Aqueous dispersions and coatings

[0001] A variety of coatings are used to coat the surface of packaging articles (e.g., food and beverage cans). For example, metal cans are sometimes coated using "coil coating" technology, i.e. a flat sheet of a suitable substrate (e.g., steel or metallic aluminum) is coated with a suitable composition and cured. A lid or can body is then formed from the coated substrate. The substrate may optionally be applied with liquid coating compositions (e.g. by spraying, dipping, rolling, etc.) and then cured.

[0002] Packaging films should preferably be capable of being applied to the substrate at a high rate and provide suitable properties after hardening in order to obtain the desired parameters with such a demanding end use. For example, the coating should be safe in contact with food, have excellent adhesion to the substrate and be resistant to degradation for a long time, even if it is exposed to harsh environmental conditions.

they do not cause any health risk to people, some believe that these relationships are potentially harmful to human health. Therefore, there is a significant desire to eliminate these compounds from coatings in contact with food.

[0004] From the foregoing, it should be understood that there is a need in the art for a packaging container (e.g. a food or beverage can) coated with a composition not containing amounts of such compounds that could be extracted. Such packaging, compositions and methods for making them are disclosed and claimed herein.

Summary [0005] The present invention relates to new aqueous dispersions suitable for use as coating compositions as well as methods for coating substrates using these dispersions.

[0006] The dispersion according to the present invention preferably comprises a reaction product of the oxirane vinyl addition polymer (s); (ii) an acid-functional polymer (e.g., a vinyl acid addition polymer addition polymer or an acid-functional polyester resin); and (iii) a tertiary amine. The reaction product is preferably dispersed in a carrier (e.g., water) together with optional crosslinking agents and other optional adjuvants. Preferred compositions and dispersions substantially do not contain mobile BPA and derivatives of aromatic glycidyl ethers (e.g., BADGE, BFDGE and epoxide Novalac).

[0007] In one embodiment, the method comprises: providing a vinyl oxirane-functional adduct polymer in which the oxirane functional group content is 0.5 to 5; providing a polymer with acid functional groups, whose acid number is 30 to 500; performing a reaction of an oxirane vinyl addition polymer with an acidic functional group in the presence of a tertiary amine to form a water-dispersible polymer; and dispersing the water-dispersible polymer in a water-containing carrier.

[0008] In one presently preferred embodiment: (i) a vinyl polymer with oxirane functional groups is the reaction product of 1 to 10 wt.%. monomer with oxirane functional groups, 0 to 60% by weight a monomer with hydroxyl functional groups and the remainder is another monomer (e.g., a monomer lacking a functional group); and the polymer has an oxirane functional group content of 0.5 to 5 and a molecular weight average of 2500 to 20,000; (ii) an acid-functional polymer is a vinyl polymer formed as a reaction product of an acid-functionalized monomer (more preferably at least 15 wt.% of an acidic functional monomer) and the remainder is another monomer (e.g., a non-functional monomer); and the polymer has an acid number of 30 to 500 (more preferably 100 to 500) and a molecular weight average of 2000 to 15,000; (iii) the tertiary amine is dimethyl ethanolamine or the like; (iv) wherein the reaction of the above polymers in the presence of a tertiary amine to form at least some quaternary ammonium salt, the weight ratio (i) :( ii) is 90:10 to 50:50 and the ratio of amine to oxirane groups is 0, 8: 1 to 5: 1; and (v) reacted polymers are dispersed in water.

[0009] In another embodiment, the present invention provides a method which comprises: providing a vinyl oxirane-functional adduct polymer in which the oxirane functional content is 0.5 to 5; providing a polymer with acid functional groups, whose acid number is 30 to 500; providing a tertiary amine; combining the polymer with acid functional groups with a tertiary amine to form a mixture and at least partially neutralizing the polymer with acid functional groups; and a combination of an oxirane functional vinyl addition polymer and this mixture to form a water-dispersible polymer; and dispersing the water-dispersible polymer in a water-containing carrier. In some embodiments, the mixture is added to the oxirane functional vinyl addition polymer for a period of time. [0010] In another embodiment, the present invention provides a method that comprises: providing a first set of monomers for preparing an oxirane functional oxirane vinyl addition polymer in which the oxirane functional group content is 0.5 to 5; providing a second set of monomers for preparing an acid-functional polymer having an acid number of 30 to 500; tierccey tiarcceenee; polymerizing at least one set of monomers to form the first polymer; polymerizing a second set of monomers in the presence of a first polymer; addition of a tertiary amine to form a water-dispersible polymer; and dispersing the water-dispersible polymer in a water-containing carrier. In some embodiments, the polymerization of at least one set of monomers occurs in the presence of a second set of monomers. Alternatively, in some other embodiments, the polymerization of at least one set of monomers occurs prior to the addition of a second set of monomers. The present invention also provides a composition comprising an aqueous dispersion of a quaternary ammonium salt, the salt comprising a reaction product of an oxirane functional vinyl addition polymer, in which the oxirane functional content is 0.5 to 5; an acid functional polymer having an acid number of 30 to 500; and tertiary amine. [0012] In another embodiment, the present invention includes a coating composition comprising: an aqueous dispersion of a quaternary ammonium salt, the salt comprising a reaction product of an oxirane functional vinyl addition polymer in which the oxirane functional content is 0.5 to 5; an acid functional polymer having an acid number of 30 to 500; and tertiary amine; and a crosslinking agent.

[0013] The present invention provides methods for coating an article. Such methods include applying the composition of the present invention to the surface of the substrate and curing this composition.

[0014] The present invention also provides products. In one embodiment, the article comprises a substrate on which there is an uncured thin layer, wherein the thin layer comprises an aqueous dispersion of a quaternary ammonium salt, the salt comprising a reaction product of an oxirane functional vinyl addition polymer in which the oxirane functional content is 0. , 5 to 5; an acid functional polymer having an acid number of 30 to 500; and tertiary amine. In some embodiments, the uncured thin layer further comprises a crosslinking agent.

[0015] In another embodiment, the article comprises a substrate on which a cured thin film is provided, wherein the cured film may be made from a coating composition comprising an aqueous dispersion of a quaternary ammonium salt, the salt comprising a reaction product of an oxirane functional vinyl addition polymer. wherein the oxirane functional group content is 0.5 to 5; an acid functional polymer having an acid number of 30 to 500; tertiary amine; and optionally a crosslinking agent.

[0016] In another embodiment, the article comprises a substrate on which a cured thin film is provided, wherein the cured film comprises a cross-linked polymer comprising a cross-linked segment of general formula:

YC (R 2) -C (R) (OH) -C (R2) -O- (O) CX_r- wherein: Y is a divalent organic group, more preferably a divalent organic group containing a C (O) O moiety; X is a divalent organic group; R is H or a C1 to C6 organic group, preferably H; and r is 0 or 1, preferably 0.

Definitions [0017] The term "substantially free" of a specific mobile compound means that the compositions of the present invention contain less than 1000 parts per million (ppm) of the mobile compound administered. The term "substantially free" of a specific mobile compound means that the compositions of the present invention contain less than 100 parts per million (ppm) of the mobile compound administered. The term "substantially does not contain any" specific mobile compound means that the compositions of the present invention contain less than 5 parts per million (ppm) of the mobile compound administered. The term "does not contain any" specific mobile compound means that the compositions of the present invention contain less than 20 parts per billion (ppb) of the stated mobile compound.

[0018] The term "mobile" means that the compound can be extracted from the cured coating when such a coating (typically approximately 1 mg / cm thick).²) will be treated with an ethanol solution at 10 weight percent for two hours at 121 ° C, followed by exposure for 10 days in solution at 49 ° C. [0019] If the above phrases are used without the term "mobile" (e.g. "substantially free of XYZ compound"), then the compositions of the present invention contain less than the amount of compound specified before, regardless of whether the compound is mobile in the coating, or associated with the coating component.

[0020] The term "organic group" means a hydrocarbon (i.e., hydrocarbyl) group with optional elements other than carbon and hydrogen in the chain, such as oxygen, nitrogen, sulfur and silicon, classified as an aliphatic group, a cyclic group or a combination of aliphatic and cyclic groups (e.g., alkaryl and aralkyl groups). The term "aliphatic group" means a saturated or unsaturated linear or branched hydrocarbon group. This term is used to refer to, for example, alkyl, alkenyl and alkynyl groups. The term "alkyl" means a saturated linear or branched hydrocarbon group, including for example methyl, ethyl, isopropyl, t-butyl, heptyl, dodecyl, octadecyl, amyl, 2-ethylhexyl and the like. The term "alkenyl" means an unsaturated linear or branched hydrocarbon group with one or more carbon-carbon double bonds, for example a vinyl group. The term "alkynyl" means an unsaturated linear or branched hydrocarbon group with one or more carbon-carbon triple bonds. The term "cyclic group" means a hydrocarbon group with a closed ring classified as an alicyclic group, an aromatic group or a heterocyclic group. The term "alicyclic group" means a cyclic hydrocarbon group having properties similar to that of aliphatic groups. The term "aromatic group" or "aryl group" means a mono- or polycyclic aromatic hydrocarbon group. The term "heterocyclic group" means a hydrocarbon with a closed ring, wherein one or more atoms in the ring is an element other than carbon (e.g., nitrogen, oxygen, sulfur, etc.). Substitution is envisaged for the groups of organic polymers used in the coating compositions of the present invention. In order to simplify the discussion and exchange of some terms used throughout the present application, the terms "group" and "moiety" are used to distinguish chemical entities that allow substitution or substitutions, and those that do not allow substitution or which can not be substituted. . Accordingly, when the term "group" is used in the description of a chemical substituent, the chemical material described includes an unsubstituted group and a group containing, for example, O, N, Si or S atoms in the chain (as in an alkoxy group), and carbonyl groups or other conventional substituents. If the term "moiety" is used in the description of a compound or a chemical substituent, only the unsubstituted chemical material is included. For example, the term "alkyl" is intended to include not only pure saturated, open chain alkyl hydrocarbon substituents, e.g. methyl, ethyl, propyl, t-butyl and the like, but also alkyl substituents containing further substituents known in the art, such as hydroxyl. , alkoxy, alkylsulfonyl, halo, cyano, nitro, amino, carboxy, etc. Accordingly, the "alkyl" group contains ether groups, haloalkyls, nitroalkyls, carboxylalkyls, hydroxyalkyls, sulfoalkyls, and the like. On the other hand, the term "alkyl moiety" is limited and includes only pure saturated hydrocarbon alkyl substituents with an open chain, e.g. methyl, ethyl, propyl, t-butyl and the like. The term "hydrocarbyl moiety" means unsubstituted organic moieties containing only hydrogen and carbon.

[0021] The terms "vinyl addition polymer" or "vinyl addition copolymer" as used herein are meant to include acrylate, methacrylate and vinyl polymers and copolymers. Unless otherwise specified, the term "polymer" is also intended to include a copolymer. Unless otherwise specified, the term "(meth) acrylate" derivative (where "met" is in brackets) is intended to include derivatives of both acrylates and methacrylates.

[0022] The term "dispersible" in the context of a dispersible polymer means that this polymer can be mixed with the carrier to form a macroscopic homogeneous mixture without the use of high shear mixing. The term "dispersible" is meant to include the term "soluble". In other words, the soluble polymer is also a dispersible polymer.

[0023] The term "water-dispersible" in the context of a water-dispersible polymer means that this polymer can be mixed with water to form a macroscopic homogeneous mixture without the use of high shear mixing. The term "water-dispersible" is meant to include the term "water-soluble". In other words, the water-soluble polymer is also considered to be a water-dispersible polymer.

[0024] The term "dispersion" in the context of a dispersible polymer refers to a mixture of a dispersible polymer and a carrier. The term "dispersion" is intended to include the term "solution".

Detailed description of illustrative embodiments The present invention provides new dispersions (e.g., waterborne dispersions) suitable for use as coating compositions as well as methods for coating substrates using these dispersions. Preferred dispersions include a water dispersible polymer comprising oxirane and acid groups and a water containing carrier.

[0026] In one particular embodiment, the dispersion comprises the reaction product of the oxirane vinyl addition polymer (s); (ii) an acid functional polymer; and (iii) a tertiary amine. This reaction product is dispersed in a carrier (e.g., water) together with optional crosslinking agents and other optional adjuvants.

[0027] Thus, in one embodiment, the water-dispersible polymer is formed from pre-formed polymers (e.g., an oxirane-functional vinyl addition polymer and acid-functional polymer) in the presence of a tertiary amine. In another embodiment, the water-dispersible polymer is formed from at least one pre-formed polymer (e.g., an oxirane-functional vinyl addition polymer or acid-functional polymer) that has reacted with monomers to prepare another polymer in the presence of a tertiary amine. In another embodiment, the water-dispersible polymer is formed from a reaction mixture in which at least one polymer (e.g. an oxirane vinyl addition polymer or acid-functional polymer) is formed in situ prior to reaction with the monomers for the preparation of another polymer in the presence of a tertiary amine. If desired, the acid-functional polymer can be combined with the tertiary amine and the derivatives more preferably to at least partially neutralize it prior to reaction with an oxirane polymer or monomers to form an oxirane polymer.

[0028] Preferred compositions and dispersions essentially do not contain mobile BPA and derivatives of aromatic glycidyl ethers (e.g., BADGE, BFDGE and epoxide Novalac), more preferably essentially do not contain these compounds, even more preferably substantially do not contain these compounds and most preferably not at all they contain these compounds. The coating composition further preferably contains essentially no bound BPA aromatic glycidyl ethers, essentially free of these compounds, most preferably substantially none of these compounds, and optimally does not contain these compounds at all.

[0029] Suitable vinyl oxirane addition polymer polymers include acrylate, methacrylate and / or vinyl polymer copolymers containing oxirane functional groups (including, for example, (meth) acrylate copolymers containing pendant glycidyl groups).

[0030] In one embodiment, the oxirane vinyl addition polymer is formed by reacting one or more monomers with an oxirane functional group, optionally hydroxyl functional monomers, and one or more other monomers (e.g., monomers with no functional group). ). This reaction is conveniently carried out in solution, although other methods without solvent may be used if desired. [0031] Suitable oxirane monomers include monomers containing a carbon-carbon double reactor and an oxirane (i.e., glycidyl) group. The monomer is the glycidyl ester quartz of zlfz, the beta-non-saturated lrb of its anhydride. Suitable unfiltered, betz-unsaturated acids include dicarboxylic acid monocarboxylic acids.

[0032] Specific examples of suitable glycidylgroup containing monomers include glycidyl (meth) acrylate (i.e., glycidyl methacrylate and glycidyl acrylate), mono- and diglycidyl itaconate, mono- and diglycidyl maleate and mono- and diglycidyl formate. It is also contemplated that as the monomer with oxirane fractions, allyl glycidyl ether and vinyl glycidyl ether can be used. The preferred monomer is glycidyl methacrylate ("GMA").

[0033] It should furthermore be contemplated that the vinyl addition polymer with oxirane fractions may initially be a copolymer of alpha, beta-unsaturated acid and (meth) acrylate alkylr which is then reacted with the hr halogenide by tosylate glycidyl, e.g. glycidyl chloride, so that side glycidyl grindles were on the acrylate copolymer. The alpha, beta-unsaturated carboxylic acid may, for example, be the acid mentioned above. In an alternative embodiment, a vinyl addition polymer with side hydroxyl groups is first formed. The vinyl addition polymer containing side hydroxyl groups can be prepared by introducing a monomer such as 2-hydroxyethyl methacrylate or methacrylate.

3-hydroxypropyl, for the vinyl addition polymer. The polymer is then reacted so that the side glycidyl groups are on the polymer.

The amount of the oxirane functional monomer used to form the oxirane functional vinyl addition polymer depends on the desired number of oxirane functional groups and the desired molecular weight of the polymer, as well as the mass of the monomer used with the oxirane functional groups. It is now believed that the oxirane functional group content of the polymer formed is at least 0.5, preferably at least 0.9, more preferably at least 1.2 and most preferably at least 1.4. It is now believed that the content of oxirane functional groups in the polymer formed is respectively at most 5, preferably at most 3, more preferably at most 2.5 and most preferably at most 2. Without intention of limiting to a particular theory, it is believed that

[0035] Also, it is also believed that for molecular coating applications, the number average molecular weight (M._n) of an oxirane vinyl addition polymer is at least at least 2,500, preferably at least 4,000, more preferably at least 5,000 and most preferably at least 6,000. It is also now believed that for packaging applications, the number average molecular weight (Mn) of the vinyl addition polymer with oxirane functional groups is at most 20,000, preferably at most 16, 000, more preferably at most 12,000, and most preferably at most 8,000, respectively.

Using the above oxirane functional group content as a guide and using an oxirane monomer with a molecular weight similar to GMA in the case of an oxirane functional polymer with a value of M_n 7000 the amount of oxirane functional monomer to be used is at least 1, preferably at least 2, more preferably at least 2.5 and most preferably at least 3 wt.%, based on the weight of the remaining monomers used to form the polymer. Utilizing the above oxirane functional group contents as a guide and using an oxirane monomer with a molecular weight similar to GMA for an oxirane polymer with a Mn value of 7000, the amount of monomer with oxirane functional groups used is at most 10, preferably at most 5 , more preferably at most 4 and most preferably at most 3.5 wt%, based on the weight of the remaining monomers used to form the polymer.

[0037] The oxirane functional monomer is preferably reacted with suitable other monomers (and optional hydroxyl functional monomers). Suitable other monomers include alkyl (meth) acrylates, vinyl monomers, and the like. [0038] Suitable alkyl (meth) acrylates include compounds having the structure CH2 = C (R.¹) -CO-OR²in which R¹is hydrogen or methyl; and R2 is an alkyl group having preferably one to sixteen carbon atoms. The group r2 may be substituted with one or more, usually one to three, moieties, such as, for example, hydroxy, halo, phenyl and alkoxy. Suitable alkyl (meth) acrylates therefore include hydroxyalkyl (meth) acrylates. The (meth) alkyl acrylate is typically an acrylic or methacrylic acid ester. R 1 is preferably hydrogen or methyl and R 2 is an alkyl group containing two to eight carbon atoms. R1 is most preferably hydrogen or methyl and R2 is an alkyl group containing two to four carbon atoms. Examples of suitable alkyl (meth) acrylates include, without limitation thereto, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate,

Suitable vinyl monomers include styrene, methylstyrene, halostyrene, isoprene, diallyl phthalate, divinylbenzene, butadiene conjugate, alpha-methylstyrene, vinyltoluene, vinylnaphthalene and mixtures thereof. The vinyl aromatic monomers described below in connection with an acid functional polymer are also suitable for use in the polymer. Styrene is currently a preferred vinyl monomer, in part due to its relatively low cost. Preferred oxirane functional polymers are obtained with a maximum of 99% by weight, more preferably up to 80% by weight. and most preferably up to 70 wt.%. vinyl monomers or monomers, relative to the total weight of the monomers. Preferred oxirane polymers with a functional group are obtained with at least 30 wt.%, More preferably at least 40 wt.%. and most preferably at least 50 wt.%. vinyl monomers or monomers, relative to the total weight of the monomers. [0040] Other suitable polymerizable vinyl monomers include acrylonitrile, acrylamide, methacrylamide, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, isobutoxymethylacrylamide and the like.

[0041] In preferred embodiments, the polymer is formed using one or more hydroxyl functional optional monomers (e.g., hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), hydroxypropyl (meth) acrylate (HPMA), etc.). The monomer content of the hydroxyl functional groups is usually chosen so as to obtain the desired number of hydroxyl functional groups. Preferred oxirane functional polymers are prepared with at least 10 wt.%, More preferably at least 15 wt.%. and most preferably at least 30 wt.%. monomer (monomers) with hydroxyl functional groups (if used) relative to the total weight of the monomers used. Preferred oxirane functional polymers are made with at most 60 wt%, more preferably at most 50 wt%. and most preferably at most 45% by weight. monomer (monomers) with hydroxyl functional groups (if used) relative to the total weight of the monomers used.

The above-mentioned monomers may be polymerized by standard free radical polymerization methods, e.g. using initiators such as azoalkanes, peroxides or peroxyesters to provide an oxirane polymer having a number average molecular weight (Mn) of at least 2,500, preferably at least 4,000 more preferably at least 5,000 and most preferably at least 6,000. The above-mentioned monomers can be polymerized by standard free radical polymerization methods, e.g. using initiators such as azoalkanes, peroxides or peroxyesters to obtain an oxirane functional polymer having a number average molecular weight (Mn) of at most 20,000, preferably at most 16,000, more preferably at most 12,000, and most preferably at most 8,000.

[0043] This reaction can be carried out if necessary using appropriate solvents.

[0044] In one preferred general embodiment, the oxirane vinyl addition polymer addition polymer can be prepared from a reaction mixture comprising (in weight ratio) 30 to 70 parts styrene; 3 to 10 parts glycidyl (meth) acrylate; and 30 to 70 parts of hydroxyalkyl (meth) acrylate. In one specific embodiment, the oxirane vinyl addition polymer addition polymer can be made from a reaction mixture comprising (in a weight ratio) 50 parts of styrene; 5 parts of GMA; and 45 parts of HEMA. In another specific embodiment, this polymer can be made from a reaction mixture comprising (in a weight ratio) 55 parts of styrene; 3 parts of GMA; and 42 parts of HEMA. These embodiments illustrate suitable such polymers with oxirane functional groups.

[0045] It has been found that the preferred oxirane functional polymers are close to or exceed the properties of the traditional type 1007 epoxy resin (i.e., the resin of the same type as the RESOLUTION'S EPON 1007 epoxy resin, which has a number average molecular weight of 3600 to 4400 and average molecular weight). weighting 12,000 to 16,000); a type 1009 epoxy resin (i.e., a resin of the same type as the RESOLUTION'S EPON 1009 epoxy resin, which has a number average molecular weight of 4,200 to 5,000 and a weight average molecular weight of 14,000 to 18,000); and a 9-A-9 type epoxy resin (i.e. a resin obtained by reacting a type 1009 epoxy resin with an adipic acid that has a molecular weight number average of 7,000 to 8,000 and a weight average molecular weight of 24,000 to 29,000),

[0046] Suitable acid-functional polymers include polyacid or polyanhydride polymers, e.g. homopolymers or copolymers made from ethylene unsaturated acid or anhydride monomers (e.g., carboxylic acid or carboxylic anhydride monomers) and other optional monomers (e.g.

vinyl monomers). It is further envisaged that polyester polymers with acid functional groups can be used.

[0047] Preferred acid-functional polymers used in the present invention include polymers prepared by conventional free radical polymerization methods with at least 15 wt.%, More preferably at least 20 wt.%, Unsaturated monomer with acidic functionality, the remainder being a different monomer. insatiable. The choice of unsaturated monomer (s) depends on the intended use of the final coating composition and is virtually unlimited. The reaction is suitably carried out in solution, although other methods without solvent may be used if desired. Low molecular weight polymers are preferred for some applications, as discussed herein.

[0048] A series of monomers with an acidic functional group and an anhydride functional group may be used; their choice depends on the desired properties of the final polymer. Suitable monomers with acidic functional groups and ethylene unsaturated anhydride monomers in the present invention include monomers having a reactive carbon-carbon double bond and an acid or anhydride group. Preferred such monomers contain 3 to 20 carbon atoms, 1 to 4 sites of unsaturation, and 1 to 5 acid or anhydride groups or salts thereof.

Suitable acidic functional monomers include those with ethylenically unsaturated (monoprotic or diprotic), anhydrides or monoesters of dibasic acid that are copolymerized with the optional other monomer (s) used to make the polymer. Examples of monobasic acids are the acids represented by the structure CH2 = C (R.³ ) -COOH, in which R³ is hydrogen or an alkyl group having from 1 to 6 carbon atoms. Suitable dibasic acids include those represented by the formula R⁴ (COOH) C = C (COOH) R⁵ and R⁴ (R⁵) C = C (COOH) R⁶COOH, in which R⁴ and R⁵ is hydrogen, an alkyl group having 1-8 carbon atoms, a halogen, a cycloalkyl having 3 to 7 carbon atoms, or a phenyl, and R⁶ means an alkylene group having 1 to 6 carbon atoms. Also suitable are half-esters of these acids with alkanols having 1 to 8 carbon atoms.

Non-limiting examples of useful acid-functionalized ethylenically unsaturated monomers include acids such as, for example, acrylic acid, methacrylic acid, alpha-chloroacrylic acid, alpha-cyanoacrylic acid, crotonic acid, alpha-phenylacrylic acid, beta-acryloxypropionic acid. , fumaric acid, maleic acid, sorbic acid, alpha-chlorosorbic acid, angelic acid, cinnamic acid, p-chlorocinnamic acid, beta-stearyloacrylic acid, citraconic acid, mezaconic acid, glutaconic acid, aconitic acid, tricarboxyethylene, 2-methylmaleic acid, itaconic acid, 2-methyl-acetic acid, methylene glutaric acid and the like, or mixtures thereof. Preferred unsaturated acid-functional monomers include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methylmaleic acid, itaconic acid, 2-methyl-acetic acid and mixtures thereof. Preferred unsaturated acid-functional monomers include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid and mixtures thereof. The most preferred unsaturated acid-functional monomers include acrylic acid, methacrylic acid, maleic acid, crotonic acid and mixtures thereof. [0051] Non-limiting examples of suitable ethylenically unsaturated anhydride monomers include compounds derived from the above acids (e.g., in the form of the pure anhydride or mixtures thereof). Preferred anhydrides include acrylic anhydride, methacrylic anhydride and maleic anhydride. If desired, salts of the above acids can also be used. Preferred unsaturated acid-functional monomers include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid and mixtures thereof. The most preferred unsaturated acid-functional monomers include acrylic acid, methacrylic acid, maleic acid, crotonic acid and mixtures thereof. [0051] Non-limiting examples of suitable ethylenically unsaturated anhydride monomers include compounds derived from the above acids (e.g., in the form of the pure anhydride or mixtures thereof). Preferred anhydrides include acrylic anhydride, methacrylic anhydride and maleic anhydride. If desired, salts of the above acids can also be used. Preferred unsaturated acid-functional monomers include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid and mixtures thereof. The most preferred unsaturated acid-functional monomers include acrylic acid, methacrylic acid, maleic acid, crotonic acid and mixtures thereof. [0051] Non-limiting examples of suitable ethylenically unsaturated anhydride monomers include compounds derived from the above acids (e.g., in the form of the pure anhydride or mixtures thereof). Preferred anhydrides include acrylic anhydride, methacrylic anhydride and maleic anhydride. If desired, salts of the above acids can also be used. maleic acid, itaconic acid and mixtures thereof. The most preferred unsaturated acid-functional monomers include acrylic acid, methacrylic acid, maleic acid, crotonic acid and mixtures thereof. [0051] Non-limiting examples of suitable ethylenically unsaturated anhydride monomers include compounds derived from the above acids (e.g., in the form of the pure anhydride or mixtures thereof). Preferred anhydrides include acrylic anhydride, methacrylic anhydride and maleic anhydride. If desired, salts of the above acids can also be used. maleic acid, itaconic acid and mixtures thereof. The most preferred unsaturated acid-functional monomers include acrylic acid, methacrylic acid, maleic acid, crotonic acid and mixtures thereof. [0051] Non-limiting examples of suitable ethylenically unsaturated anhydride monomers include compounds derived from the above acids (e.g., in the form of the pure anhydride or mixtures thereof). Preferred anhydrides include acrylic anhydride, methacrylic anhydride and maleic anhydride. If desired, salts of the above acids can also be used. [0051] Non-limiting examples of suitable ethylenically unsaturated anhydride monomers include compounds derived from the above acids (e.g., in the form of the pure anhydride or mixtures thereof). Preferred anhydrides include acrylic anhydride, methacrylic anhydride and maleic anhydride. If desired, salts of the above acids can also be used. [0051] Non-limiting examples of suitable ethylenically unsaturated anhydride monomers include compounds derived from the above acids (e.g., in the form of the pure anhydride or mixtures thereof). Preferred anhydrides include acrylic anhydride, methacrylic anhydride and maleic anhydride. If desired, salts of the above acids can also be used.

[0052] Suitable other monomers include the above-mentioned alkyl (meth) acrylates, vinyl monomers and the like. It is generally preferred to avoid monomers with an amine functional group.

[0053] Vinyl aromatic monomers are preferably copolymerized with acid functional monomers. Suitable such monomers include the monomers represented by the structure Ar-C (R.⁸) = C (R⁹) (R¹⁰) in which R⁸, R⁹ and R¹⁰ are hydrogen or an alkyl group having from 1 to 5 carbon atoms and Ar is a substituted or unsubstituted roomatic group. Examples of these monomers are styrene, methylstyrene, vinyltoluene and the like. These vinyl aromatic monomers can be 0-80% polymer with acid functional groups, preferably 5-50% and most preferably 5-40%.

[0054] Other commonly used monomers are unsaturated nitriles represented by the structure: Rii (Ri²) C = C (R³) -CN, in which Rⁿ and Ri² are hydrogen, an alkyl group having and up to 8 carbon atoms, a tolyl group, a benzyl or a phenyl group, and the R group^at means hydrogen or methyl. The most commonly used are acrylonitrile and methacrylonitrile. The nitrile monomer may be 0-40% based on the acid functionalized polymer.

[0055] Other suitable monomers are esters of acrylic acid, methacrylic acid or a mixture thereof with C1-C16 alkanols. Preferred esters are methyl, ethyl, propyl, n-butyl, isobutyl and 2-ethylhexyl esters of acrylic acid or methacrylic acid or a mixture of such esters.

[0056] It is also possible to use hydroxyalkyl (meth) acrylate monomers, for example hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate or mixtures thereof.

[0057] For some applications, it may be desirable to include acrylamide, methacrylamide or N-alkoxymethyl (meth) acrylamide, such as N-isobutoxymethyl (meth) acrylamide in the polymer. The polymer containing the copolymerized acrylamide or methacrylamide can then optionally be reacted with formaldehyde and an alkanol to form an N-alkoxymethyl polymer. [0058] Acidic acid functional polymers can be prepared by polymerizing the appropriate monomers, in appropriate amounts, in a suitable carrier (e.g., in an organic liquid medium). The liquid medium for polymerization is preferably a mixture of alcohols. The polymerization catalyst or initiator is typically used in the polymerization of acid-functional polymers in typical amounts. It can be any free radical initiator.

[0059] Suitable acid-functional polymers have an acid value (AN) of at least 30, preferably at least 100, more preferably at least 150, and most preferably at least 200 mg KOH / gram of solid. Suitable acid-functional polymers have an acid value (AN) of at most 500, preferably at most 400, more preferably at most 350 and most preferably at most 320 mg KOH / gram of substance and solid. For example, 23 percent by weight MAA gives a polymer having an AN of approximately 150.

[0060] Suitable polymers with acid functional groups have a number average molecular weight (M_nAt least 2000, preferably at least 3000, more preferably at least 4000 and most preferably at least 5000. Suitable acid-functional polymers have a number average molecular weight (Mn) of at most 15,000, preferably at most 12,000, more preferably at most 9,000 and most preferably at most 6,000.

[0061] In one preferred general embodiment, an acid-functional polymer can be obtained from a reaction mixture comprising (in a ratio by weight) 5 to 20 parts of styrene, 30 to 70 parts of alkyl (meth) acrylate and 30 to 70 parts of an acidic monomer. . In one particular embodiment, the acid-functional polymer can be obtained from a reaction mixture comprising (in a weight ratio) 10 parts of styrene, 45 parts of butyl methacrylate and 45 parts of MAA. In another specific embodiment, an acid-functional polymer can be obtained from a reaction mixture comprising (in weight ratio) 30 parts of styrene, 10 parts of ethyl acrylate and 60 parts of MAA. These embodiments illustrate suitable such polymers.

[0062] A polymer with oxirane functional groups (or monomers for making such a polymer) and an acid-functional polymer (or monomers for making such a polymer) are preferably reacted with each other in the presence of a tertiary amine and a small amount of water. Under such conditions, the acid group, the oxirane group and the amine form a quaternary salt. This combination is advantageous because it not only combines polymers but also promotes the dispersibility of the combined polymer in water. It should be noted that the acid group and the oxirane group may also form an ester. This reaction is somewhat suitable, however this combination is less desirable when the water dispersibility is sought.

[0063] In one embodiment, the aqueous solution (or dispersion) of the tertiary amine is contacted below with a solution (or dispersion) of oxirane polymer in a suitable carrier (e.g., in a suitable organic liquid) or with a solution (or dispersion) of the polymer with oxirane functional groups and a polymer with acid functional groups. A wide variety of carriers may be used to dissolve or dispersion (preferably dissolve) polymers with oxirane functional groups and polymers with acid functional groups. Among the most commonly used carriers are alcohols, such as isopropanol, butyl alcohols, 2-hydroxy-4-methylpentane, 2-ethylhexyl alcohol, cyclohexanol, glycols such as ethylene glycol, diethylene glycol, 1,3-butylene glycol, ethereal alcohols,

[0064] Although the exact mechanism of the reaction has not been fully understood, it is believed that there is competition between the two reactions. One reaction includes a tertiary amine that first reacts with an acid functional polymer to form an ion of neutralized amine that can then react with the oxirane polymer. The second reaction may comprise a free tertiary amine that reacts directly with polymyermi with kkiiaan functional grppps. In each case, the corresponding products formed are the hydroxyl ester of an oxirane polymer with functional groups with an acid functional polymer and a polymer mixed quaternary ammonium and amine salt (from a tertiary amine, an oxirane polymer with an acid functional group). Reaction conditions, in this, the presence of water as a reaction modifier can be chosen to promote an esterification reaction or a quaternary salt formation. The substantial degree of quaternary salt formation increases the dispersibility of the water, and a significant degree of esterification gives a higher viscosity and the ability to form a gel material. By varying the substrate ratio and reaction conditions, the solids content, viscosity, particle size and properties of the product can be modified over a wide range.

[0065] If the reaction of tertiary amines with oxirane-containing materials takes place in the presence of water, a product containing both a hydroxyl group and a quaternary ammonium hydroxide can be obtained.

[0066] The preparation of the waterborne coating composition of the present invention is preferably carried out using at least one tertiary amine (including, for example, amines having the formula R¹⁴R¹⁵R¹⁶N, in which R¹⁴,> 16

R^{15 and} R1^about means substituted or unsubstituted monovalent alkyl groups (preferably containing 1 to 8 carbon atoms and more preferably containing 1 to 4 carbon atoms).

[0067] Some examples of suitable amines include (known tertiary dimethyl ethanolamine dimethylaminoethanol), ethylmethylethanolamine, dimethylpropylamine, propylamine, trimethylamine, also as methyldiethanolamine, dimethylethylamine, dimethyl-3-hydroxy-1-dimethylbenzylamine, dimethyl-2-hydroxy-1-propylamine, diethylmethylamine, dimethyl-1-hydroxy-2-propylamine, triethylamine, tributylamine, N-methylmorpholine and mixtures thereof. [0068] Other examples of tertiary amines are disclosed, for example, in US Patent Nos. 6,300,428; 6,087,417;

4,247,439; 5,830,952; 4,021,396; 5,296,525; 4,480,058;

4,442,246; 4,446,258 and 4,476,262.

[0069] Most preferably, trimethylamine or dimethyl ethanolamine is used as the tertiary amine.

[0070] The amount of tertiary amine required to produce the waterborne coating composition of the present invention depends on various factors. A minimum of 0.8 equivalents of tertiary amine is required per equivalent of oxirane groups, preferably at least 2 equivalents, more preferably at least 3 equivalents, tertiary amine on the equivalent of oxirane groups to form stable dispersions. As the ratio of the number of acidic groups in the acid functional polymer increases to the number of oxirane groups in the oxirane polymer group, the amount of amine is also increased to maintain the water dispersibility of the polymer with acid functional groups. It is believed that this excess of amine forms a salt with some or all of the excess acid groups in the polymer. It is beneficial that no excess of the amine with respect to the total equivalents of the acid groups is used in the coating composition of the present invention. [0071] It has been found that the stoichiometric ratio of amine to oxirane (A: Ox) can affect the viscosity of the composition. In general, the viscosity decreases as the A: Ox ratio increases. It should be noted that this tendency may not always be present because it has been found that the dispersion conditions also have an effect on the viscosity. The ratio of A: Ox is preferably at least 0.8: 1, more preferably at least 2: 1 and most preferably at least 2.5: 1. The ratio of A: Ox is preferably at most 5: 1, more preferably at most 4: 1 and most preferably at most 3.5: 1. If the polymer has been dispersed, an additional amine can be added to further correct the viscosity.

[0072] The weight ratio of the polymer with oxirane functional groups to the acid-functional polymer is usually at least 90:10, more preferably at least 87:13 and more preferably at least 84:16. The weight ratio of the polymer with oxirane functional groups to the acid-functional polymer is usually at most 50:50, preferably at most 70:30 and more preferably at the most 80:20.

[0073] The waterborne coating composition of the present invention can be produced irrespective of the order in which the individual components are added. Although it is preferred that a water-dispersible polymer is prepared from pre-formed polymers (e.g., an oxirane-functional vinyl addition polymer and an acid-functional polymer), it is possible that the monomers for the production of one of the polymers be reacted with a second polymer that it was created earlier or created in situ. If desired, the acid-functional polymer may be combined with a tertiary amine to at least partially neutralize the acid-functional polymer prior to reaction with an oxirane polymer or monomers to form an oxirane-functional polymer.

[0074] It is, however, preferred to first dissolve the oxirane polymer with functional groups in the acid-functional polymer in the presence of suitable carriers (e.g., organic liquids). The addition of the appropriate tertiary amine, usually dissolved in water, completes the preparation of the polymeric quaternary ammonium salt of the polymeric acid. Additional water can then be added to obtain a water dispersion. An additional amine can also be added to ensure dispersibility or to correct the viscosity.

[0075] The reaction may advantageously be carried out at a temperature of at least room temperature (e.g., 25 ° C), more preferably at least 50 ° C and most preferably at least 90 ° C. The reaction may advantageously be carried out at a temperature below the boiling point of the reaction medium and more preferably at a temperature of at most 100 ° C. In this temperature range there is a high rate of reaction. [0076] In another preferred method for preparing the coating composition, the oxirane polymer is dissolved in a suitable carrier, such as ethylene glycol or diethylene glycol monobutyl ether, followed by the addition of a suitable tertiary amine. When the formation of polymeric quaternary ammonium hydroxide is substantially completed, the polymer with acid functional groups, dissolved or dispersed in a suitable carrier, is mixed with it. The latter solution or dispersion may further contain any additional suitable amine dissolved in water which is necessary to obtain dispersibility of the coating composition. The mixing of ingredients completes the process of producing a waterborne coating composition. The sequence of the steps may further be carried out at a temperature of from room temperature to a temperature below the boiling point of the reaction medium.

[0077] The product obtained is a hardened thin layer comprising a cross-linked polymer comprising a cross-linked segment having the general formula:

YC (R 2) -C (R) (OH) -C (R2) -O- (O) CX_r- wherein: Y is a divalent organic group (preferably a C1 to C6 organic group), more preferably a divalent organic group containing a C (O) O moiety; X is a divalent organic group (preferably a C1 to C6 organic group); R is H or a C1 to C6 organic group, preferably H; and r is 0 or 1, preferably 0.

[0078] It has been found that coating compositions using the above-mentioned dispersions can be obtained using one or more optional curing agents (i.e., cross-linking resins, sometimes referred to as "cross-linking agents"). The choice of the appropriate crosslinker usually depends on the particular product being obtained. For example, some coating compositions are highly colored (e.g., gold color coatings). These coatings can usually be obtained using cross-linking agents, which in themselves often have a yellowish color. In turn, white coatings are usually obtained using crosslinking agents that do not cause yellowing or contain only a small amount of crosslinking agent causing yellowing. Preferred curing agents in principle do not contain mobile BPA and derivatives of aromatic glycidyl ethers (e.g., BADGE, BFDGE and epoxide Novalac). [0079] Any of the well-known reactive curing resins with hydroxyl groups may be used. For example, phenoplast and aminoplast curing agents may be used.

[0080] Phenoplast resins contain condensation products of aldehydes with phenols. Preferred aldehydes are formaldehyde and acetaldehyde. Various phenols such as phenol, cresol, p-phenylphenol, p-tert-butylphenol, p-tert-amylphenol and cyclopentylphenol can be used.

[0081] The aminoplast resins are condensation products of aldehydes, such as formaldehyde, acetaldehyde, crotonaldehyde and benzaldehyde, with substances containing an amine or amide group, such as urea, melamine and benzoguanamine.

Examples of suitable crosslinking resins include, without limitation: benzoguanamine formaldehyde resins, melamine-formaldehyde resins, esterified melamine-formaldehyde resins and urea-formaldehyde resins. The cross-linking agent used in the practice of the present invention preferably contains a melamine-formaldehyde resin. One particular example of a particularly useful crosslinking agent is the fully alkylated melamine-formaldehyde resin commercially available from Cytec Industries, Inc. under the trade name CYMEL 303. Examples of other substantially suitable crosslinking agents include blocked or unblocked aliphatic, cycloaliphatic or aromatic di-, tri- or multivalent isocyanates, such as hexamethylene diisocyanate, 1,

[0084] The level of curing agent necessary (i.e., the crosslinking agent) depends on the type of crosslinker, the time and temperature of annealing and the molecular weight of the polymer. The crosslinking agent is typically present in an amount of at least 5% by weight (wt%), preferably at least 10% by weight and more preferably at least 15% by weight. The crosslinking agent is typically present in an amount of at most 50% by weight, preferablyat most 40% by weight and more preferably at least 30% by weight. These weight percentages are determined with respect to the total weight of the solids constituting the resin in the coating composition. [0085] The coating composition according to the present invention may also comprise other optional polymers not adversely affecting the coating composition or the cured coating composition obtained therefrom. Such optional polymers are usually incorporated into the coating composition in the form of a filler material, but they can be used as a cross-linking material or to achieve the desired properties. Preferred optional polymers generally do not contain mobile BPA and derivatives of aromatic glycidyl ethers (e.g., BADGE,

BFDGE and epoxide Novalac).

[0086] These additional polymeric materials may be non-reactive, as a result of which they simply have the function of fillers. Alternatively, such additional polymeric materials or monomers may be reactive to a water dispersible polymer, an oxirane functional polymer and / or an acid functional polymer. If such polymers and / or monomers are appropriately selected, they can participate in cross-linking. [0087] After dispersing in the water dispersible polymer carrier, one or more optional polymers or monomers (e.g. used to form such optional polymers) may be added to the composition. Optionally, one or more optional polymers or monomers (such as those used to form such polymers) can be added to the reaction mixture at various reaction steps (i.e.

[0088] For example, the non-reactive filler polymer may be added after dispersing in the water dispersible polymer carrier. The non-reactive filler polymer may optionally be added prior to dispersion in the water-dispersible polymer carrier, which may be in the state before, during or after the reaction of the oxirane functional vinyl addition polymer and vinyl acid addition polymer with functional groups in the presence of a tertiary amine.

[0089] Such optional non-reactive filler polymers include, for example, polyesters, acrylates, polyamides, polyethers and Novalac materials.

[0090] If desired, reactive polymers may be incorporated into the compositions of the present invention to provide additional functionality for a variety of purposes, including cross-linking.

[0091] Examples of such reactive polymers include, for example, functionalized polyesters, acrylates, polyamides and polyethers.

[0092] One or more polymers (e.g., bulking polymers) may be included in a sufficient amount to serve a suitable purpose, however in an amount that does not adversely affect the coating composition or the cured coating composition obtained therefrom. [0093] The coating composition according to the present invention may also comprise other optional ingredients not adversely affecting the coating composition or the cured coating composition obtained therefrom. Such optional ingredients are usually incorporated into the coating composition to improve its aesthetic properties, facilitate the manufacture, processing, handling and use of the composition, and to further improve the specified functional property of the coating composition or the cured coating composition obtained therefrom. Such optional components include, for example, catalysts, dyes, pigments, organic pigments, fillers, fillers, lubricants, anti-corrosive agents, flow control agents, thixotropic agents, dispersing agents, antioxidants, adhesion promoters, light stabilizers, and mixtures thereof. Each optional ingredient is included in a sufficient amount to serve an appropriate purpose, but in an amount that does not adversely affect the coating composition or the cured coating composition obtained therefrom. light stabilizers and their mixtures. Each optional ingredient is included in a sufficient amount to serve an appropriate purpose, but in an amount that does not adversely affect the coating composition or the cured coating composition obtained therefrom. light stabilizers and their mixtures. Each optional ingredient is included in a sufficient amount to serve an appropriate purpose, but in an amount that does not adversely affect the coating composition or the cured coating composition obtained therefrom.

[0095] One optional component is a catalyst for increasing the curing speed. If a catalyst is used, it is preferably present in an amount of at least 0.05% and more preferably at least 0.1% by weight non-volatile material. If a catalyst is used, it is preferably present in an amount of at most 1% and more preferably at most 0.5% by weight non-volatile material.

Examples of catalysts include, without limitation, strong acids (e.g., dodecylbenzenesulfonic acid (DDBSA, available as CYCAT 600), methanesulfonic acid (MSA), p-toluenesulfonic acid (PTSA), dinonylnaphthalene disulfonic acid (DNNDSA) and acid trifluoric acid), quaternary ammonium compounds, phosphorus compounds, and tin and zinc compounds, e.g. tetraalkylammonium halide, iodide or tetraalkyl or tetraarylphosphonium iodide, tin octoate, zinc octoate, triphenylphosphine, and similar catalysts known to those skilled in the art.

[0097] Another useful optional ingredient is a lubricant, such as a wax, which facilitates the production of metal closures because it imparts lubricity to the sheets of the coated metal substrate. The lubricant is preferably present in the coating composition in an amount of 0 to 2% and preferably 0.1 to 2% by weight of the non-volatile material. Preferred lubricants include, for example, carnauba wax and polyethylene type lubricants.

[0098] Another useful optional ingredient is a pigment, such as titanium dioxide. A pigment such as titanium dioxide is optionally present in the coating composition in an amount of 0 to 70 wt%, more preferably 0 to 50 wt%.

and most preferably 0 to 40 wt%, based on the total weight of the solids in the coating composition.

[0099] The above-mentioned coating composition is particularly well suited for use as a coating for packaging articles (e.g., two-part cans, three-part cans, etc.). Two-piece cans are made by connecting the can body (usually a drawn metal body) to the can end (usually a drawn metal end). The coatings of the present invention are suitable for use in food contact conditions and can be used inside such cans.

[0100] As described in the previous paragraphs, it has been shown that the present invention shows considerable suitability as a liquid coating applied by spraying on the interior of two-piece drawn and pressed food cans of tinned steel sheet (hereinafter referred to as D & I tinned steel can). The present invention is further useful in other applications. These additional applications include, but are not limited to: indirect coating, coil coating, sheet coating and side suture coating, e.g., coating side seams of food cans.

[0101] Intermediate coating is described under industrial conditions as the coating of the outer surface of two-piece drawn and pressed (D & I) cans with a thin layer of a protective coating. The outer surface of these D & I cans is coated with an intermediate layer by passing the pre-formed two-piece D & I cans under a curtain from the shell. The cans are inverted, i.e. the open end of the can is at the bottom while passing through the curtain. This curtain shell has a look reminiscent of a waterfall. When the cans pass under such a coating curtain, the liquid coating material effectively coats the outer surface of each can. Excess coating is removed using an air knife. After applying the appropriate amount of coating to the outside surface of each can, the can is placed in a heat curing oven and / or with ultraviolet and / or electromagnetic radiation to dry and cure the coating. The residence time of the coated can in the zone of the curing oven is 1-5 minutes. The curing temperature in this oven remains in the range of 150-220 ° C.

[0102] The coil coating is described as coating a continuous metal coil (e.g., steel or aluminum). After coating, the coated coil is subjected to a short-term thermal curing cycle and / or by ultraviolet and / or electromagnetic radiation, which leads to drying and curing of the coating. Coil coating provides coated metal substrates (e.g., steel and / or aluminum) from which molded products can be manufactured, e.g. two-piece drawn food cans, three-piece food cans, food can ends, pulled cans, and pressed ends of beverage cans and the like.

[0103] Coating of sheets is described as coating separate pieces of a variety of materials (e.g., steel or aluminum) that have been pre-cut into square or rectangular sheets. Typical dimensions of these sheets are approximately one square meter. After coating, each sheet hardens. After drying and curing, the sheets of the coated substrate are collected and prepared for subsequent manufacture. Coil coatings provide a coated metal substrate (e.g., steel or aluminum) from which molded articles can be successfully manufactured, e.g. two-piece drawn food cans, three-piece food cans, food can ends, pulled cans, and pressed ends of cans for drinks and the like.

[0104] The suturing of lateral sutures is described as spray application of a liquid coating on the welded area of ​​molded three-piece food cans. When three-piece food cans are obtained, a cylinder is formed from a rectangular piece of the coated substrate. The created roller is fixed by welding both sides of the rectangle by welding. After welding, each can usually requires the application of a liquid coating layer that protects the exposed seal against subsequent corrosion or other action contained within the food. Liquid coatings having this function are referred to as side seam strips. Typical strips of side seams are applied by spraying and quickly cured due to residual heat from the welding process,

[0105] In addition, other industrial coating and curing methods are also sought, for example electrolytic coating, extrusion coating, lamination, powder coating and the like. In one presently preferred embodiment, the coating composition is suitable for food contact conditions and comprises 24 wt. up to 30% by weight solids and less than 0.36 kg / liter (3 pounds / gallon) of VOC.

[0106] Preferred embodiments are summarized below:

A process comprising providing a vinyl oxirane-functional adduct polymer in which the oxirane functional content is 0.5 to 5;

providing a polymer with acid functional groups, whose acid number is 30 to 500;

performing a reaction of an oxirane vinyl addition polymer with an acidic functional group in the presence of a tertiary amine to form a water-dispersible polymer; and dispersing the water-dispersible polymer in a water-containing carrier.

2. The method according to item 1, wherein the water-dispersible polymer substantially contains no mobile BPA and derivatives of aromatic glycidyl ethers.

3. The method of item 1, wherein the water-dispersible polymer is substantially free of BPA and aromatic glycidyl ether derivatives.

4. The method according to item 1, wherein the water-dispersible polymer does not contain BPA and aromatic glycidyl ether derivatives at all.

5. The method of item 1, wherein the oxirane vinyl addition polymer is formed by the reaction of one or more monomers with an oxirane functional group with one or more other monomers.

6. The method of item 1, wherein the vinyl oxirane vinyl addition polymer is formed by the reaction of one or more monomers with an oxirane functional group with one or more other monomers in the carrier.

7. Method according to item 5, wherein the monomer with the oxirane functional group is a glycidyl ester of alpha, beta-unsaturated acid or its anhydride.

8. Method according to item 5, wherein the monomer with an oxirane functional group is selected from the group consisting of glycidyl (meth) acrylate, mono- and diglycidyl itaconate, mono- and diglycidyl maleate, and mono- and diglycidyl formate and mixtures thereof.

9. The method according to item 1, wherein the vinyl oxirane vinyl addition polymer is formed by reacting a copolymer of alpha, beta-unsaturated acid and alkyl (meth) acrylate with a halide or glycidyl tosylate so that the side glycidyl groups are on the acrylate copolymer.

10. The method of item 1, wherein the oxirane vinyl addition polymer is oxirane functional content of 0.9 to 3. 11. The method of item 1, wherein the oxirane vinyl addition polymer has a molecular weight number average numerical 2500 to 20,000. 12. The method of item 5, wherein the one or more other monomers are selected from the group consisting of alkyl (meth) acrylate and vinyl monomers.

13. Method according to item 5, wherein the one or more other monomers comprise a vinyl monomer selected from the group consisting of styrene, halostyrene, isoprene, diallyl phthalate, divinylbenzene, conjugated butadiene, alpha-methylstyrene, vinyltoluene, vinylnaphthalene and mixtures thereof.

14. The method of item 1, wherein the oxirane vinyl addition polymer is formed by the reaction of one or more oxirane monomers with one or more hydroxyl functional monomers and with one or more other monomers.

15. The method of item 14, wherein the one or more oxirane monomer monomers are selected from the group consisting of glycidyl (meth) acrylate, mono- and diglycidyl itaconate, mono- and diglycidyl maleate, and mono- and diglycidyl formate; and mixtures thereof; one or more hydroxyl functional monomers are selected from the group consisting of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and mixtures thereof; and the one or more other monomers are selected from the group consisting of styrene, halostyrene, isoprene, diallyl phthalate, divinylbenzene, conjugated butadiene, alpha-methylstyrene, vinyltoluene, vinylnaphthalene and mixtures thereof.

16. The method of item 1, wherein the vinyl oxirane-containing adduct polymer has (in a weight ratio) 30 to 70 parts of styrene; 3 to 10 parts glycidyl (meth) acrylate; and 30 to 70 parts of hydroxyalkyl (meth) acrylate.

17. The process according to item 1, wherein the acid-functional polymer is a vinyl acid addition polymer addition group and comprises homopolymers or copolymers made from ethylenically unsaturated acid or anhydride monomers and other optional monomers. 18. The method of item 17, wherein the acidic acid functional vinyl addition polymer has a number average molecular weight of 2000 to 15,000. 19. Method according to item 17, wherein the vinyl acid addition functional polymer comprises 5 to 20 parts (by weight). ) styrene, 30 to 70 parts of alkyl (meth) acrylate and 30 to 70 parts of monomer with an acid function. 20. Method according to item 1, wherein the tertiary amine is selected from the group R¹⁴R¹⁵R¹⁶N, in which R¹⁴, R¹⁵ and R¹⁶means substituted or unsubstituted monovalent alkyl groups having one from eight carbon atoms in the alkyl portion.

21. The process according to item 1, wherein the tertiary amine is selected from the group consisting of trimethylamine, dimethylethanolamine, methyldiethanolamine, ethylmethylethanolamine, dimethylethylamine, dimethylpropylamine, dimethyl-3-hydroxy-1-propylamine, dimethylbenzylamine, dimethyl-2-hydroxy-1-propylamine, diethylmethylamine, dimethyl-1-hydroxy-2-propylamine and mixtures thereof.

22. The method of item 1, wherein the water-dispersible polymer comprises at least 0.8 equivalents of tertiary amine per equivalent of oxirane groups. 23. The method of item 1, wherein the water-dispersible polymer is provided in a coating composition comprising a crosslinking resin.

24. The method of item 1, further comprising adding a non-reactive filler polymer before or after dispersion in the water-dispersible polymer carrier.

25. A method according to item 24, wherein the non-reactive filler polymer is added before, during or after the reaction of the oxirane vinyl addition polymer with the addition of a vinyl acid addition polymer function in the presence of a tertiary amine. 26. The method of item 1, further comprising adding a reactive polymer or monomers before or after dispersion in the water-dispersible polymer carrier.

27. The method of item 6, wherein the reactive polymer or monomers are added before, during or after the reaction of the oxirane functional vinyl addition polymer and the acid addition polymer addition polymer in the presence of a tertiary amine.

28. A composition comprising: an aqueous dispersion of a quaternary ammonium salt, the salt comprising a reaction product of an oxirane functional vinyl addition polymer in which the oxirane functional content is 0.5 to 5; an acid functional polymer having an acid number of 30 to 500; and tertiary amine.

29. A coating composition comprising:

an aqueous dispersion of a quaternary ammonium salt, the salt comprising a reaction product of an oxirane functional vinyl addition polymer in which the oxirane functional content is 0.5 to 5; an acid functional polymer having an acid number of 30 to 500; and tertiary amine; and a crosslinking agent.

30. A method for coating an article, the method comprising applying the composition according to item 28 to a surface of the substrate and curing the composition.

31. A method for coating an article, the method comprising applying the composition according to item 29 to a substrate surface and curing the composition.

32. A treatment comprising a substrate on which the unhardened thin film is located, wherein the thin layer comprises an aqueous dispersion of a quaternary ammonium salt, the salt comprising a reaction product of an oxirane functional vinyl addition polymer in which the oxirane functional content is 0.5 to 5;

an acid functional polymer having an acid number of 30 to 500; and tertiary amine.

33. The article according to item 32, wherein the thin layer further comprises a crosslinking agent.

34. An article comprising a substrate on which a cured thin film is provided, wherein the cured film may be made from a coating composition comprising an aqueous dispersion of a quaternary ammonium salt, the salt comprising a reaction product of an oxirane functional vinyl addition polymer in which the content of oxirane groups functionalities is 0.5 to 5; an acid functional polymer having an acid number of 30 to 500; tertiary amine; and optionally a crosslinking agent.

35. An article comprising a substrate on which the cured thin film is provided, wherein the cured film comprises a cross-linked polymer comprising a cross-linked segment of general formula:

YC (R 2) -C (R) (OH) -C (R2) -O- (O) CX_r- wherein: Y is a divalent organic group; X is a divalent organic group; R is H or a C1 to C6 organic group; and r is 0 or 1.

36. A method comprising:

providing a vinyl addition polymer with oxirane functional groups in which the oxirane functional group content is 0.5 to 5;

providing a polymer with acid functional groups, whose acid number is 30 to 500; providing a tertiary amine;

combining the polymer with acid functional groups with a tertiary amine to form a mixture and at least partially neutralizing the polymer with acid functional groups;

combining the oxirane-functional vinyl addition polymer and mixtures to form a water-dispersible polymer; and dispersing the water-dispersible polymer in a water-containing carrier.

37. The method of item 36, wherein the mixture is added to the oxirane vinyl addition polymer group for a period of time.

38. A method comprising:

providing a first set of monomers for the production of an oxirane-functional vinyl addition polymer in which the oxirane functional content is 0.5 to 5;

providing a second set of monomers for preparing an acid-functional polymer having an acid number of 30 to 500;

providing a tertiary amine;

polymerizing at least one set of monomers to form the first polymer;

polymerizing a second set of monomers in the presence of a first polymer;

addition of a tertiary amine to form a water-dispersible polymer; and dispersing the water-dispersible polymer in a water-containing carrier.

39. The method of item 38, wherein the polymerization to form the first polymer is carried out in the presence of a second set of monomers.

40. A method comprising:

providing an oxirane vinyl addition polymer group, wherein the oxirane functional group content is 0.5 to 5, and the number average molecular weight is 2500 to 20,000; wherein the vinyl polymer with oxirane functional groups is the reaction product of 1 to 10 wt.%. Oxirane functional monomer, 0 to 60% by weight a hydroxyl functional monomer and the remainder is a different monomer;

providing a polymer with acid functional groups, whose acid number is 30 to 500, and the number average molecular weight is 2000 to 15,000; wherein the polymer with acid functional groups is a vinyl polymer formed as a reaction product of at least 15 wt% an acid-functionalized monomer, the remainder being a different monomer;

performing a reaction of an oxirane vinyl addition polymer with an acidic functional group in the presence of a tertiary amine to form a water-dispersible polymer; and dispersing the water dispersible polymer in a water containing carrier;

wherein the weight ratio of the vinyl addition polymer with oxirane functional groups to the acid-functional polymer is 90:10 to 50:50 and the ratio of amine to oxirane groups is 0.8: 1 to 5: 1.

EXAMPLES [0107] The following examples are intended to facilitate the understanding of the present invention and are not intended to limit its scope in any way. Unless otherwise indicated, all parts and percentages are given in a weight ratio. The aforementioned constructions were evaluated using the following tests:

Uniformity of the coating / metal exposure:

[0108] In this test method, the size of the inner surface of the can is determined which has not been effectively covered by the spray coating. This determination is made by using an electrically conductive solution (1% NaCl in deionized water). The coated can is filled with this conductive solution. Attach the electric probe contacting the outer surface of the can (uncoated, electrically conductive), and the other probe is immersed in a saline solution in the middle of the inner part of the can. If there is any uncoated metal inside the box, there is a current flow between the two probes, which is recorded as a reading on the LED display. This display shows the current flow in milliamps, which is more often referred to as the abbreviation mAs. The flowing current is directly proportional to the amount of metal, which has not been effectively coated. The goal is to get 100% coverage inside the can, which means the reading on the LED display is 0.0 mAs. Acceptable in industrial conditions, the values ​​of exposed metal are usually less than 3.0 mAs.

The ability to spread the coating / wettability:

[0109] This test is essentially a visual assessment of the ability of the coating to effectively wet or uniformly disperse on the inner surface of the spray can. It is desirable that the sprayed coating be uniformly dispersed without visual defects, such as openings, creep, peeling or other, which can cause a higher value of metal exposure or other visually disadvantageous phenomena. It is believed that the perfect assessment indicates that the can has quality acceptable in industrial conditions. A verbal rating scale is used, which is defined as follows: perfect: no visual defects; good: very few minimum defects; satisfactory: few significant defects; unsuitable: frequent occurrence of significant defects.

Creating bubbles:

[0110] This test is essentially a visual assessment of the tendency of the coatings to form bubbles or the formation of undesired air bubbles at locations inside the spray can. It is undesirable for industrial reasons that the coating inside the can contains visible blisters. Therefore, the perfect blister evaluation relates to cans that are believed to be of acceptable quality under industrial conditions. A verbal rating scale is used, which is defined as follows: perfect: no visible blisters; good: very few small blisters; satisfactory: frequent occurrence of small blisters; unsuitable: frequent occurrence of large blisters.

Usage parameters of the hardened thin film:

[0111] A wide variety of food products packaged under industrial conditions in coated D & I tinned tin cans are known. As part of the research and development of coatings, a number of coating screening tests have been developed that help predict if the coating will have the required performance parameters for staining, adhesion and corrosion to be an acceptable internal varnish for industrial and filled D & I tin cans tinned steel or not. The useful parameters of the coating in the cycles of food sterilization, which are more often referred to as food autoclaves, are of particular importance. Such an autoclave serves for thermal sterilization of the filled can which is carried out in superheated steam under pressure and / or water.

[0112] In typical industrial sterilization autoclaves, filled food cans are exposed to superheated steam or water for a time in the range of 10 minutes to several (1-3) hours, depending on factors such as size of the can and the food product. The steam or water temperature is approximately 121 ° C. Under these autoclaving conditions, deterioration of the operational parameters of the interior of the can, such as stain resistance, adhesion or corrosion resistance, may begin. The function of the internal coating is to ensure the protection of the can against the action of the packaged product (corrosion, stain resistance), as well as to protect the packed product from the influence of the can (metal exposure, adhesion). It is undesirable for industrial reasons that the inner coating of the can And showed very significant deficiencies in these areas under filling, sterilization or storage conditions. Therefore, an effective test protocol was developed to predict the operational parameters of any proposed new interior surfaces of D & I cans under industrial conditions.

[0113] Of particular importance is the cavity, in which it is usually the hardest to meet the requirements for performance. The empty space is a small space at the top of the can (usually 0.5-1.0 cm) in which there is no food product. The empty space is left in each can to allow expansion of the product during autoclaving so that the can does not explode under the pressure of its contents. In some cases, an additional assessment was made in the areas of the dome and the rim of cans. [0114] To carry out this evaluation, a sufficient number of test cans are obtained using the variable coating parameters under investigation. After a complete coating of the cans, a number of test centers constituting food products are selected with suitable coatings to carry out tests on the immunity of foodstuffs. In the case of gold coating variables, selected products are representative of many products typically packaged under industrial conditions in gold D & I cans. After selecting the food products used, they are filled into a can body at a temperature which is used in industrial conditions. More detailed information or references are given in the canning industry guidelines. Each can is usually filled with 1.25 cm (empty space) to allow expansion of the product during autoclaving. After filling, each can is appropriately closed by means of a double closure with the end of a food can with an appropriate diameter. After closing, the cans are subjected to a cycle of autoclaving (time, temperature) in accordance with industrial practice. After autoclaving, cans are suitably cooled and opened using a conventional manual can opener. After opening, the contents are removed, the interior of the can is rinsed with clean water, the can is cut at four points down the side wall and the flattened can is suitably dried. At this stage, the cans are ready for the following evaluation of the thin film:

Adhesion:

[0115] The obsolete space of the empty can is cut into a grid with a sharp object. After making this pattern, the checkered area is tested with Scotch® # 610 to assess the ability of the coating to maintain adhesion in this area. The adhesion rating scale 0-10 is used, with 10 indicating that 100% of the coating in this area has remained adhered. 0 means that 100% of the coating in this area has been torn off with tape. The adhesion rating given is the average rating for three cans.

Corrosion:

[0116] The empty can is visually inspected for visible corrosion. The corrosion rating scale is also used in the 0-10 range, with 10 indicating no visible corrosion and 0 indicating that 100% of the empty space shows signs of corrosion. The corrosion rating given is the average rating for three cans.

[0117] The following filling and autoclaving conditions apply:

1. Mixed corn heated to 71 ° C before filling and closing the can. Autoclaving conditions: 1.5 hours at 121 ° C.

2. Salted carrots: salted brine heated to 88 ° C before filling and closing the can. Autoclaving conditions: 1.5 hours at 121 ° C.

3. Green beans, filling at room temperature. Autoclaving conditions: 1.5 hours at 121 ° C.

4. Spoon warmed up to 88 ° C before filling and closing the can. Autoclaving conditions: 1.5 hours in

121 ° C.

5. Chicken broth preheated to 82 ° C before filling and closing the can. Autoclaving conditions: 1.5 hours at 121 ° C.

6. Tomatoes heated to 88 ° C before filling and closing the can. Autoclaving conditions: 1.5 hours at 121 ° C.

7. Peas heated to 71 ° C before filling and closing the can. Autoclaving conditions: 1.5 hours at 121 ° C.

Example 1

Preparation of polymers with oxirane functional groups

Example 1, test # 1 [0118] A stirrer, reflux condenser, thermocouple, heating mantle and nitrogen blanket were attached to a 5-liter flask. In a separate vessel, a masterbatch of monomers containing 1162 parts of styrene, 888 parts of hydroxyethyl methacrylate, 64.1 parts of glycidyl methacrylate and 90.4 parts of t-butyl peroctoate was prepared. Into a 5-liter flask, 245 parts of butanol and 804 parts of Cellosolve butyl were introduced. The flask was heated to 98 ° C and 14.2 parts of t-butyl peroctoate was added. After 5 minutes, the premix was added to the flask over two and a half hours maintaining the temperature at 97 ° C to 101 ° C. An initiator masterbatch was prepared containing 105 parts of Cellosolve butyl and 45.1 parts of t-butyl peroctoate. After completing the addition of the monomer masterbatch, the pre-mixed vessel was rinsed with 43 parts of butyl Cellosolve. The initiator masterbatch was added immediately over a period of one hour. After completing the addition of the initiator masterbatch, the vessel was rinsed with 27 parts of butyl Cellosolve. The mixture was held at 98 ° C to 99 ° C for one hour. After one hour, 4.34 parts of t-butyl peroctoate was added and the mixture was held for one hour. After one hour, 4.34 parts of t-butyl peroctoate was added a second time and the mixture was maintained for one more hour. After one hour, 4.34 parts of t-butyl peroctoate was added for the third time and the mixture was held for one hour. The mixture was then cooled to give a polymer having a NV value of 62.5% NV, a number of oxirane groups of 0.018 eq / 100 grams of solid resin, an acid number of 2.6 and a viscosity of 210,000 centipoises at 26.7 ° C.

[0119] The additional batch obtained by the above procedure gave a polymer having a NV value of 62.6%, a number of oxirane groups of 0.019, an acid value of 2.5 and a viscosity of 222,000 centipoise. The second additional batch yielded a polymer having an NV value of 64.8%, a number of oxirane groups of 0.019, an acid number of 1.8 and a viscosity of 268,000 centipoise.

Example 1, test # 2 [0120] A stirrer, reflux condenser, thermocouple, heating mantle and nitrogen blanket were attached to a 5-liter flask. In a separate vessel, a masterbatch of monomers containing 1162 parts of styrene, 888 parts of hydroxyethyl methacrylate, 64.1 parts of glycidyl methacrylate and 90.4 parts of t-butyl peroctoate was prepared. 524.5 parts of butanol and was introduced into a 5-liter flask

524,5 parts of Cellosolve butyl. The flask was heated to 98 ° C and 14.2 parts of t-butyl peroctoate was added. After 5 minutes, the premix was added to the flask over two and a half hours maintaining the temperature at 97 ° C to 101 ° C. An initiator masterbatch was prepared containing 105 parts of Cellosolve butyl and 45.1 parts of t-butyl peroctoate. After the addition of the monomer masterbatch, the pre-mixed vessel was rinsed with 43 parts of Cellosolve butyl. The initiator masterbatch was added immediately over a period of one hour. After completing the addition of the initiator masterbatch, the vessel was rinsed with 27 parts of butyl Cellosolve. The mixture was held at 98 ° C to 99 ° C for one hour. After one hour, 4.34 parts of t-butyl peroctoate was added and the mixture was held for one hour. After one hour, a second time was added 4, 34 parts of t-butyl peroctoate and the mixture was maintained for one more hour. After one hour, 4.34 parts of t-butyl peroctoate was added for the third time and the mixture was held for one hour. The mixture was then cooled to give a polymer having an NV value of 62.3%, an oxirane group of 0.020 eq / 100 grams of solid resin and a viscosity of 183,000 centipoises at 26.7 ° C.

[0121] Additional batches were prepared by the above method and polymers having a NV value of 62.4% were obtained, the number of oxirane groups was 0.018 to 0.019 and the viscosity was 166,000 to 17500 centipoises.

Example 1, test # 3 [0122] A stirrer, a reflux condenser, a thermocouple, a heating mantle, and a nitrogen blanket were added to a 12-liter flask. In a separate vessel, a masterbatch of monomers containing 1726 parts, 1 part styrene, 1319,2 parts of hydroxyethyl methacrylate, 95.2 parts of glycidyl methacrylate and 134.3 parts of t-butyl peroctoate was prepared. To a 12-liter flask, 363,9 parts of butanol and 1149.3 parts of Cellosolve butyl were introduced. The flask was heated to 98 ° C and 21.0 parts of t-butyl peroctoate was added. After 5 minutes the premix was added to the flask over three and a half hours maintaining the temperature at 97 ° C to 101 ° C. An initiator masterbatch was prepared containing 156 parts of Cellosolve butyl and 67 parts of t-butyl peroctoate. After completing the addition of the monomer masterbatch, the pre-mixed vessel was rinsed 63, 9 parts of butyl Cellosolve. The initiator masterbatch was added immediately over a period of one hour. After complete addition of the initiator masterbatch, the vessel was rinsed with 39.6 parts of Cellosolve butyl. The mixture was held at 98 ° C to 99 ° C for one hour. After one hour, 6.5 parts of t-butyl peroctoate was added and the mixture was held for one hour. After one hour, 6.5 parts of t-butyl peroctoate were added a second time and the mixture was maintained for one more hour. After one hour, 6.5 parts of t-butyl peroctoate were added for the third time and the mixture was held for one hour. The mixture was then cooled to give a polymer having an NV value of 64.5%, a number of oxirane groups of 0.018 eq / 100 grams of solid resin and an acid number of 3.3. The initiator masterbatch was added immediately over a period of one hour. After complete addition of the initiator masterbatch, the vessel was rinsed with 39.6 parts of Cellosolve butyl. The mixture was held at 98 ° C to 99 ° C for one hour. After one hour, 6.5 parts of t-butyl peroctoate was added and the mixture was held for one hour. After one hour, 6.5 parts of t-butyl peroctoate were added a second time and the mixture was maintained for one more hour. After one hour, 6.5 parts of t-butyl peroctoate were added for the third time and the mixture was held for one hour. The mixture was then cooled to give a polymer having an NV value of 64.5%, a number of oxirane groups of 0.018 eq / 100 grams of solid resin and an acid number of 3.3. The initiator masterbatch was added immediately over a period of one hour. After complete addition of the initiator masterbatch, the vessel was rinsed with 39.6 parts of Cellosolve butyl. The mixture was held at 98 ° C to 99 ° C for one hour. After one hour, 6.5 parts of t-butyl peroctoate was added and the mixture was held for one hour. After one hour, 6.5 parts of t-butyl peroctoate were added a second time and the mixture was maintained for one more hour. After one hour, 6.5 parts of t-butyl peroctoate were added for the third time and the mixture was held for one hour. The mixture was then cooled to give a polymer having an NV value of 64.5%, a number of oxirane groups of 0.018 eq / 100 grams of solid resin and an acid number of 3.3. After complete addition of the initiator masterbatch, the vessel was rinsed with 39.6 parts of Cellosolve butyl. The mixture was held at 98 ° C to 99 ° C for one hour. After one hour, 6.5 parts of t-butyl peroctoate was added and the mixture was held for one hour. After one hour, 6.5 parts of t-butyl peroctoate were added a second time and the mixture was maintained for one more hour. After one hour, 6.5 parts of t-butyl peroctoate were added for the third time and the mixture was held for one hour. The mixture was then cooled to give a polymer having an NV value of 64.5%, a number of oxirane groups of 0.018 eq / 100 grams of solid resin and an acid number of 3.3. After complete addition of the initiator masterbatch, the vessel was rinsed with 39.6 parts of Cellosolve butyl. The mixture was held at 98 ° C to 99 ° C for one hour. After one hour, 6.5 parts of t-butyl peroctoate was added and the mixture was held for one hour. After one hour, 6.5 parts of t-butyl peroctoate were added a second time and the mixture was maintained for one more hour. After one hour, 6.5 parts of t-butyl peroctoate were added for the third time and the mixture was held for one hour. The mixture was then cooled to give a polymer having an NV value of 64.5%, a number of oxirane groups of 0.018 eq / 100 grams of solid resin and an acid number of 3.3. After one hour, 6.5 parts of t-butyl peroctoate was added and the mixture was held for one hour. After one hour, 6.5 parts of t-butyl peroctoate were added a second time and the mixture was maintained for one more hour. After one hour, 6.5 parts of t-butyl peroctoate were added for the third time and the mixture was held for one hour. The mixture was then cooled to give a polymer having an NV value of 64.5%, a number of oxirane groups of 0.018 eq / 100 grams of solid resin and an acid number of 3.3. After one hour, 6.5 parts of t-butyl peroctoate was added and the mixture was held for one hour. After one hour, 6.5 parts of t-butyl peroctoate were added a second time and the mixture was maintained for one more hour. After one hour, 6.5 parts of t-butyl peroctoate were added for the third time and the mixture was held for one hour. The mixture was then cooled to give a polymer having an NV value of 64.5%, a number of oxirane groups of 0.018 eq / 100 grams of solid resin and an acid number of 3.3. 5 parts of t-butyl peroctoate and the mixture was maintained for one hour. The mixture was then cooled to give a polymer having an NV value of 64.5%, a number of oxirane groups of 0.018 eq / 100 grams of solid resin and an acid number of 3.3. 5 parts of t-butyl peroctoate and the mixture was maintained for one hour. The mixture was then cooled to give a polymer having an NV value of 64.5%, a number of oxirane groups of 0.018 eq / 100 grams of solid resin and an acid number of 3.3.

The batch gave a polymer having an NV value of 64.2%, a number of oxirane groups of 0.017 eq / 100 grams of solid resin, an acid number of 2.2 and a Brookfield viscosity of 216 400 centipoises.

Example 1, test # 4 [0124] A stirrer, reflux condenser, thermocouple, heating mantle and nitrogen blanket were added to a 12-liter flask. In a separate vessel, a masterbatch of monomers was prepared containing 1412,4 parts of styrene, 1079, 4 parts of hydroxypropyl methacrylate, 77.9 parts of glycidyl methacrylate and 109.9 parts of t-butyl peroctoate. To a 12 liter flask, 297.8 parts of butanol and 967.3 parts of Cellosolve butyl were introduced. The flask was heated to 94 ° C and 17.3 parts of t-butyl peroctoate was added. After 5 minutes, the premix was added to the flask over three and a half hours maintaining the temperature at 97 ° C to 100 ° C. An initiator masterbatch was prepared containing 127.7 parts of Cellosolve butyl and 54.8 parts of t-butyl peroctoate. After completing the addition of the monomer masterbatch, the pre-mixed vessel was rinsed 52, 3 parts of butyl Cellosolve. The initiator masterbatch was added immediately over a period of one hour. After complete addition of the initiator masterbatch, the vessel was rinsed with 32.4 parts of Cellosolve butyl. The mixture was held at 98 ° C to 99 ° C for one hour. After one hour, 5.3 parts of t-butyl peroctoate was added and the mixture was held for one hour. After one hour, 5.3 parts of t-butyl peroctoate were added a second time and the mixture was maintained for one more hour. After one hour, 5.3 parts of t-butyl peroctoate were added for the third time and the mixture was held for one hour. The mixture was then cooled to give an acrylic prepolymer having an NV value of 63.6%, an oxirane group of 0.021 eq / 100 grams of solid resin, an acid number of 2.0 and a Brookfield 89 viscosity,

Example 2

Preparation of polymers with acid functional groups

Example 2, Test # 1 A masterbatch containing 163.6 parts of glacial methacrylic acid, 163.6 parts of butyl methacrylate, 36.4 parts of styrene and 23.4 parts of benzoyl peroxide (70% water) was prepared in a separate vessel. A stirrer, reflux condenser, thermocouple, heating mantle and nitrogen blanket were added to the one liter flask. Ten percent of premixes were added to the flask along with

129.6 parts of butanol and 9.8 parts of deionized water. 183.0 parts of butanol and 12.2 parts of deionized water were added to the remainder of the premix. While purging the flask with nitrogen, the contents were heated to 93 ° C. When the temperature of the contents reached 93 ° C, the external heating was turned off and the material was allowed to rise in fifteen minutes. After fifteen minutes, the temperature of the mixture was 97 ° C and the remaining premix was uniformly added over two hours while maintaining the temperature at 97 ° C to 100 ° C. Foaming was controlled by slowing the mixing. After three hours, the heating was turned off and 75 parts of butyl Cellosolve were added. The acrylic prepolymer obtained had an NV value of 44.9%, an acid number of 300 and a viscosity of 24,000 centipoises.

[0126] Two additional batches were produced by the same method. The first additional batch gave a polymer having an NV value of 44.7%, an acid number of 304 and a viscosity of 30 100 centipoise. The second additional batch yielded a polymer having an NV value of 44.7%, an acid number of 306 and a viscosity of 27,500 centipoise.

Example 2, Test # 2 [0127] A premix comprising 512,6 parts of glacial methacrylic acid, 512.6 parts of butyl acrylate, 114.0 parts of styrene and 73.2 parts of benzoyl peroxide (70% water) was prepared in a separate vessel. A stirrer, reflux condenser, thermocouple, heating mantle and nitrogen blanket were added to the 3-liter flask. Ten percent of premix was added to the flask along with 405.9 parts butanol and 30.6 parts deionized water. To the remainder of the pre-mix, 496.1 parts of butanol and 38.3 parts of deionized water were added. While purging the flask with nitrogen, the contents were heated to 93 ° C. When the temperature of the contents reached 93 ° C, the external heating was turned off and the material was allowed to rise in the course of fifteen minutes. After fifteen minutes, the temperature of the mixture was 97 ° C and the remaining premix was uniformly added over two hours while maintaining the temperature at 97 ° C to 100 ° C. After the addition of the premixes was completed, the premixed vessel was rinsed with 5 parts of butanol. The batch was kept at this temperature for two and a half hours. The heating was turned off and 317.7 parts of Cellosolve butyl was added. The acrylic prepolymer obtained had an NV value of 44.4%, an acid number of 314 and a viscosity of 5080 centipoise.

Example 3

Preparation of dispersion

Example 3, test # 1 [0128] A 3-liter flask was prepared as described above. 894.6 parts of the acrylic prepolymer from example 1, test No. 2, 277.3 parts of the prepolymer of example 2, test no. 1, and 13.7 parts of deionized water were added to the flask. The contents of the flask were heated to 99 ° C. After this temperature was reached, five minutes were added

30.3 parts of dimethylethanolamine. The mixture was maintained at 96 ° C to 99 ° C for four hours. After four hours, the heat was turned off, in one hour and fifteen minutes 1036 parts of deionized water were added with strong stirring while the temperature was lowered. The resulting dispersion had a NV value of 30.4%, a particle size of 0.25 micron, a pH 6.75, an acid value of 49.3 and a Brookfield viscosity of 307 centipoise.

Example 3, Test # 2 [0129] Using the process scheme of Example 3, Test No. 1, 881 parts of the acrylic prepolymer from Example 1, Test No. 2, 273.1 parts of the prepolymer from Example 2, Test No. 2, 13.5 parts of water deionized, 29.8 parts of dimethyl ethanolamine and 1020 parts of deionized water were used to prepare the dispersion. The dispersion had a NV value of 30.3%, a particle size of 0.21 micron, a pH of 6.96 and a Brookfield viscosity of 3700 centipoises.

[0130] The repeated batch had a NV value of 30.4%, a particle size of 0.22 wetron and a viscosity of 7500 centipoise.

Example 3, Test # 3 [0131] Using the process scheme of Example 3, Test No. 1, 1417 parts of the acrylic prepolymer from Example 1, Test No. 2, 434.8 parts of the prepolymer of Example 2, Test No. 1, 21.5 parts of water deionized, 47.5 parts of dimethyl ethanolamine and 945 parts of deionized water were used to prepare the dispersion. The dispersion had a NV value of 37.8%, a particle size of 0.25 micron, a pH of 6.71, an acid value of 47.1 and a Brookfield viscosity of 14 300 centipoise.

[0132] The repeated batch had a NV value of 37.7%, a particle size of 0.29 microns, an acid number of 50.0 and a viscosity of 16 600 centipoises. The third batch recovered had a NV value of 37.8%, a particle size of 0.29 micron, an acid value of 50.2 and a viscosity of 16 600 centipoise.

Example 3, Test # 4 [0133] Using the process scheme of Example 3, Test No. 1, 1672 parts of the acrylic prepolymer of Example 1, Test No. 1, 513 parts of the prepolymer of Example 2, Test No. 1, 25.4 parts of deionized water, 56.0 parts of dimethyl ethanolamine and 1115.1 parts of deionized water were used to prepare the dispersion. The dispersion had a NV value of 37.9%, a particle size of 0.30 micron, and an acid number

50.2 and Brookfield viscosity of 8.270 centipoise. [0134] The first repeated batch had a NV value of 37.3%, a 0.25 micron particle size, an acid value of 50.2 and a Brookfield viscosity of 8150 centipoises. The second batch was NV 37.9%, the particle size was 0.29 micron, the acid value was 49.2 and the Brookfield viscosity was 580 centipoise.

Example 3, test # 5 [0135] Using the process diagram of example 3, sample No. 1,

4,920.6 parts of the acrylic prepolymer from example 1, test no. 3, 1509.3 parts of the prepolymer of example 2, test no. 1, 74.8 parts of deionized water, 164.6 parts of dimethyl ethanolamine and 3280.7 parts of deionized water were used to prepare the dispersion . The dispersion had a NV value of 38.2%, a particle size of 0.31 micron, a pH of 6.84 and a Brookfield viscosity of 27.500 centipoises.

[0136] The repeated batch had a NV value of 38.0%, a particle size of 0.34 micron, a pH of 6.91 and a Brookfield viscosity of 32,000 centipoises.

Example 3, test # 6 [0137] A 12-liter flask was prepared as described above. 4740.4 parts of the acrylic prepolymer from example 1, test no. 3, and 1454 parts of the prepolymer from example 2, test no. 1 were added to the flask. The contents of the flask were heated to 98 ° C. When this temperature was reached, 72 parts of deionized water and 158.6 parts of dimethylethanolamine were added in five minutes. The mixture was maintained at 99 ° C to 100 ° C for three and a half hours. After three and a half hours, 791.1 parts of Rutaphen 9989 LB (phenol resin solution containing 60% solids from Bakelite AG) were added, 401, 1 part Santolink EP 560 (phenol resin solution containing 80% solids from Solutia) and 326 parts of Varcum 2227-B-55 (phenol resin solution 55% solids from Reichhold), and the temperature has been adjusted to 90 ° C to 95 ° C. The mixture was held for 30 minutes. The heating was turned off and added

3160.6 parts of deionized water with strong stirring for three hours, while the temperature was decreasing. The following day, additional 2963 parts of deionized water were added. The dispersion obtained had a NV value of 37.5% and a pH of 7.21.

Example 3, test No. 7 [0138] A 12 liter flask was prepared as described above. 4072.2 parts of the acrylic prepolymer from example 1, test no. 4, and 1249.3 parts of the prepolymer from example 2, test no. 1 were added to the flask. The contents of the flask were heated to 97 ° C. After this temperature was reached, 61.8 parts of deionized water and 61.8 parts were added over five minutes

136.3 parts of dimethyl ethanolamine. The mixture was maintained at 99 ° C to 100 ° C for four hours. After four hours, the heating was turned off and added

2715,2 parts of deionized water, stirring strongly within two hours, while the temperature decreased.

Immediately after addition, 400 parts of deionized water were added within fifteen minutes. The dispersion obtained had a NV value of 36.9%, a particle size of 0.29 micron, a pH of 6.84, an acid value of 56.6 and a Brookfield viscosity of 6320 centipoise.

Example 4

Preparation of a paste composition

Example 4, test # 1 [0139] In the container, 481.1 parts of the product from example 3 were mixed, sample number 3, 518.9 parts of pigment (zinc oxide), 130 parts deionized water, 33 parts of cellosolve butyl and 85.3 parts of butylcarbitol. . After homogeneity, the contents were introduced into a ball mill and ground to a grain size> 7.

Example 4, test # 2 [0140] 383,8 parts of the product of example 3, sample No. 4, 416.2 parts of pigment (zinc oxide) and 170.0 parts of butylcarbitol were mixed in a suitable container. After homogeneity, the contents were introduced into a ball mill and ground to a grain size> 7.5.

Example 4, Test # 3 [0141] A white paste containing a TiO2 pigment was prepared by mixing 125 parts of the product from example 3, test number 3, and 46.6 parts deionized water, 0.5 part dimethyl ethanolamine, 5 parts Cellosolve butyl and 250 parts pigment (T1O2). The mixture was then stirred with a Hockmeyer mixer to obtain milled material. After milling, the material was diluted by adding 40 parts of the product from example 3, test no. 3, 28 parts deionized water and 0.8 parts dimethylethanolamine.

Example 4, test # 4 [0142] 378, 15 parts of the product of example 3, sample No. 5, and 98.4 parts of deionized water, 1.5 parts of dimethylethanolamine, 756.1 parts of pigment were mixed into a suitable container using a Hockmeyer. TiCy), 15.15 parts of butyl cellosolve and 42.6 parts deionized water. After grinding, the material was diluted by adding 121.05 parts of the product of example 3, test no. 5, 84.6 parts of deionized water and 1.0 parts of dimethylethanolamine.

Example 4, test # 5 [0143] 60 parts of a 3610HVL coating (available from The Valspar Corporation) and 40 parts of a pigment (zinc oxide) were mixed into a suitable container. After homogeneity, the contents were introduced into a ball mill and ground to a grain size> 7.5.

Example 4, test no. 6 [0144] In the corresponding container, 1238.4 parts of the product from example 3, sample No. 4, 1208.4 parts of pigment (zinc oxide) and 522.2 parts of butylcarbitol were mixed. After homogeneity, the contents were introduced into a ball mill and ground to a grain size> 7.

Example 4, Test # 7 [0145] In a suitable container, a Hockmeyer stirrer was used to mix 1471,5 parts of the product from example 3, sample No. 6, and 277.9 parts of deionized water, 5.5 parts of dimethyl ethanolamine, 2776.1 parts of pigment ( TiCl 2), 55.7 parts of butyl cellosolve and 156.4 parts of deionized water. After milling, the material was diluted by adding 470.9 parts of the product of example 3, test no. 6, 284.1 parts of deionized water and 1.8 parts of dimethylethanolamine.

Example 5

Production of golden coating compositions

Example 5, test no. 1 [0146] In a glass container with one-fourth container capacity with plastic agitator, 715 parts of the product from example 3 were mixed, sample No. 1. Stirring slowly added

44.2 parts of Rutaphen 9989 LB, 22.5 parts of Santolink EP 560, 18.2 parts of Varcum 2227-B-55 and 5.4 parts of the zinc oxide paste from example 4, test no 5. Gradually deionized water was added, to get a viscosity of 20.4 seconds in the Ford No. 4 container. This material was then corrected with deionized water and dimethylethanolamine to get a 30% NV value and viscosity

21.2 seconds in the Ford No. 4 container.

Using the process diagram of example 5, sample No. 1, additional gold coatings were made:

<td colspan="9">Table 5</td>

<td>Example 5, test no .:</td><td>2</td><td>3</td><td>4</td><td>5</td><td>6</td><td>7</td><td>8</td><td>9</td>

<td>Ingredient (parts by weight)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Example 3, test number 2</td><td>800</td><td>878</td><td>715</td><td>774.6</td><td>-</td><td>-</td><td>-</td><td>-</td>

<td>Example 3, test no. 1</td><td>-</td><td>-</td><td>-</td><td>-</td><td>715</td><td>-</td><td>-</td><td>-</td>

<td>Example 3, trial No. 4</td><td>-</td><td>-</td><td>-</td><td>-</td><td>-</td><td>723.1</td><td>1674</td><td>604</td>

<td>Example 4, sample number 5</td><td>-</td><td>4.3</td><td>5.4</td><td>-</td><td>5.4</td><td>7.1</td><td>-</td><td>-</td>

<td>Example 4, test no. 1</td><td>-</td><td>-</td><td>-</td><td>-</td><td>-</td><td>-</td><td>-</td><td>6.3</td>

<td>Rutaphen 9989</td><td>-</td><td>-</td><td>44.2</td><td>47.9</td><td>44.2</td><td>58.6</td><td>135.7</td><td>49</td>

<td>Santolink EP560</td><td>-</td><td>-</td><td>22.5</td><td>24.4</td><td>22.5</td><td>29.8</td><td>69.1</td><td>24.9</td>

<td>Varcum 227-B-55</td><td>-</td><td>-</td><td>18.2</td><td>19.7</td><td>18.2</td><td>24.0</td><td>55.6</td><td>20.1</td>

<td>Water</td><td>20.2</td><td>22.5</td><td>118.6</td><td>108.4</td><td>80.9</td><td>107.3</td><td>248</td><td>89.4</td>

Example 6

Preparation of a white coating composition

Example 6, test # 1 [0147] A container of one-fourth container equipped with a metal stirrer incorporates 115.9 parts of the product from example 3, test No. 1. While stirring, 115.9 parts of pigment PW0099B (TiCg) was added, 17.2 parts of Cellosolve. butyl and 2.2 parts of dimethylethanolamine. This material was ground to a grain size of 7 to 7.5 measured in a Hegman grinding meter. Then added

439, 6 parts of the product with the mixture of 2, 3, 3, and No. 1 were mixed

2.6 parts of zinc oxide paste from example 4, test no. 5, 18.0 parts of Cymel 303, 9.7 parts of a phenol resin solution based on bisphenol A, 227.0 parts of deionized water were added and mixed until homogeneous. The viscosity of the mixture was then adjusted to be equal

25.6 seconds in the Ford No. 4 container with dimethylethanolamine.

Example 7

Production of gold and white coating compositions

Example 7, tests no. 1 and 2 [0148] Table 7 gives details of the components of the gold and white coating preparations. Each coating was made in a plastic container (polyethylene) with a capacity of 4 liters. A Hochmeyer stainless steel mixing blade was used to mix and then mix in a container. The rotational speed of the stirrer 1000 rpm is used for each coating. The individual raw materials were introduced into the container in order to maintain the rotational speed of the stirrer of 1000 rpm. After the addition of the component, the mixture was left to stand for 5-10 minutes so that the ingredient was properly mixed and the coating mixture was completely homogenized. After all ingredients were added, the coating was allowed to stir for a further 20-30 minutes so that all ingredients were mixed properly. After this period, leave for 20-30 minutes for each coating to pass through a fabric filter with an inner mesh size of 10 microns. This step was carried out to check if there were no undesirable solid particles or insoluble materials in the coating that could adversely affect the sprayability or performance of the cured thin film in the case of varying coating properties.

<td colspan="3">Table 7</td>

<td>Example 7, sample number:</td><td>1</td><td>2</td>

<td>Components</td><td>wt%</td><td>wt%</td>

<td>Example 3, test no. 5, dispersion</td><td>47.63%</td><td>36.36%</td>

<td>Example 4, test no. 4, paste with titanium dioxide</td><td>0,00%</td><td>22.54%</td>

<td>Example 4, test no. 2, zinc oxide paste</td><td>0.69%</td><td>0.25%</td>

<td>Deionized water</td><td>16.60%</td><td>0,00%</td>

<td>Phenolic resin Rutaphen 9989</td><td>3.90%</td><td>0.73%</td>

<td>Santolink EP 560 phenolic resin</td><td>1.90%</td><td>0,00%</td>

<td>Phenolic resin Varcum 2227</td><td>1.60%</td><td>0,00%</td>

<td>Cymel 303</td><td>0,00%</td><td>1.76%</td>

<td>Ethylene glycol, monobutyl ether</td><td>0,00%</td><td>0.90%</td>

<td>Deionized water</td><td>22.91%</td><td>35.26%</td>

<td>N-butanol</td><td>4.50%</td><td>1.80%</td>

<td>Dimetyloetanolamina</td><td>0.27%</td><td>0.40%</td>

<td>Sum:</td><td>100.00%</td><td>100.00%</td>

<td></td><td></td><td></td>

<td>Viscosity of the coating (Ford cup, 25 ° C)</td><td>16.0 seconds</td><td>24.0 seconds</td>

Example 8

Production of additional gold and white coating compositions

Example 8, tests 1 and 2 [0149] Additional coatings were developed and tested for properties when applied by spraying. As described above, it has been found that these coatings have much better spraying properties. These coatings were prepared in accordance with the general description in Example 7, with changes in the solvent systems being made. The formulations for these two coatings are shown in Tables 8A and 8B below.

<td colspan="3">Table 8A</td>

<td>Example 8, test no .:</td><td>1</td><td>2</td>

<td>Component</td><td>wt%</td><td>wt%</td>

<td>Example 3, test no. 5, resin base</td><td>0,00%</td><td>36.33%</td>

<td>Example 3, test no. 6, resin base</td><td>65.24%</td><td>0,00%</td>

<td>Deionized water</td><td>23.20%</td><td>0,00%</td>

<td>Example 4, test no. 4, paste with titanium dioxide</td><td>0,00%</td><td>22.52%</td>

<td>Example 4, test no. 2, zinc oxide paste</td><td>0.22%</td><td>0.25%</td>

<td>Ethylene glycol, monobutyl ether</td><td>3.98%</td><td>0,00%</td>

<td>Deionized water</td><td>5.61%</td><td>0,00%</td>

<td>Diethylene glycol, monohexyl ether</td><td>1.14%</td><td>0,00%</td>

<td>Phenolic resin Rutaphen 9989</td><td>0,00%</td><td>0.73%</td>

<td>Cymel 303</td><td>0,00%</td><td>1.76%</td>

<td>Ethylene glycol, monobutyl ether</td><td>0,00%</td><td>0.90%</td>

<td>Deionized water</td><td>0.61%</td><td>35.32%</td>

<td>N-butanol</td><td>0,00%</td><td>1.79%</td>

<td>Dimetyloetanolamina</td><td>0,00%</td><td>0.4%</td>

<td>Sum:</td><td>100.00%</td><td>100.00%</td>

<td></td><td></td><td></td>

<td>Viscosity of the coating (Ford cup, 25 ° C)</td><td>20.0 seconds</td><td>24.6 seconds</td>

<td colspan="3">Table 8B</td>

<td>Example 8, test no .:</td><td>3</td><td>4</td>

<td>Component</td><td>wt%</td><td>wt%</td>

<td>Example 3, test no. 7, resin base</td><td>54.21%</td><td>38.40%</td>

<td>Deionized water</td><td>8.53%</td><td>33.44%</td>

<td>Rutaphen 9989 LB</td><td>4.31%</td><td>0.73%</td>

<td>Santolink EP 560</td><td>2.19%</td><td>0,00%</td>

<td>Varcum 2227-B-55</td><td>1.77%</td><td>0,00%</td>

<td>Cymel 303</td><td>0,00%</td><td>1.75%</td>

<td>Deionized water</td><td>6.26%</td><td>0,00%</td>

<td>Ethylene glycol, monobutyl ether</td><td>3.74%</td><td>0.90%</td>

<td>Deionized water</td><td>7.58%</td><td>0,00%</td>

<td>Ethylene glycol, monohexyl ether</td><td>1.10%</td><td>0,00%</td>

<td>Example 4, test no. 6, zinc oxide paste</td><td>0.83%</td><td>0.26%</td>

<td>Deionized water</td><td>3.94%</td><td>0,00%</td>

<td>Deionized water</td><td>5.17%</td><td>0,00%</td>

<td>Example 4, test no. 7, TiO2 paste</td><td>0,00%</td><td>22.42%</td>

<td>butanol</td><td>0,00%</td><td>1.79%</td>

<td>Dimetyloetanolamina</td><td>0.37%</td><td>0.28%</td>

<td>Cycat 600</td><td>0,00%</td><td>0.03%</td>

<td>Sum:</td><td>100.00%</td><td>100.00%</td>

<td></td><td></td><td></td>

<td>Viscosity of the coating (Ford cup, 25 ° C)</td><td>20.0 seconds</td><td>20.0 seconds</td>

Example 9

Usage parameters of the white coating compared to the control [0150]

<td colspan="3">Table 9</td>

<td></td><td>1OQ51EE (control) **</td><td>Example 6, test no. 1</td>

<td></td><td>Dome / edging / empty space</td><td>Dome / edging / empty space</td>

<td>Green beans and salted potatoes 2.5%</td><td></td><td></td>

<td>Corrosion</td><td>10/10 / 6-10</td><td>10/10 / 7-10</td>

<td>Adhesion</td><td>10/10 / 7-10</td><td>10/10/10</td>

<td>Carrot and salty sauce 2,5%</td><td></td><td></td>

<td>Corrosion</td><td>10/10 / 9-10</td><td>10/10/10</td>

<td>Adhesion</td><td>10/10 / 9-10</td><td>10/10/10</td>

<td>Peas test</td><td></td><td></td>

<td>Corrosion</td><td>10/10 / 6-10</td><td>10/10 / 4-9</td>

<td>Adhesion</td><td>10/10 / 5-9</td><td>10/10 / 4-9</td>

<td>Stains on the surface *</td><td>8-9</td><td>7-9</td>

<td>Pasta</td><td></td><td></td>

<td>Corrosion</td><td>10/10 / 7-8</td><td>10/10 / 8-9</td>

<td>Adhesion</td><td>10/10 / 8-9</td><td>10 / 9-10 / 10</td>

<td>Stains on the surface</td><td>8-9</td><td>8</td>

<td>Chicken broth</td><td></td><td></td>

<td>Corrosion</td><td>10/10 / 8-9</td><td>10/10 / 9-9</td>

<td>Adhesion</td><td>10/10 / 9-10</td><td>10/10 / 9-10</td>

<td>Stains on the surface</td><td>9</td><td>8</td>

<td>Salty pickle</td><td></td><td></td>

<td>Corrosion</td><td>10/10/10</td><td>10/10/10</td>

<td>Adhesion</td><td>10/10/10</td><td>10 / 9-10 / 9-10</td>

<td>Tomato soup with basil</td><td></td><td></td>

<td>Corrosion</td><td>10/10/10</td><td>10/10/10</td>

<td>Adhesion</td><td>10/10 / 9-10</td><td>10/10/10</td>

<td>Stains on the surface</td><td>8</td><td>8</td>

<td colspan="3">* Surface spot testing was performed on the basis of a single general reading. ** The control for the white coating was 10Q51EB, a coating acceptable for industrial use provided by The Valspar Corporation.</td>

Example 10

Usable parameters of white coatings

<td colspan="9">Table 10</td>

<td></td><td>Control* (10Q25)</td><td>Example 5, test number 2</td><td>Example 5, test number 3</td><td>Example 5, test number 4</td><td>Example 5, test no. 5</td><td>Example 5 test no. 7</td><td>Example 5, test no. 8</td><td>Example 5, test no. 9</td>

<td>Salted water 2,5%</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Corrosion</td><td>9/9/7</td><td>9.5 / 7/7</td><td>10 / 7.5 / 7</td><td>10 / 7.5 / 7</td><td>9.5 / 6/7</td><td>10/10 / 9.5</td><td>10/10 / 5.5</td><td>10/10/9</td>

<td>Adhesion</td><td>10/10/10</td><td>10 / 5.5 / 6.5</td><td>10/10 / 6.5</td><td>9 / 6.5 / 8.5</td><td>10 / 4.5 / 6</td><td>10 / 9.5 / 9.5</td><td>8.5 / 6.5 / 6.5</td><td>10 / 9.5 / 9</td>

<td>Clam chowder from New England</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Corrosion</td><td>10/10/8</td><td>10/10 / 4.5</td><td>10/10/7</td><td>10/10/8</td><td>10/10/8</td><td>10/10/9</td><td>10/10/10</td><td>10/10/9</td>

<td>Adhesion</td><td>10/10 / 9.5</td><td>10/10/5</td><td>10/10/6</td><td>10/10/8</td><td>10/10/8</td><td>10/10 / 9.5</td><td>10/10 / 9.5</td><td>10/10 / 9.5</td>

<td>stains</td><td>9</td><td>6.5</td><td>7.5</td><td>7</td><td>7.5</td><td></td><td></td><td></td>

<td>Tomato soup with basil</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Corrosion</td><td>10/10 / 9.5</td><td>10/10/7</td><td>10/10 / 6.5</td><td>10/10/9</td><td>10/10/8</td><td></td><td></td><td></td>

<td>Adhesion</td><td>10/10/8</td><td>10/10 / 7.5</td><td>10/10 / 7.5</td><td>10/10 / 8.5</td><td>10/10 / 8.5</td><td></td><td></td><td></td>

<td>Chicken broth</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Corrosion</td><td></td><td></td><td></td><td></td><td></td><td>10/10/10</td><td>10/10/10</td><td>10/10/10</td>

<td>Adhesion</td><td></td><td></td><td></td><td></td><td></td><td>10/10/10</td><td>10/10/10</td><td>10/10/10</td>

<td>stains</td><td></td><td></td><td></td><td></td><td></td><td>10/4 / 7.5</td><td>4 / 3.5 / 7.5</td><td>10 / 7.5 / 8</td>

<td>Peas test</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Adhesion</td><td></td><td></td><td></td><td></td><td></td><td>10/10 / 9.5</td><td>10 / 8.5 / 7</td><td>7/10/8</td>

<td>stains</td><td></td><td></td><td></td><td></td><td></td><td>0/3/6</td><td>0/4/7</td><td>0/4/7</td>

<td colspan="9">* The control for the gold coating parameters was 10Q25EB, an acceptable coating for industrial use provided by The Valspar Corporation.</td>

Example 11

Spray application tests [0152] One of the potential applications of the present invention is the waterborne spray coating of the interior of two-piece, drawn and pressed (D &amp; I) food cans of tinned steel sheet. These types of cans are increasingly used in the food can industry.

[0153] To facilitate application of the coating prototype by spraying on the inside of commercially available pre-formed D &amp; I cans of tinned steel sheet, the viscosity of each coating was reduced so that the flow of each coating through the Ford cup for viscosity testing (nozzle No. 4) remained in range of 16-30 seconds. The viscosity measurement was carried out using a clean, filtered coating at 25 ° C.

[0154] The application of each coating was performed using a D &amp; I laboratory can spraying machine available from HL Fisher Co. It is recognized that this laboratory device is an effective replica of industrial D &amp; I can spraying equipment. [0155] The application and testing of each coating was carried out using commercially available D &amp; I tinned tin cans, whose commercial dimensions were 300 x 407. This means the commercial dimensions of the cans, whose height is 0.113 m and the diameter is 0.076 m. This allows to obtain a can whose internal surface is 0, 032 m². In all cans used for testing, a typical side rim was also used, which increases the resistance of the can to crushing. In addition, each can had a collar that allows for effective connection and closure of the can via a commercially available end of a food can with an appropriate diameter of 300.

[0156] In the case of gold coatings, a sufficient amount of a damp coating was applied to the inside of the D &amp; I can to obtain a total mass of hardened film of 250.0 mg per can. White coatings were applied so as to obtain a total mass of cured thin film of 350.0 mg per can. These coatings are in line with the values ​​currently used in the full-scale production of industrially coated D &amp; I tinned tin cans.

[0157] The cans were thermally cured using a laboratory D &amp; I can oven available commercially from Ross Co. The furnace settings have been programmed to obtain a heat quantity consistent with the values ​​used to obtain industrially coated D &amp; I tinned tin cans. The residence time of each can in the oven was approximately 5.5 minutes. Each can has a maximum temperature of approximately 221 ° C. Each can had a minimum temperature of 213 ° C for about 2.0 minutes. After completion of this thermal drying process, the appearance of each coating, homogeneity (continuity of the dry film) and other application properties were evaluated. The detailed results of these analyzes are presented in Table 11 below.

<td colspan="5">Table 11</td>

<td>Shell code</td><td>10Q25AB *</td><td>Example 7, test no. 1</td><td>10Q51EA *</td><td>Example 7, test number 2</td>

<td>Subsoil</td><td colspan="4">Commercially available D &amp; I cans made of 300 x 407 tinned steel</td>

<td>The weight of the thin layer</td><td colspan="2">240-260 mg per can</td><td colspan="2">340-360 mg per can</td>

<td>Homogeneity coating / metal exposure Scope: Average:</td><td>0.0-1.8 mAs 0.7 mAs</td><td>0.0-7.0 mAa 2.0 mAs</td><td>0.0-7.0 mAs 0.6 mAs</td><td>0.0-2.0 mAs 0, 4 mAs</td>

<td>The ability to spread the coating / wettability</td><td>Perfect</td><td>Good</td><td>Good</td><td>Good</td>

<td>Creating bubbles</td><td>Perfect</td><td>Satisfactory</td><td>Perfect</td><td>Satisfactory</td>

<td colspan="5">* Products available for purchase at The Valspar Corporation</td>

Example 12

Usage parameters of the cured thin film [0158] Prototypes of gold and white coatings were evaluated for the properties of the hardened thin film compared to the corresponding industrial controlable white and gold spray coatings for D &amp; I cans under industrial conditions. The results of this study are presented in Tables 12A and 12B.

<td colspan="3">Table 12A</td>

<td></td><td>10Q25AB</td><td>Example 7, test no. 1</td>

<td>Pea soup with ham and bacon Adhesion</td><td>10</td><td>9</td>

<td>Corrosion</td><td>10</td><td>9</td>

<td>Fresh carrot in a salt brine 2,5% Grip</td><td>10</td><td>8</td>

<td>Corrosion</td><td>10</td><td>8</td>

<td>Salad with three types of bean Grip</td><td>10</td><td>10</td>

<td>Corrosion</td><td>8</td><td>8</td>

<td>Tomato soup with basil Adhesion</td><td>9</td><td>9</td>

<td>Corrosion</td><td>8</td><td>6</td>

<td>Chicken broth Adhesion</td><td>10</td><td>10</td>

<td>Corrosion</td><td>10</td><td>10</td>

<td>Clam chowder from New England Adhesion</td><td>9</td><td>8</td>

<td>Corrosion</td><td>7</td><td>4</td>

<td>Pasta in tomato sauce Adhesion</td><td>8</td><td>8</td>

<td>Corrosion</td><td>5</td><td>7</td>

<td>Soup with Cheddar cheese Adhesion</td><td>8</td><td>9</td>

<td>Corrosion</td><td>8</td><td>8</td>

<td colspan="3">Table 12B</td>

<td></td><td>10Q51EA</td><td>Example 7, test number 2</td>

<td>Creamy corn Adhesion</td><td>10</td><td>10</td>

<td>Corrosion</td><td>10</td><td>7</td>

<td>Fresh carrot in a salt brine 2,5% Grip</td><td>9</td><td>10</td>

<td>Corrosion</td><td>9</td><td>10</td>

<td>Green beans in salt brine 2,5% Grip</td><td>10</td><td>9</td>

<td>Corrosion</td><td>10</td><td>7</td>

<td>Fresh spinach Adhesion</td><td>9</td><td>10</td>

<td>Corrosion</td><td>9</td><td>6</td>

<td>Chicken broth Adhesion</td><td>10</td><td>10</td>

<td>Corrosion</td><td>10</td><td>10</td>

<td>Tomatoes cut Adhesion</td><td>9</td><td>10</td>

<td>Corrosion</td><td>2</td><td>3</td>

<td>Fresh peas in salt brine 2,5% Grip</td><td>10</td><td>10</td>

<td>Corrosion</td><td>10</td><td>10</td>

Example 13

Properties of gold and white coatings after spraying [0159]

The properties of gold and white coatings after spraying were evaluated and are presented below in Table 13.

<td colspan="5">Table 13</td>

<td></td><td>10Q25AB *</td><td>Example 8, test no. 1</td><td>10Q51EA *</td><td>Example 8, test number 2</td>

<td>Subsoil</td><td colspan="4">Commercially available D &amp; I cans made of 300 x 407 tinned steel</td>

<td>The weight of the thin layer</td><td colspan="2">240-260 mg per can</td><td colspan="2">340-360 mg per can</td>

<td>Uniformity of the coating / metal exposure Range: Average:</td><td>0.0-2.0 mAs 0.5 mAs</td><td>0.0 mAs 0.0 mAs</td><td>0.0-2.5 mAs 0.8 mAs</td><td>0.0-3.0 mAs 0.8 mAs</td>

<td>The ability to spread the coating / wettability</td><td>Perfect</td><td>Perfect</td><td>Good</td><td>Good</td>

<td>Creating bubbles</td><td>Perfect</td><td>Good</td><td>Perfect</td><td>Good</td>

<td colspan="5">* Products available for purchase at The Valspar Corporation</td>

Example 14 [0160] A stirrer, a reflux condenser, a thermocouple, a heating mantle, and a nitrogen blanket were attached to a 12-liter flask. In a separate vessel, a masterbatch of monomers containing 1030.8 parts of styrene, 778.8 parts of hydroxypropyl methacrylate, 56.9 parts of glycidyl methacrylate and 80.3 parts of t-butyl peroctoate was prepared. To a 12-liter flask, 217.3 parts of butanol and 706.0 parts of Cellosolve butyl were introduced. The flask was heated to 98 ° C and 12.6 parts of t-butyl peroctoate was added. After 5 minutes the premix was added to the flask over three and a half hours while maintaining the temperature at 96 ° C to 100 ° C. A second initiator masterbatch was prepared containing 93.2 parts of cellosolve butyl and 40 parts of t-butyl peroctoate. After completing the addition of the monomer masterbatch, the pre-mixed vessel was rinsed 38, 0 parts of butyl Cellosolve. A second initiator masterbatch was added immediately over a period of one hour. After complete addition of the initiator masterbatch, the vessel was rinsed

23.7 parts of butyl Cellosolve. The mixture was held at 98 ° C to 99 ° C for one hour. After one hour, 3.8 parts of t-butyl peroctoate was added and the mixture was held for one hour. After one hour, 3.8 parts of t-butyl peroctoate were added a second time and the mixture was maintained for one more hour. After one hour, 3.8 parts of t-butyl peroctoate was added a third time and the mixture was held for one hour. The mixture was then cooled. The next day the mixture was heated to 50 ° C and 950.5 parts of the product from example 2, test no. 1, and 47.1 parts of deionized water were added. The mixture was then heated to below 96 to 100 ° C and 103.6 parts of dimethyl ethanolamine were added over five minutes. The mixture was maintained at 99 ° C to 100 ° C for four hours. After four hours, 17.5 parts of dimethyl ethanolamine, 511.9 parts of Rutaphen 9989 LB (phenol resin solution with a content of 60% solids from Bakelite AG), 264.4 parts of Santolink EP 560 (80% phenol resin solution) were added. Solutia solids) and 215.3 parts of Varcum 2227-B-55 (phenolic resin solution with 55% solids content from Reichhold) and mixed for 15 minutes and warmed. After 15 minutes, the heat was turned off and 2370.0 parts deionized water was added in one hour and forty-five minutes. Then 2411,7 parts of deionized water were added over 8 minutes. Then the batch was cooled. The next day, the batch was heated to boiling and 1300 parts of the distillate were removed. The dispersion obtained had a NV value of 34.1%, pH 6.88, particle size 0,