Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
2000-12-11
2002-04-23
Niland, Patrick D. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C524S401000, C524S500000, C524S501000, C524S502000, C524S504000, C524S533000, C524S556000, C524S559000, C524S804000, C524S823000, C524S832000, C524S833000, C524S849000, C526S072000, C526S075000, C526S318400, C526S318430, C526S321000
Reexamination Certificate
active
06376600
ABSTRACT:
This invention is concerned with an aqueous composition. More particularly, the present invention concerns an aqueous composition comprising, dispersed or dissolved therein, a copolymer of a terminally unsaturated oligomer.
Aqueous based coatings, such as for example latex or emulsion polymer containing paints, constitute a significant segment of all coatings in use today. Aqueous based coatings offer the advantages of being generally easier to use than conventional oil based coatings, such as for example alkyd paints, and contain fewer or no undesirable volatile organic solvents.
Formulators of aqueous based coatings desire to match or improve upon the performance properties of alkyd based paints, including for example scrub resistance, corrosion resistance, efflorescence resistance, block resistance, dirt pick-up resistance, tack resistance. mar resistance, print resistance. stress resistance and opacifying capability, Though it may be highly desirable for a paint to demonstrate maximum performance for all relevant properties, in reality such paints cannot be achieved, for example a paint with maximum dirt pick-up resistance may not be able to demonstrate maximum stress resistance as well. Instead, formulators tend to provide no optimized paints, which are paints having a compromise of several desirable properties, for example a paint with good dirt pick-up resistance may be able to demonstrate average stress resistance.
A formulator can alter the properties of a particular coating by adjusting it's composition, such as by changing the particular amounts of the components and/or by changing the composition of those components.
Aqueous dispersions or solutions of carboxylic acid containing polymers are known to have many applications, including use as binders in coating compositions. Typically, these polymers are formed from the polymerization of a mixture of ethylenically unsaturated monomers comprising up to 20%, typically 0.05% to 10%, by weight of a carboxylic acid containing monomer, such as acrylic acid (AA) or methacrylic acid (MAA). The properties of a coating comprising such polymers can be altered by either changing the mixture of monomers to be polymerized to form a particular polymer, and/or by using two or more different polymers and/or by using multi-staged (e.g. core/shell) polymers, as disclosed for example in U.S. Pat. No. 4,193,902, EP-A-0466409, EP-A-0612805, EP-A-0694564 and EP-A-0741173.
WO-A-9532228 and WO-A-9532255 each disclose aqueous coatings including a binder based on a graft copolymer comprising 2 to 98%, preferably 60 to 95%, most preferably 60 to 85%, by weight of a polymeric backbone of polymerized ethylenically unsaturated monomers and 98 to 2%, preferably 40 to 5%, most preferably 40 to 15%, by weight of macromonomers attached to said polymeric backbone at a single terminal point of said macromonomer, said macromonomer having a number average molecular is weight of 500 to 30,000 and comprising 5 to 100%, preferably at least 10% and more preferable 20 to 40%, by weight of macromonomers, of polymerized alpha-beta ethylenically unsaturated monomers having carboxylic-acid functionalities or instead amine functionalities, and wherein at least a portion of the carboxylic-acid or amine groups have been neutralized and wherein the macromonomers are soluble or dispersed in aqueous carrier to stabilize the portion of the graft polymer which forms an insoluble particle. The graft copolymer is disclosed to have a weight average molecular weight up to 500,000, with a most preferred weight average molecular weight substantially less than 500,000 e.g. up to 300,000. The graft copolymers are described to be useful as film forming vehicles in the preparation of waterborne coating compositions such as, for example, basecoat or clearcoat compositions useful in automotive applications.
There is a continuing desire by formulators to provide aqueous coatings which demonstrate improved performance, such as scrub resistance, corrosion resistance, and/or efflorescence resistance, over other aqueous coatings. It is an object of this invention, therefore, to provide aqueous compositions which are particularly, though not exclusively, useful as performance enhancing binders for aqueous coatings. In particular, though not exclusively, it is the object of this invention to provide aqueous coatings for improving at least one of the following properties of an aqueous coating: scrub resistance, corrosion resistance, efflorescence resistance and opacifying capacity.
In accordance with the present invention, there is provided an aqueous composition comprising, dispersed or dissolved therein, a copolymer formed by polymerisation, preferably by emulsion polymerisation, of a monomer mixture consisting of:
a) 0.05 to less than 4.5% by weight of one or more terminally unsaturated oligomers of the formula:
wherein N is the residue of an ethylenically unsaturated monomer of the formula:
wherein M is the residue of an ethylenically unsaturated monomer other than N;
wherein said N and M residues are randomly arranged in said oligomer;
wherein m is the total number of M residues in said oligomer and is in the range 0 to 75;
wherein n is the total number of N residues in said oligomer and is in the range 3 to 150;
wherein n is equal to or greater than m and the sum of n and m is in the range from 3 to 150;
wherein X and each Y is independently selected from the group consisting of H, NH
4
, alkali metals and alkaline earth metals; and
wherein each Z is independently selected from the group consisting of H and CH
3
;
b) greater than 85.5 to 99.95% by weight of at least one monomer selected from the group consisting of esters of acrylic and methacrylic acid with alcohols containing from 1 to 24 carbons, amides of acrylic and methacrylic acid, vinyl esters of carboxylic acids containing from 1 to 20 carbons, vinyl-aromatic compounds containing compounds containing up to 20 carbons, ethylenically unsaturated nitriles containing from 3 to 6 carbons, vinyl halides, and non-aromatic hydrocarbons containing from 2 to 8 carbons and at least one olefinic double bond; and
c) 0 or up to 10% by weight of one or more other copolymerisable monomers.
In accordance with another aspect of the present invention, there is provided a method of improving the performance of a coating, wherein the method comprises I) applying to a substrate an aqueous coating composition comprising, dispersed or dissolved therein. a copolymer formed by polymerization, preferably emulsion polymerization, of a monomer mixture consisting of:
a) 0.05 to less than 4.5% by weight of one or more terminally unsaturated oligomers of the formula:
wherein N is the residue of an ethylenically unsaturated monomer of the formula:
wherein M is the residue of an ethylenically unsaturated monomer other than N;
wherein said N and M residues are randomly arranged in said oligomer;
wherein m is the total number of M residues in said oligomer and is in the range 0 to 75;
wherein n is the total number of N residues in said oligomer and is in the range 3 to 150;
wherein n is equal to or greater than in and the sum of n and in is in the range from 3 to 150;
wherein X and each Y is independently selected from the group consisting of H, NH
4
, alkali metals and alkaline earth metals; and
wherein each Z is independently selected from the group consisting of H and CH
3
;
b) greater than 85.5 to 99.95% by weight of at least one monomer selected from the group consisting of esters of acrylic and methacrylic acid with alcohols containing from 1 to 24 carbons, amides of acrylic and methacrylic acid, vinyl esters of carboxylic acids containing from 1 to 20 carbons, vinyl-aromatic compounds containing compounds containing up to 20 carbons, ethylenically unsaturated nitriles containing from 3 to 6 carbons, vinyl halides and non-aromatic hydrocarbons containing from 2 to 8 carbons and at least one olefinic double bond; and
c) 0 or up to 10% by weight of one or more other copolymerisable monomers; and II) drying the aqueous coating composition to form sa
Edwards Stephen Scott
Greenblatt Gary David
Hageman Bradley Keith
Larson Gary Robert
Lesko Patricia Marie
Greenblatt Gary D.
Niland Patrick D.
Rohm and Haas Company
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