Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
  • H01B3/421—Polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/12—Unsaturated polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/12—Unsaturated polyimide precursors
  • C08G73/125—Unsaturated polyimide precursors the unsaturated precursors containing atoms other than carbon, hydrogen, oxygen or nitrogen in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/12—Unsaturated polyimide precursors
  • C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
  • C08G73/127—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic containing oxygen in the form of ether bonds in the main chain
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C09D179/085—Unsaturated polyimide precursors
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
  • H01B3/306—Polyimides or polyesterimides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/308—Wires with resins

Definitions

• the present invention relates to wire enamels containing polyester based on tris-2-hydroxyethyl isocyanurate, organic solvents, catalysts,
• the present invention also relates to a method for producing these wire enamels.
• Wire enamels based on polyester resins are known and described, for example, in US Pat. No. 3,342,780, in US Pat. No. 3,249,578 and in EP-B-144 281.
• Polyol component is used in the publications mentioned tris-2-hydroxyethyl isocyanurate.
• TAEIC tris-2-hydroxyethyl isocyanurate
• Wire enamel layer or at a particularly high thermal pressure (IEC 851-6).
• IEC 851-6 particularly high thermal pressure
• wire enamels based on polyester resins compared to wire enamels based on polyesterimide resins or polyamideimide resins is that the wires coated with polyester enamels have a low thermal shock.
• THEIC modified Polyester wire enamels are therefore used in two-layer coatings for wires as a "base coat" to which, for example, a polyamideimide wire enamel is applied.
• the object underlying the present invention was to provide wire enamels which avoid the disadvantages associated with polyester wire enamels and thus improve the property profile of THEIC polyester wire enamels. These wire enamels should be stable in storage, have good adhesion to copper wires, have the highest possible heat pressure and sufficient thermal shock.
• the wire enamels should have the highest possible solids content with a viscosity that is favorable for processing.
• the surface quality of the painted wires should be improved, especially with regard to the hardness properties.
• This object is achieved by wire enamels containing polyester based on tris-2-hydroxyethyl isocyanurate (THEIC), organic solvents, catalysts, auxiliaries and additives, which are characterized in that the wire enamels a) 20 to 50% by weight of THEIC Polyester, b) 2 to 35% by weight of a bismaleimide resin, c) 0.1 to 3% by weight of a catalyst, preferably a titanate catalyst, and d) 35 to 77% by weight of organic solvents, based on the total weight of the wire enamel , which is 100% by weight. It is surprising and unpredictable that the modification of THEIC polyester wire enamels with bismaleimide resins gives wire enamels which adhere very well to copper wires and which lead to coatings with excellent technological properties.
• TEEIC tris-2-hydroxyethyl is
• polyesters (component a)) modified with tris-2-hydroxyethyl isocyanurate are known and are described, for example, in US Pat. No. 3,342,780 and EP-B-144 281.
• TEEIC tris-2-hydroxyethyl isocyanurate
• the polyesters are prepared in a known manner by esterification of polybasic carboxylic acids with polyhydric alcohols in the presence of suitable catalysts.
• an alcohol component i.a. Tris-2-hydroxyethyl isocyanurate used.
• Alcohols suitable for the production of the polyesters are, for example, ethylene glycol, 1,2-and 1,3-propylene glycol, 1,2-butanediol, 1,3 and -1,4, 1,5-pentanediol, neopentyl glycol, diethylene glycol, triethylene glycol kol and triols, such as glycerol, trimethylolethane, trimethylolpropane and tris-2-hydroxyethyl isocyanurate. Mixtures of ethylene glycol and tris-2-hydroxyethyl isocyanurate are preferably used. The use of tris-2-hydroxyethyl isocyanurate leads to high softening temperatures of the lacquer layer.
• Suitable carboxylic acids are, for example, phthalic acid, isophthalic acid, terephthalic acid and their esterifiable derivatives, such as the anhydrides, if they exist, and the lower alkyl esters of the acids mentioned, such as methyl, ethyl, propyl, butyl, amyl, hexyl and octyl phthalates, terephthalates and isophthalates. Both the half esters, the dialkyl esters and mixtures of these compounds can be used. The corresponding acid halides of these compounds can also be used.
• polyesters have a ratio of hydroxyl to carboxyl groups from 1.1: 1 to 2.0: 1, preferably from 1.15: 1 to 1.60: 1.
• Catalysts suitable for the production of the polyesters which are used in amounts of 0.01 to 5% by weight, based on the feed mixture, are conventional esterification catalysts, for example
• Heavy metal salts for example lead acetate, zinc acetate, furthermore organic titanates, for example
• Tetra-n-butyl titanate cerium compounds and organic acids, e.g. p-toluenesulfonic acid.
• a polyester a) which is produced from ethylene glycol, tris-2-hydroxyethyl isocyanurate and dimethyl terephthalate and has a hydroxyl number in the range from 80 to 150 mg KOH / g is preferably used in the wire enamels according to the invention.
• component b) of the invention is preferably used in the wire enamels according to the invention.
• Bismaleimide resins used in wire enamels are resins or prepolymers with bismaleimides as building blocks.
• the bismaleimide resins are generally obtained from the bismaleimide units and comonomers (hardeners). Mixing and heating the bismaleimides and the comonomers gives them Bismaleimide resins or prepolymers.
• Bismaleimide building blocks correspond to the general formula
• Y is an optionally substituted alkenyl group and X is a divalent radical having at least two carbon atoms.
• Monomeric bismaleimides are e.g. known from DE-A-20 40 094, DE-A-27 19 903 and DE-A-32 47 058.
• Preferred bismaleimide components are 4,4'-bismaleimidodiphenylmethane, 4,4'-Bismaleinimidodiphenylether, 3.3, -Bismaleinimidodiphenylsulfon, 1,3-bismaleimidobenzene, 2,4-Bismaleinimidotoluol, 1,6-bismaleimidohexane and 2,2,4- Trimethyl-1,6-bismaleimidohexane.
• polymaleimides and mixtures of various bismaleimides can also be used to prepare the bismaleimide resins.
• the bismaleimides can also contain up to 20% of a monoimide.
• Suitable comonomers are alkenyl compounds, aromatic and aliphatic polyamines, polyphenols, aminophenols, vinyl and allyl compounds.
• Polyamines suitable as comonomers are known, for example, from DE-A-17 70 867; 4,4'-diaminodiphenylmethane are preferred, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodicyclohexyl methane and 3,3'-diaminodiphenyl sulfone.
• polyphenols that can be used are bisphenol A, bisphenol F or novolaks; others are listed in DE-A-24 59 925.
• alkenylphenols or phenol ethers are described in DE-A-26 27 045, o, o'-diallybisphenol A is preferred.
• Oligomeric allyl- or propenyl-terminated sulfones or allylated dicyclopentadiene polyphenols are also suitable.
• Aminophenols which can be used are, for example, m- or p-aminophenol. Examples of vinyl and allyl compounds are: styrene, divinylbenzene, diallyl phthalate,
• Suitable additives are, for example
• Fillers such as chalk, kaolin, quartz flour, dolomite, heavy spar, metal powder, aluminum oxide hydrate, cement,
• Reinforcing fibers such as glass, carbon, asbestos and cellulose fibers as well as synthetic organic fibers, e.g. from polyethylene, polycarboxylic acid esters, polycarbonate or polyamides, inhibitors such as hydroquinones, quinones, nitrobenzenes, N-nitroso compounds, salts of divalent copper and quaternary ammonium salts,
• Polymerization initiators such as benzoyl peroxide
• Hardening accelerators for example octoates or naphthenates of copper, lead, calcium, magnesium, cerium and in particular of manganese and cobalt; also aromatic Amines, such as dimethylaniline and diethylaniline, imidazoles, tertiary phosphines, organic acids,
• Shrinkage-reducing polymers such as polystyrene, polymethyl methacrylate, polyvinyl acetate, polyethylene, polybutadiene and graft copolymers, copolymers and condensation polymers, such as saturated polyesters or polyester urethanes,
• - elasticizing additives e.g. rubbery
• Block copolymers and modified polytetrahydrofuran, - flame retardants and plasticizers are also known.
• the starting materials are mixed using customary techniques and at temperatures of i.a. 70 to 190 ° C heated, depending on the reaction time, a prepolymer is formed with an increase in viscosity.
• a viscous solution or a glassy solid which is either ground or dissolved in a solvent, for example dimethylformamide or N-methylpyrrolidone, is obtained after cooling.
• the bismaleimide resins can also be prepared in a solvent. Suitable bismaleimide resins are described, for example, in DE-A-38 27 120, DE-A-38 35 197 and DE-A-39 24 867.
• the solid, meltable bismaleinimide resins known from DE-A-39 24 867 are particularly preferably used in the wire enamels according to the invention. These are made from
• R C 1 -C 4 alkyl
• n 0.1 or 2
• Suitable bismaleimides A) are the bismaleimide building blocks already mentioned, 4,4'-methylene-bis- (N-phenylmaleimide) preferably being used.
• Suitable aminophenols B) are m-, o- and p-aminophenol, with m-aminophenol being preferred.
• the molar ratio A): B) is between 2.4: 1 and 1.4: 1, preferably between 2.0: 1 and 1.5: 1 and in particular between 1.8: 1 and 1.6: 1.
• Suitable ones Catalysts C) are secondary or tertiary amines or phosphines.
• Preferred amines are N, N, N ', N'-tetramethyldiaminodiphenylmethane, N, N-dimethylaniline and dimethylbenzylamine or also imidazoles, such as 1-methylimidazole.
• Triphenylphosphine is preferred for the phosphines.
• inhibitors D) for preventing the premature radical polymerization of the double bond of the bismaleimide customary, preferably phenolic compounds, in particular hydroquinone or 2,6-dimethylhydroquinone, are obtained in amounts of up to 1, preferably 0.1 to 0.5% by weight to the sum of A) + B).
• Vinyl and allyl compounds E which are admixed in amounts of up to 25, preferably from 5 to 20,% by weight, based on the sum of A) + B), are copolymerized as comonomers in the resin matrix during the curing of the prepreg. They act as thinners to lower the resin viscosity, but above all you can, by suitable choice of the type and amount of these additives, also in the form of mixtures of several vinyl or allyl compounds, the stickiness of the
• Suitable are, for example, N-vinylpyrrolidone, N-vinylcarbazole, divinylbenzene, acrylates, diallyl ethers, ethoxylated bisphenol A methacrylate, 3,3'-diallyl bisphenol A, 3,3'-dipropenyl bisphenol A, and also reaction products of a diepoxide with acrylic acid or methacrylic acid, but especially diallyl phthalate or prepolymers produced therefrom, triallyl cyanurate and triallyl isocyanurate.
• Conventional epoxy resins F) in amounts of up to 25% by weight, based on A) + B), can also act as reactive thinners which are incorporated into the resin matrix.
• polymerization initiators G) to accelerate the curing process 0 to 2, preferably 0.01 up to 2% by weight, based on the sum of A) + B), of conventional peroxides which decompose into free radicals at temperatures above 180 ° C.
• the mixture is heated to temperatures between 140 to 190 ° C., preferably to 150 to 180 °, the components melting and bismaleimide and aminophenol reacting with one another.
• the residence time of the reactants at these temperatures should be relatively short, preferably 1 to 10, in particular 2 to 4 minutes. be.
• the reaction is carried out until 70 to 90 mol% of component A and 30 to 60 mol% of component B are still present in the unreacted form in the bismaleimide resin formed.
• the degree of conversion can be controlled in a simple manner by means of the reaction temperature, reaction time and, if appropriate, the type and amount of the addition catalyst.
• the progress of the reaction can be monitored by rapid cooling and analytical determination of the unreacted starting components A) + B).
• High pressure liquid chromatography (HPLC) is used for the quantitative determination of A + B in the resin mixture, whereby the retention times and areas were previously calibrated with the pure substances A and B.
• HPLC High pressure liquid chromatography
• the melt is rapidly cooled.
• the resin can be granulated, flaked or pulverized.
• bismein imide resins b) which are particularly preferably used A) a bismaleimide
• R-Ar-O-Het-O-Ar-R with R alkenyl or alkenyloxy group with 3-6
• Ar phenylene, naphthylene or
• Het heterocyclic six-membered ring selected from the group
• Suitable comonomers B) are, for example, 2,6-bis (3-allyl-4-hydroxyphenoxy) pyridine, 2,6-bis (3-allyloxyphenoxy) pyridine, 2,6-bis (4-allyl-3- hydroxyphenoxy) pyridine, 2,6-bis [(3-allyl-4-hydroxyphenylisopropyl) phenoxy] pyridine and the corresponding pyridazine derivatives.
• 2,6-Bis (2-propenylphenoxy) pyridine is particularly preferably used as the heterocyclic comonomer.
• Suitable manufacturing processes are in the
• the starting materials are mixed using customary techniques and heated to temperatures between 70 and 190 ° C., with the formation of a prepolymer. Depending on the progress of the prepolymerization, a relatively low-viscosity melt or a glass-like solidified solid is obtained, which is ground or dissolved in a solvent.
• the resins can also be prepared in a solvent.
• the mixing ratio in the reaction of the bismaleimide with the heterocyclic alkenyl compound can be chosen relatively freely, an equivalent ratio of 1 to 0.05 to 5 being preferred.
• Additional components can be added to the bismaleimide resins described.
• Possible additional components are, for example, amines, preferably aromatic diamines (for example 4,4 , -diaminodiphenylmethane) and aminophenols, which are also an addition reaction can make double bonds with maleimide.
• Prepolymers for example of a bisimide and an amine, can also be used.
• Other components up to a share of
• vinyl monomers e.g. Styrene, ⁇ -methylstyrene, divinylbenzene, acrylic or methacrylic acid ester, diallyl phthalate, 3,3'-diallylbisphenol A, triallyl isocyanurate, triallyl cyanurate or vinyl pyrrolidone.
• the bismaleimide resins known from this laid-open publication are preferably used because they have low softening temperatures and a long gelation time, which enables processing in the melt state.
• the bismaleimide resins described are suitable for use in the wire enamels according to the invention.
• the bismaleimide resins used in the wire enamels according to the invention are available, for example, under the trademark Palimid ® S from BASF AG, for example the bismaleimide resins Palimid ® S
• Palimid ® S 410 KR, Palimid ® S 430 KR and Palimid ® S 440 KR are particularly preferred Palimid ® S 410 KR, Palimid ® S 430 KR and Palimid ® S 440 KR (BASF AG).
• Organic solvents (component d) which are suitable for the wire enamels according to the invention and can also be used for the production of THEIC polyesters NEN are cresolic and non-cresolic organic solvents such as cresol, phenol, glycol ethers such as methyl glycol, ethyl glycol, isopropyl glycol, butyl glycol, methyl diglycol, ethyl diglycol, butyl diglycol; Glycol ether esters, such as, for example, methyl glycol acetate, ethyl glycol acetate, butyl glycol acetate and 3-methoxy-n-butyl acetate; cyclic carbonates, such as propylene carbonate; cyclic esters such as ⁇ -butyrolactone and, for example, dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.
• cresolic and non-cresolic organic solvents such as cresol, phenol, glycol ether
• Aromatic solvents can also be used, if appropriate in combination with the solvents mentioned.
• the organic solvents can be partially replaced by blending agents. Either pure solvent or pure solvent mixture or solvent with up to 40% by weight, based on the total weight of component d), of cutting agent is preferably used.
• suitable blending agents are xylene, solvent naphtha ® , toluene, ethylbenzene, cumene, heavy benzene, various combinations thereof.
• the wire enamels according to the invention contain 0.1 to 3% by weight, based on the total weight of the wire enamel, including the catalyst, of a transesterification catalyst, preferably a titanate catalyst (component c)), such as tetraalkyl titanates, for example tetraisopropyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetraamyl titanate, Tetrahexyl titanate, tetraethyl titanate, tetramethyl titanate, diisopropyldibutyl titanate or aryl titanates, such as tetraphenyl titanate, tetracresyl titanate, tetraxylenyl titanate or triethanolamine titanate.
• a titanate catalyst component c
• tetraalkyl titanates for example tetraisopropyl titanate, tetrapropyl titanate, tetrabutyl titan
• the wire enamels according to the invention advantageously contain 0.2 to 5.0% by weight of a flow-promoting phenol-formaldehyde resin e), based on the total weight of the wire enamel including component e).
• Suitable phenolic resins are known condensation products of phenol, substituted phenols or bisphenol A with formaldehyde.
• the properties of the phenolic resins depend on the type of phenol component and the aldehyde component, on the pH value set during production and on the quantitative ratio of the two reactants.
• the phenolic resins can also be modified by incorporating other compounds in the polycondensation as well as by subsequent modification of the phenolic resin and different control of the reaction process.
• those with other aldehydes can also be used.
• the wire enamels according to the invention contain up to 0.3% by weight of imidazole or an imidazole derivative f), based on the total weight of the wire enamels including component f).
• imidazole derivative for example
• the wire enamels contain up to 0.3% by weight of a tertiary amine g), based on the total weight of the wire enamel, including g).
• Suitable tertiary amines are N-methylmorpholine, N-methylpyrrolidine, N-methylpyrrole, trimethylamine, triethylamine, dimethylethanolamine, diethylmethylamine, methyldiethanolamine, ethylmethylethanolamine, Dimethylethylamine, dimethylpropylamine, dimethyl-3-hydroxy-1-propylamine, dimethylbenzylamine, dimethyl-2-hydroxy-1-propylamine, dimethyl-1-hydroxy-2-propylamine and 1,4-diazabicyclo [2.2.2. ]octane.
• the wire enamels can also contain customary auxiliaries and additives in customary amounts, preferably up to 1% by weight, based on the total weight of components a) and b).
• auxiliaries for the wire enamels for example, flow-improving melamine resins or leveling agents based on polyacrylates can be used.
• Wire enamels according to the invention which a) 28 to 47% by weight of THEIC polyester, b) 4 to 10% by weight of a bismaleimide resin, c) 0.3 to 1.5% by weight lead to coatings with particularly good properties.
• a titanate catalyst d) 40 to 67% by weight of organic solvents, e) 0.4 to 4.0% by weight of a phenol-formaldehyde resin, f) 0.01 to 0.2% by weight of imidazole and / or an imidazole derivative and g) 0.01 to 0.2% by weight of a tertiary amine, based on the total weight of the wire enamel, which is 100% by weight.
• the present invention also relates to a method for the production of the wire enamels described above, which is characterized in that the polyester component a), the bismaleimide resin b), the catalyst c), organic solvent d), if appropriate the phenolic resin component e), if appropriate the imidazole or the imidazole derivative f) , if necessary the tertiary amine g) and further auxiliaries and additives by mixing and if necessary
• Dispersing can be processed into a wire coating composition.
• the THEIC polyester a) can be dissolved together with the bismaleimide resin.
• the wire enamels are applied and hardened using conventional wire enamelling machines.
• the required lacquer film thickness is built up by at least 1 to 10 individual orders, whereby each individual lacquer application is cured without bubbles before the new lacquer application.
• Usual lacquering machines operate at take-off speeds of 5 to 180 m / min, depending on the binder base of the wire enamel and the thickness of the wire to be coated. Typical oven temperatures are between 300 and 550 ° C.
• Such Wire coating machines are known and therefore do not need to be explained in more detail here.
• the wire enamels according to the invention are surprisingly stable in storage, even though they contain components as diverse as THEIC polyesters, bismaleimide resins, titanates and possibly phenolic resins.
• the wire enamel coatings obtained from the lacquers according to the invention after lacquering and baking have very good adhesion to copper wires, although - as will be shown below - bismaleimide resins alone, i.e. without the polyester component a), lead to non-stick coatings.
• the wire coatings resulting from the lacquers according to the invention have an extraordinarily good property profile.
• the wires coated with the lacquers according to the invention have excellent results in terms of thermal shock.
• a polyester resin having a hydroxyl number of 90 to 140 mgKOH / g is prepared from 125.84 g of ethylene glycol, 294.92 g of tris-2-hydroxyethyl isocyanurate, 578.57 g of dimethyl terephthalate and 0.68 g of butyl titanate by heating to 200 ° C.
• This THEIC-modified polyester resin is used in the following working examples.
• 1,2-dimethylimidazole 126.78 g of solvent naphtha and 253.15 g of cresol, the lacquer is stirred for 6 hours and then filtered.
• EXAMPLE 2 71.42 g of a bismaleimide resin based on monomeric bismaleimides and aminophenols and 0.07 g of 1,2-dimethylimidazole are added to 892.79 g of the THEIC-modified polyester resin lacquer produced under B) at room temperature with stirring. After adding 26.79 g of cresol and 8.93 g of solvent naphtha, the lacquer is stirred for 6 hours and then filtered.
• the viscosity of this solution is 630 mPas at 23 ° C.
• the solution is added with stirring at room temperature
• the lacquer is stirred for 2 hours and then filtered.
• lacquers produced under B) and C) and in Examples 1 to 5 are lacquered on a standard wire lacquering machine.
• the coated wires are tested according to IEC 851. The results are summarized in the following table:
• the wire painted with a THEIC polyester varnish (comparative example B) is characterized by very good adhesion when winding 1 x d with a pre-stretch of 25%.
• the disadvantage is a relatively weak thermal shock 1 x d of 155 ° C.
• the bismaleimide resin varnish described under C) has no liability on copper wires.
• the wire enamels according to the invention produced in Examples 1-5 have good adhesion to the copper wire which corresponds to the standard.
• the surface quality of the coated wires and the hardness of the coating film are in some cases above the level compared to conventional wires coated with THEIC polyesters.
• Wires have a thermal pressure of 430 - 450 ° C and a thermal shock, 1 x d to 220oC.
• the tan S steep rise is between 136oC and 146oC.

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• 1991
  • 1991-12-09 DE DE4140472A patent/DE4140472A1/de not_active Withdrawn
• 1992
  • 1992-12-01 RU RU94039928/04A patent/RU94039928A/ru unknown
  • 1992-12-01 WO PCT/EP1992/002776 patent/WO1993012188A1/de not_active Application Discontinuation
  • 1992-12-01 EP EP92924638A patent/EP0616628A1/de not_active Withdrawn
  • 1992-12-01 BR BR9206901A patent/BR9206901A/pt not_active Application Discontinuation
  • 1992-12-01 US US08/244,674 patent/US5536791A/en not_active Expired - Fee Related
  • 1992-12-01 JP JP5510560A patent/JPH07504692A/ja active Pending
  • 1992-12-09 TR TR01193/92A patent/TR27664A/xx unknown

Non-Patent Citations (1)

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