Temperature measuring device, protective tube, cleaning device, and method for manufacturing a temperature measuring device

Abstract

This temperature measuring device provides a significantly faster response time compared to conventional PFA-coated temperature sensors when measuring the temperature of liquids between 0°C and 300°C, enabling near real-time response speeds, and also eliminating the problem of metal ion elution from the protective tube. [Solution] The temperature measuring device for measuring the temperature of a liquid between 0°C and 300°C comprises a protective tube (10) with one end closed, and a temperature detection element (20) housed inside a temperature-sensing part at one end of the protective tube. The base material of the protective tube is a nonmetallic material having a thermal conductivity of 5 W / m·K or higher. Nonmetallic materials include glassy carbon, silicon carbide (SiC), diamond, boron nitride (BN), and aluminum nitride (AlN). The temperature detection element is one of a resistance thermometer, thermocouple, or thermistor.

Description

Technical Field

[0001] The present invention relates to a temperature measuring device, a protective tube, a cleaning device, and a method for manufacturing a temperature measuring device. In particular, the present invention relates to a temperature measuring device used for measuring the temperature of a liquid at 0°C or higher and 300°C or lower, a protective tube used for this temperature measuring device, a cleaning device using this temperature measuring device, and a method for manufacturing a temperature measuring device used for manufacturing this temperature measuring device.

Background Art

[0002] Conventionally, as a temperature measuring device used in a semiconductor cleaning device or the like, a PFA-coated temperature sensor (temperature measurement range: 0 to 200°C) in which a temperature-sensitive resistor is coated with perfluoroalkoxy alkane (PFA), which is a kind of fluororesin, has been commercially available (for example, see Non-Patent Document 1).

Prior Art Documents

Non-Patent Documents

[0003]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, according to the results of the evaluation test of the response speed during temperature measurement conducted by the present inventor, the above PFA-coated temperature sensor has an extremely slow response speed, and when the temperature of the cleaning liquid changes unintentionally, it is impossible to accurately grasp the change. Therefore, a significant improvement in the response speed of the temperature measuring device has been demanded.

[0005] Therefore, the problem that this invention aims to solve is to provide a temperature measuring device that can measure the temperature of a liquid between 0°C and 300°C with an extremely fast response speed compared to conventional PFA-coated temperature sensors, can achieve a near real-time response speed, and furthermore, does not have the problem of metal ion elution from the protective tube.

[0006] Another problem that this invention aims to solve is to provide a protective tube suitable for use in the above-mentioned temperature measuring device and a cleaning device using the above-mentioned temperature measuring device.

[0007] Another problem that this invention aims to solve is to provide a temperature measuring device that can measure the temperature of a liquid between 0°C and 300°C with an extremely fast response speed compared to conventional PFA-coated temperature sensors, enabling near real-time response speeds, and furthermore, eliminates the problem of metal ion elution from the protective tube. Moreover, even if static electricity is generated at the tip of the protective tube for any reason, it can be discharged through the ground wire, thereby preventing damage or failure of the temperature sensing element. The invention also aims to provide a cleaning device using this temperature measuring device and a suitable method for manufacturing this temperature measuring device. [Means for solving the problem]

[0008] To solve the above problems, this invention provides: A temperature measuring device for measuring the temperature of a liquid between 0°C and 300°C, A protective tube with one end closed, A temperature detection element housed inside the temperature sensing portion at one end of the protective tube, It has, The above-mentioned temperature measuring device is made of a non-metallic material with a thermal conductivity of 5 W / m·K or higher as the base material of the protective tube.

[0009] The non-metallic material that constitutes the base material of the protective tube is appropriately selected according to the specifications required for the temperature measuring device and the operating environment. However, if the liquid is a chemical solution, a material with chemical resistance is preferably selected, and to prevent static electricity buildup of the protective tube, a conductive material is preferably selected. Even if the non-metallic material does not have chemical resistance, it is possible to obtain chemical resistance by applying a chemical-resistant coating to the surface of the protective tube. Furthermore, even if the non-metallic material does not have conductivity, it is possible to obtain conductivity by applying a conductive coating such as a carbon coating or a conductive fluororesin coating to the surface of the protective tube. When a conductive fluororesin coating is used, it is possible to obtain chemical resistance in addition to conductivity. Specific examples of non-metallic materials include, but are not limited to, glassy carbon (glassy carbon), silicon carbide (SiC), diamond, boron nitride (BN), and aluminum nitride (AlN). The thermal conductivity (W / m·K) of these materials is as follows. Many of these materials are difficult to process other than by cutting in order to realize the final form of the protective tube. • Glassy carbon 6.3 (30℃) • Silicon carbide 200 (20℃) • Diamond 1000-2000°C (room temperature) Boron nitride 40-80°C (20°C) Aluminum nitride 150°C (20°C)

[0010] Protective tubes are generally constructed in a cylindrical shape. The dimensions of each part of the protective tube are appropriately selected according to the specifications required for the protective tube and the operating environment. In order to improve the response speed of a temperature measuring device using a protective tube, the outer and inner diameters of the part including the temperature sensing element (temperature measuring element) are selected to be small. Generally, for example, the outer diameter of the part including the temperature sensing element is 1 mm to 4 mm or 1 mm to 5 mm, and the inner diameter is 0.4 mm to 3 mm. Typically, the outer diameter is 1.5 mm to 3.5 mm or 1.5 mm to 4.5 mm, and the inner diameter is 0.5 mm to 2 mm or 0.5 mm to 2.5 mm. By selecting such a small outer diameter for the part including the temperature sensing element of the protective tube, combined with the fact that the base material of the protective tube has a thermal conductivity of 5 W / m·K or higher, the response speed can be dramatically improved. The protective tube may be a tube whose outer diameter does not change in the longitudinal direction, in other words, a tube whose outer diameter is the same in the central axis direction. Preferably, it has a first part containing a temperature sensing element and a second part in the direction from one end to the other, with the outer diameter of the second part being larger than the outer diameter of the first part, and the inner diameter of the second part being larger than the inner diameter of the first part. This allows the outer diameter of the first part to be selected to be small from the viewpoint of improving response speed, while the outer diameter of the second part can be matched to the part where the protective tube is attached. In addition, it is possible to improve the overall mechanical strength of the protective tube, and it is also possible to easily insert and remove the temperature sensing element housed in the protective tube and to remove the lead wires of the temperature sensing element. From the viewpoint of ensuring strength, the surface of the protective tube is typically mirror-polished to a surface roughness Ra of 0.15 to 0.7 μm.

[0011] The temperature sensing element can be basically any type as long as it can measure the temperature of a liquid between 0°C and 300°C, and is selected as needed, for example, using a resistance thermometer, thermocouple, or thermistor. The temperature sensing part of the protective tube is the part of the protective tube that corresponds to the temperature sensing part of this temperature sensing element. At least the space between the inner wall of the temperature sensing part of the protective tube and the temperature sensing element is typically filled with fine particles made of a thermally conductive and insulating material, preferably magnesium oxide (MgO) (thermal conductivity of 45-60 W / m·K), which has a high thermal conductivity, in order to minimize the obstruction of heat conduction by air.

[0012] Furthermore, this invention, A protective tube in which a temperature sensing element is housed in a temperature measuring device for measuring the temperature of a liquid between 0°C and 300°C, It is a protective tube with one end closed, and the base material is a non-metallic material having a thermal conductivity of 5 W / m·K or higher.

[0013] In this invention of the protective tube, the provisions described above in relation to the invention of the temperature measuring device are valid.

[0014] Furthermore, this invention, A cleaning apparatus that performs cleaning with a liquid at a temperature of 0°C to 300°C, The device has a temperature measuring device for measuring the temperature of the above liquid, The above temperature measuring device, A protective tube with one end closed, A temperature detection element housed inside the temperature sensing portion at one end of the protective tube, It has, The cleaning device is characterized in that the base material of the protective tube is a non-metallic material having a thermal conductivity of 5 W / m·K or higher.

[0015] The cleaning apparatus is not particularly limited, as long as it performs cleaning with a liquid at a temperature between 0°C and 300°C. The liquid used for cleaning, i.e., the cleaning solution, is appropriately selected according to the object to be cleaned, and conventionally known cleaning solutions can be used.

[0016] In the invention of this cleaning device, what has been described in relation to the invention of the above temperature measuring device holds true.

[0017] Also, this invention is a temperature measuring device for measuring the temperature of a liquid at a temperature of 0°C or higher and 300°C or lower, having a protective tube made of a non-metallic material having a thermal conductivity equal to or higher than that of vitreous carbon, chemical resistance, and conductivity, with one end closed, a temperature detection element using a resistance temperature detector, thermocouple, or thermistor housed inside the temperature sensing part on the one end side of the above protective tube, a ground wire with one end adhesively fixed to the inner wall of the above protective tube by a conductive adhesive, and the open other end of the above protective tube is sealed with resin, and the lead wires of the above temperature detection element and the above ground wire penetrate through the resin and are taken out to the outside, and is a temperature measuring device in which at least the space between the inner wall of the temperature sensing part of the above protective tube and the above temperature detection element is filled with fine particles made of a thermally conductive and insulating material.

[0018] In this temperature measuring device, the non-metallic material that is the base material of the protective tube is, for example, vitreous carbon, silicon carbide, or the like. Generally, the outer diameter of the portion including the temperature-sensitive part of the protective tube is selected to be 1 mm or more and 5 mm or less, and the inner diameter is 0.4 mm or more and 3 mm or less. Typically, the outer diameter is 1.5 mm or more and 4.5 mm or less, and the inner diameter is 0.5 mm or more and 2.5 mm or less. The protective tube may be a tube whose outer diameter does not change in the length direction, that is, whose outer diameter is the same in the central axis direction. The protective tube may also have a first part and a second part including the temperature-sensitive part in order from one end to the other end. In this case, the outer diameter of the second part is larger than the outer diameter of the first part, and the inner diameter of the second part is larger than the inner diameter of the first part. Typically, the outer diameter of the first part is 2.5 mm or more and 3.5 mm or less, and the inner diameter is 1.2 mm or more and 1.6 mm or less. In particular, when the outer diameter of the protective tube is the same in the central axis direction of the protective tube, the outer diameter of the protective tube is 1 mm or more and 5 mm or less, the inner diameter is 0.4 mm or more and 3 mm or less, and the inner diameter of the part other than the temperature-sensitive part of the protective tube is larger than the inner diameter of the part including the temperature-sensitive part. The conductive adhesive used for adhesively fixing the ground wire to the inner wall of the protective tube is selected as needed and is not particularly limited, but preferably, one with excellent thermal conductivity is used. The position for adhesively fixing one end of the ground wire to the inner wall of the protective tube is appropriately selected according to the inner diameter on the other end side of the protective tube or the like, but generally, it is within 10 mm from the other end of the protective tube, typically 5 mm or less. The resin used for sealing the other end of the protective tube is selected as needed and is not particularly limited. It may be insulating or conductive, but preferably, one with excellent thermal conductivity is used.

[0019] Preferably, the material of the protective tube is vitreous carbon, the surface roughness Ra of the surface of the protective tube is 0.15 to 0.7 μm, and the amount of residual metal elements on the surface of the protective tube is at a level that cannot be detected by analysis using energy-dispersive X-ray analysis. Since the surface roughness Ra of the surface of the protective tube is extremely small at 0.15 to 0.7 μm, it is difficult to be damaged, thereby ensuring the strength of the protective tube. In addition, since the amount of residual metal elements on the surface of the protective tube is at a level that cannot be detected by analysis using energy-dispersive X-ray analysis, the problem of elution of metal ions derived from residual metal elements when the protective tube comes into contact with a liquid can be avoided.

[0020] In temperature detection elements using resistance thermometers, preferably, the resistance thermometer is a wound element and is of the 3-wire or 4-wire type.

[0021] In this invention of a temperature measuring device, matters other than those described above are considered to have been explained in connection with the invention of the temperature measuring device described above.

[0022] Furthermore, this invention, A cleaning apparatus that performs cleaning with a liquid at a temperature of 0°C to 300°C, The device has a temperature measuring device for measuring the temperature of the above liquid, The above temperature measuring device, A protective tube, closed at one end, made of a nonmetallic material having thermal conductivity greater than that of glassy carbon, as well as chemical resistance and conductivity, A temperature detection element, such as a resistance thermometer, thermocouple, or thermistor, is housed inside the temperature sensing element at one end of the protective tube. An earth wire, with one end of which is bonded and fixed to the inner wall of the protective tube with conductive adhesive, It has, The other open end of the protective tube is sealed with resin, and the lead wires of the temperature sensing element and the ground wire are routed through the resin to the outside. This cleaning device is characterized in that at least the space between the inner wall of the temperature-sensing part of the protective tube and the temperature detection element is filled with fine particles made of a thermally conductive and insulating material.

[0023] In this invention of a cleaning apparatus, the temperature measuring device is considered to have been described in relation to the above-mentioned invention of a temperature measuring device.

[0024] Furthermore, this invention, A protective tube made of glassy carbon, with one end closed, A temperature detection element, such as a resistance thermometer, thermocouple, or thermistor, is housed inside the temperature sensing element at one end of the protective tube. An earth wire, with one end of which is bonded and fixed to the inner wall of the protective tube with conductive adhesive, It has, The other open end of the protective tube is sealed with resin, and the lead wires of the temperature sensing element and the ground wire are routed through the resin to the outside. A method for manufacturing a temperature measuring device for measuring the temperature of a liquid between 0°C and 300°C, wherein at least the space between the inner wall of the temperature-sensing part of the protective tube and the temperature detection element is filled with fine particles made of a thermally conductive and insulating material, The process of housing the temperature detection element inside the temperature sensing part of the protective tube, The process involves adhering and fixing one end of the ground wire to the inner wall of the protective tube using the conductive adhesive and bringing it out to the outside together with the lead wire. A step of filling the space between the inner wall of the temperature-sensing part of the protective tube and the temperature detection element with fine particles, A step of sealing the other open end of the protective tube with the resin, A step of cleaning the surface of the protective tube with an acid-based cleaning solution until the amount of residual metal elements on the surface of the protective tube is at a level that cannot be detected by energy-dispersive X-ray analysis, This is a method for manufacturing a temperature measuring device having [a specific feature / feature].

[0025] This method of manufacturing a temperature measuring device makes it possible to produce a temperature measuring device in which, even if metal elements adhere to the surface of the protective tube for some reason during the manufacturing process, the amount of residual metal elements on the surface of the protective tube is at a level that cannot be detected by energy-dispersive X-ray analysis. An example of metal elements adhering unintentionally to the surface of the protective tube during the manufacturing process is when some fine particles, such as magnesium oxide, that were not filled into the protective tube become airborne and adhere to the surface of the protective tube. [Effects of the Invention]

[0026] According to this invention, because the base material of the protective tube is a non-metallic material having a thermal conductivity of 5 W / m·K or higher, when measuring the temperature of a liquid between 0°C and 300°C, heat conduction occurs rapidly, causing the temperature of the protective tube to rapidly approach the liquid temperature. As a result, the temperature response speed is extremely fast compared to conventional PFA-coated temperature sensors, and it is possible to achieve a near real-time response speed. Furthermore, because the base material of the protective tube is a non-metallic material, there is no problem of metal ion elution from the protective tube. In a cleaning apparatus using this temperature measuring device, the temperature of the cleaning solution can be accurately monitored at all times, and the temperature of the cleaning solution can be stabilized by heating or cooling it as needed.

[0027] Furthermore, because the base material of the protective tube is a non-metallic material with thermal conductivity exceeding that of glassy carbon, as well as chemical resistance and conductivity, heat conduction occurs rapidly when measuring the temperature of a liquid between 0°C and 300°C, causing the temperature of the protective tube to rapidly approach the liquid temperature. As a result, the temperature response speed is extremely fast compared to conventional PFA-coated temperature sensors, and near real-time response speed is achievable. In addition, because the base material of the protective tube is a non-metallic material, there is no problem of metal ion elution from the protective tube. Moreover, even if static electricity is generated at the tip of the protective tube for any reason, it can be discharged through the ground wire, thereby preventing damage or failure of the temperature sensing element. In a cleaning apparatus using this temperature measuring device, in addition to the various advantages mentioned above, the temperature of the cleaning liquid can be accurately monitored at all times, allowing for temperature stabilization of the cleaning liquid by heating or cooling it as needed. Furthermore, according to the manufacturing method of the temperature measuring device, even if metal elements adhere to the surface of the protective tube for some reason during the manufacturing process, the amount of residual metal elements on the surface of the protective tube can be reduced to a level that is undetectable by energy-dispersive X-ray analysis, thereby avoiding the problem of metal ions derived from residual metal elements leaching into the liquid. [Brief explanation of the drawing]

[0028] [Figure 1]This is a longitudinal cross-sectional view showing a protective tube according to the first embodiment of this invention. [Figure 2] This is a longitudinal cross-sectional view showing a protective tube according to a second embodiment of the present invention. [Figure 3] This is a longitudinal cross-sectional view showing a temperature measuring device according to a third embodiment of the present invention. [Figure 4] This is an enlarged longitudinal cross-sectional view showing a first portion of the protective tube of a temperature measuring device according to a third embodiment of the present invention, and a portion of the second portion following the first portion. [Figure 5] This is a longitudinal cross-sectional view showing a temperature measuring device according to a fourth embodiment of the present invention. [Figure 6] This is an enlarged longitudinal cross-sectional view showing a first portion of the protective tube of a temperature measuring device according to a fourth embodiment of the present invention, and a portion of the second portion following the first portion. [Figure 7] This is a cross-sectional view showing the vicinity of the temperature measuring section of the piping through which the cleaning fluid flows in a cleaning device according to the fifth embodiment of this invention. [Figure 8] This is a photograph serving as a substitute for a drawing, showing the temperature measuring device according to Example 1. [Figure 9] This is a photograph serving as a substitute for a drawing, showing the temperature measuring device according to Example 2. [Figure 10] This is a photograph used as a substitute for a drawing to show a temperature measuring device in a comparative example. [Figure 11] This is a schematic diagram showing the results of an evaluation test of the response speed of the temperature measuring device according to Example 1. [Figure 12] This is a schematic diagram showing the results of an evaluation test of the response speed of the temperature measuring device according to Example 2. [Figure 13] This is a schematic diagram showing the results of an evaluation test of the response speed of a temperature measuring device using comparative examples. [Figure 14] This is a longitudinal cross-sectional view showing a temperature measuring device according to the sixth embodiment of the present invention. [Figure 15] This is a schematic diagram of the protective tube of the temperature measuring device according to the sixth embodiment of this invention, viewed from the open end side. [Figure 16]This is a schematic diagram showing an example of a wiring diagram for a resistance thermometer used as a temperature detection element in a temperature measuring device according to the sixth embodiment of this invention. [Figure 17] This is a longitudinal cross-sectional view showing a temperature measuring device according to the seventh embodiment of the present invention. [Figure 18] This is a longitudinal cross-sectional view showing a temperature measuring device according to the eighth embodiment of the present invention. [Figure 19] These are photographic representations of the protective tube of the temperature measuring device for sample 1 according to Example 3, before cleaning, and a photographic representation of a scanning electron microscope image of a part of the surface of this protective tube. [Figure 20] This is a schematic diagram showing the results of energy-dispersive X-ray analysis of the surface of the protective tube of the temperature measuring device for sample 1 according to Example 3, before cleaning. [Figure 21] This is a photograph used as a substitute for a drawing, showing a scanning electron microscope image of a portion of the surface of the protective tube of the temperature measuring device for sample 1 according to Example 3, before cleaning. [Figure 22] This is a photograph used as a substitute for a drawing, showing a scanning electron microscope image of a portion of the surface of the protective tube of the temperature measuring device for sample 1 according to Example 3, before cleaning. [Figure 23] This is a schematic diagram showing the results of energy-dispersive X-ray analysis of the surface of the protective tube of the temperature measuring device for sample 1 according to Example 3, before cleaning. [Figure 24] These are photographic representations of the appearance of the protective tube of the temperature measuring device for sample 2 according to Example 4 after one hour of cleaning, and photographic representations of the scanning electron microscope image of a part of the surface of this protective tube. [Figure 25] This is a schematic diagram showing the results of energy-dispersive X-ray analysis of the surface of the protective tube of the temperature measuring device for sample 2 according to Example 4 after one hour of cleaning. [Figure 26] This is a photograph in lieu of a drawing, showing a scanning electron microscope image of a portion of the surface of the protective tube of the temperature measuring device for sample 2 according to Example 4, after one hour of cleaning. [Figure 27] This is a photograph in lieu of a drawing, showing a scanning electron microscope image of a portion of the surface of the protective tube of the temperature measuring device for sample 2 according to Example 4, after one hour of cleaning. [Figure 28]This is a schematic diagram showing the results of energy-dispersive X-ray analysis of the surface of the protective tube of the temperature measuring device for sample 2 according to Example 4 after one hour of cleaning. [Figure 29] These are photographic representations of the appearance of the protective tube of the temperature measuring device for sample 2 according to Example 4 after 24 hours of cleaning, and photographic representations of the scanning electron microscope image of a part of the surface of this protective tube. [Figure 30] This is a schematic diagram showing the results of energy-dispersive X-ray analysis of the surface of the protective tube of the temperature measuring device for sample 2 according to Example 4 after 24 hours of cleaning. [Figure 31] This is a photograph in lieu of a drawing showing a scanning electron microscope image of a portion of the surface of the protective tube of the temperature measuring device for sample 2 according to Example 4, after 24 hours of cleaning. [Figure 32] This is a photograph in lieu of a drawing showing a scanning electron microscope image of a portion of the surface of the protective tube of the temperature measuring device for sample 2 according to Example 4, after 24 hours of cleaning. [Figure 33] This is a schematic diagram showing the results of energy-dispersive X-ray analysis of the surface of the protective tube of the temperature measuring device for sample 2 according to Example 4 after 24 hours of cleaning. [Modes for carrying out the invention]

[0029] The following describes embodiments for carrying out the invention.

[0030] <First Embodiment> [Protection tube] Figure 1 shows a protective tube 10 according to the first embodiment. This protective tube 10 is used to house a temperature sensing element in a temperature measuring device for measuring the temperature of a liquid between 0°C and 300°C.

[0031] As shown in Figure 1, the protective tube 10 has a stepped cylindrical shape overall. The base material of the protective tube 10 is a non-metallic material having a thermal conductivity of 5 W / m·K or more, and is selected from, for example, the materials already mentioned. One end of the protective tube 10 is closed and the other end is open. The protective tube 10 has a first part 11 and a second part 12, which include a temperature sensing element, in order from the closed end toward the other end. The second part 12 is used when attaching the protective tube 10 to the mounting part of a device that uses a temperature measuring device. In this case, the outer diameter D2 of the second part 12 is larger than the outer diameter D1 of the first part 11, and the inner diameter d2 of the second part 12 is larger than the inner diameter d1 of the first part 11. The outer diameter of the boundary 13 between the first part 11 and the second part 12 increases linearly from the outer diameter D1 of the first part 11 to the outer diameter D2 of the second part 12. Furthermore, the inner diameter of the boundary portion 13 increases linearly from the inner diameter d1 of the first portion 11 to the inner diameter d2 of the second portion 12. A temperature detection element (not shown) is housed in the space inside the temperature sensing portion of the first portion 11. The length L1 of the first portion 11 is typically chosen to be greater than the length of the temperature detection portion of the temperature detection element.

[0032] For example, the outer diameter D1 of the first part 11 is selected to be between 2 mm and 4 mm, and the inner diameter d1 is selected to be between 1 mm and 2 mm. Typically, the outer diameter D1 is selected to be between 2.5 mm and 3.5 mm, and the inner diameter d1 is selected to be between 1.2 mm and 1.6 mm.

[0033] The length L1 of the first part 11, the length L2 of the second part 12, the length L3 of the boundary part 13, the distance L4 between the bottom surface of the hollow part of the first part 11 and the tip of the first part 11 (thickness of the tip of the first part 11), and the total length L5 (=L1+L3+L2) are selected as needed, for example, L1 is 9-12 mm, L2 is 30-50 mm, L3 is 0.5-1 mm, L4 is 0.7-1.3 mm, and L5 is, for example, 40-60 mm.

[0034] As described above, according to this first embodiment of the protective tube 10, in addition to the fact that the base material of the protective tube 10 is a non-metallic material having a thermal conductivity of 5 W / m·K or more, the outer diameter D1 of the first portion 11 having a temperature sensing section housing the temperature sensing element is selected to be, for example, 2 mm to 4 mm, the inner diameter d1 to be 1 mm to 2 mm, or the outer diameter D1 to be, for example, 2.5 mm to 3.5 mm, and the inner diameter d1 to be 1.2 mm to 1.6 mm. As a result, when used in a temperature measuring device, the response speed when measuring the temperature of a liquid between 0°C and 300°C can be greatly improved, and a near real-time response speed can be achieved. Furthermore, because the base material of the protective tube 10 is a non-metallic material, it is possible to prevent the elution of metal ions when it comes into contact with a liquid.

[0035] <Second Embodiment> [Protection tube] Figure 2 shows a protective tube 10 according to a second embodiment. This protective tube 10 is used to house a temperature sensing element in a temperature measuring device for measuring the temperature of a liquid between 0°C and 300°C.

[0036] As shown in Figure 2, the protective tube 10, like the protective tube 10 according to the first embodiment, has an overall stepped cylindrical shape and comprises a first part 11 and a second part 12, but differs in that the length L1, outer diameter D1, and inner diameter d1 of the first part 11 are smaller than those of the protective tube 10 according to the first embodiment. Specifically, the length L1 of the first part 11 is selected to be 4.5 to 6.5 mm, the outer diameter D1 to be, for example, 1.5 mm or more and 2.5 mm or less, and the inner diameter d1 to be 0.4 mm or more and 1 mm or less, typically the outer diameter D1 to be 1.8 mm or more and 2.2 mm or less, and the inner diameter d1 to be 0.5 mm or more and 0.7 mm or less. Similar to the protective tube 10 according to the first embodiment, the outer diameter D2 of the second portion 12 is greater than the outer diameter D1 of the first portion 11, and the inner diameter d2 of the second portion 12 is greater than the inner diameter d1 of the first portion 11, and the outer diameter of the boundary portion 13 between the first portion 11 and the second portion 12 increases linearly from the outer diameter D1 of the first portion 11 to the outer diameter D2 of the second portion 12. The outer diameter D2, inner diameter d2, and total length L5 of the second portion 12 are the same as those of the protective tube 10 according to the first embodiment. The length L3 of the boundary portion 13 and the distance L4 between the bottom surface of the hollow portion of the first portion 11 and the tip of the first portion 11 are selected as needed.

[0037] Other than the above, this protective tube 10 is the same as the protective tube 10 according to the first embodiment.

[0038] According to this second embodiment of the protective tube 10, in addition to the fact that the base material of the protective tube 10 is a non-metallic material having a thermal conductivity of 5 W / m·K or higher, the outer diameter D1 of the first portion 11 having a temperature sensing section housing a temperature sensing element is selected to be, for example, 1.5 mm to 2.5 mm, the inner diameter d1 to be 0.4 mm to 1 mm, or the outer diameter D1 to be 1.8 mm to 2.2 mm, and the inner diameter d1 to be 0.5 mm to 0.7 mm. As a result, when used in a temperature measuring device, the response speed when measuring the temperature of a liquid between 0°C and 300°C can be greatly improved, and a near real-time response speed can be achieved. Furthermore, because the base material of the protective tube 10 is a non-metallic material, it is possible to prevent the elution of metal ions when it comes into contact with a liquid.

[0039] <Third Embodiment> [Temperature measurement device] Figure 3 shows a temperature measuring device according to a third embodiment. Figure 4 shows an enlarged view of the first part 11 of this temperature measuring device and a portion of the second part 12 that follows the first part 11. As shown in Figures 3 and 4, in this temperature measuring device, a temperature detection element 20 is housed inside the temperature sensing part of the first part 11 of the protective tube 10 according to the first embodiment. In this example, the temperature sensing part extends for almost the entire length of the first part 11, and the temperature detection element 20 is close to the almost entire length of the first part 11. Figures 3 and 4 show the case where the length of the temperature detection part of the temperature detection element 20 is approximately the same as the length of the temperature detection element 20. Figures 3 and 4 show the case where there is a gap between the tip of the temperature detection element 20 and the bottom surface of the hollow part of the first part 11, but are not limited to this, and there may be no gap. The temperature detection element 20 is, for example, a resistance thermometer, a thermocouple, or a thermistor. Although not shown in the diagram, the lead wires of the temperature sensing element 20 are brought out to the outside from the open end of the second part 12. The lead wires are covered with an electrically insulating tube, such as polytetrafluoroethylene (PTFE). Also, although not shown in the diagram, the inside of the protective tube 10 is preferably filled with fine particles made of a thermally conductive and insulating material such as MgO, which has high thermal conductivity, filling the space between the temperature sensing element 20 and the inner wall of the protective tube 10. This ensures good heat conduction between the protective tube 10 and the temperature sensing element 20.

[0040] According to this third embodiment of the temperature measuring device, since the temperature detection element 20 is housed inside the temperature sensing part of the first portion 11 of the protective tube 10 according to the first embodiment, an extremely fast response speed can be obtained when measuring the temperature of a liquid between 0°C and 300°C using this temperature measuring device, and a near real-time response speed can be achieved. Furthermore, the elution of metal ions from the protective tube 10 can be prevented.

[0041] <Fourth Embodiment> [Temperature measurement device] Figure 5 shows a temperature measuring device according to the fourth embodiment. Figure 6 shows an enlarged view of the first part 11 of this temperature measuring device and a portion of the second part 12 that follows the first part 11. As shown in Figures 5 and 6, in this temperature measuring device, a temperature detection element 20 is housed inside the temperature sensing portion of the first part 11 of the protective tube 10 according to the second embodiment. In this example, the temperature sensing portion is the portion of the first part 11 excluding the upper part, and the length of the temperature detection element 20 is shorter than the length L1 of the first part 11. The length of the temperature detection portion of the temperature detection element 20 is, for example, approximately the same as the length of the temperature detection element 20. In Figures 5 and 6, there is a gap between the tip of the temperature detection element 20 and the bottom surface of the hollow portion of the first part 11, but this is not limited to this, and there may be no gap. Everything else about this temperature measuring device is the same as the temperature measuring device according to the third embodiment.

[0042] The temperature measuring device according to this fourth embodiment offers similar advantages to the temperature measuring device according to the third embodiment.

[0043] <Fifth Embodiment> [Washing equipment] Figure 7 shows the area near the temperature measuring section of the piping through which the cleaning fluid flows in a cleaning apparatus according to the fifth embodiment. This cleaning apparatus is typically a semiconductor cleaning apparatus, but is not limited to it. The other components of this cleaning apparatus are the same as those of conventionally known cleaning apparatuses. As shown in Figure 7, a pipe 40 for attaching a temperature measuring device is provided perpendicular to the pipe 30 in the middle of the pipe 30 through which the cleaning fluid flows. A temperature measuring device 50 is inserted into this pipe 40. The temperature measuring device 50 is a temperature measuring device according to the third or fourth embodiment, but Figure 7 shows a temperature measuring device according to the third embodiment. The center of the temperature sensing part of the first part 11 at the tip of the temperature measuring device 50 is positioned approximately on the center line of the pipe 30. The space between the pipe 40 and the protective pipe 10 of the temperature measuring device 50 is sealed to prevent leakage of the cleaning fluid from the pipe 40. For example, when cleaning silicon wafers, a cleaning fluid such as SC1 (Standard Clean 1) is used.

[0044] According to this fifth embodiment of the cleaning apparatus, the temperature of the cleaning solution can be measured using the temperature measuring device 50 according to the third or fourth embodiment. Therefore, changes in the temperature of the cleaning solution can be grasped quickly, for example, at a near real-time rate, and the temperature of the cleaning solution can be stabilized by heating or cooling it as needed. This enables effective cleaning.

[0045] (Example 1) In Example 1, a protective tube 10 according to the first embodiment was fabricated, and a temperature measuring device according to the third embodiment was assembled using the fabricated protective tube 10. The fabricated protective tube 10 was made of glassy carbon, with D1 being 3 mm, d1 being 1.4 mm, L1 being approximately 11 mm, L3 being approximately 1 mm, L4 being approximately 1 mm, and L5 being approximately 50 mm. The surface of the protective tube 10 was mirror-polished to Ra = 0.2 μm. As the temperature detection element 20, a wound element (resistance thermometer) of model C-1210 manufactured by Netsushin Co., Ltd., with a diameter of 1.2 mm and a length of 10 mm, was used. PTFE coated wires were used for the lead wires. Figure 8 shows the temperature measuring device assembled in this way. This glassy carbon protective tube 10 has chemical resistance and conductivity.

[0046] (Example 2) In Example 2, a protective tube 10 according to the second embodiment was fabricated, and a temperature measuring device according to the fourth embodiment was assembled using the fabricated protective tube 10. The fabricated protective tube 10 was made of glassy carbon, with D1 being 2 mm, d1 being 0.6 mm, L1 being approximately 5.5 mm, L3 being approximately 0.5 mm, L4 being approximately 1 mm, and L5 being approximately 50 mm. The surface of the protective tube 10 was mirror-polished to Ra = 0.2 μm. As the temperature detection element 20, a wound element (resistance thermometer) with a diameter of 0.4 mm and a length of 3 mm, model MC-0403, manufactured by Netsushin Co., Ltd., was used. PTFE coated wires were used for the lead wires. Figure 9 shows the temperature measuring device assembled in this way. This glassy carbon protective tube 10 has chemical resistance and conductivity.

[0047] (Comparative example) As a comparative example, a PFA coating temperature sensor, model number FR-100, manufactured by Rika Kogyo Co., Ltd., was used. Figure 10 shows this PFA coating temperature sensor.

[0048] (Evaluation test of the response speed of a temperature measuring device) In Example 1, the temperature measuring device was inserted into a container filled with ice, and after measuring the freezing point, the device was instantly transferred to another container containing boiling water. Figure 11 shows the results of measuring the temperature change from the time of transfer. A similar experiment was conducted with the temperature measuring device in Example 2. Figure 12 shows the results of measuring the temperature change from the time of transfer. As shown in Figure 11, in Example 1, the time taken to detect the temperature when the temperature rose from 0°C to 100°C was 6 seconds. As shown in Figure 12, in Example 2, the time taken to detect the temperature when the temperature rose from 0°C to 100°C was 2 seconds.

[0049] The comparative example's temperature measuring device was inserted into a container of water at 25°C, and after measuring 25°C, the water was transferred to another container of water at 80°C. Figure 13 shows the results of measuring the temperature change from the time of transfer. As shown in Figure 13, the response time for the comparative example's temperature measuring device to reach 80°C from 25°C was 36 seconds.

[0050] From these results, it was found that the temperature measuring devices in Examples 1 and 2 have a response speed that is more than six times faster than the temperature measuring device in the comparative example.

[0051] <Sixth Embodiment> [Temperature measurement device] Figure 14 shows a temperature measuring device according to the sixth embodiment. Figure 15 is a view of the protective tube 10 of this temperature measuring device from the open end side. As shown in Figure 14, this temperature measuring device has a protective tube 10 and a temperature detection element 20 similar to the protective tube 10 and temperature detection element 20 of the temperature measuring device according to the third embodiment. The base material of the protective tube 10 is a non-metallic material having a thermal conductivity greater than or equal to the thermal conductivity of glassy carbon, as well as chemical resistance and conductivity, such as glassy carbon or silicon carbide. In particular, when the base material of the protective tube 10 is glassy carbon, the surface roughness Ra of the surface of the protective tube 10 is 0.15 to 0.7 μm, and the amount of residual metal elements on the surface of the protective tube 10 is at a level that cannot be detected by energy dispersive X-ray analysis. The temperature detection element 20 uses a resistance thermometer, thermocouple, or thermistor. Lead wires 21 extend from the temperature detection element 20. The lead wires 21 consist of three or four wires if the temperature sensing element 20 is a resistance thermometer consisting of a three-wire or four-wire wound element, and two wires if the temperature sensing element 20 is a thermocouple or thermistor. Figure 16 shows an example wiring diagram of a resistance thermometer consisting of a three-wire wound element. The resistor is, for example, Pt (platinum) 100 ohms. The lead wires 21 are twisted together to form a stranded wire 22, which is brought out to the outside from the open end of the protective tube 10. One end of the ground wire 60 is bonded and fixed to the inner wall of the protective tube 10 within, for example, 10 mm, typically within 5 mm from the open end, using a conductive adhesive (not shown). For example, a conductive epoxy resin is used as the conductive adhesive. The ground wire 60 is also brought out to the outside from the open end of the protective tube 10. The open end of the protective tube 10 is sealed with resin 70. The resin 70 may be insulating or conductive. For example, an epoxy resin is used as the resin 70. The stranded wire 22 and the ground wire 60 are brought out to the outside by passing through the resin 70. Although not shown in the figures, the space between the inner wall of the protective tube 10 and the temperature sensing element 20, lead wire 21 and stranded wire 22 located inside the protective tube 10 is preferably filled with fine particles made of a thermally conductive and insulating material such as MgO having high thermal conductivity, thereby ensuring good heat conduction between the protective tube 10 and the temperature sensing element 20.Other than the above, this temperature measuring device is the same as the temperature measuring device according to the third embodiment.

[0052] The temperature measuring device according to this sixth embodiment offers the same advantages as the temperature measuring device according to the third embodiment, plus the following advantages. Specifically, since one end of the ground wire 60 is bonded and fixed to the inner wall of the protective tube 10 with a conductive adhesive, even if static electricity is generated at the tip of the protective tube 10 for any reason, it can be discharged through the ground wire 60, thereby preventing damage or failure of the temperature sensing element 20. Furthermore, if the base material of the protective tube 10 is glassy carbon, the surface roughness Ra of the protective tube 10 is 0.15 to 0.7 μm, making it less susceptible to damage and thus ensuring the strength of the protective tube 10. In addition, since the amount of residual metal elements on the surface of the protective tube 10 is at a level that cannot be detected by energy-dispersive X-ray analysis, the problem of metal ions originating from residual metal elements eluting when the protective tube 10 comes into contact with the liquid whose temperature is to be measured can be avoided.

[0053] <Seventh Embodiment> [Temperature measurement device] Figure 17 shows a temperature measuring device according to the seventh embodiment. The view of the protective tube 10 of this temperature measuring device from the open end is the same as in Figure 15. As shown in Figure 17, this temperature measuring device has a protective tube 10 and a temperature detection element 20 similar to those of the temperature measuring device according to the fourth embodiment. Everything else about this temperature measuring device is the same as that of the temperature measuring device according to the sixth embodiment.

[0054] The temperature measuring device according to this seventh embodiment offers similar advantages to the temperature measuring device according to the sixth embodiment.

[0055] <Eighth Embodiment> [Temperature measurement device] Figure 18 shows a temperature measuring device according to the eighth embodiment. As shown in Figure 18, the outer diameter D of the protective tube 10 of this temperature measuring device is the same in the direction of the central axis. The inner diameter of the portion of the protective tube 10 including the temperature sensing part, i.e., the portion from one closed end of the protective tube 10 to a length L1, is d1, and the inner diameter of the portion from the other end of the protective tube 10 to a length L2 is d2, where d2 > d1. The inner diameter of the boundary portion 13 with a length L3 between portion L1 and portion L2 increases linearly from the inner diameter d1 of portion L1 to the inner diameter d2 of portion L2. However, the boundary portion 13 is not required, in which case L3 = 0.

[0056] For example, the outer diameter D of the protective tube 10 is selected to be between 2 mm and 5 mm, the inner diameter d1 of the section with length L1 is selected to be between 1 mm and 2 mm, the inner diameter d2 of the section with length L2 is selected to be between 1.2 mm and 1.6 mm, L1 is selected to be between 5 mm and 12 mm, and L2 is selected to be between 38 mm and 45 mm. In one example, D=4, d1=1.4 mm, d2=2 mm, L3=0, L1=11.5 mm, L2=38.5 mm, and the thickness of the tip of the protective tube 10 is 1 mm. In another example, D=4, d1=1.4 mm, d2=2 mm, L3=0, L1=6.5 mm, L2=33.5 mm, and the thickness of the tip of the protective tube 10 is 1 mm.

[0057] Other than the above, this temperature measuring device is the same as the temperature measuring device according to the sixth embodiment.

[0058] The temperature measuring device according to this eighth embodiment offers similar advantages to the temperature measuring device according to the sixth embodiment.

[0059] <Ninth Embodiment> [Manufacturing method for temperature measuring device] The ninth embodiment is a method for manufacturing a temperature measuring device according to the sixth to eighth embodiments. In this method for manufacturing a temperature measuring device, the temperature measuring device is manufactured as follows.

[0060] First, the temperature detection element 20 is housed inside the temperature-sensing section of the pre-prepared protective tube 10. Lead wires 21 and stranded wires 22 are connected to the temperature detection element 10.

[0061] Next, one end of the ground wire 60 is bonded and fixed to the inner wall of the protective tube 10 with a conductive adhesive and brought out to the outside together with the stranded wire 22. The position where one end of the ground wire 60 is bonded and fixed is, for example, within 10 mm, typically within 5 mm, from the open end of the protective tube 10.

[0062] Next, the space between the inner wall of the protective tube 10 and the temperature sensing element 20, lead wire 21, and stranded wire 22 located inside the protective tube 10 is filled with fine particles made of a thermally conductive and insulating material such as MgO. Typically, the powder made of fine particles such as MgO is filled from the open end of the protective tube 10.

[0063] Next, the open end of the protective tube 10 is sealed with resin 70.

[0064] Next, the surface of the protective tube 10 is cleaned with a cleaning solution containing an acid, such as hydrochloric acid. The cleaning is continued until the amount of residual metal elements on the surface of the protective tube 10 is at a level that is not detectable by energy-dispersive X-ray analysis.

[0065] In this manner, the desired temperature measuring device is manufactured.

[0066] (Example 3) In Example 3, a protective tube 10 according to the first embodiment was fabricated, and a temperature measuring device according to the sixth embodiment was assembled using the fabricated protective tube 10. The fabricated protective tube 10 was made of glassy carbon, with D1 being 3 mm, d1 being 1.4 mm, L1 being approximately 11 mm, L3 being approximately 1 mm, L4 being approximately 1 mm, and L5 being approximately 50 mm. The surface of the protective tube 10 was mirror-polished to Ra = 0.2 μm. As the temperature detection element 20, a 3-wire wound element (resistance thermometer) of model C-1210 manufactured by Netsushin Co., Ltd., with a diameter of 1.2 mm and a length of 10 mm, was used. PTFE coated wires were used for the lead wires. Figure 19A shows the temperature measuring device assembled in this way (referred to as Sample 1). Figure 19B is a scanning electron microscope image of a part of the surface of the protective tube 10.

[0067] Energy-dispersive X-ray spectroscopy was used to evaluate the elements remaining on the surface of the protective tube 10 of sample 1 (the part shown in Figure 19B). The results are shown in Figure 20. In Figure 20, sample 1, which was analyzed at the part shown in Figure 19B, is labeled as sample 1-1. From Figure 20, carbon (C), oxygen (O), sodium (Na), magnesium (Mg), sulfur (S), and potassium (K) were detected.

[0068] Energy-dispersive X-ray spectroscopy was performed on a portion of the surface of the protective tube 10 of sample 1, separate from the portion shown in Figure 19B, specifically the portions shown in Figures 21 and 22, to perform a similar evaluation. The results are shown in Figure 23. In Figure 23, the portions of sample 1 analyzed in Figures 21 and 22 are labeled as sample 1-2 and 1-3, respectively. From Figure 23, C, O, and F were detected in sample 1-2, and C, O, and Al (aluminum) were detected in sample 1-3.

[0069] As can be seen from the above results, metallic elements such as Mg and Al were detected on the surface of the protective tube 10 of sample 1.

[0070] (Example 4) In Example 4, a temperature measuring device similar to that in Example 3 was assembled, and then the wiring was protected using heat shrink tubing (this temperature measuring device was referred to as Sample 2).

[0071] The surface of the protective tube 10 of sample 2 was washed with 5% hydrochloric acid for 1 hour. The washing was performed by immersing the protective tube 10 of sample 2 in 5% hydrochloric acid. Figure 24A shows the appearance of the protective tube 10 of sample 2 after washing for 1 hour. Figure 24B is a scanning electron microscope image of a portion of the surface of the protective tube 10 of sample 2 after washing for 1 hour.

[0072] Energy-dispersive X-ray spectroscopy was used to evaluate the elements remaining on the surface of the protective tube 10 of sample 2 after 1 hour of washing (the area shown in Figure 24B). The results are shown in Figure 25. In Figure 25, sample 2 analyzed at the area shown in Figure 24B is labeled as sample 2-1. From Figure 25, C, N (nitrogen), O, Al, Si (silicon), S, and Cl (chlorine) were detected.

[0073] Energy-dispersive X-ray spectroscopy was performed on a portion of the protective tube 10 surface of sample 2, separate from the portion shown in Figure 24B, as shown in Figures 26 and 27, to perform a similar evaluation. The results are shown in Figure 28. In Figure 28, the portions of sample 2 analyzed in Figures 26 and 27 are labeled as sample 2-2 and 2-3, respectively. From Figure 28, C, N, O, Al, Si, and S were detected in the protective tube 10 of sample 2-2, while C, O, Na, Mg, Al, Si, S, Cl, and K were detected in the protective tube 10 of sample 2-3.

[0074] As can be seen from the above results, metallic elements such as Mg and Al were detected on the surface of the protective tube 10 of sample 2 after washing with 5% hydrochloric acid for 1 hour.

[0075] The surface of the protective tube 10 of sample 2 was washed with 5% hydrochloric acid for 1 hour, and then further washed with 5% hydrochloric acid for 23 hours. The total washing time was 24 hours. The washing was performed by immersing the protective tube 10 of sample 2 in 5% hydrochloric acid. Figure 29A shows the appearance of the protective tube 10 of sample 2 after 24 hours of washing. Figure 29B is a scanning electron microscope image of a portion of the surface of the protective tube 10 of sample 2 after 24 hours of washing.

[0076] Energy-dispersive X-ray spectroscopy was used to evaluate the elements remaining on the surface of the protective tube 10 of sample 2 after 24 hours of washing (the area shown in Figure 29B). The results are shown in Figure 30. In Figure 30, sample 2 analyzed at the area shown in Figure 29B is labeled as sample 2-4. From Figure 30, only C and O were detected; metallic elements such as Mg and Al were not detected.

[0077] Energy-dispersive X-ray spectroscopy was performed on a portion of the protective tube 10 surface of sample 2, separate from the portion shown in Figure 29B, after 24 hours of washing, specifically the portions shown in Figures 31 and 32, to perform a similar evaluation. The results are shown in Figure 33. In Figure 33, the portions of sample 2 analyzed in Figures 31 and 32 are labeled as sample 2-5 and 2-6, respectively. From Figure 33, only C, F, and Si were detected in the protective tube 10 of sample 2-5, and only C, N, O, Si, S, and Cl were detected in the protective tube 10 of sample 2-6; no metallic elements such as Mg or Al were detected in either sample.

[0078] As can be seen from the above results, no metallic elements such as Mg or Al were detected on the surface of the protective tube 10 of sample 2 after washing with 5% hydrochloric acid for 24 hours.

[0079] Although embodiments of this invention have been described in detail above, this invention is not limited to the embodiments described above, and various modifications based on the technical idea of ​​this invention are possible.

[0080] For example, the numerical values, structures, configurations, materials, and methods mentioned in the above-described embodiments are merely examples, and different numerical values, structures, configurations, materials, and methods may be used as needed. [Explanation of Symbols]

[0081] 10…Protective tube, 11…First part, 12…Second part, 13…Boundary section, 20…Temperature sensing element, 21…Lead wire, 22…Stranded wire, 60…Ground wire, 70…Resin

Claims

1. A temperature measuring device for measuring the temperature of a liquid between 0°C and 300°C, A protective tube, closed at one end, made of a nonmetallic material having thermal conductivity greater than that of glassy carbon, as well as chemical resistance and conductivity, A temperature detection element, such as a resistance thermometer, thermocouple, or thermistor, is housed inside the temperature sensing element at one end of the protective tube. An earth wire, with one end of which is bonded and fixed to the inner wall of the protective tube with conductive adhesive, It has, The other open end of the protective tube is sealed with resin, and the lead wires of the temperature sensing element and the ground wire are routed through the resin to the outside. A temperature measuring device in which at least the space between the inner wall of the temperature-sensing part of the protective tube and the temperature detection element is filled with fine particles made of a thermally conductive and insulating material.

2. The temperature measuring device according to claim 1, wherein the nonmetallic material is glassy carbon or silicon carbide.

3. The temperature measuring device according to claim 1, wherein the material of the protective tube is glassy carbon, the surface roughness Ra of the surface of the protective tube is 0.15 to 0.7 μm, and the amount of residual metal elements on the surface of the protective tube is at a level that cannot be detected by analysis by energy dispersive X-ray spectroscopy.

4. The temperature measuring device according to claim 1, wherein one end of the above-mentioned ground wire is adhered to and fixed to the inner wall of the above-mentioned protective tube within 10 mm from the other end.

5. The temperature measuring device according to claim 1, wherein the outer diameter of the portion of the protective tube including the temperature sensing element is 1 mm or more and 5 mm or less, and the inner diameter is 0.4 mm or more and 3 mm or less.

6. The temperature measuring device according to any one of claims 1 to 4, wherein the protective tube has a first portion and a second portion, in order from one end toward the other end, the outer diameter of the second portion being larger than the outer diameter of the first portion, and the inner diameter of the second portion being larger than the inner diameter of the first portion.

7. The temperature measuring device according to claim 6, wherein the outer diameter of the first part is 2.5 mm or more and 3.5 mm or less, and the inner diameter is 1.2 mm or more and 1.6 mm or less.

8. The temperature measuring device according to claim 1, wherein the outer diameter of the protective tube is the same in the central axis direction of the protective tube, the outer diameter of the protective tube is 1 mm or more and 5 mm or less, the inner diameter is 0.4 mm or more and 3 mm or less, and the inner diameter of the part of the protective tube other than the temperature sensing part is larger than the inner diameter of the part including the temperature sensing part.

9. The temperature measuring device according to any one of claims 1 to 5, wherein the above-mentioned resistance thermometer uses a wound element and is 3-wire or 4-wire.

10. A cleaning apparatus that performs cleaning with a liquid at a temperature of 0°C or higher and 300°C or lower, The device has a temperature measuring device for measuring the temperature of the above liquid, The above temperature measuring device, A protective tube, closed at one end, made of a nonmetallic material having thermal conductivity greater than that of glassy carbon, as well as chemical resistance and conductivity, A temperature detection element, such as a resistance thermometer, thermocouple, or thermistor, is housed inside the temperature sensing element at one end of the protective tube. An earth wire, with one end of which is bonded and fixed to the inner wall of the protective tube with conductive adhesive, It has, The other open end of the protective tube is sealed with resin, and the lead wires of the temperature sensing element and the ground wire are routed through the resin to the outside. A cleaning device in which at least the space between the inner wall of the temperature-sensing part of the protective tube and the temperature detection element is filled with fine particles made of a thermally conductive and insulating material.

11. A protective tube made of glassy carbon, with one end closed, A temperature detection element, such as a resistance thermometer, thermocouple, or thermistor, is housed inside the temperature sensing element at one end of the protective tube. An earth wire, with one end of which is bonded and fixed to the inner wall of the protective tube with conductive adhesive, It has, The other open end of the protective tube is sealed with resin, and the lead wires of the temperature sensing element and the ground wire are routed through the resin to the outside. A method for manufacturing a temperature measuring device for measuring the temperature of a liquid between 0°C and 300°C, wherein at least the space between the inner wall of the temperature-sensing part of the protective tube and the temperature detection element is filled with fine particles made of a thermally conductive and insulating material, The process of housing the temperature detection element inside the temperature sensing part of the protective tube, The process involves bonding and fixing one end of the ground wire to the inner wall of the protective tube using the conductive adhesive, and then bringing it out to the outside together with the lead wire. A step of filling the space between the inner wall of the temperature-sensing part of the protective tube and the temperature detection element with fine particles, A step of sealing the other open end of the protective tube with the resin, A step of cleaning the surface of the protective tube with an acid-based cleaning solution until the amount of residual metal elements on the surface of the protective tube is at a level that cannot be detected by energy-dispersive X-ray analysis, A method for manufacturing a temperature measuring device having the following characteristics.

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