TWI784922B - Led lamp, method of making led lamp, and method for encapsulating led device - Google Patents
Led lamp, method of making led lamp, and method for encapsulating led device Download PDFInfo
- Publication number
- TWI784922B TWI784922B TW104142616A TW104142616A TWI784922B TW I784922 B TWI784922 B TW I784922B TW 104142616 A TW104142616 A TW 104142616A TW 104142616 A TW104142616 A TW 104142616A TW I784922 B TWI784922 B TW I784922B
- Authority
- TW
- Taiwan
- Prior art keywords
- particles
- polymer
- compound
- light
- group
- Prior art date
Links
Images
Landscapes
- Led Device Packages (AREA)
Abstract
Description
本發明是關於LED燈。特定言之,本發明是關於一種LED燈,包括形成於半導體材料上之晶粒基板;用於跨越半導體材料施加偏壓以引起自其發射之光之電極;以及將晶粒基板黏合至支撐基板之接著劑。本發明亦關於LED燈之製造方法以及LED裝置之密封方法。 This invention relates to LED lamps. In particular, the invention relates to an LED lamp comprising a die substrate formed on a semiconductor material; electrodes for applying a bias voltage across the semiconductor material to cause light to be emitted therefrom; and bonding the die substrate to a support substrate Adhesives. The present invention also relates to a method for manufacturing an LED lamp and a method for sealing an LED device.
發光二極體(Light emitting diode;LED)照明系統替代傳統照明變得更廣泛使用。發光二極體燈(固態照明之實例)可由於較低能量使用率、增加之穩定性及較長使用期限、用於比螢光照明更寬泛種類之應用中之能力、調諧至所需精確顏色之能力而具有優於諸如白熾電燈泡、鹵素燈照明或螢光照明之傳統照明的優點。在一些實施例中,單一LED晶片/晶粒在所述燈內,且在其他實施例中,複數個LED在相同燈內。LED燈之外殼可以與白熾燈泡相同之規格製造,因此允許在使用白熾燈泡之情況下使用。 Light emitting diode (LED) lighting systems are becoming more widely used in place of traditional lighting. Light-emitting diode lamps (an example of solid-state lighting) can be tuned to the precise color desired due to lower energy usage, increased stability, and longer lifetime, ability to be used in a wider variety of applications than fluorescent lighting advantages over traditional lighting such as incandescent light bulbs, halogen lighting, or fluorescent lighting. In some embodiments, a single LED die/die is within the lamp, and in other embodiments, multiple LEDs are within the same lamp. The housing of the LED lamp can be manufactured to the same specifications as the incandescent bulb, thus allowing it to be used where the incandescent bulb is used.
發光二極體(LED)為將電能轉化為光之固態裝置,且一 般具有至少一種具有n摻雜部分及p摻雜部分之半導體材料。亦已知有機發光二極體。當跨越半導體材料施加偏壓時,電洞及電子噴射至主動層中,所述電洞及電子在其中重組以產生光。光自主動層發射且可主要沿一個方向,或沿任何方向定向,其取決於LED之類型。 Light-emitting diodes (LEDs) are solid-state devices that convert electrical energy into light, and a Generally have at least one semiconductor material with n-doped and p-doped parts. Organic light-emitting diodes are also known. When a bias voltage is applied across the semiconductor material, holes and electrons are ejected into the active layer where they recombine to generate light. Light is emitted from the active layer and can be directed primarily in one direction, or in any direction, depending on the type of LED.
LED可藉由單一LED(諸如藉由藍光或紫光LED)提供白光,所述LED具有將光位移至更接近於感知之白光之磷光體。LED可提供單一顏色(例如紅色、綠色或藍色),或可提供為經組合以提供白光之相同燈中之不同顏色LED。LED之實例可包括使用GaAsP之紅光LED及使用GaP之綠光LED,以及形成綠光、藍光或紫外光之氮化物半導體LED。隨著LED變得愈來愈亮,熱耗散變得愈來愈受關注,因為熱積聚可降低LED性能。 LEDs can provide white light by a single LED, such as by a blue or violet LED, with a phosphor that shifts the light closer to perceived white light. LEDs may be provided in a single color, such as red, green or blue, or may be provided as different colored LEDs in the same lamp combined to provide white light. Examples of LEDs may include red LEDs using GaAsP and green LEDs using GaP, and nitride semiconductor LEDs forming green, blue, or ultraviolet light. As LEDs become brighter, heat dissipation becomes an increasing concern because heat buildup can degrade LED performance.
包括可交聯聚合物組成物之LED燈揭示於US 2009221783、US2012123054、WO20100267、US 2011171447以及JP 2004225005中。 LED lamps comprising crosslinkable polymer compositions are disclosed in US 2009221783, US2012123054, WO20100267, US 2011171447 and JP 2004225005.
已知聚合物組成物之特性例如在熱穩定性方面不足。 It is known that polymer compositions are insufficient in properties such as thermal stability.
本發明之一個目標為提供LED燈。 One object of the present invention is to provide LED lamps.
本發明之另一目標為提供LED燈之製造方法。 Another object of the present invention is to provide a method for manufacturing an LED lamp.
本發明之第三目標為提供LED裝置之密封方法。 The third object of the present invention is to provide a sealing method for LED devices.
本發明是基於形成LED燈,所述LED燈形成自晶粒基板,其中基板上形成有半導體材料;用於跨越半導體材料施加偏壓以引起自其發射之光之電極;以及將晶粒基板黏合至支撐基板之 接著劑。 The invention is based on forming an LED lamp formed from a die substrate on which a semiconductor material is formed; electrodes for applying a bias voltage across the semiconductor material to cause light to be emitted therefrom; and bonding the die substrate to the supporting substrate Adhesive.
在本發明中,接著劑為熱導率大於0.1瓦/公尺.克耳文(W/(m.K))之聚合矽氧烷聚合物,其中接著劑不吸收光,其中矽氧烷聚合物在聚合物主鏈中具有矽及氧,以及與其結合之芳基或烷基,且其中接著劑更包括平均粒度小於100微米之粒子。 In the present invention, the adhesive has a thermal conductivity greater than 0.1 W/m. Kerven (W/(m.K)) polymerized siloxane polymer, wherein the adhesive does not absorb light, wherein the siloxane polymer has silicon and oxygen in the polymer main chain, and aryl groups bonded to it or an alkyl group, and wherein the adhesive further includes particles with an average particle size of less than 100 microns.
根據本發明,LED燈之製造方法包括以下步驟:藉由在第一基板上提供半導體材料及摻雜半導體材料以形成發光二極體;提供支撐基板;以及提供由矽氧烷聚合物形成之接著劑組成物,所述接著劑組成物更包括平均粒度小於100微米之粒子及催化劑。接著劑組成物經沈積以將第一基板接著至支撐基板。藉由施加溫度及/或光,矽氧烷聚合物之交聯基團經活化以進一步聚合矽氧烷聚合物及硬化聚合物,同時將晶粒基板及封裝基板接著在一起。 According to the present invention, the manufacturing method of an LED lamp includes the following steps: forming a light-emitting diode by providing a semiconductor material and doping the semiconductor material on a first substrate; providing a supporting substrate; and providing an adhesive formed of a siloxane polymer. An adhesive composition, the adhesive composition further includes particles with an average particle size of less than 100 microns and a catalyst. A bonding agent composition is deposited to bond the first substrate to the supporting substrate. By applying temperature and/or light, the crosslinking groups of the siloxane polymer are activated to further polymerize the siloxane polymer and harden the polymer while bonding the die substrate and the packaging substrate together.
在包括發光二極體之LED裝置之密封方法中,半導體材料提供於第一基板上且其經摻雜。提供包括密封劑組成物,所述密封劑組成物包括矽氧烷聚合物,所述矽氧烷聚合物在聚合物主鏈中具有矽及氧,以及與其結合之芳基或烷基,以及與其結合之官能性交聯基團,接著劑組成物更包括平均粒度小於10微米之粒子及催化劑。密封劑組成物經沈積以包封發光二極體,且施加溫度及/或光以活化矽氧烷聚合物之交聯基團,以進一步聚合矽氧烷聚合物及硬化聚合物。 In a method of encapsulating an LED device comprising light emitting diodes, a semiconductor material is provided on a first substrate and it is doped. Provided is a composition comprising a sealant, the sealant composition comprising a siloxane polymer having silicon and oxygen in the polymer backbone, and an aryl group or an alkyl group bonded thereto, and Combined functional crosslinking groups, the adhesive composition further includes particles and catalysts with an average particle size of less than 10 microns. An encapsulant composition is deposited to encapsulate the light emitting diodes, and temperature and/or light are applied to activate the crosslinking groups of the silicone polymer to further polymerize the silicone polymer and harden the polymer.
上文提及之聚合及硬化矽氧烷聚合物在聚合之後通常具有相比於聚合之前至少96%之質量。通常,矽氧烷聚合物不吸收大於25%入射於其上之可見光。 The above-mentioned polymerized and hardened silicone polymers generally have at least 96% mass after polymerization compared to before polymerization. Typically, silicone polymers do not absorb greater than 25% of the visible light incident thereon.
獲得相當大的優勢。因此,接著劑之熱導率較高,且接著劑為熱穩定的。亦達成極好存放期,特定言之在使用之前的儲存。通常,在儲存期間具有黏度(交聯)之最小增加,且儲存、運送以及客戶隨後應用可全部在不存在溶劑的情況下進行,避免隨後形成於最終產物的層中之溶劑捕獲(solvent capture)、聚合期間之收縮以及裝置使用期間隨時間推移之質量損失之問題。 gain a considerable advantage. Therefore, the thermal conductivity of the adhesive is high, and the adhesive is thermally stable. An excellent shelf life is also achieved, in particular storage prior to use. Typically, there is minimal increase in viscosity (cross-linking) during storage, and storage, shipping, and subsequent application by the customer can all be carried out in the absence of solvents, avoiding solvent capture in layers subsequently formed in the final product , shrinkage during polymerization and mass loss over time during device use.
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。 Example embodiments will be more clearly understood from the following description taken in conjunction with the accompanying drawings.
10、10a、10b:電極 10, 10a, 10b: electrodes
12:n摻雜氮化鎵區域 12: n-doped gallium nitride region
13:p摻雜氮化鎵區域 13: p-doped gallium nitride region
14:藍寶石基板 14: Sapphire substrate
16、40、42、44:基板 16, 40, 42, 44: substrate
17:接著劑層 17: Adhesive layer
19、20、30:封裝基板 19, 20, 30: Package substrate
22:晶粒附連接著劑 22: Die Attach Adhesive
24、51:晶粒 24, 51: grain
25、45:線結合 25, 45: line bonding
28:磷光層 28: Phosphorescent layer
29:密封劑層 29: Sealant layer
35:磷光材料 35: Phosphorescent material
37:第二密封層 37:Second sealing layer
41:半導體材料 41: Semiconductor materials
43:接著劑 43: Adhesive
46:矽氧烷粒子接著劑 46: Silicone particle adhesive
47、48:電連接區域 47, 48: Electrical connection area
49:矽氧烷材料 49: Silicone material
50:封裝基板 50: Package substrate
52:覆蓋基板 52: Covering the substrate
53:矽氧烷密封劑 53: Silicone sealant
55:保形層 55: Conformal layer
圖1說明形成於透光基板上之發光二極體之實例。 FIG. 1 illustrates an example of a light-emitting diode formed on a light-transmissive substrate.
圖2說明形成於光反射基板上之發光二極體之實例。 FIG. 2 illustrates an example of a light emitting diode formed on a light reflective substrate.
圖3為具有正面透明密封劑之LED之說明。 Figure 3 is an illustration of an LED with a front transparent encapsulant.
圖4為在空腔內具有密封劑之封裝之凹腔內之LED之說明。 4 is an illustration of an LED within a cavity of a package with encapsulant within the cavity.
圖5說明LED覆晶封裝。 Figure 5 illustrates LED flip-chip packaging.
圖6顯示不同粒子負載之折射率相對於波長之圖。 Figure 6 shows a plot of refractive index versus wavelength for different particle loadings.
圖7為透射率相對於粒子負載之圖。 Figure 7 is a graph of transmittance versus particle loading.
圖8說明在熱誘導聚合期間之矽氧烷聚合物之質量改變。 Figure 8 illustrates the mass change of siloxane polymer during thermally induced polymerization.
圖9說明在沈積及聚合之後的矽氧烷材料之熱穩定性。 Figure 9 illustrates the thermal stability of silicone materials after deposition and polymerization.
圖10a至圖10d說明LED密封之額外實例。 Figures 10a-10d illustrate additional examples of LED encapsulation.
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體現,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。 Various example embodiments will be described more fully hereinafter with reference to the accompanying drawings in which some example embodiments are shown. Inventive concepts may, however, be embodied in many different forms and should not be construed as 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 drawings, the size and relative sizes of layers and regions may be exaggerated for clarity.
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。相較之下,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 will 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. A layer is on, 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," "directly connected to" or "directly coupled to" another element or layer, there are no intervening elements or layers present. Floor. Like numbers refer to like elements throughout. 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. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the inventive concept.
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, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly dictates otherwise. should enter It is to be further understood that the term "comprises" or "comprises" 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, regions , integers, steps, operations, elements, components and/or the presence or addition of 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。 Additionally, relative terms such as "lower" or "bottom" and "upper" or "top" may be used herein to describe one element's relationship to another as illustrated in the drawings. It will be understood that relative terms are intended to encompass different orientations of the device in addition to the orientation depicted in the drawings. For example, if the device in one of the figures is turned over, elements described as being on the "lower" side of other elements would then be oriented on "upper" sides of the other elements. Thus, the exemplary term "lower" may thus encompass an orientation of "lower" as well as "upper" depending on the particular orientation of the drawings. Similarly, if the device in one of the figures is turned over, elements described as "below" or "beneath" other elements would then be oriented "above" the other elements. Thus, the exemplary terms "below" or "under" can encompass both an orientation of above and below.
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,當術語「包括」及/或「包括」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。 It should be noted that, as used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. It should also be understood that when the terms "comprises" and/or "comprising" are used in this specification, it specifies the presence of stated features, steps, operations, elements and/or components, but does not exclude the addition of one or more other features, Steps, operations, component assemblies and/or groups thereof.
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領域的一般技術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。 Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It should be further understood that terms (such as those defined in commonly used dictionaries) should be interpreted to have meanings consistent with their meanings in the relevant art and in the context of the present invention, and will not be interpreted ideally unless expressly so defined herein. over-form interpret the meaning.
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 lowercase letters used in the formulas of the following monomers and polymers especially denote integers.
如本文中所揭示之矽氧烷粒子材料可用於任何所需LED裝置中,然而,作為第一實例,可使用GaN LED。GaN類LED為稱為固態光源之特定類型之發光裝置,其具有許多優點,諸如緊密性、低能耗、長使用壽命、不含汞、具有高效率以及低服務率。GaN LED以不同形式及組合提供於照明應用中,諸如a)三種類型之單色LED(藍色、綠色、紅色)之組合;b)藍光LED與黃色螢光粉末之組合;c)紫外線LED與三色紅色-綠色-藍色螢光粉末之組合,以及其他組合及實施方案。 Silicone particle materials as disclosed herein can be used in any desired LED device, however, as a first example, a GaN LED can be used. GaN-based LEDs are a specific type of light emitting device known as solid-state light sources, which have many advantages such as compactness, low power consumption, long lifetime, contain no mercury, have high efficiency, and have low service rates. GaN LEDs are available in different forms and combinations for lighting applications, such as a) a combination of three types of monochromatic LEDs (blue, green, red); b) a combination of blue LEDs and yellow phosphor powder; c) UV LEDs Combination with three-color red-green-blue fluorescent powder, and other combinations and implementations.
可基於互補顏色理論,經由釔-鋁-石榴石結構之YAG:Ce螢光材料之組合,使用藍光LED獲得白光。由於自YAG發射之光為黃色-綠色,獲得之白光表徵為具有高色溫及冷色調以使得顯色分度並非對於所有用途均為令人滿意的。因此,可添加綠色、黃色或紅色螢光粉末以獲得具有不同色溫(冷色調至暖色調)之白光及改良顯色分度。其他磷光主體,特定言之基於矽酸鹽、硫酸鹽、氮矽酸鹽以及側氧基-氮矽酸鹽之彼等磷光主體可用於改良顯色。 Based on complementary color theory, white light can be obtained using blue LEDs through the combination of YAG:Ce fluorescent materials with yttrium-aluminum-garnet structure. Since the light emitted from YAG is yellow-green, the resulting white light is characterized by a high color temperature and a cool tint such that the color scale is not satisfactory for all uses. Therefore, green, yellow or red phosphor powders can be added to obtain white light with different color temperatures (cool to warm) and improved color rendering. Other phosphorescent hosts, in particular those based on silicates, sulfates, nitrosilicates and pendoxo-nitrosilicates, can be used to improve color rendering.
更特定言之,白光LED可使用藉由淡黃色磷光體/閃爍體塗層覆蓋之450奈米-470奈米藍光氮化鎵(GaN)LED,所述塗層可由用鈰處理之YAG:Ce釔鋁石榴石晶體製成。由於黃光刺激人眼之感紅視錐及感綠視錐,自GaN LED發射之藍光及自磷光體發射之黃光之所得混合物呈現為白光。LED及磷光體之其他組合亦可產生白光之外觀。LED之組合可給出白光之外觀,諸如同時自 其作用區發射藍光且自基板發射黃光之ZnSe基板上之同質磊晶生長之ZnSe。另外,已知紅光、綠光以及藍光LED之組合在具有或不具有磷光體之情況下產生白光。亦可能的為鎢酸鹽、碳氮化物、鉬酸鹽以及硒化物磷光體,以及量子點。 More specifically, white LEDs can use 450nm-470nm blue gallium nitride (GaN) LEDs covered by a yellowish phosphor/scintillator coating, which can be made of YAG:Ce treated with cerium. Made of yttrium aluminum garnet crystals. Since yellow light stimulates the red and green cones of the human eye, the resulting mixture of blue light emitted from the GaN LED and yellow light emitted from the phosphor appears as white light. Other combinations of LEDs and phosphors can also produce the appearance of white light. Combinations of LEDs can give the appearance of white light, such as Homoepitaxially grown ZnSe on a ZnSe substrate whose active region emits blue light and emits yellow light from the substrate. Additionally, combinations of red, green, and blue LEDs are known to produce white light with or without phosphors. Also possible are tungstate, carbonitride, molybdate and selenide phosphors, and quantum dots.
YAG磷光體及藍光LED之組合為用於不需要高顯色指數(CRI)及暖色溫之情況之常用組合。或者,矽酸鹽磷光體為可能的,例如自UV紫光源及藍光源發射綠色、黃色以及橙色(諸如507奈米至600奈米)之矽酸鹽磷光體。對於需要暖色及飽和紅色之LED應用(例如顯示器或住宅/零售店照明),可能需要紅光及/或綠光磷光體。氮化物磷光體(或氮氧化物磷光體)為可能的。紅色氮化物磷光體可發射諸如620奈米與670奈米之間的顏色。亦可能的為例如發射綠色或黃色光譜內,諸如516奈米至560奈米之光的鋁酸鹽磷光體。 The combination of YAG phosphor and blue LED is a common combination for situations where high color rendering index (CRI) and warm color temperature are not required. Alternatively, silicate phosphors are possible, eg silicate phosphors that emit green, yellow and orange (such as 507nm to 600nm) from UV violet and blue light sources. For LED applications that require warm and saturated red colors, such as displays or residential/retail lighting, red and/or green phosphors may be required. Nitride phosphors (or oxynitride phosphors) are possible. Red nitride phosphors can emit colors such as between 620 nm and 670 nm. Also possible are, for example, aluminate phosphors emitting light in the green or yellow spectrum, such as 516 nm to 560 nm.
如圖1中可見,在藍寶石基板14上,顯示n摻雜氮化鎵區域12。藉由例如矽或氧摻雜GaN可產生n型半導體區域。亦說明p摻雜氮化鎵區域13。藉由例如鎂摻雜GaN可產生p型半導體區域。說明電極10a及電極10b且用於跨越GaN半導體區域提供偏壓以引起LED發光,在此實例中,光沿所有方向發射。
As can be seen in Figure 1, on a
替代藍寶石基板,有可能使用SiC基板(上面形成有InGaN半導體),諸如克里公司(Cree,Inc.)之LED。或者,上面具有摻雜GaN半導體區域之GaN基板亦為可能的,諸如索拉公司(Soraa,Inc.)之LED,或者,上面具有GaN半導體之Si基板亦為可能的,諸如普瑞公司(Bridgelux,Inc.)或歐司朗公司(Osram,Inc.)之LED。使用矽基板具有使用大晶圓尺寸(例如6吋晶圓、 8吋晶圓或更大晶圓)之益處。 Instead of sapphire substrates, it is possible to use SiC substrates (on which InGaN semiconductors are formed), such as Cree, Inc. LEDs. Alternatively, a GaN substrate with a doped GaN semiconductor region on it is also possible, such as LEDs from Soraa, Inc., or a Si substrate with a GaN semiconductor on it, such as Bridgelux Inc. , Inc.) or OSRAM (Osram, Inc.) LED. The use of silicon substrates has the advantage of using large wafer sizes (such as 6-inch wafers, 8-inch wafers or larger) benefits.
如圖2中可見,提供SiC或Cu的基板16,其上具有p摻雜GaN區域13,及n摻雜GaN區域12。亦說明電極10。基板16與電極10之間施加之偏壓致使LED發光。如圖2中可見,光主要沿向上方向定向。在圖2之實例中,最接近晶粒基板提供p摻雜區域,而在圖1之實例中,最接近晶粒基板提供n摻雜區域。
As can be seen in FIG. 2 , a
如圖1及圖2中所說明,提供晶粒附連的接著劑層17以將基板(藍寶石、SiC、Cu、GaN、Si等)附連至支撐基板或封裝基板19。LED晶粒附連接著劑較佳但不一定為導熱的(例如在光學反射之情況下可具有大於0.5瓦/公尺.克耳文(W/(m.K)),較佳大於4.0瓦/公尺.克耳文且更佳大於10.0瓦/公尺.克耳文之熱導率。取決於選擇之材料及濃度,高得多的熱導率(諸如大於25.0瓦/公尺.克耳文或大於50.0瓦/公尺.克耳文)亦為可能的。然而,若接著劑或密封劑為透明的,則熱導率通常大於0.1瓦/公尺.克耳文(例如0.1瓦/公尺.克耳文至0.5瓦/公尺.克耳文,或諸如大於0.2瓦/公尺.克耳文,例如大於0.5瓦/公尺.克耳文)。無論作為接著劑或密封劑,矽氧烷材料可沈積為流體,例如液體或凝膠,諸如藉由諸如注射器沈積或網版印刷之方法分配。可使用其他沈積法,諸如旋塗、浸漬、噴墨、簾幕式塗佈、滴瀝、滾塗、凹版印刷、反向膠印、擠壓塗佈、狹縫塗佈、噴塗、柔版等。
As illustrated in FIGS. 1 and 2 , a die attach
LED晶粒附連接著劑可為電絕緣或導電的。在圖2之實例中,由於晶粒基板為電極中的一者,LED晶粒附連接著劑亦應導電,諸如具有小於1×10-3Ω.m之電阻率,較佳小於1×10-5Ω.m,或甚至小於1×10-7Ω.m之電阻率。在圖1之實例中,LED晶粒附 連接著劑可為電絕緣或導電的。若導電,則電阻率可在如關於圖2在上文所述之範圍內。若電絕緣,則電阻率可大於1×103歐.公尺,諸如大於1×105歐.公尺,或甚至大於1×109歐.公尺。 The LED die attach adhesive can be electrically insulating or conductive. In the example of Figure 2, since the die substrate is one of the electrodes, the LED die attach adhesive should also be conductive, such as having a value less than 1×10 -3 Ω. The resistivity of m is preferably less than 1×10 -5 Ω. m, or even less than 1×10 -7 Ω. The resistivity of m. In the example of FIG. 1, the LED die attach adhesive can be electrically insulating or conductive. If conductive, the resistivity may be within the range as described above with respect to FIG. 2 . If it is electrically insulated, the resistivity can be greater than 1×10 3 ohms. Meters, such as greater than 1 × 10 5 Euro. Meters, or even greater than 1×10 9 Euro. meter.
LED晶粒附連材料較佳在可見光譜內(或例如在LED發光-例如紫外光之光譜內)並非光學吸收的。晶粒附連層可透射可見(或UV)光,其中透射至少80%,較佳透射至少85%,更佳90%正交入射於其之可見光。亦有可能的是透射92.5%,或甚至95%或更多可見光。若使用透明晶粒附連材料,則可在必要時提供支撐基板或封裝基板上之反射層以反射光,以改良自LED燈之光輸出之亮度。 The LED die attach material is preferably not optically absorptive in the visible spectrum (or, for example, in the spectrum in which the LED emits light, such as ultraviolet light). The die attach layer is transmissive to visible (or UV) light, wherein at least 80%, preferably at least 85%, and more preferably 90% of the visible light normally incident thereon is transmitted. It is also possible to transmit 92.5%, or even 95% or more of visible light. If a transparent die attach material is used, a reflective layer on the support substrate or packaging substrate may be provided to reflect light if necessary to improve the brightness of the light output from the LED lamp.
在替代實例中,LED晶粒附連材料為高度反射的。晶粒附連材料具反射性而可幫助朝向封裝基板或支撐基板之光重定向,以定向出封裝,因此改良LED燈之亮度。較佳地,在此實例中,藉由LED晶粒附連層反射85%或更多光,或反射90%或更多,或甚至95%或更多可見光。晶粒附連材料可不僅安置於晶粒下部,而且可安置於晶粒側邊周圍以反射自裝置側邊發出的光。 In an alternative example, the LED die attach material is highly reflective. The die attach material is reflective to help redirect light towards the package substrate or support substrate to be directed out of the package, thus improving the brightness of the LED lamp. Preferably, in this example, 85% or more of light is reflected by the LED die attach layer, or 90% or more, or even 95% or more of visible light. Die attach material can be placed not only under the die, but also around the sides of the die to reflect light emanating from the sides of the device.
如本文中所揭示之矽氧烷粒子材料亦可提供於LED之前側上作為障壁層或密封劑。如圖3中可見,晶粒24經由晶粒附連接著劑22附連至封裝基板20。在此實例中,晶粒附連接著劑可如上文所述,或可為習知晶粒附連接著劑,諸如由金屬焊接、玻璃料、聚合物環氧化物等製得之晶粒附連接著劑。晶粒24為LED裝置之簡化圖示,在晶粒基板上具有半導體材料層,線結合25將晶粒電連接至封裝基板。必要時,亦提供磷光層28以將LED發射之光之波長自光之第一波長位移至光之第二波長。較佳地,光之第
二波長在可見光譜內,然而,光之第一波長可在可見光譜內,或在可見光譜外,諸如UV光。
Silicone particle materials as disclosed herein can also be provided on the front side of the LED as a barrier layer or encapsulant. As can be seen in FIG. 3 , die 24 is attached to package
亦有可能不存在磷光體,使得不提供磷光層28。若提供磷光層28,則根據此實例,在如本文中所揭示之矽氧烷材料內提供磷光體,視情況包含粒子,但較佳不包含。在具有或不具有磷光層28的情況下提供密封劑層29以圍繞及保護封裝基板上之LED裝置。若不提供磷光層28,或在不具有磷光體的情況下提供,則有可能在必要時在密封劑層29內提供磷光材料。必要時,磷光層28及密封劑層29均可配備有磷光材料。密封劑層29可由如本文中所揭示之矽氧烷材料製得,具有或不具有向其中添加之粒子。
It is also possible that no phosphor is present, so that no
替代實例顯示於圖4中,其中說明封裝基板30,其具有經由結合層與其結合之晶粒32。如關於圖3所提及,結合層可為如本文中所揭示之矽氧烷粒子組成物,或另一類型之晶粒附連材料。晶粒32為LED裝置之簡化視圖,其中較佳具有p摻雜區域及n摻雜區域,諸如摻雜GaN之半導體材料安置於諸如藍寶石、SiC、Cu、Si、GaN等之基板上。必要時,提供具有磷光材料35之第一密封層及/或提供第二密封層37。磷光材料35及第二密封層37可如關於圖3之層28及層29在上文所述。
An alternative example is shown in Figure 4, which illustrates a
圖5中所說明的為用於LED裝置之覆晶型封裝,其中在透明的基板40(例如藍寶石)上提供半導體材料41(例如GaN)。在覆晶型封裝中,半導體材料41及電連接區域47面朝基板42結合,所述基板在此狀況下為上面具有電路及電連接區域48之矽基板。基板40及基板42上之電連接區域或焊墊區域經由導電的如本文中所揭示之矽氧烷粒子接著劑46連接。必要時,可提供根據
本文中所揭示內容之矽氧烷材料49,其為電絕緣的且其提供改良之接著及CTE特性。矽氧烷材料49可不具有粒狀材料或可具有粒子,諸如不提供導電特性之氧化物或氮化物粒子。矽氧烷粒子接著劑46可由網板印刷、插針沈積或其他適合方法提供。矽氧烷材料49可為低分子量矽氧烷或與添加之溶劑一起呈液體形式提供,以經由毛細作用填充基板之間的區域。矽氧烷粒子接著劑46可在添加矽氧烷材料49之前固化,或兩種材料可一起固化。固化可視需要經由UV光或熱。
Illustrated in FIG. 5 is a flip chip package for an LED device in which a semiconductor material 41 (eg GaN) is provided on a transparent substrate 40 (eg sapphire). In a flip-chip package, the
另外,如圖5中所說明,線結合45將矽的基板42上之電路連接至封裝基板/支撐基板的基板44,其可為陶瓷基板或其他所需材料。接著劑43將基板42連接至基板44,且可為如本文中所揭示之矽氧烷粒子材料,較佳為導熱的。矽氧烷材料49可在可見(或UV)光譜內為光學透射的,或可對可見光或UV光為光學反射的。若為透射的,則反射層可提供於基板42上以沿另一相對方向將光反射回以增加LED燈之效率。
Additionally, as illustrated in FIG. 5,
更特定言之,關於上文提及之矽氧烷粒子組成物,在提供矽氧烷聚合物的情況下製得組成物。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。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。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。單體(或寡聚)偶合劑包含於組成物中,較佳具有如同在矽氧烷聚合物中,當施加熱或光時同樣具反應性之官能性交聯基團。取決於組成 物之最終用途,亦可添加額外材料,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無溶劑之黏滯流體,所述組成物照此儲存及運送。 More specifically, with regard to the above-mentioned silicone particle composition, the composition is produced in the presence of a silicone polymer. Preferably, the polymer has a silica backbone with aryl (or alkyl) substituents and functional crosslinking substituents. The filler material is mixed with the silicone polymer. The filler material is preferably a granular material comprising particles having an average particle size of 100 microns or less, preferably 10 microns or less. A catalyst is added which reacts with the functional crosslinking groups in the silicone polymer when heat or UV light (or other activation method) is provided to the composition. Monomeric (or oligomeric) coupling agents are included in the composition, preferably having functional crosslinking groups that are also reactive upon application of heat or light as in silicone polymers. depends on composition Depending on the end use of the product, additional materials such as stabilizers, antioxidants, dispersants, adhesion accelerators, plasticizers, softeners and other possible components may also be added. Although solvents may be added, in a preferred embodiment the composition is solvent-free and a solvent-free viscous fluid, and the composition is stored and shipped as such.
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。 As noted above, compositions made as disclosed herein include silicone polymers.
為了製造矽氧烷聚合物,提供具有以下化學式之第一化合物:SiR1 aR2 4-a For the manufacture of siloxane polymers, a first compound of the following formula is provided: 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。 wherein a is 1 to 3, R 1 is a reactive group, and R 2 is an alkyl or aryl group.
亦提供具有以下化學式之第二化合物:SiR3 bR4 cR5 4-(b+c) Also provided is a second compound having the 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)。 Wherein R 3 is a crosslinking functional group, R 4 is a reactive group, and R 5 is an alkyl or aryl group, and wherein b=1 to 2, and c=1 to (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。第三化合物可具有以下化學式:SiR9 fR10 g Together with the first compound and the second compound an optional third compound is provided for polymerization 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 or aryl group and 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。 The first compound, the second compound and the third compound may be provided in any order, and an oligomeric partially polymerized version of any of these compounds may be provided in place 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, as well as any compounds described below, if such compounds have more than one single type of "R" group, such as multiple aryl or alkyl groups, or multiple reactive group, or a plurality of cross-linking functional groups, etc., then independently select a plurality of R groups 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. Likewise, multiple R2 groups are independently selected to be the same or different from each other. The same is true for any other compound mentioned herein unless expressly stated otherwise.
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,連同其他視情況選用之組分,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。 A catalyst is also provided. The catalyst can be a base catalyst, or other catalysts as mentioned below. The provided catalyst should be capable of polymerizing the first compound and the second compound together. As noted above, the order of adding the compounds and catalyst can be in any desired order. The various components provided together are polymerized to produce a silicone 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, adhesion promoters, 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 specifically, in one example, a siloxane polymer is prepared by polymerizing a first compound and a second compound, wherein the first compound has the 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) wherein 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)。 Wherein R 3 is a crosslinking functional group, R 4 is a reactive group, and R 5 is an alkyl or 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 ) bonded to silicon in the compound. Combinations of different alkyl groups, combinations of different aryl groups or combinations of 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 especially more 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 can be branched with one or more, preferably two C1 to C6 alkyl groups at the alpha position or the beta position. Specifically, the alkyl group is a lower alkyl group containing 1 to 6 carbon atoms, which optionally carries 1 to 3 substituents selected from methyl and halogen. Methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl and tert-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 is aryl, aryl may be phenyl, which optionally carries 1 to 5 substituents selected from halogen, alkyl or alkenyl on the ring, or naphthyl, which optionally carries on the ring structure Carries 1 to 11 substituents selected from haloalkyl or alkenyl, optionally fluorinated (including perfluorinated or partially fluorinated). If the aryl group is a polycyclic aryl group, the polycyclic aryl group can be, for example, anthracene, naphthalene, phenanthrene, tetracene, which can carry 1-8 substituents as appropriate or can also optionally contain 1 to 12 substituents An alkyl, alkenyl, alkynyl, or aryl group of carbons is "spaced apart" from the silicon atom. Monocyclic structures such as phenyl groups can also be spaced from silicon atoms in this manner.
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選用之額外化合物可包含為聚合反應的一部分。 The siloxane polymer is prepared by polymerizing, preferably base catalyzed, between a first compound and a second compound. Optional additional compounds as set forth 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 hydroxyl, halogen, alkoxy, carboxyl, amine or acyloxy. If, for example, the reactive group in the first compound is an -OH group, more specific examples of the first compound may include silanediols, especially diphenylsilanediol, dimethylsilanediol , diisopropylsilanediol, di-n-propylsilanediol, di-n-butylsilanediol, di-tert-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實質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 hydroxyl, halogen, alkoxy, carboxyl, amine or acyloxy, 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 polymerization to form a silicone polymer - such as the third compound, etc.), such that the resulting silicone The alkane polymer is free of any or substantially any H groups directly incorporated into the Si in the siloxane polymer. The group R5, if present entirely in the second compound, is independently alkyl or aryl, such as for the group R2 in the first compound . The alkyl or aryl group R5 may be the same as or different from the group R2 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。此等官能基可選自例如任何環氧化物、環氧丙烷(oxetane)、丙烯酸酯、烯基、炔基、乙烯基以及Si-H基團。 The cross-linking reactive group R 3 of the second compound can be any functional group that can be cross-linked by acid, base, free radical or thermally catalyzed reaction. Such functional groups may be selected from, for example, any epoxy, oxetane, acrylate, alkenyl, alkynyl, vinyl and Si-H groups.
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。此等含有交聯基團的環氧化物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 may be a cyclic ether having three ring atoms that can be crosslinked using acid, base and thermally catalyzed reactions. Examples of such epoxides 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 crosslinked 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 base) propyltrimethoxysilane (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 a double bond) group is preferably located at position 2 or higher relative to the Si atom in the molecule. Branched alkenyl branched preferably at alpha or beta position with one and more preferably two C1 to C6 alkyl, alkenyl or alkynyl, 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. Alkyne group (that is, to the two carbon atoms) are preferably located at positions 2 or higher relative to Si atoms or M atoms in the molecule. Branched chain alkynyl is preferably branched at the alpha position or the beta position with one and more preferably two C1 to C6 alkyl, alkenyl or alkynyl, optionally perfluorinated alkyl, alkenyl or alkynyl groups.
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 mercapto, it may be any organosulfur compound containing a carbon-bonded sulfhydryl group. Examples of mercapto-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 an alkoxy group may be straight-chain or branched. Preferably, the alkoxy group consists of lower alkoxy groups having 1 to 6 carbon atoms (such as methoxy, ethoxy, propoxy and tert-butoxy). Specific examples of the second compound are silanes, especially such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane , 3-(trimethoxysilyl)propyl methacrylate, 3-(trimethoxysilyl)propyl acrylate, (3-glycidyloxypropyl)trimethoxysilane or 3-glycidyloxy Propyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane.
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 for polymerization 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R10為烷基或芳基,且g=4-f。 Wherein R 9 is a reactive group, and f=1 to 4, and R 10 is an alkyl or 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, dimethyldimethoxysilanesilane, vinyltrimethoxysilane, allyltrimethoxysilane, methyltrimethoxysilane Oxysilane, Methyltriethoxysilane, Methyltripropoxysilane, Propylethyltrimethoxysilane, Ethyltriethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane silane.
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 carried out using an acid catalyst, a base catalyst is preferred. The base catalyst used in the base-catalyzed polymerization between the first compound and the second compound can be any suitable basic compound. Examples of such basic compounds are, inter alia, any amine, such as triethylamine, and any barium hydroxide, 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 particular example, the base catalyst is Ba(OH) 2 . The base catalyst may be provided in a weight % of less than 0.5% relative to the first compound and the second compound together, or in a lower amount, such as in a weight % of less than 0.1%.
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。 Polymerization can be carried out in a melt 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, polymerizations are carried out at ambient pressure and the maximum temperature is set by the boiling point of any solvent used. Polymerization can be performed 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 second compound plus other compounds involved 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 group and the second compound has an alkoxy group as a reactive group. Preferably, the total number of -OH groups is no greater than the total number of reactive groups (e.g. alkoxy groups) in the second compound with respect to the amount of first compound added, and is preferably less than (or The total number of reactive groups in the second compound plus any other compound added with the alkoxy group, such as added tetramethoxysilane or other third compound involved in the polymerization reaction (as mentioned herein) . In cases where alkoxy groups outnumber hydroxyl groups, all or substantially all -OH groups will react and be removed from the siloxane, such as methanol (if the alkoxysilane is a methoxysilane), ethanol (if the alkoxysilane Base silane is ethoxysilane) and so on. 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, it is preferred that the reactive The total number of groups exceeds in number the -OH groups in the first compound by 10% or more, preferably by 25% or more. In some embodiments, the number of reactive groups of the second compound exceeds the -OH groups of the first compound by 40% or more, or even 60% or more, 75% or more, or up to 100% or more . Methanol, ethanol and other by-products of the polymerization reaction (depending on the selected compounds) are removed after polymerization, preferably evaporated in a 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 silicone polymer obtained has any desired (weight average) molecular weight, such as 500 grams/mole to 100,000 grams/mole. The molecular weight can 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 can be at the upper end of this range ( Such as 10,000 g/mol to 100,000 g/mol or more preferably 15,000 g/mol to 50,000 g/mol). It may be desirable to mix a polymeric organosiloxane material having a lower molecular weight with an organosiloxane material having a higher molecular weight.
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微米之粒子之微粒填充劑。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 end desired use of the polymer, the silicone polymer obtained can be Then combine 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, including 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 accelerators, and/or other desired components, depending on the silicone material the final desired use. In one example, a reducing agent that can reduce the oxidized surface to its metallic form is included. The reducing agent can remove oxidation from the particle, where the particle is a metal particle with surface oxidation, and/or remove oxidation, such as from a metal bond pad or other metal or conductive area that has oxidized, to improve the silicone particle material and its Electrical connection between deposited or adhered surfaces. Reducing or stabilizing agents may include ethylene glycol, β-D-glucose, polyethylene oxide, glycerol, 1,2-propylene glycol, N,N dimethylformamide, poly-sodium acrylate (PSA), β-cyclodextrin of polyacrylic acid, dihydroxybenzene, polyvinyl alcohol, 1,2-propanediol, hydrazine, hydrazine sulfate, sodium borohydride, ascorbic acid, hydroquinone family, gallic acid, pyrogallol, ethylene diol Aldehydes, Acetaldehyde, Glutaraldehyde, Aliphatic Dialdehyde Family, Paraldehyde, Tin Powder, Zinc Powder, Formic Acid. Additives such as stabilizers, for example antioxidants such as Irganox (as mentioned below) or diazine derivatives may 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-linking silicone or non-silicon resins and oligomers can be used to enhance the 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 polymerization of the silicone polymer, epoxy-functional oligomers or resins may be used. The epoxy oligomer or resin can be any difunctional, trifunctional, tetrafunctional or higher functional epoxy oligomer or resin. Examples of such epoxy oligomers or resins may be 1,3-bis-2-(3,4-epoxycyclohexyl)ethyl 1,1,3,3-tetramethyldisiloxane, 1, 3-Diglycidoxypropyl 1,1,3,3-tetramethyldisiloxane, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-cyclohexanecarboxylate Oxycyclohexyl methyl ester, 1,4-cyclohexanedimethanol diglycidyl ether, bisphenol A diglycidyl ether, 1,2-cyclohexanedicarboxylate diglycidyl ether, 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。 A 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 (eg thermal acid in case of thermally activated polymerization or photoinitiator in case of UV activated). The crosslinking groups in the silicone polymers as described above are preferably epoxy, propylene oxide, acrylate, alkenyl or alkynyl. The curing agent is selected based on the crosslinking groups 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,例如藉由在升高之溫度下使其熔化、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, curing agents for epoxy and propylene oxide groups may be selected from nitrogen-containing curing agents that exhibit blocked or reduced activity, such as primary and/or secondary amines. The definition "primary or secondary amine exhibiting blocked or reduced reactivity" shall mean either incapable or having only a very low ability to react with the resin components due to chemical or physical blocking, but may The reactivity of the amine is regenerated after release of the amine, for example by melting it at elevated temperature, by removing the sheath or coating, by the action of pressure or ultrasound or other energy types, initiating the separation of the resin components The amines of the curing reaction.
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 a borane and at least one amine. The amine can be any type that complexes the organoborane and/or borane and can decomplex to release the organoborane or borane if necessary. Amines can include a variety of structures, such as any primary or secondary amine or polyamines containing primary and/or secondary amines. Organoboranes may be selected from alkylboranes. An example of such a particularly preferred borane is boron trifluoride. Suitable amine/(organo)borane complexes are available from commercial suppliers such as King Industries, Air products, and ATO-Tech. source.
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 release strong acids at high temperatures to catalyze the crosslinking reaction of epoxy groups. Such thermal acid generators can be, for example, any onium salts with complex anions of the BF 4 - , PF 6 - , SbF 6 - , CF 3 SO 3 - and (C 6 F 5 ) 4 B -type , such as sulfonium salts and iodonium salt. Commercial examples of such thermal acid generators are K-PURE CXC-1612 and K-PURE CXC-1614 manufactured by Kings 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。 Additionally, in the case of polymer-containing epoxides and/or propylene oxides, curing agents, co-curing agents, catalysts, initiators or other additives designed to participate in or facilitate the curing of the adhesive formulation may be used, such as Acid anhydride, amine, imidazole, mercaptan, carboxylic acid, phenol, dicyandiamide, urea, hydrazine, hydrazine, amino-formaldehyde resin, melamine-formaldehyde resin, quaternary ammonium salt, quaternary phosphonium salt, triaryl sulfide 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 alkyne crosslinking group curing agents can be heat or UV activated. Examples of thermal activation are peroxides and azo compounds. Peroxides are compounds containing labile oxygen-oxygen single bonds that are readily resolved into reactive free radicals via hemolytic cleavage. Azo compounds have R-N=N-R functional groups that can be decomposed into nitrogen gas and two organic radicals. In both cases, free radicals can catalyze the polymerization of acrylate, alkenyl and alkyne linkages. Examples of peroxides and azo compounds are two-tert-butyl peroxide, 2,2-bis(tert-butyl peroxy)butane, tert-butyl peracetate, 2,5-bis( tert-butylperoxy)-2,5-dimethyl-3-hexyne, dicumyl peroxide, benzoyl peroxide, di-tert-amyl peroxide, peroxybenzoic acid Tertiary butyl ester, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-carboxamidinopropane) dihydrochloride, diphenyldiazene, 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。
Photoinitiators are compounds that decompose into free radicals when exposed to light and thus can promote the polymerization of acrylate, alkenyl, and alkynyl compounds. Commercial examples of such photoinitiators are Irgacure 149, Irgacure 184, Irgacure 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 these types of curing agents attached to silane monomers are γ-imidazolylpropyltriethoxysilane, γ-imidazolylpropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3 -Mercaptopropyltriethoxysilane, 3-(triethoxysilyl)propylsuccinic anhydride, 3-(trimethoxysilyl)propylsuccinic 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 can then be part of the composition and can 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 accelerators are functional silanes, which contain alkoxysilanes and 1 to 3 functional groups. Examples of adhesion promoters used in die attach products 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-glycidyloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane Oxysilane and 3-Acryloxypropyltrimethoxysilane.
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材料。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 polymeric siloxane formed will have a [Si-O-Si-O]n repeating backbone, on which The organofunctionality depends on the silicon-containing starting material. However, it is also possible to achieve [Si-O-Si-C]n or even [Si-O-Me-O]n (where Me is a metal) backbone.
為了獲得[Si-O-Si-C]主鏈,具有以下式之化學品:R2 3-aR1 aSiR11SiR1 bR2 3-b To obtain the [Si-O-Si-C] backbone, 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。 wherein a is 1 to 3, b is 1 to 3 , R is a reactive group as explained above, R is alkyl, alkenyl, alkynyl, alcohol, carboxylic acid, dicarboxylic acid, aryl, poly Aryl, polycycloalkyl, heterocyclic aliphatic, heterocyclic aromatic, and R 11 is independently alkyl or aryl, or an oligomer whose molecular weight is less than 1000 grams/mole; 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 base) ethane, 1,2-bis(methoxydimethylsilyl)ethane, 1,2-bis(triethoxysilyl)ethane, 1,3-bis(dimethylhydroxysilane base) 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(trimethyl Oxysilyl)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] backbone, a 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。 Wherein R3 is a crosslinking functional group, R4 is a reactive group, and R5 is an alkyl, alkenyl, alkynyl, alcohol, carboxylic acid, dicarboxylic acid, aryl, polyaryl, polycycloalkyl , heterocyclic aliphatic group, heterocyclic aromatic group, R 11 is independently alkyl or aryl, and wherein c=1 to 2, d=1 to (3-c), e=1 to 2, and f =1 to (3-e), or oligomers thereof with a molecular weight of less than 1000 g/mole, polymerized together with the first compound, the second compound, the third compound, or any combination thereof 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) Ethyldimethoxysilyl]ethane, 1,2-bis(propylmethacrylatedimethoxysilyl)ethane, 1,4-bis(vinyldimethoxysilyl)benzene, 1,4- Bis(ethynyldimethoxysilyl)benzene, 1,4-bis(ethynyldimethoxysilyl)benzene, 1,4-bis(3-glycidyloxypropyldimethoxysilyl) ) benzene, 1,4-bis[2-(3,4-epoxycyclohexyl)ethyldimethoxysilyl]benzene, 1,4-bis(propyl methacrylate dimethoxysilyl) Benzene (to name a few).
在一個實施例中,具有分子式R1 aR2 bR3 3-(a+b)Si-O-SiR2 2-O-Si R1 aR2 bR3 3-(a+b)之矽氧烷單體,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。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)。 In one embodiment, the formula 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) A siloxane monomer wherein R1 is a reactive group as explained above, R2 is an alkyl or aryl group as explained above, R3 is a crosslinking functional group as explained above, and a=0 to 3 , b=0 to 3, polymerized with the previously mentioned silanes or added as additives to the final formulation. Examples of such compounds are 1,1,5,5-tetramethoxy-1,5-dimethyl-3,3-diphenyltrisiloxane, 1,1,5,5-tetramethoxy 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, 1,1,5,5-tetramethoxy-3,3-dimethyltrisiloxane, 1,1,7,7-tetraethoxy-3, 3,5,5-tetramethyltetrasiloxane, 1,1,5,5-tetraethoxy-3,3-dimethyltrisiloxane, 1,1,5,5-tetramethoxy Base-1,5-[2-(3,4-epoxycyclohexyl)ethyl]-3,3-diphenyltrisiloxane, 1,1,5,5-tetramethoxy-1, 5-(3-glycidyloxypropyl)-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-glycidyl oxypropyl)-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) An additive added to the composition (after polymerizing the siloxane material as indicated above) may be a silane compound having the formula: R 1 a R 2 b SiR 3 4-(a+b)
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 R1 is a reactive group, such as hydroxyl, alkoxy or acetyloxy, R2 is an alkyl or aryl group, R3 is a crosslinking compound , such as epoxy, propylene oxide, alkenyl, acrylic Ester 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 tris-(3-glycidoxypropyl)phenylsilane, tris-[2-(3,4-epoxycyclohexyl)ethyl]phenylsilane, tris-(3-methyl Acryloxy)phenylsilane, Tris-(3-acryloxy)phenylsilane, Tetrakis-(3-glycidyloxypropyl)silane, Tetrakis-[2-(3,4-epoxy Cyclohexyl)ethyl]silane, tetrakis-(3-methacryloxy)silane, tetrakis-(3-acryloxy)silane, tris-(3-glycidyloxypropyl)-p-tolylsilane , Tris-[2-(3,4-epoxycyclohexyl)ethyl]p-tolylsilane, Tris-(3-methacryloxy)p-tolylsilane, Tris-(3-acryloxy ) p-tolylsilane, tris-(3-glycidyloxypropyl)hydroxysilane, tris-[2-(3,4-epoxycyclohexyl)ethyl]hydroxysilane, tris-(3-methylpropene Acryloxy)hydroxysilane, Tris-(3-acryloxy)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 can also be any organic or silicone polymer, which may or may not react with the primary 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, polysilazanes.
微粒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 alloys, silver-plated Fiber, nickel-plated copper, silver-nickel-plated copper, gold-plated copper, gold-nickel-plated copper, or polymers that can be gold-plated, silver-gold, silver, nickel, tin, platinum, titanium, such as polyacrylate, Polystyrene or silicone, but not limited to. The filler can also be a semiconductor material, such as silicon, n-type or p-type doped silicon, GaN, InGaN, GaAs, InP, SiC, but not limited thereto. Furthermore, the filler may be quantum dots or plasmonic particles or phosphor particles. Other semiconductor particles or quantum dots, such as Ge, GaP, InAs, CdSe, ZnO, ZnSe, TiO2 , ZnS, CdS, CdTe, etc. are also possible.
填充劑可為粒子,其為任何適合之金屬或半金屬粒子,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、鍍銀纖維或其合金或組合。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 or semi-metal particles, such as those 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 alloys, silver-plated fibers, or alloys or combinations thereof. Metal particles, as well as semimetals and metalloids, are envisioned as transition metal particles (whether early transition metals or late transition metals). Particles of semimetals or metalloids are envisioned, 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為可能的。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、鈣、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 oxide trihydrate, boron nitride, and the like. Fillers can be in the form of particles or flakes, and can be micron or nano sized. It is possible for the filler to include particles of ceramic compounds which are nitrides, oxynitrides, carbides and oxycarbides of metals or semimetals. In particular, the filler may be particles of silicon, zinc, aluminum, yttrium, ytterbium, tungsten, titanium silicon, titanium, antimony, calcium, nickel, nickel cobalt, molybdenum, magnesium, manganese, lanthanides, 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。 Also possible are particles comprising carbon and selected from carbon black, graphite, graphene, diamond, silicon carbonitride, titanium carbonitride, carbon nanobuds and carbon nanotubes. The filler particles can be carbide particles, such as iron carbide, silicon carbide, cobalt carbide, carbon 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,例如實質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。 Particles of any suitable size can be used depending on the end application. In many cases, small particles are used with an average particle size of less than 100 microns, and preferably less than 50 microns or even 20 microns. Submicron particles are also envisioned, such as those smaller than 1 micron, or for example 1 nm to 500 nm, such as smaller than 200 nm, such as 1 nm to 100 nm, or even smaller than 10 nm. In other examples, particles are provided 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. Particles that are not elongated, such as substantially spherical or square, or flakes with a flattened disk appearance (with smooth or rough edges) are possible, as are elongated whiskers, cylinders, wires, and other elongated particles, such as those with 5: 1 or larger, or particles with an aspect ratio of 10:1 or larger. Very elongated particles with extremely high aspect ratios, such as nanowires and nanotubes are also possible. The high aspect ratio of the nanowires or nanotubes 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 dimension (width or diameter), since the length can be quite long, even up to several centimeters long. As used herein, the term "average particle size" refers to the D50 value at the cumulative volume distribution curve at which 50% by volume of the particles have a diameter smaller than the stated 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 a first set of particles having an average particle size greater than 200 nm is provided together with a second set of particles having an average particle size less than 200 nm, e.g., wherein the average particle size of the first set The particle size is greater than 500 nm and the average particle size of the second set is less than 100 nm (eg, the average particle size of the first set is greater than 1 micron, the particle size of the second set is less than 50 nm, or even less than 25 nm). The melting point of the smaller particles is lower than that of the larger particles, and the smaller particles are smaller than Melting or sintering at the temperature at which particles of the same material of the same size are melted or sintered. In one example, the smaller particles have an average particle size of less than 1 micron and melt or sinter at a temperature less than the bulk temperature of the same material. Depending on the selected particle material and average particle size, melting and sintering temperatures will vary.
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,但在大於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,但在大於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. Thus, if desired, the melting or sintering temperature of the smaller particles can be at or below the polymer solidification temperature to form a melting or sintering linking the larger particles together prior to complete crosslinking and curing of the silicone polymer material. Web of Particles. In one example, the smaller particles are melted or sintered with the larger particles at a temperature below 130°C, such as below 120°C, or even sintered at a temperature below 110°C, while the silicone material is sintered at a higher temperature undergoes substantial crosslinking at temperatures 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 at Substantial polymerization at greater than 120°C (or 130°C). Sintering or melting of the smaller particles prior to substantial polymerization of the silicone material allows the formed metal "mesh" to have greater interconnectivity, which increases the final conductivity of the cured layer. Substantial sintering or substantial polymerization of the smaller particles prior to melting reduces the amount of metal "grid" formed and reduces the conductivity of the final solidified layer. Of course, it is also possible to provide only particles with a smaller average particle size (e.g. sub-micron size), which still achieve lower sintering and melting points compared to the same bulk (or the same particles, e.g., with an average particle size greater than 1 micron). benefit.
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 To enhance coupling with fillers and silicone polymers, coupling agents can be used. This coupling agent will increase the bond between the filler and the polymer and thus can increase the thermal and/or electrical conductivity of the final product. The coupling agent can be any silane monomer with 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。 wherein R 13 is a reactive group such as halogen, hydroxyl, alkoxy, acetyl or acetyloxy, R 14 is alkyl or aryl, and R 15 is such as epoxy, anhydride, cyano, Functional groups of propylene oxide, amine, mercapto, allyl, alkenyl or alkynyl; 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 mixed directly with the filler, silicone polymer, curing agent, and additives when making the final product or the filler particles can be treated with the coupling agent before it is 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 use in the final formulation, different methods can be used, such as deposition from alcoholic solutions, deposition from aqueous solutions, bulk deposition onto fillers, and anhydrous liquid phase deposition. In deposition from an alcoholic solution, an alcohol/water solution is prepared and the pH of the solution is adjusted to slightly acidic (pH 4.5-5.5). The 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 various time periods. After mixing, the particles were filtered, rinsed with ethanol and dried in an oven to obtain surface-treated particles with a coupling agent. Deposition from an aqueous solution is similar to deposition from an alcoholic solution, but pure water is used instead of alcohol as the solvent. If non-amine functionalization is used, the pH is adjusted again by acid. After mixing the particles with the water/silane mixture, the particles were 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 in which a silane coupling agent is mixed with a solvent without any water or pH adjustment. The filler particles are coated with the silanol solution using different methods like spray coating 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 deposition, the silane is mixed with an organic solvent such as toluene, tetrahydrofuran or a hydrocarbon, the filler particles are refluxed in this solution and the additional solvent is removed by vacuum or filtration. The particles can also be subsequently dried in an oven, but this is sometimes not required due to the direct reaction between the particles and the filler under reflux conditions.
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-aminopropylmethyldiethoxysilane, 3- Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, (N-trimethoxysilylpropyl)polyethylenediimine, trimethoxysilylpropyldiethylenetri Amine, phenyltriethoxysilane, phenyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 1-trimethoxysilyl-2 (p, m-chloromethyl) phenylethane, 2- (3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, propylisocyanate 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-(triethoxysilylpropyl)urea, 1,3-divinyltetramethyldisilazane, vinyltriethoxysilane and Vinyltrimethoxysilane (just 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(W/(m.K))之熱導率。取決於選擇之粒子類型,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較低熱導率之材料,諸如在矽氧烷粒子材料為如上文所提及之視情況存在之透射層之情況下。 Depending on the type of particles added, the siloxane-particle cured final product can be a thermally conductive layer or film, such as after final thermal or UV curing with greater than 0.5 watts/meter. Thermal conductivity of Kelvin (W/(m.K)). Depending on the particle type chosen, higher thermal conductivity materials are possible. The metal particles in the siloxane composition can produce a thermal conductivity greater than 2.0 W/m. Kerven, such as greater than 4.0 W/m. kelvin or something To greater than 10.0 W/m. Kerven's cured final film. Depending on the end application, higher thermal conductivities, such as greater than 50.0 W/m, may be required. Kerven, or even greater than 100.0 W/m. Kelvin. In other applications, however, the particles may be selected to produce materials with lower thermal conductivity where necessary, such as where the silicone particle material is an optional transmissive layer as mentioned above.
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,且更佳小於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, the final cured product may have a low resistivity, such as less than 1×10 -3 Ω, if necessary. m, preferably less than 1×10 -5 Ω. m, and preferably less than 1×10 -7 Ω. m. In addition, the sheet resistance of the deposited film is preferably less than 100,000, more preferably less than 10,000. However, many desired end uses of the material can have high resistivities.
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%。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。 In some cases, particularly where the composition will be used in devices requiring optical characteristics, it is more likely that the material will desirably be highly transmissive in the visible spectrum, although in some cases it may be desirable for the final cured silicone to have optically absorptive properties. Light in the visible spectrum (or in the spectrum in which the final device will be operated), or will desirably be highly reflective. As an example of a transparent material, a final cured layer having a thickness of 1 micron to 50 microns will transmit at least 85%, or preferably at least 90%, more preferably at least 92.5% and most preferably at least 95%, of visible light normally incident thereon. 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 materials of the 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.
在本文中包含之可適用的穩定劑或抗氧化劑中的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。 Among the applicable stabilizers or antioxidants included 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 also containing Phenolic compounds of sterically bulky free radicals. Specifically, the tert-butyl group is generally substituted on the benzene ring at least one ortho position relative to the phenolic hydroxyl group. The presence of these sterically bulky substituted radicals near the hydroxyl group serves to slow down its stretching frequency and correspondingly its reactivity; this steric hindrance thus provides the phenolic compound with its stabilizing properties. Representative hindered phenols include: 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-benzene; tetrakis-3( 3,5-di-tert-butyl-4-hydroxyphenyl)-propionyl pentaerythritol; 3(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid octaalkyl esters; 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 di-n-octylthio)ethyl-4-hydroxy-benzoate; and sorbitol hexa[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)-propionate]. Commercial examples of antioxidants are, for example, Encanox 1035, Encanox 1010, Encanox 1076, Encanox 1098, Encanox 3114, Encanox PS800, Encanox, manufactured by BASF Kesi PS802, Yanjia Knox 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 silicone polymer and filler is between 100:0 and 5:95. The ratio between silicone polymer and cross-linked silicone or non-silicon 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%. The amount of adhesion accelerator is 0 to 10% based on the total amount of the formulation. Antioxidants are present in amounts of 0 to 5% based on the total weight of the formulation.
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)。 Silicone-particle compositions can be used in various fields. It can be used as electronic or optoelectronic packaging, LED and OLED front-end and back-end processing, 3D, photovoltaic and display metallization, soldering instead of solder bumps in semiconductor packaging, printed electronic devices, OLED low work function cathode Inks, ITO replacement inks, metal grids and others Adhesives or sealants in electrodes, high-resolution photovoltaic pastes, LMO cathode pastes, photovoltaics, power electronics and EMI, touch sensors and other displays, thermal or UV curable sealants or dielectrics ( Just 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 thermal acid generator is used, the material is placed in an oven for a specified period of time. Also possible is curing by means of 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5,000公克/莫耳,且更佳約500公克/莫耳至2,000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時,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/mole to 10,000 g/mole, preferably about 400 g/mole to 5,000 g/mole, and more preferably About 500 g/mol to 2,000 g/mol. The polymer is combined with particles of any desired size, preferably with an average particle size of 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 clarity, the particles may be ceramic particles added at a lower weight %, such as 1 to 20 weight %. If conductivity is required, such as when using siloxane 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50兆帕-秒至100,000兆帕-秒,較佳1000兆帕-秒至75,000兆帕-秒且更佳5000兆帕-秒至50,000兆帕-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 polymerization of the first compound and the second compound is carried out, and the particles are mixed therewith to form 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 - Viscous fluids up to 50,000 MPa-s. Viscosity can be measured by a viscometer, such as a Brookfield viscometer or a Cole-Parmer viscometer, which rotates a disc or cylinder in a fluid sample and measures against Torque required to induce viscous resistance of motion. Can be any desired speed, such as 1rpm to 30rpm, preferably 5rpm, and preferably in the material Rotate while measuring 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 shipped to the customer as a viscous material in a container shipped at ambient temperature without cooling or freezing. As a final product, the material can be applied in a variety of applications as mentioned above, usually heat cured or UV cured to form a solid cured polymeric silicone 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,由於需要將實質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,儘管組成物實質上不含溶劑,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。 Compositions as disclosed herein are preferably free of any substantial solvent. Solvents may be added extemporaneously, such as for mixing curing agents or other additives with the polymeric viscous material. In this case, for example, a curing agent is mixed with a solvent to form a fluid material that can then be mixed with a viscous silicone polymer. However, due to the need to ship the substantially solvent-free composition to the customer and subsequently apply it to the customer's device, the solvent that has been temporarily added is removed in the dry chamber. However, although the composition is substantially solvent-free, there may be traces of residual solvent that cannot be removed during the drying process. Removing this solvent by reducing shrinkage during the final curing process facilitates deposition of the compositions disclosed herein, minimizes shrinkage over time during device lifetime, and facilitates 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 desired viscosity of the composition, and the particles to be included, it is possible to fine-tune the silicone polymer (starting compound, molecular weight, viscosity, etc.) so that when incorporated with particles and other components In the composition of the product, the desired final characteristics are achieved in terms of subsequent delivery to the customer. 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 a week or even a month after manufacture until end use by the customer.
提供以下矽氧烷聚合物實例以說明本發明,且不意欲為 限制性的。 The following silicone polymer examples are provided to illustrate the invention and are not intended to be restrictive.
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 was 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。 Silicone polymer i: diphenylsilanediol (60 grams, 45 moles%), 2-(3,4-epoxycyclohexyl) ethyl] trimethoxysilane (55.67 grams, 36.7 moles %) and tetramethoxysilane (17.20 g, 18,3 mol%) filled 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 mixture of silanes. The silane mixture was stirred at 80° C. for 30 minutes during the reaction of the diphenylsilanediol with the alkoxysilane. After 30 minutes, the methanol formed was evaporated off under vacuum. The silicone polymer has a viscosity of 1000 mPas and a Mw of 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。 Silicone polymer ii: diphenylsilanediol (30 grams, 45 moles%), 2-(3,4-epoxycyclohexyl) ethyl] trimethoxysilane (28.1 grams, 37 moles %) and dimethyldimethoxysilane (6.67 g, 18 mole %) 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 grams of barium hydroxide monohydrate dissolved in 1 milliliter of methanol was added dropwise to the mixture of silanes. The silane mixture was stirred at 80° C. for 30 minutes during the reaction of the diphenylsilanediol with the alkoxysilane. After 30 minutes, the methanol formed was evaporated under vacuum. The silicone polymer has a viscosity of 2750 mPas and a Mw of 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。 Silicone polymer iii: diphenylsilanediol (24.5 grams, 50 moles%), 2-(3,4-epoxycyclohexyl) ethyl] trimethoxysilane (18.64 grams, 33.4 moles %) and tetramethoxysilane (5.75 g, 16.7 mol%) filled with stirring 250ml round bottom flask with stirring rod and reflux condenser. The flask was heated to 80°C under a nitrogen atmosphere and 0.026 grams of barium hydroxide monohydrate dissolved in 1 mL of methanol was added dropwise to the mixture of silanes. The silane mixture was stirred at 80° C. for 30 minutes during the reaction of the diphenylsilanediol with the alkoxysilane. After 30 minutes, the methanol formed was evaporated under vacuum. The silicone polymer has a viscosity of 7313 mPas and a Mw of 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。 Silicone polymer iv: diphenylsilanediol (15 grams, 50 moles%), 2-(3,4-epoxycyclohexyl) ethyl] trimethoxysilane (13.29 grams, 38.9 moles %) 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 grams of barium hydroxide monohydrate dissolved in 1 mL of methanol was added dropwise to the mixture of silanes. The silane mixture was stirred at 80° C. for 30 minutes during the reaction of the diphenylsilanediol with the alkoxysilane. After 30 minutes, the methanol formed was evaporated under vacuum. The silicone polymer has a viscosity of 1788 mPas and a Mw of 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。 Silicone polymer v: Diphenylsilanediol (15 grams, 45 moles%), 2-(3,4-epoxycyclohexyl) ethyl] trimethoxysilane (13.29 grams, 35 moles %) and vinyltrimethoxysilane (4.57 g, 20 mol%) were filled in 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 0.018 grams of barium hydroxide monohydrate dissolved in 1 milliliter of methanol was added dropwise to the mixture of silanes. The silane mixture was stirred at 80° C. for 30 minutes during the reaction of the diphenylsilanediol with the alkoxysilane. After 30 minutes, the methanol formed was evaporated off under vacuum. The silicone polymer has a viscosity of 1087 mPas and a Mw of 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。 Silicone polymer vi: Diisopropylsilanediol (20.05 grams, 55.55 mol%), 2-(3,4-epoxycyclohexyl) ethyl] trimethoxysilane (20.0 grams, 33.33 mol%) mol%) and bis(trimethoxysilyl)ethane (7.3 g, 11.11 mol%) was filled in 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 grams of barium hydroxide monohydrate dissolved in 1 milliliter of methanol was added dropwise to the mixture of silanes. The silane mixture was stirred at 80° C. for 30 minutes during the reaction of the diphenylsilanediol with the alkoxysilane. After 30 minutes, the methanol formed was evaporated off under vacuum. The silicone polymer has a viscosity of 150 mPas and a Mw of 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。 Silicone polymer vii: Diisobutylsilanediol (18.6 grams, 60 mol%) and 2-(3,4-epoxycyclohexyl) ethyl] trimethoxysilane (17.32 grams, 40 mol%) ear%) was filled with 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 grams of barium hydroxide monohydrate dissolved in 1 mL of methanol was added dropwise to the mixture of silanes. The silane mixture was stirred at 80° C. for 30 minutes during the reaction of the diphenylsilanediol with the alkoxysilane. After 30 minutes, the methanol formed was evaporated off under vacuum. The silicone polymer has a viscosity of 75 mPas and a Mw of 710.
提供以下組成物實例以說明本發明,且不意欲為限制性的。 The following composition examples are provided to illustrate the invention 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具有環氧基作為交聯官能基之矽氧烷聚合物(18.3公克,18.3%)、平均尺寸(D50)為4微米之銀片(81公克,81%)3-甲基丙烯酸丙酯三甲氧基矽烷(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。組成物之黏度為15000mPas。 Comparative example 1, silver-filled adhesive: silver flakes with an average size (D50) of 4 microns of siloxane polymer (18.3 grams, 18.3%) with epoxy groups as cross-linking functional groups were mixed using a high-shear mixer (81 grams, 81%) 3-Propyl methacrylate trimethoxysilane (0.5 grams, 0.5%) and Kings Industries K-PURE CXC-1612 Thermal acid generator (0.2%) was mixed together. The viscosity of the composition is 15000mPas.
比較例2,氧化鋁填充接著劑:使用三輥研磨機將具有環氧基作為交聯官能基之矽氧烷聚合物(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-甲基丙烯酸丙酯三甲氧基矽烷(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。組成物之黏度為20000mPas。 Comparative example 2, alumina filled adhesive: use a three-roll mill to grind siloxane polymer (44.55 grams, 44.45%) with epoxy groups as cross-linking functional groups, and alumina with an average size (D50) of 0.9 microns (53 grams, 53%), 3-propyl methacrylate trimethoxysilane (1 grams, 1%), Yanjia Nox 1173 (1 grams, 1%) and Kings Industries K-PURE CXC-1612 heat Acid generator (0.45 g, 0.45%) was mixed together. The viscosity of the composition is 20000mPas.
比較例3,BN填充接著劑:使用三輥研磨機將具有環氧基作為交聯官能基之矽氧烷聚合物(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。組成物之黏度為25000mPas。 Comparative Example 3, BN filled adhesive: use a three-roll mill to grind a siloxane polymer (60 grams, 60%) with an epoxy group as a crosslinking functional group, and boron nitride with an average size (D50) of 15 microns Flakes (35 g, 35%), Yanjia Nox 1173 (1.3 g, 1.3%), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (3.4 g, 3.4%), and King’s Industrial K-PURE CXC-1612 Thermal Acid Generator (0.3 g, 0.3%) was mixed together. The viscosity of the composition is 25000mPas.
比較例4,半透明材料:使用三輥研磨機將具有甲基丙烯酸酯作為官能基之矽氧烷聚合物(89公克,89%)、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%)以及豔佳固917光引發劑(4公克,4%)混合在一起。組成物之黏度為25000mPas。 Comparative example 4, translucent material: a siloxane polymer (89 grams, 89%) having methacrylate as a functional group, fumed silica with an average size (D50) of 0.007 microns was made using a three-roll mill (5 grams, 5%), Yanjia Nox 1173 (2 grams, 2%) and Yanjiagu 917 photoinitiator (4 grams, 4%) were mixed together. The viscosity of the composition is 25000mPas.
比較例5,透明材料:將含二苯基矽烷二醇(20.0公克,92毫莫耳)、9-菲基三甲氧基矽烷(16.6公克,56毫莫耳)、3-甲基丙烯醯氧基丙基三甲氧基矽烷(9.2公克,37毫莫耳)以及BaO(25毫克)之甲醇置放在100毫升燒瓶中且回流1小時。減壓蒸發揮發物。獲得透明聚合物樹脂(37公克)。 Comparative Example 5, transparent material: diphenylsilanediol (20.0 grams, 92 millimoles), 9-phenanthrenyltrimethoxysilane (16.6 grams, 56 millimoles), 3-methacryloxy Propyltrimethoxysilane (9.2 g, 37 mmol) and BaO (25 mg) in methanol were placed in a 100 mL flask and refluxed for 1 h. Volatiles were evaporated under reduced pressure. A clear polymer resin (37 grams) was obtained.
比較例6,高折射率材料:將8.6公克如實例X1中所描 述製備之具有高折射率之聚合物樹脂於5.7公克ZrO2奈米粒子溶液在固體含量為50%之1,2-丙二醇單甲醚乙酸酯(PGMEA)中摻合。0.26公克光引發劑(巴斯夫之達若可(Darocur)1173)、0.4公克作為接著促進劑之寡聚3-甲基丙烯醯氧基丙基三甲氧基矽烷以及20毫克界面活性劑(畢克化學(BYK Chemie)之BYK-307)添加至溶液中。 Comparative Example 6, High Refractive Index Material: 8.6 grams of a polymer resin with a high refractive index prepared as described in Example X1 was dissolved in 5.7 grams of a ZrO nanoparticle solution in 1,2 - propanediol monohydrate with a solids content of 50%. Blended in methyl ether acetate (PGMEA). 0.26 grams of photoinitiator (Darocur 1173 of BASF), 0.4 grams of oligomeric 3-methacryloxypropyltrimethoxysilane and 20 milligrams of surfactants (Bykchem (BYK-307 from BYK Chemie)) was added to the solution.
所獲得之材料以2000rpm旋塗於100毫米矽晶圓上。膜在80℃下在熱板上烘烤5分鐘且以3000毫焦/平方公分之劑量經UV固化。藉由更改聚合物樹脂與ZrO2奈米粒子之重量比調節折射率。 The obtained material was spin-coated on a 100 mm silicon wafer at 2000 rpm. The films were baked on a hot plate at 80°C for 5 minutes and UV cured at a dose of 3000 mJ/cm2. The refractive index was tuned by changing the weight ratio of polymer resin to ZrO2 nanoparticles.
若如本文中所揭示之矽氧烷組成物安置於藉由LED發射之光之光學路徑內且經選擇以對可見(或UV)光為光學透射的,則可基於選擇之矽氧烷粒子材料來選擇折射率。可提供1.25至2.0,例如1.4至1.7或其他所需數值(1.5至1.9、1.25至1.45等)之折射率,其中折射率於632.8奈米波長下量測。可藉由提供聚合至矽氧烷聚合物中之含金屬單體達成較高折射率,例如高於玻璃,諸如1.6至2.0之折射率。如上所述,有可能獲得[Si-O-Me-O]n(其中Me為金屬)主鏈。尤其具有諸如鈦、鉭、鋁、鋯、鉿或硒之金屬之含金屬單體可幫助增加折射率。此類含金屬單體可替代如上文所提及之第一化合物、第二或第三化合物使用,或額外使用。 If the silicone composition as disclosed herein is disposed within the optical path of light emitted by the LED and is selected to be optically transmissive to visible (or UV) light, it may be based on the selected silicone particle material to choose the index of refraction. A refractive index of 1.25 to 2.0, such as 1.4 to 1.7 or other desired values (1.5 to 1.9, 1.25 to 1.45, etc.), can be provided, wherein the refractive index is measured at a wavelength of 632.8 nm. Higher refractive indices, for example higher than that of glass, such as 1.6 to 2.0, can be achieved by providing metal-containing monomers polymerized into the silicone polymer. As mentioned above, it is possible to obtain a [Si-O-Me-O]n (where Me is a metal) backbone. Especially metal containing monomers with metals such as titanium, tantalum, aluminum, zirconium, hafnium or selenium can help increase the refractive index. Such metal-containing monomers may be used instead of, or in addition to, the first, second or third compounds as mentioned above.
另外,有可能基於粒子之選擇增加折射率(替代地或除將金屬併入至如上所述之矽氧烷聚合物中之外)。特定氧化物粒子,尤其諸如鈦、鉭、鋁、鋯、鉿或硒之氧化物可幫助增加折射率。另外,可選擇改良將粒子併入至矽氧烷聚合物中之偶合劑以幫助增加折射率。作為一個實例,可提及具有以下化學式之偶合劑:R16Ar)iSiR1 j In addition, it is possible to increase the index of refraction based on particle selection (alternatively or in addition to incorporation of metals into silicone polymers as described above). Certain oxide particles, especially oxides such as titanium, tantalum, aluminum, zirconium, hafnium or selenium, can help increase the refractive index. Additionally, coupling agents that incorporate particles into the silicone polymer can be optionally modified to help increase the refractive index. As an example, mention may be made of a coupler of the formula: R 16 Ar) i SiR 1 j
其中i=1或2,且j=4-i,R16為當施加熱或UV光時與矽氧烷聚合物經歷交聯之官能性交聯基團,Ar為芳基,且其中R1為反應性基團,諸如羥基、鹵素、烷氧基、羧基、胺或醯氧基。 where i=1 or 2, and j=4-i, R 16 is a functional crosslinking group that undergoes crosslinking with the silicone polymer when heat or UV light is applied, Ar is an aryl group, and wherein R 1 is Reactive groups such as hydroxyl, halo, alkoxy, carboxyl, amine or acyloxy.
因此,化合物包括結合至一個或兩個芳基(所述芳基具有交聯取代基)之矽原子且矽原子亦結合至兩個或三個反應性基團,較佳烷氧基。芳基可為苯基、萘、菲、蒽等。R16官能性交聯基團可為環氧基、丙烯酸酯、乙烯基、烯丙基、乙炔、醇、胺、硫醇、矽烷醇等。亦可選擇偶合劑以具有金屬原子,諸如鈦、鉭、鋁、鋯、鉿或硒等來替代矽。 Thus, the compound comprises a silicon atom bonded to one or two aryl groups with crosslinking substituents and the silicon atom is also bonded to two or three reactive groups, preferably alkoxy groups. The aryl group can be phenyl, naphthalene, phenanthrene, anthracene and the like. The R 16 functional crosslinking group can be epoxy, acrylate, vinyl, allyl, acetylene, alcohol, amine, thiol, silanol, and the like. The coupling agent can also be selected to have metal atoms such as titanium, tantalum, aluminum, zirconium, hafnium, or selenium instead of silicon.
如圖6中可見,相對於光之波長標繪如本文中所揭示之固化矽氧烷粒子材料之折射率,且每一圖具有不同量的作為矽氧烷材料之一部分之粒子,其中自無粒子添加至組成物至75%粒子負載。如圖6中可見,在無粒子之情況下可達成可見光譜內1.60或更大之折射率,且在此實例中在具有粒子之情況下可達成可見 光譜內1.70或更大之折射率。如圖7中可見,相對於光之波長標繪矽氧烷材料之透射率%。如此圖中所說明,標繪自無粒子至75%之不同粒子負載,且在可見光譜內具有大於90%(實際上大於95%)之可見光之透射率%。因此,即便負載有高%粒子之矽氧烷材料亦為極透明的且適用於多種光學應用,諸如LED燈。 As can be seen in Figure 6, the refractive index of the cured silicone particle material as disclosed herein is plotted against the wavelength of light, and each plot has a different amount of particles that are part of the silicone material, with none Particles were added to the composition to 75% particle loading. As can be seen in Figure 6, a refractive index of 1.60 or greater in the visible spectrum can be achieved without particles, and in this example with particles. A refractive index of 1.70 or greater within the spectrum. As can be seen in Figure 7, the % transmission of the silicone material is plotted against the wavelength of light. As illustrated in this figure, different particle loadings from no particles to 75% are plotted, with a % transmittance of visible light greater than 90% (actually greater than 95%) within the visible spectrum. Therefore, even siloxane materials loaded with high % particles are extremely transparent and suitable for various optical applications, such as LED lights.
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1000兆帕-秒至75000兆帕-秒之黏度。 Given the disclosed methods and materials, stable compositions were formed. Part of the composition may be a siloxane polymer with a [-Si-O-Si-O]n repeating main chain, with alkyl or aryl groups on the main chain, and functional crosslinks on the main chain groups, and another part is particles mixed with siloxane material, wherein the average particle size of the particles is less than 100 microns, and the particles are any suitable particles, such as metal, semi-metal, semiconductor or ceramic particles. Compositions shipped to customers may have a molecular weight of 300 g/mole to 10,000 g/mole and a viscosity of 1000 MPa-s to 75000 MPa-s at a 5 rpm viscometer.
黏滯(或液體)矽氧烷聚合物實質上不含-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、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。在不施加較佳大於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 shipping at ambient temperature if necessary. Preferably, the siloxane material has no -OH peaks detectable from FTIR analysis. Increased stability of the formed silicone material to allow storage prior to use with minimal increase in viscosity (crosslinking) during storage, such as less than 25% over a period of 2 weeks at room temperature, preferably over 2 weeks The period is 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 solvent), avoiding solvent entrapment in layers subsequently formed in the final product , Shrinkage during polymerization, quality loss over time during device use, etc. No substantial crosslinking occurs during shipping and storage without the application of heat or UV light, preferably greater than 100°C.
當組成物經沈積及聚合(例如藉由施加熱或UV光)時,觀測到質量之極小收縮或減少。圖8中,x軸為時間(以分鐘為單位),左y軸為就起始質量之%而言之層之質量,且右y軸為以攝氏度為單位之溫度。如圖8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 was deposited and polymerized (for example by applying heat or UV light), little shrinkage or loss of mass was observed. In Figure 8, the x-axis is time in minutes, the left y-axis is the mass of the layer in terms of % of starting mass, and the right y-axis is temperature in degrees Celsius. As can be seen in Figure 8, the silicone particle mixture as disclosed herein was rapidly heated to 150°C and then held at 150°C for approximately 30 minutes. In this example, the silicone particles have a Si—O backbone with phenyl and epoxy groups, and the particles are silver particles. After thermal curing over this period, the mass loss was less than 1%. Desirably, mass loss is typically less than 4%, and generally less than 2%. In many cases, however, the difference in mass of the silicone particle composition between before and after curing is less than 1%. Curing temperatures are generally below 175°C, although higher curing temperatures are possible. Typically, the curing temperature will be 160°C or less, more typically 150°C or less. However, lower curing temperatures are possible, such as 125°C or lower.
如圖9中可見,無論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極熱穩定的。舉例而言,在藉由熱聚合或UV聚合硬化之後以每分鐘升高10℃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9之實例中,在200℃觀測到小於0.2%之質量損失)。在300℃下,在圖9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9中可見,甚至在 大於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 Figure 9, no matter 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 Polymerized and optionally hardened, the silicone particle layer or mass is extremely thermally stable. For example, after the in-situ material is heated to 600°C at a rate of 10°C per minute after hardening by thermal polymerization or UV polymerization, less than 4.0% is observed at both 200°C and 300°C, preferably Less than 2.0%, such as 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 9, less than 0.2% mass loss is 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. 9 . Similar results can be observed by heating the polymeric material at only 200°C, or 300°C for 1 hour. Less than 1% mass loss results are possible by heating the polymerized deposition material at or above 375°C for at least 1 hour. As can be seen in Figure 9, even in A mass loss of 5% or less was observed at temperatures greater than 500°C. Such thermally stable materials are desirable and in particular can be deposited at low temperatures (e.g. below 175°C, preferably below 150°C, or below 130°C for 30 minutes cure/bake time), or can be deposited by A thermally stable material as disclosed herein polymerized by UV light.
具有如本文中所揭示之矽氧烷材料之LED燈存在許多替代方案。舉例而言,在圖10a中,取決於燈之所需用途,晶粒51可結合至封裝基板50,且用覆蓋基板52覆蓋,且用其中可具有或可不具有粒子或磷光體或其他波長位移元件之矽氧烷密封劑53填充。或者,如圖10b中可見,可塗覆保形層55,其為矽氧烷材料(視需要具有或不具有添加之粒子,且視需要具有或不具有磷光體)。亦可用矽氧烷密封劑(同樣具有或不具有添加之粒子)填充保形層55與覆蓋基板52之間的區域。或者,如圖10c中可見,僅晶粒51覆蓋有具有視情況存在之粒子及磷光體之矽氧烷材料。在此實施例中,通常,矽氧烷材料在晶粒單粒化之前以晶圓級添加。或者,如圖10d中可見,可提供保形層55,諸如形成於覆蓋基板52上之層(或此可替代地為嵌入覆蓋基板52內之磷光體)。如同其他實例,矽氧烷可具有或可不具有粒子,但在來自LED之光自其穿過之此等實例中,密封劑較佳為光學透射的。在圖10a-圖10d中,晶粒在各情況下為關於前述實例提及之基板材料,且可在必要時經由如本文中所揭示之矽氧烷粒子材料附連至封裝基板。
There are many alternatives to LED lights with silicone materials as disclosed herein. For example, in Figure 10a, a
如自以上揭示內容可見,如上文揭示之矽氧烷粒子組成物可用作接著劑、保護層、波長位移層之一部分或可見光導引透鏡(以及其他實施方案)。若用作接著劑,則材料較佳不在可見光譜內 為光學吸收的,且較佳透射或反射至少75%,但較佳大於80%,或大於85%或甚至更高,諸如大於90%或95%入射於其上之可見光。作為波長位移層,磷光體、發光團、閃爍體或其他化學元件併入其中且其吸收一個波長下之光且發射第二不同波長下之光。此類波長位移元件可作為接近包括不存在任何波長位移元件之矽氧烷組成物之第二透鏡之第一矽氧烷組成物層的一部分。或者,透鏡可包括矽氧烷組成物及波長位移元件(諸如磷光體)兩者。亦有可能的是矽氧烷粒子組成物以導電材料形式存在,諸如用於覆晶晶粒附連凸塊,或用於連接基板之間的線結合。導電區域及圖案化區域亦可包括根據本發明之矽氧烷材料。 As can be seen from the above disclosure, the silicone particle composition as disclosed above can be used as an adhesive, a protective layer, part of a wavelength shifting layer, or a visible light directing lens (among other embodiments). If used as an adhesive, the material is preferably not in the visible spectrum Is optically absorptive, and preferably transmits or reflects at least 75%, but preferably greater than 80%, or greater than 85% or even higher, such as greater than 90% or 95%, of visible light incident thereon. As a wavelength shifting layer, phosphors, luminophores, scintillators or other chemical elements are incorporated and absorb light at one wavelength and emit light at a second, different wavelength. Such wavelength shifting elements may be part of a layer of the first silicone composition proximate to a second lens comprising a silicone composition in the absence of any wavelength shifting elements. Alternatively, the lens may include both a silicone composition and a wavelength shifting element such as a phosphor. It is also possible that the siloxane particle composition exists as a conductive material, such as for flip-chip die attach bumps, or for wire bonds connecting substrates. Conductive regions and patterned regions may also comprise silicone materials according to the invention.
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,在實例實施例中許多修改有可能。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但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 illustrates example embodiments and is not to be construed as limiting. Although a few example embodiments have been described, those skilled in the art will readily appreciate that many modifications are possible in the example embodiments without materially departing from the novel teachings and advantages. Accordingly, all such modifications are intended to be included within the scope of this invention as defined in the claims. Therefore, it is to be understood that the foregoing describes various example embodiments and should not be construed as limited to the particular embodiments disclosed and that modifications of the disclosed embodiments, as well as other embodiments, are intended to be included within the scope of the appended claims.
所揭示之組成物可例如用作接著劑、導熱層、密封劑、圖案化導電層、圖案化介電層、透明層、LED燈具及燈中之光反射層。本發明LED燈具有多種用途,例如作為戶外標識;用於平板顯示器之LED像素陣列;用於LCD顯示器之LED背光;用於公共活動及公共交通之室內螢幕;戶外螢幕,諸如體育或其他公共活動之大螢幕;室內及戶外廣告螢幕;消費電子產品或用於所述物品 之任何設備、裝置或機構上之LED燈;紅外LED,諸如遙控器中;交通信號及道路照明中之LED;汽車尾燈、前照燈以及內部照明;手電筒;用於室內生長農產品之溫室照明;以及一般而言,作為使用白熾燈泡或螢光照明時之替代物(以及其他實施方案)。LED將在可預見的未來主導照明領域且在節能、環境保護以及改良生活品質中起重要作用。 The disclosed compositions can be used, for example, as adhesives, thermally conductive layers, sealants, patterned conductive layers, patterned dielectric layers, transparent layers, light reflective layers in LED lamps and lamps. The LED light of the present invention has many uses, such as outdoor signage; LED pixel arrays for flat panel displays; LED backlights for LCD displays; indoor screens for public events and public transportation; outdoor screens, such as sports or other public events large screens; indoor and outdoor advertising screens; consumer electronics or for use in said articles LED lights on any equipment, device or mechanism; infrared LEDs, such as in remote controls; LEDs in traffic signals and road lighting; automobile taillights, headlights and interior lighting; flashlights; greenhouse lighting for indoor growing agricultural products; And in general, as an alternative (among other implementations) when using incandescent bulbs or fluorescent lighting. LED will dominate the lighting field in the foreseeable future and play an important role in energy saving, environmental protection, and improvement of quality of life.
專利文獻 patent documents
US 2009221783 US 2009221783
US2012123054 US2012123054
WO20100267 WO20100267
US 2011171447 US 2011171447
JP 2004225005 JP 2004225005
10a、10b:電極 10a, 10b: electrodes
12:n摻雜氮化鎵區域 12: n-doped gallium nitride region
13:p摻雜氮化鎵區域 13: p-doped gallium nitride region
14:藍寶石基板 14: Sapphire substrate
17:接著劑層 17: Adhesive layer
19:支撐基板或封裝基板 19: Support substrate or packaging substrate
Claims (14)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW104142616A TWI784922B (en) | 2015-12-18 | 2015-12-18 | Led lamp, method of making led lamp, and method for encapsulating led device |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW104142616A TWI784922B (en) | 2015-12-18 | 2015-12-18 | Led lamp, method of making led lamp, and method for encapsulating led device |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201723124A TW201723124A (en) | 2017-07-01 |
TWI784922B true TWI784922B (en) | 2022-12-01 |
Family
ID=60047163
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW104142616A TWI784922B (en) | 2015-12-18 | 2015-12-18 | Led lamp, method of making led lamp, and method for encapsulating led device |
Country Status (1)
Country | Link |
---|---|
TW (1) | TWI784922B (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200502372A (en) * | 2003-02-25 | 2005-01-16 | Kaneka Corp | Curing composition and method for preparing same, light-shielding paste, light-shielding resin and method for producing same, package for light-emitting diode, and semiconductor device |
TW200706592A (en) * | 2005-03-22 | 2007-02-16 | Shinetsu Chemical Co | Epoxy-silicone hybrid resin composition and method for producing the same composition and light-emitting semiconductor device |
TW200745216A (en) * | 2006-04-26 | 2007-12-16 | Sekisui Chemical Co Ltd | Thermosetting composition for optical semiconductor, die bond material for optical semiconductor device, underfill material for optical semiconductor device, sealing agent for optical semiconductor device, and optical semiconductor device |
CN101432331A (en) * | 2006-04-26 | 2009-05-13 | 积水化学工业株式会社 | Thermosetting composition for optical semiconductor, die bond material for optical semiconductor device, underfill material for optical semiconductor device, sealing agent for optical semiconductor de |
-
2015
- 2015-12-18 TW TW104142616A patent/TWI784922B/en active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200502372A (en) * | 2003-02-25 | 2005-01-16 | Kaneka Corp | Curing composition and method for preparing same, light-shielding paste, light-shielding resin and method for producing same, package for light-emitting diode, and semiconductor device |
TW200706592A (en) * | 2005-03-22 | 2007-02-16 | Shinetsu Chemical Co | Epoxy-silicone hybrid resin composition and method for producing the same composition and light-emitting semiconductor device |
TW200745216A (en) * | 2006-04-26 | 2007-12-16 | Sekisui Chemical Co Ltd | Thermosetting composition for optical semiconductor, die bond material for optical semiconductor device, underfill material for optical semiconductor device, sealing agent for optical semiconductor device, and optical semiconductor device |
CN101432331A (en) * | 2006-04-26 | 2009-05-13 | 积水化学工业株式会社 | Thermosetting composition for optical semiconductor, die bond material for optical semiconductor device, underfill material for optical semiconductor device, sealing agent for optical semiconductor de |
Also Published As
Publication number | Publication date |
---|---|
TW201723124A (en) | 2017-07-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11084928B2 (en) | Transparent siloxane encapsulant and adhesive | |
US10658554B2 (en) | LED lamp with siloxane particle material | |
JP6885866B2 (en) | Composition with siloxane polymer and particles | |
US11001674B2 (en) | Method of making a siloxane polymer composition | |
US11289666B2 (en) | Electrically conductive siloxane particle films, and devices with the same | |
JP2017518435A5 (en) | ||
TWI784922B (en) | Led lamp, method of making led lamp, and method for encapsulating led device | |
TWI694112B (en) | Composition having siloxane polymer and process for producing siloxane particulate composition | |
TWI785389B (en) | Siloxane polymer composition and manufacturing method thereof | |
TW202111062A (en) | Led lamp, method of making led lamp, and method for encapsulating led device | |
TW201723133A (en) | Composition, siloxane polymer film and method for making siloxane particle film | |
TWI746428B (en) | Siloxane polymer composition and manufacturing method thereof |