JPH0564679B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a lubricating oil for cold rolling of metal materials, more specifically a lubricating oil for cold rolling of metal materials that can be rolled in a wide range of thickness (hereinafter referred to as cold rolling oil). (or sometimes simply referred to as rolling oil). [Prior art] In the past, beef tallow, pork fat,
Commonly used base oils include animal and vegetable oils such as palm oil, mineral oils, or mixtures thereof, with various additives added thereto. However, in recent years, with the advancement of cold rolling technology, from the perspective of improving productivity, the number of passes during rolling has been reduced,
Higher rolling speeds are required, and in addition, lines for large-scale continuous rolling are highly automated, and demands for streamlining the rolling process and improving the surface quality and specification accuracy of finished steel sheets are becoming more stringent. There is. [Problems to be solved by the invention] However, even with conventional cold rolling oils based on fats such as beef tallow and palm oil, which are said to have high lubricity,
The above conditions were no longer satisfied, and rolling was inevitably carried out under conditions lower than the actual capacity, and a cold rolling oil that could replace it had not yet been found. In other words, in conventional cold rolling oil, under the harsh conditions assumed in actual operations, the rolling oil composition deteriorates due to thermal decomposition and thermal oxidative decomposition in the rolling oil coolant, and iron generated during rolling is degraded. When dirt such as powder and scum gets mixed into the composition, and when these dirts are mixed and adhered to the surface of the rolled steel sheet together with the rolling oil composition and subjected to the post-processing as a coil after rolling, the temperature of the steel sheet is about 130℃. Due to the heating to 200 to 300℃ during preheating and annealing, under the conditions mentioned above, chemical reactions such as oxidation and decomposition polymerization result in polymerization and resin formation, which becomes difficult to remove even during cleaning, and subsequent When subjected to the annealing process, high heat (300
~700℃), resulting in soot stains on the entire surface of the steel plate and a state similar to edge carbon with soot adhering to the edges of the rolled material, which not only impairs the appearance of the steel plate, but also impairs plating, bonding, and painting properties. There were problems such as a decrease in surface treatment properties. Therefore, it has been desired to develop a cold rolling oil that has a lubricating performance superior to conventional fat-based cold rolling oils and is capable of rolling that satisfies the above-mentioned severe conditions. [Means for Solving the Problems] Under the circumstances, the present inventor has conducted intensive research and has focused on the excellent rolling lubricity of animal and vegetable fats and oils such as beef tallow, palm oil, and lard. The residual carboxylic acid group or hydroxyl group of a polyester obtained by heat condensation of a predetermined amount of dimer acid and/or polymer acid and at least one type of dimer acid and/or polymer acid of higher aliphatic unsaturated acid and polyols and alcohol or It has been discovered that a composition containing a predetermined amount of ester reacted with a fatty acid has dramatically improved rolling lubricity compared to a single animal or vegetable oil such as beef tallow, palm oil, pork fat, etc. Furthermore, by combining a specific type of antioxidant with this lubricant, in addition to improving rolling lubricity, it also improves thermal decomposition resistance and thermal oxidative decomposition resistance when the rolling oil coolant is used repeatedly over a long period of time. It also has excellent properties that can withstand the harsh conditions expected in actual operations, such as good degreasing and surface cleanliness of the steel plate after rolling even when contaminated with iron powder, scum, etc. generated during rolling. The present invention was completed based on the discovery that it is possible to impart the following characteristics. That is, the present invention provides fats and oils with (a) 0.5 to 10% by weight (hereinafter simply expressed as %) of at least one of dimer acids and polymer acids of higher aliphatic unsaturated acids having 16 to 20 carbon atoms; (b) At least one of dimer acids and polymer acids of higher aliphatic unsaturated acids having 16 to 20 carbon atoms is thermally condensed with polyols to form a polyester, and the remaining carboxyl group or hydroxyl group of this polyester is injected with an alcohol or carbon having 1 to 22 carbon atoms. Number 12-22
5-40% ester with a molecular weight of 750-7500 obtained by reacting fatty acids of
Two or more antioxidants selected from the group consisting of sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants are blended in an amount of 0.3 to 10% each (however,
Each of two or more antioxidants selected from the group consisting of phenolic antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants.
0.3~5.0%, 0.3~8.0%, 0.3~5.0% and 0.3~
This product provides a lubricating oil for cold rolling of metal materials (excluding cases containing 5.0%). Examples of the fats and oils used as the base oil component in the present invention include beef tallow, palm oil, pork fat, and the like. As the beef tallow, any of crude beef tallow, refined beef tallow, and edible beef tallow can be used, but it is more desirable to use refined beef tallow and edible beef tallow. As the palm oil, crude palm oil, refined palm oil, and deoxidized palm oil can be used. Refined pork fat is preferable. The dimer acid and polymer acid in (a) have 16 carbon atoms.
-20 higher aliphatic monoenoic or dienoic acids, such as dimer and polymeric acids of zomaric acid, oleic acid, linoleic acid, gadoleic acid.
These dimer and polymer acids are used in the range of 0.5-10% of the total composition. If it exceeds this range, the surface cleanliness of the steel plate after rolling will be poor due to poor washability, and if it is less than this range, the lubricity will deteriorate, which is undesirable. The ester (b) is produced by heating and condensing polyols with at least one type of dimer acid or polymeric acid of a higher aliphatic unsaturated acid having 16 to 20 carbon atoms. 1-22 alcohol or carbon number 12-
Molecular weight 750-7500 made by reacting with 22 fatty acids
It is an ester of The dimer acid or polymer acid used here is
It is the same as the dimer acid or polymer acid used in (a). Examples of polyols include propylene glycol, ethylene glycol, dipropylene glycol, diethylene glycol, neopentyl glycol, butanediol, pentanediol, hexanediol, as well as polyoxypropylene glycol, polyoxyethylene glycol,
Examples include polyoxypropylene-polyoxyethylene-glycol. Examples of alcohols having 1 to 22 carbon atoms include methanol, ethanol,
Butanol, heptyl alcohol, octyl alcohol, caprylic alcohol, nonyl alcohol, decyl alcohol, stearyl alcohol,
undecyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, isostearyl alcohol, behenyl alcohol,
Examples include oleyl alcohol. Also the number of carbon
Examples of the 12-22 fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, behenic acid, and the like. If the molecular weight of the ester (b) is less than 750,
The lubricity is poor, and if it is greater than 7500, the solubility in the compounding system will be poor and the viscosity will be high, causing problems in handling, which is not preferred. These (b) esters are used in the range of 5 to 40% of the total composition,
If the content exceeds 40%, oil stain will occur significantly, and if it is less than 5%, the lubricity will deteriorate, which is not preferable. Among the antioxidants (c), examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol; 2-tert-butyl-p-cresol;
Cresol; 2,6-di-tert-butylphenol; 3-methyl-6-tert-butylphenol;
2,4-di-tert-butylphenol; 2,5-
Di-tert-butyl-p-cresol; 3,5-di-tert-butyl-4-hydroxybenzyl alcohol; 2,4,6-tri-tert-butylphenol; Catechol; p-tert-butylcatechol;
4,6-di-tert-butyl-resorcin; 6-
(4-oxy)-3,5-di-tert-butyl-anilino-2,4-bis-(n-octylthio)-1,
3,5-triazine; (4-oxy-3,5-di-tert-butyl-benzyl)-octadecyl phosphate; 4,4'-thiobis(3-methyl-6
-tert-butylphenol); 4,4'-butylidenebis(3-methyl-6-tert-butylphenol);2,2'-methylenebis(4-methyl-6-
tert-butylphenol);2,2'-thiobis(4,6-di-tert-butylresorcin); 2,
2'-methylenebis(4-ethyl-6-tert-butylphenol);4,4'-methylenebis(2,6
-di-tert-butylphenol);2,2'-(3,
5-di-tert-butyl-4-hydroxy)propane;4,4'-cyclohexylidene bis(2,6-
di-tert-butylphenol); tetrakis[methylene-3-(3,5-di-tert-butyl-4-
Hydroxyphenyl)propionate]methane;
Hexamethylene glycol bis[β-(3,5-
di-tert-butyl-4-hydroxyphenol)
propionate]; 2,2'-thio[diethyl-bis-3(3,5-di-tert-butyl-4-hydroxyphenol)propionate]; 1,3,5
-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene; bis-[3,3'-bis-(4'-hydroxy-
3'-tert-butyl-phenyl)-butyric acid] glycol ester; 1,3,5-tris-
(4-tert-butyl-3-hydroxy-2,6-
Dimethylbenzyl) isocyanuric acid, etc. can be used. Sulfur-based antioxidants include dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, laurylstearyl thiodipropionate, distearyl-β,β′-thiodibutyrate, dilauryl Sulfide, dioctadecyl sulfide, 2-
Mercaptobenzimidazole, S-(3,5-
di-tert-butyl-4-hydroxybenzyl)-
Alkylthioglycolate, 4,4'-thiobis-
(6-alkyl-3-methylphenol), N-oxy-diethylene-benzothiazylsulfenamide, tetraalkyl-thiuram-disulfide, tetraalkyl-thiuram-monosulfide, and the like. Examples of phosphorus antioxidants include triphenyl phosphite, triotadecyl phosphite,
tridecyl phosphite, trilauryl trithiophosphite, triallylphosphite,
Di-(dinonylphenyl)-mono-(p-nonylphenyl) phosphorite, diphenylisodecyl phosphorite, o-[2-tert-butyl-5-
Methyl-4-(2-methyl-5-tert-butyl-
4-(hydroxyphenylthio)phenyl]-S,
S'-bis-(laurylthio) phosphite, phenyl diisodecyl phosphite, phenyl-
Di-iso-octyl phosphite, tris (cyclohexyl phenyl) phosphite, tris (o-cyclohexylphenol) phosphite, tris (o-biphenyl) phosphite,
Typical examples include tris(p-phenylphenol) phosphite, alkyl ( _C8 - _C12 ) cyclohexyl phosphite, and alkyl ( _C8 - _C12 ) phenylcyclohexyl phosphite. In addition, the amine antioxidants include phenothiazine; N,N'-di-tert-butyl-p-phenylenediamine;4,4'-tetramethyl-diaminodiphenylmethane;4-hydroxydiphenylamine;-Amino-N'-phenylparaphenylenediamine;N,N'-bis(octylphenyl)
Amine;N,N'-diphenyl-p-phenylenediamine;N,N'-disalicylidene-1,2-
Diaminopropane;4,4'-bis(4-α,α'-
dimethylbenzine) diphenylamine; 4,4'-
Dicumyl diphenylamine; N,N'-di-2-
Naphthyl-p-phenylenediamine; N,N'-
Ditolyl-p-phenylenediamine; N-amino-N'-phenylparaphenylenediamine; N,
Examples include N'-dicyclohexylparaphenylenediamine;N,N'-diphenyl-p-phenylenediamine. Among the antioxidants mentioned in (c), phenolic antioxidants are 0.3-10.0% of the total composition, sulfur-based antioxidants are 0.3-10.0% of the total composition, and phosphorus-based antioxidants are 0.3-10.0% of the total composition. 10.0%, and amine antioxidants are used in the range of 0.3 to 10.0% in the total composition. If these exceed the above range, they will adversely affect the lubricity, and if they are less than 0.3%, the effect as an antioxidant will be reduced, which is not preferable. In addition to the above-mentioned essential components oils and fats (a), (b), and (c), the cold rolling lubricating oil of the present invention may optionally contain various conventionally known additives, such as: Surfactants, rust inhibitors, extreme pressure additives, etc. can be added. Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene polyoxypropylene ether, sorbitan alkyl ester, and alkyl phosphate esters. Salts, phosphate ester surfactants such as polyoxyethylene alkyl phosphate ester salts, etc. are used, and are usually blended in the lubricating oil for cold rolling in an amount of about 0.5 to 5%. As the rust preventive agent, for example, amines and their derivatives, alkenylsuccinic acids and their derivatives, phosphoric acid esters and their derivatives, etc. are used, and are usually blended in the lubricating oil for cold rolling in an amount of about 0.1 to 5%. As extreme pressure additives, for example, phosphorus compounds such as trialkyl phosphates and trialkyl phosphites, and organometallic compounds such as zinc dialkylthiophosphate are used, and they are usually added in an amount of 0.5 to 5% in the lubricating oil for cold rolling. It is mixed to some extent. [Effect of the invention] A composition with excellent lubricity and surface cleanliness is obtained by adding the compounds (a) and (b) to oils and fats, and further contains (c) a phenolic antioxidant and a sulfur-based antioxidant. 2 selected from antioxidants, phosphorus antioxidants, and amine antioxidants
The cold rolling oil composition of the present invention, which is composed of a combination of more than one antioxidant, has excellent heat decomposition resistance and heat oxidation resistance, and maintains stable and high lubricity over a long period of time in actual operation. The cleanliness of the steel plate after washing can be improved. Furthermore, compared to conventional products, the lubricating oil for cold rolling of the present invention has better lubricity than conventional commercially available oil-based rolling oils, and can withstand long-term use in actual operations. Also, the cleanliness of the plate surface after washing the steel plate after rolling is excellent. [Example] Next, the present invention will be explained with reference to Examples. Example 1 Various tests were conducted on various rolling oils having the compositions shown below. The results are shown in Tables 1 and 2. I Rolling oil (all composition units are weight %) (1) Rolling oil No. 1 of the present invention Refined beef tallow 60 Polymerized acid (1) 1 Ester (A) 25 Surfactant (a) 3 Phenol antioxidant (A) 5.5 Phosphate ester antioxidant (B) 5.5 No.2 Edible beef tallow 57.5 Polymerized acid (2) 5 Ester (B) 20 Surfactant (b) 3 Phenol antioxidant (B) 6 Sulfur type Antioxidant (A) 8.5 No.3 Refined palm oil 63 Polymerized acid (3) 6 Ester (C) 10 Surfactant (c) 5 Sulfur-based antioxidant (B) 9 Phosphate-based antioxidant (C ) 7 No. 4 Crude beef tallow 33 Refined palm oil 38 Polymerized acid (4) 10 Ester (D) 5 Surfactant (a) 3 Phenolic antioxidant (C) 5.5 Amine antioxidant (A) 5.5 No. 5 Refined beef tallow 40 Refined pork fat 23 Polymerized acid (5) 4 Ester (E) 15 Surfactant (b) 3 Phenol antioxidant (D) 7 Phosphate ester antioxidant (A) 8 (2) Comparison Rolling oil No.1 Refined beef tallow 93 Polymerized acid (4) 1 Ester (C) 1 Surfactant (a) 5 No.2 Refined palm oil 89.7 Polymerized acid (1) 0.3 Ester (A) 5 Surfactant (b) 5 No. 3 Crude beef tallow 94 Polymerized acid (1) 2 Surfactant (c) 3 Phenol antioxidant (A) 1 No. 4 Refined beef tallow 93 Beef tallow fatty acid 2 Surfactant (a) 3 Sulfur antioxidant (B) 1 Phosphate ester-based extreme pressure agent (A) 1 No. 5 Commercial tallow-based rolling oil No. 6 Commercially available mineral oil-based rolling oil In the above composition, polymeric acid, ester, surfactant, antioxidant agent and extreme pressure agent mean the following: Polymer acid (1)...polymer acid (dimer acid: olefinic acid and linoleic acid (equal mixing ratio of the two components))
Polymer acid (trimer acid or higher) Polymer acid (2)...Polymer acid of tall oil fatty acid (dimer acid: Polymer acid higher than trimer acid = 8:2) Polymer acid (3)...Polymer acid of soybean oil fatty acid (Dimer acid: Polymer acid higher than trimer acid = 6:4) Polymer acid (4)...Polymer acid of oleic acid (Dimer acid: Polymer acid higher than trimer acid = 9:1) Polymer acid (5)...Zomaric acid Polymer acids of oleic acid and cadreic acid (equal proportions of the three components) ((dimer acid: polymer acid higher than trimer acid =
9:1) Ester (A)...Blend 100 g of polymeric acid (2) and 25.6 g of diethylene glycol in a nitrogen stream at normal pressure, 220 g.
A mixture of 100 g of polyol polyester (hydroxyl value = 75) obtained by heating and condensation at °C and 36 g of stearic acid (acid value = 104) was mixed in a nitrogen stream at normal pressure.
Ester obtained by heat condensation at 220°C (hydroxyl value = 7, oxidation = 8, average molecular weight = 1500) Ester (B)...100 g of polymeric acid (4) and 23 g of diethylene glycol were mixed and heated in a nitrogen stream at normal pressure. ,220℃
A mixture of 100 g of polyol polyester (hydroxyl value = 44) obtained by heating and condensation with 23 g of isostearic acid (acid value = 205) was heated in a nitrogen stream at normal pressure.
Ester obtained by heating and condensing at 220°C (hydroxyl value = 6, acid value = 6, average molecular weight = 2500) Ester (C)...100 g of polymeric acid (5) and 22 g of propylene glycol were mixed in a nitrogen stream, Normal pressure, 220℃
An ester (hydroxyl value) obtained by heating and condensing a mixture of 100g of polyol polyester (hydroxyl value = 112) and behenic acid (acid value = 161) at 220°C in a nitrogen stream at normal pressure. =9,
Acid value = 8, average molecular weight = 1000) Ester (D)...obtained by blending 100g of polymeric acid (3) and 41g of polyethylene glycol (average molecular weight = 200) and heating and condensing it at 220℃ at normal pressure in a nitrogen stream. polyol polyester (hydroxyl value = 25)
Ester obtained by blending 100 g of palmitic acid (acid value = 218) and 11 g of palmitic acid (acid value = 218) and heating and condensing it at 220°C at normal pressure in a nitrogen stream (hydroxyl value = 5, acid value = 4,
Average molecular weight = 4500) Ester (E)...Polyol polyester (hydroxyl value: =
23) Ester obtained by blending 100g and 9g of palmitic acid (acid value = 256) and heating and condensing it at 220°C at normal pressure in a nitrogen stream (hydroxyl value = 4, acid value =
5. Average molecular weight = 5000) Surfactant (a)...Polyoxyethylene nonyl phenyl ether (number of moles of ethylene oxide added n
= 6) Surfactant (b)...Polyoxyethylene lauryl ether (number of moles of ethylene oxide added n = 5) Surfactant (c)...polyoxyethylene monostearate (number of moles of ethylene oxide added n = 7) Phenol type Antioxidant (A)...2,5-di-tert-
Butyl-p-cresol phenolic antioxidant (B)...4,4'-butylidenebis(3-methyl-6-tert-butylphenol) Phenolic antioxidant (C)...tetrakis[methylene-3-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionate] methanephenol antioxidant (D)...Bis-[3,3'-bis-(4'-hydroxy-3'-tert-butyl-phenyl) )-butyric acid] Glycol ester sulfur-based antioxidant (A)...lauryl stearyl thiodipropionate sulfur-based antioxidant (B)...5-(3,5-di-tert-
Butyl-4-hydroxybenzyl)-alkylthioglycolate phosphate ester antioxidant (A)...Triarylphosphate phosphate ester antioxidant (B)...Phenyl di-
iso-octyl phosphite phosphate ester antioxidant (C)...tris(o-biphenyl) phosphite amine antioxidant (A)...N,N'-di-tert-butyl-p-phenylenediamine phosphorus Acid ester extreme pressure agent (A)...Tricresyl phosphate Test items and test methods (1) Lubricating performance Using a Timken tester, concentration 5%, temperature 50
℃ rolling oil emulsion was prepared in advance in a tank, and this was circulated and supplied. The evaluation was performed based on the size of the area (OK area) within the seizure limit curve connecting the load and rotation speed just before seizure occurred, and was expressed as a ratio with the worst one being 1.0. (2) Long-term circulation stability of emulsion A rolling oil emulsion with a concentration of 5% by weight and a temperature of 60°C is prepared in advance, and further, assuming iron powder generated during rolling, iron powder (particle size of 5μ or less) is added to 0.3% by weight. It was added as follows. Next, this was continuously circulated and sprayed onto iron rolls heated to 150℃ using a gear pump at a pressure of 25 kg/ ^cm2 , and after 48 hours, the oil content of the emulsion was extracted and weighed, excluding the upper layer floating oil content, and the initial oil amount was determined. The amount of decrease was calculated. The emulsion stability index was also measured over time. ESI
is the emulsion 500 taken from the tank middle layer.
ml was allowed to stand still for 10 minutes, and then expressed as the ratio of the oil content in the upper layer 100 ml to the oil content in the lower layer 100 ml.

【table】

【table】

[Table] As is clear from Tables 1 and 2, the cold rolling lubricating oil of the present invention was superior to the comparative rolling oil in both lubrication performance and long-term circulation stability.

Claims (1)

[Claims] 1 Fats and oils contain (a) 0.5 to 10% by weight of at least one of dimer acids and polymer acids of higher aliphatic unsaturated acids having 16 to 20 carbon atoms, and (b) higher aliphatic unsaturated acids having 16 to 20 carbon atoms. Polyester is obtained by heating and condensing at least one of a dimer acid and a polymer acid with a polyol, and reacting the remaining carboxyl group or hydroxyl group with an alcohol having 1 to 22 carbon atoms or a fatty acid having 12 to 22 carbon atoms. Molecular weight 750~
7500 ester in an amount of 5 to 40% by weight, (c) two or more antioxidants selected from the group consisting of phenolic antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. 0.3-10% by weight each
(However, phenolic antioxidants,
0.3 to 5.0% by weight, 0.3 to 8.0% by weight, 0.3 to 5.0% by weight of two or more antioxidants selected from the group consisting of sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants, and A lubricating oil for cold rolling of metal materials, characterized in that it contains 0.3 to 5.0% by weight).