CN110467846A - A kind of preparation method of oiliness electric heating conversion ink and prepared ink - Google Patents
A kind of preparation method of oiliness electric heating conversion ink and prepared ink Download PDFInfo
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- CN110467846A CN110467846A CN201910773915.9A CN201910773915A CN110467846A CN 110467846 A CN110467846 A CN 110467846A CN 201910773915 A CN201910773915 A CN 201910773915A CN 110467846 A CN110467846 A CN 110467846A
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- Prior art keywords
- ink
- electric heating
- oiliness
- expanded graphite
- resin
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- 238000005485 electric heating Methods 0.000 title claims abstract description 93
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000010439 graphite Substances 0.000 claims abstract description 78
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000011231 conductive filler Substances 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000006185 dispersion Substances 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 238000005516 engineering process Methods 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 206010037660 Pyrexia Diseases 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000012528 membrane Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
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- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 claims description 3
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 claims description 3
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- YREOLPGEVLLKMB-UHFFFAOYSA-N 3-methylpyridin-1-ium-2-amine bromide hydrate Chemical compound O.[Br-].Cc1ccc[nH+]c1N YREOLPGEVLLKMB-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The present invention provides a kind of method for preparing oiliness electric heating conversion ink, including expanded graphite is crushed, with the expanded graphite that must be crushed；The expanded graphite of crushing, conductive filler, resin, auxiliary agent and solvent are premixed, to obtain pre-composition；Solvent is added in the pre-composition, and stirs, obtains the uniformly ink precursor dispersion liquid without blistering；And the ink precursor dispersion liquid is passed through into stripping technology, obtain oiliness electric heating conversion ink；Wherein, the mass percent of the resin, the solvent and the auxiliary agent is respectively 10~40%, 35~80% and 0.3~4%.Obtained oiliness electric heating conversion ink is good to printing technology adaptability, and electric heating film uniformity is high.
Description
Technical field
The present invention relates to a kind of preparation methods of oiliness electric heating conversion ink, especially with respect to a kind of electric conductivity and far infrared
The preparation method for the oiliness electric heating conversion ink haveing excellent performance.
Background technique
Far red infrared radiation electrothermal membrane has energy conservation and environmental protection, installs the advantages such as simple, various informative, health-care physical therapy.Radiation electric
Hotting mask heating system is using electric power as the energy, using pure resistance as heater, by heat in the form of far infrared heat to indoor heating.
It is made between insulating substrate film of electric heating ink, metal current-carrying item through printing, processing, hot pressing.Wherein being used to prepare has
The electric heating ink of good printability and resistance to heat aging electricity thermal conversion film is the key problem in technology of this kind of product.
Since there is grapheme material good conductive characteristic, prior art, such as CN107936686A to announce one kind
Compound carbon-based water-based electric heating ink of graphene and preparation method thereof, but its graphene used is functionalization graphene, functionalization
Graphene higher cost, pollution are larger, are unfavorable for being mass produced.In addition, CN106883684A discloses a kind of graphene three
Composite water soluble electric heating ink and preparation method thereof is tieed up, by adding conductive black and carbon nanotube between graphene two-dimensional structure
3-D nano, structure layer is formed, solves the problems, such as that graphitization causes thermal conversion efficiency to be decayed, but thirdly phase material all needs heating point
It dissipates, and dispersion process overlong time, energy consumption are excessively high.In the prior arts such as CN107760128A, CN108250844A, by graphite
Alkene and other conductive powder bodies are distributed in resin and solvent, and are stirred and are ground to enhance dispersibility.CN108530996A
Then to disclose a kind of preparation method of highly conductive ink of watersoluble plumbago alkene, however, the viscosity of water-based ink is lower, printability compared with
Difference, printing quality are difficult to control, and product electric thermal power density is not uniform enough, and surface hydrophilic group is excessive, are easy the moisture absorption.
It is led it can be seen from the above, industry still needs to the oiliness carbon system that a kind of dispersibility is good, manufacture craft is easy and conductive effect is good
The preparation method of electric ink.
Summary of the invention
First aspect present invention provides a kind of method for preparing oiliness electric heating conversion ink, comprising the following steps: will expand
Graphite crushes, with the expanded graphite that must be crushed；The expanded graphite of crushing, conductive filler, resin, auxiliary agent and solvent are carried out pre-
It is mixed, to obtain pre-composition；Solvent is added in the pre-composition, and stirs, obtains the uniformly ink precursor dispersion liquid without blistering；
And the ink precursor dispersion liquid is passed through into stripping technology, obtain oiliness electric heating conversion ink；Wherein, the resin, institute
The mass percent for stating solvent and the auxiliary agent is respectively 10~40%, 35~80% and 0.3~4%.
According to embodiments of the present invention, D50=5 to 600 μm of the expanded graphite of the crushing.
According to embodiments of the present invention, the conductive filler is selected from nickel powder, carbon nanotube, conductive black, graphite powder and acetylene
It is at least one of black.
According to embodiments of the present invention, the ratio of the expanded graphite and the conductive filler is 1:2.5 to 20:1, described swollen
The mass percent of swollen graphite and the conductive filler in oiliness electric heating conversion ink is 4~28%.
According to embodiments of the present invention, the resin be selected from acrylic resin, epoxy resin, polyurethane resin, alkyd resin,
At least one of polyester resin and polyamide.
According to embodiments of the present invention, the solvent is selected from ethyl alcohol, terpinol, Propylene glycol n-propyl ether, ethyl acetate, acetic acid fourth
Ester, n-butyl acetate, pentyl acetate, dibasic ester (DBE, dimethyl succinate, dimethyl glutarate and hexanedioic acid dimethyl ester three
The combination of kind of environmentally friendly solvent), butanone, cyclohexanone, isophorone, -2 pyrrolidones of 1- methyl, toluene, dimethylbenzene and N, N-
At least one of dimethylformamide.
According to embodiments of the present invention, the auxiliary agent is at least one of auxiliary rheological agents, coupling agent and dispersing agent.
According to embodiments of the present invention, the stripping technology is at least one in the grinding of three rollers, sand milling, high-pressure homogeneous and ball milling
Kind.
According to embodiments of the present invention, for the ink precursor dispersion liquid after stripping technology, fineness is lower than 20 μm.
Second aspect of the present invention provides a kind of oiliness electric heating conversion ink, is to utilize preparation oiliness electric heating of the present invention
Prepared by the method for converting ink.
Third aspect present invention provides a kind of fever membrane module, comprising: electric heating conversion coating, conductive layer and electrode, wherein institute
Stating electric heating conversion coating is to convert oiliness electric heating prepared by the method for ink using preparation oiliness electric heating of the present invention to convert oil
Ink solidification gained.The conductive layer deposition is on the electric heating conversion coating.The electrode contacts the conductive layer.
Compared to prior art, oiliness electric heating prepared by the method for the present invention converts ink, is filled out using multiple inks conduction
Material, the weather resistance that electric heating converts ink is good, while having compared with low-solid content, can be improved and adapts to printing or coating processes
Property, it is particularly suitable for the higher gravure printing technique of production efficiency；The oiliness electric heating converts the anti-of Electric radiant Heating Film made by ink
Flexility is also high, and the condition of cure of ink is simple.
Detailed description of the invention
Fig. 1 is that the conversion ink of oiliness electric heating obtained by the embodiment of the present invention 1 is printed on mylar PET and dried solid
The surface (A) of resulting film and (B) cross-sectional scans electromicroscopic photograph after change.
Fig. 2 be (A) for the heating film that oiliness electric heating obtained by the embodiment of the present invention 1 converts printing ink to manufacture it is in kind shine and
(B) its modular construction, wherein l is that film is long；D is that film is wide；And h is film thickness.
Fig. 3 is the far infrared wavelength graph for the heating film that oiliness electric heating obtained by the embodiment of the present invention 1 converts printing ink to manufacture
Spectrum.
Fig. 4 be the embodiment of the present invention 1 obtained by oiliness electric heating convert printing ink to manufacture fever membrane module (A) tiling and
(B) the thermal imaging picture of 180 ° of curlings.
Fig. 5 A is the heating temperature lowering curve for the fever membrane module that oiliness electric heating of the present invention converts printing ink to manufacture.
Fig. 5 B is the temperature cycles decay pattern for the fever membrane module that oiliness electric heating of the present invention converts printing ink to manufacture.
Specific embodiment
Illustrate embodiments of the present invention by particular specific embodiment below, people skilled in the art can be by this theory
The bright revealed content of book is understood other advantages and efficacy of the present invention easily.
It should be clear that this specification structure depicted in this specification institute accompanying drawings, ratio, size etc., only to cooperate specification to be taken off
The content shown is not intended to limit the invention enforceable qualifications for the understanding and reading of people skilled in the art,
Therefore not having technical essential meaning, the modification of any structure, the change of proportionate relationship or the adjustment of size are not influencing this hair
Under bright the effect of can be generated and the purpose that can reach, disclosed technology contents should all be fallen in and obtain the model that can cover
In enclosing.Meanwhile cited such as "upper" in this specification, "inner", "outside", "bottom", " one ", " in " term, be also only and be convenient for
Narration is illustrated, rather than to limit the scope of the invention, relativeness is altered or modified, without substantive change
Under technology contents, when being also considered as the enforceable scope of the present invention.
First aspect present invention provides a kind of method for preparing oiliness electric heating conversion ink, comprising the following steps: will expand
Graphite crushes, with the expanded graphite that must be crushed；The expanded graphite of crushing, conductive filler, resin, auxiliary agent and solvent are carried out pre-
It is mixed, to obtain pre-composition；Solvent is added in the pre-composition, and stirs, obtains the uniformly ink precursor dispersion liquid without blistering；
And the ink precursor dispersion liquid is passed through into stripping technology, obtain oiliness electric heating conversion ink；Wherein, the resin, institute
The mass percent for stating solvent and the auxiliary agent is respectively 10~40%, 35~80% and 0.3~4%.
According to embodiments of the present invention, the D50 of the expanded graphite of the crushing can be 5 to 600 μm.Preferably, the crushing
The D50 of expanded graphite can be for not less than 15 to 200 μm.
According to embodiments of the present invention, the conductive filler is selected from nickel powder, carbon nanotube, conductive black, graphite powder and acetylene
It is one or more of black.
According to embodiments of the present invention, the ratio of the expanded graphite and the conductive filler can be 1:2.5 to 20:1, described
The mass percent of expanded graphite and the conductive filler in oiliness electric heating conversion ink is 4~28%.
According to the present invention, carbon black can regard zero dimension material as, carbon nanotube is one-dimensional material, graphene and graphite nano plate
It is two-dimensional material, these three types of materials become dotted line face contact by simple plane-plane contact and combine, and form the conduction of steady and continuous
Network.
According to the present invention, the expanded graphite (expanded graphite, EG) is by natural graphite scale through inserting
The loose porous vermiform substance of layer, washing, one kind that is dry, being obtained through high temperature puffing.Graphite is often referred to natural graphite, mainly
It is divided into blocky graphite, crystalline flake graphite and aphanitic graphite.Graphite is carbonaceous element crystalline mineral, its crystallization screen work is hexagon
Layer structure.Distance between each stratum reticulare is 340pm, and the spacing of carbon atom is 142pm in same stratum reticulare.Belong to hexagonal crystal system, tool
Complete stratiform cleavage.Cleavage surface is weaker to van der Waals' force based on molecular link.
When expansible graphite is heated to certain temperature, is decomposed due to being occluded in compound in interlayer dot matrix, may expand stone
Ink just starts to expand, which is known as initial expansion temperature, expands completely at 1000 DEG C, reaches maximum volume.Inflatable stone
200 times or more when the swelling volume of ink can achieve initial.Graphite after expansion is known as expanded graphite or graphite worm, by
Former flakey becomes the very low vermiform of density, forms an extraordinary heat insulation layer.EG is in addition to having natural graphite itself
The excellent performances such as cold-hot, corrosion-resistant, self-lubricating other than, also there is the unexistent softness of natural graphite, compression resilience, suction
The characteristics such as attached property, ecological environment harmony, bio-compatibility, radiation resistance.The production that expanded graphite can be used as graphene is former
Material.
And graphene nanometer sheet (Graphene nanosheets, GNSs or Graphene Nano Flakes, GNFs),
Also referred to as carbon nanosheet (Carbon nanoflakes, CNFs) or carbon nanowalls (Carbon nanowalls, CNWs), thickness
For the bidimensional graphitic nanomaterials of nanoscale, common is 10 to 20 layers referred to as graphene micro-nano, it is also possible to being single
Layer graphene.
According to embodiments of the present invention, the resin can be oleoresin, such as, but not limited to acrylic resin, asphalt mixtures modified by epoxy resin
One or more of rouge, polyurethane resin, alkyd resin, polyester resin and polyamide.
According to embodiments of the present invention, the solvent can be the solvent that can dissolve each other with oleoresin, such as, but not limited to ethyl alcohol,
Terpinol, Propylene glycol n-propyl ether, ethyl acetate, butyl acetate, n-butyl acetate, pentyl acetate, dibasic ester, DBE (succinic acid
Dimethyl ester, the combination of three kinds of environmentally friendly solvents of dimethyl glutarate and hexanedioic acid dimethyl ester), butanone, cyclohexanone, different fluorine you
One or more of ketone, -2 pyrrolidones of 1- methyl, toluene, dimethylbenzene and N,N-dimethylformamide.
According to embodiments of the present invention, the auxiliary agent is at least one of auxiliary rheological agents, coupling agent and dispersing agent.
The auxiliary rheological agents one or more of can be but be not limited to fumed silica, castor oil and bentonite.
Wherein, the mass ratio of the auxiliary rheological agents and conductive filler can be 0.1% to 5%.
The dispersing agent can be but be not limited to one or more of neopelex and cetomacrogol 1000.Its
In, the mass ratio of the dispersing agent and conductive filler can be 0.1 to 10%.
The coupling agent one or more of can be but be not limited to A-171, KH-550, KH-560 and KH-570.Wherein,
The mass ratio of the silane coupling agent and conductive filler can be 0.1% to 5%.
According to embodiments of the present invention, the stripping technology can for the grinding of three rollers, be sanded, in high-pressure homogeneous and ball milling at least
It is a kind of.According to the present invention, the stripping technology can be used one kind of above-mentioned technique, and two or three etc..
According to embodiments of the present invention, for the ink precursor dispersion liquid after stripping technology, fineness is lower than 20 μm.
Second aspect of the present invention provides a kind of oiliness electric heating conversion ink, is to utilize preparation oiliness electric heating of the present invention
Prepared by the method for converting ink.
Third aspect present invention provides a kind of fever membrane module, comprising: electric heating conversion coating, conductive layer and electrode, wherein institute
Stating electric heating conversion coating is to convert oiliness electric heating prepared by the method for ink using preparation oiliness electric heating of the present invention to convert oil
Ink solidification gained.The conductive layer deposition is on the electric heating conversion coating.The electrode contacts the conductive layer.
According to embodiments of the present invention, oiliness electric heating conversion ink be applied to printing substrate can for PET film, PI film,
Polyester fiber, nylon fiber, cotton, woven dacron, silica gel, PVC cloth, alumina ceramic plate, devitrified glass, non-woven fabrics or paper,
But not limited to this.
Embodiment 1
According to the present invention, the expanded graphite of 450 multiplying powers is obtained swollen through what is crushed by being mechanically pulverized to D50=200 μm
Swollen graphite；The expanded graphite through crushing and conductive black are formed into bi-component filler by the mass ratio of 8:1 respectively；Mixing institute
State bi-component filler 10%, acrylic resin 25%, auxiliary rheological agents castor oil (dosage is the 5% of conductive filler dosage), silane
Coupling agent KH-560 (dosage be conductive filler dosage 1%) and remaining be the mass ratio group that 3:7 is pressed by terpinol and ethyl alcohol
At mixed solvent, to obtain mixture；It is stirred the mixture 10 minutes or more, is obtained uniformly without blistering with high-speed mixer
Ink precursor dispersion liquid；By the ink precursor dispersion liquid by being milled to fineness lower than 20 μm, according to different printing mode
Viscosity obtains oiliness electric heating conversion ink to 1000 to 13000mPas, and physical chemical characteristics are as shown in table 1.
Wherein, viscosity test is referring to the rotary viscosity method in GB T 10247-2008 Viscosity Measurement Methods；Adhesive force test
Referring to the cross cut test (baige method) of GB T 9286-1998 paint and varnish paint film；Square resistance test is visited using digital four
Needle tester or contactless sheet resistance tester；Ink particle size uses Hegman fineness grind instrument (fineness scraper plate)；Surface hardness test ginseng
According to 6,739 1996 hardness of film pencil measuring method of GB T.
The feature of table 1,1 gained oiliness electric heating of embodiment conversion ink
| Technological project | Experimental method | Testing result |
| Structure | Scanning electron microscope/transmission electron microscope | Graphene adds carbon black |
| Condition of cure | Oven drying | 80 DEG C 10 to 20 minutes |
| Appearance | Visual observations | The smooth no particle in surface, adherence is good, dumb light black |
| Hardness | QHQ-A coating hardness tester | HB~B |
| Adhesive strength | Cross-cut tester+3M adhesive tape is vertically drawn | 5B |
| Square resistance | Four probe sheet resistance instrument | ~2 Ω/25 μm of @ |
| Fineness | Particle Size Analyzer | D50≤10μm |
| Viscosity | Rotational viscometer | <15Pa·s |
| Bending resistance | 360 ° of bendings | Resistance change rate < 5% |
| Acid resistance | 2%H2SO4Solution impregnates 120 hours | It is unchanged |
| Alkali resistance | 2%NaOH solution impregnates 120 hours | It is unchanged |
| Printing technology | Flexibility/intaglio plate/silk screen/blade coating/bar | --- |
Referring to Figure 1, Fig. 1 is that the conversion ink of oiliness electric heating obtained by embodiment 1 is printed and dried on mylar PET
The surface (A) of resulting film and (B) cross-sectional scans electromicroscopic photograph after solidization, it can be seen that the oiliness electricity of the method for the present invention preparation
Film surface densification zero defect after thermal transition ink solidification, two-dimensional sheet material self assembly stacked in multi-layers in cross section structure, shape
At the conductive structure of continuous densification, good conductive network is formd, this is also that it has the reason of superior electrical conductivity.
Preparation fever membrane module
Ink is converted by the oiliness electric heating of the silk-screen printing embodiment of the present invention 1, dries 20 minutes and solidifies in 80 DEG C；Lead to again
One layer of conductive silver paste of more than half automatic screen printings (150 DEG C of condition of cure, 30 minutes), and stick copper electrode as soldering interface,
Required test heating film is prepared finally by packaging by hot pressing, promotes film group to convert electrical energy by applying DC voltage
Thermal energy.Fig. 2 be (A) for the heating film for converting printing ink to manufacture using oiliness electric heating obtained by the embodiment of the present invention 1 it is in kind shine and
(B) its modular construction, wherein l is that film is long；D is that film is wide；And h is film thickness.
Far-infrared radiated property test
It is the far infrared wavelength that the heating film of printing ink to manufacture is converted using 1 oiliness electric heating of embodiment referring again to Fig. 3, Fig. 3
Map.The Wien's displacement law (formula 1) of one of philosophy according to heat radiation.
λmT=b------------------------------------------------------(formula 1)
Wherein: b=0.002897mK (4-7)
Assuming that body temperature is 36.5 DEG C, substituting into equation 1 above and the peak wavelength of human body radiation can be obtained is 9.36 μm, it is contemplated that
Partes corporis humani divides the difference of temperature, and human body radiation is centered on peak wavelength, and the radiation energy of both sides wavelength declines rapidly, and
Cover wider wave-length coverage.It can be seen that the spectrum of the heating film sending of oiliness electric heating of the present invention conversion printing ink to manufacture 8 to
In 12 μ ms, belong to far infrared wave band, it is close with the far infrared light wave that human body is radiated, it can be come in the form of far infrared
Radiations heat energy, it was demonstrated that oiliness electric heating conversion ink prepared by the present invention can be applied to infrared health and health physical therapy field.
Flexible heat pyrexia test
Fig. 4 be the embodiment of the present invention 1 obtained by oiliness electric heating convert printing ink to manufacture fever membrane module tiling and
180 ° of curling thermographs.Thermal imaging system is FOTRIC232, and the fever membrane module that 1 ink of the embodiment of the present invention prepares is connect
Enter direct current 5V DC power supply, thermal imaging detection is carried out to Electric radiant Heating Film assembly surface using FOTRIC232 profession thermal imaging system.
For the fever membrane module in tiling, highest heating temperature is 50.4 DEG C, and average heat generation temperature is 50 DEG C, and temperature is uniform
Degree is ε=0.95.For the fever membrane module in 180 ° of curlings, highest heating temperature is 50.8 DEG C, and average heat generation temperature is 50.3
DEG C, and temperature uniformity is ε=0.95.Fever membrane module prepared by oiliness electric heating conversion ink of the invention is tiling or is rolling up
In the case where song, film surface temperature difference is far below heating film standard GB/T/T 286-2010 " heated by low temperature radiation electric
Film " in require operating temperature deviation.So the temperature of the fever membrane module using oiliness electric heating of the present invention conversion printing ink to manufacture
Uniformity is high and not by influence of crust deformation, conducive in the application in flexible wearing field.
Heating and stability test
Heating test method: constant direct current is applied to the fever membrane module of oiliness electric heating of the present invention conversion printing ink to manufacture
It presses (2V, 5V, 7V, 9V), carries out heating cooling using temperature polling instrument and be monitored.Fig. 5 A is referred to, is oiliness of the present invention
Electric heating convert printing ink to manufacture fever membrane module heating temperature lowering curve, it can be observed that in 30 seconds the fever membrane module hair
Hot temperature can be raised to the 80% of steady temperature, and rapid drop in temperature is to room temperature after power-off.Illustrate that oiliness electric heating of the present invention turns
The fever membrane module for changing printing ink to manufacture has fast heating ramp rate and heat dissipation effect, can bring in actual use splendid
Usage experience.
Stability test method: oiliness electric heating of the present invention is maintained to convert by the control switch of temperature sensor and voltage
The temperature of the fever membrane module of printing ink to manufacture is at 40 to 80 DEG C, iterative cycles 10 times, the stability of film group when test loop heats.
Fig. 5 B is referred to, the temperature cycles decay pattern of the heating film of printing ink to manufacture is converted for oiliness electric heating of the present invention.In this test, when
When the heating film assembly surface temperature measured reaches 80 DEG C, temperature controller can be automatically powered off；When heating film component temperature declines.Temperature
When being reduced to 40 DEG C, automatic connection voltage, temperature are increased to operating temperature to temperature controller again.It can be found from figure, by 10 temperature
The temperature curve of circulation, the fever membrane module changes less than 1%, therefore the heating film tool of oiliness electric heating of the present invention conversion printing ink to manufacture
There is good thermal stability, can't decay because of temperature change.The fever of oiliness electric heating conversion printing ink to manufacture of the present invention
Film energy high temperature resistant and voltge surge, not oxidizable, 24 hours ageing cycles are almost undamped, keeps steady in dry combustion method senile experiment
Fixed fever, and it is resistant to 3000V voltge surge.
Embodiment 2
According to the present invention, the expanded graphite of 250 multiplying powers is passed through into air-flow crushing to D50=200 μm, obtained swollen through what is crushed
Swollen graphite；The expanded graphite through crushing, high-purity nickel powder and conductive black are formed into three components by the mass ratio of 1:8:1 respectively
Filler；Mixing three component filler 20%, epoxy resin 10%, dispersing agent polyethylene glycol 100, (dosage is the matter of conductive filler
The 10% of amount), auxiliary rheological agents silica (dosage be conductive filler dosage 2%), (dosage is leads to silane resin acceptor kh-550
The 0.1% of electric amount of filler) and remaining be the mixed solvent being made of Propylene glycol n-propyl ether and DBE by the mass ratio of 1:3, with
Obtain mixture；It is stirred the mixture 10 minutes or more with high-speed mixer, obtains the uniformly ink precursor dispersion without blistering
Liquid；By the ink precursor dispersion liquid by sand milling to fineness be lower than 20 μm, according to different printing mode viscosity to 1000 to
13000mPas obtains oiliness electric heating conversion ink.
Embodiment 3
According to the present invention, the expanded graphite of 600 multiplying powers is passed through into air-flow crushing to D50=25 μm, obtained swollen through what is crushed
Swollen graphite；The expanded graphite through crushing, carbon nanotube and conductive black are formed into three components by the mass ratio of 3:1:2 respectively
Filler；Mix three component filler 4%, epoxy resin 10%, polyurethane resin 5%, dispersing agent neopelex
It is (dosage be conductive filler dosage 3%), auxiliary rheological agents bentonite (dosage be conductive filler dosage 1.5%), silane coupled
Agent A-171 (dosage be conductive filler dosage 5%) and remaining be by ethyl acetate and -2 pyrrolidones of 1- methyl by 3:2's
The mixed solvent of mass ratio composition, to obtain mixture；It is stirred the mixture 10 minutes or more, is obtained uniformly with high-speed mixer
Ink precursor dispersion liquid without blistering；The ink precursor dispersion liquid is ground to fineness by three rollers and is lower than 20 μm, according to
Different printing mode viscosity obtains oiliness electric heating conversion ink to 1000 to 13000mPas.
Embodiment 4
According to the present invention, the expanded graphite of 600 multiplying powers is obtained swollen through what is crushed by being mechanically pulverized to D50=600 μm
Swollen graphite；The expanded graphite through crushing and acetylene black are formed into bi-component filler by the mass ratio of 20:1 respectively；Mixing institute
Stating bi-component filler 20%, epoxy resin 15%, acrylic resin 25%, dispersing agent neopelex, (dosage is to lead
The 0.1% of electric amount of filler), auxiliary rheological agents castor oil the 1.5% of conductive filler dosage (dosage be), Silane coupling reagent KH-570
(dosage be conductive filler dosage 5%) and remaining be by ethyl acetate, Propylene glycol n-propyl ether and N,N-dimethylformamide
By the mixed solvent that the mass ratio of 2:1:2 forms, to obtain mixture；With high-speed mixer stir the mixture 10 minutes with
On, obtain the uniformly ink precursor dispersion liquid without blistering；The ink precursor dispersion liquid is combined by ball milling and is sanded to thin
Degree is lower than 20 μm, obtains oiliness electric heating conversion ink according to different printing mode viscosity to 1000 to 13000mPas.
Embodiment 5
According to the present invention, the expanded graphite of 400 multiplying powers is passed through into air-flow crushing to D50=50 μm, obtained swollen through what is crushed
Swollen graphite；The expanded graphite, graphite powder and acetylene black through crushing is formed three components by the mass ratio of 2:2:1 respectively to fill out
Material；Mix three component filler 28%, alkyd resin 10%, acrylic resin 15%, dispersing agent cetomacrogol 1000 (dosage
Be the 1.8% of conductive filler dosage), auxiliary rheological agents castor oil (dosage be conductive filler dosage 1.5%), silane coupling agent
KH-550 and KH-560 (dosage be respectively conductive filler dosage 1% and 2%) and remaining be by ethyl acetate and DBE by 1:
The mixed solvent of 10 mass ratio composition, to obtain mixture；It is stirred the mixture 10 minutes or more, is obtained with high-speed mixer
The uniformly ink precursor dispersion liquid without blistering；By the ink precursor dispersion liquid, by high-pressure homogeneous combination, to be milled to fineness low
In 20 μm, oiliness electric heating conversion ink is obtained according to different printing mode viscosity to 1000 to 13000mPas.
Embodiment 6
According to the present invention, the expanded graphite of 300 multiplying powers is obtained swollen through what is crushed by being mechanically pulverized to D50=300 μm
Swollen graphite；The expanded graphite through crushing, high-purity nickel powder and conductive black are formed into three components by the mass ratio of 2:4:1 respectively
Filler；Mix three component filler 12%, polyurethane resin 6%, acrylic resin 8%, dispersing agent dodecyl benzene sulfonic acid
(dosage be conductive filler dosage 3%), auxiliary rheological agents fumed silica (dosage be conductive filler dosage 3%), silane
Coupling agent A-171 (dosage be conductive filler dosage 2%) and remaining be the quality that 1:2:1 is pressed by butanone, dimethylbenzene and DBE
Than the mixed solvent of composition, to obtain mixture；It is stirred the mixture 10 minutes or more with high-speed mixer, obtains uniformly nothing and rise
The ink precursor dispersion liquid of bubble；By the ink precursor dispersion liquid by being milled to fineness lower than 20 μm, according to different printing
Mode viscosity obtains oiliness electric heating conversion ink to 1000 to 13000mPas.
Embodiment 7
According to the present invention, the expanded graphite of 350 multiplying powers is passed through into air-flow crushing to D50=15 μm, obtained swollen through what is crushed
Swollen graphite；The expanded graphite through crushing, high-purity nickel powder and carbon nanotube are formed into three components by the mass ratio of 4:8:1 respectively
Filler；Three component filler 5%, polyamide 3%, epoxy resin 18%, auxiliary rheological agents fumed silica is mixed (to use
Amount is the 0.5% of conductive filler dosage), Silane coupling reagent KH-570 (dosage be conductive filler dosage 0.2%) and remaining
For the mixed solvent being made of DBE and dimethylbenzene by the mass ratio of 3:1, to obtain mixture；It is mixed that this is stirred with high-speed mixer
Close object 10 minutes or more, obtain the uniformly ink precursor dispersion liquid without blistering；By the ink precursor dispersion liquid by being sanded
In conjunction with fineness is milled to lower than 20 μm, oiliness electric heating is obtained according to different printing mode viscosity to 1000 to 13000mPas and is turned
Carburetion ink.
Embodiment 8
According to the present invention, the expanded graphite of 500 multiplying powers is passed through into air-flow crushing to D50=8 μm, obtains the expansion through crushing
Graphite；The expanded graphite, conductive black and carbon nanotube through crushing is formed three components by the mass ratio of 5:1:1 respectively to fill out
Material；Mixing three component filler 14%, polyamide 29%, dispersing agent dodecyl benzene sulfonic acid, (dosage is conductive filler
The 8% of dosage), auxiliary rheological agents castor oil (dosage be conductive filler dosage 3.5%) and remaining be by ethyl acetate, diformazan
The mixed solvent that benzene and DBE are formed by the mass ratio of 1:1:1, to obtain mixture；The mixture 10 is stirred with high-speed mixer
Minute or more, obtain the uniformly ink precursor dispersion liquid without blistering；By the ink precursor dispersion liquid by three rollers grinding knot
It closes to be sanded to fineness and is lower than 20 μm, the conversion of oiliness electric heating is obtained according to different printing mode viscosity to 1000 to 13000mPas
Ink.
Embodiment 9 (comparative example 1)
By the 250 multiplying power expanded graphites (D50=2mm), conductive black and the carbon nanotube that do not crush respectively by the matter of 2:1:2
Amount is than three component fillers of composition；Mix three component filler 9%, acrylic resin 13%, auxiliary rheological agents fumed silica
(dosage be conductive filler dosage 3.5%) and remaining be the quality that 3:1:1 is pressed by n-butyl acetate, isophorone and DBE
Than the mixed solvent of composition, to obtain mixture；It is stirred the mixture 10 minutes or more with high-speed mixer, obtains no blistering
Ink precursor dispersion liquid；It combines three rollers to be ground to fineness by ball milling the ink precursor dispersion liquid and is lower than 20 μm, according to
Different printing mode viscosity obtains oiliness electric heating conversion ink to 1000 to 13000mPas.
Using the expanded graphite not crushed in the present embodiment, obtained ink precursor dispersion liquid homogeneity is poor, and into
When the three rollers grinding of row next step, need of long duration, charge stripping efficiency is low, and obtained oiliness electric heating conversion ink texture is coarse, In
Blade coating property is bad when printing.
Standard needed for table 2 lists different printing technique.Table 3 lists above-mentioned 9 embodiments (including 1 comparative example)
Printing performance, wherein for viscosity in the embodiment of 5000mPas or more, such as embodiment 1,2,3 and comparative example 1 can be with
For silk-screen printing technique, embodiment 4,5,6,7 and 8 can be used for common intaglio printing, and embodiment 7 can be used for spraying print
Brush.
Standard needed for table 2, different printing technique
| Mode of printing | Silk-screen printing | Inkjet printing | Intaglio printing | Spraying printing |
| Viscosity (mPa s) | 5000~12000 | 10~20 | 500~2500 | 50~2000 |
| Precision (μm) | 50~100 | 10~50 | 10~100 | Nothing |
| Hygrometric state thickness (μm) | 5~250 | 1~10 | 1 | 5~50 |
| Print speed printing speed | 70 | 1 | 1000 | 40 |
Table 3 is the performance parameter that oiliness electric heating prepared by Examples 1 to 8 and comparative example 1 converts ink, solidified bars
Part is 80 DEG C 10 minutes dry.Viscosity test is referring to the rotary viscosity method in GB T 10247-2008 Viscosity Measurement Methods；Attachment
Cross cut test (baige method) of the power test referring to GB T 9286-1998 paint and varnish paint film；Square resistance test is using number
Formula four-point probe or contactless sheet resistance tester.It can be seen that the conversion ink of oiliness electric heating prepared by the method for the present invention is attached
Put forth effort good.
Film after the conversion ink solidification of oiliness electric heating prepared by the method for the present invention is electric in the square of 25 μ m thick conditions
Resistance range is 1 to 7 Ω/.Compared to this, comparative example 1 uses the ink film for not crushing expanded graphite preparation below 25 μm of conditions
Block resistance range is 22.67 Ω/；In other prior arts, such as CN108530996A, optimal product resistance in embodiment
Rate is 0.05 Ω m, i.e. 50m Ω cm, and it is 20 Ω/ that square resistance can be scaled according to following formula (2).
Those skilled in the art understand that the square resistance of oiliness electric heating conversion ink drops to a position grade from double figures rank
It not, is the gap for belonging to order of magnitude rank, the technology of the present invention is the bottleneck place in field, rather than the regulation of simple experiment parameter is just
It is attainable.And the adhesive force of comparative example 1 is poor, it was demonstrated that the introducing of expanded graphite precomminution technique can significant improvement oiliness electric heating
Convert the electric conductivity and adhesive strength of ink.
The conversion of square resistance Ω/ and resistivity Ω cm:
Rs=ρ/t------------------------------------------------------- -- formula (2)
(wherein: Rs is square resistance；ρ is the resistivity of bulk；T is bulk thickness, and 25 μm of bulk thickness is square electricity
The standard testing specification of resistance)
Oiliness electric heating prepared by the method for the present invention converts the film of ink after hardening under the conditions of 25 μm of thickness, side
Block resistance is minimum to can reach 1.2 Ω/ hereinafter, well below the prior art, and if fixing coating in Electric radiant Heating Film printing process
All-in resistance and the gross area avoid energy consumption caused by repeatedly printing, with commercially produced product to layer of ink solid-state thickness requirement relative reduction
It compares, the conversion of oiliness electric heating prepared by the method for the present invention ink ink print pass under equal-wattage density conditions is few, uses
It measures low, there are the advantages such as printed patterns light weight, printability be good and low in cost, in addition, the condition of cure temperature of the ink
Simply with, condition of cure (80 DEG C drying 10 to 20 minutes), can a variety of different plastic films (PET, PI, PE, PVC etc.), cloth,
Printing is realized on a variety of substrates such as paper and ceramic substrate.
(condition of cure is 80 DEG C of dryings to the performance parameter of the conversion ink of oiliness electric heating prepared by table 3, embodiment 1 to 9
10 minutes)
| Embodiment | Thickness (μm) | Square resistance (Ω/) | Viscosity (mPas) | Adhesive force |
| 1 | 25 | 1.723 | 5500 | 5B |
| 2 | 25 | 2.298 | 5600 | 5B |
| 3 | 25 | 2.082 | 6200 | 5B |
| 4 | 25 | 1.462 | 3400 | 5B |
| 5 | 25 | 1.178 | 3200 | 5B |
| 6 | 25 | 2.56 | 2800 | 5B |
| 7 | 25 | 4.06 | 1600 | 5B |
| 8 | 25 | 6.112 | 2200 | 5B |
| 9 (comparative examples 1) | 25 | 22.67 | 7600 | 2B |
By the above results it can be found that since expanded graphite is ultrafast to having for solvent, adsorption capacity of superelevation, when expansion
When the partial size of graphite is too big (comparative example 1), charge stripping efficiency is poor after adsorption solvent, graphene low yield, easily stacks and loses two
Tie up the advantage of material；Furthermore after large-sized expanded graphite adsorption solvent, the excessively high applicable peel-off device of viscosity is less.Therefore
Expanded graphite is carried out precomminution by the present invention, to obtain the expanded graphite of desired size, is beneficial to the oiliness electric heating of subsequent preparation
Convert the performance of ink.
In addition, the conversion ink preparation of oiliness electric heating prepared by the method for the present invention has good resistance to acid and alkali and excellent
Flexility, and there is good adhesion to a variety of substrates.Its application in flexible wearing fever can be widened, is repeatedly bent
It not will lead to its part open circuit and cause changed power.
However, conductive effect is instead when expanded graphite average-size is crushed to 15 μm to 200 μm (embodiment 1 to 6)
More preferably, square resistance is smaller for embodiment 7 and 8 when being crushed to 5 μm or 15 μm than expanded graphite.Although this is first expanded graphite
The crushing of material is conducive to improve filler in the even distribution of ink, but crushes and undersized will lead to material and stripping media
Possibility decline is contacted, influences peeling effect, it is low that expanded graphite removes conversion ratio.Second the partial size of expanded graphite is too small, graphite
The sheet section of layer becomes smaller, and after removing, contact area is small between piece and piece, can not form the conductive network of continuous densification.It changes
Sentence is talked about, and to expanded graphite precomminution to a certain range of size, facilitates the graphene that removing obtains and formed continuously to lead
Electric network and the method for the present invention can prepare the reason of oiliness electric heating conversion ink with excellent conductivity.
It is compared compared to the conventional method for being introduced directly into the graphene removed, the method for the present invention introduces pre- smash and expands stone
The step of ink not only simplifies the technique of removing and dispersion, reduces ink cost, and effectively increase the electric conductivity of ink, makes
Obtained graphite microchip is removed simultaneously during standby electrically conductive ink or the oxygen-containing ratio of graphene is lower, and defect is less, thus leads
It is electrically good.The expanded graphite smashed in advance carries out up-stripping, obtained oiliness electric heating conversion in resin, auxiliary agent and solvent
Ink favorable dispersibility, homogeneity are stablized.The preparation method of oiliness electric heating conversion ink of the present invention is a kind of technique letter
It is single, it is easy to the method for mass production, and prepared oiliness electric heating conversion ink can adjust its viscosity for printing technology, it is right
Printing technology adaptability is good, and electric heating film uniformity is high.
Above-described embodiment is only to be illustrated the principle of the present invention and its effect, and is not intended to limit the present invention.Appoint
What those skilled in the art without departing from the spirit and scope of the present invention, modifies to above-described embodiment.Cause
This scope of the present invention, should be as listed in the claims.
Claims (11)
1. a kind of method for preparing oiliness electric heating conversion ink, which is characterized in that the described method comprises the following steps:
Expanded graphite is crushed, with the expanded graphite that must be crushed；
The expanded graphite of crushing, conductive filler, resin, auxiliary agent and solvent are premixed, to obtain pre-composition；
Solvent is added in the pre-composition, and stirs, obtains the uniformly ink precursor dispersion liquid without blistering；And
The ink precursor dispersion liquid is passed through into stripping technology, obtains oiliness electric heating conversion ink；
Wherein, the mass percent of the resin, the solvent and the auxiliary agent is respectively 10~40%, 35~80% and 0.3
~4%.
2. the method as described in claim 1, which is characterized in that D50=5 to 600 μm of the expanded graphite of the crushing.
3. the method as described in claim 1, which is characterized in that the conductive filler is selected from nickel powder, carbon nanotube, conductive charcoal
At least one of black, graphite powder and acetylene black.
4. the method as described in claim 1, which is characterized in that the ratio of the expanded graphite and the conductive filler is 1:
2.5 to 20:1, the mass percent of the expanded graphite and the conductive filler in oiliness electric heating conversion ink is 4~
28%.
5. the method as described in claim 1, which is characterized in that the resin is selected from acrylic resin, epoxy resin, polyurethane
At least one of resin, alkyd resin, polyester resin and polyamide.
6. the method as described in claim 1, which is characterized in that the solvent be selected from ethyl alcohol, terpinol, Propylene glycol n-propyl ether,
Ethyl acetate, butyl acetate, n-butyl acetate, pentyl acetate, dibasic ester (DBE, dimethyl succinate, dimethyl glutarate
With the combination of three kinds of environmentally friendly solvents of hexanedioic acid dimethyl ester), butanone, cyclohexanone, isophorone, -2 pyrrolidones of 1- methyl,
At least one of toluene, dimethylbenzene and N,N-dimethylformamide.
7. the method as described in claim 1, which is characterized in that the auxiliary agent is in auxiliary rheological agents, coupling agent and dispersing agent
It is at least one.
8. the method as described in claim 1, which is characterized in that the stripping technology be three rollers grinding, be sanded, it is high-pressure homogeneous and
At least one of ball milling.
9. the method for claim 7, which is characterized in that the ink precursor dispersion liquid is after stripping technology, carefully
Degree is lower than 20 μm.
10. a kind of oiliness electric heating converts ink, which is characterized in that the oiliness electric heating conversion ink is using such as claim 1
To prepared by 9 described in any item methods.
11. a kind of fever membrane module, which is characterized in that the fever membrane module includes:
Electric heating conversion coating, the electric heating conversion coating are to utilize oiliness prepared by method as described in any one of claim 1 to 9
Electric heating converts obtained by ink solidification；
Conductive layer is deposited on the electric heating conversion coating；
Electrode contacts the conductive layer.
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| WO2021031464A1 (en) * | 2019-08-21 | 2021-02-25 | 厦门大学 | Method for preparing graphene far infrared additive and far infrared paste |
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| CN114010949A (en) * | 2021-09-24 | 2022-02-08 | 嘉庚创新实验室 | Wearable device, wearable system and application thereof |
| CN115104783A (en) * | 2022-07-27 | 2022-09-27 | 深圳市赛尔美电子科技有限公司 | Heating assembly, preparation method thereof and electronic atomization system |
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| WO2021031464A1 (en) * | 2019-08-21 | 2021-02-25 | 厦门大学 | Method for preparing graphene far infrared additive and far infrared paste |
| CN113122072A (en) * | 2019-12-30 | 2021-07-16 | 山东欧铂新材料有限公司 | Graphene conductive ink for heating film and preparation method thereof |
| CN113061370A (en) * | 2020-01-02 | 2021-07-02 | 中国科学院福建物质结构研究所 | Graphene ink and preparation method and application thereof |
| CN112375439A (en) * | 2020-10-30 | 2021-02-19 | 陕西惠泽热能有限公司 | Preparation method of photo-curing carbon slurry for far infrared heating |
| CN112375439B (en) * | 2020-10-30 | 2022-05-24 | 陕西惠泽热能有限公司 | Preparation method of photo-curing carbon paste for far infrared heating |
| CN113502088A (en) * | 2021-08-04 | 2021-10-15 | 德州宇航派蒙石墨烯科技有限责任公司 | Graphene conductive ink, preparation method and application |
| CN113952622A (en) * | 2021-09-24 | 2022-01-21 | 嘉庚创新实验室 | Infrared device and application thereof |
| CN114010949A (en) * | 2021-09-24 | 2022-02-08 | 嘉庚创新实验室 | Wearable device, wearable system and application thereof |
| CN115104783A (en) * | 2022-07-27 | 2022-09-27 | 深圳市赛尔美电子科技有限公司 | Heating assembly, preparation method thereof and electronic atomization system |
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Effective date of registration: 20220602 Address after: No.422, Siming South Road, Siming District, Xiamen City, Fujian Province Applicant after: XIAMEN University Applicant after: Jiageng Innovation Laboratory Address before: 361000 Siming South Road, Xiamen, Fujian Province, No. 422 Applicant before: XIAMEN University |
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Application publication date: 20191119 |