ELECTROCOATING COMPOSITION
20210371679 · 2021-12-02
Assignee
Inventors
Cpc classification
C09D175/12
CHEMISTRY; METALLURGY
C09D5/4492
CHEMISTRY; METALLURGY
International classification
C09D175/12
CHEMISTRY; METALLURGY
Abstract
Cathodic electrocoating compositions and methods for coating electrically conductive substrates are provided. An exemplary cathodic electrocoating composition includes an aqueous carrier and a film forming binder dispersed in the carrier. Further, the cathodic electrocoating composition includes guar gum as an edge protective agent.
Claims
1. A cathodic electrocoating composition comprising: an aqueous carrier; a film forming binder dispersed in the carrier; and guar gum as an edge protective agent.
2. The cathodic electrocoating composition of claim 1 wherein the guar gum is present in amounts of from about 0.05 to about 2.0 wt. % based on binder solids.
3. The cathodic electrocoating composition of claim 1 wherein the guar gum is present in amounts of from about 0.08 to about 1.5 wt. % based on binder solids.
4. The cathodic electrocoating composition of claim 1 wherein the guar gum is present in amounts of from about 0.1 to about 1.0 wt. % based on binder solids.
5. The cathodic electrocoating composition of claim 1 wherein the guar gum is present in amounts of from about 0.15 to about 0.6 wt. % based on binder solids.
6. The cathodic electrocoating composition of claim 1 wherein the guar gum is present in amounts of from about 0.2 to about 0.5 wt. % based on binder solids.
7. The cathodic electrocoating composition of claim 1 wherein the guar gum is present in amounts of from about 0.2 to about 0.4 wt. % based on binder solids.
8. The cathodic electrocoating composition of claim 1 wherein the guar gum is present in amounts of from about 0.25 to about 0.35 wt. % based on binder solids.
9. The cathodic electrocoating composition of claim 1 wherein the film forming binder comprises an epoxy-amine adduct and a blocked polyisocyanate crosslinking agent.
10. The cathodic electrocoating composition of claim 1 wherein the film forming binder contains from about 35 to about 45 percent by weight solids.
11. The cathodic electrocoating composition of claim 1 further comprising a pigment paste.
12. The cathodic electrocoating composition of claim 1 further comprising a pigment paste, wherein the pigment paste contains from about 45 to about 55 percent by weight solids, and wherein the film forming binder contains from about 35 to about 45 percent by weight solids.
13. An improved aqueous cathodic electrocoating composition comprising an aqueous carrier and a film forming binder dispersed in the aqueous carrier; wherein the improvement is the incorporation of an edge protective agent comprising guar gum.
14. The improved aqueous cathodic electrocoating composition of claim 13 wherein the guar gum is present in amounts of from about 0.05 to about 2.0 wt. % based on binder solids.
15. The improved aqueous cathodic electrocoating composition of claim 13 wherein the guar gum is present in amounts of from about 0.08 to about 1.5 wt. % based on binder solids.
16. The improved aqueous cathodic electrocoating composition of claim 13 wherein the guar gum is present in amounts of from about 0.1 to about 1.0 wt. % based on binder solids.
17. The improved aqueous cathodic electrocoating composition of claim 13 wherein the guar gum is present in amounts of from about 0.2 to about 0.5 wt. % based on binder solids.
18. The improved aqueous cathodic electrocoating composition of claim 13 wherein the guar gum is present in amounts of from about 0.2 to about 0.4 wt. % based on binder solids.
19. The improved aqueous cathodic electrocoating composition of claim 13 wherein the guar gum is present in amounts of from about 0.25 to about 0.35 wt. % based on binder solids.
20. A method for coating an electrically conductive substrate, comprising: forming an electrodeposition bath of a cathodic electrocoating composition comprising: an aqueous carrier; a film forming binder dispersed in the carrier; and an edge protective agent comprising guar gum; dipping the electrically conductive substrate into the electrodeposition bath; connecting the substrate as a cathode; applying a current to the substrate to deposit a film on the substrate; removing the substrate with the deposited film from the electrodeposition bath; and baking the deposited coating film.
Description
DETAILED DESCRIPTION
[0011] The following detailed description is merely exemplary in nature and is not intended to limit the electrocoating compositions and methods for forming electrocoating compositions as described herein. Furthermore, there is no intention to be bound by any theory presented in the preceding background or summary or in the following detailed description.
[0012] As used herein, “a,” “an,” or “the” means one or more unless otherwise specified. The term “or” can be conjunctive or disjunctive. Open terms such as “include,” “including,” “contain,” “containing” and the like mean “comprising.” In certain embodiments, numbers in this description indicating amounts, ratios of materials, physical properties of materials, and/or use are may be understood as being modified by the word “about”. The term “about” as used in connection with a numerical value and the claims denotes an interval of accuracy, familiar and acceptable to a person skilled in the art. In general, such interval of accuracy is ±10%. All numbers in this description indicating amounts, ratios of materials, physical properties of materials, and/or use may be understood as modified by the word “about,” except as otherwise explicitly indicated. As used herein, the “%” or “percent” described in the present disclosure refers to the weight percentage unless otherwise indicated.
[0013] An electrocoating composition for coating a substrate is provided herein. The electrocoating composition may be utilized to coat any type of substrate known in the art. In embodiments, the substrate is a vehicle, automobile, or automobile vehicle. “Vehicle” or “automobile” or “automobile vehicle” includes an automobile, such as, car, van, minivan, bus, SUV (sports utility vehicle); truck; semi-truck; tractor; motorcycle; trailer; ATV (all-terrain vehicle); pickup truck; heavy duty mover, such as, bulldozer, mobile crane and earth mover; airplanes; boats; ships; and other modes of transport.
[0014] The electrocoating composition is utilized to form a coating layer on the substrate. Exemplary embodiments herein provide a full electrocoating bath to form a coating layer on a substrate. Certain embodiments utilize epoxy amine based resins or binders that are neutralized with acids to form emulsions.
[0015] Weak edge protection is a major source of corrosion for electrocoated surfaces. It has been observed that bubble or rupture defects are often formed at sharp edges of substrates being electrocoated. During the electrocoating process, extremely high current densities are experienced at sharp edges. Therefore, electrically initiated surface defects may develop and harm edge protection. Typically, efforts to improve edge protection have resulted in worsening other characteristics of the coating and coating appearance.
[0016] However, herein is described a composition and method for improving edge protection while maintaining coating appearance.
[0017] It has been surprisingly found that the use of guar gum as an edge protective agent within an electrocoating composition as described herein provides improved edge protection for films formed by electrocoating.
[0018] Thus, provided herein is an electrocoating composition, such as for use as an electrodeposition bath, with improved edge protection and good coating appearance that includes an aqueous carrier; a film forming binder dispersed in the carrier and comprising an epoxy-amine adduct and a blocked polyisocyanate crosslinking agent; a pigment paste; and an edge protective comprising, consisting essentially of, or consisting of guar gum. In exemplary embodiments, the edge protective agent is present in amounts of from 0.1 to 1.0% based on binder solids.
[0019] Guar Gum
[0020] Guar gum, also called guaran, is a galactomannan polysaccharide extracted from the seeds of guar beans that has thickening and stabilizing properties. For forming guar gum, guar seeds are typically mechanically dehusked, hydrated, milled and screened before processing into a powder. Chemically, guar gum is an exo-polysaccharide composed of the sugars galactose and mannose. The backbone is a linear chain of β 1,4-linked mannose residues to which galactose residues are 1,6-linked at every second mannose, forming short side-branches.
[0021] In example embodiments, guar gum is incorporated into the electrocoating composition. The guar gum may be useful in the electrocoating composition at levels of from 0.1 to 1.0, such as from 0.15 to 0.6, for example from 0.2 to 0.5, such as from 0.2 to 0.4, for example from 0.25 to 0.35, such as 0.3, percent by weight, the percentage by weight being based on weight of binder solids of the composition.
[0022] In certain embodiments, the guar gum is present in the composition in amounts of at least 0.02, such as at least 0.04, for example at least 0.06, such as at least 0.08, for example at least 0.1, such as at least 0.12, for example at least 0.14, such as at least 0.16, for example at least 0.18, such as at least 0.2, for example at least 0.22, such as at least 0.24, for example at least 0.26, such as at least 0.28, for example at least 0.3, percent by weight, based on weight of resin solids of the composition.
[0023] In certain embodiments, the guar gum is present in the composition in amounts of at most 1.0, such as at most 0.9, for example at most 0.8, such as at most 0.7, for example at most 0.6, such as at most 0.55, for example at most 0.5, such as at most 0.45, for example at most 0.425, such as at most 0.4, for example at most 0.38, such as at most 0.36, for example at most 0.35, such as at most 0.34, for example at most 0.33, such as at most 0.32, for example at most 0.31, such as at most 0.3, percent by weight, based on weight of resin solids of the composition.
[0024] Film Forming Binder
[0025] Most of the solids in the electrocoated film come from the backbone resin or film forming binder in the electrocoating bath. Common cathodic electrocoating backbone emulsions include an acid-neutralized water-soluble binder of an epoxy amine adduct blended with a crosslinking agent. Exemplary binders and crosslinking agents are disclosed in U.S. Pat. No. 4,419,467, which is hereby incorporated by reference. Typical crosslinking agents are based on blocked isocyanates which are prepared by reacting isocyanates such as hexamethylene diisocyanate, cyclohexamethylene diisocyanate, toluene diisocyanate, methylene diphenyl diisocyanate, or other suitable isocyanates, with blocking agents like oximes, alcohols, or caprolactams, which block the reactive isocyanate functionality. These blocking agents separate only during baking and provide a reactive isocyanate group which can react with hydroxy or amine group and form crosslink networks.
[0026] An exemplary film forming binder contains from 35 to 45, such as 40, percent by weight solids.
[0027] Additives
[0028] Further additives such as catalysts, anti-crater additives, etc., can be added to the emulsion to achieve desired properties.
[0029] Pigment Paste
[0030] Another major source of solids in electrocoated films come from pigments that are incorporated in the electrocoating composition in the form of a paste. Pigment paste may be prepared by de-agglomerating pigment particles and dispersing them in a grinding vehicle. An exemplary grinding vehicle includes a resin (grinding resin), water and additives like wetting agents, surfactants, catalyst and defoamers. Any suitable known pigment grinding vehicle may be used. After grinding, the particle size of the pigment should be as small as practical; generally, the particle size is from 6 to 8 using a Hegman grinding gauge.
[0031] Exemplary pigments for use in the electrocoating composition include titanium dioxide, barium sulfate, carbon black, hydrated aluminum silicate, basic lead silicate, strontium chromate, iron oxide, clay and the like. In certain embodiments, the pigment paste may include an anti-corrosive pigment or blends of anticorrosive pigments. Exemplary anti-corrosive pigments include metallic chromates, phosphates, phosphites, borates, borosilicates, phosphosilicates, molybdates, oxides, and rare earth compounds. Organic anticorrosive agents may optionally also be present; they include benzotriazoles, morpholines, azoles, calcium alkyl-aryl sulfonates, diamines, and metal salts of dinonylnapathalene sulfonates.
[0032] An exemplary pigment may have a pigment to binder weight ratio of from 2:1 to 6:1. An exemplary pigment paste may contain from 40 to 65, such as 45 to 55, percent by weight solids. General cathodic electrocoating pigment pastes can be used, such as those disclosed in U.S. Pat. No. 6,207,731.
[0033] After formation of an exemplary electrocoating composition, the cathodic electrocoating composition has a pigment to binder weight ratio of less than 0.5:1, such as less than 0.4:1, for example from 0.1:1 to 0.4:1, such as from 0.15:1 to 0.4:1. The pigment to binder weight ratio may be an important parameter. Generally, higher pigment to binder weight ratios in the composition can affect the flow of the composition and therefore, appearance.
Examples
[0034] Examples 1 and 2 were prepared and tested for edge protection performance.
[0035] Preparation of Guar Gum Stock Solution
[0036] A 2,000 g 1% guar gum stock solution was prepared by dissolving 20 g of guar gum in 1,980 g of deionized water. This solution was then stirred overnight before use.
[0037] Preparation of Electrocoating Composition for Use as Electrodeposition Bath
[0038] Each of the baths was prepared by combining a suitable emulsion with additives, water and pigment paste. This mixture was stirred for at least 4 hours before panels were electrocoated via the application of a current of from 170 to 280 volts to deposit a film having a film thickness of from 0.8 to 1.0 mils (from 20.23 to 25.4 microns). The coated panels were analyzed for surface roughness using a profilometer and edge corrosion resistance using a corrosion testing method.
TABLE-US-00001 TABLE 1 Composition of Example Baths Electrocoating composition components Example 1 Example 2 Backbone emulsion 1516.4 g 1514.1 g (40% solids) DI Water 1887.2 g 1817.4 g Pigment paste 296.3 g 274.4 g (50% solids) Guar Gum as Edge 0 0.3% Guar Protective Agent gum solids based on resin solids
TABLE-US-00002 TABLE 2 Properties of Example Baths Example 1 Example 2 Bath Solid (%) 20% 15% Bath P/B (%) 18% 18% pH 6.08 6.03 Conductivity 1945 2093 Ra (μm) 0.25 0.60 VDA 233-102 4.3 1
[0039] In Example 1, no edge protective agent was included. In Example 2, the electrocoating composition was formed with 0.3% guar gum solids, based on resin solids and represents an embodiment of the electrocoating composition with improved edge protection.
[0040] The edge protection performance was characterized via an accelerated cyclic corrosion (VDA 233-102: Cyclic corrosion testing of materials & components in automotive construction), and the coating appearance was evaluated by surface roughness (Ra). As can be seen, the coating appearance (Ra) of Example 2 was sufficient while the edge protection was improved.
[0041] The electrocoating composition may be described herein as an aqueous dispersion. The term “dispersion” as used within the context herein is believed to be a two-phase translucent or opaque aqueous resinous binder system in which the binder is in the dispersed phase and water the continuous phase. The average particle size diameter of the binder phase may be 0.1 to 10 microns, such as less than 5 microns. The concentration of the binder in the aqueous medium in general is not critical, but ordinarily the major portion of the aqueous dispersion is water. The aqueous dispersion usually contains from 3 to 50 percent, such as 5 to 40 percent by weight binder solids. Aqueous binder concentrates which are to be further diluted with water when added to an electrocoating bath, generally have a range of binder solids of 10 to 30 percent weight.
[0042] As compared to conventional aqueous cathodic electrocoating compositions, a cathodic electrocoating composition formed with the above-described edge protective agent exhibited improved edge protection and good coating appearance.
[0043] While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment. It being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope as set forth in the appended claims.