DE102006027762A1 - Sided phosphonic acid ester group-containing copolymers of olefinically unsaturated monomers, process for their preparation and their use - Google Patents

Abstract

Polyisocyanate-saturated monomers containing acidic phosphonic acid ester groups which can be prepared by reacting (A) at least one free-radically polymerizable acidic phosphonic acid ester prepared by reacting (A1) at least one phosphonic acid of the general formula I: RP (= O) (- OH) <SUB> 2 </ SUB> in which R is a substituted or unsubstituted, heteroatom-containing or free organic radical containing at least one radically polymerizable carbon-carbon double bond, with (A2) at least one of radically polymerizable groups substantially or completely free, an epoxide group-containing compound in an equivalent ratio of acid group (P-OH) to epoxide group = 2: 1 to 1.2: 1; with (B) at least one of (A) different radically polymerizable monomers radically polymerized; Process for their preparation and their use.

Description

Field of the invention

The The present invention relates to novel, pendant acid phosphonic acid ester groups containing copolymers of olefinically unsaturated monomers. It also concerns the present invention provides a novel process for the preparation of pendant acid phosphonic acid ester groups containing copolymers of olefinically unsaturated monomers. Not least The present invention relates to the use of the new, pendant acid phosphonic containing copolymers of olefinically unsaturated monomers and according to produced by the new process, pendant acid phosphonic acid ester groups containing copolymers of olefinically unsaturated monomers.

State of the art

Water-based paints, as in the automotive OEM and automotive refinish for the Production of multicoat color and / or effect paint systems used often contain Metal effect pigments, in particular aluminum effect pigments. These but are in watery Media unstable and prone to gassing, d. H. for the formation of hydrogen. The formation of hydrogen is but in storage and the High safety risk. In addition, the waterborne basecoats, which have been produced from these gassing waterborne basecoats, no longer the specifications, but point in terms of the Metallic effect, the overall visual impression, the color, the surface texture, the History, etc. disadvantages.

The gassing of the aluminum effect pigments can to some extent by the surface passivation with reaction products of vinyl phosphonic acid with polyepoxides having a number average molecular weight of 300 to 5000 daltons and optionally monoepoxides such as Versatic ^® -10-glycidyl acid ester (2,2-Dimethyloctansäure-glycidylester; Cardura ^® E10) can be suppressed (cf the European patent EP 1 213 334 B1 ). However, the known passivation layers still tend to form pinholes or pinholes, which provide points of attack for the aqueous medium and yet again lead to gases. However, this means that the safety hazard caused by the formation of hydrogen is still present and the aqueous basecoats produced from the waterborne basecoats are in need of improvement in terms of their metallic effect, their overall visual impression, their color, their surface structure and their course.

task

task It is the object of the present invention to provide novel, metallic effect pigments, in particular Aluminum effect pigments, containing, aqueous coating materials, especially water-based paints, which do not or only to a very small extent for gases, d. H. for the formation of hydrogen, tend. In particular, gassing should be <10 ml / 4 weeks. The new, watery Coating materials are color and / or effect coatings, in particular basecoats of color and / or effect Multicoat paint systems, which had an excellent surface structure, which is free of paint defects, an excellent course, an excellent metallic effect without light / dark shades (clouds), an outstanding optical Overall impression, excellent opacity, reproducible at any time Color location and have an excellent color effect.

Not last should cost-effective Metal effect pigments, in particular aluminum effect pigments used can be the none by elaborate Methods such as chromating produced passivation layers wear.

Inventive solution

• (A) mindestens einen radikalisch polymerisierbaren sauren Phosphonsäureester, herstellbar durch Umsetzung (A1) mindestens einer Phosphonsäure der allgemeinen Formel I: R-P(=O)(-OH)₂ (I), worin R für einen mindestens eine radikalisch polymerisierbare Kohlenstoff-Kohlenstoff-Doppelbindung enthaltenden, substituierten oder unsubstituierten, Heteroatome enthaltenden oder hiervon freien, organischen Rest steht; mit (A2) mindestens einer von radikalisch polymerisierbaren Gruppen im Wesentlichen oder völlig freie, eine Epoxidgruppe enthaltenden Verbindung in einem Äquivalentverhältnis von Säuregruppe (P-OH) zu Epoxidgruppe = 2 : 1 bis 1,2 : 1; mit
• (B) mindestens einem von (A) verschiedenen, radikalisch polymerisierbaren Monomeren

radikalisch polymerisiert und die im Folgenden als »erfindungsgemäße Copolymerisate« bezeichnet werden.Accordingly, the new, pendant acid phosphonic acid ester group-containing copolymers of olefinically unsaturated monomers were found which can be prepared by

• (A) at least one free-radically polymerizable acidic phosphonic acid ester preparable by reaction (A1) of at least one phosphonic acid of the general formula I: RP (= O) (-OH) ₂ (I), wherein R is a substituted or unsubstituted, heteroatom-containing or free organic radical containing at least one radically polymerizable carbon-carbon double bond; with (A2) at least one of radically polymerizable groups substantially or completely free, an epoxy group-containing compound in an equivalent ratio of acid group (P-OH) to epoxy group = 2: 1 to 1.2: 1; With
• (B) at least one of (A) different radically polymerizable monomers

free-radically polymerized and which are referred to below as "copolymers according to the invention".

It was also a new process for the preparation of the novel copolymers in which at least one free-radically polymerizable, acidic phosphonic acid ester (A) and at least one radically polymerizable monomer (B) in bulk, solution or dispersion radically copolymerized and the following referred to as "inventive method" becomes.

Not last was the new use of the novel copolymers and the method according to the invention prepared copolymers according to the invention as functional additives, in particular for the production of coating materials, Adhesives, sealants and precursors for moldings and films found, which hereinafter referred to as "inventive use" becomes.

Advantages of the invention

in the In view of the prior art, it was surprising and for the expert unpredictable that the task of the present invention underlying, with the aid of the novel copolymers, the inventive method and the use according to the invention solved could be.

Especially it was surprising it is the copolymers according to the invention and the method according to the invention prepared copolymers according to the invention permitted new metallic effect pigments, in particular aluminum effect pigments, containing, aqueous To provide coating materials, in particular aqueous basecoats, not or only to a very limited extent for gasing, d. H. to Formation of hydrogen, tended. Surprisingly, the Gassing be lowered below 10 ml / 4 weeks.

The new, watery Coating materials provided color and / or effect coatings, in particular Basecoats of multicoat color and / or effect coatings, the excellent surface structure, the free of paint defects was, an excellent course, an excellent metallic effect without light / dark shades (clouds), an outstanding optical Overall impression, excellent opacity, reproducible at any time Color location and a great color effect.

Not last could due to the novel copolymers, with Help of the method according to the invention prepared copolymers and the use according to the invention inexpensive metallic effect pigments, In particular, aluminum effect pigments are used, the no through elaborate procedures how the chromating passivation layers wear more had.

Detailed description of the invention

The copolymers according to the invention are copolymers of olefinically unsaturated monomers and carry pendant or lateral acid phosphonic acid ester groups.

Acid phosphonic are formed by only one of the two acid functions P-OH of the phosphonic acid group is esterified.

The copolymers according to the invention are formed by the radical polymerization at least one, in particular one, radically polymerizable acidic phosphonate (A).

• (A1) mindestens einer Phosphonsäure der allgemeinen Formel I: R-P(=O)(-OH)₂ (I),worin R für einen mindestens eine, insbesondere eine, radikalisch polymerisierbare Kohlenstoff-Kohlenstoff-Doppelbindung enthaltenden, substituierten oder unsubstituierten, Heteroatome enthaltenden oder hiervon freien, organischen Rest steht; mit
• (A2) mindestens einer, insbesondere einer, von radikalisch polymerisierbaren Gruppen im Wesentlichen oder völlig freien, eine Epoxidgruppe enthaltenden Verbindung in einem Äquivalentverhältnis von Säuregruppe (P-OH) zu Epoxidgruppe = 2 : 1 bis 1,2 1, insbesondere 2 : 1 bis 1,5 : 1; mit
• (B) mindestens einem, insbesondere mindestens zwei, von (A) verschiedenen, radikalisch polymerisierbaren Monomeren.

The phosphonic acid ester (A) can be prepared by the reaction

• (A1) at least one phosphonic acid of the general formula I: RP (= O) (-OH) ₂ (I), wherein R is at least one, in particular a, radically polymerizable carbon-carbon double bond-containing, substituted or unsubstituted, heteroatom-containing or free thereof, organic radical; With
• (A2) at least one, in particular one, of radically polymerizable groups substantially or completely free, an epoxy group-containing compound in an equivalent ratio of acid group (P-OH) to epoxy = 2: 1 to 1.2 1, in particular 2: 1 to 1.5: 1; With
• (B) at least one, in particular at least two, of (A) different radically polymerizable monomers.

What the phosphonic acid (A1) of general formula I, the phosphorus is the phosphonic acid group preferably with one carbon atom of the carbon-carbon double bond the organic radical R connected.

When organic radicals R can all usual and known, radically polymerizable double bonds containing Remains are used.

The organic radicals R can be substituted. Substituents are all atoms and radicals in Consider the implementation of the phosphonic acid (A1) with the epoxide groups the compounds (A2) and the later Copolymerization of the monomers (A) do not interfere, for example by inhibition, excessive acceleration, decomposition and / or formation of by-products.

Preferably the substituents are selected from the group consisting of fluorine, chlorine, Bromine and iodine atoms, nitrile groups and nitro groups selected.

The The aforementioned substituents can also be found in the following be described residues and groups.

Prefers the organic radicals R are unsubstituted.

The organic radicals R can Furthermore Heteroatoms, preferably up to 20 heteroatoms. Also the heteroatoms are allowed the implementation of phosphonic acid (A1) with the epoxide groups of the compounds (A2) and the subsequent copolymerization do not disturb the monomers (A), for example by inhibition, too strong acceleration, decomposition and / or the formation of by-products.

Preferably the heteroatoms are selected from the group consisting of boron, silicon, Nitrogen, phosphorus, oxygen and sulfur.

The mentioned heteroatoms can also contained in the radicals and groups described below be.

Prefers the organic radicals R are free of heteroatoms.

Especially The organic radicals R are preferably selected from the group consisting from vinyl, styryl-dicyclopentadienyl, norbornenyl, isoprenyl, Isopropenyl, allyl or butenyl groups, in particular vinyl groups, selected. Accordingly, vinylphosphonic acid particularly preferably used as phosphonic acid (A1).

at the reaction partner (A2) is an epoxy group-containing Compound that is substantially or completely free of radically polymerizable Is groups. Here, in the "essentially free" means that only such a small number of free-radically polymerizable double bonds that is present at the later radical copolymerization of the monomers (A) no gelation the copolymers according to the invention entry.

worin die Variablen die folgende Bedeutung haben:
X zweibindige verküpfende Gruppe,
R¹ substituierter oder unsubstiuierter, vorzugsweise unsubstituierter, Heteroatome enthaltender oder hiervon freier, vorzugsweise freier, einbindiger, organischer Rest, der mindestens eine, insbesondere eine, Gruppe, ausgewählt aus der Gruppe, bestehend aus aliphatischen, cycloaliphatischen und aromatischen Gruppen, enthält oder hieraus besteht,
R² unabhängig voneinander Wasserstoffatom, substituierter oder unsubstituierter, vorzugsweise unsubstituierter, Heteroatome enthaltender oder hiervon freier, vorzugsweise freier, einbindiger, organischer Rest, der mindestens eine, insbesondere eine, Gruppe, ausgewählt aus der Gruppe, bestehend aus aliphatischen, cycloaliphatischen und aromatischen Gruppen, enthält oder hieraus besteht,
R³ substituierter oder unsubstituierter, vorzugsweise unsubstiuierter, Heteroatome enthaltender oder hiervon freier, vorzugsweise freier, mindestens eine, insbesondere eine, aromatische Gruppe enthaltender oder hiervon freier, zweibindiger aliphatischer Rest;
ausgewählt.Suitable compounds (A2) are all customary and known monoepoxides. Preferably, the monoepoxides (A2) are selected from the group consisting of compounds of general formulas II, III and IV:

wherein the variables have the following meaning:
X two-linked linking group,
R ^{1 is} substituted or unsubstituted, preferably unsubstituted, heteroatom-containing or free thereof, preferably free, monovalent organic radical which contains or consists of at least one, in particular one, group selected from the group consisting of aliphatic, cycloaliphatic and aromatic groups .
R ^{2 are} independently hydrogen, substituted or unsubstituted, preferably unsubstituted, heteroatom-containing or free, preferably free, monovalent, organic radical containing at least one, in particular one, group selected from the group consisting of aliphatic, cycloaliphatic and aromatic groups, contains or consists of
R ^{3 is} substituted or unsubstituted, preferably unsubstituted, heteroatom-containing or free thereof, preferably free, at least one, in particular one, aromatic group-containing or free thereof, divalent aliphatic radical;
selected.

Preferably, in the general formula II, the monovalent radical R ^{1 is} a substituted or unsubstituted, preferably unsubstituted, heteroatom-containing or free thereof, preferably free, aliphatic group having 3 to 20 carbon atoms.

Preferably, in the general formula III, the two radicals R ^{2 are} hydrogen atoms.

However, it is also possible to use one of the two radicals R ² for a hydrogen atom and the other radical R ² for a substituted or unsubstituted, preferably unsubstituted, heteroatom-containing or free thereof, preferably free, aliphatic group having 1 to 6 carbon atoms, a substituted or unsubstituted preferably unsubstituted, heteroatom-containing or free thereof, preferably free, cycloaliphatic group having 3 to 8 carbon atoms or a substituted or unsubstituted, preferably unsubstituted, heteroatom-containing or free thereof, preferably free, aromatic group having 6 to 20 carbon atoms.

However, the two radicals R ² may also be identical or different, substituted or unsubstituted, preferably unsubstituted, containing hetero atoms or free thereof, preferably free, aliphatic groups having 1 to 6 carbon atoms, substituted or unsubstituted, preferably substituted, heteroatoms or free thereof , preferably free, cycloaliphatic groups having 3 to 8 carbon atoms or substituted or unsubstituted, preferably substituted, heteroatom-containing or free thereof, preferably free, aromatic groups having 6 to 20 carbon atoms.

Preferably, in the general formula IV, the radical R ^{3 is} a substituted or unsubstituted, preferably unsubstituted, heteroatom-containing or free thereof, preferably free, divalent, aliphatic radical having 2 to 20 carbon atoms or such a divalent aliphatic radical which is a substituted or unsubstituted, preferably unsubstituted, heteroatom-containing or free thereof, preferably free, aromatic group having 6 to 20 carbon atoms.

Examples of suitable compounds (A2) are from the European patent EP 1 213 334 B1 , Page 4, paragraphs [0019] and [0020].

Preference is given to monoepoxides (A2) of the general formula II in which the monovalent radical R ^{1 is} a heteroatom-free, aliphatic group having 4 to 10 carbon atoms. Particularly preferred is the monovalent, heteroatom-free, aliphatic radical R ¹ branched. Most preferably, the monovalent aliphatic radical R ^{1 is selected} from the group consisting of 1,1-dimethyl-eth-1-yl, 1,1-dimethyl-prop-1-yl, 1,1-dimethyl-but-1 -yl, 1,1-dimethyl-pent-1-yl, 1,1-dimethyl-hex-1-yl, 1,1-dimethylhept-1-yl and 1,1-dimethyl-oct-1-yl , selected.

When zweifindige verkuppfende Group X basically come all the usual and known, dodo linking groups of the organic Chemistry involving the conversion of the phosphonic acid (A1) with the epoxide groups of the compounds (A2) and the subsequent copolymerization the monomers (A) do not interfere, for example by inhibition, excessive acceleration, decomposition and / or the formation of by-products. Preference is given to the divalent linking group X is an ether group or a carboxyl group in which the oxygen atom is linked to the methylene group. In particular, the two-letter verkupfenende group X is a carboxyl group.

As a result, are the compounds or monoepoxides (A2) in particular from Group consisting of glycidyl esters of 2,2-dimethylpropionic acid, -butyric acid, -pentanoic acid, -hexanoic acid, -heptanoic acid and octanoic acid, selected.

The Preparation of free-radically polymerizable acid phosphonic acid esters (A) from the above-described compounds (A1) and (A2) has no methodological features, but can help with the procedures and devices are carried out, as they usually do be used in the implementation of epoxides. Possibly can be more common in the present and known catalysts are worked. Preferably the reaction at a temperature of 30 to 150 ° C, in particular 50 to 100 ° C carried out. Preferably, the reaction is carried out until an epoxide equivalent weight> 50,000 is reached.

at the method according to the invention be the radical polymerizable described above acidic phosphonic acid ester (A) having at least one different radically polymerizable Monomers (B) copolymerized. At least two are preferred Monomers (B) used.

in the Basically can all radically polymerizable monomers (B) are used, as they usually do for the Preparation of oligomers and polymers are used.

It is according to the invention but beneficial if the monomers (B) are substantially or completely free hydrophilic groups, in particular (potentially) ionic groups, such as As carboxyl groups or amino groups, are.

Preferably the radically polymerizable monomers (B) are selected from the group consisting of olefins, cycloolefins, vinylaromatics and olefinic unsaturated ethers, Thioethers, carboxylic esters, thiocarboxylic acid esters, Carbonates, thiocarbonates, phosphoric acid esters, thiophosphoric esters, phosphonates, Thiophosphonsäureestern, Phosphites, thiophosphites, sulfonic acid esters, amides, amines, Thioamides, phosphoric acid amides, Thiophosphorsäureamiden, Phosphonic acid amides, thiophosphonic acid amides, sulfonamides, Imides, hydrazides, urethanes, ureas, thioureas, carbonyls, Thiocarbonyls, sulfones, sulfoxides and siloxanes.

Prefers the radically polymerizable monomers (B) are selected from the group consisting of olefins, cycloolefins, vinylaromatics, olefinic unsaturated Ethers, olefinically unsaturated Carbonsäureestern and olefinically unsaturated Siloxanes, selected.

Especially the olefins (B) are preferably selected from the group consisting of ethene, Propene, isoprene, 1-butene, isobutene 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, butadiene, isoprene, acrylonitrile, vinyl chloride, Vinyl fluoride, vinylidene difluoride and tetrafluoroethylene.

Especially the cycloolefins (B) are preferably selected from the group consisting from cyclopentene, cyclohexene, cycloheptene, cyclooctene, dicyclopentadiene and norbornene, selected.

The vinylaromatics (B) are particularly preferably selected from the group consisting of styrene, alpha-alkylstyrene and compounds of the general formula V: R ⁴ R ⁵ C = CR ⁶ R ⁷ (V), wherein the radicals R ⁴ , R ⁵ , R ⁶ and R ^{7 are} each independently hydrogen or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals with the proviso that at least two of the variables R ⁴ , R ⁵ , R ⁶ and R ^{7 are} substituted or unsubstituted aryl, arylalkyl or Arylcycloalkylreste, as described for example in German Patent Application DE 199 59 923 A1 , Page 7, line 45, to page 8, line 8, are selected.

Prefers are the olefinically unsaturated Ether (B) from the group consisting of vinyl ethers, allyl ethers, Butenyl ethers, cyclohexenyl ethers, dicyclopentadienyl ethers and Norbornenyl ethers, more preferably the corresponding alkyl ethers, selected.

Prefers are the olefinically unsaturated Carbonsäureester (B) from the group consisting of (meth) acrylates, ethacrylates, Crotonates, cinnamates, maleates, fumarates and vinyl esters, particularly preferred the (meth) acrylates, most preferably the alkyl and cycloalkyl (meth) acrylates, in particular the alkylalkyl (meth) acrylates having 1 to 20 carbon atoms in the alkyl radical and cycloalkyl (meth) acrylates having 5 to 20 carbon atoms in the cycloalkyl radical.

Prefers are the olefinically unsaturated Siloxanes (B) from the group consisting of vinyl, allyl, vinyl ether, Allyl ether- and / or (meth) acryloyl-containing polysiloxanes, selected.

at the preparation of the copolymers according to the invention, the weight ratio of the monomers (A) to (B) vary widely and thus the requirements be optimally adapted to the individual case. Preferably included the copolymers according to the invention, in each case based on a copolymer, the monomer (A) in a Amount of 5 to 70 wt .-%, preferably 10 to 60 wt .-%, especially preferably 15 to 55% by weight and in particular 20 to 45 wt .-% copolymerized.

From a methodological point of view, the preparation of the copolymers according to the invention by the process according to the invention has no special features, but the apparatuses and processes can be used which are conventionally used in free-radical polymerization. Preferably, the monomers (A) and (B) are radically copolymerized in bulk, solution or dispersion, preferably in solution. In this case, the customary and known organic solvents can be used. The radical copolymerization can be carried out in one stage or in at least two stages. The copolymerization is preferred in the presence of conventional and known radical initiators, as described for example in German Patent Application DE 199 48 004 A1 , Page 13, lines 14 to 19, or the German patent application DE 199 59 923 A1 , Page 8, lines 14 to 25, performed. Preferably, the copolymerization temperature is 50 to 200 ° C, preferably 60 to 150 ° C and especially 70 to 120 ° C. The reaction time is preferably from 1 to 24 hours, preferably from 2 to 20 hours and in particular from 3 to 15 hours.

The copolymers according to the invention and the method according to the invention prepared copolymers according to the invention can in more diverse Be used way.

Preferably will you for the use according to the invention used as functional additives. Under a functional additive is a substance that is already in small quantities causes a significant technical effect.

Especially serve the functional according to the invention Additives of the production of coating materials, adhesives, Sealants and precursors for Moldings and foils for the production of coatings, adhesive layers, seals, molded parts and slides are used.

Preferably serve the functional according to the invention Additives of the preparation of coating materials, preferably aqueous Coating materials and in particular aqueous coating materials, the Metallic effect pigments included.

Especially serve the functional according to the invention Additives of the coating of metallic effect pigments. In this use according to the invention suppress she already for the formation of hydrogen in the aqueous phase is particularly effective on its own Medium.

However, it is completely surprising that the functional additives according to the invention have the effect of customary and known passivating agents, such as alkanephosphonic acids such as. Octanephosphonic acid, mixed organic phosphate esters described in the European patent EP 1 213 334 B1 described reaction products of phosphonic acids with epoxides or in the American patent US 5,429,647 described N-Acylaminomethylenphosphonate, synergistically beyond the purely additive extent.

The functional according to the invention Additives are therefore of very particular advantage in water-based paints used, preferably the production of color and / or effect Multilayer coatings serve, preferably at least one color and / or effect Basecoat and at least one clearcoat included and most preferably prepared by wet-on-wet processes become. In particular, these waterborne basecoats and color and / or effect-imparting multicoat paint systems in automotive OEM finishing and the car refinish used.

Examples of suitable aqueous basecoats to which the functional additives according to the invention can be added with particular advantage, and wet-on-wet processes for their further processing are known from the German patent application DE 199 48 004 A1 , Page 3, lines 14, to page 19, line 22, known.

Surprisingly show these waterborne basecoats to which the functional additives of the invention gassing <10 ml / 4 weeks and they provide basecoats, the excellent surface structure, the free of paint defects is, an excellent flow, an excellent metallic effect without light / dark shades (clouds), an outstanding optical Overall impression, excellent opacity, reproducible at any time Color location and have an excellent color effect.

Examples

Production Example 1

The preparation of a radically polymerizable acid phosphonic acid ester (A)

In a reaction vessel, equipped with stirrer, Indoor thermometer, reflux condenser and electric heating, 1,041.1 parts by weight of 2,2-dimethyloctanoic acid glycidyl ether and 458.9 parts by weight of vinylphosphonic acid (50 percent dissolved in N-methylpyrrolidone) while stirring at 80 ° C heated until an epoxide equivalent weight> 50,000 was reached. The resulting phosphonic acid ester (A) was excellent for the radical copolymerization with monomers (B) suitable.

example 1

The production of a lateral acid phosphonic containing copolymer

In a reaction vessel, equipped with stirrer, Indoor thermometer, reflux condenser and electric heating, were 1,062.5 parts by weight of N-methylpyrrolidone submitted and stirred at 100 ° C heated. At this temperature, while stirring, a mixture of 315.7 Parts by weight of styrene, 315.7 parts by weight of lauryl methacrylate, 265.2 Parts by weight of ethylhexyl acrylate and 580.8 parts by weight of the acidic phosphonic acid ester (A) of Preparation Example 1 During evenly for four hours given. With the beginning of the addition of the mixture was a 50 percent solution of 126.3 parts by weight of tert-butyl peroxyethylhexanoate in 126.3 Parts by weight of N-methylpyrrolidone while 4.5 hours added. The resulting reaction mixture was at 100 ° C polymerized until no more free monomers were detectable. The resulting copolymer solution had a solid of 49.8 wt .-% (one hour at 130 ° C) and an acid number of 45 mg KOH / g solids on.

The Copolymer was excellent as a functional additive for passivation of metallic effect pigments, in particular aluminum effect pigments, suitable.

Example 2

The preparation of an aluminum effect pigment preparation

There was added 4.8 parts by weight of a commercially available aluminum effect pigment (Alpate ^® 8160 N-AR Company Toyal, 6.5 parts by weight dipropylene glycol methyl ether, 1.5 parts by weight of butyl glycol, 0.32 parts by weight of the copolymer of Example 1, 0.49 parts by weight of a 50 percent Solution of a commercially available passivating agent (Passivator W from Eckart) in butyl glycol, 2.4 parts by weight of the aqueous Po polyester resin dispersion according to the German patent application DE 40 09 858 A1 , Column 16, Example D, and 0.22 parts by weight of a ten percent aqueous dimethylethanolamine solution are mixed together and the resulting mixture homogenized.

The resulting aluminum effect pigment preparation was excellent for the preparation suitable for water-based paints.

Example 3

The preparation of a water-based paint

Mischlack:

For the preparation of the water-based paint, a mixed paint was first prepared. For this purpose, 32 parts by weight of a 3 wt .-% - aqueous solution of a layered silicate (Laponite ^® RD from Laporte) were submitted. To this was added 6 weight parts of deionized water, 0.5 weight parts of a commercial wetting agent (50 percent solution of Surfynol ^® 100 from Air Products in butyl glycol) and 5 parts by weight of the polyurethane-modified polyacrylate according to Example D of the German patent application DE 44 37 535 A1 added. Subsequently, a mixture of 1.5 parts by weight of the aqueous polyester resin dispersion according to the German patent application DE 40 09 858 A1 , Column 16, Example D, 3.5 parts by weight of a commercially available water-dilutable melamine / formaldehyde resin (Cymel ^® 327), 0.5 parts by weight of the wetting agent solution described above, 2 parts by weight of polypropylene glycol (number average molecular weight 900 Daltons) and 0.4 parts by weight of a ten percent added aqueous dimethyl ethanolamine solution. To the resulting mixture 4 parts by weight of a 10 wt .-% - solution of a commercial polyacrylic acid thickener (Viscalex ^® HV3 from Allied Colloids) and 5 parts by weight of deionized water, 0.5 parts by weight of a 50 wt .-% - solution of a commercial associative thickener based on polyurethane ^(® Nopco DSX 1550 butylglycol Henkel), 18 parts by weight of the polyurethane dispersion according to the German patent application DE 199 48 004 A1 Example 2, page 20, lines 9 to 21, i. V. m. Preparation Example 1 and Example 1, page 19, line 44, to page 20, line 7, and added 5.7 parts by weight of deionized water with stirring. Subsequently, the resulting mixture was homogenized.

Water-based paint:

The above-described blend and the aluminum effect pigment preparation of Example 2 were mixed in a weight ratio of 83.8: 16.2, after which the resulting mixture was homogenized. The resulting waterborne basecoat exhibited only a very low gassing of 0.5 ml / 4 weeks at 40 ° C (measured according to the test »Correction of the test described in Eckart 's brochure,» STAPA ^® Aluminum Pastes for Waterborne Lacquer Systems Technical Information «) Gasungstabilität ").

Of the Water-based paint was mixed with a 10 wt .-% aqueous dimethylethanolamine and deionized water to a pH of 7.8 to 8.2 and a application viscosity at 23 ° C of 80 mPas at a shear of 1,000 / s.

Of the Water-based paint was excellent for the production of effect-giving Basecoats suitable.

Example 4

The production of an effect-giving Multi-layer coating

On steel panels (body panels) which had been previously coated with a cathodically deposited and baked electrodeposition coating, a commercially available filler from BASF Coatings AG was first applied, after which the resulting filler layers were flashed for 5 minutes at 20 ° C and a relative humidity of 65% and baked in a convection oven for 30 minutes at 140 ° C. After cooling the steel panels to 20 ° C, the water-based paint of Example 3 was applied in two spray coats. The first application was carried out by means of ESTA (bell speed: 45,000 rpm, directing air: 120 Nl / min, voltage: 45 kV, distance 0.25 m, outflow: 170 ml / min), corresponding to a dry film thickness of 8 to 10 μm. The second application was carried out pneumatically (distance: 0.32 m, outflow: 540 ml / min, atomizing air - amount: 300 Nl / min, atomizer - air pressure: 4.8 bar, horn air - amount: 395 Nl / min; Horn air pressure: 5.2 bar), corresponding to a dry film thickness of 4 to 6 microns. The aqueous basecoat was flashed off after the first and second application for 2 minutes each. Subsequently, the aqueous basecoat film was predried for 10 minutes at 80 ° C, cooled and overcoated with a commercial two-component clearcoat from BASF Coatings AG. Subsequently, the aqueous basecoat films and the clearcoat films were baked together at 130 ° C. for 30 minutes, whereby the multicoat paint systems resulted in basecoats having a layer thickness of 12 to 16 .mu.m and clearcoats having a layer thickness of 40 .mu.m.

The Basecoats had an excellent surface structure, that was free of paint defects, an excellent course, an excellent metallic effect without light / dark shades (clouds), an outstanding optical Overall impression and excellent hiding power on. The multicoat paint systems overall showed a high gloss (20 °) according to DIN 67530 of 94 units, an excellent rockfall according to VDA (grade 2) and an excellent condensation resistance in the Constant Climate Test (KK), combined with an outstanding Intercoat adhesion on what the following compilation substantiated:

Compilation of the results of the constant climate test (KK)

After 3 hours of regeneration: Shine: 94 units; Blistering: M0G0 Cross-cut test: GT0 After 24 hours of regeneration: Shine: 92 units Blistering: M0G0 Cross-cut test: GT0

Claims (34)

Side-chain acid phosphonic acid ester group-containing copolymers of olefinically unsaturated monomers which can be prepared by reacting (A) at least one radically polymerizable acidic phosphonic acid ester which can be prepared by reacting (A1) at least one phosphonic acid of the general formula I: RP (= O) (-OH) ₂ I, wherein R is at least one, at least one radically polymerizable carbon-carbon double bond-containing, substituted or unsubstituted, heteroatom-containing or free thereof, organic radical; with (A2) at least one of radically polymerizable groups substantially or completely free, an epoxy group-containing compound in an equivalent ratio of acid group (P-OH) to epoxy group = 2: 1 to 1.2: 1; with (B) at least one of (A) different radically polymerizable monomers radically polymerized. Copolymers according to Claim 1, characterized that the equivalent ratio of acid group (P-OH) to epoxide group = 2: 1 to 1.5: 1. Copolymers according to Claim 1 or 2, characterized in that the compound (A2) is selected from the group consisting of compounds of the general formulas II, III and IV:

wherein the index and the variables have the following meaning: X is a divalent linking group, R ^{1 is a} substituted, unsubstituted, heteroatom-containing or free, monovalent organic radical containing at least one group selected from the group consisting of aliphatic, cycloaliphatic and aromatic R ^{2 is} independently hydrogen atom, substituted or unsubstituted heteroatom-containing or free thereof, monovalent organic radical containing or containing at least one group selected from the group consisting of aliphatic, cycloaliphatic and aromatic groups R ^{3 is} substituted or unsubstituted, heteroatom-containing or free thereof containing at least one aromatic group or free, divalent, aliphatic radical; is selected. Copolymers according to claim 3, characterized in that - in general formula II, the monovalent radical R ^{1 is} a substituted or unsubstituted, heteroatom-containing or free, aliphatic group having 3 to 20 carbon atoms, - in the general formula III - the two Radicals R ^{2 represent} hydrogen atoms, - one of the two radicals R ^{2 is} a hydrogen atom and the other radical R ^{2 is} a substituted or unsubstituted, heteroatom-containing or free thereof, aliphatic group having 1 to 6 carbon atoms, a substituted or unsubstituted heteroatom-containing or Of these, free, cycloaliphatic group having 3 to 8 carbon atoms or a substituted or unsubstituted, heteroatom-containing or free thereof, aromatic group having 6 to 20 carbon atoms or - the two radicals R ^{2 are} identical or different, substituted or unsubstituted, containing heteroatoms or thereof free e, aliphatic groups having 1 to 6 carbon atoms, substituted or unsubstituted, heteroatom-containing or free thereof, cycloaliphatic groups having 3 to 8 carbon atoms or substituted or unsubstituted, heteroatom-containing or free thereof, aromatic groups having 6 to 20 carbon atoms, and - the general formula IV, the radical R ^{3 is} a substituted or unsubstituted heteroatom-containing or free thereof divalent aliphatic radical having 2 to 20 carbon atoms or for such a divalent aliphatic radical containing a substituted or unsubstituted, heteroatom-containing or free aromatic group containing from 6 to 20 carbon atoms. Copolymers according to Claim 3 or 4, characterized that the compound (A2) is selected from the group of compounds of general Formula II selected is. Copolymers according to one of claims 3 to 5, characterized in that the monovalent radical R ^{1 is} a heteroatom-free, aliphatic group having 4 to 10 carbon atoms. Copolymers according to one of claims 3 to 6, characterized in that the monovalent, heteroatom-free, aliphatic radical R ^{1 is} branched. Copolymers according to Claim 7, characterized in that the monovalent aliphatic radical R ^{1 is selected} from the group consisting of 1,1-dimethyl-eth-1-yl, 1,1-dimethyl-prop-1-yl, 1,1- Dimethyl-but-1-yl, 1,1-dimethyl-pent-1-yl, 1,1-dimethyl-hex-1-yl, 1,1-dimethyl-hept-1-yl and 1,1-dimethyl oct-1-yl, is selected. Copolymers according to one of Claims 3 to 8, characterized in that the divalent ver Kicking group X is an ether group or a carboxyl group in which the oxygen atom is connected to the methylene group. Copolymers according to Claim 9, characterized that the two-letter linking Group X is a carboxyl group. Copolymers according to one of claims 1 to 10, characterized in that the organic radical R is a radical polymerizable carbon-carbon double bonds contains. Copolymers according to Claim 11, characterized that the phosphorus of the phosphonic acid group of the general formula I with one carbon atom of the carbon-carbon double bond the organic radical R is connected. Copolymers according to Claim 11 or 12, characterized characterized in that the organic radical R from the group consisting of vinyl, styryl-dicyclopentadienyl, Norbornenyl, isoprenyl, isopropenyl, allyl or butenyl groups, selected is. Copolymers according to Claim 13, characterized the organic radical R is a vinyl group. Copolymers according to one of claims 1 to 14, characterized in that the phosphonic acid (A1) is vinylphosphonic acid. Copolymers according to one of claims 1 to 15, characterized in that the compound (A2) is selected from the group consisting of glycidyl esters of 2,2-dimethylpropionic acid, -butyric acid, -pentanoic acid, -hexanoic acid, -heptanoic acid and octanoic acid, selected is. Copolymers according to one of claims 1 to 16, characterized in that the free-radically polymerizable Monomers (B) substantially or completely free of hydrophilic groups are. Copolymers according to one of claims 1 to 17, characterized in that the radically polymerizable Monomer (B) from the group consisting of olefins, cycloolefins, Vinylaromatics and olefinically unsaturated ethers, thioethers, Carbonsäureestern, thiocarboxylic acid esters, Carbonates, thiocarbonates, phosphoric acid esters, thiophosphoric esters, phosphonates, Thiophosphonic esters, phosphites, Thiophosphites, sulfonic esters, Amides, amines, thioamides, phosphoric acid amides, thiophosphoric acid amides, phosphonic acid amides, Thiophosphonsäureamiden, sulfonamides, Imides, hydrazides, urethanes, ureas, thioureas, carbonyls, Thiocarbonyls, sulfones, sulfoxides and siloxanes. Copolymers according to Claim 18, characterized in that the radically polymerizable monomer (B) is selected from the group consisting of olefins, cycloolefins, vinylaromatics, olefinic unsaturated ethers, olefinically unsaturated Carbonsäureestern and olefinically unsaturated Siloxanes, selected is. Copolymers according to Claim 19, characterized in that - the olefins (B) are selected from the group consisting of ethene, propene, isoprene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1 Nonene, 1-decene, butadiene, isoprene, acrylonitrile, vinyl chloride, vinyl fluoride, vinylidene difluoride and tetrafluoroethylene; The cycloolefins (B) from the group consisting of cyclopentene, cyclohexene, cycloheptene, cyclooctene, dicyclopentadiene and norbornene; The vinylaromatics (B) from the group consisting of styrene, alpha-alkylstyrene and compounds of the general formula V: R ⁴ R ⁵ C = CR ⁶ R ⁷ (V), wherein the radicals R ⁴ , R ⁵ , R ⁶ and R ^{7 are} each independently hydrogen or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals with the proviso that at least two of the variables R ⁴ , R ⁵ , R ⁶ and R ^{7 are} substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals; The olefinically unsaturated ethers (B) from the group consisting of vinyl ethers, allyl ethers, butenyl ethers, cyclohexenyl ethers, dicyclopentadienyl ethers and norbornenyl ethers; - the olefinically unsaturated carboxylic acid esters (B) from the group consisting of (meth) acrylates, ethacrylates, crotonates, cinnamates, maleates, fumarates and vinyl esters; and - the olefinically unsaturated siloxanes (B) from the group consisting of polysiloxanes containing vinyl, allyl, vinyl ether, allyl ether and / or (meth) acryloyl groups; are selected. Copolymers according to one of claims 1 to 20, characterized in that the substituents from the group, consisting of fluorine, chlorine, bromine and iodine atoms, nitro groups and nitro groups selected are. Copolymers according to one of claims 1 to 21, characterized in that the heteroatoms from the group, consisting of boron, silicon, nitrogen, phosphorus, oxygen and Sulfur, selected are. Process for the preparation of pendant, acidic phosphonic containing copolymers of olefinically unsaturated monomers according to a the claims 1 to 22, characterized in that at least one radical polymerizable acidic phosphonic acid ester (A) and at least a radically polymerizable monomer (B) in bulk, solution or Dispersion radically copolymerized. Use of the pendant acid phosphonic acid ester groups containing copolymers of free-radically polymerizable monomers according to one the claims 1 to 22 and that produced by the method according to claim 23, pendant acid phosphonic acid ester groups containing copolymers of free-radically polymerizable monomers as functional additives. Use according to claim 24, characterized that the functional additives of the production of coating materials, Adhesives, sealants and precursors for moldings and films serve. Use according to claim 25, characterized that the coating materials, adhesives, sealants and precursors the production of coatings, adhesive layers, seals, moldings and Serve slides. Use according to claim 25 or 26, characterized that the coating materials aqueous Coating materials are. Use according to claim 27, characterized that the watery Coating materials contain metallic effect pigments. Use according to one of Claims 24 to 28, characterized that the functional additive of the coating of metallic effect pigments serves. Use according to claim 28 or 29, characterized that the watery Coating materials are water-based paints. Use according to claim 30, characterized that the water-based paints of the production of color and / or effect Multilayer coatings serve. Use according to claim 31, characterized that the color and / or effect multicoat paint systems at least a color and / or effect basecoat and at least a clearcoat included. Use according to claim 32, characterized that the color and / or effect multi-layer coatings after Wet-on-wet process can be produced. Use according to one of Claims 25 to 33, characterized that the coating materials in the automotive OEM and automotive refinish be used.