JP2008007544A - Cold rolling oil composition for ultra-thin steel sheet - Google Patents

Abstract

[PROBLEMS] To stabilize the emulsification, to have uniform adhesion, and to improve the adhesion efficiency, while also exhibiting the effect of reducing the rolling oil basic unit, excellent in sheet surface cleanliness, less dirt around the rolling mill, and severe A rolling oil composition that can withstand various rolling conditions is provided.
(A) 100 parts by weight of at least one base oil selected from the group consisting of mineral oils, animal and vegetable fats and oils, and (b) nonionic surfactants having an HLB of 8 to 18 5 parts by weight, (c) 0.1-20 parts by weight of an ethylene oxide adduct of a secondary alcohol, and (d) Formula (1);
R-O- (AO) _p- (BO) _q- (AO) _r- R (1)
(In the formula, R represents a 2- to 6-mer acyl group of a hydroxycarboxylic acid having 18 carbon atoms, A represents an ethylene group, B represents a propylene group, p + r is 5 to 200, and q is 0. A cold rolling oil composition for an ultrathin steel sheet, comprising 0.2 to 5 parts by weight of a polymeric nonionic surfactant represented by:
[Selection figure] None

Description

  The present invention relates to a cold rolling oil composition for ultra-thin steel sheets used for cold rolling of plain steel and the like.

  Conventional cold-rolled oils include one or more base oils such as mineral oils, animal and vegetable oils and synthetic esters, nonionic surfactants, anionic surfactants, cationic surfactants, rust inhibitors, fatty acids In general, an extreme pressure agent, an antioxidant and the like are appropriately combined, diluted with water, and used as an emulsion having a predetermined concentration.

  Due to rapid advances in rolling equipment and technology in recent years, higher rolling speeds and mass production have been achieved, and the demand for rolling oil has become increasingly severe, and the development of rolling oil that can fully meet these demands has been developed. Is desired.

  In particular, for cold rolling of ultra-thin plates (original thickness 0.22 mm, finishing thickness 0.17 mm), rolling oils based on animal and vegetable oils and fats having excellent lubricity have been used. Although it is excellent in rolling lubricity, since dirt remains on the surface of the plate after rolling or around the rolling mill, there are disadvantages in that the load in the next process is increased and the working environment is deteriorated.

  Therefore, in particular, those using synthetic esters (mono, di, triester) as base oil (see Patent Document 1), and those blended with a polyamine condensate of a secondary amine and an unsaturated fatty acid (see Patent Document 2) Has been proposed.

  However, in these methods, in order to improve the adhesion efficiency, a means to increase the emulsion particle size by adjusting the HLB or the addition amount with a nonionic surfactant is taken, but this causes an increase in the oil unit, which is inconvenient. It is an economy. On the other hand, if the particle size is too large, excessive lubrication is caused and slipping prevents normal rolling. On the other hand, when the emulsion particle size is made smaller, the adhesion efficiency is deteriorated, and seizure due to insufficient lubrication and vibration phenomena associated with fluctuations in tension and thickness may occur.

In addition, rolling oil using a cationic polymer compound (see Patent Document 3) has also been proposed. However, the emulsification variation due to wear powder is large, frequent emulsification and particle size adjustment is required, and workability is poor. It was observed. In addition, since anions such as sulfate ions, nitrate ions, chloride ions, phosphate ions, and borate ions are used as counter ions, there has been a drawback that problems with rust are always attached.
Japanese Patent Laid-Open No. 60-60193 JP 7-310086 A JP 60-203699 A

  The object of the present invention is to stabilize the emulsification, to have uniform adhesion, and to improve the adhesion efficiency, while also showing the effect of reducing the rolling oil intensity, excellent in the surface cleanliness of the plate, and dirt around the rolling mill. The object of the present invention is to provide a rolling oil that can withstand severe rolling conditions.

  As a result of intensive investigations, the present inventors have used a specific polymer nonionic surfactant to maintain the particle size of the rolling oil emulsion within a certain range and uniformly adhere to the roll and the material to be rolled. The present invention has been completed by developing a rolling oil that can reduce the basic unit of rolling oil while exhibiting high lubricity.

That is, this invention provides the cold rolling oil composition for ultra-thin steel plates as shown below.
Item 1. (A) 100 parts by weight of at least one base oil selected from the group consisting of mineral oils, animal and vegetable oils and fats, and synthetic esters;
(B) 0.1 to 5 parts by weight of a nonionic surfactant having an HLB of 8 to 18,
(C) 0.1 to 20 parts by weight of secondary alcohol ethylene oxide adduct, and (d) Formula (1);
R-O- (AO) _p- (BO) _q- (AO) _r- R (1)
(In the formula, R represents a 2- to 6-mer acyl group of a hydroxycarboxylic acid having 18 carbon atoms, A represents an ethylene group, B represents a propylene group, p + r is 5 to 200, and q is 0. A cold rolling oil composition for an ultrathin steel sheet, comprising 0.2 to 5 parts by weight of a polymeric nonionic surfactant represented by:
Item 2. The nonionic surfactant having an HLB of 8 to 18 is at least one selected from the group consisting of alkyl ether type nonionic surfactants, alkyl ester type nonionic surfactants, and sorbitan ester ether type nonionic surfactants. Item 2. The cold-rolled oil composition for ultrathin steel sheets according to item 1.
Item 3. Item 2. The electrode according to Item 1, wherein the ethylene oxide adduct of secondary alcohol is an ethylene oxide adduct of linear secondary alcohol having 10 to 14 carbon atoms, and the number of moles of ethylene oxide added is 3 to 50 mol. Cold rolling oil composition for thin steel sheet.

  Hereinafter, the present invention will be described in detail.

  As the base oil (a) used in the present invention, any of those conventionally used in this type of rolling oil composition can be used. Specific examples include mineral oils such as spindle oil, machine oil, turbine oil, and cylinder oil; whale oil, beef tallow, pig oil, rapeseed oil, castor oil, nuka oil, palm oil, coconut oil, and the like. Animal and vegetable oils and fats; monoesters of fatty acids and synthetic fatty acids obtained from beef tallow, castor oil, coconut oil, etc. and aliphatic monohydric alcohols having 1 to 22 carbon atoms, the fatty acids and synthetic fatty acids and ethylene glycol, neopentyl glycol, tri Examples thereof include synthetic esters which are di-, tri- and tetra-esters with polyhydric alcohols such as methylolpropane and pentaerythritol.

  Nonionic surfactants (b) having an HLB of 8 to 18 used in the present invention include polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxy Alkyl ether type nonionic surfactants such as ethylene oleyl ether, alkyl ester type nonionic surfactants such as polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, sorbitan ester ether type non An ionic surfactant or the like is exemplified as a preferable one. The HLB of the nonionic surfactant used in the present invention is preferably 10-14. The usage-amount of a nonionic surfactant is 0.1-5 weight part with respect to 100 weight part of base oils, Preferably it is 0.5-3 weight part.

  Nonionic surfactants consist of hydrophilic groups and lipophilic groups. HLB is a numerical value of the balance between hydrophilic groups and lipophilic groups. The higher the HLB, the stronger the hydrophilicity, the lower the surface tension, and the permeability , Has the effect of increasing the cleaning power, and contributes to the improvement of dirt due to a mixture of iron powder and oil.

  The secondary oxide ethylene oxide adduct (c) used in the present invention is a linear secondary alcohol ethylene oxide 3 to 50 mol adduct (preferably 5 to 12 mol adduct having 10 to 14 carbon atoms). ). Examples of such an ethylene oxide adduct of a secondary alcohol include Nippon Shokubai Co., Ltd., Softanol 30, 50, 70, 90, 120, and the like. The amount of the secondary alcohol ethylene oxide adduct used is 0.1 to 20 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the base oil.

  The secondary oxide ethylene oxide adduct has excellent wettability and degreasing power, and also has stability against acids and alkalis, so it is durable and effective in soil dispersibility and cleanability. Demonstrate.

  The polymer nonionic surfactant (d) of the above formula (1) used in the present invention is composed of a 2 to 6-mer (preferably 4 to 6-mer) of a hydroxycarboxylic acid having 18 carbon atoms and a polyalkylene glycol. It is a diesterified product. Specific examples of the polymeric nonionic surfactant include polycondensates of 12-hydroxystearic acid and ricinoleic acid, or polycondensates in a mixed state thereof (2 to 6-mer, preferably 4 to 6). And a diesterified product obtained by esterifying polyethylene glycol (number average molecular weight 400 to 10,000) and polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer (number average molecular weight 1250 to 10,000). Those using a polycondensate of less than a dimer are not preferred because they are poor in lipophilicity and also deteriorate in lubricity. On the other hand, those using a polycondensate of 7-mer or higher have a high viscosity and have problems in utility as well as workability. The number average molecular weight of the polymeric nonionic surfactant is preferably 1500 to 16000, more preferably 2500 to 15000, and particularly preferably 3500 to 10,000. The amount of the polymeric nonionic surfactant used is 0.2 to 5 parts by weight, preferably 0.5 to 4 parts by weight, based on 100 parts by weight of the base oil.

  The polymer nonionic surfactant of the above formula (1) is easily adsorbed to a metal and also has a hydrophilic group, and thus has a protective colloidal action in the use state (emulsion) of rolling oil, and has an emulsion particle size. In a certain range.

  In addition to the components described above, various known additives such as extreme pressure agents, oiliness improvers, antioxidants, rust inhibitors and the like can be added to the rolling oil composition of the present invention as necessary.

  Examples of the extreme pressure agent include tricresyl phosphite and zinc dialkyldithiophosphate, examples of the oiliness improver include fatty acids such as oleic acid, stearic acid, and dimer acid, and examples of the antioxidant include 2, Examples thereof include phenolic compounds such as 4-di-t-butyl-p-cresol, aromatic amines such as phenyl α-naphthylamine, and the like as rust inhibitors, alkenyl succinic acid and derivatives thereof, fatty acids such as oleic acid, Examples include esters such as sorbitan monooleate, and other amines.

  The rolling oil composition of the present invention is diluted with water to produce a 2 to 5% emulsion, and is lubricated by spraying the gap between the rolling roll and the material to be rolled while circulating, compared to conventional rolling oil. This improves the performance, improves dirt, and improves the cleanliness of the product plate. It can reduce power consumption and oil intensity without load fluctuation.

  The cold-rolled oil composition of the present invention has excellent adhesion ability, forms a uniform film on a roll or a material to be rolled, exhibits no lubrication fluctuation due to generated iron powder, and exhibits high lubricity. When the cold rolling oil composition of the present invention is used, the cleanliness of the plate surface and around the rolling mill are also improved. Further, since there is no fluctuation in emulsification, it is not necessary to supply extra rolling oil, and the rolling oil composition has a low oil basic unit and is economically superior.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. However, the following examples do not limit the present invention.

Examples 1-8 and Comparative Examples 1-4
The rolling oil composition was prepared by blending the predetermined components shown in Table 1 in a predetermined blending amount. The numerical values in Table 1 indicate parts by weight.

In addition, each component in Table 1 is as follows.
[Animal fat] Refined beef tallow [Synthetic ester] Trimethylolpropane trioleate [Polymer nonionic surfactant]
(A) Tetramer of 12-hydroxystearic acid: polyethylene glycol (number average molecular weight 1500) = 2: 1 reaction product (number average molecular weight = 3800)
(B) 12-hydroxystearic acid hexamer: polyethylene glycol (number average molecular weight 2000) = 2: 1 reaction product (number average molecular weight = 5380)
(C) hexamer of ricinoleic acid: HO- (AO) _p- (BO) _q- (AO) _r- H (number average molecular weight 2400) = 2: 1 reactant (number average molecular weight = 5760) [formula A is ethylene group, B is propylene group, p + r = 11, q = 33]
(D) A hexamer of ricinoleic acid: HO— (AO) _p — (BO) _q — (AO) _r —H (number average molecular weight 10,000) = 2: 1 reactant (number average molecular weight = 13300) [formula A is ethylene group, B is propylene group, p + r = 159, q = 34]
[Nonionic surfactant] Polyoxyethylene monooleate (HLB = 13.5)
[Secondary alcohol EO adduct] An ethylene oxide 5-mole adduct of a secondary alcohol having 12 to 14 carbon atoms (Softanol 50 manufactured by Nippon Shokubai Co., Ltd.)
[Oil improver] Oleic acid [Antioxidant] 2,4-di-t-butyl-p-cresol [Rust inhibitor] Dodecenyl succinic acid.

  About each rolling oil composition shown by Table 1, various characteristics were evaluated with the following test method. The results are shown in Table 2 and FIGS.

<Rolling test>
Using a small two-stage rolling mill, three-pass rolling was performed under the following conditions, the total rolling load (TON number) at a reduction rate of 55% was measured, and the rolling relative ratio was determined by the following formula.
[Rolling conditions]
Rolling material: SPCC material of JIS G-3141 (low carbon steel, thickness 0.8mm x width 30mm coil)
Rolling roll: Bright roll with a diameter of 76 mm and a trunk length of 90 mm (Ra = 0.05 μm)
Rolling speed: 200 m / min
Front, back tension: 5kgf / mm ²
Number of passes: 3 (rolling rate 1 pass 20%, 2 passes 25%, 3 passes 25%)
[Lubrication conditions]
Coolant temperature: 50 ° C
Coolant concentration: 3% Emulsion spray amount: 2.3 L / min
Spray pressure: 0.5 kg / cm ²
Rolling relative ratio = rolling load (TON number) of Example or Comparative Example / rolling load (TON number) of Comparative Example 1
It shows that it is excellent in rolling lubricity, so that the value of this rolling relative ratio is low.

<Cleanliness evaluation test around rolling mill>
The pickling steel plate (SPHC) was rolled for 8 passes, and the stand clean property was evaluated from the amount of dirt (mixture of iron powder and oil) adhering to a clean steel plate (dirt adhesion evaluation plate) installed under the roll. It shows that the lower the value of the amount of dirt attached, the better the cleanability around the rolling mill.
[Rolling conditions]
Roll: 150mmφ × 200mm
Plate surface cleanliness evaluation plate: Pickling plate (2.3 mm × 50 mm × 500 mm)
Dirt adhesion evaluation plate: 1.0 mm × 200 mm × 300 mm.

<Steel lightness test>
A commercially available mending tape was applied to the surface of the test rolled steel sheet, then peeled, and the brightness of the surface of the tape applied to a standard white mount was measured with a color difference meter ND-101D manufactured by Nippon Denshoku Industries Co., Ltd. The brightness of the complete black was set to 0, and the brightness of the standard white mount was set to 85. The higher this value, the higher the brightness.

<Deterioration test>
Each rolling oil composition (3% emulsion) was subjected to a deterioration test for 7 days with a circulation deterioration tester shown in FIG. 7, and the particle size distribution before and after the test was measured with a multisizer manufactured by Beckman Coulter. In FIG. 7, 1 is a tank (liquid temperature 60 ± 5 ° C.), 2 is a filter, 3 is a pump (25 L / min), and 4 is a rotating drum (30 φcm × 20 cm). The rotating drum 4 includes 150 1/2 inch steel ball balls, 8 2 cm × 2 cm × 1 cm casting blocks, and rotates at 115 rpm.

  As is apparent from Table 2, it can be seen that the rolling oil compositions of the examples have improved lubricity by 2% to 10%. Further, the amount of dirt adhered is also ½ or less of the conventional rolling oil composition based on animal fats and oils (Comparative Example 1), and is expected to greatly contribute to the improvement of dirt around the rolling mill. Moreover, from the test results of the lightness of the steel plate, it can be seen that the surface of the steel plate after rolling is clean in the example from the comparative example. Even when viewed from the change in the particle size distribution before and after the deterioration test, it can be seen that the rolling oil compositions of the examples have little change and the emulsifiability is stable even when iron powder is generated and mixed. The fact that there is no fluctuation in emulsification indicates that uniform adhesion is possible and that the rolling speed can be increased, the fluctuation in rolling load is small, and the oil unit consumption is reduced.

It is a figure which shows the particle size distribution of the emulsion before the deterioration test of Example 2. FIG. 6 is a graph showing the particle size distribution of an emulsion after a deterioration test in Example 2. FIG. It is a figure which shows the particle size distribution of the emulsion before the deterioration test of Example 8. FIG. It is a figure which shows the particle size distribution of the emulsion after the deterioration test of Example 8. FIG. It is a figure which shows the particle size distribution of the emulsion before the deterioration test of the comparative example 3. It is a figure which shows the particle size distribution of the emulsion after the deterioration test of the comparative example 3. It is the schematic of a circulation deterioration tester.

Explanation of symbols

1 Tank 2 Filter 3 Pump 4 Rotating drum

Claims (3)

(A) 100 parts by weight of at least one base oil selected from the group consisting of mineral oils, animal and vegetable oils and fats, and synthetic esters;
(B) 0.1 to 5 parts by weight of a nonionic surfactant having an HLB of 8 to 18,
(C) 0.1 to 20 parts by weight of secondary alcohol ethylene oxide adduct, and (d) Formula (1);
R-O- (AO) _p- (BO) _q- (AO) _r- R (1)
(In the formula, R represents a 2- to 6-mer acyl group of a hydroxycarboxylic acid having 18 carbon atoms, A represents an ethylene group, B represents a propylene group, p + r is 5 to 200, and q is 0. A cold rolling oil composition for an ultrathin steel sheet, comprising 0.2 to 5 parts by weight of a polymeric nonionic surfactant represented by:   The nonionic surfactant having an HLB of 8 to 18 is at least one selected from the group consisting of alkyl ether type nonionic surfactants, alkyl ester type nonionic surfactants, and sorbitan ester ether type nonionic surfactants. The cold-rolled oil composition for an ultrathin steel sheet according to claim 1.   The ethylene oxide adduct of a secondary alcohol is an ethylene oxide adduct of a linear secondary alcohol having 10 to 14 carbon atoms, and the number of moles of ethylene oxide added is 3 to 50 moles. Cold rolling oil composition for ultra-thin steel sheets.

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