JPH0577672B2 - - Google Patents
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- JPH0577672B2 JPH0577672B2 JP1061150A JP6115089A JPH0577672B2 JP H0577672 B2 JPH0577672 B2 JP H0577672B2 JP 1061150 A JP1061150 A JP 1061150A JP 6115089 A JP6115089 A JP 6115089A JP H0577672 B2 JPH0577672 B2 JP H0577672B2
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- solvent
- anhydride
- purity
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Description
（産業上の利用分野）
本発明はトリメリツト酸エステル無水物の精製
方法に関する。
（従来の技術）
トリメリツト酸エステル無水物は、有用な工業
用素材であり、これをエポキシ樹脂硬化剤、ポリ
イミド樹脂等の原料として用いた場合、丈夫で柔
軟な耐熱性に優れた樹脂成形品や皮膜を得ること
ができる。
近年における工業用素材は、高性能化・高機能
化が要求されるようになり、トリメリツト酸エス
テル無水物も例外でなく、従来以上の純度が要求
されている。
トリメリツト酸エステル無水物の製造方法とし
ては、無水トリメリツト酸（以下、「TMA」と
略称する）とポリオールを原料として直接製造す
る方法（特公昭45−29974、特公昭52−46940）が
知られているが、当該方法によれば、純度の低い
目的物しか得ることができず、高純度品を必要と
する場合は、さらに精製することが必要であつ
た。
（本発明が解決しようとする課題）
従来、トリメリツト酸エステル無水物の精製方
法としては、無水酢酸やメチルエチルケトンによ
る再結晶法が知られている（J.Poly.Mater.2(1)，
64−68，1985、米国特許US 3277117）。しかしな
がら、いずれの溶媒を用いても、１回の再結晶収
率が40％程度と低く、効率の悪いものであつた。
（課題を解決するための手段）
本発明者らは高純度のトリメリツト酸エステル
無水物を高収率で得る目的で、原料のTMAと目
的物のトリメリツト酸エステル無水物の溶解度、
さらに２種以上の混合溶媒での溶解度を検討し、
最結晶溶媒として特定の混合溶媒を選択して適用
することにより、高純度のトリメリツト酸エステ
ル無水物を高収率で得られることを見い出し、こ
の知見に基づいて本発明を完成した。原料の
TMAと目的物のトリメリツト酸エステル無水物
の溶解度を検討し、最適溶媒を選択して再結晶を
行つた例は知られておらず、さらに２種以上の再
結晶溶媒を用いて、精製した例は見当たらない。
本発明に係るトリメリツト酸エステル無水物の
精製方法は、一般式（）で表わされるトリメリ
ツト酸エステル無水物の粗物を、(A)群に属する溶
媒及び(B)群に属する溶媒からなる混合溶媒を用い
て再結晶することを特徴とする。
(Industrial Application Field) The present invention relates to a method for purifying trimellitic acid ester anhydride. (Prior art) Trimellitic acid ester anhydride is a useful industrial material, and when used as a raw material for epoxy resin curing agents, polyimide resins, etc., it can be used to produce resin molded products that are strong, flexible, and have excellent heat resistance. A film can be obtained. In recent years, industrial materials have come to be required to have higher performance and functionality, and trimellitic acid ester anhydride is no exception, requiring higher purity than ever before. As a method for producing trimellitic acid ester anhydride, a method is known in which it is directly produced using trimellitic anhydride (hereinafter abbreviated as "TMA") and polyol as raw materials (Japanese Patent Publication No. 45-29974, Japanese Patent Publication No. 52-46940). However, according to this method, only a target product with low purity can be obtained, and if a high purity product is required, further purification is required. (Problems to be Solved by the Present Invention) Conventionally, recrystallization using acetic anhydride or methyl ethyl ketone has been known as a method for purifying trimellitic acid ester anhydride (J. Poly. Mater. 2(1),
64-68, 1985, U.S. Pat. No. 3,277,117). However, no matter which solvent was used, the yield of one recrystallization was as low as about 40%, and the efficiency was poor. (Means for Solving the Problems) In order to obtain high-purity trimellitic acid ester anhydride in high yield, the present inventors determined the solubility of the raw material TMA and the target product trimellitic acid ester anhydride.
Furthermore, we investigated the solubility in a mixed solvent of two or more types,
It was discovered that highly purified trimellitic acid ester anhydride can be obtained in high yield by selecting and applying a specific mixed solvent as a crystallization solvent, and based on this knowledge, the present invention was completed. of raw materials
There are no known examples in which the solubility of TMA and the target trimellitic acid ester anhydride was examined and the optimal solvent was selected for recrystallization. Furthermore, there is an example in which purification was performed using two or more recrystallization solvents. is not found. The method for purifying trimellitic acid ester anhydride according to the present invention involves converting the crude trimellitic acid ester anhydride represented by the general formula () into a mixed solvent consisting of a solvent belonging to group (A) and a solvent belonging to group (B). It is characterized by recrystallization using.
【化】
［式中、Ｒはポリオール残基を示し、ｎは１〜
２の整数を表わす。］
(A)群：25℃における無水トリメリツト酸エステ
ル無水物の溶解度が0.001〜３ｇ／100ｇであ
る炭化水素類
(B)群：25℃における無水トリメリツト酸の溶解
度が５〜50ｇ／100ｇである有機溶媒。
(A)群に係る炭化水素類としては、トリメリツト
酸エステル無水物に対し不活性で、かつ25℃にお
ける当該無水物の溶解度が0.001〜３ｇ／100ｇの
溶媒であれば足りる。
かかる溶媒としては、ベンゼン、トルエン、キ
シレン、エチルベンゼン、イソプロピルベンゼン
等の芳香族炭化水素、ヘプタン、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
肪族環状炭化水素類が例示され、単独又は２種以
上混合して用いられる。
一方、(B)群に係る溶媒としては、トリメリツト
酸エステル無水物に対して不活性で、かつ25℃に
おけるTMAの溶解度が５〜50ｇ／100ｇの溶媒
であれば足り、具体的には、ケトン類、エーテル
類、エステル類及び脂肪族カルボン酸等が例示さ
れる。これらのケトン類、エーテル類等は単独又
は２種以上混合して用いられる。
ケトン類としては、ジイソプロピルケトン、メ
チルエチルケトン、メチルイソブチルケトン、ア
セチルアセトン、アセトフエノン、イソホロン、
シクロヘキサノン等が例示される。
エーテル類としては、ジイソプロピルエーテ
ル、エチルブチルエーテル、ジ（クロロイソプロ
ピル）エーテル、エチレングリコール又はジ、ト
リ、テトラエチレングリコールのジアルキルエー
テル（アルキル基は炭素数１〜４の直鎖又は分
岐）等が例示される。
エステル類としては、酢酸エチル、酢酸ブチ
ル、セロソルブアセテート、カルビトールアセテ
ート、アセト酢酸メチル、アセト酢酸エチル等の
酢酸エステル、プロピオン酸メチル等のプロピオ
ン酸エステル、酪酸エステル等の脂肪族エステル
類、フタル酸ジメチル、フタル酸ジエチル等の芳
香族ジエステル類が例示される。
さらに、脂肪族カルボン酸としては、プロピオ
ン酸、２−エチルヘキサン酸以外の酢酸、酪酸、
カプロン酸、カプリル酸等の低級飽和カルボン酸
が例示される。
(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１／９
〜９／１、好ましくは３／７〜８／２の範囲内で
適宜選択される。Ａ群に属する溶媒の比率が高く
なると精製物の歩留りは向上する反面、高純度品
が得られにくく、当該比率が低い場合には、この
逆の傾向が認められる。
混合溶媒の使用量は、粗製トリメリツト酸エス
テル無水物100重量部に対し、通常、100〜1000重
量部程度の範囲で選択され、好ましくは200〜400
重量部程度の範囲内で使用される。粗製トリメリ
ツト酸エステル無水物100部に対し、溶媒使用量
が100重量部より少ないと高純度品が得られにく
く、逆に1000重量部程度を超える範囲で使用され
た場合は、高純度品が得られる反面、歩留りが低
下し、工業的な方法としては好ましくない。
次に、本発明に係る精製方法の具体的内容を以
下に例示する。
即ち、精製されるべきトリメリツト酸エステル
無水物の粗物を本発明に係る所定量の混合溶媒と
混合し、100〜200℃程度に加熱し、当該無水物の
粗物を溶解させる。次に、系を室温まで徐冷後、
析出した当該無水物の結晶を別する。得られた
別結晶は(A)群の溶媒で洗浄することが好まし
い。
次に別結晶中に残存する溶媒を乾燥除去し、
精製トリメリツト酸エステル無水物を得る。
過後の混合溶媒は、蒸留等により容易にその
中に含まれている副生成物から分離され、回収さ
れる。回収された混合溶媒は、そのままで、また
わずかに組成の調整とするだけで、最結晶溶媒と
して再使用することができる。
操作は、チツソガス等の不活性ガス雰囲気下で
行うことが、色相の良好な精製物を得る上で、か
つ安全上、望ましい。
次に実施例により、本発明を詳細に説明する。
（実施例）
実施例 １
300mlの四ツ口フラスコにエチレングリコール
ビス（アンヒドロトリメリテート）（以下、
「TMEG」と略称する）の粗物（純度86.5％、液
体クロマトグラフイーにより測定）40ｇ、キシレ
ン96ｇ及びジグライム（25℃におけるTMAの溶
解度は29.3ｇ／100ｇ）24ｇをチツソガス雰囲気
下に仕込み、140℃で加熱溶解後、140℃で30分間
攪拌して、系内を均一にした。次に25℃まで徐冷
した後、過をし、得られた別結晶を60ｇのキ
シレンで洗浄した。
さらに、この別結晶を５mmHgの減圧下、100
℃の温度で10時間乾燥し、純度98.7重量％の
TMEGを33ｇ得た。収率は82.5重量％であつた。
表１に結果を示す。
実施例 ２
(B)群に属する溶媒の種類をシクロヘキサノン
（25℃におけるTMAの溶解度は38.4ｇ／100ｇ）
に代えた以外は、実施例１と同様に行つた。
その結果、純度98.5重量％のTMEGが、82.1重
量％の収率で得られた。表１に結果を示す。
実施例 ３
(B)群に属する溶媒の種類をメチルイソブチルケ
トン（25℃におけるTMAの溶解度は18.9ｇ／100
ｇ）に代えた以外は、実施例１と同様に行つた。
その結果、純度98.2重量％のTMEGが、72.8重
量％の収率で得られた。表１に結果を示す。
実施例 ４
(B)群に属する溶媒の種類をアセト酢酸メチル
（25℃におけるTMAの溶解度は10.2ｇ／100ｇ）
に代えた以外は、実施例１と同様に行つた。
その結果、純度97.9重量％のTMEGが、78.2重
量％の収率で得られた。表１に結果を示す。
実施例 ５
(B)群に属する溶媒の種類を酢酸ｎ−ブチル（25
℃におけるTMAの溶解度は17.8ｇ／100ｇ）に代
えた以外は、実施例１と同様に行つた。
その結果、純度96.9重量％のTMEGが、79.7重
量％の収率で得られた。表１に結果を示す。
実施例 ６
(B)群に属する溶媒の種類を無水酢酸（25℃にお
けるTMAの溶解度は43.4ｇ／100ｇ）に代えた以
外は、実施例１と同様に行つた。
その結果、純度96.1重量％のTMEGが、70.5重
量％の収率で得られた。表１に結果を示す。
実施例 ７
実施例１のTMEGの代わりに、グリセリント
リス（アンヒドロトリメリテート）（以下、
「TMTA」と略称する）の粗物（純度84.5％、液
体クロマトグラフイーにより測定）40ｇを用いた
以外は、実施例１と同様に行つた。
その結果、純度97.2重量％のTMTAが、82.5重
量％の収率で得られた。表１に結果を示す。
実施例 ８
実施例１のキシレン96ｇ、ジグライム24ｇの代
わりに、キシレン60ｇ、ジグライム60ｇを用いた
以外は、実施例１と同様に行つた。
その結果、純度98.8重量％のTMEGが、75.5重
量％の収率で得られた。表１に結果を示す。
比較例 １
(A)群に属する溶媒の一種であるキシレンを単独
で120ｇ用いた以外は、実施例１と同様に行つた。
その結果、純度87.5重量％のTMEGが、90.9重
量％の収率で得られた。結果を表１に示す。
比較例 ２
(B)群に属する溶媒の一種であるジグライムを単
独で120ｇ用いた以外は、実施例１と同様に行つ
た。
その結果、純度98.8重量％のTMEGが、62.0重
量％の収率で得られた。結果を表１に示す。
比較例 ３
(B)群に属する溶媒の一種であるアセト酢酸メチ
ルを単独で120ｇ用いた以外は、実施例１と同様
に行つた。
その結果、純度98.0重量％のTMEGが、51.0重
量％の収率で得られた。結果を表１に示す。
比較例 ４
(B)群に属する溶媒の一種であるカルビトールア
セテートを独で120ｇ用いた以外は、実施例１と
同様に行つた。
その結果、純度98.2重量％のTMEGが、54.7重
量％の収率で得られた。結果を表１に示す。
比較例 ５
(B)群に属する溶媒の一種である無水酢酸を単独
で120ｇ用いた以外は、実施例１と同様に行つた。
その結果、純度98.2重量％のTMEGが、17.8重
量％の収率で得られた。結果を表１に示す。
比較例 ６
溶媒としてプロピオン酸（25におけるTMAの
溶解度は５ｇ／100ｇ以下）40ｇ、キシレン80ｇ
を用いた以外は、実施例１と同様に行つた。
その結果、純度88.2重量％のTMEGが、86.7重
量％の収率で得られた。結果を表１に示す。
（発明の効果）
本発明にかかる精製方法を適用することによ
り、高純度のトリメリツト酸エステル無水物を高
収率で得ることができる。[In the formula, R represents a polyol residue, and n is 1 to
Represents an integer of 2. ] (A) Group: Hydrocarbons in which the solubility of trimellitic anhydride ester anhydride at 25°C is 0.001 to 3 g/100g (B) Group: Organics in which the solubility of trimellitic anhydride is 5 to 50 g/100g at 25°C solvent. As the hydrocarbons related to group (A), it is sufficient if the solvent is inert to trimellitic acid ester anhydride and has a solubility of the anhydride at 25°C of 0.001 to 3 g/100 g. Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and isopropylbenzene, and aliphatic chain or aliphatic cyclic hydrocarbons such as heptane, hexane, octane, and cyclohexane, which may be used alone or in combination. A mixture of the above is used. On the other hand, as a solvent related to group (B), it is sufficient to use a solvent that is inert to trimellitic acid ester anhydride and has a TMA solubility of 5 to 50 g/100 g at 25°C. Examples include esters, ethers, esters, and aliphatic carboxylic acids. These ketones, ethers, etc. may be used alone or in combination of two or more. Ketones include diisopropyl ketone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetophenone, isophorone,
Examples include cyclohexanone. Examples of ethers include diisopropyl ether, ethyl butyl ether, di(chloroisopropyl) ether, ethylene glycol, or dialkyl ether of di, tri, or tetraethylene glycol (alkyl group is linear or branched with 1 to 4 carbon atoms). Ru. Examples of esters include acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, carbitol acetate, methyl acetoacetate, and ethyl acetoacetate, propionic acid esters such as methyl propionate, aliphatic esters such as butyric acid ester, and phthalic acid. Aromatic diesters such as dimethyl and diethyl phthalate are exemplified. Furthermore, the aliphatic carboxylic acids include propionic acid, acetic acid other than 2-ethylhexanoic acid, butyric acid,
Examples include lower saturated carboxylic acids such as caproic acid and caprylic acid. The mixing weight ratio of the solvents belonging to group (A) and the solvents belonging to group (B) (solvent of group A/solvent of group B) is usually 1/9.
It is appropriately selected within the range of ~9/1, preferably 3/7 ~ 8/2. As the ratio of solvents belonging to group A increases, the yield of purified products improves, but on the other hand, it is difficult to obtain highly pure products, and when the ratio is low, the opposite tendency is observed. The amount of the mixed solvent used is usually selected in the range of about 100 to 1000 parts by weight, preferably 200 to 400 parts by weight, based on 100 parts by weight of the crude trimellitic acid ester anhydride.
It is used within a range of about parts by weight. If the amount of solvent used is less than 100 parts by weight for 100 parts of crude trimellitic acid ester anhydride, it will be difficult to obtain a high-purity product, and conversely, if it is used in an amount exceeding about 1000 parts by weight, a high-purity product will not be obtained. On the other hand, the yield decreases, making it unfavorable as an industrial method. Next, specific details of the purification method according to the present invention will be illustrated below. That is, the crude trimellitic acid ester anhydride to be purified is mixed with a predetermined amount of the mixed solvent according to the present invention, and heated to about 100 to 200°C to dissolve the crude anhydride. Next, after slowly cooling the system to room temperature,
The precipitated crystals of the anhydride are separated. The obtained separate crystals are preferably washed with a group (A) solvent. Next, the solvent remaining in another crystal is removed by drying,
Purified trimellitic acid ester anhydride is obtained. The mixed solvent after the filtration is easily separated from the by-products contained therein by distillation or the like and recovered. The recovered mixed solvent can be reused as a crystallization solvent as it is or with only slight composition adjustment. It is desirable to carry out the operation under an atmosphere of an inert gas such as chiso gas in order to obtain a purified product with a good hue and from the viewpoint of safety. Next, the present invention will be explained in detail with reference to Examples. (Example) Example 1 Ethylene glycol bis(anhydrotrimellitate) (hereinafter referred to as
40 g of crude material (abbreviated as "TMEG") (purity 86.5%, measured by liquid chromatography), 96 g of xylene, and 24 g of diglyme (TMA solubility at 25 ° C. is 29.3 g/100 g) were placed in an atmosphere of Tituso gas. After heating and dissolving at 140°C, the mixture was stirred at 140°C for 30 minutes to make the system uniform. Next, the mixture was slowly cooled to 25°C, filtered, and the obtained separate crystals were washed with 60 g of xylene. Furthermore, this other crystal was heated at 100°C under a reduced pressure of 5mmHg.
Dry for 10 hours at a temperature of ℃, purity 98.7% by weight
33g of TMEG was obtained. The yield was 82.5% by weight.
Table 1 shows the results. Example 2 The type of solvent belonging to group (B) is cyclohexanone (solubility of TMA at 25°C is 38.4g/100g)
The same procedure as in Example 1 was carried out except that . As a result, TMEG with a purity of 98.5% by weight was obtained in a yield of 82.1% by weight. Table 1 shows the results. Example 3 The type of solvent belonging to group (B) was methyl isobutyl ketone (the solubility of TMA at 25°C is 18.9 g/100
The same procedure as in Example 1 was carried out except that g) was replaced. As a result, TMEG with a purity of 98.2% by weight was obtained in a yield of 72.8% by weight. Table 1 shows the results. Example 4 The type of solvent belonging to group (B) is methyl acetoacetate (the solubility of TMA at 25°C is 10.2g/100g)
The same procedure as in Example 1 was carried out except that . As a result, TMEG with a purity of 97.9% by weight was obtained in a yield of 78.2% by weight. Table 1 shows the results. Example 5 The type of solvent belonging to group (B) was changed to n-butyl acetate (25
The same procedure as in Example 1 was carried out, except that the solubility of TMA at 17.8 g/100 g was changed. As a result, TMEG with a purity of 96.9% by weight was obtained with a yield of 79.7% by weight. Table 1 shows the results. Example 6 The same procedure as in Example 1 was carried out, except that the type of solvent belonging to group (B) was changed to acetic anhydride (the solubility of TMA at 25°C is 43.4 g/100 g). As a result, TMEG with a purity of 96.1% by weight was obtained in a yield of 70.5% by weight. Table 1 shows the results. Example 7 Instead of TMEG in Example 1, glycerin tris (anhydrotrimellitate) (hereinafter referred to as
The same procedure as in Example 1 was carried out, except that 40 g of a crude product (purity 84.5%, measured by liquid chromatography) of TMTA (abbreviated as "TMTA") was used. As a result, TMTA with a purity of 97.2% by weight was obtained in a yield of 82.5% by weight. Table 1 shows the results. Example 8 The same procedure as in Example 1 was carried out except that 60 g of xylene and 60 g of diglyme were used instead of 96 g of xylene and 24 g of diglyme in Example 1. As a result, TMEG with a purity of 98.8% by weight was obtained in a yield of 75.5% by weight. Table 1 shows the results. Comparative Example 1 The same procedure as in Example 1 was carried out except that 120 g of xylene, which is a type of solvent belonging to group (A), was used alone. As a result, TMEG with a purity of 87.5% by weight was obtained in a yield of 90.9% by weight. The results are shown in Table 1. Comparative Example 2 The same procedure as in Example 1 was carried out except that 120 g of diglyme, which is a type of solvent belonging to group (B), was used alone. As a result, TMEG with a purity of 98.8% by weight was obtained in a yield of 62.0% by weight. The results are shown in Table 1. Comparative Example 3 The same procedure as in Example 1 was carried out except that 120 g of methyl acetoacetate, which is a type of solvent belonging to group (B), was used alone. As a result, TMEG with a purity of 98.0% by weight was obtained in a yield of 51.0% by weight. The results are shown in Table 1. Comparative Example 4 The same procedure as in Example 1 was carried out except that 120 g of carbitol acetate, which is a type of solvent belonging to group (B), was used. As a result, TMEG with a purity of 98.2% by weight was obtained in a yield of 54.7% by weight. The results are shown in Table 1. Comparative Example 5 The same procedure as in Example 1 was carried out except that 120 g of acetic anhydride, which is a type of solvent belonging to group (B), was used alone. As a result, TMEG with a purity of 98.2% by weight was obtained in a yield of 17.8% by weight. The results are shown in Table 1. Comparative Example 6 40 g of propionic acid (solubility of TMA in 25 is 5 g/100 g or less) and 80 g of xylene as solvents
The same procedure as in Example 1 was carried out except that . As a result, TMEG with a purity of 88.2% by weight was obtained in a yield of 86.7% by weight. The results are shown in Table 1. (Effects of the Invention) By applying the purification method according to the present invention, highly purified trimellitic acid ester anhydride can be obtained in high yield.
Claims (1)
テル無水物の粗物を精製するに際し、(A)群及び(B)
群からなる混合溶媒を用いて再結晶することを特
徴とするトリメリツト酸エステル無水物の精製方
法。 【化】 ［式中、Ｒはポリオール残基を示し、ｎは１〜
２の整数を表す。］ (A)群：25℃における無水トリメリツト酸エステ
ル無水物の溶解度が0.001〜３ｇ／100ｇであ
る炭化水素類 (B)群：25℃における無水トリメリツト酸の溶解
度が５〜50ｇ／100ｇである有機溶媒。[Claims] 1. When purifying the crude trimellitic acid ester anhydride represented by the general formula (), group (A) and (B)
1. A method for purifying trimellitic acid ester anhydride, which comprises recrystallizing using a mixed solvent consisting of the following. [In the formula, R represents a polyol residue, and n is 1 to
Represents an integer of 2. ] (A) Group: Hydrocarbons in which the solubility of trimellitic anhydride ester anhydride at 25°C is 0.001 to 3 g/100g (B) Group: Organics in which the solubility of trimellitic anhydride is 5 to 50 g/100g at 25°C solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6115089A JPH02240074A (en) | 1989-03-13 | 1989-03-13 | Purification of trimellitic acid ester anhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6115089A JPH02240074A (en) | 1989-03-13 | 1989-03-13 | Purification of trimellitic acid ester anhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02240074A JPH02240074A (en) | 1990-09-25 |
| JPH0577672B2 true JPH0577672B2 (en) | 1993-10-27 |
Family
ID=13162801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6115089A Granted JPH02240074A (en) | 1989-03-13 | 1989-03-13 | Purification of trimellitic acid ester anhydride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02240074A (en) |
-
1989
- 1989-03-13 JP JP6115089A patent/JPH02240074A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02240074A (en) | 1990-09-25 |
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