阅读说明：本技术 用于薄涂层的聚合物组合物 (Polymer composition for thin coatings ) 是由 丁红 唐伟林 韩德辉 M·尼克纳哈德 于 2020-06-05 设计创作，主要内容包括：本申请涉及适用于双组分组合物的树脂或聚合物体系,以及被构造成用于仅具有薄涂层重量的耐用涂层的树脂或聚合物体系。本发明的树脂和聚合物体系提供高性能的极薄、光泽度低的涂层,所述涂层具有优异的粘附性、耐磨损、耐刮擦性和耐化学品性。所述树脂包含聚酯组分和聚脲组分,所述聚酯组分含有具有约50至约300的羟值的一种或多种聚酯多元醇,所述聚脲组分含有具有约20至约100的羟值的一种或多种聚酯多元醇接枝的聚脲聚合物。这些树脂或聚合物体系以及包含此类树脂或聚合物体系的双组分溶剂型涂料组合物令人惊奇地能够在约2密耳或更小,在一些情况下约1.2密耳或更小,并且在其他情况下甚至约1密耳或更小的干膜厚度下,同时实现强粘附性、优异的线性磨损和高耐化学品性。(The present application relates to resin or polymer systems suitable for two-component compositions, as well as resin or polymer systems configured for durable coatings having only a thin coating weight. The resin and polymer systems of the present invention provide high performance, extremely thin, low gloss coatings with excellent adhesion, abrasion, scratch and chemical resistance. The resin comprises a polyester component containing one or more polyester polyols having a hydroxyl number of from about 50 to about 300 and a polyurea component containing one or more polyester polyol grafted polyurea polymers having a hydroxyl number of from about 20 to about 100. These resin or polymer systems, and two-component solvent-borne coating compositions comprising such resins or polymer systems, are surprisingly capable of achieving both strong adhesion, excellent linear abrasion, and high chemical resistance at dry film thicknesses of about 2 mils or less, in some cases about 1.2 mils or less, and in other cases even about 1 mil or less.)

1. A durable polymer composition for thin coatings comprising a polyester component containing one or more polyester polyols having hydroxyl values of from about 50 to about 300 and a polyurea component containing a polyester-polyol grafted polyurea having a hydroxyl value of from about 20 to about 100.

2. The durable polymer composition for thin coatings according to claim 1, wherein the one or more polyester polyols comprise a blend of polyester polyol polymers each having a hydroxyl number of from about 50 to about 300.

3. The durable polymer composition for thin coatings according to any of the preceding claims, wherein one of the polyester polyols is the reaction product of a linear or ester diol, a cyclic diol, a polycaprolactone polyol with a cyclic dicarboxylic acid or anhydride.

4. The durable polymer composition for thin coatings according to claim 3, wherein the reaction product has a hydroxyl number of about 80 to about 150.

5. The durable polymer composition for thin coatings according to any of the preceding claims, wherein one of the polyester polyols is one or more of a linear or branched aliphatic or aromatic polyester polyol having a hydroxyl value of 150 to about 300.

6. The durable polymer composition for thin coatings according to any of the preceding claims, wherein the polyester component comprises (i) the reaction product of a linear diol or ester diol, a cyclic diol, a polycaprolactone polyol and a cyclic dicarboxylic acid or anhydride, said reaction product having a hydroxyl number of from about 80 to about 150; (ii) a branched aliphatic polyester polyol having a hydroxyl number of about 120 to about 200; and (iii) an aromatic polyester polyol having a hydroxyl number of 200 to about 300.

7. The durable polymer composition for thin coatings according to claim 6, wherein the composition comprises from about 5 to about 30 weight percent of polyester polymer (i), from about 5 to about 30 weight percent of polyester polyol (ii), and from about 40 to about 80 weight percent of polyester polyol (iii).

8. The durable polymer composition for thin coatings according to claim 6, wherein the composition comprises about 2 times to about 4 times the amount of polyester polymer (iii) compared to the sum of the amounts of polyester polymer (i) and polyester polymer (ii).

9. The durable polymer composition for thin coatings according to any of the preceding claims, wherein the polyester polyol grafted polyurea is the reaction product of dimethylolpropionic acid initiated polycaprolactone with a polymer containing at least one carbodiimide moiety, the polyester polyol grafted polyurea having a hydroxyl number of from about 50 to about 70.

10. The durable polymer composition for thin coatings of claim 9 wherein the polymer containing at least one carbodiimide moiety comprises an average of 4 to 10 carbodiimide moieties.

11. The durable polymer composition for thin coatings according to any of the preceding claims, wherein the durable polymer composition comprises from about 1 wt% to about 30 wt% of the polyester polyol grafted polyurea.

12. The durable polymer composition for thin coatings according to any of the preceding claims, wherein the weight ratio of the polyester component to the polyurea component is from about 70:30 to about 95: 5.

13. A solvent-borne coating composition suitable for providing a durable, low gloss coating having a low coating weight, said solvent-borne coating composition comprising:

the polymer system according to any one of claims 1 to 12;

an isocyanate functional component suitable for crosslinking the polymer system; and

an inert pigment sufficient to form a 60 ° gloss of 1.5 to 1.8.

14. The solvent-borne coating composition according to claim 13, wherein the cured coating has a dry film thickness of about 2 mils or less.

15. The solvent-borne coating composition according to claim 13, further comprising micronized powder particles.

16. The solvent-borne coating composition according to claim 13, which, when dried to a film thickness of about 1 mil or less, exhibits an 85 ° gloss change of about 1.5 units or less after 10 abrasion cycles, a chemical resistance rating of 2 or less after exposure to sunscreen and insect repellant, and 0% tape removal after exposure to 1240KJ xenon gas and cross-scratch abrasion.

Technical Field

The present application relates to resin or polymer systems suitable for two-component compositions, and in particular, to resin or polymer systems configured for durable thin coatings.

Background

Polymeric coatings often require multiple performance attributes to be simultaneously acceptable. In many cases, while performance can be obtained by increasing the thickness or coating weight, many applications require very thin coating weights, which can lead to challenges when attempting to simultaneously evaluate through many different properties. Formulating a composition in these cases can be challenging, as coating compositions that meet one performance attribute can unfortunately compromise other attributes. Often, formulators are involved in the dilemma that either all performance characteristics of the composition are suboptimal or one attribute is maximized while the other attributes are compromised. In many cases, both of these cases are undesirable.

Disclosure of Invention

In one aspect, a durable polymer composition for thin coatings with high performance is described herein. In one approach, a durable polymer composition includes a polyester component containing one or more polyester polyols having hydroxyl values of from about 50 to about 300 and a polyurea component containing a polyester-polyol grafted polyurea having a hydroxyl value of from about 20 to about 100.

In other aspects, the polymer compositions of the preceding paragraphs can be combined with optional features in any combination. These optional features include one or more of the following: wherein the one or more polyester polyols comprise a blend of polyester polyol polymers each having a hydroxyl number of from about 50 to about 300; and/or wherein one of the polyester polyols is the reaction product of a linear or ester diol, a cyclic diol, a polycaprolactone polyol and a cyclic dicarboxylic acid or anhydride; and/or wherein the reaction product has a hydroxyl number of about 80 to about 150; and/or wherein one of the polyester polyols is one or more of a linear or branched aliphatic or aromatic polyester polyol having a hydroxyl number of 150 to about 300; and/or wherein the polyester component comprises (i) the reaction product of a linear diol or ester diol, a cyclic diol, a polycaprolactone polyol and a cyclic dicarboxylic acid or anhydride, the reaction product having a hydroxyl number of from about 80 to about 150; (ii) a branched aliphatic polyester polyol having a hydroxyl number of about 120 to about 200; and (iii) an aromatic polyester polyol having a hydroxyl number of 200 to about 300; and/or wherein the composition comprises from about 5 to about 30 weight percent of the polyester polymer (i), from about 5 to about 30 weight percent of the polyester polyol (ii), and from about 40 to about 80 weight percent of the polyester polyol (iii); and/or wherein the composition comprises from about 2 times to about 4 times the amount of polyester polymer (iii) as compared to the sum of the amounts of polyester polymer (i) and polyester polymer (ii); and/or wherein the polyester polyol grafted polyurea is the reaction product of dimethylolpropionic acid initiated polycaprolactone with a polymer containing at least one carbodiimide moiety, said polyester polyol grafted polyurea having a hydroxyl number of from about 40 to about 80; and/or wherein the polymer containing at least one carbodiimide moiety comprises an average of from 4 to 10 carbodiimide moieties; and/or wherein the durable polymer composition comprises from about 1 wt% to about 30 wt% of a polyester polyol grafted polyurea; and/or wherein the weight ratio of the polyester component to the polyurea component is from about 70:30 to about 95: 5.

In another aspect, described herein is a solvent borne coating composition suitable for providing a durable, low gloss coating having a low coating weight. In some methods, the solvent-borne coating composition may comprise a polymer system as described by any of the features in the previous two paragraphs. The composition may also include an isocyanate functional component suitable for crosslinking the polymer system and an inert pigment sufficient to provide a gloss of 5 or less 85 ° or a gloss of 2 or less 60 °. In other methods, the solvent-borne coating composition can also have a dry film thickness of about 2 mils or less, or when dried to a film thickness of about 1 mil or less, the solvent-borne coating composition can exhibit an 85 ° gloss change of about 1.5 units or less after 10 abrasion cycles, can exhibit a chemical resistance rating of 2 or less after exposure to, for example, sun screens and insect repellents, and can exhibit a chemical resistance rating of 1240kJ/m after exposure to, for example, sun screens and insect repellents²Xenon gas and a cross-hatch mark may exhibit 0% tape removal after adhesion.

Detailed Description

Described herein are resin or polymer systems suitable for two-component, solvent-borne coating compositions that, in some applications, provide high performance in terms of adhesion, abrasion resistance, and chemical resistance in very thin coatings of low gloss. These polymer systems comprise a polyester component comprising one or more polyester polyols having hydroxyl numbers of from about 50 to about 300 and a polyurea component comprising one or more polyester polyol grafted polyurea polymers having hydroxyl numbers of from about 20 to about 100. These resins or polymer systems, and two-component solvent-borne coating compositions comprising such resins or polymer systems, are surprisingly capable of simultaneously achieving strong adhesion, low linear abrasion, and high chemical resistance at dry film thicknesses of about 2 mils or less, in some cases about 1.2 mils or less, and in other cases even about 1 mil or less.

Polyester component：

In one aspect, the resin or polymer systems herein comprise one or more polyester polyols in the polyester component, and in some methods, a blend of two or more polyester polyol polymers in the polyester component. In some methods, for example, the polymer system comprises one or more hydroxyl-terminated branched aliphatic and/or aromatic polyester polyols. These linear or branched polyester polyols are obtainable by condensation of one or more polycarboxylic acids or their corresponding anhydrides or lower alkyl (C1-C3) esters with one or more polyols, wherein at least one of the reactant species has an OH functionality of 2 or greater, and in some processes 3 or greater.

In one method, the polycarboxylic acid may comprise phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydroterephthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, chlorendic acid, trimellitic acid, hexahydrotrimellitic acid, pyromellitic acid, 1,3, and 1, 4-cyclohexanedicarboxylic acid (CHDA), cyclohexanetetracarboxylic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, endomethylenehexahydrophthalic acid, methyl-endomethylenetetrahydrophthalic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, suberic acid, pimelic acid, dimer acid (dimer of tall oil fatty acids), tetrachlorophthalic acid, naphthalenedicarboxylic acid, 4' -diphenylmethanedicarboxylic acid, terephthalic, 4,4' -dicarboxybiphenyl and the like, as well as anhydrides and lower alkyl and dialkyl esters thereof, and blends thereof.

In another approach, the polyol or polyol useful in the polyester polyols herein can be a diol or triol and blends thereof, such as ethylene glycol, Propylene Glycol (PG), 1, 4-butanediol, 1, 3-butanediol, 2, 3-butanediol, 1, 2-butanediol, 1, 5-pentanediol, 1, 4-pentanediol, 2, 3-dimethyltrimethylene glycol, 3-methylpentane-1, 5-diol, 3-methyl-4, 5-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, 1, 6-hexanediol, 1, 5-hexanediol, 1, 4-hexanediol, 2, 5-hexanediol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, diethylene glycol, dipropylene glycol, triethylene glycol, neopentyl glycol (NPG), neopentyl glycol hydroxypivalate (HPHP), glycerol, Trimethylolpropane (TMP), trimethylolethane, diglycerol, pentaerythritol, dipentaerythritol, sorbitol bis- (hydroxymethyl) -tricyclodecane (TCD-diol), and the like, as well as blends thereof. Suitable polyols may also include polycaprolactone polyols, such as polycaprolactone triols and tetraols, and when used in a monomer blend, the caprolactone content of an exemplary monomer blend may be from about 5 wt% to about 65 wt%, from about 10 wt% to about 60 wt%, from about 10 wt% to about 50 wt%, from about 15 wt% to about 20 wt%, or from about 45 wt% to about 55 wt%.

In one exemplary method, one of the polyester polyols can be a branched polyester polyol comprising the reaction product of a monomer blend having (a) the linear difunctional diol or ester diol described above; (b) the cyclic diol described above; (c) polycaprolactone as described above; and (d) a cyclic dicarboxylic acid or anhydride as described above. The reaction product may have a hydroxyl number of about 80 to about 200, in other processes about 85 to about 140, and in other processes about 80 to about 110. In other exemplary methods, one or more of the polyester polyols can be a linear or branched aliphatic or aromatic polyester polyol having a hydroxyl number of from 150 to about 300, in some cases from 120 to about 200, and/or in other cases from about 200 to about 300. In particular, the polyester polyol may be a branched aromatic polyester polyol having a hydroxyl number of about 200 to about 300 and/or a branched saturated aliphatic polyester polyol having a hydroxyl number of about 100 to about 200. In some processes, a suitable polyester polyol can be a Stepanpol polyester available from Stepan Company.

The polyester polyols may be prepared by conventional techniques. In one method, the acid value can be less than about 5, for example, by charging the reaction chamber with a suitable monomer under an inert atmosphere and stirring while gradually increasing the temperature (e.g., from ambient to about 200 ℃ to about 225 ℃), while removing water, until a useful acid value is reached. Esterification of the monomer blend may be carried out by a condensation reaction in which water condensation is removed. An amount of catalyst suitable for the esterification reaction may be used. Exemplary catalysts may include conventional tin catalysts used in polyester synthesis, such as stannous octoate, stannous oleate, dibutyltin diacetate, butylstannoic acid, dibutyltin dilaurate, and the like, and combinations thereof. The viscosity of the resulting polyester polymer resin may be adjusted with an organic solvent such as, but not limited to, methyl-n-amyl ketone, as desired.

In certain instances, each polyester polyol in the blend can have a weight average molecular weight of from about 500 to about 10,000, in other processes from about 500 to about 5,000, and in other processes from about 500 to about 3,000. In other cases, each polyester polyol can also have a low glass transition temperature (Tg) of about-40 ℃ to about 30 ℃, about-40 ℃ to about 20 ℃, about-20 ℃ to about 15 ℃, or even about 0 ℃ to about 10 ℃.

In other methods, the polyester polyol of the polyester component can be one or more of a linear or branched aliphatic or aromatic polyester polyol having a hydroxyl number of from 150 to about 300, such as a branched aliphatic polyester polyol having a hydroxyl number of from about 120 to about 200 and/or an aromatic polyester polyol having a hydroxyl number of from 200 to about 300.

Polyurea component

In another aspect, the resin or polymer system herein further comprises a polyurea component, which may be one or more polyester-polyol grafted polyurea polymers having a hydroxyl number of from about 20 to about 120, and in other methods from about 40 to about 80, and in other methods from about 60 to about 80. These polyurea polymers may also have a hydroxyl equivalent weight of from about 600 to about 1,500, in other processes from about 600 to about 700, in other processes from about 800 to about 1,000, and in other processes from about 1,000 to about 1,500. The polyester polyol grafted polyurea can be the reaction product of a compound containing at least one carbodiimide moiety and an acid functional polymer such as a polyester, fatty acid, polyether, and the like. In some processes, the acid functional polyester may be obtained by reacting a dialkanol carboxylic acid with a cyclic ester such as caprolactone. Without being limited by theory, it is believed that the resulting polyester-polyol grafted polyurea polymer may be a comb polymer having a polyurea backbone with grafted polyester polyols, fatty acids, or polyether side chains.

In one approach, the polyurea backbone has the general structure of formula I, wherein the repeating urea moieties have R₁Grafted side chain, the R₁The grafted side chains comprise the residue of a polyester polyol, a fatty acid, a polyether, or a blend thereof:

wherein R is₀An alkyl group of C1 to Cx;

wherein R is an alkyl group, and R₁Is the residue derived from polyester polyol, fatty acid or polyether grafted side chains derived from an associated acid functional resin or polymer. In some methods, the main chain of the polyurea polymer is formed from a polymer containing at least one reactive carbodiimide group, and preferably one or more reactive carbodiimide groups. In one embodiment, useful carbodiimides comprise a plurality of repeating carbodiimide groups and may comprise about 4 or more groups, such that in formula I, the integer x may be 4 or greater, such as from 4 to 10.

The carbodiimide reacts with the carboxylic acid to form an acyl-urea group. To form the polyurea polymers herein, the carbodiimide-containing compound can be reacted with any polymer or resin having carboxylic acid functionality (e.g., acid-functional polyesters, fatty acids, and acid-functional polyethers as described herein). For example, the side chain R of the above formula I₁Can include reacting a mono-or dialkanol carboxylic acid with a cyclic ester to form a polyester polyol residue or R having the structure of formula II₁Partially obtained polyester residue:

wherein each R₂Independently a C1 to C8 group; each R₃Independently hydrogen, an alkyl group or an ester group; r₄Is a C1 to C4 alkyl group, and in some methods is a methylA radical group; and n can be any integer, such as an integer from about 1 to about 20. In other methods, the side chain R₁Polyethers may also be included, such as those having the structure of formula III and/or formula IV below:

wherein R is₅May be an alkyl group; r₆May be hydrogen or a C1 to C4 alkyl group; and p can be an integer, such as an integer from 5 to 60. In other methods, the side chain R₁May be a fatty acid. Side chain R₁Combinations of the above moieties are also possible.

Methods of making such polyester polymers or resins include reacting a polyol component with an acid and/or anhydride component, optionally together with a catalyst, and typically removing by-product water in order to drive the reaction to completion. Generally, the polyol component may have an average functionality of at least about 2. The polyol component may comprise monofunctional, difunctional, trifunctional, and higher functional alcohols. In one embodiment, diols may be used. In another embodiment, higher functionality alcohols may be used when some branching of the polyester is desired. Illustrative examples of such alcohols include, but are not limited to, alkylene glycols and polyalkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol and neopentyl glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, 2, 4-trimethyl-1, 3-pentanediol, hydrogenated bisphenol a, and hydroxyalkylated bisphenols, polyether polyols, polycaprolactone polyols, and saturated and unsaturated polyols. Representative polyol diluents include glycols such as ethylene glycol, dipropylene glycol, 2, 4-trimethyl-1, 3-pentanediol, neopentyl glycol, 1, 2-propanediol, 1, 4-butanediol, 1, 3-butanediol, 2, 3-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-dimethyl-1, 3-propanediol, 1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-bis (2-hydroxyethoxy) cyclohexane, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, decanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, norbornanediol, 1, 4-benzenedimethanol, xylene glycol, 1, 4-xylene glycol, 1, 4-benzenediethanol, 2, 4-dimethyl-2-ethylhexane-1, 3-diol, 2-butene-1, 4-diol, and polyols such as trimethylolethane, trimethylolpropane, trimethylolhexane, trimethylolpropane, 1,2, 4-butanetriol, glycerol, pentaerythritol, dipentaerythritol, and the like, and combinations thereof.

The acid and/or anhydride component may include compounds having an average of at least two carboxylic acid groups and/or anhydrides thereof. In some embodiments, dicarboxylic acids or anhydrides of dicarboxylic acids may be used; however, higher functionality acids and anhydrides may also be used when some branching of the polyester is desired. Suitable polycarboxylic acid or anhydride compounds include, but are not limited to, those having from about 3 to about 20 carbon atoms. Illustrative examples of suitable compounds include, but are not limited to, phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, pyromellitic acid, succinic acid, azelaic acid, adipic acid, 1, 4-cyclohexanedicarboxylic acid, dodecane-1, 12-dicarboxylic acid, citric acid, trimellitic acid, anhydrides thereof, and combinations thereof.

In one process herein, suitable acid functional polyesters for forming polyester polyol side chains can be prepared by reacting dicarboxylic acids, such as those of the formula (HOOC-R-COOH), with diols to form acid functional polyesters, which can be mono-acid functional or di-acid functional.

In one method, one molar equivalent of a diacid and a diol may be reacted to form a monoacid-functional polyester. In an alternative embodiment, a molar excess of diacid may be reacted to form a diacid functional polyester. In such embodiments, to obtain the mono-acid functional polyester, the di-acid functional polyester may be reacted with a mono-functional alcohol (such as hexanol, cyclohexanol, benzyl alcohol, stearyl alcohol, oleyl alcohol, undecanol, and ethylene glycol butyl ether) to cap one of the acid groups on the di-acid functional polyester. Another method of forming acid functional polyesters is to react a diacid with an equimolar amount of diol while monitoring the acid number of the product in the reaction vessel. The reaction may be stopped when the product has the desired acid number. In one embodiment, the desired acid number may indicate a high concentration of acid functional resin.

In other methods, monoacid-functional polyesters involve ring-opening polymerization of a lactone or polycaprolactone initiated by a hydroxy-functional acid. Generally, such polyesters will also have one or more terminal hydroxyl groups. In these methods, and for example, the acid functional polyester and its side chain residues can include blocks derived from cyclic esters, such as lactones having 4 to 10 carbon atoms, with a cyclic ester of six carbon atoms (such as caprolactone) being one suitable example. These blocks derived from cyclic esters contain the moiety- (O (CH)₂)_xCO)_y-, where x may be an integer of 3 to 9 (in other methods, 4 to 5, and in other methods, 5), and y may be at least 3, and in other methods, an integer of 3 to 20. If included in the grafted side chains herein, the amount of cyclic ester (such as caprolactone) can be from about 20 wt% to about 90 wt%, in other processes from about 30 wt% to about 80 wt%, and in further processes from about 60 wt% to about 70 wt%, provided by at least three or more repeating units of the cyclic ester in each block.

In some methods, cyclic esters suitable for ring opening reactions initiated by hydroxy-functional acids may be those having the structure of formula V:

wherein n is an integer from 3 to 9, and in some cases, from 4 to 5, and each R₇Independently hydrogen, a C1 to C4 alkyl group, a C1 to C4 alkoxy group, and/or a halogen group. In some methods, the cyclic ester can include unsubstituted lactones, such as epsilon-caprolactone, L-lactide, DL-lactide, and,-valerolactone and/or e-lactone. In other processes, the lactone may be monoalkyl-, dialkyl-, andtrialkyl-lactones or epsilon-caprolactones, lactones such as monomethyl-, dimethyl-, trimethyl-, monoethyl-, diethyl-, triethyl-, monopropyl-, dipropyl-, tripropyl-, monoisopropyl-and-n-butyl-caprolactone and caprolactones. In a further process, the lactone may be a mono-, di-and trialkoxy-lactone or an epsilon-caprolactone, such as mono-, dimethoxy-, trimethoxy-, mono-, diethoxy-, triethoxy-, mono-n-propoxy-and mono-isobutyl-epsilon-lactone or caprolactone; chloro-epsilon-caprolactone; and so on.

For example, ring-opening polymerization of caprolactone initiated by, for example, 2-2' -bis (hydroxymethyl) propionic acid (also known as dimethylolpropionic acid or DMPA) provides a useful way to prepare monoacid-functional polyesters suitable for use in the grafted side chains of polyurea polymers. Suitable amounts of reactants may be about 70% to about 95% by weight caprolactone (or other cyclic ester or derivative) and about 5% to about 30% acid.

Another useful reaction is the reaction between dimethylol butanoic acid and caprolactone to form carboxy-modified polycaprolactone, in particular a polycaprolactone polyester diol having pendant carboxy functional groups. Other hydroxy-functional carboxylic acids and lactones may also be used to form acid-functional polyesters that can be used to prepare pigment dispersants. Without being bound by any particular theory, it is believed that the most useful degree of caprolactone modification is a resulting number average molecular weight of greater than about 500, e.g., about 1000 to about 6000, as measured by gel permeation chromatography ("GPC") using polystyrene as a standard. The use of these polyesters has the advantage of providing hydroxyl groups on the side chains for subsequent reaction with melamine, isocyanate or anhydride crosslinkers. Examples of commercially available acid functional polycaprolactone polyester diols include CAPA polyester diol available from Solvay and DICAP polyester diol available from GEO Specialty Chemicals. Polyesters using 2-ethylhexanol as the initiating alcohol and dibutyltin dilaurate as the catalyst to react with the cyclic anhydride to form caprolactone with terminal acid groups may also be used in the present invention.

In another approach, the acid functional polycaprolactone polyester diol may be end capped by the use of one or more monofunctional acids R-COOHOne or two hydroxyl groups. In one useful embodiment, R can have from about 4 to about 18 carbon atoms, for example from about 11 to about 12 carbon atoms. Examples of useful monofunctional carboxylic acids include lauric, caprylic, capric, myristic, palmitic, stearic, oleic, elaidic (9-octadecenoic), linoleic, linolenic, stearynoic, soy or other fatty acids. This forms polyesters, such as those in formula II above, where R₃Is an ester chain (O ═ C — R) derived from any of the acid groups mentioned above. In one embodiment, two moles of such monofunctional acids may react with the hydroxyl groups of the polyester to form a mono-acid functional polyester, wherein both hydroxyl groups are terminated by ester chains.

Acid functional epoxy esters may also be suitable for use in the grafted side chains of the polyurea polymers herein. In one embodiment, useful epoxy esters can be formed by the reaction of one mole of a monofunctional epoxy resin (such as CARDURA E10 available from Hexion Specialty Chemicals, Inc.) with one mole of a diacid.

In another method, fatty acids and derivatives thereof, such as monohydroxy or polyhydroxy fatty acids and esters thereof, can be used or formed in the side chain R₁. For example, fatty acids having from about 10 to about 24 carbon atoms, such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, elaidic acid (9-octadecenoic acid), linoleic acid, linolenic acid, stearynoic acid, or blends thereof, e.g., soy fatty acid or other fatty acids, and combinations thereof, can be used to react with carbodiimide groups to form the polyester polyol grafted polyurea polymers herein. In other methods, derivatives of fatty acids having 10 to 24 carbon atoms may also be used in the compounds herein. Examples include, but are not limited to, the hydroxy-substituted fatty acids described above as well as hydroxy-tetracosenoic acid, hydroxy-octadecenoic acid, hydroxy-decenoic acid, hydroxy-octadecanoic acid, hydroxy-eicosenoic acid, dihydroxy-octadecanoic acid, trihydroxy-octadecanoic acid, and the like, esters thereof, and combinations thereof, which are also useful for reacting with carbodiimide groups to form the polyester polyol grafted polymers herein.

In another embodiment, suitable acid-functional resins may be prepared by reacting an anhydride with a mono-hydroxy-functional polyether or a mono-amino-functional polyether (such as monoethers of polypropylene glycol, polyethylene glycol, and copolymers thereof, available from HuntsmanMonoamines). Suitable acid anhydrides include, but are not limited to, succinic anhydride, maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, and the like. Such reactions produce monoacid-functional diols capable of reacting with carbodiimide groups.

To form the polyurea polymer, the selected carbodiimide compound is mixed with the acid-functional resin in the presence of a solvent and may be reacted at room temperature or may be heated to about 80 ℃ to about 120 ℃, for example about 85 ℃ to about 90 ℃. Typical solvents that may be used include, but are not limited to, ketones such as methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, and acetone; alcohols such as methanol, ethanol, isopropanol, and butanol; esters such as ethyl acetate and butyl acetate; glycols such as ethylene glycol and propylene glycol; ethers such as tetrahydrofuran, ethylene glycol monobutyl ether, and propylene glycol methyl ether; and mixed ether acetates such as propylene glycol methyl ether acetate, diethylene glycol monobutyl ether acetate, and the like. In addition, aromatic solvents such as toluene, xylene, naphtha, and mixtures of the various solvents listed herein may also be used.

The carbodiimide and acid functional polymer can be mixed in a molar ratio of carbodiimide to carboxylic acid of about 0.5:1 to about 5:1, for example about 1:1, about 1.5:1, and about 2: 1. In one useful method, the polyurea polymer has an acid number of from 0 to about 50, such as from 0 to about 10. The number average molecular weight of the pigment-dispersing polymer, as measured by GPC, is at least about 500 to about 50,000, such as about 2,000 to about 20,000, also such as about 3,000 to about 12,000, and even further such as about 3,000 to about 6,000. The hydroxyl number of the resulting polyester-polyol grafted polyurea may be from about 5 to about 120, for example from about 20 to about 80, from about 40 to about 80, from about 60 to about 80, or from about 60 to about 70.

Polymer or resin systems

In one aspect of the present disclosure, the above-described resin or polymer systems are particularly suitable for use in the polymer component of solvent borne two-component compositions having low gloss values in some processes. The first component of the two-component composition may be a polymer component comprising any of the features of the polymer or resin systems described herein above. The polymer component may also include solvents, pigments, extenders, levelers, and other additives as desired for the application and to achieve low gloss values if desired. The second component of the two-component composition may be an isocyanate-functional material suitable for crosslinking one or more polyester polyols with one or more polyurea polymers contained in the polymer component. Exemplary curing components are described in more detail below.

In one approach, the polymer or resin system (based on the total weight of crosslinkable polymers in the system) may comprise from about 80 to about 99 weight percent of a conventional hydroxyl terminated polyester blend comprising one or more conventional polyester polyols (in other approaches, from about 88 to about 96 weight percent, and in other approaches, from about 88 to about 92 weight percent) and from about 1 to about 20 weight percent of a polyester-polyol grafted polyurea (in other approaches, from about 4 to about 12 weight percent, and in other approaches, from about 8 to about 12 weight percent).

In other methods, the polymer or resin system can comprise (i) from about 40 to about 80 weight percent of an aromatic polyester polyol having a hydroxyl value of from 200 to about 300, (ii) from about 5 to about 30 weight percent of a branched aliphatic polyester polyol having a hydroxyl value of from about 120 to about 200, (iii) from about 5 to about 30 weight percent of a polyester polyol having a hydroxyl value of from about 80 to about 150, the polyester polyol being derived from the reaction of a linear diol or ester diol, a cyclic diol, a polycaprolactone polyol and a cyclic dicarboxylic acid or anhydride, and (iv) from about 5 to about 30 weight percent of a polyester-polyol grafted polyurea having a hydroxyl value of from about 20 to about 120. In some methods, the composition may further comprise about 2 times to about 4 times the amount of the polyester polymer (i) relative to the sum of the amounts of the polyester polymer (ii) and the polyester polymer (iii). In further methods, the resin or polymer systems herein can further comprise a ratio of conventional polyester polyols (i.e., (i), (ii), and (iii)) to polyester-polyol grafted polyurea (iv) of about 70:30 to about 95: 5.

The resin or polymer system is particularly useful in two-component solvent-borne compositions to provide dry films on a variety of rigid and plastic substrates such as, but not limited to, acrylonitrile-butadiene-styrene (ABS), Polycarbonate (PC), and ABS/PC blends. When blended in a composition configured to achieve very low gloss (i.e., about 5 or less, about 2 or less, or 60 ° gloss between 1.5 and 1.8) and applied to such rigid surfaces at very thin dry film thicknesses (such as about 2 mils or less, about 1.2 mils or less, and especially about 1 mil or less), the resin or polymer systems described herein achieve acceptable results of linear abrasion (85 ° gloss does not change by more than 1.5 units after 10 cycles of linear abrasion), pass chemical resistance tests for sunscreen and insect repellent, as measured according to GMW 14445 (relative grade 2 or less), and at 1240kj/m as measured according to GMW 14162²After xenon exposure, adhesion to polycarbonate was acceptable (0% tape removed after exposure). The following examples provide more details of such testing.

Curing agent for two-component systems

The above-described polymer or resin systems are suitable for use in two-component solvent-borne compositions. In addition to the polymer or resin component, the two-component system may also comprise a second component of an isocyanate functional material suitable for crosslinking one or more polyester polyols and one or more polyester-polyol grafted polyurea polymers. The isocyanate functional material may be selected from the group consisting of monofunctional isocyanates, difunctional isocyanates, trifunctional isocyanates, and multifunctional isocyanates. Difunctional and trifunctional isocyanates, as well as higher functional isocyanates, are particularly useful. Representative isocyanates will have two or more isocyanate groups per molecule and may include aliphatic compounds such as ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1, 2-propylene diisocyanate, 1, 2-butylene diisocyanate, 2, 3-butylene diisocyanate, 1, 3-butylene diisocyanate, ethylene diisocyanate, and butylene diisocyanate; cycloalkylene compounds such as 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexyl isocyanate and 1, 3-cyclopentane diisocyanate, 1, 3-cyclohexane diisocyanate and 1, 2-cyclohexane diisocyanate; aromatic compounds such as m-phenylene diisocyanate, p-phenylene diisocyanate, 4' -diphenyl diisocyanate, 1, 5-naphthalene diisocyanate and 1, 4-naphthalene diisocyanate; aliphatic-aromatic compounds such as 4,4 '-xylylene diisocyanate, 2, 4-toluene diisocyanate or 2, 6-toluene diisocyanate or mixtures thereof, 4' -toluidine diisocyanate and 1, 4-xylylene isocyanate; nucleus-substituted aromatic compounds such as dianisidine diisocyanate, 4' -diphenyl ether diisocyanate and chlorodiphenylene diisocyanate; triisocyanates such as triphenylmethane-4, 4',4 "-triisocyanate, 1,3, 5-triisocyanate benzene and 2,4, 6-triisocyanate toluene; and tetraisocyanates such as 4,4' -diphenyl-dimethylmethane-2, 2' -5,5' -tetraisocyanate; polymeric polyisocyanates, such as toluene diisocyanate dimers and trimers, and other various polyisocyanates containing biuret, urethane, and/or allophanate linkages.

The amount of isocyanate functional material used in the composition will be sufficient to provide an NCO to OH ratio of about 0.8:1 to about 3:1, where OH represents the total amount of free hydroxyl groups of the polyester blend and polyester-polyol grafted polyurea in the resin system combined with free hydroxyl groups in any other optionally added reactive hydroxyl functional resin. In some methods, the isocyanate functional material may be packaged separately from the components including the polymer system described above and other optional components. The curing component comprising the isocyanate functional material may also comprise one or more solvents, catalysts and non-reactive (non-reactive with isocyanate) additives as required for a particular application.

The composition may contain an amount of one or more catalysts that catalyze the reaction of isocyanate hydroxyl groups. The catalyst may be provided in the polymer component of the composition. Examples of usable catalysts may include tertiary amines such as triethylenediamine, N-methylmorpholine, N-ethylmorpholine, diethylethanolamine, 1-methyl-4-dimethylaminoethylpiperazine, 3-methoxy-N-dimethylpropylamine, N-dimethyl-N-methylisopropylenediamine, N-diethyl-3-diethylaminopropylamine, N-dimethylbenzylamine, dicyclohexylmethylamine, 2,4, 6-trimethylaminomethylphenol, N-dimethylcyclohexylamine, triethylamine, tri-N-butylamine, 1, 8-diaza-dichloro [5,40] -undecene-7N-methyldiethanolamine, N-dimethylethanolamine, N-diethylcyclohexylamine, N-dimethylcyclohexylamine, N-dimethylpropylamine, N, dimethylpropylamine, dimethylhexyle, dimethylpropylamine, dimethylhexyle, dimethylpropylamine, dimethylhexyle, dimethylhexylamine, dimethylolmethylamine, N, N ' -tetramethylethylenediamine, 1, 4-diaza-bicyclo- [2,2,2] -octane-N-methyl-N ' -dimethylaminoethyl-piperazine, bis- (N, N-diethylaminoethyl) -adipate, N-diethylbenzylamine, pentamethyldiethylenetriamine, N ' -tetramethyl-1, 3-butanediamine, 1, 2-dimethylimidazole, 2-methylimidazole; tin compounds such as stannous chloride, dibutyltin di-2-ethylhexanoate, stannous octoate, dibutyltin dilaurate, trimethyltin hydroxide, dimethyltin dichloride, dibutyltin diacetate, dibutyltin oxide, tributyltin acetate, tetramethyltin, dimethyldioctyltin, tin ethylhexanoate, tin laurate, dibutyltin maleate, dioctyltin diacetate; other metallorganics such as zinc octoate, phenylmercuric propionate, lead octoate, lead naphthenate and copper naphthenate.

In one method, the catalyst is dibutyltin dilaurate (DBTDL). The useful amount of catalyst will be about 0.01% to 5% based on the total weight of the polyester polyol, polyester polyol grafted polyurea, and polyisocyanate. The catalyst may be provided wholly or partially with the polymer component or wholly or partially with the curing component, or may be provided partially within both the polymer component and the hardener component as required by a particular application.

Solvent(s)

In some embodiments, the compositions herein may comprise one or more solvents, such as ketone, ester, alcohol, glycol ether, and glycol ether ester solvents. Illustrative, non-limiting examples of solvents that may be useful include xylene, n-butyl acetate, t-butyl acetate, n-butyl propionate, naphtha, ethyl 3-ethoxypropionate, toluene, Methyl Ethyl Ketone (MEK), acetone, Methyl Propyl Ketone (MPK), methyl n-amyl ketone (MAK), propylene glycol methyl ether acetate (PMA), and the like, and blends thereof. Such solvents, if used, may be incorporated into the polymer component, the curing component, or both components of the two-component compositions herein. The total amount of solvent used in the composition can be selected to provide a coating having a suitable viscosity for the application method.

Other additives

The polymer component and the curing component may also comprise other additives suitable for the intended use or application. Additives as used herein refer to a general class of components or other raw materials that may be added to the compositions herein to facilitate various properties. Examples include, but are not limited to, surfactants, defoamers, biocides, mildewcides, algaecides, thickeners, antisettling agents, pH buffers, corrosion inhibitors, drying agents, antiskinning agents, UV inhibitors, wetting agents, leveling agents and other inert pigments (such as titanium dioxide, clays, amorphous and surface treated silica, calcium carbonate, and the like, and combinations thereof), leveling agents, and the like, as well as various combinations thereof as desired for a particular application.

Micronized powder additives may be used in the coating compositions of the present invention to provide excellent scratch and mar resistance in the cured coating. Examples of such additives include micronized powders, such as polymethylmethacrylate powder and Polytetrafluoroethylene (PTFE) powder, a combination of the two, and the like. The amount of the micronized powder is preferably 1 to 5% by weight with respect to the total amount of the coating composition, and the micronized powder may have a particle size of 30 μm or less. Examples of commercially available products of such micronized powders are provided in the following table.

In an exemplary embodiment, the polymer component of the two-component composition comprises from about 10 to 50 weight percent of the hydroxyl terminated polyester blend and from about 1 to 15 weight percent of the polyester polyol grafted polyurea. In another embodiment, the polymer component of the two-component composition comprises from about 15 to 40 weight percent of the hydroxyl terminated polyester blend and from about 2 to 10 weight percent of the polyester polyol grafted polyurea. In another embodiment, the polymer component of the two-component composition comprises from about 20 to 35 weight percent of the hydroxyl terminated polyester blend and from about 4 to 8 weight percent of the polyester polyol grafted polyurea. The remaining amount of the composition includes, if appropriate, pigments, levelling agents, solvents and other typical additives. The second component may be a curing agent having an isocyanate functional material as described above.

The resin or polymer systems herein are particularly useful in low gloss compositions, such as those having a 60 ° gloss of about 5 or less, about 2 or less, or between 1.5 and 1.8. Thus, the composition may include an effective amount of pigment, leveling agent, or other extender as needed to achieve a low gloss value. In one method, the composition may comprise from about 5% to about 25% by weight of pigments, silica, and other leveling agents.

Examples

The following examples demonstrate the preparation of the resin or polymer systems herein and exemplary two-component compositions such as those described above. These examples are intended to be representative of polymers and compositions that may be prepared and are not intended to limit the scope of the disclosure to the particular exemplary embodiments disclosed below. All percentages, ratios, and amounts in the examples, as well as throughout the present disclosure, are by weight unless otherwise indicated. All measurements herein were made at 23 ± 1 ℃ and 50% relative humidity, unless otherwise indicated.

Comparative resin control example

The polyester polyol resin used as a control is available under the trade name Desmophen^TM1652 (about 100% solids, OH No. 53) solvent-free, linear, saturated polyester polyol resins commercially available from Covestro Corporation.

Exemplary resins example 1

A three liter reactor equipped with a stirrer, condenser, thermocouple, and nitrogen inlet was charged with about 1216 grams of a monocarboxylic acid functionalized polycaprolactone diol having a Mw of about 2000 daltons (DICAP 2020 available from GEO Specialty Chemicals) and heated to about 90 ℃ under nitrogen. About 784 grams of polycarbodiimide having 4.5 repeating carbodiimide units (Zolidine XL-29SE from Angus) was then added to the reactor. After the reaction mixture was held at about 90 ℃ for three hours, about 1890 grams of xylene and about 630 grams of PMAc were added and the solution was drained. The reaction solution had a solids content of about 35.5 wt.%, an OH number of about 41mg KOH/g solids, an OH equivalent weight of about 1368, a Tg of about-54 ℃, a density of about 8.10lb/gal, an Mn of about 4,821 by GPC analysis and an Mw of about 16,262.

Exemplary resin example 2

A three liter reactor equipped with a stirrer, condenser, thermocouple, and nitrogen inlet was charged with about 914 grams of a monocarboxylic acid functionalized polycaprolactone diol having a Mw of about 1000 daltons (DICAP 1000 available from GEO Specialty Chemicals) and heated to about 90 ℃ under nitrogen. Then, about 1086 grams of polycarbodiimide having 4.5 repeating carbodiimide units (Zolidine XL-29SE from Angus) was added to the reactor. After the reaction mixture was held at about 90 ℃ for three hours, the solution was drained. The reaction solution had a solids content of about 72.8 wt.%, a density of about 9.0lb/gal, an OH number of about 60mg KOH/g solids, an OH equivalent weight of about 935, a Tg of about-47 ℃, an Mn of about 3,129 and an Mw of about 8,246 as analyzed by GPC.

Exemplary resin example 3

A three liter reactor equipped with a stirrer, condenser, thermocouple, and nitrogen inlet was charged with about 684 grams of a monocarboxylic acid functionalized polycaprolactone diol having a Mw of about 600 (DICAP 600 available from GEO Specialty Chemicals) and heated to about 90 ℃ under nitrogen. About 1316 grams of polycarbodiimide having 4.5 repeating carbodiimide units (Zolidine XL-29SE from Angus) was then added to the reactor. After the reaction mixture was held at about 90 ℃ for three hours, the solution was drained. The reaction solution had a solids content of about 67.1 wt.%, a density of about 8.9lb/gal, an OH number of about 80mg KOH/g solids, an OH equivalent weight of about 701, a Tg of about-36 ℃, an Mn of about 2,460 by GPC analysis, and an Mw of about 5,845.

Comparative paint example

By mixing about 377 grams of a branched aromatic polyester polyol having an OH number of about 285, about 76 grams of a branched saturated aliphatic polyester polyol having an OH number of about 167, and about 53 grams of a straight chain saturated aliphatic polyester polyol having an OH number of about 53 (Desmophen)^TM1652) And about 391 grams of solvent to prepare the resin system. After blending, about 85 grams of silica in solvent was blended into the mixture. The mixture is then ground for about 10 minutes when about 27 grams of a commercially available aliphatic polyester polyol having an OH number of about 100 is blended with other additives including UV absorbers, catalysts, and solvents to form the polymer component of the two-component system.

Paint exemplary embodiment 1

The resin system was prepared by blending about 377 grams of a branched aromatic polyester polyol having an OH value of about 285, about 76 grams of a branched saturated aliphatic polyester polyol having an OH value of about 167, about 149 grams of exemplary resin example 1 (about 36% solids), and about 295 grams of solvent. After blending, about 85 grams of silica in solvent was blended into the mixture. The mixture is then ground for about 10 minutes when about 27 grams of a commercially available aliphatic polyester polyol having an OH number of about 100 is blended with other additives including UV absorbers, catalysts, and solvents to form the polymer component of the two-component system.

Paint example 2

The resin system was prepared by blending about 377 grams of a branched aromatic polyester polyol having an OH value of about 285, about 76 grams of a branched saturated aliphatic polyester polyol having an OH value of about 167, about 73 grams of exemplary resin example 2 (about 73% solids), and about 371 grams of solvent. After blending, about 85 grams of silica in solvent was blended into the mixture. The mixture is then ground for about 10 minutes when about 27 grams of a commercially available aliphatic polyester polyol having an OH number of about 100 is blended with other additives including UV absorbers, catalysts, and solvents to form the polymer component of the two-component system.

Paint example 3

The resin system was prepared by blending about 377 grams of a branched aromatic polyester polyol having an OH value of about 285, about 76 grams of a branched saturated aliphatic polyester polyol having an OH value of about 167, about 79 grams of exemplary resin example 3 (about 67% solids), and about 365 grams of a solvent. After blending, about 86 grams of silica in solvent was blended into the mixture. The mixture is then ground for about 10 minutes when about 27 grams of a commercially available aliphatic polyester polyol having an OH number of about 100 is blended with other additives including UV absorbers, catalysts, and solvents to form the polymer component of the two-component system.

Results

Each of paint examples 1 to 3 and paint control was blended with an isocyanate functional hardener at an NCO: OH ratio of about 1.2 and each blend was applied separately to PC, ABS and PC/ABC substrates having a dry film thickness of 1.0 mil. Dry films were evaluated for sunscreen and insect repellent chemical resistance (GMW 14445-qualified as grade 2 or below 2), linear abrasion (GMW 14125-qualified as Δ 85 ° gloss less than 1.5), and at about 1240kj/m²Adhesion to polycarbonate after xenon exposure. The results for the paint control and paint examples 1-3 of the present invention are provided in table 1 below.

Table 1: evaluation of Performance

As shown in Table 1 above, a paint control comprising a conventional hydroxyl terminated polyester polyol was at 1240kJ/m²After xenon exposureFail the adhesion test and fail the sunscreen and insect repellent tests. However, the polyurea polyol was found to be 1240kJ/m²Provides excellent adhesion after xenon exposure. When the OH number of the polyurea polyol is too low, as in paint example 1, the linear abrasion is good, but the sunscreen and insect repellent tests do not work well. When the OH number of the polyurea polyol is too high, as in paint example 3, the sunscreen and repellent tests are good, but the linear abrasion is not good. These two opposing properties of the paint pass when the polyurea polyol has an OH number in the optimum range (50-70 mg KOH/g solids) and provide excellent adhesion after xenon exposure.

The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Rather, unless otherwise specified, such dimensions are intended to mean both the recited value and a functionally equivalent range surrounding that value. All ranges recited are intended to mean any endpoint within the range. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

As used herein, functionalized, functionality or functional group means a group or portion of a larger molecule or polymer that is reactive with another group or atom. For example, in the case of a dicarbonyl-functionalized polymer or oligomer, a functionality of one means a single dicarbonyl moiety, a functionality of two means two dicarbonyl moieties, and the like.

As used herein, not requiring, not having a substantial amount, not being present, or being substantially free, or not being present generally means that the polymers and/or coating compositions herein have less than about 1 wt.%, in other methods, less than about 0.5 wt.%, in other methods, less than about 0.2 wt.%, and in other methods, are free of the particular component.

The glass transition temperature or Tg generally refers to the temperature region in which an amorphous polymer transitions from a hard glassy material to a softer rubbery material. Typically, this transition is reversible. Tg is measured by Differential Scanning Calorimetry (DSC) and/or Dynamic Mechanical Analysis (DMA), such as with a TA instruments Q200 differential scanning calorimeter. Preferably, Tg is measured by DSC.

Gloss, as generally used herein, refers to the gloss intensity measured at 60 degrees or 85 degrees and is determined according to ASTM D323.

Exemplary embodiments have been described above. It will be apparent to those skilled in the art that the above-described apparatus and methods may incorporate changes and modifications without departing from the general scope of the disclosure. It is intended to include all such modifications and alterations insofar as they come within the scope of the present disclosure. Furthermore, to the extent that the term "includes" is used in either the detailed description or the claims, such term is intended to be inclusive in a manner similar to the term "comprising" as "comprising" is interpreted when employed as a transitional word in a claim.

It should be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless expressly and unequivocally limited to one referent. Thus, for example, reference to "an antioxidant" includes two or more different antioxidants. As used herein, the term "include" and grammatical variations thereof are intended to be non-limiting such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items.

For the purposes of the present specification and appended claims, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term "about", unless otherwise indicated. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

It is to be understood that each component, compound, substituent or parameter disclosed herein is to be interpreted as disclosed either alone or in combination with each and every other component, compound, substituent or parameter disclosed herein.

It will also be understood that each range disclosed herein is to be interpreted as disclosing each particular value within the disclosed range having the same number of significant digits. Thus, for example, a range of 1 to 4 is to be interpreted as an explicit disclosure of the values 1,2, 3 and 4 and any range of such values.

It will also be understood that each lower limit of each range disclosed herein is to be understood as being disclosed in connection with each upper limit within each range and each specific value within each range disclosed herein for the same component, compound, substituent or parameter. Accordingly, the disclosure is to be construed as a disclosure of all ranges obtained by combining each lower limit of each range with each upper limit of each range or with each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it is also to be understood that any range between the broad range of endpoints is also discussed herein. Thus, a range of 1 to 4 also means a range of 1 to 3,1 to 2,2 to 4, 2 to 3, etc.

Further, a particular amount/value of a component, compound, substituent or parameter disclosed in the specification or examples is to be understood as disclosing either a lower limit or an upper limit of a range, and thus, may be combined with any other lower limit or upper limit of a range of the same component, compound, substituent or parameter disclosed elsewhere in this application, or a particular amount or value, to form a range of components, compounds, substituents or parameters.

While specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended are intended to embrace all such alternatives, modifications, variations, improvements, and substantial equivalents.