KR100627248B1 - High dielectric constant polymer-barium titanate composite - Google Patents
High dielectric constant polymer-barium titanate composite Download PDFInfo
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- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229920000642 polymer Polymers 0.000 claims abstract description 33
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 24
- 125000000524 functional group Chemical group 0.000 claims abstract description 21
- 238000010306 acid treatment Methods 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 229920001187 thermosetting polymer Polymers 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 5
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- 229920001721 polyimide Polymers 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 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 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 8
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- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 239000011147 inorganic material Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 2
- XBYNNYGGLWJASC-UHFFFAOYSA-N barium titanium Chemical compound [Ti].[Ba] XBYNNYGGLWJASC-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- -1 BTO) Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
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- 230000003071 parasitic effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 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 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
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Abstract
본 발명은 산 처리에 의해 표면 개질된 티탄산바륨 및 이를 포함하는 고 유전성 고분자 복합체에 관한 것이다. 본 발명에 따른 산 처리에 의해 표면 개질된 티탄산바륨은 표면에 카르복실 관능기가 도입되고, 이러한 티탄산바륨을 포함한 고분자 복합체는 높은 유전상수와 우수한 기계적 물성을 가진다.The present invention relates to a barium titanate surface modified by acid treatment and a high dielectric polymer composite comprising the same. The barium titanate surface-modified by the acid treatment according to the present invention introduces a carboxyl functional group to the surface, and the polymer composite including the barium titanate has high dielectric constant and excellent mechanical properties.
산 처리, 티탄산바륨, 고분자 복합체, 고 유전성 Acid Treatment, Barium Titanate, Polymer Composite, High Dielectricity
Description
도 1은 실시예 1의 티탄산바륨의 전자분광 화학분석(ESCA) 그래프로 산 처리 전후의 변화를 나타낸 것이다. FIG. 1 shows changes before and after acid treatment in an electron spectrochemical analysis (ESCA) graph of barium titanate of Example 1. FIG.
도 2은 실시예 1의 고분자-티탄산바륨 복합체의 유전상수 변화를 나타낸 그래프이다. 2 is a graph showing a change in dielectric constant of the polymer-barium titanate composite of Example 1. FIG.
도 3은 실시예 1의 고분자-티탄산바륨 복합체의 우수한 유연성을 나타낸 사진이다. Figure 3 is a photograph showing the excellent flexibility of the polymer-barium titanate composite of Example 1.
도 4는 실시예 2의 고분자-티탄산바륨 복합체의 유전상수 변화를 나타낸 그래프이다. 4 is a graph showing a change in dielectric constant of the polymer-barium titanate composite of Example 2. FIG.
본 발명은 산 처리하여 표면 개질된 티탄산바륨을 포함하는 고분자-티탄산바륨의 복합체 및 이의 제조방법에 관한 것으로, 산 처리한 티탄산바륨은 표면에 카르복실 관능기가 도입되어 고분자와의 상용성이 높아, 이를 포함하는 복합체는 고유전율을 가진다. The present invention relates to a composite of a polymer-barium titanate containing barium titanate surface-modified by acid treatment and a method for preparing the same, wherein the acid-treated barium titanate has high compatibility with polymers by introducing a carboxyl functional group to the surface thereof, The composite including the same has a high dielectric constant.
최근 전자제품의 경박 단소화와 전기적 고성능화를 위하여 수동소자에 대한 관심이 점차 증가되고 있다. 휴대용 이동통신 기기의 경우 능동소자의 사용량에 대한 수동소자의 사용량의 비가 20을 넘고 있다. 현재 많은 수의 수동소자들은 대부분 개별형 부품(discrete component)의 형태로 기판의 표면에 실장되고 있어서 기판의 많은 면적을 차지할 뿐만 아니라, 표면실장 공정상의 문제로 원 상태보다 저하된 전기적 성능이 얻어지며, 소자 간 전기적 간섭 등으로 제품의 신뢰성에 문제를 일으킬 수 있는 것으로 알려져 있다. In recent years, interest in passive devices has been gradually increased to reduce the light weight and increase the electrical performance of electronic products. In the case of portable mobile communication devices, the ratio of the amount of active elements to the amount of active elements exceeds 20. At present, a large number of passive devices are mostly mounted on the surface of the substrate in the form of discrete components, which occupy a large area of the substrate, and the electrical performance is lowered than the original state due to the problem of the surface mounting process. In addition, it is known that the reliability of the product may be caused by electrical interference between devices.
이러한 문제점을 해결하기 위해 기존의 개별형 수동소자를 기판의 표면으로부터 제거하고 대신 다층구조로 만들어진 기판의 한 층에 집적시켜 주는 내장형 수동소자(integral passive 또는 embedded passive)에 대한 관심이 증가되고 있다. 내장형 소동소자의 장점으로는 수동소자가 차지하는 면적을 줄여 칩의 밀도를 높일 수 있으며, 소자간의 접속 길이를 짧게 함으로써 기생 인덕턴스 성분의 감소에 따른 전기적 성능의 향상을 얻을 수 있다. In order to solve this problem, there is a growing interest in integrated passive devices (integral passive or embedded passive) that remove existing discrete passive devices from the surface of the substrate and instead integrate them into one layer of the multilayered substrate. An advantage of the built-in passive element is that the area occupied by the passive element can be increased to increase the chip density, and the connection length between the elements can be shortened to improve the electrical performance by reducing the parasitic inductance component.
고분자 복합체는 이러한 내장형 수동소자 후보 재료 중의 하나로서, 고분자와 고유전 충진제를 함께 사용함으로써 고분자의 우수한 가공성과 고유전 충진제의 높은 유전 상수를 동시에 구현할 수 있다는 가능성에 착안하여 많은 연구가 현재 진행되고 있다. 고분자 복합체는 공정 온도가 낮고 제조 비용이 적게 들며, 균일한 유전특성과 가공성, 상온 보관성 등이 우수하여 내장형 수동소자 재료로서의 가능성이 매우 높다고 평가되고 있다. Polymer composites are one of the candidate materials for embedded passive devices, and many studies have been conducted on the possibility of using the polymer and the high dielectric filler together to realize the excellent processability of the polymer and the high dielectric constant of the high dielectric filler at the same time. . Polymer composites have a low process temperature, low manufacturing cost, and excellent dielectric properties, processability, and room temperature storage.
현재 상기 고분자 복합체에 사용되는 고유전 충진제로서는 BaTiO3 (Barium Titanate, BTO), SrTiO3 (Strontium Titanate, STO), (Ba, Sr)TiO3 (Barium Strontium Titanate, BST), (Pb, La)TiO3 (PLT) 등이 있는데, 고유전율을 얻기 위해서는 고유전 충전제의 함량이 매우 높은 조건에서 고유전 충진제가 고분자와 안정적인 분산 상태를 유지할 수 있어야 한다. 하지만, 고분자와 상기 무기계 충진제의 경우, 매우 낮은 상용성으로 인하여 충진제 함량을 높이는 면에 한계가 있으며, 충진제 함량을 조금만 높여도 점도의 급격한 상승이 유발되어 가공성도 급격히 저하되는 단점과 함께 기계적 강도, 내열성 등 물성의 심각한 저하를 초래하는 문제점이 지적되어 왔다. 따라서 높은 유전상수를 가지는 고분자 복합체의 제조가 현재까지 매우 어려운 실정이었으며, 이에 내장형 수동소자로 사용될 수 있는, 고 유전율을 가지며 기계적 물성이 증가된 고분자 복합체의 개발이 절실히 요구된다 할 것이다. BaTiO 3 is a high-k filler currently used in the polymer composite. (Barium Titanate, BTO), SrTiO 3 ( Strontium Titanate, STO), (Ba, Sr) TiO 3 (Barium Strontium Titanate, BST), (Pb, La) TiO 3 (PLT) and the like, in order to obtain a high dielectric constant, the high dielectric filler should be able to maintain a stable dispersion state with the polymer under a very high content of the high dielectric filler. However, in the case of the polymer and the inorganic filler, there is a limit in terms of increasing the filler content due to the very low compatibility, and even a small increase in the filler content causes a sharp increase in viscosity, leading to a sharp decrease in processability, and mechanical strength, Problems that cause serious deterioration of physical properties such as heat resistance have been pointed out. Therefore, the production of a polymer composite having a high dielectric constant has been very difficult to date, and thus, development of a polymer composite having high dielectric constant and increased mechanical properties, which can be used as a built-in passive device, is urgently required.
본 발명은 산 처리로 인하여 표면에 카르복실 관능기가 도입된 티탄산바륨을 제공한다. The present invention provides barium titanate having a carboxyl functional group introduced to its surface due to acid treatment.
또한, 본 발명은 티탄산바륨을 산 처리하여 티탄산바륨 표면에 카르복실 관능기를 도입하는 방법을 제공한다. The present invention also provides a method of introducing a carboxyl functional group to the barium titanate surface by acid treatment of barium titanate.
또한, 본 발명은 산 처리한 티탄산바륨을 포함하는 고분자-티탄산바륨 복합체를 제공한다. The present invention also provides a polymer-barium titanate composite containing an acid-treated barium titanate.
하나의 양태로서, 본 발명은 산 처리로 인하여 표면에 카르복실 관능기가 도입된 티탄산바륨을 제공한다. 본 발명의 티탄산바륨은 카르복실 관능기(carboxyl group)가 도입되어 고분자와의 상용성(compatibility)이 증가된 특징을 갖는다. In one embodiment, the present invention provides barium titanate having a carboxyl functional group introduced to the surface due to acid treatment. Barium titanate of the present invention has a feature that the carboxyl group (carboxyl group) is introduced to increase the compatibility (compatibility) with the polymer.
티탄산바륨(BaTiO3)은 내장형 수동 소자에 사용될 수 있는 고분자 복합체의 고유전 충진제 중의 하나이다. 본 발명의 산 처리로 인하여 카르복실 관능기가 표면에 흡착된 티탄산바륨은 고분자와 티탄산바륨 사이에 안정적인 계면을 형성하여 고분자와의 상용성을 증가된다. 즉, 이는 카르복실 관능기의 높은 쌍극자 모멘트 및 안정적인 무기-유기 계면 형성으로 인하여 크게 향상된 계면 분극 현상(interface polarization)에 기인한 것이며, 또한, 이는 기계적 강도, 내충격성 등의 증가를 가져온다. 따라서 산 처리한 티탄산바륨의 고분자와의 높은 상용성으로 인하여 티탄산바륨의 함량이 증가된 고분자-티탄산바륨 복합체를 제조할 수 있으며, 티탄산바륨의 함량이 증가된 고분자-티탄산바륨 복합체는 고유전성을 가지며, 우수한 기계적 물성을 나타낸다. Barium titanate (BaTiO 3 ) is one of the high dielectric fillers of polymer composites that can be used in embedded passive devices. Due to the acid treatment of the present invention, barium titanate having a carboxyl functional group adsorbed on the surface forms a stable interface between the polymer and barium titanate, thereby increasing compatibility with the polymer. That is, this is due to the greatly improved interface polarization due to the high dipole moment of the carboxyl functional group and the formation of a stable inorganic-organic interface, which also leads to an increase in mechanical strength, impact resistance and the like. Therefore, polymer-barium titanate composites with increased barium titanate content can be prepared due to the high compatibility with acid-treated barium titanate polymers. The polymer-barium titanate composites with increased barium titanate have high dielectric properties. , Excellent mechanical properties.
또 다른 하나의 양태로서, 본 발명은 산을 처리하여 티탄산바륨 표면에 카르복실 관능기를 도입하는 방법을 제공한다 As another aspect, the present invention provides a process for introducing an carboxyl functional group to a barium titanate surface by treating an acid.
티탄산바륨의 표면에 카르복실 관능기를 도입하기 위해 티탄산바륨, 일반적으로는 분말 형태의 티탄산바륨을 직접 산에 분산시키거나, 또는 고분자/ 산 용액에 티탄산바륨을 첨가한 후 초음파 처리하여 분산시킬 수 있다. 이때 사용될 수 있 는 산은 카르복실 관능기를 지닌 유기계 산을 모두 포함하며, 예로서 포름산, 아세트산, 프로피온산 등이 있으며, 또한 훨씬 긴 지방족 사슬 또는 방향족 사슬을 지닌 유기계 산도 모두 포함한다. 이러한 유기계 산에 직접 분산시킨 티탄산바륨은 초음파 처리, 감압여과 방법으로 추출 및 감압 조건에서 건조 과정을 거친 후, 고분자 혼합물에 첨가하여 필름 캐스팅함으로써 고분자-티탄산바륨 복합체 필름을 제조할 수 있다. 고분자/산 용액에 분산시킨 티탄산바륨 혼합액은 알코올에 침전시키고 용매를 제거하여 건조시킨 후, 가열압착방법으로 고분자-티탄산바륨 복합체 필름을 제조할 수 있다. In order to introduce carboxyl functional groups on the surface of barium titanate, barium titanate, usually in powder form, may be directly dispersed in acid, or may be dispersed by sonication after adding barium titanate to a polymer / acid solution. . Acids that may be used include all organic acids with carboxyl functionalities, for example formic acid, acetic acid, propionic acid, and the like, and also include all organic acids with much longer aliphatic or aromatic chains. The barium titanate directly dispersed in the organic acid may be extracted and dried under reduced pressure by ultrasonication, filtration under reduced pressure, and then added to the polymer mixture to cast a film, thereby preparing a polymer-barium titanate composite film. The barium titanate mixed solution dispersed in the polymer / acid solution may be precipitated in alcohol, dried by removing the solvent, and a polymer-barium titanate composite film may be prepared by a hot pressing method.
상기와 같이 산 처리 결과로 티탄산바륨의 표면에는 카르복실 관능기가 도입된다. 도 1은 티탄산바륨의 전자분광 화학분석 (ESCA) 그래프로서, 산 처리 전후의 변화를 나타낸 것이다. 이는 산 처리를 통하여 티탄산바륨의 표면에 카르복실 관능기가 존재하고 있는 것을 보여준다. 이처럼 카르복실 관능기가 표면에 흡착된 티탄산바륨은 고분자와의 상용성이 증대되어 고분자와 티탄산바륨 사이에 안정적인 계면이 형성되고, 그 결과 티탄산바륨의 함량이 매우 높은 고충진 고분자-티탄산바륨 복합체의 제조가 가능할 수 있다. As described above, as a result of the acid treatment, a carboxyl functional group is introduced to the surface of the barium titanate. FIG. 1 is an electrospectral chemical analysis (ESCA) graph of barium titanate showing changes before and after acid treatment. This shows that a carboxyl functional group exists on the surface of barium titanate through acid treatment. As such, the barium titanate adsorbed on the surface of the carboxyl functional group has increased compatibility with the polymer to form a stable interface between the polymer and the barium titanate, and as a result, the preparation of a high-filled polymer-barium titanate composite having a very high content of barium titanate May be possible.
또 다른 양태로서, 본 발명은 산 처리한 티탄산바륨을 포함하는 고분자-티탄산바륨 복합체를 제공한다. In still another aspect, the present invention provides a polymer-barium titanate composite comprising an acid treated barium titanate.
고분자-티탄산바륨의 복합체에 사용되는 고분자는 열가소성수지 또는 열경화성수지이다. 열가소성수지로는 폴리이미드(PI)수지, 폴리카보네이트(PC)수지, 폴리에스터수지, ABS 수지 또는 폴리아마이드(PA)수지 등이 있으며, 열경화성수지로 는 페놀수지, 멜라민수지, 우레아수지 또는 에폭시수지 등이 있다. The polymer used in the polymer-barium titanate composite is a thermoplastic resin or a thermosetting resin. Thermoplastic resins include polyimide (PI) resins, polycarbonate (PC) resins, polyester resins, ABS resins or polyamide (PA) resins, and thermosetting resins include phenol resins, melamine resins, urea resins or epoxy resins. Etc.
일반적으로, 고유전 충전제인 무기물과 고분자의 복합체를 제조할 경우, 무기물과 고분자간의 낮은 상용성으로 인하여, 무기물의 함량이 높아지면 고분자-무기물 혼합체의 점도가 크게 증가하여 성형가공성이 매우 나빠지며, 고분자와 무기물 사이에 심각한 응집현상이 일어나고, 이에 따라 복합체는 급격한 취성의 증가를 보인다. 따라서, 무기물 함량을 20 부피% 내지 30 부피% 이상으로 증가시킬 경우, 복합체 제조가 매우 어렵다. 하지만, 무기물의 함량이 낮아지면 유전성이 떨어지므로 무기물의 함량의 증가가 필수적이다. In general, when manufacturing a composite of the inorganic material and the polymer of the high dielectric filler, due to the low compatibility between the inorganic material and the polymer, when the content of the inorganic material increases, the viscosity of the polymer-inorganic mixture increases significantly, the molding processability is very poor, Severe agglomeration occurs between the polymer and the inorganic material, and the composite shows a sharp increase in brittleness. Therefore, when the inorganic content is increased from 20% by volume to 30% by volume or more, the preparation of the composite is very difficult. However, if the inorganic content is low, the dielectric property is low, so increasing the content of the inorganic material is essential.
본 발명의 산 처리된 티탄산바륨은 함량이 60 부피%까지 증가되어도 복합체 필름을 형성할 수 있었으며, 이렇게 얻어진 복합체 필름은 고유전율과 기계적 강도, 내 충격성 등의 우수한 기계적 물성을 보였다. 도 2는 실시예 1에서 제조한 나일론-산 처리한 티탄산바륨의 복합체 필름의 유전상수를 측정한 결과로서, 티탄산바륨의 함량이 증가함에 비례하여 복합체의 유전상수가 높아짐을 보여준다. 또한, 산 처리한 티탄산바륨이 고분자와 높은 상용성을 나타내므로, 응집현상 또는 취성의 증가 없이 기계적 강도, 내 충격성이 우수한 복합체 필름을 제조할 수 있었다. Acid-treated barium titanate of the present invention was able to form a composite film even if the content is increased to 60% by volume, the composite film thus obtained showed excellent mechanical properties such as high dielectric constant, mechanical strength, impact resistance. 2 is a result of measuring the dielectric constant of the composite film of nylon-acid treated barium titanate prepared in Example 1, showing that the dielectric constant of the composite is increased in proportion to the increase in the content of barium titanate. In addition, since the acid-treated barium titanate exhibits high compatibility with the polymer, it was possible to produce a composite film having excellent mechanical strength and impact resistance without increasing aggregation or brittleness.
이하, 실시예에 의해 본 발명을 보다 구체적으로 기술한다. 그러나, 본 발명의 범위가 이들 실시예들로 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, the scope of the present invention is not limited to these embodiments.
실시예Example 1: One: 열가소성수지Thermoplastic -산 처리한 티탄산바륨 복합체의 제조 Preparation of Acid-Treated Barium Titanium Composite
열가소성 수지로는 대표적인 폴리아마이드(polyamide) 수지인 나일론 6 (Nylon 6)을 사용하였다. 나일론 6-티탄산바륨 복합체의 제조 방법은 다음과 같다. 포름산(formic acid)에 나일론 6을 용해시킨 후, 티탄산바륨의 함량을 각각 달리하여 나일론6/포름산 용액에 첨가하고 초음파 처리를 티탄산바륨을 분산시켰다. 다음에 상기의 혼합액을 비용매인 알코올에 침전시킨 후, 용매를 제거 한 다음 건조시키고 가열압착방법을 통하여 나일론 6/티탄산바륨 복합체 필름을 제조하였다.As a thermoplastic resin, nylon 6 (Nylon 6), which is a representative polyamide resin, was used. The manufacturing method of the nylon 6-barium titanate composite is as follows. After dissolving nylon 6 in formic acid, the content of barium titanate was added to the nylon 6 / formic acid solution with varying amounts of barium titanate, and sonication was performed to disperse barium titanate. Next, after the mixed solution was precipitated in a non-solvent alcohol, the solvent was removed, dried, and a nylon 6 / barium titanate composite film was prepared by a hot pressing method.
실시예Example 2: 2: 열경화성수지Thermosetting resin -산 처리한 티탄산바륨 복합체의 제조Preparation of Acid-Treated Barium Titanium Composite
열경화성 수지로는 bisphenol-A 계열의 에폭시를 사용하였다. 에폭시-티탄산바륨 복합체의 제조방법은 다음과 같다. 산 처리를 위하여 포름산에 티탄산바륨을 분산시키고 초음파 처리를 행한 후, 감압 여과 방법으로 티탄산바륨만을 추출해내고 이를 다시 90℃에서 감압 조건에서 건조하였다. 상기 산 처리한 티탄산바륨을 에폭시와 에폭시수지의 경화반응을 일으키는 유기화합물인 아민계 경화제를 혼합물에 첨가한 후 다시 초음파 처리하였다. 상기의 혼합액을 필름 캐스팅한 다음 경화시켜 에폭시-티탄산바륨 복합체를 제조하였다. As the thermosetting resin, bisphenol-A series epoxy was used. The production method of the epoxy-barium titanate composite is as follows. After dispersing barium titanate in formic acid for sonication and performing an ultrasonic treatment, only barium titanate was extracted by vacuum filtration and dried under reduced pressure at 90 ° C. The acid-treated barium titanate was added to the mixture with an amine-based curing agent, which is an organic compound that causes the curing reaction between epoxy and epoxy resin, and then ultrasonicated again. The mixture was film cast and cured to prepare an epoxy-barium titanate composite.
실시예Example 3: 고분자 복합체 필름의 물성 확인 3: Check the physical properties of the polymer composite film
상기 실시예 1 및 실시예 2에서 제조한 복합체 필름의 티탄산바륨 함량을 0 부피% 부터 60 부피%까지 변화시키며 제조하여 물성을 비교하였다. 본 발명에서는 티탄산바륨 함량이 60 부피%까지 증가되어도 성공적으로 복합체 필름을 성형할 수 있었으며, 얻어진 복합체 필름은 유연성과 우수한 기계적 물성을 보였다. The barium titanate content of the composite films prepared in Examples 1 and 2 was changed from 0% by volume to 60% by volume to compare physical properties. In the present invention, even when the barium titanate content was increased to 60% by volume, the composite film was successfully formed, and the obtained composite film showed flexibility and excellent mechanical properties.
도 1은 티탄산바륨의 전자분광 화학분석 (ESCA) 그래프로서 산 처리 전 및 실시예 1에 따른 산 처리 후의 변화를 나타낸 것으로 티탄산바륨의 표면에 산 처리를 통하여 카르복실 관능기가 존재하고 있는 것을 보여준다. 이처럼 카르복실 관능기가 표면에 흡착된 티탄산바륨은 고분자와의 상용성이 증대되어 고분자와 티탄산바륨 사이에 안정적인 계면이 형성되고, 그 결과 티탄산바륨의 함량이 매우 높은 고충진 고분자/티탄산바륨 복합체의 제조가 가능하였다. FIG. 1 is an electron spectrochemical analysis (ESCA) graph of barium titanate, which shows changes before and after acid treatment according to Example 1, showing that carboxyl functional groups exist on the surface of barium titanate through acid treatment. As such, the barium titanate adsorbed on the surface of the carboxyl functional group has increased compatibility with the polymer to form a stable interface between the polymer and the barium titanate, and as a result, the preparation of a high-filling polymer / barium titanate composite having a very high content of barium titanate Was possible.
도 2와 4는 실시예 1 및 실시예 2의 복합체 필름의 100Hz~100MHz 범위에서 유전상수를 측정한 결과로서, 표면 개질된 티탄산바륨을 이용하여 매우 높은 유전율 증가의 효과를 얻을 수 있음을 보여주고 있다. 이는 산 처리한 티탄산바륨 표면의 카르복실 관능기의 도입으로 인한 복합체 내 티탄산바륨 함량 증가에 기인한 것이며, 이울러 도 3에 나타낸 것처럼 50 부피%의 높은 티탄산바륨 함량에서도 복합체 필름이 높은 유연성을 나타냄을 관찰하였다. 결국 산 처리를 통하여 고분자-티탄산바륨 복합체 필름은 높은 유전상수와 함께 우수한 기계적 강도 및 유연성을 동시에 확보할 수 있었다. Figures 2 and 4 as a result of measuring the dielectric constant in the range of 100Hz ~ 100MHz of the composite film of Example 1 and Example 2, showing that the effect of very high dielectric constant increase can be obtained by using the surface-modified barium titanate have. This is due to an increase in the barium titanate content in the composite due to the introduction of carboxyl functional groups on the surface of the acid-treated barium titanate, which also indicates that the composite film exhibits high flexibility even at a high barium titanate content of 50% by volume. Observed. Eventually, the acid-treated polymer-barium titanate composite film was able to secure excellent mechanical strength and flexibility simultaneously with high dielectric constant.
본 발명에 따른 산 처리한 티탄산바륨은 표면에 높은 쌍극자 모멘트의 카르복실 관능기가 도입되고, 카르복실 관능기의 도입으로 인하여 고분자와의 상용성이 크게 증가한다. 따라서 고분자-티탄산바륨 복합체 제조 시, 산 처리한 티탄산바륨을 사용할 경우 티탄산바륨의 함량이 증가된 복합체를 제조할 수 있다. 이러한 티탄산바륨의 함량이 증가된 복합체는 고 유전율을 나타내며, 또한, 기계적 강도, 내 충격성 등의 기계적 물성도 우수하다. In the acid-treated barium titanate according to the present invention, carboxyl functional groups having a high dipole moment are introduced to the surface, and compatibility with the polymer is greatly increased due to the introduction of carboxyl functional groups. Therefore, when preparing the polymer-barium titanate composite, when the acid-treated barium titanate is used, the composite having an increased content of barium titanate can be prepared. The composite having an increased content of barium titanate exhibits a high dielectric constant and is also excellent in mechanical properties such as mechanical strength and impact resistance.
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| KR (1) | KR100627248B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100879034B1 (en) | 2007-12-28 | 2009-01-15 | 한국과학기술연구원 | Organically Treated Barium Titanium / Epoxy Composite for Embedded Capacitors and Dielectric Film Fabrication Method Using the Same |
| US8779047B2 (en) * | 2006-07-27 | 2014-07-15 | Daikin Industries, Ltd. | Coating composition |
| CN106046745A (en) * | 2016-08-18 | 2016-10-26 | 上海锦湖日丽塑料有限公司 | Preparation method of novel electric-conductive PC/ABS material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990014262A (en) * | 1997-07-31 | 1999-02-25 | 가와다 미쓰구 | Manufacturing method as ceramic composite material |
| JP2003073555A (en) | 2001-08-31 | 2003-03-12 | Toray Ind Inc | Highly dielectric resin composition |
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2005
- 2005-09-13 KR KR1020050085353A patent/KR100627248B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990014262A (en) * | 1997-07-31 | 1999-02-25 | 가와다 미쓰구 | Manufacturing method as ceramic composite material |
| JP2003073555A (en) | 2001-08-31 | 2003-03-12 | Toray Ind Inc | Highly dielectric resin composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8779047B2 (en) * | 2006-07-27 | 2014-07-15 | Daikin Industries, Ltd. | Coating composition |
| KR100879034B1 (en) | 2007-12-28 | 2009-01-15 | 한국과학기술연구원 | Organically Treated Barium Titanium / Epoxy Composite for Embedded Capacitors and Dielectric Film Fabrication Method Using the Same |
| CN106046745A (en) * | 2016-08-18 | 2016-10-26 | 上海锦湖日丽塑料有限公司 | Preparation method of novel electric-conductive PC/ABS material |
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