JP2896959B2 - Vulcanized rubber-unvulcanized rubber bonded structure - Google Patents
Vulcanized rubber-unvulcanized rubber bonded structureInfo
- Publication number
- JP2896959B2 JP2896959B2 JP6063738A JP6373894A JP2896959B2 JP 2896959 B2 JP2896959 B2 JP 2896959B2 JP 6063738 A JP6063738 A JP 6063738A JP 6373894 A JP6373894 A JP 6373894A JP 2896959 B2 JP2896959 B2 JP 2896959B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- sulfur
- weight
- vulcanized
- unvulcanized
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Gasket Seals (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐久性を向上させた加
硫ゴム−未加硫ゴム接合構造体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vulcanized rubber-unvulcanized rubber bonded structure having improved durability.
【０００２】[0002]
【従来の技術】従来、ゴム製大型ガスケットのような大
型ゴム製品は、加硫ゴム部品と加硫ゴム部品とを未加硫
ゴム部品を介して接合することにより構成される。そし
て、このような加硫ゴム−未加硫ゴム接合構造体におい
ては、未加硫ゴム部品に含有される加硫剤であるイオウ
が加硫ゴム部品に移行して未加硫ゴム部品の物性を低下
させるために、通常はイオウが加硫ゴム部品に比して未
加硫ゴム部品に多く配合されている。2. Description of the Related Art Conventionally, a large rubber product such as a large rubber gasket is formed by joining a vulcanized rubber component and a vulcanized rubber component via an unvulcanized rubber component. In such a vulcanized rubber-unvulcanized rubber bonded structure, sulfur as a vulcanizing agent contained in the unvulcanized rubber part migrates to the vulcanized rubber part, and the physical properties of the unvulcanized rubber part In order to reduce the sulfur content, sulfur is usually blended more in unvulcanized rubber parts than in vulcanized rubber parts.
【０００３】しかしながら、このような加硫ゴム−未加
硫ゴム接合構造体においては、特に必要破壊荷重が150t
on/m以上の大型のものにあっては、未加硫ゴム部品に含
有されるイオウが加硫ゴム部品と未加硫ゴム部品との境
界部付近の加硫ゴム部分に集積してこの付近の物性を顕
著に低下させるので、耐久性 (耐荷重性) が損なわれる
という問題があった。However, in such a vulcanized rubber-unvulcanized rubber bonded structure, a required breaking load is particularly 150 t.
For large items with on / m or more, the sulfur contained in the unvulcanized rubber part accumulates in the vulcanized rubber part near the boundary between the vulcanized rubber part and the unvulcanized rubber part. However, there is a problem that the durability (load resistance) is impaired because the physical properties of the steel are remarkably reduced.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、必要破壊荷
重が150ton/m以上の耐久性に優れた加硫ゴム−未加硫ゴ
ム接合構造体を提供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a vulcanized rubber-unvulcanized rubber bonded structure having a required breaking load of 150 ton / m or more and excellent durability.
【０００５】[0005]
【課題を解決するための手段】本発明の加硫ゴム−未加
硫ゴム接合構造体は、加硫ゴム部品間を未加硫ゴム部品
を介して接合してなり、必要破壊荷重が150ton/m以上で
あって、前記加硫ゴム部品のイオウ含有量ｘ (重量％)
と前記未加硫ゴム部品のイオウ含有量ｙ (重量％) とが
下記式、の関係を有することを特徴とする。The vulcanized rubber-unvulcanized rubber bonded structure of the present invention is formed by bonding vulcanized rubber parts via an unvulcanized rubber part and has a required breaking load of 150 ton /. m or more, and the sulfur content x (% by weight) of the vulcanized rubber part
And the sulfur content y (% by weight) of the unvulcanized rubber component has a relationship represented by the following formula.
【０００６】 ｙ≦−1.７ｘ＋2.８ ・・・・・・・・ 0.２≦ｙ≦1.65 ・・・・・・・・ このように本発明では、加硫ゴム部品と未加硫ゴム部品
とのイオウ含有量の関係を定めたために、耐久性を向上
させることが可能となる。以下、本発明の構成につき詳
しく説明する。Y ≦ −1.7x + 2.8 (0.2 ≦ y ≦ 1.65) As described above, in the present invention, the vulcanized rubber component and the unvulcanized rubber Since the relationship between the sulfur content and the component is determined, the durability can be improved. Hereinafter, the configuration of the present invention will be described in detail.
【０００７】(１) 加硫ゴム−未加硫ゴム接合構造体に
おける必要破壊荷重と加硫ゴム部品−未加硫ゴム部品境
界部付近破壊エネルギー (以下、イオウ集積部破壊エネ
ルギーという) との関係（必要破壊荷重が150ton/m以上
の大型ゴム製品において）：必要破壊荷重 (ton/m)とイ
オウ集積部破壊エネルギー (kgf/cm2 ) とは、通常、図
１に示す関係にある。必要破壊荷重を150ton/m以上とし
て耐久性を損なわないためにはイオウ集積部破壊エネル
ギー (引張強さと伸びの積分値) は100kgf/cm2 以上を
要することが分かる。そこで、本発明においてもイオウ
集積部破壊エネルギーを100kgf/cm2 以上とする。(1) Relationship between the required breaking load and the breaking energy near the boundary between the vulcanized rubber part and the unvulcanized rubber part (hereinafter referred to as the sulfur-accumulated part breaking energy) in the vulcanized rubber-unvulcanized rubber bonded structure. (For a large rubber product having a required breaking load of 150 ton / m or more): The required breaking load (ton / m) and the breaking energy of the sulfur accumulation portion (kgf / cm 2 ) usually have the relationship shown in FIG. It can be seen that in order to maintain the required breaking load of 150 ton / m or more and the durability without impairing the durability, the sulfur-accumulated portion breaking energy (integrated value of tensile strength and elongation) needs to be 100 kgf / cm 2 or more. Therefore, also in the present invention, the energy of destruction of the sulfur accumulation portion is set to 100 kgf / cm 2 or more.
【０００８】（２）イオウ集積部破壊エネルギー１００
ｋｇｆ／ｃｍ２以上を発現するためには、イオウ集積部
全イオウ量が２．１０重量％以下であること： 図２はイオウ集積部分の全イオウ分析量と破壊エネルギ
ーとの関係図であり、この図２から前記（１）項のイオ
ウ集積部破壊エネルギー１００ｋｇｆ／ｃｍ２以上を発
現する全イオウ量が２．１０重量％以下であることが分
かる。(2) Destruction energy of sulfur accumulation part 100
In order to express kgf / cm 2 or more, the total sulfur content of the sulfur accumulation portion should be 2.10% by weight or less. FIG. 2 is a relationship diagram between the total sulfur analysis amount of the sulfur accumulation portion and the breaking energy, It can be seen from FIG. 2 that the total amount of sulfur exhibiting the sulfur-accumulated portion breaking energy of 100 kgf / cm 2 or more in the item (1) is 2.10% by weight or less.
【０００９】(３) イオウ集積部全イオウ量を2.10重量
％以下とするためには、加硫ゴム部品の配合イオウ量が
1.65重量％以下であること：この関係を図３に示す。こ
の図３は、後記の表１中のＨS 40の本体ゴム（マスター
バッチに適宜配合イオウ量を変えたゴム）を148 ℃×30
分の適正加硫で加硫し、得られた加硫シートを硫黄分析
器により全イオウ量を測定した結果と、配合イオウ量の
関係をプロットしたもので全イオウ分析量を2.10重量％
以下にするためには配合するイオウ量を1.65重量％以下
にする必要があることが分かる。(3) In order to reduce the total sulfur content of the sulfur accumulating portion to 2.10% by weight or less, the sulfur content of the vulcanized rubber component must be reduced.
1.65% by weight or less: This relationship is shown in FIG. FIG 3, a main body rubber 148 ° C. × 30 (rubber changed appropriately blended sulfur content in the master batch) of H S 40 in Table 1 below
Vulcanized sheet with the appropriate vulcanization for one minute, and the resulting vulcanized sheet was measured for the total sulfur content with a sulfur analyzer and the relationship between the combined sulfur content was plotted.
It can be seen that the amount of sulfur to be blended must be 1.65% by weight or less in order to reduce the content to below.
【００１０】(４) 加硫ゴム部品 (以下、本体ゴムとい
う) の配合イオウ量および未加硫ゴム部品 (以下、接合
ゴムという) の配合イオウ量の変動とイオウ集積部破壊
エネルギーとの関係：図４から、イオウ集積部破壊エネ
ルギー100kgf/cm2 以上を発現するためには、本体ゴム
配合イオウ量によって接合ゴム配合イオウ量が変わるこ
とが分かる。すなわち、下記の関係がある。(4) Relationship between fluctuations in the amount of sulfur contained in vulcanized rubber parts (hereinafter, referred to as main rubber) and the amount of sulfur contained in unvulcanized rubber parts (hereinafter, referred to as bonded rubber) and the sulfur-accumulated portion breaking energy: From FIG. 4, it can be seen that in order to achieve a sulfur accumulation portion breaking energy of 100 kgf / cm 2 or more, the amount of sulfur contained in the bonding rubber varies depending on the amount of sulfur contained in the main rubber. That is, there is the following relationship.
【００１１】 本体ゴム 接合ゴム 0.８重量％イオウ配合 1.46重量％以下 1.０重量％イオウ配合 1.11重量％以下 1.２重量％イオウ配合 0.73重量％以下 この図４は、表１の本体ゴムを常法によりプレス加硫
し、これに表２の未加硫接合ゴムを貼り合わせ、この
後、再び常法によりプレス加硫したサンプルの各組み合
わせ毎のイオウ集積部破壊エネルギーと接合ゴムイオウ
量の関係をプロットしたものである。 Body rubber bonded rubber 0.8% by weight of sulfur 1.46% by weight or less 1.0% by weight of sulfur 1.11% by weight or less 1.2% by weight of sulfur 0.73% by weight or less Was press-vulcanized by a conventional method, and the unvulcanized bonding rubber shown in Table 2 was bonded thereto, and then the sulfur-accumulated portion breaking energy and the bonding rubber sulfur amount of each combination of the samples press-vulcanized again by the conventional method were again measured. It is a plot of the relationship.
【００１２】(５) 100kgf/cm2 以上のイオウ集積部破
壊エネルギーを発現する本体ゴム配合イオウ量と接合ゴ
ム配合イオウ量の関係：本体ゴム配合イオウ量 (イオウ
含有量) をｘ (重量％) 、接合ゴム配合イオウ量 (イオ
ウ含有量) をｙ (重量％) とすると、図５に示す領域、
すなわち下記式、の関係を満たす領域である。(5) Relationship between the amount of sulfur contained in the main rubber and the amount of sulfur contained in the bonding rubber which exhibit a sulfur accumulation portion breaking energy of 100 kgf / cm 2 or more: The amount of sulfur contained in the main rubber (sulfur content) is x (% by weight). Assuming that the sulfur content (sulfur content) of the compounded rubber is y (% by weight), the area shown in FIG.
That is, the region satisfies the relationship of the following expression.
【００１３】 ｙ≦−1.７ｘ＋2.８ ・・・・・・・・ 0.２≦ｙ≦1.65 ・・・・・・・・ ここで、0.２≦ｙとしたのは、0.２未満ではイオウ量が
少なすぎてイオウ集積部における物性低下 (特に剥離力
低下) が生じるからである。この図５は、前記（４）項
の結果から得られたイオウ集積部破壊エネルギー100kgf
/cm2 以上を発現するための本体ゴム配合イオウ量と接
合ゴム配合イオウ量との関係をプロットして作成したも
のである。Y ≦ −1.7x + 2.8 (0.2 ≦ y ≦ 1.65) (0.2 ≦ y) is defined as 0.2 ≦ y. If the amount is less than the above, the amount of sulfur is too small, and the physical properties (particularly, the peeling strength) in the sulfur accumulation portion are reduced. FIG. 5 is a graph showing the 100 kgf of the destructive energy of the sulfur accumulation part obtained from the result of the above item (4).
It is created by plotting the relationship between the amount of sulfur contained in the main rubber and the amount of sulfur contained in the bonding rubber for expressing / cm 2 or more.
【００１４】具体的には、ｘは、ｘ＝0.7 〜1.5 重量％
であるのが好ましい。 (６) 接合ゴムの本体ゴムへの影響：下記の表１の配合
内容 (重量部) の本体ゴムの加硫サンプル100mm ×150m
m ×５mmに、下記の表２のコンパウンド (重量部) から
なる接合ゴムの未加硫サンプル100mm ×150mm ×６mmを
貼り合わせて接合構造体ａ〜ｆを作製し、常法によって
この接合構造体を加硫した後に、イオウ集積部破壊エネ
ルギー、イオウ集積部全イオウ量、本体ゴム−接合ゴム
間剥離力を評価した。この結果を表３に示す。ここで、
HsはJIS Hs硬度を表わす。また、表３における「オリジ
ナル」は、本体ゴム自身の物性を意味する。Specifically, x is x = 0.7 to 1.5% by weight.
It is preferred that (6) Influence of bonding rubber on main rubber: vulcanized sample of main rubber 100mm x 150m with blending contents (parts by weight) in Table 1 below
An unvulcanized 100 mm x 150 mm x 6 mm sample of a bonding rubber consisting of the compound (parts by weight) shown in Table 2 below was bonded to m x 5 mm to form bonding structures a to f. After vulcanization, the breaking energy of the sulfur accumulation portion, the total sulfur amount of the sulfur accumulation portion, and the peeling force between the main rubber and the bonded rubber were evaluated. Table 3 shows the results. here,
Hs represents JIS Hs hardness. “Original” in Table 3 means the physical properties of the main rubber itself.
【００１５】 注） *1 本体ゴムマスターバッチ 天然ゴム 100 重量部 SRF カーボンブラック 10 重量部 ＺｎＯ 5 重量部 アロマ油 5 重量部 計 120 重量部[0015] Note) * 1 Body rubber master batch 100 parts by weight natural rubber SRF carbon black 10 parts by weight ZnO 5 parts by weight Aroma oil 5 parts by weight Total 120 parts by weight
【００１６】 注） *2 接合ゴムマスターバッチ 天然ゴム 100 重量部 SRF カーボンブラック 10 重量部 ＺｎＯ 5 重量部 アロマ油 5 重量部 計 120 重量部[0016] Note) * 2 Bonded rubber master batch 100 parts by weight natural rubber SRF carbon black 10 parts by weight ZnO 5 parts by weight Aroma oil 5 parts by weight Total 120 parts by weight
【００１７】イオウ集積部破壊エネルギー評価方法：上
記方法で加硫したサンプルでイオウ集積部を0.5tmmで切
り出し、３号ダンベルを打ち抜き、JIS K 6251に準じて
破壊エネルギーを測定する。イオウ集積部全イオウ量評価方法 ：前記（６）で作製し
た積層構造体のイオウ集積部を0.5tmmで切り出したサン
プルを掘場製作所製EMIA-510により全イオウ量を測定す
る。イオウ集積部剥離力評価方法 ：前記（６）で作製した積
層構造体を25mm幅でたんざく状に切り出し、島津製オー
トグラフで、本体ゴム側と接合ゴム側で以下の条件で引
張剥離力を測定する。 ・180 °Ｔ型剥離 ・剥離スピード 50mm/ 分 ・測定温度 20℃ ・測定項目 剥離力 （kgf/25mm) Sulfur accumulation portion fracture energy evaluation method : A sulfur accumulation portion is cut out at 0.5 tmm from a sample vulcanized by the above method, a No. 3 dumbbell is punched out, and the fracture energy is measured according to JIS K 6251. Evaluation method of total sulfur amount in sulfur accumulation portion : A sample obtained by cutting out the sulfur accumulation portion of the laminated structure prepared in the above (6) at 0.5 tmm is measured for total sulfur amount by EMIA-510 manufactured by Dig Mfg. Seisakusho. Sulfur accumulation part peeling force evaluation method : The laminated structure produced in the above (6) was cut out in a 25 mm width into a strip shape, and the tensile peeling force was measured on the body rubber side and the bonding rubber side under the following conditions using an autograph made by Shimadzu. Measure.・ 180 ° T type peeling ・ Peel speed 50mm / min ・ Measurement temperature 20 ℃ ・ Measurement item Peel force (kgf / 25mm)
【００１８】 表３から、接合ゴム配合イオウ量が0.20重量％未満で
は、剥離力が低下することが判る。[0018] From Table 3, it can be seen that when the amount of the sulfur compounded in the bonding rubber is less than 0.20% by weight, the peeling force decreases.
【００１９】[0019]
【実施例】表４に示すイオウ配合量で前記（６）におけ
ると同様にして接合構造体を作製し（比較例、実施例１
〜２）、イオウ集積部破壊エネルギーおよび製品破壊荷
重を測定した。この結果を表４に示す。 注） * 破壊せず打ち切り 表４から、実施例１〜２は比較例に比して製品破壊荷重
が高く、耐久性に優れていることが分かる。EXAMPLE A joint structure was produced in the same manner as in the above (6) with the sulfur content shown in Table 4 (Comparative Example, Example 1).
2), the breaking energy of the sulfur accumulation portion and the breaking load of the product were measured. Table 4 shows the results. Note) * Cut off without breaking Table 4 shows that Examples 1 and 2 have a higher product breaking load and are superior in durability compared to Comparative Examples.
【００２０】[0020]
【発明の効果】以上説明したように本発明によれば、加
硫ゴム部品と未加硫ゴム部品とのイオウ含有量の関係を
定めたために、必要破壊荷重が150ton/m以上の加硫ゴム
−未加硫ゴム接合構造体について、耐久性を向上させる
ことが可能となる。As described above, according to the present invention, since the relationship between the sulfur content of the vulcanized rubber component and the unvulcanized rubber component is determined, the required destructive load of the vulcanized rubber component is 150 ton / m or more. -The durability of the unvulcanized rubber bonded structure can be improved.
【図１】加硫ゴム−未加硫ゴム接合構造体の必要破壊荷
重とイオウ集積部破壊エネルギーとの関係図である。FIG. 1 is a diagram showing the relationship between the required breaking load of a vulcanized rubber-unvulcanized rubber bonded structure and the breaking energy of a sulfur accumulation portion.
【図２】加硫ゴム−未加硫ゴム接合構造体におけるイオ
ウ集積部全イオウ量とイオウ集積部破壊エネルギーとの
関係図である。FIG. 2 is a graph showing the relationship between the total sulfur content of a sulfur accumulating portion and the sulfur accumulating portion breaking energy in a vulcanized rubber-unvulcanized rubber bonded structure.
【図３】本体ゴム配合における全イオウ量と配合イオウ
量との関係図である。FIG. 3 is a diagram showing the relationship between the total sulfur content and the compounded sulfur content in the main rubber compounding.
【図４】加硫ゴム−未加硫ゴム接合構造体における本体
ゴム配合イオウ量および接合ゴム配合イオウ量の変動と
イオウ集積部破壊エネルギーとの関係図である。FIG. 4 is a graph showing the relationship between the variation of the sulfur content of the main rubber and the sulfur content of the bonded rubber in the vulcanized rubber-unvulcanized rubber bonded structure, and the breaking energy of the sulfur accumulation portion.
【図５】加硫ゴム−未加硫ゴム接合構造体における接合
ゴム配合イオウ量と本体ゴム配合イオウ量との関係図で
ある。FIG. 5 is a graph showing the relationship between the amount of sulfur contained in the bonded rubber and the amount of sulfur contained in the main rubber in the vulcanized rubber-unvulcanized rubber bonded structure.
フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) B32B 1/00 - 35/00 C08J 5/12 Continuation of front page (58) Field surveyed (Int. Cl. 6 , DB name) B32B 1/00-35/00 C08J 5/12
Claims (2)
て接合してなり、必要破壊荷重が150ton/m以上であっ
て、前記加硫ゴム部品のイオウ含有量ｘ (重量％) と前
記未加硫ゴム部品のイオウ含有量ｙ (重量％) とが下記
式、の関係を有する加硫ゴム−未加硫ゴム接合構造
体。 ｙ≦−1.７ｘ＋2.８ ・・・・・・・・ 0.２≦ｙ≦1.65 ・・・・・・・・ 1. A vulcanized rubber part is joined via an unvulcanized rubber part, a required breaking load is 150 ton / m or more, and a sulfur content x (% by weight) of the vulcanized rubber part. And a sulfur content y (% by weight) of the unvulcanized rubber part having the following formula: vulcanized rubber-unvulcanized rubber bonded structure. y ≦ −1.7x + 2.8 ······· 0.2 ≦ y ≦ 1.65 ········
1.5 重量％である請求項１に記載の加硫ゴム−未加硫ゴ
ム接合構造体。2. A vulcanized rubber component having a sulfur content x of 0.7 to 0.7.
The vulcanized rubber-unvulcanized rubber bonded structure according to claim 1, which is 1.5% by weight.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6063738A JP2896959B2 (en) | 1994-03-31 | 1994-03-31 | Vulcanized rubber-unvulcanized rubber bonded structure |
| DE1995112237 DE19512237A1 (en) | 1994-03-31 | 1995-03-31 | Composite rubber structure useful for esp. high breaking load |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6063738A JP2896959B2 (en) | 1994-03-31 | 1994-03-31 | Vulcanized rubber-unvulcanized rubber bonded structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07266500A JPH07266500A (en) | 1995-10-17 |
| JP2896959B2 true JP2896959B2 (en) | 1999-05-31 |
Family
ID=13238061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6063738A Expired - Fee Related JP2896959B2 (en) | 1994-03-31 | 1994-03-31 | Vulcanized rubber-unvulcanized rubber bonded structure |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2896959B2 (en) |
| DE (1) | DE19512237A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19735396B4 (en) * | 1997-08-14 | 2004-04-29 | Josef Auberger | Process for the production of vulcanized and unvulcanized soft rubber sheets, with an unvulcanized adhesive layer, which are glued to the carrier material with a self-vulcanizing adhesive and permanently bonded to it |
-
1994
- 1994-03-31 JP JP6063738A patent/JP2896959B2/en not_active Expired - Fee Related
-
1995
- 1995-03-31 DE DE1995112237 patent/DE19512237A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| DE19512237A1 (en) | 1995-10-26 |
| JPH07266500A (en) | 1995-10-17 |
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