JPH11158485A - Lubricating release agent for superplastic molding - Google Patents
Lubricating release agent for superplastic moldingInfo
- Publication number
- JPH11158485A JPH11158485A JP34080897A JP34080897A JPH11158485A JP H11158485 A JPH11158485 A JP H11158485A JP 34080897 A JP34080897 A JP 34080897A JP 34080897 A JP34080897 A JP 34080897A JP H11158485 A JPH11158485 A JP H11158485A
- Authority
- JP
- Japan
- Prior art keywords
- fatty acid
- release agent
- lubricating
- acid
- superplastic
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、超塑性成形方法で
ある雌型成形、雄型成形、ドレープ、スナップバック成
形などの成形方法の超塑性成形に使用する超塑性成形用
潤滑離型剤に関するものであり、特に４００℃以上の温
度でも潤滑性及び離型性に優れた超塑性成形用潤滑離型
剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lubricating release agent for superplastic forming used in superplastic forming such as female forming, male forming, drape, snapback forming and the like which are superplastic forming methods. Particularly, the present invention relates to a lubricating release agent for superplastic forming excellent in lubricity and releasability even at a temperature of 400 ° C. or more.
【０００２】[0002]
【従来の技術】超塑性材料は、高温において２００％以
上の伸び率が得られ、超塑性金属シートを特定領域の歪
速度で引張りを与えた場合に、局部変形（ネッキング）
を発生することなく著しい伸びを示す材料で、これが開
発されて久しい。例えば、アルミニウム合金ではすでに
１９７０年代にイギリスで開発されたＳｕｐｕｒａｌ
［Ａｌ−（Ｃｕ，Ｚｎ，Ｍｇ）−Ｚｒ系］をはじめとし
て、いずれも微細結晶組織からなるＡｌ−Ｍｇ系、Ａｌ
−Ｃｕ−Ｍｎ系、Ａｌ−Ｚｎ−Ｍｇ−Ｃｕ系（ＡＡ７０
７５合金）、連続鋳造圧延などの急速冷却凝固方式で製
造したＡｌ−Ｚｎ−Ｃａ合金などが知られている。2. Description of the Related Art A superplastic material has an elongation of 200% or more at a high temperature. When a superplastic metal sheet is stretched at a strain rate in a specific region, local deformation (necking) occurs.
This is a material that shows significant elongation without causing cracks and has been developed for a long time. For example, in the case of aluminum alloys, Supalal, which was already developed in the UK in the 1970s,
[Al- (Cu, Zn, Mg) -Zr system], Al-Mg system having a fine crystal structure, Al
-Cu-Mn system, Al-Zn-Mg-Cu system (AA70
75 alloy), an Al-Zn-Ca alloy manufactured by a rapid cooling solidification method such as continuous casting and rolling, and the like.
【０００３】また上記の合金であっても超塑性の発現に
は不十分なサイズの結晶粒組織を有するシートを出発材
料として、変形の過程において動的再結晶を生起させ、
微細結晶組織を形成しつつ超塑性成形させる方法も知ら
れている。従来これらの合金シートの超塑性成形は、変
形応力が小さいので、特定の温度に加熱したシートの片
側から数気圧程度の低い流体圧（通常は気体）を印加し
てバルジ成形を行ういわゆるブロー成形方法が用いられ
ている。[0003] Further, even with the above alloy, a sheet having a grain structure of a size insufficient for the expression of superplasticity is used as a starting material to cause dynamic recrystallization in the process of deformation,
A method of superplastic forming while forming a fine crystal structure is also known. Conventionally, since superplastic forming of these alloy sheets has a small deformation stress, so-called blow forming, in which bulge forming is performed by applying a low fluid pressure (usually gas) of several atmospheres from one side of a sheet heated to a specific temperature. A method is used.
【０００４】その特徴は、優れた変形性能を利用して、
通常のプレス成形法では成形が困難とされる複雑な形状
あるいは深さが大きい成形品またはリブ付き、浮き出し
模様などを有する成形品などの成形が単一工程（一体化
成形）で行えること、コストのかさむ金型は雌型もしく
は雄型のいずれか一方で足りることなどであり、応用す
る例が多く、機器のカバー、建材、装飾品などの非強度
部材から、自動車、船舶、車両、航空機などの構造強度
部材までの広い範囲に用いられている成形方法である。
特に型形状や凹凸の転写性に優れている成形方法であ
る。[0004] The feature is, utilizing the excellent deformation performance,
It is possible to mold in a single process (integral molding) such as a molded product with a complicated shape or a large depth or a molded product with ribs, embossed patterns, etc. A bulky mold is sufficient for either a female mold or a male mold, and is often used in many applications.From non-strength members such as equipment covers, building materials, and decorative articles, to automobiles, ships, vehicles, aircraft, etc. This is a molding method used for a wide range of structural strength members.
In particular, it is a molding method that is excellent in transferability of the shape of the mold and unevenness.
【０００５】このような超塑性成形用の潤滑離型剤とし
ては、一般に３５０℃以下ではポリ四フッ化エチレン
（商品名：テフロン）製のシート、大豆油、ポリブテン
などの合成油中にグラファイトを混入させたもの、グリ
ースや鉱物油にグラファイト、二硫化モリブデンあるい
はマイカなどを混入したものが使用され、３５０℃以上
の場合にはチッ化ホウ素が使用されている。実際に、比
較的低い低温（常温）でも成形できるＺｎ系合金では、
グラファイト系のものが使用されるのに対し、３５０℃
〜５５０℃程度のＡｌ系ではグラファイト系もしくはチ
ッ化ホウ素系（商品名：ルービーエヌ）でこれ以上の温
度では、チッ化ホウ素系の潤滑離型剤が使用される。し
かしこれらの潤滑離型剤は、一般的な成形に使用する高
温離型剤であり、超塑性成形用潤滑離型剤としては問題
が多い。これらの中で、３００℃程度でも使用できるポ
リ四フッ化エチレン製のシートや、１２００℃でも使用
可能なチッ化ホウ素製の潤滑離型剤は、性能的には優れ
てはいるが、非常に高価であり、製品単価に大きく影響
を及ぼし、工業製品の製造には潤滑離型剤として使用す
ることはコスト的に困難である。[0005] As such a lubricating release agent for superplastic forming, graphite is generally used in a sheet made of polytetrafluoroethylene (trade name: Teflon) or synthetic oil such as soybean oil and polybutene at 350 ° C or lower. A mixture containing grease or mineral oil mixed with graphite, molybdenum disulfide or mica is used. When the temperature is 350 ° C. or higher, boron nitride is used. Actually, in a Zn-based alloy that can be formed even at a relatively low temperature (normal temperature),
350 ° C. while graphite-based materials are used
Graphite or boron nitride (trade name: Ruby N) is used for Al based at about 550 ° C., and a boron nitride based lubricating release agent is used at higher temperatures. However, these lubricating release agents are high-temperature release agents used for general molding and have many problems as lubricating release agents for superplastic forming. Among these, a polytetrafluoroethylene sheet that can be used even at about 300 ° C. and a lubricating release agent made of boron nitride that can be used even at 1200 ° C. are excellent in performance, but very excellent. It is expensive and greatly affects the unit price of the product, and it is difficult to use it as a lubricating release agent in the production of industrial products in terms of cost.
【０００６】これ以外の潤滑剤としては、例えば大豆
油、合成油類（ポリブテン、シリコーンオイルなど）は
高温（２００℃以上）成形においては、焼き付きまたは
分解を起こし潤滑離型性を失うと共に、臭気の発生や着
火性を増し、作業環境を悪化させる。グリースや鉱物油
中にグラファイト、二硫化モリブデン、マイカなどを混
入した潤滑剤は使用中に煙を発生し易く、また焼き付き
や成形後での脱脂を困難とする。そのほかに、温間加工
用に開発されたアルミニウム材用の温間加工用潤滑剤
（特開平８−０７３８８３号）は、４００℃以上になる
と煙が発生すると共に臭気が強く、作業環境を悪化す
る。時には発生した煙が発火する時があり、４００℃以
上で使用する際は危険があるため換気に注意すると共に
保護具などをつける必要がある。更にこの時の潤滑離型
剤は変色し、機能を失うため超塑性成形はうまく行かな
い。また超塑性成形では成形後も塗布した潤滑離型剤が
加工材表面に均一に付着している必要があるが、この点
でも温間加工用潤滑剤は劣っている。As other lubricants, for example, soybean oil and synthetic oils (polybutene, silicone oil, etc.) are burned or decomposed at a high temperature (200 ° C. or higher) and lose lubricating releasability and have an odor. And the ignitability increase, and the working environment deteriorates. A lubricant in which graphite, molybdenum disulfide, mica, or the like is mixed in grease or mineral oil easily generates smoke during use, and makes it difficult to seize or degreasing after molding. In addition, a warm working lubricant for aluminum materials developed for warm working (JP-A-8-073883) emits smoke and has a strong odor at temperatures of 400 ° C. or higher, and deteriorates the working environment. . Occasionally, the generated smoke may ignite, and when used at 400 ° C or higher, there is a danger. Therefore, it is necessary to pay attention to ventilation and wear protective equipment. Further, the lubricating release agent at this time discolors and loses its function, so that superplastic forming cannot be performed successfully. In superplastic forming, the lubricating mold release agent applied after forming must be uniformly adhered to the surface of the work material. However, the lubricant for warm working is also inferior in this point.
【０００７】ほとんどの超塑性金属シートの成形は、室
温以上の温度で成形されるため、一般の潤滑及び離型剤
とは異なった性能を必要とする。特にこれらの性能の
内、高温（例えば５００℃）での潤滑性の維持、成形後
の成形品の型離れ、潤滑離型剤の熱変質による脱脂不良
の防止、使用中における潤滑離型剤組成物から発生する
ガスや煙などによる作業環境の悪化の防止、引火などに
よる火災発生の防止、超塑性金属シート及び金型への塗
布性と平滑塗布性、超塑性成形中の咬み込み及びかじり
の防止、成形中及び成形後の均一付着性などが重要とな
る。通常のプレス成形では雄、雌の金型を使い、、材料
を絞り込んで行く方法であるが、これに対し超塑性成形
では流体を使い、低い圧力で材料を雌型に添わせること
により複雑で深い成形や一体化成形が可能であり、かつ
金型のわずかな表面粗度まで転写される程転写性に優れ
ているため、潤滑性及び離型性が重要である。そのため
潤滑離型剤が分解することなく、金属シート表面に均一
に塗膜を形成していなければならないなど、超塑性成形
用潤滑離型剤として多くの要望があり、これらのすべて
を満たすような潤滑離型剤はまだ開発されていなかっ
た。[0007] Most superplastic metal sheets are formed at a temperature higher than room temperature, and therefore require different performance from general lubrication and release agents. Among these properties, in particular, maintenance of lubricity at a high temperature (for example, 500 ° C.), mold release of a molded article after molding, prevention of degreasing failure due to thermal deterioration of a lubricating release agent, lubricating release agent composition during use Prevention of deterioration of work environment due to gas and smoke generated from objects, prevention of fire by ignition, etc., applicability and smooth applicability to superplastic metal sheet and mold, bite and galling during superplastic forming Prevention and uniform adhesion during and after molding are important. In normal press molding, male and female molds are used and the material is narrowed down.On the other hand, in superplastic molding, fluid is used and the material is attached to the female mold at low pressure, which is complicated. Deep molding and integrated molding are possible, and the transferability is excellent as the mold is transferred to a slight surface roughness. Therefore, lubricity and releasability are important. For this reason, there are many demands for lubricating release agents for superplastic forming, such as that the lubricating release agent must form a uniform coating on the surface of the metal sheet without decomposing. Lubricating release agents have not yet been developed.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、経済性に優
れていること、金属シートへの均一な塗布が可能である
こと、咬み込み及びかじりがなく連続作業が可能である
こと、加工潤滑性に優れ、加工限界を向上させること、
成形後も成形された金属表面に均一な塗布状態を維持す
ること、高温において安定した成形特性、潤滑特性を有
すること、成形後の脱脂性に優れていること、耐食性が
あること、作業環境性に優れていること、長期保存でも
安定していることの条件を満たす超塑性成形用潤滑離型
剤の開発を目的とする。DISCLOSURE OF THE INVENTION The present invention is advantageous in that it is economical, that it can be uniformly applied to a metal sheet, that it can be continuously worked without biting and galling, and that it can be processed and lubricated. To improve the processing limit,
Maintaining a uniform coating state on the formed metal surface even after molding, having stable molding characteristics and lubrication characteristics at high temperatures, excellent degreasing after molding, corrosion resistance, work environment The object of the present invention is to develop a lubricating release agent for superplastic forming that satisfies the conditions of being excellent in stability and being stable even during long-term storage.
【０００９】[0009]
【課題を解決するための手段】本発明は、（１） 高級
脂肪酸、リン酸エステル、高分子カルボン酸及び固体潤
滑剤の組成物からなり、アルカリ金属化合物により該組
成物の固体分１％分散液のｐＨが７．５〜１０．０にな
るように調整したことを特徴とする超塑性成形用潤滑離
型剤、及び（２） 粒度１００ミクロン以下のグラファ
イト、二硫化モリブデン、タルク、マイカ、フッ素系樹
脂、チッ化ホウ素の少なくとも一種を含む固体潤滑剤１
００重量部に対し、主として炭素数１０〜２２の飽和脂
肪酸またはこれに少量の不飽和脂肪酸を含む高級脂肪酸
またはヤシ油脂肪酸、牛脂脂肪酸などの天然油脂脂肪酸
１０〜２００重量部、アルキルリン酸エステル、アルキ
ル−アリールリン酸エステルまたはポリオキシアルキレ
ンリン酸エステルの少なくとも一種からなるリン酸エス
テル５〜５０重量部、酸価１０以上の高分子カルボン酸
１〜２０重量部、最終組成物の固体分１％分散液のｐＨ
が７．５〜１０．０になる量のアルカリ金属化合物を添
加した請求項１記載の超塑性成形用潤滑離型剤を開発す
ることにより上記の目的を達成した。According to the present invention, there is provided (1) a composition comprising a higher fatty acid, a phosphoric ester, a polymer carboxylic acid and a solid lubricant, wherein the solid content of the composition is 1% by an alkali metal compound. A lubricating release agent for superplastic forming, wherein the pH of the liquid is adjusted to 7.5 to 10.0; and (2) graphite having a particle size of 100 microns or less, molybdenum disulfide, talc, mica, Solid lubricant 1 containing at least one of fluorine resin and boron nitride
100 parts by weight, 10 to 200 parts by weight of a natural fatty acid or fatty acid such as a higher fatty acid or a coconut oil fatty acid or a tallow fatty acid, which mainly contains a saturated fatty acid having 10 to 22 carbon atoms or a small amount of unsaturated fatty acid, an alkyl phosphate, 5 to 50 parts by weight of a phosphoric acid ester comprising at least one of an alkyl-aryl phosphoric acid ester and a polyoxyalkylene phosphoric acid ester, 1 to 20 parts by weight of a polymer carboxylic acid having an acid value of 10 or more, and 1% dispersion of solids in the final composition PH of liquid
The above object has been achieved by developing a lubricating mold release agent for superplastic forming according to claim 1, wherein an alkali metal compound is added in such an amount as to give a value of 7.5 to 10.0.
【００１０】[0010]
【発明の実施の形態】本発明の超塑性成形用潤滑離型剤
に使用する高級脂肪酸としては、主として炭素数１０〜
２２の飽和脂肪酸、あるいはこれに少量の不飽和脂肪酸
を含むもの、またはヤシ油脂肪酸、牛脂脂肪酸などの天
然脂肪酸である。炭素数１０未満の脂肪酸においては潤
滑性が劣り、また炭素数が２２を超えると乳化分散性が
低下し、潤滑離型剤の塗布ムラができ易く、良好な成形
品が得られにくい。配合量としては、固体潤滑剤１００
重量部に対して高級脂肪酸を１０〜２００重量部配合す
ることが必要である。高級脂肪酸が１０重量部未満では
潤滑性及び離型性が劣り、一方２００重量部を超える配
合は潤滑離型剤の流動性や離型性を低下させ、塗布しに
くくなり実用性を阻害する。BEST MODE FOR CARRYING OUT THE INVENTION The higher fatty acids used in the lubricating release agent for superplastic molding of the present invention are mainly those having 10 to 10 carbon atoms.
22 saturated fatty acids, or those containing a small amount of unsaturated fatty acids, or natural fatty acids such as coconut oil fatty acids and tallow fatty acids. If the fatty acid has less than 10 carbon atoms, the lubricating properties are poor. If the number of carbon atoms exceeds 22, the emulsifying and dispersing properties are reduced, and uneven application of the lubricating release agent is likely to occur, making it difficult to obtain a good molded product. The amount of the solid lubricant is 100
It is necessary to add 10 to 200 parts by weight of higher fatty acid to parts by weight. If the higher fatty acid content is less than 10 parts by weight, the lubricity and the releasability are inferior. On the other hand, if the content exceeds 200 parts by weight, the fluidity and the releasability of the lubricating release agent are reduced, making it difficult to apply and hindering practicality.
【００１１】本発明の超塑性成形用潤滑離型剤に使用す
るリン酸エステルとしては、脂肪族アルコール、アルキ
ル−アリールアルコール、ポリオキシエチレングリコー
ル、ポリプロピレングリコールまたはそれらの誘導体の
水酸基をリン酸エステル化したものであり、例えばトリ
デシルリン酸エステル、２−エチルヘキシルリン酸エス
テル、ノニルフェニルリン酸エステル、ポリオキシエチ
レントリデシルエーテルリン酸エステルなどを挙げるこ
とができる。固体潤滑剤１００重量部に対するリン酸エ
ステルの配合量は５〜５０重量部である。この配合量が
５重量部未満では変色や腐食の防止に効果が不十分とな
り、また５０重量部を超える配合では乳化分散性を阻害
する。The phosphoric acid ester used in the lubricating mold release agent for superplastic molding of the present invention includes a phosphoric acid ester of a hydroxyl group of an aliphatic alcohol, an alkyl-aryl alcohol, polyoxyethylene glycol, polypropylene glycol or a derivative thereof. Examples thereof include tridecyl phosphate, 2-ethylhexyl phosphate, nonylphenyl phosphate, polyoxyethylene tridecyl ether phosphate, and the like. The compounding amount of the phosphoric ester with respect to 100 parts by weight of the solid lubricant is 5 to 50 parts by weight. If the amount is less than 5 parts by weight, the effect of preventing discoloration and corrosion will be insufficient, and if it exceeds 50 parts by weight, the emulsifying dispersibility will be impaired.
【００１２】本発明の超塑性成形用潤滑離型剤に使用す
る固体潤滑剤は、粒度１００ミクロン以下のグラファイ
ト、二硫化モリブデン、タルク、マイカ、四フッ化エチ
レン樹脂またはチッ化ホウ素などの固体潤滑剤の一種な
いし数種を使用する。固体潤滑剤の粒度が１００ミクロ
ンを超える時は、均一な分散が困難となり、またコスト
が高くなるので１００ミクロン以下とする。配合量が少
なくなると乾燥性が劣り、多くなると高温（６００℃）
で潤滑剤の付着性が低下し、脱落し易くなる。このため
金型表面が成形品へ転写される関係上、金型清掃の頻度
が高くなることから生産が安定しなくなる。The solid lubricant used in the lubricating release agent for superplastic forming of the present invention is a solid lubricant such as graphite, molybdenum disulfide, talc, mica, tetrafluoroethylene resin or boron nitride having a particle size of 100 microns or less. Use one or several agents. When the particle size of the solid lubricant exceeds 100 microns, uniform dispersion becomes difficult and the cost is increased. When the amount is small, the drying property is inferior, and when the amount is large, high temperature (600 ° C.)
As a result, the adhesion of the lubricant decreases, and the lubricant easily falls off. For this reason, since the surface of the mold is transferred to the molded product, the frequency of the mold cleaning is increased, so that the production becomes unstable.
【００１３】アルカリ金属化合物としてはナトリウム、
カリウムの水酸化物、酸化物または炭酸塩がコスト及び
性能の面から好ましい。その他のアルカリ金属は高級脂
肪酸との反応により高級脂肪酸塩となった時に溶解性が
劣り、ゲル化し易い傾向があり、長期保存性が劣る。こ
の化合物の配合量は高分子カルボン酸その他の配合成分
により変動し、最終組成物の固体分１％分散液のｐＨが
７．５〜１０．０の範囲になるように配合する。これは
簡単なテストでその配合量を確定できる。Sodium as the alkali metal compound,
Potassium hydroxides, oxides or carbonates are preferred in terms of cost and performance. Other alkali metals have poor solubility when converted to higher fatty acid salts by reaction with higher fatty acids, tend to gel, and have poor long-term storage properties. The compounding amount of this compound varies depending on the polymer carboxylic acid and other compounding components, and the compound is added so that the pH of the 1% solid dispersion of the final composition is in the range of 7.5 to 10.0. This allows the amount to be determined with a simple test.
【００１４】本発明の超塑性成形用潤滑離型剤に使用す
る高分子カルボン酸は、ポリエチレンの酸化物及びオレ
フィン−ビニルカルボン酸の共重合体である。オレフィ
ンはエチレン、プロピレンなどの脂肪族ビニルモノマー
またはスチレンである。ビニルカルボン酸はアクリル
酸、メタクリル酸、無水マレイン酸、マレイン酸、フマ
ール酸である。この高分子カルボン酸の酸価（ＫＯＨ
ｍｇ／ｇ）は１０以上、好ましくは３０以上である。酸
価が１０未満では疎水性が強過ぎて水に溶解または分散
しない。分子量は５００〜１０，０００である。 共重
合体のカルボキシル基はナトリウムまたはカリウムの塩
にしておいてもよい。超塑性成形加工作業の時、本発明
の超塑性成形用潤滑離型剤を塗布して予備乾燥で膜を形
成させるが、高分子カルボン酸によって膜が硬質にな
り、乾燥中に液が流れにくく、膜をしっかりと固定し易
くなる。高分子カルボン酸の配合量は、固体潤滑剤１０
０重量部に対して１〜２０重量部、好ましくは３〜１５
重量部である。この配合量が１重量部未満では硬質膜が
弱く、２０重量部を超えると最終組成物の固体分に占め
る高級脂肪酸と固体潤滑剤の割合が小さくなって潤滑性
が不足する。The high molecular carboxylic acid used in the lubricating release agent for superplastic molding of the present invention is a copolymer of polyethylene oxide and olefin-vinyl carboxylic acid. The olefin is an aliphatic vinyl monomer such as ethylene, propylene or styrene. Vinyl carboxylic acids are acrylic acid, methacrylic acid, maleic anhydride, maleic acid, fumaric acid. The acid value of this high molecular carboxylic acid (KOH
mg / g) is 10 or more, preferably 30 or more. If the acid value is less than 10, the hydrophobicity is too strong to dissolve or disperse in water. The molecular weight is between 500 and 10,000. The carboxyl group of the copolymer may be in the form of a sodium or potassium salt. At the time of superplastic forming work, the film is formed by pre-drying by applying the lubricating mold release agent for superplastic forming of the present invention, but the film is hardened by the polymer carboxylic acid, and the liquid hardly flows during drying. , It is easy to fix the membrane firmly. The compounding amount of the high molecular carboxylic acid is 10
1 to 20 parts by weight, preferably 3 to 15 parts by weight with respect to 0 parts by weight
Parts by weight. If the amount is less than 1 part by weight, the hard film is weak, and if it exceeds 20 parts by weight, the ratio of the higher fatty acid and the solid lubricant to the solid content of the final composition becomes small, resulting in insufficient lubricity.
【００１５】上記の原材料を用いて本発明の超塑性成形
用潤滑離型剤の製造の一例を説明する。８０℃の水に、
最終組成分の固形分濃度が３０％になるように高級脂肪
酸、リン酸エステル、高分子カルボン酸を投入し、攪拌
しながらアルカリ金属化合物を添加し、９５〜９８℃で
全体を可溶化、乳化または分散させる。得られた溶液、
乳化液または分散液に固体潤滑剤を加えて分散させる。
アルカリ金属化合物は水酸化ナトリウム、炭酸ナトリウ
ム、水酸化カリウムなどである。高級脂肪酸、リン酸エ
ステル、及び高分子カルボン酸は使用前にあらかじめア
ルカリ金属の塩にしておいてもよい。An example of production of the lubricating release agent for superplastic forming of the present invention using the above-mentioned raw materials will be described. In water at 80 ° C,
A higher fatty acid, a phosphoric acid ester, and a polymer carboxylic acid are added so that the solid content concentration of the final composition is 30%, and an alkali metal compound is added with stirring, and the whole is solubilized and emulsified at 95 to 98 ° C. Or disperse. The resulting solution,
A solid lubricant is added to and dispersed in the emulsion or dispersion.
Alkali metal compounds include sodium hydroxide, sodium carbonate, potassium hydroxide and the like. The higher fatty acid, the phosphoric ester, and the high molecular carboxylic acid may be converted to an alkali metal salt before use.
【００１６】なお固体分１％濃度における分散液のｐＨ
が７．５未満の時は、潤滑離型剤組成物の乳化分散性が
損なわれ、長期保存性が低下する。一方ｐＨが１０．０
を超える時は、通常の場合リン酸エステルの変色防止作
用、腐食防止作用が損なわれる可能性があるため、ｐＨ
は７．５〜１０．０の範囲内に抑えることが必要であ
る。The pH of the dispersion at 1% solids concentration
Is less than 7.5, the emulsifying and dispersing properties of the lubricating release agent composition are impaired, and the long-term storability is reduced. On the other hand, if the pH is 10.0
When it exceeds, the discoloration preventing action and the corrosion preventing action of the phosphate ester may be impaired in the usual case.
Must be kept within the range of 7.5 to 10.0.
【００１７】本発明の超塑性成形用潤滑離型剤が有効に
作用する温度領域は、超塑性合金の種類により変動する
が、３５０〜６００℃、好ましくは４００〜５６０℃の
範囲において加工する場合に特に有効に使用できる。超
塑性成形加工作業としては、成形金型やその治具関係に
あらかじめ潤滑離型剤を塗布しておくことにより成形を
安定させ、更に超塑性成形前に超塑性金属シートに塗布
し成形する。なお潤滑離型剤は塗布後できるだけ乾燥し
ていた方が作業性が良い。The temperature range in which the lubricating mold release agent for superplastic forming of the present invention works effectively varies depending on the type of the superplastic alloy, but when working in the range of 350 to 600 ° C, preferably 400 to 560 ° C. It can be used particularly effectively. In the superplastic forming work, the forming is stabilized by applying a lubricating release agent in advance to a forming die and a jig thereof, and further, a superplastic metal sheet is applied and formed before the superplastic forming. The workability is better if the lubricating release agent is dried as much as possible after application.
【００１８】潤滑離型剤は、超塑性成形加工において成
形品単価や、生産性及び超塑性成形の特性である伸び、
キャビテーション、板厚分布などに大きく影響を及ぼす
ので重要である。本発明の潤滑離型剤の構成物質は、一
般に入手可能で安価なものであるため、それにより製造
された超塑性成形用潤滑離型剤もまた安価である。この
超塑性成形用潤滑離型剤の材料のうち、高級脂肪酸とア
ルカリ金属化合物とから得られる高級脂肪酸アルカリ金
属塩はそれだけでも低温においては潤滑作用を有し、こ
れにリン酸エステルを配合すれば超塑性金属シートの変
色や腐食防止作用を有する潤滑離型剤として用いること
ができる。しかし超塑性成形の温度の２００℃以上の温
度においては潤滑性が低下するので固体潤滑剤を配合す
る必要がある。本発明の超塑性成形用潤滑離型剤は、超
塑性成形する際、予備加熱の急速加熱において水分が蒸
発し、高分子カルボン酸が比較的硬い皮膜を形成する。
この硬質膜は２００℃以上でも分解しにくいため、超塑
性成形の高温でも良好な潤滑性を示し、成形を助けると
共に、成形後の優れた離型性を発揮することになる。The lubricating mold release agent is used in superplastic forming to increase the unit cost of a molded product, elongation which is a characteristic of productivity and superplastic forming,
This is important because it has a significant effect on cavitation and thickness distribution. Since the constituent materials of the lubricating release agent of the present invention are generally available and inexpensive, the lubricating release agent for superplastic molding produced thereby is also inexpensive. Among the materials for the superplastic forming lubricating release agent, the higher fatty acid alkali metal salt obtained from the higher fatty acid and the alkali metal compound has a lubricating action at a low temperature by itself, and if a phosphate ester is added thereto, It can be used as a lubricating release agent having an action of preventing discoloration and corrosion of a superplastic metal sheet. However, at a temperature of 200 ° C. or higher of the superplastic forming temperature, the lubricating property is reduced, so that it is necessary to incorporate a solid lubricant. The superplastic forming lubricating mold release agent of the present invention evaporates water in rapid heating of preheating during superplastic forming, and forms a relatively hard film of the polymeric carboxylic acid.
Since this hard film is hardly decomposed even at 200 ° C. or higher, it exhibits good lubricity even at the high temperature of superplastic forming, assists in forming, and exhibits excellent releasability after forming.
【００１９】本発明の組成は、潤滑離型剤を安定した粘
性状態に変え、塗布性を向上させ、同時に長期保存した
時においても液体のゲル化や分離を防ぎ、長期安定に優
れた超塑性成形用潤滑離型剤となっている。配合された
高分子カルボン酸は乾燥不十分でも塗膜を硬質にする性
質があるから、塗布した液が流れにくく、膜をしっかり
と固定する。本発明の超塑性成形用潤滑離型剤は、配合
された高分子カルボン酸の硬質膜形成能と共に高級脂肪
酸、リン酸エステル及びアルカリ金属化合物が超塑性成
形の条件下で超塑性金属シート表面に潤滑離型性、かじ
り防止性、成形後の脱脂性、耐食性に優れた皮膜を形成
することになる。更にこの皮膜は固体潤滑剤を保持し、
超塑性金属シート表面に分散させ固着させる役割を果た
し、特に高温で優れた性能を有する固体潤滑離型剤の性
能を発揮させ、高温でも安定した固体潤滑離型皮膜を形
成させるものである。The composition of the present invention changes the lubricating release agent to a stable viscous state, improves the applicability, and at the same time, prevents gelling and separation of the liquid even when stored for a long period of time. It is a lubricating mold release agent for molding. The compounded high molecular carboxylic acid has the property of hardening the coating film even if it is insufficiently dried, so that the applied liquid does not easily flow and firmly fixes the film. The superplastic forming lubricating mold release agent of the present invention is characterized in that a higher fatty acid, a phosphate ester and an alkali metal compound are added to the surface of the superplastic metal sheet under the conditions of superplastic forming together with the hard film forming ability of the compounded polymer carboxylic acid. A film excellent in lubricating release property, anti-galling property, degreasing property after molding, and corrosion resistance is formed. In addition, this coating retains the solid lubricant,
It plays a role of dispersing and adhering to the surface of the superplastic metal sheet, exerts the performance of a solid lubricating release agent having excellent performance especially at high temperatures, and forms a stable solid lubricating release film even at high temperatures.
【００２０】[0020]
【実施例】［試験方法］ １．液安定性（耐分離性、耐ゲル化性） 被試験剤を１リットルポリエチレンビンに室温で１か月
保管し、液の分離、固体粉末潤滑離型剤の分離沈殿、ゲ
ル化などの状況を評価。 液に変化のないもの ○ 簡単な攪拌で元に戻るもの △ 簡単な攪拌で元に戻らないもの ×EXAMPLES [Test Method] Liquid stability (separation resistance, gelation resistance) The test agent is stored in a 1-liter polyethylene bottle at room temperature for one month, and the liquid separation, solid powder lubricating release agent separation precipitation, gelation, etc. Evaluation. No change in liquid ○ One that returns to its original state by simple stirring △ One that does not return to its original state after simple stirring ×
【００２１】２．塗布性 液安定性の◎、○、△、×のものを評価対象とした。常
温でエアスプレーガンで塗布し、３０分間室温で乾燥
し、塗布状態を評価。 濡れ性が良く均一で液ダレやブツ（固体粉末の凝集）がない。 ○ 濡れ性が良く、均一であるが液がタレる。 △ 濡れ性が悪く液タレやブツ（固体粉末の凝集）がある。 ×2. Applicability The liquid stability ◎, ○, Δ, and × were evaluated. Apply at room temperature with an air spray gun, dry at room temperature for 30 minutes and evaluate the applied state. It has good wettability and is free of liquid dripping and bumps (aggregation of solid powder). ○ Good wettability and uniform but liquid dripping. △ Poor wettability, with liquid dripping and bumps (aggregation of solid powder). ×
【００２２】３．摩擦特性 バウデン摩擦摩耗試験機で評価 摺動工具：径１０ｍｍφベアリング球、垂直荷重Ｗ：１
Ｋｇｆ、摺動速度：０．５７ｍｍ／ｍｉｎで、超塑性金
属シートの両面に被試験材を１０〜２０ｇ／ｍ2 の割合
に塗布し、室温乾燥後、設定温度（５００℃）に加熱し
たバウデン試験機摺動台上にセットし、超塑性金属シー
トが４００℃に到達した時点から摺動試験を開始し、そ
れにより摺動抵抗Ｆを測定し、μ＝Ｆ／Ｗで摩擦係数を
算出した。 摩擦係数が０．１以下 ■ 摩擦係数が０．２５以下 △ 摩擦係数が０．２５以上 ×3. Friction characteristics Evaluated with Bowden friction and wear tester Sliding tool: 10 mm diameter bearing ball, vertical load W: 1
Kgf, sliding speed: 0.57 mm / min, a material to be tested applied to both surfaces of a superplastic metal sheet at a rate of 10 to 20 g / m 2 , dried at room temperature, and then heated to a set temperature (500 ° C.). The sliding test was started when the superplastic metal sheet reached 400 ° C., the sliding resistance F was measured, and the friction coefficient was calculated by μ = F / W. . The coefficient of friction is 0.1 or less ■ The coefficient of friction is 0.25 or less △ The coefficient of friction is 0.25 or more ×
【００２３】４．かじり性 バウデン摩擦摩耗試験機で評価 摩擦係数測定と同条件で限界往復摺動回数を測定。摺動
限界は摩擦係数が０．３を超えた時の回数とする。 限界往復摺動回数５回以上 ■ 限界往復摺動回数２回以上 △ 限界往復摺動回数２回未満 ×4. Galling Evaluated with a Bowden friction and wear tester. The number of reciprocal sliding movements was measured under the same conditions as the friction coefficient measurement. The sliding limit is the number of times when the friction coefficient exceeds 0.3. Limit reciprocating sliding frequency 5 or more ■ Limit reciprocating sliding frequency 2 or more △ Limit reciprocating sliding frequency 2 or less ×
【００２４】５．脱脂性試験 超塑性合金シートの両面に被試験剤を塗布し、室温乾燥
後、設定温度（５００℃）に加熱した鋼板熱板間で２分
間挟み、その後脱脂試験を行う。 （脱脂方法）１０％硝酸（１分）→水洗→１０％苛性ソ
ーダ（６０℃、２分）→水洗→１０％硝酸（デスマッ
ト）→水洗 判定：酸化膜の剥離程度 酸化膜の剥離 １００％ ○ 酸化膜の剥離 ８０％超 △ 酸化膜の剥離 ８０％以下 ×5. Degreasing test The test agent is applied to both surfaces of the superplastic alloy sheet, dried at room temperature, sandwiched between hot steel plates heated to a set temperature (500 ° C.) for 2 minutes, and then subjected to a degreasing test. (Degreasing method) 10% nitric acid (1 minute) → water washing → 10% caustic soda (60 ° C, 2 minutes) → water washing → 10% nitric acid (desmut) → water washing Judgment: Degree of oxide film peeling Oxide film peeling 100% ○ Oxidation Film peeling more than 80% △ Oxide film peeling 80% or less ×
【００２５】６．耐食性試験 超塑性合金シートの両面に被試験剤を塗布し、室温乾燥
後、設定温度（５００℃）に加熱した鋼板熱板間で２分
間挟み、その後耐食試験を行う。 （試験条件）４０℃×湿度８０％ １か月垂直立てかけ 判定：取り出し後の外観観察 腐食なし ○ 点状腐食がわずかにあり △ 多数の点状腐食か面腐食発生 ×6. Corrosion resistance test An agent to be tested is applied to both surfaces of a superplastic alloy sheet, dried at room temperature, sandwiched between hot steel plates heated to a set temperature (500 ° C.) for 2 minutes, and then subjected to a corrosion resistance test. (Test conditions) 40 ° C x 80% humidity 1 month vertical leaning Judgment: Observation of external appearance after removal No corrosion ○ Slight spot corrosion △ Many spot corrosion or surface corrosion ×
【００２６】（高分子カルボン酸の実施例） 酸化ポリエチレンワックス（高分子カルボン酸Ａ）酸
価； １５、滴点８５℃ 酸化ポリエチレンワックス（高分子カルボン酸Ｂ）酸
価； ４１、滴点９４℃ エチレン・アクリル酸共重合体（高分子カルボン酸Ｃ）
酸価； ６１、滴点９６℃ エチレン・アクリル酸共重合体（高分子カルボン酸Ｄ）
酸価；１３０、滴点９１℃(Example of polymer carboxylic acid) Oxidized polyethylene wax (polymeric carboxylic acid A) acid value; 15, drop point 85 ° C Oxidized polyethylene wax (polymeric carboxylic acid B) acid value; 41, drop point 94 ° C Ethylene / acrylic acid copolymer (high molecular carboxylic acid C)
Acid value: 61, Drop point 96 ° C Ethylene / acrylic acid copolymer (high molecular carboxylic acid D)
Acid value: 130, drop point 91 ° C
【００２７】（実施例１〜９）高級脂肪酸として牛脂脂
肪酸、リン酸エステルとしてトリデシルリン酸エステル
及びポリオキシエチレンラウリルリン酸エステルを少量
の水に添加し、苛性ソーダ及び水を加えてその１％濃度
の分散液のｐＨが表１に示す所定の値となるように調整
した後、固体潤滑剤として粒度２ミクロンの二硫化モリ
ブデン及び粒度２ミクロンのグラファイトを表１に示す
所定量配合し、更に水を加えて全量を１００重量部とし
た。このようにして得られた超塑性成形用潤滑離型剤を
前記試験方法により測定を行った。評価の結果を表３に
示す。(Examples 1 to 9) Tallow fatty acid as a higher fatty acid and tridecyl phosphate and polyoxyethylene lauryl phosphate as phosphates were added to a small amount of water, and caustic soda and water were added thereto to adjust the concentration to 1%. After adjusting the pH of the dispersion to a predetermined value shown in Table 1, molybdenum disulfide having a particle size of 2 μm and graphite having a particle size of 2 μm were mixed as solid lubricants in predetermined amounts shown in Table 1, and water was further added. In addition, the total amount was 100 parts by weight. The lubricating release agent for superplastic forming obtained in this way was measured by the test method described above. Table 3 shows the results of the evaluation.
【００２８】[0028]
【表１】 [Table 1]
【００２９】（比較例１〜１０）高級脂肪酸として牛脂
脂肪酸、カプリン酸、ベヘニン酸を、リン酸エステルと
してトリデシルリン酸エステル、ポリオキシエチレンラ
ウリルリン酸エステルを、固体潤滑剤として粒度２ミク
ロン及び１００ミクロンの二硫化モリブデン及び粒度２
ミクロンのグラファイト及び苛性ソーダを用いて表２に
示す組成割合で実施例に準じて潤滑離型剤組成物を調製
し、実施例と同じ試験方法で評価を行った。結果を表３
に示す。Comparative Examples 1 to 10 Tallow fatty acid, capric acid and behenic acid as higher fatty acids, tridecyl phosphate and polyoxyethylene lauryl phosphate as phosphate esters, and particle sizes of 2 μm and 100 μm as solid lubricants Molybdenum disulfide and particle size 2
A lubricating release agent composition was prepared according to the examples using micron graphite and caustic soda at the composition ratios shown in Table 2, and evaluated by the same test method as in the examples. Table 3 shows the results
Shown in
【００３０】[0030]
【表２】 [Table 2]
【００３１】[0031]
【表３】 [Table 3]
【００３２】（成形例）本発明で開発した超塑性成形用
潤滑離型剤及び従来の高温成形または超塑性成形用潤滑
離型剤について超塑性成形用金型を用いて評価した一例
を表４に示す。 ［評価］： 成形特性：アルミニウム超塑性金属シートを５００℃雰
囲気の中で超塑性コアパネル金型を持ちいて超塑性成形
を行った。評価基準は下記の通り。 Ａ）成形性を成形頭部コーナーＲで評価 Ｒ形状が非常に小さい ◎ Ｒ形状が小 ○ Ｒ形状が中 △ Ｒ形状が大 × Ｂ）離型性（かじり性） 型離れが非常に良い ◎ 型離れがやや良い ○ 何とか型離れする △ 型離れが非常に悪い × Ｃ）塗布性（乾燥性） 非常に早い（速乾性） ◎ ３０分以内 ○ ３０分以上 × Ｄ）成形後の塗膜状態 均一に塗膜が残っている ◎ ほぼ均一に残っているが粉末状 ○ 凝集と粉末状の混粒 △ 塗膜が凝集している ×(Molding Example) Table 4 shows an example of the evaluation of the lubricating release agent for superplastic forming and the conventional lubricating release agent for high-temperature forming or superplastic forming, which were developed by the present invention, using a superplastic forming die. Shown in [Evaluation]: Forming properties: Superplastic forming was performed on an aluminum superplastic metal sheet while holding a superplastic core panel mold in a 500 ° C. atmosphere. The evaluation criteria are as follows. A) Evaluate moldability at corner R of molding head R shape is very small ◎ R shape is small ○ R shape is medium △ R shape is large × B) Release property (galling property) Mold release is very good ◎ Slightly good mold release ○ Somehow mold release △ Very bad mold release × C) Coatability (dryness) Very fast (quick drying) ◎ Within 30 minutes ○ 30 minutes or more × D) State of coating film after molding Coating film remains evenly ◎ Almost uniformly remaining but powdery ○ Coagulation and mixed particles of powdery △ Coating film ×
【００３３】コスト： 潤滑離型剤の価格が安い ◎ 潤滑離型剤の価格がやや安い ○ 潤滑離型剤の価格が高い △ 潤滑離型剤の価格が非常に高い ×Cost: The price of the lubricating release agent is low ◎ The price of the lubricating release agent is slightly low ○ The price of the lubricating release agent is high △ The price of the lubricating release agent is very high ×
【００３４】[0034]
【表４】 [Table 4]
【００３５】[0035]
【発明の効果】本発明は、超塑性成形方法である雌型成
形、雄型成形、ドレープ、スナップバック成形などの成
形方法の超塑性成形に使用する超塑性成形用潤滑離型剤
に関するものであり、特に４００℃以上の温度でも潤滑
性及び離型性に優れた超塑性成形用潤滑離型であって、
経済性に優れていること、金属シートへの均一な塗布が
可能であること、咬み込み及びかじりがなく連続作業が
可能であること、加工潤滑性に優れ、加工限界を向上さ
せること、成形後も成形された金属表面に均一な塗布状
態を維持すること、高温において安定した成形特性、潤
滑特性を有すること、成形後の脱脂性に優れているこ
と、耐食性があること、作業環境性に優れていること、
長期保存でも安定していることなどの条件を満たす超塑
性成形用潤滑離型剤を開発することに成功したものであ
る。本発明の超塑性成形用潤滑離型剤は、配合された高
分子カルボン酸の硬質膜形成能と共に高級脂肪酸、リン
酸エステル及びアルカリ金属化合物が超塑性成形の条件
下で超塑性金属シート表面に潤滑離型性、かじり防止
性、成形後の脱脂性、耐食性に優れた皮膜を形成するこ
とになる。更にこの皮膜は固体潤滑剤を保持し、超塑性
金属シート表面に分散させ固着させる役割を果たし、特
に高温で優れた性能を有する固体潤滑離型剤の性能を発
揮させ、高温でも安定した固体潤滑離型皮膜を形成させ
るものである。このため本発明の超塑性成形用潤滑離型
剤が有効に作用する温度領域は、超塑性合金の種類によ
り変動するが、３５０〜６００℃、好ましくは４００〜
５６０℃の範囲において加工する場合に特に有効に使用
できるものであり、超塑性加工に有利に使用できる。Industrial Applicability The present invention relates to a lubricating release agent for superplastic forming used in superplastic forming of superplastic forming methods such as female forming, male forming, drape and snapback forming. Yes, lubricating mold release for superplastic forming with excellent lubricity and mold releasability even at temperatures of 400 ° C. or more,
Excellent economy, uniform application to metal sheet, continuous work without biting and galling, excellent processing lubrication, improving processing limit, after molding Maintains a uniform coating state on the formed metal surface, has stable molding characteristics and lubrication characteristics at high temperatures, has excellent degreasing properties after molding, has corrosion resistance, and has excellent work environment That
It succeeded in developing a lubricating release agent for superplastic forming that satisfies conditions such as being stable even during long-term storage. The superplastic forming lubricating mold release agent of the present invention is characterized in that a higher fatty acid, a phosphate ester and an alkali metal compound are added to the surface of the superplastic metal sheet under the conditions of superplastic forming together with the hard film forming ability of the compounded polymer carboxylic acid. A film excellent in lubricating release property, anti-galling property, degreasing property after molding, and corrosion resistance is formed. In addition, this film holds the solid lubricant and plays a role of dispersing and adhering to the surface of the superplastic metal sheet. Particularly, the performance of the solid lubricant release agent, which has excellent performance at high temperatures, is demonstrated. This is to form a release film. Therefore, the temperature range in which the lubricating mold release agent for superplastic forming of the present invention works effectively varies depending on the type of superplastic alloy, but is 350 to 600 ° C, preferably 400 to 600 ° C.
It can be used particularly effectively when working in the range of 560 ° C., and can be advantageously used for superplastic working.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ１０Ｍ 107/38 Ｃ１０Ｍ 107/38 129/40 129/40 137/04 137/04 145/10 145/10 // Ｃ１０Ｎ 10:02 10:12 20:06 30:00 30:08 40:24 40:36 50:02 (72)発明者 古谷 啓伸 大阪府高槻市道鵜町４−22−１ 日油工業 株式会社内──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C10M 107/38 C10M 107/38 129/40 129/40 137/04 137/04 145/10 145/10 // C10N 10:02 10:12 20:06 30:00 30:08 40:24 40:36 50:02 (72) Inventor Hironobu Furuya 4-2-1 Michioumachi, Takatsuki City, Osaka Prefecture
Claims (2)
ルボン酸及び固体潤滑剤の組成物からなり、アルカリ金
属化合物により該組成物の固体分１％分散液のｐＨが
７．５〜１０．０になるように調整したことを特徴とす
る超塑性成形用潤滑離型剤。1. A composition comprising a higher fatty acid, a phosphoric acid ester, a polymer carboxylic acid and a solid lubricant, wherein the pH of a 1% solid dispersion of the composition is 7.5 to 10.0 with an alkali metal compound. A lubricating release agent for superplastic forming, characterized in that the release agent is adjusted to be:
ト、二硫化モリブデン、タルク、マイカ、フッ素系樹
脂、チッ化ホウ素の少なくとも一種を含む固体潤滑剤１
００重量部に対し、主として炭素数１０〜２２の飽和脂
肪酸またはこれに少量の不飽和脂肪酸を含む高級脂肪酸
またはヤシ油脂肪酸、牛脂脂肪酸などの天然油脂脂肪酸
１０〜２００重量部、アルキルリン酸エステル、アルキ
ル−アリールリン酸エステルまたはポリオキシアルキレ
ンリン酸エステルの少なくとも一種からなるリン酸エス
テル５〜５０重量部、酸価１０以上の高分子カルボン酸
１〜２０重量部、最終組成物の固体分１％分散液のｐＨ
が７．５〜１０．０になる量のアルカリ金属化合物を添
加した請求項１記載の超塑性成形用潤滑離型剤。2. A solid lubricant 1 containing at least one of graphite, molybdenum disulfide, talc, mica, fluororesin, and boron nitride having a particle size of 100 microns or less.
100 parts by weight, 10 to 200 parts by weight of a natural fatty acid or fatty acid such as a higher fatty acid or a coconut oil fatty acid or a tallow fatty acid, which mainly contains a saturated fatty acid having 10 to 22 carbon atoms or a small amount of unsaturated fatty acid, an alkyl phosphate, 5 to 50 parts by weight of a phosphoric acid ester comprising at least one of an alkyl-aryl phosphoric acid ester and a polyoxyalkylene phosphoric acid ester, 1 to 20 parts by weight of a polymer carboxylic acid having an acid value of 10 or more, and 1% dispersion of solids in the final composition PH of liquid
The lubricating mold release agent for superplastic forming according to claim 1, wherein an alkali metal compound is added in an amount of 7.5 to 10.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34080897A JPH11158485A (en) | 1997-11-26 | 1997-11-26 | Lubricating release agent for superplastic molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34080897A JPH11158485A (en) | 1997-11-26 | 1997-11-26 | Lubricating release agent for superplastic molding |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11158485A true JPH11158485A (en) | 1999-06-15 |
Family
ID=18340491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34080897A Pending JPH11158485A (en) | 1997-11-26 | 1997-11-26 | Lubricating release agent for superplastic molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11158485A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000053705A1 (en) * | 1999-03-05 | 2000-09-14 | Chuo Hatsumei Institute Co., Ltd. | Lubricating and releasing composition for plastic working |
| WO2005095564A1 (en) * | 2004-03-31 | 2005-10-13 | Idemitsu Kosan Co., Ltd. | Aqueous lubricant composition for metal material working |
| WO2014003074A1 (en) | 2012-06-27 | 2014-01-03 | 株式会社Uacj | Aluminum alloy sheet for blow molding and production method therefor |
| US20160075903A1 (en) * | 2013-06-07 | 2016-03-17 | Hydro Aluminium Rolled Products Gmbh | Coating of a metal sheet or strip |
-
1997
- 1997-11-26 JP JP34080897A patent/JPH11158485A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000053705A1 (en) * | 1999-03-05 | 2000-09-14 | Chuo Hatsumei Institute Co., Ltd. | Lubricating and releasing composition for plastic working |
| JP4659220B2 (en) * | 1999-03-05 | 2011-03-30 | 株式会社Ｍｏｒｅｓｃｏ | Water-based lubricating release agent composition for plastic working |
| WO2005095564A1 (en) * | 2004-03-31 | 2005-10-13 | Idemitsu Kosan Co., Ltd. | Aqueous lubricant composition for metal material working |
| JP2005290154A (en) * | 2004-03-31 | 2005-10-20 | Idemitsu Kosan Co Ltd | Aqueous lubricant composition for metal material processing |
| WO2014003074A1 (en) | 2012-06-27 | 2014-01-03 | 株式会社Uacj | Aluminum alloy sheet for blow molding and production method therefor |
| US10907241B2 (en) | 2012-06-27 | 2021-02-02 | Uacj Corporation | Aluminum alloy sheet for blow molding and production method therefor |
| US20160075903A1 (en) * | 2013-06-07 | 2016-03-17 | Hydro Aluminium Rolled Products Gmbh | Coating of a metal sheet or strip |
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