JPH0222392A - Additive for cold rolling oil of metal - Google Patents

Abstract

PURPOSE:To obtain the title additive having high lubricating properties, rolling properties and lubricating stability containing reaction product of polyalkylenepolyamine, etc., and aliphatic carboxylic acid, etc., and sulfonic acid salt of specific organic compound, etc. CONSTITUTION:(A) A reaction product of (i) 3-200N polyalkylenepolyamine or polyalkyleneimine and (ii) at least one selected from aliphatic carboxylic acid, dimeric acid or polymeric acid of aliphatic unsaturated acid, glycidyl ether of aliphatic alcohol or alkylphenol and epoxy compound of aliphatic olefin and (B) a salt neutralized by sulfonic acid (ester) of a organic compound having aliphatic or aromatic group are contained in the aimed additive as an essential ingredient.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a cold rolling oil for metals, and more particularly to an emulsified cold rolling oil for metals and additives thereof.

[Conventional technology]

Cold pumping oils that have been commonly used include, for example, oils, mineral oils, fatty acid esters, etc. as lubricating oil components, rust preventive agents, extreme pressure agents, oiliness improvers, antioxidants, antifoaming agents, etc. Add various auxiliaries. This is made into an O/w type emulsion using an emulsifier, usually from 1 to
It is supplied to the rolling section at a concentration of about 20%. However, recent advances in rolling technology have led to higher rolling speeds and mass production, and demands for pressure oil such as lubricity, workability, and wastewater treatment properties have increased. development is desired.

[Problems with conventional technology]

However, with conventional cold rolling oils using emulsifiers, the type and amount of emulsifiers added can be changed to increase or decrease the amount of oil adhering to the surface of the rolled material (plate-out amount), which improves rolling lubrication. Since the amount of plate-out and liquid circulation stability show contradictory tendencies, increasing the stability of the emulsion reduces the amount of plate-out to the rolled material and improves lubricity. However, if the amount of plate-out is not increased, the emulsion becomes unstable, causing various problems when it is recycled. In addition, the generated iron powder adheres to the unstable emulsion, causing scum to adhere to the cold-rolled steel plate, which has a negative impact on the cleaning and annealing process that is the subsequent process, and also adheres to the rolling mill itself and its surroundings. However, there were problems in that it not only spoiled the aesthetics but also made workability worse.

[Problem to be solved by the invention]

In view of the above circumstances, the problem that the present invention aims to solve is to provide a cold rolling oil for full bending that has high lubrication rolling performance and good lubrication stability.

[Means to solve the problem]

As a result of intensive research, the present inventors discovered that the problem described in item 1 can be solved, and arrived at the present invention. That is, the present invention relates to an amide compound obtained by reacting a polyalkylene polyamine or polyalkylene imine having 3 to 200 nitrogen atoms with an aliphatic carboxylic acid, a dimer acid or a polymeric acid of an aliphatic unsaturated acid, and the above-mentioned polyalkylene polyamine or polyalkylene imine. and a glycidyl ether of an aliphatic alcohol or alkylphenol, or an adduct of the polyalkylene polyamine or polyalkylene imine with an epoxy compound of an aliphatic olefin, and a sulfonic acid of an organic compound having an aliphatic or aromatic group. or an additive for metal cold rolling oil, characterized in that it contains a salt neutralized with a sulfonic acid ester as an essential component;
An additive for metal cold rolling oil containing a nonionic activator with LB6 or more, and a metal consisting of the above additive and a lubricating oil component that is at least one of animal and vegetable oils, mineral oils, synthesized fatty acid esters, or fatty acids. Cold rolling oil. The method for producing the sulfonic acid ester salt of the amide compound used in the present invention is not particularly limited, but can be produced, for example, by the following method. Stearic acid is added to polyethylene polyamine having 5 nitrogen atoms to give 120 to 180
A sulfonic acid ester of polyoxyethylene nonylphenol ether, which is used as a counterion, is added at 30 to 100 °C to obtain an amide compound by dehydration condensation under heating at 30 to 100 °C.
A sulfonic acid ester salt designated as H7 is obtained. The polyalkylene polyamines used here include diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, dipropylene triamine, and tetrapropylene pentamine, and polyalkylene imines include polyethylene imine, polypropylene imine, etc. I can give it to you. In addition, the fatty acid that reacts with the active hydrogen of the polyalkylene polyamine or polyalkylene imine has 8 to 22 carbon atoms.
Examples of higher fatty acids include 2-ethylhexylic acid, lauric acid, stearic acid, and coconut fat fatty acids. Examples include beef tallow fatty acid, oleic acid, linoleic acid, etc., and unsaturated acids such as oleic acid, linoleic acid, lilunic acid, dimer acid, and polymeric acid. In addition, glycidyl ethers that react with the active hydrogen of polyalkylene polyamines and polyalkylene imines include glycidyl ether of octyl alcohol, glycidyl ether of lauryl alcohol, glycidyl ether of stearyl alcohol, glycidyl ether of nonylphenol, and glycidyl ether of dodecylphenol. can be used, and as the epoxy compound of aliphatic saline refine, α-olefin epoxide having 8 to 26 carbon atoms, alicyclic olefin epoxide having 8 to z2 carbon atoms,
Furkyl diephoxide having 8 to 20 carbon atoms can be used, and examples thereof include addition-reacted compounds. In the present invention, a salt compound forming a counter ion with at least one of the compounds shown above is effective, and the 7-ion component of the counter ion is a sulfonic acid or sulfonic acid of an organic compound having an aliphatic or aromatic group. Use an acid ester to make a neutralized salt with a pH of 3 to 10. More preferably HL
It is particularly good to use a nonionic activator of B6 or higher.
The organic compound used for the sulfonic acid or sulfonic acid ester is an alkylbenzene having 6 to 24 carbon atoms, an alpha olefin having 8 to 26 carbon atoms, an alkylphenol having 6 to 24 carbon atoms, a higher alcohol having 6 to 22 carbon atoms, or Examples include fullylene oxide adducts of the alkylphenols and higher alcohols. The alkylene oxide is a block or random adduct of 1 mol to 30 mol of ethylene oxide or 1 mol to 10 mol of propylene oxide and 1 mol to 30 mol of ethylene oxide.
2 moles and 1 mole of other sulfones, such as sulfuric acid, oleum, sulfuric anhydride, chlorsulfone, sulfamic acid, etc.
It is sulfonated at θ°C to 120°C and used as an anion component. The nonionic activator with an HLB of 6 or more used in the present invention is obtained by adding ethylene oxide, prop#=pyrene oxide, butylene oxide, etc. to an alcohol, alkylphenol, fatty acid, or polyhydric alcohol fatty acid ester having 8 to 22 carbon atoms. I can give you something. If the HLB is less than 5, the stability of the emulsion will be poor and the generation of oil stain will be significant, which is undesirable.Charcoal IW! Alcohols with numbers 8 to 22 include octyl alcohol, lauryl alcohol, stearyl alcohol, oleyl alcohol, etc. Alkylphenols include butylphenol, octylphenol, nonylphenol, dodecylphenol, or formalin condensates thereof, and fatty acids include lauric acid and myristic acid. Examples of the acids include palmitic acid, stearic acid, and oleic acid, and polyhydric alcohol fatty acid esters include esters obtained by reacting the above fatty acids with glycerin, polyglycerin, pentaerythritol, sorbitol, ethylene glycol, propylene glycol, and the like. As the lubricating oil component used in the present invention, any of those conventionally used in this type of rolling oil can be used. A typical example is animal and vegetable oils. Mineral oil, synthesized fatty acid esters, etc.
It is also possible to use one or more of them in combination. Specifically, spindle oil, machine oil, turbine oil,
Mineral oils such as cylinder oil, animal and vegetable oils such as whale oil, beef tallow, lard, rapeseed oil, castor oil, bran oil, soybean oil, palm oil, coconut oil, or fatty acids obtained from beef tallow, coconut oil, castor oil, etc. Examples include fatty acid esters synthesized from alcohols such as aliphatic monohydric alcohols having 1 to 22 carbon atoms, propylene glycol, pentaerythritol, and sorbitol. Normal rolling oil uses animal and vegetable oils, mineral oils, and synthesized fatty acid esters as base oils, and also contains 15 oiliness improvers, extreme pressure additives, rust preventive additives, antioxidants, emulsifiers, antifoaming agents, etc. Add the seeds or a composition containing two or more seeds to water at 0.1%.
It is used as an emulsion after being diluted to a consistency of ~10%, but the composition of the present invention can also be used in the same way.The additive of the present invention is dissolved in a base oil and diluted with water before use. It is used by forming an emulsion, but it may also be used by dissolving a 1.5-polarity agent in water, and 0.1% to 10% by weight, preferably 0.5% by weight based on the total amount of the rolling oil composition. ~5%
Just mix them so that they are the same weight. In addition to the above components, the metal cold rolling oil composition of the present invention includes:
If necessary, known oiliness improvers, extreme pressure additives, antirust additives, antioxidants, antifoaming agents, etc. may not be added.

[Effect]

Cold rolling oil for metals can be made by using the product of the present invention.
Due to the protective colloid action, the lubricating oil component maintains a fairly large particle size and is stably dispersed in water, so it remains relatively large and stable under agitation conditions with high shear force, such as in-tank agitation and supply fI ring pumps. It is possible to maintain fine particle size inclusions. Furthermore, when the oil is supplied to the rolling section, if it comes into contact with the metal material to be rolled, large oil particles will thickly moisten the metal material. ') Since it forms a film, it has high lubrication rolling performance and good circulation stability. Furthermore, in order to use a cationic activator and an anionic activator as a counter ion, a compound with 1 = iti = 1 is used,
It itself has the ability to quickly attach to liquids and solid particles and make them hydrophilic, and compared to rolling oil that uses conventional emulsifiers, it is more effective against dirt, oil, and impurities such as metal powder that get mixed in during rolling operations. This eliminates the trapping phenomenon and prevents dirt from forming around the tank and mill. As a result, it has the excellent feature of realizing a clean working environment that is not found in conventional rolling oils using emulsifiers, and also maintains stable rolling lubrication properties as a constantly clean rolling oil. IY! It has characteristics superior to conventional rolling oils in terms of lubricity and mill cleanliness.

【Example】

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. Rolling oil! Table 1 shows the additives of the present invention that are added to the 11 compositions. Table 2 shows rolling oil compositions of the present invention that were blended and adjusted at predetermined blending ratios. Further, the rolling oil performance was evaluated by the following test, and the results are shown in Table 3. (1) Lubricity test Using a Chimken tester, each rolling oil was diluted with water to 5% E degree, and the rotation speed was 8000 rpm using a homomixer.
A rolling oil dispersion having a temperature of 60° C. was prepared in advance in a tank by stirring at m, and this was circulated and supplied. The evaluation was based on the area ratio within the seizure limit curve. 1.0 for the worst
It is shown as a ratio. (2), Annealing stain resistance test Iron powder (particle size 1U or less) was added to a dispersion solution with a rolling oil concentration of 5%.
A rolling oil dispersion with 1% added at a temperature of 60°C was prepared, and sprayed onto the surface of the test steel plate from a nozzle using a gear pump (0.5 cycles/win, 1 atmosphere, 5 seconds), and after drying,
After the two sheets were stacked and pressed at 40 kg/cm 2 and brought into close contact, they were heated at 130° C. for 15 hours. Then N2+5%H
After annealing at 700° C. for 2 hours in an annealing furnace under 29 gas, the degree of contamination on the surface of the steel plate was visually evaluated according to the following criteria. ■、A・1 In good condition with no kimono Oo In good condition with a slight amount of adhesion Δ In case of some adhesion × 1 Inferior with many adhesion (3) Stability test rolling of 0 dispersion Iron powder (particle size of 1 u or less) is added to a dispersion liquid with an oil concentration of 5%.
A rolling oil dispersion liquid containing 1% was prepared at a temperature of 60°C, and heated to 150°C at a pressure of 2.5 kg/cm2 using a gear pump.
It was sprayed continuously and cyclically onto a heated iron roll. After 48 hours rJI, the oil content of the dispersion liquid excluding the floating oil content was determined, and the reduction rate with respect to the initial concentration was determined and displayed. (0, Rolling oil dispersion C1 prepared in the wastewater treatment test (1)) was added with 3 g of sulfate, stirred for 2 minutes, and further Ca(OH)
2 was added, adjusted to P) 17.0, stirred for 100 minutes, then left to stand for 30 minutes, and collected the subnatant liquid.
Chemical ffp y, R consumption, KMnOa method) were measured. As is clear from Table 3, the cold rolling oil for metals of the present invention has better performance than conventionally used oils in terms of lubricity, annealing stain resistance, stability of dispersion, and wastewater treatment. It was superior to the comparative rolling oil.
(Margin below)

【Effect of the invention】

The present invention can widely contribute to the advancement of rolling technology by providing a cold rolling oil for metals having high lubrication rolling performance and good circulation stability. Patent applicant Daiichi Kogyo Seiyaku Co., Ltd.

Claims (1)

[Scope of Claims] 1. Polyalkylene polyamine or polyalkylene imine having 3 to 200 nitrogen atoms and aliphatic carboxylic acid, dimer acid or polymer acid of aliphatic unsaturated acid, glycidyl ether of aliphatic alcohol or alkylphenol, or fat It is characterized by containing as essential components a compound reacted with at least one selected from epoxy compounds of group olefins and a salt neutralized with sulfonic acid or sulfonic acid ester of an organic compound having an aliphatic or aromatic group. Additive for metal cold rolling oil. 2. An additive for metal cold rolling oil, comprising a nonionic activator having an HLB of 6 or more and the salt according to claim 1. 3. A lubricating oil component that is at least one of animal and vegetable oils, mineral oils, synthetic fatty acid esters, and fatty acids, and Claim 1.
A metal cold rolling oil characterized in that it contains at least one agent according to items 1 to 2.