EP3455309A1 - Bisphenol a-free ethylene (meth)acrylic acid copolymer composition for metal can coatings - Google Patents
Bisphenol a-free ethylene (meth)acrylic acid copolymer composition for metal can coatingsInfo
- Publication number
- EP3455309A1 EP3455309A1 EP17721184.4A EP17721184A EP3455309A1 EP 3455309 A1 EP3455309 A1 EP 3455309A1 EP 17721184 A EP17721184 A EP 17721184A EP 3455309 A1 EP3455309 A1 EP 3455309A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ethylene
- acrylic acid
- coating composition
- meth
- copolymer
- 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.)
- Withdrawn
Links
Classifications
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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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/08—Copolymers of ethene
- C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09D123/0869—Acids or derivatives thereof
- C09D123/0876—Neutralised polymers, i.e. ionomers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
- B05D7/227—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes of containers, cans or the like
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
Definitions
- the present disclosure relates to aqueous dispersions having a ethylene (meth)acrylic acid copolymer, a phenolic crosslinker, and optionally a hydroxyalkylamide crosslinker, methods of coating substrates with the foregoing, and substrates coated with the foregoing.
- Coating compositions formed from epoxy resins have been used to coat packaging and containers for foods and beverages. Although the weight of scientific evidence, as interpreted by the major global regulatory food safety agencies in the US, Canada, Europe, and Japan, shows that the levels of bisphenol A consumers are exposed to with current commercial epoxy based coatings is safe, some consumers and brand owners continue to express concern, and a coating that does not contain bisphenol A or any other endocrine disruptor is desirable. There is also a desire to eliminate surfactants from such coating compositions, because the surfactants could in theory dissolve in the beverages.
- High acid content, high melt index ethylene (meth)acrylic acid copolymers are dispersible in alkali aqueous dispersions under proper reaction conditions. Such aqueous dispersions are widely used in glues and other adhesives, personal care applications, and paper coating applications. US 7,803,865 describes a process to prepare such aqueous dispersions in an extruder.
- ethylene (meth)acrylic acid copolymer dispersions are hydrophilic and have poor chemical resistance and poor blush resistance.
- Crosslinkers such as melamine formaldehyde, urea formaldehyde, phenol formaldehyde, an alkali metal hydroxide, a zinc/zirconium complex, and an epoxy resin
- crosslinkers have been used to improve chemical and blush resistance, but these crosslinkers do not produce a coating with sufficient chemical and blush resistance required for many packaging coating applications. Also, such compositions tend to absorb flavorants from the food or beverage which affects the taste.
- US 2012/01 18785 describes aqueous dispersions containing a base polymer and a stabilizing agent, wherein the base polymer may be an ethylene acrylic-acid co-polymer.
- the ethylene acrylic-acid co-polymer described in US 2012/01 18795 as the base polymer requires the use of an additional stabilizing agent.
- the higher molecular weight provided by the base polymer was needed to provide improved coating properties, such as improved flexibility and /or ease of control of crystallinity.
- the coating compositions of the present disclosure comprise aqueous dispersions of ethylene (meth)acrylic acid copolymers.
- the coating compositions of the present disclosure include certain crosslinkers to crosslink aqueous ethylene (meth)acrylic acid copolymers and/or self-condense, thereby providing a unique combination of properties such as water resistance, flexibility, chemical resistance, corrosion resistance and excellent adhesion on substrates.
- ethylene (meth)acrylic acid copolymers refers to ethylene acrylic acid (EAA) copolymers and ethylene methacrylic acid (EMA) copolymers.
- the coating compositions of the disclosure may comprise EAA, EMA, or both.
- the coating compositions may comprise more than one EAA, and/or more than one EMA.
- the coating compositions of the present disclosure may comprise only one ethylene (meth)acrylic acid copolymer such as one EAA copolymer or one EMA copolymer.
- the present disclosure provides an alternate to epoxy resins that still allows formaldehyde-free cure, blush resistance, capability to retort and can withstand hard- to-hold beverages.
- the coating compositions of the disclosure can be made with a simple process, not requiring multiple polymers or processing stages to achieve the intended effect.
- ethylene(meth)acrylic acid copolymer having number average molecular weight of 2500-4500 Da, a weight average molecular weight of 5500- 9000Da, and a (meth)acrylic acid content of 15-20%
- the inventors discovered that it is possible to prepare coating compositions comprising ethylene(meth)acrylic acid copolymer with desirable coating properties, and without the need for a stabilizing agent.
- the coating compositions of the disclosure include a phenolic crosslinker and, optionally, a solution acrylic dispersant, an acrylic rheology modifier, a betahydroxy alkylamide crosslinker (e.g., Primid XL552), solvents and/or additives.
- a phenolic crosslinker and, optionally, a solution acrylic dispersant, an acrylic rheology modifier, a betahydroxy alkylamide crosslinker (e.g., Primid XL552), solvents and/or additives.
- the coating compositions of the disclosure are suitable, inter alia, as packaging coatings for food and beverage packaging and containers, including beer and beverage external/interior easy-open-ends and plastic bottles.
- the present disclosure also provides methods of coating substrates with the coating composition and substrates coated with the aqueous dispersions.
- the coating disclosed herein is free of Bisphenol A that is currently used in the epoxy food can coatings.
- the coating is unique in that the use of EAA and/or EMA copolymers is predominantly found in the hot melt adhesive market and not in coatings as the primary resin.
- the present disclosure includes substrates coated at least in part with an coating composition of the disclosure and methods for coating the substrates.
- substrate as used herein includes, without limitation, plastic bottles, cans, metal (such as aluminum) cans, beer and beverage easy-open-ends, packaging, containers, receptacles, or any portions thereof used to hold, touch or contact any type of food or beverage.
- substrate includes, for non-limiting example, "can ends,” which can be stamped from can end stock and used in the packaging of beverages.
- the coating composition of the disclosure comprises ethylene (meth)acrylic acid copolymer, a phenolic crosslinker, a solution acrylic dispersant, an acrylic rheology modifier, a betahydroxy alkylamide crosslinker (e.g., Primid XL552), solvents and additives.
- the ethylene (meth)acrylic acid copolymers of the coating compositions of the disclosure have a number average molecular weight of 2500 - 4500 Da, a weight average molecular weight of 5500 - 9000 Da, and a (meth)acrylic acid content of 15 - 20% (see, for example, Examples 1 -2, below).
- Ethylene (meth)acrylic acid copolymers suitable for use in the coating compositions of the disclosure are well known in the art and commercially available.
- suitable ethylene (meth)acrylic acid copolymers include Primacor® (EAA) resins available from Dow Chemical (such as Primacor® 59801 (EAA, acrylic acid 20 wt%) and Primacor® 59901 (EAA, 20.5 wt% acrylic acid ), Nucrel® resins available from DuPont (such as Nucrel® 2806 (EAA, 18 wt% acrylic acid), Nucrel® 925 (EMA, 15 wt% methacrylic acid), and Nucrel® 960 (EMA, 15 wt% methacrylic acid)), Honeywell A-C® 5180 (EAA, 20 wt% acrylic acid and acid number 185-225 mg KOH/g), and Honeywell A-C® 5120 (EAA, 15 wt% acrylic acid and acid number 1 12-130 mg KOH/g), and the like, as well as combinations thereof.
- Primacor® (EAA) resins available from Dow Chemical such as Primacor® 59801 (EAA, acrylic acid 20 wt%) and Primacor®
- the ethylene (meth)acrylic acid copolymer is first dispersed in water (20 to 35% wt% solids of ethylene (meth)acrylic acid copolymer) and neutralized with a base (e.g., an amine base such as triethanol amine (TEA), dimethylethanol amine (DMEA), or dithethylamino ethyl (DEAE)).
- a base e.g., an amine base such as triethanol amine (TEA), dimethylethanol amine (DMEA), or dithethylamino ethyl (DEAE)
- the neutralization may be conducted at temperature of about 95 to about 120 °C for about 10 minutes is suitable.
- the process of dispersing EAA is preferably carried out at a minimum of about 90 °C in an open reactor. If a closed reactor is used, temperatures of about 105 to about 120 °C may be used to make an aqueous dispersion having greater than 20% solids.
- the ethylene (meth)acrylic acid copolymer may be present in an amount from about 30 to about 90 wt% of the aqueous dispersion (e.g., 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 %).
- a parameter such as the wt % of ethylene (meth)acrylic acid copolymer in an aqueous dispersion of the disclosure
- the amount of ethylene (meth)acrylic acid copolymer can be any of the amounts just listed as well as ranges such as 45-50 wt%, 40-80 wt%, etc.).
- the aqueous dispersion of ethylene (meth)acrylic acid copolymer(s) is surfactant free.
- the aqueous dispersion of ethylene (meth)acrylic acid copolymer(s) is stable and remains dispersed without the need for a stabilizer, such that the aqueous dispersion of ethylene (meth)acrylic acid copolymer(s) is substantially stabilizer free, or contains no stabilizing agents.
- the particle size of the dispersions can been determined by dynamic light scattering (DLS) and laser diffraction spectroscopy (LDS).
- preferred dispersions have a DLS and LDS volume weighted average of less than 1 micrometer and a number weighted average of less than 0.5 micrometers particle size.
- the aqueous dispersion of ethylene (meth)acrylic acid copolymer(s) comprises more than one ethylene (meth)acrylic acid copolymer(s).
- the aqueous dispersion of ethylene (meth)acrylic acid copolymer(s) contains two ethylene (meth)acrylic acid copolymer, such as two ethylene (meth)acrylic acid copolymer(s) wherein the ratio of one ethylene (meth)acrylic acid copolymer to the other is no greater than 3:1 , or no greater than 2:1 .
- Phenolic crosslinkers can be added to the coating composition of the disclosure directly or included in the ethylene (meth)acrylic acid copolymer-containing aqueous dispersion.
- suitable phenolic crosslinkers include, without limitation, PHENODUR® EP 560, PH2028, PH2013/65B, and PR899/60MPC; Hexion's PF6535LB, SI Group's SFC1 12/65 (butyl phenol resin), Ruters's 7700 LB, or a combination thereof.
- the phenolic crosslinker is PHENODUR® EP 560 (a butyl etherified phenol formaldehyde crosslinker)
- 5 to 25 wt% may be used (e.g., 5, 10, 15, 20, and 25 wt %).
- the coating compositions of the present disclosure do not contain or are substantially free of bisphenol A.
- substantially free means that there is no more than 1 .0 % by weight, preferably no more than 0.5% by weight, and more preferably no more than 0.1 % by weight of the compound, or structural units derived from the compound, present in the coating composition.
- the coating composition of the disclosure may include a hydroxyalkylamide crosslinker. The hydroxyalkylamide crosslinker helps improve corrosion resistance when the coating composition is used as a protective coating that contacts the food or beverages, and, so, a hydroxyalkylamide crosslinker may be desirable to use when the coating is intended for such use.
- the hydroxyalkylamide crosslinker may include without limitation a beta-hydroxyalkylamide crosslinker, such as Primid® XL-552 (N,N,N',N'-tetrakis-(2-hydroxyethyl)-adipamide).
- a beta-hydroxyalkylamide crosslinker such as Primid® XL-552 (N,N,N',N'-tetrakis-(2-hydroxyethyl)-adipamide).
- additional crosslinkers may be used in the coating compositions of the disclosure.
- Suitable additional crosslinkers can include, but are not limited to, urea-formaldehyde, phenol- formaldehyde, benzoguanamine formaldehyde, phenolic resins, and combinations thereof.
- Other crosslinkers that may be used include oxazoline, oxetane and dioxetane.
- Still other crosslinkers that may be used but are less preferred are melamine formaldehyde, urea formaldehyde, phenol formaldehyde, an alkali metal hydroxide, a zinc/zirconium complex, and an epoxy resin.
- the amount of the additional crosslinker is about 0.1 to about 30 wt% based on the total polymer solids content in the aqueous dispersions.
- the crosslinker may help improve chemical resistance and/or water blush resistance. However, if the amount of the crosslinker is too high, the film may lose flexibility. Whether the amount of crosslinker is too high is routinely determinable to those skilled in the field of such coatings.
- the phenolic and hydroxyalkylamide polymers may or may not crosslink (self-condense or crosslink with EAA or EMA). But such crosslinking improves the chemical resistance of the coating and, therefore, may be desirable. Curing for 5-10 minutes at 215-220 °C, for example, is expected to result in an advantageous amount of crosslinking, but it is a routine task to vary conditions to adjust and optimize the degree of crosslinking for a particular application.
- the coating compositions of the disclosure may include a neutralizer such as without limitation ammonia/ammonium hydroxide, a tertiary amine, dimethylethanolamine, 2-dimethylamino-2-methyl-1 -propanol, tributylamine, morpholine, diethanolamine, triethanolamine, monoethanolamine, sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like, as well as combinations thereof.
- the neutralizer is present in an amount from about 20 to 100% mole-to-mole of acid in the compound to be neutralized.
- the coating compositions of the disclosure may include an organic solvent.
- Organic solvents may facilitate spray applications as well as assist in suspending the phenolic resin and solution acrylic dispersant in the water. Whether to include an organic solvent and the identity and amount of solvent can be easily determined by routine methods known in the art.
- Solvents may include without limitation xylene, benzene, ethyl benzene, toluene, alkoxy alkanols, methanol, ethanol, propanol, butanol, alkyl ethers of ethylene, alkyl ethers of propylene glycol, ethylene glycol monobutyl ether, ethylene glycol ethyl ether, diethylene glycol monobutyl ether, a ketone, an aromatic solvent, an ester solvent, a hydroxyl functional solvent, and combinations thereof.
- the amount of the solvent in the aqueous dispersion may be up to about 90% by weight of the polymeric solids, or from about 20% to about 45% by weight of the coating composition (e.g., 20, 25, 30, 35, 40, or 45 wt%).
- the amount of water in the aqueous dispersion may range from about 20 to about 50 wt%.
- the glass transition temperature (Tg) of the coating composition may depend on the total monomer composition and may contribute to blush resistance, lube bloom, and abrasion resistance. As non-limiting example, if the polymer has high amounts of methacrylic acid (e.g., between 5% and 20% of total polymer), then the polymer may have a higher Tg. In some embodiments of the disclosure, the Tg is from about 5 to about 50 °C. If the Tg is too low, the film may be too soft and may have insufficient abrasion resistance. If the Tg is too high, the film may wrinkle and may not have enough flexibility which may decrease film performance.
- the cure temperature may be about 200 to about 300 °C.
- the coating compositions can include conventional additives known to those skilled in the art, such as without limitation, additives to control foam, reduce equilibrium and dynamic surface tension, or to control rheology and surface lubricity. Amounts can vary depending on desired coating application and performance in any manner known to those skilled in the art.
- the coating compositions of the disclosure may include a solution acrylic dispersant.
- Solution acrylics are also known as solvent acrylics and are well known in the art.
- the solution acrylic dispersant serves to disperse into the water phase any component that does not readily disperse in water, including the phenolic crosslinker and solvents. Without the acrylic dispersant, the coating may separate into two distinct phases.
- Dispersants also referred to as surfactants
- Dispersants include liquids that can disperse small droplets or particles.
- dispersants can include a mixture of emulsifiers and solvents that break oil components into smaller droplets for incorporation throughout the water.
- Dispersants that can be used include polymeric or oligomeric surfactant based dispersing agents.
- the solution acrylic dispersant of Example 3 can be used, for example.
- Other solution acrylic dispersants useful in the coating compositions of the disclosure are known in the art and are commercially available (e.g. , from LU BRIZOL®, Wickliffe, Ohio).
- the acrylic dispersant can be used in an amount of 5 to 20% by weight of the aqueous dispersion (e.g. 5, 7.5, 10, 12.5, 15, 17.5, or 20 wt%).
- the coating composition of the disclosure may include an acrylic rheology modifier.
- the acrylic rheology modifier acts to swell and improve shear thinning properties required for spray application of the coating.
- Example 4 (below) describes a suitable acrylic rheology modifier for use in the aqueous dispersions of the disclosure.
- Other acrylic rheology modifiers useful in the coating compositions of the disclosure are known in the art, such as alkali swellable and hydrophobically modified alkali swellable modifiers.
- Acrylic rheology modifiers are also commercially available, such as from BASF (Rheovis AS and Rheovis HS).
- the acrylic rheology modifier can be used in an amount of 0.5 to 5% by weight of the aqueous dispersion (e.g., 0.5, 1 , 1 .5, 2, 2.5, 3, 3.5, 4, 4.5, or 5 wt%). Optimization of the balance of sag and flow of the coating compoistion is preferable to achieve uniform coverage over the bead rolls of a food can. Without the acrylic rheology modifier the shear profile of the coating may not be shear thinning, and the coating may run and not flow uniformly over the beads. It will be a routine matter for those of ordinary skill in the field of can coatings to determine the appropriate composition and amount of acrylic rheology modifiers for each type of application.
- the coating compositions of the present disclosure can be made by a multi- step process.
- An EAA or EMA dispersion can be made by dissolving the co-polymer into a solution of amine (or other neutralizing agent) and water. This mixture is then stirred until the desired particle size is achieved.
- a solution acrylic dispersion can be made by reacting acrylic monomers in a solvent blend followed by dispersing the reacted material into water and amine.
- An acrylic rheology modifier can be made as a latex in a manner well known to those skilled in the art.
- the the coating composition in the disclosure can be made by blending all the raw materials together in the following order: Phenolic resin, solvent, solution acrylic dispersant, solvent, EAA dispersion(s), hydroxyalkyl amide crosslinker, acrylic rheology modifier, solvent, water, additives.
- the resulting mixture can be blended with a cowls blade at high speed (800-1500 rpm). Modification of this method and adaptation for particular applications can be routinely conducted following the teachings of this application and common knowledge in the art of manufacturing compositions for coating food and beverage cans, plastic bottles, and the like.
- the present disclosure also provides a method of coating a substrate wherein the coating composition according to the present disclosure is applied to the substrate, which is preferably a food or beverage container, more preferably a bottle or a can.
- the coating compositions of the disclosure may be applied to a substrate alone or in combination with other coatings.
- Non-limiting example examples of other coatings that can be used in conjunction with the coating composition of the disclosure include a prime coat, which may be applied between the substrate and coating composition of the disclosure.
- Substrates on which the coating composition of the disclosure can be applied include cans, metal cans, beer and beverage easy-open ends, packaging, containers, receptacles, can ends, or any portions thereof used to hold or touch any type of food or beverage.
- the coating compositions of the disclosure can be applied to substrates in any manner known to those skilled in the art.
- the coating compositions are sprayed onto a substrate.
- the coating compositions may contain, for non-limiting example, from about 10 to about 30% by weight of the polymeric solids relative to about 70 to about 90% water including other volatiles such as, without limitation, minimal amounts of solvents, if desired.
- the coating compositions may contain, for non- limiting example, from about 20 to about 60% by weight of the polymer solids.
- Organic solvents may be utilized in some embodiments to facilitate spray or other application methods and such solvents may include, without limitation, n-butanol, 2-butoxy- ethanol-1 , xylene, toluene, and mixtures thereof. In some embodiments, n-butanol is used in combination with 2-butoxyethanol-1 .
- the coating compositions of the present disclosure may be pigmented and/or opacified with known pigments and opacifiers in some embodiments. For many uses, including food use for non-limiting example, the pigment may be titanium dioxide.
- the coating compositions may be applied in some embodiments by conventional methods known in the coating industry. Thus, for non-limiting example, spraying, rolling, dipping, and flow coating application methods can be used for both clear and pigmented films.
- the coating compositions after application onto a substrate, the coating compositions may be cured thermally at temperatures in the range from about 215 to about 250 °C, and alternatively higher for a time sufficient to effect complete curing as well as volatilizing any fugitive components therein.
- the coating compositions may be applied in some embodiments at a rate in the range from about 0.5 to about 15 milligrams per square inch of polymer coating per square inch of exposed substrate surface. In some embodiments, the coating compositions may be applied at a thickness from about 1 to about 25 microns.
- the coating compositions are applied in some embodiments at a rate in the range from about 1 .5 to about 15 milligrams of polymer coating per square inch of exposed substrate surface.
- Conventional packaging coating compositions are applied to metal at about 232 to about 247 °C.
- Some of the coating compositions of the current disclosure achieve good results at about 230 °C or below, such as at about 210 °C or below. This decreased temperature provides an energy savings to the coater, and it may allow the use of different alloys, such as tin-plated steel used for easy-open-ends. This also allows to recycle the ends together with the can body.
- the coating compositions of the present disclosure may comprise a relatively homogenous water dispersion particle structure and/or an inhomogeneous water dispersion particle structure.
- the coating composition's particle structure may be controlled by the polymerization processes, including, for example, a multi-stage polymerization process.
- Such particle structures are usually prepared by a series of consecutive emulsion polymerization sequences with different monomer types, where the second stage monomer is polymerized in the presence of seed water dispersion particles.
- the coating compositions of the disclosure can include conventional additives known to those skilled in the art, such as without limitation, additives to control foam, reduce equilibrium and dynamic surface tension, or to control rheology and surface lubricity. Amounts can vary depending on desired coating application and performance and are routinely determinable by those skilled in the art.
- EAA Ethylene Acrylic acid
- EAA Ethylene Acrylic acid
- % acrylic acid 20
- 211 bs of melted ethylene acrylic acid is added to a 10 gallon mixer fitted with N 2 blanket, overhead mixing, heating/cooling and temperature monitoring.
- the ethylene acrylic acid is heated to 125 °C, once at temperature 2.25 lbs (10% on solids) of dimethylethanolamine (Sigma Aldrich) is added and mixed for 20 minutes to combine.
- the temperature must be closely monitored due to possible exotherm.
- a separate mixer 51.75 lbs of Dl H 2 0 (Dl H 2 0 is deionized so the mineral content is less than 1 %) is heated to 95 °C.
- the heated water is added to the mixer over no more than 10 minutes. During water addition the mix speed is increased slowly to maximum. Once all water is added the temperature is allowed to rebound to 95 °C and the dispersion is mixed at high speed for 10 minutes. The dispersion is then cooled below 50 °C and filtered through a can approved 10 ⁇ filter. The non-volatiles content and particle size are measured and the dispersion is monitored for separation.
- the melted ethylene acrylic acid is added to a 10 gallon mixer fitted with N 2 blanket, overhead mixing, heating/cooling and temperature monitoring.
- the ethylene acrylic acid is heating to 1 10 °C, once at temperature 4.5lbs (12.1 % on solids) of dimethylethanolamine (Sigma Aldrich) is added and mixed for 10 minutes to combine. The temperature must be closely monitored due to possible exotherm.
- the particle size of the dispersions was determined by dynamic light scattering (DLS) and laser diffraction spectroscopy (LDS).
- the degree of neutralization was evaluated from 132% to the preferred level of 70% neutralization.
- the reduced amount of amine improved compatibility and performance of the coating(s).
- Example 5 and Example 6 were used to coat cans in a standard, art-recognized method. Briefly, application of the coating was conducted with airless spray system, the coating being pumped through a specified nozzle and spray gun and applied to the inside of the container. Simulants Tests for Food Packs
- Brine Test Method A 2% sodium chloride solution is made, using 99% pure sodium chloride and deionized water. The solution is mixed until the sodium chloride is dissolved. Cans are filled with the 2% sodium chloride solution to the top bead of the food can. The bead is the roll added to the food can to provide strength. Actual volume of solution is dependent on the size of the can. Cans are sealed with a can end using a bench top seamer. Process the cans in a retort chamber for 90 minutes at 250 °F at 17 psi. Retort is a sterilization process used in the food canning industry. Following the 90 minute process, the cans are cut open and rated for corrosion, and adhesion. The performance rating occurs in the vapor phase of the can and the liquid phase.
- the brine test is a corrosion test that examines the coating resistance to a corrosive environment such as would be seen with foods packed into metal cans.
- Adhesion is evaluated by using a cross hatch to generate a grid of squares within a 1 square area. The grid is then covered with a clear tape and pulled to determine the removal of the coating from the grid. The adhesion is rated using the 0 to
- the rating scale for corrosion and blush is as follows:
- Lactic Acid Test Method Fill cans with 1 % lactic acid solution to top of beads. Seal cans using a bench top seamer. Process in a retort for 90 minutes at 250 degrees Fahrenheit. Following the 90 minute process, the cans are cut open and rated for corrosion, blush and adhesion.
- Blush is a chemical resistance measurement of the coating to resist the uptake of water/solution that it is immersed. The absorption of water results in a white or blush appearance. The blush is rated on a scale of 0 no blush to 10 coating is completely white.
- Mushy Pea Test Soak dried peas overnight. Drain peas. To a can add 250 grams of drained peas, also add 100 mL of 5% sodium thiosulfate solution. Fill can to 0.25 inch headspace with 140 Fahrenheit degrees deionized water. Seal cans using a bench top seamer. Process in a retort for 180 minutes at 250 °F. Cans are cut in half after 24 hours and 48 hours then evaluated for sulphide staining. Test Results
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US201662333575P | 2016-05-09 | 2016-05-09 | |
EP16176797 | 2016-06-29 | ||
PCT/EP2017/060911 WO2017194464A1 (en) | 2016-05-09 | 2017-05-08 | Bisphenol a-free ethylene (meth)acrylic acid copolymer composition for metal can coatings |
Publications (1)
Publication Number | Publication Date |
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EP3455309A1 true EP3455309A1 (en) | 2019-03-20 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP17721184.4A Withdrawn EP3455309A1 (en) | 2016-05-09 | 2017-05-08 | Bisphenol a-free ethylene (meth)acrylic acid copolymer composition for metal can coatings |
Country Status (4)
Country | Link |
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EP (1) | EP3455309A1 (en) |
KR (1) | KR20180135068A (en) |
CN (1) | CN109071989B (en) |
WO (1) | WO2017194464A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2019241209A1 (en) * | 2018-06-11 | 2019-12-19 | Swimc Llc | Packaging coating containing water-dispersible acrylic block copolymer |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3894485A1 (en) * | 2018-12-13 | 2021-10-20 | PPG Industries Ohio Inc. | Polyhydroxyalkylamide materials for use as crosslinkers |
CN109880443A (en) * | 2019-01-10 | 2019-06-14 | 苏州市三新包装材料科技有限公司 | Aqueous interior coating material of side seam and preparation method thereof and spraying method in a kind of no bisphenol A-type three-piece can |
CN117377705A (en) * | 2021-05-27 | 2024-01-09 | 巴斯夫涂料有限公司 | Coating compositions based on hydroxyalkylamides |
CN115948092B (en) * | 2022-12-27 | 2024-04-09 | 福建合润包装涂料有限公司 | Internal water spraying paint for pop can |
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EP1004608B1 (en) * | 1998-11-11 | 2004-10-20 | Minnesota Mining And Manufacturing Company | Multi-layer sheet comprising a protective polyurethane layer |
US7803865B2 (en) | 2003-08-25 | 2010-09-28 | Dow Global Technologies Inc. | Aqueous dispersion, its production method, and its use |
EP2456679B2 (en) | 2009-07-24 | 2020-08-19 | Dow Global Technologies LLC | Method of making a coated container device |
US20120118795A1 (en) | 2010-11-17 | 2012-05-17 | Mark Ellery Ogram | Gold refining apparatus |
EP2794704B1 (en) * | 2011-12-21 | 2017-04-05 | Akzo Nobel Coatings International B.V. | Water-based coating compositions |
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- 2017-05-08 CN CN201780027426.8A patent/CN109071989B/en active Active
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WO2019241209A1 (en) * | 2018-06-11 | 2019-12-19 | Swimc Llc | Packaging coating containing water-dispersible acrylic block copolymer |
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CN109071989A (en) | 2018-12-21 |
WO2017194464A1 (en) | 2017-11-16 |
CN109071989B (en) | 2021-10-01 |
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