TW593438B - Silicone resin compositions having good solution solubility and stability - Google Patents
Silicone resin compositions having good solution solubility and stability Download PDFInfo
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Description
593438 五、發明說明(l) :關於具良好溶液溶解度之可溶性矽酮樹脂組合 眩 法。該石夕_樹脂用於生成具低介電常數之微 孔溥膜。 通常具有—組或多組模型化互邊平面層,該 、:自於電性連結形成積體電路(ic)之單獨電路元件。 lif in:般由絕緣薄膜或介電薄膜分隔。先前,用 化=虱相沈積(jVD)或電漿増強技術(pECVD)形成之二氧化 :m電缚膜所用之最常用材料。然㈤,由於電路元 件間之空間減少,此類氧化矽之相當高介 電常數不足以提供足夠電絕緣。 〇 為提供低於氧化;ε夕介雷舍* 為基礎之樹脂形成介電;:數;!料’頃發現用以彻 半彻形成之薄膜薄膜之實例為自聚(氫)倍 4,756,977號所述。雖妙此果/專利第3,6 1 5,272號及第 供更低介電常數。而且、亦此膜」匕=或膽〇氧化石夕提 和表面平面化,但此類,如增強間隙填充 更大。 、厚腠之介電常數卻被限制至約3或 我們知道,在需要I# 1 i593438 V. Description of the invention (l): About the soluble silicone resin combination glaze method with good solution solubility. The Shi Xi_resin is used to form a microporous rhenium film with a low dielectric constant. It usually has one or more sets of modeled mutual edge plane layers, which are: individual circuit elements that form an integrated circuit (ic) from electrical connections. lif in: Generally separated by an insulating film or a dielectric film. Previously, the most commonly used materials for the formation of dioxide: m electro-composite films using chemical = lice phase deposition (jVD) or plasma toughening (pECVD) techniques. However, due to the reduced space between circuit elements, the relatively high dielectric constant of this type of silicon oxide is insufficient to provide sufficient electrical insulation. 〇 In order to provide lower than the oxidation; ε 夕 介 雷 舍 * based resin to form a dielectric ;: number ;! An example of a thin film that is found to be completely formed is described in Self-polymerizing (hydrogen) times 4,756,977. Although this result is excellent / Patent No. 3,6 1 5,272 and No. provide a lower dielectric constant. In addition, this film is also used to enhance the surface planarization, but this type, such as enhanced gap filling, is larger. , The thickness of the dielectric constant is limited to about 3 or we know that I # 1 i
時,以上所討論絕;薄= 和信號延遲之IC,S 於1C尺寸不斷縮小,常數為-種重要因素。由 需要能夠提¥具低於3之八,ΙΛ常數重要增力”因此,非常 料及製造該材料之方法;另V數之以石夕為基,之樹脂材 低介電常數之以石夕氧貌為:夕卜非常需要提供高抗裂、 法。而且,使此類“ί;;ΓΓ製造lb”脂之方 /礼烷為基礎之樹脂由標準處理技術At the same time, the above discussion must be absent; for thin = and signal delay ICs, S is constantly shrinking in size, and the constant is an important factor. Since it is necessary to be able to raise the value below 3/8, the IΛ constant is an important boost. Therefore, the method of manufacturing this material is very expected; the V number is based on Shi Xi, and the resin material with low dielectric constant is Shi Xi oxygen. It looks like: Xi Bu is very in need of providing high crack resistance and method. Moreover, this kind of "ί; ΓΓ manufacturing lb" fat cube / leane-based resin is processed by standard technology
第6頁 593438 發明說明(2) 提供低介電常數薄膜非常合乎需要。 我們知道,固態薄膜之介電常數隨薄膜材料之密度 ^降低n開發用於半導體元件之微孔絕 進仃相當多工作。 寸眠要 ,國專利第5, 49 4, 85 9號描述一種用於積體電路結構之 二二電常數絕緣薄膜及製造該層之方法。孔性層係藉在一 ^ =構上沈積組合層形成,該組合層包括絕緣基質材料 過轉化處理時轉化成氣體之物質。釋放氣體留下旦有 二ίΐί層介電常數之絕緣材料孔性基質。基質形成材料 &马虱化矽和在經過轉化處理時能夠轉化成氣體之 枓,例如碳。 ^ 大、國,利第5, 77 6, 990揭示一種具小於丨00納米(nm)孔徑 解^ ^絕緣泡沫聚合物,該泡沫聚合物係藉由以高於可分 基=二^之分解溫度加熱一種共聚物製造,該共聚物包括 二永σ物和可熱解聚合物。所述共聚物為不含矽原子 有機聚合物。 ,界知識產權組織專利第98/4 972 1號描述一種於基材上 形烕納孔公φ、么ρ 片 ;丨電塗層之方法,該方法包括以下步驟,混合烷 材上,和洛劑組合物及選用之水,使該混合物沈積於基 时A 同時蒸發至少部分溶劑;將該基材放入密閉室中, 將该室% $ ; u I低於大氣壓壓力,使基材於低於大氣壓壓力暴 路於7jC某* …、乳’然後暴露於鹼蒸氣。 取5本特許公開專利(HEI)第1 0-287746號教示自具有有機 Γ基之以矽氧烷為基礎樹脂製備孔性薄膜,且該有機取Page 6 593438 Description of the invention (2) It is highly desirable to provide a film with a low dielectric constant. We know that the dielectric constant of a solid-state thin film decreases with the density of the thin-film material. ^ The development of micropores for semiconductor devices has significantly reduced work. Cong Mian Yao, National Patent No. 5, 49 4, 85 9 describes a two-constant dielectric film for integrated circuit structures and a method for manufacturing the same. The porous layer is formed by depositing a composite layer on a ^ = structure, and the composite layer includes a substance that is converted into a gas when the insulating matrix material undergoes a conversion treatment. The released gas leaves a porous matrix of insulating material with a dielectric constant of two layers. Matrix forming materials & horse lice silicon, and plutonium, such as carbon, which can be converted into gas when subjected to a conversion treatment. ^ Da, Guo, Li No. 5, 77 6, 990 reveals a solution with a pore size less than 00 nanometers (nm) ^ ^ insulating foam polymer, the foam polymer is decomposed by higher than separable = 2 ^ Temperature-coated manufacturing of a copolymer comprising a di-permanent sigma and a pyrolysable polymer. The copolymer is an organic polymer containing no silicon atoms. , World Intellectual Property Organization Patent No. 98/4 972 No. 1 describes a method of forming pores and holes on the substrate, and a method of electrocoating. The method includes the following steps: Agent composition and selected water, so that the mixture is deposited on the base A while evaporating at least a part of the solvent; the substrate is placed in a closed chamber, the chamber%; u I is lower than atmospheric pressure, so that the substrate is low Burst at 7jC *, milk 'at atmospheric pressure and then expose to alkali vapor. 5 patents (HEI) No. 10-287746 teaches to prepare a porous film from a siloxane-based resin having an organic Γ group, and the organic
第7頁 593438 五、發明說明(3) 代^係於2 5 0 °c或更高溫度氧化。在該文件中,能夠於 25〇 C或更高溫度氧化之所用有機基團包括經取代和未經 取代之基團’其實例為3, 3, 3—三氟丙基、石—苯乙基、第 二丁基、2-氰乙基、苄基和乙烯基。 為減小薄膜之密度和介電常數,自然化學刊(J· n Chem·)邁可斯巴等人(Mikoshiba)報告一種在聚(甲基半件 石夕氧燒)薄膜中產生埃大小孔之方法。其中將承載甲基(』 甲石夕烧氧基甲矽基)單元和烷基(三甲矽烷氧基甲矽基)單 元之共聚物旋塗於基材上,並以2 5 〇 °c加熱,以提供剛性 矽氧烷基質。然後,以45〇 t至5〇〇 t加熱薄膜,以熱移除 不t疋基團’留下相當於取代基大小之孔洞。據調查,^ 不穩定取代基為三氟丙基、氰乙基、苯乙基及丙基。 世界知識產權組織專利第98/4 794 5號揭示一種使三氯矽 烷和有機二氯矽烷反應生成有機氫矽氧烷聚合物之方法, 該聚合物具有籠構型和約〇.1至4〇莫耳%含碳取代基,據報 告,自該聚合物生成之樹脂具有小於3之介電常數。 發明之+目的包括提供一種矽酮樹脂,該樹脂溶於有機 =別(如甲苯)’具有可用溶液貯存期,而且適合在電子元 ^ T f無龜裂電絕緣薄膜。另—目的*提供—種在塗於 夠經加熱生成具窄孔徑大小分布及低介電常數 上(加半導體元件)形成具小於2介雷誉 膜。 、J ;丨電吊數之微孔無龜裂薄 本發明係關係於具良好溶液这紘痒 /合狀,合解度之可溶矽酮樹脂組合Page 7 593438 V. Description of the invention (3) Generation ^ is oxidized at 250 ° C or higher. In this document, the organic groups used which can be oxidized at 25 ° C or higher include substituted and unsubstituted groups. Examples are 3, 3, 3-trifluoropropyl, stone-phenethyl , Second butyl, 2-cyanoethyl, benzyl and vinyl. In order to reduce the film's density and dielectric constant, the journal of Natural Chemistry (J · n Chem ·) Mikoshiba et al. (Mikoshiba) reported a kind of Angstrom size produced in poly (methyl half-stone oxy-fired) film Hole method. Wherein, a copolymer carrying a methyl (X-methysilyloxysilyl) unit and an alkyl (trimethylsiloxysilyl) unit is spin-coated on a substrate, and heated at 250 ° C. To provide rigid siloxane. Then, the film is heated at 45 to 500 t to thermally remove the non-t 'group, leaving a hole corresponding to the size of the substituent. According to investigations, the unstable substituents are trifluoropropyl, cyanoethyl, phenethyl and propyl. World Intellectual Property Organization Patent No. 98/4 794 5 discloses a method for reacting trichlorosilane and organic dichlorosilane to form an organohydrosiloxane polymer. The polymer has a cage configuration and about 0.1 to 4. Mol% carbon-containing substituents are reported to have a dielectric constant of less than 3 for resins generated from the polymer. The + object of the invention includes the provision of a silicone resin which is soluble in organic solvents (such as toluene), has a usable solution storage period, and is suitable for crack-free, electrically insulating thin films of electronic elements. Another purpose is to provide a film with a diameter of less than 2 dielectric layers, which is coated on a substrate with a narrow pore size distribution and a low dielectric constant (plus a semiconductor element). , J; 丨 The number of micropores without cracks in the electric suspension number is small. This invention relates to a combination of soluble silicone resins with a good solution such as itching / combination and degree of solution.
第8頁 593438 五'發明說明(4) 製備方法。該矽酮樹脂用於生成具低介電常數之微 本發明一個具體實施例為溶於標準溶劑且 施加介電塗層之㈣樹脂。她樹脂包括一種』牛 解催化劑及(f)反應產物所用之有機溶劑存 應產物,該混合物包括(A) 15 — 70莫耳%由式 描述之四烧氧基石夕烧,其中(1)各R1為獨立經選擇 二^至^個碳原子之烧基;(B) 12_6〇莫耳%由式(2)HsiX3 η:石夕烷’其中各乂為獨立經選擇之可水解取代基; 7〇莫耳%由式(3)R2Si (OR3)描述之有機二烧氲美 =其中…含8至24個碳原子之煙基或 石反原子烴鏈之經取代烴基,各γ為獨立經選擇包 6 原子之烷基,其中該莫耳百分數係以組分 總莫耳數為基準。 之 組分(A)為由式(1)描述之四烷氧基矽烷。本人出乎預料 。毛現存在佔組分(A) + ( B) + (C)總莫耳數1 5莫耳%至7 〇莫耳 %之組分A對有機溶劑中矽酮樹脂之溶解度和安定性至關重 要。如果組分(A)之莫耳%在所述範圍外,該矽酮樹脂將至 少部分不溶於形成樹脂溶液塗料之有機溶劑。組分(a )之 莫耳%較佳在25莫耳%至5〇莫耳%範圍内。在式(1)中,各R1 為獨立經選寮含i至6個碳原子之烷基。例如,^為甲基、 乙基 丁基、第二丁基和己基。組分A較佳為四甲氧基矽 烧或四乙氧基矽烷,因為其易於獲得。 組分(B)為由式(2)描述之氫矽烷。組分(β)係以佔Page 8 593438 Five 'invention description (4) Preparation method. The silicone resin is used to generate micro-particles having a low dielectric constant. A specific embodiment of the present invention is a rhenium resin dissolved in a standard solvent and having a dielectric coating applied. Her resin includes a catabolism catalyst and (f) an organic solvent storage product used in the reaction product. The mixture includes (A) 15-70 mole% of tetrakisoxy oxylithium as described by the formula, where (1) each R1 is an independently selected alkyl group of 2 ^ to ^ carbon atoms; (B) 12-60 mole% by formula (2) HsiX3 η: Shixane 'wherein each 其中 is an independently selected hydrolyzable substituent; 7 〇mole% organic di-smoke as described by the formula (3) R2Si (OR3) = wherein ... a substituted hydrocarbon group of a nicotinyl or stone antiatomic hydrocarbon chain containing 8 to 24 carbon atoms, each of which is independently selected A 6 atom alkyl group, where the mole percentage is based on the total moles of the component. The component (A) is a tetraalkoxysilane described by the formula (1). I was unexpected. The existence of component A, which accounts for the total moles of component (A) + (B) + (C), is between 15 mol% and 70 mol%. The solubility and stability of silicone resin in organic solvents are critical. important. If the mole% of component (A) is outside the range, the silicone resin will be at least partially insoluble in the organic solvent forming the resin solution coating. The mole% of component (a) is preferably in the range of 25 mole% to 50 mole%. In formula (1), each R1 is an independently selected alkyl group containing i to 6 carbon atoms. For example, ^ is methyl, ethylbutyl, second butyl, and hexyl. Component A is preferably tetramethoxysilane or tetraethoxysilane because it is easily available. Component (B) is a hydrosilane described by formula (2). The component (β) is
111 593438111 593438
五、發明說明(5)V. Description of the invention (5)
(α) + (Β) + (〇總莫耳數12莫耳%至60莫耳%之用量加至該混 a物。以超出所述範圍加入組分(Β)能夠限制所得矽酮樹 脂在有機溶劑中之溶解度。組分(Β)較佳以15莫耳%至40莫 耳%之用量加至該混合物。在式(2)中,χ為可水解取代 基。X為任何能夠在水存在及所述方法條件下自矽原子水 解而且水解時不會不利作用矽_樹脂之溶 之取代基。可水解取代基之實例包括幽、烧氧 基。X較佳為含i至6個碳原子之烷氧基。組 三氣残、三甲氧基^或三乙氧基钱m 基石夕烧和三乙氧基石夕烧。(α) + (Β) + (〇Total moles from 12 mole% to 60 mole% is added to the mixture a. Adding component (B) beyond the stated range can limit the obtained silicone resin to Solubility in organic solvents. Component (B) is preferably added to the mixture in an amount of 15 to 40 mole%. In formula (2), χ is a hydrolyzable substituent. X is any water-soluble substituent. Substituents that are hydrolyzed from the silicon atom under the conditions of the method and that do not adversely affect the solubility of the silicon resin when hydrolyzed. Examples of hydrolyzable substituents include hydrogen and alkoxy. X preferably contains i to 6 carbons Atomic alkoxy groups. Groups of tri-gas residues, trimethoxy ^ or triethoxy groups, and base groups.
/組分(C)為由式(3)描述之有機三烷氧基矽烷。組分(c) ,以佔組分(人)+ (^ + ((:)總莫耳數15莫耳%至7〇莫耳%之用 ,加至該混合物。組分(C)重要提供自矽_樹脂形成微孔 薄膜之機制。確切而言,組分(c)包括非經取代或經取代 烴基。R2在可加熱製程中經熱解自矽原子除去,由之在所 得矽酮樹脂中產生微孔。因此,組分(C)加至該混合物之 用里係用於控制所得石夕酮樹脂在加熱固體及熱解除去r2取 代基之孔隙度。通常,組分(C)之用量低於15莫耳%將導致 石夕鋼樹脂塗層孔隙度太小,難以給予材料最佳介電性能。 而且在溶劑中溶解度差,而組分(C)用量高於70莫耳%將導 致樹脂在溶劑-中具有受限溶解度及物理性能不足(如在基 材上用作孔性塗層時之耐裂性能)。組分(c )較佳以丨5莫 〇/0至40莫耳%範圍加至該混合物。 在式(3)中,為含8至24個碳原子之烴基或包含8至24/ Component (C) is an organic trialkoxysilane described by formula (3). Component (c) is added to the mixture to account for component (human) + (^ + ((:) total moles 15 to 70 mole%). Component (C) is important to provide Mechanism of forming microporous film from silicon resin. To be precise, component (c) includes non-substituted or substituted hydrocarbon groups. R2 is removed from silicon atoms by pyrolysis in a heatable process, and is used in the resulting silicone resin. Micropores are generated in the mixture. Therefore, the component (C) is added to the mixture to control the porosity of the obtained lithone resin in heating the solid and pyrolyzing the r2 substituent. Generally, the component (C) If the amount is less than 15 mol%, the porosity of the resin coating of Shixi Steel will be too small to give the material the best dielectric properties. Moreover, the solubility in the solvent is poor, and the amount of component (C) above 70 mol% will Causes the resin to have limited solubility in solvents and insufficient physical properties (such as crack resistance when used as a porous coating on a substrate). Component (c) is preferably 5 Mo 0/0 to 40 Mo % Range is added to the mixture. In the formula (3), a hydrocarbon group containing 8 to 24 carbon atoms or containing 8 to 24
第10頁 593438 五、發明說明(6) :碳原子烴鏈之經取代烴基。R2可為線性、分 基。經取代烴基可用以下取代基取代。如齒、由 m) 土 ’描述之聚氧化稀基('經中m和父均^正整 為至之正整數)。院氧基、醯氧基、酿某、烷 =羰基及三烷基曱矽氧基。R2較佳為含8至 "· 辛?含?6至2。個碳原子之直鍵烧基更= 基、乙氧基辛基、壬基二〒乳暴辛 甲其田丄 土夭基十一烷基、十六烷基、三 土甲夕乳十六烷基、十八烷基及二十二烷基。 其在ι^Ι3,)中,各R3為獨立經選擇含1至6個碳原子之烷 土。R為(例如)曱基、乙基、丙基、異丁 及己基。R3較佳為甲基或乙基。 丁基庚基 三ΐ 表之有機三烧氧基石夕⑦之明確實例包括辛基 烷、二辛基三甲氧基矽烷、十八烷基三甲氧基矽 有機二甲氧基矽烷及十二烷基三乙氧基矽烷。該 其機 乳基錢較佳選自由辛基三乙氧基錢、十八燒 基二甲氧基矽燒和一田条丄 三饮ft里A W ,、烷基二甲乳基夕烷組成之群。有機 ^几土夕、元之進一步實例包括由以下各式描述之化合 (CHJCHOn-〇-CH2CH2)Si(OMe)3。 (ch3(ch256c(=〇)一(CH2)(CH2)Si(0Me)3 〇 产 (CH3(CH2)i7〜〇 —C(=〇)-CH2CH2)Si(OMe)3 及 義(CKCDfCbO) 一〇 一 CH2CH2)Si(0Me)3,其中Me 為甲Page 10 593438 V. Description of the invention (6): A substituted hydrocarbon group of a carbon atom hydrocarbon chain. R2 can be linear or split. The substituted hydrocarbon group may be substituted with the following substituents. Such as the teeth, the polyoxidized dilute base described by m) soil ('m and the parent are ^ positive integers to the positive integer). Alkoxy, alkoxy, alkoxy, alkane = carbonyl and trialkyl sulfo. R2 preferably contains 8 to " · Xin? Contains? 6 to 2. A straight-bonded alkyl group with more than one carbon atom is equal to a radical, an ethoxyoctyl group, a nonyl dioctyl octadecyl group, an octadecyl undecyl group, a cetyl group, and a trioctyl hexadecyl group. , Octadecyl and behenyl. In ^^ 3,), each R3 is an independently selected alkane containing 1 to 6 carbon atoms. R is, for example, fluorenyl, ethyl, propyl, isobutyl, and hexyl. R3 is preferably methyl or ethyl. Specific examples of the organic trisalkanesene group of butylheptyltrifluorene include octylalkane, dioctyltrimethoxysilane, octadecyltrimethoxysilylorganodimethoxysilane, and dodecyltriethyl Oxysilane. The organic milk base is preferably selected from the group consisting of octyltriethoxy, octadecyldimethoxysilicon, and AW's AW, and alkyl dimethyllactylxane group. Further examples of organic compounds and compounds include compound (CHJCHOn-O-CH2CH2) Si (OMe) 3 described by the following formulas. (ch3 (ch256c (= 〇)-(CH2) (CH2) Si (0Me) 3 〇Product (CH3 (CH2) i7 ~ 〇-C (= 〇) -CH2CH2) Si (OMe) 3 and CKCDfCbO)- 〇-CH2CH2) Si (0Me) 3, where Me is forma
第11頁 593438 五、發明說明(7) 入、f,(D)為水。組分(D)較佳以足夠量加入,以本所 連接組分⑴、⑻及(〇之石夕原子之可水解"基貝團元 而不曰過量大得產生減慢反應之雙相混合物 土 佳為每莫耳組分(A)、(B)和(C)使用】.4至6莫”里較 2. 5至4.5莫耳之用量加入甚佳(以相同基準)莫耳數。水以 組分(E)為水解催化劑,且可為任 化取代基“夕原子水解之技藝上已:二在^存, :。該水解催化劑可為無機驗,如或 ,催化劑亦可為無機酸,如氯化氫、納。 早獨將水解催化劑加至反應混合物,或者在組八^可 齒矽烷時,至少部分就地產生。較佳水解催化:()為二 'Τ=(β)為三氯侧,可至少部分就地產生 於組分(A)、(Β)及(C)之連接石夕 】=)了為任何利 最佳用量取決於催化劑之化學=\基,水解之用量, 0 0= 5一:Λ每莫耳組分(Α)、⑻和⑹使用 同一 i準; 催化劑用量較佳為G.l至"莫耳(以 4 ΓΓΛ反物應於產Λ所用之有㈣ ,夠使反應產物於其中形成均相機 方fe >谷劑[如甲本、二甲苯、J,3 卞 異丁酯、三氟曱苯、丙美策、’石’&一甲本米、/、丁酸 氣三氟甲苯及辛烧。有二溶 $,丁醋、丁酸丙酿、對 钱/合^之用Ϊ應足以產生反應混合Page 11 593438 V. Description of the invention (7) Into, f, (D) is water. The component (D) is preferably added in a sufficient amount, and the hydrolyzable " kibe group " radicals of the Shixi atom of the linked components 连接, ⑻ and (0) are not excessively large to produce a biphasic phase that slows down the reaction. Mixtures are preferably used per mole of components (A), (B), and (C)]. 4 to 6 moles "is better than the amount of 2.5 to 4.5 moles (on the same basis). Water uses the component (E) as a hydrolysis catalyst, and may be an arbitrary substituent. The technique of the atomic hydrolysis has been: two in existence, the hydrolysis catalyst may be inorganic, such as or, the catalyst may also be Inorganic acids, such as hydrogen chloride, sodium. Early addition of a hydrolysis catalyst to the reaction mixture, or at least partially generated in place when a group of ^ dentable silanes. Preferred hydrolysis catalysis: () is two 'T = (β) is The trichloride side can be generated at least partially in situ from the connecting stones of the components (A), (B) and (C).] =) For any benefit, the optimal amount depends on the catalyst's chemistry. , 0 0 = 5 a: Λ per mole component (Α), ⑻ and ⑹ use the same standard; the amount of catalyst is preferably Gl to " Moore (with 4 ΓΓΛ reaction products should be produced in Λ is used for ㈣, which can make the reaction products form homogeneous squares & grains [such as methylben, xylene, J, 3 卞 isobutyl ester, trifluoroxobenzene, propylmetraz, 'stone' & a Gelben rice, /, butyric acid, trifluorotoluene, and sauté. There are two soluble solvents, butyric acid, butyric acid, and acetic acid. It should be sufficient for reaction mixing.
$ 12頁 593438 五、發明說明(8) = 容液。該有機溶劑—般佔組分⑴至(F)總重量7〇 至95重篁%,較佳85至95重量%。 在製造含刪脂巧應產物之較佳方法中,首先將組 έ八、(c)和(F)/tc*合成第—混合物。然後(在混合 作為:入刀』⑻力一混合物、二者可單獨加入或 =二物,入,以一形成反應產•。生成反應產物係於15 3 Λ她圍溫度貫 佳在環境溫度。在該較佳方 …元成所得反應產物後,將揮發物在減壓下自反應產 :移除’ u分離樹脂溶液。此類揮發物包括副產物醇、過 :水、催化劑及溶劑。如需要’彳自樹脂溶劑除去全部溶 劑’以形成固冑。當除去所有溶劑分離樹脂固體,樹脂溶 液溫度應保持於60 °C以下,較佳在30 t至5〇艺範圍内。過 熱可此導致不溶樹脂生成。若需要,可經一次或多次水清 洗以臨時相分離自反應產物分離催化劑和醇副產物,以= 收溶於溶劑矽酮溶液。 上述含石夕_樹脂之反應產物含Si-OH官能度,且可含 Si -OR3官能度,其中r3如前所述,該矽_樹 至30 莫耳 %Si〇H 及0至10 莫耳 %Si_0R3。 1 ' "3l° 本發明之進一步具體實施例為增加上述所製備含石夕酮樹 月曰之反應產物之分子罝及改良貯存安定性之方法(以後稱 為”增重方法0。增重方法包括,(i)使矽酮樹脂在選用之 縮合催化劑存在下以1 〇至6 〇重量%於溶劑中形成溶液, (i i)以足夠溫度加熱該溶液,使該石夕_樹脂縮合至 1 0 0, 0 0 0至40 0, 0 0 0之重均分子量,及(iU)中和該石夕酮樹$ 12 pages 593438 V. Description of the invention (8) = Liquid storage. The organic solvent generally accounts for 70 to 95% by weight, preferably 85 to 95% by weight, based on the total weight of components VII to (F). In a preferred method for making fat-removing products, the first mixtures (c) and (F) / tc * are first synthesized. Then (in the mixing as: entering the knife), a mixture of the two can be added separately or = two, and the reaction product is formed by one. The reaction product is generated at 15 3 Λ her ambient temperature is good at ambient temperature. In the preferred method, after the reaction product is obtained, the volatiles are separated from the reaction product to remove the resin solution under reduced pressure. Such volatiles include by-product alcohols, water: catalysts, and solvents. It is necessary to 'remove all solvents from the resin solvent' to form solids. When all the solvents are removed to separate the resin solids, the temperature of the resin solution should be kept below 60 ° C, preferably within the range of 30 to 50 ° C. Overheating can cause this Insoluble resin is formed. If necessary, the catalyst and alcohol by-product can be separated from the reaction product by temporary phase separation after one or more water washings, so as to = dissolve in the solvent silicone solution. -OH functionality, and may contain Si -OR3 functionality, where r3 is as previously described, the silicon-tree to 30 mole% SiOH and 0 to 10 mole% Si_0R3. 1 '" 3l ° The present invention A further specific embodiment is to add the above Preparation of molecular compounds containing the reaction product of syringone, and methods for improving storage stability (hereinafter referred to as "weight-increasing method 0." Weight-increasing methods include, (i) making the silicone resin in the presence of the selected condensation catalyst A solution is formed in a solvent at 10 to 60% by weight, and (ii) the solution is heated at a sufficient temperature to condense the resin to a weight-average molecular weight of 10, 0, 0 to 40, 0, 0 0 , And (iU) to neutralize the stone ketone tree
第13頁Page 13
593438 五、發明說明(9) 一 脂之溶劑溶液。在本方法之步驟(丨)中,該矽酮樹脂較佳 以2 0至3 0重量%存在於該有機溶劑。該有機溶劑可為任何 上述之有機溶劑。於步驟(i)加入之選用縮合催化劑為任 何上述形成反應產物所用水解催化劑之酸和鹼。較佳縮合 催化劑為佔樹脂固體5至200重量%ppm濃度之氯化氫。該縮 合催化劑更佳為佔樹脂固體1〇至5〇重量ppm濃度之氯化 氫0 於步驟(1 1 )加熱矽酮樹脂溶液之溫度係自5 〇艺至該溶液 之回流溫度二在一種較佳方法中,該矽酮樹脂之溶液係以 回流增加重量平均分子量。在步驟(i i )巾,較佳將該溶液 加熱,使該矽酮樹脂在加熱後具有15〇,〇⑽至25〇,〇⑽之 量!均分子量:?方法之步驟⑴i)係中和矽_樹脂之溶 劑溶液。巾和係藉用一或多部分水清洗該溶液實現,或者 Ϊ劑,將矽_樹脂再溶於一或多部分有機溶 劑、。用於中和步驟之溶劑為任何上述有機溶劑。 為進一步改良經中和矽_樹脂之溶液安定性,將 脂溶於有機溶劑或有機溶劑之人 设 ^ A <汁匕σ物 並加入佔石夕0¾樹 月曰、溶 >彳和水總重量〇. 0 5至〇 4重# y j ^ 基準。.i至。.25重量%水。=重二7卜佳加入佔同- $免、曰人輪h , 該有機洛劑為任何上述有機溶劑 或其此3物,較佳溶劑為異丁酸異丁酯。 該矽酮樹脂在電子元株以^n 常數薄膜,# IT T _/· Α β如積體日日片)特別角作低介電 :“轨:t 中用作填充物。該矽酮樹脂經固 步具體實施例係關於孔性本毛月之進 /】W月曰和孔性矽酮樹脂薄膜及 593438 五、發明說明(ίο) 其製造方法。 明確而言’本發明之進—步具體實施例係關於形成納孔 矽酮樹脂之方法。"納孔"指具小於2 〇納米孔之矽酮樹脂。 本發明之一個杈佳具體實施例為含矽酮樹脂納孔塗層之電 子晶;在該具體實施例中,該納孔塗層具有G. 3納米至2 納米直控。如果為固體,則將該包含石夕嗣樹脂之反應產物 溶解及稀釋於上述有機溶劑,異丁酸異丁酯和菜3 5一 三甲苯)為形成塗料溶液之較佳溶劑。有機溶劑中石夕酮 脂之濃度對本發明不特別關冑,可為溶解㈣且對塗覆製 ,所用液提供可接受流動性能之濃度。有機溶劑中矽酮 樹脂之浪度較佳為1。至2 5重量%。石夕酮樹脂係藉於電子元 件上形成塗層之標準方法塗於基片上,如旋塗、流塗、浸 塗和喷塗。然後,較佳將具矽嗣樹脂塗層之基片在惰性氣 氛以足夠溫度加熱,以固化矽酮樹脂塗層以及自矽原子熱 解R2基團。加熱可作為單步方法或雙步方法進行。在雙步 方法中。首先將矽酮樹脂在惰性氣氛以足夠溫度加埶固 化,。但不顯著自矽原子熱解R2基團。該溫度一般自20艺至 =。然後將經固化石夕嗣樹脂進一步加熱,其溫度大於 C,取尚至小於矽酮樹脂聚合物骨架裂解之溫度或基 =上R2基團自石夕原子熱解產生不理想作用之溫度。熱解步 =般較佳在高於35(rc至6G(rc進行,最佳術至55〇t。 rrt法中,固化石夕綱樹脂和自石户原子熱冊基團係藉由 :熱具矽酮樹脂之基材同時進行’其溫度大於35〇它,最 间至小於矽酮聚合物骨架裂解之溫度或對基材產生不利影 593438 五、發明說明(11) 響之溫度。單步驟加熱一般較佳在大於35〇 t至6〇 進行’最佳在40(TC至55〇t。 皿度 於基材上形成納孔塗層之方法(單步驟或雙步驟加熱 法)較隹在惰性氣氛中進行。因為存在氧能夠氧化§丨咄鍵 及增加薄膜中殘餘矽醇含量,導致矽酮樹脂介電常數辦 加,所以惰性氣氛較為理想。然而,如果需要,可在^ 中存在少量氧化劑(如氧),以適應所得納孔矽酮樹脂之性 能。惰性氣氛為技藝上所熟悉,如氬、氦或氮氣。 由上述方法形成之納孔矽酮樹脂特別適合在電子元件上 (如整合晶片)用作低介電常數薄膜。以本方法製備 矽酮樹脂塗層較佳具有小於2之介電常數。亦可藉標準 法以顆粒形態製造此等納孔石夕_樹月旨,如嘴霧乾燥:上述 產生納孔之加熱方法,用於色譜柱中填充物及其它使用孔 性材料之場合。 以了實例係以說明本發明之方法提供。在各實例中,所 有份數均為重量份數,莫耳%係以組分(八)+ (]6) + ((:)之總莫 耳數為基礎。分子量係作為重量平均分子量報告,且由凝 膠滲透色譜法(GPC)用甲苯流動相及聚苯乙烯標準樣校準* 進行測定。 -樣品 1 -1 $ 1 - izi 為製備矽酮樹脂,在玻璃容器中以表i所示. 述組分(A)、(B)、(C)及(F): 用里此5下 (A)四乙氧基矽烷,(3)三乙氧基矽烷, (C)十八烧基三曱氧基矽烷及(F)曱基-異丁基酮(ΜΙΒΚ)593438 V. Description of the invention (9) A lipid solvent solution. In step (丨) of the method, the silicone resin is preferably present in the organic solvent at 20 to 30% by weight. The organic solvent may be any of the above-mentioned organic solvents. The optional condensation catalyst added in step (i) is the acid and base of any of the hydrolysis catalysts used to form the reaction product described above. A preferred condensation catalyst is hydrogen chloride in a concentration of 5 to 200% by weight of the solids of the resin. The condensation catalyst is more preferably hydrogen chloride at a concentration of 10 to 50 ppm by weight of the resin solids. The temperature for heating the silicone resin solution in step (1 1) is from 500 to the reflux temperature of the solution. However, the solution of the silicone resin is added to increase the weight average molecular weight by reflux. In step (i i), the solution is preferably heated so that the silicone resin has an amount of 150,000 to 250,000 after heating! Average molecular weight:? Step (i) of the method is a solvent solution that neutralizes the silicon resin. Towels are made by washing the solution with one or more parts of water, or tincture, and redissolving the silicone resin in one or more parts of the organic solvent. The solvent used in the neutralization step is any of the above-mentioned organic solvents. In order to further improve the stability of the solution of the neutralized silicon resin, the person who dissolves the fat in an organic solvent or an organic solvent sets ^ A < Juice, and adds Zhan Shixi 0¾ tree month, soluble > 彳 and water Total weight 0.05 to 04 weight # yj ^ benchmark. .i 至。 To. .25% by weight of water. =============================================================================== The organic solvent is any of the above organic solvents or three thereof, and the preferred solvent is isobutyl isobutyrate. The silicone resin has a thin film of ^ n constant film, # IT T _ / · Α β (such as integrated solar panels) with a special angle for low dielectric: "Orbital: t is used as a filler. The silicone resin The specific example of the solid step is about the progress of the pores of this hair month /] W Yueyue and pores of the silicone resin film and 593438 V. Description of the invention (ίο) The manufacturing method. Specifically, 'progress of the invention-step The specific embodiment relates to a method for forming a nanoporous silicone resin. &Quot; Nanoporous " refers to a silicone resin having less than 20 nanometer pores. A preferred embodiment of the present invention is a nanoporous coating containing a silicone resin. Electronic crystal; in this specific embodiment, the nanoporous coating has G. 3 nanometers to 2 nanometers direct control. If it is a solid, then the reaction product containing Shi Xiyu resin is dissolved and diluted in the above organic solvent, Isobutyl isobutyrate and chlorotrimethylbenzene are the preferred solvents for forming coating solutions. The concentration of lithone ester in organic solvents is not particularly critical to the present invention, and can be dissolved and used for coating. Provides acceptable concentration of flow properties. The silicone resin in organic solvents The degree is preferably 1. to 25% by weight. The lithone resin is applied to a substrate by a standard method of forming a coating on an electronic component, such as spin coating, flow coating, dip coating, and spray coating. The substrate with a silicon resin coating is heated in an inert atmosphere at a sufficient temperature to cure the silicone resin coating and pyrolyze the R2 groups from the silicon atoms. Heating can be performed as a single step method or a two-step method. In a two-step method In the method, the silicone resin is first cured at a sufficient temperature in an inert atmosphere, but the R2 group is not significantly pyrolyzed from the silicon atom. The temperature is generally from 20 ° C to =. Then, the cured stone resin is further heated. , Whose temperature is greater than C, which is still lower than the temperature at which the silicone resin polymer skeleton is cracked or the radical = the temperature at which the R2 group produces an undesired effect from the pyrolysis of the Shi Xi atom. The pyrolysis step = generally better than 35 (rc to 6G (rc, the best operation to 55 ot.) In the rrt method, the curing of the Shixigang resin and the self-heating group of the Ishido atom is performed simultaneously by: heating the base material of the silicone resin. The temperature is higher than 35 ° C, and the temperature is lower than the temperature at which the silicone polymer framework cracks or The substrate has an adverse effect 593438 V. Explanation of the invention (11) The temperature of the invention. Single-step heating is generally preferred to be performed at a temperature of greater than 350,000 to 60, and the best is at 40 (TC to 550,000). The method of forming a nanoporous coating (single-step or two-step heating method) is performed more in an inert atmosphere. Because the presence of oxygen can oxidize the bond and increase the residual silanol content in the film, the dielectric constant of the silicone resin is caused. Add, so the inert atmosphere is ideal. However, if necessary, a small amount of oxidant (such as oxygen) can be present in ^ to adapt the properties of the resulting nanoporous silicone resin. The inert atmosphere is familiar to the art, such as argon, helium or nitrogen The nanoporous silicone resin formed by the above method is particularly suitable for being used as a low-dielectric-constant film on an electronic component (such as an integrated wafer). The silicone resin coating prepared by this method preferably has a dielectric constant of less than 2. These nanopores can also be manufactured in the form of particles by standard methods, such as mouth mist drying: the above-mentioned heating method to generate nanopores is used for packing in chromatographic columns and other occasions where porous materials are used. Examples are provided to illustrate the method of the invention. In each example, all parts are parts by weight, and mole% is based on the total mole number of component (eight) + (] 6) + ((:). Molecular weight is reported as weight average molecular weight, It was determined by gel permeation chromatography (GPC) with toluene mobile phase and polystyrene standard calibration. * Sample 1 -1 $ 1-izi is a silicone resin prepared in a glass container as shown in Table i. The components (A), (B), (C) and (F): 5 times (A) tetraethoxysilane, (3) triethoxysilane, (C) octadecyltriazine Ethoxysilane and (F) fluorenyl-isobutyl ketone (ΜΙΒΚ)
第16頁 593438 五、發明說明(12) 和甲苯之混合物(重量比為8 5 : i 5 )。 將(D )水和(E )氯化氫之混合物加至該混合物,其用量如 表1所示’在樣品1-;[至中,組分(c)之重量份數為1。 將所得反應產物在減壓下以6 〇它吸除揮發物。完全吸除 後’將8 · 3克甲基加至1 · 7克固態矽酮樹脂,經2 4小時檢測 所得固態矽酮樹脂對曱苯之溶解度。如果形成澄清溶液, 或者視覺觀察沒有顆粒或凝膠,則認為該固體溶於曱苯。 甲笨溶解度亦報告於表1中。表1數據證明組分(A)和(B)之 莫耳%對石夕酮樹脂溶解之重要性。 表1組分(A)和(B)之莫耳%對矽酮樹脂在曱苯中 溶解度之影響Page 16 593438 5. Description of the invention (12) and toluene (weight ratio of 8 5: i 5). A mixture of (D) water and (E) hydrogen chloride was added to the mixture in an amount shown in Table 1 'In Sample 1-; [To, the component (c) was 1 part by weight. The resulting reaction product was removed under reduced pressure at 60 ° C. After complete absorption, 8.3 g of methyl was added to 1.7 g of the solid silicone resin, and the solubility of the obtained solid silicone resin in toluene was measured over 24 hours. If a clear solution is formed, or no particles or gels are visually observed, the solid is considered to be soluble in toluene. Methabenz solubility is also reported in Table 1. The data in Table 1 demonstrate the importance of the mole% of components (A) and (B) to the dissolution of the syringone resin. Table 1 Effect of mole% of components (A) and (B) on the solubility of silicone resin in toluene
樣品 重量份數 莫耳 甲苯一 一編號 (A) (B) (D) — (E) (F) (A) (B) 溶解 ΓΤ-1 0.56 1.32 0.84 0.078 12.0 20 60 是 1-2 0.70 1.21 0.86 0.079 12.1 25 55 1-3 0.84 1.10 0.87 0.080 12.2 30 50 是 1_4 0.97 0.98 0.88 0.081 12.2 35 45 是 1 -5 1.11 0.88 0.90 0.082 12.3 40 40 —- ~T6l 1.25 0.77 0.91 0.084 12.4 ~45> 35 -- 是一 1 -7 1.39 0.66 0.92 0.085 12.5 50 30 是 1-8 1.67 0.44 0.95 0.087 12.6 60 20 是 1-9 1.81 0.33 0.96 0.088 12.7 65 15 --- 是 1_10* 0.00 1.75 0.79 0.073 11.7 0 80 _-- 否 Ml* 0.28 1.53 0.82 0.075 11.9 10 70 M2* 0.42 1.42 0.83 0.076 12.0 15 65 否 1-13* 1.95 0.22 0.98 0.090 12.8 70 Ρ ίο 否/ 1-14* 2.22 0.00 1.00 0.092 12.9 80 0 否HI 非本發明實例Sample weight parts Mol toluene one-to-one number (A) (B) (D) — (E) (F) (A) (B) dissolved ΓΤ-1 0.56 1.32 0.84 0.078 12.0 20 60 is 1-2 0.70 1.21 0.86 0.079 12.1 25 55 1-3 0.84 1.10 0.87 0.080 12.2 30 50 Yes 1_4 0.97 0.98 0.88 0.081 12.2 35 45 Yes 1 -5 1.11 0.88 0.90 0.082 12.3 40 40 --- ~ T6l 1.25 0.77 0.91 0.084 12.4 ~ 45 > 35-Yes 1 1 -7 1.39 0.66 0.92 0.085 12.5 50 30 Yes 1-8 1.67 0.44 0.95 0.087 12.6 60 20 Yes 1-9 1.81 0.33 0.96 0.088 12.7 65 15 --- Yes 1_10 * 0.00 1.75 0.79 0.073 11.7 0 80 _-- No Ml * 0.28 1.53 0.82 0.075 11.9 10 70 M2 * 0.42 1.42 0.83 0.076 12.0 15 65 No 1-13 * 1.95 0.22 0.98 0.090 12.8 70 Ροο / 1-14 * 2.22 0.00 1.00 0.092 12.9 80 0 No HI is not an example of the present invention
第17頁Page 17
593438 五、發明說明(13) ---- 進一步由Si29和C13 NMR分析檢測样αu 一 丨饿,則樣品1 - 3所述樹脂、其具 有25莫耳%SiOH和SiOR3,其中R3 Λ审|斗、 ^ 、两Τ基或乙基。 iiM2 製備與實例1所述樣品相似之樣品2-1至2_6,但且有以 下例外,組分(A)之莫耳%恒保持於3〇莫耳(1重量份數)。 如實例1所述其它組分之各個濃度與所得矽酮樹脂之甲苯 溶解度顯示於表2中。 組分((:丄莫耳%對矽酮樹:笨之溶解唐之影響 樣品 重量份數 莫耳 甲苯 編號 (B) (C) (D) (E) (F) (B) (C) ---- 溶解 2-1 1.05 1.80 1.047 0.0960 18.8 40 30 是 2-2 1.16 1.56 1.045 0.0959 17.1 44 26 是 2-3 1.29 1.26 1.046 0.0959 15.0 49 21 ------- 2-4 1.42 0.96 1.046 0.0959 13.0 54 16 是 2-5* 1.50 0.78 1.045 0.0958 11.7 57 13 ---—. 否 2 - 6* 1.58 0.60 1.046 0.0959 10.5 60 10 否 ---------- *非本發明之實例 iJ13 按實例1所述方法製備樣品3_1至3-3,但組分(C)為 (C-1)十六烷基三甲氧基矽烷或(〇2)辛基三乙氧基石夕烷, 如表3所示。各組分之用量(佔(a )之重量份數)與所得樹脂 之甲笨溶解度於表3中提供。593438 V. Description of the invention (13) ---- The sample αu is further detected by Si29 and C13 NMR analysis, then the resin described in samples 1 to 3, which has 25 mole% SiOH and SiOR3, among which R3 Bucket, ^, two T group or ethyl. iiM2 Samples 2-1 to 2-6 similar to those described in Example 1 were prepared, with the following exceptions, and the mole% of component (A) was kept constant at 30 moles (1 part by weight). The respective concentrations of the other components as described in Example 1 and the toluene solubility of the obtained silicone resin are shown in Table 2. Components ((: Moore% on Silicone Tree: Stupid Dissolving Tang Effect of Sample Weight Parts Moore Toluene Number (B) (C) (D) (E) (F) (B) (C)- --- Dissolve 2-1 1.05 1.80 1.047 0.0960 18.8 40 30 Yes 2-2 1.16 1.56 1.045 0.0959 17.1 44 26 Yes 2-3 1.29 1.26 1.046 0.0959 15.0 49 21 ------- 2-4 1.42 0.96 1.046 0.0959 13.0 54 16 Yes 2-5 * 1.50 0.78 1.045 0.0958 11.7 57 13 -----. No 2-6 * 1.58 0.60 1.046 0.0959 10.5 60 10 No ---------- * Not an example of the invention iJ13 Samples 3_1 to 3-3 were prepared according to the method described in Example 1, but component (C) was (C-1) hexadecyltrimethoxysilane or (〇2) octyltriethoxylxane, as shown in Table As shown in Table 3. The amount of each component (parts by weight of (a)) and the solubility of the obtained resin in methylbenzyl are provided in Table 3.
第18頁 593438 五、發明說明(14) 表3 樣品 重量份數 莫耳 甲苯 編號 (C)類型 (B) (C) (D) (E) (F) ㈧ ⑼ (C) 溶解 3-1 C-1 0.99 1.80 1.05 0.096 20.13 30 37.5 32.5 是 3-2 C-2 0.92 1.55 1.05 0.10 13.73 30 35 35 3-3 C-2 0.63 2.92 1.24 0.11 21.88 25 20 55 是 實例4 用原地生成之氯化氫水解催化劑製備矽酮樹脂。混合 (A)l份四乙氧基矽烷、(Β)1·08份三氯矽烷、(C)1.19份十Λ· 八烷基三甲氧基矽烷,(D)l · 03份水及(F)14· 87份MIBK與 甲苯之混合物(重量比8 5 : 1 5 ),以類似實例1所述之方法生 成矽酮樹脂。將該混合物回流5分鐘,在真空下以4 0 °C除 去揮發物。由實例1所述方法檢測,得矽酮樹脂溶於甲 苯。 實例5 加熱和烴取代對矽酮樹脂重量平均分子量之影響。以類 似實例1所述之方法製備樣品5-1至5-6。組分(C)為表4所 示之(C-1)十八烷基三曱氧基矽烷或(C-2)辛基三乙氧基矽 烷。表4中亦提供如實例1所述之組分(C)和組分(A)及(B) 之莫耳%。組务(D)和(E)之用量與實例1所述相同。在真空 下以3 0 °C除去揮發物,回收固體矽酮樹脂。將固態矽酮樹 脂在甲苯中溶解至30重量%,經表4所述時間加熱回流,以 連續除去經釋出水。在加熱前後由GPC法測定該矽酮樹脂Page 18 593438 V. Description of the invention (14) Table 3 Sample weight parts Mol toluene Number (C) Type (B) (C) (D) (E) (F) ㈧ ⑼ (C) Dissolved 3-1 C -1 0.99 1.80 1.05 0.096 20.13 30 37.5 32.5 Yes 3-2 C-2 0.92 1.55 1.05 0.10 13.73 30 35 35 3-3 C-2 0.63 2.92 1.24 0.11 21.88 25 20 55 Yes Example 4 Hydrogen chloride hydrolysis catalyst generated in situ Preparation of silicone resin. (A) 1 part of tetraethoxysilane, (B) 1.08 parts of trichlorosilane, (C) 1.19 parts of decyl octadecyltrimethoxysilane, (D) 1.03 parts of water and (F ) 14.87 parts of a mixture of MIBK and toluene (weight ratio 8 5: 1 5). A silicone resin was produced in a similar manner as described in Example 1. The mixture was refluxed for 5 minutes and the volatiles were removed under vacuum at 40 ° C. According to the method described in Example 1, the silicone resin was dissolved in toluene. Example 5 Effects of heating and hydrocarbon substitution on the weight average molecular weight of silicone resins. Samples 5-1 to 5-6 were prepared in a manner similar to that described in Example 1. Component (C) is (C-1) octadecyltrimethoxysilane or (C-2) octyltriethoxysilane as shown in Table 4. Table 4 also provides mole% of component (C) and components (A) and (B) as described in Example 1. The amount of the tasks (D) and (E) is the same as that described in Example 1. The volatiles were removed under vacuum at 30 ° C and the solid silicone resin was recovered. The solid silicone resin was dissolved in toluene to 30% by weight, and heated under reflux for the time described in Table 4 to continuously remove the released water. Determination of the silicone resin by GPC method before and after heating
第19頁 593438 五、發明說明(15) 之重量平均分子量,結果報告於表4中。如實例1所述測定 矽酮樹脂之甲苯溶解度,所有樹脂均加熱處理前後溶於甲 苯。 表4 加熱處理前後矽酮樹脂之Mw 樣品 莫耳% 時間 Mw 編號 類型(C) ㈧ (B) (C) (小時) 加熱前 加熱後 5-1 C-1 30 47 23 1 12,700 55,000 5-2 C-1 30 47 23 2 12,700 91,500 5-3 C-1 30 47 23 3 12,700 139,400 5-4 C-1 30 49 21 1 11,600 81,500 5-5 C-2 30 30 40 1 5,240 23,800 5-6 C-2 30 25 45 1 7,540 16,3〇〇 實例6 以實例1之方法製成可溶矽酮樹脂,將樣品加熱,以產 生孔及測量孔隙度,將樣品塗於基材上,對基材測量樣品 之物理性能。生成可溶矽酮樹脂係加入表5所述迷用量之 各組分。 表5 組分 説明 重量份數 莫耳% (A) 四乙氧基矽烷 1 30 (B) 三乙氧基矽烷 1.31 ^ 50 (C) 十八烷基三甲氧基矽烷 1.20 20 (D) 水 0.57 - (E) 氯化氫 0.096 - (F) MIBK和甲苯之混合物(85:15重量比) 15.8 -Page 19 593438 5. The weight average molecular weight of the description of the invention (15). The results are reported in Table 4. The toluene solubility of the silicone resin was measured as described in Example 1. All resins were soluble in toluene before and after heat treatment. Table 4 Mw samples of silicone resin before and after heat treatment Molar% Time Mw Number type (C) ㈧ (B) (C) (hours) Before heating After heating 5-1 C-1 30 47 23 1 12,700 55,000 5-2 C-1 30 47 23 2 12,700 91,500 5-3 C-1 30 47 23 3 12,700 139,400 5-4 C-1 30 49 21 1 11,600 81,500 5-5 C-2 30 30 40 1 5,240 23,800 5-6 C- 2 30 25 45 1 7,540 16,300. Example 6 A soluble silicone resin was prepared by the method of Example 1. The sample was heated to generate pores and measure porosity. The sample was coated on a substrate and measured on the substrate. Physical properties of the sample. The soluble silicone resin was produced by adding the components described in Table 5. Table 5 Component description Molar% by weight (A) Tetraethoxysilane 1 30 (B) Triethoxysilane 1.31 ^ 50 (C) Octadecyltrimethoxysilane 1.20 20 (D) Water 0.57 -(E) Hydrogen chloride 0.096-(F) Mixture of MIBK and toluene (85:15 weight ratio) 15.8-
第20頁 593438 五、發明說明(16) ^ 將固態樹脂樣品放入熔鍋(或坩堝)、在氮氣中以5 0 〇 加熱0.5小時。用測微(%1(:]:〇11161:1^〇3)人3八? 20 0 0加速表 面積和孔度計系統[喬治亞、諾克羅斯、測微儀器公司 (Micrometries Instrument Corporation, Norcross, GA)]測量所得固體於77〇k之氮吸收。經測定,BEt比表面 積為 913 in2/克。H-K 分析[赫瓦茲(Horvath). J. Chera.Page 20 593438 V. Description of the invention (16) ^ Put the solid resin sample into the crucible (or crucible) and heat it under nitrogen at 500 for 0.5 hour. Using micrometer (% 1 (:): 〇11161: 1 ^ 〇3) person 38? 2 0 0 0 accelerating surface area and porometer system [Georgia, Norcross, Microcross Instrument Company (Micrometries Instrument Corporation, Norcross, GA)] The nitrogen absorption of the obtained solid was measured at 770k. The specific surface area of BEt was determined to be 913 in2 / g. HK analysis [Hovaz (Horvath). J. Chera.
Eng· jpn·, 1 98 3, 16期,476頁]吸收數據顯示。該固體 具有0·41立方厘米/克之孔體積,窄孔徑大小分布及〇. 83 納米之中孔大小。 亦將固態矽酮樹脂樣品以1 7重量%溶於曱苯,用於旋塗 4 石=晶圓。將經塗覆矽晶圓在氮氣氣氛中以45〇。〇加熱1小 ^ 所仔 >專膜具1 · 2微米厚度,且厚度變化〇 · 9 %。介電常 數為1. 8。Eng. Jpn., 1 98 3, Issue 16, p. 476] Absorption data show. The solid had a pore volume of 0.41 cubic centimeters / gram, a narrow pore size distribution and a mesopore size of 0.83 nm. A solid silicone resin sample was also dissolved in xylene at 17% by weight for spin-coating 4 stone = wafer. The coated silicon wafer was placed in a nitrogen atmosphere at 45 °. 〇Heating for 1 hour ^ Soot > The special film has a thickness of 1.2 micrometers, and the thickness varies by 0.9%. The dielectric constant is 1.8.
實例J 為製備樣品7-1至7-4,以表6所述用量在玻璃容器中混 合下述組分(A)、(B)、(C)及(F), (A) 四乙氧基矽烷。 (B) 如表6所示。 (C) 十八烷基三甲氧基矽烷,及 (F)甲基,異丁基酮(MIBK)和甲苯之混合物(85:15重量^戀 比)。 · . 、胃以表6所示用量將(〇)水和(E)氯化氫之混合物加至以上 此合物。組分(C)之重量份數為丨。各樣品中(A)、(B)和 (c )之莫耳%為3 0 %、5 0 %及2 〇 %。將所得反應產物在減壓下Example J is the preparation of samples 7-1 to 7-4. The following components (A), (B), (C), and (F), (A) tetraethoxy are mixed in a glass container in the amounts described in Table 6. Silane. (B) As shown in Table 6. (C) octadecyltrimethoxysilane, and (F) a mixture of methyl, isobutyl ketone (MIBK) and toluene (85:15 weight ^ love ratio). In the stomach, a mixture of (0) water and (E) hydrogen chloride was added to the above mixture in the amount shown in Table 6. The weight part of component (C) is 丨. Molar% of (A), (B), and (c) in each sample was 30%, 50%, and 20%. The obtained reaction product is under reduced pressure
第21頁 593438 五、發明說明(17) ---- 以6 0 °C吸除揮發物。吸险6入 ^▽ 士 凡全後,將8.3克MIBK加至1· 7克 f悲夕嗣树曰,經24小時檢挪所得固體矽酮樹脂對MIBK之 岭解度如困生成澄清溶液且視覺觀察沒有顆粒或凝勝, 則認為該固體可溶。 物之特徵 樣品 類型 —— ________ r—_重量份數 MIBK 編號 (B) ⑷ (B) (D) (E) (F) 溶解 7-1 MeSi(OMe)3 0.83 _0.91 0.87 0.081 14.4 是 7-2 MeSiCl3 0.83 1.00 0.87 0 13.5 是 7-3 PrSiCl3 0.83 1.18 0.87 0 15.3 是 7-4 PhSiCl3 0.83 [Τ4Γ~ 0.87 0 17.6 是 加熱樣品7 -1、7 - 3和7 - 4,以產生孔及測量孔隙度。將 固態樹脂樣品放入熔鍋,在氮氣中以5 〇 〇加熱〇 · 5小時。 用測微ASAP 2 00 0加速表面積及孔度計系統(喬治亞、諾克 羅斯、測微儀器公司)測量所得固體於77°K之氮吸收。用 Η-Κ 分析(赫瓦兹 ’J\ Chem, Eng. Jpn·,1983,16 期’第 476頁)數據測量中孔(平均孔徑)大小及微孔體積。結果顯 示於表7中。 表7 納孔樹脂Μ合物之氮吸收數據 可溶Λ脂 樣品編"5虎 BET比表面積 米2/克 微孔體積 ^方厘米/克 平均孔徑 納米 7-1 386 0.180 0.62 7-3 437 .0.203 0.60 7-4 564 0.263 0.57Page 21 593438 V. Description of the invention (17) ---- Absorb volatile matter at 60 ° C. After entering the risk 6 ^ ▽ Shi Fanquan, add 8.3 grams of MIBK to 1.7 grams f sad evening tree said, after 24 hours inspection, the obtained solid silicone resin has a clear solution to the ridges of MIBK and produces a clear solution and Visually, if there are no particles or coagulation, the solid is considered to be soluble. Sample characteristics—— ________ r—_ parts by weight MIBK number (B) ⑷ (B) (D) (E) (F) Dissolve 7-1 MeSi (OMe) 3 0.83 _0.91 0.87 0.081 14.4 is 7 -2 MeSiCl3 0.83 1.00 0.87 0 13.5 Yes 7-3 PrSiCl3 0.83 1.18 0.87 0 15.3 Yes 7-4 PhSiCl3 0.83 [Τ4Γ ~ 0.87 0 17.6 Yes Heat samples 7 -1, 7-3 and 7-4 to generate holes and measure Porosity. The solid resin sample was placed in a melting pot and heated under nitrogen at 500 for 5 hours. The nitrogen absorption of the obtained solid at 77 ° K was measured using a micrometer ASAP 2000 accelerated surface area and porometer system (Georgia, Norcross, Micrometer Corporation). The size of mesopores (mean pore size) and micropore volume were measured using Η-K analysis (Hertz ‘J \ Chem, Eng. Jpn ·, 1983, Issue 16’ p. 476) data. The results are shown in Table 7. Table 7: Nitrogen absorption data of nanoporous resin M compounds. Soluble Λ lipid sample. "5 Tiger BET specific surface area m2 / g micropore volume ^ cm / g average pore diameter nano 7-1 386 0.180 0.62 7-3 437 .0.203 0.60 7-4 564 0.263 0.57
第22頁 593438 五、發明說明(18) 將樣品7-1、7-2和7-4塗於基材上,測定基材上塗層之 物理性能。將固態矽酮樹脂樣品以1 7重量%溶於Μ I BK,以 用於旋塗矽晶圓。將經塗覆矽晶圓在氮氣氣氛中以450 °C 加熱1小時。薄膜數據顯示於表8中。 表8 薄膜數據 可溶樹脂 (樣品編號) 薄膜厚度 (納米) 介電常數 7-1 887 1.87 7-2 698 L97 7-4 693 2.60Page 22 593438 V. Description of the invention (18) Samples 7-1, 7-2 and 7-4 were coated on the substrate, and the physical properties of the coating on the substrate were measured. A solid silicone resin sample was dissolved in MI BK at 17.7% by weight for spin-coated silicon wafers. The coated silicon wafer was heated at 450 ° C for one hour in a nitrogen atmosphere. The film data is shown in Table 8. Table 8 Film data Soluble resin (sample number) Film thickness (nm) Dielectric constant 7-1 887 1.87 7-2 698 L97 7-4 693 2.60
第23頁 593438Page 23 593438
第24頁Page 24
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US09/425,901 US6541107B1 (en) | 1999-10-25 | 1999-10-25 | Nanoporous silicone resins having low dielectric constants |
US09/425,306 US6359096B1 (en) | 1999-10-25 | 1999-10-25 | Silicone resin compositions having good solution solubility and stability |
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US20060047034A1 (en) | 2004-09-02 | 2006-03-02 | Haruaki Sakurai | Composition for forming silica-based film, method of forming silica-based film, and electronic component provided with silica-based film |
FR2889850B1 (en) * | 2005-08-19 | 2007-11-02 | Rhodia Chimie Sa | SILICONE COATING OF LOW DIELECTRIC CONSTANT, PROCESS FOR PREPARATION AND APPLICATION TO INTEGRATED CIRCUITS |
CN114316269B (en) * | 2021-12-28 | 2023-01-13 | 万华化学集团股份有限公司 | Preparation method and application of silicone resin |
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KR100361043B1 (en) * | 1993-12-27 | 2003-04-10 | 가와사키 마이크로 엘렉트로닉스 가부시키가이샤 | Manufacturing method of coating liquid and insulating film for forming insulating film and insulating film of semiconductor device |
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US6218497B1 (en) * | 1997-04-21 | 2001-04-17 | Alliedsignal Inc. | Organohydridosiloxane resins with low organic content |
US5973095A (en) * | 1997-04-21 | 1999-10-26 | Alliedsignal, Inc. | Synthesis of hydrogensilsesquioxane and organohydridosiloxane resins |
US6143855A (en) * | 1997-04-21 | 2000-11-07 | Alliedsignal Inc. | Organohydridosiloxane resins with high organic content |
US6043330A (en) * | 1997-04-21 | 2000-03-28 | Alliedsignal Inc. | Synthesis of siloxane resins |
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US6318124B1 (en) * | 1999-08-23 | 2001-11-20 | Alliedsignal Inc. | Nanoporous silica treated with siloxane polymers for ULSI applications |
US6143360A (en) * | 1999-12-13 | 2000-11-07 | Dow Corning Corporation | Method for making nanoporous silicone resins from alkylydridosiloxane resins |
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