Process for preparing pigment and filler containing formulations

Patent metadata

Field	Value
Publication number	US-9914840-B2
Application number	US-201315105069-A
Country	US
Kind code	B2
Filing date	Dec 20, 2013
Priority date	Dec 20, 2013
Publication date	Mar 13, 2018
Grant date	Mar 13, 2018

Abstract

The invention relates to aqueous, cationically stabilized primary dispersions comprising dispersed polymer particles that have a Z-average particle diameter of 5 to 500 nm and are obtainable by emulsion polymerization of at least one olefinically unsaturated monomer (A), wherein the emulsion polymerization takes place in the presence of one or more emulsifiers (E) having the following general formula: R 1 —(R 2 )(R 3 ), where: R is a moiety that contains at least one aromatic group and at least one aliphatic group, has 15 to 40 carbon atoms, and contains at least one functional group selected from hydroxy groups, thiol groups, and primary or secondary amino groups and/or comprises at least one carbon-carbon multiple bond; and R 1 , R 2 , and R 3 are, independently of each other, identical or different aliphatic moieties having 1 to 14 carbon atoms. The invention also relates to a method for producing the primary dispersions, coating agents comprising the primary dispersions, use of the primary dispersions to produce electrocoats, and conductive substrates that have been coated with the coating agent compositions.

First claim

The invention claimed is:

1. A method for producing a pigment- and/or filler-containing formulation, wherein one or more solids selected from the group of the pigments and fillers are mixed with an aqueous, cationically stabilized primary dispersion comprising:
(1) dispersed polymer particles, which
i. have a Z-average particle diameter of 5 to 500 nm, and
ii. which are obtained through emulsion polymerization of at least one olefinically unsaturated monomer (A), wherein the emulsion polymerization takes place in the presence of one or more emulsifiers selected from the group consisting of (E), (EQ), and mixtures thereof and wherein (E) and (EQ) having the following formulas:
R 1 —N(R 2 )(R 3 )  (E),

R 1 —N ⊕ (R 2 )(R 3 )(R 4 )X ⊖   (EQ),

where:
R 1 is a moiety that contains at least one aromatic group and at least one aliphatic group, has 15 to 40 carbon atoms, and contains at least one functional group selected from the group consisting of hydroxy groups, thiol groups, primary amino groups, secondary amino groups, at least one carbon-carbon multiple bond, and mixtures thereof;
R 2 , R 3 , and R 4 are, independently of each other, identical or different aliphatic moieties having 1 to 14 carbon atoms;
and X ⊖ stands for the acid anion of an organic or inorganic acid HX, and

(2) optionally wherein the pigments and/or fillers are mechanically crushed.

2. The method according to claim 1 , wherein the moiety R 1 — has the structure Gr ali1 -Gr arom -Gr ali2 , where Gr arom stands for an aromatic group, Gr ali1 stands for a first aliphatic group, and Gr ali2 stands for a second aliphatic group.

3. The method according to claim 2 , wherein the moiety R 1 has at least one carbon-carbon multiple bond in the aliphatic group Gr ali1 .

4. The method according to claim 2 , wherein the moiety R 1 has at least one functional group selected from the group consisting of hydroxy groups, thiol groups, primary amino groups, secondary amino groups, and mixtures thereof in the aliphatic group Gr ali2 .

5. The method according to claim 4 , wherein the moiety R 1 has, in the aliphatic group Gr ali2 , at least one functional group selected from the group consisting of hydroxy groups, thiol groups, primary amino groups, and secondary amino groups in the beta position to the nitrogen atom of the general formulas of the emulsifiers (E) and (EQ) according to claim 1 .

6. The method according to claim 2 , wherein
Gr ali1 is linear, unsubstituted, and heteroatom-free, and has one to three carbon-carbon double bonds;
Gr arom is a phenylene or naphthylene group; and
Gr ali2 is linear, bears a hydroxy group in the beta position to the nitrogen atom in the general formulas of the emulsifiers (E) and (EQ), and additionally contains O as a heteroatom, in the form of an ether group.

7. The method according to claim 1 , wherein at least two of the moieties R 1 , R 2 , R 3 , and R 4 bear a functional group selected from the group consisting of hydroxy groups, thiol groups, primary amino groups, secondary amino groups, and mixtures thereof.

8. The method according to claim 7 , wherein in addition to the at least one group selected from hydroxy groups, thiol groups, primary amino groups, secondary amino groups, the at least two of the moieties R 2 , R 3 , and R 4 bear at least one other functional group selected from the group consisting of ether groups, ester groups, and amide groups.

9. The method according to claim 1 , wherein X ⊖ is the acid anion of an acid HX that is selected from the group of non-hydroxy-functional carboxylic acids and monohydroxy-functional carboxylic acids.

10. The method according to claim 1 , wherein a mixture of different emulsifiers selected from (E), (EQ), and mixtures thereof is used, in which more than 50 mol % of the moiety R 1 contains carbon-carbon multiple bonds.

11. The method according to claim 1 , wherein the olefinically unsaturated monomer (A) is selected from the group consisting of:
a1) acid group-free (meth)acrylic acid esters;
a2) monomers that: bear at least one hydroxy group, one primary or secondary, or tertiary, or quaternary amino group, one alkylxymethylamino group, or one imino group per molecule; are acid group-free; and are different from the emulsifiers (E) and (EQ);
a3) monomers bearing, per molecule, at least one acid group that can be converted into the corresponding acid anion group;
a4) vinyl esters of α-branched monocarboxylic acids having 5 to 18 carbon atoms in the molecule;
a5) reaction products of acrylic acid and/or methacrylic acid with the glycidyl ester of an α-branched monocarboxylic acid having 5 to 18 carbon atoms per molecule;
a6) cyclic or acyclic olefins;
a7) (meth)acrylamides;
a8) epoxy group-containing monomers;
a9) vinyl aromatic hydrocarbons;
a10) acrylonitrile or methacrylonitrile;
a11) vinyl compounds selected from the group of vinyl halides, vinylidene dihalides, N-vinylamides, vinyl ethers, and vinyl esters that are different from the monomers a4);
a12) allyl compounds;
a13) polysiloxane macromonomers having a number-average molecular weight M n of 1000 to 40,000 and a mean of 0.5 to 2.5 ethylenically unsaturated double bonds per molecule;
a14) acryloxy silane-containing vinyl monomers; and
mixtures thereof.

12. The method according to claim 11 , wherein the olefinically unsaturated monomer (A) is selected from the group consisting of the monomers a1), a2), a9), and mixtures thereof.

13. The method according to claim 11 , wherein a mixture of olefinically unsaturated monomers (A) is used, comprising:
monomers a1) selected from the group of (meth)acrylic acid alkyl esters or (meth)acrylic acid cycloalkyl esters having up to 20 carbon atoms in the alkyl or cycloalkyl group;
monomers a2) selected from the group consisting of monomers bearing at least one hydroxy group one primary amino group, one secondary amino group, one tertiary amino group, or one quaternized amino group; and
styrene as a monomer a9).

14. The method according to claim 1 , wherein, in order to produce the aqueous, cationically stabilized primary dispersion:
(1) the olefinically unsaturated monomer(s) (A) and the emulsifier(s) (E) and/or (EQ) are placed in an aqueous medium, optionally with a cross-linking agent and/or additional binders,
(2) and then converted into a miniemulsion by using high shear forces, and
(3) then an emulsion polymerization is performed.

15. The method according to claim 14 , wherein one or more cross-linking agents selected from the group consisting of blocked polyisocyanates, trs(alkoxycarbonylamino) triazines, and fully etherified aminoplast resins are used as the cross-linking agents.

16. The method according to claim 14 , wherein an epoxy amine adduct is used as an additional binder.

17. The method according to claim 14 , wherein the polymerization is performed at a temperature of 25° C. to 95° C. and/or a pressure of 1.5 to 3000 bar.

18. The method according to claim 14 , wherein the emulsion polymerization is initiated by water-soluble initiators selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, tert-butyl hydroperoxide, and mixtures thereof.

19. A pigment- and/or filler-containing formulation, which is produced according to the method of claim 1 .

20. An aqueous preparation comprising a cathodically depositable binder and a pigment- and/or filler-containing formulation according to claim 19 .

21. The aqueous preparation according to cla

Assignees

• Basf Coatings Gmbh
• Henkel Ag & Co Kgaa

Inventors

• Markou Konstantinos
• Niegemeier Andreas
• Holtschulte Sabine
• Moebius Jerome

Classifications

• C09D5/08

  Anti-corrosive paints · CPC title

• C09D17/008

  Titanium dioxide · CPC title

• C09D5/4457 Primary

  containing special additives, e.g. pigments, polymeric particles · CPC title

• C09D17/007

  Metal oxide · CPC title

• C25D13/06

  with polymers {(not used, see C09D5/44)} · CPC title