JP2018523016A - Plating method for plastic surface - Google Patents

Abstract

The present invention relates to plastic surfaces, in particular plastic surfaces composed of acrylonitrile / butadiene / styrene copolymers (ABS) and plastic surfaces composed of mixtures of these copolymers with other plastics (ABS blends). A method for coating a metal with an etching solution (composition C) containing an ionic liquid IL, which comprises treating the plastic surface with an aqueous rinse solution RS while applying ultrasonic waves after etching. .

Description

  The present invention relates to plastic surfaces, in particular plastic surfaces composed of acrylonitrile / butadiene / styrene copolymers (ABS) and plastic surfaces composed of mixtures of these copolymers with other plastics (ABS blends). A method for coating a metal with an etching solution (composition C) containing an ionic liquid IL, which comprises treating the plastic surface with an aqueous rinse solution RS while applying ultrasonic waves after etching. .

  The coating of metal on the surface of plastic parts (also called plastic plating) is becoming increasingly important. By the plastic plating method, a composite material having the advantages of plastic and metal can be obtained. Plastic can be converted into virtually any desired shape by simple processing methods such as injection molding or extrusion. Furthermore, the use of plastic components can achieve a clear weight loss compared to metal parts. Subsequent plating of the resulting plastic molding is often carried out for decorative purposes or to obtain a shielding effect.

  For example, sanitary wares, automotive equipment, joinery hardware, jewelry and buttons / knobs are plated either in whole or in part to give the parts an attractive appearance. In addition, plastics may be plated for functional reasons. For example, electronics housings are plated to shield them from the emission or exposure of electromagnetic radiation. Furthermore, the surface properties of the plastic part can be altered in a controlled manner through the metal coating. Very often, copolymers of acrylonitrile, butadiene and styrene (ABS copolymers) and mixtures of these copolymers with other polymers, such as blends of ABS and polycarbonate (ABS / PC blends) are used.

  In order to produce a metal coating on a plastic part, the plastic part is usually fixed to a frame and contacted with a plurality of different processing liquids in a specific process sequence. In the first step, for this purpose, the plastic is generally pretreated to remove impurities such as fats and oils from the surface. Subsequently, an etching method is usually used to roughen the surface so that the subsequent metal layer is sufficiently fixed. In the etching operation, it is particularly important that a defined homogeneous structure with a concave shape is formed on the plastic surface.

  Thereafter, the roughened surface is treated with what is called an activator to form a catalytic surface for subsequent chemical plating. For this purpose, often so-called ionogen activators or colloidal systems will be used. “Plastic Plating (Kunststoffmetallisung)”, Handbook for theory and practice “Handbuch the Theory und Praxis” [“Plastic Metallization”, Handbook for Thel. 47)), for example, a plastic surface for activation by an ionogenic system is first treated with tin (II) ions, and after the treatment and rinsing with water, the gelation of tin oxide hydrate is brought about. It states that In subsequent treatment with a palladium salt solution, palladium nuclei are formed on the surface through redox reactions with tin (II) species, which act as catalysts for chemical plating. For activation by colloidal systems, a colloidal palladium solution formed by reacting palladium chloride and tin (II) chloride in the presence of excess hydrochloric acid is generally used (Annual Book of). ASTM Standard, Vol. 02.05 “Metallic and Inorganic Coatings; Metal Powders, Sintered P / M Structural Partners”, Designed by B727-83, Standard Practicing. ).

  After activation, plastic parts are generally first chemically plated using a metastable solution of a plating bath. These baths generally contain the metal to be deposited in the form of a salt in an aqueous solution and a reducing agent for the metal salt. Only when the chemical plating bath is in contact with a metal nucleus on the plastic surface, such as a palladium seed, a metal is formed by reduction, and the metal is deposited on the surface as a pinned layer. Often deposited during the chemical plating step is a nickel alloy with copper, nickel or phosphorus and / or boron.

  Furthermore, further metal layers can be electrolytically deposited by using a chemical plating bath on the coated plastic surface. Often it is the case that a copper layer or a further nickel layer is first electrodeposited before the desired decorative chromium layer is applied electrochemically.

  An important process step in plastic plating is pretreatment of the plastic surface. One reason that pre-treatment is necessary is to improve the adhesion of the metal to the plastic surface and generally make it possible. For this purpose, the plastic surface should be roughened to obtain more hydrophilic properties. In this connection, it is particularly important that a defined homogeneous structure of a concave shape is formed on the plastic surface. These recesses serve as starting points for the growth of metal nuclei in later plating processes.

  Since roughening has also been performed by mechanical methods in earlier stages, chemical swelling and etching of plastic surfaces has recently become established for this purpose. 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 measures in process progression, post-treatment and disposal. Due to chemical processes in the etching process, such as reduction of the chromium compounds used, the chromium-sulfuric acid etchants are used up and are not generally reused.

A method for chemical plating using a chromium-containing etching solution on a plastic surface is described in, for example, German Patent Application Publication No. 10054544.
Further known is the use of ionic liquids for the pretreatment (etching) of plastic surfaces in connection with plating. WO 2010/142567 is a method for coating a plastic with a metal, wherein the plastic comprises at least one salt (ionic liquid) having a melting point of less than 100 ° C. at 1 bar. Describes the preprocessed method. The pretreatment of various thermoplastic resins such as polyamides, polyolefins, polyesters, polyethers, polystyrene and styrene copolymers such as acrylonitrile / butadiene / styrene copolymer (ABS) has been described.

  Ionic liquids have been known since the end of the 1940s. The ionic liquid is a fluid molten salt that is liquid at temperatures below 100 ° C., preferably at room temperature (25 ° C., 1 bar), especially below room temperature. Ionic liquids are a new class of solvents that are non-molecular and have ionic characteristics.

  Typical cation / anion combinations resulting in ionic liquids are, for example, combinations of dialkylimidazolium, pyridinium, ammonium and phosphonium cations with halide anions, tetrafluoroborate anions, methylsulfate anions . In addition, there are many more possible cation and anion combinations that result in low melting salts.

  It is known that ionic liquids are used in a wide variety of different technical fields. In the context of polymers, the use of ionic liquids as antistatic agents or plasticizers has been described in the prior art, for example in WO 2004/005391, WO 2007/090755 and WO 2008/006422. Have been described. The document DE 102009003011 discloses the use of ionic liquids as adhesives for polymers.

  The object of the present invention is to provide an improved method for coating plastic surfaces with metal, wherein an ionic liquid is used in the pretreatment of plastic parts. It is possible to eliminate the use of toxic and disadvantageous chromium-containing etchants that have been conventional. One improvement in the coating process is firstly the improved strength / adhesion on the surface of the metal layer and the nature of the surface of the metal layer, as well as process engineering such as lower entrainment of the etchant. There is also improvement from the viewpoint. The process should be very simple and inexpensive to perform, and the recovery and / or recycling of the etchant should be very efficient.

  Surprisingly, it has been found that an improved metal coating can be achieved by a rinsing process using ultrasound after treating the plastic surface with an etchant containing at least one ionic liquid. The ultrasonic rinsing process with the aqueous rinsing solution of the present invention can provide a metal surface that is homogeneous, glossy, defect free and exhibits very good adhesion. More specifically, the process according to the invention makes it possible to obtain advantageous metal coatings having a layer sequence of chemically deposited nickel, copper, nickel, chromium.

The present invention is a method for coating a plastic surface, in particular a plastic molding, with a metal,
a) pretreating a plastic surface, in particular a plastic molded article, with a composition C (etching liquid) containing at least one ionic liquid IL;
b) treating the plastic surface from step a), in particular a plastic molding, with an aqueous rinse solution RS while applying ultrasound;
c) The plastic surface from step b), in particular a plastic molding, is subjected to at least one ionogen activator and / or colloidal activator, in particular at least one palladium component P, preferably at least one colloidal. Treating with activator composition A comprising palladium component P;
d) treating the plastic surface from step c), in particular a plastic molding, with an accelerator composition B comprising an acid and / or a reducing agent;
e) The surface from step d) is subjected to at least one metal salt, preferably at least one metal salt selected from nickel, copper and chromium salts and at least one reducing agent, preferably in situ reduction. Chemically depositing a metal layer, preferably a metal layer consisting essentially of nickel, copper, chromium or an alloy thereof, by treatment with a coating composition M1 containing an agent;
f) The surface from step e), in particular the plastic molding, is at least one comprising at least one metal compound, in particular at least one metal salt, preferably at least one copper salt, chromium salt and / or chromic acid. By electrochemical treatment with the seed coating composition M ′, the surface from step e), in particular the plastic molding, is treated with at least one further metal layer, preferably a metal layer consisting essentially of copper and / or It relates to a method comprising the step of electrochemically coating with a metal layer consisting essentially of chromium.

  Compared to the known use of ionic liquids, it is possible to achieve a further noticeable improvement in the coating results, for example better adhesion of the subsequent metal layer on the plastic surface. It has been found that the ultrasonic rinsing process can particularly advantageously exfoliate partially dissolved plastic particles from its surface, thus resulting in a more homogeneous surface structuring and an improved subsequent metal coating.

  The standard definition of ionic liquids distinguishes ionic liquids from known molten salts by melting points below 100 ° C, preferably below 80 ° C, or even below room temperature. In the context of the present application, ionic liquids shall be understood to mean those salts which have a melting point of less than 100 ° C. at 1 bar in the pure state.

  It is a feature of the method of the present invention that a more uniform and better adherence metal coating is obtained compared to a conventional water rinsing step. Preferably, any metal layer, in particular a metal layer in the layer sequence of nickel, copper, nickel and chromium, which is chemically deposited, has advantageous properties. Furthermore, water consumption in the rinsing process can be reduced.

  More advantageously, in the method according to the invention, the plastic surface is etched without the use of metal salts, and it is possible to dispense with the use of toxic and disadvantageous chromium-containing etchants.

It is the ABS (acrylonitrile / butadiene / styrene) surface (upper figure) obtained by Comparative Example C1, and the ABS (acrylonitrile / butadiene / styrene) surface (lower figure) obtained by Example I1 of the present invention. This is a possible configuration of steps a) and b) according to the invention.

Plastics and metals In the context of the present invention, molded articles or plastic molded articles are articles made from primary molding processes, such as primary molding processes such as casting, die casting, injection molding, extrusion blow molding, extrusion molding, firing. Conclusion and optionally an article made of essentially plastic made by a subsequent molding process. This molded product includes in particular processed products and semi-finished products, such as molded processed products, injection molded processed products, films or foils.

  In the method according to the invention, plastics, in particular plastics with a non-conductive surface, are coated with metal in several steps. The plastic is preferably a thermoplastic resin. The thermoplastic resin can be melted and converted into the desired shape by various methods, for example, by injection molding, extrusion molding, thermoforming or blow molding.

  Suitable thermoplastic resins include polyamides, polyolefins, polyesters, polyethers, polyacetals, especially polyoxymethylene, polycarbonates, polyurethanes, polyacrylates, polystyrene or styrene copolymers, especially styrene / acrylonitrile copolymers (SAN), acrylic esters / styrene. / Acrylonitrile copolymer (ASA) and acrylonitrile / butadiene / styrene copolymer (ABS).

  Polyamides include polycondensates of aminocarboxylic acids such as 6-aminocarboxylic acid or ε-caprolactam, or polycondensates of diamino compounds and dicarboxylic acids such as hexane-1,6-diamine and adipic acid.

  Suitable polyolefins are polyethylene, polypropylene and copolymers of ethylene or propylene.

  Suitable polyesters are polycondensation products of polyhydric alcohols such as butanediol, hexanediol, glycerol or trimethylolpropane and polybasic carboxylic acids, in particular phthalic acid and its isomers, adipic acid or trimellitic anhydride.

  One specific polyacetal is polyoxymethylene (POM).

  Polycarbonates are esters of carboxylic acids and polyhydric alcohols, such as bisphenol A, and also include polyester carbonates that contain additional polybasic carboxylic acids as constituents.

  Generally, polyethers contain repeating ether groups. Of particular industrial importance are, for example, polyetherimides containing aromatic ring systems and imide groups, especially linked via repeating ether groups, in particular polyethers containing phenylene and ketone groups linked by repeating ethers. Ketones, polyether sulfides containing ether and thioether groups in the polymer backbone, and polyether sulfones containing repeating ether and sulfone groups in the polymer backbone.

  Polyurethanes are typical polyadducts formed from polyfunctional isocyanates and polyhydric alcohols, and useful examples are both aliphatic and aromatic compounds. The polyacrylate is a homopolymer or copolymer of acrylic acid or methacrylic acid monomers, one specific example being polymethyl methacrylate (PMMA).

  It is also possible to carry out the method of the invention where the plastic comprises a carbon fiber reinforced epoxy resin (or consists of a carbon fiber reinforced epoxy resin). Carbon fiber reinforced epoxy resins are generally known and generally contain 10% to 90% by volume, preferably about 50% to 70% by volume, of reinforced carbon fibers. Suitable epoxy resins are polyethers obtained by reaction of compounds having hydroxyl groups, such as bisphenol, with epoxy compounds, such as epichlorohydrin. In general, epoxy resins can be cured by reaction with curing agents such as amines, acids, acid anhydrides, and thiols.

  Preferred polymers are styrene homopolymers and copolymers such as polystyrene, styrene / acrylonitrile copolymers and especially acrylonitrile / butadiene / styrene copolymers (ABS).

  A preferred embodiment is the method of the present invention, wherein the plastic surface is polyamide, polyolefin, polyester, polyether, polyacetal, polycarbonate, polyurethane, polyacrylate, polystyrene or styrene / acrylonitrile copolymer (SAN), acrylic. It relates to a process which is a surface comprising or comprising a copolymer of styrene selected from ester / styrene / acrylonitrile copolymers (ASA) and acrylonitrile / butadiene / styrene copolymers (ABS). The plastic to be coated may 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 above-mentioned plastics.

  A further preferred embodiment is the method of the invention as described above, wherein the plastic is a polyamide, polyolefin, polyester, polyether, polyacetal, polycarbonate, polyurethane, polyacrylate, polystyrene or styrene / acrylonitrile copolymer (SAN), acrylic. Comprising (or one or more plastics selected from ester / styrene / acrylonitrile copolymers (ASA), copolymers of styrene selected from acrylonitrile / butadiene / styrene copolymers (ABS) and carbon fiber reinforced epoxy resins (Consisting of the above).

  One preferred embodiment is the method of the present invention as described above, wherein the plastic surface is polyamide, polystyrene or styrene / acrylonitrile copolymer (SAN), acrylic ester / styrene / acrylonitrile copolymer (ASA) and acrylonitrile / butadiene / styrene copolymer. It relates to a process which is a surface comprising a copolymer of styrene selected from (ABS) or a blend and / or a 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 plastic comprises a multicomponent plastic comprising acrylonitrile / butadiene / styrene copolymer (ABS) or blend, such as ABS / PC (acrylonitrile / butadiene / styrene copolymer and polycarbonate) and / or ABS. ABS is supplied, for example, under the trade name Terluran (registered trademark) by Styrolution.

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

  In the method of the invention, the plastic or plastic surface is coated with metal. Useful metals are in particular nickel, aluminum, copper, chromium, tin or zinc and their alloys. The metal can be applied in one layer or operation, or preferably in more than one layer or operation. Preferably, it is possible to apply different metal layers, in particular at least three different metal layers.

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

Ionic liquid IL
Composition C used in the method of the invention comprises at least one salt (hereinafter referred to as ionic liquid IL) having a melting point of less than 100 ° C. at 1 bar.

  Preferably, the ionic liquid IL has a melting point of less than 100 ° C., more preferably less than 85 ° C., most preferably less than 60 ° 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, most preferably less than 750 g / mol, and in one specific embodiment Has a molar mass between 100 g / mol and 750 g / mol, or between 100 g / mol and 500 g / mol.

Preferred ionic liquids IL include at least one organic compound as a cation, and most preferably, the ionic liquid IL includes only an organic compound as a cation. Suitable organic cations are in particular organic compounds having heteroatoms such as nitrogen, sulfur or phosphorus, particularly preferred are organic compounds having a cationic group selected from ammonium, sulfonium and phosphonium groups. . The ionic liquid IL may in particular comprise a salt of the general formula [A] _n ⁺ [X] ^n- , where n is 1, 2, 3 or 4 and [A] ⁺ is , Ammonium cation, sulfonium cation or phosphonium cation, and [X] ⁿ⁻ is a monovalent anion, a divalent anion, a trivalent anion or a tetravalent anion.

The ionic liquid IL is also a mixed salt comprising at least two different organic cations [A] ⁺ or at least one organic cation [A] ⁺ and one or two different monovalent, divalent, trivalent. Alternatively, a mixed salt containing a tetravalent metal cation [M] ^{n +} may also be included.

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

  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, and includes the first ionic liquid IL1. IL1 includes at least one alkylammonium cation as a cation, and the second ionic liquid IL2 has a delocalized cation charge as a cation and at least one nitrogen atom including at least one nitrogen atom. This combination includes an aromatic heterocycle. Preferably, the composition comprises at least two different ionic liquids IL1 and IL2 in the range of 1 to 20, preferably in the range of 1.5 to 10, more preferably in the range of 2 to 6. Particularly preferably in the range of 3 to 5, for example 4, with a mass ratio value of IL1 to IL2.

  Preferably, the composition comprises at least two different ionic liquids IL1 and IL2 in the range of 1 to 20, preferably in the range of 3 to 18, more preferably in the range of 5 to 20. Particularly preferred is a mass ratio value of IL1 to IL2 in the range 7 to 15, for example 7.5 or 15.

Preferably, said ionic liquid IL, in particular ionic liquid IL1, comprises at least one, preferably just one, alkylammonium cation as a cation. In the context of the present invention, the alkyl ammonium cation, at least one C ₁ -C ₂₀ - alkyl group, preferably a C ₁ -C ₁₈ - having an alkyl group, and localized on the nitrogen atom positive It is understood to mean an ammonium compound having a charge. The compound may be a compound having a tetravalent nitrogen (a quaternary ammonium compound) or a compound having a trivalent nitrogen and one bond being a double bond. Preferably, the alkyl ammonium cation of the ionic liquid IL1 is a non-aromatic compound.

  Useful ring systems include monocyclic, bicyclic, non-aromatic ring systems. Examples include the bicyclic system described in WO 2008/043837. The bicyclic system of WO 2008/043837 is a diazabicyclo derivative, preferably a diazabicyclo derivative composed of one 7-membered ring and one 6-membered ring and having one amidinium group, An example is the 1,8-diazabicyclo [5.4.0] undec-7-enium cation.

Preferably, the ionic liquid IL, in particular the ionic liquid IL1, contains exactly one alkyl ammonium cation as the sole cation. Alternatively, the ionic liquid IL may be a mixed salt comprising at least one alkylammonium cation and at least one further organic cation [A] ⁺ and / or at least one further metal cation [M] ^{n +.} . Particularly preferred organic cations are quaternary ammonium cations which preferably have four C ₁ -C ₁₂ -alkyl groups as substituents on the nitrogen atom.

［式中、
Ｒは、１個〜２０個の、好ましくは１個〜１８個の、より好ましくは１個〜１２個の、特に好ましくは１個〜６個の炭素原子を含む有機基であり、ここで、前記有機基は、飽和または不飽和の非環式または環式の脂肪族基であり、該脂肪族基は、非置換であっても、または１個〜５個のヘテロ原子もしくは官能基によって中断もしくは置換されていてよく、
Ｒ¹、Ｒ²およびＲ³は、それぞれ独立して、
水素、
ハロゲン、特にフッ素、塩素、臭素およびヨウ素、好ましくは塩素、
Ｃ₁〜Ｃ₁₈−アルキル基であって、任意にＣ₁〜Ｃ₆−アルキル、Ｃ₁〜Ｃ₆−アルキルオキシ、Ｃ₁〜Ｃ₆−アルコキシカルボニル、ヒドロキシル、ハロゲン、アミノ、シアノおよびスルホから選択される官能基によって置換されていてよく、かつ／または１個以上の酸素原子および／もしくは硫黄原子および／もしくは１個以上の置換もしくは非置換のイミノ基によって中断されていてよいアルキル基、
Ｃ₂〜Ｃ₁₈−アルケニル基であって、任意にＣ₁〜Ｃ₆−アルキル、Ｃ₁〜Ｃ₆−アルキルオキシ、Ｃ₁〜Ｃ₆−アルコキシカルボニル、ヒドロキシル、ハロゲン、アミノ、シアノおよびスルホから選択される官能基によって置換されていてよく、かつ／または１個以上の酸素原子および／もしくは硫黄原子および／もしくは１個以上の置換もしくは非置換のイミノ基によって中断されていてよいアルケニル基、
Ｃ₅〜Ｃ₁₂−シクロアルキル基であって、任意にＣ₁〜Ｃ₆−アルキル、Ｃ₁〜Ｃ₆−アルキルオキシ、Ｃ₁〜Ｃ₆−アルコキシカルボニル、ヒドロキシル、ハロゲン、アミノ、シアノおよびスルホから選択される官能基によって置換されていてよいシクロアルキル基、
Ｃ₅〜Ｃ₁₂−シクロアルケニル基であって、任意にＣ₁〜Ｃ₆−アルキル、Ｃ₁〜Ｃ₆−アルキルオキシ、Ｃ₁〜Ｃ₆−アルコキシカルボニル、ヒドロキシル、ハロゲン、アミノ、シアノおよびスルホから選択される官能基によって置換されていてよいシクロアルケニル基、あるいは
５員ないし６員の複素環であって、酸素原子、窒素原子および／または硫黄原子を含み、かつ任意にＣ₁〜Ｃ₆−アルキル、Ｃ₁〜Ｃ₆−アルキルオキシ、Ｃ₁〜Ｃ₆−アルコキシカルボニル、ヒドロキシル、ハロゲン、アミノ、シアノおよびスルホから選択される官能基によって置換されていてよい複素環
であるか、あるいは２個の隣接するＲ¹基、Ｒ²基およびＲ³基は、式（Ｉ）中の窒素原子と一緒になって、不飽和または飽和の５員ないし７員の環であって、任意にＣ₁〜Ｃ₆−アルキル、Ｃ₁〜Ｃ₆−アルキルオキシ、Ｃ₁〜Ｃ₆−アルコキシカルボニル、ヒドロキシル、ハロゲン、アミノ、シアノおよびスルホから選択される官能基によって置換されていてよく、かつ１個以上の酸素原子および／もしくは硫黄原子および／もしくは１個以上の置換もしくは非置換のイミノ基によって中断されていてよい環であり、
Ｘは、アニオンであり、かつ
ｎは、１、２または３である］のイオン性液体ＩＬである。 Preference is given to general formula (I) comprising at least one, preferably just one alkylammonium cation as cation:

[Where:
R is an organic group containing 1 to 20, preferably 1 to 18, more preferably 1 to 12, particularly preferably 1 to 6 carbon atoms, wherein The organic group is a saturated or unsaturated acyclic or cyclic aliphatic group, which may be unsubstituted or interrupted by 1 to 5 heteroatoms or functional groups Or it may be replaced,
R ¹ , R ² and R ³ are each independently
hydrogen,
Halogen, in particular fluorine, chlorine, bromine and iodine, preferably chlorine,
An alkyl group, C ₁ -C ₆ optionally - - C ₁ ~C ₁₈ alkyl, C ₁ -C ₆ - alkyloxy, C ₁ -C ₆ - alkoxycarbonyl, hydroxyl, halogen, amino, cyano and sulfo An alkyl group which may be substituted by selected functional groups and / or may be interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups,
An alkenyl group, C ₁ -C ₆ optionally - - C ₂ ~C ₁₈ alkyl, C ₁ -C ₆ - alkyloxy, C ₁ -C ₆ - alkoxycarbonyl, hydroxyl, halogen, amino, cyano and sulfo An alkenyl group which may be substituted by selected functional groups and / or may be interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups,
C ₅ -C ₁₂ - a cycloalkyl group, C ₁ -C ₆ optionally - alkyl, C ₁ -C ₆ - alkyloxy, C ₁ -C ₆ - alkoxycarbonyl, hydroxyl, halogen, amino, cyano and sulfo A cycloalkyl group optionally substituted by a functional group selected from
C ₅ -C ₁₂ - a cycloalkenyl group, C ₁ -C ₆ optionally - alkyl, C ₁ -C ₆ - alkyloxy, C ₁ -C ₆ - alkoxycarbonyl, hydroxyl, halogen, amino, cyano and sulfo A cycloalkenyl group which may be substituted by a functional group selected from the above, or a 5- to 6-membered heterocyclic ring, containing an oxygen atom, a nitrogen atom and / or a sulfur atom, and optionally C ₁ -C ₆ - alkyl, C ₁ -C ₆ - alkyloxy, C ₁ -C ₆ - alkoxycarbonyl, hydroxyl, halogen, amino, or cyano and may heterocycle substituted by functional group selected from sulfo, or 2 Adjacent R ¹ , R ² and R ³ groups together with the nitrogen atom in formula (I) are unsaturated or saturated 5- to 7-membered rings. What, C ₁ -C ₆ optionally - alkyl, C ₁ -C ₆ - alkyloxy, C ₁ -C ₆ - alkoxycarbonyl, hydroxyl, halogen, amino, optionally substituted by functional groups selected from cyano and sulfo A ring which may be interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups,
X is an anion, and n is 1, 2 or 3].

Possible heteroatoms in the definition of R and R ¹ or R ³ are in principle replaced by —CH ₂ —, —CH═groups, —C≡groups or ═C═groups in a formal sense. Is any possible heteroatom. Preferred when the carbon-containing group contains a heteroatom are oxygen, nitrogen, sulfur, phosphorus and silicon. Preferred groups include in particular —O—, —S—, —SO—, —SO ₂ —, —NR′—, —N═, —PR′—, —POR′— and —SiR ′ ₂ —, In the formula, the R ′ group is the remaining part of the carbon-containing group. When the R ¹ to R ³ groups in the above formula (I) are bonded to a carbon atom and are not bonded to a heteroatom, they may be directly bonded via a heteroatom. Good.

Possible functional groups are in principle any functional group that can be bonded to a carbon atom or a heteroatom. Suitable examples include —OH (hydroxyl), ═O (particularly in the form of a carbonyl group), —NH ₂ (amino), ═NH (imino), —COOH (carboxyl), —CONH ₂ (carboxamide), —SO ₃ H (sulfo) and -CN (cyano). Functional groups and heteroatoms may be directly adjacent, thus combinations of multiple adjacent atoms such as -O- (ether), -S- (thioether), -COO- (ester), -CONH- (Secondary amide) or —CONR ′-(tertiary amide), such as di (C ₁ -C ₄ -alkyl) amino, C ₁ -C ₄ -alkyloxycarbonyl or C ₁ -C ₄ -alkyloxy Included as well.

  Halogen is fluorine, chlorine, bromine and iodine.

Preferably, the R group is
An unbranched or branched C ₁ -C ₂₀ -alkyl group which is unsubstituted or monovalent by hydroxyl, halogen, cyano, C ₁ -C ₆ -alkoxycarbonyl and / or sulfo. Alkyl groups which are substituted or polysubstituted and preferably have 1 to 20 carbon atoms in total, for example methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl -1-propyl (isobutyl), 2-methyl-2-propyl (t-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2 -Methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl -1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3 -Pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl 3,3-dimethyl-2-butyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 2-hydroxy Ethyl, 2-cyanoethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2- (n-butoxycarbonyl) ethyl, 6-hydroxyhexyl and propyls Ho,
Glycol, butylene glycol and 1 to 100, preferably 1 to 6, particularly preferably 1 to 3 units and having hydrogen or C ₁ -C ₆ -alkyl as terminal groups Those oligomers, for 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 0-3], in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12-tetraoxy Satetradecyl,
Vinyl, or unsubstituted C ₅ -C ₁₂ - cycloalkenyl group.

More preferably, the R groups are unbranched or unsubstituted C ₁ -C ₁₈ - alkyl, preferably C ₁ -C ₁₂ - alkyl, for example methyl, ethyl, 1-propyl, 1-butyl, 1 - 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 - and are, where p is 0-3.

Preferably, the R ¹ group, R ² group and R ³ group are each independently
hydrogen,
An alkyl group, C ₁ -C ₆ optionally - - C ₁ ~C ₁₈ alkyl, C ₁ -C ₆ - alkyloxy, C ₁ -C ₆ - alkoxycarbonyl, hydroxyl, halogen, amino, cyano and sulfo Alkyl groups which may be mono- or polysubstituted by selected functional groups such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (t-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3 -Methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4- Methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2- Dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl- 2-butyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, 2-hydroxyethyl, 2-cyanoethyl, 2 -Cyanopropyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxycarbonyl) ethyl, 2- (n-butoxycarbonyl) ethyl, 2-hydroxyethyl, 2-hydroxypropyl Pill, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2- Methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dimethylaminopropyl, 4-dimethylaminobutyl, 6-dimethylamino Hexyl, 2-hydroxy-2,2-dimethylethyl, 2-methoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3- Ethoxypropyl, 4-ethoxybutyl, -Ethoxyhexyl, chloromethyl, 2-chloroethyl, trichloromethyl, 1,1-dimethyl-2-chloroethyl, methoxymethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 2-isopropoxyethyl, 2-butoxypropyl 2-octyloxyethyl, 2-methoxyisopropyl and propylsulfo,
C ₅ -C ₁₂ - a cycloalkyl group, an optionally C ₁ -C ₆ - or cycloalkyl group optionally substituted by alkyl, such as cyclopentyl and cyclohexyl,
Glycol, butylene glycol and 1 to 100, preferably 1 to 6, particularly preferably 1 to 3 units and having hydrogen or C ₁ -C ₆ -alkyl as terminal groups Those oligomers, for 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 0-3], in particular 3-oxabutyl, 3-oxapentyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9,12-tetraoxatridecyl, 3,6,9,12-tetraoxate Tradecyl, 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 11-hydroxy -4,8-dioxaundecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9-hydroxy-5-oxanonyl, 14-hydroxy-5,10-dioxatetradecyl, 5-methoxy- 3-oxapentyl, 8-methoxy-3,6-dioxaoctyl, 11-methoxy-3,6,9-trioxaundecyl, 7-methoxy-4-oxaheptyl, 11-methoxy-4,8-di Oxaundecyl, 15-methoxy-4,8,12-trioxapentadecyl, 9-methoxy-5-oxanonyl, 14-methoxy 5,10-dioxatetradecyl, 5-ethoxy-3-oxapentyl, 8-ethoxy-3,6-dioxaoctyl, 11-ethoxy-3,6,9-trioxaundecyl, 7-ethoxy-4 -Oxaheptyl, 11-ethoxy-4,8-dioxaundecyl, 15-ethoxy-4,8,12-trioxapentadecyl, 9-ethoxy-5-oxanonyl or 14-ethoxy-5,10-oxatetra The decyl or two adjacent R ¹ , R ² and R ³ groups, together with the nitrogen atom in formula (I), are a saturated unsubstituted 5- to 7-membered ring For example, two adjacent R ¹ , R ² and R ³ groups are 1,4-butylene, 1,5-pentylene or 3-oxa-1,5-pentylene.

In one embodiment, two adjacent R ¹ , R ^2, and R ³ groups are taken together with the nitrogen atom in formula (I) to form an unsaturated or saturated 5- to 7-membered ring. Optionally substituted by 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 It may be a ring which may be interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups. Preferably, two adjacent R ¹ , R ² and R ³ groups together with the nitrogen atom in formula (I) form a saturated 5- to 7-membered ring, and 2 The adjacent R ¹ , R ² and R ³ groups are 1,4-butylene, 1,5-pentylene or 3-oxa-1,5-pentylene.

Most preferably, the R ¹ , R ² and R ³ groups are each independently hydrogen, unsubstituted C ₁ -C ₁₈ -alkyl, preferably C ₁ -C ₁₂ -alkyl (eg methyl, ethyl 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl), 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 - and are Where p is 0 to 3, or two adjacent R ¹ , R ² and R ³ groups are 1,4-butylene, 1,5-pentylene or 3-oxa-1 , 5-pentylene.

More preferably, R ¹ , R ² and R ³ are a hydrogen atom or a group having the above-mentioned hydrocarbon group and no further heteroatoms. Most preferably R ¹ , R ² and R ³ are hydrogen atoms or unsubstituted C ₁ -C ₁₈ -alkyl groups, more preferably C ₁ -C ₆ -alkyl groups such as methyl, ethyl, propyl Group, isopropyl group or n-butyl group.

［式中、
Ｒは、非分枝鎖状および非置換のＣ₁〜Ｃ₁₈−アルキル（例えば、メチル、エチル、１−プロピル、１−ブチル、１−ペンチル、１−ヘキシル、１−ヘプチル、１−オクチル、１−デシル、１−ドデシル、１−テトラデシル、１−ヘキサデシル、１−オクタデシル、特にメチル、エチル、１−ブチルおよび１−オクチル）、ＣＨ₃Ｏ−（ＣＨ₂ＣＨ₂Ｏ）_p−ＣＨ₂ＣＨ₂−またはＣＨ₃ＣＨ₂Ｏ−（ＣＨ₂ＣＨ₂Ｏ）_p−ＣＨ₂ＣＨ₂−であり、ここで、ｐは、０〜３であり、
Ｒ¹、Ｒ²およびＲ³は、それぞれ独立して、水素原子、非置換のＣ₁〜Ｃ₁₈−アルキル（例えば、メチル、エチル、１−ブチル、１−ペンチル、１−ヘキシル、１−ヘプチル、１−オクチル）、２−ヒドロキシエチル、２−シアノエチル、２−（メトキシカルボニル）エチル、２−（エトキシカルボニル）エチル、２−（ｎ−ブトキシカルボニル）エチル、塩素、ＣＨ₃Ｏ−（ＣＨ₂ＣＨ₂Ｏ）_p−ＣＨ₂ＣＨ₂−もしくはＣＨ₃ＣＨ₂Ｏ−（ＣＨ₂ＣＨ₂Ｏ）_p−ＣＨ₂ＣＨ₂−（前記式中、ｐは、０〜３である）であるか、あるいは２個の隣接するＲ¹基、Ｒ²基およびＲ³基は、式（Ｉ）中の窒素原子と一緒になって、飽和の非置換の５員ないし７員の環、例えば、１，４−ブチレン、１，５−ペンチレンまたは３−オキサ−１，５−ペンチレンであり、
Ｘは、アニオンであり、かつ
ｎは、１、２または３である］の、アルキルアンモニウムカチオンを含むイオン性液体である。 More preferably, the at least one ionic liquid IL1 has the formula (I):

[Where:
R is an unbranched and unsubstituted C ₁ -C ₁₈ -alkyl (eg, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1-decyl, 1-dodecyl, 1-tetradecyl, 1-hexadecyl, 1-octadecyl, in particular methyl, 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 - and is, where, p is 0-3,
R ¹ , R ² and R ³ are each independently a hydrogen atom, unsubstituted C ₁ -C ₁₈ -alkyl (eg, methyl, ethyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl 1-octyl), 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 is 0 to 3), Alternatively, two adjacent R ¹ , R ² and R ³ groups together with the nitrogen atom in formula (I) can be combined with a saturated unsubstituted 5- to 7-membered ring, for example 1, 4-butylene, 1,5-pentylene or 3-oxa-1,5- Is Nchiren,
X is an anion, and n is 1, 2 or 3.] is an ionic liquid containing an alkylammonium cation.

More preferably, the ionic liquid IL1 is represented by formula (I), wherein
R is C ₁ -C ₁₈ -alkyl, preferably C ₁ -C ₆ -alkyl, and R ¹ , R ² and R ³ are each independently a hydrogen atom or C ₁ -C ₁₈ -alkyl, Preferably it is C ₁ -C ₆ -alkyl or R is C ₁ -C ₁₈ -alkyl, preferably C ₁ -C ₆ -alkyl, R ¹ and R ^{2 taken} together are 1, 5-pentylene or 3-oxa-1,5-pentylene and R ³ comprises an alkylammonium cation which is a hydrogen atom or C ₁ -C ₁₈ -alkyl, preferably C ₁ -C ₆ -alkyl.

  Most preferred alkylammonium cations in the ionic liquid IL1 are methyltri (1-butyl) ammonium, 1-butyl-1-methylpyrrolidinium, N, N-dimethylpiperidinium and N, N-dimethylmorpholinium. is there.

Preferred anions according to formula (I), particularly preferred X ^n- anions, are described below.

  It contains methyltri (1-butyl) ammonium as a cation, and chloride ion, bromide ion, hydrogen sulfate ion, tetrachloroaluminate ion, thiocyanate ion, methyl sulfate ion, ethyl sulfate ion, methanesulfonate ion, formic acid as anions An ionic liquid IL containing an anion selected from ions, acetate ions, dimethyl phosphate ions, diethyl phosphate ions, p-tolyl sulfonate ions, tetrafluoroborate ions and hexafluorophosphate ions is particularly preferred.

  Particularly preferably, the ionic liquid IL1 is methyltri (1-butyl) ammonium methylsulfate (MTBS) or 1-butyl-1-methylpyrrolidinium dimethylphosphate, more preferably methyltri (1-butyl) ammonium methylsulfate. Fate (MTBS).

  The alkyl ammonium cation of the ionic liquid IL is a heterocyclic ring containing at least one, preferably one or two tetravalent and / or trivalent nitrogen, one bond being a double bond. It may be a ring system. For example, the cation of the ionic liquid IL, particularly the ionic liquid IL1, is piperidinium cation, pyrazolium cation, pyrazolinium cation, imidazolinium cation, pyrrolidinium cation, imidazolidinium cation, guanidinium cation. And a cyclic non-aromatic alkylammonium cation selected from the group consisting of corinium cations.

［式中、Ｒは、前記定義の通りであり、かつＲ⁴基、Ｒ⁵基、Ｒ⁶基、Ｒ⁷基、Ｒ⁸基、Ｒ⁹基、Ｒ¹⁰基、Ｒ¹¹基およびＲ¹²基は、それぞれＲ¹基、Ｒ²基およびＲ³基について前記定義の通りである］のカチオンである。 Suitable cations of said at least one ionic liquid IL, in particular ionic liquid IL1, are, for example, general formulas (IIa) to (IIj):

[Wherein, R is as defined above, and R ⁴ group, R ⁵ group, R ⁶ group, R ⁷ group, R ⁸ group, R ⁹ group, R ¹⁰ group, R ¹¹ group and R ¹² group] Are as defined above for the R ¹ , R ² and R ³ groups, respectively].

In a preferred embodiment, the composition C has at least one nitrogen atom, preferably one, two or three nitrogen atoms, with a delocalized cationic charge as cation. An ionic liquid IL (also referred to as ionic liquid IL2) containing an aromatic heterocycle of More specifically, the at least one nitrogen atom, preferably one, two or three nitrogen atoms are in the heterocyclic ring system. Preferably, the ionic liquid IL2 contains exactly one aromatic heterocycle having a delocalized cationic charge as a cation and containing at least one nitrogen atom. Alternatively, the ionic liquid IL2 is 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 +.} Good.

  The composition C contains the ionic liquid IL2 as a single ionic liquid or in combination with other ionic liquids, in particular containing at least one alkylammonium cation as a cation (ionic liquid). IL1) may be included in combination.

Most preferably, the ionic liquid IL is a 5- or 6-membered heterocyclic ring having 1, 2 or 3, preferably 1 or 2 nitrogen atoms as part of the ring system as a cation. Including aromatic ring systems of the formula In principle, the 5-membered or 6-membered heterocyclic aromatic ring system may comprise one or two further heteroatoms, in particular oxygen and / or sulfur atoms. The carbon atoms of the aromatic ring system are generally organic groups having up to 20 carbon atoms, preferably hydrocarbon groups, in particular C ₁ -C ₁₆ -alkyl groups, in particular C ₁ -C ₁₀ -alkyl groups, and more preferably C ₁ -C ₄ - may be substituted by an alkyl group.

［式中、Ｒは、前記定義の通りであり、かつＲ⁴基、Ｒ⁵基、Ｒ⁶基、Ｒ⁷基およびＲ⁸基は、それぞれＲ¹基、Ｒ²基およびＲ³基について前記定義の通りである］のカチオンである。好ましくは、Ｒ⁴基、Ｒ⁵基、Ｒ⁶基、Ｒ⁷基およびＲ⁸基は、それぞれ独立して、水素、メチル、エチル、１−プロピル、１−ブチルおよび塩素から選択される。 Suitable cations of the at least one ionic liquid IL are, for example, general formulas (IIk) to (IIs ″):

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

  Preferably, the cation of said at least one ionic liquid IL2 is a cation of formula (IIk), (IIo), (IIp), (IIq), (IIq ′) and (IIr) as described above, most preferably It is a cation of (IIo).

An ionic liquid IL, the cation of which is a pyridinium cation of formula (IIk),
One of R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is methyl, ethyl or chlorine and the remaining R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ groups are hydrogen or R ⁶ is dimethylamino and the remaining R ⁴ , R ⁵ , R ⁷ and R ⁸ groups are hydrogen or all R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen or R ⁵ is carboxyl or carboxamide and the remaining R ⁴ , R ⁶ , R ^{The 7} and R ⁸ groups are hydrogen, or the R ⁴ and R ⁵ groups or the R ⁵ and R ⁶ groups are 1,4-buta-1,3-dienylene, and the remaining R ⁴ Particularly preferred is ionic liquid IL, wherein the group, R ⁵ group, R ⁶ group, R ⁷ group and R ⁸ group are hydrogen.

An ionic liquid IL, the cation of which is a pyridinium cation of formula (IIk),
All R ⁴ groups, R ⁵ groups, R ⁶ groups, R ⁷ groups and R ⁸ groups are hydrogen or out of R ⁴ groups, R ⁵ groups, R ⁶ groups, R ⁷ groups and R ⁸ groups Particularly preferred is ionic liquid IL, one of which is methyl or ethyl and the remaining R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ groups are hydrogen.

  More specifically preferred pyridinium cations (IIk) include 1-methylpyridinium, 1-ethylpyridinium, 1- (1-butyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-hexyl) pyridinium, 1- (1-octyl) pyridinium, 1- (1-dodecyl) pyridinium, 1- (1-tetradecyl) pyridinium, 1- (1-hexadecyl) pyridinium, 1,2-dimethylpyridinium, 1-ethyl-2-methyl Pyridinium, 1- (1-butyl) -2-methylpyridinium, 1- (1-hexyl) -2-methylpyridinium, 1- (1-octyl) -2-methylpyridinium, 1- (1-dodecyl) -2 -Methylpyridinium, 1- (1-tetradecyl) -2-methylpyridinium, 1- (1-hexadec L) -2-methylpyridinium, 1-methyl-2-ethylpyridinium, 1,2-diethylpyridinium, 1- (1-butyl) -2-ethylpyridinium, 1- (1-hexyl) -2-ethylpyridinium, 1- (1-octyl) -2-ethylpyridinium, 1- (1-dodecyl) -2-ethylpyridinium, 1- (1-tetradecyl) -2-ethylpyridinium, 1- (1-hexadecyl) -2-ethyl Pyridinium, 1,2-dimethyl-5-ethylpyridinium, 1,5-diethyl-2-methylpyridinium, 1- (1-butyl) -2-methyl-3-ethylpyridinium, 1- (1-hexyl) -2 -Methyl-3-ethylpyridinium and 1- (1-octyl) -2-methyl-3-ethylpyridinium, 1- (1-dodecyl) -2- Chill-3-ethyl-pyridinium, 1- (1-tetradecyl) -2-methyl-3-ethyl pyridinium and 1- (1-hexadecyl) -2-methyl-3-ethyl pyridinium and the like.

An ionic liquid IL, the cation of which is a pyridazinium cation of formula (IIl),
All R ⁴ groups, R ⁵ groups, R ⁶ groups and R ⁷ groups are hydrogen or one of R ⁴ groups, R ⁵ groups, R ⁶ groups and R ⁷ groups is methyl or ethyl Especially preferred is ionic liquid IL, wherein the remaining R ⁴ , R ⁵ , R ⁶ and R ⁷ groups are hydrogen.

An ionic liquid IL, the cation of which is a pyrimidinium cation of the formula (IIm),
R ⁴ is hydrogen, methyl or ethyl, and R ⁵ , R ⁶ and R ⁷ are each independently hydrogen or methyl, or R ⁴ is hydrogen, methyl or ethyl, R ⁵ Particularly preferred is an ionic liquid IL, wherein R ⁶ is methyl and R ⁷ is hydrogen.

An ionic liquid IL, the cation of which is a pyrazinium cation of the formula (IIn),
R ⁴ is hydrogen, methyl or ethyl, and 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 is 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 Is particularly preferably ionic liquid IL, which is hydrogen.

An ionic liquid IL, the cation of which is an imidazolium cation of formula (IIo),
R ⁴ is hydrogen, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-octyl, 2-hydroxyethyl or 2-cyanoethyl, and R ⁵ , R ⁶ and R ⁷ Particularly preferred are ionic liquids IL, each independently of hydrogen, methyl or ethyl.

  Further 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- (1-hexadecyl) imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl)- 3-methylimidazolium, 1- (1-butyl) -3-ethylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-hexyl) -3-ethylimidazolium, 1- (1-hexyl) -3-butylimidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-octyl) -3-ethylimidazolium, 1- (1-octyl) -3-butylimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-dodecyl) -3-ethylimidazolium, 1 -(1-dodecyl) -3-octylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-ethylimidazolium, 1- (1-tetradecyl) -3 -Butylimidazolium, 1- (1-tetradecyl) -3-octylimidazolium, 1- (1-hexadecyl) -3-methylimidazolium, 1- (1-hexadecyl) -3-ethylimidazolium, 1- ( 1-hexadecyl) -3-butylimidazolium, 1- (1-hexadecyl) -3-octylimidazolium, 1,2-dimethylimidazole 1,2-3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2, 3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 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 and 1,4,5-trimethyl-3-octylimidazolium.

An ionic liquid IL, the cation of which is a pyrazolium cation of formula (IIp),
Particularly preferred is ionic liquid IL, wherein R ⁴ is hydrogen, methyl or ethyl, and R ⁵ , R ⁶ and R ⁷ are each independently hydrogen or methyl.

An ionic liquid IL, the cation of which is a thiazolium cation of formula (IIq) or (IIq ′) or an oxazolium cation of formula (IIr),
Particular preference is given to ionic liquids IL, wherein R ⁴ is hydrogen, methyl, ethyl or phenyl and R ⁵ , R ⁶ and R ⁷ are each independently hydrogen or methyl.

An ionic liquid IL, the cation of which is a 1,2,4-triazolium cation of formula (IIs), (IIs ′) or (IIs ″),
Particularly preferred are ionic liquids IL, wherein 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 the at least one ionic liquid IL2, has as its cation a pyridinium cation, pyridazinium cation, pyrimidinium cation, pyrazinium cation, imidazolium cation. , Pyrazolium cations, thiazolium cations and triazolium cations.

These cations are listed, for example, in WO 2005/113702. If necessary for a positive charge on the nitrogen atom or in the aromatic ring system, each of the nitrogen atoms is generally an organic group, preferably a hydrocarbon group, in particular a C ₁ , generally having no more than 20 carbon atoms. -C ₁₆ - alkyl group, in particular C ₁ -C ₁₀ - alkyl groups, more preferably C ₁ -C ₄ - is replaced by an alkyl group.

  Particularly preferred cations of IL are imidazolium cations, pyrimidinium cations and pyrazolium cations, which cations have an imidazolium ring system, a pyrimidinium ring system or a pyrazolium ring system, and optionally said ring system Are understood to mean compounds having any desired substituents on the carbon and / or nitrogen atoms.

  Particularly preferred cations of IL2 are imidazolium cations, pyridinium cations and pyrazolium cations, which cations have an imidazolium ring system, a pyridinium ring system or a pyrazolium ring system, and optionally carbons of said ring system It is understood to mean a compound having any desired substituent on the atom and / or nitrogen atom.

  Preferably, said ionic liquid IL, in particular said at least one ionic liquid IL2, comprises at least one, preferably just one imidazolium cation as a cation. More preferably, the ionic liquid IL comprises at least one, preferably just one imidazolium cation, as a single cation.

［式中、
Ｒ、Ｒ⁴、Ｒ⁵、Ｒ⁶およびＲ⁷は、それぞれ前記定義の通りであり、
Ｘは、アニオンであり、かつ
ｎは、１、２または３である］の化合物である。 In one particularly preferred embodiment, the ionic liquid IL comprises an imidazolium cation, formula (III):

[Where:
R, R ⁴ , R ⁵ , R ⁶ and R ⁷ are each as defined above;
X is an anion, and n is 1, 2 or 3.]

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

  The variable n is preferably 1.

Useful anions according to formulas (I) and (III), in particular as anions X ⁿ⁻ , are in principle any anions which in combination with cations become ionic liquids.

Said anions, in particular the anions X ⁿ⁻ , may be organic or inorganic anions. Particularly preferred ionic liquids consist only of a salt of an organic cation and one of the anions specified below.

のカルボキシイミド、ビス（スルホニル）イミドおよびスルホニルイミドの群、
一般式：Ｒ^aＯ^-のアルコキシドおよびアリールオキシドの群
から選択され、ここで、上記アニオン中のＲ^a、Ｒ^b、Ｒ^cおよびＲ^dは、それぞれ独立して、水素またはＣ₁〜Ｃ₁₂−アルキルおよび該アルキルのシクロアルキル置換、ハロゲン置換、ヒドロキシル置換、アミノ置換、カルボキシル置換、ホルミル置換、−Ｏ−置換、−ＣＯ−置換、−ＣＯ−Ｏ−置換もしくは−ＣＯ−Ｎ＜置換された成分、例えばメチル、エチル、１−プロピル、２−プロピル、１−ブチル、２−ブチル、２−メチル−１−プロピル（イソブチル）、２−メチル−２−プロピル（ｔ−ブチル）、１−ペンチル、２−ペンチル、３−ペンチル、２−メチル−１−ブチル、３−メチル−１−ブチル、２−メチル−２−ブチル、３−メチル−２−ブチル、２，２−ジメチル−１−プロピル、１−ヘキシル、２−ヘキシル、３−ヘキシル、２−メチル−１−ペンチル、３−メチル−１−ペンチル、４−メチル−１−ペンチル、２−メチル−２−ペンチル、３−メチル−２−ペンチル、４−メチル−２−ペンチル、２−メチル−３−ペンチル、３−メチル−３−ペンチル、２，２−ジメチル−１−ブチル、２，３−ジメチル−１−ブチル、３，３−ジメチル−１−ブチル、２−エチル−１−ブチル、２，３−ジメチル−２−ブチル、３，３−ジメチル−２−ブチル、ヘプチル、オクチル、ノニル、デシル、ウンデシル、ドデシル、メトキシ、エトキシ、ホルミル、アセチルまたはＣＦ₃から選択される。 The anions according to formulas (I) and (III), in particular the anion X ⁿ⁻ , of the ionic liquid IL are
^{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 ⁻ halide ions and halogen compounds,
A group of sulfate ions, sulfite ions and sulfonate ions of the formulas: SO ₄ ²⁻ , HSO ₄ ⁻ , SO ₃ ²⁻ , HSO ₃ ⁻ , R ^a OSO ₃ ⁻ , R ^a SO ₃ ⁻ ;
A group of phosphate ions of the formulas 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 ⁻ ;
A group of phosphonate ions and phosphinate ions of the formulas R ^a HPO ₃ ⁻ , R ^a R ^b PO ₂ ⁻ , R ^a R ^b PO ₃ ⁻ ;
General formula: R ^a COO ^- group of carboxylate ions,
General formula: BO ₃ ³⁻ , HBO ₃ ²⁻ , H ₂ BO ₃ ⁻ , R ^a R ^b BO ₃ ⁻ , R _a HBO ₃ ⁻ , R _a BO ₃ ²⁻ , B (OR ^a ) (OR ^b ) (OR ^b ) ( OR ^c ) (OR ^d ) ⁻ , B (HSO ₄ ) ⁻ , B (R ^a SO ₄ ) ⁻
A group of boronic acid ions of the general formulas: R ^a BO ₂ ²⁻ , R ^a R ^b BO ⁻ ;
A group of carbonates and carbonates of the general formula: HCO ₃ ⁻ , CO ₃ ²⁻ , R ^a CO ₃ ⁻ ;
General formula:

Carboximide, bis (sulfonyl) imide and sulfonylimide group of
Selected from the group of alkoxides and aryloxides of the general formula: R ^a O ⁻ , wherein R ^a , R ^b , R ^c and R ^d in the anion are each independently hydrogen or C ₁ -C ₁₂ -Alkyl and cycloalkyl substitution of the alkyl, halogen substitution, hydroxyl substitution, amino substitution, carboxyl substitution, formyl substitution, -O-substitution, -CO-substitution, -CO-O-substitution or -CO-N <substitution Ingredients such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (t-butyl), 1-pentyl 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl Til-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1- Butyl, 3,3-dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, heptyl, octyl, nonyl, decyl, undecyl, Selected from dodecyl, methoxy, ethoxy, formyl, acetyl or CF ₃ .

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

Particularly preferred anions, and even more particularly preferred anions X ⁿ⁻ are chloride ion, bromide ion, hydrogen sulfate ion, tetrachloroaluminate ion, thiocyanate ion, methyl carbonate ion, methyl sulfate ion, ethyl sulfate ion, methanesulfonic acid. Ion, formate ion, acetate ion, dimethyl phosphate ion, diethyl phosphate ion, p-tolyl sulfonate ion, tetrafluoroborate ion, hexafluorophosphate ion, bis (trifluoromethylsulfonyl) imide and bis (methylsulfonyl) ) Imido.

More particularly preferred anions, and even more particularly preferred anions X ⁿ⁻ are chloride ion, hydrogen sulfate ion, methyl sulfate ion, ethyl sulfate ion, methanesulfonate ion, formate ion and acetate ion.

As a cation,
1-methylimidazolium, 1-ethylimidazolium, 1- (1-butyl) imidazolium, 1- (1-octyl) imidazolium, 1- (1-dodecyl) imidazolium, 1- (1-tetradecyl) imidazole 1- (1-hexadecyl) imidazolium, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium, 1- (1-butyl) -3-methylimidazolium, 1- (1-butyl) ) -3-ethylimidazolium, 1- (1-hexyl) -3-methylimidazolium, 1- (1-hexyl) -3-ethylimidazolium, 1- (1-hexyl) -3-butylimidazolium, 1- (1-octyl) -3-methylimidazolium, 1- (1-octyl) -3-ethylimidazolium, 1- (1-octyl) -3- Tyrimidazolium, 1- (1-dodecyl) -3-methylimidazolium, 1- (1-dodecyl) -3-ethylimidazolium, 1- (1-dodecyl) -3-butylimidazolium, 1- (1 -Dodecyl) -3-octylimidazolium, 1- (1-tetradecyl) -3-methylimidazolium, 1- (1-tetradecyl) -3-ethylimidazolium, 1- (1-tetradecyl) -3-butylimidazolium 1- (1-tetradecyl) -3-octylimidazolium, 1- (1-hexadecyl) -3-methylimidazolium, 1- (1-hexadecyl) -3-ethylimidazolium, 1- (1-hexadecyl) ) -3-Butylimidazolium, 1- (1-hexadecyl) -3-octylimidazolium, 1,2-dimethylimidazolium 1,2,3-trimethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1- (1-butyl) -2,3-dimethylimidazolium, 1- (1-hexyl) -2,3- Dimethylimidazolium, 1- (1-octyl) -2,3-dimethylimidazolium, 1,4-dimethylimidazolium, 1,3,4-trimethylimidazolium, 1,4-dimethyl-3-ethylimidazolium, 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 At least one cation selected from the group consisting of 1-butyl-1-methylpyrrolidinium, preferably containing exactly one cation, and as anions chloride, bromide, hydrogen sulfate, tetra Chloroaluminate ion, thiocyanate ion, methyl sulfate ion, ethyl sulfate ion, methanesulfonate ion, formate ion, acetate ion, dimethylphosphate ion, diethylphosphate ion, p-tolylsulfonate ion, tetrafluoroborate ion Particularly preferred are ionic liquids comprising at least one anion, preferably just one anion, selected from the group consisting of and hexafluorophosphate ions.

  Further, 1,3-dimethylimidazolium methyl sulfate, 1,3-dimethylimidazolium hydrogen sulfate, 1,3-dimethylimidazolium dimethyl phosphate, 1,3-dimethylimidazolium acetate, 1-ethyl-3- Methyl imidazolium methyl sulfate, 1-ethyl-3-methyl imidazolium ethyl sulfate, 1-ethyl-3-methyl imidazolium hydrogen sulfate, 1-ethyl-3-methyl imidazolium thiocyanate, 1-ethyl-3 -Methyl imidazolium acetate, 1-ethyl-3-methylimidazolium methanesulfonate, 1-ethyl-3-methylimidazolium diethyl phosphate, 1- (1-butyl) -3-methylimidazolium methyl sulfate, 1 (1-butyl) -3-methylimidazolium hydrogen sulfate, 1- (1-butyl) -3-methylimidazolium thiocyanate, 1- (1-butyl) -3-methylimidazolium acetate, 1- (1 -Butyl) -3-methylimidazolium methanesulfonate, methyl tri (1-butyl) ammonium methyl sulfate, 1-butyl-1-methylpyrrolidinium dimethyl phosphate, N, N-dimethylpiperidinium and N, N-dimethyl An ionic liquid IL selected from the group consisting of morpholinium is particularly preferred.

  In one particularly preferred embodiment, composition C comprises 1-ethyl-3-methylimidazolium methyl sulfate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium hydrogen Rufate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium methylsulfonate, methyltri (1-butyl) ammonium methylsulfate (MTBS) and 1-butyl-1-methylpyrrolidinium At least one ionic liquid IL selected from the group consisting of dimethyl phosphate.

  In one embodiment, the composition C comprises methyltri (1-butyl) ammonium methylsulfate (MTBS) as the first ionic liquid IL1, and 1,3 as the second ionic liquid IL2. -Dimethylimidazolium methyl sulfate, 1,3-dimethylimidazolium hydrogen sulfate, 1,3-dimethylimidazolium dimethyl phosphate, 1,3-dimethylimidazolium acetate, 1-ethyl-3-methylimidazolium methylsulfate 1-ethyl-3-methylimidazolium hydrogen sulfate, 1-ethyl-3-methylimidazolium thiocyanate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium methanesulfonate, 1-Echi -3-methylimidazolium diethyl phosphate, 1- (1-butyl) -3-methylimidazolium methyl sulfate, 1- (1-butyl) -3-methylimidazolium hydrogen sulfate, 1- (1-butyl ) -3-Methylimidazolium thiocyanate, 1- (1-butyl) -3-methylimidazolium acetate, 1- (1-butyl) -3-methylimidazolium methanesulfonate, 1- (1-dodecyl) -3- Methyl imidazolium methyl sulfate, 1- (1-dodecyl) -3-methyl imidazolium hydrogen sulfate, 1- (1-tetradecyl) -3-methyl imidazolium methyl sulfate, 1- (1-tetradecyl)- 3-methylimidazolium hydrogen sulfate, 1- (1-he Sadecyl) -3-methylimidazolium methylsulfate and 1- (1-hexadecyl) -3-methylimidazolium hydrogen sulfate, preferably 1-ethyl-3-methylimidazolium methylsulfate And a compound selected from 1-ethyl-3-methylimidazolium hydrogen sulfate, 1-ethyl-3-methylimidazolium acetate and 1-ethyl-3-methylimidazolium methanesulfonate.

Additional Components of Composition C The composition of the present invention and the composition C used in the method of the present invention may comprise further components in addition to the at least one ionic liquid IL.

  These possible examples include additives by which the desired viscosity and / or the desired melting point is achieved. These include, for example, solvents, in particular organic solvents that are miscible with water and / or ionic liquids.

In a preferred embodiment, the composition C is
0% to 100%, preferably 60% to 90%, more preferably 60% to 80% by weight of the at least one ionic liquid IL, relative to the total composition C,
0% to 45% by weight, preferably 0% to 30% by weight, more preferably 1% to 30% by weight, most preferably 5% to 20% by weight, based on the entire composition C. At least one solvent S
including.

  In a preferred embodiment, the composition C consists of the components described above. That is, the above-mentioned components are added to make 100% by mass.

  Preferably, the composition C is a solution, more specifically, the components of the composition C are homogeneously miscible with each other, or the components of the composition C are in a homogeneously distributed form. Exists. More specifically, the composition C is a solution having molecular dispersion.

  The composition C may comprise as solvent S, in particular water or an organic solvent miscible with water and ionic liquid IL, or a mixture thereof.

  The viscosity of the composition C (etching composition) is preferably in the range from 20 mPas to 200 mPas, preferably in the range from 30 mPas to 100 mPas, more preferably in the range from 30 mPas to 70 mPas (in each case 60 Viscosity measured by dynamic means at ° C).

  The melting point of the composition C is generally less than 100 ° C., preferably less than room temperature (25 ° C.), particularly preferably less than 10 ° C., and more preferably less than 0 ° C.

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

  More preferably, the composition C is 1% by mass to 30% by mass, preferably 5% by mass to 20% by mass, more preferably 7% by mass to 15% by mass, based on the entire composition C. At least one solvent S selected from propylene carbonate, polyethylene glycol, in particular PEG 200, triacetin and water.

In a preferred embodiment, the composition C is
49% to 94%, preferably 55% to 85%, more preferably 60% to 80% by weight of at least one alkylammonium cation, based on the total composition C, At least one ionic liquid IL1,
5% to 50% by weight, preferably 5% to 40% by weight, preferably 10% to 40% by weight, and preferably 5% to 20% by weight, based on the total composition C More preferably 10% to 20% by weight of at least one of said ions having a delocalized cationic charge as a cation and comprising at least one aromatic heterocycle containing at least one nitrogen atom Liquid IL2,
1% to 30% by weight, preferably 5% to 20% by weight of water, propylene carbonate, polyethylene glycol, glycol and monoester of C ₁ -C ₆ -carboxylic acid, based on the total composition C, Selected from the group consisting of diesters or triesters and glycols, preferably from water, propylene carbonate, polyethylene glycol, diacetin (glyceryl diacetate), triacetin (glyceryl triacetate), ethylene glycol, diethylene glycol, triethylene glycol and tetraethylene glycol At least one solvent S selected from the group consisting of
including.

In another preferred embodiment, the composition C comprises
49% by weight to 94% by weight, preferably 55% by weight to 85% by weight, more preferably 60% by weight to 80% by weight of the at least one ionic liquid IL1, based on the entire composition C,
5% by weight to 50% by weight, preferably 5% by weight to 30% by weight, more preferably 5% by weight to 20% by weight of the at least one ionic liquid IL2, based on the entire composition C,
1% by weight to 30% by weight, preferably 10% by weight to 30% by weight, of said at least one solvent S relative to the whole composition C
including.

  In a preferred embodiment, the composition C contains only propylene carbonate as the solvent S. Furthermore, the composition comprises a mixture of propylene carbonate and water as solvent S, in which case the proportion of propylene carbonate with respect to the total solvent S is at least 30% by weight, preferably at least 50% by weight, more preferably at least 90%. It can be mass%.

  The composition preferably has a range of greater than 10% by weight, in particular greater than 30% by weight, more preferably greater than 50% by weight, most preferably greater than 80% by weight of the at least one ionic. It consists of liquid IL. In a particularly preferred embodiment, the composition consists of the at least one ionic liquid IL in a range of more than 90% by weight, in particular more than 95% by weight. In a further embodiment, the composition consists of only one or more of the ionic liquids, preferably the ionic liquids IL1 and IL2.

  The ionic liquid and the composition C comprising or consisting of the ionic liquid are preferably liquid over the entire temperature range from 20 ° C. to 100 ° C. (normal pressure, 1 bar).

Method An essential element of the method of the invention is the pretreatment of plastics or plastic surfaces as claimed. Various process steps for chemical and electrolytic coating with metals, as well as further measures for the necessary or desirable performance, preparation and finishing for that purpose, are described in a wide variety of different embodiments in the prior art, e.g. Japanese Patent Application Publication No. 10054544, “Modern Electroplating” Chapter 18, pages 450 to 457 (5th edition, 2010, John Wiley & Sons Inc., ISBN 978-0-) by Schlesinger et al. 470-16778-6) or Kanani's “Galvanotechnik” [Electroplating Technology] (Carl Hanser Publishing, 2000, ISBN 3-446-21024). -5).

  Even before the pretreatment in step a) of the present invention, it may be desirable to clean and / or degrease the plastic surface to be coated. This type of cleaning and degreasing is performed using conventional cleaning compositions or cleaning agents.

Step a)
The method according to the invention comprises in step a) a pretreatment of the plastic surface with a composition C (etching liquid) comprising at least one ionic liquid IL. Preferred ionic liquids and optional additional components of composition C are described above.

  Surprisingly, it has been found that adherence to the optimized processing conditions of the pretreatment, in particular temperature and time, results in a particularly advantageous metal coating.

  Preferably, the pretreatment of the plastic surface with composition C in step a) is at 30 ° C. to 120 ° C., more preferably at 40 ° C. to 120 ° C., particularly preferably at 50 ° C. to 65 ° C., most preferably at 50 ° C. Performed at ~ 60 ° C. Preferably, said composition C has the said temperature for that purpose. Often, prior individual heating of the plastic surface to be coated or the plastic molding to be coated is not required.

  Preferably, the pretreatment of the plastic surface with composition C in step a) is from 1 minute to 60 minutes, preferably from 1 minute to 30 minutes, particularly preferably from 2 minutes to 20 minutes, more preferably from 5 minutes to 10 minutes. Done over time.

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

  In a preferred embodiment, the present invention is a method for coating a plastic surface, in particular a plastic molding consisting of or comprising acrylonitrile / butadiene / styrene copolymer ABS, the plastic according to composition C in step a) The pretreatment of the surface, in particular the plastic molding, is carried out at a temperature in the range from 50 ° C. to 60 ° C., preferably in the range from 50 ° C. to 55 ° C. Relates to the method to be performed. A plastic surface comprising or containing acrylonitrile / butadiene / styrene copolymer (ABS) essentially comprises ABS, a blend comprising ABS, such as ABS / PC (acrylonitrile / butadiene / styrene copolymer and polycarbonate) and / or ABS. It may be a plastic molded product made of a multicomponent plastic.

  In a preferred embodiment, the plastic surface to be coated, in particular the plastic molding to be coated, is preferably immersed in the composition C having said temperature. In this case, the composition C may be agitated for better mass transfer, which can be done by stirring, pumping, air blowing and the like. Alternatively, the plastic surface itself may be rocked by specific equipment known in electroplating in composition C. Those skilled in the art are aware of suitable methods for this purpose.

  The required amount of composition C is adjusted so that the plastic surface is wetted to the desired degree. The plastic surface or plastic molding may be completely or partially immersed.

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

Step b)
The method of the invention comprises in step b) treating the plastic surface from step a) with an aqueous rinse solution RS while applying ultrasound. The treatment in step b) can in particular remove the adhering composition C, but it is also possible to remove partially dissolved plastic particles from the surface, in particular from the surface of the plastic molding.

  In a preferred embodiment, the treatment of the plastic surface with an aqueous rinsing solution RS while applying ultrasonic waves in step b) is performed by placing the plastic surface from step a) in an ultrasonic bath containing the aqueous rinsing solution RS. It is carried out by soaking for a period of 1 minute to 30 minutes, preferably 2 minutes to 20 minutes, more preferably 5 minutes to 15 minutes. In particular, sufficient rinsing can be obtained after 1 to 2 minutes, especially at about 90 seconds. Preferably, step b) immerses the plastic surface from step a) in an ultrasonic bath containing an aqueous rinse solution RS for a period of 1 minute to 2 minutes at a temperature ranging from 40 ° C to 60 ° C. Is done by.

  In a preferred embodiment, the treatment of the plastic surface in step b) with ultrasonic treatment, in particular with an aqueous rinsing solution RS of the plastic molded article, gives the plastic surface from step a), in particular the plastic molded article, By immersing in an ultrasonic bath containing an aqueous rinse solution RS at a power in the range of 40 watts / L to 60 watts / L for a period of 1 minute to 30 minutes and at a temperature of 40 ° C. to 60 ° C. Here, said aqueous rinse solution RS comprises 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 proportion of water is generally in each case relative to the total rinse solution. At least 85% by weight, preferably at least 95% by weight, more preferably at least 98% by weight. The organic solvent used may be a known polar water-miscible solvent such as alcohol or dimethyl sulfoxide (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 only of water.

  The rinse solution RS may optionally contain additives known to those skilled in the art, such as surfactants.

  The pH of the rinsing solution RS is preferably in the range from 5 to 8, in particular in the range from 6 to 7. Preferably, said rinsing step b), which may consist of a plurality of steps, is carried out in the range from 10 ° C. to 80 ° C., preferably in the range from 20 ° C. to 70 ° C., more preferably from 40 ° C. to 60 ° C. Is called.

  Sonication is preferably performed at a frequency in the range of 20 kHz to 400 kHz, preferably 30 kHz to 50 kHz. Sonication is preferably performed at an output in the range of 10 watts / L to 100 watts / L, preferably 40 watts / L to 60 watts / L. Particularly preferably, the sonication is performed at a power in the range of 40 watts / L to 60 watts / L for a period of 5 minutes to 15 minutes and at a temperature of 40 ° C. to 60 ° C. More preferably, the sonication is performed at a power ranging from 40 watts / L to 60 watts / L for a time of 1 minute to 2 minutes and at a temperature of 40 ° C to 60 ° C.

  Preferably, step b) may comprise a plurality of rinsing steps, in particular further rinsing steps without applying ultrasonic waves. Preferably, the treatment of the plastic surface with an aqueous rinse solution RS in step b) may comprise, as an additional step, treating the plastic surface with at least one further aqueous rinse solution RS, in particular with water, The treatment may be performed, for example, by spraying on or immersing the plastic surface.

One preferred embodiment is the method as described above, wherein step b) comprises the following steps:
b1) Plastic surface from step a) by spraying the first aqueous rinse solution RS1 on the plastic surface, in particular plastic molding, or by immersing the plastic surface, in particular plastic molding, in the first aqueous rinse solution RS1 , In particular the process of treating the plastic molding with the first aqueous rinsing solution RS1,
b2) relates to a method comprising (preferably consisting of) the step of treating the plastic surface from step b1), in particular a plastic molding, with a second aqueous rinse solution RS2 while applying ultrasound.

  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 completely or partially into the etching step a) (recirculation). The recycling of the composition C can be carried out, for example, by precipitating the dissolved plastic with water or an organic solvent and then removing the dissolved plastic by filtration. The medium / medium utilized for precipitation can subsequently be recovered by distillation. The dissolved plastic volatile components can also be removed from the composition by direct distillation. In this way it is possible to obtain a purified reusable composition C.

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

  Recirculation of the rinsing solution RS can be effected, for example, by removing the plastic present therein, preferably by filtration. In this way, it is possible to obtain a cleaned and reusable rinse solution (generally a mixture of water and ionic liquid IL), which is then completely or partially Thus, it may be recycled to the rinsing step b1) and / or b2). Preferably, a portion of the collected rinsing solution is drained to prevent the ionic liquid from being concentrated in the rinsing solution RS, particularly in the circuit.

Step c)
The process according to the invention comprises in step c) that the plastic surface from step b) is subjected to at least one ionogen activator and / or colloidal activator, in particular at least one palladium component P, preferably at least one. Treatment with activator composition A comprising a seed colloidal palladium component P.

  In general, step c) comprises applying a metal core, preferably of palladium, silver or gold, more preferably of palladium, particularly in combination with step d). Step b) is generally called activation. Preferably, the mode of activation and the first metal coating in step e) are adapted to each other.

  Known methods for activation include, for example, conventional colloidal activation (application of palladium / tin colloid), ionogen activation (application of palladium cation), direct metallization or Udique Plate®, Enplate MID select or LDS. It is a method known by the name of Process.

  For example, ionogen-based activation can be achieved by first treating the plastic surface with tin (II) ions, generally by rinsing with water after treatment with the tin (II) ions. A solid gel of tin hydrate is formed. In subsequent treatment with a palladium salt solution, palladium nuclei are usually formed on the plastic surface through reduction with tin (II) species, which are generally due to subsequent chemical plating (step (e)). Acting as a catalyst / metal nucleus.

  For activation by colloidal systems, it is possible to use noble metal colloid compositions, in particular colloids of the metals of the periodic table (transition group I) and of the platinum group. It is preferred to use a colloidal solution of palladium, silver or gold, particularly preferably a colloidal solution of palladium. In the colloidal solution, metal nuclei, for example palladium nuclei, are generally surrounded by a shell of protective colloid. Preferably, it is possible to use a colloidal palladium solution formed by the reaction of palladium chloride and tin (II) chloride in the presence of excess hydrochloric acid.

  The concentration of at least one ionogen activator and / or colloidal activator P in activator composition A is generally 20 mg / L to 150 mg / L.

  For further details of general palladium-containing activators and activation processes, see Annual Book of ASTM Standard, Vol. 02.05 “Metallic and Inorganic Coatings; Metal Powders, Sintered P / M Structural Parts”, Standard Practical for Preparation of Plastic Materials for Electron, No. 4 to No.

  In general, the activator P used may be a standard commercially available palladium activator, such as “Activator U” from HSO or “Surtec 961 Pd” from Surtec.

Step d)
The method 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 promoter composition B removes the protective colloid shell from the metal nuclei, in particular palladium nuclei, silver nuclei or gold nuclei adsorbed on the surface (especially in the depressions) and / or the adsorption. The reduced metal salt is reduced to a metal. Treatment of the plastic surface with accelerator composition B generally results in metal nuclei on the plastic surface, preferably palladium, silver or gold metal nuclei, more preferably palladium metal nuclei. These metal nuclei generally serve as starting points (catalysts) for subsequent chemical metal deposition in step e).

According to the invention, the promoter composition B) is at least one reducing agent which is particularly suitable for removing the protective metal colloid shell and / or for reducing the metal salts present on the surface to metal. And / or an acid. Preferably, said at least one reducing agent is an alkali metal, ammonium or alkaline earth metal fluoroborate such as sodium tetrafluoroborate (NaBF ₄ ), peroxide, sulfite, bisulfite, hydrazine and Selected from their salts, hydroxylamine and their salts. 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 can be set in particular in the range from 0 to 7, preferably in the range from 1 to 2.

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

  For further details of general accelerator compositions and acceleration processes, see Annual Book of ASTM Standard, Vol. 02.05 “Metallic and Inorganic Coatings; Metal Powders, Sintered P / M Structural Parts”, Standard Practical for Preparation of Plastic Materials for Electron, No. 4 to No.

  In general, the accelerator composition B used may be a standard commercial accelerator, such as “HSO Accelerator” from HSO or “Surtec 961 A” from Surtec.

Step e)
A further element of the method of the present invention is the application of a coating (chemical metal deposition), referred to as the first metal coating, generally performed by electroless means. Generally, the first layer (seed layer) applied by electroless means is a layer of nickel, copper, chromium or their alloys. One or more layers of nickel and / or copper are preferred. Particularly preferred is just one layer consisting essentially of nickel.

  The process according to the invention comprises in step e) the plastic surface from step d), in particular a plastic molded article, at least one metal salt, preferably a nickel (II) salt and at least one reducing agent, preferably in situ. It involves chemically depositing a metal layer, preferably a metal layer consisting essentially of nickel, by treatment with a coating composition M1 containing a chew reducing agent.

  More preferably, step e) comprises at least one nickel (II) salt and / or at least one copper (II) salt and at least one reducing agent, preferably in situ. It involves chemically depositing a metal layer consisting essentially of nickel and / or copper by treatment with a coating composition M1 containing a reducing agent.

  A typical coating composition M1 is, for example, 451 of “Modern Electroplating” by Schlesinger et al. (5th edition, 2010, John Wiley & Sons Inc., ISBN 978-0-470-16778-6). Page.

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

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

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

  The pH of the coating composition M1 is generally in the range of 4 to 11. In principle, depending on the type of buffer system, a distinction can be made between acidic or alkaline compositions. In the case of an acidic process, the pH of the coating composition M1 is generally in the range from 4 to 7, preferably from 4 to 6. In the case of alkaline processes, the pH is generally higher than 7 and up to 11, preferably 8 to 10. Preferably, the pH is set to about 9.

  Preferably, the coating composition M1 comprises hydrogen peroxide, peroxide, hypophosphite, hypophosphate (sodium hypophosphate), borane and borane derivatives (eg aminoborane such as dimethylaminoborane, boron At least one reducing agent selected from the group consisting of sodium hydride) and hydrazine, in particular in situ reducing agents.

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

  In general, coating compositions M1 for chemical nickel baths are described in, for example, “Modern Electroplating” by Schlesinger et al. (5th edition, 2010, John Wiley & Sons Inc., ISBN 978-0-470). General components and additives known to those skilled in the art described in chapter 18.3 of -16778-6) may be included. In general, the coating composition M1 is a complexing agent for nickel ions, preferably carboxylic acids and hydroxycarboxylic acids such as succinic acid, citric acid, malic acid, tartaric acid and / or lactic acid, and acetic acid, propionic acid. , Maleic acid, fumaric acid and / or itaconic acid. The buffering agents used can generally be citrate, acetate, phosphate and ammonium salts.

  In general, the coating composition M1 used is a standard commercial coating bath for electroless nickel deposition, such as “Electroless Nickel 601KB” from HSO or “Surtec 3 / 11D” from Surtec. It may be.

  The temperature in the case of the acidic method of the coating composition M1 during the implementation of step d) is generally between 60 ° C. and 100 ° C., and the temperature in the case of the alkaline method is generally between 25 ° C. and 50 ° C. Within the range.

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

  By the method according to the invention, the deposition of metal layers, in particular nickel, copper and chromium layers which are electrochemically deposited following said chemically deposited nickel layer, for example on plastic surfaces made of ABS Can be improved, or the adhesion can be made practical for many plastics anyway. The adhesion achieved of the metal layer is very good even under mechanical stress or even at high temperatures. Furthermore, the metal surface obtained by the method of the invention has a particularly uniform structure.

  The method of the invention electrochemically treats in step f) the plastic surface from step e), in particular a plastic molding, with at least one coating composition M ′ comprising at least one metal compound. By electrochemically coating the plastic surface from step e), in particular a plastic molding, with at least one further metal layer.

  Preferably step f) comprises electrochemically coating a plastic surface, in particular a plastic molding, with at least one metal layer consisting essentially of copper. For this purpose, the plastic surface, in particular a plastic molding, is subjected to electrochemical electrolysis with a coating composition M2 comprising at least one copper compound, preferably at least one copper (II) salt.

  Preferably step f) comprises electrochemically coating a plastic surface, in particular a plastic molding, with at least one metal layer consisting essentially of chromium. For this purpose, the plastic surface, in particular a plastic molding, is preferably selected from at least one chromium compound, preferably chromic acid, a chromic acid derivative, a chromium (VI) salt and a chromium (III) salt. Contacted with a coating composition M3 comprising at least one chromium compound and subjected to electrochemical electrolysis.

Preferably, the present invention is the method as described above, wherein the electrochemical coating in step f) comprises the following steps:
f1) 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) salt, on the surface from step e), in particular a plastic molding. Electrochemically coating the surface from step e), in particular the plastic molding, with a layer consisting essentially of copper and / or nickel;
f2) The surface from step f1), in particular the plastic molding, contains at least one chromium compound, in particular at least one selected from chromic acid, chromic acid derivatives, chromium (VI) salts and chromium (III) salts Electrochemically coating the surface from step f1), in particular a plastic molding, with a layer consisting essentially of chromium by treatment with a coating composition M3 comprising a chromium compound of Process).

Preferably, in step f1), the surface from step e) is the surface from step e) with a coating composition M2 comprising at least one copper compound, in particular comprising at least one Cu (II) salt. By treatment, it is electrochemically 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. A preferred coating sequence (step (e), step (f1) and step (f2)) may be as follows:
Ni (chemical)->SB-Ni->B-Ni-> Cr or Ni (chemical)->Cu->SB-Ni->B-Ni-> Cr or Cu (chemical)->SB-Ni->B-Ni-> Cr or Cu (chemical) ) → Cu → SB—Ni → B—Ni → Cr (where SB—Ni is a semi-bright nickel layer and B—Ni is a bright nickel layer.)

Generally, the coating composition M2 comprises at least one copper salt, preferably at least one copper (II) salt, such as copper sulfate (CuSO ₄ ). Generally, the coating composition M2 comprises at least one copper salt, water and an acid such as sulfuric acid, alkyl sulfonic acid such as methane sulfonic acid. In general, the coating composition M2 may contain, as further additives, additives customary for this application, such as surfactants, brighteners, inhibitors or levelers.

  In general, the coating composition M2 used may be a standard commercially available copper electrolytic bath, such as “Copper HD 500” from HSO or “Surtec 867” from Surtec.

Generally, the coating composition M3 comprises at least one chromium salt and / or chromic acid, preferably at least one chromium (III) salt and / or chromium (VI) salt, more preferably chromic acid H _2. CrO ₄ and / or chromium trioxide CrO ₃ is included. In general, the coating composition M3 comprises at least one chromium compound, in particular chromic acid, water and an acid as a catalyst, such as sulfuric acid (H ₂ SO ₄ ), hydrofluoric acid (HF), hexafluorosilicic acid. (H ₂ SiF ₆ ), at least one acid selected from alkyl sulfonic acids such as methane sulfonic acid. In general, the coating composition M3 may contain surfactants known for this application as further additives.

  The method according to the invention may comprise one or more rinsing steps in each case before and / or after the above-mentioned steps a) to f). In particular, after step f), the plastic surface, in particular the plastic molding, can be rinsed, preferably rinsed with water and / or dried.

DESCRIPTION OF THE DRAWINGS The electron micrograph in FIG. 1 is obtained by the ABS surface (upper view) obtained by Comparative Example C1 (by a simple rinsing process) and Example I1 of the present invention with sonication according to the present invention. The ABS surface (bottom view) is shown. In Examples C1 and I1, an etchant composed of MTBS: EMIM-OAc (95: 5) was used. Their ABS surfaces were etched at 70 ° C. for 10 minutes.
FIG. 2 shows one possible configuration of steps a) and b) of the present invention. The symbols here have the following meanings:
(I) Pretreatment bath (step (a))
(II) Spraying device collection container (step (b1))
(III) Spray nozzle (step (b1))
(IV) Ultrasonic rinse bath (step (b2))
(V), (VI) Filter (1) Progress path to molded article (II) (2) Progress path to molded article (IV) (3) Removal of spray solution, that is, first spray solution (4) ) Removal of the ultrasonic bath rinse solution, i.e. the second rinse solution (5) Progress path of the cleaned rinse solution (5.1), (5.2) (II) / ( IV) Recirculation to (6.1), (6.2) Discharge of the removed plastic (7) Discharge of a part of the cleaned rinse solution

  FIG. 2 shows an embodiment of the method steps a), b1) and b2). The molded article is immersed in a treatment bath (I) containing at least one ionic liquid IL (step (a)). The ionic liquid and partly on the surface of the molded product as it moves in the direction of travel through (1) to the spraying step (the spraying device consisting of (II) and (III)) Some of the dissolved plastic particles are entrained (incorporated) with it. In the spraying device (collection container (II) and spray nozzle (III)), the first rinsing solution RS is sprayed on the molded product, so that the composition C adhering to the molded product is rinsed off (step b1). ). The spent rinse solution is collected in a collection container and delivered via (3) to the filter (VI). The molded article is on the surface of the molded article as it moves in the direction of travel through (2) to the ultrasonic rinse bath (IV) containing the second rinse solution RS (step (b2)). The ionic liquid and the first rinse solution and part of the partially dissolved plastic particles are again entrained with it. The shaped article is immersed in an ultrasonic bath, removed from the bath after a residence time and sent to further process steps. In the ultrasonic bath (IV), in a continuous manner, the second rinse solution is removed from the bath via (4) and supplied to the filter (V). Further, the cleaned rinse solution is fed to (II) and (IV) via (5), (5.1) and (5.2). In the filters (V) and (VI), the polymer is filtered off from the spent rinse solution and discharged. The cleaned rinse solution is recycled to the process via (5) and a portion is discharged via (7).

  The invention is illustrated in detail by the following examples.

Example 1
1.1 General Test Method for Testing Etching Action Plaques of 60 mm × 30 mm × 2 mm in ABS (acrylonitrile / butadiene / styrene terpolymer Terluran® GP 35 from Styrolution) at 70 ° C. Immerse in 2 L of stirred ionic liquid (Composition C) for 10 minutes. After etching is complete, the substrate is rinsed with water. In an embodiment according to the invention, the plaque is subsequently processed in an ultrasonic water bath.

  When the etching action is confirmed by SEM analysis, it shows a new surface structure (see FIG. 1).

1.2 Comparison of etching results with and without ultrasonic rinsing process The etching process was carried out in the ABS test plaque as described above, at an MTBS / EMIM mass ratio of 95: 5, with methyltri (1-butyl) ammonium methylsulfate (MTBS). ) And 1-ethyl-3-methylimidazolium acetate (EMIM-OAc).

  After the etching step (step (a)), the ABS test plaque is immersed in a 50 ° C. water bath for 10 minutes (C1) or ultrasonically (6 L of water, 280 W, ie, 10 minutes at 50 ° C. Either (I1) was performed at 35 kHz) corresponding to about 50 W / L.

  The SEM image in FIG. 1 shows the ABS surface obtained by Comparative Example C1 (by a simple rinsing process) (upper figure) and the ABS surface obtained by Example I1 according to the invention with sonication according to the invention ( The lower figure).

  In the SEM image, it can be seen that the ultrasonic rinsing process resulted in a greater removal of the partially dissolved plastic particles that were partially dissolved by the etchant. In the SEM image C1 that was not subjected to sonication, a large amount of porous plastic residue is clearly seen. In the SEM image I1 subjected to the ultrasonic treatment, such a residue does not exist as a whole. The sonicated SEM image exhibits a homogeneously etched ABS surface with a morphology that has particularly good suitability for performing subsequent plating (metallization) steps.

Example 2-Variation of etching conditions ABS test plaques were processed by the general test method described above for testing of etching action.

The etchant (Composition C) used in all cases was methyltri (1-butyl) ammonium methyl sulfate (MTBS), 1- 1 at a mass ratio of MTBS / EMIM-ETSO ₄ / PC of 80:10:10. It was a mixture of ethyl-3-methyl imidazolium ethyl sulfate (EMIM-EtSO ₄₎ and propylene carbonate (PC). Various etching conditions (temperature and time) described in Table 1 below were established.

  When the etching action was confirmed by SEM analysis, it exhibited a new surface structure.

After etching and rinsing, the test plaque was plated (metallization). For this purpose, the following processing steps were performed:
Treatment with activator composition A → treatment with accelerator composition B → chemical electroless deposition of nickel using coating composition M1 → electrolytic deposition of copper using coating composition M ′.

The following products were used:
Activator composition A
"Activator U" made by HSO or "Surtec 961 Pd" made by Surtec
Accelerator composition B
"HSO Accelerator" manufactured by HSO or "Surtec 961 A" manufactured by Surtec
Coating composition M1
"Electroless Nickel 601KB" manufactured by HSO or "Surtec 3 / 11D" manufactured by Surtec
Coating composition M ′
"Copper HD 500" from HSO or "Surtec 867" from Surtec

  The quality of the metal coating is measured using a test called the cross cut test according to ISO 2409: 2007. The results are summarized in Table 1.

Table 1: Etching conditions (step (a))

  It can be seen that by treating the ABS surface at a temperature of 45 ° C. in step a), a homogeneous structuring of the surface cannot be obtained even with an etching time of 15 minutes (P1). If the etching temperature is too low and / or the processing time is too short, the surface is only roughened. The nucleation required for plating (metallization) in the subsequent process is inappropriate. It is not possible to produce a layer with adequate adhesion between the plastic surface and the metal layer (insufficient “push-button effect”).

  At higher etch temperatures of 65 ° C. and / or with excessively long etch times, the plastic surface is over attacked (P5 and P6). That is, the surface has too many crevices and exhibits a heterogeneous structure.

  In this example, a particularly advantageous homogeneous surface structure of the ABS surface at a temperature in the range of 50 ° C. to 60 ° C., more preferably in the range of 50 ° C. to 55 ° C. and for a time of 5 to 15 minutes. Was obtained (see P2 to P4). For optimal etching parameters, the depressions (also called cavities) required for the “push button effect” are formed and the subsequent metal layer shows good adhesion. Optimal etching conditions, such as time and temperature, can vary depending on the type of plastic, geometry, injection molding parameters or the age of the substrate.

  I Pretreatment bath (step a), II Blowing device collection container (step b1), III Spray nozzle (step b1), IV Ultrasonic rinsing bath (step b2), V, VI filter, 1 Molded product to II Progression path, 2 progression path to the IV, 3 removal of spray solution (first spray solution), 4 removal of ultrasonic bath rinse solution (second rinse solution), 5 of cleaned rinse solution Path of travel 5.1, 5.2 Recirculation of the cleaned rinse solution to II / IV, 6.1, 6.2 Discharge of the removed plastic, 7 Part of the cleaned rinse solution Discharge

Claims (15)

A method for coating a plastic surface with metal,
a) pretreating a plastic surface with a composition C (etching liquid) containing at least one ionic liquid IL;
b) treating the plastic surface from step a) with an aqueous rinse solution RS while applying ultrasound;
c) treating the plastic surface from step b) with an activator composition A comprising at least one ionogen activator and / or colloidal 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 surface from step e) with at least one coating composition M ′ comprising at least one metal compound, thereby treating the surface from step e) with at least one further layer. Electrochemically coating with a metal layer.   The method of claim 1, wherein the ionic liquid IL is a salt that is liquid at 100 ° C. and 1 bar.   The method of claim 1 or 2, wherein the at least one ionic liquid IL is at least one salt having a cation selected from an imidazolium cation, a pyridinium cation, a pyrazolium cation and an alkylammonium cation. . The at least one ionic liquid IL has the formula (I):

[Where:
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 - and is, where, p is 0-3,
R ¹ , R ² and R ³ are each independently a hydrogen atom, unsubstituted C ₁ -C ₁₈ -alkyl, 2-hydroxyethyl, 2-cyanoethyl, 2- (methoxycarbonyl) ethyl, 2- (ethoxy 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 is 0 to 3),
Or two adjacent R ¹ , R ² and R ³ groups, together with the nitrogen atom in formula (I), are saturated unsubstituted 5 to 7 membered rings;
The method according to any one of claims 1 to 3, wherein X is an anion, and n is 1, 2 or 3.   The method according to any one of claims 1 to 4, wherein the at least one ionic liquid IL is methyltri (1-butyl) ammonium methylsulfate (MTBS).   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 is at least 1 as a cation. Wherein the second ionic liquid IL2 has a delocalized cationic charge as a cation and includes at least one aromatic heterocycle containing at least one nitrogen atom. 6. A method according to any one of claims 1-5.   The composition C comprises methyl tri (1-butyl) ammonium methyl sulfate, 1-ethyl-3-methylimidazolium methyl sulfate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methyl Imidazolium hydrogen sulfate, 1-ethyl-3-methylimidazolium thiocyanate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium methanesulfonate and 1-ethyl-3-methylimidazolium 7. The method according to any one of claims 1 to 6, comprising at least one ionic liquid IL selected from the group consisting of diethyl phosphate.   The composition C is composed of 1% to 30% by mass of water, propylene carbonate, polyethylene glycol, diacetin, triacetin, ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol with respect to the entire composition C. The process according to claim 1, comprising at least one solvent S selected from: The composition C is
At least one ionic liquid IL1 comprising 49% to 94% by weight of at least one alkylammonium cation, based on the total composition C;
5% by weight to 50% by weight, based on the total composition C, having at least one aromatic heterocycle having a delocalized cationic charge as a cation and containing at least one nitrogen atom A seed ionic liquid IL2, and
At least 1 selected from the group consisting of 1% to 30% by weight of water, propylene carbonate, polyethylene glycol, diacetin, triacetin, ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol with respect to the entire composition C The process according to claim 1, comprising a seed solvent S.   Said plastic surface is a polyamide, polystyrene or a copolymer of styrene selected from styrene / acrylonitrile copolymers, acrylic esters / styrene / acrylonitrile copolymers and acrylonitrile / butadiene / styrene copolymers, or a blend comprising at least one of the aforementioned plastics and / or 10. A method according to any one of claims 1 to 9, which is a surface comprising or comprising a multicomponent plastic.   The method according to any one of claims 1 to 10, wherein the metal includes at least one metal selected from nickel, aluminum, copper, chromium, tin, zinc, and alloys thereof.   Said plastic surface is a plastic surface consisting of acrylonitrile / butadiene / styrene copolymer or a plastic surface comprising it, in which case the pretreatment of the plastic surface with composition C in step a) is carried out at 50 ° C. to 60 ° C. 12. A process according to any one of claims 1 to 11, which is carried out at a temperature in the range and over a period of 5 to 15 minutes.   In step b), the treatment of the plastic surface with an aqueous rinsing solution RS while applying ultrasound is carried out by applying the plastic surface from step a) in an ultrasonic bath containing the aqueous rinsing solution RS from 40 Watts / L to 60. At a power in the range of Watts / L for a period of 1 to 30 minutes and at a temperature of 40 ° C. to 60 ° C., wherein the aqueous rinse solution RS is at least 85% by weight of water The method according to claim 1, comprising: Step b) comprises the following steps:
b1) Treating the plastic surface from step a) with the first aqueous rinse solution RS1 by spraying the plastic surface with the first aqueous rinse solution RS1 or immersing the plastic surface in the first aqueous rinse solution RS1 The process of
14. The method according to any one of claims 1 to 13, comprising the step of b2) treating the plastic surface from step b1) with a second aqueous rinse solution RS2 while applying ultrasound. The electrochemical coating in step f) comprises the following steps:
f1) By treating the surface from step e) with a coating composition M2 comprising at least one copper compound and / or at least one nickel compound, the surface from step e) is essentially treated with copper and And / or electrochemically coating with a layer of nickel;
f2) Electrochemically coating the surface from step f1) with a layer consisting essentially of chromium by treating the surface from step f1) with a coating composition M3 comprising at least one chromium compound. 15. The method according to any one of claims 1 to 14, comprising a step.

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