Thermally conductive composition

Abstract

The present invention provides a thermally conductive composition which contains a matrix resin, a filler and an olefin wax. The olefin wax has a weight average molecular weight of 25,000 or less. The content ratio of the olefin wax relative to the total amount of the matrix resin, the filler and the olefin wax is more than 1% by mass.

Description

[Technical field]

[0001] The present invention relates to a thermally conductive composition and a thermally conductive filler composite. [Background technology]

[0002] Conventionally, in the field of heat dissipation materials, a thermally conductive composition containing a thermally conductive filler and a molded article thereof have been used. More specifically, the following resin compositions are known as thermally conductive compositions.

[0003] That is, this resin composition contains a conductive nanofiller (thermally conductive filler) (A), an olefin polymer (B), another resin (C), and a compound having a functional group (D). This resin composition also has a dispersed phase formed by the olefin polymer (B) and a continuous phase formed by the other resin (C). The conductive nanofiller (thermally conductive filler) (A) is unevenly distributed in the dispersed phase (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2011-195756 A Summary of the Invention [Problem to be solved by the invention]

[0005] On the other hand, molded articles of thermally conductive compositions are required to have even better thermal conductivity and also to have excellent appearance.

[0006] The present invention relates to a thermally conductive composition and a thermally conductive filler composite that can give molded articles having excellent thermal conductivity and appearance. [Means for solving the problem]

[0007] The present invention [1] is a thermally conductive composition comprising a matrix resin, a filler, and an olefin wax, wherein the weight average molecular weight of the olefin wax is 25,000 or less, and the content of the olefin wax exceeds 1 mass% relative to the total amount of the matrix resin, the filler, and the olefin wax.

[0008] The present invention [2] includes the thermally conductive composition according to the above [1], in which the olefin wax is not acid-modified.

[0009] The present invention [3] includes the thermally conductive composition according to the above [2], in which the matrix resin includes polyamide and the filler includes aluminum oxide.

[0010] The present invention [4] comprises the thermally conductive composition according to any one of the above [1] to [3], wherein the content of the olefin wax is 3 mass% or more and 5 mass% or less with respect to the total amount of the matrix resin, the filler, and the olefin wax.

[0011] The present invention [5] includes a thermally conductive filler complex comprising a filler and an olefin wax coating the filler, the olefin wax having a weight average molecular weight of 25,000 or less. Effect of the Invention

[0012] The thermally conductive composition of the present invention contains a matrix resin, a filler, and an olefin wax. The weight average molecular weight of the olefin wax is smaller than a predetermined value, and the content of the olefin wax is within a predetermined range.

[0013] Therefore, in the thermally conductive composition of the present invention, the olefin wax improves the dispersibility of the filler in the matrix resin, and as a result, the thermally conductive composition provides a molded product with excellent thermal conductivity.

[0014] The olefin wax also acts as a processing aid, so that the thermally conductive composition can provide molded products with excellent appearance.

[0015] The thermally conductive filler composite of the present invention contains a filler and an olefin wax that coats the filler and has a predetermined weight average molecular weight, and therefore, the thermally conductive filler composite can provide a molded product with excellent thermal conductivity and appearance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The thermally conductive composition contains a matrix resin, a filler, and an olefin wax. Preferably, the thermally conductive composition comprises a matrix resin, a filler, an olefin wax, and additives (described later) that are added as needed.

[0017] The matrix resin is not particularly limited, and examples thereof include thermosetting resins and / or thermoplastic resins (excluding olefin wax, which will be described later). Examples of thermosetting resins include phenolic resins, epoxy resins, melamine resins, urea resins, thermosetting polyurethane resins, and thermosetting polyimide resins. Examples of thermoplastic resins include engineering plastics. Examples of engineering plastics include polyamide, polyacetal, polybutylene terephthalate, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, modified polyphenylene ether, ultra-high molecular weight polyethylene, and liquid crystal polymers. Examples of thermoplastic resins include, in addition to the above, acrylic resins, polyolefin resins, cyclic polyolefin resins, polyester resins, polycarbonate resins, polystyrene resins, polyamide resins, polyimide resins, acetate resins, thermoplastic polyurethane resins, and thermoplastic polyimide resins. These matrix resins can be used alone or in combination of two or more types. As the matrix resin, preferably, a thermoplastic resin is used, more preferably, an engineering plastic is used, further preferably, polyamide, polybutylene terephthalate and polycarbonate are used, and particularly preferably, polyamide is used.

[0018] From the viewpoint of molding processability, the melting temperature (softening temperature) of the matrix resin is, for example, 50° C. or more, or preferably 100° C. or more. The melting temperature (softening temperature) of the matrix resin is, for example, 500° C. or less, or preferably 300° C. or less.

[0019] The density of the matrix resin is, for example, greater than the density of the olefin wax described below, and is, for example, 1000 kg / m 3 More than 1050 kg / m 3 More preferably, 1100 kg / m 3 The density of the matrix resin is, for example, 1500 kg / m 3 Less than or equal to 1300 kg / m3 Less than or equal to 1200 kg / m 3 The following is the result.

[0020] From the viewpoints of thermal conductivity and appearance, the content of the matrix resin is, for example, 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, based on the total amount of the matrix resin, the filler, and the olefin wax. From the viewpoints of thermal conductivity and appearance, the content of the matrix resin is, for example, 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably less than 50% by mass, based on the total amount of the matrix resin, the filler, and the olefin wax.

[0021] Examples of the filler include known thermally conductive materials. More specifically, examples of the filler include metals, metal oxides, metal nitrides, and metal fluorides. Examples of the metal include boron, silicon, aluminum, nickel, iron, gold, silver, copper, platinum, tungsten, chromium, titanium, tin, lead, and palladium. Examples of the metal oxide include aluminum oxide (alumina), silicon oxide, magnesium oxide, titanium dioxide, beryllium oxide, and tin oxide. Examples of the metal nitride include boron nitride, aluminum nitride, and silicon nitride. Examples of the metal fluoride include aluminum fluoride and calcium fluoride. Examples of the filler include silicon carbide, hydroxyapatite, barium titanate, and silicon carbide, in addition to the above. Examples of the filler include fillers plated (surface-coated) with the above metals.

[0022] Further, the filler may be, for example, a soft magnetic filler.The soft magnetic filler may be, for example, a magnetic stainless steel (Fe-Cr-Al-Si alloy), a sendust (Fe-Si-Al alloy), a permalloy (Fe-Ni alloy), a silicon copper (Fe-Cu-Si alloy), a Fe-Si alloy, a Fe-Si-B alloy, a Fe-Si-B-Cu-Nb alloy, a Fe-Ni-Cr-Si alloy, a Fe-Si-Cr alloy, and a Fe-Si-Al-Ni-Cr alloy.

[0023] These fillers can be used alone or in combination of two or more kinds. From the viewpoints of thermal conductivity, electrical insulation, and chemical stability, the filler is preferably a metal oxide, a metal nitride, or a metal fluoride, more preferably a metal oxide or a metal nitride, further preferably aluminum oxide or boron nitride, and particularly preferably aluminum oxide.

[0024] The electrical conductivity of the filler is preferably relatively low, for example, 1 μS / cm or more, preferably 5 μS / cm or more, and the electrical conductivity of the filler is preferably relatively low, for example, 100 μS / cm or less.

[0025] The size of the filler is not particularly limited and is appropriately set according to the purpose and use.For example, the average particle size (average secondary particle size, median size) of the filler is, for example, 0.1 μm or more, preferably 1 μm or more.In addition, the average particle size (average secondary particle size, median size) of the filler is, for example, 100 μm or less, preferably 50 μm or less, more preferably 20 μm or less.

[0026] If the BET specific surface area of ​​the filler is, for example, 0.1 m 2 / g or more, preferably 0.2m 2 / g or more. In addition, the BET specific surface area of ​​the filler is, for example, 5 m 2 / g or less, preferably 1m 2 / g or less.

[0027] From the viewpoints of thermal conductivity and appearance, the content of the filler is, for example, 20% by mass or more, preferably 40% by mass or more, based on the total amount of the matrix resin, the filler, and the olefin wax. From the viewpoints of thermal conductivity and appearance, the content of the filler is, for example, 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, based on the total amount of the matrix resin, the filler, and the olefin wax.

[0028] The filler content may be less than the matrix resin content, but is preferably greater than the matrix resin content. More specifically, the filler content is, for example, 50 parts by mass or more, preferably 100 parts by mass or more, more preferably 110 parts by mass or more, relative to 100 parts by mass of the matrix resin. The filler content is, for example, 200 parts by mass or less, preferably 150 parts by mass or less, relative to 100 parts by mass of the matrix resin.

[0029] The olefin wax is a dispersant for dispersing the filler in the matrix resin. For example, the olefin wax may be an α-olefin polymer. That is, the olefin wax may contain an α-olefin polymer. The polymer may be a homopolymer and / or a copolymer.

[0030] Examples of the α-olefin include α-olefins having 2 to 13 carbon atoms. More specifically, examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene. These can be used alone or in combination of two or more. Examples of the α-olefin include preferably ethylene, propylene, and 1-butene, more preferably ethylene and propylene, and even more preferably ethylene.

[0031] That is, the α-olefin polymer preferably contains structural units derived from ethylene. The content ratio of structural units derived from ethylene (C2 content) is, for example, 1 mol% or more, preferably 10 mol% or more, more preferably 50 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more, based on the total amount of structural units derived from α-olefin. The content ratio of structural units derived from ethylene (C2 content) is, for example, 100 mol% or less, preferably 98 mol% or less, based on the total amount of structural units derived from α-olefin. The content ratio of structural units derived from ethylene (C2 content) is, for example, 100 mol% or less, preferably 98 mol% or less, based on the total amount of structural units derived from α-olefin, based on the examples described later. 13 It can be determined by C-NMR.

[0032] The polymerization method of α-olefin is not particularly limited, and a known method is adopted. For example, α-olefin is polymerized by Ziegler-Natta catalyst and / or metallocene catalyst. The polymerization conditions are not particularly limited, but are adjusted so that the weight average molecular weight of the olefin wax falls within the range described below.

[0033] The α-olefin polymer may be modified by a known method as necessary. Examples of the modification include acid modification and aromatic ring modification. In other words, the olefin wax includes modified α-olefin polymers, more specifically, acid modified α-olefin polymers and / or aromatic ring modified α-olefin polymers.

[0034] That is, the olefin wax may contain an acid-modified product of an α-olefin polymer, and may also contain an aromatic ring-modified product of an α-olefin polymer.

[0035] Examples of acid-modified α-olefin polymers include copolymers of α-olefins and unsaturated carboxylic acids. Examples of unsaturated carboxylic acids include unsaturated monocarboxylic acids and unsaturated polycarboxylic acids. Examples of unsaturated monocarboxylic acids include unsaturated monocarboxylic acids having 3 to 30 carbon atoms. Specific examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, isocrotonic acid, and cyclohexene carboxylic acid. Examples of unsaturated polycarboxylic acids include unsaturated dicarboxylic acids having 3 to 30 carbon atoms. Specific examples of unsaturated polycarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, cyclohexene dicarboxylic acid, cycloheptene dicarboxylic acid, bicycloheptene dicarboxylic acid, methyltetrahydrophthalic acid, and acid anhydrides thereof. The unsaturated carboxylic acids can be used alone or in combination of two or more kinds. As the unsaturated carboxylic acid, preferably, an unsaturated polycarboxylic acid is used, more preferably, an unsaturated dicarboxylic acid is used, further preferably, maleic acid and its acid anhydride are used, and particularly preferably, maleic anhydride is used.

[0036] Examples of the copolymer of an α-olefin and an unsaturated carboxylic acid include a block copolymer, a random copolymer, and a graft copolymer. These can be used alone or in combination of two or more kinds.

[0037] The method for copolymerizing the α-olefin and the unsaturated carboxylic acid is not particularly limited, and a known method can be used. The ratio of the α-olefin and the unsaturated carboxylic acid is appropriately set depending on the purpose and application.

[0038] Examples of aromatic ring modified polymers of α-olefins include copolymers of α-olefins and aromatic ring-containing unsaturated monomers. Examples of aromatic ring-containing unsaturated monomers include styrene-based monomers, pyridine-based monomers, and quinoline-based monomers. Examples of styrene-based monomers include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-chlorostyrene, m-chlorostyrene, and p-chloromethylstyrene. Examples of pyridine-based monomers include 4-vinylpyridine, 2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, and 2-isopropenylpyridine. Examples of quinoline-based monomers include 2-vinylquinoline and 3-vinylisoquinoline. Examples of aromatic ring unsaturated monomers include N-vinylcarbazole and isopropenyltoluene. The aromatic ring-containing unsaturated monomers can be used alone or in combination of two or more kinds. As the aromatic ring-containing unsaturated monomer, preferably, a styrene-based monomer is used, and more preferably, styrene is used.

[0039] Furthermore, examples of the copolymer of an α-olefin and an aromatic ring-containing monomer include block copolymers, random copolymers and graft copolymers. These can be used alone or in combination of two or more kinds.

[0040] The method for copolymerizing the α-olefin and the aromatic ring-containing monomer is not particularly limited, and any known method may be used. The ratio of the α-olefin and the aromatic ring-containing monomer is appropriately set depending on the purpose and application.

[0041] The olefin wax may also contain a copolymer of α-olefin, unsaturated carboxylic acid and aromatic ring-containing monomer. The method of copolymerizing α-olefin, unsaturated carboxylic acid and aromatic ring-containing monomer is not particularly limited, and a known method is adopted. The ratio of α-olefin, unsaturated carboxylic acid and aromatic ring-containing monomer is appropriately set according to purpose and use.

[0042] The olefin wax is preferably an olefin wax that is not modified with an acid. That is, the olefin wax preferably includes an olefin wax that is not modified with an acid, and more preferably consists of an olefin wax that is not modified with an acid.

[0043] More specifically, the olefin wax is preferably a polymer of an α-olefin that is not modified with an acid. Also, the olefin wax is preferably a copolymer of an α-olefin that is not modified with an acid and an aromatic ring-containing monomer. More preferably, the olefin wax is a polymer of an α-olefin that is not modified with an acid.

[0044] When the olefin wax is not acid-modified, the intermolecular forces derived from the polar group (acid) do not act as compared with the case where the olefin wax is acid-modified, so that the flowability of the thermally conductive composition can be improved, and therefore, excellent moldability can be obtained.

[0045] The olefin wax is a wax with a relatively low molecular weight (low molecular weight wax). More specifically, the weight average molecular weight (polystyrene equivalent molecular weight measured by GPC) of the olefin wax is 25000 or less, preferably 20000 or less, more preferably 15000 or less, even more preferably 10000 or less, even more preferably 5000 or less, and particularly preferably 4500 or less, from the viewpoint of thermal conductivity and appearance. In addition, the weight average molecular weight of the olefin wax (polystyrene equivalent molecular weight measured by GPC) is, for example, 500 or more, preferably 1000 or more, more preferably 2000 or more, even more preferably 2500 or more, and particularly preferably 3000 or more, from the viewpoint of thermal conductivity and appearance. The weight average molecular weight is measured in accordance with the examples described later.

[0046] The number average molecular weight of the olefin wax (polystyrene-equivalent molecular weight measured by GPC) is, for example, 5000 or less, preferably 4500 or less, more preferably 4000 or less, even more preferably 3000 or less, even more preferably 2500 or less, and particularly preferably 2000 or less. The number average molecular weight of the olefin wax (polystyrene-equivalent molecular weight measured by GPC) is, for example, 300 or more, preferably 500 or more, more preferably 700 or more, even more preferably 1000 or more, and particularly preferably 1200 or more. The number average molecular weight is measured in accordance with the examples described later.

[0047] The density of the olefin wax is, for example, 900 kg / m 3 More than 910 kg / m 3 More preferably, 920 kg / m 3 The density of the olefin wax is, for example, 1000 kg / m 3 Less than or equal to 980 kg / m 3 Less than or equal to 970 kg / m 3 The density is measured in accordance with the examples described below.

[0048] The softening point of the olefin wax is, for example, 50° C. or higher, preferably 80° C. or higher, and more preferably 100° C. or higher. The softening point of the olefin wax is, for example, 200° C. or lower, preferably 150° C. or lower, more preferably 140° C. or lower, and even more preferably 130° C. or lower. The softening point is measured in accordance with the examples described later.

[0049] For example, when the olefin wax is acid-modified, that is, when the olefin wax contains a copolymer of an α-olefin and an unsaturated carboxylic acid, the acid value of the olefin wax is, for example, more than 0 mgKOH / g, preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, and in this case, the acid value of the olefin wax is, for example, 90 mgKOH / g or less, preferably 70 mgKOH / g or less, more preferably 50 mgKOH / g or less.

[0050] On the other hand, for example, when the olefin wax is not acid-modified, that is, when the olefin wax does not contain a copolymer of an α-olefin and an unsaturated carboxylic acid, the acid value of the olefin wax is 0 mgKOH / g. The acid value of the olefin wax is preferably 0 mgKOH / g.

[0051] The thermally conductive composition may contain a dispersant other than the above-mentioned olefin wax (hereinafter, other dispersant). Examples of other dispersants include fatty acids, fatty acid metal salts, and fatty acid amides. These may be used alone or in combination of two or more. The thermally conductive composition preferably does not contain other dispersants and contains only olefin wax as a dispersant.

[0052] From the viewpoints of thermal conductivity and appearance, the content of the olefin wax exceeds 1 mass % based on the total amount of the matrix resin, the filler, and the olefin wax, and is preferably 2 mass % or more, and more preferably 3 mass % or more. Also, from the viewpoints of thermal conductivity and appearance, the content of the olefin wax is, for example, 10 mass % or less, preferably 5 mass % or less, and more preferably 4 mass % or less based on the total amount of the matrix resin, the filler, and the olefin wax.

[0053] The content of the olefin wax is, for example, 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, relative to 100 parts by mass of the matrix resin. The content of the olefin wax is, for example, 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 10 parts by mass or less, relative to 100 parts by mass of the matrix resin.

[0054] In the thermally conductive composition, the combination of the matrix resin, the filler, and the olefin wax is appropriately selected according to the purpose and application. More specifically, from the viewpoint of appropriately adjusting the dispersibility of the filler in the matrix resin and obtaining excellent thermal conductivity, it is particularly preferable that the matrix resin contains polyamide, the filler contains aluminum oxide, and the olefin wax contains an olefin wax that is not acid-modified. By using these in combination, the dispersibility of the filler in the matrix resin is particularly appropriately adjusted. As a result, a molded product having particularly excellent thermal conductivity is obtained.

[0055] The thermally conductive composition is obtained by mixing the matrix resin, the filler, and the olefin wax by a known method. The mixing method is not particularly limited, and a known mixing device is used. More specifically, the mixing device may be, for example, a tumbler, a V-type blender, a Nauta mixer, a Banbury mixer, a kneading roll, a single-screw extruder, or a twin-screw extruder.

[0056] The order of mixing is not particularly limited, and for example, the matrix resin, the filler, and the olefin wax can be mixed in any order in sequence. Also, for example, the matrix resin, the filler, and the olefin wax can be mixed simultaneously. Preferably, the matrix resin, the filler, and the olefin wax are mixed simultaneously.

[0057] When the matrix resin, the filler, and the olefin wax are mixed simultaneously, they are mixed in the above-mentioned mixing device so as to obtain a thermally conductive composition containing the matrix resin, the filler, and the olefin wax.

[0058] The above mixing may be a single-stage mixing or a multi-stage mixing. Furthermore, for example, the matrix resin, the filler, and the olefin wax may be primarily mixed to prepare a master batch, and then the master batch may be melt-kneaded (secondary mixing) to prepare the thermally conductive composition.

[0059] Such a thermally conductive composition contains a matrix resin, a filler, and an olefin wax, the weight average molecular weight of which is smaller than a predetermined value, and the content of the olefin wax is within a predetermined range.

[0060] Therefore, in the thermally conductive composition, the olefin wax improves the dispersibility of the filler in the matrix resin, and as a result, the thermally conductive composition provides a molded product with excellent thermal conductivity.

[0061] More specifically, by mixing the matrix resin, the filler, and the olefin wax, the secondary particles of the filler are disintegrated in the matrix resin, and primary particles of the filler are obtained. The olefin wax is then localized at the interface between the matrix resin and the primary particles of the filler, and at least a part of the surface of the primary particles of the filler is coated with the olefin wax. In particular, since the weight-average molecular weight of the olefin wax is relatively low, the olefin wax is smoothly localized at the interface, and at least a part of the surface of the primary particles of the filler is more efficiently coated with the olefin wax.

[0062] This results in a thermally conductive filler composite including the filler (primary particles) and the olefin wax that covers the surface of the filler (primary particles), and also results in a thermally conductive composition including the matrix resin and the thermally conductive filler composite dispersed in the matrix resin.

[0063] In the thermally conductive composition, the filler is covered with the olefin wax, so that the filler is presumably prevented from agglomerating and forming secondary particles. As a result of the filler being prevented from forming secondary particles, the filler is presumably connected in a linear fashion, forming a thermal path.

[0064] In other words, since the thermally conductive composition contains a thermally conductive filler complex having a filler and an olefin wax that coats the surface of the filler, a molded article with excellent thermal conductivity can be obtained.

[0065] The olefin wax also acts as a processing aid, so that the thermally conductive composition can provide molded products with excellent appearance.

[0066] The thermally conductive filler composite contains a filler and an olefin wax that coats the filler and has a predetermined weight average molecular weight, so that the thermally conductive filler composite can provide a molded product with excellent thermal conductivity and appearance.

[0067] The thermally conductive composition may contain known additives. Examples of additives include flame retardants, flame retardant assistants, heat stabilizers, light stabilizers, antioxidants, release agents, flow agents, flow modifiers, lubricants, colorants, antistatic agents, plasticizers, crystal nucleating agents, defoamers, and foaming agents. These additives may be used alone or in combination of two or more. The amount and timing of the additives are appropriately set according to the purpose and application.

[0068] The molded product of the thermally conductive composition is manufactured by a known molding method. Examples of the molding method include extrusion molding, injection molding, cast molding, slush molding, and spray molding. These can be used alone or in combination of two or more. A preferred molding method is injection molding. The molding conditions are appropriately set according to the formulation of the thermally conductive composition and the molding method.

[0069] Such a molded article has excellent thermal conductivity and appearance since it is obtained using the above-mentioned thermally conductive composition.

[0070] Therefore, the above-mentioned thermally conductive composition, thermally conductive filler composite, and molded article are suitably used in various industrial fields that require thermal conductivity and appearance. Such fields include, for example, the field of heat dissipation materials in electrical and electronic components. Examples of electrical and electronic components include, for example, power modules, more specifically, lithium ion batteries. In addition to the above, examples of electrical and electronic components include, for example, light-emitting diode components, liquid crystal components, semiconductor components, generators, transformers, current transformers, and rectifiers. Examples of products in which these are implemented include office automation (OA) housings and home appliance housings, and more specifically, examples of such products include desktop computers, laptops, game machines (e.g., home game machines, commercial game machines, pachinko and slot machines), display devices (e.g., CRT, LCD, plasma, projectors and organic EL), printers, copy machines, scanners, fax machines, mobile phones, portable books, electronic dictionaries, electronic books, portable televisions, recording media (e.g., CDs, DVDs and HDDs), recording media (e.g., IC cards and memory sticks), recording medium readers, optical cameras, digital cameras, antennas, power tools, video tape recorders (VTRs), irons, hair dryers, rice cookers, microwave ovens, audio equipment, lighting equipment (e.g., LED lighting), refrigerators, washing machines, air conditioners, air purifiers and negative ion generators. EXAMPLES

[0071] Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the following examples. Note that "parts" and "%" are based on mass unless otherwise specified. In addition, the specific numerical values ​​of the blending ratio (content ratio), physical property values, parameters, etc. used in the following description can be replaced with the upper limit value (numerical value defined as "less than or equal to" or "less than") or lower limit value (numerical value defined as "more than or equal to" or "exceeding") of the corresponding blending ratio (content ratio), physical property values, parameters, etc. described in the above "Form for carrying out the invention".

[0072] <Raw materials> 1. Matrix resin (A) CM1007: Nylon 6 (polyamide resin), manufactured by Toray Industries, product name Amilan CM1007, density 1,130 kg / m 3

[0073] 2. Filler (B) CB-P15: Alumina, manufactured by Showa Denko Co., Ltd., product name Alnabeads CB-P15, average particle size 16 μm, BET specific surface area 0.3 m 2 / g CB-P05: Alumina, manufactured by Showa Denko Co., Ltd., product name Alnabeads CB-P05, average particle size 4 μm, BET specific surface area 0.7 m 2 / g MBT-010: Boron nitride, manufactured by Mitsui Chemicals

[0074] 3. Olefin wax (C) Production Example 1 (Production of Olefin Wax (W1)) (1) Preparation of catalyst In a glass autoclave with an internal volume of 1.5 liters, 25 g of commercially available anhydrous magnesium chloride was suspended in 500 ml of hexane. The suspension was kept at 30°C, and 92 ml of ethanol was added dropwise to the suspension over 1 hour while stirring, and the reaction was continued for another 1 hour. After the reaction was completed, 93 ml of diethylaluminum monochloride was added dropwise to the suspension over 1 hour, and the reaction was continued for another 1 hour. After the reaction was completed, 90 ml of titanium tetrachloride was added dropwise to the suspension, and the reaction vessel was heated to 80°C and the reaction was continued for 1 hour. After the reaction was completed, the solid portion of the suspension was washed by decantation using hexane. The washing was repeated until free titanium was no longer detected. The titanium concentration of the obtained hexane suspension was quantified by titration, and was used for the following experiment.

[0075] (2) Polymerization of olefin wax (W1) 930 ml of hexane and 70 ml of propylene were placed in a 2-liter stainless steel autoclave that had been thoroughly purged with nitrogen. Hydrogen was then pumped into the autoclave at a pressure of 20.0 kg / cm. 2 (gauge pressure) was introduced.

[0076] Next, the temperature inside the system was raised to 170° C. Thereafter, 0.1 mmol of triethylaluminum, 0.4 mmol of ethylaluminum sesquichloride, and the catalyst obtained above (hexane suspension) were injected into the autoclave with ethylene so that the amount of titanium component was 0.008 mmol in atomic terms, and polymerization was initiated.

[0077] Then, ethylene alone was continuously fed into the autoclave to maintain the total pressure at 40 kg / cm 2 The pressure was kept at 100°C (gauge pressure) and polymerization was carried out at 170°C for 40 minutes. After that, a small amount of ethanol was added to the system to terminate the polymerization. Next, unreacted ethylene and propylene were purged. The resulting solution was dried overnight under reduced pressure at 100°C. As a result, an olefin wax (W1) was obtained.

[0078] Production Example 2 (Production of Acid-Modified Olefin Wax (W2)) 500g of olefin wax (W1) was charged into a glass reactor and melted at 160°C under a nitrogen atmosphere. Then, 30g of maleic anhydride and 3g of di-t-butyl peroxide were continuously fed into the reactor over 5 hours. The contents of the reactor were then heated and reacted for 1 hour. The contents of the reactor were degassed in a molten state under a vacuum of 10mmHg for 0.5 hours to remove volatiles. The contents of the reactor were then cooled to obtain an acid-modified olefin wax (W2).

[0079] Production Example 3 (Production of Acid-Modified Olefin Wax (W3)) The catalyst (hexane suspension) was fed to the autoclave so that the amount of titanium component was 0.007 mmol in atomic terms. Ethylene was fed to the autoclave at a total pressure of 38 kg / cm. 2 (gauge pressure). Except for these, an olefin wax (w3) was obtained in the same manner as in Production Example 1. The olefin wax (w3) had a number average molecular weight of 2400, a weight average molecular weight of 6900, and a density of 920 kg / m 3 and the softening point was 113°C.

[0080] Thereafter, the olefin wax (w3) was acid-modified in the same manner as in Production Example 2 to obtain an acid-modified olefin wax (W3).

[0081] Production Example 4 (Production of Olefin Wax (W4)) Commercially available polypropylene (product name J107G, manufactured by Prime Polymer Co., Ltd., MFR 30 g / 10 min, density 910 kg / m 3 ) was placed in an autoclave and heated at 380° C. for 3 hours under a nitrogen atmosphere, thereby preparing an olefin wax (W4).

[0082] Production Example 5 (Production of Acid-Modified Olefin Wax (W5)) Commercially available polypropylene (product name J107G, manufactured by Prime Polymer Co., Ltd., MFR 30 g / 10 min, density 910 kg / m 3) was placed in an autoclave and heated at 380°C for 3.5 hours under a nitrogen atmosphere. This produced an olefin wax (w5). The olefin wax (w5) had a number average molecular weight of 3,400, a weight average molecular weight of 7,800, and a density of 900 kg / m 3 and the softening point was 139°C.

[0083] Thereafter, the olefin wax (w5) was acid-modified in the same manner as in Production Example 2 to obtain an acid-modified olefin wax (W5).

[0084] Production Example 6 (Production of Acid-Modified Olefin Wax (W6)) No propylene was charged into the autoclave. The catalyst (hexane suspension) was also fed into the autoclave so that the amount of titanium component was 0.004 millimoles in atomic terms. Except for these, an olefin wax (w6) was obtained in the same manner as in Production Example 1. The olefin wax (w6) had a number average molecular weight of 6,000, a weight average molecular weight of 12,000, and a density of 970 kg / m 3 and the softening point was 144°C.

[0085] Thereafter, the olefin wax (w6) was acid-modified in the same manner as in Production Example 2 to obtain an acid-modified olefin wax (W6).

[0086] Production Example 7 (Production of Acid-Modified Olefin Wax (W7)) The olefin wax (W4) was acid-modified in the same manner as in Production Example 2 to obtain an acid-modified olefin wax (W7).

[0087] Production Example 8 (Production of Acid-Modified Olefin Wax (W8)) The catalyst (hexane suspension) was fed to the autoclave so that the amount of titanium component was 0.004 mmol in atomic terms. Ethylene was fed to the autoclave at a total pressure of 38 kg / cm. 2 (gauge pressure) was continuously supplied. Except for these, the same method as in Production Example 1 was used to obtain an olefin wax (W8).

[0088] Production Example 9 (Production of Acid-Modified Olefin Wax (W9)) No propylene was charged into the autoclave. The catalyst (hexane suspension) was fed into the autoclave so that the amount of titanium component was 0.004 mmol in atomic terms. Ethylene was fed into the autoclave at a total pressure of 38 kg / cm. 2 (gauge pressure) was continuously supplied. Except for these, the same method as in Production Example 1 was used to obtain an olefin wax (W9).

[0089] <Physical property measurements> The physical properties of the olefin wax were measured by the following methods, and the results are shown in Table 1. 1.C2 content The ethylene-derived structural units in the olefin wax are 13 The measurement conditions are as follows: Equipment: AVANCEIIIcryo-500 nuclear magnetic resonance spectrometer, Bruker Biospin Measurement frequency; 125MHz Solvent: orthodichlorobenzene / benzene-d6 (4 / 1 v / v) Sample concentration: 60mg / 0.6ml Measurement temperature: 120℃ Number of scans: 128 Repeat time: 5.5 seconds Pulse width: 45°

[0090] 2. Number average molecular weight (Mn) and weight average molecular weight (Mw) The number average molecular weight and weight average molecular weight of the olefin wax were measured by gel permeation chromatography (GPC) under the following measurement conditions. Apparatus: Gel permeation chromatograph Alliance GPC2000 (Waters) Mobile phase: o-dichlorobenzene Columns: TSKgel GMH6-HT x 2, TSKgel GMH6-HTL columns x 2 (both manufactured by Tosoh Corporation) Flow rate; 1.0 ml / min Sample: 0.15mg / mL o-dichlorobenzene solution Temperature; 140℃ Detector; Differential refractometer Calibration curve: Commercially available monodisperse standard polystyrene (PS)

[0091] 3. Density The density of the olefin wax was measured in accordance with JIS K 7112 (1999).

[0092] 4.Softening point The softening point of the olefin wax was measured in accordance with JIS K 2207 (1996).

[0093] 5. Acid value The acid value of the olefin wax was measured in accordance with JIS K 5902 (2006).

[0094] [Table 1]

[0095] Examples 1, 2, 8, 10, 12, Reference Examples 3, 4, 5, 6, 7, 9, 11, and Comparative Examples 1 to 12 The matrix resin (A), filler (B) and olefin wax (C) were uniformly dry-blended according to the formulations shown in Tables 2 to 4. The mixture was then melt-kneaded using a co-rotating twin-screw extruder (Parker Corporation, HK25D (φ25 mm, L / D=41)). This resulted in pellets of the thermally conductive composition.

[0096] The pellets of the thermally conductive composition were dried at 120°C for 8 hours. Next, the pellets of the thermally conductive composition were injection molded using an injection molding machine (Niigata NN100, manufactured by Niigata Machine Techno Co., Ltd.) under conditions of a cylinder temperature of 280°C, a screw rotation speed of 60 rpm, an injection pressure of 130 MPa, and a mold temperature of 90°C. This resulted in a test piece of a molded product of the thermally conductive composition. The shape of the test piece was a square plate (100 mm x 100 mm x 3 mm).

[0097] <Evaluation> 1.Fluidity (molding processability) The kneading conditions for the thermally conductive composition using a twin-screw extruder were set to a screw rotation speed of 150 rpm, a feed rate of 2 kg / h, and an outlet temperature of 280° C., and the steady (final) value of the torque was measured.

[0098] 2.Appearance The appearance of the test piece (square plate) was visually observed, and the surface smoothness was evaluated according to the following criteria. 5 points: No holes with a diameter of 1 mm or more were found. 4 points: Fewer than 5 holes with a diameter of 1 mm or more but less than 2 mm were found, and no holes with a diameter of 2 mm or more were found. 3 points: Five or more holes with a diameter of 1 mm or more but less than 2 mm were found, and no holes with a diameter of 2 mm or more were found. 2 points: Fewer than five holes with a diameter of 2 mm or more were found. 1 point: 5 or more holes with a diameter of 2 mm or more were identified.

[0099] 3. Thermal Conductivity The thermal conductivity of the test specimen (square plate) was measured in accordance with ASTM E1530.

[0100] [Table 2]

[0101] [Table 3]

[0102] [Table 4]

[0103] The above invention is provided as an exemplary embodiment of the present invention, but this is merely an example and should not be interpreted as being limited. Modifications of the present invention that are obvious to those skilled in the art are included in the scope of the following claims. [Industrial Applicability]

[0104] The thermally conductive composition and thermally conductive filler composite of the present invention are suitably used, for example, in the field of heat dissipation materials.

Claims

1. A thermally conductive composition comprising a matrix resin, a filler, and an olefin wax, The weight average molecular weight of the olefin wax is 25,000 or less, The olefin wax is an olefin wax that is not modified with an acid, the filler is at least one selected from the group consisting of metal oxides, metal nitrides, and metal fluorides; A thermally conductive composition, wherein the content of the olefin wax is 3 mass % or more and 5 mass % or less with respect to the total amount of the matrix resin, the filler, and the olefin wax.

2. the matrix resin comprises a polyamide; and The thermally conductive composition of claim 1 , wherein the filler comprises aluminum oxide.

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