TWI236489B - The polymer thermistor using the metal coated ceramic particles - Google Patents

Abstract

The general conductive fillers are metal particles and carbon black. The advantage of using the metal coated ceramic particles is that the sedimentation of conductive particles in the composite, due to the gravitational forces on the particles, can be significantly reduced. Besides, the coefficient of thermal expansion (CTE) of the ceramic particles is small. So this kind of polymer thermistor has better conductive property and PTC behavior.

Description

1236489 V. Description of the invention (1) The polymer conductive composite material is a conductive filler mixed with a polymer base material, when the content of the conductive filler reaches a certain value (critical volume fraction), the conductive particles start to each other. The conductive path is formed by contact, so it is conductive. Its resin substrate includes thermosetting resin and thermoplastic resin. Commonly used thermosetting resins are epoxy resin (Epoxγ), polyimide resin (Polyimide), polyimide resin (Polyamideimide), Shi Xishi with the resin ... and so on. Commonly used thermoplastic resins are polyethylene (polyol ^, polymethyl methacrylate (pmma), polystyrene (polysty r ene), etc .. The conductive fillers include metal powder, metal oxide, carbon Black, carbon fiber, graphite, etc. In addition to being used as conductive adhesives or resistors, polymer conductive composites can also be used as antistatic materials because they are less likely to generate charge accumulation when used as coatings. And resistance to electromagnetic waves. The material itself will change the resistance value as the temperature changes-"# sr in the metal, 'the resistance value will increase as the temperature rises, this resistance value changes in the same direction as the temperature phenomenon' We call it Positive Temperature Cofficient Resistivity Behavior. For most metals, it is almost a linear relationship. Compared to the PTCR characteristics of metals, most semiconductors are Insulators exhibit Negative Resistance Temperature Coefficient Behavior (NegaUve Temperature Cofficient ReSistivity Behavi〇r) _ Resistance value increases with temperature Exponential decline in ceramic material actually "lock Chin acid (BaTiO3) is a typical perovskite

1236489 V. Description of the invention (2) (Perov sk ite) structure, the central titanium atom is surrounded by an octahedral structure composed of 6 oxygen atoms around it, and each barium atom is surrounded by 12 oxygen atoms In other words, barium and oxygen atoms form a face-centered cubic structure, and titanium atoms are located at the geometric center of the octahedron. Such a lattice structure gives barium titanate a special ferroelectric behavior: Under normal temperature, the 'Qin acid-locked lattice has a tetrahedral (Tetragonal) structure' and the Qin atoms are located away from the lattice geometry. The position of the center point therefore has a permanent dipole moment. At this time, the barium titanate material has strong electromotive (or ferroelectric) properties. However, after the temperature exceeds the Curie point (approximately 120 ° C), the four-sided cubic lattice phase changes into a cubic structure, the titanium atom is located at the geometric center of the cube, and the polarization axis (j) ipole axis ) No longer exists, so ferroelectricity also disappears. In short, after sintering, the barium titanate ceramics have ferroelectricity (ferroelectricity) at room temperature, but after the temperature exceeds the Curie Temperature, the lattice phase The change causes the ferroelectricity to disappear, so the resistance value rises sharply. The polycrystalline barium titanate (p-BaTi〇3) doped with ^ 3 has a sharp rise in resistance at its unique Curie temperature point, and has been made into a thermistor (Therm "hr) for acoustic protection. Components, sensors, and heaters. The conductor-insulator formed by pushing conductive particles in Yamani ^ Γ ^ sub-resin. It has the same temperature difference as the barium titanate ceramic at the Curie temperature point. Resistance temperature coefficient behavior. During the heating process, the expansion of the resin phase causes the distance of the conductor powder to increase, resulting in an increase in the overall resistance value-the resistance value of the system will suddenly rise sharply after the point of helium, and approaches to

1236489 V. Description of the invention (3) The resistance of the resin phase (Matrix) ⑴. The thermal expansion effect of the resin is closely related to its glass transition temperature (Tg). The thermal expansion amount increases with the increase in temperature. The turning point is the glass transition temperature. Above Tg is the rubbery state. Its thermal expansion coefficient CTE (Coefficient) The coefficient of thermal expansion is greater than that of the glassy state below the Tg point. When the temperature reaches the glass transition temperature, the thermal expansion of the resin substrate will increase, so that the distance between the conductive particles blended in it will be further expanded, causing the resistance value to increase with the temperature increase: If the thermal expansion coefficient of the rubbery state It is much larger than the thermal expansion coefficient of the glassy state. After reaching the glass transition temperature, the thermal expansion of the resin phase causes the distance between conductive particles to be stretched, and the conductive paths cannot be continuous with each other, causing the resistance value to rise sharply, or even to an open circuit state (0pen ci rcu it); In addition, the content of conductive particles in the resin substrate will also affect its PTC behavior. If the content of conductive particles is not high, the conductive paths formed by it will be loose, making the resistance value at room temperature higher. When heated, it is also easier to break due to the thermal expansion of the resin phase, so its PTC behavior is more obvious; and the size of the conductive particles will also affect its PTC behavior: Under the same filling amount, the more conductive particles, the more conductive particles. The larger the total surface area, the greater the probability that particles and particles will contact each other, and the conductive path formed by them will be smaller than Intensive, the resistance value is affected by the expansion of the resin substrate _ it will reduce the demand, a phenomenon pTc its less significant. When a polymer conductive composite material is used as a thermistor with a positive temperature coefficient of resistance behavior, its conductive filler can be a pure metal powder (4,5,6,9,1 (), 15,16).

Page 7 1236489 V. Description of the invention (4) Alloy particles (4, 16) X «^ Shancheng oxide (5), carbon black (4, 5, 7, 8, 9, 10, 11, 12, 13 , 14, 16, 17), stone antifibers (9), graphite ... conductor metals, ^ special, substances with conductive properties. Good > metal particles are used as conductive additives, although the T% @ ^ μ μ Φ resistance value, but because of metal particles? ： In the electric process of reducing the composite material, the metal particles on the substrate are processed into conductive particles in the composite material. Both are easy to access: Now:; the gold content is insufficient, and the temple is not There will be settlement questions! Carbon black or carbon fiber is less dense though. First, the volume resistance value of Π2 carbon black is about " X1. , --⑻ is much higher than / / product resistance value (about 10-6 is in line with today's saving ^; ^ stay their key users ^. Power consumption will be higher, not to overcome the above problems, you can try to Table ... Let's go to-m 4, Pottery is a powder with a density lower than that of pure metal 5r, and the settlement caused by gravity can be greatly reduced: based on the range of the thickness of the surface of the conductive material 'effect: , The transmission of electric current: the conductive properties of conductive particles and pure metal particles: with this composite number. The thermal expansion rate of ceramic materials is in ':' two: the expansion or thermal expansion system < materials in 1 ~ 3x Qing Range, while the polymer material's stubbornness, metal material 4 ~ 20x. The polymer thermistor's ρτ, the rate is caused by the thermal expansion caused by the surface of the particles to rely on the lipid substrate Formed by

1236489 V. Description of the invention (5) The thermal expansion of composite plastic conductive particles is much smaller than that of polymer substrates, which will not affect the thermal expansion of resin substrates. Therefore, using this type of conductive particles can not only obtain excellent conductive properties, but also can Very good PTC characteristics were obtained. When the polymer conductive composite material is used as a thermistor, its resin substrate may be a thermosetting resin or a thermoplastic resin. From the perspective of molecular structure, using thermoplastic resin as the system substrate will have higher thermal expansion, pTC behavior will be more obvious, and processing is simple. It can be mixed by extrusion compounding, and the molding method is also The thermoforming method can be used as the type of resin mainly used as the base material of polymer thermistors. Commonly used are PE, HDPE, PP, PMMA, PS, etc., and the cost of thermoplastic raw materials is low. Different plastic materials have different Tg, which improves the design flexibility of the component. Compared with ceramic thermistors, the process of high temperature sintering (above 1 300 ° C) must be used to make conductive polymers based on thermoplastic resins. Composite materials, in the application of thermistors, are more competitive than ceramic materials and are more resistant to thermoplastic resins. When the brightness exceeds the melting point (Tm), it is known that there will be defects such as softening, deformation and affecting conductivity. In order to improve these = missing modified resins as resin substrates. The ^ t-inch female character of the thermosetting tree is poor, but the processing of the beard and the thermal expansion of the interfacial region affect its use as a thermistor barium titanate Tao studies that because its lattice will behave with temperature and its PTC behavior is restorative. Right: and therefore has PTC t, Xie π 1u > / V for the thermistor molecular thermistor opens, the conductive path becomes less continuous , The distance between the electric particles is reversed by Lou Fuhan + inverse,, κ and thus the resistance value becomes larger; when cooling, the tree

Page 9 1236489 V. Explanation of the invention (6) The moon phase will shrink, making the tear 4 1 ^, L ^ a the distance between the particles and the particles is reduced when heated, and the probability of contact between particles and particles @ ^ ^ ^ The ruler cuts hands and adds, so the resistance value will gradually decrease. In theory, it is possible to return to the state before it went hot. In this way, the polymer thermistor: The order should also be restorative. . Such characteristics can be used in circuit design and can be used as return switches (sw i t), thermometers, adders, etc. The use of a thermistor as a protection element is to apply a voltage or electricity to it, as the applied current increases, the accumulated heat will gradually increase, and the resin substrate will expand when heated, which will cause the When the resistance value rises, once it reaches the Curie-like temperature point, the resistance value rises sharply, causing it to be able to do so, and the overcurrent suddenly drops, forming a current-limiting function like a fuse. And the larger the current value is, the shorter the action time will be. According to the applied current value and its corresponding time, the anti-time characteristic curve of current versus time can be drawn. Different system components and different conductive particle content will have different anti-time characteristic curves. You can use this characteristic parameter to select a suitable polymer thermistor as the protective element of the system. Its function can replace the over-current ml relay. (CO Re secret). In addition, when a polymer thermistor is used as a protection element, the rated power that it can withstand must be taken into consideration to avoid damage to the resin substrate caused by the overload current. < Based on the foregoing, the advantages of a system in which a plated metal layer on the surface of ceramic particles is used as the conductive particles are separately discussed. Figure 1 shows the use of pure nickel metal particles blended in epoxy resin (£? 11828 / eight 1110 & 11 ^ 1 ^ 1 769), after homogeneous chain mixing, thermal curing reaction is performed to make a conductive thick film sample , Its conductive particles =

Page 10 1236489 V. Description of the invention (7) The relationship between the content and the volume resistance means that when the test piece is non-conductive, the amount is in weight percent. The number in square brackets is the test piece%; ^ resistance ;, 2. The first figure (EP〇828 / Ancaminel 769) = Second is the conductive particle content obtained on the same resin substrate. The surface of the nickel-plated silicon dioxide particles on the surface of the conductive particle system is divided into two and the relationship diagram. The pure nickel metal is compared with the surface mineral nickel content of one (30 wt%), and the conductive test piece has a resistance value and a weight of ^ because the density of the pure metal particles is very high ^^ 'Caimu's original conductive particles are affected by gravity and the effect of gravity is very large.' 4 The top of the element is high and therefore conductive; sub; The prepared system of thermal fossil particles has electrical conductivity instead of the conductive particles prepared by the surface oxygen record of the two oxygen bonds and has a surface map of the substituted fossil particles—for pure nickel metal particles mixed with epoxy resin (Epon828 / Ancaminel769), the white, and white are the relationship between the non-hardening reaction and the system change after you have made a conductive thick film sample. Figure 4 is the lower volume resistance with temperature u mouth four horses on the same resin substrate (EpON828 / 2 particles containing 篁 volume resistance with temperature changes. The two r systems all have a certain -temperature point 丄 ^ In the system, the temperature point at which the resistance value changes sharply is higher than that of purely recorded metal particles. Page 1212489 --- ~ V. Description of the invention (8) System A of the sub particle. Particle T is subject to heavy weight. It is a system of conductive particles. In its area, the resin is affected by 萦 2; the content of conductive particles is relatively ^, so the resistance 佶 h…, the service is easier to conduct lightning in this area ii Μ resistance value is easier to spread the conductive path of XT is less Uniform, open and add. However, because of the characteristics of the particles as early as the conductive particles, the "p": '= pure earth particles system is better. As for the aspect of the invention, the invention The content is to explain how the ceramic particles of the metal layer are 々 仃 will use the surface electroplating material, named red γ 冋 thermistor, as a new use among 乂 metal or carbon black as a conductive filler and Requirements. The following will describe the specific content of this patent:

two? In the end, the range supported by the embodiment is proposed. In order to solve the problem of sedimentation of conductive particles in the resin substrate due to gravity, the conductive particles used in the present invention are composite conductive particles. The metal particles are plated with a metal layer. Non-metals in composite conductive filler particles Page 12 1236489 V. Description of the invention (9) The particles can be ceramic powder, silicon dioxide, powder with a lower density than pure metals. The low-density, small thermal expansion coefficient particle powder is electroplated with a metal layer on the helmet = electric forging or chemically or sputW to deposit the metal layer to make it conductive ^ to complete the preparation of conductive particles The deposited metal can be gold, silver, copper, nickel, etc., depending on the formula of the plating solution used or the target source. "The resin substrate of the polymer thermistor can be determined according to the application environment. Select the appropriate resin. If you want to make a positive resistance temperature coefficient type resistance (PTCR) element that depends on the resistance value and temperature change, you need to use a long-chain aliphatic thermosetting resin or thermoplastic with a thermal expansion coefficient. Tree casting, such as aliphatic epoxy resin, polyethylene, etc. If processing is considered, the system substrate can also use epoxy resin or acrylic resin with unsaturated double bonds that can be cured by ultraviolet light, or Thermo-curable and photo-curable resins are mixed to form a bifunctional resin system, which is used as a polymer substrate. The photo-curable initiator (ph〇t〇initiat〇r) in UV-curable resin can be used. Oxide peroxide) or azo compound (Azocompound). The following application examples are used for illustration, but the present invention is not limited to these examples: Example 1

1236489 Sensitization and gasification (PdC 12) activation treatment, and then placed in hydrazine nickel solution for redox reaction, the nickel ions are precipitated and reduced to the second particle / sub-surface, and finally a silicon dioxide particle is formed. The preparation of nickel metal layer with uniform thickness to form conductive particles is shown in Figure 6. The base material of the system is epoxy resin & Epon82 8) with polyamine-type hardener (Ancaminel 769), the ratio is EP〇n82 8 / AnCami nel 769 = 1: 1. A ratio of 15 to 45 wt% is uniformly blended in the prepared resin material, and is prepared as a thick film resistor by screen printing or by means of a filling mold = block resistance to perform an isothermal crosslinking reaction. The resistance value of the polymer thermistor is measured with a precision resistor. Figure 2 shows the relationship between the content of conductive particles / fraction) and the volume resistance. The number in the figure is the number of test pieces. = When the test piece is not conductive, the volume resistance value is 1012hm—cm. ^ Relation between resistance value and temperature under doping. ® is different in the second embodiment. In the first embodiment, the system substrate can be changed to A with an aromatic polyamine type hardener (DETA / ,,, two = lice resin (Epon8 28)… and then oxidized. The ratio of 15% uniformly blended in the prepared resin odor-resistant board according to 15 ~ 60wt% and the relationship with the volume resistance is shown in Figure 7. The relationship of the temperature change of the conductive particle content is shown in Figure 8. 0 ♦ In case of miscellaneous 1, the resistance value varies with page 1236489 on page 14. V. Description of the invention (11) In the first and second embodiments, the formula of the plating solution can be changed, and the surface of the silicon dioxide particles can be electroplated or electrolessly plated. Other metals such as gold, silver, copper, Shao ... etc. Or a metal layer is deposited on the surface of the silicon dioxide particles by means of physical gold bonds or chemical sputtering to complete the preparation of conductive particles. Second, the silica particles in the second can be replaced by ceramic powder or clay with a density lower than that of pure metals, and then electro-mineralized metals such as gold, silver, copper, Shao, nickel, etc. by electroplating or electroless electricity ore. Or Physical sputtering dream = chemical sputtering, in A metal layer is deposited on the surface of the ceramic powder, and 6 = the preparation of electric particles. Fan Chengzhi or the light-curable acrylic resin 2 in the first to fourth embodiments: light, hardened epoxy resin peroxide Substance (peroxide) or% compound (Azocompound).

Page 12 1236489

V. Description of the invention (12) The agent and conductive particles are prepared as a thick film of external light hardenable resin, light initiator, and the viscosity of the resin is adjusted by mixing and mixing, and the technique of screen printing or doctor film forming is used. Irradiate to completely crosslink. Example Six

In the first embodiment, the photo-curable resin and the resin system are replaced. The thermosetting resin, UV-curable resin, thermosetting agent, light initiator, resin viscosity adjuster and conductive particles are mixed and mixed into a thick film by screen printing or film forming technology. = ^ The film formation technology of external light / heat stepwise hardening, firstly, the ultraviolet curable light initiates the crosslinking reaction of the photocurable resin to form a semi-gelatinized film, which produces the structure required to support the semi-gelatinized film, commonly known as B- In this stage, the conductive filler and the heat-curable resin are coated in the mesh of the ultraviolet-curable resin. The prepared semi-gelling conductive thick film has the convenience of integration with other processes, and finally it is completely cross-linked by thermal curing. Example 7 The system substrate in Example 4 may be replaced with a polyimide resin.

Page 16 1236489 V. Explanation of the invention (13) 'The compound conductive particles are uniformly mixed therein by the solvent method or the hot melt method' and then prepared into a thick film resistor by screen printing or by means of injection molding. It can be prepared into a block-shaped resistor or injection-molded with an extruder. After the volatilizing solvent is completely evaporated or the temperature is cooled, it can be formed. A high-temperature type (applicable to more than 2000) south molecular thermistor can be obtained. Example 8 In Example 7, the polyimide resin was replaced by a general thermoplastic resin such as polyethylene (PE), high density polyethylene (HDPE), low density polyethylene (LDPE), and polypropylene (PP). , Ethylene / propylene copolymer, polymethyl methacrylate (PMMA), polystyrene (PS), etc. References: ❿

1. · GR Ruschau and RE Newnham, Journal of Composite Material s, Vol. 26, No. 18, 1 992. 2. · PW Haayman, RW Dam, and HA K 1 asens, German Patent No. 29350, June, 1 955. Page 17 1236489 V. Description of the invention (14) 3. G. Pearson, US Patent No. 2, 258 958 1941 4. Philip Shaw, Jonathan Doyle, Michael Weber, Michael • Hess, Tom Hall, '1 PTC Circuit Protection Device and Manufacturing Method', Republic of China Patent No. 30 0347, 1997 5. Ma Yunjin, Wang Shaoqiu, π Variable Thermistor Element ", Patent No. 42 49 1 6，20 0 1 6 · Eibe Hidetoshi, Nishiyama Yoshio, Hiroi Hara, Mori Seijiro, Lin Longya, Takahashi Tomoe, Murata Shiro, π organic positive temperature coefficient composition and circuit protection device using the composition ", Patent of the Republic of China No. 344828, 1998 7 · Kumiichi Iwaya, Yoshiaki Iwago, Yoshiaki Echigo, Ito Akio ,, p TC element and its production method π, Republic of China Patent No. 298653, 1997 π for circuit overcurrent protection "Electric device", Republic of China Patent No. 3 83 5 18, 2000 9 · Tokuhisa, Takatani, Mori Yasushi, Xiao Gengheng, Tian Zongguang ,, organic P D C thermal resistor ", Zhonghua Republic of China Patent No. 3 1 2794, 1997 1 0 · Richard Frantil, Richard Burns, Mike Munnons, Scott Allen, "Positive Temperature Coefficient Resistive Composition Electrical parts and methods of making them ", ROC Patent No. 41 275 6, 2000 0 11. Bannich Ann, Edward Zhu," Electrical Devices Containing Conductive Polymers ", ROC Patent No. 428179, 2001 12. Tom Hall, "Improved ρ τ c Polymer Composition", Chinese People

Page 1236489 V. Description of the invention (15) (National Patent No. 371665, 1999 1 3 · Walrus Ruder, "Electrical Equipment with Variable Circuit Protection Device", Republic of China Patent No. 3835 1 7 , 20000 14 · Cheng Daijun, "Conductive Polymer Materials with Automatic Temperature Control (PTC) Performance", Republic of China Patent No. 3571 78, 1999 15 · Henry Wattier, Folegland, Ma Lian Cowenbo, "Manufacturing Methods of Mixed Metal Oxide Powders and Their Uses in Obtaining Powders for Electric Valley and Resistors", Republic of China Patent No. 208696, 1993 φ 16 · Tom Hall, "Improved Polymeric Polybutadiene-C Composition and Its Use in Electrical Devices and Circuits", Republic of China Patent No. 4051125, 2000 () 17. Edward F. Zhu, Nielsen · Tricho, Vijay Ridi, Daniel A. Chodler, π Conductive Polymer Composition ", Republic of China Patent No. 31 4 63 3, 1997

Page 12 1236489

Figure-The relationship between the content of conductive particles and the volume resistance of a 5-electric thick film sample that was mixed with epoxy resin (Ep 828 / ΓΓ 道 elJ69) using pure nickel metal particles and homogeneously mixed and then subjected to thermal hardening. Figure Figure 2: Nickel-coated silicon dioxide particles mixed with epoxy resin

Epon828 / Ancaminel 7 69), after uniformly mixing the chain, heat curing reaction is performed to make a conductive thick film sample. The relationship between the content of conductive particles and the volume resistance is shown in Figure 3. Pure nickel metal particles are mixed with epoxy resin (Epon828 /

Ancaminel 7 69), after homogeneous mixing of the chain, the thermal hardening reaction is performed to make a conductive thick film sample, and the relationship between the volume resistance and temperature at different conductive particle contents is shown in Figure 4. The conductivity of the nickel-plated metal layer on the surface of the silicon dioxide particles The particles are blended in epoxy resin (£ 0〇) 182 8 / eight 11〇 & 11 ^ 1 ^ 1 769), and after being mixed uniformly, the thermal hardening reaction is performed to make conductive thick film samples, and different conductive particles are used. Relationship between volume resistance and temperature change at different contents. Figure SEM photo of silicon dioxide particles

SEM picture of particle after nickel plating

1236Page 20

Claims (1)

1236489 VI. Patent application hardeners are selected from amine (Amine) hardeners, Anhydride hardeners, polyamidoamine hardeners, or other latent variants at room temperature to high temperature (above 20 (TC)) Hardener. 7. The polymer thermistor according to item 1 of the scope of patent application, wherein the ceramic particles in the conductive filler can be ceramic powder, clay powder or hollow glass balls; The material of the metal layer can be gold, silver, nickel, copper, aluminum, tin, or other alloys, such as nickel-phosphorus alloys; the plating method of the metal layer includes electroplating and electroless plating; the diameter of the conductive particles after plating is 0.1 micron to 1 0 micron. 8. The polymer thermistor described in item 1 of the scope of the patent application, wherein the amount of conductive filler is based on the entire system, accounting for 45 to 80 wt%. At room temperature, its volume resistance value is less than 10 ohm-cm. 9. The polymer thermistor as described in item 1 of the scope of patent application, wherein the additives include flow control agents, dispersants, wetting agents, dryness control At least one of a rheological agent, a rheological agent, and a coupling agent is added in an amount of 0 to 5 wt ° / 0. 10. A thermal expansion coefficient of at least one kind of electroplated metal layer on the surface of ceramic particles is used as a conductive filler in a rubbery state. Thick-film polymer thermistor prepared in a resin substrate composed of a resin and a hardener having a glassy thermal expansion coefficient of more than 1.5 times. The thickness of the thick-film polymer thermistor after hardening is less than 0.3. It has a resistance value of less than 1000 ohms at 25 ° C, and its composition includes: (a) a thermosetting epoxy resin; (b) a UV-curable resin; (c) a thermosetting agent; (D) Photohardening initiator; (e) Conductive filler with a metal layer plated on the surface of ceramic particles Page 23 1236489_ VI. Filling materials for patent application, with a diameter of 0.1 micrometers to 10 micrometers, the amount of which is 15 to 80 weight percent of the total weight of the mixture composed of the resin substrate and the conductive filler; (f ) An additive for improving the fluidity and anti-settling of the mixture in an amount of 0 to 5 weight percent of the total weight of the mixture. 1 1. The thick film polymer thermistor as described in item 10 of the scope of patent application, wherein the heat-curable epoxy resin is selected from a bifunctional or polyfunctional aliphatic epoxy resin and an aromatic resin. Family epoxy resin. 1 2. The thick film polymer thermistor as described in item 10 of the scope of the patent application, wherein the content of the heat-curable epoxy resin is 10 wt% to 90 wt% relative to the (a) + (b) resin system total weight. 1 3. The thick film polymer thermistor as described in item 10 of the scope of patent application, wherein the UV-curable resin is selected from resins containing vinyl or unsaturated groups, such as UV-curable epoxy Resin and UV-curable acrylic resin. 14. The thick film polymer thermistor as described in item 10 of the scope of patent application, wherein the content of the ultraviolet light curable resin is 10 wt% to 90 wt% relative to the (a) + (b ) Total weight of resin system. 15. The thick film polymer thermistor as described in item 10 of the scope of patent application, wherein the thermal hardener is selected from the group consisting of amine (Amine) hardener, acid anhydride (A nhydride) hardener, and polyfluorene. Amine-based hardeners or other latent hardeners at room temperature to high temperature (20 or more). 16. Thick film polymer thermistors as described in item 10 of the scope of patent application, in which light curing starts The initiator is selected from the group consisting of peroxides (per ο X ide) or azo compounds (Azocompound). Page 24 1236489 6. Application for patent scope 1 7. The thick film type polymer thermistor as described in item 10 of the scope of patent application, wherein the ceramic particles in the conductive filler can be ceramic powder, clay powder or hollow Glass balls; the metal layer plated on the surface of ceramic particles can be gold, silver, nickel, copper, aluminum, tin or other alloys, such as nickel-phosphorus alloys; metal plating methods include electroplating and electroless plating; conductive after plating The diameter of the particles is from 0.1 μm to 10 μm. 18. The thick film type south molecular thermistor as described in item 10 of the scope of patent application, in which the amount of conductive filler is based on the entire system, accounting for 4 5 to 80 wt%. This thick film type has high The molecular thermistor has a volume resistance value of less than 10 ohm-cm at normal temperature. 19. The thick film polymer thermistor as described in item 10 of the scope of patent application, wherein the additives include at least one of a flow control agent, a dispersant, a wetting agent, a viscosity control agent, a rheological agent, and a coupling agent. For a thick-film polymer thermistor with an addition amount of 0 to 5 wt% 〇2 0, such as the thick-film polymer thermistor under the scope of patent application No. 10, first use ultraviolet light to trigger The cross-linking reaction of the photo-curable resin produces a semi-gelatinized film, and the cross-linking reaction of the epoxy resin is initiated by thermal curing to form a polymer conductive composite film. Page 25