JP2564136B2 - Metal rolling oil composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a metal rolling oil composition, and more particularly to an emulsifying type metal rolling oil composition.

BACKGROUND OF THE INVENTION Metal rolling oils that have been generally used in the past are generally used as a lubricating oil component, usually a base oil such as fat, mineral oil or fatty acid ester, and various antirust agents, extreme pressure agents, oiliness improvers, antioxidants and the like. An auxiliary agent is added, and this is supplied as an O / W emulsion with an emulsifier to the rolling section at a concentration of about 0.1 to 20%. However, recent developments in rolling technology have led to high rolling speeds and mass production, lubrication, circulation stability,
Demands for rolling oils such as workability and wastewater treatment are becoming more and more severe, and at present the development of rolling oils that can sufficiently meet the demands is desired. However, rolling oils using conventional emulsifiers have various problems and are not satisfactory. That is, in the rolling oil using the conventional emulsifier, the type and amount of the emulsifier are changed, and the amount of oil (plate-out amount) adhering to the surface of the rolling oil and the rolled material is increased or decreased to control the rolling lubricity. Was. However, in rolling oils using such emulsifiers, the plate-out amount and the liquid circulation stability tend to contradict each other. Decrease and lubricity becomes insufficient, and if the plate out amount is increased,
There is a drawback that the emulsion becomes unstable and causes various troubles when it is used in a circulating manner. In addition, the generated iron powder adheres to the unstable emulsion, causing so-called rolling dirt that stains the cold-rolled steel sheet, and also has a disadvantage that adversely affects the washing and annealing steps that are the subsequent steps. In addition, it adheres to the rolling mill itself and its surroundings, which not only impairs aesthetic appearance but also causes problems in work.

OBJECT OF THE INVENTION The inventor of the present invention has been eagerly researching in order to solve the drawbacks of the conventional rolling oils, but the use of a specific polymer compound in this study solves the above drawbacks. It was found that an emulsion type rolling oil with excellent liquid circulation stability can be obtained without reducing the plate-out amount.
The present invention has been completed here. That is, the present invention includes (1) (A) a lubricating oil component which is at least one of animal and vegetable oils and fats, mineral oils and fatty acid esters, and (B) (a) the following formula (In the formula, R ² and R ³ are the same or different and are H or C ₁ to
A C ₁₈ linear or branched alkyl group is shown. A is a C _{1 to} C ₁₀ linear or branched alkyl group, or a —R ⁶ —O—R ⁷ — group,
Represents —CH ₃ or R ¹ O—. Here, R ¹ represents a C _{1 to} C ₁₈ linear or branched alkyl group, and R ⁶ and R ⁷ represent a C _{1 to} C ₄ alkyl group. D represents H or CH ₃ group. n ¹ is an integer of ⁵ to 1000. ) An alkylene or vinyl ether-maleic acid-based copolymer having a repeating unit represented by: (In the formula, A, R ² and R ³ are the same as above. N ³ is an integer of 1 to 3 and n ⁴ is an integer of 5 to 1000.) Styrene-maleic acid having a repeating unit represented by -Based copolymer, and (c) the following general formula (d) (In the formula, n ² represents an integer of 5 to 1000.) or the following general formula (e) (Wherein n ³ is an integer of 1 to 3 and n ⁴ is an integer of 5 to 1000), and 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,
At least one reaction imidization substance with at least one amine compound selected from the group consisting of 2-picolylamine, 3-picolylamine, and 4-picolylamine is contained as an essential component. A metal rolling oil composition.

It is related to.

EFFECTS OF THE INVENTION In the present invention, by using at least one of the specific polymer compounds represented by the above formulas (a) to (c), excellent liquid circulation stability can be achieved without reducing the plate-out amount. Shows sex. More specifically, in the rolling composition of the present invention, the lubricating oil component maintains a fairly large particle size and stabilizes due to the excellent protective colloidal action of the specific polymer compound represented by the above formulas (a) to (c). It is dispersed in water and has a broad particle size distribution, with a very narrow width and a sharp distribution with a very narrow width, with extremely good circulation stability. Also, when it is supplied to the rolled portion, if it comes into contact with the material to be rolled, the oil particles having a large particle size form a thick and strong lubricating film on the material to be rolled, exhibiting the effect of increasing the amount of plate-out. .

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

(I) Very little influence of temperature on emulsion concentration and coolant state (state in which rolling oil is diluted with water at the time of use), the state of emulsion does not change due to temperature change, and stable use is possible. Rolling work management becomes very easy.

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

(Iii) The cleaning property of the surface of the metal-rolled material is greatly improved. At this time, if the surface of the material to be rolled is not cleaned, edge carbon or the like is undesirably generated in annealing in a later step.

(Iv) The lubricity is greatly improved by about 2 to 10% compared to the conventional rolling oil.

Composition of the Invention The rolling oil composition of the present invention basically comprises a lubricating oil component comprising at least one of fats and oils, mineral oils and fatty acid esters, and a polymer compound represented by the above formulas (a) to (c). It is a mixture of at least one kind.

As the lubricating oil component used in the present invention, any of those conventionally used in this kind 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 mixture of two or more. Specifically, for example, spindle oil,
Mineral oils such as machine oil, turbine oil and cylinder oil; animal and vegetable oils such as whale oil, beef tallow, lard oil, rapeseed oil, castor oil, nuka oil, palm oil and coconut oil; beef tallow, coconut oil, palm oil and castor oil Esters of fatty acids obtained from oils and the like with aliphatic monohydric alcohols having 1 to 22 carbon atoms, ethylene glycol, neopentyl glycol, pentaerythritol and the like can be mentioned.

The production method of the polymer compound represented by the formula (a) used in the present invention is not limited, but it is produced, for example, by the following method.

The following general formula (d) (However, B, D, and n ² are the same as above), a polymeric substance having a repeating unit represented by the following general formula () is dissolved in an appropriate solvent such as formaldehyde, N, N dimethylformamide or dioxane. A) (Provided that R ^{2 to} R ³ and A are the same as described above, R ⁴ and R ⁵ are the same as R ² and R ³ ), and 1.0 to 1.5 equivalents are added per repeating unit of the above-mentioned polymer substance, and added. It can be produced by imidization usually at about 70 to 200 ° C., preferably at about 90 to 180 ° C. under temperature.

The polymer substance (d) is produced, for example, by the following method. That is, maleic anhydride (1 molar ratio) and alkyl vinyl ether (1.2 molar ratio) are combined with a suitable solvent such as dimethylformamide or dioxane in a suitable solvent such as benzoyl peroxide, ditertiarybutyl peroxide, azobisisobutyronitrile. It can be produced by solution polymerization in the presence of a polymerization initiator. This polymer substance has a degree of polymerization of about 5 to 1000 and an average molecular weight of about 2000 to 1,000,000.

Further, the styrene-maleic acid-based copolymer represented by the above (b) also has the following general formula (e) instead of the polymer substance (d) in the production of the above (a). (Wherein n ³ is an integer of 1 to 3 and n ⁴ is an integer of 1 to 1000) can be similarly produced using a polymer substance having a repeating unit.

The reaction conditions for imidization when producing the imidized product represented by (C) above are almost the same as the reaction conditions during the production of the copolymer of (A) above.

Preferred compounds among the compounds of the above formulas (a) to (c) used in the present invention are as follows. That is, first, in the formula (a), A is a C ₂ -C ₆ straight-chain or branched alkyl group, B is CH ₃ or R ¹ O-in the formula, R ¹ is a C ₁ -C ₈ straight-chain or branched alkyl group. , D is H or CH ₃ , R ² and R ³ are C _{1 to} C ₄ linear or branched alkyl groups, and n ¹ is 100 to 600.

As for the copolymer (b), A is a C _{1 to} C ₆ linear or branched alkyl group, R ² and R ³ are C _{1 to} C ₄ linear or branched alkyl groups, and n ⁴ is 6 to 500. , belongs to.

 The imidized product (c) is N-aminopropylpiperidine.

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 it is preferable to use these compounds together with a substance that forms a counter ion. Examples of the anion as a counter ion used in this case include sulfate ion, nitrate ion,
Examples thereof include chlorine ion, glycolate ion, phosphate ion, borate ion, and fatty acid ion having 1 to 20 carbon atoms.

Usually, rolling oil is used as a base oil in the manufacturing plant such as fats and oils, minerals or esters, and if necessary, an oiliness improver,
Transport a composition containing one or more of extreme pressure additives, rust preventive additives, antioxidants, emulsifiers, etc., and dilute to 0.1 to 10% concentration in water at the actual use site Used in the form of an emulsion.

Therefore, the counter ion has 1 to 20 carbon atoms, preferably 8 to
When 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, at the site of use, like the conventional rolling oil, a uniform emulsion is formed only by diluting with water to a predetermined concentration. On the other hand, when a counter ion other than the fatty acid ion having 1 to 20 carbon atoms is used as the counter ion, the polymer compounds (a) to (c) are difficult to uniformly dissolve in the base oil and are difficult to use at the site of use. It is preferable that the rolling oil and the dispersant are each diluted with water to a predetermined concentration to form an emulsion.

In the present invention, the compounds represented by the above general formulas (A) to (C) may be used alone or in combination of two or more.

The polymer compound of the present invention is 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.

To the metal rolling oil composition of the present invention, in addition to the above components, various known additives such as a rust preventive, an oiliness improver, an extreme pressure agent, an antioxidant, and the like can be added as necessary.

The above-mentioned various additives are 0 to 10%, 0 to 20%, 0 to 3%, and 0 to the total amount of the rolling oil composition, if necessary.
It can be added at a rate of 5%.

As rust inhibitors, alkenyl succinic acid and its derivatives, fatty acids such as oleic acid, esters such as sorbitan monooleate and other amines, etc., as oiliness improvers, oleic acid, higher fatty acids such as stearic acid and its derivatives Is a dibasic acid such as an ester or dimer acid,
Examples of the extreme pressure agent include phosphorus compounds such as tricresyl phosphate and organic compounds such as zinc dialkyldithiophosphate. Examples of the antioxidant include 2,4-di-t-butyl p.
A phenolic compound such as -cresol; an aromatic amine such as phenyl α-naphthylamine;

The metal rolling oil composition of the present invention is prepared by simply simultaneously mixing the above-mentioned rolling oil component and a water-soluble polymer compound, or prepared as a concentrated solution having a water content of up to about 80%, and water when used. It is used by diluting with.

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

Polymer dispersant A: Imide product of copolymer of isobutyl vinyl ether and maleic anhydride with N, N-dimethylaminopropylamine Degree of polymerization = 400 ▲ ▼ = 112000 B: Copolymer of methyl vinyl ether and maleic anhydride
Imidization degree with N, N-diethylaminoethylamine Degree of polymerization = 600 ▲ ▼ = 15200 C: Imidation degree of copolymer of octyl vinyl ether and maleic anhydride with N, N-dimethylaminoethoxypropylamine Degree of polymerization = 60 ▲ ▼ = 23000 D: of a copolymer of ethyl vinyl ether and maleic anhydride
Imidized product with N, N-dimethylaminoneopentanamine Degree of polymerization = 200 ▲ ▼ = 56000 E: Imide product of copolymer of oleyl vinyl ether and maleic anhydride with methylaminopropylamine Degree of polymerization = 10 ▲ ▼ = 5500 F: Imidized product of copolymer of styrene and maleic anhydride with N, N-dimethylaminopropylamine Degree of polymerization = 200 ▲ ▼ = 57800 G: Imide product of copolymer of isobutyl vinyl ether and maleic anhydride with N-aminopropylpiperidine Degree of Polymerization = 800 ▲ ▼ = 250,000 Examples 1 to 7 Using the above dispersants, the predetermined components shown in Table 1 and predetermined amounts were mixed to prepare rolling oil compositions.

Various properties of each composition thus obtained were measured. The results are shown in Table 2 and FIGS. However, various characteristics were measured by the following methods.

<Adhesion amount> A 1.6 × 80 × 100 mm pickling plate is dull-rolled for 5 passes, drained, air-dried (24 hours), weighed, and w ₁ is measured. Then, it is washed with trichlene and weighed to measure w ₂ .

Adhesion amount = w ₁ −w ₂ <Rolling test> Using a two-stage test rolling machine, 7-pass rolling was performed under the following rolling conditions, and the rolling load (t number) at the elongation rate = 3.4 was measured. The relative rolling ratio was calculated by the formula.

* Rolling conditions Rolling material: Mild steel plate (SPCC) thickness 2.2 mm x width 50 mm x length 500
mm Rolling speed: 13m / min Rolling roll: Diameter 150mm, body length 200mm Bright roll Coolant temperature: 50-55 ℃ Coolant temperature: 5% Emulsion pass Schedule: 7 pass <Steel plate lightness test> A commercially available melting tape was applied to the surface of the test rolled steel plate, which was then peeled off, and the lightness of the surface of the tape was applied to a standard white mount with a color difference meter ND-101D manufactured by Nippon Denshoku Industries Co., Ltd. did. Complete black is defined as 0, and the brightness of the standard white mount is defined as 85.

<Deterioration test> The rolling oil (3% emulsion) of the present invention was subjected to a deterioration test for 7 days using a circulating deterioration tester shown in Fig. 5 to measure the particle size distribution before and after the test. However, in FIG. 5, (1) is a tank (liquid temperature 55 ° C. ± 5 ° C.), (2) is a filter, (3) is a pump (25 / min), and (4) is a rotating drum (30φcm × 20cm ^l ).
Indicates. 1/2 steel ball 150 in this rotating drum (4)
Pieces, 8 pieces of 2cm x 2cm x 1cm casting blocks, 115
It rotates at rpm.

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

[Brief description of drawings]

1 to 4 are drawings showing the results of the deterioration test of each rolling oil composition, and FIG. 5 is a drawing showing the method of the deterioration test. 1 ... Tank 2 ... Filter 3 ... Pump 4 ... Rotating drum

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area C10N 30:00 40:24

Claims (1)

(57) [Claims] 1. A lubricating oil component which is at least one of animal and vegetable oils and fats, mineral oils and fatty acid esters, and (B) (a) the following formula: (In the formula, R ² and R ³ are the same or different and are H or C ₁ to
A C ₁₈ linear or branched alkyl group is shown. A is a C _{1 to} C ₁₀ linear or branched alkyl group, or a —R ⁶ —O—R ⁷ — group,
Represents —CH ₃ or R ¹ O—. Here, R ¹ represents a C _{1 to} C ₁₈ linear or branched alkyl group, and R ⁶ and R ⁷ represent a C _{1 to} C ₄ alkyl group. D represents H or CH ₃ group. n ¹ is 5
Is an integer from ~ 1000. ) An alkylene or vinyl ether-maleic acid-based copolymer having a repeating unit represented by: (In the formula, A, R ² and R ³ are the same as above. N ³ is an integer of 1 to 3 and n ⁴ is an integer of 5 to 1000.) Styrene-maleic acid having a repeating unit represented by -Based copolymer, and (c) the following general formula (d) (However, in the formula, n ² represents an integer of 5 to 1000.) Or the following general formula (e) (Wherein n ³ is an integer of 1 to 3 and n ⁴ is an integer of 5 to 1000), and N-aminoethylpiperidine, N-aminopropylpiperidine, N- Aminoethyl-4-pipecoline, N-aminopropylpipecoline, N-aminoethylmorpholine,
N-aminopropylmorpholine, N-aminopiperidine, N-amino-4-methylpipecoline, isonicotinamide, nicotinamide, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-picolylamine, 3- A metal rolling oil composition containing as an essential component at least one kind of a reaction imidized substance with at least one kind of amine compound selected from the group consisting of picolylamine and 4-picolylamine. .