JP3117252B2 - Die for forming honeycomb structure and method for manufacturing honeycomb structure using the same - Google Patents
Die for forming honeycomb structure and method for manufacturing honeycomb structure using the sameInfo
- Publication number
- JP3117252B2 JP3117252B2 JP03286546A JP28654691A JP3117252B2 JP 3117252 B2 JP3117252 B2 JP 3117252B2 JP 03286546 A JP03286546 A JP 03286546A JP 28654691 A JP28654691 A JP 28654691A JP 3117252 B2 JP3117252 B2 JP 3117252B2
- Authority
- JP
- Japan
- Prior art keywords
- honeycomb structure
- hole
- wall
- clay
- die
- 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
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 238000000034 method Methods 0.000 title description 11
- 230000002093 peripheral effect Effects 0.000 claims description 17
- 239000000919 ceramic Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 7
- 230000001360 synchronised effect Effects 0.000 claims description 4
- 239000002689 soil Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 description 49
- 239000000463 material Substances 0.000 description 18
- 238000000465 moulding Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は内燃機関の排気ガス浄化
用および脱臭用触媒の担体、あるいは不純物除去用フィ
ルタ（ストレーナ）およびオゾン除去用フィルタ等に用
いられる、ハニカム構造体およびその成形用ダイスに関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a honeycomb structure and a die for forming the same, which are used for a carrier of a catalyst for purifying and deodorizing exhaust gas of an internal combustion engine, or a filter (strainer) for removing impurities and a filter for removing ozone. It is about.
【０００２】[0002]
【従来の技術】従来一般に使用されている触媒コンバー
タ用の一体成形したセラミックハニカム構造体は、図６
（ａ）（ｂ）にその貫通孔にそった断面図および貫通孔
に垂直な断面図を示すように、外壁２と格子状の壁３か
らなり、複数の貫通孔５を備えたものであった。そし
て、このハニカム構造体１は、図７（ａ）に示すよう
に、スクリーン１０を後端に備え、坏土供給孔８と壁形
成溝９を有する成形用ダイス７を用いて、押し出し成形
で製造することから、その壁３は全ての部分で貫通孔５
方向に直線状となっていた。2. Description of the Related Art An integrally formed ceramic honeycomb structure for a catalytic converter, which is conventionally generally used, is shown in FIG.
(A) As shown in the cross-sectional view along the through-hole and the cross-sectional view perpendicular to the through-hole in (b), the outer wall 2 and the lattice-shaped wall 3 are provided, and a plurality of through-holes 5 are provided. Was. Then, as shown in FIG. 7A, the honeycomb structure 1 is provided with a screen 10 at a rear end, and is extruded by using a forming die 7 having a clay supply hole 8 and a wall forming groove 9. Because of the manufacture, the wall 3 has through holes 5 in all parts.
It was linear in the direction.
【０００３】そのため、触媒コンバータとして用いた場
合に、ハニカム構造体１中を排気ガスが簡単に通り抜
け、圧力損失が小さいという利点はあるものの、排気ガ
スと貫通孔５の壁面との相互作用が小さく、浄化効率の
点で問題があった。そこで、この問題を解決するため
に、特開昭５８−４３２３８号公報で開示されているよ
うに、セラミックハニカム構造体の壁全体を貫通孔方向
に波状に形成したものが知られている。また、その製造
方法として押し出し成形直後のまだ柔らかい状態のハニ
カム構造体に、ねじれ、振動を加える方法が開示されて
いる。Therefore, when used as a catalytic converter, there is an advantage that the exhaust gas easily passes through the honeycomb structure 1 and the pressure loss is small, but the interaction between the exhaust gas and the wall surface of the through hole 5 is small. However, there was a problem in terms of purification efficiency. In order to solve this problem, there has been known a ceramic honeycomb structure in which the entire wall is formed in a wavy shape in the direction of a through hole, as disclosed in Japanese Patent Application Laid-Open No. 58-43238. Also disclosed is a method of applying torsion and vibration to a honeycomb structure in a soft state immediately after extrusion molding as a manufacturing method thereof.
【０００４】しかしながら、この技術ではハニカム構造
体のすべての壁が貫通孔方向に波となるため、ハニカム
構造体としての外圧強度が非常に低く、強固な保持がで
きなかった。その結果、このハニカム構造体をそのまま
自動車には搭載できないという問題があった。However, in this technique, since all the walls of the honeycomb structure have waves in the direction of the through holes, the external pressure strength of the honeycomb structure is extremely low, and the honeycomb structure cannot be firmly held. As a result, there is a problem that the honeycomb structure cannot be mounted on an automobile as it is.
【０００５】この問題を解消するために、特開平３−１
５１０４９号公報で開示されているように、触媒担体用
のセラミックハニカム構造体において、貫通孔に垂直な
断面における外周部の壁を貫通孔方向に直線状とし、中
央部の壁のみを貫通孔方向に波状に形成したセラミック
ハニカム構造体が提案されている。また、その製造方法
として、ハニカム構造体成形用のダイスに供給する坏土
を、外周部の直線状の壁の部分には少なく、中央部の波
状の壁の部分には多く供給することが示されている。ま
た、このように坏土の供給量に差をつけるための手段と
しては、 (1) 成形用ダイスの坏土供給孔において中央部の孔径を
外周部の孔径より大きくする (2) 成形用ダイスの上流側のスクリーンにおいて、中央
部のスクリーンの目開きを外周部の目開きより大きくす
る (3) 熱により流動性を発現するバインダを使用し、外部
から加熱する等の方法が開示されている。To solve this problem, Japanese Patent Laid-Open No.
As disclosed in Japanese Patent No. 51049, in a ceramic honeycomb structure for a catalyst carrier, a wall of an outer peripheral portion in a cross section perpendicular to a through hole is linear in a direction of a through hole, and only a wall at a central portion is oriented in a direction of a through hole. A ceramic honeycomb structure having a wavy shape has been proposed. Further, as a manufacturing method thereof, it is shown that the amount of the clay to be supplied to the die for forming the honeycomb structure is supplied less to the portion of the straight wall on the outer peripheral portion and more to the portion of the wavy wall at the center. Have been. Means for differentiating the supply amount of the kneaded clay in this way include (1) making the diameter of the center of the kneaded clay supply hole of the forming die larger than the diameter of the outer peripheral portion. (2) In the screen on the upstream side, the aperture of the center screen is made larger than the aperture of the outer peripheral part. .
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、上記の
ような特開平３−１５１０４９号公報で開示されている
ハニカム構造体は、中央部の波形状が貫通孔方向のみに
しか形成されず、その波高さも０．３ｍｍ以下の低いも
のであったため、触媒などとして用いた場合に浄化効率
の低いものであった。However, in the honeycomb structure disclosed in Japanese Patent Application Laid-Open No. 3-15049 described above, the wavy shape of the central portion is formed only in the direction of the through hole, and the wave height of the central portion is small. Since it was as low as 0.3 mm or less, the purification efficiency was low when used as a catalyst or the like.
【０００７】また、上記のハニカム構造体の製造方法で
は、坏土の成形用ダイスへの供給方法において、以下の
ような問題点があった。Further, the above-described method for manufacturing a honeycomb structure has the following problems in the method of supplying the kneaded material to the forming die.
【０００８】まず、(1) 坏土の成形用ダイスへの供給孔
において、中央部の孔径を外周部の孔径より大きくする
方法が開示されているが、ハニカム構造体の貫通孔方向
の波形状と押し出しダイスの坏土供給孔の孔径の間には
密接な関係があり、坏土の組成、硬さ、粘度が変わると
希望するハニカム構造体の貫通孔方向の波は得られない
という問題があった。すなわち、坏土が硬い場合または
流動性がよい場合には、ハニカム構造体の貫通孔方向の
波形状は得られにくく、ハニカム構造体の壁のほとんど
が貫通孔方向に直線状になりやすかった。逆に、坏土が
柔らかく粘度が高い場合には、ハニカム構造体の貫通孔
方向の波形状がきわめて形成されやすく、貫通孔を塞い
でしまったり、また坏土が柔らかく粘度が高い場合に得
られるハニカム構造体は極めて保形性が弱く、製造工程
において取扱が大変困難である上、ハニカム構造体の形
状を維持できない問題があった。[0008] First, (1) a method is disclosed in which the diameter of the supply hole of the clay to the forming die is made larger at the center than at the outer periphery. There is a close relationship between the diameter of the kneaded material supply hole of the extrusion die and the diameter of the kneaded material supply hole, and if the composition, hardness, and viscosity of the kneaded material change, the wave in the direction of the through hole of the desired honeycomb structure cannot be obtained. there were. That is, when the clay was hard or had good fluidity, it was difficult to obtain a wavy shape in the direction of the through hole of the honeycomb structure, and most of the walls of the honeycomb structure were likely to be linear in the direction of the through hole. Conversely, when the clay is soft and has a high viscosity, a corrugated shape in the direction of the through-hole of the honeycomb structure is extremely easily formed, and the through-hole is blocked, or the kneaded clay is obtained when the clay is soft and has a high viscosity. The honeycomb structure has a very weak shape retention property, is very difficult to handle in a manufacturing process, and has a problem that the shape of the honeycomb structure cannot be maintained.
【０００９】このように、坏土の組成、硬さ、粘度が変
わる場合には、実験データに基づき、成形用ダイスの坏
土供給孔における中央部と外周部の孔径を決定し、坏土
に適した成形用ダイスをその都度作製しなければならな
いという問題点があった。As described above, when the composition, hardness, and viscosity of the kneaded clay change, the diameters of the central portion and the outer peripheral portion of the kneaded material supply hole of the forming die are determined based on experimental data, and the kneaded material is formed. There was a problem that a suitable molding die had to be produced each time.
【００１０】次に、他の供給方法として、(2) 成形用ダ
イスの上流側のスクリーンにおいて、中央部の目開きを
外周部の目開きより大きくする方法が開示されている
が、図７（ｂ）に示すように、スクリーン１０の厚みが
薄い場合には、成形圧力が加わることによりスクリーン
１０が変形し、成形用ダイス７とスクリーン１０の間に
坏土Ｃが入り込み、乱流が発生する。そのため、供給孔
８への安定した坏土Ｃの供給ができなくなって、安定し
たセラミックハニカム構造体が得られないという問題が
あった。特に、スクリーン１０の坏土供給孔１１の孔径
が成形用ダイス７の坏土供給孔８の孔径より小さい場合
には、上記現象が更に顕著になる。この問題を解消する
には、スクリーン１０に変形を防止するに充分な厚みが
必要である。しかしながらスクリーン１０の厚みを厚く
すると、スクリーン１０の坏土供給孔１１内での圧力伝
達効率が低下して押し出し抵抗が増大するため、セラミ
ックハニカム構造体が安定して押し出されない。また、
押し出し抵抗が増大するため、坏土の部分的な発熱が生
じて坏土の乱流を引き起こし、セラミックハニカム構造
体が安定して押し出されない。この現象は、坏土が硬い
場合または粘度が高い場合は更に顕著である。[0010] Next, as another supply method, (2) a method is disclosed in which the screen at the center of the screen on the upstream side of the molding die is made larger than the screen at the outer periphery. As shown in b), when the thickness of the screen 10 is small, the screen 10 is deformed by applying a molding pressure, the clay C enters between the molding die 7 and the screen 10, and a turbulent flow is generated. . For this reason, there is a problem that stable supply of the clay C to the supply hole 8 cannot be performed, and a stable ceramic honeycomb structure cannot be obtained. In particular, when the diameter of the kneaded material supply hole 11 of the screen 10 is smaller than the diameter of the kneaded material supply hole 8 of the forming die 7, the above-described phenomenon becomes more remarkable. In order to solve this problem, the screen 10 needs to have a sufficient thickness to prevent deformation. However, when the thickness of the screen 10 is increased, the pressure transmission efficiency of the screen 10 in the clay supply hole 11 is reduced and the extrusion resistance is increased, so that the ceramic honeycomb structure is not extruded stably. Also,
Since the extrusion resistance increases, partial heating of the clay occurs, causing turbulence of the clay, and the ceramic honeycomb structure is not stably extruded. This phenomenon is more remarkable when the clay is hard or has a high viscosity.
【００１１】さらに、他の供給方法として、(3) 熱によ
り流動性を発現するバインダを使用し外部から加熱する
方法が開示されているが、実際問題として外部から加熱
をするとハニカム構造体の中央部より外周部の方が温度
が高くなって、外周部の坏土の流動性が高くなり、希望
する温度分布と逆になるため、外周部の壁を貫通孔方向
に直線状とし、中央部の壁のみを貫通孔方向に波状とす
るハニカム構造体は得られない。この問題点を解消する
には、押し出し成形機の坏土を押し出す部品であるとこ
ろのオーガースクリューまたはピストンの内部中央付近
に空間を設け、熱媒体を介してハニカム構造体の中央部
の温度を調整する方法があるが、ハニカム構造体の温度
を均一に調整することは難しく、特にハニカム構造体の
外径がφ５０以上になると調整は極めて困難になり、希
望するハニカム構造体は得られなくなる。Further, as another supply method, (3) a method of externally heating using a binder that exhibits fluidity by heat is disclosed. However, as a practical matter, when heating is performed from the outside, the center of the honeycomb structure is not heated. The temperature of the outer peripheral part is higher than that of the part, and the fluidity of the kneaded material of the outer peripheral part becomes higher, which is opposite to the desired temperature distribution. It is not possible to obtain a honeycomb structure in which only the walls are corrugated in the direction of the through holes. In order to solve this problem, a space is provided near the center of the inside of the auger screw or piston, which is a part that extrudes the clay of the extrusion molding machine, and the temperature of the central portion of the honeycomb structure is adjusted via a heat medium. However, it is difficult to uniformly adjust the temperature of the honeycomb structure, and particularly when the outer diameter of the honeycomb structure is φ50 or more, the adjustment becomes extremely difficult, and a desired honeycomb structure cannot be obtained.
【００１２】このように、従来の製造方法では、外周部
の壁が貫通孔方向に直線状で、中央部の壁が波状である
ようなハニカム構造体を、容易にかつ安定して得ること
ができなかった。また、得られたハニカム構造体は、中
央部の壁の波高さが小さいものであった。As described above, according to the conventional manufacturing method, it is possible to easily and stably obtain a honeycomb structure in which the outer peripheral wall is linear in the direction of the through hole and the central wall is wavy. could not. The obtained honeycomb structure had a small wall height at the center wall.
【００１３】[0013]
【課題を解決するための手段】上記に鑑みて、本発明の
ハニカム構造体は、複数の貫通孔を有する筒状のハニカ
ム構造体において、貫通孔に垂直な断面における外周部
の壁を貫通孔方向及び貫通孔と垂直方向共に直線状とす
るとともに、中央部の壁のみを各壁が貫通孔方向に互い
に同期した波状とし、この波形状を貫通孔方向及び貫通
孔と垂直方向の両方に形成したものである。なお、ここ
で互いに同期した波状とは、各波状壁の凹凸の向きが同
じであることを言う。SUMMARY OF THE INVENTION In view of the above, the present invention provides a honeycomb structured body having a plurality of through-holes, wherein a wall of an outer peripheral portion in a cross section perpendicular to the through-hole is formed in the honeycomb structure. Direction and the through-hole are both straight, and only the central wall is corrugated with each wall synchronized with the through-hole direction, and this wave shape is formed in both the through-hole direction and the through-hole and vertical direction. It was done. Here, the wave shape synchronized with each other means that the direction of the unevenness of each wavy wall is the same.
【００１４】また、本発明は成形用ダイスの所定の坏土
供給孔に坏土供給量調整リングを備え、この成形用ダイ
スを用いてセラミック原料を押し出し成形することによ
って、上記のハニカム構造体を得るようにしたものであ
る。Further, the present invention provides a kneaded material supply amount adjusting ring in a predetermined kneaded material supply hole of a forming die, and extrudes a ceramic raw material using the forming die to form the honeycomb structure. It is something that you get.
【００１５】[0015]
【作用】本発明のハニカム構造体の製造方法によれば、
成形用ダイスに形成した複数の坏土供給孔のうち、所定
位置に調整リングを備え、また調整リングの大きさも自
由に変化させられることから、各坏土供給孔への坏土の
供給量に差を付けることができ、壁を任意の波形状とす
ることができる。また、組成、硬さ、粘度等の異なる坏
土に対しても、同様にして壁の波高さを自由に調整する
ことができる。According to the method for manufacturing a honeycomb structure of the present invention,
Of the plurality of clay supply holes formed in the forming die, an adjustment ring is provided at a predetermined position, and since the size of the adjustment ring can be freely changed, the supply amount of the clay to each clay supply hole is Differences can be made and the walls can be of any wave shape. Also, the crest height of the wall can be freely adjusted in the same manner for clays having different compositions, hardness, viscosity, and the like.
【００１６】さらに、このような製造方法で得られた本
発明のハニカム構造体は、中央部の波形状が貫通孔方向
だけでなく、貫通孔に垂直な方向にも形成でき、その波
高さを０．５ｍｍ以上とできることから、触媒などとし
て用いた場合に、排気ガスとの接触面積が大きくなり、
効率を高められる。Further, in the honeycomb structure of the present invention obtained by such a manufacturing method, the wavy shape at the center can be formed not only in the direction of the through hole but also in the direction perpendicular to the through hole, and the wave height can be reduced. Because it can be 0.5 mm or more, when used as a catalyst, etc., the contact area with the exhaust gas increases,
Increase efficiency.
【００１７】[0017]
【実施例】以下、本発明実施例を図によって説明する。BRIEF DESCRIPTION OF THE DRAWINGS FIG.
【００１８】図１（ａ）（ｂ）は本発明のハニカム構造
体の一例の構造を示す、貫通孔方向および貫通孔に垂直
方向の断面図である。この実施例では、ハニカム構造体
１の外壁２および外周部の壁３が貫通孔５方向および貫
通孔５と垂直方向共に直線状であり、中央部の壁４は貫
通孔５方向および貫通孔５と垂直方向共に波状となって
いる。また、各壁４の波形状は貫通孔５方向に互いに同
期しており、その凹凸形状が同一方向となっている。FIGS. 1A and 1B are cross-sectional views showing a structure of an example of a honeycomb structure according to the present invention in a through hole direction and a direction perpendicular to the through hole. In this embodiment, the outer wall 2 and the outer peripheral wall 3 of the honeycomb structure 1 are linear in both the direction of the through hole 5 and the direction perpendicular to the through hole 5, and the central wall 4 is in the direction of the through hole 5 and the through hole 5. And in both vertical directions. In addition, the corrugations of the walls 4 are synchronized with each other in the direction of the through-hole 5, and the concavo-convex shape is in the same direction.
【００１９】このハニカム構造体１は、中央部の壁４が
貫通孔５方向に互いに同期した波状となっていることか
ら、触媒として用いた場合の排気ガスの流通抵抗を低下
させずに接触面積が大きくなって、浄化効率を高めるこ
とができる。また、外壁２および外周部の壁３は直線状
であるから、ハニカム構造体１自体の外圧強度は高くな
り、取付等も容易である。さらに、このハニカム構造体
１は、耐熱衝撃性の点でも、各貫通孔５内で生じた応力
を壁４の波形状が吸収できることから、全体が直線状の
ものよりも優れている。Since the honeycomb structure 1 has corrugated central walls 4 in the direction of the through holes 5, the honeycomb structure 1 has a contact area without reducing the flow resistance of exhaust gas when used as a catalyst. And the purification efficiency can be increased. Further, since the outer wall 2 and the outer peripheral wall 3 are linear, the external pressure strength of the honeycomb structure 1 itself is increased, and mounting and the like are easy. Furthermore, the honeycomb structure 1 is also superior in terms of thermal shock resistance to the whole, because the wave shape of the wall 4 can absorb the stress generated in each of the through holes 5.
【００２０】しかも、本発明のハニカム構造体１は、壁
４の波形状が貫通孔５方向および貫通孔５と垂直方向の
両方に形成されており、その波高さが０．５ｍｍ以上で
あるから、触媒として用いた場合の浄化効率をより高め
ることができる。Moreover, in the honeycomb structure 1 of the present invention, the corrugations of the wall 4 are formed both in the direction of the through-hole 5 and in the direction perpendicular to the through-hole 5, and the wave height is 0.5 mm or more. In addition, the purification efficiency when used as a catalyst can be further increased.
【００２１】ただし、中央部の壁４の波高さが大きすぎ
る場合には、ハニカム構造体１の真円度が悪くなった
り、外圧強度が弱くなってしまう。この現象を解消する
には、ハニカム構造体１において直線状の壁３をもつ外
周部の割合を大きくするか、外周部の壁３を中央部の壁
４よりも厚くすればよい。なお、通常は、波形状とする
中央部の径を、ハニカム構造体１の直径の８０〜９５％
とすればよい。However, if the wave height of the central wall 4 is too large, the roundness of the honeycomb structure 1 is deteriorated and the external pressure strength is weakened. To eliminate this phenomenon, the ratio of the outer peripheral portion having the linear wall 3 in the honeycomb structure 1 may be increased, or the outer peripheral wall 3 may be thicker than the central wall 4. In addition, usually, the diameter of the center part which is made into a wavy shape is 80 to 95% of the diameter of the honeycomb structure 1.
And it is sufficient.
【００２２】また、他の実施例を図２（Ａ）（Ｂ）に示
すように、中央部にも直線状の壁３を数カ所形成し、必
要に応じて波状の壁４の厚みよりも直線状の壁３の厚み
を大きくすれば、外圧強度を高くできる。さらに、本発
明の他の実施例を図３（Ａ）（Ｂ）（Ｃ）に示すよう
に、このハニカム構造体１は、中央部の壁３が、Ｙ−Ｙ
線方向の壁３ａは貫通孔５方向および貫通孔５と垂直方
向共に波形状となり、Ｘ−Ｘ線方向の壁３ｂは直線状と
なったものである。また、これらの本発明のハニカム構
造体１において、貫通孔５の形状は正方形に限らず、長
方形、三角形、六角形等でも良いことは言うまでもな
い。In another embodiment, as shown in FIGS. 2 (A) and 2 (B), several straight walls 3 are also formed at the center, and if necessary, the straight walls 3 are thicker than the wavy walls 4. If the thickness of the wall 3 is increased, the external pressure strength can be increased. Further, as shown in FIGS. 3A, 3B, and 3C, another embodiment of the present invention, this honeycomb structure 1 has a central wall 3 that is YY.
The wall 3a in the linear direction has a wavy shape in the direction of the through hole 5 and in the direction perpendicular to the through hole 5, and the wall 3b in the XX line direction has a straight shape. Further, in the honeycomb structure 1 of the present invention, the shape of the through-hole 5 is not limited to a square, but may be a rectangle, a triangle, a hexagon, or the like.
【００２３】次に、本発明のハニカム構造体成形用ダイ
スを説明する。Next, the honeycomb structure forming die of the present invention will be described.
【００２４】本発明のハニカム構造体成形用ダイスは、
図４に断面図を、図５に概略平面図を示すように、複数
の坏土供給孔８と、これに連続した壁形成溝９を有して
おり、この坏土供給溝８からセラミック原料を供給し、
壁形成溝９を通過させて押し出すことによってハニカム
構造体１を得ることができる。The honeycomb structure forming die of the present invention comprises:
As shown in a cross-sectional view in FIG. 4 and a schematic plan view in FIG. 5, a plurality of clay supply holes 8 and a wall forming groove 9 continuous therewith are provided. Supply,
The honeycomb structure 1 can be obtained by extruding through the wall forming groove 9.
【００２５】そして、図４（ｂ）に示すような円柱状の
調整リング６を用意しておき、この調整リングを所定の
坏土供給孔８に挿入することによって、その孔径を小さ
くし、坏土供給量に差をつけることができるため、ハニ
カム構造体１の所定部分の壁を波状とできる。また、こ
の調整リング６の高さＴ、内径Ａは自由に変化させるこ
とができるため、坏土の粘度や組成が変わった場合で
も、容易に変更することができる。さらに、調整リング
６を用いることによって、成形用ダイス７の各坏土供給
孔８は、すべて同一径としておけばよく、汎用性の高い
ものとできる。Then, a cylindrical adjusting ring 6 as shown in FIG. 4B is prepared, and the diameter of the adjusting ring is reduced by inserting the adjusting ring into a predetermined clay supply hole 8. Since the difference in the amount of soil supply can be made different, the wall of a predetermined portion of the honeycomb structure 1 can be wavy. Further, since the height T and the inner diameter A of the adjusting ring 6 can be freely changed, even when the viscosity or composition of the clay changes, it can be easily changed. Further, by using the adjustment ring 6, all the clay feeding holes 8 of the forming die 7 may be all the same in diameter, and can be highly versatile.
【００２６】次に、ハニカム構造体１の壁４を波形状と
するメカニズムについて詳細に説明する。Next, the mechanism of making the wall 4 of the honeycomb structure 1 corrugated will be described in detail.
【００２７】図５に示すように、本発明の成形用ダイス
７には、壁形成溝９の交差部に形成した坏土供給孔８ａ
（内径ｘ）と、壁形成溝９の中間部に形成した坏土供給
孔８ｂ（内径ｙ）がある。そして、ｘ≦ｙの場合、図５
に坏土の流れを示すように壁形成用溝９の交差部よりも
中間部への坏土の供給量がはるかに多くなるため、押し
出し後の成形体において、余分に供給された坏土が横方
向へ広がり波状の壁を形成することができる。As shown in FIG. 5, the molding die 7 of the present invention has a clay supply hole 8a formed at the intersection of the wall forming groove 9.
(Inner diameter x) and a clay supply hole 8b (inner diameter y) formed in an intermediate portion of the wall forming groove 9. When x ≦ y, FIG.
Since the supply amount of the kneaded clay to the intermediate portion is much larger than the intersection of the wall forming grooves 9 so as to show the flow of the kneaded clay, the excessively supplied kneaded clay in the extruded compact It is possible to form a wavy wall which spreads in the lateral direction.
【００２８】一方、坏土供給孔８ｂに調整リング６をセ
ットして内径ｙを小さくし、ｘ＞ｙとすれば、波のない
直線状の壁３を形成することができる。On the other hand, if the adjusting ring 6 is set in the kneaded material supply hole 8b to reduce the inner diameter y and x> y, the straight wall 3 without waves can be formed.
【００２９】したがって、成形用ダイス７の外周部は、
壁形成溝９の中間部の坏土供給孔８ｂに調整リング６を
セットしてｘ＞ｙとなるようにする。そして、成形用ダ
イス７の中央部は、調整リング６をセットしないか、ま
たは壁形成溝９の交差部の坏土供給孔８ａに調整リング
６をセットしてｘ≦ｙとなるようにする。このような成
形用ダイス７を用いてセラミック原料を押し出し成形す
れば、外周部が直線状の壁３で、中央部が波状の壁４を
もったハニカム構造体１を得ることができる。Therefore, the outer peripheral portion of the molding die 7 is
The adjusting ring 6 is set in the clay supply hole 8b in the middle part of the wall forming groove 9 so that x> y. Then, the adjusting ring 6 is not set at the center of the forming die 7 or the adjusting ring 6 is set in the clay supply hole 8a at the intersection of the wall forming groove 9 so that x ≦ y. If the ceramic raw material is extruded and formed using such a forming die 7, the honeycomb structure 1 having the straight wall 3 at the outer periphery and the wavy wall 4 at the center can be obtained.
【００３０】このとき、中央部において、壁４の波高さ
が希望よりも低ければ、坏土供給孔８ａにセットした調
整リング６の内径Ａを小さくし、壁形成溝９の交差部へ
の坏土供給量を少なくすればよい。また逆に波高さが希
望よりも高ければ、坏土供給孔８ａにセットした調整リ
ング６の内径Ａを大きくし、壁形成溝９の交差部への坏
土供給量を多くすればよい。さらに組成、硬さ、粘度等
の異なる坏土に対しても、調整リング６の内径Ａまたは
高さＴを変化させることにより、壁形成溝９の交差部お
よび中間部への坏土供給量を自由にコントロールできる
ため希望する形状のハニカム構造体が得られる。At this time, if the wave height of the wall 4 is lower than desired at the center, the inner diameter A of the adjustment ring 6 set in the clay supply hole 8a is reduced, and the What is necessary is just to reduce the soil supply amount. Conversely, if the wave height is higher than desired, the inner diameter A of the adjustment ring 6 set in the clay supply hole 8a may be increased, and the clay supply amount to the intersection of the wall forming grooves 9 may be increased. Further, for the clay having different composition, hardness, viscosity, etc., by changing the inner diameter A or the height T of the adjusting ring 6, the amount of the clay supplied to the intersection and the intermediate portion of the wall forming groove 9 can be reduced. Since it can be freely controlled, a honeycomb structure having a desired shape can be obtained.
【００３１】このように、本発明の製造方法によれば、
ハニカム構造体１の壁４の波高さを自由に調整できる
が、波高さは壁４のピッチよりも小さくしたものがよ
い。これは、壁４の波高さを壁４のピッチよりも高くす
ると、壁４同士が接触する部分が発生し、さらには壁４
同士が完全に付着した場合には貫通孔５が密閉状態とな
り、坏土が成形用ダイス７から押し出されるに連れて、
密閉状態の貫通孔５は減圧状態が促進され、ついには貫
通孔５が存在しなくなり、隣接する貫通孔５へ悪影響を
及ぼすためである。Thus, according to the manufacturing method of the present invention,
Although the wave height of the wall 4 of the honeycomb structure 1 can be freely adjusted, it is preferable that the wave height be smaller than the pitch of the wall 4. This is because if the wave height of the wall 4 is higher than the pitch of the wall 4, a portion where the walls 4 come into contact with each other is generated.
When they are completely adhered to each other, the through-hole 5 is in a sealed state, and as the clay is extruded from the molding die 7,
This is because the depressurized state of the through-hole 5 in the closed state is promoted, and the through-hole 5 eventually disappears, which adversely affects the adjacent through-hole 5.
【００３２】なお、本発明のハニカム構造体１を形成す
る材質は、セラミックスに限らず、活性炭や金属などさ
まざまなものを用いることができる。The material for forming the honeycomb structure 1 of the present invention is not limited to ceramics, and various materials such as activated carbon and metal can be used.
【００３３】実験例 以下に本発明の実験例について説明する。 Experimental Example An experimental example of the present invention will be described below.
【００３４】図４、５に示す成形用ダイス７を用い、壁
形成用溝９のピッチＰ＝４ｍｍ、幅ｔ＝０．３２ｍｍ、
坏土供給孔８ａの内径ｘ＝坏土供給孔８ｂの内径ｙ＝φ
１．４ｍｍ、坏土供給孔８ａ、８ｂの深さ２５ｍｍとし
た。また、押し出し成形するハニカム構造体の大きさは
φ８０×１００ｍｍとした。Using the molding die 7 shown in FIGS. 4 and 5, the pitch P of the wall forming groove 9 is 4 mm, the width t is 0.32 mm,
Inner diameter x of kneaded clay supply hole 8a = inner diameter y of kneaded clay supply hole 8b = φ
The thickness was 1.4 mm and the depth of the clay supply holes 8a and 8b was 25 mm. The size of the honeycomb structure to be extruded was φ80 × 100 mm.
【００３５】まず、最初に成形用ダイス７の壁形成溝９
の交差部の坏土供給孔８ａには調整リング６をセットせ
ず、中間部に形成した坏土供給孔８ｂの全てに調整リン
グ６をセットした。そして、コーディエライト原料１０
０重量部に対して水１５重量部およびバインダ２０重量
部を混練し、粘土状の坏土にしたものを使用し、壁３が
全ての方向に直線状であるハニカム構造体１を得るため
に、この調整リング６の内径Ａと高さＴの寸法を変更し
てテストした。その結果、調整リング６の寸法を内径Ａ
＝φ０．７ｍｍ、高さＴ＝２０ｍｍ、調整リングの外径
Ｂ1 ＝坏土供給孔の内径Ｂ2 −０．２ｍｍとすれば、壁
３が直線状であるハニカム構造体１が得られた。First, first, the wall forming groove 9 of the molding die 7 is formed.
The adjustment ring 6 was not set in the kneaded material supply hole 8a at the intersection of the above, but was set in all of the kneaded material supply holes 8b formed in the intermediate portion. And cordierite raw material 10
15 parts by weight of water and 20 parts by weight of a binder are kneaded with 0 parts by weight, and a clay-like clay is used to obtain a honeycomb structure 1 in which the wall 3 is linear in all directions. The test was performed by changing the dimensions of the inner diameter A and the height T of the adjustment ring 6. As a result, the dimension of the adjustment ring 6 is changed to the inner diameter A.
= Φ 0.7 mm, height T = 20 mm, outer diameter B 1 of the adjustment ring = inner diameter B 2 -0.2 mm of the clay supply hole, the honeycomb structure 1 having the straight wall 3 was obtained. .
【００３６】これを比較例とする。そして、本発明の実
施例１〜１０として、成形用ダイス７の外周部は上記比
較例のままにし、中央部の調整リング６の寸法を変化さ
せて中央部のみ波形状の壁４を有するハニカム構造体１
を得た。各実施例で坏土として用いたセラミック原料は
表１に示す通りであり、得られたハニカム構造体１の壁
４の波高さ、外圧強度を測定したところ、表２に示す通
りであった。This is a comparative example. Then, as Examples 1 to 10 of the present invention, the outer peripheral portion of the molding die 7 was left as in the above comparative example, and the dimension of the adjusting ring 6 at the central portion was changed so that the honeycomb having the corrugated wall 4 only at the central portion Structure 1
I got The ceramic raw materials used as the clay in each example are as shown in Table 1. The wave height and the external pressure strength of the wall 4 of the obtained honeycomb structure 1 were measured, and the results are as shown in Table 2.
【００３７】なお、外圧強度試験は、ハニカム構造体１
の上下端面にハニカム構造体１と同一の断面形状の厚さ
０．５ｍｍのウレタン・シートを介して約２０ｍｍのア
ルミニウム板をあて、側面を厚さ約０．５ｍｍウレタン
チューブで包み密封し、水を満たした圧力容器に入れ、
圧力を徐々に上げて破壊したときの圧力を測定した。The external pressure strength test was conducted on the honeycomb structure 1
An aluminum plate of about 20 mm is applied to the upper and lower end surfaces of the honeycomb structure 1 through a urethane sheet having the same cross-sectional shape as that of the honeycomb structure 1 and having a thickness of 0.5 mm, and the sides are wrapped and sealed with a urethane tube having a thickness of about 0.5 mm. Into a pressure vessel filled with
The pressure at the time of breaking by gradually increasing the pressure was measured.
【００３８】[0038]
【表１】 [Table 1]
【００３９】[0039]
【表２】 [Table 2]
【００４０】表１、２中、実施例１〜３は、壁形成溝９
の中間部への坏土供給孔８ｂにセットした調整リング６
をなくし、中間部への坏土供給量を多くすることで壁４
を波形状としたものであり、坏土として用いる原料の硬
さ、粘度の違いにより壁４の波高さ、外圧強度が異なっ
ている。また、実施例４〜６は、壁形成溝９の交差部へ
の坏土供給孔８ａに調整リング６をセットすることによ
って、より壁４の波高さを高めたものである。さらに、
実施例７〜１０は、坏土として柔らかい原料を用いたた
め、壁形成溝９の中間部への坏土供給孔８ｂに調整リン
グ６をセットしたものである。In Tables 1 and 2, Examples 1 to 3 correspond to the wall forming grooves 9.
Ring 6 set in kneaded clay supply hole 8b to the middle part of
Of the wall 4
The wave height and the external pressure strength of the wall 4 differ depending on the hardness and viscosity of the raw material used as the clay. In Examples 4 to 6, the wave height of the wall 4 was further increased by setting the adjusting ring 6 in the clay supply hole 8a to the intersection of the wall forming groove 9. further,
In Examples 7 to 10, since the soft raw material was used as the kneaded material, the adjusting ring 6 was set in the kneaded material supply hole 8b to the intermediate portion of the wall forming groove 9.
【００４１】実験例１〜１０の結果から、ハニカム構造
体１の成形用ダイス７の坏土供給孔８の所定位置に調整
リング６を装着することにより、ハニカム構造体１の壁
４に、貫通孔５方向および貫通孔５と垂直方向の波形状
を形成することができる。また、その波高さは０〜壁ピ
ッチＰの間で自由に調整でき、その値を０．５ｍｍ以上
とすることが可能である。さらに、組成、硬さ、粘度等
の異なる坏土に対しても、同様に調整可能であることが
確認できた。According to the results of Experimental Examples 1 to 10, the adjusting ring 6 was attached to the predetermined position of the clay supply hole 8 of the forming die 7 of the honeycomb structure 1 so that the adjusting ring 6 was inserted into the wall 4 of the honeycomb structure 1. A wave shape in the direction of the hole 5 and in the direction perpendicular to the through hole 5 can be formed. The wave height can be freely adjusted between 0 and the wall pitch P, and the value can be set to 0.5 mm or more. Furthermore, it was confirmed that the same adjustment can be performed for clays having different compositions, hardness, viscosity, and the like.
【００４２】また、ハニカム構造体１の希望する部分の
み壁４の波形状を形成することも可能であり、前記した
図２、３のような形状のハニカム構造体１も容易に製造
することができる。It is also possible to form the corrugated shape of the wall 4 only at a desired portion of the honeycomb structure 1, and it is possible to easily manufacture the honeycomb structure 1 having the shape shown in FIGS. it can.
【００４３】[0043]
【発明の効果】以上のように、本発明の製造によるハニ
カム構造体は、外周部の壁が直線状であり、中央部の壁
が貫通孔方向に互いに同期した波状であって、この波形
状が貫通孔方向と貫通孔と垂直方向の両方に形成してあ
ることによって、貫通孔を通過するガスとの接触面積を
高めることができるだけなく、ハニカム構造体自体の外
圧強度や耐熱性を高められる。As described above, in the honeycomb structure manufactured by the present invention, the wall at the outer peripheral portion is linear, and the walls at the central portion are corrugated in synchronization with each other in the direction of the through hole. Is formed in both the through-hole direction and the through-hole and the vertical direction, so that not only the contact area with the gas passing through the through-hole can be increased, but also the external pressure strength and heat resistance of the honeycomb structure itself can be increased. .
【００４４】したがって、本発明のハニカム構造体をコ
ンバータとして組み込むと、圧力損失が大きいため浄化
効率が優れ、そのためハニカム構造体の体積及びコンバ
ータの体積を削減できる効果もある。また、活性炭ハニ
カム構造体をオゾン除去用フィルタとして用いる場合
も、除去効果が得られると共に高濃度オゾンの除去にも
有効である。Therefore, when the honeycomb structure of the present invention is incorporated as a converter, the pressure loss is large and the purification efficiency is excellent, so that the volume of the honeycomb structure and the volume of the converter can be reduced. Also, when the activated carbon honeycomb structure is used as an ozone removing filter, the removing effect is obtained and the removal of high-concentration ozone is effective.
【００４５】また、本発明のハニカム構造体成形用ダイ
スは、所定の坏土供給孔に調整リングを備えることによ
って、この成形用ダイスを用いてセラミック原料を押し
出し成形することによって、容易にハニカム構造体の希
望する壁のみに波形状を形成することができ、しかもこ
の波形状は貫通孔方向と貫通孔に垂直な方向の両方に形
成でき、その波高さを０．５ｍｍ以上とできる。また、
上記調整リングの寸法を変化させることによって、壁の
波高さを０〜壁ピッチの範囲で自由に調整でき、かつ組
成、硬さ、粘度等の異なる坏土に対しても同様に調整可
能であり、汎用性を高くできる。In addition, the honeycomb structure forming die of the present invention is provided with an adjusting ring in a predetermined clay supply hole, so that the ceramic material is extruded and formed using the forming die, thereby easily forming the honeycomb structure. A wave shape can be formed only on the desired wall of the body, and this wave shape can be formed both in the direction of the through hole and in the direction perpendicular to the through hole, and the wave height can be 0.5 mm or more. Also,
By changing the size of the adjusting ring, the wave height of the wall can be freely adjusted in the range of 0 to wall pitch, and the composition, hardness, viscosity and the like can be similarly adjusted for different clays. , Versatility can be increased.
【図１】本発明のハニカム構造体を示し、（ａ）は貫通
孔方向の断面図、（ｂ）は貫通孔と垂直方向の断面図で
ある。FIGS. 1A and 1B show a honeycomb structure of the present invention, in which FIG. 1A is a cross-sectional view in the direction of a through-hole, and FIG.
【図２】本発明のハニカム構造体の他の実施例を示し、
（ａ）は貫通孔方向の断面図、（ｂ）は貫通孔と垂直方
向の断面図である。FIG. 2 shows another embodiment of the honeycomb structure of the present invention,
(A) is a sectional view in the direction of the through hole, and (b) is a sectional view in the direction perpendicular to the through hole.
【図３】本発明のハニカム構造体の他の実施例を示し、
（ａ）は貫通孔と垂直方向の断面図、（ｂ）は（ａ）中
のＸ−Ｘ線断面図、（ｃ）は（ａ）中のＹ−Ｙ線断面図
である。FIG. 3 shows another embodiment of the honeycomb structure of the present invention,
(A) is a sectional view in a direction perpendicular to the through hole, (b) is a sectional view taken along line XX in (a), and (c) is a sectional view taken along line YY in (a).
【図４】（ａ）は本発明のハニカム構造体成形用ダイス
の縦断面図、（ｂ）は調整リングのみの斜視図である。FIG. 4A is a longitudinal sectional view of a honeycomb structure forming die of the present invention, and FIG. 4B is a perspective view of only an adjustment ring.
【図５】本発明のハニカム構造体成形用ダイスの概略平
面図である。FIG. 5 is a schematic plan view of a die for forming a honeycomb structure according to the present invention.
【図６】従来のハニカム構造体を示し、（ａ）は貫通孔
方向の断面図、（ｂ）は貫通孔と垂直方向の断面図であ
る。6A and 6B show a conventional honeycomb structure, wherein FIG. 6A is a cross-sectional view in the direction of a through-hole, and FIG. 6B is a cross-sectional view in a direction perpendicular to the through-hole.
【図７】（ａ）（ｂ）は従来のハニカム構造体成形用ダ
イスを示す断面図である。FIGS. 7A and 7B are cross-sectional views showing a conventional die for forming a honeycomb structure.
１・・・ハニカム構造体 ２・・・外壁 ３・・・壁 ４・・・壁 ５・・・貫通孔 ６・・・調整リング ７・・・成形用ダイス ８・・・坏土供給孔 ９・・・壁形成溝 DESCRIPTION OF SYMBOLS 1 ... Honeycomb structure 2 ... Outer wall 3 ... Wall 4 ... Wall 5 ... Through-hole 6 ... Adjustment ring 7 ... Molding die 8 ... Clay supply hole 9 ... Wall-forming grooves
Claims (2)
成用溝を有し、所定の杯土供給孔中に杯土供給量調整リ
ングを備えてなるハニカム構造体成形用ダイス。 1. A plurality of fill soil supply holes and a continuous wall shape
It has a groove for filling and adjusts the amount of
A die for forming a honeycomb structure provided with a ring.
イスにセラミック原料を供給して押し出すことによっ
て、貫通孔に垂直な断面における外周部の壁を貫通孔方
向及び貫通孔と垂直な方向共に直線状とするとともに、
中央部の壁を貫通孔方向及び貫通孔と垂直方向に波状と
し、各波状の壁が貫通孔方向に互いに同期している筒状
のハニカム構造体を形成することを特徴とするハニカム
構造体の製造方法。 2. A die for forming a honeycomb structure according to claim 1.
By supplying and extruding ceramic raw materials to the chair,
The wall of the outer peripheral part in the cross section perpendicular to the through hole toward the through hole.
Direction and the direction perpendicular to the through-hole are both straight,
The center wall is wavy in the direction of the through hole and in the direction perpendicular to the through hole.
And each wavy wall is synchronous with each other in the direction of the through-hole.
Honeycomb characterized by forming a honeycomb structure of the present invention
The method of manufacturing the structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03286546A JP3117252B2 (en) | 1991-10-31 | 1991-10-31 | Die for forming honeycomb structure and method for manufacturing honeycomb structure using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03286546A JP3117252B2 (en) | 1991-10-31 | 1991-10-31 | Die for forming honeycomb structure and method for manufacturing honeycomb structure using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05123580A JPH05123580A (en) | 1993-05-21 |
| JP3117252B2 true JP3117252B2 (en) | 2000-12-11 |
Family
ID=17705817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03286546A Expired - Fee Related JP3117252B2 (en) | 1991-10-31 | 1991-10-31 | Die for forming honeycomb structure and method for manufacturing honeycomb structure using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3117252B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3784718B2 (en) * | 1999-08-30 | 2006-06-14 | 日本碍子株式会社 | Wave wall honeycomb structure and manufacturing method thereof |
| JP4505579B2 (en) * | 2004-09-03 | 2010-07-21 | 独立行政法人産業技術総合研究所 | Exhaust gas purification structure and manufacturing method thereof |
| JP4238858B2 (en) | 2005-09-20 | 2009-03-18 | 株式会社デンソー | Hex honeycomb structure and manufacturing method thereof |
| CN102877920B (en) * | 2012-10-09 | 2014-09-17 | 浙江达峰汽车技术有限公司 | Carrier for vehicle exhaust catalytic cleaner |
-
1991
- 1991-10-31 JP JP03286546A patent/JP3117252B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05123580A (en) | 1993-05-21 |
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| LAPS | Cancellation because of no payment of annual fees |