KR100638663B1 - High dielectric constant ceramic/polymer composite and dielectric film for embedded capacitor - Google Patents
High dielectric constant ceramic/polymer composite and dielectric film for embedded capacitor Download PDFInfo
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- KR100638663B1 KR100638663B1 KR1020040094494A KR20040094494A KR100638663B1 KR 100638663 B1 KR100638663 B1 KR 100638663B1 KR 1020040094494 A KR1020040094494 A KR 1020040094494A KR 20040094494 A KR20040094494 A KR 20040094494A KR 100638663 B1 KR100638663 B1 KR 100638663B1
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- 229920000642 polymer Polymers 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 239000000919 ceramic Substances 0.000 title claims abstract description 29
- 239000003990 capacitor Substances 0.000 title claims abstract description 20
- 239000000945 filler Substances 0.000 claims abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 15
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- 230000009477 glass transition Effects 0.000 claims abstract description 9
- 239000004642 Polyimide Substances 0.000 claims abstract description 5
- 239000004643 cyanate ester Substances 0.000 claims abstract description 5
- 229920001721 polyimide Polymers 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 14
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 11
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 229920000671 polyethylene glycol diacrylate Polymers 0.000 claims description 7
- 229920001897 terpolymer Polymers 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910002112 ferroelectric ceramic material Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 9
- 229920000647 polyepoxide Polymers 0.000 description 9
- 230000001965 increasing effect Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229920000131 polyvinylidene Polymers 0.000 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 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/33—Thin- or thick-film capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/301—Assembling printed circuits with electric components, e.g. with resistor by means of a mounting structure
Abstract
본 발명은 고유전상수를 갖는 세라믹/폴리머 복합체 및 내장형 캐패시터용 유전체 필름에 관한 것으로서, 에폭시, 폴리이미드, 시아네이트 에스테르 및 그 조합으로 구성된 그룹으로부터 선택된 주성분과, 10이상의 유전율을 가지며 200℃이상의 유리전이온도를 갖는 폴리머인 부성분을 포함하며 상기 부성분은 상기 주성분의 5wt%∼20wt%로 함유된 폴리머 메트릭스와, 전체 복합체 기준으로 30부피% 내지 50부피%의 세라믹 필러를 포함하는 것을 특징으로 하는 고유전상수를 갖는 세라믹/폴리머복합체 및 이를 포함한 내장형 캐패시터용 유전체 필름을 제공한다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dielectric film for ceramic / polymer composites and embedded capacitors having a high dielectric constant, comprising a main component selected from the group consisting of epoxy, polyimide, cyanate ester, and combinations thereof, having a dielectric constant of 10 or more and a glass transition of 200 ° C. or more. A high dielectric constant comprising a subcomponent which is a polymer having a temperature, wherein the subcomponent comprises a polymer matrix containing 5 wt% to 20 wt% of the main component, and 30 to 50 vol% of ceramic fillers based on the total composite. Provided are a ceramic / polymer composite having a dielectric film for an embedded capacitor including the same.
내장형 캐패시터(embedded capacitor), 유전체 필름(dielectric film), 유전상수(dielectric constant)Embedded Capacitors, Dielectric Films, Dielectric Constants
Description
본 발명은 고유전상수를 갖는 세라믹/폴리머 복합체에 관한 것으로서, 특히 내장형 캐패시터에 적합한 고유전상수를 갖는 세라믹/폴리머 복합체와 이를 이용한 내장형 캐패시터용 유전체 필름에 관한 것이다.The present invention relates to a ceramic / polymer composite having a high dielectric constant, and more particularly, to a ceramic / polymer composite having a high dielectric constant suitable for an embedded capacitor and a dielectric film for an embedded capacitor using the same.
최근에 전자제품의 소형화와 고주파화를 구현하기 위해서, 수동소자에 대한 관심이 높아지고 있다. 캐패시터와 같은 수동소자는 전자제품에서 요구되는 수가 많을 뿐만 아니라, 적층형 기판의 표면에 실장하는 경우에 차지하는 면적이 크므로 소형화에 큰 장애요인이 된다.특히, 전자제품의 운용주파수가 높아짐에 따라, 수동소자가 능동소자의 입력단자와 연결되는 거리에 의해 인덕턴스성분이 유발되므로 고주파 성능을 저하시키는 문제가 된다.Recently, in order to realize miniaturization and high frequency of electronic products, interest in passive devices is increasing. Passive devices such as capacitors are not only required in electronic products but also have a large area when they are mounted on the surface of a laminated substrate, which is a big obstacle to miniaturization. In particular, as the operating frequency of electronic products increases, Since the inductance component is induced by the distance between the passive element and the input terminal of the active element, the high frequency performance is deteriorated.
이러한 수동소자의 문제를 해결하는 방안으로서, 내장형 수동소자 기술이 각 광을 받고 있다. 이는 캐패시터와 같은 수동소자를 적층형 기판의 표면에 개별부품으로 실장하지 않고 다층 기판의 내부에 집적화시키는 기술을 말한다. 이러한 내장형 수동소자기술은 수동소자에 의한 점유면적을 줄일 뿐만 아니라, 접속길이를 단축시킬 수 있으므로, 전자제품의 소형화와 고주파화에 크게 기여할 수 있다.As a way to solve the problem of the passive element, built-in passive element technology is receiving attention. This refers to a technique for integrating passive elements such as capacitors into the multilayer substrate without mounting them as individual components on the surface of the stacked substrate. This built-in passive element technology not only reduces the area occupied by the passive element, but also can shorten the connection length, which can greatly contribute to miniaturization and high frequency of electronic products.
일반적으로, 인쇄회로기판과 같은 다층기판에는 높은 가공성과 동박과의 접착성을 갖는, 에폭시수지와 같은 폴리머가 주로 사용된다. 하지만, 이러한 에폭시수지와 같은 폴리머는 낮은 유전상수를 가지므로, 내장형 수동소자의 유전체층으로 사용되는 적합하지 않다. 이러한 유전체층의 유전율을 높히기 위해서, BaTiO3분말과 같은 강유전체성 세라믹 필러(또는 "세라믹 분말"이라고도 함)이 분산된 에폭시물질을 사용하는 방법이 사용되었으나, 메트릭스인 폴리머 수지가 유전율이 매우 낮으므로, 강유전체분말을 분산시키더라도, 직렬연결된 캐패시터형태가 형성되어 전체 유전체율은 낮은 에폭시 수지의 유전율에 지배받아 효과가 미비하며, 메트릭스법칙(matrix rule)에 따르더라도 그 증가정도는 매우 작다는 문제가 있다.In general, a polymer such as an epoxy resin having high processability and adhesiveness with copper foil is mainly used in a multilayer board such as a printed circuit board. However, such polymers, such as epoxy resins, have a low dielectric constant and are not suitable for use as dielectric layers in embedded passive devices. In order to increase the dielectric constant of such a dielectric layer, a method using an epoxy material in which ferroelectric ceramic fillers (or "ceramic powders") are dispersed, such as BaTiO 3 powder, has been used, but since the matrix polymer resin has a very low dielectric constant, Even when the ferroelectric powder is dispersed, a series-connected capacitor is formed so that the overall dielectric constant is controlled by the low dielectric constant of the epoxy resin, and the effect is insignificant, and the increase is very small according to the matrix rule. .
미국특허 6,544,651호에서는, 금속 아세틸아세토네이트(metal acetyl-acetonate)를 첨가하여 폴리머사슬의 극성을 크게하여 유전율을 향상시키는 방법을 사용하고 있다. 다만, 실제 실험에서, 상기 방법은 다른 경화제보다는 무수물 경화제(anhydride hardner)를 사용할 때에 그 효과가 있는 것으로 확인되었다. 하지만, 무수물 경화제는 경화시간이 길다는 문제가 있으며, 유리전이온도(Tg) 등의 기판재 료로서의 특성을 열화시키는 원인이 된다.In US Pat. No. 6,544,651, a method of improving the dielectric constant by increasing the polarity of the polymer chain by adding metal acetyl-acetonate is used. In actual experiments, however, the method was found to have an effect when using anhydride hardner (anhydride hardner) rather than other curing agents. However, the anhydride curing agent has a problem that the curing time is long, which causes deterioration of characteristics as a substrate material such as glass transition temperature (T g ).
본 발명은 상술된 종래기술의 문제점을 해결하기 위한 것으로서, 그 목적은 낮은 유전상수를 갖는 기존의 폴리머를 주성분으로 하고, 상대적으로 높은 유전상수를 갖는 폴리머를 적정량 혼합하여, 폴리머 메트릭스 자체의 유전율을 향상시킴으로써 높은 유전율을 갖는 세라믹/폴리머 복합체를 제공하는데 있다.SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and an object thereof is mainly based on an existing polymer having a low dielectric constant, and by mixing an appropriate amount of a polymer having a relatively high dielectric constant, thereby increasing the dielectric constant of the polymer matrix itself. The present invention provides a ceramic / polymer composite having a high dielectric constant.
본 발명의 다른 목적은 상기한 높은 유전상수를 갖는 세라믹/폴리머 복합체를 이용한 내장형 캐패시터용 유전체 필름을 제공하는데 있다.
Another object of the present invention is to provide a dielectric film for embedded capacitors using a ceramic / polymer composite having a high dielectric constant.
상기한 기술적 과제를 달성하기 위해서, 본 발명은, In order to achieve the above technical problem, the present invention,
에폭시, 폴리이미드, 시아네이트 에스테르 및 그 조합으로 구성된 그룹으로부터 선택된 주성분과, 10이상의 유전율을 가지며 200℃이상의 유리전이온도를 갖는 폴리머인 부성분을 포함하고, 상기 부성분은 상기 주성분에 대해 5wt%∼20wt%로 함유된 폴리머 메트릭스와, 전체 복합체 기준으로 30부피% 내지 50부피%의 세라믹 필러를 포함하는 것을 특징으로 하는 고유전상수를 갖는 세라믹/폴리머복합체를 제공한다.A main component selected from the group consisting of epoxy, polyimide, cyanate ester and combinations thereof, and a subcomponent which is a polymer having a dielectric constant of 10 or more and a glass transition temperature of 200 ° C. or more, wherein the subcomponent is 5wt% to 20wt% based on the main component The present invention provides a ceramic / polymer composite having a high dielectric constant comprising a polymer matrix contained in% and a ceramic filler of 30% by volume to 50% by volume based on the total composite.
본 발명에서는 기존의 기판 주재료인 폴리머에 적어도 10의 유전율을 갖고 200℃이상의 유리전이온도를 갖는 유전성강화용 폴리머를 5wt% 내지 20wt%를 혼합함으로써 유전상수를 향상시킬 수 있다. 유전성 강화용 폴리머가 5wt%미만일 때는 유전상수의 향상효과가 미비하며, 20%를 초과하면, 박리강도(peel strength)가 낮아지므로, 5wt%∼20wt%범위로 혼합하는 것이 바람직하다. In the present invention, the dielectric constant may be improved by mixing 5 wt% to 20 wt% of a dielectric strengthening polymer having a dielectric constant of at least 10 and a glass transition temperature of 200 ° C. or more with a polymer, which is a main substrate material. When the dielectric strengthening polymer is less than 5wt%, the effect of improving the dielectric constant is insignificant, and when it exceeds 20%, since the peel strength is lowered, it is preferable to mix in the range of 5wt% to 20wt%.
바람직하게, 상기 주성분인 폴리머는 에폭시일 수 있으며, 이 경우에, 상기 부성분인 폴리머는 폴리디아크릴레이트계 폴리머 또는 폴리 비닐리덴 플루로이드계 폴리머인 것이 바람직하다.Preferably, the main component polymer may be epoxy, and in this case, the subcomponent polymer is preferably a polydiacrylate-based polymer or a polyvinylidene fluoride-based polymer.
여기서, 상기 폴리디아크릴레이트계 폴리머는 폴리 에틸렌 글리콜 디아크릴레이트(PEGDA)일 수 있으며, 이와 달리, 상기 폴리 비닐리덴 플루로이드계 폴리머는, 헥사플루로프로펜(HFP) 및 트리플루로클로로에틸렌(TrFClE)으로부터 선택된 1 또는 2종의 폴리머와 비닐리덴 폴리플로라이드의 공중합체 또는 삼중합체일 수도 있다. 즉, 비닐리덴 디플루로에틸렌(PVF2) 및 비닐리덴 트리플루로에틸렌(PVF3)으로부터 선택된 비닐리덴 폴리플로라이드와, 헥사플루로프로펜(HFP) 및/또는 트리플루로클로로에틸렌(TrFClE)를 혼합한 공중합체 또는 삼중합체를 사용할 수도 있다.Herein, the polydiacrylate-based polymer may be polyethylene glycol diacrylate (PEGDA). Alternatively, the polyvinylidene fluoride-based polymer may include hexafluoropropene (HFP) and trifluorochloroethylene ( It may also be a copolymer or terpolymer of one or two polymers selected from TrFClE) and vinylidene polyfluoride. That is, vinylidene polyfluoride selected from vinylidene difluroethylene (PVF 2 ) and vinylidene trifluoroethylene (PVF 3 ) and hexafluropropene (HFP) and / or trifluorochloroethylene (TrFClE) are mixed. One copolymer or terpolymer can also be used.
바람직하게는, 상기 세라믹 필러는 BaTiO3분말과 같은 강유전성 세라믹 물질일 수 있다.Preferably, the ceramic filler may be a ferroelectric ceramic material such as BaTiO 3 powder.
본 발명의 다른 실시형태에서는, 에폭시, 폴리이미드, 시아네이트 에스테르 및 그 조합으로 구성된 그룹으로부터 선택된 주성분과, 10이상의 유전율을 가지며 200℃이상의 유리전이온도를 갖는 폴리머인 부성분를 포함하며, 상기 부성분은 상기 주성분의 5wt%∼20wt%함유된 폴리머 메트릭스와, 전체 복합체 기준으로 30부피% 내지 50부피%의 세라믹 필러와, 경화제를 포함하는 것을 특징으로 하는 고유전상수를 갖는 것을 특징으로 하는 내장형 캐패시터용 유전체 필름을 제공한다. In another embodiment of the present invention, there is provided a main component selected from the group consisting of epoxy, polyimide, cyanate ester, and combinations thereof, and a subcomponent which is a polymer having a dielectric constant of at least 10 and a glass transition temperature of at least 200 ° C. A dielectric film for embedded capacitors having a polymer matrix containing 5 wt% to 20 wt% of the main component, a ceramic filler of 30 vol% to 50 vol% based on the total composite, and a hardening agent. To provide.
본 발명의 주요한 특징은 기판재료로서의 특성(박리강도, 유리전이온도)을 저하시키지 않는 범위에서 폴리머 메트릭스 자체의 유전율을 개선함으로써 세라믹 필러 첨가시의 유전율 향상 효과를 극대화시키는데 있다. The main feature of the present invention is to maximize the dielectric constant improvement effect when the ceramic filler is added by improving the dielectric constant of the polymer matrix itself in a range that does not lower the characteristics (peel strength, glass transition temperature) as the substrate material.
이하, 본 발명의 작용과 효과를 바람직한 실시예를 통해서 보다 상세히 설명하기로 한다.Hereinafter, the operation and effects of the present invention will be described in more detail with reference to preferred embodiments.
(실시예1)Example 1
본 실시예에서는 에폭시 수지에 폴리 에틸렌 글리콜 디아크릴레이트(PEGDA)를 5wt%, 10wt%, 15%, 20wt%, 25wt%를 측량하여 각각 첨가함으로써 6개의 폴리머 복합체를 마련하였다. In this example, six polymer composites were prepared by measuring and adding 5 wt%, 10 wt%, 15%, 20 wt%, and 25 wt% of polyethylene glycol diacrylate (PEGDA) to the epoxy resin.
얻어진 각 폴리머 복합체에 대해 1㎑에서 유전율을 측정하였으며, 박리강도 를 측정하여 기존 에폭시 수지만을 사용한 경우보다 5%이상으로 강도가 저하되는 경우에는 박리강도에 대해 불량으로 평가하였다. 그 결과를 아래의 표1에 나타내었다.The dielectric constant was measured at 1 에 for each of the obtained polymer composites, and the peel strength was measured, and when the strength was lowered to 5% or more than that of the existing epoxy resin, the peel strength was evaluated as poor. The results are shown in Table 1 below.
상기한 표1과 같이, PEGDA를 5wt%로 첨가한 경우에, 기존의 에폭시만의 유전상수(3.92)에 비해 약 6%의 유전율 향상효과를 나타내었으며, PEGDA의 첨가량을 증가시킴에 따라, 각각 10%, 15%, 19% 및 21%의 유전율상승효과를 나타냈었다. 다만, 25wt%를 첨가하는 예와 같이, 접착강도가 약해져 박리강도가 저하되므로, 기판재료로서의 폴리머로서 적합하지 않은 것으로 확인되었다.As shown in Table 1, when PEGDA was added at 5 wt%, the dielectric constant improved by about 6% compared to the existing dielectric constant of epoxy only (3.92), and as the amount of PEGDA was increased, Dielectric constants were increased by 10%, 15%, 19% and 21%. However, as in the example of adding 25wt%, since the adhesive strength was weakened and the peeling strength was lowered, it was confirmed that it was not suitable as a polymer as the substrate material.
본 실시예에서 확인된 바와 같이, PEGDA를 적정량으로 첨가함으로써 기판재료의 메트릭스성분자체의 유전율을 6 내지 19%까지 향상시킬 수 있다. 이러한 효과는 다른 고유전상수의 필러 등을 첨가할 경우에 낮은 유전상수의 물질(종래의 에폭시수지)에 지배를 받는다는 점을 고려할 때에, 실제 적용시에 높은 유전상수효과를 유발할 수 있다는 것을 기대할 수 있다.As confirmed in this embodiment, by adding PEGDA in an appropriate amount, the dielectric constant of the matrix component itself of the substrate material can be improved by 6 to 19%. This effect can be expected to induce high dielectric constant effects in practical applications, considering that the addition of fillers of other high dielectric constants is subject to the low dielectric constant material (primary epoxy resin). .
(실시예2)Example 2
본 실시예에서 유전성강화 폴리머로 비닐리덴 폴리플루로이드계 폴리머를 사용하기 위해서, 폴리 비닐리덴 디플루로이드(PVF2) 40wt%와 폴리(비닐리덴 디플루로이드(VF2)/ 비닐리덴 트리플루로이드(VF3)) 60%의 공중합체를 마련하였다. 상기 비닐리덴 폴리플루로이드계 공중합체를 에폭시 수지에 5wt%, 10wt%, 15%, 20wt%, 25wt%를 측량하여 각각 첨가함으로써 6개의 폴리머 복합체를 마련하였다. In this embodiment, in order to use a vinylidene polyfluid polymer as the dielectric strengthening polymer, 40 wt% of polyvinylidene difluid (PVF 2 ) and poly (vinylidene difluid (VF 2 ) / vinylidene trifluid (VF 3 )) 60% copolymer was prepared. The vinylidene polyfluid-based copolymer was added to the epoxy resin by measuring 5 wt%, 10 wt%, 15%, 20 wt%, and 25 wt%, respectively, to prepare six polymer composites.
실시예1과 동일한 조건에서, 각 폴리머 복합체에 대해 1㎑에서 유전율을 측정하였으며, 박리강도를 측정하여 기존 에폭시 수지만을 사용한 경우보다 5%이상으로 강도가 저하되는 경우에는 박리강도에 대해 불량으로 평가하였다. 그 결과를 아래의 표2에 나타내었다.Under the same conditions as in Example 1, the dielectric constant was measured at 1 에 for each polymer composite, and the peel strength was measured. Evaluated. The results are shown in Table 2 below.
상기한 표2과 같이, 상기한 PVF계 공중합체를 5wt%로 첨가한 경우에, 기존의 에폭시만의 유전상수(3.92)에 비해 약 9%의 유전율 향상효과를 나타내었으며, 그 첨가량을 증가시킴에 따라, 각각 17%, 24%, 33% 및 40%의 유전율상승효과를 나타냈었다. 다만, 25wt%를 첨가하는 예와 같이, 접착강도가 약해져 박리강도가 저하되므 로, 기판재료로서의 폴리머로서 적합하지 않은 것으로 확인되었다.As shown in Table 2 above, when the PVF-based copolymer was added at 5wt%, the dielectric constant improved by about 9% compared to the dielectric constant of the epoxy alone (3.92), and the addition amount was increased. According to the results, the dielectric constant increases of 17%, 24%, 33% and 40%, respectively. However, as in the example of adding 25wt%, the adhesive strength was weakened and the peeling strength was lowered, and thus it was confirmed that it was not suitable as a polymer as the substrate material.
(실시예3)Example 3
본 실시예에서, 유전성강화 폴리머로서 사용된 비닐리덴 폴리플루로이드계 폴리머는 비닐리덴 폴리(2-,3-)플루로이드, 헥사플루로프로펜(HFP), 트리플루로클로로에틸렌(TrFCE)를 적절히 혼합하여 마련하였다. 구체적으로 본 실시예에 사용된 비닐리덴 폴리플루로이드계 폴리머는 P(VF3(35%)-VF2(60%)-HFP(5%))의 삼중합체와 P(VF3(35%)-VF2(60%)-TrFCIE(5%))의 삼중합체를 각각 30wt%, 70wt%를 혼합한 폴리머복합체였다.In this embodiment, the vinylidene polyfluidic polymer used as the dielectric strengthening polymer appropriately contains vinylidene poly (2-, 3-) fluid, hexafluoropropene (HFP), and trifluorochloroethylene (TrFCE). It was prepared by mixing. Specifically, the vinylidene polyfluidic polymer used in the present embodiment is a terpolymer of P (VF 3 (35%)-VF 2 (60%)-HFP (5%)) and P (VF 3 (35%)). -VF 2 (60%)-TrFCIE (5%)) was a polymer composite in which 30 wt% and 70 wt% of the terpolymer were mixed, respectively.
이러한 폴리머복합체를 에폭시 수지에 5wt%, 10wt%, 15%, 20wt%, 25wt%를 측량하여 각각 첨가함으로써 6개의 폴리머 복합체를 마련하였다. Six polymer composites were prepared by measuring and adding 5 wt%, 10 wt%, 15%, 20 wt%, and 25 wt% to the polymer composite.
얻어진 각 폴리머 복합체에 대해 1㎑에서 유전율을 측정하였으며, 박리강도를 측정하여 기존 에폭시 수지만을 사용한 경우보다 5%이상으로 강도가 저하되는 경우에는 박리강도에 대해 불량으로 평가하였다. 그 결과를 아래의 표3에 나타내었다.For each polymer composite obtained, the dielectric constant was measured at 1 ,, and the peel strength was measured. When the strength was lowered to 5% or more than that of the existing epoxy resin, the peel strength was evaluated as poor. The results are shown in Table 3 below.
상기한 표3과 같이, 유전성강화용 폴리머를 5wt%로 첨가한 경우에, 기존의 에폭시만의 유전상수(3.92)에 비해 약 11%의 유전율 향상효과를 나타내었으며, 그 첨가량을 증가시킴에 따라, 각각 27%, 33%, 45% 및 53%의 유전율상승효과를 나타냈었다. 다만, 25wt%를 첨가하는 예와 같이, 접착강도가 약해져 박리강도가 저하되므로, 기판재료로서의 폴리머로서 적합하지 않은 것으로 확인되었다.As shown in Table 3, when the dielectric strength enhancing polymer was added at 5wt%, the dielectric constant improved by about 11% compared to the dielectric constant of the epoxy alone (3.92), and as the amount added increased, The dielectric constants were 27%, 33%, 45% and 53%, respectively. However, as in the example of adding 25wt%, since the adhesive strength was weakened and the peeling strength was lowered, it was confirmed that it was not suitable as a polymer as the substrate material.
상기한 실시예2 및 실시예3에서 확인된 바와 같이, 폴리 비닐리덴 폴리머계 공중합체 또는 삼중합체(혼합물)를 적정량으로 첨가함으로써 박리강도의 저하없이 기판재료의 메트릭스성분자체의 유전율을 9 내지 45%까지 향상시킬 수 있다. 이러한 효과는 다른 고유전상수의 필러 등을 첨가할 경우에 낮은 유전상수의 물질(종래의 에폭시수지)에 지배를 받는다는 점을 고려할 때에, 실제 적용시에 보다 높은 유전상수효과를 기대할 수 있다는 것을 이해할 수 있을 것이다.As confirmed in Examples 2 and 3 above, by adding the polyvinylidene polymer copolymer or terpolymer (mixture) in an appropriate amount, the dielectric constant of the matrix component itself of the substrate material is reduced to 9 to 45 without a drop in peel strength. Up to% can be improved. It can be understood that higher dielectric constant effects can be expected in practical applications, considering that these effects are governed by low dielectric constant materials (traditional epoxy resins) when fillers of other high dielectric constants are added. There will be.
상기한 실시예와 같은 본 발명에 따라 유전성 강화 폴리머가 적정량 첨가된 폴리머메트릭스는 강유전성을 갖는 세라믹필러와 혼합되어 높은 유전성을 갖는 세라믹/폴리머 복합체를 제공할 수 있다. 이 경우에, 세라믹 필러의 첨가량은 전체 복합체 기준으로 약 30% 내지 약 50%로 첨가하는 것이 바람직하다.According to the present invention as described above, the polymer matrix added with an appropriate amount of the dielectric enhancement polymer may be mixed with a ceramic filler having ferroelectricity to provide a ceramic / polymer composite having high dielectric properties. In this case, the addition amount of the ceramic filler is preferably added at about 30% to about 50% based on the total composite.
본 발명에 따른 세라믹/폴리머복합체에 소정의 경화제를 적절히 추가함으로써 높은 유전상수를 갖는 내장형 캐패시터용 유전체 필름을 얻을 수 있다. 물론, 상기 내장형 캐패시터용 유전체 필름에는 추가적으로 고유전율의 필러를 추가적으로 첨가시킬 수 있으며, 폴리머 메트릭스의 유전상수가 높으므로, 필러에 의한 유전상수 증가효과를 보다 획기적으로 향상시킬 수 있다.By appropriately adding a predetermined curing agent to the ceramic / polymer composite according to the present invention, a dielectric film for an embedded capacitor having a high dielectric constant can be obtained. Of course, a filler having a high dielectric constant may be additionally added to the embedded capacitor dielectric film, and the dielectric constant of the polymer matrix is high, so that the effect of increasing the dielectric constant due to the filler may be further improved.
본 발명은 상술한 실시형태 및 첨부된 도면에 의해 한정되는 것이 아니며, 첨부된 청구범위에 의해 한정하고자 한다. 따라서, 청구범위에 기재된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 당 기술분야의 통상의 지식을 가진 자에 의해 다양한 형태의 치환, 변형 및 변경이 가능할 것이며, 이 또한 본 발명의 범위에 속한다고 할 것이다.It is intended that the invention not be limited by the foregoing embodiments and the accompanying drawings, but rather by the claims appended hereto. Accordingly, various forms of substitution, modification, and alteration may be made by those skilled in the art without departing from the technical spirit of the present invention described in the claims, which are also within the scope of the present invention. something to do.
상술한 바와 같이, 본 발명에 따르면, 내장형 캐패시터용 유전체 필름에 주로 사용된 저유전율의 폴리머를 메트릭스에 기판재료로서의 특성(박리강도, 유리전이온도)을 저하시키지 않는 범위에서 유전성 강화 폴리머를 추가로 첨가시킴으로써 폴리머 메트릭스 자체의 유전율을 향상시킬 수 있으며, 이로 인해 세라믹 필러 첨가시에 유전율 상승효과를 극대화시킬 수 있다. As described above, according to the present invention, a dielectric constant-reinforced polymer is further added in a range in which the low dielectric constant polymer mainly used in the dielectric film for embedded capacitors does not degrade the characteristics (peel strength, glass transition temperature) as a substrate material in the matrix. The addition can improve the dielectric constant of the polymer matrix itself, thereby maximizing the dielectric constant synergistic effect when the ceramic filler is added.
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