JP2009019697A - Vacuum heat insulating material and construction member applying vacuum heat insulating material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a vacuum heat insulating material capable of maintaining heat insulating performance for a long period of time even if material of which heat insulating performance greatly changes according to inner pressure change such as a fiber system is used as core material. <P>SOLUTION: In the vacuum heat insulating material 1 including at least a plurality of core materials 2 composed of fiber system material, a casing material 3, and gas adsorbent 4 made of ZSM-5 type zeolite subjected to copper ion exchange, the absorbent 4 has monovalent copper as not less than 73% of copper site of ZSM-5 type zeolite subjected to copper ion exchange, and is arranged at one or more core material 2 parts. Inner pressure change due to gas invasion with time is inhibited by application of the gas adsorbent 4 having excellent adsorption performance. Consequently, heat insulating performance can be maintained for a long period of time even when material of which heat insulating performance is easily affected by inner pressure change is used as the core material. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a vacuum heat insulating material and a building member to which the vacuum heat insulating material is applied.

  In recent years, as a measure against global warming, which is a global environmental problem, there has been an active movement to promote energy saving in buildings such as houses along with home appliances and industrial equipment, and a heat insulating material having excellent heat insulating performance has been demanded.

  As a high-performance heat insulating material, there is a vacuum heat insulating material, in which a core material serving as a spacer is inserted into a jacket material having a gas barrier property, and the inside is sealed under reduced pressure.

  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, in order to prevent the deterioration of the degree of vacuum in the vacuum heat insulating material and maintain the excellent heat insulating performance over a long period of time, the silica container is filled with a silica alumina-based adsorbent as a getter material together with the heat insulating spacer material, And the vacuum heat insulating structure characterized by having embedded the vacuum heat insulating material which sealed the inside of the said plastic container in the organic foam heat insulating material is proposed (for example, refer patent document 1).

  Since the silica-alumina-based adsorbent can adsorb polar inorganic gas, deterioration of the degree of vacuum due to carbon dioxide gas or water vapor can be prevented.

  Moreover, as an alloy that removes nitrogen at a low temperature, there is a Ba-Li alloy (see, for example, Patent Document 2).

  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.

  Moreover, there exists an adsorbent which consists of ZMS-5 type zeolite which carried out copper ion exchange as what removes impurity gas, such as nitrogen, from refinement | purification object gas (for example, refer patent document 3).

This is to impart nitrogen adsorption activity by introducing copper ions into a ZMS-5 type zeolite by conventional ion exchange methods and performing heat treatment, and the maximum nitrogen adsorption amount at an equilibrium pressure of 10 Pa is 0. .238 mol / kg (5.33 cc / g).
JP-A-61-103090 Japanese National Patent Publication No. 9-512088 JP 2003-31148 A

  However, in the configuration of Patent Document 1, since a low activity gas such as nitrogen cannot be adsorbed, when a vacuum heat insulating material is used over a long period of time such as a house, the effect of suppressing an increase in internal pressure due to intrusion gas is obtained. There is a problem that the amount of adsorbent required is increased due to the insufficient adsorption capacity. In particular, when a material having a property of large variation in heat insulation performance due to a change in internal pressure, such as a fiber material, is used as the core material, the problem is remarkable.

  Moreover, in the structure of the said patent document 2, although gas with low activity, such as nitrogen, can also be adsorb | sucked, since the adsorption capacity is small, the required amount of adsorbent will increase. Furthermore, since Ba is a PRTR-designated substance, it is desired that it has no problem with respect to the environment and the human body for industrial use.

  Moreover, in the structure of the said patent document 3, although gas adsorption, such as nitrogen, is possible at normal temperature, when using a vacuum heat insulating material over a long period of time, the adsorbent which can adsorb | suck a larger capacity | capacitance is desired. .

  In addition, in the vacuum heat insulating material having the above-described configuration having a plurality of core members, although it is difficult for gas from the outside to enter, there is a problem that the internal pressure tends to increase because the space volume in one space becomes small. Thus, an adsorbent capable of adsorbing a large volume even under reduced pressure has been desired.

  The present invention solves the above-mentioned conventional problems, and in a vacuum heat insulating material, even when a material having a large variation in heat insulating performance due to a change in internal pressure is used as a core material, a heat insulating performance over time is ensured. 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 is capable of adsorbing at least a plurality of core materials made of a fiber-based material, a jacket material, and nitrogen made of ZSM-5 type zeolite exchanged with copper ions. 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 outer jacket materials facing each other. The adsorbent is disposed in one or more core parts.

  Even if gas intrusion occurs due to the application of a gas adsorbent, the change in the insulation pressure is suppressed even when a material that is susceptible to the change in the internal pressure is used as the core material, such as a fiber system, as the core material. Suppress. By positioning the core material in at least two or more independent spaces, the intrusion gas from the edge of the jacket material is less likely to enter the core material part that is not adjacent to the edge of the jacket material, and the internal pressure change is unlikely to occur. Furthermore, the heat insulation performance as a whole vacuum heat insulating material can be maintained more.

  Furthermore, as a gas adsorbent, an adsorbent composed of ZSM-5 type zeolite subjected to copper ion exchange, and among copper sites of ZSM-5 type zeolite subjected to copper ion exchange, 73% or more of copper sites are copper. When an adsorbent characterized by being a monovalent site is used, it is possible to adsorb a gas having a low activity such as nitrogen, so that a change in internal pressure can be suppressed with a small amount of use.

  The vacuum heat insulating material of the present invention is not only excellent in initial heat insulating performance, but can maintain heat insulating performance over a long period of time. Moreover, the building member excellent in heat insulation performance can be obtained by applying the vacuum heat insulating material excellent in heat insulation performance.

  The invention according to claim 1 includes at least a plurality of core materials, a gas barrier outer covering material having a heat welding layer, and a gas adsorbing material capable of adsorbing nitrogen, and the heat welding layers are opposed to each other. A vacuum heat insulating material that is sealed under reduced pressure so that the core material is positioned in two or more independent vacuum spaces between the jacket materials, and the core material has a fiber orientation direction in a heat transfer direction. A molded body obtained by molding an assembly of glass fibers perpendicular to a board shape, and the adsorbent is an adsorbent made of ZSM-5 type zeolite that has been subjected to copper ion exchange, and has undergone copper ion exchange. Among the copper sites of ZSM-5 type zeolite, 73% or more of copper sites are copper monovalent sites, and the adsorbent is disposed in one or more independent vacuum spaces. By using a vacuum heat insulating material, the core material can change the internal pressure. Even if the time heat insulating performance by susceptible slight gas penetration Hibiki was used a material having worse properties, deterioration of heat insulating performance by applying the gas adsorbent can be suppressed.

  The core material of the present invention has higher heat insulation performance than the case where the orientation direction is random because the glass fibers are oriented perpendicularly to the heat transfer direction, thereby suppressing heat transfer by the fibers. 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. 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.

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.

  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 adsorbent of the present invention is an adsorbent composed of ZSM-5 type zeolite subjected to copper ion exchange, and at least 73% or more of copper sites among the copper sites of ZSM-5 type zeolite subjected to copper ion exchange, It is characterized by being a copper monovalent site.

  Copper ion-exchanged ZSM-5 type zeolite is known for its high activity for nitrogen adsorption, presumably due to the 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 specificity. 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 the ZSM-5 type zeolite subjected to the copper ion exchange is performed through a process of copper ion exchange, washing with water, drying and heat treatment of a 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 ⁺ .

  Through the above process, the copper ion exchanged ZSM-5 type zeolite imparted with gas adsorption activity has gas adsorption activity of nitrogen, moisture, oxygen, carbon monoxide, carbon dioxide, hydrogen and the like.

In the copper ion exchange ZSM-5 type zeolite, 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, it is considered that the copper ion exchange ZSM-5 type zeolite has no harmful information and has a low environmental load.

  The copper ion exchanged ZSM-5 type zeolite reported so far is ion-exchanged with an aqueous solution of a soluble salt of copper, such as an aqueous solution of copper chloride, an aqueous solution of copper ammine, and an aqueous solution of copper acetate, and then heat-treated. As a result, the copper ions were reduced to monovalent and nitrogen adsorption activity was imparted. The maximum proportion of the nitrogen adsorption active copper monovalent sites in the copper sites of the copper ion exchanged ZSM-5 type zeolite thus synthesized was about 60%.

  In the present invention, ZSM-5 type zeolite, which has excellent gas adsorption capacity in a low pressure region and has 73% or more of copper sites present as adsorption-active copper monovalent sites, is applied as a gas adsorbent. In addition to nitrogen and carbon monoxide, low-pressure adsorption of gaseous species such as water, oxygen, hydrogen and carbon dioxide is possible.

  The ratio of copper monovalent sites in the copper ion-exchanged copper sites is one in the copper ion-exchanged ZSM-5 type zeolite with respect to the total amount of copper in the copper ion-exchanged ZSM-5 type zeolite. It is obtained by calculating the carbon oxide adsorption molar amount.

  In addition, the total copper molar amount in the ZSM-5 type zeolite exchanged with copper ions was determined by dissolving the ZSM-5 type zeolite exchanged with copper ion with perchloric acid, etc., and using an ICP emission spectrometer or EDTA titration. It is possible to ask.

  Furthermore, it has been clarified that, among the copper monovalent sites, the oxygen tricoordinate copper monovalent site has a stronger interaction with gas molecules and can chemisorb gas. Furthermore, by using at least 84% of the copper monovalent sites as oxygen tricoordinate copper monovalent sites, the gas adsorption capacity increases and the gas is more strongly adsorbed under high vacuum. It is possible to increase the chemisorption capacity. Further, not only nitrogen and carbon monoxide but also gas species such as water, oxygen, hydrogen and carbon dioxide can be adsorbed at a low pressure.

  The ratio of oxygen tri-coordinated copper monovalent sites among the copper monovalent sites is calculated by calculating the number of moles of nitrogen adsorbed relative to the amount of carbon monoxide adsorbed in the ZSM-5 type zeolite subjected to copper ion exchange. Desired.

  Furthermore, when the ZSM-5 type zeolite subjected to the copper ion exchange is ion-exchanged with an ion exchange solution containing at least copper ions and ions having a buffer action, the copper ions are transferred to the ZSM-5 type zeolite. When the ions are exchanged, since the ions having a buffering action have an action of promoting the reduction of copper ions, the ratio of copper monovalent sites is increased, and as a result, an increase in gas adsorption capacity is obtained.

  In addition, when copper ions are exchanged into ZSM-5 type zeolite, the ions that have a buffering action also have the action of introducing copper ions into oxygen tricoordinate sites, so that the gas can be adsorbed more firmly. An increase in adsorption capacity is obtained.

  Here, the ion having a buffering action refers to an ion having an action of buffering the dissociation equilibrium of a solution containing copper ions.

  For example, the ion dissociation behavior in an aqueous copper acetate solution is shown in (Chemical Formula 1).

When an appropriate buffering anion, such as CH ₃ COO ^−, is added to this system, the equilibrium proceeds to the center of the formula and the production of monovalent ions (CH ₃ COOCu) ⁺ containing associated species with acetate is generated. It becomes stable. This increases the proportion of copper monovalent sites and the proportion of oxygen tricoordinate copper monovalent sites.

  The details of this factor are unknown, but probably the position of the ion exchange site active in nitrogen adsorption and the shape selectivity due to the relative relationship, such as the steric hindrance of the pore diameter and ion diameter, and the three-dimensional structure. It is thought to be due to specificity.

  It is more preferable that the ion exchange solution containing copper ions and ions having a buffer action is an ion exchange solution containing copper acetate and ammonium acetate. The reason for this is that the acetate ion has the effect of effectively introducing the copper ion to a site that is easily reduced to monovalent, so that the ratio of the copper monovalent site is increased, and as a result, the amount of gas adsorption is increased. In addition, when copper ions are exchanged into ZSM-5 type zeolite, acetate ions having a buffer action also have an action of introducing copper ions into oxygen tricoordinate sites, so An increase in the chemisorption capacity for adsorbing gas is obtained, and further, the copper-ammonium ion-associated species produced by the addition of ammonium acetate is advantageous for ion exchange to a three-coordinate site from the viewpoint of size. Has the effect of enhancing the gas adsorption activity, and the ammonium ion is preferentially ion-exchanged to the site where oxygen is 2-coordinated, so that the copper ion is selectively ion-exchanged to the 3-coordinated site. This is because the effect is obtained that is.

  Table 1 shows the relationship between the ratio of copper monovalent sites, the ratio of copper trivalent oxygen sites in the copper monovalent sites, and the nitrogen adsorption amount.

  From Table 1, the ratio of copper monovalent sites is 73% or more as in Conditions 1 to 5, the ratio of oxygen monocoordinated copper monovalent sites in the copper monovalent sites is 84% or more, and the ion exchange solution is acetic acid. It can be seen that when the ion exchange solution contains copper and ammonium acetate, the amount of nitrogen adsorption increases with respect to conditions 6 and 7. Therefore, it is desirable to satisfy these conditions.

  In addition, a laminate film having a barrier property can be used as the covering material in the present invention, and the configuration thereof is not particularly specified.

  The innermost heat-welding 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. 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.

  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.

  In the case where the adsorbent is disposed on a part of the core member, after sealing the outer periphery of the outer cover material as in the latter case, the non-core consisting only of the outer cover member between the core member and the core member When the material part is welded, since only the outer peripheral part is sealed, each core part is not in an independent space, so the adsorbent disposed in at least one core part is the gas of the entire vacuum heat insulating material. In order to divide into independent spaces after adsorbing, the initial internal pressure variation of each core material portion can be suppressed as compared with the method of simultaneously welding like the former.

  The vacuum heat insulating material according to claim 2 is the vacuum heat insulating material according to claim 1, wherein the adsorbent is disposed at least in a core portion adjacent to the end surface of the jacket material, so that the intrusion from the end surface occurs. Since the adsorbent adsorbs the gas, the heat insulation performance with time can be improved.

  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 way, 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.

  The vacuum heat insulating material according to claim 3 is the vacuum heat insulating material according to claim 1 or 2, wherein the adsorbent is arranged in all the core material portions so that an increase in internal pressure is suppressed in order to suppress an increase in internal pressure. Performance can be improved.

  Also, if it is placed on all core parts, even when nailing a part of the core part when applied to a building, intrusion gas from that part is placed on the adjacent core part It can be adsorbed by the adsorbed material.

  The vacuum heat insulating material according to claim 4 is the vacuum heat insulating material according to any one of claims 1 to 3, wherein the amount of the adsorbent used is that of the core material portion adjacent to the outer peripheral portion of the jacket material. However, since the amount of use can be suppressed by being larger than the non-adjacent core parts, the cost is reduced.

  The amount of intrusion gas is greater in adjacent core parts than in non-adjacent core parts. 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.

  Invention of Claim 5 is a building member using the vacuum heat insulating material as described in any one of Claim 1 to 4, and since there is little change of the heat insulation performance of a vacuum heat insulating material, it is like a building. Even in applications that are used for a long period of time, the heat insulation performance is hardly deteriorated and the energy saving effect can be maintained.

  Moreover, in the case of a vacuum heat insulating material having a plurality of core materials, the work efficiency is improved in construction as compared with the case where a plurality of vacuum heat insulating materials having a single core material are attached.

  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, the vacuum heat insulating material 1 is composed of a plurality of core materials 2, a gas barrier outer covering material 3, and a gas adsorbing material 4. Here, the core material 2 is a molded body in which an assembly of glass fibers whose fiber orientation direction is perpendicular to the heat transfer direction, and the adsorbent 4 is made of ZSM-5 type zeolite exchanged with copper ions. And 73% or more of copper sites are copper monovalent sites among the copper sites.

  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.

  First, the manufacturing method of the vacuum heat insulating material 1 is demonstrated. First, the adsorbent 4 is disposed on the core material 2 and the core material 2a adjacent to the end of the jacket material 2 with the heat-welded layer of the jacket material 3 facing upward. Next, this is covered with another outer covering material 3 so that the heat-welded layers face each other. Furthermore, after welding the outer peripheral part of the jacket material 3 under reduced pressure, the core material 2 is welded by a method such as placing it in a high temperature environment under atmospheric pressure, and the heat welding part 5 is provided.

  By using the core material having the above configuration as the core material 2, a very high initial heat insulating performance was obtained. Furthermore, since the adsorbent 4 having the above-described configuration is used as the adsorbent 4, even when a material whose heat insulating performance is easily affected by the change in internal pressure is used for the core material 2, The change of the heat insulation performance was suppressed.

  FIG. 2 is a plan view of the 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. In addition, 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. 3 is a plan view of the vacuum heat insulating material according to the second embodiment of the present invention. In FIG. 3, the vacuum heat insulating material 6 is composed of a plurality of core materials 7, a gas barrier outer covering material 8, and a gas adsorbing material 9. Here, the core material 7 is a molded body in which an assembly of glass fibers whose fiber orientation direction is perpendicular to the heat transfer direction, and the adsorbent 9 is made of ZSM-5 type zeolite exchanged with copper ions. And 73% or more of copper sites are copper monovalent sites among the copper sites.

  In the vacuum heat insulating material 6, the core material 7 is arranged at a predetermined interval, and the adsorbing material 9 is arranged in a predetermined core material 7 portion, and is vacuum-sealed by the outer cover material 8. Moreover, the heat welding part 10 is provided in the circumference | surroundings of the core material 7 so that each core material 2 may be located in the independent vacuum space. The adsorbent 9 was disposed in the core material 7a adjacent to the outer peripheral portion of the jacket material with the aim of adsorbing the intruding gas from the end of the jacket material.

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

  By using the core material having the above configuration as the core material 7, a very high initial heat insulating performance was obtained. Furthermore, since the adsorbent 9 having the above-described configuration is used as the adsorbent 9, even when a material whose heat insulation performance is easily affected by the change in internal pressure is used for the core material 7, The change of the heat insulation performance was suppressed.

  Gases such as air and water vapor enter the space of the 20 core members 7a adjacent to the outer periphery of the jacket material depending on the difference in pressure between the atmospheric pressure and the core material 7a, but the adsorbent 9 enters. Adsorption of gas suppresses changes in internal pressure. Further, the 16 core members 7b not adjacent to the outer peripheral portion of the jacket material are configured such that the adsorbent 9 disposed in the core material 2a portion efficiently adsorbs gas from the end portion, and the outer peripheral portion of the jacket material. Since the core material 7a adjacent to the core material 7a is in another independent space via the heat welding part 10, the deterioration of the heat insulation performance is suppressed more than the core material 7a adjacent to the outer peripheral part of the jacket material. Therefore, it becomes possible to maintain the heat insulation performance of the whole vacuum heat insulating material over a long period of time.

  The location of the adsorbent is not limited to the core 2a portion adjacent to the outer periphery of the jacket material. If the place to be nailed 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. 4 is a plan view of the vacuum heat insulating material in Embodiment 3 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 a gas adsorbing material 14. Here, the core material 12 is a molded body in which an assembly of glass fibers whose fiber orientation direction is perpendicular to the heat transfer direction, and the adsorbent material 14 is made of ZSM-5 type zeolite exchanged with copper ions. And 73% or more of copper sites are copper monovalent sites among the copper sites.

  In the vacuum heat insulating material 11, the core material 12 is disposed at a predetermined interval, and the adsorbent 14 is disposed 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 was disposed on all the core parts 12.

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

  By using the core material having the above configuration as the core material 12, a very high initial heat insulation performance was obtained. Further, since the adsorbent having the above-described configuration is used as the adsorbent 14, even when a material whose heat insulating performance is easily affected by the change in internal pressure is used for the core material 2, the adsorbent is excellent in adsorbing capacity. The change of the heat insulation performance was suppressed.

  Since the adsorbents 14 are arranged in all the core material 12 parts, even when a vacuum break occurs in some core material parts by nailing or the like, or when a hole is opened in the heat welded part between the core materials Since the adsorbent disposed in the core portion adjacent to the holed portion adsorbs the intruding gas, it is possible to suppress the deterioration of the heat insulation performance.

  Note that the amount of intrusion gas is greater in the core material 12a portion adjacent to the outer periphery of the jacket material than in the core material 12b portion not adjacent to the outer periphery of the jacket material. It is possible to change the amount of application. Of the core material 12a adjacent to the outer peripheral portion, it is more desirable to increase the amount of the core material adjacent to the end portions of two or more sides that are more likely to invade the gas. In addition, when the place where nailing is known in advance, it is desirable to increase the amount of the adsorbent 14 used for the surrounding core 12 portion.

(Embodiment 4)
FIG. 5 is a cross-sectional view of a building to which the vacuum heat insulating material in Embodiment 4 of the present invention is applied.

  In the building 16 according to the present embodiment, the vacuum heat insulating material 11 according to the third embodiment is arranged between the outer wall 17 and the inner wall 18, below the floor in contact with the floor board 19, or in the attic in contact with the roof material 20. The building 16 configured in this manner exhibited excellent heat retention and energy saving effect by applying a vacuum heat insulating material having excellent heat insulating performance. In addition, since the fluctuation of the heat insulation performance of the vacuum heat insulating material was small, the energy saving effect could be maintained for a long time.

  In this embodiment, the vacuum heat insulating material of the third embodiment is used. However, even the vacuum heat insulating materials of the first and second embodiments can provide an excellent energy saving effect.

  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. 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, and projectors that require high thermal insulation performance in a small space. It can also be applied to uses that require cold storage such as container boxes and cooler boxes.

The top view of the vacuum heat insulating material in Embodiment 1 of this invention The top view of another vacuum heat insulating material in Embodiment 1 of this invention The top view of the vacuum heat insulating material in Embodiment 2 of this invention The top view of the vacuum heat insulating material in Embodiment 3 of this invention Sectional drawing of the building which applied the vacuum heat insulating material in Embodiment 4 of this invention

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Vacuum heat insulating material 2 Core material 3 Outer material 4 Adsorbent material 6 Vacuum heat insulating material 7 Core material 8 Outer material 9 Adsorbent material 11 Vacuum heat insulating material 12 Core material 13 Outer material 14 Adsorbent material 16 Building

Claims (5)

  At least a plurality of core materials, a gas barrier outer cover material having a heat-welded layer, and an adsorbent made of ZSM-5 type zeolite subjected to copper ion exchange, wherein the heat-welded layers face each other. A vacuum heat insulating material sealed under reduced pressure so that the core material is positioned in two or more independent vacuum spaces between workpieces, wherein the core material has a fiber orientation direction with respect to the heat transfer direction. It is a molded body obtained by forming an assembly of vertical glass fibers into a board shape, and 73% or more of copper sites in the copper sites of ZSM-5 type zeolite in which the adsorbent is exchanged with copper ions are copper. A vacuum heat insulating material which is a monovalent site and wherein the adsorbent is disposed in one or more core portions.   The vacuum heat insulating material according to claim 1, wherein the adsorbent is disposed at least in a core portion adjacent to the outer peripheral portion of the jacket material.   The vacuum heat insulating material according to claim 1, wherein the adsorbent is disposed in all core portions.   The amount of the adsorbent is larger in the adsorbent disposed in the core portion adjacent to the outer peripheral portion of the jacket material than in the adsorbent disposed in the non-adjacent core portion. The vacuum heat insulating material as described in any one of 3 to 3.   The building member which applied the vacuum heat insulating material as described in any one of Claim 1 to 4.