Resin member and vacuum insulation material

Abstract

The present invention addresses the problem of providing: a vacuum heat-insulating material which has a good surface smoothness level as a vacuum heat-insulating material, excellent strength in the thickness direction, and good workability; and a core material for the vacuum heat-insulating material. The resin member is a substantially flat plate-shaped resin member, the density of the resin member is 50 kg / m3 or more and 250 kg / m3 or less, and when the amount of depression (mm) of the resin member when a load generated by cylindrical stainless steel SUS304 having a diameter of 6 mm and a mass of 3 kg is applied to the resin member in a direction parallel to the thickness direction of the resin member is defined as Dh0, Dh0 is less than 7.5 mm.

Description

Technical Field

[0001] This invention relates to resin components and vacuum insulation materials. Background Technology

[0002] In recent years, due to concerns about global warming, reducing greenhouse gas emissions has become a top priority. Among the means to reduce greenhouse gas emissions through energy conservation, the high insulation of buildings and other structures, i.e., insulation materials, has been identified as extremely important. High-performance foamed plastic insulation materials are the mainstream, but from the perspective of further improving insulation performance and addressing environmental concerns, the application of vacuum insulation materials is also increasing. As core materials for vacuum insulation materials, fibers, powders, and foams are known to be usable. However, in the most commonly used fibers and powders, most vacuum insulation materials have poor surface smoothness. Even in vacuum insulation materials with foam as the core material, surface smoothness remains problematic both immediately after manufacturing and over time. Furthermore, especially when using fibers as the core material, the thickness (thickness change) under atmospheric pressure is greater than the thickness under depressurization, resulting in poor workability when filling airtight bags to manufacture vacuum insulation materials. On the other hand, in vacuum insulation materials that use foam as the core material, there is a known technique that uses so-called interconnected bubble foam that maintains the bubble structure as the core material, but its strength in the thickness direction can barely withstand decompression (atmospheric pressure). Therefore, there is a concern that if a load is applied in the thickness direction during on-site construction or other operations, the bubbles will be destroyed, that is, the surface smoothness will be further deteriorated.

[0003] Patent document 1 discloses a technology involving a vacuum insulation material in which a core material composed of a phenolic resin cured foam contains bubbles of 50 to 500 μm and micropores of 0.5 to 30 μm are formed on the outer periphery of the bubbles, thereby increasing the porosity of the phenolic resin cured foam to more than 50%, thereby improving the structural strength and enabling the overall weight to be reduced.

[0004] In addition, Patent Document 2 discloses a vacuum insulation material that uses a lightweight, high-performance, and fluorine-free insulation material. The insulation material is a continuous bubble foam body with a core material formed by compressing the bubbles after foaming to flatten them into a flat shape. The pressure reduction is set to 0.1 to 0.01 Torr, thereby further reducing the thermal conductivity.

[0005] Furthermore, Patent Document 3 discloses the following technology: by not setting deformable bubble films at the apex or ridge of the core material constituting the vacuum insulation body, the deformation of continuous bubble polyurethane caused by atmospheric compression after vacuum exhaust can be suppressed on the whole insulation body, and the vacuum degree and insulation performance of the vacuum insulation body can be maintained for a long time.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Publication No. 2014-503054

[0009] Patent Document 2: Japanese Patent Application Publication No. 6-213561

[0010] Patent Document 3: Japanese Patent Application Publication No. 2020-020431 Summary of the Invention

[0011] The problem the invention aims to solve

[0012] However, in Patent Document 1, the bubble-connected phenolic foam is used as the core material of the vacuum insulation material while retaining its bubble structure. Therefore, the bubble structure of the phenolic foam core material is only superficially maintained under reduced pressure, resulting in the following problems: it cannot withstand reduced pressure (atmospheric pressure), leading to localized bubble destruction; the surface smoothness is poor immediately after manufacturing; and the surface smoothness becomes unstable as the bubbles break over time. Furthermore, because the bubble structure is maintained, its strength in the thickness direction can only barely withstand reduced pressure (atmospheric pressure). Therefore, when impacts such as loads exceeding atmospheric pressure are applied in the thickness direction, the bubbles are easily destroyed, further deteriorating the surface smoothness.

[0013] Patent Document 2 discloses a technology involving a vacuum insulation material using a continuously compressed rigid polyurethane foam as the core material. While its characteristic is that the interconnected bubbles in the foam are maintained in a flattened shape to increase the decompression to 0.1 to 0.01 Torr, it suffers from the following problems, similar to Patent Document 1: immediately after manufacturing and over time, some bubbles are destroyed due to their inability to withstand atmospheric pressure, resulting in poor surface smoothness. Furthermore, the surface smoothness becomes unstable over time due to the restoring force of the deformed bubbles. Additionally, similar to Patent Document 1, because the bubble structure is maintained, its thickness-direction strength can only barely withstand decompression (atmospheric pressure). Therefore, during on-site construction or other operations, if an impact such as a load exceeding atmospheric pressure is applied in the thickness direction, the bubbles are easily destroyed, further deteriorating the surface smoothness.

[0014] In addition, Patent Document 3 describes a technique characterized by the following: as a method to improve the compressive strength of continuous bubble polyurethane foam, deformable bubble films are not provided at the apex or ridge of the core material constituting the vacuum insulation body. As a result, although the deformation caused by atmospheric compression after vacuum exhaust can be suppressed in the insulation body as a whole, the compressive strength is not high. When an impact such as a load is applied in the thickness direction, the bubbles are easily destroyed, resulting in poor surface smoothness.

[0015] Therefore, the object of the present invention is to provide a vacuum insulation material and its core material that have good surface smoothness, excellent strength in the thickness direction, and good workability as a vacuum insulation material.

[0016] Solution for solving the problem

[0017] To solve the aforementioned problems, the inventors conducted repeated and in-depth research, and discovered that by pre-compressing and molding a foam to destroy the bubble structure, creating a resin component that is substantially bubble-free, and then inserting it as a core material into a thin film bag containing an outer sheath material, while setting the bag under reduced pressure, a vacuum insulation material with excellent surface smoothness was developed. Furthermore, due to the excellent load-bearing capacity in the thickness direction of this vacuum insulation material, the surface smoothness level can be well maintained. That is, the present invention is as follows.

[0018] [1] A resin component, which is a generally flat resin component,

[0019] The density of the aforementioned resin component is 50 kg / m³. 3 Above and 250kg / m 3 the following,

[0020] When the amount of indentation (mm) of the aforementioned resin component is defined as Dh0 when a load generated by a cylindrical stainless steel SUS304 with a diameter of 6 mm and a mass of 3 kg is applied to the aforementioned resin component in a direction parallel to the thickness direction of the aforementioned resin component, Dh0 is less than 7.5 mm.

[0021] [2] According to the resin component described in [1], in a 0.25mm × 0.25mm photograph taken by electron microscopy at 500x magnification with the center of the thickness direction of the aforementioned resin component located in the center of the field of view and the vertical direction of the field of view being the thickness direction of the resin component, the connected resin skeleton surrounding the bubble film is 0 or 1.

[0022] [3] The resin component according to [1] or [2], wherein the aforementioned resin component is selected from one or more of the group consisting of phenolic resin, polyurethane resin and styrene resin.

[0023] [4] The resin component according to any one of [1] to [3], wherein the aforementioned resin component is phenolic resin.

[0024] [5] A vacuum insulation material comprising:

[0025] Sealed bags; and

[0026] The resin component described in any one of [1] to [4] is sealed in the aforementioned bag under reduced pressure.

[0027] [6] According to the vacuum insulation material described in [5], wherein the density of the aforementioned vacuum insulation material is 60 kg / m³. 3 Above and 260kg / m 3 the following.

[0028] [7] According to the vacuum insulation material described in [5] or [6], wherein the aforementioned vacuum insulation material has a thermal conductivity of less than 0.010 W / (m·K) at 23°C.

[0029] [8] The vacuum insulation material according to any one of [5] to [7], wherein the surface smoothness level of the aforementioned vacuum insulation material is 1.8 mm or less.

[0030] [9] The vacuum insulation material according to any one of [5] to [8], wherein when the amount of indentation (mm) of the vacuum insulation material when a load generated by a cylindrical stainless steel SUS304 with a diameter of 6 mm and a mass of 5 kg is applied to the vacuum insulation material in a direction parallel to the thickness direction of the aforementioned resin component is defined as Dh1, Dh1 is less than 7.5 mm.

[0031] The effects of the invention

[0032] According to the present invention, a vacuum insulation material and its core material with good surface smoothness and excellent strength in the thickness direction can be provided as a vacuum insulation material. Attached Figure Description

[0033] Figure 1 This is a perspective view schematically showing the resin component of Example 1.

[0034] Figure 2 This is a schematic perspective view of the vacuum insulation material of Example 1.

[0035] Figure 3 This is a schematic top view illustrating the vacuum insulation material of Example 1.

[0036] Figure 4 This is a side view schematically showing a cross-section of the vacuum insulation material of Example 1.

[0037] Figure 5 This is a schematic top view illustrating the vacuum insulation material of Example 4.

[0038] Figure 6 The photograph, measuring 0.25mm × 0.25mm, is taken using an electron microscope at 500x magnification, with the center of the resin component raw material (resin foam before bubble destruction) of Example 1 located in the center of the field of view and the vertical direction of the field of view being the thickness direction of the resin component.

[0039] Figure 7 The photograph is a 0.25mm × 0.25mm image taken by magnifying it 500 times using an electron microscope, with the center of the resin component in the thickness direction of Example 1 located in the center of the field of view and the vertical direction of the field of view being the thickness direction of the resin component.

[0040] Figure 8 The photograph is a 0.25mm × 0.25mm image taken by magnifying it 500 times using an electron microscope, with the center of the thickness direction of the resin component of Comparative Example 1 located in the center of the field of view and the vertical direction of the field of view being the thickness direction of the resin component.

[0041] Figure 9 It is shown in Figure 8 The photo shows the connected resin skeleton surrounding the bubble wrap.

[0042] Figure 10 This is a schematic diagram of an example of a Dh0 measuring device. Detailed Implementation

[0043] The following is a detailed description of the method for implementing the present invention (hereinafter referred to as "this embodiment"). It should be noted that the present invention is not limited to the following embodiment, and various modifications can be made within its scope.

[0044] The density, closed-cell ratio, and indentation amount of the resin component in this embodiment when a load of cylindrical stainless steel SUS304 with a diameter of 6 mm and a mass of 3 kg is applied to the resin component in a direction parallel to the thickness direction of the resin component; the presence or absence of substantial bubble structure at the center position of the resin component in the thickness direction (i.e., the number of connected resin skeletons surrounding the bubble film in a 0.25 mm × 0.25 mm field of view photograph taken using an electron microscope at 500x magnification); and the thermal conductivity, density, and surface smoothness level of the vacuum insulation material of this embodiment at 23°C; and the indentation amount of the vacuum insulation material when a load of cylindrical stainless steel SUS304 with a diameter of 6 mm and a mass of 5 kg is applied to the vacuum insulation material in a direction parallel to the thickness direction of the resin component are determined by the method described in the examples.

[0045] (Resin component)

[0046] The resin component in this embodiment is a generally flat resin component.

[0047] The density of the aforementioned resin component is 50 kg / m³. 3 Above and 250kg / m 3 the following,

[0048] When a load generated by a cylindrical stainless steel SUS304 with a diameter of 6 mm and a mass of 3 kg is applied to the resin component in a direction parallel to the thickness direction of the resin component, the indentation amount (mm) of the resin component is set as Dh0, and Dh0 is less than 7.5 mm.

[0049] Figure 4 This is a schematic side view of a cross-section of the vacuum insulation material of Embodiment 1 described below. In this embodiment, the vacuum insulation material 3 is obtained by covering the resin component 1 with a highly airtight bag-shaped film 4, followed by venting, and then sealing the bag-shaped film with a heat-sealing part 5.

[0050] In this embodiment, a resin component refers to a solid component made of resin. It can be a homogeneous resin, or it can contain gases such as air, either uniformly or non-uniformly, and the presence or absence of surface material is not limited. Furthermore, it may contain adhesives, coating agents, etc., and its processing form is not restricted. Moreover, the resin component may also contain additives other than the main components of the resin component. It should be noted that the raw materials used to manufacture the resin component are referred to as resin component raw materials.

[0051] The resin component is generally flat. Examples of generally flat shapes include cuboids, prisms, and disks. In this embodiment, "generally cuboid" means that the faces forming the cuboid are not necessarily flat, and also includes cases where the faces are curved, or where the faces are connected by curved surfaces, or where the corners are curved.

[0052] The density of the resin component in this embodiment is 50 kg / m³. 3 Above and 250kg / m 3 The preferred value is 80 kg / m³. 3 Above and 170kg / m 3 The following is more preferably 90 kg / m 3 Above and 160kg / m 3 The following is a further preferred value: 100 kg / m 3 Above and 150kg / m 3 The optimal value is 110 kg / m³. 3 Above and 140kg / m 3 The following applies if the density of the resin component is 50 kg / m³. 3 Therefore, when a load is applied to the resin component in a direction perpendicular to the thickness direction, it is less prone to indentation. Consequently, when this resin component is used as the core material of a vacuum insulation material, the surface smoothness of the vacuum insulation material is good, and the mechanical strength, such as load-bearing capacity, is ensured, preventing indentation and breakage. On the other hand, if the density of the resin component is 250 kg / m³... 3Therefore, when used as the core material of vacuum insulation, the weight of the vacuum insulation material does not increase, resulting in excellent operability. Furthermore, the thermal conductivity of the vacuum insulation material is also affected by the density of the resin component, and remains within a suitable range.

[0053] The resin component in this embodiment has the following characteristics: the indentation amount (mm) is small when a load generated by a cylindrical stainless steel SUS304 with a diameter of 6 mm and a mass of 3 kg is applied in a direction parallel to its thickness direction. That is, when this indentation amount is set as Dh0, if Dh0 is less than 7.5 mm, then during operations such as on-site construction of vacuum insulation materials with this resin component as the core material, it is not easy to deform even when impact is applied in its thickness direction, and performance degradation is not easily caused. Dh0 is preferably less than 6 mm, more preferably less than 4 mm, further preferably less than 2.5 mm, and most preferably less than 1.5 mm. Dh0 is, for example, 0 mm or more. The thickness direction is the direction of the distance between the two shortest distances between two opposing surfaces of the generally flat resin component. It should be noted that in this evaluation, when the cylindrical object penetrates the resin component, Dh0 is determined by re-evaluating after multiple resin components are overlapped.

[0054] Figure 10 This is a schematic diagram of an example of the measuring apparatus for Dh0. The resin component 9 is placed on two parallel wooden pieces 14 spaced 20mm apart, with the overlap between the resin component 9 and each wooden piece 14 being at least 5mm. Above the resin component, a position adjustment handle 13 is rotated using a pulley 12, thereby allowing a line 11 to move up and down. A cylindrical stainless steel SUS304 (symbol 10) with a diameter of 6mm and a mass of 3kg is suspended by this line 11.

[0055] SUS304 stainless steel is equivalent to ISO standard X5CrNi18-10 (4301-304-00-I).

[0056] When using fibers as the core material, the thickness (thickness variation) under atmospheric pressure is greater than the thickness under decompression, resulting in poor workability when filling a highly airtight bag to manufacture vacuum insulation material. More specifically, for example, (1) inserting a fiber-based core material with a large thickness under atmospheric pressure into a bag with a small thickness (fold width) is cumbersome; (2) when decompressing the bag after inserting the fiber-based core material, unevenness is easily generated on the surface of the bag or the bag is easily bent, resulting in poor workability. Based on this, compared with fibers, which usually have a large thickness difference between the core material and the vacuum insulation material, it is more ideal to use a material formed from resin foam (resin component raw material) as the core material of vacuum insulation material.

[0057] Therefore, for the resin component of this embodiment, in a 0.25mm × 0.25mm photograph taken with an electron microscope at 500x magnification, where the center position (half the thickness) of the aforementioned resin component is located in the center of the field of view and the vertical direction of the field of view is the thickness direction of the resin component, the number of connected resin skeletons surrounding the bubble film is preferably 0 or 1 (also referred to as "substantially not having a bubble structure").

[0058] Field of view refers to a 0.25mm × 0.25mm area captured by magnification 500x using an electron microscope. Figure 7 The area at the bottom of the photograph that contains information such as magnification and scale is not the area being photographed and therefore is not included in the field of view.

[0059] Figure 8 This is a 0.25mm × 0.25mm photograph taken using an electron microscope at 500x magnification, with the center of the resin component in the thickness direction of Comparative Example 1 centered in the field of view, and the vertical direction of the field of view corresponding to the thickness direction of the resin component. Figure 8 In the photograph, the bubble membrane 7 surrounded by the bubble skeleton 6 can be observed. It should be noted that the bubble skeleton 6 refers to the resin skeleton that forms the foam, and the bubble membrane 7 refers to the resin membrane surrounded by the resin skeleton.

[0060] Figure 9 This is to demonstrate the purpose of evaluating the presence or absence of substantial bubble structures. Figure 8 The photograph shows the connected resin skeleton surrounding the bubble wrap. A and B, enclosed in black lines, represent the connected resin skeleton surrounding the bubble wrap. Therefore, in Figure 8 and Figure 9 In the photo, there are two connected resin skeletons (A and B) surrounding the bubble wrap.

[0061] Figure 7 This is a 0.25mm × 0.25mm photograph taken using an electron microscope at 500x magnification, with the center of the resin component in the thickness direction of Example 1 centered in the field of view and the vertical direction of the field of view corresponding to the thickness direction of the resin component. In this photograph, the number of connected resin skeletons surrounding the bubble film is 0.

[0062] If there is no substantial bubble structure at the center position in the thickness direction, the strength of the vacuum insulation material is easily sufficient when it is used as the core material of the vacuum insulation material, the surface smoothness is good, and it is less likely to cause indentation when a load is applied in the direction perpendicular to the thickness direction, so it is preferred.

[0063] The presence or absence of bubble structures in areas other than the center position in the thickness direction is not limited. However, since it is easy to improve the surface smoothness and the strength in the thickness direction, the thermal conductivity of the vacuum insulation material used as the core material becomes easier to reduce. Therefore, it is more preferable that the bubble structure is substantially absent, similar to the center position in the thickness direction.

[0064] The size of the resin component can also be appropriately set according to the purpose. In the case of a roughly rectangular shape, the side other than the thickness direction is preferably 30mm or more and 6000mm or less, more preferably 50mm or more and 3000mm or less, further preferably 100mm or more and 2000mm or less, and most preferably 200mm or more and 1200mm or less. Furthermore, the thickness of the resin component is preferably 1mm or more and 120mm or less, more preferably 2mm or more and 80mm or less, further preferably 3mm or more and 50mm or less, and most preferably 5mm or more and 50mm or less.

[0065] The closed-cell ratio of the resin component in this embodiment is not particularly limited, but is, for example, 10% or less, preferably 5% or less, more preferably 1% or less, further preferably 0.5% or less, and most preferably 0%. If the closed-cell ratio of the resin component is 5% or less, Dh0 can be reduced, and in the case of a resin foam, the amount of gas contained in the bubbles is reduced, so it can be suppressed without relying on the heat conduction of the contained gas, thus reducing the thermal conductivity of the vacuum insulation material when it is used as the core material of the vacuum insulation material.

[0066] The raw materials for the resin component in this embodiment are not particularly limited, and can include phenolic resin, polystyrene, polyolefins such as polyethylene or polypropylene, polyacrylate, vinyl chloride, polyurethane, etc. Additionally, the resin component can be obtained through operations such as compression of the foam. In particular, phenolic resin foam, rigid polyurethane resin foam, and polystyrene resin foam, whose bubble structures are easily destroyed by excessive compression, are preferred, with phenolic resin foam, being a highly brittle raw material, being more preferred. It is preferable to compress these resin foams so that the bubble structure at the center of the thickness direction substantially disappears. For objects with surface materials such as phenolic resin, the resin component can be either with the surface material attached or with the surface material peeled off.

[0067] In one embodiment, the resin component is one or more selected from the group consisting of phenolic resin, polyurethane resin, and styrene resin. In another embodiment, the resin component is phenolic resin.

[0068] In one embodiment of the resin component, the thickness of the resin component under reduced pressure (130 Pa) is 50 to 100% of the thickness under atmospheric pressure.

[0069] As the raw material for the resin component in this embodiment, scraps (fragments) of one or more resin foams can also be used. Scraps of the same thickness can be arranged perpendicular to the thickness direction or overlapped along the thickness direction; the combination of multiple scraps is not limited. In this case, the resin component can also be made from scraps of one or more resin foams. However, even when used as the core material of a vacuum insulation material, the pressure inside the highly airtight bag-shaped film covering the resin component decreases, improving the adhesion between the resin components and achieving integration, thus enabling the manufacture of an excellent vacuum insulation material.

[0070] The resin component of this embodiment can be manufactured as follows: A resin foam of desired size is prepared, and air bubbles are destroyed by uniformly pressing the entire surface area of ​​its upper and lower layers in the thickness direction. When using the resin foam as raw material, the foaming agent contained therein diffuses and the thickness is reduced (volume reduction) during the pressing (compression). This preferably results in a resin component that does not substantially have a bubble structure at its center in the thickness direction. Here, the method of uniformly pressing the entire surface area of ​​the upper and lower layers in the thickness direction can utilize a roller press or the like, but is not particularly limited. It should be noted that the value obtained by dividing the thickness of the obtained resin component by the thickness of the resin component raw material is defined as the volume reduction ratio.

[0071] Figure 6 The photograph, measuring 0.25mm × 0.25mm, is taken using an electron microscope at 500x magnification, with the center of the resin component raw material (resin foam before bubble destruction) of Example 1 below located in the center of the field of view and the vertical direction of the field of view being the thickness direction of the resin component.

[0072] For the resin component of this embodiment, it can be covered with a highly airtight bag-shaped film, and then the air is vented to airtightly seal and block the bag-shaped film, thereby producing a vacuum insulation material.

[0073] (Vacuum insulation material)

[0074] The vacuum insulation material of this embodiment includes: a sealed bag; and

[0075] The resin component described in any one of the preceding statements is sealed in the aforementioned bag under reduced pressure.

[0076] In vacuum insulation materials, the resin component disposed inside the bag is the aforementioned resin component, and further explanation is omitted.

[0077] The thermal conductivity of the vacuum insulation material in this embodiment is preferably 0.010 W / (m·K) or less at 23°C. More preferably, it is 0.009 W / (m·K) or less, more preferably 0.008 W / (m·K) or less, even more preferably 0.007 W / (m·K) or less, and most preferably 0.006 W / (m·K) or less. If the thermal conductivity of the vacuum insulation material at 23°C is 0.01 W / (m·K) or less, it can exhibit high thermal insulation performance even when thin.

[0078] The density of the vacuum insulation material in this embodiment is, for example, 60 kg / m³. 3 Above and 260kg / m 3 The preferred value is 70 kg / m³. 3 Above and 200kg / m 3 The following is more preferably 85 kg / m 3 Above and 175kg / m 3 The following is a further preferred value: 110 kg / m 3 Above and 170kg / m 3 The optimal value is 125 kg / m³. 3 Above and 155kg / m 3 The following applies if the density of the vacuum insulation material is 60 kg / m³. 3 The above ensures mechanical strength, such as load-bearing capacity, and prevents breakage. On the other hand, if the density of the vacuum insulation material is 260 kg / m³... 3 Therefore, the weight of the vacuum insulation material will not increase, resulting in excellent operability. Furthermore, the thermal conductivity of the vacuum insulation material is also affected by the density of the resin component, and remains within a suitable range.

[0079] The surface smoothness level of the vacuum insulation material in this embodiment is, for example, 1.8 mm or less, preferably 1.5 mm or less, more preferably 1.1 mm or less, further preferably 0.9 mm or less, and most preferably 0.8 mm or less. It should be noted that if the surface smoothness level of the vacuum insulation material is 1.8 mm or less, it is possible to achieve high airtightness during construction by utilizing its surface smoothness, and the operability is also excellent.

[0080] For the vacuum insulation material of this embodiment, when the indentation amount (mm) of the vacuum insulation material is applied to the vacuum insulation material in a direction parallel to the thickness direction of the aforementioned resin component or vacuum insulation material, and a load generated by a cylindrical stainless steel SUS304 with a diameter of 6 mm and a mass of 5 kg is applied, it is defined as Dh1. Preferably, Dh1 is less than 7.5 mm. If Dh1 is less than 7.5 mm, it is less likely to deform even when impact is applied in the thickness direction during on-site construction and other operations, and performance degradation is less likely to occur. Dh1 is preferably less than 6.0 mm, more preferably less than 4.0 mm, further preferably less than 2.5 mm, and most preferably less than 1.5 mm. Dh1 is, for example, 0 mm or more. It should be noted that in this evaluation, even if the highly airtight film bag on the surface of the vacuum insulation material is ruptured, it is evaluated as the indentation amount. In addition, in this evaluation, when the cylindrical object penetrates the vacuum insulation material, Dh1 is determined by re-evaluating after multiple pieces of vacuum insulation material are overlapped.

[0081] There are no particular limitations on the airtight bag-shaped film covering the resin components used in the manufacture of vacuum insulation materials; its material, size, thickness, etc., can be appropriately selected according to the purpose. Preferred films include composite films, particularly multilayer composite films containing a metal (e.g., aluminum) layer that has been vapor-deposited or laminated. Suitable films include, for example, polyester; polyvinyl chloride; polyolefins such as polyethylene or polypropylene; or polyvinyl alcohol.

[0082] The size of the vacuum insulation material is influenced by the size of the resin component and can be appropriately set according to the purpose. In the case of a roughly rectangular shape, the thickness of one side (excluding the thickness direction) is preferably 30 mm or more and 60 mm or less, more preferably 50 mm or more and 30 mm or less, further preferably 100 mm or more and 20 mm or less, and most preferably 200 mm or more and 12 mm or less. Furthermore, the thickness of the vacuum insulation material is preferably 1 mm or more and 120 mm or less, more preferably 2 mm or more and 80 mm or less, further preferably 3 mm or more and 50 mm or less, and most preferably 5 mm or more and 50 mm or less.

[0083] The shape of the vacuum insulation material is influenced by the shape of the resin component, but is not particularly limited and can be any shape. Examples include cuboids (e.g., plate-like, layered, sheet-like, etc.), prisms, cylinders, disks, and polyhedra other than cuboids (e.g., regular tetrahedrons, regular octahedrons, regular dodecahedrons, regular icosahedrons, etc.). In this embodiment, "approximately cuboid" means that the faces forming the cuboid are not necessarily planar, and also includes cases where the face is curved, or where the faces are connected by curved surfaces, or where the corners are curved surfaces.

[0084] There are no particular limitations on the method of sealing the bag-shaped film; for example, known methods such as heat sealing can be used. As long as the resin component is sealed by the bag-shaped film, the film is sealed airtightly after the air inside the bag containing the resin component is vented. It should be noted that materials that absorb moisture and other gases, such as getters, can also be appropriately attached to or inserted into the bag.

[0085] Vacuum insulation materials are obtained by enclosing resin components within a bag-shaped film, depressurizing the pressure inside the film, and then sealing it using heat sealing or other methods. The pressure inside the bag-shaped film is, for example, 1 Pa or more and 1000 Pa or less, preferably 5 Pa or more and 500 Pa or less, and more preferably 10 Pa or more and 200 Pa or less. Setting the pressure inside the bag-shaped film to 1000 Pa or less reduces the thermal conductivity of the resulting vacuum insulation material at 23°C. Furthermore, setting it to 1 Pa or more prevents damage to the bag-shaped film caused by pressure differences with atmospheric pressure.

[0086] Example

[0087] The present invention will now be described in more detail through examples and comparative examples, but the present invention is not limited thereto.

[0088] (Examples 1-3, Examples 5-8, Example 11, and Comparative Example 2)

[0089] <Preparation of Resin Component Raw Materials A-E and J>

[0090] In the manufacture of phenolic resin foam according to Example 1 of Japanese Patent Application Publication No. 2021-192962, the amount of foaming agent was set to 4.5 parts by weight, and a phenolic resin foam (resin component raw material A) with a thickness of 45 mm was obtained in the same manner. The density and closed-cell ratio of the phenolic resin foam were measured using the following method, and the density was found to be 30 kg / m³. 3 The closed-pore rate is 93%.

[0091] Similarly, phenolic resin foam obtained by adjusting the amount of foaming agent, acidic curing agent, height of the free roller in the preforming process, and temperature in the main forming process was cured at 120°C for 4 hours to obtain the resin component raw materials B to E and J recorded in Table 1.

[0092] <Fabrication of Resin Components A1-A3, B1-E1, E2 and J1>

[0093] Resin components are obtained by reducing the volume of resin component raw materials using a roller compression device. The roller compression device consists of an input platform and a roller compression unit. The resin component raw material is fed between an upper roller (hydraulic cylinder lifting type) and a fixed lower roller. While moving at a constant speed, the material is compressed to a volume reduction ratio of 0.1 to 0.9 by applying pressure between the two rollers. By adjusting the type (thickness) of the resin component raw material and the interval between the upper and lower rollers, resin components A1 to A3, B1 to E1, E2, and J1, as shown in Table 1, are obtained. The density, closed-cell ratio, Dh0, and number of connected resin skeletons surrounding the bubble film at the center position in the thickness direction of these resin components A1 to A3, B1 to E1, E2, and J1 are shown in Table 2.

[0094] Figure 1 This is a perspective view schematically showing the resin component of Example 1. Figure 1 In the figure, symbol 2 represents the thickness of resin component 1.

[0095] <Fabrication of vacuum insulation materials A1S~A3S, B1S~E1S, E2S and J1S>

[0096] After resin components A1-A3, B1-E1, E2, and J1 are made into a size of 270mm×270mm, they are placed inside an aluminum bag (polyethylene terephthalate / aluminum foil / polyethylene vapor-deposited bag) manufactured by Mitsubishi Gas Chemical (standard AB350500PL; 350mm×500mm). Then, the pressure inside the aluminum bag is reduced to 130Pa using an FVCII-G "small vacuum gas packaging machine" manufactured by Furukawa Manufacturing Co., Ltd., and the opening of the aluminum bag is sealed by heat sealing to obtain vacuum insulation materials A1S-A3S, B1S-E1S, E2S, and J1S.

[0097] Figure 2 This is a schematic perspective view of the vacuum insulation material of Example 1. The resin component 1 is housed within a highly airtight, bag-shaped film bag 4 of the vacuum insulation material 3. Furthermore, Figure 3 This is a schematic top view illustrating the vacuum insulation material of Example 1.

[0098] (Example 4)

[0099] <Making of Resin Components A4>

[0100] Resin component A1 was obtained in the same manner as in Example 1. Three pieces of 90mm × 270mm size were cut from resin component A1 (one of which was designated as resin component 1'), resulting in three test pieces A1(1) to A1(3). These three test pieces were collectively referred to as A4. For each of A1(1) to A1(3), the density, closed-cell ratio, Dh0, and the number of connected resin skeletons surrounding the bubble film at the center position in the thickness direction were evaluated, and the average values ​​of A1(1) to A1(3) were calculated. These average values ​​were then used as the density, closed-cell ratio, and Dh0 of A4. After evaluating A1(1) to A1(3) for the number of connected resin skeletons surrounding the bubble film at the center position in the thickness direction, since all of them were substantially bubble-free structures, the evaluation result for A4 was "0". The results are shown in Table 2.

[0101] <Fabrication of Vacuum Insulation Material A4S>

[0102] By arranging three test pieces A1(1) to A1(3) perpendicular to the thickness direction to form an apparent size of 270mm × 270mm, and then placing them inside an aluminum bag manufactured by Mitsubishi Gas Chemical (standard AB350500PL; 350mm × 500mm), the pressure inside the aluminum bag was reduced to 130Pa using an FVCII-G "small vacuum gas packaging machine" manufactured by Furukawa Manufacturing Co., Ltd. The opening of the aluminum bag was then sealed by heat sealing to obtain vacuum insulation material A4S.

[0103] Figure 5 This is a schematic top view illustrating the vacuum insulation material of Example 4.

[0104] (Example 9)

[0105] <Fabrication of Resin Component F1>

[0106] As the raw material for the resin component, a "Q1 Board, 30mm" manufactured by Achilles Corporation was used to obtain resin component F1 in the same manner as in Example 1. For F1, the density, closed-cell ratio, Dh0, and the number of connected resin skeletons surrounding the bubble film at the center position in the thickness direction were determined. The results are shown in Table 2.

[0107] <Fabrication of Vacuum Insulation Material F1S>

[0108] Regarding the resin component F1, except for the resin component used, the vacuum insulation material F1S was obtained by performing the same operation as in Example 1.

[0109] (Example 10)

[0110] <Fabrication of Resin Component G1>

[0111] As the raw material for the resin component, "Styrofoam (registered trademark) IB, 30mm" manufactured by DuPont Styro Corporation was used, and resin component G1 was obtained in the same manner as in Example 1. For G1, the density, closed-cell ratio, Dh0, and the number of connected resin skeletons surrounding the bubble film at the center position in the thickness direction were determined. The results are shown in Table 2.

[0112] <Fabrication of Vacuum Insulation Material G1S>

[0113] Regarding the resin component G1, except for the resin component used, the vacuum insulation material G1S was obtained by performing the same operation as in Example 1.

[0114] (Comparative Example 1)

[0115] <Preparation of Resin Component Raw Material H>

[0116] In the manufacture of phenolic resin foam according to Example 1 of Japanese Patent Application Publication No. 2021-192962, 1.0 part of a composition containing 50% by mass each of an ethylene oxide-propylene oxide block copolymer (as a surfactant) and polyoxyethylene dodecyl phenyl ether (by mass ratio) was set relative to 100 parts by mass of phenolic resin; 3.5 parts of Dow Toray Co., Ltd. additive 8032 were added; and the water content was set to 9%. Similarly, a phenolic resin foam (resin component raw material H) with a thickness of 35 mm was obtained. The density was 33 kg / m³. 3 The closed-pore rate was 4.1%.

[0117] <Fabrication of Resin Component H1>

[0118] Without using a roller compression device to reduce volume, the resin component raw material H is directly used as the resin component (the resin component is labeled H1). The density, closed-cell ratio, Dh0, and presence or absence of substantial bubble structure at the center position in the thickness direction of the resin component H1 are shown in Table 2.

[0119] <Fabrication of vacuum insulation material H1S>

[0120] Regarding the resin component H1, except for the resin component used, the vacuum insulation material H1S was obtained by performing the same operation as in Example 1.

[0121] (Comparative Example 3)

[0122] <Preparation of Resin Component Raw Material K>

[0123] In the manufacture of phenolic resin foam according to Example 1 of Japanese Patent Application Publication No. 2021-192962, 1.75 parts by weight of a composition containing 50% by weight of ethylene oxide-propylene oxide block copolymer and polyoxyethylene dodecyl phenyl ether as surfactant, respectively, were added, relative to 100 parts by weight of phenolic resin. 1.75 parts by weight of Dow Toray Co., Ltd. additive 8032 were also added. Otherwise, a phenolic resin foam (resin component raw material K) with a thickness of 35 mm was obtained. The density and closed-cell ratio of the phenolic resin foam were measured using the following method, and the density was found to be 31 kg / m³. 3 The closed-cell rate was 62%. The obtained phenolic resin foam was used as raw material K for resin components.

[0124] <Fabrication of Resin Component K1>

[0125] Using resin component raw material K, resin component K1 was obtained in the same manner as in Example 1. Regarding K1, the density, closed-cell ratio, Dh0, and presence or absence of substantial bubble structure at the center position in the thickness direction are shown in Table 2.

[0126] <Fabrication of K1S Vacuum Insulation Material>

[0127] Regarding the resin component K1, except for the resin component used, the vacuum insulation material K1S was obtained by performing the same operation as in Example 1. Afterwards...

[0128] <Density of resin component raw materials>

[0129] A 200mm square piece of resin component raw material was used as a sample, and its mass and apparent volume were determined according to JIS K7222. When the resin component raw material was smaller than 200mm, the size was adjusted appropriately, and the mass and apparent volume were measured to determine the density. It should be noted that when using multiple resin component raw materials, the density obtained from various evaluations was averaged to obtain the "density of the resin component raw material".

[0130] <Density of resin components>

[0131] Using the resin component as a sample, its mass was first measured. Next, to determine the volume, four measurements were taken at each of the three sides of the roughly flat plate. The average value of each side was then calculated as the volume of the roughly flat plate. It should be noted that the thickness and consequently volume of the sample varied during the measurements; therefore, a ruler was used instead of calipers to avoid pressing. The density of the resin component was calculated by dividing the mass by the volume. It should also be noted that when using multiple resin components, the density obtained from evaluating each component individually was averaged to obtain the "density of the resin component".

[0132] <Closed porosity>

[0133] The closed-cell ratio of resin components was determined according to ASTM-D-2856 (Method C). Specifically, after removing the surface material from the resin component, five approximately 1 cm cubes were cut from the sample with surface material attached, centered along the thickness direction of the resin component. The sample volume was measured using an air comparative hydrometer (Tokyo Science, Model 1000). The volume of the bubble walls (bubble skeleton and bubble film) was calculated from the sample mass and the density of the resin component. The apparent volume was calculated from the external dimensions of the sample. The closed-cell ratio was obtained by subtracting the volume of the bubble walls (bubble skeleton and bubble film) from the sample volume and dividing the result by the apparent volume. The density of phenolic resin is 1.3 kg / L. For resins other than phenolic resin, an appropriate density value was used after confirming the suitable material. It should be noted that when using multiple resin components, the closed-cell ratio obtained from each evaluation was averaged to obtain the "closed-cell ratio of the resin component".

[0134] <Indentation amount under applied load: Dh0>

[0135] The thickness of the resin component was measured at four points 20 mm inward from the four corners using vernier calipers, and the average value was taken as the thickness of the resin component. Then, a sample was placed on a smooth surface with the thickness direction aligned vertically. Furthermore, as... Figure 10 As shown, a sample 9 is placed on two parallel wooden pieces 14 spaced 20 mm apart, with the resin component 9 overlapping each wooden piece 14 by at least 5 mm. A position adjustment handle 13 is rotated from above using a pulley 12, thereby suspending a cylindrical stainless steel SUS304 (symbol 10) with a diameter of 6 mm and a mass of 3 kg from above using a vertically movable line 11. The stainless steel 10 is slowly lowered from above relative to the sample 9 to a position corresponding to the middle of the two wooden pieces 14 spaced 20 mm apart. The stainless steel 10 then stands upright on the sample 9, and after the line 11 is relaxed, it is held for 30 seconds. Then, the line 11 is lifted, and the indentation of the sample 9 is measured using vernier calipers. For one of the two samples 9, the upper surface is measured, and for the remaining sample, the lower surface is measured. The average value of these two measurements is taken as Dh0 (mm). It should be noted that when using multiple resin components, each component is evaluated individually, and the resulting amount of indentation is averaged, which is then used as "Dh0".

[0136] <Number of connected resin skeletons surrounding the bubble membrane at the center position in the thickness direction>

[0137] Regarding the resin component (which serves as the core material when used as vacuum insulation), its thickness was measured. In a 0.25mm × 0.25mm photograph taken using an electron microscope at 500x magnification, with the center of the thickness direction (half the thickness) in the field of view and the vertical direction of the field of view corresponding to the thickness direction of the resin component, the number of connected resin skeletons surrounding the bubble membrane was counted within the aforementioned field of view. The same operation was performed three times in photographs of other locations, for a total of four measurements. The maximum value among the four measurements was used as the "number of connected resin skeletons surrounding the bubble membrane" for evaluation. It should be noted that the bubble membrane may also have ruptures or openings. Furthermore, when using multiple resin components, the minimum value among the number of connected resin skeletons surrounding the bubble membrane obtained from each individual evaluation was used as the "number of connected resin skeletons surrounding the bubble membrane at the center of the thickness direction".

[0138] The density, thermal conductivity at 23°C, surface smoothness level, and Dh1 of the vacuum insulation materials obtained in the examples and comparative examples were measured. The results are shown in Table 2.

[0139] <Density of vacuum insulation materials>

[0140] In the case of an approximate cuboid, use vernier calipers to measure four points on each of the three sides, calculate the average value of each side, and use this average value as the volume of the approximate cuboid. Ignore the volume of the portion of the bag-shaped film that is only placed on the surface (excluding the heat-sealed part), and use this volume as the density of the area where the resin sample is located.

[0141] Thermal conductivity of vacuum insulation materials at 23°C

[0142] According to JIS A 1412-2:1999, the thickness-direction thermal conductivity of vacuum insulation materials at 23°C was determined using the following method. The specific steps are as follows: A sample of the vacuum insulation material was placed in an atmosphere of 23±1°C and 50±2% humidity. After at least 24 hours, it was then introduced into a thermal conductivity apparatus similarly placed in an atmosphere of 23±1°C and 50±2% humidity. For the thermal conductivity measurement, a single-piece test body / object configuration (Eihong Precision Machinery Co., Ltd., trade name "HC-074 / FOX304") was used under the condition that the thermal conductivity at 23°C was 13°C for the low-temperature plate and 33°C for the high-temperature plate. It should be noted that the above method is not limited to determining the thermal conductivity of large or very small vacuum insulation materials; an appropriate measuring apparatus can be selected.

[0143] <Surface smoothness level: ΔH>

[0144] The thickness of the vacuum insulation material was measured using vernier calipers. Specifically, for one side, the thickness was measured at 20 different points, including its center, and the difference between the maximum and minimum values, Δhx, was calculated. Similarly, for the side perpendicular to the aforementioned side, the thickness was measured at 20 different points, including its center, and the difference between the maximum and minimum values, Δhy, was calculated. The larger of Δhx and Δhy was then taken as ΔH and evaluated as the surface smoothness level (mm).

[0145] <Indentation amount under applied load: Dh1>

[0146] Cylindrical SUS304 stainless steel with a diameter of 6 mm and a mass of 5 kg was used. Otherwise, the measurements were performed in the same manner as those for Dh0. The upper surface of one of the two samples was measured, and the lower surface of the remaining sample was measured. A total of two measurements were taken, and the average value was calculated as Dh1 (mm).

[0147] [Table 1]

[0148]

[0149] In Table 1, F represents rigid polyurethane resin foam, and G represents polystyrene resin foam.

[0150] [Table 2]

[0151]

[0152] It can be seen that the vacuum insulation materials and their core materials obtained in Examples 1 to 11 are vacuum insulation materials and their core materials with good surface smoothness and excellent strength in the thickness direction compared with the vacuum insulation materials and their core materials obtained in Comparative Examples 1 to 3.

[0153] Explanation of reference numerals in the attached figures

[0154] 1: Resin components

[0155] 1': Resin component (using scrap materials)

[0156] 2: Thickness of resin components

[0157] 3: Vacuum insulation materials

[0158] 4: Highly airtight bag-shaped film bags

[0159] 5: Heat sealing section

[0160] 6: Bubble skeleton

[0161] 7: Bubble wrap

[0162] 8: Connected resin skeleton surrounding the bubble wrap

[0163] 9: Sample

[0164] 10: Cylindrical Stainless Steel SUS304

[0165] 11: Line

[0166] 12: Pulley

[0167] 13: Position adjustment handle

[0168] 14: Wood chips

[0169] Industrial availability

[0170] According to the present invention, a vacuum insulation material and its core material can be provided that have good surface smoothness, excellent strength in the thickness direction, and good workability as a vacuum insulation material.

Claims

1. A resin component, which is a generally flat resin component, The density of the resin component is 50 kg / m³. 3 Above and 250kg / m 3 the following, When the amount of indentation (mm) of the resin component when a load generated by a cylindrical stainless steel SUS304 with a diameter of 6 mm and a mass of 3 kg is applied to the resin component in a direction parallel to the thickness direction of the resin component is defined as Dh0, Dh0 is less than 7.5 mm.

2. The resin component according to claim 1, wherein, In a 0.25mm × 0.25mm photograph taken with an electron microscope at 500x magnification, where the center of the resin component in the thickness direction is located in the center of the field of view and the vertical direction of the field of view is the thickness direction of the resin component, there are 0 or 1 connected resin skeletons surrounding the bubble film.

3. The resin component according to claim 1, wherein, The resin component is selected from one or more of the group consisting of phenolic resin, polyurethane resin and styrene resin.

4. The resin component according to claim 1, wherein, The resin component is phenolic resin.

5. A vacuum insulation material, comprising: Sealed bags; and The resin component of any one of claims 1 to 4, sealed in the bag under reduced pressure.

6. The vacuum insulation material according to claim 5, wherein, The density of the vacuum insulation material is 60 kg / m³. 3 Above and 260kg / m 3 the following.

7. The vacuum insulation material according to claim 5, wherein, The thermal conductivity of the vacuum insulation material is below 0.010 W / (m·K) at 23°C.

8. The vacuum insulation material according to claim 5, wherein, The surface smoothness level of the vacuum insulation material is below 1.8 mm.

9. The vacuum insulation material according to claim 5, wherein, When the indentation (mm) of the vacuum insulation material is defined as Dh1 when a load generated by a cylindrical stainless steel SUS304 with a diameter of 6 mm and a mass of 5 kg is applied to the vacuum insulation material in a direction parallel to the thickness direction of the resin component, Dh1 is less than 7.5 mm.

Images