JP3521236B2 - Modification method of chemical blowing agent - Google Patents
Modification method of chemical blowing agentInfo
- Publication number
- JP3521236B2 JP3521236B2 JP15173793A JP15173793A JP3521236B2 JP 3521236 B2 JP3521236 B2 JP 3521236B2 JP 15173793 A JP15173793 A JP 15173793A JP 15173793 A JP15173793 A JP 15173793A JP 3521236 B2 JP3521236 B2 JP 3521236B2
- Authority
- JP
- Japan
- Prior art keywords
- foaming agent
- parts
- chemical
- silane coupling
- present
- 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.)
- Expired - Fee Related
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- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、化学発泡剤の改質法に
関する。FIELD OF THE INVENTION The present invention relates to a method for modifying a chemical blowing agent.
【０００２】[0002]
【従来技術とその課題】化学発泡剤は、現在ポリエチレ
ン、ポリプロピレン、エチレン−酢酸ビニル共重合体、
ポリ塩化ビニル、ゴム等の発泡剤として、その優れた発
泡特性を利用して広く使用されている。BACKGROUND OF THE INVENTION Chemical blowing agents are currently polyethylene, polypropylene, ethylene-vinyl acetate copolymer,
It is widely used as a foaming agent for polyvinyl chloride, rubber, etc., due to its excellent foaming characteristics.
【０００３】化学発泡剤は通常微粉末状の化合物であ
り、一般の無機、有機粉体と同様、経時固化により製品
の品質が低下したり、樹脂中での分散不良が発生する等
の問題を有している。The chemical foaming agent is usually a fine powdery compound, and like general inorganic and organic powders, it suffers from problems such as deterioration of product quality due to solidification over time and poor dispersion in resin. Have
【０００４】このような問題を解決するために、現在
（１）無機系粉末微粒子のシリカ、タルク、ケイ酸金属
塩等の固化防止剤を添加する方法、（２）化学発泡剤の
乾燥方式をバッチ式にして付着水分を減少させる方法等
が採用されている。In order to solve such problems, at present (1) a method of adding a solidification inhibitor such as silica, talc, metal silicate of fine particles of an inorganic powder, and (2) a method of drying a chemical foaming agent are used. A method of reducing the adhering water content by a batch method is adopted.
【０００５】しかしながら、これらの方法を採用した場
合には種々の欠点が生ずる。即ち、（１）の方法では、
見掛上は流動性が改善され、ある程度の経時固化防止効
果が認められるが、その効果の発現は短期間に止まり、
特に微粒子の化学発泡剤に対しては効果が少ない。また
（２）の方法は、バッチ式のため乾燥に長時間を要し、
生産能力がかなり低下するので連続生産に対応できない
という問題がある。However, when these methods are adopted, various drawbacks occur. That is, in the method (1),
Apparently, the fluidity is improved, and a certain degree of solidification prevention effect over time is recognized, but the onset of that effect stops in a short period of time,
In particular, it is less effective against fine chemical blowing agents. In addition, the method (2) requires a long time for drying because it is a batch method,
There is a problem that continuous production cannot be supported because the production capacity is considerably reduced.
【０００６】また、特開平４−３２０４３２号公報に
は、有機発泡剤にシラン系化合物を添加する方法が開示
されている。しかしながら、該方法では、ある程度粒子
の大きな化学発泡剤に対しては、所期の効果が認められ
るものの、微粒子の化学発泡剤に対しては効果が不充分
である。Further, JP-A-4-320432 discloses a method of adding a silane compound to an organic foaming agent. However, in this method, although a desired effect is recognized for a chemical foaming agent having large particles to some extent, the effect is insufficient for a fine chemical foaming agent.
【０００７】[0007]
【課題を解決するための手段】本発明者は、上記従来技
術での課題を解決するため、鋭意検討を進めた結果、従
来より使用されていた無機系シリカ（ホワイトカーボ
ン）と化学発泡剤とをシラン系カップリング剤で表面処
理をして、シラン系カップリング剤により化学発泡剤の
結晶表面にシリカの微細粒子を結合させたところ、この
結合したシリカ微粒子が化学発泡剤の結晶間での潤滑効
果を高めることができ、その結果流動性、経時固化性、
樹脂中での分散性が従来より大幅に改良されることを見
い出した。本発明は、斯かる知見に基づき完成されたも
のである。The inventors of the present invention have made extensive studies in order to solve the above-mentioned problems in the prior art, and as a result, have found that inorganic silica (white carbon) and a chemical foaming agent which have been conventionally used are used. Was surface-treated with a silane coupling agent, and fine silica particles were bonded to the crystal surface of the chemical foaming agent with the silane coupling agent. The lubrication effect can be enhanced, resulting in fluidity, solidification property over time,
It has been found that the dispersibility in the resin is greatly improved as compared with the conventional one. The present invention has been completed based on such knowledge.
【０００８】即ち、本発明は、シラン系カップリング剤
で化学発泡剤と無機シリカとを結合させることを特徴と
する化学発泡剤の改質法に係る。That is, the present invention relates to a method for modifying a chemical foaming agent, which comprises bonding the chemical foaming agent and the inorganic silica with a silane coupling agent.
【０００９】本発明で処理される化学発泡剤としては、
粉末状である限り従来公知のものを広く使用でき、例え
ばアゾジカルボンアミド、ｐ，ｐ´−オキシビスベンゼ
ンスルホニルヒドラジド、ジニトロソペンタメチレンテ
トラミン、ｐ−トルエンスルホニルヒドラジド、ベンゼ
ンスルホニルヒドラジド、炭酸水素ナトリウム、炭酸ナ
トリウム等を挙げることができる。斯かる化学発泡剤の
粒子径は、特に限定されるものではないが、本発明では
通常２〜７０μｍ程度、殊に５〜３０μｍ程度の微粒子
の化学発泡剤を用いるのが望ましい。The chemical foaming agent treated in the present invention includes:
As long as it is in powder form, conventionally known compounds can be widely used, and examples thereof include azodicarbonamide, p, p'-oxybisbenzenesulfonylhydrazide, dinitrosopentamethylenetetramine, p-toluenesulfonylhydrazide, benzenesulfonylhydrazide, sodium hydrogencarbonate, Examples thereof include sodium carbonate. The particle diameter of such a chemical foaming agent is not particularly limited, but in the present invention, it is desirable to use a fine chemical foaming agent having a particle size of usually about 2 to 70 μm, particularly about 5 to 30 μm.
【００１０】本発明で処理される無機シリカとしては、
特に限定がなく、通常充填剤として市販されているＳｉ
Ｏ2 を主成分とするホワイトカーボン等を広く使用でき
る。The inorganic silica treated in the present invention includes:
There is no particular limitation, and Si which is usually marketed as a filler is used.
A wide variety of white carbons containing O 2 as a main component can be used.
【００１１】本発明で使用されるシラン系カップリング
剤としては、特に限定されず従来公知のものを広く使用
でき、例えばトリメチルメトキシシラン、メチルトリエ
トキシシラン、メチルジメトキシシラン等のアルコキシ
シラン化合物、γ−アミノプロピルトリメトキシシラ
ン、γ−（２−アミノエチル）アミノプロピルトリメト
キシシラン、３−アミノプロピルメチルジエトキシシラ
ン、トリメトキシシリルプロピルジエチレントリアミ
ン、ビニルトリエトキシシラン等の有機官能性シラン化
合物等を挙げることができる。The silane coupling agent used in the present invention is not particularly limited and widely known ones can be widely used. For example, an alkoxysilane compound such as trimethylmethoxysilane, methyltriethoxysilane and methyldimethoxysilane, γ -Organofunctional silane compounds such as -aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, trimethoxysilylpropyldiethylenetriamine and vinyltriethoxysilane. be able to.
【００１２】本発明において、化学発泡剤、無機シリカ
及びシラン系カップリング剤の使用割合は特に制限され
るものではないが、通常化学発泡剤１００重量部当り、
無機シリカを０．２〜１０重量部、好ましくは０．５〜
２重量部、シラン系カップリング剤を０．０１〜５重量
部、好ましくは０．１〜１重量部使用するのがよい。無
機シリカの使用量が少なすぎると、本発明の所期の効果
が発現され難くなる傾向となり、逆に無機シリカの使用
量が多すぎると、発泡剤としての純度が低下し、セル荒
れの原因になる傾向が生ずるので、いずれも好ましくな
い。またシラン系カップリング剤の使用量が少なすぎる
と本発明の所期の効果が発現され難くなる傾向となり、
逆にシラン系カップリング剤の使用量が多すぎると、発
泡剤の発泡特性に影響を及ぼす傾向が生ずるので、いず
れも好ましくない。In the present invention, the use ratio of the chemical foaming agent, the inorganic silica and the silane coupling agent is not particularly limited, but is usually 100 parts by weight of the chemical foaming agent.
0.2 to 10 parts by weight of inorganic silica, preferably 0.5 to
2 parts by weight and 0.01 to 5 parts by weight, preferably 0.1 to 1 part by weight of the silane coupling agent are used. If the amount of the inorganic silica used is too small, the desired effect of the present invention tends to be difficult to be expressed. Conversely, if the amount of the inorganic silica used is too large, the purity as a foaming agent decreases and the cause of cell roughening occurs. However, both of them are not preferable. When the amount of the silane coupling agent used is too small, the desired effect of the present invention tends to be difficult to be expressed,
On the other hand, if the amount of the silane coupling agent used is too large, the foaming properties of the foaming agent tend to be affected, which is not preferable.
【００１３】化学発泡剤及び無機シリカをシラン系カッ
プリング剤で処理するに当っては、通常ミキシングに使
用される混合機、例えばヘンシェルミキサー、スーパー
ミキサー等に上記３成分を入れて混合するのがよい。こ
れら３成分を混合するに際しては、３成分を一度に混合
してもよいし、２成分を先に混合した後、残りの１成分
を混合してもよい。またシランカップリング剤は、直接
混合してもよい（乾式法）し、適当な有機溶剤に溶かし
て混合してもよい（湿式法）。In treating the chemical foaming agent and the inorganic silica with the silane coupling agent, the above three components are put into a mixer which is usually used for mixing, such as a Henschel mixer and a super mixer, and mixed. Good. When mixing these three components, the three components may be mixed at once, or the two components may be mixed first and then the remaining one component may be mixed. The silane coupling agent may be directly mixed (dry method) or may be dissolved in an appropriate organic solvent and mixed (wet method).
【００１４】[0014]
【発明の効果】本発明の方法で処理された化学発泡剤
は、処理前に比し流動性が極めて良好であり、経時固化
性が充分に改良され、その結果樹脂中での分散性に良好
で、品質低下のない優れたものであった。本発明の処理
によって化学発泡剤の純度に悪影響を受けることは殆ん
どない。従って、本発明により、化学発泡剤の製造から
出荷まで、また出荷からユーザーでの使用までのストッ
ク、流通段階での製品の経時固化の不安を解消できた。The chemical foaming agent treated by the method of the present invention has extremely good fluidity as compared with that before the treatment and has sufficiently improved solidification property over time, resulting in good dispersibility in the resin. It was an excellent product with no deterioration in quality. The purity of the chemical blowing agent is hardly adversely affected by the treatment of the present invention. Therefore, according to the present invention, it is possible to eliminate the anxiety of solidification of the product over time at the stock and distribution stages from the production of the chemical foaming agent to the shipment, and from the shipment to the use by the user.
【００１５】[0015]
【実施例】以下に実施例を掲げて本発明をより一層明ら
かにする。尚、単に「部」とあるのは「重量部」をそれ
ぞれ意味する。EXAMPLES The present invention will be further clarified with reference to the following examples. The term "parts" simply means "parts by weight".
【００１６】実施例１
アゾジカルボンアミド１００部、ホワイトカーボン０．
５部及びγ−アミノプロピルトリメトキシシラン〔Ｓ−
３３０、チッソ（株）製〕０．２部をスーパーミキサー
を用いて、室温、６００ｒｐｍにて５分間混合処理して
発泡剤組成物を得た。Example 1 100 parts of azodicarbonamide, 0.
5 parts and γ-aminopropyltrimethoxysilane [S-
330, manufactured by Chisso Corp.] 0.2 part was mixed with a supermixer at room temperature and 600 rpm for 5 minutes to obtain a foaming agent composition.
【００１７】実施例２
アゾジカルボンアミド１００部、ホワイトカーボン０．
５部及びγ−（２−アミノエチル）アミノプロピルトリ
メトキシシラン〔ＳＨ−６０２０、東レシリコーン
（株）製〕０．２部をスーパーミキサーを用いて、室
温、６００ｒｐｍにて５分間混合処理して発泡剤組成物
を得た。Example 2 100 parts of azodicarbonamide, 0.
5 parts and 0.2 part of γ- (2-aminoethyl) aminopropyltrimethoxysilane [SH-6020, manufactured by Toray Silicone Co., Ltd.] are mixed at room temperature and 600 rpm for 5 minutes using a super mixer. A foaming agent composition was obtained.
【００１８】比較例１
アゾジカルボンアミド１００部をスーパーミキサーを用
いて、室温、６００ｒｐｍにて５分間処理して発泡剤組
成物（無処理）とした。Comparative Example 1 100 parts of azodicarbonamide was treated with a supermixer at room temperature and 600 rpm for 5 minutes to obtain a foaming agent composition (untreated).
【００１９】比較例２
アゾジカルボンアミド１００部及びホワイトカーボン
０．５部をスーパーミキサーを用いて、室温、６００ｒ
ｐｍにて５分間混合処理して発泡剤組成物を得た。Comparative Example 2 100 parts of azodicarbonamide and 0.5 part of white carbon were mixed with a supermixer at room temperature for 600 r.
A foaming agent composition was obtained by mixing for 5 minutes at pm.
【００２０】比較例３
アゾジカルボンアミド１００部及びγ−アミノプロピル
トリメトキシシラン〔Ｓ−３３０、チッソ（株）製〕
０．２部をスーパーミキサーを用いて、室温、６００ｒ
ｐｍにて５分間混合処理して発泡剤組成物を得た。Comparative Example 3 100 parts of azodicarbonamide and γ-aminopropyltrimethoxysilane [S-330, manufactured by Chisso Corporation]
0.2 parts using a super mixer, room temperature, 600r
A foaming agent composition was obtained by mixing for 5 minutes at pm.
【００２１】実施例３
ｐ，ｐ´−オキシビスベンゼンスルホニルヒドラジド１
００部、ホワイトカーボン１．０部及びγ−アミノプロ
ピルトリメトキシシラン〔Ｓ−３３０、チッソ（株）
製〕０．５部をスーパーミキサーを用いて、室温、６０
０ｒｐｍにて５分間混合処理して発泡剤組成物を得た。Example 3 p, p'-oxybisbenzenesulfonyl hydrazide 1
00 parts, white carbon 1.0 parts and γ-aminopropyltrimethoxysilane [S-330, Chisso Corporation
Manufactured] 0.5 part using a super mixer at room temperature, 60
A mixing treatment was performed at 0 rpm for 5 minutes to obtain a foaming agent composition.
【００２２】実施例４
ｐ，ｐ´−オキシビスベンゼンスルホニルヒドラジド１
００部、ホワイトカーボン１．０部及びγ−（２−アミ
ノエチル）アミノプロピルトリメトキシシラン〔ＳＨ−
６０２０、東レシリコーン（株）製〕０．５部をスーパ
ーミキサーを用いて、室温、６００ｒｐｍにて５分間混
合処理して発泡剤組成物を得た。Example 4 p, p'-oxybisbenzenesulfonyl hydrazide 1
00 parts, white carbon 1.0 part and γ- (2-aminoethyl) aminopropyltrimethoxysilane [SH-
6020, manufactured by Toray Silicone Co., Ltd.] 0.5 part was mixed with a supermixer at room temperature and 600 rpm for 5 minutes to obtain a foaming agent composition.
【００２３】比較例４
ｐ，ｐ´−オキシビスベンゼンスルホニルヒドラジド１
００部をスーパーミキサーを用いて、室温、６００ｒｐ
ｍにて５分間処理して発泡剤組成物（無処理）とした。Comparative Example 4 p, p'-oxybisbenzenesulfonyl hydrazide 1
00 parts using a super mixer at room temperature, 600 rp
m for 5 minutes to obtain a foaming agent composition (untreated).
【００２４】比較例５
ｐ，ｐ´−オキシビスベンゼンスルホニルヒドラジド１
００部及びホワイトカーボン１．０部をスーパーミキサ
ーを用いて、室温、６００ｒｐｍにて５分間混合処理し
て発泡剤組成物を得た。Comparative Example 5 p, p'-oxybisbenzenesulfonyl hydrazide 1
Using a super mixer, 00 parts and 1.0 part of white carbon were mixed at room temperature for 5 minutes at 600 rpm to obtain a foaming agent composition.
【００２５】比較例６
ｐ，ｐ´−オキシビスベンゼンスルホニルヒドラジド１
００部及びγ−アミノプロピルトリメトキシシラン〔Ｓ
−３３０、チッソ（株）製〕０．５部をスーパーミキサ
ーを用いて、室温、６００ｒｐｍにて５分間混合処理し
て発泡剤組成物を得た。Comparative Example 6 p, p'-oxybisbenzenesulfonyl hydrazide 1
00 parts and γ-aminopropyltrimethoxysilane [S
-330, manufactured by Chisso Co., Ltd.] 0.5 part was mixed with a super mixer at room temperature and 600 rpm for 5 minutes to obtain a foaming agent composition.
【００２６】上記実施例及び比較例で得られた各発泡剤
組成物につき、下記に示す方法で堆積固化テスト、実包
装固化テスト及び安息角の測定を行ない、結果を表１に
示す。With respect to each of the foaming agent compositions obtained in the above Examples and Comparative Examples, a deposition solidification test, an actual packaging solidification test, and an angle of repose were measured by the following methods, and the results are shown in Table 1.
【００２７】（１）堆積固化テスト；各発泡剤組成物
（サンプル）４００ｇを２３ｃｍ×１３ｃｍのポリ袋に
充填し、充分脱気後開口部をヒートシールしたものを重
ねて、上から０．０７ｋｇ／ｃｍ2 の荷重を加えた。２
週間後サンプルを取出し、１４ｍｅのフルイにて篩分け
して不通過物の量を測定し、％に換算して求めた値を堆
積固化テスト値とした。(1) Deposition solidification test: 400 g of each foaming agent composition (sample) was filled in a polybag of 23 cm × 13 cm, sufficiently deaerated, and then heat-sealed at the opening, and then 0.07 kg from the top. A load of / cm 2 was applied. Two
After a week, the sample was taken out, sieved with a 14-me sieve to measure the amount of non-passing substances, and the value obtained by converting into% was used as a deposition solidification test value.
【００２８】（２）実包装固化テスト；各発泡剤組成物
（サンプル）を製品流通包装であるダンボールケースに
２５ｋｇ充填包装し、温度４０℃、湿度８０％の条件下
に１ヶ月間放置し、その後１４ｍｅのフルイにて篩分け
して不通過物の量を測定し、％に換算して求めた値を実
包装固化テスト値とした。(2) Real package solidification test: 25 kg of each foaming agent composition (sample) was packed in a corrugated cardboard case, which is a product distribution package, and allowed to stand for 1 month at a temperature of 40 ° C. and a humidity of 80%. After that, it was sieved with a 14-me screen to measure the amount of non-passing substances, and the value obtained by converting into% was used as the actual packaging solidification test value.
【００２９】（３）安息角の測定；バウダーテスター
〔粉体特性総合測定装置、ＰＴ−Ｅ型、ホソカワミクロ
ン（株）製〕を用いて各発泡剤組成物（サンプル）の安
息角を調べた。(3) Measurement of angle of repose: The angle of repose of each foaming agent composition (sample) was examined using a Bowder tester [Powder property comprehensive measuring device, PT-E type, manufactured by Hosokawa Micron Co., Ltd.].
【００３０】[0030]
【表１】 [Table 1]
【００３１】表１から次のことが判る。即ち、化学発泡
剤をシラン系カップリング剤及び無機シリカと混合処理
することにより、シラン系カップリング剤、無機シリカ
単独処理では考えられない相乗効果が得られ、流動性の
目安である安息角、経時固化性が大きく改良された結
果、樹脂との分散性の高い発泡剤組成物が得られた。こ
のようにシラン系カップリング剤により、化学発泡剤の
結晶表面に無機シリカを結合させることにより、微粉体
の性質として根本的に存在する経時固化、分散性の問題
を解決することが可能になった。The following can be seen from Table 1. That is, by mixing the chemical foaming agent with the silane coupling agent and the inorganic silica, a synergistic effect which cannot be expected by the silane coupling agent and the inorganic silica alone treatment is obtained, and the angle of repose is a measure of fluidity, As a result of the greatly improved solidification property over time, a foaming agent composition having high dispersibility with the resin was obtained. Thus, by binding the inorganic silica to the crystal surface of the chemical foaming agent by the silane coupling agent, it becomes possible to solve the problems of solidification with time and dispersibility which are fundamentally present as the properties of the fine powder. It was
フロントページの続き (72)発明者 舘 良 文 徳島県鳴門市里浦町里浦字花面649−２ 大塚化学株式会社鳴門工場内 (56)参考文献 特開 平６−179862（ＪＰ，Ａ) 特開 平４−320432（ＪＰ，Ａ) 特開 平５−70619（ＪＰ，Ａ) 特開 平６−128402（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C09K 3/00 111 Continuation of the front page (72) Inventor Yoshifumi Tate 649-2 Satoura, Satoura-cho, Naruto City, Tokushima Prefecture Inside the Naruto Plant, Otsuka Chemical Co., Ltd. (56) Reference JP-A-6-179862 (JP, A) JP-A-4 -320432 (JP, A) JP-A-5-70619 (JP, A) JP-A-6-128402 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C09K 3/00 111
Claims (2)
無機シリカとを結合させることを特徴とする化学発泡剤
の改質法。1. A method for modifying a chemical foaming agent, which comprises bonding the chemical foaming agent and inorganic silica with a silane coupling agent.
カを０．２〜１０重量部、シラン系カップリング剤を
０．０１〜５重量部使用する請求項１記載の化学発泡剤
の改質法。2. Modification of the chemical blowing agent according to claim 1, wherein 0.2 to 10 parts by weight of inorganic silica and 0.01 to 5 parts by weight of a silane coupling agent are used per 100 parts by weight of the chemical blowing agent. Law.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15173793A JP3521236B2 (en) | 1993-06-23 | 1993-06-23 | Modification method of chemical blowing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15173793A JP3521236B2 (en) | 1993-06-23 | 1993-06-23 | Modification method of chemical blowing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0711234A JPH0711234A (en) | 1995-01-13 |
| JP3521236B2 true JP3521236B2 (en) | 2004-04-19 |
Family
ID=15525194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15173793A Expired - Fee Related JP3521236B2 (en) | 1993-06-23 | 1993-06-23 | Modification method of chemical blowing agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3521236B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY129168A (en) * | 1998-03-03 | 2007-03-30 | Otsuka Chemical Co Ltd | Substantially anhydrous blowing agent and process for producing the same |
| KR101217865B1 (en) * | 2006-10-17 | 2013-01-03 | 주식회사 제이앤드제이 캐미칼 | A method for modifying a blowing agent |
| KR101327439B1 (en) * | 2006-10-17 | 2013-11-08 | 주식회사 제이앤드제이 캐미칼 | Modified blowing agent surface-treated with metallic siloxylated compound and polymer resin composition including the same |
| CN111411250B (en) * | 2020-04-07 | 2021-07-09 | 广东广纳新材料有限公司 | Expandable microsphere foaming agent, preparation method thereof and foaming material |
-
1993
- 1993-06-23 JP JP15173793A patent/JP3521236B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0711234A (en) | 1995-01-13 |
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