TWI694112B - Composition having siloxane polymer and process for producing siloxane particulate composition - Google Patents
Composition having siloxane polymer and process for producing siloxane particulate composition Download PDFInfo
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Description
本發明是關於矽氧烷材料及填充劑材料之組成物。 The present invention relates to a composition of silicone material and filler material.
US 2009258216揭示一種產生矽氧烷組成物之方法,所述組成物與平均粒度介於0.26微米至4微米範圍內的粒子混合。 US 2009258216 discloses a method of producing a siloxane composition which is mixed with particles having an average particle size in the range of 0.26 microns to 4 microns.
先前技術亦揭示於吉恩,J(Jin,J)等人,有機電子(Organic Electronic),2012,第13卷,第53-57頁及WO 2008046142中。 The prior art is also disclosed in Jean, J (Jin, J), et al., Organic Electronic, 2012, Volume 13, pages 53-57 and WO 2008046142.
已知組成物當用作單組分黏著劑時,需要在低溫下運送及儲存以避免過早交聯。將需要具有可在室溫下運送及儲存而不發生實質性聚合或其他非所要反應的組成物。 Known compositions, when used as single-component adhesives, need to be transported and stored at low temperatures to avoid premature crosslinking. It will be necessary to have a composition that can be transported and stored at room temperature without substantial polymerization or other undesirable reactions.
本發明的目標為解決至少一部分本領域的問題。 The object of the present invention is to solve at least a part of the problems in the art.
本發明之目標為提供一種製造矽氧烷聚合物材料之新穎 製造方法。 The object of the present invention is to provide a novel material for manufacturing silicone polymer materials Manufacturing method.
組成物具有具有[-Si-O-Si-O]n的重複主鏈之矽氧烷聚合物,所述重複主鏈上具有烷基或芳基,以及所述重複主鏈上具有官能性交聯基團。一部分組成物為平均粒度小於100微米之粒子,粒子為金屬、半金屬或陶瓷粒子或其他適合之粒子。矽氧烷聚合物之分子量為400公克/莫耳至200,000公克/莫耳,特定言之300公克/莫耳至10,000公克/莫耳。具有組合之矽氧烷聚合物及粒子的組成物之黏度在5rpm下為500毫帕-秒至500,000毫帕-秒,特定言之1000毫帕-秒至75,000毫帕-秒,其如(例如)在25℃下以5rpm在黏度計上量測。 The composition has a siloxane polymer having a repeating main chain of [-Si-O-Si-O]n, the repeating main chain has an alkyl group or an aryl group, and the repeating main chain has a functional crosslink Group. Part of the composition is particles with an average particle size of less than 100 microns, and the particles are metal, semi-metal, or ceramic particles or other suitable particles. The molecular weight of the silicone polymer is 400 g/mol to 200,000 g/mol, specifically 300 g/mol to 10,000 g/mol. The viscosity of the composition with the combined siloxane polymer and particles is 500 mPa-s to 500,000 mPa-s at 5 rpm, specifically 1000 mPa-s to 75,000 mPa-s, such as (eg ) Measured on a viscometer at 5 rpm at 25°C.
在一個實施例中,藉由包括以下步驟之方法獲得產物:在存在鹼催化劑的情況下聚合矽烷醇及烷氧基矽烷以形成黏滯透明的矽氧烷材料;提供平均粒度小於100微米之粒子;在溶劑中混合偶合劑與矽氧烷聚合物;藉由乾燥移除溶劑;以及將矽氧烷聚合物、粒子以及偶合劑之組成物置於容器中。 In one embodiment, the product is obtained by a method including the steps of: polymerizing silanol and alkoxysilane in the presence of an alkali catalyst to form a viscous and transparent silicone material; providing particles with an average particle size of less than 100 microns ; Mix the coupling agent and the siloxane polymer in the solvent; remove the solvent by drying; and place the composition of the siloxane polymer, particles, and coupling agent in the container.
本發明提供一種具有矽氧烷聚合物的組成物,包括藉由以下方法製造之矽氧烷:提供具有化學式SiR1 aR2’ 4-a之作為第一單體之第一化合物,其中a為1至3,R1為反應性基團,且R2’為烷基或芳基,或其分子量小於1000公克/莫耳之寡聚物;提供具有化學式SiR3 bR4 cR5 4-(b+c)之第二化合物,其中R3為交聯官能基,R4為反應性基團,且R5為烷基或芳基,且其中b=1至2,且c=1至(4-b),或其分子量小於1000公克/莫耳之寡聚物;以 及將第一化合物及第二化合物聚合在一起以形成矽氧烷聚合物;且組成物更包括平均粒度小於100微米之粒子;其中矽氧烷聚合物之分子量為300公克/莫耳至10,000公克/莫耳;其中組成物在5rpm黏度計下之黏度為1000毫帕-秒至75000毫帕-秒;以及其中矽氧烷聚合物實質上不含-OH基團。 The present invention provides a silicone composition having a siloxane polymers, including silicon by a method for manufacturing the alumoxane: providing a 'first compound of a first monomer of 4-a, as a chemical formula SiR 1 a R 2, where a From 1 to 3, R 1 is a reactive group, and R 2′ is an alkyl or aryl group, or an oligomer with a molecular weight of less than 1000 g/mol; provides the chemical formula SiR 3 b R 4 c R 5 4 -a second compound of (b+c) , wherein R 3 is a cross-linking functional group, R 4 is a reactive group, and R 5 is an alkyl group or an aryl group, and wherein b=1 to 2 and c=1 To (4-b), or an oligomer with a molecular weight of less than 1000 g/mol; and polymerizing the first compound and the second compound together to form a siloxane polymer; and the composition further includes an average particle size of less than 100 Micron particles; wherein the molecular weight of the silicone polymer is 300 g/mol to 10,000 g/mol; the viscosity of the composition at a 5 rpm viscometer is 1000 mPa-s to 75000 mPa-s; and The silicone polymer is substantially free of -OH groups.
本發明組成物可用於多個領域,諸如半導體封裝中之接著劑、密封劑、焊料層或其他層或類似物。 The composition of the present invention can be used in various fields, such as adhesives, sealants, solder layers or other layers in semiconductor packages or the like.
本發明組成物可在室溫下以單組分接著劑形式運送及儲存而不發生實質性聚合或其他非所要反應。 The composition of the present invention can be transported and stored as a one-component adhesive at room temperature without substantial polymerization or other undesirable reactions.
100、102、104、106、108:步驟 100, 102, 104, 106, 108: steps
自結合隨附圖式獲取之以下實施方式,將更清楚地理解實例實施例,在所述隨附圖式中:圖1為製造矽氧烷聚合物及粒子組成物之一個實例之說明。 The following embodiments obtained from the accompanying drawings will understand the example embodiments more clearly. In the accompanying drawings: FIG. 1 is an illustration of an example of manufacturing a silicone polymer and a particle composition.
圖2說明在熱誘導聚合期間之矽氧烷聚合物之質量改變。 Figure 2 illustrates the change in mass of the silicone polymer during thermally induced polymerization.
圖3說明在沈積及聚合之後的矽氧烷材料之熱穩定性。 Figure 3 illustrates the thermal stability of the silicone material after deposition and polymerization.
將在下文中參看繪示一些實例實施例的隨附圖式,以更充分地描述各種實例實施例。然而,本發明概念可以許多不同形式實施,且不應被理解為限於本文所闡述的實例實施例。相反地,提供此等實例實施例以使得本說明書將為透徹且完整的,且將向本領域的技術人員充分傳達本發明概念之範疇。在圖式中,為了清楚 起見,可能會誇大層及區域的大小及相對大小。 The accompanying drawings illustrating some example embodiments will be referred to hereinafter to more fully describe the various example embodiments. However, the inventive concept can be implemented in many different forms and should not be construed as being limited to the example embodiments set forth herein. Rather, these example embodiments are provided so that this description will be thorough and complete, and will fully convey the scope of the inventive concept to those skilled in the art. In the diagram, for clarity For the sake of clarity, the size and relative size of layers and regions may be exaggerated.
應理解,當一元件或層被稱作在另一元件或層「上」、「連接至」或「耦接至」另一元件或層時,所述元件或層可直接在另一元件或層上、直接連接至或耦合至另一元件或層,或可能存在介入元件或層。相對地,當元件被稱作「直接在另一元件或層上」、「直接連接至另一元件或層」或「直接耦接至另一元件或層」時,不存在介入元件或層。全文中類似標號是指類似元件。如本文中所使用,術語「及/或」包含相關聯所列項目中之一或多者之任何及所有組合。 It should be understood that when an element or layer is referred to as being “on”, “connected to” or “coupled to” another element or layer, the element or layer can be directly on the other element or layer. On a layer, directly connected to or coupled to another element or layer, or intervening elements or layers may be present. In contrast, when an element is referred to as being "directly on another element or layer", "directly connected to another element or layer" or "directly coupled to another element or layer", there are no intervening elements or layers present. Similar symbols throughout the text refer to similar elements. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
亦應理解,儘管可能在本文中使用術語第一、第二、第三等描述各種元件、組件、區域、層及/或區段,但此等元件、組件、區域、層及/或區段不應受此等術語限制。此等術語僅用以將一個元件、組件、區域、層或區段與另一元件、組件、區域、層或區段區別。因此,在不脫離本發明概念的教示的情況下,下文論述的第一元件、組件、區域、層或區段可被稱為第二元件、組件、區域、層或區段。 It should also be understood that although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, such elements, components, regions, layers and/or sections Should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Therefore, without departing from the teachings of the inventive concept, the first element, component, region, layer, or section discussed below may be referred to as the second element, component, region, layer, or section.
本文中所使用之術語僅出於描述特定實施例之目的且並不意欲為限制性的。如本文中所使用,除非上下文另有清晰地指示,否則單數形式「一」以及「所述」意欲亦包含複數形式。應進一步理解,術語「包含」或「包括」在用於本說明書中時指定所陳述特徵、區域、整數、步驟、操作、元件及/或組件的存在,但不排除一或多個其他特徵、區域、整數、步驟、操作、元件、組件及/或其群組的存在或添加。 The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, unless the context clearly indicates otherwise, the singular forms "a" and "said" are intended to include the plural forms as well. It should be further understood that the term "comprising" or "including" when used in this specification specifies the presence of stated features, regions, integers, steps, operations, elements and/or components, but does not exclude one or more other features, The presence or addition of regions, integers, steps, operations, elements, components, and/or groups thereof.
此外,相對術語,諸如「下部」或「底部」及「上部」或 「頂部」可在本文中用於描述一個元件與另一元件之關係,如圖式中所說明。將理解,相對術語意欲涵蓋除圖式中所描繪的定向以外的裝置的不同定向。舉例而言,若一個圖式中之裝置翻轉,則描述成位於其他元件之「下部」側面上之元件將接著定向於所述其他元件之「上部」側面上。因此,例示性術語「下部」可因此取決於圖式之特定定向而涵蓋「下部」及「上部」之定向。類似地,若將圖式中之一者中的裝置翻轉,則描述為在其他元件「下方」或「之下」的元件將定向於其他元件「上方」。因此,例示性術語「下方」或「之下」可涵蓋上方及下方兩種定向。 In addition, relative terms such as "lower" or "bottom" and "upper" or "Top" can be used herein to describe the relationship between one element and another element, as illustrated in the figure. It will be understood that the relative terms are intended to cover different orientations of the device than those depicted in the drawings. For example, if the device in one drawing is turned over, the element described as being located on the "lower" side of the other element will then be oriented on the "upper" side of the other element. Therefore, the exemplary term "lower portion" may therefore cover the orientation of "lower portion" and "upper portion" depending on the particular orientation of the drawing. Similarly, if the device in one of the figures is turned over, elements described as "below" or "beneath" other elements will be oriented "above" the other elements. Therefore, the exemplary terms "below" or "below" can encompass both upper and lower orientations.
應注意,除非上下文另外明確規定,否則如本文所用,單數形式「一」及「所述」包含複數個指示物。另外應理解,術語「包括」當用於本說明書中時,指定所陳述特徵、步驟、操作、元件及/或組件之存在,但不排除添加一或多個其他特徵、步驟、操作、元件組件及/或其族群。除非另有定義,否則本文使用的全部術語(包含技術及科學術語)的意義與本發明所屬技術領域中具有通常知識者通常理解的意義相同。應進一步理解,術語(諸如,常用詞典中所定義之術語)應解釋為具有與其在相關技術及本發明之上下文中的意義一致之意義,且除非本文中明確地如此定義,否則將不以理想化或過度形式化意義進行解釋。 It should be noted that unless the context clearly dictates otherwise, as used herein, the singular forms "a" and "said" include plural indicators. It should also be understood that the term "comprising", when used in this specification, specifies the presence of the stated features, steps, operations, elements and/or components, but does not exclude the addition of one or more other features, steps, operations, elements and components And/or its ethnic group. Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by those with ordinary knowledge in the technical field to which the present invention belongs. It should be further understood that terms (such as those defined in commonly used dictionaries) should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology and the present invention, and unless expressly defined as such herein, will not be ideal Explain in a formal or over-formal sense.
以下單體及聚合物之式中所用之小寫字母尤其表示整數。 The lower case letters used in the formulas of the following monomers and polymers especially represent integers.
具有矽氧烷聚合物及粒狀材料之組成物提供為黏滯材料,視情況具有催化劑及偶合劑(用於幫助組成物隨後之熱聚合或UV聚合),以及穩定劑、抗氧化劑、分散劑、界面活性劑等。組成 物具有適合黏度易於塗覆及最終聚合,而不需要溶劑。矽氧烷-粒狀組成物可用作晶粒附連接著劑,較佳為具有熱導率特性之晶粒附連接著劑,或作為半導體封裝中之密封劑或其他層,例如導熱但電絕緣之光學透射層。當然,取決於選擇之矽氧烷及粒子,多種特徵(密度、CTE、熱導率、電導率、光學透射率等)為可能的。 Compositions with silicone polymers and granular materials are provided as viscous materials, optionally with catalysts and coupling agents (used to assist the subsequent thermal or UV polymerization of the composition), as well as stabilizers, antioxidants, and dispersants , Surfactant, etc. composition The material has a suitable viscosity and is easy to coat and eventually polymerize, without requiring a solvent. The silicone-granular composition can be used as a die attach agent, preferably a die attach agent with thermal conductivity characteristics, or as a sealant or other layer in a semiconductor package, such as a thermally conductive but electrically Insulating optical transmission layer. Of course, depending on the selected silicone and particles, various characteristics (density, CTE, thermal conductivity, electrical conductivity, optical transmittance, etc.) are possible.
參見圖1,製造組成物,其中在步驟100處提供矽氧烷聚合物。較佳地,聚合物具有氧化矽主鏈,其具有芳基(或烷基)取代基以及官能性交聯取代基。在圖1中之步驟102處,填充劑材料與矽氧烷聚合物混合。填充劑材料較佳為包括平均粒度為100微米或小於100微米,較佳10微米或小於10微米之粒子之粒狀材料。在步驟104處,添加催化劑,當向組成物提供熱或UV光(或其他活化方法)時,催化劑與矽氧烷聚合物中之官能性交聯基團反應。在步驟106處,單體(或寡聚)偶合劑較佳具有在如同矽氧烷聚合物施加熱或光時同樣具反應性之官能性交聯基團。最後,在步驟108處,取決於組成物之最終用途,添加額外材料,諸如穩定劑、抗氧化劑、分散劑、接著促進劑、塑化劑、軟化劑以及其他可能組分。儘管可添加溶劑,但在一較佳實施例中,組成物不含溶劑且為儲存在不透光的容器中用於隨後使用或運送之黏滯流體。
Referring to FIG. 1, a composition is manufactured in which a silicone polymer is provided at
如上文所指出,如本文中所揭示製造之組成物包括矽氧烷聚合物。為了製造矽氧烷聚合物,提供具有化學式SiR1 aR2’ 4-a之第一化合物,其中a為1至3,R1為反應性基團,且R2’為烷基或芳基。亦提供具有化學式SiR3 bR4 cR5 4-(b+c)之第二化合物,其中R3為交聯官能基,R4為反應性基團,且R5為烷基或芳基,且其中b=1至2,且c=1至(4-b)。連同第一化合物及第二化合物提供視情況 選用之第三化合物以與其聚合。第三化合物可具有化學式SiR9 fR10 g,其中R9為反應性基團且f=1至4,且其中R10為烷基或芳基且g=4-f。第一化合物、第二化合物以及第三化合物可以任何順序提供,且可提供這些化合物中之任一者之寡聚部分聚合型式來替代上文所提及之單體。 As noted above, the composition made as disclosed herein includes a silicone polymer. In order to manufacture the siloxane polymer, a first compound having the chemical formula SiR 1 a R 2′ 4-a is provided, wherein a is 1 to 3, R 1 is a reactive group, and R 2′ is an alkyl or aryl group . A second compound with the chemical formula SiR 3 b R 4 c R 5 4-(b+c) is also provided, where R 3 is a cross-linking functional group, R 4 is a reactive group, and R 5 is an alkyl or aryl group , And where b=1 to 2, and c=1 to (4-b). Together with the first compound and the second compound, a third compound is optionally selected to polymerize with it. The third compound may have the chemical formula SiR 9 f R 10 g , where R 9 is a reactive group and f=1 to 4, and where R 10 is an alkyl or aryl group and g=4-f. The first compound, the second compound, and the third compound may be provided in any order, and the oligomeric partial polymerization pattern of any of these compounds may be provided instead of the monomers mentioned above.
第一化合物、第二化合物及第三化合物以及下文中敍述的任何化合物,若此類化合物具有多於一個單一類型之「R」基團,諸如複數個芳基或烷基,或複數個反應性基團,或複數個交聯官能基等,則獨立地選擇多個R基團以在每次出現時相同或不同。舉例而言,若第一化合物為SiR1 2R2’ 2,則獨立地選擇多個R1基團以使彼此相同或不同。同樣,獨立地選擇多個R2’基團以使彼此相同或不同。除非另外明確陳述,否則本文中提及之任何其他化合物為相同情況。 The first compound, the second compound and the third compound and any of the compounds described below, if such compounds have more than one single type of "R" group, such as a plurality of aryl or alkyl groups, or a plurality of reactivity Group, or a plurality of cross-linking functional groups, etc., multiple R groups are independently selected to be the same or different at each occurrence. For example, if the first compound is SiR 1 2 R 2′ 2 , multiple R 1 groups are independently selected to be the same or different from each other. Similarly, a plurality of independently selected R 2 'group is the same or different from each other so that. Unless expressly stated otherwise, any other compounds mentioned herein are the same.
亦提供催化劑。催化劑可為鹼催化劑,或如下文所提及之其他催化劑。提供之催化劑應能夠將第一化合物及第二化合物聚合在一起。如上所述,添加化合物及催化劑之次序可為任何所需次序。一起提供之各種組分經聚合以產生具有所需分子量及黏度之矽氧烷聚合物材料。在聚合之後,添加粒子,諸如微米粒子、奈米粒子或其他所需粒子,連同其他視情況存在之組分,諸如偶合劑、催化劑、穩定劑接著促進劑以及類似物。組成物之組分之組合可按任何所需次序進行。 Catalysts are also provided. The catalyst may be a base catalyst, or other catalysts as mentioned below. The provided catalyst should be able to polymerize the first compound and the second compound together. As mentioned above, the order of adding the compound and the catalyst may be any desired order. The various components provided together are polymerized to produce a siloxane polymer material having the desired molecular weight and viscosity. After polymerization, particles, such as microparticles, nanoparticles, or other desired particles, are added, along with other optional components such as coupling agents, catalysts, stabilizers followed by accelerators, and the like. The components of the composition can be combined in any desired order.
更特定言之,在一個實例中,藉由聚合第一化合物及第二化合物製得矽氧烷聚合物,其中第一化合物具有以下化學式:SiR1 aR2’ 4-a More specific words, in one example, by polymerizing the first compound and the second compound prepared silicon siloxane polymer, wherein the first compound has the following chemical formula: SiR 1 a R 2 '4 -a
其中a為1至3,R1為反應性基團,且R2’為烷基或芳基,且第二化合物具有以下化學式:SiR3 bR4 cR5 4-(b+c) Where a is 1 to 3, R 1 is a reactive group, and R 2'is an alkyl or aryl group, and the second compound has the following chemical formula: SiR 3 b R 4 c R 5 4-(b+c)
其中R3為交聯官能基,R4為反應性基團,且R5為烷基或芳基,且其中b=1至2,且c=1至(4-b)。 Where R 3 is a cross-linking functional group, R 4 is a reactive group, and R 5 is an alkyl group or an aryl group, and wherein b=1 to 2, and c=1 to (4-b).
第一化合物可具有1至3個結合至化合物中之矽之烷基或芳基(R2’)。不同烷基之組合、不同芳基之組合或烷基及芳基兩者之組合為可能的。在烷基之情況下,烷基較佳含有1至18個,更佳1至14個且尤其更佳1至12個碳原子。預想較短烷基,諸如1至6個碳(例如2至6個碳原子)。烷基可與一或多個,較佳兩個C1至C6烷基在α位置或β位置處分支。特定言之,烷基為含有1至6個碳原子之低碳數烷基,其視情況攜有1至3個選自甲基及鹵素之取代基。甲基、乙基、正丙基、異丙基、正丁基、異丁基以及第三丁基尤其更佳。環烷基亦為可能的,如環己基、金剛烷基、降冰片烯或降冰片烷基。 The first compound may have 1 to 3 alkyl or aryl groups (R 2' ) incorporated into the silicon in the compound. Combinations of different alkyl groups, different aryl groups, or both alkyl and aryl groups are possible. In the case of an alkyl group, the alkyl group preferably contains 1 to 18, more preferably 1 to 14, and particularly preferably 1 to 12 carbon atoms. Shorter alkyl groups are envisioned, such as 1 to 6 carbons (eg, 2 to 6 carbon atoms). The alkyl group may branch with one or more, preferably two C1 to C6 alkyl groups at the α position or β position. In particular, the alkyl group is a low-carbon alkyl group containing 1 to 6 carbon atoms, which optionally carries 1 to 3 substituents selected from methyl and halogen. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tertiary butyl are especially preferred. Cycloalkyl groups are also possible, such as cyclohexyl, adamantyl, norbornene or norbornyl.
若R2’為芳基,則芳基可為苯基,其視情況在環上攜有1至5個選自鹵素、烷基或烯基之取代基,或萘基,其視情況在環結構上攜有1至11個選自鹵素烷基或烯基之取代基,所述取代基視 情況經氟化(包含全氟化或部分氟化)。若芳基為多環芳基,則多環芳基可例如為蒽、萘、菲、并四苯,其視情況可攜有1-8個取代基或亦可視情況藉由含有1至12個碳之烷基、烯基、炔基或芳基與矽原子「間隔開」。諸如苯基之單環結構亦可以此方式與矽原子間隔開。 If R 2'is an aryl group, the aryl group may be a phenyl group, which optionally carries 1 to 5 substituents selected from halogen, alkyl, or alkenyl groups on the ring, or naphthyl, which may optionally be in the ring structure It carries 1 to 11 substituents selected from halogen alkyl or alkenyl, which are optionally fluorinated (including perfluorinated or partially fluorinated). If the aryl group is a polycyclic aryl group, the polycyclic aryl group may be, for example, anthracene, naphthalene, phenanthrene, naphthacene, which may carry 1-8 substituents as appropriate or may contain 1 to 12 as appropriate Carbon alkyl, alkenyl, alkynyl or aryl groups are "spaced" from the silicon atom. Single-ring structures such as phenyl can also be spaced from silicon atoms in this way.
藉由在第一化合物與第二化合物之間進行聚合反應(較佳鹼催化之聚合反應)製得矽氧烷聚合物。如下文闡述之視情況存在之額外化合物可包含為聚合反應的一部分。 Siloxane polymers are prepared by performing a polymerization reaction (preferably an alkali-catalyzed polymerization reaction) between the first compound and the second compound. The optional additional compounds as described below may be included as part of the polymerization reaction.
第一化合物可具有任何適合之反應性基團R1,諸如羥基、鹵素、烷氧基、羧基、胺或醯氧基。若舉例而言,第一化合物中之反應性基團為-OH基團,則第一化合物之更特定實例可包含矽烷二醇,尤其為諸如二苯基矽烷二醇、二甲基矽烷二醇、二異丙基矽烷二醇、二正丙基矽烷二醇、二正丁基矽烷二醇、二-第三丁基矽烷二醇、二異丁基矽烷二醇、苯基甲基矽烷二醇以及二環己基矽烷二醇。 The first compound may have any suitable reactive group R 1 , such as hydroxy, halogen, alkoxy, carboxy, amine or acetyloxy. If, for example, the reactive group in the first compound is an -OH group, a more specific example of the first compound may include silane diol, especially such as diphenyl silane diol, dimethyl silane diol , Diisopropylsilanediol, di-n-propylsilanediol, di-n-butylsilanediol, di-third butylsilanediol, diisobutylsilanediol, phenylmethylsilanediol And dicyclohexylsilanediol.
第二化合物可具有任何適合之反應性基團R4,諸如羥基、鹵素、烷氧基、羧基、胺或醯氧基,其可與第一化合物中之反應性基團相同或不同。在一個實例中,反應性基團在第一化合物或第二化合物(或任何參與聚合反應以形成矽氧烷聚合物之化合物-例如第三化合物等)中均不為-H,使得所得矽氧烷聚合物不存在任何或大體上任何直接結合至矽氧烷聚合物中之Si之H基團。基團R5若完全存在於第二化合物中,則獨立地為烷基或芳基,諸如針對第一化合物中之基團R2’。烷基或芳基R5可與第一化合物中之基團R2’相同或不同。 The second compound may have any suitable reactive group R 4 , such as hydroxy, halogen, alkoxy, carboxy, amine or acetyl, which may be the same as or different from the reactive group in the first compound. In one example, the reactive group is not -H in either the first compound or the second compound (or any compound that participates in the polymerization reaction to form a siloxane polymer-such as a third compound, etc.), so that the resulting siloxane The alkane polymer does not have any or substantially any H groups directly bonded to the Si in the silicone polymer. If the group R 5 is completely present in the second compound, it is independently an alkyl or aryl group, such as for the group R 2′ in the first compound. The alkyl or aryl group R 5 may be the same as or different from the group R 2′ in the first compound.
第二化合物之交聯反應性基團R3可為任何可藉由酸、鹼、自由基或熱催化之反應交聯之官能基。此等官能基可例如為任何環氧化物、環氧丙烷(oxetane)、丙烯酸酯、烯基、炔基或巰基。 The crosslinking reactive group R 3 of the second compound may be any functional group that can be crosslinked by an acid, base, free radical, or thermally catalyzed reaction. Such functional groups may for example be any epoxide, oxetane, acrylate, alkenyl, alkynyl or mercapto group.
在環氧基團之情況下,其可為具有三個可使用酸、鹼以及熱催化之反應交聯之環原子之環醚。此等含有環氧化物之交聯基團之實例為縮水甘油氧基丙基及(3,4-環氧環己基)乙基(僅舉數例)。 In the case of an epoxy group, it can be a cyclic ether with three ring atoms that can be cross-linked using acid, base, and thermally catalyzed reactions. Examples of such epoxide-containing crosslinking groups are glycidoxypropyl and (3,4-epoxycyclohexyl)ethyl (to name a few).
在環氧丙烷基團之情況下,其可為具有四個可使用酸、鹼以及熱催化之反應交聯之環原子之環醚。此類含有環氧丙烷之矽烷之實例包含3-(3-乙基-3-氧雜環丁基甲氧基)丙基三乙氧基矽烷、3-(3-甲基-3-氧雜環丁基甲氧基)丙基三乙氧基矽烷、3-(3-乙基-3-氧雜環丁基甲氧基)丙基三甲氧基矽烷或3-(3-甲基-3-氧雜環丁基甲氧基)丙基三甲氧基矽烷(僅舉數例)。 In the case of a propylene oxide group, it can be a cyclic ether with four ring atoms that can be cross-linked using acid, base, and thermally catalyzed reactions. Examples of such propylene oxide-containing silanes include 3-(3-ethyl-3-oxetanylmethoxy)propyltriethoxysilane, 3-(3-methyl-3-oxetanylmethyl Oxy)propyltriethoxysilane, 3-(3-ethyl-3-oxetanylmethoxy)propyltrimethoxysilane or 3-(3-methyl-3-oxetanylmethoxy) Group) propyl trimethoxy silane (to name a few).
在烯基之情況下,此類基團可具有較佳2至18個、更佳2至14個且尤其更佳2至12個碳原子。烯系(亦即,與雙鍵鍵結之兩個碳原子)基團較佳位於相對於分子中之Si原子之位置2或更高位置。分支鏈烯基較佳在α位置或β位置與一個且更佳兩個C1至C6烷基、烯基或炔基、視情況存在之氟化或全氟化烷基、烯基或炔基分支。 In the case of alkenyl groups, such groups may have preferably 2 to 18, more preferably 2 to 14, and especially more preferably 2 to 12 carbon atoms. The olefinic (ie, two carbon atoms bonded to the double bond) group is preferably located at position 2 or higher relative to the Si atom in the molecule. The branched alkenyl group is preferably branched at the α position or β position with one and more preferably two C1 to C6 alkyl, alkenyl or alkynyl groups, optionally fluorinated or perfluorinated alkyl, alkenyl or alkynyl groups .
在炔基之情況下,其可具有較佳2至18個、更佳2至14個且尤其更佳2至12個碳原子。炔系基團(亦即,與參鍵鍵結之兩個碳原子)較佳位於相對於分子中之Si原子或M原子之位置2或更高位置。分支鏈炔基較佳在α位置或β位置與一個且更佳兩個C1至C6烷基、烯基或炔基、視情況存在之全氟化烷基、烯基 或炔基分支。 In the case of an alkynyl group, it may have preferably 2 to 18, more preferably 2 to 14, and especially more preferably 2 to 12 carbon atoms. The alkyne group (that is, the two carbon atoms bonded to the reference bond) is preferably located at position 2 or higher relative to the Si atom or M atom in the molecule. The branched alkynyl group is preferably in the α position or β position with one and more preferably two C1 to C6 alkyl, alkenyl or alkynyl groups, optionally perfluorinated alkyl groups, alkenyl groups Or alkynyl branch.
在巰基之情況下,其可為任何含有碳鍵結之硫氫基之有機硫化合物。含巰基之矽烷之實例為3-巰基丙基三甲氧基矽烷及3-巰基丙基三乙氧基矽烷。 In the case of a mercapto group, it can be any organic sulfur compound containing a carbon-bonded sulfhydryl group. Examples of mercapto group-containing silanes are 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.
第二化合物中之反應性基團可為烷氧基。烷氧基之烷基殘基可為直鏈或分支鏈的。較佳地,烷氧基由具有1至6個碳原子之低碳數烷氧基(諸如甲氧基、乙氧基、丙氧基以及第三丁氧基)組成。第二化合物之特定實例為矽烷,尤其為諸如2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三乙氧基矽烷、3-(三甲氧基矽基)甲基丙烯酸丙酯、3-(三甲氧基矽基)丙烯酸丙酯、(3-縮水甘油基氧基丙基)三甲氧基矽烷或3-縮水甘油氧基丙基三乙氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷。 The reactive group in the second compound may be an alkoxy group. The alkyl residue of the alkoxy group may be linear or branched. Preferably, the alkoxy group is composed of a low-carbon alkoxy group having 1 to 6 carbon atoms (such as methoxy, ethoxy, propoxy, and third butoxy). A specific example of the second compound is silane, especially such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane , 3-(trimethoxysilyl)propyl methacrylate, 3-(trimethoxysilyl)propyl acrylate, (3-glycidoxypropyl)trimethoxysilane or 3-glycidoxy Propylpropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-propenyloxypropyltrimethoxysilane.
第三化合物可連同第一化合物及第二化合物提供以與其聚合。第三化合物可具有以下化學式:SiR9 fR10 g The third compound may be provided together with the first compound and the second compound to polymerize therewith. The third compound may have the following chemical formula: SiR 9 f R 10 g
其中R9為反應性基團,且f=1至4,且其中R10為烷基或芳基,且g=4-f。 Wherein R 9 is a reactive group, and f=1 to 4, and wherein R 10 is an alkyl group or an aryl group, and g=4-f.
一個此類實例為四甲氧基矽烷。其他實例尤其包含苯基甲基二甲氧基矽烷、三甲基甲氧基矽烷、二甲基二甲氧基矽烷矽烷、乙烯基三甲氧基矽烷、烯丙基三甲氧基矽烷、甲基三甲氧基矽 烷、甲基三乙氧基矽烷、甲基三丙氧基矽烷、丙基乙基三甲氧基矽烷、乙基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷。 One such example is tetramethoxysilane. Other examples include, inter alia, phenylmethyldimethoxysilane, trimethylmethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, methyltrimethyl Oxysilicon Alkane, methyltriethoxysilane, methyltripropoxysilane, propylethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane.
儘管第一化合物及第二化合物之聚合可使用酸催化劑進行,鹼催化劑為較佳的。用於第一化合物與第二化合物之間的鹼催化之聚合之鹼催化劑可為任何適合之鹼性化合物。此等鹼性化合物之實例尤其為任何胺,如三乙胺,及任何鋇氫氧化物,如氫氧化鋇、單水合氫氧化鋇、八水合氫氧化鋇。其他鹼性催化劑包含氧化鎂、氧化鈣、氧化鋇、氨、過氯酸銨、氫氧化鈉、氫氧化鉀、咪唑或正丁胺。在一個特定實例中,鹼催化劑為Ba(OH)2。可相對於在一起的第一化合物及第二化合物以小於0.5%之重量%,或以較低量,諸如以小於0.1%之重量%提供鹼催化劑。 Although the polymerization of the first compound and the second compound can be performed using an acid catalyst, an alkali catalyst is preferred. The base catalyst used for base-catalyzed polymerization between the first compound and the second compound may be any suitable basic compound. Examples of such basic compounds are especially any amines, such as triethylamine, and any barium hydroxides, such as barium hydroxide, barium hydroxide monohydrate, barium hydroxide octahydrate. Other basic catalysts include magnesium oxide, calcium oxide, barium oxide, ammonia, ammonium perchlorate, sodium hydroxide, potassium hydroxide, imidazole or n-butylamine. In a specific example, the base catalyst is Ba(OH) 2 . The base catalyst may be provided at less than 0.5% by weight relative to the first compound and the second compound together, or at a lower amount, such as less than 0.1% by weight.
聚合可在熔融相或液體介質中進行。溫度在約20℃到200℃,通常約25℃到160℃,尤其約40℃到120℃範圍內。總體上,聚合在環境壓力下進行且最大溫度藉由使用之任何溶劑之沸點設定。聚合可在回流條件下進行。其他壓力及溫度亦為可能的。第一化合物與第二化合物之莫耳比可為95:5至5:95,尤其90:10至10:90,較佳80:20至20:80。在一較佳實例中,第一化合物與第二化合物(或第二化合物加上參與聚合反應之其他化合物-參見下文)之莫耳比為至少40:60,或甚至45:55或更高。 The polymerization can be carried out in the molten phase or in a liquid medium. The temperature is in the range of about 20°C to 200°C, usually about 25°C to 160°C, especially about 40°C to 120°C. Generally, the polymerization is carried out at ambient pressure and the maximum temperature is set by the boiling point of any solvent used. The polymerization can be carried out under reflux conditions. Other pressures and temperatures are also possible. The molar ratio of the first compound to the second compound may be 95:5 to 5:95, especially 90:10 to 10:90, preferably 80:20 to 20:80. In a preferred embodiment, the molar ratio of the first compound to the second compound (or the second compound plus other compounds participating in the polymerization reaction-see below) is at least 40:60, or even 45:55 or higher.
在一個實例中,第一化合物具有-OH基團作為反應性基團且第二化合物具有烷氧基作為反應性基團。較佳地,就添加之第一化合物之量而言,-OH基團之總數不大於第二化合物中之反應性基團(例如烷氧基)之總數,且較佳小於第二化合物中(或第二 化合物加上與烷氧基一起添加之任何其他化合物,例如添加之四甲氧基矽烷或聚合反應中涉及之其他第三化合物(如本文所提及)中)之反應性基團之總數。在烷氧基數目超過羥基的情況下,所有或基本上所有-OH基團將反應且自矽氧烷移除,諸如甲醇(若烷氧基矽烷為甲氧基矽烷)、乙醇(若烷氧基矽烷為乙氧基矽烷)等。儘管第一化合物中之-OH基團之數目及第二化合物中之反應性基團(較佳除-OH基團以外)之數目可基本上相同,較佳的是第二化合物中之反應性基團之總數在數目上超過第一化合物中之-OH基團10%或更多,較佳25%或更多。在一些實施例中,第二化合物反應性基團之數目超過第一化合物-OH基團40%或更多,或甚至60%或更多,75%或更多,或高達100%或更多。在聚合之後移除甲醇、乙醇或聚合反應之其他副產物(取決於所選化合物),較佳在乾燥腔室蒸發出。 In one example, the first compound has an -OH group as a reactive group and the second compound has an alkoxy group as a reactive group. Preferably, in terms of the amount of the first compound added, the total number of -OH groups is not greater than the total number of reactive groups (such as alkoxy groups) in the second compound, and is preferably less than that in the second compound ( Or second The total number of reactive groups of the compound plus any other compounds added together with the alkoxy group, such as added tetramethoxysilane or other third compounds involved in the polymerization reaction (as mentioned herein). In the case where the number of alkoxy groups exceeds the hydroxyl groups, all or substantially all -OH groups will react and be removed from the siloxane, such as methanol (if the alkoxysilane is methoxysilane), ethanol (if the alkoxy group The base silane is ethoxy silane). Although the number of -OH groups in the first compound and the number of reactive groups (preferably other than -OH groups) in the second compound may be substantially the same, the reactivity in the second compound is preferred The total number of groups exceeds the number of -OH groups in the first compound by 10% or more, preferably 25% or more. In some embodiments, the number of reactive groups of the second compound exceeds the first compound-OH group by 40% or more, or even 60% or more, 75% or more, or up to 100% or more . After the polymerization, methanol, ethanol or other by-products of the polymerization reaction (depending on the selected compound) are removed, preferably evaporated in the drying chamber.
獲得之矽氧烷聚合物具有任何所需(重量平均)分子量,諸如500公克/莫耳至100,000公克/莫耳。分子量可在此範圍之下端(例如500公克/莫耳至10,000公克/莫耳或更佳500公克/莫耳至8,000公克/莫耳)或有機矽氧烷材料之分子量可在此範圍之上端(諸如10,000公克/莫耳至100,000公克/莫耳或更佳15,000公克/莫耳至50,000公克/莫耳)。可能需要將具有較低分子量之聚合物有機矽氧烷材料與具有較高分子量之有機矽氧烷材料混合。 The obtained siloxane polymer has any desired (weight average) molecular weight, such as 500 g/mol to 100,000 g/mol. The molecular weight may be at the lower end of this range (e.g., 500 g/mole to 10,000 g/mole or more preferably 500 g/mole to 8,000 g/mole) or the molecular weight of the organosiloxane material may be at the upper end of this range ( (Such as 10,000 g/mole to 100,000 g/mole or more preferably 15,000 g/mole to 50,000 g/mole). It may be necessary to mix polymer organosiloxane materials with lower molecular weight with organosiloxane materials with higher molecular weight.
可另外調節獲得之聚合物之組成以達成在最終固化之後產生良好接著。此接著可在將與聚合物混合之填充劑或將塗覆聚合物之基板上。為達成良好接著,在聚合物製造期間使用具有良好接著特性之矽烷。具有極性基團(如羥基、環氧基、羧基、酸酐或 胺基)之化合物為在各種基板上具有良好接著特性之矽烷之實例。 The composition of the polymer obtained can be additionally adjusted to achieve good adhesion after final curing. This can then be on the filler to be mixed with the polymer or the substrate to be coated with the polymer. To achieve good adhesion, silanes with good adhesion properties are used during polymer manufacturing. Have polar groups (such as hydroxyl, epoxy, carboxyl, anhydride or Amino groups) are examples of silanes with good adhesion properties on various substrates.
取決於聚合物之最終所需用途,獲得之矽氧烷聚合物可接著與額外組分組合。較佳地,矽氧烷聚合物與填充劑組合以形成組成物,諸如具有平均粒度小於100微米,較佳小於50微米,包含小於20微米之粒子之粒狀填充劑。額外組分可為組成物之一部分,諸如催化劑或固化劑、一或多種偶合劑、分散劑、抗氧化劑、穩定劑、接著促進劑及/或其他所需組分,其取決於矽氧烷材料之最終所需用途。在一個實例中,包含可將氧化表面還原為其金屬形式之還原劑。還原劑可在粒子為具有表面氧化之金屬粒子之情況下自粒子移除氧化,及/或自例如金屬接合墊或已經氧化之其他金屬或導電區域移除氧化,以改良矽氧烷粒子材料與其所沈積或接著之表面之間的電連接。還原劑或穩定劑可包含乙二醇、β-D-葡萄糖、聚環氧乙烷、甘油、1,2-丙二醇、N,N二甲基甲醯胺、聚-丙烯酸鈉(PSA)、具有聚丙烯酸之β-環糊精、二羥基苯、聚乙烯醇、1,2-丙二醇、肼、硫酸肼、硼氫化鈉、抗壞血酸、對苯二酚家族、五倍子酸、連苯三酚、乙二醛、乙醛、戊二醛、脂族二醛家族、三聚甲醛、錫粉、鋅粉、甲酸。亦可添加添加劑,諸如穩定劑,例如抗氧化劑,諸如豔佳諾克司(Irganox)(如下文中所提及)或二嗪衍生物。 Depending on the ultimate desired use of the polymer, the obtained siloxane polymer can then be combined with additional components. Preferably, the silicone polymer is combined with a filler to form a composition, such as a particulate filler having an average particle size of less than 100 microns, preferably less than 50 microns, and containing particles less than 20 microns. Additional components may be part of the composition, such as catalysts or curing agents, one or more coupling agents, dispersants, antioxidants, stabilizers, adhesion promoters, and/or other desired components, depending on the silicone material The final required use. In one example, a reducing agent that can reduce the oxidized surface to its metal form is included. The reducing agent can remove oxidation from the particles when the particles are metal particles with surface oxidation, and/or remove oxidation from, for example, metal bonding pads or other metals or conductive regions that have been oxidized, to improve the siloxane particle material and The electrical connection between the deposited or subsequent surfaces. The reducing agent or stabilizer may include ethylene glycol, β-D-glucose, polyethylene oxide, glycerin, 1,2-propylene glycol, N,N dimethylformamide, poly-sodium acrylate (PSA), Polyacrylic acid β-cyclodextrin, dihydroxybenzene, polyvinyl alcohol, 1,2-propanediol, hydrazine, hydrazine sulfate, sodium borohydride, ascorbic acid, hydroquinone family, gallic acid, pyrogallol, ethanediol Aldehyde, acetaldehyde, glutaraldehyde, aliphatic dialdehyde family, paraformaldehyde, tin powder, zinc powder, formic acid. Additives such as stabilizers, such as antioxidants, such as Irganox (as mentioned below) or diazine derivatives can also be added.
交聯矽或非矽類樹脂及寡聚物可用於增強矽氧烷聚合物之間的交聯。藉由矽氧烷聚合物之官能性選擇添加之交聯寡聚物或樹脂之官能性。若舉例而言,在矽氧烷聚合物之聚合期間使用環氧類烷氧基矽烷,則可使用環氧官能性寡聚物或樹脂。環氧寡聚物或樹脂可為任何二官能性、三官能性、四官能性或更高官能性環氧 寡聚物或樹脂。此等環氧寡聚物或樹脂之實例可為1,3-雙2-(3,4-環氧環己基)乙基1,1,3,3-四甲基二矽氧烷、1,3-雙環氧丙氧基丙基1,1,3,3-四甲基二矽氧烷、己二酸雙(3,4-環氧環己基甲基)酯、3,4-環氧基環己烷甲酸3,4-環氧環己基甲酯、1,4-環己烷二甲醇二縮水甘油醚、雙酚A二縮水甘油醚、1,2-環己烷二甲酸二縮水甘油酯(僅舉數例)。 Cross-linked silicone or non-silicone resins and oligomers can be used to enhance cross-linking between silicone polymers. The functionality of the added cross-linked oligomer or resin is selected by the functionality of the silicone polymer. If, for example, epoxy-based alkoxysilanes are used during the polymerization of the siloxane polymer, epoxy-functional oligomers or resins can be used. The epoxy oligomer or resin may be any difunctional, trifunctional, tetrafunctional or higher functional epoxy Oligomer or resin. Examples of such epoxy oligomers or resins can be 1,3-bis 2-(3,4-epoxycyclohexyl) ethyl 1,1,3,3-tetramethyl disilaxane, 1, 3-bisglycidoxypropyl 1,1,3,3-tetramethyldisilaxane, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy 3,4-epoxycyclohexyl methyl cyclohexanecarboxylate, 1,4-cyclohexane dimethanol diglycidyl ether, bisphenol A diglycidyl ether, 1,2-cyclohexane dicarboxylic acid diglycidyl ether Ester (to name a few).
添加至最終調配物之固化劑為可起始及/或加速矽氧烷聚合物中之官能基之固化過程之任何化合物。此等固化劑可為熱及/或UV活化的(例如聚合反應經熱活化之情況下之熱酸或經UV活化之情況下之光引發劑)。如上所述之矽氧烷聚合物中之交聯基團較佳為環氧化物、環氧丙烷、丙烯酸酯、烯基或炔基。基於矽氧烷聚合物中之交聯基團選擇固化劑。 The curing agent added to the final formulation is any compound that can initiate and/or accelerate the curing process of the functional groups in the silicone polymer. These curing agents may be thermally and/or UV activated (e.g., thermal acid in the case where the polymerization reaction is thermally activated or photoinitiator in the case of UV activation). The crosslinking group in the above-mentioned silicone polymer is preferably an epoxide, propylene oxide, acrylate, alkenyl or alkynyl group. The curing agent is selected based on the crosslinking group in the silicone polymer.
在一個實施例中,用於環氧基及環氧丙烷基團之固化劑可選自顯示經阻斷或減少之活性之含氮固化劑,諸如一級胺及/或二級胺。定義「顯示經阻斷或減少之反應性之一級胺或二級胺」應意指由於化學或物理阻斷而不能與樹脂組分反應或僅具有與樹脂組分反應之極低能力,但可在釋放胺之後再生其反應性,例如藉由在增加之溫度下使其熔化、藉由移除外鞘或塗層、藉由壓力或超音波或其他能量類型之作用,開始樹脂組分之固化反應之彼等胺。 In one embodiment, the curing agent for epoxy groups and glycidyl groups can be selected from nitrogen-containing curing agents that exhibit blocked or reduced activity, such as primary amines and/or secondary amines. The definition "a primary or secondary amine showing blocked or reduced reactivity" shall mean that it cannot react with the resin component due to chemical or physical blockage or only has a very low ability to react with the resin component, but may Regenerate the reactivity after releasing the amine, for example by melting it at an increased temperature, by removing the sheath or coating, by pressure or ultrasound or other energy types to start the curing of the resin component Reaction of other amines.
熱可活化固化劑之實例包含至少一種有機硼烷或硼烷與至少一種胺之複合物。胺可為複合有機硼烷及/或硼烷且可在必要時解複合以釋放有機硼烷或硼烷之任何類型。胺可包括多種結構,例如任何一級胺或二級胺或含有一級胺及/或二級胺之多元胺。有機硼烷可選自烷基硼烷。此等熱尤其更佳硼烷之實例為三氟化硼。 適合之胺/(有機)硼烷複合物購自諸如金氏工業(King Industries)、空氣產品(Air products)以及ATO技術公司(ATO-Tech)之商業來源。 Examples of heat-activatable curing agents include at least one organoborane or a complex of borane and at least one amine. The amine may be a compound organoborane and/or borane and may be decomplexed as necessary to release organoborane or any type of borane. The amine may include various structures, for example, any primary or secondary amine or a polyamine containing primary and/or secondary amines. The organoborane can be selected from alkylborane. An example of a particularly preferred borane for such heat is boron trifluoride. Suitable amine/(organic) borane complexes are purchased from commercial sources such as King Industries, Air products, and ATO-Tech.
用於環氧基之其他熱活化固化劑為熱酸產生劑,其可在高溫下釋放強酸以催化環氧基之交聯反應。此等熱酸產生劑可例如為具有BF4 -、PF6 -、SbF6 -、CF3SO3 -以及(C6F5)4B-型複合陰離子之任何鎓鹽,如硫鎓鹽及碘鎓鹽。此等熱酸產生劑之商業實例為金氏工業製造之K-PURE CXC-1612及K-PURE CXC-1614。 Other thermally activated curing agents for epoxy groups are thermal acid generators, which can release strong acids at high temperatures to catalyze the crosslinking reaction of epoxy groups. These thermal acid generating agent may be, for example, 4 having a BF -, PF 6 -, SbF 6 -, CF 3 SO 3 - and (C 6 F 5) 4 B - anion of any compound of onium salt type, such as sulfonium salts and Iodonium salt. Commercial examples of these thermal acid generators are K-PURE CXC-1612 and K-PURE CXC-1614 manufactured by King's Industries.
另外,就含有聚合物之環氧化物及/或環氧丙烷而言,可使用經設計以參與或促進接著劑調配物之固化的固化劑、共固化劑、催化劑、引發劑或其他添加劑,如酸酐、胺、咪唑、硫醇、羧酸、酚、二氰二胺、脲、肼、醯肼、胺基-甲醛樹脂、三聚氰胺-甲醛樹脂、四級銨鹽、四級鏻鹽、三芳基硫鎓鹽、二芳基碘鎓鹽、重氮鹽以及類似物。 In addition, for epoxides and/or propylene oxide containing polymers, curing agents, co-curing agents, catalysts, initiators, or other additives designed to participate in or promote the curing of adhesive formulations, such as Anhydride, amine, imidazole, thiol, carboxylic acid, phenol, dicyandiamide, urea, hydrazine, hydrazine, amino-formaldehyde resin, melamine-formaldehyde resin, quaternary ammonium salt, quaternary phosphonium salt, triarylsulfide Onium salts, diaryliodonium salts, diazonium salts and the like.
對於丙烯酸酯,烯基及炔基交聯基團固化劑可為熱或UV活化的。熱活化之實例為過氧化物及偶氮化合物。過氧化物為含有不穩定氧-氧單鍵之化合物,所述單鍵易於經由溶血性裂解拆分成反應性自由基。偶氮化合物具有可分解為氮氣及兩個有機自由基之R-N=N-R官能基。在此兩種情況下,自由基均可催化丙烯酸酯、烯基及炔基鍵之聚合。過氧化物及偶氮化合物之實例為二-第三丁基過氧化物、2,2-雙(第三丁基過氧基)丁烷、過乙酸第三丁酯、2,5-二(第三丁基過氧基)-2,5-二甲基-3-己炔、過氧化二異丙苯、過氧化苯甲醯、二-第三戊基過氧化物、過氧基苯甲酸第三丁酯、4,4'-偶氮雙(4-氰基戊酸)、2,2'-偶氮雙(2-甲脒基丙烷)二鹽酸鹽、二苯基二 氮烯、偶氮二甲酸二乙酯以及1,1'-偶氮雙(環己烷甲腈)(僅舉數例)。 For acrylates, alkenyl and alkynyl crosslinking group curing agents can be thermally or UV activated. Examples of thermal activation are peroxides and azo compounds. Peroxides are compounds containing unstable oxygen-oxygen single bonds that are easily resolved into reactive free radicals via hemolytic cleavage. Azo compounds have R-N=N-R functional groups that can be decomposed into nitrogen and two organic radicals. In both cases, free radicals can catalyze the polymerization of acrylate, alkenyl and alkynyl bonds. Examples of peroxides and azo compounds are di-tert-butyl peroxide, 2,2-bis(tert-butylperoxy)butane, tert-butyl peracetate, 2,5-di( (Third butylperoxy)-2,5-dimethyl-3-hexyne, dicumyl peroxide, benzoyl peroxide, di-third pentyl peroxide, peroxybenzoic acid Third butyl ester, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-carboxamidopropane) dihydrochloride, diphenyl di Azene, diethyl azodicarboxylate, and 1,1'-azobis (cyclohexanecarbonitrile) (to name a few).
光引發劑為當暴露於光時分解為自由基且因此可促進丙烯酸酯、烯基以及炔基化合物之聚合之化合物。此等光引發劑之商業實例為由巴斯夫(BASF)製造之豔佳固(Irgacure)149、豔佳固184、豔佳固369、豔佳固500、豔佳固651、豔佳固784、豔佳固819、豔佳固907、豔佳固1700、豔佳固1800、豔佳固1850、豔佳固2959、豔佳固1173、豔佳固4265。
A photoinitiator is a compound that decomposes into free radicals when exposed to light and thus can promote the polymerization of acrylate, alkenyl, and alkynyl compounds. Commercial examples of these photoinitiators are Irgacure 149, Yanjiagu 184, Yanjiagu 369,
將固化劑併入至系統之一種方法為將固化劑或可充當固化劑之官能基附接至矽烷單體。因此,固化劑將加速矽氧烷聚合物之固化。附接至矽烷單體之此等種類之固化劑之實例為γ-咪唑基丙基三乙氧基矽烷、γ-咪唑基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-(三乙氧基矽基)丙基丁二酸酐、3-(三甲氧基矽基)丙基丁二酸酐、3-胺基丙基三甲氧基矽烷以及3-胺基丙基三乙氧基矽烷(僅舉數例)。 One method of incorporating a curing agent into the system is to attach the curing agent or a functional group that can act as a curing agent to the silane monomer. Therefore, the curing agent will accelerate the curing of the silicone polymer. Examples of such kinds of curing agents attached to the silane monomer are γ-imidazolylpropyltriethoxysilane, γ-imidazolylpropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3 -Mercaptopropyltriethoxysilane, 3-(triethoxysilyl)propyl succinic anhydride, 3-(trimethoxysilyl)propyl succinic anhydride, 3-aminopropyltrimethoxy Silane and 3-aminopropyltriethoxysilane (to name a few).
接著促進劑可為組成物之一部分且可為可增強固化產品與已塗覆產品之表面之間的接著之任何適合之化合物。最常用之接著促進劑為官能性矽烷,其中包含烷氧基矽烷及1至3個官能基。用於晶粒附接產物中之接著促進劑之實例可為辛基三乙氧基矽烷、巰基丙基三乙氧基矽烷、氰基丙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三乙氧基矽烷、3-(三甲氧基矽基)甲基丙烯酸丙酯、3-(三甲氧基矽基)丙烯酸丙酯、(3-縮水甘油基氧基丙基)三甲氧基矽烷或3-縮水甘油氧基丙基三乙氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷以及3-丙 烯醯氧基丙基三甲氧基矽烷。 The accelerator may then be part of the composition and may be any suitable compound that can enhance the adhesion between the cured product and the surface of the coated product. The most commonly used adhesion promoter is functional silane, which contains alkoxy silane and 1 to 3 functional groups. Examples of the adhesion promoter used in the die attach product may be octyltriethoxysilane, mercaptopropyltriethoxysilane, cyanopropyltrimethoxysilane, 2-(3,4-cyclo Oxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(trimethoxysilyl)propyl methacrylate, 3-(trimethyl Oxysilyl) propyl acrylate, (3-glycidyloxypropyl) trimethoxysilane or 3-glycidoxypropyl triethoxysilane, 3-methacryloxypropyl trimethyl Oxysilane and 3-propane Enyloxypropyltrimethoxysilane.
形成之聚合矽氧烷將具有[Si-O-Si-O]n重複主鏈,其上的有機官能基取決於含矽起始物質。然而,亦有可能達成[Si-O-Si-C]n或甚至[Si-O-Me-O]n(其中Me為金屬)主鏈。 The formed polymeric siloxane will have a repeating main chain of [Si-O-Si-O]n, and the organic functional groups on it will depend on the silicon-containing starting material. However, it is also possible to achieve a [Si-O-Si-C]n or even [Si-O-Me-O]n (where Me is a metal) main chain.
為了獲得[Si-O-Si-C]主鏈,具有下式之之化學品:R2 3-aR1 aSiR11SiR1 bR2 3-b In order to obtain the [Si-O-Si-C] main chain, a chemical with the following formula: R 2 3-a R 1 a SiR 11 SiR 1 b R 2 3-b
其中a為1至3,b為1至3,R1為如上文解釋之反應性基團,R2為烷基、烯基、炔基、醇、羧酸、二羧酸、芳基、聚芳基、多環烷基、雜環脂族基、雜環狀芳族基且R11獨立地為烷基或芳基,或其分子量小於1000公克/莫耳之寡聚物,可與如上所述之第一化合物、第二化合物以及第三化合物或此等的任何組合一起聚合。 Where a is 1 to 3, b is 1 to 3, R 1 is a reactive group as explained above, R 2 is alkyl, alkenyl, alkynyl, alcohol, carboxylic acid, dicarboxylic acid, aryl, poly The aryl group, polycyclic alkyl group, heterocyclic aliphatic group, heterocyclic aromatic group and R 11 are independently an alkyl group or an aryl group, or an oligomer with a molecular weight of less than 1000 g/mole, as described above The first compound, the second compound and the third compound or any combination thereof are polymerized together.
此等化合物之實例為1,2-雙(二甲基羥基矽烷基)乙烷、1,2-雙(三甲氧基矽烷基)乙烷、1,2-雙(二甲氧基甲基矽烷基)乙烷、1,2-雙(甲氧基二甲基矽烷基)乙烷、1,2-雙(三乙氧基矽烷基)乙烷、1,3-雙(二甲基羥基矽烷基)丙烷、1,3-雙(三甲氧基矽烷基)丙烷、1,3-雙(二甲氧基甲基矽烷基)丙烷、1,3-雙(甲氧基二甲基矽烷基)丙烷、1,3-雙(三乙氧基矽烷基)丙烷、1,4-雙(二甲基羥基矽烷基)丁烷、1,4-雙(三甲氧基矽烷基)丁烷、1,4-雙(二甲氧基甲基矽烷基)丁烷、1,4-雙(甲氧基二甲基矽烷基)丁烷、1,4-雙(三乙氧基矽烷基)丁烷、1,5- 雙(二甲基羥基矽烷基)戊烷、1,5-雙(三甲氧基矽烷基)戊烷、1,5-雙(二甲氧基甲基矽烷基)戊烷、1,5-雙(甲氧基二甲基矽烷基)戊烷、1,5-雙(三乙氧基矽烷基)戊烷、1,6-雙(二甲基羥基矽烷基)己烷、1,6-雙(三甲氧基矽烷基)己烷、1,6-雙(二甲氧基甲基矽烷基)己烷、1,6-雙(甲氧基二甲基矽烷基)己烷、1,6-雙(三乙氧基矽烷基)己烷、1,4-雙(三甲氧基矽烷基)苯、雙(三甲氧基矽烷基)萘、雙(三甲氧基矽烷基)蒽、雙(三甲氧基矽烷基)菲、雙(三甲氧基矽烷基)降冰片烯、1,4-雙(二甲基羥基矽烷基)苯、1,4-雙(甲氧基二甲基矽烷基)苯以及1,4-雙(三乙氧基矽基)苯(僅舉數例)。 Examples of such compounds are 1,2-bis(dimethylhydroxysilyl)ethane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(dimethoxymethylsilane) Group) ethane, 1,2-bis(methoxydimethylsilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1,3-bis(dimethylhydroxysilane) Group) propane, 1,3-bis(trimethoxysilyl)propane, 1,3-bis(dimethoxymethylsilyl)propane, 1,3-bis(methoxydimethylsilyl) Propane, 1,3-bis(triethoxysilyl) propane, 1,4-bis(dimethylhydroxysilyl) butane, 1,4-bis(trimethoxysilyl) butane, 1, 4-bis(dimethoxymethylsilyl)butane, 1,4-bis(methoxydimethylsilyl)butane, 1,4-bis(triethoxysilyl)butane, 1,5- Bis(dimethylhydroxysilyl)pentane, 1,5-bis(trimethoxysilyl)pentane, 1,5-bis(dimethoxymethylsilyl)pentane, 1,5-bis (Methoxydimethylsilyl)pentane, 1,5-bis(triethoxysilyl)pentane, 1,6-bis(dimethylhydroxysilyl)hexane, 1,6-bis (Trimethoxysilyl)hexane, 1,6-bis(dimethoxymethylsilyl)hexane, 1,6-bis(methoxydimethylsilyl)hexane, 1,6- Bis(triethoxysilyl)hexane, 1,4-bis(trimethoxysilyl)benzene, bis(trimethoxysilyl)naphthalene, bis(trimethoxysilyl)anthracene, bis(trimethoxyl) Silyl)phenanthrene, bis(trimethoxysilyl) norbornene, 1,4-bis(dimethylhydroxysilyl)benzene, 1,4-bis(methoxydimethylsilyl)benzene and 1,4-bis(triethoxysilyl)benzene (to name a few).
在一個實施例中,為了獲得[Si-O-Si-C]主鏈,具有下式之化合物R5 3-(c+d)R4 dR3 cSiR11SiR3 eR4 fR5 3-(e+f) In one embodiment, in order to obtain the [Si-O-Si-C] main chain, the compound having the formula R 5 3-(c+d) R 4 d R 3 c SiR 11 SiR 3 e R 4 f R 5 3-(e+f)
其中R3為交聯官能基,R4為反應性基團,且R5為烷基、烯基、炔基、醇、羧酸、二羧酸、芳基、聚芳基、多環烷基、雜環脂族基、雜環芳族基,R11獨立地為烷基或芳基,且其中c=1至2,d=1至(3-c),e=1至2,且f=1至(3-e),或其分子量小於1000公克/莫耳之寡聚物,與本文中如所提及之第一化合物、第二化合物、第三化合物或此等之任何組合一起聚合。 Where R 3 is a cross-linking functional group, R 4 is a reactive group, and R 5 is an alkyl group, alkenyl group, alkynyl group, alcohol, carboxylic acid, dicarboxylic acid, aryl group, polyaryl group, polycyclic alkyl group , Heterocyclic aliphatic group, heterocyclic aromatic group, R 11 is independently an alkyl group or an aryl group, and wherein c=1 to 2, d=1 to (3-c), e=1 to 2, and f =1 to (3-e), or an oligomer whose molecular weight is less than 1000 g/mole, polymerized together with the first compound, second compound, third compound, or any combination of these as mentioned herein .
此等化合物之實例為1,2-雙(乙烯基二甲氧基矽烷基)乙烷、1,2-雙(乙炔基二甲氧基矽烷基)乙烷、1,2-雙(乙炔基二甲氧基) 乙烷、1,2-雙(3-縮水甘油氧基丙基二甲氧基矽烷基)乙烷、1,2-雙[2-(3,4-環氧環己基)乙基二甲氧基矽烷基]乙烷、1,2-雙(甲基丙烯酸丙酯二甲氧基矽烷基)乙烷、1,4-雙(乙烯基二甲氧基矽烷基)苯、1,4-雙(乙炔基二甲氧基矽烷基)苯、1,4-雙(乙炔基二甲氧基矽烷基)苯、1,4-雙(3-縮水甘油氧基丙基二甲氧基矽烷基)苯、1,4-雙[2-(3,4-環氧環己基)乙基二甲氧基矽烷基]苯、1,4-雙(甲基丙烯酸丙酯二甲氧基矽烷基)苯(僅舉數例)。 Examples of such compounds are 1,2-bis(vinyldimethoxysilyl)ethane, 1,2-bis(ethynyldimethoxysilyl)ethane, 1,2-bis(ethynyl (Dimethoxy) Ethane, 1,2-bis(3-glycidoxypropyldimethoxysilyl)ethane, 1,2-bis[2-(3,4-epoxycyclohexyl)ethyldimethoxy Silane-based) ethane, 1,2-bis (propyl methacrylate dimethoxysilyl) ethane, 1,4-bis (vinyl dimethoxysilyl) benzene, 1,4-bis (Ethynyldimethoxysilyl)benzene, 1,4-bis(ethynyldimethoxysilyl)benzene, 1,4-bis(3-glycidoxypropyldimethoxysilyl) Benzene, 1,4-bis[2-(3,4-epoxycyclohexyl)ethyldimethoxysilyl]benzene, 1,4-bis(propylmethacrylate dimethoxysilyl)benzene (To name just a few).
在一個實施例中,具有以下分子式之矽氧烷單體R1 aR2’ bR3 3-(a+b)Si-O-SiR2’ 2-O-Si R1 aR2’ bR3 3-(a+b) In one embodiment, the siloxane monomer R 1 a R 2′ b R 3 3-(a+b) Si-O-SiR 2′ 2 -O-Si R 1 a R 2′ b R 3 3-(a+b)
其中R1為如上文解釋之反應性基團,R2’為如上文解釋之烷基或芳基,R3為如上文解釋之交聯官能基,且a=0至3,b=0至3,與先前提及之矽烷聚合或作為添加劑添加至最終調配物。 Where R 1 is a reactive group as explained above, R 2′ is an alkyl or aryl group as explained above, R 3 is a cross-linked functional group as explained above, and a=0 to 3, b=0 to 3. Polymerize with the previously mentioned silane or add it as an additive to the final formulation.
此等化合物之實例為1,1,5,5-四甲氧基-1,5-二甲基-3,3-二苯基三矽氧烷、1,1,5,5-四甲氧基-1,3,3,5-四苯基三矽氧烷、1,1,5,5-四乙氧基-3,3-二苯基三矽氧烷、1,1,5,5-四甲氧基-1,5-二乙烯基-3,3-二苯基三矽氧烷、1,1,5,5-四甲氧基-1,5-二甲基-3,3-二異丙基三矽氧烷、1,1,1,5,5,5-六甲氧基-3,3-二苯基三矽氧烷、1,5-二甲基-1,5-二乙氧基-3,3-二苯基三矽氧烷、1,5-雙(巰基丙基)-1,1,5,5-四甲氧基-3,3-二苯基三矽氧烷、1,5-二乙烯基-1,1,5,5-四甲氧基-3-苯基-3-甲基三矽氧烷、1,5-二乙烯基-1,1,5,5-四甲氧基-3-環己基-3-甲基三矽氧烷、1,1,7,7-四甲氧基-1,7-二乙烯基-3,3,5,5-四甲基四矽氧 烷、1,1,5,5-四甲氧基-3,3-二甲基三矽氧烷、1,1,7,7-四乙氧基-3,3,5,5-四甲基四矽氧烷、1,1,5,5-四乙氧基-3,3-二甲基三矽氧烷、1,1,5,5-四甲氧基-1,5-[2-(3,4-環氧環己基)乙基]-3,3-二苯基三矽氧烷、1,1,5,5-四甲氧基-1,5-(3-縮水甘油氧基丙基)-3,3-二苯基三矽氧烷、1,5-二甲基-1,5-二甲氧基-1,5-2-(3,4-環氧環己基)乙基]-3,3-二苯基三矽氧烷、1,5-二甲基-1,5-二甲氧基-1,5-(3-縮水甘油氧基丙基)-3,3-二苯基三矽氧烷(僅舉數例)。 Examples of these compounds are 1,1,5,5-tetramethoxy-1,5-dimethyl-3,3-diphenyltrisiloxane, 1,1,5,5-tetramethoxy Yl-1,3,3,5-tetraphenyltrisiloxane, 1,1,5,5-tetraethoxy-3,3-diphenyltrisiloxane, 1,1,5,5 -Tetramethoxy-1,5-divinyl-3,3-diphenyltrisiloxane, 1,1,5,5-tetramethoxy-1,5-dimethyl-3,3 -Diisopropyltrisiloxane, 1,1,1,5,5,5-hexamethoxy-3,3-diphenyltrisiloxane, 1,5-dimethyl-1,5- Diethoxy-3,3-diphenyltrisiloxane, 1,5-bis(mercaptopropyl)-1,1,5,5-tetramethoxy-3,3-diphenyltrisiloxane Oxane, 1,5-divinyl-1,1,5,5-tetramethoxy-3-phenyl-3-methyltrisiloxane, 1,5-divinyl-1,1, 5,5-tetramethoxy-3-cyclohexyl-3-methyltrisiloxane, 1,1,7,7-tetramethoxy-1,7-divinyl-3,3,5, 5-tetramethyltetrasiloxane Alkanes, 1,1,5,5-tetramethoxy-3,3-dimethyltrisiloxane, 1,1,7,7-tetraethoxy-3,3,5,5-tetramethyl Tetrasiloxane, 1,1,5,5-tetraethoxy-3,3-dimethyltrisiloxane, 1,1,5,5-tetramethoxy-1,5-[2 -(3,4-epoxycyclohexyl)ethyl]-3,3-diphenyltrisiloxane, 1,1,5,5-tetramethoxy-1,5-(3-glycidoxy Propyl)-3,3-diphenyltrisiloxane, 1,5-dimethyl-1,5-dimethoxy-1,5-2-(3,4-epoxycyclohexyl) Ethyl]-3,3-diphenyltrisiloxane, 1,5-dimethyl-1,5-dimethoxy-1,5-(3-glycidoxypropyl)-3, 3-Diphenyltrisiloxane (to name a few).
添加至組成物(在聚合如上文所指出之矽氧烷材料之後)之添加劑可為具有下式之矽烷化合物:R1 aR2’ bSiR3 4-(a+b)w Additive added to the composition (after the polymerization silicon alumoxane of material as noted above) may be of the formula of Silane compound: R 1 a R 2 'b SiR 3 4- (a + b) w
其中R1為反應性基團,如羥基、烷氧基或乙醯氧基,R2’為烷基或芳基,R3為交聯化合物,如環氧基、環氧丙烷、烯基、丙烯酸酯或炔基,a=0至1且b=0至1。 Where R 1 is a reactive group, such as hydroxy, alkoxy or acetoxy, R 2′ is an alkyl or aryl group, and R 3 is a cross-linking compound, such as epoxy, propylene oxide, alkenyl, Acrylate or alkynyl, a=0 to 1 and b=0 to 1.
此類添加劑之實例為三-(3-縮水甘油氧基丙基)苯基矽烷、三-[2-(3,4-環氧環己基)乙基]苯基矽烷、三-(3-甲基丙烯醯氧基)苯基矽烷、三-(3-丙烯醯氧基)苯基矽烷、四-(3-縮水甘油氧基丙基)矽烷、四-[2-(3,4-環氧環己基)乙基]矽烷、四-(3-甲基丙烯醯氧基)矽烷、四-(3-丙烯醯氧基)矽烷、三-(3-縮水甘油氧基丙基)對甲苯基矽烷、三-[2-(3,4-環氧環己基)乙基]對甲苯基矽烷、三-(3-甲基丙烯醯氧基)對甲苯基矽烷、三-(3-丙烯醯氧基)對甲苯基矽烷、三-(3-縮水甘油氧基丙基)羥基矽烷、三-[2-(3,4-環氧環己基)乙基]羥基矽 烷、三-(3-甲基丙烯醯氧基)羥基矽烷、三-(3-丙烯醯氧基)羥基矽烷。 Examples of such additives are tri-(3-glycidoxypropyl) phenyl silane, tri-[2-(3,4-epoxycyclohexyl) ethyl] phenyl silane, tri-(3-methyl Acrylic Acryloyloxy)phenyl Silane, Tri-(3-Acryloyloxy)phenyl Silane, Tetra-(3-Glycidoxypropyl) Silane, Tetra-(2-(3,4-Epoxy (Cyclohexyl) ethyl) silane, tetra-(3-methacryloxy) silane, tetra-(3-propenyl oxy) silane, tri-(3-glycidoxypropyl) p-tolyl silane , Tri-[2-(3,4-epoxycyclohexyl)ethyl] p-tolyl silane, tri-(3-methacryl acetyloxy) p-tolyl silane, tri-(3-propenyl oxy) ) P-tolyl silane, tri-(3-glycidoxypropyl) hydroxy silane, tri-[2-(3,4-epoxycyclohexyl) ethyl] hydroxy silane Alkane, tri-(3-methacryloxy)hydroxysilane, tri-(3-propenyloxy)hydroxysilane.
添加劑亦可為任何有機或矽酮聚合物,其可與主要聚合物基質反應或可不與主要聚合物基質反應,因此充當塑化劑、軟化劑或基質改質劑,如矽酮。添加劑亦可為無機聚縮合物,諸如SiOx、TiOx、AlOx、TaOx、HfOx、ZrOx、SnOx、聚矽氮烷。 The additive may also be any organic or silicone polymer, which may or may not react with the main polymer matrix, thus acting as a plasticizer, softener or matrix modifier, such as silicone. The additives may also be inorganic polycondensates such as SiOx, TiOx, AlOx, TaOx, HfOx, ZrOx, SnOx, polysilazane.
粒狀填充劑可為導電材料,諸如碳黑、石墨、石墨烯、金、銀、銅、鉑、鈀、鎳、鋁、鍍銀銅、鍍銀鋁、鉍、錫、鉍-錫合金、鍍銀纖維、鍍鎳銅、鍍銀及鎳之銅、鍍金銅、鍍金及鎳之銅,或其可為鍍金、銀-金、銀、鎳、錫、鉑、鈦之聚合物,諸如聚丙烯酸酯、聚苯乙烯或矽酮,但不限於此。填充劑亦可為半導體材料,諸如矽、n型或p型摻雜矽、GaN、InGaN、GaAs、InP、SiC,但不限於此。此外,填充劑可為量子點或表面電漿子粒子或磷光體粒子。其他半導體粒子或量子點,諸如Ge、GaP、InAs、CdSe、ZnO、ZnSe、TiO2、ZnS、CdS、CdTe等亦為可能的。 The particulate filler may be a conductive material such as carbon black, graphite, graphene, gold, silver, copper, platinum, palladium, nickel, aluminum, silver-plated copper, silver-plated aluminum, bismuth, tin, bismuth-tin alloy, plated Silver fiber, nickel-plated copper, silver-plated and nickel-plated copper, gold-plated copper, gold-plated and nickel-plated copper, or it may be a polymer of gold-plated, silver-gold, silver, nickel, tin, platinum, titanium, such as polyacrylate , Polystyrene or silicone, but not limited to this. The filler may also be a semiconductor material, such as silicon, n-type or p-type doped silicon, GaN, InGaN, GaAs, InP, SiC, but is not limited thereto. In addition, the filler may be quantum dots or surface plasmon particles or phosphor particles. Other semiconductor particles or quantum dots such as Ge, GaP, InAs, CdSe, ZnO, ZnSe, TiO 2 , ZnS, CdS, CdTe, etc. are also possible.
填充劑可為粒子,其為任何適合之金屬粒子或半金屬粒子,諸如選自金、銀、銅、鉑、鈀、銦、鐵、鎳、鋁、碳、鈷、鍶、鋅、鉬、鈦、鎢、鍍銀銅、鍍銀鋁、鉍、錫、鉍-錫合金、鍍銀纖維或此等物質之合金或組合。預想為過渡金屬粒子(無論前過渡金屬或後過渡金屬)之金屬粒子,如同半金屬及類金屬一樣。預想半金屬或類金屬粒子,諸如砷、銻、碲、鍺、矽以及鉍。 The filler may be particles, which are any suitable metal particles or semi-metal particles, such as selected from gold, silver, copper, platinum, palladium, indium, iron, nickel, aluminum, carbon, cobalt, strontium, zinc, molybdenum, titanium , Tungsten, silver-plated copper, silver-plated aluminum, bismuth, tin, bismuth-tin alloy, silver-plated fiber or alloys or combinations of these substances. The metal particles envisioned as transition metal particles (whether before or after transition metals) are like semi-metals and metalloids. It is envisioned that semi-metallic or metalloid particles, such as arsenic, antimony, tellurium, germanium, silicon and bismuth.
或者,其可為不導電材料,諸如二氧化矽、石英、氧化鋁、氮化鋁、塗佈有二氧化矽之氮化鋁、硫酸鋇、三水合氧化鋁、氮化硼等。填充劑可為粒子或薄片形式,且可為微米尺寸或奈米尺寸。填充劑可包括為金屬或半金屬之氮化物、氮氧化物、碳化物以及碳 氧化物之陶瓷化合物粒子。特定言之,填充劑可為粒子,所述粒子為矽、鋅、鋁、釔、鐿、鎢、鈦矽、鈦、銻、釤、鎳、鎳鈷、鉬、鎂、錳、鑭系元素、鐵、銦錫、銅、鈷鋁、鉻、銫或鈣之氧化物之陶瓷粒子。 Alternatively, it may be a non-conductive material, such as silicon dioxide, quartz, aluminum oxide, aluminum nitride, aluminum nitride coated with silicon dioxide, barium sulfate, aluminum trihydrate, boron nitride, and the like. The filler may be in the form of particles or flakes, and may be micron-sized or nano-sized. Fillers can include nitrides, oxynitrides, carbides and carbons that are metals or semi-metals Oxide ceramic compound particles. Specifically, the filler may be particles, and the particles are silicon, zinc, aluminum, yttrium, ytterbium, tungsten, titanium silicon, titanium, antimony, samarium, nickel, nickel cobalt, molybdenum, magnesium, manganese, lanthanide, Ceramic particles of oxides of iron, indium tin, copper, cobalt aluminum, chromium, cesium or calcium.
亦可能的為包括碳之粒子且選自碳黑、石墨、石墨烯、金剛石、碳氮化矽、碳氮化鈦、碳奈米芽(nanobud)以及碳奈米管。填充劑之粒子可為碳化物粒子,諸如碳化鐵、碳化矽、碳化鈷、碳化鎢、碳化硼、碳化鋯、碳化鉻、碳化鈦或碳化鉬。粒子可替代地為氮化物粒子,諸如氮化鋁、氮化鉭、氮化硼、氮化鈦、氮化銅、氮化鉬、氮化鎢、氮化鐵、氮化矽、氮化銦、氮化鎵或氮化碳。 It is also possible that the particles include carbon and are selected from carbon black, graphite, graphene, diamond, silicon carbonitride, titanium carbonitride, carbon nanobuds, and carbon nanotubes. The particles of the filler may be carbide particles, such as iron carbide, silicon carbide, cobalt carbide, tungsten carbide, boron carbide, zirconium carbide, chromium carbide, titanium carbide, or molybdenum carbide. The particles may alternatively be nitride particles such as aluminum nitride, tantalum nitride, boron nitride, titanium nitride, copper nitride, molybdenum nitride, tungsten nitride, iron nitride, silicon nitride, indium nitride, Gallium nitride or carbon nitride.
取決於最終應用,可使用任何適合尺寸之粒子。在許多情況下,使用平均粒度小於100微米,且較佳小於50微米或甚至20微米之小粒子。亦預想亞微米粒子,諸如小於1微米,或例如1奈米至500奈米,諸如小於200奈米,諸如1奈米至100奈米,或甚至小於10奈米之彼等。在其他實例中,提供平均粒度為5奈米至50奈米、或15奈米至75奈米、小於100奈米或50奈米至500奈米之粒子。並非細長,例如大體上球形或正方形之粒子,或具有扁平盤形外觀(具有平滑邊緣或粗糙邊緣)之薄片為可能的,如同細長晶鬚、圓筒、導線以及其他細長粒子,諸如具有5:1或更大,或10:1或更大之縱橫比的粒子。具有極高縱橫比之極細長粒子,諸如奈米線及奈米管亦為可能的。奈米線或奈米管之高縱橫比可為25:1或更大、50:1或更大或甚至100:1或更大。奈米線或奈米管之平均粒度是參考最小尺寸(寬度或直徑),因為長度可相當長,甚至達至幾公分長。如本文所用,術語「平均粒度」是指50體積 %之粒子之直徑小於所述值之累積體積分佈曲線處之D50值。 Depending on the final application, particles of any suitable size can be used. In many cases, small particles with an average particle size of less than 100 microns, and preferably less than 50 microns or even 20 microns are used. Submicron particles, such as less than 1 micron, or, for example, 1 nanometer to 500 nanometers, such as less than 200 nanometers, such as 1 nanometer to 100 nanometers, or even less than 10 nanometers are also envisioned. In other examples, particles having an average particle size of 5 nm to 50 nm, or 15 nm to 75 nm, less than 100 nm, or 50 nm to 500 nm are provided. Not elongated, such as particles that are generally spherical or square, or flakes with a flat disc-shaped appearance (with smooth or rough edges) are possible, like elongated whiskers, cylinders, wires, and other elongated particles, such as having 5: Particles with an aspect ratio of 1 or larger, or 10:1 or larger. Very elongated particles with extremely high aspect ratio, such as nanowires and nanotubes, are also possible. The high aspect ratio of the nanowire or nanotube can be 25:1 or greater, 50:1 or greater, or even 100:1 or greater. The average particle size of nanowires or nanotubes refers to the smallest size (width or diameter) because the length can be quite long, even up to a few centimeters long. As used herein, the term "average particle size" refers to 50 volumes % Of the particles have a diameter smaller than the D50 value at the cumulative volume distribution curve of the value.
粒子可為如本文中他處所提及之粒子之混合物,其中平均粒度大於200奈米之第一組粒子與平均粒度小於200奈米之第二組粒子一起提供,例如其中第一組之平均粒度大於500奈米且第二組之平均粒度小於100奈米(例如第一組之平均粒度大於1微米,第二組之粒度小於50奈米,或甚至小於25奈米)。較小粒子之熔點低於較大粒子之熔點,且較小粒子在小於具有加大微米尺寸的相同材料之粒子或質量的溫度下熔融或燒結。在一個實例中,較小粒子之平均粒度小於1微米且在小於相同材料之總體溫度之溫度下熔融或燒結。取決於所選粒子材料及平均粒度,熔化及燒結溫度將不同。 The particles may be a mixture of particles as mentioned elsewhere herein, wherein the first group of particles having an average particle size greater than 200 nanometers and the second group of particles having an average particle size less than 200 nanometers are provided together, for example where the average of the first group The particle size is greater than 500 nanometers and the average particle size of the second group is less than 100 nanometers (eg, the average particle size of the first group is greater than 1 micrometer and the particle size of the second group is less than 50 nanometers, or even less than 25 nanometers). The melting point of the smaller particles is lower than the melting point of the larger particles, and the smaller particles are melted or sintered at a temperature smaller than the particles or mass of the same material with an enlarged micron size. In one example, the smaller particles have an average particle size of less than 1 micrometer and are melted or sintered at a temperature less than the overall temperature of the same material. Depending on the selected particulate material and average particle size, the melting and sintering temperatures will be different.
作為一個實例,極小銀奈米粒子可在低於120℃下熔融,且在甚至更低溫度下燒結。因此,必要時,較小粒子之熔化或燒結溫度可等於或低於聚合物固化溫度,以在矽氧烷聚合物材料之完全交聯及固化之前形成將較大粒子連接在一起之熔化或燒結粒子之網。在一個實例中,較小粒子在低於130℃,例如低於120℃之溫度下與較大粒子一起熔化或燒結,或甚至在低於110℃下燒結,而矽氧烷材料在較高溫度下經歷實質性交聯,例如在低於110℃下實質性燒結或熔化,但在高於110℃下實質性聚合(或例如在低於120℃(或130℃)下實質性燒結或熔化,但在高於120℃(或130℃)下實質性聚合)。較小粒子在矽氧烷材料之實質性聚合之前的燒結或熔化允許形成之金屬「網格」具有較大互連性,其增加固化層所述最終導電性。較小粒子之實質性燒結或熔化之前的實質性聚合減小形成之金屬「網格」之量且降低最終固化層之導電性。當 然,亦有可能僅提供較小平均粒度(例如亞微米尺寸)之粒子其仍可達成相比於相同塊體(或例如平均粒度大於1微米之相同粒子)之較低燒結點及熔點之效益。 As an example, very small silver nanoparticles can be melted below 120°C and sintered at even lower temperatures. Therefore, if necessary, the melting or sintering temperature of the smaller particles may be equal to or lower than the polymer curing temperature to form a melting or sintering linking the larger particles together before the silicone polymer material is completely crosslinked and solidified The web of particles. In one example, the smaller particles are melted or sintered with the larger particles at a temperature below 130°C, for example below 120°C, or even sintered below 110°C, while the siloxane material is at a higher temperature Undergoes substantial cross-linking, such as substantially sintering or melting below 110°C, but substantially polymerizing above 110°C (or, for example, substantially sintering or melting below 120°C (or 130°C), but (Substantially polymerized above 120°C (or 130°C)). The sintering or melting of the smaller particles before the substantial polymerization of the silicone material allows the formed metal "mesh" to have greater interconnectivity, which increases the final conductivity of the cured layer. The substantial polymerization of the smaller particles before substantial sintering or melting reduces the amount of metal "grid" formed and reduces the conductivity of the final cured layer. when However, it is also possible to provide only particles with a smaller average particle size (e.g. sub-micron size) which can still achieve the benefit of a lower sintering point and melting point compared to the same bulk (or the same particles with an average particle size greater than 1 micron) .
為了增強與填充劑及矽氧烷聚合物之偶合,可使用偶合劑。此偶合劑將增加填充劑與聚合物之間的接著且因此可增加最終產物之導熱性及/或導電性。偶合劑可為任何具有下式之矽烷單體:R13 hR14 iSiR15 j In order to enhance coupling with fillers and silicone polymers, coupling agents can be used. This coupling agent will increase the adhesion between the filler and the polymer and thus may increase the thermal conductivity and/or electrical conductivity of the final product. The coupling agent can be any silane monomer having the following formula: R 13 h R 14 i SiR 15 j
其中R13為反應性基團,如鹵素、羥基、烷氧基、乙醯基或乙醯氧基,R14為烷基或芳基,且R15為包含如環氧基、酸酐、氰基、環氧丙烷、胺、巰基、烯丙基、烯基或炔基之官能基,h=0至4,i=0至4,j=0至4且h+i+j=4。 Where R 13 is a reactive group, such as halogen, hydroxy, alkoxy, acetyl or ethoxy, R 14 is an alkyl or aryl group, and R 15 is comprised of, for example, epoxy, anhydride, cyano , Propylene oxide, amine, mercapto, allyl, alkenyl or alkynyl functional group, h=0 to 4, i=0 to 4, j=0 to 4 and h+i+j=4.
偶合劑可在製備最終產物時直接與填充劑、矽氧烷聚合物、固化劑以及添加劑混合或填充劑粒子可在其與粒子混合之前藉由偶合劑處理。 The coupling agent can be directly mixed with the filler, the silicone polymer, the curing agent, and the additives when preparing the final product or the filler particles can be treated with the coupling agent before they are mixed with the particles.
若粒子在用於最終調配物之前以偶合劑處理,則可使用不同方法,如自醇溶液沈積、自水溶液沈積、大量沈積至填充劑上以及無水液相沈積。在自醇溶液沈積中,製備醇/水溶液且將溶液pH調節至略微酸性(pH 4.5-5.5)。將矽烷添加至此溶液且混合幾分鐘以允許部分水解。接著,添加填充劑粒子且持續不同時間段自室溫至回流溫度混合溶液。在混合之後,過濾粒子,用乙醇沖洗且 在烘箱中乾燥以藉由偶合劑獲得表面處理之粒子。自水溶液沈積類似於自醇溶液沈積,但使用純水而非醇作為溶劑。若使用非胺官能化,則藉由酸再次調節pH。在將粒子與水/矽烷混合物混合之後,過濾粒子,沖洗且乾燥。 If the particles are treated with a coupling agent before being used in the final formulation, different methods can be used, such as deposition from alcohol solutions, deposition from aqueous solutions, bulk deposition onto fillers, and anhydrous liquid phase deposition. In deposition from an alcohol solution, an alcohol/water solution is prepared and the pH of the solution is adjusted to be slightly acidic (pH 4.5-5.5). Silane was added to this solution and mixed for a few minutes to allow partial hydrolysis. Next, filler particles are added and the solution is mixed from room temperature to reflux temperature for different periods of time. After mixing, the particles are filtered, rinsed with ethanol and Dry in an oven to obtain surface-treated particles with a coupling agent. Deposition from an aqueous solution is similar to deposition from an alcohol solution, but uses pure water instead of alcohol as the solvent. If non-amine functionalization is used, the pH is adjusted again with acid. After mixing the particles with the water/silane mixture, the particles are filtered, rinsed and dried.
大量沈積方法為矽烷偶合劑與溶劑在無任何水或pH調節的情況下混合之方法。使用如噴塗之不同方法使填充劑粒子塗佈有矽烷醇溶液且接著在烘箱中乾燥。 The bulk deposition method is a method of mixing the silane coupling agent and the solvent without any water or pH adjustment. The filler particles are coated with the silanol solution using different methods such as spraying and then dried in an oven.
在無水液相沈積中,矽烷與如甲苯、四氫呋喃或烴之有機溶劑混合,填充劑粒子在此溶液中回流且藉由真空或過濾移除額外溶劑。粒子亦可隨後在烘箱中乾燥,但由於回流條件下粒子與填充劑之間的直接反應,其有時不需要。 In anhydrous liquid phase deposition, silane is mixed with an organic solvent such as toluene, tetrahydrofuran, or hydrocarbon, the filler particles are refluxed in this solution and the extra solvent is removed by vacuum or filtration. The particles can also be subsequently dried in an oven, but due to the direct reaction between the particles and the filler under reflux conditions, they are sometimes not needed.
此類矽烷偶合劑之實例為雙(2-羥乙基)-3-胺基丙基三乙氧基矽烷、烯丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基甲基二乙氧基矽烷、3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、(N-三甲氧基矽烷基丙基)聚乙二亞胺、三甲氧基矽烷基丙基二伸乙基三胺、苯基三乙氧基矽烷、苯基三甲氧基矽烷、3-氯丙基三甲氧基矽烷、1-三甲氧基矽基-2(對,間氯甲基)苯乙烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、異氰酸丙酯三乙氧基矽烷、雙[3-(三乙氧基矽基)丙基]四硫化物、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、2-(二苯膦基)乙基三乙氧基矽烷、1,3-二乙烯基四甲基二矽氮烷、六甲基二矽氮烷、3-(N-苯乙烯基甲基-2-胺基乙胺基)丙基三甲氧基矽烷、N-(三乙氧基矽烷基 丙基)脲、1,3-二乙烯基四甲基二矽氮烷、乙烯基三乙氧基矽烷以及乙烯基三甲氧基矽烷(僅舉數例)。 Examples of such silane coupling agents are bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, allyltrimethoxysilane, N-(2-aminoethyl)-3- Aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropylmethyl diethoxysilane, 3- Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, (N-trimethoxysilylpropyl) polyethyleneimine, trimethoxysilylpropyl diethylidene tris Amine, phenyltriethoxysilane, phenyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 1-trimethoxysilyl-2 (p, m-chloromethyl) styrene, 2- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, propyl isocyanate triethoxysilane, bis[3-(triethoxy (Silyl)propyl]tetrasulfide, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 2- (Diphenylphosphino) ethyltriethoxysilane, 1,3-divinyltetramethyldisilazane, hexamethyldisilazane, 3-(N-styrylmethyl-2- Aminoethylamino)propyltrimethoxysilane, N-(triethoxysilyl Propyl)urea, 1,3-divinyltetramethyldisilazane, vinyltriethoxysilane and vinyltrimethoxysilane (to name a few).
取決於添加之粒子之類型,矽氧烷-粒子固化最終產物可為熱傳導層或膜,諸如在最終熱固化或UV固化之後具有大於0.5瓦/公尺.克耳文(kelvin)(W/(m.K))之熱導率。取決於選擇之粒子之類型,較高熱導率材料為可能的。矽氧烷組成物中之金屬粒子可產生熱導率大於2.0瓦/公尺.克耳文,諸如大於4.0瓦/公尺.克耳文或甚至大於10.0瓦/公尺.克耳文之固化最終膜。取決於最終應用,可能需要更高的熱導率,諸如大於50.0瓦/公尺.克耳文,或甚至大於100.0瓦/公尺.克耳文。然而,在其他應用中,可選擇粒子以在必要時產生具有低熱導率之材料。 Depending on the type of particles added, the final product of the silicone-particle curing may be a thermally conductive layer or film, such as after final thermal curing or UV curing with greater than 0.5 W/m. The thermal conductivity of kelvin (W/(m.K)). Depending on the type of particles selected, higher thermal conductivity materials are possible. The metal particles in the silicone composition can produce a thermal conductivity greater than 2.0 watts/meter. Kelvin, such as greater than 4.0 watts/meter. Kelvin or even greater than 10.0 watts/meter. Creven's cured final film. Depending on the final application, higher thermal conductivity may be required, such as greater than 50.0 watts/meter. Kelvin, or even greater than 100.0 watts/meter. Kelvin. However, in other applications, particles can be selected to produce materials with low thermal conductivity when necessary.
另外,必要時,最終固化產物可具有低電阻率,諸如小於1×10-3Ω.m,較佳小於1×10-5Ω.m,且更佳1×10-7Ω.m。另外,沈積薄膜之薄層電阻較佳小於100000,更佳小於10000。然而,材料之多種所需最終用途可具有高電阻率。 In addition, if necessary, the final cured product may have a low resistivity, such as less than 1×10 -3 Ω. m, preferably less than 1×10 -5 Ω. m, and better 1×10 -7 Ω. m. In addition, the sheet resistance of the deposited film is preferably less than 100,000, and more preferably less than 10,000. However, the various desired end uses of the material can have high resistivity.
在一些情況下,特別是組成物將應用於需要光學特徵之裝置中時,儘管在一些情況下可能需要最終固化矽氧烷具有光學吸收特性,更可能的是材料將合意地高度透射可見光譜內(或操作最終裝置之光譜內)的光,或將合意地高度反射可見光譜內(或操作裝置之光譜內)的光。作為透明材料之實例,厚度為1微米至50微米之最終固化層將透射至少85%之垂直入射至其之可見光,或較佳透射至少90%,更佳至少92.5%且最佳至少95%。 In some cases, especially when the composition will be used in devices that require optical features, although in some cases it may be required that the final cured silicone has optical absorption properties, it is more likely that the material will desirably be highly transmissive within the visible spectrum (Or within the spectrum of the operating device), or will desirably highly reflect light within the visible spectrum (or within the spectrum of the operating device). As an example of a transparent material, the final cured layer with a thickness of 1 micrometer to 50 micrometers will transmit at least 85% of normal light incident on it, or preferably at least 90%, more preferably at least 92.5%, and most preferably at least 95%.
作為反射層之實例,最終固化層可反射至少85%入射至其之光,較佳反射至少95%以90度之角入射至其之光。 As an example of a reflective layer, the final cured layer can reflect at least 85% of light incident on it, preferably at least 95% of light incident on it at an angle of 90 degrees.
本發明之材料亦可含有穩定劑及/或抗氧化劑。添加此等化合物以保護材料免於由藉由諸如熱、光或來自原料之殘餘催化劑之物質誘導的與氧氣之反應而引起之降解。 The material of the present invention may also contain stabilizers and/or antioxidants. These compounds are added to protect the material from degradation caused by reactions with oxygen induced by substances such as heat, light, or residual catalyst from raw materials.
本文中可適用的穩定劑或抗氧化劑為高分子量受阻酚及多官能性酚,諸如含硫及磷之酚。受阻酚已為本領域的技術人員所熟知,且可表徵為亦含有與其酚類羥基非常接近之立體大型(sterically bulky)自由基之酚類化合物。特定言之,第三丁基一般在相對於酚類羥基之至少一個鄰位取代至苯環上。羥基附近之此等立體大型經取代自由基之存在用以延緩其拉伸頻率,且相應地延緩其反應性;此位阻因此提供具有其穩定特性之酚類化合物。代表性受阻酚包含:1,3,5-三甲基-2,4,6-三-(3,5-二-第三丁基-4-羥基苯甲基)-苯;四-3(3,5-二-第三丁基-4-羥基苯基)-丙酸異戊四醇酯;3(3,5-二-第三丁基-4-羥基苯基)-丙酸正十八烷酯;4,4'-亞甲基雙(2,6-第三丁基-酚);4,4'-硫基雙(6-第三丁基鄰甲酚);2,6-二-第三丁基酚;6-(4-羥基苯氧基)-2,4-雙(正辛基-硫基)-1,3,5三嗪;3,5-二-第三丁基-4-羥基-苯甲酸二正辛硫基)乙酯;以及山梨糖醇六[3-(3,5-二-第三丁基-4-羥基-苯基)-丙酸酯]。抗氧化劑之商業實例為例如由巴斯夫製造之豔佳諾克司1035、豔佳諾克司1010、豔佳諾克司1076、豔佳諾克司1098、豔佳諾克司3114、豔佳諾克司PS800、豔佳諾克司PS802、豔佳諾克司168。 Stabilizers or antioxidants suitable for use herein are high molecular weight hindered phenols and polyfunctional phenols, such as sulfur and phosphorus containing phenols. Hindered phenols are well known to those skilled in the art and can be characterized as phenolic compounds that also contain sterically bulky radicals very close to their phenolic hydroxyl groups. In particular, the third butyl group is generally substituted on the benzene ring in at least one ortho position relative to the phenolic hydroxyl group. The presence of these three-dimensional large-scale substituted free radicals near the hydroxyl group serves to delay its stretching frequency and accordingly its reactivity; this steric hindrance thus provides phenolic compounds with their stable properties. Representative hindered phenols include: 1,3,5-trimethyl-2,4,6-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene; tetra-3( 3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid isopentitol ester; 3(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid n-decyl Octane; 4,4'-methylenebis(2,6-tert-butyl-phenol); 4,4'-thiobis(6-tert-butyl-o-cresol); 2,6- Di-tert-butylphenol; 6-(4-hydroxyphenoxy)-2,4-bis(n-octyl-thio)-1,3,5 triazine; 3,5-di-tert-butyl 4-hydroxy-benzoic acid di-n-octylthio) ethyl ester; and sorbitol hexa[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)-propionate]. Commercial examples of antioxidants are, for example, Yanjia Nox 1035, Yanjia Nox 1010, Yanjia Nox 1076, Yana Nox 1098, Yana Nox 3114, Yana Nox PS800, Yana Nox made by BASF. PS802, Yanjia Nuoxi 168.
取決於產物之最終用途,矽氧烷聚合物與填充劑之間的重量比在100:0至5:95之間。矽氧烷聚合物與交聯矽或非矽類樹脂或寡聚物之間的比率在100:0至75:25之間。計算自矽氧烷聚合物量之固化劑之量為0.1%至20%。基於調配物之總量之接著促進 劑之量為0至10%。基於調配物之總重量之抗氧化劑之量為0至5%。 Depending on the end use of the product, the weight ratio between the silicone polymer and the filler is between 100:0 and 5:95. The ratio between the silicone polymer and the cross-linked silicone or non-silicone resin or oligomer is between 100:0 and 75:25. The amount of curing agent calculated from the amount of silicone polymer is 0.1% to 20%. Promotion based on the total amount of formulation The amount of agent is 0 to 10%. The amount of antioxidant based on the total weight of the formulation is 0 to 5%.
矽氧烷-粒子組成物可用於多個領域。其可用作電子學或光電子學封裝、LED及OLED前端及後端處理、3D、光伏打及顯示器金屬化、替代例如半導體封裝中之焊料凸塊之焊接、印刷電子裝置、OLED低功函數陰極油墨、ITO更換油墨、金屬網格及其他電極、高解析度光伏打糊、LMO陰極糊、光伏打、功率電子裝置及EMI、觸控感測器及其他顯示器、熱或UV可固化密封劑或介電質中之接著劑或密封劑(僅舉數例)。 The silicone-particle composition can be used in many fields. It can be used as electronics or optoelectronics packaging, LED and OLED front-end and back-end processing, 3D, photovoltaic and display metallization, solder replacement for solder bumps in semiconductor packages, printed electronic devices, OLED low work function cathodes, for example Inks, ITO replacement inks, metal grids and other electrodes, high-resolution photovoltaic pastes, LMO cathode pastes, photovoltaic pastes, power electronics and EMI, touch sensors and other displays, thermal or UV curable sealants or Adhesives or sealants in dielectrics (to name a few).
取決於固化機制及催化劑活化之類型,最終調配物通常藉由加熱材料至較高溫度固化。舉例而言,若使用熱酸產生劑,則將材料置於烘箱中特定時段。亦可能的為藉由電磁輻射,諸如UV光固化。 Depending on the curing mechanism and the type of catalyst activation, the final formulation is usually cured by heating the material to a higher temperature. For example, if a hot acid generator is used, the material is placed in an oven for a certain period of time. It is also possible to cure by electromagnetic radiation, such as UV light.
由聚合第一化合物及第二化合物形成之矽氧烷聚合物之分子量為約300公克/莫耳至10,000公克/莫耳,較佳約400公克/莫耳至5000公克/莫耳,且更佳約500公克/莫耳至2000公克/莫耳。聚合物與任何所需尺寸之粒子組合,平均粒度較佳小於100微米,更佳小於50微米,或甚至小於20微米。矽氧烷聚合物以10%至90%之重量%添加,且粒子以1%至90%之重量%添加。若矽氧烷材料之最終用途需要光學透明度,則粒子可為以較低重量%,諸如1重量%至20重量%添加之陶瓷粒子。若需要導電性時,諸如在半導體封裝中使用矽氧烷材料,則粒子可為以60重量%至95重量%添加之金屬粒子。 The molecular weight of the siloxane polymer formed by polymerizing the first compound and the second compound is about 300 g/mol to 10,000 g/mol, preferably about 400 g/mol to 5000 g/mol, and more preferably About 500 g/mole to 2000 g/mole. The combination of the polymer and particles of any desired size has an average particle size of preferably less than 100 microns, more preferably less than 50 microns, or even less than 20 microns. The silicone polymer is added at 10% to 90% by weight, and the particles are added at 1% to 90% by weight. If the end use of the silicone material requires optical transparency, the particles may be ceramic particles added at a lower weight %, such as 1% to 20% by weight. If conductivity is required, such as the use of silicone materials in semiconductor packaging, the particles can be metal particles added at 60% to 95% by weight.
進行第一化合物及第二化合物之聚合,且粒子與其混合 以形成黏度為50毫帕-秒至100,000毫帕-秒,較佳1000毫帕-秒至75,000毫帕-秒且更佳5000毫帕-秒至50,000毫帕-秒之黏滯流體。黏度可藉由黏度計,諸如布氏(Brookfield)黏度計或科爾-帕默(Cole-Parmer)黏度計量測,所述黏度計旋轉流體樣品中之圓盤或圓筒且量測克服針對誘導運動之黏滯抗性所需的扭矩。可以任何所需速率,諸如1rpm至30rpm,較佳5rpm,且較佳在材料在25℃下量測之情況下旋轉。 The first compound and the second compound are polymerized, and the particles are mixed with it To form a viscous fluid having a viscosity of 50 mPa-s to 100,000 mPa-s, preferably 1000 mPa-s to 75,000 mPa-s and more preferably 5000 mPa-s to 50,000 mPa-s. Viscosity can be measured with a viscometer, such as a Brookfield viscometer or Cole-Parmer viscometer, which rotates a disc or cylinder in a fluid sample and measures to overcome The torque required to induce the viscous resistance of movement. It can be rotated at any desired speed, such as 1 rpm to 30 rpm, preferably 5 rpm, and preferably with the material measured at 25°C.
在聚合之後,可添加任何額外所需組分至組成物,諸如粒子、偶合劑、固化劑等。組成物以可無需冷卻或冷凍而在環境溫度下運送之容器中之黏滯材料形式運送給客戶。作為最終產物,材料可應用於上文所提及之多種用途中,通常經熱固化或UV固化以形成固體固化聚合矽氧烷層。 After polymerization, any additional desired components may be added to the composition, such as particles, coupling agents, curing agents, and the like. The composition is delivered to the customer in the form of a viscous material in a container that can be shipped at ambient temperature without cooling or freezing. As the final product, the material can be used in the various applications mentioned above, usually by heat curing or UV curing to form a solid cured polymer siloxane layer.
如本文中所揭示之組成物較佳無任何實質性溶劑。可臨時添加溶劑,諸如用於將固化劑或其他添加劑與聚合黏滯材料混合。在此情況下,例如固化劑與溶劑混合以形成可隨後與黏滯矽氧烷聚合物混合之流體材料。然而,由於需要將大體上無溶劑之組成物運送給客戶,及隨後應用於客戶裝置上,在乾燥腔室中移除已臨時添加之溶劑。然而,儘管組成物大體上不含溶劑,可能存在不能夠在乾燥過程期間移除之痕量殘留溶劑。藉由減少最終固化過程期間之收縮以移除此溶劑,有助於本文所揭示之組成物的沈積,在裝置使用期限期間內隨時間推移使收縮最小化,並在裝置使用期限期間內有助於材料之熱穩定性。 The composition as disclosed herein is preferably free of any substantial solvent. Solvents may be added temporarily, such as for mixing curing agents or other additives with polymeric viscous materials. In this case, for example, a curing agent is mixed with a solvent to form a fluid material that can be subsequently mixed with a viscous siloxane polymer. However, due to the need to deliver the substantially solvent-free composition to the customer and subsequent application to the customer's device, the temporarily added solvent is removed in the drying chamber. However, although the composition is substantially free of solvents, there may be traces of residual solvent that cannot be removed during the drying process. Removal of this solvent by reducing shrinkage during the final curing process facilitates the deposition of the compositions disclosed herein, minimizes shrinkage over time during the lifetime of the device, and helps during the lifetime of the device Due to the thermal stability of the material.
知道組成物之最終應用、組成物之所需黏度以及待包含之粒子,有可能精細調整矽氧烷聚合物(起始化合物、分子量、黏 度等),以使得當併入具有粒子及其他組分之組成物中時,達成在後續傳遞給客戶方面之所需最終特性。由於組成物之穩定性,有可能無需分子量或黏度之任何實質性改變而在環境溫度下運送組成物,即使在製造後一週或甚至一個月至客戶最終使用時也是如此。 Knowing the final application of the composition, the required viscosity of the composition, and the particles to be included, it is possible to fine-tune the silicone polymer (starting compound, molecular weight, viscosity Degree, etc.), so that when incorporated into a composition with particles and other components, the desired final characteristics in terms of subsequent delivery to the customer are achieved. Due to the stability of the composition, it is possible to ship the composition at ambient temperature without any substantial change in molecular weight or viscosity, even within a week or even a month after manufacturing until the customer's final use.
以下矽氧烷聚合物實例以說明方式給出且不意欲為限制性的。 The following silicone polymer examples are given by way of illustration and are not intended to be limiting.
藉由布氏黏度計(主軸14)量測矽氧烷聚合物之黏度。藉由安捷倫(Agilent)GPC量測聚合物之分子量。 The viscosity of the silicone polymer is measured by a Brookfield viscometer (spindle 14). The molecular weight of the polymer was measured by Agilent GPC.
矽氧烷聚合物i:以二苯基矽烷二醇(60公克,45莫耳%)、2-(3,4-環氧環己基)乙基]三甲氧基矽烷(55.67公克,36.7莫耳%)以及四甲氧基矽烷(17.20公克,18,3莫耳%)填充具有攪拌棒及回流冷凝器之500毫升圓底燒瓶。燒瓶在氮氣氛圍下加熱至80℃且將0.08公克溶解於1毫升甲醇中之單水合氫氧化鋇逐滴添加至矽烷之混合物中。在二苯基矽烷二醇與烷氧基矽烷反應期間在80℃下攪拌矽烷混合物30分鐘。在30分鐘之後,在真空下蒸發出形成之甲醇。矽氧烷聚合物之黏度為1000mPas且Mw為1100。 Siloxane polymer i: with diphenylsilanediol (60 g, 45 mol%), 2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane (55.67 g, 36.7 mol %) and tetramethoxysilane (17.20 g, 18.3 mol%) were filled in a 500 ml round bottom flask with a stir bar and reflux condenser. The flask was heated to 80°C under a nitrogen atmosphere and 0.08 g of barium hydroxide monohydrate dissolved in 1 ml of methanol was added dropwise to the silane mixture. The silane mixture was stirred at 80°C for 30 minutes during the reaction of diphenylsilanediol and alkoxysilane. After 30 minutes, the methanol formed was evaporated under vacuum. The viscosity of the silicone polymer is 1000 mPas and the Mw is 1100.
矽氧烷聚合物ii:以二苯基矽烷二醇(30公克,45莫耳%)、2-(3,4-環氧環己基)乙基]三甲氧基矽烷(28.1公克,37莫耳%)以及二甲基二甲氧基矽烷(6.67公克,18莫耳%)填充具有攪拌棒及回流冷凝器之250毫升圓底燒瓶。燒瓶在氮氣氛圍下加熱至80℃且將0.035公克溶解於1毫升甲醇中之單水合氫氧化鋇逐滴添加至矽烷之混合物中。在二苯基矽烷二醇與烷氧基矽烷反應 期間在80℃下攪拌矽烷混合物30分鐘。在30分鐘之後,在真空下蒸發形成之甲醇。矽氧烷聚合物之黏度為2750mPas且Mw為896。 Siloxane polymer ii: with diphenylsilanediol (30 g, 45 mol%), 2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane (28.1 g, 37 mol) %) and dimethyldimethoxysilane (6.67 g, 18 mol%) filled a 250 ml round bottom flask with a stir bar and reflux condenser. The flask was heated to 80°C under a nitrogen atmosphere and 0.035 g of barium hydroxide monohydrate dissolved in 1 ml of methanol was added dropwise to the silane mixture. The reaction of diphenylsilanediol and alkoxysilane During this period, the silane mixture was stirred at 80°C for 30 minutes. After 30 minutes, the methanol formed was evaporated under vacuum. The viscosity of the silicone polymer is 2750 mPas and the Mw is 896.
矽氧烷聚合物iii:以二苯基矽烷二醇(24.5公克,50莫耳%)、2-(3,4-環氧環己基)乙基]三甲氧基矽烷(18.64公克,33.4莫耳%)以及四甲氧基矽烷(5.75公克,16.7莫耳%)填充具有攪拌棒及回流冷凝器之250毫升圓底燒瓶。燒瓶在氮氣氛圍下加熱至80℃且將0.026公克溶解於1毫升甲醇中之單水合氫氧化鋇逐滴添加至矽烷之混合物中。在二苯基矽烷二醇與烷氧基矽烷反應期間在80℃下攪拌矽烷混合物30分鐘。在30分鐘之後,在真空下蒸發形成之甲醇。矽氧烷聚合物之黏度為7313mPas且Mw為1328。 Siloxane polymer iii: with diphenylsilanediol (24.5 g, 50 mol%), 2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane (18.64 g, 33.4 mol %) and tetramethoxysilane (5.75 g, 16.7 mol%) filled a 250 ml round bottom flask with a stir bar and reflux condenser. The flask was heated to 80°C under a nitrogen atmosphere and 0.026 g of barium hydroxide monohydrate dissolved in 1 ml of methanol was added dropwise to the silane mixture. The silane mixture was stirred at 80°C for 30 minutes during the reaction of diphenylsilanediol and alkoxysilane. After 30 minutes, the methanol formed was evaporated under vacuum. The viscosity of the silicone polymer is 7313 mPas and the Mw is 1328.
矽氧烷聚合物iv:以二苯基矽烷二醇(15公克,50莫耳%)、2-(3,4-環氧環己基)乙基]三甲氧基矽烷(13.29公克,38.9莫耳%)以及雙(三甲氧基矽基)乙烷(4.17公克,11.1莫耳%)填充具有攪拌棒及回流冷凝器之250毫升圓底燒瓶。燒瓶在氮氣氛圍下加熱至80℃且將0.0175公克溶解於1毫升甲醇中之單水合氫氧化鋇逐滴添加至矽烷之混合物中。在二苯基矽烷二醇與烷氧基矽烷反應期間在80℃下攪拌矽烷混合物30分鐘。在30分鐘之後,在真空下蒸發形成之甲醇。矽氧烷聚合物之黏度為1788mPas且Mw為1590。 Siloxane polymer iv: with diphenylsilanediol (15 g, 50 mol%), 2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane (13.29 g, 38.9 mol %) and bis(trimethoxysilyl)ethane (4.17 g, 11.1 mol %) filled a 250 ml round bottom flask with a stir bar and reflux condenser. The flask was heated to 80°C under a nitrogen atmosphere and 0.0175 g of barium hydroxide monohydrate dissolved in 1 mL of methanol was added dropwise to the silane mixture. The silane mixture was stirred at 80°C for 30 minutes during the reaction of diphenylsilanediol and alkoxysilane. After 30 minutes, the methanol formed was evaporated under vacuum. The viscosity of the silicone polymer is 1788 mPas and the Mw is 1590.
矽氧烷聚合物v:以二苯基矽烷二醇(15公克,45莫耳%)、2-(3,4-環氧環己基)乙基]三甲氧基矽烷(13.29公克,35莫耳%)以及乙烯基三甲氧基矽烷(4.57公克,20莫耳%)填充具有攪 拌棒及回流冷凝器之250毫升圓底燒瓶。燒瓶在氮氣氛圍下加熱至80℃且將0.018公克溶解於1毫升甲醇中之單水合氫氧化鋇逐滴添加至矽烷之混合物中。在二苯基矽烷二醇與烷氧基矽烷反應期間在80℃下攪拌矽烷混合物30分鐘。在30分鐘之後,在真空下蒸發出形成之甲醇。矽氧烷聚合物之黏度為1087mPas且Mw為1004。 Siloxane polymer v: with diphenylsilanediol (15 g, 45 mol%), 2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane (13.29 g, 35 mol) %) and vinyl trimethoxysilane (4.57 g, 20 mol%) filled with stir 250ml round bottom flask with stir bar and reflux condenser. The flask was heated to 80°C under a nitrogen atmosphere and 0.018 g of barium hydroxide monohydrate dissolved in 1 mL of methanol was added dropwise to the silane mixture. The silane mixture was stirred at 80°C for 30 minutes during the reaction of diphenylsilanediol and alkoxysilane. After 30 minutes, the methanol formed was evaporated under vacuum. The viscosity of the silicone polymer is 1087 mPas and the Mw is 1004.
矽氧烷聚合物vi:以二異丙基矽烷二醇(20.05公克,55.55莫耳%)、2-(3,4-環氧環己基)乙基]三甲氧基矽烷(20.0公克,33.33莫耳%)以及雙(三甲氧基矽基)乙烷(7.3公克,11.11莫耳%)填充具有攪拌棒及回流冷凝器之250毫升圓底燒瓶。燒瓶在氮氣氛圍下加熱至80℃且將0.025公克溶解於1毫升甲醇中之單水合氫氧化鋇逐滴添加至矽烷之混合物中。在二苯基矽烷二醇與烷氧基矽烷反應期間在80℃下攪拌矽烷混合物30分鐘。在30分鐘之後,在真空下蒸發出形成之甲醇。.矽氧烷聚合物之黏度為150mPas且Mw為781。 Siloxane polymer vi: with diisopropylsilanediol (20.05 g, 55.55 mole %), 2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane (20.0 g, 33.33 mole Ear%) and bis(trimethoxysilyl)ethane (7.3 g, 11.11 mol%) filled a 250 ml round bottom flask with a stir bar and reflux condenser. The flask was heated to 80°C under a nitrogen atmosphere and 0.025 g of barium hydroxide monohydrate dissolved in 1 mL of methanol was added dropwise to the silane mixture. The silane mixture was stirred at 80°C for 30 minutes during the reaction of diphenylsilanediol and alkoxysilane. After 30 minutes, the methanol formed was evaporated under vacuum. The viscosity of the silicone polymer is 150 mPas and the Mw is 781.
矽氧烷聚合物vii:以二異丁基矽烷二醇(18.6公克,60莫耳%)及2-(3,4-環氧環己基)乙基]三甲氧基矽烷(17.32公克,40莫耳%)填充具有攪拌棒及回流冷凝器之250毫升圓底燒瓶。燒瓶在氮氣氛圍下加熱至80℃且將0.019公克溶解於1毫升甲醇中之單水合氫氧化鋇逐滴添加至矽烷之混合物中。在二苯基矽烷二醇與烷氧基矽烷反應期間在80℃下攪拌矽烷混合物30分鐘。在30分鐘之後,在真空下蒸發出形成之甲醇。矽氧烷聚合物之黏度為75mPas且Mw為710。 Siloxane polymer vii: with diisobutylsilanediol (18.6 g, 60 mol%) and 2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane (17.32 g, 40 mol Ear %) Fill a 250 ml round bottom flask with a stir bar and reflux condenser. The flask was heated to 80°C under a nitrogen atmosphere and 0.019 g of barium hydroxide monohydrate dissolved in 1 ml of methanol was added dropwise to the silane mixture. The silane mixture was stirred at 80°C for 30 minutes during the reaction of diphenylsilanediol and alkoxysilane. After 30 minutes, the methanol formed was evaporated under vacuum. The viscosity of the silicone polymer is 75 mPas and the Mw is 710.
以下組成物實例以說明方式給出且不意欲為限制性的。 The following composition examples are given by way of illustration and are not intended to be limiting.
比較例1,銀填充接著劑:使用高剪切混合器將矽氧烷聚合物(18.3公克,18.3%)、平均尺寸(D50)為4微米之銀片(81公克,81%)、3-甲基丙烯酸酯基丙基三甲氧基矽烷(0.5公克,0.5%)以及金氏工業K-PURE CXC-1612熱酸產生劑(0.2%)混合在一起。 Comparative Example 1, silver-filled adhesive: using a high-shear mixer, a silver polymer (18.3 g, 18.3%), silver sheet (81 g, 81%) with an average size (D50) of 4 microns, 3- Methacrylate propyltrimethoxysilane (0.5 g, 0.5%) and King's Industrial K-PURE CXC-1612 thermal acid generator (0.2%) were mixed together.
比較例2,氧化鋁填充接著劑:使用三輥研磨機將矽氧烷聚合物(44.55公克,44.45%)、平均尺寸(D50)為0.9微米之氧化鋁(53公克,53%)、3-甲基丙烯酸酯基丙基三甲氧基矽烷(1公克,1%)、豔佳諾克司1173(1公克,1%)以及金氏工業K-PURE CXC-1612熱酸產生劑(0.45公克,0.45%)混合在一起。 Comparative Example 2: Alumina filled adhesive: Alumina (53 g, 53%) with a silicone polymer (44.55 g, 44.45%), average size (D50) of 0.9 μm, 3-roll grinder, 3- Methacrylate propyltrimethoxysilane (1 g, 1%), Yanjia Nuoxi Division 1173 (1 g, 1%) and King's Industrial K-PURE CXC-1612 thermal acid generator (0.45 g, 0.45 %)Mix together.
比較例3,BN填充接著劑:使用三輥研磨機將矽氧烷聚合物(60公克,60%)、平均尺寸(D50)為15微米之氮化硼薄片(35公克,35%)、豔佳諾克司1173(1.3公克,1.3%)、2-(3,4-環氧環己基)乙基三甲氧基矽烷(3.4公克,3.4%)以及金氏工業K-PURE CXC-1612熱酸產生劑(0.3公克,0.3%)混合在一起。 Comparative Example 3, BN filled adhesive: A three-roll mill was used to combine a boron nitride flake (35 g, 35%), a silicone polymer (60 g, 60%) with an average size (D50) of 15 microns, Ganox Division 1173 (1.3 g, 1.3%), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (3.4 g, 3.4%), and K-PURE CXC-1612 thermal acid generation from Kings Industries Agents (0.3 g, 0.3%) are mixed together.
比較例4,半透明材料:使用三輥研磨機將矽氧烷聚合物(92.5公克,92.5%)、平均尺寸(D50)為0.007微米之煙霧狀二氧化矽(5公克,5%)、豔佳諾克司1173(2公克,2%)以及金氏工業K-PURE CXC-1612熱酸產生劑(0.5公克,0.5%)混合在一起。 Comparative Example 4, translucent material: using a three-roll grinder, aerosol silica (52.5 g, 5%), cyanosiloxane polymer (92.5 g, 92.5%), average size (D50) of 0.007 micron, bright Canox 1173 (2g, 2%) and King's Industrial K-PURE CXC-1612 thermal acid generator (0.5g, 0.5%) were mixed together.
比較例5,金剛石填充:使用三輥研磨機將矽氧烷聚合物(97.5公克,97.5%)、平均尺寸(D50)為0.500微米之亞微米金剛石粒子(18公克,18%)、豔佳諾克司1173(2公克,2%)以及 金氏工業K-PURE CXC-1612熱酸產生劑(0.5公克,0.5%)混合在一起。 Comparative Example 5, diamond filling: using a three-roll grinder, submicron diamond particles (18 g, 18%) with a silicone polymer (97.5 g, 97.5%), an average size (D50) of 0.500 μm, and Yanjia Nuo Kex 1173 (2 grams, 2%) and King's Industrial K-PURE CXC-1612 thermal acid generator (0.5 g, 0.5%) is mixed together.
考慮到揭示之方法及材料,形成穩定組成物。組成物可有一部分為具有[-Si-O-Si-O]n重複主鏈之矽氧烷聚合物,所述主鏈上具有烷基或芳基,且所述主鏈上具有官能性交聯基團,且有另一部分為與矽氧烷材料混合之粒子,其中所述粒子之平均粒度小於100微米,所述粒子為任何適合之粒子,諸如金屬、半金屬、半導體或陶瓷粒子。運送給客戶之組成物可具有300公克/莫耳至10,000公克/莫耳之分子量,及在5rpm黏度計下1000毫帕-秒至75000毫帕-秒之黏度。 Considering the disclosed methods and materials, a stable composition is formed. A part of the composition may be a siloxane polymer having a repeating main chain of [-Si-O-Si-O]n, the main chain has an alkyl group or an aryl group, and the main chain has a functional crosslink Group, and another part is particles mixed with siloxane material, wherein the average particle size of the particles is less than 100 microns, the particles are any suitable particles, such as metal, semi-metal, semiconductor or ceramic particles. The composition delivered to the customer may have a molecular weight of 300 g/mol to 10,000 g/mol, and a viscosity of 1000 mPa-s to 75000 mPa-s at a 5 rpm viscometer.
黏滯(或液體)矽氧烷聚合物大體上不含-OH基團,因此提供延長之存放期,且允許必要時在環境溫度下儲存或運送。較佳地,矽氧烷材料不具有可自FTIR分析偵測之-OH峰。形成之矽氧烷材料之穩定性增加以允許在使用之前儲存,其中在儲存期間黏度(交聯)的增加幅度最小,諸如在室溫下儲存2週時段小於25%,較佳經2週時段小於15%,且更佳小於10%。另外,儲存、運送以及隨後由客戶應用可全部在不存在溶劑的情況下進行(除了在乾燥以移除溶劑之後保留的可能的微量殘餘物),避免隨後形成於最終產物的層中之溶劑捕獲(solvent capture)、聚合期間之收縮、裝置使用期間隨時間推移質量損失等問題。在不施加較佳高於100℃之熱或UV光的情況下,在運送及儲存期間不出現實質性交聯。 Viscous (or liquid) silicone polymers are substantially free of -OH groups, thus providing extended shelf life and allowing storage or transportation at ambient temperature if necessary. Preferably, the silicone material does not have a -OH peak detectable from FTIR analysis. The stability of the formed siloxane material is increased to allow storage before use, where the increase in viscosity (crosslinking) during storage is minimal, such as storage at room temperature for less than 25% for 2 weeks, preferably over 2 weeks Less than 15%, and more preferably less than 10%. In addition, storage, shipping, and subsequent application by the customer can all be carried out in the absence of solvent (except for possible trace residues remaining after drying to remove the solvent), avoiding subsequent solvent traps formed in the layer of the final product (solvent capture), shrinkage during polymerization, and quality loss over time during device usage. Without the application of heat or UV light preferably above 100°C, no substantial crosslinking occurs during transportation and storage.
如本文中所揭示之具有矽氧烷聚合物、粒子以及其他可能的添加劑(諸如偶合劑、接著促進劑等)之組成物可在室溫下以單組分接著劑形式運送。一般而言,單組分接著劑在-40℃下運送, 或各組分分開運送(「雙組分」接著劑),其中購買者必須將不同組分混合在一起,且通常應較佳在24小時或48小時內進行接著。一般而言,單組分接著劑可能不涉及混合多種組分,然而,一旦使接著劑自例如-40℃至室溫,接著應較佳在24小時或48小時內進行。相較之下,本文所揭示之組成物可以單組分接著劑形式運送且其可在室溫下運送及儲存,例如在室溫下運送及存儲2週而不發生實質性聚合或其他非所要反應。 As disclosed herein, compositions with silicone polymers, particles, and other possible additives (such as coupling agents, adhesion promoters, etc.) can be shipped as a one-component adhesive at room temperature. Generally speaking, single-component adhesives are shipped at -40°C, Or each component is shipped separately ("two-component" adhesive), where the purchaser must mix the different components together, and generally should preferably be within 24 hours or 48 hours of bonding. In general, a one-component adhesive may not involve mixing multiple components, however, once the adhesive is brought from, for example, -40°C to room temperature, then it should preferably be performed within 24 hours or 48 hours. In contrast, the composition disclosed herein can be shipped as a single-component adhesive and it can be shipped and stored at room temperature, for example, at room temperature for 2 weeks without substantial polymerization or other undesirable reaction.
當組成物經沈積及聚合(例如施加熱或UV光)時,觀測到質量之極小收縮或減少。圖2中,x軸為時間(以分鐘為單位),左方y軸為就起始質量之%而言之層之質量,且右方y軸為以攝氏度為單位之溫度。如圖2中可見,如本文中所揭示之矽氧烷粒子混合物快速加熱至150℃,接著在150℃保持大致30分鐘。在此實例中,矽氧烷粒子具有具有苯基及環氧基之Si-O主鏈,且粒子為銀粒子。在經此時段之熱固化之後,質量損失小於1%。合意地,質量損失通常小於4%,且一般小於2%。然而,在許多情況下,固化之前與之後間的矽氧烷粒子組成物之質量差異小於1%。固化溫度一般低於175℃,儘管較高固化溫度為可能的。通常,固化溫度將為160℃或更低,更通常150℃或更低。然而,較低固化溫度為可能的,諸如125℃或更低。 When the composition is deposited and polymerized (for example, heat or UV light is applied), minimal shrinkage or reduction in mass is observed. In Figure 2, the x-axis is time (in minutes), the left y-axis is the mass of the layer in terms of% of the initial mass, and the right y-axis is the temperature in degrees Celsius. As can be seen in Figure 2, the mixture of siloxane particles as disclosed herein is rapidly heated to 150°C and then held at 150°C for approximately 30 minutes. In this example, the siloxane particles have a Si-O backbone with phenyl and epoxy groups, and the particles are silver particles. After this period of thermal curing, the mass loss is less than 1%. Desirably, the mass loss is usually less than 4%, and generally less than 2%. However, in many cases, the mass difference between the silicone particle composition before and after curing is less than 1%. The curing temperature is generally below 175°C, although higher curing temperatures are possible. Typically, the curing temperature will be 160°C or lower, more usually 150°C or lower. However, lower curing temperatures are possible, such as 125°C or lower.
如圖3中可見,不管上文所揭示之組成物用作接著劑、導熱層、密封劑、圖案化導電層、圖案化介電層、透明層、光反射層等,一旦組成物經沈積及聚合以及視需要硬化,矽氧烷粒子層或質量為相當熱穩定的。舉例而言,在藉由熱聚合或UV聚合硬化之後,以每分鐘10℃增加之升溫速率將原位材料加熱至600℃,在 200℃及300℃兩者下觀測到小於4.0%,較佳小於2.0%,例如小於1.0%之質量損失(通常在200℃觀測到小於0.5%之質量損失,或如同圖3之實例中,在200℃觀測到小於0.2%之質量損失)。在300℃下,在圖3之實例中觀測到小於1%,或更特定言之小於0.6%之質量損失。可藉由僅在200℃或300℃下加熱聚合材料1小時,觀測到類似結果。藉由在375℃或高於375℃加熱聚合沈積材料至少1小時之小於1%質量損失之結果為可能的。如圖3中可見,甚至在高於500℃之溫度下觀測到5%或小於5%之質量損失。此類熱穩定材料為所需的,特定言之,可在低溫(例如低於175℃,較佳低於150℃,或低於130℃,30分鐘固化/烘烤時間)下沈積,或可藉由UV光聚合之如本文中所揭示之熱穩定材料。 As can be seen in FIG. 3, regardless of whether the composition disclosed above is used as an adhesive, a thermally conductive layer, a sealant, a patterned conductive layer, a patterned dielectric layer, a transparent layer, a light reflective layer, etc., once the composition is deposited and Polymerization and, if necessary, hardening, the layer or quality of the siloxane particles is quite thermally stable. For example, after hardening by thermal polymerization or UV polymerization, the in-situ material is heated to 600°C at a temperature increase rate of 10°C per minute, at Less than 4.0%, preferably less than 2.0% is observed at both 200°C and 300°C, for example less than 1.0% mass loss (usually less than 0.5% mass loss is observed at 200°C, or as in the example of Figure 3, in A mass loss of less than 0.2% was observed at 200°C). At 300°C, a mass loss of less than 1%, or more specifically less than 0.6%, was observed in the example of FIG. 3. Similar results can be observed by heating the polymeric material only at 200°C or 300°C for 1 hour. The result of mass loss of less than 1% by heating the polymer deposited material at or above 375°C for at least 1 hour is possible. As can be seen in Figure 3, a mass loss of 5% or less was observed even at temperatures above 500°C. Such thermally stable materials are desired, in particular, they can be deposited at low temperatures (eg, below 175°C, preferably below 150°C, or below 130°C, 30 minutes curing/baking time), or Thermally stable materials as disclosed herein polymerized by UV light.
前述內容說明實例實施例,且並非解釋為限制性的。儘管已描述了數個實例實施例,但本領域的技術人員將易於瞭解,在實質上不偏離新穎教示內容及優點的情況下,在實例實施例中有可能進行許多修改。因此,所有此類修改意欲包含於如申請專利範圍中所界定的本發明之範疇內。因此,應理解,前述內容說明各種實例實施例不應解釋為限於所揭示的特定實施例,且對所揭示實施例以及其他實施例的修改意欲包含在隨附申請專利範圍的範疇內。 The foregoing description illustrates example embodiments and is not to be construed as limiting. Although several example embodiments have been described, those skilled in the art will readily understand that many modifications are possible in the example embodiments without materially departing from the novel teaching content and advantages. Therefore, all such modifications are intended to be included within the scope of the invention as defined in the scope of the patent application. Therefore, it should be understood that the foregoing description illustrates that various example embodiments should not be construed as being limited to the specific embodiments disclosed, and modifications to the disclosed embodiments and other embodiments are intended to be included within the scope of the patent scope of the accompanying application.
引用清單 Citation list
專利文獻 Patent Literature
US 2009258216 US 2009258216
WO 2008046142 WO 2008046142
非專利文獻 Non-patent literature
吉恩,J(Jin,J)等人,用於透明OLED密封之二氧化矽奈米例子嵌入之溶膠-膠凝有機/無機混合奈米複合物(Silica nanoparticle-embedded sol-gel organic/inorganic hybrid nanocomposite for transparent OLED encapsulation).有機電子(Organic Electronic),2012,第13卷,第53-57頁。 Gene, J (Jin, J), et al. Silica nanoparticle-embedded sol-gel organic/inorganic hybrid nanocomposite for transparent OLED encapsulation). Organic Electronic (Organic Electronic), 2012, Volume 13, pages 53-57.
100、102、104、106、108:步驟 100, 102, 104, 106, 108: steps
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TW200951182A (en) * | 2007-12-19 | 2009-12-16 | Bayer Materialscience Ag | Siloxane-containing binder dispersions |
TW201024377A (en) * | 2008-11-19 | 2010-07-01 | Dow Corning | A silicone composition and a method for preparing the same |
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