Aqueous polyvinylidene fluoride coating composition

Abstract

The coating composition includes water, a plurality of polyvinylidene fluoride particles, and a surfactant having a hydrophobe branching degree of 5 or greater, wherein the composition does not include a fluorinated surfactant.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates to coating compositions, and more particularly to coating compositions comprising polyvinylidene fluoride. [Background technology]

[0002] Introduction Polyvinylidene fluoride ("PVDF") and other fluoropolymers such as polytetrafluoroethylene ("PTFE") are typically formed in a multi-step process. For example, U.S. Patent Application Publication No. 2021 / 0032381 describes that a method frequently used to produce PTFE involves aqueous emulsion polymerization of fluorinated monomers. The aqueous emulsion polymerization typically uses a fluorinated surfactant and may include a nonionic surfactant such as a polyoxyethylene alkyl ether surfactant. The fluorinated surfactant is essential to maintain the emulsion. After the emulsion polymerization is complete, a step is performed to concentrate the solids and remove the fluorinated surfactant. The solid fluoropolymer can then be recovered and used.

[0003] PVDF is a fluoropolymer used in the production of high-performance coatings, offering good resistance to solvents, chemicals, weather, and heat. Unlike PTFE and other fluoropolymers, PVDF is not a fully fluorinated polymer but rather has a repeating chemical structure of CH2CF2. This unique chemical structure results in PVDF with low surface energy and a relatively high density of 1.8 grams per cubic centimeter ("g / cc") to 1.9 g / cc. PVDF's low surface energy and high density typically result in agglomeration and separation of PVDF particles when used in aqueous dispersions; therefore, fluorinated surfactants are typically used. The use of such aqueous dispersions in coating applications is challenging because agglomeration and separation result in uneven coating of particles on the substrate. Additionally, the agglomerates tend to become tightly packed within seven days of the formation of the aqueous dispersion. Tightly packed agglomerates can no longer be redispersed, thereby limiting the usable life of the aqueous dispersion. Therefore, it would be advantageous to achieve a stable dispersion that can retain its homogeneity or is at least redispersible after a seven-day period.

[0004] Fluorinated surfactants are typically required to prepare stable aqueous dispersions, but the inclusion of fluorinated surfactants raises environmental concerns regarding disposal. Various attempts have been made to prepare stable PVDF aqueous dispersions without fluorinated surfactants. For example, U.S. Patent Application Publication No. 2015 / 0030906 provides for the formation of an aqueous dispersion of PVDF using a non-fluorinated surfactant, but such dispersions are readily used because PVDF tends to rapidly aggregate and separate.

[0005] In view of the above teachings, the discovery of an aqueous dispersion of PVDF that is initially homogeneous and redispersible after a seven day period would be surprising. Summary of the Invention

[0006] The present disclosure provides an aqueous dispersion of PVDF that is initially uniform and redispersible after a seven-day period. The present invention is the result of the discovery that not only can highly branched surfactants produce initially uniform aqueous dispersions of PVDF, but also that highly branched surfactants can maintain the redispersibility of PVDF after extended storage times. Without being bound by theory, it is believed that surfactants with a hydrophobe branching degree of 5 or greater can prevent tight agglomeration of PVDF particles, at least in part due to steric hindrance. By preventing tight agglomeration of PVDF particles, the aqueous dispersion can maintain a uniform dispersion over time or be rapidly redispersible.

[0007] The present disclosure is particularly useful in forming coating compositions.

[0008] According to a first aspect of the present disclosure, a coating composition includes water, a plurality of polyvinylidene fluoride particles, and a surfactant having a hydrophobe branching degree of 5 or greater, wherein the composition does not include a fluorinated surfactant.

[0009] According to a second feature of the present disclosure, the surfactant is a nonionic surfactant.

[0010] According to a third feature of the present disclosure, the weight ratio of the surfactant to the polyvinylidene fluoride particles is 2.0% to 15.0%.

[0011] According to a fourth aspect of the present disclosure, the coating composition comprises 20 wt % to 70 wt % of polyvinylidene fluoride particles, based on the total weight of the coating composition.

[0012] According to a fifth aspect of the present disclosure, the coating composition further comprises 0.1 wt % to 10.0 wt % of a dispersant, wherein the dispersant is a random copolymer of diisobutylene and maleic anhydride.

[0013] According to a sixth feature of the present disclosure, the coating composition further comprises 0.1 wt. % to 10.0 wt. % of a dispersant, the dispersant having structure (II), wherein each AO can independently be ethylene oxide, propylene oxide, butylene oxide, and combinations thereof in random or block order, and further wherein each n in structure (II) can independently be 5 to 40.

[0014] According to a seventh feature of the present disclosure, a surfactant has structure (I), wherein n in structure (I) is 3 to 11, and R1 for each n is independently selected from the group consisting of H or alkyl having 1 or 2 carbons.

[0015] According to an eighth feature of the present disclosure, n in structure (I) is 8 to 11 and R1 is H.

[0016] According to a ninth feature of the present disclosure, a method includes dispersing a plurality of polyvinylidene fluoride particles in a mixture of water and a surfactant having a hydrophobe branching degree of 5 or greater, wherein the composition does not include a fluorinated surfactant.

[0017] According to a tenth aspect of the present disclosure, a method for coating a substrate comprises applying the coating composition according to claim 9 to the substrate. DETAILED DESCRIPTION OF THE INVENTION

[0018] As used herein, the term "and / or," when used with a list of two or more items, means that any one of the listed items can be used by itself, or any combination of two or more of the listed items can be used. For example, if a composition is described as containing components A, B, and / or C, the composition can contain A alone, B alone, C alone, A and B in combination, A and C in combination, B and C in combination, or A, B, and C in combination.

[0019] Unless otherwise stated, all ranges are inclusive of the endpoints.

[0020] As used herein, the term weight percent ("wt %"), unless otherwise specified, refers to the weight percentage that a component represents of the total weight of the coating composition.

[0021] As used herein, "CAS Number" is a Chemical Service Registry Number assigned by the Chemical Abstracts Service.

[0022] Coating Composition The present disclosure is directed to a coating composition. The coating composition includes water, a plurality of polyvinylidene fluoride particles, and a surfactant having a hydrophobe branching degree of 5 or greater. The coating composition is free of fluorinated surfactants. As used herein, the term "free of" is defined to mean that the coating composition contains 0.001% by weight or less of the material from which it is said to be free. The coating composition may include a dispersant and / or other additives. For example, the coating composition may contain 20 wt% or more, or 25 wt% or more, or 30 wt% or more, or 35 wt% or more, or 40 wt% or more, or 45 wt% or more, or 50 wt% or more, or 55 wt% or more, or 60 wt% or more, or 65 wt% or more, while simultaneously containing 70 wt% or less, or 65 wt% or less, or 60 wt% or less, or 55 wt% or less, or 50 wt% or less, or 45 wt% or less, or 40 wt% or less, or 35 wt% or less, or 30 wt% or less, or 25 wt% or less, based on the total weight of the coating composition. The coating composition may be useful in forming coatings on battery separators and other applications where uniform deposition of PVDF particles using an aqueous dispersion is advantageous. Furthermore, because the coating composition does not contain a fluorinated surfactant, the coating composition has a lower associated environmental impact.

[0023] Polyvinylidene Fluoride The coating composition includes polyvinylidene fluoride. The PVDF is in the form of a plurality of particles. PVDF may include homopolymers, copolymers, and terpolymers within its meaning. The PVDF may be 50 mole percent ("mol%) or more, or 75 mole% or more, or 80 mole% or more, or 85 mole% or more polyvinylidene fluoride copolymerized with at least one comonomer selected from the group consisting of tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, hexafluoropropene, vinyl fluoride, pentafluoropropene, tetrafluoropropene, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether, other monomers, and combinations thereof. The PVDF may be 100 mole% polyvinylidene fluoride and may contain no additional comonomers. The PVDF particles may have a diameter or maximum linear dimension of 20 nm or more, or 50 nm or more, or 100 nm or more, or 200 nm or more, or 300 nm or more, or 400 nm or more, or 500 nm or less. PVDF can be formed by aqueous free radical emulsion polymerization, suspension polymerization, solution polymerization, and supercritical CO2 polymerization.

[0024] For example, the coating composition may comprise 20 wt% or more, or 25 wt% or more, or 30 wt% or more, or 35 wt% or more, or 40 wt% or more, or 45 wt% or more, or 50 wt% or more, or 55 wt% or more, or 60 wt% or more, or 65 wt% or more, while simultaneously 70 wt% or less, or 65 wt% or less, or 60 wt% or less, or 55 wt% or less, or 50 wt% or less, or 45 wt% or less, or 40 wt% or less, or 35 wt% or less, or 30 wt% or less, or 25 wt% or less PVDF particles, based on the total weight of the coating composition.

[0025] surfactants The coating composition comprises a surfactant. The surfactant comprises both a hydrophobic portion ("hydrophobe") and a hydrophilic portion. The hydrophobe of the surfactant may be linear (i.e., straight chain) or branched (thus having a degree of branching of 2 or greater). The degree of branching is determined by counting the number of hydrophobes extending from the backbone of the hydrophobe. The surfactant has a degree of hydrophobe branching of 5 or greater, or 6 or greater, or 7 or greater, or 8 or greater, or 9 or greater. The surfactant can be a single surfactant or a mixture of surfactants. The surfactant has the structure (I):

[0026] [ka] wherein n in structure (I) is 3 to 11, and R1 for each n is independently selected from the group consisting of H, or alkyl having 1 or 2 carbons. For example, n in structure (I) can be 3, or 4, or 5, or 6, or 7, or 8, or 9, or 10, or 11.

[0027] The coating composition comprises 0.1 wt.% to 10.0 wt.% of a surfactant, based on the total weight of the coating composition. For example, the coating composition may comprise 0.1 wt.% or more, or 0.5 wt.% or more, or 1.0 wt.% or more, or 1.5 wt.% or more, or 2.0 wt.% or more, or 2.5 wt.% or more, or 3.0 wt.% or more, or 3.5 wt.% or more, or 4.0 wt.% or more, or 4.5 wt.% or more, or 5.0 wt.% or more, or 5.5 wt.% or more, or 6.0 wt.% or more, or 6.5 wt.% or more, or 7.0 wt.% or more, or 7.5 wt.% or more, or 8.0 wt.% or more, or 8.5 wt.% or more, or 9.0 wt.% or more, or 9.5 wt.% or more, based on the total weight of the coating composition. On the other hand, it may contain 10.0% by weight or less, or 9.5% by weight or less, or 9.0% by weight or less, or 8.5% by weight or less, or 8.0% by weight or less, or 7.5% by weight or less, or 7.0% by weight or less, or 6.5% by weight or less, or 6.0% by weight or less, or 5.5% by weight or less, or 5.0% by weight or less, or 4.5% by weight or less, or 4.0% by weight or less, or 3.5% by weight or less, or 3.0% by weight or less, or 2.5% by weight or less, or 2.0% by weight or less, or 1.5% by weight or less, or 1.0% by weight or less, or 0.5% by weight or less, or 0.2% by weight or less of a surfactant.

[0028] The coating composition can have a surfactant to PVDF weight ratio of 2% to 15%. For example, the surfactant to PVDF weight ratio is 2.0% or more, or 2.5% or more, or 3.0% or more, or 3.5% or more, or 4.0% or more, or 4.5% or more, or 5.0% or more, or 5.5% or more, or 6.0% or more, or 6.5% or more, or 7.0% or more, or 7.5% or more, or 8.0% or more, or 8.5% or more, or 9.0% or more, or 9.5% or more, or 10.0% or more, or 10.5% or more, or 11.0% or more, or 11.5% or more, or 12.0% or more, or 12.5% ​​or more, or 13.0% or more, or 13.5% or more, or 14.0% or more, or 14.5% or more. % or more, while at the same time being 15.0% or less, or 14.5% or less, or 14.0% or less, or 13.5% or less, or 13.0% or less, or 12.5% ​​or less, or 12.0% or less, or 11.5% or more, or 11.0% or less, or 10.5% or less, or 10.0% or less, or 9.5% or less, or 9.0% or less, or 8.5% or less, or 8.0% or less, or 7.5% or less, or 7.0% or less, or 6.5% or less, or 6.0% or less, or 5.5% or less, or 5.0% or less, or 4.5% or less, or 4.0% or less, or 3.5% or less, or 3.0% or less, or 2.5% or less. The weight ratio of surfactant to PVDF is determined as described in detail below.

[0029] Dispersants The coating composition may include one or more dispersants. For purposes of this disclosure, a dispersant is a non-surfactant material that, when added to a suspension of solid particles in a liquid, promotes the dispersion of the particles or maintains the dispersed particles in suspension. Dispersants may include inorganic dispersants, polymeric dispersants, and small molecule dispersants. The dispersant may be a copolymer of diisobutylene (CAS No. 25167-70-8) and maleic anhydride (CAS No. 108-31-6). In one such example, the dispersant may comprise 30% by weight or more, or 35% by weight or more, or 40% by weight or more, or 45% by weight or more, or 50% by weight or more, or 55% by weight or more, or 60% by weight or more, or 65% by weight or more, while simultaneously 70% by weight or less, or 65% by weight or less, or 60% by weight or less, or 55% by weight or less, or 50% by weight or less, or 45% by weight or less, or 40% by weight or less, or 35% by weight or less diisobutylene, based on the total weight of the dispersant. The dispersant may comprise 30% by weight or more, or 35% by weight or more, or 40% by weight or more, or 45% by weight or more, or 50% by weight or more, or 55% by weight or more, or 60% by weight or more, or 65% by weight or more, while at the same time 70% by weight or less, or 65% by weight or less, or 60% by weight or less, or 55% by weight or less, or 50% by weight or less, or 45% by weight or less, or 40% by weight or less, or 35% by weight or less, of maleic anhydride, based on the total weight of the dispersant.

[0030] In the example of a diisobutylene and maleic anhydride copolymer of the dispersant, the dispersant may have a weight average molecular weight of from 10,000 Daltons to 30,000 Daltons. For example, the dispersing agent may have a molecular weight of 10,000 daltons or more, or 11,000 daltons or more, or 12,000 daltons or more, or 13,000 daltons or more, or 14,000 daltons or more, or 15,000 daltons or more, or 16,000 daltons or more, or 17,000 daltons or more, or 18,000 daltons or more, or 19,000 daltons or more, or 20,000 daltons or more, or 21,000 daltons or more, or 22,000 daltons or more, or 23,000 daltons or more, or 24,000 daltons or more, or 25,000 daltons or more, or 26,000 daltons or more, or 27,000 daltons or more, or 28,000 daltons or more, or 29,000 daltons or more, while simultaneously or less, or a weight average molecular weight of 30,000 daltons or less, or 29,000 daltons or less, or 28,000 daltons or less, or 27,000 daltons or less, or 26,000 daltons or less, or 25,000 daltons or less, or 24,000 daltons or less, or 23,000 daltons or less, or 22,000 daltons or less, or 21,000 daltons or less, or 20,000 daltons or less, or 19,000 daltons or less, or 18,000 daltons or less, or 17,000 daltons or less, or 16,000 daltons or less, or 15,000 daltons or less, or 14,000 daltons or less, or 13,000 daltons or less, or 12,000 daltons or less, or 11,000 daltons or less. The weight average molecular weight of the dispersant is determined using gel permeation chromatography.

[0031] Another example of a suitable dispersant is a compound having the structure (II):

[0032] [ka] wherein each alkylene oxide ("AO") can independently be ethylene oxide, propylene oxide, butylene oxide, and / or combinations thereof in random or block order. Each n in structure (II) can independently be 5 to 40. For example, n can be 5 or more, or 10 or more, or 15 or more, or 20 or more, or 25 or more, or 30 or more, or 35 or more, while simultaneously being 40 or less, or 35 or less, or 30 or less, or 25 or less, or 20 or less, or 15 or less, or 10 or less, or 9 or less, or 8 or less, or 7 or less, or 6 or less. Ethylene oxide may comprise 25% or more by weight of the total weight of structure (II). For example, ethylene oxide may account for 25% by weight or more, or 30% by weight or more, or 40% by weight or more, or 50% by weight or more, or 60% by weight or more, or 70% by weight or more, or 80% by weight or more, while simultaneously 90% by weight or less, or 80% by weight or less, or 70% by weight or less, or 60% by weight or less, or 50% by weight or less, or 40% by weight or less, or 30% by weight or less.

[0033] The coating composition can include 0 wt. % or 0.1 wt. % to 10.0 wt. % of dispersant, based on the total weight of the coating composition. For example, the coating composition can include 0.1 wt. % or more, or 0.5 wt. % or more, or 1.0 wt. % or more, or 1.5 wt. % or more, or 2.0 wt. % or more, or 2.5 wt. % or more, or 3.0 wt. % or more, or 3.5 wt. % or more, or 4.0 wt. % or more, or 4.5 wt. % or more, or 5.0 wt. % or more, or 5.5 wt. % or more, or 6.0 wt. % or more, or 6.5 wt. % or more, or 7.0 wt. % or more, or 7.5 wt. % or more, or 8.0 wt. % or more, or 8.5 wt. % or more, or 9.0 wt. % or more, or 9.5 wt. % of dispersant, based on the total weight of the coating composition. or more, while at the same time comprising 10.0% by weight or less, or 9.5% by weight or less, or 9.0% by weight or less, or 8.5% by weight or less, or 8.0% by weight or less, or 7.5% by weight or less, or 7.0% by weight or less, or 6.5% by weight or less, or 6.0% by weight or less, or 5.5% by weight or less, or 5.0% by weight or less, or 4.5% by weight or less, or 4.0% by weight or less, or 3.5% by weight or less, or 3.0% by weight or less, or 2.5% by weight or less, or 2.0% by weight or less, or 1.5% by weight or less, or 1.0% by weight or less, or 0.5% by weight or less, or 0.2% by weight or less of dispersant.

[0034] Methods of Making Coating Compositions and Coating Substrates The coating composition is formed by a method including dispersing a plurality of polyvinylidene fluoride particles in a mixture of water and a surfactant having a hydrophobe branching degree of 5 or greater, wherein the composition does not contain a fluorinated surfactant. Dispersing the polyvinylidene fluoride particles in the mixture of water and surfactant can be accomplished in a variety of ways. For example, the coating composition can be placed in a grinding jar along with beads (e.g., glass, ZrO, Al2O3, etc.) and ground for a predetermined period of time. Such grinding methods are advantageously used when the PVDF particles are added to the coating composition at a size larger than desired in the dispersion. Additionally, or alternatively, the PVDF particles may be directly mixed or stirred in the combined water and surfactant. It will be understood that the PVDF particles, surfactant, water, dispersant, and any other additives can be added together in any order.

[0035] The coating composition is useful for forming a coated substrate. A method for coating a substrate can be carried out by applying the coating composition to the substrate. The coating composition can be applied to the substrate in various ways. For example, the substrate can be immersed in the composition, the composition can be sprayed onto the substrate, the substrate can be a continuous sheet passing through a bath separated from the coating composition, and / or other methods can be used to apply the coating composition to the substrate. The substrate can include polymeric materials, metals, ceramics, amorphous materials (e.g., glass), and / or other types of materials. Examples of polymeric substrates can include low-density polyethylene, medium-density polyethylene, high-density polyethylene, polyolefin elastomers, copolymers of one or more alpha-olefins with another monomer, and other types of polymeric materials. In an exemplary use, the coating composition can be applied to a polymeric substrate to form a separator layer for a battery. [Example]

[0036] material The following materials were used in forming the inventive examples ("IE") and comparative examples ("CE").

[0037] Surfactant 1 is a surfactant having a 90% by weight actives aqueous solution and structure (I) where n is 8 and R1 is H. Surfactant 1 has a hydrophobe branching level of 5. Surfactant 1 is available from The Dow Chemical Company, Midland, Michigan.

[0038] Surfactant 2 is a surfactant having a 90% by weight actives aqueous solution and structure (I) where n is 11 and R1 is H. Surfactant 2 has a hydrophobe branching level of 5. Surfactant 2 is available from The Dow Chemical Company, Midland, Michigan.

[0039] Dispersant 1 is formed from 45% to 55% by weight of diisobutylene monomer units, the remainder being maleic anhydride. The dispersant has a weight average molecular weight of about 16,500 daltons and is available from The Dow Chemical Company, Midland, Michigan.

[0040] Dispersant 2 is a dispersant having structure (II) where each AO chain is composed of ethylene oxide and propylene oxide units in block sequence, and the average repeat unit n in each branch is about 37. Dispersant 2 is available from The Dow Chemical Company, Midland Michigan.

[0041] Surfactant 3 is 3,5,5-trimethylhexyl ethoxylate with a hydrophobe branching level of 4 and is available from Sigma Aldrich, St. Louis, Missouri.

[0042] Surfactant 4 is a 2-ethylhexanol EO-PO nonionic surfactant having a CAS number of 64366-70-7 and a hydrophobe branching level of 2. Surfactant 4 is available from The Dow Chemical Company, Midland Michigan.

[0043] Surfactant 5 is a C12-14-secondary alcohol ethoxolate having a CAS number of 84133-50-6 and a hydrophobe branch of 2. Surfactant 5 is available from The Dow Chemical Company, Midland Michigan.

[0044] Surfactant 6 is an isotridecyl alcohol ethoxylate having an average hydrophobe branching of 4 and is commercially available as LUTENSOL™ TO from BASF corporation, Ludwigshafen, Germany.

[0045] PVDF is a polyvinylidene fluoride homopolymer particle commercially available as KYNAR™ HSV900 from Arkema, Colombes, France.

[0046] The ZrO beads were 0.8–1.2 mm diameter ZrO beads from Sinopharm Chem.Reagent Co.Ltd., China.

[0047] Sample preparation Comparative examples and inventive examples were prepared by charging a premixed mixture of surfactant, PVDF powder, dispersant (IE1), and water into a grinding jar. ZrO beads were weighed and added. The jar was placed in a sand mill from Shanghai Dedong, and water cooling for the grinding jar was initiated before the grinding process began. The grinding process was carried out for 4 hours at 1400 revolutions per minute. After the allotted time, the ZrO beads were filtered out by passing the ground mixture through a 500-mesh nylon sieve. A sample of the ground PVDF dispersion was applied to conductive tape for characterization using a NOVA™ Nanosem 630 scanning electron microscope from FEI Company. All examples were stored without stirring at approximately 23°C for 7 days to observe for aggregation and sedimentation. The weight ratio of surfactant to PVDF was calculated by dividing the weight in grams of surfactant present (taking into account any diluents in the surfactant) by the weight in grams of PVDF particles and multiplying by 100. Examples were evaluated both visually and using a scanning electron microscope. Examples that could not be redispersed after storage were referred to as agglomerated or tightly agglomerated, the difference being the amount of material that could be liberated from the bottom of the jar by agitation. Examples in which the PVDF could be agitated to resume a uniform dispersion were classified as redispersible.

[0048] result Table 1 provides the compositions of IE1 to IE5 and CE1 to CE4. The compositions of the examples are provided in grams.

[0049] [Table 1]

[0050] Table 2 provides the results for the different surfactants used in terms of the initial dispersion appearance, the morphology after 7 days of storage, and the average particle size peak present.

[0051] [Table 2]

[0052] Referring now to Tables 1 and 2, all of the inventive examples and comparative examples 1 and 4 exhibited uniform, milky dispersions after the milling process. However, after 7 days of storage at 23°C, CE1 to CE4 exhibited phase separation, resulting in the formation of a strong sediment at the bottom of the sample container. The sediment in CE1 to CE4 could not be redispersed by manual shaking. IE1 remained uniform even after 7 days of storage. IE2 to IE5 exhibited phase separation, but the sediment could be redispersed by manual shaking. CE1 to CE4 demonstrate that selecting a surfactant with hydrophobe branching of 4 or less cannot prevent aggregation, even though different surfactants are used. However, IE1 to IE5, which utilize surfactants with hydrophobe branching of 5, all achieved aqueous dispersions of PVDF that were initially uniform and redispersible after a 7-day period. Surfactants with a hydrophobe branching level of 6 or greater exhibited the same resistance to aggregation and are believed to be redispersible due to even greater steric hindrance effects. The present application also relates to the following aspects: (1) 1. A coating composition comprising: Water and a plurality of polyvinylidene fluoride particles; a surfactant having a hydrophobe branching degree of 5 or greater; A coating composition, wherein the composition does not comprise a fluorinated surfactant. (2) The coating composition according to (1) above, wherein the surfactant is a nonionic surfactant. (3) The coating composition according to (1) above, wherein the weight ratio of the surfactant to the polyvinylidene fluoride particles is 2.0% to 15.0%. (4) The coating composition according to (1) above, wherein the coating composition contains 20 wt % to 70 wt % of the polyvinylidene fluoride particles based on the total weight of the coating composition. (5) The coating composition according to (1) above, further comprising 0.1 wt % to 10.0 wt % of a dispersant, wherein the dispersant is a random copolymer of diisobutylene and maleic anhydride. (6) further comprising 0.1 wt. % to 10.0 wt. % of a dispersant, wherein the dispersant has Structure (II): [ka] wherein each AO can independently be ethylene oxide, propylene oxide, butylene oxide, or a combination thereof in a random or block order; and further, each n in structure (II) can independently be 5 to 40. (7) The surfactant has the structure (I):

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Claims

1. 1. A coating composition comprising: Water and a plurality of polyvinylidene fluoride particles; Structure (I): 【Chemistry 1】 wherein n in said structure (I) is 3 to 11, and R 1 for each n is independently selected from the group consisting of H or alkyl having 1 or 2 carbons; A coating composition, wherein the composition does not comprise a fluorinated surfactant.

2. The coating composition of claim 1 , wherein the surfactant is a nonionic surfactant.

3. 2. The coating composition of claim 1, wherein the weight ratio of the surfactant to the polyvinylidene fluoride particles is 2.0% to 15.0%.

4. The coating composition of claim 1, wherein the coating composition comprises 20% to 70% by weight of the polyvinylidene fluoride particles, based on the total weight of the coating composition.

5. 10. The coating composition of claim 1, further comprising 0.1 wt. % to 10.0 wt. % of a dispersant, said dispersant being a random copolymer of diisobutylene and maleic anhydride.

6. further comprising 0.1 wt. % to 10.0 wt. % of a dispersant, said dispersant having Structure (II): 【Chemistry 2】 wherein each AO can independently be ethylene oxide, propylene oxide, butylene oxide, and combinations thereof in random or block order; and further wherein each n in structure (II) can independently be 5 to 40.

7. n in structure (I) is 8 to 11, and R １ The coating composition of claim 1 , wherein: is H.

8. 1. A method of forming a coating composition, comprising: A plurality of polyvinylidene fluoride particles are mixed with water, Structure (I): 【Transformation 3】 wherein n in said structure (I) is 3 to 11, and R 1 for each n is independently selected from the group consisting of H or alkyl having 1 or 2 carbons. wherein the composition is free of fluorinated surfactants.

9. 1. A method of coating a substrate, comprising: A method comprising applying the coating composition of claim 8 to a substrate.

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