JPH1192758A - Heat-storing agent composition and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat-storing agent which can contain a larger amt. of an oily substance, exhibiting a high heat-storing efficiency, and can prevent the oily substance from oozig in a wide temp. range, being excellent in safety, by mixing a building or civil engineering material with an oily gel retaining an oily substance having heat-storing properties. SOLUTION: A substance of which the latent heat on phase change or phase transition can be utilized is pref. as the oily substance having heat-storing properties. Paraffin is a pref. example of the substance. Pref., the oily gel comprises a polymer having a three-dimensional network for retaining the oily substance by shape retention due to gellation. Such a polymer can be prepd. by the polymn. of a monomer component which contains a monomer having a lipophilic part affinitive to the oily substance, e.g. having a solubility parameter of 9 or lower, and having a polymerizable group in the molecule. The polymer is pref. prepd. by the polymn. of the monomer component in the presence of the oily substance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat storage agent composition used for building materials for floors and walls, and for civil engineering materials for partition walls and the like, and a method for producing the same.

[0002]

2. Description of the Related Art A phase change thermal energy storage system uses an oily substance such as paraffin or a higher alcohol as a phase change substance, and obtains 30 cal / g by a phase change between a liquid phase and a solid phase in the oily substance. It has the advantage that a relatively high latent heat of fusion can be used, and its melting point is from a low temperature of −20 ° C. to a high temperature range exceeding 100 ° C. by selecting from each oily substance or mixing each of the above oily substances. It also has the advantage that it can be set freely.

Conventionally, such a phase change thermal energy storage system utilizes the above-described relatively high latent heat of fusion to reduce the influence of a change in environmental temperature such as external air temperature by eliminating another external heat source. Therefore, various uses have been proposed because the energy cost for reducing the influence can be suppressed.

For example, Japanese Patent Application Laid-Open No. 8-86476 discloses that n-octadecane (95%), a kind of paraffin,
A latent heat storage board in which heat storage pellets using + n-hexadecane (5%) and gypsum are mixed is disclosed.

Japanese Patent Application Laid-Open No. 63-75083 discloses that a phase change material is incorporated in a matrix material such as an inorganic cement-like material, and the phase change material has 14 or more carbon atoms. Has a heat of fusion of 30 cal / g
A composition useful for thermal energy storage using a mixture of at least two paraffins, which are crystalline linear alkyl hydrocarbons as described above, is disclosed.

Further, Japanese Patent Application Laid-Open No. 6-57241 discloses a heat storage structural material in which a heat storage material is dispersed in a building material, wherein the heat storage material is 100 parts by weight of paraffins as a heat storage component and a hydrocarbon-based material as a binder component. A heat storage structural material in which 5 to 30 parts by weight of an organic polymer is mixed in a state where at least a part of a paraffin and a hydrocarbon organic polymer as a binder component at 50 to 250 ° C. are melted by mechanical means. Is disclosed.

Japanese Patent Publication No. 5-41677 discloses a composition containing a phase change material and a matrix material into which the phase change material is incorporated, wherein the phase change material has an alkyl hydrocarbon incorporated into a carrier material. Wherein the alkyl hydrocarbon is a crystalline linear alkyl hydrocarbon having 14 or more carbon atoms and having a heat of fusion of 30 cal / g or more, and the carrier material is such that the alkyl hydrocarbon is dispersed therein. Disclosed are compositions for use in thermal energy storage that are compatible with alkyl hydrocarbons and remain.

[0008]

However, in each of the above publications, there is a danger that a heat storage agent such as paraffin oozes out, causing a danger of ignition or fire spread, heat storage properties being deteriorated with time, and heat storage. When the content is such that the bleeding of the agent can be prevented, the heat storage efficiency is reduced, and both the safety and the heat storage property are difficult to improve. Since the heat storage agent such as a heat storage material or the like exhibits hydrophobicity, in order to uniformly disperse the heat storage agent, there is a problem that forcible stirring or mixing using a dispersant is required, and it takes time to manufacture. I have.

That is, any of the latent heat storage boards and compositions useful for thermal energy storage proposed in the above publications contain a large amount of paraffin due to repetition of a phase change (solidification and melting) of paraffin as a heat storage agent. Because of exudation and fluidization, latent heat storage boards mainly composed of gypsum and heat storage agents such as paraffin leaked from the matrix material, increasing the risk of inflammation and fire spread due to the exuded heat storage agents. In addition, there is a problem that the heat storage agent content decreases due to oozing of the heat storage agent, and the heat storage property deteriorates with time.

On the other hand, in the thermal storage building material proposed in the above publication, paraffin is mixed with a hydrocarbon organic polymer as a binder component by a mechanical means, and the paraffin is contained in the binder component. The hydrocarbon-based organic polymer has a low paraffin holding power, and cannot increase the paraffin bleeding when the paraffin content is increased. Therefore, in the heat storage structure building material, there is a problem that it is difficult to achieve both an improvement in heat storage efficiency due to a high paraffin content and an improvement in safety by suppressing oozing of paraffin.

[0011] Further, in the heat storage structure building material, even if the content of paraffins does not exude at room temperature, the paraffins may start to flow at a high temperature (60 to 90 ° C), and the high temperature may be locally reduced. Roads,
The portion near the wall and the heater cannot be used due to inconvenience such as ignition due to oozing, and has a problem that the range of use is limited.

In addition, the production methods described in the above publications have a problem that the content of the heat storage agent such as paraffin is low, and the heat storage efficiency is low.

[0013]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, an oily gelled substance holding a heat storage oily substance in a three-dimensional network structure,
The heat storage composition containing the building material and the civil engineering material containing the oil-based gelled substance dispersed therein can contain more oil-based substances and has good heat storage efficiency, and also exudes oil-based substances in a wide temperature range. The present invention was found to be excellent in safety because it was possible to suppress the occurrence of the present invention, and completed the present invention.

That is, in order to solve the above-mentioned problems, the heat storage agent composition according to the first aspect of the present invention has a building / civil engineering material and an oil-based gelled body holding an oil-based substance having heat storage properties. It is characterized by having.

According to the first aspect of the present invention, since the oily substance has heat storage properties, for example, when the ambient temperature rises in response to a change in ambient temperature such as a change in the outside air temperature, the oil storage substance becomes oily due to heat storage properties. When the substance absorbs heat and the ambient temperature decreases, the oily substance releases heat due to heat storage. From this, by having an oily gel containing the above oily substance,
It is possible to suppress a temperature change of building and civil engineering materials.

Further, in the above configuration, since the oily substance is held in the oily gelled substance, the oozing and fluidization of the oily substance from the oily gelated substance can be reduced as compared with the prior art, and the exposure of the oily substance can be suppressed. The flammability and fire spread of the oily substance can be significantly reduced.

[0017] In addition, in the above configuration, since the oily substance is held by the oily gelled body, it is possible to suppress the oozing of the oily substance even when the temperature becomes high. It can be applied, and its range of application can be expanded while improving safety as compared with the related art.

The heat storage agent composition according to the second aspect of the present invention is further characterized in that the oily substance is a compound having a heat storage property due to a phase change between a liquid phase and a solid phase. According to the above configuration, in the oily substance, the heat storage amount based on the latent heat due to the phase change between the liquid phase and the solid phase can be set to a large value, and the setting range of the temperature at which the phase changes is set around the room temperature. Because it can be set widely, it is easy to optimally set the temperature that changes phase according to the applied temperature,
Therefore, the heat storage efficiency can be improved.

The heat storage agent composition according to the third aspect of the present invention is further characterized in that the oily gel has a three-dimensional network structure for retaining an oily substance. According to the above configuration, in the oil-based gelled body having the three-dimensional network structure, the oily substance can be held three-dimensionally by the three-dimensional network structure of the oil-based gelled body. From this, in the above configuration,
More oily substances can be retained by the oily gelled body, and the ratio of the oily substances can be increased. Therefore, in the above configuration, the heat storage efficiency can be further improved by increasing the retention ratio of the oily substance.

Further, the oily gel body holds the oily substance by a three-dimensional network structure, so that the oily substance can be held three-dimensionally, that is, from above, below, right and left. Even after that, the oily substance can be held while preventing its oozing. Therefore, with the above configuration, it is possible to further expand the applicable range while improving the safety more reliably than before.

[0021] In the heat storage agent composition according to the fourth aspect of the present invention, the oil-based gelled product may further include a solubility parameter (SP).
(Value) of 9 or less is provided with a polymer obtained by polymerizing a monomer component containing the monomer (A) having a value of 9 or less.

According to the above-mentioned constitution, the oily gel is provided with a polymer obtained by polymerizing a monomer component containing a monomer (A) having a solubility parameter (SP value) of 9 or less. By this, lipophilicity with respect to the oily substance can be further secured, and the retention of the oily substance can be further ensured.

According to a fifth aspect of the present invention, there is provided a method for producing a heat storage agent composition, wherein the lipophilic portion having an affinity for the oily substance in the presence of a heat storage oily substance. Is obtained by polymerizing the monomer (Y) having the formula (I) to obtain an oil-based gelled substance holding the oil-based substance, and then mixing the oil-based gelled substance with a building / civil engineering material.

According to the above method, when the monomer (Y) is polymerized in the presence of an oily substance, the lipophilic portion of the monomer (Y) allows the monomer (Y) to be interpolymerized. The oily substance is interposed in the oil. Therefore, when the monomers (Y) are polymerized with each other in such a state that the oily substance is interposed, more oily substances can be contained, that is, the oily property obtained from each monomer (Y) can be contained. A space that can hold more oily substances can be secured inside the gelled body. Therefore, in the above method, it is possible to obtain an oily gelled body capable of holding more oily substances, and in a molded article of a building / civil engineering material including the oily gelled body, the heat storage efficiency can be improved. .

According to a sixth aspect of the present invention, there is provided a method for producing a heat storage agent composition, comprising: a lipophilic portion having an affinity for the oily substance in the presence of an oily substance and water. Is obtained by subjecting the monomer (Y) to suspension polymerization to obtain an oil-based gelled aqueous dispersion, and then mixing the aqueous dispersion with a building / civil engineering material.

According to the above method, the building and civil engineering material is usually used by suspending it in water and molding it, and then drying or solidifying it by a hydration reaction to form a molded article. For this reason, in the above method, by using the water dispersion of the oily gelled body, the water of the water dispersion can be used as at least a part of the water for suspending the building / civil engineering material. Become. Therefore, it is possible to simplify the formation of the heat storage agent composition which is a molded article containing the oily gel.

In the above method, the oily gel obtained by suspension polymerization becomes substantially spherical, and its particle size can be adjusted within a narrow range. Therefore, the oil-based gelled product can be more uniformly dispersed in a building / civil engineering material or on a building / civil engineering material because the oil-based gelled material is substantially spherical and has a uniform particle size. In the above method, since the suspension polymerization is performed in the presence of water, the solution in which the suspension polymerization has been completed can be directly used as an aqueous dispersion of an oily gel containing an oily substance. Can be simplified.

Further, in the above method, the oily substance and the monomer (Y) can stably form an emulsion, that is, a suspension, in the presence of water by mixing the oily substance and the monomer (Y) by the lipophilic moiety having an affinity for the oily substance. It can be formed. Therefore, in the above method, the formation of the emulsion can be stabilized by having the affinity portion, so that the suspension polymerization can be performed more reliably.

[0029] The method for producing a heat storage agent composition according to the present invention is a mixed solution of a liquid oily gelling precursor having a lipophilic portion having an affinity for an oily substance and the oily substance, And, after mixing the porous building and civil engineering materials with each other, the oily gelling precursor is polymerized and / or cross-linked in the presence of the oily substance to form the oily gelled body holding the oily substance, It is characterized by being formed in civil engineering materials.

[0030] According to the above method, a liquid mixed solution;
After mixing with a porous building and civil engineering material, the oily gelling precursor is polymerized or / and cross-linked to obtain an oily gelling product, which corresponds to the internal shape of the building and civil engineering material, that is, It becomes possible to form an oil-based gelled body that matches the internal voids of building and civil engineering materials.

From the above, according to the above method, even when the oil-based gelled material containing an oily substance has an irregular or complicated shape, the oil-based gelled material can be reliably applied to a building / civil engineering material. Can be formed.

[0032] In the method for producing a heat storage agent composition according to the present invention, an oily substance, a granular polymer which holds the oily substance in a gel state, and a building / civil engineering material are prepared in the presence of water. It is characterized in that the oily substance is retained in the polymer by mixing to form an oily gel, and the oily gel is dispersed in the solidified building / civil engineering material.

According to the above method, since the granular polymer holds the oily substance in a gel state, the polymer, the oily substance, and the building / civil engineering material are mixed with each other, and the oily substance is mixed. It is possible to simultaneously promote the formation of an oily gel by holding the coalesced particles in the presence of water, and to promote the formation of an oily gel by holding the oily substance in the polymer. Become. Thereby, in the above method, the mixing and the holding can be advanced simultaneously and the holding can be promoted, so that the production of the heat storage agent composition can be simplified.

[0034]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described below in detail. The heat storage agent composition according to the present invention,
It has an architectural / civil engineering material and an oily gelled body holding an oily substance having heat storage properties. Examples of building and civil engineering materials include plaster, concrete, mortar, sealing materials, panel materials such as walls, roof materials, floor materials, asbestos slate, blocks, tiles, bricks, and mixtures thereof, and the like. And kneading materials such as water and a solvent for solidifying the compound by a hydration reaction or drying.

The oily substance having a heat storage property is an oily substance which becomes substantially insoluble or hardly soluble in water at about normal temperature (25 ° C.) and normal pressure (1 atm), and a monomer component described later. It is one that can prevent polymerization and crosslinking of a polymer described below from being inhibited, and can store and release heat energy such as sensible heat storage, latent heat storage, and chemical reaction heat storage,
Although it is not particularly limited, a substance having latent heat storage utilizing a latent heat at the time of a phase change or a phase transition as a heat storage property is preferable because the heat storage density is high and the storage and heat dissipation can be performed at around a certain temperature.

Examples of such oily substances capable of storing latent heat include alcohols, esters, ethers, and the like.
Hydrocarbon compounds such as paraffin can be mentioned. Of these, paraffin is preferred.

This has the advantage that paraffin has a high latent heat of fusion with a clear freezing point and that the freezing point can be freely selected. In addition, it easily dissolves the monomer components and polymers described below. Further, it is avoided that the above-mentioned cross-linking is not inhibited without reacting with the polyfunctional compound at the time of polymerization of the monomer component or cross-linking of the polymer. This is because each of the oily gels that can be used in the temperature range can be easily and stably produced.

The reason why such an oily gel can be easily and stably prepared is that paraffins having different structures have a wide melting point temperature range and have various melting points. It is because each can be selected.

Specific examples of the hydrocarbon compound include C
Medium paraffin which is liquid at room temperature such as _{14 to} C ₁₆ paraffin, C _{15 to} C ₁₆ paraffin, pentadecane, C ₁₄ paraffin and C ₁₆ paraffin, or higher paraffin which is solid at room temperature or higher alcohol such as 1-decanol. Can be mentioned. One of these oily substances may be used alone, or two or more of them may be used as a mixture.

The oil-based gelled body is provided with a polymer having a three-dimensional network structure for holding the oil-based substance by shape preservation by gelation. It is desirable to be able to maintain a wide temperature range around the center.

As the polymer, 0.5 g / g of the polymer was used.
g or more, preferably 3 g or more, more preferably 8 g or more, capable of holding a gel-like oily substance. Among them, the equilibrium retention ratio at 25 ° C. to paraffin, especially pentadecane, is 3 g / g. 1 point higher than the melting point of the polymer having the above or the oily substance used
Polymers having an equilibrium retention ratio of 3 g / g or more with respect to oily substances at a temperature higher by 0 ° C. are particularly preferred.

The above-mentioned polymer is provided with a lipophilic portion having lipophilicity to an oily substance. For example, a polymer having a solubility parameter (SP value) of 9 or less and having one polymerizable group in the molecule. It can be obtained by polymerizing a monomer component containing the monomer (A). Further, the polymer is preferably obtained by polymerizing the monomer component in the presence of an oily substance.

The above-mentioned solubility parameter is a parameter generally used as a scale indicating the polarity of a compound. In the present invention, a value (unit) derived by substituting Hoy's cohesive energy constant into Small's equation is used. (Cal / cm ³ )
^1/2 ) is applied.

Further, in order to form a three-dimensional network structure of the polymer, the monomer component preferably contains a crosslinkable monomer described below. Alternatively, in order to form the three-dimensional network structure of the polymer, the monomer component contains a reactive monomer, and after the monomer component is polymerized, a It is desirable that a reactive agent resulting from each reactive monomer be crosslinked with a condensing agent.

As a method for producing such a polymer, the monomer component is polymerized in the presence of an oily substance having a heat storage property, preferably in the presence of an oil-soluble radical polymerization initiator. It is preferable to use a method in which the oily substance is retained in a polymer obtained by polymerizing the monomer components so that the fluidity of the oily substance that is liquefied by the phase change is reduced. Further, it is preferable to select a combination in which the polymer obtained from the above monomer component and the oily substance are basically compatible with each other (ones having similar polarities).

The polymerizable group contained in the monomer (A) is, for example, a polymerizable group capable of polymerizing a polymer by a polymerization method such as radical polymerization, radiation polymerization, addition polymerization, or polycondensation. There is no particular limitation. Among the above-mentioned monomers (A), a monomer having a polymerizable unsaturated group (hereinafter, referred to as monomer (a) for convenience of description) that can easily produce a polymer by radical polymerization is used. Is preferred.

As the monomer (a), specifically,
For example, propyl (meth) acrylate, n-butyl (meth) acrylate, iso-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) Unsaturated carboxylic acid esters such as acrylate, isobornyl (meth) acrylate, dibutyl maleate, didodecyl maleate, dodecyl rotonate, didodecyl itaconate; (di) butyl (meth) acrylamide, (di) dodecyl (meth) acrylamide ,
(Di) stearyl (meth) acrylamide, (di) butylphenyl (meth) acrylamide, (di) octylphenyl (meth) acrylamide, and other hydrocarbon-containing (meth) acrylamide; alicyclic vinyl compounds such as vinylcyclohexane Allyl ethers having a hydrocarbon group such as dodecyl allyl ether; vinyl esters having a hydrocarbon group such as vinyl caproate, vinyl laurate, vinyl palmitate and vinyl stearate; hydrocarbons such as butyl vinyl ether and dodecyl vinyl ether Vinyl ether having a group; aromatic vinyl compounds such as styrene, t-butylstyrene, and octylstyrene; and the like, but are not particularly limited thereto.

Further, as the monomer (A), in addition to the monomer (a), for example, a norbornene-based monomer can be used. When, for example, a norbornene-based monomer is used as the monomer (A), a desired polymer can be easily obtained by employing a polymerization method such as ring-opening polymerization or radical polymerization.

One of these monomers (A) may be used alone, or two or more of them may be used as a mixture.

The other monomer contained as required in the above-mentioned monomer component, that is, other monomer other than the monomer (A), includes the monomer (A) It is not particularly limited as long as it is a copolymerizable monomer. Examples of the other monomer include a monomer having a solubility parameter of more than 9 and having one polymerizable unsaturated group in a molecule.

Examples of the monomer having a solubility parameter exceeding 9 and having one polymerizable unsaturated group in the molecule include (meth) acrylic acid, acrylonitrile, and maleic anhydride. , Fumaric acid, hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate and the like.

Examples of the crosslinkable monomer include, for example, 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, tetramethylolmethanetetra (meth) acrylate, polyhydric alcohol (for example, glycerin, tri Examples include polyfunctional (meth) acrylates and divinylbenzene obtained by esterification of an alkylene oxide adduct of methylolpropane or tetramethylolmethane with (meth) acrylic acid. These other monomers may be used alone or as a mixture of two or more as necessary.

The amount of each monomer used, that is, the content of the monomer (A) in the monomer component is preferably 50% by weight or more, more preferably 70% by weight or more. If the content of the monomer (A) is less than 50% by weight, there is a possibility that a polymer having excellent holding performance of an oily substance may not be obtained.

The other monomers in the monomer component may be used within a range of 50% by weight or less as long as physical properties such as retention of an oily substance in the obtained polymer are not impaired.

As described above, the monomer component includes a crosslinkable monomer having at least two polymerizable unsaturated groups in the molecule, and a content of the crosslinkable monomer in the monomer component. Is preferably 0.001% by weight to 4% by weight in order to form a three-dimensional network structure for retaining an oily substance in the obtained polymer.

That is, when the monomer component contains a crosslinkable monomer, the mixing ratio of each monomer is as follows:
96% by weight of the total amount of monomers other than the crosslinkable monomer
To 99.999% by weight of the crosslinking monomer 0.00
1% by weight to 4% by weight (however, the total amount of each monomer, ie,
The total amount of the monomer components is 100% by weight, and the ratio of the monomer (A) in the monomer components is preferably 50% by weight or more).

If the proportion of the crosslinkable monomer in the monomer component exceeds 4% by weight, the crosslink density of the obtained polymer becomes too high, so that a large amount of oily substance cannot be retained, which is not preferable. . On the other hand, when the proportion of the crosslinkable monomer is less than 0.001% by weight, a remarkable effect due to the addition of the crosslinkable monomer cannot be obtained.

Alternatively, as described above, in order to form a three-dimensional network structure in the polymer, a reactive monomer having a reactive substituent as a functional group for crosslinking is added to the monomer component. , With respect to the total thereof, 0.0
It may contain from 0.05 to 10% by weight.

As such a reactive monomer, a condensable functional group (Y) which is condensed with a condensable functional group (Y) of a cross-linking agent described later to form a chemical bond (covalent bond or ionic bond) is used. Any compound having X) and a polymerizable unsaturated bond may be used. Such a condensable functional group (X) includes a carboxyl group, a hydroxyl group, a mercapto group,
A nitrile group, an amino group, an amide group, an isocyanate group,
Examples include an epoxy group and a polymerizable unsaturated group of an acid anhydride.

Examples of the reactive monomer include a vinyl monomer having a carboxyl group, a vinyl monomer having a hydroxyl group, a vinyl monomer having a mercapto group, and a vinyl monomer having a nitrile group. Monomer, a vinyl monomer having an amino group, a vinyl monomer having an amide group, a vinyl monomer having an isocyanate group, a vinyl monomer having an epoxy group, and a polymerizable unsaturated group. Acid anhydrides and the like.
Species or two or more can be used.

Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, fumaric acid, and itaconic acid. Examples of the vinyl monomer having a hydroxyl group include hydroxyethyl (meth) acrylate,
Examples thereof include polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycerin (meth) acrylate, trimethylolpropane (meth) acrylate, and hydroxystyrene.

The vinyl monomers having a mercapto group include vinyl mercaptan, mercaptoethyl (meth)
Acrylate and the like. Examples of the vinyl monomer having a nitrile group include (meth) acrylonitrile. As a vinyl monomer having an amino group,
Aminoethyl (meth) acrylate, vinylpyridine and the like can be mentioned.

Examples of the vinyl monomer having an amide group include (meth) acrylamide and the like. Examples of the vinyl monomer having an isocyanate group include vinyl isocyanate. Examples of the vinyl monomer having an epoxy group include glycidyl (meth) acrylate. Examples of the acid anhydride having a polymerizable unsaturated group include maleic anhydride.

The crosslinking agent has at least two condensable functional groups (Y) in the molecule, and is contained in a polymer obtained by polymerizing a monomer component containing the reactive monomer. It is appropriately selected according to the condensable functional group (X). Examples of such a crosslinking agent include phenol resins such as dimethylol phenol and polymethylol phenol, which can be condensed when the condensable functional group (X) is a carboxyl group, a mercapto group, a nitrile group, or an epoxy group. No.

As another example of the crosslinking agent, when the condensable functional group (X) is a carboxyl group or a hydroxyl group, an amino compound such as melamine, benzoguanamine or urea which can be condensed with formaldehyde or alcohol is used. An addition-condensed amino resin may be used.

Further examples of the crosslinking agent include hexamethylenediamine, diethylenetriamine and tetraethylenepentamine which can be condensed when the condensable functional group (X) is a carboxyl group, an isocyanate group or an epoxy group. And polyvalent amino compounds.

As still another example of the crosslinking agent, a condensable functional group (X) may be a carboxyl group, a hydroxyl group,
Mercapto group, isocyanate group, amide group, amino group, condensable when it is an epoxy group, hexamethylene diisocyanate, isophorone diisocyanate, p-
Phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, and blocked isocyanates obtained by condensing methanol, phenol, etc. with these isocyanates And isocyanate compounds.

Further examples of the above-mentioned cross-linking agent include malonic acid, succinic acid, adipic acid, phthalic acid, terephthalic acid and the like, which are condensable when the condensable functional group (X) is an isocyanate group or an epoxy group. And polycarboxylic acids such as acids.

Further examples of the crosslinking agent include phthalic anhydride and pyromellitic anhydride, which can be condensed when the condensable functional group (X) is a hydroxyl group, an isocyanate group or an epoxy group. Acid anhydrides such as benzophenonetetracarboxylic acid anhydride are exemplified.

Further examples of the crosslinking agent include aldehyde compounds such as glyoxal and terephthalaldehyde which can be condensed when the condensable functional group (X) is a hydroxyl group, a mercapto group, an amino group or an amide group. Is mentioned.

Further examples of the crosslinking agent include ethylene glycol, diethylene glycol, propylene glycol and hexanediol which can be condensed when the condensable functional group (X) is a hydroxyl group, an isocyanate group or an epoxy group. And other polyhydric alcohols.

As still another example of the crosslinking agent, the condensable functional group (X) may be a carboxyl group, a hydroxyl group,
Epoxy compounds such as toluene glycidyl ether, hexamethylene glycidyl ether, bisphenol A diglycidyl ether, and polypropylene glycol diglycidyl ether, which can be condensed when they are a mercapto group or an isocyanate group, are exemplified.

The combination of each compound as such a crosslinking agent is appropriately determined depending on the type of the condensable functional group (X) contained in the polymer, and one or more of these compounds are used.

Among these, a combination of the condensable functional group (X), which is particularly preferable, and the condensable functional group (Y) of the crosslinking agent 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, and at least one functional group selected from the group consisting of an isocyanate group, an epoxy group, and a carboxylic anhydride group; It is a combination of

By selecting the condensable functional group (X) and the condensable functional group (Y) of the crosslinking agent from the above combinations, it is possible to obtain a polymer in which the residual amount of the unreacted functional groups is reduced. it can. Therefore, by causing the polymer to retain the oily substance, an oily gelled body that does not inhibit the heat storage characteristics of the oily substance can be obtained.

A combination in which the condensable functional group (X) is a hydroxyl group and the condensable functional group (Y) of the crosslinking agent is an isocyanate group, that is, the reactive monomer has a hydroxyl group By selecting a combination in which the crosslinking agent has at least two isocyanate groups in the molecule, the oily substance can be gelled at a low temperature. Therefore, the oily substance can be held in a gel state without using a heat-resistant container, and an oily gel having excellent long-term stability can be obtained.

The ratio of the crosslinking agent used to the polymer to be crosslinked is determined by the number of moles of the condensable functional group (X) which is a constituent unit of the polymer and the condensable functional group (Y) of the crosslinking agent.
And the number of moles of the condensable functional group (Y) is 0.1 to 10 per mole of the condensable functional group (X).
Is preferably within the range.

When the number of moles of the condensable functional group (Y) is less than 0.1 with respect to 1 mole of the condensable functional group (X), the crosslinked polymer cannot be sufficiently crosslinked and has low strength. It is not preferable because only the above may be obtained. On the other hand, if it exceeds 10, undesirably, a crosslinked polymer having excellent properties such as retaining a large amount of oily substances may not be formed.

In order to obtain an effective oil-based gelled product by using such a crosslinking agent, a polymer (oil-based gelling precursor) before crosslinking obtained by polymerizing a monomer component is mixed with a crosslinking agent. Thereafter, before the crosslinking reaction proceeds, for example, the mixture is poured into a container, the oily substance can be melted and maintained in a liquid state, and 0 to
What is necessary is just to carry out a crosslinking reaction at a temperature such as 80 ° C. and to cure. Further, if necessary, the reaction rate can be increased by selecting and using a catalyst that promotes various polymerization reactions and crosslinking reactions.

Further, in order to prevent the condensable functional group (X) and the condensable functional group (Y) from remaining unreacted after the cross-linking reaction, these condensable functional groups (X) and (Y) may be used within a range not hindering the cross-linking reaction. A compound having a reactive group capable of polycondensation with the functional group (X) or 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. It is not preferable that the functional groups (X) and (Y) remain unreacted, since the heat storage properties of the oily substance may be impaired.

As described above, when the monomer component contains a crosslinkable monomer or a reactive monomer, a crosslinked structure that forms a three-dimensional network structure is introduced into the obtained polymer, and the weight of the oily substance is reduced. It is effective in suppressing the solubility of coalescence.

When the polymer has a crosslinked structure that forms a three-dimensional network structure, it is easy to control the amount of the oily substance retained in the obtained oily gelled product, and furthermore, the fluidization or bleeding of the oily substance Dashi can be more reliably prevented. As a result, it is possible to ensure the shape retention of the obtained oily gel.

In the oil-based gelled product provided with such a polymer, since the leakage of the oil-based material from the oil-based gelled product is reduced, other components such as water and powder are added to the leaked oil-based material. It is possible to suppress a decrease in the freezing point of the oily substance, that is, a decrease in the phase change temperature of the oily substance due to the mixture of the building and civil engineering material. Therefore, the overall state of the oily substance is further stabilized by the oily gelled body, so that the freezing point can be prevented from lowering and the phase change temperature of the oily substance can be clarified.

Among these polymers, polyolefins and polymers other than polymers having high crystallinity, especially at least one aliphatic hydrocarbon group having 3 to 30 carbon atoms as a lipophilic portion for an oily substance. At least one selected from the group consisting of alkyl (meth) acrylates, alkylaryl (meth) acrylates, alkyl (meth) alkylamides, alkylaryl (meth) acrylamides, fatty acid vinyl esters, alkyl vinyl esters and alkylstyrenes A polymer obtained by polymerizing a monomer component containing 50% by weight or more of one type of monomer (unsaturated compound, hereinafter, referred to as monomer (a ') for convenience of description) is an oily substance. Is preferred because it has good compatibility and affinity and can obtain an oily gelled substance with less oozing out of an oily substance.

Further, as the above polymer, particularly, a polymer obtained by polymerizing a monomer component containing 50% by weight or more of a monomer (a ′) having 4 to 24 carbon atoms as a lipophilic portion is used. The compatibility and affinity between the polymer and the oily substance are further improved,
It is possible to obtain an oily gel without exudation of an oily substance.

Further, when the polymer obtained by polymerizing a monomer component containing 50% by weight or more of a monomer (a ′) having 8 to 18 carbon atoms as a lipophilic portion is used, An oily gel having appropriate flexibility can be obtained.

Therefore, when the above oily gel is used,
In addition to the above-mentioned effects, since it is excellent in flexibility, the obtained oil-based gelled body has good adhesion in the molded body of the building and civil engineering material, and the heat transfer property is improved, and the vibration absorption property is improved. Since it is excellent, it is possible to improve the vibration damping effect of a molded article made of such a heat storage agent composition.

In addition, the above polymer is preferably prepared by adding an alkyl (meth) acrylate to the monomer (a ′) in an amount of 50% by weight.
When the monomer component contained is polymerized, the transparency of the oily gel is maintained high even by repeated freezing and thawing, so that a heat storage agent composition having light transmittance can be obtained.

When the above polymer is used, the oily substance can be maintained in a gel state at a relatively low temperature. Therefore, at a relatively low temperature, the oily gel, that is, the heat storage agent composition of the present invention can be prepared. In addition to being able to be manufactured, separation of the oily substance from the oily gelled substance is prevented by the retention of the oily substance by gelation, the oozing of the oily substance is less than before, and the flammability and fire spread in the event of a fire are reduced. A remarkably reduced heat storage agent composition with high safety can be obtained.

The heat storage agent composition of the present invention can be used as it is in a molded article of a building or civil engineering material for the purpose of heat storage or cold storage.

The method for producing the heat storage agent composition of the present invention is a method in which the above oily gel is mixed with a building and civil engineering material in an aqueous dispersion of the above oily gel. In the above method, the aqueous dispersion of the oily gel is obtained by suspension polymerization of a monomer (Y) having an lipophilic portion having affinity for the oily substance in the presence of the oily substance and water. Preferably, it is obtained.

Another method for producing the heat storage agent composition of the present invention is as follows.
A mixed solution of a liquid oily gelling precursor having the lipophilic portion having an affinity for the oily substance and the above oily substance, and a porous building and civil engineering material mixed with each other, and then mixed with the oily gelling precursor This is a method of forming an oily gel body holding an oily substance in the building and civil engineering material by polymerizing and / or crosslinking the body.

The method for producing the heat storage agent composition of the present invention is more specifically (1) a method of mixing a polymer and an oily substance, and (2) a method of cross-linking polymerization in the presence of an oily substance. (3) a method in which polymerization is carried out in the presence of an oily substance followed by crosslinking, and (4) a method in which a polymer is formed by polymerization in building and civil engineering materials.

(1) As a method for mixing a polymer and an oily substance, a. A method of retaining the oily substance in the polymer and then mixing the polymer with a building / civil engineering material and water; b. A method of mixing an oily substance with an aqueous dispersion of a polymer to hold the oily substance in the polymer, and then mixing the aqueous dispersion of the polymer with architectural / civil engineering materials; c. A method of mixing a polymer with a building / civil engineering material and water, and then mixing an oily substance to retain the oily substance in the polymer; d. After mixing the aqueous dispersion of the polymer with building and civil engineering materials,
There is a method in which an oily substance is mixed and the above-mentioned oily substance is retained in a polymer.

The above a. ~ D. According to the method, a heat storage agent composition having a high content of an oily substance can be obtained. The above c. According to the method, since the polymer has an affinity for the oily substance due to its property of retaining the oily substance in a gel state, the presence of water promotes the retention of the oily substance by the polymer. It becomes possible. Thereby, in the above method, the retention of the oily substance can be promoted, so that the production of the heat storage agent composition can be simplified.

(2) As a method of crosslinking and polymerizing in the presence of an oily substance, e. A method of mixing an oily gel obtained by bulk polymerization of a monomer component (including a crosslinkable monomer) in the presence of an oily substance with a building / civil engineering material and water; f. Mixing a monomer component (including a crosslinkable monomer) with an aqueous dispersion of an oily gel obtained by suspension polymerization in water in the presence of an oily substance and a building / civil engineering material, g. A mixed solution of a monomer component (including a crosslinkable monomer) (oil-based gelling precursor) and an oil-based substance is dispersed in a building or civil engineering material, and during or after curing of the building or civil engineering material, A method of polymerizing the above monomer component may be used.

E. ~ G. According to the method, the oil-based gelled body containing the oil-based substance can be manufactured in a single step, so that the manufacture of the oil-based gelled body can be simplified. In addition, b. , F. In the method, the oil-based gelled body is mixed with the building and civil engineering material in the form of an aqueous dispersion, so that the oil-based gelled body can be more uniformly dispersed and supported on the building and civil engineering material. .

Further, the above f. According to the method of, the aqueous dispersion of the oily gelled body obtained in one step, as it is,
When mixed with architectural and civil engineering materials, the oily gel is easily and uniformly dispersed in the architectural and civil engineering materials. Therefore, the above method is particularly effective in terms of performance and productivity of the obtained heat storage agent composition.

(3) After polymerization in the presence of an oily substance,
As a method of crosslinking, h. The monomer component (including the reactive monomer) is polymerized in the presence of an oily substance, and then the oily gel obtained by polycondensing with a crosslinking agent is mixed with the building / civil engineering material and water. The method, i. A mixed solution obtained by mixing a polymer solution obtained by polymerizing a monomer component in the presence of an oily substance and a crosslinking agent (oily gelation precursor)
Is mixed with an architectural / civil engineering material and water, and during or after curing of the architectural / civil engineering material, polycondensation of the polymer liquid and a crosslinking agent is mentioned.

E. ~ I. According to the method of a. ~
d. The polymer is formed in the presence of the oily substance as compared with the method of the above, so that the free (not retained in the oily gelled substance) oily substance can be significantly reduced, so that the oozing of the oily substance is extremely suppressed. can do.

The above i. According to the method of (1), the oily gelation precursor before obtaining the oily gelation body can be handled as a liquid, so that the oily gelation precursor can be easily applied to a porous building and civil engineering material, for example, a concrete block. Can be impregnated. By gelling the impregnated oil-based gelling precursor by crosslinking, the above-mentioned method j described below can be most easily performed.

(4) A method for forming an oily gel by polymerizing or / and cross-linking a building or civil engineering material, j. A method according to any one of the above (1) to (3), in which a porous building and civil engineering material is impregnated in a liquid state and then gelled. J. The methods that can be used are specifically as described in the following (A) to (C).

(A) An oily substance is added to a polymer, and impregnated in a porous building or civil engineering material while the oily substance is being gelled, that is, held (in a state of fluidity), and then the gelation is completed. A method of retaining oily gel bodies in building and civil engineering materials.

(A) Monomer component (including crosslinkable monomer)
A method of impregnating a porous building and civil engineering material with a mixed solution comprising a water and an oily substance, and then polymerizing the monomer component to thereby retain an oily gelled body in the building and civil engineering material.

(C) Monomer component (including a crosslinkable monomer)
After impregnating a mixed solution comprising a polymerization solution obtained by polymerizing the polymer in an oily substance and a cross-linking agent into a porous building and civil engineering material, the functional group of the reactive monomer and the functional group of the cross-linking agent overlap. A method in which an oily gel is condensed and consequently retained in architectural and civil engineering materials.

Such j. According to the method, oil-based gelled material having heat storage properties for existing building and civil engineering materials,
It is possible to stably obtain a heat storage agent composition which can be easily and uniformly supported and in which oozing of an oily substance is prevented.

In the method for manufacturing a heat storage structural material described in Japanese Patent Application Laid-Open No. Hei 6-57241, at least a part of the paraffins and the hydrocarbon organic polymer of the binder component is melted while heating at 50 to 250 ° C. In the state
Since it is necessary to mix the paraffins and the hydrocarbon-based organic polymer, there is a problem that the preparation takes time.

However, in the heat storage agent composition and the method for producing the same according to the present invention, since the oily gelled substance can retain the oily substance at room temperature, the preparation of the oily gelated substance retaining the oily substance has been conventionally carried out. It can be simplified.

The method for producing the polymer is not particularly limited, and various known methods such as radical polymerization, radiation polymerization, addition polymerization and polycondensation may be employed. Can be. The polymer is easily prepared, for example, by dispersing a monomer component in an aqueous medium in the presence of a protective colloid or a surfactant, and then subjecting the monomer component to suspension polymerization with a polymerization initiator such as an oil-soluble radical polymerization initiator. Can be manufactured. If necessary, the monomer component may be dissolved in a water-insoluble organic solvent before suspension polymerization.

The protective colloid agent and the surfactant are not particularly limited, and their amounts are not particularly limited. Specific examples of the protective colloid agent include, for example, polyvinyl alcohol, hydroxyethyl cellulose, gelatin and the like. Specific examples of the surfactant include sodium alkyl sulfonate, sodium alkyl benzene sulfonate, polyoxyethylene alkyl ether, fatty acid soap and the like. One of these protective colloid agents and surfactants may be used alone, or two or more of them may be used as a mixture.

The polymerization initiator is not particularly limited, but specific examples thereof include organic peroxides such as benzoyl peroxide, lauroyl peroxide and cumene hydroperoxide; Examples include azo compounds such as azobisisobutyronitrile and 2,2'-azobisdimethylvaleronitrile. These polymerization initiators may be used alone or as a mixture of two or more as needed. The amount of the polymerization initiator used depends on the type and amount of the monomer component, but is preferably used in the range of 0.1% by weight to 5% by weight based on the monomer component. .

The polymerization temperature at the time of conducting the above polymerization reaction is not particularly limited, but is preferably from 0 ° C.
The temperature may be appropriately set within the range of 150 ° C. according to the type of the monomer component, the polymerization initiator, and the like. Furthermore, the polymerization time when performing the polymerization reaction is not particularly limited, either, the type of the monomer component or the polymerization initiator or the amount used, the reaction temperature, etc., the reaction is terminated. like,
What is necessary is just to set suitably.

Among these methods, suspension polymerization or suspension polycondensation is preferred since a granular polymer, in particular, a spherical polymer can be directly obtained after polymerization. If the polymer is granular, the surface area of the polymer increases, and the gelation rate of the oily substance can be improved.

That is, the oily gelled product can be easily obtained by keeping the oily substance in a liquid phase in the polymer under a temperature condition exceeding the freezing point of the oily substance. When the oily substance in the liquid phase is retained in the polymer, the polymer may be heated for the purpose of shortening the time for retaining the oily substance by gelation.

The proportion of the polymer and the oily substance used, that is,
The content of the polymer and the oily substance in the oily gel is not particularly limited, but is in the range of 4% to 20% by weight of the polymer and 96% to 80% by weight of the oily substance. It is preferable to be within the range. If the proportion of the polymer is less than 4% by weight, the oily substance cannot be completely gelled and retained, and bleeding or fluidization when the oily substance is in a liquid state may occur. On the other hand, when the polymer ratio is 2
If it exceeds 0% by weight, the content of oily substances is small,
The phase change latent heat of the obtained heat storage agent composition may be small, and the heat storage efficiency may be reduced.

Further, when the polymer is granular, when the polymer retains an oily substance, it can expand into a similar shape to obtain a granular oily gel. Therefore, suspension polymerization or suspension polycondensation capable of obtaining a spherical polymer and a spherical oily gel is particularly preferable as a method for producing the polymer.

When a granular polymer is obtained by a method other than suspension polymerization or suspension polycondensation, the oily gel obtained from the polymer becomes an aggregate of granular heterogeneous substances (amorphous). However, as compared to the case where a spherical oily gel is used, the uniformity when the additive is added is inferior. In addition, since a crushing operation is required when the polymer is made into a spherical shape, the polymer is likely to contain air bubbles, and air bubbles may be included inside the obtained oily gelled product.

The average particle size of the independent unit in the granular polymer is preferably 5 mm or less, more preferably 3 mm or less, and particularly preferably 1 mm or less. When the average particle size is 5 mm or less, the time for forming the oily gel is shortened, so that the productivity is improved. When the average particle size is 1 mm or less, heating at a high temperature is not required, and an oily gel can be formed at a relatively low temperature. Further, the granular polymer is preferably a polymer having a high molecular weight or a crosslinked structure having a three-dimensional network structure.

When a conventional polymer is used, that is, as the polymer, polyethylene pellets or SEB are used.
When S (styrene-ethylene / butylene-styrene block polymer) powder is used, when the polymer forms an oily gel by mechanical mixing and holds an oily substance by gelation, the oily gel is formed into granular oily gel. Since the bodies are easily brought into contact with each other under pressure and melted to be integrated, it is easy to obtain a massive oil-based gelled body. As described above, when the oil-based gelled substance is a large integrated gel, the oil-based gelled substance may ooze out of the oily substance due to a larger strain due to a volume change during freeze-thawing of the oily substance. .

However, in the heat storage agent composition and the method for producing the same according to the present invention, the oily gelled body can retain the oily substance at room temperature, so that even if the respective oily gelled bodies come into contact with each other, the oily gelled body can be kept in a conventional manner. It is possible to prevent the oily substance from being unified due to the melting and to prevent the oily substance from bleeding due to strain caused by a change in volume during freeze-thawing of the oily substance.

Further, as a method for producing the polymer of the present invention, a bulk polymerization method may be employed. When a polymer is obtained by a bulk polymerization method, for example, a monomer component is poured into a mold in the presence of a polymerization initiator, and preferably at 50 ° C.
By heating to 150 ° C., a polymer can be easily obtained. As the polymerization initiator, the same polymerization initiator as the above-described polymerization initiator can be used. When bulk polymerization is employed, the polymer may be obtained as a bulk material, and, if necessary, the obtained bulk material may be subjected to an operation such as pulverization to adjust the particle size, thereby obtaining a granular material. May be obtained as a polymer.

For the purpose of increasing the gelation rate of the oily substance of the polymer, the water-insoluble compound is mixed with the water-insoluble compound as long as the oily substance retention performance of the polymer is not reduced.
It may be a granular polymer. As the water-insoluble compound,
The compound is not particularly limited as long as it is a compound having a water insolubility or poor water solubility of 1 g or less in 100 g of water at 20 ° C.

Specific examples of the water-insoluble compound include minerals such as silica, talc and diatomaceous earth; metals such as iron and alumina; inorganic salts such as calcium carbonate; organic acid salts such as metal soap; , Polyethylene, polyvinyl acetate and other resins; organic compounds such as wax; cotton;
Fibers such as pulp and the like are included. These water-insoluble compounds may be used alone or as a mixture of two or more as necessary.

Among these water-insoluble compounds, compounds in the form of powder that can effectively prevent the polymer from being powdered with a small amount of use are preferable. Organic acid metal salts having a solubility in 100 g of water at 20 ° C. of 1 g or less are preferable. Further, a powder of a hydrophobic inorganic compound having a methanol value of 25% by weight or less is particularly preferred. The methanol value is a measure of the degree of hydrophobicity of the water-insoluble compound, and is represented by the volume% of methanol in the aqueous methanol solution that allows the water-insoluble compound to become wettable.

The heat storage agent composition may contain a substance other than the constituents of the oily gelled substance, for example, a flame retardant substance. In particular, when the heat storage agent composition according to the present invention further contains a flame retardant, the safety of the heat storage agent composition can be further improved. The non-combustible substance is not particularly limited as long as it can reduce the heat of combustion and the spreadability of the heat storage agent composition, but water and inorganic powder are preferable.

[0126]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. [Example 1] In a 500 ml flask equipped with a thermometer, a stirrer, a gas inlet tube and a reflux condenser, 3 parts of gelatin was added to 3 parts of water.
Dissolved in 00 parts and charged. Next, the inside of the flask was replaced with nitrogen, and the aqueous solution in the flask was removed under a nitrogen stream for 4 hours.
The temperature was raised to 0 ° C.

On the other hand, 99.823 parts of dodecyl acrylate (SP value: 7.9) as a monomer (A) and 0.17 parts of ethylene glycol diacrylate as a crosslinkable monomer
A mixed solution was prepared by mixing 7 parts and 0.5 part of benzoyl peroxide as a polymerization initiator.

Thereafter, the mixed solution was added to the flask at one time, and the mixture was stirred at 400 rpm to obtain a uniform solution. Next, the temperature inside the flask was raised to 80 ° C., and the mixture was stirred at this temperature for 2 hours. Thereafter, the temperature was further raised to 90 ° C., and the mixture was stirred for 2 hours to perform a suspension polymerization reaction.

Next, the obtained substantially spherical polymer (having a particle size of 1
100 to 1000 μm), the total amount of the aqueous dispersion containing 30 ×
Transfer to a 40 × 6 cm SUS vat, add 400 parts of hexadecane (phase change temperature: 20 ° C.) as an oily substance, and stir to cause the above hexadecane to gel with the above polymer and retain hexadecane An aqueous dispersion of a substantially spherical oily gel was obtained.

Subsequently, the above aqueous dispersion, 1200 parts of water as a building and civil engineering material and 2000 parts of gypsum were added to each other and mixed uniformly, as shown in FIG. Then, a heat storage agent composition (1) of the present invention was obtained in which substantially granular oily gels were dispersed.

The above thermal storage composition (1) was prepared at 70 ° C.
After standing for 5 hours, it was confirmed that a molded product in which the gypsum had hardened was formed, and the molded product was taken out of the vat to disperse the spherical oil-based gelled substance containing hexadecane and contained in the gypsum board. A heat storage agent molded product (1) was obtained. Such a heat storage agent molded product (1) was useful as an energy-saving wall material, a heat-increasing material for frame heat storage, and the like.

Example 2 95 parts of dodecyl acrylate (SP value: 7.9) as monomer (A), 4.5 parts of ethylene glycol diacrylate, and 2,2′-azobis ( A mixed solution in which 0.5 part of 4-methoxy-2,4-dimethylvaleronitrile and 400 parts of tetradecane (phase change temperature: 5 ° C.) as an oily substance were mixed so as to be uniform with each other was 26 × 26 × 1 cm. In a SUS casting polymerization container.

Next, a sufficient amount of nitrogen gas was introduced into the mixed solution through a gas inlet tube mounted on the upper portion of the container, and oxygen in the mixed solution was replaced with nitrogen gas. Subsequently, the container was allowed to stand in a thermostat kept at 40 ° C. for 8 hours while maintaining the nitrogen gas atmosphere, and then peeled off from the container to obtain an oily gelled substance holding the oily substance. Was.

On the other hand, the sand 67
3 parts and 200 parts of cement were kneaded, and then a mixed solution consisting of 126 parts of water and 1 part of a naphthalenesulfonic acid formaldehyde condensate was added and kneaded to prepare a mortar.

Further, the mortar was mixed with
And the entire amount of the oil-based gelled substance obtained by the polymerization is added and kneaded, and the oil-based gelled substance is crushed, and the oily gelated substance in the form of irregular shaped particles is dispersed and contained. A heat storage agent composition (2) of the present invention comprising a building and civil engineering material was obtained.

Subsequently, the heat storage agent composition (2) was poured into the vat described in Example 1 and allowed to stand for 24 hours.
By peeling off, a heat storage agent molded product (2) comprising a plate-like concrete containing an oil-based gelled body containing tetradecane was obtained. Such a heat storage agent molded product (2) was useful for snowmelt roads and the like.

Example 3 A 3 liter flask equipped with a thermometer, a stirrer, a gas inlet tube and a reflux condenser was prepared by dissolving 15 parts of polyvinyl alcohol in 1485 parts of water.
Under stirring, the inside of the flask was replaced with nitrogen, and the temperature was raised to 80 ° C. under a nitrogen stream.

Thereafter, 95 parts of dodecyl acrylate (SP value: 7.9) as the monomer (A), 4.5 parts of ethylene glycol diacrylate as a crosslinkable monomer, and benzoyl peroxide as a polymerization initiator 0.5
Part and, as an oily substance, a melting point of 4
What melted 400 parts of paraffin at 0 ° C. at 50 ° C.
The mixed solutions mixed so as to be uniform with each other were added to the flask at once, and a suspension polymerization reaction was performed for 2 hours under a nitrogen gas stream while stirring at 400 rpm. Thereafter, the temperature inside the flask was further raised to 90 ° C.
The polymerization was completed over a period of time to obtain an aqueous dispersion containing a paraffin-containing oily gel.

Next, the whole amount of the obtained aqueous dispersion was transferred to the vat described in Example 1, and 200 parts of gypsum were further added to obtain a heat storage agent composition (3) of the present invention.

Subsequently, the heat storage agent composition (3) was mixed with 70
C. for 2.5 hours, confirming that the gypsum has hardened,
By peeling from the bat, on a gypsum board,
A heat storage agent molded product (3) containing a paraffin-containing oily gel was obtained. Such a heat storage agent molded product (3) was useful for a heat storage type floor heating or the like.

Example 4 A 500 equipped with a thermometer, a stirrer, a gas inlet tube, two dropping funnels and a reflux condenser was prepared.
In a milliliter flask, 10 g of a mixture of pentadecane and hexadecane (85/15 weight ratio, phase change temperature: 10 ° C.) as an oily substance is charged, and the flask is purged with nitrogen under stirring and heated to 65 ° C. under a nitrogen stream. did.

Next, 2-ethylhexyl acrylate (SP value: 7.0) was added to one dropping funnel as a monomer component.
8) 38 g and 2 g of hydroxyethyl acrylate,
And a solution consisting of 40 g of a mixture of pentadecane and hexadecane (85/15 by weight) as an oily substance was added to another dropping funnel as 2,2′-polymerization initiator.
Azobis (4-methoxy-2,4-dimethylvaleronitrile)
0.1 g, and a mixture of pentadecane and hexadecane as oily substance and diluent (85/15 weight ratio)
10 g of each solution were charged.

Subsequently, the solution and the solution were simultaneously dropped into the flask over 1 hour to carry out a polymerization reaction. Thereafter, the temperature in the flask was further raised to 80 ° C.
The polymerization was completed by maintaining for a time to obtain a polymer before crosslinking.

After cooling, 2.3 g of toluene diisocyanate as a cross-linking agent, 0.1 g of dibutyltin dilaurate, and a mixture of pentadecane and hexadecane as a diluent (85 g) were added to the flask.
Immediately after adding and mixing a solution consisting of 100 g / 15% by weight, the entire amount was 1260 cm ³ (10 × 6 × 2
1 cm) absorbed into a concrete block having a porosity of 20% by volume. Then, the mixture is allowed to stand for 4 hours in a constant temperature bath at 60 ° C. to allow the crosslinking reaction to proceed, whereby the heat storage agent composition of the present invention comprising the oily gelled product containing a mixture of pentadecane and hexadecane in a concrete block ( 4)
That is, a heat storage agent molded product (4) was obtained. Such a heat storage agent molded product (4) was useful for a wall for a water heat storage water tank and the like.

Comparative Example 1 The above-mentioned JP-A-8-86476 was used.
Comparative heat storage agent molded product (1) corresponding to the latent heat storage board disclosed in Japanese Patent Application Laid-Open Publication No. H11-157,086 was prepared. That is, 400 parts of hexadecane and 1500 parts of water were added to the bat described in the first embodiment.
Parts and 200 parts of gypsum were added to each other and mixed.
The gypsum was cured by standing at 0 ° C. for 2.5 hours. After cooling down,
By peeling the cured product from the vat, the comparative heat storage agent molded product (1) containing hexadecane on the gypsum board was obtained.

[Comparative Example 2] The above-mentioned JP-A-6-57241
A comparative heat storage agent molded product (2) corresponding to the heat storage structure building material disclosed in Japanese Patent Application Publication No. H10-115,086 was prepared. That is, 100 parts of SEBS thermoplastic elastomer (manufactured by Shell Chemical Co., trade name: Clayton G) in a stirring and mixing machine kept at a temperature of 140 ° C.,
400 parts of hexadecane was melt-stirred and stirred for 1 hour. After cooling, cut into cubic chips with an average of 5 mm.
After putting 1500 parts of water and 200 parts of gypsum into the vat and mixing, the mixture was allowed to stand at 70 ° C. for 2.5 hours to harden the gypsum.

After cooling, the cured product is peeled from the vat to form a comparative heat storage agent molded product in which a heat storage material obtained by mechanically mixing hexadecane with a thermoplastic elastomer is dispersed in a gypsum board. (2) was obtained.

Next, the heat storage agent moldings (1) to (4) from the heat storage agent compositions (1) to (4) of Examples 1 to 4 described above,
And each comparative heat storage agent molded product (1) described in Comparative Examples 1 and 2
About (2), the physical property change with time by a repeated test and the appearance change by a high temperature test were measured. The results are shown in Table 1.

[0149]

[Table 1]

That is, the heat storage agent molded products (1) to (4),
And the comparative heat storage agent molded products (1) and (2) were respectively put into a thermostat, and the phase change temperature of each oily substance was centered.
According to a time program in which the upper limit temperature and the lower limit temperature shown in Table 1 are each set to 8 hours, freeze-thaw of the oily substance is repeated 20 times, and then the heat storage agent molded product (1)
To (4) and from the comparative heat storage agent molded products (1) to (2), the presence or absence of seepage of the liquid oily substance was visually observed.
Changes in physical properties over time were measured.

The heat storage agent molded products (1) to (4) and the comparative heat storage agent molded products (1) and (2) were each heated to 70 ° C.
After standing for 24 hours under the above temperature conditions, the presence or absence of seepage of the oily substance from each of the molded products was visually measured as the presence or absence of a change in appearance due to a high temperature test.

As a result, in the thermal storage agent molded product (1) and the comparative thermal storage agent molded product (2), when the freezing and thawing of the oily substance before and after the phase change temperature of the used oily substance were repeated, Although slight seepage of the substance was observed,
It can be seen that it can be used stably and safely in a normal use temperature range utilizing latent heat due to a phase change of an oily substance.

Further, in the heat storage agent molded products (2) to (4), bleeding of the oily substance was observed even after repeated freezing and thawing of the oily substance before and after the phase change temperature of the used oily substance. In other words, it can be seen that it can be used stably and safely in a normal use temperature range utilizing latent heat due to a phase change of an oily substance.

However, in the comparative heat storage agent molded product (1), oozing of the oily substance was greatly observed, and the oozing oily substance was liable to catch fire or spread fire. It turns out that safety and stability are inferior because heat storage property deteriorates.

From the results of the high-temperature test described in Table 1,
In the heat storage agent molded products (1) to (4), bleeding of an oily substance was not observed even under a high temperature environment, and the heat storage agent composition of the present invention can be applied to a place where a high temperature environment is provided. Is obtained.

On the other hand, in the comparative heat storage molded products (1) and (2), seepage of oily substances was observed, and in places where high temperature environment was present, there was a great risk of ignition or fire spread. Is decreased with the passage of time, which indicates that it is inferior in safety and stability and cannot be applied.

As described above, even if the flammable oily substance is liquefied by the phase change for heat storage, the heat storage agent composition of the present invention reduces the fluidity of the oily substance to form a gel. Or, it can be stably maintained in a solid state to prevent leakage from the oily gelled product, and even under normal use conditions where freezing and melting are repeated for heat dissipation and heat storage, it can be used for molding from building and civil engineering materials. It is excellent in stability over time of physical properties such as avoiding leakage of oily substances.

Further, in the method for producing a heat storage agent composition of the present invention, the oily gelled product is prepared by mixing a monomer component which is in a liquid state at room temperature or a polymer before crosslinking in a container at 80 ° C. It is obtained by keeping the oily substance in a gel or solid state in building and civil engineering materials by polymerizing or crosslinking at around 40 ° C. or around room temperature as described below.

From the above, it can be seen that the above method can reliably and easily produce a heat storage agent composition having excellent stability as described above, and can optimally fill an oil-based gelled material into the building and civil engineering material. Therefore, the heat storage agent composition can be stably manufactured at low cost.

The heat storage agent composition of the present invention can be used as a sheet, board, panel, thick slate, clay tile, tile, or brick having excellent heat storage properties for walls, floors, and tiles.
Use in a wide range of fields such as building air conditioning, hot water supply, heat and cold insulation in food factories and chemical factories, floor and wall heating building materials, heat and cold transport systems, floor materials, roof materials, solar heat collectors, etc. Can be.

[0161]

As described above, the heat storage agent composition of the present invention has a construction having an architectural / civil engineering material and an oil-based gelled body holding an oil-based substance having heat storage properties.

According to the above configuration, since the oily substance is held in the oily gelled substance, bleeding and fluidization of the oily substance from the oily gelated substance can be reduced as compared with the related art, and the exposure of the oily substance is suppressed. Therefore, the flammability and the spread of fire caused by the oily substance can be significantly reduced.

In addition, in the above configuration, since the oily substance is held by the oily gelled body, it is possible to suppress the oozing of the oily substance even at a high temperature as compared with the conventional case. It is possible to apply the present invention, and it is possible to expand the applicable range while improving safety as compared with the related art.

As described above, the method for producing a heat storage agent composition according to the present invention provides a monomer (Y) having a lipophilic moiety having an affinity for the oily substance in the presence of the oily substance having heat storage properties. ) Is polymerized to obtain an oily gelled substance holding the oily substance, and then the oily gelated substance is mixed with a building / civil engineering material.

According to the above-mentioned method, it is possible to obtain an oily gelled substance capable of holding more oily substances, so that the heat storage efficiency of a molded article of a building / civil engineering material containing the oily gelled substance is improved. It has the effect of being able to do so.

The method for producing another heat storage agent composition of the present invention is as follows.
In the presence of an oily substance and water, the monomer (Y) having an lipophilic moiety having an affinity for the oily substance is subjected to suspension polymerization to obtain an aqueous dispersion of an oily gel, Building water dispersion
It is a method of mixing with civil engineering materials.

According to the above method, the building and civil engineering material is usually used by suspending it in water and molding it, and then forming it by drying or solidifying by a hydration reaction. For this reason, in the above method, by using the water dispersion of the oily gelled body, the water of the water dispersion can be used as at least a part of the water for suspending the building / civil engineering material. Become. Therefore, there is an effect that the formation of the molded article can be simplified.

Still another method for producing a heat storage agent composition according to the present invention is a method for producing a mixture of a liquid oily gelling precursor having a lipophilic portion having an affinity for an oily substance and the above oily substance; After the porous building and civil engineering materials are mixed with each other, the oily gelling precursor is polymerized and / or cross-linked in the presence of the oily substance, and the oily gelled body holding the oily substance is converted into the above-mentioned building and civil engineering material. This is a method of forming a material.

According to the above method, the liquid mixed solution is
After mixing with a porous building and civil engineering material, the oily gelling precursor is polymerized or / and cross-linked to obtain an oily gelling product, which corresponds to the internal shape of the building and civil engineering material, that is, It becomes possible to form an oil-based gelled body that matches the internal voids of building and civil engineering materials.

From the above, according to the above method, even when the oil-based gelled material containing an oily substance has an irregular or complicated shape, the oil-based gelled material can be reliably applied to a building / civil engineering material. The effect that it becomes possible to form it is produced.

[0171] Still another method of producing a heat storage agent composition according to the present invention is to mix an oily substance, a granular polymer that holds the oily substance in a gel state, and a building / civil engineering material in the presence of water. Then, the oily substance is held in the polymer to form an oily gelled body, and the oily gelled body is dispersed in the solidified building / civil engineering material.

According to the above method, since the polymer has an affinity for the oily substance due to its property of retaining the oily substance, the polymer, the oily substance, and the building / civil engineering material are mixed with each other. This makes it possible to simultaneously promote the retention of the oily substance by the polymer due to the presence of water and promote the retention of the oily substance by the polymer. Thereby, in the above method, since the mixing and the holding can be advanced simultaneously and the holding can be promoted, there is an effect that the production of the heat storage agent composition can be simplified.

[Brief description of the drawings]

FIG. 1 is a schematic view of a heat storage agent composition of the present invention.

[Explanation of symbols]

 1 Oily gel 2 Building and civil engineering materials

Claims (8)

[Claims] 1. A heat storage agent composition comprising a building and civil engineering material, and an oily gelled substance holding an oily substance having heat storage properties. 2. The heat storage agent composition according to claim 1, wherein the oily substance is a compound having heat storage properties due to a phase change between a liquid phase and a solid phase. 3. The heat storage composition according to claim 1, wherein the oily gel has a three-dimensional network structure for retaining an oily substance. 4. The oil-based gelled product has a solubility parameter (S
4. The heat storage agent composition according to claim 1, comprising a polymer obtained by polymerizing a monomer component containing a monomer (A) having a P value of 9 or less. 5. An oily gel which retains the oily substance by polymerizing a monomer (Y) having an lipophilic moiety having an affinity for the oily substance in the presence of an oily substance having a heat storage property. A method for producing a heat storage agent composition, comprising mixing the oily gel body with a building / civil engineering material after obtaining a body. 6. In the presence of an oily substance and water, a monomer (Y) having an lipophilic moiety having an affinity for the oily substance is subjected to suspension polymerization to obtain an aqueous dispersion of an oily gel. And then mixing the aqueous dispersion with a building and civil engineering material. 7. A mixed solution of a liquid oily gelation precursor having a lipophilic portion having an affinity for an oily substance and the above oily substance, and a porous building and civil engineering material mixed with each other. Polymerizing the oily gelling precursor in the presence of an oily substance and / or
Or crosslinked, the oily gel body holding the oily substance,
A method for producing a heat storage agent composition, wherein the composition is formed on the building and civil engineering material. 8. An oily substance, a granular polymer which holds the oily substance in a gel state, and a building / civil engineering material are mixed in the presence of water, and the oily substance is retained in the polymer to form an oily substance. A method for producing a heat storage agent composition, which comprises forming a gelled body and dispersing the oily gelled body in a solidified building / civil engineering material.