(19) TZZ Z_T (11) EP 2 576 708 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C09D 5/00 (2006.01) 21.09.2016 Bulletin 2016/38 (86) International application number: (21) Application number: 11738854.6 PCT/US2011/039283 (22) Date of filing: 06.06.2011 (87) International publication number: WO 2011/153534 (08.12.2011 Gazette 2011/49) (54) AQUEOUS CROSS-LINKING COMPOSITIONS AND METHODS WÄSSRIGE VERNETZUNGSZUSAMMENSETZUNGEN UND VERFAHREN COMPOSITIONS DE RÉTICULATION AQUEUSES ET PROCÉDÉS (84) Designated Contracting States: • SHEERIN, Robert J. AL AT BE BG CH CY CZ DE DK EE ES FI FR GB N. Caldwell, NJ 07006 (US) GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO • MAUCK, Jean Fredrick PL PT RO RS SE SI SK SM TR Hackettstown, NJ 07840 (US) • TILARA, Navin (30) Priority: 04.06.2010 US 351657 P Roseland, NJ 07068 (US) 03.06.2011 US 201113152856 • GARCIA DE VISICARO, Johanna Lake Hopatcong, NJ 07849 (US) (43) Date of publication of application: 10.04.2013 Bulletin 2013/15 (74) Representative: Gerbino, Angelo et al Jacobacci & Partners S.p.A. (73) Proprietor: Benjamin Moore & Co. Corso Emilia 8 Montvale, NJ 07645 (US) 10152 Torino (IT) (72) Inventors: (56) References cited: • YANG, Yong EP-A1- 0 945 495 EP-A2- 0 219 047 Hillsborough, NJ 08844 (US) WO-A1-00/31197 JP-A- 2000 001 633 • CHEN, Yue US-A1- 2006 231 487 US-A1- 2008 307 587 Edison, NJ 08820 (US) Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 576 708 B1 Printed by Jouve, 75001 PARIS (FR) EP 2 576 708 B1 Description CROSS-REFERENCE TO RELATED APPLICATIONS 5 [0001] This application claims the benefit of United States Patent Application No. 13/152,856, filed 3 June 2011, which claims the benefit of United States Provisional Patent Application Serial No. 61/351,657, filed 4 June 2010, both references are incorporated herein by reference in their entirety as if fully set forth below. FIELD OF THE INVENTION 10 [0002] The invention concerns water-borne cross-linking polymeric compositions and related embodiments, such as methods of making and using the compositions, as well as products formed with said compositions. BACKGROUND 15 [0003] Water-borne paints, primers, coatings, inks, adhesives, and other water-borne film-forming compositions ("wa- ter-borne compositions") may comprise solvents, binder, pigments and other additional components that favorably affect various properties of the compositions, such as polymeric surfactants and dispersants. The binder and the pigment, if present, are the primary solid components of the water-borne composition and remain on surfaces to which they have 20 been applied forming a solid layer as solvent evaporates. In water-borne compositions, the primary solvent is water. Typical water-borne compositions include latex paints. [0004] Polymer latexes or dispersions are widely used in water-based coatings. The polymer latex or dispersion is dried to form a film via coalescence to obtain desired mechanical and physical properties. Coalescence is a process whereby polymer particles in aqueous dispersion come into contact with one another during drying, and polymer chains 25 form (i.e., diffuse) across boundaries of latex/dispersion particles to yield continuous films with good bonding of the particles. [0005] A method of improving the properties of films formed by water- borne compositions is to include polymers that are capable of cross-linking. The polymers may be self cross-linking or require a cross-linking agent to react with the polymers. The cross-linking agents can be used to cross-link the binders and/or other polymeric additives such as 30 polymeric surfactants and dispersants (U.S. Patent No. 5,348,997) or rheology modifiers (U.S. Published Patent Appli- cation No. 2009/0162669). Cross-linking of polymers in coatings, inks, and other water-borne film-forming compositions can improve physical and mechanical strength, adhesion, and durability. In coating applications, cross-linking may also improve scrubability, blocking resistance, chemical resistance, and weatherability (See U.S. Patent No. 7,547,740 and U.S. Patent Application Publication No. 2007/0265391). Cross-linking of polymer constituents may also enhance adhe- 35 sion and bonding strength for adhesives. Additionally, cross-linking is widely utilized in the formulation of printing inks, in order to improve the mechanical and chemical resistance of prints. [0006] Cross-linking during and after coalescence further enhances the physical and mechanical properties of the films. However, if the polymer cross-linking reaction begins before the water-borne composition is applied to a surface, the resultant film may have poor physical and mechanical properties. Premature cross-linking is that which occurs within 40 the polymer latex or dispersion before it is applied to a surface and may prevent coatings from forming coalesced films. [0007] Premature cross-linking in compositions used for paints, inks, adhesives, dispersants, polymeric surfactants or rheology modifiers can also be disadvantageous in causing viscosity instability, thus reducing shelf-life. For example, typical latex base paints are manufactured in bulk and then dispensed into retail containers for shipping and storage. The retail container and its contents may be kept in a warehouse or a retail store prior to sale and ultimate use. During 45 this storage period, cross-linking of the polymers may occur, thereby reducing the quality of the latex paint. The cross- linked polymers may gel and/or build up viscosity in the can and a paint film formed therefrom can have reduced physical and mechanical properties such as reduced scrubability. [0008] Thus, in an effort to improve properties, water-borne compositions have been produced with polymers com- prising a monomer such as diacetone acrylamide ("DAAM") and the cross-linking agent adipic acid dihydrazide ("ADH"). 50 Without significant pre-application cross -linking, such water-borne compositions give improved properties over paint comprising non-cross-linkable polymer, but the improvement is not realized if there is any substantial pre-application cross-linking. Studies have shown that the cross-linking of polymers comprising DAAM with ADH cross-linking agent through a keto-hydrazide reaction has a substantial reaction rate in an aqueous solution. ("The diacetone acrylamide cross-linking reaction and its influence on the film formation of an acrylic latex", Journal of Coatings Technology and 55 Research, 5(3), 285-297, 2008.) Consequently, premature cross-linking impedes the attainment of desired properties. [0009] Other polymers are self-cross-linking. Self-cross-linking polymers such as polymers containing acetoacetox- yethylmethacrylate ("AAEM"), glycidyl methacrylate, and oxidative or UV curable functional groups are also used in water-borne coatings, inks, and adhesives. Unfortunately, self-cross-linked polymers yield only minimally improved 2 EP 2 576 708 B1 mechanical properties in the resultant films, particularly for scrubability of water-borne paints. [0010] An attempt to address the problem of cross-linking prior to application of a polymeric composition containing a polyhydrazide or the like, appears in U.S. Patent No. 4,786,676. There it is taught that polymeric compositions which have a long shelf life in aqueous solutions or dispersions and which undergo cross-linking after drying at room temperature 5 or elevated temperatures are obtainable by reacting polymeric organic compounds possessing carbonyl and carboxyl groups with polyhydrazides in the presence of monoketones and/or monoaldehydes. However, the development dis- cussed in the patent is not adequate for reliably suppressing premature cross-linking because there are side reactions which introduce impurities that degrade the desired stoichiometry, because any chemical species that might prevent premature cross-linking would not be produced in sufficient quantity within a time frame that the undesired reaction could 10 be precluded, and because the use of (at least) ketones can present a safety hazard. Therefore, the patent’s teaching does not afford a practical solution. [0011] US-2008/307587 discloses the deposition of a colorant-containing composition on a surface, wherein the com- position includes a rheology modifier, a stabilizer, a surfactant, a colorant, a resin, and a curative catalyst, which may comprise polyamines and especially dihydrazides. 15 [0012] US-2006/231487 discloses a coating composition applied to a filtration medium, which composition comprises a polymer, a cross-linking agent, and a compatibilizing agent having the functions of solubilizing the reactive polymer and reacting with the polymer to prevent cross-linking. [0013] WO 00/31197 discloses a coating composition comprising a polymer, a silane, and a pigment, wherein the polymer is said to include at least one hydrazide group. 20 [0014] EP-0945495 relates to a powder coating composition comprising a multilayer polymer particle, in which at least one inner layer is a polymer layer having a glass transition temperature of not over 20°C, and an outermost layer is a polymer layer having a glass transition temperature of not less than 60°C. The inner layer(s) has monomer components having an unsaturated double bond, including 0.3 to 5 weight % of a cross-linking monomer and 1 to 10 weight % of a grafting monomer. A curing agent, such as adipic acid dihydrazide, can be incorporated. 25 [0015] JP-2000 001633 discloses a powder coating composition exhibiting dispersibility in various powder coating materials, which is apparently much like that of the above-mentioned EP-0945495. [0016] There exists a need for a water-borne composition with improved physical, chemical and mechanical properties, such as, scrubability.