US3788991A

US3788991A - Metal working agents

Info

Publication number: US3788991A
Application number: US00220489A
Authority: US
Inventors: H Diery; S Rittner; H Lorke
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1971-01-26
Filing date: 1972-01-24
Publication date: 1974-01-29
Anticipated expiration: 1991-01-29
Also published as: IT946874B; SU444373A3; DE2103419A1; GB1375631A; CH575990A5; BE778533A; BR7200420D0; NL7200884A; DE2103419B2; CS161789B2; USB378891I5; FR2123426A1; DD95357A5; SE379547B; FR2123426B1; CA979422A; DE2103419C3

Abstract

THE USE OF OIL-FREE AQUEOUS METAL WORKING AGENTS, ESSENTIALLY CONSISTING OF WATER AND (A) 0.1 TO 5.0% BY WEIGHT OF A WATER-SOLUBLE AMINE SALT OF AN ARYL-SULFONAMIDO-ALKYLENE-CARBOXYLIC ACID, AND (B) 0.5 TO 12.0% BY WEIGHT OF A WATER-SOLUBLE POLYADDITION PRODUCT OF ETHYLENE OXIDE AND PROPYLENE OXIDE AND/OR BUTYLENE OXIDE WITH A COMPOUND HAVING 1 TO 8 ACTIVE HYDROGEN ATOMS FOR COLD ROLLING OF IRON SHEET METAL.

Description

United States Patent 3,788,991 METAL WORKING AGENTS Helmut Diery, Kelkheim, Taunus, Siegbert Rittner, Frankfurt am Main, and Horst Lorke, Oberliederbach, Taunus, Germany, assignors to Farbwerke Hoechst 58ktiengesellschaft vormals Meister Lucius & Brumng, Frankfurt am Main, Germany No Drawing. Filed Jan. 24, 1972, Ser. No. 220,489 Claims priority, application Germany, Jan. 26, 1971, P 21 03 419.5 Int. Cl. Cm 1/34 US. Cl. 25233.6 6 Claims ABSTRACT OF THE DISCLOSURE The use of oil-free aqueous metal working agents, essentially consisting of water and (A) 0.1 to 5.0% by weight of a water-soluble amine salt of an aryl-sulfonamido-alkylene-carboxylic acid, and (B) 0.5 to 12.0% by weight of a water-soluble polyaddition product of ethylene oxide and propylene oxide and/or butylene oxide with a compound having 1 to 8 active hydrogen atoms for cold rolling of iron sheet metal.

In the cold rolling process for obtaining a certain reduction of the thickness of hot prerolled sheet metal, it is customary to use aqueous emulsions of mineral oils or of fatty oils which contain anionic or nonionogenic emulsifiers or mixtures of such emulsifiers. However, the use of these sensitive emulsion systems in cold rolling implies a number of disadvantages. Often, these emulsions do not have a sufiicient stability, they are liable to the attack by bacteriae, they leave residues and their corrosion-inhibiting action is in most cases not satisfactory. Even the rolling effect is strongly influenced, for example by the particle size of the emulsions which are often undergoing modifications of their consistency under the process conditions. Thus, thicker emulsions provide better lubricating action, but they are less stable than fine dispersions and they have, for this reason, not optimum properties for rolling processes. The life times of the rolling emulsions are highly reduced by the acid and electrolyte proportions dragged-in during the foregoing pickling. A great disadvantage of emulsions on the basis of mineral oil or of vegetable or animal oils is furthermore the deposition of coal and ash residues on the annealed metal sheets. A further disadvantage is also that, owing to the content of emulsifier of the emulsions, the lubricating oils contained in the roller bearings are dragged-in in emulsified form into the rolling liquids. Still another disadvantage is that these rolling emulsions do not provide a satisfactory corrosion inhibition of the work pieces.

Now, the present invention provides new oil-free, aqueous metal working agents, especially for rolling processes, which contain (A) water-soluble amine salts of aryl-sulfonamido-alkylenecarboxylic acids, and

(B) water-soluble poly-addition products of ethylene oxide and propylene oxide and/or butylene oxide with compounds containing active hydrogen atoms,

instead of the known oily emulsion systems in the cold rolling of sheet metal.

The use of the oil-free metal working agents for rolling according to the invention avoids the disadvantages of the rolling oil emulsions mentioned before and, in addition thereto, provides further advantages.

The new oil-free, aqueous metal working agents for ice rolling processes can be adjusted, with the aid of the amine salts of arylsulfonamido-alkylene-carboxylic acids, advantageously in such a manner as to be transparent at room temperature and, at a higher temperature, watersoluble and opal and that at still higher temperatures, for example at temperatures exceeding C. they separate oil-like droplets. Upon cooling, these modifications of the consistency proceed in the reverse direction, i.e. the oily droplets become water-soluble again and the rolling liquid is then present in the storage tank in the form of a clear, aqueous solution. It is also possible, however not preferred in most cases, to adjust the rolling liquids with the aid of the polyaddition products of ethylene oxide and propylene oxide and/or butylene oxide with compounds containing active hydrogen atoms in such a manner that the rolling liquid is present in the form of a dispersion during the whole process. It is preferred to use as components (A) and (B) for the preparation of the rolling liquid of the invention such products which are water-soluble in the cold. The term water-soluble shall encompass here, and also in the following description, also the state of a colloidal solution or dispersion.

As aryl-sulfonamido alkylene carboxylic acids contained in the form of their amine salts as component (A) in the rolling liquids of the invention, there are used compounds of the general formula In this formula, R and R represent hydrogen, halogen atoms such as fluorine, chlorine or bromine atoms, a nitro group or an alkyl or alkoxy group having 1 to 4 carbon atoms, the sum of the carbon atoms of both groups R and R should not exceed 7, preferably not the number 3, Ar represents the benzene, naphthalene, anthracene, diphenyl, diphenylmethane, diphenyl oxide, diphenyl sulfide, diphenyl-sulfoxide or diphenyl sulfone group, preferably benzene, R stands for hydrogen, an alkyl group having 1 to 4 carbon atoms, the fi-cyano-ethyl group or a hydroxy-alkyl group having 2 to 4 carbon atoms, R represents an alkylene group having 4-15 carbon atoms in the chain, which may also be substituted by one or several methyl or ethyl groups, and n represents the number 1 or 2.

Such compounds of the General Formula I are, for example:

benzene-sulfonyl-e-amino-valeric acid, benzene-sulfonyl-N-methyl fi-amino-valeric acid, benzenesulfonyl-s-aminocaproic acid, benzene-sulfonyl-N-methyl-e-aminocaproic acid,- p-toluene-sulfonyl-e-aminocaproic acid, benzene-sulfonyl-N-ethyl-e-aminocaproic acid, benzene-sulfonyl-N-butyl-e-aminocaproic acid, xylene-sulfonyl-N-methyl-e-aminocaproic acid, benzene- 1,3 -di- (N-methyl-sulfonamido-e-caproic acid), naphthalenel,6-di( N-methylsulfonamido-e-caproic acid), anthracene-(2)-sulfonyl-N-methyl-e-aminocaproic acid, benzenesulfonyl-N-methyb -aminocaprylic acid, p-toluene-sulfonyl-N-methyl-v-aminooctane-a-carboxylic acid, benzene-sulfonyl--r-aminononane-u-carboxylic acid, p-toluene-sulfonyl-w-amino-undecanoic acid, 4-methoxy-benzene-sulfonyl-N-methyl-e-aminocaproic acid, 4-chlorobenzene-sulfonyl-N-methyl-e-aminovaleric acid, 2,4-dichloro-benzene-sulfonyl-N-methyl-e-aminocaproic acid,

hexyl-benzeneand isopropyl-benzene-sulfonyl-N- methyl-e-aminocaproic acid, diphenyl-sulfonamido-6-valeric acid, diphenyl-N-methyl-sulfone-amidocaproic acid, 2,2-dimethyl-diphenyl-sulfonamido-e-valeric acid, 2,4'-dimethyl-diphenyl-N-methylsulfonamido-e-caproic acid, 2-bromo-diphenyl-sulfonamido-w-undecanoic acid, 3 bromo-diphenyl-N-methyl-sulfonamido-ti-valeric acid, 2-chlorodiphenyl-N-methyl-sulfonamido-e-caproic acid, 2-fluoro-diphenyl-sulfonamido-e-caproic acid, diphenyl-sulfonamido-w-undecanoic acid, diphenyl-oxide-sulfonamidofi-valeric acid, diphenyl-oxide-N-butyl-sulfonamido-fi-valeric acid, diphenyl-oxide-sulfonamido-e-caproic acid, diphenyl-oxide-N-rnethyl-sulfonamido-fi-caproic acid, 4-chlorodiphenyl-oxide-sulfonamido-fi-valeric acid, diphenyl-oxide-sulfonarnido-w-undecanoic acid, diphenyl-oxide-N-methyl-sulfonyl-v;-aminocaprylic acid, diphenyl-methane-sulfonamido-a-valeric acid, diphenyl-methane-N-methyl-sulfonamido-e-caproic acid, diphenyl-methanesulfonamido-w-undecanoic acid, diphenyl-sulfide-sulfonamido-6-valeric acid, diphenyl-sulfide-sulfonamido-e-caproic acid, diphenyl-sulfide-N-methyl-sulfonamido-e-caproic acid, diphenyl-sulfone-sulfonamido-a-valeric acid, diphenylsulfone-N-methylsulfonamido-e-caproic acid, 4-chloro-diphenyl-4'-sulfonamido-e-caproic acid, diphenyl-sulfone-sulfonamido-w-undecanoic acid, diphenyl-sulfoxide-sulfonamido-fi-valeric acid, diphenyl-sulfoxide-N-methyl-sulfonamido-e-caproic acid, diphenylsulfoxide-sulfonamido-w-undecanoic acid, 2,2'-dichloro-dipehnyl-sulfonamido-B-valeric acid, o-nitro-benzene-sulfonyl-6-aminova1eric acid, o-nitrobenzene-sulfonyl-N-methyl-a-aminovaleric acid, m-nitro-benzene-sulfonyl-e-aminocaproic acid, o-nitrobenzene-sulfonyl-N-ethyl-e-aminocaproic acid, m-nitrobenzene-sulfonyl-N-butyl-e-aminocaproic acid, 4-methoxy-2-nitrobenzene-sulfonyl-B-aminovaleric acid, 3,S-dinitro-4-chlorobenzene'sulfonyl-e-amino-valeric acid, 3,5-dinitro-4-chlorobenzene-sulfonyl-N-methyl-e-aminocaproic acid, m-nitr-obenzenesulfonyl-N-methyl-e-aminooctane-a-carboxylic acid, 1-nitronaphthalene-sulfonyl-e-aminocaproic acid, 1-nitro-naphthalene-sulfonyl-N-methyl-w-aminocaproic acid, m-nitrobenzene-sulfonyl-w-aminoundecanoic acid, nitrotoluene-sulfonyl-N-methyl-e-amiuocaproic acid, m-nitrobenzene-sulfonyl-fi-aminobutyric acid, etc.

For the formation of the amine salts of the above-mentioned aryl-sulfonamido-alkylene-carboxylic acids, there may be used any desired amines. There is only one condition, i.e. that they yield with the arylsulfonamido-alkylenecarboxylic acids water-soluble products. Suitable amines for the salt formation are, for example mono-, diand trimethylamines, mono-, diand tri-ethylamines, mono-isopropyl amines, monoand di-butylaminc, 3-methoxypropylamine, mono-Z-ethyl-hexylamine, dimethylaminopropylamine, mono-, diand triethanol-amines as well as the corresponding isopropanol amines, 3-amino-propanol, monomethyl-ethanol amine, dimethyl-ethanol amine, diisopropylamine, triisopropylamine, cyclohexylamino, N, N-dimethyl-cyclohexyl amine, morpholine, pyridine, quinoleine, ethylene diamine, diethylene triamine, pentaethylene hexamine. Fatty amines or, for improving the solubility in water, fatty amines that have been reacted with ethylene oxide may also be used. For the salt formation, acid and amine may be used in a stoichiometrical ratio; however, the arylsulfonamido-alkylene carboxylic acid or, preferably, the amine may also be used in excess. For economical reasons and in view of the low toxicity, the mono-, dior tri-ethanolamines or -isopropanolamines are vtcferably used.

While the amine salts of the arylsulfonamido alkene carboxylic acids (component A) are responsible for the corrosion inhibition of the metal working agents of the invention, the poly-addition products of ethylene oxide and propylene oxide and/or butylene oxide with compounds containing active hydrogen atoms (component B) are responsible for the lubricating properties of these agents. This component B having a lubricating action is constituted from poly-addition products of alkylene oxides having 2 to 4 carbon atoms with aliphatic or aromatic compounds containing up to 30 carbon atoms and 1 to 8, preferably 1 to 5, hydrogen atoms which are capable of reacting with alkylene oxides; these poly-addition products may contain, in any desired sequence, once or several times, groups of the formula --(C H.,O)- as well as groups of the formula (C H O)- and/or of the formula -(C.,H O) in one chain and may have molecular weights in the range of from 1000 to 30,000, preferably 2500 up to 20,000. The proportion of ethylene oxide groups in these poly-addition products is in general about 15 to 85, preferably 40 to 60 percent by weight with a content of at least 10 propylene or butylene oxide residues in the molecule.

In the poly-addition products, the ethylene oxide and propylene oxide and/or butylene oxide radicals may be arranged in alternating or blockwise alternating manner by alternating or blockwise alternating alkoxylation with ethylene oxide and propylene oxide and/or butylene oxide or, for example, by alkoxylation of the compounds containing the active hydrogen atoms with a mixed oxide having a defined composition (for example, ethylene oxidezpropylene oxide 1:1) to obtain a statistical dis tribution.

Organic compounds which contain 1 to 8, preferably 1 to 5, hydrogen atoms which are capable of reacting with alkylene oxide, are in particular saturated or unsaturated, straight chain or branched monohydric aliphatic alcohols, diols or polyols, primary or secondary monoamines, polyamines or alkanolamines as well as carboxylic acids or dicarboxylic acids and their amides. Phenols and monoor dialkyl phenols are likewise suitable. Examples of such compounds having mobile hydrogen atoms are in particular: alkanols and alkenols having 1 to 20 carbon atoms such as methanol, ethanol, 11- or iso-propanol, nor iso-butanol, Z-ethylhexanol, dodecano1-(1), octadecanol-(l), singly unsaturated alcohols such as allyl-alcohol or oleyl-alcohol; furthermore diols and polyols having 2 to 22 carbon atoms such as ethylene glycol, propane-diol-(1,3), propane-diol-(l, 2), butane-diol-( 1,4), dodecanediol-(1,7), hexadecanedio1-( 1,4), octadccane-diol-( 1,6), glycerin, pentaerythritol, sorbitol and saccharose; furthermore primary or secondary, saturated or unsaturated, aliphatic mono-, dior tri-amines having 2 to 20 carbon atoms such as butylamine, hexylamine, dodecylamine, octadecylamine, oleylamine, ethylenediamine, diethylene-triamine, ethanolamine, di-ethanolamiue and triethanol-amine; furthermore saturated or singly unsaturated aliphatic monoor di-carboxylic acids containing 2 to 22 carbon atoms such as caprylic acid, laurylic acid, oleic acid, stearic acid, arachic acid, behenic acid, and the amides of these carboxylic acids; and furthermore phenols and monoor di-alkyl-phenols having 1 to 8 carbon atoms in the respective alkyl group such as phenol, cresols, butyl-phenol, tert.butyl-phenol;, nonyl-phenol, dodecylphenol and di-dodecyl-phenol.

The poly-addition products used as the lubricating components B in the rolling liquids of the invention are water-soluble products despite their higher molecular structure and can be obtained by fixing, according to methods known per se, ethylene oxide and propylene oxide and/or butylene oxide onto the aforementioned basic substances having mobile hydrogen atoms.

An essential advantage with regard to application of the corrosion-inhibiting rolling liquids of the invention is that they can be used within a wide range of concentration and have a good action and stability in all processing stages. A suflicient activity is ensured in many cases with as low concentrations of the solutions of salts of aryl-sulfonamido-alkylene-carboxylic acids (A) as of 0.1% by Weight and with concentrations of the alkylene-oxide poly-addition products as lubricatingv component (B) of 0.5% by weight.

The preferred range of concentration of the rolling liquids of the invention is 13% by weight for component A and 28% by weight for the lubricating component B. Rolling liquids having higher concentrations of both components are equally well active, but they are less preferred, for economical reasons. Thus, in general, concentrations exceeding about 5% by weight for component A and those exceeding about 12% by weight for the lubricating component B are not used.

The technical advantage of the rolling liquids of the invention is also proved by the fact that they meet the high demands required from a rolling liquid in the manufacture of defined sheet metal with exactly constant thickness, for example in the manufacture of automobile bodies.

The good lubricating properties and the synergistic efiect of the two compounds of the new metal working agents with regard to their lubricating action have been proved in the following tests shown with examples of the rolling liquids of the present invention. In these tests, there were measured, with the rubbing tear-off balance according to Reichert, the specific surface pressure (P in kg./cm. as the measure for the lubricating action of aqueous solutions each time containing 2% by weight of the products indicated hereunder:

(a) The triethanol-ammonium salt of benzene-sulfonyl-N-methyl-e-aminocaproic acid.

(b) The triethanol-amine salt of m-nitrobenzene-sulfonyl-N-methyl-e-aminocaproic acid.

(1) The addition compound of ethylene oxide onto a polypropylene glycol having a molecular weight of 2000 up to a final molecular weight of the poly-addition product of 2500.

(1a) A mixture of equal parts of products (a) and (1).

(lb) A mixture of equal parts of products (b) and (2) The addition compound of ethylene oxide onto a polypropylene glycol having a molecular weight of 1900 up to a final molecular weight of the poly-addition product of 4200.

(2a) A mixture of equal parts of products (a) and (2).

(2b) A mixture of equal parts of products (b) and (3) The addition compound of propylene oxide onto 1 mole of ethylene diamine up to a molecular weight,- of 750, further reacted with ethylene oxide up to a total molecular weight of the poly-addition product of 1365.

(3a) A mixture of equal parts of products (a) and (3 (3b) A mixture of equal parts of products (b) an (3).

(4) The addition compound of propylene oxide onto 1 mole of ethylene diamine up to a molecular weight of 2750, further reacted with ethylene oxide up to a total molecular weight of 3235.

(4a) A mixture of equal parts of products (a) and (4b) A mixture of equal parts of products (b) and (5) The addition compound of propylene oxide onto 1 mole of ethylene diamine up to a molecular weight of 2750, further reacted with ethylene oxide up to a total molecular weight of 3670.

(5a) A mixture of equal parts of products (a) and (5).

(5b) A mixture of equal parts of products (b) and (5).

(6) The addition compound of propylene oxide onto 1 mole of ethylene diamine up to a molecular weight of 2750, further reacted with ethylene oxide up to a total molecular weight of the polyaddition compound of 5000.

(6a) A mixture of equal parts of products (a) and (6).

(6b) A mixture of equal parts of products (b) and (6).

(7) The addition compound of propylene oxide onto 1 mole of ethylene diamine up to a molecular weight of 2750, further reacted with ethylene oxide up to a final molecular weight of the polyaddition product of 11,000.

(7a) A mixture of equal parts of products (a) and (7).

(7b) A mixture of equal parts of products (b) and (8) The addition compound of propylene oxide onto 1 mole of ethylene diamine up to a molecular weight of 4000, further reacted with ethylene oxide up to a final molecular weight of the polyaddition product of 7270.

(8a) A mixture of equal parts of products (a) and (8).

(8b) A mixture of equal parts of products (b) and (8).

(9) The addition product of propylene oxide onto 1 mole of ethylene diamine up to a molecular weight of 4000, further reacted with ethylene oxide up to a final molecular weight of the polyaddition product of 26,650.

(9a) A mixture of equal parts of products (a) and (9).

(9b) A mixture of equal parts of products (b) and (9).

(10) fie addition compound of propylene oxide onto 1 mole of ethylene diamine up to a molecular weight of 3540, further reacted with ethylene oxide up to a final molecular weight of the polyaddition compound of 4860.

(10a) A mixture of equal parts of products (a) and (10).

(10b) A mixture of equal parts of products (b) and (c) The triethanol-ammonium salt of naphthalene- 1,5 -di(N-methylsulfonamido-caproic acid) (60) A mixture of equal parts of products (c) and (d) The triethanol-ammonium salt of diphenyl-oxide- N-methyl-sulfonamido-caproic acid.

(6d) A mixture of equal parts of products (d) and (6).

(e) The triethanol-ammonium salt of diphenyl-N- methyl-sulfonamide-caproic acid.

(6e) A mixture of equal parts of products (e) and (6).

(f The triethanol-ammonium salt of 4-chlorobenzenesulfonyl-e-amino-caproic acid.

(6f) A mixture of equal parts of products (f) and (6).

The products (a) and (b) are examples of component (a) of the coolants of the invention. Products (1) to (10) are examples of the lubricating component (B) of the rolling liquids and the products denoted with these figures and with (a) and (b), i.e., from (la) to (10a) and (lb) to (10b) represent the active components of the rolling liquids of the invention in the form of mixtures of each time equal parts of products 1 to 10 on the one hand and of products (a) and (b) on the other hand.

The results of these tests are compiled in Table 1; this table shows in column I the values for the lubricating action of the individual components, i.e. of products (a) and (b) (Component A) and of products 1 to 10 (lubricating component B) and in column II the values of the lubricating action of the mixtures, i.e. of products (la) to (10a) and (1b) to (10b) (metal working agents ac- TABLE 1 Lubricating action (kg/em!) Product number as 2% aqueous solution I A comparison of the values of the single component products (1) to with the corresponding values of the mixed products (1a) to (102.) and (1b) to (10b) shows that, despite the reduction to half the concentration of the lubricating component in the mixed products, the high lubricating actionis maintained or is reduced by an insignificant degree only. The lubricating action of the mixed products is considerably higher than it could have been expected on the basis of the values of the single components. Thus, the results of these tests show the surprising synergistic eflect of the two components of the metal working agents of the invention with regard to their lubricating action.

In further tests, some of the properties which are essential for the effectiveness of metal working agents, have been tested with a liquid according to the invention in comparison with a known mineral oil emulsion used for rolling processes.

For these tests, there were used:

Product 11 consisting of: I

50.0 parts by Weight of an 85% aqueous solution of a basic triethanol-ammonium salt of benzene-sulfonyl-N- methyl-s-aminocaproic acid, and 50.0 parts by weight of an addition product of ethylene oxide and polypropylene-glycol having a molecular weight of 1900 up to a final molar weight of the polyaddition production of 3200.

Product 12 (comparison product) consisting of 70.0 parts by weight of mineral oil (3 E./20 C.), 15.0

parts by weight of the sodium salt of an aliphatic sulfonamidoacetic acid having 12-18 carbon atoms in the alkyl moiety, 12.0 parts by weight of an addition product of 7 moles of ethylene oxide and 1 mole of oleylalcohol, and 3.0 parts by weight of water.

Product 13 (comparison product) consisting of: 72.0 parts by weight of mineral oil (3 E./20 C.), 12.0

parts by weight of the reaction product of 10 moles of ethylene oxide and 1 mole of tributyl-phenol, 10.5 parts by weight of the sodium salt of an aliphatic sulfonamido-acetic acid having 1218 carbon atoms in the alkyl moiety, 3.0 parts by weight of oleyl-sarcoside, and 2.5 parts by weight of water.

(a) Rolling tests The rolling tests were carried out on a test rolling ap paratus comprising hardened chromium steel rolls with a .diameter of mm. The rolling speed was constantly 6.0 m./min. The three products to be tested were sprayed in a dilution with water in a weight proportion of 1:20 onto the upper and lower side of the test material at the inlet of the rolling apparatus. As test materials, 50 mm. wide strips of Siemens-Martin steel cast in killed state and having the quality MR St 4 according to DIN 1624 (German Industrial Standard) were used. The 2.5 mm. thick warm strips had been previously rolled to 1.0 mm. The values of the reduction of the thickness of the strips obtained with the three products are listed in Table 2.

TABLE 2 Percent reduction of thickness per pass Product number (diluted 1:20 with Water) 1 2 3 4 5 6 Rolled in dry state 30 40 45 50 52 53 61 68 74 77 49 58 66 71 74 51 59 67 73 76 These results show that the aqueous rolling liquid of the invention permits at least the same reduction of thickness, but provides a smoother surface than that obtained with oil emulsions.

(b) Measurement of the friction The measurement of the friction permits the prediction of the lubricating action of the products to be tested in the rolling slot. In these friction measurements, the angle changes of the drawing jaws were determined in drawing tests. The values in a obtained for the angle changes are shown in Table 3.

(c) Determination of residues Rolling liquids shall have as low a tendency as possible of forming carbon or ash residues, since this small residue formation is essential for a clean surface of the material rolled after annealing under an atmosphere of nitrogen.

For testing the residue formation, the rolling liquid to be tested was weighed into a special glass flask and the latter was then introduced into a metal bath heated to 550 C. In this manner, the sample was heated as rapidly as possible to temperatures at which all volatile components escaped, whereas the sparingly volatile components are cracked and coked in the flask. After a heating time of 5 minutes, the flask was removed from the heating bath, cooled and again weighed. The residue remained behind in the flask was calculated in percent by weight, referred to the product weighed in, as Ramsbottom carbon residue.

The results of these tests shown in Table 4 illustrate the considerably lower residue formation of the rolling agent of the invention in comparison to that of the comparative products.

(d) Corrosion inhibition For preventing the corrosion during rolling and storage of the rolled metal sheets as well as for protecting the rolls themselves, rolling liquids are required to provide an as high corrosion inhibition as possible. The test for the corrosion inhibition was effected according to the Herbert test (IF-Standards for Petroleum and its Products, IP 125/ 63 (I) and (11)), in which steel chips were placed onto a plate of cast iron and wetted with the solution to be tested. After an action time of 24 hours, the chips were removed from the cast iron plate and the plate was evaluated visually with regard to rust formation. The evaluation was efiected according to the following scale:

Scale:

+ no rust. traces of rust. slight rust. distinct rust.

- strong rust. very strong rust.

In these tests, solutions of products 11-13 in distilled water and in tape water having a German hardness of 20 were tested in concentrations of 1, 3 and by weight, respectively. The results of these tests are indicated in Table 5.

TABLE 5 Distilled water Hard water (20 GH) Sample number 1% 3% 5% 1% 3% 5% (e) Emulsifying properties A disadvantage of the known oil-containing rolling liquids is their property to separate by emulsification the lubricating oils contained in the roller bearings and thereby to drag these lubricating oils into the rolling liquids. The rolling liquids of the invention do not have these disadvantages, as was also shown by the tests for the emulsifying properties.

For testing the emulsifying properties, the products 11- 13 were mixed with mineral oil in a ratio of 1:1. The mixtures obtained were evaluated with regard to their nature and, for testing the emulsifying properties, they were stirred into water.

TAB LE 6 Emulsiiyability of the mixture Mixture 1:1 1:1 with mineral Product number with mineral oil oil in water 11 Separates None. 12.-- 13 2. An oil-free aqueous metal working agent as claimed in claim 1, which contains as the component A an amine salt of an acid of the general Formula I in which R and R represent hydrogen, fluorine, chlorine or bromine, a nitro group or an alkyl or alkoxy group having 1 to 4 carbon atoms, the sum of the carbon atoms of both groups R and R not exceeding the number 7, Ar represents the benzene, naphthalene, anthracene, diphenyl, diphenyl-methan, diphenyl-oxide, diphenyl-sulfide, diphenyl-sulfoxide or diphenyl-sulfone group, R represents hydrogen, an alkyl group having 1 to 4 carbon atoms, the B-cyano-ethyl group or a hydroxy-alkyl group having 2 to 4 carbon atoms, R represents an alkylene group having 4 to 15 carbon atoms in the chain and n represents the number 1 or 2.

3. An oil-free aqueous metal working agent as claimed in claim 1., which contains the component A in a concentration of 1 to 3% by weight and the component B in a concentration of 2 to 8% by weight.

4. In the process of cold rolling of iron sheet metal, the step consisting of applying as an oil-free rolling liquid an aqueous mixture essentially consisting of water,

(A) 0.1 to 5.0% by weight of a water-soluble amine salt of an aryl-sulfonamido-alkylene-carboxylic acid, and

(B) 0.5 to 12.0% by Weight of a water-soluble polyaddition product of ethylene oxide and propylene oxide with propylene glycol or ethylene diamine, the polyaddition product having a molecular weight in the range of from 2500 to 20,000 and having a proportion of about 15 to percent by weight oxyethylene radicals in its molecular structure.

5. The process step as claimed in claim 4, wherein as component A an amine salt of an acid of the general in which R and R represent hydrogen, fluorine, chlorine or bromine, a nitro group or an alkyl or alkoxy group having 1 to 4 carbon atoms, the sum of the carbon atoms of both groups R and R not exceeding the number 7, Ar represents the benzene, naphthalene, anthracene, diphenyl, diphenyl-methan, diphenyl-oxide, diphenyl-sulfide, diphenyl-sulfoxide or diphenyl-sulfone group, R represents hydrogen, an alkyl group having 1 to 4 carbon atoms, the B-cyano-ethyl group or a hydroxy-alkyl group having 2 to 4 carbon atoms, R represents an alkylene group having 4 to 15 carbon atoms in the chain and n represents the number 1 or 2, is used.

6. The process step as claimed in claim 4, wherein the component A is used in a concentration of 1 to 3% by weight and the component B in a concentration of 2 to 8% by weight.

References Cited UNITED STATES PATENTS 2,958,661 11/1960 Reamer et al 25233.6 2,981,686 4/1961 Reamer 25233.6 3,046,225 7/1962 Murray et a1. 25233.6 3,556,994 1/-197l Diery et al 25233.6 3,027,405 3/1962 Spivack et al. 25233.6

HELEN M. S. SNEED, Primary Examiner