JP2003237868A - Heat storage material and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a safe heat storage material with sealability of a packaging container and high temperature waterproofness, and a heat storage material manufacturing method excellent in workability and efficiency. <P>SOLUTION: The heat storage material comprises a heat storage material composition containing an oily substance having heat storage ability by a change of phase as an essential component, which is sealed in a packaging container. The heat storage material contains the heat storage material composition present in a sealed region of the container per unit area of 0.1 kg/m<SP>2</SP>or less. The manufacturing method of the heat storage material includes a process of sealing the heat storage material composition containing the oily substance which liquifies due to the change of phase and obtains the heat storage ability and an oil thickener which reduces fluidity of the oily substance as essential components, which are sealed in the packaging container. The manufacturing method comprises a step of sealing the heat storage material composition so that the composition present in the sealed region of the container per unit area is 0.1 kg/m<SP>2</SP>or less. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a heat storage material and a method for manufacturing the same.

[0002]

2. Description of the Related Art A heat storage facility is installed in a corner of a building for the purpose of labor saving and efficiency improvement of air conditioning and heating energy for large buildings such as office buildings and factories, household use, etc., and environmental protection. For air conditioning, a system for temporarily storing heat by installing a plurality of heat storage devices each having a size of 4, 5 meters square has attracted attention. In such a heat storage device, a large number of heat storage materials having a side of several cm to several tens of cm are filled in the device, and a medium such as circulating water that transfers heat is passed through the device to store heat by energy such as electric power. By changing the phase of a substance, the latent heat of radiating heat at the phase change from solid to liquid and absorbing heat at the phase change from liquid to solid is utilized. For example, the heat storage material is cooled and solidified by night-time electric power, and the endothermic effect when the heat storage material is melted is used for cooling in the daytime.

Examples of the heat storage substance constituting the heat storage material include clathrate, a mixture of ethylene glycol and water, a paraffin mixture having about 10 to 20 carbon atoms, and the like.
It is said that those which are cooled and solidified at about 4 ° C. and have a large heat of fusion are preferable. In a heat storage device filled with such a heat storage material, a medium such as circulating water guided from a water conduit (inlet) of the heat storage device moves while exchanging heat by passing through the gap of the filled heat storage material. Then, it reaches the water supply pipe (outlet) of the heat storage device, exits the heat storage device in a state where heat is sufficiently exchanged, and circulates in the building or the like through the pipeline.

Such a heat storage material is manufactured by filling an organic material or an inorganic material having a heat storage property by a phase change into a packaging container and sealing it. As a method of sealing the packaging container, (1) a method of filling a sealed portion of the packaging container with or without a filling material in contact with the filling material, and then heat-sealing by pressing with a heated mold,
(2) A method of heat-sealing by filling a sealed portion of a packaging container in a state where the filled material is in contact with the filled container and pressing the sealed portion with a heated mold while pressing the sealed portion.
(3) A method of sealing and sealing the sealed portion with a metal fitting such as a wire while filling the sealed portion of the packaging container with the filling material in contact with the sealed portion is performed.

Among these sealing methods, the sealing method (2) is preferable from the viewpoint of improving the filling efficiency and improving the heat storage performance by preventing air from being mixed in the packaging container. When an organic substance having a heat storage property due to a phase change is used, the organic substance enters into the seal portion as a contaminant, the sealability becomes insufficient, and the heat resistance of the seal portion becomes insufficient. On the other hand, when an inorganic substance having a heat storage property due to a phase change is used, these problems are less than those when an organic substance is used. big,
There is a practical problem that solidification is hindered even when the temperature is lower than the melting point, and the heat density for radiating heat is significantly reduced. Further, in the case of the sealing method of (3), there is a practical problem that industrial waste treatment such as landfill is required due to metal fittings such as wires when the heat storage material is discarded.

As an example of devising a heat storage material, for example, in JP-A-58-108391, a heat storage structure in which a latent heat storage material is filled in a tubular container made of a flexible sheet material, is disclosed in JP-A-57-65584. Heat storage tank in the bulletin,
JP-A-58-107123 discloses a vinyl house cultivation method in which a cylindrical container containing a latent heat storage agent is covered with a multi-film, and JP-A-59-41792 discloses a thermoplastic resin or a sheet-like material. A container for filling a heat storage agent in the form of a hollow body having the periphery sealed by fusion polymerization, JP-A-59-145489 discloses a heat storage tank having a heat storage material containing a heat storage material in a film and a supporting means therefor, JP-A-60-40046. Publication and JP-A-6
No. 0-88550 discloses a flexible container in which a heat storage material is sealed, and JP-A No. 60-235994 discloses a pair of films joined together leaving an inlet, and the latent heat storage material is injected from the inlet. And then the vicinity of the inlet is washed and the outside of the inlet is sealed.
No. 240095 discloses a heat storage element in which a latent heat storage material is housed in a flexible container, and JP-A-3-188188.
In the publication, a PET / NY (nylon) / PP accommodation bag,
Japanese Unexamined Patent Publication No. 8-94269 discloses a cylindrical heat storage capsule, and Japanese Patent No. 3136330 discloses a heat storage device including a flexible plastic container and a heat storage agent.

However, when a heat storage material is manufactured by the sealing method (2) or the like using an organic material having heat storage properties due to a phase change, heat storage is improved by improving the sealing property and heat resistance of the seal portion. Although it has been desired to improve the performance and durability of the material, there has been no research on the sealing property of the heat storage material so far, and the technology disclosed in these publications is There was room for improvement.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above situation, and is a safe heat storage material having sealing property of packaging containers and high temperature water resistance, and workability of the heat storage material. It is an object of the present invention to provide a highly efficient manufacturing method.

[0009]

[Means for Solving the Problems] The inventors of the present invention have studied various heat storage materials obtained by sealing a heat storage material composition containing an oily substance having heat storage properties as an essential component. It was found that the oily substance existing as a contaminant in the (sealing part) is related to the performance and durability of the heat storage material. When the amount of the foreign material is reduced, the adhesive strength of the sealing part is increased, and the heat storage material from the sealing part is increased. It has been conceived that the safety is increased due to the elimination of the leakage of the composition. That is, even if there are impurities in the sealing portion of the packaging container filled with the heat storage material composition having an oily substance having heat storage properties as an essential component, by defining the amount of impurities, the above problems can be solved satisfactorily. Was conceived. Furthermore, while filling the sealed portion of the packaging container with the filling material in contact with it, while squeezing the sealed portion in advance with a roller or the like, or by squeezing and then crimping with a heated mold, heat sealing is performed. When the method is applied, in addition to being excellent in workability and efficiency in the production of the heat storage material, the efficiency of filling the heat storage material composition into the packaging container is high because air is not mixed, and the pressure inside the packaging container is improved during sealing. It has been found that the present invention has the effect of preventing damage to the packaging container due to overfilling because it can be controlled, and has reached the present invention.

That is, the present invention relates to a heat storage material obtained by sealing a heat storage material composition containing an oily substance having a heat storage property due to a phase change as an essential component in a packaging container, wherein the heat storage material is a package container. A heat storage material in which the heat storage material composition present per unit area of the stop portion is 0.1 kg / m ² or less. less than,
The present invention will be described in detail.

The heat storage material of the present invention is obtained by sealing a heat storage material composition containing an oily substance having a heat storage property due to a phase change as an essential component in a packaging container. The above-mentioned "the heat storage material composition is sealed in a packaging container" means that the heat storage material composition is filled (enclosed) in the packaging container, and the sealed portion of the packaging container is sealed to thereby form the heat storage material composition. Is to be contained in a packaging container. In the present invention, the sealing method is not particularly limited, but from the viewpoint of workability and efficiency, a method of filling the sealed portion of the packaging container in a state where the heat storage material composition is in contact is suitable. As a specific method, (1) a method of tube-filling a laminate film with the heat storage material composition by a bag-making filling and packaging machine with a squeeze roller, and (2) sausage-type bag-making packaging machine (bundling) It is also possible to use a method of using a thread for pressure sealing. Among them, the sealing method (1) is preferable because the amount of impurities is easily measured. The bag-making filling and packaging machine with a squeeze roller means a bag-making and packaging machine that can push out impurities at the sealed part by a squeeze roller, and a sausage-type bag-making and packaging machine is a tube made of binding yarn or the like. It means a bag-making filling and packaging machine capable of sealing a film.

The packaging method in the above-mentioned sealing method (1) includes, for example, pillow, square, and pyramid pouch (tetrapack). What is the pillow form?
The lower part of the tubular film is sealed with a sealer (device for sealing the film by heat), and the upper part is sealed in the same direction after filling the filling material. The tetragonal form is laminated. The three sides of the film are sealed with a sealer, and the top is sealed after filling with the filling.The pyramid pouch is a tubular film in which the bottom is sealed with a sealer and the filling is filled. 9 after the upper part
This is a form in which sealing is performed in directions different by 0 °.

In the heat storage material of the present invention, the heat storage material composition present per unit area of the sealing portion of the packaging container is 0.1 kg / m 2.
² or less. The heat storage material composition present per unit area of the sealed portion of the packaging container is also referred to as a contaminant. 0.1k
If it exceeds g / m ² , the adhesive strength of the sealed portion of the packaging container becomes insufficient, and the heat storage material composition leaks from the sealed portion. When it is 0.1 kg / m ² or less, the heat storage material has a sealing property of the packaging container and high temperature water resistance that realizes high safety. More preferably at 0.05 kg / m ² or less, still more preferably 0.02 kg / m ² or less.

In the present invention, the amount of contaminants is controlled as described above, but the sealing site for controlling the amount of contaminants is only the site sealed in contact with the heat storage material composition. It is preferable that In addition, normally, when the heat storage material composition is filled in a sealed portion of the packaging container while touching the heat storage material composition, the amount of the above-mentioned impurities cannot be set to 0 kg / m ² , but the heat storage material composition is not touched. In the case of filling with, the amount of the above contaminants can be set to 0 kg / m ² .
The method of controlling the amount of impurities is not particularly limited, for example, after adjusting the amount of impurities by squeezing the sealing site in advance using a rubber plate, a rubber roller, a metal roller, etc., the sealing site is a hot plate or impulse. The amount of impurities can be controlled by heat-sealing with a sealer or the like, or by sealing with a binding thread or the like.

As a method of measuring the amount of impurities, for example, the sealing site of the packaging container is cut out, the film containing the impurities is weighed, and the basis weight (kg / m ² ) of the film is measured from the film layer at another site. , Can be measured from the difference. The specific method is shown below. The basis weight X (kg / m ² ) of the film used is measured. Cut out the sealing part,
The area S (m ² ) of the sealed portion is measured. Next, the weight Y (kg) of the film containing the attached contaminants and the total area S '(m ² ) of the film covering the cut-out sealing portion were measured, and the packaging container was calculated from the difference from the basis weight of the film by the following formula. Amount of heat storage material composition (contamination) per unit area of sealed part of Z (k
g / m ² ) is calculated. Amount of heat storage material composition (contamination) per unit area of the sealing portion of the packaging container Z (kg / m ² ) = (film weight Y (kg) including the adhered contaminants) -area weight X (kg / m ² ) × total area S ′ (m ² )) of the film covering the cut-out sealing part / area S (m ² ) of the sealing part

The present invention also liquefies by phase change to store heat.
Oily substances that have the property of reducing the fluidity of the above oily substances
Packing a heat storage material composition containing an oil thickening agent as an essential component
A method of manufacturing a heat storage material including a step of sealing in a container.
Therefore, the manufacturing method of the heat storage material is as follows.
0.1 kg / m of heat storage material composition present per unit area
²In the method of manufacturing the heat storage material that is sealed as follows
is there.

In the heat storage material manufacturing method, since the heat storage material composition contains an oil thickener that reduces the fluidity of the oily substance, the fluidity of the oily substance is reduced, so that heat storage and heat dissipation are performed. When freezing and thawing are repeated, leakage such as exudation of the oily substance is suppressed, ignition of the oily substance is suppressed, and a highly safe heat storage material can be stably obtained. Similarly, by sealing so that the amount of contaminants becomes a certain value or less, the heat storage material has the sealing property of the packaging container and the high temperature water resistance that realizes high safety. The preferred forms of the amount of impurities and the sealing method are the same as above.

In the above method for producing a heat storage material, a heat storage material composition containing an essential substance, an oily substance and an oil thickener, may be produced and filled in a packaging container to be sealed. After each of them is filled in a packaging container, the heat storage material composition may be manufactured and sealed in the packaging container.

The present invention further provides a method for producing a heat storage material obtained by encapsulating a heat storage material composition obtained by polymerizing a monomer component in an oily substance having a heat storage property by liquefying by a phase change into a packaging container. In the method for producing a heat storage material, the heat storage material composition present per unit area of the sealing portion of the packaging container is 0.1
It is also a method of manufacturing a heat storage material which is sealed so as to be less than kg / m ² .

In the above method for producing a heat storage material, the oily substance is liquefied by a phase change to polymerize a monomer component in an oily substance having a heat storage property to form a polymer, so that the oily substance is dispersed in the polymer. The held heat storage material composition constitutes the heat storage material. Thereby, in the polymer obtained by polymerizing the monomer component, since it is possible to hold the oily substance so that the fluidity of the oily substance is reduced, in order to store heat or radiate heat as described above. When freezing and thawing are repeated, leakage such as exudation of the oily substance is suppressed, ignition of the oily substance is suppressed, and a highly safe heat storage material can be stably obtained. Similarly, by sealing so that the amount of contaminants becomes a certain value or less, the heat storage material has the sealing property of the packaging container and the high temperature water resistance that realizes high safety. The preferred forms of the amount of impurities and the sealing method are the same as above.

In the above method for producing a heat storage material, a polymer obtained by polymerizing a monomer component is used in order to more stably maintain the state of holding an oily substance having a heat storage property by liquefying due to a phase change. It is preferable to have a crosslinked structure. As a method of imparting such a crosslinked structure to a polymer, for example, at least 2 polymerizable unsaturated groups are present in the molecule.
A method of polymerizing a monomer component containing at least one crosslinkable monomer to form a polymer is suitable. That is, in the present invention, the monomer component preferably contains a crosslinkable monomer, and by polymerizing a monomer component containing such a crosslinkable monomer, a polymer having a crosslinked structure Will be generated.

As a method of imparting the above-mentioned crosslinked structure to the polymer, a method of polymerizing a monomer component containing a reactive monomer having a condensable functional group to form a polymer can also be applied. . In this case, a polymer obtained by polymerizing the above monomer component in an oily substance, in a state of containing the oily substance,
With a cross-linking agent having at least two condensable functional groups,
By condensing the condensable functional group of the polymer with the condensable functional group of the crosslinking agent to crosslink, a polymer having a crosslinked structure can be obtained. Such a method may be used in combination with the method using the above-mentioned crosslinkable monomer.
In these polymerization reaction and crosslinking reaction, the reaction rate can be increased by appropriately selecting and using a catalyst that accelerates the reaction.

In the above method for producing a heat storage material,
It is preferable to add an oil thickener and / or a crosslinking agent that reduces the fluidity of the oily substance to the heat storage material composition. More preferred is a form in which an oil thickener and a crosslinking agent are added. In this case, as the method for forming the heat storage material composition, (1) after polymerizing a monomer component in an oily substance to form a polymer, adding an oil thickener and / or a crosslinking agent A method of introducing a cross-linking structure into a polymer, (2) polymerizing a monomer component in an oily substance and an oil thickener to form a polymer, and adding a cross-linking agent as necessary to the above polymer. Examples thereof include a method of introducing a crosslinked structure.

In the method for producing a heat storage material of the present invention, the state of the heat storage material composition filled in the packaging container is not particularly limited, and examples thereof include a liquid state, a gel state, a solid state and the like, and a mixture thereof. May be Further, the solid heat storage material composition may be liquefied by heating or the like, or the liquid heat storage material composition may be used in the form of gel or solid. Among these, since a container having a complicated shape can be easily filled with the heat storage material composition without a gap, a liquid state is preferable, and the heat storage material composition is densely filled in the container,
A heat storage material having excellent thermal efficiency can be manufactured. Most preferably, it is filled in a packaging container in a liquid state and gelled or cured in the container to form a heat storage material.

The shape of the packaging container in the present invention is not particularly limited, and examples thereof include a cylinder type, an envelope type, a (standing) pouch type, a tetrapack type, a spherical type, a prismatic type, a gourd type, a tube type, a sausage type, Examples include a coil type, a bottle type, and a shape in which these are formed into a continuous envelope. Also,
Examples thereof include a bag-like material that forms such a shape by sealing the heat storage material composition. Among these, a cylindrical type, an envelope type, a (standing) pouch type, a tetrapack type, and a container formed by continuously packaging these are preferable.

When the packaging container is a container having the above-mentioned shape, the heat storage material composition can be filled in the container to enclose the heat storage material. When the packaging container is a bag-shaped product having a three-dimensional shape as described above by sealing the heat storage material composition, the heat storage material composition is injected into the bag-shaped product or the heat storage material composition is The heat storage material composition can be sealed in the bag by wrapping it in a bag.

The material of the packaging container in the present invention includes:
Usually, it is not particularly limited as long as the heat storage material composition constituting the heat storage material can be prevented from being mixed into a medium such as circulating water in the heat storage device. For example, polyethylene (PE), polypropylene (PP ), Poly-1-butene, α-olefin polymers, α-olefin copolymers and other polyolefins (PO); nylon (NY) and other polyamides (PA); polyvinyl chloride (PVC); polyvinylidene chloride (PVDC) ); Polyesters such as polyethylene terephthalate (PET); polyols; polyethers; films of graft-modified unsaturated carboxylic acid / derivatives and the like. Further, a laminated film in which films of these materials are laminated or a film on which an aluminum vapor deposition layer (Al) is formed may be used. As such a film, a polyamide-polyolefin film, a polyester-polyamide-polyolefin film, a polyester-aluminum-polyolefin film, a polyester-aluminum-polyester-polyolefin film, a polyester-nylon-aluminum-polyolefin film, a polyester-nylon-polyolefin film. Etc. In a preferred embodiment of the present invention, the fusion layer with the heat storage material composition is polyolefin, and at least one film selected from the group consisting of polyolefin, polyamide, polyester, polyol, polyether and aluminum vapor deposition layer is packaged. It is a multilayer laminate film used for.

The thickness of the packaging container is not particularly limited and may be appropriately set depending on the material and the like.
It is preferably 001 to 10 mm. 0.001m
When it is less than m, the heat storage material composition may be mixed in a medium such as circulating water in the heat storage device, and when it is more than 10 mm, the heat transfer property and the filling rate may be decreased. More preferably, it is 0.01 to 0.5 mm.

As the packaging container, specifically, those having the following shapes, materials and thicknesses are suitable. (1) When the heat storage material has a cylindrical shape, an envelope shape, a plate shape, a spherical shape, a prismatic shape, a gourd shape, etc. Material: a plastic film such as PE, PP, PET, NY, PA / PO, polyester / PA / Laminated film of PO, polyester / Al / PO, polyester / Al / polyester / PO Film thickness: 25 to 300 μm, Al ≦ 10 μm Container size: length 50-300 mm, long diameter 7-50 m
m, short diameter 3-30 mm (2) When the shape of the heat storage material is bottle / tube Material: PE, PP, PVC, poly-1-butene Container size and shape: Diameter 10-50 mm (30-40 m)
m), tubular shape with length ≧ 150 mm (200-300 mm)

The amount of the heat storage material composition enclosed in the packaging container is not particularly limited, and for example, the total volume of the container is 100.
%, It is preferably 20 to 100%. Two
If it is less than 0%, the heat storage efficiency may be insufficient. More preferably, it is 95% or less in consideration of expansion and contraction of the heat storage material composition. More preferably, 40-
90%.

Specific embodiments of the heat storage material composition of the present invention will be described below. The heat storage material composition of the present invention contains an oily substance having a heat storage property by a phase change as an essential component, and can store and release thermal energy such as sensible heat storage, latent heat storage, and chemical reaction heat storage. Having a heat storage property by a phase change means having a latent heat storage that utilizes latent heat at the time of a phase change or a phase transition as a heat storage property, and such an oily substance has a high heat storage density and near a constant temperature. It is capable of storing and radiating heat. Further, as an oily substance that liquefies due to a phase change, in the case of a heat storage material for building air conditioning, specifically, at around room temperature (25 ° C) and atmospheric pressure (about 1
It is preferably liquid at 01.3 kPa). In addition, in this specification, a heat storage material composition shall mean all the materials with which the packaging container which comprises a heat storage material will be filled.

Examples of the oily substance having a heat storage property due to the above phase change include hydrocarbon compounds such as alcohols, esters, ethers and paraffins, and specifically, C _{14 to} C ₁₆ paraffins and C Examples thereof include intermediate paraffins that are liquid at room temperature such as _{15 to} C ₁₆ paraffins, pentadecane, C ₁₄ paraffins, and C ₁₆ paraffins; higher paraffins that are solid at room temperature; and higher alcohols such as 1-decanol. These may be used alone or in combination of two or more. Of these, the heat storage material for building air conditioning is at room temperature (25
It is preferable to use an oily substance that is oily at (° C.) and normal pressure (about 101.3 kPa). Further, since it is possible to easily and stably produce a heat storage material that can be easily obtained and used in a wide temperature range,
Paraffin is preferable, and for cold heat use of building air conditioning,
Among paraffins, pentadecane is preferable.

The oil thickener in the heat storage material composition is not particularly limited as long as it has an action of reducing the fluidity of the oily substance, and examples thereof include the following (1) to
The compounds and substances described in (7) can be used. These may be used alone or in combination of two or more.

(1) Polyolefin-based polymers and halides obtained by halogenating a part of the polyolefin-based polymers: polyolefin homopolymers such as polyethylene, polypropylene and polybutene; ethylene as a main component and ethylene and 3 to 12 carbon atoms. Polyolefin copolymer formed by copolymerization with α-olefin of 1; Polyolefin copolymer such as polyolefin formed by copolymerizing propylene as a main component with α-olefin having 2, 4 to 12 carbon atoms; vinyl acetate , A copolymer obtained by copolymerizing a monomer such as ethyl acrylate or ethyl methacrylate with an α-olefin.

(2) In the field of rubber and plastics, a compound known as a so-called thermoplastic elastomer having rubber elasticity at room temperature or higher: a block of polystyrene and polybutadiene, polyisoprene or a hydrogenated product of these polyolefins. Styrene-based elastomers such as copolymers; Mixtures of polyolefin copolymers and polyolefin copolymers; Olefin-based elastomers such as copolymers obtained by graft-polymerizing polyolefins with olefins; Urethane-based elastomers; Ester-based elastomers etc.

(3) Hydrocarbon rubber: natural rubber, styrene-butadiene copolymer rubber, butyl rubber, butadiene rubber, isoprene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene terpolymer rubber, Styrene-ethylene-butylene terpolymer rubber,
Ethylene-vinyl acetate copolymer rubber, ethylene-ethyl acrylate copolymer rubber and the like.

(4) N-acyl amino acid amide: N-lauroyl glutamic acid diamide, N-lauroyl glutamic acid dibutyl amide, N-lauroyl glutamic acid distearyl amide, N-acetyl glutamic acid distearyl amide, N-octyl glutamic acid dioctyl amide, N, N-dicapryloyl lysine amide, N, N-dicapryloyl lysine lauryl amide, N, N-dilauroyl lysine octyl amide, N-lauroyl valine lauryl amide, N-lauroyl phenylalanine lauryl amide and the like.

(5) N-acyl amino acid amine salt: N,
N-dilauroyl lysine octyl amine salt, N, N-dilauroyl lysine stearyl amine salt, N, N-dicapryloyl lysine lauryl amine salt, N-stearoyl glutamic acid stearyl amine salt and the like.

(6) N-acyl amino acid derivative: N, N
-N-acyl amino acid esters such as dicapryloyl lysine lauryl ester, N, N-dilauroyl lysine lauryl ester, N, N-dilauroyl lysine stearyl ester and N-stearoyl glutamic acid stearyl ester. (7) Others: benzylidene sorbitol, 12-hydroxystearic acid and the like.

The above polyolefin polymer and its halide may be non-crystalline, low crystalline, or crystalline. However, the amorphous or low crystalline polyolefin polymer may be classified as a hydrocarbon rubber depending on its physical properties. As the thermoplastic elastomer, a compound having rubber elasticity at room temperature or higher is suitable. More preferably, it is a compound having rubber elasticity at room temperature or higher and up to 20 ° C. higher than the melting point (crystal transition temperature) of the oily substance, and further preferably, it is more than the melting point of the oily substance. It is a compound having rubber elasticity in the range up to 10 ° C higher.

The amount of the oil thickener used is, for example,
The amount is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the oily substance. If the amount is less than 0.1 parts by weight, the effect of lowering the fluidity of the oily substance may be insufficient without impairing the heat storage property of the oily substance, and the liquid oily substance may be removed from the heat storage material composition. May separate and ooze out. If the amount is more than 50 parts by weight, the heat storage material composition becomes a solid or highly viscous composition, so that the heat storage material composition may not be able to be filled into a container having a complicated shape without a gap. Further, since the reaction to form a polymer or a cross-linked polymer described below and the reaction to introduce a cross-linked structure into the polymer are inhibited by the oil thickener, it is necessary to produce a heat storage material composition having excellent shape retention. May not be possible. It is more preferably 0.2 to 30 parts by weight, and even more preferably 0.4 to 4 parts by weight.

A method for forming a polymer by polymerizing a monomer component in an oily substance having a heat storage property by liquefying due to a phase change will be described below. As the monomer component,
There is no particular limitation as long as it contains the monomer (a) having one polymerizable unsaturated group as a main component in the molecule. Further, as described above, a crosslinkable monomer (b) having at least two polymerizable unsaturated groups in the molecule.
It is preferable to include a reactive monomer (c) having a condensable functional group. Examples of the monomer (a) include a solubility parameter (SP) because, for example, the heat storage material composition is easily made into a gel or solid state and the retention of the oily substance is improved.
It is preferable to use a monomer whose value) is 18.4 or less.
The solubility parameter (SP value) is a value generally used as a measure of the polarity of a compound, and in the present specification, a value derived by substituting the Hoy cohesive energy constant into the Small calculation formula is used. It is a value represented by (J / cm ³ ) ^1/2 as applied.

The solubility parameter (SP value) is 1
Examples of the monomer (a) having 8.4 or less include those described below. These may be used alone or in combination of two or more. (1) Unsaturated carboxylic acid ester: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, is
o-butyl (meth) acrylate, t-butyl (meth)
Acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate,
Phenyl (meth) acrylate, octylphenyl (meth) acrylate, nonylphenyl (meth) acrylate, dinonylphenyl (meth) acrylate, cyclohexyl (meth) acrylate, menthyl (meth) acrylate, isobornyl (meth) acrylate, dibutyl (meth) Acrylate, dibutyl maleate, didodecyl maleate, dodecyl crotonate, didodecyl itaconate, etc.

(2) Hydrocarbon group-containing (meth) acrylamide: (di) butyl (meth) acrylamide,
(Di) dodecyl (meth) acrylamide, (di) stearyl (meth) acrylamide, (di) butylphenyl (meth) acrylamide, (di) octylphenyl (meth) acrylamide and the like.

(3) α-olefin: 1-hexene, 1
-Octene, isooctene, 1-nonene, 1-decene and the like. (4) Alicyclic vinyl compound: vinylcyclohexane and the like. (5) Allyl ether having an aliphatic hydrocarbon group: dodecyl allyl ether and the like. (6) Vinyl ester having an aliphatic hydrocarbon group: vinyl caproate, vinyl laurate, vinyl palmitate, vinyl stearate and the like. (7) Vinyl ether having an aliphatic hydrocarbon group: butyl vinyl ether, dodecyl vinyl ether and the like. (8) Aromatic vinyl compounds: styrene, t-butyl styrene, octyl styrene, etc.

Among the above-mentioned monomer components, alkyl (meth) acrylate, alkylaryl (meth) acrylate, alkyl (meth) acrylamide, alkylaryl (meth) acrylamide, fatty acid vinyl ester,
It is preferable to use at least one unsaturated compound selected from the group consisting of alkylstyrene and α-olefin as the main component. Such an unsaturated compound preferably has at least one aliphatic hydrocarbon group having 1 to 30 carbon atoms.

The amount of the above-mentioned monomer (a) having a solubility parameter (SP value) of 18.4 or less in the above-mentioned monomer component is not particularly limited as long as it is the main component, and for example, 50% by weight. The above is preferable. 50% by weight
If the amount is less than the range, the content of the oily substance retained in the polymer may decrease. More preferably 70% by weight
That is all.

The above-mentioned monomer component may contain a monomer (a) having a solubility parameter (SP value) of more than 18.4. Examples of such a monomer (a) include methoxy polyethylene glycol (meth) acrylate and phenoxy polyethylene glycol (meth) acrylate. These may be used alone or in combination of two or more.

Examples of the crosslinkable monomer (b) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polyethylene glycol-polypropylene glycol di (meth) acrylate. , Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
N, N'-methylenebisacrylamide, N, N'-propylenebisacrylamide, glycerin tri (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate; by esterification of alkylene oxide adducts of polyhydric alcohols such as glycerin, trimethylolpropane, tetramethylolmethane with (meth) acrylic acid The polyfunctional (meth) acrylate and divinylbenzene etc. which are obtained are mentioned. These may be used alone or in combination of two or more.

The mixing ratio of the monomer (a) and the crosslinkable monomer (b) is, for example, 100 weight% of the total weight of the monomer (a) and the crosslinkable monomer (b). %,
It is preferable that the amount of the monomer (a) is 90 to 99.999% by weight and the amount of the crosslinkable monomer (b) is 0.001 to 10% by weight.

The reactive monomer (c) is at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, a mercapto group, a nitrile group, an amino group, an amide group, an isocyanate group and an epoxy group. Examples thereof include vinyl monomers having a group and acid anhydrides having a polymerizable unsaturated group. These may be used alone,
You may use 2 or more types together. Specific examples of these are:
For example, the following may be mentioned.

(1) Carboxyl group-containing vinyl monomer: (meth) acrylic acid, fumaric acid, itaconic acid, etc. (2) Vinyl monomer having a hydroxyl group: hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycerin (meth) acrylate, Trimethylolpropane (meth) acrylate, hydroxystyrene, etc.

(3) Vinyl-based monomers having a mercapto group: vinyl mercaptan, mercaptoethyl (meth) acrylate and the like. (4) Vinyl-based monomer having a nitrile group: (meth) acrylonitrile and the like. (5) A vinyl-based monomer having an amino group: aminoethyl (meth) acrylate, vinylpyridine and the like.

(6) Vinyl-based monomer having an amide group:
(Meth) acrylamide and the like. (7) Vinyl-based monomer having an isocyanate group: vinyl isocyanate and the like. (8) Epoxy group-containing vinyl monomer: glycidyl (meth) acrylate and the like. (9) Acid anhydride having a polymerizable unsaturated group: maleic anhydride and the like.

The mixing ratio of the monomer (a) and the reactive monomer (c) is, for example, the total of the monomer (a) and the reactive monomer (c). It is preferable to set the weight to 100% by weight, and the monomer (a) to 90 to 99.995% by weight, and the reactive monomer (c) to 0.005 to 10% by weight.

When the above monomer component contains the reactive monomer (c), the condensable functional group and the condensable functional group are crosslinked with a crosslinking agent having two condensable functional groups. As a result, a crosslinked structure is formed. Examples of the cross-linking agent include those described below depending on the condensable functional group (X) of the reactive monomer (c). These may be used alone or in combination of two or more. (1) When the condensable functional group (X) is a carboxyl group, a mercapto group, a nitrile group, or an epoxy group, examples thereof include phenol resins such as dimethylolphenol and polymethylolphenol. (2) When the condensable functional group (X) is a carboxyl group or a hydroxyl group, examples thereof include an amino resin obtained by addition-condensing an amino compound such as melamine, benzoguanamine and urea with formaldehyde and alcohol.

(3) When the condensable functional group (X) is a carboxyl group, an isocyanate group or an epoxy group,
Examples include polyvalent amino compounds such as hexamethylenediamine, diethylenetriamine, and tetraethylenepentamine. (4) When the condensable functional group (X) is a carboxyl group, a hydroxyl group, a mercapto group, an isocyanate group, an amide group, an amino group or an epoxy group, hexamethylene diisocyanate, isophorone diisocyanate,
p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate,
1,5-naphthalene diisocyanate; isocyanate compounds such as blocked isocyanates obtained by condensing these isocyanates with methanol or phenol.

(5) When the condensable functional group (X) is an isocyanate group or an epoxy group, a polyvalent carboxylic acid such as malonic acid, succinic acid, adipic acid, phthalic acid, terephthalic acid, etc. may be mentioned. To be (6) When the condensable functional group (X) is a hydroxyl group, an isocyanate group, or an epoxy group, phthalic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, or the like acid anhydride, etc. Can be mentioned.

(7) When the condensable functional group (X) is a hydroxyl group, a mercapto group, an amino group or an amide group, aldehyde compounds such as glyoxal and terephthalaldehyde can be used. (8) When the condensable functional group (X) is a hydroxyl group, an isocyanate group, or an epoxy group, polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and hexanediol can be used.

(9) When the condensable functional group (X) is a carboxyl group, a hydroxyl group, a mercapto group or an isocyanate group, toluene glycidyl ether, hexamethylene glycidyl ether, bisphenol A diglycidyl ether, polypropylene glycol Examples thereof include epoxy compounds such as diglycidyl ether.

In the reactive monomer (c) and the cross-linking agent, the condensable functional group (X) of the reactive monomer (c),
The combination with the condensable functional group (Y) of the cross-linking agent is such that one of the functional groups is at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, a mercapto group, an amino group and an amide group. It is preferable that the other functional group is at least one functional group selected from the group consisting of an isocyanate group, an epoxy group, and a carboxylic acid anhydride group. More preferably, since the oily substance can be gelled at a low temperature, the condensable functional group (X)
Is a hydroxyl group, and the condensable functional group (Y) is an isocyanate group.

The ratio of the reactive monomer (c) to the crosslinking agent is, for example, 0.1 to 10 mol of the condensable functional group (Y) per 1 mol of the condensable functional group (X). It is preferable to set it so that it becomes a mole. If it is less than 0.1, the strength of the heat storage material composition may become insufficient, and if it exceeds 10, the retentivity of the oily substance may become insufficient.

When the above-mentioned monomer component contains the reactive monomer (c), a polymer obtained by polymerizing the monomer component together with an oily substance and a crosslinking agent are mixed to form a mixture, and then the oily substance is added. The crosslinking reaction may be carried out at a temperature of 0 to 80 ° C. so that the substance can be melted and maintained in a liquid state. Furthermore, in order to prevent the condensable functional group (X) and the condensable functional group (Y) from remaining unreacted after the crosslinking reaction, the condensable functional group (X) and A compound having a reactive group capable of polycondensation with the condensable functional group (Y) may be added in advance or after the crosslinking reaction. For example, when the condensable functional group (X) or the condensable functional group (Y) is a polyvalent isocyanate, a long chain carboxylic acid or the like can be used as the compound.

As a method for polymerizing a monomer component with an oily substance having a heat storage property to form a polymer, polymerization is usually performed in the coexistence of an oil-soluble radical polymerization initiator. An oil-soluble radical in a state in which an oily substance and a monomer component are mutually compatible and mixed and suspended in an aqueous surfactant solution in which a protective colloid agent or a surfactant is dissolved in an aqueous medium such as It is also possible to use a method of suspension polymerization in the presence of a polymerization initiator (suspension polymerization in water). At this time, the polymerization may be carried out in the presence of an oil thickener that reduces the fluidity of the above-mentioned oily substance.

Examples of the oil-soluble radical polymerization initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide and cumene hydroperoxide; 2,2'-azobisisobutyronitrile,
Examples thereof include azo compounds such as 2,2'-azobisdimethylvaleronitrile. These may be used alone or 2
You may use together 1 or more types.

The amount of the oil-soluble radical polymerization initiator used is, for example, 100% by weight of the monomer component,
It is preferably 0.1 to 5% by weight. In the above-mentioned polymerization, the polymerization temperature is preferably a temperature at which the oily substance can maintain a liquid state at 0 to 150 ° C. in consideration of the melting point of the oily substance, the type of the monomer component and the type of the polymerization initiator. . More preferably, it is 0 to 90 ° C.

Examples of the protective colloid agent include polyvinyl alcohol, hydroxyethyl cellulose, gelatin and the like, and examples of the surfactant include sodium alkylsulfonate, sodium alkylbenzenesulfonate, polyoxyethylene alkyl ether, fatty acid. Examples include soap and the like. These may be used alone or in combination of two or more.

The heat storage material composition may further contain additives having the functions described below. These may be used alone or in combination of two or more. (1) For improving heat transfer: Metal powder such as iron and copper: metal fiber; metal oxide; carbon; carbon fiber and the like. (2) For adjusting specific gravity: sand; clay; stone; metal powder such as lead and iron.

(3) For imparting flame retardancy: water; water gel; metal powder; inorganic compounds such as calcium carbonate; bromine-based, chlorine-based,
Flame retardants such as phosphorus. In addition, flame retardance means reduction of flammability,
This includes prevention of fire spread, extinction of flash point due to steam, and reduction of combustion heat. (4) To prevent supercooling: Metal powder, polymer paraffin (wax), etc. (5) For freezing point adjustment: waxes and the like. (6) For preventing oxidation and deterioration over time: Phenolic type,
Thio-type and phosphorus-type antioxidants, etc. (7) Others: colorants, pigments, antistatic agents, antibacterial agents, etc.

The amount of the additive used is, for example, 10 to 4 with respect to the total amount of the oily substance and the polymer when calcium carbonate is used to reduce flammability.
It is preferably 0% by weight.

An inclusion compound for adjusting the latent heat property may be added to the oily substance. Examples of the inclusion compound include C ₄ H ₈ · O · 17H ₂ O and (CH ₃ ) ₃ N ·
10.25H ₂ O, (C ₄ H ₉ ) ₄ NCHO ₂ · 32H ₂ O,
_{(C 4 H 9) 4 NCH} 3 CO 2 · 32H 2 O , and the like.
These may be used alone or in combination of two or more.

In the case where the monomer component is polymerized with the oily substance having heat storage property to form a polymer as a heat storage material, when the above additive is used, an oily substance such as metal powder is used. When a substance having a large specific gravity difference of 1 or more with the substance is used, or the difference in the numerical value of the solubility parameter between the additive and the oily substance is 4 or more apart,
Even when the compatibility between the additive and the oily substance is poor, the additive can be held in the heat storage material composition in a uniform state, and the effect of the additive can be more effectively exhibited.

As the method for producing a heat storage material of the present invention, for example, when a heat storage material composition is prepared by polymerizing a monomer component with an oily substance having heat storage properties to form a polymer, the heat storage material composition When enclosing an item in a packaging container, a bag-like object having the above-mentioned three-dimensional shape formed of a plastic film, or a packaging container having the above-mentioned three-dimensional shape,
A monomer component or a polymer before cross-linking may be filled in a liquid state together with an oily substance and cured (gelled) in the container or the bag. As a result, it becomes easy to densely fill the container or the bag with the heat storage material composition, and it is possible to obtain a heat storage material with improved heat storage efficiency due to the oily substance.

As the above-mentioned production method, for example, (1) an oily substance and a monomer component containing a monomer (a) and a crosslinkable monomer (b) in a liquid state in the container or the bag A method of casting by filling into a solid and filling, and performing bulk cross-linking polymerization in the coexistence of an oil-soluble radical polymerization initiator (casting polymerization method),
(2) Oily substance and monomer (a) and reactive monomer (c)
A mixture of a cross-linking agent and a pre-crosslinking polymer obtained by polymerizing a monomer component containing a polymer in the coexistence of an oil-soluble radical polymerization initiator, the container in a liquid state before the cross-linking reaction is completed. A method of charging by filling in or in the bag-like material, and then completing the crosslinking reaction to cure (crosslinking method after casting),
(3) Oily substance and monomer (a) and crosslinkable monomer (b)
Into a container such as a stainless steel vat in a liquid state with a monomer component containing, a heat storage material cured by bulk cross-linking polymerization in the coexistence of an oil-soluble radical polymerization initiator with an extruder such as a meat chopper. Examples thereof include a method of filling the plastic container (encapsulating method after forming the heat storage material).

INDUSTRIAL APPLICABILITY The heat storage material of the present invention is excellent as a material for forming a heat storage device for the purpose of labor saving and efficiency improvement of cooling and heating energy for large buildings such as office buildings and factories, household use, etc., and environmental protection. It is a safe one having sealing property of packaging container and high temperature water resistance. Further, the method for producing a heat storage material of the present invention is a method capable of producing such a heat storage material with improved workability and efficiency.

[0076]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

In the examples, the amount of impurities was measured by the following method. (Measurement method of amount of impurities) The basis weight X (kg / m ² ) of the film used as the packaging container was measured. The sealing area is cut out, and the area S (m ² ) of the sealing area and the film weight Y (kg) including the attached contaminants and the total area S ′ (m ² ) of the film covering the cut out area are shown. The amount Z (kg / m ² ) of the heat storage material composition (contaminant) per unit area of the sealing portion of the packaging container was calculated from the difference between the measured value and the basis weight of the film by the following formula. Amount of heat storage material composition (contamination) per unit area of the sealing portion of the packaging container Z (kg / m ² ) = (film weight Y (kg) including the adhered contaminants) -area weight X (kg / m ² ) × total area S ′ (m ² )) of the film covering the cut-out sealing part / area S (m ² ) of the sealing part

Example 1 A 500 ml flask equipped with a thermometer, a stirrer, a gas inlet tube, two dropping funnels and a reflux condenser was charged with 10 g of pentadecane as an oily substance, and stirred.
The inside of the flask was replaced with nitrogen, and the flask was heated to 65 ° C. under a nitrogen stream. Then, 2-ethylhexyl acrylate (SP value: 15.
9) A solution consisting of 38 g, hydroxyethyl acrylate 2 g, and pentadecane 40 g as an oily substance.
(1) was added to another dropping funnel, 0.1 g of 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) as a polymerization initiator, and 10 g of pentadecane as an oily substance and a diluent. A solution (2) consisting of

Subsequently, the solution (1) was placed in the flask.
The solution (2) and the solution (2) were simultaneously added dropwise over 1 hour to carry out a polymerization reaction, and then the temperature inside the flask was further raised to 80 ° C.
Polymerization (1) before cross-linking by maintaining for a while to complete the polymerization
Got

A solution (3) consisting of 2.3 g of toluene diisocyanate as a crosslinking agent, 0.1 g of dibutyltin dilaurate, and 100 g of pentadecane as an oily substance and a diluent was prepared.

Polyethylene terephthalate 15 is used as the base material layer.
μm and stretched nylon 15 μm are laminated in this order from the outside, and a multi-layer laminate film (width 10 μm) made of low-density linear polyethylene 100 μm in the sealant layer.
cm roll, back seal portion 5 mm width) was used in a liquid filling and packaging machine (Orihiro Co., ONPACK-2020ASII) to prepare a mixed solution obtained by mixing the polymer (1) before crosslinking and the solution (3) obtained by the above method. Filled, tubular (length 20c
m) A filled product was obtained. The amount of the heat storage material composition after filling was 85 g. This tubular filled product was placed in a constant temperature oven at 60 ° C. for 6 hours to obtain a heat storage material (1) filled with a gel heat storage material composition. Sealing site at this time (4.3 cm × 1.
5 cm) was cut out and the amount of impurities per unit area was measured and found to be 0.0493 kg / m ² .

Comparative Example 1 The multilayer laminate film described in Example 1 was used in a vertical multipurpose wrapping machine (WF-3900MN, manufactured by Sanwa Joki Co., Ltd.), and the weight before crosslinking obtained in the same manner as in Example 1 Coalescing (1)
The mixture solution obtained by mixing the solution (3) with and was filled to obtain a tubular (length 20 cm) filled article. The amount of the heat storage material composition after filling was 95 g. This tubular filled product was placed in a constant temperature oven at 60 ° C. for 6 hours to obtain a comparative heat storage material (1) filled with a gel heat storage material composition. At this time, the sealed portion (4.3 cm × 1.5 cm) was cut out and the amount of impurities per unit area was measured and found to be 0.112 kg / m ² .

The heat storage material (1) obtained in Example 1 and Comparative Example 1 and the comparative heat storage material (1) were immersed in a constant temperature water bath at 60 ° C.,
When the heat storage material (1) was not peeled off at the sealed portion when left for 1 week and then taken out, the heat storage material (1) was peeled off at the sealed portion.

Example 2 First, 15 μm of polyethylene terephthalate and 15 μm of stretched nylon were laminated on the base material layer in this order from the outside, and the sealant layer was formed of the low-density linear polyethylene 10
A multi-layer laminate film consisting of 0 μm is 80 mm long,
A film container was cut into a width of 135 mm and a tetrapak-shaped film container was sealed with a margin of 5 mm except for one side with a heat sealer (T-230 manufactured by Fuji Impulse Co., Ltd.).
Next, dodecyl acrylate (SP
Value: 16.2) 39 g and ethylene glycol dimethacrylate 0.8 g, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) 0.2 g as a polymerization initiator, and pentadecane as an oily substance. 1
A mixed solution was prepared by uniformly mixing 60 g with each other.

Then, 40 g of the mixed solution was filled in the container, and a gas introducing pipe was attached to the upper part of the container to sufficiently introduce nitrogen into the mixing solution to remove oxygen in the mixed solution. did. Then, this container was allowed to stand in a constant temperature bath kept at 40 ° C. for 8 hours while maintaining the nitrogen atmosphere, whereby the mixed solution was polymerized and crosslinked to form a polymer in which pentadecane was held in a gel state. After visually confirming this, the gas introduction pipe was removed. With the gel polymer in contact with the remaining seal portion of the container, the seal portion was squeezed with a rubber roller and then sealed with a heat sealer (scale 4) to obtain a heat storage material (2). The amount of heat storage material composition after sealing is 32
It was g. Sealing site at this time (6.2 cm x 0.5
cm) was cut out and the amount of impurities per unit area was measured to be 0.0160 kg / m ² .

Example 3 1 equipped with a thermometer, a stirrer, a gas introduction pipe and a reflux condenser
In a liter flask, gelatin 6g, distilled water 594g
Dissolved in and charged, while stirring, the inside of the flask was replaced with nitrogen,
It heated at 80 degreeC under nitrogen stream. After that, 39 g of dodecyl acrylate as a monomer component and 0.8 g of ethylene glycol dimethacrylate, 0.2 g of benzoyl peroxide as a polymerization initiator, and 160 g of pentadecane as an oily substance were mixed so as to be uniformly mixed. Add the liquid to the flask at once and
2 under nitrogen flow while mixing under the condition of 00 rpm
The suspension polymerization reaction was carried out for a period of time.

Then, the inside of the flask was further heated to 90 ° C. and maintained for 2 hours to complete the polymerization, thereby forming a polymer in which pentadecane was held in a gel form. After the completion of the polymerization, a granular product (average particle size 0.3 mm) was obtained from the contents in the flask by vacuum filtration. 100 g of the above granular product was filled in a film container in which the back seal and one end of the multilayer laminate film described in Example 1 were pre-sealed with a heat sealer (T-230 manufactured by Fuji Impulse Co., Ltd.). With the granular product in contact with the seal portion at the other end of the container, after squeezing the seal portion with a rubber roller,
A heat storage material (3) was obtained by sealing with a heat sealer (scale 4). The heat storage material composition amount after sealing was 85 g. The sealing site (4.3 cm × 1.5 cm) at this time was cut out and the amount of impurities per unit area was measured to be 0.0344 kg /
It was m ² .

Example 4 Polymer (1) before crosslinking and solution obtained in the same manner as in Example 1
40 g of the mixed solution obtained by mixing (3) was filled in the film container described in Example 2, and the seal part was squeezed with a rubber roller while the remaining seal part of the container was in contact with the mixed solution. (T-23 manufactured by Fuji Impulse Co., Ltd.
A heat storage material (4) containing pentadecane and held in a gel state was obtained by sealing with 0, graduation 4), allowing to stand at room temperature for 4 hours, and crosslinking. The heat storage material composition amount after sealing was 32 g. Sealing part at this time (6.2 cm
(× 0.5 cm) was cut out and the amount of impurities per unit area was measured and found to be 0.0449 kg / m ² .

Example 5 First, dodecyl acrylate (SP
Value: 16.2) A mixing liquid consisting of 39 g, ethylene glycol dimethacrylate 0.8 g, and 0.2 g of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) as a polymerization initiator, A mixing liquid was prepared by adding to 160 g of paraffin wax (manufactured by Nippon Seiro Co., Ltd., product name PW-120) having a melting point of 50 ° C. as an oily substance that was previously melted at 0 ° C. and mixing them so as to be uniform with each other. Then, 40 g of the mixed solution was filled in a film container prepared in the same manner as in Example 2.

Next, while maintaining the container at 60 ° C. in a constant temperature bath, a gas introduction pipe was attached to the upper part of the container to sufficiently introduce nitrogen into the mixed solution to remove oxygen in the mixed solution. Furthermore, keep this container at 60 ° C while maintaining a nitrogen atmosphere.
After standing for 8 hours, the mixed solution was polymerized and cross-linked to form a polymer in which the paraffin wax was held in a gel state, and then the gas introduction tube was removed. In a state where the gel polymer is in contact with the remaining seal portion of the container, the seal portion is squeezed with a rubber roller, and then sealed with a heat sealer (T-230, scale 4 manufactured by Fuji Impulse Co., Ltd.) to store a heat storage material. (5) was obtained. The heat storage material composition amount after sealing was 32 g. Sealing site at this time (6.2 cm x 0.5 c
When m) was cut out and the amount of impurities per unit area was measured, it was 0.0503 kg / m ² .

Example 6 100 g of pentadecane was added to a flaky styrene-ethylene-butylene-styrene block polymer (Shell Chemical Co., Ltd., styrene-based thermoplastic elastomer, Kraton G).
1650) 25 g are mixed and heated to 60 ° C. to obtain a uniform solution.
I got (6). The uniform solution (6) was filled with the multi-layer laminate film using a liquid filling and packaging machine in the same manner as in Example 1 to obtain a tubular (length 20 cm) filled product. The amount of the heat storage material composition after filling was 85 g.
The tubular filled product was cooled to room temperature to obtain a heat storage material (6) filled with a gel heat storage material composition. The sealed portion (4.3 cm × 1.5 cm) at this time was cut out, and the amount of impurities per unit area was measured and found to be 0.0283 kg / m ² .

Example 7 100 g of pentadecane was mixed with 25 g of 12-hydroxystearic acid and heated to 60 ° C. to obtain a uniform solution (7). Using a liquid-filled packaging machine with a multi-layer laminate film in the same manner as in Example 1, a uniform solution was maintained at 40 ° C.
(7) was filled to obtain a tubular (length 20 cm) filled product. The amount of the heat storage material composition after filling was 85 g. The tubular filled product was cooled to room temperature to obtain a heat storage material (7) filled with the gel heat storage material composition. The sealed portion (4.3 cm × 1.5 cm) at this time was cut out and the amount of impurities per unit area was measured and found to be 0.0181 kg / m ² .

Example 8 100 g of pentadecane was mixed with 25 g of polynorbornene (Nosolex, manufactured by Nippon Zeon Co., Ltd.) and heated to 60 ° C. to obtain a uniform solution (8). 40 g of the homogeneous solution (8) was filled in the film container described in Example 2 while keeping the temperature at 40 ° C. or higher, and the seal part was covered with a rubber roller while the gel polymer was in contact with the remaining seal part of the container. After squeezing, it was sealed with a heat sealer (T-230, scale 4 manufactured by Fuji Impulse Co., Ltd.) to obtain a heat storage material (8). The heat storage material composition amount after sealing was 32 g. Sealing site at this time (6.2 cm x
0.5 cm) was cut out and the amount of impurities per unit area was measured to be 0.0217 kg / m ² .

Example 9 Solution (9) consisting of 2.3 g of toluene diisocyanate as a cross-linking agent, 0.1 g of dibutyltin dilaurate, and 180 g of an oily substance and pentadecane as a diluent.
Prepared.

Using a liquid-filled packaging machine in the same manner as in Example 1, using a liquid filling and packaging machine, the polymer (1) before crosslinking obtained in the same manner as in Example 1 and the above solution (9) were mixed. The solution was filled to obtain a tubular (length 20 cm) filled article. The amount of the heat storage material composition after filling was 85 g. The tubular filled product was cooled to room temperature to obtain a heat storage material (9) filled with the gel heat storage material composition. At this time, the sealed portion (4.3 cm × 1.5 cm) was cut out and the amount of impurities per unit area was measured and found to be 0.0869 kg / m ² .

Example 10 A solution (10) consisting of 2.3 g of toluene diisocyanate as a crosslinking agent, 0.1 g of dibutyltin dilaurate, and 40 g of pentadecane as an oily substance and a diluent was prepared.

Multilayer laminate film as in Example 1
Was obtained in the same manner as in Example 1 using a liquid filling and packaging machine.
A mixture of the polymer (1) before crosslinking and the solution (10)
Fill the combined solution and fill the tube (length 20 cm)
Obtained. The amount of the heat storage material composition after filling was 85 g. this
Gel-shaped heat storage material assembly that cools the tubular filling to room temperature
A heat storage material (10) filled with the product was obtained. Sealing at this time
Cut out a part (4.3 cm x 1.5 cm) and hit the unit area
The amount of foreign matter is 0.0357 kg / m ²And
It was.

Heat storage materials (2) obtained in Examples 2 to 10
When (10) was immersed in a constant temperature water bath at 60 ° C. and allowed to stand for 1 week and then taken out, the heat storage materials (2) to (10) did not peel off at the sealed site.

Comparative Example 2 100 g of pentadecane was mixed with 25 g of low-density polyethylene pellets (Mirason C-2499, manufactured by Mitsui Chemicals, Inc.) and heated to 130 ° C. to obtain a uniform solution (11). The film container described in Example 2 was filled with 40 g of the solution (11) cooled to 70 ° C., and the solution (11) was in contact with the remaining seal portion of the container, and a heat sealer (manufactured by Fuji Impulse Co., T
Comparative heat storage material (2) was obtained by sealing with -230, scale 4). The heat storage material composition amount after sealing was 38 g. The sealing area (6.2 cm × 0.5 cm) at this time was cut out and the amount of impurities per unit area was measured to be 0.147 kg / m.
It was ² .

The comparative heat storage material (2) obtained in Comparative Example 2 was mixed with 6
When the comparative heat storage material (2) was immersed in a constant temperature water bath of 0 ° C. and allowed to stand for 1 week and then taken out, the sealed portion was peeled off. Table 1 shows the above Examples 1 to 10 and Comparative Examples 1 and 2.

[0101]

[Table 1]

[0102]

EFFECTS OF THE INVENTION The heat storage material of the present invention has the above-mentioned structure, and is used for the purpose of labor saving and efficiency improvement of cooling and heating energy for large buildings such as office buildings and factories, household use, and environmental protection. It is an excellent material for constituting a heat storage device, and is a safe material having sealing property of a packaging container and high temperature water resistance. Further, the method for producing a heat storage material of the present invention is a method having the above-mentioned configuration and capable of producing such a heat storage material with improved workability and efficiency.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masanobu Hinohara             2-6-1, Nishi-Shinjuku, Shinjuku-ku, Tokyo Stocks             In-house company (72) Inventor Hiroshi Nagamura             Hyogo prefecture Himeji city             1 Within Nippon Shokubai Co., Ltd. (72) Inventor Teruhisa Kajiwara             Hyogo prefecture Himeji city             1 Within Nippon Shokubai Co., Ltd. F-term (reference) 3E035 AA20 BA08 BC02 BD06 CA07

Claims (5)

[Claims] 1. A heat storage material obtained by sealing a heat storage material composition containing an oily substance having a heat storage property by phase change as an essential component in a packaging container, wherein the heat storage material is a sealing site unit of the packaging container. The heat storage material composition existing per area is 0.1 kg / m ²
A heat storage material characterized by being: 2. A heat storage material composition comprising, as essential components, an oily substance that liquefies due to a phase change and has heat storage properties, and an oil thickener that reduces the fluidity of the oily substance is sealed in a packaging container. A method for producing a heat storage material, which comprises the steps of: (1) wherein the heat storage material composition present per unit area of the sealing portion of the packaging container is 0.1 kg / m ² or less. A method for manufacturing a heat storage material, which is characterized by being sealed. 3. A method for producing a heat storage material, which is obtained by sealing a heat storage material composition obtained by polymerizing a monomer component in an oily substance having a heat storage property by liquefying by a phase change into a packaging container. The heat storage material manufacturing method is characterized in that the heat storage material composition is sealed so that the heat storage material composition present per unit area of the sealing portion of the packaging container is 0.1 kg / m ² or less. Production method. 4. The method for producing a heat storage material according to claim 3, wherein the monomer component contains a crosslinkable monomer. 5. The heat storage material according to claim 3, further comprising an oil thickener and / or a cross-linking agent, which reduces fluidity of the oily substance, to the heat storage material composition. Production method.