KR100373980B1 - Expoxy resin composition of ignition coil for motor vehicles - Google Patents
Expoxy resin composition of ignition coil for motor vehicles Download PDFInfo
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- KR100373980B1 KR100373980B1 KR1019960006836A KR19960006836A KR100373980B1 KR 100373980 B1 KR100373980 B1 KR 100373980B1 KR 1019960006836 A KR1019960006836 A KR 1019960006836A KR 19960006836 A KR19960006836 A KR 19960006836A KR 100373980 B1 KR100373980 B1 KR 100373980B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/226—Mixtures of di-epoxy compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C08K7/00—Use of ingredients characterised by shape
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- C08K7/14—Glass
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
Description
본 발명은 자동차 이그니션 코일에 적용되는 절연 충전물로 사용가능한 에폭시수지 조성물에 관한 것으로, 1000시간 동안 프레스쿠커 시험(press cooker test)및 열충격 시험(thermal shock test)후에 나타나는 박리현상, 경화물의 균열, 수축성을 개선시킴으로써 높은 신뢰성이 요구되는 자동차 이그니션 코일에 사용가능한2액형 에폭시수지 조성물에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition that can be used as an insulating filler applied to automotive ignition coils. The present invention relates to a peeling phenomenon, cracks and shrinkages that occur after 1000 hours of press cooker test and thermal shock test. The present invention relates to a two-component epoxy resin composition that can be used in automotive ignition coils requiring high reliability.
에폭시수지는 반응성이 풍부한 옥시란 기를 1분자 중에 2개이상 가지고 있는 화합물로서, 그 기본 골격구조에 여러가지 기를 도입하면 독특한 물리적 특성을 나타내므로 용도에 따라 다양한 방법으로 구조를 변형시킬 수 있는데 수지에 조합되는 경화제, 충진제의 종류에 따라 다양한 물리적 특성을 나타내므로 전기, 전자 소재 분야에 있어서 중요한 재료중의 하나이다.Epoxy resin is a compound having two or more reactive oxirane groups in one molecule. When various groups are introduced into the basic skeleton structure, epoxy resins exhibit unique physical properties. It is one of the important materials in the field of electrical and electronic materials because it exhibits various physical properties depending on the type of curing agent and filler.
특히 자동차 이그니션 코일 수지 절연 조성물로서의 에폭시 수지는, 코일내의 우수한 함침성과 더불어 열충격 시험시 이그니션 하우징(housing)과 2차 코일 와이어(coil wire) 사이의 균열 또는 수축의 방지, 및 일정수준 이상의 전기 절연성이 요구된다.In particular, the epoxy resin as an automotive ignition coil resin insulating composition has excellent impregnation in the coil, prevents cracking or shrinkage between the ignition housing and the secondary coil wire during thermal shock test, and has a certain level of electrical insulation. Required.
이러한 요구에 부응하기 위하여 종래의 기술에서는 에폭시수지에 단순 충진제(비실란 처리)를 다량 첨가하여 주제 수지를 제조하였는데, 이 때 산 무수물 경화제를 사용함으로써 높은 발열에 따른 큰 수축과 점도 상승으로 인한 작업성 감소로 코일내의 함침성이 저하되는 문제가 있었다.In order to meet these demands, in the related art, a main resin was prepared by adding a simple filler (non-silane treatment) to an epoxy resin, and at this time, by using an acid anhydride curing agent, workability due to large shrinkage and viscosity increase due to high heat generation There is a problem that the impregnation in the coil is lowered due to the decrease.
이를 개선하기 위한 방법으로 희석제나, 저점도 에폭시를 주제 수지에 첨가하는 방법을 사용하였으나, 이는 작업 점도 및 함침성에 대한 일부 개선은 가능하였지만 열충격 시험 및 열사이클링 시험(thermal cycling test)에서 이그니션 하우징과 2차 코일내의 균열 및 박리현상 문제를 야기하였다.In order to improve this, a diluent or a low viscosity epoxy was added to the main resin, but it was possible to improve the working viscosity and impregnation, but the ignition housing and the thermal shock test were performed in the thermal shock test and thermal cycling test. It caused the problem of cracking and peeling in the secondary coil.
최근에는 이러한 균열 및 수축을 최소화시키려는 방법으로서 에폭시수지내에 변성된 고무계 화합물 및 글리콜계 화합물을 혼합하는 방법이 고안되었다. 그러나고무계 화합물 변성방법의 경우는 내열성이 저하하고 경화 조건에 따라 물리적 특성이 크게 변하는 단점이 있었으며, 글리콜 변성 방법은 열적 특성 및 내아아크성(arc resistance)이 기존 제품에 비하여 크게 떨어지는 문제가 있었다.Recently, as a method for minimizing such cracking and shrinkage, a method of mixing a modified rubber compound and a glycol compound in an epoxy resin has been devised. However, in the case of the rubber compound modification method, there is a disadvantage in that the heat resistance is lowered and the physical properties are greatly changed according to the curing conditions, and the glycol modification method has a problem in that the thermal properties and arc resistance are significantly lower than those of the conventional products.
본 발명의 목적은 신뢰성이 요구되는 자동차 이그니션 코일내에 사용가능한 절연 충진물을 제조함에 있어서, 환상지환족 에폭시수지 및 비스페놀에폭시를 예비 혼합 교반시킨 수지 조성물에 실란 처리된 규회석과 유리섬유 충진제를 배합하여 주제 수지 조성물로 하고, 주제 수지 조성물에 지방족 또는 지환족 산 무수물로 변성된 경화제를 첨가하여 이루어지는 우수한 함침성, 작업성과 더불어 프레스쿠커 시험 후 열충격 시험에서 수축에 의한 균열 발생을 개선시키는 2액형 수지 조성물을 제공하기 위한 것이다.SUMMARY OF THE INVENTION An object of the present invention is to prepare an insulating filler that can be used in automotive ignition coils requiring reliability, by combining silane-treated wollastonite and glass fiber filler in a resin composition prepared by premixing and stirring a cycloaliphatic epoxy resin and bisphenol epoxy. A two-component resin composition comprising a resin composition, which has excellent impregnation and workability by adding a curing agent modified with aliphatic or cycloaliphatic acid anhydride to the main resin composition, and improves the occurrence of cracking by shrinkage in the thermal shock test after the press cooker test. It is to provide.
본 발명에서 사용되는 환상지환족 에폭시수지로는 에폭시 당 량이 120 내지 220g/몰로, 에폭시 기를 1분자내에 2개이상 가지고 있는 것으로, 상세한 예로는 지환족 디에폭시아세탈, 지환족 디에폭시아디페이트, 지환족 디에폭시카복실레이트, 지환족 작용기 유도체 등이 있다. 비스페놀에폭시계 수지로는 디글리시딜에테르 비스페놀 수지가 있으며, 환상지환족 에폭시수지 10 내지 45중량%와 비스페놀 에폭시 55내지 90중량%를 가열온도 80℃, 질소 분위기하에서 1시간동안 혼합 교반하며, 이때 중간 촉매로서는 테트라메틸암모늄클로라이드를 사용할 수 있다. 또한, 사용한 비스페놀계 에폭시는 가수분해성 염소 함량이 200ppm 이하인 것이 유리하다.The cycloaliphatic epoxy resin used in the present invention is an epoxy equivalent of 120 to 220 g / mole, having two or more epoxy groups in one molecule, and examples of the cycloaliphatic diepoxycetal, cycloaliphatic diepoxydiate, alicyclic Family diepoxycarboxylates, cycloaliphatic functional derivatives, and the like. The bisphenol epoxy resin is a diglycidyl ether bisphenol resin, 10 to 45% by weight of the cycloaliphatic epoxy resin and 55 to 90% by weight bisphenol epoxy is mixed and stirred for 1 hour under a heating temperature of 80 ℃, nitrogen atmosphere, At this time, tetramethylammonium chloride may be used as the intermediate catalyst. In addition, the bisphenol-based epoxy used is advantageously a hydrolyzable chlorine content of 200 ppm or less.
예비반응시킨 에폭시 수지 조성물에는 경화물의 기계적, 전기적 물성을 향상시키기 위하여 무기 충진제를 배합하여 주제 수지 조성물을 만드는데, 무기물중에서도 실리카, 알루미나, 운모, 규회석, 탄산칼슘, 점토, 유리 섬유 등이 사용가능하지만 성형하는 제품의 용도, 가공 방법, 외부 환경에 따라서 충전제의 입자 분포, 불순물 함량에 유의하여 선정하여야 한다.The pre-reacted epoxy resin composition is formulated with inorganic fillers to improve the mechanical and electrical properties of the cured product.Since inorganic, silica, alumina, mica, wollastonite, calcium carbonate, clay, and glass fiber can be used. The particle distribution of the filler and the impurity content should be selected carefully according to the use of the product to be molded, the processing method, and the external environment.
무기 충진제는 주제 수지 조성물 전체 조성의 45 내지 80중량%가 되도록 혼합한다.The inorganic filler is mixed so as to be 45 to 80% by weight of the total composition of the main resin composition.
충진제는 알파글리시톡시프로필트리메톡시실란으로 코팅시켜 진공 오븐에서 3내지 5시간 동안 건조시킨다. 특히 충진제로서 규회석을 실란처리하지 않고 사용할 경우 상온에서의 수분 흡수가 심하여 최종 경화물의 수축 및 전기 특성이 오히려 저하되는 단점이 있다. 사용된 규회석의 물리적 특성은 평균 입경이 7 내지 35㎛, 최대 입경이 120㎛ 이하이고 입경 형상이 침상형이며, 주제 수지 반응물의 25 내지 75중량%가 적당하였다.The filler is coated with alphaglyoxymethoxypropyltrimethoxysilane and dried in a vacuum oven for 3 to 5 hours. In particular, when the wollastonite is used as a filler without silane treatment, there is a disadvantage in that water absorption at room temperature is severe and the shrinkage and electrical properties of the final cured product are deteriorated. The physical properties of wollastonite used were 7-35 micrometers in average particle diameter, 120 micrometers or less in maximum particle size, needle shape, and 25-75 weight% of the main resin reactants were suitable.
또한 충진제인 유리 섬유의 경우는 길이가 0.1 내지 0.5mm, 직경이 0.0001 내지 0.01mm이되, 상기 직경에 대한 길이의 비율이 100이상이고, 표면적이 5 내지 12m2/g인 단섬유로서, 주제 수지 조성물의 5 내지 20중량%가 적당하였다. 유리 섬유는 최종 경화물의 유연성 및 수축성을 개선시켜 균열을 줄일 수 있으나, 상기 함량보다 많을 경우에는 점도가 증가함에 따라 함침성과 작업성이 저하되는 결과를 가져올 수 있다.In addition, in the case of the glass fiber as a filler, the length is 0.1 to 0.5mm, the diameter is 0.0001 to 0.01mm, the ratio of the length to the diameter is 100 or more, the surface fiber 5-12m 2 / g as a short fiber, the main resin 5 to 20% by weight of the composition was suitable. Glass fiber can reduce the cracks by improving the flexibility and shrinkage of the final cured product, but when the glass fiber is more than the content, the glass fiber may result in impregnation and workability as the viscosity increases.
또한, 충진제의 침강방지 및 틱소트로피(thixotropy)를 부여하기 위하여 벤토나이트(bentonite), 운모, 활석 등을 사용하였으며, 수지의 표면장력을 낮추어정적 유동을 증가시킴으로써 주조성형시 수지 표면에 기포가 맺히는 핀홀(pinhole) 현상이 방지되도록 실리콘 오일이나, 파인 오일(pine oil), 폴리올테르펜 중합체 등을 소량으로 첨가하여 주제 수지 조성물을 만들었다.In addition, bentonite, mica, and talc were used to prevent sedimentation and thixotropy of the filler, and pinholes were formed on the resin surface during casting by increasing the static flow by lowering the surface tension of the resin. The main resin composition was made by adding a small amount of silicone oil, pine oil, polyol terpene polymer, and the like to prevent pinhole phenomenon.
본 발명에서는 고온 경화시 높은 발열에 따른 코일 와이어의 손상 및 하우징의 균열을 줄이기 위한 방법으로 산 무수물을 폴리에스테르지방산으로 변성시킨 경화제를 주제 수지 조성물 100중량부에 대하여 20 내지 60중량부로 주제 수지 조성물에 첨가한다.In the present invention, the curing agent in which the acid anhydride is modified with polyester fatty acid as a method for reducing damage to the coil wire and cracking of the housing due to high heat generation during high temperature curing is 20 to 60 parts by weight based on 100 parts by weight of the main resin composition. Add to
변성 경화제는 지환족, 지방족 산 무수물을 분자내에 카복실 기와 알켄 기를 포함하는 폴리에스테르지방산(탄소원자 수 4 내지 32개)으로 변성시킨 것이며, 폴리에스테르지방산의 예로는 스테아르산, 올레산, 리놀레산, 리시놀레산, 팔미트산, 이량체산 등 및 이들의 유도체가 있으며, 산 무수물 중량 65 내지 95중량%와 폴리에스테르산 2 내지 32중량%로 함이 적당하였다.The modified curing agent is a modified product of alicyclic and aliphatic acid anhydride with polyester fatty acid (4 to 32 carbon atoms) containing carboxyl group and alkene group in the molecule. Leic acid, palmitic acid, dimer acid and the like and derivatives thereof, and it is suitable to use 65 to 95% by weight of acid anhydride and 2 to 32% by weight of polyester acid.
변성 경화제에 사용된 산 무수물의 예로는 말레산 무수물, 테트라하이드로프탈산 무수물, 메틸테트라하이드로프탈산 무수물, 헥사하이드로프탈산 무수물, 메틸헥사하이드로프탈산 무수물, 프탈산 무수물, N-옥실-숙신산 무수물, 숙신산 무수물 또는 이들의 유도체 등이 있다.Examples of acid anhydrides used in the modified curing agents include maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phthalic anhydride, N-oxyl-succinic anhydride, succinic anhydride or these Derivatives and the like.
또한 경화를 촉진하기 위해 벤질디메틸아민, 트리(디메틸아미노메틸)페놀, 2-(디메틸아미노메틸)페놀, 트리(디메틸아미노메틸)페놀의 2-에틸헥실산염 등 지방족, 방향족 3급아민의 유도체 염을 경화촉진제로 사용할 수 있고, 이미다졸이나 그의 유도체도 사용할 수 있다.Also, derivative salts of aliphatic and aromatic tertiary amines, such as benzyldimethylamine, tri (dimethylaminomethyl) phenol, 2- (dimethylaminomethyl) phenol, and 2-ethylhexyl acid salt of tri (dimethylaminomethyl) phenol, to promote curing. Can be used as a curing accelerator, and imidazole and derivatives thereof can also be used.
제조예: 변성 경화제의 제조방법 Preparation Example : Manufacturing Method of Modified Curing Agent
융점이 53℃인 무수 말레인산 850g을 질소 분위기하에서 4구 둥근 플라스크에 넣고, 90℃까지 승온시키고, 리놀레산 150g을 첨가한 후 110℃에서 4시간 동안 반응시켜서, 리놀레산중의 디엔 기가 무수 말레인산과 딜스-알더 반응(Diels-Alder reaction)을 하여 본 발명에 사용되는 하기 일반식(I)과 같은 구조의 변성된 경화제를 얻었다:850 g of maleic anhydride having a melting point of 53 ° C. was placed in a four-necked round flask under nitrogen atmosphere, heated to 90 ° C., 150 g of linoleic acid was added, and then reacted at 110 ° C. for 4 hours. The diene group in linoleic acid was dissolved in maleic anhydride and dils- A Diels-Alder reaction gave a modified hardener of the structure as shown in general formula (I) used in the present invention:
상기 식에서,Where
R1은 알킬 기(탄소원자 수 1 내지 12개)이고,R 1 is an alkyl group (1-12 carbon atoms),
R2는 저급 알킬 기(탄소원자 수 1 내지 5개)또는 수소이며,R 2 is a lower alkyl group (1-5 carbon atoms) or hydrogen,
X는 알켄 기(탄소원자 수 1 내지 4개), 아릴 기(탄소원자 수 6 내지 12개), 폴리사이클로알칸 기(탄소원자 수 1 내지 10개), 아릴로 치환된 알킬 기(탄소원자 수 6 내지 15개)이다.X is an alkene group (1-4 carbon atoms), an aryl group (6-12 carbon atoms), a polycycloalkane group (1-10 carbon atoms), an alkyl group substituted with aryl (carbon atoms) 6 to 15).
실시예 1 및 2:Examples 1 and 2:
제조예 1에서 얻어진 변성된 산 무수물을, 환상지환식 에폭시 수지와 디글리시딜에테르비스페놀 에폭시를 가열온도 80℃, 질소 분위기 하에서 1시간동안 혼합교반시킨 수지 조성물과 충진제인 실란 처리된 규회석, 및 유리 단섬유를 포함하는 주제 수지 조성물에 표 1과 같은 비율로 배합하여 2 내지 3토르의 진공하에서 이그니션 하우징내에 함침시켰다. 경화를 위해 80℃에서 3시간 동안 1차 경화 후, 120℃에서 4시간 동안 후경화시켰다. 그 결과물의 성질을 표 2 내지 4에 나타내었다.Silane-treated wollastonite as a filler and a resin composition obtained by mixing the modified acid anhydride obtained in Preparation Example 1 with a cyclic alicyclic epoxy resin and a diglycidyl ether bisphenol epoxy at a heating temperature of 80 ° C. under a nitrogen atmosphere for 1 hour, and The main resin composition including the short glass fibers was blended in the same ratio as in Table 1 and impregnated in the ignition housing under a vacuum of 2 to 3 torr. The primary cure for 3 hours at 80 ℃ for curing, and after curing for 4 hours at 120 ℃. The properties of the result are shown in Tables 2 to 4.
비교예 1 내지 4:Comparative Examples 1 to 4:
조성을 표 1에 나타낸 것과 같이 한 것을 제외하고는 실시에 1과 동일 방법으로 실험을 실시하였고, 그 결과를 표 2 내지 4에 기술하였다.The experiment was conducted in the same manner as in Example 1, except that the composition was as shown in Table 1, and the results are described in Tables 2 to 4.
제 1 도는 에폭시수지 조성물에 의하여 코팅된 이그니션 코일(ignition coil)내 두번째 보빈에서 발생한 균열을 나타내는 상태도이다.FIG. 1 is a state diagram showing cracks occurring in a second bobbin in an ignition coil coated with an epoxy resin composition.
제 2 도는 경화후 이그니션 코일내의 수지에 대한 함침성 평가 부분을 나타낸 것이다.Figure 2 shows the impregnation evaluation part for the resin in the ignition coil after curing.
도면의 주요 부분에 대한 부호의 설명Explanation of symbols for the main parts of the drawings
1: 이그니션 코일 하우징 2: 코일 와이어에 함침된 수지 조성물1: Ignition coil housing 2: Resin composition impregnated in coil wire
3: 균열 부분 4: 함침성을 평가하기 위해 커팅된 부분3: crack part 4: part cut to evaluate impregnation
A, C: 함침률 검사 부위A, C: impregnation rate test site
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0455463A (en) * | 1990-06-26 | 1992-02-24 | Meidensha Corp | Production of epoxy resin composition |
| KR930012974A (en) * | 1991-12-31 | 1993-07-21 | 공정곤 | Epoxy resin composition |
| JPH0680803A (en) * | 1992-09-03 | 1994-03-22 | Matsushita Electric Works Ltd | Resin-impregnated base material and electrical laminate |
| KR970004664A (en) * | 1995-06-21 | 1997-01-29 | Digital display of the remaining battery capacity of the camcorder | |
| KR970008210A (en) * | 1995-07-18 | 1997-02-24 | 김광호 | Fast Redundancy Decoder Circuit in Semiconductor Memory |
| KR0124545B1 (en) * | 1993-12-01 | 1997-12-01 | 박홍기 | Moulding epoxy resin composition |
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1996
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0455463A (en) * | 1990-06-26 | 1992-02-24 | Meidensha Corp | Production of epoxy resin composition |
| KR930012974A (en) * | 1991-12-31 | 1993-07-21 | 공정곤 | Epoxy resin composition |
| JPH0680803A (en) * | 1992-09-03 | 1994-03-22 | Matsushita Electric Works Ltd | Resin-impregnated base material and electrical laminate |
| KR0124545B1 (en) * | 1993-12-01 | 1997-12-01 | 박홍기 | Moulding epoxy resin composition |
| KR970004664A (en) * | 1995-06-21 | 1997-01-29 | Digital display of the remaining battery capacity of the camcorder | |
| KR970008210A (en) * | 1995-07-18 | 1997-02-24 | 김광호 | Fast Redundancy Decoder Circuit in Semiconductor Memory |
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