JPS59232187A - Cold rolling oil - Google Patents

Abstract

PURPOSE:To provide a cold rolling oil useful in high-speed and high pressure rolling under high shear stress and at high ratio of pressing and exhibiting excellent working stability, prepd. by adding a specified water-sol. macromolecular compd. to a lubricating oil component. CONSTITUTION:The cold rolling oil consists of about 99.9-50wt% lubricating oil component having a viscosity of below 40 cs at 40 deg.C, obtained by adding 90% or lower hydrocarbon oil (e.g. gas oil) to at least one of oil and fat such as beef tallow, mineral oil such as spindle oil and fatty acid ester such as ethylene glycol ester of beef tallow fatty acid and about 0.1-20wt% water-sol. macromolecular compd. and further contains additives. Used as water-sol. macromolecular compd. is a cationic or amphoteric polymer contg. nitrogen atom(s) in the molecule or a deriv. of natural high polymer (or salt thereof) (e.g. phosphate of diethylaminoethyl methacrylate polymer or copolymer of phosphate of diethylaminoethyl methacrylate with sodium methacrylate).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a cold rolling oil, particularly a rolling oil suitable for double reduction.

Double reduction is a method for producing ultra-thin steel sheets with high hardness (toughness) that is difficult to produce by tandem cold rolling, and the rolling oil used for this process requires various conditions, such as (a) electrolytic cleaning process. Since the oil is directly attached to the plating line and subjected to a simple acid-alkali cleaning process without a plating line, the oil must be completely degreased by the cleaning conditions alone before it can withstand plating. ) - In addition to being extremely thinly rolled, it is necessary to have a good pressure regulating effect in both shape and surface texture. The present invention is suitable for use as a cold rolling oil for double reduction as described above, and is also extremely useful as a cold rolling oil for purposes other than double reduction due to its good washability.

The rolling oil that has been commonly used in the past consists of lubricating oil components such as fats, mineral oils, or fatty acid esters, plus lubricating oil auxiliaries such as oiliness improvers, extreme pressure agents, rust preventives, and antioxidants.
This is normally supplied to the rolling department in the form of an emulsion such as 07zW type with an emulsifier at a concentration of 1 to 20%, but due to rapid advances in rolling equipment and technology in recent years, the rolling speed has increased rapidly.
With the advent of mass production, the requirements for rolling oil, such as lubricity, circulation stability, workability, and wastewater treatment properties, have become increasingly severe. There is a need for a rolling oil that can be easily cleaned from the effects of rolling oil, high lubricity that can withstand ultra-thin rolling, temper rolling properties such as shape, etc., and there is a need to develop a rolling oil that can fully meet these requirements. The current situation is that However, conventional rolling oils using emulsifiers have various drawbacks and are not satisfactory.

In other words, with conventional rolling oil using an emulsifier, the type and amount of emulsifier added can be changed to completely increase or decrease the amount of oil that adheres to the rolling oil and the surface of the rolled material (plate-out amount), thereby improving rolling lubricity. I was in control. However, in rolling oils using such emulsifiers, the amount of plate-out and emulsion stability show contradictory trends; that is, increasing the stability of the emulsion reduces the amount of plate-out in the rolled material. The lubricity becomes insufficient, resulting in rolling properties, surface contamination due to processing heat, shape defects, etc., and if the amount of plateout is not increased, the emulsion becomes unstable, resulting in sudden problems in double reduction, for example. There were inherent problems with work stability and the shape of the plate surface when ultra-thin rolling was performed.

Therefore, the present inventor conducted research to solve the above-mentioned drawbacks of conventional emulsified rolling oils, and developed a hydrophilic dispersant (a water-soluble By using an anionic polymer compound), it is stably suspended and dispersed in water in a solid state below the melting point, and becomes unstable when being supplied to the processing section, that is, above the melting point. We succeeded in improving defect (9) and filed a patent application (Japanese Unexamined Patent Publication No. 5
5-147593).

However, as the present inventor conducted further research, it was found that the rolling oil disclosed in JP-A No. 5 S-147593 was significantly improved compared to the conventional emulsified rolling oil. As shown in 1 to 4, above a certain shear condition (10.01 Orpm for a homomixer), the particles become finer and it is difficult to form a thick and strong lubricating film on the rolled metal material. found.

Therefore, the present inventor developed a cold rolling oil that can be used for rolling under high-shear conditions and high-speed, high-pressure conditions with a high rolling speed and large reduction ratio, which are assumed in practical use, and that allows for easy process control such as work stability. As a result of intensive research, it was discovered that the above object can be achieved by using a specific water-soluble polymer compound.

More specifically, conventional emulsion type products are affected by temperature changes, coagulation temperature of rolling oil, etc., and usually use hot water of 50C or higher, but specific (10) water-soluble polymer compounds are used. The rolling oil of the present invention is stabilized by the strong colloidal action of the polymer compound (no HLB balance is affected by emulsifiers), so it is not affected by temperature changes or freezing point, and is stable even at low temperatures. It can be sprayed even at low temperatures.Also, unlike conventional emulsifiers, the oil surface is made hydrophilic using a water-soluble polymer compound, and after a certain amount of the stabilized oil is attached to the active steel plate or roll surface, The oil surface is made hydrophilic so that it gets wet evenly.Therefore, once a certain amount of oil has adhered, there is no further accumulation of oil, and the adhesion is even, preventing motslinking caused by uneven oil adhesion. Furthermore, due to the extreme pressure properties of the water-soluble polymer compound, the rolling load can be reduced, power consumption can be reduced, and seizure of the steel plate with the roll can be prevented.

1 That is, the lubricating oil component of the present invention U (a lubricating oil component with a viscosity of 40 Cs/40 C or less by adding hydrocarbon oil in an amount of 90% or less to one or more of Al oil, mineral oil, or fatty acid ester) , and (b1 Contains as an essential component one or more water-soluble polymer compounds consisting of a cationic or zwitterionic polycondensate containing a nitrogen atom in the molecule, or a natural day molecule derivative or a salt thereof. The objective is to provide a cold rolling oil that

Examples of the lubricating oil component (al component) of the cold rolling oil of the present invention include spindle oil, machine oil, turbine oil,
Mineral oils such as cylinder oil; animal and vegetable oils such as whale oil, beef tallow, liver fat, rapeseed oil, castor oil, bran oil, palm oil, coconut oil; fatty acids obtained from beef tallow, coconut oil, palm oil, castor oil, etc. and aliphatic monohydric alcohols having 1 to 22 carbon atoms, ethylene glycol, neopentyl alcohol, pentaerythritol, and the like. Each of these components may be used alone, or two types may be mixed and used.

Examples of hydrocarbon oils include low viscosity paraffin and light oil, which are mixed with the above fats and oils, mineral oils, and fatty acid esters.
In addition to the amount of 0% or less, the viscosity as a lubricating oil component? 11
-40Cs/ Adjust to below 40C.

Further, as the water-soluble polymer compound of component (b), the following polycondensates can be mentioned.

(2) Homopolymers or copolymers of two or more nitrogen-containing monomers or salts thereof represented by the following general formulas (1) to (IX).

[R1 is H or CH3, and R3 is H or carbon number 1
-3 alkyl group] R1 (II) (m' is a number from 1 to 3, nl is a number from 1 to 3, R+,
R12゜R3 is the same as formula (1)] (13) ■ Melon ("4 is H or an alkyl or alkylol group having 1 to 3 carbon atoms, R1 is the same as formula (11)] R1 (IV) [m" R2 is the number of θ~3, R1, 几2.R3 is the formula %
Formula %] [A is 10- or [, -NH-1R,, R2, R3, n'
is the same as formula (11 and (11))] R1 (14) (R,, R2, R,, n' Ir1 formula (11 and (II
] (R, ld formula (same as Il. Pyridine substitution position is 2 or 4 position) I (1° (R,,, R21d formula (same as 11. Piperidine substitution position 1lSr, 2 or 4 position)) R1 [R8, 几2.R3 are the same as in formula (1)] Specific examples of these monomers include the following.

3-methacryloxy-2-hydroxypropyldimethylamine of formula (1), 3-methacryloxy-2-hydroxypropyldimethylamine, 3-methacryloxy-2-hydroxypropyldimethylamine,
2-hydroxypropylethylmethylamine, 3-methacryloxy-2-hydroxypropyldiethylamine,
3-methacryloxy-2-hydroxyprobyldiprobylamine, etc.; N,N-dimethylaminomethylene capped ethylene glycol methacrylate of the formula (■);
N,N-dimethylaminoethylene capped ethylene glycol methacrylate, N,N-dimethylamine propylene capped ethylene glycol methacrylate, N,N-dimethylaminomethylene capped diethylene glycol methacrylate, N,N-dimethylamino Ethylene-capped diethylene glycol methacrylate, N,N-dimethylamine propylene-capped diethylene glycol methacrylate, N,N-
diethylaminomethylene capped ethylene glycol methacrylate, N,N-diethylaminoethylene capped ethylene glycol methacrylate), N,N
- diethylaminopropylene capped ethylene glycol methacrylate, N,N-diethylaminomethylene capped diethylene glycol methacrylate,
N,N-diethylaminoethylene-capped diethylene glycol methacrylate, N,N-diethylaminopropylene-capped diethylene glycol methacrylate, etc.; N-2-hydroxymethyl-2 of formula (M)
-α-methylvinylimidazole, N-2-hydroxyethyl-2-α-methylvinylimidazole, N-2-
Hydroxypropyl-2-α-methylvinylimidazole, etc.; N-dimethyldiethyleneimine methacrylamide, N,N-diethylmethyleneimine methacrylamide, N.

N-diethylethyleneimine methacrylamide, N,
N-diethyldimethyleneimine methacrylamide, N
, N-diethyldiethyleneimine methacrylamide, etc. (17). (Dimethylaminoethyl acrylate, diethylamine ethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropylacrylamide, diethylamine propyl acrylamide, dimethylamine propyl methacrylamide, diethylaminopropyl methacrylamide, etc. of the formula (■); methylethylene,
Diethylaminomethylethylene, dimethylaminomethylpropene, diethylaminomethylpropene, etc.; (VID
Examples include vinylpyridine, etc. of the formula; (b) vinylpiperidine, vinyl-N-methylpiperidine, etc. of the formula 0; and (■) dimethylbenzylamine, etc. of the formula 0.

(1) One or more nitrogen-containing monomers or salts thereof represented by the general formulas Il to ω, and an α,β-unsaturated carboxylic acid or a salt thereof or a derivative thereof, a sulfonic acid group-containing vinyl compound, or A copolymer with one or more vinyl monomers selected from the group consisting of salts thereof, acrylonitrile, vinylpyrrolidone, and aliphatic olefins having 2 to 20 carbon atoms.

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; vinylsulfonic acid, methallylsulfonic acid, 2-acrylamide-2
Examples include -methylpropanesulfonic acid, p-styrenesulfonic acid, and alkali metal salts or ammonium salts of these acids.

(ψ A salt of a ring-opening polymer of ethyleneimine or a quaternary ammonium salt or a derivative thereof.

Specifically, the repeating unit is represented by the following general formula (XI)
and the average molecular weight is 1,000 to 1
There are 10 million things to list.

CH, CH2NH2 [In the formula, R3 is an integer of 1 to 5, R4 is an integer of O to 5] ■ A salt or a condensation product of an aliphatic dicarboxylic acid and a polyethylene polyamine or a dipolyoxyethylene alkylamine Quaternary ammonium salt.

Specifically, these repeating units are a condensation product with polyethylene polyamine represented by the general formula (■) and a condensation product with a dipolyoxyethylene alkylamine represented by the general formula (Xlll), with a molecular weight of 1, 000~1000
Thousands of things can be mentioned.

-(-QC-1(,,-CONI-1+R'-NH etc.-
R'-NHmo(XII) [In the formula, R7 is a dimer acid residue or an alkylene acid having 1 to 10 carbon atoms, R is -CH2CH2-, and n' is an integer of 2 to 7] (Xl[) [ In the formula, B is the same as the formula (Xll). R8 has 1 carbon number
~8 alkyl group, Ro is H or 14 CI-I,
n' and n? represents an integer of 1-10] Examples of the aliphatic dicarboxylic acids include dimer acid and adipic acid, and examples of polyethylene polyamines include:
Diethylenetriamine, triethylenetetramine, etc. can be used.

■ Dihaloalkane-polyalkylenepolyamine condensation product.

Specifically, dihaloalkanes such as 1,2-dichloroethane, 1°z-)bromoethane, and 1,3-dichloropropane, and polyalkylene polyamines having two or more tertiary amine groups in the molecule. It is a condensation product which is a quaternary ammonium salt of
o to 10 million.

Examples of the polyalkylene polyamines mentioned above include the following.

(21) (Tetramethylpropylenediamine) (Pentamethyldiethylenetriamine) ■ Epino-rohydrin-amine condensation product Specifically, the repeating unit is represented by the following general formula (X!V), and the average molecular weight is 1, 000
There are ~10,000,000 (22) of them.

-E-0-J:H2CH-1- Crystal 2 R11 [wherein R,. , 'I(,,,i CH3 or C2H
,, Xo represents... rogane ion] ■ Salt of chitosan or cationically modified product of starch or cellulose.

(2) A polyether polyol or fl polyol polyether derivative having a molecular weight of 6 to 600,000, which can be obtained by adding an alkylene oxide to a polyalkylimine having 6 to 200 nitrogen atoms or a derivative thereof.

The polyalkylene polyamine has five or more consecutive skeletons represented by the following formula (XV) in the molecule, and one or more of them is a skeleton represented by the following formula (XVI), and the terminal ends with 01- (Nitrogen atom 6, which is cleverly NH2
-100 polyethyleneimines are preferred.

-C1-12-O1 (2N≦ (XV)
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 8 ( )% by weight is preferred.

The polycondensates of the above ■ to ■ have an average molecular weight of 1 tl.
Ofl to 10,000 is more preferable.

Furthermore, examples of the counteranion forming the salt of the polycondensate include the following (1) to (2).

(1) Phosphoric acid, phosphorous acid, or their thio or ester compound CI+) E- or syric acid ester having one or more hydroxyl groups in the alkyl, alkylaryl, or allyl group, or their thio compound (iii) Carbonial~ Mono- or diphosphonic acids having 8 alkyl, alkylaryl or allyl groups or thio compounds thereof or derivatives thereof Ov) Mono- or diphosphinic acids having all alkyl, alkylaryl or allyl groups having 1 to 8 carbon atoms or thio compounds thereof or derivatives thereof (V) mono-, di-, or triphosphonic acid containing a nitrogen atom (vl) boric acid Specific examples of this phosphoric acid compound include the following.

Examples of (1) include orthophosphoric acid, phosphorous acid, and carbon number 1.
- 8 mono- or silicic acid esters of aliphatic, alicyclic or aromatic alcohols and orthophosphoric acid, or thio compounds thereof, or phosphite esters of the above-mentioned alcohols, or these thio compounds are exemplified. An example of (11) is 2-hydroxypropyl phosphate. [25] Phosphonic acids represented by a ru group, an alkylaryl group, or an allyl group], such as methylphosphonic acid having 1 carbon number, dimethylphosphonic acid to n-octylphosphonic acid having 8 carbon atoms,
Moro-octylphosphonic acid, 2-ethylhexylphosphonic acid, di-2-ethylhexylphosphonic acid, benzylphosphonic acid, dibenzylphosphonic acid, phenylphosphonic acid, diphenylphosphonic acid, hydroxyethane diphosphonic acid, and thiophosphonic acid thereof An example is an acid. Hydroxyethane diphosphonic acid is a compound represented by the following formula.

f-10-1'-C-P-OH 111 0H01-10H (26) Phosphinic acid, such as methylphosphinic acid with 1 carbon number, dimethylphosphinic acid to n-octylphosphinic acid with 8 carbon atoms, moro-octylphosphine acid, 2-ethylhexylphosphinic acid, di-2-ethylhexylphosphinic acid, benzylphosphinic acid, dibenzylphosphinic acid, phenylphosphinic acid, diphenylphosphinic acid,
Also, these thiophosphinic acids are exemplified. IVI
Examples of the organic compound include hexamethylphosphoric mono(or di)amide and nitrilotrismethylenephosphonic acid. Nitriloto 1 Rismethylenephosphonic acid is a compound represented by the following formula.

The following margin HO-P=0 i-I The cold rolling oil of the present invention is prepared by blending each of the above components, and the blending amount is (al
The lubricating oil component of the component is 99.9 to 50 weight (hereinafter simply referred to as ``chi''), especially 99.9 to 70 weight, (the water-soluble polymer compound of the BL component is 0.1 to 20 weight, especially 0. 1-10
Person in charge is preferred.

In addition to the above-mentioned components, the cold rolling oil of the present invention may contain various known additives, such as rust preventives, oiliness improvers, extreme pressure agents, antioxidants, etc., as necessary.

The above various additives may be added in an amount of 0 to 2%, 0 to 20%, 0 to 3%, and 0 to 5%, respectively, based on the total amount of cold rolling oil as necessary.
It can be added at a ratio of .

As rust inhibitors, alkenylsuccinic acid and its derivatives,
Fatty acids such as oleic acid, esters such as sorbitan monooleate, or other amines, etc. are used as oiliness improvers. In addition, as extreme pressure agents, phosphorus compounds such as tricresyl phosphate and organometallic compounds such as zinc dialkyldithiophosphate are used, and as antioxidants, phenols such as 2,4-di-t-butyl p-cresol are used. system compounds,
Examples include aromatic amines such as phenyl α-naphthylamine.

The cold rolling oil of the present invention is used by simply mixing the above components before use, or by preparing a concentrated solution with a water content of up to about 80% and diluting it with water before use.

The thus obtained cold rolling oil of the present invention has a relatively large, uniform particle size and stable particle size distribution under stirring conditions with high shear force, and the rolling oil is uniformly spread over the steel sheet surface in tx by ftN.
(29) It provides rolling oil with smooth rolling performance and little change over time, and also has the following five features. That is, the water-soluble polymer compound used in the present invention itself has the ability to quickly adsorb to liquids and solid particles and make them hydrophilic, but it has the ability to lower the interfacial tension between water and oil and emulsify it. Since it does not have any emulsification, the lubricating oil components do not become emulsified, and compared to rolling oils that use conventional emulsifiers, there is less of the so-called entrapment phenomenon of dirt, oil, and foreign substances such as dull powder that occur during operation. ,
As a rolling oil that is always clean, it can eliminate problems such as mottling by achieving a homogeneous wetting state, rather than the emulsion-repelling state that adheres to the steel plate as in the case of emulsifiers, and is also water-resistant. It has the advantage of maintaining high lubrication properties due to the extreme pressure effect caused by the counter ions of the polymer compound.

In addition, due to the functions of the above ingredients, dirt in the working environment is improved and wastewater treatment properties are also excellent. The cold rolling oil having the characteristic (30) is particularly suitable for double reduction.

Although the mechanism of action of the water-based polymer compound in the present invention has not been completely elucidated, it is thought to be roughly as follows. That is, the water-based polymer compound completely uniformly dissolved in the water layer absorbs the particles of the lubricating oil component, which have been made into fine particles in response to mechanical shearing force, before they begin to coalesce, and the polymer compound The compound makes oil particles into large particles through a kind of aggregation effect, and the sterically and electrically protective colloid effect of the polymer compound allows the large particles to be stably dispersed in water.

In the case of the water-soluble anionic polymer compound disclosed in JP-A No. 55-147593, the agglomerating effect on oil particles is weak, so the fine particles are stabilized as captured colloids, and once they are made fine, they are stabilized as colloids. This is different from not being able to recover oil particles into larger particles.

Next, an example will be given and explained.

Water-soluble polymer compound: (5) Polymer of diethylaminomethyl methacrylate 'k IJ phosphate (MW = 3 million tons (B-1
) Borate of diethylamine ethyl methacrylate/vinylpyrrolidone/sodium acrylate = 5/4/
]-(expressed in molar ratio. The same applies below for the wood surface) copolymer (MW = 200,000) CB-2) (M
W = 50,000) CB-3) (MW = 15
t) tl ) (C) Phosphate of diethylamine ethyl methacrylate/copolymer of sodium methacrylate 415 (MW = 20,000) (D-1) Phosphate of ring-opening polymer of ethyleneimine (M
W=10,000] <D-2) Phosphite of ring-opening polymer of ethyleneimine (
MW=700) CD-3) 5 for polyethyleneimine (MW=70,000)
% Myristicin ek reaction was made into ethyl phosphinate (E) Ethyl phosphonate of dimethylaminoethyl methacrylate/2-acrylamide-2-methylpropanesulfonic acid sodium"' 4
/ l copolymer [MW=100,000] CF) Vinylpyridine phosphate/vinylpyrrolidone/
Sodium acrylate = 6/3/l copolymer (MW = 45
(G) Polycondensate metal of diethylenetriamine thiophosphate and dimer acid (MW = so 10,000) (H) Diethylamine ethylmethacrylamide phosphate/sodium acrylate/sodium vinyl sulfonate = 3
/1 Copolymer of /1 (MW = 400,000) CI) Water-soluble polymer compound (D) with ethyleneimine phosphate as borate (J) Quaternary ammonium of cationically modified cellulose Salt (MW = 10,000) (Io Polycondensate of phosphate of 112-dichloroethane and hexamethylenetetramine (MW = s, 10,000) (L) Ring-opening of phosphite of trimethylamine quaternary ammonium compound of epichlorohydrin Polymer (MW=10,000) CM) Tetramethylpropylene diamine diethyl (33
) Polycondensate of quaternary ammonium salt with phosphonic acid (
MW=100,000) (N) Compound of dimethylamine ethyl methacrylate phosphate/Na salt of 2-acrylamido-2-methylpropanesulfonic acid = 2/1 (MW=30,000) (0) Dimethyl Copolymer of aminoethyl methacrylate phosphate/acrylamide = 3/l (MW = 10,000) CP) Water-based polymer compound (E) dimethylamine ethyl methacrylate ethyl phosphonate total hydrochloride (Q) Phosphate of ethyleneimine (in water-soluble polymer compound) Total acetate (R) Quaternary ammonium salt of vinylpyridine with dimethyl sulfate/vinylpyrrolidone/sodium acrylate=
6/3/l copolymer (MW = 450,000) (S) Addition of 20% ethylene oxide to total polyethyleneimine (34) MW = 50,000) and phosphate (T) Add 30 parts of ethylene oxide and 30 parts of propylene oxide to polyethyleneimine.
W = 150,000), phosphite (U) phosphonic acid group of ethyleneimine/ethyl phosphinate of dimethylamine ethyl methacrylate = l/1
Copolymer of (MW = 60,000) or less margin (37 Example 1 Seizure resistance load test (Falex test method) Seizure resistance load test was carried out in accordance with ASTM standard D-3233 pressure load test (Falex test). .Preparation of the test sample is as follows:
Each cold rolling oil was diluted with water to a concentration of 3%, and this was stirred using a homomixer at a rotation speed of IQ and OO rpm. To apply the test sample, spray the above stirred solution at an amount of 5 (1 mE) for 7 minutes (pressure: 0.5 kg).
7cm2) and a dispersion temperature of 50C, a gear pump was used and the coating was applied to the rotating pin at the center of the fixed block.

The results are shown in Table 2.

Blank space below (38) Example 2 Seizure load test (four-ball test method) Seizure load was measured according to the Defense Agency provisional standard NDS XXI (2
The test was conducted according to the 740 oil film strength test method (deployment four-ball test method). To prepare the test sample, each cold rolling oil was diluted with water to a concentration of 3.
．． Stir at Ofl Orpm.

To apply the test sample, spray the above stirred solution in an amount of 0.5,
．． Using a gear pump under the conditions of 0.7 minutes (pressure 0.5 ky/crn2) and a sample solution temperature of 50C, the test was carried out from below the three test steel balls fixed with ball holders through the space at the center of the three contact points. This was done by applying it to the rotating steel ball above.

The results are shown in Table 3.

Below is the margin Example 3 Particle size measurement To prepare the test sample, each cold rolling oil was diluted with water to a concentration of 3%, brought to a temperature of 60°C, and rotated with a homomixer at a rotation speed of 10.00 t) for 60 minutes. This was done by stirring. The particle size of the test sample was measured using the Coulter counter method using a 21) 0 μm aperture.

The results are shown in Table 4.

Margin below (42) Example 4 Coating amount test To prepare the test sample, dilute each cold rolling oil to 3 parts with water, bring it to a temperature of 60C, and use a homomixer! +1
This was done by stirring at 0.00 rpm for 60 minutes. The test sample was applied to a surface-cleaned steel plate (50X
150X0.2 +11111) at a temperature of 150C
and spray amount 5oo++tl/min (pressure 1kg 7
cm") using a gear pump for 2 seconds. The amount of adhesion was measured by extracting the coated steel plate with a solvent using a solvent. The results are shown in Table 5. .

Below is a blank space Example 5 The test liquid (IJ) prepared in the same manner as in Example 2 of the wastewater treatment test was added with pan sulfate ±
3? After the addition, the mixture was stirred for 2 minutes, and then Ca(0) was added to adjust the pH to 7.0, followed by stirring for 10 minutes. Then, after standing still for 30 minutes, the subnatant liquid was collected and COD (KMnO, method)
Measure the position.

The results are shown in Table 6.

Blank space below (46) Table 6 (47) Supplementary procedural devices (methods) 1. Description of the case 1983 Patent Application No. 108380 2 Name of the invention Cold rolling oil 3 Relationship to the case by the person making the amendment Patent applicant address 1-14-10, Kayaba-cho, Nihonbashi, Chuo-ku, Tokyo Name Name (091) Kao Soap Co., Ltd. Representative Yoshibe Maruta Address 1-1-2 Marunouchi, Chiyoda-ku, Tokyo Name Name
(412) Nippon Kokan Co., Ltd. Representative: Minoru Kaneo 4, Agent address: 1-3-6 Nihonbashi Ningyocho, Chuo-ku, Tokyo (?
103) 5. Date of amendment order: September 27, 1982 (dispatch) 6. Full text of the specification to be amended 7. Engraving of the specification of the contents of the amendment (no change in content) 2- 610-

Claims (1)

[Claims] (1(a) Hydrocarbon oil in an amount of 90% or less is added to one or more of fats, oils, mineral oils, or fatty acid esters to obtain a viscosity of 40 CS / 40 C or less. A lubricating oil component, and one or two of a cationic or zwitterionic addition polymer, a ring-opening polymer, a polycondensation product, or a natural polymer derivative or a salt thereof containing a nitrogen atom in the molecule.
A cold rolling oil characterized by containing at least one water-soluble polymer compound as an essential component. (2) The cold rolling oil according to claim 1, wherein the salt-forming counteranion is a compound selected from the group consisting of the following (I) to D. (1) Phosphoric acid, phosphorous acid, or thio or ester compounds thereof (11) Mono- or syringic acid esters having one or more hydroxyl groups in the alkyl, alkylaryl, or allyl group, or thio compounds thereof cm) C1-C Mono- or diphosphonic acids having 8 alkyl, alkylaryl or allyl groups or thio compounds thereof or derivatives thereof qv) Mono- or diphosphinic acids having alkyl, alkylaryl or allyl groups having 1 to 8 carbon atoms or thio compounds thereof or a derivative thereof (V) a nitrogen atom-containing mono-, di-, or triphosphonic acid to 1) boric acid (3) a water-soluble polymer compound selected from the group consisting of the following ■ to ■. Cold rolling oil according to item 1. ■ A homopolymer or a copolymer of two or more nitrogen-containing monomers or their salts represented by the following general formulas (11 to (■)). H or carbon number 1~
3 alkyl group] R1 (m+ is the number of 1 to 3, n,', ld l is the number of 3, R
1゜''21!'8 is the same as the formula (1)] 4 C''4 is H or an alkyl or alkylol group having 1 to 3 carbon atoms, R.1 is the same as the formula CI+]R. (IV) (m2 and R2 are the numbers of O to 3, R1, R are the same as the formula (1>)] [A is -〇- or -NH-1'R, R2, R3',
n' is the same as formula (1) and (Ill) R7 [1(+1.R2, R3, n' is the same as formula (I) and (Ill)
l Same as above] R1 [Rt is the same as formula (11. Substitution position of pyridi/ is 2 or 4
Rank] 几. [Rt, 'R2u formula (same as 11. 2nd or 4th substitution position of piperidine)] (R,,,11,2+' R3 is the same as formula (I))
one or more nitrogen-containing monomers or salts thereof represented by the general formulas (I) to m, and α. β-unplated carboxylic acid or a salt thereof or a derivative thereof,
A copolymer with one or more vinyl monomers selected from the group consisting of sulfonic acid group-containing vinyl compounds or salts thereof, acrylonitrile, vinylpyrrolidone, and aliphatic olefins having 2 to 20 carbon atoms. ■ Salts of open polymers of ethyleneimine or quaternary ammonium salts or derivatives thereof. ■ Salts or quaternary ammonium salts of condensation products of aliphatic dioxylic acids and polyethylene polyamines or dipolyoxyethylene alkylamines. ■ Dihaloalkane-polyalkylenepolyamine condensation product. ■ Shrimp halohydrin-amine condensation polymer. ■ Chitosan salt, starch or cellulose, or cationically modified products thereof. (5) (5) A polyether polyol or a polyol polyether derivative having a molecular weight of 600 to 600,000, obtained by adding an alkylene oxide to a polyalkylimine having 6 to 200 nitrogen atoms or a derivative thereof. (4) The α,β-unsaturated carboxylic acid copolymerized with the nitrogen-containing monomer is acrylic acid, methacrylic acid, or maleic acid, and the salt thereof is an alkali metal or ammonium, and!
4. The cold rolling oil according to claim 3, wherein the derivative is an alkyl amide, an alkyl ester or acrylonitrile. (5) The sulfonic acid group-containing vinyl compound copolymerized with the nitrogen-containing monomer is vinyl sulfonic acid, methallyl sulfonic acid, 2
- acrylamide-2-methylpropanesulfone fi,
The cold rolling oil according to claim 3, which is Up-styrene sulfonic acid and the salt thereof is an alkali metal or ammonium salt. (6) The amount of water-soluble polymer compound is 0.1 (6) of the total composition.
) to 20% by weight, the cold rolling oil according to any one of claims 1 to 5.