KR20070108658A - Method for preparation method of coating composition for insulating membrane of semiconductor device and prepared coating composition) - Google Patents
Method for preparation method of coating composition for insulating membrane of semiconductor device and prepared coating composition) Download PDFInfo
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- KR20070108658A KR20070108658A KR1020060040978A KR20060040978A KR20070108658A KR 20070108658 A KR20070108658 A KR 20070108658A KR 1020060040978 A KR1020060040978 A KR 1020060040978A KR 20060040978 A KR20060040978 A KR 20060040978A KR 20070108658 A KR20070108658 A KR 20070108658A
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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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
Abstract
Description
본 발명은 전자 디바이스 혹은 디스플레이 디바이스 등 반도체 장치의 제조에 쓰이는 절연 막 형성용 도포액 조성물에 관한 발명으로, 더욱 상세하게는 실란화합물 및 금속알콕사이드를 가수분해 및 공중합하여 수득된 반도체 장치의 절연막 형성용 도포액 조성물의 제조방법 및 제조된 도포액에 관한 발명이다.The present invention relates to a coating liquid composition for forming an insulating film used in the manufacture of a semiconductor device such as an electronic device or a display device, and more particularly, for forming an insulating film of a semiconductor device obtained by hydrolyzing and copolymerizing a silane compound and a metal alkoxide. The invention relates to a method for producing a coating liquid composition and to a prepared coating liquid.
액정 디스플레이 소자의 대형화에 따라 투명 전극의 절연, 보호의 목적으로 산화물 피막을 형성하는 일이 행해지고 있으며, 전자 디바이스의 기판상에 투명한 절연 피막을 형성하는 공정은, 디스플레이 소자, 반도체 장치, 인쇄 배선판, 미소 기계 장치 등을 막론하고 널리 진행되고 있다.As the size of liquid crystal display devices increases, an oxide film is formed for the purpose of insulating and protecting the transparent electrodes. The process of forming the transparent insulating film on the substrate of the electronic device includes a display element, a semiconductor device, a printed wiring board, It is widely progressed regardless of micromechanical devices.
산화물 피막의 형성방법은 증착법, 스퍼터링법 등으로 대표되는 기상법과 산화물 피막 형성용 도포액을 사용하는 도포법이 알려져 있으나 생산성, 대형 기판에 대한 피막형성의 용이성으로 인하여 도포법이 많이 사용되고 있으며, 도포법에 의한 절연 피막형성은 투명 도전막의 저항변화, 에너지 절감, 유리의 변형 등의 문제 가 있으므로 300℃ 이하의 온도에서 가열 경화하는 것이 요망되고 있다.As a method of forming an oxide film, a vapor deposition method such as a vapor deposition method and a sputtering method and a coating method using an oxide film forming coating are known, but coating methods are widely used due to productivity and ease of forming a film on a large substrate. The insulating film formation by the method has problems such as resistance change of the transparent conductive film, energy saving, deformation of glass, and the like, and heat curing at a temperature of 300 ° C. or lower is desired.
그 중에서도, 액체를 도포 코팅해서 절연 막을 형성하는 방법은, 필요로 하는 설비가 간편하고 높은 막의 재현성 및 균일성을 보이며, 또한 요철을 완화해서 평탄화 하는 능력이 높기 때문에, 비용 대비 높은 생산성을 나타내어 양산 방법으로써 주목되어 있다.Among them, the method of forming an insulating film by coating and coating a liquid has a high productivity compared to cost because the equipment required is simple, exhibits high reproducibility and uniformity of the film, and has a high ability to alleviate unevenness and flattening. It is noted as a method.
일반적으로, 코팅에 의해서 피막을 형성하기 위한 도포 액의 주성분에는, 폴리이미드 수지나 폴리아크릴수지 등의 유기 폴리머를 쓰는 경우와, 폴리실록산 수지 등의 무기 폴리머를 쓰는 경우가 있다.Generally, organic polymers, such as a polyimide resin and a polyacrylic resin, and inorganic polymers, such as a polysiloxane resin, may be used for the main component of the coating liquid for forming a film by coating.
코팅 재료로써 유기 폴리머를 쓴 경우는, 수 ㎛ 두께의 막은 쉽게 얻을 수 있지만, 막의 내열성, 내후성이나 전기적 특성이 뒤떨어지고, 막에서의 가스발생이 문제가 되기 때문에, 사용하는데 있어서의 장애가 되고 있었다.In the case of using an organic polymer as the coating material, a film having a thickness of several micrometers can be easily obtained, but since the film is inferior in heat resistance, weather resistance and electrical properties, and gas generation in the film is a problem, it has been an obstacle in use.
한편, 실록산 결합 (-O-Si-O-)를 골격을 가지는 실록산계 무기 폴리머에서 수득된 피막은, 300℃ 이상의 내열성이 있고, 전기적 특성도 좋기 때문에, 특히 유리를 기판으로 하는 경우의 투명 절연 막으로써 주목되고 왔다.On the other hand, since the film obtained from the siloxane inorganic polymer which has a siloxane bond (-O-Si-O-) frame | skeleton has heat resistance of 300 degreeC or more, and electrical property is also good, it is transparent insulation especially when glass is used as a board | substrate. Attention has been drawn to.
그러나, 실록산계의 무기 폴리머는, 건조 수축이 크게 나타나고, 또 막 강도가 낮기 때문에, 건조 후에 크랙이 발생하는 한계막 두께는 1 ㎛ 미만으로 낮기 때문에 1㎛ 이상의 막 형성을 필요로 하는 용도에는 적용이 곤란하다고하는 문제점이 있었다.However, since the siloxane-based inorganic polymer exhibits a large dry shrinkage and a low film strength, the limit film thickness at which cracks occur after drying is low at less than 1 µm, so that it is applicable to applications requiring a film formation of 1 µm or more. There was a problem that this was difficult.
따라서, 수 ㎛ 정도까지의 두께를 갖는 피막이 크랙발생 없이 형성할 수 있고, 내열성이 300 ℃ 이상으로, 충분한 내후성과 전기적 특성을 가지고, 막에서의 물이나 유기 성분의 유출이 적은 피막을 형성할 수 있는 도포액에 대한 요구가 있어 왔다.Therefore, a film having a thickness of up to several micrometers can be formed without cracking, and a film having a heat resistance of 300 ° C. or more, having sufficient weather resistance and electrical characteristics, and having a low flow of water or organic components from the film can be formed. There has been a need for an applied coating liquid.
본 발명은 이러한 종래의문제점을 해결하고자 발명된 것으로서,The present invention has been invented to solve such a conventional problem,
수 ㎛의 두께를 갖는 막을 형성시에도 크랙을 발생하지 않고, 내열성, 내후성 및 전기적 특성이 우수하고 막에서의 가스발생이 적은 절연막 형성용 도포액의 제조방법을 제공하고자 한다. It is intended to provide a method for preparing an insulating film forming coating liquid which is excellent in heat resistance, weather resistance and electrical properties and little gas generation in the film without cracking even when a film having a thickness of several μm is formed.
또한, 본 발명은 이러한 제조 방법으로 제조된 절연막 형성용 도포액을 제공하고자 한다. In addition, the present invention is to provide a coating liquid for forming an insulating film prepared by such a manufacturing method.
이하, 본 발명을 상세하게 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명의 반도체 장치의 절연막 형성용 도포액 조성물의 제조방법은 하기의 단계를 포함한다.: The method for preparing a coating liquid composition for forming an insulating film of a semiconductor device of the present invention includes the following steps:
하기 일반식 Ⅰ로 나타내어지는 실란 화합물을 산성조건하에서 가수 분해 시키는 단계;Hydrolyzing the silane compound represented by Formula I below under acidic conditions;
일반식 Ⅰ : RSi(OR')3 Formula Ⅰ: RSi (OR ') 3
(이때, R은 페닐기 또는 불포화결합을 하나 이상 함유하는 1가 치환기이고, R'는 탄소수 3 이하의 1가 치환기)(Wherein R is a monovalent substituent containing one or more phenyl groups or unsaturated bonds, and R 'is a monovalent substituent having 3 or less carbon atoms)
티타늄, 지르코늄, 알루미늄 및 주석으로 구성된 군에서 선택된 하나 또는 2 이상의 금속의 알콕시드와 상기 알콕시드의 금속과 배위 결합을 형성할 수 있는 배위결합제를 혼합시키는 단계; 및 Mixing an alkoxide of one or more metals selected from the group consisting of titanium, zirconium, aluminum and tin with a coordinating agent capable of forming a coordinating bond with the metal of the alkoxide; And
상기 두 단계에서 각각 수득된 화합물을 몰비 3-97: 97-3로 공중합시켜서 중량 평균 분자량 500 이상 또한 10,000 이하의 금속실록산 올리고머를 수득하는 단계. Copolymerizing the compounds obtained in each of the two steps in a molar ratio of 3-97: 97-3 to obtain metalsiloxane oligomers having a weight average molecular weight of 500 or more and 10,000 or less.
일반식 Ⅰ의 실란이 3 이하시는 크랙 발생 위험이 높고 97 이상시는 내열성에 문제가 발생한다. 그러나, 이 비율은 본 발명에서 큰 의미를 갖는 것은 아니다.When the silane of Formula I is 3 or less, there is a high risk of cracking, and when it is 97 or more, there is a problem in heat resistance. However, this ratio does not have a great meaning in the present invention.
상기에서 일반식 Ⅰ의 화합물을 산성 조건하에서 가수분해 시키는 이유는 산성조건하에서 가수분해 되어야만 Si-OH 의 반응성이 크게 향상되어 금속알콕시드와 중합반응이 원활하게 진행되기 때문이다.The reason why the compound of Formula I is hydrolyzed under acidic conditions is that the reactivity of Si-OH is greatly improved only when it is hydrolyzed under acidic conditions so that the polymerization reaction with metal alkoxide proceeds smoothly.
상기에서 배위 결합제와 결합시키는 것은 일반적으로 실란 화합물과 금속 알콕시드의 가수 분해 속도는 크게 다르기 때문에, 동시에 가수분해 반응을 균일하게 진행하는 것은 쉽지 않으므로, 이를 해결하기 위한 것이다.Coupling with the coordinating binder in the above is generally because the hydrolysis rate of the silane compound and the metal alkoxide are greatly different, and therefore it is not easy to uniformly proceed the hydrolysis reaction at the same time.
예를 들면, 가수 분해 속도가 상대적으로 빠른 금속 알콕시드만이 급속히 중합 하여 때때로 침전이나 겔화되어버리므로, 알콕시드의 금속과 배위 결합을 형성할 수 있는 화합물을 배합한 용액을, 임의의 비율로 혼합해서 첨가하여 이와 같은 불균일인 중합을 일으키지 않고, 실란 화합물과 금속 알콕시드를 균일하게 중합시 키고자 하는 것이다.For example, only a metal alkoxide having a relatively high hydrolysis rate rapidly polymerizes and sometimes precipitates or gels. Thus, a solution containing a compound capable of forming a coordinating bond with the metal of the alkoxide is mixed at an arbitrary ratio. It is intended to uniformly polymerize the silane compound and the metal alkoxide without mixing and adding to cause such heterogeneous polymerization.
상기 일반식 Ⅰ 중 의 R은 페닐기 또는 불포화결합, 즉 에티닐기를 하나 이상 함유하는 1가 치환기이고, R'는 탄소수 3 이하의 1가 치환기이다.R in the general formula (I) is a monovalent substituent containing at least one phenyl group or an unsaturated bond, ie an ethynyl group, and R 'is a monovalent substituent having 3 or less carbon atoms.
본 발명에서 R이 에티닐기를 포함하는 것은 매우 중요한데, 이는 이러한 경우만이 크랙이 발생하지 않는 강도를 부여하기 때문이다. It is very important for R to include an ethynyl group in the present invention, because only in this case, it gives strength that cracking does not occur.
이때, R은 구체적으로는 페닐기 (C6H5),비닐기 (CH2=CH-), 아릴기 (CH2=CH-CH2-),3 -아크릴록시프로필기 (CH2=CHCOOCH2CH2CH2-)， 3 - 메타크릴록시프로필기 (CH2=C(CH3)COOCH2CH2CH2-)등을 들수있다.In this case, R is specifically a phenyl group (C 6 H 5 ), vinyl group (CH 2 = CH-), aryl group (CH 2 = CH-CH 2- ), 3-acryloxypropyl group (CH 2 = CHCOOCH 2 CH 2 CH 2- ), 3-methacryloxypropyl group (CH 2 = C (CH 3 ) COOCH 2 CH 2 CH 2- ), and the like.
또한, 일반식 Ⅰ 중 R'는 탄소수 3 이하의 임의의 1가 치환기로서 3개의 R'는 서로 동일 또는 상이할 수 있으며, 반응용이성 또는 용제에서의 용해성을 고려해서 선택할 수 있다. In addition, in General Formula I, R 'is an arbitrary monovalent substituent of 3 or less carbon atoms, and three R's may be the same or different from each other, and may be selected in consideration of reaction solubility or solubility in a solvent.
R'에 포함되는 탄소수가 3를 넘으면, 실란 단량체의 가수 분해 중합 반응이 늦어지기 때문에, 3 이하 인 것이 바람직하고, 더욱 매우 적합하게는 메틸기, 에틸기 혹은 아세틸기인 것이 바람직하다.When carbon number contained in R 'exceeds 3, since hydrolysis-polymerization reaction of a silane monomer becomes slow, it is preferable that it is 3 or less, More preferably, it is preferable that it is a methyl group, an ethyl group, or an acetyl group.
일반식 Ⅰ을 충족시키는 실란 화합물의 구체적인 예는 하기와 같다.Specific examples of the silane compound satisfying the general formula (I) are as follows.
페닐트리메톡시실란 (C6H4Si(OCH3)3)， 페닐트리에톡시실란 (C6H4Si(OC2H5)3 )， 페닐 트리아세톡시실란 (C6H4Si(OCOCH3)3)， 페닐트리이소시아네이트실란 (C6H4Si(NCO)3 )， 페닐트리스(아세톡심)실란(C6H4Si[ONC(CH3)2]3)， 비닐트리메톡시실란 (CH2=CH2Si(OCH3)2)， 비닐트리에톡시실란(CH2=CH2Si(OC2H5)3 )， 비닐트리아세톡시실란 (CH2=CH2Si(OCOCH3)3)，비닐트리이소시아네이트실란 (CH2=CH2Si(NCO)3 )， 비닐트리스(아세톡심)실란(CH2=CH2Si[ONC(CH3)2]3 )， 3 -아크릴록시프로필트리메톡시실란(CH2=CHCOOCH2CH2CH2Si(OCH3)3)， 3 - 메타크릴록시프로필트리에톡시실란(CH2=CHCOOCH2CH2CH2Si(OC2H5)3)， 3 - 메타크릴록시프로필트리아세톡시실란 (CH2=CHCOOCH2CH2CH2Si(OCOCH3)3)， 3 - 메타크릴록시프로필트리이소시아네이트실란(CH2=CHCOOCH2CH2CH2Si(NCO)3)， 3 - 메타크릴록시프로필트리스(아세톡심) 실란 (CH2=CHCOOCH2CH2CH2Si[ONC(CH3)2]3 )， 3 -아크릴록시프로필트리메톡시실란(CH2=CHCOOCH2CH2CH2Si(OCH3)3 )， 3 -아크릴록시프로필트리에톡시실란(CH2=C(CH3)COOCH2CH2CH2Si(OC2H5)3 )， 3 -아크릴록시프로필트리아세톡시실란(CH2=C(CH3)COOCH2CH2CH2Si(OCOCH3)3 )， 3-아크릴록시프로필트리이소시아네이트실란(CH2=C(CH3)COOCH2CH2CH2Si(NCO)3 )， 3 -아크릴록시프로필트리스(아세톡심)실란 (CH2=C(CH3)COOCH2CH2CH2-Si[ONC(CH3)2]3)등을 들수있다.Phenyltrimethoxysilane (C 6 H 4 Si (OCH 3 ) 3 ), Phenyltriethoxysilane (C 6 H 4 Si (OC 2 H 5 ) 3 ), Phenyl triacetoxysilane (C 6 H 4 Si ( OCOCH 3 ) 3 ), Phenyltriisocyanatesilane (C 6 H 4 Si (NCO) 3 ), Phenyltris (acetoxim) silane (C 6 H 4 Si [ONC (CH 3 ) 2 ] 3 ), Vinyltrimethoxy Silane (CH 2 = CH 2 Si (OCH 3 ) 2 ), Vinyltriethoxysilane (CH 2 = CH 2 Si (OC 2 H 5 ) 3 ), Vinyltriacetoxysilane (CH 2 = CH 2 Si (OCOCH) 3 ) 3 ), vinyltriisocyanate silane (CH 2 = CH 2 Si (NCO) 3 ), vinyl tris (acetoxim) silane (CH 2 = CH 2 Si [ONC (CH 3 ) 2 ] 3 ), 3-acryl Roxypropyltrimethoxysilane (CH 2 = CHCOOCH 2 CH 2 CH 2 Si (OCH 3 ) 3 ), 3-methacryloxypropyltriethoxysilane (CH 2 = CHCOOCH 2 CH 2 CH 2 Si (OC 2 H 5 3 ), 3-methacryloxypropyltriacetoxysilane (CH 2 = CHCOOCH 2 CH 2 CH 2 Si (OCOCH 3 ) 3 ), 3 -methacryloxypropyltriisocyanate (CH 2 = CHCOOCH 2 CH 2 CH 2 Si (NCO) 3 ), 3-methacryloxypropyltris (acetoxim) silane (CH 2 = CHCOOCH 2 CH 2 CH 2 Si [ONC (CH 3 ) 2 ] 3 ), 3-acryloxy Propyltrimethoxysilane (CH 2 = CHCOOCH 2 CH 2 CH 2 Si (OCH 3 ) 3 ), 3-acryloxypropyltriethoxysilane (CH 2 = C (CH 3 ) COOCH 2 CH 2 CH 2 Si (OC 2 H 5 3 ), 3-acryloxypropyltriacetoxysilane (CH 2 = C (CH 3 ) COOCH 2 CH 2 CH 2 Si (OCOCH 3 ) 3 ), 3-acryloxypropyltriisocyanatesilane (CH 2 = C ( CH 3 ) COOCH 2 CH 2 CH 2 Si (NCO) 3 ), 3-acryloxypropyltris (acetoxime) silane (CH 2 = C (CH 3 ) COOCH 2 CH 2 CH 2 -Si [ONC (CH 3 ) 2 ] 3 ), and so on.
실란화합물이 3개의 관능기를 갖지 않는 경우는 금속알콕사이드와 공중합체 형성이 매우 어려우며, 공중합체가 형성되었다고 해도 만족할만한 두께나 평활도, 강도 등을 갖는 우수한 막을 제조하는 데는 곤란함이 많았다.When the silane compound does not have three functional groups, metal alkoxide and copolymer formation are very difficult, and even when a copolymer is formed, it is difficult to produce an excellent film having satisfactory thickness, smoothness, strength, and the like.
일반식 Ⅰ을 충족시키는 실란 화합물을 1종 또는 2종 이상을 조합하여 사용할 수 있다.The silane compound which satisfy | fills General formula I can be used 1 type or in combination of 2 or more types.
또한, 일반식 Ⅰ의 실란 단량체를, 가수 분해 가능한 다른 일반적 실레인 화합물과 조합하여 사용할 수도 있다.Moreover, the silane monomer of General formula I can also be used in combination with the other general silane compound which can be hydrolyzed.
본 발명에서 일반식 Ⅰ의 3개의 관능기를 갖는 실란 화합물은 임의의 4개의 관능기를 갖는 실란화합물, 페닐기 또는 불포화 결합을 가지지 않는 3 관능기를 갖는 실란류 및 2 관능기를 가진 실란류와 조합하여 사용가능하다.In the present invention, the silane compound having three functional groups of general formula (I) may be used in combination with a silane compound having any four functional groups, a phenyl group or a silane having a trifunctional group having no unsaturated bond, and a silane having a bifunctional group. Do.
상기 3 관능기 실란 단량체와 공중합 가능한 다른 실란 화합물의 예 로서는, 테트라메톡시실란(Si(OCH3)4), 테트라에톡시실란(Si(OC2H5)4), 테트라아세톡시실란 (Si(OCOCH3)4), 테트라이소시아네이트실란 (Si(NCO)4), 테트락스 (아세톡시) 실란 (Si[ONC(CH3)2]4), 트리메톡시실란 (HSi(OCH3)3), 트리에톡시실란 (HSi(OC2H5)3), 메틸트리메톡시실란 (CH3Si(OCH3)3), 메틸트리에톡시실란 (CH3Si(OC2H5)3), 메틸트리아세톡시실란 (CH3Si(OCOCH3)3), 메틸트리이소시아네이트실란 (CH3Si(NCO)3), 메틸트리스(아세톡시)실란 (CH3Si[ONC(CH3)2]3), 3-아미노프로필트리메톡시실란 (NH2CH2CH2CH2Si(OCH3)3), 3-아미노프로필트리에톡시시란 (NH2CH2CH2CH2Si(OC2H5)3), 3- 글리시독시프로필트리메톡시실란 (CH2OCHOCH2CH2CH2Si(OCH3)3),디메틸디메톡시실란 ((CH3)2Si(OCH3)2), 디메틸디에톡시실란 ((CH3)2Si(OC2H5)2), 디메틸디아세톡시실란 ((CH3)2Si(OCOCH3)2), 디메틸메톡시아세톡시실란, 디메틸디이소시아네이트실란 ((CH3)2Si(NCO)2), 디메틸메톡시이소시아네이트실란((CH3)2Si(OCH3)(NCO)), 디메틸비스(아세톡시)실란 ((CH3)2Si[ONC(CH3)2]), 메틸페닐디메톡시실란 ((CH3)(C6H4)Si(OCH3)2), 디페닐디메톡시실란 ((C6H4)2Si(OCH3)2) 등이며, 이중 1종 또는 2종이상을 결합하여 사용할 수 있다. Examples of the other silane compound copolymerizable with the trifunctional silane monomer include tetramethoxysilane (Si (OCH 3 ) 4 ), tetraethoxysilane (Si (OC 2 H 5 ) 4 ), tetraacetoxysilane (Si ( OCOCH 3 ) 4 ), tetraisocyanatesilane (Si (NCO) 4 ), tetrax (acetoxy) silane (Si [ONC (CH 3 ) 2 ] 4 ), trimethoxysilane (HSi (OCH 3 ) 3 ), Triethoxysilane (HSi (OC 2 H 5 ) 3 ), methyltrimethoxysilane (CH 3 Si (OCH 3 ) 3 ), methyltriethoxysilane (CH 3 Si (OC 2 H 5 ) 3 ), methyl Triacetoxysilane (CH 3 Si (OCOCH 3 ) 3 ), methyltriisocyanatesilane (CH 3 Si (NCO) 3 ), methyltris (acetoxy) silane (CH 3 Si [ONC (CH 3) 2 ] 3 ), 3-aminopropyltrimethoxysilane (NH 2 CH 2 CH 2 CH 2 Si (OCH 3 ) 3 ), 3-aminopropyltriethoxysilane (NH 2 CH 2 CH 2 CH 2 Si (OC 2 H 5 ) 3 ), 3-glycidoxypropyltrimethoxysilane (CH 2 OCHOCH 2 CH 2 CH 2 Si (OCH 3 ) 3 ), dimethyldimethoxysilane ((CH 3 ) 2 Si (OC H 3 ) 2 ), dimethyldiethoxysilane ((CH 3 ) 2 Si (OC 2 H 5 ) 2 ), dimethyldiacetoxysilane ((CH 3 ) 2 Si (OCOCH 3 ) 2 ), dimethylmethoxyacetoxy Silanes, Dimethyl Diisocyanatesilane ((CH 3 ) 2 Si (NCO) 2 ), Dimethylmethoxyisocyanatesilane ((CH 3 ) 2 Si (OCH 3 ) (NCO)), Dimethylbis (acetoxy) silane ((CH 3 ) 2 Si [ONC (CH 3 ) 2 ]), methylphenyldimethoxysilane ((CH 3 ) (C 6 H 4 ) Si (OCH 3 ) 2 ), diphenyldimethoxysilane ((C 6 H 4 ) 2 Si (OCH 3 ) 2 ) and the like, and can be used in combination of one or two or more of them.
상기 실란 화합물과, 티타늄, 지르코늄, 알루미늄, 주석으로 구성된 군에서 선택되는 하나 이상의 금속의 알콕시드와 반응하여 가수분해 공중합시킨다.The silane compound is reacted with an alkoxide of at least one metal selected from the group consisting of titanium, zirconium, aluminum, and tin to hydrolyze and copolymerize.
티탄, 지르코늄, 알루미늄, 주석의 알콕시드는, 구체적으로는, 테트라에톡시티타늄, 테트라프로폭시티타늄, 테트라이소프로폭시티타늄, 테트라푸톡시티타늄, 테트라에톡시지르코늄, 테트라프로폭시지르코늄, 테트라이소프로폭시지르코늄, 테트라푸톡시지르코늄, 트리에톡시알루미늄, 트리프로폭시알루미늄, 트리이소프로폭시알루미늄, 트리부톡시알루미늄, 트리스(2-메틸프로필)알루미늄, 테트라에톡시주석, 테트라프로폭시주석, 테트라이소프로폭시주석, 테토라푸톡시주석 등의 알콕시드이다.The alkoxides of titanium, zirconium, aluminum and tin are, specifically, tetraethoxytitanium, tetrapropoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, tetraethoxyzirconium, tetrapropoxyzirconium and tetraisopropoxy Zirconium, tetrabutoxyzirconium, triethoxyaluminum, tripropoxyaluminum, triisopropoxyaluminum, tributoxyaluminum, tris (2-methylpropyl) aluminum, tetraethoxytin, tetrapropoxytin, tetraisopro Alkoxides, such as a foxy tin and tetoraputoxytin.
상기 금속 알콕시드에 바꿔서, 일부를 β디케톤등의 킬레이트 화합물로 바꿔 놓은 부분 알콕시드, 구체적으로는 아세틸아세트네이트트리이소프로폭시티타늄 이나 비스아세토네이트디이소프로폭시티타늄 등의 부분 금속 알콕시드도 매우 적합하게 사용할 수 있다.Partial alkoxides in which part of the alkoxide is replaced with a chelate compound such as β-diketone, specifically, partial metal alkoxides such as acetylacetate triisopropoxytitanium and bisacetonate diisopropoxytitanium It can be used very suitably.
상기 실란 화합물과 상기 금속 알콕시드를 가수분해 중합해서 공중합체를 얻는다.The copolymer is obtained by hydrolyzing and polymerizing the silane compound and the metal alkoxide.
구체적으로는, 실란 성분과 금속 알콕시드 성분을 필요에 따라서 에탄올, 2 -프로판올, 아세톤, 초산부틸 등의 임의의 용매에 희석하고, 반응에 필요한 물과 촉매양의 염산, 초산, 질산 등의 산을 가하고, 임의의 온도로 교반 내지 환류 함으로써 진행한다.Specifically, the silane component and the metal alkoxide component are diluted in an optional solvent such as ethanol, 2-propanol, acetone, butyl acetate, and the like, and the water required for the reaction and acids such as hydrochloric acid, acetic acid, nitric acid, etc. are required. It adds and advances by stirring to reflux at arbitrary temperature.
여기서 쓰는 용매, 산 촉매의 종류나 양에는 각별 규정은 없이, 임의로 선택할 수 있다.The type and amount of the solvent and acid catalyst used herein can be arbitrarily selected without particular regulation.
가수 분해 중합 반응은 20 ℃ 이하의 저온이라도 진행하지만, 가열이나 환류 조작에 의해서 반응을 촉진할 수 있다.The hydrolysis polymerization reaction proceeds even at a low temperature of 20 ° C. or lower, but the reaction can be promoted by heating or reflux operation.
본 발명의 제조방법은 구체적으로는, 일반식 Ⅰ로 나타나는 실란 화합물을 미리 산성 조건에서 가수 분해한 용액 (A)을 준비하고, 티타늄, 지르코늄, 알루미늄, 주석으로 구성된 군에서 선택된 하나 이상의 금속의 알콕시드에, 그 금속과 배위 결합을 형성하는 배위결합제를 첨가한 용액 (B)을 준비한다.Specifically, in the production method of the present invention, a solution (A) obtained by previously hydrolyzing the silane compound represented by the general formula (I) under acidic conditions is prepared, and an alkoxy of at least one metal selected from the group consisting of titanium, zirconium, aluminum, and tin The solution (B) which added the coordination binder which forms a coordination bond with this metal is prepared.
용액 (A)와 (B)를 임의의 비율로 혼합해서 공중합시키는 것에 따라, 침전ㅇ석출 등이 생기지 않는 균일한 중합체를 얻는다.By mixing and copolymerizing the solutions (A) and (B) in an arbitrary ratio, a uniform polymer which does not cause precipitation or the like is obtained.
용액 (A)에 있어서, 산성 조건하에서의 일반식 Ⅰ의 실란 화합물의 가수 분해는, 에탄올, 2-프로판올, 아세톤, 초산부틸 등의 임의의 용매로 일반식 Ⅰ의 실란 화합물을 희석하고, 반응에 필요한 물과 촉매양의 유기산, 염산, 초산 또는 질산을 가하고, 실온 내지 임의의 온도로 교반 내지 환류 함으로써 진행한다.In the solution (A), hydrolysis of the silane compound of the general formula (I) under acidic conditions requires dilution of the silane compound of the general formula (I) with any solvent such as ethanol, 2-propanol, acetone, butyl acetate, and the like. It proceeds by adding water and a catalytic amount of organic acid, hydrochloric acid, acetic acid or nitric acid and stirring to reflux at room temperature to an arbitrary temperature.
상기 가수 분해 생성물은, 시간이 지날수록 자신의 축중합으로 인하여 분자량이 증대하기 때문에, 몇일 이상의 장시간 그대로 방치하는 것은 바람직하지 못하다.Since the molecular weight of the hydrolyzate increases over time due to its condensation polymerization, it is not preferable to leave the hydrolysis product as it is for a long time of several days or more.
용액 (B)는 금속 알콕시드를 필요에 따라서 에탄올, 2 -프로판올, 아세톤, 초산부틸 등의 임의의 용매로 희석한 뒤, 그 금속과 배위 결합을 형성하는 화합물을 첨가한다.The solution (B) is diluted with an optional solvent such as ethanol, 2-propanol, acetone, butyl acetate and the like, after the metal alkoxide is added to the compound which forms a coordination bond with the metal.
배위결합을 형성하는 배위결합제는, β디케톤류, 하이드록시카본산류, 하이드록시카본산에스테르류, 하이드록시케톤류, 아미노알코올류가 매우 적합하다.Β diketones, hydroxy carboxylic acids, hydroxy carboxylic acid esters, hydroxy ketones, and amino alcohols are very suitable as coordination binders for forming coordination bonds.
구체적으로는, β디케톤류로써 아세틸아세톤, 헥사플로로아세틸아세톤, 아세트초산메틸, 아세트초산에틸, 마론산, 마론산모노에틸, 마론산디에틸, 1,3-아세톤디카르본산, 4-메톡시초산메틸, 벤조일아세톤, 1,3 - 시클로펜탄디올, 3,5 -헤푸탄디온, 1,3-인단디온, 3 -옥소펜탄산메틸, 아세트아세트아미드, 하이드록시 카본산류로써 글리콜산, 젓산, 3 - 하이드록시프로판산 ; 하이드록시카르본산에스테르류로써 젓산에틸, 젓산메틸 ; 하이드록시케톤류로써 아세톨, 아세토인; 아미노 알콜류로써 N- 메칠아미노아탄올, N- 디메칠아미노아탄올, 모노에타놀아민, 디에탄올아민, 트리에타놀아민 등을 들수 있다.Specifically, acetylacetone, hexafluoroacetylacetone, methyl acetic acid, ethyl acetate, maronic acid, monoethyl maronic acid, diethyl maronic acid, 1,3-acetone dicarboxylic acid, and 4-methoxy as β diketones Methyl acetate, benzoyl acetone, 1,3-cyclopentanediol, 3,5-hefutanedione, 1,3-indandione, methyl 3-oxopentanate, acetacetamide, glycolic acid, lactic acid, 3-hydroxypropanoic acid; As hydroxycarboxylic acid esters, ethyl acetate and methyl acetate; As hydroxyketones, acetol and acetoin; Examples of the amino alcohols include N-methylaminoethanol, N-dimethylaminoethanol, monoethanolamine, diethanolamine, and triethanolamine.
배위결합을 형성하는 배위결합제와 금속 알콕시드의 혼합 비율은 배위수에 의해서 변할 수 있지만, 일반적으로는 금속 원자 1몰에 대해서 0.2 내지 4몰을 배합한다.Although the mixing ratio of the coordinating agent and the metal alkoxide forming the coordinating bond can be changed by the coordination number, generally 0.2 to 4 moles are added per 1 mole of the metal atom.
상기 (A)성분과 (B)성분의 공중합은, 실온 내지 환류 조건하에서 수행되고, 수득가능한 올리고머의 중량 평균 분자량을 500 이상 또한 10,000 이하로 조정하는 것이 바람직하다.It is preferable to perform copolymerization of the said (A) component and (B) component at room temperature to reflux conditions, and to adjust the weight average molecular weight of the oligomer which can be obtained to 500 or more and 10,000 or less.
중량 평균 분자량이 500에 못 미치면, 도포에 의해서 막을 형성하는 것이 곤란해지고, 또 10,000를 넘으면 올리고머의 용제 용해성이 손상되고, 도포막 형태의 결함 등이 생기기 쉬워진다.When the weight average molecular weight is less than 500, it becomes difficult to form a film by coating, and when it exceeds 10,000, the solvent solubility of an oligomer is impaired and defects in the form of a coating film tend to occur.
상기 공중합체의 용액은, 그대로, 또는 적당한 용매로 희석해서 쓸 수도 있다.The solution of the copolymer may be used as it is or diluted with a suitable solvent.
또한 상기 필수 성분외에, 물이나 임의의 유기용매, 유기 아민염 등의 pH 조정제, 유기 암모늄 화합물 등의 반응 촉진 촉매, 임의의 계면 활성제, 소 포제, 실란 커플링제등의 밀착 촉진제등을 소정의 목적으로 도포 액에 첨가할 수도 있다.In addition to the above essential components, a pH adjusting agent such as water, an arbitrary organic solvent, an organic amine salt, a reaction promoting catalyst such as an organic ammonium compound, an optional surfactant, an antifoaming agent, an adhesion promoter such as a silane coupling agent, or the like may be used for a predetermined purpose. It can also be added to the coating liquid.
상기의 방법으로 제조한 도포 액을, 유리등의 기판상에 도포 하고, 실온 내지 350 ℃ 이하의 임의의 온도로 건조해서 도포 피막을 얻는다.The coating liquid manufactured by the said method is apply | coated on board | substrates, such as glass, and it dries at arbitrary temperature from room temperature to 350 degrees C or less, and obtains a coating film.
이 때의 건조 수단은 특히 규정되지 않지만, 통상 핫플레이트를 쓰고, 1∼60분의 시간으로 처리한다.Although the drying means at this time is not specifically defined, Usually, a hotplate is used and it processes in 1 to 60 minutes.
하기 실험예는 본 발명의 실시예이나, 본 발명이 이에 제한받지 않는다. The following experimental examples are examples of the present invention, but the present invention is not limited thereto.
[실시예 1]Example 1
페닐트리메톡시실란 198.3 g, 2 - 프로판올 100 g(Aldrich사제)를 가열 장치가 부착된 2리터의 용량의 3구 플라스크에 주입한 후, 플라스크의 내용물을 격렬하게 교반하면서, 1몰 /리터 농도의 질산 1 ml 과 순수 53 ml을 혼합한 용액을, 플라스크에 설치한 적하 깔때기에서 30분을 걸려서, 내용물의 격렬한 교반을 계속 계속한 채 적하했다.198.3 g of phenyltrimethoxysilane and 100 g of 2-propanol (manufactured by Aldrich) were injected into a two-necked flask having a capacity of 2 liters equipped with a heating device, and then the contents of the flask were stirred vigorously while being 1 mol / liter concentration. The solution which mixed 1 ml of nitric acid and 53 ml of pure waters was dripped for 30 minutes with the dropping funnel which installed in the flask, and it dripped continuously with vigorous stirring of the contents.
플라스크 내용물의 온도를 50 ℃ 이하에 유지하면서, 교반을 더욱 2 시간 계속하여 무색 투명의 용액 (A)을 얻었다.Stirring was further continued for 2 hours, maintaining the temperature of the flask contents at 50 degrees C or less, and the colorless and transparent solution (A) was obtained.
한편, 다른 플라스크에 테트라이소프로폭시티탄(Aldrich사제) 204.2 g를 2 - 프로판올 100 g에 용해하고, 1몰 /리터의 질산 1 ml과 배위형성제로써 아세틸 100.1 g 의 혼합 용액을 30분 걸려서 적하하고, 짙은 적색의 용액 (B)을 얻었다.On the other hand, 204.2 g of tetraisopropoxycitane (manufactured by Aldrich) was dissolved in 100 g of 2-propanol in another flask, and a mixed solution of 1 ml of 1 mol / liter of nitric acid and 100.1 g of acetyl as a coordination agent was added dropwise over 30 minutes. And the dark red solution (B) was obtained.
용액 (B)를 용액 (A)가 있는 플라스크에 첨가하고, 1시간 실온으로 교반후, 환류 냉각기를 설치해서 열을 가하고 상압하에서 4시간 환류를 했다.The solution (B) was added to the flask with solution (A), and after stirring at room temperature for 1 hour, a reflux condenser was installed, heat was applied, and reflux was performed at atmospheric pressure for 4 hours.
이 용액을 채취하고, 테트라히드로퓨란으로 열배로 희석하고, 테트라히드로퓨란을 전달체로서 하여 굴절율 검출기가 부착된 겔 침투 크로마토그래피 장치를 써서 중량 평균 분자량을 측정했더니, 약 1,200이였다.The solution was collected, diluted 10 times with tetrahydrofuran, and the weight average molecular weight was measured using a gel permeation chromatography apparatus equipped with a refractive index detector using tetrahydrofuran as a carrier, which was about 1,200.
이 용액 100부를, 프로필렌글리콜모노메틸에테르아세테이트 50부로써 희석 용해해서 도포 액을 얻었다.100 parts of this solution was diluted and dissolved in 50 parts of propylene glycol monomethyl ether acetates, and the coating liquid was obtained.
이 도포액보로실리케이트 상에서 회전수 100 - 3000 rpm에서 도포 하고, 각 종 두께의 피막을 얻었다.It applied on this coating liquid borosilicate at rotation speed 100-3000 rpm, and obtained the film of each thickness.
수득된 피막을 250 ℃ 30분, 핫플레이트상에서 베이크해서, 투명 절연 막을 얻었다.The obtained film was baked on 250 degreeC 30 minutes on a hotplate, and the transparent insulating film was obtained.
수득된 피막의 특성은 표 1과 같다.The properties of the obtained film are shown in Table 1.
막의 두께는 에립소미터로, 가시광선 투과율은 UV 가시광 분광계를 써서 측정했다.The thickness of the film was measured by an lipometer and the visible light transmittance was measured using a UV visible light spectrometer.
크랙한계는, 회전수를 조정함으로써 얻어진 각종 두께의 막을 외관 검사하고, 크랙이 발생하지 않는 최대의 막두께를 정하였다.The crack limit inspected the film | membrane of various thickness obtained by adjusting rotation speed, and set the largest film thickness which a crack does not generate | occur | produce.
절연 파괴 내압과 리크 전류는, ITO를 스퍼터링 해서 얻은 기판을 별도로 준비하고, 수은 프로브와 아지렌트사제 CV, IV 측정기를 써서 측정했다.The breakdown breakdown voltage and the leak current were separately prepared by sputtering ITO and measured using a mercury probe and CV and IV measuring instruments manufactured by Azirent.
내열성은, 유리 기판상에 작성한 패턴을 질소 분위기중에서 가열하고, 백탁·황변 등의 외관상의 이상이나 막두께의 감소 유무로 판단하였다.Heat resistance heated the pattern created on the glass substrate in nitrogen atmosphere, and judged by the presence or absence of apparent abnormalities, such as cloudiness and yellowing, and reduction of the film thickness.
[실시예 2]Example 2
실시예 1의 페닐트리메톡시실란을, 3 -아크릴록시프로필트리에톡시실란234.3 g으로 바꾸고, 또한 금속알콕시드를 테트라이소프로폭시티탄에서 테트라부톡시지르코늄 383.7 g(Aldrich사제)에 바꾼 이외는, 실시예 1와 동일의 조건으로 합성하여 막을 제조하였다.Except having changed the phenyl trimethoxysilane of Example 1 into 234.3 g of 3-acryloxypropyl triethoxysilanes, and also changing the metal alkoxide to 383.7 g of tetrabutoxy zirconium (made by Aldrich) from tetraisopropoxycitane And synthesized under the same conditions as in Example 1.
결과는 표1과 같다. The results are shown in Table 1.
[실시예 3]Example 3
실시예 1의 페닐트리메톡시실란을, 비닐트리에톡시실란 149.3 g로 바꾸고, 금속알콕시드를 테트라이소프로폭시티탄에서 트리인프로폭시알루미늄 204.2 g (Aldrich사제)에 바꾸고, 배위형성제로써의 아세틸아세테이트를 아세트초산에틸 130.1 g 에 바꾼 이외는, 실시례 1와 동일의 조건으로 합성하여 막을 제조하였다.The phenyltrimethoxysilane of Example 1 was changed to 149.3 g of vinyltriethoxysilane, and the metal alkoxide was changed from tetraisopropoxytane to 204.2 g of triinpropoxyaluminum (manufactured by Aldrich) as a coordination agent. A membrane was prepared by synthesizing under the same conditions as in Example 1 except that acetyl acetate was changed to 130.1 g of ethyl acetate.
결과는 표1과 같다. The results are shown in Table 1.
[실시예 4]Example 4
실시예 1의 페닐트리메톡시실란을, 3 - 메타크리록시프로필트리메톡시실란 248.3 g으로 바꾸고, 금속 알콕시드를 테트라이소프로폭시티탄에서 테트라부틸주석 411.16 g(Aldrich사제)로 바꾼 것이외는, 실시예 1와 동일의 조건으로 합성하여 막을 제조하였다.Except for changing the phenyltrimethoxysilane of Example 1 to 248.3 g of 3-methacryloxypropyltrimethoxysilane and changing the metal alkoxide from tetraisopropoxycitane to 411.16 g of tetrabutyltin (manufactured by Aldrich), A film was prepared by synthesizing under the same conditions as in Example 1.
결과는 표1과 같다. The results are shown in Table 1.
표 1Table 1
상기의 표로서 알 수 있는 것은, 종래 발명의 문제점과는 달리, 막의 두께가 2-3 내지 5㎛가 되어도 크랙이 발생하지 않으며, 내열성에서도 300℃ 이상으로서 문제가 없는 바, 유용한 효과를 나타냄을 확인할 수 있다.As can be seen from the above table, unlike the problems of the conventional invention, cracks do not occur even when the thickness of the film is 2-3 to 5 µm. You can check it.
본 발명에 의하여 제조된 반도체 장치의 절연막 형성용 도포액 조성물은 전자디바이스에 도포하여 투명한 절연 피막을 형성 시 수 ㎛의 두께로 도포시에도 크랙이 생기지 않아 피막형성에 용이한 기술적 효과를 갖는다.The coating liquid composition for forming an insulating film of a semiconductor device manufactured according to the present invention does not have cracks even when applied to an electronic device to form a transparent insulating film with a thickness of several μm, thereby having an easy technical effect in forming a film.
또한, 본 발명에 의하여 생성된 절연피막은 실제 산업에서 응용가능하도록 300℃ 이상의 내열성을 갖는 것인 바, 고온에서도 작업이 가능한 효과를 갖는다.In addition, the insulating film produced by the present invention has a heat resistance of 300 ℃ or more to be applicable in the actual industry, it has an effect that can work at high temperatures.
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|---|---|---|---|---|
| JPH021778A (en) * | 1988-02-02 | 1990-01-08 | Hitachi Chem Co Ltd | Coating liquid for forming oxide coating film and production of oxide coating film |
| WO1996000758A1 (en) * | 1994-06-30 | 1996-01-11 | Hitachi Chemical Company, Ltd. | Material for forming silica-base coated insulation film, process for producing the material, silica-base insulation film, semiconductor device, and process for producing the device |
| KR19990062725A (en) * | 1997-12-02 | 1999-07-26 | 마쯔모또 에이찌 | Composition and film for film formation |
| KR20050030596A (en) * | 2003-09-25 | 2005-03-30 | 제이에스알 가부시끼가이샤 | Composition for forming film, process for preparing the same, material for forming insulating film, process for forming film and silica film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH021778A (en) * | 1988-02-02 | 1990-01-08 | Hitachi Chem Co Ltd | Coating liquid for forming oxide coating film and production of oxide coating film |
| WO1996000758A1 (en) * | 1994-06-30 | 1996-01-11 | Hitachi Chemical Company, Ltd. | Material for forming silica-base coated insulation film, process for producing the material, silica-base insulation film, semiconductor device, and process for producing the device |
| KR19990062725A (en) * | 1997-12-02 | 1999-07-26 | 마쯔모또 에이찌 | Composition and film for film formation |
| KR20050030596A (en) * | 2003-09-25 | 2005-03-30 | 제이에스알 가부시끼가이샤 | Composition for forming film, process for preparing the same, material for forming insulating film, process for forming film and silica film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2256147A1 (en) * | 2008-03-07 | 2010-12-01 | Central Glass Company, Limited | Thermosetting organic-inorganic hybrid transparent material |
| EP2256147A4 (en) * | 2008-03-07 | 2011-07-27 | Central Glass Co Ltd | Thermosetting organic-inorganic hybrid transparent material |
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