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WO2012161278A1 - Composition pour des matières de stockage de chaleur, matière de stockage de chaleur et dispositif pour un stockage de chaleur - Google Patents

Composition pour des matières de stockage de chaleur, matière de stockage de chaleur et dispositif pour un stockage de chaleur Download PDF

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Publication number
WO2012161278A1
WO2012161278A1 PCT/JP2012/063376 JP2012063376W WO2012161278A1 WO 2012161278 A1 WO2012161278 A1 WO 2012161278A1 JP 2012063376 W JP2012063376 W JP 2012063376W WO 2012161278 A1 WO2012161278 A1 WO 2012161278A1
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Prior art keywords
heat storage
composition
storage material
conjugated diene
polymer block
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English (en)
Japanese (ja)
Inventor
小宮山　晋
健太郎 鼎
暢之 豊田
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JSR Corp
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JSR Corp
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Publication of WO2012161278A1 publication Critical patent/WO2012161278A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
    • F28D20/02—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using latent heat
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

Definitions

  • the present invention relates to a heat storage material composition, a heat storage material, and a heat storage device.
  • a heat storage material made of a composition for a heat storage material is a material containing a substance having a large heat capacity, and can store heat in the substance and take out the heat as needed.
  • Various types of heat storage materials such as air conditioners for residences, hotels, airports, underground shopping areas, canisters for cars, electronic parts, refrigerators, thermos and other home appliances, clothing fibers, organ transport insulation containers, curved mirrors, bridge concrete materials, etc. It is used in the field of
  • heat storage materials using water are common.
  • water when water is used as the heat storage material, only sensible heat due to the specific heat of the substance is often used. For this reason, heat storage materials that can also use latent heat due to phase change have attracted attention.
  • paraffin compound As a compound that can utilize latent heat due to phase change.
  • the container or the like may be easily damaged, and the paraffin compound may leak or overflow, which causes a problem in long-term use.
  • a heat storage material composition containing a paraffin compound and a thermoplastic elastomer as main components is disclosed (for example, see Patent Document 1).
  • This heat storage material composition has a high level of latent heat with a heat of fusion of 30 kcal / kg or more (126 kJ / kg or more) measured in accordance with JIS K-7122 in the operating temperature range, and is a paraffin compound as a component No phase separation or paraffin compound bleed even above the melting point of the above, and it is not brittle even below the melting point of the paraffin compound (the paraffin compound presents a solid state), and it does not crack even when molded into a sheet form.
  • Has flexibility has flexibility.
  • the composition for a heat storage material composed of a paraffin compound and a thermoplastic elastomer as disclosed in Patent Document 1 has a problem of poor fluidity during molding. This is because a styrene-ethylene / butylene-styrene copolymer is used as a thermoplastic elastomer having a function of immobilizing paraffin compounds, so when heated to a polymer solution, styrene blocks at both ends are used. This is thought to be due to aggregation. If the fluidity at the time of forming the heat storage material is poor, it is difficult to make the heat storage material into a precise shape, or the productivity is deteriorated.
  • a heat storage material composition comprising a paraffin compound, a hydrocarbon rubber, and a crystalline polyolefin is disclosed (for example, see Patent Document 2).
  • This composition for a heat storage material is said to be able to achieve shape retention while having appropriate flexibility in combination with crystalline polyolefin and hydrocarbon rubber.
  • An object of the present invention is obtained by using a composition and a heat storage material for a heat storage material that are excellent in fluidity at the time of molding, have a low bleed property of paraffin compounds even in a high temperature region, and have excellent shape retention, and the composition.
  • the object is to provide a heat storage device.
  • the present inventors diligently studied to solve the above problems.
  • the above problem is caused by the compatibility between the crystalline polyolefin and the hydrogenated conjugated diene copolymer.
  • the present invention has been completed.
  • the composition for thermal storage materials containing (i) a hydrogenated conjugated diene copolymer, (ii) a paraffin compound, and (iii) a crystalline polyolefin different from the hydrogenated conjugated diene copolymer
  • the polymer (i) includes a structural unit (a-1) derived from a conjugated diene compound, a polymer block (A) having a vinyl bond content of less than 30 mol%, and a structural unit derived from a conjugated diene compound (b -1), and a polymer obtained by hydrogenating a block copolymer (i-1) having a polymer block (B) having a vinyl bond content of 30 to 95 mol%, for a heat storage material Composition.
  • the content of the structural unit derived from the alkenyl aromatic compound is 30% by mass or less based on the block copolymer (i-1).
  • the composition for a heat storage material according to any one of [1] to [3].
  • the composition for heat storage materials according to one item.
  • the melting point of the paraffin compound (ii) measured by differential scanning calorimetry (DSC method) is in the range of ⁇ 30 to 130 ° C., according to any one of the above [1] to [5]
  • the heat storage material composition and the heat storage material which are excellent in fluidity during molding, have low bleed properties of paraffin compounds even in a high temperature region, and have excellent shape retention, and obtained using the composition.
  • An apparatus for heat storage can be provided.
  • composition for heat storage material has different crystallinity from the hydrogenated conjugated diene copolymer (i), the paraffin compound (ii), and the hydrogenated conjugated diene copolymer (i). Containing polyolefin (iii).
  • the hydrogenated conjugated diene copolymer (i) is compatible with the crystalline polyolefin (iii) having a high melting point, the paraffin compound (ii) can be used even in a high temperature region. Low bleeding and excellent shape retention.
  • the composition for heat storage materials of this invention contains hydrogenated conjugated diene copolymer (i), it shows the fluidity
  • the “high temperature region” is not particularly limited, but refers to a temperature region lower than the melting point of the crystalline polyolefin (iii) and higher than the melting point of the paraffin compound (ii), for example, 60 to 120 ° C., preferably 80 to 100 ° C. It is an area of the degree.
  • the hydrogenated conjugated diene copolymer (i) can be obtained by hydrogenating the following block copolymer (i-1).
  • the block copolymer (i-1) specifically includes a structural unit (a-1) derived from a conjugated diene compound (hereinafter, also simply referred to as “structural unit (a-1)”). And a polymer block (A) having a vinyl bond content of less than 30 mol% and a structural unit (b-1) derived from a conjugated diene compound (hereinafter also simply referred to as “structural unit (b-1)”). And a polymer block (B) having a vinyl bond content of 30 to 95 mol%.
  • the hydrogenated conjugated diene copolymer (i) is a block copolymer having an olefin crystal block and an ethylene / ⁇ -olefin copolymer block as described later.
  • the ethylene / ⁇ -olefin copolymer block is preferably an ethylene / butylene copolymer block.
  • the “structural unit derived from a compound” usually means a structural unit based on the reaction of a polymerizable double bond portion of the compound. Hydrogenation is also referred to as “hydrogenation”.
  • the conjugated diene compound forming the structural unit (a-1) is also referred to as “first conjugated diene compound”, and the conjugated diene compound forming the structural unit (b-1) is also referred to as “second conjugated diene compound”.
  • the hydrogenated conjugated diene copolymer (i) having the above structure is highly compatible with the crystalline polyolefin (iii) as compared with the ethylene / propylene rubber and the styrene elastomer having styrene blocks at both ends, and Also, it has excellent fluidity when molding a heat storage material.
  • Polymer block (A) Examples of the first conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3 -Hexadiene, 4,5-diethyl-1,3-octadiene, chloroprene.
  • 1,3-butadiene, isoprene, and 1,3-pentadiene are preferable, and 1,3-butadiene is more preferable in order to obtain a composition for a heat storage material that can be used industrially and has excellent physical properties.
  • the 1st conjugated diene compound may be used individually by 1 type, and may use 2 or more types together.
  • the structural unit (a-1) is preferably a structural unit containing 95 to 100% by mass of a structural unit derived from 1,3-butadiene, and is a structural unit composed only of a structural unit derived from 1,3-butadiene. It is particularly preferred.
  • the content of the structural unit (a-1) in the polymer block (A) is preferably 95% by mass or more with respect to the polymer block (A) from the viewpoint of maintaining fluidity during the molding process of the heat storage material. More preferably, the combined block (A) comprises only the structural unit (a-1).
  • the vinyl bond content in the polymer block (A) is less than 30 mol%, preferably 20 mol, from the viewpoint of maintaining shape retention in a high temperature region when the heat storage material is formed using the composition for heat storage material. %, More preferably 18 mol% or less.
  • the lower limit of the vinyl bond content in the polymer block (A) is not particularly limited.
  • vinyl bond content means a conjugate incorporated in the polymer block before hydrogenation in the form of 1,2-bond, 3,4-bond and 1,4-bond. This is the total proportion (based on mol%) of conjugated diene compounds incorporated in a 1,2-bond and 3,4-bond bonding mode among the diene compounds.
  • the second conjugated diene compound for example, the same compound as the first conjugated diene compound described above can be used, and preferred compounds are also the same.
  • the second conjugated diene compound and the first conjugated diene compound may be the same or different.
  • the bonding state of each conjugated diene compound that is, the bonding state of 1,2-bond or 3,4-bond
  • the bonding state of 4-bonds it is possible to form a polymer block (A) and a polymer block (B) having different vinyl bond contents.
  • the polymer block (B) is a polymer block containing the structural unit (b-1) derived from the second conjugated diene compound, and has an effect of imparting softening to the composition for heat storage material, or From the viewpoint of preventing crystallization of the combined block (B), a structural unit derived from an alkenyl aromatic compound (hereinafter referred to as “structural unit (b-2)”) within a range not impeding the fluidity of the composition for a heat storage material. It may be a polymer block further comprising:
  • the structural unit (b-1) is preferably a structural unit containing a total of 95 to 100% by mass of structural units derived from 1,3-butadiene and / or isoprene, and includes 1,3-butadiene and / or isoprene. More preferably, it is a structural unit consisting only of the derived structural unit.
  • the content ratio of the structural unit (b-1) in the polymer block (B) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more with respect to the polymer block (B). .
  • the content of the structural unit (b-2) is determined from the viewpoint of maintaining fluidity during the heat processing of the heat storage material. ) Is preferably 50% by mass or less.
  • the mass ratio of the structural unit (b-1) / structural unit (b-2) in the polymer block (B) is preferably 100/0 to 50/50, more preferably 100/0 to 70/30, and even more preferably. Is 100/0 to 80/20.
  • alkenyl aromatic compound examples include styrene, t-butylstyrene, ⁇ -methylstyrene, p-methylstyrene, divinylbenzene, N, N-diethyl-p-aminostyrene, and vinylpyridine. Of these, styrene and ⁇ -methylstyrene are preferable.
  • the polymer block (B) is a copolymer block including the structural unit (b-1) and the structural unit (b-2), the distribution of the structural unit (b-1) is random, tapered. (The structural unit (b-1) increases or decreases along the molecular chain), a partial block shape, or any combination thereof.
  • the vinyl bond content in the polymer block (B) is 30 to 95 mol%, preferably 30 to 85 mol%, more preferably 40 to 75 mol%. From the viewpoint of preventing bleeding of the paraffin compound (ii) when the heat storage material is formed using the composition for heat storage material, the vinyl bond content in the polymer block (B) is preferably 30 mol% or more.
  • the block copolymer (i-1) includes, in addition to the polymer block (A) and the polymer block (B), a structural unit derived from an alkenyl aromatic compound (hereinafter referred to as “structural unit (c-1)”). May contain a polymer block (C) containing more than 50% by mass, preferably a polymer block (C) consisting only of the structural unit (c-1).
  • the block copolymer (i-1) preferably has a block configuration of polymer block (A) -polymer block (B) -polymer block (C).
  • alkenyl aromatic compound in the structural unit (c-1) examples include the same compounds as the alkenyl aromatic compound in the structural unit (b-2), and preferred compounds are also the same.
  • the mass conversion ratio ((A) / (B)) of the polymer block (A) and the polymer block (B) is usually 5/95. -50/50, preferably 10 / 90-40 / 60. From the viewpoint of securing shape retention in a high temperature region when the heat storage material is formed using the heat storage material composition, the ratio of the polymer block (A) is 5 or more, and the ratio of the polymer block (B) is 95. The following is preferable.
  • the ratio of the polymer block (A) is 50 or less, and the ratio of the polymer block (B). Is preferably 50 or more.
  • the block copolymer (i-1) further has a polymer block (C)
  • the polymer block (A) and the mass-converted ratio of the polymer block (B) and the polymer block (C) ( ⁇ ( A) + (B) ⁇ / (C)) is usually 80/20 to 99/1, preferably 85/15 to 95/5.
  • the ratio of the polymer block (C) is preferably 20 or less.
  • the content ratio of the structural unit derived from the alkenyl aromatic compound is relative to the block copolymer (i-1) from the viewpoint of maintaining fluidity during the molding process of the heat storage material. It is preferably 30% by mass or less, and more preferably 20% by mass or less.
  • the content ratio of the structural unit derived from the alkenyl aromatic compound is, for example, that of the structural unit (b-2) in the polymer block (B) and the structural unit (c-1) in the polymer block (C). Refers to the total content (of course, either may not be included).
  • the structure of the block copolymer (i-1) may be any structure as long as it satisfies the above requirements, and examples thereof include structures represented by the following structural formulas (1) to (6).
  • Structural formula (1) ( AB ) n1 Structural formula (2): ( AB ) n2 -A Structural formula (3): ( BA ) n3 -B Structural formula (4): ( ABC ) n4 Structural formula (5): A- ( BC ) n5 Structural formula (6): ( AB ) n6 -C
  • A represents a polymer block (A)
  • B represents a polymer block (B)
  • C represents a polymer block (C)
  • n1 to n6 are 1 or more. Indicates an integer.
  • each polymer block may be the same or different.
  • the structure of the block copolymer (i-1) is such that the copolymer block is extended via a coupling agent residue, such as the structures represented by the following structural formulas (7) to (12). Alternatively, it may be branched.
  • Structural formula (7) (AB) m X Structural formula (8): (BA) m X Structural formula (9): (ABA) m X Structural formula (10): (BAB) m X Structural formula (11): (ABC) m X Structural formula (12): (ABC) X (CB)
  • A represents a polymer block (A)
  • B represents a polymer block (B)
  • C represents a polymer block (C)
  • m represents an integer of 2 or more.
  • X represents a coupling agent residue.
  • the structure of the block copolymer (i-1) is represented by the structural formula (1), (2), (4) or (7) among the structures represented by the structural formulas (1) to (12).
  • the structure is preferred. Since the shape retention in the composition for heat storage material and the heat storage material to be obtained is excellent and the bleedability of the paraffin compound (ii) is low, the block copolymer (i) having the polymer block (A) on the outer side or both ends (i) -1) is preferred.
  • the coupling rate in the block copolymer (i-1) is preferably 50 to 90% in consideration of the workability of the heat storage material and the bleeding property of the paraffin compound (ii).
  • numerator is connected through a coupling agent be a coupling rate.
  • the coupling agent examples include 1,2-dibromoethane, methyldichlorosilane, dimethyldichlorosilane, trichlorosilane, methyltrichlorosilane, tetrachlorosilane, tetramethoxysilane, divinylbenzene, diethyl adipate, dioctyl adipate, benzene- 1,2,4-triisocyanate, tolylene diisocyanate, epoxidized 1,2-polybutadiene, epoxidized linseed oil, tetrachlorogermanium, tetrachlorotin, butyltrichlorotin, butyltrichlorosilane, dimethylchlorosilane, 1,4 -Chloromethylbenzene, bis (trichlorosilyl) ethane.
  • the block copolymer (i-1) can be produced, for example, by the method described in Japanese Patent No. 3134504 and Japanese Patent No. 3360411.
  • the above block copolymers can be used alone, or two or more block copolymers can be mixed and used.
  • Examples of combinations of the block copolymers (i-1) include ABA / AB, (AB) 2 -X / AB, and (AB) 4 -X / A- B, (AB) 4 -X / (AB) 2 -X / AB, (AB) 4 -X / (AB) 3 -X / (AB) 2 -X / A-B, A-B -C / A-B, (A-B-C) 2 / A-B, (A-B-C) 2 -X / A-B ( however, A represents a polymer block (A), B represents a polymer block (B), C represents a polymer block (C), and X represents a coupling agent residue.
  • the hydrogenated conjugated diene copolymer (i) has a polystyrene equivalent weight average molecular weight (hereinafter also referred to as “Mw”) of preferably 10,000 to 700,000, and more preferably 100,000 to 500,000. Particularly preferred is 200,000 to 500,000. In order to obtain required mechanical properties, Mw is preferably 10,000 or more, and Mw is preferably 700,000 or less in order to ensure fluidity for molding the heat storage material.
  • Mw polystyrene equivalent weight average molecular weight
  • the hydrogenated conjugated diene copolymer (i) preferably has a melting point measured by differential scanning calorimetry (DSC method) in the range of 70 to 140 ° C., and preferably in the range of 80 to 120 ° C. More preferred.
  • the melting point of the hydrogenated conjugated diene copolymer (i) in the present specification corresponds to the extrapolated melting start temperature (Tim) at the crystal melting peak as measured according to JIS K-7121.
  • the value of the melt flow rate (hereinafter also referred to as “MFR”) of the hydrogenated conjugated diene copolymer (i) is not particularly limited, but is generally preferably 0.01 to 100 g / 10 min.
  • the MFR of the hydrogenated conjugated diene copolymer (i) is a value measured under a load of 230 ° C. and 10 kg in accordance with JIS K-7210.
  • the hydrogenated conjugated diene copolymer (i) can be used alone or in combination of two or more hydrogenated conjugated diene copolymers (i).
  • Examples of the combination of the hydrogenated conjugated diene copolymer (i) include, for example, ABA hydrogenated product / AB hydrogenated product, (AB) 2 -X hydrogenated product / A- B hydrogenated product, (AB) 4 -X hydrogenated product / AB hydrogenated product, (AB) 4 -X hydrogenated product / (AB) 2 -X water Additives / AB Hydrogenated, (AB) 4 -X Hydrogenated / (AB) 3 -X Hydrogenated / (AB) 2 -X Hydrogenated / AB hydrogenated product, ABC hydrogenated product / AB hydrogenated product, (ABBC) 2 hydrogenated product / AB hydrogenated product, (A- BC) 2- X hydrogenated product / AB hydrogenated product (where A represents the polymer block (A), B represents the polymer block (
  • the polymer block (A) is a polymer block having a vinyl bond content of less than 30 mol%. Therefore, the polymer block (A) becomes a structure similar to polyolefin having good crystallinity by hydrogenation, that is, an “olefin crystal block”. For example, when the first conjugated diene compound is 1,3-butadiene, the structure is similar to polyethylene with good crystallinity.
  • the polymer block (B) is a polymer block having a vinyl bond content of 30 to 95 mol%. Therefore, the polymer block (B) becomes a structure similar to the ethylene / ⁇ -olefin copolymer by hydrogenation, that is, an “ethylene / ⁇ -olefin copolymer block”.
  • the second conjugated diene compound is 1,3-butadiene, it has a structure similar to a rubbery ethylene-butylene copolymer, resulting in a soft polymer block.
  • the resulting heat storage material composition and the heat storage material are excellent in shape retention, and the bleedability of the paraffin compound (ii) is reduced. Therefore, the hydrogenated conjugated diene copolymer having the olefin crystal block on the outer side or both ends (i ) Is preferred.
  • the hydrogenated conjugated diene copolymer (i) has an olefin crystal-ethylene / butylene-olefin crystal block polymer structure.
  • the hydrogenated conjugated diene copolymer (i) having such a structure is used, the crystalline polyolefin (iii) and the hydrogenated conjugated diene copolymer (i) are compatible with each other. It is possible to provide a composition for a heat storage material capable of producing a heat storage material having excellent fluidity.
  • the method for producing the hydrogenated conjugated diene copolymer (i) is not particularly limited.
  • the prepared block copolymer (i-1) is prepared. It can be produced by hydrogenation.
  • the block copolymer (i-1) is obtained, for example, by subjecting the first conjugated diene compound to living anion polymerization using an organic alkali metal compound as a polymerization initiator in an inert organic solvent, and then the second conjugated diene compound and If necessary, it can be prepared by further adding an alkenyl aromatic compound and conducting living anionic polymerization.
  • inert organic solvent examples include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and octane; alicyclic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane; benzene, xylene, toluene, An aromatic hydrocarbon solvent such as ethylbenzene can be used.
  • aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and octane
  • alicyclic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane
  • benzene xylene, toluene
  • An aromatic hydrocarbon solvent such as ethylbenzene can be used.
  • the second conjugated diene compound when introducing a coupling agent residue into the block copolymer, can be simply reacted by adding a coupling agent without performing an operation such as isolation after living anion polymerization. Can be introduced.
  • the vinyl bond content of polymer block (A) and polymer block (B) is combined with ether compounds, tertiary amines, alkoxides of alkali metals (sodium, potassium, etc.), phenoxides, sulfonates, etc. And it can control easily by selecting the kind, usage-amount, etc. suitably.
  • the hydrogenated conjugated diene copolymer (i) can be easily prepared by hydrogenating the block copolymer (i-1).
  • the hydrogenation rate can be arbitrarily selected by changing the amount of the hydrogenation catalyst, the hydrogen pressure during the hydrogenation reaction, or the reaction time.
  • Examples of the hydrogenation catalyst include JP-A-1-275605, JP-A-5-271326, JP-A-5-271325, JP-A-5-222115, JP-A-11-292924, and JP-A-11-292924.
  • JP 2000-37632 A, JP 59-133203 A, JP 63-5401 A, JP 62-218403 A, JP 7-90017 A, JP 43-19960 A Examples thereof include hydrogenation catalysts described in JP-A-47-40473.
  • the said hydrogenation catalyst may be used only 1 type, and can also use 2 or more types together.
  • the hydrogenation rate of the double bond derived from the conjugated diene compound (including the first conjugated diene compound and the second conjugated diene compound) in the hydrogenated conjugated diene copolymer (i) is determined by shape retention and mechanical properties. In order to satisfy
  • the hydrogenated conjugated diene is added from the solution containing the hydrogenated conjugated diene copolymer (i).
  • Copolymer (i) is isolated. Isolation of the hydrogenated conjugated diene copolymer (i) can be carried out, for example, by adding acetone or alcohol to a solution containing the hydrogenated conjugated diene copolymer (i) and precipitating the solution, hydrogenated conjugated diene copolymer ( i) A solution containing i) is poured into hot water with stirring, and the solvent is distilled off. A hydrogenated conjugated diene copolymer (i) in which an appropriate amount of paraffin compound (ii) contained in the composition for a heat storage material is mixed in advance. ) Is added to hot water with stirring, and the solvent is distilled off.
  • paraffin compound (ii) examples of the paraffin compound (ii) contained in the composition for a heat storage material of the present invention include paraffin compounds having 10 to 100 carbon atoms. In addition, paraffin compound (ii) may be used individually by 1 type, and may use 2 or more types together.
  • the paraffin compound (ii) is more preferably a compound having an alkylene group having 12 to 30 carbon atoms.
  • specific examples include linear paraffins such as n-dodecane, n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, n-icosane, and branched paraffins. Can be mentioned.
  • paraffin wax As an embodiment of a paraffin compound having 10 to 100 carbon atoms, petroleum wax can be used.
  • petroleum waxes include paraffin wax (a wax that is solid at room temperature, which is produced by separating and refining oil or natural gas as a raw material from a vacuum distillation distillate), and microcrystalline wax (a reduced pressure using petroleum as a raw material).
  • paraffin wax a wax that is solid at room temperature, which is produced by separating and refining oil or natural gas as a raw material from a vacuum distillation distillate
  • microcrystalline wax a reduced pressure using petroleum as a raw material.
  • Aliphatic hydrocarbons such as wax produced at a normal temperature by separation and purification from distillation residue oil or heavy distillate oil.
  • paraffin wax having about 20 to 40 carbon atoms and microcrystalline wax having about 30 to 60 carbon atoms are preferable.
  • paraffin wax products include “HNP-9”, “HNP-51”, “FNP-0090”, and “FT115” (all manufactured by Nippon Seiwa Co., Ltd.).
  • the paraffin compound (ii) preferably has a melting point measured by differential scanning calorimetry (DSC method) in the range of ⁇ 30 to 130 ° C. from the viewpoint of effective use of heat in the living temperature region and high temperature region. More preferably, it is in the range of ⁇ 20 to 100 ° C. Further, the heat of fusion measured by the differential scanning calorimetry (DSC method) of the paraffin compound (ii) is desirably 100 kJ / kg or more from the viewpoint of utilizing latent heat due to the phase change in various fields.
  • the melting point of the paraffin compound (ii) in this specification corresponds to the extrapolated melting start temperature (Tim) at the crystal melting peak when measured according to JIS K-7121.
  • n-dodecane ( ⁇ 10 ° C., 185 kJ / kg), n-tetradecane (6 ° C., 230 kJ / kg), n-pentadecane (9 ° C., 165 kJ / kg), n-hexadecane (18 ° C., 230 kJ / kg), n -Heptadecane (21 ° C, 170 kJ / kg), n-octadecane (28 ° C, 240 kJ / kg), n-nonadecane (32 ° C, 170 kJ / kg), n-icosane (37 ° C, 250 kJ / kg), HNP-9 (73 ° C., 215 kJ / kg), HNP-51 (73 ° C., 2
  • the content of the paraffin compound (ii) is preferably 50 to 4000 parts by mass with respect to 100 parts by mass of the hydrogenated conjugated diene copolymer (i), preferably 300 to The amount is more preferably 3000 parts by mass, and still more preferably 400 to 2000 parts by mass.
  • the heat storage material is formed using the heat storage material composition, it is preferably 50 parts by mass or more in order to ensure sufficient latent heat, and the shape retention in the high temperature region is reduced, and the paraffin compound (ii) In order to prevent bleeding, it is preferably 4000 parts by mass or less.
  • Crystalline polyolefin (iii) The crystalline polyolefin (iii) contained in the composition for heat storage material of the present invention will be described.
  • the crystalline polyolefin (iii) and the hydrogenated conjugated diene copolymer (i) have compatibility by using the crystalline polyolefin (iii) and the hydrogenated conjugated diene copolymer (i). Thereby, the shape retainability in the high temperature area
  • the crystalline polyolefin (iii) When measured by the differential scanning calorimetry (DSC method), the crystalline polyolefin (iii) has a melting point higher than that of the paraffin compound (ii) from the viewpoint of shape retention of the heat storage material in the high temperature region and bleed suppression. Preferably, it has a melting point that is 20 ° C. higher than the melting point of the paraffin compound (ii). From the same viewpoint, it is preferable to have a melting point higher than that of the hydrogenated conjugated diene copolymer (i).
  • the melting point of the crystalline polyolefin (iii) in the present specification corresponds to the extrapolated melting start temperature (Tim) at the crystal melting peak when measured according to JIS K-7121.
  • the crystalline polyolefin (iii) preferably has a polystyrene-reduced weight average molecular weight (hereinafter also referred to as “Mw”) of 1,000 to 10,000,000, preferably 10,000 to 5,000,000. More preferred is 10,000 to 1,000,000.
  • Mw polystyrene-reduced weight average molecular weight
  • polyolefin means a polymer obtained by polymerizing at least one olefin selected from ethylene and ⁇ -olefin.
  • polymerization method There is no restriction
  • polymerizing by a conventionally well-known polymerization method can be used.
  • Examples of the ⁇ -olefin include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene and 3-ethyl- Examples thereof include ⁇ -olefins having 3 to 12 carbon atoms such as 1-pentene, 1-octene, 1-decene and 1-undecene.
  • Examples of the crystalline polyolefin (iii) include crystalline polyethylene, crystalline polypropylene, crystalline polybutene, and crystalline methylpentene. From the viewpoint of versatility, it is preferable to use crystalline polyethylene and crystalline polypropylene. It is particularly preferable to use crystalline polyethylene.
  • crystalline polyethylene examples include low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE), linear low density polyethylene (LLDPE), ethylene / propylene copolymer, and ethylene / octene copolymer. It is done.
  • the crystalline polyethylene may also be biopolyethylene made from ethylene made from renewable (plant) resources.
  • crystalline polypropylene examples include homopolypropylene, random polypropylene, propylene / ⁇ -olefin copolymer, propylene / ethylene copolymer, propylene / butene copolymer, and propylene / ethylene / butene copolymer.
  • the melting point of crystalline polyethylene measured by differential scanning calorimetry is preferably 80 to 140 ° C., more preferably 90 to 140 ° C. Furthermore, crystalline polyethylene having a melting point equal to or higher than that of paraffin compound (ii) is preferred. Moreover, it is preferable that the heat of fusion measured by the differential scanning calorimetry (DSC method) of crystalline polyethylene is 50 kJ / kg or more from the viewpoint of shape retention of the heat storage material in a high temperature region.
  • the melting point of crystalline polypropylene measured by differential scanning calorimetry is preferably 100 to 170 ° C., more preferably 120 to 170 ° C. Furthermore, crystalline polypropylene having a melting point equal to or higher than that of paraffin compound (ii) is preferred. Moreover, it is preferable that the heat of fusion measured by the differential scanning calorimetry (DSC method) of crystalline polypropylene is 50 kJ / kg or more from the viewpoint of shape retention of the heat storage material in a high temperature region.
  • the melt flow rate (MFR) of crystalline polyethylene according to JIS K-7210 at a temperature of 190 ° C. and a load of 2.16 kg is preferably 0.01 to 100 g / 10 min, more preferably 0.1 to 80 g. / 10 minutes.
  • the melt flow rate (MFR) of crystalline polypropylene according to JIS K-7210 at a temperature of 230 ° C. and a load of 2.16 kg is preferably 0.01 to 100 g / 10 min, more preferably 0.1 to 80 g. / 10 minutes.
  • the moldability and the like are further improved.
  • the bleed suppression of the paraffin compound (ii) is further improved.
  • Crystalline polyolefin (iii) may be used individually by 1 type, and may use 2 or more types together.
  • the content of the crystalline polyolefin (iii) is preferably 0.1 to 1000 parts by mass with respect to 100 parts by mass of the hydrogenated conjugated diene copolymer (i).
  • the amount is more preferably 1 to 500 parts by mass, and further preferably 1 to 100 parts by mass.
  • the content of the crystalline polyolefin (iii) is in the above range, it is preferable from the viewpoint of increasing the compatibility and suppressing bleeding of the paraffin compound (ii).
  • composition for a heat storage material of the present invention may contain a filler (iv) within a range not impairing the effects of the present invention for the purpose of imparting a function according to the application.
  • the filler (iv) include colorants such as titanium oxide and carbon black, metal powders such as ferrite, inorganic fibers such as glass fibers and metal fibers, organic fibers such as carbon fibers and aramid fibers, aluminum nitride, and boron nitride.
  • a filler (iv) may be used individually by 1 type, and may use 2 or more types together.
  • the composition for a heat storage material of the present invention includes, besides the filler (iv), an anti-aging agent, an antioxidant, an antistatic agent, a weathering agent, an ultraviolet absorber, and an anti-blocking agent as long as the effects of the present invention are not impaired.
  • Crystal nucleating agents, flame retardants, vulcanizing agents, vulcanization aids, antibacterial / antifungal agents, dispersants, anti-coloring agents, foaming agents, rust preventing agents, and the like may be blended.
  • the content of the filler (iv) varies depending on the type in order to impart the desired function, but from the viewpoint of maintaining the productivity at the time of filling the composition for a heat storage material, the composition for a heat storage material It is desirable that the content be such that the fluidity can be maintained above the melting point of the crystalline polyolefin (iii).
  • the content of the filler (iv) is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass with respect to 100% by mass of the heat storage material composition. 30% by mass is particularly preferred. From the viewpoint of imparting a desired function to the composition for a heat storage material, 1% by mass or more is particularly preferable. From the viewpoint of maintaining fluidity and maintaining productivity at the time of filling the composition for a heat storage material, 30 mass% or less is especially preferable.
  • a compound such as silica or expanded graphite having pores is a filler (iv) from the viewpoint that the components contained in the composition for a heat storage material can penetrate into the pores and can provide a desired function with a small filling amount. As preferred.
  • Examples of the silica having pores include conventionally known foamed silica.
  • Expanded graphite having pores can be produced by a known method. For example, natural graphite, pyrolytic graphite or quiche graphite as a graphite material is immersed in a mixed acid of a strong acid such as concentrated sulfuric acid and a strong oxidizing agent such as a perchloric acid aqueous solution or nitric acid to form an intercalation compound, which is usually 100 It can be obtained by performing a heat treatment at a temperature of at least 500 ° C, preferably at least 500 ° C.
  • the bulk density of expanded graphite can be adjusted by acid treatment conditions or heat treatment conditions after acid treatment, a high bulk density is obtained in advance, and this is adjusted to the desired bulk density by mechanical operation such as compression or crushing. It is also possible to do.
  • thermal Storage Material of the present invention is formed using the thermal storage material composition described in “I. Thermal Storage Material Composition”.
  • the shape include various shapes such as a sheet shape, a granular shape, and a pellet shape. Although it does not specifically limit as a shaping
  • the hydrogenated conjugated diene copolymer (i) and the crystalline polyolefin (iii) are first melt mixed to obtain a mixture thereof, and then the paraffin compound (ii) is added to the mixture.
  • a uniform heat storage material composition can be obtained.
  • operativity will improve if hydrogenated conjugated diene copolymer (i) and crystalline polyolefin (iii) are made into a pellet form, a granular form, and a powder form before addition.
  • the addition temperature is preferably not less than the melting points of the hydrogenated conjugated diene copolymer (i) and the crystalline polyolefin (iii), and is usually 100 to 200 ° C.
  • the composition for a heat storage material in a solution state is molded as it is or after being slightly cooled.
  • the molding may be performed by pouring into a mold to obtain a desired sheet shape or plate shape.
  • the heat storage material since the heat storage material is solidified when it becomes less than the melting point of the paraffin compound (ii), it may be cut into a sheet shape or a plate shape after being formed into a block shape.
  • the heat storage material composition may be attached, applied, or impregnated on a film, cloth, fiber or the like to form a sheet or plate. Further, it can be packed in a bag of polyethylene or the like and formed into a sheet shape, a plate shape, or a rod shape in the cooling process.
  • an extruder if used, it can be extruded into a sheet or plate. Further, it can be formed into a rod shape or a pipe shape by an extruder, and if a rod-like or pipe-like heat storage material is chopped, it becomes both a granular shape and a pellet shape.
  • Thermal Storage Device III. Thermal Storage Device
  • the thermal storage device of the present invention is obtained by filling a container with the thermal storage material composition described in “I. Thermal Storage Material Composition”.
  • the apparatus is superior to other forms from the viewpoint of maintaining productivity, safety, and heat storage performance.
  • a packaging container using a known material, a metal container, or the like can be appropriately selected or used in combination.
  • the heat storage device of the present invention can be used in combination with known heat insulating members such as a vacuum heat insulating material, a urethane foam material, a phenol foam material, a polystyrene foam material, a glass wool material, and a rock wool material depending on the application.
  • packaging container materials include films made of polyolefin resins such as polyethylene (PE) and polypropylene (PP) (polyolefin resin films), films made of polyester resins such as polyethylene terephthalate (PET) (polyester resin films), and stretching Base films known as packaging materials, such as films made of nylon (ONy), polyamide (PA), ethylene / vinyl alcohol copolymer (EVOH), etc .; metal foils for soaking, such as aluminum foil; A laminated film formed by laminating these base film and metal foil by a known laminating method is exemplified.
  • PE polyolefin resin
  • PP polypropylene
  • polyester resins such as polyethylene terephthalate (PET) (polyester resin films)
  • stretching Base films known as packaging materials such as films made of nylon (ONy), polyamide (PA), ethylene / vinyl alcohol copolymer (EVOH), etc .
  • metal foils for soaking such as aluminum foil
  • a base film heat seal layer having heat-fusibility
  • a method of filling the composition for a heat storage material into a container for example, a container containing a heat seal layer as an innermost layer is filled with the composition for a heat storage material using a known filling device, and this is then performed with a heat seal bar.
  • a method of heat sealing and sealing is preferable in terms of productivity.
  • the heat seal layer is preferably a polyolefin resin film (heat-sealable olefin layer) having heat-sealability, more preferably a PE film or PP film, and a linear low-density polyethylene (LLDPE) film from the viewpoint of productivity. Is particularly preferred.
  • paraffin compound (ii) may ooze out (bleed) when a container composed of these single layers is used. is there.
  • a laminated film including the heat seal layer (innermost layer) and a layer (oil-resistant polar resin layer) made of an oil-resistant polar resin (oil-resistant polar resin) is provided.
  • the heat seal layer innermost layer
  • a layer oil-resistant polar resin layer
  • oil-resistant polar resin oil-resistant polar resin
  • Examples of the oil-resistant polar resin layer in the laminated film include a PA film and a PET film. By covering the heat seal layer (innermost layer) with an oil-resistant polar resin layer, oil bleed can be further prevented.
  • the film thickness of each layer of the heat seal layer and the oil-resistant polar resin layer is preferably 50 ⁇ m or more in the heat seal layer from the viewpoint of sufficiently exhibiting the functions of each layer and obtaining mechanical strength. Is 50 to 200 ⁇ m, and in the oil-resistant polar resin layer, it is preferably 10 ⁇ m or more, and more preferably 10 to 100 ⁇ m. Moreover, in order to give these layers further functionality, a heat-resistant resin film or a gas barrier resin film can be laminated.
  • containers having the following layer structure In the following examples of layer configurations, the outermost layer to the innermost layer are sequentially arranged from the left side, and “film” may be omitted in the PE film and the like, and the base film shown in parentheses is The base film described on the left side can be used instead.
  • PA / PE PP
  • the film thickness of each substrate film is preferably 50 ⁇ m or more in PE and PP, and preferably 10 ⁇ m or more in PA.
  • the container may be required to have further heat resistance.
  • PA is used as a substrate film
  • the film thickness of each substrate film is preferably 50 ⁇ m or more in PE and PP, preferably 10 ⁇ m or more in PA, and preferably 10 ⁇ m or more in PET.
  • each substrate film is preferably 50 ⁇ m or more for PE and PP, 10 ⁇ m or more for PA, 10 ⁇ m or more for EVOH, and preferably 10 ⁇ m or more for PET.
  • a known method such as a co-extrusion method, a dry laminating method, or a heat sealing method is used.
  • Weight average molecular weight Using gel permeation chromatography (GPC, trade name: HLC-8120GPC, manufactured by Tosoh Finechem, column: manufactured by Tosoh, GMH-XL), the weight average molecular weight was calculated in terms of polystyrene. .
  • MFR (g / 10 min) MFR (g / 10 min) was measured at 230 ° C. under a load of 10 kg in accordance with JIS K-7210.
  • the melting points of the paraffin compound (ii) and the crystalline polyolefin (iii) are also measured by the same method.
  • MFR (g / 10 min) Physical properties of crystalline polyethylene [MFR (g / 10 min)]: MFR (g / 10 min) was measured at 190 ° C. under a load of 2.16 kg according to JIS K-7210.
  • the melting point and latent heat of the composition for heat storage material are measured by a differential scanning calorimeter. (DSC) was used for measurement. The measurement was carried out by holding the sample at 140 ° C. for 10 minutes, cooling to ⁇ 30 ° C. at a rate of 10 ° C./minute, then holding at ⁇ 30 ° C. for 10 minutes and then increasing to 140 ° C. at a rate of 10 ° C./minute. This was performed by measuring the melting peak when warmed.
  • the extrapolated melting start temperature of the melting peak corresponding to the blended paraffin compound (ii) is the melting point of the heat storage material composition
  • the heat of fusion is the latent heat amount of the heat storage material composition.
  • fusing point of the composition for thermal storage materials which has a some melting peak was made into the extrapolated melting start temperature of the melting peak with a larger amount of heat of fusion, and the latent heat amount was made into the heat of fusion of the melting peak. When there were multi-peaks and individual melting peaks could not be distinguished, they were treated as one melting peak.
  • the composition for a heat storage material was formed into a sheet having a thickness of 2 mm, cut into a size of 40 mm ⁇ 40 mm, and three sheets thereof were stacked to obtain a test sample.
  • the sample was put into a gear oven set to the test temperature described in Tables 1 and 2, and after 1 hour, the sample was taken out and cooled sufficiently, and then the thickness of the sample was measured. evaluated.
  • AA The thickness of the sample after the test is more than 80% of the thickness of the sample before the test, and the shape retainability is particularly excellent.
  • BB The thickness of the sample after the test is 30 to 80% of the thickness of the sample before the test, and the shape retainability is excellent.
  • CC The sample thickness after the test is less than 30% of the sample thickness before the test, and the shape retainability is poor.
  • a composition for a heat storage material is formed into a sheet having a thickness of 2 mm, cut into a size of 40 mm ⁇ 40 mm, and three sheets thereof are laminated together with a polyethylene film (inner layer) and a polyamide film (outer layer).
  • a test sample was obtained by packaging with a laminated film consisting of The sample was put into a gear oven set to the test temperature described in Tables 1 and 2 and allowed to stand. One hour later, the sample was taken out and sufficiently cooled, and then visually confirmed whether or not the paraffin compound (ii) was separated, and the bleeding property was evaluated according to the following criteria. AA: Almost no separation is observed, and no bleed is observed. BB: A slight amount of bleed is observed, but there is no practical problem. CC: Separation is clearly confirmed, and there are many bleeds.
  • Fluidity 50 g of the composition for a heat storage material was put in a 200 mL glass beaker and heated and dissolved in a gear oven set to the test temperature described in Tables 1 and 2 for 1 hour. After moving the beaker on the horizontal table, the beaker was tilted by 90 °, and the appearance of the composition was visually observed. The fluidity was evaluated according to the following criteria. AA: Since the solution of the composition flows out from the edge of the beaker within 5 seconds, the fluidity is good. BB: Since the solution of the composition does not flow out from the edge of the beaker within 5 seconds, the fluidity is poor.
  • the block copolymer includes a structural unit derived from 1,3-butadiene, includes a polymer block (A) having a vinyl bond content of 14 mol%, and a structural unit derived from 1,3-butadiene. It was a block copolymer having a polymer block (B) having a bond content of 46 mol%. In addition, the block copolymer had a weight average molecular weight of 280,000 and a coupling rate of 80%.
  • reaction solution containing the block copolymer was brought to 80 ° C., and 2.0 g of bis (cyclopentadienyl) titanium furfuryloxychloride and 1.2 g of n-butyllithium were added to maintain a hydrogen pressure of 1.0 MPa. For 2 hours.
  • the reaction solution was returned to room temperature and normal pressure, extracted from the reaction vessel, stirred into water, and the solvent was removed by steam distillation to obtain the desired hydrogenated conjugated diene copolymer (H1). .
  • the hydrogenation rate of the hydrogenated conjugated diene copolymer (H1) was 98%, the MFR was 3.5 g / 10 min, and the melting point was 82.0 ° C.
  • the block copolymer includes a structural unit derived from 1,3-butadiene, a polymer block (A) having a vinyl bond content of 15 mol%, and a structural unit derived from 1,3-butadiene. It was a block copolymer having a polymer block (B) having a bond content of 48 mol%.
  • the block copolymer had a weight average molecular weight of 320,000 and a coupling rate of 79%.
  • the block copolymer includes a structural unit derived from 1,3-butadiene, a polymer block (A) having a vinyl bond content of 15 mol%, and a structural unit derived from 1,3-butadiene. It was a block copolymer having a polymer block (B) having a bond content of 50 mol%. Moreover, in the said block copolymer, the weight average molecular weight was 230,000 and the coupling rate was 78%.
  • Example 1 50 parts of “H1” as the hydrogenated conjugated diene copolymer (i), 50 parts of “PO1” (Novatech LD LC600A manufactured by Nippon Polyethylene Co., Ltd.) as the crystalline polyolefin (iii), and n ⁇ as the paraffin compound (ii)
  • a composition for a heat storage material was manufactured by heating and mixing 900 parts of dodecane and 5 parts of “AO-60” (manufactured by ADEKA Co., Ltd.) as an anti-aging agent at 120 ° C. in a glass flask.
  • the produced heat storage material composition has a melting point of ⁇ 11 ° C., a latent heat amount of 155 kJ / kg, a shape retention evaluation of AA, a bleeding property evaluation of AA, and a fluidity evaluation of AA. Met.
  • Example 1 compositions for heat storage materials of Examples 2 to 15 and Comparative Examples 1 to 8 were produced in the same manner as Example 1 except that the distribution composition was changed as described in Tables 1 and 2. .
  • the heating and mixing in Examples 9, 11 to 15, and Comparative Example 6 were performed at 140 ° C.
  • Each component used in the examples and comparative examples is as follows.
  • H1 Hydrogenated conjugated diene copolymer (H1) obtained in Synthesis Example 1
  • H2 Hydrogenated conjugated diene copolymer (H2) obtained in Synthesis Example 2
  • H3 Hydrogenated conjugated diene copolymer (H3) obtained in Synthesis Example 3
  • Anti-aging agent AO-60 Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by ADEKA Corporation)
  • the composition for a heat storage material of the present invention is excellent in fluidity at the time of molding, has low bleed properties of paraffin compounds and excellent shape retention even in a high temperature region. Therefore, various fields such as air conditioning equipment for residences, hotels, airports, underground malls, canisters for automobiles, electronic parts, refrigerators, thermos and other home appliances, clothing fibers, thermal containers for organ transport, curve mirrors, concrete materials for bridges, etc. In particular, it can be used in facilities that require a heat source in a high temperature region, such as a heat storage mechanism that uses a motor or compressor as a heat source.

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Abstract

L'invention a pour but de proposer : une composition pour des matières de stockage de chaleur, qui a une excellente fluidité pendant un moulage et une excellente performance de rétention de forme, tout en ayant un épanchement diminué d'un composé de paraffine même dans une plage de températures élevées ; une matière de stockage de chaleur ; et un dispositif pour un stockage de chaleur, qui est obtenu à l'aide de la composition. A cet effet, l'invention propose une composition pour des matières de stockage de chaleur, qui contient (i) un copolymère diène conjugué hydrogéné, (ii) un composé de paraffine et (iii) une polyoléfine cristalline qui est différente du copolymère diène conjugué hydrogéné. Le copolymère diène conjugué hydrogéné (i) est un polymère qui est obtenu par hydrogénation d'un copolymère à bloc (i-1) qui a un bloc de polymère (A) qui contient une unité constitutive (a-1) issue d'un composé diène conjugué et qui a une teneur en liaison vinylique inférieure à 30 % en mole et un bloc de polymère (B) qui contient une unité constitutive (b-1) issue d'un composé diène conjugué et qui a une teneur en liaison vinylique de 30-95 % en mole.
PCT/JP2012/063376 2011-05-26 2012-05-24 Composition pour des matières de stockage de chaleur, matière de stockage de chaleur et dispositif pour un stockage de chaleur Ceased WO2012161278A1 (fr)

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WO2015156416A1 (fr) * 2014-04-09 2015-10-15 住友化学株式会社 Composition de résine, produit réticulé et procédé permettant la fabrication de produit réticulé
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JP2020189914A (ja) * 2019-05-21 2020-11-26 昭和電工マテリアルズ株式会社 組成物、シート及び物品
JPWO2021241432A1 (fr) * 2020-05-29 2021-12-02
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WO2013077379A1 (fr) * 2011-11-22 2013-05-30 Jsr株式会社 Matière de stockage de chaleur, dispositif de stockage de chaleur, microcapsule de stockage de chaleur
EP3044251A1 (fr) * 2013-09-12 2016-07-20 Benecke-Kaliko AG Feuille et son procédé de fabrication
WO2015156416A1 (fr) * 2014-04-09 2015-10-15 住友化学株式会社 Composition de résine, produit réticulé et procédé permettant la fabrication de produit réticulé
JPWO2015156416A1 (ja) * 2014-04-09 2017-04-13 住友化学株式会社 樹脂組成物、架橋物、および架橋物の製造方法
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WO2017010410A1 (fr) * 2015-07-16 2017-01-19 Ｊｘエネルギー株式会社 Composition d'élastomère thermoplastique, article moulé, matériau de construction, panneau de matériau de construction et matériau de plâtre
JP2020189914A (ja) * 2019-05-21 2020-11-26 昭和電工マテリアルズ株式会社 組成物、シート及び物品
JPWO2021241432A1 (fr) * 2020-05-29 2021-12-02
WO2021241432A1 (fr) * 2020-05-29 2021-12-02 住友化学株式会社 Composition de stockage de chaleur
JP7747630B2 (ja) 2020-05-29 2025-10-01 住友化学株式会社 蓄熱組成物
KR102898695B1 (ko) * 2020-05-29 2025-12-10 스미또모 가가꾸 가부시끼가이샤 축열 조성물

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