JP2018130933A - Laminate complex and heat insulation material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate complex that can exhibit sufficiently excellent heat insulation performance even when being wound around a heat insulation object, and can be thinned, and a heat insulation material provided therewith.SOLUTION: A laminate complex 10 includes a laminate 5 at least including a porous spacer layer and a support having a heat ray reflection function or a heat ray absorption function, and a joint member 9 that prevents the porous spacer layer and the support from being separated from each other. The joint member is provided along a peripheral part of the laminate.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a laminated composite and a heat insulating material.

  In recent years, business demand for realizing a hydrogen society has increased. For example, the development of liquid hydrogen tank trucks and the like is on an expanding trend. Thermal insulation is used in containers that contain liquid hydrogen and other cryogenic substances (liquid nitrogen, liquid helium, etc.). The said container has a double wall structure which consists of an inner container and an outer container, and it has become the vacuum between the inner container and the outer container, and is filled with the heat insulating material. As a heat insulating material for filling the vacuum space, for example, Patent Document 1 discloses a laminated heat insulating material in which a reflective film in which a metal layer is formed on one or both sides of a polyimide film and a net-like spacer made of plastic yarn are laminated. Has been.

  Patent Document 2 discloses a multilayer heat insulating material used as an exterior material in various spacecraft such as artificial satellites and space stations. The multilayer heat insulating material includes a heat insulating member interposed between layers of the heat insulating film, and a fixing unit that binds the heat insulating film, the heat insulating separator, and the heat insulating member in the stacking direction.

JP-A-9-109323 JP 2012-132494 A

  By the way, according to the study by the present inventors, when a multilayer heat insulating material is wound around a large facility such as a liquid hydrogen tank lorry, the multilayer heat insulating material can be obtained only by binding the central portion of the multilayer heat insulating material as disclosed in Patent Document 2. The phenomenon that the member, film, etc. which comprise material will shift | deviate in the edge part of a multilayer heat insulating material tends to arise. Such a shift may cause a region with a small number of layers per unit area of the object to be insulated, which may reduce the thermal insulation performance. In addition, from the viewpoint of increasing the storage amount of the cryogenic substance, the heat insulating material itself is required to be as thin as possible.

  The present invention has been made in view of the above circumstances, and a laminated composite capable of exhibiting sufficiently excellent heat insulating properties and capable of being thinned even when wound around an object to be insulated and used. It aims at providing a heat insulating material provided with this.

  The laminated composite according to the present invention includes a laminate comprising at least a porous spacer layer and a support having a heat ray reflecting function or a heat ray absorbing function, and a joining member for preventing the porous spacer layer and the support from separating from each other. The joining member is provided along the peripheral edge of the laminate.

  By keeping the porous spacer layer and the support joined at the periphery of the laminate including at least the porous spacer layer and the support having a heat ray reflection function or a heat ray absorption function, the two are prevented from separating from each other. it can. In addition to this, even when the laminated composite is wrapped around an object, it can be sufficiently suppressed that the end of the laminated body is displaced, so that when the laminated composite is wound around the object, per unit area Variation of the number of layers can be prevented. Examples of the joining member include a pin that penetrates the laminated body in the thickness direction, a thread-like member that stitches the laminated body, or a combination of a bolt that penetrates the laminated body in the thickness direction and a nut corresponding to the bolt.

  Instead of the bonding member, the porous spacer layer and the support may be bonded along the peripheral edge by pressure bonding, thermocompression bonding, laser pressure bonding, or binding to the laminate. That is, the laminated composite according to the present invention prevents the laminated body including at least a porous spacer layer and a support having a heat ray reflecting function or a heat ray absorbing function, and the porous spacer layer and the support from being separated from each other. It is a joining part, Comprising: The joining part formed by the pressurization crimping | compression-bonding with respect to a laminated body, thermocompression bonding, laser pressure bonding, or binding, The joining member may be provided along the peripheral part of a laminated body.

  From the viewpoint of improving the heat insulating performance of the laminated composite, the porous spacer layer may be a layer composed of a material containing at least one selected from the group consisting of nylon fiber, polyester fiber, polyimide fiber, and glass fiber. . Further, when the porous spacer layer is a layer containing a glass nonwoven fabric, a polyester nonwoven fabric, a glass fiber paper, a polyester net, or a nylon mesh, a further excellent heat insulating property can be achieved.

  From the viewpoint of achieving better heat insulation performance, an airgel layer may be adopted as the porous spacer layer. For example, the porous spacer layer may be a layer containing an airgel having a structure derived from polysiloxane. Accordingly, the thickness of the porous spacer layer and the laminated composite including the porous spacer layer can be reduced, and the effect of improving the heat insulating property of the laminated composite can be more easily expressed.

  The porous spacer layer is at least selected from the group consisting of a hydrolyzable functional group or a polysiloxane compound having a condensable functional group, and a hydrolysis product of a polysiloxane compound having a hydrolyzable functional group. It may be an airgel layer made of a dried product of a wet gel that is a condensate of a sol containing one kind of compound. A laminated composite provided with such an airgel layer has an excellent balance between heat insulation and flexibility.

  The porous spacer layer may be an airgel layer made of a dried product of a wet gel that is a condensate of a sol containing silica particles. Thereby, the further outstanding heat insulation and softness | flexibility can be achieved. The average primary particle diameter of the silica particles can be 1 nm or more and 500 nm or less. Thereby, it becomes easy to improve heat insulation and a softness | flexibility further.

  The said support body can have a layer comprised from the material containing at least 1 type chosen from the group which consists of carbon graphite, aluminum, magnesium, silver, titanium, carbon black, a metal sulfate, and an antimony compound. Moreover, when the said support body is an aluminum foil and an aluminum vapor deposition film, the further outstanding heat insulation can be achieved.

  This invention can also provide a heat insulating material provided with the laminated composite mentioned above. Such a heat insulating material is excellent in handling property, and can exhibit excellent heat insulating performance after its thickness is reduced.

  ADVANTAGE OF THE INVENTION According to this invention, even if it wraps around the target object which should be insulated and can be used, the laminated composite which can exhibit the heat insulation sufficiently excellent and can be reduced in thickness can be provided. And a heat insulating material provided with such a laminated composite is excellent in handleability, and can express the outstanding heat insulation performance, after reducing thickness.

FIG. 1 is a cross-sectional view schematically showing one embodiment of a laminated composite according to the present invention. FIG. 2A is a cross-sectional view schematically showing an example of a mode in which the pin (joining member) integrates the laminated body, and FIG. 2B is an example of the pin installation location in the rectangular laminated composite. It is a top view shown typically. FIG. 3A is a plan view schematically showing a laminated composite in which joint portions are formed along two sides forming a pair among the peripheral portions of the rectangular laminated body, and FIG. It is a top view which shows typically the laminated composite in which the junction part was formed along the four sides of a laminated body. 4 is a cross-sectional view schematically showing a multilayer laminate in which the laminate composite shown in FIG. 1 is laminated. FIG. 5 is a diagram showing a method for calculating the biaxial average primary particle diameter of particles. FIG. 6 is a plan view schematically showing the configuration of the laminated heat insulating material according to Comparative Example 2. FIG. 7 is a plan view schematically showing the configuration of the laminated heat insulating material according to Comparative Example 3. FIG. 8 is a schematic cross-sectional view of a liquid nitrogen container for heat insulation evaluation. FIG. 9 is a schematic diagram of a heat insulation performance test apparatus.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as the case may be. However, the present invention is not limited to the following embodiments.

<Laminated composite>
FIG. 1 is a cross-sectional view schematically showing the laminated composite of this embodiment. The laminated composite 10 shown in the figure includes a laminated body 5 in which a porous spacer layer 1 and a support 2 having a heat ray reflecting function or a heat ray absorbing function are laminated, and a constituent member of the laminated body 5 (porous spacer layer) 1 and the support body 2) are provided with a joining member (for example, a pin 8 shown in FIG. 2A) for preventing the separation from each other. That is, the laminated composite 10 has a configuration in which the laminated body 5 is bound in the stacking direction by the joining member. Although FIG. 1 shows a structure in which the porous spacer layer 1 is laminated on only one surface of the support 2, a structure in which the porous spacer layer 1 is laminated on both surfaces of the support 2 may be used.

  2A is a cross-sectional view schematically showing a state in which the constituent members of the laminate 5 are joined (integrated) by the pins (joining members) 8, and FIG. 2B is a pair of long sides ( It is a top view which shows typically an example of the installation location of the pin 8 in the laminated composite 10 which has a right-and-left side in FIG.2 (b). As shown in FIG. 2B, in the laminated composite 10, a plurality of pins 8 are arranged along the peripheral edge 5 a of the laminated body 5. The region where the pins 8 are installed is preferably a region of 10 to 200 mm (more preferably 20 to 100 mm) from the peripheral edge 5a of the laminate 5. In addition, when using the laminated composite 10 wound around the object which should be insulated, it is preferable that the laminated composite 10 is strip | belt shape.

  The distance between connection positions of adjacent joining members (distance D1 in FIG. 2B) is preferably 10 to 200 mm, more preferably 20 to 100 mm. If the interval between adjacent connection positions is 10 mm or more, the laminated composite 10 can be easily manufactured efficiently, and the flexibility of the laminated composite 10 can be easily maintained and the handleability is excellent. On the other hand, if the interval between adjacent joining members is 200 mm or less, it is easy to sufficiently maintain the state in which the laminate 5 is integrated, and the displacement of the constituent members at the end portions can be sufficiently suppressed.

  As the joining member, in addition to the pin 8 as shown in FIG. 2A, a thread-like member for sewing the laminated body 5 or a combination of a bolt penetrating the laminated body in the thickness direction and a nut corresponding to the bolt. Can be mentioned.

  Instead of the joining member, a joining portion 9 that joins the constituent members of the laminate 5 by press-bonding, thermocompression bonding, laser press-bonding, or binding to the laminate 5 may be provided. As shown in FIG. 3A, when the laminate 5 has a strip shape, the joint portion 9 may be formed along a pair of long sides (left and right sides in FIG. 3A). As shown to 3 (b), when the laminated body 5 is a rectangle, you may form the junction part 9 along a peripheral part (four sides).

  The distance between adjacent joints 9 (distance D2 in FIGS. 3A and 3B) is preferably 1 to 50 cm, and more preferably 5 to 25 cm. If the interval between adjacent joints 9 is 1 cm or more, the laminated composite 10 can be easily produced efficiently, and the flexibility of the laminated composite 10 can be easily maintained and the handleability is excellent. On the other hand, if the interval between adjacent joints 9 is 50 cm or less, it is easy to sufficiently maintain the state in which the laminated body 5 is integrated, and the displacement of the constituent members at the ends can be sufficiently suppressed. In addition, there is no restriction | limiting in particular in the shape of the junction part 9, A linear form may be sufficient, and a round shape, an ellipse shape, a rectangle, or a curvilinear form may be sufficient.

  A plurality of laminated composites 10 may be prepared to form a multilayer laminate in which a plurality of porous spacer layers 1 and supports 2 are alternately laminated as shown in FIG. When a plurality of laminated composites 10 are stacked in this way, the porous spacer layer 1 having heat insulation is interposed between the support 2 and the support 2, so that heat conduction by contact between the supports 2 is performed. Can be suppressed. The number of laminated composites 10 may be 5 or more, 10 or more, 20 or more, or 30 or more. By stacking a plurality of laminated composites 10, it is possible to develop excellent heat insulation performance that cannot be obtained with one laminated composite 10.

(Porous spacer layer)
The porous spacer is a general term for materials containing a large number of porous structures, and is referred to as a porous spacer in this embodiment regardless of the pore size. The porous spacer layer 1 according to this embodiment is also a layer that has a porous structure and can function as a heat insulating layer under high vacuum.

  The thickness of the porous spacer layer 1 (except when the porous spacer layer 1 is an airgel layer described later) is not particularly limited, but can be 1 μm or more from the viewpoint of handling properties, and can be 10 μm or more. It may be 50 μm or more. On the other hand, from the viewpoint of improving the heat insulating properties, the thickness of the porous spacer layer 1 can be 300 μm or less, 200 μm or less, or 100 μm or less. That is, the thickness of the porous spacer layer 1 may be 1 to 300 μm, may be 10 to 200 μm, and may be 50 to 100 μm.

  The porosity of the porous spacer layer 1 is not particularly limited, but can be 5% or more, 20% or more, or 30% or more from the viewpoint of improving heat insulation. On the other hand, from the viewpoint of handling properties, the porosity of the porous spacer layer 1 can be 98% or less, may be 95% or less, and may be 90% or less. That is, the porosity of the porous spacer layer 1 can be 5 to 95%, 20 to 95%, or 30 to 90%.

  The configuration of the porous spacer layer 1 is not particularly limited, and may be a single layer or multiple layers. The porous spacer layer 1 is not particularly limited as long as it is composed of a layer having a porous structure. The porous spacer layer 1 may be composed of the same kind of porous spacer or may be composed of different kinds of porous spacers.

  Examples of the material constituting the porous spacer layer 1 include nylon fibers, polyester fibers, polypropylene fibers, polyethylene fibers, polyacrylonitrile fibers, polyimide fibers, aramid fibers, carbon fibers, and other organic fibers, glass fibers, rock wool, ceramics. Examples thereof include inorganic fibers such as fibers. These may be used alone or in combination of two or more. The porous spacer layer 1 is a layer composed of a material including at least one selected from the group consisting of nylon fiber, polyester fiber, polyimide fiber, and glass fiber from the viewpoint of easily improving heat insulation and excellent handling properties. There may be. Although it does not specifically limit as a form of the fiber which comprises the porous spacer layer 1, For example, a textile fabric, a knitted fabric, a nonwoven fabric, paper, a net | network, a mesh etc. are mentioned. The porous spacer layer 1 may be a layer including a glass nonwoven fabric, a polyester nonwoven fabric, a glass fiber paper, a polyester net, or a nylon mesh from the viewpoint of easily improving the heat insulating property, and being excellent in low cost and handling properties.

  In addition, when a laminated composite is used for an application where flame retardancy is required while ensuring a certain heat insulating property, the material constituting the porous spacer layer 1 is, for example, copper fiber, iron fiber, stainless steel fiber, gold Metal fibers such as fibers, silver fibers, and aluminum fibers may be used. You may use this metal fiber in combination with the above-mentioned organic fiber or inorganic fiber.

  As a material constituting the porous spacer layer 1, an airgel described later may be employed. Further, as the structure of the porous spacer layer 1, a multilayer structure in which a layer made of the above-described material (non-aerogel layer) is laminated on the airgel layer may be adopted. By adopting such a configuration, the degree of vacuum of the airgel layer having nano-sized pores can be improved.

  Airgel is excellent in flexibility. Conventionally, airgel has been difficult to handle, but it is possible to form a sheet of airgel by integrating the layer made of airgel (porous spacer layer 1) and support 2 with a joining member (for example, pin 8). . Thereby, when the laminated composite 10 is used as a heat insulating material, the heat insulating layer can be thinned, and the heat insulating material including the heat insulating layer is excellent in handleability. The support 2 that is a non-aerogel layer can act as a radiator and can play a role of blocking heat from the outside. The laminated composite 10 having such a configuration can be thinned and has excellent heat insulation and flexibility.

  In a narrow sense, aerogel is a dry gel obtained by using a supercritical drying method on a wet gel, an aerogel, a dry gel obtained by drying under atmospheric pressure, a xerogel, and a dry gel obtained by lyophilization. In this embodiment, the obtained low-density dried gel is referred to as “aerogel” regardless of the drying method of the wet gel. That is, in this embodiment, “aerogel” is a gel in a broad sense, “Gel composed of a microporous solid in which the dispersed phase is a gas” (a gel composed of a microporous solid in which the dispersed phase is a gas). "Means. In general, the inside of the airgel has a network-like fine structure, and has a cluster structure in which airgel particles of about 2 to 20 nm (particles constituting the airgel) are bonded. There are pores less than 100 nm between the skeletons formed by these clusters. Thereby, the airgel has a three-dimensionally fine porous structure. In addition, the airgel in this embodiment is a silica airgel which has a silica as a main component, for example. Examples of the silica airgel include so-called organic-inorganic hybrid silica airgel into which an organic group (such as a methyl group) or an organic chain is introduced. The porous spacer layer 1 may be a layer containing an airgel having a structure derived from polysiloxane.

  The airgel according to the present embodiment includes a silicon compound having a hydrolyzable functional group or a condensable functional group (in the molecule) and a hydrolysis product of the silicon compound having the hydrolyzable functional group. It may be a dried product of a wet gel that is a condensate of a sol containing at least one selected from the group. That is, the airgel according to the present embodiment includes a hydrolyzable functional group or a silicon compound having a condensable functional group (in the molecule) and a hydrolysis product of the silicon compound having the hydrolyzable functional group. It may be obtained by drying a wet gel produced from a sol containing at least one selected from the group consisting of: The condensate may be obtained by a condensation reaction of a hydrolysis product obtained by hydrolysis of a silicon compound having a hydrolyzable functional group, and is not a functional group obtained by hydrolysis. It may be obtained by a condensation reaction of a silicon compound having a group. The silicon compound may have at least one of a hydrolyzable functional group and a condensable functional group, and may have both a hydrolyzable functional group and a condensable functional group. In addition, each airgel mentioned later is a group which consists of a hydrolysis product of the silicon compound which has a hydrolyzable functional group or a condensable functional group, and the said hydrolyzable functional group in this way. It may be a dried product of a wet gel that is a condensate of a sol containing at least one selected from the above (obtained by drying a wet gel produced from the sol).

  The porous spacer layer 1 is at least selected from the group consisting of a hydrolyzable functional group or a silicon compound having a condensable functional group, and a hydrolysis product of the silicon compound having the hydrolyzable functional group. It may be a layer composed of a dried product of a wet gel that is a condensate of a sol containing one kind. That is, the porous spacer layer 1 is selected from the group consisting of a hydrolyzable functional group or a silicon compound having a condensable functional group and a hydrolysis product of the silicon compound having the hydrolyzable functional group. It may be composed of a layer formed by drying a wet gel produced from a sol containing at least one of the above.

  The airgel according to the present embodiment can contain polysiloxane having a main chain including a siloxane bond (Si—O—Si). The airgel can have the following M unit, D unit, T unit or Q unit as a structural unit.

In the above formula, R represents an atom (hydrogen atom or the like) or an atomic group (alkyl group or the like) bonded to a silicon atom. The M unit is a unit composed of a monovalent group in which a silicon atom is bonded to one oxygen atom. The D unit is a unit composed of a divalent group in which a silicon atom is bonded to two oxygen atoms. The T unit is a unit composed of a trivalent group in which a silicon atom is bonded to three oxygen atoms. The Q unit is a unit composed of a tetravalent group in which a silicon atom is bonded to four oxygen atoms. Information on the content of these units can be obtained by ²⁹ Si-NMR.

The airgel according to the present embodiment may contain silsesquioxane. Silsesquioxane is a polysiloxane having the above T unit as a structural unit, and has a composition formula: (RSiO _1.5 ) _n . Silsesquioxane can have various skeletal structures such as a cage type, a ladder type, and a random type.

  Examples of the hydrolyzable functional group include an alkoxy group. Examples of the condensable functional group (excluding the functional group corresponding to the hydrolyzable functional group) include a hydroxyl group, a silanol group, a carboxyl group, and a phenolic hydroxyl group. The hydroxyl group may be contained in a hydroxyl group-containing group such as a hydroxyalkyl group. Each of the hydrolyzable functional group and the condensable functional group may be used alone or in admixture of two or more.

  The silicon compound can include a silicon compound having an alkoxy group as a hydrolyzable functional group, and can also include a silicon compound having a hydroxyalkyl group as a condensable functional group. The silicon compound can have at least one selected from the group consisting of an alkoxy group, a silanol group, a hydroxyalkyl group and a polyether group from the viewpoint of further improving the flexibility of the airgel. The silicon compound can have at least one selected from the group consisting of an alkoxy group and a hydroxyalkyl group from the viewpoint of improving the compatibility of the sol.

  From the viewpoint of improving the reactivity of the silicon compound and reducing the thermal conductivity of the airgel, the number of carbon atoms of the alkoxy group and the hydroxyalkyl group may be 1 to 6, and the flexibility of the airgel is further improved. 2-4 may be sufficient. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. Examples of the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

  The following aspects are mentioned as an airgel which concerns on this embodiment. By adopting these aspects, it becomes easy to obtain an airgel excellent in heat insulation, flame retardancy, heat resistance and flexibility. In particular, since the flexibility is excellent, it is possible to form the heat insulating layer more easily even for shapes that have been difficult to form in the past. By employ | adopting each aspect, the airgel which has the heat insulation according to each aspect, a flame retardance, and a softness | flexibility can be obtained.

[First aspect]
The aerogel according to this embodiment may be a wet gel (inside the molecule). That is, the airgel according to the present embodiment includes a hydrolyzable polysiloxane compound having a hydrolyzable functional group or a condensable functional group (in the molecule) and a polysiloxane compound having the hydrolyzable functional group. It may be obtained by drying a wet gel produced from a sol containing at least one selected from the group consisting of products. In addition, each airgel mentioned later is also from the hydrolysis product of the polysiloxane compound which has a hydrolyzable functional group or a condensable functional group, and the polysiloxane compound which has the said hydrolyzable functional group in this way. It may be a wet gel dried product (obtained by drying a wet gel generated from the sol), which is a condensate of a sol containing at least one selected from the group.

  The porous spacer layer 1 is selected from the group consisting of a polysiloxane compound having a hydrolyzable functional group or a condensable functional group, and a hydrolysis product of the polysiloxane compound having a hydrolyzable functional group. It may also be a layer composed of a dried product of a wet gel that is a condensate of a sol containing at least one kind. That is, the porous spacer layer 1 is composed of a polysiloxane compound having a hydrolyzable functional group or a condensable functional group and a hydrolysis product of the polysiloxane compound having the hydrolyzable functional group. You may be comprised from the layer formed by drying the wet gel produced | generated from the sol containing at least 1 type selected.

  A polysiloxane compound having a hydrolyzable functional group or a condensable functional group is a reactive group different from the hydrolyzable functional group and the condensable functional group (hydrolyzable functional group and condensable functional group). May further have a functional group that does not fall under. The reactive group is not particularly limited, and examples thereof include an epoxy group, a mercapto group, a glycidoxy group, a vinyl group, an acryloyl group, a methacryloyl group, and an amino group. The epoxy group may be contained in an epoxy group-containing group such as a glycidoxy group. You may use the polysiloxane compound which has the said reactive group individually or in mixture of 2 or more types.

  Examples of the polysiloxane compound having a hydroxyalkyl group include compounds having a structure represented by the following formula (A).

In formula (A), R ^1a represents a hydroxyalkyl group, R ^2a represents an alkylene group, R ^3a and R ^4a each independently represents an alkyl group or an aryl group, and n represents an integer of 1 to 50. Here, examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group. In formula (A), two R ^{1a s} may be the same or different, and similarly, two R ^{2a s} may be the same or different. In formula (A), two or more R ^{3a s} may be the same or different, and similarly, two or more R ^{4a s} may be the same or different.

By using a wet gel that is a condensate of a sol containing the polysiloxane compound having the above structure (a wet gel generated from the sol), it becomes easier to obtain a flexible airgel having low thermal conductivity. From the same viewpoint, the following features may be satisfied. In the formula (A), examples of R ^1a include a hydroxyalkyl group having 1 to 6 carbon atoms, and specifically include a hydroxyethyl group and a hydroxypropyl group. In formula (A), examples of R ^2a include an alkylene group having 1 to 6 carbon atoms, and specific examples include an ethylene group and a propylene group. In formula (A), R ^3a and R ^4a may each independently be an alkyl group having 1 to 6 carbon atoms or a phenyl group. The alkyl group may be a methyl group. In the formula (A), n may be 2 to 30, or 5 to 20.

  As the polysiloxane compound having a structure represented by the above formula (A), a commercially available product can be used. For example, compounds such as X-22-160AS, KF-6001, KF-6002, KF-6003, etc. As well as compounds such as XF42-B0970 and Fluid OFOH 702-4% (all manufactured by Momentive Performance Materials Japan GK).

  Examples of the polysiloxane compound having an alkoxy group include compounds having a structure represented by the following formula (B).

In formula (B), R ^1b represents an alkyl group, an alkoxy group or an aryl group, R ^2b and R ^3b each independently represent an alkoxy group, and R ^4b and R ^5b each independently represent an alkyl group or an aryl group. , M represents an integer of 1-50. Here, examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group. In the formula (B), two R ^{1b s} may be the same or different, and two R ^{2b s} may be the same or different. Similarly, R ^3b may be the same or different. In the formula (B), when m is an integer of 2 or more, two or more R ^4b may be the same or different, and similarly, two or more R ^5b may be the same. May be different.

By using a wet gel (wet gel generated from the sol) that is a condensate of a sol containing the polysiloxane compound having the above structure or a hydrolysis product thereof, it becomes easier to obtain a flexible airgel having low thermal conductivity. . From the same viewpoint, the following features may be satisfied. In formula (B), R ^1b includes, for example, an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. Specifically, a methyl group, a methoxy group, and an ethoxy group include Can be mentioned. In formula (B), R ^2b and R ^3b may each independently be an alkoxy group having 1 to 6 carbon atoms. Examples of the alkoxy group include a methoxy group and an ethoxy group. In formula (B), R ^4b and R ^5b may each independently be an alkyl group having 1 to 6 carbon atoms or a phenyl group. The alkyl group may be a methyl group. In the formula (B), m may be 2 to 30, or 5 to 20.

  The polysiloxane compound having the structure represented by the above formula (B) can be obtained by appropriately referring to the production methods reported in, for example, JP-A Nos. 2000-26609 and 2012-233110. it can.

  In addition, since the alkoxy group is hydrolyzed, the polysiloxane compound having an alkoxy group may exist as a hydrolysis product in the sol. The polysiloxane compound having an alkoxy group and the hydrolysis product are It may be mixed. In the polysiloxane compound having an alkoxy group, all of the alkoxy groups in the molecule may be hydrolyzed or partially hydrolyzed.

  Each of the hydrolyzable functional group or the polysiloxane compound having a condensable functional group and the hydrolysis product of the polysiloxane compound having the hydrolyzable functional group may be used alone or in combination of two or more. May be used.

  Content of polysiloxane compound group contained in the sol (content of polysiloxane compound having hydrolyzable functional group or condensable functional group, and water content of polysiloxane compound having hydrolyzable functional group) The total content of the decomposition products) may be 1 part by mass or 3 parts by mass or more with respect to 100 parts by mass of the total amount of sol, from the viewpoint of further easily obtaining good reactivity. Alternatively, it may be 4 parts by mass or more, 5 parts by mass or more, 7 parts by mass or more, or 10 parts by mass or more. The content of the polysiloxane compound group may be 50 parts by mass or less, or 30 parts by mass or less with respect to 100 parts by mass of the total amount of sol, from the viewpoint of further easily obtaining good compatibility. 15 parts by mass or less. From these viewpoints, the content of the polysiloxane compound group may be 1 to 50 parts by mass, 3 to 50 parts by mass, or 4 to 50 parts by mass with respect to 100 parts by mass of the sol. May be 5 to 50 parts by mass, 7 to 30 parts by mass, 10 to 30 parts by mass, or 10 to 15 parts by mass. .

[Second embodiment]
As the silicon compound having a hydrolyzable functional group or a condensable functional group, a silicon compound (silicon compound) other than the polysiloxane compound may be used. That is, the airgel according to the present embodiment has (in the molecule) a hydrolyzable functional group or a silicon compound having a condensable functional group (excluding a polysiloxane compound) and the hydrolyzable functional group. It may be a wet gel dried product which is a condensate of sol containing at least one compound selected from the group consisting of hydrolysis products of silicon compounds (hereinafter sometimes referred to as “silicon compound group”). The number of silicon atoms in the molecule of the silicon compound may be 1 or 2.

  Although it does not specifically limit as a silicon compound which has a hydrolyzable functional group, For example, an alkyl silicon alkoxide is mentioned. In the alkyl silicon alkoxide, from the viewpoint of improving water resistance, the number of hydrolyzable functional groups may be 3 or less, or may be 2 to 3. Examples of the alkyl silicon alkoxide include monoalkyltrialkoxysilane, monoalkyldialkoxysilane, dialkyldialkoxysilane, monoalkylmonoalkoxysilane, dialkylmonoalkoxysilane and trialkylmonoalkoxysilane. Examples of the alkyl silicon alkoxide include methyltrimethoxysilane, methyldimethoxysilane, dimethyldimethoxysilane, and ethyltrimethoxysilane.

  The silicon compound having a condensable functional group is not particularly limited. For example, silane tetraol, methyl silane triol, dimethyl silane diol, phenyl silane triol, phenyl methyl silane diol, diphenyl silane diol, n-propyl silane triol, Examples include hexyl silane triol, octyl silane triol, decyl silane triol, and trifluoropropyl silane triol.

  The number of hydrolyzable functional groups is 3 or less, and as a silicon compound having a reactive group, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, N-phenyl-3-aminopropyl Trimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and the like can also be used.

  As a silicon compound having a condensable functional group and having the above-mentioned reactive group, vinyl silane triol, 3-glycidoxy propyl silane triol, 3-glycidoxy propyl methyl silane diol, 3-methacryloxy propyl silane triol, 3-methacryloxypropylmethylsilanediol, 3-acryloxypropylsilanetriol, 3-mercaptopropylsilanetriol, 3-mercaptopropylmethylsilanediol, N-phenyl-3-aminopropylsilanetriol, N-2- (aminoethyl) ) -3-Aminopropylmethylsilanediol and the like can also be used.

  As the alkyl silicon alkoxide, bistrimethoxysilylmethane, bistrimethoxysilylethane, bistrimethoxysilylhexane, or the like, which is a silicon compound having more than three hydrolyzable functional groups at the molecular terminals, can also be used.

  Each of the hydrolyzable functional group or the silicon compound having a condensable functional group (excluding the polysiloxane compound) and the hydrolyzate of the silicon compound having the hydrolyzable functional group, either alone or 2 You may mix and use a kind or more.

  Content of silicon compounds contained in the sol (contents of silicon compounds having hydrolyzable functional groups or condensable functional groups (excluding polysiloxane compounds) contained in the sol because it becomes easier to obtain good reactivity. , And the total content of hydrolysis products of the silicon compound having a hydrolyzable functional group) can be 5 parts by mass or more with respect to 100 parts by mass of the total amount of the sol. It may be 12 mass parts or more, 15 mass parts or more, or 18 mass parts or more. Since it becomes easier to obtain good compatibility, the content of the silicon compound group can be 50 parts by mass or less with respect to 100 parts by mass of the total amount of the sol, and may be 30 parts by mass or less. It may be 25 parts by mass or less, or 20 parts by mass or less. That is, the said content of a silicon compound group can be 5-50 mass parts with respect to 100 mass parts of total amounts of sol, may be 10-30 mass parts, and is 12-30 mass parts, 15-25 mass parts may be sufficient and 18-20 mass parts may be sufficient.

  The sum of the content of the polysiloxane compound group and the content of the silicon compound group may be 5 parts by mass or more with respect to 100 parts by mass of the sol from the viewpoint of further easily obtaining good reactivity. It may be 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, or 22 parts by mass or more. The sum of the content of the polysiloxane compound group and the content of the silicon compound group may be 50 parts by mass or less with respect to 100 parts by mass of the total amount of the sol, from the viewpoint of easily obtaining good compatibility. 30 parts by mass or less, or 25 parts by mass or less. From these viewpoints, the sum of the content of the polysiloxane compound group and the content of the silicon compound group may be 5 to 50 parts by mass with respect to 100 parts by mass of the sol, or 10 to 30 parts by mass. May be sufficient, 15-30 mass parts may be sufficient, 20-30 mass parts may be sufficient, and 22-25 mass parts may be sufficient.

  The ratio of the content of the polysiloxane compound group and the content of the silicon compound group (polysiloxane compound group: silicon compound group) is 1: 0.5 or more from the viewpoint of further easily obtaining good compatibility. Or 1: 1 or more, 1: 2 or more, or 1: 3 or more. The ratio of the content of the polysiloxane compound group to the content of the silicon compound group (polysiloxane compound group: silicon compound group) is 1: 4 or less from the viewpoint of further easily suppressing gel shrinkage. It may be 1: 2 or less. From these viewpoints, the ratio of the content of the polysiloxane compound group to the content of the silicon compound group (polysiloxane compound group: silicon compound group) may be 1: 0.5 to 1: 4. It may be 1: 1 to 1: 2, may be 1: 2 to 1: 4, and may be 1: 3 to 1: 4.

[Third embodiment]
The airgel which concerns on this embodiment can have a structure represented by following formula (1). The airgel which concerns on this embodiment can have a structure represented by a following formula (1a) as a structure containing the structure represented by Formula (1). By using the polysiloxane compound having the structure represented by the above formula (A), the structures represented by the formula (1) and the formula (1a) can be introduced into the skeleton of the airgel.

In formula (1) and formula (1a), R ¹ and R ² each independently represent an alkyl group or an aryl group, and R ³ and R ⁴ each independently represent an alkylene group. Here, examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group. p shows the integer of 1-50. In formula (1a), two or more R ^{1 s} may be the same or different, and similarly, two or more R ^{2 s} may be the same or different. In formula (1a), two R ^{3 s} may be the same or different, and similarly, two R ^{4 s} may be the same or different.

By introducing the structure represented by the above formula (1) or formula (1a) into the skeleton of the airgel, a flexible airgel having low thermal conductivity can be easily obtained. From the same viewpoint, the following features may be satisfied. In Formula (1) and Formula (1a), R ¹ and R ² may each independently be an alkyl group having 1 to 6 carbon atoms or a phenyl group. The alkyl group may be a methyl group. In formula (1) and formula (1a), R ³ and R ⁴ may each independently be an alkylene group having 1 to 6 carbon atoms. The alkylene group may be an ethylene group or a propylene group. In formula (1a), p can be set to 2 to 30, and may be 5 to 20.

[Fourth aspect]
The airgel according to the present embodiment may be an airgel having a ladder type structure including a support portion and a bridge portion, and the bridge portion may be an airgel having a structure represented by the following formula (2). . By introducing such a ladder structure into the airgel skeleton, heat resistance and mechanical strength can be easily improved. By using a polysiloxane compound having a structure represented by the above formula (B), a ladder type structure including a bridge portion having a structure represented by the formula (2) can be introduced into the skeleton of the airgel. it can. In the present embodiment, the “ladder structure” is a structure having two struts and bridges connecting the struts (a structure having a so-called “ladder” form). ). In this embodiment, the airgel skeleton may have a ladder structure, but the airgel may partially have a ladder structure.

In formula (2), R ⁵ and R ⁶ each independently represent an alkyl group or an aryl group, and b represents an integer of 1 to 50. Here, examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group. In formula (2), when b is an integer of 2 or more, two or more R ^{5 s} may be the same or different, and similarly, two or more R ^{6 s} are the same. Or different.

  By introducing the above structure into the skeleton of the airgel, for example, it is superior to an airgel having a structure derived from a conventional ladder-type silsesquioxane (that is, having a structure represented by the following formula (X)). Airgel having high flexibility. In addition, as shown in the following formula (X), in the airgel having a structure derived from a conventional ladder-type silsesquioxane, the structure of the bridge portion is —O—. The structure of the part is a structure (polysiloxane structure) represented by the above formula (2).

  In formula (X), R represents a hydroxy group, an alkyl group or an aryl group.

  The structure of the column part and its chain length, and the interval between the structures of the bridge part are not particularly limited, but from the viewpoint of further improving the heat resistance and mechanical strength, the ladder type structure is represented by the following formula ( It may have a ladder structure represented by 3).

In formula (3), R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent an alkyl group or an aryl group, a and c each independently represent an integer of 1 to 3000, and b is 1 to 50 Indicates an integer. Here, examples of the aryl group include a phenyl group and a substituted phenyl group. Examples of the substituent of the substituted phenyl group include an alkyl group, a vinyl group, a mercapto group, an amino group, a nitro group, and a cyano group. In Formula (3), when b is an integer of 2 or more, two or more R ^{5 s} may be the same or different, and similarly, two or more R ^{6 s} may be the same. May be different. In formula (3), when a is an integer of 2 or more, two or more R ^{7 s} may be the same or different. In formula (3), when c is an integer of 2 or more, two or more R ^{8 s} may be the same or different.

From the viewpoint of obtaining further excellent flexibility, in formula (2) and formula (3), R ⁵ , R ⁶ , R ⁷ and R ⁸ (wherein R ⁷ and R ⁸ are only in formula (3)) are: It may be independently an alkyl group having 1 to 6 carbon atoms or a phenyl group. The alkyl group may be a methyl group. In the formula (3), a and c may be independently 6 to 2000 or 10 to 1000. In Formula (2) and Formula (3), b may be 2-30 or 5-20.

[Fifth aspect]
The airgel which concerns on this embodiment may contain the silica particle from a viewpoint of achieving the further outstanding heat insulation and a softness | flexibility. The sol that gives the airgel may further contain silica particles. That is, the airgel according to this embodiment may be a support (obtained by drying a wet gel generated from the sol). That is, the porous spacer layer 1 according to the present embodiment is a dried product of a wet gel (wet gel derived from the sol) that is a condensate of a sol containing silica particles (wet the wet gel generated from the sol). An aerogel that is obtained as a result). The porous spacer layer 1 may be a layer composed of a dried product of a wet gel, which is a condensate of sol containing silica particles, and is obtained by drying a wet gel generated from a sol containing silica particles. It may be composed of layers. In addition, the airgel described so far is also a dried product of a wet gel that is a condensate of a sol containing silica particles (obtained by drying a wet gel generated from the sol). May be.

  The silica particles can be used without particular limitation, and examples thereof include amorphous silica particles. Examples of the amorphous silica particles include fused silica particles, fumed silica particles, and colloidal silica particles. Among these, colloidal silica particles have high monodispersity and are easy to suppress aggregation in the sol.

  The shape of the silica particles is not particularly limited, and examples thereof include a spherical shape, a cage shape, and an association type. Among these, by using spherical particles as silica particles, it becomes easy to suppress aggregation in the sol. The average primary particle diameter of the silica particles may be 1 nm or more, or 5 nm or more, from the viewpoint that it is easy to impart an appropriate strength and flexibility to the airgel, and an airgel excellent in shrinkage resistance during drying is easily obtained. It may be 10 nm or more, or 20 nm or more. The average primary particle diameter of the silica particles may be 500 nm or less, may be 300 nm or less, may be 300 nm or less, and may be 250 nm from the viewpoint that it is easy to suppress the solid heat conduction of the silica particles and easily obtain an airgel excellent in heat insulation. Or 100 nm or less. From these viewpoints, the average primary particle diameter of the silica particles may be 1 to 500 nm, 5 to 300 nm, 10 to 250 nm, or 20 to 100 nm.

  In the present embodiment, the average particle size of the particles (average primary particle size of silica particles, etc.) is obtained by directly observing the cross section of the airgel layer using a scanning electron microscope (hereinafter abbreviated as “SEM”). be able to. For example, the particle size of each airgel particle or silica particle can be obtained from the mesh-like microstructure inside the airgel based on the diameter of the particles exposed in the cross section of the airgel layer. The “diameter” here means a diameter when the cross section of the particle exposed in the cross section of the airgel layer is regarded as a circle. The “diameter when the cross section is regarded as a circle” is the diameter of the true circle when the area of the cross section is replaced with a true circle having the same area. In calculating the average particle diameter, the diameter of a circle is obtained for 100 particles, and the average is taken.

  In addition, the average particle diameter of a silica particle can be measured from a raw material. For example, the biaxial average primary particle diameter is calculated as follows from the result of observing 20 arbitrary particles by SEM. That is, for example, colloidal silica particles having a solid content concentration of 5 to 40% by mass dispersed in water as an example, a chip obtained by cutting a wafer with a pattern wiring into 2 cm squares is dispersed in a dispersion of colloidal silica particles. After soaking for 30 seconds, the chip is rinsed with pure water for about 30 seconds and blown with nitrogen. Thereafter, the chip is placed on a sample stage for SEM observation, an acceleration voltage of 10 kV is applied, the silica particles are observed at a magnification of 100,000, and an image is taken. 20 silica particles are arbitrarily selected from the obtained image, and the average of the particle diameters of these particles is defined as the average particle diameter. At this time, when the selected silica particles have a shape as shown in FIG. 5, a rectangle (circumscribed rectangle L) circumscribing the silica particles P and arranged so that the long side is the longest is led. And the long side of the circumscribed rectangle L is X, the short side is Y, and the biaxial average primary particle diameter is calculated as (X + Y) / 2, and is defined as the particle diameter of the particle.

The number of silanol groups per gram of silica particles may be 10 × 10 ¹⁸ pieces / g or more, or 50 × 10 ¹⁸ pieces / g or more from the viewpoint of easily obtaining an airgel having excellent shrinkage resistance. 100 × 10 ¹⁸ pieces / g or more. The number of silanol groups per gram of silica particles may be 1000 × 10 ¹⁸ pieces / g or less, may be 800 × 10 ¹⁸ pieces / g or less, and 700 × It may be 10 ¹⁸ pieces / g or less. From these viewpoints, the number of silanol groups per gram of the silica particles may be 10 × 10 ^{18 to} 1000 × 10 ¹⁸ pcs / g, or 50 × 10 ^{18 to} 800 × 10 ¹⁸ pcs / g. 100 × 10 ^{18 to} 700 × 10 ¹⁸ pieces / g.

  The content of the silica particles contained in the sol is 1 mass with respect to 100 mass parts of the total amount of the sol from the viewpoint of easily imparting an appropriate strength to the airgel and easily obtaining an airgel excellent in shrinkage resistance during drying. Or 4 parts by mass or more. The content of the silica particles contained in the sol is 20 parts by mass or less with respect to 100 parts by mass of the total amount of the sol, from the viewpoint of easily suppressing the solid heat conduction of the silica particles and easily obtaining an airgel excellent in heat insulation. It may be 15 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, or 8 parts by mass or less. From these viewpoints, the content of the silica particles contained in the sol may be 1 to 20 parts by mass or 4 to 15 parts by mass with respect to 100 parts by mass of the sol. 12 mass parts may be sufficient, 4-10 mass parts may be sufficient, and 4-8 mass parts may be sufficient.

[Other aspects]
The airgel which concerns on this embodiment can have a structure represented by following formula (4). The airgel which concerns on this embodiment can have a structure represented by following formula (4) while containing a silica particle.

In formula (4), R ⁹ represents an alkyl group. As an alkyl group, a C1-C6 alkyl group is mentioned, for example, A methyl group is mentioned specifically ,.

  The airgel which concerns on this embodiment can have a structure represented by following formula (5). The airgel which concerns on this embodiment can have a structure represented by following formula (5) while containing a silica particle.

In formula (5), R ¹⁰ and R ¹¹ each independently represent an alkyl group. As an alkyl group, a C1-C6 alkyl group is mentioned, for example, A methyl group is mentioned specifically ,.

  The airgel which concerns on this embodiment can have a structure represented by following formula (6). The airgel which concerns on this embodiment can have a structure represented by following formula (6) while containing a silica particle.

In the formula (6), R ¹² represents an alkylene group. As an alkylene group, a C1-C10 alkylene group is mentioned, for example, Specifically, an ethylene group and a hexylene group are mentioned.

  The airgel according to the present embodiment may have a structure derived from polysiloxane. That is, the porous spacer layer 1 according to the present embodiment may be composed of a layer containing an airgel having a structure derived from polysiloxane. Examples of the structure derived from polysiloxane include structures represented by the above formula (1), (2), (3), (4), (5) or (6). The airgel which concerns on this embodiment may have at least 1 type among the structures represented by said Formula (4), (5) and (6), without containing a silica particle.

  When the porous spacer layer 1 is composed of aerogel, the thickness of the porous spacer layer 1 (aerogel layer) can be 1 μm or more because it is easy to obtain good heat insulating properties, and is 10 μm or more. It may be 30 μm or more. The thickness of the airgel layer may be 1000 μm or less, 200 μm or less, 100 μm or less, or 80 μm or less from the viewpoint of shortening the washing and solvent replacement step and the drying step described later. There may be. From these viewpoints, the thickness of the airgel layer may be 1-1000 μm, 10-200 μm, 30-100 μm, or 30-80 μm.

(Support)
The support 2 is a non-aerogel layer, and the configuration of the support 2 is not particularly limited, and may be a single layer or a multilayer. As a shape of the support body 2, since the light weight can be provided to the laminated body 5, it can be set as a film form or foil shape.

  When the support 2 has at least one layer having a heat ray reflecting function or a heat ray absorbing function, the heat insulating property of the laminate 5 can be further improved. The support 2 having a heat ray reflection function or a heat ray absorption function can function as a radiator and can play a role of blocking heat from the outside.

  The heat ray reflection function refers to a function in which reflection of light in the near infrared or infrared region of about 800 to 3000 nm is larger than light absorption and light transmission. On the other hand, the heat ray absorption function refers to a function in which light absorption in the near infrared or infrared region of about 800 to 3000 nm is larger than light reflection and light transmission. Here, light reflection includes light scattering.

  The support 2 according to the present embodiment may be composed of at least one of a layer having a heat ray reflecting function and a layer having a heat ray absorbing function, and may be composed of only a layer having a heat ray reflecting function, or a heat ray absorbing function. It may consist of only the layer which has. Moreover, the support body 2 may be a laminate of a layer having a heat ray reflecting function and a layer having a heat ray absorbing function. Further, the support 2 may be a laminate of a layer having a heat ray reflecting function or a heat ray absorbing function and a layer not having a heat ray reflecting function and a heat ray absorbing function. In this case, the layer having the heat ray reflecting function or the heat ray absorbing function may be formed on one side or both sides of the layer not having the heat ray reflecting function and the heat ray absorbing function.

  The layer having a heat ray reflective function can include a heat ray reflective material. The heat ray reflective material is not particularly limited as long as it is a material that reflects light in the near infrared or infrared region. Examples of heat-reflective materials include aluminum compounds such as aluminum and aluminum oxide, zinc compounds such as zinc aluminate, magnesium compounds such as hydrotalcite, silver compounds such as silver, titanium, titanium oxide, and strontium titanate. Examples include titanium compounds, copper compounds such as copper and bronze, microballoons such as stainless steel, nickel, tin, and shirasu balloons, ceramic balloons, and pearl mica. These may be used alone or in combination of two or more.

  Among these, a material containing aluminum, magnesium, silver, or titanium can be used as a heat ray reflective material from the viewpoint of easily reducing thermal conductivity and being inexpensive and excellent in handleability.

  The layer having a heat ray reflecting function may be composed of a metal foil such as an aluminum foil or a copper foil. The layer having a heat ray reflecting function may be a resin film prepared by kneading an aluminum paste or titanium oxide with a resin such as polyolefin, polyester, polycarbonate, or polyimide. Furthermore, the layer having a heat ray reflecting function may be a deposited film obtained by depositing aluminum, silver or the like on a resin film such as polyolefin, polyester, polycarbonate, polyimide, etc. by physical vapor deposition such as sputtering or vacuum vapor deposition or chemical vapor deposition.

The layer having a heat ray absorbing function can include a heat ray absorbing material. The heat-absorbing material is not particularly limited as long as it is a substance that absorbs light in the near infrared or infrared region. Examples of heat-absorbing materials include carbon graphite such as flaky graphite, earthy graphite, and artificial graphite, carbon powder such as carbon black; barium sulfate, strontium sulfate, calcium sulfate, mercalite (KHSO ₄ ), halotristone, Metal sulfates such as alumite and iron alumite; antimony compounds such as antimony trioxide; metal oxides such as tin oxide, indium oxide, indium tin oxide, zinc oxide and anhydrous zinc antimonate; ammonium-based, urea-based, Imonium, aminium, cyanine, polymethine, anthraquinone, dithiol, copper ion, phenylenediamine, phthalocyanine, benzotriazole, benzophenone, oxalic anilide, cyanoacrylate, or benzotriazole dyes Or face It can be mentioned.

  Among these, as the heat ray-absorbing material, a material containing carbon graphite, carbon black, metal sulfate, or an antimony compound can be used from the viewpoint of easily reducing the thermal conductivity, and being inexpensive and easy to handle. . From the viewpoint of further reducing the thermal conductivity, the layer having a heat ray absorbing function may be a resin film prepared by kneading carbon black, antimony oxide or barium sulfate.

  From the viewpoint of further improving the heat insulating properties, the support 2 is a layer composed of a material containing at least one selected from the group consisting of carbon graphite, aluminum, magnesium, silver, titanium, carbon black, metal sulfate and antimony compounds. Can have. From the viewpoint of excellent handling properties and improved heat insulation, the support 2 may be an aluminum foil, an aluminum deposited film, a silver deposited film, or an antimony oxide-containing film.

  The surface of the support 2 on the side where the porous spacer layer 1 is not provided may have a protective layer for the purpose of protecting the porous spacer layer 1 when a plurality of laminated bodies 5 are stacked. Examples of the constituent material of the protective layer include a urethane resin, a polyester resin, an acrylic resin, a phenol resin, and the like, and may be the same material as the resin layer described above. These resin layers may be a single layer or multiple layers.

  The surface of the support 2 on the side where the porous spacer layer 1 is not laminated may be subjected to a mold release treatment.

  The thickness of the support 2 is not particularly limited, but may be 3 μm or more from the viewpoint of handling properties, may be 5 μm or more, and may be 7 μm or more. On the other hand, from the viewpoint of improving heat insulation, the thickness of the support 2 can be 100 μm or less, may be 80 μm or less, and may be 50 μm or less. That is, the thickness of the support 2 can be 3 to 100 μm, 5 to 80 μm, or 7 to 50 μm.

<Method for producing laminated composite>
Next, the manufacturing method of a laminated composite is demonstrated. Although the manufacturing method of a laminated composite is not specifically limited, For example, it can manufacture with the following method. That is, in the laminated composite of the present embodiment, the first step of producing a laminate 5 including the porous spacer layer 1 and the support 2, and the porous spacer layer 1 and the support 2 in the laminate 5 are combined. It is produced through the second step of joining at the joining member or joint.

[First step]
The first step is a step for producing a laminate 5 including the porous spacer layer 1 and the support 2. When the porous spacer layer 1 is a sheet or a film, the laminate 5 can be obtained by overlapping the porous spacer layer 1 and the support 2. When airgel is adopted as the material of the porous spacer layer 1, the laminate 5 can be obtained by forming the airgel layer as the porous spacer layer 1 on the surface of the support 2. Hereinafter, a method for forming an airgel layer on the surface of the support 2 will be described.

  The laminate 5 including the airgel layer (porous spacer layer) and the support 2 includes, for example, a sol generation step for generating a sol for forming an airgel, and a sol coating liquid containing the sol as a surface of the support 2. A sol coating film forming step of forming a sol coating film by coating on the top, a wet gel generating step of generating a wet gel from the sol coating film, a step of washing and (if necessary) replacing the solvent with the wet gel; It can be obtained through a drying step of drying the washed and solvent-substituted wet gel. The sol refers to a state before the gelation reaction occurs. In the present embodiment, for example, it means a state in which a silicon compound (if necessary, further silica particles) is dissolved or dispersed in a solvent. The wet gel means a gel solid in a wet state that contains a liquid medium but does not have fluidity. Hereinafter, each process of an airgel layer formation process is demonstrated.

(Sol generation process)
In the sol production step, for example, a silicon compound (and if necessary, further silica particles) and a solvent are mixed and hydrolyzed to produce a sol. In this step, an acid catalyst may be further added to promote the hydrolysis reaction. Further, as shown in Japanese Patent No. 5250900, a surfactant, a thermally hydrolyzable compound, and the like can be added. Furthermore, components such as carbon graphite, aluminum compounds, magnesium compounds, silver compounds, and titanium compounds may be added for the purpose of suppressing heat ray radiation.

  As the solvent, for example, water or a mixed solution of water and alcohols can be used. Examples of alcohols include methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol, and t-butanol. Among these, methanol, ethanol, 2-propanol etc. are mentioned as alcohol with a low surface tension and a low boiling point at the point which reduces the interfacial tension with a gel wall. You may use these individually or in mixture of 2 or more types.

  For example, when alcohol is used as the solvent, the amount of alcohol may be, for example, 4 to 8 mol or 4 to 6.5 with respect to 1 mol of the total amount of the silicon compound and the polysiloxane compound. It may be 4.5 to 6 moles. By making the amount of alcohols 4 mol or more, it becomes easier to obtain good compatibility, and by making the amount 8 mol or less, it becomes easier to suppress gel shrinkage.

  Examples of the acid catalyst include hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, bromic acid, chloric acid, chlorous acid, hypochlorous acid, and other inorganic acids; acidic phosphoric acid Acidic phosphates such as aluminum, acidic magnesium phosphate and acidic zinc phosphate; organic carboxylic acids such as acetic acid, formic acid, propionic acid, oxalic acid, malonic acid, succinic acid, citric acid, malic acid, adipic acid and azelaic acid Etc. Among these, an organic carboxylic acid is mentioned as an acid catalyst which improves the water resistance of the obtained airgel layer more. Examples of the organic carboxylic acids include acetic acid, but may be formic acid, propionic acid, oxalic acid, malonic acid and the like. You may use these individually or in mixture of 2 or more types.

  By using an acid catalyst, the hydrolysis reaction of the silicon compound is promoted, and a sol can be obtained in a shorter time. The addition amount of an acid catalyst can be 0.001-0.1 mass part with respect to 100 mass parts of total amounts of a silicon compound, for example.

  As the surfactant, a nonionic surfactant, an ionic surfactant, or the like can be used. You may use these individually or in mixture of 2 or more types.

  Examples of the nonionic surfactant include those containing a hydrophilic part such as polyoxyethylene and a hydrophobic part mainly composed of an alkyl group, and those containing a hydrophilic part such as polyoxypropylene. Examples of those containing a hydrophilic part such as polyoxyethylene and a hydrophobic part mainly composed of an alkyl group include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether and the like. Examples of those containing a hydrophilic portion such as polyoxypropylene include polyoxypropylene alkyl ethers, block copolymers of polyoxyethylene and polyoxypropylene, and the like.

  Examples of the ionic surfactant include a cationic surfactant, an anionic surfactant, and an amphoteric surfactant. Examples of the cationic surfactant include cetyltrimethylammonium bromide and cetyltrimethylammonium chloride, and examples of the anionic surfactant include sodium dodecylsulfonate. Examples of amphoteric surfactants include amino acid surfactants, betaine surfactants, amine oxide surfactants, and the like. Examples of amino acid surfactants include acyl glutamic acid. Examples of betaine surfactants include lauryldimethylaminoacetic acid betaine and stearyldimethylaminoacetic acid betaine. Examples of the amine oxide surfactant include lauryl dimethylamine oxide.

  These surfactants are thought to act to reduce phase differences by reducing the difference in chemical affinity between the solvent in the reaction system and the growing siloxane polymer in the wet gel formation process. It is done. The addition amount of the surfactant depends on the kind of the surfactant or the kind and amount of the silicon compound, but may be, for example, 1 to 100 parts by mass with respect to 100 parts by mass of the total amount of the silicon compound. 5-60 mass parts may be sufficient.

  The thermohydrolyzable compound is considered to generate a base catalyst by thermal hydrolysis, thereby making the reaction solution basic, and promoting the sol-gel reaction in the wet gel formation step. Therefore, the thermohydrolyzable compound is not particularly limited as long as it is a compound that can make the reaction solution basic after hydrolysis. Urea; formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N -Acid amides such as methylacetamide and N, N-dimethylacetamide; cyclic nitrogen compounds such as hexamethylenetetramine and the like. Among these, urea is particularly easy to obtain the above-mentioned promoting effect.

  The amount of the thermally hydrolyzable compound added is not particularly limited as long as it can sufficiently promote the sol-gel reaction in the wet gel formation step. For example, the addition amount of the thermohydrolyzable compound (urea or the like) may be, for example, 1 to 200 parts by mass or 2 to 150 parts by mass with respect to 100 parts by mass of the total amount of the silicon compound. . By making the addition amount 1 mass part or more, it becomes easier to obtain good reactivity, and by making it 200 mass parts or less, it becomes easier to further suppress the precipitation of crystals and the decrease in gel density.

  The hydrolysis in the sol production step depends on the type and amount of silicon compound, silica particles, acid catalyst, surfactant and the like in the mixed solution, but for example, in a temperature environment of 20 to 60 ° C. for 10 minutes to It may be performed for 24 hours, or may be performed in a temperature environment of 50 to 60 ° C. for 5 minutes to 8 hours. Thereby, the hydrolyzable functional group in a silicon compound is fully hydrolyzed, and the hydrolysis product of a silicon compound can be obtained more reliably.

  When adding a thermohydrolyzable compound in a solvent, you may adjust the temperature environment of a sol production | generation process to the temperature which suppresses the hydrolysis of a thermohydrolyzable compound and suppresses gelatinization of a sol. The temperature at this time may be any temperature as long as the hydrolysis of the thermally hydrolyzable compound can be suppressed. For example, when urea is used as the thermally hydrolyzable compound, the temperature environment in the sol production step may be 0 to 40 ° C or 10 to 30 ° C.

(Sol coating film forming process)
The sol coating film forming step is a step of forming a sol coating film by coating a sol coating liquid containing the sol on the surface of the support 2. The sol coating liquid may be an embodiment made of the sol. Further, the sol coating solution may be a solution obtained by gelling (semi-gelling) the sol to the extent that it has fluidity. The sol coating liquid may contain a base catalyst in order to promote gelation, for example.

  Base catalysts include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; ammonium compounds such as ammonium hydroxide, ammonium fluoride, ammonium chloride, and ammonium bromide; sodium metaphosphate Basic sodium phosphates such as sodium pyrophosphate and sodium polyphosphate; allylamine, diallylamine, triallylamine, isopropylamine, diisopropylamine, ethylamine, diethylamine, triethylamine, 2-ethylhexylamine, 3-ethoxypropylamine, diisobutylamine, 3 -(Diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, tetramethylethylenediamine, t-butylamine, sec- Aliphatic amines such as tilamine, propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxyamine, dimethylethanolamine, methyldiethanolamine, diethanolamine, triethanolamine; morpholine, N -Nitrogen-containing heterocyclic compounds such as methylmorpholine, 2-methylmorpholine, piperazine and derivatives thereof, piperidine and derivatives thereof, imidazole and derivatives thereof, and the like. Among these, ammonium hydroxide (ammonia water) is excellent in that it has high volatility and does not easily remain in the airgel layer after drying, and thus does not impair water resistance. You may use said base catalyst individually or in mixture of 2 or more types.

  By using a base catalyst, the dehydration condensation reaction, the dealcoholization condensation reaction, or both of the silicon compounds (polysiloxane compound group and silicon compound group) and silica particles in the sol can be promoted. Gelation can be performed in a shorter time. Thereby, a wet gel with higher strength (rigidity) can be obtained. In particular, ammonia is highly volatile and hardly remains in the airgel layer. Therefore, by using ammonia as a base catalyst, an airgel layer with better water resistance can be obtained.

  The addition amount of the base catalyst may be, for example, 0.5 to 5 parts by mass or 1 to 4 parts by mass with respect to 100 parts by mass of the total amount of silicon compounds (polysiloxane compound group and silicon compound group). Also good. By setting the addition amount to 0.5 parts by mass or more, gelation can be performed in a shorter time, and by setting the addition amount to 5 parts by mass or less, a decrease in water resistance can be further suppressed.

  When the sol is semi-gelled, the gelation may be performed in a sealed container so that the solvent and the base catalyst do not volatilize. In this case, the gelation temperature may be, for example, 30 to 90 ° C or 40 to 80 ° C. By setting the gelation temperature to 30 ° C. or higher, gelation can be performed in a shorter time. Moreover, since it becomes easy to suppress volatilization of a solvent (especially alcohol) by making gelation temperature into 90 degrees C or less, it can gelatinize, suppressing volume shrinkage.

  When the sol is semi-gelled, the gelation time varies depending on the gelation temperature, but when silica particles are contained in the sol, the gelation time is shortened compared to sols applied to conventional aerogels. can do. The reason is presumed that the hydrolyzable functional group or the condensable functional group of the silicon compound in the sol forms a hydrogen bond or a chemical bond with the silanol group of the silica particles. The gelation time may be, for example, 10 to 360 minutes or 20 to 180 minutes. When the gelation time is 10 minutes or longer, the viscosity of the sol is moderately improved, and the coating property on the surface of the support 2 is improved. When the gelation time is 360 minutes or less, the sol is completely gelled. It is easy to suppress this, and good adhesiveness with the surface of the support 2 is easily obtained.

  The method for applying the sol coating liquid to the surface of the support 2 is not particularly limited, and examples thereof include dip coating, spray coating, spin coating, and roll coating.

(Wet gel production process)
A wet gel production | generation process is a process of producing | generating a wet gel from the said sol coating film, for example. In the wet gel generation step, for example, the sol coating film is gelled by heating the sol coating film, and then the resulting gel is aged as necessary to generate a wet gel. You may perform a wet gel production | generation process in an airtight container so that a solvent and a base catalyst may not volatilize. When the gel is aged in the wet gel production process, the components of the wet gel are strongly bound, and as a result, a wet gel with sufficient strength (rigidity) to suppress shrinkage during drying is easily obtained. . The heating temperature and the aging temperature in the wet gel production step may be, for example, 30 to 90 ° C or 40 to 80 ° C. By setting the heating temperature or aging temperature to 30 ° C. or higher, a wet gel with higher strength (rigidity) can be obtained, and by setting the heating temperature or aging temperature to 90 ° C. or lower, the solvent (particularly alcohols) Since it becomes easy to suppress volatilization, it can be gelled while suppressing volume shrinkage.

(Washing and solvent replacement process)
The washing and solvent replacement step is a step of washing the wet gel obtained by the wet gel generation step (washing step), and a step of replacing the washing liquid in the wet gel with a solvent suitable for the drying conditions (the drying step described later). It is a process which has (solvent substitution process). The washing and solvent replacement step can be performed in a form in which only the solvent replacement step is performed without performing the step of washing the wet gel, but the impurities such as unreacted substances and by-products in the wet gel are reduced, and more The wet gel may be washed from the viewpoint of enabling production of a highly pure airgel layer. In addition, when the silica particle is contained in the gel, the solvent replacement step is not necessarily essential as described later.

  In the washing step, the wet gel obtained in the wet gel production step is washed. The washing can be repeatedly performed using, for example, water or an organic solvent. At this time, washing efficiency can be improved by heating.

  Examples of the organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, acetonitrile, hexane, toluene, diethyl ether, chloroform, ethyl acetate, tetrahydrofuran, Various organic solvents such as methylene chloride, N, N-dimethylformamide, dimethyl sulfoxide, acetic acid and formic acid can be used. You may use said organic solvent individually or in mixture of 2 or more types.

  In the solvent replacement step described below, a low surface tension solvent can be used to suppress gel shrinkage due to drying. However, low surface tension solvents generally have very low mutual solubility with water. Therefore, when using a low surface tension solvent in the solvent replacement step, examples of the organic solvent used in the washing step include hydrophilic organic solvents having high mutual solubility in both water and a low surface tension solvent. Note that the hydrophilic organic solvent used in the washing step can serve as a preliminary replacement for the solvent replacement step. Among the above organic solvents, examples of the hydrophilic organic solvent include methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, and the like. Methanol, ethanol, methyl ethyl ketone and the like are excellent in terms of economy.

  The amount of water or organic solvent used in the washing step can be set to an amount that can sufficiently wash the solvent in the wet gel and wash it. The amount can be, for example, 3 to 10 times the amount of the wet gel volume. The washing can be repeated, for example, until the moisture content in the wet gel after washing is 10% by mass or less with respect to the mass of silica.

  The temperature environment in the washing step can be a temperature not higher than the boiling point of the solvent used for washing. For example, when methanol is used, the temperature may be about 30 to 60 ° C.

  In the solvent replacement step, the solvent of the washed wet gel is replaced with a predetermined replacement solvent in order to suppress shrinkage in the drying step described later. At this time, the replacement efficiency can be improved by heating. Specific examples of the solvent for substitution include a low surface tension solvent described later in the drying step when drying is performed under atmospheric pressure at a temperature lower than the critical point of the solvent used for drying. On the other hand, when performing supercritical drying, examples of the substitution solvent include ethanol, methanol, 2-propanol, dichlorodifluoromethane, carbon dioxide, and the like, or a solvent obtained by mixing two or more of these.

  Examples of the low surface tension solvent include those having a surface tension at 20 ° C. of 30 mN / m or less. The surface tension may be 25 mN / m or less, or 20 mN / m or less. Examples of the low surface tension solvent include pentane (15.5), hexane (18.4), heptane (20.2), octane (21.7), 2-methylpentane (17.4), 3- Aliphatic hydrocarbons such as methylpentane (18.1), 2-methylhexane (19.3), cyclopentane (22.6), cyclohexane (25.2), 1-pentene (16.0); (28.9), toluene (28.5), m-xylene (28.7), p-xylene (28.3) and other aromatic hydrocarbons; dichloromethane (27.9), chloroform (27.2) ), Carbon tetrachloride (26.9), 1-chloropropane (21.8), 2-chloropropane (18.1) and other halogenated hydrocarbons; ethyl ether (17.1), propyl ether (20.5) ), Isop Ethers such as pyrether (17.7), butyl ethyl ether (20.8), 1,2-dimethoxyethane (24.6); acetone (23.3), methyl ethyl ketone (24.6), methyl propyl ketone (25.1), ketones such as diethyl ketone (25.3); methyl acetate (24.8), ethyl acetate (23.8), propyl acetate (24.3), isopropyl acetate (21.2), Examples include esters such as isobutyl acetate (23.7), ethyl butyrate (24.6), etc. (in parentheses indicate surface tension at 20 ° C., and the unit is [mN / m]). Among these, aliphatic hydrocarbons (hexane, heptane, etc.) have a low surface tension and an excellent working environment. Among these, by using a hydrophilic organic solvent such as acetone, methyl ethyl ketone, or 1,2-dimethoxyethane, it can be used as the organic solvent in the washing step. Among these, those having a boiling point of 100 ° C. or less at normal pressure may be used in terms of easier drying in the drying step described later. You may use said solvent individually or in mixture of 2 or more types.

  The amount of the solvent used in the solvent replacement step can be an amount that can sufficiently replace the solvent in the wet gel after washing. The amount can be, for example, 3 to 10 times the amount of the wet gel volume.

  The temperature environment in the solvent replacement step can be a temperature not higher than the boiling point of the solvent used for the replacement. For example, when heptane is used, the temperature may be about 30 to 60 ° C.

  In addition, as above-mentioned, when a silica particle is contained in the gel, a solvent substitution process is not necessarily essential. The inferred mechanism is as follows. When silica particles are not included, it is preferable to replace the wet gel solvent with a predetermined substitution solvent (a low surface tension solvent) in order to suppress shrinkage in the drying step. On the other hand, when silica particles are contained, the silica particles function as a support for a three-dimensional network-like skeleton, whereby the skeleton is supported, and it is considered that the shrinkage of the gel in the drying process is suppressed. Therefore, it is considered that the gel can be directly subjected to the drying step without replacing the solvent used for washing. In this way, although the drying process can be simplified from the washing and solvent replacement process, it is not excluded at all to perform the solvent replacement process.

(Drying process)
In the drying step, the wet gel that has been washed and solvent-substituted (if necessary) as described above is dried.

  The drying method is not particularly limited, and known atmospheric pressure drying, supercritical drying, or freeze drying can be used. Among these, atmospheric drying or supercritical drying can be used from the viewpoint of easy production of a low-density airgel layer. Further, from the viewpoint that production is possible at low cost, atmospheric pressure drying can be used. In the present embodiment, the normal pressure means 0.1 MPa (atmospheric pressure).

  The airgel layer according to the present embodiment can be obtained, for example, by drying a wet gel that has been washed and solvent-substituted (if necessary) at a temperature below the critical point of the solvent used for drying under atmospheric pressure. it can. The drying temperature varies depending on the type of substituted solvent (the solvent used for washing if solvent substitution is not performed), but especially when drying at a high temperature increases the evaporation rate of the solvent and causes large cracks in the gel. In view of the fact that there is, for example, it may be 20 to 150 ° C or 60 to 120 ° C. Moreover, although drying time changes with the capacity | capacitances and drying temperature of a wet gel, it can be 4 to 120 hours, for example. In the present embodiment, it is also included in the atmospheric pressure drying that the drying is accelerated by applying a pressure less than the critical point within a range not inhibiting the productivity.

  In the airgel layer forming step according to the present embodiment, predrying may be performed before the drying step from the viewpoint of suppressing airgel cracks due to rapid drying. The pre-drying temperature may be, for example, 60 to 180 ° C or 90 to 150 ° C. The pre-drying time varies depending on the capacity of the airgel layer and the drying temperature, but may be, for example, 1 to 30 minutes.

  The drying method in the drying step may be, for example, supercritical drying. Supercritical drying can be performed by a known method. Examples of the supercritical drying method include a method of removing the solvent at a temperature and pressure higher than the critical point of the solvent contained in the wet gel. Alternatively, as a method of supercritical drying, all or part of the solvent contained in the wet gel is obtained by immersing the wet gel in liquefied carbon dioxide, for example, under conditions of about 20 to 25 ° C. and about 5 to 20 MPa. And carbon dioxide having a lower critical point than that of the solvent, and then removing carbon dioxide alone or a mixture of carbon dioxide and the solvent.

  The airgel layer obtained by such normal pressure drying or supercritical drying may be additionally dried at 105 to 200 ° C. for about 0.5 to 2 hours under normal pressure. This makes it easier to obtain an airgel layer having a low density and having small pores. The additional drying may be performed at 150 to 200 ° C. under normal pressure.

[Second step]
Next, the laminated body is integrated in the laminating direction by installing the joining member or forming the joining portion so that the constituent members constituting the laminated body 5 obtained as described above are not separated from each other. For example, from the viewpoint of preventing variations in the number of layers per unit area when winding around a member, examples of the joining member include a pin, a thread-like member to be sewn, a bolt and a nut. Adhesion, thermocompression bonding, laser pressure bonding or bundling can be mentioned. By integrating the laminated body 5, the intensity | strength of a laminated composite can be reinforced and heat insulation can be improved.

<Insulation material>
The heat insulating material of the present embodiment includes at least one of the laminated composites 10 described so far, and has high heat insulating properties and excellent flexibility. The heat insulating material may be one in which a plurality of laminated composites 10 are laminated. The heat insulating material provided with the laminated composite 10 is excellent in handleability, and can exhibit excellent heat insulating performance after the thickness is reduced.

  Because of such advantages, the laminated composite 10 of the present embodiment is insulated in the cryogenic field (superconducting, cryogenic container, etc.), the space field, the building field, the automobile field, the home appliances, the semiconductor field, and industrial equipment. It can be applied to use as a material. Moreover, the laminated composite of this embodiment can be used as a water-repellent sheet, a sound absorbing sheet, a static vibration sheet, a catalyst-carrying sheet, etc. in addition to the use as a heat insulating material.

  Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.

Example 1
[Laminated composite 1]
As a support (a film having a heat ray reflecting function or a heat ray absorbing function), (longitudinal) 1000 mm × (horizontal) 500 mm × (thickness) 12 μm double-sided aluminum vapor deposited PET film (manufactured by Hitachi IC Corporation, product name: VM-PET) ) Was prepared. As a porous spacer layer, a polyester net having a basis weight of 16 g / m ² , a mesh number: 75 / cm ² , (vertical) 1000 mm × (horizontal) 500 mm × (thickness) 190 μm was prepared. A laminated body was obtained by superimposing these. Using a special gun, the laminate was joined with space pins (manufactured by JAXA) along the peripheral edge (four sides) of the laminate to obtain a laminate composite 1. The space between adjacent space pins (distance D2b in FIG. 3) was 10 cm.

(Example 2)

[Laminated composite 2]
The laminated composite 2 was the same as in Example 1 except that a polyester yarn (product name: Ace Crown # 40) manufactured by Onuki Fiber Co., Ltd. was used instead of the space pin as a joining means of the laminated body. Got.

(Example 3)
The laminated composite 3 was obtained in the same manner as in Example 1 except that the joining of the laminated body was performed by pressurization using a stapleless staple (product name: Harinacs KOKUYO) instead of the space pin. It was.

(Comparative Example 1)
[Laminated insulation 1]
By bonding the polyester net used in Example 1 as a heat insulating layer to a double-sided aluminum vapor-deposited PET film (product name: VM-PET, manufactured by Hitachi IC Corporation) as a support, a joined body (laminated heat insulating material 1) Got. That is, the laminated body was not joined.

(Comparative Example 2)
[Laminated insulation 2]
First, a support was prepared in the same manner as in Comparative Example 1. The laminated heat insulating material 2 was obtained by joining one place of the center part of the produced support body with a pin (see FIG. 6).

(Comparative Example 3)
[Laminated insulation 3]
Instead of joining one central part of the laminated body with pins, the laminated body was joined with a plurality of pins arranged so as to extend in the longitudinal direction of the laminated body and line up on a line passing through the central part as shown in FIG. Otherwise, the laminated heat insulating material 2 was obtained in the same manner as in Comparative Example 2. The pin installation interval was 10 cm.

[Evaluation]
The laminated composite obtained in each example and the laminated heat insulating material obtained in each comparative example were measured or evaluated according to the following conditions.

(1) Preparation of Liquid Nitrogen Container for Thermal Insulation Evaluation The laminated composite and the laminated thermal insulation material are (vertical) 606 mm × (horizontal) 343 mm sheet A, (vertical) 612 mm × (horizontal) 362 mm sheet B, (vertical ) 618mm x (width) 38
The sheet was processed into a size of 0 mm sheet C, (diameter) 105 mm sheet D, (diameter) 112 mm sheet E, and (diameter) 118 mm sheet F, respectively.

  Next, as a liquid nitrogen container outer peripheral sheet, a sheet A10 in which 10 sheets A are laminated so that adjacent supports are not in direct contact with each other via a porous spacer layer or a heat insulating layer, and a sheet in which 10 sheets B are laminated B10 and the sheet | seat C10 which laminated | stacked the sheet | seat C 10 layers were each produced. Similarly, as a liquid nitrogen container upper and lower sheet, a sheet D10 obtained by laminating 10 layers of sheet D, a sheet E10 obtained by laminating 10 layers of sheet E, and a sheet F10 obtained by laminating 10 layers of sheet F were produced.

  A liquid nitrogen container having a height of 600 mm and a diameter of 100 mm is prepared, a sheet A10 is disposed on the side surface, sheets D10 are disposed above and below the liquid nitrogen container, and wound around the liquid nitrogen container to form a laminated composite or laminated insulation. A liquid nitrogen container for thermal insulation evaluation in which 10 layers of materials were laminated was obtained. Next, the sheet B10 was disposed on the sheet A10, the sheet E10 was disposed on the sheet D10, and a liquid nitrogen container for thermal insulation evaluation in which 20 layers of the laminated composite or the laminated heat insulating material were laminated was obtained. Furthermore, the sheet C10 was arrange | positioned on the sheet | seat B10, the sheet | seat F10 was arrange | positioned on the sheet | seat D10, and the liquid nitrogen container for heat insulation evaluation by which 30 layers of lamination | stacking composites or lamination | stacking heat insulation materials were laminated | stacked was obtained. In addition, the joining part of the sheet | seat of a side surface and the upper and lower sheets was affixed with the aluminum tape.

  FIG. 8 schematically shows the structure of a liquid nitrogen container for thermal insulation evaluation in which a heat insulating material 30 formed by laminating a plurality of laminated composites (Examples) or laminated heat insulating materials (Comparative Example) is wound around the liquid nitrogen container 12. It is sectional drawing represented to. The heat insulating material 30 is laminated on the liquid nitrogen container 12 having the inlet 11 so as to cover the outer periphery.

(2) Measurement of thickness of heat insulating material The total thickness D (mm) of the heat insulating material provided on the outer periphery of the liquid nitrogen container 12 was calculated from the following equation.
D ₌ D c /2-50.0
In formula, _Dc (mm) shows the diameter of the liquid nitrogen container after winding a heat insulating material.

(3) Thermal insulation performance (heat flux)
Thermal insulation performance was measured using a liquid nitrogen container for thermal insulation evaluation. In FIG. 9, the schematic of a heat insulation performance test apparatus is shown. First, the liquid nitrogen container 12 around which the heat insulating material 30 was wound was placed in the thermostatic chamber 14 set to 283K and installed in the vacuum container 16. Next, evacuation in the vacuum vessel 16 was performed with the turbo molecular pump 20, and the vacuum pressure inside the vacuum vessel 16 was measured with the Pirani vacuum gauge 22 and the ion vacuum gauge 24. After operating the turbo molecular pump 20 and confirming that the Pirani vacuum gauge 22 showed a vacuum pressure of 4 × 10 ⁻¹ Pa or less, the vacuum pressure was measured with the ion vacuum gauge 24 and the pressure in the vacuum vessel 16 was 1. The evacuation was performed for 7 days until the pressure reached 10 ⁻² Pa or less. After that, after injecting liquid nitrogen into the liquid nitrogen container 12 installed in the vacuum container 16, the temperature of the neck pipe 18 and the flow rate of the evaporated nitrogen gas are substantially constant values, and it is confirmed that they are in a steady state. The heat flux q passing through the heat insulating material 30 was calculated.

式（Ｉ）中、ρ_ｇ，Ｔは室温のガス密度（ｋｇ／ｍ^３）、Ｖ_ｇ，Ｔは室温のガス流量（ｍ^３／ｓ）を示し、湿式流量計２６の出力と湿式流量計２６内部の温度により計測される値である。 The evaporative gas mass flow rate m (kg / s) of liquid nitrogen was obtained from the following formula (I).

In the formula (I), ρ _{g, T} represents a room temperature gas density (kg / m ³ ), V _{g, T} represents a room temperature gas flow rate (m ³ / s), and the output of the wet flow meter 26 and the wet flow meter 26 is a value measured by the internal temperature.

式（ＩＩ）中、Ｌは液体窒素の蒸発潜熱（Ｊ／ｋｇ）、ρ_ｇ，Ｓは大気圧飽和温度における窒素ガス密度（ｋｇ／ｍ^３）、ρ_ｌ，Ｓは液体窒素密度（ｋｇ／ｍ^３）を示す。 Next, the sum of the amount of radiant heat Q _r (W) entering through the heat insulating material 30 and the conduction heat Q _c (W) from the neck pipe 18 connecting the flange 17 and the liquid nitrogen container 12 is expressed by the following formula (II) )

In the formula (II), L is the latent heat of vaporization of liquid nitrogen (J / kg), ρg _{, S} is the nitrogen gas density (kg / m ³ ) at the atmospheric pressure saturation temperature, ρl _{, S} is the liquid nitrogen density (kg / m ³ ).

式（ＩＩＩ）中、（ ）内は首配管１８の伝導熱を示し、Ａ_ｓ（ｍ^２）は、首配管１８の断面積、Ｌ_ｃ（ｍ）は、首配管１８の長さを示し、Ｔ_ｈ（Ｋ）は、恒温温度、Ｔ_ｌ（Ｋ）は、低温温度を示し、λ_ｓｕｓ（Ｗ／（ｍ・Ｋ））は、ステンレスの熱伝導率を示す。首配管１８の伝導熱は、蒸発ガスの熱伝達によって首配管１８の表面から熱を奪うので効率φの係数が関わる。 Moreover, Qc was _{calculated |} required from following Formula (III).

In the formula (III), () indicates the conduction heat of the neck pipe 18, A _s (m ² ) indicates the cross-sectional area of the neck pipe 18, and L _c (m) indicates the length of the neck pipe 18, T _h (K) represents a constant temperature, T _l (K) represents a low temperature, and λ _sus (W / (m · K)) represents the thermal conductivity of stainless steel. Since the conduction heat of the neck pipe 18 takes heat from the surface of the neck pipe 18 by the heat transfer of the evaporating gas, the coefficient of efficiency φ is involved.

式（ＩＶ）中、Ｃ_ｐ（Ｊ／（ｋｇ・Ｋ））は、比熱を示す。なお、本評価において、上記Ａ_ｓの値は、０．２４３×１０^−４（ｍ^２）であり、上記Ｌの値は、１９９０００（Ｊ／ｋｇ）である。 The efficiency φ was obtained from the following formula (IV).

In formula (IV), C _p (J / (kg · K)) represents specific heat. In the present evaluation, the value of the _{A s,} a ^{0.243 × 10 -4 (m 2)} , the value of the L is 199000 (J / kg).

式（Ｖ）中、Ａ_ｒ（ｍ^２）は、液体窒素容器の表面積を示し、その値は、０．２０４１（ｍ^２）である。 The heat flux q (W / m ² ) passing through the laminated composite and the laminated heat insulating material was obtained from the following formula (V). The heat flux was measured three times, and the average value was used as the heat flux of this evaluation.

In formula (V), A _r (m ² ) represents the surface area of the liquid nitrogen container, and the value is 0.2041 (m ² ).

(4) Variation in number of layers A laminate in which the number of layers per unit area at both ends coincided with the central portion was evaluated as non-variable, and a non-matched laminate was evaluated as varied.

  Table 1 shows the evaluation results of the heat insulating properties of the laminated composites obtained in the respective examples and the laminated heat insulating materials obtained in the respective comparative examples.

  From the results shown in Table 1, it can be confirmed that when the laminated composite produced in the example is used, the heat flux is small and the heat insulation performance is excellent. Moreover, it can confirm that the laminated composite produced in the Example can obtain an equivalent heat flux with few layers compared with a comparative example, and can make the thickness of a heat insulating material thin.

DESCRIPTION OF SYMBOLS 1 ... Porous spacer layer, 2 ... Support body, 5 ... Laminate body, 5a ... Peripheral part, 8 ... Pin (joining member), 9 ... Joining part, 10 ... Laminated composite, 11 ... Inlet, 12 ... Liquid nitrogen Container, 14 ... thermostatic chamber, 16 ... vacuum vessel, 17 ... flange, 18 ... neck piping, 20 ... turbo molecular pump, 22 ... Pirani vacuum gauge, 24 ... ion vacuum gauge, 26 ... wet flow meter, 30 ... heat insulating material, L: circumscribed rectangle, P: silica particles.

Claims (13)

A laminate comprising at least a porous spacer layer and a support having a heat ray reflecting function or a heat ray absorbing function;
A bonding member for preventing the porous spacer layer and the support from separating from each other;
With
A laminated composite in which the joining member is provided along a peripheral edge of the laminated body.   The joining member is a pin that penetrates the laminate in the thickness direction, a thread-like member that stitches the laminate, or a combination of a bolt that penetrates the laminate in the thickness direction and a nut corresponding to the bolt. The laminated composite according to claim 1. A laminate comprising at least a porous spacer layer and a support having a heat ray reflecting function or a heat ray absorbing function;
A joint that prevents the porous spacer layer and the support from separating from each other, and is formed by pressure-bonding, thermocompression bonding, laser-bonding, or binding to the laminate;
With
The joined part is a laminated composite formed along the peripheral edge of the laminated body.   The said porous spacer layer is a layer comprised from the material containing at least 1 type chosen from the group which consists of a nylon fiber, a polyester fiber, a polyimide fiber, and a glass fiber. Laminated composite.   The laminated composite according to any one of claims 1 to 3, wherein the porous spacer layer is a layer containing a glass nonwoven fabric, a polyester nonwoven fabric, a glass fiber paper, a polyester net, or a nylon mesh.   The laminated composite according to any one of claims 1 to 5, wherein the porous spacer layer is a layer containing an airgel having a structure derived from polysiloxane.   The porous spacer layer is selected from the group consisting of a hydrolyzable functional group or a polysiloxane compound having a condensable functional group, and a hydrolysis product of the polysiloxane compound having a hydrolyzable functional group. The laminated composite according to any one of claims 1 to 6, which is an airgel layer made of a dried product of a wet gel that is a condensate of a sol containing at least one compound.   The laminated composite according to any one of claims 1 to 7, wherein the porous spacer layer is an airgel layer made of a dried product of a wet gel that is a condensate of a sol containing silica particles.   The laminated composite according to claim 8, wherein an average primary particle diameter of the silica particles is 1 nm or more and 500 nm or less.   The said support body has a layer comprised from the material containing at least 1 type chosen from the group which consists of carbon graphite, aluminum, magnesium, silver, titanium, carbon black, a metal sulfate, and an antimony compound of Claims 1-9. The laminated composite according to any one of the above.   The laminated composite according to any one of claims 1 to 10, wherein the support is an aluminum foil, an aluminum deposited film, a silver deposited film, or an antimony oxide-containing film.   The laminated composite according to any one of claims 1 to 11, wherein the support is an aluminum foil or an aluminum deposited film.   A heat insulating material comprising the laminated composite according to any one of claims 1 to 12.

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