JPS61283694A - Metal rolling oil composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. which is excellent in lubricity, liquid circulation stability, workability and waste water treatability, causes no significant staining due to cold rolling and excellent in rolling efficiency, by incorporating at least one member selected from among specific three kinds of vinyl polymers in a lubricating oil component. CONSTITUTION:A lubricating component comprising at least one member selected from animal oils, vegetable oils, mineral oils and aliphatic acid esters is incorporated with 0.1-10wt% at least one member selected from polyvinyl ether polymers having a repeating unit of the formula I (wherein n is an integer of 5-3,000; R is a lower alkyl), vinyl ether-maleic acid copolymers having a repeating unit of the formula II (wherein R<1> is a 1-18C alkyl; with respect to X, any one of the two is a group of the formula III (wherein m is an integer of 1-3; R<2>-R<3> are each a 1-3 alkyl), and the other is H, a group of the formu lae IV-VI (wherein m' is an integer of 1-20; m'' is an integer of 1-10; R<4> is a 1-20C alkyl), R<1>, alkali metal, etc.; n' is an integer of 10-3,050] and vinyl-maleic acid copolymers having a repeating unit of the formula VII (wherein R<7> is H, CH3; and n'' is an integer of 300-1,300).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a metal rolling composition, and more particularly to an emulsified metal rolling 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 auxiliaries such as rust preventive agents, extreme pressure agents, oiliness improvers, and antioxidants are added, and this is made into an 0/W type emulsion using an emulsifier.
It is usually supplied to the rolling section at a concentration of about 1 to 20%. However, recent rolling technology and technical advances have enabled high rolling speeds and mass production, improving lubricity, circulation stability, post-rolling surface cleanliness, so-called cold rolling stains, workability, etc.
The requirements for rolling oils, such as wastewater treatment properties, are becoming increasingly severe, and there is currently a need for the development of rolling oils that can fully meet these requirements. 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 oils using such emulsifiers, plate-out and liquid circulation stability tend to contradict each other, and if the stability of the emulsion is improved, the amount of plate-out to the rolled material can be reduced. If the amount of plate-out is increased, the lubricity becomes insufficient, and if the amount of plate-out 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, resulting in the disadvantage that it adversely affects the subsequent cleaning and annealing processes. In addition, it adheres to the rolling mill itself and its surroundings, which not only impairs the aesthetic appearance but also causes problems in terms of the working environment.

[Object and outline of the invention]

The present inventor has been conducting extensive research in order to solve the above-mentioned drawbacks of conventional rolling oil, and in this research, the above-mentioned drawbacks were solved by using a specific polymer compound, 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: (A) a lubricating oil component that is at least one of animal and vegetable oils, mineral oils, and fatty acid esters; A polyvinyl ether polymer compound having a repeating unit represented by the following formula (R' represents the same or different lower alkyl group), (b) the following formula (b) →CH2CHCHCH moiety, (b) R'0O=CC
=0 ox x.

and the other is Hl (C2H40, H1, alkyl group having 1 to 18 carbon atoms, alkali metal, NH(CH2), 11-N)12, NH2R' or N)(R'Re), and n is 10 ~3050
m is an integer of 1 to 3, m is an integer of 1 to 20, and m is an integer of 1 to 10. Further, R2 and R3 are the same or different alkyl groups having 1 to 3 carbon atoms, and R8 and R3 are the same or different alkyl groups having 1 to 3 carbon atoms.
6 represents the same or different alkyl group having 1 to 20 carbon atoms) When the repeating unit is represented by the following, it is a nyl ether-maleic acid copolymer, and (c) the following formula (c) 0X X○... ...(c) (However, in the formula, X is the same as above. R7 represents H or CH3, and n represents an integer from 3oo to 13oo) of a vinyl-maleic acid copolymer containing a repeating unit represented by This relates to a full flexion rolling composition characterized in that it contains at least one component as an essential component.

〔Effect of the invention〕

In the present invention, by using at least 1 ni of the specific polymer compound represented by the above formulas (3) to (3), excellent liquid circulation stability is exhibited without reducing the amount of plateout. Specifically, in the rolling oil composition of the present invention, the lubricating oil component maintains a fairly large particle size and is stable due to the excellent protective colloidal action of the specific polymer compounds represented by formulas (a) to (c) above. It is dispersed in water, and the particle size distribution does not have a broad width, but rather shows a narrow and sharp distribution, and has extremely good circulation stability.Furthermore, when supplied to the rolling processing section, When these oil particles come into contact with the rolled metal material, the large oil particles form a thick and strong lubricating film on the rolled metal material, which has the effect of increasing the amount of plateout.

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

(i) The emulsion concentration and coolant (rolling oil diluted with water during use! 3) are extremely unaffected by temperature, and the emulsion state does not change due to temperature changes and can be used stably. , rolling operation management becomes very easy.

(ii) There is very little change in the particle size of the lubricating oil component in the emulsion even if scum or metal powder is mixed in.
3. Also, since it makes scum and iron powder hydrophilic, it improves mill (rolling mill) stains.

(iii) Cleaning of the surface of the rolled metal material after cold rolling is greatly improved. At this time, if the surface of the rolling oil is not cleaned, edge carbon and the like will occur in the subsequent annealing process, which is undesirable.

(iv>/I!lI lubricity is 7 to 10 compared to conventional rolling oil.
% is also greatly improved.

[Structure of the invention]

The rolling oil composition of the present invention basically includes a lubricating oil component consisting of at least one of animal and vegetable oils, mineral oils, and fatty acid esters, 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 oil composition can be used, representative examples of which include animal and vegetable oils, mineral oils, and fatty acid esters. These are type 1 or 2 ft.
It can be used in a mixed system of the above. Specifically, mineral oils such as spindle oil, machine oil, turbine oil, and cylinder oil; fish oil, whale oil, beef tallow, pork oil, rapeseed oil, and mustard oil;
Animal and vegetable oils such as bran oil, palm oil, and coconut oil; beef tallow,
Examples include esters of fatty acids obtained from coconut oil, palm oil, castor oil, etc., and aliphatic monohydric alcohols having 1 to 36 carbon atoms, ethylene glycol, neopentyl alcohol, penquerythritol, and the like.

The production method of the polymer compound represented by formula (a) used in the present invention is not limited in any way, but for example, as shown in the reaction formula below, it can be produced by reacting polyvinyl alcohol with ethylamine halide. I can do it.

H (where n and R are the same as above, and XI represents a halogen atom).

More specifically, polyvinyl alcohol and ethylamine halide such as 2-chloro-N.

After stirring and mixing N-dialkylethylamine hydrochloride and adding an aqueous caustic alkali solution, stir vigorously and then heat (for example, around 80 to 100°C) and maintain for a while, then pour into boiling water and add 1 to 2 Boil for hours. This liquid is neutralized with an acid such as hydrochloric acid and decanted.

A typical method for producing the compound represented by the general formula (b) is to heat an organic solvent solution of a copolymer of alkyl vinyl ether and maleic anhydride to usually 100°C or higher while blowing nitrogen gas. N,N-dialkylamine ethyl alcohol is reacted. The product thus obtained is subjected to, for example, one of the following treatments. That is, the desired product is obtained by reaction with ethylene oxide, esterification with an alkyl alcohol having about 1 to 18 carbon atoms, reaction with an alkali metal, or amidation. Also, as another method,
A solution of an alkyl vinyl ether-maleic anhydride copolymer in an organic solvent is reacted with ethyl alcohol under reflux in the presence of a suitable catalyst such as sodium methoxide while blowing nitrogen gas, and then N,N-dialkylaminoethyl alcohol is used. Transesterify.

Further, as a method for producing the compound represented by the general formula (c), the following methods can be exemplified. That is, an isobutylene-maleic anhydride copolymer is dissolved in a suitable solvent, such as dimethylformamide or dimethyl sulfoxide, and heated to about 130 to 150°C while blowing nitrogen gas, without a catalyst or in the presence of sodium methoxide. Esterify with aminoethyl alcohol. The product thus obtained is then subjected to one of the same treatments as in general formula (b).

In the present invention, it is essential to use at least one of the compounds represented by the above general formulas (a) to (c), but preferably these compounds and a substance that forms a counter ion are used in combination. The anions used as counterions at this time include Tayoe, Eioa, and Iio7. j
jiyo io, 1,2 licholate ion, phosphate ion,
Examples include boric acid ions and fatty acid ions having 1 to 20 carbon atoms.

Normally, rolling oil is manufactured at the manufacturing factory using fats, mineral oils, esters, etc. as a base oil, and if necessary, oiliness improvers, extreme pressure additives, anti-rust additives, antioxidants, emulsifiers, etc. !
Alternatively, a composition containing two or more of them is transported, diluted with water to a concentration of 0.1 to 10%, and emulsified at the site where it is actually used.

Therefore, the counter ion has 1 to 20 carbon atoms, preferably 8 to 20 carbon atoms.
When No. 20 fatty acid ions are used, the polymeric substances (a) to (c) used in the present invention are uniformly dissolved in the base oil of the rolling oil. Therefore, in the field 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, as a counter ion, carbon number 1 to 2
When using counterions other than 0 fatty acid ions,
The polymer compounds (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 with water to a predetermined concentration at the site of use.

In the present invention, the compounds represented by the above general formulas (a) to (c) may be one of these or 2f! The above may be used in combination.

These polymer compounds of the present invention are blended in an amount of 0.1 to 10% by weight, preferably 0.1 to 8% by weight, based on the total amount of the rolling oil composition.

In addition to the above-mentioned components, the metal rolling oil composition of the present invention may contain known f! Additives such as rust preventives, oiliness improvers, extreme pressure agents, emulsifiers, antioxidants, etc. can be added.

The various additives mentioned above may be added in an amount of 0 to 2%, 0 to 20%, 0 to 3%, and 0 to 1%, respectively, based on the total amount of the rolling oil composition as necessary.
It can be added at a rate of 0% or 0 to 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.
High fatty acids such as oleic acid and stearic acid and their derivatives esters or dibasic acids such as dimer acid,
Extreme pressure agents include phosphorus compounds such as tricresyl phosphate and organic compounds such as zinc dialkyldithiophosphate; antioxidants include phenolic compounds such as 2,4-di-t-butyl p-cresol; Examples include aromatic amines such as phenyl α-naphthylamine.

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

Example 1 Beef tallow, , , , , , , , , , , , , , , ,
,,, 99 Gravimeter high setting element dispersant (A), ,,,,,
. 90. . , 1 Phosphoric acid 141010000. .

0. . 93. . ,,,,,, 0.7 Water 910
170191.5100149800.7°,. ,,,
51 Example 2 Beef tallow, , , , , , , , , , , , , , ,
,,, 97 parts by weight polymer dispersant (B), ,,,,
,,□,,, 3g parts boric acid, ,,,,,,,,,
,,,,,,,,,,,,,,,,,],29 Water,
,,,,,,,,,,,,,,,,,,,,,,,,,,,
,, 5 〃, Example 3 Beef tallow , , , , , , , , , , , , , , , , , , ,
,,, 95i parts polymer dispersant (C), ,,,,,
,,,,,, 5 Glycolic acid,,,,,,
,,,,,,,,,,,,, 2.4 Water,,,,
,,,,,,,,,,,,,,,,,,,,,,,,,,
5 Example 4 Beef tallow...
,,, 99.5 i-position polymer dispersant (D), ,,,
,,,,,,, 0.5 Lauric acid...
, , , , , , , , , , , 0.7 parts by weight Example 5 Beef tallow 0. ,,,,. 9. ,,,,,,,,,,,,,,,
,,, 93 parts by weight polymer dispersant (E), ,,,,,,
,,,,, 7' Hydrochloric acid, ,,,0. ．． ．． ．． ．．
．． ．． ．． ,,,,,,,,,,,. 1.61 〃Water...
, , , , , , , , , , 0. ,,,,,,,,,,
, 5 Example 6 Beef tallow , , , , , 09. ,． 8. ,,,,,,,,
,,, 96 parts by weight polymer dispersant (F);
,,,,,, 4 Boric acid, ,,,,,,,,
21 parts water
,,,,,,,,,,,,,,,,,,,,,,,,,,,
, 5 Example 7 Mineral oil , , , , , , , , , , , , , , , ,
,,, 97 parts by weight polymer dispersant (E), ,,,,
,,,,,, 3-phosphoric acid,,,,,,,,,,
, , , , , , , , , , 1.9 - Water 0. ．．
．． ．． ．． ．． ．． ．． ．． ．． ．． ．． ．． ．． ．． ,,,,,,,,,,,,,
5 〃Example 8 Mineral oil・・・・・・・・・・・・・・・・・・・・・
... 77i parts oleyl octanoate, ...
,,, 20 Polymer dispersant (B), ,,,,
,,,,,, 3 Lauric acid, ,,,,,,
, , , , , , , , 4.2 Example 9 Beef tallow -00
, 90.5 parts by weight Oleic acid (counter ion and oleic acid) 5 Phosphorous extreme pressure agent , , , , , , , , , , , ,,,,
1 part by weight antioxidant,
,,,,, O,S #Polymer dispersant (C),,,
,,,,,,,,, 3 #Comparative Example 1 Beef tallow, ,,,,,,,,,,,,,,,,,
,,, 92 parts by weight oleic acid (counterion and oil property)
5 parts by weight supernatant) Phosphorous extreme pressure agent, , , , , , , , , , ,
l 〃Antioxidant, , , , , , , , , , ,
,,,,,, 0.5 Polyoxyethylene nonylphenol, ,,,,,,,,,,,, 3
- Comparative Example 2 Mineral oil 5.6°, , , , , , , , , , , , , , ,
77 parts by weight oleyl octanoate
,,,, 20 〃Polyoxyethylene nonylphenol ether, ,,,,,,, 3 〃
The following performance tests were conducted on each of the compositions of Examples 1 to 9 and Comparative Examples 1 to 2 thus obtained.

The results are shown in Table 1 and Figures 1-4.

<Rolling test> Using a two-stage test rolling mill, rolling was performed for 7 passes under the following rolling conditions, the rolling load (number) at elongation rate = 3.4 was measured, and the rolling relative ratio was determined using the following formula. .

*Rolling conditions Rolling material: Mild steel plate (S P CC) thickness 2.2wm x medium 5ON x length 500m Rolling speed: 13m/min Roll: diameter 150m, body length 200m Bride roll Coolant temperature: 50-55℃ Coolant 41.5% emulsion bath schedule: 7 passes steel plate brightness test> A commercially available melting tape was pasted on the surface of the test rolled steel plate.
Then, the tape was peeled off, and the brightness of the surface of the tape pasted on a standard white mount was measured using a color difference needle ND-1OtD model manufactured by Nippon Heavy Industries. Completely black with O1 standard white mount brightness of 85
Find it as.

Deterioration Test> The rolling oil of the present invention (3% emulsion) was subjected to a 7-day deterioration test using a 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 a tank (liquid temperature 55℃±5℃), (2) is a filter, (3) is a pump (251/m1n), and (4) is a rotating drum (30φcm
X2Qe11'), this rotating drum (4) contains 150 1/2 steel balls, 2cIl x 2CI11 x 1
It contains eight c11 cast broncs and rotates at 125 rps.

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

Table 1

[Brief explanation of the drawing]

1 to 4 are drawings showing the results of deterioration tests for each rolling oil composition, and FIG. 5 is a drawing showing the method of deterioration testing. 1 , , , , tank 2゜0010. Filter 3, Pump 4, Rotating drum (and above) Figure 3 Figure 4 Figure 5

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)
A polyvinyl ether-based polymer compound having a repeating unit represented by the following formula, ▲Mathematical formula, chemical formula, table, etc.▼ (where n in the formula is an integer of 5 to 3000, and R represents the same or different lower alkyl group) , (b) The following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R^1 is an alkyl group having 1 to 18 carbon atoms,
One of them is ▲There is a mathematical formula, chemical formula, table, etc.▼, and the other is H, (C_2H_4O)-_(m')H,
Alkyl group having 1 to 18 carbon atoms, alkali metal, -NH(CH_2)_(m″)NH_2, NH_2R4
^ or NHR^5R^8, and n' is 10 to 3
050 integer, m is an integer of 1 to 3, m' is an integer of 1 to 20, m'' is an integer of 1 to 10. Also, R^2 and R
^3 is the same or different alkyl group having 1 to 3 carbon atoms, R^4 is an alkyl group having 1 to 20 carbon atoms, and R^5 and R^6 are the same or different alkyl groups having 1 to 20 carbon atoms. vinyl ether-maleic acid copolymer having a repeating unit represented by (representing a group), and (c) the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, X is the same as above. R^7 is H or CH_3
and n'' is an integer from 300 to 1300) A metal rolling composition characterized by containing as an essential component at least one vinyl-maleic acid copolymer having a repeating unit represented by .