JPH0240120B2 - REIKANATSUENNIOKERUCHOKUSETSUSHIKIATSUENYUKYOKYUHOHOHO - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for supplying rolling oil in a direct rolling oil supply system, and more particularly to a direct rolling oil supply method using a specific water-soluble polymer compound. As a rolling oil supply system in cold rolling, there is a circulating rolling oil supply system RC that recirculates the rolling oil emulsion, and after supplying the rolling oil emulsion to the rolls and rolled steel plates, the used rolling oil is used as waste oil. There are two direct rolling oil supply systems DA to process. The present invention relates to a rolling oil supply method for the latter direct rolling oil supply system. In the direct rolling oil supply system, beef tallow,
Using palm oil, etc., before supplying the rolling oil to the processing area between the strip and the rolls during cold rolling, the used water and rolling oil are mixed, the rolling oil is made into an emulsion called premixing, and this emulsion is processed. At present, only water is sprayed onto the roll surface for the purpose of lubrication, and at the same time, water is separately sprayed onto the roll surface for the purpose of cooling the roll. In this system, the rolling oil alone is often used as a forced emulsion, but it is also related to the fact that a relatively high concentration emulsion is prepared, and rolling oil particles coalesce in the emulsion, causing the emulsion to form. The problem is that it is unstable. This coalescence destabilizes the emulsion, which means non-uniform oil particles are supplied to the processing area, uneven adhesion to the surface of the steel plate, and clogging of spray nozzles when spraying onto the processing area, which destabilizes the rolling operation. , contamination due to adhesion of scum generated during rolling around the mill, non-uniformity of emulsion temperature in the pre-mixing tank, etc.
Although it has many drawbacks, one of the major problems is that it is difficult to dispose of the rolling oil emulsion produced together with a large amount of roll cooling water after rolling. Therefore, in order to eliminate these drawbacks and improve stable rolling operation and wastewater treatment performance in the above-mentioned rolling oil supply system, the present inventors conducted extensive research and found that a specific water-soluble polymer compound was added to the rolling oil supply system. By applying it during mixing and making it into an emulsion of rolling oil, pre-mixing can make the rolling oil uniform and large.
In addition, stable oil particles can be generated and a uniform amount of adhesion can be obtained on the strip surface, that is, stable rolling operation is possible, and the oil particles in this rolling oil dispersion are uniform and large, so they float easily. Due to these characteristics, it was discovered that waste oil after rolling has extremely good drainage treatment properties, and the present invention was completed. That is, the present invention provides a direct rolling oil supply method in cold rolling in which the rolling oil emulsion is not circulated and is directly supplied to the rolling processing section, during premixing or a step before that to prepare a highly concentrated rolling oil emulsion. (a) A water-soluble polymer selected from cationic or zwitterionic addition polymers, ring-opening polymers, polycondensates, or natural polymer compounds containing nitrogen atoms in the molecule with a molecular weight of 10 to 10 million. Direct rolling in cold rolling characterized by adding one or more molecular compounds or (b) an anionic water-soluble polymer compound containing a carboxyl group or a sulfonic acid group in the molecule. The present invention provides a rolling oil supply method. According to the supply method of the present invention, it is possible to homogenize and stabilize the emulsified oil particles in the emulsion of rolling oil such as beef tallow or palm oil during pre-mixing, and it is possible to uniformize and stabilize the emulsified oil particles in the rolling oil strip. It has the advantage that it improves the adhesion of the dispersion, enables stable rolling operations, and simplifies drainage treatment of the dispersion after use. The cationic or amphoteric water-soluble polymer compounds used in the method of the present invention include the following a○ to h○
Examples include: a○ A homopolymer or a copolymer of two or more nitrogen-containing monomers or salts thereof represented by the following general formulas () to (). [R ₁ is H or CH ₃ , R ₂ and R ₃ are H or an alkyl group having 1 to 3 carbon atoms] [m ¹ is a number from 1 to 3, n ¹ is a number from 1 to 3, R ₁ , R ₂ ,
R ₃ is the same as formula ()] [R ₄ is H or an alkyl or alkylol group having 1 to 3 carbon atoms, R ₁ is the same as formula ()] [m ² and n ² are numbers from 0 to 3, R ₁ , R ₂ and R ₃ are the same as formula ()] [A is -0- or -NH-, R ₁ , R ₂ , R ₃ , n ¹
is the same as expressions () and ()] [R ₁ , R ₂ , R ₃ , n ¹ are the same as formulas () and []] [R ₁ is the same as formula (). Pyridine substitution position is 2 or 4] [R ₁ and R ₂ are the same as formula (). Substitution position of piperidine is 2 or 4] [R ₁ , R ₂ , R ₃ are the same as formula ()] Dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropylacrylamide, diethylaminopropylacrylamide, dimethylaminopropyl of formula () Methacrylamide, diethylaminopropylmethacrylamide, etc.; dimethylaminomethylethylene of the formula (),
Diethylaminomethylethylene, dimethylaminomethylpropene, diethylaminomethylpropene, etc.; Vinylpyridine, etc. of formula (); Vinylpiperidine, vinyl-N-methylpiperidine, etc. of formula (); Vinylbenzylamine, vinyl-
Examples include N,N-dimethylbenzylamine. b○ One or more nitrogen-containing monomers or salts thereof represented by the above general formulas () to (),
A group consisting of α,β-unsaturated carboxylic acids or their salts, their amides, esters, or acid anhydrides, sulfonic acid group-containing vinyl compounds or their salts, acrylonitrile, vinylpyrrolidone, and aliphatic olefins having 2 to 20 carbon atoms. A copolymer with one or more vinyl monomers selected from: Examples of the vinyl monomer include vinylpyrrolidone, acrylonitrile; acrylic acid,
Methacrylic acid, maleic acid or alkali metal salts, ammonium salts, amide compounds or esters of these acids; vinyl sulfonic acid,
Methallylsulfonic acid, 2-acrylamide-2
- Methylpropanesulfonic acid, p-styrenesulfonic acid, or alkali metal salts or ammonium salts of these acids. c○ Salts of ring-opening polymers of ethyleneimine or quaternary
grade ammonium salt. Specifically, the repeating unit is represented by the following general formula (), and the average molecular weight is 1000 to 1000.
Thousands of things can be mentioned. [In the formula, n ³ is an integer of 1 to 5, and n ⁴ is an integer of 0 to 5] d○ A salt of a condensation product of an aliphatic dicarboxylic acid and a polyethylene polyamine or a dipolyoxyethylene alkylamine or a quaternary salt grade ammonium salt. Specifically, those repeating units are a condensation product with polyethylene polyamine represented by the general formula (XII) and a condensation product with a dipolyoxyethylene alkylamine represented by the general formula (), with a molecular weight of 1000 to 1000. Thousands of things can be mentioned. [―OC―R ₇ ―CONH (―R′―NH―) _o5 ――R′―
NH-] (XII) [In the formula, R ₇ is a dimer acid residue or a carbon number of 1
~10 alkylene group, R' is -CH ₂ CH ₂ -, n ⁵ is an integer from 2 to 7] [In the formula, R ₉ is the same as formula (XII). R ₈ is an alkyl group having 1 to 8 carbon atoms, R ₉ is H or CH ₃ , and n ⁶ and n ⁷ are integers of 1 to 10. Examples of the aliphatic dicarboxylic acids include dimer acid and adipic acid. As the polyethylene polyamine, diethylenetriamine, triethylenetetramine, etc. can be used. e○ Dihaloalkane-polyalkylenepolyamine condensation product. Specifically, 1,2-dichloroethane, 1,
It is a condensation product which is a quaternary ammonium salt of a dihaloalkane such as 2-dibromoethane or 1,3-dichloropropane and a polyalkylene polyamine having two or more tertiary amino groups in the molecule, Its average molecular weight is 1000~
There are 10 million things to list. Examples of the polyalkylene polyamines mentioned above include the following. f○ Epihalohydrin-amine condensation product. Specifically, the repeating unit is represented by the following general formula () and the average molecular weight is 10 million to 10 million. [In the formula, R ₁₀ to _{R 12} are CH ₃ or C ₂ H ₅ , and X represents a halogen ion] g○ Cationized starch, cationized cellulose, a salt of chitosan, or a quaternary salt of chitosan. h○ Polyether polyols or polyether polyols with a molecular weight of 1000 to 600,000 obtained by adding alkylene oxide to polyalkylimines having 6 to 20 nitrogen atoms (including esterified products of OH at the terminals of polyether polyols; The same applies hereinafter) Polyalkylene polyamines have five or more consecutive skeletons shown in the following formula () in the molecule,
At least one of them has a skeleton represented by the following formula (), and is preferably a polyethyleneimine containing 6 to 100 nitrogen atoms with OH and/or NH ₂ terminals. Further, the alkylene oxide in the polyether polyol is one or more selected from the group consisting of ethylene oxide, propylene oxide, styrene oxide, and butylene oxide, and the content thereof is 3 to 30% of the polyether polyol.
Preferably it is 80% by weight. The polycondensates of a○ to h○ above have an average molecular weight of
10 million to 1 million is more preferable. These cationic and zwitterionic polymer compounds are preferably salts, and examples of the counter anions include the following phosphoric acid compounds (i) to (v) or boric acid. (i) Phosphoric acid, phosphorous acid or their thio or ester compounds (ii) Alkyl, alkylaryl or allyl group with 1
(iii) Mono- or diphosphonic acid esters having 1 or more hydroxyl groups, or thio compounds thereof; (iii) Mono- or diphosphones having an alkyl, alkylaryl, or allyl group having 1 to 8 carbon atoms, or thio compounds thereof; (iv) thio compounds thereof, having 1 to 8 carbon atoms; Mono- or diphosphines having an alkyl, alkylaryl or allyl group in No. 8 or their thio compound (v) Mono-, di- or triphosphonic acid containing a nitrogen atom Specific examples of this phosphoric acid compound include the following: . Examples of (i) include orthophosphoric acid, phosphorous acid, mono- or diphosphoric acid esters of aliphatic, alicyclic or aromatic alcohols having 1 to 8 carbon atoms and orthophosphoric acid, or thio compounds thereof; Examples include phosphorous acid esters with the above alcohols or thio compounds thereof. An example of (ii) is 2-hydroxypropyl phosphate. For (iii), the general formula

[Formula] or

[Formula] (R ₀ , R′ ₀ is an alkyl group having 1 to 8 carbon atoms, an alkylaryl group or an allyl group), such as methylphosphonic acid having 1 carbon number, dimethylphosphonic acid to n having 8 carbon atoms ―
Octylphosphonic acid, di-n-octylphosphonic acid, 2-ethylhexylphosphonic acid, di-2-ethylhexylphosphonic acid, benzylphosphonic acid,
Examples include dibenzylphosphonic acid, phenylphosphonic acid, diphenylphosphonic acid, hydroxytandiphosphonic acid, and these thiophosphonic acids. Hydroxyethane diphosphonic acid is a compound represented by the following formula. For (iv), the general formula

[Formula] or

[Formula] (R ₀ , R′ ₀ are the same as above) Phosphinic acid, for example, methylphosphinic acid with 1 carbon number, dimethylphosphinic acid with 8 carbon atoms
n-octylphosphinic acid, di-n-octylphosphinic acid, 2-ethylhexylphosphinic acid,
Examples include di-2-ethylhexylphosphinic acid, benzylphosphinic acid, dibenzylphosphinic acid, phenylphosphinic acid, diphenylphosphinic acid, and these thiophosphinic acids. Examples of (v) include tetramethylphosphoric diamide, dimethylphosphoric monoamide, and nitrilotrismethylenephosphonic acid. Nitrilotrismethylenephosphonic acid is a compound represented by the following formula. Examples of anionic water-soluble polymer compounds having carboxyl groups or sulfonic acid groups in the molecule include copolymers of olefin and maleic acid, (meth)
Copolymers of acrylic acid and maleic acid, copolymers of acrylonitrile and maleic acid, copolymers of acrylamide and maleic acid, homopolymers of (meth)acrylic acid, or salts of these copolymers or homopolymers; Examples include salts of copolymers with the above monomers. The amount of these water-soluble polymer compounds added is 0.1 to 20% by weight (hereinafter simply expressed as %), preferably 0.1 to 10% by weight, based on the rolling oil. The mechanism of stabilization of rolling oil particles by this water-soluble polymer compound has not been elucidated in detail, but its effect is that the rolling oil particles are finely divided in response to mechanical shearing forces such as those caused by stirring during premixing. This water-soluble polymer compound is quickly adsorbed on the particle surface before the oil particles coalesce, forming a sufficient adsorption film on the surface and making the particles larger due to a kind of aggregation effect. Furthermore, the steric and electrical protective colloid effects of these water-soluble polymer compounds allow large oil particles to stably exist in water. Oil particles that have been subjected to protective colloidal action or the like by a water-soluble polymer compound become extremely stable once they are generated by mixing or the like. For this reason, although a dispersion with a uniform concentration can be obtained by stirring during mixing, if no stirring force is applied, oil particles easily float to the surface of the dispersion, unlike in the case of conventional emulsions, for example, when static This is different from the continuation of the milky state in the lower layer when it is placed in a container. This means that uniform and stable oil particles can be supplied to the processing section during processing, and waste oil can be disposed of after processing by simply letting it stand still.
The oil content in the lower layer is drastically reduced. Furthermore, by adding ordinary treatments such as coagulation and sedimentation, wastewater treatment can be easily carried out, and rolling oil can be separated and recovered from the used emulsion. In addition, this polymer compound is thought to have strong dispersion power, and it does not have the emulsifying power of emulsifiers, etc., so clean rolling oil is supplied to the processing section, cleaning the plate surface, and spray nozzles, etc. It is possible to prevent clogging with foreign matter and contamination caused by scum around the rolling mill. Furthermore, water-soluble polymer compounds have the effect of making iron powder, scum, etc. hydrophilic, so they have excellent effects on work surfaces and other environmental aspects, such as removing these stains around rolling mills. . Next, an example will be given and explained. In the examples, the following water-soluble polymer compounds and rolling oil were used. Water-soluble polymer compound: (A) Polymer of diethylaminomethyl methacrylate as phosphate (MW = 300,000) (B-1) Borate of diethylaminoethyl methacrylate/vinylpyrrolidone/sodium acrylate = 5/4 /1 (shown as a molar ratio; the same applies hereinafter in this table) (MW = 200,000) (B-2) (MW = 50,000) (B-3) (MW = 1500) (C ) Copolymer of diethylaminoethyl methacrylate phosphate/sodium methacrylate = 4/5 (MW = 20,000) (D-1) Ring-opening polymer of ethyleneimine phosphate (MW = 100,000) ( D-2) Polyethyleneimine (MW=70,000)
A phosphate is obtained by reacting propionic acid to a concentration of 15%. (E) Ethyl phosphonate of diethylaminoethyl methacrylate/sodium 2-acrylamino-2-methylpropanesulfonate = 4/1 copolymer (MW = 100,000) (F) Phosphate of vinylpyridine/vinylpyrrolidone/ Copolymer of sodium acrylate = 6/3/1 (MW = 450,000) (G) Cocondensate of diethylenetriamine thionate and dimer acid (MW = 800,000) (H) Phosphoric acid of diethylaminoethylmethacrylamide Copolymer of salt/sodium acrylate/sodium vinyl sulfonate = 3/1/1 (MW = 400,000) (I) Borate of ethyleneimine phosphate of water-soluble polymer compound (D) . (J) Quaternary ammonium salt of cationized cellulose (MW = 1 million) (K) Co-condensate of phosphate of 1,2-dichloroethane and hexamethylenetetramine (MW = 50,000) (L) Trimethylamine of epichlorohydrin Fourth
Ring-opening polymer of phosphite of grade ammonium compound (MW=100,000) (M) Cocondensate of quaternary ammonium salt of tetramethylpropylenediamine with diethylphosphonic acid (MW=100,000) (N) Water-soluble Water-soluble polymer compound (F) vinylpyridine phosphate as sulfate (O) Water-soluble polymer compound (G) diethylenetriamine thiophosphate as nitrate (P) Water-soluble polymer compound (E) Hydrochloride of dimethylaminoethyl methacrylate ethyl phosphonate (Q) Water-soluble polymer compound (D) ethyleneimine phosphate as acetate (R) Dimethyl vinylpyridine Copolymer of quaternary ammonium salt with sulfuric acid/vinylpyrrolidone/sodium acrylate=6/3/1 (MW=
450,000) (S) Polyethyleneimine with 20% ethylene oxide added to polyethyleneimine (MW = 50,000) (T) Na salt of acrylic acid-maleic acid = 1/1 copolymer (MW = 10,000) (U) Methacrylic acid-isobutylene = 3/1
(MW=5000) (V) Na salt of a homopolymer of 2-acrylamide-2-methylpropanesulfonic acid (MW=
10,000) (W) Na salt of 2-acrylamide-2-methylpropanesulfonic acid/acrylamide = 2/1 copolymer (MW = 20,000) Rolling oil: (1) Palm oil alone (2) Beef tallow 97.0 % Antioxidant (phenol type) 1.0 Beef tallow fatty acid 2.0 (3) Mineral oil (50cst/40℃) 61.0% Beef tallow 30.0 Beef tallow fatty acid 5.0 Antioxidant (phenol type) 1.0 Extreme pressure agent (phosphate ester type) 2.0 Emulsifier 1.0 (4) Butyl stearate 61.0% Beef tallow 33.0 Beef tallow fatty acid 5.0 Extreme pressure agent (phosphate ester type) 1.0 Antioxidant (phenol type) 1.0 Emulsifier 1.0 (5) Mineral oil 61.0% Octyl stearate 30.0 Beef tallow fatty acid 5.0 Extreme Pressure agent (phosphate ester type) 2.0 Antioxidant (phenol type) 1.0 Emulsifier 1.0 Emulsifier: Polyoxyethylene nonyl phenyl ether (HLB=7.6)

【table】

【table】

[Table] Example 1 Particle size and particle size distribution of rolling oil by premixing Premixing is performed to form a forced emulsion of rolling oil and water in the direct rolling oil supply system of a cold rolling mill. Te, 2
of the rolling oil/water mixture at a temperature above the melting point of the rolling oil.
Emulsion was carried out by applying mechanical shearing force at 60° C. using an M-type homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. at a rotation speed of 4000 rpm for 60 minutes. Next, the average particle size and particle size distribution of the rolling oil in this emulsion were measured using a Coulter counter, which is commonly used for particle size measurement. In addition, when stirring this rolling oil/water mixture, the homomixer rotation speed was set at 4000 rpm, but the mechanical shearing force exerted on the rolling oil due to this rotation speed is the same as that of the direct rolling oil of an actual cold rolling mill. This corresponds to the shear force during premixing in the feed system. The results of measuring the average particle size of the rolling oil after mixing the mixture shown in Table 1 below are shown in Table 2, and a representative example of a chart showing the particle size distribution is shown in Figure 1. Table 2 shows the mixing ratio of rolling oil/water, the application method of the polymer compound (addition to the rolling oil or added to the water used), and the applied concentration of the polymer compound to the rolling oil when emulsifying rolling oil and water. The performance of rolling oil was investigated by changing the As is clear from the results in Table 2, by applying the polymer compound of the present invention to the direct rolling oil supply system, the particle size of rolling oil can be made larger and more uniform compared to the comparative example, and the particle size distribution can also be improved. By supplying the oil particles to the processing section as an emulsion, it is possible to improve the uniform adhesion of rolling oil to the surface of the rolling mill, increase the amount of adhesion, and increase the concentration of rolling oil during premixing. The rolling operation is stabilized based on the uniformity of the rolling process. The polymer compound used in the supply method of the present invention has the same effect on the type of rolling oil, such as tallow-based rolling oil, palm oil alone, etc. It has the same effect whether it is added to oil or water used for emulsification. Regarding the applied concentration of polymer compounds during premixing, if the concentration of the polymer compound is less than 0.1% by weight, the average particle size of the rolling oil, which exhibits the performance of the polymer compound, will be disturbed and the particle size distribution will not be sharp. . In addition, the applied concentration of polymer dispersant is 10% by weight.
If it exceeds this, the average particle diameter tends to become smaller because the absolute concentration of the polymer compound in the aqueous solution increases, and the amount added also increases, which is economically disadvantageous. Therefore, the concentration of the polymer compound to be applied is preferably 0.1 to 20% by weight based on the rolling oil. As shown in the examples, there is no difference in performance even when two or more of these polymer compounds are mixed, and a plurality of them can be used simultaneously. When the molecular weight of the polymer compound used in the supply method of the present invention is 1,000 or more, the effect is almost the same and is excellent, but when it is less than 1,000, the performance is poor. In addition, when the molecular weight is 1000 or more, there is no difference in the effect, but
If it exceeds 1,000,000, the viscosity of the polymer compound increases significantly, making it unusable in terms of handling, etc. Therefore, the viscosity of the polymer compound is 1000~
1000000 is preferred.

【table】

[Table] Indicates that it is not a group.
Example 2 Adhesion weight test The adhesion weight test was conducted by diluting the emulsion prepared in Example 1 with water for each metal processing composition.
% concentration, and mix it with a homomixer at 60℃.
This was done by applying the emulsion to the test piece by spraying while stirring at 4000 rpm. The test piece for measuring the amount of adhesion was a surface-cleaned cold-rolled steel plate (50 x 150 x 0.2 mm) that was preheated to a temperature of 150°C before spraying, and the test liquid was applied to it using a gear pump at a spray rate of 500 ml/min. It was applied to the surface of a steel plate for 2 seconds at a pressure of 1 Kg/cm ² . The amount of adhesion was measured by drying the sprayed test piece and extracting the oil with a solvent.
The results are shown in Table-3.

【table】

[Table] As shown in Table 3, the adhesion amount measurement results clearly show an increase in the adhesion amount by applying the water-soluble polymer compound. If this compound is not applied, the particle size distribution of the rolling oil is broad and particles of various sizes are spread on the steel plate surface, and the stability of the emulsion is poor and the adhesion concentration is uneven (for example, as oil However, by applying a water-soluble polymer compound, it is possible to supply an emulsion that is uniform, stable, and has a large particle size, which reduces the amount of rolling oil that adheres compared to the comparative example. To increase. Here, the concentration of water-soluble polymer compound relative to rolling oil is
If it is less than 0.1%, as shown in Example 1, the particle size becomes unstable (enlarges and tends to float), so the concentration of rolling oil in the lower layer decreases, the amount of adhesion decreases, and the water-soluble polymer On the other hand, if the amount of the compound exceeds 10%, the particle size becomes smaller and the amount of adhesion tends to decrease. When measuring the amount of adhesion, the application of the water-soluble polymer compound showed that the wettability of the rolling oil emulsion when sprayed onto the surface of the steel plate (possibly based on the effect of making the surface of the rolling oil particles hydrophilic, etc.) It was found to be good. In the case of the comparative example, the emulsion is repelled when sprayed, but when a water-soluble polymer compound is applied, the wetting property is good, so that uniform adhesion of the rolling oil can be achieved. Example 3 Seizure load test (Soda four-ball test method) Seizure load measurement is based on the Defense Agency provisional standard NDS
XXK2740 Oil film strength test method (Soda four-ball test method)
I followed the instructions. The test sample was prepared using a sample prepared in the same manner as in Example 2, and was stirred using a homomixer at a rotational speed of 4000 rpm. The test sample was applied using a gear pump at a spray rate of 0.5/min (pressure: 0.5 Kg/cm ² ) and a sample solution temperature of 50°C, and applied to three test steel balls fixed with a ball holder. The coating was applied from below to the rotating steel ball above through the space at the center of the three contact points. In addition, the test samples were representative ones. The results are shown in Table-4.

[Table] The effect of uniformly enlarging the particle size of the rolling oil of water-soluble polymer compounds, the wetting effect of the emulsion, and the extreme pressure effect of using phosphoric acid and borate as counterions work to increase the water-soluble polymer compound. The product of the present invention to which a molecular compound is applied has superior lubricity compared to comparative products. Example 4 Wastewater treatment test The test solution (2) prepared in the same manner as in Example 2 was allowed to stand, and after 60 minutes, 500 ml of the lower layer was collected (using a separating funnel).
did. After ±3 g of ban sulfate was added to this solution, the mixture was stirred for 2 minutes, and then Ca(OH) ₂ was added to adjust the pH to 7.0, followed by stirring for 10 minutes. Next, after standing for 30 minutes, the subnatant liquid was collected and the COD (KMnO ₄ method) was measured. The results are shown in Table-5.

【table】

[Table] In terms of wastewater treatment properties, the product of the present invention to which a water-soluble polymer compound is applied is significantly superior to comparative products. This is thought to be because the water-soluble polymer compound has the effect of making the oil particle diameter uniform and large, and furthermore, the water-soluble polymer compound itself acts as a flocculant.

[Brief explanation of drawings]

Figure 1 is a diagram showing the particle size distribution of rolling oil.
is the invention product No. 1, 2 is the invention product No. 6, 3 is the invention product No. 11, 4 is the invention product No. 19, 5 is the invention product No. 28,
6 is the invention product No. 29, 7 is the invention product No. 30, 8 is the invention product No. 32, 9 is the invention product No. 40, and 10 is the invention product No.
43, 11 is the invention product No. 45, 12 is the comparison product No. 1, 1
3 shows the particle size distribution of comparative product No. 2, 14 shows the comparative product No. 3, 15 shows the comparative product No. 4, and 16 shows the particle size distribution of comparative product No. 5.

Claims (1)

[Scope of Claims] 1. A step during or before premixing to prepare a highly concentrated rolling oil emulsion in a direct rolling supply method in cold rolling where the rolling oil emulsion is not circulated and is directly supplied to the rolling processing section. (a) One type selected from cationic or zwitterionic addition polymers, ring-opening polymers, polycondensates, or natural polymer compounds containing nitrogen atoms in the molecule with a molecular weight of 10 million to 10 million; Cold rolling characterized by adding either two or more water-soluble polymer compounds, or (b) an anionic water-soluble polymer compound containing a carboxyl group or a sulfonic acid group in the molecule. Direct rolling oil supply method. 2. Claim 1, wherein the amount of the water-soluble polymer compound added is 0.1 to 20% by weight based on the rolling oil.
Direct rolling oil supply method described in Section 1. 3. The direct rolling oil supply method according to claim 1, wherein the cationic or amphoteric polymer compound is selected from the group consisting of the following a○ to h○. a○ A homopolymer or a copolymer of two or more nitrogen-containing monomers or salts thereof represented by the following general formulas () to (). [R ₁ is H or CH ₃ , R ₂ and R ₃ are H or an alkyl group having 1 to 3 carbon atoms] [m ¹ is a number from 1 to 3, n ¹ is a number from 1 to 3, R ₁ , R ₂ ,
R ₃ is the same as formula ()] [R ₄ is H or an alkyl or alkylol group having 1 to 3 carbon atoms, R ₁ is the same as formula ()] [m ² and n ² are numbers from 0 to 3, R ₁ , R ₂ and R ₃ are the same as formula ()] [A is -O- or -NH-, R ₁ , R ₂ , R ₃ , n ¹
is the same as expressions () and ()] [R ₁ , R ₂ , R ₃ , n ¹ are the same as formulas () and ()] [R ₁ is the same as formula (). Pyridine substitution position is 2 or 4] [R ₁ and R ₂ are the same as formula (). The substitution position of piperidine is the 2nd or 4th position] [R ₁ , R ₂ , R ₃ are the same as formula ()] b○ One or more nitrogen-containing monomers or salts thereof represented by the above general formulas () to (),
A group consisting of α,β-unsaturated carboxylic acids or their salts, their amides, esters, or acid anhydrides, sulfonic acid group-containing vinyl compounds or their salts, acrylonitrile, vinylpyrrolidone, and aliphatic olefins having 2 to 20 carbon atoms. A copolymer with one or more vinyl monomers selected from: c○ Salts of ring-opening polymers of ethyleneimine or quaternary
grade ammonium salt. d○ Salt or quaternary ammonium salt of a condensation product of aliphatic dicarboxylic acid and polyethylene polyamine or dipolyoxyethylene alkylamine. e○ Dihaloalkane-polyalkylene polyamide condensation product. f○ Epihalohydrin-amine condensation product. g○ Cationized starch, cationized cellulose, or chitosan salt, or chitosan quaternary salt. h○ Polyether polyols with a molecular weight of 1,000 to 600,000 obtained by adding alkylene oxide to polyalkylimines having 6 to 20 nitrogen atoms. 4. The α,β-unsaturated carboxylic acid copolymerized with the nitrogen-containing monomer is acrylic acid, methacrylic acid, maleic acid, or an alkyl amide, alkyl ester, or acrylonitrile thereof, and the salt thereof is an alkali metal or ammonium salt. A direct rolling oil supply method according to claim 3. 5 The sulfonic acid group-containing vinyl compound copolymerized with the nitrogen-containing monomer is vinyl sulfonic acid, methallyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, or p-styrene sulfonic acid, and its salt is alkali 4. The direct rolling oil supply method according to claim 3, wherein the oil is metal or ammonium. 6 Anionic water-soluble polymer compounds having carboxyl groups or sulfonic acid groups in the molecule include copolymers of olefin and maleic acid, copolymers of (meth)acrylic acid and maleic acid, and copolymers of acrylonitrile and maleic acid. Copolymers, copolymers of acrylamide and maleic acid, homopolymers of (meth)acrylic acid or salts of these copolymers or homopolymers, salts or homopolymers of 2-acrylamide-2-methylpropanesulfonic acid The direct rolling oil supply method according to claim 1, which is a salt of a product or a salt of a copolymer with the monomer.