WO2010084845A1 - Resin composition and molded article comprising the same - Google Patents
Resin composition and molded article comprising the same Download PDFInfo
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- WO2010084845A1 WO2010084845A1 PCT/JP2010/050516 JP2010050516W WO2010084845A1 WO 2010084845 A1 WO2010084845 A1 WO 2010084845A1 JP 2010050516 W JP2010050516 W JP 2010050516W WO 2010084845 A1 WO2010084845 A1 WO 2010084845A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
- C08L77/08—Polyamides derived from polyamines and polycarboxylic acids from polyamines and polymerised unsaturated fatty acids
Definitions
- the present invention relates to a resin composition and a molded body comprising the same, and more particularly to a resin composition having melt fluidity during molding and a molded body comprising the same.
- thermoplastic resins used as raw materials for molding include polypropylene (PP), ABS, polyamide (PA6, PA66, etc.), polyester (PET, PBT, etc.), polycarbonate (PC), liquid crystal polyester (LCP), polyphenylene sulfide. (PPS). These resins are widely used in fields such as various electronic devices, electronic parts, and machine parts. These thermoplastic resins are improved in strength and heat resistance by blending reinforcing fillers such as talc and glass fiber, and various functions can be achieved by blending fillers having specific functions. Has been granted.
- Amorphous thermoplastic resins such as polycarbonate resin and ABS resin, which are excellent in surface appearance and low warpage of molded products, have been used in the casings of portable electronic devices such as PDAs, mobile phones, and personal computers.
- casings are also required to be thin molded products.
- talc, glass fiber, and the like have been blended as reinforcing materials in the aforementioned polycarbonate resin and ABS resin.
- the strength of the casing and the like is improved as the amount of the reinforcing material is increased, but the fluidity of the resin is lowered. For this reason, it is particularly difficult to form a thin and complex product such as a housing.
- JP62-1331033A has a thermally conductive resin molded product in which a thermoplastic resin is filled with graphite powder
- JP2001-151905A has a resin heat sink in which polyphenylene sulfide resin is filled with magnesium oxide or aluminum oxide.
- a highly heat conductive resin composition it is necessary to add a large amount of filler. As a result, there is a problem in that the moldability is remarkably lowered and the use of the resin composition is limited.
- an object of the present invention is to provide a resin composition excellent in melt fluidity at the time of processing such as injection molding and a molded body comprising the same.
- the gist of the present invention is as follows.
- the melt viscosity reducing agent (C) is a polyfunctional allyl compound (C1), and the polyfunctional allyl compound (C1) with respect to 100 parts by mass in total of the thermoplastic resin (A) and the filler (B).
- the content is 3 to 20 parts by mass.
- the melt viscosity reducing agent (C) is a dimer acid-based thermoplastic resin (C2), and the dimer acid-based thermoplastic resin (C2) for a total of 100 parts by volume of the thermoplastic resin (A) and the filler (B). ) Content is 10 to 45 parts by volume.
- the polyfunctional allyl compound (C1) is obtained by reacting the primary amine compound (D) represented by the following formula (i) with the polyfunctional compound (E) having an allyl group and a glycidyl group.
- the resin composition according to (1) which is an allyl compound.
- n 1 to 4 and R represents an aromatic or aliphatic 1 to 4 substituted residue.
- filler (B) is a thermally conductive filler (B1) having a thermal conductivity of 10 W / (m ⁇ K) or more. Resin composition.
- the thermally conductive filler (B1) is composed of flaky graphite having an average particle diameter of 1 to 300 ⁇ m, graphitized carbon fiber having an average fiber diameter of 1 to 30 ⁇ m and an average fiber length of 1 to 20 mm, and a hexagonal crystal structure.
- Scaly boron nitride having an average particle size of 1 to 200 ⁇ m, aluminum oxide having an average particle size of 0.5 to 150 ⁇ m, magnesium oxide having an average particle size of 0.5 to 150 ⁇ m, and an average particle size of 0.5 to 150 ⁇ m
- the resin composition according to (7) or (8) which is at least one selected from magnesium carbonate and zinc oxide having an average particle diameter of 0.5 to 150 ⁇ m.
- thermoplastic resin (A) is a polyamide resin.
- melt viscosity reducing agent (C) since it contains a predetermined amount of melt viscosity reducing agent (C), it is possible to provide a resin composition having excellent melt fluidity during processing and a molded product obtained thereby.
- melt viscosity reducing agent (C) is a polyfunctional allyl compound (C1)
- the polyfunctional allyl compound (C1) has a large number of allyl groups in one molecule.
- a resin composition having excellent mechanical properties and excellent melt fluidity during processing, and a molded product comprising the same Obtainable.
- thermoplastic resin (A) that can be used in the present invention is not particularly limited, but ethylene- ⁇ -olefin copolymers such as polyethylene, polypropylene, and ethylene-propylene copolymers, polymethylpentene, Polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyvinyl acetal, fluororesin (polyvinylidene fluoride, polytetrafluoroethylene, etc.), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate , Polylactic acid, polystyrene, polyacrylonitrile, styrene-acrylonitrile copolymer, ABS resin, polyphenylene ether (PPE), modified PPE, polyamide, polyimide, polyamideimide, polyether Ruimido, polymethacrylic acid esters of polymethyl methacrylate, poly
- polyamide resin examples include homopolyamide and copolyamide obtained by polymerization of lactam or aminocarboxylic acid, or polycondensation of diamine and carboxylic acid, and mixtures thereof.
- polyamide resin examples include polycapramide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polycoupleramide / polyhexamethylene adipamide copolymer (nylon 6/66) , Polyundecamide (nylon 11), polycapramide / polyundecamide copolymer (nylon 6/11), polydodecamide (nylon 12), polycoupler / polydodecamide copolymer (nylon 6/12), polyhexamethylene sebamide (nylon 610) , Polyhexamethylene dodecamide (nylon 612), polyundecamethylene adipamide (nylon 116), polyhexamethylene isophthalamide (nylon 6I), polyhexamethylene terephthalamide (Niro) 6T), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polycapramide (n
- the liquid crystal polymer that can be used in the present invention refers to a melt-processable polymer having a property capable of forming an optically anisotropic melt phase.
- a liquid crystal polymer has a property that polymer molecular chains take a regular parallel arrangement by receiving a shear stress in a molten state.
- Such polymer molecules are generally elongated, flat, fairly rigid along the long axis of the molecule, and have a plurality of chain extension bonds that are usually either coaxial or parallel. Examples include wholly aromatic or semi-aromatic polyesters, polyester imides, polyester amides, and mixtures thereof.
- liquid crystal polymer examples include liquid crystal polyester, liquid crystal polyester amide, liquid crystal polyester carbonate, and liquid crystal polyester elastomer.
- liquid crystalline polyester is preferable in terms of moldability.
- liquid crystal polyester examples include a polyester that forms an anisotropic melt phase composed of a structural unit selected from an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic dicarbonyl unit, an ethylenedioxy unit, and the like.
- the resin composition of the present invention contains a filler (B).
- a filler (B) used by this invention The thing used for the purpose of improving a mechanical property, a thermal property, etc., electroconductivity, thermal conductivity, magnetism, piezoelectricity, electromagnetic wave absorption As typical examples, those used for the purpose of imparting functions such as flame retardancy and ultraviolet absorption can be given.
- Examples of the form of the filler (B) include a spherical shape, a powder shape, a fiber shape, a needle shape, a scale shape, a scale shape, a whisker shape, a microcoil shape, and a nanotube shape.
- the filler (B) include acetylene black, ketjen black, carbon nanotube, carbon nanofiber, metal powder (silver, copper, aluminum, titanium, nickel, tin, iron, stainless steel, etc.), conductive zinc oxide , Tin oxide, indium oxide, various ferrites, magnetic iron oxide, aluminum oxide, magnesium oxide, zinc oxide, magnesium carbonate, silicon carbide, aluminum nitride, boron nitride, silicon nitride, carbon, graphite, barium titanate, zirconate titanate Lead, potassium titanate, zonotlite, mica, talc, montmorillonite, hydrotalcite, calcium carbonate, zinc carbonate, wollastonite, barium sulfate, molybdenum disulfide, ethylene fluoride (for example, Teflon (registered trademark) powder, silica, Glass beads, Las balloon, titanium oxide, aluminum hydroxide, magnesium hydroxide, antimony trioxide, boric acid, zinc borate, ce
- the volume ratio (A / B) between the thermoplastic resin (A) and the filler (B) [including a heat conductive filler (B1) described later] is 20/80 to 95. / 5 is preferable, 30/70 to 90/10 is more preferable, and 30/70 to 60/40 is particularly preferable.
- the blending amount of the filler (B) is less than 5% by volume, the effect of blending the filler may not be sufficiently obtained.
- the blending amount exceeds 80% by volume the fluidity is remarkably lowered during molding. In some cases, the load of the engine becomes too high and the operability is lowered.
- a thermally conductive filler (B1) having a thermal conductivity of 10 W / (m ⁇ K) or more is used as the filler (B).
- the heat conductive filler (B1) either a conductive filler or an insulating filler can be used.
- the thermal conductivity of the heat conductive filler (B1) can be measured using the sintered product.
- thermally conductive filler (B1) (representing a representative value of thermal conductivity [unit: W / (m ⁇ K)] in parentheses), aluminum oxide (36), magnesium oxide (60 ), Zinc oxide (25), magnesium carbonate (15), silicon carbide (160), aluminum nitride (170), boron nitride (210), silicon nitride (40), carbon (10 to several hundreds), graphite (10 to Hundreds of inorganic fillers, silver (427), copper (398), aluminum (237), titanium (22), nickel (90), tin (68), iron (84), stainless steel (15), etc. Metal-based fillers. These can be used alone or in combination of two or more.
- the average particle diameter of the heat conductive filler (B1) is preferably 0.5 to 300 ⁇ m, more preferably 1 to 150 ⁇ m, excluding specific particles described later. If the average particle size is less than 0.5 ⁇ m, an agglomerate is likely to occur due to poor dispersion, and a uniform molded product cannot be obtained, resulting in a decrease in mechanical properties and a variation in thermal conductivity. If the average particle size exceeds 300 ⁇ m, it may be difficult to fill the resin in a high concentration or the surface of the molded product may become rough.
- thermally conductive filler (B1) because of its high thermal conductivity efficiency when blended into the thermoplastic resin (A). It is preferable. In view of economy, it is preferable to use aluminum oxide, magnesium oxide, magnesium carbonate, or zinc oxide.
- Examples of the form of the graphite filler that can be used in the present invention include a spherical shape, a powder shape, a fiber shape, a needle shape, a scale shape, a whisker shape, a microcoil shape, and a nanotube shape.
- scaly graphite and graphitized carbon fiber are particularly preferable because they can increase the heat conduction efficiency when blended with the thermoplastic resin (A).
- the average particle size of the flake graphite is preferably 1 to 300 ⁇ m, and more preferably 5 to 150 ⁇ m. If the average particle size is less than 1 ⁇ m, agglomerates are likely to occur due to poor dispersion, and thus a uniform molded product cannot be obtained, and the mechanical properties may be lowered or the thermal conductivity may be varied. When the average particle size exceeds 300 ⁇ m, it becomes difficult to fill the resin composition at a high concentration, and the surface of the molded product may become rough.
- the graphitized carbon fiber is preferably pitch-based carbon fiber, which is described in, for example, JP2003-49327A.
- graphite is obtained by firing at a high temperature of 1000 to 3000 ° C. using mesophase pitch as a raw material.
- Pitch-based carbon fibers with improved chemical conversion are preferred.
- the degree of graphitization is not particularly limited, but the thermal conductivity in the length direction increases as the graphite fiber is approached.
- the thermal conductivity in the length direction of the graphitized carbon fiber is usually 100 W / (m ⁇ K) or more, preferably 500 W / (m ⁇ K) or more.
- the average fiber diameter of the graphitized carbon fiber is preferably 1 to 30 ⁇ m, more preferably 5 to 20 ⁇ m.
- the average fiber diameter is less than 1 ⁇ m, sufficient thermal conductivity cannot be obtained, and when the average fiber diameter exceeds 30 ⁇ m, moldability and the like may be deteriorated.
- the average fiber length of the graphitized carbon fiber is preferably 1 to 20 mm, and more preferably 3 to 15 mm. If the average fiber length is less than 1 mm, sufficient thermal conductivity cannot be obtained. The longer the average fiber length, the higher the thermal conductivity, the higher the bending strength and the bending elastic modulus. However, when the average fiber length exceeds 20 mm, the fluidity is greatly lowered, which is not preferable in terms of moldability.
- Examples of commercially available products of graphitized carbon fiber include the product name “GRANOC” manufactured by Nippon Graphite Fiber Co., Ltd., and the product name “Dialead” manufactured by Mitsubishi Chemical Corporation.
- Examples of the form of boron nitride that can be used in the present invention include a spherical shape, a powdery shape, a fibrous shape, a needle shape, a scale shape, a whisker shape, a microcoil shape, and a nanotube shape. Since it becomes easy to orient in a surface direction when it is set as a molded body, and as a result, heat conductivity can be raised, it is preferable that it is scaly. By containing boron nitride, thermal conductivity can be improved without reducing the insulating properties of the resin composition.
- the average particle size of boron nitride is preferably 1 to 200 ⁇ m, and more preferably 5 to 100 ⁇ m.
- the average particle size is less than 1 ⁇ m, agglomerates are likely to occur due to poor dispersion, and therefore, a uniform molded product cannot be obtained, and mechanical properties may be deteriorated or thermal conductivity may be varied.
- the average particle diameter exceeds 200 ⁇ m, it becomes difficult to fill the resin composition at a high concentration, and the surface of the molded product may become rough.
- the crystal system of boron nitride is not particularly limited. Boron nitride having any crystal structure such as hexagonal system, cubic system, and the like is applicable. Of these, boron nitride having a hexagonal crystal structure is preferable because of its high thermal conductivity.
- Examples of the form of aluminum oxide, magnesium oxide, magnesium carbonate, and zinc oxide that can be used in the present invention include a spherical shape, a fiber shape, a spindle shape, a rod shape, a needle shape, a cylindrical shape, and a columnar shape. Since it can suppress the fall of the fluidity
- the average particle diameter of aluminum oxide, magnesium oxide, magnesium carbonate, and zinc oxide is preferably 0.5 to 150 ⁇ m, and more preferably 1 to 100 ⁇ m. If the average particle size is less than 0.5 ⁇ m, agglomerates are likely to occur due to poor dispersion, and therefore, a uniform molded product cannot be obtained, and mechanical properties may deteriorate or thermal conductivity may vary. When the average particle diameter exceeds 150 ⁇ m, it becomes difficult to fill the resin composition at a high concentration, and the surface of the molded product may become rough.
- the filler (B) used in the present invention may be subjected to a surface treatment with a coupling agent in order to improve adhesion to the thermoplastic resin (A).
- a coupling agent include silane coupling agents and titanium coupling agents such as ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- Aminosilane coupling agents such as ⁇ - (aminoethyl) - ⁇ -aminopropyldimethoxymethylsilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylethoxysilane, ⁇ - (3,4-epoxy Mention may be made of epoxy silane coupling agents such as (cyclohexyl) ethyltrimethoxysilane, and titanium coupling agents such as isopropyl tristearoyl titanate, isoprop
- the resin composition of the present invention contains a predetermined amount of fluidity improver (C).
- the fluidity improver (C) used in the present invention is either a polyfunctional allyl compound (C1) or a dimer acid-based thermoplastic resin (C2).
- the polyfunctional allyl compound (C1) is not particularly limited, but is required to be liquid at the melt processing temperature of the resin composition. Moreover, since the polyfunctional allyl compound (C1) can reduce the melt viscosity of the added resin, it will effectively act as a plasticizer.
- polyfunctional allyl compound (C1) examples include triallyl isocyanurate, monoglycidyl diallyl isocyanurate, diglycidyl monoallyl isocyanurate, trimethallyl isocyanurate, monoglycidyl dimethallyl isocyanurate, diglycidyl monometa.
- a polyfunctional allyl compound (C1) in addition to the above compound, a primary amine compound (D) represented by the following formula (i), a polyfunctional compound (E) having an allyl group and a glycidyl group, An allyl compound obtained by the above reaction can be used.
- n 1 to 4 and R represents an aromatic or aliphatic 1 to 4 substituted residue.
- a plurality of these amines can be used in combination for the purpose of adjusting various properties.
- the polyfunctional compound (E) having an allyl group and a glycidyl group to be reacted with the primary amine compound (D) is not particularly limited as long as it is a monomeric compound having both an allyl group and a glycidyl group.
- Examples of the polyfunctional compound (E) include monoglycidyl diallyl isocyanurate, diglycidyl monoallyl isocyanurate, monoglycidyl dimethallyl isocyanurate, diglycidyl monomethallyl isocyanurate, monoglycidyl diallyl cyanurate, diglycidyl monoary Lucyanurate, monoglycidyl dimethallyl cyanurate, diglycidyl monomethallyl cyanurate, allyl glycidyl amine, diallyl monoglycidyl amine, monoallyl diglycidyl amine, monoglycidyl dimethallyl amine, diglycidyl monomethallyl amine, glycidyl acrylic chlorene Tate, allyl glycidyl adipate, allyl glycidyl carbonate, allyl glycidyl dimethyl ammonium chloride, allyl glycid
- the polyfunctional compound (E) is preferably a compound having an isocyanurate in the skeleton, and particularly preferably monoglycidyl diallyl isocyanurate.
- the mixing ratio of the primary amine compound (D) and the polyfunctional compound (E) in the reaction may be such that the glycidyl group is 1 to 2 equivalents relative to 1 equivalent of the primary amine compound (D).
- the primary amine compound (D) is aliphatic, since the nucleophilicity of the amine is strong, two glycidyl groups can be added to one amine.
- a glycidyl group reacts in a 4 mol amount with respect to 1 mol of an aliphatic diamine.
- the primary amine compound (D) is aromatic
- the nucleophilicity of the amine is relatively weak, and the two glycidyl groups may not be added. That is, for example, it is considered that the glycidyl group reacts in an amount of approximately 2 moles per mole of the aromatic diamine.
- the method of reacting the primary amine compound (D) and the polyfunctional compound (E) is not particularly limited.
- the primary amine compound (D) and the polyfunctional compound are reacted.
- an appropriate reaction solvent may be used as necessary. What is necessary is just to set the heating temperature for making it react normally in the range of 80-200 degreeC.
- the atmosphere at the time of making it react is not specifically limited, What is necessary is just to react in air
- the atmosphere may be replaced with an inert gas such as nitrogen gas.
- reaction product thus obtained has a high boiling point, it is difficult to volatilize during melt processing, and can be used effectively as a crosslinking aid, end-capping agent and the like. Moreover, since it has many allyl groups in 1 molecule, an allyl group and resin can be bridge
- the addition amount of the polyfunctional allyl compound (C1) is 3 to 20 parts by mass with respect to 100 parts by mass in total of the thermoplastic resin (A) and the filler (B).
- the amount is preferably 4 to 15 parts by mass.
- the addition amount is less than 3 parts by mass, sufficient melt fluidity may not be obtained.
- the amount exceeds 20 parts by mass, the melt viscosity may be too low and pelletization may not be possible at the time of melt-kneading, or the physical properties of the resulting molded product may be significantly reduced.
- the polyfunctional allyl compound (C1) has a large number of allyl groups in one molecule, according to a known method, it can be used in combination with a crosslinking agent, or in combination with irradiation treatment such as electron beam or ⁇ -ray.
- the thermoplastic resin (A) can be crosslinked. Among them, it is preferable to crosslink with an electron beam or a ⁇ ray from the viewpoint that it can be processed in a short time after being formed into a desired shape. Since gamma rays are more permeable than electron rays and therefore irradiation is uniform, crosslinking using gamma rays is more preferred.
- a known electron accelerator or the like can be used for electron beam irradiation, and an irradiation apparatus such as a known cobalt 60 radiation source can be used for ⁇ -ray irradiation.
- the irradiation dose of the electron beam is preferably 1 to 300 kGy, more preferably 50 to 100 kGy. In the case of ⁇ -ray irradiation, the irradiation dose is preferably 10 to 100 kGy, more preferably 20 to 40 kGy. If the radiation dose exceeds the upper limit, the strength is reduced due to the decomposition of the resin, which is not preferable. Moreover, if less than the said lower limit, since the effect by bridge
- Irradiation atmosphere can be usually in the presence of air, but irradiation can be performed in a nitrogen atmosphere or in vacuum as desired.
- the dimer acid-based thermoplastic resin (C2) is a dimer acid that is a dimer of fatty acids such as soybean oil, tung oil, or toll oil, or a derivative that can produce an amide thereof, or an ester thereof. It is a thermoplastic resin obtained by polycondensation of a dicarboxylic acid containing a derivative that can be produced as a main acid component with components such as diamine and glycol.
- the main component of the dimer acid is a dimer, but may further contain a monomer or a trimer.
- the dicarboxylic acid containing the dimer acid which is a dimer of a fatty acid, a derivative capable of generating an amide thereof, or a derivative capable of generating an ester thereof may be hydrogenated.
- the dimer acid-based thermoplastic resin (C2) has a lower melt viscosity than the thermoplastic resin (A), and the addition of the dimer acid-based thermoplastic resin effectively reduces the melt viscosity of the resin.
- the dimer acid-based thermoplastic resin (C2) is a resin, has a high decomposition temperature, and does not volatilize during melt processing, so that it can be used effectively as a plasticizer. Furthermore, even if this is added, it is effective in that the mechanical strength is hardly lowered and bleeding does not occur.
- the dimer acid-based thermoplastic resin (C2) is not particularly limited, and examples thereof include polyamide and polyester. Of these, polyamide is preferable from the viewpoint of handleability and economy.
- the dimer acid-based polyamide is not particularly limited, and examples thereof include a polyamide resin composed of a dicarboxylic acid component containing a dimer acid or a derivative capable of forming an amide thereof and a diamine.
- Examples include reaction products of dimer acid, which is a dimer of fatty acids such as soybean oil, tung oil, and toll oil, and alkylpolyamines such as ethylenediamine and diethylenetriamine.
- the dimer acid-based polyester is not particularly limited, and examples thereof include a polyester resin composed of a dicarboxylic acid component containing a dimer acid or a derivative capable of forming an ester thereof and glycol.
- dimer acid which is a dimer of fatty acids such as soybean oil, tung oil, and toll oil, and a reaction product of a glycol component such as ethylene glycol or 1,4-butanediol with terephthalic acid or isophthalic acid. You can list things.
- the dimer acid-based polyamide and the dimer acid-based polyester can be used individually or in combination.
- the amount of the dimer acid-based thermoplastic resin (C2) added is 10 to 45 parts by volume with respect to 100 parts by volume in total of the thermoplastic resin (A) and the filler (B). It is necessary that it is 10 to 25 parts by volume. If the blending amount of the dimer acid-based thermoplastic resin (C2) is less than 10 parts by volume, the effect of blending the dimer acid-based thermoplastic resin (C2) may not be sufficiently obtained. On the other hand, if the blending amount exceeds 45 parts by volume, mechanical properties may be remarkably lowered, or pelletization may not be possible during melt kneading.
- the resin composition of the present invention has a pigment, a heat stabilizer, an antioxidant, a weathering agent, a flame retardant, a lubricant, a release agent, an antistatic agent, a crystal nucleus material, and a compatibilization as long as the characteristics are not significantly impaired An agent or the like can be added.
- heat stabilizers and antioxidants include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides, and the like.
- Examples of the flame retardant include hydrated metal compounds (such as aluminum hydroxide and magnesium hydroxide), nitrogen-containing compounds (melamine-based and guanidine-based), phosphorus-based flame retardants, halogen-based flame retardants, and inorganic flame retardants.
- Examples of the crystal nucleus material include a sorbitol compound, benzoic acid and a metal salt of the compound, a phosphate metal salt, a rosin compound, and the like.
- Examples of the compatibilizer include ionomer compatibilizers, oxazoline compatibilizers, elastomer compatibilizers, reactive compatibilizers, and copolymer-based compatibilizers. These additives may be used alone or in combination of two or more. The method for mixing these with the resin composition of the present invention is not particularly limited.
- the resin composition of the present invention comprises a thermoplastic resin (A), a filler (B), a polyfunctional allyl compound (C1) or a dimer acid-based thermoplastic resin (C2), and if necessary.
- Various additives can be produced by melt-kneading using a general extruder such as a single screw extruder, a twin screw extruder, a roll kneader, or a Brabender. At this time, it is also effective to use a static mixer or a dynamic mixer together. In order to improve the kneading state, it is preferable to use a twin screw extruder.
- the filler (B) and the polyfunctional allyl compound (C1) or the dimer acid-based thermoplastic resin (C2) are not particularly limited, but in the extruder, from a hopper or using a side feeder. Can be added.
- the resin composition of the present invention can be formed into a molded body by molding it into a desired shape using a known melt molding technique such as injection molding, compression molding, extrusion molding, transfer molding, or sheet molding. After the resin composition is molded into a desired shape, the resin can be crosslinked by irradiation with radiation as described above.
- a molded body obtained by molding a resin composition containing a thermally conductive filler (B1) having a thermal conductivity of 10 W / (m ⁇ K) or more include semiconductor elements and resistors.
- Electrical and electronic parts such as sealing materials for connectors, connectors, sockets, relay parts, coil bobbins, optical pickups, oscillators, computer-related parts; VTRs, TVs, irons, air conditioners, stereos, vacuum cleaners, refrigerators, rice cookers Household electrical product parts such as lighting fixtures; Heat dissipation members for releasing heat from electronic components such as heat dissipation sheets, heat sinks and fans; Lighting fixture components such as lamp sockets, lamp reflectors and lamp housings; Compact discs, laser discs Audio product parts such as speakers; optical cable ferrules, mobile phones, fixed phones, fax machines Communication equipment parts such as modems and modems; Copying machines such as separation claws and heater holders, printer-related parts; machine parts such as impellers, fan gear
- test methods for various physical property values are as follows.
- MFR melt flow rate
- Thermal conductivity Thermal conductivity (lambda) calculated
- ⁇ ⁇ Cp ⁇ : thermal conductivity (W / (m ⁇ K)) ⁇ : Thermal diffusivity (m 2 / sec) ⁇ : Density (g / m 3 ) Cp: Specific heat (J / g ⁇ K)
- the thermal diffusivity ⁇ was measured by a laser flash method using a laser flash method thermal constant measuring device TC-7000 (manufactured by ULVAC-RIKO, Inc.) in the resin flow direction of the bending test piece prepared in [2].
- the density ⁇ was measured using an electronic hydrometer ED-120T (manufactured by Mirage Trading Co.).
- the specific heat Cp was measured using a differential scanning calorimeter DSC-7 (manufactured by Perkin Elmer) under the condition of a heating rate of 10 ° C./min.
- PA6A polyamide 6 obtained by polymerization of lactam (relative viscosity 2.6, density 1.13 g / cm 3 )
- PA6B Polyamide 6 obtained by polymerization of lactam (relative viscosity 1.9, density 1.13 cm 3 )
- PA66 polyamide 66 obtained by polymerization of hexamethylenediamine and adipic acid (relative viscosity 2.8, density 1.14 cm 3 )
- LCP Liquid crystalline polyester (Rodlan LC-5000 manufactured by Unitika Ltd., density 1.41 g / cm 3 )
- PA12 Polyamide 12 (Rilsan AMN manufactured by Arkema, relative viscosity 2.3, density 1.01 g / cm 3 )
- -PP Polypropylene (Nippon Polypro Corporation MA1B, density 0.9 g / cm3)
- a 5 mg sample was heated from room temperature to 600 ° C. at a temperature increase rate of 20 ° C./min in a nitrogen-substituted atmosphere, and the sample mass change was measured. did.
- decrease temperature by the TGA measurement of the obtained powder was 375 degreeC.
- the 5% mass reduction temperature measured by MXDA TGA was 52 ° C.
- the melting point of the obtained powder was in the range of 55-70 ° C.
- DAMGIC was adjusted to 1 equivalent with respect to 1 equivalent of MXDA. Otherwise, synthesis was carried out in the same manner as in C11 to obtain a colorless and transparent liquid. The obtained liquid was gradually cooled to room temperature, and the solidified solid was pulverized to obtain a white powder of a polyfunctional allyl compound (C12).
- the 5% mass reduction temperature of the obtained powder by TGA measurement was 335 ° C.
- the melting point of the obtained powder was in the range of 50-60 ° C.
- HMDA Hexamethylenediamine
- D the primary amine compound
- synthesis was carried out in the same manner as in C11 to obtain a colorless and transparent liquid.
- the obtained liquid was gradually cooled to room temperature, and the solid produced at that time was pulverized to obtain a white powder of a polyfunctional allyl compound (C13).
- the 5% mass reduction temperature of the obtained powder by TGA measurement was 356 ° C.
- the 5% mass reduction temperature by TGA measurement of HMDA was 76 ° C.
- the melting point of the obtained powder was in the range of 35 to 45 ° C.
- MFR melt flow rate
- Plasticizer-HB p-hydroxybenzoic acid alkyl ester
- Example 1 30 parts by mass of polyamide 6 resin (PA6A) and 5 parts by mass of polyfunctional allyl compound (C12) are supplied to a main hopper of a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd .: TEM26SS, screw diameter 26 mm) at 260 ° C. And melted. In the middle, 70 parts by mass of glass fiber (GF) was supplied from the side feeder and sufficiently melt-kneaded. And after extruding in the shape of a strand and cooling and solidifying, it cut
- PET-B twin-screw extruder
- Example 1 Comparative Example 1 Compared with Example 1, it changed so that polyfunctional allyl compound (C1) might not be added. Other than that obtained the resin composition like Example 1, this was injection-molded, and the moldability was evaluated. The evaluation results are shown in Table 1. During the kneading and injection molding operations, no generation of volatile gases was observed.
- Examples 2 to 8, Comparative Examples 2 to 7 Compared with Example 1, the thermoplastic resin (A), the filler (B), and the polyfunctional allyl compound (C1) were changed to the types and amounts shown in Table 1, respectively. Other than that was carried out similarly to Example 1, and obtained the resin composition. And this was injection-molded and the moldability was evaluated.
- the fibrous filler is supplied from the middle by the side feeder, the other fillers are supplied from the main hopper, and triallyl cyanurate (TAIC), which is a liquid, is injected from the middle of the kneader using a pump, and melt-kneaded. Carried out.
- TAIC triallyl cyanurate
- Example 9 In the main hopper of the same twin-screw extruder used in Example 1, 41 parts by mass of polyamide 6 resin (PA6B), 59 parts by mass of flaky graphite (GrA) as a thermally conductive filler (B1), 4 parts by mass of monoglycidyl isocyanurate (DAMGIC) was supplied and melt-kneaded at 250 ° C. And after extruding in the shape of a strand and cooling and solidifying, it cut
- PA6B polyamide 6 resin
- RhA flaky graphite
- DAMGIC monoglycidyl isocyanurate
- the MFR was measured under the conditions of 250 ° C. and a load of 100 kg, and it was 100 g / 10 min.
- this resin composition was injection-molded by the same injection molding machine used in Example 1 at a cylinder temperature of 260 ° C., a mold temperature of 100 ° C., an injection time of 20 seconds, and a cooling time of 10 seconds. A molded body of was obtained. Note that generation of volatile gas was not observed in the kneading and injection molding operations.
- thermoplastic resin (A), the thermally conductive filler (B1), the polyfunctional allyl compound (C1), other fillers, and other plasticizers are shown in Table 2, respectively. I changed the amount. Other than that was carried out similarly to Example 1, and obtained the resin composition. The resin composition was injection molded and various physical properties were measured. At that time, the fibrous filler was supplied from the middle by the side feeder, and the other fillers were supplied from the main hopper.
- Triallyl cyanurate (TAIC) which is a liquid, was injected from the middle of the kneader using a pump to carry out melt kneading.
- Example 16 a large amount of volatile gas was generated during kneading and injection molding.
- Example 16 triallyl cyanurate bleeded out on the surface of the obtained molded body.
- the molded bodies obtained in Examples 10, 12, 14, 16, 17, 19 and Comparative Examples 8, 11, and 14 were irradiated with gamma rays using cobalt 60 as a radiation source at 30 kGy, intensity measurements were then performed, and gamma irradiation was performed. The physical properties before and after were compared.
- Table 2 summarizes the evaluation results of Examples 9 to 27 and Comparative Examples 8 to 18.
- Examples 9 to 27 had a large MFR value and excellent moldability because the polyfunctional allyl compound (C1) functions as a plasticizer. In contrast, in Comparative Examples 8 to 13 and Comparative Examples 15 to 17, the polyfunctional allyl compound (C1) as a plasticizer was not blended or was too little. The MFR value was small and inferior in moldability as compared with the examples in which the amount was appropriate and the other conditions were the same.
- Examples 21 to 26 and Comparative Examples 15 to 17 were blended with a large amount of the filler (B), but Examples 21 to 26 had a predetermined amount of the polyfunctional allyl compound (C1). It was possible to lower the molding temperature as compared with Comparative Examples 15 to 17.
- Comparative Example 14 when a commercially available plasticizer was blended, the MFR value was high and the moldability was excellent, but the mechanical performance of the molded body was inferior to that of the Example.
- Comparative Example 18 since the blending amount of the polyfunctional allyl compound (C1) was too large, the melt viscosity was too low, and it was not possible to extrude into a strand shape during melt kneading and solidify by cooling. could not be produced.
- Example 28 The main hopper of the same twin-screw extruder used in Example 1 was supplied with 35% by volume of polyamide 6 resin (PA6A) and 15% by volume of dimer acid-based thermoplastic resin (C21) and melted at 260 ° C. . In the middle, 50% by volume of glass fiber (GF) was supplied from the side feeder, and after sufficiently melt-kneaded, the melt-kneaded product was extruded into a strand shape and cooled and solidified. Then, it cut
- PA6A polyamide 6 resin
- C21 dimer acid-based thermoplastic resin
- Example 19 (Comparative Example 19) Compared to Example 28, no dimer acid based thermoplastic resin (C2) was added. Otherwise in the same manner as in Example 28, a resin composition was obtained. The obtained resin composition was injection-molded to evaluate moldability. The evaluation results are shown in Table 3. During the kneading and injection molding operations, no generation of volatile gases was observed.
- Example 29 to 37 Comparative Examples 20 to 26
- the thermoplastic resin (A), the filler (B), and the dimer acid-based thermoplastic resin (C2) were changed to the types and amounts shown in Table 3, respectively. Otherwise in the same manner as in Example 28, a resin composition was obtained. At that time, the fibrous filler was supplied from the middle by the side feeder, and the other fillers were supplied from the main hopper to carry out melt kneading. The obtained resin composition was injection-molded to evaluate moldability. The evaluation results are summarized in Table 3.
- Examples 28 to 37 had good moldability because the dimer acid-based thermoplastic resin (C2) was blended.
- the dimer acid-based thermoplastic resin (C2) was not blended or the blending amount was too small. Therefore, under the same molding conditions as in Examples 28 to 37, the surface of the molded piece was smooth. It was inferior in property, or a molded piece having a predetermined size could not be obtained.
- Example 38 In the main hopper of the same twin-screw extruder used in Example 1, polyamide 6 resin (PA6A) 50% by volume, scaly graphite (GrA) 40% by volume as the heat conductive filler (B1), 10% by volume of dimer acid-based polyamide (C21) was supplied, and melt kneading was performed at 260 ° C. Then, the melt-kneaded product was extruded into a strand shape, cooled and solidified, and cut into a pellet shape to obtain a resin composition.
- PA6A polyamide 6 resin
- GrA scaly graphite
- C21 dimer acid-based polyamide
- MFR was measured under the conditions of 270 ° C. and a load of 100 kg, and it was 158 g / 10 min.
- this resin composition was injection molded at a cylinder temperature of 270 ° C., a mold temperature of 80 ° C., an injection time of 20 seconds, and a cooling time of 10 seconds.
- a shaped sample was injection molded.
- Example 39 to 56 Comparative Examples 27 to 40
- thermoplastic resin (A) the thermally conductive filler (B1), the dimer acid-based thermoplastic resin (C2), other fillers, and other plasticizers are shown in Table 4, respectively. And changed the amount. Otherwise in the same manner as in Example 38, a resin composition was obtained. The resin composition was injection molded and various physical properties were measured. At that time, the fibrous filler was supplied from the middle by the side feeder, and the other fillers were supplied from the main hopper to carry out melt kneading.
- Table 4 shows the evaluation results of Examples 38 to 46 and Comparative Examples 27 to 34
- Table 5 shows the evaluation results of Examples 47 to 56 and Comparative Examples 35 to 40.
- Examples 38 to 56 since the dimer acid-based thermoplastic resin (C2) functioned as a plasticizer, the MFR value was large and the moldability was excellent. On the other hand, in Comparative Examples 27 to 30 and Comparative Examples 32 to 40, since the dimer acid-based thermoplastic resin (C2) was not blended or was too little, the blending amount of the dimer acid-based thermoplastic resin (C2) was changed. The MFR value was small and inferior in moldability as compared with the examples that were appropriate and other conditions were the same.
- Examples 44 to 46 and Comparative Examples 32 to 34 were blended with a large amount of the filler (B), but Examples 44 to 46 had a predetermined amount of dimer acid-based thermoplastic resin (C2 ), The molding temperature could be lowered as compared with Comparative Examples 32-34.
- Comparative Example 31 a commercially available plasticizer was blended. In this case, although the MFR value was high and the moldability was excellent, the plasticizer was volatilized at the time of melt kneading, and the mechanical performance of the molded product was inferior to that of the example.
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Abstract
Description
ここで、n=1~4、Rは芳香族系もしくは脂肪族系の1~4置換残基を示す。 R- (NH 2 ) n (i)
Here, n = 1 to 4 and R represents an aromatic or aliphatic 1 to 4 substituted residue.
ここで、n=1~4、Rは芳香族系もしくは脂肪族系の1~4置換残基を示す。 R- (NH 2 ) n (i)
Here, n = 1 to 4 and R represents an aromatic or aliphatic 1 to 4 substituted residue.
熱可塑性樹脂組成物のペレットについて、降下式フローテスター(東洋精機製作所社製)を用い、所定荷重、所定温度でのMFR値を測定した。このときのオリフィスは、直径1mm×長さ10mmのものを使用した。 [1] MFR (melt flow rate):
The pellets of the thermoplastic resin composition were measured for MFR values at a predetermined load and a predetermined temperature using a descending flow tester (manufactured by Toyo Seiki Seisakusho). At this time, an orifice having a diameter of 1 mm and a length of 10 mm was used.
ASTM規格D-790に記載の方法に準じて測定した。 [2] Flexural strength, flexural modulus:
The measurement was performed according to the method described in ASTM standard D-790.
ASTM規格D-256に記載の方法に準じて、ノッチ付試験片を用いてアイゾッド衝撃強度を測定した。 [3] Impact strength:
According to the method described in ASTM standard D-256, Izod impact strength was measured using a notched specimen.
熱伝導率λは、熱拡散率α、密度ρ、比熱Cpを下記方法により求め、その積として次式で算出した。 [4] Thermal conductivity:
Thermal conductivity (lambda) calculated | required thermal diffusivity (alpha), density (rho), and specific heat Cp by the following method, and computed it with the following Formula as the product.
λ:熱伝導率(W/(m・K))
α:熱拡散率(m2/sec)
ρ:密度(g/m3)
Cp:比熱(J/g・K)
熱拡散率αは、[2]で作製した曲げ試験片の樹脂流れ方向について、レーザーフラッシュ法熱定数測定装置TC-7000(アルバック理工社製)を用い、レーザーフラッシュ法にて測定した。密度ρは、電子比重計ED-120T(ミラージュ貿易社製)を用いて測定した。比熱Cpは、示差走査熱量計DSC―7(パーキンエルマー社製)を用い、昇温速度10℃/分の条件で測定した。 λ = αρCp
λ: thermal conductivity (W / (m · K))
α: Thermal diffusivity (m 2 / sec)
ρ: Density (g / m 3 )
Cp: Specific heat (J / g · K)
The thermal diffusivity α was measured by a laser flash method using a laser flash method thermal constant measuring device TC-7000 (manufactured by ULVAC-RIKO, Inc.) in the resin flow direction of the bending test piece prepared in [2]. The density ρ was measured using an electronic hydrometer ED-120T (manufactured by Mirage Trading Co.). The specific heat Cp was measured using a differential scanning calorimeter DSC-7 (manufactured by Perkin Elmer) under the condition of a heating rate of 10 ° C./min.
供試樹脂組成物を十分に乾燥した後、射出成形機(東芝機械社製:EC-100型)を用い、幅13mm、長さ130mm、厚さ0.8mmの短冊状試料を射出成形した。得られた成形片の状態について、下記に示す基準で3段階の評価を行った。 [5] Moldability After sufficiently drying the test resin composition, a strip-shaped sample having a width of 13 mm, a length of 130 mm, and a thickness of 0.8 mm using an injection molding machine (Toshiba Machine Co., Ltd .: EC-100 type). Was injection molded. The state of the obtained molded piece was evaluated in three stages according to the following criteria.
やや劣る:所定のサイズに成形はできているが、成形片表面の平滑性が悪かった
不良:流動性が悪く、所定のサイズに成形できなかった
実施例と比較例で用いた原料を以下に示す。 Good: There was no problem in appearance and it could be molded to the specified size. Slightly inferior: Molded to the specified size, but the smoothness of the surface of the molded piece was bad. The raw materials used in Examples and Comparative Examples that could not be performed are shown below.
・PA6A:ラクタムの重合によって得られたポリアミド6(相対粘度2.6、密度1.13g/cm3)
・PA6B:ラクタムの重合によって得られたポリアミド6(相対粘度1.9、密度1.13cm3)
・PA66:ヘキサメチレンジアミンとアジピン酸の重合によって得られたポリアミド66(相対粘度2.8、密度1.14cm3)
・LCP:液晶ポリエステル(ユニチカ社製 ロッドランLC-5000、密度1.41g/cm3)
・PA12:ポリアミド12(アルケマ社製 リルサンAMN、相対粘度2.3、密度1.01g/cm3)
・PP:ポリプロピレン(日本ポリプロ社製 MA1B、密度0.9g/cm3)
・PLA:ポリ乳酸(NatureWorks社製、重量平均分子量(MW)=190,000、密度1.25g/cm3)
(2)充填材(B)
・GrA:鱗片状黒鉛(日本黒鉛工業社製、平均粒径40μm、熱伝導率100W/(m・K)、密度2.25g/cm3)
・GrB:鱗片状黒鉛(日本黒鉛工業社製、平均粒径130μm、熱伝導率100W/(m・K)、密度2.25g/cm3)
・GrCF:黒鉛化炭素繊維(日本グラファイトファイバー社製、平均繊維径9μm、平均繊維長3mm、密度2.2g/cm3)
・BN:六方晶系鱗片状窒化ホウ素(電気化学工業社製、平均粒径15μm、密度2.26g/cm3)
・ALOA:酸化アルミニウム(電気化学工業社製、平均粒径10μm、熱伝導率38W/m・K、密度3.97g/cm3)
・ALOB:酸化アルミニウム(電気化学工業社製、平均粒径50μm、熱伝導率38W/(m・K)、密度3.97g/cm3)
・TC:タルク(日本タルク社製 K-1、平均粒径8μm、密度2.7g/cm3)
・MgO:酸化マグネシウム(神島化学社製、平均粒径5μm、熱伝導率50W/(m・K)、密度3.58g/cm3)
・MgCO:炭酸マグネシウム(神島化学社製、平均粒径10μm、熱伝導率15W/(m・K)、密度3.05g/cm3)
・ZnO:酸化亜鉛(堺化学工業社製、平均粒径10μm、熱伝導率25W/(m・K)、密度 5.78g/cm3)
・AF:コポリパラフェニレン-3,4′-オキシジフェニレンテレフタルアミド繊維(帝人テクノプロダクツ社製、平均繊維径12μm、平均繊維長3mm、密度1.39g/cm3)
・GF:ガラス繊維(オーウェンスコーニング社製、平均繊維径10μm、平均繊維長3mm、密度2.50g/cm3)
(3)多官能性アリル化合物(C1)
・TAIC:トリアリルイソシアヌレート(日本化成社製 TAIC、液体、沸点150℃)
・DAMGIC:モノグリシジルジアリルイソシアヌレート(四国化成社製 DA-MGIC、固体、融点40℃、TGA測定による5%重量減少温度178℃)
・C11
1級アミン化合物(D)として1,3-ビス(アミノメチル)ベンゼン(MXDA)を用い、多官能性化合物(E)としてモノグリシジルイソシアヌレート(DAMGIC)を用い、MXDA1当量に対し、DAMGICが2当量になるよう秤り採り、これらを丸底フラスコに加え、攪拌しながら80℃で30分間加熱した。さらに180℃で30分間加熱して、無色透明な液状物を得た。得られた液状物を室温まで徐冷し、そのときに生成した固形物を粉砕して、多官能性アリル化合物(C11)の白色粉末を得た。 (1) Thermoplastic resin (A)
PA6A: polyamide 6 obtained by polymerization of lactam (relative viscosity 2.6, density 1.13 g / cm 3 )
PA6B: Polyamide 6 obtained by polymerization of lactam (relative viscosity 1.9, density 1.13 cm 3 )
PA66: polyamide 66 obtained by polymerization of hexamethylenediamine and adipic acid (relative viscosity 2.8, density 1.14 cm 3 )
LCP: Liquid crystalline polyester (Rodlan LC-5000 manufactured by Unitika Ltd., density 1.41 g / cm 3 )
PA12: Polyamide 12 (Rilsan AMN manufactured by Arkema, relative viscosity 2.3, density 1.01 g / cm 3 )
-PP: Polypropylene (Nippon Polypro Corporation MA1B, density 0.9 g / cm3)
PLA: Polylactic acid (manufactured by NatureWorks, weight average molecular weight (MW) = 190,000, density 1.25 g / cm 3 )
(2) Filler (B)
GrA: scaly graphite (manufactured by Nippon Graphite Industries Co., Ltd., average particle size 40 μm, thermal conductivity 100 W / (m · K), density 2.25 g / cm 3 )
GrB: scaly graphite (manufactured by Nippon Graphite Industry Co., Ltd., average particle size 130 μm, thermal conductivity 100 W / (m · K), density 2.25 g / cm 3 )
GrCF: graphitized carbon fiber (manufactured by Nippon Graphite Fiber, average fiber diameter 9 μm, average fiber length 3 mm, density 2.2 g / cm 3 )
BN: hexagonal scaly boron nitride (manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 15 μm, density 2.26 g / cm 3 )
ALOA: aluminum oxide (manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 10 μm, thermal conductivity 38 W / m · K, density 3.97 g / cm 3 )
ALOB: aluminum oxide (manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 50 μm, thermal conductivity 38 W / (m · K), density 3.97 g / cm 3 )
TC: Talc (K-1 manufactured by Nippon Talc Co., Ltd., average particle diameter 8 μm, density 2.7 g / cm 3 )
MgO: Magnesium oxide (manufactured by Kamishima Chemical Co., Ltd., average particle size 5 μm, thermal conductivity 50 W / (m · K), density 3.58 g / cm 3 )
MgCO: Magnesium carbonate (manufactured by Kamishima Chemical Co., Ltd., average particle size 10 μm, thermal conductivity 15 W / (m · K), density 3.05 g / cm 3 )
ZnO: Zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd., average particle size 10 μm, thermal conductivity 25 W / (m · K), density 5.78 g / cm 3 )
AF: Copolyparaphenylene-3,4'-oxydiphenylene terephthalamide fiber (manufactured by Teijin Techno Products, average fiber diameter 12 μm, average fiber length 3 mm, density 1.39 g / cm 3 )
GF: Glass fiber (Owens Corning, average fiber diameter 10 μm, average fiber length 3 mm, density 2.50 g / cm 3 )
(3) Polyfunctional allyl compound (C1)
・ TAIC: triallyl isocyanurate (TAIC, Nippon Kasei Co., Ltd., liquid, boiling point 150 ° C.)
DAMGIC: monoglycidyl diallyl isocyanurate (DA-MGIC, solid, melting point 40 ° C., 5% weight loss temperature 178 ° C. measured by TGA measurement)
・ C11
1,3-bis (aminomethyl) benzene (MXDA) is used as the primary amine compound (D), monoglycidyl isocyanurate (DAMGIC) is used as the multifunctional compound (E), and 2 DAMGICs per 1 equivalent of MXDA. They were weighed to an equivalent weight, added to a round bottom flask, and heated at 80 ° C. for 30 minutes with stirring. Furthermore, it heated at 180 degreeC for 30 minute (s), and the colorless and transparent liquid material was obtained. The obtained liquid was gradually cooled to room temperature, and the solid produced at that time was pulverized to obtain a white powder of a polyfunctional allyl compound (C11).
MXDA1当量に対し、DAMGICが1当量になるようにした。それ以外はC11の場合と同様にして合成を行い、無色透明な液状物を得た。得られた液状物を室温まで徐冷し、固化した固形物を粉砕して、多官能性アリル化合物(C12)の白色粉末を得た。 ・ C12:
DAMGIC was adjusted to 1 equivalent with respect to 1 equivalent of MXDA. Otherwise, synthesis was carried out in the same manner as in C11 to obtain a colorless and transparent liquid. The obtained liquid was gradually cooled to room temperature, and the solidified solid was pulverized to obtain a white powder of a polyfunctional allyl compound (C12).
1級アミン化合物(D)としてヘキサメチレンジアミン(HMDA)を用いた。それ以外はC11の場合と同様にして合成を行い、無色透明な液状物を得た。得られた液状物を室温まで徐冷し、そのときに生成した固形物を粉砕して、多官能性アリル化合物(C13)の白色粉末を得た。 ・ C13:
Hexamethylenediamine (HMDA) was used as the primary amine compound (D). Otherwise, synthesis was carried out in the same manner as in C11 to obtain a colorless and transparent liquid. The obtained liquid was gradually cooled to room temperature, and the solid produced at that time was pulverized to obtain a white powder of a polyfunctional allyl compound (C13).
・製造例1(C21)
ダイマー酸(築野食品工業社製、水素添加なし)/1,3-ビス(アミノメチル)ベンゼン=46.5/53.5(モル比)の割合の原料を反応槽に仕込み、240℃で2時間反応させた。反応終了後に払い出し、切断して、ダイマー酸ベースポリアミド樹脂ペレットを得た。得られたペレットの230℃、21.18Nでのメルトフローレート(MFR)は、1800g/minであった。 (4) Dimer acid based thermoplastic resin (C2)
・ Production Example 1 (C21)
Dimer acid (manufactured by Tsukino Food Industry Co., Ltd., without hydrogenation) / 1,3-bis (aminomethyl) benzene = 46.5 / 53.5 (molar ratio) was charged into the reaction vessel at 240 ° C. The reaction was performed for 2 hours. After completion of the reaction, it was discharged and cut to obtain dimer acid-based polyamide resin pellets. The resulting pellet had a melt flow rate (MFR) at 230 ° C. and 21.18 N of 1800 g / min.
ダイマー酸(築野食品工業社製、水素添加なし)/65.3%ヘキサメチレンジアミン水溶液/カプロラクタム=10.3/7.3/82.4(モル比)の割合の原料を反応槽に仕込み、250℃で2時間反応させた。反応終了後に払い出し、切断してダイマー酸ベースポリアミド樹脂ペレットを得た。得られたペレットの230℃、21.18Nでのメルトフローレート(MFR)は、1300g/minであった。 ・ Production Example 2 (C22)
Dimer acid (manufactured by Tsukino Food Industry Co., Ltd., without hydrogenation) /65.3% hexamethylenediamine aqueous solution / caprolactam = 10.3 / 7.3 / 82.4 (molar ratio) were charged into the reaction vessel. And reacted at 250 ° C. for 2 hours. After completion of the reaction, it was discharged and cut to obtain dimer acid-based polyamide resin pellets. The resulting pellet had a melt flow rate (MFR) at 230 ° C. and 21.18 N of 1300 g / min.
ダイマー酸(築野食品工業社製、水素添加なし)/テレフタル酸/1,4ブタンジオール=13.2/26.8/60(モル比)の割合の原料を反応槽に仕込み、240℃にてエステル化反応を行い、次いで定法により、チタン触媒を添加し240℃にて3時間重縮合反応を行った。反応終了後に払い出し、切断して、ダイマー酸ベースポリエステル樹脂を得た。得られたペレットの200℃、21.18Nでのメルトフローレート(MFR)は、800g/minであった。 ・ Production Example 3 (C23)
Dimer acid (manufactured by Tsukino Food Industry Co., Ltd., without hydrogenation) / terephthalic acid / 1,4 butanediol = 13.2 / 26.8 / 60 (molar ratio) was charged into the reaction vessel and brought to 240 ° C. Then, an esterification reaction was carried out, and then a titanium catalyst was added by a conventional method, and a polycondensation reaction was carried out at 240 ° C. for 3 hours. After completion of the reaction, it was discharged and cut to obtain a dimer acid-based polyester resin. The resulting pellet had a melt flow rate (MFR) at 200 ° C. and 21.18 N of 800 g / min.
・HB:p-ヒドロキシ安息香酸アルキルエステル(花王社製 エキセパールHD-PB、液体、TGA測定による5%質量減少温度285℃)
(実施例1)
二軸押出機(東芝機械社製:TEM26SS、スクリュ径26mm)の主ホッパーに、ポリアミド6樹脂(PA6A)30質量部と、多官能性アリル化合物(C12)5質量部とを供給し、260℃で溶融した。途中、サイドフィーダーよりガラス繊維(GF)70質量部を供給し、十分に溶融混練した。そしてストランド状に押出して冷却固化した後、ペレット状に切断して、樹脂組成物を得た。 (5) Plasticizer-HB: p-hydroxybenzoic acid alkyl ester (Exepar HD-PB, liquid, Kao company, 5% mass reduction temperature 285 ° C. measured by TGA measurement)
Example 1
30 parts by mass of polyamide 6 resin (PA6A) and 5 parts by mass of polyfunctional allyl compound (C12) are supplied to a main hopper of a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd .: TEM26SS, screw diameter 26 mm) at 260 ° C. And melted. In the middle, 70 parts by mass of glass fiber (GF) was supplied from the side feeder and sufficiently melt-kneaded. And after extruding in the shape of a strand and cooling and solidifying, it cut | disconnected to the shape of a pellet, and obtained the resin composition.
実施例1に比べて、多官能性アリル化合物(C1)を添加しないように変更した。それ以外は実施例1と同様にして樹脂組成物を得て、これを射出成形して成形性の評価を行った。その評価結果を表1に示す。混練および射出成形操作の際において、揮発ガスの発生は観測されなかった。 (Comparative Example 1)
Compared with Example 1, it changed so that polyfunctional allyl compound (C1) might not be added. Other than that obtained the resin composition like Example 1, this was injection-molded, and the moldability was evaluated. The evaluation results are shown in Table 1. During the kneading and injection molding operations, no generation of volatile gases was observed.
実施例1と比べて、熱可塑性樹脂(A)、充填材(B)、多官能性アリル化合物(C1)をそれぞれ表1に示す種類と量に変えた。それ以外は実施例1と同様にして、樹脂組成物を得た。かつ、これを射出成形して成形性の評価を行った。繊維状充填剤はサイドフィーダーにより途中から供給し、それ以外の充填材は主ホッパーより供給し、液体であるトリアリルシアヌレート(TAIC)は混練機途中からポンプを用いて注入して、溶融混練を実施した。 (Examples 2 to 8, Comparative Examples 2 to 7)
Compared with Example 1, the thermoplastic resin (A), the filler (B), and the polyfunctional allyl compound (C1) were changed to the types and amounts shown in Table 1, respectively. Other than that was carried out similarly to Example 1, and obtained the resin composition. And this was injection-molded and the moldability was evaluated. The fibrous filler is supplied from the middle by the side feeder, the other fillers are supplied from the main hopper, and triallyl cyanurate (TAIC), which is a liquid, is injected from the middle of the kneader using a pump, and melt-kneaded. Carried out.
実施例1で用いたのと同じ二軸押出機の主ホッパーに、ポリアミド6樹脂(PA6B)41質量部と、熱伝導性充填材(B1)としての鱗片状黒鉛(GrA)59質量部と、モノグリシジルイソシアヌレート(DAMGIC)4質量部とを供給し、250℃で溶融混練した。そしてストランド状に押出して冷却固化した後、ペレット状に切断して、樹脂組成物を得た。 Example 9
In the main hopper of the same twin-screw extruder used in Example 1, 41 parts by mass of polyamide 6 resin (PA6B), 59 parts by mass of flaky graphite (GrA) as a thermally conductive filler (B1), 4 parts by mass of monoglycidyl isocyanurate (DAMGIC) was supplied and melt-kneaded at 250 ° C. And after extruding in the shape of a strand and cooling and solidifying, it cut | disconnected to the pellet form and obtained the resin composition.
実施例9と比べて、熱可塑性樹脂(A)、熱伝導性充填材(B1)、多官能性アリル化合物(C1)、その他の充填材、その他の可塑剤を、それぞれ表2に示す種類と量に変えた。それ以外は実施例1と同様にして、樹脂組成物を得た。この樹脂組成物を射出成形して、各種物性を測定した。その際に、繊維状充填剤はサイドフィーダーにより途中から供給し、それ以外の充填材は主ホッパーより供給した。液体であるトリアリルシアヌレート(TAIC)は混練機途中からポンプを用いて注入して、溶融混練を実施した。 (Examples 10 to 27, Comparative Examples 8 to 18)
Compared to Example 9, the thermoplastic resin (A), the thermally conductive filler (B1), the polyfunctional allyl compound (C1), other fillers, and other plasticizers are shown in Table 2, respectively. I changed the amount. Other than that was carried out similarly to Example 1, and obtained the resin composition. The resin composition was injection molded and various physical properties were measured. At that time, the fibrous filler was supplied from the middle by the side feeder, and the other fillers were supplied from the main hopper. Triallyl cyanurate (TAIC), which is a liquid, was injected from the middle of the kneader using a pump to carry out melt kneading.
実施例1で用いたのと同じ二軸押出機の主ホッパーに、ポリアミド6樹脂(PA6A)35容量%とダイマー酸ベース熱可塑性樹脂(C21)15容量%とを供給し、260℃で溶融した。途中、サイドフィーダーよりガラス繊維(GF)50容量%を供給し、十分に溶融混練したうえで溶融混練物をストランド状に押出して冷却固化した。その後、ペレット状に切断して樹脂組成物を得た。 (Example 28)
The main hopper of the same twin-screw extruder used in Example 1 was supplied with 35% by volume of polyamide 6 resin (PA6A) and 15% by volume of dimer acid-based thermoplastic resin (C21) and melted at 260 ° C. . In the middle, 50% by volume of glass fiber (GF) was supplied from the side feeder, and after sufficiently melt-kneaded, the melt-kneaded product was extruded into a strand shape and cooled and solidified. Then, it cut | disconnected to the pellet form and obtained the resin composition.
実施例28と比べて、ダイマー酸ベース熱可塑性樹脂(C2)を添加しなかった。それ以外は実施例28と同様にして、樹脂組成物を得た。得られた樹脂組成物を射出成形して、成形性の評価を行った。その評価結果を表3に示す。混練および射出成形操作の際において、揮発ガスの発生は観測されなかった。 (Comparative Example 19)
Compared to Example 28, no dimer acid based thermoplastic resin (C2) was added. Otherwise in the same manner as in Example 28, a resin composition was obtained. The obtained resin composition was injection-molded to evaluate moldability. The evaluation results are shown in Table 3. During the kneading and injection molding operations, no generation of volatile gases was observed.
実施例28と比べて、熱可塑性樹脂(A)、充填材(B)、ダイマー酸ベース熱可塑性樹脂(C2)を、それぞれ表3に示す種類と量に変えた。それ以外は実施例28と同様にして、樹脂組成物を得た。その際に、繊維状充填剤はサイドフィーダーにより途中から供給し、それ以外の充填材は主ホッパーより供給して、溶融混練を実施した。得られた樹脂組成物を射出成形して、成形性の評価を行った。評価結果をまとめて表3に示す。 (Examples 29 to 37, Comparative Examples 20 to 26)
Compared with Example 28, the thermoplastic resin (A), the filler (B), and the dimer acid-based thermoplastic resin (C2) were changed to the types and amounts shown in Table 3, respectively. Otherwise in the same manner as in Example 28, a resin composition was obtained. At that time, the fibrous filler was supplied from the middle by the side feeder, and the other fillers were supplied from the main hopper to carry out melt kneading. The obtained resin composition was injection-molded to evaluate moldability. The evaluation results are summarized in Table 3.
実施例1で用いたのと同じ二軸押出機の主ホッパーに、ポリアミド6樹脂(PA6A)50容量%と、熱伝導性充填材(B1)としての鱗片状黒鉛(GrA)40容量%と、ダイマー酸ベースポリアミド(C21)10容量%とを供給し、260℃で溶融混練を行った。そして、溶融混練物をストランド状に押出して冷却固化し、これをペレット状に切断して、樹脂組成物を得た。 (Example 38)
In the main hopper of the same twin-screw extruder used in Example 1, polyamide 6 resin (PA6A) 50% by volume, scaly graphite (GrA) 40% by volume as the heat conductive filler (B1), 10% by volume of dimer acid-based polyamide (C21) was supplied, and melt kneading was performed at 260 ° C. Then, the melt-kneaded product was extruded into a strand shape, cooled and solidified, and cut into a pellet shape to obtain a resin composition.
実施例38と比べて、熱可塑性樹脂(A)、熱伝導性充填材(B1)、ダイマー酸ベース熱可塑性樹脂(C2)、その他の充填材、その他の可塑剤を、それぞれ表4に示す種類と量に変えた。それ以外は実施例38と同様にして、樹脂組成物を得た。この樹脂組成物を射出成形して、各種物性を測定した。その際に、繊維状充填剤はサイドフィーダーにより途中から供給し、それ以外の充填材は主ホッパーより供給して、溶融混練を実施した。 (Examples 39 to 56, Comparative Examples 27 to 40)
Compared with Example 38, the thermoplastic resin (A), the thermally conductive filler (B1), the dimer acid-based thermoplastic resin (C2), other fillers, and other plasticizers are shown in Table 4, respectively. And changed the amount. Otherwise in the same manner as in Example 38, a resin composition was obtained. The resin composition was injection molded and various physical properties were measured. At that time, the fibrous filler was supplied from the middle by the side feeder, and the other fillers were supplied from the main hopper to carry out melt kneading.
Claims (12)
- 熱可塑性樹脂(A)と、充填材(B)と、所定量の溶融粘度低下剤(C)とを含み、前記所定量の溶融粘度低下剤(C)は、下記(a)と(b)とのいずれかであることを特徴とする樹脂組成物。
(a)溶融粘度低下剤(C)が多官能性アリル化合物(C1)であり、熱可塑性樹脂(A)と充填材(B)との合計100質量部に対する多官能性アリル化合物(C1)の含有量が3~20質量部である。
(b)溶融粘度低下剤(C)がダイマー酸ベース熱可塑性樹脂(C2)であり、熱可塑性樹脂(A)と充填材(B)との合計100容量部に対するダイマー酸ベース熱可塑性樹脂(C2)の含有量が10~45容量部である。 The thermoplastic resin (A), the filler (B), and a predetermined amount of the melt viscosity reducing agent (C), the predetermined amount of the melt viscosity reducing agent (C) are the following (a) and (b) And a resin composition characterized by that.
(A) The melt viscosity reducing agent (C) is a polyfunctional allyl compound (C1), and the polyfunctional allyl compound (C1) with respect to 100 parts by mass in total of the thermoplastic resin (A) and the filler (B). The content is 3 to 20 parts by mass.
(B) The melt viscosity reducing agent (C) is a dimer acid-based thermoplastic resin (C2), and the dimer acid-based thermoplastic resin (C2) for a total of 100 parts by volume of the thermoplastic resin (A) and the filler (B). ) Content is 10 to 45 parts by volume. - 多官能性アリル化合物(C1)が、骨格にイソシアヌレートを有する化合物であることを特徴とする請求項1記載の樹脂組成物。 The resin composition according to claim 1, wherein the polyfunctional allyl compound (C1) is a compound having isocyanurate in the skeleton.
- 多官能性アリル化合物(C1)が、下記式(i)で示される1級アミン化合物(D)と、アリル基及びグリシジル基を有する多官能性化合物(E)との反応によって得られるアリル化合物であることを特徴とする請求項1記載の樹脂組成物。
R-(NH2)n (i)
ここで、n=1~4、Rは芳香族系もしくは脂肪族系の1~4置換残基を示す。 The polyfunctional allyl compound (C1) is an allyl compound obtained by reacting a primary amine compound (D) represented by the following formula (i) with a polyfunctional compound (E) having an allyl group and a glycidyl group. The resin composition according to claim 1, wherein the resin composition is present.
R- (NH 2 ) n (i)
Here, n = 1 to 4 and R represents an aromatic or aliphatic 1 to 4 substituted residue. - アリル基及びグリシジル基を有する多官能性化合物(E)が、骨格にイソシアヌレートを有する化合物であることを特徴とする請求項3記載の樹脂組成物。 The resin composition according to claim 3, wherein the polyfunctional compound (E) having an allyl group and a glycidyl group is a compound having an isocyanurate in a skeleton.
- 骨格にイソシアヌレートを有する化合物が、モノグリシジルジアリルイソシアヌレートであることを特徴とする請求項2または4記載の樹脂組成物。 5. The resin composition according to claim 2, wherein the compound having isocyanurate in the skeleton is monoglycidyl diallyl isocyanurate.
- ダイマー酸ベース熱可塑性樹脂(C2)がポリアミド樹脂および/またはポリエステル樹脂であることを特徴とする請求項1記載の樹脂組成物。 The resin composition according to claim 1, wherein the dimer acid-based thermoplastic resin (C2) is a polyamide resin and / or a polyester resin.
- 充填材(B)が、10W/(m・K)以上の熱伝導率を有する熱伝導性充填材(B1)であることを特徴とする請求項1記載の樹脂組成物。 The resin composition according to claim 1, wherein the filler (B) is a thermally conductive filler (B1) having a thermal conductivity of 10 W / (m · K) or more.
- 熱可塑性樹脂(A)と熱伝導性充填材(B1)との容量比(A/B1)が、20/80~95/5であることを特徴とする請求項7記載の樹脂組成物。 The resin composition according to claim 7, wherein the volume ratio (A / B1) of the thermoplastic resin (A) and the thermally conductive filler (B1) is 20/80 to 95/5.
- 熱伝導性充填材(B1)が、平均粒径1~300μmの鱗片状黒鉛と、平均繊維径1~30μm、平均繊維長1~20mmの黒鉛化炭素繊維と、六方晶系結晶構造を有する平均粒径1~200μmの鱗片状窒化ホウ素と、平均粒径0.5~150μmの酸化アルミニウムと、平均粒径0.5~150μmの酸化マグネシウムと、平均粒径0.5~150μmの炭酸マグネシウムと、平均粒径0.5~150μmの酸化亜鉛とから選ばれる少なくとも一種であることを特徴とする請求項7記載の樹脂組成物。 The heat conductive filler (B1) has a flake graphite having an average particle diameter of 1 to 300 μm, a graphitized carbon fiber having an average fiber diameter of 1 to 30 μm and an average fiber length of 1 to 20 mm, and an average having a hexagonal crystal structure. Scaly boron nitride having a particle size of 1 to 200 μm, aluminum oxide having an average particle size of 0.5 to 150 μm, magnesium oxide having an average particle size of 0.5 to 150 μm, and magnesium carbonate having an average particle size of 0.5 to 150 μm, 8. The resin composition according to claim 7, wherein the resin composition is at least one selected from zinc oxide having an average particle size of 0.5 to 150 μm.
- 熱可塑性樹脂(A)がポリアミド樹脂であることを特徴とする請求項1記載の樹脂組成物。 2. The resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyamide resin.
- 請求項1から10までのいずれか1項記載の樹脂組成物を成形したものであることを特徴とする成形体。 A molded article obtained by molding the resin composition according to any one of claims 1 to 10.
- 請求項1から10までのいずれか1項記載の樹脂組成物を成形したうえで放射線を照射したものであることを特徴とする成形体。 A molded body, which is formed by molding the resin composition according to any one of claims 1 to 10 and irradiating with radiation.
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Also Published As
Publication number | Publication date |
---|---|
JP5686605B2 (en) | 2015-03-18 |
CN103122140B (en) | 2015-07-22 |
TW201035204A (en) | 2010-10-01 |
CN102203191A (en) | 2011-09-28 |
CN102203191B (en) | 2014-07-09 |
CN103122140A (en) | 2013-05-29 |
JPWO2010084845A1 (en) | 2012-07-19 |
TWI468453B (en) | 2015-01-11 |
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