Heater element with functional material-containing layer, heater unit with functional material-containing layer, vehicle interior purification system, and honeycomb structure

Abstract

Provided is a heater element 200 equipped with a functional-material-containing layer, said heater element 200 comprising: a honeycomb structure 10 having an outer peripheral wall 11 and a partition wall 14 that is disposed on the inside of the outer peripheral wall 11 and that defines and forms a plurality of cells 13 forming a flow passage extending from a first end surface 12a to a second end surface 12b, at least the partition wall 14 being configured from a material having PTC characteristics; a pair of electrodes 30 provided to the first end surface 12a and the second end surface 12b of the honeycomb structure 10; and a functional-material-containing layer 20 provided to a surface of the partition wall 14.

Description

[Technical Field]

[0001] The present invention relates to a heater element with a functional material-containing layer, a heater unit with a functional material-containing layer, a vehicle interior purification system, and a honeycomb structure. [Background technology]

[0002] There is a growing demand for improved cabin environments in automobiles and other vehicles. Specific demands include reducing CO2 emissions in the cabin to suppress driver drowsiness and removing harmful volatile components such as odorous components and allergy-inducing substances from the cabin. Ventilation is the most effective way to address these demands, but ventilation can significantly reduce heating energy in winter, resulting in poor energy efficiency. This energy loss, particularly in battery electric vehicles (BEVs), poses a significant problem: it significantly reduces the vehicle's driving range.

[0003] As a method for solving the above problems, Patent Document 1 discloses a vehicle interior purification system that captures components to be removed, such as CO2, in the air in the vehicle interior using a functional material such as an adsorbent, and then reacts or desorbs the components by heating, causing them to be released outside the vehicle. Such a vehicle interior purification system requires as much contact between the air and the functional material as possible to ensure the ability to capture the components to be removed, and requires that the functional material be able to be heated to a predetermined temperature to facilitate the release of the captured components from the functional material.

[0004] On the other hand, Patent Document 2 discloses a heater element including a columnar honeycomb structure having an outer peripheral side wall and partition walls disposed inside the outer peripheral side wall and defining a plurality of cells that form flow paths from a first end face to a second end face, the partition walls having PTC characteristics, an average thickness of 0.13 mm or less, and an opening ratio at the first and second end faces of 0.81 or more. This heater element is used as a heater for heating a vehicle interior. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2020-104774 [Patent Document 2] International Publication No. 2020 / 036067 Summary of the Invention [Problem to be solved by the invention]

[0006] The heater element described in Patent Document 2 is used for heating the vehicle interior, but is also thought to be useful as a support for supporting functional materials. In particular, the heater element described in Patent Document 2 can be heated by passing current and has PTC properties, so it is thought that it can easily heat functional materials while also suppressing heating to excessive temperatures and suppressing thermal degradation of the functional materials. However, the inventors' investigations revealed that when a functional material is applied to the heater element described in Patent Document 2, the cells of the columnar honeycomb structure are clogged with the functional material, or the opening area of ​​the cells carrying the functional material becomes too small. In such a state, contact between the air and the functional material is hindered, and pressure loss increases when the air passes through the cells, making it impossible to ensure a sufficient air flow rate. Therefore, the heater element described in Patent Document 2 is not suitable for applications that utilize the functions of the functional material, and there is room for improvement.

[0007] The present invention has been made to solve the above-mentioned problems, and aims to provide a heater element with a functional material-containing layer, a heater unit with a functional material-containing layer, and a vehicle interior purification system that can fully utilize the functions of the functional material. Another object of the present invention is to provide a honeycomb structure suitable for producing the above-mentioned heater element with a functional material-containing layer. [Means for solving the problem]

[0008] The above problems are solved by the present invention, which is as follows.

[0009] [1] a honeycomb structure including an outer peripheral wall and partition walls disposed inside the outer peripheral wall and defining a plurality of cells that serve as flow paths extending from a first end face to a second end face, wherein at least the partition walls are made of a material having PTC properties; a pair of electrodes provided on the first end surface and the second end surface of the honeycomb structure; provided on the surface of the partition wall , including adsorbents whose main component is aluminosilicate Functional material-containing layer Equipped with The honeycomb structure has a partition wall thickness of 0.14 to 0.36 mm and a cell density of 15.5 to 46.5 cells / cm. 2 The aperture ratio of the cell is 70 to 94%, and The thickness of the functional material-containing layer is 200 A heater element with a functional material-containing layer having a thickness of 400 μm or less.

[0011] [2] The honeycomb structure ,before The heater element with a functional material-containing layer according to [1], wherein the opening ratio of the cells is 80 to 94%.

[0015] [ 3 ] The functional material-containing layer contains a catalyst. [1] or [2] 2. A heater element with a functional material-containing layer according to claim 1.

[0016] [ 4 ] The honeycomb structure has a length in the flow path direction of 2 to 20 mm and a cross-sectional area perpendicular to the flow path direction of 10 cm 2 That's all, [1]~[ 3 ] A heater element with a functional material-containing layer according to any one of the above items.

[0017] [ 5 ] The material having PTC properties is composed mainly of barium titanate, has a Curie point of 100 to 250°C, and is substantially free of lead, [1] to [ 4 ] A heater element with a functional material-containing layer according to any one of the above items.

[0018] [ 6 ] [1]~[ 5 10. A heater unit with a functional material-containing layer, comprising two or more heater elements with a functional material-containing layer according to any one of the above items.

[0019] [ 7 ] [1]~[ 5 or a heater unit with a functional material-containing layer, comprising two or more of the heater elements with a functional material-containing layer; a battery for applying a voltage to the heater element with a functional material-containing layer or the heater unit with a functional material-containing layer; an inlet pipe communicating a vehicle compartment with an inlet of the heater element with a functional material-containing layer or the heater unit with a functional material-containing layer; an outlet pipe communicating an outlet of the heater element with a functional material-containing layer or the heater unit with a vehicle interior and an exterior of the vehicle; a switching valve provided in the outflow pipe, which can switch the flow of air passing through the outflow pipe to the vehicle compartment or to the outside of the vehicle; A vehicle interior purification system.

[0020] [ 8 ] a first mode in which the voltage applied from the battery is turned off and the switching valve is switched so that the flow of air passing through the outlet pipe is directed toward the vehicle compartment, thereby capturing the components to be removed that are contained in the air from the vehicle compartment in the functional material-containing layer of the heater element with a functional material-containing layer or the heater unit with a functional material-containing layer; a second mode in which the target components to be removed that have been captured in the functional material-containing layer are discharged to the outside of the vehicle by turning on the voltage applied from the battery and switching the switching valve so that the air flowing through the outflow pipe is directed to the outside of the vehicle; and A control unit that alternately executes 7 ] A vehicle interior purification system described in.

[0021] [ 9 ] It contains an adsorbent whose main component is aluminosilicate and has a thickness of 200 to 400 μm. A honeycomb structure used in a heater element with a functional material-containing layer, The fuel cell has an outer peripheral wall and partition walls disposed inside the outer peripheral wall and defining a plurality of cells that serve as flow paths extending from a first end face to a second end face, at least the partition walls being made of a material having PTC properties, the thickness of the partition walls being 0.14 to 0.36 mm, and the cell density being 15.5 to 46.5 cells / cm. 2 The honeycomb structure has an opening ratio of the cells of 70 to 94%. [Effects of the Invention]

[0022] According to the present invention, it is possible to provide a heater element with a functional material-containing layer, a heater unit with a functional material-containing layer, and a vehicle interior purification system that can fully utilize the functions of the functional material. Furthermore, according to the present invention, it is possible to provide a honeycomb structure suitable for producing the above-mentioned heater element with a functional material-containing layer. [Brief explanation of the drawings]

[0023] [Figure 1] FIG. 2 is a schematic diagram of an end face of a heater element according to an embodiment of the present invention. [Figure 2] 2 is a schematic diagram of a cross section parallel to the flow path direction of a heater element according to an embodiment of the present invention. FIG. [Figure 3] 2 is a schematic front view of the heater unit according to the embodiment of the present invention, viewed from the first end face side. FIG. [Figure 4] 1 is a schematic diagram showing a configuration example of a vehicle interior purification system according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0024] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. The present invention is not limited to the following embodiments, and it should be understood that modifications and improvements made to the following embodiments based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention are also within the scope of the present invention.

[0025] (1. Heater element with functional material layer) A heater element with a functional material-containing layer (hereinafter abbreviated as "heater element") according to an embodiment of the present invention can be suitably used as a heater element for use in passenger compartment purification systems in various vehicles, such as automobiles. Examples of vehicles include, but are not limited to, automobiles and trains. Examples of automobiles include, but are not limited to, gasoline-powered vehicles, diesel-powered vehicles, gas-fueled vehicles using CNG (compressed natural gas) or LNG (liquefied natural gas), fuel cell vehicles, electric vehicles, and plug-in hybrid vehicles. The heater element according to an embodiment of the present invention can be suitably used in vehicles without internal combustion engines, particularly electric vehicles and trains.

[0026] Fig. 1 is a schematic diagram of an end face of a heater element with a functional material-containing layer according to an embodiment of the present invention, and Fig. 2 is a schematic diagram of a cross section parallel to the flow path direction of the heater element with a functional material-containing layer according to an embodiment of the present invention. 1 and 2, the heater element 200 includes a honeycomb structure 10 having an outer peripheral wall 11 and partition walls 14 disposed inside the outer peripheral wall 11 to define a plurality of cells 13 that serve as flow paths extending from a first end face 12a to a second end face 12b, a pair of electrodes 30 provided on the first end face 12a and the second end face 12b of the honeycomb structure 10, and a functional material-containing layer 20 provided on the surface of the partition walls 14. Furthermore, at least the partition walls 14 are made of a material having PTC properties. This configuration reduces the in-plane temperature difference of the honeycomb structure 10 (the temperature difference within a cross section perpendicular to the flow path direction of the honeycomb structure 10), allowing the functional material-containing layer 20 to be heated uniformly, thereby making it possible to fully utilize the function of the functional material-containing layer 20. Each component of the heater element 200 will be described in detail below.

[0027] (1-1. Honeycomb structure 10) The shape of the honeycomb structure 10 is not particularly limited. For example, the cross section (external shape) of the honeycomb structure 10 perpendicular to the flow path direction (the direction in which the cells 13 extend) can be polygonal (quadrilateral (rectangle, square), pentagon, hexagon, heptagon, octagon, etc.), circular, or oval (egg, ellipse, oval, rounded rectangle, etc.). The end faces (first end face 12a and second end face 12b) have the same shape as the cross section. When the cross section and end faces are polygonal, the corners may be chamfered.

[0028] The shape of the cells 13 is not particularly limited, but can be polygonal (such as quadrilateral, pentagonal, hexagonal, heptagonal, or octagonal), circular, or oval in a cross section perpendicular to the flow path direction. These shapes may be used alone or in combination of two or more. Among these shapes, quadrilaterals or hexagons are preferred. By providing cells 13 with such shapes, pressure loss during air flow can be reduced. Note that Figures 1 and 2 show an example of a honeycomb structure 10 in which the cross section (outer diameter) and the shape of the cells 13 are quadrilateral in a cross section perpendicular to the flow path direction.

[0029] The honeycomb structure 10 may be a honeycomb bonded body having a plurality of honeycomb segments and a bonding layer bonding the honeycomb segments together. By using the honeycomb bonded body, it is possible to increase the total cross-sectional area of ​​the cells 13, which is important for ensuring the air flow rate, while suppressing the occurrence of cracks. The bonding layer can be formed using a bonding material. The bonding material is not particularly limited, but a ceramic material with a solvent such as water added to form a paste can be used. The bonding material may contain ceramics having PTC properties, or may contain the same ceramics as the outer peripheral wall 11 and the partition walls 14. In addition to the role of bonding the honeycomb segments together, the bonding material can also be used as an outer peripheral coating material after bonding the honeycomb segments.

[0030] The thickness of the partition walls 14 is not particularly limited, but is preferably determined based on the following viewpoints. First, from the viewpoint of ensuring the strength of the honeycomb structure 10, the thickness of the partition walls 14 is preferably 0.10 mm or more, more preferably 0.12 mm or more, even more preferably 0.14 mm or more, even more preferably 0.15 mm or more, and particularly preferably 0.20 mm or more. However, if the thickness of the partition walls 14 is too large, the pressure loss when air passes through the cells 13 may increase. Therefore, from the viewpoint of suppressing an increase in pressure loss, the thickness of the partition walls 14 in the honeycomb structure 10 is preferably 0.36 mm or less, more preferably 0.35 mm or less, and even more preferably 0.30 mm or less. The thickness of the partition walls 14 refers to the length of a line segment that connects the centers of gravity of adjacent cells 13 in a cross section perpendicular to the flow path direction and that line segment crosses the partition walls 14. The thickness of the partition walls 14 refers to the average value of the thicknesses of all the partition walls 14.

[0031] The thickness of the peripheral wall 11 is not particularly limited, but is preferably determined based on the following viewpoints. First, from the viewpoint of reinforcing the honeycomb structure 10, the thickness of the peripheral wall 11 is preferably 0.05 mm or more, more preferably 0.06 mm or more, and even more preferably 0.08 mm or more. On the other hand, from the viewpoint of increasing the electrical resistance to suppress the initial current and reducing the pressure loss when air flows through, the thickness of the peripheral wall 11 is preferably 1.0 mm or less, more preferably 0.5 mm or less, even more preferably 0.4 mm or less, and even more preferably 0.3 mm or less. The thickness of the outer wall 11 refers to the length in the normal direction of the side surface from the boundary between the outer wall 11 and the outermost cell 13 or partition wall 14 to the side surface of the honeycomb structure 10 in a cross section perpendicular to the flow path direction.

[0032] The cell density of the honeycomb structure 10 is not particularly limited, but is preferably determined based on the following viewpoints: First, from the viewpoint of preventing clogging while supporting as much functional material as possible, the cell density of the honeycomb structure 10 is preferably 100 cells / cm. 2 Less than or equal to 46.5 cells / cm, preferably 46.5 cells / cm 2 or less, more preferably 45.0 cells / cm 2 Less than 43.0 cells / cm is particularly preferred 2 However, if the cell density is too small, the contact area with the air may become insufficient. Therefore, from the viewpoint of ensuring a sufficient contact area with the air, the cell density of the honeycomb structure 10 is preferably 15.5 cells / cm or less. 2 More preferably, 18.0 cells / cm 2 More preferably, 20.0 cells / cm 2 That's all. The cell density of the honeycomb structure 10 is a value obtained by dividing the number of cells by the area of ​​each end face of the honeycomb structure 10.

[0033] The opening ratio of the cells 13 of the honeycomb structure 10 is not particularly limited, but is preferably determined based on the following viewpoints. First, from the viewpoint of maximizing the amount of functional material supported, the opening ratio of the cells 13 of the honeycomb structure 10 is preferably 70% or more, more preferably 80% or more, even more preferably 83% or more, and particularly preferably 85% or more. However, if the opening ratio of the cells 13 is too large, the strength of the honeycomb structure 10 may decrease. Therefore, from the viewpoint of ensuring the strength of the honeycomb structure 10, the opening ratio of the cells 13 of the honeycomb structure 10 is preferably 94% or less, more preferably 92% or less, and even more preferably 90% or less. The opening ratio of the honeycomb structure 10 is a value obtained by dividing the area of ​​the cells 13 in a cross section perpendicular to the flow direction of the honeycomb structure 10 by the area of ​​the entire cross section (the total area of ​​the outer wall 11, partition walls 14 and cells 13), and expressing the value as a percentage.

[0034] The length of the honeycomb structure 10 in the flow path direction and the cross-sectional area perpendicular to the flow path direction are not particularly limited and may be adjusted according to the required size of the heater element 200. For example, when used in a compact heater element 200 while ensuring a predetermined function, the honeycomb structure 10 has a length in the flow path direction of 2 to 20 mm and a cross-sectional area perpendicular to the flow path direction of 10 cm. 2 The upper limit of the cross-sectional area perpendicular to the flow path direction is not particularly limited, but may be, for example, 300 cm 2 is.

[0035] The partition walls 14 constituting the honeycomb structure 10 are made of a material having a PTC (Positive Temperature Coefficient) property. If necessary, the outer peripheral wall 11 may also be made of a material having a PTC property like the partition walls 14. A material with PTC characteristics is a material that can generate heat when electricity is applied. The functional material-containing layer 20 can be heated by heat transfer from the heat-generating outer peripheral wall 11 and partition walls 14. Furthermore, a material with PTC characteristics has a characteristic in that, when the temperature rises and exceeds the Curie point, the resistance value rises sharply, making it difficult for electricity to flow. Therefore, when the heater element 200 becomes hot, the partition walls 14 (and the outer peripheral wall 11, if necessary) limit the current flowing therethrough, thereby suppressing excessive heat generation by the heater element 200. Therefore, it is also possible to suppress thermal degradation of the functional material-containing layer 20 caused by excessive heat generation.

[0036] Although there are no particular limitations on the material having PTC properties, it is preferable that it be a material whose main component is barium titanate (BaTiO3), and more preferable that it be a ceramic composed of a material whose main component is barium titanate (BaTiO3)-based crystal particles in which a portion of the Ba has been replaced with a rare earth element. In this specification, the term "main component" refers to a component that accounts for more than 50 mass% of the total components. The content of BaTiO3-based crystal particles can be determined, for example, by fluorescent X-ray analysis or EDAX (energy dispersive X-ray) analysis. Other crystal particles can also be measured in a similar manner.

[0037] The composition formula of BaTiO3-based crystal particles in which part of Ba is replaced by rare earth elements is (Ba 1-x A x )TiO3, where A represents one or more rare earth elements and 0.001≦x≦0.010. A is not particularly limited as long as it is a rare earth element, but is preferably one or more selected from the group consisting of La, Ce, Pr, Nd, Eu, Gd, Dy, Ho, Er, and Yb, and more preferably La. From the viewpoint of preventing the electrical resistance at room temperature from becoming too high, x is preferably 0.001 or more, more preferably 0.0015 or more, and even more preferably 0.002 or more. On the other hand, from the viewpoint of preventing the electrical resistance at room temperature from becoming too high due to insufficient sintering, x is preferably 0.010 or less, more preferably 0.009 or less, and even more preferably 0.008 or less.

[0038] In BaTiO3-based crystal particles in which a portion of Ba has been substituted with a rare earth element, the (Ba + rare earth element) / Ti ratio is preferably 1.005 to 1.050. By controlling the (Ba + rare earth element) / Ti ratio within this range, the electrical resistance at room temperature can be stably reduced. The element ratio of Ba, rare earth element, and Ti can be determined, for example, by X-ray fluorescence analysis, ICP-MS (inductively coupled plasma mass spectrometry), etc.

[0039] The BaTiO3-based crystal particles in which a portion of Ba is substituted with a rare earth element preferably have an average crystal grain size of 5 to 200 μm, more preferably 5 to 180 μm, and even more preferably 5 to 160 μm. By controlling the average crystal grain size within this range, it is possible to stably reduce the electrical resistance at room temperature. The average crystal grain size of these BaTiO3-based crystal grains can be measured as follows. A square specimen measuring 5 mm x 5 mm x 5 mm is cut from the ceramic and embedded in resin. The embedded specimen is mechanically polished to a mirror finish and then observed using an SEM. SEM observation is performed using, for example, a Hitachi High-Technologies Corporation S-3400N microscope at an accelerating voltage of 15 kV and a magnification of 3000. In the SEM observation image (30 μm long x 45 μm wide), four straight lines, each 0.3 μm thick, are drawn at 10 μm intervals across the entire vertical direction of the field of view, and the number of BaTiO3-based crystal grains that are partially intersected by these lines is counted. The length of the lines is divided by the number of BaTiO3-based crystal grains, and the average of this length, obtained over four or more SEM observation images, is taken as the average crystal grain size.

[0040] The content of BaTiO3-based crystal particles in the ceramic, in which Ba is partially substituted with a rare earth element, is not particularly limited as long as it is an amount that serves as the main component, but is preferably 90 mass% or more, more preferably 92 mass% or more, and even more preferably 94 mass% or more. The upper limit of the content of BaTiO3-based crystal particles is not particularly limited, but is generally 99 mass%, preferably 98 mass%. The content of the BaTiO3-based crystal particles can be measured by, for example, fluorescent X-ray analysis or EDAX (energy dispersive X-ray) analysis. Other crystal particles can also be measured in the same manner.

[0041] The ceramics used for the outer wall 11 and the partition wall 14 are Ba6Ti 17 O 40 It is preferable that the ceramic contains crystal grains. 17 O 40 The presence of crystalline particles can reduce the electrical resistance at room temperature. 17 O 40 It is believed that the crystal particles become liquid during the firing process, promoting rearrangement, grain growth and densification of BaTiO3-based crystal particles, resulting in a decrease in electrical resistance at room temperature.

[0042] Ba6Ti in ceramics 17 O 40 The content of the crystal particles is 1.0 to 10.0 mass %, preferably 1.2 to 8.0 mass %, and more preferably 1.5 to 6.0 mass %. 17 O 40 By making the crystal grains 1.0 mass% or more, Ba6Ti 17 O 40 The effect of the presence of crystal particles (i.e., the effect of reducing electrical resistance at room temperature) can be obtained. 17 O 40 By keeping the crystal grain content at 10.0 mass % or less, the PTC characteristics can be ensured.

[0043] The ceramics used for the outer peripheral wall 11 and the partition walls 14 may further contain BaCO3 crystal particles. The BaCO3 crystal particles are crystal particles derived from BaCO3 powder, which is a raw material for ceramics. BaCO3 crystal particles have almost no effect on the electrical resistance of ceramics at room temperature, so they may not be present in ceramics. However, if the content of BaCO3 crystal particles in ceramics is too high, it may affect the electrical resistance at room temperature and may reduce the amount of other crystal particles, making it difficult to achieve the desired characteristics. Therefore, the content of BaCO3 crystal particles is preferably 2.0% by mass or less, more preferably 1.8% by mass or less, and even more preferably 1.5% by mass or less. The lower limit of the content of BaCO3 crystal particles is not particularly limited, but is generally 0.1% by mass, preferably 0.2% by mass.

[0044] The ceramic used for the outer peripheral wall 11 and the partition walls 14 may further contain components that are conventionally added to PTC materials in addition to the above-mentioned crystal particles. Such components include additives such as shifters, property improvers, metal oxides, and conductor powders, as well as unavoidable impurities.

[0045] From the viewpoint of reducing environmental impact, it is desirable that the ceramics used for the outer peripheral wall 11 and the partition walls 14 contain substantially no lead (Pb). Specifically, the Pb content of the ceramics is preferably 0.01% by mass or less, more preferably 0.001% by mass or less, and even more preferably 0% by mass. A low Pb content allows, for example, air heated by contact with the ceramics to be safely applied to living organisms such as humans. Note that the Pb content of the ceramics, calculated as PbO, is preferably less than 0.03% by mass, more preferably less than 0.01% by mass, and even more preferably 0% by mass. The lead content can be determined, for example, by X-ray fluorescence analysis, ICP-MS (inductively coupled plasma mass spectrometry), or the like.

[0046] The ceramics used for the outer peripheral wall 11 and the partition walls 14 preferably do not substantially contain alkali metals, which may affect the electrical resistance at room temperature. Specifically, the content of alkali metals in the ceramics is preferably 0.01% by mass or less, more preferably 0.001% by mass or less, and even more preferably 0% by mass. By controlling the alkali metal content within this range, the electrical resistance at room temperature can be stably reduced. The alkali metal content can be determined, for example, by X-ray fluorescence analysis, ICP-MS (inductively coupled plasma mass spectrometry), or the like.

[0047] The Curie point of the material forming the outer peripheral wall 11 and the partition wall 14 is preferably 100° C. or higher, more preferably 110° C. or higher, and even more preferably 125° C. or higher, from the viewpoint of efficient heating of air. The upper limit of the Curie point is preferably 250° C., more preferably 225° C., even more preferably 200° C., and even more preferably 150° C., from the viewpoint of safety as a part placed in or near the vehicle interior.

[0048] The Curie point of the material forming the outer peripheral wall 11 and the partition walls 14 can be adjusted by the type and amount of the shifter added. For example, the Curie point of barium titanate (BaTiO) is approximately 120°C, but by substituting part of the Ba and Ti with one or more of Sr, Sn, and Zr, the Curie point can be shifted to a lower temperature.

[0049] In the present invention, the Curie point is measured by the following method: A sample is attached to a sample holder for measurement and placed in a measurement tank (e.g., MINI-SUBZERO MC-810P, manufactured by Espec Corporation), and the change in the sample's electrical resistance with respect to temperature change when the temperature is raised from 10°C is measured using a DC resistance meter (e.g., Multimeter 3478A, manufactured by YHP). The Curie point is determined as the temperature at which the resistance value is twice the resistance value at room temperature (20°C) based on the electrical resistance-temperature plot obtained by the measurement.

[0050] (1-2.Functional material containing layer 20) The functional material-containing layer 20 is provided on the surfaces of the partition walls 14 of the honeycomb structure 10. Specifically, the functional material-containing layer 20 is provided on the surfaces of the partition walls 14 and the outer wall 11 that face the cells 13 of the honeycomb structure 10.

[0051] The functional material-containing layer 20 provided on the partition walls 14 of the honeycomb structure 10 is indirectly heated by the heat of the honeycomb structure 10 heated by the pair of electrodes 30. Therefore, in order to fully utilize the function of the functional material-containing layer 20, it is essential to reduce the in-plane temperature difference (in-plane temperature distribution) of the honeycomb structure 10 and uniformly raise the entire functional material-containing layer 20 to the activation temperature. In fact, when the in-plane temperature difference of the honeycomb structure 10 is large, sufficiently raising the temperature of the low-temperature portion may cause the temperature of the high-temperature portion to become excessive, resulting in partial deterioration of the functional material-containing layer 20. If there is a region in the functional material-containing layer 20 where partial deterioration has occurred, the function of the functional material-containing layer 20 cannot be fully utilized. In the embodiment of the present invention, a pair of electrodes 30 is provided on the first end face 12a and the second end face 12b of the honeycomb structure 10, and the partition walls 14 are made of a material having PTC properties, so that the electrical resistance is high at high temperatures and low at low temperatures. Therefore, when a voltage is applied to the pair of electrodes 30, current flows preferentially to the low-temperature parts of the honeycomb structure 10, reducing the in-plane temperature difference, and as a result, it becomes possible to uniformly heat the entire functional material-containing layer 20 to the activation temperature.

[0052] Furthermore, by controlling the thickness of the partition walls 14, the cell density, and the opening ratio of the cells 13 of the honeycomb structure 10, it is possible to prevent the cells 13 of the honeycomb structure 10 from becoming clogged or the opening area of ​​the cells 13 from becoming too small, even when the functional material-containing layer 20 is provided. Therefore, it is possible to ensure sufficient contact between the functional material-containing layer 20 and the air, so that the function of the functional material can be stably obtained and also to prevent an increase in pressure loss when air passes through the cells 13.

[0053] The thickness of the functional material-containing layer 20 is not particularly limited and may be determined depending on the size of the cells 13. For example, from the viewpoint of ensuring sufficient contact with air, the thickness of the functional material-containing layer 20 is preferably 20 μm or more, more preferably 25 μm or more, and even more preferably 30 μm or more. On the other hand, from the viewpoint of preventing peeling of the functional material-containing layer 20 from the partition walls 14 and the outer peripheral wall 11, the thickness of the functional material-containing layer 20 is preferably 400 μm or less, more preferably 380 μm or less, and even more preferably 350 μm or less. The thickness of the functional material-containing layer 20 refers to the shortest length between the partition wall 14 and the cell 13 on which the functional material-containing layer 20 is provided, in a cross section perpendicular to the flow path direction.

[0054] The functional material contained in the functional material-containing layer 20 is not particularly limited, but an adsorbent, a catalyst, or the like can be used. In one embodiment, the functional material-containing layer 20 preferably contains an adsorbent material, which can capture components to be removed, such as CO2 and harmful volatile components, in the air inside the vehicle cabin. In another embodiment, the functional material-containing layer 20 preferably contains a catalyst. The use of a catalyst can purify the components to be removed. Furthermore, an adsorbent and a catalyst may be used in combination to enhance the ability of the adsorbent to capture the components to be removed.

[0055] The adsorbent preferably has the ability to adsorb components to be removed, such as CO2 and harmful volatile components (e.g., aldehydes, odor components, etc.), at temperatures between -20 and 40°C and desorb them at high temperatures of 60°C or higher. Examples of adsorbents with such capabilities include materials whose main components are aluminosilicates (e.g., zeolites), silica gel, activated carbon, alumina, silica, low-crystalline clay, and amorphous aluminum silicate complexes. The type of adsorbent may be selected appropriately depending on the type of components to be removed. The catalyst preferably has a function capable of promoting the oxidation-reduction reaction, such as metal catalysts such as Pt, Pd, and Ag, and oxide catalysts such as CeO2 and ZrO2.

[0056] Harmful volatile components contained in the air inside a vehicle cabin include, for example, volatile organic compounds (VOCs) and odor components. Specific examples of harmful volatile components include ammonia, acetic acid, isovaleric acid, nonenal, formaldehyde, toluene, xylene, paradichlorobenzene, ethylbenzene, styrene, chlorpyrifos, di-n-butyl phthalate, tetradecane, di-2-ethylhexyl phthalate, diazinon, acetaldehyde, and fenobucarb. In addition to CO2 and harmful volatile components, moisture can also be included as a target component for removal.

[0057] (1-3. Electrode 30) The pair of electrodes 30 are provided on the first end face 12a and the second end face 12b of the honeycomb structure 10. In Figs. 1 and 2, the pair of electrodes 30 are provided on the surface of the outer peripheral wall 11, but they may be provided not only on the surface of the outer peripheral wall 11 but also on the surface of the partition wall 14. By applying a voltage to the pair of electrodes 30 in a direction parallel to the flow path direction of the honeycomb structure 10, it becomes possible to pass electricity and cause the honeycomb structure 10 to generate heat by Joule heat. The electrode 30 may have an extension portion that extends toward the outside of the honeycomb structure 10. By providing the extension portion, it becomes easier to connect with a connector that serves to connect with the outside.

[0058] The electrode 30 is not particularly limited, and may be, for example, a metal or alloy containing at least one selected from Cu, Ag, Al, Ni, and Si. Alternatively, an ohmic electrode capable of making ohmic contact with the outer peripheral wall 11 and / or the partition wall 14 having PTC characteristics may be used. The ohmic electrode may contain, for example, at least one selected from Au, Ag, and In as a base metal and at least one selected from Ni, Si, Ge, Sn, Se, and Te as a dopant for n-type semiconductors. The electrode 30 may have a single-layer structure or a stacked structure of two or more layers. When the electrode 30 has a stacked structure of two or more layers, the materials of the layers may be the same or different.

[0059] The thickness of the electrode 30 is not particularly limited and can be set appropriately depending on the method for forming the electrode 30. Examples of methods for forming the electrode 30 include metal deposition methods such as sputtering, vapor deposition, electrolytic deposition, and chemical deposition. The electrode 30 can also be formed by applying an electrode paste and then baking it, or by thermal spraying. Furthermore, the electrode 30 may be formed by joining metal or alloy plates. The thickness of the electrode 30 is preferably about 5 to 80 μm when baking an electrode paste, about 100 to 1000 nm when dry plating such as sputtering and vapor deposition, about 10 to 100 μm when thermal spraying, and about 5 to 50 μm when wet plating such as electrolytic deposition and chemical deposition. Furthermore, when joining metal or alloy plates, the thickness of the electrode 30 is preferably about 5 to 100 μm.

[0060] (1-4. Manufacturing method of heater element 200) Next, a method for manufacturing the heater element 200 according to the embodiment of the present invention will be described by way of example. When the material of the honeycomb structure 10 is ceramic, the manufacturing method of the honeycomb structure 10 includes a molding step and a firing step. In the molding step, a clay containing ceramic raw materials including BaCO3 powder, TiO2 powder, and powder of a rare earth nitrate or hydroxide is molded to produce a honeycomb molded body with a relative density of 60% or more. The ceramic raw material can be obtained by dry mixing each powder to obtain a desired composition. The clay can be obtained by adding a dispersion medium, a binder, a plasticizer, and a dispersant to a ceramic raw material and kneading the mixture. The clay may contain additives such as a sifter, a metal oxide, a property improver, and a conductive powder, as needed. The blending amount of components other than the ceramic raw materials is not particularly limited as long as the amount is such that the relative density of the honeycomb formed body is 60%.

[0061] Here, in this specification, the "relative density of the honeycomb formed body" means the ratio of the density of the honeycomb formed body to the true density of the entire ceramic raw material. Specifically, it can be calculated by the following formula. Relative density (%) of honeycomb formed body = Density of honeycomb formed body (g / cm 3 ) / true density of the entire ceramic raw material (g / cm 3 ) x 100 The density of the honeycomb formed body can be measured by the Archimedes method using pure water as a medium. The true density of the entire ceramic raw material is calculated by multiplying the total mass (g) of each raw material by the total volume (cm) of each raw material. 3 ) can be calculated by dividing by

[0062] Examples of the dispersion medium include water and a mixed solvent of water and an organic solvent such as alcohol, with water being particularly preferred.

[0063] Examples of binders include organic binders such as methyl cellulose, hydroxypropoxyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and polyvinyl alcohol. It is particularly preferable to use a combination of methyl cellulose and hydroxypropoxyl cellulose. While one binder may be used alone or two or more binders may be used in combination, it is preferable that the binder does not contain an alkali metal element.

[0064] Examples of the plasticizer include polyoxyalkylene alkyl ether, polycarboxylic acid polymer, and alkyl phosphate ester.

[0065] The dispersant may be a surfactant such as polyoxyalkylene alkyl ether, ethylene glycol, dextrin, fatty acid soap, polyalcohol, etc. The dispersant may be used alone or in combination of two or more.

[0066] The honeycomb formed body can be produced by extrusion molding of a clay. In extrusion molding, a die having a desired overall shape, cell shape, partition wall thickness, cell density, etc. can be used.

[0067] The relative density of the honeycomb formed body obtained by extrusion molding is 60% or more, preferably 61% or more. By controlling the relative density of the honeycomb formed body within this range, it is possible to densify the honeycomb formed body and reduce its electrical resistance at room temperature. The upper limit of the relative density of the honeycomb formed body is not particularly limited, but is generally 80%, preferably 75%.

[0068] The honeycomb molded body can be dried before the firing step. The drying method is not particularly limited, and for example, a conventionally known drying method such as hot air drying, microwave drying, dielectric drying, reduced pressure drying, vacuum drying, freeze drying, etc. Among these, a drying method that combines hot air drying with microwave drying or dielectric drying is preferred because it can dry the entire molded body quickly and uniformly.

[0069] The firing step includes a step of holding the temperature at 1150 to 1250°C, then raising the temperature to a maximum temperature of 1360 to 1430°C at a rate of 20 to 500°C / hour, and holding the temperature for 0.5 to 5 hours. By holding the honeycomb formed body at a maximum temperature of 1360 to 1430°C for 0.5 to 5 hours, a honeycomb structure 10 containing, as a main component, BaTiO3-based crystal particles in which part of Ba has been substituted with a rare earth element can be obtained. Furthermore, by maintaining the temperature at 1150 to 1250°C, Ba2TiO4 crystal particles generated during the firing process can be easily removed, and the honeycomb structure 10 can be made dense. Furthermore, by setting the heating rate from 1150 to 1250°C to the maximum temperature of 1360 to 1430°C at 20 to 500°C / hour, 1.0 to 10.0 mass% of Ba6Ti 17 O 40 Crystal grains can be generated in the honeycomb structure 10 .

[0070] The holding time at 1150 to 1250°C is not particularly limited, but is preferably 0.5 to 5 hours. By setting the holding time at such a time, Ba2TiO4 crystal particles generated during the firing process can be stably and easily removed.

[0071] The firing step preferably includes a step of holding the mixture at 900 to 950°C for 0.5 to 5 hours before the above step. By holding the mixture at 900 to 950°C for 0.5 to 5 hours, BaCO3 is efficiently decomposed, and it becomes easier to obtain a honeycomb structure 10 having a predetermined composition.

[0072] Before the firing step, a degreasing step may be carried out to remove the binder. The degreasing step is preferably carried out in an air atmosphere to completely decompose the organic components. Furthermore, the firing step is preferably carried out in an air atmosphere from the viewpoint of controlling electrical properties and reducing manufacturing costs. The firing furnace used in the firing step and degreasing step is not particularly limited, but an electric furnace, a gas furnace, or the like can be used.

[0073] The functional material-containing layer 20 is formed on the partition walls 14 of the honeycomb structure 10 obtained in this manner. The method for forming the functional material-containing layer 20 is not particularly limited, but for example, the honeycomb structure 10 is immersed in a slurry containing a functional material, an organic binder, and water, and excess slurry is removed from the end faces and outer periphery of the honeycomb structure 10 by blowing and wiping. Thereafter, the functional material-containing layer 20 can be formed on the partition walls 14 by drying at a temperature of about 550°C. This process may be performed once, but by repeating it multiple times, a functional material-containing layer 20 of a desired thickness can be provided on the partition walls 14.

[0074] Next, a pair of electrodes 30 are formed on the first end face 12a and the second end face 12b of the honeycomb structure 10 on which the functional material-containing layer 20 has been formed. The pair of electrodes 30 may be a single layer, or may be multiple layers with different compositions. The pair of electrodes 30 may be formed before the functional material-containing layer 20 is formed.

[0075] (1-5. How to use the heater element 200) The heater element 200 according to the embodiment of the present invention can capture the components to be removed, such as CO2 and harmful volatile components, by passing air containing the components to be removed through the cell 13 at temperatures between -20 and 40°C, preferably at room temperature. The heater element 200 according to the embodiment of the present invention can generate heat in the honeycomb structure 10 by heating it from the outside. Furthermore, the heater element 200 according to the embodiment of the present invention can generate heat in the honeycomb structure 10 by applying a voltage via a pair of electrodes 30. From the viewpoint of rapid heating, the applied voltage is preferably 200 V or more, and more preferably 250 V or more. By generating heat in the honeycomb structure 10, the captured components to be removed can be desorbed from the functional material-containing layer 20 and removed to the outside. The heating temperature of the honeycomb structure 10 can be set appropriately depending on the type of functional material, and is, for example, 60 to 150°C.

[0076] (2. Heater unit with functional material layer) A heater unit with a functional material-containing layer (hereinafter abbreviated as "heater unit") according to an embodiment of the present invention can be suitably used as a heater unit for use in a vehicle interior purification system in various vehicles, such as automobiles. The heater unit according to an embodiment of the present invention includes two or more heater elements 200. By using two or more heater elements 200 that are excellent in the functionality of the functional material (particularly, the functionality of capturing components to be removed and the functionality of desorbing the captured components to be removed upon heating), the functionality of the functional material (particularly, the purification performance of the vehicle interior) can be improved. Furthermore, because the heater element 200 can be made compact, it is possible to prevent the heater unit from becoming too large.

[0077] FIG. 3 is a schematic front view of a heater unit including two heater elements 200, viewed from the first end face side of the heater elements. 3, a heater unit 400 according to an embodiment of the present invention includes two heater elements 200. In this heater unit 400, the heater elements 200 are stacked and arranged so that the side surfaces parallel to the flow path direction of the honeycomb structure 10 face each other.

[0078] The electrode 30 of the heater element 200 is provided with a terminal 410 that can be connected to an external power source. The terminal 410 is preferably connected to the surface of the extended portion of the electrode 30 that faces the honeycomb structure 10. This configuration allows the heater element 200 to be made compact. The method for connecting the electrode 30 and the terminal 410 is not particularly limited as long as they are electrically connected, and they can be connected by, for example, diffusion bonding, a mechanical pressure mechanism, welding, etc. The material of terminal 410 is not particularly limited, but may be, for example, a metal. As the metal, a single metal or an alloy may be used, but from the viewpoints of corrosion resistance, electrical resistivity, and linear expansion coefficient, an alloy containing at least one selected from the group consisting of Cr, Fe, Co, Ni, Cu, and Ti is preferable, and stainless steel, an Fe-Ni alloy, and phosphor bronze are more preferable.

[0079] The heater elements 200 arranged in a stack are housed in a case (housing member) 420. The material of housing 420 is not particularly limited, and examples thereof include metal and resin. Among these, resin is preferable as the material of housing 420. By using resin housing 420, electric shock can be suppressed even without grounding.

[0080] An insulating material 430 may be disposed between the stacked heater elements 200. With this configuration, electrical short circuits between the multiple heater elements 200 can be suppressed. The insulating material 430 may be a plate, mat, cloth, or the like made of an insulating material such as alumina or ceramics.

[0081] (3. Vehicle compartment purification system) The vehicle interior purification system of the present invention can be suitably used as a vehicle interior purification system for various vehicles such as automobiles. In particular, the vehicle interior purification system according to the embodiment of the present invention uses the heater element 200 or heater unit 400 described above, which has excellent functional material functions (particularly, the function of capturing components to be removed and the function of desorbing the captured components to be removed when heated), thereby improving the vehicle interior purification performance of the vehicle interior purification system.

[0082] FIG. 4 is a schematic diagram showing an example of the configuration of a vehicle interior purification system according to an embodiment of the present invention. As shown in Figure 4, the vehicle interior purification system 1000 according to an embodiment of the present invention comprises the above-mentioned heater element or heater unit 1100, a battery (power source) 1200 for applying voltage to the heater element or heater unit 1100, an inlet pipe 1300 connecting the vehicle interior with the inlet 1110 of the heater element or heater unit 1100, an outlet pipe 1400 connecting the outlet 1120 of the heater element or heater unit 1100 with the vehicle interior and the outside of the vehicle, and a switching valve 1500 provided in the outlet pipe 1400, which can switch the flow of air circulating through the outlet pipe 1400 to either the vehicle interior or the outside of the vehicle.

[0083] The heater element or heater unit 1100 can be configured, for example, to be connected to a battery 1200 by an electric wire 1210, and by turning on a power switch in between, the heater element or heater unit 1100 can be energized to generate heat. The power switch can be turned on and off by a control unit 1600 electrically connected to the power switch. The switching valve 1500 can also be switched by the control unit 1600 electrically connected to the switching valve 1500.

[0084] In the vehicle interior purification system 1000 having the above-described structure, air from the vehicle interior is supplied to the heater element or heater unit 1100 from the inlet 1110 through the inlet piping 1300. After a predetermined process is performed on the air in the heater element or heater unit 1100 in response to instructions from the control unit 1600, the air is discharged from the outlet 1120 and returned to the vehicle interior or discharged outside the vehicle through the outlet piping 1400. An example of the predetermined process is a process of alternately executing a first mode and a second mode. In the first mode, the applied voltage from the battery 1200 is turned off, and the switching valve 1500 is switched so that the air flowing through the outlet pipe 1400 is directed toward the vehicle compartment, thereby capturing the components to be removed that are contained in the air from the vehicle compartment in the functional material-containing layer 20 of the heater element or heater unit 1100. In addition, in the second mode, the applied voltage from the battery 1200 is turned on, and the switching valve 1500 is switched so that the air flowing through the outlet pipe 1400 is directed outside the vehicle, thereby allowing the components to be removed that are captured in the functional material-containing layer 20 to be discharged outside the vehicle. By repeating the on / off of the applied voltage and the switching of the switching valve 1500 in a fixed cycle as described above, it becomes possible to stably discharge the components to be removed from inside the vehicle cabin to the outside of the vehicle.

[0085] In order to stably ensure the above-mentioned functions, it is desirable that the heater element or heater unit 1100 of the vehicle interior purification system 1000 be located close to the vehicle interior. Therefore, from the viewpoint of preventing electric shock, etc., it is preferable that the driving voltage be 60 V or less. The honeycomb structure 10 used in the heater element or heater unit 1100 has low electrical resistance at room temperature, so that the honeycomb structure 10 can be heated at this low driving voltage. The lower limit of the driving voltage is not particularly limited, but is preferably 10 V or more. If the driving voltage is less than 10 V, the current when heating the honeycomb structure 10 will be large, and therefore the electric wire 1210 must be made thicker. [Example]

[0086] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0087] <Experiment 1> BaCO3 powder, TiO2 powder, and La(NH3)3·6H2O powder were prepared as ceramic raw materials. These powders were weighed so that the desired composition would be obtained after firing, and then dry-mixed to obtain a mixed powder. Dry mixing was carried out for 30 minutes. Next, water, binder, plasticizer, and dispersant were added in appropriate amounts in the range of 3 to 30 parts by mass in total to 100 parts by mass of the obtained mixed powder, and kneaded to obtain a clay body with a relative density of 64.8% after extrusion molding. Methylcellulose was used as the binder, and polyoxyalkylene alkyl ether was used as the plasticizer and dispersant.

[0088] Next, the obtained clay was put into an extrusion molding machine and extrusion molded using a predetermined die so as to obtain a honeycomb molded body having the shape shown below after firing. Cross section and end face shape of honeycomb formed body perpendicular to the flow direction: square Cell shape perpendicular to the flow direction: square Partition thickness: 0.14mm Outer wall thickness: 0.4 mm Cell density: 100 cells / cm 2 Cell aperture ratio: 73.9% Size of cross section perpendicular to the flow direction of honeycomb molded body: 30mm x 30mm Length of honeycomb body in the flow direction: 30 mm Curie point of the material that makes up the outer wall and partition wall: 120°C

[0089] Next, the obtained honeycomb molded body was subjected to dielectric drying and hot air drying, and then degreased in an air atmosphere in a firing furnace (450°C x 4 hours), and then fired in an air atmosphere to obtain a honeycomb structure. The firing was performed by holding at 950°C for 1 hour, then increasing the temperature to 1200°C and holding at 1200°C for 1 hour, then increasing the temperature to 1400°C (maximum temperature) at a heating rate of 200°C / hour, and holding at 1400°C for 2 hours.

[0090] Next, Al-Ni electrode paste and Ag electrode paste were applied sequentially to both end faces (first end face and second end face) of the obtained honeycomb structure (sample number 5), and then baked at 700°C to form a two-layer electrode (Al-Ni electrode layer 10 μm + Ag electrode layer 30 μm) (A-1 to A-5). For comparison, two types of electrode paste were applied sequentially to the opposing side surfaces (opposing outer surfaces parallel to the flow path direction) of the obtained honeycomb structure (sample number 5) in the same manner as above, and then baked to form two-layer electrodes (Al-Ni electrode layer 10 μm + Ag electrode layer 30 μm) (B-1 to B-5).

[0091] Next, the honeycomb structure with the electrodes formed thereon was immersed in a slurry containing zeolite (functional material), an organic binder, and water, and excess slurry from the end faces and outer periphery was removed by blowing and wiping. After that, the structure was dried at a temperature of approximately 550°C to form a functional material-containing layer 0.2 mm thick on the partition wall.

[0092] Next, the in-plane temperature difference was evaluated for each sample of the functional material-containing layer-attached heater element obtained as described above. The in-plane temperature difference was measured using thermocouples at four corners and one central point on the outlet end face while heating the honeycomb structure by applying a voltage of 48 V between a pair of electrodes and flowing air at an average speed of 0.1 m / s through the cells of the honeycomb structure. The maximum difference between the temperatures at each corner and the central point was calculated as the in-plane temperature difference. A temperature difference of 20°C or less can be considered to be sufficient to uniformly heat the entire structure to its activation temperature without deteriorating the functional material-containing layer. The results are shown in Table 1.

[0093] [Table 1]

[0094] As shown in Table 1, it was found that the heater element with a functional material-containing layer (Example) having a pair of electrodes on both end surfaces of the honeycomb structure had a smaller in-plane temperature difference and could heat the entire functional material-containing layer uniformly compared to the heater element with a functional material-containing layer (Comparative Example) having a pair of electrodes on opposing side surfaces of the honeycomb structure.

[0095] <Experiment 2> The clay prepared in the same manner as in Experiment 1 was placed in an extrusion molding machine and extruded using a predetermined die so as to obtain a honeycomb molded body having the shape shown in Table 2 after firing. The results of visual evaluation of this extrusion molding are shown in Table 2. In this evaluation, A indicates good moldability, B indicates cells were deformed, and C indicates cells were crushed and the desired honeycomb shape could not be formed. If the moldability is A or B in this evaluation, it can be evaluated that a functional material-containing layer can be provided on the surface of the partition walls.

[0096] Other conditions for the honeycomb formed body were as follows. Cross section and end face shape of honeycomb formed body perpendicular to the flow direction: square Cell shape perpendicular to the flow direction: square Outer wall thickness: 0.4 mm Size of cross section perpendicular to the flow direction of honeycomb molded body: 35mm x 35mm Length of honeycomb body in the flow direction: 10 mm Curie point of the material that makes up the outer wall and partition wall: 120°C

[0097] Next, the obtained honeycomb molded body was subjected to dielectric drying and hot air drying, and then degreased in an air atmosphere in a firing furnace (450°C x 4 hours), and then fired in an air atmosphere to obtain a honeycomb structure. The firing was performed by holding at 950°C for 1 hour, then increasing the temperature to 1200°C and holding at 1200°C for 1 hour, then increasing the temperature to 1400°C (maximum temperature) at a heating rate of 200°C / hour, and holding at 1400°C for 2 hours.

[0098] Next, the resulting honeycomb structure was immersed in a slurry containing zeolite (functional material), an organic binder, and water. Excess slurry was removed from the end faces and periphery by blowing and wiping, and the structure was then dried at approximately 550°C to form a functional material-containing layer on the partition walls. The end faces of the honeycomb structures on which the functional material-containing layer was formed were visually observed to evaluate cell clogging. The results are shown in Table 2. In this evaluation, a clogging ratio (number of clogged cells / total number of cells × 100) of less than 1% was designated A, a clogging ratio of 1% to 10% was designated B, a clogging ratio of more than 10% to 15% was designated C, a clogging ratio of more than 15% to 20% was designated D, and a clogging ratio of more than 20% was designated E. Note that this evaluation was not performed on honeycomb structures with a moldability rating of C (those that could not be molded). If the clogging rate in this evaluation is 20% or less, it can be evaluated that the minimum necessary functional material-containing layer can be provided on the surface of the partition walls.

[0099] [Table 2]

[0100] As shown in Table 2, the partition wall thickness is 0.10 to 0.36 mm, and the cell density is 15.5 to 100 cells / cm. 2 The honeycomb structures with cell opening ratios in the range of 70 to 94% had good moldability and little clogging of the cells. In contrast, honeycomb structures in which any one of the partition wall thickness, cell density, and cell opening ratio is outside the above ranges have insufficient formability and / or have frequent clogged cells.

[0101] As can be seen from the above results, the present invention can provide a heater element with a functional material-containing layer, a heater unit with a functional material-containing layer, and a vehicle interior purification system that can fully utilize the functions of the functional material. Furthermore, the present invention can provide a honeycomb structure suitable for producing the above-mentioned heater element with a functional material-containing layer. [Explanation of symbols]

[0102] 10 Honeycomb structure 11 Peripheral wall 12a 1st end surface 12b 2nd end face 13 cells 14 Bulkhead 20 Functional material containing layer 30 electrodes 200 heater element 400 heater unit 410 terminal 420 cabinet 430 Insulation 1000 Vehicle Interior Purification System 1100 Heating element or heating unit 1110 Inlet 1120 Outlet 1200 battery 1210 Electric wire 1300 Inlet piping 1400 Outlet piping 1500 Switching Valve 1600 Control Unit

Claims

1. a honeycomb structure including an outer peripheral wall and partition walls disposed inside the outer peripheral wall to define a plurality of cells that serve as flow paths extending from a first end face to a second end face, wherein at least the partition walls are made of a material having PTC characteristics; a pair of electrodes provided on the first end surface and the second end surface of the honeycomb structure; a functional material-containing layer provided on the surface of the partition wall and containing an adsorbent mainly composed of aluminosilicate; Equipped with The honeycomb structure has a partition wall thickness of 0.14 to 0.36 mm and a cell density of 15.5 to 46.5 cells / cm. 2 , the opening ratio of the cell is 70 to 94%, and A heater element with a functional material-containing layer, wherein the thickness of the functional material-containing layer is 200 to 400 μm.

2. 2. The heating element with a functional material-containing layer according to claim 1, wherein the honeycomb structure has an opening ratio of the cells of 80 to 94%.

3. The heating element with a functional material-containing layer according to claim 1 , wherein the functional material-containing layer contains a catalyst.

4. The honeycomb structure has a length in the flow path direction of 2 to 20 mm and a cross-sectional area perpendicular to the flow path direction of 10 cm 2 The heating element with a functional material-containing layer according to claim 1 .

5. 2. The heating element with a functional material-containing layer according to claim 1, wherein the material having PTC properties is composed of a material that is mainly composed of barium titanate, has a Curie point of 100 to 250°C, and is substantially free of lead.

6. A heater unit with a functional material-containing layer, comprising two or more heater elements with a functional material-containing layer according to any one of claims 1 to 5.

7. a heater unit with a functional material-containing layer comprising the heater element with a functional material-containing layer according to any one of claims 1 to 5 or two or more of the heater elements with a functional material-containing layer; a battery for applying a voltage to the heater element with a functional material-containing layer or the heater unit with a functional material-containing layer; an inlet pipe communicating a vehicle compartment with an inlet of the heater element with a functional material-containing layer or the heater unit with a functional material-containing layer; an outlet pipe communicating an outlet of the heater element with a functional material-containing layer or the heater unit with a vehicle interior and an exterior of the vehicle; a switching valve provided in the outflow pipe, which can switch the flow of air passing through the outflow pipe to the vehicle compartment or to the outside of the vehicle; A vehicle interior purification system.

8. a first mode in which the voltage applied from the battery is turned off and the switching valve is switched so that the flow of air circulating through the outlet pipe is directed toward the vehicle compartment, thereby capturing the components to be removed that are contained in the air from the vehicle compartment in the functional material-containing layer of the heater element with a functional material-containing layer or the heater unit with a functional material-containing layer; a second mode in which the voltage applied from the battery is turned on and the switching valve is switched so that the air flowing through the outlet pipe is directed outside the vehicle, thereby discharging the removal target components captured in the functional material-containing layer to the outside of the vehicle; The vehicle interior purification system according to claim 7 , further comprising a control unit that alternately executes the steps of:

9. A honeycomb structure used in a heater element with a functional material-containing layer, which contains an adsorbent mainly composed of aluminosilicate and has a thickness of 200 to 400 μm, The fuel cell has an outer peripheral wall and partition walls disposed inside the outer peripheral wall and defining a plurality of cells that serve as flow paths extending from a first end face to a second end face, at least the partition walls being made of a material having PTC characteristics, the thickness of the partition walls being 0.14 to 0.36 mm, and the cell density being 15.5 to 46.5 cells / cm. 2 The honeycomb structure has an opening ratio of the cells of 70 to 94%.

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