KR20160141820A - Branched polyester polymers and soft touch coatings comprising the same - Google Patents

Abstract

Disclosed is a crosslinkable, branched polyester prepared by the free radical polymerization of an unsaturated polyester prepolymer wherein the polymerization occurs primarily by the reaction of an unsaturated group. Also disclosed is a coating comprising said polyester, and a substrate at least partially coated with said coating.

Description

[0001] BRANCHED POLYESTER POLYMERS AND SOFT TOUCH COATINGS COMPRISING THE SAME [0002]

The present invention relates to a crosslinkable, branched polyester polymer prepared by free radical polymerization of double bonds of a first unsaturated polyester prepolymer and a second unsaturated polyester prepolymer. The polyester polymer has a Tg of 25 DEG C or less. The invention also relates to a coating comprising said polyester and to a substrate to which said coating is applied, said coating giving a soft touch to the substrate upon curing.

Cross-reference to related application

This application is a continuation-in-part of U.S. Patent Application No. 12 / 752,570, filed April 1, 2010, titled " Branched Polyester Polymer "

Conventional linear and branched polyester resins prepared by polycondensation of different combinations of polyols and polyacids are widely used in the coating industry. It is used to coat a wide variety of metal and non-metal substrates used in numerous different industries. Such industries include, in particular, industries in which flexible coatings are desirable. Particularly suitable examples include substrates used in the packaging industry, coil coatings and certain industrial and automotive coatings. Coatings have a particular "touch feel ", for example in consumer electronics, it is often desirable to have a coating with a" soft feel "or" soft feel ". A soft touching coating can impart a variety of tactile sensations, such as a velvet feel, silk feel, or rubber feel to the substrate. Despite the feel of such a coating, it is preferred that the coating is at least somewhat resistant to wear, marring, scratching and / or contamination.

The present invention relates to a crosslinkable, branched polyester polymer 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 The prepolymer independently comprises (a) a polyol segment, and (b) an unsaturated polycarboxylic acid and / or an anhydride and / or ester thereof, wherein the branched polyester polymer has a Tg of 25 占 폚 or lower. Coatings comprising such polyesters are also within the scope of the present invention, and substrates coated at least partially with the coating are also within the scope of the present invention.

The present invention relates generally to cross-linkable branched polyester polymers comprising a reaction product of components comprising a polyol fraction and an unsaturated polycarboxylic acid and / or an anhydride and / or ester thereof. The prepolymer is an unsaturated polyester, sometimes referred to herein as an "unsaturated polyester prepolymer "," prepolymer "or similar term. Free radical initiators are used to initiate polymerization through unsaturated groups of the unsaturated polyester prepolymer to provide branched polyesters. The branched polyester is cross-linkable, which means that it can be cross-linked with another compound. That is, the polyester has a functional group capable of reacting with the functional group on another compound. The reaction of the unsaturated groups of the prepolymer produces a cross-linkable, branched polyester. This polyester is a polymer. This is not a cured coating. Thus, the present invention differs from the prior art in that it crosslinks unsaturated points on the monomer and / or polymer to produce a cured coating.

The unsaturated polyester prepolymer comprises a polyol fraction. As used herein, "polyol" and similar terms refer to compounds having two or more hydroxyl groups. The polyols used to form the polyol fraction are commonly referred to herein as "polyol fraction monomers ". The polyol may be selected to contribute to the softness of the prepolymer. The polyol may also contribute to hardness, but the amount of polyol (s) used and each amount should be selected so that the unsaturated prepolymer produces a branched polyester having a Tg of at least 25 캜 in the reaction. The polyols suitable for use in the present invention may be any polyols known for the production of polyesters or mixtures thereof. 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 Cole, 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 and ethylene glycol); Hydroxy-alkylated 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 fraction may also comprise some, such as 10% or less, or 5% by weight, based on the total weight of the polyol fraction. In certain embodiments, the polyol fraction accounts for 10 to 90 wt%, such as 30 to 50 wt%, of the polyester prepolymer. The percentage of polyol in the prepolymer may vary greatly depending on the molecular weight of the polyol fraction.

The unsaturated polyester prepolymer also includes an unsaturated polycarboxylic acid / anhydride / ester. An unsaturated polyacid suitable for use in the present invention may be any unsaturated carboxylic acid containing two or more carboxy groups and / or their esters and / or anhydrides, or mixtures thereof. Examples include, but are not limited to, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, teraconic acid, and / or their esters and / or anhydrides. When the unsaturated polyacid ester is in the form of an ester, such esters may be formed using any suitable alcohol and include, for example, C ₁ -C ₁₈ alcohols such as methanol, ethanol, 1-propanol, C ₁ -C ₁₈ alkyl esters formed by the reaction of a polyol with isobutanol, butanol, isobutanol, 1-pentanol, 2-pentanol and 1-hexanol. Particularly suitable unsaturated polyacids are the C ₁ -C ₆ alkyl esters of maleic acid, maleic anhydride, or maleic acid. In certain embodiments, the unsaturated polycarboxylic acid / anhydride / ester comprises 3 to 25 weight percent, such as 5 to 20 weight percent polyester prepolymer.

The polyester prepolymer may further comprise one or more monomers that contribute to the overall properties of the polyester (including "soft"). For example, one or more monomers that contribute to the "soft fraction" can be used with the at least one polyol and at least one unsaturated polycarboxylic acid / anhydride / ester. As used herein, the term "soft fraction" and similar terms refers to a monomer or residue thereof, or a mixture thereof, which can impart flexibility to the prepolymer and aid in obtaining the desired Tg and / or viscosity of the branched polyester Quot; The soft fraction may be, for example, a residue of a polyacid. As used herein, the term " polyacid "and similar terms refers to a compound having two or more acid groups and includes esters and / or anhydrides of such acids. Such acids include, for example, linear acids which impart flexibility. Examples include, but are not limited to, saturated polyacids such as adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, decanoic acid, dodecanoic acid and their esters and anhydrides. Suitable monoacids include but are not limited to C ₁ -C ₁₈ aliphatic carboxylic acids such as acetic, propanoic, butanoic, hexanoic, oleic, linoleic, undecanoic, lauric, isonic, other fatty, Hydrogenated fatty acids, and / or any esters and / or anhydrides thereof.

In certain embodiments, one or more additional acids may also be used. For example, the additional acid is an aromatic or alicyclic acid, suitable examples of which include, but are not limited to, phthalic acid, isophthalic acid, 5- tert -butylisophthalic acid, tetrachlorophthalic acid, benzoic acid, But are not limited to, the following: hydrophthalic acid, naphthalene polycarboxylic acid, terephthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, dimethylterephthalate, cyclohexanedicarboxylic acid, chlorendanic anhydride, 1,3-cyclohexanedicarboxylic acid, , Tricyclodecane polycarboxylic acid, endomethylene tetrahydrophthalic acid, endoethylenehexahydrophthalic acid, cyclohexanetetracarboxylic acid, cyclobutanetetracarboxylic acid, and esters and anhydrides thereof and / or combinations thereof. It will be appreciated that some of the additional acids enumerated above may impart rigidity to the branched polyester to increase the Tg of the branched polyester. Thus, when one or more of the above acids are used, the acid used and the amount of each acid should be selected so that the branched polyester has a Tg of 25 DEG C or less when the prepolymer is reacted.

Other monomer components may also be used in the formation of the prepolymer to impart one or more additional properties to the branched polyester and / or the coating comprising it. For example, the phthalic anhydride may be included, for example, in an amount of from 2 to 20% by weight of the prepolymer, and the phthalic anhydride may impart greater resistance to the coating. In addition, copolymerization of the unsaturated prepolymer with PDMS silmer acrylate can also impart flexibility to the final coating and / or improve fingerprint resistance. Such cyanoacrylate monomers may be used in any suitable amount, for example, in an amount of from 0.1 to 10% by weight. Aliphatic diacids may be added to improve hydrophobicity and polyethers such as poly THF may be used to make the branched polyester more hydrophilic.

The unsaturated polyester prepolymer may be prepared by any method known in the art. In one embodiment, the soft fraction and the polyol fraction are pre-reacted to form a material, commonly referred to herein as a "polyol prepolymer ", which is then further reacted with the unsaturated polycarboxylic acid / anhydride / ester. In another embodiment, the polyol fraction and the unsaturated polycarboxylic acid / anhydride / ester together are reacted in the presence or absence of a soft fraction. The polyol is typically present in excess when compared to the soft fraction, if a soft fraction is included. For example, the ratio of the reactants on the soft fraction monomers to the reactants on the polyol fraction monomers can be 1: 2, 2: 3, or more. The higher the ratio, the larger the molecular weight of the reaction product. Since an excess of polyol is used, the reaction product has a terminal hydroxyl functional group. This functional group remains unreacted in the preparation of the branched polyester, making the polyester "crosslinkable" with another compound. Similarly, when a soft fraction is not used, the prepolymer has a terminal hydroxyl or acid functionality that can cross-link with another compound.

As described above, according to the present invention, the Tg of the cross-linkable branched polyester is 25 占 폚 or less. In certain embodiments, the Tg of the prepolymer that is reacted to form the branched polyester is also 25 占 폚 or less. In another embodiment, the Tg of the at least one prepolymer is greater than 25 DEG C, and the Tg of the at least one prepolymer is less than 25 DEG C such that the resulting branched polyester has a Tg of 25 DEG C or less.

After formation of the unsaturated polyester prepolymer, the prepolymer is then polymerized in the presence of a free radical initiator. That is, the unsaturated groups on the first polyester prepolymer are reacted with the unsaturated groups on the second polyester prepolymer. It will be appreciated that the reaction occurs through free radical polymerization. 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. 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 initiator to double bond may be from 0.001 to 1.0, such as from 0.01 to 0.9, or from 0.5 to 1.

If a larger amount of initiator is used, a larger branch will be achieved. Increased branching typically means more functional groups in the polyester. In certain embodiments, a smaller amount of initiator (e. G. 0.1) may be used to minimize the amount of branch in the polyester and leave some unsaturation. Such an embodiment will provide particularly desirable flexibility to the final coating.

The unsaturated groups from one acid / anhydride / ester residue in the prepolymer react with the unsaturation of the other prepolymer. 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 branched polyester depending on the starting material used. Typically, when an initiator is used with an unsaturated acid or an anhydride or ester thereof, a linear polymer is produced. Thus, it was surprising and unexpected to achieve the branched polyester 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. While 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 the polymerization of unsaturated groups of polycarboxylic acids and polyesters can be carried out using conventional branched polyesters such as those prepared using tri- or tetra- Will understand that it is quite unique.

In certain embodiments, the branched polyester of the present invention has a Mark-Howink variable or segmentation measured by a triple detector GPC of less than 0.58, such as 0.50 or less or 0.48 or less.

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. In certain embodiments, the initiator is added over 10 minutes until the molecular weight of the polyester is doubled or tripled. The free radical polymerization can be carried out under a variety of conditions to allow control of parameters such as molecular weight, functionality, branching amount of the branched polyester, so as to obtain a branched polyester which gives the desired feel and properties to the final coating have.

Whether the polyol prepolymer is formed first, whether the polyol prepolymer is formed first, or whether the soft fraction monomers (if used) and the polyol fraction monomers are reacted directly with the polycarboxylic acid / anhydride / ester, The resulting branched polyester will in fact be a mixture of polyesters having varying degrees of unsaturation, chain length, 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 or its anhydride or ester, the polyol fraction monomer, the soft fraction monomer (if used), the composition of the initiator, the solvent and 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, the higher the temperature, the more concentrated free radical initiator is produced, which again causes the relatively low molecular weight chain to polymerize more. 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 a surprising result, as one skilled in the art would not expect the polymerization of the present invention to occur. However, too much initiator can cause gelation. Thus, in certain embodiments, the polyesters of the present invention are not gelled.

Although any means can be used to carry out such polymerization, for ease of handling, free radical polymerization can be carried out using a solution of an unsaturated acid or an anhydride or ester thereof and a polyol prepolymer (or soft fraction monomer and polyol fraction monomer) . ≪ / RTI > 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, methoxypropyl acetate and xylenes. The production of polyesters in solvents is commonly referred to herein as a "solvent based system ", which means that greater than 50%, such as less than 100% of the solvent is an organic solvent and less than 50%, such as less than 20% , Less than 5%, or less than 2% is water.

Alternatively, the polyester may be prepared in an aqueous system. By "aqueous system" is meant that the solvent is water in an amount greater than 50%, such as less than 100%, and less than 50%, such as less than 20%, less than 10%, less than 5%, or less than 2% However, in certain embodiments, the polymerization is carried out without a solvent. That is, all steps for preparing the polyester from the preparation of the prepolymer can be carried out in the absence of a solvent.

In any solvent system, water system, or solvent-free system, the resulting polyester may be a liquid, such as a viscous liquid.

As described above, the branched polyester of the present invention is formed by free radical polymerization through a double bond of the first and second unsaturated polyester prepolymers. The first and second prepolymers may be the same or different. In certain embodiments, two or more different unsaturated polyester prepolymers may be reacted together. By context, "different" means that the amount of one or more components used in the unsaturated polyester prepolymer and / or the amount of one or more components used in the unsaturated polyester prepolymer may be different. For example, a polyester according to the present invention can be prepared using a polyol prepolymer composed of the same components, and in another embodiment can be prepared using two or more polyol prepolymers formed from different components . That is, a first polyol prepolymer containing a terminal hydroxyl group and a second polyol prepolymer containing a terminal hydroxyl group are reacted with an unsaturated acid / anhydride / ester, and the components used in the production of the first and second prepolymers May have different and / or may have one or more different components and / or may have one or more different components if the same components are used. In such embodiments, the resulting polyester will have random units derived from each type of prepolymer used. Accordingly, the present invention includes polyesters made by the same or different amounts of polyol fraction monomers and / or unsaturated acids / anhydrides / esters, and / or any of these, and also each prepolymer May have the same or different soft segmented monomers and / or unsaturated acid monomers, and / or the same or different amounts of any of these. Using different polyol prepolymers, soft fraction monomers, polyol fraction monomers, additional monomers, unsaturated acids / anhydrides / esters and / or amounts of either, it is possible to provide polyesters having different properties. In this way, a polyester having a Tg of 25 DEG C or lower, and other desirable properties that can be derived using the specific components used in the prepolymer, can be formed.

In certain suitable embodiments, the prepolymer used in accordance with the present invention comprises adipic acid (soft fraction) in an amount of, for example, 10 to 60 wt%, 2-methyl-1,3-propanediol By weight, for example from 0 to 50% by weight, of maleic anhydride, for example up to 25% by weight, for example from 5 to 20% by weight, based on the weight of the prepolymer, . Additional monomers such as isophthalic acid or terephthalic acid, phthalic acid, succinic acid, and neopentyl glycol may be used.

As described above, the branched polyester is formed using free radical polymerization, wherein the unsaturated groups of the polycarboxylic acid / anhydride / ester moiety in the prepolymer are polymerized. In the specific embodiments described above, this reaction is carried out such that substantially all of the unsaturated groups react in the formation of the branched polyester, and in another embodiment, the resulting polyester also contains some unsaturated groups. For example, the resulting polyester may contain sufficient unsaturation to make the polyester reactive with the other functional group through the unsaturation point.

Since the branched polyester according to the present invention is formed mainly through the free radical polymerization of the unsaturated groups in the prepolymer, the terminal hydroxyl groups in the branched polyester of the present invention will remain unreacted. These unreacted hydroxyl groups can then be cross-linked with other components. Thus, the present invention is distinguished from a technique in which a gelled polyester, i. E., An extremely networked polyester, is formed. The polyesters of the present invention are thermosetting and thus distinguishable from the technique of teaching thermoplastic polyesters.

In certain embodiments, it may be desirable to convert some or all of the unsaturated polyester prepolymer and / or the hydroxyl functionality on the branched polyester prior to polymerization to another functional group. For example, such hydroxyl groups can react with cyclic anhydrides to provide acid functionality. An acid ester may also be formed.

In certain other embodiments, the unsaturated polyester prepolymer may comprise other bonds besides ester linkages. For example, the polyester prepolymer may also comprise at least one urethane bond. Urethane bonds can be introduced by reacting an excess of the polyol prepolymer or the unsaturated polyester polymer with a polyisocyanate. The resulting unsaturated polyester prepolymer will still have terminal functional groups and unsaturation groups, but will have a urethane bond in addition to the ester linkage. Other chemistries may also be introduced. Thus, in certain embodiments, the unsaturated polyester prepolymer comprises one or more other bonds besides ester linkages.

In certain other embodiments, the use of unsaturated monomers other than the unsaturated polyacid / anhydride / ester of the prepolymer is excluded. For example, in certain embodiments, the use of vinyl monomers such as (meth) acrylate, styrene, vinyl halide, and the like can be ruled out. In such embodiments, the PDMS cymeacrylate can still be used if the double bond of the remainder of the acrylate is reacted upon formation of the prepolymer. Similarly, if the double bond of the remainder of the acrylate is reacted upon formation of the prepolymer, any other acrylate or methacrylate containing monomer or polymer may be used. That is, since the acrylate double bond is reacted, it can not be used to react with the unsaturated group of the second prepolymer during free radical polymerization. The branched polyester of the present invention is not a polyester / acrylic graft copolymer well known in the art and not formed by the reaction of unsaturated groups on the first and second polyester prepolymer.

In certain embodiments, the polyesters of the present invention specifically exclude polyesters made from prepolymers formed by reaction with aldehydes. Thus, in this embodiment, acyl succinic acid polyesters are specifically excluded. Similarly, in certain embodiments of the present invention, the use of aldehydes in solvents is specifically excluded.

The branched polyester of the present invention may have a relatively high molecular weight and functional group as compared with conventional linear polyester resins. Typically, the ratio of M _W of the branched polyester of the present invention to the weight average molecular weight ("M _W ") of the unsaturated polyester prepolymer is 1.2 to 100, such as 4 or 5 to 50, , Which can be higher.

In certain embodiments, the polyester prepolymer may have a Mw of from 1,000 to 50,000, such as from 5,000 to 10,000 or from 7,000 to 8,000. In addition, the final branched polyester may have a Mw of 2,000 to 100,000, for example 4,000 to 10,000. The prepolymer Mw can be related to the properties of the branched polyester as well as the properties of the coating comprising said polyester. For example, a branched polyester having a Mw in the low end range, such as less than 10,000, will have a higher cross-link density or hardness in the coating, since it will have more functional groups, while a segment with a Mw greater than 10,000 Topographic polyesters will have different tactile sensations and will provide coatings with lower crosslink density or hardness.

In certain embodiments, the equivalent weight of the polyester is 1000 or less. Equivalent is Mw divided by mean action. The equivalent contributes to the crosslinking density, which will affect the properties of a soft touch coating as described above. For example, higher equivalents can provide lower crosslink density.

In addition to the molecular weights described above, the branched polyester of the present invention may also have a relatively high degree of functionality. In some cases, the degree of functionality is higher than would be expected in a conventional polyester with such a molecular weight. The average functionality of the polyester may be 2.0 or more, such as 2.5 or more, 3.0 or more, or more. As used herein, "average functionality" refers to the average number of functional groups on the branched polyester. The functionality of the branched polyester is measured by the number of hydroxyl groups remaining unreacted in the branched polyester, not by unreacted unsaturation. In certain embodiments, the hydroxyl value of the branched polyester of the present invention may be between 10 and 500 mg KOH / gm, such as between 30 and 250 mg KOH / gm. In certain embodiments, the branched polyester of the present invention has both high M _w and high activity, such as greater than 15,000, such as from 20,000 to 40,000, or greater than 40,000 M _W , and greater than or equal to 100 mg KOH / gm will be.

Because the polyesters of the present invention comprise functional groups, they are suitable for use in coating compositions in which hydroxyl groups (and / or other functional groups) are crosslinked with other resins and / or crosslinkers typically used in coating compositions. The invention therefore also relates to a coating comprising a branched polyester according to the invention and a crosslinking agent therefor. Such cross-linking agents, or cross-linking resins or agents, may be any suitable cross-linking or crosslinking resins 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 a crosslinking agent with a hydroxyl group and / or other functional groups, not through a double bond of the polycarboxylic acid or its anhydride or ester residue to the extent that any unsaturated groups are present in the branched polyester ≪ / RTI >

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. In certain embodiments, the crosslinking agent is 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 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 a polycarbodiimide, such as those disclosed in U.S. Patent No. 8,389,113, Quot; 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.

In preparing the coatings of the present invention, the branched polyester 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. In certain embodiments, 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 another embodiment, the coating is aqueous or aqueous. This means that at least 50% of the solvent is water. Such embodiments have less than 50%, such as less than 20%, less than 10%, less than 5%, or less than 2% of the solvent.

In certain embodiments, the coating of the present invention also comprises 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 dibutyltin dilaurate, phosphoric acid, alkylarylsulfonic acid, dodecylbenzenesulfonic acid, dynonylnaphthalenesulfonic acid, and dynonylnaphthalenesulfonic acid.

It will be appreciated that the various factors must be balanced to provide the desired "feel" As discussed above, monomer selection and content can play an important role, and Mw, equivalence and branching are also such. The Tg of the branch may be reduced, which may increase the "soft feel" quality of the coating. In addition, selection of a crosslinking agent can also contribute to soft touch. For example, the amount of cross-linking agent and cross-linker used can be selected to provide the desired cross-linking density associated with tactile as described above. In certain embodiments, the 60 degree gloss of the coating is from 0.5 to 1.5.

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

As used herein, the term "colorant" means any component that imparts color and / or other opacity and / or other visual effects (e.g., gloss) 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 matting pigments, dyes and tints, such as those used in the paint industry and / or listed in the Dry Color Manufacturer Association (DCMA) as well as special effect compositions. 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, Anthanthrone, anthanthrone, anthanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, anthanthrone, anthraquinone, (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 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, for example, in U.S. Patent No. 7,605,194 (Curr. Column 3, line 56 to column 16, line 25) do.

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 embodiment, the special effect composition can 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 identified in U.S. Patent No. 6,894,086, which is 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 >

In certain non-limiting embodiments, the photosensitive composition and / or photochromic composition (which reversibly changes color upon exposure to one or more light sources) may be used in 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. In one non-limiting embodiment, 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 include a photochromic dye.

In a non-limiting embodiment, the photosensitive composition and / or photochromic composition may be associated with and / or at least partially conjugated (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, photosensitive compositions connected and / or at least partially bonded to the polymer and / or the polymerizable component in accordance with a non-limiting embodiment of the present invention and / The composition moves to a minimum out of the coating. Exemplary photosensitive compositions and / or photochromic compositions and methods of making them are identified in U.S. Patent No. 8,153,344, 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 can 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.

According to the present invention, any slip agent, such as those available from BYK Chemie or Dow Corning, may be used.

In certain embodiments, the polyesters of the present invention can be used as coating additives. For example, it has been found that the polyesters of the present invention can replace all or part of sagging control agents, such as cellulose esters, used in coating compositions comprising metallic flakes. It will be appreciated that the branched polyester of the present invention and the crosslinking agent therefor may form all or part of the film-forming resin of the coating. In certain embodiments, 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. In certain embodiments, 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 branched polyester have. In certain other embodiments, thermosetting film-forming polymers or resins with self-reactive functional groups are used, and in this way, the thermosetting coating is self-crosslinked.

The coatings of the present invention may comprise from 1 to 100 weight percent, such as from 10 to 90 weight percent, or from 20 to 80 weight percent, of the branched polyester of the present invention, based on the total weight of the coating. The coating compositions of the present invention may also comprise from 0 to 90 weight percent, such as from 5 to 60 weight percent, or from 10 to 40 weight percent, of the crosslinking agent for the branched polyester, based on the total solids weight of the coating . If desired, the additional component may comprise from 1 wt% to 70 wt% or more, based on the total solids weight of the coating.

The coating formulations according to the present invention may have a soft touch and / or a smooth feeling upon curing on the substrate. For example, the coating may have a softness of 1 to 20 N / mm ² , such as 2 to 10 N / mm ² as measured by Fisher micro-hardness test. The coating may further have a coefficient of friction of from 0.01 to 0.5, for example from 0.05 to 0.2, as measured by ASTM Method D1894. The "coefficient of friction" refers to the ratio of the force holding the contact between the object and the surface to the friction force resisting the movement of the object. The coating can have a wear resistance of 50 to 500 cycles, for example 250 to 500 cycles, as measured by ASTM Method F2357, at a thickness of 50 microns. The cured coating also has a surface roughness of 1 to 80 탆, such as 10 to 60 탆, 20 to 50 탆, or 35 to 45 탆, as measured by a Taylor Hobson Precision Duo Profilometer Lt; / RTI > The surface roughness can be changed through compounding, for example, through the use of an additive (an example of which is silica). Those skilled in the art will appreciate that achieving this level of hardness, coefficient of friction, wear resistance, and surface roughness in the same coating is a significant achievement. The result is a soft, durable coating when touched. The inventors believe that this combination of properties is achieved due to the branching of the polyester, but is not intended to be bound by any mechanism.

("BPA") and bisphenol A diglycidyl ether ("BADGE") and its derivatives or moieties such as bisphenol A ) May be substantially, essentially and / or completely free. Such prepolymers, branched polyesters and / or coatings are sometimes referred to as "BPA unintentionalities" because BPA (including derivatives or residues thereof) are not intentionally added and may be present in minor amounts due to inevitable contamination or impurities from the environment. Quot; The prepolymer, the branched polyester and / or the coating may contain substantially, essentially and / or completely free of bisphenol F and its derivatives or moieties such as bisphenol F and bisphenol F diglycidyl ether ("BFDGE & I can not. As used herein, "substantially free" means that the prepolymer, the branched polyester and / or the coating contains less than 1000 ppm, "essentially free" means less than 100 ppm, and " Quot; or "absent " means containing less than 20 ppb of any of the above compounds, derivatives or moieties thereof.

The coatings 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 housings and circuit boards (such as consumer electronics, A notebook, a smart phone, a tablet, a television, a game machine, a computer equipment, a computer accessory, an MP3 player, etc.), a glass and a transparent body, 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. In another embodiment, 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.

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.

In certain embodiments, the coating is a clear coat. The clearcoat will be understood as a substantially transparent or translucent coating. Thus, a clearcoat can have a certain degree of color or opacity, provided that it does not opacify the clearcoat or have any other significant effect on the ability to view the underlying substrate. The clearcoat of the present invention can be used, for example, with a colored base coat. The clearcoat may be formulated as is known in the art.

In certain other embodiments, the coating includes a colored base coat, or a pigmented monocoat, for use with a colorant, such as a clearcoat. Such coating layers are used, for example, in the automotive industry to impart a decorative and / or protective finish to the vehicle. Vehicle "is used in its broadest sense and includes all types of vehicles such as, but not limited to, automobiles, trucks, buses, vans, golf carts, motorcycles, bicycles, trains, and the like. It will be appreciated that the portion of the vehicle that is coated in accordance with the present invention may vary depending on why the coating is used. For example, the anti-chip primer may be applied to a part of the vehicle as described above. When used as a pigmented base coat or monocoat, the coating of the present invention is typically applied to a portion of a visible vehicle such as a roof, hood, door, trunk lid, etc., but may be applied to other areas, , Interior of the door, etc., which may also be applied to parts of the vehicle that are in contact with the driver and / or passengers, such as steering handles, dashboards, gear shifts, controls, door handles, The clearcoat will typically be applied to the exterior of the vehicle.

In another embodiment, the present invention relates to a substrate that is at least partially coated with a coating of the present invention, wherein said substrate comprises a consumer electronic component. "Consumer electronic components" include, for example, notebooks, smart phones, tablets, televisions, game equipment, computer equipment, computer accessories, any parts or housings of MP3 players, and the like. The coating is typically applied to at least the exterior of the housing of such equipment, but it may also be applied wholly or partially to the interior of such a housing. The coatings of the present invention are particularly suitable for use in consumer electronics applications, which can provide the desired tactile and durability.

Coil coatings that are widely applied in many industries are also substrates that can be coated according to the present invention. The coatings of the present invention are particularly 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 certain embodiments, the package is 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. A metal "bottle" which resembles the shape of a glass bottle is also a "metal can" according to the invention. The term "metal can" specifically includes food cans, and in particular includes a "can end" that is typically stamped from the can end stock and used in conjunction 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. In some embodiments, the coating is applied to the coil or sheet by roll coating. The coating is then cured by radiation, and the can end is stamped and made into a finished product (i.e., can end). In another embodiment, the coating is applied to the bottom of the can as a rim coat. This application can be carried out by roll coating. Rim coats function to reduce friction for subsequent manufacturing of can and / or improved handling during processing. In certain embodiments, the coating is applied to the cap and / or lid. This application is particularly advantageous when, for example, the protective varnish applied before and / or after the formation of the cap / lid and / or the coloring that is post-applied to the cap (especially with a seam at the bottom of the cap) Enamel < / 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 electrical coating 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, the term "polyester", "branched polyester", "unsaturated acid / anhydride / ester", "polyol prepolymer", "soft fraction", "soft monomer", "polyol fraction" Quot ;, " polyol soft monomer ", "prepolymer "," crosslinking agent ", and the like, one or more of each and any other component may be used. The term "polymer" herein refers to both oligomers and homopolymers and copolymers, and the term "poly" refers to two or more. For example, "comprising" and similar terms means, for example, "including but not limited to. Where a range is provided, any end of such range and / or numerical values within this range may be combined within the scope of the present invention.

[Example]

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

The HM2000S Fisher microhardness instrument was used to measure the hardness according to the instructions described in the FisherScope HM2000 manual. Three measurements were made and the average hardness values were recorded and reported.

Friction coefficient testing was performed using a Dynisco 1055 coefficient of friction tester, a Chatillion DGGS force gauge and a green felt sled. Five tests were performed on each sample. Five measurements were made and the average hardness values were recorded and reported.

The surface hardness was measured according to the instructions provided by the manufacturer by means of a taylor Hobson Precision Surtronic Duo Profilometer.

The abrasion resistance was measured according to ASTM method F2357.

Example 1

The branched polyester according to the present invention was prepared as follows. Methyl methane-1,3-propanediol, 177 g of adipic acid, 287 g of isophthalic acid, 179 g of phthalic anhydride, 223 g of maleic anhydride and 1.5 g of butyl stannate were mixed with a stirrer, Was added to a 3-liter four-neck round bottom flask equipped with a steam-cooled column with a distillation head and a thermometer. The contents were slowly heated under a stream of nitrogen gas. The contents of the flask were heated to about 95 캜, at which time the contents were melted and stirring was continued. The batch was heated to 155 < 0 > C, at which time the water began to distil. Heating was continued to the batch temperature of 220 캜. 160 g of water was removed from the reaction. The final acid value of the resin was determined to be 3.8. The contents of the batch were cooled to 150 캜 and 316 g of Aromatic 100 was added. The material in the flask was then cooled and taken out. The solid content was 81% by weight. The OH number of the resin was 50.2 at 81% solids. The weight average molecular weight of the product was 5700 for the polystyrene control material. The Tg of the prepolymer was -11 占 폚.

988 g of the above resin was placed in a 3 l 4-neck round bottom flask equipped with a stirrer, a water-cooled condenser, an addition funnel and a thermometer. The contents of the flask were heated to 120 占 폚. 2 g of tertiary butyl peroctoate and 153 g of butyl acetate were mixed and placed in the addition funnel. The contents of the addition funnel was added to the flask over 10 minutes. The temperature of the reaction was maintained at 120 캜 for 1 hour. Then, it was cooled and the contents were taken out. The final resin had a solids content of 70% by weight. The OH number of the resin was 41 at 70% solids. The resin had a weight average molecular weight of 7900 as measured on a polystyrene standard material. The Tg of the polyester was -18 ° C as measured by Dynamic Scanning Calorimetry.

Example 2

The branched polyester according to the present invention was prepared as follows. 650 g of 2-methyl-1,3-propanediol, 282 g of adipic acid, 166 g of isophthalic acid, 179 g of phthalic anhydride, 223 g of maleic anhydride and 1.5 g of butyltin acid, Was added to a 3-liter four-neck round bottom flask equipped with a steam-cooled column with a distillation head and a thermometer. The contents were slowly heated under a stream of nitrogen gas. The contents of the flask were heated to about 95 캜, at which time the contents were melted and stirring was continued. The batch was heated to 155 < 0 > C, at which time the water began to distil. Heating was continued to the batch temperature of 220 캜. 162 g of water was removed from the reaction. The final acid value of the resin was measured to be 6.1. The contents of the batch were cooled to 150 캜 and 313 g of Aromatic 100 was added. The material in the flask was then cooled and taken out. The solid content was 81% by weight. The OH number of the resin was 43 in 81% solids. The weight average molecular weight of the product was 6600 for the polystyrene control material. The Tg of the prepolymer was -18 占 폚.

988 g of the above resin was placed in a 3 l 4-neck round bottom flask equipped with a stirrer, a water-cooled condenser, an addition funnel and a thermometer. The contents of the flask were heated to 120 占 폚. 2 g of tertiary butyl peroctoate and 153 g of butyl acetate were mixed and placed in the addition funnel. The contents of the addition funnel was added to the flask over 10 minutes. The temperature of the reaction was maintained at 120 캜 for 1 hour. Then, it was cooled and the contents were taken out. The final resin had a solids content of 71% by weight. The OH number of the resin was 32 at 71% solids. The resin had a weight average molecular weight of 9300 as measured on a polystyrene standard material. The Tg of the polyester was -22 ° C as measured by a dynamic scanning calorimeter.

Example 3

The branched polyester according to the present invention was prepared as follows. 650 g of 2-methyl-l, 3-propanediol, 711 g of adipic acid, 152 g of maleic anhydride and 1.5 g of butyltin acid were mixed with a stirrer, a steam-cooled column with a distillation head and a thermometer Was added to a 3 l 4-necked round bottomed flask equipped with a stirrer. The contents were slowly heated under a stream of nitrogen gas. The contents of the flask were heated to about 112 DEG C, at which time the contents had melted and stirring was continued. The batch was heated to 173 < 0 > C, at which time the water began to distil. Heating was continued to the batch temperature of 220 캜. A total of 196 g of water was removed from this reaction. The final acid value of the resin was measured to be 2.6. The contents of the batch were cooled to 150 캜 and 307 g of Aromatic 100 was added. The material in the flask was then cooled and taken out. The solid content was 81% by weight. The OH number of the resin was 52 at 81% solids. The weight average molecular weight of the product was 5700 for the polystyrene control material. The Tg of the prepolymer was -47 캜.

982 g of the above resin were placed in a 3 l 4-neck round bottom flask equipped with a stirrer, a water-cooled condenser, an addition funnel and a thermometer. The contents of the flask were heated to 120 占 폚. 2 g of tertiary butyl peroctoate and 158 g of butyl acetate were mixed and placed in the addition funnel. The contents of the addition funnel was added to the flask over 10 minutes. The temperature of the reaction was maintained at 120 캜 for 1 hour. Then, it was cooled and the contents were taken out. The final resin had a solids content of 71% by weight. The OH number of the resin was 50 at 71% solids. As measured for polystyrene standards, the resin had a weight average molecular weight of 6700 and a Tg of -48 ° C.

Example 4

The coatings according to the invention were prepared as follows. 59 g of polyester resin from Example 1, 17 g of ethyl acetate, 5 g of diacetone alcohol, 5 g of PM acetate and 0.4 g of DISPERBYK-103 (commercially available from BYK Wettable dispersing additive) was added to a half pint metal can equipped with an overhead mechanical stirrer. The mixture was gently stirred for 5 to 10 minutes and then 6.5 g of ACEMATT TS-100 silica (thermal silica commercially available from Evonik Industries) was added. The mixture was mixed at high speed for 20 to 30 minutes. A total of 1 g of SILOK-3200 (a coating feeling agent commercially available from Guangzhou Silok Polymers Co., Ltd.), 0.6 g of BLS 292 (available from Mayzo, And 0.1 g of dibutyltin dilaurate were finally added to the metal can and mixed for an additional 5 minutes. The resulting mixture was mixed with 21 g of XPH80002 curing agent (HDI trimmer commercially available from Pfizer Industries, Inc.) and mixed with a GXS73037 reducer (available from Pfizer Industries, Inc.) Solvent mixture). The resulting soft touch paint was sprayed onto a polycarbonate substrate and cured at 60 占 폚 for 30 minutes to produce a dry film of approximately 50 占 퐉. The final soft touch coating on the polycarbonate substrate exhibited a hardness of 4.2 N / mm ² , a coefficient of friction of 0.06, a surface roughness of 42, and a wear resistance of 480 cycles. The coatings were tested for resistance to conventional housewares and showed resistance to mustard, ketchup, lipstick, sunscreen, petrolatum, and hand lotion.

Example 5

The coatings according to the invention were prepared as follows. 59 g of the polyester resin from Example 2, 17 g of ethyl acetate, 5 g of diacetone alcohol, 5 g of PM acetate and 0.4 g of DISPERBYK-103 were mixed with an overhead mechanical stirrer Pint metal can provided. The mixture was gently stirred for 5-10 minutes and then 6.5 g of ACEMATT TS-100 silica was added. The mixture was mixed at high speed for 20 to 30 minutes. A total of 1 g of SILOK-3200, 0.6 g of BLS 292 and 0.1 g of dibutyltin dilaurate were finally added to the metal can and mixed for an additional 5 minutes. The resulting mixture was mixed with 16 g of XPH80002 curing agent and diluted to a suitable spray viscosity with GXS73037 diluent. The resulting soft-touch paint was sprayed onto a polycarbonate substrate and cured at 60 占 폚 for 30 minutes to produce a dry film of approximately 55 占 퐉. The final soft touch coating on the polycarbonate substrate showed a hardness of 3.3 N / mm ² , a coefficient of friction of 0.07, a surface roughness of 44, and a wear resistance of 300 cycles. The coatings were tested for resistance to conventional housewares and exhibited resistance to ketchup, lipstick, sunscreen, vaseline, and hand lotion, with some contamination in the case of mustard.

Example 6

The coatings according to the invention were prepared as follows. 59 g of the polyester resin from Example 3, 17 g of ethyl acetate, 5 g of diacetone alcohol, 5 g of PM acetate and 0.4 g of DISPERBYK-103 were mixed with an overhead mechanical stirrer Pint metal can provided. The mixture was gently stirred for 5-10 minutes and then 6.5 g of ACEMATT TS-100 silica was added. The mixture was mixed at high speed for 20 to 30 minutes. A total of 1 g of SILOK-3200, 0.6 g of BLS 292 and 0.1 g of dibutyltin dilaurate were finally added to the metal can and mixed for an additional 5 minutes. The resulting mixture was mixed with 26 g of XPH80002 curing agent and diluted to a suitable spray viscosity with GXS73037 diluent. The resulting soft-touch paint was sprayed onto a polycarbonate substrate and cured at 60 占 폚 for 30 minutes to produce a dry film of approximately 55 占 퐉. The final soft touch coating on the polycarbonate substrate showed a hardness of 3.0 N / mm ² , a coefficient of friction of 0.07, a surface roughness of 38, and 350 cycles after the initial cure and 600 cycles after 5 days . The above coatings were tested for resistance to conventional housewares and showed resistance to ketchup, sunscreen, vaseline, and hand lotion, and a slight contamination in the case of mustard and lipstick.

Claims (21)

1. A crosslinkable, branched polyester polymer 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 fraction, and
(b) an unsaturated polycarboxylic acid and / or an anhydride and / or ester thereof
Lt; / RTI >
Wherein said branched polyester polymer has a Tg of 25 DEG C or less. The method according to claim 1,
Wherein the prepolymer further comprises a soft segment. 3. The method of claim 2,
Wherein the soft fraction comprises adipic acid. The method according to claim 1,
Wherein the prepolymer further comprises isophthalic acid. The method according to claim 1,
Wherein the polyol fraction comprises 2-methyl-1,3-propanediol. The method according to claim 1,
Wherein the unsaturated polycarboxylic acid / anhydride / ester comprises maleic acid / anhydride / ester and / or itaconic acid / anhydride / ester. 3. The method of claim 2,
Wherein the at least one prepolymer comprises adipic acid, 2-methyl-1,3-propanediol, and maleic acid / anhydride / ester. The method according to claim 1,
A polyester of the prepolymer is from 5,000 to 10,000 M _W. The method according to claim 1,
A polyester of said polyester is from 4,000 to 10,000 M _W. The method according to claim 1,
Wherein the polyester has a Mark Howling variable of 0.48 or less. A coating comprising the polyester of claim 1 and a crosslinking agent therefor. 12. The method of claim 11,
A hardness of 2 to 10 N / mm ² as measured by Fischer microhardness test,
A coefficient of friction of 0.05 to 0.2 as measured by ASTM Method D 1894,
Abrasion resistance of 250 to 500 cycles as measured by ASTM method F2357, and / or
When measured with a Taylor Hobson Precision Duo Profilometer, surface roughness of 20 to 50 占 퐉
≪ / RTI > 12. The method of claim 11,
Wherein the at least one prepolymer comprises adipic acid, 2-methyl-1,3-propanediol, and maleic acid / anhydride / ester. 12. The method of claim 11,
Wherein the coating further comprises a colorant. 12. The method of claim 11,
Wherein the crosslinking agent comprises an isocyanate. 11. A substrate at least partially coated with the coating of claim 11. 17. The method of claim 16,
Wherein the substrate comprises a consumer electronic component. 17. The method of claim 16,
Wherein the substrate comprises PC / ABS. 17. The method of claim 16,
Wherein the substrate comprises a metal can. The method according to claim 1,
Wherein the polyester does not comprise (meth) acrylates or residues thereof. The method according to claim 1,
Wherein the unsaturated group of said prepolymer is derived only from said component (b).