JPH0645382A - Resin injection mold - Google Patents
Resin injection moldInfo
- Publication number
- JPH0645382A JPH0645382A JP19735792A JP19735792A JPH0645382A JP H0645382 A JPH0645382 A JP H0645382A JP 19735792 A JP19735792 A JP 19735792A JP 19735792 A JP19735792 A JP 19735792A JP H0645382 A JPH0645382 A JP H0645382A
- Authority
- JP
- Japan
- Prior art keywords
- mold
- resin
- molding
- cavity
- runner
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/26—Moulds
- B29C45/37—Mould cavity walls, i.e. the inner surface forming the mould cavity, e.g. linings
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、半導体装置のパッケー
ジを熱硬化性合成樹脂を用いて形成する際に使用する樹
脂成形金型に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin molding die used when a semiconductor device package is formed using a thermosetting synthetic resin.
【0002】[0002]
【従来の技術】周知の通り、半導体装置には、リードフ
レームに搭載された半導体チップをエポキシ系の熱硬化
性合成樹脂で樹脂封止するようにしてパッケージを形成
したものがある。2. Description of the Related Art As is well known, there are semiconductor devices in which a semiconductor chip mounted on a lead frame is sealed with an epoxy thermosetting synthetic resin to form a package.
【0003】従来、このような熱硬化性合成樹脂を成形
して行う樹脂封止は、トランスファモールドによって行
われる。また使用する成形金型は、合成樹脂が流動する
ランナ及び所定のパッケージ形状に成形するキャビティ
の表面が平滑に仕上げられ、さらに平滑に仕上げられた
表面に硬質クロムめっきが2〜5μmの厚さで施されて
いる。Conventionally, resin molding performed by molding such a thermosetting synthetic resin is performed by transfer molding. The molding die used is such that the surface of the runner through which the synthetic resin flows and the cavity to be molded into a predetermined package shape are smoothed, and the surface of the smoothed surface is coated with hard chrome with a thickness of 2 to 5 μm. It has been subjected.
【0004】しかしながら上記の従来技術においては、
合成樹脂と接触する金型表面に硬質クロムめっきを施
し、めっき膜によって表面の硬度を高めると共に、防錆
や成形品の離型性をよくしているが、このような樹脂成
形金型には、継続してより多数の成形加工ができるよう
表面硬度を高くして金型寿命を延ばし、また離型性もよ
り向上させて成形品の離型時に生じる変形や割れをなく
し成形歩留を向上させ、さらに金型への樹脂かすの付着
を少なくし金型の清掃の頻度を少なくすることが求めら
れている。However, in the above prior art,
Hard chrome plating is applied to the surface of the mold that comes in contact with the synthetic resin, and the plating film enhances the hardness of the surface, as well as improves rust prevention and mold release of molded products. , The surface hardness is increased to extend the mold life so that more molding processes can be continuously performed, and the mold releasability is also improved to eliminate the deformation and cracks that occur during mold release and improve the molding yield. In addition, it is required to reduce the frequency of cleaning the mold by reducing the adhesion of resin residue to the mold.
【0005】一方、硬質クロムめっきは膜厚を比較的薄
くできるものの、膜厚のばらつきの範囲が場合によって
は5μm以上と大きくなってしまったり、また、例えば
縦150mm、横200mmの範囲に膜厚5μmの硬質
クロムめっきを行おうとしたところ、めっき膜の膜厚が
7〜10μmとなり、膜厚のばらつき範囲は3μm程度
であったものの膜厚の平均値を所定の5μmとすること
ができず、所定の膜厚を得ることが困難である。On the other hand, although the hard chrome plating can make the film thickness relatively thin, the range of film thickness variation may become as large as 5 μm or more in some cases, and the film thickness may be, for example, 150 mm in length and 200 mm in width. When an attempt was made to perform hard chromium plating of 5 μm, the thickness of the plated film was 7 to 10 μm, and although the variation range of the film thickness was about 3 μm, the average value of the film thickness could not be set to a predetermined value of 5 μm. It is difficult to obtain a predetermined film thickness.
【0006】このため集積度が高く、狭ピッチで多数の
アウターリードを持つ半導体装置等の小型のパッケージ
で、外観上見苦しくならないよう精度を要する成形を行
う成形金型では、めっきを行った後にその金型の主体部
分や組み付けられる組み合わせ部品の寸法を測定する。
そして、成形金型として組み上げた時に各部が所定寸法
となり隙間ができないように、組み合わせ部品の選別や
選択組み立てなどの調整・組み立て等の余分な作業を行
わなければならず、金型寸法の精度を向上させることも
求められている。For this reason, in a compact package such as a semiconductor device having a high degree of integration and having a large number of outer leads at a narrow pitch, which requires high precision so as not to be unsightly in appearance, a molding die is used after plating. Measure the dimensions of the main part of the mold and the assembled parts to be assembled.
Then, extra work such as adjustment and assembly such as selection of combined parts and selective assembly must be performed so that each part has a predetermined dimension when assembled as a molding die and no gaps are formed, and the accuracy of the die dimension is improved. There is also a demand for improvement.
【0007】[0007]
【発明が解決しようとする課題】上記のように従来は金
型表面に硬質クロムめっきを行い表面硬度を高め、離型
性をよくするようにしているが、さらに金型寿命が長
く、離型性がより向上することによって成形の歩留が向
上すること、及び金型寸法に高い精度を要する場合でも
余分な作業を必要としないことが求められている。この
ような状況に鑑みて本発明はなされたもので、その目的
とするところは金型寿命が長く、成形歩留がより向上す
ると共に高い金型寸法精度を要する場合でも余分な作業
を必要としない樹脂成形金型を提供することにある。As described above, conventionally, the surface of the mold is hard chrome plated to increase the surface hardness and improve the mold releasability. However, the mold life is longer and the mold release is better. It is required that the molding yield is improved by further improving the moldability and that extra work is not required even when the mold dimension requires high accuracy. The present invention has been made in view of such a situation, and the purpose thereof is to have an extra work even if the die life is long, the molding yield is further improved, and high die dimensional accuracy is required. Not to provide a resin molding die.
【0008】[0008]
【課題を解決するための手段】本発明の樹脂成形金型
は、ランナを介してキャビティ内に熱硬化性合成樹脂を
導入して成形を行う樹脂成形金型において、熱硬化性合
成樹脂と接触するキャビティ及びランナの表面にチタン
化合物膜が被着されていることを特徴とするものであ
り、チタン化合物膜が窒化チタンであることを特徴とす
るものである。The resin molding die of the present invention is a resin molding die for molding by introducing a thermosetting synthetic resin into a cavity through a runner, and is in contact with the thermosetting synthetic resin. The titanium compound film is deposited on the surfaces of the cavity and the runner, and the titanium compound film is titanium nitride.
【0009】[0009]
【作用】上記のように構成された樹脂成形金型は、熱硬
化性合成樹脂と接触するキャビティ及びランナの表面に
窒化チタン等のチタン化合物膜を被着しており、これに
よって金型の表面硬度が高いものとなり成形時の樹脂流
動による磨耗等に対する強度が増して金型寿命が延び、
また離型性もより向上したものとなって成形品の離型時
に生じる変形や割れが低減し成形歩留が向上すると共
に、金型に樹脂かすが付着し難くなり金型の清掃の頻度
が少なくなる。さらに被着したチタン化合物膜の膜厚の
ばらつきが少なく、金型寸法の精度が向上して余分な作
業を必要としなくなる。In the resin molding die constructed as described above, a titanium compound film such as titanium nitride is deposited on the surfaces of the cavity and the runner which come into contact with the thermosetting synthetic resin, whereby the surface of the die is formed. The hardness becomes high and the strength against abrasion etc. due to resin flow during molding increases and the mold life extends,
In addition, the mold releasability is also improved, and the deformation and cracks that occur during mold release of the molded product are reduced, the molding yield is improved, and the resin residue is less likely to adhere to the mold, so the frequency of cleaning the mold is reduced. Become. Further, the variation in the film thickness of the deposited titanium compound film is small, the precision of the mold dimension is improved, and no extra work is required.
【0010】[0010]
【実施例】以下、本発明の一実施例を図1乃至図5を参
照して説明する。図1は部分断面図であり、図2は下金
型の要部平面図であり、図3は図2の一部を拡大して示
す斜視図であり、図4は成形状態を説明するための斜視
図であり、図5は成形品の斜視図である。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below with reference to FIGS. 1 is a partial cross-sectional view, FIG. 2 is a plan view of a main part of a lower mold, FIG. 3 is a perspective view showing a part of FIG. 2 in an enlarged manner, and FIG. 4 is for explaining a molding state. FIG. 5 is a perspective view of the molded product.
【0011】図1乃至図3において、樹脂成形金型1
は、上金型2と下金型3によって構成された上下方向に
分割される割り型で、両金型2,3にはそれぞれ成形品
の所定形状に合わせた略方形の複数のキャビティ4が削
設されている。また両金型2,3には、樹脂成形金型1
外からキャビティ4の成形を行う熱硬化性合成樹脂を導
入するランナ5が削設されている。1 to 3, the resin molding die 1 is shown.
Is a split mold which is composed of an upper mold 2 and a lower mold 3 and which is divided in the vertical direction. The molds 2 and 3 each have a plurality of substantially square cavities 4 matched to a predetermined shape of a molded product. It has been cut down. Also, for both molds 2 and 3, a resin molding mold 1
A runner 5 for introducing a thermosetting synthetic resin for molding the cavity 4 from the outside is cut.
【0012】ランナ5は、外から樹脂成形金型1内に熱
硬化性合成樹脂を導入する主ランナ部6と、この主ラン
ナ部6から各キャビティ4に熱硬化性合成樹脂を送り込
む分岐ランナ部7で構成され、分岐ランナ部7の片端が
キャビティ4の角部に接続しキャビティ4内に開口して
いる。なお4aは空気抜きであり、7aはゲートであ
る。そしてランナ5の形状や各キャビティ4への接続位
置等はキャビティ4内の熱硬化性合成樹脂の流れや硬化
状況等によって適宜決定される。The runner 5 includes a main runner portion 6 for introducing a thermosetting synthetic resin into the resin molding die 1 from the outside, and a branch runner portion for feeding the thermosetting synthetic resin from the main runner portion 6 to each cavity 4. 7, the branch runner portion 7 has one end connected to a corner portion of the cavity 4 and opened into the cavity 4. In addition, 4a is an air vent and 7a is a gate. The shape of the runner 5 and the connection position to each cavity 4 are appropriately determined depending on the flow of the thermosetting synthetic resin in the cavity 4, the curing state, and the like.
【0013】また、樹脂成形の際に熱硬化性合成樹脂が
直接接触するキャビティ4とランナ5の表面には、膜厚
が3μmの窒化チタン(TiN)膜8が均一に被着され
ている。なお2点鎖線で示した9は、成形加工時に樹脂
成形金型1の上金型2と下金型3の間に装着されるリー
ドフレームを示す。A titanium nitride (TiN) film 8 having a thickness of 3 μm is uniformly deposited on the surfaces of the cavity 4 and the runner 5 which are directly contacted with the thermosetting synthetic resin during resin molding. Reference numeral 9 indicated by a chain double-dashed line indicates a lead frame mounted between the upper mold 2 and the lower mold 3 of the resin molding mold 1 during molding.
【0014】そして、樹脂成形金型1の製作は、上金型
2と下金型3の母材となる高速度鋼等の金属ブロックの
それぞれに所定形状のキャビティ4やランナ5を構成す
る凹部を削設し、またキャビティ4やランナ5に取着さ
れる組み合わせ部品等を製作した後、それぞれ成形品の
表面にその形状が反映されるキャビティ4の表面や、ま
たランナ5の表面が平滑に仕上げられる。Then, the resin molding die 1 is manufactured by forming a cavity 4 and a runner 5 of a predetermined shape in each of metal blocks such as high-speed steel which is a base material of the upper die 2 and the lower die 3. After manufacturing the combined parts and the like to be attached to the cavity 4 and the runner 5, the surface of the cavity 4 whose surface is reflected on the surface of the molded product and the surface of the runner 5 are made smooth. Can be finished.
【0015】平滑に仕上げられたキャビティ4とランナ
5の表面に、それぞれ窒化チタン膜8が公知のイオンプ
レーティング法により膜厚が3μm〜6μm程度の範囲
で所定の値となるよう処理条件を設定して被着される。
因みに被着された窒化チタン膜8の膜厚が3μmの場
合、その膜厚のばらつきは0.3μm程度で膜厚の10
%以下の非常に小さいものになっている。On the surfaces of the cavity 4 and the runner 5 which have been finished to be smooth, the treatment conditions are set so that the titanium nitride film 8 has a predetermined value in the range of 3 μm to 6 μm by a known ion plating method. And then put on.
Incidentally, when the film thickness of the deposited titanium nitride film 8 is 3 μm, the variation in the film thickness is about 0.3 μm and the film thickness is 10 μm.
It is very small, less than or equal to%.
【0016】このようにして窒化チタン膜8が被着され
た後、上金型2や下金型3が各組み合わせ部品を適宜組
み合わせることによって樹脂成形金型1は完成される。
なお樹脂成形金型1には、図示しないガイドピンやノッ
クピン、あるいは金型温度を所定の値に維持するヒータ
等が取り付けられる。After the titanium nitride film 8 is thus deposited, the upper mold 2 and the lower mold 3 appropriately combine the respective combination parts to complete the resin molding mold 1.
The resin molding die 1 is provided with a guide pin, a knock pin (not shown), a heater or the like for maintaining the die temperature at a predetermined value.
【0017】そして、このように構成された樹脂成形金
型1を用いての成形は次ぎのようにして行われる。すな
わち、樹脂成形金型1は図示しない成形機に取り付けら
れ、トランスファーモールドが行われる。先ず初めに図
4に示すように樹脂成形金型1の上金型2と下金型3の
間に合成樹脂性のパッケージが形成されるリードフレー
ム9が配置される。Then, the molding using the resin molding die 1 thus constructed is carried out as follows. That is, the resin molding die 1 is attached to a molding machine (not shown) and transfer molding is performed. First, as shown in FIG. 4, a lead frame 9 in which a synthetic resin package is formed is arranged between the upper mold 2 and the lower mold 3 of the resin molding mold 1.
【0018】リードフレーム9には、そのインナリード
10の先端にボンディングによって取着された半導体チ
ップ11が所定ピッチで取り付けられており、リードフ
レーム9を樹脂成形金型1に装着した際、半導体チップ
11がキャビティ4の略中央部に位置するようになって
いる。A semiconductor chip 11 attached by bonding to the tip of the inner lead 10 is attached to the lead frame 9 at a predetermined pitch. When the lead frame 9 is mounted on the resin molding die 1, the semiconductor chip is attached. 11 is located substantially in the center of the cavity 4.
【0019】次いで、上金型2と下金型3を閉じ樹脂成
形金型1にリードフレーム9を装着した後、ランナ5の
主ランナ部6を通じて樹脂成形金型1内にエポキシ系の
熱硬化性合成樹脂が導入される。導入された熱硬化性合
成樹脂は、主ランナ部6から各分岐ランナ部7を流動し
ゲート7aを介して各キャビティ4内に導入され、熱硬
化性合成樹脂がキャビティ4内に充填される。この時キ
ャビティ4内の空気は空気抜き4aを通じて抜かれる。Next, the upper mold 2 and the lower mold 3 are closed, the lead frame 9 is mounted on the resin molding mold 1, and then the epoxy-based thermosetting is performed in the resin molding mold 1 through the main runner portion 6 of the runner 5. Synthetic resin is introduced. The introduced thermosetting synthetic resin flows from the main runner portion 6 through each branch runner portion 7 and is introduced into each cavity 4 through the gate 7a, and the thermosetting synthetic resin is filled in the cavity 4. At this time, the air in the cavity 4 is evacuated through the air bleeder 4a.
【0020】そして、キャビティ4及びランナ5内の熱
硬化性合成樹脂を所定時間加熱加圧して硬化成形させ
る。その後、上金型2と下金型3を開きリードフレーム
9を樹脂成形金型1から取り外す。取り外したリードフ
レーム9からランナ5内で硬化した樹脂を除去し、図5
に示すようなキャビティ4の形状に習って形成されたパ
ッケージ12によって半導体チップ11が樹脂封止され
たリードフレーム9を得る。Then, the thermosetting synthetic resin in the cavity 4 and the runner 5 is heated and pressed for a predetermined time to be cured and molded. After that, the upper mold 2 and the lower mold 3 are opened, and the lead frame 9 is removed from the resin molding mold 1. The resin cured in the runner 5 is removed from the removed lead frame 9,
The lead frame 9 in which the semiconductor chip 11 is resin-sealed by the package 12 formed following the shape of the cavity 4 as shown in FIG.
【0021】このように構成された本実施例では、樹脂
成形金型1の熱硬化性合成樹脂と直接接触するキャビテ
ィ4とランナ5の表面に、比較的薄くて膜厚のばらつき
が非常に少ない窒化チタン膜8が被着されているので、
寸法精度を要する成形においても金型の再調整・再組み
立て等の余分な作業を行う必要がない。そして成形され
たパッケージ12の外観不良の発生を防止することがで
きる。In this embodiment having such a structure, the surfaces of the cavity 4 and the runner 5 that are in direct contact with the thermosetting synthetic resin of the resin molding die 1 are relatively thin and have very little variation in film thickness. Since the titanium nitride film 8 is deposited,
Even in molding that requires dimensional accuracy, it is not necessary to perform extra work such as readjustment and reassembly of the mold. Further, it is possible to prevent the appearance defect of the molded package 12 from occurring.
【0022】また、キャビティ4やランナ5の表面は、
硬度がヴィッカース硬さ(Hv)で2000Kg/mm
2 以上の硬い窒化チタン膜8を有し、従来の硬質クロム
めっき膜のヴィッカース硬さ(Hv)で800Kg/m
m2 〜1100Kg/mm2より硬いため、1つの金型
での成形できる成形品の個数を増加させることができ、
金型寿命を延ばすことができる。The surfaces of the cavity 4 and the runner 5 are
The hardness is 2000 Vg / mm in Vickers hardness (Hv)
Has 2 or more hard titanium nitride films 8 and 800 kg / m in Vickers hardness (Hv) of the conventional hard chromium plating film
Since it is harder than m 2 to 1100 kg / mm 2, it is possible to increase the number of molded products that can be molded with one mold,
Mold life can be extended.
【0023】さらに、キャビティ4で成形されたパッケ
ージ12や、ランナ5で硬化した不要部材の離型性もよ
り向上したものとなり、パッケージ12に変形や割れを
生じず、成形歩留が向上する。そして樹脂成形金型1へ
の樹脂かすの付着がを少なくなり、金型の清掃の頻度を
少なくなって成形作業の能率が向上する。Further, the releasability of the package 12 molded in the cavity 4 and the unnecessary member hardened by the runner 5 is further improved, the package 12 is not deformed or cracked, and the molding yield is improved. The adhesion of resin residue to the resin molding die 1 is reduced, the frequency of cleaning the die is reduced, and the efficiency of the molding operation is improved.
【0024】尚、上記の実施例においては樹脂成形金型
1の熱硬化性合成樹脂と接触するキャビティ4とランナ
5の表面に窒化チタン膜8を被着したが、炭化チタン
(TiC)膜等他のチタン化合物膜を被着してもよく、
その他要旨を逸脱しない範囲内で適宜変更して本発明は
実施し得るものである。In the above embodiment, the titanium nitride film 8 is deposited on the surfaces of the cavity 4 and the runner 5 which are in contact with the thermosetting synthetic resin of the resin molding die 1, but a titanium carbide (TiC) film or the like is used. Other titanium compound films may be deposited,
The present invention can be implemented with appropriate changes within the scope not departing from the gist.
【0025】[0025]
【発明の効果】以上の説明から明らかなように、本発明
は、熱硬化性合成樹脂と接触するキャビティ及びランナ
の表面にチタン化合物膜を被着した構成とすることによ
り、金型寿命が長く、成形歩留がより向上すると共に高
い金型寸法精度を要する場合でも余分な作業を必要とし
ない等の効果を奏する。As is apparent from the above description, according to the present invention, the life of the mold is extended by forming the titanium compound film on the surfaces of the cavity and runner which are in contact with the thermosetting synthetic resin. Further, the molding yield is further improved, and even when high mold dimensional accuracy is required, extra work is not required.
【図1】本発明の一実施例を示す部分断面図である。FIG. 1 is a partial sectional view showing an embodiment of the present invention.
【図2】同上における下金型を示す要部平面図である。FIG. 2 is a plan view of an essential part showing a lower mold in the above.
【図3】図2の一部を拡大して示す斜視図である。3 is an enlarged perspective view showing a part of FIG. 2. FIG.
【図4】本発明の一実施例による成形状態を説明するた
めに示す斜視図である。FIG. 4 is a perspective view shown for explaining a molding state according to an embodiment of the present invention.
【図5】同上における成形品の斜視図である。FIG. 5 is a perspective view of a molded product of the above.
1…樹脂成形金型 2…上金型 3…下金型 4…キャビティ 5…ランナ 8…窒化チタン膜 DESCRIPTION OF SYMBOLS 1 ... Resin molding die 2 ... Upper die 3 ... Lower die 4 ... Cavity 5 ... Runner 8 ... Titanium nitride film
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 B29L 31:34 4F ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display location B29L 31:34 4F
Claims (2)
合成樹脂を導入して成形を行う樹脂成形金型において、
前記熱硬化性合成樹脂と接触する前記キャビティ及びラ
ンナの表面にチタン化合物膜が被着されていることを特
徴とする樹脂成形金型。1. A resin molding die for molding by introducing a thermosetting synthetic resin into a cavity through a runner,
A resin molding die, wherein a titanium compound film is deposited on the surfaces of the cavity and the runner which are in contact with the thermosetting synthetic resin.
を特徴とする請求項1記載の樹脂成形金型。2. The resin molding die according to claim 1, wherein the titanium compound film is titanium nitride.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19735792A JPH0645382A (en) | 1992-07-24 | 1992-07-24 | Resin injection mold |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19735792A JPH0645382A (en) | 1992-07-24 | 1992-07-24 | Resin injection mold |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0645382A true JPH0645382A (en) | 1994-02-18 |
Family
ID=16373143
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP19735792A Pending JPH0645382A (en) | 1992-07-24 | 1992-07-24 | Resin injection mold |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0645382A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10176258A (en) * | 1996-12-17 | 1998-06-30 | Tokai Rubber Ind Ltd | Steel product having rubber and/or resin peelable surface and its production |
-
1992
- 1992-07-24 JP JP19735792A patent/JPH0645382A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10176258A (en) * | 1996-12-17 | 1998-06-30 | Tokai Rubber Ind Ltd | Steel product having rubber and/or resin peelable surface and its production |
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