JP2009168092A - Vacuum heat insulation material and building component using vacuum heat insulation material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To keep heat insulation performance over a long time in a vacuum heat insulation material. <P>SOLUTION: The heat insulation performance can be kept over a long time in such a way that an adsorbent 4 enclosed in decompression within a jacket material 3 with a core material 2b comprises a gas adsorbent and a moisture adsorbent within a hardly gas permeable vessel, and the gas adsorbent and the moisture adsorbent are housed in each independent vacuum space by a partition. Because the gas adsorbent and the moisture adsorbent are housed within the hardly gas permeable vessel, deterioration of the gas adsorbent due to handling in atmospheric air can be suppressed. Because gas dewatered by the moisture adsorbent is adsorbed after adapted to the vacuum heat insulation material 1, deactivation caused by moisture adsorption of the gas adsorbent can be suppressed. Properties possessed by the gas adsorbent can be exhibited fully to keep the heat insulation performance for a long time. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a vacuum heat insulating material in which a plurality of core materials and an adsorbing material are sealed under reduced pressure in a jacket material, and a building member to which the vacuum heat insulating material is applied.

  In recent years, expectations for industrial technology that requires high vacuum are increasing. For example, energy saving is strongly desired from the viewpoint of preventing global warming, and energy saving is an urgent issue for household appliances.

  In particular, a heat insulating material having excellent heat insulating performance is required from the viewpoint of efficiently using heat in a heat and cold insulation device such as a refrigerator, a freezer, and a vending machine.

  As general heat insulating materials, fiber materials such as glass wool and foams such as urethane foam are used. However, in order to improve the heat insulation performance of these heat insulating materials, it is necessary to increase the thickness of the heat insulating material, and there is a limit to the space that can be filled with the heat insulating material, so when space saving and effective use of the space are necessary It cannot be applied.

  Therefore, vacuum heat insulating materials have been proposed as high performance heat insulating materials. This is a heat insulator in which a core material serving as a spacer is inserted into a jacket material having a gas barrier property and the inside is decompressed and sealed.

  Here, the vacuum heat insulating material has a configuration having a plurality of core materials, and is a configuration in which a heat welding portion is provided between the core materials so that each core material is located in an independent vacuum space. (1) Since the core material part away from the end face of the jacket material is less affected by the intrusion gas from the end face, it is easy to maintain the thermal insulation performance as a whole vacuum heat insulating material. (2) Vacuum break in one place Even if this occurs, the effect on other core material parts is small, so deterioration of heat insulation performance can be minimized. (3) High flexibility in the shape of the core material and vacuum heat insulating material, depending on the application Compared to a vacuum heat insulating material having a single core material, it has various merits, such as being able to design different shapes. For this reason, expansion to a wide range of applications can be expected.

  On the other hand, the vacuum insulation material has a problem that the degree of vacuum deteriorates due to the intrusion of water vapor or air from the outside, and the heat insulation performance deteriorates with the deterioration of the vacuum degree. In addition, it has been difficult to apply to applications that require heat insulation performance over a long period of time.

  Therefore, there is a technique in which an adsorbent is applied in order to prevent deterioration of the degree of vacuum in the vacuum heat insulating material and maintain excellent heat insulating performance for a long period of time.

  As an example of the adsorbent, there is a Ba—Li alloy that removes nitrogen at a low temperature (see, for example, Patent Document 1).

  The Ba-Li alloy, along with the desiccant, was used as a device to maintain a vacuum in the insulation jacket and was able to adsorb gases such as nitrogen even at room temperature.

  Further, when a vacuum heat insulating material is used as a heat insulating material, a thin and high heat insulating performance can be expected, and there is a technique applied to a building (see, for example, Patent Documents 2 and 3).

By applying vacuum insulation to the building, a very high thermal insulation was obtained.
Japanese National Patent Publication No. 9-512088 JP 2006-90070 A JP 2007-198004 A

  However, in the configuration of Patent Document 1, it is possible to adsorb even a low activity gas such as nitrogen, but since Ba is a PRTR designated substance, there is no problem for the environment and the human body for industrial use. Is desired.

  In addition, it is described that it does not require heat treatment for activation and can adsorb nitrogen even at room temperature and can be handled in an air atmosphere for several minutes, but industrially manufactures products using gas adsorbents. In some cases, a longer allowable time is desired for handling.

  In addition, when using gas adsorbents in applications where performance must be ensured over a long period of time, such as building materials, deactivation of the adsorbents in the manufacturing process is suppressed as much as possible, and it is used as a building member. It is desirable that the gas adsorbent has sufficient characteristics when it is used.

  In addition, in order to suppress deterioration of the gas adsorbent due to moisture, the gas adsorbent is covered with a drying material (moisture adsorbent). As a result, the function retention and expression of the gas adsorbent and the gas adsorbent are achieved. The thickness of the device (gas adsorption device) that assists is greater than the sum of the thicknesses of the gas adsorbent and the moisture adsorbent.

  One of the features of vacuum insulation is that heat insulation performance can be obtained with a thinner thickness compared to other insulations. Then, since the minimum of the thickness of a vacuum heat insulating material becomes the thickness of a gas adsorption device, it will prevent thinning of a heat insulating material.

  The configurations of Patent Documents 2 and 3 are for the purpose of improving workability, and there is no detailed description in terms of maintaining the temporal heat insulation performance. However, the required durability of buildings is very long, several decades compared to several to a dozen years for home appliances, and without the optimization of the materials that make up the vacuum insulation material, It is difficult to maintain its thermal insulation performance.

  The present invention solves the above-mentioned conventional problems, and provides a vacuum heat insulating material that is excellent in both initial heat insulating performance and time-dependent heat insulating performance by making the gas adsorbent into a gas adsorbing device that can be stored in the atmosphere for a long time. Moreover, it aims at providing the building member excellent in heat insulation performance by applying the vacuum heat insulating material excellent in heat insulation performance.

  In order to achieve the above object, the vacuum heat insulating material of the present invention includes at least a plurality of core materials, a gas barrier outer covering material having a heat welding layer on one surface, and an adsorbing material, and the heat welding layer. The core material is sealed under reduced pressure so that the core material is located in two or more independent vacuum spaces between the jacket materials facing each other, and the adsorbent is disposed in one or more core material portions. A vacuum heat insulating material, wherein the adsorbing material comprises a gas adsorbing material, a moisture adsorbing material, and a container made of a gas poorly permeable material, and the inside of the container is at least 2 by a partition whose air permeability can be controlled. The gas adsorbent and the moisture adsorbent are respectively stored in different spaces of the container.

  Since the gas adsorbent and moisture adsorbent are housed in a gas-impermeable container, they can be stored in the atmosphere for a long time even if they are highly active, and adsorb gas and moisture during production. The deterioration of the gas adsorbent due to this can be suppressed, and the characteristics of the gas adsorbent can be fully exhibited. For this reason, the temporal heat insulation performance of a vacuum heat insulating material improves more, and also when a vacuum heat insulating material is applied to a building member, temporal heat insulation performance improves.

  Since the gas adsorbent is highly active against moisture, the gas adsorbent is deactivated when moisture is adsorbed, and the characteristics cannot be fully exhibited. Therefore, if the gas adsorbent adsorbs moisture with the moisture adsorbent and then the dried gas component is adsorbed, the desorption of the gas adsorbent due to moisture can be suppressed, and the characteristics of the gas adsorbent are fully exhibited. It becomes possible to do. For this reason, the time-insulating performance of the vacuum heat insulating material can be improved, and even when used as a building member, a high energy saving effect can be achieved over a long period of time.

  By accommodating the gas adsorbent and the moisture adsorbent in parallel in a plurality of spaces, the thickness of the gas adsorbing device becomes substantially equal to the thickness of one of these adsorbents. For this reason, the vacuum heat insulating material can be thinned, and a thin and high-performance building member can be obtained even when applied as a building member.

  The vacuum heat insulating material of the present invention has a configuration in which the gas adsorbing device obtained by converting the adsorbing material into a device can sufficiently exhibit the characteristics of the gas adsorbing material, so that the heat insulating performance of the vacuum heat insulating material can be maintained over a long period of time. In addition, even when used as a building member, it has excellent heat-insulating performance over time, so that a high energy-saving effect can be obtained over a long period of time.

  The invention described in claim 1 includes at least a plurality of core members, a gas barrier outer covering material having a heat welding layer on one side, and an adsorbing material, and the outer coverings facing each other. A vacuum heat insulating material that is sealed under reduced pressure so that the core material is located in two or more independent vacuum spaces between the materials, and the adsorbent material is disposed in one or more core material portions. The adsorbent comprises a container made of a gas adsorbent, a moisture adsorbent, and a gas-impermeable material, and the container is partitioned into at least two or more spaces by a partition capable of controlling air permeability. The gas adsorbent and the moisture adsorbent are respectively housed in different spaces of the container.

  In general, since the gas adsorbent has a property of easily adsorbing moisture, when the gas around the gas adsorption device contains moisture, the adsorption capacity of the gas is reduced by adsorbing moisture.

  In such a case, it is possible to obtain the required air adsorption amount by increasing the amount of the gas adsorbent accommodated in the gas adsorption device, but in general, the gas adsorbent is more expensive than the moisture adsorbent. Adsorbing moisture that can be adsorbed by the moisture adsorbing material with the air adsorbing material is not a good idea from the viewpoint of cost. Therefore, it is desirable to adsorb moisture with a moisture adsorbent and to adsorb gas with a gas adsorbent.

  However, since the gas adsorbent adsorbs moisture faster than the moisture adsorbent, the gas adsorbent adsorbs moisture when the moisture adsorbent and the gas adsorbent are mixed. The gas adsorption ability cannot be fully exhibited. That is, it is necessary to optimize the arrangement of the container for storing the adsorbent and the adsorbent in the container.

  First, the gas adsorbing device is configured such that the gas adsorbing material and the moisture adsorbing material are accommodated in independent spaces, and appropriate air permeability is ensured between the independent spaces. Further, the gas outside the gas adsorbing device passes through the space containing the moisture adsorbing material and then reaches the space containing the gas adsorbing material. Accordingly, since the moisture adsorbing material adsorbs moisture, the gas that reaches the space containing the gas adsorbing material becomes a gas with less moisture, and the characteristics of the gas adsorbing material can be sufficiently exhibited.

  If the air permeability of the partition is too large, the moisture adsorbing material cannot fully absorb moisture, the moisture reaches the air adsorbing material, and the moisture adsorbing material deteriorates. Conversely, if the air permeability of the partition between the space for accommodating the gas adsorbent and the space for accommodating the moisture adsorbent is too small, the gas does not reach the gas adsorbent, and the adsorption characteristics of the gas adsorbent can be exhibited. It becomes difficult. Therefore, the air permeability of the partition is important. The air permeability of the partition depends on the gas permeability, the cross-sectional area, and the length, and the above mechanism is achieved by optimizing this.

  In addition, by parallelizing both the space for the gas adsorbent and the moisture adsorbent, the maximum thickness of the gas adsorbent device will depend on the maximum thickness of the gas adsorbent or moisture adsorbent. Can be made thinner. Therefore, it is possible to reduce the thickness of the application.

  In addition, since the gas adsorption device (adsorbent) used in the present invention can be thinned and has a high degree of freedom in shape, it can take advantage of the thin and high heat insulation characteristics unique to vacuum insulation materials, and the degree of freedom in shape. Therefore, the thickness of the building member can be reduced and the workability can be improved.

  The higher the activity of the gas adsorbent used and the greater the specific surface area, the more severe the handling conditions. That is, in order to maintain the activity of the gas adsorbent, the time that can be contacted with air is shortened, and the pressure that can be contacted is also reduced. These requirements are achieved by accommodating the gas adsorbing material in a container made of a gas permeable material.

Here, for example, the container divides the space into the inside and outside like a spherical shell, and the gas poorly permeable material has a gas permeability of 10 ⁴ [cm ³ / (m ² · day · atm). The following materials, more preferably 10 ³ [cm ³ / (m ² · day · atm)] or less.

  Further, such a gas adsorbent has a problem of deterioration when applied to an application in addition to storage. A vacuum heat insulating material will be described as an example.

  The vacuum heat insulating material is a gas-impermeable outer jacket material in which a core material and a gas adsorbent material are inserted in a chamber, the chamber is decompressed, the interior of the outer jacket material is decompressed, and the opening of the outer jacket material Is produced by sealing.

  At this time, the pressure in the chamber is reduced by a vacuum pump. In the normal pressure region, that is, before vacuum sealing, the pressure can be reduced by either a pump or an adsorbent.

  On the other hand, in the low pressure region, that is, inside the jacket material after vacuum sealing, there is a gas that could not be decompressed by the vacuum pump, a gas that penetrates through the jacket material after vacuum sealing, and a gas generated from the core material, These can be adsorbed only with a gas adsorbent.

  Therefore, in order to fully demonstrate the capability of the gas adsorbent inside the outer jacket material after vacuum sealing, it is necessary to communicate with the outside after vacuum sealing.

  Here, the term “communication” means that a gas can pass through the space inside the container and the space outside the container when a through hole is formed in the container of the gas adsorption device.

  Furthermore, since communication is performed after sealing the vacuum heat insulating material, if there is a gas that is difficult to adsorb with the gas adsorbing material in the gas adsorbing device, the gas will increase the internal pressure of the vacuum heat insulating material and cause deterioration of the heat insulating performance. Therefore, the inside of the gas adsorption device needs to be evacuated in advance. The pressure is desirably 100 Pa or less.

  Moreover, when a gas adsorption device is used for vacuum equipment covered with soft packaging materials such as a vacuum heat insulating material, atmospheric pressure is applied to the gas adsorption device. At this time, if the container of the gas adsorption device is a soft wrapping material, the atmospheric pressure is applied to the partition that connects the two spaces, so the gas permeability is reduced, so the cross-sectional area of the space is maintained against atmospheric pressure. A spacer is required to do this.

  Therefore, a continuous porous body is used as a partition. Thereby, since the bulk part of a continuous porous body acts as a spacer and the void part acts as a partition through which gas passes, these conditions can be satisfied.

  In the present invention, the partition controls air permeability between the spaces, and includes a tubular member, an open-cell porous body, a nonwoven fabric, paper, and the like. Is not particularly specified as long as the gap can be maintained and the voids communicate with each other.

  Here, when a nonwoven fabric or paper is used, the compression rate when pressure is applied can be controlled by selecting an appropriate material and manufacturing method. Therefore, the space | gap of the partition which connects the space of a gas adsorption device can be hold | maintained appropriately also under atmospheric pressure. Therefore, even when an air adsorbent having higher activity is used, deterioration due to moisture can be suppressed while sufficiently exhibiting adsorption characteristics.

  Furthermore, since non-woven fabric and paper have a large degree of freedom in shape with respect to the bending force, if the container of the gas adsorption device is a soft wrapping material, the degree of freedom in bending of the gas adsorption device will also be large and can be used for more general purposes. become.

  The soft wrapping material is easily deformed by an external force and follows the shape of the housed member, and a plastic laminate film or the like corresponds to this. The plastic laminate film is a soft packaging material and has a high degree of freedom in shape with respect to bending force. Therefore, by using the plastic laminate film as a container, the degree of freedom in shape with respect to the bending force of the gas adsorption device is increased. Furthermore, by laminating the aluminum foil, excellent barrier properties can be obtained, and the gas adsorbent can be stored for a long period of time.

  In addition, in the configuration of the vacuum heat insulating material itself, when the size of the vacuum heat insulating material is the same, if it is configured with a plurality of core materials, the volume of one core material portion is reduced, so that the internal pressure increases due to a slight gas intrusion. It becomes easy.

  However, since the adsorbent in the present invention has a structure that can fully exhibit the characteristics of the gas adsorbent, it suppresses the internal pressure increase over time, ensures the heat insulation performance of the vacuum heat insulation material, and ensures the heat insulation performance over time as a building material. To do.

  In addition, the shapes of the core material and the vacuum heat insulating material in the present invention can be any shape made of a triangle, a quadrangle, a polygon, a circle, an L shape, or a combination thereof depending on the location where heat insulation is required.

  Further, in the production of the vacuum heat insulating material, the method of forming an independent space includes a method of heating and pressurizing the outer cover material including a portion having the core material under reduced pressure, and an outer peripheral portion of the outer cover material under reduced pressure. There is no particular designation such as a method in which only the heat-welded layers that are pressed by atmospheric pressure after the core material is heat-welded and the core material is sealed under reduced pressure are heated to the melting point of the heat-welded layer in a high-temperature atmosphere.

  The core material in the present invention is a material that retains the shape of the vacuum heat insulating material from compression by atmospheric pressure, and if it has a high porosity, fiber, powder, foamed resin, porous material, thin film laminate, etc. , Not particularly specified.

  For example, glass fiber, glass fiber, alumina fiber, silica alumina fiber, silica fiber, rock wool, silicon carbide fiber etc. in fiber system, silica, perlite, carbon black in powder system, urethane foam, phenol foam, styrene in foamed resin There are forms. Moreover, it is also possible to use these mixtures and a molded object.

  The jacket material in the present invention shuts off the space inside the vacuum heat insulating material and the outside space, and a laminate film having a barrier property can be used, and its configuration is not particularly specified.

  The innermost heat-bonding layer includes low-density polyethylene, linear low-density polyethylene, high-density polyethylene, unstretched polypropylene, polyacrylonitrile, unstretched polyethylene terephthalate, unstretched nylon, unstretched ethylene-polyvinyl alcohol copolymer resin. Etc. can be used and is not particularly specified.

  Moreover, in order to suppress gas intrusion from the outside, a metal foil, a vapor deposition film, a coating film, or the like can be used. The type and number of layers are not particularly specified. The metal foil is not particularly specified such as aluminum, stainless steel, iron or a mixture thereof. Moreover, the material of the plastic film used as the base material for vapor deposition or coating is not particularly specified, such as polyethylene terephthalate, ethylene-polyvinyl alcohol copolymer resin, polyethylene naphthalate, nylon, polypropylene, polyamide, and polyimide. Further, the material for vapor deposition is not particularly specified such as aluminum, cobalt, nickel, zinc, copper, silver, silica, alumina, diamond-like carbon, and a mixture thereof. Also, the coating material is not particularly specified such as PVA, polyacrylic acid resin or a mixture thereof.

  Further, it is possible to further provide a film on the outer layer or the intermediate layer for the purpose of improving pinhole resistance and abrasion resistance, imparting flame retardancy, and further improving barrier properties.

  Here, the film provided on the outer layer or the intermediate layer is nylon, ethylene / tetrafluoroethylene copolymer resin, polyethylene terephthalate, polyethylene naphthalate, polypropylene, ethylene-polyvinyl alcohol copolymer resin, etc. , Not particularly specified.

  The moisture adsorbent in the present invention adsorbs moisture contained in a gas, and includes activated carbon, silica gel, calcium oxide, etc., but is not particularly specified.

  The gas adsorbent in the present invention is for adsorbing non-condensable gas contained in the gas, such as oxides of alkali metals and alkaline earth metals, hydroxides of alkali metals and alkaline earth metals, etc. For example, there are lithium oxide, lithium hydroxide, barium oxide, barium hydroxide, etc., but there is no particular designation.

  Here, the shape of the moisture adsorbing material is not particularly specified, such as a granular shape or a pellet shape, but is preferably a powder shape.

  When the moisture adsorbing material is in a powder form, the surface area per unit weight is increased, so that it is possible to adsorb the surrounding moisture more quickly. Therefore, it is easy to design a partition that connects the space for accommodating the gas adsorbent and the moisture adsorbent.

  This is for the following reason. In order to reduce moisture adsorption leakage by the moisture adsorbent, the air permeability of the partition connecting the space containing the gas adsorbent and the space containing the moisture adsorbent must be smaller than a certain value.

  This is to secure a time for the gas containing moisture to remain in the space containing the moisture adsorbing material, and this time can be shortened as the rate at which the moisture adsorbing material adsorbs moisture is increased. This means that the air permeability of the partition connecting the space containing the gas adsorbing material and the space containing the water adsorbing material can be increased.

  Therefore, more gas outside the gas adsorption device can be adsorbed per unit time, and the gas adsorption device can be used for applications that need to increase the gas adsorption rate.

  Here, the powder form has an average particle diameter of 50 μm or less, and preferably has an average particle diameter of 10 μm or less.

  The invention according to claim 2 is characterized in that, in the invention according to claim 1, the adsorbent is disposed at least in a core portion adjacent to the outer peripheral portion of the jacket material.

  Even if the barrier property of the laminate surface of the jacket material is strengthened by using metal foil, the edge of the jacket material is adjacent to the edge of the jacket material because the heat-welded layer with high gas permeability is exposed. The degree of vacuum tends to worsen as the core part is made, and the heat insulation performance tends to deteriorate.

  Therefore, by applying an air adsorbing material to this portion, the invading gas from the end is efficiently adsorbed, and deterioration of the heat insulating performance is suppressed.

  Further, when the adsorbing material is arranged in this manner, even in the core material portion that is not adjacent to the end portion of the jacket material, the intruding gas is adsorbed by the core material portion adjacent to the end portion, so that the gas becomes more difficult to enter. This makes it difficult to change the internal pressure.

  In addition, it is more desirable that the adsorbent is disposed in a core portion adjacent to the end portions of two or more sides, which is a portion where gas is more likely to enter.

  Moreover, you may arrange | position an adsorbent other than the core part adjacent to the outer peripheral part. If it is placed on all core parts, even if some core parts are nailed when applied to a building, intrusion gas from that part is placed on the adjacent core part. It can be adsorbed by an adsorbent.

  In this case, the amount of the intrusion gas is larger in the adjacent core portion than in the non-adjacent core portion. Therefore, it is possible to change the amount of adsorbent used according to the amount of intrusion gas.

  In addition, it is more desirable to increase the amount of the core material adjacent to the outer peripheral portion to be used in the core material portion adjacent to the end portions of two or more sides, which is a portion where gas is more likely to enter. Since the amount of the adsorbent used in the core portion adjacent to the outer peripheral portion of the jacket material is larger than the core portion that is not adjacent, the amount used can be suppressed, resulting in a reduction in cost.

  In addition, when the site to be nailed is known in advance, it may be arranged on the core material portion adjacent to the portion adjacent to the nail driving portion.

  The invention according to claim 3 is the invention according to claim 1 or 2, characterized in that the gas adsorbent is made of ZSM-5 type zeolite subjected to copper ion exchange.

  Since the ZSM-5 type zeolite subjected to the copper ion exchange has a high gas adsorption capacity, the heat insulation performance with time can be maintained with a small amount of use.

  The copper ion-exchanged ZSM-5 type zeolite is very active against both gas and moisture. For this reason, it is necessary to make the gas which has adsorbed moisture by the moisture adsorbing material reach the gas adsorbing material.

  By optimizing the air permeability of the partition that connects the space where the gas adsorbent and the moisture adsorbent are accommodated, the amount of water-containing gas is reduced by increasing the time that the gas stays near the moisture adsorbent. Reaching is achieved.

  Copper ion-exchanged ZSM-5 type zeolite is known for its high activity against nitrogen adsorption, probably shape selectivity due to the relative relationship between the pore diameter and the molecular diameter of nitrogen, and its three-dimensional structure. I think it depends on the specificity of Furthermore, it has adsorption activity to gas species other than nitrogen, that is, oxygen, moisture, carbon monoxide, carbon dioxide, hydrogen and the like.

  The production of ZSM-5 type zeolite subjected to copper ion exchange is carried out through processes of copper ion exchange, water washing, drying, and heat treatment of commercially available ZSM-5 type zeolite.

Copper ion exchange can be performed by a known method, but a method of immersing in an aqueous solution of a soluble salt of copper, such as an aqueous solution of copper chloride or an aqueous solution of copper ammine, is generally used, particularly copper (II) propionate or acetic acid. Those prepared by a method using a Cu ²⁺ solution containing carboxylate such as copper (II) have high nitrogen adsorption activity.

Wash with water thoroughly after ion exchange. Next, heat drying or drying under reduced pressure is performed to remove surface adhering water. Thereafter, an appropriate heat treatment is performed under a low pressure. This is necessary to reduce Cu ²⁺ introduced by ion exchange to Cu ⁺ and develop nitrogen adsorption ability. The pressure during the heat treatment is 10 mPa or less, preferably 1 mPa or less, and the temperature is about 300 ° C. or more, preferably about 500 ° C. to 600 ° C. in order to promote the reduction to Cu ⁺ .

  By passing through the above process, gas adsorption activity such as nitrogen, moisture, oxygen, carbon monoxide, carbon dioxide, hydrogen, etc. is expressed.

In the ZSM-5 type zeolite subjected to copper ion exchange, copper is first ion exchanged as Cu ²⁺ . Next, by performing an appropriate heat treatment under low pressure, Cu ²⁺ is reduced to Cu ⁺ and exhibits gas adsorption activity.

Therefore, regarding the silica to alumina ratio of the ZSM-5 type zeolite, when the silica to alumina ratio is low, that is, when a large amount of −1 valent aluminum is present, Cu ²⁺ is more stable, and heat treatment makes Cu ⁺ become Cu ⁺ . Since the sites to be reduced are reduced, the nitrogen adsorption activity is also reduced.

On the other hand, when the silica to alumina ratio is large, i.e., when there is little −1 valent aluminum, less copper is introduced by ion exchange and thus less Cu ⁺ sites, which also reduces the nitrogen adsorption activity. Therefore, in order to develop nitrogen adsorption activity, it is desirable that the silica to alumina ratio is in an appropriate range, and a range of 8 to 25 is desirable.

  Further, ZSM-5 type zeolite subjected to copper ion exchange has no harmful information and is considered to have a low environmental load.

  According to a fourth aspect of the present invention, in the invention according to any one of the first to third aspects, the core material is a board of glass fiber aggregates in which the fiber orientation direction is perpendicular to the heat transfer direction. It is the molded object shape | molded in the shape.

  Since the glass fibers are oriented perpendicularly to the heat transfer direction, the heat transfer performance by the fibers is suppressed, so that the heat insulation performance is higher than when the orientation directions are random. In addition, when the glass fiber aggregate is molded by a hot press or the like, an effect of stretching the fiber can be expected, so that the laminated arrangement of the glass fibers is improved, so that the heat insulation performance is further improved. Therefore, when using for a building member, the outstanding heat insulation performance is expressed.

  Furthermore, when the core material is a molded body, the handleability during production and the surface properties and dimensional accuracy of the vacuum heat insulating material are improved. By improving the surface property and dimensional accuracy of the vacuum heat insulating material, it becomes easy to design as a building material.

  In general, when using a fiber-based core material, the initial heat insulation performance is excellent, but when used over a long period of time, because the gap diameter is large, the heat insulation performance is easily affected by changes in internal pressure, and the heat insulation performance deteriorates. There is a problem that it gets bigger. Therefore, the intrusion gas is adsorbed by the gas adsorbent to reduce the change in internal pressure and suppress the deterioration of the heat insulation performance.

The density of the molded body at this time is not particularly specified, but is 100 kg / m ³ or more from the viewpoint of maintaining the shape as the molded body, and 300 kg / m ³ or less from the viewpoint of obtaining good heat insulation performance. A range of is desirable.

  Further, the glass fiber to be used is not particularly specified, but a glass-forming oxide that can be in a glass state is desirable, a thermal deformation temperature is low, and those that are laminated in the thickness direction are desirable, and as a general-purpose industrial product Glass wool is more desirable from the viewpoint of low cost and handleability.

  Further, the fiber diameter is not particularly specified, but 10 μm or less is more desirable because a finer fiber diameter provides better heat insulation performance.

  The invention according to claim 5 is the invention according to any one of claims 1 to 4, wherein the adsorbent is a container that forms a space in which the moisture adsorbent is accommodated by remote control. An unsealing means for unsealing is provided.

  In order to reduce the deterioration of the highly active gas adsorbent, it is desirable to open the gas adsorber device after sealing the vacuum heat insulating material. However, the vacuum heat insulating material has a configuration in which the internal space and the outside are isolated from each other by the jacket material. It is. For this reason, it is difficult to open the gas adsorption device directly from the outside. Therefore, it is desirable that the gas adsorption device can adsorb gas by remote control.

  As a remote operation method, for example, when both the gas adsorption device container and the vacuum heat insulating material are soft packaging materials, a protrusion is included in the vacuum heat insulating material in advance, and the container of the gas adsorption device is applied by the atmospheric pressure applied after the pressure reduction. There is a method of opening by being pressed on, and a method of pressing when a force higher than atmospheric pressure is required, but it is not particularly specified as long as it is a method of opening by remote operation after sealing the vacuum heat insulating material. .

  The invention according to claim 6 is a building member to which the vacuum heat insulating material according to any one of claims 1 to 5 is applied.

  By making the gas adsorbent a gas adsorbing device as described above, it is possible to reduce the deactivation due to moisture at the time of manufacturing and when applying vacuum heat insulating material, so that the ability of the gas adsorbent can be fully demonstrated. Can do. That is, even when applied to a building member, the energy saving effect can be maintained over a long period of time.

  The building member in the present invention is a member that can be attached to a wall surface, a floor surface, a roof, etc. for the purpose of heat insulation of a building or the like, and at least a vacuum heat insulating material may be applied, and the vacuum heat insulating material itself. However, the combination of a vacuum heat insulating material and a heat insulating material, and the combination of a vacuum heat insulating material and another material may be sufficient.

  As a material to be combined, for example, styrene foam, urethane foam, phenol foam, glass wool, gypsum and the like can be considered, but there is no particular designation. In the case of the vacuum heat insulating material itself, it is easy to visually distinguish the difference between the core material portion and the other portions, so that it is easy to perform nailing so as not to cause a vacuum break.

  Further, in this case, the work efficiency is improved in the construction as compared with the case where a plurality of vacuum heat insulating materials having a single core material are pasted, when the vacuum heat insulating material has a plurality of core materials. Further, when combined with other materials, if the vacuum heat insulating material is not exposed, the risk of a vacuum break due to scratches and piercings is reduced, so that handling is very easy during construction in a building.

  In addition, since the gas adsorption device can be thinned, the thin and high heat insulation characteristics unique to the vacuum heat insulating material can be utilized, so that it can also be thinned as a building member.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present invention will be described with reference to the drawings. The same reference numerals are given to the same configurations as those of the conventional example or the embodiments described above, and detailed descriptions thereof will be omitted. The present invention is not limited to the embodiments.

(Embodiment 1)
FIG. 1 is a plan view of a vacuum heat insulating material according to Embodiment 1 of the present invention. In FIG. 1, a vacuum heat insulating material 1 includes a plurality of core materials 2, a gas barrier outer covering material 3 having a heat welding layer on one side, and an adsorbing material 4, and the outer coverings facing each other. The core material 2 is sealed under reduced pressure so that the core material 2 is located in two or more independent vacuum spaces between the materials 3, and the adsorbent material 4 is arranged in one core material portion.

  First, the configuration of the vacuum heat insulating material 1 will be described. In the vacuum heat insulating material 1, the core materials 2 are arranged at predetermined intervals, respectively, and the adsorbent 4 is arranged in a predetermined core material 2 portion, and is sealed under reduced pressure by the jacket material 3. Moreover, the heat welding part 5 is provided in the circumference | surroundings of the core material 2 so that each core material 2 may be located in the independent vacuum space.

  The adsorbing material 4 is arranged in the core material portion 2b not adjacent to the outer periphery of the jacket material, assuming nailing to the core material portion 2a adjacent to the outer periphery of the jacket material.

  Moreover, FIG. 2 is sectional drawing of the adsorbent used for the vacuum heat insulating material in Embodiment 1 of this invention. The adsorbent 4 is disposed in the vacuum heat insulating material 1 as a gas adsorbing device, and has a gas adsorbent 7 and a moisture adsorbent 8 in a gas-impermeable container 6. The adsorbent 8 has a structure that is accommodated in separate vacuum spaces by partitions 9. Further, a protrusion 10 is attached to the surface of the space of the container 6 in which the moisture adsorbing material 8 is accommodated, and a through-hole is formed in the container 6 after the vacuum heat insulating material 1 is sealed. The space where 8 is arranged and the space inside the vacuum heat insulating material 1 can be trained.

  The adsorbent (gas adsorbing device) of the present embodiment is composed of a soft wrapping material made of a gas adsorbing material 7, a moisture adsorbing material 8, and a plastic laminate film (gas impermeable material) including, for example, aluminum foil. The container 6 is divided into two spaces by a partition 9 made of, for example, a nonwoven fabric, the inside of which can adjust the air permeability. The gas adsorbent 7 and the moisture adsorbent 8 are different from each other in the container 6. Contained in space. Note that the two spaces partitioned by the partition 9 are arranged in a direction substantially perpendicular to the thickness direction of the space that accommodates the gas adsorbent 7 or the moisture adsorbent 8. In addition, the container in which the protrusion (opening means) 10 for opening the container 6 forming the space in which the moisture adsorbing material 8 is accommodated by remote operation forms the space in which the moisture adsorbing material 8 is accommodated. 6 is in contact.

  The protrusion (opening means) 10 is made of, for example, a plastic molded product, and one surface is convex, the other surface is concave, and an external force that presses the convex surface is not applied to the concave portion of the concave surface. The projection has a height that is the same as or slightly lower than the depth of the dent, and when an external force that pushes the convex surface is applied, the projections (opening means) 10 become smaller and the height of the projection is higher than the depth of the dent. The container 6 that is configured to be deformable and that forms a space in which the moisture adsorbing material 8 is accommodated is disposed on the concave surface side having the protrusions, and the convex surface is pushed by a force of about atmospheric pressure. Then, the protrusion of the protrusion (opening means) 10 comes into contact with the container 6 forming the space in which the moisture adsorbing material 8 is accommodated, and eventually forms a space in which the moisture adsorbing material 8 is accommodated. The container 6 is configured to pass through.

  In addition, since the gas adsorbent 7 is vacuum-sealed inside the container 6 made of a gas permeable material, the gas adsorbent 7 does not touch the gas even if the gas adsorbing device is left in the atmosphere for a long time. Therefore, deactivation can be suppressed and it can be stored in the atmosphere for a long time. For the same reason, deactivation during production can be suppressed.

  Next, the manufacturing method of the vacuum heat insulating material 1 is demonstrated. First, a plurality of core members 2 (a core member 2a adjacent to the outer periphery of the outer cover member 3 and a core member 2b not adjacent to the outer periphery of the outer cover member 3) with the heat welding layer of the outer cover member 3 facing upward, The adsorbent 4 is disposed in the core material 2b portion that is not adjacent to the end portion of the jacket material 3. Next, this is covered with another outer covering material 3 so that the heat-welded layers face each other. Further, the outer peripheral portion of the jacket material 3 is welded under reduced pressure, and the core material 2 is welded by a method such as placing it in a high temperature environment under atmospheric pressure, thereby providing the heat welded portion 5.

  When the adsorbent 4 is disposed in the core material 2b portion, the core material 2b in a state in which the gas adsorbing device 1 is embedded on the one surface portion to the extent that the protrusion (opening means) 10 is exposed, The convex surface of the object (opening means) 10 is in contact with the outer cover material 3, and the concave surface with the protrusion of the protrusion (opening means) 10 forms a space in which the moisture adsorbing material 8 is accommodated. The container 6 is brought into contact.

  The gas adsorption device is opened inside the vacuum heat insulating material as follows.

  Since the jacket material 3 of the vacuum heat insulating material 1 is a plastic laminate film, it is deformed by the atmospheric pressure applied after vacuum sealing, and applies a compressive force to the gas adsorption device. As a result, since the protrusion 10 applies a piercing force to the container 6 made of the soft packaging material, a through-hole is formed in the container 6 so that the gas in the outer cover material 3 can be adsorbed.

  Through this through hole, the gas in the vacuum heat insulating material 1 first enters the space containing the moisture adsorbing material 8. Here, moisture is removed from the gas by the moisture adsorbing material 8. Next, the gas whose moisture has decreased passes through the partition 9 and moves to the space in which the gas adsorbent 7 is accommodated. Therefore, since the gas adsorbent 7 can exhibit most of its adsorption capacity for gas adsorption, it efficiently adsorbs gas.

  Moreover, since the air permeability of the through-hole produced by the protrusion 10 is made larger than the air permeability of the partition 9, the gas that has entered the space containing the moisture adsorbing material 8 stagnates inside. Since the moisture contained in the gas is removed by the moisture adsorbing material 8 during this period, the amount of moisture contained in the gas that reaches the gas adsorbing material 7 through the partition 9 is greatly reduced.

  Therefore, since the gas adsorbent 7 can exert most of its adsorption capacity for gas adsorption, it can adsorb gas efficiently.

  By making the adsorbent 4 a gas adsorbing device having the above-described configuration, the characteristics of the gas adsorbent 7 can be fully exhibited, so that the change in the heat insulating performance of the vacuum heat insulating material 1 over time can be suppressed.

  FIG. 3 is a plan view of a vacuum heat insulating material in which the arrangement of the core material in the present embodiment is changed. As in FIG. 1, nail driving to the core 2a adjacent to the outer periphery is assumed, but a plurality of adsorbents may be arranged according to the number of cores. Further, the arrangement location at this time is not particularly specified, and may be only the core portion adjacent to the core portion to be nailed as shown in FIG. It is not necessary to arrange, and it can arrange as needed. Moreover, when the place to nail is known beforehand, it is desirable to arrange in the surrounding core part.

(Embodiment 2)
FIG. 4 is a plan view of the vacuum heat insulating material in Embodiment 2 of the present invention. In FIG. 4, the vacuum heat insulating material 11 includes a plurality of core materials 12, a gas barrier outer covering material 13, and an adsorbing material 14.

  First, the configuration of the vacuum heat insulating material 11 will be described. In the vacuum heat insulating material 11, the core materials 12 are arranged in a grid pattern at predetermined intervals, respectively, and the adsorbent 14 is arranged in a predetermined core material 12 portion and sealed under reduced pressure by an outer covering material 13. In addition, a heat welding portion 15 is provided around the core material 12 so that the core materials 12 are located in independent vacuum spaces. The adsorbent 14 is disposed in the core material 12 a adjacent to the outer peripheral portion of the jacket material 13 with the aim of adsorbing intrusion gas from the end of the jacket material 13.

  Since the configuration and mechanism of the adsorbent 14 are the same as those in the first embodiment, description thereof is omitted.

  Moreover, since the manufacturing method of the vacuum heat insulating material 11 is the same as that of the vacuum heat insulating material 1 of Embodiment 1, description is abbreviate | omitted.

  By making the adsorbent material 14 a gas adsorbing device, the characteristics of the gas adsorbent material can be fully exhibited, so that the change in heat insulation performance of the vacuum heat insulating material 11 over time can be suppressed.

  A gas such as air or water vapor enters the space of the 20 core members 12a adjacent to the outer peripheral portion of the jacket member 13 depending on the difference in pressure between the atmospheric pressure and the core member 12a. 14 adsorbs the intruding gas, thereby suppressing a change in internal pressure.

  Further, the 16 core members 12b that are not adjacent to the outer peripheral portion of the jacket material 13 are configured such that the adsorbent 13 disposed in the core material 12a portion efficiently adsorbs gas from the end portion, Since the core material 12a adjacent to the outer peripheral portion is in a separate space through the heat welded portion 15, the deterioration of the heat insulating performance is suppressed as compared with the core material 12a adjacent to the outer peripheral portion of the jacket material 13. Therefore, the heat insulation performance of the whole vacuum heat insulating material can be maintained over a long period of time.

  The location of the adsorbent is not limited to the core 12a portion adjacent to the outer periphery of the jacket material. If the place to be naild is known in advance, the adsorbent is also adsorbed to the surrounding core portion. It is more desirable to arrange the material.

(Embodiment 3)
FIG. 5 is a sectional view of a building to which the vacuum heat insulating material in Embodiment 3 of the present invention is applied.

  In the building 16 according to the third embodiment of the present invention, the vacuum heat insulating material according to the second embodiment is applied between the outer wall 17 and the inner wall 18, below the floor in contact with the floorboard 19, or on the attic in contact with the roofing material 20. Building member 21 is arranged. The building 16 configured in this manner exhibited excellent heat retention and energy saving effect by applying the building member 21 having excellent heat insulation performance. In addition, since the fluctuation of the heat insulation performance was small, the energy saving effect could be maintained for a long time.

  In this embodiment, the vacuum heat insulating material of the second embodiment is used. However, the vacuum heat insulating material of the first embodiment also provides an excellent energy saving effect.

  In the vacuum heat insulating material of Embodiment 2, the specifications of the adsorbent were variously changed to compare the heat insulating performance over time.

Example 1
As a core material, a molded body in which an assembly of glass fibers whose fiber orientation direction is perpendicular to the heat transfer direction is formed into a board shape, ZSM-5 type zeolite as a gas adsorbent, and calcium hydroxide as a moisture adsorbent. used.

  The heat insulation performance after 50 years was predicted by the temperature acceleration test of the vacuum heat insulating material, and further the energy saving effect of the building using this vacuum heat insulating material as a building member was predicted.

  By using the core material having the above configuration as the core material, a very high initial heat insulation performance of 0.0020 W / mK was obtained. Regarding the heat insulation performance over time, generally, the fiber-based material has a large amount of change in heat insulation performance relative to the amount of change in internal pressure, so the heat insulation performance over time is likely to deteriorate, but by using the gas adsorbent of this configuration, It was predicted that the deterioration was suppressed to 0.0050 W / mK and a high energy saving effect could be maintained.

(Comparative Example 1)
In Example 1, only the moisture adsorbent was applied without applying the gas adsorbent.

  The initial value was 0.0020 W / mK, which was the same as in Example 1, but the thermal insulation performance deteriorated before exceeding 0.0250 W / mK, and the energy saving effect was maintained even when applied as a building member. I predicted I couldn't. The moisture adsorbent is considered to have deteriorated the heat insulation performance over time because it cannot adsorb gases such as nitrogen and oxygen that enter the vacuum heat insulating material.

(Comparative Example 2)
In Example 1, the gas adsorbent and the moisture adsorbent were used in combination without forming the adsorbent as a device.

  The initial value was 0.0020 W / mK, which was the same as in Example 1, but the temporal heat insulation performance deteriorated to 0.0200 W / mK. Since the gas adsorbent is more active against moisture than the moisture adsorbent, the gas adsorbent is deactivated by adsorbing the moisture that enters the vacuum heat insulating material, so that the gas adsorption capacity can be fully demonstrated. I think it was not.

  As described above, the vacuum heat insulating material according to the present invention can maintain heat insulating performance for a long period of time. For this reason, it can be used for buildings that require heat insulation performance for a very long time. In addition to buildings, the present invention can also be applied to walls such as vehicles such as trains and automobiles that form a space requiring heat insulation. Moreover, if it is used for a cold insulation device such as a refrigerator, or a thermal insulation device such as an electric water heater, a rice cooker, a thermal insulation cooker, or a hot water heater, it shows an excellent energy saving effect over a long period of time. It can also be applied to office equipment such as notebook computers, copiers, printers, projectors, etc., which require space-saving and high thermal insulation performance. Also, it can be applied to uses such as container boxes and cooler boxes that require cold storage.

The top view of the vacuum heat insulating material in Embodiment 1 of this invention Sectional drawing of the adsorbent used for the vacuum heat insulating material of the same embodiment The top view which shows the modification of the vacuum heat insulating material of the embodiment The top view of the vacuum heat insulating material in Embodiment 2 of this invention Sectional drawing of the building which applied the vacuum heat insulating material in Embodiment 3 of this invention

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Vacuum heat insulating material 2 Core material 3 Cover material 4 Adsorbent material 6 Container 7 Gas adsorbent material 8 Moisture adsorbent material 9 Partition 10 Protrusion (opening means)
DESCRIPTION OF SYMBOLS 11 Vacuum heat insulating material 12 Core material 13 Cover material 14 Adsorbent material 21 Building member

Claims (6)

  The core material has at least a plurality of core materials, a gas barrier coating material having a heat welding layer on one side, and an adsorbing material, and the core material is between the coating materials facing each other. Two or more independent vacuum spaces, and the adsorbent is a vacuum heat insulating material disposed in one or more core parts, wherein the adsorbent is a gas adsorbent And a water adsorbent and a container made of a gas-impermeable material, wherein the container is partitioned into at least two spaces by a partition that can control air permeability, and the gas adsorbent and the gas Each of the moisture adsorbents is accommodated in a different space of the container.   The vacuum heat insulating material according to claim 1, wherein the adsorbent is disposed at least in a core portion adjacent to an outer peripheral portion of the jacket material.   The vacuum heat insulating material according to claim 1 or 2, wherein the gas adsorbent is made of ZSM-5 type zeolite subjected to copper ion exchange.   The said core material is a molded object which shape | molded the aggregate | assembly of the glass fiber with which the orientation direction of a fiber was perpendicular | vertical with respect to the heat-transfer direction in the board shape. Vacuum insulation material.   The vacuum heat insulating material as described in any one of Claim 1 to 4 with which the said adsorbent was equipped with the opening means which opens the container which forms the space in which the water | moisture-content adsorbent is accommodated by remote control.   The building member which applied the vacuum heat insulating material as described in any one of Claim 1 to 5.