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WO2016187380A1 - Composition de revêtement époxy - Google Patents

Composition de revêtement époxy Download PDF

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Publication number
WO2016187380A1
WO2016187380A1 PCT/US2016/033192 US2016033192W WO2016187380A1 WO 2016187380 A1 WO2016187380 A1 WO 2016187380A1 US 2016033192 W US2016033192 W US 2016033192W WO 2016187380 A1 WO2016187380 A1 WO 2016187380A1
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WO
WIPO (PCT)
Prior art keywords
epoxy resin
curable
composition
curable composition
cured
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2016/033192
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English (en)
Inventor
Yinzhong Guo
Jia Tang
Ray E. Drumright
Kiran K. Baikerikar
Rebecca S. Ortiz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Blue Cube IP LLC
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Blue Cube IP LLC
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Filing date
Publication date
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Publication of WO2016187380A1 publication Critical patent/WO2016187380A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/44—Amides

Definitions

  • the present disclosure generally relates to high solids, low solvent borne epoxy coating compositions, processes for preparing these compositions, and cured coatings prepared using these compositions.
  • Solvent-borne (SB), two-component epoxy coatings have been widely used in marine coatings, protective coatings, and in other application fields since these coatings exhibit excellent adhesion, corrosion resistance and chemical resistance.
  • various types of hardeners are used to achieve the required balanced properties for specific applications.
  • Polyamide hardeners are most commonly used in marine and protective coating markets because these hardeners provide SB epoxy coatings that are relatively low cost, an extended pot-life; excellent corrosion resistance, and chemical resistance as compared to SB epoxy coatings prepared from other classes of hardeners.
  • curable epoxy resin compositions comprising: (a) an epoxy resin, (b) a polyamide hardener; and (c) a compatibilizer wherein the
  • Z is oxygen or NH; n is a number from 1 to 3; m is a number from 0 to 2 with the proviso that 4-n-m must be at least 1 ;
  • A is independently hydrogen (H), an alkyl, or substituted alkyl having from 1 to 3 carbon atoms;
  • X is independently OH, N(R) 2 or CH 2 Y; Y is OH or N(R) 2 ; and each R is independently an alkyl, substituted alkyl, or a hydroxyalkyl having from 1 to 3 carbon atoms.
  • cured products prepared by curing the curable epoxy resin composition.
  • Figure 1 shows a group of four photographs showing four coated articles. Two of the photographs show a coated article that has been coated with a control composition (Comparative Example B) and a coated article that has been coated with a composition of the present invention (Example 6) using Versamid 125 in each composition, respectively. The two remaining photographs show a coated article that has been coated with a control composition (Comparative Example D) and a composition of the present invention (Example 12) using Versamid 140 in each composition, respectively.
  • the compatibilizer modified coated articles of the present invention (Examples 6 and 12) show better methyl ethyl ketone (MEK) double rub resistance than the control coatings (Comparative Examples B and D).
  • curable epoxy resin compositions which comprise at least one epoxy resin compound, at least one polyamide hardener, and at least one compatibilizer. After the curable epoxy resin compositions are applied and cured, the coatings have improved chemical, corrosion resistance, and do not display significant blooming and/ or significant blushing.
  • the curable epoxy resin composition comprises at least one epoxy resin compound, at least one polyamide hardener, and at least one compatibilizer.
  • the curable epoxy resin composition has a viscosity ranging from 50 mPa-s to about 10,000 mPa-s and a high solid content.
  • the epoxy resin compound, component (a) can be any epoxy resin compound, component (a), can be any epoxy resin compound, component (a),
  • the epoxy resin can be a single epoxy resin compound used alone or a mixture of two or more epoxy compounds used in combination, i.e., component (a) of the curable epoxy resin composition which is cured to form the coating material of the present invention includes at least one epoxy resin.
  • Non-limiting embodiments of these epoxy resins may be trimethylpropane epoxide, cyclohexanedimethanol diglycidyl ether, diglycidyl-1 ,2-cyclohexane dicarboxylate, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, resorcinol diglycidyl ether, triglycidyl ethers of para-aminophenols, halogen (for example, chlorine or bromine)-containing epoxy resins such as diglycidyl ether of tetrabromobisphenol A, epoxidized phenol novolac, epoxidized bisphenol A novolac, an oxazolidone-modified epoxy resin, an epoxy-terminated polyoxazolidone, and mixtures thereof.
  • halogen for example, chlorine or bromine
  • Non-limiting examples of suitable commercially available epoxy resin compounds may include the D.E.R.TM 300 series, the D.E.N.TM 400 series, the D.E.R.TM 500 series, the D.E.R.TM 600 series and the D.E.R.TM 700 series of epoxy resins commercially available from The Dow Chemical Company.
  • epoxy resins may include LERs, such as D.E.R. 331 (a bisphenol A diglycidyl ether), D.E.R. 354 (a bisphenol F diglycidyl ether), D.E.R.
  • D.E.R. 330, DER 331 , D.E.R. 332, D.E.R. 354, D.E.R. 324, and DLVE 18, DLVE 19, DLVE 52 are commercially available epoxy resins from The Dow Chemical Company.
  • the epoxy resin compound may include a liquid epoxy resin, such as D.E.R. 383 a diglycidylether of bisphenol A (DGEBPA) having an epoxide equivalent weight of from about 175 to about 185, a viscosity of about 9.5 Pa-s and a density of about 1 .16 g/cc.
  • the commercial epoxy resin compounds may include epoxidized novolac bisphenol F type resins such as D.E.N. 431 , D.E.N. 438 or D.E.N. 439; epoxidized novolac bisphenol F type resins with solvent including for example D.E.N.
  • One of the key properties of the epoxy resin is the capability of the epoxy resin to be useful as a binder for coating films.
  • the concentration of the epoxy resin compound used in the curable composition may range from 1 weight percent (wt%) to about 99 wt%. In various embodiments, the concentration of the epoxy resin compound may range from 1 wt% to about 99 wt%, from 5wt% to about 80 wt%, from 10 wt% to about 70 wt%, from 20 wt% to about 60 wt%, or from 25 wt% to about 50 wt% based on the total weight of all of the components present in the curable composition. Using the epoxy resin compound below 1 wt % or above 99 wt % would result in less curing of the curable composition; and would result in poor coating performance.
  • the polyamide hardener compound, component (b) may be a single polyamide hardener compound, a mixture of two or more polyamide hardener compounds, or a mixture of at least one polyamide hardener compound and another co- curing agent compound different from the polyamide hardener compound.
  • the polyamide hardener compound, component (b), may include at least one polyamide hardener.
  • the hardener compound (or "hardener”; also referred to as a "curing agent” or a "crosslinking agent”) may be blended with the epoxy resin, component (a), and the other components of the composition, to prepare the curable epoxy resin formulation or composition.
  • the curable epoxy resin composition may then be cured under curing conditions to form a cured product or thermoset which is in the form of a solid cured coating.
  • the polyamide hardener is one that is adapted to being compatible with the epoxy resin, component (a), when the polyamide hardener is in the presence of the epoxy resin and the compatibilizer agent. Another key property of the polyamide hardener compound is to cure epoxy resin to form a hard coating material.
  • the polyamide hardener compound, component (b) may be selected from one or more of the following chemical compounds including amino polyamides, amidopolyamines, and mixtures thereof.
  • Non-limiting examples of some commercial polyamide hardeners may include Versamid 125, Versamid 140, Versamid 228, Versamid 280B75, and other compounds under the Versamid trade name which are commercially available from BASF.
  • the Versamid polyamide hardeners are condensation products of fatty acids or dimer fatty acids and polyamines.
  • Other non- limiting examples of other polyamide hardeners may be BCA P445 and BCA P050 commercially available from BRENNTAG Specialties; EPIKURETM polyamide curing agents commercially available from Momentive; and mixtures thereof.
  • the polyamide hardener compound, component (b) may include condensation products of dimer fatty acid and polyamines; and condensation products of fatty acids with polyamines; and mixtures thereof.
  • the molar stoichiometry of epoxy to the hardener may range from 1 .4:1 to about 1 :1 .4. In various embodiments, the molar stoichiometry of epoxy to the hardener may range from 1 .4:1 to about 1 :1 .4, from 1 .2:1 to about 1 :1 .2, from 1 .1 :1 to about 1 :1 .1 or from 1 .05:1 to about 1 :1 .05.
  • the epoxy and polyamide hardener at a stoichiometric ratio of epoxy to NH may range from 1 .2:1 to about 1 :1 .2; or from 1 .1 :1 to about 1 :1 .1 .
  • the concentration of the hardener present may be measured in terms of an equivalent ratio of nucleophile (i.e., amine NH) to electrophile (i.e., epoxy and acrylate functionality).
  • the equivalent ratio of nucleophile to the electrophile functionality may range of from 0.5:1 to about 1 .5:1 .
  • equivalent ratio of nucleophile to the electrophile functionality may range of from 0.5:1 to about 1 .5:1 , from 0.6:1 to about 1 .4:1 , from 0.7:1 to about 1 .3:1 , from 0.8:1 to about 1 .2:1 , or from 0.8:1 to about 1 .1 :1 .
  • the resulting coating film properties may suffer due to poor network formation from a stoichiometric imbalance.
  • a compatibilizer (or "compatibilizer agent” or “compatibilizing agent”), as component (c), may be added to the curable epoxy resin coating
  • composition to effect several benefits including: (i) to significantly improve the compatibility between the epoxy resin in the composition and the hardener in the composition; (ii) to reduce or resolve the blooming and blushing problems of the final cured coating product; and (iii) to beneficially reduce the initial viscosity of the curable epoxy resin composition.
  • the compatibilizer may be a reactive compatibilizer agent.
  • reactive herein is meant that the compatibilizer, component (c), includes a reactive functionality that can react with the curing agent.
  • the reactive compatibilizer agent is an acrylate-based compound.
  • the reactive compatibilizer agent may include a polar functionality which may be a hydroxyl functionality or a tertiary amine functionality. In a preferred embodiment, the polar functionality of the reactive compatibilizer agent may be a hydroxyl functionality.
  • the compatibility improving component i.e., the compatibilizer, may include a compound having the following general chemical structure, Structure (I):
  • Z is oxygen or NH; n is a number from 1 to 3; m is a number from 0 to 2 with the proviso that 4-n-m must be at least 1 ;
  • A is independently hydrogen (H), an alkyl, or substituted alkyl having from 1 to 3 carbon atoms;
  • X is independently OH, N(R) 2 or CH 2 Y; Y is OH or N(R) 2 ; and each R is independently an alkyl, substituted alkyl, or a hydroxyalkyl having from 1 to 3 carbon atoms.
  • Specific compatibilizers may include a hydroxyl functional acrylate, a hydroxyl functional di-acrylate, a hydroxyl functional tri-acrylate, a di-hydroxyl functional di-acrylate, an alkylaminoalkyl acrylate, a monohydroxyl polyglycol acrylate, and the like; or blends of the above compounds.
  • Other acrylate oligomers or polymers that may react with curing agents and also contain hydroxyl groups or polar groups that improve the compatibility of the epoxy resin and the polyamide curing agent may be used.
  • the amount of compatibilizer may include a hydroxyl functionalized additive in an amount of from 0.1 wt% to about 20 wt% based on the epoxy portion, component (a), of the composition.
  • amount of compatibilizer may range from 0.1 wt% to about 20 wt%, from 1 wt% to about 15 wt%, from 2 wt% to about 10 wt% or from 3 wt% to about 5 wt% based on the weight of the epoxy resin in the curable epoxy resin composition.
  • optional components may be added to the curable composition for various intended purposes.
  • the optional components may be used at a concentration sufficient to prepare the curable epoxy resin composition with minimal impact to the thermal and mechanical properties of the final curable composition; and minimal impact to the thermal and mechanical properties of the cured thermoset product made from the curable
  • a curing catalyst compound may optionally be added to facilitate the curing of the at least one epoxy resin.
  • the curing catalyst functions to speed up the curing reaction between the epoxy and the hardener.
  • Another additional component may include at least one other hardener or co-curing agent different from the polyamide hardener compound.
  • the co-curing agent may be used for assisting in curing the epoxy resin.
  • the co-curing agent component may include any conventional co-curing agent known in the art.
  • Still another additional component may include at least one solvent. The solvent may be used to lower the initial viscosity of the curable composition to a lower final viscosity.
  • the solvent component that can be used to form the curable composition may include any solvent or diluent which is essentially inert to the other components used in the curable composition at the mixing temperature of the components; and which provides the necessary solubility to lower the initial viscosity of the curable composition.
  • the solvent component that can be added to the curable composition may include any conventional solvent known in the art.
  • Other optional components may include compounds that are normally used in curable resin formulations known to those skilled in the art.
  • the optional components may include compounds that can be added to the composition to enhance application properties (e.g., surface tension modifiers, rheology modifiers, or flow aids), reliability properties (e.g., adhesion promoters), the reaction rate, the selectivity of the reaction, and/or the catalyst lifetime.
  • application properties e.g., surface tension modifiers, rheology modifiers, or flow aids
  • reliability properties e.g., adhesion promoters
  • the reaction rate e.g., the selectivity of the reaction, and/or the catalyst lifetime.
  • Non-limiting examples of these optional components may be fillers; inorganic and organic pigments;
  • anticorrosive pigments anti-settling agents; dispersants; toughening agents; flexibilizing agents; processing aides; flow and leveling modifiers; slip and mar aids; defoamers; deaerators, adhesion promoters; diluents; stabilizers; plasticizers; curing catalysts; catalyst de-activators; flame retardants; aromatic hydrocarbon resins; coal tar pitch; petroleum pitch; carbon nanotubes; graphene; carbon black; carbon fibers; or mixtures thereof.
  • the amount of the optional compounds may range from 0 wt % to about 80 wt%.
  • the amount of the optional components may range from 0 wt% to about 80wt %, from 0.01 wt% to about 70 wt%, from 0.1 wt% to about 60wt %, or from 1 wt % to about 50wt % based on the total weight of all of the components present in the curable composition.
  • the amount of the wetting agent may be range from 0 wt% to 1 wt%. In various embodiments, the amount of the wetting agent may range from 0 wt% to about 1 wt%, from 0.2 wt% to about 0.8 wt%, from 0.3 wt% to about 0.7 wt%, or from 0.4 wt% to about 0.6 wt%. Generally, the amount of the pigment may range from 0 wt% to about 90 wt%.
  • the amount of the pigment may range from 0 wt% to about 90 wt%, from 20 wt% to about 70 wt%, or from 30 wt% to about 50 wt%.
  • concentrations of the optional compounds may range from 0 wt% to about 90 wt%, from 20 wt% to about 70 wt%, or from 30 wt% to about 50 wt%.
  • the curable epoxy resin composition has many beneficial properties. These properties are important to allow the curable epoxy resin composition to be processed into a cured solid state. One of the most important property is the viscosity which is allows for the curable epoxy resin composition to be flowable.
  • the curable composition exhibits a low viscosity sufficient to allow the curable composition to be processed and handled in conventional formulation equipment.
  • the viscosity of the curable epoxy resin composition may vary depending on whether the composition is pigmented or non-pigmented or other additives; and may depend on other considerations.
  • the viscosity of the composition comprising the epoxy resin, the polyamide hardener; and the compatibilizer is such that the initial viscosity of the composition is lower than that of a composition of epoxy resin and polyamide hardener (i.e., lacking a compatibilizer). It is beneficial that the initial viscosity of the composition be as low as possible. Also, the difference in the viscosity (i.e., the reduction in viscosity) of the composition having a compatibilizer when compared to a composition lacking a compatibilizer be as high as possible.
  • the initial viscosity of the composition having a compatibilizer when compared to the initial viscosity of a composition lacking a compatibilizer, may be at least about 50 % lower in viscosity than the viscosity of the composition lacking a compatibilizer.
  • the initial viscosity of the composition having a compatibilizer may range from 1 % lower in viscosity to about 20%.
  • the initial viscosity of the composition having a compatibilizer may range from 1 % lower in viscosity to about 20%, from about 2% to about 18%, from about 5% to about 15%, to from about 8% to about 12% lower in viscosity than the viscosity of the composition lacking a compatibilizer, measured at 25°C.
  • the viscosity of curable formulation may range from 50 mPa-s to about 10,000 mPa-s. In various embodiments, the viscosity of curable formulation may range from 50 mPa-s to about 10,000 mPa-s, from about 100 mPa-s to about 8,000 mPa-s, or from 1 ,000 mPa-s to about 5,000 mPa-s measured at 25°C.
  • the curable composition having the above viscosity can be easily processed and readily handled in end use processes for forming thermoset products.
  • the curable may comprise a low VOC, high volume solids, and high pigment volume content (PVC).
  • the low VOC of the curable composition may range from 0 g/L to about 300 g/L. In various embodiments, the low VOC may range from 0 g/L to about 300 g/L, from 50 g/L to about 250 g/L, or from about 100 g/L to about 150 g/L.
  • the high volume solids of the curable composition may range from about 50 % to about 100 %. In various embodiments, the high volume solids of the curable composition may range from about 50 % to about 100 %, from 60 % to about 95 %, or from 70 % to about 90 %.
  • the high PVC of the curable composition may range from 0 % to about 60 %. In various embodiments, the high PVC of the curable composition may range from 0 % to about 60 %, from 10 % to about 50 %, or from 20 % to about 40 %.
  • the process of preparing the curable epoxy resin composition may be achieved by blending, in known mixing equipment, (a) at least one epoxy resin; (b) at least one polyamide hardener; and (c) at least one compatibilizer agent; and optionally any other desirable additives.
  • the components described above are mixed in the following permissible component ranges for the curable composition: from 5 wt % to about 80 wt % of an epoxy resin; from 15 wt % to about 50 wt % of a polyamide hardener; and from 0.5 wt % to about 10 wt % of a compatibilizing agent.
  • the above epoxy resin-based curable composition may advantageously be used for preparing a coating material, a product, or a thermoset.
  • Components in the curable epoxy resin composition may be mixed in any order to provide the curable epoxy resin composition of the present invention. Any of the above- mentioned optional components may also be added to the composition during the mixing or prior to the mixing to form the composition.
  • the temperature during the mixing of all components may be generally from about -10°C to about 40°C. In various embodiments, the temperature during the mixing may range from -10°C to about 40°C, from 0°C to about 30°C, or from 10°C to about 20°C.
  • the preparation of curable epoxy resin composition and/or any of the steps thereof may be a batch or a continuous process.
  • the mixing equipment used in the process may be any vessel and ancillary equipment well known to those skilled in the art.
  • Another aspect provides processes for preparing a cured
  • the processes comprise providing a curable epoxy resin composition, which is detailed above, applying the curable epoxy resin composition, and exposing the curable composition to heat and pressure to form the cured coating.
  • the curable composition is applied to at least a portion of a surface of an article to be coated, prior to subjecting it to heat for curing.
  • Suitable curable epoxy resin compositions are described above.
  • an article comprising a cured or uncured curable epoxy resin composition adhering to at least one portion of the substrate.
  • the article in broad terms, may be defined as a material wherein the curable epoxy resin composition is initially applied and adheres to at least a portion of at least one surface of the substrate.
  • the curable epoxy resin composition may be cured at a exposing the composition to heat to form a thermoset or cured composition such that the coating bonds to the substrate.
  • the article may be any material that can withstand the curing temperature to form a cured coating.
  • the article may be a metal.
  • the article, as defined herein, may be a single metal or an alloy of various metals.
  • Non-limiting examples of these metals include cast iron, aluminum, tin, brass, steel, copper, zinc aluminum alloy, nickel, or combinations thereof.
  • the substrate may be a cellulose product.
  • cellulose products may be paper, paperboard, paper cardstock, cardboard, wood, and balsawood.
  • the substrate may be a plastic.
  • plastics may be bakelite, polyester, polyethylene terephthalate, polyethylene, high density polyethylene, polyvinyl chloride, polyvinylidene chloride, polypropylene, polystyrene, polyamides (Nylon), acrylonitrile butadiene styrene, polycarbonates, polyurethanes, and combinations thereof.
  • the article may be a stone.
  • stones may be granite, brick, limestone, concrete, and combinations thereof.
  • the article may be foam.
  • foams may be a polyurethane foams, high density foams, evlon foams, high resilience foams, latex rubber foams, rebond foams, memory foams, closed cell foams, dry fast foams, polyethersulfone foams, polyvinylchloride foams, polyethylene foams, polystyrene foams, and syntactic foams.
  • the article may be a structural laminate or a composite.
  • structural laminates or composites may be laminate floor, carbon fiber laminates, carbon fiber composites, fiber composites, polymer matrix composites, metal matrix composites, and ceramic matrix composites.
  • the article may be in various embodiments.
  • Non-limiting configuration examples of the article may be a roll, a coil, a plate, a sheet, a tube, a brick, a slab, a boulder, or a pipe.
  • the configuration of the article may be of various dimensions, shapes, thicknesses, and weights.
  • the process further comprises applying the curable epoxy resin composition to a portion of at least one surface of an article.
  • Suitable articles are detailed above.
  • Application of the curable coating composition may be applied through various means.
  • the coating composition may be applied using a drawdown bar, a roller, a knife, a paint brush, a sprayer, dipping, or other methods known to the skilled artisan.
  • the curable coating composition may be applied to one or more surfaces of the article to be coated.
  • the process further comprises curing the curable epoxy resin composition to a portion of at least one surface of an article.
  • the curable epoxy resin composition as detailed herein, may be cured by exposing the composition to heat and pressure to form a cured composition or thermoset.
  • the process for producing the cured coating material includes carrying out the curing reaction at process conditions to enable the preparation of an effective cured material having the desired balance of properties for a particular application, such as a film, a coating, a solid, or a thermoset.
  • the temperature for curing the curable composition may range from -10°C to about 100°C. In various embodiments, the curing temperature may range from -10°C to about 100°C, from 20°C to about 80°C, or from 40°C to about 60°C.
  • the application pressure to carry out the curing process may range of from about 1 psig (6.9 kPa) to about 150 psig (1 ,034.2 kPa).
  • the application pressure may range from 1 psig (6.9 kPa) to about 150 psig (1 ,034.2 kPa), from 5 psig (34.5 kPa) to about 80 psig (551 ,6 kPa), or from 10 psig (68.9 kPa) to about 20 psig (137.9 kPa).
  • the curing time can and will vary depending on the curable epoxy resin composition such as the hardener, compatibilizer, and optional components used in the formulation.
  • the curing time to may range from 0.1 hour to about 14 days, from 0.5 hours to about 7 days, from 1 hour to about 24 hours, or from 2 hours to 12 hours.
  • the preparation of the cured coating material and/or any of the steps thereof, may be a batch or a continuous process.
  • the equipment employed to carry out the reaction includes equipment known to those skilled in the art.
  • Some non-limiting examples of end use applications for these coated products may be clear epoxy coatings, pigmented epoxy based coatings, and epoxy based primer coatings.
  • the cured coating material prepared by the process exhibits unexpected and unique properties.
  • the cured coating material exhibits a gloss, hardness, and MEK solvent resistance better than that of a cured coating produced with the same curable composition except that the composition does not contain the compatibilizers.
  • the cured coating material (i.e., the cross-linked product made from the curable composition) shows several improved and beneficial performance properties over conventional cured thermosets made from conventional curable compositions containing conventional curing agents and catalysts.
  • the cured coating material may advantageously exhibit an improvement in several properties such blooming/blushing; gloss; MEK resistance; hardness; dry-time; impact; conical bend; and cross-hatch.
  • the cured coating material exhibits a reduction of blooming/blushing compared to cured coatings of the prior art.
  • the blooming/blushing of the cured coating is typically determined according to a visual observation of the coating. Then, the amount of blooming/blushing observed on the coating is given a rating based on a scale of from "0" to "5" wherein "0" is the worst result and "5" is best result.
  • the rating scale of blooming/blushing used herein is described in the following Table I: Table I - Rating Scale for Blooming/Blushing
  • the blooming/blushing of the cured coating is generally from 3 to 5.
  • the blooming/ blushing is generally from 3 to 4, from 4 to 5, or from 3 to 5.
  • the cured coating material of the present invention can exhibit a change in the coatings gloss by losing or gaining its gloss property.
  • One advantageous property of the coating material is to maintain its original gloss property as much as possible.
  • a measure of gloss of a coating is its "gloss change" property after wiping with finger or paper towel.
  • the gloss change percentage of the coating should be as low as possible.
  • the gloss change may be at least 20%. In various embodiments, the gloss change may be less than 20%, less than 10%, less than 5%, less than 3%, and less than 1 %. If the coating exhibits a gloss change of more than about 20 %, blooming and/or blushing can occur and typically has already occurred.
  • the MEK double rub resistance of the cured coating material may range from 100 times to about 2,000 times. In various embodiments, the MEK double rub resistance may range from 100 times to about 2,000 times, from 150 times to about 1 ,000 times, or from 200 times to about 500 times. A MEK double rub of less than about 100 times means the coating has a poor solvent resistance.
  • the cured coating material may exhibits pendulum hardness ranging from 50 s to about 200 s.
  • the pendulum hardness may range from 50 s to about 200 s, from 80 s to about 180 s, from 100 s to about 160 s, or from 120 s to about 140 s.
  • the cured coating material exhibits a dry-hard time may range from 1 hr to about 48 hr.
  • the dry-hard time of the cured coating material may range from 1 hr to about 48 h, from 2h to about 24h, from 3h to about 18h, or from 4 h to about 12 h.
  • the cured coating material may exhibits an impact generally above 1 .0 kilogram-meter (kg-meter) direct impact; above 1 .3 kg-meter; above 1 .5 kg-meter for clear coating; and exhibits an impact generally above 0.06 kg-meter direct impact;
  • the cured coating material may exhibit conical bend from 0.3175 - 3.81 cm generally less than 20 millimeters (mm); less than 10 mm; less than 5 mm; and 0 mm. [0073] The cured coating material exhibits a cross-hatch adhesion of greater than 4B or 5B.
  • compatible refers to the ability for two or more different materials or compounds to exist together as a mixture in a composition in close and permanent association for an indefinite period or exist in intimate contact as a mixture in a composition for long periods with no adverse effect of one compound on the other compound in the composition.
  • composition refers to a compound used in the curable composition. This compound provides compatibility between two or more different compounds in a composition.
  • the terms “blooming” refers to an ingredient, substance, or “gluelike” material present on a coating surface in the cured epoxy composition.
  • the term "blushing” refers to an unsightly graying of a dried coating which typically includes a whitish or grayish particulate material formed on a coating surface during curing of a curable composition.
  • no substantial blooming and blushing or “without substantial blooming and blushing” is in reference when a finger (e.g., an index finger) or a piece of paper (e.g., a paper towel) is rubbed across the surface of a cured clear coating, such rubbing action does not leave a mark on the surface of the cured clear coating and/or such rubbing action does not pick up residue and leaves the residue on the surface of the finger or paper towel as determined by visual observation.
  • no substantial blooming or blushing refers to a value of 4 or 5.
  • Blooming and blushing can be measured based on the gloss change of a cured clear coating after wiping with a finger or paper towel; and therefore "no substantial blooming and blushing" herein, in reference to a cured clear coating, means the coating exhibits a gloss change of less than 20 percent (%), less than 10 %, and less than 1 %.
  • induction time refers to the initial reaction time period needed to allow compounds in a formulated curable composition to become compatible with each other before applying the curable composition onto a substrate.
  • halogen or halo as used herein alone or as part of another group refer to chlorine, bromine, fluorine, and iodine.
  • alkyl as used herein describes saturated hydrocarbyl groups that contain from 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and most preferably 1 -10 carbon atoms. They may be linear, branched, or cyclic, may be substituted as defined below, and include methyl, ethyl, propyl, isopropyl, butyl, hexyl, heptyl, octyl, nonyl, and the like.
  • substituted alkyl as used herein describes saturated hydrocarbyl groups which are substituted with at least one atom other than carbon, including moieties in which a carbon chain atom is substituted with a heteroatom such as nitrogen, oxygen, silicon, phosphorous, boron, or a halogen atom, and moieties in which the carbon chain comprises additional substituents.
  • substituents include alkyl, alkoxy, acyl, acyloxy, alkenyl, alkenoxy, aryl, aryloxy, amino, amido, acetal, carbamyl, carbocyclo, cyano, ester, ether, halogen, heterocyclo, hydroxyl, keto, ketal, phospho, nitro, and thio.
  • hydrocarbon and “hydrocarbyl” as used herein describe organic compounds or radicals consisting exclusively of the elements carbon and hydrogen.
  • moieties include alkyl, alkenyl, alkynyl, and aryl moieties. These moieties also include alkyl, alkenyl, alkynyl, and aryl moieties substituted with other aliphatic or cyclic hydrocarbon groups, such as alkaryl, alkenaryl and alkynaryl. They may be straight, branched, or cyclic. Unless otherwise indicated, these moieties preferably comprise 1 to 20 carbon atoms.
  • HEA hydroxylethyl acrylate
  • HEMA hydroxyethyl methacrylate
  • PETA pentaerythritol triacrylate
  • DMAPA dimethylaminopropyl acrylate
  • DMP- 30 which stands for tris(dimethylaminomethyl)phenol and which is commercially available from Aldrich
  • Versamid 140 which is a polyamide hardener and which is commercially available from BASF
  • DLVE-18 which is a proprietary epoxy resin having a viscosity of about 860-960 mPa-s at 25°C, and an EEW of about 170-180, and which is available from The Dow Chemical Company
  • M-Cure 201 which is a multifunctional acrylate and which is commercially available from Sartomer
  • Versamid 125 which is a polyamide hardener and which is commercially available from BASF
  • BYK 9076 which is a dispersant and which is commercially available from B
  • Coating blooming evaluations and measurements were conducted by direct eye (visual) observation before and after wiping the coating surface with a gloved index finger to see if any oily material trace was deposited on the surface of the coating. After wiping the coating surface, the amount of blooming was qualitatively rated according to the standard rating scale described in Table I above.
  • the blooming coating surface measurements described above were also confirmed by comparing the gloss of a blooming surface to a non-blooming surface.
  • the coating gloss measurements were obtained with a BYK Micro Tri-Gloss Meter (RS-232 Output, 20/60/85 Degree); a gloss meter available from BYK.
  • HADVIII+ Viscometer using Spindle # 31 at 10-200 revolutions per minute (rpm) by adjust torque to 25-25 % and at ambient temperature (i.e., 23°C-25°C).
  • Methyl ethyl ketone (MEK) resistance measurements were obtained using the standard test procedure described according to ASTM D5402.
  • Coating hardness measurements were obtained using a pendulum hardness instrument, BYK Gardner Konig pendulum apparatus, and the standard test procedure described according to ISO 1522. Coating Dry-Time Measurements:
  • Curable epoxy resin coating compositions as described in Tables II and III, were prepared and then polished cold rolled steel panels, with dimensions of 4 inches in width, 6 or 12 inches in length, and 0.025 inch in thickness (these are standard panels used in coating testing with dimensions for example as follows: 10.16 centimeter (cm) X 15.24 cm X 0.0635 cm), were coated with the compositions after being formulated without an induction time. The coatings were cured at ambient temperature for 7 days to form clear coatings.
  • the clear coatings were prepared using the curable compositions of the Examples of the present invention (with the acrylate additive components); and the curable compositions of the Comparative Examples (without acrylic additives), as described in Table II.
  • the curable compositions were formulated with Versamid 125 polyamide curing agent. All the clear coating curable formulations contained 3 % tris(dimethylaminomethyl)phenol (DMP-30) reaction accelerator based on the amount of DLVE-18 and 5 % of xylene based on total formulation.
  • DMP-30 tris(dimethylaminomethyl)phenol
  • the stoichiometry of the epoxy groups to the N-H groups in the coating formulation was 1 to 1 .
  • Each acrylate additive was evaluated at each of the following loading levels: 1 %, 3 %, and 5 %.
  • Table II shows the results of the blooming property exhibited by the clear coating products prepared in these examples and comparative examples.
  • HEA, PETA, and DMAPA are used in Examples 1 , 2 and 3, respectively, of the present invention.
  • the Control is Comparative Example A.
  • Table III shows the coating performance based on Examples 1 , 3, and 5 from Table II at 5 % of different acrylate additives. The results show that an amount of 5 % of the acrylate additive significantly improves the coating hardness but does not affect other coating performance.
  • Table V shows the pigmented coating performance by curing with Versamid 125 for both with and without DMP-30 for comparison.
  • the results indicate the compatibility of epoxy resin and curing agent was improved by the addition of acrylic additive, as indicated by the coating gloss, whether DMP-30 was present or absent. However, due to pigmented system, there was no significant difference in blooming observed.
  • the Controls in Table V are Comparative Examples B and C.
  • Example Example 9 Example 10 Example 1 1
  • Table VI shows the pigmented coating performance by curing with
  • HEA additive was also evaluated in different pigmented coating systems based on DLVE-18 and Versamid 140.
  • Table VII is an example of a pigmented DLVE-18 / Versamid 140 formulation containing 10 % HEA and DMP 30.
  • Table VIII shows paint viscosity, coating appearance and dry time.
  • HEA effectively reduced formulated paint viscosity and improved the appearance of the coatings after 7 days of cure (Examples 13 and 14).
  • the early drying speed such as dry to touch was also improved due to the fast reaction introduced by HEA component.
  • Viscosity is measured using Brookfield CAP 1000 cone-and- plate viscometer using spindle CAP 05.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne une composition de revêtement à base de résine époxy durcissable utile pour la préparation d'un revêtement comprenant (a) au moins une résine époxy ; (b) au moins un durcissant polyamide ; (c) au moins un agent de compatibilité réactif ayant au moins une fonctionnalité polaire ; et (d) éventuellement, d'autres composés tels qu'un catalyseur de durcissement ; où la composition de revêtement à base de résine époxy durcissable possède une teneur en matières solides en volume supérieure à environ 70 pour cent ; et où la composition de revêtement à base de résine époxy durcissable, lorsqu'elle est durcie, ne présente pas d'efflorescence ni de formation de voile ; et un matériau de revêtement durci fabriqué à partir de la composition durcissable ci-dessus.
PCT/US2016/033192 2015-05-20 2016-05-19 Composition de revêtement époxy Ceased WO2016187380A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN115216169A (zh) * 2021-04-15 2022-10-21 株式会社Kcc 船舶用无溶剂型环氧涂料组合物

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Publication number Priority date Publication date Assignee Title
GB990603A (en) * 1962-05-02 1965-04-28 Ciba Ltd New amides and process for their manufacture, and use
EP0918071A1 (fr) * 1997-11-19 1999-05-26 Air Products And Chemicals, Inc. Durcisseurs polyamides à base de polyéthylèneamines et de dérivés de pipérazine
WO2007054304A1 (fr) * 2005-11-10 2007-05-18 Ppg B.V. Revetements a base d’epoxy
EP2551321A1 (fr) * 2010-03-25 2013-01-30 YAMAHA Corporation Composition de durcisseur pour adhésif à base de résine époxy, et adhésif pour matériaux poreux
CN104277526A (zh) * 2014-09-04 2015-01-14 青岛佳尚创意文化有限公司 一种防水涂料及其生产方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB990603A (en) * 1962-05-02 1965-04-28 Ciba Ltd New amides and process for their manufacture, and use
EP0918071A1 (fr) * 1997-11-19 1999-05-26 Air Products And Chemicals, Inc. Durcisseurs polyamides à base de polyéthylèneamines et de dérivés de pipérazine
WO2007054304A1 (fr) * 2005-11-10 2007-05-18 Ppg B.V. Revetements a base d’epoxy
EP2551321A1 (fr) * 2010-03-25 2013-01-30 YAMAHA Corporation Composition de durcisseur pour adhésif à base de résine époxy, et adhésif pour matériaux poreux
CN104277526A (zh) * 2014-09-04 2015-01-14 青岛佳尚创意文化有限公司 一种防水涂料及其生产方法

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KIRK- OTHMER: "Encyclopedia of Chemical Technology", vol. 9, pages: 267 - 289
LEE, H.; NEVILLE, K.: "Handbook of Epoxy Resins", 1967, MCGRAW-HILL BOOK COMPANY, pages: 257 - 307

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115216169A (zh) * 2021-04-15 2022-10-21 株式会社Kcc 船舶用无溶剂型环氧涂料组合物

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