Aqueous acidic copper electroplating bath and method for electrolytically depositing of a copper coating

Abstract

Aqueous acidic copper electroplating bath comprising: copper ions; at least one acid; halide ions; at least one sulfur containing compound selected form the group consisting of sodium 3-mercaptopropylsulfonate, bis(sodiumsulfopropyl)disulfide, 3-(N,N-dimethylthiocarbamoyl)-thiopropanesulfonic acid or the respective sodium salt thereof and mixtures of the aforementioned; at least one amine reaction product of diethylamine with epichlorohydrin or an amine reaction product of isobutyl amine with epichlorohydrin or mixtures of these reaction products; at least one ethylene diamine compound selected from the group having attached EO-PO-block polymers, attached EO-PO-block polymers and sulfosuccinate groups and mixtures thereof; at least one aromatic reaction product of benzylchloride with at least one polyalkylenimine and a method for electrolytically depositing of a copper coating using the electroplating bath.

Claims

1. Aqueous acidic copper electroplating bath comprising: 20 to 270 g/l of copper ions; 50 to 150 g/l of at least one acid; 40 to 160 mg/l of halide ions; at least one sulfur containing compound selected from the group consisting of sodium 3-mercaptopropylsulfonate, bis(sodiumsulfopropyl)disulfide, 3-(N,N-dimethylthiocarbamoyl)-thiopropanesulfonic acid and the respective sodium salt thereof; 5 to 200 mg/I of at least one of an amine reaction product of diethylamine with epichlorohydrin or an amine reaction product of isobutyl amine with epichlorohydrin or mixtures thereof wherein the at least one amine reaction product of diethylamine with epichlorohydrin or isobutyl amine with epichlorohydrin comprises a mixture of at least tertiary and/or quaternary ammonium compounds; at least one ethylene diamine compound selected from ethylene diamine compounds having attached EO-PO-block polymers, ethylene diamine compounds having attached EO-PO-block polymers and sulfosuccinate groups and mixtures thereof; at least one aromatic reaction product of benzylchloride with at least one polyalkylenimine, wherein the at least one aromatic reaction product comprises a benzylated polyalkylenimine or a mixture of benzylated polyalkylenimines; and one or more polyethylene glycol having a molecular weight from 1000 to 20000 g/mol.

2. The electroplating bath according to claim 1 wherein the benzylated polyalkylenimine or the mixture of benzylated polyalkylenimines has each 2 or more nitrogen atoms.

3. The electroplating bath according to claim 1 wherein, in the mixture of benzylated polyalkylenimines, the benzylated polyalkyleneimines contain benzylated polyalkylenimines having benzylated amino groups which are primary, secondary, or tertiary amino groups which are benzylated with 0 to 3 benzyl groups and wherein the benzylated amino groups can be interlinked to each other by alkylene groups with the proviso that at least one amino group is benzylated.

4. The electroplating bath according to claim 1 wherein the at least one aromatic reaction product is the aromatic reaction product of the benzylchloride with polyethylenimine.

5. The electroplating bath according to claim 1 wherein the attached EO-PO-block polymers have a molecular weight between 500 and 7000 g/mol and the attached EO-PO-block polymers have an EO/PO ratio of 0.88.

6. The electroplating bath according to claim 1 wherein the bath further comprises at least one inhibitor compound selected from the group consisting of one or more polypropylene glycol having a molecular weight from 400 to 2000 g/mol and EO-PO co-polymer having a molecular weight from 1000 to 10000 g/mol.

7. The electroplating bath according to claim 1 wherein the at least one amine reaction product of diethylamine with epichlorohydrin or isobutyl amine with epichlorohydrin comprises a quaternary ammonium compound.

8. The electroplating bath according to claim 1 wherein the at least one acid is selected from the group consisting of mineral acids, an alkylsulfonic acid, and mixtures thereof.

9. The electroplating bath according to claim 1 wherein the pH value of the bath is below 1.

10. The electroplating bath according to claim 1 wherein the bath further comprises a source of Fe (II) ions in a concentration of 50 to 1000 mg/I.

11. The electroplating bath according to claim 1 wherein the bath contains a mixture of amine reaction products, and total concentration of the mixture of amine reaction products in the bath is from 5 to 200 mg/l.

12. The electroplating bath according to claim 1 wherein the concentration of the at least one ethylene diamine compound in the bath is from 50 to 400 mg/l.

13. The electroplating bath according to claim 1 wherein the concentration of the at least one aromatic reaction product in the bath is from 0.1 to 6 mg/l.

14. Method for electrolytically depositing of a copper coating onto a substrate from the electroplating bath according to claim 1 comprising the steps in the following order: providing the substrate having a surface to be electroplated, bringing the substrate into contact with the bath having a temperature from 15° C. to 45° C., and applying a current between the substrate and an anode, and thereby depositing the copper coating onto the surface of the substrate.

15. Aqueous acidic copper electroplating bath comprising: 20 to 270 g/l copper ions; 50 to 150 g/l of at least one acid; 40 to 160 mg/l of halide ions; 5 to 50 mg/l bis(sodiumsulfopropyl)disulfide; 5 to 200 mg/L of at least one of an amine reaction product of diethylamine with epichlorohydrin or an amine reaction product of isobutyl amine with epichlorohydrin or mixtures thereof wherein the at least one amine reaction product of diethylamine with epichlorohydrin or isobutyl amine with epichlorohydrin comprises a mixture of at least tertiary and/or quaternary ammonium compounds; 20 to 250 mg/l of at least one ethylene diamine compound selected from ethylene diamine compounds having attached EO-PO-block polymers, ethylene diamine compounds having attached EO-PO-block polymers and sulfosuccinate groups and mixtures thereof; 0.1 to 6 mg/l of at least one aromatic reaction product of benzylchloride with at least one polyalkylenimine, wherein the at least one aromatic reaction product comprises a benzylated polyalkylenimine or a mixture of benzylated polyalkylenimines; one or more polyethylene glycol having a molecular weight from 1000 to 20000 g/mol; and one or more polypropylene glycol having a molecular weight from 400 to 2000 g/mol.

16. Method for electrolytically depositing of a copper coating onto a substrate from the electroplating bath according to claim 15 comprising the steps in the following order: providing the substrate having a surface to be electroplated, bringing the substrate into contact with the bath having a temperature from 15° C. to 45° C., and applying a current between the substrate and an anode, and thereby depositing the copper coating onto the surface of the substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) Preferred embodiments of the invention are explained in the following and also more detailed in the examples.

(2) The aqueous acidic copper electroplating bath according to the present invention is substantially free of dyes or dye-containing additives, respectively. That means, no dyes or dye-containing additives, such as phenazine dyes, in particular no strong-staining dyes under visible light (VIS) conditions are added to the electroplating bath because the dye-containing additives have the disadvantage of undesired strong levelling effects and also have very strong colours which stain the electrolyte, the equipment and the surrounding of the plating tank.

(3) The basic aqueous acidic copper electroplating bath may vary within wide limits. Generally, an aqueous acidic copper electroplating bath is used, having: copper (II) ions, preferably in a concentration from 20 to 300 g/l, more preferably from 120 to 270 g/l; at least one acid, preferably in a concentration from 50 to 350 g/l, more preferably from 50 to 150 g/l; halide ions preferably in a concentration from 10 to 250 mg/l, more preferably from 40 to 160 mg/l; a sulfur containing compound selected from the group consisting of sodium 3-mercaptopropylsulfonate, bis(sodiumsulfopropyl)disulfide (SPS), 3-(N,N-dimethylthiocarbamoyl)-thiopropanesulfonic acid the respective sodium salt thereof and mixtures of the aforementioned are added to the electroplating baths of the invention, preferably in a concentration from 2 to 70 mg/l, more preferably from 5 to 50 mg/l.

(4) As a source of copper ions preferably copper (II) sulfate (CuSO.sub.4×5H.sub.2O) is used. At least in parts, other copper salts than copper sulfate can be used.

(5) The at least one acid is preferably selected from the group consisting of a mineral acid, an alkylsulfonic acid, and mixtures thereof. In a preferred embodiment the at least one acid is sulfuric acid and/or hydrochloric acid as mineral acid, which also can be replaced in part by methanesulfonic acid and/or propanesulfonic acid. The pH value of the bath is preferably 1 or below 1.

(6) As halide ions preferably chloride ions are used and added preferably as alkali chloride (e.g. sodium chloride) or in the form of hydrochloric acid. The addition of halide ions can be omitted in part or in whole if the compounds or reaction products of the inventive electroplating bath already contain halide ions.

(7) To complete and provide the electroplating bath according to the invention, the further compounds and reaction products are added to the basic electroplating bath.

(8) The concentration of the amine reaction product of diethylamine with epichlorohydrin in the electroplating bath and the concentration of the amine reaction product of isobutyl amine with epichlorohydrin in the electroplating bath is from 5 to 200 mg/l. If mixtures of amine reaction products are used, the total concentration of the mixture in the bath is from 5 to 200 mg/l.

(9) According to the invention the amine reaction product of diethylamine with epichlorohydrin or isobutyl amine with epichlorohydrin comprises a mixture of at least tertiary and/or quaternary ammonium compounds, more preferred both reaction products comprise quaternary ammonium compounds. In an even more preferred embodiment an amine reaction product of diethylamine with epichlorohydrin is a product obtainable under CAS-No. 88907-36-2, CAS-No. 80848-16-4 or CAS-No. 80848-02-8.

(10) The at least one polyalkylenimine used for the reaction with benzylchloride has preferably 2 or more nitrogen atoms, preferably 2 to 60 nitrogen atoms, more preferred 2 to 50 nitrogen atoms, even more preferred 5 to 40 nitrogen atoms or 10 to 25 nitrogen atoms.

(11) The polyalkylenimine have preferably the general formula (I),

(12) ##STR00001##
wherein m and n are integers and m is 1-2 and n>2, preferably 2-60, more preferred 2 to 50, even more preferred 5 to 40 or 10 to 25.

(13) The used polyalkylenimines can be branched polyalkylenimines or linear polyalkylenimines or mixtures thereof. The linear polyalkylenimines contain predominantly secondary amino groups. The branched polyalkylenimines contain primary, secondary and tertiary amino groups. Preferably, the polyalkylenimine is a polyethylenimine or a polypropylenimine.

(14) The at least one aromatic reaction product of benzylchloride with polyalkylenimine means in this context a reaction products of benzylchloride with one or more polyalkylenimines resulting in a benzylated polyalkylenimine or benzylated polyalkylenimines forming a mixture. The benzylated polyalkylenimine or the benzylated polyalkylenimine of mixture has each 2 or more nitrogen atoms, preferred 2 to 60 nitrogen atoms, more preferred 2 to 50 nitrogen atoms, even more preferred 5 to 40 nitrogen atoms or 10 to 25 nitrogen atoms.

(15) In one embodiment of the invention, the reaction of a mixture of polyalkylenimine having each 5 to 40 nitrogen atoms with benzylchloride results in an aromatic reaction product comprising benzylated polyalkylenimines having nitrogen atoms, e.g. 5 to 40 nitrogen atoms forming a mixture.

(16) Preferably the benzylated polyalkylenimines or mixture of benzylated polyalkylenimines contains benzylated polyalkylenimines having benzylated amino groups which are primary, secondary, or tertiary amino groups which are benzylated with 0 to 3 benzyl groups and wherein the benzylated amino groups can be interlinked to each other by alkylene (also referred to as alkanediyl groups in the art) groups with the proviso that at least one amino group is benzylated.

(17) In a more preferred embodiment the at least one aromatic reaction product is an aromatic reaction product of benzylchloride with polyethylenimine. Preferably, the polyethylenimine has 2 to 60 nitrogen atoms, more preferred 2 to 50 nitrogen atoms, even more preferred 50 to 40 nitrogen atoms or 10 to 25 nitrogen atoms. More preferably the polyethylenimine has 2 to 60 nitrogen atoms, more preferred 2 to 50 nitrogen atoms, even more preferred 5 to 40 nitrogen atoms or 10 to 25 nitrogen atoms.

(18) In a more preferred embodiment a benzylated polyalkylenimine is a product obtainable under CAS-No. 68603-67-8.

(19) The concentration of the at least one aromatic reaction product in the electroplating bath is from 0.1 to 6 mg/l, preferably from 1 to 5 mg/l. If mixtures of aromatic reaction products are used, the total concentration of the mixture in the electroplating bath is from 1 to 5 mg/l.

(20) In the preferred embodiment of the invention the concentration in the electroplating bath of the at least one the ethylene diamine compounds which have attached EO-PO-block polymers only, or attached EO-PO-block polymers and sulfosuccinate groups or mixtures thereof is from 50 to 400 mg/l. EO-PO-block polymers in this context means polymers without having cap-groups as sulfosuccinate groups. If mixtures of ethylene diamine compounds are used, the total concentration of the mixture in the electroplating bath is from 50 to 400 mg/l, preferably from 20 to 250 mg/l.

(21) Preferably, the attached EO-PO-block polymer of the ethylene diamine compounds has a molecular weight between 500 and 7000 g/mol and preferably the block polymer has an EO/PO ratio of 0.88.

(22) In a more preferred embodiment an ethylene diamine compound having attached EO-PO-block polymers only is a product obtainable under CAS No. 26316-40-5. In another preferred embodiment of an ethylene diamine compound which have attached EO-PO-block polymers and sulfosuccinate groups is a product obtainable under CAS No. 26316-40-5sulf (sulf means sulfosuccinated).

(23) If higher levelling performance beside the still improved brightness of the coatings is needed, the concentration of the additives—amine reaction product, ethylene diamine compound and aromatic reaction product—can be adjusted at higher concentrations to provide more levelled coatings, wherein the concentration of the at least one amine reaction product of diethylamine with epichlorohydrin is from 50 to 200 mg/l preferably from 50 to 150 mg/l; the concentration of the at least one ethylene diamine compound is from 50 to 400 mg/l and the concentration of at least one aromatic reaction product is from 0.1 to 6 mg/l.

(24) In a preferred embodiment of the invention the electroplating bath additionally comprises at least one inhibitor compound selected from the group consisting of one or more polyethylene glycols having a molecular weight from 1000 to 20000 g/mol, preferably between 3000 and 10000 g/mol; polypropylene glycol having a molecular weight from 400 to 2000 g/mol; and EO-PO co-polymer (block or random) having a molecular weight from 1000 to 10000 g/mol, preferably from 1000 to 1500 g/mol. The concentration of the inhibitor compound in the bath is from 0.5 to 200 mg/l. If mixtures of inhibitor compounds are used, the total concentration of the mixture in the electroplating bath is from 7 to 200 mg/l.

(25) Preferred inhibitors which can be used alone or in combination are PEG-DME 2000, PEG 6000, PEG 10000 and PPG 900.

(26) The inhibitor compound helps to prevent or further reduces the formation of pores within the copper coatings.

(27) In a preferred embodiment of the invention the electroplating bath additionally comprises further Fe (II) ions in a concentration of 50 to 1000 mg/l. The addition of Fe (II) ions has positive influences of the consumptions of organic additives. The Fe (II) ions preferably derived from water soluble iron salts, e.g. FeSO.sub.4×7H.sub.2O.

(28) The invention further provides a method for electrolytically depositing of a copper coating onto a substrate from an electroplating bath according to the invention above comprising the steps in the following order: providing the substrate having a surface to be electroplated, bringing the substrate into contact with the electroplating bath, and applying a current between the substrate and an anode, and thereby depositing a copper coating onto the surface of the substrate.

(29) The operating conditions of the bath during deposition can preferably be adjusted as follows: pH value: <1, Temperature: 15° C. to 45° C., preferably from 20° C. to 35° C., Cathodic current density: 0.5 to 12 A/dm.sup.2, preferably from 2 to 6 A/dm.sup.2

(30) The electrolyte motion can be caused by electrolyte circulation, cathode movement and/or blowing in air.

(31) The following examples are used to explain the invention and are not-limiting:

(32) General Procedure:

(33) The plating experiments were conducted in a Hull-cell in order to simulate a wide range of local current densities on the substrate (“Hull-cell panel”) during electroplating. The substrate material was brass and the size was 100 mm×75 mm.

(34) The desired technical effect of an improved brightness performance of the plating bath was determined by visual inspection of the deposited copper coatings in view of brightness over the whole Hull-cell panel. The inspection of the Hull cell panels was made from high local current density (HCD) point to the low local current density (LCD) point of the Hull cell panels. The HCD point was specified as a starting point from the left border of the Hull cell. Starting at this point, the current density over the Hull cell panel decreases locally step by step to the LCD point at the right border of the Hull cell panel. The distance from the left to the right border of the Hull cell panels refers to a value of 100%, if no changes over the length of 100 mm in brightness in direction to the LCD point is observed. If e.g. 90% of the distance in direction of the LCD point is not visual changed, the remaining 10% of the distance in direction to LCD point of the Hull cell panel is visual decrease in quality of brightness in contrast to the remaining 90%.

(35) The brightness performance of the plating bath tested was determined by the visual inspection of the Hull cell panel between HCD and LCD point, and the effect of the different additives alone or in combination was determined by comparing the panels prepared, using a basic aqueous acidic copper electroplating bath with different additives alone or in combination as explained in the examples.

(36) The applied electrical current at the left border of the Hull cell panel was 2 A. Plating time was 10 min. Temperature of the bath was 25° C.

(37) Basic aqueous acidic copper electroplating:

(38) TABLE-US-00001 CuSO.sub.4 × 5H.sub.2O 220.0 g/l Sulfuric acid (96% per weight) 70.0 g/l NaCl 80.0 mg/l

(39) The indication of concentration of the additives within the examples refers to final concentrations of the plating bath.

Example 1-3 (Comparative Examples)

Example 1

(40) The brightness performance of a basic aqueous acidic coper electroplating bath comprising 1a) 20 mg/l 3-mercaptopropylsulfonate (SPS) and 200 mg/l PEG 6000, 1b) composition 1a)+30 mg/l amine reaction product of diethylamine with epichlorohydrin (CAS-No. 88907-36-2), 1c) composition 1b)+40 mg/l ethylene diamine compound which have attached EO-PO-block polymers (EO-PO EDA; CAS No. 26316-40-5) were tested. The Hull cell panel showed over a distance of:

(41) 1a) 60% a semi-bright to weak-bright coating and 40% satin appearance;

(42) 1b) 70% a weakly bright and 30% satin coating;

(43) 1c) 80% a weakly bright and 20% satin coating.

Example 2

(44) The brightness performance of a basic aqueous acidic coper electroplating bath comprising 2a) 5 mg/l SPS, 50 mg/l PEG 6000 and 80 mg/l ethylene diamine compound which have attached EO-PO-block polymers (EO-PO EDA; CAS No. 26316-40-5), 2b) composition 2a)+25 mg/l amine reaction product of diethylamine with epichlorohydrin (CAS-No. 88907-36-2), 2c) composition 2b)+25 mg/l amine reaction product of diethylamine with epichlorohydrin (CAS-No. 88907-36-2), 2d) composition 2c)+50 mg/l amine reaction product of diethylamine with epichlorohydrin (CAS-No. 88907-36-2) were tested.

(45) The Hull cell panel showed over a distance of:

(46) 2a) 70% a semi-bright to weak-bright coating and 30% satin appearance;

(47) 2b) 70% a semi-bright to weak-bright coating and 30% satin appearance;

(48) 2c) 70% a semi-bright to weak-bright coating and 30% satin appearance;

(49) 2d) 70% a semi-bright to weak-bright coating and 30% satin appearance.

Example 3

(50) The brightness performance of a basic aqueous acidic coper electroplating bath comprising 3a) 20 mg/l SPS and 200 mg/l EO-PO (random, average molar mass M.sub.w: 1100-1300 g/mol) 3b) composition 3a)+0.8 mg/l benzylated polyalkylenimine (CAS-No. 68603-67-8); 3c) composition 3a)+1.6 mg/l benzylated polyalkylenimine (CAS-No. 68603-67-8); and 3d) composition 3a)+3.2 mg/l benzylated polyalkylenimine (CAS-No. 68603-67-8) were tested.

(51) The Hull cell panel showed over a distance of:

(52) a) 75% a semi-bright to weak-bright coating;

(53) b) 85% a semi-bright to weak-bright coating;

(54) c) 50% a bright and 50% satin bright coating;

(55) d) 65% a bright and 35% satin bright coating.

Example 4 (Inventive Example)

(56) The brightness performance of a basic aqueous acidic coper electroplating bath comprising 4a) 5 mg/l SPS, 50 mg/l PEG 6000, 40 mg/l ethylene diamine compound having attached EO-PO-block polymers (EO-PO EDA; CAS No. 26316-40-5), 30 mg/l amine reaction product of diethylamine with epichlorohydrin (CAS-No. 88907-36-2), and 0.4 mg/l benzylated polyalkylenimine (CAS-No. 68603-67-8) was tested.

(57) The Hull cell panel showed over a distance of

(58) 4a) 85% a bright coating and 15% satin bright coating.

Examples 5-7 (Inventive Examples)

(59) For the following inventive examples comparable substrates were used as above but the substrates were provided with identically arranged scratches over the whole surface of the substrate. According to the basic aqueous acidic copper electroplating bath, it was slightly altered in concentration of SPS from 7 to 31 mg/l according to the examples:

(60) TABLE-US-00002 CuSO.sub.4 × 5H.sub.2O 220.0 g/l Sulfuric acid (96% per weight) 70.0 g/l NaCl 130.0 mg/l

(61) The desired technical effect of an improved brightness and levelling performance of the plating bath was determined again by visual inspection of the deposited copper coatings in view of brightness and levelling over the whole Hull-cell panel.

(62) The examples showed that higher concentrations of the additives (i.e. the amine reaction product, the ethylene diamine compound and the aromatic reaction product) of the inventive electroplating bath results beside good brightness and levelling performance also in an additionally improved levelling performance.

Example 5 (Inventive Example)

(63) The brightness and levelling performance of a basic aqueous acidic coper electroplating bath comprising 5a) 38.0 mg/l amine reaction product of diethylamine with epichlorohydrin (CAS-No. 68391-06-0), 50.0 mg/l ethylene diamine compound which have attached EO-PO-block polymers (EO-PO EDA; CAS No. 26316-40-5), 2.0 mg/l benzylated polyalkylenimine (CAS-No. 68603-67-8), 15 mg/l PEG 6000 and 25.0 mg/l SPS; and 5b) 94.0 mg/l amine reaction product of diethylamine with epichlorohydrin (CAS-No. 88907-36-2), 125.0 mg/l ethylene diamine compound which have attached EO-PO-block polymers (EO-PO EDA; CAS No. 26316-40-5), 5.0 mg/l benzylated polyalkylenimine (CAS-No. 68603-67-8), 40 mg/l PEG 6000 and 13.0 mg/l SPS, was tested.

(64) The Hull cell panel showed over a distance of

(65) 5a) 80% a bright and 20% satin bright coating plus additionally weak levelling effect;

(66) 5b) 80% a bright and 20% satin bright coating plus very strong levelling effect.

Example 6 (Inventive Example)

(67) The brightness and levelling performance of a basic aqueous acidic coper electroplating bath comprising 6a) 50.0 mg/l amine reaction product of diethylamine with epichlorohydrin (CAS-No. 88907-36-2, 130.0 mg/l ethylene diamine compound which have attached EO-PO-block polymers and sulfosuccinate groups (EO-PO EDAsulf; CAS No. 26316-40-5sulf), 1.0 mg/l benzylated polyalkylenimine (CAS-No. 68603-67-8), 25 mg/l PEG 6000 and 7.0 mg/l SPS; and 6b) 150.0 mg/l amine reaction product of diethylamine with epichlorohydrin (CAS-No. 88907-36-2), 390.0 mg/l ethylene diamine compound which have attached EO-PO-block polymers and sulfosuccinate groups (EO-PO EDAsulf; CAS No. 26316-40-5sulf), 3.0 mg/l benzylated polyalkylenimine (CAS-No. 68603-67-8), 80 mg/l PEG 6000 and 13.0 mg/l SPS, was tested.

(68) The Hull cell panel showed over a distance of

(69) 6a) 75% a bright and 25% satin bright coating plus additionally weak levelling effect;

(70) 6b) 85% a bright and 15% satin bright coating plus very strong levelling effect.

Example 7

(71) The brightness and levelling performance of a basic aqueous acidic coper electroplating bath comprising 7a) 5.0 mg/l amine reaction product of diethylamine with epichlorohydrin (CAS-No. 88907-36-2), 20.0 mg/l ethylene diamine compound which have attached EO-PO-block polymers and sulfosuccinate groups (EO-PO EDAsulf; CAS No. 26316-40-5sulf), 4.0 mg/l ethylene diamine compound which have attached EO-PO-block polymers (EO-PO EDA; CAS No. 26316-40-5), 0.2 mg/l benzylated polyalkylenimine (CAS-No. 68603-67-8), 5 mg/l PEG 6000 and 8.0 mg/l SPS; and 7b) 50.0 mg/l amine reaction product of diethylamine with epichlorohydrin (CAS-No. 88907-36-2), 200.0 mg/l ethylene diamine compound which have attached EO-PO-block polymers and sulfosuccinate groups (EO-PO EDAsulf; CAS No. 26316-40-5sulf), 40.0 mg/l ethylene diamine compound which have attached EO-PO-block polymers (EO-PO EDA; CAS No. 26316-40-5), 2.0 mg/l benzylated polyalkylenimine (CAS-No. 68603-67-8), 50 mg/l PEG 6000 and 31.0 mg/l SPS, was tested.

(72) The Hull cell panel showed over a distance of

(73) a) 75% a bright and 25% satin bright coating plus additionally weak levelling effect;

(74) b) 85% a bright and 15% satin bright coating plus very strong levelling effect.