KR20180034611A - How to Metallize a Plastic Surface - Google Patents

Abstract

The present invention relates to a process for the preparation of a coating composition comprising a plastic surface, in particular an acrylonitrile / butadiene / styrene copolymer (ABS), using an etching solution comprising at least one ionic liquid (IL) And a mixture of other plastics (ABS blend), the method comprising treating the plastic surface after etching with an aqueous rinse solution (RS) while applying ultrasonic waves.

Description

How to Metallize a Plastic Surface

The present invention relates to a process for the preparation of a coating composition comprising a plastic surface, in particular an acrylonitrile / butadiene / styrene copolymer (ABS), using an etching solution comprising at least one ionic liquid (IL) And a mixture of other plastics (ABS blend), the method comprising treating the plastic surface after etching with an aqueous rinse solution (RS) while applying ultrasonic waves.

Coating the surface of plastic parts with metal, so-called plastic galvanizing, is becoming increasingly important. By the plastic zinc plating method, a composite material in which advantages of plastic and metal are combined is obtained. Plastics can be converted into virtually any desired shape by simple processing methods such as injection molding or extrusion. In addition, the use of plastic parts can achieve a significant reduction in weight compared to metal parts. Subsequent zinc plating of the resulting plastic molding is often performed for decorative purposes or to achieve a shielding effect.

For example, sanitary equipment, automotive accessories, furniture hardware, costume ornaments and buttons / knobs are metallized in whole or in part only to give the parts an attractive appearance. Furthermore, plastics can also be metallized for functional reasons. For example, the housing of the electronics is metallized to protect it from radiation or imitation of electromagnetic radiation. In addition, the surface properties of plastic parts can be changed in a controlled manner through a metallic coating. In a considerable number of cases, copolymers of acrylonitrile, butadiene and styrene (ABS copolymers) and mixtures of such copolymers with other copolymers such as ABS / polycarbonate blends (ABS / PC blends) are used .

For the production of a metallic coating on a plastic part, the plastic part is typically fixed in a frame and brought into contact with a plurality of different processing fluids in a specific process sequence. For this purpose, in the first step, plastics are typically pretreated to remove impurities such as grease from the surface. Etching methods are then typically used to roughen the surface so that the subsequent metal layer is adhered sufficiently firmly. In the etching operation, the formation of a predetermined homogeneous structure in the form of a recess on the plastic surface is particularly important.

The rough surface is then treated with a so-called activator to form a catalyst surface for subsequent chemical metallization. For this purpose, so-called ionogenic activators or colloidal systems are often used. For example, in the case of activation using an ion-generating system (see, for example, Kunststoffmetallisierung, Handbuch fur Theorie und Praxis ["Plastic Metallization", Handbook for Theory and Practice] (Eugen G. Leuze Verlag, Saulgau, 1991, pages 46-47) , The plastics surface is treated first with tin (II) ions, and after the treatment and rinsing with water, the gel of tin oxide hydrate is firmly adhered. In subsequent treatment with a palladium salt solution, the palladium nuclei are formed on the surface through a redox reaction with the tin (II) species, which is catalytically active for chemical metallization. In the case of activation using a colloidal system, a colloidal palladium solution is generally used which is formed by the reaction of palladium chloride with tin (II) chloride in the presence of excess hydrochloric acid (Annual Book of ASTM Standard, Vol. 02.05 "Metallic and Inorganic Metal Powders, Sintered P / M Structural Parts ", Designation: B727-83, Standard Practice for Preparation of Plastic Materials for Electroplating, 1995, pages 446-450).

After activation, plastic parts are first chemically metallized, typically using a metastable solution of a metallized bath. Such bases generally include a metal deposited in the form of a salt in aqueous solution, and a reducing agent for the metal salt. The metal is formed by reduction only when the chemical metallization bath is in contact with a metal nucleus, for example a palladium seed, on the plastic surface, which is deposited on the surface as a firmly bonded layer. In the chemical metallization step, a nickel alloy of copper, nickel, or phosphorus and / or boron is often deposited.

An additional metal layer can then be electrolytically deposited on the coated plastic surface with the aid of a chemical metallization bath. Electrolytic deposition of a copper layer or an additional nickel layer is often done first before the desired ornamental chromium layer is applied electrochemically.

An important process step in plastic galvanizing is pretreatment of plastic surfaces. One reason for the need for pretreatment is to improve, and typically substantially enable, the adhesion of the metal on the plastic surface. For this purpose, the plastic surface must be roughened and have a greater hydrophilicity. In this context, the formation of a predetermined homogeneous structure in the form of a groove on a plastic surface is particularly important. This groove serves as a starting point for the growth of metal nuclei in subsequent metallization steps.

Since roughening has also been carried out by mechanical methods at an early stage, swelling and etching of plastic surfaces using chemicals for this purpose have been recently established. The most commonly used etchant is a chromium-sulfuric acid etchant (chromium trioxide in sulfuric acid), especially for ABS (acrylonitrile-butadiene-styrene copolymer) or polycarbonate. Chromium-sulfuric acid etchants are very toxic and require special precautions in process, post-treatment and disposal. Due to the chemical process in the etching process, for example the reduction of the chromium compound used, the chromium-sulfuric acid etchant is used in its entirety and is generally not reusable.

Methods of chemical metallization of plastic surfaces using chromium-containing etching solutions are described, for example, in DE-A 100 54 544. [

The use of ionic liquids for the pretreatment (etching) of plastic surfaces in the context of metallization is also known. WO 2010/142567 describes a method of coating a plastic with a metal, wherein the plastic is pretreated with a composition comprising at least one salt having a melting point of from 1 bar to less than 100 DEG C (ionic liquid). Pre-treatment of copolymers of various thermoplastic plastics such as polyamides, polyolefins, polyesters, polyethers, polystyrenes, and styrenes such as acrylonitrile / butadiene / styrene copolymers (ABS) is described.

Ionic liquids have been known since the late 40's. It is a liquid salt melt which is liquid at a temperature below 100 ° C, preferably at room temperature (25 ° C, 1 bar) and especially below room temperature. Ionic liquids are a new class of solvents with non-molecular, ionic character.

Typical cation / anion combinations for deriving ionic liquids are, for example, combinations of dialkylimidazolium, pyridinium, ammonium and phosphonium, halide, tetrafluoroborate, methyl sulfate. Further, combinations of cations and anions that lead to a plurality of low-melting salts may be further considered.

The use of ionic liquids in a wide variety of different technical fields is known. With respect to polymers, the use of ionic liquids as antistatic or plasticizers is described in the prior art, for example in WO 2004/005391, WO 2007/090755 and WO 2008/006422. Document DE 10 2009 003 011 discloses the use of ionic liquids as adhesives for polymers.

It is an object of the present invention to provide an improved method of coating a plastic surface with a metal, which uses an ionic liquid in the pretreatment of plastic parts. This may obviate the conventional and conventional use of toxic and adverse chromium-containing etching solutions. The improvement in the coating method may be in the improvement of process technology, such as improved strength / adhesion on the plastic surface firstly and the nature of the metal layer surface, and also a small influx of etching solution. The method must be feasible in a very simple and inexpensive manner, and the recovery and / or recycling of the etching solution must be feasible in a highly effective manner.

Surprisingly, it has been found that a rinse step using ultrasound after treating the plastic surface with an etching solution comprising at least one ionic liquid can achieve an improved metal coating. The ultrasonic rinse step of the present invention using an aqueous rinse solution can provide a homogeneous, glossy, defect-free, and very well-adhered metal surface. More particularly, by the method of the present invention, advantageous metal coatings having a layer sequence of chemically deposited nickel, copper, nickel, chromium can be obtained.

The present invention relates to a method of coating a plastic surface, in particular a plastic molding, with a metal, comprising the following steps:

a) Pre-treating the plastic surface, in particular the plastic molding, with a composition (C) (etching solution) comprising at least one ionic liquid (IL);

b) Treating the plastic surface from step a), in particular the plastic molding, with an aqueous rinse solution (RS), while applying ultrasonic waves;

c) Characterized in that the plastic surface from step b), in particular the plastic molding, comprises at least one ion-generating and / or colloidal activator, especially at least one palladium component (P), preferably at least one colloidal palladium component Treating with the activator composition (A);

d) Treating the plastic surface, in particular the plastic molding, from step c) with an accelerator composition (B) comprising an acid and / or a reducing agent;

e) Wherein the surface from step d) comprises at least one metal salt selected from at least one metal salt, preferably nickel, copper and chromium salts, and at least one reducing agent, preferably an in situ reducing agent Chemically depositing a metal layer, preferably a metal layer consisting essentially of nickel, copper, chromium or alloys thereof, by treating with a coating composition (M1);

f) The plastic surface, in particular the plastic molding, from step e) is applied to at least one coating composition comprising at least one metal compound, in particular at least one metal salt, preferably at least one copper salt, chromium salt and / M '), the plastic surface, in particular the plastic molding, from step e) can be treated with at least one further metal layer, preferably a metal layer consisting essentially of copper and / or a metal consisting essentially of chromium Electrochemically coating the layer.

In addition to the known use of ionic liquids, further distinct improvements in coating results, such as better adhesion of the subsequent metal layer on the plastic surface, can be achieved. The ultrasonic rinse step has been found to be particularly advantageous in that it allows the partially dissolved plastic particles to be desorbed from the surface, leading to a more homogenous structure of the surface and an improved subsequent metallic coating.

The standard definition of an ionic liquid distinguishes it from known salt melts by melting points below 100 ° C, preferably below 80 ° C, or even below room temperature. In the context of such an application, it is to be understood that the ionic liquid, in its pure state, means a salt having a melting point of less than 100 DEG C at 1 bar.

A feature of the process of the present invention is that a more homogeneous and better adherent metal coating is obtained as compared to a conventional rinsing step with water. Preferably, the metal layer in the order of the layers of all metal layers, in particular the chemically deposited nickel, copper, nickel and chromium, has advantageous properties. In addition, the water consumption in the rinsing step can be reduced.

It is further advantageous in the process of the present invention that the plastic surface is etched without a metal salt, and the use of toxic and adverse chromium-containing etching solutions can be omitted.

Plastics and metals

In the context of the present invention, molding or plastic molding may be carried out using articles derived from a primary molding process, such as, for example, primary molding methods such as casting, die casting, injection molding, extrusion blow molding, Means an article made from an essentially plastic material, which is derived by extrusion, sintering, and optionally subsequent molding methods. This includes in particular workpieces and semi-finished products, such as molded workpieces, injection molded workpieces, films or foils.

In the process of the present invention, plastics, in particular plastics having a non-conductive surface, are coated with a metal in multiple steps. It is preferably a thermoplastic. The thermoplastic can be melted and converted to the desired shape by a different method, for example by injection molding, extrusion, thermoforming or blow molding.

Suitable thermoplastics include copolymers of polyamides, polyolefins, polyesters, polyethers, polyacetals, especially polyoxymethylene, polycarbonates, polyurethanes, polyacrylates, polystyrenes or styrenes, especially styrene / acrylonitrile Styrene / acrylonitrile copolymer (ASA) and acrylonitrile / butadiene / styrene copolymer (ABS).

Polyamides include, but are not limited to, polycondensates of aminocarboxylic acids such as 6-aminocarboxylic acid or epsilon-caprolactam, or diamino compounds and dicarboxylic acids such as hexane-1,6-diamine and adipate Polycondensates of acids.

Suitable polyolefins are polyethylenes, polypropylenes, and copolymers of ethylene or propylene.

Suitable polyesters are polycondensation products of polyhydric alcohols, such as butanediol, hexanediol, glycerol or trimethylol propane, with polybasic carboxylic acids, especially phthalic acid and its isomers, adipic acid or trimellitic anhydride.

A specific polyacetal is polyoxymethylene (POM).

The polycarbonate is a polycarboxylic acid and a polyhydric alcohol, for example, an ester of bisphenol A; In addition, polyester carbonates containing an additional polybasic carboxylic acid as a forming element are mentioned.

Typically, the polyether comprises a repeating ether group. For example, polyetherimides, particularly including polyetherimides including aromatic ring systems bonded through repeated ether and imide groups, in particular polyether ketones comprising phenylene groups bonded by repeating ether and ketone groups, ether and thio Polyether sulfides containing ether groups and polyethersulfones containing repeating ether groups and sulfone groups in the polymer backbone are of particular industrial importance.

Polyurethanes are typical polyadducts formed from polyfunctional isocyanates and polyhydric alcohols, useful examples being both aliphatic and aromatic compounds. Polyacrylates are homo- or copolymers of acrylic monomers or methacrylic monomers; A specific example is polymethylmethacrylate (PMMA).

It is also possible to carry out the method of the invention in which the plastic comprises (or consists of) a carbon-fiber-reinforced epoxy resin. Carbon-fiber-reinforced epoxy resins are conventionally known and typically comprise from 10 to 90% by volume, preferably from about 50 to 70% by volume, of reinforcing carbon-fiber. Suitable epoxy resins are polyethers obtained by reaction of a compound having a hydroxyl group, such as a bisphenol, with an epoxy compound, for example epichlorohydrin. Typically, the epoxy resin can be cured by reaction with a curing agent, such as an amine, an acid, an acid anhydride, or a thiol.

Preferred polymers are homo- and copolymers of styrene such as polystyrene, styrene / acrylonitrile copolymers and in particular acrylonitrile / butadiene / styrene copolymers (ABS).

A preferred embodiment is characterized in that the plastic surface is a polyamide, polyolefin, polyester, polyether, polyacetal, polycarbonate, polyurethane, polyacrylate, polystyrene or styrene / acrylonitrile copolymer (SAN) / Styrene / acrylonitrile copolymer (ASA) and styrene copolymer selected from acrylonitrile / butadiene / styrene copolymer (ABS). The plastic to be coated may also comprise a blend of two or more of the above-mentioned plastics and / or a plastic part (two-component plastic) of two or more of the plastics mentioned above

A further preferred embodiment is characterized in that the plastic is selected from the group consisting of polyamides, polyolefins, polyesters, polyethers, polyacetals, polycarbonates, polyurethanes, polyacrylates, polystyrenes or styrene / acrylonitrile copolymers (SAN) A styrene / styrene / acrylonitrile copolymer (ASA), a copolymer of styrene selected from acrylonitrile / butadiene / styrene copolymer (ABS), and a carbon-fiber-reinforced epoxy resin (Or consists thereof). ≪ / RTI >

A preferred embodiment is characterized in that the plastic surface is made of polyamide, polystyrene or styrene / acrylonitrile copolymer (SAN), acrylic ester / styrene / acrylonitrile copolymer (ASA) and acrylonitrile / butadiene / styrene copolymer ), Or a blend and / or multicomponent plastic comprising at least one, preferably at least two, of the above-mentioned plastics, .

Particularly preferred plastics are polyamide and ABS. Most preferably, the plastics are selected from the group consisting of acrylonitrile / butadiene / styrene copolymers (ABS) or blends such as ABS / PC (acrylonitrile / butadiene / styrene copolymers and polycarbonates) and / Includes multi-component plastics. ABS is supplied, for example, under the trade name Terluran® from Styrolution.

The article to be coated may consist entirely of one or more of the plastics. This type of article can have any desired shape and can be obtained by thermoplastic plastic molding methods such as, for example, injection molding, extrusion, thermoforming and blow molding. Alternatively, it can be made of different materials. What is essential is that the surface to be coated is made of plastic.

In the method of the present invention, the plastic or plastic surface is coated with a metal. Useful metals are, in particular, nickel, aluminum, copper, chromium, tin or zinc, and alloys thereof. The metal may be applied in one or preferably more than one layer or work. The application of layers of different metals, in particular at least three different metal layers, may be desirable.

A preferred embodiment relates to the described method of the invention wherein the metal comprises at least one metal selected from nickel, aluminum, copper, chromium, tin, zinc and alloys thereof.

The ionic liquid (IL)

The composition (C) used in the process of the present invention comprises at least one salt (hereinafter referred to as an ionic liquid (IL)) having a melting point of less than 100 DEG C at 1 bar.

Preferably, the ionic liquid (IL) has a melting point of less than 100 DEG C, more preferably less than 85 DEG C and most preferably less than 60 DEG C, in each case at 1 bar (standard conditions).

The molar mass of the ionic liquid (IL) is preferably less than 2000 g / mol, more preferably less than 1500 g / mol, more preferably less than 1000 g / mol and most preferably less than 750 g / mol ; In certain embodiments, the molar mass is 100 to 750 g / mol or 100 to 500 g / mol.

A preferred ionic liquid (IL) comprises at least one organic compound as a cation; Most preferably, it comprises exclusively organic compounds as cations. Suitable organic cations are, in particular, organic compounds having heteroatoms such as nitrogen, sulfur or phosphorus; An organic compound having a cationic group selected from an ammonium group, a sulfonium group and a phosphonium group is particularly preferable. The ionic liquid (IL) is especially a compound represented by the general formula [A] _n ⁺ [X] ^n- wherein n is 1, 2, 3 or 4 and [A] ⁺ is an ammonium cation, a sulfonium cation or a phosphonium cation And [X] ^n- is a mono-, di-, tri-, or tetravalent anion.

The ionic liquid (IL) may also be a mixed salt comprising at least two different organic cations [A] ⁺ , or a mixture of at least one organic cation [A] ⁺ and one or two different mono-, di-, Or a mixed salt comprising a divalent metal cation [M] ^{n +} .

In a preferred embodiment, the at least one ionic liquid (IL) is at least one salt having a cation selected from imidazolium cations, pyridinium cations, pyrazolium cations and alkylammonium cations.

In a preferred embodiment, the ionic liquid (IL) is a combination of at least one first ionic liquid (IL1) and at least one second ionic liquid (IL2), wherein the first ionic liquid (IL1) , Wherein the second ionic liquid (IL2) comprises at least one alkylammonium cation and the second ionic liquid (IL2) comprises, as a cation, at least one aromatic heterocycle having a delocalized cationic charge and comprising at least one nitrogen atom It is a combination. Preferably, the combination comprises at least two different ionic liquids (IL1) and (IL2) in an amount of from 1 to 20, preferably from 1.5 to 10, more preferably from 2 to 6, particularly preferably from 3 to 5 , As a mass ratio of (IL1) to (IL2) of 4, for example.

Preferably, said combination comprises at least two different ionic liquids (IL1) and (IL2) in an amount of from 1 to 20, preferably from 3 to 18, more preferably from 5 to 20, particularly preferably from 7 to 15 As a mass ratio of (IL1) to (IL2), e.g., 7.5 or 15.

Preferably, the ionic liquid (IL), in particular the ionic liquid (IL1), comprises at least one, and preferably exactly one, alkylammonium cation as the cation. In the context of the present invention, an alkylammonium cation means an ammonium compound having at least one C _1-20 -alkyl radical, preferably a C _1-18 -alkyl radical, and a singulated positive charge on the nitrogen atom . The compound may be a compound having a tetravalent nitrogen (quaternary ammonium compound) or a compound having a trivalent nitrogen, wherein one bond is a double bond. Preferably, the alkylammonium cation of the ionic liquid (IL1) is a non-aromatic compound.

Useful ring systems include monocyclic, bicyclic, non-aromatic ring systems. Examples of such include bicyclic systems as described in WO 2008/043837. The bicyclic system of WO 2008/043837 is preferably a diazabicyclo derivative consisting of one 7-membered ring and one 6-membered ring containing an amidinium group; A specific example is the 1,8-diazabicyclo (5.4.0) undec-7-enium cation.

Preferably, the ionic liquid (IL), especially the ionic liquid (IL1), contains exactly one alkylammonium cation as the only cation. The ionic liquid IL may alternatively be a mixed salt comprising at least one alkylammonium cation and at least one additional organic cation [A] ⁺ and / or at least one further metal cation [M] ^{n +} . Particularly preferred organic cations are preferably quaternary ammonium cations having four C _{1 -12} -alkyl groups as substituents on the nitrogen atom.

As a cation, an ionic liquid (IL) comprising at least one, preferably exactly one, alkylammonium cation of general formula (I) is preferred:

[Wherein,

R Is an organic group comprising 1 to 20, preferably 1 to 18, more preferably 1 to 12 and particularly preferably 1 to 6 carbon atoms, wherein the organic group is unsubstituted or substituted with 1 to 5 Is a saturated or unsaturated, non-cyclic or cyclic aliphatic radical which may be interrupted or substituted with one or more heteroatoms or functional groups;

R ¹ , R ² and R ³ are each independently:

Hydrogen;

Halogen, especially fluorine, chlorine, bromine and iodine, preferably chlorine;

Which may optionally be substituted with a functional group selected from C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkyloxy, C ₁ -C ₆ -alkoxycarbonyl, hydroxyl, halogen, amino, cyano and sulfo, Or a C ₁ -C ₁₈ -alkyl radical which may be interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups;

Which may optionally be substituted with a functional group selected from C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkyloxy, C ₁ -C ₆ -alkoxycarbonyl, hydroxyl, halogen, amino, cyano and sulfo, Or a C ₂ -C ₁₈ -alkenyl radical in which one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups may intervene;

Which may optionally be substituted with a functional group selected from C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkyloxy, C ₁ -C ₆ -alkoxycarbonyl, hydroxyl, halogen, amino, cyano and sulfo, A C ₅ -C ₁₂ -cycloalkyl radical;

Which may optionally be substituted with a functional group selected from C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkyloxy, C ₁ -C ₆ -alkoxycarbonyl, hydroxyl, halogen, amino, cyano and sulfo, A C ₅ -C ₁₂ -cycloalkenyl radical; or

Oxygen, nitrogen and / or containing a sulfur atom, and C ₁ -C ₆ - alkyl, C ₁ -C ₆ - alkyloxy, C ₁ -C ₆ - alkoxycarbonyl, hydroxyl, halogen, amino, cyano, and alcohol Lt; / RTI > is a 5- to 6-membered heterocycle optionally substituted with a functional group selected from the group consisting of

The two adjacent R ¹ , R ² and R ³ radicals in formula (I), together with the nitrogen atom, represent C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkyloxy, C ₁ -C ₆ -alkoxycarbonyl , Optionally substituted with a functional group selected from hydroxyl, halogen, amino, cyano and sulfo, optionally substituted with one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups Unsaturated or saturated 5- to 7-membered ring;

X Is an anion;

n Is 1, 2 or 3;

Possible heteroatoms in the definitions of R and R ¹ to R ³ radicals are, in theory, any heteroatom which in the formal sense can replace -CH ₂ -, -CH═, -C≡ or ═C═ groups. Where the carbon-containing radical comprises a heteroatom, oxygen, nitrogen, sulfur, phosphorus and silicon are preferred. Preferred groups include, in particular _{-O-, -S-, -SO-, -SO 2} -, -NR'-, -N =, -PR'-, -POR'- and -SiR _'2 - (wherein, R Quot; radical is the remainder of the radical comprising the carbon atom). When the radicals R ¹ to R ³ in the above-mentioned formula (I) are bonded to a carbon atom and not to a heteroatom, it can also be bonded directly via a heteroatom.

Possible functional groups are, in theory, all functional groups capable of bonding to carbon atoms or heteroatoms. Suitable examples include, -OH (hydroxyl), = O (especially in the form of a carbonyl group), -NH ₂ (amino), = NH (imino), -COOH (carboxyl), -CONH ₂ (carboxamide) , -SO ₃ H (sulfo), and -CN (cyano). The functional groups and heteroatoms may also be immediately adjacent and thus may be a combination of a plurality of adjacent atoms, for example, -O- (ether), -S- (thioether), -COO- (ester) primary amide) or -CONR'- (3 primary amide), as well as, for example, di (C ₁ -C ₄ - alkyl) amino, C ₁ -C ₄ - alkyloxycarbonyl, or C ₁ -C ₄ - alkyloxy .

Halogen is fluorine, chlorine, bromine and iodine.

Preferably, the R radical is:

Unsubstituted or branched, unsubstituted or mono- to polysubstituted with hydroxyl, halogen, cyano, C ₁ -C ₆ -alkoxycarbonyl and / or sulfo, preferably having 1 to 20 carbon atoms in total, C ₁ -C ₂₀ -alkyl radicals such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, Butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, Butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, Methyl-2-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl- 3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, Octyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl, , 2-cyanoethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2- (n-butoxycarbonyl) ethyl, 6-hydroxyhexyl and propylsulfo;

Glycol, butylene glycol, and oligomers thereof having from 1 to 100, preferably from 1 to 6 and particularly preferably from 1 to 3, units and hydrogen or C ₁ -C ₆ -alkyl as an end group, example _{^{R A O- (CHR B -CH 2}} -O) p -CHR B -CH 2 - , or ^{_{R A O- (CH 2 CH 2}} CH 2 CH 2 O) p -CH 2 CH 2 CH 2 CH 2 O- (Wherein R ^A and R ^B are preferably hydrogen, methyl or ethyl and p is preferably 0 to 3), especially 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3 , 6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxydecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12-tetra Oxatetradecyl;

vinyl; or

Unsubstituted C ₅ -C ₁₂ -cycloalkenyl radical.

More preferably, the R radical is selected from unbranched and unsubstituted C ₁ -C ₁₈ -alkyl, preferably C ₁ -C ₁₂ -alkyl, such as methyl, ethyl, 1-propyl, 1-butyl, - pentyl, 1-hexyl, 1-heptyl or 1-octyl, or _{CH 3 O- (CH 2 CH 2} O) p -CH 2 CH 2 - and _{CH 3 CH 2 O- (CH 2} CH 2 O) p -CH ₂ CH ₂ - (wherein p = 0 to 3).

Preferably, the R ¹ , R ² and R ³ radicals are each, independently,

Hydrogen;

Optionally mono- to poly-substituted with a functional group selected from C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkyloxy, C ₁ -C ₆ -alkoxycarbonyl, hydroxyl, halogen, amino, cyano and sulfo which may be, C ₁ -C ₁₈ - alkyl radical, such as methyl, ethyl example, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2 Methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, Butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, Methyl-2-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl Butyl, 2,3-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 1-decyl, 1-undecyl, 1-undecyl, 1-hexadecyl, 1-octadecyl, 2-hydroxyethyl, 2- (Methoxycarbonyl) ethyl, 2- (n-butoxycarbonyl) ethyl, 2-hydroxyethyl, 2-hydroxy Propyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, , 2-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 2-hydroxyethyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2- Ethoxypropyl, 4-ethoxybutyl, 6-ethoxyhexyl, chloromethyl, 2-chloroethyl, trichloromethyl, 1,1-dimethyl- Methoxymethyl, 2-butoxyethyl, di Ylmethyl, diethoxyethyl, 2-isopropoxy ethyl, 2-butoxy-propyl, 2-ethyl-octyloxy, 2-methoxy isopropyl, and propyl sulfonate;

A C ₅ -C ₁₂ -cycloalkyl radical which may optionally be substituted by C ₁ -C ₆ -alkyl; For example, cyclopentyl and cyclohexyl;

Glycol, butylene glycol, and oligomers thereof having from 1 to 100, preferably from 1 to 6 and particularly preferably from 1 to 3, units and hydrogen or C ₁ -C ₆ -alkyl as an end group, example _{^{R A O- (CHR B -CH 2}} -O) p -CHR B -CH 2 - , or ^{_{R A O- (CH 2 CH 2}} CH 2 CH 2 O) p -CH 2 CH 2 CH 2 CH 2 O- (Wherein R ^A and R ^B are preferably hydrogen, methyl or ethyl and p is preferably 0 to 3), especially 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3 , 6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxydecyl, 3,6,9,12-tetraoxatridecyl, 3,6,9,12-tetra 3-oxapentyl, 8-hydroxy-3,6-dioxaoctyl, 11-hydroxy-3,6,9-trioxydecyl, 7-hydroxy- Hydroxy-5-oxanonyl, 14-hydroxy-5-oxoheptyl, 11-hydroxy-4,8-dioxandecyl, Dioctatetradecyl, 5- Oxepentyl, 8-methoxy-3,6-dioxaoctyl, 11-methoxy-3,6,9-trioxydoundyl, 7-methoxy- Dioxanedecyl, 15-methoxy-4,8,12-trioxamantadecyl, 9-methoxy-5-oxanonyl, 14- Ethoxy-3-oxepentyl, 8-ethoxy-3,6-dioxaoctyl, 11-ethoxy-3,6,9-trioxydoundyl, 7-ethoxy- -Ethoxy-4,8-dioxydecyl, 15-ethoxy-4,8,12-trioxam pentadecyl, 9-ethoxy-5-oxanonyl or 14- Decyl; or

Two adjacent R ¹ , R ² and R ³ radicals in formula (I), together with the nitrogen atom, are a saturated and unsubstituted 5- to 7-membered ring; For example, two adjacent R ¹ , R ² and R ³ radicals are 1,4-butylene, 1,5-pentylene or 3-oxa-1,5-pentylene.

In one embodiment, Formula (I) 2 of the adjacent R ^1, R ² and R ³ radicals are, together with the nitrogen atom, C ₁ -C ₆ at -alkyl, C ₁ -C ₆ - alkyloxy, C ₁ - Which may be optionally substituted with a functional group selected from halogen, C ₁ -C ₆ -alkoxycarbonyl, hydroxyl, halogen, amino, cyano and sulfo and which may contain one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted im Unsaturated or saturated 5- to 7-membered ring in which an anger may optionally be interposed. Preferably, two adjacent R ¹ , R ² and R ³ radicals in formula (I) together with the nitrogen atom form a saturated 5- to 7-membered ring and two adjacent R ¹ , R ² and R ³ radical is 1,4-butylene, 1,5-pentylene or 3-oxa-1,5-pentylene.

Most preferably, the radicals R ¹ , R ² and R ³ are each, independently, hydrogen, unsubstituted C ₁ -C ₁₈ -alkyl, preferably C ₁ -C ₁₂ -alkyl (eg methyl, ethyl (1-pentyl, 1-hexyl, 1-heptyl, 1-octyl), 2-hydroxyethyl, 2-cyanoethyl, 2- (methoxycarbonyl) carbonyl) ethyl, 2- (n- butoxycarbonyl) ethyl, _{chlorine, CH 3 O- (CH 2 CH} 2 O) p -CH 2 CH 2 - or _{CH 3 CH 2 O- (CH 2} CH 2 O) _p- CH ₂ CH ₂ - wherein p = 0 to 3, or two adjacent R ¹ , R ² and R ³ radicals are 1,4-butylene, 1,5-pentylene or 3- Pentylene.

More preferably, R ¹ , R ² and R ³ are hydrocarbyl groups as described above which do not have a hydrogen atom or a further hetero atom. Most preferably, R ¹ , R ² and R ³ are a hydrogen atom or an unsubstituted C ₁ -C ₁₈ alkyl group, more preferably a C ₁ -C ₆ alkyl group such as a methyl group, an ethyl group, a propyl group, an iso Propyl group or n-butyl group.

More preferably, the at least one ionic liquid (IL1) comprises an alkylammonium cation of formula (I):

[Wherein,

R is selected from the group consisting of unbranched and unsubstituted C ₁ -C ₁₈ -alkyl (for example, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, Ethyl, 1-butyl and 1-octyl), CH ₃ O- (CH ₂ CH ₂ O) _p -CH ₂ CH ₂ - or CH ₃ CH ₂ O- (CH ₂ CH ₂ O) _p -CH ₂ CH ₂ - (wherein p = 0 to 3);

R ¹ , R ² and R ³ are each independently:

A hydrogen atom, an unsubstituted C ₁ -C ₁₈ - alkyl (e.g. methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl), 2-hydroxyethyl, 2- (Methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2- (n-butoxycarbonyl) ethyl, chlorine, CH ₃ O- (CH ₂ CH ₂ O) _p -CH ₂ CH ₂ - or CH ₃ CH ₂ O- (CH ₂ CH ₂ O) _p -CH ₂ CH ₂ - (wherein p = 0 to 3), or

Two adjacent R ¹ , R ² and R ³ radicals in formula (I), together with the nitrogen atom, form a saturated and unsubstituted 5- to 7-membered ring such as 1,4-butylene, 1,5 - pentylene or 3-oxa-1,5-pentylene,

X Is an anion;

n Is 1, 2 or 3;

More preferably, the ionic liquid (IL1) comprises an alkylammonium cation of formula (I) as follows:

R is C ₁ -C ₁₈ - alkyl, preferably C ₁ -C ₆ - alkyl, R ^1, R ² and R ³ are each independently a hydrogen atom or a C ₁ -C ₁₈ - is a C ₁ alkyl, preferably -C ₆ - alkyl; or

R is C ₁ -C ₁₈ - alkyl, preferably C ₁ -C ₆ - alkyl; R ¹ and R ² together are 1,5-pentylene or 3-oxa-1,5-pentylene and R ³ is a hydrogen atom or a C ₁ -C ₁₈ -alkyl, preferably C ₁ -C ₆ -alkyl being.

The alkylammonium cations in the most preferred ionic liquids (IL1) are selected from the group consisting of methyltri (1-butyl) ammonium, 1-butyl- 1 -methylpyrrolidinium, N, N-dimethylpiperidinium and N, Lt; / RTI >

Preferred anions, in particular the preferred X ^n- anions according to formula (I), are as described below.

As the cation, methyltri (1-butyl) ammonium and an anion such as chloride, bromide, hydrogensulfate, tetrachloroaluminate, thiocyanate, methylsulfate, ethylsulfate, methanesulfonate, formate, acetate, Particularly preferred is an ionic liquid (IL) comprising an anion selected from dimethyl phosphate, diethyl phosphate, p-tolylsulfonate, tetrafluoroborate and hexafluorophosphate.

Particularly preferably, the ionic liquid (IL1) is selected from the group consisting of methyltri (1-butyl) ammonium methylsulfate (MTBS) or 1-butyl- 1- methylpyrrolidinium dimethylphosphate, more preferably methyltri ) Ammonium methyl sulfate (MTBS).

The alkylammonium cation of the ionic liquid (IL) also contains at least one and preferably one or two quadrivalent and / or trivalent nitrogen (s), wherein one bond is a double bond, Ring system. For example, the cation of the ionic liquid (IL), in particular of the ionic liquid (IL1), is selected from the group consisting of a piperidinium cation, a pyrazolium cation, a pyrazolinium cation, an imidazolinium cation, a pyrrolidinium cation, And a cyclic nonaromatic alkylammonium cation selected from the group consisting of zirconium, zirconium, zirconium, zirconium, zirconium, zirconium, zirconium, zirconium and zirconium cations.

Suitable cations of the at least one ionic liquid (IL), in particular of the ionic liquid (IL1), are, for example, cations of the formulas (IIa) to (IIj)

Wherein R is as defined above and the radicals R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are respectively the radicals R ¹ , R ² and R ³ Lt; / RTI >

In a preferred embodiment, the composition (C) comprises, as the cation, at least one aromatic heterocycle having a delocalized cationic charge and containing at least one nitrogen atom, preferably 1, 2 or 3 nitrogen atoms, (Also referred to as an ionic liquid (IL2)). More particularly, at least one nitrogen atom, preferably 1, 2 or 3 nitrogen atoms, is present in the ring system of the heterocycle. Preferably, the ionic liquid (IL2) comprises exactly one aromatic heterocycle, as a cation, having a delocalized cationic charge and containing at least one nitrogen atom. The ionic liquid IL2 may alternatively be a mixed salt comprising at least one aromatic heterocycle and at least one further organic cation [A] ⁺ and / or at least one further metal cation [M] ^{n +} .

The composition (C) can be prepared by mixing the ionic liquid (IL2) with the above-described ionic liquid (ionic liquid) containing at least one alkylammonium cation as a unique ionic liquid or in combination with other ionic liquids, (IL1)). ≪ / RTI >

Most preferably, the ionic liquid (IL) comprises, as a cation, a 5- or 6-membered heterocyclic aromatic ring having 1, 2 or 3, preferably 1 or 2 nitrogen atoms as part of the ring system System. In theory, a 5- or 6-membered heterocyclic aromatic ring system may contain one or two additional heteroatoms, especially oxygen and / or sulfur atoms. Carbon atom of the ring system is, in general, an organic group having carbon atoms of 20 or less, preferably the hydrocarbyl group is a hydrocarbyl, particularly C ₁ -C ₁₆ alkyl, especially C ₁ -C ₁₀ and more preferably C ₁ - C ₄ alkyl group.

Suitable cations of at least one ionic liquid (IL) are, for example, cations of the formulas (IIk) to (IIs "):

Wherein R is as defined above and the radicals R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined above for the radicals R ¹ , R ² and R ³ , respectively. Preferably, the R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ radicals are each independently selected from hydrogen, methyl, ethyl, 1-propyl, 1-butyl and chlorine.

Preferably, the cation of at least one ionic liquid (IL2) is a cation of the above-mentioned formula (IIk), (IIo), (IIp), (IIq), (IIq ') and Lt; RTI ID = 0.0 > (IIo). ≪ / RTI >

Very particularly preferred is an ionic liquid (IL), wherein the cation is a pyridinium cation of the formula (IIk) as follows:

One of the R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ radicals is methyl, ethyl or chlorine and the remaining R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ radicals are hydrogen; or

R ⁶ is dimethylamino and the remaining R ⁴ , R ⁵ , R ⁷ and R ⁸ radicals are hydrogen; or

R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ radicals are all hydrogen; or

R ⁵ is a carboxyl or carboxamide and the remaining R ⁴ , R ⁶ , R ⁷ and R ⁸ radicals are hydrogen; or

R ⁴ and R ⁵ , or R ⁵ and R ⁶ are 1,4-buta-1,3-dienylene, and the remaining R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ radicals are hydrogen.

Particularly preferred is an ionic liquid (IL), wherein the cation is a pyridinium cation of the formula (IIk) as follows:

R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ radicals are all hydrogen; or

One of the R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ radicals is methyl or ethyl and the remaining R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ radicals are hydrogen.

Very particularly preferred pyridinium cations (IIk) include 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-octadecyl) pyridinium, 1- (1-octadecyl) pyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1- (1-hexadecyl) -2-methylpyridinium, 1- (1-tetradecyl) -2-methylpyridinium, 1- , 1-methyl-2-ethylpyridinium, 1,2-diethylpyridinium, 1- (1-butyl) -2-ethylpyridinium, 1- (1-octyl) -2-ethylpyridinium, 1- (1-dodecyl) -2-ethylpyridinium, 1- Ethyl-2-methylpyridinium, 1- (1-butyl) -2-methyl-3-ethylpyridinium, 1- (1 (1-octyl) -2-methyl-3-ethylpyridinium, 1- (1-octyl) , 1- (1-tetradecyl) -2-methyl-3-ethylpyridinium and 1- (1-hexadecyl) -2-methyl-3-ethylpyridinium.

Particularly preferred is an ionic liquid (IL), wherein the cation is a pyridazinium cation of formula (IIl) as follows:

R ⁴ , R ⁵ , R ⁶ and R ⁷ radicals are all hydrogen; or

One of the R ⁴ , R ⁵ , R ⁶ and R ⁷ radicals is methyl or ethyl and the remaining R ⁴ , R ⁵ , R ⁶ and R ⁷ radicals are hydrogen.

Particularly preferred is an ionic liquid (IL), wherein the cation is a pyrimidinium cation of the formula (IIm) as follows:

R ⁴ is hydrogen, methyl or ethyl, R ⁵ , R ⁶ and R ⁷ are each independently hydrogen or methyl; or

R ⁴ is hydrogen, methyl or ethyl, R ⁵ and R ⁶ are methyl and R ⁷ is hydrogen.

Particularly preferred is an ionic liquid (IL), wherein the cation is a pyridinium cation of the formula (IIn) as follows:

R ⁴ is hydrogen, methyl or ethyl, R ⁵ , R ⁶ and R ⁷ are each independently hydrogen or methyl; or

R ⁴ is hydrogen, methyl or ethyl, R ⁵ and R ⁶ are methyl and R ⁷ is hydrogen; or

R ⁴ , R ⁵ , R ⁶ and R ⁷ are methyl, or

R ⁴ , R ⁵ , R ⁶ and R ⁷ are hydrogen.

Particularly preferred is an ionic liquid (IL), wherein the cation is an imidazolium cation of formula (IIo) as follows:

R ⁴ is hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 2-hydroxyethyl or 2-cyanoethyl, R ^5, R ⁶ and R ⁷ Are each independently hydrogen, methyl or ethyl.

Very particularly preferred imidazolium cations (IIo) include 1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) imidazolium, 1- (1-octyl) imidazolium, 1- (1-dodecyl) imidazolium, 1- (1-tetradecyl) imidazolium, 1- Imidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-butyl) (1-hexyl) -3-ethylimidazolium, 1- (1-hexyl) -3-butylimidazolium, 1- (1-dodecyl) -3-ethylimidazolium, 1- (1-octyl) -3-butylimidazolium, 1- Ethylimidazolium, 1- (1-dodecyl) -3-octylimidazolium, 1- (1-tetradecyl) Imidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- (1-tetradecyl) Sol , 1- (1-hexadecyl) -3-ethylimidazolium, 1- (1-hexadecyl) -3-butylimidazolium, 1- , 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1-methylimidazolium, - (1-hexyl) -2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4- -Butyl imidazolium, 1,4-dimethyl-3-octylimidazolium, 1,4,5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1,4,5- Trimethyl-3-ethylimidazolium, 1,4,5-trimethyl-3-butylimidazolium and 1,4,5-trimethyl-3-octylimidazolium.

Particularly preferred is an ionic liquid (IL), wherein the cation is a pyrazolium cation of the formula (IIp) as follows:

R ⁴ is hydrogen, methyl or ethyl, and R ⁵ , R ⁶ and R ⁷ are each independently hydrogen or methyl.

Particularly preferred is an ionic liquid (IL) wherein the cation is a thiazolium cation of the formula (IIq) or (IIq '), or an oxazolium cation of the formula (IIr)

R ⁴ is hydrogen, methyl, ethyl or phenyl, and R ⁵ , R ⁶ and R ⁷ are each independently hydrogen or methyl.

Particularly preferred is an ionic liquid (IL), wherein the cation is a 1,2,4-triazolium cation of the formula (IIs), (IIs') or (IIs "

R ⁴ and R ⁵ are each independently hydrogen, methyl, ethyl or phenyl and R ⁶ is hydrogen, methyl or phenyl.

In a preferred embodiment, the ionic liquid (IL), in particular at least one ionic liquid (IL2), comprises, as cation, at least one, preferably exactly one, pyridinium cation, pyridazinium cation, pyrimidinium cation , Pyrazinium cations, imidazolium cations, pyrazolium cations, thiazolium cations and triazolium cations.

Such cations are listed, for example, in WO 2005/113702. If the positive charge necessary to, on the nitrogen atom or aromatic ring system, the nitrogen atoms are each generally an organic group having carbon atoms of 20 or less, preferably a hydrocarbyl group, in particular C ₁ -C ₁₆ alkyl, especially C ₁ - C ₁₀ an alkyl group, and more preferably be substituted with a C ₁ -C ₄ alkyl group.

(IL) are imidazolium cations, pyrimidinium cations and pyrazolium cations which have an imidazolium, pyrimidinium or pyrazolium ring system, optionally substituted with carbon and / or nitrogen atoms of the ring system Quot; is understood to mean a compound having any desired substituent on the molecule.

(IL2) are imidazolium cations, pyridinium cations and pyrazolium cations which have an imidazolium, pyridinium or pyrazolium ring system, optionally substituted on the carbon and / or nitrogen atom of the ring system Is understood to mean a compound having any desired substituent.

Preferably, the ionic liquid (IL), especially at least one ionic liquid (IL2), comprises at least one, and preferably exactly one, imidazolium cation as the cation. More preferably, the ionic liquid (IL) comprises at least one, preferably exactly one, imidazolium cation as the only cation.

In a particularly preferred embodiment, the ionic liquid (IL) is a compound of formula (III) comprising an imidazolium cation:

[Wherein,

R, R ⁴ , R ⁵ , R ⁶ and R ⁷ are each as defined above;

X Is an anion,

n Is 1, 2 or 3;

Preferably, the R ⁴ , R ⁵ , R ⁶ and R ⁷ and R ⁸ radicals are each independently selected from hydrogen, C ₁ -C ₁₂ -alkyl, preferably C ₁ -C ₆ -alkyl, and halogen, Especially hydrogen, methyl, ethyl, 1-propyl, 1-butyl and chlorine.

The variable n is preferably one.

In particular, anions usable as anions X < ^n- > according to formulas (I) and (III) are, in theory, any anion which, together with the cation, induces an ionic liquid.

The anion, especially the anion X < ^n- >, may be an organic or inorganic anion. Particularly preferred ionic liquids consist exclusively of salts of one of the organic cations and the anions specified below.

Anions according to formulas (I) and (III) of the ionic liquid (IL), in particular the anion X ^n-, are, for example:

Groups of halides and halogen compounds of the formula:

F ^- ; Cl ^- ; Br ^- ; I ^- ; BF ₄ ^- ; PF ₆ ^- ; AlCl ₄ ^- ; Al ₂ Cl ₇ ^- , Al ₃ Cl ₁₀ ^- , AlBr ₄ ^- ; CF ₃ SO ₃ ^- , (CF ₃ SO ₃ ) ₂ N ^- , CF ₃ CO ₂ ^- , CCl ₃ CO ₂ ^- , CN ^- , SCN ^- , OCN ^- , NO ₂ ^- , NO ₃ ^- ;

Groups of sulfates, sulfites and sulfonates of the formula:

SO ₄ ^2- , HSO ₄ ^- , SO ₃ ^2- , HSO ₃ ^- , R ^a OSO ₃ ^- , R ^a SO ₃ ^- ;

Groups of phosphates of the formula:

PO ₄ ^3- , HPO ₄ ^2- , H ₂ PO ₄ ^- , R ^a PO ₄ ^2- , HR ^a PO ₄ ^- , R ^a R ^b PO ₄ ^- ;

Groups of phosphonates and phosphinates of the formula:

R ^a HPO ₃ ^- , R ^a R ^b PO ₂ ^- , R ^a R ^b PO ₃ ^- ;

Groups of carboxylates of the general formula:

R ^a COO ^- ;

Groups of borates of the general formula:

_{^{BO 3 3-, HBO 3 2-,}} H 2 BO 3 -, R a R b BO 3 -, RaHBO 3 -, RaBO 3 2-, B (OR a) (OR b) (OR c) (OR d) ^- , B (HSO ₄ ) ^- , B (R ^a SO ₄ ) ^- ;

Groups of boronates of the general formula:

_{^{R a BO 2 2-, R a}} R b BO -;

Groups of carbonates and carbonic esters of the general formula:

HCO ₃ ^- , CO ₃ ^2- , R ^a CO ₃ ^- ;

Groups of carboximides, bis (sulfonyl) imides and sulfonylimides of the general formula:

;

;

Groups of alkoxides and aryl oxides of the general formula:

R ^a O ^-

≪ / RTI >

In the above-mentioned anions, R ^a , R ^b , R ^c and R ^d are each, independently,

-CO-, -CO-O- or -CO-O-, in which R < ₁ &gt; is hydrogen or C1- _C12 -alkyl and cycloalkyl-, halogen-, hydroxyl-, amino-, carboxyl-, formyl-, Propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl- butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2-methyl-1 -butyl, 2-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, Pentyl, 2-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl Butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl- , undecyl, dodecyl, methoxy, ethoxy, formyl, acetyl, or is selected from CF _3.

More preferably, in the abovementioned anions R ^a , R ^b , R ^c and R ^d are each independently a hydrogen atom or an unsubstituted C ₁ -C ₁₂ -alkyl group, preferably a C ₁ -C ₆ -alkyl group .

Particularly preferred anions, especially very particularly preferred anions X &lt; ^{n- &gt;} are:

The organic solvent is selected from the group consisting of chloride, bromide, hydrogensulfate, tetrachloroaluminate, thiocyanate, methyl carbonate, methylsulfate, ethylsulfate, methanesulfonate, formate, acetate, dimethyl phosphate, diethyl phosphate, (Tetrafluoroborate), hexafluorophosphate, bis (trifluoromethylsulfonyl) imide, and bis (methylsulfonyl) imide.

Very particularly preferred anions, especially very particularly preferred anions X &lt; ^{n- &gt;} are:

Chloride, hydrogensulfate, methylsulfate, ethylsulfate, methanesulfonate, formate and acetate.

Particularly preferred is a cation,

(1-octyl) imidazolium, 1- (1-dodecyl) imidazolium, 1-methylimidazolium, 1- (1-butyldimethylsilyl) imidazolium, 1- (1-hexadecyl) imidazolium, 1,3-dimethylimidazolium, Methylimidazolium, 1- (1-butyl) -3-ethylimidazolium, 1- (1-hexyl) (1-octyl) -3-ethylimidazolium, 1- (1-pentyl) -3-methylimidazolium, 1- 1-octyl) -3-butylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-hexadecyl) -3-ethylimidazolium, 1- (1-tetradecyl) -3-butylimidazolium, 1- Methylimidazolium, 1- (1-hexadecyl) -3- (1-hexadecyl) -3-butylimidazolium, 1- (1-hexadecyl) -3-octylimidazolium, Dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3-dimethyl Imidazolium, 1, 3-dimethylimidazolium, 1, 4-dimethylimidazolium, 1, 4-dimethyl-3-ethyl Imidazolium, imidazolium, 3-butylimidazolium, 1,4-dimethyl-3-octylimidazolium, 1,4,5-trimethylimidazolium, 1,3,4,5-tetramethylimidazolium, 1 , 4,5-trimethyl-3-ethylimidazolium, 1,4,5-trimethyl-3-butylimidazolium, 1,4,5-trimethyl-3-octylimidazolium; And 1-butyl-1-methylpyrrolidinium, and preferably comprises exactly one cation;

As an anion,

And the like. Examples of the organic solvent include chlorides, bromides, hydrogensulfates, tetrachloroaluminates, thiocyanates, methylsulfates, ethylsulfates, methanesulfonates, formates, acetates, dimethylphosphates, diethylphosphates, p-tolylsulfonates, At least one anion selected from the group consisting of borate and hexafluorophosphate, preferably one precursor anion,

Ionic liquid (IL).

Also particularly preferred are ionic liquids (IL) selected from the group consisting of:

1,3-dimethylimidazolium methylsulfate, 1,3-dimethylimidazolium hydrogensulfate, 1,3-dimethylimidazolium dimethylphosphate, 1,3-dimethylimidazolium acetate, 1-ethyl-3 Methylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium ethylsulfate, 1-ethyl-3-methylimidazolium hydrogensulfate, 1-ethyl-3-methylimidazolium thiocyanate Ethyl-3-methylimidazolium methanesulfonate, 1-ethyl-3-methylimidazolium diethylphosphate, 1- (1-butyl) -3 Methylimidazolium thiocyanate, 1- (1-butyl) -3-methylimidazolium hydrogensulfate, 1- (1-butyl) Butyl-3-methylimidazolium acetate, 1- (1-butyl) -3-methylimidazolium methanesulfonate, methyltri (1-butyl) ammonium methylsulfate, N, N- &lt; RTI ID = 0.0 &gt; Dimethylpiperidinium and N, N-dimethylmorpholinium.

In a particularly preferred embodiment, the composition (C) is selected from the group consisting of 1-ethyl-3-methylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium ethylsulfate, Ethyl-3-methylimidazolium methanesulfonate, methyltri (1-butyl) ammonium methylsulfate (MTBS) and 1-butyl- And at least one ionic liquid (IL) selected from the group consisting of methyl pyrrolidinium dimethyl phosphate.

In one embodiment, the composition (C)

As the first ionic liquid (IL1), methyltri (1-butyl) ammonium methyl sulfate (MTBS); And

As the second ionic liquid (IL2)

1,3-dimethylimidazolium methylsulfate, 1,3-dimethylimidazolium hydrogensulfate, 1,3-dimethylimidazolium dimethylphosphate, 1,3-dimethylimidazolium acetate, 1-ethyl-3 1-ethyl-3-methylimidazolium thiocyanate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium hydrogensulfate, Ethyl-3-methylimidazolium diethylphosphate, 1- (1-butyl) -3-methylimidazolium methylsulfate, 1- (1- Methylimidazolium thiocyanate, 1- (1-butyl) -3-methylimidazolium acetate, 1- (1-butyl) Methylimidazolium methanesulfonate, 1- (1-dodecyl) -3-methylimidazolium methylsulfate, 1- (1-dodecyl) -3-methylimidazolium hydro- Gentafate, 1- (1-tetradecyl) -3-methylimidazole (1-hexadecyl) -3-methylimidazolium methylsulfate and 1- (1-hexadecyl) -3-methylimidazolium hydrogensulfate, 1- ) -3-methylimidazolium hydrogensulfate. &Lt; RTI ID = 0.0 &gt;

Preferably 1-ethyl-3-methylimidazolium methyl sulfate, 1-ethyl-3-methylimidazolium hydrogensulfate, 1-ethyl-3-methylimidazolium acetate, &Lt; / RTI &gt; imidazolium methanesulfonate.

The additional constituents of composition (C)

The composition of the present invention and the composition (C) used in the method of the present invention may contain, in addition to the at least one ionic liquid (IL), additional components.

Possible examples of these include additives that allow the desired viscosity and / or the desired melting point to be established. Examples thereof include, for example, solvents which are miscible with ionic liquids, in particular water and / or organic solvents.

In a preferred embodiment, the composition (C) comprises:

From 0 to 100% by weight, preferably from 60 to 90% by weight and more preferably from 60 to 80% by weight, based on the total composition (C), of at least one ionic liquid (IL) ;

0 to 45% by weight, preferably 0 to 30% by weight, more preferably 1 to 30% by weight and most preferably 5 to 20% by weight, based on the total composition (C) % Of at least one solvent (S).

In a preferred embodiment, the composition (C) consists of the above-mentioned ingredients, i.e. the sum of the above-mentioned ingredients is 100% by weight.

Preferably, composition (C) is a solution; More particularly, the components of composition (C) can be homogeneously mixed with one another, or the components of composition (C) are in a homogeneously distributed form. More particularly, composition (C) is a solution having a molecular dispersion.

Composition (C) may comprise, as solvent (S), in particular water or an organic solvent which is miscible with water and an ionic liquid (IL), or mixtures thereof.

The viscosity of the composition (C) (etching composition) is preferably in the range of 20 to 200 mPas, preferably in the range of 30 to 100 mPas and more preferably in the range of 30 to 70 mPas (in each case, Lt; / RTI &gt;

The melting point of the composition (C) is typically less than 100 占 폚, preferably less than room temperature (25 占 폚), particularly preferably less than 10 占 폚, more preferably less than 0 占 폚.

Preferably, the composition (C) is selected from the group consisting of water, propylene carbonate, polyethylene glycol, mono-, di- or triesters of glycols and C ₁ -C ₆ carboxylic acids, in particular diacetin (glyceryl diacetate) Triacetin (glyceryl triacetate), glycol, especially at least one solvent (S) selected from ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol. Polyethylene glycols having a molecular weight in the range of 200-4000 g / mol, preferably 200-1000 g / mol, more preferably 200-600 g / mol, are preferred.

More preferably, the composition (C) comprises 1 to 30% by weight, preferably 5 to 20% by weight and more preferably 7 to 15% by weight, based on the total composition (C) Of at least one solvent (S) selected from propylene carbonate, polyethylene glycol, especially PEG 200, triacetin and water.

In a preferred embodiment, the composition (C) comprises:

Comprises at least one alkylammonium cation in an amount of from 49% by weight to 94% by weight, preferably from 55% by weight to 85% by weight and more preferably from 60% by weight to 80% by weight, based on the total composition (C) , At least one ionic liquid (IL) as described above;

, Preferably from 5% to 40% by weight, preferably from 10% to 40% by weight and more preferably from 5% by weight to 20% by weight, based on the total composition (C) And more preferably from 10% to 20% by weight of at least one aromatic heterocycle having at least one aromatic heterocycle having a cationic charge and a cationic charge, Liquid (IL2);

1 to 30% by weight, preferably 5 to 20% by weight, of water, propylene carbonate, polyethylene glycol, glycols and C ₁ -C ₆ carboxylic acids, based on the total composition (C) Propylene carbonate, polyethylene glycol, diacetin (glyceryl diacetate), triacetin (glyceryl triacetate), ethylene glycol (ethylene glycol), ethylene glycol At least one solvent (S) selected from the group consisting of glycol, diethylene glycol, triethylene glycol and tetraethylene glycol.

In another preferred embodiment, the composition (C) comprises:

At least one ionic liquid (IL1), based on the total composition (C), of 49 to 94% by weight, preferably 55 to 85% by weight and more preferably 60 to 80% ;

At least one ionic liquid (IL2), based on the total composition (C), of from 5% to 50%, preferably from 5% to 30% and more preferably from 5% ;

At least one solvent (S) as described above, from 1% to 30% by weight, preferably from 10% to 30% by weight, based on the total composition (C).

In a preferred embodiment, the composition (C) comprises propylene carbonate exclusively as solvent (S). Also, it may comprise a mixture of propylene carbonate and water as solvent (S), in which case the proportion of propylene carbonate is at least 30% by weight, preferably at least 50% by weight, based on the total solvent (S) By weight, more preferably at least 90% by weight.

The composition preferably comprises at least 10% by weight, in particular in the range of more than 30% by weight, more preferably in the range of more than 50% by weight, and most preferably in the range of more than 80% And one ionic liquid (IL). In a particularly preferred embodiment, it consists of at least one ionic liquid (IL) in the range of more than 90% by weight and in particular in the range of more than 95% by weight. In a further embodiment, the composition consists exclusively of one or more of the ionic liquids described above, preferably ionic liquids (IL1) and (IL2).

The composition (C) comprising or consisting of an ionic liquid and an ionic liquid is preferably a liquid over the entire temperature range of from 20 to 100 DEG C (1 bar at standard pressure).

Way

An essential element in the method of the present invention is the pretreatment according to the claims of the plastic or plastic surface. Various process steps for metal-based chemical and electrolytic coatings and the additional means for performing, recommending and implementing, producing and finishing them are described in various different embodiments of the art, for example DE-A 100 54 544, Schlesinger et al. "Modern Electroplating" chapter 18, pages 450-457 (5th edition, 2010, John Wiley & Sons Inc., ISBN 978-0-470-16778-6) or Kanani "Galvanotechnik" [Electroplating Technology] (Carl Hanser Verlag, 2000 , ISBN 3-446-21024-5).

Even prior to the pretreatment of the invention in step a), cleaning and / or degreasing of the plastic surface to be coated may be recommended. This type of cleaning and degreasing may be performed using standard cleaning compositions or detergents.

Step a)

The method of the present invention comprises, in step a), a pretreatment of the plastic surface to a composition (C) (etching solution) comprising at least one ionic liquid (IL). The preferred ionic liquid of composition (C) and optional additional components are described above.

Surprisingly, it has been found that it is particularly advantageous to observe the optimized treatment conditions, in particular the temperature and duration of the pretreatment.

Preferably, the pretreatment of the plastic surface to the composition (C) in step a) is carried out at a temperature of 30 to 120 캜, more preferably 40 to 120 캜, particularly preferably 50 to 65 캜 and most preferably 50 to 60 Lt; 0 &gt; C. Preferably, the composition (C) has this temperature for this purpose. There is often no need for the preceding plastic surface to be coated, or the preceding, separate heating of the plastic molding to be coated.

Preferably, the pretreatment of the plastic surface to the composition (C) in step a) is carried out for 1 to 60 minutes, preferably 1 to 30 minutes, particularly preferably 2 to 20 minutes and more preferably 5 to 10 minutes &Lt; / RTI &gt;

Preferably, the pretreatment of the plastic surface to the composition (C) in step a) is carried out at a temperature in the range from 50 to 65 占 폚 and over a period of from 5 to 20 minutes. More preferably, the pretreatment of the plastic surface to the composition (C) in step a) is carried out at a temperature in the range of from 50 to 60 DEG C and for a period of from 5 to 15 minutes.

In a preferred embodiment, the present invention relates to a method of coating a plastic surface, in particular a plastic molding, comprising or consisting of an acrylonitrile / butadiene / styrene copolymer (ABS) Wherein the pretreatment of the surface, in particular the plastic molding, is carried out at a temperature in the range from 50 to 60 DEG C, preferably from 50 to 55 DEG C, and from 5 to 15 minutes, preferably from 5 to 10 minutes. The plastic surface comprising or consisting of acrylonitrile / butadiene / styrene copolymer (ABS) is particularly suitable for blends comprising ABS, ABS, for example ABS / PC (acrylonitrile / butadiene / styrene copolymer and polycarbonate Nate), and / or ABS. &Lt; / RTI &gt;

In a preferred embodiment, the plastic surface to be coated, in particular the plastic molding to be coated, is dipped into the composition (C), wherein the composition (C) preferably has this temperature. In this case, the composition (C) can be stirred for better mass transfer, which can be carried out by stirring, pumping, air injection, and the like. Alternatively, the plastic surface itself may also be agitated in composition (C), using a specific apparatus known in electroplating. Those skilled in the art are aware of suitable methods for this.

The required amount of composition (C) is adjusted in such a way that the plastic surface is wetted to the desired extent. The plastic surface or plastic molding may be completely or partially submerged.

The viscosity of the composition (C) (etching solution) is preferably in the range of 20 to 200 mPas, preferably in the range of 30 to 100 mPas, and more preferably in the range of 30 to 70 mPas (dyn, 60 DEG C).

Step b)

The method of the present invention comprises, in step b), treating the plastic surface from step a) with an aqueous rinse solution (RS), while applying ultrasonic waves. The treatment in step b) can remove not only the bonding composition (C) but also the partially dissolved plastic particles from the surface, in particular from the surface of the plastic molding.

In a preferred embodiment, treating the plastic surface with an aqueous rinse solution (RS) with the application of ultrasonic waves in step b) can be accomplished by placing the plastic surface from step a) in an ultrasonic bath containing an aqueous rinse solution (RS) For a period of 1 to 30 minutes, preferably 2 to 20 minutes and more preferably 5 to 15 minutes. In particular, a sufficient rinse can be obtained after 1 to 2 minutes, especially after about 90 seconds. Preferably, step b) is carried out by dipping the plastic surface from step a) into an ultrasonic bath containing an aqueous rinse solution (RS) for a period of 1 to 2 minutes at a temperature in the range of 40 to 60 占 폚.

In a preferred embodiment, treating the plastic surface, in particular the plastic molding, with an aqueous rinse solution (RS) while applying ultrasonic waves in step b) is carried out by applying the plastic surface from step a), in particular the plastic moldings, In a range of 40 to 60 W / L, at a temperature of 40 to 60 DEG C, and for a period of 1 to 30 minutes, wherein the aqueous rinse solution (RS) is at least 85 By weight, preferably at least 95% by weight of water.

The aqueous rinse solution (RS) preferably comprises water or a mixture of water and one or more water-miscible organic solvents, wherein the ratio of water is generally at least 85% by weight, in each case based on the total rinse solution, , Preferably at least 95 wt% and more preferably at least 98 wt%. The organic solvent used may be a known polar water-miscible solvent such as an alcohol or dimethylsulfoxide (DMSO). The organic solvent used may in particular be a water-miscible alcohol such as methanol, ethanol or propanol. In a preferred embodiment, the rinsing solution RS consists exclusively of water.

The rinsing solution (RS) optionally comprises additives known to the person skilled in the art, for example a surfactant.

The pH of the rinsing solution (RS) preferably ranges from 5 to 8, in particular from 6 to 7. Preferably, the rinsing step b), which may also consist of a plurality of steps, is carried out at a temperature in the range from 10 to 80 캜, preferably from 20 to 70 캜, more preferably from 40 to 60 캜.

The ultrasonic treatment is preferably performed at a frequency in the range of 20 to 400 kHz, preferably 30 to 50 kHz. The ultrasonic treatment is preferably carried out at a power in the range of 10 to 100 W / L, preferably 40 to 60 W / L. Particularly preferably, the ultrasonic treatment is carried out at a power in the range of 40 to 60 watt / L, at a temperature of 40 to 60 占 폚 and for a period of 5 to 15 minutes. It is more preferred that the ultrasonic treatment is performed at a power in the range of 40 to 60 watt / L, at a temperature of 40 to 60 占 폚 and for a period of 1 to 2 minutes.

Advantageously, step b) may comprise a plurality of rinsing steps, especially an additional rinsing step, without applying ultrasonic waves. Preferably, treating the plastic surface with an aqueous rinse solution (RS) in step b) comprises, as an additional step, treating the plastic surface with at least one further aqueous rinse solution (RS), in particular water, This can be done, for example, by spraying or dipping the plastic surface.

A preferred embodiment relates to a process as described, wherein step b) comprises (and preferably comprises) the following steps:

b1) Especially the plastic surface from step a), by spraying a first aqueous rinse solution RS1 onto a plastic surface, in particular a plastic molding, or by dipping a plastic surface, in particular a plastic molding, into a first aqueous rinse solution RS1. Treating the molding with a first aqueous rinse solution (RS1);

b2) Treating the plastic surface, in particular the plastic molding, from step b1) with a second aqueous rinse solution (RS2) while applying ultrasonic waves.

The process according to the invention, in particular steps a) and / or b), can be carried out partially or completely continuously or semi-continuously.

In one embodiment, the composition (C) is recovered after step a) and fed (recycled) completely or partially back to the etching step a). Recirculation of the composition (C) can be carried out, for example, by precipitation of dissolved plastics using water or an organic solvent, and subsequent removal of the dissolved plastics by filtration. The media / media used in the precipitation can then be recovered by distillation. In addition, by direct distillation, the volatile constituents of the dissolved plastic can be removed from the composition. In this way, a purified and reusable composition (C) can be obtained.

In a preferred embodiment, the rinsing solution RS is recovered after step b), in particular after step b1) and / or b2) and completely or partially in the rinsing step b), in particular the rinsing step b1) and / (Recirculated). Preferably, the spent rinsing solution is pre-cleaned, for example by filtration.

Recirculation of the rinsing solution RS can be performed, for example, by removing the plastic present therein, preferably by filtration. In this way, a cleaned and reusable rinsing solution, which is generally a mixture of water and an ionic liquid (IL), can be obtained and then completely or partially recycled to the rinsing step b1) and / or b2) . Preferably, a portion of the recovered rinse solution is discharged, in particular to prevent concentration of the ionic liquid in the rinse solution (RS) in the circulation.

Step c)

The process according to the invention is characterized in that in step c) the plastic surface from step b) is treated with at least one ion generating and / or colloidal activator, especially at least one palladium component (P), preferably at least one colloidal palladium With an activator composition (A) comprising component (P).

Typically, step c) comprises applying a metal nucleus, preferably palladium, silver or gold, more preferably palladium, in combination with step d) in particular. Step b) is typically referred to as activation. Preferably, the first metal coating and activation method in step e) are matched to each other.

Known methods for activation include, for example, conventional colloid activation (application of palladium / tin colloid), ion production activation (application of palladium cations), direct metallization, or Udique Plato®, Enplate MID selection or LDS Process Is a method known by name.

For example, activation using an ion generating system can be accomplished by first treating the plastic surface with tin (II) ions and, generally, after treatment with tin (II) ions, rinse with water, Lt; RTI ID = 0.0 &gt; gel. &Lt; / RTI &gt; In subsequent treatment with a palladium salt solution, the palladium nuclei are typically formed on the plastic surface by reduction with a tin (II) species, which is typically used as catalyst / metal nuclei for subsequent chemical metallization (step e) It plays a role.

In the case of activation using a colloidal system, noble metal colloid compositions, in particular, gold (transition group I) and platinum group colloids of the periodic table can be used. It is preferable to use a colloidal solution of palladium, silver or gold, particularly preferably a colloidal solution of palladium. In a colloidal solution, metal nuclei, such as palladium nuclei, are typically surrounded by a protective colloidal shell. It may be desirable to use a palladium colloid solution which is formed through the reaction of palladium chloride and tin (II) chloride in the presence of excess hydrochloric acid.

The concentration of at least one of the ion generation and / or colloidal activator (P) in the activator composition (A) is typically from 20 to 150 mg / L.

For a more detailed description of a typical palladium-containing activator system and activation step, see [Annual Book of ASTM Standard, Vol. 02.05 "Metallic and Inorganic Coatings, Metal Powders, Sintered P / M Structural Parts ", Standard Practice for Preparation of Plastic Materials for Electroplating, 1995, pages 446-450.

Typically, the activator (P) used may be a standard commercial palladium activator such as "Activator U" from HSO or Surtec 961 Pd from Surtec.

Step d)

The process of the present invention comprises, in step d), treating the plastic surface from step c) with an accelerator composition (B) comprising an acid and / or a reducing agent.

The treatment of the plastic surface with the accelerator composition (B) is particularly advantageous for liberating / liberating or absorbing the palladium, silver or gold nuclei of metal nuclei, especially protective colloidal shells, adsorbed on the surface (especially at depression) Thereby reducing the metal salt to metal. Treatment of the plastic surface with the accelerator composition (B) typically produces metal nuclei of metal nuclei, preferably palladium, silver or gold, more preferably palladium, on the plastic surface. These metal nuclei typically serve as starting points (catalysts) for subsequent chemical metal deposition in step e).

In the present invention, the promoter composition (B) comprises at least one reducing agent and / or acid which is particularly suitable for removal of the protective metal colloidal shell and / or reduction of the metal salt present on the surface to a metal. Preferably, the at least one reducing agent is selected from the group consisting of alkali metal, ammonium or alkaline earth metal fluoroborates such as sodium tetrafluoroborate (NaBF ₄ ), peroxide, sulfite, hydrogensulfite, hydrazine and its salts, &Lt; / RTI &gt; Preferably, the at least one acid is selected from hydrochloric acid, methanesulfonic acid, citric acid, ascorbic acid, tartaric acid, tetrafluoroboric acid (HBF ₄ ).

The pH of the accelerator composition (B) may be set within a range of from 0 to 7, preferably from 1 to 2, in particular.

The concentration of the acid and / or reducing agent in the accelerator composition (B) is typically 0.4 to 0.5 N; The concentration is particularly 0.45 N (pH 1.5).

For further details of typical accelerator compositions and promoting steps, see [Annual Book of ASTM Standard, Vol. 02.05 "Metallic and Inorgaic Coatings, Metal Powders, Sintered P / M Structural Parts ", Standard Practice for Preparation of Plastic Materials for Electroplating, 1995, pages 446-450.

Typically, the accelerator composition (B) used may be a standard commercial promoter such as HSO Accelerator from HSO or Surtec 961 A from Surtec.

Step e)

A further component of the method of the present invention is the application of a so-called first metal coating, typically carried out by means of electroless (chemical metal deposition). Generally, the first layer (seed layer) applied by the electroless means is a layer of nickel, copper, chromium or alloys thereof. At least one layer of nickel and / or copper is preferred. Precisely one layer consisting essentially of nickel is particularly preferred.

The process according to the invention is characterized in that in step e) the plastic surface from step d), in particular the plastic molding, is treated with at least one metal salt, preferably at least one nickel (II) salt and at least one reducing agent, Comprises chemical vapor deposition of a metal layer, preferably consisting essentially of nickel, by treating with a coating composition (M1) comprising a reducing agent.

More preferably, step e) comprises applying the surface from step d) at least one nickel (II) salt and / or one copper (II) salt and at least one reducing agent, And / or &lt; RTI ID = 0.0 &gt; copper, &lt; / RTI &gt;

A typical coating composition (M1) is described, for example, in Schlesinger et al. "Modern Electroplating" (5th edition, 2010, John Wiley & Sons Inc., ISBN 978-0-470-16778-6, page 451).

Preferably, the plastic surface or plastic molding from step d) is coated with a metal layer of nickel, copper, chromium or alloys thereof, more preferably nickel or a nickel alloy.

Preferably, the metal salt is selected from nickel, copper and chromium salts, such as halides or sulfates. Preferably, the coating composition (M1) comprises at least one nickel salt, for example nickel sulfate.

The concentration of at least one metal salt, in particular at least one nickel salt, in the coating composition (M1) is typically in the range 15 to 35 g / L.

The pH of the coating composition (M1) is typically in the range of 4 to 11. In theory, acidic or alkaline compositions can be distinguished, depending on the type of buffer system. In the case of an acidic process, the pH of the coating composition (M1) is typically in the range of from 4 to 7, preferably from 4 to 6. For alkaline processes, the pH is typically in the range of more than 7 to 11, preferably in the range of 8 to 10. [ Preferably, the pH is set at about 9.

Preferably, the coating composition (M1) is selected from the group consisting of hydrogen peroxide, peroxides, hypophosphites, hypophosphates such as sodium hypophosphate, borane and borane derivatives such as aminoborane such as dimethylaminoborane, Hydride) and hydrazine, in particular an in situ reducing agent.

The concentration of the reducing agent in the coating composition (M1) is typically 15 to 30 g / L.

Typically, a coating composition (M1) for a chemical nickel bath is prepared by a method known in the art such as, for example, Schlesinger et al. May include typical additional components and additives as described in chapter 18.3 of "Modern Electroplating" (5th edition, 2010, John Wiley & Sons Inc., ISBN 978-0-470-16778-6). Typically, the coating composition (M1) is prepared by dissolving a nickel ion, preferably a carboxylic acid and a hydroxycarboxylic acid, such as succinic acid, citric acid, malic acid, tartaric acid and / or lactic acid, and acetic acid, propionic acid, And / or a complexing agent for itaconic acid. The buffer used may typically be citrate, acetate, phosphate and ammonium salts.

Typically, the coating composition (M1) used may be a standard commercial coating bath for electroless nickel deposition, such as "Electroless Nickel 601 KB" from HSO or "Surtec 3 / 11D" from Surtec.

In the case of acidic processes, the temperature of the coating composition (M1) during the performance of step d) is typically from 60 to 100 캜, and in the case of alkaline processes, typically from 25 to 50 캜.

Step f)

Step f) of the process of the present invention finally involves electrochemical deposition of a metal layer, preferably one or more metal layers, consisting essentially of nickel, copper and / or chromium. Step f) in particular comprises more than one, two or more than two different electrochemical coatings.

By the method of the present invention, the adhesion of the metal layer, especially the chemically deposited nickel layer described, and subsequent electrochemically deposited nickel, copper and chromium layers, to plastic surfaces made of, for example, ABS, Or, indeed, make the adhesive force possible to multiple plastics. The achieved adhesion of the metal layer is very good, even at mechanical stress or at high temperatures. In addition, the metal surface obtained by the method of the present invention has a particularly advantageous regular structure.

The process according to the invention is characterized in that in step f), the plastic surface from step e), in particular the plastic molding, is electrochemically treated with at least one coating composition (M ') comprising at least one metal compound, e) electrochemical coating of plastic surfaces, in particular of plastic molding, into at least one further metallic layer.

Advantageously, step f) comprises an electrochemical coating of the plastic surface, in particular plastic molding, into at least one metallic layer consisting essentially of copper. For this purpose, plastic surfaces, especially plastic moldings, are applied to electrochemical electrolysis using a coating composition (M2) comprising at least one copper compound, preferably at least one copper (II) salt.

Preferably, step f) comprises an electrochemical coating of a plastic surface, in particular plastic molding, into at least one metallic layer consisting essentially of chromium. For this purpose, the plastic surface, in particular the plastic molding, preferably comprises a coating composition (M3) comprising at least one chromium compound, preferably selected from chromic acid, chromic acid derivatives, chromium (VI) salts and chromium (III) And is applied to electrochemical electrolysis.

Preferably, the invention relates to a method as described above, wherein the electrochemical coating in step f) comprises (and preferably consists of) the following steps:

f1) The plastic surface from step e), in particular the plastic molding, is coated with a coating composition M2 comprising at least one copper compound, in particular a Cu (II) salt, and / or at least one nickel compound, in particular a Ni (II) Electrochemically coating the plastic surface from step e), in particular the plastic molding, with a layer consisting essentially of copper and / or nickel; And

f2) Characterized in that the plastic surface from step f1, in particular the plastic molding, comprises at least one chromium compound selected from chromium acid, chromic acid derivative, chromium (VI) salt and chromium (III) Electrochemically coating the plastic surface from step f1), in particular the plastic molding, with a layer consisting essentially of chromium by treating with a coating composition (M3).

Preferably, in step f1), the surface from step e) comprises a coating composition (M2) comprising at least one Cu (II) salt, wherein the surface from step e) comprises at least one copper compound, Lt; RTI ID = 0.0 &gt; electrochemically &lt; / RTI &gt; coated with a layer consisting essentially of copper. More preferably, in step f1), the surface from step e) is electrochemically coated with one or more layers consisting essentially of copper and one or more layers consisting essentially of chromium. The preferred coating order (step e), f1) and f2) may be as follows:

Ni (chem) → SB-Ni → B-Ni → Cr or Ni → chem → Cu → SB-Ni → B-Ni → Cr or Cu → chem → SB-Ni → B- ) - &gt; Cu - SB - Ni - B - Ni - Cr;

Where SB-Ni is a partially bright nickel layer and B-Ni is a bright nickel layer.

Typically, the coating composition (M2) is, at least one of the copper salt, and preferably include at least one copper (II) salt such as copper sulfate (CuSO _4). Typically, the coating composition M2 comprises at least one copper salt, water and an acid, for example an alkylsulfonic acid such as sulfuric acid, methanesulfonic acid. Typically, the coating composition M2 may comprise, as further additives, additives customary in such applications, for example, surfactants, brighteners, inhibitors or levelers.

Typically, the coating composition M2 used may be a standard commercial copper electrolytic bath, such as "Copper HD 500" from HSO or Surtec 867 from Surtec.

Typically, the coating composition (M3) comprises at least one chromium salt and / or chromic acid, preferably at least one chromium (III) salt and / or one chromium (VI) salt, more preferably chromium H ₂ CrO ₄ and / or chromium trioxide include CrO _3. Typically, the coating composition (M3) includes at least one chromium compound, in particular chromate, water and an acid as catalyst, such as sulfuric acid (H ₂ SO _4), hydrofluoric acid (HF), silicic acid (H ₂ SiF hexafluoro ₆ ), and an alkylsulfonic acid such as methanesulfonic acid. Typically, the coating composition (M3), as a further additive, may comprise a surfactant known for this application.

The method of the present invention may comprise one or more rinsing steps before and / or after each of the described steps a) to f). Particularly after step f), the plastic surface, in particular the plastic moldings, can be rinsed, preferably rinsed with water and / or dried.

Description of Drawings

The electron micrograph of FIG. 1 shows the ABS surface (upper image) obtained according to Comparative Example C1 (including a simple rinse step), and the ABS surface obtained according to Example I1 of the present invention, including the ultrasonic treatment according to the present invention (Lower image). In Examples C1 and I1, an etching solution composed of MTBS: EMIM-OAc (95: 5) was used. The ABS surface was etched at 70 占 폚 for 10 minutes.

Figure 2 shows one possible arrangement of steps a) and b) of the present invention. The label here has the following meaning:

(I) Pre-treatment bath (step a)

(II) The container for collecting the spraying apparatus (step b1)

(III) The spray nozzle (step b1)

(IV) Ultrasonic rinsing bath (step b2)

(V), (VI) filter

(One) (II) &lt; / RTI &gt;

(2) (IV) &lt; / RTI &gt;

(3) Spray solution, removal of the first spray solution

(4) Ultrasonic bath rinse solution, removal of second rinse solution

(5) The forward path of the rinsed rinse solution

(5.1), (5.2) (II) / (IV) of the washed rinse solution

(6.1), (6.2) Emission of removed plastic

(7) The discharge of a part of the washed rinse solution

Figure 2 shows one embodiment of process steps a), b1) and b2). The molding is immersed in a treatment bath I comprising at least one ionic liquid (IL) (step a). When the molding is advanced and moved through (1) to the spraying stages ((II) and (III)), the part of the ionic liquid and the partially dissolved plastic particles on the surface of the molding, Is accompanied. In the spraying apparatuses (collecting container (II) and spraying nozzle (III)), the adhesive composition (C) is rinsed by spraying the first rinsing solution (RS) onto the molding (step b1). The spent rinse solution is collected in a collecting container and transferred to filter (VI) through (3). When the molding is moved forward (step b2) to the ultrasonic rinsing bath IV containing the second rinsing solution RS via step (2)), a portion of the ionic liquid and the first rinsing solution, and the surface of the molding The partially dissolved plastic particles are again entrained together. The molding is immersed in an ultrasonic bath, removed from the bath after residence time, and sent to further processing steps. In the ultrasonic bath (IV), in a continuous manner, the second rinse solution is removed from the bath (4) and fed to the filter (V). Further, the washed rinse solution is supplied to (II) through (IV) through (5), (5.1) and (5.2). In filters (V) and (VI), the polymer is filtered from the spent rinse solution and drained. The washed rinse solution is recycled to the process via (5); Some are discharged through (7).

The present invention is illustrated in detail by the following examples.

Example 1

1.1 General Test Methods for Investigation of Etching Behavior

A plaque of ABS (acrylonitrile / butadiene / styrene terpolymer, Terluran® GP 35 from Styrolution) having dimensions of 60 x 30 x 2 mm was coated with 2 L of stirred ionic liquid Composition (C)). After the etching was completed, the substrate was rinsed with water. In an embodiment of the present invention, plaques were subsequently treated in an ultrasonic bath.

The etching behavior was confirmed by SEM analysis, which indicated a new structure of the surface (see FIG. 1).

1.2 Comparison of etch results with and without ultrasonic rinse step

Using an etching solution composed of methyltri (1-butyl) ammonium methyl sulfate (MTBS) and 1-ethyl-3-methylimidazolium acetate (EMIM-OAc) (MTBS / EMIM weight ratio 95: 5) The etching step was performed as described above on the test plaque.

After the etching step (step a), the ABS test plaque is immersed (C1) in a water bath at 50 DEG C for 10 minutes, or sonicated (6 L water, 280 W, about 50 W / , At 35 kHz) (I1).

The SEM image in FIG. 1 shows the ABS surface (upper image) obtained according to Comparative Example C1 (including a simple rinse step) and the ABS surface obtained according to Example I1 of the present invention including the ultrasonic treatment according to the present invention (Lower image).

In the SEM image, it is clear that the ultrasonic rinse step provided better removal of the partially dissolved plastic particles which had been partially dissolved by the etching solution. In SEM image C1, which does not include ultrasonic treatment, bulky porous plastic residues are evident. In the SEM image I1 including the ultrasonic treatment, there is no such residue at all. The SEM image, including the ultrasonic treatment, shows a homogeneously etched ABS surface with a morphology of particularly good fit for performing subsequent metallization steps.

Example 2 - Change in etching conditions

The ABS test plaque was treated with the general test method described above for the investigation of the etching action.

The etching solution (composition (C)) is methyl tri (1-butyl) ammonium methyl sulfate (MTBS), ethyl 1-ethyl-3-methylimidazolium sulfate (EMIM-EtSO ₄₎ and propylene used in all cases Carbonate (PC) (MTBS / EMIM-ETSO ₄ / PC weight ratio 80:10:10). Various etching conditions (temperature and time) were established as described in Table 2 below.

The etching behavior was confirmed by SEM analysis, which indicated a new structuring of the surface.

After etching and rinsing, the test plaque was metallized. For this purpose, the following treatment steps were performed:

Treatment with activator composition (A) → treatment with accelerator composition (B) → chemical electroless deposition of nickel with coating composition (M1) → electrodeposition of copper with coating composition (M ').

The following products were used:

Activator composition A HSO's "Activator U" or Surtec's "Surtec 961 Pd"

Promoter composition B "HSO Accelerator" from HSO or "Surtec 961 A" from Surtec Co.,

Coating composition M1 HSO's "Electroless Nickel 601KB" or Surtec's "Surtec 3 / 11D"

The coating composition M ' HSO's "Copper HD 500" or Surtec's "SurtSurtec 867"

According to ISO 2409: 2007, the quality of the metal coating was measured using a so-called cross-cut test. The results are summarized in Table 1.

It has been found that the treatment of the ABS surface at a temperature of 45 DEG C in step a) can not achieve a homogeneous structure of the surface P1 even with an etching time of 15 minutes. If the etch temperature is too low and / or the treatment time is too short, the surface becomes insufficiently rough. The nucleation necessary for the metallization in subsequent steps is inadequate. It is not possible to produce a layer between the plastic surface and the metal layer with adequate adhesion (insufficient "push-button effect").

For higher etch temperatures of 65 占 폚 and / or excessively long etch times, the plastic surface is under attack (P5 and P6), which means that the surface is too cracked to exhibit unevenly structured.

In this embodiment, a particularly advantageous and homogeneous surface structuring of the ABS surface is achieved at a temperature in the range of 50 to 60 占 폚, more preferably 50 to 55 占 폚, with a duration of 5 to 15 minutes (P2 to P4 ). For optimal etch parameters, depressions (so-called caves) necessary for the "push-button effect" are formed, and the subsequent metal layer has good adhesion. The optimal etch conditions, such as time and temperature, may vary depending on the type of plastic, the geometry, the injection molding parameters, or the degree of aging of the substrate.

Claims (15)

A method of coating a plastic surface with a metal, comprising the steps of:
a) pre-treating the plastic surface with a composition (C) (etching solution) comprising at least one ionic liquid (IL);
b) treating the plastic surface from step a) with aqueous rinse solution (RS), while applying ultrasonic waves;
c) treating the plastic surface from step b) with activator composition (A) comprising at least one ion generating and / or colloid activator;
d) treating the plastic surface from step c) with an accelerator composition (B) comprising an acid and / or a reducing agent;
e) chemically depositing the metal layer by treating the plastic surface from step d) with a coating composition (M1) comprising at least one metal salt and at least one reducing agent;
f) electrochemically treating the plastic surface from step e) with at least one coating composition (M ') comprising at least one metal compound to form a plastic surface from step e) into at least one further metal layer Electrochemical coating. 2. The method of claim 1, wherein the ionic liquid (IL) is a salt that is liquid at 100 DEG C, 1 bar. 3. A process according to claim 1 or 2, wherein at least one ionic liquid (IL) comprises at least one salt having a cation selected from an imidazolium cation, a pyridinium cation, a pyrazolium cation and an alkylammonium cation, METHOD OF COATING WITH METAL. 4. A method according to any one of claims 1 to 3, wherein at least one ionic liquid (IL) is a salt having an alkylammonium cation of formula (I)

[Wherein,
R is unbranched and unsubstituted C ₁ -C ₁₈ -alkyl, CH ₃ O- (CH ₂ CH ₂ O) _p -CH ₂ CH ₂ - or CH ₃ CH ₂ O- (CH ₂ CH ₂ O) _p -CH ₂ CH ₂ - (wherein p = 0 to 3);
R ¹ , R ² and R ³ are each independently:
A hydrogen atom, an unsubstituted C ₁ -C ₁₈ - alkyl, 2-hydroxyethyl, 2-cyanoethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2- (n - butoxycarbonyl) ethyl, _{chlorine, CH 3 O- (CH 2 CH} 2 O) p -CH 2 CH 2 - or _{CH 3 CH 2 O- (CH 2} CH 2 O) p -CH 2 CH 2 - ( Wherein p = 0 to 3, or
Two adjacent R ¹ , R ² and R ³ radicals in formula (I), together with the nitrogen atom, are saturated and unsubstituted 5- to 7-membered rings;
X is an anion;
n is 1, 2 or 3; 5. The method according to any one of claims 1 to 4, wherein the at least one ionic liquid (IL) is methyl tri (1-butyl) ammonium methyl sulfate (MTBS). 6. The method according to any one of claims 1 to 5, wherein the ionic liquid (IL) is a combination of at least one first ionic liquid (IL1) and at least one second ionic liquid (IL2) Wherein the ionic liquid (IL1) comprises, as a cation, at least one alkylammonium cation and the second ionic liquid (IL2) comprises, as a cation, at least one nitrogen atom having a delocalized cationic charge A method of coating a plastic surface with a metal comprising at least one aromatic heterocycle. 7. The composition according to any one of claims 1 to 6, wherein the composition (C) is selected from the group consisting of methyltri (1-butyl) ammonium methylsulfate, 1-ethyl-3-methylimidazolium methylsulfate, Methylimidazolium ethylsulfate, 1-ethyl-3-methylimidazolium hydrogensulfate, 1-ethyl-3-methylimidazolium thiocyanate, 1-ethyl-3-methylimidazolium acetate, 1 -Ethyl-3-methylimidazolium methanesulfonate, and 1-ethyl-3-methylimidazolium diethyl phosphate. 2. The process of claim 1, wherein the at least one ionic liquid (IL) Lt; / RTI &gt; 8. The composition according to any one of claims 1 to 7, wherein the composition (C) comprises from 1% to 30% by weight of water, propylene carbonate, polyethylene glycol, diacetin , At least one solvent (S) selected from the group consisting of triacetin, ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol. 9. A method according to any one of claims 1 to 8, wherein the composition (C) comprises:
49 to 94% by weight, based on the total composition (C), of at least one ionic liquid (IL1) comprising at least one alkylammonium cation;
A composition comprising, as a cation, from 5% to 50% by weight, based on the total composition (C), of at least one aromatic heterocycle having a delocalized cationic charge and comprising at least one nitrogen atom Ionic liquids (IL2); And
A composition comprising 1% to 30% by weight of water, based on the total composition (C), of water, propylene carbonate, polyethylene glycol, diacetin, triacetin, ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol At least one solvent (S). 10. A method according to any one of claims 1 to 9, wherein the plastic surface is selected from the group consisting of polyamide, polystyrene, or styrene / acrylonitrile copolymer, acrylate / styrene / acrylonitrile copolymer and acrylonitrile / butadiene / Or a blend comprising at least one of the plastics mentioned above, and / or a multicomponent plastic. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; 11. A method of coating a plastic surface with a metal according to any one of claims 1 to 10, wherein the metal comprises at least one metal selected from nickel, aluminum, copper, chromium, tin, zinc and alloys thereof . 12. The composition according to any one of claims 1 to 11, wherein the plastic surface comprises or consists of an acrylonitrile / butadiene / styrene copolymer, in which case the plastic surface in step a) Lt; RTI ID = 0.0 &gt; 50 C &lt; / RTI &gt; to &lt; RTI ID = 0.0 &gt; 60 C &lt; / RTI &gt; and over a period of 5 to 15 minutes. Process according to any one of the preceding claims, wherein applying the ultrasonic wave in step b) while treating the plastic surface with an aqueous rinse solution (RS) comprises applying the plastic surface from step a) (RS) at a power in the range of 40 to 60 watts / L, at a temperature of 40 to 60 占 폚 and for a period of 1 to 30 minutes, wherein the aqueous rinse solution RS) comprises at least 85% by weight of water. 14. A method according to any one of claims 1 to 13, wherein step b) comprises the following steps:
b1) spraying a first aqueous rinse solution (RS1) onto the plastic surface from step a), or dipping the plastic surface from step a) into a first aqueous rinse solution (RS1) With a first aqueous rinse solution (RS1);
b2) treating the plastic surface from step b1) with a second aqueous rinse solution (RS2) while applying ultrasonic waves. 15. A method according to any one of claims 1 to 14, wherein the electrochemical coating in step f) comprises the following steps:
f1) treating the plastic surface from step e) with a coating composition (M2) comprising at least one copper compound and / or at least one nickel compound, whereby the plastic surface from step e) consists essentially of copper and / or nickel &Lt; RTI ID = 0.0 &gt; electrochemically &lt; / RTI &gt; And
f2) electrochemically coating the plastic surface from step f1) with an essentially chromium layer by treating the plastic surface from step f1) with a coating composition (M3) comprising at least one chromium compound.

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