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

Description

  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.

  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.

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

  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.

  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.

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.

  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.

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.

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.

  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.

  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.

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).

  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.

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).

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.

  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.

  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.

  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.

  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.

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.

  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.

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.

  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.

  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.

  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.

  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.

  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.

  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.

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.

  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.

  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.

  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.

  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.

  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.

  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.

  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.

  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.

  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.

  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.

  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.

  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.).

  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.

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 >.

  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.

  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) 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)>

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.

<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)

<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

<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) 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) 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) 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

<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

<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

<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

  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.

Claims (11)

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. 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. 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. 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. 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. 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. 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. 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. 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. 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 . 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.