JP2593176B2 - Modified graphite material - Google Patents
Modified graphite materialInfo
- Publication number
- JP2593176B2 JP2593176B2 JP63079732A JP7973288A JP2593176B2 JP 2593176 B2 JP2593176 B2 JP 2593176B2 JP 63079732 A JP63079732 A JP 63079732A JP 7973288 A JP7973288 A JP 7973288A JP 2593176 B2 JP2593176 B2 JP 2593176B2
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- Prior art keywords
- expanded graphite
- graphite
- graphite material
- modifier
- weight
- 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.)
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は新規な改質黒鉛材、より詳しくは、内燃機関
のシリンダーブロックとシリンダーヘッド間のヘッドガ
スケット、或は排気マニホールドと排気管との管継手に
用いられるシール用ガスケットとして用いるに適当な改
質黒鉛材に関するものである。The present invention relates to a novel modified graphite material, and more particularly, to a head gasket between a cylinder block and a cylinder head of an internal combustion engine, or between an exhaust manifold and an exhaust pipe. The present invention relates to a modified graphite material suitable for use as a sealing gasket used in a pipe joint.
従来、このようなヘッドガスケット或いはシール用ガ
スケットとしては、積層構造を有する黒鉛粒子を酸処理
等の方法で処理してから、加熱膨張してえられる膨張黒
鉛を圧延してつくられるシート状の黒鉛材が用いられて
いた。しかしこのようにしてつくられたシート状黒鉛材
はガスケット材として必要な耐不凍液性、耐油性、耐酸
化性が充分でなく、又引張り強度等の物性においても不
足しており、そのため各種の改質法が提案されている。Conventionally, as such a head gasket or a sealing gasket, a sheet-like graphite produced by treating graphite particles having a laminated structure by a method such as acid treatment and then rolling expanded graphite obtained by heating and expanding. Wood was used. However, the sheet-like graphite made in this way does not have sufficient antifreeze, oil, and oxidation resistance required for gasket materials, and also lacks in physical properties such as tensile strength. A quality method has been proposed.
たとえば、膨張黒鉛にバインダーとしてフェノール樹
脂、アクリル樹脂、ポリイミド樹脂等の合成樹脂を混合
し、圧縮成形する方法が知られており、これによりえら
れた成形物においては耐不凍液性、耐油性等は改善され
ているが、ガスケット材として特に要求される圧縮率、
復元率等の特性が損なわれるのみならず、流体シール特
性に関して必要とされる柔軟性も低下する傾向がみられ
る。For example, a method of mixing a synthetic resin such as a phenolic resin, an acrylic resin, or a polyimide resin as a binder with expanded graphite and compressing and molding the same is known. In a molded product obtained by this method, antifreeze resistance, oil resistance, and the like are known. Compressibility, which has been improved, but is particularly required as a gasket material,
Not only properties such as the restoration rate are impaired, but also the required flexibility for the fluid sealing properties tends to decrease.
一方、膨張黒鉛材を有機ケイ素化合物で処理してその
耐酸化物や引張り強度の改善をはかる方法も知られてい
るが、この場合まず含浸し、長時間かけて乾燥してから
非酸化性雰囲気中で500〜2000℃もの高温に加熱処理す
ることが必要とされており、作業性に難があるとともに
製造コスト、設備コスト面においても不利を免がれなか
った。On the other hand, a method of treating an expanded graphite material with an organosilicon compound to improve its oxide resistance and tensile strength is also known, but in this case, it is impregnated first, dried for a long time, and then dried in a non-oxidizing atmosphere. Therefore, heat treatment at a high temperature of 500 to 2000 ° C. is required, and workability is difficult, and disadvantages are unavoidable in terms of manufacturing cost and equipment cost.
かくて本発明はこのような従来の黒鉛材の問題点を解
決して圧縮率、復元率のような特性を損なうことなく、
又製造コスト、設備コストの上昇を来すことなく製造す
ることができて、耐不凍液性、耐油性、耐酸化性を大き
く改善することができる改質黒鉛材を提供することを目
的とするものであり、本発明者らによれば、かかる目的
は膨張黒鉛を有機チタネート系改質剤により処理するこ
とによって達成することが見出された。Thus, the present invention solves such problems of the conventional graphite material, without impairing properties such as compression ratio and restoration ratio,
It is another object of the present invention to provide a modified graphite material which can be manufactured without increasing manufacturing costs and equipment costs, and which can greatly improve antifreeze liquid resistance, oil resistance, and oxidation resistance. According to the present inventors, it has been found that such an object is achieved by treating expanded graphite with an organic titanate-based modifier.
よって本発明は、黒鉛材を有機チタネート系改質剤に
より処理してなる改質黒鉛材を提供するものである。Accordingly, the present invention provides a modified graphite material obtained by treating a graphite material with an organic titanate-based modifier.
以下本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明は上記のように黒鉛材を有機チタネート系改質
剤により処理してえられた改質黒鉛材に係るものである
が、出発物質として用いられる黒鉛材としては膨張黒
鉛、そのマット状成形物及びシート状成形物をあげるこ
とができる。ここに膨張黒鉛とは積層構造を有する黒鉛
粒子を濃硫酸と濃硝酸との混酸、濃硫酸と過マンガン酸
カリウムとの混合物、或は濃硫酸と過酸化水素との混合
物など強酸化性の処理液で処理してフレーク状の層間化
合物を生成させ、水洗してから急速加熱し、黒鉛結晶の
Ｃ軸方向に膨張させてえられたものであり、その比容積
は約200〜300cc/gである。The present invention relates to a modified graphite material obtained by treating a graphite material with an organic titanate-based modifier as described above, but the graphite material used as a starting material is expanded graphite, and a mat-like molding thereof. And sheet-like molded articles. Here, expanded graphite is a strongly oxidizing treatment such as a mixed acid of concentrated sulfuric acid and concentrated nitric acid, a mixture of concentrated sulfuric acid and potassium permanganate, or a mixture of concentrated sulfuric acid and hydrogen peroxide, which is a graphite particle having a laminated structure. It is obtained by treating with a liquid to form a flake-like intercalation compound, washing with water, rapidly heating and expanding in the C-axis direction of the graphite crystal, and its specific volume is about 200 to 300 cc / g. is there.
膨張黒鉛のマット状成形物は、上記のようにしてえら
れた膨張黒鉛をロール又はプレスにより圧縮してかさ密
度0.05〜0.5g/cm2、厚さ２〜20mmに成形されたウエハー
ス状のものであり、又シート状成形物は上記膨張黒鉛を
ロール又はプレスにより更につよく圧縮圧延してかさ密
度0.5〜1.5g/cm2、厚さ0.05〜2.0mmに成形されたもので
ある。The expanded graphite mat-like molded product is a wafer-like molded product obtained by compressing the expanded graphite obtained as described above with a roll or a press to a bulk density of 0.05 to 0.5 g / cm 2 and a thickness of 2 to 20 mm. Further, the sheet-like molded product is obtained by further compressively rolling the above-mentioned expanded graphite by a roll or a press to form a bulk density of 0.5 to 1.5 g / cm 2 and a thickness of 0.05 to 2.0 mm.
ガスケット材として用いるときは上記の如きシート状
成形物を用いるのが好ましいが、初め膨張黒鉛又はその
マット状成形物を用いて改質剤で処理し、その後圧縮し
てシート状成形物とし、それをガスケット材として用い
ることもできる。その方が後の改質剤の含浸処理が容易
である。When used as a gasket material, it is preferable to use a sheet-like molded product as described above, but first, it is treated with a modifier using expanded graphite or its mat-like molded product, and then compressed to form a sheet-like molded product. Can be used as a gasket material. This makes it easier to impregnate the modifier later.
本発明で用いる改質剤は基本構造にTi−Ｏ−Ｃ結合を
有する有機チタネート化合物であり、リンを含有する含
リン有機チタネート化合物も有利に用いることができ
る。本発明で用いるに好適な有機チタネート化合物又は
含リン有機チタネート化合物としては、チタニウム・ア
シレート、チタニウム・アルコラート、チタニウム・ヒ
ドロキシ・カルボキシレート、チタニウム・フォスフェ
ート、リン酸塩配位のチタニウム・アシレートなどをあ
げることができる。これらの改質剤はそのまま無溶剤で
用いることができるが、水、トルエン、イソプロパノー
ル、メチル・エチル・ケトン等の溶剤で稀釈して用いる
のが好ましい。The modifier used in the present invention is an organic titanate compound having a Ti—O—C bond in a basic structure, and a phosphorus-containing organic titanate compound containing phosphorus can also be advantageously used. Suitable organic titanate compounds or phosphorus-containing organic titanate compounds used in the present invention include titanium acylate, titanium alcoholate, titanium hydroxy carboxylate, titanium phosphate, phosphate coordinated titanium acylate and the like. I can give it. These modifiers can be used without solvent, but are preferably used after dilution with a solvent such as water, toluene, isopropanol or methyl ethyl ketone.
このような有機チタネート化合物の一般式を第１表に
示す。Table 1 shows the general formula of such an organic titanate compound.
一般式中でａ＋ｂ＝４ R1,R2,R3＝ＨあるいはC1〜C20のアルキル基 R4,R5＝C3〜C22のアルキル基を示す。 In the general formula, a + b = 4 R 1 , R 2 , R 3 = H or C 1 -C 20 alkyl group R 4 and R 5 = alkyl groups of C 3 to C 22 .
R1〜R5は同じであっても異なっていてもよい。R 1 to R 5 may be the same or different.
このような改質剤で黒鉛材たとえば膨張黒鉛、マット
又は膨張黒鉛成形シートを処理する。その処理は改質剤
を溶剤で稀釈してなる溶液を黒鉛材に塗布したり、噴霧
したりして行なうことができるが通常はかかる溶液の含
浸処理によって行なわれる。その含浸方法は黒鉛材を溶
液中に含浸する自然含浸法の外に真空注入法、加圧注入
法等によることができる。A graphite material such as expanded graphite, matte or expanded graphite molded sheet is treated with such a modifier. The treatment can be carried out by applying a solution obtained by diluting the modifier with a solvent to the graphite material, or by spraying the solution, but is usually carried out by impregnation of such a solution. The impregnation method may be a natural impregnation method in which a graphite material is impregnated in a solution, or a vacuum injection method, a pressure injection method, or the like.
真空注入法とは、減圧に耐え得る容器中で膨張黒鉛、
マット、あるいは膨張黒鉛成形シートを溶剤に稀釈した
改質剤溶液中に浸漬し、系内を減圧にした後、大気圧に
もどす操作である。温度は常温でよく、系内圧力は200m
mHg程度の減圧にする。With vacuum injection method, expanded graphite in a container that can withstand reduced pressure,
This is an operation in which a mat or an expanded graphite molded sheet is immersed in a modifier solution diluted with a solvent, the pressure in the system is reduced, and then the pressure is returned to the atmospheric pressure. The temperature may be room temperature, and the system pressure is 200m
Reduce the pressure to about mHg.
加圧注入法とは、加圧に耐え得る容器中で、膨張黒
鉛、マット、あるいは膨張黒鉛成形シートを溶剤に稀釈
した改質剤、溶液中に浸漬し、系内を乾燥空気により加
圧した後、大気圧に圧力をもどす操作である。温度は常
温でよく圧力は5kg/cm2Gで十分である。The pressure injection method is to immerse the expanded graphite, matte, or expanded graphite molded sheet in a modifier or solution diluted with a solvent, and pressurize the system with dry air in a container that can withstand pressure. Later, the operation is to return the pressure to the atmospheric pressure. The temperature is normal, and a pressure of 5 kg / cm 2 G is sufficient.
自然含浸法の他にこれらの方法でも改質剤を含浸する
ことが出来るが、一般的に真空注入法あるいは加圧注入
法の如き方法は短時間に多量の含浸を目的とする場合、
あるいは自然含浸法では含浸に長時間を要する場合に行
なわれるが、本発明の場合、自然含浸法でも充分含浸は
行なわれる。Modifiers can be impregnated by these methods in addition to the natural impregnation method.However, methods such as the vacuum injection method and the pressure injection method are generally used when a large amount of impregnation is intended in a short time.
Alternatively, the natural impregnation method is performed when a long time is required for the impregnation, but in the case of the present invention, the natural impregnation method is also sufficient for the impregnation.
含浸時間及び溶液濃度は目標とする含浸量に応じて適
宜選択するが、膨張黒鉛又はマットへの含浸は膨張黒鉛
成形シートの場合より、急速に含浸が進行し、この急速
含浸中に溶液より引き上げると含浸量のバラツキが大き
くなる。従って、膨張黒鉛又はマットへの含浸は、溶液
濃度を低くし、含浸時間を長くして、含浸量が安定する
の待って、引き上げるのが好ましい。一方、膨張黒鉛成
形シートへの含浸の場合、含浸時間を10秒以上にする
と、シートが膨潤し、本来の厚み、あるいは外見等がそ
こなわれるため、含浸時間は10秒以下にすることが好ま
しい。The impregnation time and the solution concentration are appropriately selected according to the target impregnation amount, but the impregnation into the expanded graphite or mat progresses more rapidly than in the case of the expanded graphite molded sheet, and the impregnation is withdrawn from the solution during the rapid impregnation. And the dispersion of the impregnation amount increases. Therefore, when impregnating the expanded graphite or mat, it is preferable to lower the solution concentration, lengthen the impregnation time, and wait until the impregnation amount is stabilized, and then pull up. On the other hand, in the case of impregnating the expanded graphite molded sheet, if the impregnation time is 10 seconds or more, the sheet swells and the original thickness or appearance is impaired, so the impregnation time is preferably 10 seconds or less. .
含浸あるいは噴霧等された改質剤は水分により硬化す
るが、通常は加熱して硬化させる。加熱温度は加水分解
後発生するアルコールの沸点、あるいは溶剤を使用する
ときは溶剤の沸点を考慮して定められるが通常は100〜1
50℃の比較的低い温度範囲であり、120〜130℃の範囲が
好ましく、この温度で１〜２時間加熱される。The impregnated or sprayed modifier is cured by moisture, but is usually cured by heating. The heating temperature is determined in consideration of the boiling point of the alcohol generated after hydrolysis, or the solvent when using a solvent, but is usually 100 to 1
It is a relatively low temperature range of 50 ° C, preferably in the range of 120-130 ° C, and heated at this temperature for 1-2 hours.
加熱硬化して黒鉛材に付着される改質剤の付着量は含
浸等処理前の黒鉛材100重量部に対して、硬化後の改質
剤量が0.01〜20重量部の範囲であり特に0.1〜10重量部
の範囲が好ましい。付着量がそれより少ないと耐不凍液
性、耐油性、耐酸化性向上の効果がでないし、又これよ
り多すぎると、黒鉛材の柔軟性、自己潤滑性が損なわ
れ、ガスケットのシート性が低下する。The amount of the modifier attached to the graphite material by heat curing is 100 parts by weight of the graphite material before impregnation or the like, and the amount of the modifier after curing is in the range of 0.01 to 20 parts by weight, particularly 0.1%. A range of from 10 to 10 parts by weight is preferred. If the amount is less than this, the effect of improving antifreeze resistance, oil resistance and oxidation resistance is not achieved, and if it is more than this, the flexibility and self-lubricating property of the graphite material will be impaired, and the sheet properties of the gasket will decrease. I do.
このようにして改質された黒鉛材がえられるが、これ
は下記実施例に示したデータからも明らかなように、圧
縮率、復元率を低下させることなく、耐不凍液性、耐油
性、耐酸化性等がすぐれており、内燃機関のガスケット
材としてきわめて有効に用いることができる。A graphite material modified in this manner is obtained. As is clear from the data shown in the following examples, this can be achieved without lowering the compression ratio and the recovery ratio, and is effective in preventing the antifreeze, oil and acid resistance. It has excellent chemical properties and can be used very effectively as a gasket material for an internal combustion engine.
（実施例１） 厚さ0.38mm、嵩密度1.05g/cm3膨張黒鉛成形シート
（ユニオン・カーバイト製、商品明GRAFOIL）を幅25m
m、長さ50mmの試験片に切り、チタニウム・アシレート
系改質剤（日本曹達製、商品名チタコートＳ−582）10
重量部と、トルエン90重量部の溶液に５秒間浸漬し、引
き上げ後120℃、２時間加熱した。(Example 1) A thickness of 0.38 mm and a bulk density of 1.05 g / cm 3 expanded graphite molded sheet (manufactured by Union Carbide, product name GRAFOIL) is 25 m in width.
m, cut into 50 mm long test pieces, titanium-acylate modifier (trade name: Titacoat S-582, manufactured by Nippon Soda) 10
The solution was immersed in a solution containing 90 parts by weight of toluene and 90 parts by weight of toluene for 5 seconds.
この時の改質剤の付着量は処理前の膨張黒鉛成形シー
ト100重量部に対して1.4重量部であった。At this time, the attached amount of the modifier was 1.4 parts by weight based on 100 parts by weight of the expanded graphite molded sheet before the treatment.
（実施例２） 実施例１と同じ膨張黒鉛シートを使用し、チタニウム
・アルコラート系改質剤（三菱瓦斯化学製、商品名TS
T）を使用した以外は実施例１と同じ処理をした。この
時の改質剤の付着量は処理前の膨張黒鉛成形シート100
重量部に対して、1.6重量部であった。(Example 2) Using the same expanded graphite sheet as in Example 1, a titanium / alcohol-based modifier (trade name: TS manufactured by Mitsubishi Gas Chemical Co., Ltd.)
The same processing as in Example 1 was performed except that T) was used. At this time, the adhering amount of the modifier is the expanded graphite molded sheet 100 before the treatment.
It was 1.6 parts by weight based on parts by weight.
（実施例３） 実施例１と同じ膨張黒鉛成形シートを使用し、チタニ
ウム・ヒドロキシカルボキシレート系改質剤（三菱瓦斯
化学製、商品名TLA）10重量部と水90重量部の溶液に５
秒間浸漬し、引き上げ後、120℃、２時間加熱した。こ
の時の改質剤の付着量は処理前の膨張黒鉛成形シート10
0重量部に対して0.45重量部であった。(Example 3) Using the same expanded graphite molded sheet as in Example 1, 5 parts by weight of a solution of 10 parts by weight of a titanium-hydroxycarboxylate-based modifier (trade name: TLA, manufactured by Mitsubishi Gas Chemical Company) and 90 parts by weight of water were used.
It was immersed for 2 seconds, pulled up, and heated at 120 ° C. for 2 hours. At this time, the adhering amount of the modifier is the expanded graphite molded sheet 10 before the treatment.
It was 0.45 parts by weight with respect to 0 parts by weight.
（実施例４） 実施例１と同じ膨張黒鉛成形シートを使用し、リンを
含むチタニウム・フォスフェート系改質剤（日本曹達
製、商品名チタコートＰ−151P）を使用した以外は、実
施例１と同じ処理をした。この時の改質剤の付着量は、
処理前の膨張黒鉛シート100重量部に対して1.3重量部で
あった。Example 4 Example 1 was repeated except that the same expanded graphite molded sheet as in Example 1 was used, and a titanium-phosphate-based modifier containing phosphorus (trade name: Titacoat P-151P, manufactured by Nippon Soda) was used. The same process was performed. At this time, the adhering amount of the modifier is
It was 1.3 parts by weight based on 100 parts by weight of the expanded graphite sheet before the treatment.
（実施例５） 積層構造を有する黒鉛粒子を酸処理し、水洗して得ら
れた膨張性黒鉛フレーク（ユニオン・カーバイド製GTC
フレーク）を1000℃で５〜10秒加熱し膨張黒鉛を得た。Example 5 Expandable graphite flakes obtained by acid-treating graphite particles having a laminated structure and washing with water (GTC manufactured by Union Carbide)
The flakes were heated at 1000 ° C. for 5 to 10 seconds to obtain expanded graphite.
該膨張黒鉛をチタニウム・アシレート系改質剤（日本
曹達製、商品名チタコートＳ−582）0.3重量部とトルエ
ン99.7重量部の溶液に60秒間浸漬した。引き上げ後120
℃、２時間加熱し、その後圧延ロールにより厚さ0.38m
m、嵩密度1.05g/cm3の膨張黒鉛成形シートを得た。この
時の改質剤の付着量は、処理前の膨張黒鉛100重量部に
対して1.4重量部であった。The expanded graphite was immersed in a solution of 0.3 parts by weight of a titanium / acylate-based modifier (trade name: Titacoat S-582, manufactured by Nippon Soda) and 99.7 parts by weight of toluene for 60 seconds. 120 after raising
℃ 2 hours, then 0.38m thick by rolling roll
m, an expanded graphite molded sheet having a bulk density of 1.05 g / cm 3 was obtained. At this time, the attached amount of the modifier was 1.4 parts by weight based on 100 parts by weight of the expanded graphite before the treatment.
（実施例６） 実施例５のように黒鉛フレークを加熱してえられた膨
張黒鉛を、ロールにより圧延し、厚さ4.5mm、嵩密度0.1
g/cm3のウェハース状のマットを得た。該マットをチタ
ニウム・フォスフェート系改質剤（日本曹達製、商品名
チタコートＰ−151P）0.4重量部とトルエン99.6重量部
の溶液に60秒間浸漬し、引き上げ後120℃、２時間加熱
した。その後ロールにより厚さ0.38mm、嵩密度1.05g/cm
3の膨張黒鉛成形シートを得た。この時の改質剤の付着
量は処理前のマット100重量部に対して1.3重量部であっ
た。(Example 6) Expanded graphite obtained by heating graphite flakes as in Example 5 was rolled by a roll to have a thickness of 4.5 mm and a bulk density of 0.1.
A wafer-like mat of g / cm 3 was obtained. The mat was immersed in a solution of 0.4 part by weight of a titanium / phosphate-based modifier (trade name: Titacoat P-151P, manufactured by Nippon Soda) and 99.6 parts by weight of toluene for 60 seconds, pulled up and heated at 120 ° C. for 2 hours. After that, 0.38 mm thick and 1.05 g / cm bulk density by roll
Thus, an expanded graphite molded sheet of No. 3 was obtained. At this time, the attached amount of the modifier was 1.3 parts by weight based on 100 parts by weight of the mat before the treatment.
（比較例） 実施例１により供したものと同じ膨張黒鉛成形シート
により何ら処理を加えず比較試料とした。(Comparative example) The same expanded graphite molded sheet as that used in Example 1 was used as a comparative sample without any treatment.
実施例１〜６、及び比較例で製造した膨張黒鉛成形シ
ートをJIS Ｒ−3453に準じて測定した圧縮率、復元率
の結果を第２表に示す。Table 2 shows the results of the compression ratio and the restoration ratio of the expanded graphite molded sheets manufactured in Examples 1 to 6 and Comparative Example, which were measured according to JIS R-3453.
次に実施例１〜６、及び比較例で製造した膨張黒鉛シ
ートの特性結果を第３表に示す。 Next, Table 3 shows the characteristic results of the expanded graphite sheets manufactured in Examples 1 to 6 and Comparative Example.
（第３表の項目の説明） ＊１ 耐不凍液性：耐不凍液性を調べるためASTM Ｆ−
146に準じ、水20重量部と不凍液（いすず自動車製 商
品名ロングライフクーラントスーパー）80重量部の混合
液に22時間浸漬煮沸後の、質量増加率、厚さ増加率の測
定結果。(Explanation of items in Table 3) * 1 Antifreeze resistance: ASTM F-
According to 146, the results of measurement of the rate of mass increase and the rate of thickness increase after immersion in a mixture of 20 parts by weight of water and 80 parts by weight of antifreeze (Isuzu Motors, Long Life Coolant Super) for 22 hours.
＊２ 耐油性：耐油性を調べるためJIS Ｒ−3453に基
づき、潤滑油No.3オイルに150℃、５時間浸漬加熱後の
質量増加率、厚さ増加率の測定結果。* 2 Oil resistance: Measurement of mass increase and thickness increase after immersion heating in lubricating oil No. 3 oil at 150 ° C for 5 hours based on JIS R-3453 to check oil resistance.
＊３ 耐酸化性：耐酸化性を調べるためマッフル炉770
℃雰囲気中での加熱重量減少率の測定結果。* 3 Oxidation resistance: Muffle furnace 770 to check oxidation resistance
Measurement result of heating weight loss rate in an atmosphere of ° C.
本発明にかかる改質黒鉛材の場合、ガスケット材、パ
ッキング材として重要である圧縮率、復元率が損なわれ
ていないことが第２表から明らかであり、又耐不凍液
性、耐油性、耐酸化性がすぐれており、改質剤の効果が
顕著にあらわれていることが、第３表により明らかであ
る。In the case of the modified graphite material according to the present invention, it is clear from Table 2 that the compressibility and the restoration rate, which are important as gasket materials and packing materials, are not impaired, and the antifreeze solution resistance, oil resistance, oxidation resistance It is clear from Table 3 that the properties are excellent and the effect of the modifier is remarkably exhibited.
〔発明の効果〕 上述のところから明らかなように、本発明に従って黒
鉛材を有機チタネート系改質剤で処理して得られた改質
黒鉛材は、ガスケット材として必要な圧縮率や復元率、
従って可撓性、柔軟性を損なうことなく、耐不凍液性、
耐油性や耐酸化性等各種特性を向上させることができ
る。しかも工業的に製造するに当って特殊な処理雰囲気
や高い温度を用いることなく短時間、低温度での加熱硬
化により連続的に容易に製造しうるため製造コスト、設
備コストを節減しうるなど作業性、経済性も良好であ
る。 [Effects of the Invention] As is clear from the above description, the modified graphite material obtained by treating the graphite material with the organic titanate-based modifier according to the present invention has a compression ratio and a restoration ratio required as a gasket material,
Therefore, without impairing flexibility, flexibility, antifreeze resistance,
Various properties such as oil resistance and oxidation resistance can be improved. In addition, in the case of industrial production, it can be easily and continuously produced by heating and curing at a low temperature for a short time without using a special processing atmosphere or high temperature, so that production costs and equipment costs can be reduced. The properties and economy are also good.
従って本発明による改質材は特に内燃機関のシリンダ
ーブロックとシリンダーヘッド間、或いは高温部のシー
ル用ガスケットとして用いるに有効である。Therefore, the modified material according to the present invention is particularly effective for use between a cylinder block and a cylinder head of an internal combustion engine or as a gasket for sealing a high-temperature portion.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 国広 宏之 兵庫県佐用郡佐用町佐用208 (72)発明者 岡本 卓也 兵庫県佐用郡上月町早瀬636 (72)発明者 永見 久之 兵庫県揖保郡太子町鵤762―４ (72)発明者 宮下 勝次 埼玉県南埼玉郡宮代町東688―79 (72)発明者 服部 雅毅 東京都練馬区南大泉６丁目９―13 サン ハイツＡ―201 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroyuki Kunihiro 208, Sayo-cho, Sayo-cho, Hyogo Prefecture (72) Inventor Takuya Okamoto 636, Hayase, Kamitsuki-cho, Sayo-gun, Hyogo (72) Inventor Hisayuki Nagami Taiko-cho, Ibo-gun, Hyogo 762-4 (72) Inventor Katsuji Miyashita 688-79, Miyashiro-cho, Minami-Saitama-gun, Saitama Prefecture (72) Inventor Masaki Hattori 6-9-13 Minami Oizumi, Nerima-ku, Tokyo Sun Heights A-201
Claims (5)
てなる改質黒鉛材。1. A modified graphite material obtained by treating a graphite material with an organic titanate-based modifier.
鉛材。2. The modified graphite material according to claim 1, wherein the graphite material is expanded graphite.
成形物である請求項１の改質黒鉛材。3. The modified graphite material according to claim 1, wherein the graphite material is a mat-like molded product obtained by compressing expanded graphite.
成形物である請求項１の改質黒鉛材。4. The modified graphite material according to claim 1, wherein the graphite material is a sheet-like molded product obtained by rolling expanded graphite.
ネート系改質材である請求項１の改質黒鉛材。5. The modified graphite material according to claim 1, wherein the organic titanate-based modifier is a phosphorus-containing organic titanate-based modifier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63079732A JP2593176B2 (en) | 1988-03-31 | 1988-03-31 | Modified graphite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63079732A JP2593176B2 (en) | 1988-03-31 | 1988-03-31 | Modified graphite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01252512A JPH01252512A (en) | 1989-10-09 |
| JP2593176B2 true JP2593176B2 (en) | 1997-03-26 |
Family
ID=13698381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63079732A Expired - Lifetime JP2593176B2 (en) | 1988-03-31 | 1988-03-31 | Modified graphite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2593176B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101261261B1 (en) * | 2012-06-18 | 2013-05-07 | 장주택 | Manufacturing method for thin film with expanded graphite |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7867615B2 (en) | 1920-09-26 | 2011-01-11 | Oiles Corporation | Heat-resistant exfoliated graphite sheet |
| EP1550821B1 (en) | 2002-10-08 | 2010-04-14 | Oiles Corporation | Spherical zone seal body |
| CN110015658A (en) * | 2019-03-21 | 2019-07-16 | 安徽工程大学 | A kind of water-based graphite alkene dispersion liquid and preparation method thereof |
| CN116478750A (en) * | 2023-04-23 | 2023-07-25 | 广东嘉福新材料科技有限公司 | Additive for lubricating oil and preparation method and application thereof |
-
1988
- 1988-03-31 JP JP63079732A patent/JP2593176B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101261261B1 (en) * | 2012-06-18 | 2013-05-07 | 장주택 | Manufacturing method for thin film with expanded graphite |
| WO2013191410A1 (en) * | 2012-06-18 | 2013-12-27 | Chang Joo Taek | Method for manufacturing ultra-thin thermal diffusion film using expanded graphite, and ultra-thin thermal diffusion film manufactured thereby |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01252512A (en) | 1989-10-09 |
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