[0001] The present invention relates to enameled wires having good self-lubricating properties.
[0002] Recently, manufacturers of electric apparatuses that use enameled wires have come
to use high-speed automatic winding machines to increase the speed of the production
line. The enameled wire is subjected to friction and other mechanical stresses during
winding which causes the insulation coating to be damaged mechanically. If such damaged
wire is assembled in an electric machine, layer shorting (short-circuiting between
wires) occurs and the loss factor is increased to an undesirably high level. Therefore,
to minimize the mechanical damage to the insulation coating, enameled wires having
good self-lubricating properties have been demanded. Wires with self-lubricating properties
are needed not only for use in connection with an automatic winder but also when enameled
wires are inserted manually into a small slot in a motor.
[0003] On the other hand, to achieve energy saving, additional improvements in the efficiency
of various motors and transformers are desired. This requirement is particularly great
for motors to be immersed in refrigerants for coolers, air conditioners and refrigerators,
and to meet this end, the space factor is increased by inserting more enameled wires
into small slots in motors.
[0004] Since enameled wires themselves do not have good self-lubricating properties, a layer
of various liquid lubricants such as liquid paraffin and refrigerator oil has been
conventionally applied to the enameled wires. However, as more enameled wires are
inserted into the small slot to reduce the amount of space needed and hence increase
the efficiency of motors, many problems have arisen which cannot be solved by using
a conventional enameled wire coated with liquid lubricants such as refrigerator oi3.
For one thing, liquid lubricants such as refrigerator oil do not have very high lubricating
properties and slip properties. Accordingly, a great number of enameled wires cannot
be easily inserted into a small slot, and if they are inserted with great force, the
enamel coating is damaged mechanically which increases the chance of layer shorting..
The low self-lubricating properties of the enameled wire causes another disadvantage
in that even after the coil of enameled wire is inserted in the motor, the enamel
coating is subjected to mechanical damage due to electromagnetic vibration. As a result
of the mechanical damage, layer shorting occurs and the motor fails to perform its
function. Improving the self-lubricating properties of enameled wires by applying
a large quantity of liquid lubricants has little effect. On the contrary, the use
of such lubricants causes more dirt to collect on the enameled wires and the bonding
strength of adhesive tape used to fix the ends of the coil is adversely affected.
[0005] Attempts have been made to eliminate these defects by coating enameled wires with
solid lubricants such as solid paraffin and carnauba wax having better lubricating
properties and slip properties than liquid lubricants. However, because most of the
solid lubricants are insoluble or sparingly soluble in solvents, they are usually
applied to the enameled wire from a solution having a few percent of the lubricant
dissolved. in solvents such as petroleum benzine and xylene, and the solvent is subsequently
evaporated. This method requires wasting a large. quantity of solvents. Furthermore,
the method requires a vapor scrubber to protect the health of workers as well as a
burner and other means to remove the discharged vapor and convert it into a harmless
form. The use of solvents having low flash points presents a fire hazard; and a heating
furnace is necessary for drying the applied wire enamel coating. As a further defect,
the solvent on the insulation coating of some wires can cause creasing or crazing
that makes the wires no longer acceptable as commercial products. Therefore, the coating
of solid lubricants can only be applied to limited types of electric wires. Furthermore,
the lubricant solution has such a low concentration and viscosity that the thickness
of the lubricant coating cannot be controlled satisfactorily. All the operator can
do is to simply pass the electric wire through the lubricant solution and let it deposit
on the wire surface. It is, therefore, very difficult to apply the lubricant solution
in a controlled amount.
[0006] If the enameled wires having a coating of these solid lubricants are applied to motors
to be immersed in refrigerants, the lubricant coating is extracted by the refrigerant
and can clog the opening of the compressor valve or the refrigerant expansion nozzles
in the refrigerator. This will reduce the refrigerating capacity of the machine. In
addition, if the lubricant is extracted by the refrigerant, the self-lubricating properties
and slip properties of the enamel wire are reduced and the enamel coating becomes
vulnerable to mechanical damage due to electromagnetic vibration.
[0007] Another method that has been proposed for providing enameled wires with high self-lubricating
properties is to use wire enamel compositions containing synthetic resins having good
lubricating properties such as polyethylene, polypropylene and polytetrafluoroethylene,
silicone oil, fluorine containing surfactants, and liquid as well as solid lubricants
such as paraffin wax, carnauba wax and montan wax. But synthetic resins such as polyethylene,
polypropylene and polytetrafluoroethylene are sparingly soluble in wire enamel compositions
and are difficult to disperse in the enamel uniformly, and the resulting enamel is
not highly stable. What is more, these polymers are not highly miscible with the components
of the enamel so it is difficult to disperse them in the enamel coating uniformly
and the resulting enamel coating does not have a good appearance. Liquid lubricants
in the wire enamel composition provide a wire enamel coating whose slip properties
and self-lubricating properties are as low as those of the coating formed by applying
them onto the enameled wire. Solid lubricants in the wire enamel composition are sometimes
extracted by refrigerants or solvents after the wire enamel is applied to the electric
wire (the same thing happens when solid lubricants are directly applied to the enameled
wire). Enameled wires so produced are not desirably applied to motors that are to
be immersed in refrigerants. Furthermore, like synthetic resins, the solid lubricants
are sparingly soluble in solvents for making wire enamel and they are not highly miscible
with the insulating components of the enamel. Therefore, the resulting wire enamel
is not stable and the lubricants are difficult to disperse in the enamel coating uniformly
and hence the so produced coating does not have good appearance.
SUMMARY OF THE INVENTION
[0008] As a result of various studies to eliminate the above defects of the conventional
enameled wires, the present inventors have found that a desired enameled wire can
be produced by forming one or more wire enamel coatings on a conductor and a lubricating
wire enamel coat on the outermost layer of said wire enamel coat that is made by applying
and baking a wire enamel composition consisting essentially of a resin at least one
molecule of which is terminated with a straight alkyl group having 21 or more carbon
atoms. The enamel wire of the present invention itself has self-lubricating properties
equal to those of the wire that has a layer of solid lubricants such as solid paraffin
and carnauba wax, or those of the wire that is produced by coating the conductor with
a wire enamel composition containing such solid lubricants or synthetic resins such
as polyethylene and polypropylene having good lubricating properties.
[0009] In the enameled wi.re of the present invention, the wire enamel coating itself has
high self-lubricating properties. In this respect, the wire differs greatly from the
conventional product wherein a lubricant is present on the surface of the enameled
wire or within the wire enamel coat. The wire enamel composition used in the present
invention is more stable and uniform than wire enamel compositions containing synthetic
resins having good lubricating properties such as polyethylene and polypropylene,
or solid lubricants such as solid paraffin and carnauba wax. Furthermore, the resulting
enameled wire has a better appearance than those having a wire enamel coating made
from the latter type of wire enamel. There is little chance that the wire enamel coating
of the present invention will be extracted by refrigerants or solvents and clog the
opening of the compressor valve or the refrigerant expansion nozzles in comparison
with the wire enamel coating formed by applying solid lubricants such as solid paraffin
or carnauba wax on the surface of the enameled wire or the coating formed from a wire
enamel composition containing these solid lubricants. For these reasons, the enameled
wire of the present invention can be applied with advantage to motors that are to
be immersed in refrigerants and which are required to have high refrigerant resistance.
BRIEF DESCRIPTION OF THE DRAWING
[0010] Figure 1 is a cross section of the insulated electric wire of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0011] The enameled wire of the present invention comprises a conductor, one or more wire
enamel coatings formed on the conductor, and a lubricating wire enamel coat formed
on the outermost layer of said wire enamel coat. It is essential for the present invention
that the lubricating wire enamel coat be formed on the outermost layer of the one
or more wire enamel coatings on the conductor. If the lubricating wire enamel coat
is formed directly on the conductor, the desired mechanical characteristics may not
be obtained. The proportion of the lubricating wire enamel coat to the total thickness
of the coating on the conductor is preferably as small as possible to avoid any adverse
effect on the mechanical characteristics of the resulting enameled wire.
[0012] A wire enamel coat is usually formed on the conductor by 3 to 20 cycles of application
and baking of the wire enamel until a coating of desired thickness is formed. Therefore,
the best way to minimize the proportion of the wire enamel coat to the total thickness
of the coating is to effect only the last cycle of application and baking using a
wire enamel composition for making the lubricating wire enamel coat. For achieving
the desired mechanical characteristics, the thickness of the lubricating wire enamel
coat is preferably not more than 20% of the total thickness of the coating on the
resulting enameled wire.
[0013] The wire enamel coat formed as a base coat in the enameled wire of the present invention
may be made of any material such as polyurethane, polyvinyl formal, polyester, polyester
imide, polyhydantoin, polyamideimide, polyimide, polyester amideimide and polyamide.
These resins may be combined in the form of, say, polyurethane-polyamide, polyester-polyamide,
polyester- polyamideimide, polyester imide-polyamideimide, and polyimide-polyvinyl
formal. Since the enameled wire of the present invention may be applied to motors
to be immersed in refrigerants, the base wire enamel coat is preferably made of vinyl
formal, polyester, polyester imide, polyamideimide, polyester amideimide and polyimide,
and mixtures thereof.
[0014] The lubricating wire enamel coat formed as a top coat in the enameled wire of the
present invention is formed by applying and baking a wire enamel composition that
consists essentially of a resin at least one molecule of which is terminated with
a straight alkyl group having 21 or more carbon atoms and preferably 27 to 31 carbon
atoms. The polymer backbone may be bonded to the terminal straight alkyl group in
any - fashion such as amido bond, imido bond, ester bond, urethane bond or urea bond.
The straight alkyl group bonded to a terminal of the polymer chain must have at least
21 carbon atoms to provide good lubricating properties, and the desired lubricating
properties are not achieved if said alkyl group has less than 21 carbon atoms. Briefly
stated, if the terminal is represented by -(CH
2)
n-1CH
3, n must be 21 or more. The alkyl group is preferably in a completely linear form,
but it may be partially branched as long as the straight portion has at least 21 carbon
atoms.
[0015] The polymer chain to a terminal of which the straight alkyl group having 21 or more
carbon atoms is to be attached may be made of any resin such as polyamideimide, polyimide,
polyester, polyester imide, polyurethane, polyester amideimide, polyamide or polyhydroxyether.
Two typical methods of introducing the straight alkyl group having 21 or more carbon
atoms at a terminal of the molecule of these resins are 1) reacting the materials
for preparing the polymer chain of the resin to be produced with a compound that is
described hereunder and which is used to introduce the straight alkyl group having
21 or more carbon atoms at a terminal of the molecule of the resin, so as to form
the polymer chain and introduce the straight alkyl group at the terminal of its molecule,
and 2) reacting the materials for preparing the polymer chain among themselves, then
depolymerizing the resulting resin with a compound that is used to introduce the straight
alkyl group having 21 or more carbon atoms at a terminal of its molecule so as to
introduce said alkyl group at the terminal.
[0016] Examples of the compound that is used to introduce a straight alkyl group having
21 or more carbon atoms at a terminal of the molecule of the resin used to form the
lubricating wire enamel coat include aliphatic acids, alkyl esters and acid halides
thereof, as well as higher alcohols, amines and aliphatic acid amides. Illustrative
examples of aliphatic acids include docosanoic acid, tricosanoic acid, tetracosanoic
acid, pentacosanoic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid,
nonacosanoic acid and triacontanoic acid, and derivatives of these aliphatic acids
are esters, acid anhydrides and acid halides. Illustrative examples of higher alcohols
include n-heneicosanol, n-docosanol, n-tetracosanol, n-hexacosanol, n-octacosanol,
and n-triacontanol. Illustrative examples of amines include heneicosylamine, docosylamine,
tricosylamine, pentacosylamine, hexacosylamine, and octacosylamine. Illustrative examples
of aliphatic acid amides include docosylamide, hexacosylamide and octa- cosylamide.
It is, of course, necessary that if these compounds are used to introduce the straight
alkyl group at a terminal of the polymer chain, they should have functional groups
that are capable of reacting with the materials used to prepare the polymer chain.
These compounds need not be used individually and may be used in admixture. For instance,
Hoechst Wax S sold by Hoechst Japan Ltd. that is based on montan wax acid (chain length:
C 28-32), Hoechst Wax E (ester of montan wax acid) or Hoechst Wax OP (partially saponified
ester of montan wax acid) also sold by Hoechst Japan Ltd. may be used.
[0017] Any solvent can be used to dissolve the resin at least one molecule of which is terminated
with a straight alkyl group having 21 or more carbon atoms. When preparing a wire
enamel composition, preferred solvents are those which consist essentially of N-methyl-2-pyrrolidone,
N,N-dimethylacetamide, m-cresol, p-cresol and various xylenols because the resulting
polymer solution can be directly used as wire enamel for making enameled wires. Suitable
solvents that can be used to control the viscosity of the polymer solution are toluene,
xylene, solvent naphtha, acetone, methyl ethyl ketone, cyclohexanone and Cellosolve
acetate.
[0018] The wire enamel composition according to the present invention which consists essentially
of a resin . at least one molecule of which is terminated with a straight alkyl group
having 21 or more carbon atoms is either a polymer solution per se of the resin at
least one molecule of which is terminated with a straight alkyl group having 21 or
more carbon atoms, or such polymer solution that contains one or more additives such
as other thermoplastic resins, thermosetting resins, curing agents, fillers, pigments
and dyes in an amount that does not impair the characteristics of said solution. The
polymer solution per se is preferred.
[0019] The present invention is now described in greater detail by reference to the following
examples and comparative examples which are given here for illustrative purposes only
and are by no means intended to limit its scope. Unless otherwise noted, all reactions
were performed in the following reference examples under thorough stirring in a reaction
vessel having a 3 liter capacity four-necked flask equipped with a cooling tube, a
fractionating column, a thermometer and a stirrer. The reaction vessel was heated
with a mantle heater. Baking of the polymer solution coated wires was carried out
in a vertical furnace at a furnace temperature of 360°C in the top, 320°C in the middle
and 260°C in the bottom as the wire was supplied at a linear speed of 15 m/min. All
characteristics except the coefficient of static friction of the enameled wires prepared
were measured in accordance with JIS C3003. The coefficient of static friction was
measured by the following method in terms of the coefficient of static friction between
enameled wires: two parallel enameled wires were placed on a horizontal plane; a metal
block to the bottom of which two parallel enameled wires were fastened was placed
on said horizontal plane so that the respective pairs of wires crossed each other
at a right angle; the metal block was moved along the two wires on the horizontal
plane; and the minimum load necessary for moving the block was divided by the weight
of the block to determine the coefficient of static friction of the wires.
REFERENCE EXAMPLE 1
[0020] Diphenylmethane-4,4'-diisocyanate (500.5 g) was gradually added to a mixture of trimellitic
anhydride (384.3 g) and N-methyl-2-pyrrolidone (1,653.8 g) under stirring, and the
resulting mixture was heated at 80°C for 3 hours. Thereafter, the temperature of the
reaction mixture was increased at a rate of 20°C per hour. During the reaction, the
viscosity of the solution gradually increased, accompanied by the generation of carbon
dioxide gas. When the temperature of the reaction mixture reached 160°C, the heat
was removed, and the reaction was continued at that temperature for 2 more hours until
a polyamideimide polymer solution was obtained. The polymer had a reduced specific
viscosity of 0.38 dℓ/g as measured at 30°C in 100 m2 of N,N'- dimethylacetamide having
0.5 g of the resin dissolved. The polymer solution was diluted with xylol to form
a wire enamel composition having a resin content of 25%. The wire enamel had a viscosity
of 17 poises as measured with a Brookfield type viscometer at 30°C.
REFERENCE EXAMPLE 2
[0021] Diphenylmethane-4,4'-diisocyanate (500.5 g) was gradually added to a mixture of trimellitic
anhydride (381.2 g), Hoechst Wax S (14.1 g, montan wax acid having a chain length
of 28 to 32 from Hoechst Japan Ltd.) and N-methyl-2-pyrrolidone (1,679.8 g) under
stirring, and the resulting mixture was heated at 80°C for 3 hours. Thereafter, the
reaction mixture was heated at a rate of 20°C per hour. When the temperature of the
reaction mixture reached 170°C, the heat was removed, and the reaction was continued
at that temperature for 1.5 hours until a polyamide resin solution wherein at least
one molecule of the resin was terminated with a straight alkyl group having 27 to
31 carbon atoms was obtained. The resin had a reduced specific viscosity of 0.49 dℓ/g.
The resin solution was diluted with xylol to form a wire enamel composition having
a resin content of 25%. The wire enamel had a viscosity of 38 poises.
REFERENCE EXAMPLE
[0022] Diphenylmethane-4,4'-diisocyanate (500.5 g) was added to a mixture of trimellitic
anhydride (382.4 g), docosanoic acid (6.8 g) and N-methyl-2-pyrrolidone (1,667.0 g)
under stirring and the resulting mixture was heated to 80°C where it was subjected
to reaction for 3 hours. Thereafter, the reaction mixture was heated at a rate of
20°C per hour. When the temperature reached 175°C, the heat was removed and the reaction
was further continued for 1 hour and 45 minutes until a polyamideimide resin solution
wherein at least one molecule of the resin was terminated with a straight alkyl group
having 21 carbon atoms was obtained. The resin had a reduced specific viscosity of
0.70 dℓ/g. The solution was diluted with xylol to form a wire enamel composition having
a resin content of 25%. The wire enamel had a viscosity of 60 poises.
REFERENCE EXAMPLE 4
[0023] The following components were charged in a flask.

Under stirring, the mixture was gradually heated to 140°C at which temperature it
was subjected to reaction for 2 hours. It was then heated so that its temperature
increased at a rate of 20°C per hour. Throughout the reaction, xylene and by-products
were distilled out of the reaction system through the cooling tube. The viscosity
of the mixture increased gradually. When the temperature of the mixture reached 240°C,
the flask was evacuated and the reaction was continued at that temperature. The viscosity
of the mixture increased further. Thirty minutes after the evacuation of the flask
started, the pressure in the flask'was returned to atmospheric and the heat was removed.
Cresol was added to achieve a resin content of 40% and to dissolve the resin in cresol.
Two percent by weight each of tetrabutyl titanate and zinc octanoate (based on the
resin) was added to make a polyester wire enamel composition. The wire enamel had
a viscosity of 72 poises.
REFERENCE EXAMPLE 5
[0024] The following components were charged in a flask.

The mixture was treated as in Reference Example 4 to produce a polyester wire enamel
composition wherein at least one molecule of the polymer was terminated with a straight
alkyl group having 21 carbon atoms. The enamel had a viscosity of 69 poises.
REFERENCE EXAMPLE 6
[0025]

[0026] Under stirring, the temperature of the mixture was elevated to 140°C at which temperature
the mixture was subjected to reaction for 1.5 hours. The temperature was further increased
at a rate of 20°C per hour. When the temperature reached 200°C, the reaction was further
continued for one hour at that temperature. Throughout the reaction, xylene and by-product
(methanol) were distilled out of the reaction system through the cooling tube. Then,
the mixture was cooled to 110°C and the following compounds were added to the reaction
mixture:

When the temperature of the mixture was increased again, a yellow precipitate was
formed at about 120°C and the mixture solidified. Then, the mixture was held at 140°C
for 30 minutes without stirring, and thereafter, it was heated to 180°C over about
one hour. Throughout the reaction, water that was produced as a by-product was distilled
out of the reaction system through the cooling tube. Since the mixture became somewhat
fluid, it was heated to 230°C over one hour under stirring, whereupon it became transparent
and its viscosity increased gradually. The reaction was continued at 230°C for 2 hours,
and after the interior of the flask was evacuated, the reaction was further continued
for one hour. Then, the pressure in the flask was returned to atmospheric and immediately
thereafter, cresol was added to achieve a resin content of about 35%. The reaction
was discontinued and the mixture was dissolved in cresol. Two parts by weight each
of tetrabutyl titanate and zinc octanoate (per 100 parts by weight of the resin) was
added to make a polyester imide wire enamel composition, which had a viscosity of
30 poises.
REFERENCE EXAMPLE 7
[0027] The following components were charged in a flask:

Under stirring, the temperature of the mixture was elevated to 140°C at which temperature
it was subjected to reaction for 1.5 hours. The temperature was further increased
at a rate of 20°C per hour. When the temperature reached 200°C, the reaction was further
continued for one hour at that temperature. Throughout the reaction, xylene and by-product
methanol were distilled out of the reaction system through the cooling tube. Then,
the mixture was cooled to 110°C and the following compounds were added to the reaction
mixture:

When the temperature of the mixture was increased again, a yellow precipitate was
formed at about 120°C and the F mixture solidified. Then, the mixture was held at
140°C for 30 minutes without stirring, and thereafter, it was heated to 180°C over
about one hour. Throughout the reaction, water that was produced as a by-product was
distilled out of the reaction system through the cooling tube. Since the mixture became
somewhat fluid, it was heated to 230°C over one hour under stirring, whereupon it
became transparent and its viscosity increased gradually. The reaction was continued
at 230°C for 2 hours, and after the interior of the flask was evacuated, the reaction
was further continued for one hour. Then, the pressure in the flask was returned to
atmosphere and immediately thereafter, cresol was added to achieve a resin content
of about 35%. The reaction was discontinued and the mixture was dissolved in cresol.
Two parts by weight each of tetrabutyl .titanate and zinc octanoate (per 100 parts
by weight of the resin) was added to make a polyester imide wire enamel composition
wherein at least one molecule of the polymer was terminated with a straight alkyl
group having 27 to 31 carbon atoms. The wire enamel had a viscosity of 44 poises.
COMPARATIVE EXAMPLES 1 TO 9 AND EXAMPLES 1 TO 6
[0029] Table 1 clearly shows that the enameled wires of the present invention had far better
self-lubricating properties than the conventional products. In addition, the enameled
wires of the present invention had better mechanical characteristics than the samples
of Comparative Examples 2, 4 and 8 wherein the wire enameled coating was entirely
made of the lubricating wire enamel coat.
[0030] While the invention has been described in detail and with reference to specific embodiments
thereof, it will be apparent to one skilled in the art that various changes and modifications
can be made therein without departing from the spirit and scope thereof.