JP3043573B2 - Carbon material having glassy carbon coating layer and method for producing the same - Google Patents
Carbon material having glassy carbon coating layer and method for producing the sameInfo
- Publication number
- JP3043573B2 JP3043573B2 JP6189036A JP18903694A JP3043573B2 JP 3043573 B2 JP3043573 B2 JP 3043573B2 JP 6189036 A JP6189036 A JP 6189036A JP 18903694 A JP18903694 A JP 18903694A JP 3043573 B2 JP3043573 B2 JP 3043573B2
- Authority
- JP
- Japan
- Prior art keywords
- coating layer
- carbon material
- resin
- glassy carbon
- glassy
- 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
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5001—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with carbon or carbonisable materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Products (AREA)
- Carbon And Carbon Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ガラス状炭素被覆層を
有する炭素材およびその製造方法に関する。The present invention relates to a carbon material having a glassy carbon coating layer and a method for producing the same.
【０００２】[0002]
【従来の技術】炭素材は耐熱性、耐薬品性に優れた素材
であるが、発塵があるため、その用途が限定されてい
た。従って、炭素材の発塵を抑制する処理方法の開発が
要望されており、その一つとして、炭素材の表面を発塵
しにくいガラス状炭素で被覆する方法が提案されてい
る。2. Description of the Related Art Carbon materials are materials having excellent heat resistance and chemical resistance, but their use is limited due to dust generation. Therefore, there is a demand for the development of a treatment method for suppressing the generation of dust of a carbon material. As one of the methods, a method of coating the surface of a carbon material with glassy carbon which is difficult to generate dust has been proposed.
【０００３】従来の、ガラス状炭素を被覆する方法は、
被覆材に高分子化合物（樹脂）またはそれを熱分解して
得られるピッチ状物質を用い、これを溶剤に溶解して得
られた溶液を用い、これを炭素材表面に塗布し、溶剤を
乾燥後、不活性ガス中で焼成する方法である（例えば特
公平２−７９１５号公報等参照）。[0003] Conventional methods of coating glassy carbon include:
Using a polymer compound (resin) or a pitch-like substance obtained by thermally decomposing it as a coating material, using a solution obtained by dissolving this in a solvent, applying it to the carbon material surface, and drying the solvent After that, it is a method of firing in an inert gas (for example, see Japanese Patent Publication No. 2-7915).
【０００４】しかしながら、この方法は、上記のように
被覆材を溶剤に溶解して得られる溶液を使用するため下
記の欠点がある。However, this method has the following drawbacks because it uses a solution obtained by dissolving the coating material in a solvent as described above.
【０００５】 炭素材表面に樹脂被覆層を形成するた
めには数回の塗布が必要である。 炭素材の気孔径や気孔率が大きくなると樹脂被覆層
の形成が困難になる。 樹脂被覆層に残留した溶剤の揮発により、焼成によ
って得られるガラス状炭素被覆層にクラックやヒビ等の
欠陥が発生しやすい。 樹脂の均一被覆が困難である。[0005] In order to form a resin coating layer on the surface of a carbon material, several applications are required. When the pore diameter and the porosity of the carbon material are large, it becomes difficult to form the resin coating layer. Due to volatilization of the solvent remaining in the resin coating layer, defects such as cracks and cracks are likely to occur in the glassy carbon coating layer obtained by firing. It is difficult to uniformly coat the resin.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、これら従来
技術の課題を解消し、高硬度で、発塵を抑制でき、クラ
ックやヒビ等の欠陥を生じることなく、厚みの均一なガ
ラス状炭素被覆層を有する炭素材およびその簡便な製造
方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, has high hardness, can suppress dust generation, and has a uniform thickness of glassy carbon without generating defects such as cracks and cracks. An object of the present invention is to provide a carbon material having a coating layer and a simple production method thereof.
【０００７】[0007]
【課題を解決するための手段】本発明者等は、上記目的
を達成すべく鋭意検討の結果、炭素材にフィルム状に成
型した樹脂を熱圧着することにより、炭素材表面に樹脂
被覆層を容易に形成でき、これを硬化、焼成することに
よりガラス状炭素被覆層を有する炭素材を製造できるこ
とを見い出し、本発明に到達した。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, a resin formed in a film shape on a carbon material has been thermocompressed to form a resin coating layer on the carbon material surface. The present inventors have found that a carbon material having a glassy carbon coating layer can be manufactured by easily forming and curing and firing the same, and arrived at the present invention.
【０００８】すなわち、本発明は、厚さ５〜５０μｍの
フィルム状に成型した炭素化可能な樹脂を炭素材に加熱
圧着し、１００〜２００℃で該樹脂を硬化後、不活性ガ
ス雰囲気下、焼成温度８００℃以上、昇温速度１５℃／
分以下の条件で焼成することを特徴とするガラス状炭素
被覆層を有する炭素材の製造方法にある。That is, according to the present invention, a carbonizable resin molded into a film having a thickness of 5 to 50 μm is heat-pressed to a carbon material, and the resin is cured at 100 to 200 ° C., and then heated under an inert gas atmosphere. Firing temperature 800 ° C or higher, heating rate 15 ° C /
The present invention provides a method for producing a carbon material having a glassy carbon coating layer, characterized in that the carbon material is fired under a condition of not more than minutes.
【０００９】本発明に用いられる樹脂は、フィルム状に
成型でき、加熱圧着により炭素材に接着でき、しかも炭
素化可能な樹脂である。具体的には、ＣＯＰＮＡ樹脂
（多環芳香族縮合化合物）、ポリイミド樹脂、塩化ビニ
ル樹脂、酢酸ビニル樹脂、ポリビニルアルコール樹脂、
フェノール樹脂等が例示される。The resin used in the present invention is a resin that can be formed into a film, can be bonded to a carbon material by heat compression, and can be carbonized. Specifically, COPNA resin (polycyclic aromatic condensed compound), polyimide resin, vinyl chloride resin, vinyl acetate resin, polyvinyl alcohol resin,
Phenol resins and the like are exemplified.
【００１０】この樹脂のフィルム化の方法は特に限定さ
れることはないが、例えば、樹脂を離型フィルムと共に
加熱ロール間を通過させる方法を使用できる。この際、
樹脂の粘度を低下させる目的で溶剤を使用しても良い。
この溶剤は加熱ロール間を通過する際に、製造工程や最
終製品に影響をおよぼさないレベルまで除去できる。The method of forming the resin into a film is not particularly limited, and for example, a method of passing the resin together with a release film between heating rolls can be used. On this occasion,
A solvent may be used for the purpose of reducing the viscosity of the resin.
This solvent can be removed as it passes between the heating rolls to a level that does not affect the manufacturing process or the final product.
【００１１】フィルムの厚みは５〜５０μｍであること
が必要で、フィルムの厚みが５μｍ未満では最終的に得
られるガラス状炭素被覆層の厚みが薄くなり、被覆によ
る発塵抑制の効果が低くなる。フィルムの厚みが５０μ
ｍを超えるとガラス状炭素被覆層にクラックやヒビ等の
欠陥が発生する。The thickness of the film must be 5 to 50 μm. If the thickness of the film is less than 5 μm, the thickness of the finally obtained glassy carbon coating layer becomes thin, and the effect of suppressing dust generation by coating becomes low. . Film thickness is 50μ
If it exceeds m, defects such as cracks and cracks occur in the glassy carbon coating layer.
【００１２】次に、上記のフィルム状に成型された樹脂
（樹脂フィルム）を炭素材に加熱圧着する。この加熱圧
着は、例えば乾燥器あるいは電気アイロン等でフィルム
を炭素材に圧着することによりなされる。Next, the resin (resin film) molded into a film is heated and pressed on a carbon material. The thermocompression bonding is performed by, for example, pressing the film against the carbon material using a dryer or an electric iron.
【００１３】次いで、空気中で１００〜２２０℃の温度
で樹脂を硬化する。硬化温度が１００℃未満または２２
０℃を超えると、得られるガラス状炭素被覆層にヒビ等
の不都合が発生する。Next, the resin is cured at a temperature of 100 to 220 ° C. in the air. Curing temperature below 100 ° C or 22
If the temperature exceeds 0 ° C., inconveniences such as cracks occur in the obtained glassy carbon coating layer.
【００１４】最後に、焼成によって硬化樹脂フィルムを
炭素化し、ガラス状炭素被覆層を形成する。焼成は窒素
ガス等の不活性ガス雰囲気下で行ない、焼成温度は８０
０℃以上、昇温速度１５℃／分以下の条件で行なう。焼
成温度が８００℃未満では炭素化の温度として不充分で
ある。また、昇温速度が１５℃／分を超えると、ガラス
状炭素被覆層にクラックやヒビ等の不都合が発生する。Finally, the cured resin film is carbonized by baking to form a glassy carbon coating layer. The firing is performed in an atmosphere of an inert gas such as nitrogen gas.
The reaction is performed at a temperature of 0 ° C. or more and a temperature rising rate of 15 ° C./min or less. If the firing temperature is lower than 800 ° C., the temperature for carbonization is insufficient. On the other hand, if the heating rate exceeds 15 ° C./min, inconveniences such as cracks and cracks occur in the glassy carbon coating layer.
【００１５】このようにして、本発明のガラス状炭素被
覆層を有する炭素材が得られる。この炭素材は、ガラス
状炭素被覆層が高硬度で、発塵を抑制できると同時に耐
摩耗性に優れ、また炭素材と剥離し難い等の利点を有す
る。Thus, the carbon material having the glassy carbon coating layer of the present invention is obtained. This carbon material has such advantages that the glassy carbon coating layer has high hardness, can suppress dust generation, has excellent abrasion resistance, and is hardly peeled off from the carbon material.
【００１６】[0016]
【実施例】以下、実施例に基づき本発明を具体的に説明
する。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments.
【００１７】実施例１ ＣＯＰＮＡ樹脂（商品名：ＳＫレジン ＳＫＲ−Ｎ、住
金化工（株）製）を７５℃に加熱したロール間に通し、
厚さ３０μｍのフィルムを得た。これを１７０℃に加熱
した電気アイロンを用いて板状に加工した嵩比重１．６
の炭素材（商品名：ＥＲ−３８、日本カーボン（株）
製）に圧着し、空気中、２００℃で硬化した後、窒素ガ
ス雰囲気下、１０００℃まで５℃／分の昇温速度で昇温
して焼成し、ガラス状炭素被覆層を有する炭素材を得
た。 Example 1 A COPNA resin (trade name: SK Resin SKR-N, manufactured by Sumikin Kako Co., Ltd.) was passed between rolls heated to 75 ° C.
A film having a thickness of 30 μm was obtained. This was processed into a plate using an electric iron heated to 170 ° C. and had a bulk specific gravity of 1.6.
Carbon material (trade name: ER-38, Nippon Carbon Co., Ltd.)
And cured at 200 ° C. in the air, and then heated to 1000 ° C. in a nitrogen gas atmosphere at a rate of 5 ° C./min and fired to obtain a carbon material having a glassy carbon coating layer. Obtained.
【００１８】ガラス状炭素被覆層の特性は表１に示すよ
うに、外観は良好であり、クラックやヒビ等の欠陥はほ
とんど観察されず、発塵も認められなかった。As shown in Table 1, the properties of the glassy carbon coating layer were good in appearance, almost no defects such as cracks and cracks were observed, and no dust generation was observed.
【００１９】実施例２ 市販の塩化ビニル樹脂フィルム（厚み２０μｍ）を嵩比
重１．８の炭素材（商品名：ＥＧＦ−２６４、日本カー
ボン（株）製）に１５０℃に加熱した電気アイロンを用
いて圧着した。これを空気中、１６０℃で硬化した後、
窒素ガス雰囲気下、１０００℃まで２℃／分の昇温速度
で昇温して焼成し、ガラス状炭素被覆層を有する炭素材
を得た。 Example 2 A commercially available vinyl chloride resin film (thickness: 20 μm) was applied to a carbon material having a bulk density of 1.8 (trade name: EGF-264, manufactured by Nippon Carbon Co., Ltd.) using an electric iron heated to 150 ° C. And crimped. After curing this at 160 ° C in air,
In a nitrogen gas atmosphere, the temperature was raised to 1000 ° C. at a rate of 2 ° C./min, followed by firing to obtain a carbon material having a glassy carbon coating layer.
【００２０】ガラス状炭素被覆層の特性は表１に示すよ
うに、外観は良好で、クラックやヒビ等の欠陥は観察さ
れず、発塵も認められなかった。As shown in Table 1, the properties of the glassy carbon coating layer were good in appearance, no defects such as cracks and cracks were observed, and no dust generation was observed.
【００２１】実施例３ フェノール樹脂（商品名：ベルパールＳ−８９９、鐘紡
（株）製）に同量のメタノールを加えてワニス化し、こ
れを８０℃に設定した加熱ロール間に通し、３０μｍの
フィルムを得た。これを１２０℃に加熱した電気アイロ
ンで実施例２で使用したのと同様の炭素材に圧着し、空
気中、２１０℃で硬化した後、窒素ガス雰囲気下、１０
００℃まで１０℃／分で昇温し、さらに２０００℃で焼
成し、ガラス状炭素被覆層を有する炭素材を得た。 Example 3 The same amount of methanol was added to a phenolic resin (trade name: Bellpearl S-899, manufactured by Kanebo Co., Ltd.) to form a varnish, which was passed through a heating roll set at 80 ° C., and a 30 μm film was formed. I got This was pressed against the same carbon material as used in Example 2 with an electric iron heated to 120 ° C., cured in air at 210 ° C., and then dried under nitrogen gas atmosphere.
The temperature was raised to 00 ° C. at a rate of 10 ° C./min, followed by firing at 2000 ° C. to obtain a carbon material having a glassy carbon coating layer.
【００２２】ガラス状炭素被覆層の特性は表１に示すよ
うに、外観は良好で、クラックやヒビ等の欠陥は観察さ
れず、発塵も認められなかた。As shown in Table 1, the characteristics of the glassy carbon coating layer were good in appearance, no defects such as cracks and cracks were observed, and no dust generation was observed.
【００２３】比較例１ 実施例１におけるフィルムの厚みを７０μｍとする以外
はすべて実施例１と同様にしてガラス状炭素被覆層を有
する炭素材を得た。 Comparative Example 1 A carbon material having a glassy carbon coating layer was obtained in the same manner as in Example 1 except that the thickness of the film in Example 1 was changed to 70 μm.
【００２４】しかしながら、このガラス状炭素被覆層に
は、表１に示すように多数のヒビが観察された。However, many cracks were observed in the glassy carbon coating layer as shown in Table 1.
【００２５】比較例２ 実施例１における硬化温度を２５０℃とする以外はすべ
て実施例１と同様にしてガラス状被覆層を有する炭素材
を得た。 Comparative Example 2 A carbon material having a glassy coating layer was obtained in the same manner as in Example 1 except that the curing temperature in Example 1 was changed to 250 ° C.
【００２６】しかしながら、このガラス状炭素被覆層に
は、表１に示すように多数のクラックが観察された。However, many cracks were observed in the glassy carbon coating layer as shown in Table 1.
【００２７】比較例３ 実施例１における焼成の昇温速度を３０℃／分とする以
外はすべて実施例１と同様にしてガラス状炭素被覆層を
有する炭素材を得た。 Comparative Example 3 A carbon material having a glassy carbon coating layer was obtained in the same manner as in Example 1 except that the heating rate of firing in Example 1 was changed to 30 ° C./min.
【００２８】しかしながら、このガラス状炭素被覆層に
は、表１に示すように多数のヒビが認められた。However, many cracks were observed in the glassy carbon coating layer as shown in Table 1.
【００２９】比較例４ 実施例１で用いたのと同様のＣＯＰＮＡ樹脂２０ｇを１
００ｇのクロロホルムに溶解し、均一な溶液を得た。こ
れを実施例１で用いたのと同様の炭素材表面に塗布、乾
燥する操作を５回繰り返し、１０〜８０μｍ（平均３０
μｍ）の樹脂被覆層を形成した。これを実施例１と同様
にして焼成し、ガラス状炭素被覆層を有する炭素材を得
た。 Comparative Example 4 20 g of the same COPNA resin as used in Example 1 was added to 1
It was dissolved in 00 g of chloroform to obtain a uniform solution. The same operation of applying and drying the same on the surface of the carbon material as used in Example 1 was repeated 5 times,
μm). This was fired in the same manner as in Example 1 to obtain a carbon material having a glassy carbon coating layer.
【００３０】しかしながらこの、ガラス状炭素被覆層に
は、表１に示すように全面に多数のクラックやヒビが認
められた。However, as shown in Table 1, a large number of cracks and cracks were observed on the entire surface of the glassy carbon coating layer.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【発明の効果】以上説明したように、本発明の製造方法
では、次のような効果を奏する。 フィルムの厚みを制御することにより、樹脂被覆層
の厚みを、そして最終的に得られるガラス状炭素被覆層
の厚みを制御できる。 １回の処理により炭素材表面に樹脂被覆層を形成で
きる。 気孔径や気孔率の大きな炭素材の表面に樹脂被覆層
を形成できる。 均一な膜厚の樹脂被覆層が得られる。As described above, the manufacturing method of the present invention has the following effects. By controlling the thickness of the film, the thickness of the resin coating layer and the thickness of the finally obtained glassy carbon coating layer can be controlled. A resin coating layer can be formed on the carbon material surface by one treatment. A resin coating layer can be formed on the surface of a carbon material having a large pore diameter or porosity. A resin coating layer having a uniform thickness can be obtained.
【００３３】また、本発明で得られるガラス状炭素被覆
層を有する炭素材では、次のような効果を奏する。 ガラス状炭素被覆層の硬度が高く、発塵を抑制でき
ると同時に耐摩耗性に優れる。 ガラス状炭素被覆層と炭素材の密着性が良いため、
両者の剥離等がない。 ガラス状炭素被覆層の熱膨張係数は３．２×１０-6
／℃、炭素材が３〜６×１０-6／℃であるため、急昇温
や急冷却で両者が剥離することがない。 ガラス状炭素被覆層の気体や液体の不浸透性が高
い。The carbon material having the glassy carbon coating layer obtained in the present invention has the following effects. The glassy carbon coating layer has high hardness, can suppress dust generation, and has excellent wear resistance. Good adhesion between glassy carbon coating layer and carbon material,
There is no separation of both. The thermal expansion coefficient of the glassy carbon coating layer is 3.2 × 10 -6.
/ ° C., and the carbon material is 3 to 6 × 10 −6 / ° C., so that the two are not separated by rapid temperature rise or rapid cooling. Gas and liquid impermeability of the glassy carbon coating layer is high.
【００３４】このような利点を有するガラス状炭素被覆
層を有する炭素材は、従来の発塵する炭素材が展開でき
なかった用途、例えば、半導体分野、食品分野等への展
開が可能になる。The carbon material having the glassy carbon coating layer having such advantages can be applied to applications where conventional dusting carbon materials could not be developed, for example, to the field of semiconductors and foods.
フロントページの続き (56)参考文献 特開 昭59−21512（ＪＰ，Ａ) 特開 平４−83779（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C04B 41/80 - 41/91 C04B 35/52 - 35/54 Continuation of the front page (56) References JP-A-59-21512 (JP, A) JP-A-4-83779 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C04B 41 / 80-41/91 C04B 35/52-35/54
Claims (2)
た炭素化可能な樹脂を炭素材に加熱圧着し、１００〜２
００℃で該樹脂を硬化後、不活性ガス雰囲気下、焼成温
度８００℃以上、昇温速度１５℃／分以下の条件で焼成
することを特徴とするガラス状炭素被覆層を有する炭素
材の製造方法。1. A carbonizable resin molded into a film having a thickness of 5 to 50 μm is pressure-bonded to a carbon material by heating and pressing.
A method for producing a carbon material having a glassy carbon coating layer, wherein the resin is cured at 00 ° C. and then fired in an inert gas atmosphere at a firing temperature of 800 ° C. or more and a heating rate of 15 ° C./min or less. Method.
覆層を有する炭素材。2. A carbon material having a glassy carbon coating layer obtained according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6189036A JP3043573B2 (en) | 1994-07-20 | 1994-07-20 | Carbon material having glassy carbon coating layer and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6189036A JP3043573B2 (en) | 1994-07-20 | 1994-07-20 | Carbon material having glassy carbon coating layer and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0826858A JPH0826858A (en) | 1996-01-30 |
| JP3043573B2 true JP3043573B2 (en) | 2000-05-22 |
Family
ID=16234229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6189036A Expired - Fee Related JP3043573B2 (en) | 1994-07-20 | 1994-07-20 | Carbon material having glassy carbon coating layer and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3043573B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101784608B1 (en) * | 2016-05-09 | 2017-10-12 | 이경우 | Denture With Gum Having Pinholes |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005206411A (en) * | 2004-01-22 | 2005-08-04 | Nippon Kouatsu Electric Co | Carbon film formation method to ceramics |
-
1994
- 1994-07-20 JP JP6189036A patent/JP3043573B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101784608B1 (en) * | 2016-05-09 | 2017-10-12 | 이경우 | Denture With Gum Having Pinholes |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0826858A (en) | 1996-01-30 |
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