CN103937078A - Thermal conductive resin composition and molded body - Google Patents
Thermal conductive resin composition and molded body Download PDFInfo
- Publication number
- CN103937078A CN103937078A CN201410026074.2A CN201410026074A CN103937078A CN 103937078 A CN103937078 A CN 103937078A CN 201410026074 A CN201410026074 A CN 201410026074A CN 103937078 A CN103937078 A CN 103937078A
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- CN
- China
- Prior art keywords
- resin composition
- conductive resin
- particle
- thermally conductive
- heat conductivity
- Prior art date
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- 239000002245 particle Substances 0.000 claims abstract description 85
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- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- OGWLTJRQYVEDMR-UHFFFAOYSA-F tetramagnesium;tetracarbonate Chemical compound [Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O OGWLTJRQYVEDMR-UHFFFAOYSA-F 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- CZIRZNRQHFVCDZ-UHFFFAOYSA-L titan yellow Chemical compound [Na+].[Na+].C1=C(C)C(S([O-])(=O)=O)=C2SC(C3=CC=C(C=C3)/N=N/NC3=CC=C(C=C3)C3=NC4=CC=C(C(=C4S3)S([O-])(=O)=O)C)=NC2=C1 CZIRZNRQHFVCDZ-UHFFFAOYSA-L 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/42—Insulated conductors or cables characterised by their form with arrangements for heat dissipation or conduction
- H01B7/421—Insulated conductors or cables characterised by their form with arrangements for heat dissipation or conduction for heat dissipation
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/267—Magnesium carbonate
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
Abstract
The invention provides a thermal conductive resin composition and a molded body formed by using the thermal conductive resin composition. The thermal conductive resin composition, although containing large amount of thermal conductive particles, has excellent molding processability, and can be used for obtaining, for example in injection molding, a molded body with excellent size stability, or in extrusion molding, a molded body with excellent smoothness and good mechanical properties. The thermal conductive resin composition provided by the invention contains terminal conductive particles with an average primary particle size of 0.1-30[mu]m, and thermoplastic resin. The terminal conductive particle includes a magnesium carbonate particle and a coating which is formed through a surface treating agent including methoxysilyl and alkyl.
Description
Technical field
The present invention relates to relate to a kind of can be for removing the thermally conductive resin composition of heat of the generations such as electric/electronic device and the formed body that makes this thermally conductive resin composition moulding.
Background technology
In recent years, in electric/electronic device field, be accompanied by high mechanization or densification, the signal of the progressive conduction of the simplicity high frequency more that becomes, the heat producing from the parts such as semi-conductor or power supply, light source is also increasing.Similarly, using the LED of wiring circuit to throw light in such equipment, the heat of generation is also increasing.Therefore, in such equipment, be the operation of guaranteeing that it is stable, heat radiation countermeasure just becomes extremely important.
Described heat radiation countermeasure a kind of, is arranged on the heat transmission parts of heating panel etc. on equipment sometimes.So-called heating panel is that the heat that radiating part is produced is passed on to radiating part effectively, and effectively makes heat disperse the parts of use by being full of the gap between the radiating parts such as heating part in electric/electronic device and scatterer.
In addition, the heat transmission parts of electric/electronic device, due to favourable aspect light weight and electric insulating quality, so can promote the sharply conversion from metallic substance to plastic material.But it is lower that the inorganicss such as plastic material and metallic substance are compared heat conductivity, the exothermicity that has heat transmission parts that obtain is low problem also.For solving described problem, by will be a large amount of the inorganics of (30% weight above or, be sometimes more than 50 % by weight) heat conductivity be coupled in plastic material, attempting improving its heat conductivity.
Yet if inorganics is coupled on plastic material in a large number, the melt viscosity of the resin combination obtaining can rise, exist cannot moulding by forming process afterwards problem.In addition,, even if can obtain formed body, also can there is its formed body weak problem that is highly brittle.
Therefore, patent documentation 1 discloses and has comprised the resin combination of implementing surface-treated heat conductivity inorganic filler and silicon rubber.In addition, patent documentation 2 discloses the resin combination of the interpolymer, thermoplastic elastomer, paraffin softening agent and the heat conductivity inorganic filler that comprise aromatic ethenyl compound and conjugated diene compound.
(conventional art document)
Patent documentation
Patent documentation 1: Unexamined Patent 11-209618 communique
Patent documentation 2: JP 2005-75895 communique
Summary of the invention
(problem that invention will solve)
But, there is following problem in the resin combination of patent documentation 1: if increase the use level of heat conductivity inorganic filler, a little less than the formed body obtaining can be highly brittle, if reduce the use level of heat conductivity inorganic filler, the formed body heat conductivity obtaining is not high.In addition, silicon rubber is owing to cannot recycle meeting bringing load to environment.And, in this resin combination, as heat conductivity inorganic filler, can use aluminum oxide, silicon-dioxide.Yet aluminum oxide hardness is high, there is the problem that makes mixing roll or forming machine wearing and tearing, on the other hand, silicon-dioxide heat conductivity is bad.In addition, the resin combination of patent documentation 2 is owing to also containing a large amount of tenderizers except main resin, so forming process is low, the mechanical property of formed body is insufficient.
The formed body that the object of this invention is to provide a kind of thermally conductive resin composition and make this thermally conductive resin composition moulding.Although it contains a large amount of heat conductivity particles, its forming process is excellent.For example, during injection molding, the formed body of excellent in dimensional stability can be obtained, during extrusion molding, smoothness excellence can be accessed, and the formed body of satisfactory mechanical property.
(solving the method for problem)
Thermally conductive resin composition of the present invention comprises heat conductivity particle and the thermoplastic resin that average primary particle diameter is 0.1～30 μ m.Described heat conductivity particle has magnesiumcarbonate particle and tectum.Described tectum, forms by having the surface treatment agent of alkoxysilane group and alkyl.
(effect of invention)
According to the present invention, the tectum covering carbonic acid magnesium particle forming by thering is the surface treatment agent of alkoxysilane group and alkyl, and use the heat conductivity particle with specific average primary particle diameter.Like this, for example, even if resin combination is in the situation that comprise a large amount of heat conductivity particles, its melt viscosity is also difficult to rise.Therefore, when making this resin combination injection molding, because resin combination is distributed on whole mould equably, so the dimensional stability of the formed body obtaining is good.In addition,, when this resin combination of extruding, can obtain the good formed body of smoothness.
In addition, owing to comprising described heat conductivity particle, so can obtain not damaging the formed body of mechanical property.In addition, the mechanical properties in the present invention refers to the tensile elongation of breaking point.Herein, the tensile elongation of the breaking point of formed body is higher, this means that thermoplastic resin maintains the extendability originally just having in formed body.Thermally conductive resin composition of the present invention, comprises above-mentioned thermoplastic resin, and can have moulding on the formed body of various shapes.
Therefore, according to the present invention, can provide a kind of thermally conductive resin composition, although it comprises a large amount of heat conductivity particles, but its forming process is excellent, for example, injection molding situation under, can obtain the formed body of excellent in dimensional stability, in the situation of extrusion molding, can obtain smoothness excellence, and the formed body of satisfactory mechanical property.
Embodiment
Thermally conductive resin composition of the present invention comprises heat conductivity particle and the thermoplastic resin that average primary particle diameter is 0.1～30 μ m.Described heat conductivity particle has magnesiumcarbonate particle and tectum.Described tectum forms by having the surface treatment agent (hereinafter referred to as " surface treatment agent ") of alkoxysilane group and alkyl.
In the present invention, heat conductivity particle, is covered and is formed by coating cap rock, and its magnesiumcarbonate particle (coatingparticles consisting of calcium carbonate) has heat conductivity.Described tectum, by having been used the surface treatment (cover and process) of the surface treatment agent with alkoxysilane group and alkyl to form described magnesiumcarbonate particle.By described tectal existence, described heat conductivity particle, its polymerization is controlled, and the dispersiveness of thermoplastic resin is improved.By like this, even resin combination in the situation that comprise a large amount of heat conductivity particles, also can obtain good forming process.Therefore the formed body satisfactory mechanical property, obtaining.In addition,, by described tectal existence, can improve the affinity of magnesiumcarbonate particle and thermoplastic resin.Like this, just can be suppressed in magnesiumcarbonate particle and thermoplastic interface and produce space, so can obtain the good formed body of heat conductivity.
In the present invention, as magnesiumcarbonate, preference is as anhydrous magnesium carbonate, magnesium basic carbonate etc.Described magnesiumcarbonate can be any one in natural product and synthetics.
The average primary particle diameter of described magnesiumcarbonate particle is 0.1～30 μ m degree preferably.Because median size is in described scope, so heat conductivity particle self is difficult to polymerization (i.e. the favorable dispersity to thermoplastic resin), there is sufficient heat conductivity simultaneously.Therefore, the mechanical property of the forming process of thermally conductive resin composition or the formed body that obtains can improve.In addition, in the present invention, average primary particle diameter is used electron microscope (scanning electronic microscope S-4300, Hitachi's system), for example, in enlarged image (3,000 times～10,000 times degree), ask for the mean value of the particle diameter on the particle of 20 observed～50 degree.
In the present invention, surface treatment agent is the compound with alkoxysilyl and alkyl.Particularly, as surface treatment agent, can enumerate methyltrimethoxy silane, dimethyldimethoxysil,ne, trimethylammonium methoxy silane, Union carbide A-162, ethyl trimethoxy silane, propyl trimethoxy silicane, propyl-triethoxysilicane, butyl trimethoxy silane, butyl triethoxyl silane, hexyl Trimethoxy silane, hexyl triethoxyl silane, octyl group Trimethoxy silane, octyltri-ethoxysilane, decyl trimethoxy, Trimethoxy silane, dodecyltrimethoxysilane, triethoxyl silane dodecyl etc.These surface treatments can be used singly or two or more kinds mixed.
The described surface treatment agent more preferably carbon number of alkyl is 6～12.If the carbon number of alkyl reaches more than 6, the hydrophobicity of heat conductivity particle can improve.Therefore, the affinity of heat conductivity particle and thermoplastic resin also can improve, and thermal conduction particle is further enhanced to the dispersiveness of thermoplastic resin.On the other hand, if the carbon number of alkyl, below 12, more easily forms the tectum to magnesiumcarbonate particle.
In addition, described surface treatment agent does not preferably contain the surface treatment agent of alkoxysilane group reactive functional groups in addition.In this case, surface treatment agent is not owing to comprising reactive functional group, i.e. wetting ability base, so the hydrophobicity of the heat conductivity particle after surface treatment uprises, the dispersiveness in thermoplastic resin also further improves.
Described tectum, preferably for magnesiumcarbonate particle 100 weight parts, the tectum forming with the surface treatment agent of 0.05～3 weight part.Because tectum is that surface treatment agent with the amount of described scope forms, so heat conductivity particle can further improve the dispersiveness to thermoplastic resin.
In described tectal formation (surface treatment), for example, the method that can use the public such as direct facture (such as drying process, slurry process, spraying etc.), integral blend method (such as direct method, mother material etc.), concentrate drying method to know.Wherein, as carrying out surface-treated method to magnesiumcarbonate particle simply, can be direct facture, preferred dry method wherein.
In described drying process, for example, on one side by Henschel mixer, be uniformly mixed magnesiumcarbonate particle, surface treatment agent splashed into magnesiumcarbonate particle or spray make its mixing on one side, by carrying out as required heat treated, obtain heat conductivity particle.Heat conductivity particle after tectum forms, due to polymerization sometimes, so preferably use ball mill etc. to pulverize.In addition, surface treatment agent, preferably by after the organic solvent dilutings such as alcohol, then splashes into magnesiumcarbonate particle or it is sprayed, thereby forms tectum.
The ratio of the heat conductivity particle that thermally conductive resin composition of the present invention comprises, in thermally conductive resin composition 100 % by weight, preferably 40～80 % by weight degree, more preferably 60～80 % by weight degree.By containing described heat conductivity particles more than 40 % by weight, the heat conductivity of thermally conductive resin composition further improves.On the other hand, by containing the described heat conductivity particle below 80 % by weight, the mechanical property of the forming process of thermally conductive resin composition and the formed body obtaining is also further enhanced.
In the present invention, as thermoplastic resin, such as polyolefin-based resins, polystyrene resin, Polyphony Ether resin, Acrylonitrile-butadiene-styrene Copolymer resin (ABS resin), polycarbonate resin, polyamide resin, polyacetal resin, polyester based resin, polyvinyl chloride (PVC) RESINS, plexiglass and the polyetherimide resin that can be polyvinyl resin, acrylic resin etc.In addition, as thermoplastic resin, the thermoplastic elastomer of the styrenic elastomerics of the olefin type elastomer of preferred α-olefin copolymer, ethene-acrylate copolymer (EEA, EMA, EBA, EMMA etc.) etc., SBS, SEBS, SEPS etc. etc.In addition, described thermoplastic resin can carry out sex change by special functional group or acid etc.Above-mentioned thermoplastic resin can be used separately or mix two or more use.
As described polyolefin-based resins, such as multipolymer, ethylene-vinyl acetate ester copolymer, ethene-methylmethacrylate copolymer, ethene-ethyl acrylate copolymer and the ethene-acrylic copolymer etc. that can be random, block or graft copolymer, α-alkene and ethene or the propylene of crystallinity or amorphous poly propylene, polybutene-1, poly--4-methylpentene, low density or high density polyethylene(HDPE), ethene-propylene.Wherein, as polyolefin-based resins, preferably random, the block of crystallinity or amorphous poly propylene, low density or high density polyethylene(HDPE), ethene-propylene or the multipolymer of graft copolymer, α-alkene and ethene or propylene.
Thermally conductive resin composition of the present invention can also comprise nitride.By using described nitride, can further improve the thermal conductivity of thermally conductive resin composition.Can cover described nitride by the mulch film that uses described surface treatment agent to form.
As described nitride, such as enumerating boron nitride, aluminium nitride etc.Described nitride can be used singly or two or more kinds mixed.In the situation that thermally conductive resin composition comprises described nitride, its ratio is preferably 1～30 % by weight degree in thermally conductive resin composition 100 % by weight.
In addition, the shape of nitride is not particularly limited, but can enumerate particle shape, particle shape, coccoid, flakey etc.
In not damaging the scope of object of the present invention, thermally conductive resin composition of the present invention can contain tinting material or other various additives as required.
Described tinting material, can be used dyestuff, pigment dyestuff and the mineral dye of public domain.
According to composition and classification, as described fuel, can enumerate such as styryl dye, pyridone azo dyes, pyrazoles azoic dyestuff (pyrazole azo), anthraquinone dye, assorted azoic dyestuff, phenylazo-fuel (Benzeneazo), naphthoquinone dyestuff, indoaniline dyes, cyanine dyes etc.In addition,, according to purpose classification, as described fuel, can enumerate dispersed dye, vat dyes, oil-soluble colourant.
As described pigment dyestuff, such as enumerating the condensation polycyclic series pigments (polycyclic dye) such as azo pigment, phthalocyanine, quinacridone, perylene, purple cyclic ketones, dioxazines, anthraquinone, isoindoline of azo lake, Hansom (Hanza), benzimidazolone, diaryl, pyrazolone, diarylide yellow, azoic dyestuff and nigrosine etc.
As described mineral dye, such as enumerating the mineral dyes such as zinc oxide, titan yellow, ferric oxide, Zh 1, ultramarine, Prussian blue, cobalt blue, chromoxide green, chrome yellow, cadmium yellow, cadmium red, iron oxide black and carbon black etc.
As other additive, can by using the purposes such as formed body suitably to select, for example, can be thermo-stabilizer, softening agent, dispersion agent, compatilizer, lubricant, antioxidant, photostabilizer, UV light absorber, crystallization nucleating agent, antiblocking agent, sealing property improving agent, releasing agent, the lubricants such as polyethylene wax, tinting material, pigment, inorganic filler (talcum, mica, clay, wollastonite, calcium carbonate, glass fibre, granulated glass sphere, glass sphere, milled fiber, glass flake, carbon fiber, carbon plate, carbon pearl, carbon milled fibre, sheet metal, steel fiber, the glass fibre of metal coated, the carbon fiber of washing, the glass flake of washing, silicon-dioxide, aluminum oxide, ceramic particle, ceramic fiber, aromatic poly amide particle, Kevlar, polyarylester fiber, graphite, carbon black and various whiskers etc.), whipping agent is (organic, inorganic, microcapsule system etc.), fire retardant (halogen, phosphoric acid ester, metal-salt, red phosphorus, metal hydroxides etc.), flame retardant, defoamer (PTFE particle etc.), white dyes, phosphorescent pigment, fluorescence dye, static inhibitor, flow ability modifying agent, crystallization nucleating agent, inorganic and organic antiseptic-germicide, represent the impact modifier of graft rubber, infrared absorbent and photochromic agent etc.Above-mentioned additive, can add separately or combine two or more interpolation.
Thermally conductive resin composition of the present invention, can manufacture by above-mentioned raw materials is dropped into melting mixings such as the such batch kneader of Banbury mixer or twin screw extruder, single screw extrusion machine or rotor-type Dual-screw kneader.In addition,, although the form of thermally conductive resin composition is not particularly limited, be generally particle, Powdered and beading.
Formed body of the present invention, can obtain by using forming machine that described thermally conductive resin composition is carried out to melting mixing.The method of moulding can be used known method.As forming method, such as enumerating extrusion molding, injection molding, blow molding, extrusion forming, calendering formation, T shape mold forming, inflation moulding, compressed moulding, tube extrusion moulding, laminated into type and vacuum forming etc.
Formed body of the present invention can have following purposes.For example, container and wrapping material [foodstuffs material (fresh provisions material, processed food material, refreshment drink etc.) with container and wrapping material, groceries (tableware, toy, stationery, electric elements, household electrical appliances, furniture, preference etc.) with container and wrapping material, fibre product (clothes, footwear, bedclothes, carpet, ground cushion, toilet paper, newspaper, handkerchief, towel etc.) with container and wrapping material, medicine (industrial medicine, pharmaceuticals etc.) with container and wrapping material, various covering material (agricultural chamber covering materials for industry, automobile coating for surface protection plate etc.), other purposes (plastic shopping bag, shopping bag, refuse bag etc.) with container and wrapping material], [the dashboard of part for automobile, door trim, the interior materials such as pillar, the outer exterior material such as collision bumper, gasoline tank, the internalies such as valve etc.], family's electrical article [TV, record player (video, hard disk, DVD, BD etc.), tuner, satellite antenna, electric iron, hair dryer, shaver, electric toothbrush, curler, facial-care apparatus, health-care appliance, dryer for quilt or cotton-padded mattress, washing machine, refrigerator, wine cellar, electric cooker, microwave oven, electronic scales, tableware dryer, food-processor, hot plate, electric kettle, coffee pot, electromagnetic oven, refuse treatment, suction cleaner, clock and watch, telephone set, set lights, ventilation blower fan, air-conditioning, fan, calorifier, dehumidifier, humidifier, air purifier, anion generator, massage armchair, foot sole massager, health care electrical equipment, power tool, home video game machine and Games Software, sound equipment accessory, pick up camera, stereo set, electronic musical instrument, telepilot, charger etc.] casing and internals etc., computer equipment [basic computer, indicating meter (CRI, liquid crystal, plasma body, projector and organic EL etc.), notebook computer, printer, recording medium drive (hard disk, MO, storage card, CD, DVD, BD, floppy disk etc.), recording medium (USB storage, IC-card etc.), mouse etc.] casing and internals etc., small portable apparatus [wireless, mobile telephone, PHS, PDA, smart mobile phone, portable game machine and computer game software, televisor, navigational aid, GPS equipment, stereophone, optical camera, digital camera and electronic dictionary and computer etc.] casing and internals etc., business equipment [duplicates fax, scanner and compounding machine thereof, shredder, folding machine, electronic blackboard, real-time clock, IP Camera, smoking counter, label machine, electronic cash register, eCheck numeric key punch, plastic packaging machine and binder etc.] casing and internals etc., the casing of game machine [arcade game machine, ball spring game machine, Slot Machine etc.] and internals etc., the casing of medical facilities [dry image forming instrument, medical printer, medical records, medical camera, x-ray television system, CT scanner system, Singh's graphic system, angioradiographic system and ultrasonic diagnostic system etc.] and internals etc., electronic component [various situations, various supports, cover, radiator fan, gear, sensor, valve, junctor, socket, transformer framework, resistor, button, switch, handle, switchboard, isolating switch, electrical condenser, supply socket, motor, transformer, tuner, Mgs, optical pick-up, vibrator, terminal strip, transformer, plug, timer and printed circuit board (PCB) etc.], transporting material [freight container, freight container flexibly, truck, pallet, carrier band, pallet, safety tread (transportation automotive seat), be wound around film (preventing that luggage from breaking), strapping tape, foamed damping material, air cap (cushioning material) etc.] [furniture (the chair of products formed for living material, desk, clothes hanger etc.), (the various doors such as entry is indoor such as the material of construction of house etc., inside and outside wall material, ceiling material, roof Material, ceramic tile, insulation thermal shield material etc.)], hobby articles for use [sports goods (racket, ski, skiing veneer etc.), garden supplies (seed sower etc.), outdoor appliances (fishing rod etc.) etc.], and other daily necessities [tableware, toy, stationery, oral care implement, bath article (bath, urinal etc.), health promoting appliance etc.)] etc.
In such use, formed body of the present invention is applicable to using household electrical appliances, OA equipment component, AV equipment part, automotive trim and exterior trimming parts.Particularly formed body of the present invention is in the household appliances or OA equipment of a lot of heatings, can effectively the heat producing by heating part be passed to radiating part, and for the radiator element of efficiently radiates heat, and then make to force, in electronics that cooling raio is more difficult, to can be used as the exterior trim materials'use that the heat for inside is produced sheds to outside thering is pyrotoxin by inside.Therefore, formed body of the present invention, preferably or portable type electronic product class, LED lamp or battery small-sized at the portable computers such as notebook, PDA, mobile telephone, portable game machine, portable music player, portable television/video equipment, field camera etc. around the thermal source such as part around, for must be with the heat-conduction component of the part of high efficiency heat radiation etc.
Embodiment
Below will be described in more detail the present invention.Only otherwise depart from technological thought of the present invention, the present invention just can not be defined in these embodiment, in addition, below " weight part " referred to as " portion ", " % by weight " referred to as " % ".
The material composition that below shows used composition in embodiment and comparative example.
1. magnesiumcarbonate particle
A1: synthetic Carbon Dioxide magnesium particle (average primary particle diameter: 1 μ m)
A2: synthetic Carbon Dioxide magnesium particle (average primary particle diameter: 4 μ m)
A3: synthetic Carbon Dioxide magnesium particle (average primary particle diameter: 10 μ m)
A4: synthetic Carbon Dioxide magnesium particle (average primary particle diameter: 20 μ m)
A5: synthetic Carbon Dioxide magnesium particle (average primary particle diameter: 28 μ m)
A6: synthetic Carbon Dioxide magnesium particle (average primary particle diameter: 40 μ m)
2. the surface treatment agent with alkoxysilyl and alkyl
B1: ethyl trimethoxy silane
B2: n-hexyl Trimethoxy silane
B3: n-octyl Trimethoxy silane
B4: positive decyl Trimethoxy silane
B5: dodecyl Trimethoxy silane
B6: Octadecane base Trimethoxy silane
B7:3-aminopropyl trimethoxy
B8: vinyltrimethoxy silane
B9: dimethyl silicone oil
3. thermoplastic resin
C1: linear low density polyethylene resin (LLDPE, MFR=10g/10min)
C2: polycarbonate resin (PC, MFR=15g/10min)
4. nitride
D1: boron nitride particles (hexagonal structure, median size 18 μ m)
[surface treatment of magnesiumcarbonate particle]
100 parts of magnesiumcarbonate particle A1 are carried out to mix and blend by Henschel mixer, as surface treatment agent, by 1 B1: ethyl trimethoxy silane is sprayed, and carries out the surface treatment (coating processing) of magnesiumcarbonate particle A1.Like this, form and cover the coating of carbonic acid magnesium particle A1 and obtain heat conductivity particle.Use electron microscope, the average primary particle diameter of asking for from 30 heat conductivity particles that obtain is 1.1 μ m.
In addition, use the same method, according to the cooperation described in table 1, by surface treatment agent, 100 parts of magnesiumcarbonate particles are carried out to surface treatment, obtain heat conductivity particle.Use electron microscope, from 30 heat conductivity particles that obtain, measure average primary particle diameter.Its result is illustrated in table 1.
[table 1]
[embodiment 1]
[manufacture of thermally conductive resin composition]
100 parts of magnesiumcarbonate particle A1 being carried out to 80 parts of heat conductivity particles and 20 parts of thermoplastic resin C1 that surface treatment obtains by 1 part of surface treatment agent B1 and drop into Henschel mixers, is that 20 ℃, time are under the condition of 3 minutes, to carry out premix to merge and obtain mixture in temperature.Afterwards; this mixture is supplied to screw diameter 30mm, L/D(screw diameter/spiro rod length)=38～42 extrusion machine; and in rotation number, be to carry out melting mixing under the condition of 220 ℃ of 250rpm, design temperature, use tablets press to make the mixing thing being squeezed out be shaped to coccoid.By like this, obtain thermally conductive resin composition.
[evaluation method]
The thermally conductive resin composition that use obtains, tests following assessment item.Its result is illustrated in table 2.
[melt viscosity]
In temperature, be under 190 ℃, the load condition that is 2.16kg, the melt viscosity (melt flow rate (MFR): MFR) that the JIS K-7210 of take is reference measurement thermally conductive resin composition.MFR(g/10 divides) degree higher, mobility during thermally conductive resin composition melting is better.
[thermal conductivity]
Thermally conductive resin composition is dropped into hot pressing panel forming machine, be heated to 200 ℃, make the sheet material of 2 vertical 30mm * horizontal 30mm * thick 3mm.Use hot dish method thermal physical property measuring device (TPS-500 capital of a country electronic industry system), and use diameter is 7mm
the thermal conductivity (unit: W/mK) of each sheet material of sensor measurement.Thermal conductivity is higher, and the thermal diffusivity of sheet material is better.
[tensile elongation of breaking point]
Thermally conductive resin composition is dropped into hot pressing panel forming machine, be heated to 200 ℃, after making the compressing tablet of thick 1mm, No. 5 dumbbell shape punchings and be used as test film.At draw speed, be under the 100mm/ condition of dividing, take the tensile elongation of JIS K-712 as the breaking point of reference measurement test film.In addition, use thermoplastic resin C1 to make and identical test film noted earlier, and by measuring the tensile elongation of the breaking point of this test film with identical method noted earlier.
Like this, use the tensile elongation of the breaking point of the test film that thermoplastic resin C1 makes to be set as at 100 o'clock, use the ratio of tensile elongation of the breaking point of the test film that thermally conductive resin composition makes to be obtained as conservation rate.The conservation rate of the tensile elongation of breaking point is higher, and test film Shen Long is better.
[injection moulding]
Thermally conductive resin composition is dropped into injection moulding machine (toshiba machine system), is that 220 ℃, injection pressure are 50MPa, die temperature while being 40 ℃ in injection temperature, uses vertical 250mm * horizontal 200mm(area 50000mm
2), the mould of 2 types of thick 5mm and 1mm, make 2 kinds of tabular formed bodys.
About 2 kinds of formed bodys that obtain, after measuring respectively its area, calculate the conservation rate of itself and die area 100, and evaluate with benchmark below.In addition, metewand A and B are realistic scales.
A: the area conservation rate of tabular formed body is more than 95%.
B: the area conservation rate of tabular formed body does not contain 95% at 90%～95%() between.
C: the area conservation rate less than 90% of tabular formed body.
[extrusion molding]
Thermally conductive resin composition is dropped into T-Die film forming machine (Japan essence mechanism), by being that 220 ℃, screw rod rotation number are melted extrusion modeling under 80rpm at mold temperature, obtain the formed body of the film like of wide 100mm * thick 300 μ m.
About the film 1m obtaining, each region that is 100mm in the direction of extrusion (length direction), from the position of each 100mm of two ends in each region and to the equidistant position (central point) at two ends, these are in 3, the variable quantity of the thickness of measurement from 300 μ m, and with benchmark below, extrusion molding is evaluated.In addition, metewand A and B are realistic scale.
A: the maximum variable quantity less than 15 μ m of the thickness of film.
B: the maximum variable quantity of the thickness of film does not contain 30 μ m at 15 μ m～30 μ m() between.
C: the maximum variable quantity of the thickness of film is more than 30 μ m.
The above results represents in table 2.
[embodiment 2～25, comparative example 1～3]
With the cooperation of the heat conductivity resin described in table 2, making bead identical with embodiment 1, and evaluate with the method identical with aforesaid method.Its result is illustrated in table 2.
[comparative example 4]
Except having used, do not carry out surface-treated magnesiumcarbonate particle A1, other making bead identical with embodiment 1, and evaluate with method same as described above.Its result is illustrated in table 2.
[comparative example 5～7]
With the cooperation of the thermally conductive resin composition described in table 2, making bead identical with embodiment 4, and evaluate with method same as described above, its result is illustrated in table 2.
[table 2]
[embodiment 26]
By 1 part of surface treatment agent B1,100 parts of magnesiumcarbonate particle A1 are carried out 40 parts of heat conductivity particles that surface treatment obtains, by 1 part of surface treatment agent B1,100 parts of magnesiumcarbonate particle A4 carried out to 40 parts of heat conductivity particles and the 20 parts of thermoplastic resin C1 that surface treatment obtains, except using above-mentioned these 3 kinds, other making bead identical with embodiment 1, and evaluate by method same as described above, its result is illustrated in table 3.
[embodiment 27～29]
With the cooperation of the thermally conductive resin composition described in table 3, making bead identical with embodiment 26, and evaluate by aforesaid method.Its result is illustrated in table 3.
[table 3]
[embodiment 30]
[manufacture of thermally conductive resin composition]
Identical with aforesaid method, to to 100 parts of magnesiumcarbonate particle A1, carry out 60 parts of heat conductivity particles and 40 parts of thermoplastic resin C2 that surface treatment obtains by 1 part of surface treatment agent B1 and drop into Henschel mixers, and be that 20 ℃, time are to make its pre-mixing obtain mixture under the condition of 3 minutes in temperature.Afterwards; described mixture is supplied to screw diameter 30mm; the extrusion machine of L/D(screw diameter/spiro rod length)=38～42, and in rotation number, be to carry out melting mixing under the condition of 260 ℃ of 250rpm, design temperature, use tablets press to make the mixing thing squeezing out be shaped to coccoid.By like this, obtain thermally conductive resin composition.
[evaluation method]
The thermally conductive resin composition that use obtains, carries out the test identical with embodiment 1.Its result is illustrated in table 4.
[melt viscosity]
In temperature, be under 300 ℃, the load condition that is 2.16kg, the melt viscosity (melt flow rate (MFR): MFR) that the JIS K-7210 of take is reference measurement thermally conductive resin composition.MFR(g/10 divides) degree higher, mobility during thermally conductive resin composition melting is better.
[thermal conductivity]
Thermally conductive resin composition is dropped into hot pressing panel forming machine, be heated to 280 ℃, make the sheet material of 2 vertical 30mm * horizontal 30mm * thick 3mm.Use hot dish method thermal physical property measuring device (TPS-500 capital of a country electronic industry system), and use diameter is 7mm
the thermal conductivity (unit: W/mK) of each sheet material of sensor measurement.Thermal conductivity is higher, and the thermal diffusivity of sheet material is better.
[tensile elongation of breaking point]
Thermally conductive resin composition is dropped into hot pressing panel forming machine, be heated to 280 ℃, after making the compressing tablet of thick 1mm, No. 5 dumbbell shape punchings and be used as test film.At draw speed, be under the 100mm/ condition of dividing, take the tensile elongation of JIS K-7127 as the breaking point of reference measurement test film.In addition, use thermoplastic resin C2 to make and identical test film noted earlier, and by measuring the tensile elongation of the breaking point of this test film with identical method noted earlier.
Like this, use the tensile elongation of the breaking point of the test film that thermoplastic resin C2 makes to be set as at 100 o'clock, use the ratio of tensile elongation of the breaking point of the test film that thermally conductive resin composition makes to be obtained as conservation rate.The conservation rate of the tensile elongation of breaking point is higher, and the extensibility of test film is better.
[injection moulding]
Thermally conductive resin composition is dropped into injection moulding machine (toshiba machine system), is that 260 ℃, injection pressure are that 50MPa, die temperature are at 80 ℃ in injection temperature, uses vertical 250mm * horizontal 200mm(area 50000mm
2), the mould of 2 types of thick 5mm and 1mm, make 2 kinds of tabular formed bodys.
About 2 kinds of formed bodys that obtain, after measuring respectively its area, calculate the conservation rate of itself and die area 100, and with benchmark below, injection molding is evaluated.In addition, metewand A and B are realistic scales.
A: the area conservation rate of tabular formed body is more than 95%.
B: the area conservation rate of tabular formed body does not contain 95% at 90%～95%() between.
C: the area conservation rate less than 90% of tabular formed body.
[extrusion molding]
Thermally conductive resin composition is dropped into T-Die film forming machine (Japan essence mechanism), by mold temperature being 280, screw rod rotation number is melted extrusion modeling under 80rpm, obtains the formed body of the film like of wide 100mm * thick 300 μ m.
About the film 1m obtaining, each region that is 100mm in the direction of extrusion (length direction), to the position of each 10mm of two ends in each region and in this 3 place, equidistant position (central point) at two ends, the variable quantity of the thickness of measurement from 300 μ m, and with benchmark below, extrusion molding is evaluated.In addition, metewand A and B are realistic scale.
A: the maximum variable quantity less than 15 μ m of the thickness of film.
B: the maximum variable quantity of the thickness of film does not contain 30 μ m at 15 μ m～30 μ m() between.
C: the maximum variable quantity of the thickness of film is more than 30 μ m.
The above results is illustrated in table 4.
[embodiment 31～44, comparative example 8～10]
With the cooperation of the thermally conductive resin composition described in table 4, making bead identical with embodiment 30, and evaluate with method same as described above.Its result is illustrated in table 4.
[comparative example 11]
Except having used, do not carry out surface-treated magnesiumcarbonate particle A1, other making bead identical with embodiment 30, and evaluate with the method identical with aforesaid method.Its result is illustrated in table 4.
[comparative example 12,13]
With the cooperation of the thermally conductive resin composition described in table 4, making bead identical with comparative example 11, and evaluate with the method identical with aforesaid method.Its result is illustrated in table 4.
[table 4]
[embodiment 45]
By 1 part of surface treatment agent B1,100 parts of magnesiumcarbonate particle A1 are processed 30 parts of heat conductivity particles obtaining, by 1 part of surface treatment agent, 100 parts of magnesiumcarbonate particle A4 processed 30 parts of heat conductivity particles and the 40 parts of thermoplastic resin C2 that obtain, except using above-mentioned 3 kinds, other making bead identical with embodiment 30, and evaluate with method same as described above.Its result is illustrated in table 5.
[embodiment 46～48]
With the cooperation of the thermally conductive resin composition described in table 5, making bead identical with comparative example 45, and evaluate with the method identical with aforesaid method.Its result is illustrated in table 5.
[table 5]
As clearly represented in table 2～table 5, even thermally conductive resin composition of the present invention comprises a large amount of heat conductivity particles in embodiment 1～48, forming process is also very excellent, so also can obtain the formed body that has dimensional stability, smoothness, can change the extensibility of shape.On the other hand, used the formed body of the thermally conductive resin composition of comparative example 1～13, the decline of its dimensional stability, smoothness, extensibility is obvious, poorer than the formed body of embodiment 1～48.
Claims (5)
1. a thermally conductive resin composition, is characterized in that, comprising average primary particle diameter is heat conductivity particle and the thermoplastic resin of 0.1～30 μ m,
Described heat conductivity particle has magnesiumcarbonate particle and tectum,
Described tectum forms by having the surface treatment agent of alkoxysilyl and alkyl.
2. thermally conductive resin composition according to claim 1, is characterized in that, the carbon number of the described alkyl that described surface treatment agent has is 6～12.
3. thermally conductive resin composition according to claim 1 and 2, is characterized in that, for described magnesiumcarbonate particle 100 weight parts, with the described surface treatment agent that contains 0.05～3 weight part, forms described tectum.
4. thermally conductive resin composition according to claim 1 and 2, is characterized in that, also comprises nitride.
5. a formed body, is characterized in that, the thermally conductive resin composition moulding described in any one in described claim 1～4 is formed.
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| JP2013008872 | 2013-01-22 | ||
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151731A (en) * | 2014-09-01 | 2014-11-19 | 苏州卓越工程塑料有限公司 | Photochromic injection material |
| CN105585835A (en) * | 2016-02-29 | 2016-05-18 | 欧士玺 | Heat-insulation cushion for vehicles and manufacturing method thereof |
| CN109587377A (en) * | 2017-09-29 | 2019-04-05 | 韩国以事美德有限公司 | The method for opening and closing of camera model check device and its socket with automatic socket |
| CN115651494A (en) * | 2022-11-03 | 2023-01-31 | 南雄市星隆化工有限公司 | Epoxy glass flake anticorrosive paint |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7100429B2 (en) * | 2016-05-31 | 2022-07-13 | 三井化学株式会社 | Molded article containing a thermally conductive composition |
| WO2017209215A1 (en) | 2016-05-31 | 2017-12-07 | 三井化学株式会社 | Thermally-conductive composition |
| JP7044484B2 (en) * | 2016-05-31 | 2022-03-30 | 三井化学株式会社 | Thermally conductive composition |
| KR102541617B1 (en) * | 2023-03-17 | 2023-06-13 | 주식회사 케이리사이클링 | Recycled Plastic Composition Using Daily Waste Plastics and Preparation Methods of Recycled Plastic Using Thereof |
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| JP2005194491A (en) * | 2003-12-09 | 2005-07-21 | Mitsubishi Plastics Ind Ltd | Resin composition and resin film using thereof |
| JP4455911B2 (en) * | 2004-03-26 | 2010-04-21 | 神島化学工業株式会社 | Anhydrous magnesium carbonate filler, method for producing the same, and resin composition |
| JP2006160979A (en) | 2004-12-10 | 2006-06-22 | Konoshima Chemical Co Ltd | Filler, its preparation and resin composition |
| JP4884691B2 (en) | 2005-04-13 | 2012-02-29 | 神島化学工業株式会社 | Synthetic rubber composition |
| JP2007261922A (en) | 2006-03-30 | 2007-10-11 | Konoshima Chemical Co Ltd | Anhydrous magnesium carbonate-based powder, resin composition and molding |
| JP5381829B2 (en) * | 2010-03-16 | 2014-01-08 | 信越化学工業株式会社 | Surface-treated inorganic powder |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151731A (en) * | 2014-09-01 | 2014-11-19 | 苏州卓越工程塑料有限公司 | Photochromic injection material |
| CN105585835A (en) * | 2016-02-29 | 2016-05-18 | 欧士玺 | Heat-insulation cushion for vehicles and manufacturing method thereof |
| CN109587377A (en) * | 2017-09-29 | 2019-04-05 | 韩国以事美德有限公司 | The method for opening and closing of camera model check device and its socket with automatic socket |
| CN109587377B (en) * | 2017-09-29 | 2020-12-29 | 韩国以事美德有限公司 | Camera module inspection device with automatic socket and method for opening and closing socket |
| CN115651494A (en) * | 2022-11-03 | 2023-01-31 | 南雄市星隆化工有限公司 | Epoxy glass flake anticorrosive paint |
Also Published As
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| JP6311321B2 (en) | 2018-04-18 |
| JP2014159554A (en) | 2014-09-04 |
| KR101874147B1 (en) | 2018-07-03 |
| KR20140094473A (en) | 2014-07-30 |
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Application publication date: 20140723 |