Heating paste composition, and sheet heating element, heating roller, heating unit and heating module using same

Abstract

A heating paste composition, and a sheet heating element, a heating roller, a heating unit and a heating module, which use the composition, are disclosed. In one aspect, the heating paste composition includes 0.2 parts to 6 parts by weight of carbon nanotube particles, 0.5 parts to 30 parts by weight of graphite particles, 5 parts to 30 parts by weight of a binder mixture, 29 parts to 80 parts by weight of an organic solvent and 0.5 parts to 5 parts by weight of a dispersant, wherein the weights are with respect to 100 parts by weight of the heating paste composition.

Claims

1. A heating paste composition, comprising: 0.2 parts to 6 parts by weight of carbon nanotube particles; 0.5 parts to 30 parts by weight of graphite particles; 5 parts to 30 parts by weight of a binder mixture; 29 parts to 80 parts by weight of an organic solvent; and 0.5 parts to 5 parts by weight of a dispersant, wherein the weights are with respect to 100 parts by weight of the heating paste composition, wherein the binder mixture includes (i) a polyvinyl acetal resin, (ii) a phenol resin, and (iii) epoxy acrylate or hexamethylene diisocyanate, wherein the weight of the polyvinyl acetal resin with respect to 100 parts by weight of epoxy acrylate or hexamethylene diisocyanate is 10 parts to 150 parts, and wherein the weight of the phenol resin with respect to 100 parts by weight of epoxy acrylate or hexamethylene diisocyanate is 100 parts to 500 parts.

2. The composition of claim 1, further comprising 0.5 parts to 5 parts by weight of a silane additive with respect to 100 parts by weight of the heating paste composition.

3. The composition of claim 1, wherein the carbon nanotube particles comprise multi-walled carbon nanotube particles.

4. The composition of claim 1, wherein the organic solvent comprises a solvent mixture including at least one of the following: carbitol acetate, butyl carbitol acetate, dibasic ester (DBE), ethyl carbitol, ethyl carbitol acetate, dipropylene glycol methylether, cellosolve acetate, butyl cellosolve acetate, butanol and octanol.

5. A sheet heating element comprising a heating paste composition configured to be integrated into a protective layer or an electrode and comprising: 0.2 parts to 6 parts by weight of carbon nanotube particles; 0.5 parts to 30 parts by weight of graphite particles; 5 parts to 30 parts by weight of a binder mixture; 29 parts to 80 parts by weight of an organic solvent; and 0.5 parts to 5 parts by weight of a dispersant, wherein the weights are with respect to 100 parts by weight of the heating paste composition, and wherein the binder mixture comprises a polyvinyl acetal resin, a phenol resin, and hexamethylene diisocyanate, wherein the weight of the polyvinyl acetal resin with respect to 100 parts by weight of hexamethylene diisocyanate is 10 parts to 150 parts, and wherein the weight of the phenol resin with respect to 100 parts by weight of hexamethylene diisocyanate is 100 parts to 500 parts.

6. The sheet heating element of claim 5, wherein the sheet heating element is formed using screen printing, gravure printing or comma coating of the heating paste composition.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 illustrates a specimen of a sheet heating element manufactured using a heating paste composition according to an embodiment.

(2) FIG. 2 illustrates a heating test for the sheet heating element according to an embodiment of FIG. 1.

(3) FIG. 3 illustrates the sheet heating element according to the embodiment of FIG. 1, taken by a thermographic camera.

(4) FIG. 4 illustrates a heating property of the sheet heating element according to the embodiment of FIG. 1.

(5) FIG. 5 illustrates driving of a heating roller according to one exemplary embodiment.

(6) FIG. 6 illustrates the heating roller according to another embodiment.

(7) FIG. 7 illustrates components of the heating roller according to another embodiment.

(8) FIG. 8 illustrates driving of a heating module according to one exemplary embodiment.

(9) FIG. 9 illustrates the heating module according to another embodiment.

(10) FIG. 10 illustrates components of a heating unit according to one exemplary embodiment.

DETAILED DESCRIPTION

(11) A typical sheet heating element using carbon processes a paste prepared by dispersing carbon-based powder such as carbon black in a proper form. The sheet heating element is driven while the temperature of a material is maintained at a desired level by supplying a current to both ends of the sheet heating element. However, such a carbon-black based carbon sheet heating element cannot be used to develop a heating element having heat resistance at 200 C. or higher due to a characteristic positive coefficient temperature (PCT) of the carbon-black. Additionally, due to a relatively high specific resistance of the composition and a difficult thick film process, it is difficult for the heating roller or heating unit including the heating element to be driven at low voltage and low power, and time for continuous operation is also short.

(12) The present disclosure relates to a heating paste composition, and a sheet heating element and a heating roller, which include the corresponding composition. Hereinafter, embodiments of the present disclosure will be described in further detail with reference to the accompanying drawings.

(13) In one embodiment, the heating paste composition includes carbon nanotube particles, graphite particles, a binder mixture, an organic solvent and a dispersant.

(14) In one embodiment, the heating paste composition includes 0.2 parts to 6 parts by weight of carbon nanotube particles, 0.5 parts to 30 parts by weight of graphite particles, 5 parts to 30 parts by weight of a binder mixture, 29 parts to 80 parts by weight of an organic solvent, and 0.5 parts to 5 parts by weight of a dispersant with respect to 100 parts by weight of the heating paste composition.

(15) The carbon nanotube particles may be selected from single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes or a mixture thereof. For example, the carbon nanotube particles may be multi-walled carbon nanotubes. When the carbon nanotube particles are multi-walled carbon nanotubes, the particle may have a diameter of 5 nm to 30 nm and a length of 3 m to 40 m.

(16) The graphite particles may have a diameter of 1 m to 25 m.

(17) The binder mixture allows the heating paste composition to have heat resistance at a temperature of approximately 300 C., and is a mixture of two or more selected from polyester, epoxy, epoxy acrylate, hexamethylene diisocyanate, polyvinyl acetal and a phenol resin. The binder mixture may be a mixture of polyester, polyvinyl acetal and a phenol resin, a mixture of epoxy, polyvinyl acetal and a phenol resin, or a mixture of epoxy acrylate, polyvinyl acetal and a phenol resin, or a mixture of hexamethylene diisocyanate, polyvinyl acetal and a phenol resin. In some embodiments, as the heat resistance of the binder mixture increases, there is no change in resistance of the material or no damage to a coated film even when the composition is heated to a high temperature of approximately 300 C.

(18) Here, the phenol resin refers to a phenolic compound including phenol and phenol derivatives. For example, the phenol derivatives include p-cresol, o-guaiacol, creosol, catechol, 3-methoxy-1,2-benzenediol, homocatechol, vinylguaiacol, syringol, iso-eugenol, methoxyeugenol, o-cresol, 3-methyl-1,2-benzenediol, (z)-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-benzenetriol, 2-methoxy-6-methylphenol, 2-methoxy-4-vinylphenol, and 4-ethyl-2-methoxy-phenol, but the described technology is not limited thereto.

(19) The mixing ratio of the binder mixture may be 10 parts to 150 parts by weight of a polyvinyl acetal resin and 100 parts to 500 parts by weight of a phenol resin with respect to 100 parts by weight of polyester, epoxy, epoxy acrylate or hexamethylene diisocyanate. In some embodiments, when the content of the phenol resin is 100 parts by weight or less, heat resistance of the heating paste composition is degraded, and when the content of the phenol resin is more than 500 parts by weight, flexibility is degraded (increased brittleness).

(20) In some embodiments, the organic solvent is used to disperse conductive particles and the binder mixture, and may be a solvent mixture of two or more selected from carbitol acetate, butyl carbitol acetate, dibasic ester (DBE), ethyl carbitol, ethyl carbitol acetate, dipropylene glycol methylether, cellosolve acetate, butyl cellosolve acetate, butanol and octanol.

(21) Meanwhile, for a process of dispersion, a variety of generally used methods such as ultra-sonication, roll milling, bead milling or ball milling may be applied.

(22) In some embodiments, the dispersant is used to further facilitate dispersion, and may be a general dispersant, for example, BYK types, an amphoteric surfactant such as Triton X-100, or an ionic surfactant such as SDS.

(23) The heating paste composition may further include 0.5 parts to 5 parts by weight of a silane coupling agent with respect to 100 parts by weight of the heating paste composition.

(24) In some embodiments, the silane coupling agent serves as an adhesion promoter to improve adhesion strength between resins when the components of the heating paste composition are mixed. The silane coupling agent may be an epoxy-containing silane or a mercapto-containing silane. Examples of the silane coupling agents include epoxy-containing silanes such as 2-(3,4 epoxy cyclohexyl)-ethyltrimethoxysilane, 3-glycidoxytrimethoxysilane, and 3-glycidoxypropyltriethoxysilane, amine-containing silanes such as N-2(aminoethyl)3-aminopropylmethyldimethoxysilane, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine and N-phenyl-3-aminopropyltrimethoxysilane, mercapto-containing silanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltriethoxysilane, and an isocyanate-containing silane such as 3-isocyanatepropyltrimethoxysilane, but the described technology is not limited thereto.

(25) Some embodiments provide a sheet heating element including the heating paste composition formed on a substrate or the circumferential surface of a roller by screen printing, gravure printing (or roll-to-roll gravure printing) or comma coating (or roll-to-roll comma coating).

(26) The substrate may be polycarbonate, polyethyleneterephthalate (PET), polyethylenenaphthalate (PEN), polyimide, cellulose ester, nylon, polypropylene, polyacrylonitrile, polysulfone, polyestersulfone, polyvinylidenefluoride, glass, glass fiber (matt), ceramic, SUS, a copper or aluminum substrate, but the described technology is not limited thereto. For example, the substrate can be suitably selected according to an application or a temperature at which the heating element is used.

(27) The sheet heating element may be formed by printing the heating paste composition on the substrate through screen printing or gravure printing in a desired pattern, and forming an electrode by printing and drying/curing a silver paste or conductive paste thereon. The sheet heating element may also be formed by printing and drying/curing a silver paste or a conductive paste, and screen printing or gravure printing the heating paste composition.

(28) The sheet heating element may further include a protective layer formed to coat a top surface thereof. In some embodiments, the protective layer is formed of silica (SiO.sub.2). In some embodiments, the flexibility of a heating element can be maintained even though a heating surface is coated when a protective layer is formed of resins including silica.

(29) Hereinafter, the heating paste composition and the sheet heating element using the same will be described in detail with reference to experimental examples. The following experimental examples are merely provided to illustrate the present embodiments, and described technology is not limited to the following experimental examples.

Experimental Examples

(30) (1) Preparation of Examples and Comparative Examples

(31) Examples (3 types) and comparative examples (3 types) were prepared as shown in Table 1. Composition ratios shown in Table 1 are given as wt %.

(32) TABLE-US-00001 TABLE 1 Example Example Example Comparative Comparative Comparative Composition 1 2 3 Example 1 Example 2 Example 3 Carbon nanotube 4 5 6 4 4 5 particles Graphite particles 15 9 15 Carbon black 15 15 9 particles Binder mixture 20 15 22 12 Ethyl cellulose 10 14 Organic solvent 57 66 54 67 65 68 Dispersant 4 4 5 4 4 4

(33) In the case of the examples, a heating paste was prepared by predispersing carbon nanotube particles, graphite particles, a binder mixture, an organic solvent and a dispersant using a predispersion instrument for 1 hour according to the compositions shown in Table 1 (Examples 1 to 3), and completely stirring a predispersed paste using a 3-roll mill. Subsequently, the heating paste was aged at room temperature for 12 hours, and then printed using a 325 mesh screen, thereby manufacturing a heating element.

(34) In the case of the comparative examples, according to the compositions shown in Table 1 (Comparative Examples 1 to 3), a heating paste was prepared by predispersing carbon nanotube particles, carbon black particles, a binder mixture or ethyl cellulose, an organic solvent and a dispersant using a predispersion instrument for 1 hour, and completely stirring a predispersed paste using a 3-roll mill. The heating paste was aged at room temperature for 12 hours, and then printed using a 325 mesh screen, thereby manufacturing a heating element.

(35) (2) Evaluation of Properties of Sheet Heating Element

(36) FIG. 1 illustrates a specimen of a sheet heating element manufactured using a heating paste composition, FIG. 2 illustrates a heating test for the sheet heating element according to the embodiment of FIG. 1, and FIG. 3 illustrates the sheet heating element according to the embodiment of FIG. 1, taken by a thermographic camera.

(37) 1) Evaluation of Specific Resistance

(38) As shown in FIG. 1, a composition was cured after screen printing in a size of 10 cm10 cm, a linear resistance between both ends was determined, and a thickness of a printed electrode was measured through SEM, thereby calculating a specific resistance.

(39) 2) Evaluation of Properties of Composition For Sheet Heating Element

(40) As shown in FIG. 1, a composition was cured after screen printing in a size of 10 cm10 cm, thereby constituting a heating element, as shown in FIG. 2, an electrode material was printed on both ends of the heating element to manufacture a sample for a heating test, and as shown in FIG. 3, temperature uniformity of each part of the heating element was measured using a thermographic camera while an electrode voltage was applied.

(41) Here, to confirm a temperature-increasing effect according to power supplied, a sheet heating element corresponding to each example or comparative example is increased in temperature up to 150 C., 180 C., or 220 C., and a DC power when the sheet heating element reached the corresponding temperature was measured.

(42) In addition, heating stability was tested for each example and comparative examples at 200 C.

(43) Test results are shown in Table 2 below.

(44) TABLE-US-00002 TABLE 2 Comparative Comparative Comparative Property Example 1 Example 2 Example 3 Example 1 Example 2 Example 3 Specific resistance 1.9 2.55 2.96 49.3 60.5 59.3 (10.sup.2 cm) DC power (w) required 22.3 24.5 25.6 127.3 136.5 132.9 to reach 150 C. DC power (w) required 30.8 33.0 36.5 146.5 172.3 168.5 to reach 180 C. DC power (w) required 44.0 47.5 48.6 162.5 200.3 185.6 to reach 220 C. Heating stability (day) 20 days or 20 days or 20 days or Fail 5 days Fail longer longer longer

(45) Referring to Table 2, the measured specific resistance of the sheet heating element corresponding to each example was smaller than that corresponding to each comparative example. Also, the measured DC power required to heat the sheet heating element up to 150 C., 180 C. or 220 C. was also lower than those of comparative examples. That is, it can be confirmed that the sheet heating elements of the examples have lower power consumption and improved heating performance than those of the comparative examples.

(46) Also, the sheet heating elements according to Examples 1 to 3, maintained stability for 20 days while being driven even at 200 C. (without a separate protective layer). However, in Comparative Examples 1 to 3, swelling of a heating surface is observed within 2 hours or a maximum of 5 days after the sheet heating elements are driven at 200 C. Therefore, it can be confirmed that the sheet heating elements of the examples are driven more stably even at high temperatures of 200 C. or higher than those of the comparative examples.

(47) FIG. 4 illustrates a heating property of the sheet heating element according to the embodiment of FIG. 1.

(48) In FIG. 4, the y-axis represents heating temperature and the x-axis represents time, which shows heating behavior when 31.5V DC was applied to the sheet heating element of the examples.

(49) In FIG. 4, it can be confirmed that the time for reaching 180 C. is only 6 seconds or less, which demonstrates that fast warm-up and an improved printing speed can be achieved by short temperature-increasing time.

(50) The sheet heating element of the examples may reach 180 C. within 12 seconds even when the sheet heating element is coated with a protective film or a release layer such as Teflon.

(51) The described technology further provides a heating roller employing a sheet heating element consisting of the above-described heating paste composition.

(52) FIG. 5 illustrates driving of a heating roller 10 according to one embodiment, FIG. 6 illustrates the heating roller 10 according to one embodiment, and FIG. 7 illustrates components of the heating roller 10 according to one embodiment.

(53) Referring to FIGS. 5 to 7, an image-forming device such as a printer fuses a toner image to paper 30 using a heating roller 10 and a press roller 20, which are installed at a paper discharging unit.

(54) Here, the heating roller 10 may transfer heat to the paper 30 passing between the heating roller 10 and the press roller 20, and the press roller 20 includes an elastic material such as rubber and thus may transfer a suitable pressure to the paper 30 between the heating roller 10 and the press roller 20. Therefore, the toner image transferred to the paper 30 may be fixed using heat and pressure.

(55) The heating roller 10 includes a roller 11, an insulating layer 12, an electrode 13 and a sheet heating element 14.

(56) The roller 11 can be a cylindrical rotating body, which is rotating about an axis of rotation.

(57) The insulating layer 12 may be formed of a glass powder paste such as a glass frit, and is formed on the circumferential surface of the roller 11 and positioned between the roller 11 and the sheet heating element 14.

(58) The sheet heating element 14 includes the above-described heating paste composition, which may include 0.2 parts to 6 parts by weight of carbon nanotube particles, 0.5 parts to 30 parts by weight of graphite particles, 5 parts to 30 parts by weight of a binder mixture, 29 parts to 80 parts by weight of an organic solvent, and 0.5 parts to 5 parts by weight of a dispersant with respect to 100 parts by weight of the heating paste composition. The sheet heating element 14 is formed on the circumferential surface of the insulating layer 12.

(59) The electrode 13 is installed at both ends of the sheet heating element 14 to provide power to the sheet heating element. The electrode 13 may include a lead electrode formed on the right and left sides of the sheet heating element 14 by coating, and electrodes for power connection, which are formed to be attached to the corresponding lead electrode. In some cases, the electrodes for power connection may be directly connected to the sheet heating element. The electrode 13 may be formed with a silver paste, a copper paste, or a copper tape.

(60) A Teflon release layer may be formed for preventing the toner from adhering to the circumferential surface of the sheet heating element 14. Here, the Teflon release layer may be formed by powder coating or spray coating.

(61) The present disclosure further provides a heating unit employing a sheet heating element including the above-described heating paste composition and a heating module using the corresponding heating unit.

(62) FIG. 8 illustrates driving a heating module according to one embodiment, FIG. 9 illustrates the heating module according to one embodiment, and FIG. 10 illustrates components of a heating unit 40 according to one embodiment.

(63) Referring to FIGS. 8 to 10, an image-forming device such as a printer fuses a toner image to paper 60 using a heating unit 40 and a press roller 50, which is installed at a paper discharging unit.

(64) In some embodiments, the heating unit 40 transfers heat to the paper 60 passing between the heating unit 40 and the press roller 50. The press roller 50 can include an elastic material such as rubber and thus may transfer a suitable pressure to the paper 60 between the heating roller 40 and the press roller 60. Therefore, the toner image transferred to the paper 60 may be fixed using heat and pressure.

(65) The heating unit 40 constitutes a heating module along with a fixing film 1. The fixing film 1 is a component for fixing the heating unit 40, and can form a cylindrical shape having one flat side with the heating unit 40. Here, the fixing film 1 may have an opening area in a cylindrical lengthwise direction, and may allow the heating unit 40 to be fixed to the opening area of the fixing film 1.

(66) The heating unit 40 may have a structure in which a substrate 41, a protective layer 42, an electrode 43, a sheet heating element 44, a polyimide sheet 45 and a Teflon release layer 46 are stacked. Here, the heating unit 40 in a parallel-stacked form may be bound to the opening area of the fixing film 1, and as shown in FIGS. 8 and 9. For example, the heating unit 40 is bound to the opening area of the fixing film 1 while edges of the heating unit 40 are bent along the lengthwise direction of the fixing film 1 in a shape.

(67) The substrate 41 can have a planar structure made of a metal, such as copper, aluminum or stainless steel.

(68) The protective layer 42 is formed on one surface of the substrate 41 and positioned between the substrate 41 and the sheet heating element 44. The protective layer 42 is formed to enhance voltage resistance and heat resistance, and may include a silica (SiO.sub.2)-based thermosetting resin, and even maintain flexibility when being formed to coat the sheet heating element 44.

(69) The sheet heating element 44 includes the above-described heating paste composition, which may include 0.2 parts to 6 parts by weight of carbon nanotube particles, 0.5 parts to 30 parts by weight of graphite particles, 5 parts to 30 parts by weight of a binder mixture, 29 parts to 80 parts by weight of an organic solvent, and 0.5 parts to 5 parts by weight of a dispersant. The sheet heating element 44 is formed on one surface of the protective layer 42 opposite to the substrate 41, and positioned between the protective layer 42 and the polyimide sheet 45.

(70) The electrode 43 is installed at both ends of the sheet heating element 44 to provide power to the sheet heating element. The electrode 43 may include lead electrodes formed at right and left sides of the sheet heating element 44 by coating, and electrodes for a power connection, which are bound to the corresponding lead electrodes. In some cases, the electrodes for a power connection may be directly connected to the sheet heating element. The electrode 43 may be formed using a silver paste, a copper paste, or a copper tape.

(71) The polyimide sheet 45 in a film form is formed on one surface of the sheet heating element 44 opposite to the protective layer 42. The polyimide sheet 45 may have excellent mechanical strength, electrical property and heat resistance.

(72) The Teflon release layer 46 is formed on one surface of the substrate 41 opposite to the protective layer 42. The Teflon release layer 46 prevents a toner from adhering to the substrate 41, and may be formed by powder coating or spray coating.

(73) Such a heating unit 40 may be manufactured by coating one surface of the substrate 41 with the Teflon release layer 46, and sequentially forming the protective layer 42, the electrode 43, the sheet heating element 44 and the polyimide sheet 45 from the other surface of the substrate 41.

(74) Also, the heating unit 40 may be manufactured, for example, by sequentially forming the electrode 43, the sheet heating element 44 and the protective layer 42 on one surface of the polyimide sheet 45, and attaching the surface of the protective layer 42 opposite to the sheet heating element 44 to one surface of the substrate 41.

(75) The embodiments disclosed in the specification and the drawings are merely examples, and are not intended to limit the scope of the described technology. It will be apparent to those of ordinary skill in the art that, other than the embodiments disclosed herein, modifications based on the technological scope of the present disclosure may also be implemented. Also, specific terms have been used in the specification and the drawings, but they are merely used in a general sense to facilitate the understanding of the present disclosure, and are not intended to limit the scope of the present disclosure.