WO2019111358A1 - Resinous member, sheet, heat-storage material, and production method for resinous member - Google Patents

Resinous member, sheet, heat-storage material, and production method for resinous member Download PDF

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Publication number
WO2019111358A1
WO2019111358A1 PCT/JP2017/043848 JP2017043848W WO2019111358A1 WO 2019111358 A1 WO2019111358 A1 WO 2019111358A1 JP 2017043848 W JP2017043848 W JP 2017043848W WO 2019111358 A1 WO2019111358 A1 WO 2019111358A1
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Prior art keywords
resin member
member according
component
olefin
sheet
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PCT/JP2017/043848
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French (fr)
Japanese (ja)
Inventor
晃 永井
森本　剛
古川　直樹
木沢　桂子
望 松原
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日立化成株式会社
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Priority to JP2019557927A priority Critical patent/JP7124833B2/en
Priority to PCT/JP2017/043848 priority patent/WO2019111358A1/en
Priority to CN201780097420.8A priority patent/CN111433276A/en
Publication of WO2019111358A1 publication Critical patent/WO2019111358A1/en

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    • 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
    • C08L23/08—Copolymers of ethene
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention relates to a resin member, a sheet using the same, a method of manufacturing the resin member, a heat storage material, and a thermal control sheet using the same.
  • heat storage materials are provided in air conditioners in automobiles, buildings, underground malls, etc., engines of automobiles, electronic parts, etc. in order to temporarily save thermal energy and take out the thermal energy as needed.
  • the heat storage material for example, a material that stores or dissipates heat using phase transition of a substance is mentioned.
  • a heat storage material for example, one using a saturated hydrocarbon compound is known.
  • the saturated hydrocarbon compound has excellent heat storage properties by reversibly performing phase transition. However, since the saturated hydrocarbon compound is in a liquid state on the high temperature side of the phase transition, and the saturated hydrocarbon compound may exude, some sort of anti-spill measures must be taken.
  • Patent Document 1 discloses a heat storage material including a styrene-ethylene-ethylene-propylene-styrene copolymer and a paraffin wax as a heat storage material that suppresses bleeding. There is.
  • thermal storage material may be used for thermal storage members, such as a heat pipe, in this case, not only a high thermal storage capacity but the rapidity of heat exchange is requested
  • the thermal conductivity of the heat storage material as described in Patent Document 1 is low, the heat storage material does not necessarily satisfy such a requirement.
  • the present invention has been made in view of such circumstances, and provides a resin member capable of achieving high heat storage capacity and high thermal conductivity while suppressing bleeding of a saturated hydrocarbon compound, and a method for producing the same. It is the main purpose.
  • Another object of the present invention is to provide a sheet and a heat storage material using the resin member.
  • the present invention in one aspect, is a resin member comprising a copolymer of ethylene and an olefin having 3 or more carbon atoms, a saturated hydrocarbon compound, and carbon fibers.
  • the thermal conductivity of the carbon fiber may be 300 W / mK or more.
  • the carbon number of the olefin may be 3-8.
  • the melting point of the saturated hydrocarbon compound may be less than 50 ° C., and the carbon number of the olefin may be 8.
  • the aspect ratio of the carbon fiber may be 100 to 1000.
  • the content of the carbon fiber may be 15% by mass or more based on the total amount of the resin member.
  • the resin member may further contain a gelling agent.
  • the resin member may further contain at least one selected from the group consisting of carboxylic acids and carboxylic acid metal salts.
  • This invention is a sheet
  • the thermal conductivity of the resin layer may be 1 W / mK or more, and the heat of fusion of the resin layer may be 90 J / g or more.
  • the present invention in another aspect, is a heat storage material provided with the above resin member.
  • the present invention comprises the step of heat melting and molding a composition comprising a copolymer of ethylene and an olefin having 3 or more carbon atoms, a saturated hydrocarbon compound, and carbon fibers. And a method of manufacturing a resin member.
  • the composition can be molded by injection molding, compression molding or transfer molding in the above-described steps.
  • the present invention it is possible to provide a resin member capable of achieving high heat storage capacity and high thermal conductivity while suppressing bleeding of a saturated hydrocarbon compound, and a method for producing the same, and using the resin member It becomes possible to provide a sheet and a heat storage material.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of a resin member.
  • the resin member 1 is a copolymer of ethylene and an olefin having 3 or more carbon atoms (hereinafter, also referred to as “component (A)”), and a saturated hydrocarbon compound (hereinafter, “component (B)”) And carbon fibers (hereinafter, also referred to as “component (C)”).
  • component (A) ethylene and an olefin having 3 or more carbon atoms
  • component (B) saturated hydrocarbon compound
  • component (C) carbon fibers
  • the resin member 1 may be, for example, a sheet (film).
  • the carbon number of the olefin (hereinafter, also simply referred to as “olefin”) constituting the component (A) is 3 or more, for example, 3 to 8.
  • the olefin may be linear or branched.
  • a copolymer of ethylene and an olefin having 3 or more carbon atoms for example, a copolymer of ethylene and propylene (C3 (carbon number, the same applies hereinafter)), a copolymer of ethylene and butene (C4), Copolymer of ethylene and pentene (C5), copolymer of ethylene and hexene (C6), copolymer of ethylene and heptene (C7), copolymer of ethylene and octene (C8), ethylene Copolymers of nonene (C9), copolymers of ethylene and decene (C10), and the like can be mentioned.
  • C3 carbon number, the same applies hereinafter
  • copolymers of ethylene and an olefin having 3 to 8 carbon atoms are preferably used because they are easily available.
  • the copolymer of ethylene and an olefin having 3 or more carbon atoms may be used alone or in combination of two or more.
  • the content of the component (A) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more, based on the total amount of the resin member.
  • the content of the component (A) is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, based on the total amount of the resin member.
  • the component (B) has, for example, a melting point in the range of 0 to 100 ° C. from the viewpoint of obtaining a heat storage effect in a practical range.
  • the component (B) is preferably a linear saturated hydrocarbon compound.
  • chain-like means linear or branched.
  • the component (B) is preferably linear.
  • the component (B) is n-tetradecane (C14 (carbon number, the same applies hereinafter), 6 ° C.
  • n-pentadecane C15, 9 ° C.
  • n-hexadecane C16, 18 ° C
  • n-heptadecane C17, 21 ° C
  • n-octadecane C18, 28 ° C
  • n-nanodecane C19, 32 ° C
  • n-eicosane C20, 37 ° C
  • n-henicosane C21, 41 ° C.
  • n-docosane C22, 46 ° C.
  • n-trichosan C23, 47 ° C.
  • n-tetracosane C24, 50 ° C.
  • n-pentacosane C25, 54 ° C.
  • n-hexacosane C26, 56 ° C
  • n-heptacosane C27, 60 ° C
  • n-pentadecane C15, 9 °
  • the melting point of the component (B) is a melting point (endothermic of a thermogram obtained when heated at a temperature rising rate of 10 ° C./min using a differential scanning calorimeter (for example, “8500” manufactured by PerkinElmer Co., Ltd.) ) The temperature of the point where the tangent of the maximum slope of the peak intersects the baseline.
  • the component (B) may be a petroleum wax mainly composed of a linear saturated hydrocarbon compound.
  • Petroleum wax is a separated and refined product from a vacuum distillation component of petroleum or natural gas which is a raw material.
  • Specific examples of petroleum wax include Paraffin Wax (48-69 ° C. (melting point, the same applies hereinafter)), HNP (64-77 ° C.), SP (60-74 ° C.), EMW manufactured by Nippon Seiwa Co., Ltd. (49 ° C.) and the like. These components (B) may be used alone or in combination of two or more.
  • the content of the component (B) is preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, based on the total amount of the resin member.
  • the content of the component (B) is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, based on the total mass of the resin member.
  • the number of carbon atoms of the olefin in the component (A) is preferably 8 from the viewpoint of being excellent in suppression of the fluidity of the saturated hydrocarbon compound.
  • the carbon fiber (component (C)) is defined as a fibrous (long and narrow shape) carbon material having an aspect ratio of 20 or more.
  • the aspect ratio is calculated from the scanning electron micrograph of the carbon material, the maximum length of the carbon material (fiber length) and the minimum length of the carbon material in the direction perpendicular to the direction having the maximum length (fiber diameter ) Is defined as the ratio (maximum length / minimum length).
  • the carbon fiber has a small density (specific gravity) and can be added to the resin member in a large amount as compared to, for example, a metal fiber, so that the heat storage amount and the thermal conductivity of the resin member can be enhanced.
  • the aspect ratio of carbon fiber is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more, from the viewpoint of easily increasing the contact probability between carbon fibers and easily increasing the thermal conductivity of the resin member even with a small addition amount. is there.
  • the aspect ratio of the carbon fiber is preferably 1000 or less, more preferably 800 or less, and still more preferably 700 or less, from the viewpoint of excellent handling properties and dispersibility, and stable characteristics of the resin member.
  • the aspect ratio of the carbon fiber is preferably 100 to 1000, 100 to 800, 100 to 700, 200 to 1000, 200 to 800, 200 to 700, 300 to 1000, 300 to 300 from the viewpoint of compatibility with these points. 800 or 300 to 700.
  • the carbon fiber has a thermal conductivity of preferably 300 W / mK or more, more preferably 400 W / mK or more, and still more preferably 500 W / mK or more, from the viewpoint of easily increasing the thermal conductivity of the resin member even with a small addition amount.
  • a thermal conductivity of the carbon fiber There is no upper limit to the thermal conductivity of the carbon fiber, and the thermal conductivity of the resin member can be increased as the thermal conductivity of the carbon fiber is higher.
  • the content of the component (C) is preferably 15% by mass or more, more preferably 18% by mass or more, still more preferably 20% by mass or more, based on the total amount of the resin member, from the viewpoint of further enhancing the thermal conductivity of the resin member. It is.
  • the content of the component (C) is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, based on the total amount of resin members, from the viewpoint of maintaining the heat of fusion as high as possible.
  • the resin member 1 may further contain a gelling agent (hereinafter, also referred to as “component (D)”).
  • component (D) is not particularly limited as long as it is a component capable of gelling the component (B).
  • the component (D) may be, for example, at least one selected from the group consisting of carboxylic acids and carboxylic acid metal salts. That is, in one embodiment, the resin member 1 is selected from the group consisting of a copolymer of ethylene and an olefin having 3 or more carbon atoms, a saturated hydrocarbon compound, a carbon fiber, a carboxylic acid and a carboxylic acid metal salt. And at least one of the
  • the carboxylic acid is preferably a chain aliphatic carboxylic acid from the viewpoint of good compatibility with the saturated hydrocarbon compound.
  • the carbon number of the carboxylic acid is preferably 10 or more, and for example, 10 to 40, 10 to 30, or 10 to 25.
  • the carboxylic acids may be saturated or unsaturated.
  • the carboxylic acid is not particularly limited.
  • lauric acid C12 (carbon number, the same applies hereinafter)
  • myristic acid C14
  • palmitic acid C16
  • stearic acid C18
  • isostearic acid C18
  • docosahexaene Acid C22
  • behenic acid C21
  • undecylenic acid C11
  • oleic acid C18
  • erucic acid C22
  • linoleic acid C18
  • arachidonic acid C20
  • linolenic acid C18
  • sapienic acid C18 C16
  • the carboxylic acids may be used alone or in combination of two or more.
  • the carboxylic acid constituting the carboxylic acid metal salt is preferably a chain aliphatic carboxylic acid from the viewpoint of good compatibility with the saturated hydrocarbon compound (compatibility with the carboxylic acid when using the carboxylic acid in combination).
  • the carbon number of the carboxylic acid constituting the carboxylic acid metal salt is preferably 6 or more, and for example, 6 to 30, 6 to 25 or 8 to 20.
  • the carboxylic acid which comprises carboxylic acid metal salt may be saturated or unsaturated.
  • the metal which comprises carboxylic acid metal salt is a metal which can form a salt with carboxylic acid, for example, is aluminum.
  • carboxylic acid metal salts include aluminum stearate (C18 (number of carbon atoms, the same applies hereinafter)), aluminum laurate (C12), aluminum oleate (C18), aluminum behenate (C21), and aluminum palmitate ( C16), aluminum 2-ethylhexanoate (C8) and the like.
  • the carboxylic acid metal salts may be used alone or in combination of two or more.
  • the content of the component (D) may be 3% by mass or more, and 10% by mass or less, 8% by mass or less, or 6% by mass or less, based on the total amount of the resin member.
  • the resin member 1 may further contain a polymer having a melting point of 100 ° C. or higher (hereinafter, also referred to as “component (E)”).
  • component (E) is a component other than a copolymer of ethylene and an olefin having 3 or more carbon atoms (component (A)).
  • the melting point of the component (E) may be 100 ° C. or more, 120 ° C. or more, or 140 ° C. or more, and may be 250 ° C. or less, 230 ° C. or less, or 200 ° C. or less.
  • the component (E) desirably has good compatibility with the components (A) and (B) described above.
  • the component (E) may be, for example, polyethylene (ethylene homopolymer), polypropylene (propylene homopolymer), etc., a modified polymer of polyethylene or polypropylene further containing ethylene or monomer units other than propylene, ethylene or propylene It may be a copolymer (copolymer) or the like with one or more other monomers.
  • the copolymer (copolymer) may, for example, be a block copolymer.
  • one type may be used alone, or two or more types may be used in combination.
  • the resin member 1 is preferably polyethylene as the component (E) from the viewpoint of further excellent in fluidity suppression and shape maintenance in a temperature range of 50 ° C. or higher. It further includes at least one selected from the group consisting of (ethylene homopolymer) and polypropylene (propylene homopolymer).
  • the content of the component (E) may be 5% by mass or more, 30% by mass or less, 25% by mass or less, or 20% by mass or less, based on the total amount of the resin member.
  • the resin member 1 may further contain other components in addition to the components (A) to (E).
  • the other components include carbon materials (for example, graphite) other than the above-mentioned carbon fibers, metal fibers, glass, inorganic components such as talc, light absorbers that suppress photodegradation, and the like.
  • the content of the other components may be, for example, 10% by mass or less based on the total amount of the resin member.
  • the resin member 1 described above is obtained, for example, by the following method. That is, in the state where the saturated hydrocarbon compound (component (B)) is heated to the melting point or higher, a copolymer of ethylene and an olefin having 3 or more carbon atoms (component (A)) and, if necessary, a melting point Add the polymer (component (E)) at 100 ° C. or higher and mix uniformly. Thereafter, at least one member (component (D)) selected from the group consisting of carboxylic acids and carboxylic acid metal salts is added, if necessary, and homogeneous mixing is further performed.
  • a carbon fiber (component (C)) is added and the mixture is kneaded by a pressure heating press to obtain a resin member.
  • the sheet-like resin member 1 can also be obtained by heating and melting this resin member and molding it. That is, in the method for producing the resin member 1, the composition containing the components (A) to (C) and, if necessary, the components (D), (E) and other components is heat-melted and molded.
  • a process molding process
  • Molding in the molding process may be injection molding, compression molding or transfer molding.
  • seat may be a sheet
  • the thickness of the resin layer may be, for example, 1 to 30 mm, 2 to 20 mm, or 5 to 10 mm.
  • the thickness of the metal layer may be, for example, 100 ⁇ m or less.
  • the resin layer has high thermal conductivity.
  • the thermal conductivity of the resin layer may be preferably 1 W / mK or more, 1.1 W / mK or more, or 1.2 W / mK or more.
  • the thermal conductivity of the resin layer is measured using a thermal conductivity meter (for example, "QTM-500" manufactured by Kyoto Denshi Kogyo Co., Ltd.).
  • the resin layer has a high heat storage capacity (heat of fusion).
  • the heat of fusion of the resin layer may be preferably 90 J / g or more, 95 J / g or more, or 100 J / g or more.
  • the heat of fusion of the resin layer is the melting of the thermogram obtained when heated at a temperature rising rate of 10 ° C./min using a differential scanning calorimeter (for example, “8500” manufactured by PerkinElmer Co., Ltd.) (endothermic) Calculated from the area of the peak.
  • the resin member 1 and the sheet using the same can be suitably used as a heat storage material because it is possible to store or release heat using phase transition. That is, another embodiment of the present invention is a heat storage material provided with the above-mentioned resin member 1.
  • the heat storage material (resin member, sheet) of the present embodiment can be used in various fields.
  • Thermal storage materials (resin members, sheets) are, for example, air conditioners (improve the efficiency of air conditioners) in automobiles, buildings, public facilities, underground malls, etc., pipes (heat storage in pipes) in factories etc, engine of automobile (around the engine Heat insulation), electronic parts (preventing temperature rise of electronic parts), fibers of underwear, etc.
  • the heat storage material (resin member, sheet) can be stuck to the object to be attached or wound because it can suppress the increase in the fluidity of the component (B) and the generation of bleeding associated therewith even above the melting point of the component (B). It can be installed in various ways.
  • Examples 1 to 7 A resin member having a composition shown in Table 1 using a copolymer of ethylene and an olefin having 3 or more carbon atoms, a chain-like saturated hydrocarbon compound, a carbon fiber, and a carboxylic acid and a carboxylic acid metal salt shown below Made. Specifically, in the state where the saturated hydrocarbon compound was heated to the melting point or higher, a copolymer of ethylene and an olefin having 3 or more carbon atoms was added and uniformly mixed. Thereafter, carboxylic acid and carboxylic acid metal salt were added and mixed more uniformly.
  • A-1 Copolymer of ethylene and octene (Dow Chemical Japan Ltd., product name "ENGAGE 8150") (Chain-like saturated hydrocarbon compound)
  • B-1 n-hexadecane (melting point: 18 ° C.)
  • Carbon fiber C-1: GRANOC XN-90C-06S (manufactured by Nippon Graphite Fiber Co., Ltd., aspect ratio 600 (fiber diameter 10 ⁇ m, fiber length 6 mm), thermal conductivity 500 W / mK)
  • C-2 Lahema R-A301 (manufactured by Teijin Limited, aspect ratio 25 (fiber diameter 8 ⁇ m, fiber length 0.2 mm), thermal conductivity 550 W / m K)
  • C-3 Dona Carbo S201 (Osaka Gas Chemical Co., Ltd., aspect ratio 833 (fiber diameter: 18 ⁇ m, fiber length: about 15 mm), thermal conductivity
  • the melting point of the saturated hydrocarbon compound was calculated by differential thermal analysis (DSC) from the peak temperature of melting in the heating process at a heating rate of 10 ° C./min.
  • Comparative Example 1 A resin member was obtained in the same manner as Example 1, except that the following carbon material C-6 was used instead of the carbon fiber.
  • C-6 Fine powder graphite (manufactured by Showa Denko KK, aspect ratio less than 20, fine powder diameter 7 ⁇ m or less)
  • Comparative Example 2 A resin member was obtained in the same manner as Example 1, except that carbon fiber was not used.
  • the thermal conductivity in the sheet surface was measured using QTM-500 (manufactured by Kyoto Denshi Kogyo Co., Ltd.) and using PD-11N as a probe.

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Abstract

The present invention, in one aspect, is a resinous member which comprises a copolymer of ethylene with a C3 or higher olefin, a saturated hydrocarbon compound, and carbon fibers.

Description

樹脂部材、シート、蓄熱材、及び樹脂部材の製造方法Resin member, sheet, heat storage material, and method of manufacturing resin member
　本発明は、樹脂部材及びそれを用いたシート、樹脂部材の製造方法、並びに蓄熱材及びそれを用いた熱制御シートに関する。 The present invention relates to a resin member, a sheet using the same, a method of manufacturing the resin member, a heat storage material, and a thermal control sheet using the same.
　従来、自動車、建築物、地下街等における空調設備、自動車のエンジン、電子部品などには、熱エネルギーを一時的に貯蓄しておき随時その熱エネルギーを取り出すために蓄熱材が備えられている。 2. Description of the Related Art Conventionally, heat storage materials are provided in air conditioners in automobiles, buildings, underground malls, etc., engines of automobiles, electronic parts, etc. in order to temporarily save thermal energy and take out the thermal energy as needed.
　蓄熱材としては、例えば物質の相転移を利用して蓄熱又は放熱するものが挙げられる。このような蓄熱材として、例えば、飽和炭化水素化合物を用いたものが知られている。飽和炭化水素化合物は、可逆的に相転移をすることにより、優れた蓄熱性を有する。しかし、飽和炭化水素化合物は相転移の高温側では液体状態であり、飽和炭化水素化合物が滲みだす可能性があるため、何らかの滲みだし防止策を施さなければならない。 As the heat storage material, for example, a material that stores or dissipates heat using phase transition of a substance is mentioned. As such a heat storage material, for example, one using a saturated hydrocarbon compound is known. The saturated hydrocarbon compound has excellent heat storage properties by reversibly performing phase transition. However, since the saturated hydrocarbon compound is in a liquid state on the high temperature side of the phase transition, and the saturated hydrocarbon compound may exude, some sort of anti-spill measures must be taken.
　このような問題に対し、例えば特許文献１には、滲みだしを抑制する蓄熱材として、スチレン－エチレン－エチレン－プロピレン－スチレン共重合体と、パラフィン系ワックスと、を含む蓄熱材が開示されている。 For such a problem, for example, Patent Document 1 discloses a heat storage material including a styrene-ethylene-ethylene-propylene-styrene copolymer and a paraffin wax as a heat storage material that suppresses bleeding. There is.
特開２０１４－８８５１７号公報JP 2014-88517 A
　ところで、蓄熱材は、ヒートパイプ等の蓄熱部材に用いられることがあるが、この場合、蓄熱材には、高い蓄熱容量のみならず、熱交換の迅速性が要求される。しかし、特許文献１に記載されているような蓄熱材の熱伝導率は低いため、当該蓄熱材はこのような要求を必ずしも満たしていない。 By the way, although a thermal storage material may be used for thermal storage members, such as a heat pipe, in this case, not only a high thermal storage capacity but the rapidity of heat exchange is requested | required of a thermal storage material. However, since the thermal conductivity of the heat storage material as described in Patent Document 1 is low, the heat storage material does not necessarily satisfy such a requirement.
　本発明は、このような実情に鑑みてなされたものであり、飽和炭化水素化合物の滲みだしを抑制すると共に、高蓄熱容量及び高熱伝導率を達成できる樹脂部材及びその製造方法を提供することを主な目的とする。また、本発明の他の目的は、該樹脂部材を用いたシート及び蓄熱材を提供することである。 The present invention has been made in view of such circumstances, and provides a resin member capable of achieving high heat storage capacity and high thermal conductivity while suppressing bleeding of a saturated hydrocarbon compound, and a method for producing the same. It is the main purpose. Another object of the present invention is to provide a sheet and a heat storage material using the resin member.
　本発明は、一態様において、エチレンと炭素数が３以上のオレフィンとの共重合体と、飽和炭化水素化合物と、炭素繊維と、を含む樹脂部材である。 The present invention, in one aspect, is a resin member comprising a copolymer of ethylene and an olefin having 3 or more carbon atoms, a saturated hydrocarbon compound, and carbon fibers.
　この樹脂部材において、炭素繊維の熱伝導率は、３００Ｗ／ｍＫ以上であってよい。オレフィンの炭素数は、３～８であってよい。飽和炭化水素化合物の融点が５０℃未満であり、オレフィンの炭素数が８であってよい。炭素繊維のアスペクト比は、１００～１０００であってよい。炭素繊維の含有量は、樹脂部材の全量を基準として１５質量％以上であってよい。樹脂部材は、ゲル化剤を更に含んでいてよい。樹脂部材は、カルボン酸及びカルボン酸金属塩からなる群より選ばれる少なくとも１種を更に含んでいてよい。 In the resin member, the thermal conductivity of the carbon fiber may be 300 W / mK or more. The carbon number of the olefin may be 3-8. The melting point of the saturated hydrocarbon compound may be less than 50 ° C., and the carbon number of the olefin may be 8. The aspect ratio of the carbon fiber may be 100 to 1000. The content of the carbon fiber may be 15% by mass or more based on the total amount of the resin member. The resin member may further contain a gelling agent. The resin member may further contain at least one selected from the group consisting of carboxylic acids and carboxylic acid metal salts.
　本発明は、他の一態様において、上記の樹脂部材からなる樹脂層を備えるシートである。このシートにおいて、樹脂層の熱伝導率は１Ｗ／ｍＫ以上であってよく、樹脂層の融解熱は９０Ｊ／ｇ以上であってよい。 This invention is a sheet | seat provided with the resin layer which consists of said resin member in another one aspect | mode. In this sheet, the thermal conductivity of the resin layer may be 1 W / mK or more, and the heat of fusion of the resin layer may be 90 J / g or more.
　本発明は、他の一態様において、上記の樹脂部材を備える蓄熱材である。 The present invention, in another aspect, is a heat storage material provided with the above resin member.
　本発明は、他の一態様において、エチレンと炭素数が３以上のオレフィンとの共重合体と、飽和炭化水素化合物と、炭素繊維と、を含む組成物を加熱溶融して成形する工程を備える、樹脂部材の製造方法である。この製造方法では、上記の工程において、射出成形、圧縮成形又はトランスファー成形により組成物を成形することができる。 In another aspect, the present invention comprises the step of heat melting and molding a composition comprising a copolymer of ethylene and an olefin having 3 or more carbon atoms, a saturated hydrocarbon compound, and carbon fibers. And a method of manufacturing a resin member. In this manufacturing method, the composition can be molded by injection molding, compression molding or transfer molding in the above-described steps.
　本発明によれば、飽和炭化水素化合物の滲みだしを抑制すると共に、高蓄熱容量及び高熱伝導率を達成できる樹脂部材及びその製造方法を提供することが可能となり、また、該樹脂部材を用いたシート及び蓄熱材を提供することが可能となる。 According to the present invention, it is possible to provide a resin member capable of achieving high heat storage capacity and high thermal conductivity while suppressing bleeding of a saturated hydrocarbon compound, and a method for producing the same, and using the resin member It becomes possible to provide a sheet and a heat storage material.
樹脂部材の一実施形態を示す模式断面図である。It is a schematic cross section which shows one Embodiment of a resin member.
　以下、図面を適宜参照しながら、本発明の実施形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as appropriate.
　図１は、樹脂部材の一実施形態を示す模式断面図である。樹脂部材１は、一実施形態において、エチレンと炭素数が３以上のオレフィンとの共重合体（以下、「（Ａ）成分」ともいう）と、飽和炭化水素化合物（以下、「（Ｂ）成分」ともいう）と、炭素繊維（以下、「（Ｃ）成分」ともいう）とを含む。樹脂部材１は、例えばシート状（フィルム状）であってよい。 FIG. 1 is a schematic cross-sectional view showing an embodiment of a resin member. In one embodiment, the resin member 1 is a copolymer of ethylene and an olefin having 3 or more carbon atoms (hereinafter, also referred to as “component (A)”), and a saturated hydrocarbon compound (hereinafter, “component (B)”) And carbon fibers (hereinafter, also referred to as “component (C)”). The resin member 1 may be, for example, a sheet (film).
　（Ａ）成分を構成するオレフィン（以下、単に「オレフィン」ともいう）の炭素数は、３以上であり、例えば３～８である。オレフィンの炭素数が４以上である場合、オレフィンは、直鎖状であっても分岐鎖状であってもよい。エチレンと炭素数が３以上のオレフィンとの共重合体としては、例えば、エチレンとプロピレン（Ｃ３（炭素数、以下同様））との共重合体、エチレンとブテン（Ｃ４）との共重合体、エチレンとペンテン（Ｃ５）との共重合体、エチレンとヘキセン（Ｃ６）との共重合体、エチレンとヘプテン（Ｃ７）との共重合体、エチレンとオクテン（Ｃ８）との共重合体、エチレンとノネン（Ｃ９）との共重合体、エチレンとデセン（Ｃ１０）との共重合体等が挙げられる。これらの中でも、エチレンと炭素数が３～８のオレフィンとの共重合体は、入手が容易であるため、好ましく用いられる。エチレンと炭素数が３以上のオレフィンとの共重合体は、１種単独で用いられても、２種以上を組み合せて用いられてもよい。 The carbon number of the olefin (hereinafter, also simply referred to as “olefin”) constituting the component (A) is 3 or more, for example, 3 to 8. When the olefin has 4 or more carbon atoms, the olefin may be linear or branched. As a copolymer of ethylene and an olefin having 3 or more carbon atoms, for example, a copolymer of ethylene and propylene (C3 (carbon number, the same applies hereinafter)), a copolymer of ethylene and butene (C4), Copolymer of ethylene and pentene (C5), copolymer of ethylene and hexene (C6), copolymer of ethylene and heptene (C7), copolymer of ethylene and octene (C8), ethylene Copolymers of nonene (C9), copolymers of ethylene and decene (C10), and the like can be mentioned. Among these, copolymers of ethylene and an olefin having 3 to 8 carbon atoms are preferably used because they are easily available. The copolymer of ethylene and an olefin having 3 or more carbon atoms may be used alone or in combination of two or more.
　（Ａ）成分の含有量は、樹脂部材全量基準で、好ましくは５質量％以上、より好ましくは１０質量％以上、更に好ましくは１５質量％以上である。（Ａ）成分の含有量は、樹脂部材全量基準で、好ましくは５０質量％以下、より好ましくは４０質量％以下、更に好ましくは３０質量％以下である。 The content of the component (A) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more, based on the total amount of the resin member. The content of the component (A) is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, based on the total amount of the resin member.
　（Ｂ）成分は、実用範囲で蓄熱効果を得る観点から、例えば０～１００℃の範囲内に融点を有する。（Ｂ）成分は、好ましくは鎖状の飽和炭化水素化合物である。本明細書において、「鎖状」とは、直鎖状又は分岐鎖状を意味する。（Ｂ）成分は、好ましくは直鎖状である。（Ｂ）成分は、具体的には、ｎ－テトラデカン（Ｃ１４（炭素数、以下同様）、６℃（融点、以下同様））、ｎ－ペンタデカン（Ｃ１５、９℃）、ｎ－ヘキサデカン（Ｃ１６、１８℃）、ｎ－ヘプタデカン（Ｃ１７、２１℃）、ｎ－オクタデカン（Ｃ１８、２８℃）、ｎ－ナノデカン（Ｃ１９、３２℃）、ｎ－エイコサン（Ｃ２０、３７℃）、ｎ－ヘンイコサン（Ｃ２１、４１℃）、ｎ－ドコサン（Ｃ２２、４６℃）、ｎ－トリコサン（Ｃ２３、４７℃）、ｎ－テトラコサン（Ｃ２４、５０℃）、ｎ－ペンタコサン（Ｃ２５、５４℃）、ｎ－ヘキサコサン（Ｃ２６、５６℃）、ｎ－ヘプタコサン（Ｃ２７、６０℃）、ｎ－オクタコサン（Ｃ２８、６５℃）、ｎ－ノナコサン（Ｃ２９、６６℃）、ｎ－トリアコンタン（Ｃ３０、６７℃）、ｎ－テトラコンタン（Ｃ４０、８１℃）、ｎ－ペンタコンタン（Ｃ５０、９１℃）、ｎ－ヘキサコンタン（Ｃ６０、９８℃）等であってよい。（Ｂ）成分の融点は、示差走査熱量計（例えば、（株）パーキンエルマー製「８５００」）を用いて、昇温速度１０℃／分で加熱したときに得られたサーモグラムの融解（吸熱）ピークの最大傾斜の接線がベースラインと交わる点の温度である。 The component (B) has, for example, a melting point in the range of 0 to 100 ° C. from the viewpoint of obtaining a heat storage effect in a practical range. The component (B) is preferably a linear saturated hydrocarbon compound. As used herein, "chain-like" means linear or branched. The component (B) is preferably linear. Specifically, the component (B) is n-tetradecane (C14 (carbon number, the same applies hereinafter), 6 ° C. (melting point, the same applies hereinafter)), n-pentadecane (C15, 9 ° C.), n-hexadecane (C16, 18 ° C), n-heptadecane (C17, 21 ° C), n-octadecane (C18, 28 ° C), n-nanodecane (C19, 32 ° C), n-eicosane (C20, 37 ° C), n-henicosane (C21, 41 ° C.), n-docosane (C22, 46 ° C.), n-trichosan (C23, 47 ° C.), n-tetracosane (C24, 50 ° C.), n-pentacosane (C25, 54 ° C.), n-hexacosane (C26, 56 ° C), n-heptacosane (C27, 60 ° C), n-octacosane (C28, 65 ° C), n-nonacosan (C29, 66 ° C), n-triacontan (C30, 67 ° C), n- Torakontan (C40,81 ℃), n- pentacontanoic (C50,91 ℃), may be n- Hekisakontan (C60,98 ℃) or the like. The melting point of the component (B) is a melting point (endothermic of a thermogram obtained when heated at a temperature rising rate of 10 ° C./min using a differential scanning calorimeter (for example, “8500” manufactured by PerkinElmer Co., Ltd.) ) The temperature of the point where the tangent of the maximum slope of the peak intersects the baseline.
　（Ｂ）成分は、直鎖状の飽和炭化水素化合物を主成分とする石油ワックスであってもよい。石油ワックスは、原料である石油又は天然ガスの減圧蒸留成分からの分離精製品である。石油ワックスの具体的な例としては、日本精蝋（株）製のＰａｒａｆｆｉｎ　Ｗａｘ（４８～６９℃（融点、以下同様））、ＨＮＰ（６４～７７℃）、ＳＰ（６０～７４℃）、ＥＭＷ（４９℃）等が挙げられる。これらの（Ｂ）成分は、１種単独で用いられても、２種以上を組み合わせて用いられてもよい。 The component (B) may be a petroleum wax mainly composed of a linear saturated hydrocarbon compound. Petroleum wax is a separated and refined product from a vacuum distillation component of petroleum or natural gas which is a raw material. Specific examples of petroleum wax include Paraffin Wax (48-69 ° C. (melting point, the same applies hereinafter)), HNP (64-77 ° C.), SP (60-74 ° C.), EMW manufactured by Nippon Seiwa Co., Ltd. (49 ° C.) and the like. These components (B) may be used alone or in combination of two or more.
　（Ｂ）成分の含有量は、樹脂部材全量基準で、好ましくは４０質量％以上、より好ましくは４５質量％以上、更に好ましくは５０質量％以上である。（Ｂ）成分の含有量は、樹脂部材全量基準で、好ましくは９０質量％以下、より好ましくは８０質量％以下、更に好ましくは７０質量％以下である。 The content of the component (B) is preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, based on the total amount of the resin member. The content of the component (B) is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, based on the total mass of the resin member.
　飽和炭化水素化合物の融点が５０℃未満である場合、飽和炭化水素化合物の流動性の抑制により優れる観点から、（Ａ）成分におけるオレフィンの炭素数は好ましくは８である。 When the melting point of the saturated hydrocarbon compound is less than 50 ° C., the number of carbon atoms of the olefin in the component (A) is preferably 8 from the viewpoint of being excellent in suppression of the fluidity of the saturated hydrocarbon compound.
　炭素繊維（（Ｃ）成分）は、アスペクト比が２０以上である繊維状（細長形状）の炭素材料として定義される。アスペクト比は、炭素材料の走査型電子顕微鏡写真から算出される、炭素材料の最大長さ（繊維長）と、当該最大長さを有する方向に垂直な方向における炭素材料の最小長さ（繊維径）との比（最大長さ／最小長さ）として定義される。炭素繊維は、密度（比重）が小さく、例えば金属繊維に比べて、樹脂部材に多量に添加することができるため、樹脂部材の蓄熱量及び熱伝導率を高めることを可能にする。 The carbon fiber (component (C)) is defined as a fibrous (long and narrow shape) carbon material having an aspect ratio of 20 or more. The aspect ratio is calculated from the scanning electron micrograph of the carbon material, the maximum length of the carbon material (fiber length) and the minimum length of the carbon material in the direction perpendicular to the direction having the maximum length (fiber diameter ) Is defined as the ratio (maximum length / minimum length). The carbon fiber has a small density (specific gravity) and can be added to the resin member in a large amount as compared to, for example, a metal fiber, so that the heat storage amount and the thermal conductivity of the resin member can be enhanced.
　炭素繊維のアスペクト比は、炭素繊維同士の接触確率を更に高め、少ない添加量でも樹脂部材の熱伝導率を高めやすい観点から、好ましくは１００以上、より好ましくは２００以上、更に好ましくは３００以上である。炭素繊維のアスペクト比は、ハンドリング性及び分散性に優れ、樹脂部材の特性が安定する観点から、好ましくは１０００以下、より好ましくは８００以下、更に好ましくは７００以下である。これらの点を両立するか点から、炭素繊維のアスペクト比は、好ましくは、１００～１０００、１００～８００、１００～７００、２００～１０００、２００～８００、２００～７００、３００～１０００、３００～８００、又は３００～７００である。 The aspect ratio of carbon fiber is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more, from the viewpoint of easily increasing the contact probability between carbon fibers and easily increasing the thermal conductivity of the resin member even with a small addition amount. is there. The aspect ratio of the carbon fiber is preferably 1000 or less, more preferably 800 or less, and still more preferably 700 or less, from the viewpoint of excellent handling properties and dispersibility, and stable characteristics of the resin member. The aspect ratio of the carbon fiber is preferably 100 to 1000, 100 to 800, 100 to 700, 200 to 1000, 200 to 800, 200 to 700, 300 to 1000, 300 to 300 from the viewpoint of compatibility with these points. 800 or 300 to 700.
　炭素繊維は、少ない添加量でも樹脂部材の熱伝導率を高めやすい観点から、好ましくは３００Ｗ／ｍＫ以上、より好ましくは４００Ｗ／ｍＫ以上、更に好ましくは５００Ｗ／ｍＫ以上の熱伝導率を有する。炭素繊維の熱伝導率に上限はなく、炭素繊維の熱伝導率が高いほど樹脂部材の熱伝導率も高めることができる。 The carbon fiber has a thermal conductivity of preferably 300 W / mK or more, more preferably 400 W / mK or more, and still more preferably 500 W / mK or more, from the viewpoint of easily increasing the thermal conductivity of the resin member even with a small addition amount. There is no upper limit to the thermal conductivity of the carbon fiber, and the thermal conductivity of the resin member can be increased as the thermal conductivity of the carbon fiber is higher.
　（Ｃ）成分の含有量は、樹脂部材の熱伝導率を更に高められる観点から、樹脂部材全量基準で、好ましくは１５質量％以上、より好ましくは１８質量％以上、更に好ましくは２０質量％以上である。（Ｃ）成分の含有量は、融解熱をできるだけ高く維持する観点から、樹脂部材全量基準で、好ましくは５０質量％以下、より好ましくは４０質量％以下、更に好ましくは３０質量％以下である。 The content of the component (C) is preferably 15% by mass or more, more preferably 18% by mass or more, still more preferably 20% by mass or more, based on the total amount of the resin member, from the viewpoint of further enhancing the thermal conductivity of the resin member. It is. The content of the component (C) is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, based on the total amount of resin members, from the viewpoint of maintaining the heat of fusion as high as possible.
　樹脂部材１は、ゲル化剤（以下、「（Ｄ）成分」ともいう）を更に含んでいてもよい。（Ｄ）成分は、（Ｂ）成分をゲル化し得る成分であれば特に制限されない。（Ｄ）成分は、例えば、カルボン酸及びカルボン酸金属塩からなる群より選ばれる少なくとも１種であってよい。すなわち、樹脂部材１は、一実施形態において、エチレンと炭素数が３以上のオレフィンとの共重合体と、飽和炭化水素化合物と、炭素繊維と、カルボン酸及びカルボン酸金属塩からなる群より選ばれる少なくとも１種とを含む。 The resin member 1 may further contain a gelling agent (hereinafter, also referred to as “component (D)”). The component (D) is not particularly limited as long as it is a component capable of gelling the component (B). The component (D) may be, for example, at least one selected from the group consisting of carboxylic acids and carboxylic acid metal salts. That is, in one embodiment, the resin member 1 is selected from the group consisting of a copolymer of ethylene and an olefin having 3 or more carbon atoms, a saturated hydrocarbon compound, a carbon fiber, a carboxylic acid and a carboxylic acid metal salt. And at least one of the
　カルボン酸は、飽和炭化水素化合物との相性が良い観点から、好ましくは鎖状の脂肪族カルボン酸である。カルボン酸の炭素数は、好ましくは１０以上であり、例えば１０～４０、１０～３０又は１０～２５である。カルボン酸は、飽和であっても不飽和であってもよい。カルボン酸としては、特に限定されないが、例えば、ラウリン酸（Ｃ１２（炭素数、以下同様））、ミリスチン酸（Ｃ１４）、パルミチン酸（Ｃ１６）、ステアリン酸（Ｃ１８）、イソステアリン酸（Ｃ１８）、ドコサヘキサエン酸（Ｃ２２）、ベヘニン酸（Ｃ２１）、ウンデシレン酸（Ｃ１１）、オレイン酸（Ｃ１８）、エルカ酸（Ｃ２２）、リノール酸（Ｃ１８）、アラキドン酸（Ｃ２０）、リノレン酸（Ｃ１８）、サピエン酸（Ｃ１６）等が挙げられる。カルボン酸は、１種単独、あるいは２種以上を組み合わせて用いられてよい。 The carboxylic acid is preferably a chain aliphatic carboxylic acid from the viewpoint of good compatibility with the saturated hydrocarbon compound. The carbon number of the carboxylic acid is preferably 10 or more, and for example, 10 to 40, 10 to 30, or 10 to 25. The carboxylic acids may be saturated or unsaturated. The carboxylic acid is not particularly limited. For example, lauric acid (C12 (carbon number, the same applies hereinafter)), myristic acid (C14), palmitic acid (C16), stearic acid (C18), isostearic acid (C18), docosahexaene Acid (C22), behenic acid (C21), undecylenic acid (C11), oleic acid (C18), erucic acid (C22), linoleic acid (C18), arachidonic acid (C20), linolenic acid (C18), sapienic acid (C18) C16) and the like. The carboxylic acids may be used alone or in combination of two or more.
　カルボン酸金属塩を構成するカルボン酸は、飽和炭化水素化合物との相性（カルボン酸を併用する場合はカルボン酸との相性）が良い観点から、好ましくは鎖状の脂肪族カルボン酸である。カルボン酸金属塩を構成するカルボン酸の炭素数は、好ましくは６以上であり、例えば６～３０、６～２５又は８～２０である。カルボン酸金属塩を構成するカルボン酸は、飽和であっても不飽和であってもよい。カルボン酸金属塩を構成する金属は、カルボン酸と塩を形成できる金属であり、例えばアルミニウムである。具体的なカルボン酸金属塩としては、ステアリン酸アルミニウム（Ｃ１８（炭素数、以下同様。））、ラウリン酸アルミニウム（Ｃ１２）、オレイン酸アルミニウム（Ｃ１８）、ベヘニン酸アルミニウム（Ｃ２１）、パルミチン酸アルミニウム（Ｃ１６）、２－エチルヘキサン酸アルミニウム（Ｃ８）等が挙げられる。カルボン酸金属塩は、１種単独、あるいは２種以上を組み合わせて使用されてよい。 The carboxylic acid constituting the carboxylic acid metal salt is preferably a chain aliphatic carboxylic acid from the viewpoint of good compatibility with the saturated hydrocarbon compound (compatibility with the carboxylic acid when using the carboxylic acid in combination). The carbon number of the carboxylic acid constituting the carboxylic acid metal salt is preferably 6 or more, and for example, 6 to 30, 6 to 25 or 8 to 20. The carboxylic acid which comprises carboxylic acid metal salt may be saturated or unsaturated. The metal which comprises carboxylic acid metal salt is a metal which can form a salt with carboxylic acid, for example, is aluminum. Specific examples of carboxylic acid metal salts include aluminum stearate (C18 (number of carbon atoms, the same applies hereinafter)), aluminum laurate (C12), aluminum oleate (C18), aluminum behenate (C21), and aluminum palmitate ( C16), aluminum 2-ethylhexanoate (C8) and the like. The carboxylic acid metal salts may be used alone or in combination of two or more.
　（Ｄ）成分の含有量は、樹脂部材全量基準で、３質量％以上であってよく、また、１０質量％以下、８質量％以下、又は６質量％以下であってよい。 The content of the component (D) may be 3% by mass or more, and 10% by mass or less, 8% by mass or less, or 6% by mass or less, based on the total amount of the resin member.
　樹脂部材１は、融点が１００℃以上であるポリマー（以下、「（Ｅ）成分」ともいう）を更に含んでいてもよい。ただし、（Ｅ）成分は、エチレンと炭素数が３以上のオレフィンとの共重合体（（Ａ）成分）以外の成分である。樹脂部材１が（Ｅ）成分を含むことにより、物理的な相互網目構造体の形成が期待でき、高温（例えば５０℃以上）での流動性抑制及び形状維持の点で更に優れる樹脂部材１が得られる。 The resin member 1 may further contain a polymer having a melting point of 100 ° C. or higher (hereinafter, also referred to as “component (E)”). However, the component (E) is a component other than a copolymer of ethylene and an olefin having 3 or more carbon atoms (component (A)). When the resin member 1 contains the component (E), formation of a physical mutual network structure can be expected, and the resin member 1 is further excellent in terms of flowability suppression and shape maintenance at high temperatures (for example, 50 ° C. or higher). can get.
　（Ｅ）成分の融点は、１００℃以上、１２０℃以上、又は１４０℃以上であってよく、また、２５０℃以下、２３０℃以下、又は２００℃以下であってよい。 The melting point of the component (E) may be 100 ° C. or more, 120 ° C. or more, or 140 ° C. or more, and may be 250 ° C. or less, 230 ° C. or less, or 200 ° C. or less.
　（Ｅ）成分は、上記の（Ａ）成分及び（Ｂ）成分との相溶性がよいことが望ましい。（Ｅ）成分は、例えば、ポリエチレン（エチレン単独重合体）、ポリプロピレン（プロピレン単独重合体）等であってよく、エチレン又はプロピレン以外のモノマー単位を更に含む、ポリエチレン又はポリプロピレンの変性ポリマー、エチレン又はプロピレンとその他のモノマーとのコポリマー（共重合体）等であってもよい。コポリマー（共重合体）は、例えばブロック共重合体であってよい。（Ｅ）成分は、１種単独で用いられてもよく、２種以上を組み合わせて用いられてもよい。 The component (E) desirably has good compatibility with the components (A) and (B) described above. The component (E) may be, for example, polyethylene (ethylene homopolymer), polypropylene (propylene homopolymer), etc., a modified polymer of polyethylene or polypropylene further containing ethylene or monomer units other than propylene, ethylene or propylene It may be a copolymer (copolymer) or the like with one or more other monomers. The copolymer (copolymer) may, for example, be a block copolymer. As the component (E), one type may be used alone, or two or more types may be used in combination.
　（Ｂ）成分の融点が５０℃以上である場合、５０℃以上の温度領域における流動性抑制及び形状維持の点で更に優れる観点から、樹脂部材１は、（Ｅ）成分として、好ましくは、ポリエチレン（エチレン単独重合体）及びポリプロピレン（プロピレン単独重合体）からなる群より選ばれる少なくとも１種を更に含む。 When the melting point of the component (B) is 50 ° C. or higher, the resin member 1 is preferably polyethylene as the component (E) from the viewpoint of further excellent in fluidity suppression and shape maintenance in a temperature range of 50 ° C. or higher. It further includes at least one selected from the group consisting of (ethylene homopolymer) and polypropylene (propylene homopolymer).
　（Ｅ）成分の含有量は、樹脂部材全量基準で、５質量％以上であってよく、また、３０質量％以下、２５質量％以下、又は２０質量％以下であってよい。 The content of the component (E) may be 5% by mass or more, 30% by mass or less, 25% by mass or less, or 20% by mass or less, based on the total amount of the resin member.
　樹脂部材１は、上記（Ａ）～（Ｅ）成分に加えて、その他の成分を更に含んでいてもよい。その他の成分としては、上述の炭素繊維以外の炭素材料（例えば黒鉛）、金属繊維、ガラス、タルク等の無機成分、光劣化を抑制する光吸収剤などが挙げられる。その他の成分の含有量は、樹脂部材全量基準で、例えば１０質量％以下であってよい。 The resin member 1 may further contain other components in addition to the components (A) to (E). Examples of the other components include carbon materials (for example, graphite) other than the above-mentioned carbon fibers, metal fibers, glass, inorganic components such as talc, light absorbers that suppress photodegradation, and the like. The content of the other components may be, for example, 10% by mass or less based on the total amount of the resin member.
　以上説明した樹脂部材１は、例えば以下の方法により得られる。すなわち、飽和炭化水素化合物（（Ｂ）成分）を融点以上に加温した状態で、エチレンと炭素数が３以上のオレフィンとの共重合体（（Ａ）成分）と、必要に応じて融点が１００℃以上であるポリマー（（Ｅ）成分）とを加え均一に混合する。その後、必要に応じてカルボン酸及びカルボン酸金属塩からなる群より選ばれる少なくとも１種（（Ｄ）成分）を添加して、更に均一混合する。続いて、炭素繊維（（Ｃ）成分）を加えて、加圧加熱プレスで混練することにより樹脂部材を得る。この樹脂部材を加熱溶融して成形することにより、シート状の樹脂部材１を得ることもできる。すなわち、樹脂部材１の製造方法は、（Ａ）～（Ｃ）成分と、必要に応じて（Ｄ）成分、（Ｅ）成分及びその他の成分とを含有する組成物を加熱溶融して成形する工程（成形工程）を備えている。成形工程における成形は、射出成形、圧縮成形又はトランスファー成形であってよい。 The resin member 1 described above is obtained, for example, by the following method. That is, in the state where the saturated hydrocarbon compound (component (B)) is heated to the melting point or higher, a copolymer of ethylene and an olefin having 3 or more carbon atoms (component (A)) and, if necessary, a melting point Add the polymer (component (E)) at 100 ° C. or higher and mix uniformly. Thereafter, at least one member (component (D)) selected from the group consisting of carboxylic acids and carboxylic acid metal salts is added, if necessary, and homogeneous mixing is further performed. Subsequently, a carbon fiber (component (C)) is added and the mixture is kneaded by a pressure heating press to obtain a resin member. The sheet-like resin member 1 can also be obtained by heating and melting this resin member and molding it. That is, in the method for producing the resin member 1, the composition containing the components (A) to (C) and, if necessary, the components (D), (E) and other components is heat-melted and molded. A process (molding process) is provided. Molding in the molding process may be injection molding, compression molding or transfer molding.
　本発明の他の一実施形態は、樹脂部材１からなる樹脂層を備えるシートである。当該シートは、樹脂層のみからなるシートであってよく、例えば、樹脂層と金属層とが積層されたシートであってよい。 Another embodiment of the present invention is a sheet provided with a resin layer made of the resin member 1. The said sheet | seat may be a sheet | seat which consists only of a resin layer, for example, may be a sheet | seat on which the resin layer and the metal layer were laminated | stacked.
　樹脂層の厚さは、例えば、１～３０ｍｍ、２～２０ｍｍ、又は５～１０ｍｍであってよい。金属層の厚さは、例えば１００μｍ以下であってよい。 The thickness of the resin layer may be, for example, 1 to 30 mm, 2 to 20 mm, or 5 to 10 mm. The thickness of the metal layer may be, for example, 100 μm or less.
　樹脂層は、高い熱伝導率を有している。樹脂層の熱伝導率は、好ましくは、１Ｗ／ｍＫ以上、１．１Ｗ／ｍＫ以上、又は１．２Ｗ／ｍＫ以上であってよい。樹脂層の熱伝導率は、熱伝導率計（例えば、京都電子工業（株）製「ＱＴＭ－５００」）を用いて測定される。 The resin layer has high thermal conductivity. The thermal conductivity of the resin layer may be preferably 1 W / mK or more, 1.1 W / mK or more, or 1.2 W / mK or more. The thermal conductivity of the resin layer is measured using a thermal conductivity meter (for example, "QTM-500" manufactured by Kyoto Denshi Kogyo Co., Ltd.).
　樹脂層は、高い蓄熱容量（融解熱）を有している。樹脂層の融解熱は、好ましくは、９０Ｊ／ｇ以上、９５Ｊ／ｇ以上、又は１００Ｊ／ｇ以上であってよい。樹脂層の融解熱は、示差走査熱量計（例えば、（株）パーキンエルマー製「８５００」）を用いて、昇温速度１０℃／分で加熱したときに得られたサーモグラムの融解（吸熱）ピークの面積から算出される。 The resin layer has a high heat storage capacity (heat of fusion). The heat of fusion of the resin layer may be preferably 90 J / g or more, 95 J / g or more, or 100 J / g or more. The heat of fusion of the resin layer is the melting of the thermogram obtained when heated at a temperature rising rate of 10 ° C./min using a differential scanning calorimeter (for example, “8500” manufactured by PerkinElmer Co., Ltd.) (endothermic) Calculated from the area of the peak.
　樹脂部材１及びそれを用いたシートは、相転移を利用して蓄熱又は放熱することが可能であるため、蓄熱材として好適に用いられる。つまり、本発明の他の一実施形態は、上述の樹脂部材１を備える蓄熱材である。 The resin member 1 and the sheet using the same can be suitably used as a heat storage material because it is possible to store or release heat using phase transition. That is, another embodiment of the present invention is a heat storage material provided with the above-mentioned resin member 1.
　本実施形態の蓄熱材（樹脂部材、シート）は様々な分野に活用されうる。蓄熱材（樹脂部材、シート）は、例えば、自動車、建築物、公共施設、地下街等における空調設備（空調設備の効率向上）、工場等における配管（配管の蓄熱）、自動車のエンジン（当該エンジン周囲の保温）、電子部品（電子部品の昇温防止）、下着の繊維などに用いられる。蓄熱材（樹脂部材、シート）は、（Ｂ）成分の融点以上でも、（Ｂ）成分の流動性の上昇及びそれに伴う滲みだしの発生を抑制できるため、取り付ける対象物に貼り付けられたり、巻き付けられたり、様々な状態で取り付けられることが可能である。 The heat storage material (resin member, sheet) of the present embodiment can be used in various fields. Thermal storage materials (resin members, sheets) are, for example, air conditioners (improve the efficiency of air conditioners) in automobiles, buildings, public facilities, underground malls, etc., pipes (heat storage in pipes) in factories etc, engine of automobile (around the engine Heat insulation), electronic parts (preventing temperature rise of electronic parts), fibers of underwear, etc. The heat storage material (resin member, sheet) can be stuck to the object to be attached or wound because it can suppress the increase in the fluidity of the component (B) and the generation of bleeding associated therewith even above the melting point of the component (B). It can be installed in various ways.
　本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 The present invention will be specifically described based on examples, but the present invention is not limited to these examples.
＜実施例１～７＞
　以下に示すエチレンと炭素数が３以上のオレフィンとの共重合体、鎖状の飽和炭化水素化合物、炭素繊維、並びにカルボン酸及びカルボン酸金属塩を用いて、表１に示す組成の樹脂部材を作製した。具体的には、飽和炭化水素化合物を融点以上に加温した状態で、エチレンと炭素数が３以上のオレフィンとの共重合体を加えて均一に混合した。その後、カルボン酸及びカルボン酸金属塩を添加して、更に均一に混合した。続いて、炭素繊維を加えて、加圧加熱プレス（上板８０℃／下板４０℃、加圧１４０ｋＰａ）で混練することにより樹脂部材を得た。得られた樹脂部材を加圧加熱プレス（上下熱板８０℃、加圧１ＭＰａ）することにより、１７０×６０×１ｍｍのシート状の樹脂部材を得た。 Examples 1 to 7
A resin member having a composition shown in Table 1 using a copolymer of ethylene and an olefin having 3 or more carbon atoms, a chain-like saturated hydrocarbon compound, a carbon fiber, and a carboxylic acid and a carboxylic acid metal salt shown below Made. Specifically, in the state where the saturated hydrocarbon compound was heated to the melting point or higher, a copolymer of ethylene and an olefin having 3 or more carbon atoms was added and uniformly mixed. Thereafter, carboxylic acid and carboxylic acid metal salt were added and mixed more uniformly. Subsequently, carbon fibers were added, and the mixture was kneaded by a pressure heating press (upper plate 80 ° C./lower plate 40 ° C., pressure 140 kPa) to obtain a resin member. The obtained resin member was subjected to pressure heating press (upper and lower heat plates 80 ° C., pressure 1 MPa) to obtain a sheet-like resin member of 170 × 60 × 1 mm.
（エチレンと炭素数が３以上のオレフィンとの共重合体）
Ａ－１：エチレンとオクテンとの共重合体（ダウ・ケミカル日本（株）製、製品名「ＥＮＧＡＧＥ８１５０」）
（鎖状飽和炭化水素化合物）
Ｂ－１：ｎ－ヘキサデカン（融点：１８℃）
（炭素繊維）
Ｃ－１：ＧＲＡＮＯＣ　ＸＮ－９０Ｃ－０６Ｓ（日本グラファイトファイバー（株）製、アスペクト比６００（繊維径１０μｍ、繊維長６ｍｍ）、熱伝導率５００Ｗ／ｍＫ）
Ｃ－２：ラヒーマ　Ｒ－Ａ３０１（帝人（株）製、アスペクト比２５（繊維径８μｍ、繊維長０．２ｍｍ）、熱伝導率５５０Ｗ／ｍＫ）
Ｃ－３：ドナカーボ　Ｓ２０１（大阪ガスケミカル（株）製、アスペクト比８３３（繊維径１８μｍ、繊維長１５ｍｍ程度に切断して使用）、熱伝導率３Ｗ／ｍＫ）
Ｃ－４：ＧＲＡＮＯＣ　ＸＮ－１００－０３Ｚ（日本グラファイトファイバー（株）製、アスペクト比３００（繊維径１０μｍ、繊維長３ｍｍ）、熱伝導率９００Ｗ／ｍＫ）
Ｃ－５：ＧＲＡＮＯＣ　ＸＮ－１００－０６Ｚ（日本グラファイトファイバー（株）製、アスペクト比６００（繊維径１０μｍ、繊維長６ｍｍ）、熱伝導率９００Ｗ／ｍＫ）
（カルボン酸又はカルボン酸金属塩）
Ｄ－１：２－エチルヘキサン酸アルミニウム
Ｄ－２：オレイン酸 (Copolymer of ethylene and olefin having 3 or more carbon atoms)
A-1: Copolymer of ethylene and octene (Dow Chemical Japan Ltd., product name "ENGAGE 8150")
(Chain-like saturated hydrocarbon compound)
B-1: n-hexadecane (melting point: 18 ° C.)
(Carbon fiber)
C-1: GRANOC XN-90C-06S (manufactured by Nippon Graphite Fiber Co., Ltd., aspect ratio 600 (fiber diameter 10 μm, fiber length 6 mm), thermal conductivity 500 W / mK)
C-2: Lahema R-A301 (manufactured by Teijin Limited, aspect ratio 25 (fiber diameter 8 μm, fiber length 0.2 mm), thermal conductivity 550 W / m K)
C-3: Dona Carbo S201 (Osaka Gas Chemical Co., Ltd., aspect ratio 833 (fiber diameter: 18 μm, fiber length: about 15 mm), thermal conductivity: 3 W / m K)
C-4: GRANOC XN-100-03Z (manufactured by Nippon Graphite Fiber Co., Ltd., aspect ratio 300 (fiber diameter 10 μm, fiber length 3 mm), thermal conductivity 900 W / mK)
C-5: GRANOC XN-100-06Z (manufactured by Nippon Graphite Fiber Co., Ltd., aspect ratio 600 (fiber diameter 10 μm, fiber length 6 mm), thermal conductivity 900 W / mK)
(Carboxylic acid or carboxylic acid metal salt)
D-1: 2-Aluminum Ethyl Hexanoic Acid D-2: Oleic Acid
　飽和炭化水素化合物の融点は、示差熱分析（ＤＳＣ）により、昇温速度１０℃／分の昇温過程における融解のピーク温度から算出した。 The melting point of the saturated hydrocarbon compound was calculated by differential thermal analysis (DSC) from the peak temperature of melting in the heating process at a heating rate of 10 ° C./min.
＜比較例１＞
　炭素繊維に代えて下記の炭素材料Ｃ－６を用いた以外は、実施例１と同様にして樹脂部材を得た。
Ｃ－６：微粉黒鉛（昭和電工（株）製、アスペクト比２０未満、微粉径７μｍ以下） Comparative Example 1
A resin member was obtained in the same manner as Example 1, except that the following carbon material C-6 was used instead of the carbon fiber.
C-6: Fine powder graphite (manufactured by Showa Denko KK, aspect ratio less than 20, fine powder diameter 7 μm or less)
＜比較例２＞
　炭素繊維を用いなかった以外は、実施例１と同様にして樹脂部材を得た。 Comparative Example 2
A resin member was obtained in the same manner as Example 1, except that carbon fiber was not used.
　各実施例及び比較例のシート状の樹脂部材について、以下に示す各評価を行った。結果を表１に示す。 Each evaluation shown below was performed about the sheet-like resin member of each Example and a comparative example. The results are shown in Table 1.
（滲みだしの評価）
　各樹脂部材の融点付近において、液体の滲みだしの有無を目視及び触感で判断した。 (Evaluation of bleeding)
In the vicinity of the melting point of each resin member, the presence or absence of the bleeding of the liquid was judged visually and by touch.
（熱伝導率の測定）
　ＱＴＭ－５００（京都電子工業（株）製）を用い、また、プローブとしてＰＤ－１１Ｎを用いて、シート面内の熱伝導率を測定した。 (Measurement of thermal conductivity)
The thermal conductivity in the sheet surface was measured using QTM-500 (manufactured by Kyoto Denshi Kogyo Co., Ltd.) and using PD-11N as a probe.
（融点、融解熱、凝固点及び凝固熱の測定）
　ＤＳＣ－８５００（（株）パーキンエルマー製）を用いて、１０℃／分の昇温過程における融解のピーク温度及び凝固のピーク温度から融点及び凝固点をそれぞれ求め、それぞれの面積から融解熱及び凝固熱を算出した。なお、融解熱が大きいほど蓄熱容量が大きいことを意味する。 (Measurement of melting point, heat of fusion, freezing point and heat of solidification)
Using DSC-8500 (manufactured by PerkinElmer Co., Ltd.), determine the melting point and the freezing point from the peak temperature of melting and the peak temperature of solidification in a temperature rising process of 10 ° C./min. Was calculated. The larger the heat of fusion, the larger the heat storage capacity.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　１…樹脂部材。 1 ... resin member.

Claims (14)

  1. 　エチレンと炭素数が３以上のオレフィンとの共重合体と、
    　飽和炭化水素化合物と、
    　炭素繊維と、
    を含む樹脂部材。     A copolymer of ethylene and an olefin having 3 or more carbon atoms,
    A saturated hydrocarbon compound,
    Carbon fiber,
    Resin member containing.
  2. 　前記炭素繊維の熱伝導率が３００Ｗ／ｍＫ以上である、請求項１に記載の樹脂部材。 The resin member according to claim 1, wherein the thermal conductivity of the carbon fiber is 300 W / mK or more.
  3. 　前記オレフィンの炭素数が３～８である、請求項１又は２に記載の樹脂部材。 The resin member according to claim 1 or 2, wherein the olefin has 3 to 8 carbon atoms.
  4. 　前記飽和炭化水素化合物の融点が５０℃未満であり、前記オレフィンの炭素数が８である、請求項１～３のいずれか一項に記載の樹脂部材。 The resin member according to any one of claims 1 to 3, wherein the melting point of the saturated hydrocarbon compound is less than 50 属 C, and the carbon number of the olefin is 8.
  5. 　前記炭素繊維のアスペクト比が１００～１０００である、請求項１～４のいずれか一項に記載の樹脂部材。 The resin member according to any one of claims 1 to 4, wherein the aspect ratio of the carbon fiber is 100 to 1000.
  6. 　前記炭素繊維の含有量が、前記樹脂部材全量基準で１５質量％以上である、請求項１～５のいずれか一項に記載の樹脂部材。 The resin member according to any one of claims 1 to 5, wherein the content of the carbon fiber is 15% by mass or more based on the total amount of the resin member.
  7. 　ゲル化剤を更に含む、請求項１～６のいずれか一項に記載の樹脂部材。 The resin member according to any one of claims 1 to 6, further comprising a gelling agent.
  8. 　カルボン酸及びカルボン酸金属塩からなる群より選ばれる少なくとも１種を更に含む、請求項１～６のいずれか一項に記載の樹脂部材。 The resin member according to any one of claims 1 to 6, further comprising at least one selected from the group consisting of carboxylic acids and carboxylic acid metal salts.
  9. 　請求項１～８のいずれか一項に記載の樹脂部材からなる樹脂層を備える、シート。 A sheet comprising a resin layer comprising the resin member according to any one of claims 1 to 8.
  10. 　前記樹脂層の熱伝導率が１Ｗ／ｍＫ以上である、請求項９に記載のシート。 The sheet according to claim 9, wherein the thermal conductivity of the resin layer is 1 W / mK or more.
  11. 　前記樹脂層の融解熱が９０Ｊ／ｇ以上である、請求項９又は１０に記載のシート。 The sheet according to claim 9, wherein a heat of fusion of the resin layer is 90 J / g or more.
  12. 　請求項１～８のいずれか一項に記載の樹脂部材を備える、蓄熱材。 A heat storage material comprising the resin member according to any one of claims 1 to 8.
  13. 　エチレンと炭素数が３以上のオレフィンとの共重合体と、飽和炭化水素化合物と、炭素繊維と、を含む組成物を加熱溶融して成形する工程を備える、樹脂部材の製造方法。 A method for producing a resin member, comprising the step of heating and melting a composition containing a copolymer of ethylene and an olefin having 3 or more carbon atoms, a saturated hydrocarbon compound, and carbon fibers.
  14. 　前記工程において、射出成形、圧縮成形又はトランスファー成形により前記組成物を成形する、請求項１３に記載の樹脂部材の製造方法。 The method for producing a resin member according to claim 13, wherein the composition is formed by injection molding, compression molding or transfer molding in the step.
PCT/JP2017/043848 2017-12-06 2017-12-06 Resinous member, sheet, heat-storage material, and production method for resinous member WO2019111358A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021241432A1 (en) * 2020-05-29 2021-12-02 住友化学株式会社 Heat storage composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006316194A (en) * 2005-05-13 2006-11-24 Hasec:Kk Heat storage material
JP2015054918A (en) * 2013-09-12 2015-03-23 Jsr株式会社 Composition for heat storage material
WO2017073010A1 (en) * 2015-10-27 2017-05-04 ソニー株式会社 Electronic apparatus
JP2017095529A (en) * 2015-11-18 2017-06-01 三菱樹脂インフラテック株式会社 Paraffin-based composition and heat storage material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006316194A (en) * 2005-05-13 2006-11-24 Hasec:Kk Heat storage material
JP2015054918A (en) * 2013-09-12 2015-03-23 Jsr株式会社 Composition for heat storage material
WO2017073010A1 (en) * 2015-10-27 2017-05-04 ソニー株式会社 Electronic apparatus
JP2017095529A (en) * 2015-11-18 2017-06-01 三菱樹脂インフラテック株式会社 Paraffin-based composition and heat storage material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021241432A1 (en) * 2020-05-29 2021-12-02 住友化学株式会社 Heat storage composition

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