JPH10259391A - Lubricant for high-temperature plastic working - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lubricant for high-temp. plastic working which does not cause the seizure of a steel material to a tool surface, the abrasion or roughening of a tool surface, and the pollution of the working environment in the high-temp. plastic working of a steel material or a nonmetallic material by compounding a base oil with a branched fatty acid (salt) and a highly alkaline earth metal salicylate. SOLUTION: An oil material obtd. as a by-product in a process for producing a hardened oil by hydrogenating a natural oil (e.g. soybean oil, cotton seed oil, or a fish oil) is heated in the presence of 0.2-0.5% nickel catalyst in a hydrogen stream under a pressure of 2-3 atm at about 180 deg.C for 2-3 hr, and the resultant product contg. a hardened oil and a branched fatty acid is subjected to vacuum distillation to remove the hardened oil, thus giving a 6-60 deg.C branched fatty acid (salt). The objective lubricant is prepd. by compounding 10-99.9 wt.% base oil selected from among mineral oils, synthetic esters, animal and vegetable oils, and polymerized oils with 0.1-90 wt.% branched fatty acid above-obtd. and, if necessary, 1-50 wt.% highly basic alkaline earth metal salicylate contg. CaCO3 in a concn. (in terms of base value) of 40 or higher, pref. 100 or higher, still pref. 150 or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to high-temperature plastic working of steel and non-ferrous metal materials,
The present invention relates to a lubricant for high-temperature plastic working which prevents wear and roughening of the tool surface and does not pollute the working environment.

[0002]

2. Description of the Related Art In recent years, hot rolling of steel and non-ferrous metal materials,
In high-temperature plastic working such as hot forging, hot die working, and hot pressing, a lubricant for high-temperature plastic working is used to protect tools, and the effect is reduced. Examples of such lubricants include solid lubricants such as graphite, water glass, boron nitride, mica, molybdenum disulfide, iron oxide, calcium carbonate, and fluorinated graphite, which have a lubricating effect at high temperatures; Extreme pressure lubricants such as dialkyldithiophosphates and phosphate esters; mineral oils, fats and oils, fat and oil polymers,
An oiliness improver such as a synthetic ester; an adhesion improver / pour point depressant such as a methacrylate copolymer or a butylene butadiene copolymer, alone or in combination of two or more kinds; and in some cases, ditertiary butyl cresol or alpha Add an antioxidant such as naphthylamine,
It is commonly used.

[0003] The high-temperature plastic working of the steel or non-ferrous metal material is performed at a high temperature, for example, a temperature in the range of 700 to 1200 ° C. At such a temperature, the extreme pressure additive and the oiliness improver described above cause oxidation and thermal decomposition, and do not exert a sufficient effect on the lubricating surface. For this reason, a large amount of oil is supplied to the lubricated surface in high-temperature plastic working as compared with low-temperature plastic working, but it is difficult to obtain a sufficient effect. On the other hand, solid lubricants such as graphite and iron oxide are hardly decomposed even at a high temperature of 700 ° C. or more and have a sufficient effect, and are therefore widely used as lubricants for high-temperature plastic working.

However, solid lubricants have the following problems. First, since it is composed of solid particles, when it is used as a lubricant, it must be dispersed in a base oil. However, since the solid lubricant has a higher density than the base oil, the solid lubricant separates and sediments from the base oil when stored for a long time. Therefore, a lubricant containing a solid lubricant cannot be stored for a long period of time, and it is necessary to re-disperse the separated solid lubricant in a liquid by stirring it periodically. However, some solid lubricants are difficult to redisperse due to secondary agglomeration of particles. In this case, the performance of the lubricant deteriorates, and a solid lubricant that cannot be re-dispersed clogs the strainer, the oil supply valve and the like. Therefore, in order to solve this problem, the addition of a dispersant having the function of improving the dispersion of the solid lubricant in the base oil and the stabilization treatment of the surface of the solid lubricant particles are performed to improve the dispersibility in the base oil. And so on. However, all of these formulations are expensive and require complicated steps for production. Further, solid lubricants such as graphite, iron oxide, and molybdenum disulfide are black, and if a lubricant containing these is used, it remarkably pollutes a refueling site and a working environment. Recently, white-based solid lubricants are also present, but fluorinated graphite and boron nitride, which have good lubricity, are extremely expensive. Inexpensive solid lubricants of white color include calcium carbonate and mica, but their lubricity is insufficient. For the above reasons, graphite, iron oxide, molybdenum disulfide, etc., which are inexpensive and have good lubricity, are currently used as high-temperature plastic working lubricants, although they have the problem of contaminating the surroundings with black. It is.

Japanese Patent Application Laid-Open No. 48-79211 discloses a hot rolling method comprising a polymer of linoleic acid or linoleic acid as a main component and a balance of a monomer of linoleic acid or linoleic acid. For lubricants
Japanese Patent No. 7087 discloses a lubricant for hot rolling based on a tallow-lard mixture containing a free fatty acid, but does not have a sufficiently satisfactory lubricating performance. Further, JP-A-8-41486 discloses a metal plastic working lubricant containing a carboxylic acid or a carboxylate, but the lubricating performance of a fatty acid metal salt such as a metal octylate is not sufficient. It is described.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a lubricant for high-temperature plastic working which prevents seizure of a steel material on a tool surface, abrasion of a tool surface, and roughness of a tool surface and does not contaminate a working environment. More specifically, 700 ° C.
Hot rolling, hot forging of steel materials such as carbon steel and stainless steel or non-ferrous metal materials,
In high-temperature plastic working such as hot die working and hot press working, one or both of the tool and material are air sprayed,
An object of the present invention is to provide a lubricant for high-temperature plastic working which does not cause roughening or wear of a tool due to lack of lubricity and does not contaminate a lubricating part and a working environment when lubricated by a water injection method.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is attained by a lubricant for high-temperature plastic working, comprising a base oil and at least one selected from the group consisting of branched fatty acids and salts thereof. Is done. The lubricant of the present invention sufficiently exhibits its intended effect by containing at least one selected from the group consisting of branched fatty acids and salts thereof, but further contains a highly basic alkaline earth metal salicylate. Thereby, a better lubrication effect can be obtained.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the lubricant of the present invention, any of a synthetic branched fatty acid and a natural branched fatty acid can be used as the branched fatty acid. Specific examples of such branched fatty acids include synthetic branched fatty acids synthesized from petroleum-based materials such as propylene and α-olefins, and natural branched fatty acids synthesized from natural fatty acids. The number of carbon atoms of the branched fatty acid is preferably 6 to 60, more preferably 9 to 40. Specific examples of the branched fatty acid used in the present invention include branched nonanoic acid (CEKANOIC C-9ACID. Exxon Chemical Co., Ltd.),
Branched lauric acid (Isocarb C12. Manufactured by Condea), branched tridecanoic acid (CEKANOIC C-13ACID. Manufactured by Exxon Chemical), branched palmitic acid (Isocarb C16. Manufactured by Condea), branched triacontanic acid, branched tetracontanic acid,
Synthetic fatty acids such as branched pentacontanic acid; and natural branched fatty acids such as branched oleic acid, branched stearic acid (Emersol 871.873, Emery), and branched behenic acid.

Next, examples of the method for producing these branched fatty acids will be described, but the present invention is not limited thereto. The description will be made by taking branched oleic acid, which is a naturally branched fatty acid, as an example. In general, branched oleic acid is used when hydrogenating natural oils such as soybean oil, cottonseed oil and fish oil to obtain a hardened oil.
Obtained as a by-product. Specifically, 0.
After adding a nickel catalyst of 2 to 0.5% and heating the mixture at 180 ° C. and a pressure of 2 to 3 atm for 2 to 3 hours while passing hydrogen,
A hardened oil and branched oleic acid are obtained. When this is distilled under reduced pressure, branched oleic acid is obtained as a residue. Also,
The description will be made by taking branched stearic acid which is a synthetic branched fatty acid as an example. Aldol condensation of nonylaldehyde in the presence of sodium hydroxide gives branched stearyl alcohol. When this is alkali-dissolved together with potassium hydroxide, the terminal hydroxyl group is oxidized to obtain branched stearic acid.

[0010] Specific examples of the salt of the branched fatty acid used in the present invention include an amine salt and a metal salt.
Representative examples of the branched fatty acid amine salts include aliphatic amines such as laurylamine and oleylamine; alicyclic amines such as cyclopentylamine and cyclohexylamine; alkylalkanolamines such as ethanolamine and triethanolamine; and aromatics such as aniline and naphthylamine. And branched fatty acid amine salts such as aromatic amines. Representative examples of branched fatty acid metal salts include lithium salts, sodium salts,
Alkali metal salts such as potassium salts; alkaline earth metal salts such as magnesium salts, calcium salts, and barium salts; and other metal salts such as zinc and lead. The salt of the branched fatty acid is
It can be easily produced by reacting an equivalent amount of the above amine or the above metal with a branched fatty acid.

Any of these synthetic branched fatty acids, natural branched fatty acids, and salts thereof can be transparently dissolved in the base oil in an arbitrary amount. The content of the branched fatty acid and / or salt thereof used in the present invention is preferably 0.1% by weight or more in the lubricant, more preferably 0.1 to 90% by weight.
If the content is less than 0.1% by weight, sufficient lubricity cannot be exhibited.

Specific examples of the overbased alkaline earth metal salicylate used in the lubricant of the present invention include overbased calcium salicylate, overbased magnesium salicylate, and overbased barium salicylate.
The same effect can be obtained by using any of them. Therefore, in this specification, a highly basic calcium salicylate will be described, but the present invention is not limited thereto. The overbased calcium salicylate used in the present invention is a known substance. For example, commercially available products include OSCA431 and OSCA45 of Oska Chemical Co., Ltd.
3, OSCA435, OSCA438, and SAP005Ca salicylate manufactured by Shell Chemical Company. Each of these high-basic calcium salicylates is a transparent liquid substance, and any amount can be transparently dissolved in a lubricant obtained by adding a branched fatty acid and / or a branched fatty acid salt to a base oil. is there.

In the lubricant of the present invention, when high-basic calcium salicylate is used, its content is arbitrary, but it is preferably 1% by weight or more, preferably 3% by weight or more. When the content is less than 1% by weight, the effect of the addition is not sufficiently exhibited. The upper limit is not particularly limited, but is usually 50% by weight or less.

The highly basic calcium salicylate used in the present invention has a base number of 40 or more, preferably 1 or more.
It is desirable to contain CaCO ₃ of 00 or more, more preferably 150 or more. The base number is the number of mg of potassium hydroxide equivalent to hydrochloric acid required to neutralize all base components contained in 1 gram of a sample. This base number is
It is defined as a total base number in JIS2501. Therefore, the base number of a highly basic calcium salicylate increases as the content of CaCO ₃ as a base component increases. Base number of highly basic calcium salicylate is 40
If it is less than 3, a sufficient lubricity improving effect cannot be expected.

Examples of the base oil used in the present invention include mineral oil (spindle oil, machine oil, cylinder oil, etc.), synthetic ester (fatty acid octyl ester, trimethylolpropane fatty acid ester, pentaerythritol fatty acid ester, etc.), oils and fats (Seed oil, beef tallow, lard, etc.), polymerized fats (soy polymerized oil, rapeseed polymerized oil, castor polymerized oil, etc.), and a mixture of two or more of these. Each of these base oils has a function of forming a lubricating film between a roll and a lubricant, lowering a coefficient of friction, and suppressing roughening and seizure of a tool. In order to sufficiently exhibit this effect of lowering the friction coefficient,
It is desirable that the lubricant of the present invention contains a base oil in an amount of 10% by weight or more. If the content of the base oil in the lubricant is less than 10% by weight, sufficient lubricity may not be exhibited.
The upper limit of the content of the base oil is 99.9% by weight.

The performance as a lubricant can be further improved by adding various lubricant additives to the lubricant of the present invention. Specific examples of such additives include extreme pressure agents (zinc dialkyl dithiophosphate, molybdenum carbamate, oil-soluble organometallic compounds containing zinc such as cobalt octylate, molybdenum, cobalt, etc., sulfurized oils and fats, sulfurized synthetic fatty acids). Sulfurized fatty acid ester compounds such as esters, dihexyl polysulfide, dinonyl polysulfide, aliphatic and aryl aliphatic or alicyclic olefinic hydrocarbon sulfide compounds such as dialkyl polysulfide compounds such as didodecyl polysulfide, highly basic calcium sulfonate, Phosphorus compounds such as highly basic metal salt compounds other than highly basic alkaline earth metal salicylates, such as highly basic calcium phenate and highly basic calcium carboxylate, orthophosphate esters, phosphite esters, acidic phosphate esters, etc. ), Adhesion improver and pour point depressant (polyisobutylene, polymethacrylate polymer, etc.), antioxidant (alpha naphthylamine, ditertiary butylphenol, etc.), surfactant (polyoxyethylene coconut oil fatty acid sorbitan and polyoxy monooleate) Polyoxyalkylene alkyl sorbitan compounds such as ethylene sorbitan; polyoxyethylene lauryl ether; polyoxyalkylene alkyl ether compounds such as polyoxyethylene oleyl ether; polyoxyethylene nonyl phenyl ether; polyoxyethylene such as polyoxyethylene lauryl phenyl ether Alkyl phenyl ether compounds,
Neutral metal salt sulfonate compounds such as neutral sodium sulfonate and neutral calcium sulfonate). The use amount of these additives is not particularly limited, but is usually 0.1 to 85% by weight in the lubricant.

The lubricant of the present invention can be produced by a known method. For example, a predetermined amount of a base oil, a branched fatty acid or a branched fatty acid salt, a highly basic calcium salicylate, and a lubricating oil additive are charged into a stainless steel heating kettle having a stirrer.
It can be easily produced by stirring at 0 to 80 ° C for 1 to 2 hours. The lubricant after production is preferably a transparent liquid. The lubricant of the present invention uses a gear type or plunger type lubricant pump, and is used to lubricate one or both of the tool and the material by air spray or water injection, and at the time of high-temperature plastic working of steel material. , Suppresses tool wear and rough skin.

[0018]

The lubricant of the present invention is a transparent liquid lubricant which does not contain a black solid lubricant.
In high-temperature plastic working performed in the range of
Even if the material is machined twice or more times, it is effective in suppressing tool wear and rough skin, and does not contaminate the refueling equipment and the working environment.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below by way of examples by taking hot rolling of steel as an example, but the present invention is not limited thereto. Table 1 in a stainless steel heating pot with a stirrer
, Base oils, branched fatty acids, branched fatty acid salts, highly basic calcium salicylates, and lubricating oil additives shown in Tables 1 to 3 were added at a weight ratio shown in Tables 1 to 3, and the mixture was stirred at 50 to 80 ° C for 1 to 2 hours, A lubricant with a transparent appearance was produced. Further, as shown in Table 4, a lubricant of a comparative example using a linear fatty acid instead of a branched fatty acid was produced in the same manner. Next, the lubricant was lubricated with the following hot rolling conditions and lubricant lubrication using a water injection lubrication system using a liquid lubrication oil lubrication pump on the roll surface of a double hot rolling mill. Refueled in quantity. In the case of the comparative examples (Comparative Examples 9 and 10 using a commercially available product) in which the lubricant is viscous and cannot be lubricated by a liquid lubricating oil supply pump, the lubricant is directly applied to the roll surface by hand. The sex was evaluated.
Comparative Examples 9 and 1 in which a lubricant was manually applied to the roll surface
In the case of Comparative Example 11 in which no lubricant was used, only dilution water was injected from a water injection type refueling facility. The results are shown in Tables 1 to 4.

Hot Rolling Conditions and Lubricant Lubrication Amount Roll Roll High carbon high alloy cast iron roll 150mmΦ × 150mmL Rolled material SUS430 steel plate 4mm thick 25mm length 100mm 100 rolls (rolled at the same location of roll) Rate, speed 10%, 14mpm Steel heating temperature Tested under two conditions of 700 ° C and 1200 ° C Finished thickness 3.6mm Lubricant lubrication amount Total 0.1L / min for upper and lower rolls Lubricant lubrication pump model Plunger pump Dilution water Total 1.0L / min for upper and lower rolls Roll drainer Rubber

Evaluation of Lubricant Appearance of Lubricant: O is transparent, X is opaque Pollution: Whether there is contamination around the equipment and working environment during use Lubricity evaluation: After completion of the hot rolling test, abrasion of the roll and skin The condition was observed and evaluated according to the following five grades. AA: Roll wear and skin roughness are not observed at all A: Almost not observed B: Slightly observed C: Accepted D: Notably observed

[0022]

[Table 1]Example 1 2 3 4 5 6 7 8 9 10 Base oil (1) 99.9 99.9 90.0 97.0 97.0 97.0 97.0 97.0 99.9 − (2) − − − − − − − − − − 99.9 (3) − − − − − − − − − − − Branched fatty acids (4) − − − 3.0 − − − − − − (5) 0.1 0.05 10.0 − − − − − 0.05 0.1 (6) − 0.05 − − 3.0 − − − − − (7) − − − − − 3.0 − − − − (8) − − − − − − 3.0 − 0.05 −(9) − − − − − − − 3.0 − − Appearance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Pollution No No No No No No No No No No No Lubricity 700 ℃ A A A A A A A A A A A A 1200 ℃ A A A A A A A A A A A A

[0023]

[Table 2]Example 11 12 13 14 15 16 17 18 19 20 Base oil (1) − 99.9 10.0 − 25.0 96.9 96.0 96.7 96.5 96.9 (2) − − − 5.0 25.0 − − − − −(3) 99.9 − − 5.0 25.0 − − − − − − Branched fatty acids (5) − − 90.0 90.0 25.0 0.1 1.0 0.3 0.5 0.1 (9) 0.1 0.1 − − − − − − − − − Salicylate (10) − − − − − 3.0 − − 1.5 − (11) − − − − − − 3.0 − 1.5 1.5 (12) − − − − − − − 3.0 − 1.5 Appearance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Pollution No No No No No No No No No No No Lubricity 700 ℃ A A A A A A A A A A A A A A A A 1200 ℃ A A A A A A A A A A A A A A

[0024]

[Table 3]Example 21 22 23 24 25 26 27 28 29 30 31 Base oil (1) 89.9 94.9 94.9 76.9 76.9 93.9 93.9 78.9 75.0 6.0 12.0 (2) − − − − − − − − − − 6.0 − Branched fatty acids (5) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 1.0 3.0 3.0 Salicylate (12) 10.0 − − 3.0 3.0 3.0 3.0 3.0 3.0 40.0 65.0 Additive (17) − 5.0 − − − − − − − − 15.0 (18) − − 5.0 − − − − − 3.0 − 5.0 (19) − − − 20.0 − − − − − 30.0 − (20) − − − − 20.0 − − − 3.0 − − (21) − − − − − 3.0 − 3.0 − − − (22) − − − − − − 3.0 − − − −(23) − − − − − − − 15.0 15.0 15.0 − Appearance ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Pollution No No No No No No No No No No No No Lubricity 700 ℃ AA AA AA AA AA AA AA AA AA AA AA 1200 ℃ AA AA AA AA AA AA AA AA AA AA AA

[0025]

Table 4 Comparative Example 1 2 3 4 5 6 7 8 9 9 Base oil (1) 100 − − 9.0 97.95 97.0 97.0 97.0 97.0 (2) − 99.95 99.95 − − − − − − (3) − − − − − − − − − Branched fatty acids (5) − 0.05 − 91.0 0.05 − − − − (8) − − 0.05 − − − − − − − Salicylate (12) − − − − 2.0 − − − − Linear fatty acids (13) − − − − − 3.0 − − − − (14) − − − − − − 3.0 − − (15) − − − − − − − 3.0 − (16) − − − − − − − − − 3.0 Appearance ○ ○ ○ ○ ○ ○ ○ ○ ○ Contamination No No No No No No No No No Lubricity 700 ℃ DC C C D D D D 1200 C DC C C D D D D

Notes: (1) Base oil A (refined mineral oil ISO VG46) (2) Trimethylolpropane triolate (3) Rapeseed oil (4) Branched nonanoic acid (brand name CEKANOIC C-9 ACID) (5) Branched laurin Acid (trade name: Isocarb 12) (6) Branched stearic acid (trade name: Emersol 871) (7) Branched pentaacontantanic acid (8) Branched calcium laurate (9) Branched dicyclohexylamine laurate (10) High base calcium salicylate Base number 60, (Product name
(OSCA431) (11) High base calcium salicylate base number 230, particle size distribution 0.05-0.5 μm, (trade name OSCA435) (12) High base calcium salicylate base number 320, particle size distribution 0.05-0.5 μm, (trade name OSCA438) (13) oleic acid (14) linoleic acid (15) oleic acid dicyclohexylamine salt (16) zinc octylate (17) zinc dialkyl dithiophosphate (18) polyisobutylene (19) dinonyl polysulfide (20) didodecyl polysulfide ( 21) Polyoxyethylene nonyl phenyl ether (22) Calcium dinonyl naphthalene sulfonate neutral salt (23) Highly basic calcium sulfonate base number 400

Comparative Example 10 is a commercially available lubricant A for high temperature plastic working.
It is. Ingredients: triiron tetroxide particles (particle size 0.5-1.0 μm) 30.0% heavy calcium carbonate particles (particle size 10-20 μm) 18.8% mineral oil-based lithium grease 51.2% Properties: NLGI butterfly When measured in degrees, Two grades, viscous. Comparative Example 11 is a commercially available lubricant B for high-temperature plastic working. Ingredients: triiron tetroxide particles (particle size 0.5-1.0 μm) 30.0% heavy calcium carbonate particles (particle size 10-20 μm) 18.8% water 49.2% sodium alginate 2.0% : The viscosity is 49000 cp at 25 ° C. and is viscous.

In Comparative Examples 10 and 11, the appearance was x, contamination was found, and the lubricity was C at 700 ° C and 1200 ° C. As is clear from Tables 1 to 3, the lubricant for high-temperature plastic working of the present invention containing a predetermined amount of base oil and a branched fatty acid or a salt thereof has a transparent appearance and may contaminate the surroundings. And excellent lubricity.
On the other hand, as shown in Table 4, Comparative Example 1 containing no branched fatty acid, Comparative Examples 2 and 3 containing less branched fatty acid content
And 5, in Comparative Example 4 in which the content of the base oil is small, and in Comparative Examples 6 to 9 in which a linear fatty acid is used instead of a branched fatty acid, the appearance is transparent and the surroundings are not contaminated, but the lubricity is remarkable. It turns out that it is low.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C10N 30:04 30:06 30:08 40:24 (72) Inventor Hiroshi Ueyapo 1-4-1, Tsujido Shindai, Fujisawa-shi, Kanagawa Kyodo Yushi Co., Ltd.

Claims (5)

[Claims] 1. A high-temperature plastic working lubricant comprising a base oil and at least one member selected from the group consisting of branched fatty acids and salts thereof. 2. The lubricant for high-temperature plastic working according to claim 1, further comprising a highly basic alkaline earth metal salicylate. 3. The lubricant for high-temperature plastic working according to claim 1, wherein the branched fatty acid has 6 to 60 carbon atoms. 4. The lubricant for high-temperature plastic working according to claim 1, wherein the base number of the highly basic alkaline earth metal salicylate is 40 or more. 5. The highly basic alkaline earth metal salicylate is a highly basic calcium salicylate.
5. The lubricant for high-temperature plastic working according to any one of 4.