KR20170098341A - Heating composition having graphene oxide and heater using the same - Google Patents

Heating composition having graphene oxide and heater using the same Download PDF

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KR20170098341A
KR20170098341A KR1020160019443A KR20160019443A KR20170098341A KR 20170098341 A KR20170098341 A KR 20170098341A KR 1020160019443 A KR1020160019443 A KR 1020160019443A KR 20160019443 A KR20160019443 A KR 20160019443A KR 20170098341 A KR20170098341 A KR 20170098341A
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parts
particles
graphene oxide
metal powder
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KR101777691B1 (en
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김윤진
조진우
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전자부품연구원
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/23—Oxidation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/02—Details
    • H05B3/03—Electrodes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H05B3/141—Conductive ceramics, e.g. metal oxides, metal carbides, barium titanate, ferrites, zirconia, vitrous compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H05B3/145—Carbon only, e.g. carbon black, graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/34—Length
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/36—Diameter

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Ceramic Engineering (AREA)
  • Surface Heating Bodies (AREA)
  • Resistance Heating (AREA)

Abstract

The present invention relates to a heat-emitting composite including a graphene oxide and a heat-emitting body using the same, capable of providing stable heat resistance even at approximately 300C. According to the present invention, the heat-emitting body includes: a ceramic substrate; and a heat-emitting element formed by printing the heat-emitting composite on the upper surface of the ceramic substrate. The heat-emitting composite includes a mixing binder, a graphene oxide particle, a conductive particle, an organic solvent, and a dispersant. The mixing binder includes epoxy acrylate or hexamethylene diisocyanate, polyvinyl acetal, and phenol resin. The conductive particle includes at least two among a carbon nanotube particle, a graphite particle, and metal powder.

Description

TECHNICAL FIELD The present invention relates to a heating composition comprising graphene oxide and a heating element using the same,

TECHNICAL FIELD The present invention relates to a heat-generating composition and a heat-generating body using the same, and more particularly, to a heat-generating composition including a graphene oxide having stable heat resistance even at a temperature of around 300 DEG C and a heat-generating body using the same.

Unlike linear heating elements, plane heating elements generate uniform heat on the surface, which is 20 ~ 40% more energy efficient than linear heating elements. In addition, the surface heating element is a relatively safe heating element because there is no electromagnetic wave emission during DC driving.

Typically, the surface heating element may be formed by uniformly spraying or printing a metal heating element such as iron, nickel, chromium, or platinum having a high thermal conductivity on a film-type resin or the like, or by forming a conductive inorganic particle heating element such as carbon, graphite, or carbon black Is mixed with a polymer resin. In recent years, many carbon-based surface heating elements having heat and durability, good thermal conductivity and low thermal expansion coefficient and light characteristics have been researched.

The surface heating element using a carbonaceous material is made of a paste formed by mixing a conductive carbonaceous powder such as carbon, graphite, carbon black or carbon nanotube with a binder, and the amount of the conductive material and the binder used is Accordingly, conductivity, workability, adhesion, scratch resistance and the like are determined.

However, in the case of the exothermic paste based on carbon nanotubes, it has been difficult to have high heat resistance. In particular, a heat-generating paste having high heat resistance at a temperature of about 200 ° C. to 300 ° C. while being capable of screen printing, gravure printing, There is no report. Further, in the case of designing to have high heat resistance, since the drying temperature (curing temperature) is close to 300 캜, it is pointed out that it is difficult to apply it to a plastic substrate made of a plastic material.

On the other hand, the conventional carbonaceous heating paste has a relatively high resistivity and is not easy to form a thick film, so that it is difficult to drive a heating element using the carbonaceous heating paste with low voltage and low power.

In order to solve such a problem, Korean Patent No. 10-1572802 discloses an exothermic paste composition containing a mixed binder and nano carbon particles. The heat generating paste composition disclosed in Korean Patent No. 10-1572802 has a stable characteristic because it can maintain heat resistance at a temperature near 200 ° C and has a small change in resistance with temperature.

However, the exothermic paste composition disclosed in Korean Patent No. 10-1572802 has a problem that the heat resistance is poor at a temperature of around 300 캜 because there is no chemical bonding between the nanocarbon particles and the binder binder. Accordingly, the heat generating paste composition disclosed in Korean Patent No. 10-1572802 can be applied to applications requiring heat resistance at a temperature of 200 ° C or less, but it is applied to applications requiring heat resistance at temperatures near 300 ° C There was a problem in doing.

Korean Patent No. 10-1572802 (November 24, 2015)

Accordingly, an object of the present invention is to provide a heat-generating composition comprising graphene oxide having stable heat resistance even at a temperature of around 300 캜, and a heating element using the same.

Another object of the present invention is to provide a heat-generating composition comprising graphene oxide which can increase heat resistance through chemical bonding with a mixed binder, and a heating element using the same.

In order to accomplish the above object, the present invention provides a mixed binder comprising a mixture of epoxy acrylate or hexamethylene diisocyanate, polyvinyl acetal and phenolic resin; Graphene oxide particles; Conductive particles comprising at least two of carbon nanotube particles, graphite particles and metal powder; Organic solvent; And a dispersing agent.

The graphene oxide particles have an insulating property within 1 to 20 layers and are partially graphitized particles.

The exothermic composition preferably contains 8 to 10 parts by weight of a mixed binder, 0.1 to 5 parts by weight of carbon nanotube particles, 0.1 to 20 parts by weight of graphite particles, and 0.0001 to 1 part by weight of graphene oxide particles per 100 parts by weight of the exothermic composition. 20 to 80 parts by weight of the organic solvent, and 0.5 to 5 parts by weight of the dispersing agent.

Or the exothermic composition may contain 8 to 10 parts by weight of a mixed binder, 0.1 to 5 parts by weight of carbon nanotube particles, 0.1 to 20 parts by weight of graphite particles, 10 to 60 parts by weight of metal powder, , 0.0001 to 1 part by weight of graphene oxide particles, 20 to 80 parts by weight of organic solvent, and 0.5 to 5 parts by weight of dispersing agent.

The mixed binder may include 10 to 150 parts by weight of a polyvinyl acetal resin and 10 to 500 parts by weight of a phenolic resin based on 100 parts by weight of epoxy acrylate or hexamethylene diisocyanate.

The carbon nanotube particles have a diameter of 1 nm to 20 nm and a length of 1 占 퐉 to 100 占 퐉.

The graphite particles have a diameter of 1 탆 to 25 탆 and a length of 1 nm to 25 탆.

The metal powder includes metal powder of silver or copper. The metal powder of the silver material may have a flake, a round shape, a polygonal plate shape, or a rod shape. The metal powder of the copper material may include copper coated with silver or nickel coated with nickel.

The exothermic composition is thermally cured at 100 ° C to 180 ° C and can be aged at 250 to 350 ° C.

The present invention provides a heating element including a ceramic substrate and a heating electrode formed by printing the heating composition on an upper surface of the ceramic substrate.

Since the exothermic composition according to the present invention includes graphene oxide, it can induce direct chemical covalent bond with a mixed binder which is an organic binder. Accordingly, the exothermic composition according to the present invention has stable heat resistance even at a temperature of around 300 ° C.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagram showing various functional groups formed in graphene oxide.
2 is a plan view showing a heating element using a heating composition according to the present invention.
3 is a sectional view taken along line 3-3 of Fig.
4 is a cross-sectional view taken along line 4-4 of Fig.

In the following description, only parts necessary for understanding embodiments of the present invention will be described, and descriptions of other parts will be omitted to the extent that they do not disturb the gist of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary meanings and the inventor is not limited to the meaning of the terms in order to describe his invention in the best way. It should be interpreted as meaning and concept consistent with the technical idea of the present invention. Therefore, the embodiments described in the present specification and the configurations shown in the drawings are merely preferred embodiments of the present invention, and are not intended to represent all of the technical ideas of the present invention, so that various equivalents And variations are possible.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The exothermic composition according to the present invention includes a mixed binder, conductive particles, graphene oxide (GO) particles, an organic solvent and a dispersant. The conductive particles include at least two of carbon nanotube particles, graphite particles, and metal powder.

The exothermic composition according to the present invention can be realized in the form of a paint, ink or paste by controlling the amount of the organic solvent used.

The exothermic composition according to the present invention comprises 8 to 10 parts by weight of a binder, 0.1 to 5 parts by weight of carbon nanotube particles, 0.1 to 20 parts by weight of graphite particles, and 0.0001 To 1 part by weight, the organic solvent may be 20 to 80 parts by weight, and the dispersing agent may be 0.5 to 5 parts by weight.

The exothermic composition according to the present invention comprises 8 to 10 parts by weight of a mixed binder, 0.1 to 5 parts by weight of carbon nanotube particles, 0.1 to 20 parts by weight of graphite particles, 10 to 60 parts by weight of metal powder, The graphene oxide particles may be 0.0001 to 1 part by weight, the organic solvent may be 20 to 80 parts by weight, and the dispersant may be 0.5 to 5 parts by weight.

In this case, when the conductive particles include the metal powder, the heating element formed of the heating composition according to the present invention is a three-dimensional structure in which the metal powder forms a main electrical network, and carbon nanotube particles or graphite particles are filled in spaces between the metal powders And has a random network structure.

The mixed binder functions to allow the exothermic composition to have heat resistance even in a temperature range of about 300 DEG C, and is preferably an epoxy acrylate or a hexamethylene diisocyanate, a polyvinyl acetal, or a phenol (Phenol resin) are mixed with each other. That is, the mixed binder may be a mixture of epoxy acrylate, polyvinyl acetal and phenolic resin, or a mixture of hexamethylene diisocyanate, polyvinyl acetal and phenolic resin. In the present invention, by increasing the heat resistance of the mixed binder, it is possible to suppress the resistance change of the heat generating element and the breakage of the heat generating element even when the heat is generated at a high temperature of about 300 캜.

For example, the mixing ratio of the mixed binder may be 10 to 150 parts by weight of the polyvinyl acetal resin and 10 to 500 parts by weight of the phenolic resin with respect to 100 parts by weight of the epoxy acrylate or hexamethylene diisocyanate. When the content of the phenolic resin is 10 parts by weight or less, the heat-resistant property of the exothermic composition is deteriorated. When the content of the phenolic resin exceeds 500 parts by weight, the flexibility is lowered and the brittleness is increased.

Here, the phenolic resin means a phenolic compound including phenol and phenol derivatives. For example, phenol derivatives include p-cresol, o-Guaiacol, Creosol, Catechol, 3-methoxy-1,2-benzenediol (3- methoxy-1,2-benzenediol, Homocatechol, Vinylguaiacol, Syringol, Iso-eugenol, Methoxyeugenol, o- Cresol, 3-methyl-1,2-benzenediol and (z) -2-methoxy-4- (1-propenyl) -phenol 2-methoxy-4- (1-propenyl) -phenol, 2,6-dimethoxy-4- (2-propenyl) Phenol, 3,4-dimethoxy-Phenol, 4-ethyl-1,3-benzenediol, Resole phenol, 4-methyl-1,2-benzenediol, 1,2,4-benzene triol, 2-methoxy-6-methylphenol 2-Methoxy-6-methylphenol, 2-Methoxy-4-vinylphenol or 4-ethyl-2-methoxy- , Etc. It is not.

Carbon nanotube particles and graphite particles impart black body radiation and electrical conductivity.

The carbon nanotube particles can be selected from single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, or mixtures thereof. For example, the carbon nanotube particles may be multi wall carbon nanotubes. When the carbon nanotube particles are multi-walled carbon nanotubes, the diameter may be 1 nm to 20 nm, and the length may be 1 to 100 mu m.

The graphite particles may have a diameter of 1 탆 to 25 탆 and a thickness of 1 nm to 25 탆.

The metal powder is a predominantly electrically conductive material and includes powders of silver or copper. In the case of silver powder, it may have the form of a flake, a circle, a polygonal plate, a rod, or the like. Examples of the copper powder include silver coated Cu, nickel coated Cu powder, and the like.

As described above, the exothermic composition according to the present invention includes carbon particles and a metal powder, thereby enhancing energy efficiency and heat generation rate of the exothermic composition. That is, the metal powder does not have a blackbody radiation function, but a black body radiation function can be realized by including carbon particles in the exothermic composition. The carbon particles can increase the heat resistance of the exothermic composition. And carbon particles can increase the heating rate and energy efficiency.

Graphene oxide particles have insulating properties within 1 to 20 layers and are partially graphitized particles. The graphene oxide particles may be included in an amount of 0.0001 to 1 part by weight based on 100 parts by weight of the exothermic composition.

The graphene oxide particles have various functional groups as shown in Fig. Using these various functional groups, graphene oxide particles can induce direct chemical covalent bonding with the organic binder binder. Accordingly, the exothermic composition according to the present invention has stable heat resistance even at a temperature of around 300 ° C. 1 is a view showing various functional groups formed on graphene oxide.

The graphene oxide particles have functional groups with excellent chemical reactivity such as carboxyl, amine, imine, hydroxyl, carbonyl, and lactone on the surface and edge. The functional groups contained in graphene oxide particles can be chemically covalently bonded to functional groups contained in diisocyanate, phenol, and epoxy. Thus, graphene oxide particles form chemical covalent bonds with the epoxy acrylate, hexamethylene diisocyanate and phenolic resin contained in the mixed binder. The chemical covalent bond between the graphene oxide particles and the binder binder forms a three-dimensional three-dimensional network and inhibits the movement of the polymer chain, which can lead to an increase in the glass transition temperature and the decomposition initiation temperature.

The organic solvent is for dispersing the carbon particles, the metal powder and the binder. The organic solvent is selected from the group consisting of Carbitol acetate, Butyl carbotol acetate (BCA), DBE (dibasic ester), Ethyl Carbitol, Ethyl Carbitol (Dipropylene Glycol Methyl Ether (DPM), Cellosolve Acetate, Butyl Cellosolve Acetate, Butanol, and Octanol.

Meanwhile, various methods commonly used may be applied to the dispersion process. For example, ultrasonic treatment (roll-milling), bead milling or ball milling Lt; / RTI >

The dispersing agent is used to make the dispersion more smooth. Examples thereof include conventional dispersants used in the art such as BYK, amphoteric surfactants such as Triton X-100, ionic surfactants such as sodium dodecyl sulfate (SDS) Surfactants can be used.

The heating element using the heating composition according to the present invention will now be described with reference to FIGS. 2 to 4. FIG. 2 is a plan view showing a heating element using a heating composition according to the present invention. 3 is a sectional view taken along line 3-3 of Fig. And Fig. 4 is a sectional view taken along line 4-4 of Fig. 2 to 4, the ceramic heater used for the heating roller is illustrated as the heating element, but the present invention is not limited thereto.

2 to 4, the heating element 50 includes a ceramic substrate 51 and a heating electrode 57, and may further include a wiring electrode 53 and an insulating film 59.

The ceramic substrate 51 is a support on which the heating electrode 57 is formed and has the insulating property for suppressing the power applied to the heating electrode 57 from being externally applied and the heat generated from the heating electrode 57 to the roller 30, And is made of a ceramic material having thermal conductivity to stably transmit the ceramic material. For example the material of the ceramic substrate 51 is a silicon carbide (SiC), silicon nitride (Si 3 N 4), alumina (Al 2 O 3), zirconia (ZrO 2), barium titanate (BaTiO 3), magnesium oxide (MgO ), Tin oxide (SnO 2 ), mica stone, and the like.

At this time, wiring electrodes 55 are formed on the upper surface of the ceramic substrate 51, and connection wirings 53 connecting the heating electrodes 57 and the wiring electrodes 55 are formed. The connection wiring 53 and the wiring electrode 55 can be formed by attaching a thin film made of silver or copper to the upper surface of the ceramic substrate 51. Or the connection wiring 53 and the wiring electrode 55 may be formed by printing, drying and curing silver paste or copper paste on the upper surface of the ceramic substrate 51.

The heating electrode (57) is formed by printing a heating composition on the upper surface of the ceramic substrate (51). That is, the heating electrode 57 is formed by printing a heating composition on the upper surface of the ceramic substrate 51, followed by thermosetting and aging. As the printing method of the exothermic composition, screen printing, gravure printing (to roll to roll gravure printing), comma coating (to roll to roll comma coating), flexo, imprinting, offset printing and the like can be used. Curing may be performed at 100 ° C to 180 ° C, and aging may be performed at 250 ° C to 350 ° C.

The exothermic electrodes 57 may be connected in series to one line by the connection wirings 53 formed on the ceramic substrate 51. For example, since the example in which the heating electrodes 57 are formed parallel to each other with two lines in FIG. 2, in order to connect the two heating electrodes 57 with one line, the connection wiring 53 is formed by two heating electrodes Quot; U "character with the character string " 57 ". When the two heating electrodes 57 are referred to as a first heating electrode 57a and a second heating electrode 57b at this time, the connection wiring 53 is connected to the first connection wiring 53a, the second connection wiring 53b, And a third connection wiring 53c. The first connection wiring 53a is connected to one end of the first heating electrode 57a. The second connection wiring 53b is connected to one end of the second heating electrode 57b on the side where one end of the first heating electrode 57a is located. The third connection wiring 53c connects the other ends of the first and second heating electrodes 57a and 57b to each other.

The insulating film 59 is formed so as to cover the heat generating electrode 57 formed on the upper surface of the ceramic substrate 51 and the connecting wiring 53. The insulating film 59 is formed so that the wiring electrode 55 is exposed to the outside. As the material of the insulating film 59, polyimide, epoxy resin, optically clear adhesive (OCA), or optically clear resin (OCR) may be used, but the present invention is not limited thereto.

The wiring electrode 55 is connected to both ends of the heating electrode 57 to apply a power from the outside to the heating electrode 57. The wiring electrode 55 is exposed to the outside of the insulating film 59 and is electrically connected to the heating electrode 57 through the first and second connection wirings 53a and 53b. The wiring electrode 55 includes a first wiring electrode 55a connected to the first connection wiring 53a and a second wiring electrode 55b connected to the second connection wiring 53b.

On the other hand, Fig. 2 shows an example in which the heating electrode 57 is formed by two lines, but the invention is not limited thereto. The heating electrode 57 may be formed of one or more lines. For example, the heating electrode may be formed as one line. In this case, the wiring electrodes are connected to both ends of the exothermic electrode. Or three lines, the three lines are connected in alphabetical letter "S" by connecting wiring, and the wiring electrodes are connected to opposite ends of the first and third flare electrodes. That is, when the odd number of heating electrodes are formed, the wiring electrodes are connected to the opposite sides, and when the even number of heating electrodes are formed, the wiring electrodes may be connected to the same side.

Hereinafter, the exothermic composition and the exothermic body using the exothermic composition according to the present invention will be described in detail with reference to test examples. The following test examples are only illustrative of the present invention, and the present invention is not limited by the following test examples.

Test Example

[Example 1]

First, 2 wt% of CNT and 1 wt% of graphene oxide (GO) are added to a mixture composed of a hybrid binder, BCA, DPM and a dispersant, and stirred using a planetary mixer. Then 15 wt% of graphite particles having a diameter of 100 탆 and a thickness of 1 탆 or less is added to the mixture to which CNT and GO have been added and re-crosslinked. Then, the linearly dispersed mixture was sufficiently stirred for 30 minutes using a 3-roll mill to prepare the exothermic composition according to Example 1.

[Example 2]

2% by weight of CNT and 0.05% by weight of graphene oxide (GO) are added to a mixture composed of a mixed binder, BCA, DPM and a dispersant, and stirred using a plant mixer. Then 15 wt% of graphite particles having a diameter of 100 탆 and a thickness of 1 탆 or less is added to the mixture to which CNT and GO have been added and re-crosslinked. Then, the linearly dispersed mixture was thoroughly stirred for 30 minutes using a three-roll mill to prepare the exothermic composition according to Example 2.

[Example 3]

5% by weight of CNT and 0.1% by weight of graphene oxide (GO) are added to a mixture composed of a mixed binder, BCA, DPM and a dispersant, and stirred using a plant mixer. Then, 10 wt% of graphite particles having a diameter of 100 mu m and a thickness of 1 mu m or less is added to the mixture to which CNT and GO have been added and re-crosslinked. Then, the linearly dispersed mixture was thoroughly stirred for 30 minutes using a 3-roll mill to prepare the exothermic composition according to Example 3.

[Comparative Example 1]

To the mixture composed of the mixed binder, BCA, DPM and dispersant, 2 wt% of CNT was added first and stirred using a flannel mixer. Then 15 wt% of graphite particles having a diameter of 100 mu m and a thickness of 1 mu m or less is added to the mixture to which CNT is added and re-crosslinked. Then, the linearly dispersed mixture was thoroughly stirred for 30 minutes using a three-roll mill to prepare a heat-generating composition according to Comparative Example 1. [

[Comparative Example 2]

First, 5 wt% of CNT was added to a mixture composed of a hybrid binder, BCA, DPM and a dispersant, and the mixture was stirred using a plant mixer. Then, 10 wt% of graphite particles having a diameter of 100 mu m and a thickness of 1 mu m or less is added to the mixture to which CNT is added and re-crosslinked. Then, the linearly dispersed mixture was thoroughly stirred for 30 minutes using a 3-roll mill to prepare the exothermic composition according to Comparative Example 2.

[Comparative Example 3]

First, 1 wt% of CNT is added to a mixture composed of a hybrid binder, BCA, DPM and a dispersant, and the mixture is stirred using a plant mixer. 10 wt% of graphite particles having a diameter of 100 탆 and a thickness of 1 탆 or less and 50 wt% of a flake-type silver powder are added to the mixture to which CNT is added, and then re-crosslinked. Then, the linearly dispersed mixture was thoroughly stirred for 30 minutes using a three-roll mill to prepare a heat-generating composition according to Comparative Example 3. [

The exothermic compositions according to Examples 1 to 3 and Comparative Examples 1 to 3 thus prepared were screen-printed on alumina ceramic substrates each having wiring electrodes formed thereon using a 250 mesh screen mask. The printed ceramic substrate was thermally cured in a convection oven at 150 ° C for 30 minutes and then annealed at 290 ° C for 30 minutes to prepare a heating element according to Examples 1 to 3 and Comparative Examples 1 to 3 in which a heating electrode was formed .

 The glass transition temperatures of the heating bodies according to Examples 1 to 3 and Comparative Examples 1 to 3 were measured by differential scanning calorimetry (DSC), and the glass transition temperature was measured by TGA (thermogravimetric analysis) Were measured.

As a result of measuring the glass transition temperature by DSC, it was confirmed that the glass transition temperature of Examples 1 to 3 in which graphene oxide was added was higher than that of Comparative Examples 1 to 3 in which no graphene oxide was added.

The TGA analysis was carried out in an air atmosphere at a heating rate of 10 ° C / min up to 500 ° C, and the decomposition starting temperature was set at 5% mass reduction point in consideration of moisture and volatilization of the residual solvent, Respectively. The evaluation results are shown in Table 1 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Decomposition start temperature (캜) 326 321 322 319 292 289

Referring to Table 1, it can be seen that in Examples 1 to 3 in which graphene oxide was added, the decomposition initiation temperature was increased by about 30 ° C as compared with Comparative Examples 1 to 3 in which no graphene oxide was added.

Thus, since the exothermic compositions according to Examples 1 to 3 contain graphene oxide, it is possible to induce direct chemical covalent bonding with the mixed binder which is an organic binder. As a result, the exothermic compositions according to Examples 1 to 3 can raise the glass transition temperature and the decomposition initiation temperature. Therefore, the exothermic compositions according to Examples 1 to 3 have stable heat resistance even at a temperature around 300 캜.

It should be noted that the embodiments disclosed in the present specification and drawings are only illustrative of specific examples for the purpose of understanding, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that other modifications based on the technical idea of the present invention are possible in addition to the embodiments disclosed herein.

50: heating element
51: Ceramic substrate
53: Connection wiring
53a: first connection wiring
53b: second connection wiring
53c: third connection wiring
55: wiring electrode
55a: first wiring electrode
55b: second wiring electrode
57: heating electrode
57a: first heating electrode
57b: second heating electrode
59: Insulating film

Claims (8)

A mixed binder in which epoxy acrylate or hexamethylene diisocyanate, polyvinyl acetal, and phenolic resin are mixed;
Graphene oxide particles;
Conductive particles comprising at least two of carbon nanotube particles, graphite particles and metal powder;
Organic solvent; And
Dispersing agent;
≪ / RTI > The method according to claim 1,
Wherein the graphene oxide particles have an insulating property within 1 to 20 layers and are partially graphitized particles. The method according to claim 1,
Wherein the mixed binder is 8 to 10 parts by weight, the carbon nanotube particles are 0.1 to 5 parts by weight, the graphite particles are 0.1 to 20 parts by weight, the graphene oxide particles are 0.0001 to 1 part by weight based on 100 parts by weight of the exothermic composition, 20 to 80 parts by weight of a dispersing agent, and 0.5 to 5 parts by weight of a dispersing agent. The method according to claim 1,
Wherein the mixed binder is 8 to 10 parts by weight, the carbon nanotube particles are 0.1 to 5 parts by weight, the graphite particles are 0.1 to 20 parts by weight, the metal powder is 10 to 60 parts by weight, the graphene oxide particles are 0.0001 To 1 part by weight, the organic solvent is 20 to 80 parts by weight, and the dispersing agent is 0.5 to 5 parts by weight. The method according to claim 1,
Wherein the mixed binder is a mixture of 10 to 150 parts by weight of a polyvinyl acetal resin and 10 to 500 parts by weight of a phenolic resin based on 100 parts by weight of epoxy acrylate or hexamethylene diisocyanate. The method according to claim 1,
The carbon nanotube particles have a diameter of 1 nm to 20 nm and a length of 1 占 퐉 to 100 占 퐉,
The graphite particles have a diameter of 1 탆 to 25 탆 and a length of 1 nm to 25 탆,
Wherein the metal powder comprises a metal powder of silver or copper,
The metal powder of the silver material has a flake, a circular shape, a polygonal plate shape or a rod shape,
Wherein the metal powder of the copper material comprises copper coated with silver or copper coated with nickel. The method according to claim 1,
Wherein the exothermic composition is thermally cured at 100 占 폚 to 180 占 폚 and aged at 250 占 폚 to 350 占 폚. A ceramic substrate;
And a heating electrode formed by printing a heating composition on an upper surface of the ceramic substrate,
The exothermic composition of the exothermic electrode
A mixed binder in which epoxy acrylate or hexamethylene diisocyanate, polyvinyl acetal, and phenolic resin are mixed;
Graphene oxide particles;
Conductive particles comprising at least two of carbon nanotube particles, graphite particles and metal powder;
Organic solvent; And
Dispersing agent;
.
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CN110819074A (en) * 2019-11-28 2020-02-21 深圳市烯碳复合材料有限公司 Preparation method of graphene composite material
CN114641102A (en) * 2020-12-15 2022-06-17 安徽宇航派蒙健康科技股份有限公司 Preparation method of graphene composite heating body
KR20220089789A (en) * 2020-12-21 2022-06-29 주식회사 세라핀 Volumetric heating materials comprising graphene oxide and method for manufacturing the same
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CN109811382A (en) * 2019-03-28 2019-05-28 烟台恒诺新材料有限公司 A kind of application of graphene oxide conductive paste in black holesization is directly electroplated
CN109811382B (en) * 2019-03-28 2021-04-20 烟台恒诺新材料有限公司 Application of graphene oxide conductive paste in black hole direct electroplating
CN110819074A (en) * 2019-11-28 2020-02-21 深圳市烯碳复合材料有限公司 Preparation method of graphene composite material
CN110819074B (en) * 2019-11-28 2022-06-28 深圳市图特美高分子材料有限公司 Preparation method of graphene composite material
CN114641102A (en) * 2020-12-15 2022-06-17 安徽宇航派蒙健康科技股份有限公司 Preparation method of graphene composite heating body
CN114641102B (en) * 2020-12-15 2024-01-26 安徽宇航派蒙健康科技股份有限公司 Preparation method of graphene composite heating body
KR20220089789A (en) * 2020-12-21 2022-06-29 주식회사 세라핀 Volumetric heating materials comprising graphene oxide and method for manufacturing the same
KR20220169865A (en) * 2021-06-21 2022-12-28 고려대학교 산학협력단 Flexible Planar Heater and Manufacturing Method Thereof

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