Patent Application
20080146381
The present invention is directed to golf balls comprising a core and a layer disposed about the core; the layer comprises polyurea formed from the reaction of an isocyanate and a (meth)acrylated amine.
The use of amines and polyamines as crosslinkers or “curatives” is well known. For example, amines are known to crosslink with isocyanates to form urea compounds. Amines are also known to be reactive with, and therefore used with, activated unsaturated groups, epoxy groups, aromatic activated aldehyde groups, cyclic carbonate groups, and acid and anhydride and ester groups. Polyamine crosslinkers with primary amino groups can be quite reactive with some of these functionalities under ambient or low temperature conditions (i.e. less than 100° C.). This high reactivity can result in too short a potlife. Certain aliphatic secondary amines, however, are not reactive enough with these various functionalities. It is therefore desired to provide amine curatives that are sufficiently reactive, but that provide an adequate potlife. Such curatives can be reacted, for example, with isocyanates to produce polyureas that can be used in the formation of golf balls.
The present invention is directed to golf balls comprising a core, and a layer disposed about the core, wherein the layer comprises a polyurea formed from the reaction of an isocyanate and a (meth)acrylated amine. The present invention is further directed to sports equipment comprising a polyurea formed from the reaction of an isocyanate and a (meth)acrylate amine.
The present invention is directed to golf balls comprising a core and a layer disposed about the core, wherein the layer comprises a polyurea formed from the reaction of an isocyanate and a (meth)acrylated amine. These acrylated amines are generally prepared by reacting a (meth)acrylate and a polyamine. In certain embodiments, the (meth)acrylated amines are generally prepared by reacting a (meth)acrylate, a dialkyl maleate and/or dialkyl fumarate, and a polyamine. Dialkyl maleate and/or dialkyl fumarate are sometimes referred to herein as “maleate(s)—fumarate(s)”, and like terms. All of these reaction products are referred to collectively herein as “(meth)acrylated amine”, “(meth)acrylated amine curative” and like terms. Those embodiments in which maleates-fumarates are also used in the reaction product may sometimes be referred to herein as a (meth)acrylate/aspartate amine, a (meth)acrylate/aspartate amine curative and like terms, but these embodiments are also included in the more general terms “(meth)acrylated amine” and “(meth)acrylated amine curative” and like terms.
The (meth)acrylate can be any suitable mono or poly (meth)acrylate. In certain embodiments, the polyacrylate comprises di(meth)acrylate, in certain embodiments the polyacrylate comprises tri(meth)acrylate, and in certain embodiments the polyacrylate comprises tetra(meth)acrylate. Suitable monoacrylates include but are not limited to those having the formula:
wherein R is H or methyl and R1 may be, without limitation, alkyl or hydroxyalkyl, such as methyl, ethyl, 2-hydroxyethyl, 1-methyl-2-hydroxyethyl, 2-hydroxypropyl, propyl, isopropyl, n-butyl, 2-hydroxybutyl, 4-hydroxybutyl, isobutyl, sec-butyl, tert-butyl, hexyl, 2-ethylhexyl, cyclohexyl, methylcyclohexyl, trimethylcyclohexyl, isobornyl, lauryl, stearyl and the like. Non-limiting examples of mono (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and adducts of hydroxy (meth)acrylates with lactones such as the adducts of hydroxyethyl (meth)acrylate with ε-caprolactone. Suitable diacrylates include ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 2,3-dimethylpropane 1,3-di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, ethoxylated hexanediol di(meth)acrylate, propoxylated hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, alkoxylated neopentyl glycol di(meth)acrylate, hexylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polybutadiene di(meth)acrylate, thiodiethyleneglycol di(meth)acrylate, trimethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, alkoxylated hexanediol di(meth)acrylate, alkoxyolated neopentyl glycol di(meth)acrylate, pentanediol di(meth)acrylate, cyclohexane dimethanol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, and mixtures thereof. Non-limiting examples of tri and higher (meth)acrylates include glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Other suitable acrylate oligomers include (meth)acrylate of epoxidized soya oil, urethane acrylates of polyisocyanates and hydroxyalkyl (meth)acrylates and polyester acrylates. Mixtures of (meth)acrylate monomers may also be used, including mixtures of mono, di, tri, and/or tetra (meth)acrylates. (Meth)acrylates higher than di (meth)acrylates (e.g. tri, tetra, and the like) will typically only be used in minor amounts to avoid gelling of the product. One skilled in the art can determine what amount of these (meth)acrylates is suitable.
Any suitable polyamine can be used according to the present invention. A “polyamine” is an amine with at least 2 primary amino groups. In certain embodiments, the polyamine is a diamine, and the amine nitrogens on the diamine are equally reactive; that is, all of the amine nitrogens are equally likely to react with another functional group. In certain other embodiments, the amine nitrogens of the diamine may be unequal in reactivity toward, for example, (meth)acrylates and/or maleates-fumarates. Examples of suitable diamines include but are not limited to ethylene diamine, 1,2-diaminopropane, 1,5-diamino-2-methylpentane (DYTEK A, Invista), 1,3-diaminopentane (DYTEK EP, Invista), 1,2-diaminocyclohexane (DCH-99, Invista), 1,6-diaminohexane, 1,11-diaminoundecane, 1,12-diaminododecane, 3-(cyclohexylamino)propylamine, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, (isophorone diamine (“IPDA”)), 4,4′-diaminodicyclohexylmethane (PACM-20, Air Products; DICYKAN, BASF), 3,3′-dimethyl-4,4′-diaminodicyclohexyl methane (DIMETHYL DICYKAN or LAROMIN C260, BASF; ANCAMINE 2049, Air Products), 3,3′-[1,4-butanediylbis-(oxy)bis]-1-propanamine, menthanediamine, and diamino functional polyetherpolyamines having aliphatically bound primary amino groups, examples of which include JEFFAMINE D-230, JEFFAMINE D-400, JEFFAMINE D-2000, and JEFFAMINE D-4000, Huntsman Corporation. It will be appreciated that when the amine is hindered, the reaction time between the (meth)acrylated amine and the isocyanate will be slower. This gives a longer pot-life or work processing time in those situations where a longer processing time is desired.
In certain embodiments the amine is a triamine. Examples of suitable triamines include but are not limited to diethylene triamine, dipropylene triamine, bis(hexamethylene) triamine and triamino functional polyetherpolyamines having aliphatically bound primary amino groups (JEFFAMINE T-403, T-3000, T-5000, Huntsman Corporation). For example, the amine can be an amine terminated (that is, an amine on each end, thus rendering the amine difunctional) polyethylene or polypropylene glycol, such as a polypropylene having an average molecular weight of 4000 or a polyethylene having an average molecular weight of 600. One skilled in the art will understand that these types of products are sold with a mixture of polymers having a relatively wide range of molecular weight, such as 4000+/−500 or 600+/−200 but that the average molecular weight is 4000 or 600. In other embodiments the amine can be a tetraamine or other higher functional amine.
In certain specific embodiments of the present invention, the (meth)acrylate is acrylate and the polyamine is diaminodicyclohexyl methane. In other certain specific embodiments, the (meth)acrylate is acrylate and the polyamine is 3,3′-dimethyl-4,4′-diaminodicyclohexyl methane. In certain other specific embodiments, the amine is JEFFAMINE D4000, a difunctional, amine terminated polypropylene glycol having an average molecular weight of 4000, and in other specific embodiments the amine is XTJ 500, a difunctional, amine terminated polyethylene glycol having an average molecular weight of 600, and commercially available from Huntsman. The amine and acrylate can be reacted in any ratio to give a suitable product. In certain embodiments, the equivalent ratio of amine to (meth)acrylate is substantially stoichiometric.
In certain other embodiments, both a monoacrylate and a polyacrylate can be reacted with the polyamine. The polyacrylates, polyamines, and monoacrylates can be as described above. In particularly suitable embodiments, the polyacrylate is hexanediol diacrylate, the amine is 3,3′-dimethyl-diaminodicyclohexyl methane, and the monoacrylate is methyl acrylate. In other particularly suitable embodiments, the polyacrylate is HDDA, the amine is IPDA, and the monoacrylate is butylacrylate.
The ratio of poly(meth)acrylate to amine to mono(meth)acrylate can be any suitable ratio to give the desired properties to the (meth)acrylated amine curative. For example, when the (meth)acrylate is a diacrylate, the equivalent ratio of poly(meth)acrylate:amine:mono(meth)acrylate can be 0.20-0.40: 1:0.75-0.55, such as 0.30:1:0.65; 2:3:1; 1:2:1; or 1:3:2. When the poly(meth)acrylate is a triacrylate, the equivalent ratio of triacrylate:amine:mono(meth)acrylate can be 1:3:2 or 1:2:1. It will be appreciated that these ratios are just examples, and that any other suitable ratio can be used according to the present invention.
The (meth)acrylated amines used in the present invention can be formed, for example, in the manner described in the examples, or any other suitable manner. When both a mono(meth)acrylate and poly(meth)acrylate are used, the poly(meth)acrylate and amine can be reacted first, and then reacted with a mono(meth)acrylate in sequential steps, or the polyamine can be reacted with the poly(meth)acrylate and mono(meth)acrylate simultaneously. The equivalent ratio of (meth)acrylated:polyamine and/or poly(meth)acrylate:polyamine:mono(meth)acrylate can be any of those described above or any other suitable ratio; it will be appreciated, however, that use of a stoichiometrically equivalent amount of polyamine, or an excess of polyamine, may be desired. In this manner, the polyamine and poly(meth)acrylate react such that there is at least some amine termination. The result is a (meth)acrylated amine that is reactive and thus can function as a curative.
Any dialkyl maleates and/or dialkyl fumarates can be used according to present invention. Examples of maleates and fumarates include but are not limited to esters of maleic acid and fumaric acid with monoalcohols such as dimethyl, diethyl, di-n-propyl, di-isopropyl, di-n-butyl, di-sec-butyl, di-tert-butyl, di-isobutyl, di-penyl, di-t-amyl, di-hexyl, cyclohexyl and di-2-ethylhexyl maleates or the corresponding fumarates. In certain embodiments, dialkyl maleates or dialkyl fumarates with two different alkyl groups and/or mixtures of dialkyl maleates and dialkyl fumarates can be used. The alkyl groups of dialkyl maleate and/or dialkyl fumarate may comprise additional functional groups such as hydroxyl groups, such as the reaction product of maleic anhydride, an alcohol, and an epoxy, the reaction product of maleic acid or fumaric acid with an alcohol and an epoxy, or the reaction product of maleic acid or fumaric acid with an epoxy. Suitable alcohols include but are not limited to methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, various isomeric pentanols, various isomeric hexanols, cyclohexanol, 2-ethylhexanol, and the like. Suitable epoxies include but are not limited to ethylene oxide, propylene oxide, 1,2-epoxybutane, and glycidyl neodecanoate (an example of which is CARDURA E10P, Hexion Speciality Chemicals, Inc.).
It will be appreciated that the (meth)acrylated amine curatives described above can be reacted with any other functionality to form, for example, a coating. In a particular example, the (meth)acrylated amine curative is reacted with an isocyanate to form a urea. It will be appreciated that the various polyamines, (meth)acrylates and in certain embodiments maleates-fumarates as described above can be selected so as to impart the desired properties to the resulting coating. Certain desired properties that can be affected through selection of various polyamines and/or (meth)acrylates and/or maleates-fumarates include glass transition temperature (“Tg”), softening point (“Ts”), “tack time”, and Shore D hardness.
For example, when the (meth)acrylated amine curatives described above are reacted with an isocyanate to form a urea coating, the urea coating will have different physical properties as compared with when other amine curatives are used. Any suitable isocyanate can be reacted with the acrylated amine to form a polyurea.
As used herein, the term “isocyanate” includes unblocked compounds capable of forming a covalent bond with a reactive group such as a hydroxyl or amine functional group. In alternate non-limiting embodiments, the isocyanate of the present invention can be monomeric containing one isocyanate functional group (NCO) or the isocyanate of the present invention can be polymeric, i.e. “polyisocyanates”, containing two or more isocyanate functional groups (NCOs). The polyisocyanates can be selected from monomers, prepolymers, oligomers, or blends thereof. In an embodiment, the polyisocyanate can be C2-C20 linear, branched, cyclic, aromatic, or blends thereof.
Suitable isocyanates for use in the present invention may include but are not limited to isophorone diisocyanate (IPDI), which is 3,3,5-trimethyl-5-isocyanato-methyl-cyclohexyl isocyanate; hydrogenated materials such as cyclohexylene diisocyanate, 4,4′-methylenedicyclohexyl diisocyanate (H12MDI); mixed aralkyl diisocyanates such as tetramethylxylyl diisocyanates, OCN—C(CH3)2—C6H4C(CH3)2—NCO; polymethylene isocyanates such as 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HMDI), 1,7-heptamethylene diisocyanate, 2,2,4-and 2,4,4-trimethylhexamethylene diisocyanate, 1,10-decamethylene diisocyanate and 2-methyl-1,5-pentamethylene diisocyanate; and mixtures thereof.
Examples of aromatic isocyanates for use in the present invention may include but are not limited to phenylene diisocyanate, toluene diisocyanate (TDI), xylene diisocyanate, 1,5-naphthalene diisocyanate, chlorophenylene 2,4-diisocyanate, bitoluene diisocyanate, dianisidine diisocyanate, tolidine diisocyanate, alkylated benzene diisocyanates, methylene-interrupted aromatic diisocyanates such as methylenediphenyl diisocyanate, 4,4′-isomer (MDI) including alkylated analogs such as 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, polymeric methylenediphenyl diisocyanate; and mixtures thereof.
In certain embodiments, an excess of polyisocyanate monomer (i.e., residual free monomer from the preparation of prepolymer) may be used to decrease the viscosity of the polyurea composition thereby improving its flowability, and, when used in a coating, may provide improved adhesion of the polyurea coating to a previously applied coating and/or to an uncoated substrate. In alternate embodiments of the present invention, at least 1 percent by weight, or at least 2 percent by weight, or at least 4 percent by weight of the isocyanate component comprises at least one polyisocyanate monomer (i.e. residual free polyisocyanate monomer).
In a further embodiment of the invention, the isocyanate can include oligomeric polyisocyanates including but not limited to dimers, such as the uretdione of 1,6-hexamethylene diisocyanate, trimers, such as the biuret and isocyanurate of 1,6-hexanediisocyanate and the isocyanurate of isophorone diisocyanate, and polymeric oligomers. Modified polyisocyanates can also be used, including but not limited to carbodiimides and uretone-imines, and mixtures thereof. Suitable materials include but are not limited to those available under the name DESMODUR from Bayer Corporation of Pittsburgh, Pa. and include, for example, DESMODUR N 3200, DESMODUR N 3300, DESMODUR N 3400, DESMODUR XP 2410, and DESMODUR XP 2580.
In certain embodiments, the isocyanate is in the form of a prepolymer. As used herein, “prepolymer” means polyisocyanate that is pre-reacted with polyamine and/or another isocyanate reactive group such as polyol. Suitable polyisocyanates include those disclosed herein. Suitable polyamines are numerous and selected from a wide variety known in the art. Non-limiting examples of suitable polyamines may include but are not limited to primary, and secondary triamines and tetraamines, and mixtures thereof, such as any of those listed above. Amines comprising tertiary amine functionality can be used provided that the amine further comprises at least two primary and/or secondary amino groups. In certain embodiments an isocyanate such as 4,4′-methylenedicyclohexyl diisocyanate (DESMODUR W) is reacted with JEFFAMINE D4000, JEFFAMINE D2000, and/or a difunctional, amine terminated polypropylene glycol having a molecular weight higher than 4000 to form the isocyanate prepolymer. Suitable polyols are numerous and selected from a wide variety known in the art. Examples of suitable polyols may include but are not limited to polyether polyols, polyester polyols, polyurea polyols (e.g. the Michael reaction product of an amino functional polyurea with a hydroxyl functional (meth)acrylate), polycaprolactone polyols, polycarbonate polyols, polyurethane polyols, polyvinyl alcohols, addition polymers of unsaturated monomers with pendant hydroxyl groups, such as those containing hydroxy functional (meth)acrylates, allyl alcohols and mixtures thereof.
In certain embodiments, the polyurea compositions of the present invention can additionally include other amines such as those known in the art, including but not limited to any polyamines or combinations thereof listed herein. Other suitable amines include, but are not limited to, monoamines, secondary cycloaliphatic diamines, aspartic ester functional materials, polyoxyalkyleneamines, (meth)acrylate modified amines, reaction products of materials having primary amines and acrylonitrile, and oligomers or polymers formed by addition polymerization, such as free radical or cationic polymerization of unsaturated monomers that comprise pendant amino groups. Suitable monoamines include but are not limited to primary amines of the formula R2—NH2, where R2 is a hydrocarbon radical that may be represented by a straight chain or branched alkyl group, an aryl-alkyl group, a hydroxyalkyl group or an alkoxyalkyl group.
The polyurea composition disclosed above may be used to form, in whole or in part, one or more portions of a layer of a golf ball, such as a cover layer, an intermediate layer, a barrier layer, a coating layer, and the like. The golf ball cover layer or at least one sub-layer thereof (such as an inner cover layer and/or an outer cover layer) may preferably be formed from one of the compositions disclosed herein; that is, a polyurea formed from the reaction of an isocyanate and a (meth)acrylated amine curative as described herein. The layer can have a thickness from 0.001 inches to 0.125 inches, such as from 0.005 inches to 0.1 inches, or from 0.015 inches to 0.04 inches, like 0.035 inches. Alternatively, the thickness of the layer can be 0.5 inches or less, such as 0.05 inches to 0.2 inches, or 0.5 inches to 0.1 inches. The layer may have a flexural modulus of 1,000 to 100,000 psi, such as 1,000 psi to 80,000 psi, 1,000 to 50,000 psi, 1,000 psi to 30,000 psi, 2,000 psi to 25,000 psi, or 10,000 psi to 80,000 psi. The Shore D hardness of the layer may be 90 or less, such as, 20 to 70, 20 to 60, 25 to 55, 30 to 55, or 40 to 55. The layer may have a WVTR of 2 g/(m2×day) or less. The layer can have a Ts of 55° C. to 110° C., such as 85° C. In certain embodiments, the layer has a Shore D hardness of 15 to 80. Ts and Tg can be measured by methods known in the art, such as differential scanning calorimetry (DSC) and thermal mechanical analysis (TMA). Shore D and WVTR are also measurable by methods known in the art. The golf ball itself can have a Shore D hardness of 38 to 65; this will vary depending on the material(s) used in the outer layer as well as the material(s) used in any other layers of the golf ball, such as the core.
The core of the golf ball may be solid, fluid-filled, gel-filled, or gas-filled, having a single-piece construction or a multi-piece construction that includes a center and one or more outer core layers. Non-limiting examples of materials and compositions suitable for forming the core or one or more layers of the core will be known to those skilled in the art, and are described in U.S. Publication No. 2006/0014923 and the references cited therein, all of which are hereby incorporated by reference. Suitable compositions for solid cores include a base rubber (such as polybutadiene rubbers having a 1,4-cis content of at least about 40%), a crosslinking agent (such as ethylenically unsaturated acids having 3 to 8 carbon atoms and metal salts thereof), an initiator (such as peroxides, carbon-carbon initiators, and blends of two or more thereof) and, optionally, one or more additives (such as halogenated organsulfur compounds).
The golf ball core may have a diameter of 0.5 inches or greater, such as 1 inch or greater, or 1.5 inches of greater, 1.54 inches or greater, 1.545 inches or greater, or 1.55 inches or greater, typically about 1.65 or less, or about 1.6 inches or less.
The golf balls of the present invention may have a variety of constructions, typically comprising at least a core and a layer disposed about the core. The layer can be a cover layer. One or more intermediate layers may be disposed between the core and the cover; an intermediate layer can include, for example, a moisture barrier layer. The core may be a single solid mass, or include a solid, liquid-filled, gel-filled or gas-filled center and one or more outer core layers. The cover may include an outer cover layer and one or more inner layers. Any of the outer core layers, the intermediate layers, or the inner cover layers may be a continuous layer, a discontinuous layer, a wound layer, a molded layer, a lattice network layer, a web or net, an adhesion or coupling layer, a barrier layer, a layer of uniformed or non-uniformed thickness, a layer having a plurality of discrete elements such as islands or protrusions, a solid layer, a metallic layer, a liquid-filled, a gas-filled layer, or a foamed layer.
The compositions for golf balls as disclosed herein may be used in sporting equipment in general. “Sports equipment” includes but is not limited to game balls, golf club shafts, golf club head inserts, golf shoe components, and the like.
Any standard additives can be used with the polyurea according to the present invention. Such additives include, for example, catalysts, rheology modifiers, flow additives, thickeners, fillers, antistatic agents, stabilizers, adhesion promoters, antioxidants, UV absorbers, hindered amine light stabilizers, and colorants.
As used herein, the term “colorant” means any substance that imparts color and/or other opacity and/or other visual effect to the composition. The colorant can be added to the coating in any suitable form, such as discrete particles, dispersions, solutions and/or flakes. A single colorant or a mixture of two or more colorants can be used in the coatings of the present invention.
Example colorants include pigments, dyes and tints, such as those used in the paint industry and/or listed in the Dry Color Manufacturers Association (DCMA), as well as special effect compositions. A colorant may include, for example, a finely divided solid powder that is insoluble but wettable under the conditions of use. A colorant can be organic or inorganic and can be agglomerated or non-agglomerated. Colorants can be incorporated into the coatings by use of a grind vehicle, such as an acrylic grind vehicle, the use of which will be familiar to one skilled in the art.
Example pigments and/or pigment compositions include, but are not limited to, carbazole dioxazine crude pigment, azo, monoazo, disazo, naphthol AS, salt type (lakes), benzimidazolone, condensation, metal complex, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments, diketo pyrrolo pyrrole red (“DPPBO red”), titanium dioxide, carbon black and mixtures thereof. The terms “pigment” and “colored filler” can be used interchangeably.
Example dyes include, but are not limited to, those that are solvent and/or aqueous based such as pthalo green or blue, iron oxide, bismuth vanadate, anthraquinone, perylene, aluminum and quinacridone.
Example tints include, but are not limited to, pigments dispersed in water-based or water miscible carriers such as AQUA-CHEM 896 commercially available from Degussa, Inc., CHARISMA COLORANTS and MAXITONER INDUSTRIAL COLORANTS commercially available from Accurate Dispersions division of Eastman Chemical, Inc.
As noted above, the colorant can be in the form of a dispersion including, but not limited to, a nanoparticle dispersion. Nanoparticle dispersions can include one or more highly dispersed nanoparticle colorants and/or colorant particles that produce a desired visible color and/or opacity and/or visual effect. Nanoparticle dispersions can include colorants such as pigments or dyes having a particle size of less than 150 nm, such as less than 70 nm, or less than 30 nm. Nanoparticles can be produced by milling stock organic or inorganic pigments with grinding media having a particle size of less than 0.5 mm. Example nanoparticle dispersions and methods for making them are identified in U.S. Pat. No. 6,875,800 B2, which is incorporated herein by reference. Nanoparticle dispersions can also be produced by crystallization, precipitation, gas phase condensation, and chemical attrition (i.e., partial dissolution). In order to minimize re-agglomeration of nanoparticles within the coating, a dispersion of resin-coated nanoparticles can be used. As used herein, a “dispersion of resin-coated nanoparticles” refers to a continuous phase in which is dispersed discreet “composite microparticles” that comprise a nanoparticle and a resin coating on the nanoparticle. Example dispersions of resin-coated nanoparticles and methods for making them are identified in United States Patent Application Publication 2005-0287348 A1, filed Jun. 24, 2004, U.S. Provisional Application No. 60/482,167 filed Jun. 24, 2003, and U.S. patent application Ser. No. 11/337,062, filed Jan. 20, 2006, which is also incorporated herein by reference.
Example special effect compositions that may be used in the coating of the present invention include pigments and/or compositions that produce one or more appearance effects such as reflectance, pearlescence, metallic sheen, phosphorescence, fluorescence, photochromism, photosensitivity, thermochromism, goniochromism and/or color-change. Additional special effect compositions can provide other perceptible properties, such as opacity or texture. In a non-limiting embodiment, special effect compositions can produce a color shift, such that the color of the coating changes when the coating is viewed at different angles. Example color effect compositions are identified in U.S. Pat. No. 6,894,086, incorporated herein by reference. Additional color effect compositions can include transparent coated mica and/or synthetic mica, coated silica, coated alumina, a transparent liquid crystal pigment, a liquid crystal coating, and/or any composition wherein interference results from a refractive index differential within the material and not because of the refractive index differential between the surface of the material and the air.
In certain non-limiting embodiments, a photosensitive composition and/or photochromic composition, which reversibly alters its color when exposed to one or more light sources, can be used in the coating of the present invention. Photochromic and/or photosensitive compositions can be activated by exposure to radiation of a specified wavelength. When the composition becomes excited, the molecular structure is changed and the altered 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 return to a state of rest, in which the original color of the composition returns. In one non-limiting embodiment, the photochromic and/or photosensitive composition can be colorless in a non-excited state and exhibit a color in an excited state. Full color-change can appear within milliseconds to several minutes, such as from 20 seconds to 60 seconds. Example photochromic and/or photosensitive compositions include photochromic dyes.
In a non-limiting embodiment, the photosensitive composition and/or photochromic composition can be associated with and/or at least partially bound to, such as by covalent bonding, a polymer and/or polymeric materials of a polymerizable component. In contrast to some coatings in which the photosensitive composition may migrate out of the coating and crystallize into the substrate, the photosensitive composition and/or photochromic composition associated with and/or at least partially bound to a polymer and/or polymerizable component in accordance with a non-limiting embodiment of the present invention, have minimal migration out of the coating. Example photosensitive compositions and/or photochromic compositions and methods for making them are identified in U.S. application Ser. No. 10/892,919 filed Jul. 16, 2004 and incorporated herein by reference.
In general, the colorant can 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 weight percent of the present compositions, such as from 3 to 40 weight percent or 5 to 35 weight percent, with weight percent based on the total weight of the compositions.
As used herein, unless otherwise expressly specified, all numbers such as those expressing values, ranges, amounts or percentages may be read as if prefaced by the word “about”, even if the term does not expressly appear. Also, any numerical range recited herein is intended to include all subranges subsumed therein. Singular encompasses plural and vice versa. For example, although reference is made herein including the claims to “a” (meth)acrylated amine curative, “a” (meth)acrylate, “a” polyamine, “a” layer, “a” polyurea, “an” isocyanate and the like, one or more of any of these compounds or things can be used. As used herein, the term “polymer” refers to oligomers and both homopolymers and copolymers, and the prefix “poly” refers to two or more.
The following examples are intended to illustrate the invention, and should not be construed as limiting the invention in any way.
An acrylated amine curative was prepared as follows:
1DIMETHYLDICYKAN
1DIMETHYLDICYKAN, available from BASF Corporation.
Charge #1 was added to an appropriate sized, 4-necked flask equipped with a motor driven stainless steel stir blade, water-cooled condenser, and a heating mantle with a thermometer connected through a temperature feedback control device. The contents of the flask were heated to 40° C. under a nitrogen blanket and Charge #2 was added over 15 minutes. The reaction was heated to 60° C. and held for 6 hours. The temperature was increased to 70° C. and held an additional 5 hours.
Acrylated amine curatives were prepared as follows:
2Hexanediol diacrylate
2Available from Sartomer Corporation
Charge #1 was added to an appropriate sized, 4-necked flask equipped with a motor driven stainless steel stir blade, water-cooled condenser, and a heating mantle with a thermometer connected through a temperature feedback control device. The contents of the flask were heated to 71-75° C. and held until residual methyl acrylate was <2.0% (HPLC).
An acrylated amine curative was prepared as follows:
3Polyetheramine
3XTJ-510, available from Huntsman Petrochemical Corporation.
Charge #1 was added to an appropriate sized, 4-necked flask equipped with a motor driven stainless steel stir blade, water-cooled condenser, and a heating mantle with a thermometer connected through a temperature feedback control device. Charge 2 was added at a rate to keep the temperature <75° C. The contents of the flask were heated to 71-75° C. and held until residual methyl acrylate was <1.0% (HPLC).
An acrylated amine curative was prepared as follows:
4polyether triamine
4JEFFAMINE T403, available from Huntsman Petrochemical Corporation.
Charge #1 was added to an appropriate sized, 4-necked flask equipped with a motor driven stainless steel stir blade, water-cooled condenser, and a heating mantle with a thermometer connected through a temperature feedback control device. Charge 2 was added over 15 minutes. Charge #3 was added at a rate to keep the temperature <75° C. The contents of the flask were heated to 71-75° C. and held until residual methyl acrylate was <3.0% (HPLC).
An acrylated amine curative was prepared as follows:
5Polyether amine
5XTJ-502, available from Huntsman Petrochemical Corporation.
Charge #1 was added to an appropriate sized, 4-necked flask equipped with a motor driven stainless steel stir blade, water-cooled condenser, and a heating mantle with a thermometer connected through a temperature feedback control device. The contents of the flask were heated to 71° C. and held until residual methyl acrylate was <1.0% (HPLC
An isocyanate functional prepolymer was prepared as follows:
6Polyisocyanate
7Polyetherpolyamine
8Polyisocyanate
9p-Toluenesulfonyl Isocyanate
6DESMODUR W, available from Bayer Material Science LLC.
7JEFFAMINE D2000, available from Huntsman Petrochemical Corporation.
8DESMODUR N 3300A, available from Bayer Material Science LLC.
9p-Toluenesulfonyl Isocyanate, available from Aldrich.
Charge #1 was added to an appropriate sized, 4-necked flask equipped with a motor driven stainless steel stir blade, water-cooled condenser, and a heating mantle with a thermometer connected through a temperature feedback control device. The contents of the flask were heated to 50-60° C. with stirring under a nitrogen blanket. Charge #2 was added at an appropriate rate to keep the temperature <75° C. Upon completion of Charge #2, the reaction temperature was set to 70° C. and Charge #3 was added. The reaction was held at temperature until the NCO equivalent weight was close to the theory indicated in the table. Charge #4 was added and the batch was mixed for 15 minutes. Charge #5 was added and the reaction was held at temperature until the desired final NCO equivalent weight was reached.
An isocyanate functional prepolymer was prepared as follows:
10IPDI Trimer
10VESTANAT T 1890, available from Degussa Corporation.
Charge #1 was added to an appropriate sized, 4-necked flask equipped with a motor driven stainless steel stir blade, water-cooled condenser, and a heating mantle with a thermometer connected through a temperature feedback control device. The contents of the flask were heated to 50-60° C. with stirring under a nitrogen blanket. Charge #2 was added at an appropriate rate to keep the temperature <75° C. Upon completion of Charge #2, the reaction temperature was set to 70° C. and Charge #3 was added. The reaction was held 2.5 hours and the temperature set point was raised to 85° C. The reaction was held at temperature until the NCO equivalent weight was close to the theory indicated in the table. Charge #4 was added, and the temperature was increased to 115° C. to melt the solid. The temperature was then reduced to 100° C. and held until the desired final NCO equivalent weight was reached.
Isocyanate functional prepolymers were prepared as follows:
Charge #1 was added to an appropriate sized, 4-necked flask equipped with a motor driven stainless steel stir blade, water-cooled condenser, and a heating mantle with a thermometer connected through a temperature feedback control device. The contents of the flask were heated to 50-55° C. with stirring under a nitrogen blanket. Charge #2 (melted if necessary) was added at an appropriate rate to keep the temperature <75° C. Upon completion of Charge #2, the reaction temperature was set to 70° C. and Charge #3 was added. The reaction was held at temperature until the desired final NCO equivalent weight was reached.
Various polyurea cast samples (Examples 18-28) were prepared using the acrylated amine curatives and isocyanate prepolymers prepared as described above and indicated in the table below. Generally, for each sample, approximately 80 grams of the isocyanate prepolymer were measured into a paper cup. The amine curative was measured into a FlackTek cup (FlackTek Inc., Landrum S.C.) along with a pigment paste and in some cases Dibutyl Tin Dilaurate. This mixture is referred to as “curative blend”, below. The curative blend was then placed into a FlackTek SpeedMixer (FlackTex SpeedMixer DAC 400FVZ, from FlackTek Inc.), and allowed to spin for 1 minute at 2,500 rpm.
The isocyanate prepolymer was placed in the microwave oven and heated for 15 seconds on high power. Immediately after the microwave oven stopped, the curative blend was placed in the oven, together with the isocyanate prepolymer, and heated for 15 seconds on high power. These two materials were then transferred to the degassing chamber, where both materials were degassed until minimal bubbling occurred in the two samples. Once minimal to no bubbling had occurred, the materials were transferred into the microwave for an additional heating for 15 seconds on high power.
The curative blend was placed on the balance (Mettler PG5002), tared, and the isocyanate prepolymer in the amount in grams indicated in the table below was added. This mixture was sealed with a lid and was then placed into the FlackTek SpeedMixer, and allowed to spin for 5 seconds at 2,500 rpm. The sample was immediately removed from the mixer, the lid was quickly removed, and the mixed sample was poured into the Teflon mold cavity (6″×6″×⅛″, from Accrotool, Inc., New Kensington, Pa.).
The “Pour Time” was measured by a stopwatch. When the sample was placed in the mixer and started, the stopwatch was started. When the cast sample no longer flowed freely from the cup, the stopwatch was stopped. This gave a “Pour Time” range as shown in the table below.
A flat metal lid covered with Tedlar film (1.4 mil, from DuPont) was placed over the Teflon cavity containing the polyurea casting. This mold assembly was then transferred to a Carver Press (Hydraulic Unit Model #3912, from Carver, Inc., Wabash, Ind.), and heated to 150° F. Force between 10,000 lbf to 15,000 lbf was applied to the mold assembly. The sample was then cured for 15 minutes under these conditions. After 15 minutes, the Carver Press was opened, the mold assembly was removed, the metal lid with the Tedlar film was removed. An article of approximately 6 inch by 6 inch by ⅛ inch thick article was removed from the Teflon mold, and placed in a 150° F. electric oven for 120 minutes to complete curing.
After the sample was removed from the oven, the sample was allowed to equilibrate for greater than 12 hours. The sample hardness was measured by an Instron Shore D probe (Shore Instruments, Norwood, Mass.). Shore D was measured initially, when the probe hit the sample, and recorded again after two seconds.
The sample was measured for thermo-mechanical performance on a TMA 2940 Thermomechanical Analyzer (TA Instruments, New Castle, Del.). The test parameters were to start testing at 25° C., apply a temperature ramp of 10° C./min, and finish testing at 125° C. The applied force load was 0.7 lbforce. The initial softening point (“Ts”) is reported in the table below.
QUV exposure testing was performed as follows. Plaques approximately 2″ by 3″ were cut from the cast samples prepared as described above and placed into aluminum holders. A QUV Weathering Tester, Model QUV/se, from Q-Lab Corporation, Cleveland Ohio, was used with a UVA 340 bulb. The testing procedure employed a 4 hour UV light cycle at a temperature of 60° C. followed by a 4 hour humidity cycle at a temperature of 50° C. The UV irradiance on the samples was 1.00W/m2. Results are given in DE*ab in the table below.
Example 18 reflects a control, using a non-acrylated amine. The other examples, using an acrylated amine according to the present invention, have a greater thermal stability as compared to example 18, as illustrated by the greatly increased Ts values. Examples 25-28 had a markedly increased Ts as compared with the control. In addition, the TMA graphs of temperature (y axis) and dimension change (%) (x axis) (not shown) demonstrated that the rate of softening was much slower for the compositions according to the present invention than that of the control.
For purposes of QUV comparison and light stability evaluation, another control sample was prepared following the format outlined above using two commercially available products, namely 53.7 g of S28804 isocyanate prepolymer (from PPG Industries) and 10.0 g of S28774Q curative (from PPG Industries). No other ingredients were used. The Shore D of this second control was approximately 46D (initial) and approximately 44D (two seconds) and the Ts was 101° C. The DE*ab values were 49.6001 (48 hours) and 45.2553 (120 hours), demonstrating the superior QUV resistance of the present samples as compared with a commercially available product.
11Prepared as described in the Examples above, as indicated.
12Prepared as described in the Examples above, as indicated, unless indicated otherwise.
13CLEARLINK 1000, cycloaliphatic diamine, from Dorf-Ketal Chemicals, Mumbai, INDIA.
14STAN-TONE IOET03 WHITE tint paste, from Poly One Corporation, Avon Lake, OH.
The examples above were repeated, but the STAN-TONE paste was replaced with a white pigment dispersion made as described below, and the acrylated amine of Example 5 was used in addition to the acrylated amine curative indicated in the table below. The pigment dispersion was prepared by placing 100 parts of the acrylated amine of Example 5 and 127.3 parts of R-960 TiO2 pigment (DuPont Titanium Technologies, Mississauga, Ontario) into a FlackTek SpeedMixer for 5 minutes at 2,500 rpm.
15Prepared as described in the Examples above, as indicated.
16Prepared as described in the Examples above, as indicated, unless indicated otherwise.
This example illustrates that by increasing the amount of “soft segment” in the product (that is, the acrylated amine of Example 5) the Shore D can be lowered without affecting the Ts.
Whereas particular embodiments of this invention have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present invention may be made without departing from the invention as defined in the appended claims.
