CN103232608A - Method for preparing faceted heater from ultraviolet crosslinking macromolecular positive temperature coefficient (PTC) material through adopting three-dimensional (3D) printing mode - Google Patents
Method for preparing faceted heater from ultraviolet crosslinking macromolecular positive temperature coefficient (PTC) material through adopting three-dimensional (3D) printing mode Download PDFInfo
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Abstract
The invention relates to a method for preparing a faceted heater from an ultraviolet crosslinking macromolecular positive temperature coefficient (PTC) material through adopting a three-dimensional (3D) printing mode. The method comprises the following steps: a, stirring and mixing 100 parts of polyolefin and/or ethylene-propylene-diene-terpolymer rubber, 15-30 parts of carbon powder, 1-1.5 parts of an ultraviolet initiator and 1-1.5 parts of a crosslinking agent to form a mixed material; b, pouring the mixed material and 100 parts of tetrahydrofuran into an internal mixer to internally mix, and pulping the mixture in a three-roll mill after cooling so as to form a PTC size; c, preparing a PTC faceted heating body from the PTC size through 3D printing; d, irradiating the formed PTC faceted heating body through an ultraviolet light source to form a crosslinking PTC faceted heating body; and e, laminating the crosslinking PTC faceted heating body through laminating equipment to form the faceted heater. By utilizing the method, various 3D printing materials can be provided, and macromolecular PTC materials and devices thereof are simple in technology, energy-saving and environmental-friendly.
Description
Technical field
The invention belongs to high molecular PTC material technology field, relate in particular to a kind of method for preparing planar heater with ultraviolet light cross-linking high molecular PTC material employing 3D printing type.
Background technology
" 3D printing " is popular call, academic name is called rapid shaping technique, be also referred to as and increase the material manufacturing technology, be that a kind of traditional cutter, anchor clamps and lathe of no longer needing just can be created arbitrary shape, according to the three-dimensional modeling data of part or object, the mode that adds up with material by molding device is made the technology of mock-up.The article that the 3D printer can be made are more and more, from automobile, airplane parts, to food, arrive human organ etc.The 3D printing technique is an important breakthrough in world's manufacturing technology field over the past two decades.Be the integrated of multidisciplinary technology such as mechanical engineering (the accurate manufacturing), computer technology (Software development), Numeric Control Technology, Materials science, it is the most difficult, also is that the technology of thinking most crucial is the limitation of printed material, and 3D prints the reality of having to face.The expansion of 3D printed material, what determined the 3D printer can force boundary.Therefore develop more various 3D printed material.Become research from now on and focus and the key point used as intelligent material, Functionally Graded Materials, nano material, heterogeneous material and matrix material etc.
Usually the high molecular PTC material adopts polyethylene-carbon black system, and crosslinking technological is that high-energy radiation is crosslinked, and the electronic component of its preparation and ptc heater are applied to various occasions.
In addition, what existing high molecular PTC material and device thereof generally used is with polymkeric substance and electroconductive particle melting mixing, utilizes the method for extrusion machine moulding then.And existing high molecular PTC material and device thereof are not suitable for making the out-of-shape product, even create, its technology is also quite complicated.Particularly need to make Heating element hemispherical or be approximately oval, almost can't realize by prior art.
Therefore, be badly in need of providing a kind of high molecular PTC material of the 3D of can be used for printing and the production method of PTC planar heater thereof.
Summary of the invention
The purpose of this invention is to provide that technology is simple, a kind of method for preparing planar heater with ultraviolet light cross-linking high molecular PTC material employing 3D printing type of energy-conserving and environment-protective.
Basic design of the present invention is: about can be used for high molecular PTC material that 3D prints and the production method of PTC planar heater thereof, be that the present invention is the high molecular PTC material that a kind of suitable 3D prints, adopt the 3D printing type can prepare various obform body planar heaters.This high molecular PTC planar heater can obtain to have good in limitting warm heat characteristic, and its 3D prints manufacturing process and obviously demonstrates managerial great advantages.Can use be in floor heating, roof thaw ice and snow, the snow melting in parking lot and the removal that auto mirror condenses steam, as special case more by dexterously for the manufacture of life health fields such as transfusion device thermal insulation nursing bottles.Ultraviolet light irradiation causes crosslinked polyolefine material and has been widely used in many fields, compares with chemical crosslink technique with the high-energy radiation method, and photo-crosslinking has many advantages: (l) installation of ultraviolet source generating unit, operation are easier to, and less investment; (2) in the cross-linking process, side reactions such as degraded and oxidation are few.In recent years, polyethylene body ultraviolet light cross-linking new technology successfully is applied in the cable industry, there are materials such as a large amount of Low Density Polyethylenes and high density polyethylene(HDPE) to be made into crosslinked polyethylene, and are widely used in wire cable insulating material, heat-shrinkable tube, film and the foam.Ranby study group is the progress of making a breakthrough property in this respect, and domestic mainly to be that Qu protects the research of equal seminar comparatively deep.Vinyl-vinyl acetate copolymer (EVA) is mainly used in the electric wire and cable industry of producing insulation.The crosslinked of appropriateness can increase performances such as the thermostability of EVA, anti-discharge, anti-solvent and anti-creep, expands its Application Areas.But the photo-crosslinking research of high molecular PTC material is still blank at home.The present invention is raw material with EVA, adopts the uv irradiation method to prepare crosslinked EVA high molecular PTC product.The cross-linked polymer ptc material possesses electrical property excellence, life-time service temperature advantages of higher, is widely used in the application of circuit protection, the heating of middle cryogenic thermostat.What high molecular PTC material and device thereof generally used is with polymkeric substance and electroconductive particle melting mixing, utilizes the method for extrusion machine moulding then.Moulding is compared with extrusion machine, utilize to print or print process is made Heating element various advantages are arranged: when being fit to make planar Heating element in irregular shape, for example, manufacturing is during as the permanent wave moisture eliminator of planar Heating element, because the Heating element that makes is hemispherical, so, make the planar Heating element that can make hemisphere face expand into the plane, this situation utilizes print process just relatively good.Radiator as the anti-steam of auto mirror need be approximately oval in addition, and be not that simple electrode constitutes, utilize this moment print or print process also very effective. utilize this method can be directly on article that need heat, parts etc., to print or print.The characteristics that ultraviolet light cross-linking high molecular PTC material of the present invention and 3D print the production method of planar heater are to adopt ultraviolet initiator to cooperate specific ultraviolet source to carry out the method for ultraviolet light irradiation cross-linking, this method equipment investment cost is low and the cross-linking radiation cost is low, and technology is simple, energy-conserving and environment-protective, product cost inferior quality are good.In order to make the high molecular PTC material become the material that can print, it must be prepared into slurry or printing ink mode because polythene material is dissolved in any solvent hardly, in order to realize the printing inkization of high molecular PTC material, must abandon the use of polythene material.Because the high molecular PTC material must promote reliability of material by crosslinking technological, prolong the life-span of PTC device.
The present invention will adopt vinyl-vinyl acetate copolymer (EVA) to replace polyethylene (PE), adopt ultraviolet light irradiation to cause crosslinking technological simultaneously.Because vinyl-vinyl acetate copolymer (EVA) dissolves in tetrahydrofuran (THF), thereby has paved road for high molecular PTC material printing inkization.High molecular PTC material printing inkization is printed the 3D that realizes planar heater becomes possibility.The printing inkization of high molecular PTC can make ptc material more homogenize, thereby the more even heating of the heating member resistivity of preparation is more even, the each point temperature is more balanced.
The present invention replaces the crosslinked or chemically crosslinked of high-energy radiation by the ultraviolet-crosslinkable technology and has promoted the high molecular PTC reliability of material in the high molecular PTC material, prolonged the life-span of PTC planar heater.The ultraviolet-crosslinkable technology lead in material introduce under ultraviolet light irradiation, finish behind ultraviolet initiator and the linking agent mixing moulding last.The photo-crosslinking research of high molecular PTC material is still blank at home, and the present invention has filled up this blank.
The polyolefine material optical cross-linking method is just to begin to realize the new cross-linking method used in recent years. absorbs and the macromolecular radical that a series of optical physics and photoprocess produce takes place after the UV-light carries out the three-dimensional netted crosslinking structure of rapid compound generation by adding light trigger in the polyolefine material base-material or photosensitizer.
Polyolefine material itself is with the chromophore that can absorb UV-light, must rely on to add light trigger and cause crosslinked.After so-called light trigger refers to absorb the ultraviolet luminous energy of suitable wavelength and intensity, self be cracked into free radical or the energy by excited state and shift and then cause the material of a series of free radical reactions, but only still can not satisfy industrial requirement with light trigger, must adopt and strengthen crosslinked light initiation system.In strengthening crosslinked light initiation system, having increased a new component at least is the multi-group crosslink agent.The photo-crosslinking process has been accelerated in the adding of linking agent widely, especially at the initial stage of crosslinking reaction, compare with the system that does not add linking agent, added the system of linking agent after 5s illumination, gel content sharply rises to more than 65% from not enough l0%, allows the present invention have unforeseeable technique effect.Linking agent all contains two or more unsaturated structures, and linking agent mainly participates in crosslinking reaction by forming allyl radical.
In strengthening cross-linking system, the effect of linking agent mainly shows the following aspects:
(1) quantum yield of raising light trigger.According to polyethylene photo-crosslinking kinetic equation, the quantum yield K of light trigger
lCan be expressed as:
In the formula, T is linking agent; P is light trigger; k
1Be light trigger deactivation rate constant; k
2Reaction rate constant for polymkeric substance and initiator; k
3Reaction rate constant for linking agent.Because the allylic hydrogen in the linking agent is more active than the hydrogen atom on the polymer chain, the light trigger of the easier attitude that is excited is captured, i.e. k
3〉=k
2So k
1≈ l.This explanation multi-group crosslink agent's participation has suppressed the reaction of deactivating of excited state light trigger, makes more excited state light trigger be used for initiation reaction.
(2) speed of quickening crosslinking reaction.When not having linking agent, crosslinkedly only can directly be compounded to form by two macromolecular radicals.Because the macromolecular chain reactivity is poor, the probability of two macromolecular radical collisions is very low.Secondly, because cross-linker molecules has a plurality of functional groups, therefore can be used as the connection that bridge is realized two macromolecular radicals; Micromolecular reactivity is much better, and much bigger with the probability of macromolecular radical collision again, this has accelerated crosslinked formation greatly.
(3) improve crosslinked homogeneity.The linking agent allyl radical of light-initiated generation is relatively stable, do not disappear immediately, can continue to react with other linking agent, free radical is introduced the deep layer of sample, increased the probability of deep polyethylene crosslinking, this has solved the shortcoming of UV-light penetrance difference to a great extent, has improved crosslinked homogeneity.
Ketyl is compounded to form the initiator photolytic product:
Macromolecular radical is compounded to form cross-link bond:
In recent years, ultraviolet light irradiation causes crosslinked polyolefine material and has been widely used in many fields, compare with chemical crosslink technique with the high-energy radiation method, photo-crosslinking has many advantages: (l) installation of ultraviolet source generating unit, operation are easier to, and less investment; (2) in the cross-linking process, side reactions such as degraded and oxidation are few.
Specifically, of the present inventionly a kind ofly adopt the 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material, it is characterized in that making according to following steps:
A, batch mixing: by weight, 100 parts of polyolefine and/or terpolymer EP rubber, 15 ~ 50 parts of carbon dusts, 0.5 ~ 4 part of ultraviolet initiator, 0.5 ~ 4 part of linking agent are put into homogenizer and mixed at normal temperatures, mixing time 3 minutes forms compound; Optimally, 20～30 parts of carbon blacks; 1～1.5 part of ultraviolet initiator; 1～1.5 part of linking agent;
B, make slurry: compound and 100 parts of tetrahydrofuran (THF)s are poured in the Banbury mixer, under 100～160 ℃ of temperature, carried out banburying, 15 minutes banburying time, allow it naturally cool to normal temperature then, cooling back slurrying in three-high mill
,Repeat-rolling forms the PTC slurry 4 times, and the rotating ratio of three-high mill is made as
1:3:9Optimally, under 130 ℃ of temperature, carry out banburying;
C, 3D printing shaping: the PTC slurry is printed the planar heating member of preparation PTC through 3D; The planar heating member print thickness control of PTC is about 0.05mm; Be of a size of 10*10mm, interelectrode distance 10mm;
D, ultraviolet light irradiation: the planar heating member of PTC that forms is formed the planar heating member of crosslinked PTC through ultraviolet source irradiation;
E, overlay film, cooling and shaping: the planar heating member of crosslinked PTC is used the equipment for coating film overlay film under 120～160 ℃ of temperature, thickness 20 μ, the naturally cooling typing namely forms planar heater.Optimally, under 130 ℃ of temperature, use the equipment for coating film overlay film.
Be selected from a kind of or its combination in the following material at polyolefine described in the step a of the present invention: ethene one acetate ethylene copolymer (EVA), ethene one methyl acrylate copolymer (EMA), Ethylene ethylacrylate copolymer (EEA), ethene one butyl acrylate copolymer (EBA), ethylene-propylene diene copolymer (E Β DM).Better preferably ethene one acetate ethylene copolymer (EVA).
Be selected from a kind of or its combination in the following material at carbon dust described in the step a of the present invention: carbon black, graphite and carbon element are fine plain.Better preferably carbon black, 20～30 parts of content.
Be a kind of or its combination in benzoin dimethylether, dialkoxy methyl phenyl ketone, Oxoxanthone, grace ketone, Fluorenone or benzophenone and the derivative thereof at ultraviolet initiator described in the step a of the present invention.Better preferably benzophenone BP; 1～1.5 part of content.
Be cyanacrylate (TAIC), Viscoat 295 (PMPTA), pentaerythritol triacrylate (PETA) or Viscoat 295 (TMPTA) at linking agent described in the step a of the present invention.Better preferably Viscoat 295 (TMPTA); 1～1.5 part of content.
Be the solvent of polyolefine and/or ethylene propylene diene monomer (EPDM) material at tetrahydrofuran (THF) described in the step b of the present invention.
Ultraviolet light irradiation described in the steps d of the present invention system adopt thermoelectron excite in the pressure mercuryarc lamp, H type lamp is housed, is added with the D type lamp of ferro element or is added with the electrodeless lamp of V-type microwave-excitation of gallium element.The ultraviolet light irradiation cross-linking apparatus of these specific light sources carries out cross-linking radiation to the planar heating member of PTC that forms.
System carried out the on-line continuous ultraviolet light irradiation 0.5 ~ 20 second to the planar heating member of PTC in ultraviolet light irradiation step described in the steps d of the present invention, also can be 1～10 second, so that it is crosslinked to make planar heating member obtain the degree of depth, optimally was 5 seconds.Light intensity 400-4000mW/cm
2, wavelength: 300-500nm.
Compared with the aforementioned existing similar products, the present invention not only provides more various 3D printed material, and allows high molecular PTC material and device technology is simpler and energy-conserving and environment-protective.
Content of the present invention further illustrates with the following Examples, but content of the present invention is not limited only to content related among the embodiment.
Embodiment
By describing technology contents of the present invention in detail, being realized purpose and effect, give explanation below in conjunction with embodiment is detailed, but protection domain of the present invention is not limited to the following example.
Embodiment 1: a kind of described in the present embodiment adopts the 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material, it is characterized in that making according to following steps:
A, batch mixing: by weight, 100g ethene one acetate ethylene copolymer (EVA), 20g carbon black, 1g benzophenone BP, 1g Viscoat 295 (TMPTA) are put into homogenizer and mixed at normal temperatures, mixing time 3 minutes forms compound;
B, make slurry: compound and 100g tetrahydrofuran (THF) are poured in the Banbury mixer, under 130 ℃ of temperature, carried out banburying, 15 minutes banburying time, allow it naturally cool to normal temperature then, cooling back slurrying in three-high mill
,Repeat-rolling forms the PTC slurry 4 times, and the rotating ratio of three-high mill is made as
1:3:9
C, 3D printing shaping: the PTC slurry is printed the planar heating member of preparation PTC through 3D; The planar heating member print thickness control of PTC is about 0.05mm; The experiment body is of a size of 10*10mm, interelectrode distance 10mm;
D, ultraviolet light irradiation: the planar heating member of PTC that forms is formed the planar heating member of crosslinked PTC through ultraviolet source irradiation; Light intensity 400mW/cm
2, wavelength 300nm, irradiation time is 5 seconds;
E, overlay film, cooling and shaping: the planar heating member of crosslinked PTC is used the equipment for coating film overlay film under 130 ℃ of temperature, thickness 20 μ form the exhausted rafter protective membrane of one deck on the planar heating member of crosslinked PTC surface at last, and the naturally cooling typing namely forms planar heater.
The planar heater that above-mentioned ultraviolet light cross-linking is produced is measured, and the result is as follows: side's resistance=720 Ω; PTC effect=5.3*10
2Use temperature scope-55 ~ 125 ℃; Insulation voltage 〉=1500V; Insulation resistance 〉=10
8Ω .cm; Tensile strength=15.6MPa; By 125 ℃ of * 168h thermal ageing tests.
Embodiment 2: a kind of described in the present embodiment adopts the 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material, it is characterized in that making according to following steps:
A, batch mixing: by weight, 100g ethene one acetate ethylene copolymer (EVA), 25g carbon black, 1g benzophenone BP, 1g Viscoat 295 (TMPTA) are put into homogenizer and mixed at normal temperatures, mixing time 3 minutes forms compound;
B, make slurry: compound and 100g tetrahydrofuran (THF) are poured in the Banbury mixer, under 130 ℃ of temperature, carried out banburying, 15 minutes banburying time, allow it naturally cool to normal temperature then, cooling back slurrying in three-high mill
,Repeat-rolling forms the PTC slurry 4 times, and the rotating ratio of three-high mill is made as
1:3:9
C, 3D printing shaping: the PTC slurry is printed the planar heating member of preparation PTC through 3D; The planar heating member print thickness control of PTC is about 0.05mm; The experiment body is of a size of 10*10mm, interelectrode distance 10mm;
D, ultraviolet light irradiation: the planar heating member of PTC that forms is formed the planar heating member of crosslinked PTC through ultraviolet source irradiation; Light intensity 4000mW/cm
2, wavelength 500nm, irradiation time is 5 seconds;
E, overlay film, cooling and shaping: the planar heating member of crosslinked PTC is used the equipment for coating film overlay film under 130 ℃ of temperature, thickness 20 μ, the naturally cooling typing namely forms planar heater.
The planar heater that above-mentioned ultraviolet light cross-linking is produced is measured, and the result is as follows: side's resistance=220 Ω; PTC effect=2.3*10
2Use temperature scope-55 ~ 125 ℃; Insulation voltage 〉=1500V; Insulation resistance 〉=10
8Ω .cm; Tensile strength=14.3MPa; By 125 ℃ of * 168h thermal ageing tests.
Embodiment 3: a kind of described in the present embodiment adopts the 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material, it is characterized in that making according to following steps:
A, batch mixing: by weight, 100g ethene one acetate ethylene copolymer (EVA), 30g carbon black, 1g benzophenone BP, 1.5g Viscoat 295 (TMPTA) are put into homogenizer and mixed at normal temperatures, mixing time 3 minutes forms compound;
B, make slurry: compound and 100g tetrahydrofuran (THF) are poured in the Banbury mixer, under 130 ℃ of temperature, carried out banburying, 15 minutes banburying time, allow it naturally cool to normal temperature then, cooling back slurrying in three-high mill
,Repeat-rolling forms the PTC slurry 4 times, and the rotating ratio of three-high mill is made as
1:3:9
C, 3D printing shaping: the PTC slurry is printed the planar heating member of preparation PTC through 3D; The planar heating member print thickness control of PTC is about 0.05mm; The experiment body is of a size of 10*10mm, interelectrode distance 10mm;
D, ultraviolet light irradiation: the planar heating member of PTC that forms is formed the planar heating member of crosslinked PTC through ultraviolet source irradiation; Light intensity 1000mW/cm
2, wavelength: 400nm, irradiation time is 5 seconds;
E, overlay film, cooling and shaping: the planar heating member of crosslinked PTC is used the equipment for coating film overlay film under 130 ℃ of temperature, thickness 20 μ, the naturally cooling typing namely forms planar heater.
The planar heater that above-mentioned ultraviolet light cross-linking is produced is measured, and the result is as follows: side's resistance=40 Ω; PTC effect=51; Use temperature scope-55 ~ 125 ℃; Insulation voltage 〉=1500V; Insulation resistance 〉=10
8Ω .cm; Tensile strength=13.6MPa; By 125 ℃ of * 168h thermal ageing tests.
Embodiment 4: a kind of described in the present embodiment adopts the 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material, it is characterized in that making according to following steps:
A, batch mixing: by weight, 100g ethene one acetate ethylene copolymer (EVA), 25g carbon black, 1g benzophenone BP, 1.5g Viscoat 295 (TMPTA) are put into homogenizer and mixed at normal temperatures, mixing time 3 minutes forms compound;
B, make slurry: compound and 100g tetrahydrofuran (THF) are poured in the Banbury mixer, under 130 ℃ of temperature, carried out banburying, 15 minutes banburying time, allow it naturally cool to normal temperature then, cooling back slurrying in three-high mill
,Repeat-rolling forms the PTC slurry 4 times, and the rotating ratio of three-high mill is made as
1:3:9
C, 3D printing shaping: the PTC slurry is printed the planar heating member of preparation PTC through 3D; The planar heating member print thickness control of PTC is about 0.05mm; The experiment body is of a size of 10*10mm, interelectrode distance 10mm;
D, ultraviolet light irradiation: the planar heating member of PTC that forms is formed the planar heating member of crosslinked PTC through ultraviolet source irradiation; Light intensity 2000mW/cm
2, wavelength: 350nm, irradiation time is 5 seconds;
E, overlay film, cooling and shaping: the planar heating member of crosslinked PTC is used the equipment for coating film overlay film under 130 ℃ of temperature, thickness 20 μ, the naturally cooling typing namely forms planar heater.
The planar heater that above-mentioned ultraviolet light cross-linking is produced is measured, and the result is as follows: side's resistance=470 Ω; PTC effect=6.7*10
2Use temperature scope-55 ~ 125 ℃; Insulation voltage 〉=1500V; Insulation resistance 〉=10
8Ω .cm; Tensile strength=13.9MPa; By 125 ℃ of * 168h thermal ageing tests.
Embodiment 5: a kind of described in the present embodiment adopts the 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material, it is characterized in that making according to following steps:
A, batch mixing: by weight, 100g ethene one acetate ethylene copolymer (EVA), 25g carbon black, 1.5g benzophenone BP, 1g Viscoat 295 (TMPTA) are put into homogenizer and mixed at normal temperatures, mixing time 3 minutes forms compound;
B, make slurry: compound and 100g tetrahydrofuran (THF) are poured in the Banbury mixer, under 130 ℃ of temperature, carried out banburying, 15 minutes banburying time, allow it naturally cool to normal temperature then, cooling back slurrying in three-high mill
,Repeat-rolling forms the PTC slurry 4 times, and the rotating ratio of three-high mill is made as
1:3:9
C, 3D printing shaping: the PTC slurry is printed the planar heating member of preparation PTC through 3D; The planar heating member print thickness control of PTC is about 0.05mm; The experiment body is of a size of 10*10mm, interelectrode distance 10mm;
D, ultraviolet light irradiation: the planar heating member of PTC that forms is formed the planar heating member of crosslinked PTC through ultraviolet source irradiation; Light intensity 3000mW/cm
2, wavelength: 450nm, irradiation time is 5 seconds;
E, overlay film, cooling and shaping: the planar heating member of crosslinked PTC is used the equipment for coating film overlay film under 130 ℃ of temperature, thickness 20 μ, the naturally cooling typing namely forms planar heater.
The planar heater that above-mentioned ultraviolet light cross-linking is produced is measured, and the result is as follows: side's resistance=310 Ω; PTC effect 4.8*10
2Use temperature scope-55 ~ 125 ℃; Insulation voltage 〉=1500V; Insulation resistance 〉=10
8Ω .cm; Tensile strength=13.8MPa; By 125 ℃ of * 168h thermal ageing tests.
Embodiment 6: a kind of described in the present embodiment adopts the 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material, it is characterized in that making according to following steps:
A, batch mixing: by weight, 100g ethene one acetate ethylene copolymer (EVA), 15g carbon black, 1g benzophenone BP, 1g Viscoat 295 (TMPTA) are put into homogenizer and mixed at normal temperatures, mixing time 3 minutes forms compound;
B, make slurry: compound and 100g tetrahydrofuran (THF) are poured in the Banbury mixer, under 130 ℃ of temperature, carried out banburying, 15 minutes banburying time, allow it naturally cool to normal temperature then, cooling back slurrying in three-high mill
,Repeat-rolling forms the PTC slurry 4 times, and the rotating ratio of three-high mill is made as
1:3:9
C, 3D printing shaping: the PTC slurry is printed the planar heating member of preparation PTC through 3D; The planar heating member print thickness control of PTC is about 0.05mm; The experiment body is of a size of 10*10mm, interelectrode distance 10mm;
D, ultraviolet light irradiation: the planar heating member of PTC that forms is formed the planar heating member of crosslinked PTC through ultraviolet source irradiation; Light intensity 400mW/cm
2, wavelength: 300nm, irradiation time is 5 seconds;
E, overlay film, cooling and shaping: the planar heating member of crosslinked PTC is used the equipment for coating film overlay film under 130 ℃ of temperature, thickness 20 μ, the naturally cooling typing namely forms planar heater.
The planar heater that above-mentioned ultraviolet light cross-linking is produced is measured, and the result is as follows: side resistance=1.04M Ω; PTC effect=1.8*10
4Use temperature scope-55 ~ 125 ℃; Insulation voltage 〉=1500V; Insulation resistance 〉=10
8Ω .cm; Tensile strength=16.6MPa; By 125 ℃ of * 168h thermal ageing tests.
Embodiment 7: a kind of described in the present embodiment adopts the 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material, it is characterized in that making according to following steps:
A, batch mixing: by weight, 100g terpolymer EP rubber, 25g carbon black, 1g benzophenone BP, 1g Viscoat 295 (TMPTA) are put into homogenizer and mixed at normal temperatures, mixing time 3 minutes forms compound;
B, make slurry: compound and 100g tetrahydrofuran (THF) are poured in the Banbury mixer, under 130 ℃ of temperature, carried out banburying, 15 minutes banburying time, allow it naturally cool to normal temperature then, cooling back slurrying in three-high mill
,Repeat-rolling forms the PTC slurry 4 times, and the rotating ratio of three-high mill is made as
1:3:9
C, 3D printing shaping: the PTC slurry is printed the planar heating member of preparation PTC through 3D; The planar heating member print thickness control of PTC is about 0.05mm; The experiment body is of a size of 10*10mm, interelectrode distance 10mm;
D, ultraviolet light irradiation: the planar heating member of PTC that forms is formed the planar heating member of crosslinked PTC through ultraviolet source irradiation; Light intensity 4000mW/cm
2, wavelength: 500nm, irradiation time is 5 seconds;
E, overlay film, cooling and shaping: the planar heating member of crosslinked PTC is used the equipment for coating film overlay film under 130 ℃ of temperature, thickness 20 μ, the naturally cooling typing namely forms planar heater.
The planar heater that above-mentioned ultraviolet light cross-linking is produced is measured, and the result is as follows: side's resistance=980 Ω; PTC effect=32; Use temperature scope-55 ~ 125 ℃; Insulation voltage 〉=1500V; Insulation resistance 〉=10
8Ω .cm; Tensile strength=17.6MPa; By 125 ℃ of * 168h thermal ageing tests.
In sum, the characteristics that ultraviolet light cross-linking high molecular PTC material of the present invention and 3D print the production method of planar heating member body are to adopt ultraviolet initiator to cooperate specific ultraviolet source to carry out the method for ultraviolet light irradiation cross-linking, and this method equipment investment cost is low, technology simple, energy-conserving and environment-protective and cross-linking radiation cost are low; It is the desirable mode of production of producing planar heating member of new generation.Low, the good quality of this product cost has the very strong market competitiveness; The characteristics of the times that meet personalized customization, market outlook are very wide.
The preferred benzophenone BP of ultraviolet initiator, selected specific ultraviolet source carry out the key technical problem that ultraviolet light irradiation cross-linking can solve UV-light deep layer penetrativity difference and cause PTC performance and the serious deterioration of material mechanical performance.
The present invention is not limited in above-mentioned specific embodiment, and those skilled in the art that also can make multiple variation accordingly, but any and the present invention are equal to or similar variation all should be encompassed in the scope of claim of the present invention.
Claims (7)
1. one kind is adopted the 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material, it is characterized in that making according to following steps:
A, batch mixing: by weight, 100 parts of polyolefine and/or terpolymer EP rubber, 15 ~ 30 parts of carbon dusts, 1～1.5 part of ultraviolet initiator, 1～1.5 part of linking agent are put into homogenizer and mixed at normal temperatures, mixing time 3 minutes forms compound;
B, make slurry: compound and 100 parts of tetrahydrofuran (THF)s are poured in the Banbury mixer, under 130 ℃ of temperature, carried out banburying, 15 minutes banburying time, allow it naturally cool to normal temperature then, cooling back slurrying in three-high mill
,Repeat-rolling forms the PTC slurry 4 times, and the rotating ratio of three-high mill is made as
1:3:9
C, 3D printing shaping: the PTC slurry is printed the planar heating member of preparation PTC through 3D;
D, ultraviolet light irradiation: the planar heating member of PTC that forms is formed the planar heating member of crosslinked PTC through ultraviolet source irradiation;
E, overlay film, cooling and shaping: the planar heating member of crosslinked PTC is used the equipment for coating film overlay film under 130 ℃ of temperature, thickness 20 μ, the naturally cooling typing namely forms planar heater.
2. as claimed in claim 1ly a kind ofly adopt the 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material, it is characterized in that in step
a, described in polyolefine be selected from a kind of or its combination in the following material: ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-butyl acrylate copolymer (EBA), ethylene-propylene diene copolymer (E Β DM).
3. a kind ofly adopt the 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material as claim 1 is described, it is characterized in that step a, described in carbon dust be selected from a kind of or its combination in the following material: carbon black, graphite and carbon element are fine plain.
4. a kind ofly adopt the 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material as claim 1 is described, it is characterized in that step a, described in ultraviolet initiator be a kind of or its combination in benzoin dimethylether, dialkoxy methyl phenyl ketone, Oxoxanthone, grace ketone, Fluorenone or benzophenone and the derivative thereof.
5. a kind ofly adopt the 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material as claim 1 is described, it is characterized in that step a, described in linking agent be cyanacrylate (TAIC), Viscoat 295 (PMPTA), pentaerythritol triacrylate (PETA) or Viscoat 295 (TMPTA).
6. as claimed in claim 1ly a kind ofly adopt the 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material, it is characterized in that the system of ultraviolet light irradiation described in the steps d adopt thermoelectron excite in the pressure mercuryarc lamp, H type lamp is housed, is added with the D type lamp of ferro element or is added with the electrodeless lamp of V-type microwave-excitation of gallium element.
7. as claimed in claim 1ly a kind ofly adopt the 3D printing type to prepare the method for planar heater with ultraviolet light cross-linking high molecular PTC material, its feature was carried out the on-line continuous ultraviolet light irradiation 5 seconds in the system of ultraviolet light irradiation described in the steps d to the planar heating member of PTC.
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