JP5554947B2 - Thermally conductive thermoplastic resin composition, sheet or film thereof, hot melt adhesive - Google Patents

Description

  The present invention relates to a thermoplastic resin composition having high thermal conductivity and excellent adhesion to a difficult-to-adhere substrate, a heat-weldable sheet or film obtained from the composition, and a hot melt adhesive. More specifically, at least one compound selected from an epoxy group-containing vinyl monomer, an unsaturated acid, and an unsaturated acid anhydride and an aromatic vinyl monomer in the presence of a polyolefin resin and a radical polymerization initiator. The present invention relates to a modified polyolefin resin modified by addition, a highly heat conductive thermoplastic resin composition containing a heat conductive filler, a heat-weldable sheet or film obtained from the composition, and a hot melt adhesive.

  Conventionally, as a heat conductive resin material, a material based on a thermoplastic resin or rubber and blended with a heat conductive filler is known. In addition, heat radiating material parts mainly for electronic parts have been made using such heat conductive resin materials. As such a heat conductive resin material, for example, resin material (Patent Document 1) in which aluminum nitride is blended with high density polyethylene, polyolefin thermoplastic elastomer or polypropylene, and metal hydroxide is blended with (meth) acrylate polymer. Resin materials (Patent Document 2), resin materials for battery storage batteries (Patent Document 3) in which a thermal conductive filler is blended with a thermoplastic resin, resin materials (Patent Document 3) in which a thermal conductive filler is blended with an ethylene copolymer resin (Patent Document 3) Patent Document 4) and the like are disclosed.

  However, in the case of a conventional thermally conductive resin material based on a polyolefin resin, the tackiness and adhesiveness with a difficult-to-adhere substrate such as metal has not been sufficient. For this reason, adhesive sheets, adhesives, and the like have been used for the purpose of improving the adhesiveness and adhesiveness with metals. However, it has been pointed out that these adhesive sheets, adhesives and the like have problems in that their heat conductivity is not sufficient so that the heat dissipation efficiency is lowered, or the adhesiveness and tackiness are lowered due to deterioration due to long-term use. .

  Moreover, even if the adhesion to a metal or the like is improved, it may be difficult to ensure sufficient thermal conductivity even if a large amount of thermally conductive filler is blended.

  Further, in the case of rubber, the contamination due to the additive blade is another problem, and in the case of silicone rubber, the contact failure due to the low molecular siloxane is a problem.

JP-A-10-132493 JP 2002-285121 A JP 2003-187757 A JP 2009-67877 A

  In view of the present situation, the present invention provides a thermoplastic resin composition having high heat conductivity and excellent adhesion to a difficult-to-adhere substrate, a heat-weldable sheet or film obtained from the composition, and a hot melt adhesive The task is to do.

  As a result of intensive studies on measures that can satisfy high thermal conductivity, adhesiveness, and heat-weldability, the present inventors obtained unprecedented high thermal conductivity by using a modified polyolefin resin having a specific structure. And it discovered that high adhesiveness and heat weldability could be achieved, and came to complete this invention.

That is, the present invention
(1) (a) at least one compound selected from (a) an epoxy group-containing vinyl monomer, an unsaturated acid, and an unsaturated acid anhydride in the presence of (b) a radical polymerization initiator in the polyolefin-based resin; And (d) modified by adding an aromatic vinyl monomer, and the ratio of (c) in the total weight of (a), (c) and (d) is in the range of 0.1 to 50% by weight. The modified polyolefin resin (A) and the thermally conductive filler (B) are contained, and the volume ratio of (A) / (B) is in the range of 85/15 to 25/75, Thermoplastic resin composition.

  (2) The modified polyolefin resin (A) is (b) in the presence of a radical polymerization initiator, (c) an epoxy group-containing vinyl monomer, an unsaturated acid, and an unsaturated resin. The thermoplastic resin composition according to (1), which is obtained by melt-kneading at least one compound selected from acid anhydrides and (d) an aromatic vinyl monomer.

  (3) The thermoplastic resin composition according to (1) or (2), wherein (a) the polyolefin-based resin is a polypropylene-based resin having a majority of propylene units.

  (4) Thermally conductive filler (B) is a carbon compound, metal oxide, metal nitride, metal carbide, metal hydroxide, metal carbonate, crystalline silica, organic polymer fired product, nitrogen carbide, Zn ferrite The thermoplastic resin composition according to any one of (1) to (3), wherein the thermoplastic resin composition is at least one selected from composite ferrite, Fe—Al—Si ternary alloy, and metal powder .

  (5) The thermally conductive filler (B) is selected from graphite, diamond, aluminum oxide, magnesium oxide, boron nitride, aluminum nitride, aluminum hydroxide, magnesium carbonate, and Fe—Al—Si ternary alloy. The thermoplastic resin composition according to any one of (1) to (4), which is at least one kind.

  (6) A polyolefin-based sheet or film having heat-weldability, obtained from the thermoplastic resin composition according to any one of (1) to (5).

  (7) A hot-melt adhesive having a heat-weldability obtained from the thermoplastic resin composition according to any one of (1) to (5).

(8) At least selected from the group consisting of the thermoplastic resin composition according to (1) to (5), the polyolefin-based sheet or film according to (6), and the hot melt adhesive according to (7). An adhesive body formed by bonding at least one.
About.

  According to the present invention, a thermoplastic resin composition having high heat conductivity and excellent adhesion to a difficult-to-adhere substrate is obtained, and a heat-welding sheet or film having high heat dissipation from the composition, and heat conductive hot melt adhesion An agent is obtained.

  The modified polyolefin resin (A) used in the present invention includes (a) a polyolefin resin in the presence of (b) a radical polymerization initiator, (c) an epoxy group-containing vinyl monomer, an unsaturated acid, and an unsaturated acid. It is modified by adding at least one compound selected from anhydrides and (d) an aromatic vinyl monomer.

  (A) Examples of the polyolefin-based resin include polyethylene; polypropylene; poly-1-butene; polyisobutylene; random copolymer or block copolymer in any ratio of propylene and ethylene and / or 1-butene; Ethylene / propylene / diene terpolymers having a diene component of 50% by weight or less in any proportion to propylene; polymethylpentene; cyclic polyolefins such as copolymers of cyclopentadiene and ethylene and / or propylene; ethylene or Examples thereof include a random copolymer or block copolymer of propylene and 50% by weight or less of a vinyl compound. Among these, polypropylene, polyethylene, and polyisobutylene are preferable, and polypropylene is particularly preferable.

  In addition, a polyolefin-based resin into which a polar group is introduced can also be used because it is easily compatible with an unsaturated carboxylic acid monomer having a polar group. Specific examples of polyolefin resins having a polar group introduced include acid-modified polypropylene such as maleic anhydride-modified polypropylene, maleic acid-modified polypropylene, and acrylic acid-modified polypropylene; ethylene / vinyl chloride copolymer, ethylene / vinylidene chloride copolymer Polymer, ethylene / acrylonitrile copolymer, ethylene / methacrylonitrile copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylamide copolymer, ethylene / methacrylamide copolymer, ethylene / acrylic acid copolymer, ethylene / Methacrylic acid copolymer, ethylene / maleic acid copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / isopropyl acrylate copolymer, ethylene / butyl acrylate copolymer , Ethylene / a Isobutyl acrylate copolymer, ethylene / 2-ethylhexyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / isopropyl methacrylate copolymer, ethylene / butyl methacrylate Copolymer, ethylene / isobutyl methacrylate copolymer, ethylene / 2-ethylhexyl methacrylate copolymer, ethylene / maleic anhydride copolymer, ethylene / ethyl acrylate / maleic anhydride copolymer, ethylene / acrylic acid Metal salt copolymer, ethylene / methacrylic acid metal salt copolymer, ethylene / vinyl acetate copolymer or saponified product thereof, ethylene / vinyl propionate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / acrylic Ethylate / Glycidyl methacrylate copolymer Body, ethylene or α- olefin / vinyl monomer copolymers such as ethylene / vinyl acetate / glycidyl methacrylate copolymer; chlorinated polypropylene, chlorinated polyolefins such as chlorinated polyethylene.

  These polyolefin resins may be used alone or in combination of two or more.

  The polyolefin resin preferably has a majority of propylene units from the viewpoint that radicals are easily generated with respect to the polyolefin resin. The majority amount here means that the propylene component is 50% by weight or more based on the polyolefin resin.

  When two or more types of polyolefin resins are used in combination, the total weight of the propylene components in each polyolefin resin may be 50% by weight or more with respect to the total weight of the mixed polyolefin resins. preferable.

  If necessary, other raw materials or rubbers may be added to the raw material polyolefin resin within the range where the effects of the present invention are exhibited.

  Such other resins or rubbers include, for example, polyethylene; poly α-olefins such as polypropylene, polybutene-1, polyisobutene, polypentene-1, polymethylpentene-1, etc .; ethylene / propylene having a propylene content of less than 75% by weight Copolymers, ethylene / butene-1 copolymers, ethylene or α-olefin / α-olefin copolymers such as propylene / butene-1 copolymers having a propylene content of less than 75% by weight; propylene content of 75 Less than wt% ethylene / propylene / 5-ethylidene-2-norbornene copolymer or other ethylene or α-olefin / α-olefin / diene monomer copolymer; polybutadiene copolymer such as polybutadiene or polyisoprene ; Vinyl monomers such as styrene / butadiene random copolymers / diene monomers Romer random copolymer; Vinyl monomer / diene monomer / vinyl monomer block copolymer such as styrene / butadiene / styrene block copolymer; Hydrogenation (styrene / butadiene random copolymer), etc. Hydrogenation (vinyl monomer / diene monomer random copolymer); Hydrogenation (vinyl monomer / diene monomer / vinyl) such as hydrogenation (styrene / butadiene / styrene block copolymer) Monomer block copolymer); vinyl monomer / diene monomer / vinyl monomer graft copolymer such as acrylonitrile / butadiene / styrene graft copolymer, methyl methacrylate / butadiene / styrene graft copolymer Coalescence: polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, ethyl polyacrylate, polybutyl acrylate, poly Vinyl polymers such as methyl tacrylate and polystyrene; vinyl copolymers such as vinyl chloride / acrylonitrile copolymer, vinyl chloride / vinyl acetate copolymer, acrylonitrile / styrene copolymer, methyl methacrylate / styrene copolymer Etc.

  The amount of the other resin or rubber added to the polyolefin-based resin varies depending on the type of the resin or rubber, and may be within the range where the effects of the present invention can be achieved as described above. It is preferable that it is below a grade.

  Further, the polyolefin-based resin may contain an antioxidant, a metal deactivator, a phosphorous heat stabilizer, an ultraviolet absorber, a light stabilizer, a fluorescent brightener, a metal soap, an antacid adsorbent, etc., if necessary. Addition of stabilizers, cross-linking agents, chain transfer agents, nucleating agents, lubricants, plasticizers, fillers, reinforcing agents, pigments, dyes, flame retardants, antistatic agents, etc. within the range where the effects of the present invention are exhibited. You may do it.

  In addition, these polyolefin resins (which may contain various additive materials) may be in the form of particles or pellets, and the size and shape are not particularly limited.

  Furthermore, when the additive material (other resin, rubber, stabilizer and / or various additives) is used, the polyolefin resin is melted even if the additive material is previously added to the polyolefin resin. In addition, it may be added when the modified polyolefin resin is produced, or may be added to the modified polyolefin resin by an appropriate method after the modified polyolefin resin is produced.

  Examples of the radical polymerization initiator (b) used in the present invention generally include peroxides or azo compounds. Examples thereof include ketone peroxides such as methyl ethyl ketone peroxide and methyl acetoacetate peroxide; 1,1-bis ( t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2, Peroxyketals such as 2-bis (t-butylperoxy) butane; permethane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, etc. Hydroperoxide; Dicumyl peroxide 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, di-t Dialkyl peroxides such as butyl peroxide and 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; Diacyl peroxides such as benzoyl peroxide; Di (3-methyl-3-methoxy Butyl) peroxydicarbonate, peroxydicarbonate such as di-2-methoxybutylperoxydicarbonate; t-butylperoxyoctate, t-butylperoxyisobutyrate, t-butylperoxylaurate, t -Butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyisopropyl Peroxyesters such as carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, etc. One or more organic peroxides may be mentioned.

  Among these, those having particularly high hydrogen abstraction ability are preferable. Examples of such radical polymerization initiators include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1. Peroxyketals such as bis (t-butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane; Peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, di -Dialkyl peroxides such as t-butyl peroxide and 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; benzo Diacyl peroxides such as ruperoxide; t-butylperoxyoctate, t-butylperoxyisobutyrate, t-butylperoxylaurate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, etc. 1 type, or 2 or more types, such as peroxyesters.

  The addition amount of the radical polymerization initiator is preferably in the range of 0.01 to 10 parts by weight, and in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the (a) polyolefin resin. Is more preferable. If the addition amount of the radical polymerization initiator is in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of (a), (a) a polyolefin-based resin without causing a decrease in fluidity and mechanical properties. At least one compound selected from (c) an epoxy group-containing vinyl monomer, an unsaturated acid, and an unsaturated acid anhydride can be sufficiently grafted to the resin, and the modification proceeds sufficiently.

  Examples of at least one compound selected from (c) an epoxy group-containing vinyl monomer, an unsaturated acid, and an unsaturated acid anhydride used in the present invention include glycidyl methacrylate, glycidyl acrylate, and maleic acid mono Glycidyl, diglycidyl maleate, monoglycidyl itaconate, diglycidyl itaconate, monoglycidyl allyl succinate, diglycidyl allyl succinate, glycidyl p-styrenecarboxylate; allyl glycidyl ether, methallyl glycidyl ether, styrene-p-glycidyl ether; p-glycidyl Styrene; Epoxy olefins such as 3,4-epoxy-1-butene and 3,4-epoxy-3-methyl-1-butene; Vinylcyclohexene monooxide; Unsaturated acrylic acid, methacrylic acid, maleic acid, fumaric acid, etc. Acid; unsaturated acid anhydrides such as maleic anhydride; one or more, and the like.

  Among these, glycidyl methacrylate, glycidyl acrylate, maleic acid, fumaric acid, and maleic anhydride are preferable because they are inexpensive. (C) The addition amount of at least one compound selected from an epoxy group-containing vinyl monomer, an unsaturated acid, and an unsaturated acid anhydride is 0.1% with respect to 100 parts by weight of the (a) polyolefin resin. It is preferably ˜100 parts by weight, and more preferably 0.5 to 50 parts by weight. In addition, the ratio of at least one compound selected from (c) an epoxy group-containing vinyl monomer, an unsaturated acid, and an unsaturated acid anhydride is (a) a polyolefin-based resin, and (c) an epoxy group-containing vinyl monomer. It is preferably in the range of 0.1 to 50% by weight of the total weight of at least one compound selected from a monomer, an unsaturated acid, and an unsaturated acid anhydride, and (d) an aromatic vinyl monomer. The range of 0.5 to 40% by weight is more preferable, and the range of 1 to 30% by weight is most preferable. (C) At least one compound selected from an epoxy group-containing vinyl monomer, an unsaturated acid, and an unsaturated acid anhydride is 0.1 to 50 of the total weight of (a), (c), and (d). If it is the range of weight%, adhesiveness is fully improved and it can acquire as a resin composition which has a suitable shape and external appearance.

  Examples of the (d) aromatic vinyl monomer used in the present invention include styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, dimethylstyrene, and trimethyl. Methyl styrene such as styrene; chlorostyrene such as o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, α-chlorostyrene, β-chlorostyrene, dichlorostyrene, trichlorostyrene; o-bromostyrene, m-bromostyrene , Bromostyrene such as p-bromostyrene, dibromostyrene, tribromostyrene; fluorostyrene such as o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, difluorostyrene, trifluorostyrene; o-nitrostyrene, m- Nitrostyrene, p Nitrostyrenes such as nitrostyrene, dinitrostyrene, and trinitrostyrene; vinylphenols such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, and trihydroxystyrene; o-divinylbenzene, m-divinylbenzene, 1 type, or 2 or more types, such as divinylbenzene, such as p-divinylbenzene; diisopropenylbenzene, such as o-diisopropenylbenzene, m-diisopropenylbenzene, and p-diisopropenylbenzene; Among these, methyl styrene such as styrene, α-methyl styrene, p-methyl styrene, divinylbenzene monomer or divinylbenzene isomer mixture is preferable because it is inexpensive.

  The addition amount of the aromatic vinyl monomer is preferably in the range of 0.1 to 50 parts by weight, and in the range of 0.5 to 40 parts by weight with respect to 100 parts by weight of the (a) polyolefin resin. More preferably, it is most preferably in the range of 1 to 30 parts by weight. When the addition amount of the aromatic vinyl monomer is in the range of 0.1 to 50 parts by weight with respect to (a) 100 parts by weight, (c) epoxy group-containing vinyl with respect to (a) polyolefin resin At least one compound selected from a monomer, an unsaturated acid, and an unsaturated acid anhydride can be sufficiently grafted, and the modification proceeds sufficiently.

  The order of addition of the components (a) to (d) and the method thereof are as follows. (C) An epoxy group-containing vinyl unit is added to a mixture obtained by melt-kneading (a) a polyolefin resin and (b) a radical polymerization initiator. At least one compound selected from a monomer, an unsaturated acid, and an unsaturated acid anhydride, and (d) an addition order in which an aromatic vinyl monomer is added and melt-kneaded are preferred, and by adding in this order, (A) At least one compound selected from (c) an epoxy group-containing vinyl monomer, an unsaturated acid, and an unsaturated acid anhydride can be sufficiently grafted on the polyolefin-based resin, and does not contribute to grafting. The production of low molecular weight substances can be suppressed. In addition, the order and method of mixing and melt-kneading of other materials added as necessary are not particularly limited.

  Furthermore, the heating temperature at the time of melt kneading is preferably in the range of 130 to 300 ° C. from the viewpoint that (a) the polyolefin-based resin is sufficiently melted and is not thermally decomposed. The time for melt kneading (the time after mixing the radical polymerization initiator) is usually 30 seconds to 60 minutes.

  Moreover, as an apparatus at the time of melt-kneading, an extruder, a Banbury mixer, a mill, a kneader, a heating roll, or the like can be used. From the standpoint of productivity, a method using a single screw or twin screw extruder is preferred. Moreover, in order to mix each material sufficiently uniformly, the melt kneading may be repeated a plurality of times.

  Further, in the present invention, the modified polyolefin-based resin forms a multiphase structure, and (a) the phase composed of the polyolefin-based resin includes (c) an epoxy group-containing vinyl monomer, an unsaturated acid, and an unsaturated acid anhydride. This is particularly effective when the phase comprising at least one selected compound and (d) an aromatic vinyl monomer is finely dispersed. Depending on the reaction conditions such as heating temperature, melt kneading time, etc., (a) selected from (c) epoxy group-containing vinyl monomer, unsaturated acid, and unsaturated acid anhydride in the phase composed of polyolefin resin The phase comprising at least one kind of compound and (d) the aromatic vinyl monomer is preferably 1 μm or less on average, more preferably 0.5 μm or less, and particularly preferably 0.3 μm or less. preferable. (C) at least one compound selected from an epoxy group-containing vinyl monomer, an unsaturated acid, and an unsaturated acid anhydride, and (d) a phase composed of an aromatic vinyl monomer is 1 μm or less on average Since the functional groups of the components (c) and (d) are finely dispersed, the adhesion can be improved efficiently.

  As the heat conductive filler (B) used in the present invention, a commercially available general heat conductive filler can be used. Above all, in terms of high thermal conductivity, availability, etc., carbon compounds such as graphite and diamond; acrylonitrile-based polymer fired products, furan resin fired products, cresol resin fired products, polyvinyl chloride fired products, sugar fired products Baked products of organic polymers such as baked products and charcoal; metal oxides such as aluminum oxide, magnesium oxide, beryllium oxide, titanium oxide, zirconium oxide and zinc oxide; metal nitrides such as boron nitride, aluminum nitride and silicon nitride; Metal carbides such as boron carbide, aluminum carbide and silicon carbide; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; metal carbonates such as magnesium carbonate; crystalline silica; nitrogen carbide; composite ferrite with Zn ferrite; -Al-Si ternary alloys; metal powders and the like are preferred. Furthermore, from the viewpoint of availability and thermal conductivity, graphite, aluminum oxide, magnesium oxide, boron nitride, aluminum nitride, silicon carbide, aluminum hydroxide, magnesium carbonate, crystalline silica, Mn-Zn soft ferrite, Ni-Zn -Based soft ferrite, Fe-Al-Si ternary alloy (Sendust), pure iron (purity of 95% or more), iron-nickel alloy (Permalloy) are more preferable, aluminum oxide, boron nitride, aluminum nitride, aluminum hydroxide Mn—Zn soft ferrite, Fe—Al—Si ternary alloy (Sendust), and pure iron (having a purity of 95% or more) are particularly preferable.

  The shape of the heat conductive filler is not particularly limited, and those having a desired shape such as a spherical shape, a plate shape, a fiber shape, and an indefinite shape can be used. However, when it is desired to impart flexibility such as low hardness to the sheet or film obtained from the heat conductive resin composition of the present invention, it is preferable to use a filler having a shape close to a sphere. The particle size of the heat conductive filler is not particularly limited, but is preferably about 0.1 to 500 μm from the viewpoint of compatibility with the modified polyolefin resin (A), reinforcing properties, heat conduction performance, and the like.

  In addition, the thermally conductive filler is a silane coupling agent (vinyl silane, epoxy silane, (meth) acryl silane, isocyanate silane, chloro silane, amino silane, because the dispersibility in the modified polyolefin resin (A) is improved. Etc.), titanate coupling agents (alkoxy titanate, amino titanate, etc.), or fatty acids (caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and other saturated fatty acids, sorbic acid Unsaturated acids such as elaidic acid, oleic acid, linoleic acid, linolenic acid, erucic acid, etc.) and resin acids (abietic acid, pimaric acid, levopimaric acid, neoabietic acid, parastrinic acid, dehydroapitic acid, isopimaric acid, Sandaracopimaric acid, Komuric acid Seco dehydroabietic acid, the dihydroabietic acid, etc.) or the like, it is preferable that the surface has been treated.

  The amount of the thermally conductive filler used is that the modified polyolefin resin (A) and the thermally conductive filler (B) can be used because the thermal conductivity of the thermoplastic composition of the present invention can be increased. ) Volume ratio (A) / (B) is preferably in the range of 85/15 to 25/75. The more the amount of (A) used, the better the molding processability of the resulting thermoplastic resin composition, which tends to facilitate melt-kneading, and the higher the amount of (B) used, the higher the heat. The volume ratio is preferably 80/20 to 33/67, more preferably 75/25 to 35/65, still more preferably 73/27 to 40/60, most preferably because conductivity tends to improve. Preferably it is 70/30-45/55.

  Here, the volume of the modified polyolefin resin (A) and the volume of the thermally conductive filler (B), which are the calculation criteria for the volume ratio of the present invention, were respectively determined as follows. The volume of the modified polyolefin resin (A) was a value obtained by dividing the weight of the resin (A) by the density of the (A) measured separately. The volume of the heat conductive filler (B) was a value obtained by dividing the weight of the heat conductive filler (B) by the density of the (B).

  In addition, as a method for increasing the filling rate of the filler (B) with respect to the modified polyolefin resin (A), it is preferable to use two or more kinds of fillers having different particle diameters in combination. In this case, it is preferable that the filler having a large particle diameter exceeds 10 μm and the filler having a small particle diameter is 10 μm or less. Moreover, these fillers can use not only the same kind of filler but also two or more kinds of different kinds in combination.

  Furthermore, in order to make the thermoplastic resin composition of the present invention have higher performance, various heat stabilizers such as a phenol-based heat stabilizer, a sulfur-based heat stabilizer, and a phosphorus-based heat stabilizer are used alone or in two kinds. It is preferable to add a combination of the above. Further, as required, heat stabilizers, stabilization aids, lubricants, mold release agents, plasticizers, flame retardants, flame retardant aids, ultraviolet absorbers, light stabilizers, pigments, dyes are generally well known. In addition, an antistatic agent, a conductivity imparting agent, a dispersant, a compatibilizing agent, an antibacterial agent and the like may be added singly or in combination of two or more in a range where the effects of the present invention are exhibited.

  It does not specifically limit as a manufacturing method of the thermoplastic resin composition of this invention. For example, it can be produced by drying the above-described components, additives and the like and then melt-kneading them in a melt-kneader such as a single-screw or twin-screw extruder. Moreover, when a compounding component is a liquid, it can also manufacture by adding to a melt-kneader on the way using a liquid supply pump etc. In addition, supply each specified component to mixers and / or mixing kneaders such as ribbon blenders, super mixers, tumbler mixers, Banbury mixers, Henschel mixers, mixing rolls, kneaders, feeder ruders, etc., hot blending, cold blending, etc. It can also be produced by a method such as uniform mixing or mixing and kneading by the conventional method. The supply method of each component is not particularly limited, and each component may be mixed and mixed and / or mixed and kneaded, or may be mixed and / or mixed and kneaded in multiple stages.

  In the thermoplastic resin composition of the present invention, the moldability can be further improved by adding a crystallization accelerator such as a nucleating agent as necessary.

  Examples of the crystallization accelerator used in the present invention include higher fatty acid amides, urea derivatives, sorbitol compounds, higher fatty acid salts, aromatic fatty acid salts and the like, and these can be used alone or in combination of two or more. . Of these, higher fatty acid amides, urea derivatives, and sorbitol compounds are preferred because of their high effects as crystallization accelerators.

  Examples of the higher fatty acid amide include behenic acid amide, oleic acid amide, erucic acid amide, stearic acid amide, palmitic acid amide, N-stearyl behenic acid amide, N-stearyl erucic acid amide, ethylenebisstearic acid amide, ethylene Bisoleic acid amide, ethylene biserucic acid amide, ethylene bislauric acid amide, ethylene biscapric acid amide, p-phenylenebisstearic acid amide, ethylenediamine, stearic acid and sebacic acid polycondensate, etc. Acid amides are preferred.

  Examples of the urea derivative include bis (stearylureido) hexane, 4,4′-bis (3-methylureido) diphenylmethane, 4,4′-bis (3-cyclohexylureido) diphenylmethane, 4,4′-bis (3- Cyclohexylureido) dicyclohexylmethane, 4,4′-bis (3-phenylureido) dicyclohexylmethane, bis (3-methylcyclohexylureido) hexane, 4,4′-bis (3-decylureido) diphenylmethane, N-octyl-N ′ -Phenylurea, N, N'-diphenylurea, N-tolyl-N'-cyclohexylurea, N, N'-dicyclohexylurea, N-phenyl-N'-tribromophenylurea, N-phenyl-N'-tolylurea N-cyclohexyl-N′-phenylurea , Etc. are exemplified, especially bis (stearyl ureido) hexane are preferred.

  Examples of the sorbitol compound include 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene. Sorbitol, 1,3-benzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p- Ethylbenzylidene) sorbitol, 1,3,2,4-di (pn-propylbenzylidene) sorbi 1,3,2,4-di (p-i-propylbenzylidene) sorbitol, 1,3,2,4-di (pn-butylbenzylidene) sorbitol, 1,3,2,4-di ( p-s-butylbenzylidene) sorbitol, 1,3,2,4-di (pt-butylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenzylidene) sorbitol, 1,3,2 , 4-Di (p-ethoxybenzylidene) sorbitol, 1,3-benzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidenesorbitol, 1,3-p- Chlorbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1 3-p-methylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol, and 1,3,2,4-di (p-chloro) Benzylidene) sorbitol, and the like. Among these, 1,3,2,4-di (p-methylbenzylidene) sorbitol and 1,3,2,4-dibenzylidenesorbitol are preferable.

  The amount of the crystallization accelerator used in the thermoplastic resin composition of the present invention is in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the modified polyolefin resin (A) from the viewpoint of moldability. Is preferable, it is more preferable that it exists in the range of 0.03-4 weight part, and it is still more preferable that it exists in the range of 0.05-3 weight part. When the amount of the crystallization accelerator used is in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of (A), the effect as a crystallization accelerator is exerted without excess and deficiency, and the appearance and physical properties are impaired. There is nothing.

  Moreover, the thermoplastic resin composition of the present invention is required to have high thermal conductivity. The thermal conductivity is preferably 0.5 W / m · K or more, more preferably 1 W / m · K or more, and most preferably 1.5 W / m · K or more. When the thermal conductivity is 0.5 W / m · K or more, for example, when a sheet or film obtained from the thermoplastic resin composition or a hot melt adhesive is applied to an internal heat dissipation member of an electronic device or the like In addition, the heat generated inside can be efficiently radiated to the outside.

  The thermal conductivity of the thermoplastic resin composition of the present invention is obtained by, for example, obtaining a nickel foil sensor having a double spiral structure from the thermoplastic resin composition of the present invention using a hot disk method thermal property measuring device. It can be calculated from the temperature rise of the sensor by sandwiching it between two sheet-like or film-like samples and heating the sensor with constant power.

  Furthermore, the sheet or film of the present invention can be exemplified by a thickness of 3 μm to 3 mm, preferably 10 μm to 1 mm, and can be used as an adhesive sheet or film having heat-welding properties.

  The method for producing the heat-welding polyolefin-based sheet or film having excellent adhesiveness of the present invention is not particularly limited. For example, from the thermoplastic resin composition of the present invention, various extruders, injection molding It can be formed into a sheet or film using a machine, a calendar molding machine, an inflation molding machine, a roll molding machine, or a hot press molding machine.

  The adhesive sheet or film having heat weldability obtained in this way is used in various applications such as electronic materials, magnetic materials, catalyst materials, structural materials, optical materials, medical materials, automotive materials, building materials, and the like. It can be used widely.

  As the heat conductive hot melt adhesive of the present invention, the thermoplastic resin composition of the present invention can be used as it is, or for example, in the form of an adhesive film or sheet having the heat welding property of the present invention.

  The hot melt adhesive is made of metal such as gold, silver, copper, iron, tin, lead, aluminum, silicon, inorganic materials such as glass and ceramics; cellulosic polymer materials such as paper and cloth; melamine resin and acrylic・ Synthetic polymer materials such as urethane resin, urethane resin, (meth) acrylic resin, styrene / acrylonitrile copolymer resin, polycarbonate resin, polyester resin, phenol resin, alkyd resin, epoxy resin, silicone resin, etc. Can be used for heat bonding, assembly of various parts, laminating, etc., such as aircraft, ships, vehicles, household appliances, electronic equipment, precision equipment, printed wiring, flock processing, wall materials, solar equipment, furniture materials, building materials, etc. It is applicable to various uses.

  The material of the adherend used in the present invention is, for example, a material that can be bonded to the thermoplastic resin of the present invention. Specifically, for example, as described above, metals such as gold, silver, copper, iron, tin, lead, aluminum and silicon, inorganic materials such as glass and ceramics; cellulosic polymer materials such as paper and cloth; Melamine resin, acrylic / urethane resin, urethane resin, (meth) acrylic resin, styrene / acrylonitrile copolymer resin, polycarbonate resin, polyester resin, phenol resin, alkyd resin, epoxy resin, silicone resin, etc. Examples include synthetic polymer materials.

  Two or more different materials may be mixed and combined as the material of the adherend. When the laminate is formed by adhering two different adherends through the adhesive sheet or film having the heat-welding property of the present invention, the materials constituting the two adherends are the same. Either a kind of material or a different kind of material may be used. Although it does not specifically limit as a property of a to-be-adhered body, For example, a film form, a sheet form, plate shape, a fiber form etc. are mentioned. In addition, the adherend may be subjected to a surface treatment such as a release agent, a coating such as plating, a coating with a paint, surface modification by plasma or laser, surface oxidation, etching, etc., as necessary. good. Specific examples of the adherend include, for example, an exothermic heater, a temperature sensor, a CPU, a transistor, a heat sink, a mounting board inside an electronic device, a mounting board for a light emitting element such as an LED, and the like. It is not limited to these.

  Next, the present invention will be described in more detail based on examples, but the present invention is not limited only to such examples.

[Production Example 1]
(A) 90 parts by weight of random polypropylene (J229E manufactured by Prime Polymer Co., Ltd., MFR = 50), (b) 1,3-di (t-butylperoxyisopropyl) benzene (Perbutyl P manufactured by Nippon Oil & Fats Co., Ltd., 1 0.5 parts by weight of a half-life temperature of 175.4 ° C. per minute was supplied to Nippon Steel Works Co., Ltd. Co-Directional Twin Screw Extruder TEX30 (L / D = 28) set at 200 ° C. and melt kneaded Then, 5 parts by weight of (c) glycidyl methacrylate and (d) 5 parts by weight of styrene were added and melt-kneaded from the middle of the cylinder to obtain modified polyolefin resin pellets (A-1). The average particle diameter of the domain consisting of the components of (A-1) glycidyl methacrylate and styrene was 0.1 μm.

[Production Example 2]
(A-1) 40 parts by weight of random polypropylene (J229E manufactured by Prime Polymer Co., Ltd., MFR = 50), (a-2) 40 parts by weight of polypropylene ethylene rubber (Versify 3401 manufactured by Dow Chemical Company, MFR = 8), (b ) 1.5 parts by weight of 1,3-di (t-butylperoxyisopropyl) benzene (Nippon Yushi Co., Ltd., Perbutyl P, 1 minute half-life 175.4 ° C.) set to 200 ° C. Japan Co., Ltd. Supply to a steel mill same direction meshing type twin screw extruder TEX30 (L / D = 28) and melt knead, then (c) 10 parts by weight of glycidyl methacrylate and (d) 10 parts by weight of styrene from the middle of the cylinder In addition, it was melt kneaded to obtain modified polyolefin resin pellets (A-2). The average particle size of the domain (A-2) composed of the components of glycidyl methacrylate and styrene was 0.1 μm.

[Production Example 3]
(A) 90 parts by weight of polypropylene ethylene rubber (Versify 3401 manufactured by Dow Chemical Co., MFR = 8), (b) 1,3-di (t-butylperoxyisopropyl) benzene (Perbutyl P, manufactured by Nippon Oil & Fats Co., Ltd., 1 0.5 parts by weight of a half-life of 175.4 ° C. per minute is supplied to Nippon Steel Works Co., Ltd., in-direction meshing twin screw extruder TEX30 (L / D = 28) set at 200 ° C. and melt-kneaded. Then, (c) 5 parts by weight of glycidyl methacrylate and (d) 5 parts by weight of styrene were added and melt kneaded from the middle of the cylinder to obtain a modified polyolefin resin pellet (A-3). The average particle size of the domain consisting of the components of (A-3) glycidyl methacrylate and styrene was 0.1 μm.

[Example 1]
As the modified polyolefin resin (A), 100 parts by weight of the modified polyolefin resin pellet (A-1) produced in Production Example 1 was used, and a phenol stabilizer (ADE-60 manufactured by ADEKA Co., Ltd.) 0.2 was used. What mixed the weight part was prepared (raw material 1). Separately, 100 parts by weight of hexagonal boron nitride (PT-110 manufactured by Momentive Performance Materials, hereinafter referred to as “FIL-1”) is used as the thermally conductive filler (B), and this is an epoxysilane coupling agent. (KBS-303 manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part by weight and 5 parts by weight of ethanol were mixed with a super floater, stirred for 5 minutes, and then dried at 80 ° C. for 4 hours (raw material 2). Raw material 1 and raw material 2 are set in separate weight type feeders and mixed so that the volume ratio of (A) / (B) is 67/33, and then the same direction meshing type twin screw extrusion manufactured by Nippon Steel Co., Ltd. It was introduced from a hopper provided near the screw root of the machine TEX44XCT. The set temperature was 150 ° C. in the vicinity of the raw material supply port. The set temperature was sequentially increased toward the screw tip, and the screw tip temperature was set to 200 ° C. Under these conditions, a film having a thickness of 0.1 mm was obtained from the T-die, and subjected to T-shaped peel evaluation and shear strength evaluation. Separately, a thermally conductive thermoplastic resin composition obtained by extrusion under the same conditions was pressed at 200 ° C. for 3 minutes to obtain a sheet having a thickness of 3 mm, and used for evaluation of thermal conductivity.

[Examples 2 to 11, Comparative Examples 1 to 4]
Except having changed the kind and quantity of a compounding raw material as shown in Table 1, it carried out similarly to Example 1, and obtained the film and the sheet | seat and used for each evaluation.

  Of the raw materials used in Examples and Comparative Examples, the raw materials other than those exemplified in Production Examples 1 to 3 are as follows.

[Resin or resin composition]
<PP-1>: Random polypropylene (J229E manufactured by Prime Polymer Co., Ltd., MFR = 50)

[Thermal conductive filler]
<FIL-1>: Hexagonal boron nitride (PT-110 manufactured by Momentive Performance Materials)
<FIL-2>: Hexagonal boron nitride (SGP manufactured by Denki Kagaku Kogyo Co., Ltd.)
<FIL-3>: Spherical boron nitride (PTX-60 manufactured by Momentive Performance Materials)
<FIL-4>: Spherical alumina (AS-40 manufactured by Showa Denko KK)
<FIL-5>: Spheroidized graphite (CGC-100 manufactured by Nippon Graphite Industry Co., Ltd.)
<FIL-6>: Magnesium carbonate (Magnesite MSL manufactured by Kamishima Chemical Industry Co., Ltd.)
<FIL-7>: Mn—Zn soft ferrite (BSF-547 manufactured by Toda Kogyo Co., Ltd.)
<FIL-8>: Aluminum hydroxide (BF013 manufactured by Nippon Light Metal Co., Ltd.)
Moreover, each evaluation was implemented with the following evaluation methods.

[Measurement of Particle Diameter of Domain in Modified Polyolefin Resin Composition]
The particle size was measured and observed using a transmission electron microscope JEM-1200EX manufactured by JEOL Ltd. at an acceleration voltage of 80 kV. The sample at that time was stained with ruthenium oxide and prepared by the frozen ultrathin section method.

[Thermal conductivity]
Using two disk-shaped samples having a thickness of 3 mm and a diameter of 21 mm, the thermal conductivity was measured by a method of sandwiching a sensor having a diameter of 4 mm with a hot disk method thermal property measuring apparatus TPA-501 manufactured by Kyoto Electronics Industry Co., Ltd.

[T-shaped peeling evaluation]
T-shaped peel evaluation was performed in accordance with “Test method for peel adhesive strength of adhesive” defined in JIS K 6854, using an autograph AG-2000A manufactured by Shimadzu Corporation, and a tensile test speed of 50 mm / min at 23 ° C. I went there. The test sample was prepared by sandwiching a film between two aluminum plates (25 mm × 150 mm × 0.5 mm thickness) and pressing and bonding at 200 ° C. for 1 minute.

[Shear strength evaluation]
Shear strength evaluation is in accordance with “Test method for tensile shear bond strength of adhesive” defined in JIS K 6850, using an autograph AG-2000A manufactured by Shimadzu Corporation, and a tensile test speed of 50 mm / min at 23 ° C. I went there. The test sample was prepared by sandwiching a film between a steel plate (25 mm × 100 mm) and a polypropylene plate (25 mm × 100 mm) and pressing and bonding at 200 ° C. for 1 minute. “Substrate rupture” means that the steel plate or the polypropylene plate itself is ruptured, and “interfacial peeling” means that it is peeled off at the bonding surface between the steel plate and polypropylene.

  The respective formulations and results are shown in Table 1. From Table 1, it can be seen that the thermoplastic resin composition of the present invention is a thermoplastic resin composition having both high thermal conductivity and good adhesion as compared with a composition outside the range of the composition.

  Further, as is clear from Examples 2, 3, 4 and Comparative Example 2 shown in Table 1, even if the same amount of the same kind is used as the thermally conductive filler (B), the modified polyolefin resin (A ) (Examples 2, 3 and 4) are surprisingly effective in that not only the adhesive property but also the thermal conductivity is significantly higher than when an unmodified polyolefin resin is used (Comparative Example 2). It can be seen that

  In the table, “impossible” was indicated for those that could not be measured because the molding process was difficult.

Claims (8)

(A) at least one compound selected from (b) an epoxy group-containing vinyl monomer, an unsaturated acid, and an unsaturated acid anhydride in the presence of a radical polymerization initiator in (b) a polyolefin-based resin, and (d) Modified polyolefin added with an aromatic vinyl monomer, wherein the proportion of (c) in the total weight of (a), (c) and (d) is in the range of 0.1 to 50% by weight A thermoplastic resin comprising a resin (A) and a thermally conductive filler (B), wherein the volume ratio of (A) / (B) is in the range of 85/15 to 25/75 Composition. Modified polyolefin resin (A) is (a) polyolefin resin, (b) in the presence of a radical polymerization initiator, (c) epoxy group-containing vinyl monomer, unsaturated acid, and unsaturated acid anhydride The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is obtained by melt-kneading at least one compound selected from the group consisting of: (d) an aromatic vinyl monomer. The thermoplastic resin composition according to claim 1 or 2, wherein the (a) polyolefin resin is a polypropylene resin having a majority amount of propylene units. Thermally conductive filler (B) is a composite of carbon compound, metal oxide, metal nitride, metal carbide, metal hydroxide, metal carbonate, crystalline silica, fired organic polymer, nitrogen carbide, Zn ferrite The thermoplastic resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin composition is at least one selected from ferrite, Fe-Al-Si ternary alloys, and metal powders. The thermally conductive filler (B) is at least one selected from graphite, diamond, aluminum oxide, magnesium oxide, boron nitride, aluminum nitride, aluminum hydroxide, magnesium carbonate, and Fe—Al—Si ternary alloy. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the composition is a thermoplastic resin composition. The polyolefin-type sheet | seat or film which has the heat welding property obtained from the thermoplastic resin composition of any one of Claims 1-5. The hot-melt-adhesive agent which has the heat-weldability obtained from the thermoplastic resin composition of any one of Claims 1-5. Bonded with at least one or more selected from the group consisting of the thermoplastic resin composition according to claim 1, the polyolefin sheet or film according to claim 6, and the hot melt adhesive according to claim 7. An adhesive body.