Polymer compositions and methods of making and using same

Abstract

A phosphoric acid ester composition comprising a polymerizable phosphoric acid monoester compound or a salt thereof and a polymerizable phosphoric acid diester compound or a salt thereof. A phosphate ester composition produced by polymerization using a polymerizable phosphate monoester compound or salt thereof and a polymerizable phosphate diester compound or salt thereof. Methods of making and using such polymer compositions, for example, as aqueous coating compositions, and coating compositions having improved adhesion, corrosion resistance, water resistance, gloss, gloss retention, and hiding power. A method for improving adhesion, corrosion resistance, water resistance, gloss, gloss retention and hiding power of a coating composition by using a polymer composition in the coating composition.

Description

Polymer compositions and their manufacturing and use methods

[0001] This application claims priority to the application filed on August 3, 2023, in international proceedings under the number CN 2023 / 111031, the entire contents of which are incorporated herein by reference for all purposes. Technical Field

[0002] This invention relates to an emulsion polymer composition produced by emulsion polymerization using polymerizable monophosphate compounds or salts and polymerizable diester compounds or salts thereof. The invention also relates to methods of manufacturing such emulsion polymer compositions, for example as waterborne coating compositions, and coating compositions having improved adhesion, corrosion resistance, water resistance, gloss, gloss retention, and hiding power. This invention relates to a method of using emulsion polymer compositions to improve the adhesion, corrosion resistance, water resistance, gloss, gloss retention, and hiding power of coating compositions. This is particularly useful in direct-to-metal applications, providing improved adhesion, improved gloss, improved corrosion resistance, and improved water resistance. This invention provides waterborne paints and industrial coating formulations to avoid solvent-based formulations. Background Technology

[0003] Latex and emulsion (aqueous dispersions of polymers obtained through emulsion polymerization) are widely used in a variety of applications, such as paints, adhesives, paper coatings, and carpet backings. While some applications do not require it, a key property of latex is its ability to bond to a wide variety of substrates. Therefore, adhesion is a critical factor, and one of the most challenging aspects is wet adhesion. However, the adhesion of such paints or coatings to substrates is often adversely affected by the large amounts of emulsifiers (surfactants) required in the emulsion polymerization process. These emulsifiers, for example, affect adhesion, and particularly wet adhesion, in many ways.

[0004] One way these emulsifiers affect adhesion is by migrating to the interface during the drying process. Emulsifiers tend to migrate to the surface during drying and accumulate at the interface between the paint or coating and the substrate. At the coating-substrate interface, the emulsifier reduces adhesion by forming a bilayer structure that is less adhesive and more sensitive to moisture or other external water. This effect can compromise the properties of the coating. At the coating / air interface, this effect reduces the interfacial tension of the coating, allowing water to spread easily on the surface and increasing water diffusion across the interface.

[0005] Another way such emulsifiers affect adhesion is by forming interconnected clusters in the coating. Surfactants are often incompatible with paints and pigments and tend to separate during and after the drying process. One negative effect is that they can create fogging in the coating due to differences in refractive index, which is particularly detrimental to varnishes (binders for paints). The main problem is the extremely strong ability of these clusters to carry water throughout the film and at the film / substrate interface, which impairs the mechanical properties of the coating, especially adhesion.

[0006] In addition, many of these emulsifiers are often incompatible with other paint or coating components and tend to separate, carry water, and cause fogging.

[0007] In addition, surfactants can increase foaming and require the addition of defoamers, which can have other problems, such as causing coating dehydration (e.g., fisheye formation in the paint film). Finally, cross-interactions often exist in coatings, which can cause latex surfactants to migrate to pigments, resulting in paint instability. This phenomenon is detrimental to paint quality and water resistance. Unfortunately, although some experiments have been conducted on a laboratory scale to run emulsion polymerization without surfactants, there is no known industrial method to do so. Surfactants remain a necessary evil. Decades ago, functional monomers with stabilizing groups (carboxyl, sulfate, sulfonate, etc.) emerged and helped to significantly reduce the amount of surfactant, thereby improving properties. However, they are not surfactant materials and therefore cannot stabilize monomer pre-emulsions or be used alone during the nucleation phase.

[0008] Therefore, it is desirable for the existence of available polymerizable monomers that enable the elimination or reduction of the amount of such emulsifiers required in the emulsion polymerization process. Summary of the Invention

[0009] This invention provides a phosphate ester composition comprising:

[0010] (a) At least one polymerizable phosphate monoester compound having formula (I) or a salt thereof:

[0011] R 1 -C(O)-R 2 –X 1 (I)

[0012] in:

[0013] R 1 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, and typically the vinyl group is methyl-substituted;

[0014] R 2It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units;

[0015] X 1 It is a phosphate ester group.

[0016] The salt—if present, preferably a sodium, potassium, or ammonium salt; and

[0017] (b) At least one polymerizable phosphate diester compound having formula (II) or a salt thereof:

[0018] R 3 -C(O)-R 4 –X 2 -R 4 -C(O)-R 3 (II)

[0019] in:

[0020] R 3 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, and typically the vinyl group is methyl-substituted;

[0021] R 4 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units;

[0022] X 2 It is a phosphate ester group.

[0023] The salt—if present—is preferably a sodium, potassium, or ammonium salt; and

[0024] The weight ratio of the polymerizable monophosphate compound having formula (I) to the polymerizable diester compound having formula (II) ranges from 1.2 to 2.1:1, or typically 1.4 to 2.1:1, 1.5 to 2.1:1, 1.5 to 2.0:1, 1.6 to 1.9:1, 1.7 to 1.9:1 or 1.8 to 1.9:1.

[0025] This invention provides a polymer composition comprising monomer units derived from the following:

[0026] (A) A phosphate ester composition comprising at least one polymerizable monophosphate compound or a salt thereof and at least one polymerizable diester compound or a salt thereof as described in this specification, wherein the phosphate ester composition comprises:

[0027] (a) At least one polymerizable phosphate monoester compound having formula (I) or a salt thereof:

[0028] R 1 -C(O)-R 2 –X 1 (I)

[0029] in:

[0030] R 1 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, and preferably the vinyl group is methyl-substituted;

[0031] R 2 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units;

[0032] X 1 It is a phosphate ester group.

[0033] The salt—if present, preferably a sodium, potassium, or ammonium salt; and

[0034] (b) At least one polymerizable phosphate diester compound having formula (II) or a salt thereof:

[0035] R 3 -C(O)-R 4 –X 2 -R 4 -C(O)-R 3 (II)

[0036] in:

[0037] R 3 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group;

[0038] R 4 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units;

[0039] X 2 It is a phosphate ester group.

[0040] The salt—if present—is preferably a sodium, potassium, or ammonium salt.

[0041] The weight ratio of the polymerizable monophosphate compound of formula (I) to the polymerizable diester compound of formula (II) ranges from 1.2-2.1:1, or typically 1.4-2.1:1, 1.5-2.1:1, 1.5-2.0:1, 1.6-1.9:1, 1.7-1.9:1, or 1.8-1.9:1; and

[0042] (B) At least one other polymerizable monomer.

[0043] In another aspect, the present invention also provides a method for producing the polymer composition of the present invention.

[0044] In particular, the present invention relates to a method for producing a polymer composition, the method comprising:

[0045] Combining (A) the phosphate ester composition described herein with (B) at least one other polymerizable monomer to form a mixture; and

[0046] To polymerize at least one polymerizable monophosphate compound or salt thereof, and at least one polymerizable diester compound or salt thereof, and at least one other polymerizable monomer of a phosphate ester composition.

[0047] Typically, the polymer composition further comprises a surfactant, preferably anionic surfactant, and most preferably a phosphate anionic surfactant, and polymerization is carried out by emulsion polymerization. However, polymerization can be carried out in the presence of polymerizable monophosphate compounds, polymerizable diester compounds, and polymerizable monomers without the addition of surfactants, for example, the polymerization of these components in a solvent.

[0048] Preferably, the polymerizable monophosphate compound or its salt and the polymerizable diester compound or its salt do not have an oxypropylidene unit.

[0049] Polymerizable monophosphate compounds and polymerizable diester compounds act as polymerizable "monomers". These monomers can be used in acidic and basic forms. For basic forms, sodium hydroxide, potassium hydroxide, or ammonium hydroxide are typically used for neutralization.

[0050] This invention provides beneficial results, particularly for improving the performance of water-based industrial coatings. Preferably, this invention provides industrial coatings that meet ISO 12944 classifications C3 and C4.

[0051] The polymerizable phosphate monomers of the present invention, which are highly mono- or diester-based, enable the elimination or reduction of conventional emulsifiers (surfactants) used in emulsion polymerization and eliminate or reduce the problems or disadvantages associated with their presence in the resulting latex (emulsion) used in paints or coatings. Attached Figure Description

[0052] Figure 1 compares paint C and paint D.

[0053] Figure 2 compares polished CRS panels with the following coatings: Coating C; Coating A; and Coating B.

[0054] Figure 3 shows the standard grading based on the adhesion test results of ASTM D3359 cross-cut adhesion test.

[0055] Figure 4 shows the results of testing the adhesion of the paint to the metal according to the ASTM D3359 method.

[0056] Figure 5 shows the results of testing the adhesion of the paint to the metal according to the ASTM D3359 method using the procedure used to obtain Figure 4.

[0057] Figure 6 shows a comparison of gloss retention rates of paint applied to treated aluminum plates at a DFT of 50 µm, tested using the ASTM G154 method (using a UV-A lamp).

[0058] Figure 7 compares the percentage of opacity and opacity of a paint made with a styrene-acrylic latex polymer (made with 2 wt.% MAA and 3 wt.% of the monomer C of the present invention) with a control latex made with 5% MAA and without the monomer C of the present invention.

[0059] Figure 8 summarizes the benefits of using latex emulsified with the phosphate ester composition C of the present invention to manufacture paints.

[0060] Figure 9 compares the paint E1 and paint E2 of the present invention.

[0061] Figure 10 shows a comparison of the control paint and the paint of the present invention.

[0062] Figure 11 shows the gloss retention of the test sample coated with paint F2 containing benzophenone.

[0063] Figure 12A shows a test sample coated with paint AA made of Ex.10 latex AA.

[0064] Figure 12B shows a test sample coated with a paint BB made of Ex.10 latex BB.

[0065] Figure 12C shows a test sample coated with paint CC made from Ex.10 latex CC. Detailed Implementation

[0066] General definition

[0067] The terms and phrases “invention,” “present invention,” and similar terms and phrases used herein are non-limiting and are not intended to limit the subject matter of the invention to any single embodiment, but rather to cover all possible embodiments as described.

[0068] Throughout this specification, including the claims, unless otherwise specified, the term "a" and the phrase "at least one" are synonymous, and similarly, the phrase "comprising one (or comprising a)" should be understood to be synonymous with the term "comprising at least one." Additionally, "between" should be understood to include the limit. Furthermore, throughout this specification, including the claims, the terms "comprising" and "having" are used interchangeably and should be understood to be synonymous.

[0069] It should be noted that when specifying any range of concentration, weight ratio, or amount, any specific upper limit concentration, weight ratio, or amount can be associated with any specific lower limit concentration, weight ratio, or amount.

[0070] As used herein, the term "alkyl (or alkyl group)" means a saturated hydrocarbon group that can be straight-chain, branched, or cyclic, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, n-hexyl, and cyclohexyl.

[0071] As used herein, the term "bicyclic" or "bicyclic group" means a group containing at least two connecting rings having at least two common atoms. In some embodiments, a bicyclic group may contain at least two fused, bridged, or both rings.

[0072] As used herein, the term "cycloalkyl (or cycloalkyl group)" refers to a saturated hydrocarbon group that contains one or more cyclic alkyl rings, such as cyclopentyl, cyclooctyl, and adamantyl.

[0073] As used herein, the term "hydroxyalkyl (or hydroxyalkyl group)" refers to an alkyl group that has been substituted with a hydroxyl group, more typically an alkyl group such as hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxydecyl.

[0074] As used herein, the term "alkylene (or alkylene group)" means a divalent acyclic saturated hydrocarbon group, including but not limited to methylene, polymethylene, and alkyl-substituted polymethylene, such as dimethylene, tetramethylene, and 2-methyltrimethylene.

[0075] As used herein, the term "alkenyl (or alkenyl group)" refers to an unsaturated straight-chain, branched, or cyclic hydrocarbon group containing one or more carbon-carbon double bonds, such as vinyl, 1-propenyl, or 2-propenyl.

[0076] As used herein, the term "aryl (or aryl group)" refers to a monovalent unsaturated hydrocarbon group containing one or more six-membered carbon rings, wherein the degree of unsaturation can be represented by three conjugated double bonds, which can be substituted at one or more carbons of the ring with hydroxyl, alkyl, alkenyl, halogen, haloalkyl, or amino groups, such as phenoxy, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, chlorophenyl, trichloromethylphenyl, and aminophenyl.

[0077] As used herein, the term "aralkyl (or aralkyl group)" refers to an alkyl group substituted with one or more aryl groups, such as phenylmethyl, phenylethyl, and triphenylmethyl.

[0078] As used in this article, "AGE" stands for allyl glycidyl ether.

[0079] As used herein, the term "(C)" refers to organic groups. n -C m (where n and m are integers) indicates that the group can contain from n to m carbon atoms per group.

[0080] As used herein, the terms “olefin unsaturation,” “olefin unsaturated,” or similar terms refer to terminal (i.e., α, β) carbon-carbon double bonds.

[0081] As used in this article, "DPUR" means stain resistance.

[0082] Phosphate ester composition

[0083] In one aspect, the present invention relates to a phosphate ester composition comprising:

[0084] (a) At least one polymerizable phosphate monoester compound having formula (I) or a salt thereof:

[0085] R 1 -C(O)-R 2 –X 1 (I)

[0086] in:

[0087] R 1 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, and typically the vinyl group is methyl-substituted;

[0088] R2 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units;

[0089] X 1 It is a phosphate ester group.

[0090] The salt—if present, preferably a sodium, potassium, or ammonium salt; and

[0091] (b) At least one polymerizable phosphate diester compound having formula (II) or a salt thereof:

[0092] R 3 -C(O)-R 4 –X 2 -R 4 -C(O)-R 3 (II)

[0093] in:

[0094] R 3 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, and typically the vinyl group is methyl-substituted;

[0095] R 4 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units;

[0096] X 2 It is a phosphate ester group.

[0097] The salt—if present—is preferably a sodium, potassium, or ammonium salt; and

[0098] The weight ratio of the polymerizable monophosphate compound having formula (I) to the polymerizable diester compound having formula (II) ranges from 1.2 to 2.1:1, or typically 1.4 to 2.1:1, 1.5 to 2.1:1, 1.5 to 2.0:1, 1.6 to 1.9:1, 1.7 to 1.9:1 or 1.8 to 1.9:1.

[0099] Typically, the weight ratio of a polymerizable monophosphate compound having formula (I) to a polymerizable diester compound having formula (II) ranges from 55:45 to 67:33, preferably from 60:40 to 67:33, and more preferably from 64:36 to 67:33, wherein the sum of the weight parts of the polymerizable monophosphate compound and the polymerizable diester compound equals 100 parts by weight. For example, the weight ratio range of 55:45 to 67:33 covers 55:45, 60:40, or 67:33; however, the weight ratio range of 55:45 to 67:33 does not cover 55:33 or 67:45.

[0100] The polyoxyalkylene unit can be derived from a variety of alkyl oxide compounds (including ethylene oxide, propylene oxide, butane oxide, and phenylene oxide); other alkyl, cycloalkyl, or aryl-substituted alkyl oxides; or alkyl or aryl glycidyl ethers. It may additionally contain a hydrocarbon segment, such as by ring-opening caprolactone via 2-hydroxyethyl methacrylate.

[0101] Typically, the R of phosphate ester compositions 1 Choose the group consisting of CH2=CH-, CH2=C(CH3)-, or cis-CH(COOH)=CH.

[0102] Typically, the R of phosphate ester compositions 2 It has one to five, preferably one to three oxyethylidene units.

[0103] Typically, the R of phosphate ester compositions 2 It has at least one oxyethylidene unit.

[0104] Typically, having R 2 R of phosphate ester compositions 2 It lacks an oxypropylidene unit.

[0105] Typically, the R of phosphate ester compositions 3 Choose the group consisting of CH2=CH-, CH2=C(CH3)-, or cis-CH(COOH)=CH-.

[0106] Typically, the R of phosphate ester compositions 4 It is a divalent polyoxyalkylene group having at least one oxyethylidene unit.

[0107] Typically, the R of phosphate ester compositions 4 It is a divalent polyoxyalkylene group having one to three oxyethylidene units.

[0108] Preferably, the polymerizable monophosphate compound or its salt and the polymerizable diester compound or its salt of the ester composition do not have oxypropylidene units.

[0109] Typical polymerizable monophosphate compounds with formula (I) (also known as monoalkyl phosphate esters (MAPs)) have structural formula (Ia):

[0110] Ia

[0111] Where R is an optional substituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group; n is the molar number of ethylene oxide; and M is H, NH4, Na, or K.

[0112] Typical polymerizable phosphate diester compounds having formula (II) (also known as dialkyl phosphate esters (DAP)) have structural formula (IIa):

[0113] IIa

[0114] Where R is an optional substituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group; n is the molar amount of ethylene oxide; and M is H, NH4, or K.

[0115] Typical polymerizable monophosphate compounds of formula (I) (also known as monoalkyl phosphate esters (MAPs)) have structural formula (Ib):

[0116] (Ib)

[0117] Where R is H or Me, R1 is H or Me, n is 1-5, and each R2 is independently H, NH4, Na, or K, typically H. Preferably, each R1 is H, or at least two R1s are H and at least one R1 is Me.

[0118] Typical polymerizable phosphate diester compounds having formula (II) (also known as dialkyl phosphate esters (DAP)) have structural formula (IIb):

[0119] (IIb)

[0120] Where R is H or Me, R1 is H or Me, n is 1-5, and R2 is H, NH4, Na, or K, typically H. Preferably, for the portion on each side of the phosphate ester group, each R1 is H, or at least two R1s are H and at least one R1 is Me.

[0121] Typically, ((2-methyl-1-oxopropane-1,3-diyl)bis(oxy))bis(ethane-2,1-diyl)bis(2-methacrylate) is 10 wt.% to 20 wt.% of the phosphate ester composition, more typically 15 wt% to 20 wt%.

[0122] Typically, ethylene glycol dimethacrylate is 1 wt.% to 10 wt.% of the phosphate ester composition, more typically 3 wt% to 7 wt%.

[0123] Typically, the phosphate ester composition further comprises phosphoric acid, preferably in a weight ratio of phosphoric acid to the sum of a polymerizable monophosphate compound having formula (I) and a polymerizable diester compound having formula (II) of 10:90 to 25:75, more preferably 12:90 to 20:70.

[0124] At least one polymerizable monophosphate compound having formula (I) or a salt thereof and a polymerizable diester compound having formula (II) may be neutralized by one or more of sodium hydroxide, potassium hydroxide or ammonium hydroxide, preferably ammonium hydroxide.

[0125] Method for producing the above-mentioned phosphate ester composition

[0126] In another aspect, the present invention also provides a method for producing the above-described phosphate ester composition having a high ratio of poly(meth)acrylate polymerizable monophosphate and poly(meth)acrylate polymerizable diester.

[0127] Polymerizable phosphate monoesters and diesters can be prepared by different routes. For example, preferred polymerizable phosphate monoesters or diesters (where X is a phosphate ester -OPO3H2 group) can be prepared by phosphorylation of an esterification product of a polyalkylene glycol with a vinyl functional carboxylic acid or its anhydride or acyl halide. Phosphorylation can be carried out as disclosed in U.S. Patents 5,463,101, 5,550,274 and 5,554,781 and European Patent Publication No. EP 0 675,076 A2. Polymerizable phosphate monoesters or diesters (where X is a sulfate ester -OSO3H2 group or a sulfonate ester -SO3H group) can be prepared by sulfating one of the hydroxyl groups of the polyalkylene glycol or replacing the hydroxyl group with a sulfonate group, and then esterifying the remaining hydroxyl groups of the polyalkylene glycol with a vinyl functional carboxylic acid or its anhydride or acyl halide.

[0128] In particular, the present invention relates to a method for producing a phosphate ester composition comprising:

[0129] (a) At least one polymerizable phosphate monoester compound having formula (I) or a salt thereof:

[0130] R 1 -C(O)-R 2 –X 1 (I)

[0131] in:

[0132] R 1 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, and typically the vinyl group is methyl-substituted;

[0133] R 2 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units;

[0134] X 1 It is a phosphate ester group.

[0135] The salt—if present, preferably a sodium, potassium, or ammonium salt; and

[0136] (b) At least one polymerizable phosphate diester compound having formula (II) or a salt thereof:

[0137] R 3 -C(O)-R 4 –X 2 -R 4 -C(O)-R 3 (II)

[0138] in:

[0139] R 3 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, and typically the vinyl group is methyl-substituted;

[0140] R 4 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units;

[0141] X 2 It is a phosphate ester group.

[0142] The salt—if present—is preferably a sodium, potassium, or ammonium salt; and

[0143] The weight ratio of the polymerizable phosphate monoester compound having formula (I) to the weight ratio of the polymerizable phosphate diester compound having formula (II) ranges from 1.2 to 2.1:1, or typically 1.4 to 2.1:1, 1.5 to 2.1:1, 1.5 to 2.0:1, 1.6 to 1.9:1, 1.7 to 1.9:1, or 1.8 to 1.9:1; and

[0144] The method includes the following steps:

[0145] A) Prepare the phosphate-alcohol reactant solution by the following method.

[0146] i) In the reactor under essentially non-reactive temperature conditions:

[0147] Dissolve a) about 75% by weight to about 117% by weight of phosphoric acid or polyphosphoric acid in...

[0148] b) At least one having the formula R 1 -C(O)-R 2 -OH (where R) 1 and R 2 In an alcohol medium (e.g., hydroxyethyl methacrylate) as defined above;

[0149] B) Then

[0150] ii) Blend a stoichiometric amount of phosphoric anhydride into the reactant solution, and

[0151] iii) Reacting the phosphoric acid in the reactant solution with a stoichiometric amount of phosphoric anhydride; and

[0152] C) Typically, the phosphorylating agent thus generated is reacted with an alcoholic medium at about 75°C to about 100°C for a reaction holding time of about 4 to about 20 hours. After holding, deionized water is typically added to the reactor to hydrolyze any residual pyrophosphate, followed by holding for another 1–4 hours, and then cooling. To suppress unwanted homopolymerization, methoxyhydroquinone (MEHQ) or other suitable inhibitors can be added to the reactor and dissolved in the reactant solution.

[0153] For the purposes of this specification, the stoichiometric amount of the term phosphoric anhydride means the amount that, when combined with other components, is sufficient to prepare a phosphate ester composition.

[0154] Typically, the weight ratio of a polymerizable monophosphate compound having formula (I) to a polymerizable diester compound having formula (II) ranges from 55:45 to 67:33, preferably from 60:40 to 67:33, and more preferably from 64:36 to 67:33, wherein the sum of the weight parts of the polymerizable monophosphate compound and the polymerizable diester compound equals 100 parts by weight. For example, the weight ratio range of 55:45 to 67:33 covers 55:45, 60:40, or 67:33; however, the weight ratio range of 55:45 to 67:33 does not cover 55:33 or 67:45.

[0155] Preferably, the polymerizable phosphate composition has residual phosphoric acid, wherein the weight ratio of phosphoric acid to the sum of the polymerizable monophosphate compound having formula (I) and the polymerizable diester compound having formula (II) is 10:90 to 25:75, typically 10:90 to 20:80, more typically 10:90 to 18:82, for example 11:89-16:84. For example, the polymerizable phosphate composition has residual phosphoric acid, which is 10 wt.%-16 wt.% of the polymerizable phosphate composition.

[0156] Preferably, the polymerizable phosphate composition has less than 6% by weight of alcohol residue.

[0157] Preferably, the polymerizable monophosphate compound or its salt and the polymerizable diester compound or its salt do not have an oxypropylidene unit.

[0158] Polymerizable monophosphate compounds and polymerizable diester compounds act as polymerizable "monomers". These monomers can be used in acidic and basic forms. For basic forms, sodium hydroxide, potassium hydroxide, or ammonium hydroxide are typically used for neutralization.

[0159] Polymers comprising units derived from the aforementioned polymerizable monophosphate compounds and polymerizable diester compounds Composition

[0160] The present invention also relates to a polymer composition comprising units derived from the above-described polymerizable monophosphate compound and polymerizable diester compound.

[0161] In particular, the present invention provides a polymer composition comprising monomer units derived from:

[0162] (A) A phosphate ester composition comprising at least one polymerizable monophosphate compound or a salt thereof and at least one polymerizable diester compound or a salt thereof as described in this specification, wherein the phosphate ester composition comprises:

[0163] (a) At least one polymerizable phosphate monoester compound having formula (I) or a salt thereof:

[0164] R 1 -C(O)-R 2 –X 1 (I)

[0165] in:

[0166] R 1 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, and preferably the vinyl group is methyl-substituted;

[0167] R 2 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units;

[0168] X 1 It is a phosphate ester group.

[0169] The salt—if present, preferably a sodium, potassium, or ammonium salt; and

[0170] (b) At least one polymerizable phosphate diester compound having formula (II) or a salt thereof:

[0171] R 3 -C(O)-R 4 –X 2 -R 4 -C(O)-R 3 (II)

[0172] in:

[0173] R 3 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group;

[0174] R 4 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units;

[0175] X 2 It is a phosphate ester group.

[0176] The salt—if present—is preferably a sodium, potassium, or ammonium salt.

[0177] The weight ratio of the polymerizable monophosphate compound of formula (I) to the polymerizable diester compound of formula (II) ranges from 1.2–2.1:1, typically 1.4–2.1:1, 1.5–2.1:1, 1.5–2.0:1, 1.6–1.9:1, 1.7–1.9:1, or 1.8–1.9:1; and

[0178] (B) At least one other polymerizable monomer.

[0179] Typically, the weight ratio of a polymerizable monophosphate compound having formula (I) to a polymerizable diester compound having formula (II) ranges from 55:45 to 67:33, preferably from 60:40 to 67:33, and more preferably from 64:36 to 67:33, wherein the sum of the weight parts of the polymerizable monophosphate compound and the polymerizable diester compound equals 100 parts by weight. For example, the weight ratio range of 55:45 to 67:33 covers 55:45, 60:40, or 67:33; however, the weight ratio range of 55:45 to 67:33 does not cover 55:33 or 67:45.

[0180] The mixture typically further comprises a surfactant, wherein the composition contains 0.5 wt.% to 3 wt.% of the surfactant based on the total monomers including polymerizable monophosphate compounds, polymerizable diester compounds, and other polymerizable monomers. The surfactant is preferably anionic, more preferably a phosphate ester anionic surfactant. The polymer composition is typically an emulsion polymer composition.

[0181] Other polymerizable monomers are preferably one or more polymerizable monomers, including acrylate monomers, styrene monomers, vinyl ester monomers, butadiene, ethylene or vinyl chloride.

[0182] Other polymerizable monomers are typically selected from: methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, other acrylates, methacrylates and their blends, acrylic acid, methacrylic acid, cyclohexyl methacrylate, styrene, vinyltoluene, vinyl acetate, vinyl esters (e.g., vinyl tert-carbonate), acrylonitrile, acrylamide, butadiene, ethylene, vinyl chloride, etc., and mixtures thereof.

[0183] The present invention can also provide an aqueous coating comprising a polymer composition.

[0184] The present invention may also provide a method for improving the corrosion resistance of a metal substrate, the method comprising contacting at least a portion of the surface of the metal substrate with a coating composition comprising a polymer composition, compared to coating the metal substrate with a coating composition which does not contain monomer units from the polymerizable monoester compound or its salt and the polymerizable diester compound or its salt.

[0185] The present invention may also provide a method for improving the water resistance of a coating composition for a substrate, the method comprising contacting at least a portion of the surface of the substrate with the coating composition, wherein the coating composition comprises a polymer composition, compared to coating the substrate with a coating composition that is identical to, but does not contain, monomer units from the polymerizable monoester compound or its salt and the polymerizable diester compound or its salt.

[0186] The present invention may also provide a method for improving any one or more of the gloss, gloss retention and hiding power of a coating composition on a substrate, the method comprising contacting at least a portion of the surface of the substrate with a coating composition, wherein the coating composition comprises an emulsion polymer composition, compared to coating the substrate with a coating composition that is identical to but does not contain monomer units from the polymerizable monophosphate compound or its salt and the polymerizable diester compound or its salt.

[0187] The present invention can also provide a method for improving the adhesion of a coating composition to a metal substrate, the method comprising contacting at least a portion of the surface of the substrate with the coating composition, wherein the coating composition comprises the polymer composition. The substrate is typically a metal, such as aluminum, steel, or galvanized steel.

[0188] The present invention also provides a method for improving the adhesion of a coating composition intended for application to a metal substrate, the method comprising contacting at least a portion of the surface of the substrate with a coating composition, referred to as a conversion coating, wherein the conversion coating comprises the polymer composition of the present invention. The substrate is typically a metal, such as aluminum, steel, or galvanized steel.

[0189] As mentioned above, the present invention relates to different methods for improving certain properties of a substrate due to the coating composition of the present invention.

[0190] In some of these cases, the coating compositions of the present invention can be used as a base coat or undercoat in substrate pretreatment and are referred to as a “conversion coating” because the polymer reacts with and adheres to the metal, thereby improving properties such as the corrosion resistance of the substrate and / or the adhesion of the coating composition to be subsequently applied to the conversion coating.

[0191] According to an embodiment, a conversion coating is applied to the surface by reacting the metal surface to be treated with the corresponding conversion composition (in other words, the conversion composition is applied to the metal surface for forming a conversion coating thereon).

[0192] Contact between the metal surface and the conversion coating can be made by any means known per se, such as dip coating in a conversion bath or spray coating.

[0193] Therefore, the coating composition of the present invention can be used both as a conversion coating (in pretreatment) and a coating composition (such as paint, varnish or adhesive) to treat the same substrate.

[0194] When the coating composition is used as a conversion coating, the latter is first applied to the metal surface of the substrate. Then, a coating composition containing a polymer composition (the same or different but still according to the invention) is applied to the pretreated substrate. In other words, the polymer composition of the invention is used in both the conversion coating and the coating composition applied to the conversion coating.

[0195] The obtained material includes a metal surface covered with:

[0196] -Including the first layer of the conversion coating, and

[0197] - A second layer comprising a coating composition (particularly paint, varnish, or adhesive).

[0198] An additional layer can be applied between the treated metal surface and the coating. This is, for example, in the case where a metal foil is treated at a first site and then coated (e.g., painted) at a second site: in this case, a lubricant can be applied to the treated foil to allow it to be wound and facilitate its transport.

[0199] Any metal surface can be treated with the conversion composition of the present invention, but the present invention is particularly suitable for treating the following metal surfaces:

[0200] - Aluminum or aluminum-based alloys; or

[0201] - Steel, such as galvanized steel (hot-dip galvanized HDG or electro-galvanized EG); or cold-rolled steel (CRS); or

[0202] - Magnesium or magnesium-based alloys; or

[0203] - Zinc or zinc-based alloys

[0204] - Titanium or titanium-based alloys.

[0205] The present invention is of particular interest for the metallic surfaces of aluminum and aluminum alloys (such as aluminum alloy AA 5005 tested in the appended examples or other alloys such as the 1xxx, 2xxx, 3xxx, 4xxx, 5xxxx, 6xxx series (such as AA1050, 2024, 3003, 5182, 5754, 6111, 6016, 6060, 6063, 6182, 7075).

[0206] The conversion compositions used according to the present invention typically contain fluorine anions and cationic metals, such as compounds like H2CrF6, or more preferably chromium-free compounds such as H2TiF6, H2ZrF6, H2HfF6, H2AlF6, H2SiF6, H2GeF6, H2SNF4, HBF4, or TiZr.

[0207] The conversion composition may also contain other compounds, such as silane precursors, and / or cerium salts, and / or terbium molybdate.

[0208] The present invention also relates to a method for treating a first metal surface S1 of a first substrate and imparting adhesive resistance to adhesion failure, the first metal surface being intended to be bonded to a second surface S2 of a second substrate by an adhesive, the method comprising bringing at least a portion of the first metal surface S1 into contact with the coating composition.

[0209] Another advantage of the adhesive bond obtained according to the invention is its high resistance to corrosive and humid atmospheres, which results in durable adhesive bonding. In most cases, coating compositions are also used to achieve this additional effect (i.e., to further impart resistance to corrosive and humid atmospheres to the bond, in other words, to achieve both highly effective and durable adhesion). In other words, the method also provides very good resistance to adhesive bond aging. This property can be measured by tensile testing of so-called “single lap-shear” (SLS) components, as defined in ASTM D-1002 10, on newly bonded SLS components, and on SLS components aged in repeated cycles of corrosive, humid, or corrosive followed by humid atmospheres, as in ASTM G85 A3. Other tests combine corrosive stress and mechanical stress (e.g., compressive load), such as Bv 101-07, known as the Ford Durability Stress Test for Adhesive Lap-shear Bonds, or the Arizona Proven Ground Exposure (APGE).

[0210] Preferably, the metal surface S1 is a surface containing a metal selected from aluminum, steel, zinc, magnesium, titanium, copper and their alloys, or cobalt-nickel alloys.

[0211] The metal surface S1 is preferably obtained by:

[0212] - Aluminum or aluminum-based alloys; or

[0213] - Steel, such as galvanized steel (hot-dip galvanized HDG or electro-galvanized EG); or cold-rolled steel (CRS); or

[0214] - Magnesium or magnesium-based alloys; or

[0215] - Zinc or zinc-based alloys

[0216] - Titanium or titanium-based alloys.

[0217] The present invention is of particular interest for the metallic surfaces of aluminum and aluminum alloys (such as aluminum alloy AA 5005 tested in the appended examples or other alloys such as the 1xxx, 2xxx, 3xxx, 4xxx, 5xxxx, 6xxx series (such as AA1050, 2024, 3003, 5182, 5754, 6111, 6016, 6060, 6063, 6182, 7075).

[0218] Preferably, the second surface S2 is a metallic surface. However, the second surface S2 can be a non-metallic surface, such as a plastic surface or a composite surface.

[0219] According to an embodiment, the second surface S2 is a surface containing a metal, which is advantageously selected from aluminum, steel, zinc, magnesium, titanium, copper and their alloys, or cobalt-nickel alloys.

[0220] According to one embodiment, surfaces S1 and S2 have the same properties, but they may also be different according to other possible embodiments of the invention. According to variations, both surfaces S1 and S2 are metallic surfaces of aluminum or an aluminum alloy.

[0221] According to another possible embodiment, the second surface S2 is a non-metallic surface, such as a plastic surface (e.g., a plastic surface based on polyamide, polyether ether ketone (PEEK) or acrylonitrile butadiene styrene (ABS); or a composite surface (based on, for example, carbon fiber reinforced plastic (CFRP) or glass fiber reinforced plastic).

[0222] Typically (but not necessarily), the second surface S2 is also a metallic surface, with or without the same properties as the first surface S1. According to an advantageous embodiment, the second surface S2 is a metallic surface also treated with a coating composition, which is typically, but not necessarily, the same as the coating composition used to treat the first surface S1.

[0223] More generally, the polymer coating used in the method according to the invention is preferably used to treat the two surfaces S1 and S2 before the adhesive bonds the two surfaces, especially when S2 is a metallic surface.

[0224] Method for manufacturing the above polymer

[0225] In another aspect, the present invention relates to a method for preparing the above-mentioned polymer, the method comprising the following steps:

[0226] Combine the following items:

[0227] (A) At least one polymerizable phosphate monoester compound having formula (I) or a salt thereof:

[0228] R 1 -C(O)-R 2 –X 1 (I)

[0229] in:

[0230] R 1 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, and typically the vinyl group is methyl-substituted;

[0231] R 2 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units;

[0232] X 1 It is a phosphate ester group.

[0233] The salt—if present, preferably a sodium, potassium, or ammonium salt; and

[0234] (b) At least one polymerizable phosphate diester compound having formula (II) or a salt thereof:

[0235] R 3 -C(O)-R 4 –X 2 -R 4 -C(O)-R 3 (II)

[0236] in:

[0237] R 3 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, and typically the vinyl group is methyl-substituted;

[0238] R 4It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units;

[0239] X 2 It is a phosphate ester group.

[0240] The salt—if present—is preferably a sodium, potassium, or ammonium salt; and

[0241] The weight ratio of the polymerizable phosphate monoester compound having formula (I) to the polymerizable phosphate diester compound having formula (II) ranges from 1.2-2.1:1, or typically 1.4-2.1:1, 1.5-2.1:1, 1.5-2.0:1, 1.6-1.9:1, 1.7-1.9:1, or 1.8-1.9:1, and

[0242] (B) at least one other polymerizable monomer to form a mixture; and

[0243] To polymerize at least one polymerizable monophosphate compound or salt thereof, and at least one polymerizable diester compound or salt thereof, and at least one other polymerizable monomer of a phosphate ester composition.

[0244] Typically, the weight ratio of a polymerizable monophosphate compound having formula (I) to a polymerizable diester compound having formula (II) ranges from 55:45 to 67:33, preferably from 60:40 to 67:33, and more preferably from 64:36 to 67:33, wherein the sum of the weight parts of the polymerizable monophosphate compound and the polymerizable diester compound equals 100 parts by weight. For example, the weight ratio range of 55:45 to 67:33 covers 55:45, 60:40, or 67:33; however, the weight ratio range of 55:45 to 67:33 does not cover 55:33 or 67:45.

[0245] Typically, (A) the phosphate ester composition of the present invention and (B) at least one other polymerizable monomer are combined to form a mixture, wherein the weight ratio of the phosphate ester monomer to the at least one other polymerizable monomer is typically 1-10 : 99-90, more typically 1-5 : 99-95, wherein the total weight parts of the phosphate ester monomer and the at least one other polymerizable monomer are equal to 100 parts by weight. Therefore, a weight ratio of 1-10 : 99-90 means that for every 100 parts by weight of the total monomers of the phosphate ester monomer and the at least one other polymerizable monomer, there are 1-10 parts by weight of the phosphate ester monomer.

[0246] Typically, the mixture further comprises phosphoric acid, preferably wherein the weight ratio of phosphoric acid to the sum of a polymerizable monophosphate compound having formula (I) and a polymerizable diester compound having formula (II) is 10:90 to 25:75, preferably 12:88 to 20:80.

[0247] Preferably, the polymerizable monophosphate compound or its salt and the polymerizable diester compound or its salt produced by this method do not contain oxypropylidene units.

[0248] Phosphate esters can be neutralized with (NH4)OH, KOH, or NaOH to convert some phosphate esters into salts.

[0249] Polymerizable phosphate monoesters and phosphate diesters are olefinically unsaturated monomers and can therefore be polymerized from these unsaturated monomers. Monomers can be used in a variety of homopolymers and copolymers, such as those produced by solution polymerization, bulk polymerization, or suspension polymerization, but they are most useful as comonomers in the production of latexes with low crosslinking densities via emulsion polymerization. Emulsion polymerization is discussed in G. Pohlein, “Emulsion Polymerization”, Encyclopedia of Polymer Science and Engineering, Vol. 6, pp. 1-51 (John Wiley & Sons, New York, NY, 1986), the disclosure of which is incorporated herein by reference. Emulsion polymerization is a multiphase reaction process in which unsaturated monomers or monomer solutions are dispersed in a continuous phase by means of an emulsifier system and polymerized with a free radical or redox initiator. The product, a colloidal dispersion of the polymer or polymer solution, is called a latex.

[0250] The mixture typically further comprises a surfactant, wherein the composition contains 0.5 to 3 wt.% of the surfactant based on total monomers, said total monomers including polymerizable monophosphate compounds, polymerizable diester compounds, and other polymerizable monomers. The surfactant is preferably anionic, more preferably a phosphate anionic surfactant. The polymer composition is typically an emulsion polymer composition.

[0251] Suitable surfactants that can be used with polymerizable monophosphate and dieplex phosphate compounds include ionic and nonionic surfactants, such as alkyl polyethylene glycol ethers, such as ethoxylated products of lauryl alcohol, tridecyl alcohol, oleyl alcohol, and stearyl alcohol; alkylphenol polyethylene glycol ethers, such as ethoxylated products of octylphenol or nonylphenol, diisopropylphenol, and triisopropylphenol; alkali metal salts or ammonium salts of alkyl, aryl, or alkylaryl sulfonates, sulfates, phosphates, etc., including sodium lauryl sulfate, sodium octylphenol glycol ether sulfate, sodium dodecylbenzene sulfonate, sodium lauryl diethylene glycol sulfate, and ammonium tri-tert-butylphenol and ammonium penta-ethylene glycol and octa-ethylene glycol sulfonate; sulfosuccinates such as disodium ethoxylated nonylphenol half ester of sulfosuccinic acid, disodium n-octyldecyl sulfosuccinate, sodium dioctyl sulfosuccinate, etc. Preferably, the surfactant is anionic, and most preferably, a phosphate ester anionic surfactant.

[0252] Typical phosphate ester surfactants have structures (III) and (IV):

[0253] (III)

[0254] (IV)

[0255] Wherein R is an alkyl group, typically C10-20 alkyl, preferably C12-C16;

[0256] n is the number of moles of ethylene oxide, typically n is 4-20; and

[0257] M is H, Na, K, or NH4.

[0258] Typical comonomers used include monomers such as methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, other acrylates, methacrylates and their blends, acrylic acid, methacrylic acid, cyclohexyl methacrylate, styrene, vinyltoluene, vinyl acetate, vinyl esters (e.g., ethylene tert-carbonate), acrylonitrile, acrylamide, butadiene, ethylene, vinyl chloride, etc., and mixtures thereof. Typical polymers (copolymers) are any of styrene, methyl methacrylate, methacrylic acid, cyclohexyl methacrylate, ethylhexyl acrylate, and / or acetoacetoxyethyl methacrylate.

[0259] Polymerization can be carried out via emulsion polymerization. In the above methods, suitable initiators, reducing agents, catalysts, and surfactants are well-known in the field of emulsion polymerization. Typical initiators include ammonium persulfate (APS), hydrogen peroxide, sodium persulfate, potassium persulfate or ammonium persulfate, benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, 2,2'-azobisisobutyronitrile, tert-butyl hydroperoxide, benzoyl peroxide, etc.

[0260] Suitable reducing agents are those that increase the polymerization rate and include, for example, sodium bisulfite, sodium dithionite, sodium formaldehyde sulfoxylate, ascorbic acid, isoascorbic acid, and mixtures thereof.

[0261] Suitable catalysts are those compounds that increase the polymerization rate, and which, in combination with the aforementioned reducing agents, promote the decomposition of the polymerization initiator under the reaction conditions. Suitable catalysts include transition metal compounds, such as ferrous sulfate heptahydrate, ferrous chloride, copper sulfate, copper chloride, cobalt acetate, cobalt sulfate, and mixtures thereof.

[0262] Typical methods of emulsion polymerization preferably involve charging a reactor with water and feeding it as a separate stream of monomer pre-emulsion and initiator solution. A small amount of pre-emulsion and a portion of the initiator can be initially charged at the reaction temperature that produces the "seed" latex. This "seed" latex process produces better particle size reproducibility. Under "normal" initiation conditions (i.e., initiation conditions where the initiator is activated by heat), polymerization is typically carried out at about 60°C–90°C. A typical "normal" initiation process may, for example, use ammonium persulfate as the initiator at a reaction temperature of 80°C ± 2°C. Under "redox" initiation conditions, i.e., initiation conditions where the initiator is activated by a reducing agent, polymerization is typically carried out at 60°C–70°C. Typically, the reducing agent is added as a separate solution. A typical "redox" initiation process may, for example, use potassium persulfate as the initiator and sodium metabisulfite as the reducing agent at a reaction temperature of 65°C ± 2°C.

[0263] In the above emulsion, the polymer preferably exists as generally spherical particles dispersed in water, having a diameter of about 50 nanometers to about 500 nanometers. The gel content can be determined using the method taught in U.S. Patent No. 5,371,148 (incorporated herein by reference). Glass transition temperature (Tg) g () is based on the proportion of each monomer used and the corresponding T of the homopolymer of that monomer. g The calculated values. In addition to preparing emulsion polymers, the polymerizable surfactants of this invention are also considered for use in forming solution copolymers.

[0264] In particular, the phosphate monoester and phosphate diester compounds of the present invention can be incorporated in effective amounts into aqueous polymer systems (e.g., paints) to enhance the stability of the polymer emulsion. Commonly used monomers in the preparation of acrylic paints include butyl acrylate, methyl methacrylate, ethyl acrylate, and cyclohexyl methacrylate. In the acrylic paint composition, the polymer is composed of one or more esters of acrylic acid or methacrylic acid, typically of, for example, about 50 / 50 high-T... g Monomers (e.g., methyl methacrylate) and low T g The composition consists of a monomer (e.g., butyl acrylate) along with a small proportion (e.g., about 0.5% to about 2% by weight) of acrylic acid or methacrylic acid. Vinyl-acrylic paints typically contain vinyl acetate and butyl acrylate and / or 2-ethylhexyl acrylate and / or vinyl tert-carbonate. In vinyl-acrylic paint compositions, at least 50% of the formed polymer is composed of vinyl acetate, with the remainder being esters selected from acrylic acid or methacrylic acid. Styrene / acrylic polymers are typically similar to acrylic polymers, except that styrene replaces all or part of its methacrylic acid monomers. The monophosphate and diester compounds of the present invention can be copolymerized with typical monomers used to prepare latexes for paints to produce paints with enhanced stability and adhesion to surfaces.

[0265] If any disclosure of any patent, patent application, or publication incorporated herein by reference conflicts with this specification to the extent that it may obscure the terminology, this specification shall prevail.

[0266] Example 1

[0267] Manufacturing the phosphate monomer mixture of the present invention

[0268] A 500 mL round-bottom, four-necked flask was equipped with a thermocouple, a paddle stirrer, a pressure-equalizing feed funnel, and a double-ended CLAISEN adapter with a needle-shaped inlet for dry air and a water condenser leading to a silicone-filled bubbler. 214.72 g of hydroxyethyl methacrylate was added to the flask. Stirring and a slow flow (20 ml / min) of dry air under the surface into the liquid were initiated. To suppress unwanted homopolymerization, 1.75 g of methoxyhydroquinone (MEHQ) was added to the reactor and allowed to dissolve completely. 61.14 g of 105% polyphosphoric acid was added to the feed funnel, followed by controlled addition over 35 minutes, during which the liquid temperature increased from 35°C to 42°C. The liquid feed funnel was replaced with a spiral powder-adding funnel containing 70.64 g of phosphoric anhydride, which was slowly added over 2.5 hours, with the highest reaction temperature reaching 55°C. The liquid temperature was then increased to 80°C and maintained for 18 hours. After holding, 1.75 g of deionized water was added to the reactor to hydrolyze any remaining pyrophosphate, followed by holding for another 2 hours. The reactants were then cooled and bottled as is.

[0269] The special monomer composition of the present invention contains a first monomer monophosphate ester (MAP), a second monomer diester phosphate ester (DAP), residual alcohol, and residual phosphoric acid.

[0270] Phosphate monoesters are ethylene glycol methacrylate phosphate esters having the structural formula (V):

[0271] (V)

[0272] Phosphate diesters are bis(ethylene glycol methacrylate) phosphate esters having structural formula (VI):

[0273] (VI)

[0274] The average MAP:DAP molar ratio of the five samples of monomer C produced in this invention is 74.4:25.6. The average MAP (ethylene glycol methacrylate phosphate):DAP (bis(ethylene glycol methacrylate) phosphate) weight ratio of the five samples of monomer C produced in this invention is 65.4:34.6.

[0275] Example 2

[0276] This example compares the coating C of the present invention, which comprises the latex polymer C of the present invention made using the phosphate ester composition C of the present invention, with a comparative coating.

[0277] The contrast coating is either contrast coating A made of contrast latex polymer A (made using contrast phosphate ester composition A) or contrast coating B made using contrast latex polymer B (made using contrast phosphate ester composition B).

[0278] Phosphate ester compositions have formula (VII):

[0279] (VII)

[0280] The comparative phosphate ester composition A has R = methyl; R1 = H; n = 1; the ratio of monophosphate to diester is 60:40 molar ratio; and 1:1 mass ratio.

[0281] The phosphate ester composition B has R = methyl; R1 = methyl; n = 5; and the ratio of phosphate monoester to diester is 13:1 molar ratio and 88:12 mass ratio (7.33:1 mass ratio).

[0282] The phosphate ester composition C of this invention has R = methyl; R1 = H; n = 1; the average ratio of monophosphate to diester in the five samples is 74.4:25.6 molar ratio and 65.4:34.6 mass ratio (1.89:1 mass ratio). The mass ratio range of the five monomer C samples of this invention is 1.82-1.98:1.

[0283] This example demonstrates that the comparative phosphate composition C of the present invention in Example 1 stabilizes the pre-emulsion of monomers such as styrene, methyl methacrylate (MMA), 2-ethylhexyl acrylate (2HEA), and methacrylic acid (MAA).

[0284] The formulation of the pre-emulsion is shown in Table 1.

[0285] Table 1 - Pre-emulsification of monomer blends of latex polymer C used in this invention

[0286]

[0287] Monomer composition: STY / MMA / 2EHA / MMA / specialty monomers in a weight ratio of 42.2 / 23.5 / 29.3 / 3.0 / 2.0.

[0288] The monomer composition was dispersed in water at a 50 / 50 weight ratio and neutralized with concentrated ammonia to pH = 7. The total PEMA content was 2.0% based on total monomers (BOTM).

[0289] The pre-emulsification of the monomer blend of the latex polymer C used in this invention is combined with an emulsifier in an amount of 1.0 wt.% BOTM (based on total materials). The emulsifier is RHODAFAC RS 710 K25 phosphate anionic surfactant (potassium salt) that is free of APE (alkylphenol ethoxylate).

[0290] A small laboratory homogenizer (ULTRA-TURRAX T25 homogenizer from IKA-Labortechnik) was used to obtain a stable pre-emulsion that could be used for emulsion polymerization (>3 hours without separation). The nucleation step still requires some specialty monomer composition. A specialty monomer composition of 0.2% BOTM was used in the initial charge. A complete list of the components is given in Table 2. The pre-emulsion containing the phosphate ester composition C of the present invention was then used to manufacture the latex polymer C of the present invention.

[0291] Table 2 - Emulsion polymerization components used to manufacture the latex polymer C of the present invention

[0292]

[0293] Procedure for manufacturing the polymer of the present invention using the phosphate ester composition C of the present invention:

[0294] 1. Heat the reactor contents to 78°C-80°C; add initiator solution C and 29.4 g monomer emulsion B (5%); maintain the temperature at 80°C for 15 minutes.

[0295] 2. Add the remaining D and B over 3 hours. Maintain 80°C during the addition process.

[0296] 3. After adding, keep at 80°C for 60 minutes.

[0297] 4. Cool to room temperature and adjust the pH to 8.0 using a 28% ammonia solution.

[0298] The emulsification of the monomer blends used in the latex polymer C of the present invention produces a styrene-acrylic latex polymer with the following properties:

[0299] The glass transition temperature Tg is approximately 36°C. For the purposes of this specification, Tg... g Calculated using Fox's equation (1):

[0300] 1 / T g,mix ≈ ∑ i ω i / T g,i (1)

[0301] Where T g,mix and Tg,i These are the glass transition temperatures of the mixture / polymer and the component, respectively, and ω i This is the mass fraction of component i. For two components A and B, the Fox equation simplifies to the equation used to calculate T. g The simplified Fox equation (2):

[0302] 1 / T g,mix ≈ ω A / T g,A + ω B / T g,B (2).

[0303] For particle sizes from 100 to 120 nm, latex particle size measurements are typically performed by dynamic light scattering (DLS), which yields substantially the same results (within 1%). Unless otherwise indicated, particle size in this disclosure is “Z-mean”. The Z-mean is an intensity-weighted average hydrodynamic size of an ensemble of particles measured by dynamic light scattering (DLS). The Z-mean is derived from a cumulative analysis of the measured correlation curves, where a single particle size is assumed and a single exponential fit is applied to the autocorrelation function. Particle size can also be determined by electron microscopy.

[0304] 40.0% solids (in wt.%), and

[0305] It has a pH of about 7.0 to about 8.0.

[0306] Example 3 - Painting Manufacturing

[0307] This example demonstrates the preparation of a coating for comparing the properties of the following direct-to-metal (DTM) applications:

[0308] Paint C is formulated using the latex polymer C of the present invention (made from an emulsified latex blend having 2 wt% of the phosphate ester composition C of the present invention and 3 wt% MAA);

[0309] Paint A was formulated with a comparative latex polymer A (made from 2 wt% phosphate ester composition A and 3% MAA);

[0310] Paint B was formulated with a contrast latex polymer B (made from 2 wt% phosphate ester composition B and 3 wt% MAA); and

[0311] Paint D was formulated with a comparative latex polymer D (made with 5% MAA and without the phosphate ester composition C of the present invention).

[0312] The latex used for coating is the aforementioned styrene-acrylic latex with a Tg of approximately 36°F in a coating formulation containing 18% PVC, 36% VS, and approximately 150 g / l VOC.

[0313] The average ratio of MAP determined by NMR was as follows: the DAP in the phosphate composition C of the present invention had a MAP:DAP ratio of 74.4:25.6 (±0.7) mol.% and 65.4:34.6 (±0.8) wt.%. DAP is ethylene glycol methacrylate phosphate. MAP is bis(ethylene glycol methacrylate) phosphate. The phosphate composition C of the present invention contains phosphoric acid in the range of 11.4 to 16.0 wt.%.

[0314] The average proportions of MAP were determined by NMR: the MAP:DAP molar ratio in the comparative phosphate composition A was found to be 60.4:39.6; and the MAP:DAP weight ratio was 49.8:50.2 wt.%. MAP is ethylene glycol methacrylate phosphate. DAP is bis(ethylene glycol methacrylate) phosphate. The comparative phosphate composition A contains phosphoric acid in the range of 2.5 to 2.8 wt.%.

[0315] The average ratio of MAP was determined by NMR: the DAP in the comparative phosphate ester composition B had a MAP:DAP molar ratio of approximately 93.2:6.8 and a MAP:DAP mass ratio of approximately 88.5:11.5.

[0316] The paint has the composition listed in Table 3.

[0317]

[0318] The paint has the composition listed in Table 4.

[0319]

[0320] PVC is pigment volume concentration, a measure of the volume of pigment in a coating relative to the volume of the solid binder, calculated as Vpigment / (Vpigment + VBinder) × 100%, where Vpigment and VBinder are the volumes of pigment and binder, respectively. Gloss varnishes have 0 PVC. Flat coatings have PVC ranging from 55 wt.% to 80 wt.%. Depending on the color, gloss coatings can have PVC ranging from 0 wt% to 20 wt%.

[0321] VOC stands for volatile organic compound content.

[0322] Table 5 lists the characteristics of the screened latexes, with the difference being the variation of phosphate esters in different latexes.

[0323] Table 5 - Screening Latex

[0324]

[0325] Methyl methacrylate (MMA); 2-Ethylhexyl acrylate (2EHA); Methacrylic acid (MMA)

[0326] Example 4 - Salt spray / corrosion resistance test

[0327] The salt spray / corrosion resistance of the coating was tested in the CCT-600 (cyclic corrosion chamber) corrosion chamber according to ASTM B117 using neutral salt spray (35°C / 5% NaCl).

[0328] Apply the paint to a 4 × 6 cold-rolled steel (CRS) sheet.

[0329] The coating was cured for 7 days under controlled temperature and humidity (CTCH) (50% RH / 72°F (22°C)).

[0330] The board is then wrapped in tape to expose the painted side. The film thickness is then measured, and a two-inch vertical scribe line is made on the board using a scriber with a 60° tungsten carbide tip.

[0331] The target dry film thickness (DFT) is approximately 2 mils (approximately 50 μm).

[0332] The degree of rust (corrosion) on the painted surface is evaluated according to ASTM D610-95.

[0333] The degree of blistering of the paint should be evaluated according to ASTM D714-87.

[0334] The degree of scratch corrosion of the paint should be evaluated according to ASTM D 1654.

[0335] Figures 1 and 2 show the results of this salt spray / corrosion resistance test on a polished CRS (cold-rolled steel) sheet with a dry film thickness of 50 μm using neutral salt spray (35°C / 5% NaCl) according to ASTM B117, after the polished CRS sheet underwent 7 days of curing at CTCH (72°F / 50% relative humidity (RH)).

[0336] Figure 1 compares paint C made with latex polymer C of the present invention (made from an emulsified latex blend having 3 wt% of the phosphate ester composition C of the present invention) with paint D made with latex D (made from an emulsified latex blend without any phosphate ester composition).

[0337] Figure 2 compares polished CRS panels coated with the following paints: paint C made with the latex polymer C of the present invention (made from a latex blend emulsified with 3 wt% of the phosphate composition C of the present invention); paint A made with comparative latex A (made with comparative phosphate composition A); and paint B made with comparative latex B (made with comparative phosphate composition B).

[0338] The data shows that, compared with (1) paint A formulated with comparative latex polymer A (made with 3 wt% phosphate composition A and 2 wt% MAA), (2) paint B formulated with comparative latex polymer B (made with 3 wt% phosphate composition B and 2 wt% MAA), and (3) paint D formulated with comparative latex polymer D (made with 5% MAA and without the phosphate composition C of the present invention), paint C formulated with the latex polymer C of the present invention (made from an emulsified latex blend having 3 wt% phosphate composition C of the present invention and 2 wt% MAA) has superior direct-to-metal (DTM) application properties.

[0339] Example 5 - Metal Adhesion

[0340] The adhesion of painted metals was tested according to ASTM D3359 – Cross-cut Adhesion (Adhesion Tape: ELCOMETER 99 ASTM D3359-09 Cross-cut Adhesion Test Tape). Samples were each polished CRS plates (hot roller A653) of bare aluminum with a dry film thickness of 50 µm, cured for 1 day and 7 days in CTCH (72°F / 50% relative humidity (RH)). Wet adhesion was tested after 30 minutes of immersion and 30 minutes of recovery.

[0341] Figure 3 shows the standard grading based on the adhesion test results of ASTM D3359 cross-cut adhesion test.

[0342] In the test, as shown in Figure 3: ASTM rating: 0B = complete failure (no adhesion); 5B = perfect adhesion (no paint removal).

[0343] Figure 4 shows the results of testing the adhesion of the paint to the metal according to the ASTM D3359 method. Figure 4 compares the following:

[0344] Paint C is formulated using the latex polymer C of the present invention (made from an emulsified latex blend having 3 wt% of the phosphate ester composition C of the present invention and 2 wt% MAA);

[0345] Paint A was formulated with contrast latex polymer A (made from 3 wt% phosphate ester composition A and 2% MAA); and

[0346] Paint B was formulated with contrast latex polymer B (made from 3 wt% phosphate ester composition B and 2 wt% MAA).

[0347] The latex used for the coating was the aforementioned styrene-acrylic latex with a Tg of approximately 36°F in a coating formulation of 18PVC / 36% VS / approximately 150 g / l VOC. The tested sheets were bare aluminum, polished cold-rolled steel (CRD), and hot-dip galvanized exposed steel (HDGE).

[0348] The board is tested as shown below.

[0349] Apply the coating to a dry film thickness of approximately 50 µm.

[0350] Cur the board in CTCH (72°F / 50% RH).

[0351] The adhesion of the plates was evaluated after 1 day of drying and 7 days of drying (if necessary).

[0352] For dry adhesion, two copies of the board are scribed for testing. Adhesive tape is then applied directly to the scribe area, pressed firmly down onto the film, and then removed from the board at approximately a 180-degree angle. The scribe lines are rated based on the ASTM D3359 method.

[0353] For wet adhesion, scribble two copies of the board for testing. Then cover the scribbles with a double-layered towel and soak in DI water for 30 minutes. After 30 minutes, remove the towel, pat the board dry, and then allow it to air dry completely for 30 minutes. After 30 minutes, test the adhesion in the same manner as for dry adhesion.

[0354] Figure 4 illustrates that paint C, formulated with the latex polymer C of the present invention (made from an emulsified latex blend having 3 wt% of the phosphate ester composition C of the present invention and 2 wt% MAA), exhibits excellent early wet and dry adhesion on a metal substrate. It performs better than paint A, formulated with comparative latex polymer A (made with 3 wt% phosphate ester composition A and 2% MAA); and paint B, formulated with comparative latex polymer B (made with 3 wt% phosphate ester composition B and 2 wt% MAA).

[0355] Figure 5 shows the results of testing the metal adhesion of the paint according to the procedure used to obtain Figure 4, according to ASTM D3359. Figure 5 compares paint C formulated with the latex polymer C of the present invention (made from an emulsified latex blend having 3 wt% of the phosphate ester composition C of the present invention and 2 wt% MAA) with paint D formulated with a control latex polymer D (made with 5% MAA and without the phosphate ester composition). The latex is the aforementioned styrene-acrylic latex with a Tg of about 36°F in a paint formulation of 19 PVC / 36% VS / about 150 g / l VOC. The tested sheets were bare aluminum, polished cold-rolled steel (CRD), and hot-dip galvanized exposed steel (HDGE).

[0356] Figures 4 and 5 show that the latex polymer C of the present invention, prepared from an emulsified latex blend having 3 wt% of the phosphate ester composition C of the present invention, can improve adhesion to difficult-to-find metal substrates.

[0357] Example 6 - Gloss Formation / Improvement

[0358] According to ASTM D-523-89, the paint was applied to a Leneta Type 3B chart and allowed to dry in a controlled temperature chamber (CTR) at CTCH for 7 days. Gloss was measured by placing a Byk micro-triangle gloss meter on the paint and recording the gloss values ​​at 20° and 60° angles. Three measurements were performed for each paint, and the average was used for the final result. This is a 3-mil wet-applied paint on a Type 3B chart. Cured at CTCH (72°F / 50% RH). Gloss measurements were recorded after 1 day and 7 days of drying. As in the example above, the latex is a styrene-acrylic latex with a Tg of 36°C, and the paint formulation contains 18% PVC / 36% VS / approximately 150 g / l VOC (volatile organic compound content).

[0359] Table 6 compares the gloss improvements for the following items:

[0360] Paint C is formulated using the latex polymer C of the present invention (made from an emulsified latex blend having 3 wt% of the phosphate composition C of the present invention and 2 wt% MAA).

[0361] Paint A is formulated with contrast latex polymer A (made from 3 wt% phosphate ester composition A and 2% MAA).

[0362] Paint B was formulated with a contrast latex polymer B (made from 3 wt% phosphate ester composition B and 2 wt% MAA), and...

[0363] Paint D was formulated with contrast latex polymer D (made with 5% MAA and without phosphate ester composition).

[0364] Table 6

[0365]

[0366] Table 6 shows the improved gloss formation achieved using the phosphate ester composition C of the present invention.

[0367] Example 7 - Gloss Retention / Yellowing

[0368] The gloss retention of the painted panels was also tested using a UVA lamp via a cyclic method according to ASTM G154 - QUV. This test was performed according to the following procedure.

[0369] Cycle 1: 8 hours, UV light 0.89 w / m 2 60°C

[0370] Cycle 2: 4 hours, darkness, continuous condensation

[0371] repeat

[0372] The coating was applied to a bare aluminum plate (A36 plate from the Q-lab Condensation Tester (QCT) humidity chamber) used for testing and allowed to dry in CTCH (72°F / 50% RH) for 7 days. As in the example above, the latex was a styrene-acrylic latex with a Tg of 36°C, and the coating formulation contained 18% PVC / 36% VS / approximately 150 g / l VOC.

[0373] Initial gloss measurement was performed at 20 / 60 degrees.

[0374] Perform initial L a b Measure and record.

[0375] The board underwent a 1000-hour test, during which gloss and L were evaluated. a b Measurements are taken regularly.

[0376] Figure 6 and Table 7 show a comparison of gloss retention rates of paint applied to treated aluminum sheets at a DFT of 50 µm, tested using the ASTM G154 method (using a UV-A lamp). The following comparisons were made.

[0377] Paint C is formulated using the latex polymer C of the present invention (made from an emulsified latex blend having 3 wt% of the phosphate ester composition C of the present invention and 2 wt% MAA);

[0378] Paint A was formulated with contrast latex polymer A (made from 3 wt% phosphate ester composition A and 2% MAA);

[0379] Paint B formulated with contrast latex polymer B (made from 3 wt% phosphate ester composition B and 2 wt% MAA); and

[0380] Paint D is formulated using a comparative latex polymer D (made with 5% MAA and without a phosphate ester composition). As in the examples above, the latex is a styrene-acrylic latex with a Tg of 36°C, and the paint formulation contains 18% PVC / 36% VS / approximately 150 g / l VOC. The paint of the present invention exhibits consistently good gloss retention.

[0381] Table 7 - Gloss retention rate measured by ASTM G154 method

[0382]

[0383] Example 8 - Coverage / Opacity

[0384] The hiding power / opacity of the painted panels was also tested. In this test, the paint was applied to a Leneta 3B opacity test card using a 3-mil wet film applicator and allowed to dry for 7 days in a temperature and humidity controlled room (CTCH) (22°C / 50% RH) before measurement.

[0385] Then, using an X-rite handheld spectrophotometer, the reflectance of the white paint over the black and white portions of the scratch test card was measured, and the opacity was measured by comparing the contrast ratio. The contrast ratio (C / R) is defined by formula (V) as the apparent reflectance of the material when contrasted against a fully absorbing surface (black) divided by the apparent reflectance of the material when contrasted against a white surface.

[0386] C / R = (Black "L" value / White "L" value)(V)

[0387] The higher the value, the stronger the hiding power of the paint.

[0388] Contrast ratio can also be expressed as opacity of opacity. Opacity is calculated according to formula (VI).

[0389] Opacity (%) = (Reflectance over black / Reflectance over white) × 100% (VI)

[0390] Figure 7 compares the percentage of opacity of a paint made with a styrene-acrylic latex polymer (made with 2 wt.% MAA and 3 wt.% of the monomer C of the present invention) with that of a control latex made with 5% MAA and not containing the monomer C of the present invention. As in the example above, the latex is a styrene-acrylic latex with a Tg of 36°C, and the paint formulation contains 18 PVC / 36% VS / about 150 g / l VOC. The paint of the present invention has an improved opacity of 98.32% compared to 97.34% for the control latex without the monomer C of the present invention.

[0391] Unless otherwise specified, the percentage of monomer composition in this specification is based on the weight percentage of the total monomer weight.

[0392] Example 9 - Comparison of Multiple Features

[0393] Figure 8 summarizes the benefits of manufacturing paints from latex emulsified with the phosphate ester composition C of the present invention. In Figure 8, 0 is the lowest rating and 10 is the highest rating. Compared with (1) paint A formulated with comparative latex polymer A (made with 3 wt% phosphate ester composition A and 2% MAA), (2) paint B formulated with comparative latex polymer B (made with 3 wt% phosphate ester composition B and 2 wt% MAA), or (3) paint D formulated with comparative latex polymer D (made with 5% MAA and not with phosphate ester composition), paint C formulated with the latex polymer C of the present invention (made from a latex blend emulsified with 3 wt% phosphate ester composition C of the present invention and 2 wt% MAA) has a better balance of properties such as corrosion resistance, gloss, aluminum adhesion, CRD adhesion, galvanized metal adhesion, and gloss retention.

[0394] Example 10

[0395] Unlike the styrene-acrylic latex tested above, which was made from the composition Sty 42.2 / MMA 23.5 / 2EHA 29.3 / MAA 3.0 / phosphate ester composition C 2.0 of the present invention, another styrene-acrylic latex was also manufactured. This other styrene-acrylic latex was made from Sty 41.66 / MMA 22.56 / 2EHA 27.07 / AAEM 3.8 / MAA 2.93 / phosphate ester composition C 2.0 of the present invention (special monomer composition). These values ​​are based on wt.% of the total monomers (BOTM) in the emulsion polymerization mixture. AAEM is acetylacetoxyethyl methacrylate (also known as 2-[(2-methyl-1-oxo-2-propenyl)oxy]ethyl 3-oxobutanol ester) and has formula (VII):

[0396] (VII)

[0397] The combination of AAEM with the polymerizable monoester and diester compositions of the present invention further improves the properties. AAEM is typically a crosslinking agent.

[0398] The styrene-acrylic latex is produced by emulsion polymerization of the phosphate ester composition C 2.0 of the present invention (Sty 41.66 / MMA 22.56 / 2EHA 27.07 / AAEM 3.8 / MAA 2.93) in the presence of an anionic surfactant as an emulsifier, based on 1.0 wt.% of the total monomers. The anionic surfactant is RHODAFACRS 710 K25 phosphate anionic surfactant (potassium salt) free of APE (alkylphenol ethoxylate).

[0399] The styrene-acrylic latex polymer has a Tg of about 37°C, a particle size of about 90-100 nm, and is 40.0 wt.% solids with a pH of about 7-8.

[0400] The data in Figure 9 compares the paint E1 of the present invention, made with the styrene-acrylic latex polymer E (made with the phosphate ester composition C of the present invention and AAEM), with the paint E2 of the present invention, made with the styrene-acrylic latex polymer E (made with the phosphate ester composition C of the present invention, without AAEM). The paint was applied to form a 50 μm thick coating on the treated Al plate. The coating was then dried at room temperature for 20 minutes, and then dried at 80°C for 2 hours. The painted plate was then subjected to a Cleveland condensation test, in a QTC condensation tester, at 40°C and 100% relative humidity for 120 hours.

[0401] Figure 9 shows that adding AAEM enhances gloss retention under high humidity conditions.

[0402] Figure 10 shows a photograph comparing a control paint made with a control latex having (by parts by weight, pbw) Sty 41.66 / MMA 22.56 / 2EHA 27.07 / AAEM 3.8 / MAA 4.93 with a paint of the present invention made with latex Sty 41.66 / MMA 22.56 / 2EHA 27.07 / AAEM 3.8 / MAA 2.93 / phosphate ester composition C of the present invention 2.0. The paint of the present invention containing latex having MAA units and phosphate ester composition C of the present invention exhibits significantly better corrosion resistance than the control paint.

[0403] Example 11 - Comparison of cases with and without benzophenone.

[0404] The performance of the paint and coating compositions of the present invention can be important in the presence of typical paint additives. Therefore, this example tests the paint compositions of the present invention with and without benzophenone, a typical ultraviolet (UV) stabilizer component in paints and coatings.

[0405] The styrene-acrylic latex is produced by emulsion polymerization of the phosphate composition C 2.0 of the present invention (by weight, pbw) as described above (Sty 42.2 / MMA 23.5 / 2EHA29.3 / MAA 3.0), in the presence of an anionic surfactant as an emulsifier, based on 1.0 wt.% of the total monomers. The anionic surfactant is RHODAFAC RS 710 K25 phosphate anionic surfactant (potassium salt) free of APE (alkylphenol ethoxylate).

[0406] The styrene-acrylic latex polymer has a Tg of about 36°C, a particle size of about 100-120 nm, and is 40.0 wt.% solids with a pH of about 7-8.

[0407] This example compares paint F1 made with the latex containing 0.27 wt.% benzophenone with paint F2 made with the same latex but without benzophenone.

[0408] The abrasives (solid components, such as pigments and fillers) used to manufacture the paint formulations tested have the composition shown in Table 8.

[0409] Table 8

[0410]

[0411] The paint mix used to manufacture the tested coating formulations has the composition shown in Table 9. The paint mix is ​​formed when the remaining paint (resin, water, and additives) are combined and mixed. Once the paint mix and abrasive are complete, the abrasive is added to the paint mix under stirring. At this stage, any final additions are made and mixed in if required by the formulation.

[0412] Table 9

[0413]

[0414] Abrasives and paint mixes are combined to produce paint formulations having the parameters shown in Table 10.

[0415] Table 10

[0416]

[0417] The paint was applied to the corresponding treated Al-6 mil metal squares and then subjected to 7 days of dry CTCH (50% RH / 72°F (22°C)). Gloss retention / yellowing was then tested according to ASTM G154 - QUV gloss retention (cyclic method, UVA lamp), which includes:

[0418] 1. Cycle 1: 8 hours, UV light 0.89 w / m2, 60°C

[0419] 2. Cycle 2: 4 hours, darkness, continuous condensation.

[0420] 3. Repeat

[0421] The coating was applied to a bare aluminum sheet (A36 sheet from QCT) and allowed to dry for 7 days in CTCH (50% RH / 72°F (22°C)). Initial gloss was measured at 20°C / 60°C. Initial L... a b Measure and record. The board is tested for up to 1000 hours, including measurements of gloss and L. a b Measurements are taken regularly.

[0422] Figure 11 shows the excellent gloss retention of the test sample coated with paint F2 containing benzophenone. This demonstrates that the monomer units of the polymerizable phosphate monoester compound in the latex of the paint and the polymerizable phosphate monoester compound do not interfere with the UV protection function of benzophenone.

[0423] Example 12

[0424] This example compares the corrosion resistance of the latex polymer C of the present invention with that of the comparative phosphate ester composition A.

[0425] Comparison 258-04, Comparison 256-01 (2% of the latex polymer C of the present invention), Comparison 255-03 (comparison phosphate ester composition A).

[0426] Latex has the composition listed in Table 11.

[0427] Table 11

[0428]

[0429] Note: SM (styrene monomer) / CHMA (cyclohexyl methacrylate) / 2EHA (2-ethylhexyl acrylate) / MAA (methacrylic acid)

[0430] Figure 12A shows a test sample coated with paint AA made of useful Ex. 10 latex AA.

[0431] Figure 12B shows a test sample of a coated BB made with useful Ex. 10 latex BB.

[0432] Figure 12C shows a test sample coated with paint CC made from useful Ex. 10 latex CC.

[0433] The comparison in Figures 12A-12C shows that the BB coating made from Ex. 10 latex BB is better than the AA coating made from Ex. 10 latex AA or the CC coating made from Ex. 10 latex CC.

[0434] This invention's terms

[0435] The following clauses describe various aspects of the present invention:

[0436] Clause 1. A phosphate ester composition comprising:

[0437] (a) At least one polymerizable phosphate monoester compound having formula (I) or a salt thereof:

[0438] R 1 -C(O)-R 2 –X 1 (I)

[0439] in:

[0440] R 1 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, and typically the vinyl group is methyl-substituted;

[0441] R 2 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units;

[0442] X 1 It is a phosphate ester group.

[0443] The salt—if present, preferably a sodium, potassium, or ammonium salt; and

[0444] (b) At least one polymerizable phosphate diester compound having formula (II) or a salt thereof:

[0445] R 3 -C(O)-R 4 –X 2 -R 4 -C(O)-R 3 (II)

[0446] in:

[0447] R 3 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, and typically the vinyl group is methyl-substituted;

[0448] R 4 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units;

[0449] X 2 It is a phosphate ester group.

[0450] The salt—if present, preferably a sodium, potassium, or ammonium salt; and

[0451] The weight ratio of the polymerizable monophosphate compound having formula (I) to the polymerizable diester compound having formula (II) ranges from 1.2 to 2.1:1, or typically 1.4 to 2.1:1, 1.5 to 2.1:1, 1.5 to 2.0:1, 1.6 to 1.9:1, 1.7 to 1.9:1 or 1.8 to 1.9:1.

[0452] Clause 2. The phosphate ester composition as described in Clause 1, wherein the polymerizable phosphate monoester compound is 30 wt.%-60 wt.%, typically 40 wt.%-50 wt.%, or more typically 43 wt.%-47 wt.% of the phosphate ester composition on a dry (anhydrous) basis.

[0453] Clause 3. The phosphate ester composition as described in Clause 1 or 2, wherein the yield of the polymerizable phosphate diester compound is 15-40 wt%, 20-30 wt%, or more typically 21-26 wt% of the phosphate ester composition, based on the total weight of the reactants.

[0454] Clause 4. The phosphate ester composition as described in any of the preceding clauses, wherein R 1 Choose the group consisting of CH2=CH-, CH2=C(CH3)-, or cis-CH(COOH)=CH.

[0455] Clause 5. The phosphate ester composition as described in any of the preceding clauses, wherein R 2 It has one to five, preferably one to three oxyethylidene units.

[0456] Clause 6. The phosphate ester composition as described in any one of the preceding clauses, wherein R 2It has at least one oxyethylidene unit.

[0457] Clause 7. The phosphate ester composition as described in any of the preceding clauses, wherein R 2 It lacks an oxypropylidene unit.

[0458] Clause 8. The phosphate ester composition as described in any of the preceding clauses, wherein R 3 Choose the group consisting of CH2=CH-, CH2=C(CH3)-, or cis-CH(COOH)=CH-.

[0459] Clause 9. The phosphate ester composition as described in any of the preceding clauses, wherein R 4 It is a divalent polyoxyalkylene group having at least one oxyethylidene unit.

[0460] Clause 10. The phosphate ester composition as described in any of the preceding clauses, wherein R 4 It is a divalent polyoxyalkylene group having one to three oxyethylidene units.

[0461] Clause 11. The phosphate composition as described in any of the preceding clauses, wherein ((2-methyl-1-oxopropane-1,3-diyl)bis(oxy))bis(ethane-2,1-diyl)bis(2-methacrylate) is 10 wt.% to 20 wt.% of the phosphate composition, more typically 15 wt% to 20 wt%, for example 16 wt% to 18 wt%.

[0462] Clause 12. The phosphate composition as described in any of the preceding clauses, wherein ethylene glycol dimethacrylate is 1 wt.% to 10 wt.%, typically 2 wt% to 8 wt%, more typically 3 wt% to 7 wt%, for example 4 wt% to 6 wt% of the phosphate composition.

[0463] Clause 13. The phosphate ester composition as described in any of the preceding clauses, further comprising, preferably, phosphoric acid, in a weight ratio of phosphoric acid to the sum of a polymerizable monophosphate compound having formula (I) and a polymerizable diester compound having formula (II) of 10:90 to 25:75, typically 10:90 to 20:80, more typically 10:90 to 18:82, and even more typically 11:89 to 16:84.

[0464] Clause 14. The phosphate composition as described in any of the preceding clauses, wherein the at least one polymerizable monophosphate compound having formula (I) or a salt thereof and the at least one polymerizable diester compound having formula (II) or a salt thereof have been neutralized with one or more of sodium hydroxide, potassium hydroxide or ammonium hydroxide, preferably ammonium hydroxide.

[0465] Clause 15. A polymer composition comprising monomer units derived from:

[0466] (A) A phosphate ester composition comprising at least one polymerizable monophosphate compound or a salt thereof and at least one polymerizable diester compound or a salt thereof, as described in any of the preceding clauses, wherein the phosphate ester composition comprises:

[0467] (a) At least one polymerizable phosphate monoester compound having formula (I) or a salt thereof:

[0468] R 1 -C(O)-R 2 –X 1 (I)

[0469] in:

[0470] R 1 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, and preferably the vinyl group is methyl-substituted;

[0471] R 2 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units;

[0472] X 1 It is a phosphate ester group.

[0473] The salt—if present, preferably a sodium, potassium, or ammonium salt; and

[0474] (b) At least one polymerizable phosphate diester compound having formula (II) or a salt thereof:

[0475] R 3 -C(O)-R 4 –X 2 -R 4 -C(O)-R 3 (II)

[0476] in:

[0477] R 3 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group;

[0478] R 4 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units;

[0479] X 2 It is a phosphate ester group.

[0480] The salt—if present—is preferably a sodium, potassium, or ammonium salt.

[0481] The weight ratio of the polymerizable monophosphate compound of formula (I) to the polymerizable diester compound of formula (II) ranges from 1.2-2.1:1, or typically 1.4-2.1:1, 1.5-2.1:1, 1.5-2.0:1, 1.6-1.9:1, 1.7-1.9:1, or 1.8-1.9:1; and

[0482] (B) At least one other polymerizable monomer.

[0483] Clause 16. The polymer composition as described in Clause 15,

[0484] The mixture further comprises a surfactant, wherein the composition contains 0.5 wt.% to 3 wt.% of the surfactant based on total monomers, the total monomers including polymerizable monophosphate compounds, polymerizable diester compounds and other polymerizable monomers;

[0485] The surfactant is preferably an anionic surfactant, and more preferably a phosphate anionic surfactant.

[0486] The polymer composition is an emulsion polymer composition.

[0487] Clause 17. The polymer composition as described in Clause 15 or 16, wherein the other polymerizable monomers are selected from: methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, other acrylates, methacrylates and blends thereof, acrylic acid, methacrylic acid, cyclohexyl methacrylate, styrene, vinyltoluene, vinyl acetate, vinyl esters, such as vinyl tert-carbonate, acrylonitrile, acrylamide, butadiene, ethylene, vinyl chloride, etc., and mixtures thereof.

[0488] Clause 18. A water-based coating comprising a polymer composition as described in any one of Clauses 15 to 17.

[0489] Clause 19. A coating composition comprising a polymer formed from:

[0490] (A) A phosphate ester composition comprising at least one polymerizable monophosphate compound or a salt thereof and at least one polymerizable diester compound or a salt thereof, the phosphate ester composition comprising:

[0491] (a) At least one polymerizable phosphate monoester compound having formula (I) or a salt thereof:

[0492] R 1 -C(O)-R 2 –X 1 (I)

[0493] in:

[0494] R 1 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, and typically the vinyl group is methyl-substituted;

[0495] R 2 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units;

[0496] X 1 It is a phosphate ester group.

[0497] The salt—if present, preferably a sodium, potassium, or ammonium salt; and

[0498] (b) At least one polymerizable phosphate diester compound having formula (II) or a salt thereof:

[0499] R 3 -C(O)-R 4 –X 2 -R 4 -C(O)-R 3 (II)

[0500] in:

[0501] R 3 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, and typically the vinyl group is methyl-substituted;

[0502] R 4 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units;

[0503] X 2 It is a phosphate ester group.

[0504] The salt—if present—is preferably a sodium, potassium, or ammonium salt; and

[0505] The weight ratio of the polymerizable phosphate monoester compound having formula (I) to the polymerizable phosphate diester compound having formula (II) ranges from 1.2-2.1:1, or typically 1.4-2.1:1, 1.5-2.1:1, 1.5-2.0:1, 1.6-1.9:1, 1.7-1.9:1, or 1.8-1.9:1;

[0506] (B) At least one other polymerizable monomer.

[0507] Clause 20. A method for improving the corrosion resistance of a metal substrate, the method comprising contacting at least a portion of the surface of the metal substrate with a coating composition, wherein the coating composition comprises a polymer composition as described in any one of Clauses 15 to 17, compared to coating the metal substrate with a coating composition that is identical but does not contain monomer units from the polymerizable monoester compound or a salt thereof and the polymerizable diester compound or a salt thereof.

[0508] Clause 21. A method for improving the water resistance of a coating composition for a substrate, the method comprising contacting at least a portion of the surface of the substrate with the coating composition, wherein the coating composition comprises a polymer composition as described in any one of Clauses 15 to 17, compared to coating the substrate with a coating composition that is identical but does not contain monomer units from said polymerizable monoester phosphate compound or a salt thereof and said polymerizable diester phosphate compound or a salt thereof.

[0509] Clause 22. A method for improving gloss, gloss retention and hiding power of a coating composition on a substrate, the method comprising contacting at least a portion of the surface of the substrate with the coating composition, wherein the coating composition comprises an emulsion polymer composition as described in any one of Clauses 15 to 17, compared to coating the substrate with a coating composition that is identical to but does not contain monomer units from said polymerizable monophosphate compound or a salt thereof and said polymerizable diester compound or a salt thereof.

[0510] Clause 23. A method for improving the adhesion of a coating composition to a metal substrate, the method comprising contacting at least a portion of the surface of the substrate with the coating composition, wherein the coating composition comprises a polymer composition as described in any one of Clauses 15 to 17.

[0511] Clause 24. A method for improving the adhesion of a coating composition intended to be coated onto a metal substrate, the method comprising contacting at least a portion of the surface of the substrate with a coating composition called a conversion coating, wherein the conversion coating comprises a polymer composition as described in any one of Clauses 15 to 17.

[0512] Clause 25. A method for treating a first metal surface S1 of a first substrate and imparting adhesive resistance to adhesion failure, the first metal surface being intended to be bonded to a second surface S2 of a second substrate by an adhesive, the method comprising contacting at least a portion of the first metal surface S1 with a coating composition, wherein the coating composition comprises a polymer composition as described in any one of Clauses 15 to 17.

[0513] Clause 26. The method as described in Clauses 20-25, wherein the substrate is aluminum, steel or galvanized steel.

[0514] Clause 27. A method for manufacturing a polymer composition, the method comprising:

[0515] Combining (A) the phosphate ester composition as described in any one of clauses 1 to 14 and (B) at least one other polymerizable monomer to form a mixture; and

[0516] To polymerize at least one polymerizable monophosphate compound or salt thereof, and at least one polymerizable diester compound or salt thereof, and at least one other polymerizable monomer of a phosphate ester composition.

[0517] Clause 28. As described in Clause 27,

[0518] The mixture further comprises a surfactant, wherein the mixture contains 0.5 wt.% to 3 wt.% of the surfactant based on total monomers, the total monomers including polymerizable monophosphate compounds, polymerizable diester compounds and other polymerizable monomers;

[0519] The surfactant is preferably an anionic surfactant, more preferably a phosphate ester anionic surfactant; and

[0520] The composition is an emulsion polymer composition, and

[0521] The polymerization is carried out by emulsion polymerization of the mixture.

[0522] Clause 29. The method as described in Clause 27 or 28, wherein the mixture further comprises phosphoric acid, preferably wherein the weight ratio of the phosphoric acid to the sum of the polymerizable monophosphate compound having formula (I) and the polymerizable diester compound having formula (II) is 10:90 to 25:75, preferably 12:88 to 20:80.

[0523] The invention has been described in detail with reference to preferred embodiments and specific examples thereof, and it will be apparent that modifications and variations are possible without departing from the spirit and scope of this disclosure and the claims.

Claims

1. A phosphate ester composition comprising: (a) at least one polymerizable phosphate monoester compound having formula (I) or a salt thereof: R 1 -C(O)-R 2 –X 1 (I) Wherein: R 1 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, typically with methyl-substituted vinyl groups; R 2 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units; X 1 (a) is a phosphate ester group, wherein the salt—if present, is preferably a sodium, potassium, or ammonium salt; and (b) at least one polymerizable phosphate diester compound having formula (II) or a salt thereof: R 3 -C(O)-R 4 –X 2 -R 4 -C(O)-R 3 (II) Wherein: R 3 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, typically with methyl-substituted vinyl groups; R 4 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units; X 2 It is a phosphate ester group, wherein the salt—if present, preferably a sodium, potassium, or ammonium salt; and wherein the weight ratio of the polymerizable monophosphate compound having formula (I) to the polymerizable diester compound having formula (II) ranges from 1.2 to 2.1:1, or typically 1.4 to 2.1:1, 1.5 to 2.1:1, 1.5 to 2.0:1, 1.6 to 1.9:1, 1.7 to 1.9:1, or 1.8 to 1.9:

1.

2. The phosphate ester composition according to claim 1, wherein, The polymerizable phosphate monoester compound is 30 wt.%-60 wt.%, typically 40 wt.%-50 wt.%, and more typically 43 wt.%-47 wt.% of the phosphate ester composition on a dry (anhydrous) basis.

3. The phosphate ester composition according to claim 1 or 2, wherein, Based on the total weight of the reactants, the yield of the polymerizable phosphate diester compound is 15-40 wt%, 20-30 wt%, or more typically 21-26 wt% of the phosphate ester composition.

4. The phosphate ester composition as described in any of the preceding claims, wherein, R 1 Choose the group consisting of CH2=CH-, CH2=C(CH3)-, or cis-CH(COOH)=CH.

5. The phosphate ester composition as described in any one of the preceding claims, wherein, R 2 It has one to five, preferably one to three oxyethylidene units.

6. The phosphate ester composition as described in any one of the preceding claims, wherein, R 2 It has at least one oxyethylidene unit.

7. The phosphate ester composition as claimed in any of the preceding claims, wherein, R 2 It lacks an oxypropylidene unit.

8. The phosphate ester composition as described in any one of the preceding claims, wherein, R 3 Choose the group consisting of CH2=CH-, CH2=C(CH3)-, or cis-CH(COOH)=CH-.

9. The phosphate ester composition as claimed in any one of the preceding claims, wherein, R 4 It is a divalent polyoxyalkylene group having at least one oxyethylidene unit.

10. The phosphate ester composition as claimed in any of the preceding claims, wherein, R 4 It is a divalent polyoxyalkylene group having one to three oxyethylidene units.

11. The phosphate ester composition as described in any one of the preceding claims, wherein, ((2-methyl-1-oxopropane-1,3-diyl)bis(oxy))bis(ethane-2,1-diyl)bis(2-methacrylate) is 10 wt.% to 20 wt.%, more typically 15 wt% to 20 wt%, typically 16 wt% to 18 wt% of the phosphate ester composition.

12. The phosphate ester composition as described in any one of the preceding claims, wherein, Ethylene glycol dimethacrylate is 1 to 10 wt.%, typically 2-8 wt%, more typically 3-7 wt%, and most typically 4-6 wt% of the phosphate ester composition.

13. The phosphate ester composition as claimed in any of the preceding claims, further comprising phosphoric acid, preferably in a weight ratio of the phosphoric acid to the sum of a polymerizable monophosphate compound having formula (I) and a polymerizable diester compound having formula (II) of 10:90 to 25:75, typically 10:90 to 20:80, more typically 10:90 to 18:82, and even more typically 11:89 to 16:

84.

14. The phosphate ester composition as described in any of the preceding claims, wherein, The at least one polymerizable monophosphate compound having formula (I) or a salt thereof and the at least one polymerizable diester compound having formula (II) or a salt thereof have been neutralized with one or more of sodium hydroxide, potassium hydroxide or ammonium hydroxide, preferably ammonium hydroxide.

15. A polymer composition comprising monomer units derived from: (A) at least one polymerizable monophosphate compound or a salt thereof of a phosphate ester composition as described in any of the preceding claims, and at least one polymerizable diester compound or a salt thereof, the phosphate ester composition comprising: (a) at least one polymerizable monophosphate compound or a salt thereof having formula (I): R 1 -C(O)-R 2 –X 1 (I) Wherein: R 1 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, and preferably the vinyl group is methyl-substituted; R 2 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units; X 1 (a) is a phosphate ester group, wherein the salt—if present, is preferably a sodium, potassium, or ammonium salt; and (b) at least one polymerizable phosphate diester compound having formula (II) or a salt thereof: R 3 -C(O)-R 4 –X 2 -R 4 -C(O)-R 3 (II) Wherein: R 3 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group; R 4 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units; X 2 The salt is a phosphate group, wherein the salt—if present, preferably a sodium, potassium, or ammonium salt—is in a weight ratio of the polymerizable monophosphate compound having formula (I) to the polymerizable diester compound having formula (II) in the range of 1.2–2.1:1, or typically 1.4–2.1:1, 1.5–2.1:1, 1.5–2.0:1, 1.6–1.9:1, 1.7–1.9:1, or 1.8–1.9:1; and (B) at least one other polymerizable monomer, preferably one or more polymerizable monomers, including acrylate monomers, styrene monomers, vinyl ester monomers, butadiene, ethylene, or vinyl chloride.

16. The polymer composition of claim 15, wherein, The mixture further comprises a surfactant, wherein the composition comprises 0.5 to 3 wt.% of the surfactant based on total monomers, the total monomers including the polymerizable monophosphate compound, polymerizable diester compound and other polymerizable monomers; wherein the surfactant is preferably an anionic surfactant, more preferably a phosphate anionic surfactant; wherein the polymer composition is an emulsion polymer composition.

17. The polymer composition of claim 15 or 16, wherein, The other polymerizable monomers are selected from: methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, other acrylates, methacrylates and their blends, acrylic acid, methacrylic acid, cyclohexyl methacrylate, styrene, vinyltoluene, vinyl acetate, vinyl esters, acrylonitrile, acrylamide, butadiene, ethylene, vinyl chloride, etc., and mixtures thereof.

18. A water-based coating comprising the polymer composition as described in any one of claims 15 to 17.

19. A coating composition comprising a polymer formed from: (A) a phosphate ester composition comprising at least one polymerizable monophosphate compound or a salt thereof and at least one polymerizable diester compound or a salt thereof, the phosphate ester composition comprising: (a) at least one polymerizable monophosphate compound or a salt thereof having formula (I): R 1 -C(O)-R 2 –X 1 (I) Wherein: R 1 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, typically with methyl-substituted vinyl groups; R 2 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units; X 1 (a) is a phosphate ester group, wherein the salt—if present, is preferably a sodium, potassium, or ammonium salt; and (b) at least one polymerizable phosphate diester compound having formula (II) or a salt thereof: R 3 -C(O)-R 4 –X 2 -R 4 -C(O)-R 3 (II) Wherein: R 3 It is a substituted or unsubstituted vinyl group, preferably C2-C5, more preferably C2-C3 vinyl group, typically methyl-substituted; R 4 It is a divalent polyoxyalkylene group having one to five, preferably one to three oxyethylidene units, oxypropylene units or mixtures thereof, more preferably one to five, or one to three oxyethylidene units; X 2 (I) is a phosphate ester group, wherein the salt—if present, preferably a sodium, potassium, or ammonium salt; and wherein the weight ratio of the polymerizable monophosphate compound having formula (I) to the polymerizable diester compound having formula (II) is in the range of 1.2–2.1:1, or typically 1.4–2.1:1, 1.5–2.1:1, 1.5–2.0:1, 1.6–1.9:1, 1.7–1.9:1, or 1.8–1.9:1; (B) at least one other polymerizable monomer.

20. A method for improving the corrosion resistance of a metal substrate, the method comprising contacting at least a portion of the surface of the metal substrate with a coating composition, wherein the coating composition comprises a polymer composition as described in any one of claims 15 to 17, compared to coating the metal substrate with a coating composition that is the same but does not contain monomer units from the polymerizable monophosphate compound or a salt thereof and the polymerizable diester compound or a salt thereof.

21. A method for improving the water resistance of a coating composition for a substrate, the method comprising contacting at least a portion of the surface of the substrate with the coating composition, wherein the coating composition comprises a polymer composition as described in any one of claims 15 to 17, compared to coating the substrate with a coating composition that is the same as but does not contain monomer units from the polymerizable monoester compound or a salt thereof and the polymerizable diester compound or a salt thereof.

22. A method for improving gloss, gloss retention and hiding power of a coating composition on a substrate, the method comprising contacting at least a portion of the surface of the substrate with the coating composition, wherein the coating composition comprises an emulsion polymer composition as described in any one of claims 15 to 17, compared to coating the substrate with a coating composition that is identical to but does not contain monomer units from said polymerizable monophosphate compound or a salt thereof and said polymerizable diester compound or a salt thereof.

23. A method for improving the adhesion of a coating composition to a metal substrate, the method comprising contacting at least a portion of the surface of the substrate with the coating composition, wherein the coating composition comprises a polymer composition as described in any one of claims 15 to 17.

24. A method for improving the adhesion of a coating composition intended to be coated onto a metal substrate, the method comprising contacting at least a portion of the surface of the substrate with a coating composition called a conversion coating, wherein the conversion coating comprises a polymer composition as described in any one of claims 15 to 17.

25. A method for treating a first metal surface S1 of a first substrate and imparting adhesive resistance to adhesion failure, the first metal surface being intended to be bonded to a second surface S2 of a second substrate by an adhesive, the method comprising contacting at least a portion of the first metal surface S1 with a coating composition, wherein the coating composition comprises a polymer composition as claimed in any one of claims 15 to 17.

26. The method according to any one of claims 20 to 25, wherein, One or more substrates are aluminum, steel, or galvanized steel.

27. A method for manufacturing a polymer composition, the method comprising: The phosphate ester composition of any one of claims 1-14 (A) and at least one other polymerizable monomer (B) are combined to form a mixture; And to polymerize at least one polymerizable monophosphate compound or salt thereof, at least one polymerizable diester compound or salt thereof, and at least one other polymerizable monomer of the phosphate ester composition.

28. The method of claim 27, wherein, The mixture further comprises a surfactant, wherein the mixture contains 0.5 wt.% to 3 wt.% of the surfactant based on total monomers, the total monomers including the polymerizable monophosphate compound, polymerizable diester compound and other polymerizable monomers; wherein the surfactant is preferably an anionic surfactant, more preferably a phosphate anionic surfactant; and the composition is an emulsion polymer composition, and the polymerization is carried out by emulsion polymerization of the mixture.

29. The method of claim 27 or 28, wherein, The mixture further comprises phosphoric acid, preferably wherein the weight ratio of the phosphoric acid to the sum of the polymerizable monophosphate compound having formula (I) and the polymerizable diester compound having formula (II) is 10:90 to 25:75, preferably 12:88 to 20:80.

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