KR20040040208A - Preparation method of boron nitride thick film with binder - Google Patents

Preparation method of boron nitride thick film with binder Download PDF

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KR20040040208A
KR20040040208A KR1020020068555A KR20020068555A KR20040040208A KR 20040040208 A KR20040040208 A KR 20040040208A KR 1020020068555 A KR1020020068555 A KR 1020020068555A KR 20020068555 A KR20020068555 A KR 20020068555A KR 20040040208 A KR20040040208 A KR 20040040208A
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binder
inorganic binder
powder
slurry
boron nitride
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KR100482279B1 (en
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임경란
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한국과학기술연구원
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/342—Boron nitride
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron

Abstract

PURPOSE: A method for manufacturing thick boron nitride (BN) film having chemical resistance and superior thermal conductivity and insulating property by heat treating the BN/inorganic binder slurry coated on the sample after coating a sample with a BN/inorganic binder slurry prepared by mixing BN powder with silica based inorganic binder. CONSTITUTION: The method for manufacturing thick boron nitride film using binder comprises a step(1) of preparing slurry by adding boron nitride (BN) powder to alcohol; a step(2) of preparing a BN/inorganic binder slurry by agitating the mixture after adding a silica based inorganic binder in which alkali metal is not contained to the BN/alcohol slurry of the step(1); a step(3) of coating the BN/inorganic binder slurry of the step(2) on a sample; a step(4) of drying the sample coated with the BN/inorganic binder slurry at a room temperature; and a step(5) of forming a thick BN film by heat treating the dried sample, thereby removing organic matter, wherein the method further comprises a step of pretreating the BN powder with a coupling agent before adding alcohol to the BN powder in the step(1).

Description

바인더를 이용한 질화붕소 후막의 제조방법{PREPARATION METHOD OF BORON NITRIDE THICK FILM WITH BINDER}Method for manufacturing boron nitride thick film using a binder {PREPARATION METHOD OF BORON NITRIDE THICK FILM WITH BINDER}

본 발명은 바인더를 이용한 질화붕소(Boron Nitride, 이하 BN이라 한다) 후막의 제조방법에 관한 것으로, 보다 구체적으로는 BN 분말과 알칼리 금속이 포함되지 않은 실리카계 무기 바인더를 혼합한 BN/무기 바인더 슬러리를 시편에 코팅한 다음 열처리하여 내화학성이고 열전도성 및 절연성이 우수한 질화붕소 후막을 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a boron nitride (BN) thick film using a binder, and more specifically, to a BN / inorganic binder slurry in which a BN powder and a silica-based inorganic binder containing no alkali metal are mixed. To a specimen and then heat treated to produce a boron nitride thick film having excellent chemical resistance, thermal conductivity and insulation.

BN은 절연성이며 열전도도가 우수함은 물론, 내화학성이 우수하여 용융금속 특히 아연에 의한 침식이 심한 금속의 보호막으로 사용되며, 고온 이형제로도 사용된다. 또한 BN의 뛰어난 전기 절연성으로 인해 전기, 전자 부품에 사용되고 있다.BN is used as a protective film for molten metal, especially metal with severe corrosion by zinc because it has insulation and excellent thermal conductivity as well as excellent chemical resistance. In addition, BN's excellent electrical insulation makes it used in electrical and electronic components.

종래, 물질의 표면에 BN을 코팅하는 방법으로는 기상 증착법(Chemical Vapor Deposition, CVD)과 BN/무기 바인더 슬러리를 이용하는 방법이 있다. 이 때, 사용되는 무기 바인더는 수성의 알카리금속을 포함한 실리케이트 종류가 일반적이다.Conventionally, as a method of coating BN on the surface of a material, there is a method using chemical vapor deposition (CVD) and a BN / inorganic binder slurry. At this time, the inorganic binder used is generally a type of silicate containing an aqueous alkali metal.

그러나 기존의 BN/무기 바인더 슬러리법에서 무기 바인더로서 주로 사용되던 나트륨 또는 칼륨 실리케이트는 강알카리이고 접착력이 우수하여 내화학성을 필요로 하는데는 사용될 수 있으나, K+, Na+등의 알카리 이온으로 인하여 절연성을 필요로 하는 데는 사용할 수 없다. 따라서 절연성이 높은 BN의 특성을 요구하는 제품에는 알카리금속이 포함된 무기 바인더를 사용할 수 없는 바, BN/무기 바인더 슬러리를 이용하여 물질 표면에 BN을 코팅하는 방법은 그 적용에 한계가 있다.However, sodium or potassium silicate, which is mainly used as an inorganic binder in the conventional BN / inorganic binder slurry method, is a strong alkali and can be used to require chemical resistance due to its excellent adhesion, but due to alkali ions such as K + and Na + It cannot be used to require insulation. Therefore, inorganic binders containing alkali metals cannot be used in products requiring high insulating properties of BN. Therefore, the method of coating BN on the surface of a material using a BN / inorganic binder slurry has a limitation in its application.

또한 CVD 공정에 의한 BN 박막 제조의 경우, BCl3와 NH3또는 N2를 사용하여 고온(1000 ℃ ~ 1400 ℃), 저압(~ 0.01 기압) 하에서 BN 합성이 이루어지고 이어 증착이 일어나므로 박막 형성 시간이 길며, 수율이 낮을 뿐 아니라, 시편이 커지고, 모양이 단순하지 않으며, 고른 박막을 형성하기 어려운 단점이 있다. 특히 막의 두께가 커지게 되면 반응 시간이 매우 길어져 수십 시간에 이르게 되고, 어느 정도의 두께에 다다르면 입자의 크기도 커지며 잘 붙지도 않는 경향마저 있어 식혔다 다시 입히는 과정을 거쳐야 하므로 후막은 겹겹이 층을 이루게 되는 문제점이 있다.In addition, in the case of BN thin film production by CVD process, BN synthesis is performed under high temperature (1000 ° C. to 1400 ° C.) and low pressure (˜0.01 atm) using BCl 3 and NH 3 or N 2 , followed by deposition to form a thin film. In addition to the long time, the yield is low, the specimen is large, the shape is not simple, it is difficult to form an even thin film. In particular, when the thickness of the membrane increases, the reaction time becomes very long, leading to several tens of hours, and when the thickness reaches a certain thickness, the particles grow in size and do not stick well, so they have to be cooled and re-coated so that the thick layer forms a layer. There is a problem.

이에, 본 발명자는 알카리금속이 포함되지 않은 무기 바인더를 이용하여 BN 후막을 제조한다면 절연성을 요구하는 제품에도 BN 후막의 적용이 가능하다는 점과 나아가 본 발명에 따른 BN/무기 바인더 슬러리 코팅을 CVD 공정에 의한 BN 후막 제조에 도입함으로써 상기 문제점을 상당 부분 개선할 수 있을 것이라는 점에 착안하여 거듭 노력한 결과, 본 발명을 완성하게 된 것이다.Thus, the inventors of the present invention, if the BN thick film is manufactured using an inorganic binder that does not contain alkali metal, it is possible to apply the BN thick film to a product requiring insulation, and furthermore, the BN / inorganic binder slurry coating according to the present invention is CVD process. As a result of repetitive efforts, the present invention has been completed by focusing on the fact that the above problems can be substantially improved by introducing them into BN thick film production.

본 발명은 상기와 같은 문제점을 감안하여 안출한 것으로, 본 발명의 목적은알카리금속이 포함되지 않은 실리카계 무기 바인더를 이용하여 탄소, 세라믹, 금속류 등에 내화학성은 물론 전기 절연성 및 열전도성이 우수한 BN 후막을 제조하는 방법을 제공하는 것이다.The present invention has been made in view of the above problems, and an object of the present invention is to use a silica-based inorganic binder that does not contain alkali metal, carbon, ceramics, metals, etc., as well as chemical resistance, electrical insulation and thermal conductivity of BN It is to provide a method for producing a thick film.

또한 본 발명의 또 다른 목적은 CVD 공정으로 제조되던 BN 후막의 대부분의 두께를 본 발명에 따른 BN/무기 바인더 슬러리를 이용하여 코팅한 다음 바깥층(수 ㎛)만 CVD 공정으로 코팅함으로써 후막 형성 시간이 단축되고 공정 단가를 낮춘 BN 후막을 제조하는 방법을 제공하는 것이다.In addition, another object of the present invention is to coat most of the thickness of the BN thick film produced by the CVD process using the BN / inorganic binder slurry according to the present invention, and then only the outer layer (a few μm) by coating the CVD process to increase the thick film formation time The present invention provides a method for producing a BN thick film that has been shortened and has a lower process cost.

상기한 목적을 달성하기 위하여, 본 발명에 따른 바인더를 이용한 질화붕소 후막의 제조방법은,In order to achieve the above object, the method for producing a boron nitride thick film using a binder according to the present invention,

(가) BN 분말을 알코올에 첨가하여 슬러리 상태로 만드는 단계;(A) adding the BN powder to the alcohol to make a slurry;

(나) 알카리금속이 포함되지 않은 실리카계 무기 바인더를 상기 (가) 단계의 BN 알코올 슬러리에 첨가한 다음, 교반시켜 BN/무기 바인더 슬러리를 제조하는 단계;(B) adding a silica-based inorganic binder containing no alkali metal to the BN alcohol slurry of step (a), followed by stirring to prepare a BN / inorganic binder slurry;

(다) 시편에 상기 (나) 단계의 BN/무기 바인더 슬러리를 코팅시키는 단계;(C) coating the specimen with the BN / inorganic binder slurry of step (b);

(라) 코팅된 시편을 실온 건조하는 단계; 및(D) drying the coated specimens at room temperature; And

(마) 건조된 시편을 열처리하여 유기물을 제거하여 BN 후막을 형성하는 단계를 포함하여 이루어지는 것을 특징으로 한다.(E) heat treating the dried specimen to remove organic material to form a BN thick film.

이하, 본 발명의 제조방법을 보다 구체적으로 설명한다.Hereinafter, the manufacturing method of the present invention will be described in more detail.

본 발명에 따른 무기 바인더는 우수한 접착력을 가지며, 절연성이 있어야 한다. 따라서 유전율 4 정도 되는 실리카가 유전율 5 정도 되는 BN의 바인더로 적합하다. 또한 알카리이온을 포함하는 무기 바인더를 이용하여 제조된 BN 후막은 절연성을 필요로 하는 대상물에 적용될 수 없으므로, 알카리금속이 포함되지 않은 무기 바인더가 적합하다.The inorganic binder according to the present invention has excellent adhesion and should be insulative. Therefore, silica having a dielectric constant of about 4 is suitable as a BN binder having a dielectric constant of about 5. In addition, since the BN thick film prepared by using an inorganic binder containing alkali ions cannot be applied to an object requiring insulation, an inorganic binder containing no alkali metal is suitable.

본 발명에서 사용되는 실리카계 무기 바인더는, 에틸실리케이트 또는 Si(OC2H5)4를 산 가수분해하여 생성되는 실리카졸과 RxSi(OR')4-x(x= 1 ~ 3, R = H, CH3, C2H5, C3H7, R' = CH3, C2H5)을 중합반응시켜 제조된다. 보다 구체적으로, 알코올에 희석된 에틸실리케이트 또는 Si(OC2H5)4를 염산 또는 개미산을 촉매로 가수분해하여 실리카 졸을 만들고 여기에 RXSi(OR')4-X(x = 1 ~ 3, R = H, CH3, C2H5, C3H7, R1= CH3, C2H5)을 첨가하고 가열하여 실리카 졸과 중합반응시킴으로써 젖음성과 접착력이 우수한 실리카계 무기 바인더를 합성할 수 있다. 즉, 본 발명에 따른 실리카계 무기 바인더는 실리콘 알콕사이드와 알킬알콕시 실리콘 화합물을 가수분해 및 중합시켜 만든 폴리실록산계 실리카 졸이라 할 수 있다.In the silica-based inorganic binder used in the present invention, silica sol formed by acid hydrolysis of ethyl silicate or Si (OC 2 H 5 ) 4 and R x Si (OR ') 4-x ( x = 1 to 3, R = H, CH 3 , C 2 H 5 , C 3 H 7 , R '= CH 3 , C 2 H 5 ) It is prepared by polymerization. More specifically, ethyl silicate or Si (OC 2 H 5 ) 4 diluted in alcohol is hydrolyzed with hydrochloric or formic acid to form a silica sol, and R X Si (OR ') 4-X (x = 1 ~ 3, R = H, CH 3 , C 2 H 5 , C 3 H 7 , R 1 = CH 3 , C 2 H 5 ) silica-based inorganic binder with excellent wettability and adhesive strength by heating and polymerizing with silica sol Can be synthesized. That is, the silica-based inorganic binder according to the present invention may be referred to as a polysiloxane silica sol made by hydrolyzing and polymerizing a silicon alkoxide and an alkylalkoxy silicon compound.

본 발명에 따른 BN/무기 바인더 슬러리는, 먼저 BN 분말을 알코올에 첨가하여 슬러리 상태를 만든 다음, 알카리금속이 포함되지 않은 실리카계 무기 바인더를 BN 알코올 슬러리에 첨가하고 잘 혼합함으로써 제조된다. 이 때 점도는 알코올 양으로 조절할 수 있다. 본 발명에 따른 실리카계 무기 바인더는 BN 분말에 대한 실리카의 양이 2 ~ 10 중량%인 범위 내에서 첨가하여 사용할 수 있다.The BN / inorganic binder slurry according to the present invention is prepared by first adding BN powder to alcohol to make a slurry state, and then adding silica-based inorganic binder containing no alkali metal to the BN alcohol slurry and mixing well. At this time, the viscosity can be adjusted by the amount of alcohol. The silica-based inorganic binder according to the present invention can be used by adding the amount of silica to 2 to 10% by weight of the BN powder.

다음으로, 시편에 BN/무기 바인더 슬러리를 코팅시켜 코팅된 시편을 실온에서 건조시킨다. 코팅 방법으로는 시편을 슬러리에 담갔다 꺼내는 방법과 시편에 슬러리를 붓으로 칠하는 방법이 가능하다.Next, the specimen is coated with a slurry of BN / inorganic binder to dry the coated specimen at room temperature. As a coating method, the specimen may be immersed in the slurry and taken out, and the slurry may be applied to the specimen with a brush.

코팅된 시편을 실온 건조시킨 후에는 진공, 질소 또는 아르곤 분위기에서 400 ~ 1200 ℃, 1 ~ 4 시간에서 열처리하여 유기 물질을 제거하고 실리카와 BN만을 남긴다. 상기 온도 및 시간 범위가 더 이상의 실리카 무게의 손실 없이 실리카막을 형성하기에 적합한 범위이다.After the coated specimen is dried at room temperature, it is heat-treated at 400 to 1200 ° C. for 1 to 4 hours in a vacuum, nitrogen, or argon atmosphere to remove organic materials, leaving only silica and BN. The temperature and time range is a range suitable for forming a silica film without any further loss of silica weight.

열처리 후 BN 코팅의 두께는 0.07 mm 정도이며, 슬러리의 농도에 따라 BN 두께는 0.07 mm 미만으로도 가능하나, 슬러리 농도가 진해지면 코팅층이 두꺼워져 실온 건조 조건을 잘 조절하지 않으면 건조되면서 떨어지게 된다.After the heat treatment, the thickness of the BN coating is about 0.07 mm, and depending on the concentration of the slurry, the thickness of the BN may be less than 0.07 mm. However, as the slurry concentration increases, the coating layer becomes thicker, and if the room temperature drying conditions are not well controlled, the dryness falls.

적절한 두께로 코팅된 BN 막은 시료에 잘 접착되어 있고, 절연성을 나타내나, BN이 유리 테이프에 조금 묻어난다는 문제점이 있다. 이와 같이 BN 분말이 묻어난다는 것은 막이 견고하지 못하고 닳기 쉽다는 것을 의미한다.The BN film coated with the appropriate thickness is well adhered to the sample and exhibits insulation, but there is a problem that the BN is slightly buried in the glass tape. The smearing of the BN powder in this way means that the film is not firm and wearable.

따라서 이와 같이 BN 분말이 묻어나는 경우, BN 분말을 커플링제로 먼저 처리함으로써 BN 분말과 무기 바인더 사이의 접착력을 증진시켜 문제점을 해결할 수 있다.Therefore, when the BN powder is buried in this way, by first treating the BN powder with a coupling agent, it is possible to solve the problem by improving the adhesion between the BN powder and the inorganic binder.

커플링제로는 CH3Si(OEt)3, γ-글라이시독시프로필트리메톡시실란(γ-glycidoxypropyltrimethoxysilane), 비닐트리메톡시실란(vinyltrimethoxysilane), γ-메타크릴옥시프로필트리메톡시실란(γ-methacryloxypropyltrimethoxysilane),비닐트리에톡시실란(vinyltriethoxysilane)으로 이루어진 군 중에서 선택되는 알킬알콕시실리콘 화합물을 사용할 수 있으며, 이 때 커플링제의 양은 BN 분말을 기준으로 0.2 ~ 5 중량%, 바람직하게는 0.2 ~ 1.0 중량%이다. 이 정도 양의 커플링제를 첨가하는 것이 열전도도를 유지하는 동시에(열전도도는 순수 BN인 경우가 가장 우수함), BN 분말이 묻어나는 문제점을 해결하기에도 적당하다. 또한 추후에 CVD로 BN 후막의 바깥층을 코팅할 때도 열 팽창계수 차이에 따른 크랙(crack)을 방지하는 데 도움이 된다.Coupling agents include CH 3 Si (OEt) 3 , γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane (γ- Alkoxyalkoxysilicon compounds selected from the group consisting of methacryloxypropyltrimethoxysilane) and vinyltriethoxysilane may be used, wherein the amount of coupling agent is 0.2 to 5% by weight, preferably 0.2 to 1.0% by weight, based on the BN powder. %to be. It is also suitable to add this amount of coupling agent to maintain the thermal conductivity (the best thermal conductivity is pure BN) and to solve the problem of BN powder. In addition, when later coating the outer layer of the BN thick film by CVD, it helps to prevent cracks due to thermal expansion coefficient difference.

커플링제로 BN 분말을 처리하는 방법은, BN 분말을 알코올에 첨가하기 이전에, 먼저 커플링제를 알코올에 넣고 소량의 물을 첨가하여 가수분해가 일어나게 한 다음, BN 분말을 첨가하고 교반시켜 분말의 표면을 흡착되게 한다. BN 분말을 가라앉힌 후 윗용액을 버리고 실리카 바인더를 2 ~ 10 % 첨가하고 교반하여 BN/무기 바인더 슬러리를 제조한다. 이 슬러리를 입힌 시편은 실온 건조 후나, 열처리 후에도 스카치 테이프에 묻어나지 않는다.The method of treating the BN powder with the coupling agent is, prior to adding the BN powder to the alcohol, first adding the coupling agent to the alcohol to add a small amount of water to cause hydrolysis, and then adding and stirring the BN powder to Allow the surface to adsorb. After the BN powder is settled, the upper solution is discarded, and 2-10% of silica binder is added and stirred to prepare a BN / inorganic binder slurry. The specimen coated with the slurry does not adhere to the Scotch tape even after drying at room temperature or after heat treatment.

또는 BN 코팅된 시편을 열처리하여 BN 후막을 형성하고 나서 실리카계 무기 바인더를 입힘으로써 BN 막이 묻어나는 것을 방지할 수도 있다. 이 때 실리카 막의 두께는 1 ㎛ 이하이다.Alternatively, the BN-coated specimen may be heat-treated to form a BN thick film and then coated with a silica-based inorganic binder to prevent the BN film from being buried. At this time, the thickness of the silica film is 1 m or less.

추가로, 본 발명에 따라 제조된 BN 후막의 바깥층을 CVD 공정으로 수 ㎛ 두께로 코팅하여 사용할 수 있다.In addition, the outer layer of the BN thick film prepared according to the present invention can be used by coating to a thickness of several μm by a CVD process.

이하 실시예를 통하여 본 발명을 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 상세히 설명하기 위한 것으로, 이들 실시예에 의해 본 발명의 범위가 한정되는 것은 아니다.Through the following examples will be described the present invention in detail. These examples are only for illustrating the present invention in detail, and the scope of the present invention is not limited to these examples.

[실시예]EXAMPLE

실시예 1: 무기 바인더 (A) 제조Example 1: Preparation of Inorganic Binder (A)

테트라에틸오르소실리케이트(tetraethylorthosilicate, TEOS) 22.4 ml를 에탄올 35 ml로 희석한 후, 이 혼합용액에 0.01 N HCl 5.0 ml와 에탄올 15 ml를 혼합한 용액을 천천히 첨가하며 실온에서 약 30 분간 교반한 다음, 이어서 환류(reflux)를 2 시간 동안 행한 후 디메틸디에톡시실란(dimethyldiethoxysilane, DMDE) 5 ml를 첨가하고 다시 2 시간 동안 환류시켜 투명한 졸을 제조하였다.After diluting 22.4 ml of tetraethylorthosilicate (TEOS) with 35 ml of ethanol, 5.0 ml of 0.01 N HCl and 15 ml of ethanol were slowly added to the mixed solution and stirred at room temperature for about 30 minutes. Subsequently, reflux was performed for 2 hours, and then 5 ml of dimethyldiethoxysilane (DMDE) was added and refluxed for 2 hours to prepare a transparent sol.

실시예 2: 무기 바인더 (B) 제조Example 2: Preparation of Inorganic Binder (B)

에틸실리케이트(ethylsilicate)(Silbond 40) 28 ml와 에탄올 35 ml를 혼합한 용액에 0.01 N HCl 6.0 ml와 에탄올 15 ml를 혼합한 용액을 천천히 첨가하며 실온에서 약 30 분간 교반한 후, 이어서 환류를 2 시간 동안 행한 후 디메틸디에톡시실란(dimethyldiethoxysilane, DMDE) 10 ml를 첨가하고 다시 2 시간 동안 환류시켜 투명한 졸을 제조하였다.To a solution of 28 ml of ethylsilicate (Silbond 40) and 35 ml of ethanol, a solution of 6.0 ml of 0.01 N HCl and 15 ml of ethanol was slowly added and stirred at room temperature for about 30 minutes, followed by refluxing. After performing for a period of time, 10 ml of dimethyldiethoxysilane (DMDE) was added and refluxed for 2 hours to prepare a transparent sol.

실시예 3Example 3

BN 분말 (17.0 g)을 에탄올 10 ml에 넣어 걸죽한 슬러리를 만든 다음, 여기에 실시예 2에 따른 바인더 (B)를 5.0 g 첨가하고 교반하여 묽은 BN 슬러리를 제조하였다(4.0 중량% SiO2). 이 슬러리에 탄소 막대기를 집어넣었다 꺼내 실온 건조시켜 BN을 입혔다. 이것을 진공(10-2mmHg)에서 950 ℃/1시간 열처리하였다. BN코팅(0.07 mm)이 해리되지는 않았으나 유리 테이프 테스트에서는 BN이 조금 묻어났다.BN powder (17.0 g) was added to 10 ml of ethanol to make a thick slurry, and then 5.0 g of a binder (B) according to Example 2 was added thereto, followed by stirring to prepare a thin BN slurry (4.0 wt% SiO 2 ). . Carbon sticks were put into the slurry, taken out, and dried at room temperature to coat BN. It was heat treated at 950 ° C./1 hour in vacuum (10 −2 mmHg). The BN coating (0.07 mm) did not dissociate, but BN was slightly buried in the glass tape test.

이것을 다시 BN 슬러리에 넣었다 꺼내 BN 2차 코팅을 하였다. 위와 같은 방법으로 열처리하여 해리가 일어나지 않은 BN 코팅층(0.14 mm)을 입혔다. 그러나 역시 유리 테이프에는 묻어났다.This was put back into the BN slurry and then taken out of the BN secondary coating. Heat treatment was performed in the same manner as above to coat the BN coating layer (0.14 mm) without dissociation. But also on the glass tape.

실시예 4Example 4

BN 분말(17.0 g)에 에탄올 5 ml와 실시예 2에 따른 바인더 (B) 10 g을 첨가하여 묽은 BN 슬러리를 제조하였다. 여기에 실시예 3과 같은 방법으로 탄소 막대기에 BN 코팅층 (0.15 mm)을 제조하였다. 그러나 역시 유리 테이프에 BN이 약간 묻어났다.Dilute BN slurry was prepared by adding 5 ml of ethanol and 10 g of binder (B) according to Example 2 to BN powder (17.0 g). A BN coating layer (0.15 mm) was prepared on the carbon rod in the same manner as in Example 3. However, there was also some BN on the glass tape.

실시예 5Example 5

실시예 1에 따른 바인더 (A)를 사용하여 실시예 4와 같은 방법으로 제조한 BN 슬러리에 탄소 막대기를 한번 넣었다 꺼내 실온 건조 후 열처리하여 0.07 mm BN 코팅을 얻었다. 그러나 역시 유리 테이프에 BN이 묻어났다.Using a binder (A) according to Example 1, a carbon stick was once added to a BN slurry prepared in the same manner as in Example 4, and then taken out and dried at room temperature, followed by heat treatment to obtain a 0.07 mm BN coating. However, BN also got on the glass tape.

실시예 6Example 6

에탄올 10 ml에 증류수 1.2 ml를 혼합하고, CH3Si(OEt)30.2 g을 첨가하고 실온에서 약 1 시간 교반 후 BN 3.13 g을 첨가한 후 약 2 시간 교반한 다음 85 ℃ 오븐에서 2 시간 열처리한 다음 실온으로 식힌 후 윗 용액을 따라낸 다음 실시예 2에 따른 바인더 (B) 2.0 g을 첨가하고 교반하여 묽은 슬러리를 제조하였다. 여기에 탄소 막대를 넣었다 꺼내 BN 코팅을 하였다. 실온 건조 후 실시예 3과 같은 방법으로 열처리하였다. 약 0.07 mm의 층이 입혀졌다. 위의 실시예들보다는 BN이 적게 유리 테이프에 묻어났다.1.2 ml of distilled water was mixed with 10 ml of ethanol, 0.2 g of CH 3 Si (OEt) 3 was added and stirred at room temperature for about 1 hour, followed by addition of 3.13 g of BN, followed by stirring for about 2 hours, followed by heat treatment at 85 ° C. in an oven for 2 hours. After cooling to room temperature, the upper solution was decanted, and then 2.0 g of binder (B) according to Example 2 was added and stirred to prepare a thin slurry. The carbon rod was put in and taken out there, and BN coating was carried out. After drying at room temperature it was heat-treated in the same manner as in Example 3. A layer of about 0.07 mm was coated. Less BN was deposited on the glass tape than the above examples.

실시예 7Example 7

CH3Si(OEt)03대신 γ-glycidoxypropyltrimethoxysilane 0.2 g을 사용하는 것을 제외하고는 실시예 6과 동일한 방법을 수행하여 BN 슬러리를 제조하였다. 이 슬러리를 사용하여 실시예 3에 기술한 방법으로 코팅한 BN 층은 스카치 테이프에 묻어나지 않았다. 코팅층의 두께는 약 0.07 mm이었다.A BN slurry was prepared in the same manner as in Example 6, except that 0.2 g of γ-glycidoxypropyltrimethoxysilane was used instead of CH 3 Si (OEt) 0 3 . Using this slurry, the BN layer coated by the method described in Example 3 did not adhere to the Scotch tape. The thickness of the coating layer was about 0.07 mm.

실시예 8Example 8

스카치 테이프에 묻어나는 BN 층을 보호하기 위하여 열처리된 BN 코팅된 탄소 막대를 실시예 2에 따른 바인더 (B)에 담갔다 꺼내 실온 건조 후 900 ℃에서 30 분간 열처리하였다. 이 결과로 BN은 스카치 테이프에 묻어나지 않았다.In order to protect the BN layer on the Scotch tape, the heat-treated BN-coated carbon rod was immersed in the binder (B) according to Example 2, taken out and dried at room temperature for 30 minutes at 900 ° C. As a result, BN did not adhere to Scotch tape.

실시예 9Example 9

실시예 3, 6, 7의 BN 슬러리에 유리 막대를 담궜다 꺼내서 실온에서 건조한 다음 공기 중에서 400 ℃/30분 열처리하여 BN 코팅층을 입혔다. 유리 테이프 테스트에서 3, 6의 슬러리를 입힌 것은 묻어나나, 7의 슬러리를 이용한 것은 묻어나지 않았다.BN slurries were immersed in the BN slurries of Examples 3, 6, and 7, dried at room temperature, and then heat treated at 400 ° C./30 minutes in air to coat a BN coating layer. In the glass tape test, the slurry of 3 and 6 was smeared, but the thing using the slurry of 7 was not.

본 발명에 의하면 알카리금속이 포함되지 않은 실리카계 무기 바인더를 이용하여 탄소, 세라믹, 금속류 등에 내화학성은 물론 전기 절연성이고 열전도성이 우수한 BN 후막을 제조하는 것이 가능하며, 또한 CVD 공정으로 제조되던 BN 후막의 대부분의 두께를 본 발명에 따른 BN/무기 바인더 슬러리를 이용하여 코팅한 다음 바깥층(수 ㎛)만 CVD 공정으로 코팅하여 BN 후막을 제조하는 방법을 제공함으로써 BN 후막을 필요로 하는 대상물에 손쉽게 후막을 형성시킬 수 있을 뿐만 아니라 후막 형성 시간 단축, 에너지 절감, 및 국부적인 BN 후막 형성이 가능하다.According to the present invention, it is possible to produce a BN thick film having excellent chemical resistance as well as electrical insulation and thermal conductivity by using a silica-based inorganic binder that does not contain alkali metals, and is also manufactured by the CVD process. Most of the thick film is coated using the BN / inorganic binder slurry according to the present invention, and then only the outer layer (a few μm) is coated by a CVD process to provide a method for producing a BN thick film, thereby making it easy to an object requiring a BN thick film. Not only can a thick film be formed, but also short film formation time, energy saving, and local BN thick film formation are possible.

Claims (9)

(가) BN 분말을 알코올에 첨가하여 슬러리 상태로 만드는 단계;(A) adding the BN powder to the alcohol to make a slurry; (나) 알카리금속이 포함되지 않은 실리카계 무기 바인더를 상기 (가) 단계의 BN 알코올 슬러리에 첨가한 다음, 교반시켜 BN/무기 바인더 슬러리를 제조하는 단계;(B) adding a silica-based inorganic binder containing no alkali metal to the BN alcohol slurry of step (a), followed by stirring to prepare a BN / inorganic binder slurry; (다) 시편에 상기 (나) 단계의 BN/무기 바인더 슬러리를 코팅시키는 단계;(C) coating the specimen with the BN / inorganic binder slurry of step (b); (라) 코팅된 시편을 실온 건조하는 단계; 및(D) drying the coated specimens at room temperature; And (마) 건조된 시편을 열처리하여 유기물을 제거하여 BN 후막을 형성하는 단계를 포함하여 이루어지는, 바인더를 이용한 질화붕소 후막의 제조방법.(E) a method of producing a boron nitride thick film using a binder comprising the step of forming a BN thick film by removing the organic material by heat-treating the dried specimen. 제 1항에 있어서, (가) 단계에서 BN 분말을 알코올에 첨가하기 이전에 커플링제로 전처리하는 단계를 추가로 포함하는 것을 특징으로 하는, 바인더를 이용한 질화붕소 후막의 제조방법.The method of manufacturing a boron nitride thick film using a binder according to claim 1, further comprising a step of pretreatment with a coupling agent before adding the BN powder to the alcohol in step (a). 제 2항에 있어서, BN 분말을 커플링제로 전처리하는 단계는 (i) 커플링제를 알코올에 넣고 소량의 물을 첨가하여 가수분해가 일어나게 하고, (ii) BN 분말을 첨가하고 교반시켜 분말의 표면을 흡착되게 하고, (iii)BN 분말을 가라앉힌 후 윗용액을 버리는 것읕 특징으로 하는, 바인더를 이용한 질화붕소 후막의 제조방법.The method of claim 2, wherein the pretreatment of the BN powder with the coupling agent comprises (i) adding the coupling agent to alcohol to add a small amount of water to cause hydrolysis, and (ii) adding and stirring the BN powder to the surface of the powder. And (iii) discarding the upper solution after the BN powder has settled. A method for producing a thick boron nitride film using a binder. 제 1항 또는 제 2항에 있어서, (나) 단계의 실리카계 무기 바인더는 에틸실리케이트 또는 Si(OC2H5)를 산 가수분해하여 생성되는 실리카졸과 RxSi(OR')4-x(x= 1 ~ 3, R = H, CH3, C2H5, C3H7, R' = CH3, C2H5)을 중합반응시켜 제조된 것을 특징으로 하는, 바인더를 이용한 질화붕소 후막의 제조방법.The silica-based inorganic binder according to claim 1 or 2, wherein the silica-based inorganic binder is a silica sol formed by acid hydrolysis of ethyl silicate or Si (OC 2 H 5 ) and R x Si (OR ') 4-x. Nitride using a binder, characterized in that prepared by polymerization of ( x = 1 to 3, R = H, CH 3 , C 2 H 5 , C 3 H 7 , R '= CH 3 , C 2 H 5 ) Method for producing a boron thick film. 제 1항 또는 제 2항에 있어서, 상기 실리카계 무기 바인더는 BN 분말에 대한 실리카의 양이 2 ~ 10 중량%의 범위 내에서 첨가되는 것을 특징으로 하는, 바인더를 이용한 질화붕소 후막의 제조방법.The method of claim 1 or 2, wherein the silica-based inorganic binder is added to the amount of silica in the range of 2 to 10% by weight of the BN powder, the method of producing a boron nitride thick film using a binder. 제 1항 또는 제 2항에 있어서, 열처리는 진공, 질소 또는 아르곤 분위기에서 400 ~ 1200 ℃, 1 ~ 4 시간 동안 행하는 것을 특징으로 하는, 바인더를 이용한 질화붕소 후막의 제조방법.The method for producing a thick boron nitride film using a binder according to claim 1 or 2, wherein the heat treatment is performed at 400 to 1200 ° C for 1 to 4 hours in a vacuum, nitrogen, or argon atmosphere. 제 2항 또는 제 3항에 있어서, 커플링제는 CH3Si(OEt)3, γ-글라이시독시프로필트리메톡시실란, 비닐트리메톡시실란, γ-메타크릴옥시프로필트리메톡시실란, 비닐트리에톡시실란으로 이루어진 군 중에서 선택되는 알킬알콕시실리콘 화합물인 것을 특징으로 하는, 바인더를 이용한 질화붕소 후막의 제조방법.The coupling agent according to claim 2 or 3, wherein the coupling agent is CH 3 Si (OEt) 3 , γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyl A method for producing a boron nitride thick film using a binder, which is an alkylalkoxysilicon compound selected from the group consisting of triethoxysilane. 제 1항 또는 제 7항에 있어서, 상기 커플링제의 양은 BN 중량을 기준으로0.2 ~ 5 중량%, 바람직하게는 0.2 ~ 1 중량%인 것을 특징으로 하는, 바인더를 이용한 질화붕소 후막의 제조방법.8. The method of claim 1, wherein the amount of the coupling agent is 0.2 to 5 wt%, preferably 0.2 to 1 wt%, based on the BN weight. 9. 제 1항 또는 제 2항에 있어서, (마) 단계에 이어 추가로 수 ㎛의 BN 층을 CVD 공정으로 코팅하는 것을 특징으로 하는, 바인더를 이용한 질화붕소 후막의 제조방법.The method for producing a thick boron nitride film using a binder according to claim 1 or 2, further comprising: coating a BN layer of several μm in a CVD process subsequent to the step (e).
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