• 专利附录
  • 专利说明
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    • 专利摘要:
    The present invention relates to powder coating compositions that can be cured at low temperatures. The powder coating composition of the present invention comprises a unique combination of branched oligoester polyols and uretdione crosslinkers which, when cured, result in a coating binder having the desired hardness, flexibility, solvent resistance, corrosion resistance, weather resistance and gloss. do.
    公开号:KR20010075172A
    申请号:KR1020017003448
    申请日:1999-09-09
    公开日:2001-08-09
    发明作者:파난디커캄레쉬피.；브롱크존마이클；스피틀러프랭클린폴
    申请人:게리 엘. 쿠베라；맥워터 테크날러자이즈 인코포레이티드；
    IPC主号:
    专利说明:

    Powder coating based on branched oligoesters and non-releasing uretdione polyisocyanates {POWDER COATINGS BASED ON BRANCHED OLIGOESTERS AND NON-EMISSIVE URETDIONE POLYISOCYANATES}
    [2] Thermosetting powder coating compositions are well known in the art and are widely used as coating agents for electrical appliances, bicycles, outdoor furniture, automotive industry accessories, general metal parts and the like. Thermosetting powders consist of a mixture of a primary resin and one or more crosslinkers, often referred to as solidifying or curing agents. The general approach associated with powder coating techniques is to combine and mix coatings from solid components, disperse pigments (and other insoluble components) in the matrix of the main binder component and grind the blend into powder. As far as possible, each particle contains all the elements in the formulation. The powder is applied to a substrate (usually metal, but not limited to), to fuse into a continuous film by baking.
    [3] Compositions comprising organic polyhydroxy compounds and blocked to include internal or self-blocked polyisocyanates and solid at room temperature are important binders for thermally crosslinkable powder coatings (see US Pat. Nos. 3,857,818 and US Pat. 4,375,539). During thermal crosslinking, it is a common disadvantage for these systems that the compounds used as blocking agents split apart and release into the environment, except for self / internally blocked reagents. Therefore, during curing and crosslinking, special care must be taken to purify the waste air and recover the blockers for environmental and occupational hygiene reasons.
    [4] Attempts have been made to use barrier-free uretdione group-containing polyurethane (PUR) powder coating binders to remove release from curing of powder coatings. In these compositions, cross-linking occurs with thermal cleavage of uretdione groups (see, for example, US Pat. Nos. 5,621,064 and 4,413,079). Typically, however, films produced from these types of uretdione crosslinkers do not have optimum film properties in terms of hardness, flexibility, solvent resistance, corrosion resistance, weather resistance and gloss.
    [5] Another problem with powder coating compositions is that they usually have a low glass transition temperature (Tg) and will aggregate or sinter upon storage at elevated temperatures for extended periods of time. This phenomenon may not allow the application of powder coatings with the appropriate particle size as the powder coating compositions taken in storage are agglomerated and cause application problems that require re-grinding.
    [6] It is an object of the present invention to provide a powder coating composition having a relatively high glass transition temperature and resisting coagulation during storage.
    [7] It is an object of the present invention to provide a powder coating composition that maximizes film properties such as hardness, flexibility, solvent resistance, corrosion resistance, weather resistance and gloss, in addition to providing a coating composition with a relatively high glass transition temperature. .
    [8] Still another object of the present invention is to avoid the use of an effective amount of urethane catalyst at temperatures as low as about 160 ° C. or to lower 1,5-diazabicyclo (4.3.0) non-5-ene, 1, Can be cured using an effective amount of a urethane catalyst such as 8-diazabicyclo (5.4.0) undec-7-ene, dibutyltin dilaurate, butane tartaric acid, dibutyltin oxide and other materials known in the art. To provide a powder coating composition.
    [9] It is a further object of the present invention to provide a thermosetting powder coating composition comprising a crosslinker which does not release the blocker into the environment upon curing.
    [10] It is yet another object of the present invention to provide a powder coating composition having an accelerated curing schedule and 0T bend performance at temperatures higher than about 160 ° C. which are typical requirements for coil coating applications.
    [11] It is another object of the present invention to provide a powder coating composition having a preferred melt viscosity.
    [12] Other objects, advantages, features and characteristics of the present invention will become more apparent upon consideration of the following detailed description and the appended claims.
    [1] The present invention relates to a powder coating composition which can be cured at low temperatures with or without the use of a urethane catalyst. More specifically, the present invention relates to branched hydroxyl terminal oligoesters which provide improved performance properties at low curing temperatures upon crosslinking and do not release the blocking agent from the crosslinker to the environment.
    [13] The present invention provides a powder coating composition that can be cured using no urethane catalyst at temperatures as low as about 160 ° C. or a urethane catalyst at temperatures lower than about 160 ° C. and does not readily aggregate during storage. Moreover, the present invention has the additional advantage of utilizing crosslinkers, and does not release the blockers into the environment when blocked.
    [14] The powder coating composition of the present invention comprises a unique combination of crosslinking linkages and branched oligoester polyols which results in coatings having a desired hardness, flexibility, solvent resistance, corrosion resistance, weather resistance and gloss upon curing. Branched chain oligoester polyols have a unique combination of side chain structure, average molecular weight, hydroxyl value, and acid number, which provide a relatively high glass transition temperature and consequently become coagulated. When the latter side chain oligoester polyols are cured with uretdione, the combination of side chain oligoesters and uretdione results in coatings with good performance properties that do not produce volatile organic compounds (VOCs) with or without urethane catalysts. to provide. The present invention provides an increase in high cure rates and reactivity at lower temperatures without VOCs without sacrificing storage stability due to aggregation or firing.
    [15] The branched oligoester polyols have a Tg of at least about 40 ° C. to about 80 ° C., a number average molecular weight of about 1000 to about 7500 Daltons, a hydroxyl functionality of about 1.5 to about 5.0, a hydroxyl value of about 15 to about 250, and about 1 to about 250 An acid value of about 25, and in a very important aspect, an acid value of about 5 to about 7. In another important aspect, the side chain oligoesters will have a viscosity of about 20 to about 90 poise at about 200 ° C.
    [16] The powder coating composition of the present invention comprises branched oligoester polyols and uretdione powder coating crosslinkers, each of the relative amounts being from about 0.8 to about 180 ° C. when curing is performed at temperatures below about 160 ° C. and up to about 350 ° C. It is effective to provide a crosslinked coating composition having a pencil hardness of at least about HB, a direct impact resistance of at least about 80 lb and a reverse impact resistance of at least about 80 lb at a binder thickness of about 4 mils. The powder coating composition of the present invention comprising branched oligoester polyols and uretdione has a Tg of about 40 ° C to about 80 ° C. In an important aspect, the powder coating composition comprises from about 40 to about 97 weight percent of the branched hydroxyl terminal oligoesters based on the weight of the branched oligoester polyol and crosslinker.
    [17] The branched oligoester polyols react with the diol and the double acid and then multiplex the resulting hydroxyl terminal oligoester diol with a carboxyl functionality of at least about 3 less than the stoichiometric amount (relative to hydroxyl to oligoester). By reaction with an acid to form a generally linear hydroxyl terminated oligoester diol. Less than the stoichiometric amount provides some carboxyl groups for the oligomer, but its more important purpose is generally to provide complex branching of oligoester polyols so that the oligomer chain can in some cases extend from all carboxyl functionalities of the polyacid. And some of the polyacids can be linked internally by oligomeric chains. In an important aspect, the carboxyl functionality from the polyacid reacting with the oligoester is no more than about 15% equivalent of the stoichiometric amount of carboxyl equivalent required to react with all the hydroxyl groups of the oligoester. In an important aspect, the ratio of hydroxyl terminated oligoester diol to triacid is from about 9.0: 1 to about 30: 1, preferably from about 10: 1 to about 20: 1.
    [18] In an important aspect of the present invention, hydroxyl terminated diols provide hydroxyl terminated oligoester diols having aromatic groups as reaction products of aliphatic diols (open chain or cycloaliphatic) with aromatic diacids, diacid halides, or diacid anhydrides such as terephthalic acid. . Alternatively in this aspect, the acid may be a straight or cycloaliphatic biacid, a biacid anhydride or a biacid halide, and the diol may be hydroquinone to provide oligoesters with aromatic monomers along its main chain.
    [19] In another important aspect, the diols used for the oligoester diols are straight-chain aliphatic or cycloaliphatic diols and the biacid is an alicyclic biacid, a biacid anhydride, or a biacid halide, with the monomer providing an oligoester diol having an alicyclic group.
    [20] In another aspect, if the diacids, diacid anhydrides or halides and diols used to make the oligoester diols are all straight chains, aromatic monomers having hydroxyl and carboxyl functionality can be used to improve the properties of the final coating composition. These aromatic monomers having hydroxyl and carboxyl functionality include ortho, meta and parahydroxybenzoic acid. While not wishing to be bound by any theory, ring and straight chain blending, or aromatic cycloaliphatic blending, appears to provide desirable film properties.
    [21] Hydroxyl terminated oligoester diols are the reaction products of diacids and excessive amounts of diols. Dual acids are neopentin glycol, 1,6 hexane diol, 2-butyl-2-ethyl-1,3-propane diol, 1,4 cyclohexanedimethanol, diethylene glycol, 1,3 propanediol, hydrogenated bisphenol A, 2,3,4,4-tetramethyl-1,3-cyclobutanediol, ethylene glycol, propylene glycol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2-ethyl-2-isobutyl- 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, thiodiethanol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1, 4-xylylenediol, ethoxylated bisphenol A, ester diol 204 (Union Carbide), 3-hydroxy-2,2-dimethyleneproprionate, unoxol 6 diol, methyl propanediol, 2-methyl-1 , 3-propane diol, hydroxypivalyl hydroxypivalate (HPHP), vinyl cyclohexanediol, dipropylene glycol, ester diol, dimethylol proprioric acid (DMPA), and mixtures thereof It may be one or more diols.
    [22] The aromatic acids / anhydrides / acid anhydrides used in the present invention include terephthalic acid, phthalic acid, phthalic anhydride, dimethyl terephthalic acid, naphthalene dicarboxylate, tetrachlorophthalic acid, terephthalic acid bisglycol ester, isophthalic acid, t-butyl isophthalic acid, and their Selected from the group consisting of mixtures.
    [23] Aliphatic acids / anhydrides / acid anhydrides useful in the present invention include fumaric acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, glutaric acid, succinic acid, oxalic acid, itaconic acid, dimer fatty acids, maleic anhydride, succinic anhydride, Chloric acid, diglycolic acid, nadic acid, and mixtures thereof.
    [24] Alicyclic acids / anhydrides / acid anhydrides used in the present invention include 1,4-cyclohexane diacid, 1,3-cyclohexane dicarboxylic acid, hexahydrophthalic anhydride, dimethyl cyclohexane dicarboxylate, and mixtures thereof It may include acid / anhydrides such as. Mixtures of these compounds can also be used for the preparation of ester diols.
    [25] Aromatic diols or dihydroxy phenolic compounds that can be used to make oligoesters include hydroquinone, catechol, resorcinol, p, p'-dihydroxy diphenyl methane, bisphenol A, p, p'-dihydroxy di Phenyl ketone, p, p'-dihydroxydiphenyl, and mixtures thereof. Usually when dihydroxy compounds of this phenol type are used to make oligoester diols, base catalysis is usually required.
    [26] The reaction to form the hydroxyl terminated oligoester diols is carried out at a time and temperature effective to provide oligoester diols having a number average molecular weight in the range from about 400 to about 1500 Daltons, and then the reaction is from about 170 ° C to about 200 ° C. Slowed by cooling of the furnace to give the latter oligoester diol. In general, the reaction providing the oligoester diol is carried out at a temperature of 240 ° C. for about 4 to about 15 hours before the reaction is cooled.
    [27] This relatively low molecular weight hydroxyl terminated oligoester diol is then multiplexed selected from citric acid, pyromellitic anhydride, trimellitic anhydride, trimethylolpropane, trimethylolethane, pentaerythritol, and ditrimetholol propane. React with acids / anhydrides / polyols or mixtures thereof. In an important aspect of the present invention, the polyacid or triacid reacted with hydroxyl terminated oligoester diols is an aromatic acid. The branching reaction is carried out at a time and temperature effective to provide the branched oligoester polyols described herein. The reaction to form the branched oligoester polyols is carried out for about 4 to about 15 hours at a temperature of about 180 ° C to about 240 ° C.
    [28] Uretdione is an important crosslinker of the present invention. The amount of crosslinker in the composition is effective to provide an equivalent ratio of isocyanate groups to hydroxyl groups of about 0.5: 1 to about 1.8: 1.
    [29] In an important aspect of the present invention, uretdione has the following structure.
    [30]
    [31] Wherein R is 4,4'-diisocyanatodicyclohexylmethane, 1,4-diisocyanatobutane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl Cyclohexane, 1,3- and 1,4-phenylene diisocyanate, naphthylene-1,5-diisocyanate, 2,4- and / or 2,6-toluylene diisocyanate, diphenylmethane-2,4 '-And / or 4,4'-isocyanates, 1,3- and 1,4-diisocyanatocyclohexane, 1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 2 Monomers such as 2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,5-diisocyanato-2,2-dimethylpentane, and other substances known in the art Compounds from acidic diisocyanates.
    [32] The uretdione structure is separated from unreacted excess of isocyanate monomer in the presence of a catalyst as a result of catalytic dimerization of monomeric diisocyanate. Unreacted isocyanate groups of uretdione structure are then chain stretched with the ester diols. A typical uretdione structure may be a dimerization product of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (isophorone diisocyanate; IPDI). Typical functionalities of these oligomers are approximately two. Known uretdione dimers are thermally cut in the presence of a catalyst at lower temperatures to give cured powder coatings at low temperature bake schedules. The uncatalyzed uretdione dimer reacts with the hydroxyl groups of the branched oligoester polyols, usually at approximately 160 ° C., to form thermally cut and further cured powder coating compositions. Catalyzed uretdione dimers in powder coatings react with the hydroxyl groups of the branched oligoester polyols in thermally cut and even cured powder coating compositions at temperatures lower than 160 ° C.
    [33] Incision of the uretdione ring in the presence of the hydroxyl functional reactant is initiated at a temperature as low as about 160 ° C., and the curing of the powder coating composition proceeds without requiring an effective amount of polyurethane catalyst. Generally less than about 0.02 weight percent urethane catalyst, based on the weight of the powder coating composition, is not effective for urethane catalysis and does not increase the reaction rate. When cured by mixing with the branched oligoester polyols, uretdione is opened to produce a hardened powder coating by producing isocyanate (NCO) groups such that the uretdione ring crosslinks with the hydroxyl groups of the branched oligoesters. It also does not emit volatiles. In an important aspect, when uretdione is used as a crosslinking agent in the composition, the composition comprises from about 3 to about 60 weight percent of a uretdione powder coating crosslinking agent based on the weight of the side chain oligoester polyol and the crosslinking agent. Include.
    [34] In another aspect, the invention provides a powder wherein the side chain oligoester polyols prepared as described herein are blended with uretdione powder coating crosslinkers and optionally other materials commonly used in the preparation of powder coatings. Provided are methods for preparing the coating composition.
    [35] As used herein, “coating binder” is the polymeric portion of the coating film after baking and after crosslinking.
    [36] “Polymer vehicle” is in a compounded coating; That is, it means all the polymeric and resinous components before film formation. The pigments and additives may be mixed with the polymer vehicle to provide a blended powder coating composition.
    [37] "Diol" is a compound having two hydroxyl groups. "Polyol" is a compound having two or more hydroxyl groups.
    [38] "Diacid" is a compound with two carboxyl groups. A "polyacid" is a compound having two or more carboxyl groups, which may be an acid or an acid anhydride.
    [39] A "film" is formed by applying a powder coating composition to a base or substrate and crosslinking it.
    [40] By "firing" is meant the loss of particulate properties of agglomerates and condensates during storage, or, in severe cases, powders causing a solid mass. An amount of material effective to provide a substantially non-fired powder coating is used in the compositions of the present invention. "Substantially non-fired" means that the powder retains its particle properties such that it has only a few agglomerates that can be easily broken at moderate pressure after exposure to the prescribed conditions of room temperature after cooling.
    [41] A "catalyst" is defined as an additive that is added to the resin / cured or powder coating composition at a desired concentration level that accelerates the chemical reaction at the defined temperature and pressure. The type of catalyst used may be described as gas, liquid and / or solid. Solid catalysts may be coated onto the support / carrier to provide a defined catalyst level per weight of catalyst for a defined level of activity. The catalysts described are not limited to esterification, transesterification and urethane cure chemical reactions.
    [42] "Polyester" is used in the polymer main chain It means a polymer having a connection. "Oligomer" means a compound that generally has repeating monomer units and is similar to a polymer, but has a number average weight not greater than about 7500 Daltons, with or without repeating monomer units. A "polymer" will have a number average molecular weight of greater than about 7500 Daltons.
    [43] Acid number or acid value means the number of milligrams of potassium hydroxide required for the neutralization of the free acid present in 1 g of the resin.
    [44] "Hydroxy number" or "hydroxyl number", also called "acetyl number", is a number indicating the extent to which a substance can be acetylated; This is the number of milligrams of potassium hydroxide required for the neutralization of free acetic acid to saponify 1 g of acetylated sample.
    [45] Side-chain hydroxyl terminated oligoester resin
    [46] Both Tg and melt viscosity of the resin are greatly influenced by the choice of monomers. In an important aspect of the invention, the side chain hydroxyl terminated oligoester resin is made by a two step process. In step 1, hydroxyl terminated oligoester diols are prepared, and in step 2 side chain hydroxyl terminated oligoester polyols are formed.
    [47] Step 1 : The hydroxyl terminated oligoester diol in step 1 is used to convert stoichiometric molar excess of diol (relative to carboxyl to acid) to dicarboxylic acid, such as dicarboxylic acid, dicarboxylic anhydride, or acid chloride. It is formed by esterification or condensation reaction with a halide.
    [48] (1) Diols that may be used in the reaction are neopentyl glycol, 1,6 hexane diol, 2-butyl-2-ethyl-1,3-propane diol, 1,4 cyclohexanedimethanol, diethylene glycol, 1,3 Propanediol, hydrogenated bisphenol A, 2,3,4,4-tetramethyl-1,3-cyclobutanediol, ethylene glycol, propylene glycol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2 -Ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, thiodiethanol, 1,2-cyclohexanedimethanol, 1,3 -Cyclohexanedimethanol, 1,4-xylylenediol, ethoxylated bisphenol A, ester diol 204 (Union Carbide), 3-hydroxy-2,2-dimethylproprionate, unoxol 6 diol, methyl Propanediol, 2-methyl-1,3-propane diol, hydroxypivalyl hydroxypivalate (HPHP), vinyl cyclohexanediol, dipropylene glycol, ester diol, dimethylol proprioric acid (DMPA), and their Group consisting of mixtures Can be selected from.
    [49] Hydroquinone, catechol, resorcinol, p, p'-dihydroxy diphenyl methane, bisphenol A, p, p'-dihydroxy diphenyl ketone, p, p'-dihydroxydiphenyl, and their Aromatic diols, such as mixtures, can also be reacted with straight or alicyclic biacids.
    [50] (2) Aromatic biacids, aliphatic biacids and / or cycloaliphatic biacids or anhydrides or acid halides can be used to make hydroxyl terminated diols.
    [51] In an important aspect, the aromatic acid / anhydride / acid anhydride is terephthalic acid, phthalic acid, phthalic anhydride, dimethyl terephthalic acid, naphthalene dicarboxylate, tetrachlorophthalic acid, terephthalic acid bisglycol ester, isophthalic acid, t-butyl isophthalic acid, and mixtures thereof It is selected from the group consisting of or acid halides thereof.
    [52] Aliphatic acids / anhydrides / acid halides that may be used in the present invention include fumaric acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, glutaric acid, succinic acid, oxalic acid, itaconic acid, dimer fatty acids, maleic anhydride, succinic acid Anhydrides, chloric acid, diglycolic acid, nadic acid and mixtures thereof.
    [53] Alicyclic acids / anhydrides / acid anhydrides that may be used in the present invention include 1,4-cyclohexane diacid, 1,3-cyclohexane dicarboxylic acid, hexahydrophthalic anhydride, dimethyl cyclohexane dicarboxylate, and their Acid / anhydrides such as mixtures.
    [54] Mixtures of these compounds can also be used for the preparation of ester diols as mixed functional intermediates. Ester diols are those prepared by known methods from dihydric alcohols and lactones as starting molecules via ring opening reactions. The preparation of ester diols comprises β-propiolactone, γ-butyrolactone, γ- and delta-valerolactone, ε-caprolactone, 3,5,5- and 3,3,5-trimethylcaprolactone or their Lactones such as mixtures. Suitable starting materials include the dihydric alcohols listed.
    [55] In a very important aspect of the present invention, the aromatic acid is at least one aromatic acid selected from the group consisting of terephthalic acid (TPA), isophthalic acid (IPA), and t-butyl isophthalic acid. They react with aliphatic or cycloaliphatic diols such as neopentyl glycol, 1,6 hexane diol, 2-butyl-2-ethyl, 1,3-propanediol, and 1,4-cyclohexane dimethanol.
    [56] The diol component and the biacid component are each present in an effective amount to provide a coating composition having the described properties and subsequent coating. In an important aspect of the present invention, the combination of neopentyl glycol and 1,6 hexane diol in a molar ratio of about 4.0: 1 to about 7.0: 1, preferably about 5.6: 1, comprises TPA, IPA or t-butyl isophthalic acid. And a coating composition having an acceptable Tg.
    [57] The reaction to obtain the hydroxyl terminated oligoester diol can be carried out at about 240 ° C. for about 4 to about 15 hours and then cooled to obtain a generally linear product with Mn of about 400 to about 1500 Daltons. Aliphatic acids include hydroquinone, catechol, resorcinol, p, p'-dihydroxy diphenyl methane, bisphenol A, p, p'-dihydroxy diphenyl ketone, p, p'-dihydroxydiphenyl, and When reacting with aromatic dihydroxy compounds such as mixtures thereof, the use of a base catalyst is usually required.
    [58] Step 2 : In step 2, the hydroxyl terminated oligoester diol prepared in step 1 is reacted to form side chain hydroxyl terminated oligoester polyol. In an important aspect of the invention, the hydroxyl terminated oligoester prepared in step 1 reacts with a blend of polyacid / anhydride or polyacid / anhydride that is at least triacid. The triacid, or triacid blend, is selected from the group consisting of trimellitic anhydride (TMA) and citric acid. In a very important aspect, the triacid is an aromatic acid such as trimellitic anhydride.
    [59] In an important aspect of the invention, the resulting side chain hydroxyl terminal oligoesters have a hydroxyl functionality of about 1.5 to about 5.0, a hydroxyl number of about 15 to about 250, an acid value of about 1 to about 25, and about 1000 to about It has a number average molecular weight in the range of 7500 Daltons. The side chain hydroxyl terminal oligoesters have a Tg of at least about 40 ° C., in an important aspect, from about 40 ° C. to about 80 ° C. In a very important aspect, the ratio of hydroxyl terminal oligoesters to polyacids is from about 9.0: 1 to about 30: 1.
    [60] Crosslinking agent
    [61] Uretdione crosslinkers : In an important aspect of the invention, the uretdione crosslinkers are internally blocked isocyanates or dimers of isocyanates. Examples of uretdione crosslinkers acceptable for use in the present invention include Crelan LS2147 (Bayer) and Alcure 4147 (McWhorter Technologies). The preparation of the uretdione crosslinker provides an average NCO functionality of about 1.9 based on the free NCO groups. The free NCO content is typically less than about 1%. In a very important aspect, the powder coating composition comprises from about 3 to about 60 weight percent of uretdione crosslinker based on the weight of the side chain hydroxyl terminated oligoester polyol and the crosslinker.
    [62] Preparation and Application of Thermosetting Powders
    [63] For the preparation of thermosetting powder compositions, side chain hydroxyl terminated oligoester resins, crosslinkers, and various auxiliary materials commonly used for the preparation of powder coatings and paints are mixed uniformly. This homogenization allows the oligoesters, crosslinkers and various auxiliary materials to be used at temperatures ranging from about 70 ° C. to about 130 ° C., preferably extruders, such as Buss-Ko-Kneader extruders or twins of the Werner-Pfleiderer or Baker Perkins type. -By melting, for example in a screw extruder. The extrudate is then cooled, crushed and sieved to obtain the appropriate powder for electrostatic or fluidized bed applications.
    [64] Another factor affecting viscosity and flow is the level of pigments and fillers in the system. High levels of pigments and / or fillers reduce the flow of the system by increasing the melt viscosity. Fine particle sized organic pigments such as carbon black, phthalocyanine blue, quinacridone result in a significant increase in melt viscosity even at low levels.
    [65] Auxiliary materials which can be added to the thermosetting powder compositions according to the invention are ultraviolet absorbing compounds such as Tinubin 900 (from CIBA-GEIGY Corp.), light stabilizers based on steric hindrance amines (eg from CIBA-GEIGY Corp.). Tinuvin 144), phenolic antioxidants (such as Irganox 1010 and Irgafos from CIBA-GEIGY Corp.) and stabilizers of the phosphonite or phosphite type. In addition, various pigments may be added to the thermosetting powder composition according to the present invention. Examples of pigments that can be used in the present invention include metal oxides such as titanium dioxide, iron oxides, zinc oxides, metal hydroxides, metal powders, sulfides, sulfates, carbonates, carbon blacks, iron blues, organic red pigments, organic yellow pigments, organic chestnuts. Pigments and the like. Auxiliary materials also include flow regulators such as Resiflow PV5 (from WORLEE), Modaflow 3 and 2000 (from Monsanto), Acronal 4F (from BASF), Resiflow P-67 (from Estron), dicyclohexyl phthalate, triphenyl phosphate Plasticizers, milling aids and degassing agents such as benzoin may also be included. Examples of fillers are calcium carbonate, magnesium carbonate, blanc fixe, barite, silicate, talc, Chinese clay and the like. These auxiliary materials will be added in conventional amounts, but if the thermosetting powder composition of the present invention is used as a clear coating, it should be understood that the auxiliary material to make it opaque is omitted.
    [66] In addition, urethane catalysts may also be mixed with the thermosetting powder compositions of the present invention. Catalysts useful in the present invention include 1,5-diazabicyclo (4.3.0) non-5-ene, 1,8-diazabicyclo (5.4.0) undec-7-ene, dibutyltin dilaurate, Butane tartaric acid, dibutyltin oxide, tin oxide and others known in the art.
    [67] Powder coating compositions of the present invention are conventional techniques such as electrostatic or tribostatic spray guns; It is suitable for application to articles to be coated by means of Powder Cloud technology (Material Science Corporation) or by, but not limited to, well-known fluidized bed coating techniques. In an important aspect, the compositions of the present invention can be used to supply very thick coatings.
    [68] After being applied on the article in question, the deposited coating is cured by heating in an oven. In an important aspect, catalyst-free curing is performed for less than about 35 minutes at temperatures as low as about 160 ° C. to obtain sufficient crosslinking to provide the described coating properties. Alternatively, desirable coating properties can be obtained by curing at about 200 ° C. for about 5 minutes, heating at about 180 ° C. for about 15 minutes and heating at about 350 ° C. for about 40 seconds. Curing by infrared (IR) or induction heating is also applicable. In an aspect of the invention wherein a urethane catalyst is used, preferred coating properties can be obtained by curing for about 10 to about 30 minutes at temperatures as low as about 130 ° C.
    [69] The following examples illustrate the methods for practicing the present invention and should be understood as illustrative and not for limiting the scope of the invention as defined in the appended claims.
    [70] Example 1
    [71] Step 1
    [72] Preparation of hydroxyl terminal oligomers
    [73] Reactant weight
    [74] Neopentyl glycol (Eastman) 805 grams
    [75] 1,6 hexanediol (UBE) 161 g
    [76] Terephthalic Acid (Amoco) 1145 grams
    [77] Butylchlorotin Dioxide (Elf-Atochem) 2.1 grams
    [78] Antioxidant (Weston 618-General Electric) 4.6 g
    [79] The mixture is gradually heated to 205 ° C. and then treated at 240 ° C. with an acid value of 4 to 7 mg KOH / gram resin with a plate viscosity of 10-14 poises and an ICI cone at 125 ° C. The hydroxyl number of this oligomer was found to be about 130-140 mg KOH / gram resin.
    [80] Step 2
    [81] Preparation of hydroxyl terminal side chain oligoesters
    [82] The oligomer is cooled to 180 ° C. and 153.5 grams of trimellitic anhydride are added. Raise the temperature to 210-215 ° C. and slowly apply vacuum over a 50 minute period until a vacuum of 23-24 inches of mercury is obtained. Samples are taken regularly and the reaction is monitored by measuring the acid value and ICI cone and plate viscosity at 200 ° C. When a plate viscosity of ICI cones and 50-60 poises and an acid value of 4-10 mg KOH / gram resin are obtained, the melt is cooled to 195 ° C. and released from the flask. The color of the resin is almost colorless / transparent to light yellow. Further examples of hydroxyl terminal side chain oligoesters are shown in Table 1.
    [83] Example 2
    [84] Preparation of Powder Coating
    [85] All oligoesters are made of high gloss, white powder coatings prepared as follows:
    [86] 1000 grams of oligoester resin of Example 1
    [87] Alcure 4147 (McWhorter Technologies) 310 g
    [88] Modaflow 2000 (Flow Level-Monsanto) 15 g
    [89] 6 grams of benzoin (degassed)
    [90] Titanium Dioxide (DuPont R-960) 450g
    [91] All the above elements are initially mixed in a high speed mill such as a Welex mixer to ensure uniform mixing. The resulting mixture is treated with Zone 1 at 80 ° C and Zone 2 at 122 ° C via a twin screw extruder (ZSK 30 Werner-Phleider). The resulting melt is discharged into a pair of water cooled squeeze rolls from which the cooling sheet is roughly broken before grinding in a Brinkman mill. The resulting powder is sieved through a 100 mesh screen. This powder coating is electrostatically sprayed onto the ground steel panel. The physical properties of the blended powder coatings are evaluated after 5 minutes curing at 200 ° C. for 1.5-2.2 mill film thickness. These powder coating compositions and test results are provided in Table 2.
    [92] Table 1 below contains examples of oligoesters prepared by the same technique as shown in Example 1.
    [93] Table 1
    [94] Compositions and Properties of Oligoesters
    [95] Composition (grams)One234567 Neopentyl Glycol 1,6 Hexane Diol Terephthalate Butyl Chlorotin DihydrateWeston 618 Trimellitic Anhydride953-11452.264.52161.008818011442.264.52163.008818011442.264.52163.008788011402264.52171.0080916111452.264.52155.0080616011382.264.52163.0080416011352.264.52171.00 Gun-H 2 O2265.78265.782274.78274.782274.78274.782275.78275.782276.78276.782273.78273.782276.78276.78 yield2000.002000.002000.002000.002000.002000.002000.00 ICI Viscosity at 200 ° C Number of Resin Properties Acid Hydroxide Glass Transition Temperature ° C Number Average Molecular Weight (GPC)10.160556629508.355625931407.262626036669.565575931905.264525131237.464555331799.36461523042
    [96] TABLE 2
    [97] Film evaluation of oligoester
    [98] SuzyOne23456730-3000 controlCompetitive Balance 1Competitive Resin 2 Glossy 60 ° 20 °9282928090729276927789759076907691788866 Impact resistance (lb)1601601601601601601601601601601601601601608010160160160160 MEK Rubs * (50 double friction)44433.54433.53 Flow / Leveling **6666666742 Gel Time 400 ° F89908377948077929847 45 ° Tilted Plate Fill Flow @ 375 ℉, mm15014812614714513912615015098 * Visually evaluated on a scale of 0-5 (0 = very bad, 5 = excellent) ** PCI flow scale on a scale of 1-10 (0 = bad flow, 10 = smooth)
    [99] Numerous variations and modifications in the practice of the invention are expected to occur to those skilled in the art in view of the foregoing detailed description. Accordingly, such modifications and variations are intended to be included within the scope of the following claims.
    权利要求:
    Claims (46)
    [1" claim-type="Currently amended] About 15 to about 250 hydroxyl value, about 1 to about 25 acid value, and about 1000 to about 7500 daltons, which is a reaction product of a hydroxyl terminal oligoester diol with a polyacid or anhydride having at least about 3 carboxyl functionality Branched hydroxyl terminal oligoester polyols having a number average molecular weight in the range; And a uretdione crosslinker, wherein the side chain hydroxyl terminated oligoester polyol and the crosslinker are each at a temperature of about 160 ° C. without using an effective amount of a urethane catalyst and using a urethane catalyst. A pencil hardness of at least about HB, a direct impact resistance of at least about 80 lb and at least about 80 at a cured film thickness of about 0.8 to about 4.0 mils, present in a relative amount effective to cure the powder coating composition at temperatures lower than 160 ° C. A powder coating composition having a Tg of at least about 40 ° C., which provides a cured coating with a reverse impact resistance of lb.
    [2" claim-type="Currently amended] The powder coating composition of claim 1 wherein the ratio of hydroxyl terminal oligoester diol to polyacid is from about 9: 1 to about 30: 1.
    [3" claim-type="Currently amended] The hydroxyl-terminated oligoester diol of claim 2 wherein the open chain aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid, open chain aliphatic dicarboxylic acid anhydride, alicyclic dicarboxylic acid anhydride Is a reaction product of a diol and a diacid reactant selected from the group consisting of aromatic dicarboxylic anhydrides, open chain dicarboxylic acid halides, alicyclic dicarboxylic acid halides, aromatic dicarboxylic acid halides, and mixtures thereof, and diol The reaction of the double acid with the diacid is conducted at a time and temperature effective to provide a hydroxyl terminated oligoester diol having a molecular weight ranging from about 400 to about 1500 Daltons.
    [4" claim-type="Currently amended] The diol of claim 3 wherein the diol is neopentyl glycol, 1,6 hexane diol, 2-butyl-2-ethyl-1,3-propane diol, 1,4 cyclohexanedimethanol, diethylene glycol, 1,3 propanediol Hydrogenated bisphenol A, dimethylol proprioric acid, 2,3,4,4-tetramethyl-1,3-cyclobutanediol, ethylene glycol, propylene glycol, 2,4-dimethyl-2-ethylhexane-1,3 -Diol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, thiodiethanol, 1,2-cyclohexanedimethanol , 1,3-cyclohexanedimethanol, 1,4-xylylenediol, ethoxylated bisphenol A, 3-hydroxy-2,2-dimethylproprionate, methyl propanediol, 2-methyl-1, Powder coating composition selected from the group consisting of 3-propane diol, hydroxypivalyl hydroxypivalate, vinyl cyclohexanediol, dipropylene glycol, dimethylol proprioric acid, aromatic diol compounds, and mixtures thereof .
    [5" claim-type="Currently amended] The aromatic acid of claim 4, wherein the diacid reactant is a terephthalic acid, phthalic acid, phthalic anhydride, dimethyl terephthalic acid, naphthalene dicarboxylate, tetrachlorophthalic acid, terephthalic acid bisglycol ester, isophthalic acid, t-butyl isophthalic acid, and mixtures thereof A powder coating composition comprising an aromatic biacid reactant which is an acid anhydride or an acid halide.
    [6" claim-type="Currently amended] The biacid reactant according to claim 4, wherein the biacid reactant is fumaric acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, glutaric acid, succinic acid, oxalic acid, itaconic acid, dimer fatty acid, maleic anhydride, succinic anhydride, chloric acid A powder coating composition comprising an open chain aliphatic diacid reactant which is an open chain aliphatic acid, acid anhydride or acid halide of diglycolic acid, nad acid and mixtures thereof.
    [7" claim-type="Currently amended] The cycloaliphatic acid of claim 4, wherein the diacid reactant is a 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, hexahydrophthalic acid, dimethyl cyclohexane dicarboxylic acid, and mixtures thereof. Powder coating composition comprising a cycloaliphatic biacid reactant which is an alicyclic anhydride or an alicyclic acid halide.
    [8" claim-type="Currently amended] The diol of claim 5 wherein the diol is selected from the group consisting of neopentyl glycol, 1,6 hexane diol, 2-butyl-2-ethyl-1,3-propane diol, 1,4 cyclohexanedimethanol, and mixtures thereof Powder coating composition.
    [9" claim-type="Currently amended] The powder coating composition of claim 8 wherein the biacid reactant is an aromatic acid, anhydride of an aromatic acid, or an acid halide selected from the group consisting of terephthalic acid, isophthalic acid, t-butyl isophthalic acid, and mixtures thereof.
    [10" claim-type="Currently amended] The oligoester diols of claim 1 wherein the oligoester diols are β-propiolactone, γ-butyrolactone, γ- and delta-valerolactone, ε-caprolactone, 3,5,5- and 3,3,5-trimethyl A powder coating composition, which is a reaction product of a captone, and a dihydric alcohol compound selected from the group consisting of caprolactone and mixtures thereof.
    [11" claim-type="Currently amended] 10. The powder coating composition of claim 1, 2, 5, 8 or 9 wherein the polyacid is at least triacid.
    [12" claim-type="Currently amended] The powder coating composition of claim 11 wherein the triacid is selected from the group consisting of trimellitic anhydride, citric acid, and mixtures thereof.
    [13" claim-type="Currently amended] The powder coating composition of claim 11, wherein the triacid is trimellitic anhydride.
    [14" claim-type="Currently amended] The powder coating composition of claim 1, wherein the side chain hydroxyl terminated oligoester polyol has a hydroxyl functionality of about 1.5 to about 5.0.
    [15" claim-type="Currently amended] 3. The powder of claim 1, wherein the powder coating composition has from about 40 to about 97 wt% of the side chain hydroxyl terminated oligoester polyol, based on the weight of the side chain hydroxyl terminated oligoester polyol and crosslinking agent. Coating composition.
    [16" claim-type="Currently amended] 3. The powdered cow of claim 1, wherein the powder coating composition has from about 3 to about 60% by weight of a uretdione crosslinker based on the weight of the side chain hydroxyl terminated oligoester polyol and the crosslinker. Composition.
    [17" claim-type="Currently amended] The reaction of claim 3, 8, or 9, wherein the reaction to form the hydroxyl terminal oligoester diols is cooled to about 170 ° C. to about 200 ° C. to provide oligoester diols having a molecular weight of about 400 to about 1500 Daltons. Powder coating composition.
    [18" claim-type="Currently amended] Powder coating effective to provide coatings having a pencil hardness of at least about HB, direct impact resistance of at least about 80 lb, and reverse impact resistance of at least about 80 lb when applied to a substrate in a binder film of about 0.8 to about 4.0 mils. As a method of preparing the composition,
    Hydroxyl products ranging from about 15 to about 250, acid values from about 1 to about 25, and from about 1000 to about 7500 daltons as reaction products of a polyacid / anhydride having at least about 3 carboxyl functionalities and a hydroxyl terminated oligoester diol The side chain hydroxyl terminal oligoester polyols having a number average molecular weight in the range are prepared at a temperature of about 160 ° C. without using an effective amount of a urethane catalyst and at a temperature below about 160 ° C. using an effective amount of a urethane catalyst. A method of making a powder coating composition comprising blending with a uretdione crosslinker present in an amount effective to cure and effective to provide an equivalent ratio of isocyanate groups to hydroxyl groups of about 0.5: 1 to about 1.8: 1. .
    [19" claim-type="Currently amended] The method of claim 18, wherein the ratio of hydroxyl terminal oligoester diol to polyacid is from about 9: 1 to about 30: 1.
    [20" claim-type="Currently amended] The hydroxyl-terminated oligoester diol of claim 19 wherein the open chain aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid, open chain aliphatic dicarboxylic anhydride, alicyclic dicarboxylic acid anhydride Is a reaction product of a diol and a diacid reactant selected from the group consisting of aromatic dicarboxylic anhydrides, open chain dicarboxylic acid halides, alicyclic dicarboxylic acid halides, aromatic dicarboxylic acid halides, and mixtures thereof, diol And the reaction of the biacid is conducted at a time and temperature effective to provide a hydroxyl terminated oligoester diol having a molecular weight ranging from about 400 to about 1500 Daltons.
    [21" claim-type="Currently amended] 21. The aromatic acid of claim 20, wherein the biacid reactant is an aromatic acid of terephthalic acid, phthalic acid, phthalic anhydride, dimethyl terephthalic acid, naphthalene dicarboxylate, tetrachlorophthalic acid, terephthalic acid bisglycol ester, isophthalic acid, t-butyl isophthalic acid, and mixtures thereof. A method for producing a powder coating composition comprising an aromatic biacid reactant which is an acid anhydride, an acid halide.
    [22" claim-type="Currently amended] The cycloaliphatic acid of claim 20, wherein the diacid reactant is 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, hexahydrophthalic acid, dimethyl cyclohexane dicarboxylic acid, and mixtures thereof. And a cycloaliphatic biacid reactant which is a cycloaliphatic anhydride or a cycloaliphatic acid halide.
    [23" claim-type="Currently amended] The diol of claim 20 wherein the diol is selected from the group consisting of neopentyl glycol, 1,6 hexane diol, 2-butyl-2-ethyl-1,3-propane diol, 1,4 cyclohexanedimethanol, and mixtures thereof And the diacid reactant is selected from the group consisting of aromatic diacid reactants, cycloaliphatic biacid reactants, and mixtures thereof, wherein the aromatic diacid reactant is terephthalic acid, phthalic acid, phthalic anhydride, dimethyl terephthalic acid, naphthalene dicarboxylate, tetrachlorophthalic acid, Aromatic acids, acid anhydrides or acid halides of terephthalic acid bisglycol esters, isophthalic acid, t-butyl isophthalic acid, and mixtures thereof, and the alicyclic reactants are 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane Cycloaliphatic acid, cycloaliphatic anhydride or cycloaliphatic acid hala of dicarboxylic acid, hexahydrophthalic acid, dimethyl cyclohexane dicarboxylic acid and mixtures thereof Deuin, process for preparing a powder composition Koh Ting.
    [24" claim-type="Currently amended] The method of claim 23, wherein the polyacid is at least triacid.
    [25" claim-type="Currently amended] The method of claim 24, wherein the side chain hydroxyl terminated oligoester polyol has a hydroxyl functionality of about 1.5 to about 5.0.
    [26" claim-type="Currently amended] The powder coating composition of claim 24, wherein the reaction to form the hydroxyl terminated oligoester diol is cooled to about 170 ° C. to about 200 ° C. to provide an oligoester diol having a molecular weight of about 400 to about 1500 Daltons. How to.
    [27" claim-type="Currently amended] A reaction product of a hydroxyl terminated oligoester diol having a molecular weight ranging from about 400 to about 1500 Daltons and a polyacid having a carboxyl functionality of at least about 3, wherein the hydroxyl value ranges from about 15 to about 250, from about 1 to about 25 And branched hydroxyl terminal oligoester polyols having an acid value of and a number average molecular weight ranging from about 1500 to about 7500 Daltons.
    [28" claim-type="Currently amended] The hydroxyl-terminated oligoester diol of claim 27 wherein the open chain aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid, open chain aliphatic dicarboxylic anhydride, alicyclic dicarboxylic acid anhydride , A side chain hydroxide which is a reaction product of a diol and a diacid reactant selected from the group consisting of aromatic dicarboxylic anhydrides, open chain dicarboxylic acid halides, alicyclic dicarboxylic acid halides, aromatic dicarboxylic acid halides, and mixtures thereof Oxyl terminated oligoester polyols.
    [29" claim-type="Currently amended] The method of claim 28, wherein the diol is neopentyl glycol, 1,6 hexane diol, 2-butyl-2-ethyl-1,3-propane diol, 1,4 cyclohexanedimethanol, diethylene glycol, 1,3 propanediol Hydrogenated bisphenol A, dimethylol proprioric acid, 2,3,4,4-tetramethyl-1,3-cyclobutanediol, ethylene glycol, propylene glycol, 2,4-dimethyl-2-ethylhexane-1, 3-diol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, thiodiethanol, 1,2-cyclohexanedi Methanol, 1,3-cyclohexanedimethanol, 1,4-xylylenediol, ethoxylated bisphenol A, 3-hydroxy-2,2-dimethylproprioonate, methyl propanediol, 2-methyl-1 Side chain hydroxyl selected from the group consisting of, 3-propane diol, hydroxypivalyl hydroxypivalate, vinyl cyclohexanediol, dipropylene glycol, dimethylol proprioric acid, aromatic diol compounds, and mixtures thereof Terminal oligoester polyols.
    [30" claim-type="Currently amended] 30. The aromatic acid of claim 29, wherein the biacid reactant is a terephthalic acid, phthalic acid, phthalic anhydride, dimethyl terephthalic acid, naphthalene dicarboxylate, tetrachlorophthalic acid, terephthalic acid bisglycol ester, isophthalic acid, t-butyl isophthalic acid, and mixtures thereof And branched hydroxyl terminal oligoester polyols comprising an aromatic biacid reactant which is an acid anhydride or an acid halide.
    [31" claim-type="Currently amended] The method of claim 29, wherein the biacid reactants are fumaric acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, glutaric acid, succinic acid, oxalic acid, itaconic acid, dimer fatty acids, maleic anhydride, succinic anhydride, chloric acid , Open chain aliphatic diacid reactant which is an open chain aliphatic acid, acid anhydride or acid halide of diglycolic acid, nad acid and mixtures thereof.
    [32" claim-type="Currently amended] The cycloaliphatic acid of claim 29, wherein the biacid reactant is a 1,4-cyclohexane dicarboxylic acid, a 1,3-cyclohexane dicarboxylic acid, a hexahydrophthalic acid, a dimethyl cyclohexane dicarboxylic acid, and mixtures thereof. , Branched hydroxyl terminal oligoester polyol comprising an alicyclic diacid reactant which is an alicyclic anhydride or an alicyclic acid halide.
    [33" claim-type="Currently amended] The diol of claim 28 wherein the diol is selected from the group consisting of neopentyl glycol, 1,6 hexane diol, 2-butyl-2-ethyl-1,3-propane diol, 1,4 cyclohexanedimethanol, and mixtures thereof And the diacid reactant is selected from the group consisting of aromatic diacid reactants, cycloaliphatic biacid reactants, and mixtures thereof, wherein the aromatic diacid reactant is terephthalic acid, phthalic acid, phthalic anhydride, dimethyl terephthalic acid, naphthalene dicarboxylate, tetrachlorophthalic acid, Aromatic acids, acid anhydrides or acid halides of terephthalic acid bisglycol esters, isophthalic acid, t-butyl isophthalic acid, and mixtures thereof, and the alicyclic reactants are 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane Cycloaliphatic acid, cycloaliphatic anhydride or cycloaliphatic acid hala of dicarboxylic acid, hexahydrophthalic acid, dimethyl cyclohexane dicarboxylic acid and mixtures thereof Deuin, branched hydroxyl terminated oligoester polyol.
    [34" claim-type="Currently amended] The oligoester diol of claim 28 wherein the oligoester diol is β-propiolactone, γ-butyrolactone, γ- and delta-valerolactone, ε-caprolactone, 3,5,5- and 3,3,5-trimethyl Side chain hydroxyl-terminated oligoester polyols which are the reaction products of caprolactone and lactones selected from the group consisting of mixtures thereof, and dihydric alcohol compounds.
    [35" claim-type="Currently amended] 34. The side chain hydroxyl terminated oligoester polyol of claim 28, 29, 30, 31, 32 or 33 wherein the polyacid is at least triacid.
    [36" claim-type="Currently amended] 36. The branched hydroxyl terminal oligoester polyol of claim 35, wherein the triacid is selected from the group consisting of trimellitic anhydride, citric acid, and mixtures thereof.
    [37" claim-type="Currently amended] 37. The side chain hydroxyl terminated oligoester polyol of claim 36, wherein the triacid is trimellitic anhydride.
    [38" claim-type="Currently amended] As a process for preparing the side chain hydroxyl terminated oligoester polyols:
    Blending the hydroxyl terminated oligoester diol with a polyacid having a carboxyl functionality of at least about 3;
    Hydroxyl terminated diols and polyacids are provided with side chain hydroxyl terminated oligoester polyols having a hydroxyl value ranging from about 15 to about 250, an acid value ranging from about 1 to about 25, and a number average molecular weight ranging from about 1500 to about 7500 daltons. Reaction at an effective time and temperature, wherein the hydroxyl terminated oligoester diols are open chain aliphatic dicarboxylic acids, cycloaliphatic dicarboxylic acids, aromatic dicarboxylic acids, open chain aliphatic dicarboxyls Selected from the group consisting of acid anhydrides, alicyclic dicarboxylic acid anhydrides, aromatic dicarboxylic acid anhydrides, open chain dicarboxylic acid halides, alicyclic dicarboxylic acid halides, aromatic dicarboxylic acid halides, and mixtures thereof Reaction products of diacid reactants and diols, diols and diacids have a number average molecular weight ranging from about 400 to about 1500 Daltons React at the time and temperature to give an excited hydroxyl terminated diol, and diol and biacid at a time such that the oligoester diol reaches a number average molecular weight in the range of about 400 to about 1500 before reacting the hydroxyl terminated diol and the polyacid. A process for producing side chain hydroxyl terminated oligoester polyols, in which the reaction of is cooled.
    [39" claim-type="Currently amended] The process of claim 38, wherein the ratio of hydroxyl terminal oligoester to polyacid is from about 9: 1 to about 30: 1.
    [40" claim-type="Currently amended] 40. The aromatic acid of claim 39, wherein the biacid reactant is an aromatic acid of terephthalic acid, phthalic acid, phthalic anhydride, dimethyl terephthalic acid, naphthalene dicarboxylate, tetrachlorophthalic acid, terephthalic acid bisglycol ester, isophthalic acid, t-butyl isophthalic acid, and mixtures thereof. A process for preparing side chain hydroxyl terminated oligoester polyols comprising an aromatic biacid reactant which is an acid anhydride or an acid halide.
    [41" claim-type="Currently amended] The cycloaliphatic acid of claim 39, wherein the biacid reactant is 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, hexahydrophthalic acid, dimethyl cyclohexane dicarboxylic acid, and mixtures thereof. And a cycloaliphatic diacid reactant which is a cycloaliphatic anhydride or a cycloaliphatic acid halide.
    [42" claim-type="Currently amended] 40. The compound of claim 39 wherein the diol is selected from the group consisting of neopentyl glycol, 1,6 hexane diol, 2-butyl-2-ethyl-1,3-propane diol, 1,4 cyclohexanedimethanol, and mixtures thereof And the diacid reactant is selected from the group consisting of aromatic diacid reactants, cycloaliphatic biacid reactants, and mixtures thereof, wherein the aromatic diacid reactant is terephthalic acid, phthalic acid, phthalic anhydride, dimethyl terephthalic acid, naphthalene dicarboxylate, tetrachlorophthalic acid, Aromatic acids, acid anhydrides or acid halides of terephthalic acid bisglycol esters, isophthalic acid, t-butyl isophthalic acid, and mixtures thereof, and the alicyclic reactants are 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane Cycloaliphatic acid, cycloaliphatic anhydride or cycloaliphatic acid hala of dicarboxylic acid, hexahydrophthalic acid, dimethyl cyclohexane dicarboxylic acid and mixtures thereof Deuin oligonucleotide branched hydroxyl terminated process for producing a polyester polyol.
    [43" claim-type="Currently amended] 40. The process of claim 39, wherein the polyacid is at least triple acid.
    [44" claim-type="Currently amended] 44. The method of claim 43, wherein the side chain hydroxyl terminated oligoester polyol has a hydroxyl functionality of about 1.5 to about 5.0.
    [45" claim-type="Currently amended] 43. The process of claim 38 or 42, wherein the reaction between the diol forming the hydroxyl terminated oligoester diol and the biacid is cooled to between about 170 [deg.] C and about 200 [deg.] C.
    [46" claim-type="Currently amended] The reaction of claim 38 or 43, wherein the reaction between the hydroxyl terminated oligoester diol and the triacid forming the side chain hydroxyl terminated oligoester polyol is carried out at a temperature of about 180 ° C. to about 240 ° C. for about 4 to about 15 hours. A process for preparing side chain hydroxyl terminated oligoester polyols.
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    同族专利:
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    KR100650829B1|2006-11-27|
    ZA200102125B|2002-06-14|
    US6255523B1|2001-07-03|
    EP1114020B1|2004-08-25|
    JP2002526569A|2002-08-20|
    WO2000017148A1|2000-03-30|
    CN1318045A|2001-10-17|
    EP1114020A4|2001-12-12|
    US20020091206A1|2002-07-11|
    EP1114020A1|2001-07-11|
    AU769617B2|2004-01-29|
    CA2344540A1|2000-03-30|
    EP1481963A1|2004-12-01|
    AT274488T|2004-09-15|
    CN100357247C|2007-12-26|
    BR9913799B1|2012-02-07|
    CZ2001980A3|2001-08-15|
    DE69919730D1|2004-09-30|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-09-18|Priority to US09/156,254
    1998-09-18|Priority to US09/156,254
    1999-09-09|Application filed by 게리 엘. 쿠베라, 맥워터 테크날러자이즈 인코포레이티드
    2001-08-09|Publication of KR20010075172A
    2006-11-27|Application granted
    2006-11-27|Publication of KR100650829B1
    优先权:
    申请号 | 申请日 | 专利标题
    US09/156,254|US6255523B1|1998-09-18|1998-09-18|Power coatings based on branched oligoesters and non-emissive uretdione polyisocyanates|
    US09/156,254|1998-09-18|
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