Coating composition

Abstract

The present invention relates to a coating composition comprising a blend of polyesters, said blend comprising: Based on the total weight of polyester (A) and (B), - 0.1 to 99.9% by weight of one or more saturated polyesters (A); - 99.9 to 0.1% by weight of one or more unsaturated polyesters (B), The one or more (A) and the one or more (B) have a weight average molecular weight (Mw) of at least 15,000 g / mol, measured by gel permeation chromatography using tetrahydrofuran as solvent, and a glass transition temperature of at least 60° C., measured by differential scanning calorimetry according to DIN EN 61006, method A. The present invention also relates to such high molecular weight polyesters, to a method for producing a coated substrate, to such a coated substrate, and to the use of the coating composition.

Description

[Technical Field]

[0001] Field of Invention The present invention relates to a coating composition comprising a blend of high molecular weight polyesters, and to such high molecular weight polyesters. The present invention also relates to a method for producing a coated substrate, such a coated substrate, and the use of the coating composition. [Background technology]

[0002] Background technology Beyond aesthetic reasons, coatings are intended to protect the substrate from destructive effects that may occur intentionally or accidentally. Coatings must meet various requirements, including heat resistance, UV resistance, chemical resistance, and mechanical strength.

[0003] It is well known that coatings are applied to metal substrates to slow down or inhibit corrosion.

[0004] Generally, coatings are applied to a wide variety of substrates either as a liquid using any suitable procedure such as spray coating, roll coating, curtain coating, immersion coating, or dip coating, or as a solid using a fluidized bed or electrostatic deposition methods such as a corona gun or tribogun. Roll coating is particularly suitable for coating metal sheets and coils.

[0005] Typical applications of coatings relate to (light) metal packaging materials, more specifically to the inside and sometimes outside of the metal can body and can edges, to prevent the contents of a can from coming into contact with metal. Contact between metal and packaging can lead to metal corrosion and contamination of the packaging.

[0006] The coating compositions for the interior of beer cans, beverage cans, and food cans must be approved for direct contact with food. The basic function of the interior coating applied to the can body and edges (see, for example, "Polymeric Materials Science and Engineering", Volume 65, Fall Meeting 1991, New York, pages 277-278) is to protect the packaged product to maintain its nutritional value, texture, color, and flavor when purchased and used by consumers. To meet these requirements, the organic film must not contain any substances that could contaminate the packaged product and must maintain its integrity throughout the product's recommended shelf life.

[0007] Many coating compositions for food and beverage containers are based on polyether resins derived from bisphenol A polyglycidyl ether. The bisphenol A in container coatings can be either bisphenol A itself or its derivatives, such as bisphenol A diglycidyl ether, epoxy novolac resin, or polyols prepared from bisphenol A and bisphenol F. However, there are problems. Trace amounts of bisphenol A diglycidyl ether can leach from epoxy resin coatings into the inner coating of storage containers and be absorbed into the human body along with the food. In fact, unacceptably high concentrations of bisphenol A diglycidyl ether leaching from the inner coating have been measured in oil-containing fish cans. Bisphenol A diglycidyl ether is currently suspected of being carcinogenic and estrogenic when ingested by humans. While the balance of scientific evidence to date suggests that trace amounts of bisphenol A or bisphenol A diglycidyl ether that may be released from existing coatings are not likely to cause harm to human health, some still perceive these compounds as harmful to human health. Therefore, there is a strong desire to eliminate these compounds from coatings for food and beverage containers. Consequently, there is a need for can coating compositions for food and beverage containers that do not contain extractable amounts of bisphenol A, bisphenol A diglycidyl ether, or other derivatives of bisphenol A, and that possess commercially acceptable properties.

[0008] Coatings for food and beverage containers should preferably be able to be applied to the substrate at high speed, such as in coil coating or sheet coating operations, and should provide the required properties upon curing. The coating should generally be able to maintain proper film integrity during container manufacturing and withstand the processing conditions that the container may experience during product packaging. Pre-coated metal sheets are subjected to severe tensile and compressive stresses during the can forming process.

[0009] To address the shortcomings of currently applied coating formulations, the packaging coating industry has been exploring coatings based on alternative binder systems, such as polyester resins. However, formulating polyester-based coatings that strike a balance between the required coating properties (e.g., flexibility, adhesion, solvent resistance, sterilization resistance, etc.) has been challenging.

[0010] Polyester-based coatings for the inner surfaces of can bodies and can edges have already been disclosed in a vast number of prior art documents.

[0011] US 4,452,954(A) discloses a coating comprising a polymer having a backbone containing both ester and urethane bonds and one or more polycyclic groups including saturated bicyclic groups, aromatic bicyclic groups, at least tricyclic groups, or combinations thereof, wherein the polymer is formed by the reaction of a polyisocyanate compound with a hydroxyl-functionalized polyester oligomer or polymer having 25 to 200 hydroxyl numbers.

[0012] EP 2416962 B1 discloses a binder polymer having one or more skeleton unsaturated cyclic aliphatic groups having double bonds located between carbon atoms of the ring, wherein the unsaturated cyclic aliphatic groups include at least bicyclic unsaturated groups and have an iodine value of at least 10 as determined by test method E "iodine value"; and a coating composition comprising a resol-type phenol crosslinking agent.

[0013] US 10,563,010 B2 discloses a coating composition comprising an unsaturated polyester polymer having an iodine value of at least 10, wherein the polyester polymer comprises an ether linkage, or the coating composition comprises a metal desiccant, or the polyester polymer comprises an ether linkage and the coating composition comprises a metal desiccant.

[0014] US 9,200,176 B2 discloses a coating composition comprising a polyester polymer having a backbone or pendant unsaturated monocyclic cycloaliphatic group.

[0015] US 8,449,960 B2 discloses a coating composition comprising a binder polymer having a glass transition temperature of at least 25 °C, a backbone or pendant unsaturated at least bicyclic group having a double bond located between carbon atoms of the ring, and an iodine value of at least about 10; and a crosslinking agent.

[0016] US 8,168,276 B2 discloses a coating prepared from a composition comprising a resin system containing carboxyl groups, hydroxyl groups, or a combination thereof; a crosslinking agent containing a phenolic crosslinking agent, an amino crosslinking agent, or a combination thereof; and a catalyst containing a titanium-containing catalyst, a zirconium-containing catalyst, or a combination thereof, the composition being substantially free of bisphenol A.

[0017] WO 2016 / 073711 (A1) discloses a thermosetting composition comprising: a curable polyester resin; and a crosslinking agent composition containing a resol-type phenolic resin, the phenolic resin containing residues of unsubstituted phenol and / or meta-substituted phenol, the crosslinking agent composition.

[0018] US 7,144,975 B2 discloses an unsaturated amorphous polyester containing at least one α,β-unsaturated dicarboxylic acid component and one alcohol component, the alcohol component being an isomeric compound 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 decane, 4,8-bis(hydroxymethyl)tricyclo[5.2.1.0 2,6 decane and 5,8-bis-(hydroxymethyl)tricyclo[5.2.1.0 2,6The mixture contains a mixture of decane isomers, each isomer may be present in a proportion of 20 to 40% of the mixture, the sum of the three isomers being 90 to 100%, and at least 5% of the mixture is present in the polyester alcohol component. An example of an unsaturated polyester resin is characterized by an acid value of about 25 mg KOH / g, a hydroxyl value of about 36 mg KOH / g, a glass transition temperature of 12°C or less, and a weight-average molecular weight of 5,500 or less.

[0019] WO 2009 / 013063 A1 discloses a non-yellowing, low-viscosity, unsaturated, amorphous polyester comprising an acid component comprising 10 to 100 mol% of at least one α,β-unsaturated dicarboxylic acid and 0 to 90 mol% of at least one linear and / or branched, aliphatic and / or cyclic aliphatic and / or aromatic di- and / or polyfunctional carboxylic acid; and an alcohol component comprising 5 to 100 mol% of a disidol mixture and 0 to 95 mol% of at least one di- and / or polyfunctional alcohol, wherein the polyester is characterized by a glass transition temperature of -30°C and +90°C, and a weight-average molecular weight of 900 to 27,000, preferably 1,000 to 15,000 g / mol.

[0020] US 6,143,841(A) discloses coating formulations including the following: A) Thermoplastic base polyesters comprising a copolymer product of at least one aliphatic, cyclic aliphatic and / or aromatic polybasic acid and / or its anhydride, or at least one hydroxycarboxylic acid or its derivative, and at least one diol; B) An unsaturated addition polyester resin prepared by condensing at least one unsaturated dicarboxylic acid and optionally at least one saturated dicarboxylic acid monomer with at least one diol and / or triol, wherein the ratio of the unsaturated addition polyester to the base polyester is in the range of 0.1 to 15 parts to 99.9 to 85 parts; and C) At least one substance selected from the group consisting of coloring pigments, fillers, stabilizers, leveling agents, and glossing agents. The diol used to prepare the unsaturated addition polyester is 3(4),8(9)bis-(hydroxymethyl)tricyclo-(5,2,10,2,6)decane; the unsaturated dicarboxylic acid monomers used to prepare the unsaturated addition polyester are maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid and / or tetrahydrophthalic acid. The glass transition temperature of the base polyester is 10-40°C, and the melting point is 160-180°C.

[0021] Polyester-based coating systems, being substantially bisphenol-free, generally lack one or more film properties compared to coating systems based on polyether resins containing (or containing) bisphenol polyglycidyl ethers. [Overview of the project]

[0022] Purpose of the invention The present invention aims to provide a coating composition that does not exhibit the drawbacks of the prior art.

[0023] The object of the present invention is to provide a coating composition with improved solvent resistance, substrate adhesion, and flexibility.

[0024] A further object of the present invention is to provide coating compositions for coils and cans.

[0025] Another objective is to provide a can coating composition that exhibits a combination of properties equivalent to or better than the most advanced products on the market, while not using HSE / FDA-concerned substances such as bisphenol A, bisphenol F, formaldehyde, and isocyanates.

[0026] Summary of the Invention The present invention discloses a coating composition comprising a polyester blend, the blend comprising: Based on the total weight of polyester (A) and (B), - One or more saturated polyesters (A) in an amount of 0.1 to 99.9% by weight, and - 99.9 to 0.1% by weight of one or more unsaturated polyesters (B), The one or more (A) and one or more (B) described above have a weight-average molecular weight (Mw) of at least 15,000 g / mol, as measured by gel permeation chromatography using tetrahydrofuran as the solvent, and a glass transition temperature of at least 60°C, as measured by differential scanning calorimetry according to DIN EN 61006, Method A.

[0027] Preferably, one or more (A) and / or one or more (B) include an aliphatic cyclic group;

[0028] Preferred embodiments of the present invention disclose one or more of the following features: - One or more (A) and / or one or more (B) include an aliphatic bicyclic group and / or a tricyclic group, preferably an aliphatic tricyclic group; - One or more (A) and / or one or more (B) are obtained by esterification of a polycarboxylic acid (and / or anhydride) with a polyol comprising an aliphatic polycyclic diol selected from the group consisting of bicyclic diols, tricyclic diols and mixtures thereof; - Preferably, one or more (A) and / or one or more (B) are 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ]decane, and 5,8-bis-(hydroxymethyl)-tricyclo[5.2.1.0 2,6 Obtained from the esterification of a polyol containing an aliphatic tricyclic diol selected from the group consisting of decane and mixtures thereof with a polycarboxylic acid; - One or more (B) includes unsaturated dicarboxylic acids, α,β-unsaturated acid anhydrides, unsaturated diacides containing an isolated ethylenically unsaturated double bond, unsaturated acid anhydrides containing an isolated ethylenically unsaturated double bond, and mixtures thereof, selected from the group consisting of unsaturated diacides or anhydrides; - The coating composition comprises 35-50% by weight of a blend containing one or more (A) and one or more (B), and 50-65% by weight of one or more organic solvents selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, ketones, esters, glycols, glycol ethers, glycol esters, and mixtures thereof.

[0029] The present invention further discloses a method for manufacturing a coated metal substrate, comprising the following steps: - The coating composition is applied to at least one side of a metal substrate, which may be pre-treated and / or containing a primer, to a coating thickness adjusted to a dry coating (or dry film) thickness of less than 60 μm; - The applied coating composition is heated at a temperature of at least 150°C for at least 20 seconds to form a cross-linked coating layer on the metal substrate;

[0030] The present invention further discloses a method for manufacturing a coated can body and can end, comprising the following steps: - Cut the coated metal substrate into metal pieces of the desired dimensions and shape to form the can body and can end, ready for assembly, or - The coated metal substrate is cut into metal pieces of the desired dimensions and shape, the metal pieces are embossed onto the can body, and the can ends are cut into the desired shape to prepare them for assembly. In connection with the present invention, the following is further disclosed. [1] A coating composition comprising a polyester blend, wherein the blend comprises: Based on the total weight of polyester (A) and (B), One or more saturated polyesters (A) in an amount of 0.1 to 99.9% by weight, and 99.9-0.1% by weight of one or more unsaturated polyesters (B), The one or more (A) and one or more (B) have a weight-average molecular weight (Mw) of at least 15,000 g / mol, as measured by gel permeation chromatography using tetrahydrofuran as the solvent, and have a glass transition temperature of at least 60°C, as measured by differential scanning calorimetry according to DIN EN 61006, Method A. The aforementioned coating composition. [2] The coating composition according to [1], wherein one or more (A) and / or one or more (B) comprises one or more aliphatic cyclic groups. [3] A coating composition according to [1] or [2], wherein one or more (A) and / or one or more (B) comprises an aliphatic polycyclic group. [4] A coating composition according to any one of [1] to [3], wherein one or more (A) and one or more (B) have a weight-average molecular weight (Mw) of 20,000 to 50,000 g / mol and / or a glass transition temperature of 80 to 120°C. [5] A coating composition according to any one of [1] to [4], Here, one or more (B) are the following reaction products: - Acid components comprising 50-90 mol% terephthalic acid and / or isophthalic acid, 10-50 mol% unsaturated diacitors or their anhydrides, and 0-30 mol% saturated aliphatic, saturated cyclic aliphatic or aromatic diacitors or their anhydrides, and - A glycol component comprising 5-30 mol% of one or more aliphatic and / or cyclic aliphatic diols and 70-95 mol% of one or more aliphatic polycyclic diols; and / or Here, one or more (A) are the following reaction products: - An acid component comprising 50-100 mol% terephthalic acid and / or isophthalic acid, and 0-50 mol% saturated aliphatic, saturated cyclic aliphatic or aromatic diacitors or their anhydrides, and - A glycol component comprising 5-30 mol% of one or more aliphatic and / or cyclic aliphatic diols and 70-95 mol% of one or more aliphatic polycyclic diols. [6] The coating composition according to [5], wherein one or more aliphatic polycyclic diols of one or more (A) and / or one or more (B) are diols selected from the group consisting of bicyclic diols, tricyclic diols and mixtures thereof. [7] A coating composition according to any one of [5] to [6], wherein one or more aliphatic polycyclic diols of one or more (A) and / or one or more (B) comprises a hetero-bicyclic diol, the hetero-bicyclic diol having a bicyclic aliphatic ring in which one or more hydrocarbons in the ring are substituted with heteroatoms, and the hetero-bicyclic diol is selected from the group consisting of isosorbide, isomannide, isoidide, and derivatives thereof. [8] One or more aliphatic polycyclic diols of one or more (A) and / or one or more (B) are 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ]decane, and 5,8-bis-(hydroxymethyl)-tricyclo[5.2.1.0 2,6 A coating composition according to any one of [5] to [6], comprising a tricyclic diol selected from the group consisting of decane and mixtures thereof. [9] A coating composition according to any one of [5] to [8], wherein one or more unsaturated diacids or anhydrides of one or more of (B) are selected from the group consisting of α,β-unsaturated dicarboxylic acids; α,β-unsaturated acid anhydrides, unsaturated diacids containing an isolated ethylenically unsaturated double bond; unsaturated acid anhydrides containing an isolated ethylenically unsaturated double bond; and mixtures thereof.

[10] A coating composition according to any one of [5] to [9], wherein one or more unsaturated diacids or anhydrides of (B) are selected from the group consisting of maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, tetrahydrophthalic acid, nadic acid, methylnadic acid, or anhydrides thereof, and mixtures thereof.

[11] A coating composition according to any one of [1] to

[10] , wherein one or more (B) has an unsaturated equivalent weight containing 300 to 6,000 g / equiv.

[12] One or more (A) are terephthalic acid, 1,4-butanediol, and 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ]decane, and 5,8-bis-(hydroxymethyl)-tricyclo[5.2.1.0 2,6 A coating composition according to any one of [1] to

[11] , which is a reaction product with a mixture of decanes.

[13] One or more (B) are terephthalic acid, maleic anhydride and / or fumaric acid, 1,4-butanediol, and 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ]decane, and 5,8-bis-(hydroxymethyl)-tricyclo[5.2.1.0 2,6 A coating composition according to any one of [1] to

[12] , which is a reaction product with a mixture of decanes.

[14] A coating composition according to any one of [1] to

[13] , comprising 35% to 50% by weight of a blend containing one or more (A) and one or more (B), and 50% to 65% by weight of one or more organic solvents selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, ketones, esters, glycols, glycol ethers, and glycol esters, and mixtures thereof.

[15] A coating composition according to any one of [1] to

[14] , comprising one or more additives selected from the group consisting of carriers, additive polymers, emulsifiers, pigments, metal powders or pastes, fillers, migration prevention aids, antimicrobial agents, thickeners, lubricants, mixtures, wetting agents, biocides, plasticizers, crosslinking agents, crosslinking catalysts, defoamers, colorants, waxes, antioxidants, rust inhibitors, flow control agents, thixotropic agents, dispersants, adhesion promoters, ultraviolet stabilizers, and scavengers.

[16] A coating composition according to any one of [1] to

[15] , comprising 0.05% to 1.5% by weight of an adhesion promoter based on the weight of a non-volatile substance in the coating composition.

[17] A coating composition according to any one of [1] to

[16] , comprising 0.05% to 1.5% by weight of tetraalkyl titanate, preferably tetrabutyl titanate, based on the weight of nonvolatile substances in the coating composition.

[18] A coating composition according to any one of [1] to

[17] , comprising less than 10,000 ppm of a component selected from the group consisting of BPA-NI (intentionally free of bisphenol A), formaldehyde, isocyanates, and mixtures thereof.

[19] The reaction product is an unsaturated polyester (B) as follows: - Acid components including 50-90 mol% terephthalic acid and / or isophthalic acid, 10-50 mol% unsaturated diacitors or their anhydrides, and 0-30 mol% saturated aliphatic, saturated cyclic aliphatic or aromatic diacitors or their anhydrides, - A glycol component comprising 5-30 mol% of one or more aliphatic and / or one or more cyclic aliphatic diols, and 70-95 mol% of one or more aliphatic polycyclic diols, moreover The unsaturated polyester (B) having the following: - The weight-average molecular weight measured by gel permeation chromatography using tetrahydrofuran as the solvent is at least 15,000 g / mol. - A glass transition temperature of at least 60°C, as measured by differential scanning calorimetry according to Method A of DIN EN 61006, and - Unsaturated equivalent weight is 300~6,000g / equiv.

[20] A substrate selected from the group consisting of metals, glass, polymers, composite materials, concrete, ceramics and artificial wood, preferably a metal substrate, coated with any of the compositions described in [1] to

[18] .

[21] The substrate according to

[20] , wherein the metal substrate is a metal coil or a can, preferably a can for food and beverage applications.

[22] A method for manufacturing a coated metal substrate, comprising the following steps: - Apply the coating compositions described in [1] to

[18] to at least one side of a metal substrate, optionally pre-treated and / or containing a primer, to a coating thickness adjusted so that the dry coating thickness is less than 60 μm; - The applied coating composition is subjected to stove treatment at a temperature of at least 150°C for at least 20 seconds to form a cross-linked coating layer on the metal substrate.

[23] A method for manufacturing a coated can body and can end, including the following steps: - Cut the coated metal substrate of

[22] into metal pieces of the desired dimensions and shape to form the can body and can end, and prepare for assembly, or - Cut the coated metal substrate

[22] into metal pieces of the desired dimensions and shape, emboss the metal pieces onto the can body, cut the can ends into the desired shape, and prepare for assembly.

[24] Use of any of the coating compositions described in [1] to

[18] for coating a metal substrate. [Modes for carrying out the invention]

[0031] Detailed description of the invention The coating formulation (or coating composition) according to the present invention comprises a blend of one or more saturated polyesters (A) and one or more unsaturated polyesters (B), wherein the blend comprises: Based on the total weight of polyester (A) and (B), - One or more saturated polyesters (A) in an amount of 0.1 to 99.9% by weight, preferably 0.5 to 99.5% by weight, more preferably 1 to 99% by weight, even more preferably 5 to 95% by weight, still more preferably 10 to 90% by weight, still more preferably 15 to 85% by weight, or still more preferably 20 to 80% by weight, most preferably 35 to 80% by weight; and - One or more unsaturated polyesters (B) in an amount of 99.9 to 0.1% by weight, preferably 99.5 to 0.5% by weight, more preferably 99 to 1% by weight, even more preferably 95 to 5% by weight, still more preferably 90 to 10% by weight, still more preferably 85 to 15% by weight, or even more preferably 80 to 20% by weight, most preferably 65 to 20% by weight.

[0032] Preferably, one or more saturated polyesters (A) and / or one or more unsaturated polyesters (B) contain one or more aliphatic cyclic groups in the polyester backbone, more preferably, one or more saturated polyesters (A) and / or one or more unsaturated polyesters (B) contain one or more aliphatic cyclic groups in an amount of 10 to 70% by weight, more preferably 15 to 65% by weight, even more preferably 20 to 60% by weight, and most preferably 25 to 60% by weight.

[0033] More preferably, both one or more saturated polyesters (A) and one or more unsaturated polyesters (B) each contain one or more aliphatic cyclic groups in the polyester backbone, and even more preferably, both one or more saturated polyesters (A) and one or more unsaturated polyesters (B) each contain 10 to 70% by weight, more preferably 15 to 65% by weight, or even more preferably 20 to 60% by weight, and most preferably 25 to 60% by weight of one or more aliphatic cyclic groups.

[0034] An aliphatic cyclic group refers to either an aliphatic monocyclic group or an aliphatic polycyclic group.

[0035] By aliphatic monocyclic group, the present invention means a C4-C6 cyclic group (for example, in the C4-C6 cyclic group, one or more hydrocarbons (-CH2-) are substituted with heteroatoms, and / or the C4-C6 cyclic group has substituents that constitute heteroatoms).

[0036] The aliphatic monocyclic group is incorporated into the polyester backbone, preferably in the presence of a polyol and a polycarboxylic acid, and preferably by esterification of an aliphatic monocyclic diol, such as 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-butanediol and / or 1,4-cyclohexanediol and / or monocyclic dicarboxylic acid and / or anhydride, such as 2-cyclohexanedicarboxylic acid or its anhydride, 1,3-cyclohexanedicarboxylic acid, or 1,4-cyclohexanedicarboxylic acid.

[0037] Preferably, the aliphatic polycyclic group is an aliphatic bicyclic group and / or an aliphatic tricyclic group, and more preferably an aliphatic tricyclic group.

[0038] Preferably, the aliphatic polycyclic group does not contain an ethylenically unsaturated double bond in the polycyclic ring structure.

[0039] The aliphatic tricyclic diol is preferably 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane, 5,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 Decane, and mixtures thereof (these mixtures are referred to as TCD-diols).

[0040] Preferably, the aliphatic tricyclic diol comprises at least one aliphatic tricyclic compound, and more preferably, the aliphatic tricyclic diol comprises a mixture of at least two aliphatic tricyclic compounds.

[0041] The aliphatic bicyclic diol is preferably an aliphatic heterobicyclic diol selected from the group consisting of isosorbide, isomannide, isoidide, and their derivatives.

[0042] In this specification, the term "aliphatic heterobicyclic diol" means an aliphatic bicyclic diol having a bicyclic aliphatic ring, wherein the ring contains at least one heteroatom, that is, in the ring, one or more hydrocarbons (-CH2-) are substituted with heteroatoms (e.g., oxygen).

[0043] Preferably, the aliphatic bicyclic diol comprises at least one aliphatic bicyclic diol, and more preferably, the aliphatic bicyclic diol comprises a mixture of at least two aliphatic bicyclic diols.

[0044] Aliphatic polycyclic groups are preferably incorporated into the polyester skeleton by esterification of an aliphatic polycyclic diol with a polycarboxylic acid and / or anhydride and / or polyol.

[0045] In some cases, aliphatic polycyclic groups are incorporated into the polyester backbone by esterification of a mixture containing one or more aliphatic bicyclic diols and one or more aliphatic tricyclic diols with polycarboxylic acids and / or anhydrides and polyols.

[0046] Preferably, one or more saturated polyesters (A) are the following reaction products: - An acid component comprising 50 to 100 mol%, preferably 60 to 100 mol%, more preferably 70 to 100 mol%, most preferably 80 to 100 mol%, of an aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid, and mixtures thereof, and 0 to 50 mol%, preferably 0 to 40 mol%, more preferably 0 to 30 mol%, most preferably 0 to 20 mol%, of one or more saturated aliphatic, saturated cyclic aliphatic, or aromatic diacitors or their anhydrides, and - A glycol component comprising 5-30 mol%, preferably 10-25 mol%, of one or more aliphatic and / or cyclic aliphatic diols, and 70-95 mol%, preferably 75-90 mol%, of one or more aliphatic polycyclic diols. One or more saturated polyesters (A) have a weight-average molecular weight of at least 15,000 g / mol, as measured by gel permeation chromatography using tetrahydrofuran as the solvent, and a glass transition temperature of at least 60°C, as measured by differential scanning calorimetry according to DIN EN 61006, Method A.

[0047] More preferably, one or more saturated polyesters (A) are the following reaction products: - An acid component comprising 50 to 100 mol%, preferably 60 to 100 mol%, more preferably 70 to 100 mol%, most preferably 80 to 100 mol%, of an aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid, and mixtures thereof, and 0 to 50 mol%, preferably 0 to 40 mol%, more preferably 0 to 30 mol%, most preferably 0 to 20 mol%, of one or more saturated aliphatic, saturated cyclic aliphatic, or aromatic diacitors or their anhydrides, and - A glycol component comprising 5-30 mol%, preferably 10-25 mol%, one or more aliphatic and / or cyclic aliphatic diols, and 70-95 mol%, preferably 75-90 mol%, one or more aliphatic polycyclic diols; Here - Saturated aliphatic diacids are selected from the group consisting of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and mixtures thereof; - Saturated cyclic aliphatic diacids are selected from the group consisting of 1,2-cyclohexanedicarboxylic acid or its anhydride, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and mixtures thereof; - Aromatic diacids are selected from the group consisting of phthalic acids, 2,6-naphthalenedicarboxylic acids, 2,7-naphthalenedicarboxylic acids, and mixtures thereof; and - Aliphatic diols are selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, neopentyl glycol hydroxypivalate, and mixtures thereof; - The cyclic aliphatic diols are selected from the group consisting of 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-butanediol, 1,4-cyclohexanediol, and mixtures thereof.

[0048] More preferably, one or more saturated polyesters (A) are terephthalic acid as a dicarboxylic acid component, 1,4-butanediol as an aliphatic diol component, and 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane, aliphatic polycyclic diol component: 5,8-bis-(hydroxymethyl)-tricyclo[5.2.1.0 2,6 It is a mixture of decanes.

[0049] Preferably, one or more unsaturated polyesters (B) are the following reaction products: - An acid component comprising 50 to 90 mol%, preferably 60 to 85 mol%, of an aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and mixtures thereof; 10 to 50 mol%, preferably 15 to 40 mol%, of one or more unsaturated diacids or their anhydrides; and 0 to 30 mol%, preferably 0 to 20 mol%, of one or more saturated aliphatic, saturated cyclic aliphatic, or aromatic diacids or their anhydrides, - A glycol component comprising 5 to 30 mol%, preferably 10 to 25 mol%, of one or more aliphatic and / or cyclic aliphatic diols, and 70 to 95 mol%, preferably 75 to 90 mol%, of one or more aliphatic polycyclic diols. Here, one or more unsaturated polyesters (B) have a weight-average molecular weight of at least 15,000 g / mol as measured by gel permeation chromatography using tetrahydrofuran as the solvent, a glass transition temperature of at least 60°C as measured by differential scanning calorimetry according to DIN EN 61006, Method A, and an unsaturated equivalent weight of 300-6,000 g / equiv.

[0050] More preferably, one or more unsaturated polyesters (B) are the following reaction products: - An acid component comprising 50 to 90 mol%, preferably 60 to 85 mol%, of an aromatic dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and mixtures thereof; 10 to 50 mol%, preferably 15 to 40 mol%, of one or more unsaturated diacids or their anhydrides; and 0 to 30 mol%, preferably 0 to 20 mol%, of one or more saturated aliphatic, saturated cyclic aliphatic, or aromatic diacids or their anhydrides, - A glycol component comprising 5 to 30 mol%, preferably 10 to 25 mol%, of one or more aliphatic and / or cyclic aliphatic diols, and 70 to 95 mol%, preferably 75 to 90 mol%, of one or more aliphatic polycyclic diols; Here - Saturated aliphatic diacids are selected from the group consisting of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and mixtures thereof; - Saturated cyclic aliphatic diacids are selected from the group consisting of 1,2-cyclohexanedicarboxylic acid or its anhydride, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and mixtures thereof; - Aromatic diacids are selected from the group consisting of phthalic acids, 2,6-naphthalenedicarboxylic acids, 2,7-naphthalenedicarboxylic acids, and mixtures thereof; - Unsaturated diacids or anhydrides are selected from the group consisting of maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, tetrahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid (also called nadic acid), methylnadic acid, or their anhydrides, and mixtures thereof; and - Aliphatic diols are selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, neopentyl glycol hydroxypivalate, and mixtures thereof; - The cyclic aliphatic diols are selected from the group consisting of 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-butanediol, 1,4-cyclohexanediol, and mixtures thereof.

[0051] More preferably, one or more unsaturated polyesters (B) are terephthalic acid as a dicarboxylic acid component, maleic anhydride and / or fumaric acid as unsaturated dicarboxylic acid components, 1,4-butanediol as an aliphatic diol component, and 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane, aliphatic polycyclic diol component: 5,8-bis-(hydroxymethyl)-tricyclo[5.2.1.0 2,6 It is a blend (mixture) of decane.

[0052] Depending on the circumstances, terephthalic acid and / or isophthalic acid in one or more polyesters (A) and / or one or more polyesters (B) may be entirely or partially substituted with 2,5-franzicarboxylic acid, where partial substitution should be understood as substituting 5 to 95 mol% of terephthalic acid and / or isophthalic acid with 95 to 5 mol% of 2,5-franzicarboxylic acid.

[0053] Each of the one or more polyesters (A) and one or more unsaturated polyesters (B) has a weight-average molecular weight (Mw) of at least 15,000 g / mol, as measured by gel permeation chromatography using tetrahydrofuran as the solvent, and preferably has a polydispersity (DPI = Mw / Mn) of at least 2.

[0054] Preferably, both one or more polyesters (A) and one or more unsaturated polyesters (B) have a weight-average molecular weight (Mw) between 15,000 and 50,000 g / mol, more preferably between 20,000 and 50,000 g / mol, even more preferably between 20,000 and 45,000 g / mol, even more preferably between 25,000 and 45,000 g / mol, even more preferably between 25,000 and 45,000 g / mol, most preferably between 25,000 and 35,000 g / mol, and preferably have a polydispersity (DPI = Mw / Mn) of 2 to 6, more preferably 2 to 5.5, and even more preferably 2 to 5.3.

[0055] Both one or more polyesters (A) and one or more unsaturated polyesters (B) have a glass transition temperature, as measured by differential scanning calorimetry according to DIN EN 61006, Method A, of at least 60°C, preferably at least 70°C, more preferably 80 to 130°C, even more preferably between 90 and 120°C, and most preferably between 95 and 120°C, wherein each of the one or more (A) and one or more (B) meets the glass transition temperature range, or a blend of one or more (A) and one or more (B) meets the glass transition temperature range.

[0056] Preferably, one or more saturated polyesters (A) and one or more unsaturated polyesters (B) have an intrinsic viscosity in chloroform containing 10 to 50 ml / g, preferably 15 to 45 ml / g, more preferably 20 to 40 ml / g, according to DIN 51562 T1; where each of the one or more (A) and one or more (B) has the intrinsic viscosity range, or a blend of one or more (A) and one or more (B) has the intrinsic viscosity range.

[0057] One or more unsaturated polyesters (B) further have an unsaturated equivalent weight including 300 to 6,000 g / equivalent, preferably 500 to 4,000 g / equivalent, more preferably 500 to 2,000 g / equivalent, and most preferably 700 to 1,600 g / equivalent.

[0058] One or more saturated polyesters (A) and / or one or more unsaturated polyesters (B) are prepared in a single or multi-stage condensation process including the following steps: - A step of adding one or more dicarboxylic acids to one or more diols in a stoichiometric excess of 5-15%, and - React by reflux distillation in the presence of an azeotropic hydrocarbon solvent and an esterification catalyst, under nitrogen purging, at a temperature of at least 170°C to 250°C, until an acid value of less than 5 mg KOH / g is obtained.

[0059] Preferably, one or more polyesters (A) are prepared in a one-step process in which one or more diols in stoichiometric excess, one or more diacids, an azeotropic hydrocarbon solvent, and an esterification catalyst are reacted at a temperature between 225 and 250°C until the acid value is less than 5 mg KOH, preferably less than 4 mg KOH / g, and more preferably less than 3 mg KOH / g. If, in particular cases, the intended molecular weight is not obtained, a small amount of saturated aliphatic acid and / or aromatic dicarboxylic acid and / or their anhydrides are added, and the condensation is continued therein until the acid value is less than 5 mg KOH / g, preferably less than 4 mg KOH / g, and more preferably less than 3 mg KOH / g.

[0060] Preferably, one or more unsaturated polyesters (B) are prepared in a two-step process in which one or more diols and one or more diacids in stoichiometric excess are reacted with an azeotropic hydrocarbon solvent and an esterification catalyst at a temperature consisting of 225 to 250°C until the acid value is less than 5 mg KOH, preferably less than 4 mg KOH / g, more preferably less than 3 mg KOH / g. The reaction mixture is then cooled to a temperature consisting of 170 to 190°C, where one or more α,β-unsaturated dicarboxylic acids or their anhydrides, and / or one or more dicarboxylic acids containing an isolated ethylenically unsaturated double bond, or their anhydrides, or their anhydrides are added, and condensation is continued at a temperature of 170 to 190°C until an acid value of less than 5 mg KOH / g, preferably less than 4 mg KOH / g, more preferably less than 3 mg KOH / g is obtained.

[0061] Examples of esterification catalysts used include tin derivatives such as dibutyltin dilaurate, dibutyltin oxide, monobutyltin oxide, or n-butyltin trioctanoate, or titanium derivatives such as tetrabutoxytitanium (also known as tetrabutyl titanate, butyl titanate, or titanium butoxide). The preferred catalyst for polyester preparation in this invention is a tin derivative.

[0062] 0-1% of a phenol derivative, such as IRGANOX® 1010 (manufactured by BASF), alone, or various stabilizers, such as trialkyl phosphite (WESTON TM It can be mixed with a phosphite ester stabilizer such as ) and added to the esterification mixture at any stage of the reaction, i.e., at the start, middle, or end of polyesterization.

[0063] Preferably, one or more saturated polyesters (A) and one or more unsaturated polyesters (B) are diluted in a suitable solvent to obtain the intended viscosity for liquid coating.

[0064] Suitable organic solvents include aliphatic hydrocarbons (e.g., mineral spirits, kerosene, high flash point VM&P naphtha, etc.); aromatic hydrocarbons (e.g., toluene, xylene, solvent naphtha 100, 150, 200, etc.); alcohols (e.g., ethanol, n-propanol, isopropanol, n-butanol, iso-butanol, etc.); ketones (e.g., acetone, 2-butanone, cyclohexanone, etc.); esters (e.g., ethyl acetate, ethyl aryl ketone, ethyl aryl ketone, methyl isoamyl ketone, etc.). Ethyl acetate, butyl acetate, etc.; glycols (butyl glycol, etc.); glycol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, methoxypropanol, etc.); glycol esters (butyl glycol acetate, methoxypropyl acetate, etc.); and mixtures thereof.

[0065] Preferred organic solvents include aliphatic hydrocarbons, aromatic hydrocarbons, glycol esters, and mixtures thereof.

[0066] A mixture comprising one or more saturated polyesters (A) and one or more unsaturated polyesters (B) to which one or more additives selected from the group consisting of carriers, additional polymers, emulsifiers, pigments, metal powders or pastes, fillers, migration prevention aids, antimicrobial agents, thickeners, lubricants, combining agents, wetting agents, biocides, plasticizers, crosslinking agents, crosslinking catalysts, defoamers, colorants, waxes, antioxidants, rust inhibitors, colorants, waxes, antioxidants, rust inhibitors, flow control agents, thixotropic agents, dispersants, adhesion promoters, UV stabilizers, and scavengers is added.

[0067] Depending on the circumstances, the coating formulation of the present invention may further include one or more crosslinking agents. Any suitable crosslinking agent or combination of crosslinking agents can be used. For example, phenol crosslinking agents (e.g., phenoplast), amino crosslinking agents (e.g., aminoplast), blocked isocyanate crosslinking agents, epoxy functional crosslinking agents, and combinations thereof can be used. Preferred crosslinking agents are those that are at least substantially free, more preferably completely free, of the bound bisphenol A and aromatic glycidyl ether.

[0068] When an additional crosslinking agent is used in the coating formulation of the present invention, a phenolic crosslinking agent is preferably used.

[0069] Examples of suitable phenol crosslinking agents include reaction products of aldehydes and phenols. Formaldehyde and acetaldehyde are preferred aldehydes. Non-limiting examples of suitable phenols that can be used include phenol, cresol, p-phenylphenol, p-tert-butylphenol, p-tert-amylphenol, cyclopentylphenol, cresyl acid, and combinations thereof.

[0070] If present, the concentration of one or more arbitrary crosslinking agents in the coating formulation may vary depending on the desired result. For example, in some embodiments, the coating composition may contain one or more crosslinking agents in an amount of 0.01 to 50% by weight, preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and most preferably 15 to 30% by weight, based on the total weight of one or more saturated polyesters (A), one or more unsaturated polyesters (B), and one or more crosslinking agents.

[0071] In the case of a specific optional use of an additional crosslinking agent, the coating composition preferably includes: - Mixture containing 35-50% by weight of the following: · 50-95% by weight of one or more saturated polyesters (A) and one or more unsaturated polyesters (B), • One or more crosslinking agents in an amount of 5-50% by weight, - One or more organic solvents in an amount of 50-65% by weight.

[0072] Preferably, the use of additional crosslinking agents is completely omitted (i.e., the coating formulation of the present invention contains 0.0% crosslinking agent).

[0073] A crosslinking catalyst may be added depending on the circumstances.

[0074] Suitable crosslinking catalysts include peroxides, hydroperoxides, peresters, metal catalysts, strong acids, tertiary and quaternary ammonium compounds, phosphorus compounds, sulfur-containing compounds, and combinations thereof. More specifically, metal catalysts may be added as needed.

[0075] Suitable metal catalysts are selected from the group consisting of aluminum (Al), antimony (Sb), barium (Ba), bismuth (Bi), calcium (Ca), cerium (Ce), chromium (Cr), cobalt (Co), copper (Cu), iridium (Ir), iron (Fe), lead (Pb), lanthanum (La), lithium (Li), manganese (Mn), neodymium (Nd), nickel (Ni), rhodium (Rh), ruthenium (Ru), palladium (Pd), potassium (K), osmium (Os), platinum (Pt), sodium (Na), strontium (Sr), tin (Sn), titanium (Ti), vanadium (V), yttrium (Y), zinc (Zn), and zirconium (Zr), and their salts or complexes. Preferably, suitable metal catalysts are titanium, iron, or manganese, and more preferably, iron or manganese (or their salts or complexes). In this specification, the term "metal catalyst" means "metal crosslinking catalyst."

[0076] When used, the crosslinking catalyst is preferably present in an amount of 0.01 to 3% by weight, more preferably 0.1 to 1.0% by weight based on the weight of the non-volatile substance in the coating composition.

[0077] More preferably, in the coating formulation of the present invention, the addition of a crosslinking catalyst is completely omitted (i.e., the coating formulation of the present invention contains 0.0% of a crosslinking catalyst).

[0078] According to one embodiment, when one or more unsaturated polyesters contain α,β-unsaturated ester moieties, preferably obtained from the esterification of maleic anhydride and / or fumaric acid, the amount of metal catalyst is small, preferably less than 0.1% by weight, more preferably less than 0.001% by weight, based on the weight of nonvolatile substances in the coating composition. Most preferably, no metal catalyst is added (i.e., the coating formulation of the present invention contains 0.0% metal catalyst).

[0079] Furthermore, organometallic compounds and / or organotaloid compounds can be added to the coating composition as adhesion promoters in an amount of up to 1.5% by weight, preferably up to 1.2% by weight, and more preferably up to 0.9% by weight, based on the weight of nonvolatile substances in the coating composition.

[0080] Suitable adhesion-promoting compounds are selected from the group consisting of titanates, zirconates, silanes, and mixtures thereof.

[0081] Preferably, the titanate is selected from the group consisting of tetraalkyl titanates, and more preferably, the tetraalkyl titanate is tetrabutyl titanate.

[0082] Preferably, the zirconate is selected from the group consisting of tetraalkyl zirconates; more preferably, the tetraalkyl zirconate is tetrabutyl zirconate.

[0083] Preferably, the silane is selected from the group consisting of functionalized di- or trialkoxysilanes; more preferably, the functionalized di- or trialkoxysilane is a di- or trimethoxysilane containing an acrylate, amino, or epoxy functional group, such as methacryloxypropylmethyldimethoxysilane, aminopropyltrimethoxysilane, (2-aminoethyl)-3-aminopropyltrimethoxysilane, or 3-glycidoxypropyltrimethoxysilane.

[0084] Preferably, the coating composition contains at least 0.05% by weight, more preferably at least 0.1% by weight, of the adhesion promoter based on the weight of the nonvolatile substance in the coating composition. More preferably, the coating composition contains between 0.05% by weight and 1.5% by weight, more preferably between 0.1% by weight and 1.5% by weight, and most preferably between 0.1% by weight and 1.2% by weight, of the adhesion promoter based on the weight of the nonvolatile substance in the coating composition.

[0085] Preferably, the coating composition contains 0.05% to 1.5% by weight, more preferably 0.1% to 1.5% by weight, and most preferably 0.1% to 1.2% by weight of tetraalkyl titanate, based on the weight of nonvolatile substances in the coating composition; more preferably tetrabutyl titanate.

[0086] According to another embodiment, one or more unsaturated polyesters are present, preferably nadic acid or methylnadic acid or its anhydride, which contain an isolated ethylenically unsaturated double bond, obtained from the esterification of an unsaturated diacid or an anhydride containing an isolated ethylenically unsaturated double bond, such as tetrahydrophthalic acid, preferably a metal catalyst, and more preferably iron or manganese (or its salt or complex), in an amount comprising at least 0.01% by weight, more preferably 0.01 to 3% by weight, and most preferably 0.1 to 1.0% by weight based on the weight of nonvolatile substances in the coating composition.

[0087] Preferably, the coating composition of the present invention contains less than 10,000 ppm, more preferably less than 5,000 ppm, even more preferably less than 1,000 ppm, even more preferably less than 500 ppm, even more preferably less than 100 ppm, or even more preferably less than 50 ppm, and most preferably less than 20 ppm of a component selected from the group consisting of bisphenol-A(NI) (i.e., intentionally bisphenol A-free), formaldehyde, isocyanates, and mixtures thereof.

[0088] The coating compositions of the present invention can be applied to a substrate using any suitable procedure such as spray coating, roll coating, coil coating, curtain coating, dip coating, electrostatic deposition coating, and other types of pretreatment coatings. In one embodiment, when the coating is used to coat a metal sheet or coil, the coating can be applied by roll coating.

[0089] In this invention, "can" refers to various types of cans, such as two-part cans, three-part cans, and 18-liter cans.

[0090] The coating composition of the present invention can be applied to a wide variety of substrates selected from the group consisting of metals, glass, polymers (such as polyimide-amide, polyetherketone, polyethersulfone, polyphenylsulfone, or polybenzimidazole), composite materials, concrete, ceramics, and artificial wood (such as medium-density fiberboard or high-density fiberboard, particleboard, or oriented strand board), provided that the substrate is resistant to stobbing cycle conditions.

[0091] The coating composition of the present invention can be applied to at least one side, preferably two sides, of a substrate.

[0092] Preferably, the substrate is a metal substrate, and more preferably, a tinplate, tin-free steel, or aluminum substrate.

[0093] Preferably, the coating compound is applied to a thickness such that the resulting coating after curing has a dry film thickness of less than 60 μm, preferably less than 30 μm, more preferably 3 to 20 μm, even more preferably 5 to 15 μm, and most preferably 8 to 12 μm.

[0094] The solvent evaporation and curing of the coating can be carried out in a convection oven at a temperature of at least 150°C, preferably 150-250°C, more preferably 170-230°C, even more preferably 180-220°C, and most preferably 190-210°C for at least 20 seconds, preferably 1-25 minutes, more preferably 2-22 minutes, even more preferably 5-20 minutes, even more preferably 8-18 minutes, and most preferably 10-15 minutes.

[0095] Alternatively, the coating can be cured by infrared irradiation such as near-infrared, short-infrared, or mid-infrared radiation, induction heating, or a combination thereof. In embodiments where an infrared or induction system is used, the curing cycle is in the range of 2 to 160 seconds, depending on the heating system or combination of heating systems.

[0096] Finding the appropriate combination of gelatinization temperature and time is quite possible for those skilled in the art.

[0097] The coating formulation according to the present invention is preferably used for coil coating applications, which include the following steps: - Rewind the coil on the metal substrate. - Apply the coating formulation of the present invention to at least one side of the unwound metal substrate to an appropriate coating thickness; - A step of heating the applied coating formulation with a suitable heating system in order to form a metal substrate covered with a crosslinked coating layer; and - The metal substrate is unwound to form a metal substrate coil containing a cross-linked coating layer.

[0098] Before coating, the metal substrate is preferably pre-treated and / or primed. In one embodiment, a coil of metal substrate provided by the supplier is pre-treated and / or primed.

[0099] The coating formulations according to the present invention are preferably used for (light) metal packaging, and more particularly for can coating applications, including the following steps: - Unwind a coated metal substrate coil coated with the curing coating formulation of the present invention; - To manufacture a three-piece can, cut the can body and can ends to the desired shape; - A metal piece is embossed onto the can body, and the can end is cut into the desired shape to manufacture a two-piece can; - Assemble the can body and the can end.

[0100] Preferably, the outer surface of the can includes one or more prints.

[0101] Preferably, the cans are for food and beverages.

[0102] When used for coating coils or cans, the inside and / or outside of the coil or can can be coated with the coating composition of the present invention.

[0103] Preferably, the inside and outside of the coil or can are coated with the coating composition of the present invention.

[0104] Using the coating composition of the present invention yields a coating with good coating performance, and more specifically, improved solvent resistance (compared to using coating compositions already described in the prior art), without losing flexibility. In fact, when the coating composition of the present invention is used, the resulting coating exhibits good sterilization resistance, flexibility, and substrate adhesion after sterilization, more specifically, when the coating composition of the present invention is applied to a metal substrate such as a coil or a can. Furthermore, the preferred coating composition of the present invention does not contain additional crosslinking agents or crosslinking catalysts, and does not contain BPA-NI (intentionally bisphenol A-free, also referred to herein as bisphenol A(NI) or intentionally bisphenol A-free) or formaldehyde. example

[0105] The following illustrative examples are for illustrative purposes only and are not intended to limit or otherwise define the scope of the invention. Example 1: Synthesis of saturated polyester (A)

[0106] A 1-liter four-necked round-bottom flask fitted with a stirrer, reflux condenser with water separator, nitrogen inlet and thermosensor was used to prepare 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane and 5,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 Decane (the mixture is called TCD-diol), 27 g of 1,4-butanediol, 332 g of terephthalic acid, 22 g of Solvent Nafta 150 / 180, and 0.6 g of monobutyltin oxide were mixed under nitrogen purge. The mixture was heated to 180°C under a nitrogen stream and stirred for 90 minutes. The temperature was maintained at 180°C for 30 minutes. Subsequently, the temperature was increased to 240°C at a heating rate of 10°C / h, and reflux distillation was performed by adding 150 / 180 solvent naphtha while separating the reaction water. Reflux distillation was maintained for approximately 3 hours until 70 g of water fraction was recovered. The dynamic viscosity of the sample diluted to 40% solids with the solvent Nafta 150 / 180 was measured at 23°C and was found to be 900–1,000 mPa.s. Subsequently, the temperature was lowered to 180°C, and reflux distillation was restarted by adding Nafta 150 / 180 in small amounts. Reflux distillation was continued for approximately 6 hours until 3.5 g of water fraction was recovered. The acid value was less than 4 mg KOH / g, and the dynamic viscosity at 23°C of the sample diluted to 40% solids with solvent Nafta 150 / 180 was measured to be 3200–3800 mPa.s. The reaction mixture was cooled to 145°C and diluted in small batches with Solvent Nafta 150 / 180 under good stirring conditions, aiming for a target dynamic viscosity of less than 5000 mPa·s at 23°C. The characteristics of this saturated polyester are as follows: non-volatile content according to DIN 55671 (foil method), 180°C, 10 min; acid value of 39.9% according to DIN EN ISO 2114 at 1.5 mg KOH / g; dynamic viscosity according to DIN EN ISO 3219 (Anton Paar, Physica MCR1) at 4,610 mPa.s at 23°C and a shear rate of 10.1 / s; number-average molecular weight and weight-average molecular weight measured by gel permeation chromatography in tetrahydrofuran are 8,826 g / mol and 34,260 g / mol, respectively; and glass transition temperature is 109°C, measured by differential scanning calorimeter according to DIN EN 61006 (Method A). Example 2: Synthesis of unsaturated polyester (B)

[0107] A 1-liter four-necked round-bottom flask fitted with a stirrer, reflux condenser with water separator, nitrogen inlet and thermosensor was used to prepare 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane and 5,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6Decane (TCD-diol), 27 g of 1,4-butanediol, 266 g of terephthalic acid, 18 g of Solvent Nafta 150 / 180, and a mixture of isomers of monobutyltin oxide were charged under nitrogen purging. The mixture was heated to 180°C under a nitrogen stream and stirred for 90 minutes. The temperature was maintained at 180°C for 30 minutes. Subsequently, the temperature was increased to 240°C at a heating rate of 10°C / h, and reflux distillation was performed by adding 150 / 180 solvent naphtha while separating the reaction water. Reflux distillation was continued for approximately 5 hours until 58 g of hydrodistillate was recovered and an acid value of less than 4 mg KOH / g was measured. The reaction mixture was cooled to 170°C, and 39 g of maleic anhydride and 0.7 g of butylhydroxytoluene were added while stirring. The temperature was raised to 180°C, Solvent Nafta 150 / 180 was added, and reflux distillation was restarted. Reflux distillation was continued for approximately 8 hours until 8 g of aqueous distillate was recovered and an acid value of less than 4 mg KOH / g was measured. The reaction mixture was cooled to 145°C and diluted in small batches with Solvent Nafta 150 / 180 under good stirring, with the target dynamic viscosity at 23°C being less than 5,000 mPa.s. The characteristics of this unsaturated polyester are as follows: DIN 55671 (foil method), 180°C, 10 min, 44.7%; acid value 3.4 mg KOH / g according to DIN EN ISO 2114; dynamic viscosity 4,702 mPa.s. according to DIN EN ISO 3219 at 23°C and a shear rate of 10.1 / s; intrinsic viscosity 31.9 ml / g according to DIN 51562 T1-3 using chloroform as the solvent; number-average molecular weight and weight-average molecular weight measured by gel permeation chromatography in tetrahydrofuran are 7,792 g / mol and 34,080 g / mol, respectively; glass transition temperature measured by differential scanning calorimeter according to DIN EN 61006 (Method A) is 105°C; and unsaturated equivalent weight is 1,547 g / equivalent.

[0108] In Examples 2-6, the unsaturated equivalent weight was calculated by dividing the weight of the polyester by the number of moles of ethylenically unsaturated diacid present in the initial reaction mixture, where the weight of the polyester was the sum of the weights of the polyol, polyacid, and ethylenically unsaturated diacid, minus the weight of the water formed during polycondensation. Examples 3-5: Synthesis of unsaturated polyester (B)

[0109] Unsaturated polyesters (B) in Examples 3, 4, and 5 (Table 1) were prepared according to the method in Example 2.

[0110] In Example 3, tetrahydrophthalic anhydride was used as one of the comparative examples shown in Table 8 below, instead of maleic anhydride (as appropriate in Table 1), for further preparation and evaluation of the coating formulation in the absence of saturated polyester (A) in Example 1.

[0111] Example 4a in Table 1 corresponds to the synthesis of unsaturated polyester (B) using an alternative esterification catalyst (i.e., tetrabutyl titanate is used as the esterification catalyst in Example 4a, while monobutyltin oxide is used as the esterification catalyst in Examples 3, 4, and 5.5), and is prepared as follows: A 1-liter four-necked round-bottom flask fitted with a stirrer, reflux condenser with water separator, nitrogen inlet and thermosensor was used to prepare 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane and 5,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 353 g of an isomer mixture of decane (TCD-diol), 27 g of 1,4-butanediol, 232 g of terephthalic acid, 18 g of solvent naphtha 150 / 180, and 2.4 g of tetrabutyl titanate were charged under nitrogen purging. The mixture was heated to 180°C within 90 minutes under a continuous nitrogen stream and stirring. The temperature was maintained at 180°C for 30 minutes. Subsequently, the temperature was increased to 240°C at a heating rate of 10°C / h, and reflux distillation was initiated by adding solvent naphtha 150 / 180 while continuing the separation of reaction water. Reflux distillation was continued for approximately 5 hours until 50 g of hydrodistillate was recovered and an acid value of less than 4 mg KOH / g was measured. The reaction mixture was cooled to 140°C, and 59 g of maleic anhydride and 0.7 g of butylhydroxytoluene were added while stirring. The temperature was raised to 175°C, and more Naphta 150 / 180 solvent was added, and reflux distillation was restarted. Reflux distillation was continued for 8 hours until 11 g of aqueous distillate was recovered and an acid value of less than 4 mg KOH / g was measured. The reaction mixture was cooled to 145°C and diluted in small batches with Solvent Naphta 150 / 180 under good stirring, with the target dynamic viscosity at 23°C being less than 5,000 mPa.s. The characteristics of this unsaturated polyester are as follows: DIN 55671 (foil method), 180°C, 10 min, 44.7%; acid value of 2.7 mg KOH / g according to DIN EN ISO 2114; dynamic viscosity of 2,509 mPa.s. at 23°C and shear rate of 10.1 / s according to DIN EN ISO 3219; intrinsic viscosity of 28.9 ml / g according to DIN 51562 T1-3 with chloroform as the solvent; number-average molecular weight and weight-average molecular weight of 7,066 g / mol and 28,550 g / mol, respectively, as determined by gel permeation chromatography in tetrahydrofuran; glass transition temperature of 105°C and unsaturated equivalent weight of 1,017 g / equivalent, as determined by differential scanning calorimetry according to DIN EN 61006 (Method A). Example 6: Synthesis of unsaturated polyester (B)

[0112] Prepare the unsaturated polyester (B) in Example 6 of Table 1 as follows: A 1-liter four-necked round-bottom flask fitted with a stirrer, reflux condenser with water separator, nitrogen inlet and thermosensor was used to prepare 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6] Decane, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane and 5,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 Decane (TCD-diol), 131 g of isosorbide, 27 g of 1,4-butanediol, 232 g of terephthalic acid, 60 g of solvent naphtha 150 / 180, and 0.6 g of monobutyltin oxide were added under nitrogen purging. The mixture was heated to 180°C within 90 minutes under a continuous nitrogen stream and stirring. The temperature was maintained at 180°C for 30 minutes. Subsequently, the temperature was increased to 240°C at a heating rate of 10°C / h, and reflux distillation was set up by adjusting the amount of 150 / 180 solvent naphtha while continuing the separation of reaction water. When reflux distillation was continued at 240°C for 1 hour, a clear brown reaction mixture was obtained (i.e., no undissolved terephthalic acid remained). The reaction mixture was cooled to 170°C, and 59 g of maleic anhydride and 0.7 g of butylhydroxytoluene were added while stirring. The temperature was raised to 180°C, Solvent Nafta 150 / 180 was added, and reflux distillation was restarted. Reflux distillation was continued at 180°C for 7 hours, and then at 200°C for 10 hours, producing a total of 61 g of reaction water, and the acid value decreased to 1.5 mg KOH / g. The reaction mixture was cooled to 120°C and diluted little by little with methoxypropyl acetate while stirring well. The characteristics of this unsaturated polyester are as follows: DIN 55671 (foil method), 180°C, 10 min, 42.0%; acid value of 1.5 mg KOH / g according to DIN EN ISO 2114; dynamic viscosity of 2,350 mPa.s. at 23°C and shear rate of 10.1 / s according to DIN EN ISO 3219; intrinsic viscosity of 20.2 ml / g in chloroform as solvent according to DIN 51562 T1-3; number-average molecular weight and weight-average molecular weight of 2,840 g / mol and 20,360 g / mol, respectively, as determined by gel permeation chromatography in tetrahydrofuran; glass transition temperature of 96°C and unsaturated equivalent weight of 942 g / equivalent, as determined by differential scanning calorimetry according to DIN EN 61006 (Method A). [Table 1] Example 7: Coating formulation

[0113] Coating formulations were prepared by combining the unsaturated polyesters (B) from Examples 2, 4, 4a, 5, and 6 with the saturated polyester (A) from Example 1 in a ratio of 25:75 to 50:50 (B:A) (calculated by solid content). These formulations were then diluted to 40% solid content with Solvent Naphtha 150 / 180 under stirring, and 0.3% Additol XW 6580 (fluid and substrate wetting agent, Allnex) was added and homogenized for several minutes.

[0114] For details on the various coating formulations prepared, please refer to Tables 2 to 7, and Tables 8 and 9 below. Example 8: Coating application and evaluation .

[0115] A coating agent with 40% solid content was applied to a tin-plated steel sheet panel to a wet film thickness of 40 μm. After a flash-off time of 5 minutes, the coated panel was oven-dried at 200°C for 12 minutes, resulting in a dry film thickness of 10 ± 2 μm. Testing: The evaluation of various paints prepared and applied to panels is carried out based on the following tests. - The cross-cut test, in accordance with DIN EN ISO 2409, tests the adhesion of a dried coating to a substrate by making a series of cuts in the coating. Two parallel cuts intersect at different angles to produce a pattern of 25 or 100 similar squares. For hard substrates, the area is briefly treated with adhesive tape or a stiff brush, and then evaluated using a chart. The classification ranges from 0 to 5, with 0 corresponding to a state where the edges of the cuts are perfectly smooth and no squares in the grid have peeled off. - The surface, flow, leveling, and defects of the coating film are visually evaluated and rated on a 5-point scale from best (0) to worst (5). - The degree of "hardening" or crosslinking is measured as resistance to acetone. This test is performed by the method described in ASTM D5402. The number of double rubs (i.e., the number of reciprocating motions until the metal substrate is visible) is reported. Preferably, acetone solvent resistance is at least 30 double rubs. - Impact tests are measured according to ASTM 2794, and the coating is evaluated with an impact of 32 inch-pounds. Damage to the coating is determined visually or at low magnification. The organic coating under test is applied to four or more suitable thin metal panels. After the coating has cured, it is stored at 20°C for 1 hour. Then, a standard weight is dropped from a standard height to deform the coating and substrate. This indentation is either penetrating (direct impact; coating side) or pushing out (reverse impact; metal side). - The wedge bending test was performed according to ASTM D3281 using a Type 471 Erichsen bending impact tester (cone bolt diameter 5 mm). The test wedge was formed from a coated rectangular metal test sheet (length 10 cm × width 2 cm). The test wedge was formed from the coated sheet by bending (i.e., folding) the sheet around a mandrel with a diameter of 5 mm. Therefore, the mandrel was placed on the coated sheet parallel to the long side of the sheet and equidistant from the long side of the sheet. The resulting test wedge had a diameter of 5 mm and a length of 100 mm. To evaluate the wedge bending properties of the coating, the test wedge was placed vertically on the metal block of the wedge bending tester, and a weight of 1,800 ± g was dropped onto the test wedge from a height of 50 cm. The deformed test wedge was then immersed in an acidic copper sulfate test solution for 5 minutes. This solution is prepared by dissolving 132 g of CuSO45H2O in 900 g of water containing 20 g of concentrated hydrochloric acid. The panel is removed from the solution, rinsed with tap water, wiped dry, and examined under a microscope to measure the millimeters of coating fracture along the deformation axis of the test wedge. The data is expressed as wedge bending ratio using the following calculation: 100% × [(wedge length 100 mm) - (breakage mm)] / (wedge length 100 mm). If the wedge bending ratio is 70% or higher, the coating is considered to have passed the wedge bending test. - Deep drawing test - The Erichsen cup test is performed according to DIN EN 1669, and the metal substrate constituting the coating is formed into a cup. In this test, the metal substrate is placed on the die surface and drawn into a cup by a drawing punch. An asymmetrical so-called "four-corner box" (40 × 40 mm) with four different angles is formed, with the first radius being the largest and the fourth radius being the smallest. Forming is performed in one drawing process with a drawing force of 10 kN and a sheet holder force of 5 kN. The height of the box is 25 mm. Visual inspection of the coated surface is performed after the drawing process to check for defects on the top and sides, and the fracture rate of the sides relative to the total height of 25 mm is calculated. "0%" means that no fracture is observed and the flank coating is fine throughout the entire height of the flank, while the fracture rate is given as "(Y / 25) × 100%". - Teak resistance (whitening resistance) measures the ability of a coating film to withstand attack by various solutions. When a coating film absorbs a solution, it generally becomes cloudy or appears white. A rating of "0" indicates no redness, while a rating of "5" indicates severe whitening of the coating.

[0116] For details on the preparation of various coating agents and their corresponding evaluation results, please refer to Tables 2-9 below. Examples 9-25: Coating formulations and evaluation

[0117] A coating formulation was prepared containing 75% by weight of the saturated polyester from Example 1 and 25% by weight of either the unsaturated polyester from Example 2 or Example 5 (Table 2). The metal catalyst used in Example 9 and Example 11 was OCTA-SOLIGEN® Iron (Borchers GmbH). [Table 2]

[0118] The cured coatings of Examples 9 to 14 were subjected to deep drawing tests (Table 3), and then sterilized in deionized water at a temperature of 129°C for 1 hour. [Table 3]

[0119] The cured coatings of Examples 9 to 14 were subjected to deep drawing tests (Table 4), and then sterilized in a 2% by weight lactic acid aqueous solution at 129°C for 1 hour. [Table 4]

[0120] The coating agents from Examples 9-14 were applied to a flat metal substrate and cured, and their fluidity, whitening, and adhesion were evaluated (Table 5). [Table 5]

[0121] Coatings from Examples 9 to 14, applied to a flat surface and cured, were sterilized in a 0.05 wt% cysteine ​​solution at 121°C for 90 minutes, and their fluidity, whitening, and adhesion were evaluated. The cysteine ​​solution consisted of 3.56 g of KH₂PO₄. 24 and 7.22g Na HPO 24 0.5 g of cysteine ​​was added to 1 liter of phosphate buffer prepared from (Table 6). [Table 6]

[0122] Table 7 shows coating agents formulated by blending saturated polyester (A) from Example 1 with unsaturated polyester (B) from Examples 2 and 5 in different ratios. Coating evaluations are reported in the same table. [Table 7] [Table 7]

[0123] Table 8 shows coating formulations (=Examples 19, 20, and 21, respectively) containing the unsaturated polyester (B) of Example 2, Example 3, and Example 4, respectively, in the absence of the saturated polyester (A) of Example 1. The same table shows coating formulations containing the unsaturated polyester (B) from Example 4 and the saturated polyester (A) from Example 1 in different ratios (= Example 22 and Example 23, respectively). Furthermore, Table 8 shows coating formulations containing the unsaturated polyester (B) from Example 4a and the saturated polyester (A) from Example 1 (=Example 22a).

[0124] Furthermore, Table 8 shows Example 22b, in which tetrabutyl titanate was added to the paint formulation as an adhesion promoter, compared with Example 22a, in which tetrabutyl titanate was added as an esterification catalyst in the synthesis of unsaturated polyester (B). In Example 22b, monobutyltin oxide was used as the esterification catalyst in the synthesis of unsaturated polyester (B).

[0125] The coating evaluation is reported in the table. Examples 19 to 21 of the coating formulations are shown as comparative examples. The metal catalyst used in Example 20 is OCTA-SOLIGEN® Iron (Borchers GmbH). [Table 8] [Table 8]

[0126] A comparison between Example 18, which includes a blend of saturated polyester (A) and unsaturated polyester (B), and Example 19, which includes only unsaturated polyester (B) from Example 2, clearly demonstrates the advantageous synergistic effect on coating properties when using a coating formulation containing a blend of one or more (A) and one or more (B). It is worth noting that the binders in Example 18 and Comparative Example 19 have the same amount of ethylenically unsaturated binder.

[0127] Table 9 shows coating formulations obtained by mixing saturated polyester from Example 1 (=Example 24) or DUROBTAL® VPE 6104 / 60MPAC, or saturated polyester from Allnex (=Example 25), respectively, with PHENODUR® PR 521 / 60B, a phenolic resin from Allnex, and CYCAT® XK 406 N, which are based on an acidic catalyst derived from a phosphoric acid derivative from Allnex. The coating compositions are formulated with a solid content of 40%, corresponding to the formaldehyde content benchmark. The evaluation of the coatings is reported in the same table. [Table 9]

[0128] The above examples of coating formulations according to the present invention (Examples 9-18, and Examples 22, 22a, 22b, and 23) are clearly equivalent to or better than state-of-the-art products on the market (Benchmark coating formulations, Examples 24 and 25) and exhibit a superior combination of properties compared to Comparative Examples 19-21.

[0129] In Example 22a, butyl titanate is used as the esterification catalyst for the synthesis of the unsaturated polyester in Example 4a (as a substitute for monobutyltin oxide, which is used as the esterification catalyst for the synthesis of the unsaturated polyester in Example 4 and used in the formulations of Example 22 and Example 22b). This result demonstrates that butyl titanate can be used as an esterification catalyst for polyester formation as a substitute for tin derivatives.

[0130] Furthermore, the presence of butyl titanate in the coating formulation, either derived from the polyester esterification catalyst (Example 22a) or added to the coating formulation during preparation (Example 22b), results in an overall improvement in coating performance. In particular, when butyl titanate is added to the coating formulation during preparation (Example 22b), a significant improvement in coating performance is observed after sterilization testing (i.e., it leads to improved sterilization performance of the coating without impairing other properties of the coating).

Claims

1. A coating composition comprising a polyester blend, wherein the blend comprises: Based on the total weight of polyester (A) and (B), One or more saturated polyesters (A) in 5-95% by weight, and 95-5% by weight of one or more unsaturated polyesters (B), The one or more (A) and one or more (B) have a weight-average molecular weight (Mw) of at least 15,000 g / mol, as measured by gel permeation chromatography using tetrahydrofuran as the solvent, and have a glass transition temperature of at least 60°C, as measured by differential scanning calorimetry according to DIN EN 61006, Method A. The aforementioned coating composition, Furthermore, a coating composition wherein one or more (A) and / or one or more (B) comprises one or more aliphatic cyclic groups.

2. The coating composition according to claim 1, wherein one or more (A) and / or one or more (B) comprises an aliphatic polycyclic group.

3. The coating composition according to claim 1 or 2, wherein one or more (A) and one or more (B) have a weight-average molecular weight (Mw) of 20,000 to 50,000 g / mol and / or a glass transition temperature of 80 to 120°C.

4. A coating composition according to any one of claims 1 to 3, Here, one or more (B) are the following reaction products: - Acid components comprising 50-90 mol% terephthalic acid and / or isophthalic acid, 10-50 mol% unsaturated diacitors or their anhydrides, and 0-30 mol% saturated aliphatic, saturated cyclic aliphatic or aromatic diacitors or their anhydrides, and - A glycol component comprising 5–30 mol% of one or more aliphatic and / or cyclic aliphatic diols and 70–95 mol% of one or more aliphatic polycyclic diols; and / or Here, one or more (A) are the following reaction products: - An acid component comprising 50 to 100 mol% terephthalic acid and / or isophthalic acid, and 0 to 50 mol% saturated aliphatic, saturated cyclic aliphatic or aromatic diacitors or their anhydrides, and - A glycol component comprising 5–30 mol% of one or more aliphatic and / or cyclic aliphatic diols and 70–95 mol% of one or more aliphatic polycyclic diols.

5. The coating composition according to claim 4, wherein one or more aliphatic polycyclic diols of one or more (A) and / or one or more (B) comprises diols selected from the group consisting of bicyclic diols, tricyclic diols and mixtures thereof.

6. The coating composition according to any one of claims 4 to 5, wherein one or more aliphatic polycyclic diols of one or more (A) and / or one or more (B) comprises a hetero-bicyclic diol, the hetero-bicyclic diol having a bicyclic aliphatic ring in which one or more hydrocarbons in the ring are substituted with heteroatoms, and the hetero-bicyclic diol is selected from the group consisting of isosorbide, isomannide, isoidide, and derivatives thereof.

7. One or more aliphatic polycyclic diols of one or more (A) and / or one or more (B) are 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ]decane, and 5,8-bis-(hydroxymethyl)-tricyclo[5.2.1.0 2,6 A coating composition according to any one of claims 4 to 5, comprising a tricyclic diol selected from the group consisting of decane and mixtures thereof.

8. The coating composition according to any one of claims 4 to 7, wherein one or more of (B) one or more unsaturated diacids or anhydrides are selected from the group consisting of α,β-unsaturated dicarboxylic acids; α,β-unsaturated acid anhydrides; unsaturated diacids containing an isolated ethylenically unsaturated double bond; unsaturated acid anhydrides containing an isolated ethylenically unsaturated double bond; and mixtures thereof.

9. The coating composition according to any one of claims 4 to 8, wherein one or more unsaturated diacids or anhydrides of one or more of (B) are selected from the group consisting of maleic acid, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, tetrahydrophthalic acid, nadic acid, methylnadic acid, or anhydrides thereof, and mixtures thereof.

10. The coating composition according to any one of claims 1 to 9, wherein one or more (B) has an unsaturated equivalent weight containing 300 to 6,000 g / equiv.

11. One or more (A) are terephthalic acid, 1,4-butanediol, and 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ] Decane, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 ]decane, and 5,8-bis-(hydroxymethyl)-tricyclo[5.2.1.0 2,6 A coating composition according to any one of claims 1 to 10, which is a reaction product with a mixture of decanes.

12. One or more (B) is a reaction product of terephthalic acid, maleic anhydride and / or fumaric acid, 1,4-butanediol, and a mixture of 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 decane, 4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0 2,6 decane, and 5,8-bis-(hydroxymethyl)-tricyclo[5.2.1.0 2,6 decane, and the coating composition according to any one of claims 1 to 11.

13. A coating composition according to any one of claims 1 to 12, comprising 35% to 50% by weight of a blend containing one or more (A) and one or more (B), and 50% to 65% by weight of one or more organic solvents selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, ketones, esters, glycols, glycol ethers, and glycol esters, and mixtures thereof.

14. A coating composition according to any one of claims 1 to 13, comprising one or more additives selected from the group consisting of carriers, additive polymers, emulsifiers, pigments, metal powders or pastes, fillers, migration prevention aids, antimicrobial agents, thickeners, lubricants, mixtures, wetting agents, biocides, plasticizers, crosslinking agents, crosslinking catalysts, defoaming agents, colorants, waxes, antioxidants, rust inhibitors, flow control agents, thixotropic agents, dispersants, adhesion promoters, ultraviolet stabilizers, and scavengers.

15. A coating composition according to any one of claims 1 to 14, comprising 0.05% to 1.5% by weight of an adhesion promoter based on the weight of a nonvolatile substance in the coating composition.

16. A coating composition according to any one of claims 1 to 15, comprising 0.05% to 1.5% by weight of tetraalkyl titanate, preferably tetrabutyl titanate, based on the weight of nonvolatile substances in the coating composition.

17. A coating composition according to any one of claims 1 to 16, comprising less than 10,000 ppm of a component selected from the group consisting of BPA-NI (intentionally free of bisphenol A), formaldehyde, isocyanates, and mixtures thereof.

18. A substrate selected from the group consisting of metal, glass, polymer, composite material, concrete, ceramic and artificial wood, preferably a metal substrate, coated with the composition according to any one of claims 1 to 17.

19. The substrate according to claim 18, wherein the metal substrate is a metal coil or a can, preferably a can for food and beverage use.

20. A method for manufacturing a coated metal substrate, comprising the following steps: - Apply the coating composition according to claims 1 to 17 to at least one side of a metal substrate, which may include a pre-treated and / or primer, with a coating thickness adjusted so that the dry coating thickness is less than 60 μm; - The applied coating composition is subjected to stove treatment at a temperature of at least 150°C for at least 20 seconds to form a cross-linked coating layer on the metal substrate.

21. A method for manufacturing a coated can body and can end, including the following steps: - Cut the coated metal substrate of claim 20 into metal pieces of desired dimensions and shapes to form the can body and can end and prepare for assembly, or - Cutting the coated metal substrate of claim 20 into metal pieces of desired dimensions and shape, embossing the metal pieces onto the can body, cutting the can ends into desired shapes, and preparing for assembly.

22. Use of the coating composition according to any one of claims 1 to 17 for coating a metal substrate.

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