KR20080007657A - Water Based Lubrication Coating Agent For Solids - Google Patents

Abstract

Branched carboxyl having a pour point of less than 0 ° C, represented by the formula R ¹ -CH (R ² ) COOH (wherein R ¹ and R ² each independently represent a carbon group having 4 to 12 carbon atoms and a linear or branched alkyl group); As a water-based lubricating coating agent for solids formed by blending an acid and / or its salt with a solid coating component, the compounding amount of the branched carboxylic acid or its salt as a solid is 0.1-50 based on the total solids of the water-based lubricating coating agent. The water-based lubricating film treatment agent which is mass% and whose compounding quantity of a solid film component is 3-99.9 mass%. According to the present invention, an aqueous lubricating coating agent mainly for metal materials and the like, which can form a coating having low foaming, which can contain a large amount of lubricating components, and which has excellent liquid stability and exhibits good lubricity, is provided. . The solid coating component is selected from aqueous inorganic salts, aqueous organic acid salts or aqueous resins. The treatment agent may be further blended with a lubricity supplement component, a baking resistance supplement component, and the like.

Description

Aqueous LUBRICATING COATING AGENT TO BE USED FOR SOLIDS

The present invention relates to solids, such as friction generated between solid surfaces (particularly between dies and workpieces) during mechanical processing of metals such as forging, drawing, press forming, roll forming, and the like, and mechanical sliding surfaces inside an engine or compressor. Solids (especially metal materials / metal products) which are required in various applications / areas for the purpose of reducing the friction generated by the solids and the solids rub against each other, such as the friction generated between the surfaces (for example between the cylinder and the piston) It relates to an aqueous lubricating film treatment agent for forming a lubricating film on a). More specifically, in the present invention, in order to include a lubricant component having excellent performances such as soaps in an aqueous treatment liquid, a large amount of surfactants have been used in spite of the conventional problem of adverse effects on the foaming and coating performance of the treatment liquid. The present invention relates to a water-based lubricating coating agent for solids, which has to be used in combination with a polymer dispersant and has very low foaming and is capable of stably containing a large amount of lubricating components.

In plastic processing where solid surfaces, especially metal surfaces (especially dies and workpieces) rub against each other vigorously, friction generated in the mechanical sliding parts causes increased processing energy, heat generation, baking, etc. Various lubricants have been used. As lubricants, oils, soaps, and the like have been used for a long time to reduce frictional force as a fluid lubricating film. However, high-speed sliding of plastic sliding parts and mechanical sliding parts that are slid under high surface pressure accompanied by large heat generation due to surface area expansion. In cotton or the like, baking phenomenon is likely to occur due to insufficient lubricity or breakage of the lubricating film. Therefore, in order to avoid direct contact between metals even when the lubrication film is broken, an inorganic film such as borax (borax) film, a phosphate crystal film, and a solid film such as a resin film are covered in advance with the target solid surface. Technology is common and widely used.

On the other hand, in recent years, the processing and sliding energy is further reduced, and the workability is improved, the response to difficult materials is processed, and the environmental integrity of the coating process (for example, phosphate treatment generates a large amount of industrial waste such as sludge. The demand for solid coatings, such as the response to lubricating powderless or oilless processing, is rapidly increasing in various fields. In consideration of these requirements, environmental preservation is being made, and solid coatings having high lubricity have been developed. . This technique attaches a liquid coating agent to a solid surface, such as a workpiece or a mechanical sliding part, and then forms a highly lubricity coating by a simple process of only drying. As such a technique, Patent Document 1 contains (A) synthetic resin, (B) water-soluble inorganic salt and water, and (B) / (A) (solid content weight ratio) is 0.25 / 1 to 9/1, and synthetic resin is dissolved. Or a lubricant composition for plastic working of a metal material, characterized in that it is dispersed. It is preferable to contain 1-20 mass% of patent documents 1 at least 1 sort (s) chosen from the group which consists of a metal soap, wax, polytetrafluoroethylene, and oil as a lubricating component, and as said water-soluble inorganic salt, sulfate and borate Also preferred is at least one member selected from the group consisting of molybdates, vanadates and tungstates. This technology contains a lubricating component such as metal soap or wax in a dispersed form in a coating component that can be a carrier, and coats it on the surface of the workpiece to obtain a lubricating coating having high processing performance simply and dynamically. It is an excellent technique. According to this technique, since the lubrication component is immobilized in the film by an inorganic salt or a resin component, compared with the above-mentioned "solid film + lubrication component", it is not influenced by the wettability of the lubricant to a solid surface, interlayer adhesion, etc. It can provide a stable lubrication state. In addition, this technique is widely used in the field of plastic processing, and even when compared with a combination of a phosphate coating and a soap, which is a lubricating coating of a relatively large crystal unit, the effect of the lubricating component can be arbitrarily adjusted by selection of the lubricating component, dispersion state, and the like. On the basis of this technology, excellent technology has been developed for steel processing applications having a large surface area, and is a promising technology.

Patent Document 1: Japanese Unexamined Patent Publication No. 2000-063880

Disclosure of the Invention

Problems to be Solved by the Invention

However, many materials used as lubricating components lack hydrophobicity or solubility in water. For example, alkali soaps are considered to have excellent mold (die) protection performance during cold forging, but solubility in aqueous liquids. Since it is low, most of them cannot be blended, and cause extreme foaming. Moreover, metal soaps and the like have strong hydrophobicity and are difficult to disperse in an 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 coexist and disperse a surfactant, a polymer dispersing agent, etc. in a large amount, but when a surfactant, a polymer dispersing agent, etc. are coexisting in a large amount, There is also a problem of foaming and a decrease in film performance (e.g., a decrease in water resistance, non-uniformity in lubrication performance due to the segregation of surfactants and polymer dispersants during film formation, etc.), Attempting to increase the lubricating component content without the aid of a surfactant or a polymer dispersant tends to impair the stability of the lubricating coating agent.

Disclosure of Invention The present invention solves the problems of the prior art, and aims to provide an aqueous lubricating coating agent mainly for metal materials, which has low foaming and is excellent in liquid stability, although it may contain a large amount of lubricating components. do.

Means to solve the problem

The subject is general 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 branched carboxylic acid and / or its salt (A) having a pour point of less than 0 ° C; As a water-based lubricating film treatment agent for the solid formed by mix | blending a solid film component (B), the compounding quantity of branched carboxylic acid or its salt is 0.1-50 mass% as solid content based on the total solid of the water-based lubricating film treatment agent, It is solved by the water-based lubricating film treatment agent whose compounding quantity of a solid film component is 3-99.9 mass%. As a solid film component, at least 1 sort (s) chosen from aqueous inorganic salt, aqueous organic acid salt, and aqueous resin is used normally. As the water-based lubricating coating agent, at least one selected from oil, soap, metal soap, wax and polytetrafluoroethylene can be blended as a supplemental component (supplementary component (C)) for adjusting lubricity. Moreover, as this water-based lubricating coating agent, molybdenum sulfide, graphite, carbon black, an organic molybdenum compound, a zinc phosphate compound, and lime for the purpose of improving baking resistance, die protection, and / or lubrication assistance in steel processing applications. , At least one selected from melamine cyanurate and boron nitride can be blended as the supplement component (D). The present invention also relates to a metal material having a lubricating film formed on the surface of the aqueous lubricating coating agent.

Effects of the Invention

The water-based lubricating coating agent of the present invention is not only particularly excellent in the performance required for industrial stable use such as foam resistance and treatment liquid stability, but also may contain a sufficient amount of lubricating component, and the water-based lubricating coating treatment of the present invention. The zero formed film exhibits good performance as a sliding lubricating film or a cold forging lubricating film. Therefore, the present invention has a great industrial value.

Implement the invention  Best form for

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

R ¹ and R ² in the branched carboxylic acid represented by the general formula (I) in the present invention (hereinafter referred to as the branched carboxylic acid (I); also the same as those of other general formulas) are each independently, Although it is necessary to be a C4-C12 linear or branched alkyl group, it is preferable that it is a C5-C10 linear or branched alkyl group. When carbon number of R <^1> and / or R <^2> is 3 or less, or 13 or more, there exists a tendency for the balance of a hydrophilic group and a hydrophobic group to be out of a suitable range, and to be unable to express sufficient defoaming performance and dispersion performance. 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-hex Real group, 1-methyl-3, 3- dimethyl butyl 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- Methyl nonyl group, 5-methyldecyl group, 6-methyl undecyl group, etc. are mentioned.

Among the branched carboxylic acids (I), the branched carboxylic acids represented by the following general formula (I-1) are more preferable for use in the present invention. In general formula (I-1), although R <^3> and R <^4> may be a hydrogen atom or a C1-C7 linear or branched alkyl group each independently, the carbon number of both groups is 2-7 in total. in need. Of these, R ³ is straight-chain alkyl group having a carbon number of 2-5, and R ⁴ is a hydrogen atom branch-carboxylic acid (I-1), R ³ is a carbon number of 3-7 of the branched alkyl group R ⁴ is a hydrogen atom in branches The carboxylic acid (I-1) and branched carboxylic acid (I-1) whose R <^3> is a C3-C6 branched alkyl group and R <^4> is a methyl group are more preferable. Here, as a C1-C7 linear or branched chain alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pen And a methyl group, isopentyl group, neopentyl group, 2-methylpentyl group, 3-methylpentyl group, 2-methylhexyl group, 3-methylhexyl group, and 4-methylhexyl group.

As for the branched carboxylic acid used by this invention, the pour point should also be less than 0 degreeC, it is preferable that it is -1 degrees C or less, and it is more preferable that it is -15 degrees 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.

Although the following compounds are mentioned as a specific example of the branched carboxylic acid used by this invention, The branched carboxylic acid used by this invention is not limited to these.

The pour point of branched carboxylic acid (I-1-1)-branched carboxylic acid (I-1-5) is as follows.

Branched carboxylic acid (I-1-1): -30 degrees C or less, branched carboxylic acid (I-1-2): -17 degreeC, branched carboxylic acid (I-1-3): -30 degrees C or less, Branched carboxylic acid (I-1-4): -30 degrees C or less, branched carboxylic acid (I-1-5): -1 degreeC.

In addition, branched carboxylic acid (I-1-1)-branched carboxylic acid (I-1-5) are all contained in branched carboxylic acid (I-1).

When the carbon number and the pour point of the branched carboxylic acid (I) are within the above ranges, the aqueous lubricating coating agent containing such branched carboxylic acid (I) or salts thereof is less foamed, has excellent liquid stability, and has a large amount of lubricating components. In addition to this, 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 of producing dimer acid from fatty acids from (1) vegetable oils (soybean oil, tall oil, etc.), animal oils (Uji etc.); (2) olefins The aldehyde obtained by putting in the oxo reaction can be obtained by a method of hydrogenating an aldehyde having a carbon-carbon double bond obtained by putting it in aldol condensation to oxidize it as an alcohol.

Among these methods, the method (2) can be represented by the following reaction process formula. In addition, in the following reaction process formula, R <^3> and R <^4> is the same as that of branched carboxylic acid (I-1).

As a salt of the branched carboxylic acid used by this invention, Salt with alkali metals, such as sodium, potassium, lithium; Salt with alkaline-earth metals, such as calcium and magnesium; Aliphatic amines, such as methylamine, ethylamine, and propylamine And salts thereof; salts with alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; ammonium salts and the like. Among these salts, salts with alkali metals and ammonium salts are more preferred.

The branched carboxylic acid and its salt used by this invention can be used individually or in combination of 2 or more types.

The branched carboxylic acid and / or its salt, ie, the branched carboxylic acid and / or its salt (A), used in the present invention are contained in the dissolved or dispersed state in the aqueous lubricating coating agent of the present invention. In addition, the branched carboxylic acid and / or its salt (A) in the lubricating film formed of the water-based lubricating coating agent are distributed in the film or in the upper layer of the film, thereby providing excellent lubricity to the lubricating film. Moreover, when branched carboxylic acid and / or its salt (A) coexist with a polyvalent metal compound in a lubricating film, it may exist as a metathesis reaction product. For example, the zinc compound of the branched carboxylic acid precipitates on the surface of the zinc phosphate crystal in the coexistence with the zinc phosphate crystal, and the calcium compound of the branched carboxylic acid precipitates in the coexistence of the lime particles, thereby being excellent on the surface of these polyvalent metal compounds. Gives lubricity.

Since branched carboxylic acid and / or its salt (A) function as an excellent dispersing agent with respect to the various lubricating components which may coexist in an aqueous lubricating film treatment agent, the dispersion stability of various lubricating components can be improved remarkably. For this reason, by using it in large quantities so that the dispersion stability of various lubricating components can be improved, combined use of surfactant, a polymeric dispersing agent, etc. which have become the cause of foaming and a film | membrane deterioration is not required, or can be drastically reduced. Moreover, since branched carboxylic acid and / or its salt (A) also function as an excellent antifoamer, foaming in lubricating components, such as alkaline soaps, surfactant, a polymeric dispersing agent, etc. can be highly suppressed.

It is preferable to use content of a branched carboxylic acid and / or its salt (A) in 0.1-50 mass% as a ratio of solid content with respect to the total solid of an aqueous lubricating film treatment agent, and in 0.3-30 mass% It is more preferable to use. If it is less than 0.1-50 mass%, the effect by the addition, ie, a lubricity function, an antifoamer function, and a dispersing agent function, is not performed, but when it exceeds 50 mass%, these functions become saturated and it becomes an economic waste.

As the solid coating component (B) which is an essential component in the aqueous lubricating coating agent of the present invention, at least one selected from an aqueous inorganic salt, an aqueous organic acid salt and an aqueous resin can be used. "Aqueous" means water-soluble or water dispersibility here. By coating the solid coating component (B) on the target surface in advance, it has a role of avoiding baking phenomenon by avoiding direct contact between the metals at the time of plastic working of the metal or breaking of the fluid lubricating film of the mechanical sliding surface. The solid film component (B) further reduces oil, soaps, waxes, molybdenum sulfide, graphite, zinc phosphate compounds, lime, melamine cyanurate, etc. in the film, thereby reducing the friction coefficient on the surface of the lubricating film. It plays a role of providing lubricity and the like, and supplying a lubricating component and a baking component to the friction sliding surface. The solid coating component (B) in the water-based lubricating coating agent of the present invention is present in a dissolved or dispersed state in water, and volatilizes water to form a solid coating at room temperature.

The solid coating component (B) can be arbitrarily selected by the use of the lubricating coating to be formed. For example, in the case of cold forging applications in which the temperature and pressure of the friction sliding surface are very high, the melting point of the coating is higher than the material arrival temperature at the time of processing, so that the above role can be stably exhibited without being affected by the processing heat. It is preferable to use an aqueous inorganic salt from the point. As the aqueous inorganic salt having such a property, it is preferable to use at least one selected from sulfates, salts of boric acids, salts of silicic acids and salts of phosphoric acids. Boric acids include oltoboric 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. Silicates include oligosilicic acid (nSiO ₂ · (n + 1) H ₂ O), metasilicate (nSiO ₂ · nH ₂ O), mesosilicate (nSiO ₂ · (n-1) H ₂ O), and parasilicate (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, ...) (diphosphate, triphosphate, tetraphosphate, etc.), meta Phosphoric acid [(HPO ₃ ) _n ] (n = 1, 2, 3, 4, ...) (metaphosphoric acid, 2methacrylic acid, 3methacrylic acid, 4methacrylic acid, etc.).

As cations of these salts, cations (salts) formed of alkali metal ions (sodium ions, potassium ions, lithium ions, etc.), ammonium ions, amines (ethylamine, etc.) or alkanolamines (monoethanolamine, diethanolamine, etc.) (Amine salt) etc. are mentioned, Alkali metal ion and ammonium ion are more preferable. Specific examples of the aqueous inorganic salt include sodium sulfate, potassium sulfate, sodium borate (such as sodium tetraborate), potassium borate (such as potassium tetraborate), diethanolamine salt of boric acid, sodium silicate, potassium silicate, lithium silicate, and sodium metasilicate And sodium phosphate, potassium phosphate, sodium tripolyphosphate and the like. These may be used independently and may be used in combination of 2 or more type.

In particular, for salts of silicic acids, those represented by the general formula M ₂ O.nSiO ₂ (wherein n represents a number from 1 to 9 and M represents Na, K, Li or NH ₄ ) are used. desirable. From the viewpoint of the stability of the aqueous solution, the film manufacturability, and the like, M is more preferably Na or K, more preferably n is a number from 2 to 9, and still more preferably a number from 2 to 4.

Moreover, in the case of the use of a comparatively hardness plastic processing, and when it is desired to volatilize the film | membrane remaining after a process at the time of heat processing, it is preferable to use the aqueous organic acid salt which can form a firm film | membrane and has good thermal volatility as a solid film component. Do. As an aqueous organic acid salt having such a property, it is preferable to use a salt of a C3-C6 di or tribasic carboxylic acid having or without a hydroxyl group, and it is selected from malate, succinate, citrate and tartarate. It is more preferable to use at least 1 sort (s) used. As cations of these salts, cations (salts) formed of alkali metal ions (sodium ions, potassium ions, lithium ions, etc.), ammonium ions, amines (ethylamine, etc.) or alkanolamines (monoethanolamine, diethanolamine, etc.) (Amine salt) etc. are mentioned, Alkali metal ion and ammonium ion 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 independently and may be used in combination of 2 or more type.

Moreover, when a non-hygroscopic property, abrasion resistance, etc. are calculated | required by the lubricating film for mechanical sliding surfaces, etc., it is preferable to use aqueous resin as a solid film component. As an aqueous resin which has such a property, it is preferable to use at least 1 sort (s) chosen from acrylic resin, a phenol resin, a urethane resin, an epoxy resin, and polyester resin. The aqueous resin used herein is not particularly limited as long as it has a film forming property, and is generally supplied in a water-soluble or water-dispersible state. From the viewpoint of using the aqueous resin used as the water-based lubricating coating agent of the present invention for non-dehumidifying applications, it is preferable to crosslink using a crosslinking agent when forming a water-soluble resin. Moreover, since the aqueous resin has a relatively high molecular weight or a hydrophobic resin skeleton, it is preferable that the aqueous resin is an emulsion dispersed in water. These aqueous resins may be used alone or in combination of two or more thereof.

Acrylic resin is what is obtained by superposing | polymerizing at least 1 sort (s) of acryl-type monomer. As an acryl-type monomer, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, Alkyl (C = 1-8) (meth) acrylates such as octyl acrylate; methoxymethyl acrylate, methoxyethyl acrylate, ethoxymethyl acrylate, ethoxyethyl acrylate, methoxymethyl methacrylate, Lower alkoxy lower alkyl (meth) acrylates such as methoxyethyl methacrylate, ethoxymethyl methacrylate, ethoxyethyl methacrylate, and methoxybutyl acrylate; 2-hydroxyethyl (meth) acrylate, 3 Hydroxy lower alkyl (meth) acrylates, such as -hydroxypropyl (meth) acrylate; Acrylamide, methacrylamide; N-methylol acrylamide, N-methylol (Meth) acrylamides having N-unsubstituted or substituted (particularly lower alkoxy substituted) methylol groups, such as tacrylamide, N-butoxymethylacrylamide, N-butoxymethylmethacrylamide; phosphonyloxymethylacrylate Phosphonyloxy lower alkyl (meth) acrylates such as phosphonyloxyethyl acrylate, phosphonyloxypropyl acrylate, phosphonyloxymethyl methacrylate, phosphonyloxyethyl methacrylate and phosphonyloxypropyl methacrylate Acrylonitrile; Acrylic acid, methacrylic acid, etc. are mentioned. In the present invention, the acrylic resin is an acrylic monomer unit as a copolymer of at least one of the aforementioned acrylic monomers and at least one of other ethylenic monomers such as styrene, methylstyrene, vinyl acetate, vinyl chloride, vinyltoluene, and ethylene. Shall also contain 30 mol% or more. The molecular weight of the acrylic resin is preferably 1,000 to 1,000,000, particularly 100,000 to 600,000, as measured by gel permeation chromatography.

As a phenol resin, what is obtained by reaction of at least 1 sort (s) of phenols, such as a phenol, a cresol, a xylenol, and formaldehyde, may be any of a novolak-type resin and a resol-type resin. When using a novolak-type resin, it is necessary to coexist hexamethylenetetramine etc. as a hardening | curing agent. The phenol resin film is cured by a drying step described later. There is no restriction | limiting in particular about the molecular weight of a phenol resin.

A urethane resin is a synthetic resin which has a urethane bond (NHCOO), and what is obtained by the polymerization part of the polyisocyanate compound which has two or more isocyanate groups, and the polyol which has two or more active hydrogen groups generally by reaction can be used as a urethane resin. have. Such polyols include polyester polyols and polyether polyols. Examples of the polyester polyols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,2-butylene glycol, and 1,3. Low molecular weight polyols such as butylene glycol, 1,4-butylene glycol, 3-methylpentanediol, hexamethylene glycol, hydrogenated bisphenol A, trimethylolpropane, glycerin, succinic acid, glutaric acid, adipic acid, The polyester compound which has a hydroxyl group at the terminal obtained by reaction with polybasic acids, such as a baric acid, a phthalic acid, an isophthalic acid, a terephthalic acid, trimellitic acid, tetrahydrophthalic acid, an endomethylene tetrahydrophthalic acid, and hexahydrophthalic acid, is mentioned.

As the polyether polyol, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,2-butylene glycol, 1 Low molecular weight polyols such as, 3-butylene glycol, 1,4-butylene glycol, 3-methylpentanediol, hexamethylene glycol, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, glycerin, or ethylene oxide thereof; and And / or polyether polyols such as propylene oxide high additives, polyethylene glycol, polypropylene glycol, polyethylene / propylene glycol, polycaprolactone polyols, polyolefin polyols, polybutadiene polyols, and the like.

Moreover, as polyisocyanate, aliphatic, alicyclic, and aromatic polyisocyanate is mentioned, Specifically, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, hydrogenated xylylene diisocyanate, 1, 4- cyclo Hexylene diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, 2,4'-dicyclohexyl methane diisocyanate, isophorone diisocyanate, 3,3'-dimethoxy-4,4'-biphenylenedi Isocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'- diphenylmethane diisocyanate, 2,4 '-Diphenylmethane diisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, etc. are mentioned. Can be.

The molecular weight of the urethane resin is preferably 500 to 500,000 when measured by gel permeation chromatography.

As an epoxy resin, bisphenol, especially bisphenol-A epoxy resin obtained by making bisphenol A (2, 2-bis (4'-hydroxyphenyl) propane) react with epichlorohydrin, especially the bisphenol-A epoxy represented by following formula Resin is mentioned first. As another example, the novolak-type epoxy resin which glycidyl-etherylated the phenolic hydroxyl group of phenol novolak resin, the glycidyl ester of aromatic carboxylic acid, and the peroxide epoxy type which epoxidized the double bond of ethylenically unsaturated compound with peracid Etc. can be mentioned. Moreover, what added ethylene oxide or a propylene oxide to the resin skeleton of the above epoxy resin, the glycidyl ether type of polyhydric alcohol, etc. are mentioned. It is most preferable to use a bisphenol-A epoxy resin among these. When the molecular weight of an epoxy resin is measured by gel permeation chromatography, it is preferable that it is 350-5,000.

As polyester resin, polyester resin etc. which are condensates of polyol components, such as ethylene glycol and neopentyl glycol, and polybasic acids, such as terephthalic acid and trimellitic acid, are mentioned. The molecular weight of the polyester resin is preferably 1,000 to 50,000 when measured by gel permeation chromatography.

The compounding quantity of a solid film component (B) needs to be 3-99.9 mass% as solid content on the basis of the total solid of the water based lubricating film treatment agent, It is preferable that it is 3-95 mass%, It is 5-90 mass% More preferred. If it is less than 3 mass%, the baking resistance of the formed film will become inadequate, and the holding | maintenance and supply functions of a lubrication component, etc. will become inadequate. When it exceeds 99.9 mass%, the function of branched carboxylic acid and / or its salt (A) will not be exhibited.

The aqueous lubricating film treatment agent of the present invention may further contain a complementary component in order to adjust various performances of the lubricating film to be formed, if necessary. For example, it is preferable to use at least 1 type (supplementary component (C)) chosen from oil, a soap, metal soap, a wax, polytetrafluoroethylene as a supplement component used mainly when adjusting lubrication performance. . In addition, although the replenishment component (C) is normally used in order to improve lubrication performance, it may be used in order to suppress it in some cases.

Vegetable oil, synthetic oil, mineral oil, etc. can be used as oil in a supplement component (C), For example, palm oil, castor oil, rapeseed oil, machine oil, turbine oil, ester oil, silicone oil, etc. are mentioned. Soaps are alkali metal salts of fatty acids, for example sodium salts of saturated or unsaturated fatty acids having 8 to 22 carbon atoms, such as octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, icosanoic acid, oleic acid and stearic acid. And potassium salts. Examples of the metal soap include polyvalent metals such as calcium, zinc, magnesium, and barium, and salts of the fatty acids. Examples of the wax include polyethylene wax, polypropylene wax, carnauba wax, paraffin wax, and the like. Examples of polytetrafluoroethylene include polytetrafluoroethylene having a degree of polymerization of, for example, 1 million to 10 million. These may be used independently and may be used in combination of 2 or more type. The supplemental component (C) is usually contained in the aqueous or lubricating coating agent of the present invention in a dissolved or dispersed state.

It is preferable that it is 1-50 mass% as solid content, as for the compounding quantity of a supplement component (C) based on the total solid of an aqueous lubricating film treatment agent, it is more preferable that it is 2-30 mass%. More preferred. If it is less than 1 mass%, the lubrication performance adjustment function of the replenishment component (C) is not fully exhibited, and if it exceeds 50 mass%, the lubrication performance adjustment effect will be saturated and it is economically disadvantageous.

As the water-based lubricating coating agent of the present invention, further, if necessary, for the purpose of improving baking resistance for die processing, die protection, and the like, a function of assisting lubrication at a high processing load and an extreme pressure effect are exhibited. And the like can be blended. As such, one selected from molybdenum sulfide, graphite, carbon black (including graphite carbon black), organic molybdenum compound (molybdenum DTC), zinc phosphate, lime, melamine cyanurate, boron nitride and the like (supplement component ( It is preferable to use D)). These may be used independently and may be used in combination of 2 or more type.

It is preferable that it is 0.1-70 mass% as solid content, and, as for the compounding quantity of a supplement component (D) based on the total solid of an aqueous lubricating film treatment agent, it is more preferable that it is 2-60 mass% More preferred. If it is less than 0.1 mass%, functions, such as improvement of baking resistance and die | dye protection, are not exhibited, and even if it mix | blends more than 70 mass%, the new improvement of this effect cannot be desired.

In the aqueous lubricating coating agent of the present invention, since the branched carboxylic acid and / or its salt (A) is responsible for stably dispersing the replenishment component (C) and the replenishment component (D), these components are usually Although it is not necessary to mix | blend various surfactant, a polymeric dispersing agent, etc. in order to disperse | distribute or emulsify, In order to supplement the function of a component (A), etc. when compounding a supplement component (C) or a supplement component (D) in large quantities, surfactant is used. You can also use Moreover, surfactant may enter with commercially available aqueous resin, a supplement component (C), etc. As such a surfactant, it can select suitably from nonionic surfactant, anionic surfactant, amphoteric surfactant, cationic surfactant, water-soluble polymer dispersing agent, etc.

The medium in the aqueous lubricating coating agent of the present invention is water. Although there is no restriction | limiting in particular about the total solid content concentration in the water-based lubricous coating agent of this invention, Usually, about 1-50 mass% is suitable.

The manufacturing method of the aqueous lubricating coating agent of the present invention is not particularly limited as long as the produced aqueous lubricating coating agent satisfies the above conditions. For example, the aqueous lubricating coating agent of the present invention dissolves or disperses the branched carboxylic acid and / or its salt (A) in water, followed by the solid coating component (B) and, if necessary, the supplementary component (C). And / or it can manufacture by adding and stirring a supplemental component (D). In addition, the water-based lubricating coating agent of the present invention may take the form of a powder package which the user dissolves or disperses in water. In the case of a powder package, branched carboxylic acid and / or its salt (A) and the solid film component (B) of powder state are mixed, and a supplement component (C) and / or a supplement component (D) are added as needed. It can be prepared by mixing with a powder mixer or the like.

The water-based lubricating coating of the present invention can be made of iron or steel, stainless steel, plated steel (eg, plated steel such as electro galvanized, hot dip galvanized, aluminum zinc plated, aluminum plated, iron zinc plated, etc.), aluminum or aluminum. In the case of metal materials such as alloys, magnesium alloys, tin or tin alloys, titanium or titanium alloys, copper or copper alloys, for example, by cold plastic working represented by forging, drawing, fuse, press forming, roll forming, etc. It can apply to the surface of a metal material as a lubricating coating agent for reducing the friction generate | occur | produced between surfaces (for example, between a die and a metal material). There is no restriction | limiting in particular about the shape of a metal material, etc. The water-based lubricating coating agent of the present invention is also a lubrication for reducing friction generated between the surface of the sliding metal member inside the machine such as an engine or a compressor and a solid surface such as the metal member (for example, between the piston and the cylinder). It can be used as a coating agent. The water-based lubricating coating agent of the present invention can also be applied to solid surfaces (for example, ceramic surfaces, plastic surfaces, etc.) made of nonmetallic materials.

Prior to applying the water-based lubricating coating agent of the present invention, the target solid surface (for example, the surface of a metal material) is cleaned (usually using an alkali cleaner), washed with water, descaled (shot blast or hydrochloric acid, etc.). Etc.) It is preferable to clean the surface by pretreatment in the order of washing with water in order to exhibit good lubricity. In the case where the oxidation scale is not adhered, when the oxide scale is used for an application requiring the oxidation scale, or in the case of a solid surface made of a nonmetallic material, descaling → water washing may be omitted. These pretreatment may be performed by a conventional method.

The aqueous lubricating coating agent of the present invention is applied to a solid surface (for example, a metal material surface) by conventional methods such as dipping, spraying, shedding, brush coating, and the like. Application | coating should just be fully covered with the solid lubricating film treatment agent, and there is no restriction | limiting in particular in the time to apply | coat. After coating, the aqueous lubricating coating agent needs to be dried. Although drying may be left to normal temperature standing, it is preferable to perform 1 minute-60 minutes normally at 60 degreeC-150 degreeC. Although the film mass of an aqueous lubricating coating agent changes with a use, it is preferable that it is 1 g / m <2> or more as a dry film from a viewpoint of preventing baking from the plastic processing use of a metal material, It is more preferable that it is 3-30 g / m <2>, It is more preferable that it is 3-20g / m <2>.

The lubricating film formed of the water-based lubricating coating agent of the present invention has a good lubrication property and baking resistance by distributing branched carboxylic acid and / or its salt (A) in the film or in the upper layer of the film, and has a stable lubrication state on the friction sliding surface. To provide. For this reason, it shows stable performance excellently in the cold plastic working sliding under high surface pressure with high heat generation by surface area expansion, or the high speed sliding surface of a mechanical sliding part. Moreover, the supplement component (C) and supplement component (D) which are mix | blended as an arbitrary component can be distributed uniformly in a solid lubricating film by the outstanding dispersing agent function of branched carboxylic acid and / or its salt (A), It may be distributed in the upper layer of the film together with the branched carboxylic acid and / or its salt (A) at the time of lubricating film formation. For example, when the aqueous inorganic salt as a solid film component (B) and the branched carboxylic acid alkali metal salt whose solubility with respect to the aqueous solution are comparatively small are combined, the branched carboxylic acid is prevented by the precipitation floating phenomenon at the time of film formation. The alkali metal salt can be distributed in the upper layer of the coating, and each supplementary component dispersed by the branched carboxylic acid alkali metal salt is also distributed in the upper layer of the coating. The industry's advantages are great.

By incorporating the examples of the present invention with the comparative examples, the present invention will be described more specifically with the effects. In addition, this invention is not restrict | limited by these Examples.

(1) Preparation of Water-Based Lubrication Coating Agent

Using each component shown below in the combination and ratio shown in Table 1, the water-based lubricating film treatment agent of Examples 1-11 shown in Table 1 and Comparative Examples 1-6 was prepared. In all of these aqueous lubricating coating agents, the mass ratio of total solids: water in the aqueous lubricating coating agent was 1: 9.

<Branched carboxylic acid and / or its salt (A)>

Pour points of the acids constituting the compounds of a-1 to a-6 are as follows.

a-1: -1 degreeC, a-2: -17 degreeC, a-3: -30 degreeC or less, a-4: -30 degreeC or less, a-5: 10 degreeC, a-6: 7 degreeC

The compounds of a-1 to a-4 are branched carboxylic acids or salts thereof within the scope of the present invention, and the compounds of 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, 3 SiO ₂ )

b-4 sodium tripolyphosphate

b-5 ammonium citrate

b-6 Phenolic resin: Amino acidized and soluble in phenol novolac (molecular weight 500-6,000)

b-7 Acrylic resin: Emulsion polymerization of the copolymer of methyl methacrylate and n-butyl acrylate with polyoxyethylene alkyl phenyl ether (molecular weight 150,000 or more)

<Supplementary Component (C)>

c-1 sodium stearate

c-2 calcium stearate: dispersed in water with a polymeric dispersant

c-3 polyethylene wax ： Manufactured by emulsion polymerization of ethylene (molecular weight 20,000)

c-4 polytetrafluoroethylene: dispersed in water with a polymeric dispersant

<Supplementary Component (D)>

d-1 molybdenum sulfide ： 5 micron of particle diameter

d-2 carbon black ： Mitsubishi Chemical Corporation

d-3 zinc phosphate ： Nippon Parker Co., Ltd.

d-4 organic molybdenum compound (molybdenum DTC) ： Asahi Telephone Industry Co., Ltd.

(2) pretreatment and coating treatment

(2-1) Coating treatment for pretreatment and friction wear test

In Examples 7, 9 and 10 and Comparative Example 4 designed as sliding lubricating coatings, the following treatment procedures were performed.

(a) Test piece for evaluation: Cold rolled steel sheet (SPCC-SB) 150 mm x 70 mm x 0.8 mmt (t is thickness)

(b) Degreasing ： Degreasing agent (registered trademark Fine Cleaner 4360, manufactured by Nippon Parker Co., Ltd.) concentration 20 g / L, temperature 60 ° C., immersion 10 minutes

(c) water washing ： tap water, normal temperature, spray treatment 30 seconds

(d) Lubrication film treatment: Each water-based lubrication film treatment agent prepared above, 40 ° C., soaked for 10 seconds

(e) Drying ： 80 ℃ hot air drying 3 minutes

(f) Dry film mass: 5 g / m 2

(2-1) Coating treatment for pretreatment and cold forging test

About Examples 1-6, 8, and 11 and Comparative Examples 1-3, 5, and 6 which were designed as a lubricating film for cold forging, it processed in the following procedures.

(a) Test piece for evaluation: S45C spheroidizing annealing material 25 mm diameter x 30 mm

(b) Degreasing ： Degreasing agent (registered trademark Fine Cleaner 4360, manufactured by Nippon Parker Co., Ltd.) concentration 20 g / L, temperature 60 ° C., immersion 10 minutes

(c) water washing ： tap water, room temperature, soaking 30 seconds

(d) Lubrication film treatment: Each water-based lubrication film treatment agent prepared above, 40 ° C., soaked for 30 seconds

(e) Drying ： 100 ℃ hot air drying for 10 minutes

(f) Dry film mass: 10 g / m 2

(3) evaluation test

<Foam resistance>

20 mL of each water-based lubricating coating agent prepared above is collected in a 200 mL oily scalpel, shaken for 30 seconds at a liquid temperature of 40 ° C, and left to stand, and the foam resistance is evaluated by the remaining foam height after 3 minutes.

Evaluation criteria ： ○ ： Residual bubble height is less than 5mL

             △: residual bubble height is 5 mL or more and less than 10 mL

             × ： The remaining bubble height is 10 mL or more

<Processing liquid stability>

1000 mL of each aqueous lubricating coating agent prepared above was heated and stirred at 80 ° C. for 120 hours, and then the particle size distribution before and after the test was compared to evaluate the stability of the treatment liquid in the aggregation tendency of each dispersion component and the like. In addition, pure water was appropriately supplemented about the volatile moisture in a test.

Particle diameter distribution measurement: The maximum peak detection particle ratio computed by (maximum peak detection particle number / total detection particle number) was compared with the before and after a heating test using the stereoscopic and droplet monitoring system M400L by the Rayzen Tech company. The rate of change of the maximum peak detection particle ratio is calculated as (maximum peak detection particle ratio after the test / maximum peak detection particle ratio before the test). The smaller this value, the lower the number of dispersed particles due to the aggregation phenomenon.

Evaluation criteria: ○: Change rate of maximum peak detection particle ratio is 0.8 or more

             (Triangle | delta): The change rate of a maximum peak detection particle ratio is 0.6 or more and less than 0.8

             X: Change rate of maximum peak detection particle ratio is less than 0.6

<Friction wear test>

The friction wear test was carried out with the most standard Bowden test as the friction wear test after the coating treatment. About the performance as a sliding lubricating film, the number of slidings until the friction coefficient at the time of sliding exceeds 0.2 was evaluated as the number of baking slidings. The larger this number is, the better.

Test condition ： Use 10 mmφ SUJ2 steel ball as indenter

             Vertical load = 50N, sliding speed = 10mm / s, temperature = 60 ℃

Evaluation criteria ： ○ ： 100 times or more baking sliding count

             △ ： 20 times or more baking sliding frequency is less than 100 times

             × ： Number of times of baking sliding is less than 20 times

<Cold forging test>

In the cold forging test, after performing the coating treatment, a spike test treatment according to the invention of Patent No. 3227721 was performed, and the degree of film follow-up to the protrusion part of the test piece after processing and the presence or absence of the baking part were visually evaluated. Good followability has sufficient baking resistance against surface area expansion during cold plastic working, and baking is liable to occur when the film is not followed.

Evaluation criteria ： ○ ： Film is followed to protrusion, and there is no baking department

             (Triangle | delta): Although a film is not followed to a projection part, there is no baking part

             X: The film | membrane is not following a projection but there is a baking part

Table 2 shows the above test results. As is apparent from Table 2, the water-based lubricating film treatment agents of Examples 1 to 11, which are the water-based lubricating coating agents of the present invention, are further sufficient to be particularly excellent in the performance required for industrial stable use of foam resistance and treatment liquid stability. Since a positive lubrication component can be contained, the obtained lubricating film showed the outstanding performance as a sliding lubricating film or a cold forging lubricating film. On the other hand, the water-based lubricating coating agent of Comparative Examples 1 to 3, which does not contain branched carboxylic acid and / or its salt (A), and branched carboxylic acid and / or its salt (A), has a pour point and / or branched structure. In the aqueous lubricating film treatment agents of Comparative Examples 4 and 5 using salts of different branched carboxylic acids, both or one of the foam resistance and the treatment liquid stability was remarkably inferior, and was not useful for industrial stable use. Moreover, about the comparative example 6 which tried to mix | blend a large amount of sodium stearate which has the outstanding lubrication performance, since the aqueous lubricating coating agent solidified (extreme thickening) and was not established as an aqueous lubricating coating agent, it was excluded from evaluation.

Claims (12)

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 branched carboxylic acid having a pour point of less than 0 ° C. and / or a salt thereof (A) As a water-based lubricating film treatment agent for the solid formed by blending a solid film component (B), the compounding amount of the branched carboxylic acid or its salt (A) as a solid content, respectively, based on the total solids of the water-based lubricating film treatment agent, is 0.1-. It is 50 mass%, The water-based lubricating coating agent whose compounding quantity of solid film component (B) is 3-99.9 mass%. The method of claim 1, The water-based lubricating coating agent, wherein each of R ¹ and R ² independently has 5 to 10 carbon atoms and represents a linear or branched alkyl group. The method of claim 2, Branched carboxylic acid and / or branched carboxylic acid in the salt (A) is general formula (I-1) [Formula 1]

(Wherein R ³ and R ⁴ may each independently be a hydrogen atom or a linear or branched alkyl group having 1 to 7 carbon atoms, but the carbon number of both groups is 2 to 7 in total) and the pour point is 0 An aqueous lubricating coating agent which is a branched carboxylic acid less than ° C. The method according to any one of claims 1 to 3, The water-based lubricating coating agent, wherein the solid coating component (B) is at least one selected from an aqueous inorganic salt, an aqueous organic acid salt, and an aqueous resin. The method of claim 4, wherein The aqueous lubricating coating agent 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 method according to claim 4 or 5, An aqueous lubricating coating agent, wherein the aqueous organic acid salt is a salt of a C 3-6 di or tribasic carboxylic acid having or without a hydroxyl group. The method according to any one of claims 4 to 6, An aqueous lubricating film treatment agent wherein the aqueous resin is at least one selected from acrylic resins, phenolic resins, urethane resins, epoxy resins, and polyester resins. The method according to any one of claims 1 to 7, Aqueous lubricating film which mix | blended 1-50 mass% as solid content based on the total solid of the water-based lubricating coating agent, and the supplementary component (C) which is at least 1 sort (s) chosen from an oil, a soap, a metal soap, a wax, and polytetrafluoroethylene. Treatment agent. The method according to any one of claims 1 to 8, Supplementary ingredient (D) which is at least one selected from molybdenum sulfide, graphite, carbon black, organic molybdenum compound, zinc phosphate compound, lime, melamine cyanurate and boron nitride, based on the total solids of the aqueous lubricant coating agent, An aqueous lubricating film processing agent mix | blended 0.1-70 mass% as solid content. The method according to any one of claims 1 to 9, An aqueous lubricating coating agent, wherein the solid to be applied to the aqueous lubricating coating agent is a metal material. A metal material having a lubricating film formed on the surface of the water-based lubricating coating agent according to any one of claims 1 to 9. The method of claim 11, Metallic material is selected from iron or steel, stainless steel, plated steel, aluminum or aluminum alloys, magnesium alloys, tin or tin alloys, titanium or titanium alloys, and copper or copper alloys.