COATING COMPOSITIONS CONTAINING COPOLYMERS OF ETHYLENE OXIDE AND LONG CHAIN EPOXIDES

Abstract: Disclosed is a new water-based protective coating compo­ sition containing a water-soluble copolymer of ethylene oxide and at least one long chain 1,2-epoxyalkane having 8 to 26 car­ bon atoms. The water-soluble copolymer serves as a protec­ tive colloid, thickening agent, and rheology modifier for the coating composition.

Description: This invention relates to water-based protective coating compositions containing as the protective colloid, thickening agent, and rheology modifier, a copolymer of ethylene oxide and at least one 1,2-epoxyalkane having 8 to 26 carbon atoms. Water-based protective coating compositions are commonly known as latex paints or dispersion paints. The principal ingredients of a water-soluble protective coating composition are an aqueous polymer dispersion (also known as a latex), an opacifying pigment, a pigment dispersing agent, and a water-soluble protective colloid. Up until now typical water-soluble protective colloids used in the manufacture of latex paints include casein, methyl cellulose, hydroxyethylcellulose, sodium carboxymethylcellulose, polyvinyl alcohol, starch, sodium polyacrylates, etc. These colloids are used to stabilize the latices, to improve open time (wet edge property), or to aid in application properties, such as flow and leveling, or combinations thereof. Unfortunately, these colloids are not without their disadvantages. The natural-based colloids, such as the aforementioned cellulose ethers, can be susceptible to biological degradation and frequently impart poor flow and leveling properties. The synthetic materials, such as the polyvinyl alcohol, on the other hand, often lack the desirable thickening efficiency thereby providing a formulation which has reduced sag resistance when applied. Hence, there is a need for a protective colloid which is resistant to biological degradation, is an efficient rheology modifier and provides a latex paint with good flow and leveling properties. This invention provides water-based protective coating compositions characterized in that a hydrophobically modified water-soluble copolymer of ethylene oxide and at least one long chain epoxy-alkane is used as the protective colloid, and thickener, and rheology modifier. The compositions of this invention afford superior flow and leveling properties under both high and low shear conditions, and give excellent gloss. Suitable ethylene oxide copolymers include the copolymers of ethylene oxide with at least one 1,2-epoxyalkane containing from 8 to 26 carbon atoms, preferably from 12 to 24 carbon atoms. The 1,2-epoxyalkanes have the general formula EMI2.1 where n is 5 to 23. Suitable 1,2-epoxyalkanes include 1,2-epoxyhexadecane. Desirably the ethylene oxide copolymers contain, by weight of the copolymer, from about 95% to about 99.8% ethylene oxide and from about 5% to about 0.2% of the 1,2-epoxyalkane, preferably from about 1.5% to about 0.8%, and have a molecular weight from about 50,000 to about 320,000, preferably from about 80,000 to about 250,000. Generally from about 0.15% to about 1.0%, by weight of the total composition, of the ethylene oxide copolymer is used. Preferably from about 0.2% to about 0.7% of the copolymer is employed. Typical ethylene oxide copolymers and methods of preparing same are disclosed in U. S. Patent 4,304,902. There are three principal types of aqueous polymer dispersions used in the manufacture of water-based protective coating compositions, that is, the styrenebutadiene type, the vinyl acetate polymer and copolymer type, and the acrylic type. The predominant polymer used depends on the region and the particular type of water-based protective coating composition or latex paint, for example, gloss, semi-gloss, matte. Typically, the opacifying pigment is titanium dioxide (TiO2), alumina coated TiO2, or an alumina and silica coated Tit2. The rutile form of Tio2 is preferred. Any efficient dispersing agent can be employed to disperse the opacifying pigment. Suitable dispersing agents include diisobutylene-maleic anhydride copolymers. A good dispersing agent is essential for the preparation of high solids content latex paints and for good shelf stability. Moreover, the use of a pigment dispersing agent also allows some of the more costly opacifying pigment to be replaced with less expensive extender pigments, such as talc, silica, calcium carbonate, and mica. In addition to the principal ingredients, latex paints can contain additives such as defoamers, extender pigments, preservatives, surfactants, coalescing solvents, plasticizers, anti-corrosion agents, pH buffers, freeze-thaw stabilizers, storage stabilizers, and fragrances. Hercules defoamer 501 available from Hercules Incorporated is a suitable defoamer. A typical preservative is di(phenyl-mercury) dodecenyl succinate. Suitable surfactants include sodium dioctylsulfosuccinate. A typical coalescing solvent is 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate. To further illustrate this invention, various illustrative examples are set forth below. All parts and percentages are by weight, unless otherwise specified, throughout this specification. Example 1 This example illustrates the preparation of the ethylene oxide copolymers having utility in the water-based protective coating composition of this invention. A dry reaction vessel equipped with a magnetic stirring bar is charged with 50 ml of toluene, 50 ml of heptane, and 3.0 g of 1,2-epoxyalkane. The solution is sparged with nitrogen for 30 minutes and then 22 g of ethylene oxide is added via a cold syringe. The vessel is brought to 650C by heating in a water bath, and 4.0 ml of a l.3M catalyst solution is added. (The catalyst is prepared using the formulation and method set forth in Example 1 of U.S. Patent 3,642,667). The contents of the reaction vessel are kept at 65"C. for 2.5 hours at which time 2 ml of absolute ethanol is added as a shortstop. The contents of the reaction vessel are cooled and the white slurry is poured into 1.5 liters of a 50/50 hexane/acetone solution. The polymer precipitate is allowed to settle and the solvent is then decanted. The copolymer product is washed two more times with acetone, filtered, and dried. The copolymer product has a molecular weight from about 450,000 to about 600,000. The dry ethylene oxide copolymer is then treated with a sufficient amount of electron beam radiation, generally from about 0.2 to about 2.0 megarads, from a van der Graaf electron beam generator and subsequently cured at 530C. for about 18 hours to produce an ethylene oxide copolymer having a molecular weight of from about 50,000 to about 320,000. Any convenient method of degradation or depolymerization to reduce the molecular weight of the ethylene oxide copolymer can be used. For example, the molecular weight of the copolymer can be reduced by treatment with benzoyl peroxide in toluene at 800C. for 30 minutes, or with potassium peroxydisulfate in water at 600C. for 60 minutes. The ethylene oxide copolymers prepared essentially as set forth in Example 1 are listed in Table 1 with the major variations and molecular weight as indicated. Table 1 EMI5.1 <tb> <SEP> Carbon <SEP> atoms <SEP> eight <SEP> % <SEP> of <SEP> Molecular <tb> Ethylene <SEP> Oxide <SEP> in <SEP> the <SEP> epoxy- <SEP> comonomer <SEP> in <SEP> weight <SEP> of <SEP> the <tb> copolymer <SEP> No. <SEP> alkane <SEP> comonomer <SEP> copolymer <SEP> copolymer <tb> <SEP> 1 <SEP> C16 <SEP> 1.9 <SEP> 135,000 <tb> <SEP> 2 <SEP> C16 <SEP> 1.1 <SEP> 250,000 <tb> <SEP> 3 <SEP> C16 <SEP> 1.1 <SEP> 200,000 <tb> <SEP> 4 <SEP> Mixture <SEP> C20-24(a) <SEP> 1.1 <SEP> 250,000 <tb> <SEP> 5 <SEP> Mixture <SEP> C20-24 <SEP> 1.1 <SEP> 290,000 <tb> <SEP> 6 <SEP> Mixture <SEP> C20-24 <SEP> 1.1 <SEP> 320,000 <tb> <SEP> 7 <SEP> Mixture <SEP> C20-24 <SEP> 4.2 <SEP> 85,000 <tb> (a) The mixture of C20-24 consists of about 75% of a 1,2-epoxyalkane having 20 carbon atoms, about 15% of a 1,2-epoxyalkane having 22 carbon atoms, and about 10% of a 1,2-epoxyalkane having 24 carbon atoms. Examples 2-11 This example illustrates various embodiments of the water-based protective coating or latex paint composition of this invention and how to prepare it. A. Preparation of solutions of the ethylene oxide copolymer thickeners. A mixing vessel fitted with a stirrer is charged with 95g. of a 50/50, by weight, mixture of propylene glycol and water, and then 5g. of an ethylene oxide copolymer is added. The contents of the mixing vessel are stirred at room temperature (about 23"C.) for a time sufficient to dissolve the ethylene oxide copolymer in the propylene glycol and water mixture, generally about 1 hour. The resulting solution has approximately 5% concentration of the ethylene oxide copolymer thickener. B. Preparation of water-based protective coating composition. Suitable amounts of the opacifying pigment, a pigment dispersing agent, any extender pigments, defoamer, solvent and water are charged in a mixing vessel equipped with a high speed stirrer and stirred at high speed at room temperature (about 23 C.) until a homogeneous blend is obtained (about 20 minutes). The aqueous polymer dispersion or latex, water, and any other conventional additives, such as coalescing solvents, preservatives, surfactants, and the like, are added and stirred at moderate speed at room temperature until a homogeneous blend is obtained (about 20 minutes). A suitable amount of the thickener solution prepared as set forth in A. above is then added and stirring continued at room temperature at a moderate speed until a homogeneous water-based protective coating composition or latex paint is obtained (about 30 minutes). Table 2 below sets forth three embodiments of the latex paint compositions of this invention. Table 2 EMI7.1 <tb> <SEP> Parts <SEP> by <SEP> Weight <tb> Ingredients <SEP> Example <SEP> 2 <SEP> Example <SEP> 9 <SEP> Example <SEP> 11 <tb> Opacifying <SEP> pigment, <tb> TiO2 <SEP> 12.5 <SEP> 107.0 <SEP> 135.0 <tb> Pigment <SEP> dispersant <SEP> 4.25 <SEP> 3.5 <SEP> 5.4 <tb> Propylene <SEP> glycol <tb> solvent <SEP> 25.0 <SEP> 20.0 <SEP> 39.0 <tb> Defoamer <SEP> 1.0 <SEP> 1.0 <SEP> 1.0 <tb> Extender <SEP> pigment <SEP> 120.0 <SEP> - <SEP> <tb> Water <SEP> 37.0 <SEP> 80.0 <SEP> 3.0 <tb> Latex <SEP> A(1) <SEP> 250.0 <SEP> - <SEP> <tb> Latex <SEP> B(1) <SEP> - <SEP> 218.0 <SEP> <tb> Latex <SEP> C(1) <SEP> - <SEP> - <SEP> 278.0 <tb> Coalescing <SEP> solvent <SEP> 10.8 <SEP> 5.5 <SEP> 8.0 <tb> Preservative <SEP> 0.5 <SEP> 0.5 <SEP> 0.5 <tb> Surfactant <SEP> 0.25 <SEP> - <SEP> 1.0 <tb> Defoamer <SEP> 1.35 <SEP> 1.0 <SEP> 1.45 <tb> Water <SEP> 18.0 <SEP> 45.0 <SEP> 30.0 <tb> Thickener <SEP> solution <SEP> 50.0(2) <SEP> 21.5(3) <SEP> 30.5(3) <tb> Stormer <SEP> viscosity, <tb> Kreb <SEP> Units <SEP> (KU) <SEP> 92.0 <SEP> 103.0 <SEP> 86.0 <tb> (1) Latex A is Rhoplex AC-417 acrylic copolymer latex (48.0% solids); Latex B is Rhoplex AC-996 acrylic copolymer latex (60.0% solids); and Latex C is Rhoplex AC-490 acrylic copolymer latex (46.5% solids). Rhoplex is a trademark of Rohm and Haas Company for its acrylic latices. (2) 4.8% solids (3) 5.0% solids In Examples 3-8, the formulation set forth in Table 2 for Example 2 is used except that the thickener solution used contains different ethylene oxide copolymers. Likewise the formulation set forth in Table 2 for Example 9 is used for Example 10 except that the thickener solution-used contains a different ethylene oxide copolymer. The particular ethylene oxide copolymers which are used in Examples 2-11 are further identified in Table 3 below together with the properties of the water-based protective coating compositions or latex paints of this invention as compared to latex paint controls, each control containing a different weight % of hydroxyethyl cellulose (HEC) having a hydroxyethyl M.S. of 2.5 and a molecular weight of 600,000 as the thickener. (The designation M.S. refers to the average number of moles of hydroxyethyl substituent groups combined per anhydroglucose unit of the cellulose molecule.) Hydroxyethyl cellulose is used as the thickener in the controls since it is a common latex paint thickener, and since homopolymers of ethylene oxide do not satisfactorily thicken latex paints and, thus, cannot be used as meaningful controls. Table 3 EMI9.1 Copolymer <tb> or <SEP> HEC, <SEP> Wt. <SEP> % <tb> Example <SEP> Copolymer <SEP> Latex <SEP> total <SEP> Flow <SEP> and <SEP> Sag <tb> No. <SEP> No. <SEP> (Table <SEP> 1) <SEP> Type <SEP> (1) <SEP> composition <SEP> Levelling <SEP> (2) <SEP> Resistance <SEP> (3) <SEP> Spatter <SEP> (4) <tb> 2 <SEP> 3 <SEP> A <SEP> 0.40 <SEP> 10 <SEP> 9 <SEP> 8 <tb> 3 <SEP> 1 <SEP> A <SEP> 0.46 <SEP> 10 <SEP> 12 <SEP> 10 <tb> 4 <SEP> 2 <SEP> A <SEP> 0.39 <SEP> 10 <SEP> 12 <SEP> 6 <tb> 5 <SEP> 4 <SEP> A <SEP> 0.69 <SEP> 10 <SEP> 8 <SEP> 6 <tb> 6 <SEP> 5 <SEP> A <SEP> 0.35 <SEP> 10 <SEP> 8 <SEP> 7 <tb> 7 <SEP> 6 <SEP> A <SEP> 0.22 <SEP> 5 <SEP> 12 <SEP> 10 <tb> 8 <SEP> 7 <SEP> A <SEP> 0.49 <SEP> 10 <SEP> 8 <SEP> 6 <tb> Control <SEP> HEC <SEP> A <SEP> 0.23 <SEP> 3 <SEP> 12 <SEP> 5 <tb> 9 <SEP> 1 <SEP> B <SEP> 0.21 <SEP> 10 <SEP> 12 <SEP> 8 <tb> 10 <SEP> 6 <SEP> B <SEP> 0.24 <SEP> 10 <SEP> 12 <SEP> 7 <tb> Control <SEP> HEC <SEP> B <SEP> 0.51 <SEP> 4 <SEP> 12 <SEP> 4 <tb> 11 <SEP> 6 <SEP> C <SEP> 0.29 <SEP> 8 <SEP> 11 <SEP> 8 <tb> Control <SEP> HEC <SEP> C <SEP> 0.25 <SEP> 3 <SEP> 12 <SEP> 3 <tb> (1) Latex A is Rhoplex AC-417 acrylic copolymer latex (48.0% solids); Latex B is Rhoplex AC-996 acrylic copolymer latex (60.0% solids); and Latex C is Rhoplex AC-490 acrylic copolymer latex (46.5% solids). Rhoplex is a trademark of Rohm and Haas Company for its acrylic latices. (2) Visual examination of drawdowns using Leneta blade; ASTM D4062-81. Ratings are 1-10 where 1 is unacceptable flow and levelling and 10 is superior flow and levelling. (3) Leneta Anti-Sag Index; ASTM D3730-78. Ratings are 1-12 where 1 is unacceptable sag resistance and 12 is superior sag resistance. (4) Spatter is determined according the procedure described in Sward, G.G., The Paint Testing Manual, 425 (13th Ed. 1972). Ratings are 1-10 where 1 is unacceptable tendency to spatter and 10 is superior in its tendency not to spatter Thus, as the data in Table 3 illustrates, this invention provides water-based protective coating compositions having greatly reduced spatter, excellent flow and levelling properties, and largely uncompromised sag resistance. Moreover, the ethylene oxide copolymers used in the water-based protective coating compositions of this invention give excellent gloss characteristics when combined with aqueous polymer dispersions or latices. Features, advantages and other specific embodiments of this invention will become readily apparent to those exercising ordinary skill in the art after reading the foregoing disclosures. In this regard, while specific embodiments of this invention have been described in considerable detail, variations and modifications of these embodiments can be effected without departing from the spirit and scope of the invention as disclosed and claimed.

Claims: What is claimed is: 1. A water-based protective coating composition having an aqueous polymer dispersion, an opacifying pigment, a pigment dispersing agent, and a water-soluble protective colloid and thickener, characterized in that it contains a copolymer of ethylene oxide and at least one 1,3-epoxyalkane having 8 to 26 carbon atoms as the water-soluble protective colloid and thickener. 2. The composition of claim 1 wherein (d) is present in an amount from about 0.15% to about 1.0% by weight of the composition. 3. The composition of claim 1 wherein the copolymer contains, by weight of the copolymer, from about 95% to about 99.8% ethylene oxide and from about 5% to about 0.2% of the 1,2-epoxyalkane. 4. The composition of claim 3 wherein the 1,2-epoxyalkane is 1,2-epoxyhexadecane. 5. The composition of claim 1 wherein (d) has a molecular weight of from about 50,000 to about 320,000. 6. The composition of claim 1 wherein the aqueous pigment dispersion is an acrylic copolymer latex. 7. A method of impregnating or coating a substrate which comprises treating the substrate with the composition of claim 1.

Inventors: ROYCE, RICHARD DAY, JR.
Applicants: HERCULES INCORPORATED
Application year: 1984
Main classification: C09D7
IPC codes: C09D7, C08G65, C09D171