CN103281811A - Polymer composite electric heating material, preparation method thereof and application of polymer composite electric heating material - Google Patents
Polymer composite electric heating material, preparation method thereof and application of polymer composite electric heating material Download PDFInfo
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Abstract
The invention provides polymer composite electric heating material, a preparation method thereof and the application of the polymer composite electric heating material. The polymer composite electric heating material is characterized by comprising polymer composite electric heating coating and base material for bearing the polymer composite electric heating coating, wherein the polymer composite electric heating coating comprises the following compositions in part by weight: 100 parts of polymer resin base material, 1-50 parts of conductive fillers, 1-30 parts of additive and 100-600 parts of solvent, and the conductive fillers adopt one or more than two of conductive carbon black, conductive graphite, carbon fiber, metal powder and metal fiber; and the base material is thin and flexible and is suitable for coating objects in coating property. The polymer composite electric heating material is suitable for being applied in a low-temperature heating field within 0-160 DEG C and is particularly suitable for being applied to aspects of heating of buildings, heating and heat preservation of animals and plants, baking and drying of goods, far infrared therapy health care and the like.
Description
The application is to be on August 12nd, 2011 applying date of original application, and application number is 201110231697.X, and denomination of invention is divided an application for the Chinese patent application of " macromolecule composite electric hating material, its preparation method, with and uses thereof ".
Technical field
The present invention relates to the polymer composite field, particularly relate to a kind of macromolecule composite electric hating material, its preparation method, with and uses thereof.This macromolecule composite electric hating material belongs to Low-temp. electrothermal materials, has a wide range of applications with interior low-temperature heat field at 0～160 ℃.
Background technology
As everyone knows, utilize lectrothermal alloy wire to heat in the thermo electric material application and had quite long history.But because of its electric conversion efficiency low, only 50%～70%, easily oxidation become fragile and rupture, shortcoming such as poor seismic behavior, its power density is very big in addition, only be adapted at high temperature heating or middle high temperature heating field and use, and only be adapted at that heating space is less relatively, heating purposes thing relative fixed and thermo electric material are easy to the occasion safeguarding and change.
In order to overcome the shortcoming of lectrothermal alloy wire, many scholars and researcher have carried out studying widely and inquiring into, and have developed multiple thermo electric material, to satisfy the application of different field; Especially in organic chemistry filed, the discovery of structural type macromolecule conducting material and composite polymer electric conducting material, it is swift and violent, fast-developing that field of electric heating is able to, and range of application enlarges rapidly, even development and touched the every aspect of our life.The structural type macromolecule conducting material is the macromolecular material with conjugated double bond, high-performance conductive material through the preparation of mixing, its conductance, excellent performance, some conductivity of electrolyte materials even surpass metal material, but its cost costliness, processing difficulties, large-scale commercial are used and are still had numerous technical barriers.
The composite polymer electric conducting material is to be continuous phase with the high molecular polymer, be decentralized photo with inorganic conductive powder (carbon black, graphite, metal etc.), conductive fiber (carbon fiber, metallic fiber), carbon nano-tube etc., by different raw material and prescriptions, form through corresponding processing technology manufacturing.It probably can show as forms such as conductive rubber, conductive plastics, electrically conductive ink, electrically-conducting paint, electrically conducting adhesive.The composite conducting material of above-mentioned form has its characteristics and applicability separately.For example, conductive rubber and conductive plastics are mainly as antistatic and electromagnetic shielding goods, when using as thermo electric material, because the heat resistance of these two kinds of materials is limited, cause it to be adapted at 0～100 ℃ with interior scope work, and very easily decay because of the overheated electric property that makes; The thermal resistance of well-known any material is directly proportional with its thickness, because conductive rubber and conductive plastics are difficult to be processed into the film shape, therefore, its electric conversion efficiency will inevitably reduce with the increase of material thickness.Electrically conducting adhesive prepares for high-performance is electrically connected, and the characteristic that it possesses should be high conductivity, high-termal conductivity and high adhesiveness energy.Electrically conductive ink is fit to make membranaceous thermo electric material very much, but it is because the reason of manufacture craft (mode of printing) and material structure thereof makes its part that comes with some shortcomings.As, require the narrower adjustability that makes its product electric heating property of the regional number to be printed adjustable extent non-100%, electrically conductive ink of tight, efficient heat generation to the evenness on supporting substrate surface a little less than.
Summary of the invention
The objective of the invention is in order to overcome the defective of above-mentioned composite polymer electric conducting material prior art, it is that 0.2～2mm, resistance value scope are easy to adjust, suitable voltage (interchange, direct current) is in extensive range, electric conversion rate is high, be applicable to macromolecule composite electric hating material that 0～160 ℃ of scope is used with interior low-temperature heat and preparation method thereof that a kind of thickness is provided.
The objective of the invention is to be achieved through the following technical solutions:
A kind of macromolecule composite electric hating material, it is characterized in that, comprise the base material of macromolecule compound electro-thermal coating and this coating of carrying, described macromolecule compound electro-thermal coating comprises the macromolecule resin base-material of 100 weight portions, the conductive filler of 1～50 weight portion, the auxiliary agent of 1～30 weight portion and the solvent of 100～600 weight portions; Described base material is thin, material flexible and that be suitable for applying the coating object.
Described base material is plastic film, glass fabric, nonwoven fabrics, chemical fabric or cotton grey fabric.
The macromolecule resin base-material that described macromolecule compound electro-thermal coating comprises is selected from epoxy resin, mylar, polystyrene resin, acrylic resin, polyurethane resin, polycarbonate resin.
The conductive filler that described macromolecule compound electro-thermal coating comprises is selected from one or more in conductive carbon black, electrically conductive graphite, carbon fiber, metal powder, the metallic fiber.Described conductive carbon black is the neccessary composition (being also referred to as leading electric filler in the present invention) in the conductive filler, and all the other are the additional conductive filler.
Described conductive carbon black is high electric conductivity carbon black, superconduct carbon black or acetylene carbon black, and the use level in macromolecule compound electro-thermal coating must not be less than 3 weight portions for the macromolecule resin base-material with respect to 100 weight portions, preferred use level is 3～35 weight portions, and further preferred use level is 5～28 weight portions.
Electrically conductive graphite average grain diameter in the described additional conductive filler is between 1～50 μ m, its use level in macromolecule compound electro-thermal coating is 0～45 weight portion for the macromolecule resin base-material with respect to 100 weight portions, preferred use level is 0～32 weight portion, and further preferred use level is 0～25 weight portion.
The auxiliary agent that described macromolecule compound electro-thermal coating comprises is one or more of coupling agent, plasticizer, stabilizer, dispersant, lubricant and other auxiliary agent.
Described coupling agent is one or more among KH550, KH570, A151, OFS-6020, the DL602, its use level in macromolecule compound electro-thermal coating is 0.1～10 weight portion for the macromolecule resin base-material with respect to 100 weight portions, preferred use level is 0.3～6 weight portion, and further preferred use level is 0.5～3 weight portion.
Described plasticizer is dibutyl phthalate, dioctyl phthalate or dibenzoic acid binaryglycol ester, its use level in macromolecule compound electro-thermal coating is 0.1～20 weight portion for the macromolecule resin base-material with respect to 100 weight portions, preferred use level is 1～15 weight portion, and further preferred use level is 3～12 weight portions.
Described dispersant is non-ionic surface active agent, be selected from Tween20, Tween40, Tween60 or Tween80, its use level in macromolecule compound electro-thermal coating is 0.1～10 weight portion for the macromolecule resin base-material with respect to 100 weight portions, preferred use level is 0.1～6 weight portion, and further preferred use level is 0.3～3 weight portion.
Non-ionic surface active agent in the macromolecule compound electro-thermal coating of the present invention has extraordinary wetting and peptizaiton to the metal oxide of leading electric filler, additional conductive filler and described other auxiliary agent, with lubricant such as stearic mating reaction under, can shorten the time of preparation macromolecule compound electro-thermal coating, also can make the equally distributed state of electric-heating coatings keep the longer time.The visible embodiment 1 of details and Comparative Examples 1.
Described lubricant is paraffin, Tissuemat E or stearic acid, its use level in macromolecule compound electro-thermal coating is 0.1～10 weight portion for the macromolecule resin base-material with respect to 100 weight portions, preferred use level is 0.5～7 weight portion, and further preferred use level is 0.8～5 weight portion.
Described other auxiliary agent is one or more composition of calcium, magnesium, aluminium, tin, zinc, titanium, barium metal oxide, its purity should be more than 95%, use level in macromolecule compound electro-thermal coating is 0.1～20 weight portion for the macromolecule resin base-material with respect to 100 weight portions, preferred use level is 0.5～15 weight portion, and further preferred use level is 1～8 weight portion.
The metal oxide of above-mentioned other auxiliary agent possesses semi-conductive characteristic by it, but in macromolecule compound electro-thermal coating the main and auxiliary conductive filler of coordinated, improve the electrical property of macromolecule composite electric hating material of the present invention.The visible embodiment 4 of details and Comparative Examples 2.
The solvent that described macromolecule compound electro-thermal coating comprises is selected from toluene, dimethylbenzene, acetone, methylethylketone, ethanol, propyl alcohol, ethyl acetate, butyl acetate.
In the described base material, glass fabric, chemical fabric or cotton grey fabric can be to inweave electrode base material in advance, and the described electrode base material that inweaves in advance is in it weaves cotton cloth process, and the warp fiber that replaces the above-mentioned fabrics assigned address with conductive filament in groups forms; Described conductive filament is selected from metallic fiber, metal wire combined cotton yarn or filament, and diameter is 0.03～0.5mm; Described is that 5～100 conductive filament next-door neighbours form one group side by side in groups, and each group conductive filament constitutes a conductive electrode of described macromolecule composite electric hating material; The width of described conductive electrode is 3～15mm, is to occur in pairs with 2 multiple at the described electrode base material that inweaves in advance, and the distance of every pair of electrode outer (distance between the right of right electrodes and the left side of left electrodes) is 30～600mm.Has the visible Fig. 1 of the structure that inweaves electrode base material in advance.
The present invention is by to inweaving the flexible adjustment of electrode base material structure in advance, as, change the distance of every pair of electrode outer, can make the macromolecule compound electro-thermal coating a kind of prescription, be applied on the described base material of equal area with same coating weight, and the macromolecule composite electric hating material that acquisition has different resistance values.In addition, to the adjustment that inweaves electrode base material fibre diameter, conductive filament diameter in advance and the adjustment of above-mentioned fabrics warp-wise and weft fiber density, can conveniently obtain the macromolecule composite electric hating material of different-thickness and different macromolecule compound electro-thermal coating bearing capacities.
Macromolecule composite electric hating material of the present invention is the pure resistive material, and the electric current of the material of flowing through during energising almost all is converted into Joule heat, there is no luminous energy and inductive loss; In addition, macromolecule composite electric hating material thickness of the present invention is significantly smaller than conductive rubber and conductive plastics, and the heat that sends can more effectively come out, moreover its efficient heat generation zone is 100%, therefore, has higher electric conversion rate.
Above-mentioned some characteristics are added the flexible adjustment to macromolecule compound electro-thermal formulation for coating material, can demonstrate fully more that macromolecule composite electric hating material resistance value scope of the present invention is convenient to adjust, material thickness is easy to change, be suitable for the multiple advantage that voltage range is extensive, electric conversion rate is high, make it to be applicable to that 0～160 ℃ of scope is with the extensive use of interior low-temperature heat.
The manufacture method of described macromolecule composite electric hating material may further comprise the steps:
A) accurately take by weighing conductive filler and place container, and add the auxiliary agent of the accurate weighing of warp successively and be enough to fully soak into the partial solvent of the amount of above-mentioned conductive filler and auxiliary agent;
B) after fully soaking into, accurately add into the macromolecule resin base-material of solution state, and suitably stir;
C) add remaining solvent, fully stir, make each component must be in abundant mixing;
D) with high-shearing dispersion emulsifying machine said mixture is carried out high speed dispersion and grinding, 15～30 minutes time, make macromolecule compound electro-thermal coating;
E) macromolecule compound electro-thermal coating is coated on the described base material equably, coated weight is counted 50～600g/m with weight in wet base
2, through the baking of 60～120 ℃ of temperature, 3～30 minutes time, namely obtain the macromolecule composite electric hating material.
In order to make the macromolecule composite electric hating material standardization of test different model specification of the present invention, the present invention is decided to be 10 * 10cm to the specimen size unification of macromolecule composite electric hating material, and uses mode as shown in Figure 2 to carry out resistance measurement.
Preparation method of the present invention is easy, and product has good physical property and electric property convenient, that easily transfer, is particularly suitable for 0～160 ℃ of scope with the application of interior low-temperature heat.Its key technical indexes is:
A) width: 20～600mm;
B) length: 50～8000mm;
C) thickness: 0.2～2.0mm;
D) normal working temperature: 0～160 ℃;
E) resistance value: 100～40000 Ω/10 * 10cm.
Description of drawings
Fig. 1 inweaves the structural representation of electrode base material in advance for macromolecule composite electric hating material of the present invention.
Fig. 2 is the schematic diagram of test macromolecule composite electric hating material sample resistance value.
Fig. 3 is 600W/m
2Sample diaphragm (100 * 25cm) energising temperature rise variation diagrams.
Fig. 4 is 150W/m
2Sample diaphragm (50 * 50cm) energising temperature rise variation diagrams.
Fig. 5 is 250W/m
2Sample diaphragm (50 * 25cm) energising temperature rise variation diagrams.
Fig. 6 is 200W/m
2(100 * 25cm) continue energising change in resistance figure to the sample diaphragm.
Embodiment
Below by embodiment and the contrast accompanying drawing the present invention will be further described.In following each embodiment, the use level of each component is weight portion.It is important to point out that following examples are only for the present invention will be further described; can not be interpreted as limiting the scope of the invention; this art skilled person makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belongs to protection scope of the present invention.
Fig. 1 is the structural representation that inweaves electrode base material in advance of the present invention, as shown in the figure, inweaves electrode base material 1 in advance and is glass fabric, chemical fabric or cotton, and electrode band 2 is metallic fiber, metal wire combined cotton yarn or filament.
Fig. 2 is the schematic diagram of test macromolecule composite electric hating material sample resistance value and energising temperature rise, and as shown in the figure, sample 4 is of a size of 100 * 100mm for having applied the base material of macromolecule compound electro-thermal coating; Electrode 5,6,7,8 is the zinc-plated or zinc of copper plate, is of a size of 100 * 6 * 3mm, and electrode 5 is done the edge that reliably be electrically connected and clamp 4 relative both sides with 8 by lead 11 with 6 and 7, and its outer is concordant with 4 outers; Lead 9,10 is used for the lead-in wire of test sample 4 resistance values.
1) prescription of macromolecule compound electro-thermal coating is as follows by weight:
Polyurethane resin (NIPPOLAN2301, Nippon Polyurethane Industry Co., Ltd.) 100 parts, 5.3 parts of acetylene carbon blacks, 3.5 parts in magnesium oxide (purity 〉=95%), 3.5 parts in zinc oxide (purity 〉=95%), 9 parts of dioctyl phthalates, 1.8 parts of stearic acid, 0.8 part of dispersant (Tween20), 270 parts of solvents (ethyl acetate, purity 〉=95%).
2) compound method of macromolecule compound electro-thermal coating is as follows:
A) accurately take by weighing conductive filler (acetylene carbon black), other auxiliary agent (magnesium oxide, zinc oxide), dispersant (Tween20), plasticizer (dioctyl phthalate) and lubricant (stearic acid) and place container;
B) take by weighing about 2/3rds solvents (ethyl acetate), add in the said vesse;
C) above-mentioned material is after fully soaking into, and accurate weighing also adds macromolecule resin base-material (polyurethane resin);
D) add residue 1/3rd solvents, fully stir, make each component must be in abundant mixing;
E) with high-shearing dispersion emulsifying machine said mixture is carried out high speed dispersion and grinding, 25 minutes time, make macromolecule compound electro-thermal coating.
3) manufacture method of macromolecule composite electric hating material is as follows:
Above-mentioned electric-heating coatings is coated on 21 yarn cotton grey fabrics as base material equably, and the coated weight before dry namely is about 300g/m in the coated weight of weight in wet base
2, through the baking of about 80 ℃ of temperature about 10 minutes, namely obtain the macromolecule composite electric hating material that thickness is about 0.5mm.
4) method of testing of macromolecule composite electric hating material sample resistance is as follows:
A) the macromolecule composite electric hating material of step 3) being made is cut into 10 * 10cm specification;
B) press the method for Fig. 2, clamp the position at thermo electric material two ends with electrode 5 and 6,7 and 8;
C) be not less than 0.5% digital multimeter with accuracy and measure resistance value and record between the lead 9,10.
Test result: resistance R=35.5k Ω.
Electric-heating coatings is placed the no obvious lamination in a week back.
Comparative Examples 1
The prescription of Comparative Examples 1 is similar to embodiment 1, and difference is: the use level of lubricant in the Comparative Examples 1 (stearic acid) and dispersant (Tween20) is 0 part.
The result: e in the compound method of macromolecule compound electro-thermal coating) item needs just coating is uniformly dispersed with about 40 minutes time.Electric-heating coatings was placed after 24 hours can obviously observe lamination.
The prescription of embodiment 2 to embodiment 5 is similar to embodiment 1, and difference is: the use level of acetylene carbon black is 6 parts among the embodiment 2; Among the embodiment 3, acetylene carbon black is 6 parts, and electrically conductive graphite is 6 parts; Among the embodiment 4, acetylene carbon black is 6 parts, and electrically conductive graphite is 10.5 parts; Among the embodiment 5, acetylene carbon black is 8 parts.
The compound method of macromolecule compound electro-thermal coating is identical with embodiment 1 with the method for testing of the manufacture method of macromolecule composite electric hating material and sample resistance.
Test result:
Comparative Examples 2
The prescription of Comparative Examples 2 is similar to embodiment 4, and difference is: the use level of other auxiliary agent in the Comparative Examples 2 (magnesium oxide, zinc oxide) is 0 part.
The compound method of macromolecule compound electro-thermal coating is identical with embodiment 1 with the method for testing of the manufacture method of macromolecule composite electric hating material and sample resistance.
Test result:
Comparative Examples 2, resistance R=3750 Ω.Big 90 Ω of the resistance of its resistance value ratio embodiment 4.
The prescription of embodiment 6, embodiment 7 and embodiment 8 is similar to embodiment 1, and difference is: the use level of acetylene carbon black is 8 parts among the embodiment 6, and electrically conductive graphite is 12 parts; Among the embodiment 7, acetylene carbon black is 20 parts, and electrically conductive graphite is 4 parts; Among the embodiment 8, acetylene carbon black is 18 parts, and electrically conductive graphite is 8 parts; In addition, among these three embodiment, the use level of other auxiliary agent (magnesium oxide, zinc oxide) is 4 parts, and the use level of solvent (ethyl acetate) is 260 parts.
The compound method of macromolecule compound electro-thermal coating is identical with embodiment 1 with the method for testing of the manufacture method of macromolecule composite electric hating material and sample resistance.
Test result:
The prescription of macromolecule compound electro-thermal coating is as follows by weight:
Polyurethane resin (WHT-6320, Yantai Wanhua Polyurethane Co., Ltd) 100 part, 21.5 parts of acetylene carbon blacks, 14 parts of electrically conductive graphites, 3.2 parts in magnesium oxide (purity 〉=95%), 3.2 parts in zinc oxide (purity 〉=95%), 8 parts of dibutyl phthalates, 1.6 parts of stearic acid, 0.7 part of dispersant (Tween20), 350 parts of solvents (methylethylketone).
The compound method of macromolecule compound electro-thermal coating is identical with embodiment 1.
The manufacture method of macromolecule composite electric hating material is similar to embodiment 1, and difference is: the baking temperature among the embodiment 9 is 120 ℃, about 20 minutes of time.
The compound method of macromolecule compound electro-thermal coating is identical with embodiment 1 with the method for testing of the manufacture method of macromolecule composite electric hating material and sample resistance.
Test result: resistance R=350 Ω.
The prescription of macromolecule compound electro-thermal coating is as follows by weight:
100 parts of polyurethane resins (NIPPOLAN2301), 8.3 parts of acetylene carbon blacks, 3.3 parts in magnesium oxide (purity 〉=95%), 3.3 parts in zinc oxide (purity 〉=95%), 7.5 parts of dioctyl phthalates, 1.5 parts of stearic acid, 0.6 part of dispersant (Tween20), 240 parts of solvents (ethyl acetate, purity 〉=95%).
The compound method of macromolecule compound electro-thermal coating is identical with embodiment 1 with the method for testing of the manufacture method of macromolecule composite electric hating material and sample resistance.
Test result: resistance R=2630 Ω.
The prescription of embodiment 11 and embodiment 12 is similar to embodiment 10, and difference is: electrically conductive graphite is 6.5 parts among the embodiment 11; Among the embodiment 12, electrically conductive graphite is 13.3 parts; Among the embodiment 12, the use level of solvent (ethyl acetate) is 200 parts.
The compound method of macromolecule compound electro-thermal coating is identical with embodiment 1 with the method for testing of the manufacture method of macromolecule composite electric hating material and sample resistance.
Test result:
Embodiment 13
The prescription of macromolecule compound electro-thermal coating is as follows by weight:
100 parts of polyurethane resins (NIPPOLAN2301), 8.6 parts of acetylene carbon blacks, 2.8 parts in magnesium oxide (purity 〉=95%), 2.8 parts in zinc oxide (purity 〉=95%), 7 parts of dioctyl phthalates, 1.5 parts of stearic acid, 0.6 part of dispersant (Tween20), 165 parts of solvents (ethyl acetate, purity 〉=95%).
The compound method of macromolecule compound electro-thermal coating is identical with embodiment 1 with the method for testing of the manufacture method of macromolecule composite electric hating material and sample resistance.
Test result: resistance R=1930 Ω.
Embodiment 14, embodiment 15 and embodiment 16
The prescription of embodiment 14, embodiment 15 and embodiment 16 is similar to embodiment 13, and difference is: electrically conductive graphite is 2.9 parts among the embodiment 14; Electrically conductive graphite is 6 parts among the embodiment 11; Electrically conductive graphite is 11.5 parts among the embodiment 12.
The compound method of macromolecule compound electro-thermal coating is identical with embodiment 1 with the method for testing of the manufacture method of macromolecule composite electric hating material and sample resistance.
Test result:
Embodiment 14, resistance R=1290 Ω; Embodiment 15, resistance R=1000 Ω; Embodiment 16, resistance R=730 Ω.
Embodiment 17
The prescription of macromolecule compound electro-thermal coating is as follows by weight:
Polyurethane resin (IROSTIC S6558, HUNTSMAN) 100 parts, 16 parts of acetylene carbon blacks, 17 parts of electrically conductive graphites, 2.8 parts in magnesium oxide (purity 〉=95%), 2.8 parts in zinc oxide (purity 〉=95%), 6 parts of dioctyl phthalates, 1.2 parts of stearic acid, 0.5 part of dispersant (Tween20), 360 parts of solvents (methylethylketone).
The compound method of macromolecule compound electro-thermal coating is identical with embodiment 1 with the method for testing of the manufacture method of macromolecule composite electric hating material and sample resistance.
Test result: resistance R=420 Ω.
Embodiment 18
The prescription of macromolecule compound electro-thermal coating is as follows by weight:
100 parts of polyurethane resins (NIPPOLAN2301), 19 parts of acetylene carbon blacks, 13.5 parts of electrically conductive graphites, 2.5 parts in magnesium oxide (purity 〉=95%), 2.5 parts in zinc oxide (purity 〉=95%), 6 parts of dioctyl phthalates, 1.2 parts of stearic acid, 0.5 part of dispersant (Tween20), 260 parts of solvents (ethyl acetate, purity 〉=95%).
The compound method of macromolecule compound electro-thermal coating is identical with embodiment 1 with the method for testing of the manufacture method of macromolecule composite electric hating material and sample resistance.
Test result: resistance R=260 Ω.
Embodiment 19
The prescription of macromolecule compound electro-thermal coating is as follows by weight:
100 parts of polyurethane resins (NIPPOLAN2301), 15 parts of acetylene carbon blacks, 15 parts of electrically conductive graphites, 2.5 parts in magnesium oxide (purity 〉=95%), 2.5 parts in zinc oxide (purity 〉=95%), 6 parts of dioctyl phthalates, 1.2 parts of stearic acid, 0.5 part of dispersant (Tween20), 260 parts of solvents (ethyl acetate, purity 〉=95%).
The compound method of macromolecule compound electro-thermal coating is identical with embodiment 1 with the method for testing of the manufacture method of macromolecule composite electric hating material and sample resistance.
Test result: resistance R=330 Ω.
The prescription of embodiment 20, embodiment 21 and embodiment 22 is similar to embodiment 19, and difference is: the use level of acetylene carbon black is 17.5 parts among these three embodiment; The use level of electrically conductive graphite is 0 part in embodiment 20, embodiment 21 is 5 parts; Among the embodiment 22 be 10 parts.
The compound method of macromolecule compound electro-thermal coating is identical with embodiment 1 with the method for testing of the manufacture method of macromolecule composite electric hating material and sample resistance.
Test result:
Can confirm that from above embodiment the method according to this invention can easily obtain the thermo electric material that the resistance value scope is easy to adjust.Because the mode that adopts electric-heating coatings to be applied on the base material obtains thermo electric material, therefore can adjust the thickness of Electric radiant Heating Film, thereby obtain the high thermo electric material of electric conversion rate.
Below, the coating of employing embodiment 5 and embodiment 11 is coated on the base material, measures the heating temp under the specified conditions.
Energising temperature rise experiment
This experiment is adopted and is realized as the base material of macromolecule composite electric hating material to inweave electrode base material in advance.The basic structure that inweaves electrode base material in advance is as follows: fabric fibre is 21 cottons, and the density of warp thread and weft yarn is 200/10cm; The thin copper wire that conductive electrode is 0.08mm by 36 diameters constitutes, the about 6mm of electrode width; Distance has two kinds of specifications between the electrode outer, and a kind of is 22cm, and another kind is 44cm.
Will the coating identical with embodiment 11, be coated on that distance is on the base material of 22cm between the electrode outer, a slice of getting long 100cm is sample, feeds the voltage of 220V, forms power density and is about 600W/m
2Electric radiant Heating Film.Measure the result of temperature under 25 ℃ of room temperature conditions, reach 90 ℃ through 10 minutes temperature, switched on 24 hours always, temperature is stabilized in about 95 degree always as a result.The results are shown in Figure 3.
Will the coating identical with embodiment 11, be coated on that distance is on the base material of 44cm between the electrode outer, a slice of transferring long 50cm is sample, feeds the voltage of 220V, forms power density and is about 150W/m
2Electric radiant Heating Film.Measure the result of temperature under 25 degree room temperature conditions, reach 42 degree through 10 minutes temperature, switched on 24 hours always, temperature is stabilized in about 40 degree always as a result.The results are shown in Figure 4.
Will the coating identical with embodiment 5, be coated on that distance is on the base material of 22cm between the electrode outer, a slice of getting long 50cm is sample, feeds the voltage of 220V, forms power density and is about 250W/m
2Electric radiant Heating Film.Measure the result of temperature under 25 degree room temperature conditions, reach 50 degree through 10 minutes temperature, switched on 24 hours always, temperature is stabilized in about 52 degree always as a result.The results are shown in Figure 5.
Continue the energising experiment
The base material that this experiment is adopted is identical with energising temperature rise experiment.
Will the coating identical with embodiment 3, be coated on that distance is on the base material of 22cm between the electrode outer, a slice of getting long 100cm is sample, feeds the voltage of 220V, forms power density and is about 200W/m
2Electric radiant Heating Film.The sample diaphragm is kept flat on the insulation material, continue uninterrupted energising, the resistance value of sample diaphragm is before the experiment: 1045 Ω, measure its resistance value and be continuing energising: 1014 Ω after 600 days.The results are shown in Figure 6.
Claims (18)
1. macromolecule composite electric hating material, it is characterized in that, comprise the base material of macromolecule compound electro-thermal coating and this coating of carrying, contain the conductive filler of 1～50 weight portion, the auxiliary agent of 1～30 weight portion and the solvent of 100～600 weight portions with respect to the macromolecule resin base-material of 100 weight portions in the described macromolecule compound electro-thermal coating; Described base material is thin, material flexible and that be suitable for applying the coating object,
Described macromolecule resin base-material is selected from epoxy resin, mylar, polystyrene resin, acrylic resin, polyurethane resin, polycarbonate resin,
Described conductive filler contains conductive carbon black as neccessary composition, and the use level of described conductive carbon black is more than 3 weight portions with respect to the macromolecule resin base-material of 100 weight portions,
Described conductive carbon black is high electric conductivity carbon black, superconduct carbon black or acetylene carbon black,
Described conductive filler is the additional conductive filler except conductive carbon black, the use level of described additional conductive filler is 0～45 weight portion with respect to the macromolecule resin base-material of 100 weight portions.
2. macromolecule composite electric hating material according to claim 1 is characterized in that, described base material is plastic film, glass fabric, nonwoven fabrics, chemical fabric or cotton grey fabric.
3. macromolecule composite electric hating material according to claim 1 is characterized in that, described additional conductive filler is electrically conductive graphite, and the average grain diameter of this electrically conductive graphite is 1～50 μ m.
4. macromolecule composite electric hating material according to claim 1 is characterized in that, described auxiliary agent is one or more in coupling agent, plasticizer, stabilizer, dispersant, lubricant and other auxiliary agent.
5. macromolecule composite electric hating material according to claim 4 is characterized in that, described coupling agent is one or more among KH550, KH570, A151, OFS-6020, the DL602; The use level of described coupling agent in macromolecule compound electro-thermal coating is 0.1～10 weight portion for the macromolecule resin base-material with respect to 100 weight portions.
6. macromolecule composite electric hating material according to claim 4 is characterized in that, described plasticizer is dibutyl phthalate, dioctyl phthalate or dibenzoic acid binaryglycol ester; The use level of described plasticizer in macromolecule compound electro-thermal coating is 0.1～20 weight portion for the macromolecule resin base-material with respect to 100 weight portions.
7. macromolecule composite electric hating material according to claim 4 is characterized in that, described dispersant is Tween20, Tween40, Tween60 or Tween80; The use level of described dispersant in macromolecule compound electro-thermal coating is 0.1～10 weight portion for the macromolecule resin base-material with respect to 100 weight portions.
8. macromolecule composite electric hating material according to claim 4 is characterized in that, described lubricant is paraffin, Tissuemat E or stearic acid; The use level of described lubricant in macromolecule compound electro-thermal coating is 0.1～10 weight portion for the macromolecule resin base-material with respect to 100 weight portions.
9. macromolecule composite electric hating material according to claim 4 is characterized in that, one or more of the oxide that described other auxiliary agent is calcium, magnesium, aluminium, tin, zinc, titanium, barium; The use level of described other auxiliary agent in macromolecule compound electro-thermal coating is 0.1～20 weight portion for the macromolecule resin base-material with respect to 100 weight portions.
10. macromolecule composite electric hating material according to claim 1 is characterized in that, described solvent is toluene, dimethylbenzene, acetone, methylethylketone, ethanol, propyl alcohol, ethyl acetate or butyl acetate.
11. macromolecule composite electric hating material according to claim 2, it is characterized in that, described base material is glass fabric, chemical fabric or the cotton grey fabric as fabric, and be to inweave electrode base material in advance, the described electrode base material that inweaves in advance is in it weaves cotton cloth process, and the warp fiber that replaces the above-mentioned fabrics assigned address with conductive filament in groups forms; Described conductive filament is selected from metallic fiber, metal wire combined cotton yarn or filament, and diameter is 0.03～0.5mm; Described is that 5～100 conductive filament next-door neighbours form one group side by side in groups, and each group conductive filament constitutes a conductive electrode of described macromolecule composite electric hating material.
12. macromolecule composite electric hating material according to claim 11 is characterized in that, the width of described conductive electrode is 3～15mm, is to occur in pairs with 2 multiple at the described electrode base material that inweaves in advance, and the distance of every pair of electrode outer is 30～600mm.
13. each described macromolecule composite electric hating material according to claim 1～12, it is characterized in that, described macromolecule composite electric hating material is adapted at 0～160 ℃ with interior low-temperature heat application, especially is fit to be applied to baking drying and the far-infrared physiotherapy health care of building heating, vegeto-animal heating and insulation, grain.
14. the described macromolecule composite electric hating material of each of claim 1～12 0～160 ℃ of application with interior low-temperature heat field, especially is fit to be applied to baking drying and the far-infrared physiotherapy health care of building heating, vegeto-animal heating and insulation, grain.
15. the manufacture method of macromolecule composite electric hating material is characterized in that, this manufacture method may further comprise the steps:
A) conductive filler is placed container, add auxiliary agent and partial solvent;
B) after fully soaking into, add the macromolecule resin base-material, and stir;
C) add residual solvent, be stirred to each component and fully mix, obtain mixture;
D) with high-shearing dispersion emulsifying machine said mixture is carried out high speed dispersion and grinding, the time is 15～30 minutes, finally makes macromolecule compound electro-thermal coating;
E) macromolecule compound electro-thermal coating is coated on the base material equably, coated weight is counted 50～600g/m with weight in wet base
2, 60～120 ℃ of temperature bakings 3～30 minutes, obtain the macromolecule composite electric hating material.
16. one kind inweaves electrode base material in advance as the application of the base material of macromolecule composite electric hating material, this inweaves electrode base material in advance is that the warp fiber that replaces the assigned address of fabric with conductive filament in groups forms in the process of weaving cotton cloth of fabric; Described conductive filament is selected from metallic fiber, metal wire combined cotton yarn or filament, and diameter is 0.03～0.5mm; Described is that 5～100 conductive filament next-door neighbours form one group side by side in groups, and each group conductive filament constitutes a conductive electrode of described macromolecule composite electric hating material.
17. the electrode base material that inweaves in advance according to claim 16 is as the application of the base material of macromolecule composite electric hating material, it is characterized in that, the width of described conductive electrode is 3～15mm, be to occur in pairs with 2 multiple at the described electrode base material that inweaves in advance, the distance of every pair of electrode outer is 30～600mm.
18. as the application of the base material of macromolecule composite electric hating material, it is characterized in that each described macromolecule composite electric hating material that described macromolecule composite electric hating material is claim 1～12 according to claim 16 or the 17 described electrode base materials that inweave in advance.
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| CN103269528B (en) | 2016-05-18 |
| CN102300346A (en) | 2011-12-28 |
| CN103281811B (en) | 2016-03-23 |
| CN103269528A (en) | 2013-08-28 |
| CN102300346B (en) | 2013-05-29 |
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