JP2021025163A - Heat-conductive particle-filled fiber - Google Patents
Heat-conductive particle-filled fiber Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 368
- 239000000835 fiber Substances 0.000 title claims abstract description 137
- 239000011347 resin Substances 0.000 claims abstract description 119
- 229920005989 resin Polymers 0.000 claims abstract description 119
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000011049 filling Methods 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims description 40
- 239000011342 resin composition Substances 0.000 claims description 32
- 238000004519 manufacturing process Methods 0.000 claims description 31
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000000395 magnesium oxide Substances 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 19
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000470 constituent Substances 0.000 claims description 14
- 238000001523 electrospinning Methods 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000009987 spinning Methods 0.000 claims description 9
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000002113 nanodiamond Substances 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 229920002050 silicone resin Polymers 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 239000000945 filler Substances 0.000 description 11
- 239000010408 film Substances 0.000 description 10
- 229920002189 poly(glycerol 1-O-monomethacrylate) polymer Polymers 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 6
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- 239000010409 thin film Substances 0.000 description 5
- -1 phosphate ester compound Chemical class 0.000 description 4
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002296 dynamic light scattering Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011852 carbon nanoparticle Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 229910003472 fullerene Inorganic materials 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000005325 percolation Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
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- 229920000768 polyamine Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Nonwoven Fabrics (AREA)
Abstract
Description
本発明は、熱伝導性粒子充填ファイバー及びその製造方法、並びに、樹脂組成物及びその製造方法に関する。 The present invention relates to a thermally conductive particle-filled fiber and a method for producing the same, and a resin composition and a method for producing the same.
樹脂、カーボン、金属酸化物などを用いた微細繊維は、一般に、ナノファイバーと称される、繊維径がナノスケールの繊維である。微細繊維は、表面積が非常に大きく、種々の用途（例えば、高性能フィルター、電池セパレーター、電磁波シールド材、人工皮革、細胞培養基材、ＩＣチップ、有機ＥＬ、太陽電池、等）に応用されることが期待されている。 Fine fibers using resins, carbons, metal oxides, etc. are generally called nanofibers and have a fiber diameter of nanoscale. Fine fibers have a very large surface area and are applied to various applications (for example, high-performance filters, battery separators, electromagnetic wave shielding materials, artificial leather, cell culture substrates, IC chips, organic EL, solar cells, etc.). Is expected.
微細繊維の特性、例えば、物理的特性や電気的特性などを変えるために、また、所定の機能を付与するために、目的に応じた材料を当該微細繊維と複合化させることが提案されている。
特許文献１には、有機樹脂中に繊維状アルミナフィラーが分散した、所定の熱伝導率を有するフィラー分散有機樹脂複合体が開示されている。
特許文献２には、樹脂中に樹脂繊維を配合してなる材料で構成された樹脂シートであって、前記樹脂繊維は、樹脂にフィラーを分散して構成されたものである、樹脂シートが開示されている。
特許文献３には、樹脂中に樹脂繊維を配合してなる材料で構成された樹脂シートであって、前記樹脂繊維は、樹脂に極性基を有するポリエステル樹脂を表面に有するフィラーを含むものである、樹脂シートが開示されている。
特許文献４には、熱伝導性無機粒子とセルロースナノファイバーの複合材からなる放熱材であって、前記セルロースナノファイバーは、その表面をエステル化及び／又はエーテル化して修飾してある、放熱材が開示されている。
特許文献５には、樹脂とフィラーとを含有する高熱伝導性樹脂硬化物であって、前記フィラーは、所定の小粒径フィラー、所定の中粒径フィラー、及び所定の大粒径フィラーを所定範囲の質量％でそれぞれ含有し、前記フィラーの最大粒子径、及び前記大粒径フィラーの平均粒子径が、前記高熱伝導性樹脂硬化物の膜厚に対してそれぞれ所定の範囲内であり、前記フィラーの含有量が、前記高熱伝導性樹脂硬化物全体の所定の範囲内である、高熱伝導性樹脂硬化物が開示されている。
特許文献６には、樹脂と平均粒径が１０〜１０００ｎｍの熱伝導性粒子とを含有し、平均繊維径が５０〜１００００ｎｍである、熱伝導性粒子充填ファイバーが開示されている。
It has been proposed to combine a material according to the purpose with the fine fiber in order to change the characteristics of the fine fiber, for example, physical property or electrical property, and to impart a predetermined function. ..
Patent Document 1 discloses a filler-dispersed organic resin composite having a predetermined thermal conductivity in which a fibrous alumina filler is dispersed in an organic resin.
Patent Document 2 discloses a resin sheet made of a material obtained by blending resin fibers in a resin, wherein the resin fibers are made by dispersing a filler in a resin. Has been done.
Patent Document 3 describes a resin sheet made of a material in which resin fibers are blended in a resin, wherein the resin fibers contain a filler having a polyester resin having a polar group in the resin on the surface. The sheet is disclosed.
Patent Document 4 describes a heat radiating material composed of a composite material of thermally conductive inorganic particles and cellulose nanofibers, wherein the surface of the cellulose nanofibers is modified by esterification and / or etherification. Is disclosed.
Patent Document 5 describes a cured product of a high thermosetting resin containing a resin and a filler, wherein the filler is a predetermined small particle size filler, a predetermined medium particle size filler, and a predetermined large particle size filler. The maximum particle size of the filler and the average particle size of the large particle size filler are each within a predetermined range with respect to the film thickness of the cured thermosetting resin. A highly thermosetting resin cured product having a filler content within a predetermined range of the entire thermosetting resin cured product is disclosed.
Patent Document 6 discloses a thermally conductive particle-filled fiber containing a resin and thermally conductive particles having an average particle diameter of 10 to 1000 nm and having an average fiber diameter of 50 to 10,000 nm.
本発明は、熱伝導性粒子の充填量が多く、優れた熱伝導性を示すとともに、樹脂に配合する際の作業性にも優れた熱伝導性粒子充填ファイバー、及びこれを含む樹脂組成物を提供する。 The present invention provides a thermally conductive particle-filled fiber having a large amount of thermally conductive particles and exhibiting excellent thermal conductivity and also having excellent workability when blended with a resin, and a resin composition containing the same. provide.
本発明は、熱伝導性粒子、及び重量平均分子量３０，０００〜３００，０００の樹脂を含有する熱伝導性粒子充填ファイバーであって、熱伝導性粒子は、粒径１０〜９００ｎｍの熱伝導性粒子（Ｘ）を含み、熱伝導性粒子（Ｘ）中、粒径１００ｎｍ以上の粒子〔（以下、粒子（Ｘ100）という〕の割合が５〜５０質量％である、熱伝導性粒子充填ファイバーに関するものである。 The present invention is a thermally conductive particle-filled fiber containing thermally conductive particles and a resin having a weight average molecular weight of 30,000 to 300,000, wherein the thermally conductive particles have a particle size of 10 to 900 nm. Thermally conductive particle-filled fiber containing particles (X) and having a proportion of particles having a particle size of 100 nm or more [(hereinafter referred to as particles (X 100 )] of 5 to 50% by mass in the thermally conductive particles (X)). It is about.
また本発明は、平均粒径１００ｎｍ未満の熱伝導性粒子（Ｘ１）、平均粒径１００ｎｍ以上９００ｎｍ以下の熱伝導性粒子（Ｘ２）、及び重量平均分子量３０，０００〜３００，０００の樹脂を混合する、本発明の熱伝導性粒子充填ファイバーの製造方法に関するものである。 Further, the present invention is a mixture of thermally conductive particles (X1) having an average particle diameter of less than 100 nm, thermally conductive particles (X2) having an average particle diameter of 100 nm or more and 900 nm or less, and a resin having a weight average molecular weight of 30,000 to 300,000. The present invention relates to a method for producing a thermally conductive particle-filled fiber of the present invention.
また本発明は、本発明の熱伝導性粒子充填ファイバーとマトリックス樹脂とを含有する樹脂組成物に関するものである。 The present invention also relates to a resin composition containing the thermally conductive particle-filled fiber of the present invention and a matrix resin.
更に本発明は、本発明の熱伝導性粒子充填ファイバーの製造工程（Ｉ）と、前記工程（Ｉ）で得られた熱伝導性粒子充填ファイバーと熱伝導性粒子（Ｙ）とをマトリックス樹脂に配合する工程（II）とを有する樹脂組成物の製造方法であって、前記工程（Ｉ）が、樹脂、熱伝導性粒子（Ｘ１）、熱伝導性粒子（Ｘ２）及び溶媒を含有するポリマー溶液を用いて電界紡糸法により紡糸する工程である樹脂組成物の製造方法に関するものである。 Further, in the present invention, the heat conductive particle-filled fiber manufacturing step (I) of the present invention, and the heat conductive particle-filled fiber and the heat conductive particles (Y) obtained in the step (I) are made into a matrix resin. A method for producing a resin composition having a step (II) of blending, wherein the step (I) is a polymer solution containing a resin, thermally conductive particles (X1), thermally conductive particles (X2), and a solvent. The present invention relates to a method for producing a resin composition, which is a step of spinning by an electrospinning method using the above.
本発明によれば、熱伝導性粒子の充填量が多く、優れた熱伝導性を示すとともに、樹脂に配合する際の作業性にも優れた熱伝導性粒子充填ファイバー、及びこれを含む樹脂組成物が提供される。 According to the present invention, a thermally conductive particle-filled fiber having a large amount of thermally conductive particles filled, exhibiting excellent thermal conductivity, and excellent workability when blended with a resin, and a resin composition containing the same. Things are provided.
＜熱伝導性粒子充填ファイバー及びその製造方法＞
本発明の熱伝導性粒子充填ファイバーは、熱伝導性粒子、及び重量平均分子量３０，０００〜３００，０００の樹脂を含有する熱伝導性粒子充填ファイバーであって、熱伝導性粒子は、粒径１０〜９００ｎｍの熱伝導性粒子（Ｘ）を含み、熱伝導性粒子（Ｘ）中、粒径１００ｎｍ以上の粒子（Ｘ100）の割合が５〜５０質量％である。
<Thermal conductive particle-filled fiber and its manufacturing method>
The thermally conductive particle-filled fiber of the present invention is a thermally conductive particle-filled fiber containing the thermally conductive particles and a resin having a weight average molecular weight of 30,000 to 300,000, and the thermally conductive particles have a particle size. The ratio of the particles (X 100 ) having a particle size of 100 nm or more in the heat conductive particles (X) containing the heat conductive particles (X) of 10 to 900 nm is 5 to 50% by mass.
本発明の熱伝導性粒子充填ファイバーは、熱伝導性粒子の含有量を多くできる、すなわち熱伝導性粒子が高充填されたファイバーとすることができるため、ファイバー内のパーコレーション効果が増大し熱伝導率が向上すると推察される。また、ファイバー表面にも熱伝導性粒子が露出し、無機フィラーを含有する樹脂組成物に配合した際に、無機フィラーとの接触も増えて樹脂組成物片全体のパーコレーション効果が増大し、熱伝導率はより良好となる。
また、本発明の熱伝導性粒子充填ファイバーは、製法にもよるが、綿状で得ることができるため、例えば、樹脂組成物に配合する場合は、マトリックス樹脂の浸透性が良くなり、樹脂組成物中での本発明の熱伝導性粒子充填ファイバーの分散性が向上し、偏在も少なくなる。
このような効果は、本発明において、所定粒径の熱伝導性粒子（Ｘ）を用い、且つ粒子（Ｘ）中、粒径が相対的に大きい粒子（Ｘ100）の量を特定範囲として、重量平均分子量が前記範囲の樹脂と組み合わせることで得られる。
これに対して、本発明の粒度分布を満たさない熱伝導性粒子を用いた場合は、ファイバー中に高充填しようとすると、使用する分散液の濃度を上げなくてはならず、それに伴い粒子凝集が生じやすくなり、凝集した塊がファイバーに多く導入されてしまうため、均一なパーコレーション効果が得られず、本発明の効果も得られないものと推察される。
The heat conductive particle-filled fiber of the present invention can have a large content of heat conductive particles, that is, can be a fiber highly filled with heat conductive particles, so that the percoration effect in the fiber is increased and heat conduction It is estimated that the rate will improve. In addition, the heat conductive particles are also exposed on the fiber surface, and when blended in the resin composition containing the inorganic filler, the contact with the inorganic filler increases and the percolation effect of the entire resin composition piece increases, resulting in heat conduction. The rate will be better.
Further, the thermally conductive particle-filled fiber of the present invention can be obtained in the form of cotton, although it depends on the production method. Therefore, for example, when blended in a resin composition, the permeability of the matrix resin is improved and the resin composition is improved. The dispersibility of the thermally conductive particle-filled fiber of the present invention in the object is improved, and uneven distribution is also reduced.
Such an effect is obtained in the present invention by using thermally conductive particles (X) having a predetermined particle size and setting the amount of particles (X 100 ) having a relatively large particle size among the particles (X) as a specific range. It is obtained by combining with a resin having a weight average molecular weight in the above range.
On the other hand, when thermally conductive particles that do not satisfy the particle size distribution of the present invention are used, if the fiber is to be highly filled, the concentration of the dispersion liquid to be used must be increased, and the particles are aggregated accordingly. Is likely to occur, and a large amount of agglomerated lumps are introduced into the fiber, so that a uniform percolation effect cannot be obtained, and it is presumed that the effect of the present invention cannot be obtained.
本発明において、熱伝導性粒子とは、熱伝導率が、１．０Ｗ／ｍ・Ｋ以上である粒子をいう。 In the present invention, the thermally conductive particles refer to particles having a thermal conductivity of 1.0 W / m · K or more.
本発明の熱伝導性粒子充填ファイバーは、熱伝導性粒子として、粒径が１０〜９００ｎｍの熱伝導性粒子（Ｘ）を含有する。本発明者らは、微細な樹脂ファイバーに充填する熱伝導性粒子として、粒径が１０〜９００ｎｍの範囲にある粒子（熱伝導性粒子（Ｘ））が、充填量を多くした場合のファイバー形状の保持に影響することを見出した。そして、そのような所定の粒径を有する熱伝導性粒子（Ｘ）中、粒径１００ｎｍ以上の粒子（Ｘ100）の割合を５〜５０質量％として、所定の重量平均分子量の樹脂と組み合わせることで、熱伝導性粒子の充填量が多く、優れた熱伝導性を示すとともに、樹脂に配合する際の作業性にも優れた熱伝導性粒子充填ファイバーを得たものである。 The thermally conductive particle-filled fiber of the present invention contains thermally conductive particles (X) having a particle size of 10 to 900 nm as the thermally conductive particles. As the heat conductive particles to be filled in the fine resin fiber, the present inventors have formed a fiber shape in which particles having a particle size in the range of 10 to 900 nm (heat conductive particles (X)) have a large filling amount. It was found to affect the retention of. Then, among the thermally conductive particles (X) having such a predetermined particle size, the proportion of the particles (X 100 ) having a particle size of 100 nm or more is set to 5 to 50% by mass, and the particles are combined with a resin having a predetermined weight average molecular weight. As a result, a thermally conductive particle-filled fiber having a large amount of thermally conductive particles filled, exhibiting excellent thermal conductivity, and also having excellent workability when blended into a resin was obtained.
なお、熱伝導性粒子は、平均粒径が１０〜９００ｎｍであってよい。
また、熱伝導性粒子の粒径分布は、下限値は、５ｎｍ、更に１０ｎｍ、そして、上限値は１，０００ｎｍ、更に８００ｎｍから選択されてよい。
The heat conductive particles may have an average particle size of 10 to 900 nm.
The particle size distribution of the thermally conductive particles may be selected from a lower limit of 5 nm and further 10 nm, and an upper limit of 1,000 nm and further 800 nm.
また、本発明では、ファイバー中に熱伝導性粒子を高充填するための観点から、熱伝導性粒子（Ｘ）中、粒径１００ｎｍ以上の粒子（Ｘ100）の割合が、５〜５０質量％であり、好ましくは５〜３０質量％、より好ましくは５〜１５質量％である。
したがって、本発明では、熱伝導性粒子（Ｘ）中、粒径１００ｎｍ未満の粒子の割合は、９５〜５０質量％であり、好ましくは９５〜７０質量％、より好ましくは９５〜８５質量％である。
Further, in the present invention, from the viewpoint of highly filling the fiber with the heat conductive particles, the ratio of the particles (X 100 ) having a particle size of 100 nm or more in the heat conductive particles (X) is 5 to 50% by mass. It is preferably 5 to 30% by mass, and more preferably 5 to 15% by mass.
Therefore, in the present invention, the proportion of particles having a particle size of less than 100 nm in the thermally conductive particles (X) is 95 to 50% by mass, preferably 95 to 70% by mass, and more preferably 95 to 85% by mass. is there.
また、本発明では、ファイバー中に熱伝導性粒子を高充填する際に繊維形状を維持するための観点から、熱伝導性粒子中、熱伝導性粒子（Ｘ）の割合は、好ましくは９０質量％以上、より好ましくは９０〜１００質量％、更に好ましくは９５〜１００質量％である。 Further, in the present invention, the ratio of the thermally conductive particles (X) to the thermally conductive particles is preferably 90 mass from the viewpoint of maintaining the fiber shape when the fibers are highly filled with the thermally conductive particles. % Or more, more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass.
本発明の熱伝導性粒子充填ファイバーは、パーコレーション構造が増え熱伝導率を向上するための観点から、熱伝導性粒子（Ｘ）を７０〜９５質量％、好ましくは８０〜９５質量％、より好ましくは８５〜９５質量％含有する。 The thermally conductive particle-filled fiber of the present invention contains 70 to 95% by mass, preferably 80 to 95% by mass, more preferably the thermally conductive particles (X) from the viewpoint of increasing the percoration structure and improving the thermal conductivity. Contains 85-95% by mass.
本発明の熱伝導性粒子充填ファイバーは、パーコレーション構造が増え熱伝導率を向上するための観点から、熱伝導性粒子を、好ましくは８０〜９５質量％、より好ましくは８５〜９５質量％含有する。 The thermally conductive particle-filled fiber of the present invention preferably contains 80 to 95% by mass, more preferably 85 to 95% by mass of thermally conductive particles from the viewpoint of increasing the percoration structure and improving the thermal conductivity. ..
熱伝導性粒子、更に熱伝導性粒子（Ｘ）の粒径は、動的光散乱法（ＤＬＳ：Ｄｙｎａｍｉｃ Ｌｉｇｈｔ Ｓｃａｔｔｅｒｉｎｇ Ｍｅａｓｕｒｅｍｅｎｔ）により測定されたものである。具体的には、熱伝導性粒子を分散媒にマグネチックスターラーで２４時間程度撹拌することにより分散し、得られた分散液をダイナミック光散乱光度計（例えば、大塚電子株式会社製、型番：ＤＬＳ−７０００ＨＬ）を用いて測定することができる。 The particle size of the thermally conductive particles and further, the thermally conductive particles (X) is measured by a dynamic light scattering method (DLS: Dynamic Light Scattering Measurement). Specifically, the thermally conductive particles are dispersed in a dispersion medium by stirring with a magnetic stirrer for about 24 hours, and the obtained dispersion is dispersed by a dynamic light scattering photometer (for example, manufactured by Otsuka Electronics Co., Ltd., model number: DLS). -7000HL) can be used for measurement.
熱伝導性粒子としては、具体的には、酸化マグネシウム粒子、酸化アルミニウム粒子、酸化ケイ素粒子等の金属酸化物粒子、窒化ホウ素粒子、窒化アルミニウム粒子、窒化ケイ素粒子等の金属窒化物粒子、及び活性炭粒子、ナノダイヤ粒子、カーボンナノ粒子、フラーレン粒子、グラフェン粒子等の炭素粒子から選ばれる１種以上が挙げられる。熱伝導性がよい点で、酸化マグネシウム粒子、酸化アルミニウム粒子、窒化ホウ素粒子、窒化アルミニウム粒子、ナノダイヤ粒子、カーボンナノチューブ粒子、及びグラフェン粒子から選ばれる１種以上が好ましく、酸化マグネシウム粒子がより好ましい。 Specific examples of the thermally conductive particles include metal oxide particles such as magnesium oxide particles, aluminum oxide particles and silicon oxide particles, metal nitride particles such as boron nitride particles, aluminum nitride particles and silicon nitride particles, and activated carbon. One or more selected from carbon particles such as particles, nanodiamond particles, carbon nanoparticles, fullerene particles, and graphene particles can be mentioned. From the viewpoint of good thermal conductivity, one or more selected from magnesium oxide particles, aluminum oxide particles, boron nitride particles, aluminum nitride particles, nanodiamond particles, carbon nanotube particles, and graphene particles are preferable, and magnesium oxide particles are more preferable.
上記のような粒径をもつ熱伝導性粒子、例えば酸化マグネシウム粒子は、例えば気相酸化法により入手できる。 Thermally conductive particles having the above particle size, for example, magnesium oxide particles, can be obtained by, for example, a vapor phase oxidation method.
本発明の熱伝導性粒子充填ファイバーは、重量平均分子量３０，０００〜３００，０００の樹脂を含有する。樹脂は、エポキシ樹脂、アクリル樹脂、アミド・イミド樹脂、フェノール樹脂、シリコーン樹脂などから選ばれる１種以上の樹脂が挙げられる。後述する熱伝導性粒子充填ファイバー製造の際の作業性がよい点で、エポキシ樹脂かアクリル樹脂が少なくとも１種含まれることが好ましい。より具体的には、ポリグリシジルメタクリレートが含まれることが好ましい。 The thermally conductive particle-filled fiber of the present invention contains a resin having a weight average molecular weight of 30,000 to 300,000. Examples of the resin include one or more resins selected from epoxy resins, acrylic resins, amide / imide resins, phenol resins, silicone resins and the like. It is preferable that at least one epoxy resin or acrylic resin is contained from the viewpoint of good workability in the production of the heat conductive particle-filled fiber described later. More specifically, it preferably contains polyglycidyl methacrylate.
樹脂の重量平均分子量は、熱伝導性粒子の充填量を高め、熱伝導性がよい点及び樹脂に配合する際の作業性がよい点で、３０，０００〜３００，０００であり、５０，０００〜３００，０００がより好ましく、１００，０００〜２５０，０００が更に好ましい。ここで、樹脂の重量平均分子量は、ＧＰＣ（ゲル浸透クロマトグラフィー）により測定されたものである。 The weight average molecular weight of the resin is 30,000 to 300,000, which is 50,000 in terms of increasing the filling amount of the heat conductive particles, good heat conductivity, and good workability when blended with the resin. ~ 300,000 is more preferable, and 100,000 to 250,000 is even more preferable. Here, the weight average molecular weight of the resin is measured by GPC (gel permeation chromatography).
本発明の熱伝導性粒子充填ファイバーは、平均繊維径が、好ましくは５０〜１０，０００ｎｍ、より好ましくは１００〜５，０００ｎｍ、更に好ましくは１００〜１，０００ｎｍである。
ここで、熱伝導性粒子充填ファイバーの平均繊維径は、得られたナノファイバーを走査型電子顕微鏡（日立ハイテクノロジーズ製ＳＵ１５１０）により撮影して得た画像から、ランダムに５０箇所を選んで平均値を求めることにより測定できる。
The thermally conductive particle-filled fiber of the present invention has an average fiber diameter of preferably 50 to 10,000 nm, more preferably 100 to 5,000 nm, and even more preferably 100 to 1,000 nm.
Here, the average fiber diameter of the thermally conductive particle-filled fibers is an average value of 50 locations randomly selected from images obtained by photographing the obtained nanofibers with a scanning electron microscope (SU1510 manufactured by Hitachi High-Technologies Corporation). Can be measured by finding.
本発明の熱伝導性粒子充填ファイバーは、平均繊維長が、好ましくは１００μｍ以上、より好ましくは５００μｍ以上、更に好ましくは１，０００μｍ以上である。
ここで、熱伝導性粒子充填ファイバーの平均繊維長は、得られたナノファイバーを走査型電子顕微鏡（日立ハイテクノロジーズ製ＳＵ１５１０）により撮影して得た画像から、ランダムに５０箇所を選んで平均値を求めることにより測定できる。
The thermally conductive particle-filled fiber of the present invention has an average fiber length of preferably 100 μm or more, more preferably 500 μm or more, still more preferably 1,000 μm or more.
Here, the average fiber length of the thermally conductive particle-filled fibers is an average value of 50 locations randomly selected from images obtained by photographing the obtained nanofibers with a scanning electron microscope (SU1510 manufactured by Hitachi High-Technologies Corporation). Can be measured by finding.
本発明は、平均粒径１００ｎｍ未満の熱伝導性粒子（Ｘ１）、平均粒径１００ｎｍ以上９００ｎｍ以下の熱伝導性粒子（Ｘ２）、及び重量平均分子量３０，０００〜３００，０００の樹脂を混合する、本発明の熱伝導性粒子充填ファイバーの製造方法を提供する。 The present invention mixes thermally conductive particles (X1) having an average particle diameter of less than 100 nm, thermally conductive particles (X2) having an average particle diameter of 100 nm or more and 900 nm or less, and a resin having a weight average molecular weight of 30,000 to 300,000. , The present invention provides a method for producing a thermally conductive particle-filled fiber.
本発明の熱伝導性粒子充填ファイバーの製造方法では、熱伝導性粒子（Ｘ１）と熱伝導性粒子（Ｘ２）とを混合することで、熱伝導性粒子、更に熱伝導性粒子（Ｘ）を含み、熱伝導性粒子（Ｘ）中の粒子（Ｘ100）の割合が所定範囲にある本発明のファイバーを製造することができる。 In the method for producing thermally conductive particle-filled fibers of the present invention, thermally conductive particles (X1) and thermally conductive particles (X2) are mixed to obtain thermally conductive particles and further thermally conductive particles (X). It is possible to produce the fiber of the present invention containing the particles (X 100 ) in the thermally conductive particles (X) in a predetermined range.
本発明の熱伝導性粒子充填ファイバーの製造方法では、熱伝導性粒子（Ｘ１）と熱伝導性粒子（Ｘ２）とを、質量比（Ｘ１）：（Ｘ２）が１：１〜２５：１で混合することが、熱伝導性粒子の充填量を高め熱伝導性がよい点及び樹脂に配合する際の作業性がよい点で好ましく、１：１〜１５：１がより好ましく、１：１〜１０：１が更に好ましい。 In the method for producing thermally conductive particle-filled fibers of the present invention, the thermally conductive particles (X1) and the thermally conductive particles (X2) have a mass ratio (X1) :( X2) of 1: 1 to 25: 1. Mixing is preferable in terms of increasing the filling amount of the thermally conductive particles and having good thermal conductivity and good workability when blended with the resin, more preferably 1: 1 to 15: 1, and more preferably 1: 1 to 1. 10: 1 is more preferred.
熱伝導性粒子（Ｘ１）の平均粒径は、好ましくは１０〜９９ｎｍ、より好ましくは１０〜７０ｎｍ、更に好ましくは１０〜５０ｎｍである。熱伝導性粒子（Ｘ１）は、粒径１０以上１００ｎｍ未満の粒子から構成されていてよい。
また、熱伝導性粒子（Ｘ２）の平均粒径は、好ましくは１００〜９００ｎｍ、より好ましくは１００〜７００ｎｍ、更に好ましくは１００〜５００ｎｍである。熱伝導性粒子（Ｘ２）は、粒径１００以上９００ｎｍ以下の粒子から構成されていてよい。
ここで、熱伝導性粒子（Ｘ１）、（Ｘ２）の「平均」粒径は、熱伝導性粒子（Ｘ）の粒径（平均でない）と同様に測定することができる。
The average particle size of the thermally conductive particles (X1) is preferably 10 to 99 nm, more preferably 10 to 70 nm, and even more preferably 10 to 50 nm. The thermally conductive particles (X1) may be composed of particles having a particle size of 10 or more and less than 100 nm.
The average particle size of the heat conductive particles (X2) is preferably 100 to 900 nm, more preferably 100 to 700 nm, and even more preferably 100 to 500 nm. The thermally conductive particles (X2) may be composed of particles having a particle size of 100 or more and 900 nm or less.
Here, the "average" particle size of the thermally conductive particles (X1), (X2) can be measured in the same manner as the particle size (not average) of the thermally conductive particles (X).
本発明では、熱伝導性粒子（Ｘ１）と熱伝導性粒子（Ｘ２）と前記樹脂とを、熱伝導性粒子（Ｘ１）及び熱伝導性粒子（Ｘ２）の混合量が、熱伝導性粒子（Ｘ１）、熱伝導性粒子（Ｘ２）及び樹脂の混合量に対して、７０〜９５質量％、更に８０〜９５質量％、更に８５〜９５質量％となるように混合することが好ましい。 In the present invention, the mixed amount of the thermally conductive particles (X1), the thermally conductive particles (X2), and the resin, and the thermally conductive particles (X1) and the thermally conductive particles (X2) is the thermally conductive particles (X1). It is preferable to mix X1), the heat conductive particles (X2), and the resin so as to be 70 to 95% by mass, further 80 to 95% by mass, and further 85 to 95% by mass with respect to the mixed amount.
本発明の熱伝導性粒子充填ファイバーは、熱伝導性粒子の凝集を抑制するため、少なくとも一部が樹脂の繊維内部に高分散していることが好ましい。このような状態を得るために、本発明の熱伝導性粒子充填ファイバーの製造方法では、電界紡糸法を用いることが好ましい。電界紡糸法は、前記樹脂、熱伝導性粒子（Ｘ１）、熱伝導性粒子（Ｘ２）及び溶媒を含有するポリマー溶液を用いて行うことができる。 In order to suppress the aggregation of the heat conductive particles, at least a part of the heat conductive particle-filled fiber of the present invention is preferably highly dispersed inside the resin fiber. In order to obtain such a state, it is preferable to use an electric field spinning method in the method for producing a thermally conductive particle-filled fiber of the present invention. The electrospinning method can be carried out using a polymer solution containing the resin, the heat conductive particles (X1), the heat conductive particles (X2) and a solvent.
樹脂は、前記のものが使用されるが、製造工程及び加工工程での作業性がよい点で、熱硬化性、ＵＶ硬化性など硬化性である樹脂が少なくとも１種含まれることが好ましく、エポキシ基を含有する樹脂が少なくとも１種含まれることが更に好ましい。樹脂が硬化性である場合は、硬化剤はポリマー溶液に含有させることができる。 As the resin, the above-mentioned ones are used, but it is preferable that at least one kind of curable resin such as thermosetting and UV curable is contained, and epoxy is used, because the workability in the manufacturing process and the processing process is good. It is more preferable that at least one resin containing a group is contained. If the resin is curable, the curing agent can be included in the polymer solution.
ポリマー溶液の溶媒は、樹脂を溶解させるものであれば特に限定はなく、例えば、メチルエチルケトン、メチルイソブチルケトン、アセトン、シクロヘキサノン等のケトン、ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素、メタノール、エタノール、イソプロピルアルコール、ブタノール、イソブチルアルコール等のアルコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル等のエーテル、酢酸エチル、酢酸ブチル、乳酸エチル、γ−ブチロラクトン、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等のエステル、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアセトアミド、Ｎ−メチルピロリドン等のアミドが挙げられる。 The solvent of the polymer solution is not particularly limited as long as it dissolves the resin. For example, ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetone and cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, methanol, etc. Alcohols such as ethanol, isopropyl alcohol, butanol, isobutyl alcohol, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethyl acetate, butyl acetate, ethyl lactate, Examples thereof include esters such as γ-butyrolactone, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, and amides such as N, N-dimethylformamide, N, N-dimethylacetacetamide and N-methylpyrrolidone.
ポリマー溶液は、例えば、熱伝導性粒子（Ｘ１）と熱伝導性粒子（Ｘ２）と溶媒の混合物を樹脂と混合することにより調製することができる。その際、熱伝導性粒子（Ｘ１）と熱伝導性粒子（Ｘ２）の含有量の総和は、熱伝導性がよい点で、熱伝導性粒子（Ｘ１）、熱伝導性粒子（Ｘ２）及び樹脂の含有量の総和に対して、好ましくは５０〜９９質量％、より好ましく７０〜９９質量％、更に好ましくは８０〜９９質量％である。 The polymer solution can be prepared, for example, by mixing a mixture of thermally conductive particles (X1), thermally conductive particles (X2) and a solvent with a resin. At that time, the sum of the contents of the thermally conductive particles (X1) and the thermally conductive particles (X2) is that the thermally conductive particles (X1), the thermally conductive particles (X2), and the resin have good thermal conductivity. It is preferably 50 to 99% by mass, more preferably 70 to 99% by mass, and further preferably 80 to 99% by mass with respect to the total content of the particles.
ポリマー溶液は、分散剤を含有してもよい。分散剤としては、多価カルボン酸を含む脂肪酸や不飽和脂肪酸などを含むアニオン系分散剤、高分子系イオン性分散剤、リン酸エステル系化合物などが挙げられる。分散剤は、熱伝導性粒子（Ｘ１）と熱伝導性粒子（Ｘ２）の含有量の総和に対して、１〜２５質量％の割合で用いられることが好ましい。 The polymer solution may contain a dispersant. Examples of the dispersant include an anionic dispersant containing a fatty acid containing a polyvalent carboxylic acid and an unsaturated fatty acid, a polymer ionic dispersant, and a phosphate ester compound. The dispersant is preferably used in a proportion of 1 to 25% by mass with respect to the total content of the thermally conductive particles (X1) and the thermally conductive particles (X2).
樹脂としてエポキシ基を含有する樹脂を用い、エポキシ基の硬化剤を併用することが製造工程の操作が簡便な点で好ましい。具体的には、グリシジル基を有する樹脂と、硬化剤であるアミン化合物との組み合わせを用いることができる。より具体的には、ポリグリシジルメタクリレートと、鎖状脂肪族ポリアミン、例えばジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ジプロプレンジアミン、ジエチルアミノプロピルアミン等との組み合わせが挙げられる。硬化剤であるアミン化合物は、ポリマーに対して、１〜１０質量％の割合で用いられることが好ましい。 It is preferable to use a resin containing an epoxy group as the resin and to use an epoxy group curing agent in combination because the operation of the manufacturing process is simple. Specifically, a combination of a resin having a glycidyl group and an amine compound as a curing agent can be used. More specifically, a combination of polyglycidyl methacrylate and a chain aliphatic polyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diproprenedamine, diethylaminopropylamine and the like can be mentioned. The amine compound as a curing agent is preferably used in a proportion of 1 to 10% by mass with respect to the polymer.
得られたポリマー溶液を用いた電界紡糸法は、公知の方法に準じて行うことができる。 The electric field spinning method using the obtained polymer solution can be carried out according to a known method.
＜樹脂組成物及びその製造方法＞
本発明の樹脂組成物は、本発明の熱伝導性粒子充填ファイバーと、マトリックス樹脂とを含有する。本発明の熱伝導性粒子充填ファイバーを用いると、マトリックス樹脂と混練する際の粘度の過度な上昇を抑制できるため、取り扱い性や該ファイバーのマトリックス樹脂への分散性が良好となる。
樹脂組成物におけるマトリックス樹脂は、熱伝導性粒子充填ファイバーを構成する樹脂と同一でも異なっていてもよい。樹脂組成物におけるマトリックス樹脂としては、エポキシ樹脂、アクリル樹脂、アミド・イミド樹脂、フェノール樹脂、シリコーン樹脂などから選ばれる１種以上の樹脂が挙げられる。熱伝導性及び熱伝導性粒子充填ファイバー製造工程での作業性がよい点で、エポキシ樹脂が好ましいが、エポキシ基を含有する樹脂でもよい。より具体的には、ビスフェノールＡジグリシジルエーテルを構成モノマーとして含むエポキシ樹脂が好ましい。
<Resin composition and its manufacturing method>
The resin composition of the present invention contains the thermally conductive particle-filled fiber of the present invention and a matrix resin. When the thermally conductive particle-filled fiber of the present invention is used, it is possible to suppress an excessive increase in viscosity when kneading with the matrix resin, so that the handleability and the dispersibility of the fiber in the matrix resin are improved.
The matrix resin in the resin composition may be the same as or different from the resin constituting the heat conductive particle-filled fiber. Examples of the matrix resin in the resin composition include one or more resins selected from epoxy resin, acrylic resin, amide / imide resin, phenol resin, silicone resin and the like. Epoxy resins are preferable in terms of good workability in the thermal conductivity and the process of producing the thermally conductive particle-filled fibers, but a resin containing an epoxy group may also be used. More specifically, an epoxy resin containing bisphenol A diglycidyl ether as a constituent monomer is preferable.
用途によっては、本発明の樹脂組成物は、マトリックス樹脂中に更に熱伝導性粒子（Ｙ）を含有していてもよい。熱伝導性粒子（Ｙ）としては本発明の熱伝導性粒子充填ファイバー中の熱伝導性粒子（Ｘ）と同じ種類のものでも異なる種類のものでもいずれでもよく、具体的には酸化マグネシウム粒子、酸化アルミニウム粒子、酸化ケイ素粒子等の金属酸化物粒子、窒化アルミニウム粒子、窒化ホウ素粒子、窒化ケイ素粒子等の金属窒化物粒子、及び活性炭粒子、ナノダイヤ粒子、カーボンナノ粒子、フラーレン粒子、グラフェン粒子等の炭素粒子から選ばれる１種以上が挙げられる。 Depending on the application, the resin composition of the present invention may further contain thermally conductive particles (Y) in the matrix resin. The thermally conductive particles (Y) may be of the same type or different types as the thermally conductive particles (X) in the thermally conductive particle-filled fibers of the present invention, and specifically, magnesium oxide particles. Metal oxide particles such as aluminum oxide particles and silicon oxide particles, metal nitride particles such as aluminum nitride particles, boron nitride particles and silicon nitride particles, and activated carbon particles, nanodiamond particles, carbon nanoparticles, fullerene particles, graphene particles and the like. One or more selected from carbon particles can be mentioned.
熱伝導性粒子（Ｙ）の平均粒径は、添加目的に応じて選定できるが、０．１〜１０μｍであることが、熱伝導性がよい点で好ましい。熱伝導性粒子（Ｙ）の平均粒径は、前記の方法で測定することができる。 The average particle size of the thermally conductive particles (Y) can be selected according to the purpose of addition, but it is preferably 0.1 to 10 μm from the viewpoint of good thermal conductivity. The average particle size of the thermally conductive particles (Y) can be measured by the above method.
本発明の樹脂組成物は、熱伝導性粒子（Ｙ）を、好ましくは１〜９９質量％、より好ましくは２５〜９９質量％含有する。 The resin composition of the present invention contains the thermally conductive particles (Y) in an amount of preferably 1 to 99% by mass, more preferably 25 to 99% by mass.
本発明の樹脂組成物は、マトリックス樹脂１００質量部に対して、本発明の熱伝導性粒子充填ファイバーを、好ましくは１〜９０質量部、より好ましくは２５〜８０質量部、更に好ましくは３０〜７５質量部含有する。 In the resin composition of the present invention, the thermally conductive particle-filled fiber of the present invention is preferably 1 to 90 parts by mass, more preferably 25 to 80 parts by mass, and further preferably 30 to 30 parts by mass with respect to 100 parts by mass of the matrix resin. Contains 75 parts by mass.
本発明の樹脂組成物の一例として、以下のような組成が挙げられる。
マトリックス樹脂 ５〜９９質量部
熱伝導性粒子（Ｙ） ０〜９５質量部
本発明の熱伝導性粒子充填ファイバー １〜９０質量部
Examples of the resin composition of the present invention include the following compositions.
Matrix resin 5 to 99 parts by mass Thermally conductive particles (Y) 0 to 95 parts by mass Thermally conductive particle-filled fiber of the present invention 1 to 90 parts by mass
本発明の樹脂組成物が熱伝導性粒子（Ｙ）を含有する場合、マトリックス樹脂と熱伝導性粒子（Ｙ）の合計１００質量部に対して、本発明の熱伝導性粒子充填ファイバーを、好ましくは１〜９０質量部、より好ましくは１〜５０質量部、更に好ましくは１〜２５質量部含有する。更に熱伝導性粒子充填ファイバー中の熱伝導性粒子（Ｘ）が熱伝導性粒子（Ｙ）に対して、１〜７５質量％となるように用いることが好ましい。 When the resin composition of the present invention contains the heat conductive particles (Y), the heat conductive particle-filled fiber of the present invention is preferably used with respect to a total of 100 parts by mass of the matrix resin and the heat conductive particles (Y). Is contained in an amount of 1 to 90 parts by mass, more preferably 1 to 50 parts by mass, still more preferably 1 to 25 parts by mass. Further, it is preferable to use the heat conductive particles (X) in the heat conductive particle-filled fiber so as to be 1 to 75% by mass with respect to the heat conductive particles (Y).
本発明の樹脂組成物の用途として、各種電子デバイスの放熱材料、熱交換材料などが挙げられる。 Applications of the resin composition of the present invention include heat dissipation materials and heat exchange materials for various electronic devices.
本発明の樹脂組成物は、本発明の熱伝導性粒子充填ファイバーを製造する工程（Ｉ）と、得られた熱伝導性粒子充填ファイバーをマトリックス樹脂に配合する工程（II）を順次行うことにより製造することができる。 The resin composition of the present invention is obtained by sequentially performing a step (I) of producing the thermally conductive particle-filled fiber of the present invention and a step (II) of blending the obtained thermally conductive particle-filled fiber into a matrix resin. Can be manufactured.
本発明は、本発明の熱伝導性粒子充填ファイバーの製造工程（Ｉ）と、前記工程（Ｉ）で得られた熱伝導性粒子充填ファイバーを樹脂に配合する工程（II）とを有する樹脂組成物の製造方法であって、前記工程（Ｉ）が、樹脂、熱伝導性粒子（Ｘ１）、熱伝導性粒子（Ｘ２）及び溶媒を含有するポリマー溶液を用いて電界紡糸法により紡糸する工程を有する、樹脂組成物の製造方法を提供する。 The present invention has a resin composition comprising a step (I) of manufacturing the thermally conductive particle-filled fiber of the present invention and a step (II) of blending the thermally conductive particle-filled fiber obtained in the step (I) into a resin. A method for producing a product, wherein the step (I) is a step of spinning by an electrospinning method using a polymer solution containing a resin, a heat conductive particle (X1), a heat conductive particle (X2) and a solvent. Provided is a method for producing a resin composition having.
工程（Ｉ）は、前記樹脂、熱伝導性粒子（Ｘ１）、熱伝導性粒子（Ｘ２）及び溶媒を含有するポリマー溶液を用いた電界紡糸法により紡糸する、本発明の熱伝導性粒子充填ファイバーの製造方法と同じである。 The step (I) is the heat conductive particle-filled fiber of the present invention, which is spun by an electrospinning method using a polymer solution containing the resin, the heat conductive particles (X1), the heat conductive particles (X2) and a solvent. It is the same as the manufacturing method of.
工程（II）では、熱伝導性粒子充填ファイバーをマトリックス樹脂の構成モノマーと混合し、該構成モノマーを重合させることで、熱伝導性粒子充填ファイバーをマトリックス樹脂に配合することができる。また、熱伝導性粒子充填ファイバーとマトリックス樹脂とを混練して配合することもできる。 In step (II), the thermally conductive particle-filled fiber is mixed with the constituent monomer of the matrix resin, and the constituent monomer is polymerized, whereby the thermally conductive particle-filled fiber can be blended with the matrix resin. Further, the heat conductive particle-filled fiber and the matrix resin can be kneaded and blended.
また、工程（II）では、熱伝導性粒子（Ｙ）をマトリックス樹脂に配合することができる。 Further, in the step (II), the thermally conductive particles (Y) can be blended with the matrix resin.
工程（II）では、例えば、工程（Ｉ）で得られた熱伝導性粒子充填ファイバー、及びマトリックス樹脂の構成モノマー、任意に熱伝導性粒子（Ｙ）を混合し、該構成モノマーを重合させることで、熱伝導性粒子充填ファイバーと任意に熱伝導性粒子（Ｙ）とをマトリックス樹脂に配合することができる。
工程（II）では、工程（Ｉ）で得られた熱伝導性粒子充填ファイバー、マトリックス樹脂の構成モノマー、及び熱伝導性粒子（Ｙ）を混合し、該構成モノマーを重合させることで、熱伝導性粒子充填ファイバーと熱伝導性粒子（Ｙ）とをマトリックス樹脂に配合することができる。
In the step (II), for example, the thermally conductive particle-filled fiber obtained in the step (I), the constituent monomer of the matrix resin, and optionally the thermally conductive particle (Y) are mixed, and the constituent monomer is polymerized. Then, the thermally conductive particle-filled fiber and optionally the thermally conductive particles (Y) can be blended in the matrix resin.
In the step (II), the heat conductive particle-filled fiber obtained in the step (I), the constituent monomer of the matrix resin, and the heat conductive particle (Y) are mixed, and the constituent monomer is polymerized to conduct heat conduction. The sex particle-filled fiber and the thermally conductive particles (Y) can be blended in the matrix resin.
更に工程（II）の後に、得られた樹脂組成物を成型する工程（III）を設けることができる。すなわち、本発明により、工程（Ｉ）、工程（II）及び工程（III）から成る樹脂成型品の製造方法が提供される。工程（II）において、マトリックス樹脂の構成モノマーを重合させる方法を採用する場合は、重合用の混合物を型枠に充填したり支持体に塗布したりした後、硬化させて、樹脂組成物の製造と成型を同時に行っても良い。例えば、工程（Ｉ）で得られた熱伝導性粒子充填ファイバー、熱伝導性粒子（Ｙ）、及びマトリックス樹脂の構成モノマーを混合し、得られた混合物を型枠に充填し、該型枠中で前記構成モノマーを重合させることで、工程（II）と工程（III）を同時に行い、熱伝導性粒子充填ファイバーと熱伝導性粒子（Ｙ）とを含有する樹脂組成物を成型することができる。また、工程（II）で得られた前記混合物の塗膜を硬化させて薄膜を形成する工程も工程（III）に含んでいてもよい。 Further, after the step (II), a step (III) for molding the obtained resin composition can be provided. That is, the present invention provides a method for producing a resin molded product including step (I), step (II) and step (III). When the method of polymerizing the constituent monomers of the matrix resin is adopted in the step (II), the mixture for polymerization is filled in a mold or applied to a support and then cured to produce a resin composition. And molding may be performed at the same time. For example, the thermally conductive particle-filled fibers obtained in step (I), the thermally conductive particles (Y), and the constituent monomers of the matrix resin are mixed, and the obtained mixture is filled in a mold and contained in the mold. By polymerizing the constituent monomers in the above step (II) and step (III) at the same time, a resin composition containing the thermally conductive particle-filled fiber and the thermally conductive particles (Y) can be molded. .. Further, the step (III) may also include a step of curing the coating film of the mixture obtained in the step (II) to form a thin film.
また、本発明の熱伝導性粒子充填ファイバー又は本発明の樹脂組成物と、他の部材とを複合させた複合物品を得ることもできる。例えば、本発明の熱伝導性粒子充填ファイバーと、シート、密着性フィルムなどとを複合させた物品が挙げられる。 Further, it is also possible to obtain a composite article in which the heat conductive particle-filled fiber of the present invention or the resin composition of the present invention is composited with another member. For example, an article obtained by combining the thermally conductive particle-filled fiber of the present invention with a sheet, an adhesive film, or the like can be mentioned.
本発明により、本発明の熱伝導性粒子充填ファイバーとマトリックス樹脂用の構成モノマーと混合し、該混合物中の前記モノマーを硬化させる、成型品の製造方法が提供される。
更に、本発明により、本発明の熱伝導性粒子充填ファイバーとマトリックス樹脂用の構成モノマーと混合し、該混合物を薄膜とした後、該薄膜中の前記モノマーを硬化させる、硬化薄膜の製造方法が提供される。前記混合物を薄膜にする方法は、例えば、支持体に前記混合物を塗布する方法が挙げられる。
INDUSTRIAL APPLICABILITY The present invention provides a method for producing a molded product, which comprises mixing the thermally conductive particle-filled fiber of the present invention with a constituent monomer for a matrix resin and curing the monomer in the mixture.
Further, according to the present invention, there is a method for producing a cured thin film, in which the thermally conductive particle-filled fiber of the present invention and a constituent monomer for a matrix resin are mixed to form a thin film, and then the monomer in the thin film is cured. Provided. Examples of the method of forming the mixture into a thin film include a method of applying the mixture to a support.
＜熱伝導性粒子充填ファイバーの製造＞
ポリマー溶液の調製
熱伝導性粒子（Ｘ１）として平均粒径３５ｎｍの酸化マグネシウム粒子と溶媒であるメチルエチルケトンとを混合して分散液を調製した。分散液中の酸化マグネシウム粒子の濃度は、３５質量％であった。また、熱伝導性粒子（Ｘ２）として平均粒径５００ｎｍの酸化マグネシウムとメチルエチルケトンとを混合して分散液を調製した。分散液中の酸化マグネシウム粒子の濃度は、３５質量％であった。なお、前記平均粒径３５ｎｍの酸化マグネシウム粒子は、１０ｎｍ以上１００ｎｍ未満の粒子で構成されていた。また、前記平均粒径５００ｎｍの酸化マグネシウムは、粒径が１００ｎｍ以上９００ｎｍ以下の粒子で構成されていた。
樹脂として、本発明の樹脂である、粉末状のポリグリシジルメタクリレート（重量平均分子量２００，０００）（ＰＧＭＡ（１）とする）と、比較の樹脂である、粉末状のポリグリシジルメタクリレート（重量平均分子量１２，０００）（比較ＰＧＭＡとする）を用いた。
樹脂の硬化剤としてトリエチレンテトラミン（ＴＥＴＡ）を用いた。
前記２種の分散液を、熱伝導性粒子（Ｘ１）と熱伝導性粒子（Ｘ２）の混合比が表１の通りとなるように用い、該分散液と前記樹脂を、表１の組成となるように組み合わせて、及び前記硬化剤と共にシェイカーを用いて混合し、電解紡糸法に用いるポリマー溶液を調製した。
一例として、実施例１のポリマー溶液の組成は、酸化マグネシウム粒子３２．０質量％、メチルエチルケトン５９．６質量％、ＰＧＭＡ８．０質量％、ＴＥＴＡ０．４質量％であった。
<Manufacturing of thermally conductive particle-filled fibers>
Preparation of Polymer Solution A dispersion was prepared by mixing magnesium oxide particles having an average particle size of 35 nm as thermally conductive particles (X1) and methyl ethyl ketone as a solvent. The concentration of magnesium oxide particles in the dispersion was 35% by mass. Further, magnesium oxide having an average particle size of 500 nm and methyl ethyl ketone were mixed as heat conductive particles (X2) to prepare a dispersion. The concentration of magnesium oxide particles in the dispersion was 35% by mass. The magnesium oxide particles having an average particle diameter of 35 nm were composed of particles having a diameter of 10 nm or more and less than 100 nm. Further, the magnesium oxide having an average particle size of 500 nm was composed of particles having a particle size of 100 nm or more and 900 nm or less.
As the resin, powdered polyglycidyl methacrylate (weight average molecular weight 200,000) (PGMA (1)), which is the resin of the present invention, and powdered polyglycidyl methacrylate (weight average molecular weight), which is a comparative resin, are used. 12,000) (referred to as comparative PGMA) was used.
Triethylenetetramine (TETA) was used as a resin curing agent.
The two types of dispersions were used so that the mixing ratio of the thermally conductive particles (X1) and the thermally conductive particles (X2) was as shown in Table 1, and the dispersion and the resin were used with the composition of Table 1. The polymer solutions used in the electrolytic spinning method were prepared by combining them in such a manner and mixing them together with the curing agent using a shaker.
As an example, the composition of the polymer solution of Example 1 was 32.0% by mass of magnesium oxide particles, 59.6% by mass of methyl ethyl ketone, 8.0% by mass of PGMA, and 0.4% by mass of TETA.
（２）電界紡糸法による熱伝導性粒子充填ファイバーの製造
前記（１）で調製したポリマー溶液を用いて、電界紡糸用装置（ＮＥＵナノファイバーエレクトロスピニングユニット、カトーテック株式会社）で電界紡糸し、溶媒であるメチルエチルケトンを揮発させて、平均繊維径が８６５ｎｍ及び平均繊維長５００μｍ以上の熱伝導性粒子充填ファイバーを製造した。電界紡糸用装置の条件は、シリンジ速度：０．６０ｍｍ／分、ノズル内径：０．８２ｍｍ、回転式ターゲット（捕集体）：ステンレス製ドラム（直径１０ｃｍ）、回転式ターゲット速度：３．００ｍ／分、ノズルへの印加電圧：２５ｋＶ、ノズル先端から回転式ターゲットまでの距離：１０ｃｍとした。
この熱伝導性粒子充填ファイバーでは、酸化マグネシウム粒子の少なくとも一部が繊維内部に存在していた。電解紡糸法後の熱伝導性粒子充填ファイバーの組成は、一例として、実施例１では、酸化マグネシウム粒子８０質量％、ＰＧＭＡの架橋樹脂２０質量％（ＰＧＭＡ１９質量％とＴＥＴＡ１質量％に相当）であった。熱伝導性粒子充填ファイバーの平均繊維径と平均繊維長は、一例として、実施例１では、平均繊維径８００ｎｍ、平均繊維長５００μｍであった。
表１に、実施例、比較例の熱伝導性粒子充填ファイバー中のＭｇＯの含有量（熱伝導性粒子の含有量）、熱伝導性粒子（Ｘ）の含有量、及び熱伝導性粒子（Ｘ）中の粒子（Ｘ100）の割合を示した。
(2) Production of thermally conductive particle-filled fiber by electrospinning method Using the polymer solution prepared in (1) above, electrospinning is performed with an electrospinning device (NEU nanofiber electrospinning unit, Katotech Co., Ltd.). The solvent, methyl ethyl ketone, was volatilized to produce thermally conductive particle-filled fibers having an average fiber diameter of 865 nm and an average fiber length of 500 μm or more. The conditions of the electric field spinning device are syringe speed: 0.60 mm / min, nozzle inner diameter: 0.82 mm, rotary target (collector): stainless steel drum (diameter 10 cm), rotary target speed: 3.00 m / min. The voltage applied to the nozzle was 25 kV, and the distance from the tip of the nozzle to the rotary target was 10 cm.
In this thermally conductive particle-filled fiber, at least a part of magnesium oxide particles was present inside the fiber. As an example, the composition of the thermally conductive particle-filled fiber after the electrolytic spinning method is, in Example 1, 80% by mass of magnesium oxide particles and 20% by mass of a crosslinked resin of PGMA (corresponding to 19% by mass of PGMA and 1% by mass of TETA). It was. As an example, the average fiber diameter and the average fiber length of the thermally conductive particle-filled fibers were 800 nm in the average fiber diameter and 500 μm in the average fiber length in Example 1.
Table 1 shows the content of MgO (content of thermally conductive particles), the content of thermally conductive particles (X), and thermally conductive particles (X) in the thermally conductive particle-filled fibers of Examples and Comparative Examples. ) The proportion of particles (X 100 ) in.
（３）作業性の評価
前記（２）で得られた熱伝導性粒子充填ファイバーにおいて、マトリックス樹脂に混練する際の取り扱いやすさを、以下の基準で評価した。
◎：熱伝導性粒子充填ファイバーを添加した際に粘度が大きく上昇せず、マトリックス樹脂に分散しやすかった。
○：熱伝導性粒子充填ファイバーを添加した際に粘度がやや上昇したが、マトリックス樹脂への分散には支障がなかった。
△：熱伝導性粒子充填ファイバーを添加した際の粘度上昇があり、マトリックス樹脂へ分散しづらかった。
×：熱伝導性粒子充填ファイバーを添加した際に大きな粘度上昇があり、マトリックス樹脂中に分散せずファイバーの塊として残った。
(3) Evaluation of Workability In the heat conductive particle-filled fiber obtained in (2) above, the ease of handling when kneading with the matrix resin was evaluated according to the following criteria.
⊚: When the heat conductive particle-filled fiber was added, the viscosity did not increase significantly, and it was easy to disperse in the matrix resin.
◯: The viscosity increased slightly when the heat conductive particle-filled fiber was added, but there was no problem in dispersing in the matrix resin.
Δ: There was an increase in viscosity when the thermally conductive particle-filled fiber was added, and it was difficult to disperse in the matrix resin.
X: When the heat conductive particle-filled fiber was added, there was a large increase in viscosity, and the fiber was not dispersed in the matrix resin and remained as a lump of fiber.
＜評価用フィルムの製造＞
得られた熱伝導性粒子充填ファイバーと、マトリックス樹脂用モノマーであるビスフェノールＡジグリシジルエーテル（ＢＰＡＤＧＥ）と、熱伝導性粒子（Ｙ）である酸化アルミニウム（平均粒径３μｍ）とを超音波ホモジナイザーで混合し、モノマー溶液を調製した。調製したモノマー溶液にトリエチレンテトラミンを添加し、テフロン（登録商標）枠へ流し込み、１００℃で１時間加熱後、室温まで冷却して、１５ｍｍ×３０ｍｍ四方の評価用フィルムを製造した。
本評価では、ＢＰＡＤＧＥと酸化アルミニウム（Ａｌ２Ｏ３）の合計中、酸化アルミニウムの量が５０質量％である組成を採用した。また、熱伝導性粒子充填ファイバーは、酸化マグネシウム粒子の含有量が１０〜９０質量％のものを任意に選択して採用した。そして、ＢＰＡＤＧＥと酸化アルミニウムの合計１００質量部に対して、熱伝導性粒子充填ファイバーを１０質量部添加してフィルムを製造した。実施例のフィルムでは、マトリックス樹脂中に熱伝導性粒子充填ファイバーが分散していた。
なお、本評価では、便宜的に、ＢＰＡＤＧＥと酸化アルミニウムとを合わせて、マトリックス樹脂と表記した。
<Manufacturing of evaluation film>
The obtained thermally conductive particle-filled fiber, bisphenol A diglycidyl ether (BPADGE) which is a monomer for a matrix resin, and aluminum oxide (average particle size 3 μm) which is a thermally conductive particle (Y) are combined with an ultrasonic homogenizer. Mixing prepared a monomer solution. Triethylenetetramine was added to the prepared monomer solution, poured into a Teflon (registered trademark) frame, heated at 100 ° C. for 1 hour, and then cooled to room temperature to produce a 15 mm × 30 mm square evaluation film.
In this evaluation, a composition in which the amount of aluminum oxide is 50% by mass in the total of BPADGE and aluminum oxide (Al 2 O 3) was adopted. Further, as the heat conductive particle-filled fiber, those having a magnesium oxide particle content of 10 to 90% by mass were arbitrarily selected and adopted. Then, 10 parts by mass of the thermally conductive particle-filled fiber was added to 100 parts by mass of the total of BPADGE and aluminum oxide to produce a film. In the film of the example, the heat conductive particle-filled fibers were dispersed in the matrix resin.
In this evaluation, for convenience, BPADGE and aluminum oxide are collectively referred to as a matrix resin.
＜フィルムの評価＞
得られた評価用フィルムの熱拡散率、比熱、密度を測定し、熱伝導率（Ｗ／ｍ・Ｋ）を下記の式により算出した。
熱伝導率＝熱拡散率×比熱×密度
熱拡散率は熱物性測定装置（ベテルハドソン研究所：サーモウェーブアナライザＴＡ３）を使用し測定した。フィルムの垂直方向に対して中心と、そこから左前、右前、左奥、右奥に１ｍｍずつずらした計５か所を測定し、垂直平均を算出した。
比熱は示差走査熱量計（株式会社島津製作所製：ＤＳＣ−６０）を使用し測定した。
比重は電子比重計（アルファーミラージュ株式会社製：ＥＷ−３００ＳＧ）を使用し測定した。
結果を表１に示した。なお、表１には、参考例として、熱伝導性粒子充填ファイバーを添加せずに製造したフィルムの熱伝導率も示した。
<Evaluation of film>
The thermal diffusivity, specific heat, and density of the obtained evaluation film were measured, and the thermal conductivity (W / m · K) was calculated by the following formula.
Thermal conductivity = thermal diffusivity x specific heat x density The thermal diffusivity was measured using a thermophysical property measuring device (Bethel Hudson Laboratory: Thermowave Analyzer TA3). The vertical average was calculated by measuring a total of five locations shifted by 1 mm from the center in the vertical direction of the film and to the front left, front right, back left, and back right.
The specific heat was measured using a differential scanning calorimeter (manufactured by Shimadzu Corporation: DSC-60).
The specific gravity was measured using an electronic hydrometer (manufactured by Alpha Mirage Co., Ltd .: EW-300SG).
The results are shown in Table 1. In addition, Table 1 also shows the thermal conductivity of the film produced without adding the thermally conductive particle-filled fiber as a reference example.
添加量は、マトリックス樹脂（ＢＰＡＤＧＥと酸化アルミニウムの合計）１００質量部に対する添加量である。 The addition amount is an addition amount with respect to 100 parts by mass of the matrix resin (total of BPADGE and aluminum oxide).
表１の実施例１〜４の結果から、重量平均分子量２００，０００のＰＧＭＡ（１）をマトリックス樹脂として用い、粒径１００ｎｍ〜９００ｎｍの熱伝導粒子（Ｘ１００）を５〜５０質量％含むファイバーを作成することにより、熱伝導率が高く作業性にも優れた熱伝導性ファイバーが製造できることがわかった。一方、比較例１及び２のように粒子（Ｘ）中の粒子（Ｘ１００）の割合が５０質量％よりも大きいと、重量平均分子量２００，０００のＰＧＭＡ（１）をマトリックス樹脂として用いても熱伝導率及び作業性が実施例に比べて劣ることがわかった。また、重量平均分子量が１２，０００の比較ＰＧＭＡをマトリックス樹脂とした比較例３の熱伝導率及び作業性は、ＭｇＯの含有量、粒子（Ｘ）の含有量、粒子（Ｘ）中の粒子（Ｘ１００）の割合が同じ実施例３に比べていずれも劣ることがわかった。このことから、重量平均分子量２００，０００のＰＧＭＡ（１）をマトリックス樹脂として用いることの効果が明白であるといえる。 From the results of Examples 1 to 4 in Table 1, a fiber containing 5 to 50% by mass of heat conductive particles (X 100 ) having a particle size of 100 nm to 900 nm using PGMA (1) having a weight average molecular weight of 200,000 as a matrix resin. It was found that a thermally conductive fiber having high thermal conductivity and excellent workability can be produced by producing the above. On the other hand, when the ratio of the particles (X 100 ) in the particles (X) is larger than 50% by mass as in Comparative Examples 1 and 2, even if PGMA (1) having a weight average molecular weight of 200,000 is used as the matrix resin. It was found that the thermal conductivity and workability were inferior to those of the examples. Further, the thermal conductivity and workability of Comparative Example 3 using Comparative PGMA having a weight average molecular weight of 12,000 as a matrix resin are the MgO content, the particle (X) content, and the particles in the particles (X). It was found that the ratio of X 100 ) was inferior to that of Example 3 which was the same. From this, it can be said that the effect of using PGMA (1) having a weight average molecular weight of 200,000 as the matrix resin is clear.
Claims (18)
熱伝導性粒子は、粒径１０〜９００ｎｍの熱伝導性粒子（Ｘ）を含み、
熱伝導性粒子（Ｘ）中、粒径１００ｎｍ以上の粒子〔（以下、粒子（Ｘ100）という〕の割合が５〜５０質量％である、
熱伝導性粒子充填ファイバー。 A thermally conductive particle-filled fiber containing thermally conductive particles and a resin having a weight average molecular weight of 30,000 to 300,000.
The thermally conductive particles include thermally conductive particles (X) having a particle size of 10 to 900 nm.
The proportion of particles having a particle size of 100 nm or more [(hereinafter referred to as particles (X 100 )]] among the thermally conductive particles (X) is 5 to 50% by mass.
Thermally conductive particle-filled fiber.
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| WO2014112464A1 (en) * | 2013-01-15 | 2014-07-24 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, laminate, metal foil-clad laminate, and printed wiring board |
| JP2014162914A (en) * | 2013-02-28 | 2014-09-08 | Sumitomo Bakelite Co Ltd | Resin sheet and film |
| WO2019044045A1 (en) * | 2017-08-28 | 2019-03-07 | 関東電化工業株式会社 | Thermally conductive particle-filled fiber |
| JP2019065354A (en) * | 2017-10-02 | 2019-04-25 | リンテック株式会社 | Film-like firing material, and film-like firing material with support sheet |
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| JP2010285569A (en) * | 2009-06-15 | 2010-12-24 | Panasonic Corp | Thermoconductive resin material and production method thereof |
| WO2014112464A1 (en) * | 2013-01-15 | 2014-07-24 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, laminate, metal foil-clad laminate, and printed wiring board |
| JP2014162914A (en) * | 2013-02-28 | 2014-09-08 | Sumitomo Bakelite Co Ltd | Resin sheet and film |
| WO2019044045A1 (en) * | 2017-08-28 | 2019-03-07 | 関東電化工業株式会社 | Thermally conductive particle-filled fiber |
| JP2019065354A (en) * | 2017-10-02 | 2019-04-25 | リンテック株式会社 | Film-like firing material, and film-like firing material with support sheet |
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