CN1992102A - PTC element - Google Patents
PTC element Download PDFInfo
- Publication number
- CN1992102A CN1992102A CN 200610156581 CN200610156581A CN1992102A CN 1992102 A CN1992102 A CN 1992102A CN 200610156581 CN200610156581 CN 200610156581 CN 200610156581 A CN200610156581 A CN 200610156581A CN 1992102 A CN1992102 A CN 1992102A
- Authority
- CN
- China
- Prior art keywords
- ptc
- plain body
- protective layer
- epoxy resin
- ptc element
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Thermistors And Varistors (AREA)
Abstract
A PTC element comprising a PTC element body containing a polymer matrix and conductive particles, a pair of electrodes in contact with the PTC element body, and a protective layer composed of a cured epoxy resin composition containing an epoxy resin and a thiol-based curing agent, and covering the PTC element body so as to seal the PTC element body.
Description
Technical field
The present invention relates to PTC (Positive Temperature Coefficient) element.
Background technology
The PTC element is the element that the positive temperature coefficient of resistance value when reaching certain specific temperature province increases rapidly.In the past, as this PTC element, known have a PTC element (spy opens the 2002-164201 communique) that possesses the plain body of thermistor, and the plain body of its thermistor contains matrix resin (matrix resin) (polymer matrix) and the metal dust that is made of crystalline polymer.
Summary of the invention
But, PTC element in the past, after the manufacturing, through after long-time, when standing thermal history, the problem that exists the plain body deterioration of PTC, room temperature resistance value to increase greatly.When room temperature resistance value becomes big, during inoperative and the resistance change rate between when work just diminish, so, as the PTC element, just become the state that can not normally bring into play function.
Therefore, the object of the present invention is to provide after the manufacturing, the PTC element that the deterioration of the plain body of the PTC when standing thermal history is fully suppressed through after long-time.
PTC element of the present invention has: the plain body of PTC that contains resin and conductive particle; The pair of electrodes that contacts with the plain body of this PTC; Constitute, cover the plain body of this PTC with solidfied material and make the sealed protective layer of the plain body of this PTC by the composition epoxy resin that contains epoxy resin and thio-alcohol curing agent.
In PTC element in the past, can think after manufacturing, that when long-time oxygen is from invade the plain body of PTC on every side.Then, under this state, when the PTC element stood thermal history, resin and conductive particle in the plain body of PTC were oxidized owing to the oxygen of invading, and can think by this oxidation, and the plain body deterioration of PTC causes the increase of room temperature resistance value.PTC element of the present invention becomes the element that the plain body of PTC is covered, do not exposed at outer surface by the protective layer of specific composition.Thus, the oxygen of invading in the plain body of PTC reduces, the resin when preventing to stand thermal history and the oxidation of conductive particle, and its result, the deterioration that is produced by the thermal history of the plain body of PTC is suppressed.And, if according to the inventor's etc. opinion, use as protective layer by solidfied material with the composition epoxy resin that uses the thio-alcohol curing agent, suppressed especially significantly through long-time back, the deterioration of the plain body of PTC when standing thermal history.
Form the composition epoxy resin of the solidfied material of protective layer, preferably also contain amines.Thus, improve the oxygen shielding of protective layer more.
PTC element of the present invention possesses: the plain body of PTC that contains polymer matrix and conductive particle; The pair of electrodes that contacts with the plain body of this PTC; With cover the plain body of this PTC and make the sealed protective layer of the plain body of this PTC, protective layer can comprise: epoxy resin and thio-alcohol curing agent react formed solidfied material layer; With constitute by the material lower than the oxygen permeability of this solidfied material layer, be scattered in the filler in the solidfied material layer.As filler, preferred inorganic filler.
If opinion according to inventor etc.; utilization comprises the protective layer of the filler that uses solidfied material layer that the thio-alcohol curing agent forms and be made of the material lower than its oxygen permeability; the plain body of protection PTC is suppressed at the deterioration through long-time back, the plain body of the PTC when standing thermal history more.
At least a portion of above-mentioned filler is preferably tabular.Bring into play the effect that the plain body of PTC of the present invention suppresses deterioration thus more significantly.
Above-mentioned protective layer is benchmark, preferably contains the above-mentioned filler of 5～50 quality % with the protective layer all-mass.The ratio of filler is during less than 5 quality %, and the effect that the plain body of PTC of the present invention suppresses deterioration just has the tendency of decline, and during greater than 50 quality %, protective layer and the adaptation of PTC element body and electrode just have the tendency of decline.
Above-mentioned protective layer preferably forms in the mode that also covers at least a portion of pair of electrodes when covering the plain body of PTC.
At this moment, protective layer is crossed at electrode and the plain body of PTC and is formed, and suppresses oxygen thus to invade from the electrode and the interface of the plain body of PTC, prevents that the effect of PTC element body deterioration from becoming more remarkable.In addition, protective layer forms by using the thio-alcohol curing agent, and is good with the adaptation of electrode, also can bring into play the effect that prevents that electrode from peeling off from the plain body of PTC.
Description of drawings
Fig. 1 is the stereogram of an execution mode of expression PTC element of the present invention.
Fig. 2 is the sectional view along the II-II line of Fig. 1.
Fig. 3 is the amplification sectional view of the part of presentation graphs 2.
Embodiment
Below describe preferred implementation of the present invention in detail.But, the invention is not restricted to following execution mode.
Fig. 1 is the stereogram of an execution mode of expression PTC element of the present invention, and Fig. 2 is the sectional view along the II-II line of Fig. 1.At the PTC element 1 shown in Fig. 1,2 is polymer PTC device, is contacted one side pair of electrodes facing 12,14 with PTC element 10 and covered the plain body 10 of PTC by the plain body 10 of PTC, one side to make the plain body 10 sealed protective layers 20 of PTC constitute.
Protective layer 20 cover in the plain bodies of PTC 10 surfaces with pair of electrodes 12,14 contact portions beyond part.Thus, the plain body 10 of PTC is capped into its surface and does not expose.Then, protective layer 20 forms in the mode that also covers the part on pair of electrodes 12,14 surfaces when covering the plain body of PTC 10 surfaces.Like this, form on the surface of electrode 12,14 and the surface of the plain body 10 of PTC, suppress oxygen and invade, prevent that the effect of PTC element body 10 deteriorations from becoming more remarkable from the interface of electrode 12,14 and the plain body 10 of PTC by protective layer 20 leaps.
Protective layer 20 is formed by the solidfied material of the composition epoxy resin that contains epoxy resin and thio-alcohol curing agent.The thickness of the protective layer 10 of the part that contacts with the plain body 10 of PTC is preferably 5～500 μ m.
As the epoxy resin in the composition epoxy resin of the solidfied material that forms protective layer 20; can use the resin that obtains with methods such as one-stage process, two-phase method, oxidizing process etc. with being not particularly limited, but the glycidol ether of optimization aromatic amine and have polar group or when solidifying, generate the resin of polar group.As the object lesson of the epoxy resin that is fit to, this type of glycidyl thing, the amino phenol-type epoxy resin of aromatic amine of glycidyl thing, four glycidyl group m-xylene diamine, four glycidyl group diaminodiphenyl-methane of bisphenol A type epoxy resin, bisphenol f type epoxy resin and aliphatic amine arranged.
As the thio-alcohol curing agent,, just can use if having the mercaptan compound of 2 above mercaptos with being not particularly limited.As the object lesson of the thio-alcohol curing agent that is fit to, have pentaerythrite four thioglycol esters and trimethylolpropane tris thiopropionate this type of aliphatic poly monothioester and aliphatic poly thioether, contain the polythiaether of aromatic rings.The amount of the thio-alcohol curing agent in the composition epoxy resin is understood as the practitioner, and the equivalent proportion of consideration and epoxy resin etc. suitably determines.
Be used to form the composition epoxy resin of protective layer 20, preferably also contain amines with secondary amino group or uncle's amino.As this amines, optimization aromatic amine and aliphatic amine, amine-epoxy adduct, imidazoles, imidazoles adduct etc.
Composition epoxy resin, except that mentioned component, the filler that can also contain silicon dioxide, mica, talcum powder particle etc., with the inorganic salts of magnesium hydroxide, aluminium hydroxide etc., other curing agent of carboxylic acid and phenol etc. or curing accelerator, be the solvent of purpose with the viscosity of adjusting resin combination.
Fig. 3 is the amplification sectional view of the part of the Fig. 2 when being illustrated in composition epoxy resin and containing filler.Protective layer 20 reacts formed solidfied material layer 21 by epoxy resin and thio-alcohol curing agent and the plate-like fillers 22 that is scattered in the solidfied material layer 21 constitutes.
Solidfied material layer 21 is to react the polymer matrix that formed cross-linked polymer is a main component with epoxy resin and thio-alcohol curing agent.The solidfied material layer 21 that constitutes protective layer 20 forms by using the thio-alcohol curing agent, and is good with the adaptation of electrode 12,14, and also performance prevents the effect that electrode 12,14 is peeled off from the plain body 10 of PTC.
By for example heating the composition epoxy resin that contains epoxy resin, thio-alcohol curing agent and filler, make epoxy resin and thio-alcohol curing agent react (curing reaction), form protective layer 20.When forming solidfied material layer 21, also can be, other curing agent and epoxy resin are reacted with the thio-alcohol curing agent.
As filler 22, can use the filler that constitutes by the material lower than the oxygen permeability of solidfied material layer 21.As filler 22, can enumerate the inorganic filler of mica, silicon dioxide, talcum powder, clay (natural or synthetic montmorillonite or these mixture etc.), glass, aluminium hydroxide, magnesium hydroxide and pottery etc., with the metallic stuffing of silver powder, bronze, copper powder and nickel powder etc., the organic filler of carbon black and polyamide etc.Wherein, preferably will contain the inorganic filler that is selected from least a kind of material in mica, silicon dioxide, talcum powder, clay, glass, aluminium hydroxide, magnesium hydroxide and the pottery uses as filler 22.Contain the inorganic filler of these materials, the effect that its anti-block sees through is big, in addition, generally is insulating properties, has the advantage that the insulating properties between the electrode 12,14 keeps easily.
Filler 22 in the present embodiment is tabular.Thus, can obtain high oxygen shielding with lower addition.As tabular filler, can preferably use mica.But, replace tabular filler 22, also can use spherical, fibrous, amorphous etc. filler.In addition, also two or more kinds may be used difform filler.
With protective layer 20 all-mass is benchmark, and protective layer 20 preferably contains the filler 22 of 5～50 quality %.The ratio of filler 22 more preferably more than the 10 quality %, in addition, is more preferably below the 20 quality %.When the ratio of filler 22 was hanged down, the effect that suppresses plain body 10 deteriorations of PTC just had the tendency of decline, and when the ratio of filler 22 was high, the adaptation of plain body 10 of protective layer 20 and PTC and electrode 12,14 just had the tendency of decline.In addition, when the ratio of filler 22 was high, the viscosity of the composition epoxy resin that uses when forming protective layer 20 uprised, and the epoxy resin coating composition forms the tendency that protective layer 20 just has the difficulty of becoming.
In the plain body 10 of PTC, in polymer matrix, be dispersed with conductive particle.Polymer matrix can be thermoplastic resin, also can be the solidfied material of thermosetting resin, still, when being a kind of crystallinity or noncrystalline thermoplastic resin, can obtain the effect that is produced by the present invention more significantly.In addition, in this manual, " thermoplastic resin " also comprises the resin of the state that is crosslinked between the macromolecular chain in the thermoplastic resin.
When the plain body 10 of PTC contains low-molecular-weight organic compound described later, low-molecular-weight organic compound fusion when preventing work produces flows and the distortion of the plain body 10 of PTC, the fusing point of thermoplastic resin or softening point preferably are higher than the fusing point of low molecular compound, and be more preferably high more than 30 ℃, be more preferably high scope below 110 ℃ more than 30 ℃.In addition, the fusing point of thermoplastic resin or softening point are preferably 70 ℃～200 ℃.
The molecular weight of thermoplastic resin, preferable weight-average molecular weight Mw are about 10,000～5,000,000.In addition, thermoplastic resin with the melt flow rate of ASTM D1238 definition preferably 0.1～30g/10 minute.
As polymer matrix by suitably used thermoplastic resin, can enumerate polyolefin (for example polyethylene), (the ethene for example of alkene more than a kind or 2 kinds, propylene) with the copolymer (for example ethylene-vinyl acetate copolymer) that contains the alkene unsaturated monomer more than a kind or 2 kinds of polar group, the inferior ethene of polyvinylhalogenides or poly-halogenation (for example, polyvinyl chloride, Vingon, polyvinyl fluoride, Kynoar), polyamide (for example, 12-nylon), polystyrene, polyacrylonitrile, thermoplastic elastomer (TPE), polyethylene glycol oxide, polyacetals, the thermoplasticity modified cellulose, polysulfones, poly-methyl (methyl) acrylate etc.Wherein, preferred polyolefm, special preferably polyethylene in polyolefin.
Example more specifically as thermoplastic resin, (for example can enumerate high density polyethylene (HDPE), " Hizex 2100JP " (trade name, the Mitsui petrochemistry is produced), " Marlex 6003 " (trade name, philippe company produces)), low density polyethylene (LDPE) (for example, LC500 (trade name, Japan polychem produces), " DYNH-1 " (trade name, Union Carbide company produces)) and medium density polyethylene is (for example, " 2604M " (trade name, Gulf company produces)), ethylene-ethyl acrylate copolymer (for example, " DPD6169 " (trade name, Union Carbide company produces)), ethylene-acrylic acid copolymer (" EAA455 " (trade name for example, DowChemical company produces)), hexafluoroethylene-TFE copolymer (for example, " FEP100 " (trade name, DuPont company produces)), Kynoar (for example, " Kynar461 " (trade name, ペ Application バ Le ト society produces)).
Above thermoplastic resin can a kind or make up more than 2 kinds and use.In addition, polymer matrix is preferred only to be made of thermoplastic resin, but according to circumstances, also can contain the solidfied material of elastomer, thermosetting resin or these mixture.
Conductive particle if find the particle of ptc characteristics when making up with polymer matrix, just has no particular limits, but as its material, preferred especially Ni.When using the Ni particle, there is the tendency that is easy to generate the plain body deterioration of PTC by oxidation, the present embodiment that imports protective layer 20 becomes particularly useful.
Conductive particle preferably has the particle of nail (spike) shape projection.Conductive particle with spike projection is the conductive particle that forms a plurality of (normally 10～500) spike projection (being typically the projection of 1/3～1/50 height of particle diameter) on its surface.
Conductive particle can be the powder that primary particle individually exists also, but is preferably formed about 10～1000 chain second particles that connect of primary particle.As the former example, have as " INCO Type 123 nickel powders (nickelpowder) " with spherical Ni particle of spike projection (trade name, Inco company produce).The average grain diameter of this Ni particle is about 3～7 μ m, and apparent density is 1.8～2.7g/cm
3, specific area is 0.34～0.44m
2About/g.
As the example of the Ni particle that forms the chain second particle, have as " INCO Type 255 nickel powders ", " INCO Type 270 nickel powder " of (filament) shape Ni particle, " INCO Type287 nickel powder " or " INCO Type 210 nickel powders " (above trade name, Inco company produce) by commercially available particle.Wherein, preferred INCO Type 255,277 and 287.The apparent density of the Ni particle that these are thread is 0.3～1.0g/cm
3About, specific area is 0.4～2.5m
2About/g.
The average grain diameter of the primary particle of thread Ni particle (with the value of Fisher subsieve (Off イ Star シ ユ one サ Block シ one Block) method mensuration), be preferably more than the 0.1 μ m, more preferably below the above 4.0 μ m of 0.5 μ m, being more preferably is below the above 4.0 μ m of 1.0 μ m.In addition, in the average grain diameter of primary particle is more than the 1.0 μ m in the thread Ni particle below the 4.0 μ m, can be less than the thread Ni particle of 1.0 μ m with the average grain diameter of the combination of the ratio below the 50 quality % of whole conductive particles primary particle more than the 0.1 μ m.
Containing of conductive particle in the plain body 10 of thermistor is proportional, can suitably determine the feasible ptc characteristics of finding.Particularly, relative whole volumes of the plain body 10 of thermistor, this conductive particle contain proportional 20～50 volume % that are preferably.
Except that polymer matrix and conductive particle, the plain body 10 of PTC also preferably contains low-molecular-weight organic compound.Low-molecular-weight organic compound as this moment can preferably use the crystallinity compound of molecular weight below 1000.This low-molecular-weight organic compound is a solid under normal temperature (about 25 ℃) preferably.In addition, low-molecular-weight organic compound, preferred fusing point (mp) is 40～100 ℃.
Preferred object lesson as low-molecular-weight organic compound, (for example can enumerate hydrocarbon, the straight-chain hydrocarbons of the alkanes of carbon number more than 22), aliphatic acid (for example, the aliphatic acid of the straight-chain hydrocarbons of the alkanes of carbon number more than 22), fatty acid ester (for example, can be by the saturated fatty acid of carbon number more than 20 and the methyl esters of the saturated fatty acid that obtains of lower alcohol such as methyl alcohol), fatty acid amide (for example, saturated fatty acid primary amide and the oleamide of carbon number below 10, the unrighted acid acid amides of erucyl amide etc.), aliphatic amine (for example, the Armeen of carbon number more than 16), higher alcohol (the positive alkylol of carbon number more than 16 particularly).Low-molecular-weight organic compound according to working temperature etc., can use a kind or appropriate combination to use more than 2 kinds.In addition, low-molecular-weight organic compound can use with the state with these waxes that contain as composition or grease.
As the wax that contains these low-molecular-weight organic compounds, can enumerate with the petroleum-type wax of paraffin and microwax etc. is this type of the native paraffin of plant class wax, animal class wax, mineral substance wax of representative.In addition, as the grease that contains these low-molecular-weight organic compounds, can enumerate the grease that is called as fat or solid fat.
Low-molecular-weight organic compound or contain the wax and the grease of these compounds can access as commercially available product.As the commercially available product of paraffin, " lignocerane C for example, is arranged
24H
50" (49～52 ℃ of mp), " hexatriacontane C
36H
74" (73 ℃ of mp), " HNP-10 " (trade name, Japanese smart wax company produce, mp 75 ℃), " HNP-3 " (trade name, Japanese smart wax company produce, mp66 ℃).Commercially available product as microwax, " Hi-Mic-1080 " (trade name for example, is arranged, Japan smart wax company produces, 83 ℃ of mp), " Hi-Mic-1045 " (trade name, Japan smart wax company produces, 70 ℃ of mp), " Hi-Mic2045 " (trade name, Japan smart wax company produces, 64 ℃ of mp), " Hi-Mic3090 " (trade name, Japan smart wax company produces, 89 ℃ of mp), " セ ラ Star 104 " (trade name, the refining company of Japan petroleum produces, 96 ℃ of mp), " 155micro wax " (trade name, the refining company of Japan petroleum produces, 70 ℃ of mp).As the commercially available product of aliphatic acid, for example, behenic acid (Japan refine production, mp 81 ℃), stearic acid (Japan refine production, mp 72 ℃), hexadecanoic acid (Japan refine production, mp 64 ℃) are arranged.As the commercially available product of fatty acid ester, for example, arachic acid methyl esters (Tokyo changes into 48 ℃ of production, mp) is arranged.As the commercially available product of fatty acid amide, for example, oleamide (Japan refine production, mp 76 ℃) is arranged.
In PTC element 1, pair of electrodes 12,14 its parts separately dispose relatively.Electrode 12,13 is made of conductive materials such as metals, is configured as about thickness 0.1mm.As the conductive material that constitutes electrode 12,14, preferred Ni or Ni alloy.In the surface of electrode 12,14, the part that contacts with the plain body 10 of PTC preferably is roughened at least.When the surface of electrode 12,14 was roughened, by anchoring effect, with respect to the plain body 10 of PTC, electrode 12,14 was more firmly fixing.
Polymer matrix in the plain body 10 of PTC is when containing the polymer matrix of thermoplastic resin, can obtain PTC element 1 by the manufacture method that for example comprises following operation: the mixture that contains thermoplastic resin and conductive particle is carried out mixing, obtain containing the operation of these mixing thing; Mixing thing is configured as sheet, forms the operation of the plain body 10 of PTC in polymer matrix conductive particle is scattered in contain thermoplastic resin; With respect to the plain body 10 of PTC, by the fixing operation of pair of electrodes 12,14 of thermo-compressed; With form to cover the plain body 10 of PTC and make the operation of the protective layer 20 that the plain body of PTC 10 is sealed.
Obtain the operation of mixing thing, can will mix on one side the above temperature (preferably than fusing point or high 5～40 ℃ temperature of softening point) of fusing point that each mixture of ingredients is heated to thermoplastic resin or softening point Yi Bian carry out.Perhaps, also can by adding be dissolved with thermoplastic resin solvent, with the state of lowering viscousity mixture is carried out mixingly, do not heat and conductive particle be dispersed in the thermoplastic resin.Mixing can carrying out with known method such as grinding mill, pressurization kneading machine, double screw extruders.
The mixing thing that will obtain by methods such as hot pressing is configured as sheet, forms the plain body 10 of PTC.In this stage, also can the plain body 10 of PTC be cut out the size of regulation by die-cut grade.
By the cramping body that accompanies the plain body 10 of PTC between pair of electrodes 12,14 is carried out hot pressing, with respect to the plain body 10 of PTC, pair of electrodes 12,14 is fixed.With electrode 12,14 fixing after, preferably by radiation exposure etc., make the thermoplastic resin in the polymer matrix crosslinked.Crosslinked by this, the stability of 1 pair of heat of PTC element becomes better.
By the above-mentioned composition epoxy resin of surface attachment at plain body 10 of PTC and electrode 12,14, the composition epoxy resin that heating is adhered to carries out this curing reaction (reaction of epoxy resin and thio-alcohol curing agent) and forms protective layer 20.The method that composition epoxy resin is adhered to is not particularly limited, and can utilize methods such as dipping (dip) method, print process, spray-on process to carry out.In addition, also can or disperse the state of composition epoxy resin, after plain body 10 grades of thermistor, remove by drying and to desolvate with dissolving in solvent.At this moment, also can or carry out continuously drying and curing while.
The condition of cure of composition epoxy resin according to the suitably decision of curing accelerator (tertiary amine etc.) of the kind of thio-alcohol curing agent and combination therein, but preferably is heated to below the working temperature of PTC element, forms protective layer 20.With the temperature heating that is higher than working temperature, when forming protective layer 20, the situation that the resistance value of the PTC element when returning normal temperature exists the resistance value than the PTC element before the cured epoxy resin to rise.Here, working temperature refers to, in the resistance-temperature curve of the resistance change when expression makes the PTC element heat up with 2 ℃/minute programming rate, in the regional low temperature province than the expression ptc characteristics, resistance value is the connecting line of almost certain part and resistance value with the temperature intersection point temperature of the connecting line of the part of rising rapidly that rises.Particularly, when using the composition epoxy resin of thio-alcohol curing agent, preferably be heated to 50～90 ℃, form protective layer 20.At this moment, preferred 5～120 minutes of heating time.
Below, enumerate embodiment, be described more specifically the present invention.But, the invention is not restricted to following embodiment.
Embodiment 1
At low density polyethylene (LDPE) (122 ℃ of fusing points, density 0.92g/cm as polymer matrix
3) in, total volume with respect to polymer matrix and low density polyethylene (LDPE), add the thread Ni particle of the amount of 35 volume %,, obtain being dispersed with the mixing thing of Ni particle while be heated to 150 ℃, in laboplustmill (ラ ボ プ ラ ス ト ミ Le) mixing 30 minutes.Utilize 150 ℃ hot press, the mixing thing that obtains is configured as the sheet of thickness 0.8mm, cut out the size of 3 * 4mm, obtain the plain body of thermistor.
Then, clamp the plain body of this thermistor, utilize hot press, will all heat and pressurize, fixing Ni paper tinsel in the plain body of thermistor as electrode with 2 Ni paper tinsels of single face roughening.After this, on the plain body of thermistor, shine radioactive ray, make low density polyethylene cross-linked.
In addition, by dipping, make the composition epoxy resin (host/curing agent mixture of the production of Ajinomoto Fine-Techno company, " AE-10 " (trade name)) that contains epoxy resin and thio-alcohol curing agent adhere to into the about 20 μ m of thickness, make in the surface that all the plain body of covering thermistor exposes, cover the part on Ni paper tinsel surface.With the 60 ℃ of composition epoxy resin heating that will adhere to 60 minutes, form protective layer by solidfied material (Tg40 ℃) formation of composition epoxy resin.As operate abovely, make the PTC element.
Embodiment 2
In the mixture of bisphenol A type epoxy resin (big Japanese INK production, trade name " 850 ") 50 weight portions and bisphenol f type epoxy resin (big Japanese INK production, trade name " 830 ") 50 weight portions, equivalent cooperates the pentaerythrite four thioglycol esters as the thio-alcohol curing agent, obtain mixture, mixture 100 weight portions with respect to above-mentioned gained, add the imidazoles adduct (production of Ajinomoto Fine-Techno company, trade name " PN-23J ") of 10 weight portions and the silicon dioxide of 10 weight portions, disperse, prepare composition epoxy resin with roller.By dipping, make the composition epoxy resin that obtains adhere to into the about 20 μ m of thickness similarly to Example 1, make when all covering the surface that the plain bodies of thermistors expose, cover the part on Ni paper tinsel surface.The composition epoxy resin that adheres to 80 ℃ of heating 60 minutes forms the protective layer that the solidfied material (Tg55 ℃) by composition epoxy resin constitutes.As above operation, make the PTC element.
Comparative example 1
Except that not forming protective layer, operate equally with embodiment, make the PTC element.
Comparative example 2
In addition, operate similarly to Example 1 except the composition epoxy resin (host/curing agent mixture of the production of aerochemistry company of Mitsubishi, " MAXIVE " (trade name)) that replaces AE-10, use containing epoxy resin and amine curing agent, make the PTC element.The Tg of protective layer is 106 ℃.
Embodiment 3
At low density polyethylene (LDPE) (122 ℃ of fusing points, density 0.92g/cm as polymer matrix
3) in, with respect to the total volume of polymer matrix and Ni particle, add the thread Ni particle of the amount of 35 volume %, be heated to 150 ℃, and meanwhile in laboplustmill mixing 30 minutes, obtain being dispersed with the mixing thing of Ni particle.The mixing thing that will be obtained by 150 ℃ hot presses is configured as the sheet of thickness 0.8mm, cuts out the size of 3 * 4mm, obtains the plain body of PTC.
Then, clamp the plain body of this PTC, will all heat and pressurize, fixing Ni paper tinsel in the plain body of PTC as electrode by hot press with 2 Ni paper tinsels of single face roughening.After this, on the plain body of PTC, shine radioactive ray, make low density polyethylene cross-linked.
In addition, by dipping, the composition epoxy resin that contains epoxy resin and thio-alcohol curing agent is adhered to becomes the about 20 μ m of thickness, makes when all covering the surface that the plain bodies of PTC expose, covers the part on Ni paper tinsel surface.(big Japanese INK produces at bisphenol A type epoxy resin, trade name " 850 ") (big Japanese INK produces for 50 weight portions and bisphenol f type epoxy resin, trade name " 830 ") in the mixture of 50 weight portions, equivalent cooperates the trimethylolpropane tris thiopropionate as the thio-alcohol curing agent, (AjinomotoFine-Techno company produces to add the imidazoles adduct again, trade name " PN-23J "), obtain resin compound, with respect to this resin compound of 100 weight portions, (mica industry in mountain pass is produced to add the mica of the 5 quality % become whole composition epoxy resins, trade name " A-11 "), disperse with roller, as composition epoxy resin, use this adjusted resin compound.The composition epoxy resins heating that to adhere to 80 ℃ 30 minutes forms the protective layer that the solidfied material by composition epoxy resin constitutes.As above operation, make the PTC element.
Embodiment 4
Except that the amount of mica was 10 quality % of whole composition epoxy resins, the PTC element was made in operation similarly to Example 1.
Embodiment 5
Except that the amount of mica was 20 quality % of whole composition epoxy resins, the PTC element was made in operation similarly to Example 1.
Embodiment 6
Except that the amount of mica was 50 quality % of whole composition epoxy resins, the PTC element was made in operation similarly to Example 1.
Embodiment 7
Remove the replacement mica, use silicon dioxide (electrochemical industrial production, trade name " FS-44 "), its amount is beyond the 10 quality % of whole composition epoxy resins, operation similarly to Example 1, making PTC element.
Embodiment 8
Except that the amount of silicon dioxide was 20 quality % of whole composition epoxy resins, the PTC element was made in operation similarly to Example 5.
Embodiment 9
Remove and use the composition epoxy resin that does not add filler (mica) and prepare, form beyond the protective layer, the PTC element is made in operation similarly to Example 1.
Reference example
Except that the amount of mica was 60 quality % of whole composition epoxy resins, the composition epoxy resin of preparation was used in operation similarly to Example 1, attempts forming protective layer, but because the viscosity height can not adhere to resin with dipping method, can not make the PTC element.
The resistance value of PCT element
To the PTC element of making, the variation of the resistance value when cooling off with 2 ℃/minute programming rate intensification back with 4 terminal methods mensuration obtains temperature resistance curve, obtains room temperature (25 ℃) resistance value from this curve.After with normal temperature the PTC element being placed 180 again, use drying machine after 5 hours, to operate too, obtain room temperature resistance value with 100 ℃ of heating.In addition, the temperature when obtaining resistance value and be 75 Ω by the temperature resistance curve at initial stage, the situation of arbitrary thermistor element all in 100 ℃ ± 8 ℃ scope, is represented to bring into play the ptc characteristics of function in embodiment and the comparative example with the working temperature below 100 ℃.
Adaptation
S face (rolling drum surface of electrolysis paper tinsel) at Ni paper tinsel (production of company of FUKUDA METAL, electrolysis paper tinsel, thickness 25 μ m) is gone up the composition epoxy resin that uses in coating embodiment or the comparative example; heated 60 minutes down at 60 ℃, on the Ni paper tinsel, form the resin bed that is equivalent to above-mentioned PTC element protection layer.Then, the test film that will form resin bed on the Ni paper tinsel is fixed on the substrate, makes the Ni paper tinsel become the surface, removes the Ni paper tinsel, stays the thin rectangular segment of width 10mm.Then, the end of the short brink of thin rectangle Ni paper tinsel is fixed on the pincette, uses autoplotter, with 50mm/ minute speed, on the direction vertical, peel off, measure the peel load of this moment with the interarea of Ni paper tinsel.Estimate the adaptation of protective layer by this value.
Table 1
| Protective layer | Room temperature resistance value (m Ω) | ||||
| Curing agent | Tg(℃) | Adaptation (kgf/cm) | Initial stage | After the normal temperature placement+heat treated | |
| Embodiment 1 | The thio-alcohol curing agent | 40 | ?0.7 | ?4 | ?15 |
| Embodiment 2 | Thio-alcohol curing agent+imidazoles adduct | 55 | ?0.5 | ?4 | ?13 |
| Comparative example 1 | The unprotect layer | - | ?- | ?3 | ?40 |
| Comparative example 2 | Amine curing agent | 106 | ?0.2 | ?4 | ?50 |
As shown in table 1, do not have protective layer comparative example 1 the plain body of thermistor and forms the plain body of thermistor of the comparative example 2 of protective layer by the composition epoxy resin of amine curing agent, normal temperature places afterwards, when standing thermal history, room temperature resistance value enlarges markedly.With respect to this, form the plain body of thermistor of the embodiment of protective layer by the composition epoxy resin that uses the thio-alcohol curing agent, suppress increase fully as room temperature resistance value.In addition, have the protective layer of the PTC element of embodiment, also obviously excellent to the adaptation of Ni paper tinsel than the protective layer in the comparative example 2.
Table 2
| Filler | Adaptation (kgf/cm) | Room temperature resistance value [Ω] | ||||
| Kind | Shape | Addition (quality %) | Initial stage | After the normal temperature placement+heat treated | ||
| Embodiment 3 | Mica | Tabular | 5 | ?0.9 | ?4 | ?13 |
| Embodiment 4 | Mica | Tabular | 10 | ?0.6 | ?4 | ?11 |
| Embodiment 5 | Mica | Tabular | 20 | ?0.5 | ?4 | ?8 |
| Embodiment 6 | Mica | Tabular | 50 | ?0.1 | ?4 | ?6 |
| Embodiment 7 | Silicon dioxide | Amorphous | 10 | ?0.8 | ?4 | ?13 |
| Embodiment 8 | Silicon dioxide | Amorphous | 20 | ?0.6 | ?4 | ?11 |
| Embodiment 9 | Do not have | - | 0 | ?1.1 | ?4 | ?18 |
| Comparative example 1 | The unprotect layer | - | - | ?- | ?3 | ?40 |
| Reference example | Mica | Tabular | 60 | Non-cohesive | ?- | ?- |
As shown in table 2; form the PTC element of the embodiment of protective layer by the composition epoxy resin that contains the thio-alcohol curing agent; compare with the thermistor element of the comparative example 3 that does not have protective layer, be suppressed at the increase that normal temperature is placed back, the room temperature resistance value when standing thermal history.Particularly the protective layer of the PTC element of the embodiment 3～5,7,8 of the amount of filler in 5～20 quality % scopes shows good adaptation.
If according to PTC element of the present invention, after the manufacturing, suppressed fully through long-time back, the deterioration of PTC element when standing thermal history.In addition, suppressed fully in increase through the room temperature resistance value after long-time, when standing thermal history.PTC element of the present invention is gone back the oxygen shielding excellence because of protective layer, so, the oxidative resistance excellence.
The protective layer in the PTC element of the present invention and the adaptation excellence of electrode also cover at least a portion of pair of electrodes and when forming one, prevent to peel off from the plain body of the PTC of electrode when protective layer covers the plain body of PTC.
Claims (8)
1. PTC element is characterized in that having:
The plain body of PTC that contains polymer matrix and conductive particle;
The pair of electrodes that contacts with the plain body of this PTC; With
Constitute, cover the plain body of this PTC by the solidfied material of the composition epoxy resin that contains epoxy resin and thio-alcohol curing agent and make the sealed protective layer of the plain body of this PTC.
2. PTC element as claimed in claim 1 is characterized in that:
Described composition epoxy resin also contains amines.
3. PTC element as claimed in claim 1 is characterized in that:
Described protective layer forms in the mode that also covers at least a portion of this pair of electrodes when covering the plain body of this PTC.
4. PTC element is characterized in that:
Have: the plain body of PTC that contains polymer matrix and conductive particle;
The pair of electrodes that contacts with the plain body of this PTC; With
Cover the plain body of this PTC and make the sealed protective layer of the plain body of this PTC,
Described protective layer comprises: epoxy resin and thio-alcohol curing agent react formed solidfied material layer; With the filler that constitutes, is scattered in by the material lower in this solidfied material layer than the oxygen permeability of this solidfied material layer.
5. PTC element as claimed in claim 4 is characterized in that:
Described filler is inorganic filler.
6. PTC element as claimed in claim 4 is characterized in that:
At least a portion of described filler is tabular.
7. PTC element as claimed in claim 4 is characterized in that:
All-mass with described protective layer is a benchmark, and described protective layer contains the described filler of 5～50 quality %.
8. PTC element as claimed in claim 4 is characterized in that:
Described protective layer forms in the mode that also covers at least a portion of this pair of electrodes when covering the plain body of this PTC.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005378925 | 2005-12-28 | ||
| JP2005378925A JP4283803B2 (en) | 2005-12-28 | 2005-12-28 | PTC element |
| JP2006045607 | 2006-02-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1992102A true CN1992102A (en) | 2007-07-04 |
Family
ID=38214275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610156581 Pending CN1992102A (en) | 2005-12-28 | 2006-12-28 | PTC element |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4283803B2 (en) |
| CN (1) | CN1992102A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103189935A (en) * | 2010-07-02 | 2013-07-03 | 泰科电子日本合同会社 | PTC device and secondary battery having same |
| CN103238236A (en) * | 2010-05-06 | 2013-08-07 | 泰科电子日本合同会社 | Ptc device and secondary battery equipped with same |
| CN102007586B (en) * | 2008-04-18 | 2013-09-25 | 株式会社半导体能源研究所 | Thin film transistor and method for manufacturing the same |
| CN109907878A (en) * | 2018-12-14 | 2019-06-21 | 华南理工大学 | A kind of fast heating constant temperature hot compress medicine and preparation method thereof |
| CN110353875A (en) * | 2019-06-18 | 2019-10-22 | 华南理工大学 | A kind of wearable human body constant temperature hyperthermia clothes of whole body |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012054099A (en) * | 2010-09-01 | 2012-03-15 | Fdk Twicell Co Ltd | Battery |
| JP5579544B2 (en) * | 2010-09-01 | 2014-08-27 | Ｆｄｋトワイセル株式会社 | Alkaline storage battery |
-
2005
- 2005-12-28 JP JP2005378925A patent/JP4283803B2/en not_active Expired - Fee Related
-
2006
- 2006-12-28 CN CN 200610156581 patent/CN1992102A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102007586B (en) * | 2008-04-18 | 2013-09-25 | 株式会社半导体能源研究所 | Thin film transistor and method for manufacturing the same |
| CN103238236A (en) * | 2010-05-06 | 2013-08-07 | 泰科电子日本合同会社 | Ptc device and secondary battery equipped with same |
| CN103189935A (en) * | 2010-07-02 | 2013-07-03 | 泰科电子日本合同会社 | PTC device and secondary battery having same |
| CN109907878A (en) * | 2018-12-14 | 2019-06-21 | 华南理工大学 | A kind of fast heating constant temperature hot compress medicine and preparation method thereof |
| CN110353875A (en) * | 2019-06-18 | 2019-10-22 | 华南理工大学 | A kind of wearable human body constant temperature hyperthermia clothes of whole body |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007180382A (en) | 2007-07-12 |
| JP4283803B2 (en) | 2009-06-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1992102A (en) | PTC element | |
| CN1230837C (en) | Electrically conductive polymer composition | |
| CN1111876C (en) | Electrical device | |
| US8044763B2 (en) | Surface-mounted over-current protection device | |
| CN103797548B (en) | Polymer-based conducing composite material and PTC-element | |
| CN1715329A (en) | Resin composition for forming a thermistor body, and thermistor | |
| CN1301511C (en) | Positive temp. coefficient thermal resistance | |
| CN105321640B (en) | Positive temperature coefficient element | |
| JP6831830B2 (en) | Conductive polymer compositions, conductive polymer sheets, electrical components and methods of manufacturing them | |
| TWI480900B (en) | Radial-leaded over-current protection device | |
| CN1914694A (en) | Metal/plastic hybrid and shaped body produced therefrom | |
| CN1950447A (en) | Resin composition for sealing and semiconductor device sealed with resin | |
| CN1744792A (en) | Electrical devices having an oxygen barrier coating | |
| KR20070070092A (en) | Ptc devices | |
| CN102522172A (en) | Resistance positive temperature effect conductive composite material and thermistor element | |
| CN1495807A (en) | On-machine posistor and its mfg. method | |
| CN101162632A (en) | Overcurrent protection component | |
| CN1111310C (en) | Thermosensitive resistor and its manufacture | |
| CN102522173A (en) | Conducting composite material with resistance positive-temperature effect and overcurrent-protecting element | |
| CN1252206C (en) | Binder and adhesive film | |
| CN1801406A (en) | Thermistor | |
| CN1290943A (en) | Voltage nonlinear resistor and its producing method | |
| JP2000012307A (en) | Organic positive temperature coefficient thermistor | |
| CN101399105A (en) | Thermistor | |
| CN1487533A (en) | PTC thermosensitive resistor parts and PTC thermosensitive resistor and producing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20070704 |