KR20180093032A - Branched polyester-urethane resins and coatings comprising same - Google Patents

Abstract

Uncyclosed branched polyester-urethane resins prepared by free radical polymerization of unsaturated polyester prepolymers having polyol segments, unsaturated polycarboxylic acids and / or anhydrides and / or esters thereof and urethane segments are disclosed. Also disclosed are a coating comprising the same and a substrate at least partially coated with the coating.

Description

Branched polyester-urethane resins and coatings comprising same

The present invention relates to an uncured, branched polyester-urethane resin prepared by free radical polymerization of a double bond of an unsaturated polyester-urethane prepolymer. The invention also relates to a coating comprising said polyester-urethane resin and a substrate to which said coating is applied.

Cross-reference to related application

This application is a continuation-in-part of U.S. Patent Application No. 12 / 752,570, entitled "Branched Polyester Polymer and Coating Containing It, " filed April 1,

In the automotive industry, it is often desirable to apply protective and / or decorative coatings to the vehicle. Such coatings can provide resistance to abrasive chipping of road dust and debris, such as sand and gravel, which can, for example, cause aesthetically unpleasant chipping of the vehicle paint. A coating composition having acceptable chip resistivity and decorative properties is preferred.

The present invention relates to an uncured, branched, polyester-urethane resin prepared by free radical polymerization of a double bond of an unsaturated polyester-urethane prepolymer, comprising (a) a polyol segment, (b) an unsaturated And / or an anhydride and / or ester thereof, (c) a urethane segment. Coatings comprising the polyester-urethane resin and substrates coated at least partially with the coating are also within the scope of the present invention.

The present invention also relates to a method of forming a multilayer coating system on a substrate,

Forming a first basecoat layer over at least a portion of the substrate by depositing a first basecoat composition over at least a portion of the substrate;

Optionally, drying or curing the first basecoat layer;

Depositing a second basecoat composition that is the same as or different from the first basecoat composition on at least a portion of the first basecoat layer to form a second basecoat layer on at least a portion of the first basecoat layer step;

Optionally, drying or curing the second basecoat layer; And

Curing the uncured coating layer

Wherein at least one of the first and second basecoat compositions comprises a coating composition comprising a polyester-urethane resin.

The present invention

a) free radical polymerization of a double bond of at least one unsaturated polyester prepolymer having hydroxyl functional groups to form a polyester polymer, and

b) reaction of the polyester polymer of step a) with an isocyanate

Curable branched polyester-urethane resin, wherein the polyester prepolymer is prepared from

i) a polyol segment; And

ii) unsaturated polycarboxylic acids and / or anhydrides and / or ester segments

.

The present invention also provides an uncured branched polyester-urethane resin prepared by free radical polymerization of a double bond of a first unsaturated polyester prepolymer and a double bond of a second unsaturated polyester prepolymer, wherein each Lt; RTI ID = 0.0 >

a) a polyol segment; And

b) an unsaturated polycarboxylic acid and / or anhydride and / or ester segment

Wherein at least one of said unsaturated polyester prepolymers comprises a urethane segment and wherein said polyester prepolymer is the same or different.

The present invention relates generally to uncured branched branched polyester-urethane resins comprising polyol segments, unsaturated polycarboxylic acids and / or anhydrides and / or esters thereof, and reaction products comprising urethane segments. Free radical initiators are used to initiate polymerization through unsaturated groups of the unsaturated polyester-urethane prepolymer to provide uncured branched polyesters. The branched polyester-urethane resins are not cured or in other words "curable" and / or "crosslinkable", which can crosslink with other compounds to form a cured coating, But not a cured coating. That is, the polyester-urethane polymer has a functional group capable of reacting with a functional group on another compound such as a crosslinking agent. The reaction of the unsaturated groups of the prepolymer produces an uncured, cross-linkable, branched polyester-urethane resin. For clarity, this polyester-urethane is a polymeric resin. This is not a cured coating. Thus, the present invention is distinguished from the technique of reacting unsaturated points on the monomers and / or polymers to cure the coating.

The polyester-urethane prepolymer is prepared by reacting at least one polyol with at least one unsaturated polycarboxylic acid / anhydride / ester and at least one isocyanate.

As used herein, "polyol" and like terms refer to compounds having two or more hydroxy groups. The polyol or "residual moiety of the polyol" used to form the polyol segment is sometimes referred to herein as the "polyol segment monomer ". "Residual residue" means a residue or segment of a molecule derived from a particular monomer. For example, "residual moiety of polyol" means a moiety derived from a polyol monomer. The polyol may also be selected to impart hardness or softness to the prepolymer, but the amount of polyol used and the amount of each will depend upon the type of prepolymer being used, Should be selected to produce a polyester. The polyol may have from 2 to 36 atoms. The polyols suitable for use in the present invention may be any polyols known for the production of polyesters. Examples thereof include, but are not limited to, alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol and neopentyl glycol; Hydrogenated bisphenol A; Cyclohexanediol; Propanediol, such as 1,2-propanediol, 1,3-propanediol, butylethylpropanediol, 2-methyl-1,3-propanediol, 3-propanediol; Butanediols such as 1,4-butanediol, 1,3-butanediol, and 2-ethyl-1,4-butanediol; Pentanediols such as trimethylpentanediol and 2-methylpentanediol; Cyclohexane dimethanol; Hexanediols such as 1,6-hexanediol; Caprolactone diol (e. G., The reaction product of epsilon-caprolactone with ethylene glycol); Hydroxyalkylated bisphenols; Polyether glycols such as poly (oxytetramethylene) glycol; Trimethylol propane, pentaerythritol, di-pentaerythritol, trimethylolethane, trimethylolbutane, dimethylolcyclohexane, glycerol, and the like. Unsaturated polyols suitable for use in the present invention may be any unsaturated alcohol containing two or more hydroxyl groups. Examples include, but are not limited to, trimethylolpropane monoallyl ether, trimethylolethane monoallyl ether, and prop-1-en-1,3-diol. The polyol segment may also comprise some, such as 10% or less, or 5% by weight, based on the total weight of the polyol segment. The polyol segment can be saturated.

The unsaturated polyester-urethane prepolymer also includes unsaturated polycarboxylic acids, anhydrides and / or esters, or residual moieties derived therefrom. An unsaturated polyacid suitable for use in the present invention may be any unsaturated carboxylic acid containing two or more carboxy groups and / or esters and / or anhydrides thereof. Examples include, but are not limited to, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, teraconic acid, and / or esters and / or anhydrides thereof. Particularly suitable unsaturated polyacids are maleic acid, maleic anhydride, or C ₁ -C ₆ alkyl esters of maleic acid. The unsaturated polycarboxylic acid or an anhydride or ester thereof may comprise from 3 to 10%, such as from 4 to 7% by weight of the polyester-urethane prepolymer.

As mentioned previously, the unsaturated polyester-urethane prepolymer comprises urethane segments. "Urethane segments" will be understood to have urethane (NHCOO) functional groups. At least one of the polyester-urethane prepolymers used according to the present invention may have urethane segments, and one or both of the prepolymers used may have such urethane segments. The use of one or more of the polyester-urethane prepolymers with urethane segments will cause the urethane segments to be present in the final polyester-urethane resin and thus also to be present in the coating formed of such resins. The urethane segment may comprise from 5 to 45% by weight, for example from 10 to 25% by weight, based on the total weight of the polyester-urethane prepolymer.

Urethane segments can be incorporated into the polyester-urethane prepolymer by reaction with isocyanates having (NCO) groups or isocyanate functionality. The isocyanate may have from 4 to 25 carbon atoms. Suitable isocyanates include aromatic and aliphatic polyisocyanates (including alicyclic polyisocyanates), representative examples being diphenylmethane-4,4'-diisocyanate (MDI), 2,4- or 2,6-toluene di Isocyanate, isocyanate (TDI) (including mixtures thereof), p-phenylene diisocyanate, tetramethylene and hexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, phenylmethane- , A mixture of 4'-diisocyanate and polymethylene polyphenyl isocyanate. More advanced polyisocyanates such as triisocyanates, such as triphenylmethane-4,4 ', 4 "-triisocyanate, may be used. Isocyanates may be blocked or unblocked according to the present invention. Neopentyl glycol and tri Polyol such as methylol propane and isocyanate prepolymer (with an NCO / OH equivalence ratio greater than 1) prepared with a polymeric polyol such as polycaprolactone diol and triol may also be used.

According to the present invention, an isocyanate can be reacted with a polyol segment and an unsaturated polycarboxylic acid / anhydride / ester segment or reacted with a pre-reacted polyester prepolymer. The polyester-urethane prepolymer may also be formed by reacting together a polyol segment, an unsaturated polycarboxylic acid / anhydride / ester segment and an isocyanate. As used herein, "polyester prepolymer" means the reaction product of a polyol segment and an unsaturated polycarboxylic acid / anhydride / ester segment. In the case of a polyester prepolymer, the ratio of reactive hydroxyl groups (OH) on the polyol segment to acid groups on the unsaturated polycarboxylic acid / anhydride / ester segment may be 2: 0.5, 2: 1.5 or more. The higher the ratio, the larger the molecular weight of the reaction product. Because an excess of polyol is used, the reaction product polyester prepolymer has a terminal hydroxyl functionality.

As described in more detail below, the polyester-urethane resins may be prepared for use in solvent based systems or aqueous systems. For solvent-based systems, the isocyanate reacts with one of the hydroxyl functionalities of the polyol segment or polyester prepolymer such that the polyester-urethane prepolymer has an isocyanate functionality (NCO) of from 1: 2 to 1: 1.5, (OH). ≪ / RTI > For aqueous systems, the polyester-urethane prepolymer may be prepared to contain unreacted OH-functional groups and unreacted NCO-functional groups, which may be further reacted with acid functionalities with hydroxyl group containing carboxylic acids . The acid functionalized prepolymer may then be neutralized with a base, dispersed in water and polymerized. Thus, the polyester-urethane prepolymer may have 10 to 30% unreacted NCO groups and 70 to 90% unreacted OH groups. Typically, the reaction with the isocyanate is carried out at a temperature of from 50 캜 to 120 캜. According to the present invention, the reaction with the isocyanate can be carried out in any non-alcohol organic solvent. Suitable non-alcohol organic solvents include butylacetate, amyl acetate, methyl isobutyl ketone, methyl ethyl ketone, propylene glycol monomethyl ether, or mixtures thereof.

According to the present invention, the resulting unsaturated polyester-urethane prepolymer will have a hydroxyl end functional group and an unsaturated group. The average functionality of the unsaturated groups of the polyester-urethane prepolymer may range from 1 to 5, such as from 2 to 4, and may be 2 or more. Although not wishing to be bound by this mechanism, the higher hydroxyl functionality also means that the resulting resin and any coating containing such resin are more likely to react with the crosslinking agent in the proposed coating composition and / or the adjacent coating layer and / Or crosslinked sites, thereby providing better intercoat adhesion, better chip resistance and sag resistance properties between two adjacent coating layers.

The unsaturated polyester-urethane prepolymer may additionally comprise one or more monomers that contribute to the overall properties of the polyester, including "softness ", stain resistance, durability, chemical resistance and / . For example, one or more monomers that contribute to a "soft segment" can be used as one or more polyols and one or more unsaturated polycarboxylic acid / anhydride / esters. As used herein, the term " soft segment "and similar terms refers to a monomer or moiety or moieties or moieties capable of imparting flexibility to the prepolymer and obtaining the desired Tg and / or viscosity of the branched polyester- Lt; / RTI > The soft segment may be, for example, a residue of a polyacid. As used herein, "polyacid" and similar terms refers to a compound having two or more acid groups and includes esters and / or anhydrides of such acids. Such an acid may include, for example, a flexibility-imparting linear acid. Examples include, but are not limited to, saturated polyacids such as adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, decanedioic acid, dodecanedioic acid, and esters and anhydrides thereof. Suitable mono-acids include C1-C18 aliphatic carboxylic acids such as acetic acid, propanoic acid, butanoic acid, hexanoic acid, oleic acid, linoleic acid, undecanoic acid, lauric acid, isononanoic acid, other fatty acids and hydrogenated fatty acids of natural oils; And / or esters and / or anhydrides thereof.

The uncured branched branched polyester-urethane prepolymer of the present invention may further comprise hard segments. As used herein, the term " hard segment "and similar terms refer to monomers or moieties that impart rigidity to the prepolymer rather than flexibility. The hard segment may be, for example, a residue of a polyacid. The polyacid can be an aromatic or aliphatic acid, and suitable examples include, but are not limited to, phthalic acid, isophthalic acid, 5-tert-butylisophthalic acid, tetrachlorophthalic acid, tetrahydrophthalic acid, naphthalene polycarboxylic acid, terephthalic acid, hexahydrophthalic acid, methyl But are not limited to, hexahydrophthalic acid, dimethylterephthalate, cyclohexanedicarboxylic acid, chlorendic anhydride, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, tricyclodecanepolycarboxylic acid, endomethylenetetrahydrophthalic acid, Ethylene hexahydrophthalic acid, cyclohexanetetracarboxylic acid, cyclobutanetetracarboxylic acid, esters and anhydrides thereof, and / or combinations thereof. Monomers that contribute to the hard segment are sometimes referred to herein as "hard segment monomers ". Thus, one skilled in the art will need to determine the amount of acid and the amount of each acid used to impart to the final coating other desirable properties such as the desired flexibility or hardness and feel, as well as resistance to contamination.

Other monomer components may also be used in forming the prepolymer to impart one or more additional properties to the branched polyester-urethane resin and / or coatings comprising the same. For example, the phthalic anhydride may be included in an amount of from 2 to 20% by weight of the prepolymer; The phthalic anhydride may impart greater stain resistance to the coating. Aliphatic diacids may be added to increase hydrophobicity, and polyethers such as poly THF may be used to render the branched polyester-urethane resin more hydrophilic. Diene monomers such as butadiene may also contribute to soft touch, chemical and / or flexibility, and dicyclopentadiene may contribute to durability and rubbery feel.

According to the present invention, the unsaturated polyester-urethane prepolymer is polymerized in the presence of a free radical initiator. Any free radical initiator typically used to initiate polymerization of unsaturated compounds containing double bonds can be used in the free radical polymerization. For example, the free radical initiator may be an azo initiator or a peroxide initiator such as tert-butylperoxy-2-ethylhexanoate, tert-butylperoxybenzoate or dibenzoyl peroxide. Such free radical initiators are commercially available as LUPEROX 26 from Arkema. The ratio of initiator to unsaturated acid / anhydride / ester may vary depending on the degree of branching of the desired polyester chain. For example, the molar ratio of the initiator to the average number of double bonds per chain of unsaturated acid / anhydride / ester may be 0.001 to 1.0, such as 0.01 to 0.9, or 0.5 to 1.

Thus, the unsaturated groups from one acid / anhydride / ester moiety in the reaction product react with other unsaturated groups. The result is a branched polyester polymer. At least a portion of the branch, although not all branches, will have a terminal hydroxyl group. It may also be a pendant functional group of a branched polyester depending on the starting material used. Typically, when an initiator is used with an unsaturated acid / anhydride / ester, a linear polymer is produced. Thus, it has been very surprising and unexpected to achieve the branched polyester-urethane resin according to the present invention. It will be appreciated that in the present invention, the branching is accomplished primarily through the reaction of the unsaturated groups. Although the use of tri- or tetra-ols may contribute to a lesser degree of branching, the amount of such compounds should be chosen to avoid gelation. The process of the present invention for achieving branching using polymerizing unsaturated groups of polycarboxylic acids and the polyester produced therefrom can be carried out using conventional branched polyester-urethane resins such as those prepared using tri- or tetra- It will be appreciated that it is quite unique compared to the method of using.

Depending on the extent to which the desired polymerization is controlled, initiators can be added in different fractions at different times. For example, the entirety of the free radical initiator may be added at the start of the reaction, or the initiator may be divided into fractions to add fractions at intervals during the reaction, or the initiator may be added as a continuous feed. It will be appreciated that adding the initiator at set intervals or as a continuous feed provides a controlled method rather than adding all of the initiator at the start of the reaction.

Whether the polyester prepolymer is formed first or whether the polyol segment and the polycarboxylic acid / anhydride / ester react directly with the isocyanate, when and how the initiator is added, The polyester-urethane resin may actually be a mixture of polyester-urethane resins having varying degrees of unsaturation, chain length, and branching. Some of the product may even be a monoester, but this is also included in the term "polyester " as used herein.

The temperature at which the free radical polymerization reaction is carried out will vary depending on factors such as the nature of the unsaturated acid / anhydride / ester, the polyol segment monomer, the urethane segment, the initiator, the composition of the solvent and the desired properties in the polyester. Typically, the free radical polymerization is carried out at a temperature of from 50 캜 to 150 캜. In typical polymerization, such as acrylic polymerization, higher temperatures provide a higher concentration of free radical initiator, which allows more chains of relatively lower molecular weight to polymerize. Surprisingly, it has been found that in the system of the present invention, especially when maleic acid is used, the higher the initiator concentration, the higher the molecular weight of the resulting polymer. This is an astounding result, since those skilled in the art have not anticipated that the proposed polymerization of the present invention will occur. However, too much initiator may cause gelation if polymerization occurs on a solvent. The polyester-urethane resin of the present invention may be a non-gelled type.

Although any means can be used to carry out the polymerization, for ease of handling, free radical polymerization can be carried out using a solution of unsaturated acid / anhydride / ester, urethane segments and polyol segment monomers. Free radical polymerization can be carried out in a solvent-based or water-based system. Any solvent can be used as long as it can dissolve the components including the free radical initiator to a sufficient extent so that polymerization can be effectively carried out. Typical examples of suitable solvents include butyl glycol, propylene glycol monomethyl ether, glycol diethers, methoxypropyl acetate and xylenes. The production of polyester-urethane resins in solvents is often referred to herein as a "solvent system ", which is an organic solvent in which more than 50%, such as less than 100%, of the solvent is an organic solvent and less than 50% Less than 10%, less than 5%, or less than 2% is water.

Alternatively, the polyester-urethane resin may be prepared in an aqueous system. A "water-based system" is one in which greater than 50%, such as less than 100% of the solvent is water and less than 50%, such as less than 20%, less than 10%, less than 5%, or less than 2% . If the unsaturated polyester-urethane prepolymer has a sufficient carboxylic acid group, it can be converted to the material that has been water-diluted by neutralization or partial neutralization using a suitable base and then addition of water. Non-limiting examples of bases suitable for such neutralization include dimethylethanolamine, triethylamine and 2-amino-2-methylpropanol. This aqueous material can then be polymerized with free radicals as described above. Alternatively, the unsaturated polyester prepolymer may be mixed with a surfactant and / or polymeric stabilizer material and then mixed with water prior to free radical polymerization, as described above. It will also be apparent to those skilled in the art that such an aqueous mixture may contain additional organic co-solvents, examples of which include, but are not limited to, butyl glycol, butyl diglycol, glycol diethers, and propylene glycol monomethyl ether . Such organic co-solvents are commercially available as PROGLYDE DMM from Dow Chemical Company.

The present invention relates to a process for producing a polyester-urethane prepolymer by reacting an isocyanate with a polyol segment and an unsaturated polycarboxylic acid / anhydride / ester segment or by reacting with a polyol ester prepolymer and then polymerizing it by free radical polymerization Respectively. The polyester-urethane resin may also be prepared by reacting a polyol segment and an unsaturated polycarboxylic acid / anhydride / ester segment to form at least one polyester prepolymer and subjecting the at least one polyester prepolymer to polymerization through free radical polymerization of the double bond ≪ / RTI > to form a hydroxyl functional polyester polymer. The polyester polymer may have an equivalence ratio of more than one hydroxyl group (OH) group to isocyanate (NCO) group. The polyester polymer may then be reacted with an isocyanate to form a polyester-urethane polymer. The polyester-urethane polymer can be prepared to have an excess of NCO functionality. The excess NCO functionality causes the polyester-urethane polymer to react with the hydroxyl group containing carboxylic acid and neutralize with a base before being dispersed in the aqueous medium.

In solvent or aqueous systems, the resulting polyester may be either solid or liquid.

As described above, the polyester-urethane polymer of the present invention is formed by free radical polymerization through a double bond of an unsaturated polyester prepolymer containing a terminal hydroxyl group. According to the present invention, two or more different unsaturated polyester-urethane prepolymers can be reacted together. By context, "different" means that the amount of one or more components used in the two or more unsaturated polyester-urethane prepolymers and / or the amount of one or more components used in the two or more unsaturated polyester-urethane prepolymers may differ . For example, the polyester-urethane polymer according to the present invention can be prepared by the reaction of a polyester-urethane prepolymer composed of the same components. The polyester-urethane resin can be prepared by the reaction of two or more polyester-urethane prepolymers formed from different components. That is, a first polyester prepolymer comprising a terminal hydroxyl group and a second polyester prepolymer comprising a terminal hydroxyl group reacts with an unsaturated isocyanate, and the components used in the preparation of the first and second prepolymers are different Or may have one or more different components. In this example, the resulting polyester-urethane resin will have random units derived from each type of prepolymer used. Thus, the present invention includes polyester-urethane resins made by the same or different amounts of urethane segments, polyol segment monomers and / or unsaturated acids / anhydrides / esters, and / or any of the foregoing . The use of different polyester prepolymers, urethane segments, polyol segment monomers, unsaturated acids / anhydrides / esters and / or amounts can provide polyester-urethane resins with different properties. In this way, a polyester-urethane resin having the desired properties derived using the specific components used in the reaction product can be formed.

As described above, the polyester-urethane polymer is formed using free radical polymerization, wherein the unsaturated groups of the polycarboxylic acid / anhydride / ester moiety in the prepolymer are polymerized. This reaction can be carried out so that substantially all of the unsaturated groups react in the formation of the polyester-urethane polymer. However, in some instances, the resulting polyester-urethane polymer also contains some unsaturated groups. For example, the resulting polyester-urethane polymer may include unsaturated groups sufficient to provide a polyester-urethane polymer that is reactive with other functional groups.

Since the branched polyester-urethane resin according to the present invention is mainly formed through the free radical polymerization of unsaturated groups from an unsaturated acid / anhydride / ester, a part of the terminal hydroxyl groups in the polyester- It will remain untouched. These unreacted hydroxyl groups can then be cross-linked with other components. Thus, the present invention is distinguished from the art of forming a gelled polyester, i. E. An extremely networked polyester. The polyester-urethane resins of the present invention can be thermoset when reacted with a crosslinking agent, and thus are distinguished from techniques that also teach thermoplastic polyesters.

According to the present invention, it may be desirable to convert some or all of the hydroxyl functionalities on the unsaturated polyester prepolymer and / or the branched polyester to other functional groups, for example, prior to polymerization taking place. For example, such hydroxyl groups can react with cyclic anhydrides to provide acid functionality. An acid ester may also be formed.

The present invention contemplates that the use of unsaturated monomers other than the unsaturated polyacid / anhydride / ester of the reaction product is excluded. For example, the use of vinyl monomers such as (meth) acrylate, styrene, vinyl halide and the like can be excluded. Thus, it will be appreciated that the branched polyester-urethane resins of the present invention are not polyester / acrylic graft copolymers well known in the art.

The polyester-urethane resins of the present invention can specifically exclude polyester-urethane resins made from prepolymers formed by reaction with aldehydes, and thus, acylsuccinic acid polyesters can be specifically excluded. Similarly, the use of aldehydes in solvents can be particularly excluded.

The polyester-urethane resins of the present invention may have a relatively high molecular weight and functionality as compared to conventional linear polyester-urethane resins. Typically, the ratio of the M _w of the branched polyester-urethane resin of the present invention to the weight average molecular weight ("M _W ") of the unsaturated polyester-urethane prepolymer is 1.2 to 100, such as 4 or 5 to 50 to be.

Branched polyester of the present invention is a urethane resin has a lower M _W 600 or so, and may have more than 1000, such as 5000, greater than 10,000, greater than 15,000, greater than 25,000, greater than 50,000 or greater than the M _W. Molecular weights of 80,000 to 100,000 are also contemplated by the present invention. A molecular weight of greater than 100,000 but less than 10,000,000 can be achieved. The molecular weight increase can be controlled by one or more factors such as the type and / or amount of the initiator used, the degree of unsaturation on the prepolymer, the temperature and the type and / or amount of the solvent. All molecular weights disclosed herein are determined by gel permeation chromatography using polystyrene standards for assay.

In addition to the molecular weights mentioned above, the branched unsaturated polyester-urethane resins of the present invention may also have relatively many functional groups. In some cases, the functional groups are more than would be expected in conventional polyester-urethane resins having the same molecular weight. The average functionality of the polyester-urethane resin may be 2.0 or more, such as 2.5 or more, 3.0 or more, or more. The term "average functionality" as used herein refers to the average number of functional groups on the branched polyester. The functionality of the branched polyester-urethane resin is measured by the number of hydroxyl groups remaining unreacted in the branched polyester-urethane resin, but not by unreacted unsaturation. The hydroxyl value of the branched polyester-urethane resin of the present invention may be 10 to 500 mg KOH / gm, such as 30 to 250 mg KOH / gm, such as 75 to 120 mg KOH / gm, as measured by ASTM D4274. The branched polyester-urethanes of the present invention will have both high M _w and many functional groups, such as greater than 15,000, such as from 20,000 to 40,000, or greater than 40,000 M _W , and greater than 100 mg KOH / gm of functional groups.

Because the polyester-urethane resins of the present invention comprise functional groups, they are suitable for use in coating compositions in which other resins and / or crosslinking agents and typically hydroxyl groups (and / or other functional groups) used in coating compositions are crosslinked Do. Accordingly, the present invention also relates to a coating comprising a branched polyester-urethane resin according to the invention and a crosslinking agent therefor. Such a cross-linking agent, or cross-linking resin or material, may be any suitable cross-linking or crosslinking resin known in the art and will be selected to be reactive with the functional group (s) on the polyester. The coatings of the present invention can be prepared by reacting hydroxyl groups and / or other functional groups and crosslinking agents, not through a double bond of the polycarboxylic acid / anhydride / ester moiety, to the extent that any unsaturated groups are present in the branched polyester- Lt; / RTI > will be cured through the reaction.

Non-limiting examples of suitable crosslinking agents include phenolic resins, amino resins, epoxy resins, isocyanate resins, beta-hydroxy (alkyl) amide resins, alkylated carbamate resins, polyacids, anhydrides, organometallic acid- , Polyamines, polyamides, aminoplasts, and mixtures thereof. The crosslinking agent may be a phenolic resin comprising an alkylated phenol / formaldehyde resin having three or more functional groups and a bifunctional o-cresol / formaldehyde resin. Such cross-linking agents are commercially available from Hexion as BAKELITE 6520LB and Bakelite 7081LB.

Suitable cross-linking isocyanates include multifunctional isocyanates. Examples of multifunctional polyisocyanates include aliphatic diisocyanates such as hexamethylene diisocyanate and isoprene diisocyanate; And aromatic diisocyanates such as toluene diisocyanate and 4,4'-diphenylmethane diisocyanate. The polyisocyanate may be blocked or unblocked. Examples of other suitable polyisocyanates include isocyanurate trimer, allophanate, and urethane ion of a diisocyanate and polycarbodiimide, such as U.S. Patent Application No. 12 / 056,304, filed March 27, 2008 The relevant portions of which are incorporated herein by reference. Suitable polyisocyanates are well known in the art and are widely available. For example, suitable polyisocyanates are disclosed in U.S. Patent No. 6,316,119, column 6, line 19 to column 36, which is incorporated herein by reference. Examples of commercially available polyisocyanates include DESMODUR VP2078 and DEA all N3390 available from Bayer Corporation and TOLONATE HDT90 available from Rhodia Inc. .

Suitable aminoplasts include condensates of amines and / or amides and aldehydes. For example, condensates of melamine and formaldehyde are suitable aminoplasts. Suitable aminoplasts are well known in the art. Suitable aminoplasts are disclosed, for example, in U.S. Patent No. 6,316,119, column 5, lines 45 to 55, which is incorporated herein by reference. Commercially available resins for aminoplast crosslinking include RESIMEN HM 2608 sold by Ineos Melamines, LLC.

In preparing the coatings of the present invention, the branched polyester-urethane polymer and crosslinking agent may be dissolved or dispersed in a single solvent or mixture of solvents. Any solvent capable of causing the composition to be coated on the substrate can be used, which is well known to those skilled in the art. Typical examples include water, organic solvent (s), and / or mixtures thereof. Suitable organic solvents include glycols, glycol ether alcohols, alcohols, ketones, and aromatics such as xylene and toluene, acetate, mineral spirits, naphtha and / or mixtures thereof. "Acetate" includes glycol ether acetate. The solvent is a non-aqueous solvent. By "non-aqueous solvent" and like terms, it is meant that less than 50% of the solvent is water. For example, less than 10%, or even less than 5% or less than 2% of the solvent may be water. It will be appreciated that a mixture of solvents that contain or exclude water in an amount less than 50% may constitute a "non-aqueous" solvent. In some instances, the coating is aqueous or aqueous. This means that at least 50% of the solvent is water. For example, the water-based coating may have less than 50%, such as less than 20%, less than 10%, less than 5%, or less than 2% solvent.

 The present invention also contemplates a coating comprising a curing catalyst. Any curing catalyst typically used to promote the crosslinking reaction between the polyester resin and the crosslinking agent (e.g., phenolic resin) can be used, and there are no particular restrictions on the catalyst. Examples of such curing catalysts include phosphoric acid, alkylarylsulfonic acids, dodecylbenzenesulfonic acid, dynonylnaphthalenesulfonic acid, and dynonylnaphthalenesulfonic acid.

If desired, the coating composition may also comprise, among other components, other optional materials well known in the art of coating compositions such as colorants, plasticizers, abrasion resistant particles, antioxidants, sterically hindered amine light stabilizers, UV light absorbers and stabilizers, , Flow control agents, thixotropic agents, fillers, organic co-solvents, reactive diluents, catalysts, grinding vehicles, and other conventional adjuvants.

The term "colorant" as used herein refers to any component that imparts color and / or other opacity and / or other visual effects to the composition. The colorant may be added to the composition in any suitable form, e. G., As individual particles, dispersions, solutions and / or flakes. A single colorant or a mixture of two or more colorants may be used in the coating of the present invention.

Exemplary colorants include pigments, dyes and tints, such as those used in the paint industry and / or special effect compositions as well as those listed in the Dry Color Manufacturer Association (DCMA). The colorant may comprise, for example, a finely divided solid powder that is insoluble but wettable under the conditions of use. The colorant may be organic or inorganic and may be coherent or non-coherent. The colorant may be introduced into the coating by using a pulverizing vehicle, for example an acrylic milling vehicle, whose use is familiar to those skilled in the art.

Examples of pigment and / or pigment compositions include, but are not limited to, carbazole dioxyphosphoric acid pigments, azo, monoazo, disazo, naphthol AS, salt forms (rake), benzimidazolone, condensates, metal complexes, Pyranthrone, anthanthrone, pyranthrone, anthrone, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, (DPPBO red), titanium dioxide, carbon black, carbon fibers, graphite, other conductive pigments and / or fillers, and mixtures thereof. . The terms "pigment" and "colored filler" may be used interchangeably.

Examples of dyes include, but are not limited to, solvent based and / or aqueous dyes such as acid dyes, azo dyes, basic dyes, direct dyes, disperse dyes, reactive dyes, solvent dyes, sulfur dyes, mordant dyes, Such as, for example, bismuth vanadate, anthraquinone, perylene, aluminum, quinacridone, thiazole, thiazine, azo, indigo, nitro, nitroso, oxazine, phthalocyanine, quinoline, stilbene, to be.

Examples of tints include, but are not limited to, pigments dispersed in an aqueous or water-miscible carrier such as AQUA-CHEM 896, available from Degussa Inc., Eastman Chemical CHARISMA COLORANTS and MAXITONER INDUSTRIAL COLORANTS, both available from Accurate Dispersions division of Eastman Chemical Inc., all of which are incorporated herein by reference.

As discussed above, the colorant may be in the form of a dispersion, including, but not limited to, nanoparticle dispersions. The nanoparticle dispersion may comprise one or more highly dispersed nanoparticle coloring agents and / or colorant particles that produce the desired visible color and / or opacity and / or visual effects. The nanoparticle dispersion may comprise a colorant, for example a pigment or dye having a particle size of less than 150 nm, for example less than 70 nm or less than 30 nm. The nanoparticles may be prepared by milling a stock organic or inorganic pigment with a milling media having a particle size of less than 0.5 mm. Examples of such nanoparticle dispersions and methods for their preparation are found in U.S. Patent No. 6,875,800 B2, the relevant portions of which are incorporated herein by reference. The nanoparticle dispersion may also be prepared by crystallization, precipitation, gas phase condensation, and chemical wiping (i.e., partial dissolution). In order to minimize the re-agglomeration of the nanoparticles in the coating, a dispersion of resin-coated nanoparticles may be used. As used herein, the term " dispersion of resin-coated nanoparticles " refers to a continuous phase in which individual "composite microparticles" comprising nanoparticles and resin coatings on the nanoparticles are dispersed. Examples of dispersions of resin coated nanoparticles and methods of making the same are described in U.S. Patent Application Publication No. 2005/0287348 A1, filed June 24, 2004, U.S. Provisional Patent Application No. 60 / And U.S. Patent Application No. 11 / 337,062, filed January 20, 2006, the relevant portions of which are incorporated herein by reference.

Examples of special effect compositions that can be used are those which exhibit one or more cosmetic effects such as, for example, reflection, pearl luster, metallic luster, phosphorescence, fluorescence, photochromism, photosensitivity, thermal discoloration, goniochromism and / / RTI > and / or < / RTI > Additional special effect compositions may provide other perceptible properties such as, for example, opacity or texture. In a non-limiting example, a special effect composition may cause a color shift such that the color of the coating changes when the coating is viewed at different angles. Examples of such color effect compositions are found in U.S. Patent No. 6,894,086, the relevant portions of which are incorporated herein by reference. The additional color effect composition may be selected from the group consisting of transparent coated mica and / or synthetic mica, coated silica, coated alumina, transparent liquid crystal pigment, liquid crystal coating, and / RTI ID = 0.0 > interfering < / RTI >

 The present invention may also include a photosensitive composition and / or a photochromic composition, wherein the color reversibly changes upon exposure to one or more light sources and may be used in the coating of the present invention. The photochromic and / or photosensitive composition may be activated by exposure to radiation of a particular wavelength. When the composition is excited, the molecular structure changes, and the modified structure exhibits a new color that is different from the original color of the composition. When the exposure to radiation is removed, the photochromic and / or photosensitive composition can be returned to rest, with the original color of the composition returning. The photochromic and / or photosensitive composition is colorless in the non-excited state and may exhibit color in the excited state. Complete color-change can occur within milliseconds to a few minutes, for example within 20 seconds to 60 seconds. Examples of the photochromic and / or photosensitive composition may include a photochromic dye.

Moreover, the photosensitive composition and / or the photochromic composition may be connected and / or at least partially bonded (e.g., covalently bonded) to the polymeric and / or polymeric material of the polymerizable component. Unlike some coatings in which the photosensitive composition is moved out of the coating and crystallized into the substrate, the photosensitive composition and / or photochromic composition, which is connected and / or at least partially bonded to the polymer and / or the polymerizable component according to the invention, Move to the minimum. The photosensitive compositions and / or photochromic compositions of the present invention and methods of making them are identified in U.S. Patent Application Publication No. 10 / 892,919, filed July 16, 2004, the disclosure of which is incorporated herein by reference .

In general, the colorant may be present in the coating composition in any amount sufficient to impart the desired visual and / or color effect. The colorant may comprise from 1 to 65% by weight, for example from 3 to 40% by weight or from 5 to 35% by weight, based on the total weight of the composition.

"Abrasion-resistant particles" are particles that, when used in coatings, impart a certain level of abrasion resistance to the coating as compared to the same coating without such particles. Suitable abrasion-resistant particles include organic and / or inorganic particles. Examples of suitable organic particles include, but are not limited to, diamond particles, such as diamond dust particles, and particles formed from carbide materials. Examples of carbide particles include, but are not limited to, titanium carbide, silicon carbide, and boron carbide. Examples of suitable inorganic particles include, but are not limited to, silica; Alumina; Alumina silicate; Silica alumina; Alkali aluminosilicates; Borosilicate glass; Nitrides such as boron nitride and silicon nitride; Oxides such as titanium dioxide and zinc oxide; quartz; Nepheline syenite; Zircon, such as zirconium oxide; Buddeluyite; And eudialyte. Particles of any size may be used, and mixtures of different particles and / or particles of different sizes may be used. For example, the particles may be fine particles having an average particle size of 0.1 to 50 μm, 0.1 to 20 μm, 1 to 12 μm, 1 to 10, or 3 to 6 μm, or any combination within this range. The particles may be nanoparticles having a diameter of less than 0.1 mu m, such as 0.8 to 500 nm, 10 to 100 nm, or 100 to 500 nm, or any combination within this range.

It will be appreciated that the polyester-urethane resin of the present invention and the crosslinking agent therefor may form all or part of the film-forming resin of the coating. According to the present invention, one or more additional film-forming resins may also be used in the coating. For example, the coating composition may comprise any of a variety of thermoplastic and / or thermosetting compositions known in the art. The coating composition can be an aqueous or solvent-based liquid composition or, alternatively, in the form of a solid particulate, i. E. A powder coating.

The thermosetting or curable coating composition typically comprises a film-forming polymer or resin having functional groups that are reactive with, or reactive with, the cross-linking agent. Such additional film-forming resins may be selected, for example, from acrylic polymers, polyester polymers, polyurethane polymers, polyamide polymers, polyether polymers, polysiloxane polymers, copolymers thereof and mixtures thereof. In general, such polymers may be any polymer of the type produced by any method known to those skilled in the art. Such polymers may be solvent based, water-dispersible, emulsifiable, or have limited water-solubility. The functional groups of the film-forming resin may be any of a variety of reactive functional groups such as a carboxylic acid group, an amine group, an epoxide group, a hydroxyl group, a thiol group, a carbamate group, an amide group, a urea group, Isocyanate group), a mercaptan group, and combinations thereof. Suitable mixtures of film-forming resins may also be used in the preparation of the coating compositions of the present invention.

The thermosetting coating composition typically comprises a cross-linking agent that can be selected from any of the cross-linking agents described above. For example, the coating of the present invention comprises a thermosetting film-forming polymer or resin and a crosslinking agent therefor, which crosslinking agent may be the same or different from the crosslinking agent used to crosslink the polyester- have. The present invention may comprise a thermosetting film-forming polymer or resin having a functional group that is self-reactive, and in this way the thermosetting coating is self-crosslinked. The coating of the present invention may comprise from 1 to 100 wt%, such as from 10 to 90 wt%, or from 20 to 80 wt%, of the polyester-urethane resin of the present invention, based on the total weight of the coating. The coating composition of the present invention also comprises a crosslinking agent for the branched polyester-urethane resin of from 2 to 90 wt%, such as from 5 to 60 wt%, or from 10 to 40 wt%, based on the total solids weight of the coating can do. If desired, the additional component may comprise from 1 wt% to 70 wt% or more, based on the total solids weight of the coating.

According to the present invention, the coating comprising the polyester-urethane resin and / or the polyester-urethane resin is substantially free of epoxy. The expression "substantially free of epoxy" herein means that the polyester-urethane resin and / or the coating comprising it is substantially free of epoxy or epoxy moieties, residues of oxiran ring or oxiran ring, bisphenol A, BADGE or BADGE , Adduct of bisphenol F, BFDGE or BFDGE. The polyester-urethane resin and / or coatings comprising it may be substantially free of bisphenols or residues thereof, such as bisphenol A, bisphenol F, BADGE and BFDGE. The polyester-urethane resin and / or coatings comprising it may also be substantially free of polyvinyl chloride or related halide-containing vinyl polymers. "Substantially free" means that the polyester and / or coating is not more than 10% by weight, such as not more than 5% by weight, not more than 2% by weight, or not more than 1% by weight, based on the total solids weight, Quot; is meant to include any form of compound. Thus, it will be appreciated that the polyester-urethane resins and / or coatings according to the present invention may contain minor or minor amounts of these components, but that they may be " substantially free ". The present invention also contemplates that the polyester-urethane resin and / or coatings comprising it have no or any of the enumerated derivatives listed above.

The coating of the present invention may be applied to any substrate known in the art such as automotive substrates, industrial substrates, packaging substrates, wood flooring and furniture, garments, electronics such as housing and circuit substrates, glass and transparencies, Golf balls and the like. Such a substrate may be, for example, metallic or non-metallic. Metallic substrates include tin, steel, tin-plated steel, chrome-passivated steel, zinc-plated steel, aluminum, aluminum foil. The non-metallic substrate may be a polymeric, plastic, polyester, polyolefin, polyamide, cellulose, polystyrene, polyacrylic, poly (ethylene naphthalate), polypropylene, polyethylene, nylon, EVOH, polylactic acid, ("PC / ABS"), polyamide, wood, veneer, wood composite, particulate board, polycarbonate, Medium density fiber boards, cement, stone, glass, paper, cardboard, fabrics, synthetic and natural leather. The substrate may be already processed in a predetermined manner, for example, to give a visual or color effect.

The coatings of the present invention can be applied by any standard method in the art, such as electrocoating, spraying, electrostatic spraying, dipping, rolling, brushing, and the like.

The coating may be applied at a dry film thickness of 0.04 to 4 mils, such as 0.3 to 2 mils, or 0.7 to 1.3 mils. It is also contemplated that the coating may be applied at a dry film thickness of greater than 0.1 mil, greater than 0.5 mil, greater than 1.0 mil, greater than 2.0 mil, greater than 5.0 mil, or even thicker. The coatings of the present invention may be used alone or in combination with one or more other coatings. For example, the coating of the present invention may or may not include a colorant and may be used as a primer, a basecoat, and / or a topcoat. For substrates coated with multiple coatings, one or more of these coatings may be a coating as described above. The coatings of the present invention may also be used as packaging "size" coatings, wash coats, spray coats, end coats, and the like.

As mentioned previously, the polyester-urethane resins of the present invention can be used in automotive coating compositions. In addition, the polyester resin may be used in the formation of a multilayer coating system, which may include two or more coating layers, at least one of which includes a polyester-urethane resin as described herein. For example, the multilayer coating system may include a first basecoat layer and an optional clearcoat layer. The multilayer coating system may further comprise a second base coat layer and an optional electrodeposited coat layer. The coating compositions of the present invention are particularly suitable for use in compact coating processes. A "compact coating process" or "compact process" is a process in which at least one curing step is removed in a standard automotive coating process. In other words, in a compact coating process, one or more curing steps may be combined to deposit one or more coating layers on a prior coating layer that may not be cured, although it may be optionally dried, in a "wet-on-wet" These layers are cured simultaneously. Often, the compact process needs to eliminate and cure the use of a primer-surfacer; In a compact process, a standard primer-print layer can be replaced with a first base coat layer. Some compact processes apply two base coat layers to the substrate, also known as a first basecoat layer (B1) and a second basecoat layer (B2). The polyester-urethane resins disclosed herein may be used in a basecoat composition forming one or both of a first base coat layer and a second base coat layer.

Optional electrodeposition coating compositions of the multilayer coating system may comprise conventional anionic or cationic electrodepositable coating compositions such as epoxy or polyurethane-based coatings. Suitable electrodepositable coating compositions are described in U.S. Patent Nos. 4,933,056; 5,530,043; 5,760,107 and 5,820,987. The cured electrodeposited layer, if used, may be about 100 micrometers in dry film thickness, for example 15 to 50 micrometers.

As described above, when one or more base coats are used in the multilayer coating system, they can be deposited from the coating composition of the present invention. Other suitable basecoat compositions that can be used in the multilayer coating systems of the present invention are described in U.S. Patent Nos. 8,152,982 and 8,846,156. When two or more base coats are used, these base coats may be the same or different. "Different" can include two or more different coating compositions, at least one of which is a coating composition incorporating a branched, unsaturated polyester-urethane resin according to the present invention. "Different" may also include at least two different coating compositions, including but not limited to, branched polyester-urethane resins, but in different amounts, in proportions and / or containing other components or additives. After application to at least a portion of the substrate, the first basecoat composition may be dried or thermally cured at ambient or elevated temperature, for example, by forced air. Means to remove at least water and / or solvent from the coating composition at a temperature lower than the temperature necessary to cure the coating when used in connection with the application of the coating layer, Such as flashing or dewatering processes. For example, drying includes "flashing ", where generally the coated substrate removes some of the solvent, but at ambient or slightly elevated temperatures for a short time (typically 30 seconds to 20 minutes) Typically less than 40 ° C), in which the coated substrate is sufficient to remove the solvent, but at a predetermined temperature for a period of time insufficient to cure the coated substrate, such as 1 to 10 minutes, 121 < 0 > C). Drying at "ambient" may be accomplished by heating at least a portion of the solvent (including, for example, water or organic solvent) in the coating composition, without the aid of heat or energy (e.g., calcining in an oven, And so on) can be removed.

Similarly, if used, a second base coat layer may be deposited on at least a portion of the substrate coated with the first base coat, and the coated substrate may be reapplied to the drying step as described above. If the first basecoat is dried and uncured, then the second basecoat can be cured at the same time. Thus, it will be appreciated that one curing step may be omitted by wet-on-wet application of the second base coat over the uncured first base coat and co-curing of the two base coats. The dry film thickness of the first and second basecoat layers (or, alternatively, if applicable, a single base coat layer) may be as high as 100 micrometers, but is typically from 1 to 50 micrometers, such as from 5 to 30 micrometers , Or 10 to 25 micrometers.

The multilayer coating system may optionally comprise a clearcoat layer. When used, the clearcoat composition may comprise a branched unsaturated polyester-urethane resin of the present invention. Alternatively, the present invention can include the use of conventional clearcoat compositions. The clear coat will be understood as a substantially transparent coating. Thus, the clearcoat may have some color, provided that it does not have any appreciable effect on the ability to opacify the clearcoat or to view the underlying substrate. The clearcoat may be used, for example, with a colored base coat layer. The clearcoat may be formulated as is known in the coating arts. Other suitable clearcoat compositions are disclosed in U.S. Patent Nos. 4,650,718; 5,814, 410; And 5,814,410. The multilayer coating system of the present invention may comprise any clearcoat layer deposited, for example, on at least a portion of a substrate coated with one or more basecoat layers as described above. The clearcoat layer is applied to the base coat layer and can be cured using any conventional means. The clearcoat can be applied to a dried but uncured base coat and the layers can be cured simultaneously or the base coat can be cured before the clearcoat is applied. Once applied and cured, the dry-film thickness of the clearcoat layer can be as high as 100 micrometers, but is usually in the range of 15 to 80 micrometers, such as 30 to 60 micrometers.

According to the present invention, the coating can be used as a primer, for example, as an anti-chip primer. Anti-chip primer coating compositions are known in the automotive OEM industry and are commonly used in various parts of the vehicle, such as the leading edge of the door, the fenders, the hood and the vehicle A, prior to application of the primer- Can be applied to a pillar surface. The anti-chip primer coating composition need not be cured prior to application of one or more subsequent coating layers. Rather, the anti-chip primer coating composition is treated with an ambient flash step, wherein it is exposed to ambient air for a certain period of time to evaporate a portion of the organic solvent from the anti-chip coating composition. The curing of the anti-chip primer coating composition occurs simultaneously with the at least one additional coating layer (co-curing). Primers, such as anti-chip primers, according to the present invention typically comprise several colorants and are typically used after one or more additional coatings, e. G., After the electrocoat layer and before the primer surface layer, the colored basecoat layer, the clearcoat layer, Layer.

It will be appreciated that the coatings described above can be a one-component ("1K") composition or a multi-component composition, such as a two component ("2K" 1K composition will be understood to refer to a composition in which all of the coating components are retained in the same container after and during storage. The 1K coating is applied to the substrate and can be cured by any conventional method, such as heating, forced air, and the like. The coatings of the present invention may also be multi-component coatings, which are understood as coatings in which the various components are individually retained until just prior to application. As described above, the coating of the present invention may be thermoplastic or thermosetting.

The present invention also relates to a method of forming a multilayer coating system on a substrate comprising forming a first basecoat layer on at least a portion of a substrate by depositing a first basecoat composition on at least a portion of the substrate, ; Optionally, drying or curing the first basecoat layer; Depositing a second basecoat composition that is the same as or different from the first basecoat composition on at least a portion of the first basecoat layer to form a second basecoat layer on at least a portion of the first basecoat layer step; Optionally, drying or curing the second basecoat layer; Optionally forming a clearcoat layer on at least a portion of the outermost basecoat layer by depositing a clearcoat composition on at least a portion of the outermost basecoat layer; And simultaneously curing the uncured coating layer, wherein at least one of the first basecoat composition and the second basecoat composition comprises the polyester-urethane resin of the present invention. If used, the second basecoat composition may be the same as or different from the first basecoat composition. If used, the first and second base coats may be cured separately and may be cured both at the same time, or may be cured at the same time as the optional clear coat, before forming the subsequent coating. The method may further comprise forming an electrodeposition coating layer by electrodepositing the electrodepositable coating composition onto at least a portion of the substrate prior to forming the first basecoat layer. The electrodeposition coating layer may be dried or cured prior to forming the first base coat layer.

Surprisingly, a multilayer coating system having a coating composition (e.g., a basecoat composition) containing an uncured branched polyurethane-urethane resin of the present invention can be applied to a similar polyester-urethane resin composition using a conventional polyester-urethane resin and a polyurethane resin coating composition It has been found that improved coating interlayer adhesion, chip resistance and sag resistance characteristics can be imparted to the coating as compared to multiple coating systems. This is especially true when 10% to 30% of OH remains unreacted in the polyester-urethane prepolymer. For example, such a coating may have a chip resistance of less than 2 measured at 2 bar and 25 ° C in an Erichstenstone hammer blow tester model 508. This coating was also cured by using Sikaflex windshield adhesive (250HMV-2 +) obtained from Silka Schweiz AG for 10 days at a temperature of 40 ° C and 100% humidity, Can have intercoating properties of greater than 90%, even greater than 95%, when subjected to a glass adhesion test. In addition, the coating of the present invention may have a 15 촉 force and a sag resistance of, for example, 20 袖 m or more. In other words, the coating of the present invention can be applied to a dry film thickness of greater than 15 mu before the paint slag reaches a tolerance of less than 3 mm, as described below.

Coil coatings that are widely applied in many industries are also within the scope of the present invention. The coatings of the present invention are suitable for coil coating due to the unique combination of flexibility and hardness as described above. Coil coatings also typically include coloring agents.

The coatings of the present invention are also suitable for use in packaging coatings. The application of various pretreatments and coatings to packaging is well established. Such treatments and / or coatings can be used in the case of metal cans, where the treatments and / or coatings are used to slow or inhibit corrosion, provide decorative coatings and facilitate handling during the manufacturing process. The coating can be applied to the interior of such a can to prevent the contents from contacting the container metal. For example, contact between the metal and the food or beverage can cause corrosion of the metal container, which can contaminate the food or beverage. This is especially so when the contents of the can are acidic in nature. The coating applied to the interior of the metal can also prevents corrosion in the can head space which is the space between the fill line of the product and the can lead. Corrosion in the head space is particularly problematic in foods with high-salt contents. The coating can also be applied to the exterior of the metal can. Certain coatings of the present invention include coiled metal stocks, such as metal stocks ("can end stock") for making can end portions and coiled metal stocks ("cap / lid stock" ). ≪ / RTI > Coatings designed for use in can end feedstocks and cap / lid raw materials are typically soluble and extensible, typically because they are applied prior to cutting of the part and prior to stamping of the coiled metal stock. For example, these materials are typically coated on both sides. Thereafter, the coated metal raw material is punched. In the case of the can end, the metal is then scored for a "pop-top" opening and then attached to the pop-top loop with a separately fabricated pin. The end portion is then attached to the can body by an edge rolling process. A similar process is performed for the "easy openable" can end. In the case of an easily openable can end, the marks substantially around the periphery of the lead typically facilitate the opening or removal of the leads from the can by the pull tab. In the case of caps and lids, the cap / lid raw material is typically coated with, for example, a roll coating, and the cap or lid is stamped from the raw material. However, it is also possible to coat the cap / cap after molding. Coatings for cans that are treated with relatively stringent temperature and / or pressure requirements must also be resistant to popping, corrosion, blushing and / or blistering.

Thus, the present invention also relates to a package at least partially coated with any of the coating compositions described above. In some examples, the package may be a metal can. The term "metal can" includes any type of metal can, container or any type of bowl or part thereof used to hold something. One example of a metal can is a food can. The term "food cans" is used herein to refer to cans, containers or any type of bowl, or a portion thereof, used to hold any type of food and / or drink. The "metal can" includes in particular food can, and in particular includes a "can end" which is typically stamped from the can end feedstock and used with packaging of the beverage. In addition, the term "metal can" includes, in particular, metal caps and / or lids, such as bottle caps, screw top caps and leads of any size, lug caps and the like. Metal cans can be used to hold food and / or beverages as well as other articles such as, but not limited to, personal care products, insect sprays, spray paints, and any other compounds suitable for packaging in aerosol cans. The can includes not only a "two-piece can" and a "three-piece can" but also a drawn and ironed one-piece can . These one-piece cans often have aerosol product applications. Coated packages according to the present invention may also include plastic bottles, plastic tubes, laminates, and flexible packaging such as those made of PE, PP, PET, and the like. Such packaging may include, for example, food, toothpaste, personal care products, and the like.

The coating can be applied to the interior and / or exterior of such a package. For example, the coating can be roll coated onto a metal used to make a two-piece food can, a three-piece food can, a can end ingredient and / or a cap / lid ingredient. The present invention contemplates that the coating is applied to the coil or sheet by roll coating and then the coating is cured by radiation and the can end is stamped and made into a finished product (i.e., can end) do. It is also contemplated that the coating is applied to the bottom of the can as a rim coat and that such application may be performed by roll coating. Rim coats function to reduce friction for subsequent manufacturing of can and / or improved handling during processing. The coating of the present invention may be applied to a cap and / or a lid, which may be applied, for example, to a protective varnish, and / or a cap (especially to the bottom of the cap) applied before and / (E. G., Having a greenish seam). ≪ / RTI > The decorated can feedstock can also be partially coated with the coating described above, and such decorated and coated can feedstock is used to form a variety of metal can.

The substrate coated in accordance with the present invention may be coated with any of the compositions described above by any method known in the art, such as spraying, rolling, dipping, brushing, flow coating, and the like. The coating may also be applied as an electrocoat if the substrate is conductive. Suitable methods for such application may be determined by those skilled in the art based on the type of substrate being coated and the function with which the coating is used. The coatings described above can be applied as a single layer or, if desired, as multiple layers using multiple heating steps between each layer, on a substrate. After applying the coating composition to the substrate, it can be cured by any suitable method.

Unless expressly stated otherwise herein, all numerical values expressing values, ranges, amounts, or percentages are read as if they were modified to such terms, even though the term "about" Also, any numerical range recited herein is intended to include all sub-ranges subsumed therein. The singular includes a plural, and vice versa. For example, reference herein to "polyester-urethane resin", "unsaturated acid or an anhydride or ester thereof", "polyester prepolymer", "urethane segment", "polyol segment", "crosslinking agent" The term "polymer" as used herein refers to both oligomers and homopolymers and copolymers, and the prefix "poly" refers to two or more. Comprising " and " comprising "and " including, but not limited to" means "including but not limited to. &Quot; Therefore, the present invention relates specifically to the following aspects 1 to 20, but is not limited thereto.

Mode 1.

I) i. The residue of the polyol; ii. Ethylenically unsaturated polycarboxylic acids, residual anhydrides and / or esters, and iii. Free radical polymerization of an ethylenically unsaturated polyester prepolymer comprising a residual moiety of an isocyanate-functional compound, or

II) i. The residue of the polyol; And ii. Formation of a hydroxy-functional polyester polymer by free radical polymerization of a hydroxy-functional ethylenically unsaturated polyester prepolymer comprising an ethylenically unsaturated polycarboxylic acid, anhydride and / or residual residues of an ester, - reaction of a functional polyester polymer with an isocyanate-functional compound

≪ / RTI > wherein the curable branched polyester-urethane polymer is a polyurethane.

2. The process of embodiment 1, wherein the ethylenically unsaturated polyester prepolymer comprises: i. The residue of the polyol; ii. Ethylenically unsaturated polycarboxylic acids, residual anhydrides and / or esters, and optionally iii. Wherein the free radical polymerisation occurs in the presence of a polyester prepolymer comprising a residual moiety of an isocyanate-functional compound or a second ethylenically unsaturated prepolymer which is a polyester-urethane prepolymer.

3. The process of embodiment 1 wherein the polyol comprises neopentyl glycol and / or the ethylenically unsaturated polycarboxylic acid, anhydride and / or ester comprises maleic acid, maleic anhydride and / or ester. - urethane polymer.

4. The polyester-urethane polymer according to any one of modes 1 to 3, wherein the isocyanate functional compound comprises isophorone diisocyanate.

5. The process of any one of modes 1 to 4 wherein the polyester-urethane prepolymer is reacted with a carboxylic acid, anhydride or ester prior to free radical polymerization and neutralized with an amine, or is reacted with a hydroxy-functional polyester polymer and an isocyanate Wherein the reaction product with the functional compound is reacted with a carboxylic acid, neutralized with an amine and dispersed in water.

6. The polyester-urethane polymer of embodiment 5, wherein the carboxylic acid comprises 2,2-dimethylol propionic acid and the amine comprises triethylamine.

Embodiment 7. The polyester-urethane polymer according to any one of modes 1 to 6, wherein the free radical polymerization takes place in an aqueous solution.

The process of any one of modes 1 to 7, wherein the weight average molecular weight (Mw) is greater than or equal to 15,000, such as greater than or equal to 30,000, or greater than or equal to 15,000, Lt; RTI ID = 0.0 > 100,000. ≪ / RTI >

The process of any one of modes 1 to 8 wherein the weight average molecular weight (Mw) of the polyester-urethane prepolymer is greater than or equal to 2,500 as determined by gel permeation chromatography using a polystyrene standard material for calibration, Ester-urethane polymer.

10. The process of any one of modes 1 to 9, wherein the (meth) acrylate or (polyester-urethane polymer not containing residual moieties of methacrylic acid.

11. The polyester-urethane polymer of any one of embodiments 1 to 10, wherein the polyester-urethane polymer has a hydroxyl value of 75 to 120 mg KOH / g.

Mode 12.

(a) a polyester-urethane polymer according to any one of modes 1 to 11,

(b) a curing agent having a plurality of functional groups reactive with the polyester-urethane polymer (a)

≪ / RTI > preferably a base coat composition.

13. A method of forming a multilayer coating on a substrate,

Forming a first basecoat layer over at least a portion of the substrate by applying a first basecoat composition over at least a portion of the substrate;

Optionally, drying or curing the first basecoat layer;

Applying a second basecoat composition that is the same as or different from the first basecoat composition to at least a portion of the first basecoat layer to form a second basecoat layer on at least a portion of the first basecoat layer;

Optionally, drying or curing the second basecoat layer; And

Curing the uncured coating layer

Wherein at least one of the first basecoat composition and the second basecoat composition comprises the curable coating composition according to embodiment 12.

Embodiment 14. The method of embodiment 13 wherein the second basecoat composition is different from the first basecoat composition and / or comprises a curable coating composition according to embodiment 12.

15. The method of embodiment 13 or 14 further comprising electrodepositing the electrodepositable coating composition onto at least a portion of the substrate prior to forming the first basecoat layer to form an electrodeposited coating layer.

16. The method of any one of embodiments 13-15 further comprising forming a clearcoat layer over at least a portion of the second basecoat layer by depositing a clearcoat composition over at least a portion of the second basecoat layer Way.

Mode 17.

(a) applying the curable coating composition according to embodiment 12 to at least a portion of a surface of a substrate, and

(b) at least partially curing the applied curable coating composition

Lt; RTI ID = 0.0 > at least < / RTI >

Mode 18 The coating substrate of embodiment 17, wherein the coating has a chip resistivity of less than 2 as measured with an Ericsson Stone Hammer Blow Test Equipment Model 508 operating at 2 bar and 25 占 폚.

Embodiment 19. A coated substrate according to Mode 17 or 18, which is a substrate coated with a multilayer coating formed according to the method according to any one of Embodiments 13 to 16. [

Embodiment 20. The coated substrate according to any one of modes 17 to 19, wherein the substrate is part of a vehicle.

Example

The following examples are intended to illustrate the invention and should not be construed as limiting the invention in any way.

Preparation of unsaturated polyester prepolymer

Unsaturated polyester prepolymer was prepared from the following components as described below: A total of 3327.5 g neopentyl glycol, 3350.9 g adipic acid, 321.5 g maleic anhydride and 0.203 g butylstannic acid were mixed with a stirrer, temperature probe And a suitable reaction vessel equipped with a nitrogen recovery apparatus and a glycol recovery apparatus (filled column with an empty column at the top and a distillation head connected to a water-cooled condenser). The contents of the flask were heated to 215 캜, starting at about 140 캜, while continuously removing the water distillate. The temperature of the contents was maintained at 215 캜 until about 892 g of water was distilled and the acid value of the reaction mixture was found to be 1.86 mg KOH / g. The contents of the reactor were cooled to 160 DEG C and then diluted to 75% theoretical solids using 2040 g of PROGLYDE DMM. The reaction product had a measured solids content of 73.7%, a hydroxyl value of 72.8 mg KOH / g and a weight average molecular weight of 3434, as measured on a polystyrene standard material.

Preparation of Uncured Bifurcated Polyester-Urethane Resin

Example 1

A total of 1316.9 grams of the unsaturated polyester prepolymer prepared as described above and 187.1 grams of proglide DDM were placed in a suitable reaction vessel equipped with a stirrer, temperature probe, reflux condenser, and nitrogen blanket. The contents of the flask were mixed and heated to 45 캜, 231.7 g of isophorone diisocyanate was added dropwise from the addition funnel over 30 minutes to the reaction contents, followed by rinsing the funnel with 20.4 g of proglide DMM. After about 98 minutes, the contents of the flask were heated to 55 占 폚. The isocyanate (NCO) equivalents were checked by titration every 30 minutes until the NCO value reached about 1655. A total of 69.7 g of 2,2-dimethylol propionic acid was added to the flask and then 42.1 g of trimethylamine was added and rinsed with 10.2 g of proglide DMM. The contents of the flask were heated to 80 DEG C until the isocyanate peak at about 2265 cm <" ¹ > in the Fourier Transform Infrared Spectroscopy (FTIR) spectrum disappeared. A total of 19.8 g of anhydrous trimellitic acid was added to the flask via a powder funnel. The contents of the flask were maintained at 80 DEG C until the anhydrous peak at about 1790 cm <" ¹ > in the FTIR spectrum disappeared. The milliequivalents (meq) of the base were measured to be 0.186. 24.0 g of triethylamine was added to the flask to bring about the theoretical total neutralization to about 80%. Triethylamine was rinsed with 6.1 g of proglide DMM. After stirring for about 15 minutes, 1747.8 g of deionized water was added to the reaction contents over 30 minutes. The contents of the flask were heated to 80 DEG C over 30 minutes. Once the contents had reached a temperature of 80 DEG C, a mixture of 20.5 g of LUPEROX® 26 (available from Arkema) and 10.3 g of proglide DMM was added to the flask over about 1 minute, And rinsed with 10.2 g of proglide DMM. The contents of the flask were left at 80 占 폚 for 1 hour and then cooled to 45 占 폚. At 45 [deg.] C, 17.7 g of deionized water was added to the flask. The contents of the reactor were stirred for 3 minutes and then discharged to the outside. The final resin had a measured solids of 35.4%, a Brookfield viscosity of about 103 cp (# 1 spindle, 50 rpm, 25 캜) and a weight average molecular weight of 37334 measured against a polystyrene standard material. This polyurethane dispersion had a theoretical hydroxyl group value of 24.9 mg KOH / g for the solid resin.

Example 2

A total of 1316.9 g of the unsaturated polyester prepolymer prepared as described above and 187.1 g of proglide DDM were placed in a suitable reaction vessel equipped with a stirrer, a temperature probe, a reflux condenser and a nitrogen blanket.

The contents of the flask were heated to 45 DEG C and 247.5 grams of isophorone diisocyanate was added from the addition funnel over 30 minutes followed by rinsing the funnel with 20.4 grams of Proglide (TM) DMM. After about 70 minutes, the flask was warmed to 55 < 0 > C. The equivalent of isocyanate (NCO) was titrated every 30-60 minutes and checked until it reached about 1574. 69.3 g of 2,2-dimethylol propionic acid were then placed in the flask, followed by the addition of 41.9 g of triethylamine and rinsing with 10.1 g of Proglly (trade name) DMM. The contents of the flask from the FTIR spectrum until it disappears the isocyanate peak at about 2265 cm ^-1 were heated to 80 ℃. Then, 19.7 g of anhydrous trimellitic acid was added to the flask via a powder funnel. The contents of the flask were maintained at 80 DEG C until the anhydrous peak at about 1790 cm <" ¹ > in the FTIR spectrum disappeared. The milliequivalents (meq) of the base were determined to be 0.212. 18.6 g of triethylamine was added to give a theoretical total neutralization of about 80%. Triethylamine was rinsed with 6.0 g of Proglide (trade name) DMM. After stirring for about 15 minutes, 1771.8 g of deionized water was added over 30 minutes. The contents of the flask were heated to 80 DEG C over 30 minutes. When the contents reached a temperature of 80 ° C., a mixture of 20.4 g of Luperox® 26 (available from Arkema) and 10.2 g of Proglide (trade name) DMM was added to the flask over about 1 minute and 10.2 g of proglide Product name) DMM. The contents of the flask were maintained at 80 占 폚 for 1 hour and then cooled to 45 占 폚. At 45 캜, 17.6 g of deionized water was added. The contents of the reactor were stirred for several minutes and then discharged. The final polyurethane dispersion had a measured solids (110 캜 / hour) of about 35.7%, a meq acid of 0.203, a meq base of 0.149, a pH of 7.23 and a Brookfield viscosity of about 423 cp (# 1 spindle, 50 rpm, 25 캜). This polyurethane dispersion had a theoretical hydroxyl value of 18.6 mgKOH / gg for the solid resin.

Example 3

A total of 1316.9 grams of the unsaturated polyester prepolymer prepared as described above and 187.1 grams of proglide DDM were placed in a suitable reaction vessel equipped with a stirrer, temperature probe, reflux condenser, and nitrogen blanket. The contents of the flask were heated to 45 DEG C and 247.5 grams of isophorone diisocyanate was added from the addition funnel over 30 minutes followed by rinsing the funnel with 20.4 grams of Proglide (TM) DMM. The flask was warmed to 55 < 0 > C. The isocyanate (NCO) equivalent was titrated every 30 minutes and checked until it reached about 1505. Then, 69.5 g of 2,2-dimethylol propionic acid was added to the flask and then 42.0 g of triethylamine was added and rinsed with 10.1 g of Proglide (trade name) DMM. The contents of the flask from the FTIR spectrum until it disappears the isocyanate peak at about 2265 cm ^-1 were heated to 80 ℃. Then, 19.8 g of anhydrous trimellitic acid was added to the flask via a powder funnel. The contents of the flask were maintained at 80 DEG C until the anhydrous peak at about 1790 cm <" ¹ > in the FTIR spectrum disappeared. The milliequivalents (meq) of the base were measured as 0.207. 19.8 g of triethylamine was added to bring the theoretical total neutralization to about 80%. Triethylamine was rinsed with 6.1 g of proglide (trade name) DMM. After stirring for about 15 minutes, 1806.3 g of deionized water was added over 30 minutes. The contents of the flask were heated to 80 DEG C over 30 minutes. Once the contents had reached a temperature of 80 ° C, a mixture of 20.5 g of Luperox® 26 (available from Arkema) and 10.2 g of Proglide (trade name) DMM was added to the flask over about 1 minute and then 10.2 g of And rinsed with Proglide (trade name) DMM. The contents of the flask were maintained at 80 DEG C for about 1 hour. After about half of this 1 hour maintenance period, 538 grams of deionized water was slowly added to the flask. After the one hour hold was complete, the contents of the flask were cooled to 45 占 폚. At 45 캜, 17.6 g of deionized water was added. The contents of the reactor were stirred for several minutes and then discharged. The final polyurethane dispersion had a measured solids (110 캜 / hour) of about 31.3%, a meq acid of 0.174, a meq base of 0.127, a pH of 7.26 and a Brookfield viscosity (# 1 spindle, 50 rpm, 25 캜) Respectively. This polyurethane dispersion had a theoretical hydroxyl value of 12.4 mg KOH / g for the solid resin.

Uncured branched polyester-urethane resin

Table 1 shows the results of a comparison of the five uncured base-coat samples (samples 1 and 2) of the present uncured, branched, polyester-urethane resin (polyester-urethane resin of Example 1) List the components used to make colored base coat samples (Samples 3, 4 and 5).

The comparative sample 1 does not use the commercially available polyurethane resin or the polyester-urethane resin of the present invention. The comparative sample 2 uses a commercially available polyurethane resin. Samples 3, 4 and 5 use the polyester-urethane resin of the present invention.

[Table 1]

¹ The polyester-urethane resin of Example 1

² Polyurethane resin available from Chemtura Corp. Witco Bond 272.

³ Polyurethane Acrylic Latex - Polymer of Example IIA as described in U.S. Patent No. 5,972,809.

^{4 An} acrylic dispersion (84.5 wt% deionized water) consisting of 30.0 wt% styrene, 35.0 wt% n-butyl acrylate, 18.0 wt% n-butyl methacrylate, 8.5 wt% 2-hydroxyethyl acrylate, and 8.5 wt% acrylic acid / RTI > solid of 26.1 wt% in a 15.5 wt% butylcarbitol solvent mixture and 54% neutralized with dimethylethanolamine).

⁵ Polyester resin - Polymer of Example 2 described in U.S. Patent No. 5,468,802.

⁶ dimethylethanolamine (50% aqueous solution)

⁷ Phosphorylated epoxy made from Epon 828 (polyglycidyl ether of bisphenol A), available from Shell Chemical Co.; Phosphoric acid in a weight ratio of 83:18.

⁸ Additives available from Byk Chemie.

⁹ Polyether polyols available from Bayer Material Science.

¹⁰ Melamine curing agent available from INEOS Melamine.

¹¹ , ¹² Solvent available from Dow Co.

¹³ Solvent available from Shell Chemical Company

¹⁴ Surfactants available from Air Products & Chemicals.

¹⁵ containing 50% TiO _2, and the solid content is 62% of the white tint paste.

¹⁶ Red hue paste with 34% iron oxide (II) and a solids content of 46%.

¹⁷ Violet tint paste with 12% Hostaperm Violet RL Special, commercially available from Clariant Pigments and having a solids content of 25%.

¹⁸ A black paste paste containing 5% Monarch 120 and having a solids content of 24%.

¹⁹ A 9% dispersion of Aerosil R812 commercially available as a 21% acrylic polymer blend from Evonik Degussa and having a solids content of 31%.

The basecoat was coated on a 12 inch x (10 cm x 10 cm) coated with a cured Electrocoat (ED 6060CZ) and Primer (A-F106820-4P5) available from PPG Industries, Sprayed in a controlled environment at 70-75 ° F (21-24 ° C) and 50-60% relative humidity on a 20 inch steel panel using a LabPainter instrument manufactured by LacTec GmbH . For chip resistance and adhesion testing, the basecoat was spray applied to the panel and flashed at ambient temperature for 5 minutes and then calcined at 80 < 0 > C for 10 minutes. A clear coat (A-F105359-4C0) available from PPG Industries, Italy was spray applied onto the base coat and flashed at room temperature for 10 minutes. The entire laminated system was calcined at 140 占 폚 for 30 minutes. The dried film thicknesses of the base coat and the clear coat were 0.7 to 0.8 mil and 1.6 to 2.3 mil, respectively.

For Sag resistance, a 12 inch x 20 inch steel panel coated with a cured electrocoat (ED 6060CZ) and a primer (A-F106820-4P5) available from PPG Industries, Italy, The coat composition was sprayed. Holes (10 mm diameter each) were punched equidistance apart by the length of each steel test panel. To apply each basecoat composition, the test panels were placed vertically, with the holes going from left to right. Each of the basecoat compositions of each of Samples 1 to 5 was sprayed using automated spraying equipment in an environment adjusted to 70-75 DEG F (21-24 DEG C) and 50-60% relative humidity using the composition in each pass To produce a film thickness wedge, also known as a "wedge panel " (i.e., film thickness increasing from left to right of the test panel). Each coated test panel was then "flashed" at ambient temperature for 5 minutes and then calcined at 80 ° C for 10 minutes. A clear coat (A-F105359-4C0) available from PPG Industries, Italy was spray applied onto the base coat and flashed at room temperature for 10 minutes. The entire laminated system was calcined at 140 占 폚 for 30 minutes. The test panels were held vertically suspended until fully cured. Sag resistance was measured by recording the length of the "sag", ie, the length of the coating (millimeter) leaving the bottom of the hole at a given dry film thickness. For the purposes of the present invention, an acceptable coating slag was measured when the coated bird reached a tolerance limit of less than 3 mm from the bottom of the hole at a given dry film thickness. In the present invention, the dry film thickness of the base coat is 0.2 to 1.4 mils, and the clear coat has a dry film thickness of 1.6 to 2.3 mils (measured from left to right on the steel sheet). Sag resistance test results are shown in Table 2 below, where higher values indicate better sag resistance.

Table 2 provides a summary of the performance and physical properties obtained for each of the samples.

[Table 2]

¹¹ coating adhesion test was performed using Walter Cleaning Systems steam jet test equipment model LTA1-HA-T80-LP-PA and 1/4 HP nozzle (PMEG-2506) as follows: A test panel was prepared as described above for Samples 1-5. Several cuts were formed in a cross pattern on the coated test panels. The scribed test panel was sprayed with a high pressure steam jet at a temperature of 60 ° C, a pressure of 70 bar, a distance of 10 cm from the nozzle to the test panel, and a duration of 1 minute at an angle of 90 ° to the test panel, Respectively. The paint adhesion was visually inspected and measured by the Volkswagen (VW) test method PV1503B. The higher the percentage value, the better the paint adhesion.

¹² Windshield adhesion test was performed and measured as follows: The bead of windshield adhesive was applied to the clearcoat surface within 1-4 hours after final calcination (30 minutes at 140 ° C). A Sikaflex windshield adhesive (250HMV-2 +) obtained from Silka Schweiz AG was used. Approximately 20 mm x 200 mm x 50 mm adhesive beads were placed on the cured color + clear substrate. The adhesive was cured at a temperature of 40 占 폚 for 10 days under 100% humidity. After 10 days of curing, the adhesive bead was cut into a razor blade and the edge of the adhesive was pulled back at an angle of 180 °. At least 10 incisions were performed for each system. Any delamination of the multi-coating layer was visually inspected and measured. The result that 90-100% of the coating remains on the substrate remains "acceptable" or "passed" in the automotive industry. This is considered "failure" when 0% -10% of the coating is delaminated from the substrate.

^{13 The} chip resistance test was performed using a Stone Hammer Blow Test Equipment Model 508 manufactured by ERICHSEN GMBH & CO KG as follows: On each coated test panel, the size 500 g of 4-5 mm shredded steel shot were hit twice with a pressure of 200 Kpa. The Stonehammer Blow Test determines the ability of a multi-coating system to withstand impacts caused by small objects hitting high speed test substrates similar to rocks that hit the vehicle body at high speeds. The panel was evaluated using a visible rating scale of DIN EN ISO 20567-1. The rating scale is between 0.5 and 5, the lower the value, the better the resistance to chipping.

¹⁴ Sag resistance was measured by visual inspection and recording of the length of the bird (in millimeters), with higher values indicating better sag resistance.

The results shown in the above Table 2 demonstrate that a base coat having suitable intercoat adhesion, chip resistance and sag resistance can be produced according to the present invention.

Claims (27)

An uncured, branched, polyester-urethane resin prepared by free radical polymerization of a double bond of an unsaturated polyester-urethane prepolymer,
The polyester-urethane resin comprises (a) a polyol segment, (b) an unsaturated polycarboxylic acid and / or an anhydride and / or ester thereof, and (c) a urethane segment. The method according to claim 1,
Wherein the polyol segment comprises neopentyl glycol and the unsaturated polycarboxylic acid, anhydride and / or ester segment comprises maleic acid, maleic anhydride and / or maleic acid ester. The method according to claim 1,
The polyester-urethane prepolymer is reacted with a carboxylic acid, anhydride or ester prior to free radical polymerization and is neutralized with an amine. The method of claim 3,
Wherein the carboxylic acid comprises 2,2-dimethylol propionic acid and the amine comprises triethylamine. The method according to claim 1,
Wherein the urethane segment is formed by reaction of an isocyanate with at least one hydroxyl group from the polyol segment. The method according to claim 1,
Wherein the isocyanate comprises isophorone diisocyanate. The method according to claim 1,
Wherein the free radical polymerization takes place in aqueous solution. The method according to claim 1,
Polyester-urethane resin M is _W, as measured by gel permeation chromatography using a polystyrene standard for calibration, of 15,000 to 100,000, and a polyester-urethane resin. The method according to claim 1,
Polyester-urethane resin of a M _W, as measured by gel permeation chromatography using a polystyrene standard for calibration, 30,000 or more, a polyester-urethane resin. The method according to claim 1,
Polyester-urethane is M _W of the prepolymer, as determined by gel permeation chromatography using a polystyrene standard for calibration, a polyester, characterized in that more than 2,500-urethane resin. The method according to claim 1,
A polyester-urethane resin wherein the polyester-urethane resin does not comprise (meth) acrylate or residues thereof. The method according to claim 1,
Wherein the polyester-urethane resin has a hydroxyl value of 75 to 120 mg KOH / g as measured by ASTM Method D4274. A coating composition comprising the polyester-urethane resin of claim 1 and a crosslinking agent therefor. 14. The method of claim 13,
2 chip and a chip resistance of less than 2 when measured with an Erichsen stone hammer blow test equipment Model 508 at 25 < 0 > C. 14. The method of claim 13,
Wherein the polyol segment comprises neopentyl glycol and the unsaturated polycarboxylic acid, anhydride and / or ester segment comprises maleic acid, maleic anhydride and / or maleic acid ester. 14. The method of claim 13,
Wherein the coating is a basecoat. 13. A substrate that is at least partially coated with the coating of claim 13. 18. The method of claim 17,
Wherein said substrate is part of a vehicle. A method of forming a multilayer coating system on a substrate,
Forming a first basecoat layer over at least a portion of the substrate by depositing a first basecoat composition over at least a portion of the substrate;
Optionally, drying or curing the first basecoat layer;
Depositing a second basecoat composition that is the same as or different from the first basecoat composition on at least a portion of the first basecoat layer to form a second basecoat layer on at least a portion of the first basecoat layer step;
Optionally, drying or curing the second basecoat layer; And
Curing the uncured coating layer
Wherein at least one of the first and second basecoat compositions comprises the coating composition of claim 13. 20. The method of claim 19,
Further comprising depositing a clearcoat composition over at least a portion of the second basecoat layer to form a clearcoat composition on at least a portion of the second basecoat layer. 20. The method of claim 19,
Further comprising electrodepositing the electrodepositable coating composition on at least a portion of the substrate prior to forming the first basecoat layer to form an electrodeposited coating layer. 20. The method of claim 19,
Wherein the second basecoat composition is different from the first basecoat composition. 20. The method of claim 19,
Wherein the second basecoat composition comprises the coating composition of claim 13. a) free radical polymerization of a double bond of at least one unsaturated polyester prepolymer having hydroxyl functional groups to form a polyester polymer, and
b) reaction of the polyester polymer of step a) with an isocyanate
As an uncured branched polyester-urethane resin,
The polyester prepolymer
i) a polyol segment; And
ii) unsaturated polycarboxylic acids and / or anhydrides and / or ester segments
Wherein the polyester-urethane resin is a polyester-urethane resin. 25. The method of claim 24,
Wherein the reaction product of step b) is reacted with a carboxylic acid, neutralized with an amine and dispersed in water. 25. The method of claim 24,
A polyester-urethane resin, wherein the isocyanate comprises isophorone diisocyanate. An uncured, branched polyester-urethane resin prepared by free radical polymerization of a double bond of a first unsaturated polyester prepolymer and a double bond of a second unsaturated polyester prepolymer,
Each prepolymer may be independently < RTI ID = 0.0 >
a) a polyol segment; And
b) an unsaturated polycarboxylic acid and / or anhydride and / or ester segment
/ RTI >
Wherein at least one of said unsaturated polyester prepolymers comprises urethane segments, wherein said prepolymers are the same or different, branched polyester-urethane resins.