PTC conductive polymer compositions

Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...

Reexamination Certificate

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C524S496000, C524S191000

Reexamination Certificate

active

06660795

ABSTRACT:

BACKGROUND OF THE INVENTION
The invention relates generally to polymeric positive temperature coefficient (PTC) compositions and electrical PTC devices. In particular, the invention relates to polymeric PTC compositions containing medium structure, large particle size, carbon blacks which exhibit improved over voltage capabilities and an enhanced PTC effect.
Electrical devices comprising conductive polymeric compositions that exhibit a PTC effect are well known in electronic industries and have many applications, including their use as constant temperature heaters, thermal sensors, low power circuit protectors and over current regulators for appliances and live voltage applications, by way of non-limiting example. A typical conductive polymeric PTC composition comprises a matrix of a crystalline or semi-crystalline thermoplastic resin (e.g., polyethylene) or an amorphous thermoset resin (e.g., epoxy resin) containing a dispersion of a conductive filler, such as carbon black, graphite chopped fibers, nickel particles or silver flakes. Some compositions additionally contain flame retardants, stabilizers, antioxidants, anti-ozonants, accelerators, pigments, foaming agents, crosslinking agents, dispersing agents and inert fillers.
At a low temperature (e.g. room temperature), the polymeric PTC composition has an ordered structure that provides a conducting path for an electrical current, presenting low resistivity. However, when a PTC device comprising the composition is heated or an over current causes the device to self-heat to a melting temperature, a transition from a crystalline phase to an amorphous phase, resulting in a large thermal expansion presents a high resistivity. In electrical PTC devices, for example, this resistivity limits the load current, leading to circuit shut off. In the context of this invention T
s
is used to denote the “switching” temperature at which the “PTC effect” (a rapid increase in resistivity) takes place. The sharpness of the resistivity change as plotted on a resistance versus temperature curve is denoted as “squareness”, i.e., the more vertical the curve at the T
S
, the smaller is the temperature range over which the resistivity changes from the low to the maximum values. When the device is cooled to the low temperature value, the resistivity will theoretically return to its previous value. However, in practice, the low temperature resistivity of the polymeric PTC composition may progressively increase as the number of low-high-low temperature cycles increases, an electrical instability effect. Crosslinking of a conductive polymer by chemicals or irradiation, or the addition of inert fillers or organic additives may be employed to improve electrical stability.
Attempts to enhance the voltage capability of PTC compositions have fairly recently involved the inclusion of specialized carbon blacks. For example, U.S. Pat. No. 5,174,924 to Yamada et al. demonstrates the usefulness of large particle size/high structure carbon blacks in place of other carbon blacks. The foregoing patent appears to disclose PTC compositions having improved voltage capabilities and a trade-off between device resistance and voltage capability. The improvements demonstrated by the foregoing patent are specifically limited, however, to the use of large particle size/high structure carbon blacks.
In view of the foregoing, there is still a need for the development of polymeric PTC compositions and devices comprising them that exhibit a high PTC effect, have a low initial resistivity, that exhibit substantial electrical and thermal stability, and that are capable of use over a broad voltage range.
SUMMARY OF THE INVENTION
The invention provides polymeric PTC compositions and electrical PTC devices having increased voltage capabilities while maintaining a low RT resistance. In particular, the polymeric compositions also demonstrate a high PTC effect (the resistivity at the T
S
is at least 10
3
times the resistivity at 25° C.) and a low initial resistivity at 25° C. (preferably 10 &OHgr;cm or less, more preferably 5 m&OHgr; or less). The electrical PTC devices comprising these polymeric PTC compositions preferably have a resistance at 25° C. of 500 m&OHgr; or less (preferably about 5 m&OHgr; to about 500 m&OHgr;, more preferably about 7.5 m&OHgr; to about 200 m&OHgr;, typically about 10 m&OHgr; to about 100 m&OHgr;) with a desirable design geometry.
The polymeric PTC compositions of the invention, demonstrating the above characteristics, comprise an organic polymer, a conductive filler including carbon black having an iodine adsorption of less than about 60 mg/g carbon and a dibutyl phthalate absorption of greater than about 115 cc/100 g, and, optionally, one or more additives selected from the group consisting of inert fillers, flame retardants, stabilizers, antioxidants, anti-ozonants, accelerators, pigments, foaming agents, crosslinking agents, coupling agents, co-agents and dispersing agents. The compositions may or may not be crosslinked to improve electrical stability before or after their use in the electrical PTC devices of the invention. Preferably, the polymer component of the composition has a melting point (T
m
) of 100° C. to 250° C.
The electrical PTC devices of the invention have, for example, the high voltage capability to protect equipment operating on Line current voltages from overheating and/or overcurrent surges. The devices are particularly useful as self-resetting sensors for AC motors, such as those of household appliances, such as dishwashers, washers, refrigerators and the like. Additionally, PTC compositions for use in low voltage devices such as batteries, actuators, disk drives, test equipment and automotive applications are also described below.


REFERENCES:
patent: 4237441 (1980-12-01), van Konynenburg et al.
patent: 4388607 (1983-06-01), Toy et al.
patent: 4534889 (1985-08-01), van Konynenburg et al.
patent: 5174924 (1992-12-01), Yamada et al.
patent: 5229452 (1993-07-01), Green et al.
patent: 5456750 (1995-10-01), Mackay et al.
patent: 5747559 (1998-05-01), Whitehouse et al.
patent: 6156837 (2000-12-01), Branan et al.

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