Review

Coatings for Solderable Wires for the Modern Electric Industry

Simon Rost*

The scientic and industrial history of polyurethane wire enamels during the previous six decades is reviewed. Their main use is as coatings for wires in miniature electrical devices and in electronics, where fast solderability at low temperatures is crucial. Market trends for polyurethane enamels are discussed, and an outlook is provided as to how future developments might inuence the industrial use of polyurethane wire enamels.

Introduction
In 1937 a new polymer type, the polyurethane, was discovered by Bayer.[1] This poly-addition product of polyisocyanates and polyols opened a new chapter in the varnish and wire enamel chemistry. During the Second World War, Bayer AG developed the use of isocyanates and polyurethanes for coatings. Desmodur1 (polyisocyanates) and Desmophen1 (polyols) were registered as trade marks and, therefore, polyurethane coating materials are still called DD-varnish today. The rst polyurethane wire enamel (PU-WE), introduced in 1950, consisted of an alkyd or polyol, made of dicarboxylic acids, three functional alcohols, like glycerin, and Desmodur AP stable, a phenol blocked trimethylol propane-toluene diisocyanate adduct.[2] These polyurethane coatings were exible, had excellent electrical properties and good abrasion and chemical resistance. Additionally, PU-WE having the
S. Rost Elantas Beck GmbH, Grossmannstrasse 105, 20539 Hamburg, Germany E-mail: simon.rost@altana.com
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advantage of easy solderability, they cure at lower temperature and the wire can be enameled at faster rates.[3] In the 1950s, the dominant position of wire enamels was held by poly(vinyl formal) resin combined with a phenolic resin in a solvent mixture of cresylic acid and naphtha.[4] The long-term temperature resistance of this insulation was 105 8C (class A according to IEC 60172). A part of the market was replaced by polyurethane, especially in the ne wire segment. These coatings do not have to be stripped off wires that are tobe soldered, because the urethane bond decomposed at a soldering temperature of 360 8C, leaving a clean wire surface for the solder to adhere to. The long term temperature resistance of such solderable enamel was class A.[5] Using a polyurethane undercoat and a nylon top coat, class B (TI 130 8C, according to IEC 60172) was reached. Combinations of poly(vinyl formal) and polyurethane wire enamels were made to improve or combine their properties,[613] such as resistance to organic solvents, stability and breakdown voltage. In the early 1960s, with the introduction of terephthalic acid polyesters and polyester imides as high thermal stability wire enamels by Dr. Beck & Co. GmbH,[14] new

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Simon Rost, completed his PhD in chemistry at the University of Hamburg from 2002 to 2005. He studied biodegradable polymers in the research group of Prof. Kricheldorf at the department of macromolecular and technical chemistry, publishing ten papers. In April 2005 he joined Beck Electrical Insulation GmbH (former name) as head of R & D of Wire Enamels, Impregnating Varnishes and Insulating Fluids, where he has developed new products and authored patents in the eld of wire enamels.

possibilities were opened for modifying PU-WE for thermal upgrade. In the electrical and electronic industries, higher amounts of magnet wire were used in manufacturing motors, transformers, television yoke coils and many other products. The design of electrical equipment and machinery has required progressively smaller motors, coils and transformers with higher efciency operating at higher temperatures. This, together with increased automated production, lead to the demand for thermal resistant, solderable magnet wire. In the middle of the 1970s, the rst class-F (TI 155 8C, according to IEC 60172) PU-WE were developed by Dr. Wiedeking GmbH and Schweizerische Isola-Werke[15,16] using a polyester imide as polyol. Increasing the imide content of the polyester imide and using diphenyl methane diisocyanate (MDI) instead of toluene diisocyanate (TDI) lead, in the middle of the 1980s, to the introduction of a class-H (TI 180 8C, according to IEC 60172) PU-WE by Dr. Wiedeking GmbH. A lot of other modications to improve the properties of polyurethane wire enamels were made. Some of them will be discussed in the chemical part of this review, but until now the class-H PU-WE represents the top performing version of the commercially available polyurethane wire enamels.

Going through the literature, just small modications have been made. Instead of pure 1,1,1-trimethylol propane (TMP) glycerin, mixtures of TMP and glycerin and diols like ethylene glycol, diethylene glycol and 1,6-hexane diol were used,[1719] as well as alkoxylated bisphenol A.[25] Instead of TDI isomers, MDI isomers and their mixtures were used. The production process has been optimized to a single stage process using excess of the blocking agent as solvent and for molecular weight adjustment.[30,31] For polyurethane wire enamels, aromatic isocyanates are used, because they have a higher thermal stability and higher reactivity compared to the aliphatic ones. Typical isocyanates, which are used for PU-WE, are shown in Scheme 2. The electron distribution of the isocyanate group can be shown by the mesomeric structures (Scheme 3). The partial positive charge is located at the carbon atom, while partial negative charges are located at the nitrogen and oxygen atoms. The C atom can be easily attacked by a nucleophilic partner, while the N and O atoms are free for an electrophilic addition. Due to the M effect of the aromatic phenyl group, the positive charge at the C atom is increased, and the reactivity therewith (Scheme 4). The aromatic isocyanates are not used pure in the wire enamel formulations. They were reacted with aliphatic triols like TMP or diols in a ratio of aliphatic OH group to dior polyisocyanates of normally 1:1. The reaction leads to a product mixture having a molecular weight distribution. This distribution can be adjusted by small modications of the ratio, reaction temperature and reaction time to optimize the nish product. The remaining free NCO groups were blocked in the same step using phenols and cresylic acids as blocking agents (Scheme 5).

Chemistry
The general composition of a polyurethane wire enamel consist of a blocked polyisocyanate adduct, a polyester polyol, catalyst, solvents and additives. Blocked Polyisocyanate Adducts The rst blocked polyisocyanate adduct for the use in wire enamels was Desmodur1 AP stable from Bayer AG.[2] A representative structure is shown in Scheme 1. This type of blocked polyisocyanate adduct has not changed much until today.
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Scheme 1. Desmodur1 AP stable.

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Coatings for Solderable Wires for the Modern Electric Industry

Scheme 5. Blocked isocyanate adduct synthesis. Scheme 2. Typical isocyanates for PU-WE.

Scheme 3. Mesomeric structures of NCO.

There are three reasons for the use of blocked isocyanate adducts instead of the pure isocyanates in PU-WE formulations. Some isocyanates, in particular TDI, have low vapor pressure (TDI: 2.3 102 Torr at 25 8C)[20], which causes irritation when working with them. This problem is solved by increasing the molecular weight and so reducing the vapor pressure. No free monomeric isocyanates are left in the PU-WE. Forming the adduct increases the molecular weight, the branching density and the functionality. This leads to a high cross-linking density on the wire with a higher hardness and chemical resistance, since a highly branched pre-product is used. Additionally, handling and dosing is much more comfortable. The blocking of the free isocyanate groups of the adduct with aromatic alcohols was done to obtain a stable one-component formulation with long shelf life protecting the highly reactive isocyanate group. As blocking agents phenols, cresylic

Scheme 4. Mesomeric structures of aromatic NCO.

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acids, caprolactam, imidazole, malonic esters, oximes can be used, whereas phenols are preferred. The steric hindrance and acid character of the blocking agent leads to thermal labile bonds to the isocyanate. In general, the backwards reaction is easier with increased acidity of the active H atom of the blocking agent. Table 1 shows the deblocking temperatures of different urethanes.[21] As can be seen from Table 1, the lowest splitting temperatures of 120130 8C occurs using full aromatic urethane bonds like in the blocked polyisocyanate adduct. The adduct in the PU-WE formulation is stable at room temperature, in the oven at elevated temperatures deblocking occurs and the free isocyanate groups react with the polyester polyol, forming more stable urethane bonds. The split product then evaporates and disappears from the equilibrium. The splitting of urethane groups at high temperatures is the reason for the solderability of PU-WE. The highly cross-linked and polymeric structure as well as the secondary structure increased the splitting temperature. A higher amount of urethane bonds improved the solderability. The blocked isocyanate adduct shown is mainly used in the PU-WE formulations, but also some modications were made in the past. Bayer introduced a hydantoin modied polyisocyanate to increase the thermal resistance of the resulting wire enamel.[22] The reaction of a ethylene-1,2-dicarboxylic acid ester like maleic acid dimethylester with primary aminic alcohols leads to the asparaginic acid esters. After the following reaction of these esters with diiso-

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Table 1. Deblocking temperatures of urethanes.

Urethane

Deblocking temperature (approx.) -C

Scheme 7. Carbodiimide formation.

AlkylNHCOOAlkyl ArylNHCOOAlkyl AlkylNHCOOAryl ArylNHCOOAryl

230250 200 180 120130

Scheme 8. Uretoneimide formation.

cyanates hydantoin modied polyisocyanates were obtained (Scheme 6). Wires with good brazability, heat and crazing resistance were obtained using a spiroacetal glycol MDI reaction product blocked with cresol and a epoxy resin.[23] Carbodiimide modied blocked isocyanates allowed a higher enameling speed. With hydroxyl group containing reaction partners, solderable PU-WE were obtained; with carboxylic acid containing partners cross-linked, non-solderable wire enamels were obtained.[24] The NCO groups of the isocyanate used were not blocked completely. The remaining ones react in the present of a phosphoric catalyst (methylphosphacyclopentene oxide) at elevated temperatures to the carbodiimide and carbon dioxide (Scheme 7). The products may also contain uretoneimide groups from the addition reaction of isocyanate groups and carbodiimide groups (Scheme 8). These isocyanates react like blocked isocyanates. The cross-linking of carbodiimide with carboxylic acid groups in the present of metallic catalysts is shown in Scheme 9. Also, higher enameling speeds and a good adhesion behavior were obtained using a melamine

Scheme 9. Carbodiimide with carboxylic acid groups.

modied blocked polyisocyanate adduct.[29] Thus, a diisocyanate (MDI or TDI) was partially blocked with cresol. The remaining free isocyanate groups were converted with melamine and a low molecular weight polyol like TMP.

Scheme 10. Di- and trimerization of isocyanates.

Scheme 6. Hydantoin modied isocyanates.

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Scheme 11. Blocked TDI-trimer.

As additional cross-linker, blocked TDI-trimer is used in some cases for PU-WE and PEI-WE.[26] This product was introduced by Bayer under the name Desmodur1 CT stable[2] and is still under optimization.[27] In the difference to the dimerization of isocyanates to urediones, the trimerization forming an isocyanuric ring system is thermally stable (Scheme 10). The reaction is catalyzed with trimerization catalysts like potassium acetate.[28] The polymerization of the diisocyanates leads to an oligomeric mixture of isocyanurate-polyisocyanates, due to the non-stoichiometric reaction. The functionality was determined from titration of the NCO groups. Scheme 11 shows a representative structure of a phenol blocked TDI trimer with a functionality of three. Polyester Polyols As a reaction partner of the isocyanates, polyester polyols are used. They have the advantage, compared to polyether, of a higher thermal stability and a higher resistance towards oxidation. For the class A and class B PU-WE alkyd resins and simple polyesters out of ethylene glycol, diethylene glycol, triethylene glycol, glycerin, TMP, propane1,3-diol, butane-1,4-diol, pentane1,5-diol, hexane-1,6-diol, adipic acid, phthalic acids and their ester and anhydrides were used. The polyester polyols were synthesized in a poly condensation reaction of the diacids with the di- and trifunctional alcohols. As catalysts, metal (Pb, Zn, Sn, Mn, etc.) salts (acetates, octoates, etc.) or titanates can be used. The catalytic mechanism of such a poly condensation is known.[3234] During the condensation reaction, the water or methanol as by-product are eliminated by vacuum distillaScheme 12. Imide formation. tion. The process is controlled by
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measuring the viscosity and the acid- and hydroxy numbers by titration. The use of higher functional alcohols (higher than 2 like glycerin) leads to branched polyester polyols. The number of OH groups used is always in excess with regard to the number of carboxylic acid groups in the synthesis, to ensure that the polyester has enough free OH groups for the reaction with the polyisocyanate and the OH groups remaining are responsible for a good adhesion on the copper surface of the wire. Aliphatic alcohols were used, because they have a higher reactivity towards isocyanates due to their inductive effect. The aromatic acids are important for the thermal stability, while long chain aliphatics and glycols leads to a good exibility and breakdown resistance.[35,36] The introduction of the polyester imides[14] also inuenced polyurethane chemistry. The rst polyurethane wire enamel (PU-WE) reaching class F was available in 1975, invented by Dr. Wiedeking GmbH and Schweizerische Isola-Werke.[15,16] This polyurethane was prepared from a blocked isocyanate adduct and a polyester imide as hydroxy polyol component. The polyester imide was synthesized out of p,p-diaminodiphenylmethane (DADM), glycine, trimellitic acid anhydride (TMA) and diols and triols like glycols and 1,1,1-trimethylol propane (TMP). The imide was formed following the equation in Scheme 12. The primary amine is reacted with an aromatic anhydride, leading to rapid formation, occurring also at room temperature, of an amic acid. The imide group is formed after the ring closure of the amic acid, with water elimination. This mainly occurs at elevated temperatures, but may also occur in traces at room temperature. Due to the different reactivity towards amines of the two functional groups of TMA (carboxylic acid, anhydride) the formation of amic acid occurs more preferably than

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Scheme 13. Imide formation of esteried TMA.

amide formation (reaction of amine with carboxylic acid). The reaction of the formed acid with alcohols leads to the polyester imide polyols. The reaction can be carried out in a two step reaction (rstly, imide formation and secondly esterication) or in a single stage. Since the imide formation is thermodynamically preferable, the amine can form the imide also with already esteried TMA (Scheme 13). Instead of diamines (several aromatic amines are carcinogenic) the corresponding diisocyanates can be used. This has the additional advantage that carbon dioxide, not water, is the byproduct, which can be eliminated easily. The reaction can be also used for the synthesis of polyisocyanate cross-linker (Scheme 14). This type of reaction is preferred, since the diimido diacid is a basically insoluble substance, which becomes soluble in the polyester mixture, once esteried. Also in this patent, the use of tris-(2-hydroxyethyl)isocyanurate (THEIC; Scheme 15) as a trifunctional alcohol is described. This branching agent, introduced by Schenectady,[37] can improve Scheme 14. Formation of imide-containing polyisocyanates.
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mechanical and thermal properties (cut through, tan d, TI) of the resulting product. To adjust the ester-imide ratio of the polyester imide, additional acids were added. These are mainly terephthalic acid and isophthalic acid and their methyl esters as well as TMA. Since class F PU-WE were available, they were discussed as a replacement for class F solderable polyester imides.[38] Increasing the imide content of the polyester imide polyol and using MDI, which has got a higher thermal resistance than TDI, for the polyisocyanate adduct lead to the introduction of a class H polyurethane wire enamel in the mid-1980s by Dr. Wiedeking GmbH.[39] This is still now the top performance version of a high thermal stable PU-WE. To improve some

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Scheme 15. Tris(2-hydroxyethyl)isocyanurate.

properties, a couple of other modications had been made. Polyamide-imide modied polyurethane[40,42] as well as hydantoin modication of PU-WE[41] leads to higher thermal values, like cut through. The chemistry has already been described above.

Catalysts To accelerate the polyurethane formation on the wire metal (Pb, Sn, Fe, Ti, Zn) carboxylates and alcoholates, tertiary amines, like triethylamine and diazabicyclooctane (DABCO), and dendritic tertiary amines[43] were used. In general, it can be said that the organometallic compounds formed a complex with the reaction partner, lowered the reaction enthalpy and increased the reaction speed. The tertiary amines lowered the reaction enthalpy and increased the reaction speed by opening a new pathway for hydrogen transport. The activity of the amines increased with their basicity and with less steric hindrance. For example, the activity of DABCO is eight times higher compared to triethylamine[44] (Scheme 16). One main type of mechanism has been proposed to describe the amine catalyzed urethane formation in the last ve decades.[4550] The complexion of isocyanate with the tertiary amine is followed by the attack of the nucleophilic agent and the formation of a hydrogenbonded complex between them, which attacks the isocyanate in a second step (Scheme 17).

The exact mechanism depends on the electrophilicity of the isocyanate, the acidity and nucleophilicity of the hydrogen active compound and the basicity of the catalyst (Scheme 18). Hydrogen containing compounds (HX) of high acidity and low nucleophilicity like phenol should lead to the protonation of the catalytic compound (B) followed by the nucleophilic addition of the anionic species to the isocyanate compound (Scheme 18, Route a). HX compounds with low acidity and high nucleophilicity like aromatic amines being directly added to the isocyanate with formation of the X C bond (Scheme 18, Route c). Proton transfer and X C bond formation take place in one single step, if HX has moderate acidity and nucleophilicity (Scheme 18, Route b). A lot of different mechanisms for the organometalcatalyzed polyurethane formation have been described in the literature.[45] The mostly suggested and conrmed mechanism is shown in Scheme 19. First the alcoholysis of the metal catalyst occurs in a previous step before the catalytic cycle starts. The isocyanate compound coordinates to the metal alcoholate and the Nmetal carbamate is formed as intermediate by the transfer of the alkoxide ion into the isocyanate. In the presence of alcohol urethane formation and metal alcoholate regeneration is obtained. Mixtures of tertiary amines and organo metals have also been used as a balanced catalytic system.[39] The synergetic effect in the catalytic process of urethane formation consists of the catalytic effect promoted by the simultaneous addition of the catalysts that is higher than expected on the basis of the simple addition of the catalytic effect of the isolated species. A proposed explanation[45] for this non-additive effect has been the reaction of both activated reagents and the consequent formation of a quaternary donor-acceptor complex between the catalysts and the involvement of this complex with active hetero associates (Scheme 20). An interesting aminic catalyst was introduced in the 1970s. This is an aldimine, a condensation product of butyraldehyde and aniline (Scheme 21). Additionally to its catalytic effect, the aldimine crosslinks with isocyanates forming at lower temperature splittable bonds (Scheme 22). This leads to products with very low solder times.

Scheme 16. Triethylamine and DABCO.

Solvents The solvent of polyurethane wire enamel, or for wire enamels in general, is not a single solvent, but a solvent mixture or system adjusted to the enameling process. Due to the different solvents,

Scheme 17. Mechanism of the amine-catalyzed urethane formation.

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Scheme 18. Different routes of the amine-catalyzed urethane formation.

this system has got a boiling range from 150 to 250 8C to obtain a smooth wire surface during the enameling and curing process. For more than 50 years the basic solvent system has not changed much. Cresylic acids (a mixture of phenol, cresols, xylenols, other alkylated phenols and their isomers) were used. The cresylic acids have a strong solvent power, the right boiling range needed for the curing process and they are more or less cheap. Due to the polar nature of the polymers, as well as cresols, the solutions tend to have high viscosities. To reduce the viscosity on the one hand, and the price of the enamel on the other hand, aromatic hydrocarbons, such as xylene and solvent naphtha (a distillation fraction from coal and oil industry with a boiling range of 140 to 200 8C), are added as diluters. The optimal ratio between real solvents (cresols) and diluters (non-solvents) in respect to the viscosity and stable solutions was found for PU-WE to be 50:50.[51] To improve the wire surface quality and to increase the enameling speed additional solvents like dimethyl phthalate, butanol, and glycols were added.[5254]

Due to the toxic character of the solvents used, a lot of work has been done to nd alternative, environment friendly solvents. Dibasic esters, propylene carbonate, methyldiglycol, benzoic acid methyl ester, phenoxy ethanol and isophorone were found to be potential substitutes mostly invented by Altana Chemie AG and its subsidiaries.[5558] Also water soluble[59] and solvent free (hot melt) polyurethane coatings have been developed,[60] but until now they have not achieved a big market share.

Additives Additives were added to the wire enamel composition to improve the properties of the enameled wire. Phenolic resins, cyano guanidines, melamines, poly(oxyalkylene diamine)s enhanced the exibility and adhesion, and thereby improve the heat shock. Siloxanes were used as leveling agents and for a better abrasion resistance. As ame retardants, phosphoric ester derivates were used.[61] Triazoles, tetrazoles, phosphates and imidazoles and their sulfur analogues were used as corrosions inhibitors, which leads to a better adhesion. It was found that imidazole lowered the deblocking temperature of the blocked isocyanate adduct, which allowed higher enameling speeds.[62] Also, higher speeds were obtained by adding pure THEIC as an additive to the enamel.[63]

Manufacturing Process
Scheme 19. Organometal-catalyzed urethane formation.

Scheme 20. Quaternary donor-acceptor complex.

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Knowing the chemistry behind the polyurethane wire enamel, the process from the raw materials to the wire enamel will be explained as a representative example. In the rst step the polyester is synthesized. A reactor is charged with cresol, the diols, triols, carboxylic acids and the catalyst. The mixture is then heated up slowly. When the theoretically amount of distillate (water, methanol) is reached, additional solvent (cresol) is added. TMA and the aromatic diamine are added and the temperature raised. The product is adjusted by measuring the acid-number and

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Scheme 21. Condensation of butyraldehyde and aniline.

viscosity. When the specications are reached, the polyester is cooled down and diluted with solvents. Figure 1 shows the GPC curve (top) of a typical polyester polyol with average molecular weight of 4 800 Da and a polydispersity of 2.1. The peaks of the curve on the lower molecular weight end (right) of the distribution indicate different oligomers of the polyester. Going to the high

molecular weight end, eluting rst, the peaks become smaller due to higher possibility of cross-linking. In a second reaction vessel, cresol (solvent and blocking agent) is loaded, before the isocyanates are added. The exothermic blocking reaction heats the mixture up. After the exothermic reaction stops, the mixture is heated and checked for NCO number. If the specied NCO number has

Scheme 22. Cross-linking of aldimines.

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Figure 1. GPC-curves of typical polyurethane wire (middle) and its polyester (top) and blocked polyisocyanate adduct (bottom).

been reached, the aliphatic triols and diols are added at this elevated temperature. The reaction is stopped when the specied viscosity is reached. It is cooled down and diluted with solvents. A typical GPC curve of blocked polyisocyanate adduct is also shown in Figure 1 (bottom). From coupling of the isocyanate adducts, different oligomers are present, indicated by the peaks at the lower molecular weight end, which become smaller towards the high molecular weight end. The average molecular weight of the distribution is 3 400 Da with a polydispersity of 2.4. In a mixing vessel the polyester, blocked polyisocyanate adduct, catalyst, solvents and additives are added and mixed. The nal adjustments of viscosity and solid content are made to obtain the ready polyurethane wire enamel. The molecular weight distribution of the polyurethane wire enamel (middle GPC-curve, pink) is the mixture of those of the polyester and blocked polyisocyanate adduct with a average molecular weight of 3 800 Da and a polydispersity index of 2.6. Figure 2 shows the IR spectra of some typical cured polyurethane wire enamels. This method is used to identify different PU-WE characterized by different raw materials. The spectra show the typical bonds resulting from the polymer class, like the CO double bond coming from the ester-, imide- and urethane groups at 1 706 cm1 and the CO bond at 1 213 cm1. The intensity of the
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characteristic bonds and the ngerprint area differ with the enamel composition.

Properties The wire enamel is characterized by its viscosity and solid content. The solid content is measured, for example, by curing 1 g of the enamel for 1 h at 180 8C in a 50 mm disc and weighing the residue solids. The solid content of typical wire enamels are in the range of 20 to 40%, the corresponding viscosities are in the range of 20 to 2 500 mPa s. All other properties were tested at the enameled wire having a cross-linked polymer coating around the wire. The enamel is applied on the wire with felt or dies. The wire with the liquid enamel runs through the oven of temperatures of 400 to 700 8C. First, the viscosity of the enamel decreased due to the high temperature. The low boiling solvents starts to evaporate and the viscosity increased again. Then the deblocking of the blocked isocyanate adduct occurred. With the help of the catalyst, the isocyanate cross-linked with the polyol during ongoing solvent evaporation. The blocking agent diffused to the enamel surface and evaporated with the solvents. At this later state, the high boiling solvents evaporated. The wire

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Figure 2. IR-spectra of cured typical wire enamels: a) PU-WE out of MDI cross-linker and polyester imide; b) PU-WE out of TDI cross-linker and polyester.

was cooled down and the process was repeated until the desired layer thickness is reached (5 to 10 times). The low deblocking temperature and the high reactivity of the isocyanate group is the reason why lower oven temperatures, compared to other wire enamels, were possible. This and the higher diffusion speed of the phenol as blocking agent compared to ethylene glycol using polyester or polyester imide wire enamels, allowed higher enameling speeds. The specications of winding wires insulated with polyurethane are described in specic parts of standards like IEC 60317-20 (class F PU), IEC 6031721 [class F PU polyamide (PA)], IEC 60317-35 [class F PU bond coat (BC)] and IEC 60317-51 (class H PU). The properties of the enameled wire depend basically on the chemical composition of the applied enamel. But not all properties can be optimized in one wire enamel. Special requirements can be met, but only with the reduction of other properties; The best compromise has to be agreed. In general the following modications can be made to adjust the properties of the PU-WE. To improve the solderability, more urethane groups, fewer imide groups or replacement with amide groups and fewer functional polyols should be used. The thermal values like tan d, cut through and TI can be raised by a higher cross-linking density (use of higher functional educts), an increased
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heterocycle or imide content and a higher aromatic content. A higher cross-linking density improves also the hardness and abrasion resistance as well as the chemical resistance. The exibility can be improved by having more exible groups inside the molecule, like ether groups and aliphatics, as well as by the addition of phenolic resins to the enamel. The same modications improve also the heat shock. Adhesion of the coating on the conductor can be improved by adding corrosions inhibitors and adhesion promoters. The ratio between solid content and viscosity can be improved by the use of lower molecular weight polyols, aliphatic educts and alternative solvents with strong solvent power and low viscosity. PU-WE are available in all classes with different properties. Table 2 shows the some representative PU-WE. Polyurethane wire enamels can be divided into TDI-based and MDI-based ones in combination with a polyester or polyester imide. In general it can be said, that TDI-based PU-WE compared to MDI-based ones having lower solder times and lower thermal values (TI, heat shock, tan d, cut through). It can be also seen in this table that the composition of the polyester polyol inuenced the thermal and electrical values. With a polyester the lowest solder times can be obtained, whereas also the thermal values are low. THEIC- and imide modications increase the thermal resistance but also the solder time. The highest thermal

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Table 2. Properties of representative polyurethane wire enamels.

PU-Enamel

Solderability

Heat shock no stretch 1xD IEC -CS1

tan d

Cut through -C/IEC

Thermal index -C

Application range mm

Isocyanate cross-linker TDI-based TDI-based TDI-based TDI-based MDI-based MDI-based MDI-based

a)

Polyester polyol

s/ -C

-C

polyester polyester THEIC-polyester imide modied polyester imide modied polyester Polyester imide Polyester imide

3/320 0.5/360 1.5/375 8/320 9/320 2/360 2/375

180 175 180 170 180 200 200

150 160 155 150 160 180 180

220a)/210 240 250a)/245 250a)/230 230 /210 260 265a)/250

a)

158 155 174 157 171 182 195

0.020.50 0.031.00 0.020.80 0.302.00 0.021.00 0.021.00 0.021.70

Luscher test.

resistance can be obtained with imide rich polyester imides.

and eld coils for entertainment electronics and television. Class-H polyurethane wire enamels were used for automotive relays, ignition coils, transformers and solenoids.

Uses Wires can be classied into ne and ultra ne wires (d < 0.2 mm), intermediate wires (0.2 < d < 1.5 mm), heavy round and shaped wires (d > 1.5 mm). Polyurethane wire enamels are mostly used for enameling ne and ultra ne wires and intermediate wires. Such small diameters of the conductor do not allow mechanical scraping of the enamel. For this reason, solderable polyurethane enameled wires are used in small motors, dry-type transformers, telecommunications and in analytical instruments. The characteristics of various PU coated wires are depending on the nal use of the wire. Not only the thermal class is a criterion for the use, but all the different properties mentioned above, like tan d, cut through, exibility, hardness, abrasion and chemical resistance, adhesion behavior, etc. Today, mainly classes F and H polyurethane wire enamels are used. Polyurethane enameled wires are used as a single coat, or top coated with nylon or self bonding enamels. Self-bonding enamels are thermoplastic materials, like poly(vinyl butyrals), polyamides or phenoxy resins, which cure during the bonding process and have a resoftening temperature of roughly 180 8C. The coating layers are bonded into a compact structure without the need of an impregnating resin. Class-A and -B polyurethane wire enamels with nylon or bond coat are used for self supporting coils, voice coils, encapsulated coils, relays and yoke coils for toy motors and hair dryers, timer and clock coils. Class-F polyurethane wire enamels are used for motor coils, relays, ignition coils, solenoids, low voltage transformers, deection yoke coils,
Macromol. Mater. Eng. 2008, 293, 373386 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Future Trends and Technical Limitations

To overcome the increasing raw material costs, much work has been and still continues to be done to decrease the production costs (higher degree of automation) and in testing low cost raw materials. Due to the high price of cresol, attempts have been made and are ongoing to achieve high solids at standard viscosity. Special technologies have been and still are investigated, which deal with solvent free materials, like UV-curable varnishes,[6466] hot melt application,[6771] extrusion,[4648] electron beam curing and powder coating. The industrial application of these technologies is insignicant due to the investment costs. Every enameled wire manufacturer stays today with wire enamels solved in organic compounds. As already described above, alternative ecological friendly solvents with the same properties, like solvent power and boiling range, have been developed. Unfortunately they are more expensive than cresylic acids and, therefore, not very interesting for the wire producers. Improvement of the whole wire enamel level or just of some particular properties is still one major work in the R&D labs of the wire enamel producer. The market tends to go to smaller electrical devices with higher power, produced automatically in faster and faster ways. This is mostly valid for the ne wire segment, which requires for more and more thermal stable, high frequency resistant, fast solderable wire enamels. The general trend is for high thermal stable, eco-friendly and fast soldering polyurethane wire enamels, which allow a high enameling speed.

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Coatings for Solderable Wires for the Modern Electric Industry

Nanotechnology has found its way into the wire enamel chemistry,[72] improving signicant the corona resistance of the enameled wire. A lot of work is still going into this interesting technology, which has a big potential to improve properties and generate new properties to the wire.

Summary
Since its introduction almost 60 years ago, the interest and demand of polyurethane wire enamels has remained high. Over the years, the performance has been further and further optimized. Their main use, as coatings in the eld of ne and ultra ne wire for small electrical devices and electronics, where fast solderability at low temperatures is a must, makes polyurethanes especially an inalienable material for wire enamels today. The high copper price and the growing Asian market lead to an increasing ne wire market and, therefore, to a higher demand of polyurethane wire enamels. Further developments to enhance the properties and to improve the whole process will therefore be in focus in the future.
Received: November 9, 2007; Revised: January 25, 2008; Accepted: January 29, 2008; DOI: 10.1002/mame.200700366 Keywords: coatings; polyurethanes; processing; synthesis; thermal properties

[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18]

DRP 728981 (1937), inv. O. Bayer. http://www.bayercoatings.com/. Wire and wire products 1964, 231. L. J. Payette, IEEE Elect. Insulation Magn. 1990, 6, 8. T. Umekawa, S. Horikoshi, K. Iwai, I. Otake, Furukawa Denko Jiho 1964, 35, 44. US 3037959 (1962), invs. E. Lavin, A. H. Markhart;Chem. Abstr. 1962, 430107. BE 613493 (1962), invs. E. Lavin, A. H. Markhart, R. E. Krass;Chem. Abstr. 1962, 483775. US 3072596 (1963), invs. E. Lavin, A. H. Markhart;Chem. Abstr. 1963, 40965. US 3068189 (1962), invs. E. Lavin, A. H. Markhart;Chem. Abstr. 1963, 54301. US 3077462 (1963), invs. A. F. Fitzhugh, E. Lavin, R. N. Crozier;Chem. Abstr. 1963, 83085. US 3462513 (1969), invs. A. F. Fitzhugh, E. Lavin, C. F. Hunt;Chem. Abstr. 1969, 492768. G. F. Lipsey, P. W. Juneau, Power Appl. Syst. 1960, 73. Y. Saito, T. Hino, Power Appl. Syst. 1960, 653. DE 1445263 (1961), Dr. Beck & Co GmbH. US 3869428 (1975), invs. H. Mosimann, P. Heim, C. Borer;Chem. Abstr. 1975, 430069. H. Mosimann, in: Proceedings of the 12th Electrical and Electronic Insulation Conference, 1975, 152. GB 1075039 (1967), invs. J. D. Guest, A. Lowe, B. A. Mounteld;Chem. Abstr. 1968, 14172. B. Han, Tuliao Gongye 1981, 62, 10.

[19] GB 1175107 (1969), invs. A. R. Corry, J. D. Guest, A. Lowe;Chem. Abstr. 1970, 45112. [20] Polyurethane, Kunststoff-Handbuch 7, Carl Hanser Verlag, Munchen 1993, p. 84. [21] O. Bayer, Das Diisocyanat-Polyadditionsverfahren, Kunststoff Handbuch 7, 1966, p. 1. [22] DE 2750722 (1979), invs. J. Lewalter, R. Merten, W. Duenwald;Chem. Abstr. 1979, 441048. [23] JP 60067569 (1985), Tokyo Tokushu Densen;Chem. Abstr. 1985, 525166. [24] W. Dunwald, R. Halpaap, Proceedings of the FATIPEC Congress, 1988, Vol. III (19th), 185 ff. [25] JP 03043473 (1991), invs. H. Yokota, T. Suzuki, K. Hayashi, H. Asoshina;Chem. Abstr. 1991, 610342. [26] DE 2411124 (1974), invs. C. Cohen, B. Dudrif-Varambon, R. Salle, . Robert, B. Sillion;Chem. Abstr. 1975, 60035. [27] H. Li, Hecheng Shuzhi Ji Suliao 2004, 21, 26. [28] S. Petersen, Herstellung und Umwandlung von Isocyanaten, Vol. 8, 4th Ed. Houben-Weyl, 1952, 119. [29] EP 0419965 A2 (1990), invs. R. Halpaap, W. Dunwald, H. Casselmann. [30] GB 1075039 (1967), invs. D. J. Guest, A. Lowe, B. A. Mounteld. [31] GB 1175107 (1969), invs. A. R. Corry, D. J. Guest, A. Lowe. [32] K.-H. Wolf, B. Kuster, H. Herlinger, C.-J. Tschang, E. Schollmeyer, Angew. Makromol. Chem. 1978, 68, 23. [33] I. Shiihara, W. T. Schwartz, Jr., H. W. Post, Chem. Rev. 1961, 61, 1. [34] F. Weingart, Institute fur Textil- und Faser Forschung Stutt gart, 1994. [35] JP 56062823 (1979), Nitto Electric Ind. Co. Ltd. [36] JP 08188713 (1995), Hitachi Chem. Co. Ltd. [37] US 3211585 (1965), Schenectady Chemicals, Inc. [38] US 4997891 (1991), Schenectady Chemicals, Inc., inv. Cicero et al. [39] Internal paper, not published. [40] US 5514747 (1996), invs. Hsu et al. [41] DE 10051392 A1 (2002), Bayer AG, inv. R. Gertzmann. [42] JP 11111059 (1999), invs. A. Morikawa, K. Suzuki, K. Asano;Chem. Abstr. 1999, 259924. [43] P. E. Froehlich, T. Corstjens, DSM Research. [44] J. Burkus, J. Org. Chem. 1961, 26, 779. [45] A. L. Silva, J. C. Bordado, Catal. Rev. 2004, 46, 31. [46] R. Becker, L. Thiele, Polyurethane catalysis, in: Polymeric Materials Encyclopedia, Vol. 9, 1st Edition, 1996, 6940. [47] M. S. Vratasanos, Polyurethane catalysis, in: Polymeric Materials Encyclopedia, Vol. 9, 1st Edition 1996, 6947. [48] S. Wendel, Structural inuence on performance of urethane catalysts for exible moulded and slabstock foams, in: Catalysis in Polyurethane Foams, Proceedings of the seminar, Shrewsbury, UK,: 1997. [49] K. Schwetlick, R. Noack, F. Stebner, J. Chem Soc., Perkin Trans. 1994, 3, 599. [50] US 3988251 (1976), invs. Shelby et al., Rea. [51] D. K. Teer, M. H. Strunk, E. Jensen, IEEE 1991, 147. [52] DE 2747456 (1979), Dr. Wiedeking GmbH, inv. K. Ohm;Chem. Abstr. 1979, 406500. [53] JP 62086067 (1987), invs. I. Ishikawa, S. Chahata, T. Yamazawa;Chem. Abstr. 1987, 578245. [54] JP 63003069 (1988), invs. S. Chiyahata, I. Ishikawa, T. Yamazawa;Chem. Abstr. 1988, 188593. [55] DE 2632047 (1978), Dr. Beck & Co GmbH, invs. H. Wendt, H. Janen. [56] DE 2849120 (1979), Hitachi Chem. Co Ltd., invs. Y. Okada, J. Fukuhare.

Macromol. Mater. Eng. 2008, 293, 373386 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

www.mme-journal.de

385

S. Rost

[57] DE 3938058 (1991), Dr. Beck & Co GmbH, invs. K. W. Lienert, H. Lehmann, J. Runge, S. Stojanoy. [58] WO 03070845 (2003), Altana Elec. Ins. GmbH. invs. G. Stevens, G. Biondi, P. Penczek, E. Wardzinska. [59] JP 75151298 (1975), invs. E. Hosokawa, M. Waki, T. Hoshino. [60] DE 2404740 (1975), invs. W. Duenewald, J. Lewalter, W. Zecher, W. D. Last. [61] CA 979561 (1975), Schenectady Chemicals, Inc., inv. R. F. Weddleton. [62] US 3764375 (1973), Schenectady Chemicals, Inc., inv. C. M. Orlando. [63] DE 3133571 (1983), Bayer AG, invs. W. Duenewald.

[64] JP 05258617 (1993), invs. K. Suzuki, K. Asano, H. Kikuchi;Chem. Abstr. 1994, 109640. [65] JP 07057548 (1995), Hitachi Cable, invs. Kato et al.Chem. Abstr. 1995, 584174. [66] JP 07282638 (1995), Hitachi Cable, invs. Kikuchi et al.Chem. Abstr. 1996, 67401. [67] D. A. Bolon, B. Gorowitz, Schenectady Higher-Solid Coatings 1984, 9, 2. [68] US 4389457, General Electric Co. [69] EP 0024674 (1979), Dr. Beck & Co. [70] DE 2911269 (1979), Dr. Beck & Co. [71] WO 02/099821 (2001), Furukawa Electric Co. [72] US 6908692 (2004), E.I. du Pont de Nemours and Co.

386

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DOI: 10.1002/mame.200700366