KR20220010727A - Manufacturing method of thermal storage sheet - Google Patents

Abstract

A method for manufacturing a heat storage sheet according to the first aspect of the present disclosure includes a step of forming a heat storage layer comprising a heat storage component that exhibits heat storage property by a phase transition and a photocuring agent on the surface of a base film; and a step of curing the thermal storage layer by irradiating the thermal storage layer with an active energy ray in a state where the temperature is higher than the phase transition temperature of the thermal storage component. A method for manufacturing a heat storage sheet according to a second aspect of the present disclosure includes a step of forming a heat storage layer comprising a heat storage component that exhibits heat storage property through a phase transition and a thermosetting agent on the surface of a base film, and a heat storage component and curing the thermal storage layer by heating the thermal storage layer to a temperature higher than the phase transition temperature of the thermal storage layer by at least 20°C.

Description

Manufacturing method of thermal storage sheet

The present disclosure relates to a method for manufacturing a thermal storage sheet.

A thermal storage material is a material which can take out the stored energy as heat|fever as needed. BACKGROUND ART Thermal storage materials are used for air conditioning equipment, floor heating equipment, refrigerators, electronic parts such as IC chips, automobile interior and exterior materials, automobile parts such as canisters, and thermal insulation containers.

In view of the magnitude of the amount of heat, latent heat storage using a phase transition of a substance is widely used. As a latent heat storage material, water-ice is well known. Water-ice is a material with a large amount of heat, but since the phase transition temperature is limited to 0° C. under the atmosphere, the application range is also limited. Paraffin is used as a latent heat storage material having a phase transition temperature higher than 0°C and not higher than 100°C. However, when paraffin undergoes a phase change by heating, it becomes a liquid, and there is a risk of ignition and ignition. In order to use paraffin as a heat storage material, it is necessary to prevent paraffin from leaking from the heat storage material by storing it in an airtight container such as a bag or the like, thereby limiting the field of application.

In response to such a problem, a thermal storage material in which a thermal storage material is microencapsulated and dispersed in a polymer or the like has been studied. For example, Patent Document 1 discloses a heat storage material including a thermoplastic polymer, a capsule core made of a latent heat storage material, and microcapsules having a polymer as a capsule wall. Patent Document 1 discloses that a sheet having a thickness of about 5 mm is manufactured by passing through a process of discharging the melt discharged from the extruder with a sheet die in an Example.

Patent Document 1: Japanese Patent Publication No. 2014-500359

By the way, the heat storage material may be used by bending or being wound around an application target. Therefore, it is preferable that the sheet-like thermal storage material is excellent in flexibility.

The present disclosure provides a method for efficiently manufacturing a thermal storage sheet having a thermal storage layer having excellent flexibility.

The present inventors evaluated the flexibility by forming the thermal storage material in a layer having a thickness of about 200 µm in the process of developing a convenient sheet-like thermal storage material. As a result, when the layer having heat storage properties (hereinafter referred to as "thermal storage layer") is formed through curing treatment by light or heat, the heat storage layer is heated to a temperature higher than the phase transition temperature of the heat storage component included in the heat storage material. By advancing the curing reaction by light or heat in a heated state (that is, in a state in which the thermal storage component is melted or amorphous), the flexibility of the thermal storage layer is higher than when the curing reaction is carried out at a temperature lower than the phase transition temperature of the thermal storage material. I have learned that performance improves.

The method for manufacturing the thermal storage sheet according to the first aspect of the present disclosure includes a step of curing the thermal storage layer by irradiation with active energy rays (eg, ultraviolet rays). That is, the manufacturing method of this thermal-storage sheet includes the following steps.

A step of forming a heat storage layer comprising a heat storage component and a photocuring agent that expresses heat storage property by phase transition on the surface of the base film

A step of curing the thermal storage layer by irradiating the thermal storage layer with an active energy ray in a state where the temperature of the thermal storage layer is higher than the phase transition temperature of the thermal storage component.

According to this method of manufacturing the thermal storage sheet, curing treatment with active energy rays (hereinafter referred to as “photocuring treatment”) for the thermal storage layer in a state higher than the phase transition temperature (the state in which the thermal storage component is melted or an amorphous state). ), the flexibility of the heat storage layer can be improved. In addition, since the thermal storage layer in a state higher than the phase transition temperature has high transparency to active energy rays, by irradiating the thermal storage layer with active energy rays, the photocuring reaction can be sufficiently advanced throughout the thickness direction of the thermal storage layer. have.

The method for manufacturing the thermal storage sheet according to the second aspect of the present disclosure includes a step of curing the thermal storage layer by heat. That is, the manufacturing method of this thermal-storage sheet includes the following steps.

A step of forming a heat storage layer comprising a heat storage component and a thermosetting agent that express heat storage property by phase transition on the surface of the base film

A step of curing the heat storage layer by heating the heat storage layer to a temperature 20°C or more higher than the phase transition temperature of the heat storage component

→Confirm

According to the manufacturing method of this thermal storage sheet, curing treatment by heat (hereinafter referred to as "thermal curing treatment") is performed on the thermal storage layer in a state higher than the phase transition temperature (the state in which the thermal storage component is melted or an amorphous state). By doing so, the flexibility of the heat storage layer can be improved. The thermosetting treatment is useful when the photocuring treatment is not suitable, such as when the transparency of the heat storage layer with respect to the active energy ray is low. For example, when the filler is dispersed in the thermal storage layer from the viewpoint of further improving the flexibility, since the transparency of the thermal storage layer tends to decrease, thermosetting instead of or together with the photocuring treatment processing should be carried out. In addition, even if it is a case where a heat-storage layer contains a filler, depending on the filler content of a heat-storage layer or the thickness of a heat-storage layer, you may perform photocuring process independently without performing a thermosetting process.

In the method for manufacturing the thermal storage sheet according to the second aspect, before performing the thermal curing treatment on the thermal storage layer, as a thermosetting agent, the active temperature is the phase transition temperature of the thermal storage component so that the thermal curing reaction of the thermal storage layer does not proceed. It is preferable to use a higher one. That is, it is preferred that the activation temperature of the heat-curing agent and a T to _A ℃, when the phase transition temperature of the thermosensitive element to the axis T _P ℃, satisfy the conditions represented by the following inequality (1).

0<T _A -T _P ≤100...(1)

In this indication, you may employ|adopt the following process according to the kind of component contained in a thermal-storage layer, or its characteristic. For example, when the photocuring agent or thermosetting agent contained in the heat storage layer is one whose activity is reduced by oxygen, oxygen may be blocked by attaching a cover film to the heat storage layer before photocuring or thermosetting treatment is performed. . Moreover, you may implement each process (For example, formation of the heat storage layer on the surface of a base film, photocuring process, and thermosetting process) on the low oxygen condition of 5 volume% or less of oxygen concentration.

Even when the heat-storage layer does not have tackiness, the heat-storage layer may have tackiness by forming an adhesive layer on the surface of the heat-storage layer from the viewpoint of being able to easily stick the heat-storage sheet to the application target. For example, what is necessary is just to provide an adhesive layer in advance on the surface on which the heat storage layer of a base film is formed, and just to transfer the adhesive layer to the heat storage layer side by passing through a photocuring process or thermosetting process. Alternatively, the adhesive layer may be formed on the surface of the heat storage layer before or after the photocuring treatment or the thermosetting treatment by means such as laminating or coating. You may stick a cover film on the surface of an adhesion layer from a viewpoint of preventing that a foreign material adheres to an adhesion layer.

In the present disclosure, the thickness of the heat storage layer is, for example, 10 to 500 µm. When the thickness of the thermal storage layer is within this range, it is suitable as a thermal storage material for devices requiring size reduction or thickness reduction. For example, when forming a heat storage layer of 100 micrometers or less, what is necessary is just to form a heat storage layer through the coating and drying process of the varnish containing a solvent. On the other hand, when forming a heat storage layer exceeding 100 micrometers, what is necessary is just to apply the melt of the composition containing a heat storage component etc. on the surface of a base film without using a solvent. In addition, when the composition is melted by heat, the composition may be heated to a temperature at which the heat-storage component is melted but the thermosetting reaction does not proceed. Moreover, you may produce the heat-storage layer of predetermined thickness by separately preparing at least two layers of heat-storage layers before or after hardening by light or heat, and bonding these together. When the surfaces of the two heat-storage layers to be bonded are in a melted state by heat storage, the two heat-storage layers can be integrated without interposing an adhesive layer therebetween.

According to the present disclosure, a method for efficiently manufacturing a thermal storage sheet having a thermal storage layer having excellent flexibility is provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically the thermal-storage sheet which concerns on 1st Embodiment.
Fig. 2 (a) is a cross-sectional view schematically showing a state in which a heat storage layer is formed on the surface of a base film, and Fig. 2 (b) is an example of a photocuring treatment for the heat storage layer and a step of forming an adhesive layer It is a sectional view schematically shown, and FIG.2(c) is sectional drawing which shows typically another example of the photocuring process with respect to a heat storage layer, and the process of forming an adhesion layer.
3A and 3B are cross-sectional views schematically illustrating an example of an adhesive sheet including an adhesive layer.
4(a) and 4(b) are cross-sectional views schematically showing modified examples of the steps shown in FIGS. 2(b) and 2(c).
5(a) and 5(b) are cross-sectional views schematically showing a heating furnace and an ultraviolet irradiation device disposed at a rear end thereof.
6A and 6B are cross-sectional views schematically showing an example of a thermosetting treatment for the heat storage layer and a step of forming an adhesive layer.
7 is a cross-sectional view schematically showing a thermal storage sheet according to the second embodiment.
8 is a cross-sectional view schematically showing another embodiment of the thermal-storage sheet.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this indication is described in detail, referring drawings suitably. In addition, this invention is not limited to the following embodiment.

In this specification, "(meth)acryloyl" means "acryloyl" and "methacryloyl" corresponding thereto, "(meth)acrylate", "(meth)acryl", etc. The same is true for similar expressions of

The weight average molecular weight (Mw) in this specification is measured on the following conditions using gel permeation chromatography (GPC), and means the value determined using polystyrene as a standard substance.

・Measuring device: HLC-8320GPC (product name, manufactured by Tosoh Corporation)

Analysis column: TSKgel SuperMultipore HZ-H (3 pieces connected) (product name, manufactured by Tosoh Corporation)

Guard column: TSKguardcolumn SuperMP(HZ)-H (product name, manufactured by Tosoh Corporation)

·Eluent: THF

・Measurement temperature: 25℃

<First embodiment>

(heat storage sheet)

1 is a cross-sectional view schematically showing a thermal-storage sheet according to the present embodiment. The thermal-storage sheet 10 shown in the figure includes a base film 1 , a thermal-storage layer 3 , an adhesive layer 5 , and a cover film 7 , and these are laminated in this order. The heat storage sheet 10 may have a shape according to a user's request, for example, may be in the form of a tape wound on a reel, cut to an appropriate length when the user uses it, and may be in the form of a card having a predetermined area. do. The tape-shaped heat storage sheet 10 wound on a reel may be, for example, 500 to 1000 m in length, 10 to 100 m or 20 to 50 m in length, for example, 0.5 to 1.0 m in width and 0.5 to 5.0 cm in length. Or 10 to 50 cm may be sufficient. In the case of a card shape, the shape is, for example, approximately square or approximately rectangular, and the length of one side is, for example, 0.5 to 20 cm, and may be 1 to 10 cm or 3 to 5 cm. After forming the thermal storage layer 3 etc. on the surface of a raw film, a tape-shaped or card-shaped thermal-storage sheet can be manufactured by cutting to a predetermined width or size.

The base film 1 should just have resistance to the manufacturing process of the thermal-storage sheet 10 (for example, heat resistance, chemical-resistance, and tensile strength). Specific examples of the base film 1 include a polyester film, a polypropylene film (such as an OPP film), a polyethylene terephthalate film, a polyimide film, a polyetherimide film, a polyethernaphthalate film, and a methylpentene film. . The thickness of the base film 1 may be 5-200 micrometers, for example, and 10-150 micrometers or 50-100 micrometers may be sufficient as it. In addition, when using the thermal-storage sheet 10, the base film 1 may be removed, and may remain laminated|stacked on the thermal-storage layer 3.

The heat-storage layer 3 is a layer containing a heat-storage component that exhibits heat-storage property by a phase transition. The heat-storage layer 3 is made of a heat-storage material composed of a polymer matrix and a heat-storage component contained therein. This type of heat storage material is called a composite heat storage material. Moreover, the polymer matrix may have heat storage property. The thickness of the heat storage layer 3 may be, for example, 10-500 micrometers, 25-250 micrometers, or 50-200 micrometers may be sufficient as it.

It is preferable that the thermal storage component has crystallinity as typified by paraffin, for example, from the viewpoint of obtaining a thermal storage material having a particularly excellent thermal storage amount because it is difficult to ooze out of the polymer matrix. The phase transition temperature (melting point) of the crystalline component may be, for example, 0 to 200°C, or 15 to 100°C or 20 to 60°C. The phase transition temperature of the crystalline component depends on the weight average molecular weight of the crystalline component. The details of the polymer matrix and the heat storage component (crystalline component) will be described later.

The adhesive layer 5 is for imparting adhesiveness to the thermal storage layer 3 from the viewpoint of the convenience of use of the thermal storage sheet 10 . As an adhesive contained in the adhesive layer 5, a well-known thing can be used. Specific examples of the pressure-sensitive adhesive include urethane-based pressure-sensitive adhesives and acrylic pressure-sensitive adhesives. Moreover, it is preferable to use a urethane-type adhesive from a heat resistant viewpoint. The thickness of the adhesion layer 5 may be 0.1-100 micrometers, for example, and 1-50 micrometers or 5-10 micrometers may be sufficient as it.

The cover film 7 is for preventing foreign matter from adhering to the adhesive layer 5 . As a specific example of the cover film 7, the thing similar to the base film 1 mentioned above is mentioned. In addition, when the heat storage layer 3 is affixed at a predetermined position via the adhesive layer 5 , the cover film 7 is peeled from the adhesive layer 5 .

(Method for manufacturing heat storage sheet)

The thermal storage sheet 10 is manufactured through the following process. In addition, the heat storage layer 3 means a heat storage layer after a photocuring process, and the heat storage layer 3p means a heat storage layer before a photocuring process.

(A1) The process of forming the heat storage layer 3p on the surface of the base film 1 (refer FIG.2(a))

(B1) A step of curing the heat storage layer 3p by irradiating active energy rays to the heat storage layer 3p in a state where the temperature of the heat storage layer 3p is higher than the phase transition temperature of the heat storage component (see FIG. 2 ( b))

(C1) The process of forming the adhesion layer 5 and the cover film 7 on the surface of the heat storage layer 3 after photocuring process

According to the manufacturing method of this thermal storage sheet, the thermal storage layer 3 excellent in flexibility can be formed by performing photocuring process with respect to the thermal storage layer 3p in a state higher than the phase transition temperature of a thermal storage component. In addition, since the thermal storage layer 3p containing the thermal storage component in the molten state or the amorphous state has high transparency to active energy rays, by irradiating the thermal storage layer 3p with active energy rays, the thermal storage layer 3p It is possible to sufficiently advance the photocuring reaction over the entire thickness direction. Hereinafter, each process of the manufacturing method of the thermal-storage sheet 10 is demonstrated in detail.

[(A1) process]

This process is a process of forming the heat-storage layer 3p on the surface of the base film 1 . First, a varnish for forming the heat storage layer 3p is prepared. A varnish contains one or more monomers, a crystalline component, a photoinitiator (it is also called a photocuring agent or a photoradical generator), and an additive (for example, antioxidant) as needed. As long as a varnish in which each material is sufficiently and uniformly mixed is obtained, heating is not required at the time of preparation of the varnish.

The heat storage layer 3p is formed on the surface of the base film 1 by supplying a varnish on the surface of the base film 1 . For example, a single-screw or twin-screw kneading extrusion device is used for supplying the varnish. When forming the heat storage layer 3p by a roll-to-roll method, the thickness of the heat storage layer 3p can be controlled by adjusting the conveyance speed of the base film 1, and the varnish supply amount per unit time.

Here, the case where the heat storage layer 3p is formed using varnish (no solvent is used) is exemplified, but instead of the varnish, a solution containing the above material and a solvent (for example, water, methyl ethyl ketone) is prepared, After coating this on the surface of the base film 1, you may dry-remove a solvent. In addition, it is preferable to perform preparation of a varnish or a solution, and formation of the heat storage layer 3p under low oxygen conditions (for example, in an inert gas environment) with an oxygen concentration of 5 volume% or less. In addition, in order to suppress exposure of the heat-storage layer 3p to oxygen, a cover film (not shown) having oxygen barrier properties may be affixed to the heat-storage layer 3p. This cover film is peeled at the appropriate timing of a subsequent process.

[(B1) process]

This step is a step of curing the heat storage layer 3p by irradiating active energy rays to the heat storage layer 3p in a state where the temperature of the heat storage layer 3p is higher than the phase transition temperature of the heat storage component. A polymer matrix is formed by copolymerization of a plurality of monomers included in the heat storage layer 3p before curing, and the polymer matrix is in a state in which a crystalline component is included. As a specific example of an active energy ray, an ultraviolet-ray, an electron beam, and a visible light are mentioned. Hereinafter, the photocuring process by an ultraviolet-ray is demonstrated.

Fig. 2(b) is a cross-sectional view schematically showing a mode in which the heat storage layer 3p moves together with the base film 1 in the heating furnace 50 provided with the ultraviolet irradiation device 60 . The arrow A in the figure means the moving direction of the base film 1 and the thermal-storage layer 3p. In the present embodiment, at least the thermal storage layer 3p (before curing) in a state higher than the phase transition temperature of the crystalline component is photocured to form the thermal storage layer 3 (after curing) having excellent flexibility. can do. The phase transition temperature of the crystalline component means the temperature of the melting peak measured as follows using a differential scanning calorimeter. That is, the temperature is arbitrarily decreased to -40°C at a rate, held at -40°C for 1 minute, then heated to 80°C at a rate of 10°C/min, maintained at 80°C for 1 minute, and then held at a rate of 10°C/min. The temperature is lowered to -40°C, and then maintained at -40°C for 3 minutes, then the temperature is raised again to 80°C at 10°C/min to measure the thermodynamics of the crystalline component, and the temperature of the melting peak is the phase transition temperature.

In FIG.2(b), in the heating furnace 50, from the ultraviolet irradiation device 60 arrange|positioned on one side (upper side in the same figure) of the base film 1 toward the heat storage layer 3p, ultraviolet-ray Although the case of irradiating was exemplified, as shown in Fig. 2(c), the ultraviolet irradiation device 60 is also disposed on the other side (lower side in the same figure) of the base film 1, and the heat storage layer ( You may irradiate an ultraviolet-ray toward the heat storage layer 3p from both sides of 3p). In addition, in this case, as the base film 1, the film with high transparency with respect to an ultraviolet-ray is used. When the heat-storage layer 3p contains a filler, the transparency of the heat-storage layer 3p tends to decrease, but the heat-storage layer 3p is sufficiently thin or the heat-storage layer 3p is removed from both sides of the heat-storage layer 3p. By irradiating an ultraviolet ray toward it (refer to FIG. 2(c) ), the curing reaction of the heat storage layer 3p can be sufficiently advanced.

[(C1) process]

This process is a process of forming the adhesion layer 5 and the cover film 7 on the surface of the heat storage layer 3 after a photocuring process. As shown in Fig. 2 (b) and Fig. 2 (c), the roll of the adhesive layer 5 is prepared, and the adhesive layer 5 is transferred to the heat storage layer 3 via a plurality of rollers R1 and R2. ) to be attached to the A cover film 7 is affixed to the pressure-sensitive adhesive layer 5 from the viewpoint of preventing foreign matter from adhering to the pressure-sensitive adhesive layer 5 . Through these steps, the thermal-storage sheet 10 shown in Fig. 1 is produced.

In addition, when the self-reliance of the adhesive layer 5 is insufficient, as shown in Fig. 3(a), a support layer 5a such as a PET film is sandwiched between two adhesive layers 5b and 5b ( 5A) is prepared, and what is necessary is just to bond this to the heat storage layer 3 . Instead of the adhesive sheet 5A having a three-layer structure, as shown in FIG. From a viewpoint of adhesiveness with the heat storage layer 3, it is preferable that the surface 5f of the support layer 5a of the adhesive sheet 5B has suitable surface roughness.

As mentioned above, although 1st Embodiment was demonstrated in detail, you may change 1st Embodiment as follows. For example, in the step (C1) after the step (B1), the aspect in which the adhesion layer 5 is formed on the surface of the heat storage layer 3 after the photocuring treatment has been exemplified; As shown in FIG.4(b), you may form the adhesion layer 5 on the surface of the heat storage layer 3p before a photocuring process.

In the step (B1), although the aspect in which heating and ultraviolet irradiation are performed simultaneously in the heating furnace 50 is exemplified, as long as the heat storage layer 3p is a temperature higher than the phase transition temperature of the crystalline component, heating and ultraviolet irradiation are performed simultaneously you don't have to do That is, as shown in FIG.5(a) and FIG.5(b), the ultraviolet irradiation apparatus 60 may be arrange|positioned at the rear end of the heating furnace 50. As shown in FIG. What is necessary is just to irradiate an ultraviolet-ray with respect to the heat storage layer 3p which is a state in which a crystalline component is melt|dissolved by the residual heat after heating in the heating furnace 50, or an amorphous state. In addition, if the temperature of the heat storage layer 3p seems to be higher than the phase transition temperature of the crystalline component due to the irradiation of ultraviolet rays, it is not necessary to use the heating furnace 50 .

<Second embodiment>

In 1st Embodiment, although the aspect which hardens the thermal-storage layer 3p by photocuring process was illustrated, you may produce a thermal-storage sheet through the process of hardening the thermal-storage layer by thermosetting process. That is, the thermal-storage sheet 20 according to the second embodiment is manufactured through the following steps.

(A2) The process of forming the heat-storage layer 13p containing the heat-storage component which expresses heat-storage property by a phase transition, and a thermosetting agent on the surface of the base film 1

(B2) A step of curing the heat storage layer 13p by heating the heat storage layer 13p to a temperature 20°C or more higher than the phase transition temperature of the heat storage component

(C2) The process of forming the adhesion layer 5 and the cover film 7 on the surface of the heat storage layer 13 after thermosetting process

Hereinafter, the matter in which 2nd Embodiment differs from 1st Embodiment is mainly demonstrated.

[(A2) process]

Instead of the photoinitiator used in the first embodiment, a thermal polymerization initiator (also called a thermal curing agent or thermal radical generator) is used to prepare a varnish or a solution. What is necessary is just to perform preparation of a varnish or a solution on the temperature condition more than the phase transition temperature of a crystalline component, and less than the active temperature of a thermal radical generator. It is preferable that the radical generation start temperature (activation temperature) of a thermal radical generator is higher than the phase transition temperature of a crystalline component from a viewpoint of suppressing that a thermosetting reaction advances during preparation of a varnish or a solution. Specifically, preferred that the activation temperature of the heat generation radical claim to T _A ℃ and, when the phase transition temperature of the crystalline components in T _P ℃, satisfy the condition represented by inequality (1) below, and the inequality ( It is more preferable to satisfy the condition represented by 2).

0<T _A -T _P ≤100...(1)

20≤T _A -T _P ≤50...(2)

After preparing the varnish or the solution, the heat storage layer 13p is formed in the same manner as in the first embodiment.

[(B2) process]

This step is a step of curing the heat storage layer 13p by heating the heat storage layer 13p to a temperature 20° C. or more higher than the phase transition temperature of the heat storage component (preferably a temperature 20 to 50° C. higher) (FIG. 6). see (a)). A polymer matrix is formed by copolymerization of a plurality of monomers included in the heat storage layer 13p before curing, and the crystalline component is included in the polymer matrix.

[(C2) process]

This process is a process of forming the adhesion layer 5 and the cover film 7 on the surface of the heat storage layer 13 after a thermosetting process. What is necessary is just to prepare the roll of the adhesive layer 5, and just to make it bond the adhesive layer 5 to the heat storage layer 3 via several rollers R1 and R2, as shown to Fig.6 (a). A cover film 7 is affixed to the pressure-sensitive adhesive layer 5 from the viewpoint of preventing foreign matter from adhering to the pressure-sensitive adhesive layer 5 . Through these steps, the thermal-storage sheet 20 shown in Fig. 7 is produced.

In addition, here, in the (C2) process after the (B2) process, the aspect which forms the adhesion layer 5 on the surface of the heat storage layer 13 after a thermosetting process was illustrated, but FIG.6(b) As shown in , the adhesive layer 5 may be formed on the surface of the heat storage layer 13p before the deterioration treatment.

In 1st Embodiment and 2nd Embodiment, although the aspect which forms the adhesion layer 5 was illustrated with respect to the heat storage layer formed in the base film 1, For example, the adhesion layer 5 is one surface. The formed base film 1 may be prepared, and the heat-storage layers 3 and 13 may be formed on the surface of the adhesion layer 5 . What is necessary is just to transfer the adhesive layer 5 to the heat storage layer side by passing through the photocuring process or thermosetting process after that. In this case, the thermal-storage sheet 25 of the layer structure shown in FIG. 8 is obtained.

Hereinafter, the heat storage layer which concerns on 1st Embodiment and 2nd Embodiment is demonstrated in detail. The heat storage layers 3 and 13, in one embodiment, include a monomer, a photoinitiator (photocuring agent, photoradical generator) or thermal polymerization initiator (thermal curing agent, thermal radical generator), and a crystalline component It is formed by performing a photocuring process or a thermosetting process with respect to a curable composition.

In this case, in the step (B1) of the first embodiment, the heat storage layer 3p is irradiated with active energy rays in a state where the temperature of the thermal storage layer 3p is higher than the phase transition temperature of the crystalline component. When two or more types of crystalline components are included, the temperature of the heat storage layer 3p is higher than the phase transition temperature of at least one type of the crystalline component at the time of irradiation with an active energy ray, Preferably, 2 or more types of crystalline components are included. It is a state above the temperature of all phase transitions of the crystalline component.

Similarly, in the step (B2) of the second embodiment, the heat storage layer 13p is heated to a temperature 20°C higher than the phase transition temperature of the crystalline component. When two or more crystalline components are included, the temperature of the heat storage layer 3p during heating is higher than the phase transition temperature of at least one of the crystalline components, Preferably, all phase transitions of the two or more crystalline components higher than the temperature.

The monomer may be, for example, 1 type or 2 or more types of the monofunctional (meth)acrylate represented by following formula (1).

[Formula 1]

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group or a group having a polyoxyalkylene chain.

When R ² is an alkyl group, the alkyl group may be linear or branched. The number of carbon atoms of the alkyl group may be, for example, 1 to 30. 1-11, 1-8, 1-6, or 1-4 may be sufficient as carbon number of an alkyl group. The number of carbon atoms of the alkyl group may be 12 to 30, 12 to 28, 12 to 24, 12 to 22, 12 to 18, or 12 to 14, and in this case, the monomer itself can function as a heat storage component having heat storage property. Therefore, the polymer matrix itself comprised of the said monomer also has heat storage property, and the improvement of the heat storage amount is attained further.

When R ² is a group having a polyoxyalkylene chain, the monomer itself can function as a heat storage component having heat storage property. is planned The group which has a polyoxyalkylene chain represented by R<^2> may also contribute represented by following formula (3).

[Formula 2]

In the formula, R ^a represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, R ^b represents an alkylene group, n represents an integer of 2 to 90, and * represents a bond.

The ^{alkyl group represented by R a} may be linear or branched. Carbon ^{number of the alkyl group represented by R a} becomes like this. Preferably it is 1-15, More preferably, it is 1-10, More preferably, it is 1-5. R ^a is particularly preferably a hydrogen atom or a methyl group.

The ^{alkylene group represented by R b} may be linear or branched. R ^b may be, for example, an alkylene group having 2 to 4 carbon atoms. ^{A plurality of R b s} present in the polyoxyalkylene chain may be the same as or different from each other. The polyoxyalkylene chain preferably has one or more selected from the group consisting of an oxyethylene group, an oxypropylene group and an oxybutylene group, and more preferably an oxyethylene group and an oxypropylene group. It has 1 type or 2 types selected from the group, More preferably, it has an oxyethylene group.

From the viewpoint of further improving the amount of heat storage, n is preferably an integer of 4 to 80, 6 to 60, 9 to 40, 9 to 30, 10 to 30, 15 to 30, or 15 to 25.

A monomer may further contain the polyfunctional (meth)acrylate which has two or more (meth)acryloyl groups in addition to said monofunctional (meth)acrylate. In this case, crosslinking derived from polyfunctional (meth)acrylate may be formed in the polymer matrix in the heat storage layers 3 and 13 .

In addition to said monofunctional (meth)acrylate, a monomer is copolymerizable with monofunctional (meth)acrylate, and may further contain the monomer (reactive monomer) which has a reactive group. In this case, after polymerizing the monofunctional (meth)acrylate and the reactive monomer, the curable composition (thermal storage layer) can be further cured by reacting the reactive group contained in the reactive monomer with a curing agent described later.

The reactive group in the reactive monomer is a group capable of reacting with a curing agent described later, for example, at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, an isocyanate group, an amino group, and an epoxy group. to be. That is, the reactive monomer is, for example, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an isocyanate group-containing monomer, an amino group-containing monomer, or an epoxy group-containing monomer.

Examples of the carboxyl group-containing monomer include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and the like. .

As the hydroxyl group-containing monomer, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl ( hydroxyalkyl (meth)acrylates such as meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, and 12-hydroxylauryl (meth)acrylate; Hydroxyalkylcycloalkane (meth)acrylates, such as (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, etc. are mentioned. The hydroxyl group-containing monomer may be hydroxyethyl (meth)acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, or the like.

As an isocyanate group containing monomer, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, etc. are mentioned.

The isocyanate group in the isocyanate group-containing monomer may be blocked (protected) by a blocking agent (protecting group) that can be detached by heat. That is, the monomer which has a block isocyanate group represented by following formula (4-1) may be sufficient as an isocyanate group containing monomer.

[Formula 3]

In the formula, B represents a protecting group, and * represents a bond.

The protecting group in the block isocyanate group may be a protecting group capable of being detached (deprotected) by heating (eg, heating at 80 to 160°C). In the block isocyanate group, a substitution reaction between the blocking agent (protecting group) and the curing agent described later may occur under deprotection conditions (eg, under heating conditions of 80 to 160° C.). Alternatively, in a block isocyanate group, an isocyanate group may be produced|generated by deprotection, and an isocyanate group may react with the hardening|curing agent mentioned later.

As a blocking agent in a block isocyanate group, Oxime monomers, such as form aldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime; pyrazole monomers such as pyrazole, 3-methylpyrazole, and 3,5-dimethylpyrazole; lactam monomers such as ε-caprolactam, δ-valerolactam, γ-butyrolactam and β-propiolactam; mercaptan monomers such as thiophenol, methylthiophenol, and ethylthiophenol; acid amide monomers such as acetate amide and benzamide; and imide monomers such as succinic acid imide and maleic acid imide.

Examples of the monomer having a block isocyanate group include 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, 2-(0-[1'-methylpropylideneamino] carboxyamino) methacrylate.

As the amino group-containing monomer, for example, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate , N,N-diethylaminopropyl (meth)acrylate, and the like.

Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, glycidyl α-ethyl (meth)acrylate, glycidyl α-n-propyl (meth)acrylate, α-n-butyl (meth)acrylic acid Glycidyl, (meth)acrylic acid-3,4-epoxybutyl, (meth)acrylic acid-4,5-epoxypentyl, (meth)acrylic acid-6,7-epoxyheptyl, α-ethyl (meth)acrylic acid-6, 7-epoxyheptyl, (meth)acrylic acid-3-methyl-3,4-epoxybutyl, (meth)acrylic acid-4-methyl-4,5-epoxypentyl, (meth)acrylic acid-5-methyl-5,6- Epoxyhexyl, (meth)acrylic acid-β-methylglycidyl, α-ethyl (meth)acrylic acid-β-methylglycidyl, and the like.

The content of the reactive monomer may be, for example, 0.5 parts by mass or more, 1 part by mass or more, or 1.5 parts by mass or more, 10 parts by mass or less, 8 parts by mass or less, or 5 parts by mass or less may be sufficient.

The total amount of the monomer content may be 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more based on the total amount of the curable composition. , may be 99.9 mass % or less.

The photopolymerization initiator is, for example, a benzoin ether-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an α-ketol-based photopolymerization initiator, an aromatic sulfonyl chloride-based photopolymerization initiator, a photoactive oxime-based photopolymerization initiator, a benzoin-based photopolymerization initiator, and a benzyl-based photopolymerization initiator. An initiator, a benzophenone type photoinitiator, a ketal type photoinitiator, a thioxanthone type photoinitiator, an acylphosphine oxide type photoinitiator, etc. may be sufficient.

Examples of the benzoin ether-based photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1, 2-diphenylethan-1-one (trade name: Irgacure 651, manufactured by BASF), anisole methyl ether, etc. are mentioned. Examples of the acetophenone-based photopolymerization initiator include 1-hydroxycyclohexylphenylketone (trade name: Irgacure 184, manufactured by BASF), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1-[ 4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (trade name: Irgacure 2959, manufactured by BASF), 2-hydroxy-2-methyl -1-phenyl-propan-1-one (trade name: Irgacure 1173, manufactured by BASF), methoxyacetophenone, and the like.

Examples of the α-ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methylpropan-1-one, and the like. can be heard As an aromatic sulfonyl chloride type|system|group photoinitiator, 2-naphthalene sulfonyl chloride etc. are mentioned. Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime.

Benzoin etc. are mentioned as a benzoin type photoinitiator. Benzyl etc. are mentioned as a benzyl type photoinitiator. Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and α-hydroxycyclohexylphenylketone. As a ketal-type photoinitiator, benzyl dimethyl ketal etc. are mentioned. Examples of the thioxanthone-based photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, and 2,4-dichlorothioxanthone. , 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.

Examples of the acylphosphine-based photopolymerization initiator include bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, bis (2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl)phosphine oxide, bis(2,6- Dimethoxybenzoyl)-(1-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl) Cyclohexyl phosphine oxide, bis (2,6-dimethoxybenzoyl) octylphosphine oxide, bis (2-methoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2-methoxy Benzoyl) (1-methylpropan-1-yl) phosphine oxide, bis (2,6-diethoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2,6-diethoxy) Benzoyl) (1-methylpropan-1-yl) phosphine oxide, bis (2,6-dibutoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2,4-dimethoxy Benzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) (2,4-dipentoxyphenyl) phosphine oxide, bis (2,6-dimethyl Toxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, bis( 2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethyl Phosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-dia Isopropylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-4-methylphenylphosphine oxide, bis(2 ,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,3,5,6-tetramethylphenylphosphine oxide, bis( 2,4,6-trimethylbenzoyl)-2,4-di-n-butoxyphenyl Phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4, 6-trimethylbenzoyl)isobutylphosphine oxide, 2,6-dimethoxybenzoyl-2,4,6-trimethylbenzoyl-n-butylphosphine oxide, bis(2,4,6-trimethylbenzoyl) Phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-dibutoxyphenylphosphine oxide, 1,10-bis[bis(2,4,6-trimethylbenzoyl)phosphine Oxide] decane, tri(2-methylbenzoyl)phosphine oxide, etc. are mentioned.

The photoinitiator mentioned above may be used individually by 1 type or in combination of 2 or more type.

Examples of the thermal polymerization initiator include azo compounds such as azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile, and azodibenzoyl. , benzoyl peroxide, lauroyl peroxide, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-2-ethylhexanoate, 1,1-t-butylperoxy-3,3,5- Organic peroxides, such as trimethylcyclohexane and t-butylperoxyisopropyl carbonate, etc. are mentioned. A thermal polymerization initiator may be used individually by 1 type or in combination of 2 or more type.

The content of the photopolymerization initiator or thermal polymerization initiator is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, more preferably 0.01 parts by mass or more, more preferably 0.01 parts by mass or more, with respect to 100 parts by mass in total of the monomer content, from the viewpoint of appropriately advancing the polymerization. is 0.05 parts by mass or more. The content of the photopolymerization initiator or thermal polymerization initiator is within a range suitable for the molecular weight of the polymer matrix in the thermal storage layers 3 and 13, while suppressing decomposition products and obtaining suitable adhesive strength when used as a thermal storage material. With respect to 100 mass parts of total content of , monomer, Preferably it is 10 mass parts or less, More preferably, it is 5 mass parts or less, More preferably, it is 3 mass parts or less, Especially preferably, it is 1 mass part or less.

The crystalline component is appropriately selected, for example, to have a phase transition temperature suitable for the target temperature depending on the intended use. A crystalline component has a solid-phase/liquid-phase transition point (melting point) which shows a solid-phase/liquid phase transition at -30-120 degreeC, for example from a viewpoint of acquiring a thermal storage effect in a practical use range.

The crystalline component is, for example, a chain (linear or branched (branched)) saturated hydrocarbon compound (paraffinic hydrocarbon compound), fatty acids, natural wax, petroleum wax, sugar alcohol, polyalkylene glycol It may be a call or the like. The said crystalline component may be 1 type, or 2 or more types of these.

The chain saturated hydrocarbon compound (paraffinic hydrocarbon compound) is specifically, n-decane (C10 (number of carbon atoms, hereinafter the same), -29°C (phase transition temperature (melting point), hereinafter the same)), n-unde Caine (C11, -25°C), n-Dodecane (C12, -9°C), n-Tridecaine (C13, -5°C), n-Tetradecane (C14, 6°C), n-pentade Cain (C15, 9℃), n-hexadecane (C16, 18℃), n-heptadecaine (C17, 21℃), n-octadecane (C18, 28℃), n-nonadecaine ( C19, 32°C), n-eicosane (C20, 37°C), n-henicosein (C21, 41°C), n-docosein (C22, 46°C), n-tricosein (C23, 47°C) ); n-octacocein (C28, 65℃), n-nonacosane (C29, 66℃), n-triacontaine (C30, 67℃), n-tetracontaine (C40, 81℃), n- It may be pentacontaine (C50, 91°C), n-hexacontaine (C60, 98°C), n-hexane (C100, 115°C), or the like. The chain saturated hydrocarbon compound may be a branched saturated hydrocarbon compound having the same number of carbon atoms as these linear saturated hydrocarbon compounds. A mixture of 2 or more types of these compounds may be sufficient as a chain|strand-shaped saturated hydrocarbon compound.

The compound having a long-chain alkyl group may be, for example, a fatty acid ester having an alkyl group having 9 or more carbon atoms. The fatty acid ester is, for example, an ester of a fatty acid having an alkyl group having 9 or more carbon atoms (that is, a fatty acid having 10 or more carbon atoms) and an aliphatic alcohol. Carbon number of a fatty acid is 10-40, 10-30, or 10-25, for example. Carbon number of an aliphatic alcohol is 1-20, 1-10, or 1-8, for example. The aliphatic alcohol may be, for example, 1-3 alcohol, preferably monohydric alcohol. When the fatty alcohol is a dihydric or higher polyhydric alcohol, the fatty acid ester may be a partial ester in which some of the hydroxyl groups of the polyhydric alcohol are esterified, or a complete ester in which all of the hydroxyl groups of the polyhydric alcohol are esterified.

Fatty acid esters, specifically, glycerol monomyristic acid (44 to 48 ° C (phase transition temperature (melting point), the same hereinafter)), methyl stearate (37 to 41 ° C), ethyl stearate (33 to 35 ° C), Butyl palmitate (32-35 ℃), ethyl palmitate (18-21 ℃), butyl stearate (22-24 ℃), ethyl myristate (10-13 ℃), 2-ethylhexyl stearate ( 10℃), methyl laurate (5℃), tallow fatty acid 2-ethylhexyl ester (1℃), palmitic acid 2-ethylhexyl (0℃), myristic acid isopropyl (-5℃), lauric acid Ethyl acid (-10°C), methyl oleate (-20°C), ethyl oleate (-32°C), or the like may be used.

The compound having a long-chain alkyl group may be a compound having an alkyl group having 9 or more carbon atoms other than the fatty acid ester. The compound having such a long-chain alkyl group may be, for example, a fatty acid having an alkyl group having 9 or more carbon atoms, an aliphatic alcohol having an alkyl group having 9 or more carbon atoms, or an aliphatic ether having an alkyl group having 9 or more carbon atoms.

Specific examples of the sugar alcohol include erythritol including meso-erythritol, L-erythritol, D-erythritol, and DL-erythritol, pentaerythritol, dipentaerythritol, xylitol, D-arabitol, L-arabitol and arabitol including DL-arabitol, D-sorbitol, L-sorbitol, and sorbitol including DL-sorbitol, D-mannitol, L-mannitol, and DL-mannitol mannitol containing mannitol, and threitol containing D-threitol, L-threitol, and DL-threitol may be used.

Specifically, for example, polyethylene glycol, polypropylene glycol, polybutylene glycol, etc. may be sufficient as polyalkylene glycol, Preferably it is polyethylene glycol.

The weight average molecular weight (Mw) of polyalkylene glycol may be 800 or more, 900 or more, or 1000 or more, and 2000 or less, 1900 or less, or 1800 or less may be sufficient as it.

The crystalline component (heat-storage component) may be contained in the curable composition as a heat-storage capsule encapsulated in the capsule. The heat-storage capsule has a crystalline component (heat-storage component) and an outer shell (shell) containing the heat-storage component.

The outer shell (shell) containing the crystalline component is preferably formed of a material having a heat-resistant temperature sufficiently higher than the transition point (melting point) of the crystalline component. The material forming the outer shell has a heat resistance temperature of, for example, 30°C or higher, preferably 50°C or higher, with respect to the transition point (melting point) of the crystalline component. In addition, the heat resistance temperature is the temperature at which the weight decreased by 1% when the weight loss of the capsule is measured using a differential thermal thermogravimetry simultaneous measurement device (for example, TG-DTA6300 (manufactured by Hitachi High-Tech Sciences, Ltd.)). is defined

As the material for forming the outer shell, a material having strength according to the use of the thermal storage material formed of the curable composition is appropriately selected. The outer shell, Preferably, you may form from a melamine resin, an acrylic resin, a urethane resin, a silica, etc. As microcapsules which have an outer shell containing a melamine resin, BA410xxP, 6C, BA410xxP, 18C, BA410xxP, 37C made by Outlast Technology Co., Ltd., Thermomemory FP-16, FP-25, FP made from Mitsubishi Seishi Co., Ltd. product, for example -31, FP-39, Miki Riken High School Co., Ltd. Rikken resin PMCD-15SP, 25SP, 32SP, etc. are illustrated. As microcapsules which have an outer shell containing an acrylic resin (polymethyl methacrylate resin), BASF Corporation MicronalDS5001X, 5040X, etc. are illustrated. As microcapsules which have an outer shell containing silica, Miki Riken Kogyo Co., Ltd. Ricken resin LA-15, LA-25, LA-32, etc. are illustrated.

The content of the crystalline component in the thermal storage capsule is preferably 20 mass % or more, more preferably 60 mass % or more, based on the total amount of the thermal storage capsule, from the viewpoint of further enhancing the thermal storage effect, the volume of the crystalline component From a viewpoint of suppressing the breakage of the capsule by a change, Preferably it is 80 mass % or less.

The heat storage capsule may further contain graphite, metal powder, alcohol, etc. in an outer shell for the purpose of adjusting the thermal conductivity, specific gravity, etc. of a capsule.

The particle diameter (average particle diameter) of the heat-storage capsule is preferably 0.1 µm or more, more preferably 0.2 µm or more, still more preferably 0.5 µm or more, preferably 100 µm or less, and more preferably 50 µm or less. The particle diameter (average particle diameter) of the heat-storage capsule is measured using a laser diffraction particle size distribution analyzer (eg, SALD-2300 (manufactured by Shimadzu Corporation).

The content of the heat-storage capsule is preferably 20 mass% or more, more preferably 30 mass% or more, still more preferably 40 mass% or more, based on the total amount of the curable composition from the viewpoint of further enhancing the heat-storage effect. The content of the heat-storage capsule is preferably 90% by mass or less, more preferably 85% by mass or less, more preferably based on the total amount of the curable composition from the viewpoint of suppressing drop-off of the heat-storage capsule from the cured product of the curable composition. is 80% by mass or less.

When the curable composition contains the above-mentioned reactive monomer, the curable composition preferably further contains a curing agent capable of reacting with the reactive group contained in the reactive monomer.

Examples of the curing agent include an isocyanate curing agent, a phenol curing agent, an amine curing agent, an imidazole curing agent, an acid anhydride curing agent, and a carboxylic acid curing agent. According to the kind of reactive group contained in the compound represented by Formula (4), these hardening|curing agents are suitably selected as 1 type individually or in 2 or more types of combinations. For example, when the reactive group is an epoxy group, the curing agent is preferably a phenol-based curing agent or an imidazole-based curing agent.

Examples of the isocyanate-based curing agent include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate, or a mixture thereof) (TDI), phenylenedi isocyanate Anate (m- or p-phenylenediisocyanate, or mixtures thereof), 4,4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate (NDI), diphenyl Methanediisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethanediisocyanate, or mixtures thereof) (MDI), 4,4'-toluidinedia Isocyanate (TODI), 4,4'-diphenylether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate, or mixtures thereof) ) (XDI), tetramethylxylylenediisocyanate (1,3- or 1,4-tetramethylxylylenediisocyanate, or mixtures thereof) (TMXDI), ω,ω'-diisocyanate and aromatic diisocyanates such as anate-1,4-diethylbenzene.

As the isocyanate-based curing agent, trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylenedia Isocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexa Aliphatic diisos such as methylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanate methylcapate Cyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexanediisocyanate (1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (isophoronediisocyanate) (IPDI), methylene Bis (cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylenebis (cyclohexyl isocyanate), their trans, trans-forms, trans, cis- sieve, cis,cis-form, or mixtures thereof) (H12MDI), methylcyclohexanediisocyanate (methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornene diisocyanate (various isomers or mixtures thereof) (NBDI), bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanide) and alicyclic diisocyanates such as anatomethyl)cyclohexane or a mixture thereof) (H6XDI).

Examples of the phenolic curing agent include bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenylphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol F, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenylphenol, 1-(4-hydroxyphenyl)-2-[4-(1,1- Bis-(4-hydroxyphenyl)ethyl)phenyl]propane, 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis(3- methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, and a phenol compound having a diisopropylidene skeleton; phenolic compounds having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene; cresol compounds; ethylphenol compound; butylphenol compound; octylphenol compound; Novolac resins using various phenols as raw materials, such as bisphenol A, bisphenol F, bisphenol S, and naphthol compounds, phenol novolac resins containing xylylene skeleton, phenol novolac resins containing dicyclopentadiene skeleton, phenol furnace containing biphenyl skeleton Various novolak resins, such as a volak resin, a fluorene skeleton containing phenol novolak resin, and a furan skeleton containing phenol novolak resin, etc. are mentioned.

Examples of the amine-based curing agent include diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, Aromatic amines such as 1,5-diaminonaphthalene and m-xylylenediamine, ethylenediamine, diethylenediamine, hexamethylenediamine, isophoronediamine, bis(4-amino-3-methyldicyclohexyl) ) aliphatic amines such as methane and polyetherdiamine; and guanidine compounds such as dicyandiamide and 1-(o-tolyl)biguanide.

Examples of the imidazole-based curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, and 2-heptadecylimidazole. , 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-between Anoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 2,4- Diamino-6(2'-methylimidazole(1'))ethyl-s-triazine, 2,4-diamino-6(2'-undecylimidazole(1'))ethyl-s- Triazine, 2,4-diamino-6 (2'-ethyl-4-methylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6 (2'-methylimida Sol (1')) ethyl-s-triazine/isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2 -Phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoe Toxymethylimidazole etc. are mentioned.

Examples of the acid anhydride curing agent include aromatic carboxylic acid anhydrides such as phthalic anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenonetetracarboxylic acid anhydride, ethylene glycol trimellitic acid anhydride, and biphenyltetracarboxylic acid anhydride; anhydrides of aliphatic carboxylic acids such as azelaic acid, sebacic acid, and dodecane diacid;

Examples of the carboxylic acid-based curing agent include succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid.

0.01 mass % or more may be sufficient as content of a hardening|curing agent whole quantity basis, and 10 mass % or less, 5 mass % or less, or 1 mass % or less may be sufficient as it.

The curable composition preferably further contains an antioxidant from the viewpoint of improving the thermal reliability of the cured product (thermal storage layer) of the curable composition. The antioxidant may be, for example, a phenol-based antioxidant, a benzophenone-based antioxidant, a benzoate-based antioxidant, a hindered amine-based antioxidant, or a benzotriazole-based antioxidant.

The content of the antioxidant may be 0.1% by mass or more, 0.5% by mass or more, 0.8% by mass or more, or 1% by mass or more, 10% by mass or less, or 5% by mass or less, based on the total amount of the curable composition. From a viewpoint of being excellent in the softness|flexibility of hardened|cured material, Preferably it is 4 mass % or less, More preferably, it is 3 mass % or less, More preferably, it is 2.5 mass % or less, Especially preferably, it is 2 mass % or less.

In the first embodiment and the second embodiment, the case of forming a heat storage layer made of a material called a composite heat storage material was exemplified, but an acrylic resin having heat storage property is included (the above-mentioned crystalline component is not included) ) may be provided with a heat storage layer. That is, in another embodiment, instead of the curable composition described in the first embodiment and the second embodiment, the monomer component containing the first monomer represented by the following formula (1) is contained, and the crystalline component described above is contained. You may use the curable composition which does not do it.

[Formula 4]

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 12 to 30 carbon atoms or a monovalent group having a polyoxyalkylene chain.

In this case, since the first monomer itself can function as a heat-storage component having heat-storage property, the acrylic resin composed of the monomer also exhibits heat-storage property, so that a heat-storage layer can be formed even without a crystalline component. have.

In this case, in the step (B1) of the first embodiment, the heat storage layer 3p is irradiated with an active energy ray in a state where the temperature of the heat storage layer 3p is higher than the phase transition temperature of the first monomer. When two or more types of first monomers are included, the temperature of the heat storage layer 3p is higher than the phase transition temperature of at least one type of the first monomer at the time of irradiation with an active energy ray, Preferably, two or more types of first monomers are included. All phase transition temperatures of the first monomer are higher than the state.

Similarly, in the step (B2) of the second embodiment, the heat storage layer 13p is heated to a temperature 20°C higher than the phase transition temperature of the first monomer. When two or more types of first monomers are included, the temperature of the heat storage layer 3p during heating is higher than the phase transition temperature of at least one type of the first monomer, preferably, all the phase transitions of the two or more types of first monomers. higher than the temperature.

When R ² is an alkyl group, the alkyl group may be linear or branched. Carbon number of the alkyl group represented by R<^2> becomes like this. Preferably it is 12-28. When R ² is a group having ^{a polyoxyalkylene chain, the group having a polyoxyalkylene chain represented by R 2} may contribute to the group represented by the following formula (3).

[Formula 5]

In the formula, R ^a represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, R ^b represents an alkylene group, n represents an integer of 2 to 90, and * represents a bond.

The ^{alkyl group represented by R a} may be linear or branched. Carbon ^{number of the alkyl group represented by R a} becomes like this. Preferably it is 1-15, More preferably, it is 1-10, More preferably, it is 1-5. R ^a is particularly preferably a hydrogen atom or a methyl group.

The ^{alkylene group represented by R b} may be linear or branched. R ^b may be, for example, an alkylene group having 2 to 4 carbon atoms. ^{A plurality of R b s} present in the polyoxyalkylene chain may be the same as or different from each other. The polyoxyalkylene chain preferably has one or more selected from the group consisting of an oxyethylene group, an oxypropylene group and an oxybutylene group, and more preferably an oxyethylene group and an oxypropylene group. It has 1 type or 2 types selected from the group, More preferably, it has an oxyethylene group.

n is an integer of preferably 4 to 80, 6 to 60, 9 to 40, 9 to 30, 10 to 30, 15 to 30, or 15 to 25 from the viewpoint that the amount of heat storage of the thermal storage material is more excellent.

In other words, the (meth)acrylate which has the group which has a polyoxyalkylene chain represented by Formula (3) at the terminal of an ester group may be sufficient as a 1st monomer. As a 1st monomer, polyethyleneglycol (meth)acrylate (n in Formula (3) is an integer of 2-90. The same hereafter.), methoxypolyethylene glycol (meth)acrylate, polypropylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, polybutylene glycol (meth) acrylate, and selected from the group consisting of methoxy polybutylene glycol (meth) acrylate There is at least one

A commercial item can be used for the 1st monomer represented by Formula (1). Commercial products used as the first monomer are PP-500, PP-800, PP-1000, AP-400, AP-550, AP-800, 700PEP-350B, 10PEP-550B, 55PET- manufactured by Nichiyu Co., Ltd. 400, 30PET-800, 55PET-800, 30PPT-800, 50PPT-800, 70PPT-800, PME-100, PME-200, PME-400, PME-1000, PME-4000, AME-400, 50POEP-800B, 50AOEP-800B, Kyoeisha Chemical Co., Ltd. light ester 130MA, 041MA, light acrylate 130A, light acrylate NP-4EA, Nippon Nyukazai Co., Ltd. MA-30, MA-50, MA- 100, MA-150, RMA-1120, RMA-564, RMA-568, RMA-506, MPG130-MA, Antox MS-60, MPG-130MA, RMA-150M, RMA-300M, RMA-450M, RA-1020 , RA-1120, RA-1820, methoxypolyethylene glycol acrylate AM30G (n3), AM90G (n9), AM130G (n13), AM230G (n23), methoxypoly made by Shin-Nakamura Chemical Co., Ltd. Propylene glycol acrylate AM30PG, M40G, M-90G, M130G, M-230G, Sanyo Kasei Kogyo Co., Ltd. Eleminol RS-30, Osaka Yuki Chemical Co., Ltd. bisma MPE400A, bisma MPE550A or the like may be used.

The content of the first monomer may be 20 parts by mass or more, 25 parts by mass or more, or 30 parts by mass or more with respect to 100 parts by mass of the monomer component. is 60 mass parts or more, More preferably, it is 80 mass parts or more, For example, 98 mass parts or less may be sufficient.

A monomer component is copolymerizable with a 1st monomer, and may further contain the 2nd monomer which has a reactive group. The second monomer may be the same as the reactive monomer described above.

The content of the second monomer is 2 parts by mass or more, 3 parts by mass or more, 5 parts by mass or more, 7 parts by mass or more, or 8 parts by mass or more with respect to 100 parts by mass of the monomer component from the viewpoint that the amount of heat storage of the thermal storage material is more excellent. It may be sufficient, and 25 mass parts or less may be sufficient, Preferably it is 20 mass parts or less, More preferably, it is 15 mass parts or less, More preferably, it is 13 mass parts or less, Especially preferably, it is 10 mass parts or less.

In addition to a 1st monomer and a 2nd monomer, a monomer component can contain other monomers further as needed. Other monomers are, for example, dodecyl (meth) acrylate (lauryl (meth) acrylate), tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate ( Stearyl (meth) acrylate), docosyl (meth) acrylate (behenyl (meth) acrylate), tetracosyl (meth) acrylate, hexacosyl (meth) acrylate, octacosyl (meth) acrylate, etc. alkyl (meth) acrylate having a linear or branched alkyl group having 12 to 30 carbon atoms at the terminal of the ester group; Alkyl (meth) having an alkyl group having less than 12 carbon atoms (C 1 to 11) at the terminal of the ester group, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate ) acrylates; cycloalkyl (meth)acrylates having a cyclic hydrocarbon group at the terminal of the ester group, such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate; and the like. Other monomers are used individually by 1 type or in combination of 2 or more type.

In one embodiment, the monomer component is an alkyl (meth)acrylate having a first monomer, a second monomer, and, if necessary, a linear or branched alkyl group having 1 to 30 carbon atoms at the terminal of the ester group, and a cyclic It contains only at least 1 sort(s) of 3rd monomer selected from the group which consists of a cycloalkyl (meth)acrylate which has a hydrocarbon group at the terminal of an ester group. In other words, in one embodiment, a monomer component does not contain monomers other than a 1st monomer, a 2nd monomer, and a 3rd monomer (for example, the (meth)acryl monomer which has a siloxane skeleton). In one Embodiment, a monomer component may contain only a 1st monomer and a 2nd monomer, and in another one Embodiment, it may contain only a 1st monomer, a 2nd monomer, and a 3rd monomer.

The curable composition may further contain a curing agent capable of reacting with the reactive group contained in the second monomer. This hardening|curing agent may be the same as that of the hardening|curing agent mentioned above.

The curable composition may further contain a liquid medium. The liquid medium is not particularly limited as long as it is a solvent for dissolving each component or a dispersion medium for dispersing, and for example, a liquid medium made of an organic compound may be used. As the liquid medium, ethyl lactate, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N,N-dimethylformamide, methylethyl Ketone, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether, toluene, xylene, etc. are mentioned. These liquid media may be used individually by 1 type or in combination of 2 or more type.

When the curable composition contains a liquid medium, the content of the liquid medium is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 80% by mass or less, more preferably based on the total amount of the curable composition. Preferably, it is 70 mass % or less.

The curable composition may further contain a surface treating agent. The surface treatment agent may be, for example, a coupling agent. Examples of the coupling agent include an aminosilane coupling agent, an epoxysilane coupling agent, a phenylsilane coupling agent, an alkylsilane coupling agent, an alkenylsilane coupling agent, an alkynylsilane coupling agent, a haloalkylsilane coupling agent, Siloxane-based coupling agent, hydrosilane-based coupling agent, silazane-based coupling agent, alkoxysilane-based coupling agent, chlorosilane-based coupling agent, (meth)acrylsilane-based coupling agent, aminosilane-based coupling agent, isocyanurate silane Phosphorus coupling agent, ureidosilane coupling agent, mercaptosilane coupling agent, sulfide silane coupling agent, isocyanate silane coupling agent, etc. are mentioned. The coupling agent is preferably an aminosilane-based coupling agent from the viewpoint of reactivity with resin.

Content of the surface treating agent may be 0.01 mass % or more, 0.02 mass % or more, or 0.05 mass % or more, and 10 mass % or less, 5 mass % or less, or 2 mass % or less may be sufficient based on the curable composition whole quantity.

The curable composition may further contain a curing accelerator. As a hardening accelerator, an organophosphorus type hardening accelerator, a quaternary ammonium salt type hardening accelerator, a tin catalyst, etc. are mentioned, for example. You may use these hardening accelerators individually by 1 type or in combination of 2 or more type.

The content of the curing accelerator is, based on the total amount of the curable composition, preferably 0.005 mass% or more, more preferably 0.01 mass% or more, still more preferably 0.02 mass% or more, and preferably 1 mass% or less, more Preferably it is 0.5 mass % or less, More preferably, it is 0.2 mass % or less.

The curable composition can further contain other additives as needed. Examples of other additives include antioxidants, colorants, fillers, crystal nucleating agents, heat stabilizers, heat conductive materials, plasticizers, foaming agents, flame retardants, vibration dampers, dehydrating agents, and flame retardant aids (eg, metal oxides). . Other additives are used individually by 1 type or in combination of 2 or more type. 0.1 mass % or more may be sufficient as content of another additive based on curable composition whole quantity, and 30 mass % or less may be sufficient as it.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.

Each of the following components was used in the Example.

<Heat storage component>

(A-1) Cetyl acrylate ("Blemer CA" manufactured by Nichiyu Co., Ltd.)

(A-2) Stearyl acrylate ("Blemer SA" manufactured by Nichiyu Co., Ltd.)

(A-3) Methoxypolyethylene glycol acrylate (weight average molecular weight: 1000, "AM-230G" manufactured by Shin-Nakamura Chemical Co., Ltd.)

(A-4) Polyethylene glycol (weight average molecular weight: 1500, Sanyo Kasei Kogyo Co., Ltd. "PEG1540")

<Photoinitiator>

(B) 2-hydroxy-2-methyl-1-phenyl-propan-1-one ("Irgacure 1173" manufactured by BASF)

<Other ingredients>

(C-1) methyl methacrylate (manufactured by Nippon Shokubai Co., Ltd.)

(C-2) Butyl acrylate (manufactured by Fujifilm Wako Junyaku Co., Ltd.)

(C-3) aliphatic urethane diacrylate (“EBECRYL8402” manufactured by Daicel Co., Ltd.)

(C-4) Polyethylene glycol diacrylate (“A-6000” manufactured by Shin-Nakamura Chemical Co., Ltd.)

[Production of heat storage sheet]

(Examples 1-5)

Each component was heat-mixed at 50 degreeC by the compounding ratio shown in Table 1, and the curable composition was obtained. Next, on 50 degreeC conditions, using the bar coater, the curable composition was apply|coated on the PET film so that the thickness of the heat storage layer after hardening might be set to 200 micrometers. The heat storage layer was photocured by irradiating ultraviolet rays (wavelength: 365 nm, intensity: 200 mW) toward the heat storage layer in a nitrogen-substituted inert gas oven (temperature: 70°C). The irradiation amount of ultraviolet rays was 3000 mJ/cm ² .

(Comparative Examples 1 and 2)

Instead of making the temperature of the inert gas oven which carried out nitrogen substitution into 70 degreeC, except having set it as 30 degreeC, it carried out similarly to Examples 1-5, and performed the photocuring process of the heat storage layer.

[Measurement of phase transition temperature]

The phase transition temperature of the thermal storage component used in the Example and the comparative example was measured using the differential scanning calorimeter (The Perkin-Elmer company make, model number DSC8500). Specifically, the temperature was raised to 100°C at 20°C/min, held at 100°C for 3 minutes, then lowered to -30°C at a rate of 10°C/min, then held at -30°C for 3 minutes, then 10 The temperature was again raised to 100 °C at a rate of °C/min, and the thermal behavior was measured. The melting peak was taken as the phase transition temperature of the thermal-storage component. A result is shown in Table 1.

[Evaluation of flexibility]

When the PET film was peeled off and the sheet having only the heat storage layer was bent at 90° or more, fracture or partial damage was determined as B, and that no fracture or damage occurred even when bent at 90° or more was determined as A. A result is shown in Table 1.

[Table 1]

Industrial Applicability

According to the present disclosure, a method for efficiently manufacturing a thermal storage sheet having a thermal storage layer having excellent flexibility is provided.

One… base film
3, 13… Heat storage layer (after curing)
3p, 13p... Heat storage layer (before curing)
5, 5b... adhesive layer
5a… support layer
5A, 5B… adhesive sheet
7… cover film
10, 20, 25… heat storage sheet
50… heating furnace
60… UV irradiation device

Claims (17)

A step of forming a heat-storage layer comprising a heat-storage component that expresses heat-storage property by phase transition and a photocuring agent on the surface of the base film;
and curing the heat-storage layer by irradiating the heat-storage layer with active energy rays when the temperature of the heat-storage layer is higher than the phase transition temperature of the heat-storage component. The method according to claim 1,
The manufacturing method of the thermal-storage sheet which further includes the process of affixing a cover film with respect to the said thermal-storage layer before the said active energy ray irradiation. The method according to claim 1 or 2,
The base film has an adhesive layer on the surface on which the heat storage layer is formed,
The method for producing a thermal storage sheet, wherein the adhesive layer is transferred to the thermal storage layer side by passing through the step of irradiating the active energy ray. The method according to claim 1,
The manufacturing method of the thermal storage sheet which further includes the process of forming an adhesive layer on the surface of the said thermal storage layer before or after the said active energy ray irradiation. 5. The method according to claim 4,
The manufacturing method of the thermal-storage sheet further comprising the process of affixing a cover film with respect to the said adhesive layer. 6. The method according to any one of claims 1 to 5,
The manufacturing method of a thermal-storage sheet comprising the process of separately preparing at least two layers of the said thermal-storage layer before or after the said active energy ray irradiation, and bonding them together. 7. The method according to any one of claims 1 to 6,
The base film has transparency to the active energy ray,
The manufacturing method of the thermal-storage sheet which irradiates the said active energy ray toward the said thermal-storage layer from the side of the said base film. A step of forming a heat-storage layer comprising a heat-storage component that expresses heat-storage property by a phase transition and a heat curing agent on the surface of the base film;
and curing the heat-storage layer by heating the heat-storage layer to a temperature higher than the phase transition temperature of the heat-storage component by at least 20°C. 9. The method of claim 8,
The manufacturing method of the thermal-storage sheet which further includes the process of affixing a cover film with respect to the said thermal-storage layer before being heated to the said temperature. 10. The method according to claim 8 or 9,
The base film has an adhesive layer on the surface on which the heat storage layer is formed,
The method for producing a thermal storage sheet, wherein the pressure-sensitive adhesive layer is transferred to the thermal storage layer side by passing through a step of heating to the temperature. 9. The method of claim 8,
The manufacturing method of the thermal storage sheet which further includes the process of forming an adhesive layer on the surface of the said thermal storage layer before or after being heated to the said temperature. 12. The method of claim 11,
The manufacturing method of the thermal-storage sheet further comprising the process of affixing a cover film with respect to the said adhesive layer. 13. The method according to any one of claims 8 to 12,
The manufacturing method of a thermal-storage sheet comprising the process of separately preparing at least two layers of the said thermal-storage layer before or after being heated to the said temperature, and bonding them together. 14. The method according to any one of claims 8 to 13,
When the activation temperature of the thermosetting agent is T _A ° C and the phase transition temperature of the heat storage component is T _P ° C, the conditions expressed by the following inequality (1) are satisfied.
0<T _A -T _P ≤100...(1) 15. The method according to any one of claims 8 to 14,
The method for manufacturing a thermal storage sheet, wherein the thermal storage layer further includes a filler. 16. The method according to any one of claims 1 to 15,
A method for producing a thermal-storage sheet, wherein each step is performed under low oxygen conditions with an oxygen concentration of 5% by volume or less. 17. The method of any one of claims 1 to 16,
The thickness of the heat storage layer is 10-500 μm, the method of manufacturing a heat storage sheet.

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