TWI722520B - Curable organopolysiloxane composition and reflective materials for optical semiconductor, comprising the same - Google Patents

Curable organopolysiloxane composition and reflective materials for optical semiconductor, comprising the same Download PDF

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TWI722520B
TWI722520B TW108127363A TW108127363A TWI722520B TW I722520 B TWI722520 B TW I722520B TW 108127363 A TW108127363 A TW 108127363A TW 108127363 A TW108127363 A TW 108127363A TW I722520 B TWI722520 B TW I722520B
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organopolysiloxane
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崔太勳
姜承鉉
安廷謨
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南韓商Ｋｃｃ公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/1336—Illuminating devices
    • G02F1/133602—Direct backlight
    • G02F1/133605—Direct backlight including specially adapted reflectors

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Abstract

The present invention relates to a curable organopolysiloxane composition and a reflective material for an optical semiconductor, including the same. The curable organopolysiloxane composition according to the present invention includes a mixed organopolysiloxane, a pigment and silsesquioxane as a filler, and includes 20 to 50 parts by weight of a pigment; and 5 to 15 parts by weight of silsesquioxane based on 100 parts by weight of the mixed organopolysiloxane, wherein an amount of total aryl groups is 15 mol% or less of total organic groups. With this, a liquid phase with a low viscosity is achieved at room temperature, moldability and minute quantitative discharge properties are excellent, and heat resistance is increased, thereby improving the degradation problems of reflectance due to cracks and discoloration at high temperature conditions.

Description

可固化有機聚矽氧烷組合物及包括其之用於光 學半導體的反射材料 Curable organopolysiloxane composition and its use for light Learn semiconductor reflective materials

本發明是有關於一種可固化有機聚矽氧烷組合物及包括其之用於光學半導體的反射材料。 The present invention relates to a curable organopolysiloxane composition and a reflective material for optical semiconductor including it.

一般而言，表面安裝技術(surface mount technology,SMT)型光學半導體(發光二極體(LED))封裝(PKG)是以透過導線(wire)將晶片頂部上的電極和封裝底部上的電極結合的方式構成。為了保護封裝，使用具有高反射率的材料製造殼體和框架，以扮演反射板的角色。作為表面安裝技術型光半導體封裝的材料，使用聚鄰苯二甲醯胺樹脂(polyphthalamide resin,PPA resin)、縮合型樹脂等，但這些材料存在變色(discoloration)、切割時產生毛邊(burr)、在高溫時具有孔隙及裂縫等問題。 Generally speaking, the surface mount technology (SMT) optical semiconductor (light emitting diode (LED)) package (PKG) combines the electrodes on the top of the chip with the electrodes on the bottom of the package through wires. Way of composition. In order to protect the package, the case and frame are made of materials with high reflectivity to play the role of the reflector. As the material of surface mount technology type optical semiconductor package, polyphthalamide resin (PPA resin), condensation type resin, etc. are used, but these materials have discoloration, burr during cutting, and There are problems such as pores and cracks at high temperatures.

同時，根據近來對光學半導體封裝的小型化和薄化的要求，具有僅在晶片的底部上提供電極的結構的覆晶被商業化，因此，從中省略框架或其中晶片之間的間隔窄且可獲得高密度的對於晶片尺 寸封裝(CPS)的要求正在增加。另外，封裝的製造方法改變為藉由分配或模製方法使用具有高反射率的矽氧樹脂(silicone)固化晶片之間的間隔，然後切割每個單元晶片的方式。因此，已經開發了用於晶片尺寸封裝製程的各種類型的液相矽氧樹脂，但是使用液相矽氧樹脂形成的固化產物的硬度不夠穩定且可使用時間(pot life)短，並且成型性不足的缺陷及在高溫條件下包含在矽組合物中的苯基的變色以及反射率的降低的缺陷仍然存在。 Meanwhile, in accordance with recent demands for miniaturization and thinning of optical semiconductor packages, flip-chips having a structure in which electrodes are provided only on the bottom of the wafer are commercialized, and therefore, the frame is omitted from it or in which the interval between the wafers is narrow and can be High-density wafer scale The requirements for small package (CPS) are increasing. In addition, the manufacturing method of the package is changed to a method of curing the space between the chips by using a silicone resin with high reflectivity by a dispensing or molding method, and then cutting each unit chip. Therefore, various types of liquid-phase silicone resins have been developed for use in wafer-scale packaging processes, but the cured products formed using liquid-phase silicone resins are not stable enough in hardness and have a short pot life and insufficient moldability. The defects and the defects of the discoloration of the phenyl group contained in the silicon composition and the decrease of the reflectivity under high temperature conditions still exist.

因此，對於適用於微小模塑加工，並且在薄膜狀態下的可見光區域具有高反射率和優異的耐熱性的材料的要求正在增加。 Therefore, there is an increasing demand for materials that are suitable for micro-molding processing and have high reflectivity and excellent heat resistance in the visible light region in a thin film state.

本發明的一方面提供一種可固化有機聚矽氧烷，其在室溫下以液相存在並且可用於模塑薄膜的反射材料，並且在薄膜中具有高反射率且固化產物中具有高硬度，因此，切割過程中毛邊的產生很少，並且耐熱性極好。 An aspect of the present invention provides a curable organopolysiloxane that exists in a liquid phase at room temperature and can be used as a reflective material for molding a film, and has high reflectivity in the film and high hardness in the cured product, Therefore, there is little burr during the cutting process, and the heat resistance is excellent.

為了解決這些任務，本發明的一方面提供一種可固化有機聚矽氧烷組合物，其包含混合的有機聚矽氧烷、顏料和作為填料的半矽氧烷(silsesquioxane)，並且基於100重量份的混合有機聚矽氧烷，包含20至50重量份的顏料及5至15重量份的半矽氧烷，其中總芳香基的量為總有機基團的15莫耳百分比(mole%)或更少。 In order to solve these tasks, one aspect of the present invention provides a curable organopolysiloxane composition comprising a mixed organopolysiloxane, a pigment, and silsesquioxane as a filler, and based on 100 parts by weight The mixed organopolysiloxane contains 20 to 50 parts by weight of pigment and 5 to 15 parts by weight of semisiloxane, wherein the amount of total aromatic groups is 15 mole% or more of the total organic groups less.

另外，本發明的另一方面是解決上述任務，以提供一種用於光學半導體的反射材料，包括使用可固化有機聚矽氧烷組合物所形成的固化產物。 In addition, another aspect of the present invention is to solve the above-mentioned tasks to provide a reflective material for optical semiconductors, including a cured product formed by using a curable organopolysiloxane composition.

有益效果 Beneficial effect

本發明的可固化有機聚矽氧烷組合物在室溫下實現具有低黏度的液相，並且可模塑性和微小的定量排出性能(minute quantitative discharge properties)是優異的。 The curable organopolysiloxane composition of the present invention realizes a liquid phase with low viscosity at room temperature, and has excellent moldability and minute quantitative discharge properties.

此外，使用本發明的可固化有機聚矽氧烷組合物形成的固化產物，儘管在組合物中不包含過量的芳香基，但可顯示出足夠的硬度和模量(modulus)。另外，耐熱性優異，並且可以改善由於高溫條件下的裂縫和變色導致的反射率降低的缺陷。 In addition, the cured product formed using the curable organopolysiloxane composition of the present invention may exhibit sufficient hardness and modulus although it does not contain excessive aromatic groups in the composition. In addition, it is excellent in heat resistance, and it is possible to improve the defect of decrease in reflectance due to cracks and discoloration under high temperature conditions.

在下文中，將詳細解釋本發明。 Hereinafter, the present invention will be explained in detail.

1.可固化有機聚矽氧烷組合物(Curable organopolysiloxane composition) 1. Curable organopolysiloxane composition

根據本發明的一個方面，提供了一種可固化有機聚矽氧烷組合物。 According to one aspect of the present invention, a curable organopolysiloxane composition is provided.

本發明的可固化有機聚矽氧烷組合物包括混合的有機聚矽氧烷、顏料和半矽氧烷(silsesquioxane)，更具體地，基於100重量份的混合有機聚矽氧烷，可固化有機聚矽氧烷組合物包含20至50重量份的顏料及5至15重量份的半矽氧烷。 The curable organopolysiloxane composition of the present invention includes a mixed organopolysiloxane, a pigment, and a silsesquioxane, more specifically, based on 100 parts by weight of the mixed organopolysiloxane, the curable organic The polysiloxane composition includes 20 to 50 parts by weight of pigment and 5 to 15 parts by weight of semisiloxane.

混合的有機聚矽氧烷 Mixed organopolysiloxane

在本發明中，混合的有機聚矽氧烷包括第一有機聚矽氧烷、第二有機聚矽氧烷和第三有機聚矽氧烷。 In the present invention, the mixed organopolysiloxane includes a first organopolysiloxane, a second organopolysiloxane, and a third organopolysiloxane.

特別地，第一有機聚矽氧烷在一分子中包含至少一個烯基(優選兩個或更多個烯基)，和至少一個或多個二氧化矽單元(SiO2 unit)，並且可以包括例如由下式1表示的一個：[式l](R1 3SiO1/2)a(R2 3SiO1/2)b(SiO2)c In particular, the first organopolysiloxane contains at least one alkenyl group (preferably two or more alkenyl groups), and at least one or more silicon dioxide units (SiO 2 unit) in one molecule, and may include For example, one represented by the following formula 1: [Formula 1] (R 1 3 SiO 1/2 ) a (R 2 3 SiO 1/2 ) b (SiO 2 ) c

在式1中，R1和R2各自獨立地為C1至C6的烷基(alkyl group)，或C2至C6的烯基(alkenyl group)，其中R1中的至少一個為C2至C6的烯基。R1和R2中的每一個的烷基或烯基可以是直鏈或支鏈，鏈型或環型。 In Formula 1, R 1 and R 2 are each independently a C 1 to C 6 alkyl group, or a C 2 to C 6 alkenyl group, wherein at least one of R 1 is C 2 to C 6 alkenyl. The alkyl or alkenyl group of each of R 1 and R 2 may be linear or branched, chain type or cyclic type.

「C1至C6的烷基」可以選自由甲基、乙基、丙基、丁基、戊基、己基、環戊基和環己基所組成之群組，特別地，R1和R2可以各自獨立地為鏈型烷基(例如是甲基、乙基和丙基，特別是甲基)。 The "C 1 to C 6 alkyl group" can be selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl and cyclohexyl. In particular, R 1 and R 2 Each may independently be a chain alkyl group (e.g., methyl, ethyl, and propyl, especially methyl).

「C2至C6的烯基」可選自由乙烯基(vinyl)、丁烯基(butenyl)、戊烯基(pentenyl)及己烯基(hexenyl)所組成的群組，特別是乙烯基。 The "C 2 to C 6 alkenyl group" can be selected from the group consisting of vinyl, butenyl, pentenyl and hexenyl, especially vinyl.

在式1中，相對於所有的矽(Si)而言，二氧化矽單元的含量優選為40重量百分比(wt%)或更多，例如50wt%至80wt%。儘管在分子結構中不加入芳香基，如果二氧化矽單元的含量為40wt%或更多，則可以在室溫下形成具有高硬度的固化產物，並且在高溫下長時間使用之後由於變色所引起的反射率降低可能變得微不足道，並且可以確保優異的耐熱性。另外，可以形成具有高硬度的固化產物， 並且即使不使用過量的無機填料，也可以提供在室溫下為液相的可固化有機聚矽氧烷組合物，因此，可工作性(workability)之優異效果可以實現。如果二氧化矽單元的量小於40wt%，則可固化有機聚矽氧烷的黏度降低並且可工作性可能劣化。 In Formula 1, relative to all silicon (Si), the content of the silicon dioxide unit is preferably 40% by weight (wt%) or more, for example, 50wt% to 80wt%. Although no aromatic group is added to the molecular structure, if the content of the silicon dioxide unit is 40wt% or more, a cured product with high hardness can be formed at room temperature and caused by discoloration after long-term use at high temperatures The decrease in reflectance may become insignificant, and excellent heat resistance can be ensured. In addition, a cured product with high hardness can be formed, Moreover, even if an excessive amount of inorganic filler is not used, a curable organopolysiloxane composition that is a liquid phase at room temperature can be provided, and therefore, the excellent effect of workability can be achieved. If the amount of the silicon dioxide unit is less than 40 wt%, the viscosity of the curable organopolysiloxane decreases and workability may be deteriorated.

詳細地，在式1中，滿足a+b+c=1，並且「a」可以是0.05至0.25的數，例如，0.1至0.2。如果「a」小於0.05，則第一有機聚矽氧烷的交聯密度可能降低，並且可固化有機聚矽氧烷組合物的固化反應性可能劣化，並且如果「a」大於0.25，則交聯密度高且如此形成的固化產物的硬度高，並且由於隨時間的變化可能產生裂縫。「b」可以是0.1至0.5的數，例如，0.25至0.45。如果「b」小於0.1，則可固化有機聚矽氧烷組合物的黏度可能增加，流動性可能降低，並且可能降低可模塑性(例如分配工作(dispensing work))。「c」可以是0.4至0.6的數，例如，0.45至0.55。如果「c」小於0.4，則固化產物的足夠硬度的確保可能是困難的，並且如果「c」大於0.6，則可固化有機聚矽氧烷組合物的黏度可能增加，流動性可能降低，並且可模塑性(例如是分配工作)可能會降低。 In detail, in Formula 1, a+b+c=1 is satisfied, and "a" may be a number from 0.05 to 0.25, for example, from 0.1 to 0.2. If "a" is less than 0.05, the crosslinking density of the first organopolysiloxane may decrease, and the curing reactivity of the curable organopolysiloxane composition may deteriorate, and if "a" is greater than 0.25, crosslinking The density is high and the hardness of the cured product thus formed is high, and cracks may occur due to changes over time. "B" can be a number from 0.1 to 0.5, for example, from 0.25 to 0.45. If "b" is less than 0.1, the viscosity of the curable organopolysiloxane composition may increase, fluidity may decrease, and moldability (such as dispensing work) may decrease. "C" can be a number from 0.4 to 0.6, for example, from 0.45 to 0.55. If "c" is less than 0.4, it may be difficult to ensure sufficient hardness of the cured product, and if "c" is greater than 0.6, the viscosity of the curable organopolysiloxane composition may increase, the fluidity may decrease, and the Moldability (e.g. distribution work) may be reduced.

例如，第一有機聚矽氧烷可以是矽酸鹽樹脂(silicate resin)，其兩個末端分別是乙烯基二甲基矽烷氧基(vinyldimethylsiloxy group)和三甲基矽烷氧基(trimethylsiloxy group)，或者兩個末端分別是二乙烯基甲基矽烷氧基(divinylmethylsiloxy group)和三甲基矽烷氧基(trimethylsiloxy group)的矽酸鹽樹脂。兩末端分別為乙烯基二甲基矽烷氧基和三甲基矽烷氧基的矽酸鹽樹脂可以是 (ViMe2SiO1/2)0.15(Me3SiO1/2)0.35(SiO2)0.5、(ViMe2SiO1/2)0.10(Me3SiO1/2)0.40(SiO2)0.5、(ViMe2SiO1/2)0.2(Me3SiO1/2)0.3(SiO2)0.5、(ViMe2SiO1/2)0.15(Me3SiO1/2)0.45(SiO2)0.4、(ViMe2SiO1/2)0.10(Me3SiO1/2)0.50(SiO2)0.4、(ViMe2SiO1/2)0.2(Me3SiO1/2)0.4(SiO2)0.4、(ViMe2SiO1/2)0.125(Me3SiO1/2)0.375(SiO2)0.5或者(ViMe2SiO1/2)0.2(Me3SiO1/2)0.2(SiO2)0.6，且末端分別為二乙烯基甲基矽烷氧基和三甲基矽烷氧基的矽酸鹽樹脂可以是(Vi2MeSiO1/2)0.15(Me3SiO1/2)0.35(SiO2)0.5、(Vi2MeSiO1/2)0.10(Me3SiO1/2)0.40(SiO2)0.5、(Vi2MeSiO1/2)0.2(Me3SiO1/2)0.3(SiO2)0.5、(Vi2MeSiO1/2)0.15(Me3SiO1/2)0.45(SiO2)0.4、(Vi2MeSiO1/2)0.1(Me3SiO1/2)0.5(SiO2)0.4、(Vi2MeSiO1/2)0.2(Me3SiO1/2)0.4(SiO2)0.4或者(Vi2MeSiO1/2)0.2(Me3SiO1/2)0.2(SiO2)0.6。 For example, the first organopolysiloxane may be a silicate resin, the two ends of which are vinyldimethylsiloxy group and trimethylsiloxy group, respectively, Or a silicate resin whose two ends are divinylmethylsiloxy group and trimethylsiloxy group respectively. The silicate resin whose two ends are vinyl dimethylsilyloxy and trimethylsilyloxy can be (ViMe 2 SiO 1/2 ) 0.15 (Me 3 SiO 1/2 ) 0.35 (SiO 2 ) 0.5 , (ViMe 2 SiO 1/2 ) 0.10 (Me 3 SiO 1/2 ) 0.40 (SiO 2 ) 0.5 , (ViMe 2 SiO 1/2 ) 0.2 (Me 3 SiO 1/2 ) 0.3 (SiO 2 ) 0.5 , (ViMe 2 SiO 1/2 ) 0.15 (Me 3 SiO 1/2 ) 0.45 (SiO 2 ) 0.4 , (ViMe 2 SiO 1/2 ) 0.10 (Me 3 SiO 1/2 ) 0.50 (SiO 2 ) 0.4 , (ViMe 2 SiO 1/2 ) 0.2 (Me 3 SiO 1/2 ) 0.4 (SiO 2 ) 0.4 , (ViMe 2 SiO 1/2 ) 0.125 (Me 3 SiO 1/2 ) 0.375 (SiO 2 ) 0.5 or (ViMe 2 SiO 1/ 2 ) 0.2 (Me 3 SiO 1/2 ) 0.2 (SiO 2 ) 0.6 , and the silicate resin whose ends are divinylmethylsiloxy and trimethylsiloxy groups can be (Vi 2 MeSiO 1/ 2 ) 0.15 (Me 3 SiO 1/2 ) 0.35 (SiO 2 ) 0.5 , (Vi 2 MeSiO 1/2 ) 0.10 (Me 3 SiO 1/2 ) 0.40 (SiO 2 ) 0.5 , (Vi 2 MeSiO 1/2 ) 0.2 (Me 3 SiO 1/2 ) 0.3 (SiO 2 ) 0.5 , (Vi 2 MeSiO 1/2 ) 0.15 (Me 3 SiO 1/2 ) 0.45 (SiO 2 ) 0.4 , (Vi 2 MeSiO 1/2 ) 0.1 ( Me 3 SiO 1/2 ) 0.5 (SiO 2 ) 0.4 , (Vi 2 MeSiO 1/2 ) 0.2 (Me 3 SiO 1/2 ) 0.4 (SiO 2 ) 0.4 or (Vi 2 MeSiO 1/2 ) 0.2 (Me 3 SiO 1/2 ) 0.2 (SiO 2 ) 0.6 .

第二有機聚矽氧烷是線性有機聚矽氧烷組分，用於控制可固化有機聚矽氧烷組合物的黏度以賦予流動性和控制模量，在分子中包括至少一個烯基，優選兩個或更多個烯基，並且可以包括由下面的式2所示之一：[式2](R3 3SiO1/2)2(R3R4SiO)d(R4 2SiO)e The second organopolysiloxane is a linear organopolysiloxane component, used to control the viscosity of the curable organopolysiloxane composition to impart fluidity and control modulus, and include at least one alkenyl group in the molecule, preferably Two or more alkenyl groups, and may include one represented by the following formula 2: [Formula 2] (R 3 3 SiO 1/2 ) 2 (R 3 R 4 SiO) d (R 4 2 SiO) e

在式2中，R3各自獨立地為C1至C6的烷基，C2至C6的烯基，或C6至C12的芳基，R4各自獨立地為C1至C6的烷基，或者C6至C12的芳香基，其中R3中的至少一個或多個是C2至C6的烯基。 In Formula 2, R 3 is each independently a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, or a C 6 to C 12 aryl group, and R 4 is each independently a C 1 to C 6 Or a C 6 to C 12 aromatic group, wherein at least one or more of R 3 is a C 2 to C 6 alkenyl group.

烷基和烯基與以上定義的相同，並且R3可以優選為甲基作為C1至C6的烷基，並且可以優選為乙烯基作為C2至C6的烯基。「C6至C12的芳香基」可以是苯基(phenyl)、甲苯基(tolyl)、二甲苯基(xylyl)、萘基(naphthyl)、二亞苯基(bisphenylene)等，特別是苯基(phenyl)。 The alkyl group and the alkenyl group are the same as defined above, and R 3 may preferably be a methyl group as a C 1 to C 6 alkyl group, and may preferably be a vinyl group as a C 2 to C 6 alkenyl group. "C 6 to C 12 aromatic group" can be phenyl, tolyl, xylyl, naphthyl, bisphenylene, etc., especially phenyl (phenyl).

在式2中，「d」和「e」各自獨立地為0或1或更大的整數，其中滿足10

Figure 108127363-A0305-02-0009-4
d+e
Figure 108127363-A0305-02-0009-5
10,000且0
Figure 108127363-A0305-02-0009-6
d/(d+e)
Figure 108127363-A0305-02-0009-19
0.1。如果d+e小於10，則可固化有機聚矽氧烷組合物可能在固化期間揮發並且反射材料的厚度可能減小，因此可能出現顏色坐標變化。如果d+e大於10,000，則可固化有機聚矽氧烷組合物的流動性可能降低，顏料在組合物中的分散可能降低並且顏料的混合量可能降低，結果，在薄膜可能會出現反射率降低的缺陷。如果d/(d+e)大於0.1，則第二有機聚矽氧烷的反應性可能劣化，可固化有機聚矽氧烷組合物的密度可能增加，並且由於隨著時間之固化產品的控制性(harness)的變化可能產生裂縫。 In formula 2, "d" and "e" are each independently an integer of 0 or 1 or greater, where 10
Figure 108127363-A0305-02-0009-4
d+e
Figure 108127363-A0305-02-0009-5
10,000 and 0
Figure 108127363-A0305-02-0009-6
d/(d+e)
Figure 108127363-A0305-02-0009-19
0.1. If d+e is less than 10, the curable organopolysiloxane composition may volatilize during curing and the thickness of the reflective material may be reduced, and thus color coordinate changes may occur. If d+e is greater than 10,000, the fluidity of the curable organopolysiloxane composition may decrease, the dispersion of the pigment in the composition may decrease, and the mixing amount of the pigment may decrease. As a result, the reflectance of the film may decrease. Defects. If d/(d+e) is greater than 0.1, the reactivity of the second organopolysiloxane may deteriorate, the density of the curable organopolysiloxane composition may increase, and due to the controllability of the cured product over time (Harness) changes may cause cracks.

例如，第二有機聚矽氧烷可包括乙烯基二甲基矽烷氧基末端的二甲基矽氧烷聚合物(vinyldimethylsiloxy group-terminated dimethylsiloxane polymer)、乙烯基二甲基矽烷氧基末端的甲基乙烯基矽氧烷-二甲基矽氧烷嵌段聚合物(vinyldimethylsiloxy group-terminated methylvinylsiloxane-dimethylsiloxane block polymer)、三甲基矽烷氧基末端的甲基乙烯基矽氧烷-二甲基矽氧烷 嵌段聚合物(trimethylsiloxy group-terminated methylvinylsiloxane-dimethylsiloxane block polymer)、乙烯基二甲基矽烷氧基末端的甲基苯基矽氧烷-二甲基矽氧烷嵌段聚合物(vinyldimethylsiloxy group-terminated methylphenylsiloxane-dimethylsiloxane block polymer、乙烯基二甲基矽烷氧基末端的二苯基矽氧烷-二甲基矽氧烷嵌段聚合物(vinyldimethylsiloxy group-terminated diphenylsiloxane-dimethylsiloxane block polymer)等。 For example, the second organopolysiloxane may include vinyldimethylsiloxy group-terminated dimethylsiloxane polymer, vinyldimethylsiloxy group-terminated dimethylsiloxane polymer, and vinyldimethylsiloxy group-terminated dimethylsiloxane polymer. Vinyldimethylsiloxy group-terminated methylvinylsiloxane-dimethylsiloxane block polymer, trimethylsiloxy group-terminated methylvinylsiloxane-dimethylsiloxane block polymer Block polymer (trimethylsiloxy group-terminated methylvinylsiloxane-dimethylsiloxane block polymer), vinyldimethylsiloxy group-terminated methylphenylsiloxane -dimethylsiloxane block polymer, vinyldimethylsiloxy group-terminated diphenylsiloxane-dimethylsiloxane block polymer, etc.

乙烯基二甲基矽烷氧基末端的二甲基矽氧烷聚合物可以是(ViMe2SiO1/2)(Me2SiO)n1(ViMe2SiO1/2)。特別是，可包括(ViMe2SiO1/2)(Me2SiO)60(ViMe2SiO1/2)、(ViMe2SiO1/2)(Me2SiO)120(ViMe2SiO1/2)、(ViMe2SiO1/2)(Me2SiO)150(ViMe2SiO1/2)、(ViMe2SiO1/2)(Me2SiO)225(ViMe2SiO1/2)、(ViMe2SiO1/2)(Me2SiO)500(ViMe2SiO1/2)、(ViMe2SiO1/2)(Me2SiO)1000(ViMe2SiO1/2)或(ViMe2SiO1/2)(Me2SiO)1250(ViMe2SiO1/2)。 The dimethylsiloxane polymer at the end of the vinyl dimethylsilyloxy group may be (ViMe 2 SiO 1/2 )(Me 2 SiO) n1 (ViMe 2 SiO 1/2 ). In particular, it may include (ViMe 2 SiO 1/2 )(Me 2 SiO) 60 (ViMe 2 SiO 1/2 ), (ViMe 2 SiO 1/2 )(Me 2 SiO) 120 (ViMe 2 SiO 1/2 ) , (ViMe 2 SiO 1/2 )(Me 2 SiO) 150 (ViMe 2 SiO 1/2 ), (ViMe 2 SiO 1/2 )(Me 2 SiO) 225 (ViMe 2 SiO 1/2 ), (ViMe 2 SiO 1/2 )(Me 2 SiO) 500 (ViMe 2 SiO 1/2 ), (ViMe 2 SiO 1/2 )(Me 2 SiO) 1000 (ViMe 2 SiO 1/2 ) or (ViMe 2 SiO 1/2) ) (Me 2 SiO) 1250 (ViMe 2 SiO 1/2 ).

乙烯基二甲基矽烷氧基末端的甲基乙烯基矽氧烷-二甲基矽氧烷嵌段聚合物可以是(ViMe2SiO1/2)(ViMeSiO)n2(Me2SiO)n3(ViMe2SiO1/2)。特別是，可包括(ViMe2SiO1/2)(ViMeSiO)1(Me2SiO)59(ViMe2SiO1/2)、(ViMe2SiO1/2)(ViMeSiO)10(Me2SiO)95(ViMe2SiO1/2)、 (ViMe2SiO1/2)(ViMeSiO)30(Me2SiO)400(ViMe2SiO1/2)或(ViMe2SiO1/2)(ViMeSiO)50(Me2SiO)1000(ViMe2SiO1/2)。 The methyl vinyl siloxane-dimethyl siloxane block polymer at the end of the vinyl dimethyl siloxane group can be (ViMe 2 SiO 1/2 )(ViMeSiO) n2 (Me 2 SiO) n3 (ViMe 2 SiO 1/2 ). In particular, it may include ( ViMe 2 SiO 1/2 )(ViMeSiO) 1 (Me 2 SiO) 59 (ViMe 2 SiO 1/2 ), (ViMe 2 SiO 1/2 )(ViMeSiO) 10 (Me 2 SiO) 95 (ViMe 2 SiO 1/2 ), ( ViMe 2 SiO 1/2 )(ViMeSiO) 30 (Me 2 SiO) 400 (ViMe 2 SiO 1/2 ) or (ViMe 2 SiO 1/2 )(ViMeSiO) 50 (Me 2 SiO) 1000 (ViMe 2 SiO 1/2 ).

三甲基矽烷氧基末端的甲基乙烯基矽氧烷-二甲基矽氧烷嵌段聚合物可以是(Me3SiO1/2)(ViMeSiO)n4(Me2SiO)n5(Me3SiO1/2)。特別是，可包括(Me3SiO1/2)(ViMeSiO)30(Me2SiO)400(Me3SiO1/2)、(Me3SiO1/2)(ViMeSiO)5(Me2SiO)540(Me3SiO1/2)、(Me3SiO1/2)(ViMeSiO)50(Me2SiO)1000(Me3SiO1/2)或(Me3SiO1/2)(ViMeSiO)6(Me2SiO)60(Me3SiO1/2)。 The methylvinylsiloxane-dimethylsiloxane block polymer at the end of the trimethylsilyloxy group can be (Me 3 SiO 1/2 )(ViMeSiO) n4 (Me 2 SiO) n5 (Me 3 SiO 1/2 ). In particular, it may include (Me 3 SiO 1/2 )(ViMeSiO) 30 (Me 2 SiO) 400 (Me 3 SiO 1/2 ), (Me 3 SiO 1/2 )(ViMeSiO) 5 (Me 2 SiO) 540 (Me 3 SiO 1/2 ), (Me 3 SiO 1/2 )(ViMeSiO) 50 (Me 2 SiO) 1000 (Me 3 SiO 1/2 ) or (Me 3 SiO 1/2 )(ViMeSiO) 6 (Me 2 SiO) 60 (Me 3 SiO 1/2 ).

乙烯基二甲基矽烷氧基末端的二甲基矽氧烷-甲基苯基矽氧烷嵌段聚合物(vinyldimethylsiloxy group-terminated dimethyl siloxane-methylphenylsiloxane block polymer)可以是(ViMe2SiO1/2)(Me2SiO)n6(MePhSiO)n2(ViMe2SiO1/2)。特別是，可包括(ViMe2SiO1/2)(Me2SiO)20(MePhSiO)2(ViMe2SiO1/2),(ViMe2SiO1/2)(Me2SiO)40(MePhSiO)2(ViMe2SiO1/2)或(ViMe2SiO1/2)(Me2SiO)125(MePhSiO)10(ViMe2SiO1/2)。 Vinyldimethylsiloxy group-terminated dimethyl siloxane-methylphenylsiloxane block polymer (vinyldimethylsiloxy group-terminated dimethyl siloxane-methylphenylsiloxane block polymer) can be (ViMe 2 SiO 1/2 ) (Me 2 SiO) n6 (MePhSiO) n2 (ViMe 2 SiO 1/2 ). In particular, it may include (ViMe 2 SiO 1/2 )(Me 2 SiO) 20 (MePhSiO) 2 (ViMe 2 SiO 1/2 ), (ViMe 2 SiO 1/2 )(Me 2 SiO) 40 (MePhSiO) 2 (ViMe 2 SiO 1/2 ) or (ViMe 2 SiO 1/2 )(Me 2 SiO) 125 (MePhSiO) 10 (ViMe 2 SiO 1/2 ).

乙烯基二甲基矽烷氧基末端的二甲基矽氧烷-二苯基矽氧烷嵌段聚合物(vinyldimethylsiloxy group-terminated dimethylsiloxane-diphenylsiloxane block polymer)可以是(ViMe2SiO1/2)(Me2SiO)n8(Ph2SiO)n9(ViMe2SiO1/2)。特別是，可包括(ViMe2SiO1/2)(Me2SiO)40(Ph2SiO)2(ViMe2SiO1/2)或(ViMe2SiO1/2)(Me2SiO)225(Ph2SiO)10(ViMe2SiO1/2)。 Vinyldimethylsiloxy group-terminated dimethylsiloxane-diphenylsiloxane block polymer (vinyldimethylsiloxy group-terminated dimethylsiloxane-diphenylsiloxane block polymer) can be (ViMe 2 SiO 1/2 )(Me 2 SiO) n8 (Ph 2 SiO) n9 (ViMe 2 SiO 1/2 ). In particular, it may include (ViMe 2 SiO 1/2 )(Me 2 SiO) 40 (Ph 2 SiO) 2 (ViMe 2 SiO 1/2 ) or (ViMe 2 SiO 1/2 )(Me 2 SiO) 225 (Ph 2 SiO) 10 (ViMe 2 SiO 1/2 ).

較佳地，可以使用在25℃下黏度為0.1至100Pa．s(例如0.3至80Pa．s，0.5至70Pa．s)的第二有機聚矽氧烷。如果第二有機聚矽氧烷的黏度在上述範圍內，可能是優先考慮到可固化有機聚矽氧烷的性能(例如是流動性和模量等)的改善，但如果黏度小於或大於上述範圍，可能出現降低性能(例如是流動性和模量等)的缺陷。在-個實施例中，使用由安東帕有限公司(Anton Paar Co.)製造的流變儀(Rheometer)MCR系列，使用ASTM D4283-98(2015)的方法測量第二有機聚矽氧烷的黏度。 Preferably, a viscosity of 0.1 to 100 Pa at 25°C can be used. s (for example, 0.3 to 80 Pa·s, 0.5 to 70 Pa·s) of the second organopolysiloxane. If the viscosity of the second organopolysiloxane is within the above range, the improvement of the curable organopolysiloxane's properties (such as fluidity and modulus) may be given priority, but if the viscosity is less than or greater than the above range , There may be defects that reduce performance (for example, fluidity and modulus, etc.). In one embodiment, the Rheometer MCR series manufactured by Anton Paar Co. is used to measure the viscosity of the second organopolysiloxane using the method of ASTM D4283-98 (2015) .

第三有機聚矽氧烷是藉由將作為主要組分的第一有機聚矽氧烷以及作為用於控制黏度的組分的第二有機聚矽氧烷進行交聯作用形成固化產物的組分，並且包括至少一個直接鍵合於分子中的矽原子的氫基團，且可以包括由下式3所示：[式3]HfR5 gSiO(4-f-g)/2 The third organopolysiloxane is a component that forms a cured product by cross-linking the first organopolysiloxane as the main component and the second organopolysiloxane as the component for controlling the viscosity. , And includes at least one hydrogen group directly bonded to the silicon atom in the molecule, and may include the following formula 3: [Formula 3] H f R 5 g SiO (4-fg)/2

在式3中，R5各自獨立地為C1至C6的烷基，或C6至C12的芳香基，並且烷基和芳香基與以上定義的相同。特別地，R5可以優選為甲基作為烷基，並且可以優選為苯基作為芳香基，最優選為C1至C6的烷基，例如甲基。 In Formula 3, R 5 is each independently a C 1 to C 6 alkyl group, or a C 6 to C 12 aryl group, and the alkyl group and the aryl group are the same as defined above. In particular, R 5 may preferably be a methyl group as an alkyl group, and may preferably be a phenyl group as an aromatic group, and most preferably a C 1 to C 6 alkyl group, such as a methyl group.

在式3中，「f」是0.001至2的數，例如小於2的數，0.01至1的數。如果「f」大於2，則交聯密度可以增加，由於在固化過程中產生氫氣，經固化的產品表面可能形成空隙，固化的產品可能容易破裂，並且如果固化產品用作光學反射材料，則發光二極體封裝 的產量可能降低。「g」是0.7至2的數，例如，0.8至2的數，1.2至2的數。如果「g」小於0.7，則交聯密度可能增加，固化產物可能容易破裂，由於在固化過程中產生氫氣，可能在固化產物的表面形成空隙，從而降低發光二極體封裝的產量。如果「g」大於2，則反應性可能降低，分子量可能變小，容易發生揮發以減小厚度，並且可能出現色坐標(color coordinate)變化。f+g是滿足0.8

Figure 108127363-A0305-02-0013-7
f+g
Figure 108127363-A0305-02-0013-8
3的數，例如，滿足1
Figure 108127363-A0305-02-0013-9
f+g
Figure 108127363-A0305-02-0013-10
2.7的數，滿足1.8
Figure 108127363-A0305-02-0013-11
f+g
Figure 108127363-A0305-02-0013-12
2.4的數。如果f+g小於0.8，則有機聚矽氧烷組合物的流動性降低，並且可模塑性(例如是分配可工作性)可能劣化。如果f+g大於3，則反應性可能降低以延遲固化，分子量可能變小，容易發生揮發以減小厚度並產生色坐標變化。 In Formula 3, "f" is a number from 0.001 to 2, for example, a number less than 2, and a number from 0.01 to 1. If "f" is greater than 2, the crosslinking density can be increased. Because hydrogen is generated during the curing process, voids may be formed on the surface of the cured product, the cured product may be easily broken, and if the cured product is used as an optical reflective material, it will emit light The output of the diode package may be reduced. "G" is a number from 0.7 to 2, for example, a number from 0.8 to 2, and a number from 1.2 to 2. If "g" is less than 0.7, the cross-linking density may increase, and the cured product may be easily broken. Due to the generation of hydrogen gas during the curing process, voids may be formed on the surface of the cured product, thereby reducing the output of the light-emitting diode package. If "g" is greater than 2, the reactivity may decrease, the molecular weight may become smaller, volatilization is likely to occur to reduce the thickness, and color coordinate changes may occur. f+g satisfies 0.8
Figure 108127363-A0305-02-0013-7
f+g
Figure 108127363-A0305-02-0013-8
The number of 3, for example, satisfies 1
Figure 108127363-A0305-02-0013-9
f+g
Figure 108127363-A0305-02-0013-10
The number of 2.7, which satisfies 1.8
Figure 108127363-A0305-02-0013-11
f+g
Figure 108127363-A0305-02-0013-12
The number of 2.4. If f+g is less than 0.8, the fluidity of the organopolysiloxane composition is reduced, and moldability (for example, dispensing workability) may be deteriorated. If f+g is greater than 3, the reactivity may be reduced to delay curing, the molecular weight may become small, and volatilization may easily occur to reduce the thickness and produce color coordinate changes.

例如，第三有機聚矽氧烷可包括氫化二甲基矽烷氧基末端的二甲基矽氧烷聚合物(hydrogendimethylsiloxy group-terminated dimethylsiloxane polymer)、三甲基矽烷氧基末端的甲基氫矽氧烷聚合物(trimethylsiloxy group-terminated methylhydrogensiloxane polymer)、三甲基矽烷氧基末端的甲基氫矽氧烷-二甲基矽氧烷嵌段聚合物(trimethylsiloxy group-terminated methylhydrogensiloxane-dimethylsiloxane block polymer)、氫化二甲基矽烷氧基末端的二甲基矽氧烷-氫甲基矽氧烷嵌段聚合物(hydrogendimethylsiloxy group-terminated dimethylsiloxane-hydrogenmethylsiloxane block polymer)、或兩個末端各自為氫化二甲基矽烷氧基(hydrogendimethylsiloxy group)和三甲基甲矽烷氧基(trimethylsiloxy group)的矽氧烷樹脂，並且可 更包括含芳香基的寡聚物(oligomer)。 For example, the third organopolysiloxane may include hydrogendimethylsiloxy group-terminated dimethylsiloxane polymer (hydrogendimethylsiloxy group-terminated dimethylsiloxane polymer), trimethylsiloxy group-terminated dimethylsiloxane polymer, and trimethylsiloxy group-terminated dimethylsiloxane polymer. Trimethylsiloxy group-terminated methylhydrogensiloxane polymer, trimethylsiloxy group-terminated methylhydrogensiloxane-dimethylsiloxane block polymer, hydrogenated Hydrogendimethylsiloxy group-terminated dimethylsiloxane-hydrogenmethylsiloxane block polymer (hydrogendimethylsiloxy group-terminated dimethylsiloxane-hydrogenmethylsiloxane block polymer) or both ends are hydrogenated dimethylsiloxy group-terminated dimethylsiloxane-hydrogenmethylsiloxane block polymer (hydrogendimethylsiloxy group) and trimethylsiloxy group (trimethylsiloxy group) silicone resin, and can It also includes oligomers containing aromatic groups.

氫化二甲基矽烷氧基末端的二甲基矽氧烷聚合物可以是(HMe2SiO1/2)(Me2SiO)n10(HMe2SiO1/2)。特別地，可以包括(HMe2SiO1/2)(Me2SiO)25(HMe2SiO1/2)、(HMe2SiO1/2)(Me2SiO)45(HMe2SiO1/2)或(HMe2SiO1/2)(Me2SiO)125(HMe2SiO1/2)。 The dimethylsiloxane polymer at the end of the hydrogenated dimethylsilyloxy group may be (HMe 2 SiO 1/2 )(Me 2 SiO) n10 (HMe 2 SiO 1/2 ). In particular, it may include (HMe 2 SiO 1/2 )(Me 2 SiO) 25 (HMe 2 SiO 1/2 ), (HMe 2 SiO 1/2 )(Me 2 SiO) 45 (HMe 2 SiO 1/2 ) Or (HMe 2 SiO 1/2 )(Me 2 SiO) 125 (HMe 2 SiO 1/2 ).

三甲基矽烷氧基末端的甲基氫矽氧烷聚合物可以是(Me3SiO1/2)(HMeSiO)n11(Me3SiO1/2)。特別地，可包括(Me3SiO1/2)(HMeSiO)20(Me3SiO1/2)或(Me3SiO1/2)(HMeSiO)40(Me3SiO1/2)。 The methylhydrosiloxane polymer at the end of the trimethylsilyloxy group may be (Me 3 SiO 1/2 )(HMeSiO) n11 (Me 3 SiO 1/2 ). In particular, (Me 3 SiO 1/2 )(HMeSiO) 20 (Me 3 SiO 1/2 ) or (Me 3 SiO 1/2 )(HMeSiO) 40 (Me 3 SiO 1/2 ) may be included.

三甲基矽烷氧基末端的甲基氫矽氧烷-二甲基矽氧烷嵌段聚合物可以是(Me3SiO1/2)(Me2SiO)n12(HMeSiO)n13(Me3SiO1/2)。特別是，(Me3SiO1/2)(Me2SiO)20(HMeSiO)20(Me3SiO1/2)、(Me3SiO1/2)(Me2SiO)25(HMeSiO)12(Me3SiO1/2)、(Me3SiO1/2)(Me2SiO)19(HMeSiO)21(Me3SiO1/2)、(Me3SiO1/2)(Me2SiO)46(HMeSiO)20(Me3SiO1/2)、(Me3SiO1/2)(Me2SiO)100(HMeSiO)10(Me3SiO1/2)或(Me3SiO1/2)(Me2SiO)7(HMeSiO)3(Me3SiO1/2)。 The methylhydrosiloxane-dimethylsiloxane block polymer at the end of the trimethylsilyloxy group can be (Me 3 SiO 1/2 )(Me 2 SiO) n12 (HMeSiO) n13 (Me 3 SiO 1 /2 ). In particular, (Me 3 SiO 1/2 )(Me 2 SiO) 20 (HMeSiO) 20 (Me 3 SiO 1/2 ), (Me 3 SiO 1/2 )(Me 2 SiO) 25 (HMeSiO) 12 (Me 3 SiO 1/2 ), (Me 3 SiO 1/2 )(Me 2 SiO) 19 (HMeSiO) 21 (Me 3 SiO 1/2 ), (Me 3 SiO 1/2 )(Me 2 SiO) 46 (HMeSiO ) 20 (Me 3 SiO 1/2 ), (Me 3 SiO 1/2 )(Me 2 SiO) 100 (HMeSiO) 10 (Me 3 SiO 1/2 ) or (Me 3 SiO 1/2 )(Me 2 SiO ) 7 (HMeSiO) 3 (Me 3 SiO 1/2 ).

氫化二甲基矽烷氧基和三甲基矽烷氧基末端的矽酸鹽樹脂可以是(HMe2SiO1/2)n14(Me3SiO1/2)n15(SiO2)n16。例如，可以包括(HMe2SiO1/2)0.6(Me3SiO1/2)0.1(SiO2)0.2或(HMe2SiO1/2)0.5(Me3SiO1/2)0.2(SiO2)0.3。 The silicate resin at the ends of the hydrogenated dimethylsilyloxy and trimethylsilyloxy groups may be (HMe 2 SiO 1/2 ) n14 (Me 3 SiO 1/2 ) n15 (SiO 2 ) n16 . For example, it may include (HMe 2 SiO 1/2 ) 0.6 (Me 3 SiO 1/2 ) 0.1 (SiO 2 ) 0.2 or (HMe 2 SiO 1/2 ) 0.5 (Me 3 SiO 1/2 ) 0.2 (SiO 2 ) 0.3 .

含有芳香基的寡聚物可以是(HMe2SiO1/2)3(PhSiO1.5)or(HMeSiO1/2)2(Ph2SiO)。 The aromatic group-containing oligomer may be (HMe 2 SiO 1/2 ) 3 (PhSiO 1.5 ) or (HMeSiO 1/2 ) 2 (Ph 2 SiO).

第三有機聚矽氧烷在25℃下的黏度可以為0.005-0.15Pa．s。如果第三有機聚矽氧烷在25℃下的黏度偏離數值範圍，則存在模塑可工作性(mold workability)顯著劣化的問題。 The viscosity of the third organopolysiloxane at 25°C can be 0.005-0.15Pa. s. If the viscosity of the third organopolysiloxane at 25°C deviates from the numerical range, there is a problem that mold workability is significantly deteriorated.

基於混合的有機聚矽氧烷的總重量，可以包括30至50wt%(例如40wt%)的第一有機聚矽氧烷、40至60wt%(例如50wt%)的第二有機聚矽氧烷及剩餘量(例如10wt%)的第三有機聚矽氧烷。 Based on the total weight of the mixed organopolysiloxane, it may include 30 to 50wt% (for example, 40wt%) of the first organopolysiloxane, 40 to 60wt% (for example, 50wt%) of the second organopolysiloxane, and The remaining amount (for example, 10wt%) of the third organopolysiloxane.

更具體地，第三有機聚矽氧烷的含量優選使得氫的莫耳數相對於混合的有機聚矽氧烷中的總烯基的莫耳數為0.5至5(例如0.8至3)。 More specifically, the content of the third organopolysiloxane is preferably such that the mole number of hydrogen relative to the mole number of the total alkenyl groups in the mixed organopolysiloxane is 0.5 to 5 (for example, 0.8 to 3).

如果第一有機聚矽氧烷的量小於30wt%，則硬度降低並且鋸切可工作性(sawing workability)劣化，並且如果該量大於50wt%，則室溫下的流動性消失並且可工作性劣化。如果第二有機聚矽氧烷的量小於40wt%，則交聯密度增加並且通過熱衝擊可能在固化產物中容易產生裂縫，並且如果該量大於60wt%，則硬度可能降低。 If the amount of the first organopolysiloxane is less than 30wt%, the hardness is reduced and sawing workability is deteriorated, and if the amount is more than 50wt%, fluidity at room temperature disappears and workability is deteriorated . If the amount of the second organopolysiloxane is less than 40 wt%, the crosslinking density increases and cracks may be easily generated in the cured product through thermal shock, and if the amount is more than 60 wt%, the hardness may decrease.

另外，如果第三有機聚矽氧烷的氫莫耳數相對於總烯基的莫耳數小於0.5，則固化產物形成不充分，硬度降低，在此期間產生大量毛邊。在鋸切過程中，可能降低光學半導體封裝(發光二極體封裝)的產量。如果氫的莫耳數大於5，則交聯密度增加，固化產物容易破裂，並且由於產生氫氣而在固化產物的表面形成空隙，從而降 低光學半導體封裝(發光二極體封裝)的產率。 In addition, if the number of hydrogen moles of the third organopolysiloxane is less than 0.5 relative to the number of moles of the total alkenyl groups, the cured product is insufficiently formed, the hardness is reduced, and a lot of burrs are generated during this period. During the sawing process, the output of optical semiconductor packages (light emitting diode packages) may be reduced. If the molar number of hydrogen is greater than 5, the crosslinking density increases, the cured product is easily broken, and voids are formed on the surface of the cured product due to the generation of hydrogen, thereby reducing Low yield of optical semiconductor packages (light emitting diode packages).

顏料 pigment

在本發明中，顏料是用於降低固化產物的透射率，實現白色，從而在可見光區域中實現反射的組分，並且優選是白色顏料。例如，顏料可選自由氧化鈦(titanium oxide)、氧化鋁(alumina)、氧化鋅(zinc oxide)、氧化鋯(zirconium oxide)、氧化鎂(magnesium oxide)、硫酸鋇(barium sulfate)和硫酸鋅(zinc sulfate)所組成的群組，優選二氧化鈦(titanium dioxide)。 In the present invention, the pigment is a component for reducing the transmittance of the cured product to achieve white color, thereby achieving reflection in the visible light region, and is preferably a white pigment. For example, the pigment can be selected from titanium oxide, aluminum oxide, zinc oxide, zirconium oxide, magnesium oxide, barium sulfate, and zinc sulfate ( The group consisting of zinc sulfate, titanium dioxide (titanium dioxide) is preferred.

此外，顏料優選具有0.05至10μm的粒徑，例如，粒徑為0.1至1μm。如果粒徑小於0.05μm，則分散性可能降低，並且組合物的黏度可能容易增加，並且如果粒徑大於10μm，則在分配器中使用的噴嘴的種類等，可能會受到限制，並且可能引起噴嘴堵塞，從而降低了可工作性。 In addition, the pigment preferably has a particle diameter of 0.05 to 10 μm, for example, a particle diameter of 0.1 to 1 μm. If the particle size is less than 0.05μm, the dispersibility may decrease, and the viscosity of the composition may easily increase, and if the particle size is greater than 10μm, the types of nozzles used in the dispenser, etc., may be restricted and may cause nozzles Blockage, thereby reducing workability.

可以使用表面處理劑(例如是矽烷偶聯劑(silane coupling agent)、二氧化矽(silica)、氧化鋁(alumina))等對顏料進行表面處理，以改善與混合的有機聚矽氧烷的相容性和在組合物中的分散性。 Surface treatment agents (such as silane coupling agent, silica, alumina) can be used to treat the surface of the pigment to improve the phase of the mixed organopolysiloxane. Compatibility and dispersibility in the composition.

基於100重量份的混合有機聚矽氧烷，顏料的含量可以為20至50重量份(例如25至45重量份)。如果含量小於20重量份，則可以降低小於250μm的薄膜中的透光率，並且可以降低反射率，並且如果該量大於50重量份，則觸變指數(thixotropic index)。可增加並且組合物的黏度可能增加，從而降低了可工作性(例如分 配)。 Based on 100 parts by weight of the mixed organopolysiloxane, the content of the pigment may be 20 to 50 parts by weight (for example, 25 to 45 parts by weight). If the content is less than 20 parts by weight, the light transmittance in a film of less than 250 μm can be reduced, and the reflectance can be reduced, and if the amount is more than 50 parts by weight, the thixotropic index (thixotropic index). Can increase and the viscosity of the composition may increase, thereby reducing workability (such as With).

在一個實施例中，在將表面處理的顏料與表面處理劑一起使用的情況下，基於表面處理的顏料的總重量，顏料的表面處理重量可以小於5w%，並且顏料可代表表面處理顏料的重量。 In one embodiment, in the case of using a surface-treated pigment together with a surface treatment agent, based on the total weight of the surface-treated pigment, the surface-treated weight of the pigment may be less than 5w%, and the pigment may represent the weight of the surface-treated pigment .

填料 filler

在本發明中，包含半矽氧烷作為增強填料，並且可以改善可固化的有機聚矽氧烷組合物的可工作性，並且在固化產品中，可以增加模量，熱膨脹係數(coefficient of thermal expansion，CTE)可以減少，且硬度可能會增加。在本發明中，透過包含半矽氧烷，可以減少顏料(特別是白色顏料)的量，並且可以確保根據時間的穩定性並且可以顯著改善組合物中的反射率。 In the present invention, semisiloxane is included as a reinforcing filler, and the workability of the curable organopolysiloxane composition can be improved, and in the cured product, the modulus and coefficient of thermal expansion (coefficient of thermal expansion) can be increased. , CTE) can be reduced, and hardness may increase. In the present invention, by including semisiloxane, the amount of pigments (especially white pigments) can be reduced, and stability according to time can be ensured and the reflectance in the composition can be significantly improved.

另外，半矽氧烷可以僅由T單元或Q單元組成，或者它們的混合類型。然而，為了顯示包含半矽氧烷的組合物的低觸變指數(thixotropic index)，由T單元組成的半矽氧烷優於由Q單元組成的半矽氧烷。半矽氧烷可由下式4表示：[式4](R6SiO3/2)n In addition, the semisiloxane may be composed of only T units or Q units, or a mixed type of them. However, in order to show the low thixotropic index of the composition containing the semisiloxane, the semisiloxane composed of T units is superior to the semisiloxane composed of Q units. Semisiloxane can be represented by the following formula 4: [Formula 4](R 6 SiO 3/2 ) n

在式4中，n是4至1,000的數，R6各自獨立地是氫、C1至C6的烷基，C2至C6的烯基，或C6至C12的芳香基，較佳地，C1至C6的烷基，更佳地為甲基。特別地，半矽氧烷是增強填料，並且為了藉由改善固化產物的模量和增加硬度來改善加工性，可以優選使用其中R6是甲基的甲基半矽氧烷(methylsilsesquioxane)。 In Formula 4, n is a number from 4 to 1,000, and R 6 is each independently hydrogen, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, or a C 6 to C 12 aromatic group, and R 6 is each independently hydrogen, a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, or a C 6 to C 12 aromatic group. Preferably, the C 1 to C 6 alkyl group is more preferably a methyl group. In particular, semisiloxane is a reinforcing filler, and in order to improve processability by improving the modulus of the cured product and increasing the hardness, methylsilsesquioxane in which R 6 is a methyl group can be preferably used.

此外，半矽氧烷優選為平均直徑為0.5至20μm(例如2至10μm)的球形顆粒，以改善分散性和流動性。如果平均粒徑小於0.5μm，則比表面積大，並且分散不容易，因此，組合物的黏度可能增加。如果平均粒徑大於20μm，則用於分配器等的噴嘴受到限制並且可能引起堵塞現象，從而降低了可工作性。 In addition, the semisiloxane is preferably spherical particles having an average diameter of 0.5 to 20 μm (for example, 2 to 10 μm) in order to improve dispersibility and fluidity. If the average particle diameter is less than 0.5 μm, the specific surface area is large, and dispersion is not easy, and therefore, the viscosity of the composition may increase. If the average particle diameter is greater than 20 μm, nozzles used for dispensers and the like are restricted and clogging may be caused, thereby reducing workability.

基於100重量份的混合有機聚矽氧烷，半矽氧烷的含量可以為5至15重量份(例如7至13重量份)。如果該量小於5重量份，則作為增強填料的功能可能不足，並且如果該量大於15重量份，則固化產物的模量、熱膨脹係數、硬度等的改善可能無法達成，可能會降低經濟可行性，增加觸變指數，並且可能增加黏度，從而降低可工作性。 Based on 100 parts by weight of the mixed organopolysiloxane, the content of semisiloxane may be 5 to 15 parts by weight (for example, 7 to 13 parts by weight). If the amount is less than 5 parts by weight, the function as a reinforcing filler may be insufficient, and if the amount is greater than 15 parts by weight, the improvement of the modulus, thermal expansion coefficient, hardness, etc. of the cured product may not be achieved, which may reduce economic feasibility , Increase the thixotropic index, and may increase the viscosity, thereby reducing workability.

此外，根據本發明的可固化的有機基聚矽氧烷組合物包括氫化矽烷化催化劑(hydrosilylation catalyst)。氫化矽烷化催化劑是用於加速第一有機聚矽氧烷、第二有機聚矽氧烷的烯基和與第三有機聚矽氧烷的矽鍵合的氫基的羥基的氫化矽烷化反應的反應催化劑組分。氫化矽烷化催化劑可以是(例如)一或多個選自由鉑基催化劑(platinum-based catalyst)、銠基催化劑(rhodium-based catalyst)和鈀基催化劑(palladium-based catalyst)所組成之群組中，並且較佳地，可以使用鉑基催化劑。鉑基催化劑可以使用細碎的鉑粉、氯鉑酸(chloroplatinic acid)、氯鉑酸(alcohol solution of chloroplatinic acid)的醇溶液(揭露於美國公開專利公開No.3,220,972中)、鉑-烯基矽氧烷複合物(platinum-alkenylsiloxane complex)、鉑-烯烴 複合物(platinum-olefin complex)、鉑-羰基複合物(platinum-carbonyl)等，並且較佳使用鉑-烯基矽氧烷複合物。 In addition, the curable organopolysiloxane composition according to the present invention includes a hydrosilylation catalyst. The hydrosilylation catalyst is used to accelerate the hydrosilylation reaction of the first organopolysiloxane, the alkenyl group of the second organopolysiloxane, and the hydroxyl group of the hydrogen group bonded to the silicon of the third organopolysiloxane Reaction catalyst components. The hydrosilylation catalyst may be, for example, one or more selected from the group consisting of platinum-based catalysts, rhodium-based catalysts and palladium-based catalysts , And preferably, a platinum-based catalyst can be used. The platinum-based catalyst may use finely divided platinum powder, chloroplatinic acid (chloroplatinic acid), alcohol solution of chloroplatinic acid (disclosed in U.S. Patent Publication No. 3,220,972), platinum-alkenyl silicate Platinum-alkenylsiloxane complex, platinum-olefin A platinum-olefin complex, a platinum-carbonyl complex, etc., and a platinum-alkenylsiloxane complex is preferably used.

基於混合有機聚矽氧烷的總重量，如果使用鉑基催化劑作為催化劑，則鉑基催化劑的加入量是優選使得鉑原子包含0.01至100ppm(例如0.1至50ppm)。如果該量小於0.01ppm，則反應速率可能降低或反應可能不充分，並且如果該量大於100ppm，則反射率可能由於變色而降低。 Based on the total weight of the mixed organopolysiloxane, if a platinum-based catalyst is used as a catalyst, the addition amount of the platinum-based catalyst is preferably such that the platinum atom contains 0.01 to 100 ppm (for example, 0.1 to 50 ppm). If the amount is less than 0.01 ppm, the reaction rate may decrease or the reaction may be insufficient, and if the amount is greater than 100 ppm, the reflectance may decrease due to discoloration.

添加劑 additive

只要不妨礙本發明的目的，本發明的可固化的有機基聚矽氧烷組合物可以進一步包括通常包含在有機聚矽氧烷組合物中的添加劑。這種添加劑可包括，例如，黏合促進劑(adhesion promoter)、無機填料、矽粉、樹脂粉、耐熱劑(heat resistant agent)、抗氧化劑、自由基清除劑、光穩定劑、阻燃添加劑(flame retardant additive)、矽基稀釋劑(silicon-based diluent)和阻燃劑。本發明的可固化的有機聚矽氧烷組合物還可包含選自這些添加劑中的至少一種。 As long as the object of the present invention is not hindered, the curable organopolysiloxane composition of the present invention may further include additives usually contained in the organopolysiloxane composition. Such additives may include, for example, adhesion promoters, inorganic fillers, silica powder, resin powder, heat resistant agents, antioxidants, free radical scavengers, light stabilizers, flame retardants, etc. retardant additive, silicon-based diluent and flame retardant. The curable organopolysiloxane composition of the present invention may further include at least one selected from these additives.

類似這樣的本發明的可固化的有機聚矽氧烷組合物優選在室溫下(例如在25℃下)為液相，並且藉由在室溫下為液相，在模塑過程中處理可固化的有機聚矽氧烷組合物(例如分配和射出成型(dispensing and injection molding))可以是容易的，並且複雜模製品的製造可以是容易的。此外，本發明的可固化有機聚矽氧烷組合物優選具有小於6Pa．s的黏度，例如，在室溫下(例如在25℃下)的黏度為2.7至5.5Pa．s。如果黏度為6Pa．s或更高，則可能難以定量 排出微量，並且可能在固化表面處形成空隙，因為組合物難以在固化期間容易地填充晶片和電極之間的間隔。另外，如果黏度小於2.7Pa．s，則晶片和電極之間的初始黏合性可能降低，並且可能由於搖動等而導致晶片表面的污染。 The curable organopolysiloxane composition of the present invention like this is preferably a liquid phase at room temperature (for example, at 25°C), and by being a liquid phase at room temperature, it can be processed during the molding process. The cured organopolysiloxane composition (for example, dispensing and injection molding) can be easy, and the manufacture of complex molded articles can be easy. In addition, the curable organopolysiloxane composition of the present invention preferably has less than 6 Pa. The viscosity of s, for example, the viscosity at room temperature (for example, at 25°C) is 2.7 to 5.5Pa. s. If the viscosity is 6Pa. s or higher, it may be difficult to quantify A trace amount is discharged, and voids may be formed at the cured surface because the composition is difficult to easily fill the gap between the wafer and the electrode during curing. In addition, if the viscosity is less than 2.7Pa. s, the initial adhesion between the wafer and the electrode may be reduced, and the surface of the wafer may be contaminated due to shaking, etc.

此外，基於總有機基團，可固化有機聚矽氧烷組合物優選包含15mol%或更少的芳香基(例如苯基(phenyl group))。如果芳香基的含量大於15mol%，則由於芳香基在高溫條件下的氧化反應而變色，耐熱反射率可能降低。 In addition, based on the total organic groups, the curable organopolysiloxane composition preferably contains 15 mol% or less of aromatic groups (for example, phenyl groups). If the content of the aromatic group is greater than 15 mol%, the aromatic group is discolored due to oxidation reaction of the aromatic group under high temperature conditions, and the heat-resistant reflectance may be reduced.

因此，本發明的可固化有機聚矽氧烷組合物包含半矽氧烷作為增強填料，並且儘管芳香基不包含在總有機基團中或包含少於總有機基團的15mol%，固化產物可以具有優異的硬度，可以防止變色(變黃)，因為芳香基含量小並且可能降低高溫條件下芳香基的氧化反應，可能降低由於熱引起的反射率劣化，以及耐熱反射率降低的問題可能會有所改善。 Therefore, the curable organopolysiloxane composition of the present invention contains semisiloxane as a reinforcing filler, and although the aromatic group is not contained in the total organic group or contains less than 15 mol% of the total organic group, the cured product can be It has excellent hardness and can prevent discoloration (yellowing), because the aromatic group content is small and may reduce the oxidation reaction of aromatic groups under high temperature conditions, may reduce the reflectance deterioration caused by heat, and the heat-resistant reflectance may be reduced. Improved.

在本發明中，芳香基的量可以例如透過使用氫核磁共振(1H-NMR)測量。特別地，其量可以確定為芳香基的莫耳數相對於有機基團的總莫耳數。 In the present invention, the amount of aromatic groups can be measured, for example, by using hydrogen nuclear magnetic resonance (1H-NMR). In particular, the amount can be determined as the number of moles of the aromatic group relative to the total number of moles of the organic group.

2.用於光學半導體的反射材料 2. Reflective materials for optical semiconductors

根據本發明的另一個方面，提供了一種用於光學半導體的反射材料，包括使用可固化有機聚矽氧烷組合物形成的固化產物。 According to another aspect of the present invention, there is provided a reflective material for an optical semiconductor, including a cured product formed using a curable organopolysiloxane composition.

藉由固化可固化有機聚矽氧烷組合物形成固化產物。固化產物的形狀沒有特別限制，並且可以包括片形、膜形、凸透鏡形、 凹透鏡形、菲涅耳透鏡形(Fresnel lens shape)、截錐形(truncated cone shape)和方錐形平台(square cone platform)。固化產物可以單獨處理，或者相對於光學半導體等處理為覆蓋、密封或附著狀態。 The cured product is formed by curing the curable organopolysiloxane composition. The shape of the cured product is not particularly limited, and may include a sheet shape, a film shape, a convex lens shape, Concave lens shape, Fresnel lens shape, truncated cone shape and square cone platform. The cured product may be processed alone, or processed into a covered, sealed, or attached state with respect to an optical semiconductor or the like.

固化產物的肖氏硬度(shore hardness)優選為肖氏A85或更高，並且如果固化產物的硬度小於肖氏A85，則在切割模塑材料期間可能容易產生毛邊並且可工作性可能劣化。 The shore hardness of the cured product is preferably Shore A85 or higher, and if the hardness of the cured product is less than Shore A85, burrs may be easily generated during cutting of the molding material and workability may be deteriorated.

固化產物的厚度優選為200至1,000μm，並且在該數值範圍內，450nm的可見光透射率可以為3%或更小。 The thickness of the cured product is preferably 200 to 1,000 μm, and within this numerical range, the visible light transmittance at 450 nm may be 3% or less.

另外，在高溫下(例如在250℃下)儲存12小時後，固化產物可以保持優異的薄膜反射率、分配可工作性、鋸切可工作性等，並且反射率降低小於5%。 In addition, after 12 hours of storage at a high temperature (for example, at 250° C.), the cured product can maintain excellent film reflectivity, dispensing workability, sawing workability, etc., and the reflectivity is reduced by less than 5%.

用於光學半導體的反射材料(包括固化產品)的使用沒有特別限制，並且可以是例如用於液晶顯示器的背光模組、用於行動電話的閃光模組，以及用於車輛的發光模組。 The use of reflective materials (including cured products) for optical semiconductors is not particularly limited, and may be, for example, backlight modules for liquid crystal displays, flash modules for mobile phones, and light-emitting modules for vehicles.

在下文中，將參考實施例詳細解釋本發明以幫助理解本發明。然而，根據本發明的實施例可以改變為各種其他類型，但是不應該被解釋為將本發明的範圍限制於實施例。提供本發明的實施例僅是為了向本領域中具有通常知識這更完整地解釋本發明。 Hereinafter, the present invention will be explained in detail with reference to the examples to help understand the present invention. However, the embodiments according to the present invention may be changed to various other types, but should not be construed as limiting the scope of the present invention to the embodiments. The embodiments of the present invention are provided only for the purpose of explaining the present invention more completely to those skilled in the art.

實施例及比較例 Examples and comparative examples

使用下表1中所述的組合物製備可固化有機聚矽氧烷組合物。 The curable organopolysiloxane composition was prepared using the composition described in Table 1 below.

混合物的製備方法沒有特別限制，可以使用本領域公知 的分散裝置，例如行星式混合器(planetary mixer)製備。 The preparation method of the mixture is not particularly limited, and well-known in the art can be used Dispersion device, such as planetary mixer (planetary mixer).

Figure 108127363-A0305-02-0022-1
Figure 108127363-A0305-02-0022-1

- (A)第一有機聚矽氧烷：25℃下粉末相的矽樹脂， 其中矽中的二氧化矽單元為50wt%，總有機基團含量為20.8mmol/g，乙烯基含量為1.5mmol/g((ViMe2SiO1/2)0.125(Me3SiO1/2)0.375(SiO2)0.5，CAS No.68584-83-8)。 -(A) The first organopolysiloxane: a powder phase silicone resin at 25°C, in which the silicon dioxide unit in the silicon is 50wt%, the total organic group content is 20.8mmol/g, and the vinyl content is 1.5mmol /g((ViMe 2 SiO 1/2 ) 0.125 (Me 3 SiO 1/2 ) 0.375 (SiO 2 ) 0.5 , CAS No. 68584-83-8).

- (B-1)第二有機聚矽氧烷：兩末端為二甲基乙烯基矽烷氧基(dimethylvinylsiloxy group)的聚二甲基矽氧烷(polydimethylsiloxane)，總有機基團含量為27mmol/g，乙烯基含量為0.12mmol/g，25℃下的黏度為1Pa．s((ViMe2SiO1/2)(Me2SiO)225(ViMe2SiO1/2)，CAS號68083-19-2)。 -(B-1) The second organopolysiloxane: polydimethylsiloxane with dimethylvinylsiloxy group at both ends, the total organic group content is 27mmol/g , The vinyl content is 0.12mmol/g, and the viscosity at 25°C is 1Pa. s((ViMe 2 SiO 1/2 )(Me 2 SiO) 225 (ViMe 2 SiO 1/2 ), CAS number 68083-19-2).

- (B-2)第二有機聚矽氧烷：兩個末端為二甲基乙烯基矽烷氧基的聚甲基苯基矽氧烷(polymethylphenylsiloxane)，總有機基團含量為16.1mmol/g，苯基含量為6.73mmol/g，乙烯基含量為0.9mmol/g，和25℃的黏度為1Pa‧s((ViMe2SiO1/2)(Me2SiO)40(MePhSiO)2(ViMe2SiO1/2)，CAS號156206-81-4)。 -(B-2) The second organopolysiloxane: two polymethylphenylsiloxane ends with dimethylvinylsiloxy groups, the total organic group content is 16.1mmol/g, The phenyl content is 6.73mmol/g, the vinyl content is 0.9mmol/g, and the viscosity at 25°C is 1Pa‧s((ViMe 2 SiO 1/2 )(Me 2 SiO) 40 (MePhSiO) 2 (ViMe 2 SiO 1/2 ), CAS number 156206-81-4).

- (C-1)第三有機聚矽氧烷：兩個末端為三甲基矽烷氧基(trimethylsiloxy group)的聚二甲基甲基氫矽氧烷(polydimethylmethylhydrogensiloxane)，總有機基團含量為30.32mmol/g，氫含量為7.3mmol/g，25℃下的黏度為0.04Pa．s((Me3SiO1/2)(Me2SiO)19(HMeSiO)21(Me3SiO1/2)，CAS號68037-59-2)。 -(C-1) The third organopolysiloxane: polydimethylmethylhydrogensiloxane with two ends of trimethylsiloxy group (trimethylsiloxy group), the total organic group content is 30.32 mmol/g, the hydrogen content is 7.3mmol/g, and the viscosity at 25°C is 0.04Pa. s((Me 3 SiO 1/2 )(Me 2 SiO) 19 (HMeSiO) 21 (Me 3 SiO 1/2 ), CAS number 68037-59-2).

- (C-2)第三有機聚矽氧烷：3-[二甲基甲矽烷基]氧基] -1,1,5,5-四甲基-3-苯基三矽氧烷(3-[dimethylsilyl]oxy]-1,1,5,5-tetramethyl-3-phenyltrisiloxane，CAS No.18027-45-7)。 -(C-2) The third organopolysiloxane: 3-[dimethylsilyl]oxy] -1,1,5,5-Tetramethyl-3-phenyltrisiloxane (3-[dimethylsilyl]oxy]-1,1,5,5-tetramethyl-3-phenyltrisiloxane, CAS No.18027-45 -7).

- (D)顏料：二氧化鈦，其主要平均粒徑為0.25μm，二氧化鈦(TiO2)含量為95%，表面用氧化鋁(Al2O3)、氧化鋅(ZrO2)和三羥甲基丙烷(TMP)處理(CAS No.13463-67-7)。 -(D) Pigment: Titanium dioxide, the main average particle size is 0.25μm, the content of titanium dioxide (TiO 2 ) is 95%, and the surface uses aluminum oxide (Al 2 O 3 ), zinc oxide (ZrO 2 ) and trimethylolpropane (TMP) processing (CAS No. 13463-67-7).

(E)半矽氧烷：主要平均粒徑為4μm的聚甲基半矽氧烷(polymethyl silsesquioxane)(CAS No.68554-70-1)。 (E) Semisiloxane: polymethyl silsesquioxane (CAS No. 68554-70-1) with a main average particle size of 4μm.

(F)氫化矽烷化催化劑：鉑/1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷(platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane)的1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷溶液(1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution)(鉑含量：1wt%)(CAS號68478-92-2)。 (F) Hydrosilylation catalyst: platinum/1,3-divinyl-1,1,3,3-tetramethyldisiloxane (platinum/1,3-divinyl-1,1,3,3- 1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution (1,3-divinyl-1,1,3,3-tetramethyldisiloxane solution) (platinum content: 1wt %) (CAS No. 68478-92-2).

- (G-1)：(3-縮水甘油氧基丙基)三甲氧基矽烷((3-glycidyloxypropyl)trimethoxysilane)(CAS No.2530-83-8)。 -(G-1): (3-glycidyloxypropyl)trimethoxysilane ((3-glycidyloxypropyl)trimethoxysilane) (CAS No. 2530-83-8).

- (G-2)：1-乙烯基-1-環己醇(1-ethenyl-1-cyclohexanol)(CAS No.78-27-3)。 -(G-2): 1-ethenyl-1-cyclohexanol (CAS No. 78-27-3).

- (G-3)：主要平均粒徑為4μm且表面用六甲基二矽氮烷(HMDZ)處理的二氧化矽(CAS No.67762-90-7)。 -(G-3): Silicon dioxide (CAS No. 67762-90-7) whose main average particle size is 4μm and the surface is treated with hexamethyldisilazane (HMDZ).

實驗例 Experimental example

- 黏度(mPa．s)，觸變性：使用安東帕有限公司(Anton Paar GmbH)製造的流變儀(型號名稱MCR301，MCR302)在25 ℃下測量剪切速率1/s值和10/s值。通過黏度指定10/s值，並透過以下等式獲得觸變指數：觸變指數=(1/s黏度)/(10/s黏度) -Viscosity (mPa.s), thixotropy: Use an Anton Paar GmbH (Anton Paar GmbH) rheometer (model name MCR301, MCR302) at 25 Measure the shear rate 1/s value and 10/s value at ℃. Specify the 10/s value by viscosity, and obtain the thixotropic index through the following equation: thixotropic index=(1/s viscosity)/(10/s viscosity)

-硬度(肖氏A)：在用於模塑厚度為6mm的樣品的模具中將組合物在150℃下固化2小時後，使用肖氏A型硬度測試儀在25℃下測量硬度。 -Hardness (Shore A): After curing the composition at 150°C for 2 hours in a mold for molding a sample with a thickness of 6 mm, the hardness is measured at 25°C using a Shore A hardness tester.

- 反射率(%)：對組合物進行脫氣(deaerating)並使用方形塗佈器形成250μm的塗佈層且在150℃下固化2小時而獲得的樣品，並藉由珀金埃爾默股份有限公司(Perkin Elmer Inc.)製造的紫外-可見光譜儀(UV-Vis Spectrometer)(型號名稱Lamda 950)測量此樣品的反射率。基礎是由測量設備製造商提供的硫酸鋇(barium sulfate)標準樣品。 -Reflectance (%): A sample obtained by deaerating the composition and using a square coater to form a 250μm coating layer and curing it at 150°C for 2 hours. The sample was obtained by PerkinElmer The UV-Vis Spectrometer (model name Lamda 950) manufactured by Perkin Elmer Inc. measures the reflectance of this sample. The basis is a barium sulfate standard sample provided by the manufacturer of the measurement equipment.

- 耐熱反射率(%)：將已測量其初始反射率的樣品在250℃下熱儲存12小時後測量反射率，並且根據以下等式指定反射率降低值：耐熱反射率(%)=在250℃下儲存12小時後的反射率-初始反射率 -Heat-resistant reflectance (%): The sample whose initial reflectance has been measured is heat-stored at 250°C for 12 hours and then the reflectance is measured, and the reflectance reduction value is specified according to the following equation: Heat-resistant reflectance (%)=250 Reflectance after storage at ℃ for 12 hours-initial reflectance

-分配可工作性(Dispensing workability)：使用韋密斯公司(Vermes Co.)的壓電型200μm機器人分配器透過將排出量設定為每次0.3mg來排出組合物，並且將20次的累積排出量確定為1組。如果相對於100組的變異係數(coef.var)為0.5或更小，則用「通過」表示，如果大於0.5，則用「失敗」表示。 -Dispensing workability: Use Vermes Co.'s piezoelectric 200μm robot dispenser to discharge the composition by setting the discharge volume to 0.3mg each time, and the cumulative discharge volume of 20 times Determined as 1 group. If the coefficient of variation (coef.var) relative to the 100 groups is 0.5 or less, it is expressed as "pass", and if it is greater than 0.5, it is expressed as "failure".

- 鋸切可工作性(Sawing workability)：將組合物在150℃下固化2小時，以製造具有片形狀至250μm厚度的固化產物。將如此製造的固化產物，使用迪思科(Disco Co.)的200μm刮刀切鋸製造3,000個矩形加工製品，並且使用電子顯微鏡驗證切割表面處的毛邊的產生。如果產生的毛邊數小於10，則用「通過」表示，如果10或更多，則用「失敗」表示。 -Sawing workability: The composition is cured at 150°C for 2 hours to produce a cured product having a sheet shape to a thickness of 250 μm. The cured product thus manufactured was cut using a 200 μm scraper saw from Disco Co. to manufacture 3,000 rectangular processed products, and the generation of burrs at the cut surface was verified using an electron microscope. If the number of flashes produced is less than 10, it is expressed as "Pass", and if it is 10 or more, it is expressed as "Fail".

Figure 108127363-A0305-02-0026-2
Figure 108127363-A0305-02-0026-2
Figure 108127363-A0305-02-0027-3
Figure 108127363-A0305-02-0027-3

請參照表1及表2，與實施例1-5相比，確認含有大量苯基的比較例1的案例由於苯基的變色而顯示出降低的耐熱反射率，並且在不遵循本發明的含有小量顏料(比較例2)或大量顏料(比較例3)的案例下，確認顯示出薄膜反射率、黏度、觸變指數、加工性等的降低。另外，在不遵循本發明的含有少量半矽氧烷(比較例4)或大量(比較例5)半矽氧烷的案例，證實顯示出控制性(harness)、鋸切可工作性或黏度、觸變指數、分配可工作性等的降低。此外，發現其中未使用半矽氧烷但使用二氧化矽作為增強填料的比較例6的物理性能降低。 Please refer to Table 1 and Table 2. Compared with Examples 1-5, it was confirmed that the case of Comparative Example 1 containing a large amount of phenyl groups showed reduced heat-resistant reflectance due to the discoloration of the phenyl groups, and it was confirmed that the case of those that did not comply with the present invention In the case of a small amount of pigment (Comparative Example 2) or a large amount of pigment (Comparative Example 3), it was confirmed that the film reflectance, viscosity, thixotropy index, processability, etc. decreased. In addition, in the case where a small amount of semisiloxane (Comparative Example 4) or a large amount (Comparative Example 5) of semisiloxane is not in accordance with the present invention, it was confirmed that it exhibited harness, sawing workability or viscosity, Decrease in thixotropy index, distribution workability, etc. In addition, it was found that the physical properties of Comparative Example 6 in which no hemisiloxane was used but silica was used as a reinforcing filler was lowered.

綜上所述，雖然本發明已以實施例揭露如上，然其並非用以限定本發明。本發明所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾。因此，本發明之保護範圍當視後附之申請專利範圍所界定者為準。 To sum up, although the present invention has been disclosed as above by embodiments, it is not intended to limit the present invention. Those with ordinary knowledge in the technical field to which the present invention belongs can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be subject to those defined by the attached patent scope.

Claims (8)

一種可固化有機聚矽氧烷組合物，包括：100重量份的混合有機聚矽氧烷；20至50重量份的顏料；以及5至15重量份的半矽氧烷；其中總芳香基的量為總有機基團的15莫耳%或更少，及該半矽氧烷的平均粒徑為0.5至20μm。 A curable organopolysiloxane composition comprising: 100 parts by weight of mixed organopolysiloxane; 20 to 50 parts by weight of pigment; and 5 to 15 parts by weight of semisiloxane; the amount of total aromatic groups in it It is 15 mol% or less of the total organic groups, and the average particle size of the semisiloxane is 0.5 to 20 μm. 如申請專利範圍第1項所述之可固化有機聚矽氧烷組合物，其中該混合有機聚矽氧烷包含：由下列式1所示的一第一有機聚矽氧烷；具有直鏈的一第二有機聚矽氧烷，由下列式2所示；以及由下式3所示的一第三有機聚矽氧烷：[式1](R1 3SiO1/2)a(R2 3SiO1/2)b(SiO2)c在式1中，R1與R2各自獨立地為C1-C6的烷基或C2-C6的烯基，其中R1中的至少一個為C2-C6的烯基，「a」為0.05至0.25的數，「b」為0.1至0.5的數，且「c」為0.4至0.6的數；[式2](R3 3SiO1/2)2(R3R4SiO)d(R4 2SiO)e在式2中，R3各自獨立地為C1-C6的烷基、C2-C6的烯基或C6-C12的芳香基，R4各自獨立地為C1-C6的烷基或C6至C12芳香基，且「d」和「e」各自獨立地為0或1或更大的整數，其中滿足10
Figure 108127363-A0305-02-0028-13
d+e
Figure 108127363-A0305-02-0028-14
10,000且0
Figure 108127363-A0305-02-0028-15
d/(d+e)
Figure 108127363-A0305-02-0028-16
0.1；以及 [公式3]HfR5 gSiO(4-f-g)/2在式3中，R5各自獨立地為C1至C6的烷基或C6至C12的芳香基，「f」為0.001至2的數，並且「g」為0.7至2的數，其中滿足0.8
Figure 108127363-A0305-02-0029-17
f+g
Figure 108127363-A0305-02-0029-18
3。 The curable organopolysiloxane composition according to item 1 of the scope of patent application, wherein the mixed organopolysiloxane comprises: a first organopolysiloxane represented by the following formula 1; A second organopolysiloxane represented by the following formula 2; and a third organopolysiloxane represented by the following formula 3: [Formula 1](R 1 3 SiO 1/2 ) a (R 2 3 SiO 1/2 ) b (SiO 2 ) c In formula 1, R 1 and R 2 are each independently a C 1 -C 6 alkyl group or a C 2 -C 6 alkenyl group, wherein at least one of R 1 A C 2 -C 6 alkenyl group, "a" is a number from 0.05 to 0.25, "b" is a number from 0.1 to 0.5, and "c" is a number from 0.4 to 0.6; [Formula 2](R 3 3 SiO 1/2 ) 2 (R 3 R 4 SiO) d (R 4 2 SiO) e In formula 2, R 3 is each independently a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group or A C 6 -C 12 aromatic group, R 4 is each independently a C 1 -C 6 alkyl group or a C 6 to C 12 aromatic group, and "d" and "e" are each independently 0 or 1 or greater Integer, which satisfies 10
Figure 108127363-A0305-02-0028-13
d+e
Figure 108127363-A0305-02-0028-14
10,000 and 0
Figure 108127363-A0305-02-0028-15
d/(d+e)
Figure 108127363-A0305-02-0028-16
0.1; and [Formula 3] H f R 5 g SiO (4-fg)/2 In formula 3, R 5 is each independently a C 1 to C 6 alkyl group or a C 6 to C 12 aromatic group, "f" is a number from 0.001 to 2, and "g" is a number from 0.7 to 2, which satisfies 0.8
Figure 108127363-A0305-02-0029-17
f+g
Figure 108127363-A0305-02-0029-18
3. 如申請專利範圍第2項所述之可固化有機聚矽氧烷組合物，更包括基於該混合有機聚矽氧烷之總重量的30至50wt%的該第一有機聚矽氧烷、40至60wt%的該第二有機聚矽氧烷以及剩餘量的該第三有機聚矽氧烷。 The curable organopolysiloxane composition described in item 2 of the scope of the patent application further comprises 30 to 50 wt% of the first organopolysiloxane, 40 to 40% by weight based on the total weight of the mixed organopolysiloxane 60wt% of the second organopolysiloxane and the remaining amount of the third organopolysiloxane. 如申請專利範圍第2項所述之可固化有機聚矽氧烷組合物，其中該第三有機聚矽氧烷的加入量使得相對於該混合有機聚矽氧烷中的總烯基的氫的莫耳數為0.5至5。 The curable organopolysiloxane composition as described in item 2 of the scope of patent application, wherein the third organopolysiloxane is added in an amount such that the amount of hydrogen in the mixed organopolysiloxane is relative to the total alkenyl hydrogen in the mixed organopolysiloxane. The number of moles is 0.5 to 5. 如申請專利範圍第1項所述之可固化有機聚矽氧烷組合物，其中該半矽氧烷由下列式4所示：[式4](R6SiO3/2)n在式4中，「n」是4至1,000的整數，R6各自獨立地是C1至C6的烷基、C2至C6的烯基或C6至C12的芳香基。 The curable organopolysiloxane composition described in item 1 of the scope of patent application, wherein the semisiloxane is represented by the following formula 4: [Formula 4](R 6 SiO 3/2 ) n is in the formula 4 , "N" is an integer from 4 to 1,000, and R 6 is each independently a C 1 to C 6 alkyl group, a C 2 to C 6 alkenyl group, or a C 6 to C 12 aromatic group. 如申請專利範圍第1項所述之可固化有機聚矽氧烷組合物，在25℃下為液相並且具有小於6Pa．s的黏度。 The curable organopolysiloxane composition described in item 1 of the scope of the patent application is a liquid phase at 25°C and has less than 6Pa. The viscosity of s. 一種用於光學半導體的反射材料，包括使用如申請專利範圍第1至6項中任一項所述的可固化有機基聚矽氧烷組合物所形成的固化產物。 A reflective material for optical semiconductors includes a cured product formed by using the curable organopolysiloxane composition described in any one of items 1 to 6 of the scope of the patent application. 如申請專利範圍第7項所述之光學半導體的反射材料，其中該光學半導體是用於液晶顯示器的背光模組、用於行動電話的閃光模組、以及用於車輛的照明模組。 The reflective material of the optical semiconductor as described in item 7 of the scope of patent application, wherein the optical semiconductor is a backlight module for liquid crystal displays, a flashlight module for mobile phones, and a lighting module for vehicles.
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