CN1243150A - Lubricant for plastic working of metal material - Google Patents

Lubricant for plastic working of metal material Download PDF

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Publication number
CN1243150A
CN1243150A CN99109715A CN99109715A CN1243150A CN 1243150 A CN1243150 A CN 1243150A CN 99109715 A CN99109715 A CN 99109715A CN 99109715 A CN99109715 A CN 99109715A CN 1243150 A CN1243150 A CN 1243150A
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Prior art keywords
lubricant
weight
plastic working
water
composition
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CN99109715A
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CN1148437C (en
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今井康夫
永田秀二
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NIPPON BACALAIJINGU CO Ltd
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NIPPON BACALAIJINGU CO Ltd
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    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
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    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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    • C10N2050/015—Dispersions of solid lubricants
    • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Metal Extraction Processes (AREA)

Abstract

A lubricant composition for the plastic working of metals that does not require a phosphate undercoating, is waterborne, requires only a simple application process of immersion or spraying followed by drying, and provides an excellent lubricating performance comprises synthetic resin, water-soluble inorganic salt, and water. The weight ratio of the content of salt to that of synthetic resin is from 0.25:1 to 9:1. This composition can also contain liquid and/or solid lubricating agent(s) and extreme pressure additive.

Description

The lubricant for plastic working of metallic substance
The present invention relates to the good metallic substance such as iron and steel, titanium, aluminium that supply of oilness and carry out the lubricant that plastic working is used.More specifically, the present invention relates to when carrying out plastic working, machined object is coated with the Hou dry simple process of the universe immediately, the lubricant of using with the plastic working metallic substance that forms the excellent oilness film of tool by spraying or dipping.
Generally, prevent the purpose that hot glue or killed, all can use the lubricant of aqueous or solid state metallic substance plasticity being added man-hour for reducing the friction that produces because of metallic contact between machined material and the instrument.With lubricator can be divided into two kinds substantially because of the difference of using method.One is the lubricant that physical property is adhered to the what metallic surface, and another forms the lubricant that carrier thin film Hou is adhered to lubrication prescription for make the metallic surface by chemical reaction.Before a kind of lubricant for being base oil with mineral oil, vegetables oil or synthetic oil, and the lubricant of interpolation extreme pressure additive, have and adhere to the type of directly carrying out plastic working behind the what metallic surface, or make solid lubricants such as metallic soap, graphite or molybdenumdisulphide disperse what water with the tamanori composition, adhere to what metallic surface Hou and make its universe dry, carry out the type of plastic working etc. then.So these lubricants can adopt the using method of coating or dipping very easy, need advantages such as liquid management in addition hardly, therefore are used for low weight plastic working more.In addition, the processing of a kind of lubricant of Hou is that so-called chemical tunicle is handled, and is to generate phosphate film Hou that carrier function is arranged in the metallic surface by chemical reaction, handles as lubrication prescription with reaction soap such as sodium stearate or calcium stearate or non-reaction soap.This type has as the chemical tunicle of carrier and two-layer structure as the metallic soap of lubrication prescription, has the splendid anti-high hot glue property.So widely used in plastic working fields such as wire drawing, trombone slide, forgings.
But phosphatizing is a kind of chemical reaction, so complicated liquid management must be arranged, is coated with lubrication prescription on the chemical tunicle in order to form in institute again, so if when comprising washing or pickling, the multinomial treatment process of necessary outfit.In addition, need the water wash water during owing to processing or can produce a large amount of waste liquids by chemical tunicle, and for the control chemical reaction must heat, therefore, the necessary expense that spends in a large sum of facility investment or the operation.
For solving this type of problem, replace the more phosphatizing of cost, once the someone made great efforts to improve the performance of above-mentioned physical method lubricant film, in the hope of it being increased to equaling chemically treated degree.Result as this effort is the method that proposes to use oily base lubricant or hydrographic lubricant." in the multipolymer of extreme pressure additive such as clorafin, phosphoric acid ester and iso-butylene-n-butene and lubricating oil that the animals and plants wet goods cooperates, the cold working of complexed metal soap or solid lubricant with lubricator " that the oil base lubricant has that special fair 4-1798 communique discloses.Even but these high performance lubricants if handle lubrication that Hou reacts the soap swabbing relatively with chemical tunicle, still have problem on processibility, and, owing to use extreme pressure additive, add and have the shortcoming that produces foul smell man-hour.
Again, during hydrographic lubricant, use with wet type though have directly, and the lubricant that uses as universe formula tunicle, but the hydrographic lubricant that directly uses with wet type is the same with above-mentioned oily base lubricant, is directly to pour into a mould what instrument or work material use, the hydrographic lubricant that uses as universe formula film is then the same with above-mentioned chemical tunicle, be in treatment trough dip treating Hou, in universe drying process, make water evaporates, obtain the solid tunicle.The former have disclose in the special public clear 58-30358 communique " with supercarbonate (solid) is main composition; and added therein paucidisperse agent, tensio-active agent and solid lubricant for the cold of metal tube or lubricant that hot-work is used ", handle and widely used stage but still can't reach the substituted chemistry tunicle.Again, the Hou person has the spy to open " with water-soluble polymer or its water based emulsion is base material; cooperate solid lubricant to form the lubricant compositions that agent became with chemical tunicle " that clear 52-20967 communique discloses etc., but still can't obtain can with the suitable level of chemical tunicle processing.
The present invention is the invention that solves the existing problem of above-mentioned prior art, provide a kind of as lubricant for plastic working and needn't form counterdie by phosphoric acid salt, in water system, make the dry easy technology of its attached outstanding Hou universe by dipping or spraying, can obtain can be suitable with the phosphoric acid facture, has the metallic substance lubricant composition for plastic working of oilness.
The inventor etc. are for solving above-mentioned problem, through the deep result of investigation repeatedly, find if metal sheet is flooded in the aqueous solution or aqueous dispersions that what contains synthetic resins and water-soluble inorganic salt, and it is dry to carry out the universe, can obtain tack splendid rein in tunicle by force.When finding in this aqueous solution or aqueous dispersions, to contain lubrication prescription or solid lubricant etc. in addition again, can make the gained tunicle have utmost point excellent lubricating property, thereby finish the present invention.
That is to say, the present invention is a kind of lubricant composition for plastic working of metallic substance, its characteristic for contain (A) synthetic resins, (B) water-soluble inorganic salt and water, (B)/(A) (solid composition weight ratio) is 0.25/1～9/1, synthetic resins be the dissolving or dispersion state.
Be preferably in the metallic substance lubricant composition for plastic working of the present invention and also contain at least a metallic soap, wax, tetrafluoroethylene and the oil of being selected from of 1～20 weight % as the lubrication prescription composition.Above-mentioned water-soluble inorganic salt is advisable with at least a vitriol, borate, molybdate, vanadate and the tungstate of being selected from.Above-mentioned synthetic resins is advisable with at least a polyvinyl alcohol, polyvinylpyrrolidone, acrylic resin, VINYL ACETATE MONOMER (VAM), Resins, epoxy, urethane resin and the phenol resin of being selected from.Composition in the present composition (A) is that composition (A) is boratory combination for urethane resin, composition (B) with the preferable combination of composition (B).In other words, the preferable example of the present composition is with the solid composition, be composition (A) urethane that contains 0.3～10.0 weight %, and composition (B) borate that contains 1.0～10.0 weight %, and then contain the above-mentioned metallic substance lubricant composition for plastic working of lubrication prescription.More be advisable as solid lubricant in the present composition to contain at least a molybdenumdisulphide, graphite, tetrafluoroethylene, boron nitride, mica and the fluorographite of being selected from of 1～20 weight %.Again, be extreme pressure additive also to contain at least a sulphur that is selected from of 0.5～5 weight % in the present composition, organic-molybdenum is that extreme pressure additive, phosphorus are that extreme pressure additive and chlorine are that the additive of anti-characteristic of extreme pressure additive is advisable.
Below be described in more detail the present invention.Used (A) synthetic resins in the metallic substance lubricant composition for plastic working of the present invention, so long as can anti-plastic working, has tack and by the tunicle of film toughness, promptly needn't limit especially, for example available polyethylene alcohol, polyvinylpyrrolidone, acrylic resin, VINYL ACETATE MONOMER (VAM), Resins, epoxy, urethane resin and phenol resin.The resin that uses no matter be water-soluble or water dispersible all can, can be chosen as suitable by application target.Optional water-soluble synthetic resin when for example plastic working Hou must demoulding can be selected water dispersible synthetic resins when needing water tolerance.
The synthetic resins that uses among the present invention is to be dissolved or dispersed in person in the present composition.For making its dispersion, can adopt known tensio-active agent as required.
Polyvinyl alcohol is a hydrolysis polyvinyl acetate and making, but a hydrolysis 50% or above hydrolyzate also can use except the complete hydrolysis thing.Polyvinyl alcohol among the present invention contains the multipolymer that is made of 50 moles of % or above vinyl alcohol units and ethylene unit.The molecular weight of polyvinyl alcohol is preferably 300～2000 during with gel permeation chromatography.
Polyvinylpyrrolidone is polymerization N-ethene-2-Pyrrolidone and making.During with the molecular weight of gel permeation chromatography polyvinylpyrrolidone, be advisable with 500～1000.
Acrylic resin can be enumerated at least a acrylic monomer of polymerization and the resin that obtains.Acrylic monomer can be enumerated (methyl) vinylformic acid C such as methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, isopropyl methacrylate, n-butyl acrylate, n-BMA, methacrylic acid 2-ethylhexyl, Octyl acrylate 1～C 8Alkyl ester; (methyl) vinylformic acid lower alkoxy lower alkyl esters such as vinylformic acid methoxyl group methyl esters, vinylformic acid methoxyl group ethyl ester, vinylformic acid oxyethyl group methyl esters, vinylformic acid ethoxy ethyl ester, methacrylic acid methoxy base methyl esters, methacrylic acid methoxy base ethyl ester, methacrylic acid oxyethyl group methyl esters, methacrylic acid ethoxy ethyl ester, vinylformic acid methoxy butyl; (methyl) vinylformic acid hydroxyl low-grade alkyl esters such as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 3-hydroxypropyl acrylate; Acrylamide, Methacrylamide; N-such as N hydroxymethyl acrylamide, N-methylol methacrylamide, N-butoxymethyl acrylamide, N-fourth oxygen methyl acrylamide do not replace or have (methyl) acrylamide of replacement (especially lower alkoxy replacement) methylol; (methyl) vinylformic acid phosphonato lower alkyl esters such as vinylformic acid phosphonato methyl esters, vinylformic acid phosphonato ethyl ester, vinylformic acid phosphonato propyl ester, methacrylic acid phosphonato methyl esters, methacrylic acid phosphonato ethyl ester, methacrylic acid phosphonato propyl ester; Vinyl cyanide; Vinylformic acid, methacrylic acid etc.Acrylic resin among the present invention also comprises at least a monomeric multipolymer in other ethene monomers such as at least a above-mentioned acrylic monomer and vinylbenzene, vinyl toluene, vinyl acetate, ethylene chloride, ethene, and contains 30 moles of % or above acrylic monomer unit person.The molecular weight of acrylic resin is 1000～1,000,000 during with gel permeation chromatography, and especially with 100,000～600,000 is advisable.
VINYL ACETATE MONOMER (VAM) is the resin that is obtained by polymerization by vinyl acetate.VINYL ACETATE MONOMER (VAM) also comprises that the vinyl acetate unit in the polyvinyl acetate resin does not reach 50% person of being hydrolyzed among the present invention.In addition, the VINYL ACETATE MONOMER (VAM) among the present invention also comprises multipolymer (the 50 moles of % in vinyl acetate unit or the more than) person of vinyl acetate and ethene.The molecular weight of VINYL ACETATE MONOMER (VAM) is advisable with 200～2000 during with gel permeation chromatography.
Can enumerate in the Resins, epoxy, make bisphenols, especially the bisphenol-type epoxy resin of dihydroxyphenyl propane (2,2-two (4 '-hydroxyphenyl) propane) and epichlorohydrin reaction gained especially can be with bisphenol A type epoxy resin shown in the following formula.In addition for example make the phenol hydroxyl glycidyl ether gained phenolic resin varnish type epoxy resin of phenol-novolac resin in addition, the epoxy propyl ester of aromatic carboxylic acid makes the peracid epoxy type etc. of the double bond epoxidation of ethene unsaturated compound with peracid.Also can enumerate addition of ethylene oxide or propylene oxide person on the resin matrix of Resins, epoxy as mentioned above in addition, also can be the epoxy propyl ether type of polyvalent alcohol etc.Be the best wherein to use bisphenol A type epoxy resin.The molecular weight of Resins, epoxy is advisable with 350～5000 during with gel permeation chromatography.
Figure A9910971500071
Urethane resin is the general available polyisocyanate compound with two or above isocyanate group of synthetic resins with amino acyloxy associative key (NHCOO), urethane resin and the polyvalent alcohol with two or above active hydrogen base carries out the resin of polyaddition reaction gained.This polyvalent alcohol can be polyester polyalcohols and polyether polyols.The polyester polyalcohols has for example by ethylene glycol, glycol ether, triglycol, 1,2-propylene glycol, 1, ammediol, neopentyl glycol, 1,2-butyleneglycol, 1,3-butyleneglycol, 1, low molecular weight polyols such as 4-butyleneglycol, 3-methyl pentanediol, hexylene glycol, Hydrogenated Bisphenol A, TriMethylolPropane(TMP), glycerol have the petchem of hydroxyl with many alkali acid-respons gained ends such as succsinic acid, pentanedioic acid, hexanodioic acid, sebacic acid, phthalic acid, iso-phthalic acid, terephthalic acid, benzene tricarboxylic acid, tetrahydrochysene metatitanic acid, endo-methylene group tetrahydrochysene phthalandione, six hydrogen phthalandiones.
Again, polyether polyols can be for example ethylene glycol, glycol ether, triglycol, 1,2-propylene glycol, 1, ammediol, neopentyl glycol, 1,2-butyleneglycol, 1,3-butyleneglycol, 1, polyether polyols, polycaprolactone polyalcohols, polyolefine polyalcohols, polyhutadiene polyalcohols etc. such as low molecular weight polyols such as 4-butyleneglycol, 3-methyl pentanediol, hexylene glycol, dihydroxyphenyl propane, Hydrogenated Bisphenol A, TriMethylolPropane(TMP), glycerol or their oxyethane and/or the high affixture of propylene oxide, polyoxyethylene glycol, polypropylene glycol, polyethylene/propylene glycol.
Again, polyisocyanates has aliphatics, ester ring type and aromatic polyisocyanate, tetramethylene diisocyanate is particularly arranged, hexamethylene diisocyanate, rely the amino acid vulcabond, hydrogenation time xylyl vulcabond, 1, the 4-cyclohexyl diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate, 2,4 '-dicyclohexyl methane diisocyanate, isophorone diisocyanate, 3,3 '-dimethoxy-4 ', 4 '-two phenyl diisocyanate, 1, the 5-naphthalene diisocyanate, 1, the 5-tetralin diisocyanate, 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, 4,4 '-'-diphenylmethane diisocyanate, 2,4 '-diphenylmethanediisocyanate, phenyl diisocyanate, the xylylene vulcabond, tetramethyl-benzene dimethyl vulcabond etc.
With 500～500,000 is advisable the molecular weight of urethane resin with gel permeation chromatography the time.
Phenol resins can be enumerated the resin by at least a phenols such as phenol, cresols, xylenol and formaldehyde reaction gained, can be phenolic varnish type resin, the arbitrary resin in the solvable phenolic resin.When using phenolic varnish type resin, vulkacit H etc. is coexisted as stiffening agent.The phenol resins tunicle hardens in the dry step of the universe that Hou is stated.There is no particular restriction for the molecular weight of phenol resins.
Above-mentioned various synthetic resins also can use commercially available product certainly, in such cases, generally can be used as the aqueous solution at synthetic resins when being water-soluble obtains, when synthetic resins is water-insoluble, can use that Hou is stated, with obtain for the dispersion liquid that makes lubrication prescription disperse the same tensio-active agent of used tensio-active agent to make it to be scattered in water.
Secondly, water-soluble inorganic salt (B) is when forming uniform tunicle by the universe is dry with synthetic resins, has the material that hardness and intensity are added for making tunicle.Can all be dissolved in the solution so selected water-soluble inorganic salt has, can evenly separate out with synthetic resins when the universe is dry, whereby to improve by the character of film toughness.Water-soluble inorganic salt as this character is advisable to use at least a vitriol, borate, molybdate, vanadate and the tungstate of being selected from.Can be for example sodium sulfate, vitriolate of tartar, Sodium Tetraborate (sodium tetraborate etc.), potassium borate (potassium tetraborate etc.), ammonium borate (tetraboric acid ammonium etc.), ammonium molybdate, Sodium orthomolybdate, sodium wolframate, vanadic acid sodium etc.They can use separately, two kinds or above use also capable of being combined.
Synthetic resins among the present invention (A) (B)/(A) is necessary for 0.25/1～9/1 with the weight ratio (solid composition weight ratio) of water-soluble inorganic salt (B).This weight ratio can produce on the metallic substance and kill or the hot glue work less than the hardness deficiency of 0.25/1 o'clock tunicle.Again, this weight ratio then can reduce the tack and the follow-up servo-actuated of tunicle greater than 9/1 o'clock, add man-hour tunicle become easily come off, oilness reduces.Above-mentioned (B)/(A) weight ratio is preferably 0.3/1～8/1, is more preferred from 0.5/1～7/1.
The character used water dissolubility of the tunicle that forms or the weight ratio of water dispersible synthetic resins and water-soluble inorganic salt are adjusted.According to processing or the optimal weight ratio of sliding position suffered burden size decision.The ratio that is water-soluble inorganic salt is just increased by film hardness for a long time, and the withstand load performance improves, but the tack of tunicle can reduce.
For example, forge the sort of as the plastic working sealing, during the harsh situation of processing conditions, adding the more amount water-soluble inorganic salt is advisable, particularly, synthetic resins (A) (B)/(A) is advisable with 1.5/1～9/1 with the weight ratio (solids component weight ratio) of water-soluble inorganic salt (B), and 2/1～8/1 is better, and 2/1～7/1 is best.And for example during the press process of thin plate because the followability of tunicle is with greatly good, so the ratio of water-soluble inorganic salt with few for well, its weight ratio is advisable with 0.25/1～2/1,0.3/1～2/1 is better.
About the use level of synthetic resins and water-soluble inorganic salt, the total amount (solid composition total) that makes the two for 1～20 weight % of this composition for well, 1～15 weight % is better, 3～10 weight % are better.
When being used for metallic substance lubricant composition for plastic working of the present invention on the metallic surface, when if plastic working is one section plastic working, by above-mentioned composition (A), (B) and in the composition of water composition can also further contain the lubrication prescription composition as required, solid lubricant and/or extreme pressure additive, this lubricant compositions is suitable for metallic substance very much, but when if plastic working is the plastic working (for example wire drawing or the multistage processing when forging) of multistage, with above-mentioned composition (A), (B) and the composition of water coat metallic substance, the tunicle that the dry Hou of the universe is generated is coated with the lubrication prescription composition in each process segment then in the above more as required as carrier, solid lubricant and/or extreme pressure additive (for example spreading down) carry out plastic working then for well.
So metallic substance lubricant composition for plastic working of the present invention, particularly for metallic substance when carrying out one section plastic working, or the multistage add man-hour, can further contain lubrication prescription composition, solid lubricant and/or extreme pressure additive as required and be advisable.
The lubrication prescription composition is advisable to be contained in the said composition usually in the above-mentioned composition.This lubrication prescription composition is with stable in the aqueous solution, and can not reduce by film toughness person and be advisable, and this kind material can be metallic soap, wax, tetrafluoroethylene and oil.Particularly, metallic soap can be calcium stearate, aluminum stearate, barium stearate, lithium stearate, Zinic stearas etc., and wax can be polyethylene wax, Poly Propylene Wax, carnauba wax, beeswax, paraffin etc., tetrafluoroethylene can be for example tetrafluoroethylene about the polymerization degree 1,000,000～1,000 ten thousand.Again, oily available vegetables oil, mineral oil, synthetic wet goods, for example vegetables oil has plam oil, castor seeds oil, vegetable seed wet goods, mineral oil organic oil, turbine oil, spindle wet goods, and synthetic oil has ester oil, silicone oil etc.
These lubricated compositions can aqueous dispersions or the form of water emulsion mix with other compositions, it is contained in this composition.
Lubrication prescription is disperseed usually or is emulsifiable in the present composition.
For well, 1～10 weight % is more suitable with 1～20 weight % for the use level of lubrication prescription, and 2～7 weight % are better.The use level friction that tunicle is subjected to during less than 1 weight % increases, and the hot glue work takes place easily, when surpassing 10 weight %, can reduce the tack of tunicle.
The above-mentioned preferable example that contains the present composition of composition (A), composition (B), lubrication prescription and water is that to contain with the solid composition be that (A) urethane resin, (B) borate, lubrication prescription and the water of 1.0～10.0 weight %, (B)/(A) (solid composition weight ratio) of 0.3～10.0 weight % is 0.25/1～9/1 metallic substance lubricant composition for plastic working.Urethane resin be 0.3 weight % or above be the preferred values considered for the tack that prevents to reduce tunicle, 10.0 weight % or following be to prevent to reduce by film hardness because of considering, the preferred values that hot glue takes place.Again, boric acid be 1.0 weight % or above be from the hardness that prevents tunicle die down the viewpoint that causes metallic substance generation hot glue work preferred values, 10.0 weight % or following be from preventing that tunicle from reducing because of the ductility of tack or tunicle, add the easy what of tunicle in man-hour and come off, the viewpoint that causes reducing its oilness is preferred values.
The kind of lubrication prescription and use level thereof all can be with above-mentioned the same in this example.
During the more harsh plastic working of processing conditions, the present composition is advisable also to contain solid lubricant.At this moment used solid lubricant also helps the lubricated person of what and is advisable can stably exist in the what tunicle under heavier weighing load.This lubricant can be enumerated graphite, molybdenumdisulphide, boron nitride, fluorographite, mica etc.
The use level of this solid lubricant is advisable with 1～20 weight %.1～10 weight % is more suitable, and 1～5 weight % is better.Use level during less than 1 weight % heat-resistant adhesive work property the anxiety of deficiency is arranged, the worry of tack reduction is then arranged during greater than 20 weight %.
During the more harsh plastic working of processing conditions, be preferably in and further contain extreme pressure additive in the above-mentioned composition.At this moment as extreme pressure additive with stable in tunicle, can bring into play anti-extreme pressure effect person at the contact surface of instrument and metal by processing and be advisable.It is extreme pressure additive that this kind extreme pressure additive can be olefine sulfide, sulfuration ester, sulfite, carbothioic acid ester, chlorination lipid acid, phosphoric acid ester, phosphorous acid ester, dithiocarbamate molybdenum (MoDTC), molybdenum dithiophosphate (MoDTP), zinc dithiophosphate sulphur such as (ZnDTP), and organic-molybdenum is that extreme pressure additive, phosphorus are that extreme pressure additive and chlorine are extreme pressure additive.
The use level of this extreme pressure additive is advisable with 0.5～5 weight %, and 1～3 weight % is better.Use level has the worry of anti-extreme pressure effect deficiency when not reaching 0.5 weight %, the worry of tunicle tack reduction is then arranged when surpassing 5 weight %.
When making synthetic resins, lubrication prescription, solid lubricant and/or extreme pressure additive dispersion or emulsification need tensio-active agent, tensio-active agent can be used any in nonionic surfactant, anionic surfactant, amphoterics and the cationic surfactant.Though nonionic surfactant is not had special restriction, can exemplify polyxyethylated ester, sorbitan and polyoxyethylene glycol and higher fatty acid (routine C that polyethylene oxide alkyl ethers, polyoxyalkylene (ethene and/or propylene) alkane phenyl ether, polyoxyethylene glycol (or oxyethane) and higher fatty acid (for example carbon number 12～18) are constituted 12～C 18) the polyoxyethylene sorbitan alkyl ester that constituted etc.The anionic surfactant is not specially limited, but can exemplifies with soap, sulfuric acid, sulfonate, phosphate ester salt, phosphorodithioate salt etc.Amphoterics is restriction especially also, but available for example amino acid pattern and betaine type carboxylate salt, sulfuric acid, hydrochlorate, phosphate ester salt etc.Cationic surfactant is not restriction especially also, available for example aliphatics amine salt, quaternary ammonium salt etc.These tensio-active agents can be distinguished two kinds or above use alone or in combination.
About the manufacture method of lubricant compositions of the present invention,, promptly needn't be limited especially the lubricant compositions of manufacturing as long as satisfying above-mentioned condition.For example, can in the aqueous solution of water-soluble inorganic salt, add water-soluble or water dispersible synthetic resins, fully stir Hou, add lubrication prescription, solid lubricant and/or extreme pressure additive as any composition, use tensio-active agent and water as required, be dispersion liquid or emulsion Hou,, can make the present composition whereby through adding above-mentioned any composition, stirring.
Lubricant compositions of the present invention can use as lubricant when carrying out metallic substance such as cold plasticity processing (wire drawing, trombone slide, forging etc.) iron or steel, copper or copper alloy, aluminum or aluminum alloy, titanium or titanium alloy.About the shape of metallic substance, do not limit materials such as what club-shaped material or bulk material, add through the forming object (gear, axle) of heat forged Hou etc. and also can consider man-hour to use, so restriction especially.
Be coated with before the lubricant compositions of the present invention, can carry out degreasing (general available bases grease-removing agent), washing, pickling to the metallic substance of processing in regular turn (in order to remove the oxidation scale of metallic substance for obtaining better result, the tack that improves tunicle can use hydrochloric acid etc. to carry out), pre-treatment such as washing, clean its surface and be optimum.If also can not save pickling → water-washing step when being attached with oxidation scale.These pre-treatment can be implemented according to well-established law.
Lubricant compositions of the present invention can be according to well-established laws such as dipping, spraying, flow coat coating what metallic substance.Coating is the what metallic surface as long as lubricant compositions can be covered maturely, and there is no particular restriction to the what coating time.It is dry that coating Hou lubricant compositions must carry out the universe.Though the dry what normal temperature of can putting of the universe carries out, usually 60～150 ℃ of whats carry out 10～60 minutes comparatively suitable.
With the tunicle weight of present composition coating and the dry Hou of the universe, from the viewpoint that prevents that hot glue from, with 1g/m 2Or more than be advisable, again, with regard to cost with 30g/m 2Or below be advisable 5～20g/m 2Better, the best is 8～15g/m 2
Oiling system of the present invention can be considered the former by the compound tunicle of water-soluble or water dispersible synthetic resins and water-soluble inorganic salt.Promptly can think the water-soluble or water-dispersed resin and the water-soluble inorganic salt blended aqueous solution are adhered to the what metallic surface, right Hou makes the dry step of its universe in addition, therefore at first owing to evaporation of water, the concentration of the aqueous solution rises, and the crystallization of water-soluble inorganic salt promptly begins to separate out.Right Hou is because the water revaporization, and the concentration of synthetic resins raises, and separates out gradually and be attached to the what metallic surface.At this moment separate out because of existing inorganic salt crystallization, so water-soluble or water dispersible synthetic resins just becomes a kind of water-soluble inorganic salt crystalline tunicle that is dispersed with equably.Therefore, can think that the result can form with the flexibility of synthetic resins and tack, the hardness of inorganic salt and the tunicle of intensity because synthetic resins is separated out equably with inorganic salt.
Enumerate embodiments of the invention at this with comparative example, specify the present invention and effect thereof.Embodiment 1～3, comparative example 1～2
With the modulation of ratio shown in the table 1 lubricant compositions.Water-soluble inorganic salt is dissolved in water Hou, and the dissolving phenol resins fills a part stirring, modulates with this.In this lubricant compositions dipping bag step on (Bowden) rub(bing)test sheet (material: 30 Hou in seconds of SPC steel plate, 150mm * 75mm * 1.0mm), in dry 30 minutes of 100 ℃ of universes.Then, the whole tunicle after the universe is dry evenly sprinkles calcium stearate powder (Nof Corp.'s system) Hou, steps on rub(bing)test for bag and uses.
Again, coating bag is stepped on before the rub(bing)test lubricant compositions, to test film carry out following (1)～(2) pre-treatment step, to carry out the hot blast universe dry.
(1) alkali degreasing (concentration 20g/1,60 ℃ of temperature were flooded 10 minutes for Japanese Parkerlizing corporate system, meticulous lotion 4360).
(2) washing is with the tap water hydro-peening of normal temperature.
Tunicle weight (g/m 2) be that the weight difference of Hou calculates before being coated with by lubricant compositions.It is with test load 5kg that bag is stepped on rub(bing)test, and test temperature is a room temperature, and test steel ball 5mm measures frictional coefficient and hot glue work number of times (frictional coefficient reaches 0.25 o'clock slip number of times).Average friction coefficient is to measure the mean number that hot glue the preceding Hou 10 times of number of times * 1/2 time.Embodiment 4～7, comparative example 3～6
According to the modulation of ratio shown in the table 2 lubricant compositions.Water-soluble inorganic salt is dissolved in water Hou, and dissolve polyurethane resin, polyvinyl alcohol, phenol resins or acrylate resin fully stir.Add the additive 1 (lubrication prescription) shown in the table 2 (polyethylene wax dispersion liquid, calcium stearate dispersion liquid, tetrafluoroethylene or plam oil disperse liquid) again, stir, be modulated into lubricant compositions.In this lubricant compositions 30 seconds bags of dipping step on the friction test piece (material: the Hou of SPC steel plate, 150mm * 75mm * 1.0mm), in dry 30 minutes of 100 ℃ of universes, step on rub(bing)test for bag and use.Bag is stepped on the pre-treatment of rub(bing)test and bourdon's test sheet and is carried out equally by embodiment 1～3.
Hou side's drift test sheet be impregnated in 30 seconds Hous of lubricant compositions, placed 30 minutes, carry out the dry Hou of the thorough universe and be for experiment in 100 ℃ of baking ovens.
Again, Hou side's drift test sheet carried out following pre-treatment step (1)～(4) to test film before the application of lubricating composition, and it is dry to carry out the hot blast universe then.
(1) alkali degreasing: (with the meticulous lotion 4360 of Japanese Parkelizing corporate system, concentration 20g/l, 60 ℃ of temperature were flooded 10 minutes).
(2) washing: the tap water hydro-peening of usefulness normal temperature 30 seconds.
(3) pickling: hydrochloric acid, concentration 17.5 weight %, temperature room temperature, dipping time 10 minutes.
(4) washing: the tap water hydro-peening of usefulness normal temperature 30 seconds.
Material for Hou side drift test is the commercially available spherical annealed material of S45C, test film be shaped as diameter 30mm Ф, will highly be changed to 16～40mm person (13 level) with the unit of 2mm.
Hou side drift test adopts 200 tons of toggle joint presses, and the assembling mould on the cylindric test film that is fixed in the outside, can be the stamping machine of 50% diameter with draft, by top punching press perforation, make the method for cup-shaped shaping thing.At this moment Ji Ya bottom dead centre (lowerdead point) be regulate make test film bottom residual part be 10mm.Hou side's drift test is that test film is begun to process in regular turn by highly lower test film, tests till the machined surface generation scar.Evaluation is as good punching depth representing with the cup inner height of the seamless test film of inner face.Model: SKD 11 press: HAP40,16,20,24,28,32,36,40,44,48,52,56,60mm spiral shell head diameter 21.21mm test film: S45C, the annealed material hole depth of balling:.Process velocity: 30 strokes/minute are shown what Fig. 1 with Hou side's drift test.Comparative example 7
The test film same with embodiment 4～10 carries out chemical treatment to Hou side's drift test sheet and response type soap lubricant is handled according to condition shown in the table 2, and gained test film and embodiment 4～10 are the same to step on rub(bing)test and Hou side's drift test usefulness for bag.Embodiment 18～34
With the modulation of ratio shown in the table 3 lubricant compositions.Promptly, operate Hou equally according to embodiment 4～10, just be added into after the tensio-active agent (nonionic system) of additive B (molybdenumdisulphide, graphite, boron nitride, fluorographite, vulcanized vegetable oil, MoDTC, MoDTP, ZnDTP or phosphorous acid ester) and 2 weight % and water are pre-mixed.
Tunicle is handled, and rub(bing)test stepped on by bag and Hou side's drift test is all similarly carried out with embodiment 4～10.
Above test-results is shown what table 1～table 3.By table 1～table 3 as can be known, use the embodiment 1～34 of metallic substance lubricant composition for plastic working of the present invention can bring into play extremely excellent oilness with easy operation.On the other hand, beyond scope of the present invention, 1～6 of the comparative example of structure condition of the present invention be can't satisfy and the oilness of excellence and easy operation failed to satisfy simultaneously.Again, though the phosphate coating of comparative example 7 shows and the equal oilness of the present invention that technology is too many, can not adopt easy equipment.
Again, each composition that uses in the his-and-hers watches 1～table 3 is done following explanation.
Phenol resins: make phenol-phenolic varnish amination and make it become water dissolved matter (molecular weight 500～6000)
Urethane resin: the polyoxyethylene glycol of molecular weight 1000 and hexamethylene diisocyanate are carried out addition polymerization person (molecular weight 50000 or more than)
Acrylic resin: the multipolymer of vinylformic acid, methyl methacrylate and n-butyl acrylate.Molecular weight 150,000 or more than.Use tensio-active agent: polyoxyethylene alkane phenyl ether
PVA: polyvinyl alcohol (molecular weight 1000)
PE wax (polyethylene latex wax): by the emulsion polymerization manufacturing (molecular weight 16000～20000) of ethene
PTFE (tetrafluoroethylene wax): Sumitomo 3-M system
StCa dispersion liquid (calcium stearate dispersion liquid): Zhong jing grease system
Plam oil latex: disperse plam oil with polyoxyalkylene alkane phenyl ether
Vulcanized vegetable oil: Japanese grease system
Phosphorous acid ester: boundary's chemistry system
Additive 2 (solid lubricant or extreme pressure additive) all disperses with polyoxyalkylene alkane phenyl ether.
Again, the weight % of each composition represents the weight % of composition itself.Therefore for example, during the situation of aqueous dispersions, do not comprise water or for the tensio-active agent that disperses usefulness interior.Table 1 embodiment 1～3, comparative example 1,2
Content component Coating Water-soluble inorganic salt/synthetic resins Test-results
Water-soluble inorganic salt Synthetic resins Additive Tunicle amount (g/m 2) Bag is stepped on The rear punching
Composition Weight % Composition Weight % Composition Weight % Composition Average friction coefficient Hot glue number of times The good punching degree of depth (mm)
Embodiment ?1 Sodium wolframate ??2 Phenol resins ??4 ??- The calcium stearate powder ??0.50 ??8.2 ??0.15 ??625 ???-
?2 Sodium orthomolybdate ??4 Phenol resins ??6 ??- The calcium stearate powder ??0.67 ??7.1 ??0.13 ??482 ???-
?3 Potassium tetraborate ??4 Phenol resins ??6 ??- The calcium stearate powder ??0.67 ??7.0 ??0.13 ??523 ???-
Comparative example ?1 Sodium wolframate ??9.5 Phenol resins ??1 ??- The calcium stearate powder ??9.5 ??8.1 ??0.18 ??212 ???-
?2 Sodium wolframate ??0.5 Phenol resins ??4 ??- The calcium stearate powder ??0.13 ??8.7 ??0.15 ??128 ???-
Phenol resins: aminated phenol-phenolic varnish make its water-solubleization person (molecular weight 500～6000)
Urethane resin: the polyoxyethylene glycol of molecular weight 1000 and hexamethylene diisocyanate are given addition polymerization person's (molecular weight 50000 or more than)
Acrylic resin: the multipolymer of vinylformic acid, methyl methacrylate, n-butyl acrylate, more than molecular weight 150,000 formulas.Use tensio-active agent: polyoxygenated alkane phenyl ether
PVA: polyvinyl alcohol (molecular weight 1000)
PE wax (polyethylene latex wax): carry out emulsion polymerization manufacturing (molecular weight 16000～20000) by ethene
PTFE (poly-tetrafluoroethylene wax): Sumitomo 3-M system
StCa dispersion liquid (calcium stearate dispersion liquid): Zhong jing grease system
Plam oil latex: disperse plam oil with polyoxyalkylene alkane phenylate
Vulcanized vegetable oil: Japanese grease system
Phosphorous acid ester: boundary's chemistry system
MO-DTC: dithiocarbamate molybdenum
MO-DTP: molybdenum dithiophosphate
Zn-DTP: zinc dithiophosphate
Additive 2 is all to disperse with polyoxyalkylene alkane phenyl ether.Table 2 embodiment 4～17, comparative example 3～7
Content component Water-soluble inorganic salt/synthetic resins Test-results
Water-soluble inorganic salt Synthetic resins Additive 1 (lubrication prescription) Additive 2 Tunicle amount (g/m 2) Bag is stepped on The good punching degree of depth of rear punching (mm)
Composition Weight % Composition Weight % Composition Weight % Composition Weight % Average friction coefficient Hot glue number of times
Embodiment ??4 Sodium wolframate ??3 Phenol resins ??1 PE wax ??5 ??- ???3 ??8.7 ??0.08 ??635 ???44
??5 Sodium wolframate ??3 ????PVA ??1 PE wax ??3 ??- ???3 ??9.1 ??0.09 ??425 ???44
??6 Sodium wolframate ??6 Urethane resin ??2 PE wax ??5 ??- ???3 ??11.8 ??0.07 ??823 ???44
??7 Sodium orthomolybdate ??3 Phenol resins ??1 PE wax ??3 ??- ???3 ??9.2 ??0.09 ??740 ???44
??8 Sodium tetraborate gathers ammonia ??3 Phenol resins ??1 The StCa dispersion liquid ??3 ??- ???3 ??10.2 ??0.08 ??735 ???44
??9 Potassium vanadate ??3 Phenol resins ??1 The StCa dispersion liquid ??5 ??- ???3 ??10.1 ??0.07 ??631 ???44
??10 Vitriolate of tartar ??3 Acrylic resin ??1 The StCa dispersion liquid ??3 ??- ???3 ??9.7 ??0.08 ??688 ???44
??11 Sodium tetraborate ??3 Urethane resin ??1 PE wax ??5 ??- ???3 ??9.0 ??0.09 ??688 ???44
??12 Sodium tetraborate ??3 Urethane resin ??3 PE wax ??5 ??- ???1 ??12.2 ??0.08 ??823 ???44
??13 Sodium tetraborate ??3 Urethane resin ??8 PE wax ??5 ??- ??0.38 ??11.1 ??0.07 ??888 ???44
??14 Sodium tetraborate ??2 Urethane resin ??1 The StCa dispersion liquid ??3 ??- ???2 ??8.8 ??0.09 ??510 ???44
??15 Potassium tetraborate ??3 Urethane resin ??5 The StCa dispersion liquid ??3 ??- ??0.60 ??8.5 ??0.09 ??635 ???44
??16 Potassium tetraborate ??3 Urethane resin ??1 ????PTFE ??5 ??- ???3 ??12.3 ??0.07 ??912 ???44
??17 Potassium tetraborate ??8 Urethane resin ??1 The plam oil latex ??3 ??- ???8 ??9.5 ??0.08 ??823 ???44
Comparative example ??3 Sodium wolframate ?9.5 Phenol resins ??1 PE wax ??3 ??- ??9.50 ??9.1 ??0.18 ??158 ???40
??4 Sodium wolframate ?0.5 ????PVA ??4 PE wax ??3 ??- ??0.13 ??10.4 ??0.12 ??210 ???36
??5 Sodium wolframate ??3 ????- PE wax ??5 ??- ???- ??8.2 ??0.21 ??112 ???28
??6 ?????- Urethane resin ??3 PE wax ??5 ??- ???- ??9.7 ??0.11 ??69 ???20
??7 The zinc phosphate film is handled Japanese Parkelizing corporate system Parbond:181X (concentration 90g/l) treatment condition: flood 80 ℃, 10 minutes Reaction soap swabbing Japan Parkelizing corporate system Poloob2 35 (concentration 70g/L) treatment condition: flood 80 ℃, 5 minutes Chemistry tunicle weight 5.8 metallic soap amounts 2.3 thermosol soap amounts 2.5 ??0.10 ??409 ???44
Table 3 embodiment 18～34
Content component Water-soluble inorganic salt/synthetic resins Test-results
Water-soluble inorganic salt Synthetic resins Additive 1 (lubrication prescription) Additive 2 Film amount (g/m 2) Bag is stepped on The good punching degree of depth of rear punching (mm)
Composition Weight % Composition Weight % Composition Weight % Composition Weight % Average friction coefficient Hot glue number of times
Embodiment ??18 Sodium wolframate ???3 Phenol resins ??1 PE wax ??3 Molybdenumdisulphide ???2 ??3.00 ??11.2 ??0.15 ??822 ???48
??19 Sodium wolframate ???6 Phenol resins ??1 PE wax ??3 Graphite ???2 ??6.00 ??10.6 ??0.12 ??862 ???48
??20 Sodium wolframate ???3 ????PVA ??1 PE wax ??3 ??BN ???2 ??3.00 ??11.2 ??0.17 ??685 ???44
??21 Sodium wolframate ???7 ????PVA ??1 PE wax ??3 Fluorographite ???2 ??7.00 ??11.1 ??0.16 ??624 ???44
??22 Sodium wolframate ???3 ????PVA ??1 PE wax ??3 The sulfuration grease ???1 ??3.00 ??9.8 ??0.11 ??612 ???44
??23 Sodium wolframate ???3 ????PVA ??1 PE wax ??3 ??MoDTC ???1 ??3.00 ??9.2 ??0.14 ??741 ???44
??24 Sodium wolframate ???3 ????PVA ??1 PE wax ??3 ??MoDTP ???1 ??3.00 ??9.1 ??0.15 ??618 ???44
??25 Sodium orthomolybdate ???2 Acrylic resin ??1 PE wax ??3 ??ZnDTP ???1 ??2.00 ??8.2 ??0.11 ??589 ???44
??26 Potassium tetraborate ???6 Acrylic resin ??1 PE wax ??3 Molybdenumdisulphide ???2 ??6.00 ??11.5 ??0.16 ??854 ???48
??27 Potassium vanadate ???6 Acrylic resin ??1 PE wax ??3 Molybdenumdisulphide ???2 ??6.00 ??11.7 ??0.17 ??727 ???48
??28 Vitriolate of tartar ???6 Acrylic resin ??1 PE wax ??3 Molybdenumdisulphide ???2 ??6.00 ??10.7 ??0.16 ??818 ???48
??29 Sodium tetraborate ???3 Urethane resin ??3 PE wax ??3 Stone ???2 ??1 ??10.3 ??0.12 ??623 ???48
??30 Sodium tetraborate ???3 Urethane resin ??3 PE wax ??3 Molybdenumdisulphide ???2 ??1 ??9.2 ??0.11 ??624 ???48
??31 Sodium tetraborate ???3 Urethane resin ??3 PE wax ??3 Boron nitride ???2 ??1 ??10.3 ??0.12 ??521 ???48
??32 Sodium tetraborate ???3 Urethane resin ??3 PE wax ??3 Phosphorous acid ester ???2 ??1 ??9.3 ??0.08 ??812 ???44
??33 Sodium tetraborate ???3 Urethane resin ??3 PE wax ??3 ??MoDTC ???1 ??1 ??10.8 ??0.10 ??441 ???44
??34 Sodium tetraborate ???3 Urethane resin ??3 PE wax ??3 ??ZnDTP ???1 ??1 ??9.3 ??0.08 ??452 ???44
[effect of invention]
Can form the tunicle with extremely excellent lubricity with easy processing when by above explanation as can be known, using metal material lubricant composition for plastic working of the present invention. Again, without discarded object, so operating environment is splendid.
[simple declaration of accompanying drawing]
Accompanying drawing represents to use lubricant composition for plastic working of the present invention to carry out the summary of Hou side's drift test.

Claims (8)

1. the lubricant for plastic working of a metallic substance is characterized by, and it contains (A) synthetic resins, (B) water-soluble inorganic salt and water, (B)/(A) (solid composition weight ratio) is 0.25/1～9/1, and synthetic resins is for being dissolved or dispersed in wherein person.
2. the lubricant for plastic working of metallic substance as claimed in claim 1 wherein contains a kind of of 1～20 weight % or two kinds or above metallic soap, wax, the tetrafluoroethylene and oily as lubrication prescription of being selected from.
3. the lubricant for plastic working of metallic substance as claimed in claim 1 or 2, wherein water-soluble inorganic salt is a kind of or two kinds or above vitriol, borate, molybdate, vanadate and the tungstate of being selected from.
4. as the lubricant for plastic working of each described metallic substance among the claim 1-3, wherein synthetic resins is a kind of or two kinds or above polyvinyl alcohol, polyvinylpyrrolidone, acrylic resin, VINYL ACETATE MONOMER (VAM), Resins, epoxy, urethane resin and the phenol resin of being selected from.
5. the lubricant for plastic working of metallic substance as claimed in claim 1 wherein contains composition (A) urethane resin of 0.3～10.0 weight % solid composition and the borate of 1.0～10.0 weight % compositions (B), also contains lubrication prescription.
6. the lubricant for plastic working of metallic substance as claimed in claim 5 wherein contains one kind of 1～20 weight % or two kinds or above metallic soap, wax, the tetrafluoroethylene and oily as lubrication prescription of being selected from.
7. as the lubricant for plastic working of each described metallic substance among the claim 1-6, wherein contain one kind of 1～20 weight % or two kinds or above molybdenumdisulphide, graphite, boron nitride, mica and the fluorographite of being selected from as the solid lubricant person.
8. as the lubricant for plastic working of each metallic substance among the claim 1-7, wherein containing one kind of 0.5～5 weight % or two kinds or the above sulphur that is selected from is that extreme pressure additive, organic-molybdenum are that extreme pressure additive, phosphorus are that extreme pressure additive and chlorine are that extreme pressure additive is as extreme pressure additive.
CNB991097157A 1998-06-09 1999-06-09 Lubricant for plastic working of metal material Expired - Fee Related CN1148437C (en)

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AU4416299A (en) 1999-12-30
TW444056B (en) 2001-07-01
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DE69930628D1 (en) 2006-05-18
WO1999064544A1 (en) 1999-12-16
CA2334716C (en) 2009-08-18
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EP1093510B1 (en) 2006-03-29
KR20000006017A (en) 2000-01-25

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