# Patent

## Title
Aqueous-based coating composition containing an oleoresinous component

## Abstract

An aqueous-based coating composition suitable as a container coating comprising:

    
    
        (A) a resinous phase comprising
        
            (i) an organic oil,
            (ii) an at least partially neutralized acid functional polymer containing reactive functional groups,
            (iii) a phenolic compound and an aldehyde or the reaction product thereof;
            the resinous phase dispersed in
        
        
        (B) aqueous medium.

## Background
FIELD OF THE INVENTION
The present invention relates to aqueous-based coating compositions suitable as container coatings, particularly for the interior surface of cans exposed to corrosive food stuffs.
BACKGROUND OF THE INVENTION
Coatings are typically applied to the interior of metal food and beverage containers to prevent the contents from contacting the metal surface of the container. Contact with certain foods, particularly acidic products, can cause the metal container to corrode. This corrosion results in contamination and deterioration in the appearance and taste of the food or beverage product.
Corrosion problems are particularly acute with soups containing high levels of KCl such as chicken rice soup. Although coating compositions such as those based on polyglycidyl esters of bisphenol A can provide excellent corrosion protection for acidic food stuffs, coatings made with bisphenol A and derivatives thereof are problematic. These materials are perceived as being harmful to human health. Consequently there is a strong desire to eliminate these materials from coatings in contact with food stuffs.
Coatings based on oleoresinous materials such as organic oils are also known to provide excellent corrosion resistance; however, these coating compositions are organic solvent based and have high levels of volatile organic compounds (VOCs) that are also harmful to human health. It would be desirable to use aqueous-based coating compositions that have lower VOCs.
SUMMARY OF THE INVENTION
The present invention provides an aqueous-based coating composition suitable for coating the interior surface of a container in contact with food stuffs comprising:

    
    
        (A) a resinous phase comprising
        
            (i) an organic oil,
            (ii) an at least partially neutralized acid functional polymer containing reactive functional groups,
            (iii) a phenolic compound and an aldehyde or the reaction product thereof;
            the resinous phase dispersed in
        
        
        (B) aqueous medium.
    
    




DETAILED DESCRIPTION
As used herein, unless otherwise expressly specified, all numbers such as those expressing values, ranges, amounts or percentages may be read as if prefaced by the word “about”, even if the term does not expressly appear. Moreover, it should be noted that plural terms and/or phrases encompass their singular equivalents and vice versa. For example, “a” polymer, “a” crosslinker, and any other component refers to one or more of these components.
When referring to any numerical range of values, such ranges are understood to include each and every number and/or fraction between the stated range minimum and maximum.
As employed herein, the term “polyol” or variations thereof refers broadly to a material having an average of two or more hydroxyl groups per molecule. The term “polycarboxylic acid” refers to the acids and functional derivatives thereof, including anhydride derivatives where they exist, and lower alkyl esters having 1-4 carbon atoms.
As used herein, the term “polymer” refers broadly to prepolymers, oligomers and both homopolymers and copolymers. The term “resin” is used interchangeably with “polymer”.
The terms “acrylic” and “acrylate” are used interchangeably (unless to do so would alter the intended meaning) and include acrylic acids, anhydrides, and derivatives thereof, such as their C1-C5 alkyl esters, lower alkyl-substituted acrylic acids, e.g., C1-C2 substituted acrylic adds, such as methacrylic acid, ethacrylic acid, etc., and their C1-C5 alkyl esters, unless dearly indicated otherwise. The terms “(meth)acrylic” or “(meth)acrylate” are intended to cover both the acrylic/acrylate and methacrylic/methacrylate forms of the indicated material, e.g., a (meth)acrylate monomer. The terms “acrylic polymer” or “(meth)acrylic polymer” refer to polymers prepared from one or more acrylic monomers.
As used herein, the molecular weights are determined by gel permeation chromatography using a polystyrene standard. Unless otherwise indicated, molecular weights are on a number average basis (Mn).
The organic oil (i) can be an animal or vegetable oil having an iodine value of 10 to 180, such as tall oil, cotton seed oil, soybean oil, safflower oil, dehydrated castor oil, linseed oil, tung oil, cattlefish oil and sardine oil or animal or vegetable oils containing a hydroxyl group such as castor oil. Fatty acids of these oils and di- to tetra-mer oligomers of these oils can also be used.
The oil component (i) may be used singly, or if required, two or more such oil components (i) may be used in combination. The suitable amount of the component (i) is 5 to 50 percent by weight, such as 10 to 30 percent by weight, based on weight of resin solids in the coating composition. If the component (i) is used in an amount of more than 50 percent by weight, the amount of the unreacted oil component in the resin increases resulting in blush. If the amount of the component (i) is less than 5 percent by weight, corrosion resistance suffers.
The component (i) should have an iodine value of at least 100. If the iodine value is less than 100, the reactivity of the component (i) with (iii) is reduced, and consequently, corrosion resistance suffers. The iodine value may be considerably high, but animal and vegetable oils now commercially available have iodine values up to 210.
As indicated, one essential component of the compositions is an at least partially neutralized acid functional polymers containing reactive functional groups (ii). Examples of such functional groups are hydroxyl that are reactive with the phenolic compound-formaldehyde reaction product and N-alkoxymethylol groups that are also reactive with the phenolic compound reaction product and with each other. The acid functional polymer can be a (meth)acrylic polymer.
Among the monomers used in preparing the (meth)acrylic polymer are ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and maleic acid.
The ethylenically unsaturated carboxylic acid is used in amounts of 20 to 35 percent, such as 22 to 33 percent by weight based on total weight of monomer used in preparing the (meth)acrylic polymer.
The monomer with the reactive functional group can be selected from hydroxyalkyl esters of (meth)acrylic acid, typically containing 2 to 4 carbon atoms in the hydroxyalkyl group and from N-alkoxymethylol groups derived from (meth)acrylamide containing from 1 to 4 carbon atoms in the N-alkoxy group.
Examples include hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate and monomers of the structure:




where R1 is hydrogen or methyl and R2 is lower alkyl containing from 1 to 4 carbons. Specific examples of such monomers are N-ethoxymethyl (meth)acrylamide and N-butoxymethyl (meth)acrylamide.

The monomers containing the reactive functional groups are typically present in amounts of 0.2 to 30, such as 5 to 40 percent by weight based on total weight of monomers used in preparing the (meth)acrylic polymer.
Other monomers are usually used in preparing the (meth)acrylic polymer. Examples include aromatic monomers such as styrene and vinyl toluene that are present in amounts of up to 10, such as 35 percent by weight based on total weight of monomers used in preparing the (meth)acrylic polymer; alkyl esters of (meth)acrylic acid containing from 1 to 8 carbon atoms in the alkyl group, such as methyl (meth)acrylate, butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate that are present in amounts up to 15, such as 45 percent by weight based on total weight of monomers used in preparing the (meth)acrylic polymer.
The (meth)acrylic polymer is formed by free radical polymerization in the presence of a free radical initiator. Examples of initiators are azo compounds, such as, for example, alpha, alpha′-azobis(isobutyronitrile). Other useful initiators are tertiary-butyl perbenzoate, tertiary-butyl pivalate, isopropyl percarbonate, benzoyl peroxide and cumene hydroperoxide.
The (meth)acrylic polymer typically has a number average molecular weight of 3000 to 20,000, as determined by gel permeation chromatography using a polystyrene standard.
The partially neutralized acid functional polymer containing functional groups (ii) is usually present in the composition in amounts of 20 to 35, such as 25 to 30 percent by weight based on weight of resin solids in the coating composition. Amounts less than 20 percent by weight do not provide stable dispersions, whereas amounts greater than 35 percent by weight result in blistering of the film upon baking.
Component (iii) is a source of phenol and formaldehyde or the reaction product thereof. Examples of phenols are phenol, cresol, p-tert-butylphenol, p-octylphenol, p-nonylphenol and the source of formaldehyde can be paraformaldehyde.
The mole ratio of the formaldehyde-yielding substance to the phenol is suitably from 1.0 to 2.5, such as from 1.5 to 2.0.
The amount of component (iii) is usually 15 to 60 percent by weight, such as 20 to 35 percent by weight. If the amount of component (ill) exceeds 60 percent by weight, the coating becomes brittle and will fracture when the end, lid, is seamed on the can. Amounts less than 15 percent by weight result in poor corrosion resistance.
The above-mentioned ingredients in the resinous phase can be mixed together and heated, typically at 80 to 130° F. (27-54° C.) for 60 to 180 minutes. The ingredients can be heated neat or in organic solvent and the mixture partially neutralized with amine and dispersed in aqueous medium. Alternatively, the ingredients can be dispersed first in aqueous medium and heated at the above temperatures and times.
Also, component (i) can be condensed with at least a portion of component (iii) either in the form of a reaction product or in the form of a mixture of the phenolic compound and formaldehyde. Typically, this is done at 80 to 130° F. (27-54° C.).
When at least a portion of (i) and (iii) are condensed, the condensate is present in amounts of 5 to 60 percent by weight; the at least partially neutralized carboxylic acid group-containing acrylic polymer is present in amounts of 20 to 35 percent by weight and the phenol compound and the aldehyde or the reaction product thereof is present in amounts of 0 to 60 percent by weight.
The resin solids content of the aqueous-based coating composition is typically from 25 to 30 percent by weight.
The resulting product can then be combined with the acid functional polymer containing reactive functionality and the mixture dispersed in water with the aid of a neutralizing agent. Alternatively, the product can be mixed with an aqueous dispersion of component (ii).
Besides (i), (ii) and (iii), other resinous ingredients can be included in the resinous phase. Examples include polysilicone resins and amine functional polyamides, all of which further enhance adhesion and corrosion resistance of the coating.
The silicone resins that are used in the practice of the invention are functional silicone resins, that is, they contain functional groups that are reactive with functional groups associated with (iii). Typically, these groups are active hydrogen groups such as hydroxyl. Also, the silicone resins are typically phenylated silicone resins containing a C6H5—Si≡ bond. The phenyl group is beneficial in that it compatibilizes the silicone resin with the other resinous ingredients in the coating composition in that all of the resinous ingredients can be uniformly dissolved or dispersed in a diluent, that is, the silicone resin will not form a separate phase from the other resinous ingredients in the coating composition. The phenylated silicone resins typically used in the composition are alkyl-phenyl silsesquioxane resin as described in U.S. patent application Ser. No. 13/707,741, filed 7 Dec. 2012. When present, the polysilicone resin is present in amounts of up to 20 percent by weight based on weight of resin solids.
The amine-terminated polyamides are described in U.S. Pat. No. 7,475,786. When present, the amine-terminated polyamides are present in amounts of up to 20 percent by weight based on weight of resin solids.
The compositions of the invention are in the form of an aqueous dispersion in which the resinous phase is dispersed in aqueous medium. The aqueous medium of the dispersion may consist entirely of water in some cases but, more commonly, will consist of a mixture of water and water-soluble or water-miscible organic solvents. Suitable organic solvents are the ether type alcohols, such as ethylene glycol monobutyl ether (butyl Cellosolve), ethylene glycol monoethyl ether (ethyl Cellosolve) and the like, and lower alkanols having 2 to 4 carbon atoms such as ethanol, propanol, isopropanol, butanol, and the like. Minor proportions of hydrocarbon solvents such as xylene, toluene, and the like may also be present in the aqueous medium. The aqueous medium may contain from about 60 percent to about 100 percent by weight of water and from about 0 percent to about 40 percent by weight of organic solvent. The percentage by weight is based on total weight of the aqueous medium.
To disperse the resinous phase in the aqueous medium, the (meth)acrylic polymer is at least partially neutralized with a base such as an amine. Examples of amines include ammonia, monoethanolamine and diethanolamine. Typically, the amine will neutralize at least 25 percent, such as at least 50 percent of the acid equivalents in the (meth)acrylic polymer.
The other resinous ingredient can then be combined with the (meth)acrylic polymer salt and the mixture dispersed in the aqueous medium. The resin solids content of the aqueous dispersion is typically from 25 to 30, such as 26 to 28 percent by weight based on total weight of the aqueous dispersion.
In certain embodiments, the compositions used in the practice of the invention are substantially free, may be essentially free and may be completely free of bisphenol A and derivatives or residues thereof, including bisphenol A (“BPA”) and bisphenol A diglycidyl ether (“BADGE”). Such compositions are sometimes referred to as “BPA non intent” because BPA, including derivatives or residues thereof, are not intentionally added but may be present in trace amounts because of unavoidable contamination from the environment. The compositions can also be substantially free and may be essentially free and may be completely free of bisphenol F and derivatives or residues thereof, including bisphenol F and bisphenol F diglycidyl ether (“BPFG”). The term “substantially free” as used in this context means the compositions contain less than 1000 parts per million (ppm), “essentially free” means less than 100 ppm and “completely free” means less than 20 parts per billion (ppb) of any of the above-mentioned compounds, derivatives or residues thereof.
The coating compositions of the present invention can be applied to containers of all sorts and are particularly well adapted for use on food and beverage cans (e.g., two-piece cans, three-piece cans, etc.).
The compositions can be applied to the food or beverage container by any means known in the art such as roll coating, spraying and electrocoating. It will be appreciated that for two-piece food cans, the coating will typically be sprayed after the can is made. For three-piece food cans, a flat sheet will typically be roll coated with one or more of the present compositions first and then the can will be formed. As noted above, the percent solids of the composition can be adjusted based upon the means of application. The coating can be applied to a dry film weight of 24 mgs/4 in2 to 12 mgs/4 in2, such as 20 mgs/4 in2 to 14 mgs/4 in2.
After application, the coating is then cured. Cure is effected by methods standard in the art. For coil coating, this is typically a short dwell time (i.e., 9 seconds to 2 minutes) at high heat (i.e., 485° F. (252° C.) peak metal temperature); coated metal sheets typically cure longer (i.e., 10 minutes) but at lower temperatures (i.e., 400° F. (204° C.) peak metal temperature). For spray applied coatings on two-piece cans, the cure can be from 5 to 8 minutes, with a 90-second bake at a peak metal temperature of 415° F. (213° C.) to 425° F. (218° C.).
Any material used for the formation of food cans can be treated according to the present methods. Particularly suitable substrates include tin-plated steel, tin-free steel and black-plated steel.
The coatings of the present invention can be applied directly to the steel, without any pretreatment or adhesive aid being added to the metal first. In addition, no coatings need to be applied over top of the coatings used in the present methods.
The compositions of the present invention perform as desired both in the areas of adhesion and flexibility.
EXAMPLES
The following examples are offered to aid in understanding of the present invention and are not to be construed as limiting the scope thereof. Unless otherwise indicated, all parts and percentages are by weight.
Example A
A (meth)acrylic polymer was prepared by free radical polymerization in 2-butoxyethanol from the following monomer mixture: 20 percent by weight methacrylic acid, 25 percent by weight styrene, 50 percent by weight butyl acrylate and 5 percent by weight N-butoxymethylol acrylamide; the percentages by weight being based on total weight of monomers. The resulting polymer had an Mn of 3495 and a theoretical solids content of 52 percent by weight in 2-butoxyethanol.
Example B
An aqueous dispersion of a (meth)acrylic polymer was prepared by first preparing a (meth)acrylic polymer by free radical polymerization in n-butanol from the following monomer mixture: 30 percent by weight methacrylic acid, 25 percent by weight styrene, 43 percent by weight butyl acrylate and 2 percent by weight N-butoxymethylol acrylamide; the percentages by weight being based on total weight of monomers. The resulting polymer had an Mn of 10,600 and a theoretical solids content of 52 percent by weight in butanol. The polymer was partially neutralized (30 percent of the total theoretical neutralization) with dimethylethanolamine and dispersed in water at a theoretical solids content of 43.5 percent by weight.
Example 1
An aqueous coating composition was obtained by mixing together the following ingredients using a cowles disperser heating to obtain a stable dispersion.















Parts by



Ingredient
Weight



















Acrylic polymer of Example A
127.64



Phenolic resin1
484.2



Polyamide2
30.65



Silicone resin3
70.06



Linseed oil reacted with phenol and formaldehyde4
258.09



Acrylic polymer dispersion of Example B
600.41



Deionized water
763



Phenolic resin5
192.04



Deionized water
268



Caprylic acid
20



Deionized water
865







1Cresol-formaldehyde resin from Cytec as PR516.



2Amine-terminated polyamide from Momentive as EPIKURE 3115 (80% solids in butanol).



3Available from Dow Chemical as XIAMETER RSN255 (70% solids in butanol).



4Condensate of 42 percent by weight Linseed Oil, 43 percent by weight cresol and 15 percent by weight of formaldehyde.



5t-butyl phenol-formaldehyde resin from Durez as 29-401.






Example 2
An aqueous coating composition was obtained by mixing together the following ingredients and heating to obtain a stable dispersion.












Parts by


Ingredient
Weight
















Acrylic polymer of Example A
105.6


Cresol-formaldehyde phenolic resin of Example 1
618.6


Polyamide of Example 1
33.2


Linseed oil reacted with phenol and formaldehyde of
271.6


Example 1


Acrylic polymer dispersion of Example B
666


Deionized water
745


t-Butyl phenol-formaldehyde phenolic resin of Example 1
181


Deionized water
307


Caprylic acid
20


Deionized water
763









Example 3 (Comparative)
An aqueous coating composition similar to Example 1 was prepared but without the linseed oil reacted with phenol and formaldehyde.
The coating compositions of Examples 1-3 were spray applied to the interior surface of 211×400 electro tin plated steel 2-piece D&I cans at a film weight of 220 mg±10 mg and the can ends at a coating weight of 16-18 mg/4 in2. The coatings were cured by heating the can in a 4-zone IBO oven to achieve 400° F. (204° C.) on the dome (bottom of the can) for 90 seconds for 5 minutes total bake. The can ends were seamed onto the can body containing chicken rice soup filled to 1⁄2 inch (1.27 cm) head space. The can was steam processed for 90 minutes at 121° C. and stored at 120° F. (49° C.) for one week. The cans were removed from storage, cooled and cut open with four vertical cuts from top to bottom and flattened to resemble a cross and the interior coated surfaces of the can evaluated for adhesion and corrosion protection, both of which were measured on a sale of 0 to 10. Adhesion testing is performed according to ASTM D-3359, Test Method B, using SCOTCH 610 tape. A reading of 10 indicates no adhesion failure, a reading of 9 indicates 90 percent of the coating remained adhered, and a reading of 0 indicates complete adhesion failure. For corrosion protection, a “0” indicates the coating is completely corroded, observed by bubbling or blistering of the film in all areas. A “10” indicates no evidence of corrosion. Evidence of corrosion was evaluated in the head space area that is the most difficult part of the 2-piece can to get corrosion resistance because it contains the least amount of tin plating due to the drawing process.
The results of the testing on three cans are reported in the Table below.







TABLE







Adhesion and Corrosion Testing Results









Coating




Example
Adhesion
Corrosion












1
10
10


1
10
10


1
10
9.9


2
10
9


2
10
9


2
10
9


3
9
10


3
10
7.7


3
10
5.6

## Claims

1. An aqueous-based coating composition comprising:
(A) a resinous phase of
(i) 10 to 30 percent by weight of an organic oil,
(ii) 20 to 35 percent by weight of an at least partially neutralized acid functional polymer containing reactive functional groups,
(iii) 15 to 60 percent by weight of a phenolic compound and an aldehyde or the reaction product thereof;
the resinous phase dispersed in

(B) aqueous medium;

the percentages by weight being based on weight of resin solids in the coating composition.

2. The aqueous-based coating composition of claim 1 in which (i), (ii) and (iii) are heated together.

3. The aqueous-based coating composition of claim 2 in which (i), (ii) and (iii) are heated together at 80 to 130° F. (27 to 54° C.).

4. The aqueous-based coating composition of claim 3 in which (i), (ii) and (iii) are heated together for 60 to 180 minutes.

5. The aqueous-based coating composition of claim 1 in which the phenolic compound and the aldehyde are condensed and at least a portion of the resulting condensate is reacted with the organic oil at 80 to 130° F. (27 to 54° C.).

6. The aqueous-based coating composition of claim 1 in which at least a portion of the phenolic compound, at least a portion of the aldehyde and at least a portion of the organic oil are heated together simultaneously at 80 to 130° F. (27 to 54° C.).

7. The aqueous-based coating composition of claim 1 in which the phenolic compound is selected from the group consisting of phenol and an alkylated phenol.

8. The aqueous-based coating composition of claim 1 in which the aldehyde is formaldehyde.

9. The aqueous-based coating composition of claim 1 in which the organic oil has an iodine number of 10 to 180.

10. The aqueous-based coating composition of claim 1 in which the organic oil is a vegetable oil.

11. The aqueous-based coating composition of claim 1 in which the organic oil is tung oil.

12. The aqueous-based coating composition of claim 1 in which the acid functional polymer is a copolymer of (meth)acrylic monomers.

13. The aqueous-based coating composition of claim 1 in which the acid groups are carboxylic acid groups.

14. The aqueous-based coating composition of claim 12 in which the reactive functional groups are selected from hydroxyl and N-alkoxymethylol groups.

15. The aqueous-based coating composition of claim 1 containing an amine-terminated polyamide in the resinous phase.

16. The aqueous-based coating composition of claim 1 containing a polysilicone resin in the resinous phase.

17. The aqueous-based coating composition of claim 1 containing a copolymer of (meth)acrylic monomers free of acid functionality and containing reactive functional groups.

18. A coated article comprising:
(A) a substrate and
(B) a coating deposited on at least a portion of the substrate from the composition of claim 1.

19. The coated article of claim 18 in which the substrate is a container.

20. The coated article of claim 19 in which the container is a food or beverage container.

21. The coated article of claim 20 in which the coating is on the interior surface of the container.

22. The coated article of claim 18, wherein the at least a portion of the substrate comprises a metal surface.

23. The coated article of claim 22, wherein the coating is deposited directly onto the metal surface.

24. The coated article of claim 23, wherein the coating is free from a subsequently applied top coating.

25. The aqueous-based coating composition of claim 1 further comprising a functional silicone resin in the resinous phase, the functional silicone resin having a functional group that is reactive with (iii).

26. The aqueous-based coating composition of claim 25, wherein the functional group is hydroxyl.

27. The aqueous-based coating composition of claim 25, wherein the functional silicone resin comprises a phenyl group.

28. The aqueous-based coating composition of claim 26, wherein the functional silicone resin comprises a phenyl group.