WO2011085520A1 - Formulations de revêtement à base de résine alkyde - Google Patents

Formulations de revêtement à base de résine alkyde Download PDF

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Publication number
WO2011085520A1
WO2011085520A1 PCT/CN2010/000068 CN2010000068W WO2011085520A1 WO 2011085520 A1 WO2011085520 A1 WO 2011085520A1 CN 2010000068 W CN2010000068 W CN 2010000068W WO 2011085520 A1 WO2011085520 A1 WO 2011085520A1
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Prior art keywords
coating
formulation
coating formulation
surfactant
present
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PCT/CN2010/000068
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English (en)
Inventor
Yupeng Lee
Ling Chen
Haibo Fang
Jiangqiang Hu
Ping Zhang
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Dow Global Technologies Llc
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Priority to PCT/CN2010/000068 priority Critical patent/WO2011085520A1/fr
Publication of WO2011085520A1 publication Critical patent/WO2011085520A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/027—Dispersing agents

Definitions

  • the present invention relates to coating formulations. More specifically, the present invention relates to solvent-borne (SB) alkyd coating formulations, in particular to low cost SB air-drying alkyd coating formulations having low volatile organic compounds (VOC) and a low viscosity.
  • SB solvent-borne
  • VOC volatile organic compounds
  • the coating formulations of the present invention may be useful for example as protective topcoats or primer coats.
  • Alkyd coating formulations containing solvents are widely used for wall paints; and for wood and metal coatings for protective and aesthetic reasons.
  • the coating industry is continually seeking the development of lower VOC coating formulations, i.e., formulations containing no solvents or at least a solvent concentration of less than about 10 weight percent.
  • lower VOC coating formulations i.e., formulations containing no solvents or at least a solvent concentration of less than about 10 weight percent.
  • solvent prices have increased in line with oil prices, and therefore, the challenge for paint formulators and alkyd coat formulators is to develop alkyd coatings with lower solvent levels (i.e., lower VOC), that have unchanged paint and dry film properties, and which are cost effective.
  • water can be formulated in solvent based alkyd coats as a partial replacement for the solvent present in the coating formulation via the use of surfactants as emulsion stabilizers in the alkyd coats.
  • surfactants as emulsion stabilizers in the alkyd coats.
  • certain surfactants have been tried in the coating formulation. Introducing certain surfactants into a solvent-based alkyd coat may allow water to replace the solvent in the coat.
  • Performances such as viscosity, dry time, gloss, impact resistance and hardness, adhesion, flexibility, and the like are difficult to maintain in previously known coating formulations. It would be desirable to provide a coating formulation with a low VOC, a low cost and a good emulsion performance which would meet certain requirements of industry performance standards.
  • the present invention uses a combination of two or more surfactants as an emulsifier that allows water to replace solvent present in SB, self-drying alkyd coating formulations.
  • the formulations of the present invention achieve excellent performance.
  • the paint performance and dry film performance of the coating formulations can meet requirements of standards in the industry.
  • an alkyd topcoat or a primer coat of the present invention is useful for providing several performance attributes or properties to the final cured coating.
  • the alkyd coating formulation of the present invention has a lower viscosity than known coating formulations; and therefore, the coating formulation of the present invention can be easily applied to a substrate.
  • One embodiment of the present invention is directed to a coating composition or formulation including (a) at least one hydrophilic surfactant; (b) at least one hydrophobic surfactant; (c) water; (d) at least one solvent; and (e) at least one solvent borne air drying alkyd coating resin.
  • Another optional embodiment of the present invention includes adding at least one amino-methyl propanol co-dispersant such as AMP or AMP95 into the above coating formulation.
  • Yet another embodiment of the present invention is directed to an alkyd protective top coat or an alkyd primer coat utilizing the above coating formulations; wherein the coating formulation has a low VOC and a low viscosity.
  • the VOC level of the coating formulation of the present invention can be for example a VOC level of less than about 10% VOC based on the total formulation of the SB alkyd coating.
  • the coating formulation of the present invention can have a viscosity of, for example, less than about 600 mPa-s.
  • One broad scope of the present invention is directed to a coating formulation including (a) at least one hydrophilic surfactant; (b) at least one hydrophobic surfactant; (c) water; (d) at least one solvent; and (e) at least one solvent borne air drying alkyd coating resin.
  • the coating formulation optionally, may include (f) at least one amino-methyl propanol co-dispersant.
  • HLB hydrophilic- lipophilic balance of a surfactant (which is a measure of the degree to which a surfactant is hydrophilic or lipophilic, as determined by calculating values for different regions of a molecule, as described in Griffin W.C., "Classification of Surface- Active Agents by 'HLB,'” Journal of the Society of Cosmetic Chemists 1 (1949), page 311; and Griffin W.C.,
  • hydrophilic surfactant herein means a surfactant with a HLB of equal to or greater than about 10.
  • hydrophobic surfactant herein means a surfactant with a HLB of less than about 10.
  • the at least one hydrophilic surfactant used in the present invention may be selected from (i) nonionic hydrophilic surfactants, (ii) anionic hydrophilic surfactants, and (iii) mixtures thereof.
  • the nonionic hydrophilic surfactant used in the present invention may include for example ethylene oxide/propylene oxide (EO/PO) copolymers, ethoxylates; and mixtures thereof.
  • EO/PO ethylene oxide/propylene oxide
  • the at least one nonionic hydrophilic surfactant includes alkyl and alkylarylpolydiol ethers such as ethoxylation products of lauryl, oleyl, and stearyl alcohols; alkylphenol glycol ethers such as ethoxylation products of octylphenol or nonylphenol and the like; and mixtures thereof.
  • the at least one nonionic hydrophilic surfactant used in the present invention may include, for example, alkyl EO/PO copolymers such as Tergitol XH, Tergitol XD, and Tergitol L series; and nonylphenol ethoxylates (NPE) such as Tergitol NP series surfactants commercially available from The Dow Chemical Company.
  • alkyl EO/PO copolymers such as Tergitol XH, Tergitol XD, and Tergitol L series
  • NPE nonylphenol ethoxylates
  • the anionic hydrophilic surfactant used in the present invention may include for example commercially available products such as DowfaxTM 1A1, Dowfax 3B2, Dowfax CIOL, Dowfax 30599 , TRITONTM XQS-20 , TRITON H-55 (trademarks of The Dow Chemical Company), and the like; and mixtures thereof.
  • the at least one anionic hydrophilic surfactant includes for example Dowfax 1A1.
  • the concentration of nonionic or anionic hydrophilic surfactant present in the coating formulation of the present invention is generally between 0.01 weight percent (wt%) to about 1.5 wt%, preferably between about 0.1 wt% to about 1.2 wt%, and more preferably between about 0.4 wt% to about 0.8 wt%, based on the weight of the total formulation. If the usage is below the recommended concentration, water may be introduced into the coating formulation; and the formulation may not be stable, that is, the water may phase separate out of the formulation after a period of time. If the usage level is above the recommended concentration, the resulting cured coating's water resistance will be impacted detrimentally.
  • the ratio of nonionic hydrophilic surfactant to anionic hydrophilic surfactant may be generally from about 10 to about 0.5, preferably from about 8 to about 1, and more preferably from about 8 to about 5, based on the weight of the total formulation.
  • the at least one hydrophobic surfactant used in the present invention may be selected from (i) nonionic hydrophobic surfactants, (ii) anionic hydrophobic surfactants, and (iii) mixtures thereof.
  • the nonionic hydrophobic surfactant used in the present invention may include, for example, alkylphenol ethoxylates or EO/PO copolymers or ethoxylates, and mixtures thereof.
  • the nonionic hydrophobic surfactant used in the present invention includes, for example, octylphenol ethoxylates such as TRITON X-15, NP-4,
  • NP-6, TMN-3 (trademarks of The Dow Chemical Company), other oil soluble surfactants, and mixtures thereof.
  • the anionic hydrophobic surfactant used in the present invention may include for example commercially available products such as TRITON GR-7M; and the like; and mixtures thereof.
  • the at least one anionic hydrophobic surfactant includes for example TRITON GR-7M.
  • the concentration of nonionic or anionic hydrophobic surfactant present in the coating formulation of the present invention is generally between 0.001 wt% to about 0.8 wt%, preferably between about 0.01 wt% to about 0.6 wt%, and more preferably between about 0.1 wt% to about 0.4 wt%, based on the weight of the total formulation. If the concentration of the hydrophobic surfactant is above the recommended concentration, the coating formulation's viscosity may significantly increase.
  • a mixture of any of the nonionic and anionic hydrophobic surfactants described above may be used in the formulation of the present invention.
  • the ratio of nonionic hydrophobic surfactant to anionic hydrophobic surfactant may be generally from about 10 to about 1, preferably from about 8 to about 1, and more preferably from about 5 to about 1 , based on the weight of the total formulation.
  • the water component used in the coating formulation of the present invention may be preferably deionized water, tap water or a mixture thereof.
  • the concentration of the water present in the coating formulation of the present invention is generally between 1 wt% to about 30 wt%. In another embodiment the water
  • concentration may be from about 3 wt% to about 20 wt%, preferably between about 5 wt% to about 20 wt%, and more preferably between about 5 wt% to about 15 wt%, based on the weight of the total composition. If the water is added above about 30 wt%, the paint viscosity may become too high (e.g. greater than about 1000 mPa-s) to apply with air spray techniques; the system may tend to be unstable; and the resulting coating's performance may become poor such as for example low gloss for alkyd finishes. In the coating formulation of the present invention, water may be added into the coating formulation for example at the last stage of the paint making process.
  • the solvent useful for the coating formulation of the present invention may be any conventional solvent known in the art.
  • suitable organic solvents include, but are not limited to, xylene, benzene, toluene, white spirits, and mixtures thereof.
  • the solvent may include xylene, white spirit (Exxsol D40), 200# solvent and the like; and mixtures thereof.
  • concentration of solvent present in the coating formulation of the present invention is generally between 10 wt% to about 40 wt%, based on the weight of the total formulation.
  • the coating formulation of the present invention also includes at least one alkyd resin.
  • the alkyd resin useful for the coating formulation of the present invention may be any unsaturated alkyd resin well known in the art.
  • the alkyd resin may include air drying natural oil modified alkyd resin.
  • the alky resin used in the present invention includes air drying soybean oil alkyd resins, air drying tall oil alkyd resins and any other unsaturated oil modified alkyd resin which is air drying.
  • alkyd resin useful in the present invention include for example commercial alkyd resin such as Alkyd Resin 389-37; or Alkyd Resin 389-5, 389-6, 389-7, 389-8, or 389-9; or any other air drying alkyd for protective coating applications.
  • a preferred example of a commercially available alkyd resin may be for example, the alkyd resin commercially available under the trade name Alkyd Resin 389-37 or Alkyd Resin 389-9 (50-60% non- volatile mass— soybean oil alkyd resin with 60% oil length,
  • soybean oil alkyd resin types may be used for protective coatings.
  • the concentration of the alkyd resin present in the coating formulation of the present invention is generally between about 30 wt% to about 80 wt%, which is dependent on the formulation designs of the coating. If the alkyd resin usage is above or below the recommended concentration range, the final cured coating's performance such as the coating's anti-corrosive properties may be detrimentally impacted.
  • the alkyd resins useable in the present invention may include any of the conventional alkyds typically used in air drying alkyd coatings formulations. Long to medium oils length are preferred such as for example above 50% oil weight percent by weight in the alkyd resin.
  • Alkyd resins may be, for example, thermosetting reaction products of a dihydric or polyhydric alcohol (e.g., ethylene glycol or glycerol) and a mono/polybasic acid (e. g., phthalic anhydride) in the presence of a drying oil (e.g., linseed, soybean), wherein the drying oil acts as a modifier.
  • Alkyd resins may be produced for example by direct fusion of glycerol, phthalic anhydride and drying oil at from about 210° C to about 232° C. Solvents may be added to reaction mixture to produce alkyd resins and then further added to adjust the solids content of the mixture.
  • the coating formulation of the present invention may also include one or more optional components including for example at least one amino-methyl propanol co-dispersant.
  • the amino-methyl propanol co-dispersant may include for example AMP or AMP-95.
  • AMP95 may be added into the SB coating at the last stage of the paint making process.
  • the concentration of AMP95 of the present invention is generally between 0 wt% to about 0.5 wt%, preferably between about 0.01 wt% to about 0.3 wt%, and more preferably between about 0.05 wt% to about 0.15 wt%, based on the weight of the total formulation.
  • the coating formulation of the present invention may also include, as an optional component, at least one drying catalyst.
  • the drying catalyst or drying agent useful for the coating formulation of the present invention may be any conventional drying catalyst known in the art.
  • suitable drying catalyst or drying agent include, but are not limited to, various salts of cobalt, zirconium, calcium, zinc, and manganese; and mixtures thereof.
  • the drying catalyst may include calcium octoate/ naphthenate, cobalt octoate/ naphthenate, zirconium octoate/ naphthenate and other metal complex catalysts; and mixtures thereof.
  • Preferred drying catalyst or drying agent are the metal salts of
  • the concentration of drying catalyst present in the coating formulation of the present invention is generally between 0.01 wt% to about 1 wt%, based on the weight of the total formulation.
  • the usage may be based on a catalyst which has about 10 % metal content.
  • the drying catalyst or drying agent used as the drier package in the ambient cure formulation of the present invention may include any drier known in the art, so long as the drier package provides from about 0.15% to about 10% calcium content and at least about 0.01 wt% cobalt content, based on the binder solids content.
  • the coating formulation of the present invention may also include, as an optional component, at least one anti-skinning agent.
  • the anti-skinning agent useful for the coating formulation of the present invention may be any conventional anti-skinning agent known in the art.
  • the term "anti-skinning agent” herein means the additive can prevent the alkyd coating from skinning on the surface when the coating is stored in a storage container.
  • the anti-skinning agent may include methyl ethyl ketoxime (MEKO), methyl iso-butyl ketome (MIBKO); and the like; and mixtures thereof.
  • the concentration of anti-skinning agent present in the coating formulation of the present invention is generally between about 0.1 wt% to about 1 wt%, preferably between about 0.2 wt% to about 0.6 wt%, based on the weight of the total formulation. If the usage is below the recommended concentration, the coating may more readily form dry skin on a paint surface.
  • the coating formulation of the present invention may also include, as an optional component, at least one thickener agent.
  • the thickener agent useful for the coating formulation of the present invention may be any conventional thickener agent known in the art to improve a coating's rheological properties.
  • thickeners for alkyd-compatible surfactant include bentonite clays, organoclays, synthetic silicas, castor oil derivatives, modified acrylic copolymers, polyethylene glycol, polymerized oil derivatives, organic esters, complex polyolefins; and mixtures thereof.
  • the concentration of thickener agent present in the coating formulation of the present invention is generally between about 0.1 wt% to about 1 wt%, preferably between about 0.2 wt% to about 0.6 wt%, based on the weight of the total formulation. If the concentration of the thickener is below about 0.1 wt%, the resulting wet coating film may possibly sag.
  • the above formulation may be advantageously used to prepare, for example, one embodiment of a clear coating formulation which includes components (a)-(e) and/or (f) at least one amino-methyl propanol co-dispersant, as described above; and one or more of the following optional components: (g) at least one drying catalyst, (h) at least one anti- skinning agent, and (i) at least one thickener.
  • the pigmented coating formulation may comprise, in addition to components (a)-(e), and/or (f) at least one amino-methyl propanol co-dispersant, as described above; and (j) at least one pigment.
  • the pigmented coating formulation for primer coating may include one or more of the following optional components: (g) at least one drying catalyst, (h) at least one anti-skinning agent, (i) at least one thickener, and (k) at least one filler.
  • the at least one pigment useful, as an optional component, for the coating formulation of the present invention may be any conventional pigment known in the art.
  • Suitable well known pigments can comprise for example, titanium dioxide, carbon black, graphite, ceramic black, antimony sulfide, black iron oxide, aluminum pastes, yellow iron oxide, red iron oxide, iron blue, phthalo blue, nickel titanate, dianisidine orange,
  • the concentration of the pigments present in the coating formulation of the present invention may be generally between about 1 wt% to about 40 wt%, and preferably between about 10 wt% to about 30 wt%, based on the weight of the total formulation.
  • the pigment usage may be dependent on the formulations' color and PVC (pigment volume concentration) design. Too much or too less of the above concentrations may not meet the coating's performance specifications such as color, hardness and other coating properties.
  • the at least one filler of the present invention may be any conventional filler known in the art.
  • the fillers useful in the coating formulation of present invention may include clays, barium sulphate, silica, talc, quartz, or mica; flame retardant fillers such as aluminum hydroxide or magnesium hydroxide; boehmite; or zinc phosphate; and the like; and mixtures thereof.
  • the concentration of the filler present in the coating formulation of the present invention may be generally between 0 wt% to about 50 wt%, and preferably between about 0.1 wt% to about 40 wt%, based on the weight of the total formulation.
  • the filler usage may be dependent on the formulations' PVC design. Too much or too little filler may result in the coating not meeting the coating's performance specification such as color and anti-corrosive properties.
  • the average particle size of the inorganic filler is generally below about 100 micron, preferably below about 60 micron, and more preferably below about 50 micron. If the filler has too big particle size, the coating film will have poor appearance and poor protective performances to the substrate.
  • the coating formulation of the present invention may also include, as an optional component, at least one dispersant.
  • the dispersant useful in the coating may also include, as an optional component, at least one dispersant.
  • the formulation of present invention may include any conventional dispersant known in the art.
  • Other examples of the dispersant may be including the anionic and nonionic surfactants, soya lecithin, alkyl ammonium salts of fatty acids, amine salts of alkyl aryl sulfonates, unsaturated organic acids, sulfonated castor oil, mixtures of high boiling point aromatic and ester solvents, sodium salts of aryl sulfonic acid, and the like; and mixtures thereof.
  • the concentration of the dispersant present in the coating formulation of the present invention is generally between 0 wt% to about 1 wt%, preferably between about 0.1 wt% to about 0.8 wt%, and more preferably between about 0.1 wt% to about
  • the combination of surfactants of the present invention may be sufficient to act as a dispersant.
  • the commonly known dispersant agents such as ANTI-TERRA-U or soya lecithin for solvent borne alkyd coatings may not be required; and therefore, the cost for their use may be saved while achieving a very homogeneous dispersion of the pigments and fillers.
  • the coating formulation according to the present invention may further include, as an optional component, one or more additives chosen from rheology modifiers, other pigments, other fillers, plasticizers, antioxidants, thixatropes, extenders, other solvents, diluents, other drying agents, other dispersants, other surfactants, fungicides, mildewcides, preservatives, UV absorbers, anti-marring agents, flow and leveling agents, fragrances, defoaming agents, chelating agents, flattening agents, anti-rusting agents, and mixtures thereof.
  • additives chosen from rheology modifiers, other pigments, other fillers, plasticizers, antioxidants, thixatropes, extenders, other solvents, diluents, other drying agents, other dispersants, other surfactants, fungicides, mildewcides, preservatives, UV absorbers, anti-marring agents, flow and leveling agents, fragrances, defoaming agents, chelating
  • the concentration of the additional additives present in the formulation of the present invention is generally between 0 wt% to about 1 wt%, preferably between about 0.1 wt% to about 0.5 wt%, more preferably between about 0.1 wt% to about 0.3 wt%, based on the weight of the total formulation and the formulation design. If the usage is less than the above ranges, the coating's sag resistance may be poor or unacceptable. Too high of a concentration may be uneconomical and may increase the formulation cost.
  • the coating formulation of the present invention may be useful, for example, for clear coats and pigmented protective coatings.
  • a clear coating formulation may include (a) at least one hydrophilic surfactant; (b) at least one hydrophobic surfactant; (c) water; (d) at least one solvent; and
  • a pigmented coating formulation may include (a) at least one hydrophilic surfactant; (b) at least one hydrophobic surfactant; (c) water; (d) at least one solvent; and (e) at least one solvent borne air drying alkyd coating resin; and
  • (f) optionally, at least one amino-methyl propanol co-dispersant; (g) at least one drying catalyst; (h) at least one anti-skinning agent; (i) at least one thickener additive; (j) at least one pigment; and/or (k) at least one filler.
  • a dispersant, component (1) may optionally be added to the coating formulation of the present invention.
  • Suitable dispersants may also include other
  • ammonium salts of fatty acids amine salts of alkyl aryl sulfonates, unsaturated organic acids, sulfonated castor oil, mixtures of high boiling point aromatic and ester solvents, sodium salts of aryl sulfonic acid, and the like; and mixtures thereof.
  • the objectives of the present invention includes developing an air-drying alkyd protective paint formulation with lower VOC, lower cost and unchanged or improved performance for topcoat or primer coatings in protective coatings including for example marine, maintenance, or wood coatings.
  • the alkyd formulations of the present invention comprise a multi-functional additive, which is the combination of surfactants of the present invention, as an emulsifier enabling the use of, for example, approximately 4 % to about 16 % water (based on total formulation weight) replacing same amount of solvent by weight in the solvent borne alkyd formulations, which significantly reduces the VOC level while reducing cost and maintaining physical properties of the coating.
  • the new air-drying alkyd coat affords lower VOC and workable viscosity; and meets all the requirements of the industry standards for a solvent borne alkyd coating.
  • the alkyd paint may be used as coatings that are used to protect metal or wood and also give decorative functions in and around items associated with industrial production and transport, especially manufacturing plants, as corrosion protective coating for general applications such as metal coating for infrastructure components, beams, and the like, and as marine coating on above-water sections of a watercraft.
  • the unique surfactant product mixture i.e., the at least one hydrophilic surfactant mixed with the at least one hydrophobic surfactant
  • the surfactant mixture also acts as a dispersant to improve the dispersion of the pigments, which in turn, decreases or eliminates the use of a conventional dispersant agent used in the traditional SB alkyd coating or in some cases the conventional dispersant agent may be removed entirely.
  • the present invention advantageously reduces the VOC level of traditional SB alkyd coatings, achieves significant cost reduction, and at same time, maintains the same level or improves the level of coating performance when compared with traditional SB alkyd coatings of the prior art.
  • One embodiment of the coating formulation of the present invention may include (a) at least one hydrophilic surfactant; (b) at least one hydrophobic surfactant;
  • at least one dispersant such as ANTI-TERRA and optionally, AMP can be added to the above mixture.
  • the use of the surfactants of the present invention provides several benefits such as (1) the surfactants may replace or at least decrease the amount of the dispersant needed in the coating formulation; (2) the use of the surfactants may allow the use of an amount of water such that the water may replace the amount of solvent needed in the coating formulation, such as for example, up to about 10% solvent of the total coating formulation weight can be replaced with the same amount of water; and (3) utilizing the surfactants can reduce the VOC of the SB self-drying alkyd coating which, in turn, may provide a significant cost saving.
  • the coating formulations of the present invention can be prepared in a similar manner with traditional solvent borne coating.
  • the mixing order of the surfactants employed in the coating formulation of the present invention can be added and dispersed uniformly at any stage before water is introduced; the water is preferably added after all the other coating components are added and dispersed uniformly.
  • the mixing order of the surfactants employed in the coating formulation of the present invention can be before the grinding stage or after the grinding stage to make sure the pigment is dispersed uniformly in the paint formulation; the water is preferably added last after any other raw materials are added and dispersed uniformly.
  • the surfactants may be first added to the formulation and dispersed uniformly throughout the formulation before any pigments and fillers are added to the formulation.
  • the optional dispersant is used in the formulation, the surfactant may be added at a stage before water is added to the formulation. Preferably, water is added at a final stage after all of the previous components are dispersed uniformly throughout the formulation.
  • the solvent borne alkyd coating is admixed employing mixing procedures and conditions well known in the paint mixing art.
  • the equipment and conditions for preparing the coating formulation may be the same as what is used in preparing traditional solvent borne coatings, such as for example, the temperature control is preferably under 50 °C.
  • the final coating formulation or formulation displays superior properties including for example a low VOC concentration, and a low viscosity.
  • the concentration generally is from about 20 wt% to about 50 wt%; and preferably from about 2.0 wt% to about 40 wt%.
  • the solids concentration of the formulation is generally from about 40% to about 70% by weight.
  • the viscosity of the formulation is generally from about 200 mP-s to about 650 mP-s; and preferably from about 20 mP-s to about 50 mP-s.
  • the finished coating using the coating formulation of the present invention may keep excellent gloss (greater than 90 @60° as tested by method GB/T9754; China Standard) and excellent gloss retention (as test method HG 2576-94; China Standard), properties which are the same as a traditional solvent borne alkyd coating.
  • the coating formulation of the present invention may be applied to a variety of substrates such as steel, aluminum, wood and the like. Once on the substrate, the coating formulation can then be cured at ambient condition to form an attractive, hard and adherent film.
  • the alkyd coating formulation of the present invention may be coated onto a substrate and cured at room temperature (ambient cure) by methods known in the art (e.g. by spray-applying 3 to 4 mils of wet coating onto a metal panel and drying at ambient condition).
  • the substrate may be any common substrate, such as, for example metals such as, for example, aluminum or steel; glass; wood; concrete; primed (painted) substrates; and the like.
  • the coating formulation of the present invention may be applied by any well known means of application in the industry including for example, reverse roll coating, spraying, brushing, rolling, or dipping and the like; more specifically coating methods used in the application of organic solvent based coating formulations, such as spray coating, electrostatic coating, immersion coating, curtain flow coating, roll coating, shower coating; and the like.
  • Curing schedules can vary depending upon the components present in the alkyd resin coating formulation, the presence or absence of catalysts, and the environment conditions. Typical curing schedules are same as traditional solvent borne alkyd coatings include from about 10 hours to about 60 hours at from about 5 °C to about 35 °C.
  • the coating formulations or compositions of the present invention are very suitable for coating processes for various applications including for example in for protective coatings such as for general metal, tanks, bridges, and infrastructure and factory coatings, and any other substrates on which air drying alkyd coating can be used.
  • the coating of the present invention may be used as a protective coating for metal and wood substrates for protection and for decoration.
  • the coating of the present invention has less VOC and lower cost, while the coating displays same or superior properties than previously known coatings such as better storage performance and better pigment dispersing effect.
  • the coating of the present invention when the coating of the present invention is compared to a standard coating made from AMP95, the coating of the present invention has lower or similar viscosity; and most importantly, also a better storage stability.
  • Storage stability with reference to a coating herein means that the coating's phase stability is suitable to provide a useable formulation to form a coating with functional properties. Storage stability may be measured according to the following test method: Prepare a coating sample of about 100 g, in clear plastic bottle and then subject the sample @25 °C and 60% RH under storage conditions of 50 °C for 30 days.
  • the coating samples of the present invention after the above storage test, show no water phase separation by visual observation, and no grindness increase; and the coating samples have the same film properties as before the storage test.
  • standard coating samples for example those made from AMP-95, after only one week, the samples @25 °C &60%RH and 50 °C typically have water phase separation on the sample bottom; the grindness of wet paint is poor (for example, from originally
  • the coating film can have
  • rindness herein means the largest average particle size of dispersed pigments and filler in the coating. Generally, a smaller grindness is desired for better coating performances.
  • Table A shows a comparison of typical values for VOC of a coating of the present invention versus a coating of the prior art.
  • the coatings' properties such as fineness, viscosity, storage stability, film appearance, gloss, color, adhesion, flexibility, impact resistance and water resistance are measured.
  • important properties for the coating for example, include viscosity, storage stability, gloss, adhesion, and water resistance.
  • the viscosity of the coating formulation of the present invention may be below about 1000 mP-s at 25 °C and preferably less than about 600 mP-s at 25 °C.
  • the resulting coating of the present invention generally exhibits the following properties, according to HG 2576-94 alkyd enamel coating standards:
  • the water resistance is as follows: for acceptable grade 12 hour water immersion and a coating's gloss retention of greater that 80 %; and for excellent grade 18 hours water immersion and a coating's gloss retention of greater that 80 %.
  • a coating's anti-corrosive performance is directly related to the coating's water resistance performance.
  • the solvent borne alkyd coating of the present invention shows good anti-corrosive performance because its water resistance is good.
  • the final coating of the present invention displays superior properties. That is, the cured coating formulation of the present invention advantageously exhibits various properties that make the coating useful for coating substrates.
  • the coating should meet the minimum standards in the industry such as for example: wet paint properties such as condition in a paint can, viscosity, application performance and dry film properties.
  • minimum standards may be those established by the Chinese government as described in publication Chinese Chemical Industry Standards for Alkvd Finish Coatings HG 2576-94. These minimum standards for certain properties are known and
  • AMP stands for an additive commercial product of The Dow Chemical Company
  • Exxsol D 40 is a solvent commercially
  • ANTI-TERRA-U is a dispersant commercially available from BYK Company
  • 389-37 or 389-9 are two soybean oil alkyd resins with 60 % oil length, commercially available from Xinhua Resin Manufacturing Co. in China
  • a multifunctional additive in the present examples is a surfactant mixture from The Dow Chemical Company; and in the tables below, “VOC” stands for volatile organic compounds; “MS” stands for mass solid content; “PVC” stands for pigment volume concentration; and “VS” stands for volume solid content.
  • Phase separation is determined by visual observation of water phase separation. No water separation is “good”, while any water separation is “bad”.
  • Viscosity is determined by ASTM D4287 method and is generally less than about 600 mP-s.
  • Sheets of metal for testing the coatings in the examples were coated according to method GB 1727.
  • the properties of the resulting coated sheets of metal were tested as follows: the hard dry property was measured according to test method GB 9273; the flexibility property was measured according to test method GB/T 6742-1986; the adhesion property was measured according to test method GB 9286; the pencil hardness property was measured according to test method GB6739; the impact resistance property was measured according to test method GB/T 1732-1993; the gloss property was measured according to GB/T9754; the water resistance property was measured according to GB/T 9274; and the storage property was measured according to GB/T6753.
  • the dispersing machine used in the following examples for dispersing the components of the formulation was a Dispermat CN F2 manufactured by
  • step 6 of Table I Add component of step 6 of Table I into the tank and then disperse the resulting mixture of components uniformly under 800-1200 rpm.
  • step 12 of Table II Add component of step 12 of Table II into the tank and then disperse the resulting mixture of components under 1800-2000 rpm uniformly for about 15 minutes to form a paint formulation.
  • the resulting paint formulation is placed in a sealed can sealed under room temperature for one day. After one day, the resulting paint formulation is divided into two parts - one part is stored at room temperature for 30 days; and the other part is heated at 50 °C for 30 days. Then the parts are checked to determine if any water phase separation occurs.
  • Table III The results of this Comparative Example A are described in Table III below.
  • step 5 of Table IV Add component of step 5 of Table IV into the tank and then disperse the resulting mixture of components uniformly under 800-1200 rpm.
  • step 6 of Table IV Add component of step 6 of Table IV into the tank and then disperse the resulting mixture of components under 2000 rpm for about 20 minutes; control the temperature of the mixture of components at under 50°C; and when the grindness of the resulting mixture of components is less than 40 ⁇ , go to the next step.
  • step 14 of Table IV Add component of step 14 of Table IV into the tank and then disperse the resulting mixture of components under 1800-2000 rpm uniformly for about 15 minutes to form a paint formulation. After the above procedure, the resulting paint formulation is placed in a sealed can sealed under room temperature for one day. After one day, the wet paint performances were tested and coating films were applied to a substrate. The coating films were subjected to 25 °C/60 relative humidity (RH) conditions for 7 days and then the resulting film properties were tested. The results of this Example 2 are described in Tables IX-XIII below.
  • step 5 of Table V Add component of step 5 of Table V into the tank and then disperse the resulting mixture of components uniformly under 800-1200 rpm.
  • step 6 of Table V Add component of step 6 of Table V into the tank and then disperse the resulting mixture of components under 2000 rpm for about 20 minutes, control the temperature of the mixture of components at under 50 °C, and when the grindness of the mixture of components is less than 40 ⁇ , go to the next step.
  • step 14 of Table V Add component of step 14 of Table V into the tank and then disperse the resulting mixture of components under 1800-2000 rpm uniformly for about 15 minutes to form a paint formulation.
  • the resulting paint formulation is placed in a sealed can sealed under room temperature one day. After one day, the wet paint
  • step 5 of Table VI Add component of step 5 of Table VI into the tank " and then disperse the resulting mixture of components uniformly under 800-1200 rpm.
  • step 6 of Table VI Add component of step 6 of Table VI into the tank and then disperse under 2000 rpm about 20 minutes, control the temperature of the resulting mixture of components at under 50 °C; and when the grindness of the resulting mixture of components is less than 40 ⁇ , go to the next step.
  • step 14 of Table VI Add component of step 14 of Table VI into the tank and then disperse the resulting mixture of components under 1800 ⁇ 2000 rpm uniformly for about 15 minutes.
  • the resulting paint formulation is placed in a sealed can sealed under room temperature one day. After one day, the wet paint
  • step 6 of Table VII Add component of step 6 of Table VII into the tank and then disperse the resulting mixture of components uniformly under 800-1200 rpm.
  • step 7 of Table VII Add component of step 7 of Table VII into the tank and then disperse the resulting mixture of components under 2000 rpm about 20 minutes, control the temperature of the resulting mixture of components at under 50 °C, and when the paint grindness is less than 40 ⁇ , turn to next step.
  • step 13 of Table VII Add component of step 13 of Table VII into the tank and then disperse the resulting mixture of components under 1800-2000 rpm for about 15 minutes to form a paint formulation. After the above procedure, the resulting paint formulation is placed in a sealed can sealed under room temperature one day. After one day, the wet paint
  • a coating is applied with a film applicator (Sheen drawdown bar) with a 200 wet film thickness. Then the film is subjected to room temperature (25 °C/60% RH) for 7 days and the dry film's performances are tested according to the standards previously mentioned. The results of these tests are described in Tables 1X-XI.
  • a general test method for testing the stability of a coating formulation is as follows: Place 200 g of a sample in sealed can and subject the can to a temperature of 50 °C for one month. After one month, visually check if any water has phase separated out of the formulation and if any settlement has occurred. After mixing the coating formulation uniformly, manually apply the coating formulation with 250 ⁇ wet film thickness on a steel Q-panel. Then test the film performances of the resulting film coating. In addition, test the fineness of the resulting wet paint formulation. The stability and fineness test results are described in Tables XII and XIII.
  • step 6 of Table XIV Add component of step 6 of Table XIV into the tank and then disperse the resulting mixture of components uniformly under 800-1200 rpm.
  • the resulting paint formulation is placed in a sealed can sealed under room temperature for one day. After one day, the wet paint performances are tested and coating films are applied to a substrate. The coating films were subjected to 25 °C/60 RH conditions for 7 days and then the film properties were tested.
  • Example 4 The process used to make the paint formulation in this Example 4 was the same as the process described in Example 3.
  • the resulting viscosity data for this Example 4 is described in Table XVI below.
  • step 6 of Table XV Add component of step 6 of Table XV into the tank and then disperse the resulting mixture of components uniformly under 800 ⁇ 1200 rpm.
  • step 16 of Table XV Add component of step 16 of Table XV into the tank and then disperse the resulting mixture of components under 1800-2000 rpm uniformly for about 15 minutes to form a paint formulation.
  • Examples 1-4 performance can still meet the Chinese Standard for alkyd topcoat and finish coatings in terms of drying time, impact resistance, adhesion, flexibility, and water resistance.
  • the data also shows that when a formulation employs a combination of surfactants (i.e., the multifunctional additive), the viscosity of the resulting coatings made from such formulation is significantly reduced comparing with when only AMP95, alone, is used to introduce water into a solvent based alkyd coat.
  • AMP95 alone, the water is probably not stable in the solvent borne alkyd coating: for the clear coating, the water separates out after a short period time; and for the pigmented alkyd coating, it causes the paint pigment particles to flocculate; and the film coating has a poor appearance (pig skin) after the film is heated in storage for 1 month, which is a continuing problem for current users of coating technology using AMP technology.
  • the present invention can solve the viscosity and water stability problems. Also, the present invention provides formulations that have low viscosity and can still meet the requirements of users of coating formulations.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention porte sur une formulation de revêtement comprenant (a) au moins un tensioactif hydrophile ; (b) au moins un tensioactif hydrophobe ; (c) de l'eau ; (d) au moins un solvant ; (e) au moins un revêtement à base de résine alkyde au solvant et séchant à l'air ; et (f) éventuellement, au moins un co-dispersant aminométhylpropanol. La formulation de revêtement est utile pour la fabrication de couches de finition et de couches primaires.
PCT/CN2010/000068 2010-01-15 2010-01-15 Formulations de revêtement à base de résine alkyde WO2011085520A1 (fr)

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PCT/CN2010/000068 WO2011085520A1 (fr) 2010-01-15 2010-01-15 Formulations de revêtement à base de résine alkyde

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2626383A1 (fr) * 2012-02-09 2013-08-14 Akzo Nobel Chemicals International B.V. Accélérateur de durcissement de résines
CN112778885A (zh) * 2021-01-08 2021-05-11 中国科学院青海盐湖研究所 一种超疏水涂层材料及其制备方法、超疏水涂层

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4600440A (en) * 1984-12-11 1986-07-15 The Flecto Company, Inc. Water wash-up coating composition
KR20030065716A (ko) * 2002-01-30 2003-08-09 주식회사 코켐 김 서림 방지용 수분산 폴리우레탄 수지 코팅용액 조성물및 그 제조방법
WO2004037928A1 (fr) * 2002-10-25 2004-05-06 Perstorp Specialty Chemicals Ab Composition de resine d'origine aqueuse sechant a l'air
CN101307137A (zh) * 2007-05-17 2008-11-19 上海涂料有限公司技术中心 自干型丙烯酸改性醇酸树脂水分散体及以它为基料的工业面漆

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4600440A (en) * 1984-12-11 1986-07-15 The Flecto Company, Inc. Water wash-up coating composition
KR20030065716A (ko) * 2002-01-30 2003-08-09 주식회사 코켐 김 서림 방지용 수분산 폴리우레탄 수지 코팅용액 조성물및 그 제조방법
WO2004037928A1 (fr) * 2002-10-25 2004-05-06 Perstorp Specialty Chemicals Ab Composition de resine d'origine aqueuse sechant a l'air
CN101307137A (zh) * 2007-05-17 2008-11-19 上海涂料有限公司技术中心 自干型丙烯酸改性醇酸树脂水分散体及以它为基料的工业面漆

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2626383A1 (fr) * 2012-02-09 2013-08-14 Akzo Nobel Chemicals International B.V. Accélérateur de durcissement de résines
CN112778885A (zh) * 2021-01-08 2021-05-11 中国科学院青海盐湖研究所 一种超疏水涂层材料及其制备方法、超疏水涂层

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