TW202035546A - Sealing composition and semiconductor device - Google Patents
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- TW202035546A TW202035546A TW108147087A TW108147087A TW202035546A TW 202035546 A TW202035546 A TW 202035546A TW 108147087 A TW108147087 A TW 108147087A TW 108147087 A TW108147087 A TW 108147087A TW 202035546 A TW202035546 A TW 202035546A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K5/00—Use of organic ingredients
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
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Abstract
Description
本揭示是有關於一種密封組成物及半導體裝置。This disclosure relates to a sealing composition and a semiconductor device.
近年來，伴隨小型化及高積體化，擔心半導體封裝體內部的發熱。由於存在因發熱而產生具有半導體封裝體的電氣零件或電子零件的性能下降之虞，因此對半導體封裝體中所使用的構件要求高的導熱性。因此，要求對半導體封裝體的密封材進行高導熱化。 例如，藉由高填充無機填充材，密封材的高導熱化成為可能。In recent years, along with miniaturization and high integration, there is a concern about heat generation inside the semiconductor package. Since the performance of the electrical parts or electronic parts having the semiconductor package may be reduced due to heat generation, the members used in the semiconductor package are required to have high thermal conductivity. Therefore, it is required to increase the thermal conductivity of the sealing material of the semiconductor package. For example, with highly filled inorganic fillers, high thermal conductivity of the sealing material becomes possible.
作為高填充有無機填充材的密封材的例子，已知有一種半導體密封用環氧樹脂組成物，其以（A）環氧樹脂、（B）硬化劑以及（D）含有球狀氧化鋁及球狀二氧化矽的無機填充材為必需成分，所述半導體密封用環氧樹脂組成物的特徵在於，所述球狀氧化鋁包含（d1）平均粒徑40 μm以上且70 μm以下的第一球狀氧化鋁及（d2）平均粒徑10 μm以上且15 μm以下的第二球狀氧化鋁，所述球狀二氧化矽包含（d3）平均粒徑4 μm以上且8 μm以下的第一球狀二氧化矽、（d4）平均粒徑0.05 μm以上～1.0 μm以下的第二球狀二氧化矽，相對於全部無機填充材（d3）+（d4）的合計量為17%以上且23%以下，（d3）/（d4）的比率為（d3）/（d4）=1/8以上且5/4以下，無機填充劑量在全部樹脂組成物中為85質量%～95質量%（例如，參照專利文獻1）。 [現有技術文獻] [專利文獻]As an example of a sealing material highly filled with inorganic fillers, there is known an epoxy resin composition for semiconductor sealing, which contains (A) epoxy resin, (B) hardener, and (D) spherical alumina and An inorganic filler of spherical silica is an essential component, and the epoxy resin composition for semiconductor sealing is characterized in that the spherical alumina contains (d1) the first with an average particle diameter of 40 μm or more and 70 μm or less. Spherical alumina and (d2) the second spherical alumina having an average particle diameter of 10 μm or more and 15 μm or less, and the spherical silica includes (d3) the first particle having an average particle diameter of 4 μm or more and 8 μm or less. Spherical silica, (d4) the second spherical silica with an average particle size of 0.05 μm or more to 1.0 μm or less, with respect to the total amount of all inorganic fillers (d3) + (d4) is 17% or more and 23 % Or less, the ratio of (d3)/(d4) is (d3)/(d4) = 1/8 or more and 5/4 or less, and the amount of inorganic filler in the total resin composition is 85% to 95% by mass (for example , Refer to Patent Document 1). [Prior Art Literature] [Patent Literature]
[專利文獻1]日本專利特開2006-273920號公報[Patent Document 1] Japanese Patent Laid-Open No. 2006-273920
[發明所欲解決之課題] 但是，在專利文獻1中記載的半導體密封用環氧樹脂組成物中，雖藉由高填充作為高導熱填料的氧化鋁，可獲得導熱性高的硬化物，但存在密封材的流動性下降的情況。因此，難題是流動性高的高導熱密封材的開發。[The problem to be solved by the invention] However, in the epoxy resin composition for semiconductor sealing described in Patent Document 1, although high-filling alumina as a highly thermally conductive filler can obtain a cured product with high thermal conductivity, the fluidity of the sealing material is reduced. Happening. Therefore, the problem is the development of highly fluid and highly thermally conductive sealing materials.
根據本發明的一實施形態，提供一種可兼顧導熱性高的硬化物的獲得與流動性的提高的密封組成物以及使用了密封組成物的半導體裝置。According to an embodiment of the present invention, there is provided a sealing composition that can achieve both the acquisition of a cured product with high thermal conductivity and the improvement of fluidity, and a semiconductor device using the sealing composition.
[解決課題之手段] 本發明包含以下的實施形態。 ＜1＞ 一種密封組成物，含有： 環氧樹脂； 硬化劑； 無機填充材，包含比表面積為100 m2 /g以上的二氧化矽粒子；以及 矽烷化合物，具有碳數6以上的鏈狀烴基鍵結於矽原子的結構。 ＜2＞ 如＜1＞所述的密封組成物，其中將密封組成物在硬化溫度175℃及硬化時間90秒的條件下加熱硬化時所獲得的硬化物的蕭氏D所表示的熱時硬度為70以上。 ＜3＞ 如＜1＞或＜2＞所述的密封組成物，其中相對於密封組成物整體，所述無機填充材的含有率為78體積%以上。 ＜4＞ 如＜1＞至＜3＞中任一項所述的密封組成物，其中所述硬化劑含有多官能酚樹脂硬化劑。 ＜5＞ 如＜1＞至＜4＞中任一項所述的密封組成物，其中所述硬化劑含有三苯基甲烷型酚樹脂。 ＜6＞ 如＜1＞至＜5＞中任一項所述的密封組成物，其中所述鏈狀烴基具有選自由(甲基)丙烯醯基、環氧基及烷氧基所組成的群組中的至少一個官能基。 ＜7＞ 如＜1＞至＜6＞中任一項所述的密封組成物，其中所述鏈狀烴基具有(甲基)丙烯醯基。 ＜8＞ 一種半導體裝置，包含半導體元件、以及將所述半導體元件密封而成的如＜1＞至＜7＞中任一項所述的密封組成物的硬化物。[Means for Solving the Problem] The present invention includes the following embodiments. <1> A sealing composition containing: epoxy resin; hardener; inorganic filler containing silicon dioxide particles with a specific surface area of 100 m 2 /g or more; and a silane compound having a chain hydrocarbon group with 6 or more carbons Structure bonded to silicon atoms. <2> The sealing composition as described in <1>, in which the heat-time hardness of the cured product obtained when the sealing composition is heated and cured under the conditions of a curing temperature of 175°C and a curing time of 90 seconds, represented by Shore D For more than 70. <3> The sealing composition according to <1> or <2>, wherein the content of the inorganic filler is 78% by volume or more with respect to the entire sealing composition. <4> The sealing composition according to any one of <1> to <3>, wherein the curing agent contains a polyfunctional phenol resin curing agent. <5> The sealing composition according to any one of <1> to <4>, wherein the curing agent contains a triphenylmethane type phenol resin. <6> The sealing composition according to any one of <1> to <5>, wherein the chain hydrocarbon group has a group selected from the group consisting of (meth)acrylic groups, epoxy groups, and alkoxy groups At least one functional group in the group. <7> The sealing composition according to any one of <1> to <6>, wherein the chain hydrocarbon group has a (meth)acryloyl group. <8> A semiconductor device including a semiconductor element, and a cured product of the sealing composition according to any one of <1> to <7> which seals the semiconductor element.
[發明的效果] 根據本發明的一實施形態，提供一種可兼顧導熱性高的硬化物的獲得與流動性的提高的密封組成物以及使用了密封組成物的半導體裝置。[Effects of the invention] According to an embodiment of the present invention, there is provided a sealing composition that can achieve both the acquisition of a cured product with high thermal conductivity and the improvement of fluidity, and a semiconductor device using the sealing composition.
以下，對用以實施本揭示的密封組成物及半導體裝置的形態進行詳細說明。其中，本發明並不限定於以下的實施形態。在以下的實施形態中，其構成要素（例如亦包括要素步驟等）除特別明示的情況以外，並非必需。關於數值及其範圍亦同樣，並不限制本發明。Hereinafter, the form of the sealing composition and semiconductor device for implementing the present disclosure will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, its constituent elements (for example, also including element steps, etc.) are not essential unless otherwise specified. The same applies to the numerical value and its range, and does not limit the present invention.
在本揭示中，使用「～」所表示的數值範圍中包含「～」的前後所記載的數值分別作為最小值及最大值。 在本揭示中階段性記載的數值範圍中，一個數值範圍所記載的上限值或下限值亦可置換為其他階段性記載的數值範圍的上限值或下限值。而且，在本揭示中所記載的數值範圍中，該數值範圍的上限值或下限值亦可置換為實施例中所示的值。 在本揭示中，各成分亦可包含多種相符的物質。當在組成物中存在多種與各成分相符的物質時，只要無特別說明，則各成分的含有率或含量是指組成物中所存在的該多種物質的合計含有率或含量。 在本揭示中，亦可包含多種與各成分相符的粒子。當在組成物中存在多種與各成分相符的粒子時，只要無特別說明，則各成分的粒徑是指關於組成物中所存在的該多種粒子的混合物的值。 在本揭示中，「(甲基)丙烯醯基」是指丙烯醯基及甲基丙烯醯基中的至少一者，「(甲基)丙烯酸」是指丙烯酸及甲基丙烯酸中的至少一者，「(甲基)丙烯酸酯」是指丙烯酸酯及甲基丙烯酸酯中的至少一者。In the present disclosure, the numerical values described before and after "～" in the numerical range indicated by "～" are used as the minimum value and the maximum value, respectively. In the numerical ranges described stepwise in this disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise. In addition, in the numerical range described in this disclosure, the upper limit or lower limit of the numerical range may be replaced with the values shown in the examples. In the present disclosure, each component may also include multiple corresponding substances. When there are multiple types of substances corresponding to each component in the composition, unless otherwise specified, the content or content of each component refers to the total content or content of the multiple types of substances present in the composition. In the present disclosure, a plurality of particles corresponding to each component may also be included. When there are multiple types of particles corresponding to each component in the composition, unless otherwise specified, the particle size of each component refers to the value of the mixture of the multiple types of particles present in the composition. In the present disclosure, "(meth)acryl" refers to at least one of acrylic and methacryl, and "(meth)acryl" refers to at least one of acrylic and methacrylic , "(Meth)acrylate" refers to at least one of acrylate and methacrylate.
＜密封組成物＞ 本揭示的密封組成物含有：環氧樹脂；硬化劑；無機填充材，包含比表面積為100 m2 /g以上的二氧化矽粒子；以及矽烷化合物，具有碳數6以上的鏈狀烴基鍵結於矽原子的結構。 以下，有時將比表面積為100 m2 /g以上的二氧化矽粒子稱為「特定二氧化矽粒子」，將具有碳數6以上的鏈狀烴基鍵結於矽原子的結構的矽烷化合物稱為「特定矽烷化合物」。<Sealing composition> The sealing composition of the present disclosure contains: epoxy resin; hardener; inorganic filler containing silicon dioxide particles with a specific surface area of 100 m 2 /g or more; and silane compound having a carbon number of 6 or more A structure in which a chain hydrocarbon group is bonded to a silicon atom. Hereinafter, silica particles with a specific surface area of 100 m 2 /g or more are sometimes referred to as "specific silica particles", and silane compounds having a structure in which a chain hydrocarbon group with 6 or more carbon atoms is bonded to a silicon atom are sometimes referred to as silane compounds. It is a "specified silane compound".
本揭示的密封組成物含有所述特定矽烷化合物，因此可兼顧導熱性高的硬化物的獲得與流動性的提高。 一般而言，藉由高填充無機填充材，可獲得導熱性高的硬化物。但是，若不斷提高無機填充材的填充量，則除了流動性容易下降以外，亦存在即便進而提高無機填充材的填充量，硬化物的導熱性亦不易上升，而導熱性成為飽和狀態的情況。相對於此，本揭示的密封組成物中含有所述特定矽烷化合物，藉此相較於不含特定矽烷化合物的情況，流動性高，可藉由提高無機填充材的填充量來提高硬化物的導熱性。其原因雖不確定，但認為藉由含有特定矽烷化合物，密封組成物內的無機填充材的分散性提高，藉此密封組成物的流動性提高，並且容易發揮無機填充材提高導熱性的功能。根據以上的內容推測：本揭示的密封組成物可兼顧導熱性高的硬化物的獲得與流動性的提高。The sealing composition of the present disclosure contains the specific silane compound, so it can achieve both the acquisition of a cured product with high thermal conductivity and the improvement of fluidity. Generally speaking, a cured product with high thermal conductivity can be obtained by highly filled inorganic fillers. However, if the filling amount of the inorganic filler is continuously increased, the fluidity is likely to decrease, and even if the filling amount of the inorganic filler is further increased, the thermal conductivity of the hardened material is not easily increased, and the thermal conductivity may become saturated. On the other hand, the sealing composition of the present disclosure contains the specific silane compound, thereby having higher fluidity compared to the case where the specific silane compound is not included, and the cured product can be improved by increasing the filling amount of the inorganic filler. Thermal conductivity. Although the reason for this is uncertain, it is thought that by containing the specific silane compound, the dispersibility of the inorganic filler in the sealing composition is improved, thereby the fluidity of the sealing composition is improved, and the function of the inorganic filler to improve the thermal conductivity is easily performed. Based on the foregoing, it is speculated that the sealing composition of the present disclosure can achieve both the acquisition of a cured product with high thermal conductivity and the improvement of fluidity.
以下，對構成密封組成物的各成分進行說明。本揭示的密封組成物含有環氧樹脂、硬化劑、以及無機填充材，視需要亦可含有其他成分。Hereinafter, each component constituting the sealing composition will be described. The sealing composition of this disclosure contains an epoxy resin, a hardener, and an inorganic filler, and may contain other components as necessary.
-環氧樹脂- 本揭示的密封組成物含有環氧樹脂。環氧樹脂的種類並無特別限定，可使用公知的環氧樹脂。 作為環氧樹脂的具體例，可列舉：將使選自由苯酚化合物（苯酚、甲酚、二甲酚、間苯二酚、兒茶酚、雙酚A、雙酚F等）以及萘酚化合物（α-萘酚、β-萘酚、二羥基萘等）所組成的群組中的至少一種、與醛化合物（甲醛、乙醛、丙醛、苯甲醛、水楊醛等）在酸性觸媒下縮合或共縮合而獲得的酚醛清漆樹脂環氧化而得者（苯酚酚醛清漆型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂等）；選自由雙酚（雙酚A、雙酚AD、雙酚F、雙酚S等）及聯苯酚（經烷基取代或未經取代的聯苯酚等）所組成的群組中的至少一種二縮水甘油醚；苯酚·芳烷基樹脂的環氧化物；苯酚化合物與選自由二環戊二烯及萜烯化合物所組成的群組中的至少一種的加成物或聚合加成物的環氧化物；藉由多元酸（鄰苯二甲酸、二聚物酸等）與表氯醇的反應而獲得的縮水甘油酯型環氧樹脂；藉由多胺（二胺基二苯基甲烷、異三聚氰酸等）與表氯醇的反應而獲得的縮水甘油胺型環氧樹脂；利用過氧酸（過乙酸等）對烯烴鍵進行氧化而獲得的線狀脂肪族環氧樹脂；脂環族環氧樹脂等。環氧樹脂可單獨使用一種，亦可併用兩種以上。-Epoxy resin- The sealing composition of this disclosure contains epoxy resin. The type of epoxy resin is not particularly limited, and a known epoxy resin can be used. Specific examples of epoxy resins include: selected from phenol compounds (phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, etc.) and naphthol compounds ( At least one of the group consisting of α-naphthol, β-naphthol, dihydroxynaphthalene, etc.), and aldehyde compounds (formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, etc.) in an acid catalyst Condensation or co-condensation and epoxidation of novolak resin (phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, etc.); selected from bisphenols (bisphenol A, bisphenol AD, double At least one diglycidyl ether in the group consisting of phenol F, bisphenol S, etc.) and biphenol (biphenol substituted or unsubstituted with alkyl, etc.); epoxide of phenol·aralkyl resin; Phenol compounds and epoxides of at least one adduct or polymeric adduct selected from the group consisting of dicyclopentadiene and terpene compounds; by polybasic acid (phthalic acid, dimer) Acid, etc.) glycidyl ester type epoxy resin obtained by the reaction with epichlorohydrin; condensation obtained by the reaction of polyamine (diaminodiphenylmethane, isocyanuric acid, etc.) with epichlorohydrin Glycerylamine epoxy resin; linear aliphatic epoxy resin obtained by oxidizing olefin bonds with peroxy acid (peracetic acid, etc.); alicyclic epoxy resin, etc. One type of epoxy resin may be used alone, or two or more types may be used in combination.
就積體電路（Integrated Circuit，IC）等的元件上的鋁配線或銅配線的防腐蝕的觀點而言，環氧樹脂的純度以高為佳，水解性氯量以少為佳。就提高密封組成物的耐濕性的觀點而言，水解性氯量較佳為以質量基準計為500 ppm以下。From the viewpoint of corrosion prevention of aluminum wiring or copper wiring on components such as an integrated circuit (IC), the purity of the epoxy resin is preferably high, and the amount of hydrolyzable chlorine is preferably small. From the viewpoint of improving the moisture resistance of the sealing composition, the amount of hydrolyzable chlorine is preferably 500 ppm or less on a mass basis.
此處，水解性氯量是藉由將作為試樣的環氧樹脂1 g溶解於二噁烷30 mL中，添加1N-KOH甲醇溶液5 mL回流（reflux）30分鐘後，藉由電位滴定求出的值。Here, the amount of hydrolyzable chlorine is obtained by dissolving 1 g of epoxy resin as a sample in 30 mL of dioxane, adding 5 mL of 1N-KOH methanol solution and refluxing (reflux) for 30 minutes, and then determining by potentiometric titration Value.
關於環氧樹脂的熔點或軟化點，就密封組成物的成形性的觀點而言，較佳為50℃以上，就兼顧密封組成物的成形性與混煉性的觀點而言，較佳為50℃～150℃，更佳為60℃～130℃，進而佳為70℃～120℃。 此處，環氧樹脂的熔點設為利用示差掃描熱量測定（DSC）所測定的值，環氧樹脂的軟化點設為利用依據日本工業標準（Japanese Industrial Standards，JIS）K 7234:1986的方法（環球法）所測定的值。Regarding the melting point or softening point of the epoxy resin, from the viewpoint of the moldability of the sealing composition, it is preferably 50° C. or higher, and from the viewpoint of the moldability and kneading property of the sealing composition, it is preferably 50°C. ℃～150℃, more preferably 60℃～130℃, still more preferably 70℃～120℃. Here, the melting point of the epoxy resin is set to the value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is set to use the method based on Japanese Industrial Standards (JIS) K 7234:1986 ( Ring and Ball Method) measured value.
環氧樹脂的環氧基當量並無特別限定，較佳為不足300 g/eq，就成形性的觀點而言，更佳為120 g/eq～270 g/eq，進而佳為150 g/eq～240/eq。 所述「環氧基當量」是藉由秤量成為測定對象的環氧樹脂使其溶解於甲基乙基酮等的溶劑中，並加入乙酸與溴化四乙基銨乙酸溶液後，利用過氯酸乙酸標準液進行電位滴定，而進行測定。該滴定中亦可使用指示劑。The epoxy equivalent of the epoxy resin is not particularly limited, but is preferably less than 300 g/eq, and from the viewpoint of moldability, it is more preferably 120 g/eq to 270 g/eq, and still more preferably 150 g/eq ~240/eq. The "epoxy equivalent" is measured by weighing the epoxy resin to be measured, dissolving it in a solvent such as methyl ethyl ketone, adding acetic acid and tetraethylammonium bromide acetic acid solution, and using perchlor The acid acetic acid standard solution is subjected to potentiometric titration for measurement. Indicators can also be used in this titration.
環氧樹脂在分子內具有至少兩個以上的環氧基。環氧樹脂在一分子中所具有的環氧基的數量並無特別限定，可列舉2～8，較佳為2～6，更佳為2～3，特佳為2。 另外，所述環氧基亦可作為選自由縮水甘油基、縮水甘油基氧基、縮水甘油基氧基羰基、環氧基環烷基（環氧基環戊基、環氧基環己基、環氧基環辛基等）所組成的群組中的至少一種的一部分而包含在第一環氧樹脂的分子中。The epoxy resin has at least two epoxy groups in the molecule. The number of epoxy groups that the epoxy resin has in one molecule is not particularly limited, and it can be 2-8, preferably 2-6, more preferably 2-3, and particularly preferably 2. In addition, the epoxy group may also be selected from glycidyl, glycidyloxy, glycidyloxycarbonyl, epoxycycloalkyl (epoxycyclopentyl, epoxycyclohexyl, cyclohexyl) A part of at least one of the group consisting of oxycyclooctyl, etc.) is included in the molecule of the first epoxy resin.
環氧樹脂較佳為在分子內除了兩個以上的環氧基以外，亦具有下述通式（1）所表示的二價的連結基。 另外，下述通式（1）中，＊表示鍵結部，R1 ～R8 分別獨立地表示氫原子、碳數1～12的烷基或碳數4～18的芳香族基。It is preferable that the epoxy resin has a divalent linking group represented by the following general formula (1) in addition to two or more epoxy groups in the molecule. In addition, in the following general formula (1), * represents a bonding portion, and R 1 to R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbons, or an aromatic group having 4 to 18 carbons.
[化1]
所述通式（1）中，R1 ～R4 分別獨立地較佳為氫原子或碳數1～3的烷基，更佳為氫原子或甲基，進而佳為甲基。In the general formula (1), R 1 to R 4 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbons, more preferably a hydrogen atom or a methyl group, and still more preferably a methyl group.
而且，所述通式（1）中，R5 ～R8 分別獨立地較佳為氫原子或碳數1～3的烷基，更佳為氫原子或甲基，進而佳為氫原子。 環氧樹脂在密封組成物中所占的含有率較佳為2.5質量%～6質量%，更佳為2.8質量%～5.5質量%，進而佳為3.0質量%～5.0質量%。 環氧樹脂在除去無機填充材的密封組成物中所占的含有率較佳為40質量%～70質量%，更佳為45質量%～64質量%，進而佳為48質量%～55質量%。Furthermore, in the general formula (1), R 5 to R 8 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom. The content of the epoxy resin in the sealing composition is preferably 2.5% by mass to 6% by mass, more preferably 2.8% by mass to 5.5% by mass, and still more preferably 3.0% by mass to 5.0% by mass. The content of the epoxy resin in the sealing composition from which the inorganic filler is removed is preferably 40% by mass to 70% by mass, more preferably 45% to 64% by mass, and still more preferably 48% to 55% by mass .
-硬化劑- 本揭示的密封組成物含有硬化劑。硬化劑的種類並無特別限定，可使用公知的硬化劑。 作為硬化劑，可列舉：酚硬化劑、胺硬化劑、酸酐硬化劑、聚硫醇硬化劑、聚胺基醯胺硬化劑、異氰酸酯硬化劑、嵌段異氰酸酯硬化劑等。就獲得維持流動性且耐回流（reflow）性優異的密封組成物的觀點而言，硬化劑較佳為酚硬化劑、胺硬化劑及酸酐硬化劑，更佳為酚硬化劑。硬化劑可單獨使用一種，亦可併用兩種以上。-hardener- The sealing composition of the present disclosure contains a hardening agent. The type of the curing agent is not particularly limited, and a known curing agent can be used. Examples of the curing agent include phenol curing agents, amine curing agents, acid anhydride curing agents, polythiol curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents. From the viewpoint of obtaining a sealing composition that maintains fluidity and is excellent in reflow resistance, the hardener is preferably a phenol hardener, an amine hardener, and an acid anhydride hardener, and more preferably a phenol hardener. The curing agent may be used alone or in combination of two or more kinds.
作為酚硬化劑，可列舉在一分子中具有兩個以上的酚性羥基的酚樹脂、多元酚化合物等。具體而言，作為酚硬化劑，可列舉：間苯二酚、兒茶酚、雙酚A、雙酚F、經取代或未經取代的雙酚等多元酚化合物；使選自由苯酚、甲酚、二甲苯酚、間苯二酚、兒茶酚、雙酚A、雙酚F、苯基苯酚、胺基苯酚等苯酚化合物及α-萘酚、β-萘酚、二羥基萘等萘酚化合物所組成的群組中的至少一種酚性化合物與甲醛、乙醛、丙醛等醛化合物在酸性觸媒下縮合或共縮合而獲得的酚醛清漆型酚樹脂；由所述酚性化合物與二甲氧基對二甲苯（p-xylene）、雙(甲氧基甲基)聯苯等合成的芳烷基型酚樹脂（苯酚芳烷基樹脂、萘酚芳烷基樹脂等）；對伸二甲苯（p-xylylene）改質酚樹脂；間伸二甲苯（m-xylylene）改質酚樹脂；三聚氰胺改質酚樹脂；萜烯改質酚樹脂；藉由所述酚性化合物與二環戊二烯的共聚而合成的二環戊二烯型苯酚樹脂及二環戊二烯型萘酚樹脂；環戊二烯改質酚樹脂；多環芳香環改質酚樹脂；聯苯型酚樹脂；使所述酚性化合物與苯甲醛、水楊醛等芳香族醛化合物在酸性觸媒下縮合或共縮合而獲得的三苯基甲烷型酚樹脂；將該些兩種以上共聚而獲得的酚樹脂等。該些酚樹脂及多元酚化合物可單獨使用一種，亦可組合兩種以上來使用。Examples of the phenol curing agent include phenol resins and polyphenol compounds having two or more phenolic hydroxyl groups in one molecule. Specifically, as phenol hardeners, polyphenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted bisphenols; selected from phenol and cresol , Xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol and other phenolic compounds and α-naphthol, β-naphthol, dihydroxynaphthalene and other naphthol compounds Novolac-type phenol resin obtained by condensation or co-condensation of at least one phenolic compound and aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde in the group consisting of an acid catalyst; P-xylene, bis(methoxymethyl) biphenyl and other synthetic aralkyl phenol resins (phenol aralkyl resin, naphthol aralkyl resin, etc.); p-xylene ( p-xylylene) modified phenol resin; m-xylylene modified phenol resin; melamine modified phenol resin; terpene modified phenol resin; by copolymerization of the phenolic compound and dicyclopentadiene And synthetic dicyclopentadiene type phenol resin and dicyclopentadiene type naphthol resin; cyclopentadiene modified phenol resin; polycyclic aromatic ring modified phenol resin; biphenyl type phenol resin; A triphenylmethane type phenol resin obtained by condensation or co-condensation of a sexual compound with an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde under an acidic catalyst; a phenol resin obtained by copolymerizing two or more of these. These phenol resins and polyhydric phenol compounds may be used alone or in combination of two or more.
該些中，酚硬化劑較佳為多官能酚樹脂硬化劑，其中較佳為酚醛清漆型酚樹脂、芳烷基型酚樹脂及三苯基甲烷型酚樹脂，更佳為三苯基甲烷型酚樹脂。 此處，「多官能酚樹脂硬化劑」是作為在一分子中具有三個以上官能基（即，羥基）的酚樹脂的硬化劑。Among these, the phenol hardener is preferably a multifunctional phenol resin hardener, among which novolak type phenol resin, aralkyl type phenol resin and triphenylmethane type phenol resin are preferred, and triphenylmethane type is more preferred. Phenol resin. Here, the "polyfunctional phenol resin curing agent" is a curing agent for a phenol resin having three or more functional groups (ie, hydroxyl groups) in one molecule.
作為三苯基甲烷型酚樹脂，可列舉下述通式（2）所表示的酚樹脂。As a triphenylmethane type phenol resin, the phenol resin represented by the following general formula (2) is mentioned.
[化2]
所述通式（2）中，R11 ～R15 分別獨立地表示碳數1～18的一價有機基，b1～b2分別獨立地表示0～4的整數，b3表示0～3的整數，b4～b5分別獨立地表示0～4的整數，n表示0～10。In the general formula (2), R 11 to R 15 each independently represent a monovalent organic group having 1 to 18 carbon atoms, b1 to b2 each independently represent an integer of 0 to 4, and b3 represents an integer of 0 to 3. b4 to b5 each independently represent an integer of 0 to 4, and n represents 0 to 10.
作為通式（2）中的R11 ～R15 所表示的碳數1～18的一價有機基，可列舉經取代或未經取代的烷基、經取代或未經取代的烷氧基、經取代或未經取代的芳基、經取代或未經取代的芳烷基等。 通式（2）中的b1～b5較佳為0～1的整數，更佳為0。 通式（2）中的n較佳為1～7，更佳為2～5。Examples of the monovalent organic group having 1 to 18 carbons represented by R 11 to R 15 in the general formula (2) include substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, Substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, etc. In general formula (2), b1 to b5 are preferably an integer of 0 to 1, and more preferably 0. In general formula (2), n is preferably 1-7, more preferably 2-5.
硬化劑的官能基當量並無特別限制，就成形性的觀點而言，較佳為70 g/eq～500 g/eq，更佳為70 g/eq～300 g/eq，進而佳為80 g/eq～250 g/eq。另外，官能基當量是指依據JIS K0070:1992而測定的值。The functional group equivalent of the curing agent is not particularly limited. From the viewpoint of moldability, it is preferably 70 g/eq to 500 g/eq, more preferably 70 g/eq to 300 g/eq, and still more preferably 80 g /eq～250 g/eq. In addition, the functional group equivalent means a value measured in accordance with JIS K0070:1992.
在硬化劑為固體的情況下，其軟化點或熔點並無特別限制。就成形性與耐回流性的觀點而言，硬化劑的軟化點或熔點較佳為40℃～180℃，就密封組成物的製造時的處理性的觀點而言，軟化點或熔點更佳為50℃～130℃，進而佳為55℃～100℃。 硬化劑的熔點或軟化點設為與環氧樹脂的熔點或軟化點同樣地測定的值。In the case where the hardener is solid, its softening point or melting point is not particularly limited. From the viewpoints of formability and reflow resistance, the softening point or melting point of the hardener is preferably 40°C to 180°C, and from the viewpoint of handling properties during the manufacture of the sealing composition, the softening point or melting point is more preferably 50°C to 130°C, more preferably 55°C to 100°C. The melting point or softening point of the curing agent is a value measured in the same manner as the melting point or softening point of the epoxy resin.
關於環氧樹脂與硬化劑的調配比，就將各自的未反應成分抑制得少的觀點而言，較佳為以相對於環氧樹脂的環氧基1當量，硬化劑的官能基（例如，在酚樹脂的情況下為酚性羥基）的當量成為0.5當量～1.5當量的方式調配硬化劑，特佳為以成為0.7當量～1.2當量的方式調配硬化劑。Regarding the blending ratio of the epoxy resin and the hardening agent, from the viewpoint of suppressing the respective unreacted components to a minimum, it is preferable that the functional group of the hardening agent (for example, In the case of a phenol resin, it is a phenolic hydroxyl group.) The curing agent is prepared so that the equivalent weight becomes 0.5 to 1.5 equivalents, and it is particularly preferable to prepare the curing agent so that it becomes 0.7 to 1.2 equivalents.
-無機填充材- 本揭示的密封組成物至少包含特定二氧化矽粒子（即，比表面積為100 m2 /g以上的二氧化矽粒子）作為無機填充材，視需要亦可包含特定二氧化矽粒子以外的填充材（以下，亦稱為「其他填充材」）。 藉由使密封組成物包含特定二氧化矽粒子，例如可抑制藉由轉移模塑法進行半導體元件的密封時毛邊的產生。 密封組成物較佳為包含特定二氧化矽粒子與其他填充材作為無機填充材。-Inorganic filler- The sealing composition of the present disclosure contains at least specific silica particles (that is, silica particles with a specific surface area of 100 m 2 /g or more) as an inorganic filler, and may also include specific silica particles if necessary Fillers other than particles (hereinafter, also referred to as "other fillers"). By including the specific silica particles in the sealing composition, it is possible to suppress the generation of burrs when the semiconductor device is sealed by a transfer molding method, for example. The sealing composition preferably contains specific silica particles and other fillers as inorganic fillers.
特定二氧化矽粒子的比表面積為100 m2 /g以上，就所述毛邊抑制的觀點而言，較佳為150 m2 /g～300 m2 /g，更佳為170 m2 /g～270 m2 /g，進而佳為190 m2 /g～230 m2 /g。 無機填充材的比表面積（即，布厄特（Brunauer-Emmett-Teller，BET）比表面積）可依據JIS Z 8830:2013並根據氮吸收能來進行測定。作為評價裝置，可使用康塔（QUANTACHROME）公司：自動吸附-1（AUTOSORB-1）（商品名）。在進行BET比表面積的測定時，由於認為吸附於試樣表面及結構中的水分會影響氣體吸附能，所以較佳為首先藉由加熱進行去除水分的前處理。 在前處理中，將投入有0.05 g的測定試樣的測定用單元利用真空泵減壓至10 Pa以下後，以110℃進行加熱，保持3小時以上，之後在保持著減壓的狀態下自然冷卻至常溫（25℃）。進行該前處理後，將評價溫度設為77 K，將評價壓力範圍設為以相對壓（相對於飽和蒸氣壓的平衡壓力）計不足1來進行測定。The specific surface area of the specific silica particles is 100 m 2 /g or more. From the viewpoint of the burr suppression, it is preferably 150 m 2 /g to 300 m 2 /g, and more preferably 170 m 2 /g to 270 m 2 /g, more preferably 190 m 2 /g to 230 m 2 /g. The specific surface area of the inorganic filler (that is, the Brunauer-Emmett-Teller (BET) specific surface area) can be measured in accordance with JIS Z 8830:2013 and based on nitrogen absorption energy. As an evaluation device, QUANTACHROME: AUTOSORB-1 (trade name) can be used. In the measurement of the BET specific surface area, since it is considered that the moisture adsorbed on the surface and structure of the sample will affect the gas adsorption energy, it is preferable to perform the pretreatment to remove moisture by heating first. In the pre-treatment, the measuring cell containing 0.05 g of the measurement sample is reduced to 10 Pa or less with a vacuum pump, then heated at 110°C for 3 hours or more, and then cooled naturally while maintaining the reduced pressure To normal temperature (25℃). After performing this pretreatment, the evaluation temperature was set to 77 K, and the evaluation pressure range was set to be less than 1 in the relative pressure (equilibrium pressure with respect to the saturated vapor pressure).
就所述毛邊抑制及成形性的觀點而言，相對於密封組成物中所含的無機填充材整體，特定二氧化矽粒子的含有率較佳為0.15質量%～1.0質量%，更佳為0.3質量%～0.8質量%，進而佳為0.4質量%～0.7質量%。From the viewpoints of the burr suppression and moldability, the content of the specific silica particles is preferably 0.15 mass% to 1.0 mass%, and more preferably 0.3, relative to the entire inorganic filler contained in the sealing composition. Mass% to 0.8% by mass, more preferably 0.4% to 0.7% by mass.
其他填充材可單獨使用一種，亦可併用兩種以上。 作為併用兩種以上的其他填充材的情況，可列舉使用兩種以上的成分、平均粒徑、形狀等不同的無機填充材的情況。 其他填充材的形狀並無特別限制，可列舉：粉狀、球狀、纖維狀等。就密封組成物的成形時的流動性及金屬模具磨損性的方面而言，其他填充材的形狀較佳為球狀。Other fillers may be used alone or in combination of two or more. As a case where two or more other fillers are used in combination, the case where two or more types of inorganic fillers with different components, average particle diameters, shapes, etc. are used is used. The shape of other fillers is not particularly limited, and examples include powdery, spherical, and fibrous shapes. In terms of fluidity during molding of the sealing composition and mold wear properties, the shape of other fillers is preferably spherical.
就高導熱性的觀點而言，其他填充材較佳為包含氧化鋁。其他填充材可全部為氧化鋁，亦可併用氧化鋁與氧化鋁以外的其他填充材。 作為氧化鋁以外的其他填充材，可列舉：比表面積不足100 m2 /g的二氧化矽（球狀二氧化矽、結晶二氧化矽等）、鋯石、氧化鎂、矽酸鈣、碳酸鈣、鈦酸鉀、碳化矽、氮化矽、氮化硼、氧化鈹、氧化鋯等。進而，作為具有阻燃效果的無機填充材，可列舉氫氧化鋁、硼酸鋅等。From the viewpoint of high thermal conductivity, other fillers preferably contain alumina. All other fillers may be alumina, or other fillers other than alumina and alumina may be used in combination. Examples of fillers other than alumina include: silica (spherical silica, crystalline silica, etc.) with a specific surface area of less than 100 m 2 /g, zircon, magnesium oxide, calcium silicate, calcium carbonate , Potassium titanate, silicon carbide, silicon nitride, boron nitride, beryllium oxide, zirconium oxide, etc. Furthermore, as an inorganic filler having a flame retardant effect, aluminum hydroxide, zinc borate, and the like can be cited.
就吸濕性、線膨脹係數的降低、強度提高及焊料耐熱性的觀點而言，相對於密封組成物的整體，無機填充材的含有率（例如，在無機填充材包含特定二氧化矽粒子及其他填充材的情況下，為包含特定二氧化矽粒子及其他填充材的無機填充材整體的含有率）較佳為60體積%以上，更佳為70體積%以上，進而佳為75體積%以上。 而且，就高導熱性的觀點而言，相對於密封組成物的整體，無機填充材的含有率較佳為78體積%以上，更佳為80體積%以上。就密封組成物的成形性的觀點而言，相對於密封組成物的整體，無機填充材的含有率較佳為95體積%以下，更佳為90體積%以下，進而佳為85體積%以下。就兼顧高導熱性與密封組成物的成形性的觀點而言，無機填充材的含有率較佳為78體積%～90體積%，更佳為78體積%～85體積%，進而佳為80體積%～85體積%。From the viewpoints of hygroscopicity, linear expansion coefficient reduction, strength improvement, and solder heat resistance, relative to the entire sealing composition, the content of the inorganic filler (for example, the inorganic filler contains specific silicon dioxide particles and In the case of other fillers, the content of the entire inorganic filler containing specific silica particles and other fillers is preferably 60% by volume or more, more preferably 70% by volume or more, and still more preferably 75% by volume or more . Furthermore, from the viewpoint of high thermal conductivity, the content of the inorganic filler relative to the entire sealing composition is preferably 78% by volume or more, and more preferably 80% by volume or more. From the viewpoint of the moldability of the sealing composition, the content of the inorganic filler relative to the entire sealing composition is preferably 95% by volume or less, more preferably 90% by volume or less, and still more preferably 85% by volume or less. From the viewpoint of both high thermal conductivity and moldability of the sealing composition, the content of the inorganic filler is preferably 78% by volume to 90% by volume, more preferably 78% by volume to 85% by volume, and still more preferably 80% by volume %～85% by volume.
無機填充材的平均粒徑（例如，在無機填充材包含特定二氧化矽粒子及其他填充材的情況下，為包含特定二氧化矽粒子及其他填充材的無機填充材整體的平均粒徑）較佳為4 μm～100 μm，更佳為7 μm～70 μm，進而佳為7 μm～40 μm。 密封組成物的硬化物的導熱率具有隨著無機填充材的平均粒徑變大而變高的傾向。 無機填充材的平均粒徑可藉由以下的方法來測定。The average particle size of the inorganic filler (for example, when the inorganic filler contains specific silica particles and other fillers, it is the average particle size of the entire inorganic filler including specific silica particles and other fillers). It is preferably 4 μm to 100 μm, more preferably 7 μm to 70 μm, and still more preferably 7 μm to 40 μm. The thermal conductivity of the cured product of the sealing composition tends to increase as the average particle size of the inorganic filler increases. The average particle diameter of the inorganic filler can be measured by the following method.
向溶媒（純水）中添加1質量%～5質量%的範圍內的作為測定對象的無機填充材、以及1質量%～8質量%的界面活性劑，利用110 W的超音波清洗機振動30秒～5分鐘，將無機填充材分散。將分散液的約3 mL左右注入至測定用單元中並在25℃下進行測定。測定裝置是使用雷射繞射式粒度分佈計（堀場製作所股份有限公司，LA920）來測定體積基準的粒度分佈。平均粒徑是在體積基準的粒度分佈中作為自小徑側的累積成為50%時的粒徑（D50%）而求出。另外，折射率是使用氧化鋁的折射率。在無機填充材為氧化鋁與其他無機填充材的混合物的情況下，折射率設為使用氧化鋁的折射率。To the solvent (pure water), add the inorganic filler to be measured in the range of 1% to 5% by mass, and 1% to 8% by mass of surfactant, and vibrate 30 with a 110 W ultrasonic cleaner Second to 5 minutes, disperse the inorganic filler. About 3 mL of the dispersion is injected into the measurement cell and the measurement is performed at 25°C. The measuring device uses a laser diffraction particle size distribution meter (Horiba Manufacturing Co., Ltd., LA920) to measure the volume-based particle size distribution. The average particle size is calculated as the particle size (D50%) when the accumulation from the small diameter side becomes 50% in the volume-based particle size distribution. In addition, the refractive index is the refractive index of alumina used. When the inorganic filler is a mixture of alumina and other inorganic fillers, the refractive index is the refractive index of alumina.
就流動性及成形性的觀點而言，無機填充材的比表面積（例如，在無機填充材包含特定二氧化矽粒子及其他填充材的情況下，為包含特定二氧化矽粒子及其他填充材的無機填充材整體的比表面積）較佳為0.7 m2 /g～4.0 m2 /g，更佳為0.9 m2 /g～3.0 m2 /g，進而佳為1.0 m2 /g～2.5 m2 /g。 密封組成物的流動性具有隨著無機填充材的比表面積變小而變高的傾向。From the viewpoint of fluidity and formability, the specific surface area of the inorganic filler (for example, when the inorganic filler contains specific silica particles and other fillers, it is the specific surface area of the inorganic filler containing specific silica particles and other fillers). inorganic filler overall specific surface area) is preferably 0.7 m 2 /g~4.0 m 2 / g , more preferably 0.9 m 2 /g~3.0 m 2 / g , and further good as 1.0 m 2 /g~2.5 m 2 /g. The fluidity of the sealing composition tends to increase as the specific surface area of the inorganic filler decreases.
-特定矽烷化合物- 本揭示的密封組成物含有特定矽烷化合物（即，具有碳數6以上的鏈狀烴基鍵結於矽原子的結構的矽烷化合物）。 特定矽烷化合物具有碳數6以上的鏈狀烴基（以下，亦將碳數6以上的鏈狀烴基簡稱為鏈狀烴基）鍵結於矽原子的結構。鏈狀烴基可分支亦可具有取代基。另外，在本揭示中，鏈狀烴基的碳數是指不包含分支或取代基的碳的碳數。鏈狀烴基可包含不飽和鍵，亦可不包含，較佳為不包含不飽和鍵。 特定矽烷化合物被認為在密封組成物中作為無機填充材的偶合劑來發揮功能。-Specific silane compounds- The sealing composition of the present disclosure contains a specific silane compound (that is, a silane compound having a structure in which a chain hydrocarbon group having 6 or more carbon atoms is bonded to a silicon atom). The specific silane compound has a structure in which a chain hydrocarbon group with a carbon number of 6 or more (hereinafter, the chain hydrocarbon group with a carbon number of 6 or more is also simply referred to as a chain hydrocarbon group) is bonded to a silicon atom. The chain hydrocarbon group may be branched or may have a substituent. In addition, in the present disclosure, the carbon number of the chain hydrocarbon group refers to the carbon number of carbon that does not include a branch or a substituent. The chain hydrocarbon group may or may not contain an unsaturated bond, but preferably does not contain an unsaturated bond. The specific silane compound is considered to function as a coupling agent of an inorganic filler in the sealing composition.
特定矽烷化合物中鍵結於矽原子的鏈狀烴基的數量為1～4即可，較佳為1～3，更佳為1或2，進而佳為1。The number of chain hydrocarbon groups bonded to silicon atoms in the specific silane compound may be 1 to 4, preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.
當特定矽烷化合物中鍵結於矽原子的鏈狀烴基的數量為1～3時，鍵結於矽原子的、鏈狀烴基以外的原子或原子團並無特別限制，可分別獨立地為氫原子、碳數1～5的烷基、烷氧基、芳基、芳基氧基等。其中，特定矽烷化合物中的矽原子較佳為除了鏈狀烴基以外亦鍵結有一個或多個烷氧基，更佳為一個鏈狀烴基與三個烷氧基鍵結於矽原子。When the number of chain hydrocarbon groups bonded to silicon atoms in a particular silane compound is 1 to 3, there are no particular restrictions on atoms or atomic groups bonded to silicon atoms other than the chain hydrocarbon groups, and may be independently hydrogen atoms, C1-C5 alkyl group, alkoxy group, aryl group, aryloxy group, etc. Among them, the silicon atom in the specific silane compound preferably has one or more alkoxy groups bonded to the chain hydrocarbon group, and more preferably one chain hydrocarbon group and three alkoxy groups are bonded to the silicon atom.
特定矽烷化合物的鏈狀烴基的碳數為6以上，就抑制黏度的觀點而言，較佳為7以上，更佳為8以上。特定矽烷化合物的鏈狀烴基的碳數的上限並無特別限制，就在樹脂中的分散性、硬化物的物性平衡等觀點而言，較佳為12以下，更佳為11以下，進而佳為10以下。The carbon number of the chain hydrocarbon group of the specific silane compound is 6 or more, and from the viewpoint of suppressing the viscosity, it is preferably 7 or more, and more preferably 8 or more. The upper limit of the carbon number of the chain hydrocarbon group of the specific silane compound is not particularly limited. From the viewpoints of dispersibility in the resin and the balance of physical properties of the cured product, it is preferably 12 or less, more preferably 11 or less, and still more preferably 10 or less.
在鏈狀烴基具有取代基的情況下，取代基並無特別限定。取代基可存在於鏈狀烴基的末端，亦可存在於鏈狀烴基的側鏈。When the chain hydrocarbon group has a substituent, the substituent is not particularly limited. The substituent may be present at the terminal of the chain hydrocarbon group or may be present on the side chain of the chain hydrocarbon group.
鏈狀烴基較佳為具有選自由(甲基)丙烯醯基、環氧基及烷氧基所組成的群組中的至少一個官能基（以下，亦稱為「特定官能基」），更佳為具有選自由(甲基)丙烯醯基及環氧基所組成的群組中的至少一個官能基，進而佳為具有(甲基)丙烯醯基。特定官能基可存在於鏈狀烴基的末端，亦可存在於鏈狀烴基的側鏈。就抑制黏度的觀點而言，特定官能基較佳為存在於鏈狀烴基的末端。The chain hydrocarbon group preferably has at least one functional group selected from the group consisting of a (meth)acryloyl group, an epoxy group, and an alkoxy group (hereinafter, also referred to as a "specific functional group"), and more preferably It has at least one functional group selected from the group consisting of a (meth)acryloyl group and an epoxy group, More preferably, it has a (meth)acryloyl group. The specific functional group may be present at the end of the chain hydrocarbon group or may be present in the side chain of the chain hydrocarbon group. From the viewpoint of suppressing the viscosity, the specific functional group is preferably present at the end of the chain hydrocarbon group.
在鏈狀烴基具有(甲基)丙烯醯基的情況下，(甲基)丙烯醯基可直接鍵結於鏈狀烴基，亦可經由其他原子或原子團而鍵結。例如，鏈狀烴基亦可具有(甲基)丙烯醯氧基。其中，鏈狀烴基較佳為具有甲基丙烯醯氧基。When the chain hydrocarbon group has a (meth)acryloyl group, the (meth)acryloyl group may be directly bonded to the chain hydrocarbon group, or may be bonded via other atoms or atomic groups. For example, the chain hydrocarbon group may have a (meth)acryloxy group. Among them, the chain hydrocarbon group preferably has a methacryloxy group.
在鏈狀烴基具有環氧基的情況下，環氧基可直接鍵結於鏈狀烴基，亦可經由其他原子或原子團而鍵結。例如，鏈狀烴基亦可具有縮水甘油基氧基、脂環式環氧基等。其中，鏈狀烴基較佳為具有縮水甘油基氧基。When the chain hydrocarbon group has an epoxy group, the epoxy group may be directly bonded to the chain hydrocarbon group, or may be bonded via other atoms or atomic groups. For example, the chain hydrocarbon group may have a glycidyloxy group, an alicyclic epoxy group, and the like. Among them, the chain hydrocarbon group preferably has a glycidyloxy group.
在鏈狀烴基具有烷氧基的情況下，烷氧基可直接鍵結於鏈狀烴基，亦可經由其他原子或原子團而鍵結，較佳為直接鍵結於鏈狀烴基。烷氧基並無特別限定，可為甲氧基、乙氧基、丙氧基、異丙氧基等。其中，就容易獲得性的觀點而言，鏈狀烴基較佳為具有甲氧基。When the chain hydrocarbon group has an alkoxy group, the alkoxy group may be directly bonded to the chain hydrocarbon group, or may be bonded via other atoms or atomic groups, and is preferably directly bonded to the chain hydrocarbon group. The alkoxy group is not particularly limited, and may be methoxy, ethoxy, propoxy, isopropoxy and the like. Among them, from the viewpoint of easy availability, the chain hydrocarbon group preferably has a methoxy group.
特定矽烷化合物中選自由(甲基)丙烯醯基、環氧基及烷氧基所組成的群組中的至少一個官能基的當量（分子量/官能基數）並無特別限制。就密封組成物的低黏度化的觀點而言，較佳為200 g/eq～420 g/eq，更佳為210 g/eq～405 g/eq，進而佳為230 g/eq～390 g/eq。The equivalent weight (molecular weight/number of functional groups) of at least one functional group selected from the group consisting of (meth)acrylic group, epoxy group, and alkoxy group in the specific silane compound is not particularly limited. From the viewpoint of lowering the viscosity of the sealing composition, it is preferably 200 g/eq to 420 g/eq, more preferably 210 g/eq to 405 g/eq, and still more preferably 230 g/eq to 390 g/ eq.
作為特定矽烷化合物，可列舉：己基三甲氧基矽烷、庚基三甲氧基矽烷、辛基三甲氧基矽烷、己基三乙氧基矽烷、庚基三乙氧基矽烷、辛基三乙氧基矽烷、6-縮水甘油氧基己基三甲氧基矽烷、7-縮水甘油氧基庚基三甲氧基矽烷、8-縮水甘油氧基辛基三甲氧基矽烷、6-(甲基)丙烯醯氧基己基三甲氧基矽烷、7-(甲基)丙烯醯氧基庚基三甲氧基矽烷、8-(甲基)丙烯醯氧基辛基三甲氧基矽烷、癸基三甲氧基矽烷等。其中，就密封組成物的低黏度化的觀點而言，特定矽烷化合物較佳為8-縮水甘油氧基辛基三甲氧基矽烷、及8-甲基丙烯醯氧基辛基三甲氧基矽烷。特定矽烷化合物可單獨使用一種，亦可組合兩種以上來使用。Examples of specific silane compounds include: hexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, and octyltriethoxysilane , 6-glycidoxyhexyltrimethoxysilane, 7-glycidoxyheptyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 6-(meth)acryloxyhexyl Trimethoxysilane, 7-(meth)acryloxyheptyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, decyltrimethoxysilane, etc. Among them, from the viewpoint of reducing the viscosity of the sealing composition, the specific silane compound is preferably 8-glycidoxyoctyltrimethoxysilane and 8-methacryloxyoctyltrimethoxysilane. The specific silane compound may be used alone or in combination of two or more.
特定矽烷化合物可合成，亦可使用市售者。作為市售的特定矽烷化合物，可列舉：信越化學工業股份有限公司製造的KBM-3063（己基三甲氧基矽烷）、KBE-3063（己基三乙氧基矽烷）、KBE-3083（辛基三乙氧基矽烷）、KBM-4803（8-縮水甘油氧基辛基三甲氧基矽烷）、KBM-5803（8-甲基丙烯醯氧基辛基三甲氧基矽烷）、KBM-3103C（癸基三甲氧基矽烷）等。Specific silane compounds can be synthesized, and commercially available ones can also be used. Examples of commercially available specific silane compounds include: KBM-3063 (hexyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., KBE-3063 (hexyltriethoxysilane), KBE-3083 (octyltriethoxysilane) Oxysilane), KBM-4803 (8-glycidoxyoctyl trimethoxysilane), KBM-5803 (8-methacryloxy octyl trimethoxysilane), KBM-3103C (decyl trimethyl Oxysilane) and so on.
密封組成物中的特定矽烷化合物的含量並無特別限制。相對於無機填充材100質量份，特定矽烷化合物的含量可為0.01質量份以上，亦可為0.02質量份以上。而且，相對於無機填充材100質量份，特定矽烷化合物的含量較佳為5質量份以下，更佳為2.5質量份以下。若相對於無機填充材100質量份，特定矽烷化合物的含量為0.01質量份以上，則具有可獲得流動性高的組成物的傾向。若相對於無機填充材100質量份，特定矽烷化合物的含量為5質量份以下，則具有封裝體的成形性進一步提高的傾向。就兼顧流動性與封裝體的成形性的觀點而言，相對於無機填充材100質量份，特定矽烷化合物的含量較佳為0.05質量份～2.0質量份，更佳為0.1質量份～1.5質量份，進而佳為0.2質量份～1.0質量份。 而且，相對於密封組成物整體，特定矽烷化合物的含有率較佳為3質量%以下，更佳為2質量%以下，進而佳為1質量%以下，就發揮其效果的觀點而言，較佳為0.1質量%以上，更佳為0.15質量%以上，進而佳為0.2質量%以上。The content of the specific silane compound in the sealing composition is not particularly limited. The content of the specific silane compound may be 0.01 parts by mass or more, or 0.02 parts by mass or more with respect to 100 parts by mass of the inorganic filler. Furthermore, the content of the specific silane compound relative to 100 parts by mass of the inorganic filler is preferably 5 parts by mass or less, and more preferably 2.5 parts by mass or less. If the content of the specific silane compound is 0.01 parts by mass or more with respect to 100 parts by mass of the inorganic filler, a composition with high fluidity tends to be obtained. If the content of the specific silane compound is 5 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved. From the viewpoint of both fluidity and moldability of the package, relative to 100 parts by mass of the inorganic filler, the content of the specific silane compound is preferably 0.05 to 2.0 parts by mass, more preferably 0.1 to 1.5 parts by mass , More preferably 0.2 part by mass to 1.0 part by mass. Furthermore, the content of the specific silane compound relative to the entire sealing composition is preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less. From the viewpoint of exerting its effect, it is more preferable It is 0.1% by mass or more, more preferably 0.15% by mass or more, and still more preferably 0.2% by mass or more.
-其他成分- （其他偶合劑） 密封組成物除了所述特定矽烷化合物以外，亦可進而含有其他偶合劑。作為其他偶合劑，只要為使用了環氧樹脂的密封組成物中一般所使用者則並無特別限制。作為其他偶合劑，可列舉環氧基矽烷、巰基矽烷、胺基矽烷、烷基矽烷、脲基矽烷、乙烯基矽烷等矽烷系化合物（特定矽烷化合物除外）、鈦系化合物、鋁螯合物化合物、鋁/鋯系化合物等公知的偶合劑。其他偶合劑可單獨使用一種，亦可組合兩種以上來使用。-Other ingredients- (Other coupling agents) The sealing composition may further contain other coupling agents in addition to the specific silane compound. The other coupling agent is not particularly limited as long as it is generally used in sealing compositions using epoxy resin. Other coupling agents include epoxy silanes, mercapto silanes, amino silanes, alkyl silanes, ureido silanes, vinyl silanes and other silane-based compounds (except specific silane compounds), titanium-based compounds, and aluminum chelate compounds. , Aluminum/zirconium compounds and other well-known coupling agents. Other coupling agents can be used alone or in combination of two or more.
在密封組成物含有特定矽烷化合物以外的其他偶合劑的情況下，相對於無機填充材100質量份，特定矽烷化合物與其他偶合劑的合計含量可為0.01質量份以上，可為0.02質量份以上。而且，相對於無機填充材100質量份，特定矽烷化合物與其他偶合劑的合計含量較佳為5質量份以下，更佳為2.5質量份以下。若相對於無機填充材100質量份，特定矽烷化合物與其他偶合劑的合計含量為0.01質量份以上，則具有可獲得流動性高的組成物的傾向。若相對於無機填充材100質量份，特定矽烷化合物與其他偶合劑的合計含量為5質量份以下，則具有封裝體的成形性進一步提高的傾向。就兼顧流動性與封裝體的成形性的觀點而言，相對於無機填充材100質量份，特定矽烷化合物與其他偶合劑的合計含量較佳為0.05質量份～2.0質量份，更佳為0.1質量份～1.5質量份，進而佳為0.2質量份～1.0質量份。 而且，相對於密封組成物整體，特定矽烷化合物與其他偶合劑的合計含有率較佳為3質量%以下，更佳為2質量%以下，進而佳為1質量%以下，就發揮其效果的觀點而言，較佳為0.1質量%以上，更佳為0.15質量%以上，進而佳為0.2質量%以上。When the sealing composition contains a coupling agent other than the specific silane compound, the total content of the specific silane compound and the other coupling agent may be 0.01 parts by mass or more, or 0.02 parts by mass or more with respect to 100 parts by mass of the inorganic filler. Furthermore, the total content of the specific silane compound and the other coupling agent is preferably 5 parts by mass or less, and more preferably 2.5 parts by mass or less with respect to 100 parts by mass of the inorganic filler. If the total content of the specific silane compound and the other coupling agent is 0.01 parts by mass or more with respect to 100 parts by mass of the inorganic filler, a composition with high fluidity tends to be obtained. If the total content of the specific silane compound and the other coupling agent is 5 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved. From the viewpoint of both the fluidity and the moldability of the package, the total content of the specific silane compound and other coupling agents is preferably 0.05 to 2.0 parts by mass, more preferably 0.1 parts by mass relative to 100 parts by mass of the inorganic filler Parts to 1.5 parts by mass, more preferably 0.2 parts by mass to 1.0 parts by mass. Furthermore, the total content of the specific silane compound and other coupling agents relative to the entire sealing composition is preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less, from the viewpoint of exerting its effect In particular, it is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and still more preferably 0.2% by mass or more.
在密封組成物含有特定矽烷化合物以外的其他偶合劑的情況下，就良好地發揮特定矽烷化合物的作用的觀點而言，相對於特定矽烷化合物與其他偶合劑的合計量，其他偶合劑的含有率較佳為90質量%以下，更佳為70質量%以下，進而佳為50質量%以下，特佳為40質量%以下，極佳為20質量%以下，最佳為10質量%以下。When the sealing composition contains a coupling agent other than the specific silane compound, the content of the other coupling agent is relative to the total amount of the specific silane compound and the other coupling agent from the viewpoint that the specific silane compound functions well It is preferably 90% by mass or less, more preferably 70% by mass or less, still more preferably 50% by mass or less, particularly preferably 40% by mass or less, extremely preferably 20% by mass or less, and most preferably 10% by mass or less.
（硬化促進劑） 密封組成物亦可進而含有硬化促進劑。硬化促進劑的種類並無特別限制，可使用公知的硬化促進劑。 作為硬化促進劑，具體而言，可列舉：1,8-二氮雜-雙環[5.4.0]十一烯-7、1,5-二氮雜-雙環[4.3.0]壬烯、5,6-二丁基胺基-1,8-二氮雜-雙環[5.4.0]十一烯-7等環脒化合物；對環脒化合物加成馬來酸酐、1,4-苯醌、2,5-甲苯醌、1,4-萘醌、2,3-二甲基苯醌、2,6-二甲基苯醌、2,3-二甲氧基-5-甲基-1,4-苯醌、2,3-二甲氧基-1,4-苯醌、苯基-1,4-苯醌等醌化合物、重氮苯基甲烷、苯酚樹脂等具有π鍵的化合物而成的具有分子內極化的化合物；苄基二甲基胺、三乙醇胺、二甲基胺基乙醇、三(二甲基胺基甲基)苯酚等三級胺化合物；三級胺化合物的衍生物；2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑等咪唑化合物；咪唑化合物的衍生物；三丁基膦、甲基二苯基膦、三苯基膦、三(4-甲基苯基)膦、二苯基膦、苯基膦等有機膦化合物；對有機膦化合物加成馬來酸酐、所述醌化合物、重氮苯基甲烷、苯酚樹脂等具有π鍵的化合物而成的具有分子內極化的磷化合物；四苯基鏻四苯基硼酸鹽、三苯基膦四苯基硼酸鹽、2-乙基-4-甲基咪唑四苯基硼酸鹽、N-甲基嗎啉四苯基硼酸鹽等四苯基硼鹽；四苯基硼鹽的衍生物；三苯基鏻-三苯基硼烷、N-甲基嗎啉四苯基鏻-四苯基硼酸鹽等膦化合物與四苯基硼鹽的加成物等。硬化促進劑可單獨使用一種，亦可併用兩種以上。(Hardening accelerator) The sealing composition may further contain a hardening accelerator. The kind of hardening accelerator is not particularly limited, and known hardening accelerators can be used. Specific examples of the hardening accelerator include: 1,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diaza-bicyclo[4.3.0]nonene, 5 ,6-Dibutylamino-1,8-diaza-bicyclo[5.4.0]undecene-7 and other cyclic amidine compounds; p-cyclic amidine compounds add maleic anhydride, 1,4-benzoquinone, 2,5-Methylbenzoquinone, 1,4-Naphthoquinone, 2,3-Dimethylbenzoquinone, 2,6-Dimethylbenzoquinone, 2,3-Dimethoxy-5-methyl-1, Quinone compounds such as 4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, diazophenylmethane, phenol resin and other compounds with π bonds Compounds with intramolecular polarization; tertiary amine compounds such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; derivatives of tertiary amine compounds ; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and other imidazole compounds; derivatives of imidazole compounds; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, Tris (4-methylphenyl) phosphine, diphenyl phosphine, phenyl phosphine and other organic phosphine compounds; addition of maleic anhydride to organic phosphine compounds, the quinone compounds, diazophenylmethane, phenol resins, etc. have π Phosphorus compound with intramolecular polarization formed from the bond compound; tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate , N-methylmorpholine tetraphenyl borate and other tetraphenyl boron salts; derivatives of tetraphenyl boron salt; triphenyl phosphonium-triphenyl borane, N-methylmorpholine tetraphenyl phosphonium- Addition products of phosphine compounds such as tetraphenyl borate and tetraphenyl borate. A hardening accelerator may be used individually by 1 type, and may use 2 or more types together.
該些中，硬化促進劑較佳為磷系硬化促進劑，其中更佳為有機膦化合物、有機膦化合物的加成物、及膦化合物與四苯基硼鹽的加成物，進而佳為有機膦化合物及有機膦化合物的加成物，特佳為對有機膦化合物加成醌化合物而成的化合物。 另外，「磷系硬化促進劑」是具有磷原子的硬化促進劑。Among these, the hardening accelerator is preferably a phosphorus-based hardening accelerator, and among them, organic phosphine compounds, adducts of organic phosphine compounds, and adducts of phosphine compounds and tetraphenyl boron salt are more preferable, and organic The addition product of a phosphine compound and an organic phosphine compound is particularly preferably a compound obtained by adding a quinone compound to an organic phosphine compound. In addition, the "phosphorus-based hardening accelerator" is a hardening accelerator having phosphorus atoms.
相對於環氧樹脂與硬化劑的合計量，硬化促進劑的含有率較佳為0.1質量%～8質量%。The content rate of the hardening accelerator is preferably 0.1% by mass to 8% by mass relative to the total amount of the epoxy resin and the hardener.
（離子捕捉劑） 密封組成物亦可進而含有離子捕捉劑。 本揭示中可使用的離子捕捉劑只要為用於半導體裝置的製造用途中的密封材中一般所使用的離子捕捉劑，則並無特別限制。作為離子捕捉劑，可列舉下述通式（3）或下述通式（4）所表示的化合物等。(Ion trap) The sealing composition may further contain an ion scavenger. The ion scavenger that can be used in the present disclosure is not particularly limited as long as it is an ion scavenger that is generally used in sealing materials used in the production of semiconductor devices. As an ion scavenger, the compound etc. which are represented by following general formula (3) or following general formula (4) are mentioned.
Mg1-a Ala (OH)2 (CO3 )a/2 ･uH2 O （3） （通式（3）中，a為0>a≦0.5，u為正數） BiOb (OH)c (NO3 )d （4） （通式（4）中，b為0.9≦b≦1.1，c為0.6≦c≦0.8，d為0.2≦d≦0.4）Mg 1-a Al a (OH) 2 (CO 3 ) a/2 ･uH 2 O (3) (In the general formula (3), a is 0>a≦0.5, u is a positive number) BiO b (OH) c (NO 3 ) d (4) (In the general formula (4), b is 0.9≦b≦1.1, c is 0.6≦c≦0.8, and d is 0.2≦d≦0.4)
離子捕捉劑可作為市售品而獲取。作為通式（3）所表示的化合物，例如可作為市售品而獲取「DHT-4A」（協和化學工業股份有限公司，商品名）。而且，作為通式（4）所表示的化合物，例如可作為市售品而獲取「IXE500」（東亞合成股份有限公司，商品名）。The ion scavenger can be obtained as a commercially available product. As the compound represented by the general formula (3), for example, “DHT-4A” (Kyowa Chemical Industry Co., Ltd., trade name) can be obtained as a commercially available product. In addition, as the compound represented by the general formula (4), for example, "IXE500" (Toagosei Co., Ltd., trade name) can be obtained as a commercially available product.
而且，作為所述以外的離子捕捉劑，可列舉選自鎂、鋁、鈦、鋯、銻等中的元素的含水氧化物等。 離子捕捉劑可單獨使用一種，亦可併用兩種以上。Furthermore, examples of ion scavengers other than those described above include hydrated oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, and the like. One kind of ion scavenger may be used alone, or two or more kinds may be used in combination.
在密封組成物含有離子捕捉劑的情況下，就實現充分的耐濕可靠性的觀點而言，相對於環氧樹脂100質量份，離子捕捉劑的含量較佳為1質量份以上。就充分發揮其他成分的效果的觀點而言，相對於環氧樹脂100質量份，離子捕捉劑的含量較佳為15質量份以下。When the sealing composition contains an ion scavenger, from the viewpoint of achieving sufficient moisture resistance reliability, the content of the ion scavenger is preferably 1 part by mass or more with respect to 100 parts by mass of the epoxy resin. From the viewpoint of fully exerting the effects of other components, the content of the ion scavenger is preferably 15 parts by mass or less with respect to 100 parts by mass of the epoxy resin.
而且，離子捕捉劑的平均粒徑較佳為0.1 μm～3.0 μm，最大粒徑較佳為10 μm以下。離子捕捉劑的平均粒徑可與無機填充材的情況同樣地進行測定。Furthermore, the average particle diameter of the ion trap is preferably 0.1 μm to 3.0 μm, and the maximum particle diameter is preferably 10 μm or less. The average particle size of the ion scavenger can be measured in the same manner as in the case of inorganic fillers.
（脫模劑） 密封組成物亦可進而含有脫模劑。脫模劑的種類並無特別限制，可使用公知的脫模劑。具體而言，作為脫模劑，可列舉：高級脂肪酸、棕櫚蠟、褐煤蠟、聚乙烯系蠟等。脫模劑可單獨使用一種，亦可併用兩種以上。 在密封組成物含有脫模劑的情況下，相對於環氧樹脂與硬化劑的合計量，脫模劑的含有率較佳為10質量%以下，就發揮其效果的觀點而言，較佳為0.5質量%以上。(Release agent) The sealing composition may further contain a mold release agent. The kind of mold release agent is not specifically limited, A well-known mold release agent can be used. Specifically, as a mold release agent, higher fatty acid, palm wax, montan wax, polyethylene wax, etc. are mentioned. One type of release agent may be used alone, or two or more types may be used in combination. When the sealing composition contains a mold release agent, the content of the mold release agent relative to the total amount of the epoxy resin and the hardener is preferably 10% by mass or less, and from the viewpoint of exerting its effect, it is preferably 0.5% by mass or more.
（著色劑及改質劑） 密封組成物亦可含有著色劑（碳黑等）。而且，密封組成物亦可含有改質劑（矽酮、矽酮橡膠等）。著色劑及改質劑可分別單獨使用一種，亦可併用兩種以上。(Colorants and modifiers) The sealing composition may contain a colorant (carbon black, etc.). Furthermore, the sealing composition may also contain modifiers (silicone, silicone rubber, etc.). A colorant and a modifier may be used individually by 1 type, respectively, and may use 2 or more types together.
在使用碳黑等導電性粒子作為著色劑的情況下，導電性粒子較佳為粒徑10 μm以上的粒子的含有率為1質量%以下。 在密封組成物含有導電性粒子的情況下，相對於環氧樹脂與硬化劑的合計量，導電性粒子的含有率較佳為3質量%以下。In the case of using conductive particles such as carbon black as the colorant, the conductive particles preferably have a particle size of 10 μm or more and the content of particles is 1% by mass or less. When the sealing composition contains conductive particles, the content of the conductive particles is preferably 3% by mass or less with respect to the total amount of the epoxy resin and the curing agent.
（其他添加劑） 密封組成物可視需要進而包含其他添加劑。 作為其他添加劑，可列舉阻燃劑、陰離子交換體、塑化劑等。而且，密封組成物中亦可視需要添加該技術領域眾所周知的各種添加劑。(Other additives) The sealing composition may further contain other additives as needed. Examples of other additives include flame retardants, anion exchangers, and plasticizers. Furthermore, various additives well known in the technical field may be added to the sealing composition as needed.
＜密封組成物的製作方法＞ 密封組成物的製作方法並無特別限制，可藉由公知的方法進行。例如，可藉由利用混合機等將規定調配量的原材料的混合物充分混合後，利用熱輥、擠出機等加以混煉，並經過冷卻、粉碎等處理而製作密封組成物。密封組成物的狀態並無特別限制，可為粉末狀、固體狀、液體狀等。＜Method of making sealing composition＞ The manufacturing method of the sealing composition is not particularly limited, and it can be performed by a known method. For example, a mixture of raw materials in a predetermined amount can be sufficiently mixed with a mixer or the like, kneaded with a hot roll, an extruder, etc., and then cooled, pulverized, etc., to produce a sealing composition. The state of the sealing composition is not particularly limited, and may be powder, solid, liquid, or the like.
＜密封組成物的特性＞ 將密封組成物在硬化溫度175℃及硬化時間90秒的條件下加熱硬化時所獲得的硬化物的蕭氏D所表示的熱時硬度較佳為70以上，更佳為74以上，進而佳為76以上。 藉由使所述熱時硬度為所述範圍，藉由轉移模塑法進行半導體元件的密封時的連續成形性變良好。＜Characteristics of sealing composition＞ The hardness of the cured product obtained when the sealing composition is heated and cured under the conditions of a curing temperature of 175°C and a curing time of 90 seconds is preferably 70 or more, more preferably 74 or more, and still more preferably 76 or more. By setting the heat-time hardness within the above-mentioned range, the continuous moldability at the time of sealing the semiconductor element by the transfer molding method becomes good.
＜半導體裝置＞ 本揭示的半導體裝置包含半導體元件、以及將所述半導體元件密封而成的本揭示的密封組成物的硬化物。＜Semiconductor device＞ The semiconductor device of the present disclosure includes a semiconductor element and a cured product of the sealing composition of the present disclosure obtained by sealing the semiconductor element.
使用密封組成物來密封半導體元件的方法並無特別限定，可應用公知的方法。一般為轉移模塑法等，但亦可使用壓縮模塑法、噴射成形法、壓縮成形法等。The method of sealing a semiconductor element using a sealing composition is not specifically limited, A well-known method can be applied. Generally, transfer molding is used, but compression molding, injection molding, and compression molding may also be used.
本揭示的半導體裝置作為積體電路（Integrated Circuit，IC）、大規模積體電路（Large-Scale Integration，LSI）等而較佳。 [實施例]The semiconductor device of the present disclosure is preferable as an integrated circuit (Integrated Circuit, IC), a large-scale integrated circuit (Large-Scale Integration, LSI), or the like. [Example]
以下，參照以下的實施例對本發明的一實施形態進行說明，但本發明並不限定於該些。而且，表中的數值只要無特別說明，則是指「質量份」。Hereinafter, an embodiment of the present invention will be described with reference to the following examples, but the present invention is not limited to these. In addition, the numerical values in the table refer to "parts by mass" unless otherwise specified.
＜實施例1～實施例5及比較例1～比較例5＞ 將下述所示的成分按照表1及表2中所示的調配比例（質量份）預先混合（乾式摻雜）後，利用雙軸捏合機進行混煉，並進行冷卻粉碎而製造粉末狀的密封組成物。 另外，表1及表2中所示的成分的詳細情況如下。<Example 1 to Example 5 and Comparative Example 1 to Comparative Example 5> The ingredients shown below were pre-mixed (dry-doped) according to the blending ratios (parts by mass) shown in Table 1 and Table 2, and then kneaded using a biaxial kneader, and cooled and crushed to produce a powder Seal the composition. In addition, the details of the components shown in Table 1 and Table 2 are as follows.
（A）環氧樹脂 環氧樹脂A1：三菱化學股份有限公司，商品名「YX4000H」，環氧基當量「192 g/eq」，軟化點「107℃」，聯苯型環氧樹脂，具有所述通式（1）所表示的二價的連結基的環氧樹脂 （B）硬化劑 硬化劑B1：三苯基甲烷型酚樹脂，愛沃特（AirWater）股份有限公司，商品名「HE910-09」，羥基當量「104 g/eq」，軟化點「80℃」，所述通式（2）所表示的酚樹脂 （C）硬化促進劑 硬化促進劑C1：磷系硬化促進劑（三丁基膦與苯醌的加成物） （D）偶合劑 偶合劑D1：3-甲基丙烯醯氧基丙基三甲氧基矽烷，信越化學工業股份有限公司，商品名「KBM-503」，具有碳數為3的烴基的矽烷化合物 偶合劑D2：8-甲基丙烯醯氧基辛基三甲氧基矽烷，信越化學工業股份有限公司，商品名「KBM-5803」，具有碳數為8的鏈狀烴基的矽烷化合物(A) Epoxy resin Epoxy resin A1: Mitsubishi Chemical Corporation, trade name "YX4000H", epoxy equivalent "192 g/eq", softening point "107°C", biphenyl type epoxy resin, with the general formula (1) The epoxy resin of the divalent linking group represented (B) Hardener Hardener B1: Triphenylmethane type phenol resin, AirWater Co., Ltd., trade name "HE910-09", hydroxyl equivalent "104 g/eq", softening point "80°C", the general formula (2) Phenolic resin represented (C) Hardening accelerator Hardening accelerator C1: Phosphorus hardening accelerator (addition product of tributylphosphine and benzoquinone) (D) Coupling agent Coupling agent D1: 3-methacryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., trade name "KBM-503", silane compound with a hydrocarbon group with 3 carbon atoms Coupling agent D2: 8-methacryloxy octyl trimethoxysilane, Shin-Etsu Chemical Co., Ltd., trade name "KBM-5803", silane compound with a chain hydrocarbon group with 8 carbon atoms
（E）脫模劑 脫模劑E1：褐煤蠟，科萊恩（Clariant）公司，商品名「HW-E」 （F）著色劑 顏料F1：碳黑，三菱化學股份有限公司，商品名「MA600」 （G）添加劑 添加劑G1：三苯基氧化膦 （H）改質劑 改質劑H1：矽酮，東麗道康寧（Toray Dow Corning）股份有限公司，商品名「BY16-876」(E) Release agent Release agent E1: montan wax, Clariant, trade name "HW-E" (F) Coloring agent Pigment F1: Carbon black, Mitsubishi Chemical Corporation, trade name "MA600" (G) Additives Additive G1: Triphenylphosphine oxide (H) Modifier Modifier H1: Silicone, Toray Dow Corning Co., Ltd., trade name "BY16-876"
（I）無機填充材 填料I1：二氧化矽粒子，球狀，比表面積｢190 m2 /g～210 m2 /g｣，特定二氧化矽粒子 填料I2：氧化鋁粒子，球狀，平均粒徑｢0.7 μm｣ 填料I3：氧化鋁粒子，球狀，平均粒徑｢10 μm｣(I) Inorganic filler filler I1: Silica particles, spherical, specific surface area "190 m 2 /g～210 m 2 /g", specific silica particle filler I2: Alumina particles, spherical, average particle size Diameter "0.7 μm" Filler I3: Alumina particles, spherical, average particle size "10 μm"
-評價- 藉由以下的特性試驗對實施例及比較例中製作的密封組成物的特性進行評價。將評價結果示於下述表1及表2。-Evaluation- The characteristics of the sealing compositions produced in the examples and comparative examples were evaluated by the following characteristic tests. The evaluation results are shown in Table 1 and Table 2 below.
（熱時硬度） 使用上述所獲得的密封組成物，藉由轉注成形機，在金屬模具溫度175℃、成形壓力6.9 MPa、硬化時間90秒的條件下進行成形，製作直徑50 mm×厚度3 mm的圓板形狀的試驗片。成形後立即使用蕭氏D型硬度計（高分子計量器股份有限公司，阿斯卡（ASKER），類型D硬度計（type D durometer））測定熱時硬度。(Hardness when hot) Using the above-obtained sealing composition, a transfer molding machine was used to mold under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds to produce a circular plate with a diameter of 50 mm and a thickness of 3 mm. Test piece. Immediately after forming, use the Shore D durometer (ASKER, type D durometer) to measure the hot hardness.
（凝膠時間（gel time）） 硬化性是基於使用凝膠化試驗機如下測定的凝膠時間來進行評價。 將上述所獲得的密封組成物0.5 g載置於加熱為175℃的熱板上，使用夾具以20轉/分～25轉/分的旋轉速度，將試樣均勻地擴展為2.0 cm～2.5 cm的圓狀。測量將試樣載置於熱板後，至試樣的黏性消失，成為凝膠狀態而可自熱板剝離為止的時間，將其作為凝膠時間（sec）來測定。 將結果示於表1及表2。在相對於環氧基100質量份，使用了相同的觸媒量的情況下，凝膠時間越短，硬化性越優異。(Gel time) The curability is evaluated based on the gel time measured as follows using a gelation tester. Place 0.5 g of the sealing composition obtained above on a hot plate heated at 175°C, and use a jig to uniformly expand the sample to 2.0 cm to 2.5 cm at a rotation speed of 20 rpm to 25 rpm The round shape. After the sample is placed on the hot plate, the time until the viscosity of the sample disappears and becomes a gel state and can be peeled from the hot plate is measured, and this is measured as the gel time (sec). The results are shown in Table 1 and Table 2. When the same amount of the catalyst is used with respect to 100 parts by mass of the epoxy group, the shorter the gel time, the better the curability.
（圓盤狀流動（disk flow，DF）） 使上述所獲得的密封組成物通過二段篩（上段：2.38 mm、下段：0.5 mm），將下段殘留的試樣秤量7 g。將所述密封組成物放置於加熱為180℃的平滑的金屬模具之上，將同樣地加熱為180℃的8 kg的平滑的金屬模具放置於試樣之上放置60秒。其後，求出所獲得的圓板狀成形品的直徑（mm）與短徑（mm）的平均值（mm），將所述平均值（mm）設為圓盤狀流動（DF）。 將結果示於表1及表2。圓盤狀流動越長，流動性越優異。(Disk flow (DF)) The sealing composition obtained above is passed through a two-stage sieve (upper stage: 2.38 mm, lower stage: 0.5 mm), and the remaining sample in the lower stage is weighed by 7 g. The sealing composition was placed on a smooth metal mold heated to 180° C., and a smooth metal mold of 8 kg heated to 180° C. was placed on the sample for 60 seconds. After that, the average value (mm) of the diameter (mm) and the short diameter (mm) of the obtained disc-shaped molded article was determined, and the average value (mm) was defined as a disk-shaped flow (DF). The results are shown in Table 1 and Table 2. The longer the disc-like flow, the better the fluidity.
（毛邊） 將上述所獲得的密封組成物15 g載置於壓制熱板上的180℃的金屬模具上，以硬化時間90秒進行成形。成形後，使用遊標卡尺測定金屬模具中所製作的50 μm、30 μm、20 μm、10 μm、5 μm及2 μm的狹縫中密封組成物流動最長的部分的長度，將該測定值設為毛邊長度。 結果，可知：在實施例1～實施例5的任一者中，毛邊長度均為10 mm以下，毛邊的產生得到了抑制。(Burr) 15 g of the sealing composition obtained above was placed on a metal mold at 180°C on a pressing hot plate, and molded with a curing time of 90 seconds. After molding, use a vernier caliper to measure the length of the part where the sealing composition flows the longest in the 50 μm, 30 μm, 20 μm, 10 μm, 5 μm, and 2 μm slits made in the mold, and set the measured value as the burr length. As a result, it can be seen that in any of Examples 1 to 5, the burr length is 10 mm or less, and the generation of burr is suppressed.
（導熱率） 使用上述所獲得的密封組成物，藉由轉注成形機，在金屬模具溫度175℃～180℃、成形壓力7 MPa、硬化時間300秒的條件下，製作導熱率評價用的試驗片。繼而，針對成形的試驗片，測定厚度方向的熱擴散率。熱擴散率的測定是藉由雷射閃光（Laser Flash）法（裝置：LFA467奈米閃光（LFA467 nanoflash），耐馳（NETZSCH）公司）來進行。脈衝光照射是在脈衝寬度0.31（ms）、施加電壓247 V的條件下來進行。測定是在環境溫度25℃±1℃下進行。而且，所述試驗片的密度是使用電子比重計（AUX220，島津製作所股份有限公司）來進行測定。比熱是使用藉由各材料的比熱的文獻值與調配比率而算出的密封組成物的理論比熱。 繼而，使用式（5）將比熱及密度乘以熱擴散率，藉此獲得導熱率的值。 λ=α×Cp×ρ･･･式（5） （式（5）中，λ表示導熱率（W/（m･K）），α表示熱擴散率（m2 /s）、Cp表示比熱（J/（kg･K）），ρ表示密度（kg/m3 ）） 將結果示於表1及表2。(Thermal conductivity) Using the sealing composition obtained above, a transfer molding machine was used to prepare a test piece for thermal conductivity evaluation under the conditions of a mold temperature of 175°C to 180°C, a molding pressure of 7 MPa, and a curing time of 300 seconds . Then, for the molded test piece, the thermal diffusivity in the thickness direction was measured. The thermal diffusivity is measured by the laser flash method (device: LFA467 nanoflash, NETZSCH company). Pulsed light irradiation was performed under the conditions of a pulse width of 0.31 (ms) and an applied voltage of 247 V. The measurement is carried out at an ambient temperature of 25°C ± 1°C. In addition, the density of the test piece was measured using an electronic hydrometer (AUX220, Shimadzu Corporation). The specific heat is the theoretical specific heat of the sealing composition calculated from the literature value and the blending ratio of the specific heat of each material. Then, use formula (5) to multiply the specific heat and density by the thermal diffusivity to obtain the thermal conductivity value. λ=α×Cp×ρ･･･Eq. (5) (In Eq. (5), λ represents the thermal conductivity (W/(m･K)), α represents the thermal diffusivity (m 2 /s), and Cp represents the specific heat (J/(kg･K)), ρ means density (kg/m 3 )) The results are shown in Table 1 and Table 2.
[表1]
[表2]
表1及表2中，「填料的平均粒徑」是指所使用的無機填充材整體中的體積基準的平均粒徑，「填料含有率」是指所使用的無機填充材整體相對於密封組成物整體的含有率。 根據表1及表2的評價結果可明確：含有特定矽烷化合物的實施例1～實施例5的密封組成物相較於不含特定矽烷化合物的比較例1～比較例5的密封組成物，獲得了流動性高，而且導熱率高的硬化物。而且，可知：在比較例1～比較例5的密封組成物中，相對於填料含有率的增加而言，導熱性的上升率低，導熱性成為飽和狀態，相對於此，在實施例1～實施例3的密封組成物中，伴隨著填料含有率的增加，導熱率變高。In Tables 1 and 2, the "average particle size of the filler" refers to the volume-based average particle size in the entire inorganic filler used, and the "filler content" refers to the overall inorganic filler used relative to the sealing composition The content rate of the whole thing. According to the evaluation results of Table 1 and Table 2, it is clear that the sealing composition of Examples 1 to 5 containing the specific silane compound is obtained compared to the sealing composition of Comparative Example 1 to Comparative Example 5 not containing the specific silane compound A hardened product with high fluidity and high thermal conductivity. Furthermore, it can be seen that in the sealing composition of Comparative Examples 1 to 5, the increase rate of the thermal conductivity is low relative to the increase in the filler content, and the thermal conductivity becomes saturated. In contrast, in Examples 1 to 5 In the sealing composition of Example 3, as the filler content increased, the thermal conductivity became higher.
2018年12月21日申請的日本專利申請案2018-239254號的揭示的整體藉由參照而併入至本說明書中。 關於本說明書中所記載的所有文獻、專利申請案、及技術規格，與具體且各個地記載有藉由參照而併入各個文獻、專利申請案、及技術規格的情況同等程度地，併入至本說明書中。The entire disclosure of Japanese Patent Application No. 2018-239254 filed on December 21, 2018 is incorporated into this specification by reference. Regarding all the documents, patent applications, and technical specifications described in this specification, they are incorporated into the same degree as the cases where each document, patent application, and technical specifications are specifically and individually described and incorporated by reference. In this manual.
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