JP3872492B2 - Water based lubricant coating agent for solids - Google Patents

Water based lubricant coating agent for solids Download PDF

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Publication number
JP3872492B2
JP3872492B2 JP2005160834A JP2005160834A JP3872492B2 JP 3872492 B2 JP3872492 B2 JP 3872492B2 JP 2005160834 A JP2005160834 A JP 2005160834A JP 2005160834 A JP2005160834 A JP 2005160834A JP 3872492 B2 JP3872492 B2 JP 3872492B2
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water
aqueous
film
lubricating film
component
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JP2006335838A (en
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忍 小見山
充 青山
健史 藤脇
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Nihon Parkerizing Co Ltd
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Nihon Parkerizing Co Ltd
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Priority to JP2005160834A priority Critical patent/JP3872492B2/en
Priority to PCT/JP2006/309457 priority patent/WO2006129457A1/en
Priority to CN2006800195963A priority patent/CN101189322B/en
Priority to KR1020077028087A priority patent/KR100973960B1/en
Publication of JP2006335838A publication Critical patent/JP2006335838A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04—Elements
    • C10M2201/041—Carbon; Graphite; Carbon black
    • C10M2201/0413—Carbon; Graphite; Carbon black used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/0603—Metal compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/08—Inorganic acids or salts thereof
    • C10M2201/084—Inorganic acids or salts thereof containing sulfur, selenium or tellurium
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/085—Phosphorus oxides, acids or salts
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/087—Boron oxides, acids or salts
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    • C10M2201/10—Compounds containing silicon
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/042—Epoxides
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/124—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms containing hydroxy groups; Ethers thereof
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/1253—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids used as base material
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084—Acrylate; Methacrylate
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/102—Polyesters
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    • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
    • C10M2213/003—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/2203—Heterocyclic nitrogen compounds used as base material
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    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/041—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving a condensation reaction
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    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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    • C10N2030/18—Anti-foaming property
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating

Description

本発明は、鍛造加工、伸線加工、プレス加工、ロールフォーミングなどに代表される金属の塑性加工時に固体表面間（特にダイスと被加工材との間）に生じる摩擦、エンジンやコンプレッサー内部の機械摺動面などで固体表面間（例えばシリンダーとピストンとの間）に生じる摩擦などの固体と固体との擦れ合いによって生じる摩擦の低減を目的として様々な用途/分野で必要とされる、固体（特に金属材料/金属製品）上に潤滑皮膜を形成するための、水系潤滑皮膜処理剤に関するものである。さらに詳しく述べるならば、本発明は、石けん類など優れた性能を有する潤滑成分を水性処理液に含有させるために、従来、処理液の発泡や皮膜性能への悪影響が問題とされていたにも関わらず多量の界面活性剤や高分子系分散剤などを併用しなければならなかったのに対して、発泡が非常に少なく、多量の潤滑成分を安定に含有させることができる、工業的な安定使用に優れた、固体に対する水系潤滑皮膜処理剤に関するものである。   The present invention relates to friction generated between solid surfaces (particularly between a die and a workpiece) during plastic processing of metal represented by forging, wire drawing, press working, roll forming, etc., and machinery inside an engine or compressor. Solid (required in various applications / fields for the purpose of reducing friction caused by friction between the solid and the solid, such as friction generated between the solid surfaces (for example, between the cylinder and the piston) on the sliding surface, etc. In particular, the present invention relates to a water-based lubricating film treating agent for forming a lubricating film on a metal material / metal product. More specifically, in the present invention, since a lubricating component having excellent performance such as soaps is included in the aqueous processing liquid, conventionally, adverse effects on the foaming of the processing liquid and the film performance have been problems. Despite the fact that a large amount of surfactants and polymer dispersants had to be used in combination, there was very little foaming and a large amount of lubricating components could be contained stably. The present invention relates to a water-based lubricant coating agent for solids, which is excellent in use.

固体表面、特に金属表面同士（特にダイスと被加工材）が激しく擦れ合う塑性加工時や、機械摺動部に生じる摩擦は、加工エネルギーの増大、発熱、焼付き現象などの原因となるため摩擦力低減を目指した様々な潤滑剤が用いられてきた。潤滑剤としては、古くから、油や石けん類などが用いられ、摺動面に供給することで流体潤滑膜として摩擦力を低減してきたが、表面積拡大による大きな発熱を伴い高面圧下で摺動する塑性加工や、機械摺動部の高速摺動面などでは潤滑性が不十分であったり、潤滑膜切れなどにより焼付き現象が発生し易くなる。そのため、潤滑膜切れによっても金属同士の直接接触を回避することができるように、ボラックス（ホウ砂）皮膜、リン酸塩結晶皮膜等の無機皮膜、樹脂皮膜などの固体皮膜で予め対象固体表面を被覆しておく技術が一般化され、広く用いられている。   Friction forces occur during plastic working where solid surfaces, particularly metal surfaces (especially dies and workpieces) rub against each other, and friction that occurs in the machine sliding part increases processing energy, generates heat, and seizes. Various lubricants aimed at reduction have been used. As lubricants, oil and soap have been used for a long time, and the frictional force has been reduced as a fluid lubrication film by supplying it to the sliding surface, but it slides under high surface pressure with large heat generation due to surface area expansion. Such plastic working and high-speed sliding surfaces of the machine sliding portion are insufficient in lubricity, and seizure phenomenon is liable to occur due to running out of the lubricating film. Therefore, in order to avoid direct contact between metals even when the lubricating film is cut, the target solid surface is previously coated with a solid film such as a borax film, an inorganic film such as a phosphate crystal film, or a resin film. The technique of coating is generalized and widely used.

一方、近年、加工・摺動エネルギーの更なる低減化や、強加工度化、難加工材への対応、皮膜プロセスの環境保全性（例えばリン酸塩処理はスラッジ等の産業廃棄物が多量に生じさせるので環境保全上問題がある）、潤滑パウダーレスやオイルレス加工への対応など、固体皮膜への要求は多岐に亘り急速に高まりつつあり、これらの要求に対して、環境保全を考慮する一方、高度な潤滑性を有する固体皮膜が開発されつつある。この技術は、被加工材や機械摺動部などの固体表面に対して液状の皮膜剤を付着させ、ついで乾燥するだけの簡便な工程によって高度な潤滑性を有する皮膜を形成させるものである。このような技術として、特許文献１に、（Ａ）合成樹脂、（Ｂ）水溶性無機塩および水を含有し、（Ｂ）／（Ａ）（固形分重量比）が０．２５／１〜９／１であって、合成樹脂が溶解または分散していることを特徴とする金属材料の塑性加工用潤滑剤組成物が開示されている。特許文献１には、潤滑成分として、金属石けん、ワックス、ポリテトラフルオロエチレンおよび油よりなる群から選ばれる少なくとも一種を１〜２０質量％含有させるのが好ましく、前記水溶性無機塩としては、硫酸塩、ホウ酸塩、モリブデン酸塩、バナジン酸塩およびタングステン酸塩よりなる群から選ばれる少なくとも一種が好ましいことも記載されている。この技術は、キャリアとなり得る皮膜成分中に金属石けんやワックスなどの潤滑成分を分散した形で含有し、これを被加工材表面にコーティングすることで、高度な加工性能を有する潤滑皮膜を簡便かつ省力的に得ることができる優れた技術である。この技術によれば、潤滑成分が無機塩や樹脂成分によって皮膜中に固定化されているために、上述した「固体皮膜＋潤滑成分」に比べて固体表面に対する潤滑剤の濡れ性や層間密着性などに影響されず、より安定した潤滑状態を提供できるものである。また、この技術は主に塑性加工分野で広く用いられており、比較的大きな結晶単位の潤滑皮膜であるリン酸塩皮膜と石けんとの組み合わせと比較しても、潤滑成分の機能別選定、分散状態などによって潤滑成分の効果を任意に調整できる利点を有することから、この技術を基に、表面積拡大が大きい強加工用途にも優れた技術が開発されつつあり有望な技術である。
特開２０００−０６３８８０号公報 On the other hand, in recent years, the processing and sliding energy has been further reduced, the degree of workability has been increased, difficult-to-process materials can be handled, and the environmental conservation of the coating process (for example, phosphating has resulted in a large amount of industrial waste such as sludge. There is a problem in environmental conservation because of the generation), and demands for solid coatings are increasing rapidly, such as response to lubrication powderless and oilless processing, and environmental conservation is considered for these requirements On the other hand, solid coatings having high lubricity are being developed. In this technique, a liquid film agent is attached to a solid surface such as a workpiece or a machine sliding portion, and then a film having high lubricity is formed by a simple process of drying. As such a technique, Patent Document 1 contains (A) a synthetic resin, (B) a water-soluble inorganic salt and water, and (B) / (A) (solid content weight ratio) is 0.25 / 1 to 1. A lubricant composition for plastic working of a metal material, which is 9/1 and has a synthetic resin dissolved or dispersed therein, is disclosed. In Patent Document 1, it is preferable to contain 1 to 20% by mass of at least one selected from the group consisting of metal soap, wax, polytetrafluoroethylene and oil as a lubricating component, and the water-soluble inorganic salt includes sulfuric acid. It is also described that at least one selected from the group consisting of a salt, borate, molybdate, vanadate and tungstate is preferable. This technology contains a lubricant component such as metal soap or wax dispersed in a coating component that can be a carrier, and by coating this on the surface of the work material, a lubricating coating having a high level of processing performance can be easily and easily obtained. It is an excellent technology that can be obtained labor-saving. According to this technology, since the lubricating component is fixed in the film by an inorganic salt or a resin component, the wettability and interlayer adhesion of the lubricant to the solid surface compared to the above-described “solid film + lubricating component”. It is possible to provide a more stable lubrication state without being affected by the above. In addition, this technology is widely used mainly in the field of plastic working, and it is possible to select and disperse lubricating components according to their functions, even when compared to a combination of a phosphate film and soap, which is a relatively large crystal unit lubricating film. Since it has an advantage that the effect of the lubricating component can be arbitrarily adjusted depending on the state or the like, based on this technology, an excellent technology is being developed for strong processing applications with a large surface area expansion, which is a promising technology.
JP 2000-063880 A

しかし、潤滑成分として用いられている多くの物質は、疎水性、もしくは水への溶解度が乏しく、例えば、アルカリ石けんは冷間鍛造時の金型（ダイス）保護性能に優れているとされているが、水性液への溶解度が低いために多くを配合できないほか、極端な発泡の原因となり、また、金属石けんなどは疎水性が強く、水性液への分散が難しい。したがって、特許文献１の技術においては、実用レベルで潤滑成分を水性液中に含有させるためには界面活性剤や高分子分散剤などを多量に共存させて分散化する必要があるが、界面活性剤や高分子分散剤などを多量に共存させるとそこにも発泡の問題が生じ、また皮膜性能の低下（例えば耐水性の低下、皮膜形成時の界面活性剤や高分子分散剤の偏析による潤滑性能の不均一化など）の問題が生じる傾向となり、他方、界面活性剤や高分子分散剤などの助けを借りずに潤滑成分含有量を高めようとすると潤滑皮膜処理剤の安定性が損われる傾向となる。   However, many substances used as lubricating components are hydrophobic or poorly soluble in water. For example, alkali soap is said to have excellent die (die) protection performance during cold forging. However, since it has a low solubility in aqueous liquid, it cannot be added in a large amount and causes extreme foaming. Metal soap and the like are highly hydrophobic and difficult to disperse in aqueous liquid. Therefore, in the technique of Patent Document 1, in order to contain a lubricating component in an aqueous liquid at a practical level, it is necessary to disperse in a large amount of a surfactant or a polymer dispersant. Coexistence of a large amount of agents and polymer dispersants also causes foaming problems and decreases film performance (for example, water resistance, lubrication due to segregation of surfactants and polymer dispersants during film formation) On the other hand, if the content of the lubricating component is increased without the aid of a surfactant or a polymer dispersant, the stability of the lubricant film treatment agent is impaired. It becomes a trend.

本発明は、上記従来技術が抱える問題点を解決するものであり、発泡が少なく、多量の潤滑成分を含有することができるにも拘らず、液安定性に優れた、主として金属材料のための水系潤滑皮膜処理剤を提供することを目的とする。   The present invention solves the above-mentioned problems of the prior art, and is excellent for liquid stability, mainly for metal materials, although it has less foaming and can contain a large amount of lubricating components. An object of the present invention is to provide a water-based lubricating film treating agent.

上記課題は、一般式（Ｉ）
Ｒ１−ＣＨ（Ｒ２）ＣＯＯＨ （Ｉ）
（式中、Ｒ１及びＲ２はそれぞれ独立に炭素数４〜１２で、直鎖もしくは分岐鎖のアルキル基を示す）で表され、流動点が０℃未満である分岐カルボン酸及び／又はその塩（Ａ）と、固体皮膜成分（Ｂ）とを配合してなる、固体に対する水系潤滑皮膜処理剤であって、水系潤滑皮膜処理剤の全固形分を基準にして、それぞれ固形分として、分岐カルボン酸もしくはその塩の配合量が０．１〜５０質量％であり、固体皮膜成分の配合量が３〜９９．９質量％である該水系潤滑皮膜処理剤によって解決される。固体皮膜成分としては、通常、水性無機塩、水性有機酸塩及び水性樹脂から選ばれる少なくとも一種が用いられる。本水系潤滑皮膜処理剤には、油、石けん、金属石けん、ワックス及びポリテトラフルオロエチレンから選ばれる少なくとも一種を潤滑性の調整のための補足成分（補足成分（Ｃ））として配合し得る。また、本水系潤滑皮膜処理剤には、強加工用途での耐焼付き性向上、ダイス保護及び／又は潤滑性補助を目的として、二硫化モリブデン、グラファイト、カーボンブラック、有機モリブデン化合物、リン酸亜鉛化合物、石灰、メラミンシアヌレート及び窒化ホウ素から選ばれる少なくとも一種を補足成分（Ｄ）として配合し得る。本発明は、また、該水系潤滑皮膜処理剤より形成される潤滑皮膜を表面に有する金属材料に関する。 The above problem is solved by the general formula (I)
R 1 —CH (R 2 ) COOH (I)
(Wherein R 1 and R 2 each independently represents a linear or branched alkyl group having 4 to 12 carbon atoms) and a pour point is less than 0 ° C. and / or its A water-based lubricating film treatment agent for a solid, comprising a salt (A) and a solid film component (B), each branched as a solid content based on the total solid content of the water-based lubricating film treatment agent This is solved by the water-based lubricating film treating agent in which the compounding amount of carboxylic acid or a salt thereof is 0.1 to 50% by mass and the compounding amount of the solid film component is 3 to 99.9% by mass. As the solid film component, at least one selected from aqueous inorganic salts, aqueous organic acid salts and aqueous resins is usually used. At least one selected from oil, soap, metal soap, wax, and polytetrafluoroethylene can be blended in the water-based lubricating film treating agent as a supplemental component (supplementary component (C)) for adjusting lubricity. In addition, the present water-based lubricant coating treatment agent is molybdenum disulfide, graphite, carbon black, organic molybdenum compound, zinc phosphate compound for the purpose of improving seizure resistance in strong processing applications, die protection and / or lubricating aid. At least one selected from lime, melamine cyanurate and boron nitride can be blended as the supplemental component (D). The present invention also relates to a metal material having on its surface a lubricating film formed from the aqueous lubricant film treating agent.

本発明の水系潤滑皮膜処理剤は、耐発泡性、処理液安定性など、工業的な安定使用に必要な性能において特に優れている上に、十分な量の潤滑成分を含有することができ、さらに本発明の水系潤滑皮膜処理剤から形成される皮膜は摺動潤滑皮膜や冷間鍛造用潤滑皮膜として良好な性能を発揮するものである。したがって、本発明は産業上の利用価値が極めて大きい。   The water-based lubricating film treatment agent of the present invention is particularly excellent in performance necessary for industrial stable use, such as foam resistance and processing solution stability, and can contain a sufficient amount of a lubricating component, Furthermore, the film formed from the water-based lubricating film treating agent of the present invention exhibits good performance as a sliding lubricating film or a cold forging lubricating film. Therefore, the present invention has extremely great industrial utility value.

以下、本発明を詳細に説明する。
本発明における一般式（Ｉ）で表される分岐カルボン酸［以下、分岐カルボン酸（Ｉ）という；他の一般式の化合物についても同様］中のＲ１及びＲ２は、それぞれ独立に、炭素数４〜１２の直鎖もしくは分岐鎖アルキル基であることが必要であるが、炭素数５〜１０の直鎖もしくは分岐鎖アルキル基であることが好ましい。Ｒ１及び／又はＲ２の炭素数が３以下又は１３以上である場合には、親水基と疎水基とのバランスが適切な範囲を外れて、十分な消泡性能や分散性能を発現し得なくなる傾向にある。Ｒ１及び／又はＲ２は具体例としては、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、イソペンチル基、２−メチルブチル基、イソヘキシル基、３−メチルペンチル基、ｎ−ヘキシル基、１−メチル−３，３−ジメチルブチル基、３−メチルヘキシル基、４−メチルヘキシル基、イソヘプチル基、３−メチルヘプチル基、４−メチルヘプチル基、５−メチルヘプチル基、イソオクチル基、ｎ−オクチル基、３−メチル−５，５−ジメチルヘキシル基、４−メチルオクチル基、５−メチルオクチル基、６−メチルオクチル基、４−メチルノニル基、５−メチルノニル基、６−メチルノニル基、５−メチルデシル基、６−メチルウンデシル基等が挙げられる。 Hereinafter, the present invention will be described in detail.
R 1 and R 2 in the branched carboxylic acid represented by general formula (I) in the present invention [hereinafter referred to as branched carboxylic acid (I); the same applies to compounds of other general formulas] are each independently carbon. Although it is necessary that it is a linear or branched alkyl group having 4 to 12 carbon atoms, a linear or branched alkyl group having 5 to 10 carbon atoms is preferable. When the carbon number of R 1 and / or R 2 is 3 or less or 13 or more, the balance between the hydrophilic group and the hydrophobic group is out of an appropriate range, and sufficient defoaming performance and dispersion performance can be exhibited. It tends to disappear. Specific examples of R 1 and / or R 2 include n-butyl group, isobutyl group, sec-butyl group, isopentyl group, 2-methylbutyl group, isohexyl group, 3-methylpentyl group, n-hexyl group, 1- Methyl-3,3-dimethylbutyl group, 3-methylhexyl group, 4-methylhexyl group, isoheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, isooctyl group, n-octyl group 3-methyl-5,5-dimethylhexyl group, 4-methyloctyl group, 5-methyloctyl group, 6-methyloctyl group, 4-methylnonyl group, 5-methylnonyl group, 6-methylnonyl group, 5-methyldecyl group , 6-methylundecyl group and the like.

分岐カルボン酸（Ｉ）の中で以下の一般式（Ｉ−１）で表される分岐カルボン酸が本発明で使用するのにより好ましい。一般式（Ｉ−１）において、Ｒ３及びＲ４はそれぞれ独立に水素原子又は炭素数１〜７の直鎖もしくは分岐鎖アルキル基であることができるが、両基の炭素数は合計で２〜７であることを要する。これらのうち、Ｒ３が炭素数２〜５の直鎖アルキル基でＲ４が水素原子である分岐カルボン酸（Ｉ−１）、Ｒ３が炭素数３〜７の分岐鎖アルキル基でＲ４が水素原子である分岐カルボン酸（Ｉ−１）及びＲ３が炭素数３〜６の分岐鎖アルキル基でＲ４がメチル基である分岐カルボン酸（Ｉ−１）がより好ましい。ここで炭素数１〜７の直鎖もしくは分岐鎖アルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、２−メチルペンチル基、３−メチルペンチル基、２−メチルヘキシル基、３−メチルヘキシル基、４−メチルヘキシル基等が挙げられる。 Among the branched carboxylic acids (I), a branched carboxylic acid represented by the following general formula (I-1) is more preferable for use in the present invention. In the general formula (I-1), R 3 and R 4 can be each independently a hydrogen atom or a linear or branched alkyl group having 1 to 7 carbon atoms. It must be ~ 7. Of these, branched carboxylic acid R 4 is a hydrogen atom a straight-chain alkyl group R 3 is 2 to 5 carbon atoms (I-1), R 4 R 3 is branched chain alkyl group having from 3 to 7 carbon atoms The branched carboxylic acid (I-1) in which is a hydrogen atom and the branched carboxylic acid (I-1) in which R 3 is a branched alkyl group having 3 to 6 carbon atoms and R 4 is a methyl group are more preferable. Here, as the linear or branched alkyl group having 1 to 7 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, Examples include n-pentyl group, isopentyl group, neopentyl group, 2-methylpentyl group, 3-methylpentyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group and the like.

Figure 0003872492
Figure 0003872492

本発明で使用する分岐カルボン酸は、また、その流動点が０℃未満でなければならず、−１℃以下であることが好ましく、−１５℃以下であることがより好ましい。本発明で使用する分岐カルボン酸の流動点の下限については特に制限はない。   The branched carboxylic acid used in the present invention must have a pour point of less than 0 ° C, preferably -1 ° C or less, and more preferably -15 ° C or less. There is no restriction | limiting in particular about the minimum of the pour point of the branched carboxylic acid used by this invention.

本発明で使用する分岐カルボン酸の具体例として、以下のような化合物が挙げられるが、本発明で使用する分岐カルボン酸はこれらに限定されるものではない。   Specific examples of the branched carboxylic acid used in the present invention include the following compounds, but the branched carboxylic acid used in the present invention is not limited thereto.

Figure 0003872492
Figure 0003872492

分岐カルボン酸（Ｉ−１−１）〜分岐カルボン酸（Ｉ−１−５）の流動点は以下の通りである。
分岐カルボン酸（Ｉ−１−１）：−３０℃以下、分岐カルボン酸（Ｉ−１−２）：−１７℃、分岐カルボン酸（Ｉ−１−３）：−３０℃以下、分岐カルボン酸（Ｉ−１−４）：−３０℃以下、分岐カルボン酸（Ｉ−１−５）：−１℃。
なお、分岐カルボン酸（Ｉ−１−１）〜分岐カルボン酸（Ｉ−１−５）はすべて分岐カルボン酸（Ｉ−１）に包含される。 The pour points of branched carboxylic acid (I-1-1) to branched carboxylic acid (I-1-5) are as follows.
Branched carboxylic acid (I-1-1): -30 ° C or lower, branched carboxylic acid (I-1-2): -17 ° C, branched carboxylic acid (I-1-3): -30 ° C or lower, branched carboxylic acid (I-1-4): -30 ° C or lower, branched carboxylic acid (I-1-5): -1 ° C.
In addition, all branched carboxylic acid (I-1-1)-branched carboxylic acid (I-1-5) is included by branched carboxylic acid (I-1).

分岐カルボン酸（Ｉ）の炭素数及び流動点が上記範囲内にある場合、かかる分岐カルボン酸（Ｉ）もしくはその塩を含有する水系潤滑皮膜処理剤は、発泡が少なく、液安定性に優れ、多量の潤滑成分を含有させることができると共に、良好な潤滑性を有する皮膜を形成するという本発明の効果を達成し得る。   When the carbon number and pour point of the branched carboxylic acid (I) are within the above range, the aqueous lubricant coating agent containing the branched carboxylic acid (I) or a salt thereof has less foaming and excellent liquid stability. A large amount of a lubricating component can be contained, and the effect of the present invention of forming a film having good lubricity can be achieved.

分岐カルボン酸（Ｉ）は、（１）植物油（大豆油、トール油等）、動物油（牛脂等）からの脂肪酸からダイマー酸を製造する際の副生物としてダイマー酸から分離する；（２）オレフィンをオキソ反応に付して得られるアルデヒドをアルドール縮合に付し、得られる炭素−炭素二重結合を有するアルデヒドを水素添加してアルコールとし、これを酸化する等の方法により得ることができる。
これらの方法の内、（２）の方法は以下の反応工程式で表すことができる。なお、以下の反応工程式において、Ｒ３及びＲ４は分岐カルボン酸（Ｉ−１）におけると同義である。 Branched carboxylic acid (I) is separated from dimer acid as a by-product in producing dimer acid from fatty acids from (1) vegetable oil (soybean oil, tall oil, etc.) and animal oil (beef tallow, etc.); (2) olefins Can be obtained by subjecting an aldehyde obtained by subjecting to an oxo reaction to aldol condensation, hydrogenating the resulting aldehyde having a carbon-carbon double bond to give an alcohol, and oxidizing this.
Among these methods, the method (2) can be represented by the following reaction process formula. In the following reaction process formula, R 3 and R 4 have the same meaning as in the branched carboxylic acid (I-1).

Figure 0003872492
Figure 0003872492

本発明で使用する分岐カルボン酸の塩としては、ナトリウム、カリウム、リチウムなどのアルカリ金属との塩；カルシウム、マグネシウムなどのアルカリ土類金属との塩；メチルアミン、エチルアミン、プロピルアミンなどの脂肪族アミンとの塩；モノエタノールアミン、ジエタノールアミン、トリエタノールアミンなどのアルカノールアミンとの塩；アンモニウム塩等が挙げられる。これらの塩の中で、アルカリ金属との塩及びアンモニウム塩がより好ましい。
本発明で使用する分岐カルボン酸及びその塩は、各単独で、もしくは２種以上組み合わせて用いることができる。 Examples of the salt of the branched carboxylic acid used in the present invention include salts with alkali metals such as sodium, potassium and lithium; salts with alkaline earth metals such as calcium and magnesium; aliphatics such as methylamine, ethylamine and propylamine. Salts with amines; Salts with alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; ammonium salts and the like. Among these salts, alkali metal salts and ammonium salts are more preferable.
The branched carboxylic acids and salts thereof used in the present invention can be used alone or in combination of two or more.

本発明で使用する分岐カルボン酸及び／又はその塩、すなわち分岐カルボン酸及び／又はその塩（Ａ）は、本発明の水系潤滑皮膜処理剤中に溶解状態、または分散状態で含有させる。なお、水系潤滑皮膜処理剤により形成される潤滑皮膜における分岐カルボン酸及び／又はその塩（Ａ）は、皮膜中や皮膜上層に分布することで潤滑皮膜に優れた潤滑性を付与する。また、分岐カルボン酸及び／又はその塩（Ａ）は、潤滑皮膜中で多価金属化合物と共存した場合には、複分解反応生成物としても存在し得る。例えば、リン酸亜鉛結晶との共存下ではリン酸亜鉛結晶表面に分岐カルボン酸の亜鉛化合物が析出し、石灰粒子の共存下では分岐カルボン酸のカルシウム化合物が析出することによって、これら多価金属化合物表面に優れた潤滑性を付与する。   The branched carboxylic acid and / or salt thereof used in the present invention, that is, the branched carboxylic acid and / or salt (A) is contained in the aqueous lubricant film treating agent of the present invention in a dissolved state or in a dispersed state. In addition, the branched carboxylic acid and / or its salt (A) in the lubricating film formed by the water-based lubricating film treating agent impart excellent lubricity to the lubricating film by being distributed in the film or in the upper layer of the film. Further, the branched carboxylic acid and / or salt (A) thereof may also exist as a metathesis reaction product when coexisting with the polyvalent metal compound in the lubricating film. For example, a zinc compound of a branched carboxylic acid precipitates on the surface of the zinc phosphate crystal in the presence of the zinc phosphate crystal, and a calcium compound of the branched carboxylic acid precipitates in the presence of lime particles, so that these polyvalent metal compounds Gives excellent lubricity to the surface.

分岐カルボン酸及び／又はその塩（Ａ）は、水系潤滑皮膜処理剤中に共存し得る各種潤滑成分に対する優れた分散剤として機能するため、各種潤滑成分の分散安定性を飛躍的に高めることができる。このため、各種潤滑成分の分散安定性を高めるべく多量に用いることで発泡や皮膜性能の低下の原因となってきた界面活性剤や高分子分散剤などの併用を必要としないか、大幅に低減することができる。さらに、分岐カルボン酸及び／又はその塩（Ａ）は、優れた消泡剤としても機能するため、アルカリ石けん類などの潤滑成分、界面活性剤、高分子分散剤などからの発泡を高度に抑制することができる。   The branched carboxylic acid and / or salt thereof (A) functions as an excellent dispersant for various lubricating components that can coexist in the aqueous lubricating film treating agent, and thus dramatically improves the dispersion stability of various lubricating components. it can. For this reason, the use of a large amount to increase the dispersion stability of various lubricating components does not require the use of surfactants or polymer dispersants that have caused foaming or reduced film performance, or greatly reduces them. can do. Furthermore, the branched carboxylic acid and / or its salt (A) also functions as an excellent antifoaming agent, and therefore highly suppresses foaming from lubricating components such as alkali soaps, surfactants and polymer dispersants. can do.

分岐カルボン酸及び／又はその塩（Ａ）の含有量は、水系潤滑皮膜処理剤の全固形分に対する固形分の割合として、０．１〜５０質量％の範囲で用いるのが好ましく、０．３〜３０質量％の範囲で用いるのがより好ましい。０．１〜５０質量％未満では、その添加による効果、すなわち潤滑性機能、消泡剤機能、分散剤機能が働かず、５０質量％を超えると、これらの機能が飽和し経済的に無駄となる。   The content of the branched carboxylic acid and / or its salt (A) is preferably used in the range of 0.1 to 50% by mass as the ratio of the solid content to the total solid content of the aqueous lubricant film treatment agent, It is more preferable to use in the range of ˜30% by mass. If the amount is less than 0.1 to 50% by mass, the effect of the addition, that is, the lubricity function, the antifoaming agent function and the dispersant function do not work. If the amount exceeds 50% by mass, these functions are saturated and economically wasteful. Become.

本発明の水系潤滑皮膜処理剤における必須成分である固体皮膜成分（Ｂ）としては、水性無機塩、水性有機酸塩、水性樹脂から選ばれる少なくとも一種を用いることができる。ここで「水性」は水溶性又は水分散性を意味する。固体皮膜成分（Ｂ）は、予め対象表面に被覆させておくことで、金属の塑性加工時や機械摺動面の流体潤滑膜切れ時などに金属同士の直接接触を回避し焼付き現象を発生させない役割を有する。固体皮膜成分（Ｂ）は、また、油、石けん 類、ワックス類、二硫化モリブデン、グラファイト、リン酸亜鉛化合物、石灰、メラミンシアヌレートなどを皮膜中に保持することで、潤滑皮膜表面に摩擦係数を低減化するなどの潤滑性を付与したり、潤滑成分や耐焼付き成分などを摩擦摺動面に供給する役割を担っている。本発明の水系潤滑皮膜処理剤中での固体皮膜成分（Ｂ）は水に溶解もしくは分散した状態で存在し、水分が揮発することにより常温では固体状の皮膜を形成する。   As the solid film component (B) that is an essential component in the aqueous lubricant film treatment agent of the present invention, at least one selected from aqueous inorganic salts, aqueous organic acid salts, and aqueous resins can be used. Here, “aqueous” means water-soluble or water-dispersible. Solid film component (B) is coated on the target surface in advance to avoid seizure phenomenon by avoiding direct contact between metals during plastic processing of metal or when the fluid lubrication film on the sliding surface of the machine runs out. Have a role not to let. The solid film component (B) also has a coefficient of friction on the surface of the lubricating film by retaining oil, soaps, waxes, molybdenum disulfide, graphite, zinc phosphate compounds, lime, melamine cyanurate, etc. in the film. It plays a role of providing lubricity such as reducing friction and supplying a lubricating component and an anti-seizure component to the friction sliding surface. The solid film component (B) in the water-based lubricating film treatment agent of the present invention exists in a state of being dissolved or dispersed in water, and forms a solid film at room temperature by volatilization of moisture.

固体皮膜成分（Ｂ）は形成させる潤滑皮膜の用途によって任意に選ぶことができる。例えば、摩擦摺動面の温度、圧力が非常に高い冷間鍛造用途の場合には、皮膜の溶融点が加工時の材料到達温度に比べて高く加工熱の影響を受け難く、上記役割を安定的に示すことができることから水性無機塩を用いることが好ましい。このような性質を持つ水性無機塩としては、硫酸塩、ホウ酸類の塩、ケイ酸類の塩及びリン酸類の塩から選ばれる少なくとも一種を使用することが好ましい。ホウ酸類はオルトホウ酸（Ｈ３ＢＯ３）、メタホウ酸（ＨＢＯ２）、四ホウ酸（Ｈ２Ｂ４Ｏ７）、五ホウ酸（ＨＢ５Ｏ８）などを包含する。ケイ酸類はオルトケイ酸（ｎＳｉＯ２・（ｎ＋１）Ｈ２Ｏ）、メタケイ酸（ｎＳｉＯ２・ｎＨ２Ｏ）、メソケイ酸（ｎＳｉＯ２・（ｎ−１）Ｈ２Ｏ）及びパラケイ酸（ｎＳｉＯ２・（ｎ−２）Ｈ２Ｏ）（各ｎ＝１，２，３，４，．．．）を包含する。リン酸類はオルトリン酸（Ｈ３ＰＯ４）、ポリリン酸（Ｈｎ＋２ＰｎＯ３ｎ＋１）（ｎ＝２，３，４，．．．）（二リン酸、三リン酸、四リン酸など）、メタリン酸［（ＨＰＯ３）ｎ］（ｎ＝１，２，３，４，．．．）（メタリン酸、二メタリン酸、三メタリン酸、四メタリン酸など）を包含する。 The solid film component (B) can be arbitrarily selected depending on the use of the lubricating film to be formed. For example, in the case of cold forging applications where the temperature and pressure of the frictional sliding surface are very high, the melting point of the film is higher than the material arrival temperature at the time of processing, and it is less affected by processing heat, so the above role is stable It is preferable to use an aqueous inorganic salt because it can be shown as an example. As the aqueous inorganic salt having such properties, it is preferable to use at least one selected from sulfate, boric acid salts, silicic acid salts and phosphoric acid salts. Boric acids include orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ), tetraboric acid (H 2 B 4 O 7 ), pentaboric acid (HB 5 O 8 ), and the like. Silicic acids are orthosilicic acid (nSiO 2. (N + 1) H 2 O), metasilicic acid (nSiO 2 .nH 2 O), mesosilicate (nSiO 2. (N-1) H 2 O) and parasilicic acid (nSiO 2. (N-2) H 2 O) (each n = 1, 2, 3, 4,...). Phosphoric acids include orthophosphoric acid (H 3 PO 4 ), polyphosphoric acid (H n + 2 P n O 3n + 1 ) (n = 2, 3, 4,...) (Diphosphoric acid, triphosphoric acid, tetraphosphoric acid, etc.), Metaphosphoric acid [(HPO 3 ) n ] (n = 1, 2, 3, 4,...) (Metaphosphoric acid, dimetaphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, etc.) is included.

これらの酸塩の陽イオンとしてはアルカリ金属イオン（ナトリウムイオン、カリウムイオン、リチウムイオンなど）、アンモニウムイオン、アミン（エチルアミン等）やアルカノールアミン（モノエタノールアミン、ジエタノールアミン等）から形成される陽イオン（塩としてはアミン塩）などが挙げられ、アルカリ金属イオン及びアンモニウムイオンがより好ましい。水性無機塩として具体的には、硫酸ナトリウム、硫酸カリウム、ホウ酸ナトリウム（四ホウ酸ナトリウムなど）、ホウ酸カリウム（四ホウ酸カリウムなど）、ホウ酸のジエタノールアミン塩、ケイ酸ナトリウム、ケイ酸カリウム、ケイ酸リチウム、メタケイ酸ナトリウム、リン酸ナトリウム、リン酸カリウム、トリポリリン酸ナトリウムなどが挙げられる。これらは単独で用いてもよいし、２種以上組み合わせて使用してもよい。   The cations of these acid salts include cations formed from alkali metal ions (sodium ion, potassium ion, lithium ion, etc.), ammonium ions, amines (ethylamine, etc.) and alkanolamines (monoethanolamine, diethanolamine, etc.) Examples of the salt include amine salts), and alkali metal ions and ammonium ions are more preferable. Specific examples of aqueous inorganic salts include sodium sulfate, potassium sulfate, sodium borate (such as sodium tetraborate), potassium borate (such as potassium tetraborate), diethanolamine salt of boric acid, sodium silicate, and potassium silicate. , Lithium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium tripolyphosphate and the like. These may be used alone or in combination of two or more.

特にケイ酸類の塩については、一般式Ｍ２Ｏ・ｎＳｉＯ２（式中、ｎは１〜９の数を表し、ＭはＮａ、Ｋ、Ｌｉ又はＮＨ４を表す）で表されるものを使用するのが好ましい。水溶液の安定性や造膜性などの観点から、ＭはＮａ又はＫであるのがより好ましく、ｎは２〜９の数であるのがより好ましく、２〜４の数であるのがより一層好ましい。 Especially for salts of silicic acids, those represented by the general formula M 2 O.nSiO 2 (where n represents the number of 1 to 9, and M represents Na, K, Li or NH 4 ) are used. It is preferable to do this. From the viewpoint of the stability of the aqueous solution and film-forming property, M is more preferably Na or K, n is more preferably a number from 2 to 9, and even more preferably a number from 2 to 4. preferable.

また、比較的軽度な塑性加工用途であり、加工後に残存する皮膜を熱処理時に揮散させたい場合などでは、強固な皮膜を形成でき熱揮散性が良好な、水性有機酸塩を固体皮膜成分として用いることが好ましい。このような性質を持つ水性有機酸塩としては、水酸基を有するか有さない炭素数３〜６の二もしくは三塩基性カルボン酸の塩を用いるのが好ましく、リンゴ酸塩、コハク酸塩、クエン酸塩及び酒石酸塩から選ばれる少なくとも一種を使用するのがより好ましい。これらの酸塩の陽イオンとしてはアルカリ金属イオン（ナトリウムイオン、カリウムイオン、リチウムイオンなど）、アンモニウムイオン、アミン（エチルアミン等）やアルカノールアミン（モノエタノールアミン、ジエタノールアミン等）から形成される陽イオン（塩としてはアミン塩）などが挙げられ、アルカリ金属イオン及びアンモニウムイオンがより好ましい。水性有機酸塩として具体的には、リンゴ酸ナトリウム、リンゴ酸カリウム、コハク酸ナトリウム、コハク酸カリウム、クエン酸ナトリウム、クエン酸カリウム、酒石酸ナトリウム、酒石酸カリウムなどが挙げられる。これらは単独で用いてもよいし、２種以上組み合わせて使用してもよい。   In addition, it is a relatively mild plastic processing application, and when a film remaining after processing is to be volatilized at the time of heat treatment, an aqueous organic acid salt that has a good heat volatility and can form a strong film is used as a solid film component. It is preferable. As the aqueous organic acid salt having such properties, it is preferable to use a salt of a dibasic or tribasic carboxylic acid having 3 to 6 carbon atoms, which may or may not have a hydroxyl group, and malate, succinate, citric acid. It is more preferable to use at least one selected from acid salts and tartrate salts. The cations of these acid salts include cations formed from alkali metal ions (sodium ion, potassium ion, lithium ion, etc.), ammonium ions, amines (ethylamine, etc.) and alkanolamines (monoethanolamine, diethanolamine, etc.) Examples of the salt include amine salts), and alkali metal ions and ammonium ions are more preferable. Specific examples of the aqueous organic acid salt include sodium malate, potassium malate, sodium succinate, potassium succinate, sodium citrate, potassium citrate, sodium tartrate, potassium tartrate and the like. These may be used alone or in combination of two or more.

また、機械摺動面用潤滑皮膜などで、不感湿性、耐磨耗性などが求められる場合などでは、水性樹脂を固体皮膜成分として用いることが好ましい。このような性質を持つ水性樹脂としては、アクリル系樹脂、フェノール系樹脂、ウレタン樹脂、エポキシ樹脂及びポリエステル樹脂から選ばれる少なくとも一種を使用することが好ましい。ここで用いられる水性樹脂は、皮膜形成性を有するものであれば特に制限はなく、一般的には水溶性もしくは水分散状態で供給されている。本発明の水系潤滑皮膜剤に用いられる水性樹脂は、不感湿化用途にも用いる観点から、水溶性樹脂を製膜する際には架橋剤も用いて架橋するのが好ましい。また、該水性樹脂は、比較的分子量が高かったりもしくは疎水性樹脂骨格を有するので、水に分散化したエマルジョンであることが好ましい。これらの水性樹脂は単独で用いてもよいし、２種以上組み合わせて使用してもよい。   In addition, when a moisture insensitive property, wear resistance, or the like is required for a lubricating film for a machine sliding surface, it is preferable to use an aqueous resin as a solid film component. As the aqueous resin having such properties, it is preferable to use at least one selected from acrylic resins, phenol resins, urethane resins, epoxy resins, and polyester resins. The aqueous resin used here is not particularly limited as long as it has film-forming properties, and is generally supplied in a water-soluble or water-dispersed state. The aqueous resin used in the water-based lubricating coating agent of the present invention is preferably crosslinked with a crosslinking agent when forming a water-soluble resin from the viewpoint of use in moisture-insensitive applications. Moreover, since the aqueous resin has a relatively high molecular weight or has a hydrophobic resin skeleton, it is preferably an emulsion dispersed in water. These aqueous resins may be used alone or in combination of two or more.

アクリル系樹脂はアクリル系モノマーの少なくとも一種を重合して得られるものが挙げられる。アクリル系モノマーとしては、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、イソプロピルメタクリレート、ｎ−ブチルアクリレート、ｎ−ブチルメタクリレート、２−エチルヘキシルメタクリレート、オクチルアクリレート等のアルキル（Ｃ＝１〜８）（メタ）アクリレート；メトキシメチルアクリレート、メトキシエチルアクリレート、エトキシメチルアクリレート、エトキシエチルアクリレート、メトキシメチルメタクリレート、メトキシエチルメタクリレート、エトキシメチルメタクリレート、エトキシエチルメタクリレート、メトキシブチルアクリレート等の低級アルコキシ低級アルキル（メタ）アクリレート；２−ヒドロキシエチル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート等のヒドロキシ低級アルキル（メタ）アクリレート；アクリルアミド、メタクリルアミド；Ｎ−メチロールアクリルアミド、Ｎ−メチロールメタクリルアミド、Ｎ−ブトキシメチルアクリルアミド、Ｎ−ブトキシメチルメタクリルアミド等のＮ−非置換もしくは置換（特に低級アルコキシ置換）メチロール基を有する（メタ）アクリルアミド；ホスホニルオキシメチルアクリレート、ホスホニルオキシエチルアクリレート、ホスホニルオキシプロピルアクリレート、ホスホニルオキシメチルメタクリレート、ホスホニルオキシエチルメタクリレート、ホスホニルオキシプロピルメタクリレート等のホスホニルオキシ低級アルキル（メタ）アクリレート；アクリロニトリル；アクリル酸、メタクリル酸等が挙げられる。本発明においてはアクリル系樹脂は、上記のごときアクリル系モノマーの少なくとも一種とスチレン、メチルスチレン、酢酸ビニル、塩化ビニル、ビニルトルエン、エチレン等の他のエチレン性モノマーの少なくとも一種との共重合体であってアクリル系モノマー単位を３０モル％以上含有するものをも包含するものとする。アクリル系樹脂の分子量はゲルパーミエーションクロマトグラフィーで測定した場合、１，０００〜１，０００，０００、特に１００，０００〜６００，０００であることが好ましい。   Examples of the acrylic resin include those obtained by polymerizing at least one acrylic monomer. Examples of acrylic monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, alkyl such as octyl acrylate (C = 1 to 8) (meta ) Acrylate; lower alkoxy lower alkyl (meth) acrylate such as methoxymethyl acrylate, methoxyethyl acrylate, ethoxymethyl acrylate, ethoxyethyl acrylate, methoxymethyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, ethoxyethyl methacrylate, methoxybutyl acrylate; -Hydroxyethyl (meth) acrylate, 3-hydroxypropyl Hydroxy lower alkyl (meth) acrylates such as meth) acrylate; acrylamide, methacrylamide; N-unsubstituted or substituted such as N-methylolacrylamide, N-methylolmethacrylamide, N-butoxymethylacrylamide, N-butoxymethylmethacrylamide ( (Meth) acrylamide having a methylol group, especially phosphonyloxymethyl acrylate, phosphonyloxyethyl acrylate, phosphonyloxypropyl acrylate, phosphonyloxymethyl methacrylate, phosphonyloxyethyl methacrylate, phosphonyloxypropyl methacrylate, etc. Phosphonyloxy lower alkyl (meth) acrylates; acrylonitrile; acrylic acid, methacrylic acid and the like. In the present invention, the acrylic resin is a copolymer of at least one acrylic monomer as described above and at least one other ethylenic monomer such as styrene, methylstyrene, vinyl acetate, vinyl chloride, vinyltoluene, and ethylene. It also includes those containing 30 mol% or more of acrylic monomer units. The molecular weight of the acrylic resin is preferably 1,000 to 1,000,000, particularly 100,000 to 600,000 when measured by gel permeation chromatography.

フェノール系樹脂としては、フェノール、クレゾール、キシレノール等のフェノール類の少なくとも一種とホルムアルデヒドとの反応によって得られるものが挙げられ、ノボラック型樹脂、レゾール型樹脂のいずれであっても良い。ノボラック型樹脂を使用する場合には硬化剤としてヘキサメチレンテトラミン等を共存させる必要がある。フェノール樹脂皮膜は後述の乾燥工程で硬化する。フェノール樹脂の分子量については特に制限はない。   Examples of the phenolic resin include those obtained by reaction of at least one phenol such as phenol, cresol, and xylenol with formaldehyde, and may be either a novolak type resin or a resol type resin. When a novolac resin is used, it is necessary to coexist with hexamethylenetetramine as a curing agent. The phenolic resin film is cured in the drying process described later. There is no restriction | limiting in particular about the molecular weight of a phenol resin.

ウレタン樹脂は、ウレタン結合（ＮＨＣＯＯ）を有する合成樹脂であり、ウレタン樹脂としては、一般にイソシアネート基を２個以上有するポリイソシアネート化合物と活性水素基を２個以上有するポリオールとの重付加反応によって得られるものを用いることができる。かかるポリオールとしてはポリエステルポリオールおよびポリエーテルポリオールが挙げられる。ポリエステルポリオールとしては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、ネオペンチルグリコール、１，２−ブチレングリコール、１，３−ブチレングリコール、１，４−ブチレングリコール、３−メチルペンタンジオール、ヘキサメチレングリコール、水添ビスフェノールＡ、トリメチロールプロパン、グリセリン等の低分子量のポリオールと、コハク酸、グルタル酸、アジピン酸、セバチン酸、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、テトラヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、ヘキサヒドロフタル酸等の多塩基酸との反応によって得られる末端に水酸基を有するポリエステル化合物が挙げられる。   The urethane resin is a synthetic resin having a urethane bond (NHCOO), and the urethane resin is generally obtained by a polyaddition reaction between a polyisocyanate compound having two or more isocyanate groups and a polyol having two or more active hydrogen groups. Things can be used. Such polyols include polyester polyols and polyether polyols. Examples of the polyester polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1, Low molecular weight polyols such as 4-butylene glycol, 3-methylpentanediol, hexamethylene glycol, hydrogenated bisphenol A, trimethylolpropane, glycerin, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid A polyester compound having a hydroxyl group at the terminal obtained by reaction with a polybasic acid such as terephthalic acid, trimellitic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexahydrophthalic acid, etc. It is below.

また、ポリエーテルポリオールとしては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、ネオペンチルグリコール、１，２−ブチレングリコール、１，３−ブチレングリコール、１，４−ブチレングリコール、３−メチルペンタンジオール、ヘキサメチレングリコール、ビスフェノールＡ、水添ビスフェノールＡ、トリメチロールプロパン、グリセリン等の低分子量のポリオールまたはこれらのエチレンオキシドおよび／またはプロピレンオキシド高付加物、ポリエチレングリコール、ポリプロピレングリコール、ポリエチレン／プロピレングリコール等のポリエーテルポリオール、ポリカプロラクトンポリオール、ポリオレフィンポリオール、ポリブタジエンポリオール等が挙げられる。   Examples of the polyether polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,2-butylene glycol, and 1,3-butylene glycol. 1,4-butylene glycol, 3-methylpentanediol, hexamethylene glycol, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, glycerin and other low molecular weight polyols or their ethylene oxide and / or propylene oxide high adducts, Polyether glycol such as polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, polycaprolactone polyol, polyolefin polyol Le, polybutadiene polyols, and the like.

またポリイソシアネートとしては、脂肪族、脂環式および芳香族ポリイソシアネートが挙げられ、具体的には、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、リジンジイソシアネートエステル、水添キシリレンジイソシアネート、１，４−シクロヘキシレンジイソシアネート、４，４´−ジシクロヘキシルメタンジイソシアネート、２，４´−ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート、３，３´−ジメトキシ−４，４´−ビフェニレンジイソシアネート、１，５−ナフタレンジイソシアネート、１，５−テトラヒドロナフタレンジイソシアネート、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、４，４´−ジフェニルメタンジイソシアネート、２，４´−ジフェニルメタンジイソシアネート、フェニレンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート等が挙げられる。
ウレタン樹脂の分子量は、ゲルパーミエーションクロマトグラフィーで測定した場合、５００〜５００，０００であることが好ましい。 Polyisocyanates include aliphatic, cycloaliphatic and aromatic polyisocyanates. Specific examples include tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, hydrogenated xylylene diisocyanate, 1,4-cyclohexylene. Diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydro Naphthalene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diph Methane diisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and the like.
The molecular weight of the urethane resin is preferably 500 to 500,000 as measured by gel permeation chromatography.

エポキシ樹脂としては、ビスフェノール類、特にビスフェノールＡ（２，２−ビス（４´−ヒドロキシフェニル）プロパン）とエピクロルヒドリンとを反応させて得られる、ビスフェノール型エポキシ樹脂、特に下記式で表わされるビスフェノールＡ型エポキシ樹脂をまず挙げることができる。他の例として、フェノールノボラック樹脂のフェノール性水酸基をグリシジルエーテル化したノボラック型エポキシ樹脂、芳香族カルボン酸のグリシジルエステル、エチレン性不飽和化合物の二重結合を過酸でエポキシ化した過酸エポキシ型等を挙げることができる。さらに、上記のごときエポキシ樹脂の樹脂骨格にエチレンオキシドまたはプロピレンオキシドを付加したもの、多価アルコールのグリシジルエーテル型等も挙げることができる。これらの中でビスフェノールＡ型エポキシ樹脂を用いるのがもっとも好ましい。エポキシ樹脂の分子量は、ゲルパーミエーションクロマトグラフィーで測定した場合、３５０〜５，０００であることが好ましい。   As the epoxy resin, bisphenol type epoxy resin obtained by reacting bisphenols, particularly bisphenol A (2,2-bis (4′-hydroxyphenyl) propane) and epichlorohydrin, particularly bisphenol A type represented by the following formula: An epoxy resin can be mentioned first. Other examples include novolak epoxy resins in which phenolic hydroxyl groups of phenol novolac resins are glycidyl etherified, glycidyl esters of aromatic carboxylic acids, and peracid epoxy types in which double bonds of ethylenically unsaturated compounds are epoxidized with peracids. Etc. Furthermore, the thing which added ethylene oxide or propylene oxide to the resin frame | skeleton of an epoxy resin as mentioned above, the glycidyl ether type of a polyhydric alcohol, etc. can be mentioned. Among these, it is most preferable to use a bisphenol A type epoxy resin. The molecular weight of the epoxy resin is preferably 350 to 5,000 as measured by gel permeation chromatography.

Figure 0003872492
Figure 0003872492

ポリエステル樹脂としては、エチレングリコール、ネオペンチルグリコールなどのポリオール成分とテレフタル酸、トリメリット酸等の多塩基酸との縮合物であるポリエステル樹脂などが挙げられる。ポリエステル樹脂の分子量は、ゲルパーミエーションクロマトグラフィーで測定した場合、１，０００〜５０，０００であることが好ましい。   Examples of the polyester resin include a polyester resin that is a condensate of a polyol component such as ethylene glycol or neopentyl glycol and a polybasic acid such as terephthalic acid or trimellitic acid. The molecular weight of the polyester resin is preferably 1,000 to 50,000 when measured by gel permeation chromatography.

固体皮膜成分（Ｂ）の配合量は、水系潤滑皮膜処理剤の全固形分を基準にして、固形分として、３〜９９．９質量％であることが必要であり、３〜９５質量％であることが好ましく、５〜９０質量％であることがより好ましい。３質量％未満では、形成される皮膜の耐焼付き性が不十分であり、また、潤滑成分等の保持、供給機能が不十分となる傾向になる。９９．９質量％を超えると、分岐カルボン酸及び／又はその塩（Ａ）の機能が発揮されなくなる。   The blending amount of the solid film component (B) is required to be 3 to 99.9% by mass as the solid content based on the total solid content of the aqueous lubricant film treatment agent, and is 3 to 95% by mass. It is preferable that it is 5 to 90% by mass. If it is less than 3% by mass, the seizure resistance of the formed film is insufficient, and the retention and supply functions of the lubricating component and the like tend to be insufficient. When it exceeds 99.9 mass%, the function of branched carboxylic acid and / or its salt (A) will not be exhibited.

本発明の水系潤滑皮膜処理剤は、また、必要に応じて、形成される潤滑皮膜の各種性能を調整するために補足的な成分を含有してもよい。例えば、主に潤滑性能を調整する場合に用いる補足成分として、油、石けん、金属石けん、ワックス、ポリテトラフルオロエチレンから選ばれる少なくとも一種（補足成分（Ｃ））を使用することが好ましい。なお、補足成分（Ｃ）は、通常は潤滑性能をより高めるために使用するが、場合により多少抑制するために使用する場合もあり得る。   The water-based lubricating film treating agent of the present invention may also contain supplemental components to adjust various performances of the formed lubricating film, if necessary. For example, it is preferable to use at least one selected from oil, soap, metal soap, wax, and polytetrafluoroethylene (supplementary component (C)) as a supplementary component used mainly when adjusting the lubricating performance. The supplemental component (C) is usually used to further improve the lubrication performance, but may be used to suppress it to some extent.

補足成分（Ｃ）における油としては、植物油、合成油、鉱物油などを使用でき、例えばパーム油、ひまし油、菜種油、マシン油、タービン油、エステル油、シリコン油などを挙げることができる。石けんは、脂肪酸のアルカリ金属塩であり、例えばオクタン酸、デカン酸、ラウリン酸、ミリスチン酸、パルミチン酸、イコサン酸、オレイン酸、ステアリン酸などの炭素数８〜２２の飽和もしくは不飽和脂肪酸のナトリウム塩、カリウム塩などが挙げられる。金属石けんとしては、カルシウム、亜鉛、マグネシウム、バリウムなどの多価金属と上記脂肪酸との塩などが挙げられる。ワックスとしては、ポリエチレンワックス、ポリプロピレンワックス、カルナウバロウ、パラフィンワックスなどが挙げられる。ポリテトラフルオロエチレンとしては、重合度例えば１００万〜１０００万程度のポリテトラフルオロエチレンを挙げることができる。これらは単独で用いてもよいし、２種以上組み合わせて使用してもよい。補足成分（Ｃ）は、本発明の水系潤滑皮膜剤中に、通常、溶解もしくは分散した状態で含有される。   As the oil in the supplement component (C), vegetable oil, synthetic oil, mineral oil and the like can be used, and examples thereof include palm oil, castor oil, rapeseed oil, machine oil, turbine oil, ester oil, silicon oil and the like. Soap is an alkali metal salt of a fatty acid such as octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, icosanoic acid, oleic acid, stearic acid, etc. Salt, potassium salt and the like. Examples of the metal soap include salts of polyvalent metals such as calcium, zinc, magnesium and barium with the above fatty acids. Examples of the wax include polyethylene wax, polypropylene wax, carnauba wax, and paraffin wax. Examples of polytetrafluoroethylene include polytetrafluoroethylene having a polymerization degree of, for example, about 1 million to 10 million. These may be used alone or in combination of two or more. The supplemental component (C) is usually contained in a dissolved or dispersed state in the water-based lubricating coating agent of the present invention.

補足成分（Ｃ）の配合量は、水系潤滑皮膜処理剤の全固形分を基準にして、固形分として、１〜５０質量％であることが好ましく、２〜４０質量％であることがより好ましく、２〜３０質量％であることがより一層好ましい。１質量％未満では、補足成分（Ｃ）の潤滑性能調整機能が十分に発揮されず、５０質量％を超えると、潤滑性能調整効果が飽和して経済的に不利である。   The amount of supplemental component (C) is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, based on the total solid content of the water-based lubricating film treating agent. 2 to 30% by mass is even more preferable. If the amount is less than 1% by mass, the lubricating performance adjusting function of the supplement component (C) is not sufficiently exhibited. If the amount exceeds 50% by mass, the lubricating performance adjusting effect is saturated, which is economically disadvantageous.

本発明の水系潤滑皮膜処理剤には、また、必要に応じて、強加工用途での耐焼付き性向上やダイス保護等を目的として、高い加工荷重での潤滑を補助する働きや、極圧効果を発揮するものなどを配合することができる。そのようなものとして、二硫化モリブデン、グラファイト、カーボンブラック（黒鉛化カーボンブラックも含む）、有機モリブデン化合物（モリブデンＤＴＣ）、リン酸亜鉛、石灰、メラミンシアヌレート、窒化ホウ素などから選ばれる一種（補足成分（Ｄ））を使用することが好ましい。これらは単独で用いてもよいし、２種以上組み合わせて使用してもよい。   The water-based lubricating film treatment agent of the present invention, if necessary, assists in lubrication under high processing load for the purpose of improving seizure resistance and die protection in strong processing applications, and extreme pressure effect. The thing etc. which exhibit can be mix | blended. As such, one kind selected from molybdenum disulfide, graphite, carbon black (including graphitized carbon black), organic molybdenum compound (molybdenum DTC), zinc phosphate, lime, melamine cyanurate, boron nitride, etc. It is preferred to use component (D)). These may be used alone or in combination of two or more.

補足成分（Ｄ）の配合量は、水系潤滑皮膜処理剤の全固形分を基準にして、固形分として、０．１〜７０質量％であることが好ましく、０．５〜６０質量％であることがより好ましく、２〜６０質量％であることがより一層好ましい。０．１質量％未満では、耐焼付き性向上やダイス保護等の機能が発揮されず、７０質量％を超えて配合しても、かかる効果のさらなる向上は望めない。   The blending amount of the supplemental component (D) is preferably 0.1 to 70% by mass, and preferably 0.5 to 60% by mass as the solid content based on the total solid content of the aqueous lubricant film treatment agent. Is more preferable, and it is still more preferable that it is 2-60 mass%. If it is less than 0.1% by mass, functions such as improvement in seizure resistance and die protection are not exhibited, and even if it exceeds 70% by mass, further improvement of this effect cannot be expected.

本発明の水系潤滑皮膜処理剤においては、分岐カルボン酸及び／又はその塩（Ａ）が補足成分（Ｃ）や補足成分（Ｄ）を安定に分散させる機能を担うので、通常、これらの成分を分散または乳化させるために各種界面活性剤や高分子分散剤などを配合する必要はないが、補足成分（Ｃ）や補足成分（Ｄ）を多量に配合する場合などに成分（Ａ）の機能を補足するため、界面活性剤を使用してもよい。また、界面活性剤が市販の水性樹脂や補足成分（Ｃ）などに伴われて入ってくる場合もある。かかる界面活性剤としては、非イオン性界面活性剤、陰イオン性界面活性剤、両性界面活性剤、陽イオン性界面活性剤、水溶性高分子分散剤などから適宜選択することができる。   In the aqueous lubricating film treating agent of the present invention, the branched carboxylic acid and / or salt (A) has a function of stably dispersing the supplement component (C) and supplement component (D). In order to disperse or emulsify, it is not necessary to add various surfactants or polymer dispersants, but the function of component (A) is effective when a large amount of supplemental component (C) or supplemental component (D) is blended. To supplement, a surfactant may be used. In some cases, the surfactant may come in along with a commercially available aqueous resin or supplemental component (C). Such a surfactant can be appropriately selected from nonionic surfactants, anionic surfactants, amphoteric surfactants, cationic surfactants, water-soluble polymer dispersants, and the like.

本発明の水系潤滑皮膜処理剤における媒体は水である。本発明の水系潤滑皮膜処理剤における全固形分濃度については特に制限はないが、通常、１〜５０質量％程度が適当である。   The medium in the aqueous lubricant film treating agent of the present invention is water. Although there is no restriction | limiting in particular about the total solid content concentration in the water-system lubricating film processing agent of this invention, Usually, about 1-50 mass% is suitable.

本発明の水系潤滑皮膜剤の製造方法については、製造された水系潤滑皮膜剤が上記してきた条件を満足している限り、特に制限されない。例えば、本発明の水系潤滑皮膜剤は分岐カルボン酸及び／又はその塩（Ａ）を水に溶解もしくは分散し、ついで固体皮膜成分（Ｂ）、並びに、必要に応じて、補足成分（Ｃ）及び／又は補足成分（Ｄ）を添加し攪拌することにより製造することができる。また、本発明の水系潤滑皮膜剤は、使用者が水に溶解又は分散させて使用する粉末パッケージの形態を取ることも可能である。粉末パッケージの場合には、分岐カルボン酸及び／又はその塩（Ａ）と粉末状態の固体皮膜成分（Ｂ）とを混合し、必要に応じて補足成分（Ｃ）及び／又は補足成分（Ｄ）を添加しパウダーミキサーなどで混合して製造することができる。   The method for producing the aqueous lubricant film of the present invention is not particularly limited as long as the produced aqueous lubricant film satisfies the above-described conditions. For example, the water-based lubricating coating agent of the present invention dissolves or disperses the branched carboxylic acid and / or its salt (A) in water, then the solid coating component (B), and, if necessary, the supplemental component (C) and It can manufacture by adding and / or stirring supplement component (D). Moreover, the water-based lubricating coating agent of the present invention can also take the form of a powder package that is used by the user dissolved or dispersed in water. In the case of a powder package, the branched carboxylic acid and / or salt thereof (A) and the powdered solid film component (B) are mixed, and supplementary component (C) and / or supplemental component (D) as necessary. And can be produced by mixing with a powder mixer or the like.

本発明の水系潤滑皮膜剤は、鉄もしくは鉄鋼、ステンレス鋼、メッキ鋼（例えば、電気亜鉛メッキ、溶融亜鉛メッキ、アルミ亜鉛メッキ、アルミメッキ、鉄亜鉛メッキなどのメッキ処理が施された鋼）、アルミニウムもしくはアルミニウム合金、マグネシウム合金、スズもしくはスズ合金、チタンもしくはチタン合金、銅もしくは銅合金など金属材料を、例えば鍛造、伸線、伸管、プレス成形、ロールフォーミングなどに代表される冷間塑性加工に付す場合に、固体表面間（例えば、ダイスと金属材料との間）に生じる摩擦を低減するための潤滑皮膜剤として、金属材料の表面に塗布することができる。金属材料の形状などについては特に制限はない。本発明の水系潤滑皮膜剤は、また、エンジンやコンプレッサーなどの機械の内部の摺動する金属部材の表面と金属部材等の固体の表面との間（例えば、ピストンとシリンダーとの間）に生じる摩擦を低減するための潤滑皮膜剤として用いることができる。本発明の水系潤滑皮膜処理剤は、さらに、非金属材料からなる固体表面（例えば、セラミック表面、プラスチック表面など）にも適用可能である。   The water-based lubricating coating agent of the present invention is iron or steel, stainless steel, plated steel (for example, steel subjected to plating treatment such as electrogalvanization, hot dip galvanization, aluminum galvanization, aluminum plating, iron galvanization), Cold plastic processing such as aluminum, aluminum alloy, magnesium alloy, tin or tin alloy, titanium or titanium alloy, copper or copper alloy, for example, forging, wire drawing, tube drawing, press forming, roll forming, etc. Can be applied to the surface of the metal material as a lubricant film agent for reducing friction generated between the solid surfaces (for example, between the die and the metal material). There are no particular restrictions on the shape of the metal material. The water-based lubricating coating agent of the present invention is also generated between the surface of a sliding metal member inside a machine such as an engine or a compressor and a solid surface such as a metal member (for example, between a piston and a cylinder). It can be used as a lubricant film agent for reducing friction. The water-based lubricating film treating agent of the present invention can also be applied to a solid surface made of a nonmetallic material (for example, a ceramic surface, a plastic surface, etc.).

本発明の水系潤滑皮膜剤を塗布するに先立って、対象とする固体表面（例えば、金属材料表面）を洗浄（通常アルカリ洗浄剤を使用）、水洗、脱スケール（ショットブラストもしくは塩酸などによる酸洗など）、水洗の順に前処理することによって表面を清浄にすることが良好な潤滑性を発揮するために好ましい。酸化スケールが付着していな場合や酸化スケールが必要な用途に用いる場合、または非金属材料からなる固体表面の場合などは、脱スケール→水洗は省いても構わない。これらの前処理は常法により行えばよい。   Prior to application of the water-based lubricating coating agent of the present invention, the target solid surface (for example, metal material surface) is washed (usually using an alkaline detergent), washed with water, descaled (shot blasted or pickled with hydrochloric acid, etc.) Etc.), in order to exhibit good lubricity, it is preferable to clean the surface by pre-treatment in the order of water washing. When the oxide scale is not attached, when it is used for an application requiring the oxide scale, or when it is a solid surface made of a nonmetallic material, descaling → water washing may be omitted. These pretreatments may be performed by a conventional method.

本発明の水系潤滑皮膜処理剤は、浸漬、スプレー、流しかけ、刷毛塗りなどの常法により固体表面（例えば、金属材料表面）に塗布する。塗布は固体表面が該固体潤滑皮膜処理剤で十分に覆われればよく、塗布する時間に特に制限はない。塗布後、水系潤滑皮膜処理剤は乾燥する必要がある。乾燥は常温放置でも構わないが、通常６０℃〜１５０℃で１分〜６０分行うのが好適である。水系潤滑皮膜剤の皮膜質量は用途によって異なるが、金属材料の塑性加工用途では焼付きを防ぐ観点から、乾燥皮膜として１ｇ／ｍ２以上であるのが好ましく、３〜３０ｇ／ｍ２であるのがより好ましく、３〜２０ｇ／ｍ２であるのがより一層好ましい。 The water-based lubricating film treating agent of the present invention is applied to a solid surface (for example, a metal material surface) by a conventional method such as dipping, spraying, pouring or brushing. As long as the solid surface is sufficiently covered with the solid lubricating film treating agent, the application time is not particularly limited. After application, the water-based lubricating film treating agent needs to be dried. Although drying may be performed at room temperature, it is usually preferable to carry out at 60 ° C. to 150 ° C. for 1 minute to 60 minutes. Coating weight of the aqueous lubricant coating agent may vary depending on the application, the plastic working applications of the metallic material from the viewpoint of preventing seizure, but preferably not 1 g / m 2 or more as a dry film, in the range of 3 to 30 g / m 2 Is more preferable, and it is still more preferable that it is 3-20 g / m < 2 >.

本発明の水系潤滑皮膜剤により形成される潤滑皮膜は、分岐カルボン酸及び／又はその塩（Ａ）を皮膜中や皮膜上層に分布させることで、良好な潤滑性及び耐焼付き性を併せ持ち、摩擦摺動面に安定的な潤滑状態を提供する。このため、表面積拡大による大きな発熱を伴い高面圧下で摺動する冷間塑性加工や、機械摺動部の高速摺動面などで安定的に優れた性能を示す。また、任意成分として配合する補足成分（Ｃ）や補足成分（Ｄ）は、分岐カルボン酸及び／又はその塩（Ａ）の優れた分散剤機能により固体潤滑皮膜中にて均一に分布させることができる他、潤滑皮膜形成時に分岐カルボン酸及び／又はその塩（Ａ）と共に皮膜上層に分布させることもできる。例えば、固体皮膜成分（Ｂ）としての水性無機塩と、その水溶液に対しての溶解度が比較的小さい該分岐カルボン酸アルカリ金属塩とを組み合わせた場合には、皮膜形成時の析出浮上現象によって該分岐カルボン酸アルカリ金属塩を皮膜上層に分布させることができ、該分岐カルボン酸アルカリ金属塩により分散されていた各補足成分も共に皮膜上層に分布させられるなど、潤滑皮膜構造の任意な設計が可能であり、本発明の水系潤滑皮膜剤の産業上でのメリットは大きい。   The lubricating film formed by the water-based lubricating film agent of the present invention distributes the branched carboxylic acid and / or its salt (A) in the film or in the upper layer of the film, and thus has good lubricity and seizure resistance, and friction. Provide a stable lubrication state on the sliding surface. For this reason, it shows stable and excellent performance in cold plastic working that slides under high surface pressure accompanied by large heat generation due to surface area expansion, and the high-speed sliding surface of the machine sliding portion. Further, the supplement component (C) and supplement component (D) to be blended as optional components can be uniformly distributed in the solid lubricating film by the excellent dispersant function of the branched carboxylic acid and / or its salt (A). In addition, it can be distributed in the upper layer of the film together with the branched carboxylic acid and / or its salt (A) during the formation of the lubricating film. For example, when the aqueous inorganic salt as the solid film component (B) is combined with the branched carboxylic acid alkali metal salt having a relatively low solubility in the aqueous solution, the precipitation levitation phenomenon during the film formation causes Arbitrary design of lubricating coating structure is possible, such as branched alkali metal salt of carboxylic acid can be distributed in the upper layer of the coating, and each supplemental component dispersed by the alkali metal salt of branched carboxylic acid can also be distributed in the upper layer of the coating. Thus, the industrial advantage of the water-based lubricating coating agent of the present invention is great.

本発明の実施例を比較例と共に挙げることによって、本発明をその効果と共にさらに具体的に説明する。なお、本発明はこれらの実施例によって制限されるものではない。   The present invention will be described more specifically with its effects by giving examples of the present invention together with comparative examples. In addition, this invention is not restrict | limited by these Examples.

（１）水系潤滑皮膜処理剤の製造
以下に示す各成分を、表１に示す組合せ及び割合にて用いて、表１に示す実施例１〜１１及び比較例１〜６の水系潤滑皮膜処理剤を調製した。なお、これらすべての水系潤滑皮膜処理剤において、水系潤滑皮膜処理剤中の全固形分：水の質量比は１：９とした。
＜分岐カルボン酸及び／又はその塩（Ａ）＞ (1) Manufacture of water-based lubricating film treating agent The water-based lubricating film treating agents of Examples 1 to 11 and Comparative Examples 1 to 6 shown in Table 1 using the components shown below in combinations and proportions shown in Table 1. Was prepared. In all these water-based lubricant coating agents, the mass ratio of total solids: water in the water-based lubricant coating agent was 1: 9.
<Branched carboxylic acid and / or salt thereof (A)>

Figure 0003872492
Figure 0003872492

ａ−１〜ａ−６の化合物を構成する酸の流動点は以下の通りである。
ａ−１：−１℃、ａ−２：−１７℃、ａ−３：−３０℃以下、ａ−４：−３０℃以下
ａ−５：１０℃、ａ−６：７℃
ａ−１〜ａ−４の化合物は本発明範囲内の分岐カルボン酸又はその塩であり、ａ−５〜ａ−６の化合物は本発明範囲外の分岐カルボン酸の塩である。 The pour points of the acids constituting the compounds a-1 to a-6 are as follows.
a-1: -1 ° C, a-2: -17 ° C, a-3: -30 ° C or lower, a-4: -30 ° C or lower a-5: 10 ° C, a-6: 7 ° C
The compounds a-1 to a-4 are branched carboxylic acids or salts thereof within the scope of the present invention, and the compounds a-5 to a-6 are salts of branched carboxylic acids outside the scope of the present invention.

＜固体皮膜成分（Ｂ）＞
ｂ−１ 硫酸ナトリウム
ｂ−２ 四ホウ酸カリウム
ｂ−３ パラケイ酸ナトリウム（Ｎａ２Ｏ・３ＳｉＯ２）
ｂ−４ トリポリリン酸ナトリウム
ｂ−５ クエン酸アンモニウム
ｂ−６ フェノール樹脂：フェノールノボラックをアミノ化し水溶化したもの（分子量５００〜６，０００）
ｂ−７ アクリル樹脂：メチルメタクリレートおよびｎ−ブチルアクリレートの共重合物をポリオキシエチレンアルキルフェニルエーテルにて乳化重合したもの（分子量１５万以上） <Solid film component (B)>
b-1 Sodium sulfate b-2 Potassium tetraborate b-3 Sodium parasilicate (Na 2 O.3SiO 2 )
b-4 sodium tripolyphosphate b-5 ammonium citrate b-6 phenol resin: phenol novolak aminated and water-solubilized (molecular weight 500-6,000)
b-7 Acrylic resin: A copolymer of methyl methacrylate and n-butyl acrylate emulsion polymerized with polyoxyethylene alkylphenyl ether (molecular weight 150,000 or more)

＜補足成分（Ｃ）＞
ｃ−１ ステアリン酸ナトリウム
ｃ−２ ステアリン酸カルシウム：高分子分散剤にて水に分散したもの
ｃ−３ ポリエチレンワックス：エチレンの乳化重合により製造（分子量２万）
ｃ−４ ポリテトラフルオロエチレン：高分子分散剤にて水に分散したもの <Supplementary component (C)>
c-1 Sodium stearate c-2 Calcium stearate: Dispersed in water with a polymer dispersant c-3 Polyethylene wax: manufactured by emulsion polymerization of ethylene (molecular weight 20,000)
c-4 Polytetrafluoroethylene: dispersed in water with a polymer dispersant

＜補足成分（Ｄ）＞
ｄ−１ 二硫化モリブデン：粒子径５ミクロン
ｄ−２ カーボンブラック：三菱化学（株）製
ｄ−３ リン酸亜鉛：日本パーカライジング（株）製
ｄ−４ 有機モリブデン化合物（モリブデンＤＴＣ）：旭電化工業（株）製 <Supplementary component (D)>
d-1 Molybdenum disulfide: particle diameter 5 microns d-2 Carbon black: manufactured by Mitsubishi Chemical Corporation d-3 zinc phosphate: manufactured by Nippon Parkerizing Co., Ltd. d-4 organic molybdenum compound (molybdenum DTC): Asahi Denka Kogyo Made by

（２）前処理及び皮膜処理
（２−１）前処理及び摩擦磨耗試験用皮膜処理
摺動潤滑用皮膜として設計した実施例７、９及び１０並びに比較例４については、以下の処理手順にて処理を行った。
（ａ）評価用テストピース：冷延鋼板（ＳＰＣＣ−ＳＢ） １５０ｍｍ×７０ｍｍ×０．８ｍｍｔ（ｔは厚さ）
（ｂ）脱脂：脱脂剤（登録商標 ファインクリーナー４３６０、日本パーカライジング（株）製）濃度２０ｇ／Ｌ、温度６０℃、浸漬１０分
（ｃ）水洗：水道水、常温、スプレー処理３０秒
（ｄ）潤滑皮膜処理：上記で調製した各水系潤滑皮膜処理剤、４０℃、浸漬１０秒
（ｅ）乾燥：８０℃熱風乾燥３分
（ｆ）乾燥皮膜質量：５ｇ／ｍ２ (2) Pretreatment and coating treatment (2-1) Pretreatment and coating treatment for frictional wear test For Examples 7, 9 and 10 and Comparative Example 4 designed as sliding lubrication coatings, the following procedure was used. Processed.
(A) Test piece for evaluation: Cold rolled steel sheet (SPCC-SB) 150 mm × 70 mm × 0.8 mmt (t is thickness)
(B) Degreasing: Degreasing agent (registered trademark Fine Cleaner 4360, manufactured by Nihon Parkerizing Co., Ltd.) Concentration 20 g / L, temperature 60 ° C., immersion 10 minutes (c) Washing water: tap water, room temperature, spray treatment 30 seconds (d) Lubricant film treatment: Each aqueous lubricant film treatment agent prepared above, 40 ° C., immersion 10 seconds (e) Drying: 80 ° C. Hot air drying 3 minutes (f) Dry film mass: 5 g / m 2

（２−１）前処理及び冷間鍛造試験用皮膜処理
冷間鍛造用潤滑皮膜として設計した実施例１〜６、８及び１１並びに比較例１〜３、５及び６については、以下の処理手順にて処理を行った。
（ａ）評価用試験片：Ｓ４５Ｃ球状化焼鈍材 ２５ｍｍφ×３０ｍｍ
（ｂ）脱脂：脱脂剤（登録商標 ファインクリーナー４３６０，日本パーカライジング（株）製）濃度２０ｇ／Ｌ、温度６０℃、浸漬１０分
（ｃ）水洗：水道水、常温、浸漬３０秒
（ｄ）潤滑皮膜処理：上記で調製した各水系潤滑皮膜処理剤、４０℃、浸漬３０秒
（ｅ）乾燥：１００℃熱風乾燥１０分
（ｆ）乾燥皮膜質量：１０ｇ／ｍ２ (2-1) Pretreatment and Cold Forging Test Film Treatment For Examples 1-6, 8 and 11 and Comparative Examples 1-3, 5 and 6 designed as lubricating films for cold forging, the following treatment procedure Was processed.
(A) Test piece for evaluation: S45C spheroidized annealing material 25 mmφ × 30 mm
(B) Degreasing: Degreasing agent (registered trademark Fine Cleaner 4360, manufactured by Nihon Parkerizing Co., Ltd.) Concentration 20 g / L, temperature 60 ° C., immersion 10 minutes (c) water washing: tap water, room temperature, immersion 30 seconds (d) lubrication Film treatment: Each aqueous lubricant film treatment agent prepared above, 40 ° C., immersion 30 seconds (e) Drying: 100 ° C. Hot air drying 10 minutes (f) Dry film mass: 10 g / m 2

（３）評価試験
＜耐発泡性＞
上記で調製した各水系潤滑皮膜処理剤を２００ｍＬの有栓メスシリンダーに２０ｍＬ採取し、液温４０℃で３０秒間振盪後に静置し、３分後の残存泡高さで耐発泡性を評価する。
評価基準： ○：残存泡高さが５ｍＬ未満
△：残存泡高さが５ｍＬ以上、１０ｍＬ未満
×：残存泡高さが１０ｍＬ以上 (3) Evaluation test <Foaming resistance>
20 mL of each water-based lubricating film treatment agent prepared above is collected in a 200 mL stoppered graduated cylinder, left to stand after shaking for 30 seconds at a liquid temperature of 40 ° C., and the foam resistance is evaluated by the residual foam height after 3 minutes. .
Evaluation criteria: ○: Residual bubble height is less than 5 mL
Δ: Residual foam height is 5 mL or more and less than 10 mL
X: Residual bubble height is 10 mL or more

＜処理液安定性＞
上記で調製した各水系潤滑皮膜処理剤１０００ｍＬに対して８０℃で１２０時間加熱攪拌を行い、次いで試験前後の粒子径分布を比較することで、各分散成分などの凝集傾向などからの処理液安定性を評価した。なお、試験中の揮発水分に対しては適宜純水を補った。
粒子径分布測定：レーゼンテック社製 粒体・液滴モニタリングシステムM４００Lを用い、（最大ピーク検出粒子数／総検出粒子数）で算出される、最大ピーク検出粒子比を加熱試験前後で比較した。最大ピーク検出粒子比の変化率は、（試験後最大ピーク検出粒子比／試験前最大ピーク検出粒子比）で算出する。この値は小さくなるほど凝集現象などによる分散粒子数の低下を示す。
評価基準： ○：最大ピーク検出粒子比の変化率が０．８以上
△：最大ピーク検出粒子比の変化率が０．６以上０．８未満
×：最大ピーク検出粒子比の変化率が０．６未満 <Processing solution stability>
Stabilize the processing solution from the aggregation tendency of each dispersed component, etc. by stirring and heating at 80 ° C. for 120 hours with 1000 mL of each aqueous lubricant coating treatment prepared above, and then comparing the particle size distribution before and after the test. Sex was evaluated. In addition, pure water was appropriately supplemented for the volatile moisture during the test.
Particle size distribution measurement: Using a granule / droplet monitoring system M400L manufactured by Resentec, the maximum peak detected particle ratio calculated by (maximum peak detected particle number / total detected particle number) was compared before and after the heating test. The rate of change in the maximum peak detected particle ratio is calculated by (maximum peak detected particle ratio after test / maximum peak detected particle ratio before test). The smaller this value, the lower the number of dispersed particles due to the aggregation phenomenon.
Evaluation criteria: ○: Change rate of maximum peak detected particle ratio is 0.8 or more
Δ: Change rate of maximum peak detected particle ratio is 0.6 or more and less than 0.8
X: Change rate of maximum peak detected particle ratio is less than 0.6

＜摩擦磨耗試験＞
摩擦磨耗試験は、上記皮膜処理後に摩擦磨耗試験として最も標準的なバウデン試験にて行った。摺動潤滑皮膜としての性能について、摺動時の摩擦係数が０．２を超えるまでの摺動回数を焼付き摺動回数として評価した。この数値は大きいほど優れている。
試験条件： 圧子として１０ｍｍφのＳＵＪ２鋼球使用
垂直荷重＝５０Ｎ，摺動速度＝１０ｍｍ／ｓ、温度＝６０℃
評価基準： ○：焼付き摺動回数が１００回以上
△：焼付き摺動回数が２０回以上１００回未満
×：焼付き摺動回数が２０回未満 <Friction wear test>
The frictional wear test was carried out by the most standard Bowden test as the frictional wear test after the coating treatment. Regarding the performance as a sliding lubricant film, the number of sliding until the friction coefficient during sliding exceeded 0.2 was evaluated as the number of seizure sliding. The larger this number, the better.
Test conditions: 10 mmφ SUJ2 steel ball used as indenter
Vertical load = 50N, sliding speed = 10mm / s, temperature = 60 ° C
Evaluation criteria: ○: Seizure sliding number of times is 100 times or more
Δ: The seizure frequency is 20 times or more and less than 100 times.
X: Number of seizure sliding is less than 20 times

＜冷間鍛造試験＞
冷間鍛造試験は、上記皮膜処理後に特許第３２２７７２１号公報の発明に準じたスパイク試験加工を行い、加工後試験片の突起部までの皮膜追従程度と焼付き部の有無とを目視評価した。追従性が良いものは冷間塑性加工時の表面積拡大に対して十分な耐焼付き性を有し、皮膜が追従しないものでは焼付きが発生し易くなる。
評価基準： ○：突起部まで皮膜が追従していて、焼付き部無し
△：突起部まで皮膜が追従していないが、焼付き部無し
×：突起部に皮膜が追従しておらず、焼付き部有り <Cold forging test>
In the cold forging test, spike test processing according to the invention of Japanese Patent No. 3227721 was performed after the above-mentioned film treatment, and the degree of film follow-up to the protruding portion of the test piece after processing and the presence or absence of seizure portions were visually evaluated. Those having good followability have sufficient seizure resistance against surface area expansion during cold plastic working, and seizure is likely to occur if the coating does not follow.
Evaluation criteria: ○: The film follows up to the protruding part, and there is no seized part.
Δ: The film does not follow up to the protruding part, but there is no seized part.
×: The film does not follow the protrusion and there is a seizure part

以上の試験結果を表２に示す。表２から明らかなように、本発明の水系潤滑皮膜処理剤である実施例１〜１１の水系潤滑皮膜処理剤は、耐発泡性及び処理液安定性という工業的な安定使用に必要な性能において特に優れているのに加えて、十分な量の潤滑成分を含有できるので、得られる潤滑皮膜は摺動潤滑皮膜や冷間鍛造用潤滑皮膜として優れた性能を発揮するものであった。一方、分岐カルボン酸及び／又はその塩（Ａ）を含有しない比較例１〜３の水系潤滑皮膜処理剤、及び分岐カルボン酸及び／又はその塩（Ａ）とは流動点及び／又は分岐構造において異なる分岐カルボン酸の塩を使用した比較例４及び５の水系潤滑皮膜処理剤は、耐発泡性及び処理液安定性の両方もしくは一方が著しく劣っており、工業的な安定使用に供せられないものであった。また、優れた潤滑性能を有するステアリン酸ナトリウムを多量に配合しようとした比較例６については、水系潤滑皮膜処理剤が固化（極度な増粘）し、水系潤滑皮膜処理剤として成り立たなかったため評価対象外とした。   The test results are shown in Table 2. As is apparent from Table 2, the water-based lubricating film treatment agents of Examples 1 to 11 which are the water-based lubricating film treatment agents of the present invention have the performance necessary for industrial stable use such as foam resistance and processing solution stability. In addition to being particularly excellent, since a sufficient amount of lubricating components can be contained, the resulting lubricating film exhibits excellent performance as a sliding lubricating film or a cold forging lubricating film. On the other hand, the aqueous lubricant film treatment agents of Comparative Examples 1 to 3 that do not contain a branched carboxylic acid and / or salt thereof (A), and the branched carboxylic acid and / or salt thereof (A) are pour points and / or branched structures. The aqueous lubricant film treatment agents of Comparative Examples 4 and 5 using different branched carboxylic acid salts are remarkably inferior in foam resistance and / or treatment liquid stability and cannot be used for industrial stable use. It was a thing. In Comparative Example 6 in which a large amount of sodium stearate having excellent lubricating performance was to be blended, the water-based lubricant coating agent was solidified (extremely thickened), and was not evaluated as a water-based lubricant coating agent. It was outside.

Figure 0003872492
Figure 0003872492

Figure 0003872492
Figure 0003872492

Claims (11)

一般式（Ｉ）
Ｒ１−ＣＨ（Ｒ２）ＣＯＯＨ （Ｉ）
（式中、Ｒ１及びＲ２はそれぞれ独立に炭素数４〜１２で、直鎖もしくは分岐鎖のアルキル基を示す）で表され、かつ流動点が０℃未満である分岐カルボン酸及び／又はその塩（Ａ）と、固体皮膜成分（Ｂ）とを配合してなる、固体に対する水系潤滑皮膜処理剤であって、水系潤滑皮膜処理剤の全固形分を基準にして、それぞれ固形分として、分岐カルボン酸もしくはその塩（Ａ）の配合量が０．１〜５０質量％であり、固体皮膜成分（Ｂ）の配合量が３〜９９．９質量％である該水系潤滑皮膜処理剤。 Formula (I)
R 1 —CH (R 2 ) COOH (I)
(Wherein R 1 and R 2 each independently represent a linear or branched alkyl group having 4 to 12 carbon atoms) and a pour point of less than 0 ° C. and / or A water-based lubricating film treatment agent for a solid, comprising the salt (A) and the solid film component (B), each solid content based on the total solid content of the water-based lubricating film treatment agent, The water-based lubricant coating agent, wherein the amount of the branched carboxylic acid or salt (A) is 0.1 to 50% by mass and the amount of the solid coating component (B) is 3 to 99.9% by mass. Ｒ１及びＲ２がそれぞれ独立に炭素数５〜１０で、直鎖もしくは分岐鎖のアルキル基を示す請求項１記載の水系潤滑皮膜処理剤。 The water-based lubricating film treating agent according to claim 1, wherein R 1 and R 2 each independently represent a linear or branched alkyl group having 5 to 10 carbon atoms. 固体皮膜成分（Ｂ）が、水性無機塩、水性有機酸塩及び水性樹脂から選ばれる少なくとも一種である請求項１又は２記載の水系潤滑皮膜処理剤。 The aqueous lubricant coating composition according to claim 1 or 2, wherein the solid coating component (B) is at least one selected from aqueous inorganic salts, aqueous organic acid salts and aqueous resins. 水性無機塩が、硫酸塩、ホウ酸類の塩、ケイ酸類の塩及びリン酸類の塩から選ばれる少なくとも一種である請求項３記載の水系潤滑皮膜処理剤。 The water-based lubricating film treating agent according to claim 3 , wherein the aqueous inorganic salt is at least one selected from sulfates, salts of boric acids, salts of silicic acids and salts of phosphoric acids. 水性有機酸塩が、水酸基を有するか有さない炭素数３〜６の二もしくは三塩基性カルボン酸の塩である請求項３又は４記載の水系潤滑皮膜処理剤。 The water-based lubricating film treating agent according to claim 3 or 4 , wherein the aqueous organic acid salt is a salt of a dibasic or tribasic carboxylic acid having 3 to 6 carbon atoms and having or not having a hydroxyl group. 水性樹脂が、アクリル系樹脂、フェノール系樹脂、ウレタン樹脂、エポキシ樹脂及びポリエステル樹脂から選ばれる少なくとも一種である請求項３〜５のいずれか１項に記載の水系潤滑皮膜処理剤。 The aqueous lubricant film treatment agent according to any one of claims 3 to 5 , wherein the aqueous resin is at least one selected from an acrylic resin, a phenol resin, a urethane resin, an epoxy resin, and a polyester resin. 油、石けん、金属石けん、ワックス及びポリテトラフルオロエチレンから選ばれる少なくとも一種である補足成分（Ｃ）を、水系潤滑皮膜処理剤の全固形分を基準にして、固形分として、１〜５０質量％配合した請求項１〜６のいずれか１項に記載の水系潤滑皮膜処理剤。 The supplement component (C), which is at least one selected from oil, soap, metal soap, wax, and polytetrafluoroethylene, is 1 to 50% by mass as a solid content based on the total solid content of the aqueous lubricant film treatment agent. The water-based lubricating film treating agent according to any one of claims 1 to 6 , which is blended. 二硫化モリブデン、グラファイト、カーボンブラック、有機モリブデン化合物、リン酸亜鉛化合物、石灰、メラミンシアヌレート及び窒化ホウ素から選ばれる少なくとも一種である補足成分（Ｄ）を、水系潤滑皮膜処理剤の全固形分を基準にして、固形分として、０．１〜７０質量％配合した請求項１〜７のいずれか１項に記載の水系潤滑皮膜処理剤。 Supplementary component (D) which is at least one selected from molybdenum disulfide, graphite, carbon black, organic molybdenum compound, zinc phosphate compound, lime, melamine cyanurate and boron nitride, and the total solid content of the aqueous lubricant coating treatment The water-based lubricating film treating agent according to any one of claims 1 to 7 , which is blended in an amount of 0.1 to 70% by mass as a solid content. 水系潤滑皮膜処理剤の適用対象である固体が金属材料である請求項１〜８のいずれか１項に記載の水系潤滑皮膜処理剤。 The aqueous lubricant film treatment agent according to any one of claims 1 to 8 , wherein the solid to which the aqueous lubricant film treatment agent is applied is a metal material. 上記請求項１〜８のいずれか１項に記載の水系潤滑皮膜処理剤より形成される潤滑皮膜を表面に有する金属材料。 A metal material having on its surface a lubricating film formed from the aqueous lubricating film treating agent according to any one of claims 1 to 8 . 金属材料が鉄もしくは鉄鋼、ステンレス鋼、メッキ鋼、アルミニウムもしくはアルミニウム合金、マグネシウム合金、スズもしくはスズ合金、チタンもしくはチタン合金、並びに銅もしくは銅合金から選ばれる請求項１０記載の金属材料。


11. The metal material according to claim 10 , wherein the metal material is selected from iron or steel, stainless steel, plated steel, aluminum or aluminum alloy, magnesium alloy, tin or tin alloy, titanium or titanium alloy, and copper or copper alloy.


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