DE2155767A1 - Corrosion preventive agents - Google Patents

Description

The present invention relates to corrosion preventive accessories; Preparations and a Method for the Treatment of Aqueous Solutions ^ which contain aggressive metal-binding products and come into contact with metal surfaces, the method consists in adding a 5-alkyl-benzotriazole to the aqueous solution and thereby prevents the corrosion of the metals caused by such aqueous solutions.

Benzotriazole is known to be effective in preventing corrosion of metals, especially copper and copper alloys in aqueous media, the metal-binding products ("sequestering agents ") that are only slightly aggressive towards copper.

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hold, as is the case, for example, with conventional, polyphosphate-containing ketallic cleaning products and surface-active preparations. V / eil copper is "attacked only to a small extent in such media, not war.es possible to ascertain any significant difference between the protection effect against copper, which was the one hand, obtained by benzotriazole itself and on the other hand by known derivatives of benzotriazoles with ψ copper protection.

However, they become metal-binding agents in such aqueous media used, which are more aggressive towards metals than Polyphosphateι as it is e.g. with alkali metal salts Xthylenediaminetetraacetic acid or nitrilotriacetic acid of the This is the case, according to the latest findings, benzotriazole works when used in such solutions there is no longer any prevention Corrosion of copper. '-

A partial protection of the copper bev / irkenäs derivatives of the Benzotriazoles are the 5-alkyl-benzotriazoles described and claimed in British Patent No. 1,065,995. It has been found that, due to their increased hydrocarbon content, these alkylated benzotriazoles have increased solubility in media based on mineral oils and accordingly an increased protective effect compared to benzotriazole Have copper in such media.

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Surprisingly, it has now been found that alkylated benzotriasols despite their lower solubility in aqueous media containing aggressive substances compared to benzotriazole excellent protection of copper surfaces In contact with such aqueous media, this is surprising, especially when such products are used in aqueous media that contain only moderately aggressive products compared to copper, no significant difference in effectiveness-noticeable is.

The present invention thus relates to products that in addition to a water-soluble, metal ion binding product that is a copper chelate with a log stability constant greater than 10 forms, or binds a skeleton of water-soluble metal ions Products at least one of which forms such a copper chelate, a minor amount of one as tarnishing or substituted agents acting to prevent corrosion Benzotriazole of the general formula I contains5

wherein Jl is an alkyl group having 1 to 20 carbon atoms and - The bensol ring of the benzotriasol molecule misubstltuier.t or with

rreißer ^^ äer several truppen is substituted ^ άϋέ kei ne ■ never tali-

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have binding properties. The Jirfirsdung continues to affect v.'aqueous solutions of such products. · ·

The log stability cons. Is in the text published by the British Chemical Society in "London in.1957 "Stability Conste, nts" Special Publication No. 6.

Aggressive metal-binding agents which form a copper chelate and have a log stability constant greater than 10 are the alkylene, p lenamino and alkylene polyaminocarboxylic acids and their alkali metal, alkaline earth metal and aminosalic acids, nitrilopolycarboxylic acids and their salts, aminopolyphosphonic acids or their derivatives so / ie the hydroxycarboxylic acids or polyhydroxycarboxylic acids. Specific examples of such products are the di-, tri- and tetrasodium salts of Ätlxylenedianinetetraacetic acid, the Pentanatsiunisalz of diethylenetriaminepentaacetic acid, the trisodium salt of Hydropathyläthylenedianintriacetic acid, the ■ dinatriuin- and dipotassium hydroxide (o-phenylenedianin), 1-acetic acid (o-phenylenedianin) salt. iainoethane-1,1-diphosphonic acid, 1-aminopropane-1,1-diphosphonic acid and 1-arr.inotoluene-i, 1-diphosphonic acid (which are described in British Patent No. 995,462), the 1-hydro; -: yethane-1,1-diphosphonic acid, citric acid and gluconic acid and especially the trinatriuine salt of ilitrilotriacetic acid.

The metal-binding products used in products according to the invention can be a mixture of one or more of the above-mentioned highly aggressive products with one or more of the

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several only slightly aggressive products such as the alkali metal salts of the condensed phosphates, provided that the log stability constant of the with at least one of the Copper chelate formed in the mixture of metal-binding products is greater than 10.0.

Alkylbenzotriazoles and processes for their preparation are in in British Patent No. 1,065,995 and claimed. According to the invention, the 5-alkylbenzotriazoles are preferred, which have no further substituents on the benzene ring and whose alkyl chain contains 1 to 12 carbon atoms. Examples these are 5-ethyl-, 5-ethyl-, 5-n-butyl-, 5-tert-butyl-, 5-tert. -Pentyl-, 5-n-dodecyl-benzotriazole. Most notably Preferred is the 5-tert-octyl-benzotriazoi, other groups that are unable to bind metals and those in the eenzene ring of the bonzotriazole molecule can be present are in particular Halogen and nitro groups.

The metal-binding products according to the invention can be used in their Kind of a wide variety of aggressive metal-binding substances Be products. However, metal cleaning agents such as descaling products are of particular interest compositions "), cleaning agents for brewery kettles and aircraft. The products according to the invention, however, are of particular interest in connection with cleaning agents such as dishwasher

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detergents and preferably in connection with cleaning agents for textiles, especially for household and industrial ashes and cleaning methods are used therefor. 3) The products according to the invention can be used both in solid form

can also be produced in the form of aqueous solutions.

If the metal-binding product according to the invention is to be produced as a cleaning agent, it generally contains a nonionic or, preferably, anionic surfactant. Such non-ionic surface-active substances are polyalkylene glycol derivatives of long-chain pettamines or fatty alcohols. Examples of common anionic surface-active substances are the alkali metal alkyl sulfato and the alkali metal sulfate and alkyl sulfonate.

The surface-active substances I ″ which ani / esende in cleaning agents are generally present in an amount of up to 40 %, in particular 10 to 30% by weight, based on the total weight of the product.

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, Snzyne and / or mild perfumes.

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Special bleaching agents which can be used in the products according to the invention are alkali metal hypochlorites and products which generate chlorine, alkali metal carbonates and persulfates and, in particular, alkali metal perborates; suitable fillers are, for example, the alkali metal sulfates; as suspending Schinutzteilchen product is ira general Carb oi ~ fa used ethylcellulose; Triazinyldiauiinostilbenedisulphonic acid, an arainocunarine, a pyrazoline, an iiaidazolone, a benzidine sulphone, a bisoxazole or a dibenzidazole can be used as optical brighteners. An enzyme suitable for the purposes of the present invention is a product which in particular contains a protease which is produced by a spore-forming bacterium of the species Bacillus subtilis; Products with a lemon, cologne or fir base can be used as a perfume.

In cleaning agents, the metal-binding product is generally in the range from 5 to 75% by weight and the benzotriazole of the general formula I in the range from 0.01 to 5% by weight, each based on the solid substance content of the complete detergent product.

The benzotriasol of the general formula I can be used with that metal-binding product containing detergent powder in

-8th-

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solid phase according to any of the known mixing methods for such products are added / earthed, e.g. in a free-fall mixer or in a Ku ^ olLiv.liler.r.iirjcher. The received powdery product can then be used to produce aqueous Detergent can be dissolved in liasser. On the other hand an aqueous slurry can also be formed which both the metal binding agent, the cleaning agent and that contains corrosion-retarding agents and which is then spray-dried. In this way, a cleaning agent according to the invention is produced formed in solid form.

The products of the invention can be used in any type of liausholts- or industrial washing or JicinigungsvorrichtnrigerL and in particular to such Jiinsatz can, in which the product einlegierung in rcrührung with metal and in particular with metallischon surfaces of copper or K ¹ UPF en comes. Copper parts can de: · machines or metal objects on the clothes to be cleaned wio fichiiiede · - work on; Nickel-Copper Tc ;; icrunge: i be. The products according to the invention have a markedly reduced tendency to cause metal corrosion, in particular the corrosion of surfaces of copper and copper alloys.

The following examples explain the present application further ^ parts and i-: rozcntzahlon refer to the court,

unless otherwise stated. _ _C) _

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Examples 1 to 8

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

Sodium perborate 20 ^c ; i

Trinatrial salt of nitrilotriacetic acid 15 Sun

Sodium tripolyphosphate 20 ^c / o

Sodium Dodecylbenzenesulfonate 27 ⁰ A

Monoisopropanolamide of lauric acid 5 %

Sodium metasilicate 10 %

Carboxymethyl cellulose 2.9 / ό

A 1 »3» 5 ~ ^r i ¹ riazinyl "derivative of 4,4'-diarainostilbene ~ 2,2'-disulphonic acid (dinatriura salt)" 0.1 %

^{0.1, 0.5 and 0.8 c} , o-strength (Gsv./Vol.) Aqueous solutions were then prepared from the above-mentioned solid cleaning agent. A product of the general formula I in the amount given in Table I below was added to samples of these aqueous solutions. In this $ aqueous solutions eae was inserted a one square inch (2.54 χ 2.54 cm) Grossa glossy copper foil and each solution boiled for one hour. The copper pieces were then removed from the solutions, dried, and their weight loss determined and calculated in milligrams per square meter. These weight loss: -'- numbers are also given in "c.belle 1".

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For comparison purposes, data are also included in Table I, which relate to the respective control experiments and those approaches in which benzotriazole instead of the compounds of general formula "I was used.

Same results mirden when repeating the experiments using the Tetranatriusisalzes of ethyl endiaEiintetraessigsäure, * the Pontanatriumsalzc: the Hydroxyäthyläthylenaiamintriessigsäure, the disodium and Dikaliuasalzes the Äthylendiarr.in-bis (o-hydroxyphenylacetic acid), the 1-Aminoäthan-1,1- , the 1 ~ aminopropane-1,1-diphosphonic acid, the 1-aminotoluene-1,1-diphosphonic acid, the i-hydroxyethane-1,1-diphosphonic acid, the citric and gluconic acid instead of the trinatrium salt of the kitrilotriacetic acid.

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ι - CO I. ι- Λ CM IA - 11 - O ·. O IA O CJ O m t IA CvI O O O VO VD VO O • I. V " O ΓΑ O IA (D I. I. CM O V CO OJ V u \ O IA I. IA I. OJ CM tA γ— CM O tA ν- r. I. I. C \ CM , A O v ~ (D CTv OJ V ω <J I. OJ I. O IA CvJ IA - O IA I. ω V " O VD OJ I. a. O" CM v- I. IA CO O - ■ * " tA I. a CM CvI egg O) ♦ v 'Ö O Vi α • r-I r-I -! > O CJ r! H •H .O fs O O O -P ·!> H H N N 1-3 ß • f ϊ O O CJ Cj O j :: QJ N M. 'r-I • r | •H • Η Vi M. Gj a r,
r I J-I -P I. ' f_5 *> Ί •H -P • P -P Ci β O ίι c_] O O O “M • Ρ H t-1 N -ρ t ' H t, O O c \ β β β ■ r CJ O N O O O C) r * -P -p i-J JlJ O .Ω • r-! -I- ⁵ ■> i O O © I. I. I. β C:> •H , Q rH r-I rl O Ci -H CJ I. I. {>, s * •H r-I rj JJ • P C) I. β I * "' rj 5>, O C) O β H • P O 'd O 4- * - * O -P ^ i I. I. O ^ J r: to ti • • Q • rl CJ • ■ -I ..- { β I. -P -P I. / J β O O β U I, β "•1 ί. Λ
* ■ - · * cq in I. O O O -P -P IA β I. M. I. I. v- IA IA OJ IA 20th IA 9 X, 982? ^ 0 9 r-I O • r-
P. W. •H
O

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Table I (continued)

: ■ ι /
( Inhibitor concentration in % of
solid: cleaning agents, 0.1 Y 0.10
• 0.8 I. 0.1 0.25 0.8 0.1 0.50 0.8 Example 13th 22nd 5 10 1 1 Detergent concentration, % 0.5 0.5 0.5 ια, 6 5- (1 ^f , 1 ^T -dimethylpropyl) - - 17th - 4th 8th O Ί 1 O ) 982 benzotriazole 7th 7th 2 2 2 1 κ> ₇
O
(O
(O 5- (1 ', 1 ^?, 4 »-trimethyl) -
pentyl-benzotriazole - 1 O 8th 5-n-octyl-benzotriazole 7th 7th 7th

O. 2

CD

Example 9

To 100 ml of an aqueous 1 So-strength (w / v) solution of the Tri ~ sodium nitrilotriacetic acid, 0.1 mg benzotriazole resp. 5th: rt.-octyl-benzptriazole in the form of a 0.05% c (w / v) Solution added »The solutions obtained are heated to the boil, using a sintered glass with the help of be ventilated with compressed air.

A start of boiling was added to each solution. Inserted a piece of cleaned and weighed, one square (2.54 χ 2.54 era), large copper foil. After one hour the copper sample was extracted, washed, dried and weighed again.

The results obtained are shown in Table II below reproduced. ■ - - "

Table II

example Inhibitor Inhibitor concentration G'ew * ^ 'in relation
to "NTA. ■ Copper lust
in mg / dm 9 none
Benzotriazole
5-tert.
Octyl benzo-
triazole ppn
Weight / volume
in solution 0.01
^: 0.01 • 38
16
1 1.0
1.0

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The results given in Table II do not confirm them foreseeable and essential copper protection effect that does not Benzotriazole derivatives of the general formula 1 in comparison can be obtained with the benzotriazole.

Example 10 -,. .

To 100 ml of an aqueous 1 3 ~ IgERI? (Gew./YoX) solution of Trinatriunrnitrilotriessigsäiire 0.1 NJG Benzotriszol and 5-tert-butyl (1 ', 1 ₁ 3 ¹ ₁ 3' -Tetrainethylbutyll-ftenzotriazol in Fo ^ i of a 0.5% (Gevr./Vol·) solution are added, and the solutions are heated to the boil while using koiapriiaierijer air

-'a sintered glass ventilated. ! \. After boiling began, an ÖqaÖratinch (2.54 χ 2.54 i

< -! ■■■■■■ '■ -'. "-". I

cm) measuring uncL weighed piece of cleaned cropping foil | inserted into each of the solutions. After an hour the copper piece was removed, washed, dried and weighed again *

The results obtained are shown in Table III below.

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Table III

example Inhibitor iBiiibitor- m.
/ FoI. Κοϊιζ entr at-i on % iri reference
NTA Copper loss - none p.p. Weight
on - in gig / am ^ - Benzotriszoli - 0.01 "33 10 5-tert .- (1 «, 1
raethylbutyl) -
benzotriazole 1 , 0 0.01 16 "" I.
J
1 1

The results given in Table III do not confirm this predictable and essential copper protective coating associated with the Bonzotriazole derivatives of general Foriael I in comparison .with which benzotriazole is obtained

Patent claims:

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Claims (12)

changed remäS input received on .. <^> .. <^^ .. / ^ 1. Ji, <gc [| idurcli g.fckcnnzGlehnet; that there is a water-soluble, metal ion binding compound which forms a copper chelate with a 'log stability constant greater than 10 _} or a mixture of water soluble, metal ion binding compounds, of which at least one is a copper chelate with a stability constant greater than 10 forms, and as the tarnishing or corrosion of the surface preventing product, a substituted benzotriazole. contains the following general formula: wherein R is an alkyl group having 1 to 20 carbon atoms and the benzene ring of the benzotriazole molecule is unsubstituted or with one or more, no metal binding properties having Gruijpen is substituted. 2. Metal-binding product according to claim I _1, characterized in that it contains a benzotriazole of the following general formula: 209 82 2/0991 wherein R ^ is an alkyl group having 1 "to 12 carbon atoms is, ■ 3 * Metal-binding product according to claim 1 or 2, characterized in that that the metal ion binding compound is an alkylene-amino- or alkylene-polyamino-carboxylic acid or a Alkali metal, alkaline earth metal or amine salt of such Acid, a kitrilopolycarboxylic acid or a salt thereof, an aminopolyphosphonic acid or hydroxypolyphosphonic acid or a derivative thereof or a hydroxy or polyhydroxycaroonic acid is. "· 4. Metal-binding product according to claim 3, characterized in that the compound binding the metal ions is the di-, tri- or tetrasodium salt ö.er ethylenediaminetetraacetic acid, the pentasodium salt of diethylenetriaminepentaacetic acid, the sodium salt of hydroxyethylethylenediamine triacetic acid. the dinatriuin or dipotassium salt of ethylenedianine bis (o ~ hydro :: yphenyl acetic acid), 1-aminoethane-1,1-diphosphonic acid, 1-aminopropane-1,1-diphosphonic acid, 1-aminotoluene-1,1-diphosphonic acid, 1 ~ Rydroxyäthaii-1,1-displiosphonic acid, Citric acid or ,. Is gluconic acid. ^ p 209822/0991 ~ ^w ~ 5. Metal-binding product according to claim 3j, characterized in that that the metal binding compound is the tri-sodium salt which is nitrilotriacetic acid. 6. Metal-binding product according to claims 2 to 5 * thereby characterized in that the 5-alkyl-benzotriazole is the 5-methyl, 5-ethyl-, 5-n-butyl-, 5-tert-butyl-, 5-tert-pentyl or Is 5-n-dodecyl-benzotriazole. 7. Metal-binding product according to claims 1 to 5 * thereby characterized in that the 5-alkyl-benzotriazole is the 5-tert-octyl-benzotriazole is. 8. Metal-binding product according to claims 1 to "J _9, characterized in that the product in aqueous solution is part of a cleaning agent. 9 · Metal-binding product according to claim 8, characterized in that the product is part of a cleaning agent
for textiles is. 10. Metal-binding product according to claims 8 and 9? characterized in that the metal binding compound
in an amount in the range from 5 to 75 wt .- ^ and the benzotriazole compound in an amount in the range from O ₃ Ol to
% Is present and the product in addition to 10 - 5 wt.
30 wt -.% Of an anionic surfactant
contains. 209822/0991 11. Metallbindend.es product according to claim 10, characterized in that that the anionic surface-active compound is an alkali metal or ammonium alkyl sulfate or an alkali metal sulfonate or -alkylarylsulfonate. 12. Ketallbindendes product according to claim 10 or 11, characterized characterized in that es.as an additional component a binder, a bleaching agent, a protective particle suspending compound, a filler, an optical brightener, an enzyme and / or a perfume. 20982270991