JP2012013114A - Heat insulating member and building member using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat insulating panel excellent in long-term heat insulation performance as the heat insulating panel of a heat insulating member, which contributes to energy saving of environmentally friendly housing, etc.SOLUTION: A vacuum heat insulating member 1 includes: a core material 3 comprising glass wool; a getter agent 4; and a package material 2 storing the core material 3 and the getter agent 4, and the inside of the package material 2 is sealed in vacuum. In addition, the heat insulating panel 7 of the heat insulating member 10 encloses the vacuum heat insulating member 1 in open cell foam 9 and arranges a sheathing material 5, and the inside of the sheathing material 5 is decompressed and sealed.

Description

  The present invention relates to a heat insulating member and a building member using the same.

  In recent years, from the viewpoint of protecting the global environment, as a measure for energy saving of building structures such as home appliances, industrial equipment, and houses, particularly high heat insulation is demanded for buildings. At that time, if the performance of the heat insulation panel is to be improved, the thickness of the heat insulation layer must be increased, resulting in problems of space and construction. Therefore, a vacuum heat insulating material that has better heat insulating performance than glass wool or foam resin has been proposed. A vacuum heat insulating material is produced by putting a core material excellent in heat insulating properties into an outer packaging material having gas barrier properties and evacuating the inside.

  The vacuum heat insulating material has an excellent initial thermal conductivity. However, the degree of vacuum gradually lowers due to gas intrusion from the outer packaging material that wraps the core material, gas intrusion from the laminate film, moisture adhering to the inside of the vacuum heat insulating material, and the like, and the heat insulating performance gradually deteriorates. In refrigerators and the like, vacuum heat insulating materials are often used for energy saving. At that time, the long-term reliability of the vacuum heat insulating material has been deteriorating in performance assuming about 10 to 15 years, but the Arrhenius plot is used to estimate the lifetime of the electrical component due to time constraints.

  A thermal insulation panel in a thermal insulation member such as a building structure also needs a long-term reliability test, and is required to suppress deterioration for 25 years or longer than a refrigerator. In addition, the vacuum heat insulating material of the heat insulating member is required to maintain high strength for a long period of time without damaging the vacuum heat insulating material especially during transportation, storage and construction against external impacts and the like.

  Conventionally, as a protective material for a vacuum heat insulating material, a heat insulating panel covered with a urethane foam (thermal conductivity: 20 mW / m · K or more) having closed cells has been used from the viewpoint of heat insulating performance (for example, Patent Documents). 1).

Japanese Patent Laid-Open No. 10-211986

  In conventional vacuum insulation materials using closed-cell foam as a protective material, foam gas with lower thermal conductivity than air is trapped in the foam bubbles, so foam with low thermal conductivity in the initial state Become a body. On the other hand, trapping foam gas in closed cells has a good gas permeability coefficient due to good affinity with urethane resin, and carbon dioxide gas is permeated and discharged through the bubble membrane due to the difference in gas partial pressure in the air and in the atmosphere. In addition, since air having a low permeability coefficient does not enter from the outside, the inside of the bubbles is decompressed and foam contraction is likely to occur. In addition, the foaming gas present in the closed cells is diffused into the air with the passage of time, and at the same time, there is a problem that the heat conductivity of the heat insulating material is deteriorated by the air entering the heat insulating material.

  In addition, the injection of foamed resin requires filling the raw material into the narrow space of the vacuum heat insulating material, and the voids generated when the vacuum heat insulating material impedes fluidity must be attached to the mold and removed from the mold. Improvement is needed. Further, since the reaction temperature of the urethane foam reaches about 120 ° C., there is a problem that the vacuum heat insulating material is damaged due to high temperature and the thermal conductivity is deteriorated. For this reason, in direct injection in which the vacuum heat insulating material is covered with the foamed resin, it is necessary to attach the vacuum heat insulating material to the mold and to prepare a mold in consideration of the flow of the foam. In addition, storage until construction (warehouse, etc .: environmental temperature) due to air intrusion into the bubbles, adsorption of moisture in the air (moisture absorption), carbon dioxide in the foaming agent remains in the bubbles and is replaced in the air. Is about 50 ° C.), the dimensional change and shrinkage of the foam and the deterioration of the thermal conductivity are promoted, and there is a problem as a heat insulating material for a building which requires high performance and long-term reliability.

  The present invention has been made in view of the above problems of the prior art, and an object of the present invention is to provide a heat insulating member that has excellent initial thermal conductivity and can reduce deterioration of thermal conductivity.

  In order to achieve the above-mentioned object, the first aspect of the present invention comprises a glass wool core material, a getter agent, and a gas barrier outer packaging material containing the core material and the getter agent, A vacuum heat insulating material whose inside is sealed under reduced pressure, a covering material that is arranged so as to cover the periphery of the vacuum heat insulating material and has a communicating bubble, and an outer casing that houses the vacuum heat insulating material and the covering material And a heat insulating member in which the inside of the covering agent is sealed under reduced pressure.

  According to this heat insulating member, a high-performance vacuum heat insulating material having a glass wool core material and a covering material made of a foamed body having open air bubbles are combined and further sealed under reduced pressure to achieve a high thermal conductivity over a long period of time. It is possible to realize a heat insulating member for construction with less deterioration. By using a foam with open cells as the coating material, it is possible to prevent deterioration of thermal conductivity without air intrusion, moisture adsorption, dimensional change or shrinkage, which was a problem with closed-cell foams. become.

A more preferable specific configuration example in the first aspect of the present invention is as follows.
(1) The thermal conductivity of the coating material under reduced pressure is 10 mW / m · K or less.

According to this heat insulating member, the thermal conductivity can be 10 mW / m · K or less because the communication bubbles of the covering material exist in the vacuum layer. Thereby, the heat insulation member which is excellent in heat insulation performance can be provided by combining the coating material which is excellent in thermal conductivity with a high-performance vacuum heat insulating material.
(2) The heat insulating panel is such that the vacuum heat insulating material and the continuous covering material are independently formed, and the compressive strength of the covering material made of the communicating body is 0.15 MPa or more.

According to this heat insulation panel, the vacuum insulation material and the covering material of the communication body are independent, so that the compression strength can be obtained without foaming and filling the vacuum insulation material with a mold set or the high temperature damage due to the reaction temperature of the urethane foam. It is maintained, and it becomes possible to achieve both protection, reinforcement and construction of the vacuum heat insulating material.
(3) The said foam is formed with the foaming agent which consists of water or a carbon dioxide gas.

According to this heat insulating member, by applying a foam formed using a foaming agent of water or carbon dioxide gas to the covering material, it is possible to make the covering material excellent in environmental characteristics and stable in compressive strength and the like over a long period of time. Can do.
(4) The jacket material is made of a metal foil.

According to this heat insulating member, a high-barrier heat insulating panel can be obtained by combining a vacuum heat insulating material and a covering material of a foamed body having open air bubbles using a metal foil, and a long-term performance suitable for construction. Maintenance is possible. Furthermore, from the viewpoint of high barrier properties, it is desirable to vacuum seal the vacuum heat insulating material with an outer packaging material made of a laminate film.
(5) A building structure provided with a heat insulating panel of a heat insulating member installed on a surface constituting a heat insulating material of a house, and a building member applied to the building structure.

According to this heat insulation panel, it is a heat insulation member that maintains high performance heat insulation performance and high strength, and it is possible to reduce utility costs, CO ₂ generation, wall thickness, and the like.

  According to the present invention, it is possible to provide a heat insulating member that has excellent initial thermal conductivity, can reduce deterioration of thermal conductivity, and has excellent long-term heat insulating performance.

It is a cross-sectional schematic diagram of the heat insulation panel which is a heat insulation member of this invention. It is a cross-sectional schematic diagram of the heat insulation panel which is the conventional heat insulation member. It is a schematic sectional drawing of the building structure using the heat insulation member of this invention.

  Hereinafter, the contents of the present invention will be described in detail. The heat insulating member of the present invention covers the periphery of a vacuum heat insulating material obtained by inserting a glass wool core material and a getter agent into an outer packaging material and vacuum-sealing with a covering material having open air bubbles, and the outer periphery is covered with a covering material. The inside of the material is sealed under reduced pressure. Heat insulation panel (heat insulation member) that has high barrier properties and can achieve both high performance and high strength over the long term by adopting a configuration in which the inside including the vacuum insulation material and the covering material having open cells is sealed under reduced pressure in the jacket material. It can be.

  A vacuum heat insulating material using a glass wool core has an excellent characteristic of a thermal conductivity of about 1.5 mW / m · K. In contrast, a heat insulating material such as urethane foam has a high thermal conductivity of about 20 mW / m · K or more, and the heat insulating performance is inferior by about 15 times or more compared to a vacuum heat insulating material. From this, also about the foam heat insulating material and sheet material combined with a vacuum heat insulating material, if the coating material which is excellent in heat conductivity can be used, the heat insulation performance as a heat insulation panel can be improved significantly.

  In the present invention, the material for covering the vacuum heat insulating material is provided with a communication body having a high compressive strength, which is not closed cells but mostly provided with open cell foams and does not shrink even when replaced with external air. . However, the continuous foam is inferior in heat insulation performance because there is no foaming gas as in the case of closed cells. Therefore, even in the case of a continuous coating material, the heat insulation configured in a reduced pressure including the coating material to reduce the thermal conductivity. The present invention was achieved by using a member. At that time, instead of filling the vacuum insulation material in closed-cell urethane foam as in the past, by forming the vacuum insulation material and the coating material separately, filling and foaming into the mold is eliminated, and the polyol and isocyanate react. Therefore, it is not deteriorated by high temperature damage caused by the temperature (about 120 ° C.) at which the foam is formed. Furthermore, by making the jacket material that wraps the covering material, which is a foam of open cells, into a high barrier property composed of a metal foil, the manufactured heat insulating panel can achieve both excellent heat insulating performance and high strength even over a long period of time. A member can be realized.

<Core>
The core material of the vacuum heat insulating material has a function of a spacer that keeps its shape from atmospheric pressure, and is preferably a glass wool core material having a high void due to a compressive stress during decompression. If the fiber diameter of the glass wool composing the core is large, the contact of the fiber is close to a line, and the thermal conductivity is high due to the reduction of contact thermal resistance. Conversely, if the fiber diameter is extremely small, the handling becomes inconvenient and the raw material is very expensive. become. For this reason, as the glass wool, it is preferable to use a fiber having an average fiber diameter of about 3 to 6 μm as a core material of the vacuum heat insulating material, which can obtain high voids even under a compressive stress in a vacuum and reduce thermal conductivity. Further, it is preferable to use glass wool from which adsorbed moisture has been removed by an aging treatment at about 250 ° C. for 1 hour. Moreover, in order to avoid that heat conductivity becomes high by generation | occurrence | production of outgas, what does not contain binders, such as a binder, is preferable. In addition, the average fiber diameter shall have measured the fiber diameter of the visual field containing about 10 fibers using the scanning electron microscope.

<Getter agent>
A getter agent is used for the purpose of improving the reliability of a vacuum heat insulating material and a coating material. As the getter agent, any agent that absorbs gas such as carbon dioxide, oxygen, nitrogen, and water vapor can be used. Absorbents such as functional zeolite, activated carbon, and lithium hydroxide can be used.

<Coating material>
As the covering material having open cells according to the present invention, a foam is preferable, and urethane foam, isocyanurate foam, phenol foam, styrene foam and the like can be used. For example, a urethane foam has a urethane bond, a urea bond, and an isocyanurate bond. The isocyanurate bond is generated by trimerizing an isocyanate group with a catalyst and can improve mechanical strength and heat resistance. The rigid polyurethane foam obtained by a normal method has a closed cell ratio of approximately 80% or more, and if the closed cell ratio is increased, the heat insulation performance is improved. However, in order to improve the dimensional stability and shrinkage as a coating material rather than the heat insulation performance, it was found that the heat insulation performance and the compressive strength can be compatible by making most of the foam bubbles continuous. Here, as the open cell ratio, it is desirable that the ratio of open cells in the foam is 70% or more.

For example, there are a method of promoting the continuation of bubbles by blending a long-chain polyether polyol obtained by adding propylene oxide to glycerin, and a metal salt of a monocarboxylic acid such as calcium stearate or calcium myristylate. is there. In order to produce urethane foam, various apparatuses can be used as long as the polyol liquid and the isocyanate liquid can be mixed uniformly. For example, a small mixer, a low pressure or high pressure foaming machine for injection foaming, a low pressure or high pressure foaming for slab foaming. Machine, low pressure or high pressure foaming machine for continuous line, spray foaming machine for spraying, etc. That is, a polyurethane continuous foam is obtained by reacting a polyol mixture and a polyisocyanate in the presence of a catalyst, a foaming agent, a foam stabilizer, and a communicating agent, so that the foam density is about 25 to 35 kg / m ^3. A panel is obtained. As the blowing agent, water, carbon dioxide gas, or carbon dioxide gas generated by the reaction between isocyanate and water is used, and environmental protection such as global warming and reduction of CO ₂ generation is considered. It is also possible to use inorganic fibers or the like in combination with the foam.

<Outer packaging materials, outer jacket materials>
Further, as the outer packaging material or covering material having a high barrier property, an airtight portion is provided inside to cover the core material or the covering material, and a material that reflects the shape of the core material by decompression sealing is preferable. As the laminate film used for the outer packaging material, a laminate film having an innermost layer as a heat welding layer, an intermediate layer having a gas barrier layer aluminum foil or an aluminum vapor deposition layer, and an outermost layer having a surface protective layer can be applied. However, since the aluminum foil or the aluminum vapor deposition layer itself is a heat conductive material, the thickness is preferably 10 μm or less in order to suppress a decrease in heat insulation performance due to the heat bridge. Specifically, the outermost layer is made of a polyamide film to improve puncture resistance, the intermediate layer is provided with an ethylene-vinyl alcohol copolymer film having an aluminum vapor deposition layer, and the innermost layer is made of high-density polyethylene or linear low It is a plastic laminate film provided with high density polyethylene or high density polypropylene.

In addition, as the jacket material that wraps the covering material, a metal foil such as a stainless steel foil or an aluminum alloy foil is preferable in order to sufficiently protect the gas barrier property of the vacuum heat insulating material. From the viewpoint of thermal conductivity, the thickness of the stainless steel foil is preferably about 20 to 50 μm, and the thickness of the aluminum alloy foil is preferably about 15 to 30 μm. In addition, a soluble polyimide varnish is used for the weld layer of the metal foil, and is applied and formed so as to have a thickness of about 10 to 30 mm and a thickness of about 10 to 50 μm, and is heat-sealed. Specifically, a polyimide varnish is applied to the peripheral part in a frame shape using a printing machine or the like on a stainless steel foil, the coating film is semi-solidified at about 70 ° C., and a pair of stainless steel foils is about 200 by a hot press machine. It is a high barrier coating material that is hermetically sealed by applying a temperature of ℃ and a pressure of about 1.0 kg / cm ² .

  Examples of the present invention will be described below. The invention is not limited to the embodiments.

  FIG. 1 is a schematic cross-sectional view of a heat insulating member of the present invention. FIG. 2 is a schematic sectional view of a conventional heat insulating member.

  The heat insulating member of the present embodiment is a heat insulating member 7 in which the vacuum heat insulating material 1 and the covering material 9 having open air bubbles are combined. The vacuum heat insulating material 1 is configured by wrapping a glass wool core material 3 and a getter agent 4 with an outer packaging material 2 and sealing the inside of the outer packaging material 2 under reduced pressure. The vacuum heat insulating material 1 is a heat insulating member that is covered with a covering material 9 and the outer periphery of the covering material 9 is covered with an outer covering material 5 and sealed under reduced pressure. For the covering material 9, a urethane foam having open cells is used.

  On the other hand, the conventional (comparative example) heat insulating member is obtained by covering the periphery of a vacuum heat insulating material similar to that shown in FIG. 1 with a covering material 8 formed of a foam of closed cells.

  FIG. 3 is a schematic cross-sectional view of a building structure using the heat insulating member of this embodiment. In the building structure of this embodiment, a pillar 14 is assembled on a base 13 on a concrete foundation 12, and a heat insulating member 10 is disposed between the pillar 14 and a gate pillar 15 provided between the pillars. At this time, by providing the heat-insulating member 10 with a nailable portion, it can be fixed to the pillar or the gate pillar by nail driving, and has an effect of improving the heat insulation performance of the building structure over a long period of time.

Example 1
The heat insulation panel of Example 1 was produced as follows. First, the vacuum heat insulating material was produced in the following procedures. As the core material, a glass wool having an average fiber diameter of 4.5 μm and subjected to an aging treatment at 250 ° C. for 1 hour was used. Further, molecular sieve 13X was used as a gas adsorption getter agent. Further, as the outer packaging material, a laminate film of high-density polyethylene, aluminum foil (about 6 μm), nylon and polyethylene terephthalate as a heat-welding layer was used. First, the core material and the getter agent are put into the outer packaging material, and after evacuating until the internal pressure in the vacuum chamber becomes 1.5 Pa for 10 minutes with the rotary pump of the vacuum packaging machine and 10 minutes with the diffusion pump, the outer packaging material The end of was vacuum sealed by heat sealing. The size of the produced vacuum heat insulating material was 400 mm × 400 mm × 10 mm. The thermal conductivity was 1.5 mW / m · K when measured using an AUTO-Λ manufactured by Eihiro Seiki Co., Ltd. under a measurement temperature condition of 10 ° C.

  Next, as a covering material for protecting the vacuum heat insulating material, a urethane foam communication panel having open cells using carbon dioxide gas generated by the reaction of isocyanate and water as a foaming agent was used. This urethane foam having open cells is filled and injected into a mold by mixing and stirring a premix component and isocyanate mixed with polyol, water, catalyst, foam stabilizer and communication agent in a high-pressure foaming machine. Foamed. An example of a method for producing such urethane foam is as follows. 30 parts by weight of polyether polyol with propylene oxide added to m-tolylenediamine system, 20 parts by weight of polyether polyol with propylene oxide added to triethanolamine system, and propylene oxide added to o-tolylenediamine system 30 parts by weight of a polyether polyol, 20 parts by weight of a polyether polyol obtained by adding propylene oxide to a sucrose system, 100 parts by weight of a mixed polyol component, 15 parts of water and 1.2 parts by weight of tetramethylhexamethylenediamine as a reaction catalyst 2 parts by weight of trimethylaminoethylpiperazine, 2 parts by weight of organic silicone compound X-20-1614 as a foam stabilizer, 10 parts by weight of calcium stearate as a communicating agent, diphenylmethane isocyanate of Millionate MR as isocyanate It can be produced by filling and injecting 125 parts of a polynuclear body into a mold.

  Furthermore, in order to use a heat insulating member as a heat insulating panel, the above-mentioned vacuum heat insulating material and a continuous urethane panel covering material are combined to maintain the heat insulating performance for a long time. It was. At that time, a polyimide varnish was coated in a frame shape on a stainless foil having a thickness of 30 μm as a metal foil to be semi-solidified, and a pair of stainless foils were pressed with a hot press machine and hermetically sealed. After that, vacuum insulation and zeolite are put into the jacket material in a urethane cover panel (size: 500mm x 500mm x 30mm), 8 minutes by rotary pump of vacuum packaging machine, 8 minutes by diffusion pump, vacuum chamber After exhausting until the internal pressure of the inside became 1.0 Pa, the final end portion of the outer cover material was sealed under reduced pressure by heat sealing.

  When the thermal conductivity and compressive strength under reduced pressure of the communication panel were examined, it was excellent at 5.5 mW / m · K and 0.18 MPa as compared with urethane foam having closed cells. Moreover, it was 4.0 mW / m * K when the initial thermal conductivity of the heat insulation panel was measured. Thereafter, the thermal conductivity of the heat insulation panel after being left in a constant temperature bath at 60 ° C. for about 90 days was remeasured. As a result, the deterioration was as small as 7.2 mW / m · K. For this reason, a heat insulating panel in which a vacuum heat insulating material is inserted into a continuous urethane covering material uses a communication panel with a thermal conductivity of 5.5 mW / m · K, which is superior to a conventional closed cell urethane panel. In addition, because it is kept with a high-barrier outer covering material, it becomes a high-performance thermal insulation panel, providing a thermal insulation panel with a thermal insulation member that has little dimensional change and shrinkage even during storage until construction, etc. it can.

  In addition, each physical property and characteristic of Table 1 were investigated as follows. The heat conductivity of the heat insulation panel which combined the vacuum heat insulating material, the coating material, and the vacuum heat insulating material and the coating material was evaluated using HC-071 type (heat flow meter method, average temperature 10 ° C.) manufactured by Eiko Seiki Co., Ltd. Furthermore, with respect to the dimensional change rate and shrinkage at low and high temperatures, the thickness of the foam cut to 150 mm × 300 mm × 25 tmm was allowed to stand at −20 ° C. for 48 hours, and left at 70 ° C. for 48 hours. Evaluated. The compressive strength was evaluated as the compressive strength obtained by loading each foam cut at 50 mm x 50 mm x 25 tmm at a feed rate of 4 mm / min and dividing the load at 10% deformation by the original pressure-receiving area. is there.

(Comparative Example 1)
The heat insulation panel of the comparative example 1 was produced as follows. First, the vacuum heat insulating material was produced in the following procedures. As the core material, glass wool having a fiber diameter of 5.5 μm was used. Molecular sieves 13X was used as a gas adsorption getter agent. Further, as the outer packaging material, a laminate film of high-density polyethylene, aluminum foil (about 6 μm), nylon and polyethylene terephthalate as a heat-welding layer was used. Put the core material and getter agent in the outer packaging material, put it in the vacuum chamber for 10 minutes with the rotary pump of the vacuum packaging machine and 10 minutes with the diffusion pump, exhaust it until the internal pressure of the chamber becomes 1.5 Pa, and then enclose the outer packaging The end of the material was heat sealed and fabricated by vacuum sealing. It was 1.7 mW / m * K when the heat conductivity was measured for the vacuum heat insulating material on measurement temperature conditions 10 degreeC.

Moreover, as a coating material for protecting the vacuum heat insulating material, a polyol, a substitute freon blowing agent (HFC-141b), a catalyst, a foam stabilizer, a premix component and an isocyanate are mixed and stirred in a high-pressure foaming machine, A closed-cell foamed polyurethane produced by filling and injecting into a mold was used. A vacuum heat insulating material was set in the mold, and a heat insulating panel for a building material member filled and injected with the above polyurethane foam was produced. When the thermal conductivity and compressive strength of the polyurethane foam were measured, it was inferior to 0.12 MPa at 20.5 mW / m · K. In addition, as shown in Table 1, substitute chlorofluorocarbons are used as foaming agents, so the environmental impact (CO ₂ emissions, eco-recyclability) is poor, and the dimensional change rate and shrinkage (-20 ° C and 70 ° C) of urethane foam. (Thickness change rate when left for 48 hours). Further, when the initial thermal conductivity was measured at a measurement temperature condition of 10 ° C., it was as high as 8.2 mW / m · K. Furthermore, when the thermal conductivity after being left for 90 days in a constant temperature bath at 60 ° C. was measured again, it deteriorated to 18.2 mW / m · K. From this, it was the heat insulation panel of the member for building materials in which the heat insulation performance in a long term is greatly inferior.

(Example 2)
The heat insulation panel of Example 2 was produced as follows. First, the vacuum heat insulating material produced the vacuum heat insulating material from the core material which consists of glass wool with an average fiber diameter of 5.6 micrometers using the laminated film similarly to Example 1 after the aging process of 300 degreeC for 1 hour. It was 1.6 mW / m * K when the heat conductivity was measured on measurement temperature conditions 10 degreeC. In addition, a urethane foam communication panel having open cells using carbon dioxide as a foaming agent was used as a covering material for protecting the vacuum heat insulating material.
This urethane foam was foamed by mixing and stirring a premix component mixed with a polyol, a small amount of water, a catalyst, a foam stabilizer, a communicating agent, and an isocyanate with a high-pressure foaming machine, filling and injecting into a mold. Is.

In order to obtain a heat insulating panel, a metal foil was used as a high barrier covering material in order to maintain the heat insulating performance for a long time by combining the vacuum heat insulating material produced above and the covering material of the continuous urethane panel. At that time, a polyimide varnish was coated in a frame shape on a stainless foil having a thickness of 30 μm as a metal foil to be semi-solidified, and a pair of stainless foils were pressed with a hot press machine and hermetically sealed.
After that, vacuum insulation and zeolite are put into the jacket material in a urethane cover panel (size: 500mm x 500mm x 30mm), 8 minutes by rotary pump of vacuum packaging machine, 8 minutes by diffusion pump, vacuum chamber After exhausting until the internal pressure of the inside became 1.0 Pa, the final end portion of the outer cover material was sealed under reduced pressure by heat sealing.

  When the thermal conductivity and compressive strength under reduced pressure of the communication panel were examined, they were excellent at 4.8 mW / m · K and 0.19 MPa as compared with urethane foam having closed cells. Moreover, it was 4.2 mW / m * K when the initial thermal conductivity of the heat insulation panel was measured. Thereafter, the thermal conductivity of the heat insulation panel after being left in a constant temperature bath at 60 ° C. for about 90 days was remeasured. As a result, the deterioration was as small as 8.4 mW / m · K. For this reason, a heat insulating panel in which a vacuum heat insulating material is inserted into a continuous urethane covering material uses a communication panel with a thermal conductivity of 4.8 mW / m · K, which is superior to a conventional closed cell urethane panel. In addition, because it is kept with a high barrier coating material, it becomes a high-performance heat insulation panel, and there is a heat insulation panel with a heat insulation member that has little dimensional change and shrinkage even during storage until construction, etc. Can be provided.

(Comparative Example 2)
The heat insulation panel of the comparative example 2 was produced as follows. A core material made of glass wool with a fiber diameter of 7.2 μm and a gas adsorption getter agent (Molecular Sieves 13X) are inserted into an outer packaging material made of a laminate film, and 10 minutes by a rotary pump of a vacuum packaging machine and 10 minutes by a diffusion pump. After putting in a vacuum chamber and evacuating until the internal pressure of the chamber became 1.5 Pa, the end of the outer packaging material was heat sealed and a vacuum heat insulating material was produced by vacuum sealing. When the thermal conductivity of the vacuum heat insulating material was measured at a measurement temperature condition of 10 ° C., it was 2.6 mW / m · K. The closed cell isocyanurate foam that protects the vacuum insulation material is prepared by mixing and stirring a hydrocarbon cyclopentane foaming agent, a catalyst, a foam stabilizer, a premix component and an isocyanate in a high pressure foaming machine. A closed cell panel was formed by filling and injecting into a mold. A vacuum heat insulating material was set in the mold, and a heat insulating panel for a building material member filled and injected with the foamed isocyanurate was produced. When the thermal conductivity and compressive strength of the foamed isocyanurate were measured, it was inferior to 0.11 MPa at 24.2 mW / m · K. In addition, as shown in Table 1, hydrocarbons are used as blowing agents, so the flammability and environmental impact (CO ₂ emissions, eco-recyclability) of cyclopentane are poor, and the dimensional change rate and shrinkage of isocyanurate foam. (Thickness change rate when left at −20 ° C. and 70 ° C. for 48 hours) was greatly inferior. Further, when the initial thermal conductivity was measured at a measurement temperature condition of 10 ° C., it was as high as 7.6 mW / m · K. Furthermore, when the thermal conductivity after being left in a constant temperature bath at 60 ° C. for 90 days was measured again, it deteriorated to 17.8 mW / m · K.
From this, it was the heat insulation panel of the member for building materials in which the heat insulation performance in a long term is greatly inferior.

(Example 3)
The heat insulation panel of Example 3 was produced as follows. First, a vacuum heat insulating material was manufactured using a laminated film in the same manner as in Example 1 after aging treatment at 250 ° C. for 1 hour with a core material made of glass wool having an average fiber diameter of 3.0 μm as the vacuum heat insulating material. The initial thermal conductivity at 10 ° C. was measured and found to be 1.3 mW / m · K. As the covering material for protecting the vacuum heat insulating material, a continuous panel of isocyanurate foam having open cells using carbon dioxide gas generated by reaction of isocyanate and water as a foaming agent was used. This isocyanurate foam is foamed by mixing and agitating a premix component, which is a mixture of polyol, water, catalyst, foam stabilizer, and communicating agent, and isocyanate in a high-pressure foaming machine, and filling and injecting into a mold. It is a thing. An example of a method for producing such foamed isocyanurate is as follows. 30 parts by weight of a polyether polyol obtained by adding propylene oxide to a glycerin system, 30 parts by weight of a polyether polyol obtained by adding propylene oxide to a propylene glycol system, 20 parts by weight of a polyether polyol obtained by adding propylene oxide to a pentaerythritol system, Polyether polyol obtained by adding propylene oxide to sorbitol is added to 100 parts by weight of a mixed polyol component of 20 parts by weight, 13 parts of water, 1.0 part by weight of tetramethylhexamethylenediamine as a reaction catalyst, and 2 parts of pentamethyldiethylenetriamine. 2 parts by weight of organosilicone compound X-20-1614 as a foam stabilizer, 10 parts by weight of calcium myristylate as a communication agent, and 1 polymethylene polyphenyl isocyanate as an isocyanate Using 25 parts, it can be produced by filling and injecting into a mold and foaming.

  Furthermore, in order to make a heat insulating panel of the heat insulating member, in order to maintain the heat insulating performance for a long time by combining the vacuum heat insulating material produced above and the covering material of the communication isocyanurate panel, a metal foil is selected as a high barrier covering material. Using. At that time, a polyimide varnish was coated in a frame shape on a 20 μm thick aluminum alloy foil as a metal foil and semi-solidified, and a pair of aluminum alloy foils were pressurized with a hot press machine and hermetically sealed. After that, put the vacuum insulation and zeolite into the outer cover material in a continuous isocyanurate covering panel (size: 500mm x 500mm x 30mm), vacuum for 8 minutes with the rotary pump of the vacuum packaging machine, and 8 minutes with the diffusion pump. After exhausting until the internal pressure in the chamber became 1.0 Pa, the final end portion of the outer cover material was sealed under reduced pressure by heat sealing.

  When the thermal conductivity and compressive strength under reduced pressure of the communication panel were examined, it was excellent at 5.1 mW / m · K and 0.23 MPa compared to urethane foam having closed cells. Moreover, it was 4.1 mW / m * K when the initial thermal conductivity of the heat insulation panel was measured. Thereafter, the thermal conductivity of the heat insulation panel after being left in a constant temperature bath at 60 ° C. for about 90 days was remeasured. As a result, the degradation was as small as 7.5 mW / m · K. For this reason, a heat insulating panel in which a vacuum heat insulating material is inserted into a continuous urethane covering material has a communication panel body having an excellent thermal conductivity of 5.1 mW / m · K as a covering material compared to a conventional closed cell urethane panel. In addition, because it is kept with a high-barrier jacket material, it becomes a high-performance thermal insulation panel with little dimensional change and shrinkage even during storage until construction, etc. Can be provided.

Example 4
The heat insulation panel of Example 4 was produced as follows. First, a vacuum heat insulating material was formed by using a core material made of glass wool having an average fiber diameter of 6.0 μm as the vacuum heat insulating material and using an outer packaging material made of a laminate film in the same manner as in Example 1 after aging treatment at 300 ° C. for 1 hour. . It was 1.6 mW / m * K when the heat conductivity was measured on measurement temperature conditions 10 degreeC. As the covering material for protecting the vacuum heat insulating material, a communication panel of isocyanurate foam having open cells using carbon dioxide as a foaming agent was used. This isocyanurate foam is prepared by mixing and agitating a premix component, which is a mixture of a polyol, a small amount of water, a catalyst, a foam stabilizer, and a communicating agent, and an isocyanate with a high-pressure foaming machine, and filling the mold. Foamed.

  Furthermore, in order to maintain the heat insulating performance for a long time by combining the vacuum heat insulating material produced above and the covering material of the communication isocyanurate panel in order to make the heat insulating panel of the heat insulating member, metal foil etc. is selected as a high barrier covering material Used. At that time, a polyimide varnish was coated in a frame shape on a stainless foil having a thickness of 30 μm as a metal foil to be semi-solidified, and a pair of stainless foils were pressed with a hot press machine and hermetically sealed. After that, put the vacuum insulation and zeolite into the outer cover material in a continuous isocyanurate covering panel (size: 500mm x 500mm x 30mm), vacuum for 8 minutes with the rotary pump of the vacuum packaging machine, and 8 minutes with the diffusion pump. After exhausting until the internal pressure in the chamber became 1.0 Pa, the final end portion of the outer cover material was sealed under reduced pressure by heat sealing.

  When the thermal conductivity and compressive strength under reduced pressure of the communication panel were examined, it was 4.6 mW / m · K and 0.25 MPa, which were superior to the urethane foam having closed cells. The initial thermal conductivity of the heat insulating panel was measured and found to be 3.9 mW / m · K. Thereafter, the thermal conductivity of the heat insulation panel after being left in a constant temperature bath at 60 ° C. for about 90 days was remeasured. As a result, the deterioration was as small as 7.3 mW / m · K. For this reason, the heat insulating panel in which the vacuum heat insulating material is inserted into the continuous isocyanurate covering material has a thermal conductivity of 4.6 mW / m · K as a covering material superior to the conventional closed cell urethane heat insulating panel. Because it is kept with a high-barrier jacket material, it becomes a high-performance thermal insulation panel, and there is little dimensional change and shrinkage even during storage until construction, etc. Panels can be provided.

(Example 5)
The heat insulation panel of Example 5 was produced as follows. First, as the vacuum heat insulating material, a core material made of glass wool having an average fiber diameter of 5.2 μm was subjected to an aging treatment at 280 ° C. for 1 hour, and a laminate film was used to form a vacuum heat insulating material. It was 1.7 mW / m * K when the heat conductivity was measured on measurement temperature conditions 10 degreeC. In addition, for the covering material for protecting the vacuum heat insulating material, a resol type phenol resin obtained by reacting phenol and formaldehyde with water foaming agent, castor oil based ionic surfactant foam stabilizer, phenolsulfonic acid A phenol foam continuous panel having open cells foamed by mixing and stirring the acid curing agent and calcium stearate continuous agent, filling and injecting into a mold, was used.

  Furthermore, in order to make a heat insulating panel of the heat insulating member, a metal foil or the like is used as a high barrier covering material in order to maintain the heat insulating performance of the vacuum heat insulating material for a long time by combining the above-prepared vacuum heat insulating material and the covering material of the continuous phenol panel. Selected and used. At that time, polyimide varnish was coated in a frame shape on a 20 μm-thick aluminum alloy foil as a metal foil and semi-solidified, and a pair of aluminum alloy foils were pressed with a hot press machine to hermetically seal the three sides. After that, vacuum insulation and zeolite are put into the jacket material in a phenolic covering panel (size: 500mm x 500mm x 30mm), 8 minutes by rotary pump of vacuum packaging machine, 8 minutes by diffusion pump, vacuum chamber After exhausting until the internal pressure of the inside became 1.0 Pa, the final end portion of the outer cover material was sealed under reduced pressure by heat sealing.

  When the thermal conductivity and compressive strength under reduced pressure of the communication panel were examined, it was excellent at 5.3 mW / m · K and 0.17 MPa as compared with foamed urethane having closed cells. The initial thermal conductivity of the heat insulating panel was measured and found to be 4.5 mW / m · K. Thereafter, the thermal conductivity of the heat insulation panel after being left in a constant temperature bath at 60 ° C. for about 90 days was remeasured. As a result, the degradation was as small as 8.6 mW / m · K. For this reason, a heat insulating panel in which a vacuum heat insulating material is inserted into a continuous phenolic covering material has an excellent communication panel with a thermal conductivity of 5.3 mW / m · K as a covering material compared to a conventional closed cell urethane heat insulating panel. In addition, because it is kept with a high-barrier jacket material, it becomes a high-performance thermal insulation panel with little dimensional change and shrinkage even during storage until construction, etc. Can be provided.

(Example 6)
The heat insulation panel of Example 6 was produced as follows. First, a vacuum heat insulating material was formed by using a core material made of glass wool having an average fiber diameter of 4.8 μm as the vacuum heat insulating material, and using an outer packaging material made of a laminate film in the same manner as in Example 1 after aging treatment at 250 ° C. for 1 hour. . It was 1.5 mW / m * K when the heat conductivity was measured on measurement temperature conditions 10 degreeC. As the covering material for protecting the vacuum heat insulating material, a styrene foam communication panel having open cells using carbon dioxide gas and water as a foaming agent was used. This foamed styrene foam is prepared by melting and kneading 0.5 parts by weight of barium stearate as a lubricant to about 200 ° C. with respect to 100 parts by weight of a polystyrene resin, and adding 2 parts by weight of water and 2 parts by weight of carbon dioxide as a foaming agent. Press fit inside. After that, cooling is performed while kneading with an extruder and a cooler, the foamed resin temperature is foamed from the slit die to the atmosphere at about 110 to 140 ° C., and then the molding die and the molding roll are installed in close contact with the slit die. By extrusion foam filling.

  Furthermore, in order to obtain a heat insulating panel, a metal foil was selected and used as a high barrier coating material in order to maintain the heat insulating performance for a long time by combining the vacuum heat insulating material produced above and a covering material of a continuous styrene panel. At that time, a polyimide varnish was coated in a frame shape on a stainless foil having a thickness of 30 μm as a metal foil to be semi-solidified, and a pair of stainless foils were pressed with a hot press machine and hermetically sealed. After that, put the vacuum insulation and zeolite into the jacket material in a continuous styrene coating panel (size: 500mm x 500mm x 30mm), 8 minutes with the rotary pump of the vacuum packaging machine, 8 minutes with the diffusion pump, vacuum chamber After exhausting until the internal pressure of the inside became 1.0 Pa, the final end portion of the outer cover material was sealed under reduced pressure by heat sealing.

  When the thermal conductivity and compressive strength under reduced pressure of the communication panel were examined, they were excellent at 3.9 mW / m · K and 0.16 MPa compared to urethane foam having closed cells. The initial thermal conductivity of the heat insulating panel was measured and found to be 3.8 mW / m · K. Thereafter, the thermal conductivity after the thermal insulation panel was left in a constant temperature bath at 60 ° C. for about 90 days was remeasured. As a result, the degradation was as small as 7.0 mW / m · K. For this reason, a heat insulating panel in which a vacuum heat insulating material is inserted into a continuous styrene coating material has a thermal conductivity of 3.9 mW / m · K, which is superior to a conventional closed cell urethane heat insulating panel. In addition, since the high-barrier jacket material is used, it becomes a high-performance heat insulation panel, and there is little dimensional change or shrinkage even during storage until construction, etc. Can be provided.

(Comparative Example 3)
The heat insulation panel of the comparative example 3 was produced as follows. A core material made of glass wool having a fiber diameter of 6.1 μm and a gas adsorption getter agent (Molecular Sieves 13X) are inserted into an outer packaging material made of a laminate film, and 10 minutes by a rotary pump of a vacuum packaging machine and 10 minutes by a diffusion pump. After putting in a vacuum chamber and exhausting until the internal pressure of the chamber became 1.5 Pa, the end of the outer packaging material was heat-sealed, and a vacuum heat insulating material was produced by vacuum sealing. When the thermal conductivity of the vacuum heat insulating material was measured at a measurement temperature condition of 10 ° C., it was 2.3 mW / m · K. In addition, a closed cell phenol foam was used as a covering material for protecting the vacuum heat insulating material. This phenol foam is a pre-mixed cyclopentane foaming agent of resol-type phenolic resin obtained by reacting phenol and formaldehyde, a foam stabilizer of castor oil based ionic surfactant, and an acid curing agent of phenolsulfonic acid. Then, it is filled and injected into a mold and foamed. When the thermal conductivity and compressive strength of this phenol foam were measured, it was inferior at 26.5 mW / m · K and 0.10 MPa. In addition, as shown in Table 1, cyclopentane is flammable and has a poor environmental load (CO ₂ emissions, eco-recyclability). The dimensional change rate and shrinkage of phenol foam (-20 ° C and 70 ° C were left for 48 hours). The thickness change rate at the time was greatly inferior. Then, the heat insulation panel of the member for building materials which set the vacuum heat insulating material in the type | mold and was made to inject | pour and inject said phenol foam was produced. When the initial thermal conductivity was measured at a measurement temperature condition of 10 ° C., it was as high as 8.5 mW / m · K, and when the thermal conductivity after being left in a constant temperature bath at 60 ° C. for 90 days was measured again, 18 Deteriorated to 0.5 mW / m · K. From this, it was the heat insulation panel of the member for building materials in which the heat insulation performance in a long term is greatly inferior.

(Comparative Example 4)
The heat insulation panel of the comparative example 4 was produced as follows. A core material made of glass wool having a fiber diameter of 2.9 μm and a gas adsorption getter agent (Molecular Sieves 13X) are inserted into an outer packaging material made of a laminate film, 10 minutes by a rotary pump of a vacuum packaging machine, and 10 minutes by a diffusion pump. After putting in a vacuum chamber and exhausting until the internal pressure of the chamber became 1.5 Pa, the end of the outer packaging material was heat-sealed, and a vacuum heat insulating material was produced by vacuum sealing. It was 1.5 mW / m * K when the heat conductivity of the vacuum heat insulating material was measured on measurement temperature conditions 10 degreeC. In addition, a closed cell styrene foam was used as a covering material for protecting the vacuum heat insulating material. This styrene foam is a particle obtained by dispersing a styrene monomer in water with a dispersant and the like, adding a polymerization initiator, and impregnating an aliphatic hydrocarbon isobutane foaming agent into a styrene resin polymerized by suspension polymerization ( (Particle diameter of about 0.5 to 1.0 mm) is placed in a molding die, and the particles are preheated with steam or the like and heated. When the thermal conductivity and compressive strength of this styrene foam were measured, it was inferior to 29.5 mW / m · K, 0.08 MPa. In addition, as shown in Table 1, isobutane is flammable and has a poor environmental load (CO ₂ emissions, eco-recyclability). When styrene foam is left to stand at -20 ° C and 70 ° C for 48 hours. The rate of change in thickness) was greatly inferior.
Then, the heat insulating panel of the member for building materials which set the vacuum heat insulating material in the type | mold and was made to inject | pour and inject said styrene foam was produced. When the initial thermal conductivity was measured at a measurement temperature condition of 10 ° C., it was as high as 9.2 mW / m · K, and when the thermal conductivity after being left in a constant temperature bath at 60 ° C. for 90 days was measured again, 19 Deteriorated to 0.8 mW / m · K. From this, it was the heat insulation panel of the member for building materials in which the heat insulation performance in a long term is greatly inferior.

(Example 7)
Example 7 is the example used for the building structure using the heat insulation member as shown in FIG. FIG. 3 is a schematic sectional view of a building structure. In a building structure, a pillar is assembled on a foundation on a concrete foundation, and a heat insulating panel having excellent thermal conductivity is used as a heat insulating member on a gate pillar provided between the pillars and fixed with nails or the like. The heat insulating member of the present embodiment is composed of a heat insulating panel in which a vacuum heat insulating material and a covering material having open cells are combined. The vacuum heat insulating material is a core made of glass wool, and the covering material is urethane having open air bubbles. It is a heat insulating panel of a building material member formed of a foam or the like and having a vacuum heat insulating material disposed in a covering material of a communicating body. At this time, as a heat insulation panel of a heat insulation member, it produced as follows. For the vacuum insulation material, a glass wool core and a gas adsorption getter agent are placed in an outer packaging material made of a laminate film, which is vacuum sealed with a vacuum packaging machine and has a high thermal conductivity of about 1.5 mW / m · K. It uses high performance vacuum insulation. In addition, a urethane foam communication panel having open cells using carbon dioxide gas generated by the reaction of isocyanate and water as a foaming agent was used as the covering material for protecting the vacuum heat insulating material. This urethane foam was foamed by mixing and agitating a premix component in which a polyol, water, a catalyst, a foam stabilizer, and a communicating agent were mixed with an isocyanate in a high-pressure foaming machine, filling and injecting into a mold. Is. As the urethane foam, 30 parts by weight of a polyether polyol in which propylene oxide is added to m-tolylenediamine type, 20 parts by weight of polyether polyol in which propylene oxide is added to triethanolamine type, o-tolylenediamine 30 parts by weight of polyether polyol with propylene oxide added to the system, 20 parts by weight of polyether polyol with propylene oxide added to the sucrose system, 100 parts by weight of the mixed polyol component, 15 parts of water and tetramethylhexamethylene as the reaction catalyst 1.2 parts by weight of diamine and 2 parts of trimethylaminoethylpiperazine, 2 parts by weight of organosilicone compound X-20-1614 as a foam stabilizer, 10 parts by weight of calcium stearate as a communicating agent, Millionate M as an isocyanate 125 parts of diphenylmethane isocyanate polynuclear R was foam filled.

  This continuous urethane panel is put in an outer packaging material in the same manner as the vacuum heat insulating material, and is vacuum-sealed by a vacuum packaging machine, and a high-performance coating material having a thermal conductivity of about 5.5 mW / m · K is used. Furthermore, in order to maintain the heat insulation performance for a long time by combining a vacuum insulation material and a continuous urethane panel coating material, a high barrier coating material is made of stainless steel foil and polyimide varnish, and the vacuum insulation material is connected to the continuous urethane coating material. And a high-performance heat-insulating panel having a thermal conductivity of about 4.0 mW / m · K is used as a heat-insulating member. In order to provide a ventilation layer between the outer wall and the outer wall, the heat insulating member, the pillar and the gate pillar are provided in this order to fix the outer wall finishing material. When fixing a heat insulating member to a pillar and a pillar or a pillar and a gate pillar or a gate pillar and a gate pillar, a heat insulating panel that functions effectively with a low thermal conductivity after completion of the building structure by fixing the vicinity of the end of the heat insulating member with a nail or the like. By applying to a heat insulating member, the effect which maintains heat insulation performance for a long period of time compared with the thing which did not insert a heat insulation panel is acquired, and energy-saving building structures, such as a house excellent in an environment, can be provided.

  ADVANTAGE OF THE INVENTION According to this invention, it can be set as the heat insulation member with little deterioration in long-term heat insulation performance by comprising combining a vacuum heat insulating material and the foam of an open cell. Since the insulation covering the vacuum insulation does not fill and inject closed-cell foam, the reaction temperature of the mold set and urethane foam (approximately 120 ° C) can be maintained for a long time without being damaged by the vacuum insulation. It becomes. Moreover, since both the vacuum heat insulating material and the covering material having open air bubbles are present in the vacuum layer, there is no intrusion of air and no moisture adsorption in the air, and the dimensional change and shrinkage of the foam are suppressed, and it has a strong effect on water and sled. . In addition, the use of a continuous body with excellent thermal conductivity (10 mW / m · K or less) and compressive strength (0.15 MPa or more) for the covering material covering the vacuum heat insulating material, and a high barrier coating material Thus, a heat insulating member capable of maintaining the compressive strength and thermal conductivity for a long period of time can be obtained even during storage (about 50 ° C.) until construction.

  Furthermore, by applying to the heat insulating member a heat insulating panel that has a low thermal conductivity after completion of the building structure and functions effectively, the building structure is effective for energy saving such as a house that is excellent in the environment.

  Moreover, this heat insulating member can be applied to each product that needs to be kept warm or cold, such as a vehicle, a building member, an automobile, or a medical device. In particular, it is effective for all equipment that requires heat insulation, including heat exchange parts, and it can be applied to vehicles, etc., to save space on the heat insulation wall, expand the interior space of the vehicle and increase the heat insulation effect. Is resolved.

DESCRIPTION OF SYMBOLS 1 Vacuum heat insulating material 2 Outer packaging material 3 Core material 4 Getter agent 5 Cover material 6, 7, 10 Thermal insulation member 8 Coating material (closed cell foam)
9 Coating material (open cell foam)
11 Building Structure 12 Concrete Foundation 13 Base 14 Pillar 15 Gate Pillar

Claims (6)

A glass wool core material, a getter agent, a gas barrier outer packaging material containing the core material and the getter agent, and a vacuum heat insulating material that seals the inside of the outer packaging material under reduced pressure,
A covering material that is arranged so as to cover the periphery of the vacuum heat insulating material and is composed of a foamed body having open air bubbles,
An outer jacket material for housing the heat insulating panel and the covering material;
A heat insulating member in which the inside of the covering agent is sealed under reduced pressure.   The heat insulating member according to claim 1, wherein the thermal conductivity of the covering material under reduced pressure is 10 mW / m · K or less.   The heat insulating member according to claim 1, wherein the covering material has a compressive strength of 0.15 MPa or more.   2. The heat insulating member according to claim 1, wherein the foam is formed of a foaming agent made of water or carbon dioxide.   The heat insulating member according to claim 1, wherein the jacket material is made of a metal foil.   A building member using the heat insulating member according to claim 1.

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