JPH01247494A - Metal rolling oil composition - Google Patents

Abstract

PURPOSE:To improve liq. circulation stability without decreasing the amt. of plate-out, by adding a particular polymer compd. to a lubricating oil component. CONSTITUTION:A lubricating oil component (a) selected from among animal and vegetable oils and fats, mineral oils and fatty acid esters is mixed with 0.1-10wt.%, based on the amt. of component (a), polymer compd. (b) selected from among an alpha-olefin-maleic acid copolymer (i) having repeating units of formula I (wherein R<1> is a 1-50C straight-chain or branched alkyl; at least one of A's is formula II and the other is OH, formula III or IV, OR<6>, -OM, -NHR<7> or -NR<8>R<9>; n1 is 10-3000; m1 is 2-10; m2 is 1-20; m3 is 1-10; each of R<2> and R<3> is H or CH3; each of R<4> and R<5> is H or a 1-4C alkyl; each of R<6> and R<7> is a 1-20C straight-chain or branched alkyl; and each of R<8> and R<9> is H or R<6>), an alpha-olefin-maleic acid copolymer (ii) having repeating units of formula V (wherein B is a 1-10C straight-chain or branched alkyl or -R<10>-O-R<11>-; and each of R<10> and R<11> is a 1-4C alkyl) and a polymer compd. (iii) obtd. by imidization of a polymer material of formula VI with an amine compd. selected from among N-aminoethylpiperidine, N-aminopropylpiperidine, 2-aminopyridine, 3-picolylamine, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a metal rolling oil composition, and more particularly to an emulsified metal rolling oil composition.

[Prior art]

Metal rolling oils that have been commonly used in the past have lubricating oil components, usually base oils such as fats, mineral oils, or fatty acid esters.
Various auxiliary agents such as rust preventive agents, extreme pressure agents, oiliness improvers, and antioxidants are added, and this is supplied to the rolling processing section as a 0/W type emulsion using an emulsifier, usually at a concentration of about 0.1 to 20%. are doing. However, recent advances in rolling technology have led to higher rolling speeds and mass production, and the demands placed on rolling oils, such as lubricity, circulation stability, workability, and wastewater treatment properties, have become increasingly severe. Therefore, it is currently desired to develop a rolling oil that can fully meet these demands. However, conventional rolling oils using emulsifiers have various drawbacks and are not satisfactory. In other words, in conventional rolling oils that use emulsifiers, the type and amount of emulsifiers added are changed to increase or decrease the amount of oil that adheres to the rolling oil and the surface of the rolled material (plate-out amount), thereby controlling rolling lubricity. Ta.

However, in rolling oil using such an emulsifier, plate alignment +-i and liquid circulation stability tend to contradict each other, and if the stability of the emulsion is improved, plate There is a drawback that the outout e decreases, resulting in insufficient lubricity, and if the amount of plateout is not increased, the emulsion becomes unstable, causing various troubles during circulation. In addition, the generated iron powder adheres to the unstable emulsion, causing so-called rolling stains that stain the cold-rolled steel plate, which also poses the problem of adversely affecting the subsequent cleaning and annealing steps. In addition, it adheres to the rolling mill itself and its surroundings, which not only impairs its aesthetic appearance but also causes operational problems.

[Problem to be solved by the invention]

The problem to be solved by the present invention is to solve the above-mentioned drawbacks of conventional rolling oil.

[Means for Solving the Problem] To this end, the present inventor has been conducting intensive research, and in this research, the above-mentioned drawbacks can be overcome by using certain polymers and metal materials, and the plate It has been discovered that an emulsified rolling oil with excellent liquid circulation stability can be obtained without reducing the amount of outflow, and the present invention has now been completed. That is, the present invention provides (1) (A) a lubricating oil component that is at least one of animal and vegetable oils, mineral oils, and fatty acid esters, and (B) (a) the following formula (wherein R1 is C1-5° A straight chain or branched alkyl group, one of which is R4 and the other is 0H1-0-(-C2H40# H1OR6, -
OM, -NH(-CH2-)-NH2, -N HR',
πυ −NR' R9.

Here 11 is an integer between 10 and 3000 m, is 2 to 10 ~2 is 1~20 ~3 is 1-10 R2 and R3 are the same or different H or CH.

R4, R5 are the same or different I4 or C, -4 alkyl group Rh-R7 is a straight chain or branched alkyl group having 1 to 20 carbon atoms R11, R9 are the same or different H or C1 to 2
α-olefin-maleic acid copolymer having a repeating unit represented by 0 linear or branched alkyl groups (b) The following formula (wherein R', n, , R', R' are (a) Same as the formula, B is a C6 to C1° straight or branched alkyl group or -
RIOOR11- is shown.

α-olefin-maleic acid copolymer (c) having a repeating unit represented by RIG, R11 represents an alkyl group of CI""' is the same as above);
N-aminopropylmorpholine, N-aminopiperidine, N-amino-4-methylpipecoline, isonicotinamide, nicotinamide, picolinamide, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2
- Containing as an essential component at least one substance imidized by reaction with at least one amine compound selected from the group consisting of picolylamine, 3-picolylamine, and 4-picolylamine. li, a metal rolling oil composition.

[Action of the invention]

In the present invention, by using at least one of the specific polymer compounds represented by formulas (a) to (c) above, excellent liquid circulation stability can be achieved without reducing the amount of plateout. show. More specifically, in the rolling oil product of the present invention, the lubricating oil component has a considerably large particle size due to the excellent protective colloidal action of the specific polymer compounds represented by formulas (a) to (c) above. Furthermore, the dispersed particle size distribution does not have a broad width, but rather shows a narrow and sharp distribution, and has extremely good Wi ring stability. In addition, when supplied to the rolling processing section, if the oil particles come into contact with the metal material to be rolled, the large oil particles form a thick and strong lubricating film on the metal material, which has the effect of increasing the plate roughness (ffl). .

In addition to the above-mentioned effects, the rolling oil composition of the present invention has the following excellent effects.

(i) The emulsion concentration and coolant (rolling oil diluted with water during use) are extremely unaffected by temperature, and the state of the emulsion does not change due to temperature changes, allowing stable use. Work management becomes very easy.

(ii) Even if scum or metal powder is mixed in, there is very little change in the particle size of the lubricating oil component in the emulsion, and since the scum and iron powder are made hydrophilic, mill (rolling mill) fouling is improved.

(iii) The cleanliness of the surface of the metal rolled material is greatly improved. At this time, if the surface of the rolled material is not cleaned, edge carbon etc. will be produced in the subsequent annealing process, which is undesirable.

(iv) Lubricity is significantly improved by about 2 to 10% compared to conventional rolling oil.

[Structure of the invention]

The rolling oil composition of the present invention basically includes a lubricating oil component consisting of at least one of fats and oils, mineral oil, and fatty acid ester, and at least one of the polymer compounds represented by formulas (a) to (c) above. It is a mixture of seeds.

As the lubricating oil component used in the present invention, any of those conventionally used in this type of rolling composition can be used, and typical examples thereof include fats and oils, mineral oils, and fatty acid esters. can be used alone or in a mixed system of two or more. Specifically, mineral oils such as spindle oil, machine oil, turbine oil, and cylinder oil; whale oil;
Beef tallow, pork fat, rapeseed oil, castor oil, bran oil, palm oil,
Animal and vegetable oils such as coconut oil; beef tallow, coconut oil, palm oil,
Examples include esters of fatty acids obtained from castor oil and the like and aliphatic monohydric alcohols having 1 to 22 carbon atoms, ethylene glycol, neopentyl glycol, pentaerythritol, and the like.

The manufacturing method of the polymer compound represented by the formula (2) used in the uninvention is not limited in any way, but for example, it can be manufactured by the following method.

xylene, n-
After dissolving in a nonpolar medium such as hexane, the copolymer is monoamidated with 1.0 to 1.5 equivalents of diamine per repeating unit under heating, usually at about 70 to 200'C, followed by addition of ethylene oxide, alkyl It can be produced by oxidation, amination, alkali metal salting, and finally desolvation.

The polymer compound represented by formula (b) used in the present invention is
Although the manufacturing method is not limited in any way, it can be manufactured, for example, by the following method.

A polymer substance having a repeating unit represented by the following - Noshiro (d) (where R1 is the same as above and n is an integer from 10 to 3000) is dissolved in an appropriate solvent such as benzene, xylene, dimethyl sulfoxide, etc. Then, a diamine represented by the following - Noshiro (A) (where R4, R5 and B are the same as above, RIffi and RIff are the same as R4 and R5) is added in an amount of 1.0 to 1.0 per repeating unit of the polymeric substance. Add 1.2 equivalents, usually 70 to 80 on heating
It can be produced by monoamidation at about ゛C.

Also, 2.0 to 2.5 per repeating unit of the above polymeric substance.
A diamide compound can be produced by adding an equivalent amount of diamine and reacting at 170-180'C.

The polymeric substance (d) above is produced, for example, by the following method. That is, maleic anhydride (1 molar ratio) and α-olefin (1.0 to 1.2 molar ratio) are mixed without a solvent or in an appropriate solvent such as benzene, xylene, dimethyl oxide, dimethylformamide, dioxane, etc. It can be produced by polymerization in the presence of a suitable polymerization initiator such as benzoyl peroxide, di-tert-butyl peroxide, or abbisisobutyronitrile. The degree of polymerization of this polymer substance is about 10 to 3000, and the average molecular weight is 1500.
~500,000.

Among the compounds of the above formulas (a) to (c) used in the present invention, preferred ones are as follows.

That is, first, in formula (a), R'=19 to 50, ml-
2-8, mz = 2-10, ~3-2-6, R6-6
~18, R7-1~6, R8-1~6, M=Na, , n
=5 to 1000. Also, in formula (a), M
The metal represented by is not limited to the above-mentioned preferred metals, but usually includes Li. Further, in formula (b), preferably nl is 10 to 1,200.

In formula (b), R' is 3 to 50, B is a C2 to C6 linear or branched alkyl or R10Q, and RIO and RII are C, to
C4 straight or branched alkyl group, later.

Also, regarding imidide (c) N-aminopropyl biveridine, Later.

In the present invention, it is essential to use at least one of the compounds represented by Noshiro (a) to (c) above, but preferably these compounds and a substance that forms a counter ion are used in combination. . Examples of anions used as counterions include sulfate ions, nitrate ions, chloride ions, glycolate ions, phosphate ions, borate ions, and fatty acid ions having 1 to 20 carbon atoms. In addition, mono- or diesters of phosphoric acid (ester component having 1 to 18 carbon atoms), boric acid mono- or diester (ester component having 1 to 18 carbon atoms), fatty acids having 1 to 20 carbon atoms, and the like can be used.

Normally, rolling oil is manufactured at the manufacturing plant using fats, mineral oils, esters, etc. as a base oil, and if necessary, one type of oiliness improver, extreme pressure additive, rust preventive additive, antioxidant, emulsifier, etc. Alternatively, a composition containing two or more types is transported, diluted with water to a concentration of 0.1 to 10%, and emulsified at the site where it is actually used.

For this purpose, the counter ion has 1 to 20 carbon atoms, preferably 3 carbon atoms.
~20 fatty acid ions or mono- or diesters of phosphoric acid or boric acid, where the number of carbon atoms in the ester component is 6
When using ~18, the polymeric substance used in the present invention (
A) to (C) are uniformly dissolved in the base oil of rolling oil. Therefore, at the site of use, like conventional rolling oil, a uniform emulsion can be formed simply by diluting it with water to a predetermined concentration. On the other hand, when a counter ion is used as a counter ion except for a fatty acid ion having 1 to 20 carbon atoms and a mono- or diester of phosphoric acid or boric acid in which the ester component has 6 to 18 carbon atoms, the polymer compound ( (a) to (c) are difficult to dissolve uniformly in the base oil, so it is preferable to form an emulsion by diluting the rolling oil and the dispersant to predetermined concentrations at the site of use.

In the present invention, the compounds represented by Noshiro (a) to (c) above may be used alone or in combination of two or more thereof.

These polymer compounds of the present invention are blended in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the total amount of the rolling oil composition.

In addition to the above-mentioned components, various known additives such as rust preventive agents, oiliness improvers, extreme pressure agents, antioxidants, etc. can be added to the metal rolling oil composition of the present invention, if necessary.

The various additives mentioned above may be added in an amount of 0 to 10%, 0 to 20%, 0 to 3%, and 0 to 3%, respectively, based on the total amount of the rolling oil composition as necessary.
It can be added at a rate of 5%.

As rust inhibitors, alkenylsuccinic acid and its derivatives,
Fatty acids such as oleic acid, esters such as sorbitan monooleate, and other amines are used as oiliness improvers.
Higher fatty acids such as oleic acid and stearic acid and dibasic acids such as esters or dimer acids that are derivatives thereof are used.As extreme pressure agents, phosphorus compounds such as tricresyl phosphate and organic compounds such as zinc dialkyldithiophosphate The compound is 2,4-di-t-butyl P- as an antioxidant.
Examples include phenolic compounds such as cresol, aromatic amines such as phenyl α-naphthylamine, and the like.

The metal rolling oil composition of the present invention can be prepared by simply mixing the above-mentioned rolling oil component and a water-soluble polymer compound at the same time, or by preparing it as a concentrated solution with a water content of up to about 80%, and then preparing the composition before use. Used by diluting with water.

〔Example〕

EXAMPLES The present invention will be specifically explained below with reference to Examples and Comparative Examples. However, the dispersants A to C used in the following examples are as follows.

A: Dispersion A: Polymerization degree of diamide of copolymer of C12 α-olefin and maleic anhydride with N,N-diethylaminoethylamine = 40 MW = 18000B: Carbon i
Partial amidation with N,N-dimethylaminopropylamine of copolymer of several 20 α-olefins and maleic anhydride and partial Na salt Polymerization degree -50MW=25000 0: α-olefin with 50 carbon atoms and maleic anhydride degree of imidide polymerization with methylaminopropylamine of copolymer of = 10 MW = 9000D: carbon @
N of the copolymer of α-olefin and maleic anhydride of No. 6,
Diamidated polymer of N-dimethylaminopropylamine = 200 MW = 74000E: 5 moles of ethylene oxide is further added to the monoamidated product of N,N-diethylaminopropylamine, which is a copolymer of α-olefin having 18 carbon atoms and maleic anhydride. Polymerization degree = 40 MW = 26000 F: Mixture of 50 parts of dispersant A and 50 parts of dispersant C G Copolymer of N,N-diethylaminopropanediamide of nioleyl vinyl ether and maleic anhydride (degree of polymerization = 8 MW = 4960 Example 1
~6 Using the above-mentioned dispersant, a rolling oil composition was prepared by blending the specified components shown in Table 1 in the specified amounts.

Various properties were measured for each composition thus obtained. The results are shown in Table 2 and Figures 1-4. However, various characteristics were measured by the following methods.

<Amount of adhesion> After 5 passes of dull rolling, a pickled plate of 1.6 x 80 x 100 mm was drained, air-dried (24 hours), and weighed to measure W. Next, it is washed with trichloride and weighed to measure W2.

Coating amount = W, -W2 <Rolling test> Using a two-stage test rolling mill, 7 baths were rolled under the following rolling conditions, and the rolling load (number) at the elongation rate = 3.4 was measured, The rolling relative ratio was calculated using the following formula.

*Rolling conditions Rolling material: Mild steel plate (SPCC) thickness 2.2mm x width 50mm
M x length 500III11 Rolling speed = 13/min Rolling roll: diameter 150mm, body length 200mm Bride roll Coolant temperature = 50~55''C Coolant temperature: 5% Emulsion pass schedule: 7 baths <Steel plate lightness test> Test rolled steel plate Apply commercially available melting tape to the surface.
The tape was then peeled off, and the surface of the tape pasted on a standard white mount was measured for brightness using a color difference meter ND-101D manufactured by Nippon Heavy Industries. The brightness of the O1 standard white base for complete black is 85.
Find it as.

<Deterioration Test> The rolling oil of the present invention (3% emulsion) was subjected to a 7-day deterioration test using the circulation deterioration tester shown in FIG. 5 below, and the particle size distribution before and after the test was measured. However, in Figure 5, (1) is the tank (liquid temperature 55°C ± 5°C), (2) is the filter 5, (3)
"Pump (251/lll1n3), (4) indicates a rotating drum (30φcm x 20 cm").In this rotating drum (4), there are 150 1/2 steel balls, 2
It contains eight cm×2cm×IC7+1 casting blocks and rotates at ]]5 rpm.

The solid lines in Figures 1 to 4 represent the particle size distribution before the test, and the dotted lines represent the particle size distribution after the test.

(Foaming test) The rolling oil of the present invention (3% emulsion) was tested for 30 minutes using the circulation foaming tester shown in Figure 6 below to measure the height of foam from the liquid surface. ) is the tank (liquid temperature 55°C ± 5°C), (+2) is the pump (101/m
in), (13) indicates a nozzle (inner diameter 8 mm),
The distance (H) from the nozzle to the liquid level is 30 cm.

In addition, 04) indicates that the circulation pipe q is rolling oil.

[Brief explanation of the drawing]

1 to 4 are drawings showing the results of deterioration tests for each rolling oil composition, FIG. 5 shows the deterioration test method, and FIG. 6 shows the apparatus used in the foaming test. 1... Tank 2... Filter 3... Pump 4... Rotating drum 11... Tank 12... Pump I3 ... Nozzle 14 ... Pipe 15 ... Rolling oil (hereinafter referred to as "2") Fig. 1 Fig. 3

Claims (1)

[Claims] (1) (A) A lubricating oil component that is at least one of animal and vegetable oils, mineral oils, and fatty acid esters, and (B) (a)
The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R^1 is a straight chain or branched alkyl group of C_1 to _5_0, and A is both or either one ▲ There are mathematical formulas, chemical formulas, tables, etc.) and the other is OH, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, OR
^6 -OM, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -NHR
^7, -NR^8R^9. Here, n_1 is an integer from 10 to 3000 m_1 is 2 to 10 m_2 is 1 to 20 m_3 is 1 to 10 R^2 and R^3 are the same or different H or CH_3R^
4. R^5 is the same or different H or C_1 to_4 alkyl group R^6, R^7 is a straight chain or branched alkyl group having 1 to 20 carbon atoms R^8, R^9 is the same or different H or carbon number 1~
α-olefin-maleic acid copolymer (b) having a repeating unit represented by 20 straight-chain or branched alkyl groups , R^4, and R^5 are the same as in formula (A), and B represents a linear or branched alkyl group of C_1 to C_1_0 or -R^1^0-O-R^1^1-. R^1 α-olefin-maleic acid copolymer having a repeating unit represented by ^0, R^1^1 represents an alkyl group of C_1 to C_4) (c) The following general formula (d) ▲ Numerical formula, chemical formula, There are tables etc. ▼...(d) (However, R^1 and n_1 in the formula are the same as above) and the polymeric substance represented by N-aminoethylpiperidine, N-aminopropylpiperidine, N-aminoethyl-4- pipecoline, N-aminopropylpipecoline, N-aminoethylmorpholine,
N-aminopropylmorpholine, N-aminopiperidine, N-amino-4-methylpipecoline, isonicotinamide, nicotinamide, picolinamide, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2
- It is characterized by containing as an essential component at least one substance imidized by reaction with at least one amine compound selected from the group consisting of picolylamine, 3-picolylamine, and 4-picolylamine. Metal rolling oil composition.