US3654156A

US3654156A - Lubricants for cold rolling and manufacturing the same

Info

Publication number: US3654156A
Application number: US801164A
Authority: US
Inventors: Yoshio Ishii; Shizuyoshi Sakai; Shoji Shimada; Kikuro Kurokawa; Rokuji Suzuki; Nobuo Fukuda
Original assignee: Daido Chemical Industry Co Ltd
Current assignee: Daido Chemical Industry Co Ltd
Priority date: 1968-02-23
Filing date: 1969-02-20
Publication date: 1972-04-04
Anticipated expiration: 1989-04-04

Abstract

A LUBRICANT FOR COLD ROLL IS DISCLOSED WHICH COMPRISES AN ADDITION PRODUCT OF AN EPOXY COMPOUND AND AN OXIDATION PRODUCT OF AN ALIPHATIC HYDROCARBON HAVING AN ACID VALUE OF 30 TO 110; SAID ADDITION PRODUCT HAVING AN ACID VALUE OF 0 TO 30 AND CONTAINING SAID EPOXY COMPOUND IN THE MOLECULE IN AN AMOUNT SUFFICIENT TO REDUCE AT LEAST 60 PERCENT OF THE ACID VALUE OF SAID OXIDATION PRODUCT; AND SAID OXIDATION PRODUCT OF THE HYDROCARBON BEING PREPARED BY CONTACTING AT 100 TO 180*C. AN ALIPHATIC HYDROCARBON HAVING 15 TO 55 CARBON ATOMS WITH MOLECULAR OXYGEN.

Description

United States Patent Oflice 3,654,156 Patented Apr. 4, 1972 US. (:1. 252-495 6 Claims ABSTRACT or THE DISCLOSURE A lubricant for cold roll is disclosed which comprises anraddition product of an epoxy compound and an oxidation'product of an aliphatic hydrocarbon having an acid value of 30to 110; said additionproduct having an acid value of to 30 and containing said epoxy compound in the molecule in an amount sufficient to reduce at least 60 percent of the acid value of said oxidation product; and said oxidation product of the hydrocarbon being prepared by contacting at ,100 to 180 C. an aliphatic hydrocarbon having 15 to 55 carbon atoms with molecular oxygen.

This invention relates to a lubricant for cold rolling and a process for manufacturing the same.

" In the cold rolling of steel strip, it is necessary to apply a lubricant on the strip which passes through the pressure rolls. The quality of the lubricant used determines, to a large extent, the speed at which the mills are to be operated and the pressure to be applied as Well as the flatness, surface appearance and characteristics of the resultant cold rolled sheet.

Therefore, it is desired for'the lubricant to have the following properties:'

1) Causinglittle or no oil stains during a cold rolling step,thereby making it possible to produce a metal sheet having good surface appearance;

(2) Having a low order of mean yield stress, so as to reduce the roll pressure required for the production of a rolled metal sheet having a desired thickness; and

(3) Having low viscosity and good water-dispersibility, so that the lubricant can be spread quickly and completely under operating conditions in which Water is used as a coolant in connection therewith.

In the prior art palm oil has been widely used as a lubricant for cold rolling, but it fails to meet the requirements of todays cold rolling procedures which call for higher speed because of the progress in rolling techniques.

' For instance, the mean yield stress of palm oil is not sufiiciently low and the Water-dispersibility thereof is somewhat poorfor use-in the high-speed rolling of today. Further, it causes, considerable undesired oil stains during the high-speed cold rolling step.

To eliminate the drawbacks of palm oil as above mentioned many attempts have beenmade, but none of the lubricants so far proposed have proved to be superior to palm oil.

It is an object of the invention, accordingly, to provide a lubricant having improved properties for cold rolling as compared to palm oil.

Another object'of the invention is to provide a lubricant which will meet the severe rolling'mills.'--

requirements of high-speed v A further object of the invention is to provide a method for producing a lubricant having the above characteristics from materials available in large quantities.

These and other objects of the invention will be apparent from the description to follow.

According to the present invention, specific addition products of epoxy compounds and oxidation products of aliphatic hydrocarbons having an acid value of 30 to are used as lubricant for cold rolling.

The specific addition products of the invention are prepared by the addition reaction of epoxy compounds and oxidation products of aliphatic hydrocarbons having an acid value of 30 to 110. The addition product should have an acid value of 0 to 30 and contain the epoxy compounds in the molecules in an amount sufficient to reduce at least 60 percent of the acid value of the oxidation products. This reduction rate of the acid value is determined by the following equation:

Reduction rate of acid value (percent)= 2 X 100 in which A is the acid valuve of the oxidation product and B is the acid value of the resultant addition product.

The present inventors have found that when the above specific addition product is used as a lubricant for cold rolling it displays excellent lubricating effects, superior to those of palm oil.

For example, the mean yield stress thereof is lower than that of palm oil. Further, it causes less oil stains even in high-speed rolling and can be spread quickly and completely even under operating conditions in which water is used as a coolant.

The oxidation products of hydrocarbons used for the production of the above specified addition products are prepared by contacting at 100 to 180 C. aliphatic hydrocarbons having 15 to 55 carbon atoms with molecular oxygen.

The starting saturated aliphatic hydrocarbons of having 15 to 55 carbon atoms are available in large quantities and representatives thereof are, for example, parafiin wax, low polymers of ethylene, paraffins obtained by the thermal decomposition of long chain n-paraffins, etc. Accord ing to the present invention the aliphatic hydrocarbons are oxidized by contacting them with molecular oxygen to produce oxidation products of hydrocarbons having an acid value of 30 to 110. For the molecular oxygen, oxygen gas may be used alone or in combination with a diluent gas, such as nitrogen, argon, carbon dioxide, steam, etc. When the oxygen gas is diluted it is preferable that the resultant oxygen-containing gas contains oxygen in at least 5 percent by volume. Air is the most desirable source of the molecular oxygen. The oxidation reaction of the hydrocarbons with the molecular oxygen is a gas-liquid phase reaction in which oxygen-containing gas is brought into contact with liquid hydrocarbons melted if necessary. In the present process various conventional methods may be employed for contacting the gas with the liquid. For instance, oxygen-containing gas, such as air, may be contacted with hydrocarbons by blowing it into liquid hydrocarbons through porous materials or it may be contacted therewith by shaking the liquid in the oxygen-containing gas atmosphere or by using an ejector, turbine. or a like. conventional device for contacting gas with liquid.

The reaction temperature of the oxidation reaction should be in the range of 100 to 180 C. At lower temperatures the reaction cannot proceed effectively,

while at higher temperatures undesired decomposition of the starting hydrocarbons occursYThe preferred reaction temperature is in the range of to C. The. reaction pressure is usually atmospheric pressure, though increased or reduced pressures may also be employed. To accelerate the reaction various catalysts may be used, as required. Examples thereof are peroxides, azo compounds, or salts or oxides of transition metals, such as manganese, chromium, vanadium, cobalt, nickel, copper, lead, iron etc. The reaction time may vary in accordance with the reaction conditions, but usually 0.5 to 50 hours reaction is sufficient to effect the desired result.

By gas chromatographic and infrared spectroscopic analyses and the measurement of molecular weight, acid value, saponification value, hydroxyl value, carbonyl value and iodine value the resultant oxidation products have been determined to be a mixture of various compounds having different molecular weight and structures. The molecules comprise such functional groups as carboxyls, carbonyls and hydroxyls depending upon the degree of oxidation thereof. Therefore, the structural formula of the oxidation products of the hydrocarbons cannot be precisely defined. The present inventors, however, have found that the acid value of the resultant oxidation products is an important factor in producing the specific addition products useful for the present invention and that when the acid value is in the range of 30 to 110 a desirable lubrication can be obtained by the subsequent addition reaction referred to hereinbefore and hereinafter. The lubricant of the present invention cannot be produced from oxidation products having lower or higher acid values. For example, oxidation products having an acid value of lower than 30 result in the production of a lubricant having high degree of mean yield stress as well as high friction resistance, which are undesirable, while oxidation products of acid values of higher than 110 result in the production of undesired resinous byproducts. The preferred acid value of the oxidation product is in the range of 50 to 100. The oxidation products of the present invention having a 30 to 110 acid value usually have a saponification value of 60 to 400 and an average molecular weight of 250 to 800. The characteristics, however, are not so critical in the production of the present lubricant and may vary over a wide range ac cording to the starting hydrocarbons and the oxidation conditions applied.

The resultant oxidation product of the aliphatic hydrocarbon is subsequently reacted with epoxy compounds as it is or after removing low boiling byproducts, whereby the epoxy group in the epoxy compound is reacted with the carboxyl group in the oxidation products to produce the desired addition compound.

The epoxy compounds used in the invention are represented by the following formula:

wherein R is one member of the group consisting of hydrogen atom, alkyl group of 1 to carbon atoms, hydroxymethyl group, chloromethyl group, acyloxymethyl group of 2 to 7 carbon atoms, carboalkoxylrnethyl group of 2 to 7 carbon atoms, alkoxymethyl group of 2 to 7 carbon atoms, phenoxymethyl group and phenyl group; and R and R are respectively one member of the group consisting of hydrogen atom and a lower alkyl group of l to 3 carbon atoms; and when R and R are alkyl and R is hydrogen R and R may constitute a cycloalkyl group by being bonded to each other at their end positions. Representative compounds are, for example, epoxyethane, epoxypropane, 1,2-epoxybutane, 2,3-epoxybutane, epoxyisobutane, 1,2-epoxyhexane, 1,2-epoxydodecane, 4,5- epoxydodecane, 1-oxy-2,3-epoxypropane, epichlorohydrin, 1,2epoxycyclohexane, styrene oxide, phenyl glycidyl ether and the like.

Of these epoxy compounds the most desirable compounds are those having the structural formula in which R is hydrogen or a lower alkyl group of 1 to 2 carbon atoms and R and R are hydrogen. Representative compounds are epoxypropane and 1,2-epoxybutane.

The addition reaction may be carried out in the presence or absence of catalysts at a temperature higher than the melting point of the oxidation products of the hydrocarbons. The epoxy compound may be used in an amount necessary for reducing at least 60 percent of the acid value of the oxidation product and for producing addition products with an acid value of O to 30. Such an amount may be determined from the acid value of the oxidation product, since it has been determined that the acid value of the oxidation products is in proportion to the number of the carboxyl groups contained in the oxidation product and the epoxy compound is reacted with the carboxyl groups to reduce the acid value. Though from a theoretical viewpoint one mole of the epoxy com pound will react with one of the carboxyl groups, part of the epoxy compound used may be self-polymerized, so that the epoxy compound preferably is used in an excess amount. Usually it is used in the calculated amount or in an excess amount not higher than 200 percent of the calculated amount (mole). Most preferably the epoxy compound is used in 10 to 30 percent excess in the calculated amount. The reaction temperature may usually be between 60 and 250 C., and is preferably between and C. The reaction pressure may vary over a wide range, but usually it may be atmospheric pressure or an increased pressure of less than 20 kg./cm. To accelerate the reaction conventional catalysts used in the polymerization of epoxy compounds may be-used. Examples of the catalysts are triethyl amine, tributyl amine, pyridine, tributyl phosphate, potassium phosphate, ammonium phosphate, triethyl phosphite, phosphoric acid, sulfuric acid, boron trifiuoride, sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, manganese oxide, etc. The reaction may be carried out in the presence or absence of inert solvents, such as benzene, toluene, xylene petroleum ether and the like.

The reaction time may vary in accordance with the reaction conditions applied, but usually 0.5 to 30'hour's reaction is sufiicient for the purpose.

By gas chromatographic and infrared spectroscopic analyses and the measurement of molecular weight, acid value, saponification value, carbonyl value and hydroxyl value, the resultant addition product has been found to be a mixture of various products. The epoxy compound is added to the oxidation products of hydrocarbons resulting in different structures depending on the degree of the oxidation, so that as with the oxidation products, it is impossible to determine the precise structure of the addition product. The present inventors, however, have found that the resultant addition product is useful as a lubricant for cold rolling and meets the severe require: ments of the recent high-speed rolling mills, when the acid value thereof is within the range of 0 to 30 and the reduction rate of the acid value defined before is more than 60 percent, irrespective of other characteristics of the addition compounds. The preferable acid value of the addition compound is from 2 to 20. Though the addition products may contain byproducts such as polymers of the epoxy compound, there is no need to remove them as the amount thereof is small and such byproducts do not adversely affect the lubricating properties of theaddition compounds.

In fact, when the present addition product having an acid value of 0 to 30 is used as lubricant for cold rolling it displays marked advantagesover those. of palm oil and can advantageously be used as a lubricant for cold rolling at high speeds without any objections. The addition product of the invention desirably has an average molecular weight of 280 to 800.

The addition product may be used as a lubricant for cold rolling as it is, but it is usually to be used in the form of an aqueous dispersion and the addition compound is usually in a concentration of 1 to 30 wt. percent, preferably to 25 wt. percent. The lubricant of the invention can-be used" for the cold rolling of steel sheets and plates having various thicknesses.

For. example, it displays excellent lubricating effects even in cold rolling for producing steel sheet less than 0.19 mm. in thickness. It may also be admixed with animal or vegetable oil-based lubricants, such as tallow, lard, whale oil, palm oil, castor oil or rape seed oil, in an amount of 1 to 30'percent' by weight to improve the lubricating properties thereof. In fact, such admixed oils can effectively be used in cold rolling for producing steel sheets of 0.19 to 0.30 mm. in thickness and gives better results as compared with use of the animal or vegetable oil-based lubricants alone. For the production of thicker steel plates, the lubricant of the invention may be admixedin an amount of 1 to 30 percent by weight with a conventional petroleum lubricant to improve the lubricating properties thereof.

To the lubricant of the invention there may be added conventional additives, such as rust inhibitors, surfactants, extreme pressure additives, antioxidants, antifoaming agents, etc.

For better understanding of the invention examples are given below.

EXAMPLE 1 Petroleum parafiin Wax having an average of 27 carbon atoms per molecule was melted at 60 C., and manganese naphthenate was added in a proportion of mole per kilogram of the wax. kg. of the mixture thus obtained was placed in a cylindrical stainless steel reactor of 250 mm. in diameter, and 3,000 mm. in height and, while heating the mixture at 160 C., air was blown from the bottom of the reactor in a proportion of 2 l./min./kg. of the wax for hours. 14.25 kg; of product was obtained.

By gas chromatographic and infrared spectroscopic analyses the substance thus obtained was determined to be a mixture of various oxidation products having different structuresand it 'had the following characteristics: Melting pointi'41? C."

Acid'value': 68.0 Saponification value: 243.5

To 12.5 kg. of the resultant oxidation product melted at 60 C. was added 56.4 g. of a 50 weight percent aqueous solution of potassium hydroxide and the mixture was placed in -a 20 liter autoclave. To the mixture was added 800 grams of epoxyethane and the resultant mixture was heated with stirring at 135 C. under a pressure of 4 kg./cm. for 5 hours. Removal of the unreacted epoxyethane gave 13.2 kg. of waxysubstance.

By gas chromatographic andinfrared spectroscopic analyses the resultant substance was determined to be a mixture of various addition products of the oxidation product and epoxyethane, and it had the following characteristics:

Melting point: -39 C.

Acid value: 20.0

Saponification 'value: 220

Melt viscosity (at 50C.): 89 cst.

EXAMPLE 2 12.5 kg. of an oxidation product prepared in the same manner as in Example 1 was reacted with 1 kg. of epoxyethane in the same manner as in. Example 1, whereby 13.1 kg. of addition product having the following characteristics was obtained.

Melting point: 38 C.

Acid value: 10.8

Saponification value 206' Melt'viscosity'(at 50 C.): 84 cst.

EXAMPLE 3 12.5 kg. of an oxidation product prepared in the same manner as in Example 1 was reacted with 1.13 kg. of

epoxyethane in the same manner as in Example 1, whereby 13.2 kg. of addition product having the following characteristics was obtained.

Melting point: 36 C.

Acid value: 2.5

Saponification value: 202

Melt viscosity (at 50 C.): 79 cst.

In 80 parts by weight of water were dispersed 20 parts by Weight of the respective addition products of Examples 1 to 3 to produce lubricants for cold rolling.

For comparison four kinds of lubricants were prepared in the same manner as above by dispersing the followin substances in water respectively.

Comparison 1: Palm oil Comparison 2: Oxidation product of hydrocarbon prepared in the same manner as in Example 1.

Comparison 3: Addition product of the oxidation product of hydrocarbon as in Example 1 with epoxy ethane, which was prepared in the same manner as in Example 1 except that 66.5 g. of epoxy ethane was used.

Comparison 4: Addition product of the oxidation product of hydrocarbon as in Example 1 with epoxy ethane, which was prepared in the same manner as in Example 1 except that 335 g. of epoxy ethane was used.

The respective lubricants thus prepared were used as lubricants for cold rolling and the rate of oil stain, mean yield stress and water-dispersibility thereof were measured by the following methods, with the results shown in Table 1 below:

(Rate of oil stain) Each lubricant was uniformly sprayed on a steel plate, 10 x 10 cm., at the rate of 0.5 g./cm. Thereafter another steel plate of the same size was placed on it and left under pressure of 13 ton/ cm. at C. for 12 hours. The area (percent) of oil stain created was measured and the rate of oil stain was determined by the following equation:

Rate of oil stain (percent) Area of oil stain created (cm?) (Mean yield stress) Mild steel sheet of 30 mm. in width and 1 mm. in thickness was rolled by pressure rolls of mm. in diameter and 200 mm. in Width at a rolling speed of 13 m./min. and at a temperature of 60 to 65 C. for three turns. The curve of reduction-mean yield stress was obtained in known manner and the mean yield stress at 75' percent reduction is shown in Table 1 below.

(Water-dispersibility) The respective lubricants, immediately after preparation were left to stand at room temperature for 5 minutes, and the volume of the layer separated was measured.

No'rn.E.O. (moles) represents number of mole of ethylene oxide used per one COOH group in oxidation product.

7 EXAMPLE 4 15 g. of potassium permanganate was added to 10 kg. petrolatum having a melting point of 54 C. and heated to a temperature of 120 C. The mixture was placed in a 20 liter autoclave. Then the mixture was heated at 150 C., into which air was blown in a proportion of 2 l./min./kg. of the petrolatum for 20 hrs. The pressure in the autoclave was maintained at 2.5 kg./cm. 9.8 kg. of product was obtained.

By gas chromatographic and infrared spectroscopic analyses the substance thus obtained was determined to be a mixture of various oxidation products and it had the following characteristics:

Melting point: 50 C.

Acid value: 89

Saponification value: 258

Melt viscosity (at 100 C.): 167 cst.

Melting point: 47 C.

Acid value: 11

Saponification value: 254.1

Melt viscosity (at 100 C.): 162 cst.

parts by weight of the resultant addition product was dispersed in 95 parts by weight of water, and the rate of oil stain and mean yield stress of the lubricant thus obtained were measured in the same manner described with reference to Examples 1 to 3, with the following results.

Rate of oil stain (percent): 5 Mean yield stress (kg/mini): 130

EXAMPLE 5 1 kg. of paraffin having a melting point of 38 C. and an average of 18 carbons per molecule was melted at 60 C., to which g. of benzoic peroxide was added, and the mixture was placed in a 2 liter flask. The resultant mixture was heated at 110 C. and air was blown into the mixture in proportion of 2 l./min./kg. of the paraffin for 3 hours. 1.01 kg. of oxidation product having the following characteristics was obtained.

Melting point: 33 C.

Acid value: 49

Saponification value: 161

Melt viscosity (at 100 C.): 25.4 cst.

1 kg. of the resultant oxidation product was melted at 80 C., to which was added 20* g. of a weight percent ether solution of trifluoroboron ethylate, and the mixture was placed in a 2 liter autoclave. To the mixture 220 g. of epoxypropane was added and the resultant mixture was heated with stirring at 120 C. under pressure of 4.5 kg./cm. for 2 hours. 1.1 kg. of addition product having the following characteristics was obtained.

Melting point: 31 C.

Acid value: 4.5

Saponification value: 154

Melt viscosity (at 100 C.): 18.6 cst.

10 parts by weight of the resultant addition product was dispersed in 90 parts by weight of water, and the mean yield stress of the resultant lubricant measured in the same manner as described with reference to Examples 1 to 3 was 149 kg./mm.

' Melt viscosity (at C 24.5 cst.-

8 EXAMPLE 6 Melting point: 41 C.

Acid value: 72 Saponification value: 241 Melt viscosity (at 100 C.): 38.3 cst.

The resultant oxidation product wasmeltedat 60. C., 5.0 g. of sodium ethoxide was added, and the mixture was placed in a 2 liter flask. To the mixture 113 g. of epoxyethane was added and the resultantrnixture was heated with stirring at 160 C. for 4 hours, whereby 830 kg. of an addition product having thetfollowing characteristics was obtained.

Melting point: 40 C.

Acid value: 21

Saponification value: 198

Melt viscosity (at 100 C.): 34.1 cst.

In 80 parts by weight of water was dispersed 20 parts" by weight of the resultant additionproduct, and the rate of oil stain and meany'ield stress of the lubricant thus obtained were measured'in the same manner as described with reference to Examples 1 to 3, with the following results.

Rate of oil stain 5 Mean yield stress (kg/mmP): 137 7 EXAMPLE 7 10 kg. of normal paraffin havinga melting pointof 49 C. and an average of 22 carbons per moleculewas melted at 60 C., to which was added 122.5 ml. of a 5 weight percent kerosene solution of manganese naphthenate. The mixture was placed in a cylindrical reactor of 250 mm. in diameter and 3,000. mmu-in'height. The mixture was heated at 170 C. and air was blown from the bottom of" the reactor in a proportion of 20 l./min./kg. of the parafiin for 6 hours. 70kg. of oxidation product having the following characteristics was obtained. Melting point: 31 C. i Acid value:

Saponification value: 320 p Melt viscosity (at 100 C.): 27.1 cst.

1 kg. of the resultant oxidation product was placed in a 2 liter stainless steel autoclave and melted at 60 C., and

3 g. of potassium hydroxide was added. To the mixture 257 g. of epoxyisobutane was added and the resultant mixture was heated with stirring at C. under pres-. sure of 6 kg./cm. for 10 hours, whereby 1.2 kg. of addi-U tion product having the following characteristics was obtained:

Melting point: 29 C. 7 Acid value: 5.0 I, Saponification value: .302

In 80 parts by weight of water was dispersed 20 parts by weight of the resultant addition product, and the-rateof oil stain and mean yield stress of the lubricant thus obtained were measured in the same manner as described with reference to Examples 1 to 3, with theresultsshown below.

Rate of oil stain 3 Mean yield stress (kg/mun): 133

9 EXAMPLE 3 1 kg. of an oxidation product prepared in the same- In 80 parts by weight of water was dispersed 20 parts by weight of the resultant addition product, and the mean yield stress ofthe lubricant measured in the same manner as described with reference to Examples 1 to 3 was 134 kg./mm.-.

. EXAMPLE 9 1.5 kg. of an oxidation product prepared in the same manner as in Example 7 was melted at 60 C., and 6 g. of triethylamine was added thereto. The mixture was placed in a 3 liter stainless steel autoclave. To the mixture 250.5 g. of 1-oxy-2,3-epoxypropane wasadded and the resultant mixture was heated with'stirring at 90 C. under pressure of kg/cm. for 0.5 hour. 1.65 kg. of addition product having the'following characteristics was obtained.

Melting point: 30 C.

Acid value: 5.0

Saponification value: 311

Melt viscosity (at 100C): 26.1 cst.

In 80 parts byweight of water was dispersed 20 parts by weight of the resultant addition product, and the rate of oil stain and mean yield stress of the lubricant thus obtained were measured in the same manner as described with reference to Examples '1 to 3, with the results shown below: .1

Melting point: 30 C.

Acid value: 3

Saponification value: 306

Melt viscosity (at 100 C.): 25.5 cst.

In 80 parts by weight of water was dispersed 20 parts by weight of the resultant addition product, and the rate of oil stain and mean yield stress of the lubricant thus obtained were measured in the same manner as described with reference to Examples 1 to 3, with the following result.

Rate of oil stain (percent): 5 Mean yield stress (kg./mm. 133

EXAMPLE 1 1 kg. of normal paraflin having a melting point of 49 C. and an average of 22 carbons per molecule was melted at 60 C., to which was added 122.5 ml. of a 5 weight percent kerosene solution of manganese naphthenate, and the mixture was placed in a cylindrical stainless steel reactor of 250 mm. in diameter and 3,000 mm. in height. The mixture was heated at 170 C. and air was blown from the bottom of the reactor in a proportion of 30 10 l./min./kg. of the paraffin. 8.4 kg. of oxidation product having the following chracteristics was obtained.

Melting point: 40 C.

Acid value: 40

Saponification value: 148

Melt viscosity (at C.): 8.8 cst.

1 kg. of the resultant oxidation product was melted at 60 C., to which 10 g. of phosphoric acid was added, and the mixture was placed in a 2 liter autoclave. To the mixture 167 g. of styrene oxide was added and the resultant mixture was heated with stirring at 160 C. under pressure of 4 kg./cm. for 5 hours. 1.1 kg. of addition product having the following characteristics was obtained.

Melting point: 39 C.

Acid value: 22

Saponification value: 138

Melt viscosity (at 100 C.): 7.2 cst.

In 80 parts by weight of water was dispersed 20 parts by weight of the resultant addition product, and the rate of oil stain and mean yield stress of the lubricant thus obtained were measured in the same manner as described with reference to Examples 1 to 3, with the following results.

Rate of oil stain (percent): 3 Mean yield stress (kg./mm.

EXAMPLE 12 1 kg. of an oxidation product prepared in the same manner as in Example 11 was melted at 60 C., to which 5 g. of trietthylphosphite was added, and the mixture was placed in a 2 liter autoclave. To the mixture 119 g. of phenylglycidyl ether was added and the resultant mixture was heated with stirring at 120 C. under pressure of 4 kg./cm. for 8 hours, whereby 1.1 kg. of an addition product having the following characteristics was obtained.

Melting point: 38 C.

Acid value: 18

Saponification value: 129

Melt viscosity (at 100 C.): 8.6 cst.

In 80 parts by weight of water was dispersed 20 parts by weight of the addition product, and the rate of oil stain and mean yield stress were measured in the same manner as described with reference to Examples 1 to 3, with the following results.

Rate of oil stain (percent): 5 Mean yield stress (kg./mm.

EXAMPLE 13 1 kg. of an oxidation product prepared in the same manner as in Example 11 was melted at 60 C., to which 3 g. of potassium hydroxide was added, and the mixture was placed in a 2 liter autoclave. To the mixture 120 g. of 1,2-epoxycyclohexane was added and the resultant mixture was heated with stirring at C. under pressure of 4 kg./cm. for 10 hours. 1.1 kg. of addition product having the following characteristics was obtained.

Melting point: 38 C.

Acid value: 12

Saponification value: 117

Melt viscosity (at 100 C.): 8.1 cst.

In 80 parts by weight of water was dispersed 20 parts by weight of the resultant addition product, and the rate of oil stain and mean yield stress of the lubricant thus obtained were measured in the same manner as described with reference to Examples 1 to 3, with the following resu ts.

Rate of oil stain (percent): 5 Mean yield stress (kg./mm. 148

What we claim is: 1. process for cold rolling a metal which comprises applying between the roll and the metal a lubricating 1 1 amount of the additionproduct of an epoxy compound and an oxidation product of an aliphatic hydrocarbon having an acid value of 30 to 110; said addition product having an average molecular weight of 280 to 800 and an acid value of to 30 and containing said epoxy compound in the molecule in an amount from 1 to 2 moles per mole of carboxyl group inthe oxidation product but sufficient to reduce at least 60 percent of acid value of said oxidation product; said oxidation product of hydrocarbon being prepared by contacting at 100 to 180 C. aliphatic hydrocarbon of 15 to 55 carbon atoms with molecular oxygen; and said epoxy compound having the formula of R 3 1 R \I{ wherein R is one member of the group consisting of hydrogen atom, alkyl group of 1 to 10 carbon atoms, hydroxymethyl group, chloromethyl group, acyloxymethyl group of 2 to 7 carbon atoms, carboalkoxymethyl group of 2 to 7 carbon atoms, alkoxymethyl group of 2 to 7 carbon atoms, phenoxymethyl group and phenyl group and R and R are respectively one member of the group consisting of hydrogen atom and a lower alkyl group of 1 to 3 carbon atoms, and when R and R are alkyl group and R is hydrogen and R and R may constitute a cycloalkyl group being bonded to each other at their end positions.

2. The process for cold rolling according to claim 1, in which said addition compound has an acid value of 2 to 20.

3. The process for cold rolling according to claim 1, in which said oxidation product of aliphatic hydrocarbon has an acid value of 50 to 100.

4. The process for cold rolling according to claim 1 in which said epoxy compound is one member of the group consisting of epoxyethane, epoxypropane, 1,2-epoxy- :butane, 2,3-epoxybutane, epoxyisobutane, 1-oxy-2,3- epoxypropane, epichlorohydrine, 1,2-epoxycyclohexane, styrene oxide and phenyl glycidyl ether.

5. The process for cold rolling according to claim 1 in which said epoxy compound has the formula of wherein R is one member of the group consisting of hy drogen atom, methyl group and ethyl group.

6. A process for cold rolling a metal which comprises applying between the roll and the metal an aqueous dispersion having dispersed therein 1 to 30% by weight of Water of a lubricating amount of the addition product of an epoxy compound and an oxidation product of an aliphatic hydrocarbon having an acid value of 30 to 11.0; said addition product having an average molecular yweight'of 280 to 800 and an acid value oft) to 30 and containing said epoxy compound in the molecule in an amount-from 1 to 2 moles per mole of carboxyl group in the oxidation product but sufficient to reduce at least percent of acid value of said oxidation product; said oxidation product of hydrocarbon being prepared by contacting at to C. aliphatic hydrocarbon of 15 to 55 carbon atoms with molecular oxygen; and said epoxy compound having the formula of p wherein R is one member of the group consisting of hydrogen atom, alkyl group of 1 ,to 10 carbonatoms, hydroxymethyl group, chloromethyl group, acyloxymethyl group of 2 to 7 carbon atoms, carboalkoxymethyl group of 2 to 7 carbon atoms, alkoxymethyl' group of 2 to 7 carbon atoms, phenoxymethyl group and phenyl group and R and R are respectively one member of the group consisting of hydrogen atom and a lower alkyl group of 1 to 3 carbon atoms, and when R andR' are alkyl group and R is hydrogen and R and R may constitute a cycloalkyl group by being bonded to each other at their end positions. f

References Cited UNITED STATES PATENTS 10/ 1954 Great Britain 252-493 DANIEL E. WYMAN, Primary Examiner W. H. CANNON, Assistant Examiner V US. Cl. x11. 252-55, 52, 56 R