COATINGS HAVING IMPROVED RESISTANCE TO STAINS AND DIRT

• US 20190077971A1
• Filed: 10/25/2016
• Published: 03/14/2019
• Est. Priority Date: 11/10/2015
• Status: Active Grant

• Current Assignee: Arkema France (Arkema)
• Original Assignee: Arkema France (Arkema)
• Inventors: Boone, Alain, Mazajczyk, Jerome, Delmas, Gregory A., Chambat, Claire
• Granted Patent: US 10,442,936 B2
• Time in Patent Office: Days
• CPC Class Codes: C08F 2/24 with the aid of emulsifying agents
• CPC Class Codes: C08F 212/08 Styrene
• CPC Class Codes: C08F 220/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• CPC Class Codes: C08F 220/14 Methyl esters , e.g. methyl (meth)acrylate
• CPC Class Codes: C08F 220/18 with acrylic or methacrylic acids
• CPC Class Codes: C08F 220/1804 C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• CPC Class Codes: C08F 220/28 containing no aromatic rings in the alcohol moiety
• CPC Class Codes: C08F 220/283 and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
• CPC Class Codes: C08F 220/34 Esters containing nitrogen , e.g. N,N-dimethylaminoethyl (meth)acrylate
• CPC Class Codes: C08F 220/40 Esters of unsaturated alcohols , e.g. allyl (meth)acrylate
• CPC Class Codes: C08F 265/06 Polymerisation of acrylate or methacrylate esters on to polymers thereof
• CPC Class Codes: C09D 151/003 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C09D151/04, C09D151/06 take precedence
• CPC Class Codes: C09D 5/022 Emulsions, e.g. oil in water
• CPC Class Codes: C09D 5/027 Dispersing agents anti-settling agents C09D7/45

Abstract

The invention relates to aqueous coating compositions based on an aqueous polymer dispersion as binder, having high performance levels of resistance to stains and dirt without specialist functional monomers. Said aqueous polymer dispersion having an MFFT between 0 and 50° C. comprises polymer particles obtained by emulsion polymerization in at least two steps with at least two polymer phases P1 and P2, P1 representing from 75 to 90% by weight of P1+P2 having a Fox Tg1 from 0 to 40° C. and P2 having a Fox Tg2 from 0 to 40° C., said polymer P2 representing from 10 to 25% by weight of the sum of polymers P1 and P2 and having a calculated Hansch parameter <2.0 and at least one ethylenically unsaturated monomer bearing an acetoacetoxy and/or amine or ureido functional group, said acetoacetoxy and/or amine or ureido functional group being borne by the external surface of P2 phase.

Claims

1. An aqueous coating composition comprising, as binder, an aqueous polymer dispersion wherein said polymer dispersion has a minimum film-forming temperature (MFFT) according to ISO 2115 between 0 and 50°

C., and comprises polymer particles obtained by radical emulsion polymerization in at least two steps, and wherein said particles comprise at least two polymer phases P1 and P2, with the P1 polymer phase representing from 75% to 90% by weight of the total polymer P1+P2 and the P2 polymer phase representing from 10% to 25% by weight of the total polymer P1+P2, with P1 having a glass transition temperature Tg1 calculated according to Fox, ranging from 0 to 40°

C., and P2 having a glass transition temperature Tg2 calculated according to Fox, ranging from 0 to 40°

C., and for Tg1 and Tg2 ranging from 0 to 20°

C., which may be identical or different to within ±

2°

C. and with

said P1 polymer comprising structural units derived from 4 monomers M1 to M4 as follows;

at least one ethylenically unsaturated monomer M1 chosen from C₄ (meth)acrylic esters, and

at least one ethylenically unsaturated monomer M2 chosen from vinyl aromatic monomers, and

at least one ethylenically unsaturated monomer M3 bearing a carboxylic acid group, and

at least one monomer M4 having a function of internal crosslinking agent of said P1 phase,

said P2 polymer comprising structural units derived from 4 monomers M5 to M8 as follows;

at least one ethylenically unsaturated monomer M5 chosen from C₄ (meth)acrylic esters, which may be identical to or different than M1,

at least one ethylenically unsaturated monomer M6 chosen from vinyl aromatic monomers, which monomer M6 may be identical to or different than M2, and

at least one ethylenically unsaturated monomer M7, the homopolymer of which has a Tg measured by DSC at 10°

C./min of between 80 and 120°

C. and a hydrophobicity value estimated by the logarithm of the partition coefficient between octanol and water (LogKow), Estimation Program Interface Suite®

KowWin of the US Environmental Protection Agency'"'"'s Office of Pollution Prevention and Toxics and Syracuse Research Corporation (SRC) according to EPIWEB 4.1, ranging from 1 to 1.5, and

at least one ethylenically unsaturated monomer M8 bearing an acetoacetoxy or amine or ureido functional group, said acetoacetoxy, amine or ureido functional group being borne by the external surface of the shell polymer phase P2,

the P2 polymer phase thus obtained from M5, M6, M7 and M8 having a hydrophobicity characterized by the Hansch parameter rounded up to one decimal, of less than or equal to 2.0, calculated by adding the products of the mass fractions multiplied by the LogKow corresponding to each component monomer and with P2 being in the external layer of said polymer particle.

2. The composition as claimed in claim 1, wherein said binder is free of any monomer bearing a phosphate, phosphine, phosphonic, phosphodiester or fluorinated functional group, strong anionic acid group, and wherein said coating composition is free of any silicone additive, fluorinated additive or microwax additive and of any addition of polymer or oligomer additives having a Tg greater than the average Fox Tg of polymer P1+P2, whether this addition is in dispersion form or whether it is in water-dispersible form.

3. The composition as claimed in claim 1 wherein said C₄ (meth)acrylic ester monomer M1 is selected from the group consisting of:

n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate isobutyl methacrylate, tert-butyl acrylate and tert-butyl methacrylate.

4. The composition as claimed in claim 1 wherein said monomer M3 is selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid and itaconic acid.

5. The composition as claimed in claim 1 wherein said monomer M4 is chosen from the group consisting of multifunctional (meth)acrylic esters or and a (meth)acrylate bearing an alkoxy-blocked silane group —

Si(OR)₃, with R being methyl or ethyl.

6. The composition as claimed in claim 1 wherein said monomer M8 is selected, for the acetoacetoxy functional group, from the group consisting of acetoacetoxy ethyl (meth)acrylate (AAEM) and, for the amino functional group, from the group consisting of 2-dimethylaminoethyl (meth)acrylate (MADAME) and, for a ureido functional group, from the group consisting of ureido (meth)acrylates.

7. The composition as claimed in claim 1 wherein said coating is a paint, varnish or ink.

9. The composition as claimed in claim 1 which is a barrier coating composition.

10. The composition as claimed in claim 1 which is a corrosion-resistant coating composition.

11. The composition as claimed in claim 1 which is a stain-resistant and corrosion-resistant coating composition.

12. The composition as claimed in claim 1 wherein said Hansch parameter for the P1 polymer is different and higher than the Hansch parameter of the P2 polymer, by at least 0.2 unit.

8. (canceled)

13. (canceled)

14. (canceled)

15. (canceled)

16. An aqueous polymer dispersion, wherein said polymer dispersion has a minimum film-forming temperature (MFFT) according to ISO 2115 between 0 and 50°

C., and comprises polymer particles obtained by radical emulsion polymerization in at least two steps and said particles comprise at least two polymer phases P1 and P2, with the P1 polymer phase representing from 75% to 90% by weight of the total polymer P1+P2 and the P2 polymer phase representing from 10% to 25% by weight of the total polymer P1+P2, with P1 having a glass transition temperature Tg1 calculated according to Fox, ranging from 0 to 40°

C. and P2 having a glass transition temperature Tg2 calculated according to Fox, ranging from 0 to 4°

C. which may be identical or different to within ±

2°

C. and with

said P1 polymer comprising structural units derived from 4 monomers M1 to M4 as follows;

at least one ethylenically unsaturated monomer M1 chosen from C₄ (meth)acrylic esters, and

at least one ethylenically unsaturated monomer M2 chosen from vinyl aromatic monomers, and

at least one ethylenically unsaturated monomer M3 bearing a carboxylic acid group, and

at least one monomer M4 having a function of internal crosslinking agent of said P1 phase, preferably chosen from monomers bearing at least two ethylenic unsaturations that are copolymerizable with the ethylenic unsaturations of the monomers M1 to M3 or bearing an ethylenic unsaturation and a blocked silane functional group in alkoxysilane form,

said P2 polymer comprising structural units derived from 4 monomers M5 to M8 as follows;

at least one ethylenically unsaturated monomer M5 chosen from C₄ (meth)acrylic esters which may be identical to or different than M1,

at least one ethylenically unsaturated monomer M6 chosen from vinyl aromatic monomers, which monomer M6 may be identical to or different than M2, and

at least one ethylenically unsaturated monomer M7, the homopolymer of which has a Tg measured by DSC at 10°

C./min of between 80 and 120°

C. and a hydrophobicity value estimated by the logarithm of the partition coefficient between octanol and water (LogKow), Estimation Program interface Suite®

KowWin of the US Environmental Protection Agency'"'"'s Office of Pollution Prevention and Toxics and Syracuse Research Corporation (SRC) according to EPIWEB 4.1, ranging from 1 to 1.5, said monomer M7, and

at least one ethylenically unsaturated monomer M8 bearing an acetoacetoxy or amine or ureido functional group, said acetoacetoxy, amine or ureido functional group being borne by the external surface of the shell polymer phase P2,

the P2 polymer phase thus obtained from M5, M6, M7 and M8 having a hydrophobicity characterized by the Hansch parameter rounded up to one decimal, of less than or equal to 2.0, calculated by adding the products of the mass fractions multiplied by the LogKow corresponding to each component monomer and with P2 being in the external layer of said polymer particle.

17. A process for preparing the aqueous dispersion of claim 16, comprising at least two steps, of polymerization corresponding respectively to the P1 and P2 polymer phases:

i) first step of emulsion polymerization, including a step of polymer seeding, of a first composition of monomers comprising in emulsion said monomers M1, M2, M3 and M4 as defined in claim 16 and corresponding to the P1 polymer phase, with said monomer M3 being in predominantly salified form, and

followed by a

ii) second step of emulsion polymerization of a second composition of monomers comprising in emulsion said monomers M5, M6, M7 and M8 as defined in claim 16 and corresponding to the P2 polymer phase, said polymerization being carried out under pH conditions of less than or equal to 9.

18. (canceled)

19. (canceled)

20. (canceled)