JPH0380835B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of Application of the Invention] The present invention relates to a lubricant for plastic working and a method of using the same. [Background of the Invention] A lubricant for plastic working of metals must have sufficient lubrication performance against temperature rise due to deformation heat, frictional heat, etc. during processing, and increase in new surfaces. These lubricants include water-soluble and water-insoluble liquid lubricants whose main ingredients are mineral oil, synthetic oil, or a mixture of these oils, semi-solid lubricants such as metal soap and beef tallow, and sulfur-based and chlorine-based lubricants. , phosphorus-based extreme pressure agents, graphite, solid lubricants such as molybdenum disulfide, etc. are used. The above lubricants can be used in plastic working with a low degree of processing, but in cases where the degree of processing is high at high temperatures and surface pressures, or when molding parts with complex shapes, the load carrying capacity, heat resistance, etc. of the lubricant may be used. Because of the insufficient quality, seizure occurred and there was nothing that was completely satisfactory. As a lubricant when plastic deformation is large or when shaping an object with a complicated shape, there are two methods: plating the surface of the material with a soft metal such as copper, and coating the material with a synthetic resin film. In addition, a well-known method is
Degreasing of materials - Water washing - Pickling - Phosphate treatment - Water washing -
There is a treatment method consisting of a series of steps: neutralization treatment, metal soap lubrication treatment, and heating drying. All of these methods of forming a lubricating film require sufficient pretreatment, and the process of forming the film is complicated, requiring a great deal of labor and expense. Also,
There is also the problem of pollution from treated wastewater. In recent years, lubricants containing phosphoric acid and its salts, boric acid and its salts, alkali metal carbonates, nitrates, sulfates and their hydroxides, layered silicates, etc. have been proposed (Japanese Patent Application Laid-Open No. 73089-1989). Publication No.). These lubricants are
Since it is composed of a water-soluble glass powder containing P ₂ O ₅ , B ₂ O ₂ , M ₂ O (M is an alkali metal), a layered silicate, or a mixture of the above and water, it cannot be used at low temperatures such as during cold working (approx. It cannot be used for cold working because it cannot exhibit lubricity at temperatures below 300℃. In addition, polyvalent metal cations, orthophosphates and carbon atoms of 10 to
36 alkyl alcohol or alkylaryl reacted with a lubricant with a moisture content of 20 Wt% or less (Japanese Patent Application Laid-open No. 15569/1983), or a mixture of the above lubricant with mineral oil, carboxylic acid, and alkyl amine. There are added liquid or paste forms. In addition, lubricants such as mineral oil, oleic acid, and oleylamine (30 to 94 Wt%), polyvalent metal cation salts, polyphosphoric acid, and alcohols having 10 to 36 carbon atoms (metal cation: P ₂ O ₂ : alcohol = 1:3 to 60 :14~
150Wt ratio) with reaction components 5-60 _wT %, moisture 0.5-60%
A cold working lubricant comprising 10 Wt% has been proposed (US Pat. No. 3,932,287). However, although these lubricants all show good results in drawing pipes and the like, they are not suitable for processing solid steel materials with a high reduction in area. [Object of the Invention] The object of the present invention is to significantly improve the lubricity of the lubricating film under high working conditions resulting in high temperatures and high surface pressures, and to substantially improve machining performance in cold working. An object of the present invention is to provide a liquid lubricant for plastic working that does not contain water. The liquid lubricant for plastic working that does not substantially contain water as used in the present invention does not refer to a liquid lubricant that contains trace amounts of water present in the lubricating oil and additive components, but does not contain water as an additive. means a liquid lubricant without the addition of Another object of the present invention is to significantly improve the lubricity of the lubricating film at high working rates resulting in high temperatures and high surface pressures, and to provide excellent machining performance in cold working. It is an object of the present invention to provide a method for using a lubricant for plastic working in which a process for forming a lubricant film using a liquid lubricant is simple. [Summary of the Invention] The lubricant for plastic working of the present invention is characterized by the following (C), (D) and (E ),
A lubricant for plastic processing that is characterized by containing substantially no water. (C) Extreme pressure agent selected from organophosphorus compounds, organosulfur compounds, and organochlorine compounds (D) Obtained by reacting fatty acids, long-chain dibasic acids, and long-chain branched primary alcohols. A partial ester having at least one hydroxyl group in the molecule, a partial ester having at least one hydroxyl group in the molecule obtained by reacting a long chain monobasic acid with glycol, a polyol having a neopentyl type skeleton and a carbon number of 5 An oily agent (E) selected from partial esters having at least one hydroxyl group obtained by reacting with three or more fatty acids; A liquid lubricant for plastic working consisting of an organic powder selected from fatty acid amides and metal soaps. By simply supplying it to the metal surface or into the mold, it uses deformation heat and frictional heat during plastic processing to form a lubricating film with superior heat resistance and lubricity on the metal surface, making it possible to form complex shapes and process This greatly improves seizure prevention even for molded products with extremely high As the lubricating oil (A) in the present invention, ordinary commercially available lubricating oils can be used. For example, mineral oil,
Examples include synthetic oils such as α-olefin oil, diester oil, polyol ester oil, polyether oil, silicone oil, fluorine oil, polybutene oil, and polyglycol oil, and mixtures thereof. These lubricating oils can be appropriately determined depending on the processing conditions and working conditions of the processed product. The kinematic viscosity at approximately 40°C is preferably 30 mm ² /S or more. Examples of the condensed phosphoric acid and its acid salt (B) in the present invention include polyphosphoric acid, pyrophosphoric acid, metaphosphoric acid, acidic polyphosphate, acidic pyrophosphate, and acidic metaphosphate. As the acidic pyrophosphate, sodium acidic pyrophosphate and calcium acidic pyrophosphate are effective; as the acidic polyphosphate, sodium acidic polyphosphate and calcium acidic polyphosphate; and as the acidic metaphosphate, sodium acidic metaphosphate is effective. The organic phosphorus compound that is one of the components of the extreme pressure agent (C) in the present invention includes phosphorous esters and phosphoric esters. Phosphite esters include triphenyl phosphite, tris(nonylphenyl) phosphite, triisooctyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tristearylphosphite, trioleylphosphite, trilauryl trithiophosphite. Examples thereof include tertiary phosphites such as fluorite, secondary phosphites such as di-2-ethylhexylhydrodiene phosphite, dilaurylhydrodiene phosphite, and dioleylhydrodiene phosphite. Phosphate esters include trimethyl phosphate,
Tributyl phosphate, trilauryl phosphate, triphenyl phosphate, tricresyl phosphate, octyl diphenyl phosphate, tristearyl phosphate, trioleyl phosphate, monobutyl phosphate, dibutyl phosphate, monoisodecyl phosphate ,
Trichloroethyl phosphate, methyl acid phosphate, isopropyl acid phosphate,
Examples include butyl acid phosphate, 2-ethylhexyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, and oleyl acid phosphate. In addition, examples of organic sulfur compounds that are one of the components (C) include sulfurized oils and fats, sulfurized dibenzyl disulfide, polysulfide, di-ter-butysulfide, di-n-
Examples include butyl disulfide, polyoxyethylene polysulfide, and the like. Examples of the organic chlorine compound, which is another component (C), include chlorinated paraffin, chlorinated fats and oils, chlorinated fatty acid esters, pentachlorinated fatty acid esters, and the like. The partial esters and fatty acids of fatty acids having 5 or more carbon atoms which are the oily agent (D) component in the present invention include long chain dibasic acids such as adipic acid, azelaic acid, sebacic acid and long chain branched primary alcohols. , for example, 2-ethylhexanol, _C8 - _C10 oxo alcohols, or partial esters obtained from long-chain monobasic acids and glycols. Polyols having neopentyl skeletons include, for example, pentaerythritol, dipenta Examples include erythritol, trimethylolpropane, neopentyl glycol, etc. Fatty acids include fatty acids having 5 to 22 carbon atoms, such as beef tallow, lard, mutton fat, rapeseed oil, coconut oil, castor oil, perm oil, etc. , vegetable oil fatty acids, gavrylic acid, pelargonic acid, capric acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, putanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid,
Straight chain fatty acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid and 2,4-hexadienoic acid,
trans-2, cis-4 decadienoic acid, 6,10,14-
Unsaturated fatty acids such as hexadecatrienoic acid, cis-9, cis-12 octadecadienoic acid, cis-9, cis-12, cis-15 octadecatrienoic acid, oleic acid, or unsaturated fatty acids, or Synthetic fatty acids obtained by oxidizing dimerized dimer acid and paraffin using a catalyst, and branched synthetic fatty acids may be mentioned, and fatty acids having 7 to 14 carbon atoms are particularly preferred. Examples of the fatty acid amide and metal soap that are the organic powder (E) component in the present invention include hexanamide, octanamide, nonanamide, decaneamide, undecanamide, dodecanamide, tridecanamide, myristylamide, palmitylamide, stearylamide, Examples include oleinamide and linolamide. Further, the metal soap is, for example, a metal soap obtained by a reaction between a fatty acid having 22 or less carbon atoms and an alkali metal. Depending on the type of lubricant (A) used, the above
If components (B), (C), and (D) are not dissolved, use an emulsifier to uniformly suspend and disperse them. In particular, component (B), condensed phosphoric acid, is used after being suspended and dispersed. The emulsifier in this case should be arbitrarily selected depending on the type of lubricating oil, but examples include polymeric succinic acid ester and polymethacrylate, ethylene/olefin copolymer, styrene/isobutylene copolymer, Polyisobutylene etc. are effective. In that case, the amount of emulsifier to be blended is preferably 0.1 to 5% by weight. The blending ratio of the above components (B), (C), (D) and (E) to be blended into the lubricating oil (A) should be selected appropriately depending on the type of steel material, processing rate, processing shape, processing temperature, etc. Good luck, but
Usually 2 to 20% by weight of component (B), 2 to 30% by weight of component (C),
(D) component 3-30% by weight, and lubricating oil 20-93% by weight
A range of is desirable. If the amounts of components (B), (C), (D), and (E) blended into the liquid lubricant of the present invention are extremely small, a lubricating film will not be formed sufficiently, resulting in seizure. . Further, if the amount is too large, no further effect will be observed, so the above-mentioned blending ratio is preferable. The liquid lubricant for plastic working of the present invention is a mixture of a lubricating oil as a component (A), a condensed phosphoric acid and its acid salt as a component (B), an extreme pressure agent as a component (C), and an oily agent as a component (D). By simply supplying a liquid lubricant that contains at least one of the organic powders of component (E) and does not add water to the steel surface, die processing surface, or these surfaces, it reduces deformation heat and friction during processing. It uses heat to form a lubricating film with excellent heat resistance and lubricity on the surface of steel materials, greatly improving seizure prevention even for molded products with complex shapes and extremely high processing rates. The liquid lubricant for plastic working of the present invention can be used by applying it to a material such as steel to be plastic worked by, for example, a brush coating method, a spray method, a dipping method, a dripping method, etc. Bye. In addition, after heating either the liquid lubricant for plastic working of the present invention or a material such as a steel material to be processed and immersing the material in the liquid lubricant to apply a lubricant film treatment to the surface of the material, Since it can be processed, complicated processes such as conventional lubricant film treatment are not required, making it extremely simple. The liquid lubricant for plastic working of the present invention can be used for molded products with complex shapes and extremely high workability as described above, but it also uses graphite, molybdenum disulfide, etc. as a lubrication agent to improve working performance. Solid lubricants such as boron nitride, carbon fluoride, etc. can be used. In addition, an antioxidant for preventing deterioration of the liquid lubricant of the present invention and a rust preventive agent for preventing corrosion of metal materials can be added, but in this case, the lubricating film, which is the object of the present invention, can be added. There is no particular restriction as long as it does not inhibit the formation of. [Examples of the invention] Examples of the invention will be shown below. Examples 1 to 20, Comparative Examples 1 and 2 A chromium-molybdenum steel plate (SCM415) with a width of 20 mm, a length of 40 mm, and a thickness of 2 mm was heated to 100°C and 300°C in a nitrogen atmosphere, and the compositions shown in Table 1 were heated. Add to lubricant for plastic working. After being immersed for about 10 seconds, it was taken out, degreased and washed with trichlorotrifluoroethane (Daiflon S-3), and after drying, the amount (mg/cm ² ) of film produced by reaction on the steel surface was determined from the following formula. Weight after degreasing and drying - weight of steel plate before treatment/surface area of steel plate In addition, the friction coefficient was evaluated using a pendulum type oil tester, and the results are shown in Table 2. Test conditions are surface pressure ma
×150Kgf/ ^{mm2Temperature} is 100℃. Therefore, the larger the amount of film produced, the larger the reaction amount of the additive, the thicker the film is formed, which greatly contributes to improving the seizure resistance. Component C shown in Table 1 is the following partial ester. (A) Mono- and di-ester mixture of sebacic acid and 2-ethylhexanol (mono: 25.8%, di: 74.2% in gas chromatographic peak area ratio) (B) Mono- and di-ester mixture consisting of pentaerythritol and saturated fatty acids with 7 to 9 carbon atoms. A mixture of , tri, and tetraesters (mono in gas chromatography peak area ratio:
25.6%, Di: 43.9%, Tri: 27.5%, Tetra:
3.0%) (C) A mixture of mono-, di-, tri-, and tetraesters consisting of pentaerythritol and unsaturated fatty acids having 7 to 9 carbon atoms (mono:
10.0%, Di: 40.7%, Tri: 44.2%, Tetra:
5.1%) The following examples were compared with those of the present invention. <Composition of Comparative Example 1> Polyphosphoric acid (84% as P ₂ O ₅ ): 5% by weight 30% iron phosphate: 1% by weight Oleyl alcohol: 2% by weight Oleic acid: 20% by weight Oleylamine: 5% by weight Mineral oil (Viscosity 150 mm ² /S at 40°C): 65% by weight Water: 2% by weight <Composition of Comparative Example 2> Pyrophosphoric acid (80% as P ₂ O ₅ ): 5% by weight Dioleyl phosphite: 10% by weight Ethylene・Olefin copolymer: 2% by weight Mineral oil (viscosity at 40℃ 147mm ² /S): 83% by weight

【table】

【table】

【table】

【table】

[Table] As is clear from Table 2, the lubricant for plastic working of the present invention has excellent reactivity with steel materials and produces a large amount of reaction film compared to the comparative example. In addition, the coefficient of friction determined by a vibrating oil tester was low, indicating that it has excellent lubricity. After applying the plastic working lubricant shown in Table 1, as shown in Fig. 2, a mold (made of carbide _V5 ) with an extrusion angle of 120 degrees and a drawing diameter of 5 mm (processing rate 75%) 2 and a punch 3 are used to Extruded material 1 was processed and the processing performance was evaluated. The results are shown in Table 3.

【table】

[Table] The method for evaluating machining performance is to attach a band heater 4 to the mold 2, raise the mold temperature step by step from room temperature by 5 to 10°C, and then use the material 1 coated with cold working lubricant. We processed 10 pieces at a time and measured the highest mold temperature at which no seizure occurred on the surface of the processed material. The higher the temperature, the better the heat resistance and lubrication performance.
In other words, the processing performance of the lubricating oil is excellent. In addition, those of the present invention were compared and contrasted with those shown in Example 1 and a metal soap coating treatment (comparative example 3) on a phosphate coating often used in cold working of steel materials.
This is what I did. As is clear from Table 3, it can be seen that the plastic working lubricant of the present invention has significantly improved workability.
In addition, the same applies to material 1 which was heated to 100°C using lubricants No. 5, 6, 9, 15 and 19 shown in Table 1, immersed in the above lubricants, and subjected to lubricant film treatment. As a result of evaluating the machining performance, as shown in Table 3, good machining performance was shown. As is clear from the above explanation, the lubricating oil contains one or more selected from condensed phosphoric acid, sulfur, and chlorine compounds, a dibasic acid, a long chain branched primary alcohol or a polyol having a neopentyl type skeleton, and a fatty acid. A lubricant for cold working that contains one or more types of partial esters and does not add water can be applied simply to the surface of metal such as steel, and it shows high reactivity with the heat during processing and has excellent heat resistance. A lubricating film can be formed. Examples 21 to 36 As shown in Fig. 1, mineral oil and condensed phosphoric acid or its salt were applied to the surface of material 1, a cylindrical chromium-molybdenum steel material SCM415 with a nose having a diameter of 9.9 mm, a length of 30 mm, and a tip angle of 90 degrees. A plastic working lubricant of the present invention shown in Table 4 consisting of fatty acids was applied. Next, as shown in Fig. 2, the material 1 is processed by the forward extrusion method using a die (made of carbide) 2 with an extrusion angle of 120 degrees and an aperture diameter of φ6 (processing rate of 64%) and a punch 3.
Processing performance was evaluated. The evaluation results are shown in Table 4. The evaluation method for machining performance is to attach a band heater 4 to the mold 2, and increase the mold temperature from room temperature to 5 to 10 degrees Celsius.
We processed 20 pieces of material 1, which was heated step by step and coated with lubricating oil, and measured the highest mold temperature at which no seizure phenomenon occurred on the surface of the material after processing. The higher the temperature, the better the processing performance of the lubricant. In addition, the following items were compared and contrasted with those of the present invention. Comparative example 4 (commercially available processed oil) Base oil: Mineral oil Remaining amount Fatty oil content 43% by weight Additives Chlorine content 12% by weight Sulfur content 6% by weight Comparative example 5 Phosphoric acid (P ₂ O ₅ as oxide) 41.2 mol% Sodium carbonate (Na ₂ O in terms of oxide) 39.3 mol% Sodium monophosphate (K ₂ O in terms of oxide)
12.5 mol % and 7 mol % of boric acid (in terms of oxide B ₂ O ₃ ) were mixed, and this was heated and melted at 900° C. for 30 minutes to vitrify it. This vitrified sample was then placed in water for 20 minutes.
wt% dissolved. Comparative Examples 4 and 5 were also evaluated for processing performance in the same manner as Examples 21-36. These results are summarized in the fourth
Shown in the table. As is clear from Table 4, the plastic working lubricant composition of the present invention has superior working performance compared to Comparative Examples 4 and 5.

【table】

【table】
↑

Seizure occurs at room temperature
( ) Dimer/trimer ratio examples 37-53 Polyalkylene glycol oil (viscosity at 40°C 82
The processing performance was evaluated under the same processing conditions as in Example 10 using the plastic processing lubricant of the present invention shown in Table 5, which is composed of phosphoric acid (mm ² /S), condensed phosphoric acid or its salt, and fatty acid. The evaluation results are shown in Table 5. As is clear from the results in Table 5, the plastic working lubricant of the present invention obtained good results. Examples 54 to 69 Polyphosphoric acid, sodium polyphosphate and octanoic acid were added to mineral oil having a viscosity of 150 mm ² /S at 40° C. in the amounts shown in Table 6 to obtain a lubricant for plastic working of the present invention. The machining performance of the lubricant was evaluated under the same machining conditions as Examples 20 to 36. These evaluation results are shown in Table 6. As is clear from Table 6, good processing performance was obtained.

【table】

【table】

【table】

〔Effect of the invention〕

As explained above, according to the present invention, there is an effect that the lubricity of the lubricating film is significantly improved at high working rates such as high temperatures and high surface pressures.

[Brief explanation of drawings]

Figure 1 is a side view of the material used to evaluate the performance of lubricating oil, Figure 2 is a vertical cross-sectional view of the extrusion die used to evaluate the performance of lubricating oil, and Figure 3 is an example and a comparative example. Processing rate or drawing diameter and processing limit temperature (℃)
FIG. 1... Punch, 2... Material, 3... Mold processing surface, 4... Band heater for heating the mold, 5... Carbide part.

Claims (1)

[Scope of Claims] 1. A mixture of lubricating oil (A) and one or more types of condensed phosphoric acid and its acid salts (B) containing at least one or more of the following (C), (D) and (E), A lubricant for plastic processing that is characterized by containing substantially no water. (C) Extreme pressure agent selected from organophosphorus compounds, organosulfur compounds, and organochlorine compounds (D) Obtained by reacting fatty acids, long-chain dibasic acids, and long-chain branched primary alcohols. A partial ester having at least one hydroxyl group in the molecule, a partial ester having at least one hydroxyl group in the molecule obtained by reacting a long chain monobasic acid with glycol, a polyol having a neopentyl type skeleton and a carbon number of 5 An oily agent selected from partial esters having at least one hydroxyl group obtained by reacting with at least one hydroxyl group (E) An organic powder selected from fatty acid amides and metal soaps. 2. A mixture of lubricating oil (A) and one or more types of condensed phosphoric acid and its acid salts (B) contains at least one of the following (C), (D) and (E) and substantially contains water. A lubricant for plastic working, characterized in that a lubricant is applied to the surface of the workpiece, and the workpiece is subjected to plastic working in the presence of a film formed by the reaction between the lubricant and the workpiece. How to use the agent. (C) Extreme pressure agent selected from organophosphorus compounds, organosulfur compounds, and organochlorine compounds (D) Obtained by reacting fatty acids, long-chain dibasic acids, and long-chain branched primary alcohols. A partial ester having at least one hydroxyl group in the molecule, a partial ester having at least one hydroxyl group in the molecule obtained by reacting a long chain monobasic acid with glycol, a polyol having a neopentyl type skeleton and a carbon number of 5 An oily agent selected from partial esters having at least one hydroxyl group obtained by reacting with at least one hydroxyl group (E) An organic powder selected from fatty acid amides and metal soaps. 3. A method of using a lubricant for plastic working according to claim 2, characterized in that the lubricant is applied in advance before plastic working. 4. In claim 2, the lubricant and/or the metal material is heated, the metal material is immersed in the lubricant to form a lubricant film on the surface of the metal material, and then plastic working is performed. A method of using a lubricant for plastic working characterized by: 5 A metal surface treatment in which a lubricant and/or a metal material is heated and the metal material is immersed in the lubricant to form a lubricant film on the surface of the metal material, and the lubricant is a lubricant (A) and Plastic processing characterized by containing at least one of the following (C), (D) and (E) in a mixture of one or more types of condensed phosphoric acid and its acid salts (B), and containing substantially no water. How to use lubricants. (C) Extreme pressure agent selected from organophosphorus compounds, organosulfur compounds, and organochlorine compounds (D) Obtained by reacting fatty acids, long-chain dibasic acids, and long-chain branched primary alcohols. A partial ester having at least one hydroxyl group in the molecule, a partial ester having at least one hydroxyl group in the molecule obtained by reacting a long chain monobasic acid with glycol, a polyol having a neopentyl type skeleton and a carbon number of 5 An oily agent selected from partial esters having at least one hydroxyl group obtained by reacting with at least one hydroxyl group (E) An organic powder selected from fatty acid amides and metal soaps. 6. Apply a lubricant to the metal material and/or mold processing surface during plastic working, and as the lubricant, add the following ( C), (D) and (E),
A method of using a lubricant for plastic working, characterized by using a lubricant that does not substantially contain water. (C) Extreme pressure agent selected from organophosphorus compounds, organosulfur compounds, and organochlorine compounds (D) Obtained by reacting fatty acids, long-chain dibasic acids, and long-chain branched primary alcohols. A partial ester having at least one hydroxyl group in the molecule, a partial ester having at least one hydroxyl group in the molecule obtained by reacting a long chain monobasic acid with glycol, a polyol having a neopentyl type skeleton and a carbon number of 5 An oily agent selected from partial esters having at least one hydroxyl group obtained by reacting with at least one hydroxyl group (E) An organic powder selected from fatty acid amides and metal soaps.