CN101374909A - Exothermic polyphenylene sulfide compounds - Google Patents

Abstract

Use of an exothermic additive in a polyphenylene sulfide compound results in an extruded or molded thermoplastic article that is electrically conductive and exothermic when connected to a source of electrical energy. Electronic devices benefit from these articles, particularly where ink must be melted for imaging of commercial graphics on a substrate.

Description

The polyphenylene sulfide compounds of heat release

Priority request

The application requires the right of priority of following patent application: No. the 60/764th, 052, the U.S. Provisional Patent Application series number of submitting on February 1st, 2006, and agency's numbering (Attorney Docket Number) is 12006001; No. the 60/785th, 236, the U.S. Provisional Patent Application series number of submitting on March 23rd, 2006, the agency is numbered 12006010.These two applications all are incorporated by reference into herein.

Invention field

The present invention relates to can be used for the polyphenylene sulfide composition of electron device.

Background of invention

Electron device need consider that electric power is controlled, energy consumption, heat be from the conveying to crucial electronic unit of the dissipation of crucial electronic unit and heat.Along with electron device becomes more complicated, people begin to seek equivalent material and come weight reduction, reduce cost and obtain the factor that other influences price and performance.

Have many designs to be used for taking away from electronic unit the example of the thermally conductive thermoplastic compound of heat, described electronic unit needs specific service temperature so that it has productivity and high efficiency.For example, be used for heat is seen off from the key part of microprocessor and so on available from the Sai Ma of Puli ten thousand companies (PolyOne Corporation)-technology board (Therma-Tech) product.

But, many electron devices that heat delivery need be arrived key part are arranged.The example of these electron devices is that some need be in certain temperature so that tinting material is transported to the electronic printing device of display medium.United States Patent (USP) the 6th, 905 has been described for No. 201 by heating and solid ink has been fused into liquid printing ink in the business graphics printing press.

United States Patent (USP) the 6th, 086, No. 791 (Miller) disclosed the coating and the film of nonmetal conducting paint composite, they can with heating effectively under the disruptive situation is not taking place when power supply links to each other, described composition comprises: (a) tackiness agent; (b) granularity is about the conductive sheet shape carbon black of 5-500 micron; (c) granularity is about the conductive sheet shape graphite of 5-500 micron; (d) volatile solvent; Be benchmark in non-volatile solids content in the described coating composition wherein, described (b) and weight sum (c) are about 10-75 weight %.United States Patent (USP) the 6th, 818, No. 156 (Miller) have also disclosed coating and the film that uses granularity to carry out heat release as nano level and micron-sized carbon-based material.

Summary of the invention

Unfortunately, the film that discloses of Miller and the coating surface that exists only in goods for example.These films and coating can become fragment, delamination or peel off, and it is untreated to make goods become.

This area needs is only can heat release in the middle of fusing under the high temperature or degraded and the main body at compound, thereby with heat delivery to the key part of electron device reaching temperature required compound, described electron device is a business graphics printer for example.Because described compound is heat release in its main body, therefore can not be because the loss of parts surface processing is caused the loss of heat conductance.

The present invention is the polyphenylene sulfide compounds of exothermicity in its main body, thereby has solved this problem of this area by providing a kind of with when power supply is connected.

One aspect of the present invention provides a kind of high temperature exothermic compositions, and said composition comprises polyphenylene sulfide and exothermic additive.

Another aspect of the present invention relates to a kind of thermoplastic article, and it comprises above-mentioned polyphenylene sulfide composition, when described goods link to each other with power supply, all is heat release within the main body of described goods.

Another aspect of the present invention relates to a kind of electron device, and this electron device comprises that at least one contains the parts of above-mentioned thermoplastic article.

For purposes of the present invention, ＂ exothermic additive ＂ represents particle that electric conductivity is higher and the lower particulate combination of electric conductivity, and when described polyphenylene sulfide composition is shaped when making goods and energising, described combination can be used to the temperature that provides specific.

With United States Patent (USP) the 6th, 086, No. 791 (Miller) or United States Patent (USP) the 6th, 818, the mode that discloses for No. 156, by being dispersed in the particulate combination of carbon black in the polyphenylene sulfide compounds and graphite, can be become by the goods of this compound formation has electroconductibility efficiently, thus can do not make described compound or by the thermoplastic article destructive prerequisite of this compound formation under heat release.Because the fusing point of polyphenylene sulfide or other degraded point are higher than the required temperature of parts of described electron device, it can be used for reaching any specific temperature from thermoplastic article emitting heat quantity of the present invention.

Explained advantage of the present invention with reference to following embodiment.

The accompanying drawing summary

Fig. 1 is the temperature-time curve figure of embodiment 2-6.

Embodiments of the present invention

Polyphenylene sulfide

Polyphenylene sulfide is to comprise phenyl moiety and the polymkeric substance of one or more vulcanizing groups of being attached thereto.It will be recognized by those skilled in the art that the polyphenylene sulfide that can buy is suitable for the present invention on market.The non-limitative example of these polyphenylene sulfides that can buy on market (＂ PPS ＂) comprises (Woodlands, auspicious board (Ryton) the PPS powder of the various grades of cutting human relations Philips chemical company (ChevronPhillips Chemical Co.) Texas) available from the blue city of the Texas, USA martial virtue.In the document well known by persons skilled in the art arbitrarily patent can under the prerequisite that need not too much test, suitably determine suitable selection.

Exothermic additive

Be used for the combination that exothermic additive of the present invention is two kinds of multi-form carbon, preferably the combination of carbon black pellet and graphite granule.Described sooty electroconductibility is better than graphite.The non-limitative example of sooty substitute comprises carbon nanotube (single wall and many walls), nanofiber, and other form with carbon of high-aspect-ratio and electroconductibility.

A kind of acceptable commercially available carbon black is that (its granularity is about 35 nanometers for Akron, general woods tex (Printex) the XE2 superconduction carbon black pellet of Degussa Ohio) (Degussa) available from Ohio, USA Akron city.

A kind of acceptable commercially available graphite is that its granularity is approximately less than 20 microns available from super graphite company (Superior Graphite) No. 2939 pure flake graphites of heat (No.2939Thermally Pur.Flake graphite) (www.superiorgraphite.com).

Described general woods tex XE2 carbon black and No. 2939 graphite all disclose in the patent of Miller.

The size of two kinds of multi-form carbon can be nano level or micron-sized arbitrary dimension.The long-width ratio of these two kinds of multi-form carbon can be to can be used for the common any range of various carbon forms of the present invention, for example for about 20 to nanotube of the almost 1:1 of spheroidal particle, 000:1.

For United States Patent (USP) the 6th, 086, No. 791 (Miller) and United States Patent (USP) the 6th, 818, No. 156 (Miller) described reasons, the combination of carbon black pellet and graphite granule produces heat in one way, makes to produce specific temperature by the electric energy of specified quantitative that particular thermal plastic compound prescription is applied.Need not undue experimentation, specification sheets with the patent of above-mentioned Miller begins, those skilled in the art can add a certain amount of carbon black pellet and a certain amount of graphite granule prepares a kind of compound, this compound be electroconductibility and exothermicity when power supply is connected.

The balance of carbon black pellet and graphite granule can be by carbon black pellet with the main body of power delivery by polyphenylene sulfide, thus the electroconductibility of providing, simultaneously because the less conduction of graphite granule or the character of impedance produce heat.The patent of Miller institute is unexpected to be, the combination of two kinds of multi-form carbon can be dispensed in the main body that polyphenylene sulfide compounds forms electroconductibility and exothermal nature are provided.The patent of Miller does not disclose the tackiness agent that polyphenylene sulfide is suitable as its coating and film.

The weight ratio of the carbon form that higher carbon form of electroconductibility and electroconductibility are lower in the described exothermic additive is about 0.3:1 to 3:1.

Total amount in the thermoplastic compound is a benchmark, and the semi-invariant of described exothermic additive is about 1-75 weight %.In general, under the situation of the proportions constant between the lower carbon granule of the higher carbon granule/electroconductibility of electroconductibility, the concentration of exothermic additive is high more, and the specific heat release that applies thermoplastic compound under the electric energy situation is many more.

Other optional polymkeric substance

Compound of the present invention can comprise form or the rheological of other fluoropolymer resin to change described compound.Described other polymkeric substance can be compatible with PPS, and is perhaps incompatible with PPS so that form mixture, makes to form continuously/discontinuous two-phase polymer system.

The non-limitative example of other optional polymer comprises polyolefine, polymeric amide, polyester, polyalkenyl halides and urethane.Present polyolefine preferably in these optional polymer, polyethylene for example, high density polyethylene(HDPE) (HDPE) more preferably is to reduce the fragility by the molded parts of compound of the present invention.

Gross weight in the thermoplastic compound is a benchmark, and the cumulative amount of described optional other polymkeric substance can be 0 weight % to about 25 weight %.

Optional additive

Compound of the present invention can comprise conventional plastics additive, and its content is enough to make that compound obtains required technological property or performance.Described consumption should not cause the waste of additive, should the processing or the performance of compound not worked the mischief yet.The technician in thermoplastics compounding (compounding) field need not undue experimentation, only need with reference to paper, for example the plastic design Library (Www.williamandrew.com) the plastics additive database (Plastics AdditivesDatabase) (2004), just can many kinds of additives that be used for The compounds of this invention be made one's options.

In compounding PPS, other compounding component need be incorporated into PPS and prepare the compounding preparation.Other compounding component can comprise filler, pigment and tinting material, if desired, comprises lubricant, impact modifier, UV stabilizer, other processing aid and other additive, biological example agent for killing or fire retardant.

Usually reduce cost and gloss with filler, filler can comprise conventional lime carbonate, clay, talcum, mica and diatomaceous earth filler.Useful pigment and tinting material can be organically, but preferably inorganic, for example titanium dioxide (it also can be used as UV stabilizer).

Impact modifier can be used for PPS to improve toughness, can comprise polyethylene, ABS, acrylic polymers and the multipolymer of chloro, perhaps methacrylic copolymer, for example methyl methacrylate-butadiene-styrene (MBS).

Other processing aid that is used for extruding the PPS of complex configuration comprises acrylic copolymer or styrene-acrylonitrile copolymer, in case complex configuration or structure extrude the generation marginal laceration.

Can make the adhesion that with lubricator reduces the hot-work metallic surface, lubricant can comprise polyethylene, paraffin oil and the paraffin that is used in combination with metallic stearate.Other lubricant comprises metal carboxylate and carboxylic acid.

According to the kind of additive and the variation of comparing working properties or the required generation of performance with the compound that does not add this additive, gross weight in the thermoplastic compound is a benchmark, and the cumulative amount of described optional additive can be 0 weight % to about 40 weight %.Need not undue experimentation, those skilled in the art can adopt statistical technique (for example experimental design) to determine suitable consumption.

Processing

The preparation of The compounds of this invention is also uncomplicated for the technician in thermoplastics compounding field.Compound of the present invention can be by batch operation or operate continuously preparation.

The mixing that continuous processing is carried out is carried out in forcing machine usually, and described forcing machine is elevated to is enough to make polymeric matrix fused temperature, adds the solids fraction additive at the head of forcing machine or the downstream of forcing machine.Forcing machine speed can be about 50-500 rev/min (rpm), preferably is about 100-300rpm.Usually the extrudate of forcing machine is granulated, and extruding after being used for perhaps is molded as polymer product.

Be enough to melt extrude under the temperature of PPS before, use Henschel mixer (Henschelmixer) together with described component physical mixed.The patent of Miller has disclosed grinds carbon black pellet with graphite granule, on the other side is that processing of the present invention at first is that PPS is mixed with carbon black, adds graphite then.Blended has improved the dispersion of two kinds of components within the entire body of the PPS goods of extruding of exothermic additive in proper order.

The mixing of batch process is carried out in banbury mixers (Banbury mixer) usually, and the temperature of described mixing machine also is elevated to is enough to make the polymeric matrix fusing, adds wherein so that will choose the solids fraction additive that adds arbitrarily wantonly.Mixing velocity is 60-1000rpm, and mixing temperature can be normal temperature.In addition, the material that draws from mixing machine can cut into less size, extrudes or be molded as polymeric object after being used for.

Compound can form powder, cubes or spherolite, so that further extrude or molding formation polymeric electronic device components.

Subsequently extrude or molding technology is that the technician of thermoplastic polymer manufacture field is well-known.Need not undue experimentation, ＂ extrudes by reference, regular processing Guide Book (Extrusion, TheDefinitive Processing Guide and Handbook) ＂; The ＂ molded parts shrinks and warpage handbook (Handbook of Molded Part Shrinkage and Warpage) ＂; Extraordinary molding technology (the Specialized Molding Techniques) ＂ of ＂; ＂ rotational molding technology (Rotational MoldingTechnology) ＂; And ＂ molding, device and die head are repaired welding handbook (Handbook of Mold, Tool and Die Repair Welding) ＂, (these documents are published by plastic design books version) (www.williamandrew.com) can use compound manufacturing of the present invention to have the possible arbitrarily shape and the goods of outward appearance.

The application of invention

The bright compound of this law can produce the goods of heat when can be formed in and be connected with electric energy.People can be connected by the goods that electrode is made power supply and The compounds of this invention, are enough to the temperature of the parts of electron device is elevated to the heat of required degree with generation.Can import the electric energy of described thermoplastic article by varistor control, thus controlled temperature.

If worry to be transported to the amount of the electric energy of goods, also can use the current limiter of any kind of, for example placed in-line safety fuse is no more than specific amount with the amount of the electric energy of the thermoplastic article of guaranteeing to be transported to heat release of the present invention.The safety fuse of connecting will prevent excessive power delivery to goods, makes the polyphenylene sulfide in the goods that degraded or fusing take place otherwise just can produce too much heat, perhaps destroys near any parts of the electron device of thermoplastic article.

Any type of electrode all is fit to be used for goods of the present invention are linked to each other with power supply.Clip to pressure-sensitive electrode available from the merchant wholesaler of 3M company and so on from the crocodile formula metal available from the human consumer retailer of wireless room (Radio Shack) and so on, the target of electrode is that goods are linked to each other with power supply, and does not cause too much energy waste.

Fix when the residing environment of goods, the amount of exothermic additive and kind have determined the temperature that goods kept in the described compound.

The coating that patent disclosed of Miller or film are may be from the exposed surface of goods chipping or peel off, on the other sidely be, the present invention is by being dispersed in exothermic additive among the entire body of thermoplasticity polyphenylene sulfide compounds, even the exposed surface of goods scratches or damages, its continuous performance also can be guaranteed.

According to the geometrical shape of goods, may need may provide electric energy for the various piece of goods for goods provide electrode more than one group.

In addition, make that very likely goods comprise distinct portions, these parts are made by different compounds, the concentration difference of dispersive exothermic additive wherein, thus make distinct portions have different temperature by design.

The electron device that can benefit from The compounds of this invention is too many, can't be exhaustive.The non-limitative example of electron device comprises those of following document illustration: United States Patent (USP) the 4th, 814,786; 5,123,961; 5,621,444; 6,860,591; With 6,905, No. 201, and U.S. publication application US2004/0114008 and US 2004/0114010, particularly United States Patent (USP) the 6th, 905, the printing ink melting tank assembly of No. 201 announcements.

Embodiment has further explained the present invention.

Embodiment

Embodiment 1

Compounding compound sample of the present invention is extruded it, is molded as test specimen.All samples are all composed of the following components: auspicious the board PPS of 82.5 weight %, and the general woods tex XE2 board carbon black pellet of 12.25 weight %, and No. 2939 super brand graphite graphite granules of 5.25 weight %, prepare total amount is 50 pounds at every turn.

Carbon black is done in the Henschel mixing tank and was mixed about 3 minutes, adds PPS then, mixes about 4 minutes, adds graphite then, continues to mix about 6 minutes.Dry mixture with described compound adds in century (Century) 30 forcing machines then, and table 1 has been listed setting and result.

Extrudate is granulated, and is used for molding subsequently.

Use 33 Cincinnati rice to draw Cologne (Cincinnati Millacron) mould machine, use following sheet material and the anti-long test rod of setting the molding The compounds of this invention.

Table 3 has shown the physical properties of test panel, and mean value is listed in test twice.

In order to measure exothermal nature, get out two about 6 inches at interval holes at the opposed end of the tensile test bar of routine, to connect brass screws.To be connected in brass screw then from the probe of self coupling resistance transformer (Variac voltage rheostat) to produce voltage circuit.The IR rifle is fixed on the about 4 inches surface temperatures of locating to measure excellent center in tension force stick top.

At first varitran (Variac) is set in 10 volts, the varitran set(ting)value increases gradually, and up to the required surface temperature that reaches about 350-360 ℉, this is the required temperature of printing ink fusing in the business graphics ink-jet printer.Then, it is constant that the varitran set(ting)value keeps, and per minute reads temperature reading (carrying out 30-40 minute) simultaneously, observes simultaneously and detect whether temperature reading keeps constant.Table 4 has shown the measuring result when the varitran set(ting)value remains on 33 volts, and prerequisite is by exothermic compound of the present invention, and specific voltage can obtain constant temp more than 30 minutes.

Embodiment 2-6

Table 5 has shown the prescription of embodiment 2-6, and they are identical withembodiment 1, and its difference has been to add HDPE and has improved the resistance of final molded parts to becoming fragile by this compound.The used compounding of embodiment 2-6 is identical withembodiment 1 with condition of moulding.

Table 6 shown shown in the result of varitran under imposing a condition.

Fig. 1 is the figure of the numerical value that shown that table 6 is listed.Notice that very interesting a bit is that in embodiment 2, the highest voltage setting has obtained minimum temperature.This may be that embodiment has the percentage ratio of minimum carbon black with respect to total carbon content because as shown in table 5.Find to have 50% HDPE content, total carbon content much at one and identical carbon black and can under lower voltage, obtain higher temperature with respect to the embodiment 5 of total carbon content percentage ratio by comparing embodiment 2 and embodiment 5.Therefore, in component design, need to consider the existence of optional aggregation thing, so that operation obtains specified temp under specific voltage.

By comparing embodiment 2-4, find that when the amount of amount, total carbon content and the HDPE of PPS is maintained fixed the voltage of varitran is being reduced in 35 volts from 140 volts, and carbon black also can increase exothermal effect with respect to the content increase of graphite.

Table 7 has shown the resistivity data of embodiment 2-6, and these data repeat 4 times then in test at first, to obtain mean value and standard deviation.Find that by comparing embodiment 2-4 along with the increase of carbon black with respect to total carbon content, relevant decline takes place resistivity.Find that by comparing embodiment 4 and embodiment 6 the extremely small variation of formulation content may cause resistivity different significantly.Because the compounding asynchronism(-nization) of embodiment 6 is in embodiment 2-5, so the compound working method also may impact.

By the discovery of comparing with the electrical resistivity results of table 7 of the heat release result with table 6 (and Fig. 1), minimum resistivity is in the minimum heat release that has obtained top temperature under the voltage that applies.This exceeds those skilled in the art expects, and the required temperature and the resistivity of preparation are inversely proportional to.

The invention is not restricted to above embodiment.Below be claims.

Claims (15)

1. polyphenylene sulfide composition, said composition comprises:

(a) polyphenylene sulfide,

(b) exothermic additive.

2. composition as claimed in claim 1 is characterized in that described exothermic additive comprises the combination of two kinds of multi-form carbon, and wherein a kind of electric conductivity of form is better than another kind of form.

3. composition as claimed in claim 1 or 2 is characterized in that, described exothermic additive is the combination of carbon black pellet and graphite granule, and wherein the electric conductivity of carbon black pellet is better than graphite granule.

4. composition as claimed in claim 2 is characterized in that, the carbon of the form that electric conductivity is more excellent is selected from: carbon black pellet, single-walled nanotube, many walls nanotube, nanofiber and their combination.

5. composition as claimed in claim 1 or 2 is characterized in that, described exothermic additive comprises and a kind ofly has high-aspect-ratio and be the form of the carbon of electroconductibility.

6. composition as claimed in claim 1 or 2 is characterized in that, described exothermic additive is the particle of size in nano level or micron order scope.

7. composition as claimed in claim 1 or 2 is characterized in that, described exothermic additive is that long-width ratio is about 1:1 to 20, the particle of 000:1.

8. as claim 2 or 3 described compositions, it is characterized in that the weight ratio of the carbon form that carbon form that described electric conductivity is better and electric conductivity are relatively poor can be 0.3:1 to about 3:1.

9. as each described composition among the claim 1-8, it is characterized in that, is benchmark in the gross weight of composition, and the content of described exothermic additive is about 1-75 weight %.

10. as each described composition among the claim 1-9, it is characterized in that, described composition also comprises other the optional polymkeric substance that is selected from polyolefine, polymeric amide, polyester, polyalkenyl halides and urethane, gross weight in described composition is a benchmark, and the content of described optional other polymkeric substance is that 0 weight % is to about 25 weight %.

11. composition as claimed in claim 10 is characterized in that, described other optional polymkeric substance comprises high density polyethylene(HDPE).

12. as each described composition among the claim 1-11, it is characterized in that, said composition also comprises and is selected from following optional additives: filler, pigment, tinting material, lubricant, impact modifier, UV stabilizer, processing aid, biocide and fire retardant, weight in described composition is benchmark, and described optional content of additive is that 0 weight % is to about 25 weight %.

13. the described method for compositions of preparation claim 3, this method may further comprise the steps:

(a) the described carbon black pellet of dry blending in mixing tank;

(b) polyphenylene sulfide is added in the described mixing tank, proceed dry blending;

(c) described graphite granule is added in the described mixing tank, continue described dry blending step, to form dry mixture;

(d) in forcing machine, described dry mixture is extruded.

14. a thermoplastic article, it comprises each described polyphenylene sulfide composition among the claim 1-12, when described goods are connected in power supply, is exothermicity in the entire body of described goods.

15. an electron device, it comprises the described thermoplastic article of claim 14.

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