JP2004351452A - Plastic working pretreatment agent - Google Patents
Plastic working pretreatment agent Download PDFInfo
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- JP2004351452A JP2004351452A JP2003151086A JP2003151086A JP2004351452A JP 2004351452 A JP2004351452 A JP 2004351452A JP 2003151086 A JP2003151086 A JP 2003151086A JP 2003151086 A JP2003151086 A JP 2003151086A JP 2004351452 A JP2004351452 A JP 2004351452A
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Abstract
Description
【0001】
【発明の属する技術分野】
本発明は、引抜加工等の塑性加工を施す金属原材に用いられる塑性加工前処理剤に関するものである。
【0002】
【従来の技術】
鉄、鋼、ステンレス鋼の金属原材は、引抜加工やプレス加工のような塑性加工が施され、成形製品になる。
【0003】
金属原材は、その表面金属酸化被膜の酸洗浄や機械的研削の後、適度な潤滑性や防錆性を付与したり塑性加工し易くしたりするためにリン酸塩、ホウ酸塩、フッ素樹脂、石灰石鹸、シュウ酸塩等を含む塑性加工前処理剤により予め被膜形成され、必要に応じ潤滑剤存在下、塑性加工される。例えば、特許文献1にリン酸塩等を含む前処理剤、特許文献2にホウ酸塩を含む前処理剤、特許文献3に金属石鹸を含む前処理剤が開示されている。
【0004】
【特許文献1】特開平6−212444号公報
【特許文献2】特開2000−345361号公報
【特許文献3】特開昭63−69889号公報
【0005】
リン酸塩、ホウ酸塩、フッ化樹脂等は作業環境の悪化や自然環境の汚染を引き起こすおそれがあるのでそれらを含まず、また潤滑性や防錆性に一層優れた前処理剤が望まれていた。
【0006】
【発明が解決しようとする課題】
本発明は前記の課題を解決するためになされたもので、ホウ素、リン、フッ素のような元素を含まず、金属原材に適度な潤滑性や防錆性を付与できる塑性加工前処理剤を提供することを目的とする。
【0007】
【課題を解決するための手段】
前記の目的を達成するためになされた本発明の塑性加工前処理剤は、少なくとも1価および/または3価の金属イオンと、2価の金属イオンと、水酸化物イオンとで複水酸化物層を形成し、有機酸をその層間にインターカレートしている層状複水酸化物が、含有されている。
【0008】
この塑性加工前処理剤は、ホストである層状複水酸化物の機械的強度・耐熱性と、ゲストである有機酸の潤滑性とを併せ持ち、耐極圧性と展着性とに優れた被膜を金属原材上に形成させる。
【0009】
有機酸は、R1−COOH(R1−は炭素数1〜24のアルキル基、炭素数2〜24のアルケニル基、無置換またはアルキル基置換フェニル基のいずれか)で示されるモノカルボン酸であることが好ましく、より具体的にはステアリン酸、オレイン酸、パルミチン酸が挙げられる。有機酸は、R2−SO3H(R2−はR1−に同じ)で示されるモノスルホン酸であってもよく、より具体的にはドデシル硫酸、ドデシルベンゼン硫酸が挙げられる。また有機酸は、HOOC−R3−COOH(−R3−は炭素数0〜24のアルキル基、炭素数2〜24のアルケニル基、無置換またはアルキル基置換フェニレン基のいずれか)であってもよく、より具体的にはシュウ酸、マレイン酸、フマル酸が挙げられる。
【0010】
1価の金属イオンがLi+、前記2価の金属イオンがMg2+、Zn2+、Ca2+、Cu2+、Zr2+、Co2+、Ni2+、Fe2+、またはMn2+、前記3価の金属イオンがAl3+、Fe3+、またはCo3+であると好ましい。複水酸化物層は、これらイオンと水酸化物とから形成され、中でもMg2+とAl3+と水酸化物イオンとから形成されていると一層好ましい。
【0011】
塑性加工前処理剤は、硫酸カリウムを含んでいてもよく、展着助剤、分散剤、防錆剤のような添加剤を含んでいてもよい。硫酸カリウムや添加剤は、層状複水酸化物100重量部に対し、0.05〜138重量部含まれていることが好ましい。
【0012】
展着剤や分散剤は、イソブチレン/無水マレイン酸コポリマー、アルキルポリオキシエチレンエーテルカルボン酸、アラビアゴム、カルボキシメチルセルロース、デキストリン、ポリアクリル酸ナトリウム、アクリル酸/マレイン酸共重合体、アクリル酸/スルホン酸モノマー共重合体、ポリビニルピロリドン、ヘキサエチレングリコール(HEG)、ベントナイトが好ましい。中でもイソブチレン/無水マレイン酸コポリマー、アルキルポリオキシエチレンエーテルカルボン酸、アラビアゴム、ベントナイトであると一層好ましい。
【0013】
この塑性加工前処理剤は、例えば1価および/または3価の金属の水溶性塩と、2価の金属の水溶性塩または2価の金属の酸化物と、有機酸および/またはその金属塩とを、アルカリ性の水中で混合した後、生成した層状複水酸化物を分取して、得られるものである。
【0014】
塑性加工前処理剤は、粉末のままであってもよいが、層状複水酸化物が水および/または有機溶媒で希釈され懸濁された処理液にされていると好ましい。水で希釈されていると一層好ましい。固形分3〜30%好ましくは5〜15%となるよう水で希釈されているとなお一層好ましい。
【0015】
この前処理剤を用いた塑性加工前処理方法は、例えば、この処理液を塗布、噴霧、浸漬によって、金属材料と接触させた後、乾燥するというものである。処理液を温度60℃以上で金属材料と接触させると好ましい。金属原材は、例えば鉄、鋼、ステンレス鋼が挙げられる。中でも、特にステンレス鋼が適当である。
【0016】
この塑性加工前処理剤は、簡便に製造でき、安全で環境を汚染しないものである。
【0017】
【実施例】
以下、本発明の塑性加工前処理剤の実施例を詳細に説明する。
【0018】
先ず、層状複水酸化物を合成した。
【0019】
(合成例)
滴下漏斗、攪拌機、冷却管、pHメーターを備えた四つ口フラスコに、工業用ステアリン酸(ステアリン酸65%、パルミチン酸35%の混合物)5.21g、およびイオン交換水29.5gを入れ、これを70℃に加熱しながら、48%水酸化カリウム水溶液2.2gを加えてpH値10.81に調整したステアリン酸カリウム水溶液を調製した。硫酸マグネシウム7水和物12.1gおよび硫酸アルミニウム14水和物5.7gの混合物を20.1gのイオン交換水に加え、これを70℃に加熱し溶解させた混合金属水溶液を調製した。ステアリン酸カリウム水溶液に、この混合金属水溶液を滴下しながら、その反応混合液のpH値が8〜11になるように随時48%水酸化カリウム水溶液にて調整し、75〜80℃で保持して撹拌し混和した。滴下終了後、75〜80℃で6時間熟成を行なった。熟成後、生成した沈殿物を濾過し、イオン交換水で洗浄し、常温で乾燥すると、層間にインターカレートされた有機酸を有する層状複水酸化物が、13.2g得られた。この層状複水酸化物に含有されるMg2+およびAl3+を原子吸光度分析法により定量した。また、この層状複水酸化物に含有される有機酸は、酸分解法により定量した。なお、酸分解法とは、試料を5g量り取り、容量200mLの標線付きメスフラスコに入れ、次いで沸騰石を二、三個入れ、水を50mL加え、更に白塩酸(濃塩酸)を50mL加えて加熱沸騰させ、油分の分離を確認した後、油分が標線部に入るように温度約80℃で濃度約5%の食塩水を加え、標線上下の数値差から油分量を測定するというものである。
【0020】
その結果、層間に有機酸を有する層状複水酸化物は、
Mg2.6Al1.0(OH)7.2(Stearate)1.0・3.5H2Oという組成式で示されるものであると同定された。
【0021】
実施例1および2は、本発明を適用する塑性加工前処理剤を調製した例である。比較例1〜4は本発明を適用外の金属石鹸製塑性加工前処理剤の調製例である。
【0022】
(実施例1)
合成例1で得た層状複水酸化物100重量部に、添加剤として硫酸カリウム138重量部、イソブチレン/無水マレイン酸コポリマー24重量部、アルキルポリオキシエチレンエーテルカルボン酸14重量部、アラビアゴム14重量部、ベントナイト0.05重量、およびアクリル/マレイン酸共重合体の水酸化カリウム中和物0.05重量部を加え、固形分として10%となるように水で希釈し、常温でホモミキサーにより均一にミキシングし、処理剤を得た。
【0023】
(実施例2)
合成例1で得られた層状複水酸化物100重量部に、イソブチレン/無水マレイン酸コポリマー24重量部、アルキルポリオキシエチレンエーテルカルボン酸14重量部、アラビアゴム14重量部、ベントナイト0.05重量部、およびアクリル/マレイン酸共重合体の水酸化カリウム中和物0.05重量部を加え、固形分として10%となるように水で希釈し、常温でホモミキサーにより均一にミキシングし、処理剤を得た。
【0024】
(比較例1)
ステアリン酸マグネシウム100重量部、ステアリン酸アルミニウム57重量部、および硫酸カリウム138重量部の混合物に、実施例1と同じ重量比の添加剤を加え、固形分として10%となるように水で希釈し、常温でホモミキサーにより均一にミキシングし、処理剤を得た。
【0025】
(比較例2)
ステアリン酸マグネシウム100重量部、硫酸カリウム138重量部の混合物に、実施例1と同じ重量比の添加剤を加え、固形分として10%となるように水で希釈し、常温でホモミキサーにより均一にミキシングし、処理剤を得た。
【0026】
(比較例3)
ステアリン酸アルミニウム100重量部、硫酸カリウム138重量部の混合物に、実施例1と同じ重量比の添加剤を加え、固形分として10%となるように水で希釈し、常温でホモミキサーにより均一にミキシングし、処理剤を得た。
【0027】
(比較例4)
ステアリン酸カルシウム100重量部、硫酸カリウム138重量部の混合物に、実施例1と同じ重量比の添加剤を加え、固形分として10%となるように水で希釈し、常温でホモミキサーにより均一にミキシングし、処理剤を得た。
【0028】
実施例1〜2、比較例1〜4の処理剤を用いて、試験片に前処理である被膜処理を施し、その物性評価を行った。
【0029】
(被膜処理)
試験片は、SUS−304製で35×50×0.5mmの金属片であり、機械研磨などを施していないものである。実施例1〜2および比較例1〜4の処理剤の150mlを各々ビーカーに取り、温度60℃に加温し保温した。試験片を1枚毎、各ビーカー中の処理剤に1分間浸漬した後、取り出し、60℃で10分間乾燥し、被膜を形成させた試験片を得た。
【0030】
(物性評価方法)
この被膜を形成させた試験片について、バ−デンレーベン式往復摩擦摩耗試験機により物性評価を行った。試験条件は、荷重;49N(5kg)、摺動速度;20mm/sec、摺動距離;10mm、球形(材質);10mm(SUJ2)である。被膜が破断するまでの摺動回数を計測した。その摩擦摩耗試験の結果を、図1に示す。
【0031】
図1から明かなとおり、実施例1、2で得た処理剤は、比較例1〜4で得た処理剤に比べて、摩擦係数が低く、被膜が破断するまでの摺動回数が多かった。したがって、耐極圧性および展着性に優れるものであることが確認された。
【0032】
【発明の効果】
以上、詳細に説明したように本発明の塑性加工前処理剤を用いると、引抜加工等の塑性加工を施す金属原材に、優れた防錆性、潤滑性、耐極圧性および展着性を有する被膜を簡便かつ堅固に形成させることができる。
【0033】
予めこの前処理剤で被膜が形成された鉄、鋼、ステンレス鋼等金属原材は、円滑に、引抜加工やプレス加工等の塑性加工が施される。また、必要に応じて用いられる乾式、水溶性または油性の潤滑剤とこの被膜とが馴染み易いので、一層潤滑性が向上する。
【0034】
この前処理剤は、ホウ素、リン、フッ素元素を含まないので、作業環境の悪化や自然環境の汚染を引き起こさず、安全である。
【図面の簡単な説明】
【図1】本発明を適用する塑性加工前処理剤、および本発明を適用外の塑性加工前処理剤で被膜を形成させた金属片の摩擦摩耗試験の結果を示す図である。[0001]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD The present invention relates to a plastic working pretreatment agent used for a metal raw material subjected to plastic working such as drawing.
[0002]
[Prior art]
Metal raw materials such as iron, steel and stainless steel are subjected to plastic working such as drawing and press working to become molded products.
[0003]
Metallic raw materials are phosphate, borate, fluorine, etc., after acid cleaning and mechanical grinding of the surface metal oxide film, to provide appropriate lubricity and rust prevention and to facilitate plastic working. A film is formed in advance with a plastic working pretreatment agent containing a resin, lime soap, oxalate, and the like, and plastic working is performed in the presence of a lubricant as necessary. For example, Patent Document 1 discloses a pretreatment agent containing a phosphate or the like, Patent Document 2 discloses a pretreatment agent containing a borate, and Patent Document 3 discloses a pretreatment agent containing a metal soap.
[0004]
[Patent Document 1] JP-A-6-212444 [Patent Document 2] JP-A-2000-345361 [Patent Document 3] JP-A-63-69889 [0005]
Phosphates, borates, fluorinated resins, etc. may cause deterioration of the working environment and pollution of the natural environment. Therefore, a phosphate-free, pre-treating agent with better lubricity and rust prevention is desired. I was
[0006]
[Problems to be solved by the invention]
The present invention has been made in order to solve the above-mentioned problems, and does not contain elements such as boron, phosphorus, and fluorine, and provides a plastic working pretreatment agent capable of imparting appropriate lubricity and rust prevention to a metal raw material. The purpose is to provide.
[0007]
[Means for Solving the Problems]
The plastic working pretreatment agent of the present invention, which has been made to achieve the above object, comprises a double hydroxide comprising at least a monovalent and / or trivalent metal ion, a divalent metal ion and a hydroxide ion. It contains a layered double hydroxide that forms a layer and intercalates the organic acid between the layers.
[0008]
This plastic processing pretreatment agent has both the mechanical strength and heat resistance of the layered double hydroxide as the host, and the lubricity of the organic acid as the guest, and forms a coating excellent in extreme pressure resistance and spreadability. It is formed on a metal raw material.
[0009]
The organic acid is a monocarboxylic acid represented by R 1 —COOH (R 1 — is an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, or an unsubstituted or alkyl-substituted phenyl group). It is preferable that stearic acid, oleic acid, and palmitic acid be used. Organic acids, R 2 -SO 3 H (R 2 - is R 1 - same as) may be a monosulfonic acid represented by dodecyl sulfate, dodecyl benzene sulfate and the like and more specifically. The organic acid, HOOC-R 3 -COOH (-R 3 - is either an alkyl group, an alkenyl group having 2 to 24 carbon atoms, an unsubstituted or alkyl-substituted phenylene group 0-24 carbon atoms) a And more specifically, oxalic acid, maleic acid, and fumaric acid.
[0010]
The monovalent metal ion is Li + , the divalent metal ion is Mg 2+ , Zn 2+ , Ca 2+ , Cu 2+ , Zr 2+ , Co 2+ , Ni 2+ , Fe 2+ , or Mn 2+ , the trivalent metal ion Is preferably Al 3+ , Fe 3+ , or Co 3+ . The double hydroxide layer is formed from these ions and hydroxide, and more preferably, is formed from Mg 2+ , Al 3+ and hydroxide ions.
[0011]
The plastic working pretreatment agent may include potassium sulfate, and may include additives such as a spreading aid, a dispersant, and a rust inhibitor. It is preferable that potassium sulfate and additives are contained in an amount of 0.05 to 138 parts by weight based on 100 parts by weight of the layered double hydroxide.
[0012]
Spreading and dispersing agents include isobutylene / maleic anhydride copolymer, alkyl polyoxyethylene ether carboxylic acid, gum arabic, carboxymethyl cellulose, dextrin, sodium polyacrylate, acrylic acid / maleic acid copolymer, acrylic acid / sulfonic acid Preferred are a monomer copolymer, polyvinylpyrrolidone, hexaethylene glycol (HEG), and bentonite. Among them, isobutylene / maleic anhydride copolymer, alkyl polyoxyethylene ether carboxylic acid, gum arabic and bentonite are more preferable.
[0013]
The plastic working pretreatment agent includes, for example, a water-soluble salt of a monovalent and / or trivalent metal, a water-soluble salt of a divalent metal or an oxide of a divalent metal, an organic acid and / or a metal salt thereof. Are mixed in alkaline water, and the resulting layered double hydroxide is fractionated.
[0014]
The plastic working pretreatment agent may be in the form of a powder, but is preferably a treatment solution in which the layered double hydroxide is diluted and suspended with water and / or an organic solvent. More preferably, it is diluted with water. Even more preferably, it is diluted with water to have a solid content of 3 to 30%, preferably 5 to 15%.
[0015]
The plastic working pretreatment method using this pretreating agent is, for example, to apply, spray, or immerse the treatment liquid to bring it into contact with a metal material and then dry it. It is preferable that the treatment liquid is brought into contact with the metal material at a temperature of 60 ° C. or higher. Examples of the metal raw material include iron, steel, and stainless steel. Among them, stainless steel is particularly suitable.
[0016]
This plastic working pretreatment agent can be easily manufactured, is safe and does not pollute the environment.
[0017]
【Example】
Hereinafter, examples of the plastic working pretreatment agent of the present invention will be described in detail.
[0018]
First, a layered double hydroxide was synthesized.
[0019]
(Synthesis example)
In a four-necked flask equipped with a dropping funnel, a stirrer, a condenser, and a pH meter, 5.21 g of industrial stearic acid (a mixture of 65% stearic acid and 35% palmitic acid) and 29.5 g of ion-exchanged water were added. While heating the mixture to 70 ° C., 2.2 g of a 48% aqueous potassium hydroxide solution was added to adjust the pH value to 10.81 to prepare an aqueous potassium stearate solution. A mixture of 12.1 g of magnesium sulfate heptahydrate and 5.7 g of aluminum sulfate decahydrate was added to 20.1 g of ion-exchanged water, and the mixture was heated to 70 ° C. and dissolved to prepare a mixed metal aqueous solution. While the mixed metal aqueous solution was dropped into the potassium stearate aqueous solution, the reaction mixture was adjusted with a 48% aqueous potassium hydroxide solution as needed so that the pH value of the reaction mixture became 8 to 11, and kept at 75 to 80 ° C. Stir and mix. After completion of the dropwise addition, aging was performed at 75 to 80 ° C. for 6 hours. After aging, the resulting precipitate was filtered, washed with ion-exchanged water, and dried at room temperature, to obtain 13.2 g of a layered double hydroxide having an organic acid intercalated between layers. Mg 2+ and Al 3+ contained in this layered double hydroxide were quantified by atomic absorption spectrometry. The organic acid contained in the layered double hydroxide was quantified by an acid decomposition method. In the acid decomposition method, 5 g of a sample was weighed and placed in a 200-mL volumetric flask with a marked line, and then two or three boiling stones were added, 50 mL of water was added, and 50 mL of white hydrochloric acid (concentrated hydrochloric acid) was further added. After heating and boiling to confirm the separation of the oil, add about 5% saline solution at a temperature of about 80 ° C so that the oil enters the marked line, and measure the oil content from the numerical difference between the upper and lower lines. Things.
[0020]
As a result, the layered double hydroxide having an organic acid between the layers,
Mg 2.6 was identified as being Al 1.0 (OH) 7.2 (Stearate ) 1.0 · 3.5H 2 O as those represented by the composition formula.
[0021]
Examples 1 and 2 are examples in which a pretreatment agent for plastic working to which the present invention is applied was prepared. Comparative Examples 1 to 4 are preparation examples of metal soap plastic working pretreatment agents to which the present invention is not applied.
[0022]
(Example 1)
To 100 parts by weight of the layered double hydroxide obtained in Synthesis Example 1, 138 parts by weight of potassium sulfate, 24 parts by weight of isobutylene / maleic anhydride copolymer, 14 parts by weight of alkyl polyoxyethylene ether carboxylic acid, 14 parts by weight of gum arabic Parts, 0.05 parts by weight of bentonite, and 0.05 parts by weight of a neutralized potassium hydroxide of an acrylic / maleic acid copolymer, and diluted with water so as to have a solid content of 10%. The mixture was uniformly mixed to obtain a treating agent.
[0023]
(Example 2)
100 parts by weight of the layered double hydroxide obtained in Synthesis Example 1, 24 parts by weight of isobutylene / maleic anhydride copolymer, 14 parts by weight of alkyl polyoxyethylene ether carboxylic acid, 14 parts by weight of gum arabic, 0.05 parts by weight of bentonite , And 0.05 parts by weight of a neutralized potassium hydroxide of an acrylic / maleic acid copolymer, diluted with water to a solid content of 10%, and uniformly mixed at room temperature with a homomixer. Got.
[0024]
(Comparative Example 1)
An additive having the same weight ratio as in Example 1 was added to a mixture of 100 parts by weight of magnesium stearate, 57 parts by weight of aluminum stearate, and 138 parts by weight of potassium sulfate, and diluted with water to a solid content of 10%. The mixture was uniformly mixed at room temperature with a homomixer to obtain a treating agent.
[0025]
(Comparative Example 2)
An additive having the same weight ratio as in Example 1 was added to a mixture of 100 parts by weight of magnesium stearate and 138 parts by weight of potassium sulfate, diluted with water to a solid content of 10%, and homogenized at room temperature with a homomixer. Mixing was performed to obtain a treating agent.
[0026]
(Comparative Example 3)
An additive having the same weight ratio as in Example 1 was added to a mixture of 100 parts by weight of aluminum stearate and 138 parts by weight of potassium sulfate, diluted with water to a solid content of 10%, and homogenized at room temperature with a homomixer. Mixing was performed to obtain a treating agent.
[0027]
(Comparative Example 4)
An additive having the same weight ratio as in Example 1 was added to a mixture of 100 parts by weight of calcium stearate and 138 parts by weight of potassium sulfate, diluted with water to a solid content of 10%, and uniformly mixed at room temperature with a homomixer. Then, a treating agent was obtained.
[0028]
Using the treating agents of Examples 1 and 2 and Comparative Examples 1 to 4, the test pieces were subjected to a pre-coating treatment, and the physical properties thereof were evaluated.
[0029]
(Coating treatment)
The test piece is a metal piece of 35 × 50 × 0.5 mm made of SUS-304, which has not been subjected to mechanical polishing or the like. 150 ml of the treating agents of Examples 1 and 2 and Comparative Examples 1 to 4 were each placed in a beaker, and heated to a temperature of 60 ° C. and kept warm. Each test piece was immersed in the treatment agent in each beaker for 1 minute, taken out, and dried at 60 ° C. for 10 minutes to obtain a test piece on which a film was formed.
[0030]
(Physical property evaluation method)
The test pieces on which the coating was formed were evaluated for physical properties using a Baden-Leben type reciprocating friction and wear tester. The test conditions were as follows: load: 49 N (5 kg), sliding speed: 20 mm / sec, sliding distance: 10 mm, sphere (material): 10 mm (SUJ2). The number of times of sliding until the coating was broken was measured. FIG. 1 shows the results of the friction and wear test.
[0031]
As is clear from FIG. 1, the treating agents obtained in Examples 1 and 2 had a lower coefficient of friction and a larger number of times of sliding until the coating film was broken, as compared with the treating agents obtained in Comparative Examples 1 to 4. . Therefore, it was confirmed that they were excellent in extreme pressure resistance and spreadability.
[0032]
【The invention's effect】
As described in detail above, when the plastic working pretreatment agent of the present invention is used, the metal raw material subjected to plastic working such as drawing has excellent rust prevention, lubricity, extreme pressure resistance and spreadability. The coating can be easily and firmly formed.
[0033]
The metal raw material, such as iron, steel, and stainless steel, on which a film has been formed in advance with this pretreatment agent, is smoothly subjected to plastic working such as drawing or press working. Further, since the dry, water-soluble or oil-based lubricant used as required and the coating are easily compatible, the lubricity is further improved.
[0034]
Since this pretreatment agent does not contain elemental boron, phosphorus and fluorine, it does not cause deterioration of working environment or pollution of natural environment and is safe.
[Brief description of the drawings]
FIG. 1 is a diagram showing the results of a friction and wear test of a metal piece having a film formed with a plastic working pretreatment agent to which the present invention is applied and a plastic working pretreatment agent to which the present invention is not applied.
Claims (5)
Priority Applications (1)
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JP2003151086A JP2004351452A (en) | 2003-05-28 | 2003-05-28 | Plastic working pretreatment agent |
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JP2003151086A JP2004351452A (en) | 2003-05-28 | 2003-05-28 | Plastic working pretreatment agent |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006143834A (en) * | 2004-11-18 | 2006-06-08 | Kyoeisha Chem Co Ltd | Lubricant for plastic working |
WO2006068118A1 (en) * | 2004-12-22 | 2006-06-29 | Tayca Corporation | Layered double hydroxide peelable in water, and production process and use thereof |
JP2007039549A (en) * | 2005-08-03 | 2007-02-15 | Tayca Corp | Rust preventive coating material composition using layered composite hydroxide exfoliating in water |
JP2008184343A (en) * | 2007-01-29 | 2008-08-14 | Tayca Corp | Layered double hydroxide capable of being delaminated in water, its production method, and its use |
JP2010058187A (en) * | 2008-09-02 | 2010-03-18 | Three M Innovative Properties Co | Abrasive product containing clathrate compound |
-
2003
- 2003-05-28 JP JP2003151086A patent/JP2004351452A/en active Pending
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006143834A (en) * | 2004-11-18 | 2006-06-08 | Kyoeisha Chem Co Ltd | Lubricant for plastic working |
WO2006068118A1 (en) * | 2004-12-22 | 2006-06-29 | Tayca Corporation | Layered double hydroxide peelable in water, and production process and use thereof |
JPWO2006068118A1 (en) * | 2004-12-22 | 2008-06-12 | テイカ株式会社 | Layered double hydroxide that peels off in water, production method and use thereof |
JP5022038B2 (en) * | 2004-12-22 | 2012-09-12 | テイカ株式会社 | Layered double hydroxide that peels off in water, production method and use thereof |
US8388987B2 (en) | 2004-12-22 | 2013-03-05 | Tayca Corporation | Layered double hydroxides that delaminate in water, their manufacturing process and use |
JP2007039549A (en) * | 2005-08-03 | 2007-02-15 | Tayca Corp | Rust preventive coating material composition using layered composite hydroxide exfoliating in water |
JP2008184343A (en) * | 2007-01-29 | 2008-08-14 | Tayca Corp | Layered double hydroxide capable of being delaminated in water, its production method, and its use |
JP2010058187A (en) * | 2008-09-02 | 2010-03-18 | Three M Innovative Properties Co | Abrasive product containing clathrate compound |
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