DE2251611A1 - PROCEDURE FOR PRE-TREATMENT OF METAL SURFACES - Google Patents

Description

KONINKLIJKE EMBALLAGE INDUSTRIE VAN LEER B.V. Amstelveen, Netherlands

"Process for the pretreatment of metal surfaces" Priority: October 22, 1971, The Netherlands, No. 71.14590

The invention relates to a method for pretreating metal surfaces by applying a protective layer to improve the adhesion of organic paints and / or to prevent them premature roasting. Steel in particular comes into consideration for this pretreatment.

In the manufacture of steel drums it is a serious disadvantage that the surfaces of strip steel and steel sheets

often show impurities, in particular

in the form of spots of rust that often appear in spots. Special treatment is therefore required for the steel surface to make it suitable for the application of paints without side effects, like water sensitivity.

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It would therefore save time and money if a steel was used That is virtually free of rust and other undesirable contaminants and that is temporary Has rust resistance, but still provides a substrate that is suitable for painting and does not require any special treatment.

It is common knowledge that steel rusts due to its deposition an oily compound on the surface or by phosphating the surface can be prevented. It is It is also known that the phosphating of the surface and sealing of the phosphate layer, for example by means of an oil, in practice is carried out.

These processes give the steel a rust protection that satisfies practical requirements, but they have the disadvantage that they are sealed by an oily compound or oil

Phosphating protected steel no paint is applied without degreasing the steel beforehand, which affects the application and adhesion of many paints would. On the other hand, the protection provided by phosphating is solely due to the need to achieve rust resistance and adhesive strength the quantities of paint required are uneconomical.

These disadvantages lead to considerable difficulties in the manufacture of steel drums which have to be painted on the outside and usually painted on the inside. A steel protected against rust by these known methods can be practical

309817/1093 ORIGINAL BATHROOM

not painted in a satisfactory manner without removing any oil that may have been applied

must become. /

/ Consequently, the manufacturers of steel drums need the steel surface with organic solvents such as triehloroethylene, degrease or wash with aqueous alkaline solutions, e.g. with aqueous solutions of sodium hydroxide, sodium carbonate, Alkali metal silicates or condensed phosphates, especially pyrophosphates, or with aqueous acidic solutions, e.g. with aqueous solutions of monoalkali metal phosphates.

According to British Patent 625 297, the wear properties and storage times of metal surfaces are improved by applying a stabilized solution, paste or emulsion the orthophosphoric acid and a water-insoluble non-drying polar oil or fat in a weight ratio from 1: 100 to 15 ^ 00 included. Although the proportion of protective

2
substances per m not specified, obviously such an amount of polar oils or fats, in particular Degras, must be applied that a paint coating can only be applied after removing these oily compounds, but not the phosphate film.

Furthermore, U.S. Patent 3,525,651 discloses a single stage Process for applying an aqueous zinc phosphate solution, which is a finely divided solid mixture of a fatty lubricant and a water-soluble surfactant compound. An applied to a metal sheet treated in this way Although coating has the necessary for deformation

• 309817/1093

Elasticity, but it can still be provided with an additional film of lubricant ^; If the treated sheet metal is to be subjected to severe deformation.

From the foregoing it can be seen that oil films much thinner than those used to protect steel do not provide adequate protection against atmospheric rusting ^ and that phosphate coatings, which are much thinner than those used for pretreatment used for paints also do not provide adequate rust protection.

Surprisingly, however, it was found that

metal surfaces pretreated simultaneously or successively with a phosphating agent and an oily compound have excellent rust resistance and an excellent adhesive strength of organic paints.

The invention thus relates to a method for pretreating metal surfaces using a phosphating agent and an oily compound which is characterized in that it comprises the phosphating agent and the oily compound at the same time or one after the other, whereby processes

Phosphating agents /

are taken where over 50 mg / m / in a separate stage

2 directly or in connection with over 150 mg / m of an oily

Compound can be applied to the metal.

According to this procedure, a surprisingly high degree of

/ Rust resistance _t

suppleness combined with excellent. . '

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achieved. In addition, this method is even advantageous, but at least not detrimental to the adhesion of paints that may then be applied without prior degreasing will.

The term "oily compound" means oils which are insoluble in water and of which small amounts can easily be found in conventional paints, ■ Dissolve the solvents used in dyes and glues. Examples of these oils are mineral oils, vegetable oils, and animal oils other fatty oils, synthetic oils, modified oils and emollients oils.

The choice of substances depends on the intended use.

The oily compound and the phosphating agent can either as a mixture, i.e. as an emulsion or solution, or applied separately, e.g. by treating the steel surface with a ' oily compound and then with a phosphating agent. To achieve the ionization of the phosphating agent ' the treatment must be carried out in the presence of a sufficient amount of water.

The oily compound and the phosphating agent are preferred applied as an emulsion. Such an emulsion may be made from, for example, dilute phosphoric acid, a surfactant compound and dioctyl sebacate.

The preferred oily compound is dioctyl sebacate,

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which is often used in the manufacture of tinplate.

The preferred phosphating agent is orthophosphoric acid, but other phosphoric acids such as phosphorusoxy acid or acidic can also be used

Phosphating mixtures / "_ _k

I ^c * optionally together with detergents,

be used.

The preferred concentration depends on a number of parameters, e.g. the substrate, the treatment time and temperature, the Application method and the required adhesive strength,

however, it is preferably in the range of 0.01 to 1.0

Percentage by volume, based on the aqueous solution. The per m applied The amount of phosphate can be significantly less than that generally used in the prior art.

According to the process according to the invention, phosphate layers of 0.01 to 50 mg / m 2 are produced. However, both extremely thin as well as thicker phosphate layers can be produced.

If the phosphating agent contains an accelerator, for example sodium nitrate, sodium nitrite, sodium chlorate or copper or nickel salts, an improved phosphate layer is formed, the reaction temperatures and times required for the formation of such a layer being reduced. The same effect can be achieved if a phosphating accelerator is present on the steel surface to be protected. The preferred accelerator is a mixture of sodium nitrite

and sodium nitrate.

BATH ORIGINAL

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Although the amount of oily compound to be applied does not

is limited, amounts of 5 to 100 mg per m are preferred, and

depending on the parameters mentioned above.

It can be useful to use an excess of protective agent use, e.g. / an aqueous emulsion of the oily compound and the phosphating agent, in order to avoid the adverse effects of to prevent any impurities that may be present. Therefore, the usual cleaning of the steel before application a coat of paint partially or completely omitted; r:>

If surface conditions, especially a certain suppleness, which then permits metalworking, such as drawing, of the steel sheets obtained, is desired, so this can be done can be achieved by a suitable oily compound according to the method described above *

The two components can be in the form of an emulsion or solution or separately according to different processes, such as rolling, dipping,

Painting, spraying can be applied. Usually there is only one short treatment time with the solution or emulsion required, but this is not a limiting feature. Preferably the treatment time is less than 3 minutes, in particular less than 30 seconds. Mach the treatment is a short one Appropriate drying time. The method according to the invention can be used for treating both cold-rolled and pickled hot rolled steel during any machining stage can be used after tempering or pickling.

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The method according to the invention is of particular importance in the production of steel strip, in particular for production of steel barrels. The steel treated according to the invention must be packaged as usual. In general, stacks of steel flowers and steel band bundles wrapped in polyethylene-coated paper, which in turn is made of sheet steel, optionally reinforced with wooden slats covered to prevent direct exposure to the atmosphere. The inventive treatment of the Steel surface, surfaces are created that are characterized by excellent rust resistance, excellent Appearance for a considerable period of time, improved adhesion of a subsequently applied organic paint and good suppleness. :

The examples illustrate the invention.

The following test methods are used:

1. Paintability

(a) General - The paint is sprayed onto steel sheets 150 300 mm or 150 χ 100 mm in size, which are held in a low position in a spray booth of the waterfall type. Unless otherwise specified, a paint containing brilliant green is used. A conventional hand spray gun is used as the spray device. The paint is used as usual in

single
a 20 to 30 mm thick / layer applied. The trays are then left in a dust-free atmosphere for 5 minutes before they are placed in the drying oven. After the trays have passed the drying

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oven and cooled, the thickness of the paint measured with an electromagnetic induction meter. Eighteen test discs are made from a corresponding number of metal sheets 55 mm in diameter for the test methods described below. ■ ■ _

The test panels are exposed to the following conditions:

(1) room temperature and relative humidity;

(2) Immersion in a moving, thermostatically controlled hot

water bath of 40 - 0.2 ⁰ C for a certain time.

<b) Impact test - procedure and device in accordance with BS3? 00, Part E3 (1966), (impact test). · The method for evaluating the results is slightly modified.

The evaluation of the results caused by a blow to the Prüfblechrückseite 2.5 mm deformation is carried out as follows: -

A 2.5 mm wide transparent adhesive strip is stuck over the deformed part of the paint and pressed firmly so that it adheres to the paint. Then the strip is torn off with a jerk, removing any non-adherent paint. To the. The results are recorded and the paint removed is measured by placing the adhesive tape on milimeter paper. The diameter of the paint removed in the form of a disc is measured, whereby • an area that is not closed but is only removed in tiny flakes is considered a disc.
Three test panels are evaluated for each substrate, whereby

· '■ - ■ 309 * 17/1093 ■ - · ·. pad ΟΒίαΜΜ-

the type of painting and treatment as well as the average removed paint area can be recorded.

Since the test must also contain comparative values, every combination of paint / substrate is an initial value

The areas to be painted are given in mm.

2 +

Fluctuations from 20 to 30 mm, ie from -2 mm in diameter are within the error limit and do not represent any significant changes in the adhesive strength./AU)W ¹ If Sniingen from the initial value mean either an improvement or a deterioration in the adhesive strength.

If by the sudden tearing off of the adhesive strip the paint

i r \ * t γ \ ty g "^ * ΐ Τ""Ί ίΙΙί Υ \

is also removed from / non-deformed areas of the test sheet, this is noted as a severe loss of adhesive strength. Will the Painting of the entire or almost the entire test sheet surface removed, this will be seen as a complete loss of adhesion

(noted. Strong or complete loss of adhesive strength means significantly worse results than the numerical results specified. - ·

2. Erichsen cupping

Method and device according to DIN 53156 or BS39OO, Part Ek (1969), (cupping) with a single cupping. The method for evaluating the results is modified. 16, 18 or 20 BJ prefabricated steel sheets are used. The test procedure is carried out at room temperature.

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■■■■■ · ■ .-. - υ--

The evaluation of the results of a 7 rom cupping is the same as with the impact test with the exception that instead of the Measurement of the distant area an evaluation system in eight stages, is established as can be seen from Table I.

3 test panels are evaluated after the respective treatment and an average value is determined. The last two evaluations, which have not been shown in figures, are presented separately specified.

When evaluating the results, a difference of 2 or more degrees compared to the control value is considered significant One degree differences are considered changes within the margin of error. As with the evaluation of the impact test results a strong or complete loss of adhesive strength means a significantly poorer result.

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- 12 -.
Table I.
Erichsen cupping

Degree

Test sheet description

no visible loss of adhesion or only cracks

individual bits or tiny flakes removed

• · • · Pieces or tiny flakes removed in a ring or disk shape '

• *

■ ·

Bits or tiny pieces in the form of an almost closed one Ring or washer removed

Pieces or tiny flakes in the form of a closed ring or disc removed

large, closed flakes removed in the shape of a disc

strong loss of adhesive strength even in non-deformed areas

Extensive or complete loss of adhesive strength

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BATH ORIGINAL

3. Rust resistance

The evaluation of the rust resistance is carried out according to the method given in Table II

evaluation system shown.

The results represent the average value of three represents I ^{1 1} I IO χ 7 mm wide test panels at 30 - are 1 c a relative humidity of 85 to 90% exposed.

Table II is a standard table for microscopic and macroscopic corrosion testing according to Champion, "Corrosion Testing Procedures", PA Champion, 2nd edition 196 ¹ I, pages 203

to 205. 3 The relationship between description number, designation

and the number of rust spots per dm is given in Table A.

The rust spots found are always larger than 8 mm

(according to the Champion-Il method). .

BATH ORIGINAL

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Table II

very little

considerably

6th
numerous

small amount

.very numerous

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ORIGINAL INSPECTED

- 15 ·· - Table A

Evaluation of rust formation

Description number description 2
Number per dm 1 . - • 'very little 55 · 2 little 100 5 small amount 550 M- moderate ' -· - 1000 considerably 5500. 6th numerous
f 10,000 7th very numerous 55000 ''

4. Phosphate concentration on the steel surface In order to determine the phosphate concentration formed on the steel surface according to the method according to the invention, a radiotracer test is carried out. Cleaned steel sheets that have been degreased in trichlorethylene vapor for 30 minutes, as well as

2 2

Steel sheets that have been treated with 15 mg / m and 100 mg / m sebacic acid dioctyl ester, soluble salts and a mixture of these components become radioactive 90% in 10, 20 and 60 seconds in 0.01, 0.05 and 0.1 percent by volume, respectively Orthophosphoric acid solution {/ P) immersed. The amounts of radioactive phosphoric acid remaining on the sheet surface after drying are measured with the Geiger-Müller scintillation counter.

Those on the surface of 20 seconds in 0.05 percent by volume

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BAD ORICiINAL

Amounts of phosphoric acid (phosphate) remaining in metal sheets immersed in phosphoric acid solution are given in Table B in mg H _: .

The sheets were treated as follows:

Table B.

90 percent phosphoric acid immersion time

0.05 percent by volume 20 seconds

Surface treatment

Steel degreased with trichlorethylene

Steel with 50 mg / m * "

ρ steel with 15 mg / m ² sebacic acid dioctyl ester steel with 100 mg / m 2 sebacic acid dioctyl ester

ο steel with 50 mg / m NaNO ₀ and,

2
15 mg / m sebacic acid dioctyl ester

Steel with 50 mg / m NaNO ₀ and 100 mg / m dioctyl sebacate 25 30

16 9 5

12th

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^ Example 1 225Ί6Π

An aqueous emulsion is prepared which contains 1 percent by volume dioctyl sebacate, 0.1 percent by volume 90 percent orthophosphoric acid, 0.2 percent by weight sodium nitrate, 0.01 percent by weight sodium nitrite and 0.05 percent by volume of a surface-active compound TRITON X - * »5). Cold-formed plus steel sheets (according to BSIM9, Part IB (1962), CRiJ quality, with a nominal roughness of 0.0015 ¹ in 10 seconds, then allowed to drip off in a vertical position and dried for one hour at room temperature) are dipped into this emulsion. .On. The steel

ρ ■ - *

Ί7 mg / m of dioctyl sebacate were deposited on the surface. . · ■.

The steel sheets are as described above for paintability and rust resistance tested. The following results are obtained:. . ;

(a) Paintability · /. "· ^: .. '■.'·" - .; ··. "-". ·.

conditions Test procedure with trichlorethylene
degreased steel according to the example
acted.r S.tnhl space
temperature Impact test ρ
.55 mm away ρ
100 mm away 24 hour
Dive into
Water - '. · Erichsen-
test Grade 3 Grade 3 - Impact test strong strength
loss of life ρ
65 mm away Erichsen- ■
test 3rad 5 / stronger hat
Loss of strength . : Grade H

BATH ORIGINAL

309117/1093

(b) Rust resistance

conditions with trichlorethylene
degreased steel -according to the example
treated steel immediate examination .1 2h hours at 85-905?
more relative. humidity 2 1 7 days at 85-9OJS
relative humidity
•. - - ■ 5

Example 2;

A solution of 0.39 percent by weight of sodium nitrate, 0.12 percent by weight of triethanolamine and 0.05 percent by weight of a surface-active compound (PLURONIC L61 ») is prepared. Cold-formed mild steel sheets are immersed in this solution for 10 seconds, then allowed to drain and dried at room temperature. ^{50 mg / m 2 of} sodium nitrite precipitated on the steel surface. An aqueous emulsion is then produced which contains 1 percent by volume dioctyl sebacate, 0.1 percent by volume 90 percent orthophosphoric acid and 0.05 percent by volume of a surface-active compound (TRITON Χ-Ί5). The steel sheets treated with sodium nitrite are immersed in this emulsion for 10 seconds / dried for one hour at room temperature. 108 mg / m 2 of dioctyl sebacate precipitated on the steel surface.

BAD ORIGJNAL

309117/1093

The steel sheets are tested for paintability and rust resistance as described above. The following results are obtained: . . - .. '.

(a) Paintability. · '. . '- .. ··.''' .. '"V'. ·

conditions Test procedure with trichlorethylene
degreased steel according to example be
traded steel space
temperature. Impact test ρ
.55 mm away mm away 2 * 1 hour
Dive into
Water - Erichsen-
test • *
Gray 3 *
Grade .1. Impact test strong adhesive
loss of work 2
.25 mm away Erichsen- - ·.
test 5rad 5 / stronger. 'Stick
strength loss .:. Degree ^

(b) Rust resistance

•
Conditions · ■ . with. Trichlorethylene
degreased steel " according to the example
treated steel immediate examination. 1 1 . 2k hours at 85-902
relative humidity 2 * · ■■ ·. · ■ ·. '·' - ¹ · "■ '- · 7 days at 85- 905S
relative humidity ; ' -V .; ·.

BATH ORIGINAL

^ 09817/1093

An aqueous emulsion is prepared which contains 1 percent by volume linseed oil, 0.1 percent by volume 90 percent orthophosphoric acid and 0.05 percent by volume of a surface-active compound (TRITON XH $) . Cold-formed plus steel sheets are immersed in this emulsion for 10 seconds, then allowed to drain in a vertical position and dried for one hour at room temperature. 8Ί mg / m ^{2 of} linseed oil precipitated on the steel surface

The steel sheets are painted on as described above.

availability and rust resistance * tested. The following results are obtained: ■ * · ■ ·. ■ ·. ... · ..

(a) Paintability · * · * · · '* ". ^; " *.

conditions Test procedure with trichlorethylene
degreased steel according to example be
traded S.tahl space
temperature. Impact test; 2
55 mm away 2
25 mm away ZH hourly
Dive into
Water - ·· Erichsen-
test Grade 3 •
•
Grade ¹ . Impact test Jtarker adhesive
loss of work 15 mm away Erichsen- ··.
test 3rad 5 / stronger JHaCt-
residual loss ... grade 1

(b) Rust resistance

Conditions · with trichlorethylene
degreased steel " according to the example '
treated steel immediate examination 1 - ■ 1 2'I hours at 85-90?
relative humidity 1 7 days at 85-902
relative humidity

3 09817/1093

BATH ORIGINAL

- 21 ■ /
example

An aqueous emulsion is prepared which contains 1 percent by volume dioctyl sebacate, 0.01 percent by volume 90 percent orthophosphoric acid and 0.05 volume percent of a surfactant compound (TRITON X- * I5). Cold-worked in this emulsion Plus steel sheets immersed for 10 seconds, then left to drain in a vertical position and

ratur dried ... There is 43 mg / m on the steel surface Dioctyl sebacate precipitated. . ". '·

. "■ The steel sheets are as described above for paintability and rust resistance tested. The following results are obtained:. .. -. · ...- '· "."

(a) Paintability

conditions Test procedure with trichloroethyler.
degreased steel " according to example be
traded S.tahl space
temperature.
• Impact test \ 2
.55 mm away 90 mm away 2 ^ hour
Dive into
Water - . *
• * Erichsen-
test · . Grade 3 Degree . 3. Impact test strong adhesive
loss of work •
2
50 mm away Erichsen- ··.
test 3rad 5 / stronger .Hait-
"loss of strength .:. Degree \

■ BAD ORIOfNAL

309817/1093

Host persistence

conditions with trichlorethylene
degreased steel " according to the example
treated steel immediate examination. 1 1 2 ^J I hours at 85-902
relative humidity 2 ¹ ■ 7 days at 85-905g
relative humidity 5. ■ ·

Example

An aqueous emulsion is produced which contains 1 percent by volume sebacic acid dioctyl ester, 1 percent by volume 90 percent orthophosphoric acid and 0.05 percent by volume of a surface-active compound (TRITON Χ-Ί5). Cold-formed mild steel sheets are immersed in this emulsion for 10 seconds, then ⁱⁿ submerged. ^ real. position drained and one hour at Jlaumtempe

ρ ratur dried- ^ On the steel surface there are 97 mg / m

Dioctyl sebacate precipitated.

The steel sheets are as described above for paintability and Roat resistance tested. The following results are obtained:. ·. · ..'_ ·

BATH ORIGINAL

309817/1093

(a) Paintability

.2 2 ^ 1611

conditions Test procedure with trichlorethylene
degreased steel according to example be
traded steel space
temperature. Impact test \ 2
.55 mm away 2
40 mm away 2 * lhour ·
Dive into
Water _ . · Erichsen-
test • - - ·
Grade 3 •
*
Degree } . Impact test strong adhesive
loss of work 2 '
• 35 mm away Erichsen- ··.
test 5rad 5 / stronger. "
["loss of strength ^v .:. Grade ²

(b) Rust resistance

Conditions - · -with. Trichlorethylene
degreased steel ' according to the example
treated steel immediate examination ··. · ¹ · ■. " 1 . 2k hours, at 85-902
relative humidity '. ' · 1 ·. 7 days at 85- 30%
relative humidity
c .- - ..- : '5 · ■. ■ '■ ^v _ ■?
1 '■

. Example6. :

A solution is prepared which contains 0.025 percent by volume dioctyl sebacate and 0.01 percent by volume 90 percent orthophosphoric acid in 60 percent by volume isopropanol and ¹ JO percent by volume water. Cold-formed plus steel sheets are immersed in this solution for 10 seconds, then allowed to drain in a vertical position and dried for one hour at room temperature. On the steel surface, 20 mg / m of sebacin

BAD ORiGiNAL

dioctyl ester precipitated.

309817/1093

- 2k ~

The steel sheets are tested for paintability and rust resistance as described above. The following results are obtained:. . . .
(a) Paintability · /. ../ '. '. ·; ■■ ['''.'. · '' *.

conditions Test procedure with trichloroethyler
degreased steel according to example be
traded steel space
temperature
* ' Impact test \ 2
55 mm away '60 mm away Zk st and ige's
Dive into
Water -
•
• Erichsen-
test . · - - ·
Degree 3 *
•
Grade 1. Impact test strong adhesive
loss of work 50 mm away Erichsen- ··.
test 3wheel 5 / stronger! Detention
loss of strength . .:. Grade 3

(b) Rust resistance

*
Conditions .: with. Trichlorethylene
degreased steel " • according to the example
treated steel immediate examination. ■ · 1 '■ ■ ■ 2 · 2k hours at 85-9Οίί
relative humidity • "-2 ^; ■. ■ 7 days at 85-90 ?;
relative humidity 5 · ^; ;; . - - ₂ . -.

309817/1093

BATH ORIGINAL

Example 7

An aqueous emulsion is prepared which contains 1 percent by volume dioctyl sebacate, 0.1 percent by volume 90 percent orthophosphoric acid and 0.05 percent by volume of a surface-active compound (TRITON X- ^ 5). In this emulsion oiled steel sheets are degreased with trichlorethylene, hot-rolled, immersed for 10 seconds then drained i _n a vertical position and one hour at room temperature dried. 156 mg / m 2 of dioctyl sebacate precipitated on the steel surface. '

The steel sheets are tested for paintability and rust resistance as described above. The following results are obtained:. . ..-. V ■: '. ·

(a) Paintability ·; ./. * ■ '· .- ·', "". ' . ^: ''. ·

conditions Test procedure with trichlorethylene
degreased steel according to example be
traded steel space
temperature Impact test '. 90 mm away 2
HO- mm away 2-hour's
Dive into
Water - · Erichsen-
test Degree 2 •
Grade ' ² . V.
Impact test more complete
Adhesive strength
, loss .. , ρ
.. mm away Erichs en- ··.
test . ■.:. Grade 3

BATH ORIGINAL

309817/1093

(b) Rust resistance

Conditions · with. Trichlorethylene
degreased steel according to the example
treated steel immediate examination ' 1 1 ." 2 * 1 hours at 85-90, ¹ t
relative humidity 2 '■' ■; . • 1 7 days at .85- 90%
relative humidity ■ r. . "* *

Examples

An aqueous emulsion is made that is 0.025 percent by volume Dioctyl sebacate, 0.1 volume percent 90 percent Orthophosphoric acid and 0.05 percent by volume of an interfacial

/ Will contain (45 X TRITON) active compound. With this emulsion "/

/ more evenly

Cold-formed mild steel sheets painted until a liquid film has formed. / "'

7 "~ The plates are then drained i _n a vertical position and a Sturide at room temperature have dried .On the steel surface is 5 ¹ * mg / m dioctyl sebacate depressed.

The steel sheets are as described above for paintability and rust resistance tested. The following results are obtained:. . . ·

BATH

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(a) Paintability

conditions Test procedure with trichlorethylene
degreased steel geni.example be
traded steel Space-
temperature. Impact test '. 2
55 mm away ρ ■
" ^: 95 mm away 2 hours
Dive into
Water -
• Erichsen-
test . · - ·
Grade 3 Grade '5. Impact test strong adhesive
loss of work 2
35 mm away Erichsen-
test 3rad 5 / stronger. Adhesion
strength s loss .:. Grade 5

(b) Rust resistance

•
Conditions -. . - . with. Trichlorethylene
degreased steel " according to the example
treated steel immediate examination • 1 "■ ·. * ' ■ 1 · 24 hours at 85-903
relative ^ humidity '. - ¹ -ν ''' 7 days at 85-905
relative humidity : -5. '■ · - ■'"■ · ^v

OW6INAL INSPECTED

309817/1093

- 28 Example 9

An aqueous emulsion is prepared that is 0.25 volume-. Percent castor oil, 0.1 percent by volume 90 percent orthophosphoric acid and 0.05 percent by volume of a surface-active compound (TRITON X-il5). Cold-worked plus steel sheets are immersed in this emulsion for 10 seconds, then allowed to drain in a vertical position and for one hour at room temperature dried -. ■ ^{on the} steel surface have ". -

• 112 mg / m 'castor oil' precipitated. -

The steel sheets are tested for paintability and rust resistance as described above. The following results are obtained: '.. ·. ··. ■■ (a) Paintability ·;. '/ "·' .V '; -. **'·>\;>' ^v ". '.'; .. ""'.

conditions Test procedure with trichlorethylene
degreased steel according to example be
traded steel space
temperature
. ·. ■. · ·
'hm *
. ·
•. * ''
* ■ · Impact test [ • *
ρ
55 mm away. '' 2 '
50 mm away 2 hours * s
Dive into
Water -
• * -
• Erichsen-
examination · ■ ·. . · ■ ·
"Qrad 3 •
Grade 1 . Impact test itarker adhesive
loss of work •
¹ IS mm away Erichsen- ··.
test > wheel 5 / stronger. adhesion
strength loss .:. Grade 3

(b) Rust resistance

conditions

steel degreased with trichlorethylene "

Steel treated according to the example

immediate examination.

2k hours at 85-902 relative humidity

7 days at 85- 90%

relative humidity

ORIGINAL INSPECTED

Example 10

An aqueous emulsion is produced which contains 0.25 percent by volume of lubricating oil (CROD AFLUID G 6938); 0.1 percent by volume 90prozenti _K e orthophosphoric acid /. ■ &

¹ and about 05 volume percent of a surface-active

Contains compound (TRITON X-H5). In this emulsion cold worked Flusstahlbleche are immersed for 10 seconds then allowed to drain I _n and a vertical position for one hour at. Dried room temperature. - ... 135 mg / m "'of lubricating oil. Has deposited on the steel surface.. ·. __: · _Λ - ··· .: \ . ·

The steel sheets are tested for paintability and rust resistance as described above. The following results are obtained: "'· ...,.'·" ■ ·. ·. (a) Paintability ·; .. ": / '** · *.'. · '■>' .. ^; "'^:; f ' ^; '"' ."'^; .. ""

•
Baäi'nßungen Test procedure with trichlorethylene
degreased steel geni.Beispie], be
traded steel space
temperature
* ·
• ·· ».
•
«* * Impact test '. •
ρ
55 mm away 2
'50 mm away 2i | hourly
Dive into
Water _ . ·
• Erichsen- ""
examination · ■. ". · Grade. 3 Grade ' ² . Impact test strong adhesive
loss of work 50 mm ² away Erichsen- ·· .-
test 3rad 5 / stronger .Tfefb-
loss of residue .;. Degree "3

". (b) Rust resistance

Conditions ·. * . with. Trichlorethylene
degreased steel ' according to the example
treated steel immediate examination. 1 ■ ·· .; '" 2k hours at 85-9OU
relative humidity 2 7 days at 85-90 ^
relative humidity
· * ..— · ■ · ■ a ** ·
5 ··· ■ .. · ". ' Λ "r. ' -it · '■ · -;.: ■■' ■. ·. "

- 30 - 'Example 11

An aqueous emulsion is produced that contains 0.25 percent by volume epoxy-free linseed oil, 0.1 volume percent 90 percent orthophosphoric acid and 0.05 volume percent of a surfactant compound (TRITON X- ^ 5). In this emulsion, cold

deformed plus steel sheets immersed for 10 seconds, then in lowering. drained in the right position and dried for one hour at room temperature. 61 mg / m ^{2 of} epoxidized linseed oil were deposited on the steel surface.

The steel sheets are checked for paintability and rust resistance as described above. The following results are obtained: '. . . . ·· -. ' ■ '...' * (a) Anstreichbarkcit ·;. . · *. '* ^R ·· *. ·

• _a * ■
conditions Test procedure
• * * with trichlorethylene
degreased steel geni.Deispie], be
traded _t 4ta.hl space
temperature
■ ·
•
■ · "
• · Impact test '. . ·.
2
55 mm away 2
'50 mm away 2 (I st and ige s
Dive into
Water - ·
• ·
• Erich s en- * «
test · . . •
Orad. 3 Degree l. Sleep test strong adhesive
loss of work ■ ·
2
55 mm away Erichsen- - ·. *
test 3rad 5 / stronger Hait-
residual loss .:. Grade '3

. (b) Rust resistance

■ ·
Conditions ·. . * . with. Trichlorethylene
degreased steel " according to the example
treated steel immediate examination. • 1 ···· ■ -; * '"*' ■■" ι 2h hours at 85-90?
relative_humidity • ■
2 ·. ·. ·. ■ ' '· 1 7 days at 85-9055
relative humidity • * Γ · · ·:.
: · 5 ·. · ■ .. · * · 2 '
* · · "

Mk INSPECYEÖ

Example 12

An aqueous emulsion is prepared which contains 1 percent by volume sebacic acid diacid, 0.1 percent by volume 90 percent orthophosphoric acid and 0.05 percent by volume of a surface-active compound (TRITON X-H5). This emulsion is used for cold-working Plus steel sheets poured over, after 10 seconds by

/ guided in vertical nip rollers and then one hour at room temperature /

Position dried. There are 108 mg / m ^{2 on the steel surface}

Dioctyl sebacate precipitated.

The steel sheets are to be painted on as described above it and rust resistance tested. The following results are obtained: '...... .. · ". ..."

(a) Extensibility '· '''.'':':'}'' · '. *. · * ■; · .- »\

conditions Test procedure
• * * with trichlorethylene
degreased steel according to example be
hands it er ^ tahl space
temperature
' "· · · Impact test; ρ
55 mm away '55 mm away 2llsecutive -
Dive into
Water _
• Erichsen- i
test · . ". Grade. 3 Grade ' ² . Impact test strong adhesive
loss of work • ·
50 mm ² away Erichsen- "■ ·· .-"
test 3rad 5 / stronger!
"loss of strength .:. Grade ⁴

. (b) Rust resistance

* »
Conditions ·. . with. Trichlorethylene
degreased steel ' according to the example
treated steel immediate examination. '·· ■■■ ι 2k hours at 85-902
i> elative._humidity • ■ '' · Ι ·· ' 7 days at 85-90 ^
more relative. humidity • ■ '·: · · ■: ..

3, ■. · ORiGlNAL-INSPECTEO

a) An aqueous solution is prepared that is 0.1 percent by volume Contains 90 percent orthophosphoric acid and 0.05 percent by volume of a surface-active compound (TRITON X-45). With this Solution are poured over cold-formed mild steel sheets Passed through squeeze rollers for 10 seconds and then dried in a vertical position for one hour at room temperature.

b) At the same time, an aqueous emulsion is produced which

1 volume percent dioctyl sebacate and 0.05 volume percent of the surface-active compound. In this emulsion cold-formed plus steel sheets are immersed for 10 seconds, then allowed to drain in a vertical position and for one hour at Room temperature dried. 61 mg / m3 sebacic acid dioctyl ester precipitated on the steel surface.

■ ■ ·· ■ '. : '· ■: .. ■■ t''■ ·

The steel sheets are painted on as described above. Checked for availability and rust resistance. The following results are obtained: . . ·.

(a) Paintability

conditions Test procedure with trichlorethylene
degreased steel according to (a) be
traded steel space
temperature Swing test ' 2
.55 mm away 70 mm away 2 ^ lhours
Dive into
Water - Erichsen-
test Grade 3 Grade 3. Impact test 3 strong adhesive
loss of work 60 _m m away Erichsen-
test 3rad 5 / stronger adhesive
loss of strength Grade 4

ORIGINAL INSPECTED

conditions Test procedure like ', (b) be
traded steel space
temperature Impact test ' i \ 0 mm away 2k hour
Dive into
Water -
• * Erichsen-
test · O 1
Impact test more complete.
>
Loss of \
Adhesion strength ·. " Erichsen- ··. '.
test
Il. I -.— ■■■,

(b) Rust resistance

B.
Conditions ·. · . with. Trichlorethylene
degreased steel " according to (a)
treated steel immediate examination ·. '. ■■ · ■ ¹ ■ -. .. " 1 . '" 2k hours at 85-9O #
relative_humidity • 1 ·" 7 days at $ 85-90?
relative humidity

Conditions ·. . · . "according to - (b). '- -.;
b ehande It er -St ah.1 immediate examination. 1 ' · -' 2k hours at 85-903
relative. ^ humidity 1 · : · · 7 days at 85-90 ^
relative humidity
· «. · - ·. . ·· '· · · Γ · ·. :.

ORIGINAL INSPECTED

• - 34 -

The surface of cold-formed mild steel sheets is made with 289 mg / m oil containing dioctyl sebacate and 2.5 percent of a surface-active compound (TRITON X-45), pretreated. These steel sheets are then treated with an aqueous solution containing 0.1 percent by volume of 90 percent orthophosphoric acid ^ Poured over, - passed through squeeze rollers after 10 seconds and then dried for one hour at room temperature in a vertical position.

The steel sheets are painted as described above on

availability and rust resistance * tested. The following results are obtained

• ■■■ ** ·. · *

Results: .. · .-. ■. ' . . . .. ·. "

(a) Paintability

conditions Test procedure with trichlorethylene
degreased steel according to example be
traded. ^ tahl space
temperature.
• * Impact test \ ρ
.55 mm away 2
40 mm away 2 Jlst and ige's
Dive into
Water - .· ·.
• * * Erichsen-
test ;. Grade 3 •
•
Degree ^ί . Impact test strong adhesive
loss of life ²⁰ mm away Erichsen- ··.
test 3rad 5 / stronger .'Hait-
["loss of strength .:. Grade 4

(b) Rust resistance

•
Conditions ' with trichlorethylene
degreased steel " according to the example
treated steel immediate examination 1 • 1 2'1 hours at 85 ~ 9O3
relative humidity 2 " • 1 7 days at 85-90S
relative humidity •
•

'.OWQINAL INSPECTED

Cold-formed plus steel sheets with a surface of 50 to

2 "■ ·
100 mg / m of a mixture of 20 percent by weight of sebacic acid dioctyl ester, 25 percent by weight of soluble inorganic salts, 13 percent by weight of iron residues, 2 percent by weight of carbon black and insoluble silicon dioxide, 28 percent by weight of triethanolamine and 12 percent by weight of surface-active ethylene oxide compounds are immersed for 10 seconds in a solution containing 0, 1 volume percent contains 90 percent orthophosphoric acid, then allowed to drain in a vertical position and dried for one hour at room temperature.

The steel sheets are paintable as described above and rust resistance tested. The following results are ■ results:

(a) Paintability

The paint used in this experiment is a toluidine red containing epoxy resin paint ·. Only the impact test is carried out. .

*
conditions not with phosphoric acid
treated contaminant
tfiV · steel. · with phosphoric acid
■ treated contaminated
r> Pl ni ef-. ^ T St: fth1 Emancipate at-ur ρ
45 vm. - removed 40 * mm away 1 day immersion bath total imprisonment
loss of strength 2 · ·
■ 30 mm away 7 days immersion bath Il. ρ
20; mm away

(b) Rust resistance c

•
Conditions ·. · niclit with phosphoric acid
traded contaminant
ter steel * • · with phosphoric acid
treated verun
cleaned steel immediate examination- .. , 1 • · ·. r.
• 1 Zk hours at 85-902
relative humidity • ■ · ' 7 days at 85-9 ⁰ ^
relative humidity

B e 1 s ρ ie 1 1%

An aqueous emulsion is prepared which contains 1 percent by volume dioctyl sebacate, 0.1 percent by volume 90 percent ortho-, phosphoric acid and 0.05 percent by volume of a surfactant:

Contains compound (TRITON X- ^ 5). This emulsion is sprayed onto cold-formed mild steel sheets until a uniform liquid film has formed. . ,, ■ ^:

After 10 seconds the sheets will

dried by means of compressed air and left to stand at room temperature for one hour. 49 mg / m _2: sebacic acid dioctyl ester precipitated on the steel surface.

The steel sheets are as described above for paintability and rust resistance tested. : ian receives the following results:

OWGINAL INSPECTED

309817/1093

(a) Paintability

conditions Test procedure with trichlorethylene
degreased steel like. Example be
traded S.ta.hl space
temperature
• * .. ■. Impact test '. ρ
55 mm away 2
50 mm away 2 (1 hour
Dive into
Water -
• · Erichsen-
test · ... ·
Grade 3 •
Grade ¹ . . Impact test strong adhesive
loss of work 2
40 mm away Erichsen- ··. '
test 3rad 5 / stronger
loss of fitness . ; Degree. "H

' (b) Rust resistance

Conditions ·. . . · . with. Trichlorethylene
degreased steel " according to the example
treated steel immediate examination ·. 1 - ■ -... ' 2k hours at 85-903
relative ^ humidity • CVJ . - 1; ■■. 7 days at 85-905
relative humidity "■" · '■■■ ι · "'" ■ "■" ■ · ■ "'

ORIGINAL INSPECTED

309817/1093

Example 1?

An aqueous emulsion is prepared that is 1 percent by volume Dioctyl sebacate, 0.01 percent by volume 90 percent orthophosphoric acid and 0.05 percent by volume of a surfactant Contains compound (TRITON X- ^ 5). Be with this emulsion cold-formed plus steel sheets are injected until a uniform has formed a liquid film. After 10 seconds, the sheets are dried by means of compressed air and for one hour at Left to stand at room temperature. 58 mg / m 2 of dioctyl sebacate precipitated on the steel surface.

The steel sheets are tested for paintability and rust resistance as described above. The following results are obtained:
(a) Paintability · "*. .. · ■■. ". - * '

Conditions Test procedure with trichlorethylene
degreased steel according to example be
traded steel space
temperature Impact test 2
.55 mm away Cc 2
° i> mm away 2 hours
Dive into
Water - Erichsen-
test Grade 3 Degree ^A. Impact test strong adhesive
loss of work 85, mm away Erichsen- · -.
test 3rad 5 / stronger adhesive
loss of strength ..:. Degree ^

(b) Rust resistance

conditions with trichlorethylene
degreased steel " according to the example
treated steel immediate examination 1 1 2k hours at 85-902
relative humidity 2 1 7 days at 85-; 0S
relative humidity '3

30S1T7 / 1093

OWQINAL INSPECTED

"■ - .." Example l8 '9 9 R1 Ri 1

An aqueous emulsion is prepared which contains 1 percent by volume dioctyl sebacate, 0.1 percent by volume 88 percent orthophophoric acid and 0.05 percent by volume of a surfactant
Compound (TRITON X-45) contains. Cold-worked mild steel sheets are immersed in this emulsion for 10 seconds, then allowed to drain in a vertical position and for one hour at room temperature

dried. There are 83 mg / m sebacic acid diocty on the steel surface lester dejected.

At the same time, an aqueous emulsion is produced which
1 volume percent dioctyl sebacate and 0.05 volume percent of the surface-active compound. In this emulsion

ρ
Plus steel sheets are dipped with a 500 mg / m 2 phosphating layer for 10 seconds, then allowed to drip off in a vertical position and dried for one hour at room temperature. On the
phosphated steel surface 42 mg / m sebacic acid dioctyl ester precipitated. -

The steel sheets are tested for paintability and rust resistance as described above. Plan gets that into the
Tables C and D summarized results:

BATH ORIGINAL
309817/109 3

(a) Paintability

Table C.

Test procedure Room temperature with trichloro with trichloro in Sebacin- in Sebacin- Erichsen- 1 day diving- ethylene ent ethylene ent acidic acidic painting Exam bad fatter fatter octyl ester ^ octyl ester / 7 days diving stole stole emulsion phosphorus bath (0.0015 mm resp. (0.00038 to submerged acid emul 60 micro 0.00045 mm or phosphating sion immersed inch) 15-18 ter steel ter not Microinch) (0.00038 to phosphating 0.00045 mm ter steel Room temperature or 15 - Io (0.0015 mmbaw. 1 day dive Microinch) 60 microinches) exam bathroom 20th 0 40 0 Red 7 days diving 55 0 νπ 20th iron bath oxide ent 65 0 75 1 keep 2 0 4th 2 the at 2 0 νπ 1 stroked .3 0 5 1

- Ill - ·

Rust resistance Table D.

conditions in Sebacin-
acidic
octyl ester
emulsion
submerged
phosphating
ter steel in Sebacin-
acidic
octyl ester /
Phosphorus
acid emul
sion immersed
ter not
phosphating
ter steel instant
test 1 1 2k hours
at
85-90 %
more relative
humidity 1 1 7 days
at
85-90 %
more relative
humidity 1
* 1

309817/1093

-112 example i9

Cold-formed, commercially available plus steel becomes 1.25 mm

"" "- ■ · ■■> thick sheets cut. Some of these sheets are immersed in a bath for 5 seconds, tap water, 0.02 percent surface-active compound (TRITON X-IOO) as well as the respective amounts of acid specified in the table below. The sheets are then dried. Another part of these sheets is immersed in a 5 g sebacic acid dioctyl ester for 5 seconds immersed in 1 liter bath containing ethyl ethyl ketone and then

dried. On the _{steel surface there are 8o} '

up to 100 mg / m sebacic acid dioctyl ester precipitated. Another part of this sheet is first made with dioctyl sebacate and then treated with the acids specified in the table below. Finally, for comparison purposes, untreated steel sheets and sheets that only immersed in the above-mentioned sebacic acid dioctyl ester solution will be.

Steel sheets are left outdoors under a rain cover for 5 days. The formation of rust on the surface, which is visible to the naked eye, is then determined. The results are in summarized in the table below:

BATH

309817/1093

Tabel

approx - O O S. co g> 00
—K f-
Z O (O (O co m O -i • m σ

treatment g / i. • Rust formation, percent Phosphating
medium and
closing · ''
Sebacic acid dioctyl
ester Sebacic acid dioctyl
ester and then
Phosphating agents ·. middle 1
30 ' without sebacic acid
redioctylest-er 90
20 ..
20th
• 5 .. • 90 "
30 "·
20 ·
25th
5 no 'acid
85 pounds of phosphorus
acid
Polyphosphorus
acid (82%? ~ Or.)
3Ö ^ ige - ^
p'hosphorous
acid
GRANODINE 20. (Φ) '100
90
^1st 90
^; 90
• - ^v 95 ^;

(1) Conditions according to the manufacturer's instructions; Dive time 4, minutes at 90 ⁰

cn

IO I I

Some of the steel sheets are then provided with a 25 to 30 μ thick layer of gray alkyd resin paint. After 2Ί hours in a drying oven, the sheets are immersed 2H hours in distilled water at ¹ JO ⁰ C. The Erichsen test is then carried out with a deepening of 7 mm in order to determine the percentage loss of adhesive strength. Weakly adhering paint is removed with the help of an adhesive strip and the loss of adhesive strength is determined in accordance with Table I. The results are summarized in the table below:

treatment E / l Loss of adhesion. Sebacic acid
octyl ester and
afterward
Phosphating
middle Middle. 1 Phosphating
medium and then
send sebacic acid di
octyl ester • *, 85% phosphoric acid 1 ■■■■ * Polyphosphoric acid 1 i:. '. ; I. 30 # phosphorous
acid 30th GRANOLINE 20 NJl
■ severe loss of adhesion ' untreated

309817/1093

ORIGINAL fNSPECTED

Example 20

To improve the achievable with the method according to the invention Show elasticity in steel used in metalworking, the pliability in both deep drawing and stretch forming is determined from those listed below The procedure described by the authors determines:

1. J.G. Wright in "Sheet Metal Industries" 28, No. 414, October 1961, pages 731 to 741;

2. DH Lloyd in "Sheet Metal Industries" £ 9, No. 419, March 1962, pages I58 to Löoj

5. J.F. Wallace in "The British Iron and Steel Research Asso-:

ciation report "No. MW / e / 62/55;
4. U.S. Rao in Sheet Metal Industries 44, No. 486, October

1967, pages 673 to 678. '

The middle of a cold-formed mild steel strip becomes several

Sets of slices of 55 mm diameter cut. Every sentence will

in triehloroethylene vapor, degreased and according to the table below treated. For comparison, sets of steel disks are 'put together' that are not treated with a lubricant and on both sides with a 100 / λ thick film of polyethylene lower Density are provided.

Treatment oil concentration, in mg / m

cleaned steel sheets -

CRODAFLUID 0 6958 1) in excess

TELLUS-I5-ÖI 2) in excess

309817/1093

ζ / οίοι «

Thin sebacic acid dioctyl ester film from an emulsion with 1 percent by volume diiootyl sebacate and 0.05 percent by volume 73 cent of the surface-active compound TRITON X-45

Thin CRODAFLUID O 6938 film from an emulsion with 0.25 percent by volume CRODAFLUID Q 6938 and 0.05 21 percent by volume TRITON X-45

Thin film of TELLUS-15-Ö1 from an emulsion with 1 volume percent TELLUS-I5-ÖI and 0.05 Vo- 23 lumen percent TRITON X-45

Paint according to the invention of dioctyl sebacate and orthophosphoric acid from an aqueous emulsion with 1 volume percent sebacic acid dioctyl ester, 0.1 volume 114 Percent 90 percent orthophosphoric acid and 0.05 percent by volume TRITON X-45

Paint according to the invention made from CRODAFLUID Q 6938 and orthophosphoric acid an aqueous emulsion with 0.25 volume percent CRODAFLUID 0 6938, 0.1 volume

309817/1093

continuation

percent 90 percent ortho-

phosphoric acid and 0.05 percent by volume TRITON X-45

Paint according to the invention of TELLUS-15-Ö.1 and orthophosphoric acid from an aqueous emulsion with 1 percent by volume TELLUS-15 oil, 0.1 percent by volume 90 percent orthophosphoric acid and 0.05 Volume percent TRITON X-45

100 / λ thick film of low density polyethylene applied on both sides

Treatment with an aqueous solution of 0.1 percent by volume 90 percent Orthophosphoric acid

'CRODAFLUID G 6938 from Croda Chemicals Limited · i ² ^ TELLUS-15-Ö1 from Shell-Mex and BP Limited

The elasticity is measured with a hydraulic Erichsen test device of the type W 126, which is equipped with devices for measuring the load and who is endowed with depths.

The elasticity of stretch forms is measured with Erichsen

Test plates / cupping tests determined on the basis of / with a diameter of 55 mm, namely the elongation to break and the maximum load. A high aspect ratio and a low maximum

309817/1093

- ii8 -. ^:

load indicate good elasticity, with a film of low density polyethylene being considered optimal.

Elasticity during deep drawing is achieved with the Erichsen

Test sheets / device using 33 ^mm cupping tools and / from

Measured 55 mm in diameter. The relative smoothness of the various Paint is determined as the result obtained in deepening and the deepening maximum load. Low cupping values and low maximum load indicate good elasticity, with a film of low density polyethylene being optimal is applicable.

The results obtained on the deep are graphical below shown.

In all of the test sheets examined, the elasticity lies with . the process according to the invention is achieved above that of the respective individual components. It is also generally better than paints which have high concentrations of oil on the steel surface.

% 08804

309817/1093

GRADKOWSKf

Erichsen cupping

maximum load (arbitrarily selected units)

■ - - 20 50 A-O 50

treatment

without .lubricant (i) cleaned, degreased stole

(il) phosphated stole

conventional lubricant in excess

(i) CRODAFLUID G6938

33.9

36.7

(ü) TELLUS 15

thin oil films from aqueous F.mulsipnen

(i) Dioctyl sebacate.

(ii) CRODAPLuiD G6938

(JU) TELLUS 15
oils according to the invention

(i) Dioctyl sebacate

(ii) CRODAPLUID
(Ui) TELLUS 15

33.5 '

. 32.5-49 60

- three from four Test panels break - / ■ «:
V. 55 , 0 • · 38

34 ,1 one from "three Test panels breaks 15th , 6 I. 38 , 0

32.0 test panels - don't let me
Lows and breaks under stress

excellent lubricant polyethylene film

27.8

Claims (15)

Claims 1. Method of pre-treating metal surfaces using of a phosphating agent and an oily compound, characterized in that the Applying phosphating agent and the oily compound simultaneously or sequentially, with the exception of processes 2
those over 50 mg / m phosphating agent in a separate 2 stage directly or in connection with more than 150 mg / m oily Compound is applied to the metal. 2. The method according to claim 1, characterized in that the oily compound and the phosphating agent are used together brings up. 3. Process according to Claims 1 and 2, characterized in that the oily compound used is dioctyl sebacate. 4. The method according to claims 1 to 3, characterized in that an accelerator is additionally used. 5. Process according to claims 1 to 4, characterized in that an aqueous solution is used as the phosphating agent, which contains 0.01 to 1.0 volume percent phosphoric acid. 6. The method according to claims 1 to 5, characterized in that that a phosphating agent with a content of sodium * 309817/1093 - 51 -. nitrite and sodium nitrate are used as accelerators. 7. Procedure according to the. Claims 1 to 6, characterized in that 2 that the oily compound in an amount of 5 to 100 mg / m brings up. 8. The method according to claims 1 to 7, characterized in that-the oily compound and the phosphating agent in an aqueous emulsion applies. 9. The method according to claims 1 to 8, characterized in that the oily compound and the phosphating agent in an aqueous solution containing a solvent. 10. The method according to claims 1 to 9, characterized in that that the phosphating agent in an amount of 0.01 to 40 mg / m applies. 11. The method according to claims 1 to -10, characterized in that that steel is used as the starting material, the surface of which is already provided with an oily compound. 12. The method according to claims 1 to 11, characterized in that that one uses the protective agent in excess. 13. The method according to one of the preceding claims, characterized in that that steel is used as the starting material, the surface of which is treated with a phosphating accelerator 309817/1093 I ■ t ι.; - ₅₂ -. ■ * .ίΛ. Protective means is provided. 14. The method according to any one of the preceding claims, characterized in, that the surface is brought into contact with the pretreatment liquid for up to 3 minutes. 15. The method according to any one of the preceding claims, characterized in that ge * - indicates that the surface is brought into contact with the pretreatment liquid for up to 30 seconds. BATH ORIGINAL 309817/1093