KR20030097460A - A method of preparing poly methylsilsesquioxane-dimethylsiloxane copolymer - Google Patents
A method of preparing poly methylsilsesquioxane-dimethylsiloxane copolymer Download PDFInfo
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Abstract
Description
본 발명은 다이메틸실록산기가 균일하게 분산된 형태의 폴리메틸실세스퀴옥산 공중합체의 제조방법에 관한 것으로서, 더욱 상세하게는 메틸트리알콕시실란(T구조형)과 다이메틸다이클로로실란(D 구조형)을 몰비로 2 : 1 혼합한 용액을 열처리하여 두 물질이 서로 T-D-T 형으로 결합된 형태의 전구체를 얻은 후, THF와 톨루엔의 혼합용매를 사용하여 졸-겔 반응시키고 암모니아수로 중화함으로써, 다이메틸실록산 분자가 메틸실록산 골격에 분자 수준으로 제어된 방법으로 균일하게 분산된 폴리메틸실세스퀴옥산 공중합체의 제조방법에 관한 것이다.The present invention relates to a method for producing a polymethylsilsesquioxane copolymer in which dimethylsiloxane groups are uniformly dispersed. More specifically, methyltrialkoxysilane (T structure type) and dimethyldichlorosilane (D structure type) Heat treatment of the mixed solution at a molar ratio of 2 to 1 to obtain a precursor in which the two materials are bonded to each other in a TDT form, and then sol-gel reaction using a mixed solvent of THF and toluene and neutralize with dimethyl ammonia. A method for producing a polymethylsilsesquioxane copolymer in which molecules are uniformly dispersed in a molecular level controlled manner in a methylsiloxane skeleton.
본 발명의 방법으로 제조된 공중합체는 내열성이 매우 우수하므로 덴드리머 형 폴리알킬렌 옥시드 화합물과 같은 열분해성 물질과 혼합한 용액을 코팅하여 제조된 박막을 폴리알킬렌 옥시드가 분해되는 온도까지 가열하여 폴리알킬렌 옥시드를 제거하면 미세한 기공을 갖는 박막을 제조할 수 있다. 또한, 본 발명에서 제조된 공중합체는 일정한 양의 직선 골격을 가진 다이메틸실록산기의 도입으로 유연성 증가에 의하여 SOG(Spin On Glass) 및 CMP(Chemical Mechanical Polishing) 공정에서 크랙 발생이 매우 낮으므로 미세 기공을 갖는 형태의 저 유전율 반도체 층간 절연막 제조의 모재로 사용될 수 있다.Since the copolymer prepared by the method of the present invention has excellent heat resistance, a thin film prepared by coating a solution mixed with a thermally decomposable substance such as a dendrimer-type polyalkylene oxide compound is heated to a temperature at which the polyalkylene oxide is decomposed. Removing the polyalkylene oxide can produce a thin film having fine pores. In addition, the copolymer prepared in the present invention is fine because the crack generation is very low in the SOG (Spin On Glass) and CMP (Chemical Mechanical Polishing) process by increasing the flexibility by the introduction of a dimethylsiloxane group having a certain amount of linear skeleton It can be used as a base material for the production of low dielectric constant semiconductor interlayer insulating film having pores.
반도체 소자의 집적률이 높아지고 그 작동 주파수가 높아짐에 따라 반도체 칩내의 전기적인 신호 전달을 위한 금속 배선사이에서의 크로스 토크(cross-talk)에 의한 잡음이 높아지고 또한 인접 배선사이의 상호 작용에 의한 기생 커패시턴스(prasitic capacitance)의 증가로 인한 신호전달 지연현상이 나타나게 된다.As the integration rate of semiconductor devices increases and the operating frequency thereof increases, noise due to cross-talk between metal wires for electrical signal transmission in the semiconductor chip increases, and parasitics due to interaction between adjacent wires. Signal propagation delay due to an increase in the capacitance (prasitic capacitance) appears.
특히, 회로의 선폭이 0.18 ㎛ 이하인 반도체 설계에서는 고속화 및 저소비전력화를 위해, 현재 사용되고 있는 알루미늄 배선과, 산화 규소(SiO2) 절연막에서 구리 배선과, 그리고 유전율 3 이하의 저 유전율(low-k) 층간 절연막 재료의 도입이 불가피하다.In particular, in semiconductor designs with line widths of 0.18 μm or less, aluminum wirings, copper wirings in silicon oxide (SiO 2 ) insulating films, and low dielectric constants (low-k) of dielectric constant 3 or less are currently used for high speed and low power consumption. Introduction of the interlayer insulating film material is inevitable.
이러한 저 유전율 층간 절연막 재료로서 고려되고 있는 물질 중의 하나가 나노 기공의 도입이 용이한 폴리메틸실세스퀴옥산이다. 그러나, 상기 폴리메틸실세스퀴옥산의 특성상 취성이 있으므로 반도체 제조공정 중에 미세 크랙이 발생할 우려가 있다.One of the materials considered as such a low dielectric constant interlayer insulating film is polymethylsilsesquioxane, in which nanopores are easily introduced. However, due to the brittleness of the polymethylsilsesquioxane, there is a fear that fine cracks occur during the semiconductor manufacturing process.
또한, 일반적으로 산화 규소 역시 취성이 매우 약한 물질로 알려져 있다. 실리콘 화학의 참고 자료에 따르면 (SiO4)n로 결합된 구조에서 산소 대신에 유기물인 메틸기를 도입하면 유연성이 증가하는 것으로 보고되어 있다. 그러나, 실리콘에 대하여 메틸기가 하나 결합된 메틸실세스퀴옥산은 산화 규소에 비하여 약간의 유연성 증가는 있으나, CMP 및 열처리 공정을 포함하는 반도체 제조 공정 중에 받을 수도 있는 외력에 의하여 미세 크랙이 발생할 위험이 여전히 남아 있다. 이것을 방지하기 위해서는 실리콘기에 대하여 메틸기를 좀 더 포함시킬 필요가 있다.In general, silicon oxide is also known to be very brittle material. According to the reference of silicon chemistry, the introduction of organic methyl group instead of oxygen in (SiO 4 ) n bonded structure has been reported to increase the flexibility. However, although methylsilsesquioxane having one methyl group bonded to silicon has a slight increase in flexibility compared to silicon oxide, there is a risk of microcracks due to external forces that may be received during semiconductor manufacturing processes including CMP and heat treatment processes. Still remains. In order to prevent this, it is necessary to include a methyl group further with respect to a silicone group.
이러한 방법 중의 하나가 메틸실세스퀴옥산에 다이메틸실록산기를 도입하여 공중합하는 방법이 있으며, 이에 대하여 다음과 같은 여러 방법이 연구되어 왔다.One such method is a method of introducing a copolymer of dimethylsiloxane into methylsilsesquioxane and copolymerizing it, and various methods have been studied.
먼저, 일본특허 평2-279779호에 의하면 메틸세스퀴옥산에 다이메틸다이실록산을 부가함으로써 유연성을 부가하고자 시도한 바 있으며, 상기 방법에서는 메틸실록산 올리고머와 다이메틸올리고머를 유기 용제에 단순 혼합하여 코팅 용액을 조제하고 있다. 그러나, 상기 방법은 메틸실록산에 다이메틸실록산이 분자 레벨로 결합되어 있지 않아서 내열성에 문제가 있으며, 400 ℃ 이상의 열처리 공정을 거치는 저 유전(low-k)용 모재로 사용하기에는 문제가 있다.First, Japanese Patent No. Hei 2-279779 has attempted to add flexibility by adding dimethyl disiloxane to methyl sesquioxane, in which the methyl siloxane oligomer and dimethyl oligomer are simply mixed with an organic solvent in a coating solution. Is preparing. However, the method has a problem in heat resistance because the dimethyl siloxane is not bonded to the methyl siloxane at the molecular level, and there is a problem to use as a low-k substrate having a heat treatment process of 400 ° C. or higher.
또 다른 방법으로서, 두 개의 출발원료를 일정 비율로 혼합하여 가수분해시킨 후, 축중합시켜 두개의 서로 다른 알콕시실란 간의 공중합을 이루게 하는 졸-겔법을 이용하고 있다. 그러나, 상기 방법은 출발원료 물질간의 물에 대한 가수 분해 차이로 매우 균일하게 서로가 결합된 형태의 공중합체를 합성하기에는 한계가 있다. 예를 들어, 메틸트리메톡시실란과 다이메틸다이메톡시실란을 일정 비율로 혼합하여 졸-겔법으로 얻은 공중합체의 경우는 두 출발원료의 물에 대한 가수분해 속도 차이가 있어 다이메틸실록산기가 메틸실록산기에 균일하게 분산되어 결합하지 않으므로 300 ℃ 이상의 고온에서 다이메틸실록산기가 열에너지에 의해 재배열하여 테트라머(tetramer) 혹은 옥타머(octamer) 형태의 고리 화합물이 일부 생성되어 열 분해되는 문제가 있다.As another method, a sol-gel method is used in which two starting materials are mixed and hydrolyzed at a predetermined ratio, followed by condensation polymerization to copolymerize two different alkoxysilanes. However, the method has a limitation in synthesizing a copolymer in a form in which the starting material is bonded to each other very uniformly due to the difference in hydrolysis of water. For example, in the case of a copolymer obtained by mixing sol-gel method with methyltrimethoxysilane and dimethyldimethoxysilane in a predetermined ratio, there is a difference in the hydrolysis rate of the two starting materials with respect to water. Since the siloxane groups are not uniformly dispersed and bound, the dimethylsiloxane groups are rearranged by thermal energy at a high temperature of 300 ° C. or higher, so that some ring compounds having a tetramer or octamer form are generated and thermally decomposed.
또한, 일본특허 평9-324051호에서는 공중합체 합성 후 용매로 사용한 THF를 먼저 제거하고 톨루엔을 가하여 물로 산을 세척하는 방법이 알려져 있다. 그러나, 상기 방법은 공정이 여러 단계이며, 산을 수세하기 위하여 다량의 물을 사용해야할 뿐 아니라, 물층과 톨루엔층을 분리하는데 있어서 많은 시간이 필요하다.In addition, Japanese Patent No. Hei 9-324051 discloses a method of washing an acid with water by first removing THF used as a solvent after copolymer synthesis and then adding toluene. However, the process is a multi-step process, not only requires the use of a large amount of water to wash the acid, but also requires a long time to separate the water layer and the toluene layer.
이에 따라, 본 발명자들은 종래 메틸트리알콕시실란과 다이메틸다이알콕시실란을 출발원료로 두 물질을 단순 혼합하여 졸-겔법으로 다이메틸실록산이 도입된 폴리메틸실세스퀴옥산의 공중합체 합성에서 다이메틸실록산이 메틸실세스퀴옥산에 불균일하게 결합하는 문제를 최소화하기 위하여 연구 노력하였다.Accordingly, the present inventors have simply mixed two materials using methyltrialkoxysilane and dimethyldialkoxysilane as starting materials, and then, in the synthesis of a copolymer of polymethylsilsesquioxane in which dimethylsiloxane is introduced by the sol-gel method, Research efforts have been made to minimize the problem that siloxanes unevenly bind to methylsilsesquioxane.
그 결과, 알콕시실란과 클로로실란이 특정 조건에서 알킬클로라이드 화합물을 부산물로 생성하면서 서로 결합하는 반응에 주목하여, 메틸트리알콕시실란과 다이메틸다이클로로실란을 몰비로 2 : 1로 혼합하고 미리 130 ℃ 전후에서 T-D-T 형의 균일한 구조가 되도록 전구체를 합성하고(도 1참조), 여기에 메틸실록산과 다이메틸실록산이 특정한 비율이 되게 메틸트리알콕시실란을 첨가하여 졸-겔법으로 공중합하여 폴리메틸실세스퀴옥산 모재의 유연성을 부가함과 동시에, 메틸알콕시실란과 다이메틸실록산간의 물에 대한 가수분해 속도 차이에 의하여 야기되는 공중합 폴리메틸실세스퀴옥산의 불균일성을 최소화하는 신규하고도 고유한 방법을 개발함으로써 본 발명을 완성하게 되었다.As a result, paying attention to the reaction in which the alkoxysilane and the chlorosilane are bonded to each other while producing an alkyl chloride compound as a by-product under specific conditions, the methyltrialkoxysilane and the dimethyldichlorosilane are mixed at a molar ratio of 2: 1 and 130 ° C. in advance. Precursors are synthesized so as to have a uniform structure of TDT type before and after (see FIG. 1), and methyltrialkoxysilane is added thereto to make a specific ratio of methylsiloxane and dimethylsiloxane and copolymerized by sol-gel method to polymethylsilses. A novel and unique method for adding the flexibility of the quoxane base material and at the same time minimizing the heterogeneity of the copolymerized polymethylsilsesquioxane caused by the difference in the rate of hydrolysis of water between methylalkoxysilane and dimethylsiloxane. The present invention has been completed by the development.
그리고, 메틸트리알콕시실란과 다이메틸다이클로로실란간에 미 반응되어 소량 남아 있는 클로로기의 가수분해로 생성되는 염산에 의한 촉매 작용으로 졸-겔 반응이 일어나게 하고, 공중합체 합성 후 산 촉매를 제거하는 과정에서 미리 암모니아수로 중화하고 혼합 용매에 물을 직접 가하여 수세하는 매우 단순한 공정과 적은 양의 물로도 산을 제거하는 방법도 발명하게 되었다.In addition, a sol-gel reaction occurs by catalysis by hydrochloric acid which is unreacted between methyltrialkoxysilane and dimethyldichlorosilane by hydrolysis of a small amount of remaining chloro groups, and an acid catalyst is removed after the copolymer synthesis. In the process, a simple process of neutralizing with aqueous ammonia and washing with water by directly adding a mixed solvent and a method of removing acid with a small amount of water were also invented.
따라서, 본 발명은 메틸실록산과 다이메틸실록산 사이의 화학결합이 분자 수준으로 매우 균일하게 결합되어 내열성이 우수하며 유연성이 기대되는 폴리메틸실세스퀴옥산 공중합체의 제조방법을 제공하는데 그 목적이 있다.Accordingly, an object of the present invention is to provide a method for preparing a polymethylsilsesquioxane copolymer, in which chemical bonds between methylsiloxane and dimethylsiloxane are bonded very uniformly at a molecular level, which is excellent in heat resistance and is expected to be flexible. .
도 1은 메틸트리메톡시실란과 다이메틸다이클로로실란을 130 ℃에서 10시간 열처리하여 합성된 생성물의29Si NMR 스펙트럼을 나타낸 것으로서, 메틸실란과 다이메틸실란이 화학적으로 결합된 형태의 생성물을 보이고 있다.FIG. 1 shows a 29 Si NMR spectrum of a product synthesized by heat-treating methyltrimethoxysilane and dimethyldichlorosilane at 130 ° C. for 10 hours, and shows a product in which the methylsilane and dimethylsilane are chemically bonded. have.
도 2는 본 발명에 따른 폴리메틸실세스퀴옥산 공중합체의29Si NMR 스펙트럼을 나타낸 것으로서, 메틸실세스퀴옥산(T 구조)결합과 다이메틸실록산 결합(D 구조)이 잘 보이고 있다.Figure 2 shows the 29 Si NMR spectrum of the polymethylsilsesquioxane copolymer according to the present invention, the methylsilsesquioxane (T structure) bond and dimethylsiloxane bond (D structure) is well seen.
본 발명은 다이메틸실록산기가 일부 도입된 폴리메틸실세스퀴옥산 공중합체를 제조하는 방법에 있어서,The present invention provides a method for producing a polymethylsilsesquioxane copolymer in which a dimethylsiloxane group is partially introduced,
메틸트리알콕시실란(T 구조)과 다이메틸다이클로로실란(D 구조)을 2 : 1의 몰비로 혼합하여 100 ∼ 150 ℃의 온도에서 5 ∼ 20시간 열처리하여 메틸실록산기와 다이메틸실록산기가 서로 T-D-T형으로 결합된 형태의 화합물을 합성하는 공정:Methyltrialkoxysilane (T structure) and dimethyldichlorosilane (D structure) were mixed at a molar ratio of 2: 1, and heat-treated at a temperature of 100 to 150 ° C. for 5 to 20 hours, whereby the methylsiloxane group and the dimethylsiloxane group were each different from each other. Process for synthesizing compound in bound form:
상기에서 합성한 T-D-T형 화합물에, 메틸실록산기/다이메틸실록산기의 비율이 0.95/0.05 ∼ 0.70/0.30 몰비를 이루도록 추가적으로 메틸트리알콕시실란을 첨가하고 테트라하이드로퓨란 및 톨루엔의 혼합 유기용매내에서 0 ∼ 60 ℃의 조건하에 물을 첨가하여 졸-겔 반응시키는 공정; 그리고,To the TDT compound synthesized above, methyltrialkoxysilane is further added so that the ratio of methylsiloxane group / dimethylsiloxane group is 0.95 / 0.05 to 0.70 / 0.30 molar ratio, and 0 in a mixed organic solvent of tetrahydrofuran and toluene. Sol-gel reaction by adding water under the condition of -60 deg. And,
상기 졸-겔 반응된 혼합용액에 희석된 암모니아수를 가하여 pH가 6 ∼ 7되게 중화하는 공정으로 이루어진 폴리메틸실세스퀴옥산 공중합체의 제조방법을 그 특징으로 한다.It characterized by the method of producing a polymethylsilsesquioxane copolymer consisting of a step of neutralizing the pH to 6-7 by adding diluted ammonia water to the sol-gel reaction solution.
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명은 폴리메틸실세스퀴옥산(PMSSQ)의 취성을 개선하여 유연성을 부여할 목적으로 메틸실세스퀴옥산에 다이메틸실록산기를 도입하여 메틸실세스퀴옥산과 다이메틸실록산기가 분자 수준으로 매우 균일하게 결합된 폴리메틸실세스퀴옥산 공중합체의 제조방법에 관한 것이다.The present invention introduces a dimethylsiloxane group to methylsilsesquioxane for the purpose of improving the brittleness of polymethylsilsesquioxane (PMSSQ) to give flexibility, so that the methylsilsesquioxane and dimethylsiloxane groups are very uniform at the molecular level. The present invention relates to a method for preparing a polymethylsilsesquioxane copolymer which is bound together.
특히, 본 발명은 반응 생성물의 균일도가 매우 높아 200 ℃ 이상의 열처리에서도 불균일하게 결합된 다이메틸실록산에 의한 열분해 생성물이 없으며, 졸-겔법으로 공중합체 합성시 산 촉매를 첨가함이 없이 미량 남아 있는 클로로기의 가수분해에 의하여 촉매 반응이 일어나며, 공중합체 합성 완료 후 산 촉매를 희석된 암모니아수로 수세하는 방법으로 촉매 제거용 이온 교환수의 사용양을 줄이고 공중합체의 보존 안정성을 높이는 특징이 있다.In particular, the present invention has a very high uniformity of the reaction product, there is no pyrolysis product by dimethylsiloxane that is heterogeneously bonded even in the heat treatment of 200 ℃ or more, and the amount of chloro remaining in the sol-gel method without adding an acid catalyst in the synthesis of the copolymer Catalytic reaction occurs by hydrolysis of the group, and after completion of copolymer synthesis, the acid catalyst is washed with diluted ammonia water to reduce the amount of ion-exchanged water used for catalyst removal and to increase the preservation stability of the copolymer.
상기와 같은 특성의 본 발명에 따른 폴리메틸실세스퀴옥산 공중합체는 다음 화학식 1로 나타낼 수 있다.Polymethylsilsesquioxane copolymer according to the present invention having the above characteristics can be represented by the following formula (1).
상기 화학식 1에서: x는 0.05 ∼ 0.3이고, n은 0 ∼ 3이다.In Chemical Formula 1, x is 0.05 to 0.3, and n is 0 to 3.
이러한 본 발명에 따른 상기 화학식 1로 표시되는 폴리메틸실세스퀴옥산 공중합체를 그 제조방법에 의거하여 보다 구체적으로 설명하면 다음과 같은 공정으로 이루어져 있다.The polymethylsilsesquioxane copolymer represented by Chemical Formula 1 according to the present invention will be described in more detail based on the preparation method.
첫 번째 공정은 메틸트리알콕시실란(T 구조)과 다이메틸다이클로로실란(D 구조)을 2 : 1의 몰비로 혼합하여 100 ∼ 150 ℃의 온도에서 5 ∼ 20시간 열처리하여 메틸실록산기와 다이메틸실록산기가 T-D-T형으로 서로 결합된 형태의 전구체를 제조하는 공정을 수행한다. 상기 메틸트리알콕시실란으로는 메틸트리에톡시실란, 메틸트리메톡시실란, 메틸트리프로폭시실란 등이 사용될 수 있다.In the first process, methyltrialkoxysilane (T structure) and dimethyldichlorosilane (D structure) are mixed at a molar ratio of 2: 1, and heat-treated at a temperature of 100 to 150 ° C. for 5 to 20 hours to form methylsiloxane and dimethylsiloxane. A process of preparing precursors in which groups are bonded to each other in the form of TDT is performed. As the methyltrialkoxysilane, methyltriethoxysilane, methyltrimethoxysilane, methyltripropoxysilane, etc. may be used.
본 발명에 따른 T-D-T형 화합물 합성에 대하여 보다 상세히 설명하면, 상기출발원료 물질로 사용하는 혼합용액을 압력에 견디는 두꺼운 유리관내에 넣고 100 ∼ 150 ℃, 더 바람직하게는 110 ∼ 130 ℃로 유지된 실리콘 오일조(bath)에서 2 ∼ 20시간, 더 바람직하게는 5 ∼ 15시간 동안 열처리하여 T-D-T형 화합물을 합성하였다. 이때, 상기 열처리 온도가 상기 범위를 벗어나게 되면 두 다른 물질간의 리간드 교환 반응이 충분히 일어나지 않는 문제가 있다. 여기서 메틸트리알콕시실란과 다이메틸다이클로로실란간의 반응을 촉진시키기 위하여 무수 FeCl3, ZrCl4, TiCl4, AlCl3등을 촉매로 사용할 수도 있다. T-D-T형 화합물 합성에 사용된 촉매는 졸-겔 반응에서 수산화물로 침전되어 제거가 가능하다.The TDT compound synthesis according to the present invention will be described in more detail. The mixed solution used as the starting material is placed in a thick glass tube that resists pressure, and the silicone is maintained at 100 to 150 ° C., more preferably 110 to 130 ° C. TDT compound was synthesized by heat treatment in an oil bath for 2-20 hours, more preferably 5-15 hours. At this time, when the heat treatment temperature is out of the range, there is a problem that the ligand exchange reaction between two different materials does not occur sufficiently. Anhydrous FeCl 3 , ZrCl 4 , TiCl 4 , AlCl 3 , or the like may be used as a catalyst in order to promote the reaction between methyltrialkoxysilane and dimethyldichlorosilane. The catalyst used to synthesize the TDT compound can be removed by precipitation as a hydroxide in the sol-gel reaction.
두 번째는 상기에서 제조된 T-D-T형 화합물에 전체적인 메틸실록산기/다이메틸실록산기의 비율이 0.95/0.05 ∼ 0.70/0.30 몰비를 이루도록 메틸트리알콕시실란을 추가로 첨가하고 이온 교환수를 가하여 축중합반응시키는 졸-겔법으로 공중합 폴리메틸실세스퀴옥산을 합성하였다.Second, the polycondensation reaction was further performed by adding methyltrialkoxysilane and adding ion-exchanged water such that the ratio of methylsiloxane group / dimethylsiloxane group was 0.95 / 0.05 to 0.70 / 0.30 molar ratio. Copolymer polymethylsilsesquioxane was synthesize | combined by the following sol-gel method.
상기 메틸실록산기/다이메틸실록산기의 몰비에 있어 다이메틸실록산기의 몰비가 상기 범위보다 낮게 유지되면 취성을 개선하기 위한 유연성에 문제가 있고, 상기 범위를 초과하면 내열성이 낮은 문제가 있다.If the molar ratio of the dimethylsiloxane group is kept lower than the above range in the molar ratio of the methylsiloxane group / dimethylsiloxane group, there is a problem in flexibility to improve brittleness, and if it exceeds the above range, there is a problem of low heat resistance.
상기 졸-겔 반응 공정을 보다 상세히 설명하면, T-D-T형 화합물 즉, 공중합 폴리메틸실세스퀴옥산 1 몰에 대하여 THF를 2 ∼ 15 몰배, 더 바람직하게는 4 ∼ 10 몰배가 되게 하고, 여기에 다시 톨루엔을 상기 공중합 폴리메틸실세스퀴옥산 1 몰에 대하여 2 ∼ 15 몰배, 더 바람직하게는 4 ∼ 10 몰배가 되게 가하여 혼합하여THF와 톨루엔이 혼합된 혼합 용매가 되도록 하였다. 그런 다음, 가수분해 반응을 위한 물을 상기 리간드 교환된 공중합 폴리메틸실세스퀴옥산 1 몰에 대하여 1 ∼ 4 몰배, 더 바람직하게는 1.5 ∼ 3.5 몰배로 가하고, 0 ∼ 60 ℃, 더 바람직하게는 10 ∼ 40 ℃에서 3 ∼ 30시간, 더 바람직하게는 5 ∼ 20시간 동안 졸-겔 반응시킨다.The sol-gel reaction process will be described in more detail, with THF being 2 to 15 mole times, more preferably 4 to 10 mole times per mole of TDT-type compound, ie, copolymerized polymethylsilsesquioxane. Toluene was added in an amount of 2 to 15 mol times, more preferably 4 to 10 mol times with respect to 1 mol of the copolymerized polymethylsilsesquioxane, and mixed to obtain a mixed solvent in which THF and toluene were mixed. Then, water for the hydrolysis reaction is added at 1 to 4 mole times, more preferably 1.5 to 3.5 mole times, with respect to 1 mole of the ligand exchanged copolymerized polymethylsilsesquioxane, and 0 to 60 ° C, more preferably The sol-gel reaction is carried out at 10 to 40 ° C. for 3 to 30 hours, more preferably 5 to 20 hours.
마지막 공정은 희석된 암모니아수를 상기 공정에 가하여 중화하고, 여분의 이온 교환수를 가하여 층분리법으로 수세하여 자체 생성된 소량의 산 촉매를 제거하고, 톨루엔에 공중합 폴리메틸실세스퀴옥산과 미량 용해된 물을 무수 마그네슘 설페이트(Mg(SO4))로 건조하고 톨루엔을 증류하는 방법으로 본 발명을 완성하였다.The final process is neutralized by adding diluted ammonia water to the process, washing with layer separation by adding extra ion-exchanged water to remove a small amount of the self-produced acid catalyst, and dissolving a trace amount of copolymerized polymethylsilsesquioxane in toluene. The present invention was completed by drying water with anhydrous magnesium sulfate (Mg (SO 4 )) and distilling toluene.
즉, 상기 반응이 끝난 용액에 암모니아수를 가하여 pH가 6 ∼ 7 범위로 유지되도록 중화하고, 중화된 반응 용액을 분별 깔대기에 옮기고 이온 교환수를 반응 용액에 대한 부피비로 2배 가하여 격렬하게 흔든 후 정치하여 하층의 물을 제거하여 중화된 염을 수세한다. 그리고, 상층의 유기 용매 층에 녹아있는 미량의 물을 건조한다. 그런 다음, 상기 유기 용매 층을 여과 깔대기에서 여과하여 1구 라운드 플라스크에 옮기고 감압증류 방식으로 유기 용매를 제거하여 레진 혹은 고체상의 반응 생성물을 얻는 공정을 거침으로써, 공중합체의 균일성이 뛰어나고 졸-겔 반응 촉매를 보다 단순하게 제거하여 안정한 폴리메틸실세스퀴옥산 공중합체를 얻을 수 있는 특징이 있다.That is, neutralize the aqueous solution by adding ammonia water to maintain the pH in the range of 6-7, transfer the neutralized reaction solution to a separatory funnel, and shake the solution by adding twice the volume of the ion-exchanged water to the reaction solution. The lower layer of water is removed to wash the neutralized salt. Then, the trace amount of water dissolved in the upper organic solvent layer is dried. Then, the organic solvent layer was filtered in a filtration funnel, transferred to a 1-neck round flask, and the organic solvent was removed by distillation under reduced pressure to obtain a resin or a solid reaction product. The gel reaction catalyst can be more simply removed to obtain a stable polymethylsilsesquioxane copolymer.
이상과 같이, 본 발명에 따른 폴리세스퀴옥산 공중합체는 다이메틸실록산이분자수준으로 메틸실록산에 균일하게 분산되어 있어 내열성이 우수하다. 또한, 상기 화학식 1에서의 메틸기/실란(CH3/Si)의 비율이 증가하여, 즉 디메틸실록산의 함량 증가가 이루어져 이에 따른 유연성의 증가가 기대된다.As described above, the polysesquioxane copolymer according to the present invention is uniformly dispersed in methylsiloxane at the molecular level of dimethylsiloxane, and thus has excellent heat resistance. In addition, the ratio of the methyl group / silane (CH 3 / Si) in the formula (1) is increased, that is, the content of dimethylsiloxane is increased, thereby increasing the flexibility is expected.
이하, 본 발명을 다음의 실시예에 의거하여 더욱 상세하게 설명하겠는 바, 다음의 실시예는 본 발명의 예시일 뿐 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the following examples. The following examples are only examples of the present invention, and the present invention is not limited by the examples.
실시예 1Example 1
메틸트리메톡시실란 19.07 g, 다이메틸다이클로로실란 9.03 g과 촉매로서 FeCl3을 0.034 g 칭량하여 40 ㎖의 두꺼운 유리관(thick wall-glass tube)에 넣고 마개를 단단히 봉한 후 약 130 ℃로 유지된 실리콘 오일조(bath)내에 담구어서 마그네틱 바로 교반하면서 7시간 동안 유지시키는 방법으로 T-D-T형 전구체를 합성하였다. 이 용액을 1ℓ 라운드 플라스크에 옮겨 넣은 다음 메틸실록산기/다이메틸실록산기의 비율이 0.90 : 0.1 몰비 되도록 메틸트리메톡시실란 68.11 g을 추가적으로 첨가하였다. 여기에 THF 145 ㎖와 톨루엔 191 ㎖을 가하고, 이온 교환수 43.85 g을 가하여 상온에서 7시간 동안 교반하면서 축중합 반응에 의한 졸-겔법으로 공중합체를 제조하였다. 공중합 반응된 용액에 20% 암모니아 용액을 1.5 ㎖를 가하여 pH가 6 ∼ 7 되게 중화하였다. 중화된 반응 용액을 1ℓ 분별 깔대기에 옮겨 넣고 이온 교환수 500 ㎖을 가하여 격렬하게 흔든 다음 정치하였다.약 5분 후 유기층과 물층으로 분리된 두 층에서 하층의 물층을 제거하고, 이 과정을 한번 더 수행한 후 물층을 제거한 상층에 무수 MgSO4분말 약 20 g을 넣고 격렬하게 흔들어 미량 녹아 있을 수 있는 물을 제거하였다. MgSO4분말과 촉매로 사용된 FeCl3이 물과 반응하고 유기층에 분산된 고체상은 와트만 여과지 5번으로 여과하여 제거하였으며, 여과된 유기층은 1ℓ 1구 라운드 플라스크에 옮긴 후 약 10 torr의 압력에서 감압 증류 방식으로 유기 용매를 제거하고 반응 생성물을 회수하였다. 이때 반응 생성물 약 24.0 g을 얻었으며, GPC 분석 결과 평균 분자량이 3116이었다.19.07 g of methyltrimethoxysilane, 9.03 g of dimethyldichlorosilane and 0.034 g of FeCl 3 as a catalyst were weighed and placed in a 40 ml thick wall-glass tube. TDT-type precursors were synthesized by immersing in a silicone oil bath and maintained for 7 hours while stirring with a magnetic bar. This solution was transferred to a 1 L round flask, and then 68.11 g of methyltrimethoxysilane was further added so that the ratio of methylsiloxane group / dimethylsiloxane group was 0.90: 0.1 molar ratio. 145 ml of THF and 191 ml of toluene were added thereto, and 43.85 g of ion-exchanged water was added thereto to prepare a copolymer by a sol-gel method by a polycondensation reaction while stirring at room temperature for 7 hours. 1.5 mL of a 20% ammonia solution was added to the copolymerized solution to neutralize the pH to 6-7. The neutralized reaction solution was transferred to a 1 L separatory funnel, shaken vigorously by adding 500 ml of ion-exchanged water, and left standing. After about 5 minutes, the lower water layer was removed from the two layers separated by the organic layer and the water layer, and this process was repeated once more. After performing, the water layer was removed, and about 20 g of anhydrous MgSO 4 powder was added to the upper layer and shaken vigorously to remove a trace amount of water. The MgSO 4 powder and FeCl 3 used as catalyst reacted with water and the solid phase dispersed in the organic layer was removed by filtration with No. 5 filter paper, and the filtered organic layer was transferred to a 1 L one-necked round flask at a pressure of about 10 torr. The organic solvent was removed by distillation under reduced pressure and the reaction product was recovered. In this case, about 24.0 g of a reaction product was obtained, and an average molecular weight of 3116 was obtained by GPC analysis.
상기 실시예 1에서 메틸트리메톡시실란과 다이메틸다이클로로실란을 130 ℃에서 7시간 동안 열처리하여 생성된 반응생성물(T-D-T형 전구체)에 대한29Si NMR 스펙트럼을 도 1에 나타내었고, 합성된 T-D-T형 전구체에 추가적으로 첨가한 메틸트리메톡시실란과의 졸-겔 반응을 통해 생성된 폴리메틸실세스퀴옥산 공중합체의29Si NMR 스펙트럼을 도 2에 나타내었다. 29 Si NMR spectrum of the reaction product (TDT-type precursor) produced by heat-treating methyltrimethoxysilane and dimethyldichlorosilane in 130 ° C. for 7 hours in Example 1 is shown in FIG. 1, and synthesized TDT. 29 Si NMR spectrum of the polymethylsilsesquioxane copolymer produced through the sol-gel reaction with methyltrimethoxysilane added to the type precursor is shown in FIG. 2.
실시예 2Example 2
메틸트리에톡시실란 25.21 g, 다이메틸다이클로로실란 9.03 g과 촉매로서 ZrCl4을 0.48 g 칭량하여 40 ㎖의 두꺼운 유리관(thick wall-glass tube)에 넣고 마개를 단단히 봉한 후 약 140 ℃로 유지된 실리콘 오일조(bath)내에 담구어서 마그네틱 바로 교반하면서 10시간 동안 유지시키는 방법으로 T-D-T형 전구체를 합성하였다. 제조한 T-D-T 형 전구체를 1ℓ 라운드 플라스크에 옮겨 넣은 다음 메틸실록산기/다이메틸실록산기의 비율이 0.80 : 0.2 몰비 되도록 메틸트리에톡시실란 25.21 g을 추가적으로 첨가하였다. 그 후 공정은 상기 실시예 1과 동일하게 하였으며, 이때 반응 생성물 약 19.5 g을 얻었으며, GPC 분석 결과 평균 분자량이 2725이었다.Weigh 25.21 g of methyltriethoxysilane, 9.03 g of dimethyldichlorosilane and 0.48 g of ZrCl 4 as catalyst and place it in a 40 ml thick wall-glass tube. TDT-type precursors were synthesized by dipping in a silicone oil bath and maintaining for 10 hours while stirring with a magnetic bar. The prepared TDT precursor was transferred to a 1 L round flask, and then 25.21 g of methyltriethoxysilane was additionally added so that the ratio of methylsiloxane group / dimethylsiloxane group was 0.80: 0.2 molar ratio. Thereafter, the process was the same as in Example 1, wherein about 19.5 g of a reaction product was obtained, and the average molecular weight was 2725 by GPC analysis.
실시예 3Example 3
상기 실시예 1에서 사용한 바와 동일한 방법으로 제조한 T-D-T형 전구체를 1ℓ 라운드 플라스크에 옮겨 넣은 다음 메틸실록산기/다이메틸실록산기의 비율이 0.80 : 0.2 몰비 되도록 메틸트리메톡시실란 19.07 g을 추가적으로 첨가하였다. 그 후 공정은 상기 실시예 1과 동일하게 하였으며, 이때 반응 생성물 약 18 g을 얻었으며, GPC 분석 결과 평균 분자량이 2893이었다.The TDT precursor prepared in the same manner as used in Example 1 was transferred to a 1 L round flask, and then 19.07 g of methyltrimethoxysilane was further added so that the ratio of methylsiloxane group / dimethylsiloxane group was 0.80: 0.2 molar ratio. . Thereafter, the process was the same as in Example 1, wherein about 18 g of a reaction product were obtained, and the average molecular weight was 2893 as a result of GPC analysis.
비교예Comparative example
메틸트리에톡시실란 36.02 g, 다이메틸다이메톡시실란 2.53 g을 칭량하여 1ℓ 라운드 플라스크에 넣고, 열처리 없이 THF 113.6 ㎖와 톨루엔 149.1 ㎖을 가하고 이온 교환수 10.02 g, 60% 질산 1.05 g을 가하여 상온에서 15시간 동안 교반하면서 공중합 반응시켰다. 이후 공정은 상기 실시예 1과 동일하며, 다만 물 층과 유기 층을 분리하는데 장시간이 소요되어 약 30분 후 하층의 물을 제거하였다.이때 얻어진 반응 생성물은 13.4 g이었으며, GPC로 측정한 평균 분자량은 864 이었다.36.02 g of methyltriethoxysilane and 2.53 g of dimethyldimethoxysilane are weighed into a 1 L round flask, and 113.6 ml of THF and 149.1 ml of toluene are added without heat treatment, and 10.02 g of ion-exchanged water and 1.05 g of 60% nitric acid are added thereto. The copolymerization reaction was carried out with stirring for 15 hours. The process was the same as in Example 1, except that it took a long time to separate the water layer and the organic layer, and after about 30 minutes, the water of the lower layer was removed. The reaction product was 13.4 g, and the average molecular weight measured by GPC was obtained. Was 864.
실험예Experimental Example
상기 실시예 1 ∼ 3 및 비교예에서 제조한 반응 생성물의 일부를 취하여 반응 생성물의 함량이 50 중량%가 되게 THF 용액을 가하여 녹인 후 슬라이드 글래스에 약 0.5 mm 두께로 코팅한 후 약 120 ℃로 유지된 오븐에서 약 1시간 동안 열처리하였다. 열처리 후 생성된 피막형 생성물을 벗긴 후 회수하여 TG-IR로 상온에서 500 ℃까지 온도에 따른 열분해 생성물 유무를 확인하였고, 이에 대한 결과를 다음 표 1에 나타내었다.A part of the reaction product prepared in Examples 1 to 3 and Comparative Example was taken and dissolved by adding a THF solution so that the content of the reaction product was 50% by weight, and then coated on slide glass to a thickness of about 0.5 mm and maintained at about 120 ° C. Heat in an oven for about 1 hour. After peeling off the film-form product generated after the heat treatment was recovered and confirmed the presence of pyrolysis products according to the temperature from room temperature to 500 ℃ by TG-IR, the results are shown in Table 1 below.
상기 표 1에 의하면, 실시예 1 ∼ 3에서 제조한 공중합체의 경우는 상온에서 500 ℃의 온도까지 물을 제외한 분해물이 검출되지 않았다. 이에 비하여 비교예의 경우는 온도에 따라 연속적으로 옥타메틸사이클로테트라실록산 등과 같은 고리 형태의 화합물이 검출되었다.According to the said Table 1, in the copolymer manufactured in Examples 1-3, the decomposition product except water was not detected from the normal temperature to the temperature of 500 degreeC. On the other hand, in the case of the comparative example, a compound in the form of a ring such as octamethylcyclotetrasiloxane was detected continuously with temperature.
상술한 바와 같이, 본 발명에 따른 다이메틸실록산이 분자수준으로 균일하게분산된 폴리메틸실세스퀴옥산 공중합체는 메틸트리알콕시실란과 다이메틸다이클로로실란을 몰비로 2 : 1로 혼합하고 미리 130 ℃ 전후에서 T-D-T 형의 균일한 구조가 되도록 전구체를 합성하고, 여기에 메틸실록산과 다이메틸실록산이 특정한 비율이 되게 메틸트리알콕시실란을 첨가하여 졸-겔법으로 공중합하여 폴리메틸실세스퀴옥산 모재의 유연성을 부가함과 동시에, 메틸알콕시실란과 다이메틸실록산간의 물에 대한 가수분해 속도를 최소화함으로써, 균일성이 높은 공중합체를 얻을 수 있었다. 이에 따라 내열성이 우수하고 규소원자(Si)에 메틸기의 함량 증가에 의한 유연성이 기대되므로 반도체용 저 유전(low-k) 층간 재료로 활용이 가능하다.As described above, the polymethylsilsesquioxane copolymer in which the dimethylsiloxane according to the present invention is uniformly dispersed at a molecular level is mixed with methyltrialkoxysilane and dimethyldichlorosilane in a molar ratio of 2: 1 and 130 in advance. Precursors were synthesized so as to have a uniform structure of TDT type before and after < RTI ID = 0.0 > C, < / RTI > and methyltrialkoxysilane was added to make a specific ratio of methylsiloxane and dimethylsiloxane and copolymerized by sol-gel method to obtain a polymethylsilsesquioxane base material. By adding flexibility and minimizing the rate of hydrolysis of water between methylalkoxysilane and dimethylsiloxane, a highly homogeneous copolymer could be obtained. Accordingly, since it is excellent in heat resistance and flexibility by increasing the content of methyl groups in silicon atoms (Si), it can be utilized as a low-k interlayer material for semiconductors.
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