JP4696484B2 - Latent heat storage material composition - Google Patents

Description

  The present invention relates to a latent heat storage material capable of storing various heat energy at high density using latent heat generated in accordance with phase change of melting or solidification, and aliphatic hydrocarbons in a dispersion medium such as water. The latent heat storage material composition is provided by dispersing and further increasing the viscosity of the dispersion into a gel state with poor fluidity.

  Many researches have been made on heat storage / cold storage, which stores various types of energy such as waste heat, natural energy, and night electricity as heat energy, as it lowers energy costs and is also an environmental measure through effective use of energy.

  As is well known, heat storage / cold storage uses sensible heat storage using the specific heat and temperature difference of materials, latent heat storage using latent heat of fusion and latent heat of vaporization that accompanies the phase change of materials, heat generation of chemical reactions, and heat absorption. It is done by methods such as chemical heat storage. In particular, latent heat storage has a large amount of heat storage, and has various applications because it absorbs and releases heat at a constant temperature.

Conventionally, organic compounds such as water, inorganic hydrated salts, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, higher alcohols, fatty acids, ester compounds and the like have been proposed as heat storage materials using latent heat. Among them, aliphatic hydrocarbons are easy to set the temperature of phase change to the target temperature depending on the number of carbon atoms of the compound, and the form to be used is a method of dispersing aliphatic hydrocarbons as microcapsules in a continuous phase such as water. (Patent Literatures 1 to 4), a method of dispersing as an emulsion (Patent Literatures 5 to 9), dispersing and fixing in a matrix (Patent Literatures 10 to 14), and aliphatic hydrocarbon gel As a solid phase, it can be enclosed in a container (Patent Documents 15 and 16 described later), etc., and can be used in a form according to the purpose. Therefore, practical research as a latent heat storage material has been actively conducted. ing.
JP 09-176623 A Japanese Patent Laid-Open No. 11-152466 JP 2001-279233 A JP 2002-080835 A JP-A-57-040582 JP-A-06-009950 Japanese Patent Application Laid-Open No. 07-126614 Japanese Patent Laid-Open No. 09-031451 JP 2000-336350 A JP 57-096078 A JP 63-075083 A JP 09-310064 A JP-A-10-060423 JP-A-11-323321 JP-A-56-103273 Japanese Patent Laid-Open No. 05-018687

When the latent heat storage material is dispersed and fixed in the matrix, the latent heat storage material is sealed in the container, or the encapsulated or microencapsulated latent heat storage material is dispersed and fixed in the matrix, the air conditioning system It can be used for a heat storage tank (following patent documents 17 to 19), and is enclosed in building materials (following patent documents 20 to 22) or dispersed (following patent documents 23 and 24). It is also possible to reduce the energy required for air conditioning. Use of latent heat storage materials for vehicles (Patent Document 25), prevention of freezing in winter by burying latent heat storage materials in structures such as bridges (Patent Document 26), road signs and road reflectors The application in various fields, such as performing the dew condensation prevention of the surface by doing this (following patent documents 27-30), is proposed.
Japanese Patent Laid-Open No. 04-085387 Japanese Patent Laid-Open No. 06-058686 JP 09-031452 A JP 05-032964 A Japanese Patent Laid-Open No. 06-057241 JP 2002-130739 A JP-A-11-092758 JP 2001-303030 A JP 2003-200518 A Japanese Patent Laid-Open No. 10-151997 Japanese Patent Laid-Open No. 05-025808 Japanese Patent Laid-Open No. 10-317328 JP 2002-213632 A Japanese Patent Laid-Open No. 11-161213

  When a latent heat storage material is encapsulated or microencapsulated and dispersed in a matrix, if a large amount of capsules or microcapsules are dispersed in the matrix, physical properties such as the strength of the matrix itself cannot be maintained. Is difficult to contain in the matrix, and it is difficult to create a matrix having a large amount of heat storage. In the method of fixing the latent heat storage material itself to the matrix, the monomer is polymerized in the latent heat storage material to form a matrix containing the latent heat storage material, so that the latent heat storage material content rate is fixed at a high concentration of 70% or more. Is possible. However, when heat is stored / released, phase change such as solidification / melting of the latent heat storage material is repeated, so that the shape of the matrix is distorted or deteriorated, or leakage of the latent heat storage material from the matrix occurs.

  In addition, even when the shape and distortion of the matrix in which the latent heat storage material is fixed and the leakage of the latent heat storage material are prevented (aforementioned Patent Document 14), the matrix is compounded by polymerization in the heat storage material. Therefore, the size and shape of the molded product are limited, and the use range of the matrix is limited. In order to have versatility, it is necessary to fill the container with a heat storage material, but the surface area of contact with the heat medium is as large as possible, for example, a thin tube shape, donut shape, coil shape, etc. When filling a container with a complicated shape, it is difficult to pack a heat storage agent or the like without a gap in the container, and there is a problem that the gap is formed in the container and the filling rate is lowered, so that the heat efficiency is inferior. Yes.

  When a gelling agent is added to an oil-like latent heat storage material to form a gel state with poor fluidity and sealed in a container, it is versatile and a high amount of heat storage is easily obtained. Further, by adding the gelling agent after filling the container before adding the gelling agent, there is an advantage that there is no limitation on the shape of the container and the encapsulation is simple. However, the latent heat storage material in a gel state is poor in flexibility and has a problem in processing, and when storing and releasing heat, repeated solidification and melting causes leakage of the heat storage material, that is, oil, fire, etc. There is a problem that the risk of increase.

On the other hand, when the microcapsules of the latent heat storage material are dispersed in water and the gelling agent is added to the water as the dispersion medium, it is easy to prepare a flexible gel state with poor fluidity. Since is a continuous phase, it can be used in a non-flammable state. Furthermore, by storing the gel in which microcapsules of latent heat storage material are dispersed in plastic or other suitable containers, it can be used for cold storage of frozen products, fresh foods, pharmaceuticals, etc. It can be used as a cold or heat insulating material for medical use, transportation use, storage use and household use such as transportation and storage. Moreover, by enclosing in building materials, it can also be used as a cold storage type building material having heat retaining properties, cold retaining properties, and antifreezing effects. Furthermore, it can be used for air conditioning for business use and home use such as a regenerative heat air conditioning system for buildings and buildings, a regenerative heat air conditioning system for passenger cars, buses, trucks, etc., and an air conditioning system during intermittent operation. Thus, the gel in which the microcapsules of the latent heat storage material are dispersed can be used in a wide range of applications (Patent Document 31).
JP 11-293234 A

Regarding the gelling agent of the aqueous layer, carboxymethylcellulose, methylcellulose, polyvinyl alcohol, polyacrylic acid, etc. are known. In particular, carboxymethylcellulose can change the molecular weight of carboxymethylcellulose, the degree of substitution of carboxymethyl groups, and the concentration of aqueous solution. Therefore, it is easy to adjust the gel strength and flexibility and has been used as a gelling agent for a long time. Further, by adding a polyvalent metal salt, a strong gel is formed (Patent Documents 32 to 34 described later), or by using carboxymethyl cellulose having two or more kinds of measured viscosity values or different substitution degrees, the viscosity is relatively low. Nevertheless, many studies have been made in recent years, such as the ability to form a gel with high thixotropic properties (Patent Document 35 described later). The heat storage material composition, in which microcapsules of latent heat storage materials are actually dispersed in water and carboxymethyl cellulose is added to the water that is the dispersion medium, can be given an appropriate level of flexibility. There are examples used in the following (Patent Documents 36 and 37 described later).
Japanese Patent Laid-Open No. 07-090121 JP-A-11-106561 JP-A-11-343365 JP 05-214162 A JP 2001-288458 A JP 2001-299801 A

  However, when a gelling agent is added to the microcapsule aqueous dispersion, the production process of the microcapsules of the latent heat storage material is complicated, and the content of the latent heat storage material in the microcapsule is low due to the construction of the capsule wall. There exists a problem that the heat storage amount of the created heat storage material composition becomes insufficient. To solve the complexity of the manufacturing process and the problem of insufficient heat storage, it is effective to add a gelling agent to the dispersion medium as a dispersion (emulsion) in which the latent heat storage material is dispersed at a high concentration. Seem. On the other hand, dispersion of latent heat storage materials is likely to cause problems over time and stability against thermal history, and the stability is lost due to repeated heat storage and cold storage, and organic compounds used as latent heat storage materials are separated. It is not preferable to use a conventional dispersion of a latent heat storage material to which a gelling agent is added. An emulsifier is used to disperse the latent heat storage material. However, since foaming by the emulsifier is intense, it is easy to enclose bubbles during the addition and dispersion of the gelling agent, resulting in a decrease in the amount of heat storage per volume. In order to solve these problems, it is considered effective to use a polymer dispersant that improves mechanical and thermal stability and reduces foaming properties. However, known polymer dispersants have poor emulsifiability and dispersion stability with respect to latent heat storage materials such as aliphatic hydrocarbons, and the mechanical and thermal stability after adding a gelling agent is extremely poor. As far as those skilled in the art know, no suitable polymeric dispersant has been found so far.

  In view of the above circumstances, the present invention uses aliphatic hydrocarbons as a latent heat storage material, exhibits a high heat storage amount, is excellent in mechanical and thermal stability, includes a foam due to foaming during addition of a gelling agent and dispersion. It is a technical subject to provide a difficult-to-be-latent latent heat storage material composition.

  As a result of repeating many trial and error trial manufactures and experiments in order to solve the above problems, the present inventor has high emulsifiability and dispersion stability with respect to aliphatic hydrocarbons and low foaming properties. A copolymer obtained by copolymerizing a hydrophobic monomer, a carboxyl group-containing monomer and / or a salt thereof, and a nonionic hydrophilic monomer as a polymer dispersant having excellent mechanical and thermal stability after a decrease in fluidity Viscosity measurement value of 30,000 mPa · s was found by adding carboxymethyl cellulose to a dispersion obtained by emulsifying aliphatic hydrocarbons in water using the polymer dispersant. The said subject is solved by setting it as the above viscosity.

  The technical problem can be solved by the present invention as follows.

That is, the present invention relates to a latent heat storage material composition containing an aliphatic hydrocarbon (A), a polymer dispersant (B), carboxymethylcellulose (C), and a dispersion medium (D), wherein the dispersion medium (D) is Water, aliphatic hydrocarbon (A) is a dispersed phase, and polymer dispersant (B) is a copolymer obtained by copolymerizing the following monomer (a), the following monomer (b), and the following monomer (c). A latent heat storage material composition characterized by being a partially neutralized product and / or a completely neutralized product of a polymer (Invention 1).
(A) a hydrophobic monomer,
(B) a carboxyl group-containing monomer and / or a salt thereof,
(C) Nonionic hydrophilic monomer.

Further, the present invention is the latent heat storage material composition of the first invention, wherein (a) the hydrophobic monomer is the following monomer (a-1) and the following monomer (a-2) (invention). 2).
(A-1) a styrene monomer,
(A-2) (Meth) acrylic acid alkyl ester monomers.

  Further, the present invention relates to an aliphatic hydrocarbon or a latent heat storage material (α) in which the aliphatic hydrocarbon (A) is a latent heat storage material (α) in the latent heat storage material composition of the first or second aspect. It is a latent heat storage material composition which is an aliphatic hydrocarbon which is a mixture with a cooling inhibitor (β) (Invention 3).

  Further, the present invention provides the latent heat storage material composition according to any one of the inventions 1 to 3, wherein the viscosity is 25 ° C. according to a Brookfield viscometer, the rotor No. It is a latent heat storage material composition having a viscosity measured value of 30,000 mPa · s or more at 4, 6 revolutions / minute (Invention 4).

  The present invention is the latent heat storage material composition according to any one of the first to fourth inventions, wherein the latent heat of fusion is 40 to 160 J / g (Invention 5).

  Further, the present invention provides the latent heat storage material (α) in the latent heat storage material composition according to any one of the first to fifth aspects of the present invention, wherein the latent heat storage material (α) is selected from saturated aliphatic hydrocarbons having 10 to 50 carbon atoms. It is a latent heat storage material composition which is a mixture of an aliphatic hydrocarbon having a single carbon number and / or an aliphatic hydrocarbon having a different carbon number (Invention 6).

  Further, the present invention is based on the melting point of the latent heat storage material (α) to be used since the melting point of the supercooling inhibitor (β) in the latent heat storage material composition of any one of the inventions 1 to 6 is 20 to 170 ° C. It is a latent heat storage material composition which is a mixture of a high single carbon number aliphatic hydrocarbon and / or a different carbon number aliphatic hydrocarbon (Invention 7).

  Further, according to the present invention, the aliphatic hydrocarbon (A) in the latent heat storage material composition of any one of the above inventions 1 to 7 is 90 to 100% by weight of the latent heat storage material (α) and the supercooling inhibitor (β) 0. It is a latent heat storage material composition which is an aliphatic hydrocarbon consisting of -10 wt% (Invention 8).

In the present invention, the polymer dispersant (B) in the latent heat storage material composition of any one of the inventions 1 to 8 is 35 to 98% by weight of the following monomer (a) and 1 to 45% by weight of the following monomer (b). % And a latent heat storage material composition which is a partially neutralized product and / or a completely neutralized product of a copolymer obtained by copolymerizing 1% to 20% by weight of the following monomer (c) (Invention 9).
(A) a hydrophobic monomer,
(B) a carboxyl group-containing monomer and / or a salt thereof,
(C) Nonionic hydrophilic monomer.

In the latent heat storage material composition according to any one of the first to ninth aspects of the present invention, (a) the hydrophobic monomer is 5 to 95% by weight of the following monomer (a-1) and the following monomer (a-2) 5: It is a latent heat storage material composition which is a monomer consisting of ˜95 wt% (Invention 10).
(A-1) a styrene monomer,
(A-2) (Meth) acrylic acid alkyl ester monomers.

  Further, the present invention relates to the latent heat storage material composition according to any one of the inventions 1 to 10, wherein the carboxymethyl cellulose (C) is a 1% aqueous solution in terms of anhydride, and the viscosity measured at 25 ° C. by a Brookfield viscometer is 10 to 50000 mPa · s. s is a latent heat storage material composition (Invention 11).

  Further, the present invention provides the latent heat storage material composition according to any one of the inventions 1 to 11, wherein the aliphatic hydrocarbon (A) is 30 to 70% by weight and the polymer dispersant (B) is 0.3 to 10% by weight. And carboxymethylcellulose (C) 0.3 to 5.0% by weight and dispersion medium (D) 15.0 to 69.4% by weight (Latent heat storage material composition) (Invention 12).

  Further, the present invention provides the latent heat storage material composition according to any one of the inventions 1 to 12, wherein the aliphatic hydrocarbon (A) is converted into a polymer dispersant (B) or a polymer dispersant (B) and carboxymethyl cellulose ( A latent heat storage material composition in which the average particle size of the dispersion dispersed in the dispersion medium (D) using C) is 0.3 μm to 5 μm (Invention 13).

  The present invention is also a heat and cold insulation material characterized by using the latent heat storage material composition according to any one of inventions 1 to 13 (invention 14).

  The configuration of the present invention will be described in more detail as follows.

  First, the aliphatic hydrocarbon (A) used in the present invention is composed of an aliphatic hydrocarbon of the latent heat storage material (α) alone or a mixture of the latent heat storage material (α) and the supercooling inhibitor (β).

  The latent heat storage material (α) is a paraffin having a melting point of 0 to 90 ° C., specifically, an n-paraffin having 10 to 50 carbon atoms, a cyclohexyl paraffin, a methyl paraffin, or a cyclopentyl paraffin. Use a mixture of seeds or more.

  Next, the supercooling inhibitor (β) used in the present invention is to prevent supercooling in the phase change of the aliphatic hydrocarbon (A) from a liquid to a solid, and has a melting point of 20 to 170 ° C., Furthermore, aliphatic hydrocarbons that have a higher freezing point than aliphatic hydrocarbons (A) with phase changes selected as latent heat storage materials and that do not change the thermal properties of the aliphatic hydrocarbons (A), specifically paraffins, Olefin having 30 or more carbon atoms, polyethylene wax, polyethylene, polypropylene wax, and crystalline polypropylene are used alone or in combination. Among them, paraffins having a melting point higher by 20 ° C. to 100 ° C. than the aliphatic hydrocarbon (A) are preferable.

  Examples of paraffins include n-paraffin, cyclohexyl paraffin, methyl paraffin, cyclopentyl paraffin, paraffin wax and microcrystalline wax which are a mixture thereof, and paraffin wax is particularly preferable.

  The aliphatic hydrocarbon (A) used in the present invention is determined by the heat absorption and release temperature required for the target latent heat storage material composition, and specified so that its melting point or freezing point becomes the target temperature. Can be prepared by mixing paraffins having different carbon numbers, or by mixing paraffins having different carbon numbers.

  When aliphatic hydrocarbons are used as the latent heat storage material, the aliphatic hydrocarbons are more likely to be supercooled in the fine particle state between the bulk state and the fine particle state in which the aliphatic hydrocarbon is emulsified. Therefore, if the aliphatic hydrocarbon (A) is not cooled only to the latent heat storage material (α) to a temperature lower than the freezing point of the latent heat storage material (α), the aliphatic hydrocarbon (A) in the latent heat storage material composition Coagulation may not occur. When the latent heat storage material composition of the present invention is used after being cooled to a temperature sufficiently lower than the freezing point of the aliphatic hydrocarbon (A), a supercooling inhibitor is not necessarily required, but the latent heat storage material composition When it is required to solidify the product in a narrow temperature range close to the freezing point of the aliphatic hydrocarbon (A), it is preferable to use a supercooling inhibitor (β) to prevent the supercooling phenomenon. . If the amount of the supercooling inhibitor (β) in the aliphatic hydrocarbon (A) is large, the thermal properties of the latent heat storage material composition will be greatly changed, and the latent heat storage in the latent heat storage material composition Since the content of the substance (α) decreases, the heat storage amount decreases. Therefore, it is preferable to use it at 10 wt% or less in order not to greatly change the thermal properties of the latent heat storage material composition and to suppress the heat storage amount of the latent heat storage material composition as much as possible. % Is more preferable.

  In addition to the supercooling inhibitor (β) used in the present invention, a substance known as a supercooling prevention auxiliary agent can be added to the aliphatic hydrocarbon (A) (see Patent Documents 8 and 9). Aromatic compounds having higher melting points than the latent heat storage material (α), esters, carboxylic acids, alcohols, amines, amides, coal-based synthetic waxes, oil-based synthetic waxes, and the like can be used. In addition, these can be used individually or in mixture of 2 or more types.

  The supercooling prevention auxiliary agent can be used within a range that does not greatly change the thermal properties of the aliphatic hydrocarbon (A), and the amount used is 5% by weight or less based on the aliphatic hydrocarbon (A). If the supercooling prevention aid in the aliphatic hydrocarbon (A) exceeds 5% by weight, the thermal properties of the latent heat storage material composition will be greatly changed, and the heat storage amount of the latent heat storage material composition will decrease. Therefore, it is preferable to use it at 5% by weight or less.

  Furthermore, in the present invention, a specific gravity adjusting agent for the aliphatic hydrocarbon (A), a deterioration preventing agent, and the like can be added in addition to the supercooling prevention aid. Examples of the specific gravity adjusting material include pigments, carbon, and metal powder, and examples of the deterioration preventing agent include α-tocopherol, ascorbic acid, various antioxidants, and the like.

Next, the most important polymer dispersant (B) in the present invention is a partially neutralized product of a copolymer obtained by copolymerizing the following monomer (a), the following monomer (b), and the following monomer (c). And / or a completely neutralized product.
(A) a hydrophobic monomer,
(B) a carboxyl group-containing monomer and / or a salt thereof,
(C) Nonionic hydrophilic monomer.

  (A) As a hydrophobic monomer, it means a styrene monomer, a (meth) acrylic acid alkyl ester monomer-an acrylic acid alkyl ester monomer and / or a methacrylic acid alkyl ester monomer, Applicable to notation. -, N-substituted (meth) acrylamides such as benzyl (meth) acrylate, phenyl (meth) acrylate, Nn-octyl (meth) acrylamide, Nt-octyl (meth) acrylamide, and the like. Of these, styrene monomers and (meth) acrylic acid alkyl ester monomers are preferred.

  (A-1) The styrene monomer means styrene, α-methylstyrene, and a styrene monomer having an alkyl group having 1 to 8 carbon atoms on the aromatic ring of these styrenes. Of these, styrene and α-methylstyrene are preferable. These may be used alone or in combination of two or more.

In addition, (a-2) (meth) acrylic acid alkyl ester monomer is represented by the following general formula (1):
_{^{CH 2 = CR 1 -COOR 2 (}} 1).

(However, R ¹ represents hydrogen or a methyl group, and R ² represents a linear alkyl group having 1 to 22 carbon atoms, a branched alkyl group, or a cyclic alkyl group.) (Meth) acrylic acid alkyl ester represented by means. Among them, (meth) acrylic acid ester in which R ² is an alkyl group having 1 to 18 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i -Butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate are preferred. These may be used alone or in combination of two or more.

  When the amount of the monomer (a) component used is the sum of the monomer components (a), (b), and (c), that is, less than 35% of the 100% by weight or exceeds 98% by weight. In contrast, when it is within the range of 35 to 98% by weight, the effect of improving the emulsifiability of the aliphatic hydrocarbon (A) using the copolymer obtained thereby is seen, stability against heat history, Since the effect of improving the mechanical stability and stability over time is also seen, it is preferable, and when the amount of the monomer (a) component used is in the range of 60 to 90% by weight, the above effect becomes more remarkable. Further preferred.

  When the monomer (a) component comprises (a-1) a styrene monomer and (a-2) (meth) acrylic acid alkyl ester monomer, the monomer (a) in 100% by weight of the monomer (a) When using less than 5% by weight or more than 95% by weight of the monomer (a) component, and within the range of 5 to 95% by weight, aliphatics using the resulting copolymer Since the effect of improving the emulsifiability of the hydrocarbon (A) is observed, and the stability against thermal history, mechanical stability, and the effect of improving the stability over time are also observed, the monomer (a-1) component is preferred. When the content is within the range of 20 to 80% by weight, the above effect becomes more remarkable, which is further preferable. Further, when the monomer (a-2) is within the range of 5 to 95% by weight compared to the case where the monomer (a) is less than 5% by weight or exceeds 95% by weight, it is obtained. The effect of improving the emulsifiability of the aliphatic hydrocarbon (A) using the copolymer is seen, and it is preferable because the stability against heat history, mechanical stability, and the effect of improving the stability over time are also seen, If the monomer (a-2) component is in the range of 20 to 80% by weight, the above effect becomes more remarkable, which is more preferable.

  (B) A carboxyl group-containing monomer and / or a salt thereof is an unsaturated dibase such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride. It means a half ester of an acid and an unsaturated dibasic acid, and a salt obtained by neutralizing these with a basic substance. These monomers may be used alone or in combination of two or more. Of these, acrylic acid, methacrylic acid, and itaconic acid are preferable. Examples of basic substances include sodium hydroxide, potassium hydroxide, ammonium, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, butylamine, monoethanolamine, diethanolamine, triethanolamine, methylethanolamine, Examples thereof include dimethylethanolamine and methyldiethanolamine, and one or more of these are used. Of these, sodium hydroxide, potassium hydroxide, ammonium, and dimethylethanolamine are preferable.

  When the amount of the monomer (b) component used is the sum of the monomer components (a) to (c), that is, less than 1% by weight of 100% by weight or more than 45% by weight, When it is within the range of 45% by weight, the effect of improving the emulsifiability of the aliphatic hydrocarbon (A) using the resulting copolymer is seen, and it is stable against thermal history and mechanical stability. The effect of improving the stability over time is also seen, and it is preferable to use the monomer (b) component in the range of 3 to 40% by weight, since the above effect becomes more remarkable.

  When a copolymer is obtained using an unneutralized carboxyl group-containing monomer, a part or all of the carboxyl group-containing monomer may be neutralized after completion of the polymerization. Examples of basic substances include sodium hydroxide, potassium hydroxide, ammonium, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, butylamine, monoethanolamine, diethanolamine, triethanolamine, methylethanolamine, Examples thereof include dimethylethanolamine and methyldiethanolamine, and one or more of these are used. Of these, sodium hydroxide, potassium hydroxide, ammonium, and dimethylethanolamine are preferable.

The (c) nonionic hydrophilic monomer is (meth) acrylamide and / or the following general formula (2).
^{_{CH 2 = CR 1 -COO- (R}} 2 O) n -R 3 (2)
Where R ¹ represents hydrogen or a methyl group, R ² represents ethylene and / or propylene, R ³ represents hydrogen or an alkyl group having 1 to 18 carbon atoms, and n is 1 to 100. Means a monomer having a solubility in ion-exchanged water of 5 g / 100 ml or more. Among these, (meth) acrylamide and hydroxyethyl (meth) acrylate are preferable, and acrylamide and hydroxyethyl acrylate are more preferable. These monomers may be used alone or in combination of two.

  When the amount of the monomer (c) component used is the sum of the monomer components (a) to (c), that is, less than 1% by weight of 100% by weight or more than 20% by weight, When it is within the range of 20% by weight, the effect of improving the emulsifiability of the aliphatic hydrocarbon (A) using the copolymer obtained is seen, and stability against thermal history and mechanical stability. In addition, the effect of improving the stability over time is also seen, and it is preferable, and when the amount of the monomer (c) component used is in the range of 5 to 15% by weight, the above effect becomes more remarkable, which is more preferable.

  In addition, as long as the effects of the present invention are not impaired, the monomer (d) can be added within the range without any trouble in addition to the monomer components (a) to (c). The monomer (d) is a monomer having an unsaturated double bond other than the monomer (a), the monomer (b), and the monomer (c), and examples thereof include a cationic monomer, a nonionic monomer, and an anionic monomer.

  Examples of the cationic monomer include aminoalkyl (meth) acrylate, N-alkylaminoalkyl (meth) acrylate, N, N′-dialkylaminoalkyl (meth) acrylate, aminohydroxyalkyl (meth) acrylate, and N-alkylaminohydroxy. Alkyl (meth) acrylate, N, N′-dialkylaminohydroxyalkyl (meth) acrylate, aminoalkyl (meth) acrylamide, N-alkylaminoalkyl (meth) acrylamide, N, N′-dialkylaminoalkyl (meth) acrylamide, Aminohydroxylalkyl vinyl ether, N-alkylaminohydroxylalkyl vinyl ether, N, N′-dialkylaminohydroxylalkyl vinyl ether, vinyl pyridine, vinyl And quaternary ammonium salts such as methyl halide, benzyl halide and the like, which are neutralized with inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid and propionic acid. Monomer.

  Nonionic monomers such as vinyl chloride, vinyl acetate, vinyl propionate, vinyl hebalate, vinyl esters of carboxylic acids such as highly branched monocarboxylic acid vinyl esters, allyl alcohol, allyl acetate, allyl propionate, allyl hyvalinate, highly branched mono Carboxylic acid allyl esters such as carboxylic acid allyl esters, allyl alkyl ethers such as allyl methyl ether and allyl ethyl ether, alkyl esters of unsaturated monobasic acids such as alkyl crotonic acid and alkyl cinnamate, dialkyl esters of fumaric acid, maleic Acid dialkyl ester, itaconic acid dialkyl ester, citraconic acid dialkyl ester, etc., unsaturated dibasic acid dialkyl ester, aconitic acid trialkyl ester, 3-butene-1,2,3-tricarboxylic acid Alkyl esters, unsaturated tribasic acid trialkyl esters such as 4-pentene-1,2,4-tricarboxylic acid trialkyl ester, 1-pentene-1,1,4,4-tetracarboxylic acid tetraalkyl ester, 4- Unsaturated tetrabasic acid tetraalkyl esters such as pentene-1,2,3,4-tetracarboxylic acid tetraalkyl ester, 3-hexene-1,1,6,6-tetracarboxylic acid tetraalkyl ester, N-methyl ( N-substituted (meth) acrylamides such as (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, (meta ) Acrylonitrile, allyl alcohol, vinylformamide, vinylacetate Bromide, and the like.

  Unsaturated monobasic acids such as crotonic acid and cinnamic acid, anconitic acid, 3-butene-1,2,3-tricarboxylic acid, 4-pentene-1,2,4-tricarboxylic acid and the like as anionic monomers Monobasic and diesters of tribasic acid and unsaturated tribasic acid, 1-pentene-1,1,4,4-tetracarboxylic acid, 4-pentene-1,2,3,4-tetracarboxylic acid, 3-hexene- Unsaturated tetrabasic acids such as 1,1,6,6-tetracarboxylic acid and mono-, di- and triesters of unsaturated tetrabasic acids, styrene sulfonic acid, allyl sulfonic acid, vinyl sulfonic acid, isoprene sulfonic acid, 2- (Meth) acrylamide-2-methylpropanesulfonic acid, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, hydroxyethyl (meth) acrylate Ter, sulfate of hydroxypropyl (meth) acrylate, sulfate of polyoxyalkylene (meth) acrylate, sulfate of polyoxyethylene alkylpropenyl ether, acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) ) Acrylates, acid phosphooxyethylene glycol (meth) acrylates, and salts of these compounds. Examples of basic substances include sodium hydroxide, potassium hydroxide, ammonium, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, butylamine, monoethanolamine, diethanolamine, triethanolamine, methylethanolamine, Examples thereof include dimethylethanolamine and methyldiethanolamine, and one or more basic substances are used.

  These monomers (d) may be used alone or in combination of two or more.

  The amount of the monomer (d) component used is 5% by weight or less of the total of the monomer components (a) to (d), that is, 100% by weight. When the amount exceeds 5% by weight, the effect of improving the emulsifiability is small even when the aliphatic hydrocarbon (A) is emulsified in an aqueous dispersion medium using the copolymer thus obtained, and the heat history The degree of the effect of improving the stability against mechanical property, mechanical stability, and stability over time is also reduced.

  The neutralization amount of the acid group of the copolymer in the present invention by the basic substance is the sum of the monomer (a) component, the monomer (b) component and the monomer (c) component in the copolymer or the monomer (a) component, When the total of the monomer (b) component, monomer (c) component and monomer (d) component is 100% by weight, the monomer (b) component or monomer (b) in the copolymer neutralized before and after polymerization ) When the total of the component and the anionic monomer (d) is within the range of 1 to 20% by weight, compared with the case where the total is less than 1% by weight and exceeds 20% by weight, The effect of improving the emulsifiability of the used aliphatic hydrocarbon (A) is observed, and the stability against thermal history, mechanical stability, and the effect of improving the stability over time are also observed, which is preferable. Furthermore, when the total of the monomer (b) component or the monomer (b) component and the anionic monomer (d) in the neutralized copolymer is within the range of 2 to 15% by weight, the aliphatic hydrocarbon (A) The emulsifiability is further improved, and the stability against heat history, mechanical stability, and stability over time are also further improved.

  In order to synthesize the polymer dispersant (B) used in the present invention, various known methods such as solution polymerization, dispersion polymerization, emulsion polymerization and precipitation polymerization can be applied. For example, in the case of solution polymerization, the monomers (a) to (c) or the monomers (a) to (c) and the monomer (d) are combined with methyl alcohol, ethyl alcohol, isopropyl alcohol, or t. -Lower alcohols such as butyl alcohol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, diethyl ether and dioxane; ethylene glycol monoalkyl ethers or acetates thereof; propylene glycol monoalkyl ethers or acetates thereof , Or aromatics such as toluene and xylene, alone or in a mixed organic solvent, or a mixture of these organic solvent and water, using a radical polymerization catalyst, and after completion of the polymerization, the organic solvent is distilled off. Obtained byIn this case, the copolymer formed during the polymerization may become insoluble and precipitate (precipitation polymerization). At that time, polyvinyl alcohol, polyacrylamide, (meth) acrylic acid (co) polymer (salt), starch It is also possible to add a dispersion stabilizer such as to the polymerization system (dispersion polymerization). In addition, (salt) has shown the salt of these compounds, As a salt, alkali metal salts, such as a sodium salt and potassium salt, ammonium salt, an amine salt, etc. can be illustrated.

  In the case of emulsion polymerization, the monomer is dispersed in water in the presence of a known anionic, nonionic or cationic surfactant and polymerized with a radical polymerization catalyst. Moreover, it can use as a polymeric surfactant which introduce | transduced the (meth) acryl group, the (meth) allyl group, the vinyl group, etc. into the said surfactant, and can also use a polymer dispersing agent. At this time, non-emulsifier polymerization without adding a surfactant is also possible.

  Examples of the known anionic surfactant include phosphorus compounds such as polyoxyalkylene alkyl phenyl ether, polyoxyalkylene monostyryl phenyl ether, polyoxyalkylene distyryl phenyl ether, polyoxyalkylene alkyl ether, and polyoxyalkylene fatty acid ester. Acid ester, sulfonic acid, succinic acid ester and sulfosuccinic acid ester, alkylbenzene sulfonic acid, naphthalene sulfonic acid formalin condensate, alkenyl succinic acid, rosin, reinforced rosin and hexyl diphenyl ether disulfonic acid, decyl diphenyl ether disulfonic acid, dodecyl diphenyl ether disulfonic acid and hexa Alkyl diphenyl ether disulfonic acid compounds such as decyl diphenyl ether disulfonic acid, and It can be mentioned salts of these compounds. Examples of the salt include alkali metal salts such as sodium salt and potassium salt, ammonium salt and amine salt. These anionic surfactants may be used alone or in combination of two or more.

  Examples of the known nonionic surfactant include polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, polyoxypropylene polyoxyethylene glycol glycerin fatty acid ester, sorbitan fatty acid ester, and polyethylene glycol fatty acid ester. And polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, pentaerythritol fatty acid ester, propylene glycol fatty acid ester, fatty acid diethanolamide, and polyoxypropylene polyoxyethylene glycol. These nonionic surfactants may be used alone or in combination of two or more.

  Examples of the known cationic surfactants include alkylamine salts and quaternized products thereof, methylalkylamine salts and quaternized products thereof, dimethylalkylamine salts and quaternized products thereof, methyldialkylamine salts and quaternized products thereof, Examples thereof include trialkylamine salts, quaternized products thereof, and polyoxyalkylene alkylamine ethers. These cationic surfactants may be used alone or in combination of two or more.

  In the polymerization of the copolymer, a known chain transfer agent can be used. For example, mercaptans, halogenated hydrocarbons, amines, nitro compounds, methallyl compounds, aldehydes, sulfides, sulfoxides, sulfones (salts) ), Anthracene, 2,4-diphenyl-4-methyl-1-pentene, 2,4-diphenyl-4-methyl-2-pentene, 1,1,3-trimethyl-3-phenylindane, cumene, di-a Phosphoric acid (salt) and the like can be used. In addition, (salt) has shown the salt of these compounds, As a salt, alkali metal salts, such as a sodium salt and potassium salt, ammonium salt, an amine salt, etc. can be illustrated. Among these, mercaptans and 2,4-diphenyl-4-methyl-1-pentene are preferable. These may be used alone or in combination of two or more. It is preferable that the compounding quantity of a chain transfer agent is 10 weight% or less with respect to a total of 100 weight% of each monomer component of said (a)-(d).

  Mercaptans include mercaptoethanol, mercaptopropanol, n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, stearyl mercaptan, thiophenol, thiobenzoic acid, thiosalicylic acid, naphthalenethiol, toluenethiol, trimethylolpropane-tris ( β-thiopropionate), mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoglycol, thioglycerin, cysteamine hydrochloride, mercaptopropionic acid (salt), thioglycolic acid (salt), thioacetic acid (salt), thiomalic acid, Examples include mercaptopropionic acid alkyl ester, thioglycolic acid alkyl ester, thioacetic acid alkyl ester, and thiomalic acid alkyl ester. In addition, (salt) indicates a salt of these compounds, and examples of the salt include alkali metal salts such as sodium salt and potassium salt, ammonium salt, amine salt, etc. Among them, alkyl mercaptans, mercaptopropion, etc. Preferred are acid alkyl esters, thioglycolic acid alkyl esters, thioacetic acid alkyl esters, and thiomalic acid alkyl esters.

  Examples of halogenated hydrocarbons include carbon tetrachloride, carbon tetrabromide, bromotrichloroethane, bromobenzene, and the like. Examples of amines include trimethylamine, triethylamine, tripropylamine, tributylamine, N, N-dimethylaniline, and N, N-diethylaniline.

  Examples of the nitro compound include m-dinitrobenzene.

  Examples of the methallyl compound include methallyl sulfonic acid (salt), methallyl alcohol, methallyl alkyl ether, carboxylic acid methallyl ester, methallyl amine, methallyl trialkyl ammonium halide, and dimethallyl dialkyl ammonium halide. In addition, (salt) has shown the salt of these compounds, As a salt, alkali metal salts, such as a sodium salt and potassium salt, ammonium salt, an amine salt, etc. can be illustrated.

  In the polymerization of the copolymer, a known crosslinking agent can be used. For example, bifunctional vinyl monomers such as di (meth) acrylates, bis (meth) acrylamides, divinyl esters, epoxy acrylates, urethane acrylates. And trifunctional vinyl monomers, tetrafunctional vinyl monomers, water-soluble aziridinyl compounds, water-soluble polyfunctional epoxy compounds, and silicon-based compounds. These may be used individually by 1 type and can also use 2 or more types together. The blending amount of the crosslinking agent is preferably 5% by weight or less with respect to 100% by weight in total of the monomer components (a) to (d).

  Di (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and glycerin di (meth) acrylate. .

  Examples of bis (meth) acrylamides include methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, hexamethylene bis (meth) acrylamide, N, N′-bisacrylamide acetic acid, N, N′-bisacrylamide methyl acetate, N, N-benzylidenebisacrylamide may be mentioned.

  Examples of divinyl esters include divinyl adipate and divinyl sebacate.

  Bifunctional vinyl monomers other than those described above include allyl (meth) acrylate, diallyl phthalate, diallyl malate, diallyl succinate, diallyl acrylamide, divinyl benzene, di-i-propenyl benzene, N, N-diallyl methacrylamide, N- Examples include methylolacrylamide, diallyldimethylammonium, diallylchlorendate, and glycidyl (meth) acrylate.

  Examples of the trifunctional vinyl monomer include 1,3,5-triacryloylhexahydro-S-triazine, triallyl isocyanurate, N, N-diallylacrylamide, triallylamine, and triallyl trimellitate.

  Examples of the tetrafunctional vinyl monomer include tetramethylolmethane tetraacrylate, tetraallyl pyromellitate, N, N, N ′, N′-tetraallyl-1,4-diaminobutane, tetraallylamine salt, and tetraallyloxyethane.

  Examples of water-soluble aziridinyl compounds include tetramethylolmethane-tri-β-aziridinylpropionate, trimethylolpropane-tri-β-aziridinylpropionate, and 4,4′-bis (ethyleneiminecarbonylamino) diphenylmethane. Can be mentioned.

  Examples of the water-soluble polyfunctional epoxy compound include (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, (poly) glycerin diglycidyl ether, and (poly) glycerin triglycidyl ether.

  As silicon compounds, 3- (meth) acryloxymethyltrimethoxysilane, 3- (meth) acryloxypropyldimethoxymethylsilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyl Examples include dichlorosilane, 3- (meth) acryloxyoctadecyltriacetoxysilane, 3- (meth) acryloxy-2,5-dimethylhexyldiacetoxymethylsilane, and vinyldimethylacetoxysilane.

  Examples of the known radical polymerization catalyst include persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate, peroxides such as hydrogen peroxide, benzoyl peroxide, t-butyl hydroperoxide, and di-t-butyl. Peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxymaleic acid, t-butylperoxyisopropyl monocarbonate, t-hexylperoxybenzoate, t-butylperoxybenzoate, etc. Organic peroxides, bromates such as sodium bromate and potassium bromate, perborates such as sodium perborate, potassium perborate and ammonium perborate, sodium percarbonate, potassium percarbonate and ammonium percarbonate Percarbonate, sodium perphosphate, potassium perphosphate, and the like Superphosphates such as ammonium phosphate, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-) 2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxymethyl] propionamide}, 2,2′-azobis {2-methyl-N- [2- (1-hydroxybutyl)] propionamido} dimethyl, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis [N- ( -Propenyl) -2-propionamide], 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide), 2,2 ' -Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2 , 2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} 2 Hydrochloride, 2,2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis { 2- [N- (2-carbo And azo compounds such as xyethyl) amidino] propane} dihydrochloride, dimethyl 2,2′-azobis (isobutyrate), 4,4′-azobis (4-cyanovaleric acid), azodi-t-octane and salts thereof. . These radical polymerization catalysts may be used alone or in combination of two or more. The blending amount of the initiator is preferably 0.01% by weight or more and 10% by weight or less with respect to 100% by weight of the total of the monomer components (a) to (d).

  Usually, the radical polymerization catalyst is added to the monomer solution to start the polymerization, but a part of the catalyst may be added during the polymerization for the purpose of reducing the residual monomer.

  Further, the peroxide radical polymerization catalyst and a reducing agent may be used in combination as a redox polymerization initiator. As a reducing agent, sulfite, bisulfite, diethanolamine, triethanolamine, hydrazine, hydroxylamine, dimethylaminopropionitrile, dimethylaminoethanol, dimethylaminopropanol, piperazine, morpholine, N, N, N ′, N ′ -Reducing sugars such as organic amines such as tetramethylethylenediamine and aldoses, divalent iron ions and the like. These reducing agents may be used individually by 1 type, and may use 2 or more types together.

  Usually, polymerization may be performed in an inert gas atmosphere such as nitrogen in a range of a polymerization temperature of 50 to 200 ° C. and a polymerization time of 0.5 to 20 hours.

  The form of the polymer dispersant (B) thus obtained is an aqueous solution, an aqueous dispersion or a solid resin, but even when obtained as a solid resin, it is dissolved or dispersed in ion-exchanged water, It can also be used as an aqueous solution or an aqueous dispersion. At this time, a part of the organic solvent used in the polymerization may remain. A polymer having a measured viscosity of 1 to 20000 mPa · s compared to when the viscosity measured at 25 ° C. with a Brookfield viscometer of an aqueous solution or aqueous dispersion having a solid content of 25% by weight is 1 mPa · s or less or 20000 mPa · s or more. The dispersant (B) is preferable because of its good dispersion ability with respect to the aliphatic hydrocarbon (A), and the polymer dispersant (B) in the range of 5 to 10,000 mPa · s is more preferable because of its better dispersion ability. . Moreover, the fat which used the polymer dispersing agent (B) whose viscosity measured value is 1-20000 mPa * s compared with the aliphatic hydrocarbon dispersion using the polymeric dispersing agent (B) whose viscosity measured value is 20000 mPa * s or more. The group hydrocarbon dispersion is preferred because it has a lower viscosity, facilitates the dispersion of carboxymethylcellulose (C), and easily obtains a homogeneous gel, and the measured viscosity of the polymer dispersant (B) is 5 to 10,000 mPa. -When it is in the range of s, carboxymethylcellulose (C) is more easily dispersed in the aliphatic hydrocarbon dispersion, which is more preferable.

  Next, carboxymethylcellulose (C) used in the present invention is water, measured at 25 ° C. by a Brookfield viscometer of 1% aqueous solution in terms of anhydride at 25 ° C. (Daicel Chemical Industries, Ltd. and Daiichi Kogyo Seiyaku Co., Ltd.) Is used as a property value in the catalog of (2), the viscosity of a 1% aqueous solution in terms of anhydride was used as an indicator of carboxymethyl cellulose) was 10 mPa · s or more, and a gel-like product having strong viscoelasticity was obtained. It is easy to obtain, and when it is 50000 mPa · s or less, it is easy to disperse in an aliphatic hydrocarbon dispersion, and it is preferable because a gel-like product that is homogeneous but poor in fluidity is easily obtained. Moreover, in order to make a gel-like material with strong viscoelasticity and facilitate dispersion of carboxymethylcellulose (C), use carboxymethylcellulose having a measured viscosity value of 1% aqueous solution in terms of anhydride of 20 to 20000 mPa · s. Is more preferable. Further, the degree of etherification is not particularly limited as long as it has water solubility and can measure the 1% aqueous solution viscosity in terms of anhydride at 25 ° C.

  Moreover, the carboxymethyl cellulose (C) to be used is not limited to one type, and a plurality of carboxymethyl celluloses (C) having different viscosity measurement values and etherification degrees of an anhydrous 1% aqueous solution may be used.

  Next, in the latent heat storage material composition of the present invention, the aliphatic hydrocarbon (A) melt is mixed and dispersed in a mixture of the polymer dispersant (B) and the dispersion medium (D), and further, an emulsifier. It can be prepared by treating to prepare an aliphatic hydrocarbon dispersion, and then adding carboxymethylcellulose (C), but the aliphatic hydrocarbon (A) melt is dissolved in the polymer dispersant (B) and carboxymethylcellulose ( C) and water are mixed and dispersed in a mixture, and further processed by an emulsifier to make the aliphatic hydrocarbon dispersion into a gel state having poor fluidity, or carboxymethyl cellulose (C) is divided into aliphatic hydrocarbons. The melt of (A) is mixed and dispersed in a mixture of a polymer dispersant (B), a part of carboxymethyl cellulose (C) and water, and further processed by an emulsifier to prepare an aliphatic hydrocarbon dispersion. Then the rest of the carbo It is also possible to sheet by adding methylcellulose (C) and poor gel state of fluidity.

  Addition of carboxymethyl cellulose (C) is carried out by adding the carboxymethyl cellulose powder to the mixture of the polymer dispersant (B) and water before being processed by the emulsifier, or by dissolving the carboxymethyl cellulose aqueous solution or carboxymethyl cellulose in advance. Prepare a dispersion in which the powder is dispersed in alcohols such as glycerin, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, ethanol, methanol, etc., and add it to the mixture of the polymer dispersant (B) and water. Is used. Since dissolution of carboxymethyl cellulose takes time, a method of adding an aqueous carboxymethyl cellulose solution or a carboxymethyl cellulose alcohol dispersion is preferred.

  When carboxymethyl cellulose (C) is added to the aliphatic hydrocarbon dispersion after the treatment by the emulsifier, the carboxymethyl cellulose powder is added to the aliphatic hydrocarbon dispersion and dissolved, or a carboxymethyl cellulose aqueous solution is added in advance. Prepare and add to aliphatic hydrocarbon dispersion, or disperse carboxymethylcellulose powder in alcohol such as glycerin, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, ethanol, methanol, etc. A method of adding to the hydrogen dispersion is used. Since dissolution of carboxymethyl cellulose takes time and it is difficult to uniformly disperse it, a method of adding a carboxymethyl cellulose aqueous solution or a dispersion of carboxymethyl cellulose to alcohols is preferable. However, since it is difficult to prepare a carboxymethyl cellulose aqueous solution at a high concentration, the addition of the carboxymethyl cellulose aqueous solution causes a decrease in the concentration of the aliphatic hydrocarbon (A). Therefore, an alcohol capable of preparing a dispersion at a concentration of 10% by weight or more. It is more preferable to use a method of adding a dispersion to a hydrocarbon to an aliphatic hydrocarbon dispersion, and in order to prevent volatilization of the added alcohol as much as possible, the alcohol is more preferably a polyhydric alcohol.

  When preparing an aliphatic hydrocarbon dispersion with an emulsifier, it is possible to use an emulsifier / disperser such as a high pressure discharge homogenizer homomixer, an ultrasonic emulsifier, a high shear rotary emulsifier / disperser, It is also possible to use two or more of these emulsifying dispersers in combination. It is also possible to prepare an aliphatic hydrocarbon dispersion by mixing an oil-soluble solvent in advance with the aliphatic hydrocarbon (A), treating with an emulsifier, and then distilling off the solvent. In addition, the polymer dispersant (B) and a part of water are mixed with the molten aliphatic hydrocarbon (A) to form a water-in-oil dispersion, and then inverted water is added to form an oil-in-water dispersion. An emulsification method for phase transition can also be used. A high-pressure discharge type homogenizer is preferable in that the particles in the aliphatic hydrocarbon dispersion are prepared to have a finer and more uniform distribution, and more preferably, the treatment is performed twice or more with the high-pressure discharge type homogenizer.

  In preparing the aliphatic hydrocarbon dispersion of the present invention, a known surfactant or polymer dispersant is used in a range that does not impair the effect of the polymer dispersant (B), for example, the polymer dispersant (B). Can be used in combination within a range of up to 10% by weight.

  As known surfactants that can be used in combination, cationic ones include alkylamine salts and quaternized products thereof, methylalkylamine salts and quaternized products thereof, dimethylalkylamine salts and quaternized products thereof, methyldialkylamine salts and Examples thereof include quaternized compounds, trialkylamine salts and quaternized compounds thereof, and polyoxyalkylene alkylamine ethers. Nonionic compounds include polyoxyalkylene phenyl ethers, polyoxyalkylene alkyl ethers, various sorbitan emulsifiers, polyoxyalkylene block copolymers, and polyoxyalkylene-added rosin esters. Anionic ones include alkali neutralized salts of rosin and reinforced rosin, alkylbenzene sulfonate, polyoxyalkylene alkyl phenyl ether sulfate, alkyl sulfate, naphthalene sulfonate, alkenyl succinate, polyoxyalkylene alkyl ether Examples thereof include sulfates and sulfosuccinates.

  Known polymer dispersants that can be used in combination include polyvinyl alcohol, styrene-maleic anhydride copolymer hydrolyzate, α-alkylstyrene maleic anhydride copolymer hydrolyzate, methyl vinyl ether maleic anhydride copolymer hydrolyzate. Vinyl toluene maleic anhydride copolymer hydrolyzate, styrene benzyl methacrylate maleic anhydride copolymer hydrolyzate, ethylene maleic anhydride copolymer hydrolyzate, isobutylene maleic anhydride copolymer hydrolyzate, acetic acid Examples thereof include vinyl maleic anhydride copolymer hydrolyzate and (meth) acrylamide copolymer.

  The dispersion medium (D) used in the present invention is water, and water such as ion-exchanged water, soft water, and industrial water can be used as water. When the temperature range in which the latent heat storage material composition is used is 0 ° C. or less, an antifreezing agent can be used. As the antifreezing agent, alcohol can be used, and as the alcohol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, methanol, ethanol, isopropyl alcohol, or the like can be used. Of these, polyhydric alcohols such as glycerin, ethylene glycol, propylene glycol, and diethylene glycol are preferred because of low alcohol volatility, and glycerin aqueous solution is particularly preferred.

  When alcohol is used in combination with the dispersion medium (D) as an antifreeze agent, if the alcohol concentration is too high, the aliphatic hydrocarbon (A) may not be sufficiently dispersed, the fluidity may increase, and the viscosity may decrease. The alcohol concentration of the dispersion medium (D) is desirably 50% or less, and a concentration of 5% or more is desirable for functioning as an antifreezing agent.

  The blending ratio of each material constituting the latent heat storage material composition of the present invention is 30 to 70% by weight of aliphatic hydrocarbon (A), 0.3 to 7% by weight of supercooling inhibitor (β), and polymer dispersant. (B) It is preferable to mix in the ratio of 0.3-10 weight%, carboxymethylcellulose (C) 0.3-5.0 weight%, and dispersion medium (D) 8.0-69.1 weight%.

  The higher the concentration of the aliphatic hydrocarbon (A), the higher the amount of heat stored per unit weight. Therefore, it is preferable from the viewpoint of heat storage, preferably 30% by weight or more, more preferably 40% by weight or more. preferable. On the other hand, the latent heat storage material composition exists as an oil-in-water dispersion gel, and the aliphatic hydrocarbon (A) concentration is set to 70% by weight or less in order to have sufficient stability against mechanical and thermal history. It is preferable to make it 60% by weight or less. That is, the amount of the aliphatic hydrocarbon (A) used in the latent heat storage material composition is preferably set in the range of 30 to 70% by weight, and more preferably in the range of 40 to 60% by weight.

  In order for the latent heat storage material composition to exist as an oil-in-water dispersion gel and to have sufficient stability against mechanical and thermal history, the amount of the polymer dispersant (B) used in the latent heat storage material composition Is preferably 0.3% by weight or more, and more preferably 1% by weight or more. On the other hand, the amount of the polymer dispersant (B) used in the latent heat storage material composition is 10 in order to increase the content of the aliphatic hydrocarbon (A) in the latent heat storage material composition and keep the foaming property low. It is preferably no more than wt%, more preferably no more than 7 wt%. That is, the amount of the polymer dispersant (B) used in the latent heat storage material composition is preferably 0.3 to 10% by weight, and more preferably 1 to 7% by weight.

  The viscosity of the latent heat storage material composition was measured at 25 ° C. using a Brookfield viscometer, rotor No. In order to reduce the fluidity to a gel-like composition at a viscosity measurement value at 4, 6 revolutions / minute of 30,000 mPa · s or more, the amount of carboxymethyl cellulose (C) used is 0.3% by weight or more. It is preferable that it is 0.5% by weight or more. While increasing the content of the aliphatic hydrocarbon (A), the carboxymethyl cellulose (C) is sufficiently dispersed to make it easy to obtain a homogeneous gel, and the latent heat storage material composition exists as an oil-in-water dispersion gel. In order to provide sufficient stability against mechanical and thermal history, the amount of carboxymethyl cellulose (C) used is preferably 5.0% by weight or less, and preferably 3.0% by weight or less. More preferred. That is, the amount of carboxymethyl cellulose (C) used in the latent heat storage material composition is preferably 0.3 to 5.0% by weight, and more preferably 0.5 to 3.0% by weight.

  When the heat history is repeatedly added to the latent heat storage material composition of the present invention for a long time or mechanical shearing force is applied, coarse particles in the latent heat storage material composition are aggregated, and finally the aliphatic hydrocarbon. Since separation from the latent heat storage material composition of (A) may be observed, the aliphatic hydrocarbon dispersion in which the aliphatic hydrocarbon (A) is dispersed in water using the polymer dispersant (B) The average particle diameter (median diameter: cumulative 50% diameter in the weight-based particle size distribution) is preferably 5 μm or less, and more preferably 2 μm or less. On the other hand, it is preferable to make the average particle diameter of the aliphatic hydrocarbon dispersion 0.3 μm or more in order to make it difficult to cause overcooling of the latent heat storage material and to stabilize the heat storage amount due to latent heat of fusion. That is, the average particle size of the aliphatic hydrocarbon dispersion is preferably 0.3 to 5 μm, and more preferably 0.3 to 2 μm. The average particle diameter can be measured, for example, with a laser diffraction / scattering particle size distribution measuring device Microtrac MT3300EX (manufactured by Nikkiso Co., Ltd.).

  The heat insulation and cold insulation material using the latent heat storage material composition of the present invention means that the latent heat storage material composition is sealed in an appropriate container such as plastic, film, metal, ceramic, etc., refrigerated products, fresh food, pharmaceuticals Cooling materials such as ice pillows and cooling materials to replace ice non when people fever, pillows, mats, futons, beds, chairs, sofas, ears, eye masks, helmets, hats, shoes, shoulders, back, chest, It is necessary to keep cold, warm, or warm by enclosing it in a tableware such as a cup, a dish, etc. It is intended to be used as a cold and heat insulating material for medical, transportation, storage and household use, such as transportation and storage of food, etc. In addition, in building materials such as buildings and buildings, the latent heat storage material composition is contained inside. By enclosing Or to moderate the temperature change of the inside and outside of the building, which is a thermal storage building materials and go frozen in the winter, condensation prevention. Further, the heat insulation and cold insulation material using the latent heat storage material composition of the present invention is a building or the like, a thermal storage air conditioning system for buildings, a thermal storage air conditioning system for passenger cars, buses, trucks, etc., an air conditioning system for intermittent operation, etc. It can also be used as a heat storage tank in commercial air conditioning equipment. The heat insulating and cold insulating material of the present invention can be used in a wide range of applications.

  The latent heat storage material composition of the present invention can achieve the object of the present invention as a heat storage material as it is, but if necessary, an antifoaming agent, an antiseptic, a rust preventive, a metal powder, a colorant, a specific gravity adjusting material. , Dispersion aids, wetting agents and the like can be added.

  According to the present invention, an aliphatic hydrocarbon with a phase change is used as a latent heat storage material, the mechanical and thermal history stability is good, and the latent heat storage material composition is used as a container during processing by an emulsifier and dispersion of carboxymethylcellulose. It is possible to provide a latent heat storage material composition in a gel state with little foaming due to flow or the like when encapsulating in a gel and having a poor fluidity that is difficult to enclose the foam.

  Furthermore, the latent heat storage material composition according to the present invention has a large latent heat storage amount compared to the conventional product in which the microcapsule dispersion water layer of the latent heat storage material is in a gel state with poor fluidity, and the latent heat is used more efficiently. it can.

  As the aliphatic carbohydrate (A), the latent heat storage material (α) alone or a mixture of the latent heat storage material (α) and the supercooling inhibitor (β) is used, and the latent heat storage material (α) has 10 to 50 carbon atoms. These are n-paraffin, cyclohexyl paraffin, methyl paraffin and cyclopentyl paraffin. These are used alone or as a mixture of two or more, and paraffin wax is used as the supercooling inhibitor (β).

  As the polymer dispersant (B), at least one of styrene and α-methylstyrene is used as the monomer (a-1) component, and methyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate is used as the monomer (a-2) component. A copolymer comprising at least one of lauryl methacrylate, at least one of acrylic acid, methacrylic acid and itaconic acid as a monomer (b) component and at least one of acrylamide or hydroxyethyl acrylate as a monomer (c) component, A neutralized product of the copolymer obtained by neutralization with at least one of sodium hydroxide, potassium hydroxide, dimethylethanolamine and ammonia is used.

  Carboxymethylcellulose (C) is a carboxymethylcellulose having a 1% aqueous solution of carboxymethylcellulose in terms of an anhydride and having a viscosity measurement value at 25 ° C. of 10 to 50000 mPa · s (however, a measurement value using a Brookfield viscometer). Use methylcellulose.

  The latent heat storage material composition of the present invention is obtained from the aliphatic hydrocarbon (A), the polymer dispersant (B), carboxymethylcellulose (C), and water or a polyhydric alcohol aqueous solution as a dispersion medium.

  Prior to describing the present invention more specifically with reference to examples and comparative examples, the aliphatic hydrocarbon (A), polymer dispersant (B), carboxymethylcellulose (C) and comparative examples used in each of the examples and comparative examples are compared. An example polymer dispersant (E) will be described.

  In the following, “part” and “%” are all based on weight unless otherwise specified.

Synthesis example 1 of latent heat storage material (α): Production of latent heat storage material (α-1) for Examples and Comparative Examples.

After adding 600 parts of n-pentadecane, 362.5 parts of n-hexadecane, and 37.5 parts of n-heptadecane to a flask equipped with a stirrer and a thermometer, the temperature was raised to 70 ° C., followed by stirring and mixing, and a melting point of 9.7 ° C. The latent heat storage material (α-1) for Examples and Comparative Examples was obtained. In addition, melting | fusing point was measured using the differential calorimeter (Seiko Instruments Inc. make: DSC6200).

Synthesis example 2 of latent heat storage material (α): Production of latent heat storage material (α-2) for Examples and Comparative Examples.

  N-hexadecane having a melting point of 18.6 ° C. was used as a latent heat storage material (α-2) for Examples and Comparative Examples. The melting point was measured using a differential calorimeter (supra).

Synthesis example 3 of latent heat storage material (α): Production of latent heat storage material (α-3) for Examples and Comparative Examples.

  To a flask equipped with a stirrer and a thermometer, 150 parts of n-heptadecane, 600 parts of n-octadecane and 250 parts of n-nonadecane were added and heated to 70 ° C., and then stirred and mixed. A latent heat storage material (α-3) for a comparative example was obtained. The melting point was measured using a differential calorimeter (supra).

Example of latent heat storage material (α): latent heat storage material (α-4) for Examples and Comparative Examples.

  Paraffin wax having a melting point of 55.3 ° C. was used as a latent heat storage material (α-4) for Examples and Comparative Examples. The melting point was measured using a differential calorimeter (supra).

Examples of supercooling inhibitors: Supercooling inhibitors (β-1) and (β-2) for Examples and Comparative Examples.

  Paraffin wax having a melting point of 85.9 ° C. was designated as (β-1), and paraffin wax having a melting point of 90.0 ° C. was designated as (β-2). The melting point was measured using a differential calorimeter (supra).

Synthesis Example 1 of Aliphatic Hydrocarbon (A): Production of Aliphatic Hydrocarbon (A-1) for Examples and Comparative Examples.

  By mixing 950 parts of the latent heat storage material (α-1) heated to 75 ° C. and 50 parts of the supercooling inhibitor (β-1) heated to 95 ° C. and melted, fat for Examples and Comparative Examples Group hydrocarbon (A-1) was obtained.

Synthesis examples 2 to 4 and 6 to 8 of aliphatic hydrocarbon (A): Aliphatic hydrocarbons (A-2) to (A-4) and (A-6) to (A-) for Examples and Comparative Examples 8) Production.

  The latent heat storage material (α) and the supercooling inhibitor (β) in Synthesis Example 1 of the aliphatic hydrocarbon (A) were made to have the composition ratios in the corresponding columns in Table 1 and melt mixed. Aliphatic hydrocarbons (A-2) to (A-4) and (A-6) to (A-8) for examples and comparative examples were obtained.

Aliphatic hydrocarbon (A-5) for Examples and Comparative Examples.

The latent heat storage material (α-2) was an aliphatic hydrocarbon (A-5) for Examples and Comparative Examples.

Aliphatic hydrocarbon (A-9) for Examples and Comparative Examples.

The latent heat storage material (α-3) was an aliphatic hydrocarbon (A-9) for Examples and Comparative Examples.

Aliphatic hydrocarbon (A-10) for Examples and Comparative Examples.

The latent heat storage material (α-4) was an aliphatic hydrocarbon (A-10) for Examples and Comparative Examples.

Synthesis Example 1 of Polymer Dispersant (B): Production of polymer dispersant (B-1) for Examples.

  In a flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, methyl methacrylate 22.1 parts, n-butyl acrylate 160.1 parts, methacrylic acid 22.1 parts, 50% acrylamide aqueous solution 33.1 parts N-dodecyl mercaptan 4.6 parts, 2,4-diphenyl-4-methyl-1-pentene 5.3 parts, isopropanol 2.2 parts, ammonium dodecylbenzenesulfonate 1.7 parts, ion-exchanged water 614.4 The mixture was stirred and mixed in a nitrogen atmosphere, heated to 70 ° C. and 42.6 parts of a 30% aqueous ammonium persulfate solution was added, and the temperature was raised to 90 ° C. and reacted for 2 hours. Next, the mixture is cooled to 70 ° C., and 36.3 parts of a 24% aqueous sodium hydroxide solution is gradually added dropwise to 0.85 equivalent to the anion equivalent of methacrylic acid. Further, the polymer dispersant (B-1) After adding 55.5 parts of ion-exchanged water so that the solid content of the mixture became 25%, and stirring at 80 ° C. for 30 minutes, the mixture was cooled to room temperature to obtain a solid content of 24.8% and a measured viscosity value of 9.2 mPa.s. -The polymer dispersing agent (B-1) of s and pH 7.0 was obtained. Table 2 shows the materials used, equivalent ratio, solid content, measured viscosity value, and measured pH value. The viscosity was 25 ° C. using a Brookfield rotational viscometer (manufactured by Tokimec Co., Ltd .: VISCOMETER). It is a measured value at 1, 60 rpm.

Synthesis Examples 2 to 11 of Polymer Dispersant (B): Production of polymer dispersants (B-2) to (B-11) for Examples.

  The monomers in Synthesis Example 1 of the polymer dispersant (B) are made to have the composition ratios in the corresponding column described in Table 1, and the type and amount of base are the carboxyl group-containing monomers in the corresponding column described in Table 1. Polymer dispersants (B-2) to (B-11) for Examples in the same manner as in Synthesis Example 1 of the polymer dispersant (B) except that the equivalent ratio to the anion equivalent of Got. Table 2 shows each material used, each equivalent ratio, each solid content, each measured viscosity value, and each measured pH value. The viscosity was measured at 25 ° C. and 60 rpm using a Brookfield rotational viscometer (supra) (measurement with rotor No. 1 (B-2), (B-3), (B-5), (B-6), (B-8) to (B-11), measurements with rotor No. 4 (B-4), (B-7)) measured values.

Synthesis Example 1 of Polymer Dispersant (E): Production of Polymer Dispersant (E-1) for Comparative Example.

  In a flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 101.3 parts of styrene, 11.3 parts of α-methylstyrene, 101.3 parts of n-butyl acrylate, 22.5 parts of 50% acrylamide N-dodecyl mercaptan 4.7 parts, 5.4 parts 2,4-diphenyl-4-methyl-1-pentene, 2.2 parts isopropanol, 1.7 parts ammonium dodecylbenzenesulfonate, ion-exchanged water 632.1 Then, the mixture was stirred and mixed in a nitrogen atmosphere, heated to 70 ° C. and 43.5 parts of a 30% aqueous ammonium persulfate solution was added, and then heated to 90 ° C. and reacted for 2 hours. Next, the mixture was cooled to 70 ° C., 74.0 parts of ion-exchanged water was gradually added dropwise so that the solid content of the polymer dispersant (E-1) was 25%, and the mixture was stirred at 80 ° C. for 30 minutes. The polymer dispersant (E-1) having a solid content of 25.0%, a measured viscosity value of 31.2 mPa · s, and a pH of 2.9 was obtained. Table 2 shows the materials used, equivalent ratio, solid content, measured viscosity value, and measured pH value. The viscosity was 25 ° C. using a Brookfield rotational viscometer (supra), rotor No. It is a measured value at 1, 60 rpm.

Synthesis Example 2 of Polymer Dispersant (E): Production of Polymer Dispersant (E-2) for Comparative Example.

  The monomers in Synthesis Example 1 of the polymer dispersant (B) were made to have the composition ratios in the corresponding column described in Table 1, and the types and amounts of bases were the anions of methacrylic acid in the corresponding column described in Table 1. A polymer dispersant (E-2) for a comparative example was obtained in the same manner as in Synthesis Example 1 of the polymer dispersant (B) except that the amount was equivalent to the equivalent. Table 2 shows each material used, each equivalent ratio, each solid content, each measured viscosity value, and each measured pH value. The viscosity was 25 ° C. using a Brookfield rotational viscometer (supra), rotor No. It is a measured value at 2, 60 revolutions / minute.

Synthesis Example 3 of Polymer Dispersant (E): Production of Polymer Dispersant (E-3) for Comparative Example.

  In a flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, 583.0 parts of 50% acrylamide aqueous solution, 33.1 parts of acrylic acid, 64.9 parts of ion-exchanged water, 341.1 parts of isopropyl alcohol, n -8.7 parts of dodecyl mercaptan and 33.7 parts of 10% mercaptoethanol were charged, and the mixture was heated to 60 ° C under a nitrogen gas atmosphere while stirring. As a polymerization initiator, 5.3 parts of lauroyl peroxide was added, and the temperature was raised to 80 ° C. and held for 3 hours. Next, isopropyl alcohol was distilled off, and ion-exchanged water was added to obtain a polymer dispersant (E-3) having a solid content of 35.7%, a measured viscosity value of 504 mPa · s, and a pH of 8.5. Table 2 shows the materials used, equivalent ratio, solid content, measured viscosity value, and measured pH value. The viscosity was 25 ° C. using a Brookfield rotational viscometer (supra), rotor No. It is a measured value at 3, 60 rpm.

Abbreviations in Table 2 are shown below.
St: Styrene.
αMSt: α-methylstyrene.
MMA: methyl methacrylate.
BA: n-butyl acrylate.
2-EHA: 2-ethylhexyl acrylate.
LMA: lauryl methacrylate.
MAA: methacrylic acid.
AA: acrylic acid.
IA: Itaconic acid.
AAm: acrylamide.
HEA: 2-hydroxyethyl acrylate.
NaSS: Sodium styrene sulfonate.
NaOH: sodium hydroxide.
KOH: potassium hydroxide.
DMEA: Dimethylethanolamine.
NH ₃ : ammonia.

Dispersion of carboxymethylcellulose (C) Production Example 1: Aqueous carboxymethylcellulose aqueous solution (C-1) for Examples and Comparative Examples.

  10.87 parts of carboxymethyl cellulose (Daicel Chemical Industries, Ltd .: CMC Daicel 2340, purity 92%) is added to 989.13 parts of 60 ° C. ion-exchanged water, heated to 80 ° C. after the addition, and stirred for 2 hours. After stirring, it was confirmed that carboxymethylcellulose was completely dissolved, and cooled to room temperature to obtain a carboxymethylcellulose aqueous solution (C-1) having a solid content of 1.0%.

Dispersion Example 2 of Carboxymethyl Cellulose (C): An aqueous carboxymethyl cellulose solution (C-2) for Examples.

  Dispersion of carboxymethylcellulose (C) In the same manner as in Production Example 1, an aqueous solution of carboxymethylcellulose (Daicel Chemical Industries, Ltd .: CMC Daicel 2450, purity 92%) was prepared, and an aqueous carboxymethylcellulose solution (C- 2) was obtained.

Dispersion Example 3 of Carboxymethylcellulose (C): Carboxymethylcellulose glycerin dispersion (C-3) for Examples.

  Carboxymethyl cellulose (Daicel Chemical Industries, Ltd .: CMC Daicel 2340) was added to 10.87 parts of glycerin and stirred to give a carboxymethyl cellulose glycerin dispersion (C-3) having a solid content of 15.0%. Obtained.

Dispersion Production Examples 4 to 8 of Carboxymethylcellulose (C): Carboxymethylcellulose polyhydric alcohol dispersions (C-4) to (C-8) for Examples.

In the same manner as in Production Example 3 of carboxymethylcellulose (C), using the carboxymethylcellulose and dispersion medium in the corresponding column of Table 3 as the carboxymethylcellulose and dispersion medium in Dispersion Production Example 3 of carboxymethylcellulose (C), Carboxymethylcellulose polyhydric alcohol dispersions (C-4) to (C-8) for Examples were obtained.

The carboxymethyl cellulose in Table 3 is shown below. The viscosity of 1% aqueous solution of carboxymethylcellulose in terms of anhydride is a value measured at 25 ° C. and 60 revolutions / minute using a Brookfield rotational viscometer (supra).
Made by Daicel Chemical Industries, Ltd .:
CMC Daicel 2340: 6500 mPa · s (rotor No. 4 used).
CMC Daicel 2450: 4350 mPa · s (using rotor No. 4).
CMC Daicel 1390: 3960 mPa · s (rotor No. 4 used).
CMC Daicel 1120: 37 mPa · s (using rotor No. 1).
Made by Daiichi Kogyo Seiyaku Co., Ltd .:
Serogen HE 1500F: 2610 mPa · s (uses rotor No. 4).
Serogen HE600F: 796 mPa · s (using rotor No. 3).

Production Example 1 of Aliphatic Hydrocarbon Dispersion (F) Production of Aliphatic Hydrocarbon Dispersion (F-1) for Examples.

472.5 parts of an aliphatic hydrocarbon (A-1) is melted at 75 ° C., and 108.9 parts of a polymer dispersant (B-1) which is a 24.8% aqueous dispersion and ion-exchanged water 418 in advance. .6 parts was mixed with what had been heated to 75 ° C. and stirred to pre-disperse. After pre-dispersion, while maintaining the temperature at 75 ° C., the mixture is uniformly dispersed and emulsified by passing it through a high-pressure discharge type homogenizer (Manton Gorin: 15M-8TA) at a shear pressure of 200 Kg / cm ² three times, and then cooled to 10 ° C. Group hydrocarbon dispersion (F-1) was obtained.

  The obtained aliphatic hydrocarbon dispersion (F-1) has an average particle diameter (median diameter) of 1.20 μm, 8.3 μm, and a multimodal distribution. The measured viscosity is 56 mPa · s, pH 7.1. Met. These measured values are shown in Table 4. The particle diameter is a value measured by a laser diffraction / scattering particle size distribution measuring apparatus (supra), and the viscosity is 25 ° C. using a Brookfield rotary viscometer (supra). It is a measured value at 1, 60 rpm.

Production Examples 2, 4-7, 10, 11, 16, 18-21 of Aliphatic Hydrocarbon Dispersion (F): Aliphatic Hydrocarbon Dispersions (F-2), (F-) for Examples and Comparative Examples 4) to (F-7), (F-10), (F-11), (F-16), (F-18) to (F-21).

  Aliphatic hydrocarbons (A) and (A-4) to (A-4) to (A) of the aliphatic hydrocarbons (A) and the polymer dispersant (B) in the corresponding columns of Table 4 are respectively shown. -8), (A-10), polymer dispersants for examples (B-2), (B-4) to (B-7), (B-10), (B-11) or comparative examples Except for the polymer dispersants (E-1) to (E-3) or polyoxyethylene stearyl ether, 10% styrene maleic acid resin aqueous solution prepared to pH 4.5, an aliphatic hydrocarbon dispersion ( In the same manner as in Production Example 1 of F), aliphatic hydrocarbon dispersions (F-2), (F-4) to (F-7), (F-10), (F-11), (F- 16) and (F-18) to (F-21) were obtained.

  Table 4 shows the results obtained by measuring each of the obtained aliphatic hydrocarbon dispersions (F) in the same manner as in the case of the aliphatic hydrocarbon dispersion (F-1).

Production Example 3 of Aliphatic Hydrocarbon Dispersion (F): Production of Aliphatic Hydrocarbon Dispersion (F-3) for Examples.

572.5 parts of aliphatic hydrocarbon (A-1) was melted at 75 ° C., and 59.8 parts of a polymer dispersant (B-3), which was a 25.1% aqueous dispersion, and 1.0% in advance. An aqueous solution of carboxymethylcellulose (C-1) 300 parts and ion-exchanged water 67.7 parts were mixed with those heated to 75 ° C. and stirred to be predispersed. After pre-dispersion, while maintaining the temperature at 75 ° C., the mixture is uniformly dispersed and emulsified by passing twice through a high-pressure discharge type homogenizer (Manton Gorin: 15M-8TA) at a shear pressure of 100 Kg / cm ² , and then cooled to 10 ° C. Group hydrocarbon dispersion (F-3) was obtained.

  The obtained aliphatic hydrocarbon dispersion (F-3) had an average particle diameter (median diameter) of 6.35 μm and pH 4.9. The viscosity was 25 ° C. using a Brookfield rotational viscometer (supra), rotor No. The measurement at 4, 60 rpm showed a viscosity measurement value of 100,000 mPa · s or more and could not be measured. Moreover, since fluidity | liquidity was hardly seen, it was judged to be a gel state. These measured values are shown in Table 4. The particle diameter is a value measured by a laser diffraction / scattering particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd .: Microtrack MT3300EX).

Production Example 8 of Aliphatic Hydrocarbon Dispersion (F): Production of Aliphatic Hydrocarbon Dispersion (F-8) for Examples.

577.5 parts of an aliphatic hydrocarbon (A-2) was melted at 75 ° C., and 133.1 parts of a polymer dispersant (B-8), which was a 24.8% aqueous dispersion, and 1.0% in advance. 150 parts of an aqueous carboxymethyl cellulose solution (C-1) and 139.4 parts of soft water which were heated to 75 ° C. were mixed, stirred and predispersed. After pre-dispersion, while maintaining the temperature at 75 ° C., the mixture is uniformly dispersed and emulsified by passing it through a high-pressure discharge type homogenizer (above) at a shear pressure of 200 Kg / cm ² three times, and then cooled to 10 ° C. to obtain an aliphatic hydrocarbon dispersion. (E-8) was obtained.

  The obtained aliphatic hydrocarbon dispersion (F-8) had an average particle diameter (median diameter) of 1.23 μm, a viscosity measurement value of 3550 mPa · s, and a pH of 6.5. These measured values are shown in Table 4. The particle diameter is a value measured by a laser diffraction / scattering particle size distribution measuring apparatus (supra), and the viscosity is 25 ° C. using a Brookfield rotary viscometer (supra). It is a measured value at 4, 60 rpm.

Production Examples 9, 12-14, and 17 of Aliphatic Hydrocarbon Dispersion (F): Aliphatic Hydrocarbon Dispersions (F-9) and (F-12) to (F-14) for Examples and Comparative Examples , (F-17).

  Aliphatic hydrocarbon (A), polymer dispersant (B), and aqueous carboxymethyl cellulose solution (C) are each subjected to aliphatic hydrocarbons (A-5) to (A-9) in the corresponding columns of Table 4, Except for the polymer dispersants (B-9), (B-11) or polyoxyethylene sorbitan monooleate and carboxymethyl cellulose dispersions (C-1) to (C-4) used for the examples, aliphatic carbonization Aliphatic hydrocarbon dispersions (F-9), (F-12) to (F-14), and (F-17) were obtained in the same manner as in Production Example 8 of the hydrogen dispersion (E).

  Table 4 shows the results obtained by measuring each of the obtained aliphatic hydrocarbon dispersions (F) in the same manner as in the case of the aliphatic hydrocarbon dispersion (F-1).

Production Example 15 of Aliphatic Hydrocarbon Dispersion (F): Production of Aliphatic Hydrocarbon Dispersion (F-15) of Examples.

450.0 parts of aliphatic hydrocarbon (A-10) was melted at 75 ° C., and 107.6 parts of polymer dispersant (B-11), which was a 25.1% aqueous dispersion, and 52. 3 parts and 390.1 parts of ion-exchanged water were mixed with what had been heated to 75 ° C. and stirred to be predispersed. After pre-dispersion, while maintaining the temperature at 75 ° C., the mixture is uniformly dispersed and emulsified by passing it through a high-pressure discharge type homogenizer (above) at a shear pressure of 230 Kg / cm ² three times, and then cooled to 10 ° C. to obtain an aliphatic hydrocarbon dispersion. (F-15) was obtained.

  The obtained aliphatic hydrocarbon dispersion (F-15) had an average particle diameter (median diameter) of 0.79 μm, a measured viscosity value of 67 mPa · s, and a pH of 7.3. These measured values are shown in Table 4. The particle diameter is a value measured by a laser diffraction / scattering particle size distribution measuring apparatus (supra), and the viscosity is 25 ° C. using a Brookfield rotary viscometer (supra). It is a measured value at 1, 60 rpm.

The footnotes in Table 4 are shown below.
(* 1) Amount of polymer dispersant or carboxymethylcellulose added in solid content.
(* 2) Gel state with little fluidity at 25 ° C.
(* 3) A 10% ethylene glycol aqueous solution is used as an emulsifying dispersion medium.
(* 4) After emulsification, the oil layer and the aqueous layer are separated.
(* 5) Multimodal particle size distribution.

Abbreviations in Table 4 are shown below.
POES: polyoxyethylene stearyl ether.
POESO: polyoxyethylene sorbitan monooleate.
PSM: 10% styrene maleic acid resin aqueous solution prepared to pH 4.5.

  Foam test

Each dispersion prepared in Production Examples 1 to 17, 19, and 21 of the aliphatic hydrocarbon dispersion (F) was stirred at 300 rpm for 5 minutes with a mixer, and the amount of foaming of each dispersion was observed. The results are shown in Table 4.
Foaming amount: (small) 5 <4 <3 <2 <1 (many).

Example 1
Production of latent heat storage material composition (G-1).

  After raising the temperature of 100 parts of the aliphatic hydrocarbon dispersion (F-1) to 50 ° C., 3.45 parts of the carboxymethylcellulose dispersion (C-3) was added and dispersed by stirring. After dispersion, the mixture was allowed to stand indoors and allowed to cool to room temperature (25 ° C.) to obtain a latent heat storage material composition (G-1).

  The latent heat of fusion of the obtained latent heat storage material composition (G-1) was 61.9 J / g, and a gel state test of the obtained latent heat storage material composition and a stability test against thermal history were performed. These results are shown in Table 5.

  (Example 2),

  (Example 4),

  (Example 5),

  (Example 6),

  (Example 7),

  (Example 8),

  (Example 9),

  (Example 10),

  (Example 11),

  (Example 12),

  (Example 13),

  (Example 14),

(Example 16)
Is as follows.

Production of latent heat storage material compositions (G-2), (G-4) to (G-14), (G-16).

  Aliphatic hydrocarbon dispersions (F) and (F-4) to (F-14) of the aliphatic hydrocarbon dispersion (F) and carboxymethyl cellulose dispersion (C), respectively, in the corresponding column of Table 5 In the same manner as in Example 1, except that the carboxymethyl cellulose dispersions (C-3) to (C-8) were replaced, the latent heat storage material compositions (G-2) and (G-4) to (G- 14) and (G-16) were obtained.

  Table 5 shows the results obtained by measuring the obtained latent heat storage material compositions in the same manner as in Example 1.

(Example 3)
Production of latent heat storage material composition (G-3).

  After heating up 100 parts of aliphatic hydrocarbon dispersion (F-3) to 50 degreeC, it stirred. After stirring, the mixture was allowed to stand indoors and allowed to cool to room temperature (25 ° C.) to obtain a latent heat storage material composition (G-1).

  The latent heat of fusion of the obtained latent heat storage material composition (G-3) was 87.2 J / g, and the resulting latent heat storage material composition was subjected to a gel state test and a stability test against thermal history. These results are shown in Table 5.

(Example 15)
Production of latent heat storage material composition (G-15).

  After heating 100 parts of the aliphatic hydrocarbon dispersion (F-13) to 50 ° C., 6.47 parts of the carboxymethyl cellulose dispersion (C-7) and 0.60 part of 50% aqueous calcium chloride solution were added and stirred. And dispersed. After stirring, it was allowed to stand indoors and allowed to cool to room temperature (25 ° C.) to obtain a latent heat storage material composition (G-15).

  The latent heat of fusion of the obtained latent heat storage material composition (G-15) was 90.8 J / g, and the resulting latent heat storage material composition was subjected to a gel state test and a stability test against thermal history. These results are shown in Table 5.

(Example 17)
Production of latent heat storage material composition (G-17)

  After heating 100 parts of the aliphatic hydrocarbon dispersion (F-15) to 50 ° C., 7.15 parts of the carboxymethylcellulose dispersion (C-5), 0.10 parts of a 10% aluminum sulfate aqueous solution were added and stirred. And dispersed. After stirring, it was allowed to stand indoors and allowed to cool to room temperature (25 ° C.) to obtain a latent heat storage material composition (G-17).

  The latent heat of fusion of the obtained latent heat storage material composition (G-17) was 62.2 J / g, and a gel state test and a stability test against thermal history of the obtained latent heat storage material composition were performed. These results are shown in Table 5.

(Comparative Example 1)
Production of latent heat storage material composition (H-1).

  After raising the temperature of 100 parts of the aliphatic hydrocarbon dispersion (F-16) to 50 ° C., 5.63 parts of the carboxymethylcellulose dispersion (C-4) was added and dispersed by stirring. After stirring, it was allowed to stand indoors and allowed to cool to room temperature (25 ° C.) to obtain a latent heat storage material composition (H-1).

  The resulting latent heat storage material composition (H-1) had a latent heat of fusion of 65.3 J / g, and the obtained latent heat storage material composition was subjected to a gel state test and a stability test against thermal history. These results are shown in Table 5.

(Comparative Example 2) to (Comparative Example 4)
Production of latent heat storage material compositions (H-2) to (H-4) for comparative examples.

  Aliphatic hydrocarbon dispersions (F-17), (F-19), and (F-21) of aliphatic hydrocarbon dispersion (F) and carboxymethylcellulose dispersion (C), respectively, in the corresponding columns of Table 5 , Except that the carboxymethyl cellulose dispersions (C-5) to (C-7) were replaced with each other in the same manner as in Comparative Example 1, latent heat storage material compositions (H-2) to (H-4) for Comparative Examples Got.

  Table 5 shows the results obtained by measuring the obtained latent heat storage material compositions in the same manner as in Example 1.

(Comparative Example 5)
Production of latent heat storage material composition (H-5).

  After heating up 100 parts of aliphatic hydrocarbon dispersion (F-10) to 50 degreeC, it stirred. After stirring, it was allowed to stand indoors and allowed to cool to room temperature (25 ° C.) to obtain a latent heat storage material composition (H-5).

  The latent heat storage material composition (H-5) obtained had a latent heat of fusion of 94.8 J / g, and the obtained latent heat storage material composition was subjected to a gel state test and a stability test against thermal history. The gel state was a fluid liquid state, and the measured viscosity was 5880 mPa · s. These results are shown in Table 5. The viscosity was 25 ° C. using a Brookfield rotational viscometer (supra), rotor No. It is a measured value at 4, 6 rotations / minute.

(Comparative Example 6)
Production of latent heat storage material composition (H-6).

  After raising the temperature of 100 parts of the aliphatic hydrocarbon dispersion (F-10) to 50 ° C., 5.0 parts of a 10% aluminum sulfate aqueous solution was added and dispersed by stirring. After stirring, it was allowed to stand indoors and allowed to cool to room temperature (25 ° C.) to obtain a latent heat storage material composition (H-6).

Since the obtained latent heat storage material composition (H-6) started stirring, separation of aliphatic hydrocarbons started, and an oil layer was observed after cooling, so the measurement of latent heat of fusion and the gel of the latent heat storage material composition State tests and stability tests against thermal history could not be performed.

The footnotes in Table 5 are shown below.
(* 1) A liquid having a measured viscosity value of 5880 mPa · s.

Measurement of latent heat of fusion

  About each latent heat storage material composition (G) of Examples prepared in Examples 1 to 8 and Comparative Examples 1, 2, and 4, and each latent heat storage material composition (H) of Comparative Example, 100 g of latent heat storage material composition, respectively. Was cooled to 4.5 ° C., mixed with 100 g of ion exchange water at 60 ° C. in an adiabatic system, and the temperature after mixing was measured to measure the latent heat of fusion of the latent heat storage material composition. The results are shown in Table 5.

  For each of the latent heat storage material compositions (G) of Examples 9 to 16 and Comparative Examples 3 and 5, and for each of the latent heat storage material compositions (H) of Comparative Examples, 100 g of the latent heat storage material composition is 7 g. After cooling to 5 ° C., 140 g of ion exchange water at 60 ° C. was mixed in an adiabatic system, and the temperature after mixing was measured to measure the latent heat of fusion of the latent heat storage material composition. The results are shown in Table 5.

  About the latent heat storage material composition (G-17) prepared in Example 17, after heating 100g of latent heat storage material composition to 35 degreeC, it mixes with 200g of ion-exchange water of 80 degreeC by an adiabatic system, and temperature after mixing Was measured to measure the latent heat of fusion of the latent heat storage material composition. The results are shown in Table 5.

Gel condition test

  About each latent heat storage material composition (G) for Examples prepared in Examples 1-17 and Comparative Examples 1-5 and each latent heat storage material composition (H) for Comparative Examples, each latent heat storage material composition The state was observed, whether it was a viscous liquid or a gel state, and if it was a gel state, the hardness of the gel was evaluated by finger touch. The results are shown in Table 5.

The numerical values of “5” to “2” described in the table indicate that each latent heat storage material composition has no or almost no fluidity and is in a gel state, and the larger the numerical value, the harder the gel state. Indicates that The numerical value “1” described in the table indicates that each latent heat storage material composition has sufficient fluidity, is a viscous liquid, and is not in a gel state.
(Hard gel) 5>4>3> 2 (soft gel): gel state.
1: Liquid state.
-: Aliphatic hydrocarbons separated as an oil layer immediately after the preparation of the latent heat storage material composition.

Stability: Stability test against thermal history

Each latent heat storage material composition (G) of Examples prepared in Examples 1 to 16 and Comparative Examples 1 to 5 and 30 g of each latent heat storage material composition (H) of Comparative Examples were allowed to stand at 50 ° C. for 1 hour, respectively. Then, it was allowed to stand at 5 ° C. for 1 hour. After these temperature changes were repeated 5 times and 10 times, the state of the latent heat storage material composition at each time point was observed. The results are shown in Table 5.
○: Even if the temperature change is repeated 10 times, the latent heat storage material composition maintains a stable gel state.
(Triangle | delta): When a temperature change is repeated 10 times, although an aliphatic hydrocarbon oozes on the gel surface, a latent heat storage material composition maintains the state of a gel.
X: When the temperature change is repeated 5 times, the aliphatic hydrocarbon dispersion is broken and the aliphatic hydrocarbon is separated as an oil layer.
-: Aliphatic hydrocarbons separate as an oil layer immediately after the production of the latent heat storage material composition.

30 g of the latent heat storage material composition (G-17) prepared in Example 17 was allowed to stand at 70 ° C. for 1 hour, and then allowed to stand at 35 ° C. for 1 hour. After these temperature changes were repeated 5 times and 10 times, the state of the latent heat storage material composition at each time point was observed. The results are shown in Table 5.
○: Even if the temperature change is repeated 10 times, the latent heat storage material composition maintains a stable gel state.
(Triangle | delta): When a temperature change is repeated 10 times, although an aliphatic hydrocarbon oozes on the gel surface, a latent heat storage material composition maintains the state of a gel.
X: When the temperature change is repeated 5 times, the aliphatic hydrocarbon dispersion is broken and the aliphatic hydrocarbon is separated as an oil layer.
-: Aliphatic hydrocarbons separate as an oil layer immediately after the production of the latent heat storage material composition.

  300 g of the latent heat storage material composition (G-1) prepared in Example 1 is put in a nylon bag, and a thermometer is inserted in order to measure the temperature change, and then the heat and cold insulation material (I-1) is sealed. It was.

  300 g of the latent heat storage material composition (G-16) prepared in Example 16 was put in a nylon bag, and a thermometer was inserted in order to measure the temperature change. It was.

  100 g of the latent heat storage material composition (G-17) prepared in Example 17 was put in a nylon bag, sealed with a thermometer inserted to measure temperature change, and kept warm and cold (I-3). It was.

  300 g of water was put in a nylon bag, and a thermometer was inserted to measure the temperature change, followed by sealing, and a heat insulating cold insulation material (J-1) for a comparative example was obtained.

  300g of aqueous gel used in commercially available cold insulation material (Okuda Pharmaceutical Co., Ltd .: soft cool ice pillow) is put in a nylon bag, sealed with a thermometer inserted to measure temperature changes, and compared. It was set as the thermal insulation cold insulation material (J-2) for an example.

  300g of water-based gel used in a commercially available heat insulating material (manufactured by Hakugen Co., Ltd .: Yutapon by Range) is put in a nylon bag and sealed with a thermometer inserted to measure temperature changes. It was set as the heat insulating cold storage material (J-3) for use.

  100g of aqueous gel used in commercially available heat insulation material (manufactured by Hakugen Co., Ltd .: Range Yutapon) is put in a nylon bag and sealed with a thermometer inserted to measure temperature changes. It was set as the heat-retaining material (J-4) for use.

  The heat insulation and cold insulation material (I-1) and the heat insulation and cold insulation materials for comparison (J-1) and (J-2) are cooled to 4 ° C. by storing them in a constant temperature bath at 4 ° C. for 1 hour, and then 40 ° C. The temperature change was observed in the constant temperature layer. The result is shown in FIG.

  The heat insulation cold insulation material (I-2) and the heat insulation cold insulation material (J-1) for a comparative example (J-2) are cooled to 4 degreeC by preserve | saving for 1 hour in a 4 degreeC thermostat, Then, 40 degreeC The temperature change was observed in the constant temperature layer. The result is shown in FIG.

  The heat insulation and cold insulation material (I-2) and the heat insulation and cold insulation materials for comparison (J-1) and (J-3) are heated to 50 ° C. by storing them in a thermostatic bath at 50 ° C. for 1 hour, and then 8 ° C. The temperature change was observed in the constant temperature layer. The result is shown in FIG.

  Heat insulation cold insulation material (I-3) and the insulation heat insulation material (J-4) for a comparative example are heated to 70 degreeC by storing in a 70 degreeC thermostat for 1 hour, Then, it attaches to a 35 degreeC constant temperature layer, temperature Changes were observed. The result is shown in FIG.

  The latent heat storage material composition of the present invention has poor fluidity and can be easily made into a flexible gel state, and the fluidity and flexibility of the latent heat storage material composition can be changed according to the purpose of use. Moreover, since the aliphatic hydrocarbon which is a latent heat storage material is made into a dispersion and the aqueous layer of the dispersion can be made into a gel state with poor fluidity, it can be used as a latent heat storage material without flammability. In addition, by adjusting the melting point of the latent heat storage material, it is possible to easily prepare a heat insulation and cold insulation material that can be maintained for a certain period of time at the target temperature for heat insulation and cold insulation, and the latent heat storage material composition of the present invention is made of plastic, film Enclosed in appropriate containers such as made of metal, ceramic, etc., cold storage materials such as refrigerated products, fresh foods, medicines, medical products, etc., and cooling materials to replace ice pillows and ice non when people generate heat, Also suitable for pillows, mats, futons, beds, chairs, sofas, ears, eye masks, helmets, hats, shoes, shoulders, backs, chests, joints, etc. It can be held, and it can be transported and stored in foods, medicines, medical products, etc. that need to be kept cool or warm by enclosing it in cups, dishes, etc., and buildings, buildings, etc. Building materials The latent heat storage material composition to encapsulate therein, or moderate the temperature change of the inside and outside of buildings, freezing in winter, it is possible to heat storage building materials or perform condensation prevention in. Further, the heat insulation and cold insulation material using the latent heat storage material composition of the present invention is a building or the like, a thermal storage air conditioning system for buildings, a thermal storage air conditioning system for passenger cars, buses, trucks, etc., an air conditioning system for intermittent operation, etc. In commercial air-conditioning equipment, it can be used in a wide range such as being used in a heat storage tank.

  Therefore, it can be said that the industrial applicability of the present invention is very large.

It is the figure which showed the cold insulation effect in the thermal insulation cold insulating material (I-1) by this invention, and the thermal insulation cold insulation materials (J-1) for comparative examples, and (J-2).

It is the figure which showed the cold insulation effect in the thermal insulation cold insulation material (I-2) by this invention, and the thermal insulation cold insulation material (J-1) for comparative examples, and (J-2).

It is the figure which showed the thermal insulation effect in the thermal insulation cold insulation material (I-2) by this invention, and the thermal insulation cold insulation material (J-1) for comparative examples, and (J-3).

It is the figure which showed the thermal insulation effect in the thermal insulation cold insulating material (I-3) by this invention, and the thermal insulation cold insulation material (J-4) for a comparative example.

Claims (14)

In the latent heat storage material composition containing the aliphatic hydrocarbon (A), the polymer dispersant (B), the carboxymethyl cellulose (C), and the dispersion medium (D), the dispersion medium (D) is water, Hydrocarbon (A) is a dispersed phase, and the polymer dispersant (B) is a partially neutralized copolymer obtained by copolymerizing the following monomer (a), the following monomer (b), and the following monomer (c). A latent heat storage material composition characterized by being a product and / or a completely neutralized product.
(A) a hydrophobic monomer,
(B) a carboxyl group-containing monomer and / or a salt thereof,
(C) Nonionic hydrophilic monomer. The latent heat storage material composition according to claim 1, wherein (a) the hydrophobic monomer is the following monomer (a-1) and the following monomer (a-2).
(A-1) a styrene monomer,
(A-2) (Meth) acrylic acid alkyl ester monomers.   The aliphatic hydrocarbon (A) is an aliphatic hydrocarbon that is a latent heat storage material (α) or an aliphatic hydrocarbon that is a mixture of a latent heat storage material (α) and a supercooling inhibitor (β). Alternatively, the latent heat storage material composition according to claim 2.   Viscosity measured by Brookfield viscometer at 25 ° C., rotor no. The latent heat storage material composition according to any one of claims 1 to 3, which has a viscosity measured value of 30,000 mPa · s or more at 4, 6 revolutions / minute.   The latent heat storage material composition according to any one of claims 1 to 4, wherein the latent heat of fusion is 40 to 160 J / g. The latent heat storage material (α) is selected from saturated aliphatic hydrocarbons having 10 to 50 carbon atoms, single-carbon aliphatic hydrocarbons having melting points of 0 to 90 ° C. and / or aliphatic hydrocarbons having different carbon numbers. latent heat storage material composition according to any one of a mixture of claims 3 to 5. An aliphatic hydrocarbon having a single carbon number and / or a different carbon number which is higher than the melting point of the latent heat storage material (α) having a melting point of the supercooling inhibitor (β) of 20 to 170 ° C. latent heat storage material composition according to any one of claims 3 to 6, which is a mixture of. Aliphatic hydrocarbon (A) is the latent heat storage material (alpha) 90 to 100 wt% and a supercooling inhibitor (beta) any of claims 3 to 7 is an aliphatic hydrocarbon consisting of 0-10 wt% The latent heat storage material composition described in 1. A copolymer in which the polymer dispersant (B) is obtained by copolymerizing 35 to 98% by weight of the following monomer (a), 1 to 45% by weight of the following monomer (b) and 1 to 20% by weight of the following monomer (c). The latent heat storage material composition according to any one of claims 1 to 8, which is a partially neutralized product and / or a completely neutralized product.
(A) a hydrophobic monomer,
(B) a carboxyl group-containing monomer and / or a salt thereof,
(C) Nonionic hydrophilic monomer. The hydrophobic monomer (a) is a monomer comprising the following monomer (a-1) 5 to 95% by weight and the following monomer (a-2) 5 to 95% by weight. Latent heat storage material composition.
(A-1) a styrene monomer,
(A-2) (Meth) acrylic acid alkyl ester monomers.   The latent heat storage material composition according to any one of claims 1 to 10, wherein carboxymethyl cellulose (C) has a viscosity measured value at 25 ° C by a Brookfield viscometer of 10 to 50000 mPa · s in an anhydrous 1% aqueous solution thereof. object.   15. 30 to 70% by weight of aliphatic hydrocarbon (A), 0.3 to 10% by weight of polymer dispersant (B), 0.3 to 5.0% by weight of carboxymethyl cellulose (C), and dispersion medium (D) The latent heat storage material composition according to any one of claims 1 to 11, comprising 0 to 69.4% by weight.   The average particle size of the dispersion obtained by dispersing the aliphatic hydrocarbon (A) in the dispersion medium (D) using the polymer dispersant (B) or the polymer dispersant (B) and the carboxymethyl cellulose (C) is 0. It is 3 micrometers-5 micrometers, The latent heat storage material composition in any one of Claims 1 thru | or 12.   A heat insulating and cold insulating material comprising the latent heat storage material composition according to any one of claims 1 to 13.

Images