DE2419814C3 - Sulphite-containing electroplating bath for the deposition of palladium and palladium alloys - Google Patents

Description

8. Bath according to claim 1 to 5, characterized in that ME Sb ^{+ + +} , As ^{+ ++} , Cr ^{+ +} \ Fe ⁺ "" ¹ or complexes with a higher coordination number.

9. Bath according to claim 1 to 8, characterized by a content of 1 to 200 g / l sulfite ions especially in the form of alkali, alkaline earth or ammonium salts.

10. Means for refreshing the bath according to claim 1 to 9, characterized in that e: [Pd (SO ₃ ) "Y ₄ _JME _2ll _ ₂ contains.

11. Means according to claim 10, characterized by a content of Pd (SO ₃ ) · (NH _{3 I 3} or [Pd (SO _{3 I 2} - (NH ₃ ) ₂ ] (NH ₄ ) ₂ ).

or the ion

[PdX _{n + 1} Y ₃ .JME _11. , [PdZ "Y ₄ _JME _2B .. ₂ [PdQ" Y ₄ _JME ₃ "_ ₂

[PdYJ ⁺⁺

where X is a monovalent anion, Z is a divalent anion and Q is a trivalent anion and Y is a function with coordination number 1 of a unit with mono- or polyfunctional coordination and a valence of 0, ME is a monovalent cation or the m-th part of a cation with the valence is m and η or m can be 1, 2 or 3.

2. Bath according to claim 1, characterized in that a compound is used in which X is chloride, bromide, iodide, the hydroxyl group or the acetic acid residue.

3. Bath according to claim 1 or 2, characterized in that Z is the grouping SO ₄ "", SO ₃ "", [PdX ₄ ] "", SeO ₄ "or RPO ₃ "", wherein R represents an organic or polyphosphoryl group .

4. Bath according to claim 1 to 3, characterized thereby gekennteichnet, that Q is the remainder of phosphoric acid or phosphorous acid.

5. Bath according to claim 1 to 4, characterized in that X is water, ammonia, a primary, • eecondary or tertiary organic amine, the group H ₂ N-CH ₂ - of ethylenediamine or

H ₃ N-CH

of cyclohexanediamine.

6. Bath according to claim 1 to 5, characterized in that ME is an alkali metal, NH / and complexes of the formula [PdXY ₃ ] ⁺ or analogous complexes with nickel, cobalt, copper, tin, iron or gold instead of palladium.

7. Bath according to claim 1 to 5, characterized in that ME is an alkaline earth metal or a complex of the formula [PdY ₄ ] " ¹ " ⁺ , [AY ₄ ] ⁺⁺ or [AY ₆ ] ⁺⁺ , in which A is nickel, cobalt , Copper, iron, gold or precious metals of the platinum group.

The invention relates to a sulphite bath door the electrolytic deposition of palladium and palladium alloys, that does not contain free cyanide, nitrate or nitrite, and a means for freshening up of the bathroom.

There are already a wide variety of baths and processes for the deposition of palladium or its Alloys with precious metals or other alloy elements on conductive or electrolytically conductive made objects known. For baths like this

A wide variety of salts and, in particular, complexes are used, their degree of coordination is often poorly or incorrectly defined.

They are baths containing complex palladium cyanide, such as Pd (NH ₃ J ₂ (CN) ₂ (US Pat. No. 19 91995), palladium nitrates in ammonia (Electroplat. Met. Finishing, 1962, 15, p. 20) and palladium and potassium nitrate (US-PS 19 93 623) Finally, halogen-containing compounds such as palladium tetrammine halides (DT-PS 12 62 722, SU-PS 2 80 153, GBPS Il 43 i 78) and palladium dichlorodiamine hydroxide (FR-PS 14 17 567) were used. Finally, baths containing palladium nitrite are known (Metal Finishing Guidebock & Directory, Westwood NJ, USA, pp. 335 to 337) as well as those with palladium tetrammine hydroxide (SU-PS 291988) or palladium complexes with organic compounds such as palladium cyclohexanediamine tetraacetate, palladium ethylenediamine chloride and the corresponding Sulphates (GB-PS 10 51383) and salts of palladium and urea (DT-AS 17 96 110).

These known baths are neutral or basic; acidic baths are obviously more difficult to control. A strongly acidic bath containing palladium nitrate and small amounts (5 to 20%) of palladium sulfite, known (DT-OS 21 05 626). A sulfite-based bath has also been tried (DT-OS 17 96110), in which the palladium is in the form of a urea complex.

Although the known baths have certain advantages, they also have many disadvantages. In general show the coatings of palladium and palladium alloys obtained with the known baths considerable internal stresses, so that cracking can occur if the thickness of the coatings a certain critical value, e.g. B. 5 to 10 μηι, exceeds. In addition, there are such layers also very porous.

Finally, the use of palladium nitrate or nitrite baths, especially in Presence of sulfites and organic chelating agents or brighteners, sometimes becoming an undesirable one Discoloration of the layers. In baths with a high concentration of halogen, free halogen is found on the anodes released during the electrolye, which leads to their oxidation and thus destruction. The presence of cyanides in such baths is extremely undesirable because of its high toxicity and the associated problems of reconditioning the used baths.

The object of the invention is an electroplating bath for the deposition of palladium or palladium alloys, which does not have the above disadvantages and is free from cyanide, nitrate and nitrite.

The sulfite-containing galvanic bath according to the invention for the deposition of palladium or palladium alloys, free of cyanide, nitrate or nitrite, containing 1 to 50 g / l palladium, optionally 1 mg / l up to 50 g / l alloy metals and if necessary! up to 100 gl gloss additives and / or scavenger for the Contaminants in particular containing organically bound nitrogen, sulfur or phosphorus Chelating or complexing agents in the form of polyenamines, arene and alkane sulfonates and phosphonates and their alkali and ammonium salts, optionally with functional substituents - OH, -COOH or -CHO and optionally substituted by amino groups is now indicated by a content of at least one palladium compound of the formulas

[PdX _{11 + 1} Y ₃ -JME _11. ,
[PdZ _n Y ₄ , JME _2n . ₂
[PdQ _n Y ₄ , JME _3n _ ₂
or the ion

With the bath according to the invention, a long working life can be ensured, with the refreshing of the bath by adding a certain palladium complex solution or in connection with the alloying element is significantly simplified and the composition of the layers remains the same over the entire operating time.

The bath according to the invention is set up by dissolving alkali or ammonium sulfite in ■ o an aqueous-alkaline solution, in addition to the otherwise customary additions of at least one of the above palladium compounds; Then mii is refreshed a solution of a compound of the formula

[Pd (SO ₃ LY ₄ -JME _2n ^ ₂

where X is a monovalent anion, Z is a divalent anion and Q is a trivalent anion and Y is a function with coordination number 1 of a unit with mono- or polyfunctional coordination and a valence of O and ME is a monovalent cation or the m-th part of a cation with the valence is m and η or «can be 1,2 or 3. The sulfite ion content is in particular 1 to 200 g / l. Finally, the invention also relates to an agent for refreshing the bath, which is characterized by a palladium compound of the formula

[Pd (SO ₃ J _n Y ₄ -JME _2n . ₂

The bath according to the invention has two main features Points on, namely the selection of the palladium complex compounds based on the valence level of the Palladium and the limitation of the molar ratio of halogen to palladium in the bath. This The molar ratio is strictly adhered to through the selection of the appropriate complex compounds. It should be below 10, the halogen ion content in the bath being practically 0. In the invention applied palladium complex compounds, the palladium is in the second oxidation stage in the form of tetracoordinated Pd (II) ions. The pH of the bath according to the invention should be 7 to 12.

and the molar ratio of halogen to palladium is kept at <10.
A wide variety of elements can be used for the alloys; in practice, noble metal is generally used, but the following elements can also be used: Cd. Cr. Co. Cu. Ga, Au, In, Fe, Pb, Mo. Ni. Ag. Sn, V. Zn. In certain cases arsenic, antimony and bismuth or noble metals of the platinum group, such as Pt, Rh, Ru, Ir and Os, can also be used. These metals are usually present in the bath as water-soluble salts or complexes, with the exception of course the nitrates or nitrites. Suitable compounds are the halides, sulfates, sulfites, phosphates, pyrophosphors and salts of organic acids (such as acetates, formates) or chelates (such as of ethylenediamine, ethylenediaminetetraacetic acid or ethylenediaminetetramethanephosphonic acid). The selection of the metal component is made taking into account the compatibility and solubility in the bathroom.

Of course, the bath can contain more than one of the above alloying elements. The concentration of palladium and the alloying elements in the bath depends on various factors, such as working conditions in electrolysis (current density, temperature, movement) and properties of the to be deposited Layer (mechanical properties, physical properties, purity). Generally depends the purity of the deposited alloy depends on the relative proportions of metal ions present. This relation is not strictly straight, since for given concentrations it is possible to determine the composition to vary the alloy by changing the working conditions. Used for deposition a palladium-nickel alloy, a solution with an equivalent concentration (weight) of the two Metals are used, it is possible - by appropriate modification of the working conditions (e.g.

Current density) - to vary the composition of the alloy by ± 30%, whom the mean composition is usually 50:50.

The concentration of palladium and the alloying elements is generally between 1 and 50 g / l, however, these limits are not critical and in some cases it is possible with concentrations below 1 g / l, e.g. B. 1 to 1000 mg / l, or over 50 g / l, e.g. B. to saturation to work.

To keep the pH of the bath between 7 and 12, it can use a basic substance - mineral or organic - e.g. B. contain an alkali hydroxide or ammonia. About 20 to 200 cm Vl of a 25% Ammonia solution is preferred.

The sulphite content of the bath can vary between wide limits, and indeed from a relatively low level Sulphite content, e.g. B. at the beginning of the order of 1 to 10 g / l. When refreshing the invention In the bath, the sulphite content increases gradually without difficulty to about 200 g / l or more. In addition to possible sulphites of the alloying elements, the bath can also contain sulphites of alkalis and alkaline earths or ammonia or also of organic bases.

The bath according to the invention can also be used as a common component of electroplating baths. or buffering agents, brighteners, complexing agents for regulating and preventing adverse influences by impurities, surface-active or wetting agents and the like. The purpose of a means for controlling the influence of impurities is a significant amount of it in one form to block, which is electrochemically inactive during electrolysis, so that such impurities are prevented with deposited and the properties of the coatings can be deteriorated.

In addition to the sulfites and the alkali compounds used to adjust the pH, one or more salts of mineral acids or organic acids with alkali, alkaline earth or ammonium, such as alkali halides (NaCl, NH ₄ Br), Na _{2, can be used as conductive salts and / or buffer agents} SO ₄ , (NH ₄ I ₂ SO ₄ , (NH ₄ I ₁ PO ₄ , CH ₃ COONa, sodium benzoate. These agents are used to increase the conductivity of the bath and, if necessary, to prevent unexpected changes in the pH value. The concentration the conductive salts and / or buffering agents can be between 1 and 200 g / l, but this limit is not critical.However, if halides are used, care must be taken that the molar ratio to palladium does not exceed the value given above.

Chelating agents containing organic nitrogen, sulfur or phosphorus can be used as a gloss additive or to adjust the impurities, such as arenic and alkanesulphonic acids and their alkali and ammonium salts, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and their salts and their higher homologs, their phosphorana logen, in which the carboxyl groups have been completely or partially replaced by PO (OH) ₂ groups or their alkali metal or ammonium salts. Examples are:

The amounts of the above compounds depend largely on their constitution and chelating agent Effectiveness. In some cases, very low proportions, such as less than 1 g / l, are sufficient to prevent the influence of the 5 Counteract impurities and add the electrolyte under appropriate working conditions keep; in other cases higher amounts are necessary, e.g. up to 10 or 20g / l. In many cases it is even an excess of z. B. 50 g / l or more is not disadvantageous, especially if the alloying elements to these chelating agents are only weak Show affinity. For example, palladium-nickel baths are used as a chelating agent Ethylenediamine tetramethanephosphonic acid in an amount of 1 to 100 g / l.

A wide variety of substances are used as wetting or surface-active agents (»Detergents & Emulsifiers, Allured Publ. Corp., Ridgewood. N.J .. USA «). However, alkali alkyl sulfaies are preferred and alkali alkane sulfonates, such as sodium acid sulfate and Alkali or ammonium methane, ethane. -propane-. -propene, -butane or -butensulfonate and their higher molecular weight homologs.

In the above palladium compounds, X represents a monovalent anion such as chloride, bromide. .Iodide. acetic acid residue, hydroxyl group, etc .; Z is a divalent anion, like the residues of sulfuric, sulphurous, PaHadium hydrochloric or selenic acid; Q is a trivalent anion like the remainder of phosphorous or phosphoric acid; Y is e.g. B. water, ammonia, an organic amine such as CH ₃ NH ₂₅ (CH ₃ I ₂ NH, (CHj) ₃ N. or the N function of a di- or polyamine, /. B. H ₂ N - CH ₂ - (from ethylenediamine) or

H, N-CH

(HO) ₂ Op-COH (CH ₃ J-PO ₁ OH) ₂ (HO) ₂ P-CH ₂ -NH-CO-NH-Ch ₂ -PO (OH) ₂

(HO) ₂ OP- (CH ₂ ), - PO (OH) ₂

with / 1 1, 2 or 3

N [CH ₂ -PO (OH) ₂ I,
[(HO) ₂ OP-CHJ ₂ N

(from cyclohexylamine or cyclohexanediamine). It is obvious that if this amine is a chelating agent, ie if it has two or more coordination points, these can be coordinated with one or more palladium atoms. In the above formulas, ME means a monovalent or polyvalent cation, e.g. B. alkali ions or ammonium groups and complex groups, e.g. B. [PdXY ₃ ] ⁺ , where X and Y have the above meanings,

such as [PdCl (NHa) ₃ ] ⁺ . However, the palladium can also be replaced by other transition metals, including the noble metals, such as Ni, Co, Cu, Fe, Au, Re, Rh.

Examples of divalent cations are the alkaline earths in water-soluble form and complex cations such as [PdY ₄ ] ^{+ +} . Here, too, the palladium can be replaced by other metal atoms with the coordination number 4. Divalent complex cations whose central atom has a coordination number other than 4 can also be used, such as

N- [CH ₂ -PO (OHy ₂₎ Examples of trivalent cations include Sb ^{+ + +} , Cr ^{+ + +} , Fe ^{+ + +} and their complexes.

is

25th

Common compounds are preferred for the replacement of the bath:

[PdCn (S ₂ O ₃ ) J (NH _{4 I 2}

PdCl ₂ (NH ₃ ),

[PdCl ₄ ] [Pd (NH ₃ J ₄ ]

[PdCl ₃ NH ₃ ] [PdCl (NH.,).,]

PdSO ₃ (H ₂ O) ₃

K ₂ [Pd (SO ₃ J ₂ (H ₂ O) ₂ ]

PdCl ₂ (OC (NH ₂ ) ₂ ) ₂

[Pd (NH ₃ ) JCl ₂

Na [ClPdSO ₃ Cn]

Pd (SO ₃ ) (NH ₃ I ₃ and

[Pd (SO ₃ ) ₂ (NH ₃ ) ₂ ] (NH ₄ ) ₂

where en means ethylenediamine.

For palladium compounds that can be used, see F. R. Hartley: The Chemistry of Platinum and Palladium ", Applied Sc. Publ. Ltd., London (1973), and »J. Chem. Soc. "(1960), p. 2620. To freshen up the bath one prefers

Pd (SO ₃ ) (NH ₃ ),

to maintain the chloride content of the bath during his total work capacity, d. H. for at least 40 to 50 refreshments, namely for one Value that ensures that the generation of chlorine at the anode is negligible.

The bath according to the invention is suitable for working temperatures between about 20 and 80, preferably 50 to 6O ⁰ C. The current density is between about 0.1 and 5 A / dm ^2, preferably between 0.5 and 1.5 A / dm ^2. The values for temperature and current density are not critical and can be exceeded in special cases.

The bath is preferably refreshed when the initial palladium concentration drops by 20 to 50% has decreased.

The following examples explain the invention:

example 1

To produce a pure palladium layer, the following was dissolved in water:

Pd (as Pd (SO ₃ ) · (NH ₃ W 9 g / l

(NH _{4 I 2} SO ₃ 25 g / l

NH ₄ OH (25%) 100 cm ³ / l

(NH _{4 I 2} SO ₄ 40g / l

»DEQUEST 2044« *) (30%) ... 15 cm ³ , 1st

NH ₄ Cl 10g / 1

2-ethylhexyl sodium sulfate (30%) .. 0.5 cm ³ / l

pH 9.8

*) »DEQUEST 2044« is a commercially available aqueous solution of ethylenediamm - NN - teiramethanephosphonic acid. Tcilneatrahsiert From the above electrolyte at 60 ⁰ C under a current density of 1 A / dm ² one obtains a glossy gray layer, without visible cracks or defects, with a thickness of more than 10 μm.

When the palladium concentration has dropped to 4 g / l, it is _{refreshed with Pd (SO 3} ) (NH ₃ ) ₃ , and this can be done at least forty times without the bath becoming less effective.

The door freshening applied palladium triammine sulfite is made as follows:

4 g of palladium dichloride (2.356 g of Pd) are ^{suspended in 50 cm 3 of} water, 2.588 g of sodium chloride are added and the whole is kept at 60 ° C. with stirring. The solids dissolve in about 30 minutes to form a deep red solution of sodium _{chloroplatinate Na 2} [PdCl ₄ ]. At the same temperature, 20 to 30 cm ^{3 of} 25% strength ammonia solution are then added, as a result of which a pink precipitate of [Pd (NHj) ₄ ] [PdCl ₄ ] separates out. This precipitate is not obtained, but the whole maintained at 60 to 80 ⁰ C until [PdCl (NH ₃ J _3] Cl is formed, which for its part to the slightly yellowish [Fd (NH ₃ Y _4] Cl ₂ is reacted. The clear yellow solution is ^{cooled to 5 to 10 °} C. and a solution of 3.1 g (NH ₄ I ₂ SO ₃ .H ₂ O in 25 cm ^{3 of} water) was added dropwise. 5.01 g of palladium triammine sulfite (yield 94%) were obtained In the form of fine, colorless crystals, which are filtered off and dried under reduced pressure. The elemental analysis confirms the above formula.

Example 2

The following bath was used for a palladium-nickel alloy:

Pd (as PdCl ₂ [OC (NH ₂ ) ₂ ] ₂ .... 6 gΊ

Ni (as NiSO ₄ ) 6 g / l

Na ₂ SO ₃ 30 g / l

NH ₄ OH (25%) 100-110 cm ³ 1

(NHJ ₂ SO ₄ 45 g Ί

»DEQUEST 2044« (30%) .... 25 cm ³ 1
Anionic surfactant

Medium (40%) 0.5 cm ³ Ί

pH 9.5-9.8

At 50 to 60 ° C. and a current density of 1.5 A / dm ² , a shiny palladium-nickel alloy (1: 1) of high hardness (500 HV) and good ductility was obtained. With this bath, layers of more than 50 μm can be obtained without cracks with a current efficiency of 25 mg / A · min.

When the palladium and nickel content of the bath has dropped by about 20%, it is topped up with a 1: 1 mixture for palladium and nickel in the form of Pd (NH ₃ ) ₃ SO ₃ and NiSO ₄ .

With 2 or 5 μm thick palladium-nickel layers coated articles were tested for corrosion resistance used: coatings made of palladium and pure nickel of the same layer thickness.

1. Ammonia test

The items were in a closed. Vessel containing ammonia gas at room temperature kept over a saturated solution of sodium sulfite. After 24 hours, those with pure Palladium or nickel-coated objects show signs of corrosion, while those according to the invention Alloy layers were unaffected. To

Days, the comparison objects were completely corroded, whereas those coated according to the invention Objects showed only minor attack.

2. Thioacetamide test _s

The objects to be examined were placed in a closed vessel in the immediate vicinity of thioacetamide powder and a conc. Sodium sulfite solution held. After 5 days they were with Nickel or palladium-coated objects are heavily corroded, while those according to the invention with a palladium-nickel alloy coated showed only slight attack.

3. Sweat test

A solution of artificial sweat (German standards BAM) was made as follows:

NaCl 20 g / l

NH ₄ Cl 17.5 g / l

Urea 5 g / l

CH ₃ COOH 2.5 g / l

CH ₃ -CO - COOH 2.5 g / l

Butyric acid 5 g / l

Lactic acid 15 g / l

H ₂ O ad 1 1

NaOH for pH 4.7

The objects to be tested were placed on cotton pads soaked in the above solution in one placed at 40 ° C container and thermostatically controlled. After 11 days showed the objects coated according to the invention show only slight attack, while the comparison samples were badly corroded.

35 Example 3

For making a palladium-copper Ubcr-7ug the following bath was used:

Pd (as PdSO ₃ (NH ₃ ).,) 5 g / l

Cu (as CuSO ₄ ) 0.5 a I

(NH ₄ I ₂ SO ₄ 50 H / 1

Na ₂ SO ₃ 30 g / l

»DEQUEST 2044« (30%) 20cm ³ 1

Na lauryl sulfate (30%) .T 0.5 cm ³ 1

pH (adjusted with NH ₄ OH) 9.5

At 60 ° C. and a current density between 0.9 and A / dm ² , glossy gray-pink was obtained. ductile, crack-free layers even up to a thickness of over μην

Example 4

For the production of a palladium-gold coating the following bath was used:

Au (as Au ₂ SO ₃ ) 5 g / l

Pd (as PdSO ₃ (NH ₃ J ₃ ) lg / 1

Na ₂ SO ₃ 30 g / l

(NH _{4 I 2} SO ₄ 50 g / l

"DEQUEST 2044" (30%) 20 cm ³ / l

As ₂ O ₃ (0.1%) 3Cm ³ I.

Polyethylene glycol Na ₂ SO ₄ 0.05 g / l

At 50 to 60 C and 1 A dm ² , a yellowish-gray coating is obtained, which was 18 to 20 carat gold in terms of gold.

Example 5

For the production of a palladium coball overlay the following bath was used:

Pd (as LPd (NH ₁ I ₄ JCU) 5 u 1

Co (as CoSO ₄ ) 5 u I

Na ₂ SO., 30gl

Sodium allylsulfonal (30% iu) I cm ³ 1

NH ₄ OH for pH. "9.5

A glossy ductile coating of was obtained under the operating conditions of the above example Palladium-cobalt 1: 1, whose properties are comparable to the palladium-nickel alloy Example 2.

In a modification of this example, 20 cm ³ 1 of the wetting agent solution from Example 1 were added to the bath. This sad was less sensitive to the presence of impurities and had a longer working capacity.

Example 6

For the production of a palladium-zinc coating the following bath was used:

Pd (as PdCl ₂ (NHj) ₂ ) 6.5 g / l

Zn (as ZnSO ₄ ) 6 g / l

(NH ₄ J ₂ SO ₄ 50gl

(NHJ ₂ SO ₃ 40gl

OC- [NH-CH ₁ -PO (OH),], 2g 1

Dodecyl sodium sulfate (10%) ~ 1.5 cm '1

NH ₄ OH for pH 9.8

At 60X and 1 A dm ² , a crack-free, white, glossy layer with a thickness of at least about 5 μm, good corrosion resistance, was obtained. If necessary, the bathroom can be with

Pd (SO ₃ ), (NH ₃ ) ₂ Zn can be refreshed.

Example 7

The following electrolyte was used for the production of a palladium alloy with several alloy elements applied:

Pd (as PdCl, [OC (NH, K] ₂ ) 5 c / 1

Ni (as NiSO ₄ ) 5 g / l

Zn (as ZnSO ₄ ) 0.06 u / l

Cu (as CuSO ₄ ) 0.03 g / l

CH ₃ COONH ₄ 50 g / l

Na ₂ SO ₃ 25 g / l

"DEQUEST 2044" (30%) 100 cm ³ / l

NH ₄ OH (25%) for pH 9.3-10

At 50 to 60 ° C. and 1 A / dm ² , white glossy layers with a thickness of 20 μm and containing 60% Pd, 36% Ni, 2% Zn and 2% Cu were obtained.

Test specimens with a 5 ^ m layer of the above alloy were subjected to the artificial sweat test according to the example 2 subjected. No change was found after 20 days.

Claims (1)

Claims: 24 i 1. Sulphite-containing galvanic bath for the deposition of palladium or palladium alloys, p free of cyanide, nitrate or nitrite, containing 1 to 50 g / l palladium, optionally 1 mg / 1 to 50 g / l Alloy metals and possibly 1 to 100g / 1 brightening additives and / or scavenging agents for the impurities, in particular an organically bound nitrogen, sulfur or phosphorus containing chelating or complexing agents in the form of polyenamines, arene and alkane sulfonates, phosphonates and their alkali and ammonium salts, optionally with functional Substituents —OH, —COOH, —CHO and optionally substituted by amino groups, characterized by a content of at least one palladium compound of the formulas 814