DE2155766A1 - Corrosion preventing products - Google Patents

Description

The present invention relates to new ones which prevent corrosion Products and especially those products that contain benzotriazole derivatives.

It is known that benzotriazole effectively the corrosion of metals, particularly copper and copper alloys, v / äßrigen media such Metallreinigungaprodukten and polyphosphates as binding compounds containing KetalIioneη en detergents verhind ert.

However, metal-binding substances ("sequestering agents"), which are more aggressive towards metals than the polyphosphates (such as the alkali metal salts of ethylenediaminetetraacetic acid or nitrilotriacetic acid), as the sole metal-binding products or in addition to other metal! binding products in such If aqueous media are used, it must be found that Bensotriaaol

209821/1004 ~ ² ~

as a means of preventing corrosion of copper when in use shows practically no effectiveness in such solutions.

It has now been found that mixtures of benzotriazole or one Copper protective derivative thereof with special oximes surprising proved to be very effective means of protecting metal surfaces represent, especially if they are used in preparations that contain strong binders ("sequestrants") represent ions that are formed when these products come into contact with metal surfaces.

Accordingly, the present invention relates to new ones Corrosion of metals, especially copper and copper alloys preventing products, the benzotriazole or a Copper protective derivative thereof in combination with an oxime, preferably in a weight ratio from 1:20 to 20: 1 and very particularly preferably in a weight ratio of 1: 4 to 4: 1 · ■

The present invention also relates to preparations, which consist of a base material called the corrosion preventive product contain benzotriazole or a copper protective derivative thereof in combination with an Oxira.

Example of base materials are lubricants, hydraulic Liquids, petroleum products, paints and polymers

209821/1004

Products. If the base material is a lubricant, it can also be used to a corrosion inhibitor according to the invention other conventional additives such as antioxidants (e.g. aromatic Amines or sterically hindered phenols), viscosity-improving products (e.g. polyacrylates), products that lower the pouring point Products, dispersants or cleaning agents (e.g. Metal sulfonates) or additives for extremely high pressures or to increase abrasion resistance (e.g. tritolyl phosphate).

In a more specific embodiment, the present invention also relates to products containing a water-soluble metal ion binding product that forms a copper chelate with a log stability constant greater than 10, or a mixture thereof Wasserlösucher, 1 metal ion binding products, of which at least one is a copper chelate with a log stability constant forms greater than 10, and additionally as the tarnishing of the surface or. the corrosion preventing product an alkylbenzotriazole having 1 to 20 carbon atoms in the alkyl chain, bis-benzotriazoles or 4,5,6,7-

\ next /
Tetraliydro-benzotriazole ür.cf also contain an oxine.

The corrosion inhibitor is preferably a triazole of the general type formula

209821/1004

BATH ORIGINAL

wherein A is a benzene ring, an alkyl substituted benzene ring with 1 to 20 carbon atoms in the alkyl chain, one over one Pontic with the rest of the formula

e ι

II
or benzene ring linked to a cyelohexene ring is »Die

The present invention further relates to aqueous solutions of such

Products.

The log stability constant is that of the Chemical Society Publication published in London in 1957 "Stability Constants" Special Publication Mr. 6 defined.

Strongly aggressive products that bind metal ions are e.g. Alkylenamino or alkylenepolyaminocarboxylic acids and their alkali metal, Alkaline earth metal and amine salts, urilopolycarboxylic acids and their salts, aminopolyphosphonic acids or hydroxypolyphosphonic acids and derivatives thereof or hydroxy or polyhydroxycarboxylic acids. Specific examples of such metal ions binding products are the di-, tri- and tetrasodium salts of Ethylenediaminetetraacetic acid, the pentanatriuci salt of diethylenetriaminepentaacetic acid, the trisodium salt of Hydroxyäthyläthyleriäianintriacetic acid, the disodium or dipotassium salt of ethylenediamine bis (o-hydroxyphenylacetic acid), 1-aminoethane-1,1-diphosphonic acid, 1-aninopropane-i, 1-diphosphonic acid

209821/1004

and 1-aminotoluene-1,1-aiphosphoii8äLn? e, v / which in the British Patent ITr. 995 462 are described, 1-hydroxyethane-1,1-diphosphonic acid, Citric acid and gluconic acid. Trisodium as liitrilotriacetic acid is very particularly preferred. 'J

The metal-binding agents used in the products according to the invention Products can be a mixture of one or more of the above-mentioned, highly aggressive products with a or several only slightly aggressive products such as the alkali metal salts of the condensed phosphates.

Besides the benzotriazole itself, the preferred ones are copper protective benzotriazole derivatives which are substituted on the benzene ring » ated alkyl benzotriazoles with 1 to 20 carbon atoms in the alkyl chain, bis-benzotriazoles or the 4,5,6,7-tetrahydrobenzotriazole. Among the alkyl benzotriazoles with 1 to 20 Carbon atoms in the alkyl chain are particularly preferred as those described in British Patent No. 1,065,995 Compounds 5-ethyl-, 5-n-butyl-, 5-tert-butyl-, Another mentioned 5-n-doaecyl- and 5-n-octyl-benzotriazole preferred class of copper-protecting benzotriazoles are the bis-benzotriazoles, the 5: 5-methylene-bis-benzotriazole and the Bis-benzotriazoles of the general formula

-6-209821 / 1004

wherein X is an alkylene radical having 1 to 6 carbon atoms, preferably optionally with one or more alkyl groups substituted Kethylene radical is a 1,1-cycloalkylidene group with at least 5 carbon atoms, the carbonyl group, the SuIfury! Group-SOp-, oxygen or sulfur. These bisbenzotriazoles are in British patent lir. 1 081 described.

A third preferred, copper-protecting derivative of benzotriazole is 4,5,6,7-tetrahydrobenzotriazole, its production and use as a copper corrosion preventive product described in British Patent No. 1,226,099 is.

Although in the products according to the invention monooximes with good Results for the prevention of corrosion can be used, those oximes are preferred, which still have a further metal-binding Group, in particular

contain a second such group. In this case, the second group can be the following: -OH, -N ^ j ^{= 0} »-N-liiL, · Gans particularly preferably the second group is also an oxime group. The tf-dioximes are very particularly preferred as oximes.

209821/1004

Examples of Honοoxime are given by the following formula as given:

R ₁ CR ₀ II.

.Il

N-OH
Examples of the preferred dioximes correspond to the formula

R ₁ C (R ₃ ) _n CR ₂

N-OH N-OH

where in formulas II and III R ₁ and R ₂ , which can be the same or different, are an alkyl group having 1 to 12 carbon atoms, an aryl radical or an aralkyl radical having 7 to 10 carbon atoms, each of these groups optionally having one or more groups is substituted, which has no metal-binding properties, and R * is an alkyl ene radical with 1 to 4 carbon atoms and η is 0 or 1, these oximes must be substantially soluble in the aqueous system to be treated at the concentrations used.

Any substituents that may be present that are not metal-binding Have properties are, for example, halogen, alkyl, alkoxy and nitro groups.

Specific examples of ilonooximes which can be used according to the invention of formula II are acetoxime, benzophenoxime and in particular

209821/1004

Benzoin & oxime.

If a dioxime of the formula III is used, this is the case preferably those in which R., and Rp are unsubstituted Alkyl groups with 1 to 6 carbon atoms, especially 1-ethyl groups and η is 0, as well as those in which R., and Rp aryl radicals, are in particular phenyl radicals and η is 0. Specific examples of the preferred oximes of the formula III are dimethyl-P glyoxime and diphenylglyoxira.

The total amount of the corrosion inhibitor combined from the benzotriazole and the oxime is preferably in the range from 0.01 to 10% by weight, very particularly preferably in the range from 0.05 to 3 % by weight, based on the total weight of the aqueous preparation .

The metal-binding products according to the invention, in which the

> corrosion inhibitors according to the invention advantageously incorporated -

can be set, can be very different types of products containing aggressive metal-binding substances. from However, metal cleaning agents such as Descaling compositions, detergents for brewery kettles and aircraft, be it in solid material or in the form of aqueous solutions. The products according to the invention are * of particular interest in connection with cleaning agents like dishwasher detergent and preferably in combination ' with cleaning agents for textiles, such as those used in the

209821/1004

Household and industrial laundry and cleaning procedures .for this uses v / earth. Should this be the invention according to a metal binding Product manufactured as a cleaning agent contains it in the generally a non-ionic or preferably anionic surfactant. - ^ Such non-ionic surfactants Substances are polyalkylene glycol derivatives of long-chain fatty amines or fatty alcohols. Examples of common anionic surface-active agents Substances are the alkali metal and ammonium alkyl sulfates and the alkali metal sulfonates and alkyl aryl sulfonates.

The surfactants present in detergents are generally in an amount up to 40% by weight, in particular 10 to 30 yo by weight based on the total weight of the product present.

Further additives can be used in cleaning agents according to the invention be present, such as "builders" »bleaches, products that suspend dirt particles, fillers, optical brighteners, enzymes and / or mild perfumes.

Special bleaching agents used in the products according to the invention Can be used are alkali metal hypochlorites and chlorine-generating products, alkali metal percarbonates and persulfates and especially alkali metal perborates; suitable fillers are, for example, alkali metal sulfates; as suspending dirt particles Product is generally used carboxymethyl cellulose; a triazinyldiamino-

20982 1/1004

stilbene disulphonic acid, an aminocoumarin, a pyrazoline, a Imidazolone, a benzidine sulphone. Bisoxazole or a dibenzolimidazole can be used. Am for the purpose of the present Invention suitable enzyme is such a product that contains in particular a protease produced by a spore-forming Bacterium of the species Bacillus subtilis is formed; as a perfume products can be used that have a lemon, Have colognes or fir base.

In cleaning compositions the metal strip end product is generally in an amount in the range of 5 to 75 parts by weight Jo and Benzotriaz is oil compound in the range of 0.01 to 5 wt .- ^ ₅ are each inserted on the basis of the solid content of the complete detergent product .

The benzotriazole compound and the oxime can with the das metal-binding product containing detergent powder in solid phase can be admixed by any of the known mixing methods for such products, such as in a free-fall mixer or in a ball mill mixer. The powdery obtained The product can then be dissolved in water for the production of aqueous cleaning agents. On the other hand you can too an aqueous slurry can be formed which contains both the metal-binding Agent, detergent and corrosion retardant Contains agent and which is then spray-dried. In this way, a cleaning agent according to the invention is shown in

209821/1004

solid shape formed.

The metal strip products in which the inventive Corrosion inhibitors can be used in any type of household or industrial washing or cleaning equipment and in particular are used in those in which the product comes into contact with metal and in particular with metallic surfaces made of copper or copper alloys is coming ". Such metal surfaces can be copper parts of the machines or metal objects on the clothes to be cleaned v / ie forging made of nickel-copper alloys. The corrosion effect inhibited according to the invention, Metal-binding products have a remarkably reduced tendency to metal corrosion, especially the corrosion of surfaces of copper and alloys.

The following examples further illustrate the present invention. Parts and percentages relate to weight, unless otherwise stated.

Examples 1 to 7

A detergent powder was made from the following products of the following proportions based on weight:

-12-

209821/1004

BAD ORIGW _AL

I sodium perborate 20 fo

Trisodium salt of nitrilotriacetic acid 15 %

ITodium tripolyphosphate 20 fo

Sodium dodecyl sulphonate 27 ° / o

Monoisopropanolamide of lauric acid 5 $>

I Sodium Metasilicate 10 ^c ß>

Carboxymethyl cellulose 2.9 i °

A 1,3 »5-triazinyl derivative of
. 4,4 «-diaminostilbene-2,2'-di-

sulphonic acid (disodium salt) $ 0.2

From the above-mentioned pesticide detergent mixture were then 0.1, 0.5 and 0.8% (w / v) aqueous Solutions made. Dimethylglyoxime was added to the samples of these aqueous solutions together with benzotriazole or a derivative thereof added in the amounts indicated in Table I.

A one square inch (2.54 χ 2.54 cm) shiny copper foil was placed in each of these aqueous solutions and each Solution boiled for an hour. Thereafter, the copper pieces were taken out from the solutions, dried and their weight loss and calculated in milligrams per square decimeter. These weight loss figures are also given in Table I.

'\\ stretch to Vergleichsz are shown in Table I and data on gen ommen,

209821/1004

which concern the respective control attempts and those approaches, in which benzotriazole or a derivative thereof or Dirnethylglyoxime as the only active ingredient instead of the invention Inhibitorenkoir.bination were used.

j
The same results were obtained when the experiments were repeated using the tetranate triune salt of ethylenedianine tetraacetic acid, the pentasodium salt of hydroxyethylethylenediamine triacetic acid, the disodium and .dototassium salt of ethylenediamine-bis- (o-hydroxyphenyl acetic acid), 1-aminoethane-phosphonic acid, Ärainopropan-i, 1 -diphosphonic acid, 1-aminotoluene-1, 1-diphosphonic acid, 1-hydroxyethane ~ 1,1-diphosphonic acid, citric acid and gluconic acid instead of the trinatriuncal of nitrilotriacetic acid.

-H-

209821 / 100A

Table I.

example Total Inhibitor Concentration ($) I. 0.1 0.10 0.8 0.25 0.8 0.50 0.8 - Detergent concentration ($) 20th
13th 0.5 59
36 0.5 29 · 0.5 19th 1 Not an inhibitor
Whore thyl gly oxime (DMG) 16
12th 42
23 42
36 23 45
29 T 6 39
19th ro
σ 2 Bonzotriaaol (BTA)
1: 1 mixture of benzotriazole and
DHG 17th
9 34
30th 42
36 36
24 34
22nd 32
11 29
6th 3821 / 3 5-methylbenzotriazole
1: 1 mixture of 5-methyl-BTA and
DMG 11
0 36
■ 26 29 ■
26th 26th
12th 22nd
5 20th
4th ■ 5
0 1004 4th 5-n-butyl-benzotriaz oil
1: 1 mixture of 5-n-butyl-BTA
and DHG 17th
5 19th 34
19th 14th
3 11
0 1
0 0
0 5 5-n-DodecylberiS5Otriazole
1: 1 mixture of 5-n-dodecyl-BTA
and DMG - ■ 16
9 - 2
0 28
17th 0
0 25th
2 6th Tetrahydrobenaotriasol
1: 1 mixture of tetrahydrobenzo
tria ^ ol and DMG 23
9 12th 14th 7th 9: 1 mixture of 5-n-butylbenzo
triazole and dimethyltflyoxime - - 4th 8th mm 1: 9 ~ mixture of 5-n-butylbenzotri-
azole and diine thyl gly oxime - 6th -

Examples 8 to 12

The method according to Examples 1 to 7 was repeated, v / obei as a corrosion-preventing it G-lyoxiia Diphenyl glyoxim was used instead of dimethylglyoxime.

The results obtained are shown in Table II below.

209821/1004

Table II

■ 8

example Total inhibitor concentration (#) 0.10 0.1 υ, 3 ' 0.8 0.25 0.1 ' 0.5 υ.8 - Detergent concentration {%) 20th 42 .59 - - - - Not an inhibitor 0 20th 33 0 2 22nd 8th
9 Diphenylglyoxime (DPG-) 16
1
11
0 34
22nd
28
12th 42
26th
29
28 14th
0
9
0. 35
5
14th
2 45
23
22nd
5 209821 / 10 Benzotriazole
1: 1 mixture of benzotriazole and DPG
5-n-butyl benzotriaz oil
1: 1 mixture of 5-n-butyl-benzotriaz oil
and DPG 17th
0 16
0 34
0 3
0 2
0 11
0 - »
O
O 11 5-n-dodecyl-benzotriazole
1: 1 mixture of 5-n-dodecyl-benzo triaz oil
and DPG 0
0 31
2 36
26th 5
0 23
2 5 12th Tetrahydrobenzotriaz oil
1: 1 mixture of tetrahydrobenzotriazole
and DPG 7th
1 7th
0 7th
0 - _ 5-n-octyl-benzotriazole
1: 1 mixture of 5-n-octyl-benzotriazole
and DPG

cn cn -α

The results shown in Table II confirm the excellent, the corrosion of copper preventing properties of the inhibitor mixture according to the invention.

Examples 13-17 , J.

The procedure according to Examples 1 to 7 was repeated, where as a corrosion-preventing Oxira ck benzoin oxime instead of dimethylglyoxime was used.

The results obtained are shown in Table III below.

-18-

209821/1004

Table HI

example Total inhibitor filtration (#) O, -10 0.1 0.5 0.8 0.25 0.1 0.5 0.8 0.50 0.1 0.5 0.8 - Detergent concentration (j ») .20
8th 42
19th 59
28 3 8th 19th 3 0 8th 13th
14th iCein inhibitor ·. .. _.
^ L-Ben ζ ο inoxi m (oU-B. 0 ·) 11
5
17th
6th 28
18th
16
4th .29
27
33
19th 9
0
3
.0 14th
5
2
0 22nd
14th
11
0 0
0
3
0 ' 1
0
0
0 5
1
0
0 209821> 15th 5-n-butylbenzotriaz ol
1: 1 ~ mixture of 5-n-butyl-
benzotriazole and rt-BO
5-n-dodecylbenzotriazole
1: 1 combination of 5-n-dodecyl
benzotriazole and c (-BO _ 0 4th 14th M004 16 9: 1 mixture of 5-n-butyl
benzotriazole and dB.O. - 0 7th 12th 17th 1: 9, except for 5-n-butyl
tenzotriazole and o («BO« 7th
2 7th
0 7th
4th - - - - - ■ 5-n-octylbenzotriazole
1: 1 mixture of 5-n-octyl
benzotriazole and oC-BO

cn

CD cn

Example 18

A sample of shiny copper foil the size of 3 inch χ 1/2 inch χ 1/16 inch (76.2 12.7 x 1.59 ram) immersed in a total of 50 ml of an aromatic spindle oil, "the 50 p.p.m. elemental sulfur and 0.05% by weight each diphenyl · glyoxime and tert-butylbenzotriazöl contained. The copper foil passed the ASTM D-130 copper streak corrosion test for three Subjected to hours at 210 ° F (99 ° C).

At the end of the test, the copper strip was removed from the oil, washed, dried and visually inspected for corrosion. The copper strip treated in this way showed a substantial one less tarnished surface and significantly less corrosion than the same strip in the was treated in the same way in a control liver in which no inhibitor mixture was added.

Example 19

From the solid detergents produced according to Examples 1 to 7 powder, a 0.5% (w / v) solution was produced. Acetoxia and benzotriazole were added to samples of these solutions or a 1: 1 mixture of these two products was added in the amounts shown in Table IY.

The corrosion properties of each of these solutions were then examined as described in Examples 1 to 7.

-20-209821 / 1004

Table IV

example Total inMMtor concentration (° / o) . 0.1 0.25 0.5 - No IiüaiToi-tor 42 42 42 - Benzotriazole 34 36 32 - Acetoxime 33 33 30th 19th 1: 1 acetoxime / benzotriazole 28 30th 25th

ro

CD co

BoI 5-c iol 20

A 0.1% (wt / yoI) solution was prepared from the detergent powder according to Examples 1 to 7 and benzophenoxine or benzotriazole or a 1: 1 mixture of these two products

j
added products in the amounts shown in Table V.

The corrosion properties of each of these solutions were determined as described in Examples 1-7.

Table Y

example Total inhibitor
concentration (fo) 0.1 0.25 0.5 .- Not an inhibitor 20th 20th 20th - Benzophenoxime 19th 18th 16 - ' Benzotrias oil 16 14th 16 20th 1: 1 benzophenoxime /
Benzotriaaol 14th 14th 12th

Example 2 1

From the detergent powder produced according to Examples 1 to 7 A 0.8 $ 3 (w / yoI) solution was prepared and Acetophenoxime or benzotriazole or a 1: 1 mixture of these two products were added in the amounts given in Table VI.

The corroiu oa .-; oigeriscli -. F th of each of these

Z 1/1004

Table VI

example G-esanite inhibitor
concentration 0.1 0.25 - . Not an inhibitor 59 59 - Benzotriazole 42 45 - Acetophenoxime 38 40 21st 1: 1 mix eh. Made of benzo-
triazole and aceto
phenoxime 29 34

209821/1004

Claims :

Claims (22)

4 * Λ.) JletallbJnöendes product, characterized in that it a water-soluble, metal "forms a substance that is a Copper clielate with a log-stability constant greater than 10 forms, or a mixture of several water-soluble, metal-forming substances, of which at least one Copper clielate with a log stability constant greater than ε.ΐε 10 forms, and as tarnishing or corrosion preventing product a .Benzotriazole, a bis-benzotriazole or the 4,5,6,7-tetrahydrobenzotriazole and additionally contains an oxime. 2. Metal-binding product according to claim 1, characterized in that that the corrosion inhibitor is a triad of the following general formula is: N I H
wherein A is a benzene ring, an A} 3cyl-substituted benzene ring, with 1 to 20 carbon atoms in the alkyl chain, one via a bridge member with a radical of the formula 209821/1004 substituted benzene ring or a cyclohexene ring. 3. Metal-binding product according to claim 1 or 2, characterized characterized in that the corrosion inhibitor is a benzotriazole connection the general formula where R is an alkyl group having 1 to 12 carbon atoms, eiiD bis-benzotriazole compound of the general formula wherein X is an alkylene radical with 1 to 6 carbon atoms, a 1: 1 cycloalkylidene group with at least 5 carbon atoms, the carbonyl group, the suIfuryl group, oxygen or sulfur, or the 4,5,6,7-tetrahydrobenzotriazole. 4. Metal-binding product according to claim 3, characterized in that that the substituted benzotriazole is 5-methyl-, 5-ethyl-, 5-n-butyl-, 5-tert-butyl-, 5-n-octyl- or 5-n-dodecyl-benzotriazole is. —25— 2098/1 / 1004 BATH 5. Ketallbindend es product according to claims 1 to 4> characterized in that the metal-binding compound is an alkyleneamino or alkylenepolyaminopolycarboxylic acid or a Alkali metal, alkaline earth metal or amine salt thereof, a nitrilopolycarboxylic acid or a salt thereof, an aminopolyphosphonic acid or hydroxyphophonic acid or a derivative thereof or a hydroxy or polyhydroxycarboxylic acid. 6. Metal-binding product according to claim 5 »characterized by - indicates that the metal-binding compound is the di-, tri or tetranatriura salt of ethylenedianine tetraacetic acid, the Pentasodium salt of diethylenetriaminepentaacetic acid, the trisodium salt of hydroxyethylethylenediamine triacetic acid, the dinatrite or dipotassium salt of ethylenediamine bis (o-hydroxyphenyl acetic acid), 1-aminoethane-1,1-diphosphonic acid, 1-aminopropan-i, 1-diphosphoric acid, 1-aminotoluene-1,1-diphosphonic acid, 1-hydroxyethane-iji-diphosphonic acid, citric acid or C-luconic acid. 7. Metal-binding product according to claim 5, characterized in that that the metal binding compound is the trisodium salt of nitrilotriacetic acid. 8. Metal-binding product according to claims 1 to 7, characterized characterized in that the oxime is a monooxime of the following general formula: -26-20982T / 1004 ¹ Il ² N-OH wherein R .. and R ₂ , which can be the same or different, is an alkyl group having 1 "to 12 carbon atoms, an aryl radical or an aralkyl radical having 7 to 10 carbon atoms 9 · Metal-binding product according to claims 1 to 7 »thereby characterized in that the oxime is a dioxime of the following general terms Formula is: H-OH 2Ϊ-0Η wherein R- and R _{2 have} the same meaning as in claim 8 and R * is an alkylene radical having 1 to 4 carbon atoms and η is 0 or 1. 10. "Metal! Binding product according to claim 8, characterized in that" draws that the monooxime acetoxime or benzophenone oxime is. 11. Metal-binding product according to claim 8, characterized in that that the monooxime is the benzoin-Ot-oxira 12. Metal binding end es product according to claim 9, characterized in that each of the substituents Rj and Hp ^e i- ^s " ³ ^ - substituted alkyl group having 1 to 6 carbon atoms and η 0 or each of the substituents R ₁ and R _{9 is} an aryl radical and -27-209821 / 1004 '- η Ο is. 13 · Metal-binding product according to claims 9 or 12, characterized characterized in that the dioxime Dimethylglyοxita or Diphenylglyοxiα is. 14 · Ketal! Binding product according to claims 1 to 13, characterized characterized in that the weight ratio between the triaz oil compound and the oxime in the range from 1:20 to 20: 1. 15. Metal-binding product according to claim 14, characterized in that the weight ratio between the
Triazole compound and the oxime in the range of 1: 4 to 4: 1
lies. 16. Metal-binding product according to claims 1 to 15), characterized in that the product is in the form of an aqueous
Solution is available. 17 · Metal-binding product according to claim 16, characterized in that the total ratio between the triazole compound and the Oxira is in the range from 0.01 to 10 wt .- ^
based on the total weight of the aqueous preparation
amounts to. 2098z! / 1004 18. Metal-forming product according to claim. 17, · characterized in that the overall ratio between the T _r ~ iazol compound and the oxime in the range of 0.05 to 5 wt. ~ $ By weight based on the total weight of the aqueous preparation. · 19. Metal-binding product according to claims 1 to 18, characterized characterized in that the! products according to claims 1 to 14 part of a detergent product it preferably for Textiles is. 20. Metallbandend es product according to claim 19 _5, characterized in that the amount of metal-binding compound in the range from 5 to 75 wt .- $ and the amount of triazole compound in the range from 0.01 to 5 wt .-% and the product in addition Contains 10 to 30 wt .- ^ o of an anionic surfactant. 21. Metal-binding product according to claim 20, characterized in that that the anionic surfactant is an alkali metal or amino acid alkyl sulfate or an alkali metal sulfate is onate or alkylarylsulfonate. 22. Metal-binding product according to claim 19 »characterized in that that it builds off a build-up as further additives, "a bleach, a gown that suspends dirt particles, a filler, an optical brightener, an enzyme and / 20982 1/1004 BATH ORIGINAL _ ₂₉ _ 2135766 or contains a perfume. 23 · Metal! Binding product according to. Claims 1 "to 15 _}, characterized in that it is part of a lubricant _{5 of} a hydraulic fluid, a mineral oil, a lacquer product or a polymer product. 209821/1004 ~ -ORlQJNAL IWSPECTED