TWI476261B - Thermal follower - Google Patents
Thermal follower Download PDFInfo
- Publication number
- TWI476261B TWI476261B TW099111420A TW99111420A TWI476261B TW I476261 B TWI476261 B TW I476261B TW 099111420 A TW099111420 A TW 099111420A TW 99111420 A TW99111420 A TW 99111420A TW I476261 B TWI476261 B TW I476261B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- thermally conductive
- dianhydride
- conductive adhesive
- heat
- Prior art date
Links
- 239000000853 adhesive Substances 0.000 claims description 54
- 230000001070 adhesive effect Effects 0.000 claims description 52
- 239000011347 resin Substances 0.000 claims description 31
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011231 conductive filler Substances 0.000 claims description 23
- -1 aliphatic diamines Chemical class 0.000 claims description 17
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 229920002675 Polyoxyl Polymers 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 11
- MMCOUVMKNAHQOY-UHFFFAOYSA-L oxido carbonate Chemical compound [O-]OC([O-])=O MMCOUVMKNAHQOY-UHFFFAOYSA-L 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 229920002098 polyfluorene Polymers 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 125000000962 organic group Chemical group 0.000 claims description 6
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 150000004984 aromatic diamines Chemical class 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
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- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical group C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 claims description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical group C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 238000010292 electrical insulation Methods 0.000 claims description 2
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 125000005504 styryl group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
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- 125000006160 pyromellitic dianhydride group Chemical group 0.000 claims 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 24
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
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- FXFFFSRHYPNPOB-UHFFFAOYSA-N 4-[2-(3,4-dicarboxy-2,5,6-trifluorophenyl)propyl]-3,5,6-trifluorophthalic acid Chemical compound FC=1C(=C(C(=C(C=1C(=O)O)C(=O)O)F)CC(C)C=1C(=C(C(C(=O)O)=C(C=1F)F)C(=O)O)F)F FXFFFSRHYPNPOB-UHFFFAOYSA-N 0.000 description 4
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
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- 238000000862 absorption spectrum Methods 0.000 description 4
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- 150000002148 esters Chemical class 0.000 description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
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- 229920002223 polystyrene Polymers 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-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
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
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- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
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- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
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- ZACVGCNKGYYQHA-UHFFFAOYSA-N 2-ethylhexoxycarbonyloxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOC(=O)OCC(CC)CCCC ZACVGCNKGYYQHA-UHFFFAOYSA-N 0.000 description 1
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- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K7/00—Constructional details common to different types of electric apparatus
- H05K7/20—Modifications to facilitate cooling, ventilating, or heating
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Die Bonding (AREA)
Description
本發明係關於一種導熱性接著劑,特別係關於一種適用於用以接著電子元件與散熱構件或發熱構件之導熱性接著劑。BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a thermally conductive adhesive, and more particularly to a thermally conductive adhesive suitable for use in subsequent electronic components and heat dissipating members or heat generating members.
近年,伴隨電子元件例如電腦之中央運算處理裝置(CPU)及晶片組之高性能化、小型化及高密度化,電子元件及安裝該電子元件之構件的發熱會變大起來。因此,電子元件之冷卻在維持電子元件及安裝該電子元件之構件的性能上成為非常重要之技術。電子元件之散熱效率一般係藉由使導熱性佳的物質接觸電子元件而提昇。因此,具有優異導熱性的散熱材料(TIM)的需要正在增加。In recent years, with the high performance, miniaturization, and high density of electronic processing devices (CPUs) and chipsets of electronic components such as computers, the heat generation of electronic components and components to which the electronic components are mounted has increased. Therefore, the cooling of the electronic component becomes a very important technique in maintaining the performance of the electronic component and the component on which the electronic component is mounted. The heat dissipation efficiency of an electronic component is generally improved by contacting a material having good thermal conductivity to the electronic component. Therefore, the demand for a heat dissipating material (TIM) having excellent thermal conductivity is increasing.
散熱材料例如被放置於電子元件與冷卻系統(例如Heat sink)之間,擔任將來自電子元件發熱之熱有效地傳導至冷卻系統的角色。散熱材料係從其形狀或使用方法分類成薄片狀成型物及膏狀組成物。薄片狀成型物係分類成例如彈性體(具彈性之高分子物質)型的散熱片、及熱軟化型之相轉變薄片(使用隨溫度進行相變化之散熱材料的薄片)。膏狀組成物係可分類成例如非硬化型之散熱膏、及塗佈時為膏狀,同時例如藉熱處理而進行凝膠化或彈性體化之散熱凝膠或散熱性接著劑。The heat dissipating material is placed, for example, between the electronic component and a cooling system (e.g., a heat sink) to function to efficiently conduct heat from the heating of the electronic component to the cooling system. The heat dissipating material is classified into a flake-shaped molded product and a paste-like composition from its shape or method of use. The sheet-like molded product is classified into, for example, an elastic (elastic polymer) type heat sink and a thermosoftening type phase change sheet (a sheet using a heat-dissipating material that changes phase with temperature). The paste composition can be classified into, for example, a non-hardening type heat-dissipating paste, and a heat-dissipating gel or a heat-dissipating adhesive which is gelled or gelled by heat treatment, for example, at the time of coating.
此等之散熱材料一般係於有機聚合物材料中高密度填充導熱物質之複合材料。有機聚合物材料之導熱率一般很小,依有機聚合物材料之種類而無很大的相異。因而,散熱材料之導熱率係非常依存於導熱物質之有機聚合物材料中的體積填充率。因而,有機聚合物材料中如何地填充許多導熱物質乃很重要。Such heat dissipating materials are generally composite materials of high density filled thermal conductive materials in organic polymeric materials. The thermal conductivity of organic polymeric materials is generally small and does not vary greatly depending on the type of organic polymeric material. Thus, the thermal conductivity of the heat dissipating material is highly dependent on the volumetric fill rate in the organic polymeric material of the thermally conductive material. Therefore, it is important to how many thermal conductive materials are filled in the organic polymer material.
散熱性接著劑係被要求具有高導熱性同時並在各種環境或應力下具有接著力。於有機聚合物材料中愈高密度地填充導熱物質,散熱材料之散熱性愈提高。但,於有機聚合物材料中愈高密度地填充導熱物質,散熱材料本身會變脆,可撓性或與被黏體之接著力變差。Heat-dissipating adhesives are required to have high thermal conductivity while having an adhesive force under various environments or stresses. The higher the density of the organic polymer material is filled with the heat conductive material, the more the heat dissipation property of the heat dissipating material is improved. However, the higher the density of the organic polymer material is filled with the heat conductive material, the heat dissipating material itself becomes brittle, and the flexibility or adhesion to the adherend deteriorates.
散熱性接著劑之有機聚合物材料已知有環氧樹脂、聚矽氧聚合物、聚醯亞胺等。但,環氧樹脂係接著性良好,但耐熱、耐久性上有缺點。因此,對於導熱性物質之塗佈性或硬化後之柔軟性或熱安定性等而言,可適宜使用聚矽氧聚合物(例如,參照下述專利文獻1及2)。但,使用聚矽氧聚合物之散熱材料中有時不能滿足接著性及散熱性之兩者。The organic polymer material of the heat-dissipating adhesive is known as an epoxy resin, a polyoxyalkylene polymer, a polyimine or the like. However, the epoxy resin has good adhesion, but has disadvantages in heat resistance and durability. Therefore, a polyfluorene oxide polymer can be suitably used for the coating property of the thermal conductive material, the flexibility after curing, the thermal stability, and the like (for example, refer to Patent Documents 1 and 2 below). However, in the heat dissipating material using a polyoxyl polymer, both the adhesion and the heat dissipation property may not be satisfied.
又,使用已改良耐熱性之聚醯亞胺時,聚醯亞胺樹脂為固體,故無法填充導熱物質,而不得不溶解於溶劑等而填充。為避免此,必須以成為前驅體之聚醯胺酸溶液填充導熱物質,於其硬化一般必須加熱至300℃以上,故無法避免於周圍的熱負荷。Further, when a polyimide having improved heat resistance is used, since the polyimide resin is solid, it cannot be filled with a heat conductive material, and it has to be dissolved in a solvent or the like to be filled. In order to avoid this, it is necessary to fill the heat-conducting substance with a poly-proline solution which is a precursor, and it is necessary to heat it to 300 ° C or more in the hardening, so that the surrounding heat load cannot be avoided.
又,為了半導體元件及印刷基板等之配線部分的表面保護,已知有使用聚醯亞胺聚矽氧樹脂,相較於聚矽氧橡膠,在高濕條件下之基材的密著性及耐久性高(例如參照下述專利文獻3)。亦已揭示有利用含有此聚醯亞胺聚矽氧樹脂之組成物作為半導體的接著劑(例如參照專利文獻4)。但,使用此等之聚醯亞胺聚矽氧樹脂的導熱性之接著劑,尤其要求電絕緣性之導熱性接著劑尚未被硏究。Further, in order to protect the surface of a wiring portion such as a semiconductor element or a printed circuit board, it is known that a polyimide resin is used, and the adhesion of a substrate under high-humidity conditions is compared with that of a polyoxyxene rubber. The durability is high (for example, refer to Patent Document 3 below). It has also been disclosed that a composition containing the polyamidene polyoxymethylene resin is used as an adhesive for a semiconductor (for example, refer to Patent Document 4). However, the use of the thermal conductivity adhesive of the polyamidene polyoxyl resin, in particular, the thermal insulating adhesive which requires electrical insulation has not been studied.
[專利文獻1]特開2006-342200號公報[Patent Document 1] JP-A-2006-342200
[專利文獻2]特公昭61-3670號公報[Patent Document 2] Japanese Patent Publication No. 61-3670
[專利文獻3]特開2002-012667號公報[Patent Document 3] JP-A-2002-012667
[專利文獻4]特開2006-005159號公報[Patent Document 4] JP-A-2006-005159
本發明之目的在於提供一種具有優異之導熱性,進一步具有對於被接著物例如發熱構件及散熱構件優異之接著性的電絕緣性之導熱性接著劑(亦謂散熱膏)。An object of the present invention is to provide an electrically insulating thermal conductive adhesive (also known as a thermal grease) which has excellent thermal conductivity and further excellent adhesion to an adherend such as a heat generating member and a heat dissipating member.
本發明係下述之導熱性接著劑,其係含有:(A)具有以下述式(1)所示之重複單元的重量平均分子量5000~150,000的聚醯亞胺聚矽氧樹脂100質量份(B)電絕緣性之導熱性填充劑100~10,000質量份、及(C)有機溶劑;The present invention is a thermally conductive adhesive comprising: (A) 100 parts by mass of a polyamidene polyfluorene resin having a weight average molecular weight of 5,000 to 150,000 of a repeating unit represented by the following formula (1) ( B) an electrically insulating thermally conductive filler of 100 to 10,000 parts by mass, and (C) an organic solvent;
【化1】【化1】
(式(1)中,W為4價之有機基,X為二價之有機基,Y為以下述式(2)所示的2價之聚矽氧殘基,且0.05≦m≦0.8、0.2≦n≦0.95、m+n=1)(In the formula (1), W is a tetravalent organic group, X is a divalent organic group, and Y is a divalent polyfluorene residue represented by the following formula (2), and 0.05 ≦m ≦ 0.8, 0.2≦n≦0.95, m+n=1)
【化2】[Chemical 2]
(式(2)中,R1 互相獨立為碳數1~8的取代或非取代之一價的烴基,R2 為自由基聚合性基,a及b分別為1~20之整數,a+b為2~21)。(In the formula (2), R 1 is independently a substituted or unsubstituted hydrocarbon group having 1 to 8 carbon atoms, R 2 is a radical polymerizable group, and a and b are each an integer of 1 to 20, a+ b is 2 to 21).
本發明之一實施態樣中係上述導熱性接著劑,其中進一步含有(D)過氧化碳酸酯0.1~10質量份。過氧化碳酸酯係可促進自由聚合性基的聚合硬化之硬化劑的作用。In one embodiment of the present invention, the thermally conductive adhesive agent further contains (D) a peroxycarbonate in an amount of 0.1 to 10 parts by mass. The peroxycarbonate function acts as a hardener for promoting polymerization hardening of a free polymerizable group.
本發明之一實施態樣中係R2 為乙烯基、丙烯基、(甲基)丙烯醯氧丙基、(甲基)丙烯醯氧乙基、(甲基)丙烯醯氧甲基、及苯乙烯基,更宜為乙烯基。In one embodiment of the present invention, R 2 is a vinyl group, a propenyl group, a (meth) propylene oxypropyl group, a (meth) propylene oxiranyl group, a (meth) propylene fluorenyloxymethyl group, and a benzene group. Vinyl, more preferably vinyl.
本發明之一實施態樣中係上述導熱性接著劑,其中對於銅板之接著強度為3Mpa以上,更宜為5~10Mpa以上。In one embodiment of the present invention, the thermal conductive adhesive is used, wherein the bonding strength to the copper plate is 3 MPa or more, more preferably 5 to 10 MPa or more.
若將本發明之導熱性接著劑置於銅板之上而進行加熱,該導熱性接著劑會流動而於銅板之表面上潤濕展開。因此,藉熱處理,而與銅板密著,產生良好的接著。When the thermally conductive adhesive of the present invention is placed on a copper plate for heating, the thermally conductive adhesive flows to wet and spread on the surface of the copper plate. Therefore, by heat treatment, it is adhered to the copper plate, resulting in a good adhesion.
於被黏體施予本發明之導熱性接著劑,為使之硬化,若進行加熱,接著劑會流動而潤濕被黏體之表面而展開,且溶劑會揮發,故導熱性填充劑會露出於接著劑硬化物之表面。因此,可得到良好的導熱性。The heat conductive adhesive of the present invention is applied to the adherend to harden it. If heated, the adhesive will flow to wet the surface of the adherend, and the solvent will volatilize, so that the thermal conductive filler will be exposed. On the surface of the hardener of the adhesive. Therefore, good thermal conductivity can be obtained.
本發明係提供一種電子構件,其係藉由使上述之導熱性接著劑硬化所得到之物質接著於散熱構件或發熱構件之電子元件。The present invention provides an electronic component which is obtained by adhering a substance obtained by hardening the above-mentioned thermally conductive adhesive to an electronic component of a heat dissipating member or a heat generating member.
本發明之導熱性接著劑係藉由含有特定構造之聚醯亞胺聚矽氧樹脂、導熱性填充劑及有機溶劑,而具有優異之導熱性,且具有對於被接著物優異之接著性。The thermally conductive adhesive of the present invention has excellent thermal conductivity and a superior adhesion to an adherend by containing a polyfluorene-polyoxyl resin having a specific structure, a thermally conductive filler, and an organic solvent.
以下,更詳細說明本發明之導熱性接著劑。Hereinafter, the thermally conductive adhesive of the present invention will be described in more detail.
(A)聚醯亞胺聚矽氧樹脂聚醯亞胺聚矽氧樹脂係具有以下述式(1)所示之重複單元。(A) Polyimine Polysiloxane The polyimine polyoxyl resin has a repeating unit represented by the following formula (1).
【化3】[化3]
式(1)中之W係4價之有機基。W係可選自例如均苯四甲酸二酐、2,3,3',4'-聯苯基四羧酸二酐、3,3',4,4'-聯苯基四羧酸二酐、3,3',4,4'-二苯基醚四羧酸二酐、3,3',4,4'-二苯基碸四羧酸二酐、3,3',4,4'-二苯甲酮四羧酸二酐、乙二醇雙偏苯三甲酸二酐、4,4'-六氟亞丙基雙酞酸二酐、2,2-雙[4-(3,4-苯氧基二羧酸)苯基]丙酸二酐之殘基。W in the formula (1) is a tetravalent organic group. The W system may be selected, for example, from pyromellitic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride. , 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3',4,4' - benzophenone tetracarboxylic dianhydride, ethylene glycol trimellitic acid dianhydride, 4,4'-hexafluoropropylene bismuthic acid dianhydride, 2,2-bis[4-(3,4 Residue of -phenoxydicarboxylic acid)phenyl]propionic acid dianhydride.
式(1)中之X為二價之有機基。X係從可使用於例如常用之聚醯亞胺樹脂的二胺所衍生之基。該二胺係可選自由脂肪族二胺及芳香族二胺之1或2種以上的組合。脂肪族二胺例如為四亞甲基二胺、1,4-二胺基環己烷、4,4'-二胺基二環己基甲烷。芳香族二胺例如為苯二胺、4,4'-二胺基二苯基醚、2,2-雙(4-胺基苯基)丙烷。X較佳係由以下述式(3)所示之芳香族二胺所衍生之基。X in the formula (1) is a divalent organic group. X is a group derived from a diamine which can be used, for example, in a conventional polyimine resin. The diamine may be a combination of one or more of an aliphatic diamine and an aromatic diamine. The aliphatic diamine is, for example, tetramethylenediamine, 1,4-diaminocyclohexane or 4,4'-diaminodicyclohexylmethane. The aromatic diamine is, for example, phenylenediamine, 4,4'-diaminodiphenyl ether or 2,2-bis(4-aminophenyl)propane. X is preferably a group derived from an aromatic diamine represented by the following formula (3).
【化4】【化4】
式(3)中之B為以下述式(4)、(5)、及(6)之任一者所示之基。B in the formula (3) is a group represented by any one of the following formulas (4), (5), and (6).
【化5】【化5】
【化6】【化6】
【化7】【化7】
式(1)中之Y係以下述式(2)所示之二價的聚矽氧殘基。Y in the formula (1) is a divalent polyfluorene residue represented by the following formula (2).
【化8】【化8】
式(2)中之R1 為碳數1~8,較佳係1~4之取代或非取代的一價之烴基。R1 例如為甲基、乙基。R 1 in the formula (2) is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. R 1 is, for example, a methyl group or an ethyl group.
式(2)中之R2 為自由基聚合性基。R2 為例如乙烯基、丙烯基、(甲基)丙烯醯氧丙基、(甲基)丙烯醯氧乙基、(甲基)丙烯醯氧甲基、或苯乙烯基。較佳係R2 為就原料容易取得之觀點為乙烯基。若該自由基聚合性基為聚醯亞胺聚矽氧樹脂的聚矽氧部分,亦可為例如端部及中央部之任一者的部位。R 2 in the formula (2) is a radical polymerizable group. R 2 is, for example, a vinyl group, a propenyl group, a (meth)acryloxypropyl group, a (meth)acryloyloxyethyl group, a (meth)acryloxymethyl group, or a styryl group. Preferably, R 2 is a vinyl group from the viewpoint that the raw material is easily obtained. When the radical polymerizable group is a polyoxymethylene portion of the polyamidene polyoxynene resin, it may be, for example, a portion of either the end portion or the center portion.
式(2)中之a及b分別為1~20,宜為3~20之整數。a+b之合計為2以上且21以下。此處,a、b分別大於20,或a+b大於21時,對被接著體的接著力變弱。In the formula (2), a and b are each 1 to 20, and preferably an integer of 3 to 20. The total of a+b is 2 or more and 21 or less. Here, when a and b are each greater than 20, or a+b is larger than 21, the adhesion to the adherend becomes weak.
式(1)中之m及n係為顯現源自該重複單元之效果,0.05≦m≦0.8、0.2≦n≦0.95,宜為0.05≦m≦0.5、0.5<n≦0.95。若為此範圍,可得到於被接著體的良好接著性。The m and n systems in the formula (1) exhibit an effect derived from the repeating unit, 0.05 ≦ m ≦ 0.8, 0.2 ≦ n ≦ 0.95, preferably 0.05 ≦ m ≦ 0.5, 0.5 < n ≦ 0.95. If it is this range, good adhesion to the adherend can be obtained.
式(1)中之m+n的合計為1。The total of m+n in the formula (1) is 1.
聚醯亞胺聚矽氧樹脂之重量平均分子量為5,000~150,000,宜為20,000~150,000。此理由係若分子量小於上述下限,作為樹脂之強韌性未顯現,另外若分子量大於上述上限,很難與後述之導熱性填充劑混合。The polyamidene polyoxyl resin has a weight average molecular weight of 5,000 to 150,000, preferably 20,000 to 150,000. For this reason, if the molecular weight is less than the above lower limit, the toughness of the resin is not exhibited, and if the molecular weight is more than the above upper limit, it is difficult to mix with the thermally conductive filler described later.
上述聚醯亞胺聚矽氧樹脂係可以例如下述敘述之公知的方法製造。The polyamidene polyoxysiloxane resin can be produced, for example, by a known method described below.
最初,將用以衍生W之四羧酸二酐、用以衍生X之二胺及用以衍生Y之二胺基聚矽氧烷饋入於溶劑中,繼而,以低溫例如0~50℃反應。上述溶劑係選自例如N-甲基-2-吡咯烷酮(NMP)、環己酮、γ-丁內酯、及N,N-二甲基乙醯胺(DMAc)之1或2以上的組合。進一步,使於醯亞胺化時生成之水易藉共沸除去,故可併用芳香族烴類例如甲苯、二甲苯。可依上述反應而製造醯亞胺樹脂之前驅體即聚醯酸。其次,使該聚醯胺酸之溶液昇溫至宜80~200℃,尤宜140~180℃之溫度。以該昇溫而聚醯胺酸之酸醯胺脫水閉環反應,可得到聚醯亞胺聚矽氧樹脂之溶液。使該溶液投入於溶劑例如水、甲醇、乙醇或乙腈中,產生沉澱物。乾燥該產生之沉澱物,而得到聚醯亞胺聚矽氧樹脂。Initially, a tetracarboxylic dianhydride for derivatization W, a diamine for derivatizing X, and a diamine polyoxyalkylene for deriving Y are fed into a solvent, and then reacted at a low temperature, for example, 0 to 50 ° C. . The solvent is selected from, for example, a combination of N-methyl-2-pyrrolidone (NMP), cyclohexanone, γ-butyrolactone, and N,N-dimethylacetamide (DMAc) of 1 or more. Further, the water formed during the imidization of the hydrazine is easily removed by azeotropic removal, so that aromatic hydrocarbons such as toluene or xylene can be used in combination. The precursor of the quinone imine resin, that is, polydecanoic acid, can be produced according to the above reaction. Next, the solution of the poly-proline is heated to a temperature of preferably from 80 to 200 ° C, particularly preferably from 140 to 180 ° C. A solution of the polyamidene polyoxyxylene resin can be obtained by the dehydration ring closure reaction of the acid amide of the polyaminic acid at this temperature rise. The solution is placed in a solvent such as water, methanol, ethanol or acetonitrile to produce a precipitate. The resulting precipitate is dried to obtain a polyamidene polyoxymethylene resin.
相對於四羧酸二酐之二胺與二胺基聚矽氧烷之合計的莫耳比率宜為0.95~1.05,尤宜為0.98~1.02的範圍。The molar ratio of the total of the diamine of the tetracarboxylic dianhydride to the diamine polyoxyalkylene is preferably from 0.95 to 1.05, particularly preferably from 0.98 to 1.02.
為調整聚醯亞胺聚矽氧樹脂之分子量亦可於上述溶液中添加二官能性之羧酸例如酞酸酐、及一官能性之胺例如苯胺。此等化合物之添加量分別相對於四羧酸及二胺例如為2莫耳%以下。To adjust the molecular weight of the polyimine polyoxyl resin, a difunctional carboxylic acid such as phthalic anhydride, and a monofunctional amine such as aniline may also be added to the above solution. The amount of these compounds added is, for example, 2 mol% or less based on the tetracarboxylic acid and the diamine.
在醯亞胺化過程中添加脫水劑及醯亞胺化觸媒,依需要而於約50℃進行加熱,亦可使之醯亞胺化。脫水劑例如為酸酐,例如為醋酸酐、丙酸酐、及三氟醋酸酐。脫水劑之使用量相對於二胺1莫耳例如為1~10莫耳。醯亞胺化觸媒為例如第三級胺,例如吡啶、膽鹼、二甲基吡啶、及三乙胺。醯亞胺化觸媒之使用量相對於所使用之脫水劑1莫耳例如為0.5~10莫耳。In the process of hydrazine imidization, a dehydrating agent and a ruthenium-imiding catalyst are added, and if necessary, heating is carried out at about 50 ° C, and ruthenium can also be imidized. The dehydrating agent is, for example, an acid anhydride such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. The amount of the dehydrating agent used is, for example, 1 to 10 moles per diamine. The quinone imidization catalyst is, for example, a tertiary amine such as pyridine, choline, lutidine, and triethylamine. The amount of the ruthenium-based catalyst used is, for example, 0.5 to 10 moles per mole of the dehydrating agent to be used.
使用複數之二胺及/或複數之四羧酸二酐時,例如使原料預先全部混合後共聚縮合之方法,使2種以上之二胺或四羧酸二酐個別地反應同時並依序添加。但,反應方法係不特別限定於此例示。When a plurality of diamines and/or a plurality of tetracarboxylic dianhydrides are used, for example, a raw material is mixed in advance and then copolymerized and condensed, and two or more kinds of diamines or tetracarboxylic dianhydrides are separately reacted and sequentially added. . However, the reaction method is not particularly limited to this illustration.
(B)電絕緣性之導熱性填充劑(B) Electrically insulating thermal conductive filler
電絕緣性之導熱性填充劑係例如金屬氧化物及陶瓷粉體。該金屬粉體例如為氧化鋅粉、氧化鋁粉。陶瓷粉體例如為碳化矽粉、氮化矽粉、氮化硼粉、氮化鋁粉。導熱性填充劑可適當選自安定性或成本之方面。The electrically insulating thermally conductive filler is, for example, a metal oxide and a ceramic powder. The metal powder is, for example, zinc oxide powder or alumina powder. The ceramic powder is, for example, tantalum carbide powder, tantalum nitride powder, boron nitride powder, or aluminum nitride powder. The thermally conductive filler may be suitably selected from the viewpoints of stability or cost.
導熱性填充劑之形狀無特別限定,而例如為粒狀、樹枝狀、片狀、及不定形狀。亦可使用具有此等形狀之導熱性填充劑粉末的一種或2種以上之混合物。導熱性填充劑之粒徑分布無特別限定,例如於0.05~100μm之範圍為90重量%以上,宜為95重量%以上。導熱性填充劑之平均粒徑無特別限定,但例如為1~50μm之範圍。導熱性填充劑可使用例如單一分布(單峰性)者。但為使導熱性填充劑高密度且均一地分散於接著劑內,組合形狀及粒徑相異之複數的導熱性填充劑而形成多峰性分布,較使用單一分布之導熱性填充劑更有效。The shape of the thermally conductive filler is not particularly limited, and is, for example, a granular shape, a dendritic shape, a sheet shape, and an indefinite shape. One or a mixture of two or more kinds of thermally conductive filler powders having such shapes may also be used. The particle size distribution of the thermally conductive filler is not particularly limited, and is, for example, 90% by weight or more in the range of 0.05 to 100 μm, preferably 95% by weight or more. The average particle diameter of the thermally conductive filler is not particularly limited, but is, for example, in the range of 1 to 50 μm. As the thermally conductive filler, for example, a single distribution (monomodality) can be used. However, in order to disperse the thermally conductive filler in a high density and uniformly dispersed in the adhesive, a plurality of thermally conductive fillers having different shapes and particle diameters are combined to form a multimodal distribution, which is more effective than using a single distributed thermally conductive filler. .
本發明之導熱性接著劑中的上述導熱性填充劑之調配量的比例係聚醯亞胺聚矽氧樹脂每100質量份,為100~10,000質量份,宜為200~6,000質量份。若上述導熱性填充劑之調配量的比率未達上述下限,使用本發明之導熱性接著劑時無法得到充分的導熱性。又,若上述導熱性填充劑之調配量的比率超過上述上限,使用本發明之導熱性接著劑時,在與被黏體之間無法得到充分的接著強度。The ratio of the amount of the thermally conductive filler to be added to the thermally conductive adhesive of the present invention is from 100 to 10,000 parts by mass, preferably from 200 to 6,000 parts by mass, per 100 parts by mass of the polyamidene polyoxyalkylene resin. When the ratio of the amount of the thermally conductive filler is less than the above lower limit, sufficient thermal conductivity cannot be obtained when the thermally conductive adhesive of the present invention is used. Further, when the ratio of the amount of the thermally conductive filler to be added exceeds the above upper limit, when the thermally conductive adhesive of the present invention is used, sufficient adhesive strength cannot be obtained between the adherend and the adherend.
(C)有機溶劑(C) organic solvent
有機溶劑係與(A)成分具有相溶性,宜不對(B)成分之表面狀態造成影響。有機溶劑例如選自醚類、酮類、酯類、溶纖劑類、醯胺類及芳香族烴類之1或2以上的組合。醚類含有例如四氫呋喃、及茴香醚。酮類含有例如環己酮、2-庚酮、甲基異丁基酮、2-庚酮、2-辛酮、及乙醯苯。酯類含有例如醋酸丁酯、安息香酸甲酯、及γ-丁內酯。溶纖劑類含有例如丁基卡必醇乙酸酯、丁基溶纖劑乙酸酯、及丙二醇單甲基醚乙酸酯。醯胺類含有例如N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基-2-吡咯烷酮。芳香族烴類含有例如甲苯、二甲苯。有機溶劑宜選自酮類、酯類、溶纖劑類及醯胺類。有機溶劑尤宜為丁基卡必醇乙酸酯、γ-丁內酯、丙二醇單甲基醚乙酸酯、及N-甲基-2-吡咯烷酮。此等之溶劑可為單獨使用亦可組合2種以上而使用。The organic solvent is compatible with the component (A), and it is preferred not to affect the surface state of the component (B). The organic solvent is, for example, a combination of one or more selected from the group consisting of ethers, ketones, esters, cellosolves, guanamines, and aromatic hydrocarbons. The ethers contain, for example, tetrahydrofuran, and anisole. The ketones include, for example, cyclohexanone, 2-heptanone, methyl isobutyl ketone, 2-heptanone, 2-octanone, and acetophenone. The esters contain, for example, butyl acetate, methyl benzoate, and γ-butyrolactone. The cellosolve contains, for example, butyl carbitol acetate, butyl cellosolve acetate, and propylene glycol monomethyl ether acetate. The guanamines contain, for example, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone. The aromatic hydrocarbons contain, for example, toluene or xylene. The organic solvent is preferably selected from the group consisting of ketones, esters, cellosolves, and guanamines. The organic solvent is particularly preferably butyl carbitol acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate, and N-methyl-2-pyrrolidone. These solvents may be used alone or in combination of two or more.
有機溶劑之量例如考量聚醯亞胺聚矽氧樹脂之溶解性、導熱性接著劑之塗佈時之作業性或皮膜之厚度,一般聚醯亞胺聚矽氧樹脂之量相對於該樹脂與溶劑之合計為10~60重量%,宜在20~50重量%之範圍內使用。組成物保存時調製成比較高的濃度,使用時亦可稀釋至所希望的濃度。The amount of the organic solvent is, for example, considering the solubility of the polyimide, the workability of the thermal conductive adhesive or the thickness of the film, and the amount of the polyamidene polyoxyl resin is generally relative to the resin. The total amount of the solvent is from 10 to 60% by weight, preferably from 20 to 50% by weight. The composition is prepared to a relatively high concentration when stored, and may be diluted to a desired concentration during use.
本發明之導熱性接著劑亦可進一步含有(D)過氧化碳酸酯作為任意成分。在過氧化碳酸酯之存在下即使比較低溫,聚醯亞胺聚矽氧樹脂中結合於矽原子之自由基聚合性基迅速硬化,耐溶劑性等之性能會提昇。過氧化碳酸酯係可舉例如第三丁基過氧化異丙基碳酸酯、第三丁基過氧化2-乙基己基碳酸酯、第三戊基過氧化2-乙基己基碳酸酯等之單過氧化碳酸酯;二(2-乙基己基)過氧化二碳酸酯、1,6-雙(第三丁基過氧化羰基氧)己烷、雙(4-第三丁基環己基)過氧化二碳酸酯、二(2-乙氧基乙基)過氧化二碳酸酯、二(正丙基)過氧化二碳酸酯、二異丙基過氧化二碳酸酯等。過氧化碳酸酯係從硬化性、與聚醯亞胺聚矽氧樹脂之相溶性、及接著劑之保存安定性等而言,宜為第三丁基過氧化2-乙基己基碳酸酯、第三戊基過氧化2-乙基己基碳酸酯、1,6-雙(第三丁基過氧化羰基氧)己烷、雙(4-第三丁基環己基)過氧化二碳酸酯。The thermally conductive adhesive of the present invention may further contain (D) peroxycarbonate as an optional component. In the presence of a peroxycarbonate, even if it is relatively low temperature, the radical polymerizable group bonded to the ruthenium atom in the polyamidene polysiloxane resin is rapidly hardened, and the performance such as solvent resistance is improved. Examples of the peroxycarbonate include a single butyl peroxy isopropyl carbonate, a third butyl peroxy 2-ethylhexyl carbonate, and a third pentyl peroxide 2-ethylhexyl carbonate. Peroxycarbonate; bis(2-ethylhexyl)peroxydicarbonate, 1,6-bis(t-butylperoxycarbonyloxy)hexane, bis(4-tert-butylcyclohexyl)peroxidation Dicarbonate, bis(2-ethoxyethyl)peroxydicarbonate, di(n-propyl)peroxydicarbonate, diisopropylperoxydicarbonate, and the like. The peroxycarbonate is preferably a third butyl peroxy 2-ethylhexyl carbonate, or the like, in terms of curability, compatibility with a polyamidene polyoxymethylene resin, and storage stability of an adhesive. Tripentylperoxide 2-ethylhexyl carbonate, 1,6-bis(t-butylperoxycarbonyloxy)hexane, bis(4-t-butylcyclohexyl)peroxydicarbonate.
過氧化碳酸酯之量相對於聚醯亞胺聚矽氧樹脂100質量份,宜為0.1~10質量份,更宜為0.5~5質量份。若調配量超過上述上限,本發明之導熱性接著劑的保存安定性及硬化物的耐高溫高濕性有降低之傾向。The amount of the peroxycarbonate is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the polyamidene polyfluorene resin. When the blending amount exceeds the above upper limit, the storage stability of the thermally conductive adhesive of the present invention and the high temperature and high wettability of the cured product tend to be lowered.
聚醯亞胺聚矽氧樹脂係藉熱硬化而發揮優異之耐熱性、機械強度、耐溶劑性、對各種基材之密著性。The polyimide polyimide polyether resin exhibits excellent heat resistance, mechanical strength, solvent resistance, and adhesion to various substrates by thermal curing.
本發明之接著劑的硬化條件無特別限定,但為80℃以上300℃以下,宜為100℃以上200℃以下之範圍。在未達上述下限進行硬化時,於熱硬化太耗時間,而不實用。以未達上述下限之低溫進行硬化,選擇成分及組成時,於接著劑之保存安定性有可能引起問題。又,本發明之導熱性接著劑係與習知之聚醯胺酸溶液相異,為了硬化,不須以所謂300℃以上之高溫且長時間之加熱,故可抑制基材之熱劣化。The curing conditions of the adhesive of the present invention are not particularly limited, but are preferably 80° C. or higher and 300° C. or lower, and preferably 100° C. or higher and 200° C. or lower. When the hardening is not carried out below the lower limit, it is too time-consuming to be thermally hardened, and it is not practical. When the curing is carried out at a low temperature which does not reach the above lower limit, the stability and stability of the adhesive may cause problems when the composition and composition are selected. Further, the thermally conductive adhesive of the present invention is different from the conventional polyamic acid solution, and it is not required to be heated at a high temperature of 300 ° C or higher for a long period of time for curing, so that thermal deterioration of the substrate can be suppressed.
本發明之導熱性接著劑係除上述成分之外,在無損本發明之目的及導熱性接著劑的效果之範圍亦可添加例如抗老化劑、紫外線吸收劑、接著性改良劑、耐燃劑、界面活性劑、保存安定改良劑、臭氧劣化抑制劑、光安定劑、增黏劑、可塑劑、矽烷偶合劑、抗氧化劑、熱安定劑、輻射線遮蔽劑、核劑、滑劑、顏料、及物性調整劑所選出之1或2以上。The thermal conductive adhesive of the present invention may contain, in addition to the above components, an anti-aging agent, an ultraviolet absorber, an adhesion improver, a flame retardant, and an interface, without departing from the object of the present invention and the effect of the thermal conductive adhesive. Active agent, preservation stability improver, ozone degradation inhibitor, light stabilizer, tackifier, plasticizer, decane coupling agent, antioxidant, thermal stabilizer, radiation shielding agent, nucleating agent, slip agent, pigment, and physical property The regulator is selected to be 1 or more.
本發明之導熱性接著劑在25℃中宜具有0.5~2000Pa‧s,宜為1.0~1000 Pa‧s的黏度。The thermally conductive adhesive of the present invention preferably has a viscosity of from 0.5 to 2,000 Pa s at 25 ° C, preferably from 1.0 to 1,000 Pa ‧ s.
本發明之導熱性接著劑的熱傳導率(W/mK)宜為0.5以上,更宜為1.0以上,尤宜為3以上。The thermal conductivity (W/mK) of the thermally conductive adhesive of the present invention is preferably 0.5 or more, more preferably 1.0 or more, and particularly preferably 3 or more.
本發明之導熱性接著劑對銅板之接著強度(MPa)宜為3以上,更宜為5以上,尤宜為6以上。於80℃、95RH之高溫高濕環境放置240小時後之接著強度(MPa)宜與上述相同。The thermal strength of the thermal conductive adhesive of the present invention to the copper plate is preferably 3 or more, more preferably 5 or more, and particularly preferably 6 or more. The bonding strength (MPa) after leaving it at a temperature of 80 ° C and 95 RH for 240 hours is preferably the same as above.
本發明之導熱性接著劑係可適宜使用於例如為了高亮度,發熱量大之LED晶片的接著劑、或伴隨小型化、輕量化之每單位面積的發熱量大之半導體元件的接著劑。The thermal conductive adhesive of the present invention can be suitably used, for example, as an adhesive for an LED chip having a large amount of heat for high luminance, or as an adhesive for a semiconductor element having a large amount of heat per unit area which is reduced in size and weight.
以下,藉實施例更詳細說明本發明,但本發明不限定於此等實施例。Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto.
1.聚醯亞胺聚矽氧樹脂之合成1. Synthesis of polyamidene polyoxyl resin
如示於下述合成例1~4般,製造4種類之聚醯亞胺聚矽氧樹脂。Four kinds of polythenimine polyfluorene resins were produced as shown in the following Synthesis Examples 1 to 4.
合成例1Synthesis Example 1
於具備攪拌機、溫度計及氮取代裝置之燒瓶內,饋入4,4'-六氟亞丙基雙酞酸二酐88.8g(0.2莫耳)及正甲基-2-吡咯烷酮500g。然後,準備將以式7所示之二胺基矽氧烷142.2g(0.16莫耳)、及2,2-雙[4-(4-胺基苯氧基)苯基]丙烷16.4g(0.04莫耳)溶解於正甲基-2-吡咯烷酮100g之溶液中。使該溶液滴下於上述燒瓶內。滴下之際,調節反應系之溫度以免超過50℃。滴下終了後,在室溫下進一步攪拌10小時。然後,於該燒瓶安裝附有水分接受器之回流冷卻器後,加入二甲苯50g,昇溫至150℃,保持該溫度6小時。其結果,得到黃褐色之溶液。In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 88.8 g (0.2 mol) of 4,4'-hexafluoropropylenebisphthalic acid dianhydride and 500 g of n-methyl-2-pyrrolidone were fed. Then, 142.2 g (0.16 mol) and 2,2-bis[4-(4-aminophenoxy)phenyl]propane as shown in Formula 7 were prepared, 16.4 g (0.04). Mohr) was dissolved in a solution of 100 g of n-methyl-2-pyrrolidone. This solution was dropped into the above flask. At the time of dripping, the temperature of the reaction system was adjusted to avoid exceeding 50 °C. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Then, after installing a reflux condenser equipped with a water receiver in the flask, 50 g of xylene was added, and the temperature was raised to 150 ° C, and the temperature was maintained for 6 hours. As a result, a yellow-brown solution was obtained.
【化9】【化9】
使上述所得到之黃褐色的溶液冷卻至室溫(25℃),投入於甲醇中而再沉澱。乾燥所得到之沉澱物190g,測定其線吸收光譜。其結果,未顯現依未反應之聚醯胺酸的吸收(1640cm-1 ),而可確認於1780 cm-1 及1720 cm-1 依據醯亞胺基之吸收。其次,藉由以四氫呋喃作為溶劑的凝膠浸透色層分析(GPC),測定重量平均分子量(聚苯乙烯換算)之結果,為33,000。稱生成物為聚醯亞胺聚矽氧樹脂(1)。The yellow-brown solution obtained above was cooled to room temperature (25 ° C), and poured into methanol to reprecipitate. The obtained precipitate was dried (190 g), and its linear absorption spectrum was measured. As a result, the absorption of the unreacted polylysine (1640 cm -1 ) was not observed, and it was confirmed that the absorption was based on the quinone imine group at 1780 cm -1 and 1720 cm -1 . Next, the result of measuring the weight average molecular weight (in terms of polystyrene) by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent was 33,000. The product is referred to as a polyamidene polyoxyl resin (1).
合成例2Synthesis Example 2
於具備攪拌機、溫度計及氮取代裝置之燒瓶內,饋入4,4'-六氟亞丙基雙酞酸二酐88.8g(0.2莫耳)及正甲基-2-吡咯烷酮500g。然後,準備將以式8所示之二胺基矽氧烷165.3g(0.1莫耳)、及2,2-雙[4-(4-胺基苯氧基)苯基]丙烷41.1g(0.1莫耳)溶解於正甲基-2-吡咯烷酮100g之溶液中。使該溶液滴下於上述燒瓶內。滴下之際,調節反應系之溫度以免超過50℃。滴下終了後,在室溫下進一步攪拌10小時。然後,於該燒瓶安裝附有水分接受器之回流冷卻器後,加入二甲苯50g,昇溫至150℃,保持該溫度6小時。其結果,得到黃褐色之溶液。In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 88.8 g (0.2 mol) of 4,4'-hexafluoropropylenebisphthalic acid dianhydride and 500 g of n-methyl-2-pyrrolidone were fed. Then, 165.3 g (0.1 mol) of diaminocarboxane represented by Formula 8 and 41.1 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane were prepared. Mohr) was dissolved in a solution of 100 g of n-methyl-2-pyrrolidone. This solution was dropped into the above flask. At the time of dripping, the temperature of the reaction system was adjusted to avoid exceeding 50 °C. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Then, after installing a reflux condenser equipped with a water receiver in the flask, 50 g of xylene was added, and the temperature was raised to 150 ° C, and the temperature was maintained for 6 hours. As a result, a yellow-brown solution was obtained.
【化10】【化10】
使上述所得到之黃褐色的溶液冷卻至室溫(25℃),投入於甲醇中而再沉澱。乾燥所得到之沉澱物240g,測定其線吸收光譜。其結果,未顯現依未反應之聚醯胺酸的吸收(1640cm-1 ),而可確認於1780 cm-1 及1720 cm-1 依據醯亞胺基之吸收。其次,藉由以四氫呋喃作為溶劑的凝膠浸透色層分析(GPC),測定重量平均分子量(聚苯乙烯換算)之結果,為33,000。稱生成物為聚醯亞胺聚矽氧樹脂(2)。The yellow-brown solution obtained above was cooled to room temperature (25 ° C), and poured into methanol to reprecipitate. 240 g of the obtained precipitate was dried, and its linear absorption spectrum was measured. As a result, the absorption of the unreacted polylysine (1640 cm -1 ) was not observed, and it was confirmed that the absorption was based on the quinone imine group at 1780 cm -1 and 1720 cm -1 . Next, the result of measuring the weight average molecular weight (in terms of polystyrene) by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent was 33,000. The product is referred to as a polyamidene polyoxyl resin (2).
合成例3(比較用)Synthesis Example 3 (for comparison)
於具備攪拌機、溫度計及氮取代裝置之燒瓶內,饋入4,4'-六氟亞丙基雙酞酸二酐88.8g(0.2莫耳)及正甲基-2-吡咯烷酮500g。然後,準備將以式9所示之二胺基矽氧烷263.1g(0.08莫耳)、及2,2-雙[4-(4-胺基苯氧基)苯基]丙烷49.3g(0.12莫耳)溶解於正甲基-2-吡咯烷酮100g之溶液中。使該溶液滴下於上述燒瓶內。滴下之際,調節反應系之溫度以免超過50℃。滴下終了後,在室溫下進一步攪拌10小時。然後,於該燒瓶安裝附有水分接受器之回流冷卻器後,加入二甲苯50g,昇溫至150℃,保持該溫度6小時。其結果,得到黃褐色之溶液。In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 88.8 g (0.2 mol) of 4,4'-hexafluoropropylenebisphthalic acid dianhydride and 500 g of n-methyl-2-pyrrolidone were fed. Then, 263.1 g (0.08 mol) of diaminocarboxane represented by Formula 9, and 49.3 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane were prepared (0.12). Mohr) was dissolved in a solution of 100 g of n-methyl-2-pyrrolidone. This solution was dropped into the above flask. At the time of dripping, the temperature of the reaction system was adjusted to avoid exceeding 50 °C. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Then, after installing a reflux condenser equipped with a water receiver in the flask, 50 g of xylene was added, and the temperature was raised to 150 ° C, and the temperature was maintained for 6 hours. As a result, a yellow-brown solution was obtained.
【化11】【化11】
使上述所得到之黃褐色的溶液冷卻至室溫(25℃),投入於甲醇中而再沉澱。乾燥所得到之沉澱物330g,測定其線吸收光譜。其結果,未顯現依未反應之聚醯胺酸的吸收(1640cm-1 ),而可確認於1780 cm-1 及1720 cm-1 依據醯亞胺基之吸收。其次,藉由以四氫呋喃作為溶劑的凝膠浸透色層分析(GPC),測定重量平均分子量(聚苯乙烯換算)之結果,為35,000。稱生成物為聚醯亞胺聚矽氧樹脂(3)。The yellow-brown solution obtained above was cooled to room temperature (25 ° C), and poured into methanol to reprecipitate. The obtained precipitate was 330 g, and its linear absorption spectrum was measured. As a result, the absorption of the unreacted polylysine (1640 cm -1 ) was not observed, and it was confirmed that the absorption was based on the quinone imine group at 1780 cm -1 and 1720 cm -1 . Next, the result of measuring the weight average molecular weight (in terms of polystyrene) by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent was 35,000. The product is referred to as a polyamidene polyoxyl resin (3).
合成例4(比較用)Synthesis Example 4 (for comparison)
於具備攪拌機、溫度計及氮取代裝置之燒瓶內,饋入4,4'-六氟亞丙基雙酞酸二酐88.8g(0.2莫耳)及正甲基-2-吡咯烷酮500g。然後,準備將以式(10)所示之二胺基矽氧烷244.8g(0.08莫耳)、及2,2-雙[4-(4-胺基苯氧基)苯基]丙烷49.3g(0.12莫耳)溶解於正甲基-2-吡咯烷酮100g之溶液中。使該溶液滴下於上述燒瓶內。滴下之際,調節反應系之溫度以免超過50℃。滴下終了後,在室溫下進一步攪拌10小時。然後,於該燒瓶安裝附有水分接受器之回流冷卻器後,加入二甲苯50g,昇溫至150℃,保持該溫度6小時。其結果,得到黃褐色之溶液。In a flask equipped with a stirrer, a thermometer and a nitrogen substitution device, 88.8 g (0.2 mol) of 4,4'-hexafluoropropylenebisphthalic acid dianhydride and 500 g of n-methyl-2-pyrrolidone were fed. Then, 244.8 g (0.08 mol) of diaminocarboxane represented by formula (10) and 49.3 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane were prepared. (0.12 mol) was dissolved in a solution of 100 g of n-methyl-2-pyrrolidone. This solution was dropped into the above flask. At the time of dripping, the temperature of the reaction system was adjusted to avoid exceeding 50 °C. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 10 hours. Then, after installing a reflux condenser equipped with a water receiver in the flask, 50 g of xylene was added, and the temperature was raised to 150 ° C, and the temperature was maintained for 6 hours. As a result, a yellow-brown solution was obtained.
【化12】【化12】
使上述所得到之黃褐色的溶液冷卻至室溫(25℃),投入於甲醇中而再沉澱。乾燥所得到之沉澱物340g,測定其線吸收光譜。其結果,未顯現依未反應之聚醯胺酸的吸收(1640cm-1 ),而可確認於1780 cm-1 及1720 cm-1 依據醯亞胺基之吸收。其次,藉由以四氫呋喃作為溶劑的凝膠浸透色層分析(GPC),測定重量平均分子量(聚苯乙烯換算)之結果,為35,000。稱生成物為聚醯亞胺聚矽氧樹脂(4)。The yellow-brown solution obtained above was cooled to room temperature (25 ° C), and poured into methanol to reprecipitate. The obtained precipitate was dried (340 g), and its linear absorption spectrum was measured. As a result, the absorption of the unreacted polylysine (1640 cm -1 ) was not observed, and it was confirmed that the absorption was based on the quinone imine group at 1780 cm -1 and 1720 cm -1 . Next, the result of measuring the weight average molecular weight (in terms of polystyrene) by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent was 35,000. The product is referred to as a polyamidene polyoxyl resin (4).
2.接著劑之製作2. Preparation of adhesive
使用下述之原料。The following materials were used.
(A)聚醯亞胺聚矽氧樹脂:使用於上述合成例1~4所得到之聚醯亞胺聚矽氧樹脂(1)、(2)、(3)、或(4)。(A) Polyimine polyoxyl resin: used in the polyamidene polyoxyl resin (1), (2), (3), or (4) obtained in the above Synthesis Examples 1 to 4.
(B)電絕緣性之導熱性填充劑:(B) Electrically insulating thermal conductive filler:
(B1)導熱性填充劑A:平均粒徑10μm之氧化鋁(比重3.98)(B1) Thermally conductive filler A: alumina having an average particle diameter of 10 μm (specific gravity: 3.98)
(B2)導熱性填充劑B:平均粒徑1μm之氧化鋁(比重3.98)(B2) Thermally conductive filler B: alumina having an average particle diameter of 1 μm (specific gravity: 3.98)
(C)有機溶劑:丁基卡必醇乙酸酯(BCA)(C) Organic solvent: butyl carbitol acetate (BCA)
(D)過氧化碳酸酯:第三丁基過氧化-2-乙基己基碳酸酯(D) Peroxycarbonate: tert-butylperoxy-2-ethylhexyl carbonate
[實施例1~4及比較例1~2][Examples 1 to 4 and Comparative Examples 1 to 2]
(A)聚醯亞胺聚矽氧樹脂(1)~(4)分別使(B)電絕緣性之導熱性填充劑(B1及B2)、(C)有機溶劑、及(D)過氧化碳酸酯以表1所示之質量比例饋入於自轉公轉混合機中,攪拌成為均一,繼而,進行脫泡而得到接著劑。(A) Polyimine polysiloxane resins (1) to (4) respectively (B) electrically insulating thermally conductive fillers (B1 and B2), (C) organic solvents, and (D) peroxycarbonic acid The ester was fed into the autorotation mixer at a mass ratio shown in Table 1, and the mixture was stirred to be uniform, and then defoamed to obtain an adhesive.
3.評估試驗3. Evaluation test
有關實施例1~4、以及比較例1~2所得到的接著劑,依下述方法進行黏度、導熱率及接著強度之評估試驗。又,有關加熱硬化性一液型之聚矽氧橡膠C(市售品)及D(市售品),以與上述相同之順序進行評估試驗(分別為比較例3及比較例4)。With respect to the adhesives obtained in Examples 1 to 4 and Comparative Examples 1 and 2, evaluation tests of viscosity, thermal conductivity, and adhesion strength were carried out in the following manner. Further, the heat-curable one-liquid type polyoxyethylene rubber C (commercial product) and D (commercial product) were subjected to evaluation tests in the same order as above (Comparative Example 3 and Comparative Example 4, respectively).
結果表示於表2中。The results are shown in Table 2.
(1)黏度(1) Viscosity
各接著劑之黏度係使用BH型旋轉黏度計而以25℃測定。The viscosity of each adhesive was measured at 25 ° C using a BH type rotational viscometer.
(2)導熱率(2) Thermal conductivity
將各接著劑流入於鐵氟龍(商標)(杜邦公司製)板之溝,以80℃乾燥30分鐘,繼而,以150℃加熱該接著劑1小時,製成10mmΦ ×1mm之試驗片。使用雷射快閃法熱常數測定裝置(LFA 447(NETZSCH公司製)),測定該試驗片的熱擴散率及比熱容量,求出導熱率。Each of the adhesives was poured into a groove of Teflon (trademark) (manufactured by DuPont), dried at 80 ° C for 30 minutes, and then the adhesive was heated at 150 ° C for 1 hour to prepare a test piece of 10 mm Φ × 1 mm. The thermal diffusivity and specific heat capacity of the test piece were measured using a laser flash thermal constant measuring apparatus (LFA 447 (manufactured by NETZSCH)) to determine the thermal conductivity.
(3)接著強度(3) subsequent strength
使各接著劑於銅板(100mm×25mm×1mm)以塗佈面積20mm×20mm進行塗佈,與相同大小的另一個銅板貼合。將該貼合之銅板以80℃乾燥30分鐘,繼而,在4MPa之壓力下、以150℃進一步乾燥2分鐘,繼而,以150℃加熱1小時,得到試驗片。使用Autograph(STROGRAPH V10-D(東洋精機公司製))以5mm/分之速度測定試驗片之剪切接著強度。Each of the adhesives was applied to a copper plate (100 mm × 25 mm × 1 mm) at a coating area of 20 mm × 20 mm, and bonded to another copper plate of the same size. The bonded copper plate was dried at 80 ° C for 30 minutes, and then further dried at 150 ° C for 2 minutes under a pressure of 4 MPa, followed by heating at 150 ° C for 1 hour to obtain a test piece. The shear strength of the test piece was measured at a speed of 5 mm/min using Autograph (STROGRAPH V10-D (manufactured by Toyo Seiki Co., Ltd.)).
又,與上述相同做法得到之試驗片於80℃/95%RH曝露240小時(高溫高濕試驗)、與上述相同做法測定剪切接著強度(高溫高濕試驗後)。Further, the test piece obtained in the same manner as above was exposed to air at 80 ° C / 95% RH for 240 hours (high temperature and high humidity test), and the shear strength was measured in the same manner as above (after the high temperature and high humidity test).
從上述結果,接著劑1~4係具有適當的黏度,導熱率良好為1.1~3.1W/mK,接著強度良好為6~11 MPa,在高溫高濕試驗前後之接著強度的降低幾乎看不到。From the above results, the adhesives 1 to 4 have an appropriate viscosity, the thermal conductivity is preferably 1.1 to 3.1 W/mK, and the strength is preferably 6 to 11 MPa, and the decrease in the adhesion strength before and after the high temperature and high humidity test is hardly observed. .
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KR101625688B1 (en) | 2016-05-30 |
TW201102417A (en) | 2011-01-16 |
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CN101864269B (en) | 2014-05-21 |
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