JP2009504845A - Novel polyester amide imide and composition for wire covering based on polyester amide - Google Patents

Abstract

  A wire coating composition comprising a resin having a nucleophilic group and optionally a resin containing an amide group, which can be cross-linked with each other, comprising (A) OH, NHR, SH, carboxylate, and CH-acidic 5 to 95% by weight of at least one resin having a nucleophilic group selected from the group consisting of groups, (B) 0 to 70% by weight of a resin containing at least one amide group, and (C) at least one kind And the resin of component (A) or component (B) contains an α-carboxy-β-oxocycloalkylcarboxylic acid amide group, and the weight of (A) to (C) A composition with a total of 100 percent. The wire coating composition according to the present invention allows a significant increase in enamelization rate without losing the positive properties of standard wire enamel.

Description

This application claims the benefit of US Provisional Application No. 60 / 706,460, filed Aug. 8, 2005, which is hereby incorporated by reference in its entirety.

  The present invention relates to a novel polyester amide imide and a novel wire coating composition based on a polyester amide that provides an excellent enamel surface for conductive wires at high enamelization rates and is useful for coating conductors. .

  Currently commonly used wire coatings are suitable organic solvents such as cresol, phenol, benzyl alcohol, propylene carbonate, or N-methylpyrrolidone; dilution of xylene, other substituted aromatics, aliphatics, etc. And enameled wire such as THEIC [Tris (hydroxyethyl) isocyanurate] polyester, polyester, polyamide, polyamide-imide, THEIC polyesterimide, polyesterimide, or polyurethane in small amounts of additives, catalysts, and regulators It is a binder solution. The solvent evaporates during thermal curing of the wire coating. In order to obtain a high quality coating, it is necessary to eliminate the solvent as completely as possible. In addition to the solvent, the by-products of the curing reaction also move from the enamelled phase to the gas phase that arises during crosslinking by the condensation reaction.

  The user of the wire coating makes an effort to obtain the best possible method for the user by enamelling the wire coating for a short time and then increasing the yield of conductive enameled wire as much as possible. In order to achieve proper crosslinking, not only the solvent but also the cleavage products of the crosslinking reaction must be removed as completely as possible from the enamel, even at high enamelling rates. The oven temperature or catalysis of the crosslinking reaction, or both parameters, must therefore be increased to allow substantial crosslinking despite the relatively short residence time of the wire in the oven. As the cross-linking becomes faster, the viscosity rises rapidly and therefore dissipation of the solvent and condensation products should also occur in a much shorter time. Thus, the process window is much smaller and the stability of the wire enamelling process is greatly limited. Therefore, the occurrence of specific enamel defects such as bubbles and dents is almost inevitable.

  As shown in the following patents, various methods have been employed in the past to increase the rate at which the wire enamel is applied to the electrical conductor.

  EP 873198 (A) describes enamels representing polyamidoamines attached to low molecular acrylates by the Michael reaction.

  DE-A-3133571 (A) proposes a polyurethane wire enamelling system containing tris (hydroxyethyl) isocyanurate in addition to the polyol and (block) isocyanate components. This system can have a higher enamelization rate than similar compositions without tris (hydroxyethyl) isocyanurate. However, this method is limited to polyurethane wire enamel.

  German Patent Application Publication No. 19648830 (A) proposes a polyesterimide wire enameled resin that enables a high enamelization rate. First, a polyimide is formed by reacting a polyisocyanate or polyamine with an acid or acid anhydride and reacted with a polyol to form a polyesterimide, followed by reaction with an acid or anhydride. This polyesterimide is specifically characterized by having a significant number of acid groups in addition to the hydroxy groups. The enamelization rate is limited by the OH-COOH esterification reaction that generally occurs slower than the transesterification reaction.

The present invention is a wire coating composition comprising a resin having a nucleophilic group capable of crosslinking with each other, and optionally a resin containing an amide group,
(A) 5 to 95% by weight of at least one resin having a nucleophilic group selected from the group consisting of OH, NHR, SH, carboxylate, and CH-acidic groups;
(B) 0 to 70% by weight of a resin containing at least one amide group;
(C) including at least one organic solvent in an amount of 5 to 95% by weight,
When the component (A) resin or component (B) is included in the composition, the component (B) resin contains an α-carboxy-β-oxocycloalkylcarboxylic acid amide group, and (A) to (C ) In a total of 100 percent.

  The wire coating composition according to the present invention allows a significant increase in enamelization rate without losing the positive properties of standard wire enamel. The wire coating according to the present invention is stable during storage, exhibits good adhesion to a round profiled conductive wire, and has adequate heat shock resistance. Extremely high surface quality is achieved with very good electrical, thermal and mechanical properties, in particular at high enamelling rates. Surprisingly, the enamel according to the invention also has better adhesion and better mechanical properties than those of the prior art.

  In addition, phenolic and / or melamine resins, catalysts, nanoscale particles, and / or element-organic compounds, optionally commonly used additives and / or adjuvants, and pigments and / or fillers. The composition for covering electric wires is preferable.

This type of wire coating composition
(A) 5-60% by weight of at least one resin having a nucleophilic group selected from the group consisting of OH, NHR, SH, carboxylate, and CH-acidic groups;
(B) 1 to 50% by weight of a resin containing at least one amide group;
(C) at least one organic solvent in an amount of 5 to 90% by weight;
(D) 0-10% by weight of at least one catalyst, preferably 0.1-20% by weight;
(E) at least one phenolic resin and / or melamine resin and / or block isocyanate 0-20% by weight, preferably 0.1-10% by weight;
(F) 0 to 3 wt%, preferably 0.1 to 3 wt% of commonly used additives or adjuvants,
(G) 0-70% by weight of nanoscale particles, preferably 0.1-70% by weight;
(H) 0 to 60% by weight of a commonly used filler and / or pigment, preferably 0.1 to 60% by weight,
The resin of component (A) or component (B) contains an α-carboxy-β-oxocycloalkyl carboxylic acid amide group, and the weight percent of (A) to (H) is 100 percent in total.

  Resins known for covering electric wires can be used as component (A). These can be polyesters or polyesters having a heterocyclic nitrogen-containing ring, for example, polyesters having condensed imide, hydantoin and benzimidazole structures into molecules. Polyesters are specifically polybasic aliphatic, aromatic and / or alicyclic carboxylic acids and their anhydrides, polyhydric alcohols, and in the case of polyesters containing imides, compounds containing polyester amino groups, And optionally a condensation product of a predetermined amount of a monofunctional compound, for example a monohydric alcohol. Saturated polyesterimides are preferably based on terephthalic acid polyesters which can also contain, in addition to diols, polyols and the reaction product of diaminodiphenylmethane and trimellitic anhydride as an additional dicarboxylic acid component. Furthermore, unsaturated polyester resins and / or polyester imides and polyacrylates can also be used. As component A, the following: polyamides such as thermoplastic polyamides, aromatic, aliphatic and aromatic-aliphatic polyamides, and also polyamideimides of the type produced, for example, from trimelletic anhydride and diisocyanato-diphenylmethane Can also be used.

  Preferably, unsaturated polyesters and / or polyester imides are used.

  The composition according to the invention may further contain one or more other types of binders well known and common in the wire coating industry. These include, for example, polyester, polyesterimide, polyamide, polyamideimide, THEIC-polyesterimide, polytitanate-THEIC-esterimide, phenolic resin, melamine resin, polymethacrylic imide, polyimide, polybismaleimide, polyetherimide , Polybenzoxazinedione, polyhydantoin, polyvinyl formal, polyacrylate and derivatives thereof, polyvinyl acetal, and / or masked isocyanate. Preferably, a polyester and THEIC- polyesterimide (Reference: Behr, "Hochtemperaeturbestandige Kunststoffe" Hanser Verlage, Munich 1969; Cassidy, "Thermally Stable Polymers" New York: Marcel Dekker, 1980; Frazer, "High Temperature Resistant Polymers New York: Interscience, 1968; Mail, Kunststoffe 77 (1987) 204).

The resin containing the amide of component (B) contains an α-carboxy-β-oxocycloalkyl carboxylic acid amide group as a component useful in the present invention. The α-carboxy-β-oxocycloalkyl carboxylic acid amide group is preferably incorporated at the terminal site. The α-carboxy group is preferably alkyl- or aryl-esterified. On the other hand, this type of α-carboxy-β-oxocycloalkylcarboxylic acid amide is produced by reaction with an amine group from a reactive derivative such as a corresponding carboxylic acid, carboxylic acid halide or carboxylic anhydride group. can do. It is also advantageous to use an amidation aid such as dicyclohexylcarbodiimide during the synthesis from the amine and carboxylic acid. α-Carboxy-β-oxocycloalkyl carboxylic acids can be obtained, for example, by reaction with haloformates under basic conditions and subsequent selective saponification. 1-carboxy-2-oxocycloalkane can be obtained, for example, by synthesis from 1, n-carboxylic acid diester by reaction with a base accompanied by alcohol cleavage. On the other hand, the α-carboxy-β-oxocycloalkylcarboxylic acid amide can also be produced by the reaction of the 1-carboxy-2-oxocycloalkane with an isocyanate under basic conditions. Examples of the 1-carboxy-2-oxocycloalkane include glutaric acid dialkyl ester, glutaric acid diaryl ester, adipic acid dialkyl ester, adipic acid diaryl ester, pimelic acid dialkyl ester, pimelic acid diaryl ester, octanedioic acid dialkyl ester, and octane. Obtained from diacid diaryl esters and alkyl-, aryl-, alkoxy-, aryloxy-, alkylcarboxy-, arylcarboxy-, halogen-, and other substituted derivatives thereof, particularly preferably dimethyl adipate and ethyl esters it can. Examples of the isocyanate include propylene diisocyanate, trimethylene diisocyanate, tetramethyle diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, ethylethylene diisocyanate, 3,3,4 -Trimethylhexamethylene diisocyanate, 1,3-cyclopentyl diisocyanate, 1,4-cyclohexyl diisocyanate, 1,2-cyclohexyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene di- Isocyanate, 2,5-toluylene diisocyanate, 2,6-toluylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,5-naphthylene diisocyanate, 1,4-naphthylene diisocyanate, 4 , 4'- Phenyl methane diisocyanate, 2,4'-diphenylmethane diisocyanate; aniline, formaldehyde, and derived from the reaction of COCl _2,> 2 pieces of polynuclear isocyanates having a functionality; 4,4'-dicyclohexylmethane diisocyanate Narate, 2,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, triisocyanatononane, or oligomers and polymers made from these isocyanates (eg, uretdione, isocyanurate, etc.) .

  For example, ethylene glycol, propylene glycol, butanediol, 1,3-propanediol, hexanediol, neopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, and other diols, triols, tetraols, polyols, or amino alcohols, It is also possible to use an excess of urethane or urea obtained from said isocyanate which can be obtained by reaction with diamines, triamines and polyamines.

  The above-mentioned amines used for amidation are aliphatic diamines such as ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine and hexamethylenediamine, and alicyclic diamines such as 4,4'-dicyclohexylmethanediamine. Or a triamine and a secondary amine can be used. The amine can also be an aromatic amine such as diaminodiphenylmethane, phenylenediamine; a polynuclear aromatic amine having> 2 possible groups, toluylenediamine, or the corresponding derivative. Use amines with other functional groups in the molecule, for example amino alcohols such as monoethanolamine and / or monopropanolamine, or amino acids such as glycine, aminopropanoic acid, aminocaproic acid or aminobenzoic acid, and esters thereof It is also possible.

  The α-carboxy-β-oxocycloalkyl carboxylic acid amide group can also be directly incorporated into component (A). This can be achieved, for example, by reaction of the component (A) resin with a di- or polyisocyanate and at least one carboxy-β-oxocycloalkane.

  As component (C), the composition may contain one or more organic solvents such as aromatic hydrocarbons, N-methylpyrrolidone, cresol, phenol, xylenol, styrene, vinyltoluene, methyl acrylate and the like.

  Catalysts such as tetrabutyl titanate, isopropyl titanate, cresol titanate, polymer forms thereof, dibutyltin dilaurate, another tin catalyst can be used individually or as a mixture as component (D).

  Phenol resins and / or melamine resins that can be used as component (E) are, for example, novolaks obtainable by polycondensation of phenol and aldehyde, or polyvinyl formal obtainable from polyvinyl alcohol and aldehydes and / or ketones can do.

Block isocyanates such as polyols, amines, C—H-acidic compounds (eg, acetoacetate, malonate, etc.), and NCO-adducts of diisocyanates (eg, reference, Methoden der org. -Weyl, Georg Thieme Verlag, Stuttgart, 4 ^th edition, Vol. Generally used as a blocking agent.

  Common additives and adjuvants for component (F) include, for example, extenders, plastic components, accelerators (eg, metal salts, substituted amines), initiators (eg, photoinitiators, thermoresponsive initiators). Common enamel additives such as stabilizers (eg, hydroquinone, quinone, alkylphenols, alkylphenol ethers), defoamers, and flow control agents.

The nanoscale particles of the component (G) include particles having an average particle diameter in the range of 1 to 300 nm, preferably in the range of 2 to 80 nm. These include, for example _{SiO 2, Al 2 O 3,} TiO 2, boric nitride, an inorganic nanoscale particles based on compounds, such as silicon carbide. The particles are, for example, silicon, zinc, aluminum, tin, boron, germanium, gallium, lead, transition metals, and the series consisting of lanthanides and actinides, specifically silicon, titanium, zinc, yttrium, cerium, vanadium, hafnium, zirconium , Nickel, and / or a compound based on an element-oxygen network containing elements from the series consisting of tantalum. The surface of the element-oxygen network of these particles can be modified with reactive organic groups, for example as described in EP 1166283 (A).

The composition comprises, as component (H), pigments and / or fillers based on, for example, SiO ₂ , Al ₂ O ₃ , TiO ₂ , Cr ₂ O ₃ , for example color imparting inorganics such as titanium dioxide and carbon black and / or Alternatively, organic pigments and effect pigments such as metal flake pigments and / or pearlescent pigments can be included.

  The coating composition may further contain monomeric and / or polymeric element-organic compounds. Examples of polymer organic-element compounds include inorganic-organic hybrid polymers of the type described in DE 198 41 977 (A), for example. Examples of monomeric organic-element compounds include ortho-titanates such as nonyl, cetyl, stearyl, triethanolamine, diethanolamine, acetylacetone, acetoacetate, tetraisopropyl, cresyl, tetrabutyltitanate and zirconate and / or Examples include ortho-zirconate, titanium tetralactate, hafnium and silicon compounds such as hafnium tetrabutoxide and tetraethyl silicate, and / or various silicone resins. Additional polymers and / or monomeric organic-element compounds of this type can be included in the composition according to the invention, for example in a content of 0 to 70% by weight.

  Component (A) and component (B) can enter a chemical reaction during the baking process. Depending on the chemical nature of component (A) and component (B), suitable reactions well known to those skilled in the art include, for example, transesterification, polymerization, polyaddition, and condensation reactions. An addition reaction between component (A) and component (B), for example, ring opening in (B) by nucleophilic attack of (A) is preferred. The polyesteramide imide wire coating or the polyesteramide wire coating is produced by a chemical reaction during the baking process.

  The composition according to the invention can optionally be mixed with common wire enamel and subsequently applied in a conventional manner.

  The composition according to the present invention can be applied in a conventional manner regardless of the type and diameter of the conductive wire used. The wires can be coated directly with the composition according to the invention and subsequently baked (baked) in an oven. Coating and baking may be performed several times in succession. The ovens can be arranged horizontally or vertically and the coating conditions such as coating time and frequency, baking temperature, coating speed, etc. are adapted to the type of wire to be coated. For example, the coating temperature can be in the range of room temperature to 400 ° C. Furthermore, ambient temperatures above 400 ° C., for example up to 800 ° C. and above, may be possible during the enamelling process without affecting the quality of the coating according to the invention. Baking can be aided by irradiating with infrared (IR) and / or near infrared (NIR) by techniques well known to those skilled in the art.

  The composition according to the invention can be used irrespective of the type and diameter of the conductive wire. For example, an electric wire having a diameter of 5 μm to 6 mm can be covered. For example, a general metal conductor made of copper, aluminum, zinc, iron, gold, silver, or an alloy thereof can be used as the electric wire.

  The coating composition according to the invention can be contained as a component of a multilayer enamel. This multilayer enamel can contain, for example, at least one coating composition according to the invention.

  According to the present invention, the conductive wire may or may not be coated with an existing finish. Existing finishes can be, for example, insulating coatings and flame retardant coatings. In such a case, the thickness of the coating layer according to the present invention may vary greatly.

  It is also possible to apply another coating, for example another insulating coating, via the coating according to the invention. These coatings can also be used, for example, as a topcoat to improve mechanical protection, produce desired surface properties, and provide a smooth surface. For example, polyamide, polyamideimide, and polyimide based compositions are particularly suitable as topcoats.

  In particular, the composition according to the invention is also suitable for application as a single layer.

  According to the present invention, the composition can be applied with a typical layer thickness. For example, a thin layer of 5-10 μm can be applied without affecting the partial discharge resistance achieved by the present invention or the finish adhesion, strength, and extensibility. The thickness of the dried layer can vary depending on the standard values for thin conductive wires and thick conductive wires. For example, a thin wire has a thin thickness of 5 to 10 μm, and a thick wire has a thickness of about 75 to 89 μm.

  The invention is illustrated by the following examples.

test:
Solid content [%] 1 g, 1 hour, 180 ° C. (corresponding to DIN EN ISO 3251)
Viscosity at 25 ° C. [mPas] or [Pas] (corresponding to DIN 53015)

Example 1 (as component A, THEIC-polyesterimide)
122.4 g ethylene glycol, 37.5 g propylene glycol, 171.5 g dimethyl terephthalate in a 2 liter, 3-necked flask equipped with stirrer, thermometer and distillation apparatus (distillation tower and distillation bridge) (DMT) 237.7 g of tris (hydroxyethyl) isocyanurate (THEIC) and 1.0 g of ortho-titanic acid tetrabutyl ester are heated to 205 ° C. for 4 hours. 55 g of methanol are distilled off. After cooling to 150 ° C., 277.8 g trimellitic anhydride (TMA) and 143.2 g methylenedianiline (DADM) are added. The mixture is heated with stirring to 210 ° C. within 3 hours and maintained at this temperature until the viscosity of the solid resin reaches 710 mPas (1: 2, 25 ° C. in m-cresol). 52 g of water are distilled off. The residue is then cooled to 180 ° C. and 509 g of cresol is added. The solid content of the obtained polyesterimide solution is 60.3%.

Example 2 (as component A, THEIC-polyester)
105.9 g ethylene glycol, 464.5 g dimethyl terephthalate (DMT), 416.6 g in a 2 liter three-necked flask equipped with stirrer, thermometer and distillation equipment (distillation tower and distillation bridge) Of tris (hydroxyethyl) isocyanurate (THEIC), 0.4 g of zinc acetate, and 0.4 g of ortho-titanic acid tetrabutyl ester were heated to 220 ° C. within 3 hours with stirring to obtain a solid resin. Maintain at this temperature until the viscosity reaches 700 mPas (1: 2, m-cresol, 25 ° C.). 153 g of water is distilled off. The mixture is then cooled to 180 ° C. and 490.5 g of cresol is added at a maximum of 150 ° C. with 21.6 g of ortho-titanate tetrabutyl ester. The solid content of the obtained polyester solution is 59.7%.

Example 3 (component B as a polyurethane resin containing an amide group)
150.0 g of xylene, 346.5 g of Desmodur® 44 M, 0.2 g of general catalyst (in a 2 liter, 3-necked flask equipped with stirrer, reflux condenser and thermometer ( Hydroxide), 49.6 g of trimethylolpropane, and 216.5 g of 2-oxo-cyclopentylcarboxylic acid ethyl ester at 70 ° C. until the NCO number drops to <6.5% after about 4 hours. Heat. The mixture is then cooled to 40 ° C. and 160.0 g of polyesterimide resin solution (30.2% solids in cresol, hydroxyl number: 322 mg KOH / g) is added and heated to 140 ° C. After 3 hours, a viscosity of 1040 mPas (4: 4, in cresol, 25 ° C.) is achieved. The mixture is then diluted with 577.2 g of cresol and the resin is filtered. The viscosity of the obtained amide urethane resin solution is 5500 mPas at 25 ° C., and the solid content is 44.6%.

Example 4 (Polyester resin containing an amide group as component B)
150.0 g of xylene, 272.2 g of Desmodur® 44 M (described in Example 3), 0.02 in a 2 liter, 3-necked flask equipped with a stirrer, reflux condenser and thermometer. Heat 2 g of a common catalyst (eg hydroxide) and 340.0 g of 2-oxo-cyclopentylcarboxylic acid ethyl ester to 70 ° C. until the NCO number drops to <0.5% after about 4 hours. To do. The mixture is then cooled to 40 ° C. and 48.7 g of trimethylolpropane is added and heated to 140 ° C. After 3 hours, a viscosity of 1150 mPas (4: 5, in cresol, 25 ° C.) is achieved. The mixture is then diluted with 688.9 g of cresol and the resin is filtered. The resulting amide ester resin solution has a viscosity of 4800 mPas at 25 ° C. and a solid content of 44.5%.

Example 5 (resin containing an amide group as component B)
In a 2 liter, 3-neck flask equipped with a stirrer, reflux condenser, and thermometer, 150.0 g xylene, 304.0 g Desmodur® VL, 0.2 g common catalyst (eg , Hydroxide), and 356.9 g of 2-oxo-cyclopentylcarboxylic acid ethyl ester are heated to 70 ° C. until the NCO number drops to <0.5% after about 4 hours. After 3 hours, a viscosity of 980 mPas (4: 5, in cresol, 25 ° C.) is reached. The mixture is then diluted with 688.9 g of cresol and the resin is filtered. The viscosity of the obtained amide resin solution is 4200 mPas at 25 ° C., and the solid content is 44.6%.

Example 6 (Comparison of polyesterimide enamel and polyesteramide imide enamel according to the invention)
Enamel 6a (prior art):
653.1 g of the polyesterimide solution from Example 1, 211.2 g of cresol, 86.0 g of aromatic hydrocarbon mixture, 30.6 g of benzyl alcohol, 10.2 g of general commercial catalyst A, and a small amount (8.9 g) of common commercial surface additive and phenolic resin are made into enamel while stirring. The obtained wire enamel has a solid content of 39.7% and a viscosity of 1250 mPas at 25 ° C.

Enamel 6b:
479.0 g of the polyesterimide solution from Example 1, 214.0 g of the amide urethane resin solution of Example 3, 173.3 g of cresol, 84.0 g of aromatic hydrocarbon mixture, 30.6 g of benzyl alcohol, 10 .2 g of general commercial catalyst A, and a small amount (8.9 g) of general commercial surface additive and phenolic resin are made into enamel with stirring. The resulting wire enamel has a solids content of 39.9% and a viscosity of 1320 mPas at 25 ° C.

Enamel 6c:
384.0 g of the polyesterimide solution from Example 1, 342.0 g of the amide urethane resin solution of Example 3, 142.3 g of cresol, 82.0 g of an aromatic hydrocarbon mixture, 30.6 g of benzyl alcohol, 10 .2 g of general commercial catalyst A, and a small amount (8.9 g) of general commercial surface additive and phenolic resin are made into enamel with stirring. The obtained wire enamel has a solid content of 39.2% and a viscosity of 1400 mPas at 25 ° C.

Enamel 6d:
274.0 g of the polyesterimide solution from Example 1, 490.0 g of the amide urethane resin solution of Example 3, 106.3 g of cresol, 80.0 g of aromatic hydrocarbon mixture, 30.6 g of benzyl alcohol, 10 .2 g of general commercial catalyst A, and a small amount (8.9 g) of general commercial surface additive and phenolic resin are made into enamel with stirring. The obtained wire enamel has a solid content of 40.0% and a viscosity of 1420 mPas at 25 ° C.

Enamel 6e:
175.0 g of the polyesterimide solution from Example 1, 625.0 g of the amide urethane resin solution of Example 3, 72.3 g of cresol, 78.0 g of aromatic hydrocarbon mixture, 30.6 g of benzyl alcohol, 10 .2 g of general commercial catalyst A, and a small amount (8.9 g) of general commercial surface additive and phenolic resin are made into enamel with stirring. The obtained wire enamel has a solid content of 39.4% and a viscosity of 1500 mPas at 25 ° C.

Example 7 (Comparison of polyester enamel and polyesteramide enamel according to the invention)
Enamel 7a (prior art):
745.0 g of the polyester solution from Example 2, 15.0 g of cresol, 29.0 g of benzyl alcohol, 42.0 g of cyclohexanone, 52.0 g of methyldiglycol, 10.0 g of aromatic hydrocarbon mixture A, 30.0 g of aromatic hydrocarbon mixture B, and 68.0 g of common commercial surface additives and phenolic resin are made into enamel with stirring. The resulting wire enamel has a solids content of 50.4% and a viscosity of 3920 mPas at 25 ° C.

Enamel 7b:
591.0 g of the polyester solution from Example 2, 207.0 g of the amidourethane resin solution from Example 3, 11.0 g of cresol, 21.0 g of benzyl alcohol, 30.0 g of cyclohexanone, 38.0 g of methyl Diglycol, 7.0 g of aromatic hydrocarbon mixture A, 27.0 g of aromatic hydrocarbon mixture B, and 68.0 g of common commercial surface additives and phenolic resin are made into enamel with stirring. . The obtained wire enamel has a solid content of 50.0% and a viscosity of 4050 mPas at 25 ° C.

Enamel 7c:
490.0 g of the polyester solution from Example 2, 342.0 g of the amide urethane resin solution from Example 3, 9.5 g of cresol, 16.0 g of benzyl alcohol, 22.5 g of cyclohexanone, 27.0 g of methyl Diglycol, 5.0 g of aromatic hydrocarbon mixture A, 20.0 g of aromatic hydrocarbon mixture B, and 68.0 g of common commercial surface additives and phenolic resin are made into enamel with stirring. . The resulting wire enamel has a solids content of 49.6% and a viscosity of 4240 mPas at 25 ° C.

Enamel 7d:
366.0 g polyester solution from Example 2, 508.0 g amide urethane resin solution from Example 3, 6.5 g cresol, 9.5 g benzyl alcohol, 13.0 g cyclohexanone, 15.0 g methyl Diglycol, 3.0 g of aromatic hydrocarbon mixture A, 11.0 g of aromatic hydrocarbon mixture B, and 68.0 g of common commercial surface additives and phenolic resin are made into enamel with stirring. . The resulting wire enamel has a solids content of 49.9% and a viscosity of 4430 mPas at 25 ° C.

Enamel 7e:
243.0 g of the polyester solution from Example 2, 673.0 g of the amide urethane resin solution from Example 3, 1.0 g of cresol, 2.0 g of benzyl alcohol, 4.0 g of cyclohexanone, 5.0 g of methyl Diglycol, 1.0 g of aromatic hydrocarbon mixture A, 3.0 g of aromatic hydrocarbon mixture B, and 68.0 g of common commercial surface additives and phenolic resin are made into enamel with stirring. . The resulting wire enamel has a solids content of 49.4% and a viscosity of 4510 mPas at 25 ° C.

Example 8 (Comparison of polyesterimide enamel and polyesteramideimide enamel according to the invention)
Enamel 8a (prior art):
653.1 g of the polyesterimide solution from Example 1, 211.2 g of cresol, 86.0 g of aromatic hydrocarbon mixture, 30.6 g of benzyl alcohol, 10.2 g of general commercial catalyst A, and a small amount (8.9 g) of common commercial surface additive and phenolic resin are made into enamel while stirring.

  The obtained wire enamel has a solid content of 39.7% and a viscosity of 1250 mPas at 25 ° C. (corresponding to enamel 6a).

Enamel 8b:
448.8 g of the polyesterimide solution from Example 1, 254.8 g of the amide ester resin solution from Example 4, 166.7 g of cresol, 81.0 g of an aromatic hydrocarbon mixture, 30.6 g of benzyl alcohol, 10.2 g of a typical commercial catalyst A, and a small amount (8.9 g) of a typical commercial surface additive and phenolic resin are made into enamel with stirring.

  The obtained wire enamel has a solid content of 39.5% and a viscosity of 1200 mPas at 25 ° C.

Enamel 8c:
346.5 g of the polyesterimide solution from Example 1, 393.4 g of the amide ester resin solution from Example 4, 138.2 g of cresol, 78.0 g of aromatic hydrocarbon mixture, 30.6 g of benzyl alcohol, 10.2 g of a typical commercial catalyst A, and a small amount (8.9 g) of a typical commercial surface additive and phenolic resin are made into enamel with stirring.

  The resulting wire enamel has a solids content of 39.9% and a viscosity of 1250 mPas at 25 ° C.

Enamel 8d:
238.0 g of the polyesterimide solution from Example 1, 540.0 g of the amide ester resin solution from Example 4, 95.9 g of cresol, 76.0 g of aromatic hydrocarbon mixture, 30.6 g of benzyl alcohol, 10.2 g of a typical commercial catalyst A, and a small amount (8.9 g) of a typical commercial surface additive and phenolic resin are made into enamel with stirring.

  The obtained wire enamel has a solid content of 39.8% and a viscosity of 1310 mPas at 25 ° C.

Enamel 8e:
146.3 g of the polyesterimide solution from Example 1, 664.6 g of the amide ester resin solution from Example 4, 65.4 g of cresol, 74.0 g of aromatic hydrocarbon mixture, 30.6 g of benzyl alcohol, 10.2 g of a typical commercial catalyst A, and a small amount (8.9 g) of a typical commercial surface additive and phenolic resin are made into enamel with stirring.

  The resulting wire enamel has a solids content of 39.2% and a viscosity of 1290 mPas at 25 ° C.

Example 9 (Comparison of polyester enamel and polyesteramide enamel according to the invention)
Enamel 9a (prior art):
745.0 g of the polyester solution from Example 2, 15.0 g of cresol, 29.0 g of benzyl alcohol, 42.0 g of cyclohexanone, 52.0 g of methyldiglycol, 10.0 g of aromatic hydrocarbon mixture A, 39.0 g of aromatic hydrocarbon mixture B, and 68.0 g of common commercial surface additives and phenolic resin are made into enamel with stirring. The obtained wire enamel has a solid content of 50.4% and a viscosity of 3920 mPas at 25 ° C. (corresponding to enamel 7a).

Enamel 9b:
559.8 g of the polyester solution from Example 2, 249.0 g of the amide ester resin solution from Example 4, 10.0 g of cresol, 19.0 g of benzyl alcohol, 28.0 g of cyclohexanone, 35.0 g of methyl Diglycol, 6.0 g of aromatic hydrocarbon mixture A, 25.2 g of aromatic hydrocarbon mixture B, and 68.0 g of common commercial surface additives and phenolic resin are made into enamel with stirring. . The resulting wire enamel has a solids content of 49.8% and a viscosity of 3870 mPas at 25 ° C.

Enamel 9c:
448.2 g of the polyester solution from Example 2, 398.8 g of the amide ester resin solution from Example 4, 8.0 g of cresol, 14.0 g of benzyl alcohol, 18.5 g of cyclohexanone, 23.5 g of methyl Diglycol, 4.0 g of aromatic hydrocarbon mixture A, 17.0 g of aromatic hydrocarbon mixture B, and 68.0 g of common commercial surface additives and phenolic resin are made into enamel with stirring. . The resulting wire enamel has a solids content of 49.9% and a viscosity of 4010 mPas at 25 ° C.

Enamel 9d:
320.4 g of the polyester solution from Example 2, 570.2 g of the amide ester resin solution from Example 4, 4.4 g of cresol, 7.0 g of benzyl alcohol, 9.0 g of cyclohexanone, 11.0 g of methyl Diglycol, 2.0 g of aromatic hydrocarbon mixture A, 8.0 g of aromatic hydrocarbon mixture B, and 68.0 g of common commercial surface additives and phenolic resin are made into enamel with stirring. . The resulting wire enamel has a solids content of 50.2% and a viscosity of 4230 mPas at 25 ° C.

Enamel 9e:
204.0 g of the polyester solution from Example 2, 726.3 g of the amide ester resin solution from Example 4, 1.7 g of benzyl alcohol, and 68.0 g of common commercially available surface additives and phenolic resin. While stirring, make enamel. The obtained wire enamel has a solid content of 50.6% and a viscosity of 4300 mPas at 25 ° C.

Example 10 (Comparison of polyesterimide enamel and polyesteramideimide enamel according to the invention)
Enamel 10a (prior art):
653.1 g of the polyesterimide solution from Example 1, 211.2 g of cresol, 86.0 g of aromatic hydrocarbon mixture, 30.6 g of benzyl alcohol, 10.2 g of general commercial catalyst A, and a small amount (8.9 g) of commercial surface additive and phenolic resin are made into enamel while stirring. The obtained wire enamel has a solid content of 39.7% and a viscosity of 1259 mPas at 25 ° C. (corresponding to enamel 6a).

Enamel 10b:
530.7 g of the polyesterimide solution from Example 1, 143.5 g of the amide resin solution from Example 5, 185.5 g of cresol, 90.6 g of aromatic hydrocarbon mixture, 30.6 g of benzyl alcohol, 10 .2 g of a typical commercially available catalyst A, and a small amount (8.9 g) of commercially available surface additives and phenolic resin are made into enamel with stirring. The obtained wire enamel has a solid content of 39.6% and a viscosity of 1150 mPas at 25 ° C.

Enamel 10c:
454.9 g of the polyesterimide solution from Example 1, 246.0 g of the amide resin solution from Example 5, 158.5 g of cresol, 90.9 g of aromatic hydrocarbon mixture, 30.6 g of benzyl alcohol, 10 .2 g of a typical commercially available catalyst A, and a small amount (8.9 g) of commercially available surface additives and phenolic resin are made into enamel with stirring. The obtained wire enamel has a solid content of 39.5% and a viscosity of 1170 mPas at 25 ° C.

Enamel 10d:
353.8 g of the polyesterimide solution from Example 1, 382.7 g of the amide resin solution from Example 5, 124.6 g of cresol, 89.2 g of aromatic hydrocarbon mixture, 30.6 g of benzyl alcohol, 10 .2 g of a typical commercially available catalyst A, and a small amount (8.9 g) of commercially available surface additives and phenolic resin are made into enamel with stirring. The obtained wire enamel has a solid content of 39.8% and a viscosity of 1210 mPas at 25 ° C.

Enamel 10e:
244.9 g of the polyesterimide solution from Example 1, 529.9 g of the amide resin solution from Example 3, 95.3 g of cresol, 80.2 g of aromatic hydrocarbon mixture, 30.6 g of benzyl alcohol, 10 .2 g of a typical commercially available catalyst A, and a small amount (8.9 g) of commercially available surface additives and phenolic resin are made into enamel with stirring. The obtained wire enamel has a solid content of 40.1% and a viscosity of 1240 mPas at 25 ° C.

Example 11 (Comparison of polyester enamel and polyesteramide enamel according to the invention)
Enamel 11a (prior art):
745.0 g of the polyester solution from Example 2, 15.0 g of cresol, 29.0 g of benzyl alcohol, 42.0 g of cyclohexanone, 52.0 g of methyldiglycol, 10.0 g of aromatic hydrocarbon mixture A, 39.0 g of aromatic hydrocarbon mixture B, and 68.0 g of common commercial surface additives and phenolic resin are made into enamel with stirring. The obtained wire enamel has a solid content of 50.4% and a viscosity of 3920 mPas at 25 ° C. (corresponding to enamel 7a).

Enamel 11b:
643.5 g of the polyester solution from Example 2, 136.4 g of the amide resin solution from Example 5, 12.5 g of cresol, 24.0 g of benzyl alcohol, 34.5 g of cyclohexanone, 44.0 g of methyldi Glycol, 8.0 g of aromatic hydrocarbon mixture A, 29.1 g of aromatic hydrocarbon mixture B, and 68.0 g of common commercial surface additives and phenolic resin are made into enamel with stirring. The resulting wire enamel has a solids content of 49.8% and a viscosity of 3850 mPas at 25 ° C.

Enamel 11c:
566.1 g of the polyester solution from Example 2, 240.0 g of the amide resin solution from Example 5, 11.3 g of cresol, 19.6 g of benzyl alcohol, 27.9 g of cyclohexanone, 34.2 g of methyldi Glycol, 6.9 g of aromatic hydrocarbon mixture A, 26.0 g of aromatic hydrocarbon mixture B, and 68.0 g of common commercial surface additives and phenolic resin are made into enamel with stirring. The resulting wire enamel has a solids content of 49.6% and a viscosity of 3040 mPas at 25 ° C.

Enamel 11d:
456.4 g of the polyester solution from Example 2, 386.9 g of the amide resin solution from Example 5, 8.7 g of cresol, 13.9 g of benzyl alcohol, 19.6 g of cyclohexanone, 23.8 g of methyldi Glycol, 5.2 g of aromatic hydrocarbon mixture A, 17.5 g of aromatic hydrocarbon mixture B, and 68.0 g of common commercial surface additives and phenolic resin are made into enamel with stirring. The resulting wire enamel has a solids content of 49.7% and a viscosity of 4030 mPas at 25 ° C.

Enamel 11e:
328.8 g of the polyester solution from Example 2, 557.6 g of the amide resin solution from Example 5, 3.2 g of cresol, 6.3 g of benzyl alcohol, 10.3 g of cyclohexanone, 13.4 g of methyldi Glycol, 3.2 g of aromatic hydrocarbon mixture A, 9.2 g of aromatic hydrocarbon mixture B, and 68.0 g of common commercial surface additives and phenolic resin are made into enamel with stirring. The resulting wire enamel has a solids content of 49.5% and a viscosity of 4100 mPas at 25 ° C.

Results Test data according to DIN 46453 and DIN EN 60851:

Polyesterimide (Examples 6, 8, and 10)
A 0.65-mm diameter copper wire was enameled at an oven temperature of 580 ° C. at 38 and 46 m / min, respectively.

For amide urethane resin:

For amide ester resins:

For amide resin:

  From the table it can be seen that as the content of resins containing amide groups increases, the enamel maintains its general properties better when the enamelization rate is significantly changed from 38 to 48 m / min (ie according to the invention). It is clearly seen that enamel shows better performance with rapid enamelling). On the other hand, the comparative enamel (a) shows a significant loss of performance when the enamelization rate is increased.

Polyester (Examples 7, 9, and 11):
A 1.0 mm diameter copper wire was enameled at an oven temperature of 560 ° C. at 45 and 52 m / min, respectively.

For amide urethane resin:

For amide ester resins:

For amide resin:

  From the table it can be seen that as the content of resins containing amide groups increases, the enamel maintains its general properties better when the enamelization rate is significantly changed from 45 to 52 m / min (ie according to the invention). It is clearly seen that enamel shows better performance with rapid enamelling). On the other hand, the comparative enamel (a) shows a significant loss of performance when the enamelization rate is increased. Furthermore, enamels 9 and 11 show a significant improvement in heat shock compared to the standard (9a, 11a).

Claims (12)

A wire coating composition based on a resin having a nucleophilic group,
(A) 5 to 95% by weight of at least one resin having a nucleophilic group selected from the group consisting of OH, NHR, SH, carboxylate, and CH-acidic groups;
(B) 0 to 70% by weight of a resin containing at least one amide group;
(C) including at least one organic solvent in an amount of 5 to 95% by weight,
A composition in which the resin of component (A) or component (B) contains an α-carboxy-β-oxocycloalkylcarboxylic acid amide group, and the weight percent of (A) to (C) is a total of 100 percent. (A) 5-60% by weight of at least one resin having a nucleophilic group selected from the group consisting of OH, NHR, SH, carboxylate, and CH-acidic groups;
(B) 1 to 50% by weight of a resin containing at least one amide group;
(C) at least one organic solvent in an amount of 5 to 90% by weight;
(D) 0 to 10% by weight of at least one catalyst;
(E) 0-20% by weight of at least one phenolic resin and / or melamine resin and / or block isocyanate;
(F) 0-3 wt% of commonly used additives or adjuvants;
(G) 0 to 70% by weight of nanoscale particles,
(H) 0 to 60% by weight of commonly used fillers and / or pigments,
The resin of component (A) or component (B) comprises an α-carboxy-β-oxocycloalkyl carboxylic acid amide group, wherein the weight percent of (A) to (H) totals 100 percent. The composition as described.   The composition of claim 2, wherein component (B) comprises an α-carboxy-β-oxocycloalkyl carboxylic acid amide group.   The composition according to claim 1, wherein at least one polyester and / or polyesterimide is used as component (A).   The composition of Claim 2 whose average particle diameter of the particle | grains of a component (G) is the range of 1-300 nm.   The particles are based on an element-oxygen network comprising elements from the series consisting of silicon, zinc, aluminum, tin, boron, germanium, gallium, lead, transition metals and lanthanides and actinides, and the element-oxygen of these particles The composition according to claim 5, wherein the surface of the network can be modified with reactive organic groups.   The composition of claim 1 comprising an element-organic compound.   8. Composition according to claim 7, wherein ortho-titanate, ortho-zirconate, titanium tetralactate, hafnium and silicon compounds, and silicone resins are used as element-organic compounds.   A method of coating a conductive wire comprising applying the composition of claim 1 and curing the coating composition at an elevated temperature to produce a cured coating.   The method of claim 9 wherein the wire is pre-coated.   10. The method of claim 9, wherein the coating composition is applied as a single layer and / or as a base coat, middle coat, and / or top coat within a multilayer coating.   A conductive electric wire coated and cured with the coating composition according to claim 1.