１％、ＴＭＡ含有率１．４％、ＴＭＨ
Ｑモノ体１．５％であり、固形分含有率は７７％であっ
た。The TMHQ slurry was filtered and 145.2
g of filtered crystals were obtained. A part of the crystal separated by filtration is 5 mmHg.
After drying at 140 ° C. for 10 hours under reduced pressure of
MHQ purity 97.1%, TMA content 1.4%, TMH
The Q mono body was 1.5%, and the solid content was 77%.
【００７５】次いで得られた濾別結晶１２０ｇ（固形分
９２．４ｇ）とγ−ブチロラクトン５５．４ｇ及びキシ
レン２２１．８ｇを同様の装置に窒素ガス雰囲気下で仕
込み、混合溶媒の還流温度（１４２℃）で２時間攪拌し
た。次に４０℃まで冷却した後濾過し、得られた濾別結
晶をγ−ブチロラクトン７ｇ、キシレン２８ｇの混合溶
媒で洗浄した。更にこの濾別結晶を５ｍｍＨｇの減圧
下、１２０℃の温度で１０時間乾燥し、ＴＭＨＱ純度９
９．０％、ＴＭＡ含有率０．１％、ＴＭＨＱモノ体０．
９％のＴＭＨＱを８１．８ｇ得た。精製収率（対理論反
応粗物）は５４％であった。Next, 120 g (solid content: 92.4 g) of the obtained separated crystals, 55.4 g of γ-butyrolactone and 221.8 g of xylene were charged into a similar apparatus under a nitrogen gas atmosphere, and the reflux temperature of the mixed solvent (142 ° C.) ) For 2 hours. Next, the mixture was cooled to 40 ° C., and then filtered. The obtained separated crystals were washed with a mixed solvent of 7 g of γ-butyrolactone and 28 g of xylene. Further, the filtered crystals were dried at a temperature of 120 ° C. for 10 hours under a reduced pressure of 5 mmHg.
9.0%, TMA content 0.1%, TMHQ mono-form
81.8 g of 9% TMHQ was obtained. The purification yield (vs. the theoretical reaction crude) was 54%.
【００７６】得られたＴＭＨＱを実施例１と同様の操作
でＤＭＦ溶液とし、ポリイミドフィルムを作製した。Ｄ
ＭＦ溶液に濁りは見られず、且つポリイミドフィルム中
にゲル状異物は観察されず、フィルム表面は平滑であっ
た。The obtained TMHQ was converted into a DMF solution in the same manner as in Example 1 to prepare a polyimide film. D
No turbidity was observed in the MF solution, no gel-like foreign matter was observed in the polyimide film, and the film surface was smooth.
【００７７】比較例１ 製造例１と同様の装置に製造例１で得たヒドロキノンジ
アセテート９７．１ｇ（０．５モル）及びＴＭＡ３０
７．４ｇ（１．６モル）を仕込み、２６０℃まで昇温し
た。同温度で０．５時間反応し、更に８０ｍｍＨｇまで
徐々に減圧して０．５時間反応した。反応終了後、反応
粗物を２４０℃でステンレス性容器に抜き出した。抜き
出し時に反応粗物よりガス及び異臭が発生した。この反
応粗物を冷却固化した後、小型粉砕機で粉砕し、８メッ
シュ（タイラー）の篩を通して粉末状反応粗物を得た。
この粉末状粗物はＴＭＨＱ純度６５．１％、ＴＭＡ含有
率３３．２％、ＴＭＨＱモノ体１．７％で収率９５．２
％であった。Comparative Example 1 97.1 g (0.5 mol) of hydroquinone diacetate obtained in Production Example 1 and TMA30 were placed in the same apparatus as in Production Example 1.
7.4 g (1.6 mol) was charged and the temperature was raised to 260 ° C. The reaction was carried out at the same temperature for 0.5 hour, and further, the pressure was gradually reduced to 80 mmHg, and the reaction was carried out for 0.5 hour. After completion of the reaction, the reaction crude was taken out at 240 ° C. into a stainless steel container. At the time of extraction, gas and off-flavor were generated from the reaction crude. After the reaction crude was solidified by cooling, it was pulverized with a small pulverizer and passed through an 8-mesh (Tyler) sieve to obtain a powdery reaction crude.
This crude powdery product had a TMHQ purity of 65.1%, a TMA content of 33.2%, a TMHQ mono-form of 1.7% and a yield of 95.2.
%Met.
【００７８】次いでこの粉末状反応粗物２００ｇとシク
ロヘキサノン３００ｇ及びキシレン３００ｇを同様の装
置に窒素ガス雰囲気下で仕込み、混合溶媒の還流温度
（１４２℃）で２時間攪拌した。次に４０℃まで冷却濾
過し、得られた濾別結晶をシクロヘキサノン４０ｇ、キ
シレン４０ｇの混合溶媒で洗浄し、５ｍｍＨｇの減圧
下、１２０℃で１０時間乾燥しＴＭＨＱ純度９８．３
％、ＴＭＡ含有率１．２％、ＴＭＨＱモノ体０．５％の
ＴＭＨＱを８０ｇ、精製収率４０％（対反応粗物）で得
た。Next, 200 g of the powdery reaction crude product, 300 g of cyclohexanone and 300 g of xylene were charged into a similar apparatus under a nitrogen gas atmosphere, and stirred at the reflux temperature of the mixed solvent (142 ° C.) for 2 hours. Next, the mixture was cooled and filtered to 40 ° C., and the obtained separated crystals were washed with a mixed solvent of 40 g of cyclohexanone and 40 g of xylene, and dried at 120 ° C. under a reduced pressure of 5 mmHg for 10 hours, and the TMHQ purity was 98.3.
%, 80% of TMHQ having a TMA content of 1.2% and a TMHQ mono-form of 0.5% were obtained at a purification yield of 40% (vs. reaction crude).
【００７９】得られたＴＭＨＱを、実施例１と同様の操
作でＤＭＦ溶液とし、ポリイミドフィルムを作製した。
ＤＭＦ溶液に濁りが見られ、ポリイミドフィルム中に１
０〜２０μｍ程度のゲル状異物が多数観察され、またフ
ィルム表面に微細な突起状物が多数観察された。The obtained TMHQ was used as a DMF solution in the same manner as in Example 1 to prepare a polyimide film.
Turbidity was observed in the DMF solution, and 1
Many gel-like foreign substances of about 0 to 20 μm were observed, and many fine projections were observed on the film surface.
【００８０】[0080]
【発明の効果】本発明に係るＴＭＨＱの製造方法を行う
ことにより、効率よく、且つ作業性も良好な工業的に有
利な条件で、ポリイミドフィルム用の原料に適した純度
９８重量％以上の高純度ヒドロキノンビス（アンヒドロ
トリメリテート）を得ることができる。According to the method for producing TMHQ according to the present invention, a high purity of 98% by weight or more suitable for a raw material for a polyimide film can be obtained under industrially advantageous conditions with good efficiency and good workability. Purified hydroquinone bis (anhydrotrimellitate) can be obtained.
Claims (10)
３のアルキル基を表す。］で表されるヒドロキノンの低
級アルカン酸エステルと無水トリメリット酸をエステル
交換反応しヒドロキノンビス（アンヒドロトリメリテー
ト）を製造するに際し、エステル交換反応により得たヒ
ドロキノンビス（アンヒドロトリメリテート）反応粗物
を、（Ａ）群に属する溶媒を用いてスラリー状としたの
ち、（Ａ）群及び（Ｂ）群からなる混合溶媒を用いて精
製することを特徴とする高純度ヒドロキノンビス（アン
ヒドロトリメリテート）の製造方法。 （Ａ）群： ラクトン系溶媒の１種若しくは２種以上。 （Ｂ）群：炭素数が６〜２０の芳香族又は脂肪族の炭化
水素の１種若しくは２種以上。1. General formula (1) [Wherein, R 1 and R 2 are the same or different and each have 1 to 1 carbon atoms.
3 represents an alkyl group. In the production of hydroquinone bis (anhydrotrimellitate) by transesterification of a lower alkanoic acid ester of hydroquinone represented by the following formula and trimellitic anhydride, hydroquinone bis (anhydrotrimellitate) obtained by the transesterification reaction A high-purity hydroquinone bis (anthrene) is characterized in that the reaction crude is made into a slurry using a solvent belonging to the group (A) and then purified using a mixed solvent consisting of the groups (A) and (B). Hydrotrimellitate). Group (A): One or more lactone solvents. Group (B): One or more aromatic or aliphatic hydrocarbons having 6 to 20 carbon atoms.
ドロキノンビス（アンヒドロトリメリテート）反応粗物
中に（Ａ）群に属する溶媒を添加して行うことを特徴と
する、請求項１に記載の高純度ヒドロキノンビス（アン
ヒドロトリメリテート）の製造方法。2. A slurry obtained by adding a solvent belonging to the group (A) to a hydroquinone bis (anhydrotrimellitate) reaction crude product having a temperature of 200 ° C. or higher. 3. The method for producing high-purity hydroquinone bis (anhydrotrimellitate) according to item 1.
低級アルカン酸エステルと無水トリメリット酸をエステ
ル交換反応しヒドロキノンビス（アンヒドロトリメリテ
ート）を製造するに際し、エステル交換反応により得た
ヒドロキノンビス（アンヒドロトリメリテート）反応粗
物を、（Ａ）群に属する溶媒を用いてスラリー状とした
のち、更に（Ａ）群に属する溶媒を用いて精製すること
を特徴とする高純度ヒドロキノンビス（アンヒドロトリ
メリテート）の製造方法。3. A transesterification reaction between a lower alkanoic acid ester of hydroquinone represented by the general formula (1) and trimellitic anhydride to produce hydroquinone bis (anhydrotrimellitate). High purity, characterized in that a hydroquinone bis (anhydrotrimellitate) reaction crude product is made into a slurry using a solvent belonging to the group (A) and then purified using a solvent belonging to the group (A). A method for producing hydroquinone bis (anhydrotrimellitate).
ドロキノンビス（アンヒドロトリメリテート）反応粗物
中に（Ａ）群に属する溶媒を添加して行うことを特徴と
する、請求項３に記載の高純度ヒドロキノンビス（アン
ヒドロトリメリテート）の製造方法。4. The slurry is prepared by adding a solvent belonging to the group (A) to a hydroquinone bis (anhydrotrimellitate) reaction crude product having a temperature of 200 ° C. or higher. 3. The method for producing high-purity hydroquinone bis (anhydrotrimellitate) according to 1.
媒の使用量が、ヒドロキノンビス（アンヒドロトリメリ
テート）反応粗物１００重量部に対し５０〜３００重量
部である、請求項１〜４のいずれかの請求項に記載の高
純度ヒドロキノンビス（アンヒドロトリメリテート）の
製造方法。5. The slurry according to claim 1, wherein the amount of the solvent belonging to the group (A) is 50 to 300 parts by weight based on 100 parts by weight of the hydroquinone bis (anhydrotrimellitate) reaction crude product. The method for producing high-purity hydroquinone bis (anhydrotrimellitate) according to any one of claims 1 to 4.
ある請求項１〜５のいずれかの請求項に記載の高純度ヒ
ドロキノンビス（アンヒドロトリメリテート）の製造方
法。6. The method for producing high-purity hydroquinone bis (anhydrotrimellitate) according to claim 1, wherein the solvent in group (A) is γ-butyrolactone.
ン、ベンゼン、シクロヘキサン及びヘキサンの群から選
ばれる１種若しくは２種以上である請求項１又は請求項
２に記載の高純度ヒドロキノンビス（アンヒドロトリメ
リテート）の製造方法。7. The high-purity hydroquinone bis () according to claim 1 or 2, wherein the solvent in the group (B) is one or more selected from the group consisting of xylene, toluene, benzene, cyclohexane and hexane. Anhydrotrimellitate).
の重量比率が０．５／９．５〜９．５／０．５（（Ａ）
群／（Ｂ）群）である請求項１又は請求項２に記載の高
純度ヒドロキノンビス（アンヒドロトリメリテート）の
製造方法。8. The weight ratio of the mixed solvent comprising the groups (A) and (B) is 0.5 / 9.5 to 9.5 / 0.5 ((A)
The method for producing high-purity hydroquinone bis (anhydrotrimellitate) according to claim 1 or 2, which is a group / (B) group.
テート）の純度が９８重量％以上であり、且つポリイミ
ドフィルムを形成した際のフィルムの表面が平滑であり
フィルム中にゲル状異物を生じない、請求項１〜８のい
ずれかの請求項に記載の高純度ヒドロキノンビス（アン
ヒドロトリメリテート）の製造方法。9. The method according to claim 1, wherein the purity of the hydroquinone bis (anhydrotrimellitate) is 98% by weight or more, and the surface of the film when the polyimide film is formed is smooth and no gel-like foreign matter is generated in the film. The method for producing high-purity hydroquinone bis (anhydrotrimellitate) according to any one of claims 1 to 8.
リテート）の純度が９８重量％以上であり、且つポリイ
ミドフィルムを形成した際のフィルムの表面が平滑であ
りフィルム中にゲル状異物を生じない、高純度ヒドロキ
ノンビス（アンヒドロトリメリテート）。10. A high-purity hydroquinone bis (anhydrotrimellitate) having a purity of 98% by weight or more, and a polyimide film formed with a smooth surface and no gel-like foreign matter in the film. Purity hydroquinone bis (anhydrotrimellitate).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36287098A JP2000186080A (en) | 1998-12-21 | 1998-12-21 | Production of high-purity hydroquinone bis(anhydrotrimellitate) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36287098A JP2000186080A (en) | 1998-12-21 | 1998-12-21 | Production of high-purity hydroquinone bis(anhydrotrimellitate) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000186080A true JP2000186080A (en) | 2000-07-04 |
Family
ID=18477944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP36287098A Pending JP2000186080A (en) | 1998-12-21 | 1998-12-21 | Production of high-purity hydroquinone bis(anhydrotrimellitate) |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000186080A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006206486A (en) * | 2005-01-27 | 2006-08-10 | Manac Inc | Method for producing ester group-containing acid dianhydride derivative |
| WO2011158928A1 (en) * | 2010-06-18 | 2011-12-22 | 本州化学工業株式会社 | Process for producing trimellitic anhydride phenyl ester |
| CN103215048A (en) * | 2012-01-24 | 2013-07-24 | Jsr株式会社 | liquid crystal alignment agent, a liquid crystal alignment film and forming thereof, and a liquid crystal display element |
| WO2020250920A1 (en) * | 2019-06-11 | 2020-12-17 | マナック株式会社 | Method for producing ester group-containing acid dianhydride derivative |
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-
1998
- 1998-12-21 JP JP36287098A patent/JP2000186080A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006206486A (en) * | 2005-01-27 | 2006-08-10 | Manac Inc | Method for producing ester group-containing acid dianhydride derivative |
| WO2011158928A1 (en) * | 2010-06-18 | 2011-12-22 | 本州化学工業株式会社 | Process for producing trimellitic anhydride phenyl ester |
| CN102947284A (en) * | 2010-06-18 | 2013-02-27 | 本州化学工业株式会社 | Process for producing trimellitic anhydride phenyl ester |
| JPWO2011158928A1 (en) * | 2010-06-18 | 2013-08-19 | 本州化学工業株式会社 | Method for producing trimellitic anhydride phenyl esters |
| JP5809623B2 (en) * | 2010-06-18 | 2015-11-11 | 本州化学工業株式会社 | Method for producing trimellitic anhydride phenyl esters |
| KR101797794B1 (en) | 2010-06-18 | 2017-11-15 | 혼슈우 카가쿠고교 가부시키가이샤 | Process for producing trimellitic anhydride phenyl ester |
| CN103215048A (en) * | 2012-01-24 | 2013-07-24 | Jsr株式会社 | liquid crystal alignment agent, a liquid crystal alignment film and forming thereof, and a liquid crystal display element |
| WO2020250920A1 (en) * | 2019-06-11 | 2020-12-17 | マナック株式会社 | Method for producing ester group-containing acid dianhydride derivative |
| CN113727977A (en) * | 2019-06-11 | 2021-11-30 | 玛耐科股份有限公司 | Method for producing acid dianhydride derivative containing ester group |
| TWI833023B (en) * | 2019-06-11 | 2024-02-21 | 日商瑪耐科股份有限公司 | Method for producing ester group-containing acid dianhydride derivative |
| CN115301287A (en) * | 2022-08-22 | 2022-11-08 | 天津众泰材料科技有限公司 | Preparation method of high-purity p-phenylene-ditrimellitic dianhydride |
| CN115301287B (en) * | 2022-08-22 | 2023-11-10 | 天津众泰材料科技有限公司 | Preparation method of high-purity p-phenylene-bis (trimellitate) dianhydride |
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