TW202313838A

TW202313838A - Curable resin composition and electronic component device

Info

Publication number: TW202313838A
Application number: TW111132328A
Authority: TW
Inventors: 姜東哲; 畠山恵一; 西山智雄; 山本貴耶; 金貴和; 横倉亜唯
Original assignee: 日商昭和電工材料股份有限公司
Priority date: 2021-08-30
Filing date: 2022-08-26
Publication date: 2023-04-01
Also published as: CN117858924A; WO2023032860A1

Abstract

A curable resin composition, wherein in a graph obtained by measuring the dynamic viscoelasticity of a resin cured article of the curable resin composition, a vertical axis is tan[delta] and a horizontal axis is a temperature of 30 DEG C to 260 DEG C, wherein (1) a temperature at which the tan[delta] is maximum is less than 120 DEG C, (2) a maximum value of the tan[delta] is greater than 0.400, and (3) a sum of the tan[delta] values at each temperature of 220 DEG C, 230 DEG C, 240 DEG C and 250 DEG C is greater than 0.400 or a sum of the tan[delta] values at each temperature of 70 DEG C, 80 DEG C and 90 DEG C is greater than 0.600.

Description

硬化性樹脂組成物及電子零件裝置Curable resin composition and electronic component device

本揭示是有關於一種硬化性樹脂組成物及電子零件裝置。This disclosure relates to a curable resin composition and an electronic component device.

近年來，半導體元件的高密度安裝化不斷發展。伴隨於此，樹脂密封型半導體裝置相對於先前的引腳***型的封裝而表面安裝型的封裝成為主流。表面安裝型的積體電路（Integrated Circuit，IC）、大規模積體電路（Large Scale Integration，LSI）等為了提高安裝密度且降低安裝高度而成為薄型且小型的封裝。因此，元件相對於封裝的佔有面積變大，封裝的厚度變得非常薄。In recent years, high-density mounting of semiconductor elements has progressed. Along with this, the resin-sealed type semiconductor device has become the mainstream of the surface mount type package rather than the conventional pin insertion type package. Surface-mount integrated circuits (Integrated Circuit, IC) and large scale integrated circuits (Large Scale Integration, LSI), etc., have become thin and small packages in order to increase the mounting density and reduce the mounting height. Therefore, the area occupied by the element with respect to the package becomes larger, and the thickness of the package becomes very thin.

進而，該些封裝的安裝方法與引腳***型封裝不同。即，引腳***型封裝是於將引腳***至配線板後，自配線板的背面進行焊接，因此封裝不會直接暴露於高溫下。但是，表面安裝型IC是於配線板表面進行暫時固定，並利用焊料浴、回焊裝置等進行處理，因此封裝會直接暴露於焊接溫度（回焊溫度）下。其結果，於封裝吸濕的情況下，於回焊時吸濕水分氣化，所產生的蒸氣壓作為剝離應力發揮作用，產生元件、引線框架等支撐構件與密封材之間的剝離，而成為封裝裂紋的產生、電特性不良等的原因。因此，期望開發一種與支撐構件的接著性優異、進而焊料耐熱性（耐回焊性）優異的密封材料。 Furthermore, the mounting method of these packages is different from that of pin insertion type packages. That is, in the pin insertion type package, after the pins are inserted into the wiring board, soldering is performed from the back surface of the wiring board, so the package is not directly exposed to high temperature. However, surface mount type ICs are temporarily fixed on the surface of the wiring board and processed with a solder bath, reflow equipment, etc., so the package is directly exposed to the soldering temperature (reflow temperature). As a result, when the package absorbs moisture, the absorbed moisture vaporizes during reflow, and the generated vapor pressure acts as peeling stress, causing peeling between supporting members such as elements and lead frames and the sealing material, resulting in Causes of package cracks, poor electrical characteristics, etc. Therefore, development of a sealing material excellent in adhesiveness with a support member and excellent in solder heat resistance (reflow resistance) has been desired.

作為密封材料，已知有含有環氧樹脂及酚系硬化劑的硬化性樹脂組成物。As a sealing material, a curable resin composition containing an epoxy resin and a phenolic curing agent is known.

[發明所欲解決之課題] 專利文獻1中所提出的硬化性樹脂組成物的耐回焊性有進一步改善的餘地。本揭示是鑒於所述狀況而成，本揭示所欲解決的課題為欲提供一種具有優異的耐回焊性的硬化性樹脂組成物及包括由該硬化性樹脂組成物密封的元件的電子零件裝置。 [解決課題之手段] [Problem to be Solved by the Invention] The reflow resistance of the curable resin composition proposed in Patent Document 1 has room for further improvement. The present disclosure is made in view of the above situation, and the problem to be solved by the present disclosure is to provide a curable resin composition having excellent reflow resistance and an electronic component device including a component sealed with the curable resin composition . [Means to solve the problem]

用以達成所述課題的具體方法如以下所述。＜1＞一種硬化性樹脂組成物，其中，於藉由對硬化性樹脂組成物的樹脂硬化物進行動態黏彈性測定而獲得的縱軸為tanδ及橫軸為30℃～260℃的溫度的圖表中，（1）tanδ成為最大時的溫度未滿120℃，（2）tanδ的最大值超過0.400，且（3）220℃、230℃、240℃及250℃各溫度下的tanδ值的合計超過0.400。＜2＞一種硬化性樹脂組成物，其中，於藉由對硬化性樹脂組成物的樹脂硬化物進行動態黏彈性測定而獲得的縱軸為tanδ及橫軸為30℃～260℃的溫度的圖表中，70℃、80℃及90℃各溫度下的tanδ值的合計超過0.600。＜3＞如所述＜1＞或＜2＞所記載的硬化性樹脂組成物，其中，於將所述圖表中的tanδ的最大值設為100時，tanδ成為最大時的溫度-10℃的至少任一溫度下的tanδ值超過60。＜4＞如所述＜1＞至＜3＞中任一項所記載的硬化性樹脂組成物，其中，藉由對硬化性樹脂組成物的樹脂硬化物進行動態黏彈性測定而求出的260℃下的貯存黏彈性為450 MPa以下。＜5＞如所述＜1＞至＜4＞中任一項所記載的硬化性樹脂組成物，其中，以酚系硬化劑的酚性羥基相對於環氧樹脂的環氧基的當量比0.5以上且未滿1.0含有所述環氧樹脂及所述酚系硬化劑。＜6＞一種電子零件裝置，包括元件以及將所述元件密封的如所述＜1＞至＜5＞中任一項所記載的硬化性樹脂組成物的樹脂硬化物。＜7＞如所述＜6＞所記載的電子零件裝置，更包括支撐構件，所述支撐構件於其中一面上搭載所述元件。 [發明的效果] A specific method for achieving the above object is as follows. <1> A curable resin composition, wherein, in a graph obtained by measuring the dynamic viscoelasticity of a resin cured product of the curable resin composition, the vertical axis represents tan δ and the horizontal axis represents the temperature of 30°C to 260°C Among them, (1) the temperature at which tanδ becomes the maximum is less than 120°C, (2) the maximum value of tanδ exceeds 0.400, and (3) the sum of the tanδ values at each temperature of 220°C, 230°C, 240°C, and 250°C exceeds 0.400. <2> A curable resin composition, wherein, in a graph obtained by measuring the dynamic viscoelasticity of cured resin of the curable resin composition, the vertical axis represents tan δ and the horizontal axis represents the temperature of 30°C to 260°C Among them, the sum of the tanδ values at each temperature of 70°C, 80°C, and 90°C exceeded 0.600. <3> The curable resin composition according to the above <1> or <2>, wherein the maximum value of tan δ in the graph is set to 100, and the temperature at which tan δ becomes maximum is −10° C. The tan delta value exceeds 60 at at least any temperature. <4> The curable resin composition according to any one of the above <1> to <3>, wherein 260 is obtained by measuring the dynamic viscoelasticity of the cured resin of the curable resin composition. The storage viscoelasticity at ℃ is below 450 MPa. <5> The curable resin composition according to any one of <1> to <4>, wherein the equivalent ratio of the phenolic hydroxyl group of the phenolic curing agent to the epoxy group of the epoxy resin is 0.5 More than 1.0 and less than 1.0 contain the epoxy resin and the phenolic curing agent. <6> An electronic component device including an element and a cured resin product of the curable resin composition according to any one of <1> to <5>, which seals the element. <7> The electronic component device according to the above <6>, further including a support member on which the element is mounted on one surface. [Effect of the invention]

藉由本揭示，可提供一種具有優異的耐回焊性的硬化性樹脂組成物及包括由該硬化性樹脂組成物密封的元件的電子零件裝置。According to the present disclosure, it is possible to provide a curable resin composition having excellent reflow resistance and an electronic component device including an element sealed by the curable resin composition.

以下，對用以實施本揭示的形態進行詳細說明。其中，本揭示並不限定於以下實施方式。於以下實施方式中，除特別明確表示的情況以外，其結構要素（亦包括要素步驟等）並非必需。數值及其範圍亦相同，且並不限制本揭示。Hereinafter, the form for carrying out this indication is demonstrated in detail. However, this disclosure is not limited to the following embodiments. In the following embodiments, the structural elements (including elemental steps, etc.) are not essential unless otherwise specified. Numerical values and their ranges are also the same, and do not limit the present disclosure.

於本揭示中，於使用「～」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。於本揭示中階段性記載的數值範圍中，一個數值範圍中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。另外，於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合成例中所示的值。於本揭示中，可含有多種相當於各成分的化合物。於在組成物中存在多種相當於各成分的物質的情況下，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的含有率或含量。於本揭示中，可含有多種相當於各成分的粒子。於在組成物中存在多種相當於各成分的粒子的情況下，只要無特別說明，則各成分的粒子徑是指與組成物中所存在的該多種粒子的混合物相關的值。於本揭示中，「積層」一用語表示將層疊加，可使兩層以上的層結合，亦可使兩層以上的層能夠拆裝。於本揭示的基（原子團）的表述中，未記錄經取代及未經取代的表述既包含不具有取代基者，亦包含具有取代基者。於本揭示中，關於結構單元數，對於單一分子而言表示整數值，作為多種分子的集合體，表示作為平均值的有理數。於本揭示中，所謂碳數，是指某基整體中所含的碳原子的總數，於該基不具有取代基的情況下，表示形成該基的骨架的碳原子的數量，於該基具有取代基的情況下，表示形成該基的骨架的碳原子的數量加上取代基中的碳原子的數量而得的總數。 In this disclosure, the numerical values described before and after "-" are included in the numerical range represented by "-" as a minimum value and a maximum value, respectively. In the numerical ranges described step by step in this disclosure, the upper limit or lower limit described in one numerical range may also be replaced by the upper limit or lower limit of other numerical ranges described step by step. In addition, in the numerical range described in this indication, the upper limit or the lower limit of the numerical range may be replaced with the value shown in the synthesis example. In the present disclosure, a plurality of compounds corresponding to each component may be contained. When a plurality of substances corresponding to each component exist in the composition, unless otherwise specified, the content or content of each component refers to the total content or content of the plurality of substances present in the composition. In the present disclosure, a plurality of particles corresponding to each component may be contained. When multiple types of particles corresponding to each component exist in the composition, unless otherwise specified, the particle size of each component refers to a value related to a mixture of the plurality of types of particles present in the composition. In this disclosure, the term "lamination" refers to stacking layers so that two or more layers can be combined or two or more layers can be detached. In the expression of the group (atomic group) in the present disclosure, the expression that does not record substitution and unsubstituted includes both those without a substituent and those with a substituent. In the present disclosure, the number of structural units represents an integer value for a single molecule, and represents a rational number as an average value for an aggregate of multiple types of molecules. In this disclosure, the so-called carbon number refers to the total number of carbon atoms contained in a certain group as a whole, and when the group has no substituents, it means the number of carbon atoms forming the skeleton of the group. In the case of a substituent, it means the total number of carbon atoms forming the skeleton of the group plus the number of carbon atoms in the substituent.

於本揭示中，對硬化性樹脂組成物的樹脂硬化物進行的動態黏彈性測定可使用動態黏彈性測定裝置（例如，珀金埃爾默（PerkinElmer）公司製造、DMA8000）來實施。例如，可針對短邊5 mm×長邊50 mm×厚度2 mm的長方形形狀的樹脂硬化物，於試驗模式：3點彎曲模式、測定溫度：25℃～330℃、升溫速度：10℃/分鐘、試驗頻率：1 Hz的條件下實施動態黏彈性測定，並根據所獲得的圖表（縱軸：tanδ、橫軸：溫度）來確定貯存黏彈性的值、tanδ的最大值、tanδ成為最大值時的溫度等。再者，樹脂硬化物的製作是藉由如下方式來進行：利用轉移成形機於模具溫度175℃、成形壓力8.3 MPa、硬化時間120秒的條件下將硬化性樹脂組成物成形，繼而，於175℃下實施5小時的後硬化。 In the present disclosure, the dynamic viscoelasticity measurement of the resin cured product of the curable resin composition can be performed using a dynamic viscoelasticity measurement device (for example, DMA8000 manufactured by PerkinElmer). For example, for a rectangular cured resin with a short side of 5 mm x a long side of 50 mm x a thickness of 2 mm, the test mode: 3-point bending mode, measurement temperature: 25°C to 330°C, heating rate: 10°C/min , Test frequency: Perform dynamic viscoelasticity measurement under the condition of 1 Hz, and determine the value of storage viscoelasticity, the maximum value of tanδ, and the time when tanδ reaches the maximum value based on the obtained graph (vertical axis: tanδ, horizontal axis: temperature) temperature etc. Furthermore, the production of the cured resin is carried out by using a transfer molding machine to mold the curable resin composition under the conditions of a mold temperature of 175°C, a molding pressure of 8.3 MPa, and a curing time of 120 seconds, and then, at 175 5 hours post-hardening at °C.

於本揭示中，硬化性樹脂組成物的樹脂硬化物的熱膨脹係數（Coefficient of Thermal Expansion，CTE）的測定中，例如針對φ4 mm×20 mm的樹脂硬化物，使用熱機械分析裝置來進行。再者，關於樹脂硬化物的製作，如上所述。測定條件設為荷重15 g、測定溫度-50℃～220℃、升溫速度5℃/分鐘。作為熱機械分析裝置，可使用精工儀器（Seiko Instruments）股份有限公司製造的TMA/SS6100。 In the present disclosure, the measurement of the coefficient of thermal expansion (Coefficient of Thermal Expansion, CTE) of the cured resin of the curable resin composition is performed using a thermomechanical analyzer for, for example, a cured resin of φ4 mm×20 mm. In addition, about preparation of cured resin, it is as above-mentioned. The measurement conditions were a load of 15 g, a measurement temperature of -50° C. to 220° C., and a heating rate of 5° C./min. As a thermomechanical analyzer, TMA/SS6100 manufactured by Seiko Instruments Co., Ltd. can be used.

於本揭示中，重量平均分子量（Mw）及數量平均分子量（Mn）是於下述測定條件下，使用下述凝膠滲透層析（Gel Permeation Chromatography，GPC）測定裝置來測定，使用標準聚苯乙烯的校準曲線進行換算而得的值。另外，校準曲線的製作中，作為標準聚苯乙烯，使用五個樣品組（「PStQuick MP-H」及「PStQuick B」、東曹股份有限公司製造）。其中，關於由於分子量小而無法利用GPC來測定正確的Mw或Mn的化合物，採用根據化合物的化學結構而求出的分子量來作為該化合物的Mw或Mn。（GPC測定裝置） ·GPC裝置：高速GPC裝置「HCL-8320GPC」、檢測器為示差折射計或UV、東曹股份有限公司製造 ·管柱：管柱TSKgel Super Multipore HZ-H（管柱長度：15 cm、管柱內徑：4.6 mm）、東曹股份有限公司製造（測定條件） ·溶媒：四氫呋喃（tetrahydrofuran，THF） ·測定溫度：40℃ ·流量：0.35 mL/分鐘 ·試樣濃度：10 mg/THF 5 mL ·注入量：20 μL In this disclosure, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured under the following measurement conditions, using the following gel permeation chromatography (Gel Permeation Chromatography, GPC) measurement device, using standard polyphenylene Ethylene calibration curve to convert the value obtained. In addition, in preparation of the calibration curve, five sample sets ("PStQuick MP-H" and "PStQuick B", manufactured by Tosoh Corporation) were used as standard polystyrene. Among them, for compounds whose molecular weights are too small to accurately measure Mw or Mn by GPC, the molecular weight obtained from the chemical structure of the compound is used as the Mw or Mn of the compound. (GPC measurement device) ・GPC device: High-speed GPC device "HCL-8320GPC", detector is differential refractometer or UV, manufactured by Tosoh Co., Ltd. String: TSKgel Super Multipore HZ-H (string length: 15 cm, string inner diameter: 4.6 mm), manufactured by Tosoh Co., Ltd. (measurement conditions) ·Solvent: tetrahydrofuran (THF) ·Measurement temperature: 40℃ ·Flow rate: 0.35 mL/min ·Sample concentration: 10 mg/THF 5 mL ・Injection volume: 20 μL

[硬化性樹脂組成物] ＜第一態樣的硬化性樹脂組成物＞第一態樣的硬化性樹脂組成物中，於藉由對硬化性樹脂組成物的樹脂硬化物進行動態黏彈性測定而獲得的縱軸為tanδ及橫軸為30℃～260℃的溫度的圖表中，（1）tanδ成為最大時的溫度（所謂的玻璃轉移溫度）未滿120℃，（2）tanδ的最大值超過0.400，且（3）220℃、230℃、240℃及250℃各溫度下的tanδ值的合計超過0.400。 [Hardening resin composition] <The curable resin composition of the first aspect> In the curable resin composition of the first aspect, the graph obtained by measuring the dynamic viscoelasticity of the resin cured product of the curable resin composition is tan δ on the vertical axis and temperature from 30°C to 260°C on the horizontal axis Among them, (1) the temperature at which tanδ becomes maximum (so-called glass transition temperature) is less than 120°C, (2) the maximum value of tanδ exceeds 0.400, and (3) each temperature of 220°C, 230°C, 240°C, and 250°C The sum of the lower tan δ values exceeds 0.400.

第一態樣的硬化性樹脂組成物具有優異的耐回焊性。The curable resin composition of the first aspect has excellent reflow resistance.

藉由第一態樣的硬化性樹脂組成物而起到所述效果的理由並不明確，但推測如下。The reason why the above effect is exhibited by the curable resin composition of the first aspect is not clear, but it is estimated as follows.

根據第一態樣的硬化性樹脂組成物，有回焊時所產生的樹脂硬化物的內部應力得到緩和的傾向，所述第一態樣的硬化性樹脂組成物中，於藉由對硬化性樹脂組成物的樹脂硬化物進行動態黏彈性測定而獲得的縱軸為tanδ及橫軸為30℃～260℃的溫度的圖表中，（1）tanδ成為最大時的溫度（所謂的玻璃轉移溫度）未滿120℃，（2）tanδ的最大值超過0.400，且（3）220℃、230℃、240℃及250℃各溫度下的tanδ值的合計超過0.400。其結果，硬化性樹脂組成物的樹脂硬化物與支撐構件的接著性提高，因此推測具有優異的耐回焊性。作為用以評價耐回焊性的試驗，已知有作為聯合電子設備工程委員會（Joint Electron Device Engineer Council，JEDEC）標準的濕度敏感等級（Moisture Sensitive Level，MSL）試驗。根據本揭示的硬化性樹脂組成物，即便於利用溫度85℃、相對濕度85%、168小時的條件（相當於MSL等級1）的加熱加濕後，亦顯示出優異的耐回焊性，此情況令人吃驚。 According to the curable resin composition of the first aspect, the internal stress of the cured resin produced during reflow tends to be relaxed. In a graph of tan δ on the vertical axis and temperature from 30°C to 260°C on the horizontal axis obtained by dynamic viscoelasticity measurement of the cured resin of the resin composition, (1) The temperature at which tan δ becomes maximum (so-called glass transition temperature) It is less than 120°C, (2) the maximum value of tanδ exceeds 0.400, and (3) the total of tanδ values at each temperature of 220°C, 230°C, 240°C, and 250°C exceeds 0.400. As a result, the cured resin product of the curable resin composition has improved adhesiveness to the support member, and thus is presumed to have excellent reflow resistance. As a test for evaluating reflow resistance, there is known a Moisture Sensitive Level (MSL) test that is a standard of the Joint Electron Device Engineer Council (JEDEC). According to the curable resin composition of the present disclosure, even after heating and humidifying under conditions of temperature 85°C, relative humidity 85%, and 168 hours (equivalent to MSL level 1), it also shows excellent reflow resistance. The situation is surprising.

就第一態樣的硬化性樹脂組成物的耐回焊性的觀點而言，tanδ成為最大時的溫度較佳為未滿110℃。tanδ成為最大時的溫度的下限值並無特別限定，例如可設為50℃以上。From the viewpoint of the reflow resistance of the curable resin composition of the first aspect, the temperature at which tan δ becomes maximum is preferably less than 110°C. The lower limit of the temperature at which tan δ becomes maximum is not particularly limited, and may be set to, for example, 50° C. or higher.

就第一態樣的硬化性樹脂組成物的耐回焊性的觀點而言，tanδ的最大值較佳為超過0.410。tanδ的最大值的上限值並無特別限定，例如可設為1.0以下。From the viewpoint of the reflow resistance of the curable resin composition of the first aspect, the maximum value of tan δ is preferably more than 0.410. The upper limit of the maximum value of tan δ is not particularly limited, and may be, for example, 1.0 or less.

就第一態樣的硬化性樹脂組成物的耐回焊性的觀點而言，220℃、230℃、240℃及250℃各溫度下的tanδ值的合計的上限值並無特別限定，例如可設為2.0以下。From the viewpoint of the reflow resistance of the curable resin composition of the first aspect, the upper limit of the sum of tanδ values at each temperature of 220°C, 230°C, 240°C, and 250°C is not particularly limited, for example Can be set below 2.0.

就第一態樣的硬化性樹脂組成物的耐回焊性的觀點而言，於將tanδ的最大值設為100時，tanδ成為最大時的溫度-10℃的至少任一溫度下的tanδ值較佳為超過60，更佳為超過63，進而佳為超過65。From the viewpoint of the reflow resistance of the curable resin composition of the first aspect, when the maximum value of tan δ is set to 100, the tan δ value at least any one of the temperature at which tan δ becomes maximum - 10°C It is preferably more than 60, more preferably more than 63, and still more preferably more than 65.

就第一態樣的硬化性樹脂組成物的耐回焊性的觀點而言，70℃、80℃及90℃各溫度下的tanδ值的合計較佳為超過0.600，更佳為超過0.700。70℃、80℃及90℃各溫度下的tanδ值的合計的上限值並無特別限定，例如可設為2.0以下。From the viewpoint of the reflow resistance of the curable resin composition of the first aspect, the sum of the tanδ values at each temperature of 70°C, 80°C, and 90°C is preferably more than 0.600, more preferably more than 0.700.70 The upper limit of the sum of the tan δ values at each temperature of °C, 80°C, and 90°C is not particularly limited, and may be, for example, 2.0 or less.

就第一態樣的硬化性樹脂組成物的耐回焊性的觀點而言，藉由對硬化性樹脂組成物的樹脂硬化物進行動態黏彈性測定而求出的260℃下的貯存黏彈性較佳為450 MPa以下，更佳為435 MPa以下，進而佳為420 MPa以下。貯存彈性係數的下限值並無特別限定，例如可設為150 MPa以上。From the viewpoint of the reflow resistance of the curable resin composition of the first aspect, the storage viscoelasticity at 260°C obtained by measuring the dynamic viscoelasticity of the resin cured product of the curable resin composition is higher than that of It is preferably at most 450 MPa, more preferably at most 435 MPa, and still more preferably at most 420 MPa. The lower limit of the storage elastic coefficient is not particularly limited, and may be set to, for example, 150 MPa or more.

就對支撐構件的追隨性的觀點而言，藉由熱機械分析測定而求出的第一態樣的硬化性樹脂組成物的樹脂硬化物於未滿玻璃轉移溫度的溫度下的熱膨脹係數（CTE1）較佳為15 ppm/℃以下，更佳為13 ppm/℃以下，進而佳為10 ppm/℃以下。熱膨脹係數的下限值並無特別限定，例如可設為3 ppm/℃。就與支撐構件的接著性的觀點而言，玻璃轉移溫度以上的溫度下的熱膨脹係數（CTE2）較佳為10 ppm/℃～45 ppm/℃，更佳為12 ppm/℃～40 ppm/℃，進而佳為15 ppm/℃～38 ppm/℃。 From the viewpoint of followability to the supporting member, the thermal expansion coefficient (CTE1 ) is preferably at most 15 ppm/°C, more preferably at most 13 ppm/°C, still more preferably at most 10 ppm/°C. The lower limit of the coefficient of thermal expansion is not particularly limited, and may be 3 ppm/°C, for example. From the viewpoint of adhesion to the support member, the coefficient of thermal expansion (CTE2) at a temperature above the glass transition temperature is preferably 10 ppm/°C to 45 ppm/°C, more preferably 12 ppm/°C to 40 ppm/°C , and more preferably 15 ppm/°C to 38 ppm/°C.

就耐回焊性的觀點而言，第一態樣的硬化性樹脂組成物較佳為以酚系硬化劑的酚性羥基相對於環氧樹脂的環氧基的當量比0.5以上且未滿1.0含有環氧樹脂及酚系硬化劑。於本揭示中，酚系硬化劑的酚性羥基（活性氫）相對於環氧樹脂的環氧基的當量比（酚系硬化劑的活性氫的莫耳數/環氧樹脂的環氧基的莫耳數）可以如下方式求出：對硬化性樹脂組成物進行 ¹H-核磁共振（ ¹H-Nuclear Magnetic Resonance， ¹H-NMR）測定，並根據環氧基的質子與酚性羥基的質子的積分比來求出。再者，硬化性樹脂組成物的 ¹H-NMR是於以下的條件下進行測定。（測定條件） ·測定裝置：布魯克（Bruker）公司製造、AVANCE3 HD 400 Nanobay ·測定溶媒：二甲基亞碸（dimethyl sulfoxide，DMSO）-d6（0.7 ml） ·測定溫度：25℃ · ¹H共振頻率：400 MHz ·測定模式：NPROTON ·累計次數：16次 ·緩和時間：1秒 From the viewpoint of reflow resistance, the curable resin composition of the first aspect is preferably such that the equivalent ratio of the phenolic hydroxyl group of the phenolic curing agent to the epoxy group of the epoxy resin is 0.5 or more and less than 1.0 Contains epoxy resin and phenolic hardener. In this disclosure, the equivalent ratio of the phenolic hydroxyl group (active hydrogen) of the phenolic hardener to the epoxy group of the epoxy resin (the number of moles of the active hydrogen of the phenolic hardener/the epoxy group of the epoxy resin Mole number) can be obtained as follows: ¹ H-NMR ( ¹ H-Nuclear Magnetic Resonance, ¹ H-NMR) measurement is performed on the curable resin composition, and the proton of the epoxy group and the proton of the phenolic hydroxyl group Calculate the integral ratio of . In addition, ¹ H-NMR of curable resin composition was measured on the following conditions. (Measurement conditions) Measuring device: Bruker, AVANCE3 HD 400 Nanobay Measuring solvent: dimethyl sulfoxide (DMSO)-d6 (0.7 ml) Measuring temperature: 25°C ¹ H resonance Frequency: 400 MHz ・Measurement mode: NPROTON ・Cumulative count: 16 times ・Relaxation time: 1 second

以下，對第一態樣的硬化性樹脂組成物可含有的各種材料進行說明。Hereinafter, various materials that may be contained in the curable resin composition of the first aspect will be described.

（環氧樹脂）第一態樣的硬化性樹脂組成物可含有環氧樹脂。環氧樹脂只要為於一分子中具有2個以上的環氧基者，則環氧樹脂的種類並無特別限制。再者，於本揭示中，所述直鏈狀聚矽氧烷化合物設為不包含於環氧樹脂中者。以下記載環氧樹脂的具體例，但並不限定於該些。 (epoxy resin) The curable resin composition of the first aspect may contain an epoxy resin. The type of the epoxy resin is not particularly limited as long as the epoxy resin has two or more epoxy groups in one molecule. In addition, in this disclosure, the said linear polysiloxane compound is assumed not to be contained in an epoxy resin. Although the specific example of an epoxy resin is described below, it is not limited to these.

具體而言，可列舉：使選自由苯酚、甲酚、二甲酚、間苯二酚、鄰苯二酚、雙酚A、雙酚F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、丙醛等脂肪族醛化合物於酸性觸媒下縮合或共縮合而獲得酚醛清漆樹脂，並使該酚醛清漆樹脂進行環氧化而獲得的酚醛清漆型環氧樹脂（苯酚酚醛清漆型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂等）；使所述酚性化合物與苯甲醛、水楊醛等芳香族醛化合物於酸性觸媒下縮合或共縮合而獲得三苯基甲烷型酚樹脂，並使該三苯基甲烷型酚樹脂進行環氧化而獲得的三苯基甲烷型環氧樹脂；使所述苯酚化合物及萘酚化合物與醛化合物於酸性觸媒下共縮合而獲得酚醛清漆樹脂，並使該酚醛清漆樹脂進行環氧化而獲得的共聚合型環氧樹脂；作為雙酚A、雙酚F等的二縮水甘油醚的二苯基甲烷型環氧樹脂；作為烷基經取代或未經取代的聯苯酚的二縮水甘油醚的聯苯型環氧樹脂；作為二苯乙烯（stilbene）系酚化合物的二縮水甘油醚的二苯乙烯型環氧樹脂；作為雙酚S等的二縮水甘油醚的含硫原子型環氧樹脂；作為丁二醇、聚乙二醇、聚丙二醇等醇類的縮水甘油醚的環氧樹脂；作為鄰苯二甲酸、間苯二甲酸、四氫鄰苯二甲酸等多元羧酸化合物的縮水甘油酯的縮水甘油酯型環氧樹脂；將苯胺、二胺基二苯基甲烷、異三聚氰酸等的鍵結於氮原子的活性氫以縮水甘油基取代而獲得的縮水甘油胺型環氧樹脂；使二環戊二烯與苯酚化合物的共縮合樹脂進行環氧化而獲得的二環戊二烯型環氧樹脂；使分子內的烯烴鍵進行環氧化而獲得的二環氧化乙烯基環己烯、3,4-環氧基環己基甲基-3,4-環氧基環己烷羧酸酯、2-(3,4-環氧基)環己基-5,5-螺環(3,4-環氧基)環己烷-間二噁烷等脂環型環氧樹脂；作為對二甲苯改質酚樹脂的縮水甘油醚的對二甲苯改質環氧樹脂；作為間二甲苯改質酚樹脂的縮水甘油醚的間二甲苯改質環氧樹脂；作為萜烯改質酚樹脂的縮水甘油醚的萜烯改質環氧樹脂；作為二環戊二烯改質酚樹脂的縮水甘油醚的二環戊二烯改質環氧樹脂；作為環戊二烯改質酚樹脂的縮水甘油醚的環戊二烯改質環氧樹脂；作為多環芳香環改質酚樹脂的縮水甘油醚的多環芳香環改質環氧樹脂；作為含萘環的酚樹脂的縮水甘油醚的萘型環氧樹脂；鹵化苯酚酚醛清漆型環氧樹脂；對苯二酚型環氧樹脂；三羥甲基丙烷型環氧樹脂；利用過乙酸等過酸將烯烴鍵氧化而獲得的線狀脂肪族環氧樹脂；使苯酚芳烷基樹脂、萘酚芳烷基樹脂等芳烷基型酚樹脂進行環氧化而獲得的芳烷基型環氧樹脂等。進而，亦可列舉胺基苯酚的縮水甘油醚即胺基苯酚型環氧樹脂等作為環氧樹脂。該些環氧樹脂可單獨使用一種，亦可將兩種以上組合而使用。Specifically, examples include: phenol compounds selected from phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, α-naphthol, β-naphthol, At least one phenolic compound in the group consisting of naphthol compounds such as dihydroxynaphthalene and aliphatic aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde are condensed or co-condensed under an acidic catalyst to obtain a novolac resin, and the Novolak-type epoxy resins (phenol novolak-type epoxy resins, o-cresol novolac-type epoxy resins, etc.) obtained by epoxidizing novolak resins; mixing the phenolic compounds with benzaldehyde, salicylaldehyde, etc. Aromatic aldehyde compounds are condensed or co-condensed under an acidic catalyst to obtain a triphenylmethane type phenol resin, and the triphenylmethane type epoxy resin obtained by epoxidizing the triphenylmethane type phenol resin; Co-condensation of the phenol compound, naphthol compound and aldehyde compound under an acidic catalyst to obtain a novolac resin, and epoxidation of the novolac resin to obtain a copolymerized epoxy resin; as bisphenol A, bisphenol F Diphenylmethane-type epoxy resins such as diglycidyl ethers of diphenylmethane; biphenyl-type epoxy resins as diglycidyl ethers of diphenols with alkyl substituted or unsubstituted; Distyrene-type epoxy resins of diglycidyl ethers of compounds; sulfur-atom-containing epoxy resins of diglycidyl ethers such as bisphenol S; alcohols such as butanediol, polyethylene glycol, and polypropylene glycol Epoxy resin of glycidyl ether; glycidyl ester type epoxy resin as glycidyl ester of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; Glycidylamine-type epoxy resin obtained by substituting the active hydrogen bonded to the nitrogen atom of phenylmethane, isocyanuric acid, etc. with a glycidyl group; the co-condensation resin of dicyclopentadiene and phenol compound is cyclized Dicyclopentadiene-type epoxy resin obtained by oxidation; Diepoxidized vinyl cyclohexene, 3,4-epoxycyclohexylmethyl-3,4 obtained by epoxidizing olefin bonds in the molecule -Epoxy cyclohexane carboxylate, 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane etc. Cyclic epoxy resin; p-xylene modified epoxy resin as the glycidyl ether of p-xylene modified phenol resin; m-xylene modified epoxy resin as the glycidyl ether of m-xylene modified phenol resin; Terpene-modified epoxy resins as glycidyl ethers of terpene-modified phenolic resins; dicyclopentadiene-modified epoxy resins as glycidyl ethers of dicyclopentadiene-modified phenolic resins; cyclopentadiene-modified epoxy resins as glycidyl ethers Cyclopentadiene-modified epoxy resins of glycidyl ethers of alkenyl-modified phenol resins; polycyclic aromatic ring-modified epoxy resins of glycidyl ethers of polycyclic aromatic ring-modified phenol resins; as phenols containing naphthalene rings Naphthalene-type epoxy resins of glycidyl ethers of resins; halogenated phenol novolak-type epoxy resins; hydroquinone-type epoxy resins; trimethylolpropane-type epoxy resins; oxidation of olefin bonds by peracids such as peracetic acid Linear aliphatic epoxy resins obtained; aralkyl type epoxy resins obtained by epoxidizing aralkyl type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins; and the like. Furthermore, aminophenol type epoxy resin etc. which are the glycidyl ether of aminophenol, etc. are mentioned as an epoxy resin. These epoxy resins may be used alone or in combination of two or more.

聯苯型環氧樹脂只要為具有聯苯骨架的環氧樹脂，則並無特別限定。例如較佳為下述通式（II）所表示的環氧樹脂。The biphenyl-type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton. For example, an epoxy resin represented by the following general formula (II) is preferable.

[化1]

[chemical 1]

式（II）中，R ⁸表示氫原子、碳數1～12的烷基或碳數4～18的芳香族基，可分別均相同亦可不同。n為平均值，且表示0～10的整數。 In formula (II), R ⁸ represents a hydrogen atom, an alkyl group having 1 to 12 carbons, or an aromatic group having 4 to 18 carbons, which may be the same or different. n is an average value, and represents the integer of 0-10.

二苯乙烯型環氧樹脂只要為具有二苯乙烯骨架的環氧樹脂，則並無特別限定。例如較佳為下述通式（III）所表示的環氧樹脂。The stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton. For example, an epoxy resin represented by the following general formula (III) is preferable.

[化2]

[Chem 2]

式（III）中，R ⁹及R ¹⁰表示氫原子或碳數1～18的一價有機基，可分別均相同亦可不同。n為平均值，且表示0～10的整數。 In formula (III), R ⁹ and R ¹⁰ represent a hydrogen atom or a monovalent organic group having 1 to 18 carbons, and may be the same or different. n is an average value, and represents the integer of 0-10.

二苯基甲烷型環氧樹脂只要為具有二苯基甲烷骨架的環氧樹脂，則並無特別限定。例如較佳為下述通式（IV）所表示的環氧樹脂。The diphenylmethane-type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, an epoxy resin represented by the following general formula (IV) is preferable.

[化3]

[Chem 3]

式（IV）中，R ¹¹及R ¹²表示氫原子或碳數1～18的一價有機基，可分別均相同亦可不同。n為平均值，且表示0～10的整數。 In formula (IV), R ¹¹ and R ¹² represent a hydrogen atom or a monovalent organic group having 1 to 18 carbons, and may be the same or different. n is an average value, and represents the integer of 0-10.

含硫原子型環氧樹脂只要為含有硫原子的環氧樹脂，則並無特別限定。例如可列舉下述通式（V）所表示的環氧樹脂。The sulfur atom-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom. For example, the epoxy resin represented by following general formula (V) is mentioned.

[化4]

[chemical 4]

式（V）中，R ¹³表示氫原子或碳數1～18的一價有機基，可分別均相同亦可不同。n為平均值，且表示0～10的整數。 In formula (V), R ¹³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbons, and may be the same or different. n is an average value, and represents the integer of 0-10.

酚醛清漆型環氧樹脂只要為使酚醛清漆型酚樹脂進行環氧化而獲得的環氧樹脂，則並無特別限定。The novolak-type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolak-type phenol resin.

[化5]

[chemical 5]

式（VI）中，R ¹⁴表示氫原子或碳數1～18的一價有機基，可分別均相同亦可不同。R ¹⁵表示碳數1～18的一價有機基，可分別均相同亦可不同。i各自獨立地表示0～3的整數。n為平均值，且表示0～10的整數。 In the formula (VI), R ¹⁴ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbons, which may be the same or different. R ¹⁵ represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i each independently represents an integer of 0-3. n is an average value, and represents the integer of 0-10.

二環戊二烯型環氧樹脂只要為將具有二環戊二烯骨架的化合物作為原料來進行環氧化而獲得的環氧樹脂，則並無特別限定。The dicyclopentadiene-type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentadiene skeleton as a raw material.

[化6]

[chemical 6]

式（VII）中，R ¹⁶表示碳數1～18的一價有機基，可分別均相同亦可不同。i各自獨立地表示0～3的整數。n為平均值，且表示0～10的整數。 In formula (VII), R ¹⁶ represents a monovalent organic group having 1 to 18 carbon atoms, which may be the same or different. i each independently represents an integer of 0-3. n is an average value, and represents the integer of 0-10.

三苯基甲烷型環氧樹脂只要為將具有三苯基甲烷骨架的化合物作為原料的環氧樹脂，則並無特別限制。The triphenylmethane-type epoxy resin is not particularly limited as long as it is an epoxy resin made of a compound having a triphenylmethane skeleton as a raw material.

[化7]

[chemical 7]

式（VIII）中，R ¹⁷及R ¹⁸表示碳數1～18的一價有機基，可分別均相同亦可不同。i各自獨立地表示0～3的整數，k各自獨立地表示0～4的整數。n為平均值，且表示0～10的整數。 In formula (VIII), R ¹⁷ and R ¹⁸ represent monovalent organic groups having 1 to 18 carbon atoms, and may be the same or different. i each independently represent an integer of 0-3, and k each independently represent an integer of 0-4. n is an average value, and represents the integer of 0-10.

使由萘酚化合物及苯酚化合物與醛化合物所獲得的酚醛清漆樹脂進行環氧化而成的共聚合型環氧樹脂只要為將具有萘酚骨架的化合物及具有苯酚骨架的化合物作為原料的環氧樹脂，則並無特別限定。例如較佳為使利用具有萘酚骨架的化合物及具有苯酚骨架的化合物的酚醛清漆型酚樹脂進行縮水甘油醚化而獲得的環氧樹脂，更佳為下述通式（IX）所表示的環氧樹脂。 The copolymerized epoxy resin obtained by epoxidizing a novolak resin obtained from a naphthol compound, a phenol compound, and an aldehyde compound should be an epoxy resin that uses a compound having a naphthol skeleton and a compound having a phenol skeleton as raw materials. , there is no special limitation. For example, an epoxy resin obtained by glycidyl etherification of a novolak-type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton is preferable, and a ring represented by the following general formula (IX) is more preferable. oxygen resin.

[化8]

[chemical 8]

式（IX）中，R ¹⁹～R ²¹表示碳數1～18的一價有機基，可分別均相同亦可不同。i各自獨立地表示0～3的整數，j各自獨立地表示0～2的整數，k各自獨立地表示0～4的整數。l及m分別為平均值，為0～10的數，（l+m）表示0～10的數。式（IX）所表示的環氧樹脂的末端為下述式（IX-1）或式（IX-2）中的任一者。於式（IX-1）及式（IX-2）中，R ¹⁹～R ²¹、i、j及k的定義與式（IX）中的R ¹⁹～R ²¹、i、j及k的定義相同。n為1（經由亞甲基而鍵結的情況）或0（不經由亞甲基而鍵結的情況）。 In formula (IX), R ¹⁹ to R ²¹ represent monovalent organic groups having 1 to 18 carbon atoms, and may be the same or different. i each independently represent an integer of 0-3, j each independently represent an integer of 0-2, and k each independently represent an integer of 0-4. l and m are average values, respectively, and represent numbers from 0 to 10, and (l+m) represents numbers from 0 to 10. The terminal of the epoxy resin represented by formula (IX) is any one of the following formula (IX-1) or formula (IX-2). In formula (IX-1) and formula (IX-2), the definitions of R ¹⁹ to R ²¹ , i, j and k are the same as the definitions of R ¹⁹ to R ²¹ , i, j and k in formula (IX) . n is 1 (when bonding via a methylene group) or 0 (when not bonding via a methylene group).

[化9]

[chemical 9]

作為所述通式（IX）所表示的環氧樹脂，可列舉：無規地具有l個結構單元及m個結構單元的無規共聚物、交替地具有l個結構單元及m個結構單元的交替共聚物、規則地具有l個結構單元及m個結構單元的共聚物、以嵌段狀具有l個結構單元及m個結構單元的嵌段共聚物等。可單獨使用該些的任一種，亦可將兩種以上組合而使用。Examples of the epoxy resin represented by the general formula (IX) include random copolymers having one structural unit and m structural units at random, and those having one structural unit and m structural units alternately. Alternating copolymers, copolymers regularly having one structural unit and m structural units, block copolymers having one structural unit and m structural units in blocks, and the like. Any one of these may be used alone, or two or more of them may be used in combination.

芳烷基型環氧樹脂只要為將由選自由苯酚、甲酚等苯酚化合物及萘酚、二甲基萘酚等萘酚化合物所組成的群組中的至少一種，與二甲氧基對二甲苯、雙(甲氧基甲基)聯苯或該些的衍生物所合成的酚樹脂作為原料的環氧樹脂，則並無特別限定。例如較佳為使由選自由苯酚、甲酚等苯酚化合物及萘酚、二甲基萘酚等萘酚化合物所組成的群組中的至少一種與二甲氧基對二甲苯、雙(甲氧基甲基)聯苯或該些的衍生物所合成的酚樹脂進行縮水甘油醚化而獲得的環氧樹脂，更佳為下述通式（X）及通式（XI）所表示的環氧樹脂。The aralkyl type epoxy resin is at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxy p-xylol , bis(methoxymethyl)biphenyl, or a phenol resin synthesized from derivatives thereof, and the epoxy resin as a raw material is not particularly limited. For example, it is preferable to combine at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol with dimethoxy-p-xylene, bis(methoxy The epoxy resin obtained by glycidyl etherification of the phenol resin synthesized by methyl) biphenyl or these derivatives, is more preferably the epoxy resin represented by the following general formula (X) and general formula (XI) resin.

[化10]

[chemical 10]

於式（X）及式（XI）中，R ³⁸表示氫原子或碳數1～18的一價有機基，可分別均相同亦可不同。R ³⁷、R ³⁹～R ⁴¹表示碳數1～18的一價有機基，可分別均相同亦可不同。i各自獨立地為0～3的整數，j各自獨立地為0～2的整數，k各自獨立地為0～4的整數，l各自獨立地表示0～4的整數。n為平均值，且各自獨立地為0～10的整數。 In formula (X) and formula (XI), R ³⁸ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbons, which may be the same or different. R ³⁷ , R ³⁹ to R ⁴¹ represent a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i is each independently an integer of 0 to 3, j is each independently an integer of 0 to 2, k is each independently an integer of 0 to 4, and l is each independently an integer of 0 to 4. n is an average value, and is an integer of 0-10 each independently.

關於所述通式（II）～通式（XI）中的R ⁸～R ²¹及R ³⁷～R ⁴¹，所謂「可分別均相同亦可不同」，例如是指式（II）中的8個～88個R ⁸可均相同亦可不同。關於其他的R ⁹～R ²¹及R ³⁷～R ⁴¹，亦是指式中所含的各自的個數可均相同亦可不同。另外，R ⁸～R ²¹及R ³⁷～R ⁴¹可分別相同亦可不同。例如，R ⁹與R ¹⁰可均相同亦可不同。另外，通式（III）～通式（XI）中的碳數1～18的一價有機基較佳為烷基或芳基。 Regarding the R ⁸ to R ²¹ and R ³⁷ to R ⁴¹ in the general formula (II) to the general formula (XI), the so-called "may be the same or different", for example, refers to the 8 in the formula (II) ~88 R ⁸ may all be the same or different. As for the other R ⁹ to R ²¹ and R ³⁷ to R ⁴¹ , it also means that the number of each contained in the formula may be the same or different. In addition, R ⁸ to R ²¹ and R ³⁷ to R ⁴¹ may be respectively the same or different. For example, R ⁹ and R ¹⁰ may both be the same or different. In addition, the monovalent organic group having 1 to 18 carbon atoms in the general formulas (III) to (XI) is preferably an alkyl group or an aryl group.

所述通式（II）～通式（XI）中的n為平均值，較佳為各自獨立地為0～10的範圍。若n為10以下，則有樹脂成分的熔融黏度不會過高，於硬化性樹脂組成物的熔融成形時，黏度降低，可抑制填充不良、接合線（連接元件與引線的金屬線）的變形等的產生的傾向。n更佳為設定為0～4的範圍。n in the general formula (II) to general formula (XI) is an average value, preferably in the range of 0-10 each independently. If n is 10 or less, the melt viscosity of the resin component will not be too high, and the viscosity will be lowered during melt molding of the curable resin composition, thereby suppressing filling defects and deformation of bonding wires (metal wires connecting elements and leads) and so on tend to produce. n is more preferably set to the range of 0-4.

就第一態樣的硬化性樹脂組成物的耐回焊性的觀點而言，環氧樹脂較佳為包含具有源自烷基苯酚的結構單元及源自烷氧基萘的結構單元的共聚合型環氧樹脂（以下，稱為特定共聚合型環氧樹脂）。作為源自烷基苯酚的結構單元，可列舉下述結構單元（a）。From the viewpoint of the reflow resistance of the curable resin composition of the first aspect, the epoxy resin is preferably a copolymer having a structural unit derived from an alkylphenol and a structural unit derived from an alkoxynaphthalene. type epoxy resin (hereinafter referred to as specific copolymerization type epoxy resin). As a structural unit derived from an alkylphenol, the following structural unit (a) is mentioned.

[化11]

[chemical 11]

所述結構單元中，R _A各自獨立地表示碳數1～18的一價烷基，較佳為表示碳數1～6的一價烷基。X表示1～3的整數。 In the structural units, R _A each independently represents a monovalent alkyl group having 1 to 18 carbons, preferably a monovalent alkyl group having 1 to 6 carbons. X represents an integer of 1-3.

作為源自烷氧基萘的結構單元，可列舉以下的結構單元（b）。As a structural unit derived from an alkoxynaphthalene, the following structural unit (b) is mentioned.

[化12]

[chemical 12]

所述結構單元中，R _B各自獨立地表示碳數1～18的一價烷氧基，較佳為表示碳數1～6的一價烷氧基。y表示1～6的整數。再者，所述結構單元（b）中的兩個鍵結部位可存在於萘環的同一環上，亦可分別存在於萘環的兩個環上。 In the structural unit, R _B each independently represents a monovalent alkoxy group having 1 to 18 carbons, preferably a monovalent alkoxy group having 1 to 6 carbons. y represents the integer of 1-6. Furthermore, the two bonding sites in the structural unit (b) may exist on the same ring of the naphthalene ring, or may exist on two rings of the naphthalene ring respectively.

特定共聚合型環氧樹脂可具有下述結構單元（c）。下述結構單元中，n為1～10的整數，較佳為2～8的整數。再者，所述結構單元（c）中的萘環所具有的兩個鍵結部位可存在於萘環的同一環上，亦可分別存在於萘環的兩個環上。 The specific copolymerized epoxy resin may have the following structural unit (c). In the following structural units, n is an integer of 1-10, preferably an integer of 2-8. Furthermore, the two bonding sites of the naphthalene ring in the structural unit (c) may exist on the same ring of the naphthalene ring, or may exist on two rings of the naphthalene ring respectively.

[化13]

[chemical 13]

作為滿足所述結構單元（c）的結構單元，例如可列舉下述結構單元（d）。As a structural unit which satisfies the said structural unit (c), the following structural unit (d) is mentioned, for example.

[化14]

[chemical 14]

所述環氧樹脂中，就本揭示的硬化性樹脂組成物的耐回焊性的觀點而言，環氧樹脂較佳為包含特定共聚合型環氧樹脂。另外，就耐回焊性的觀點而言，環氧樹脂較佳為包含聯苯型環氧樹脂。 Among the above-mentioned epoxy resins, the epoxy resin preferably includes a specific copolymerized epoxy resin from the viewpoint of the reflow resistance of the curable resin composition of the present disclosure. In addition, the epoxy resin preferably includes a biphenyl type epoxy resin from the viewpoint of reflow resistance.

環氧樹脂的環氧當量並無特別限制。就成形性、耐熱性及電可靠性等各種特性平衡的觀點而言，環氧樹脂的環氧當量較佳為40 g/eq～1000 g/eq，更佳為45 g/eq～500 g/eq，進而佳為50 g/eq～350 g/eq。環氧樹脂的環氧當量設為利用依據日本工業標準（Japanese Industrial Standards，JIS）K 7236：2009的方法而測定的值。 The epoxy equivalent of the epoxy resin is not particularly limited. The epoxy equivalent of the epoxy resin is preferably from 40 g/eq to 1000 g/eq, more preferably from 45 g/eq to 500 g/eq from the viewpoint of a balance of various properties such as formability, heat resistance, and electrical reliability. eq, preferably 50 g/eq to 350 g/eq. The epoxy equivalent of the epoxy resin is set to a value measured by a method based on Japanese Industrial Standards (Japanese Industrial Standards, JIS) K 7236:2009.

環氧樹脂於25℃下可為固體，亦可為液體。於環氧樹脂於25℃下為固體的情況下，環氧樹脂的軟化點或熔點並無特別限制。就成形性與耐熱性的平衡的觀點而言，環氧樹脂的軟化點或熔點較佳為40℃～180℃。另外，就硬化性樹脂組成物的製造時的操作性的觀點而言，環氧樹脂的軟化點或熔點較佳為50℃～130℃。於本揭示中，軟化點是指藉由JIS K 7234：1986的環球法而測定的值。於本揭示中，熔點是指依據JIS K 0064：1992的基於目視的方法而測定的值。 Epoxy resin can be solid or liquid at 25°C. In the case that the epoxy resin is solid at 25° C., the softening point or melting point of the epoxy resin is not particularly limited. From the viewpoint of the balance between formability and heat resistance, the softening point or melting point of the epoxy resin is preferably 40°C to 180°C. In addition, the softening point or melting point of the epoxy resin is preferably from 50°C to 130°C from the viewpoint of workability during production of the curable resin composition. In the present disclosure, the softening point refers to a value measured by the ring and ball method of JIS K 7234:1986. In this indication, a melting point means the value measured by the visual inspection method based on JISK0064:1992.

就耐回焊性、成形性、耐熱性等的觀點而言，環氧樹脂的Mw較佳為550～1050，更佳為650～950。另外，就耐回焊性、成形性、耐熱性等的觀點而言，環氧樹脂的Mn較佳為250～800，更佳為350～600。 The Mw of the epoxy resin is preferably from 550 to 1050, more preferably from 650 to 950, from the viewpoint of reflow resistance, moldability, heat resistance, and the like. In addition, the Mn of the epoxy resin is preferably 250-800, more preferably 350-600, from the viewpoints of reflow resistance, moldability, heat resistance, and the like.

就耐回焊性、強度、流動性、成形性等的觀點而言，環氧樹脂相對於硬化性樹脂組成物的總質量的含有率較佳為0.5質量%～60質量%，更佳為2質量%～50質量%，進而佳為3質量%～45質量%。From the viewpoint of reflow resistance, strength, fluidity, formability, etc., the content of the epoxy resin to the total mass of the curable resin composition is preferably 0.5% by mass to 60% by mass, more preferably 2% by mass. % by mass to 50% by mass, more preferably 3% by mass to 45% by mass.

就第一態樣的硬化性樹脂組成物的耐回焊性的觀點而言，於環氧樹脂包含特定共聚合型環氧樹脂的情況下，特定共聚合型環氧樹脂相對於環氧樹脂的總質量的含有率較佳為50質量%～90質量%，更佳為55質量%～80質量%，進而佳為60質量%～75質量%。From the viewpoint of the reflow resistance of the curable resin composition of the first aspect, when the epoxy resin includes a specific copolymerization type epoxy resin, the specific copolymerization type epoxy resin relative to the epoxy resin The content of the total mass is preferably from 50% by mass to 90% by mass, more preferably from 55% by mass to 80% by mass, still more preferably from 60% by mass to 75% by mass.

就第一態樣的硬化性樹脂組成物的耐回焊性的觀點而言，於環氧樹脂包含聯苯型環氧樹脂的情況下，聯苯型環氧樹脂相對於環氧樹脂的總質量的含有率較佳為5質量%～40質量%，更佳為7質量%～35質量%，進而佳為10質量%～30質量%。From the viewpoint of the reflow resistance of the curable resin composition of the first aspect, when the epoxy resin contains a biphenyl type epoxy resin, the total mass of the biphenyl type epoxy resin relative to the epoxy resin The content rate of is preferably 5% by mass to 40% by mass, more preferably 7% by mass to 35% by mass, and still more preferably 10% by mass to 30% by mass.

（酚系硬化劑）第一態樣的硬化性樹脂組成物可含有酚系硬化劑。酚系硬化劑的種類並無特別限制，可自通常用作硬化性樹脂組成物的成分者中選擇。酚系硬化劑可單獨使用一種，亦可將兩種以上組合而使用。 (phenolic hardener) The curable resin composition of the first aspect may contain a phenolic curing agent. The type of phenolic curing agent is not particularly limited, and can be selected from those generally used as components of curable resin compositions. The phenolic curing agent may be used alone or in combination of two or more.

作為酚系硬化劑，例如可列舉於一分子中具有2個以上的酚性羥基的酚樹脂及多元酚化合物。以下記載酚系硬化劑的具體例，但並不限定於該些。作為酚系硬化劑，可列舉：間苯二酚、鄰苯二酚、雙酚A、雙酚F、經取代或未經取代的聯苯酚等多元酚化合物；使選自由苯酚、甲酚、二甲酚、間苯二酚、鄰苯二酚、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、丙醛等醛化合物於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、雙(甲氧基甲基)聯苯等所合成的苯酚芳烷基樹脂、萘酚芳烷基樹脂等芳烷基型酚樹脂；對二甲苯改質酚樹脂及/或間二甲苯改質酚樹脂；三聚氰胺改質酚樹脂；萜烯改質酚樹脂；由所述酚性化合物與二環戊二烯藉由共聚合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於酸性觸媒下縮合或共縮合而獲得的三苯基甲烷型酚樹脂；2-[4-[(2-羥基-3-(2'-乙基)己基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪等三嗪型酚樹脂；將該些的兩種以上共聚合而獲得的酚樹脂等。 Examples of the phenolic curing agent include phenol resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule. Although the specific example of a phenolic curing agent is described below, it is not limited to these. Examples of the phenolic curing agent include: polyphenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; Phenol compounds such as cresol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene A novolac type phenolic resin obtained by condensation or co-condensation of at least one phenolic compound in the group formed with formaldehyde, acetaldehyde, propionaldehyde and other aldehyde compounds under an acidic catalyst; from the phenolic compound and dimethyl Aralkyl-type phenol resins such as phenol aralkyl resins, naphthol aralkyl resins, etc. synthesized from oxy-p-xylene and bis(methoxymethyl)biphenyl; p-xylene modified phenol resins and/or m-xylene modified phenol resin; melamine modified phenol resin; terpene modified phenol resin; dicyclopentadiene type phenol resin and dicyclopentadiene synthesized by copolymerization of the phenolic compound and dicyclopentadiene Cyclopentadiene type naphthol resin; Cyclopentadiene modified phenol resin; Polycyclic aromatic ring modified phenol resin; Biphenyl type phenol resin; Make the phenolic compound and aromatic aldehydes such as benzaldehyde and salicylaldehyde Triphenylmethane-type phenolic resin obtained by condensation or co-condensation of compounds under an acidic catalyst; 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyl Triazine-type phenol resins such as phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; phenol resins obtained by copolymerizing two or more of these wait.

就第一態樣的硬化性樹脂組成物的耐回焊性的觀點而言，酚系硬化劑較佳為包含選自由芳烷基型酚樹脂及酚醛清漆型酚樹脂所組成的群組中的一種以上的酚系硬化劑，更佳為均包含。以下，對酚系硬化劑進行更具體說明，但並不限定於該些。From the viewpoint of the reflow resistance of the curable resin composition of the first aspect, it is preferable that the phenolic curing agent is selected from the group consisting of aralkyl type phenol resins and novolac type phenol resins. More than one type of phenolic curing agent is more preferably contained. Hereinafter, the phenolic curing agent will be described in more detail, but it is not limited thereto.

芳烷基型酚樹脂並無特別限定，可列舉由選自由酚化合物及萘酚化合物所組成的群組中的至少一種、二甲氧基對二甲苯、雙(甲氧基甲基)聯苯或該些的衍生物合成的酚樹脂。作為芳烷基型酚樹脂的具體例，可列舉下述通式（XII）～通式（XIV）所表示的酚樹脂。於式（XII）～式（XIV）中，R ²³表示氫原子或碳數1～18的一價有機基，可分別均相同亦可不同。R ²²、R ²⁴、R ²⁵及R ²⁸表示碳數1～18的一價有機基，可分別均相同亦可不同。R ²⁶及R ²⁷表示羥基或碳數1～18的一價有機基，可分別均相同亦可不同。i各自獨立地為0～3的整數，j各自獨立地為0～2的整數，k各自獨立地為0～4的整數，p各自獨立地為0～4的整數。n為平均值，且各自獨立地為0～10的整數。針對所述通式中的R ²²等所記載的「可分別均相同亦可不同」例如是指通式（XII）中的i個R ²²可均相同亦可相互不同。另外，R ²²～R ³⁷可分別相同亦可不同。例如，R ²²及R ²³可均相同亦可不同。 The aralkyl-type phenol resin is not particularly limited, and examples thereof include at least one selected from the group consisting of phenol compounds and naphthol compounds, dimethoxy-p-xylene, and bis(methoxymethyl)biphenyl Or the phenolic resin synthesized by these derivatives. Specific examples of the aralkyl-type phenol resin include phenol resins represented by the following general formulas (XII) to (XIV). In formulas (XII) to (XIV), R ²³ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbons, which may be the same or different. R ²² , R ²⁴ , R ²⁵ and R ²⁸ represent a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. R ²⁶ and R ²⁷ represent a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i is each independently an integer of 0-3, j is each independently an integer of 0-2, k is each independently an integer of 0-4, and p is each independently an integer of 0-4. n is an average value, and is an integer of 0-10 each independently. The "may be the same or different" described for R ²² and the like in the general formula, for example, means that i R ²² in the general formula (XII) may be all the same or different from each other. In addition, R ²² to R ³⁷ may be the same or different. For example, R ²² and R ²³ may both be the same or different.

就第一態樣的硬化性樹脂組成物的耐回焊性的觀點而言，芳烷基型酚樹脂較佳為通式（XIII）所表示的酚樹脂。就第一態樣的硬化性樹脂組成物的耐回焊性的觀點而言，另外，通式（XIII）中，i及k較佳為均為0。 From the viewpoint of the reflow resistance of the curable resin composition of the first aspect, the aralkyl-type phenol resin is preferably a phenol resin represented by the general formula (XIII). From the viewpoint of the reflow resistance of the curable resin composition of the first aspect, in the general formula (XIII), both i and k are preferably 0.

[化15]

[chemical 15]

芳烷基型酚樹脂亦可為與其他酚樹脂的共聚合型酚樹脂。作為共聚合型酚樹脂，可列舉：三苯基甲烷型酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂、水楊醛型酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂、酚醛清漆型酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂等。The aralkyl type phenol resin may also be a copolymer type phenol resin with other phenol resins. Examples of the copolymerized phenol resin include a copolymerized phenol resin of a triphenylmethane-type phenol resin and an aralkyl-type phenol resin, and a copolymerized phenol resin of a salicylaldehyde-type phenol resin and an aralkyl-type phenol resin. , Copolymerized phenolic resins of novolac type phenolic resins and aralkyl type phenolic resins, etc.

二環戊二烯型酚樹脂只要為將具有二環戊二烯骨架的化合物作為原料而獲得的酚樹脂，則並無特別限定。例如較佳為下述通式（XV）所表示的酚樹脂。The dicyclopentadiene-type phenol resin is not particularly limited as long as it is a phenol resin obtained from a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenol resin represented by the following general formula (XV) is preferable.

[化16]

[chemical 16]

式（XV）中，R ²⁹表示碳數1～18的一價有機基，可分別均相同亦可不同。i各自獨立地表示0～3的整數。n為平均值，且表示0～10的整數。 In the formula (XV), R ²⁹ represents a monovalent organic group having 1 to 18 carbon atoms, which may be the same or different. i each independently represents an integer of 0-3. n is an average value, and represents the integer of 0-10.

三苯基甲烷型酚樹脂只要為將芳香族醛化合物作為原料而獲得的酚樹脂，則並無特別限定。例如較佳為下述通式（XVI）所表示的酚樹脂。The triphenylmethane-type phenol resin is not particularly limited as long as it is a phenol resin obtained from an aromatic aldehyde compound as a raw material. For example, a phenol resin represented by the following general formula (XVI) is preferable.

[化17]

[chemical 17]

式（XVI）中，R ³⁰及R ³¹表示碳數1～18的一價有機基，可分別均相同亦可不同。i分別獨立地為0～3的整數，k分別獨立地為0～4的整數。n為平均值，且為0～10的整數。 In the formula (XVI), R ³⁰ and R ³¹ represent a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i is an integer of 0-3 each independently, and k is an integer of 0-4 each independently. n is an average value, and is an integer of 0-10.

三苯基甲烷型酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂只要為將具有苯甲醛骨架的化合物作為原料而獲得的酚樹脂與芳烷基型酚樹脂的共聚合型酚樹脂，則並無特別限定。例如較佳為下述通式（XVII）所表示的酚樹脂。The copolymerization type phenol resin of a triphenylmethane type phenol resin and an aralkyl type phenol resin is a copolymerization type phenol resin of a phenol resin obtained from a compound having a benzaldehyde skeleton as a raw material and an aralkyl type phenol resin, is not particularly limited. For example, a phenol resin represented by the following general formula (XVII) is preferable.

[化18]

[chemical 18]

式（XVII）中，R ³²～R ³⁴表示碳數1～18的一價有機基，可分別均相同亦可不同。i分別獨立地為0～3的整數，k分別獨立地為0～4的整數，q分別獨立地為0～5的整數。l及m分別為平均值，且分別獨立地為0～11的整數。其中，l與m的合計為1～11的整數。 In formula (XVII), R ³² to R ³⁴ represent monovalent organic groups having 1 to 18 carbon atoms, and may be the same or different. i is an integer of 0 to 3 each independently, k is an integer of 0 to 4 each independently, and q is an integer of 0 to 5 each independently. l and m are each an average value, and are each independently an integer of 0-11. However, the total of l and m is an integer of 1-11.

酚醛清漆型酚樹脂只要為使選自由苯酚化合物及萘酚化合物所組成的群組中的至少一種酚性化合物與醛化合物於酸性觸媒下縮合或共縮合而獲得的酚樹脂，則並無特別限定。例如較佳為下述通式（XVIII）所表示的酚樹脂。Novolak-type phenolic resins are not particularly phenolic resins as long as they are obtained by condensing or cocondensing at least one phenolic compound selected from the group consisting of phenolic compounds and naphthol compounds with an aldehyde compound under an acidic catalyst. limited. For example, a phenol resin represented by the following general formula (XVIII) is preferable.

[化19]

[chemical 19]

式（XVIII）中，R ³⁵表示氫原子或碳數1～18的一價有機基，可分別均相同亦可不同。R ³⁶表示碳數1～18的一價有機基，可分別均相同亦可不同。i各自獨立地表示0～3的整數。n為平均值，且表示0～10的整數。 In formula (XVIII), R ³⁵ represents a hydrogen atom or a monovalent organic group having 1 to 18 carbons, which may be the same or different. R ³⁶ represents a monovalent organic group having 1 to 18 carbon atoms, which may be the same or different. i each independently represents an integer of 0-3. n is an average value, and represents the integer of 0-10.

關於所述通式（XII）～通式（XVIII）中的R ²²～R ³⁶所記載的「可分別均相同亦可不同」例如是指式（XII）中的i個R ²²可均相同亦可相互不同。關於其他的R ²³～R ³⁶，亦是指式中所含的各自的個數可均相同亦可相互不同。另外，R ²²～R ³⁶分別可相同亦可不同。例如，R ²²及R ²³可均相同亦可不同，R ³⁰及R ³¹可均相同亦可不同。 Regarding R ²² to R ³⁶ in general formula (XII) to general formula (XVIII), "may be the same or different", for example, means that i R ²² in formula (XII) may all be the same or can be different from each other. Regarding other R ²³ to R ³⁶ , it also means that the respective numbers contained in the formula may be the same or different from each other. In addition, R ²² to R ³⁶ may be the same or different. For example, ^R22 and ^R23 may be both the same or different, and ^R30 and ^R31 may be both the same or different.

所述通式（XII）～通式（XVIII）中的n較佳為0～10的整數。若為10以下，則樹脂成分的熔融黏度不會過高，於硬化性樹脂組成物的熔融成形時，黏度亦變低，不易產生填充不良、接合線（連接元件與引線的金屬線）的變形等。一分子中的平均n較佳為設定為0～4的範圍。n in the general formula (XII) to general formula (XVIII) is preferably an integer of 0-10. If it is 10 or less, the melt viscosity of the resin component will not be too high, and the viscosity will also be low during melt molding of the curable resin composition, making it difficult to cause poor filling and deformation of bonding wires (metal wires that connect elements and leads). wait. The average n in one molecule is preferably set in the range of 0-4.

酚系硬化劑的羥基當量並無特別限制。就耐回焊性、成形性、電可靠性等各種特性平衡的觀點而言，較佳為10 g/eq～1000 g/eq，更佳為30 g/eq～500 g/eq。羥基當量是指基於依據JIS K 0070：1992測定所得的羥基值而算出的值。 The hydroxyl equivalent of the phenolic curing agent is not particularly limited. From the viewpoint of the balance of various properties such as reflow resistance, formability, and electrical reliability, it is preferably 10 g/eq to 1000 g/eq, and more preferably 30 g/eq to 500 g/eq. The hydroxyl equivalent is a value calculated based on the hydroxyl value measured in accordance with JIS K 0070:1992.

於酚系硬化劑於25℃下為固體的情況下，酚系硬化劑的軟化點或熔點並無特別限制。就成形性與耐熱性的觀點而言，酚系硬化劑的軟化點或熔點較佳為40℃～180℃。另外，就硬化性樹脂組成物的製造時的操作性的觀點而言，酚系硬化劑的軟化點或熔點較佳為50℃～130℃。In the case where the phenolic hardener is solid at 25° C., the softening point or melting point of the phenolic hardener is not particularly limited. From the viewpoint of formability and heat resistance, the softening point or melting point of the phenolic curing agent is preferably 40°C to 180°C. In addition, the softening point or melting point of the phenolic curing agent is preferably 50° C. to 130° C. from the viewpoint of workability at the time of production of the curable resin composition.

就第一態樣的硬化性樹脂組成物的耐回焊性的觀點而言，酚系硬化劑相對於硬化性樹脂組成物的總質量的含有率較佳為0.5質量%～40質量%，更佳為1質量%～30質量%，進而佳為2質量%～20質量%。From the viewpoint of the reflow resistance of the curable resin composition of the first aspect, the content of the phenolic curing agent relative to the total mass of the curable resin composition is preferably 0.5% by mass to 40% by mass, more preferably Preferably, it is 1 mass % - 30 mass %, More preferably, it is 2 mass % - 20 mass %.

就第一態樣的硬化性樹脂組成物的耐回焊性的觀點而言，於酚系硬化劑包含芳烷基型酚樹脂的情況下，芳烷基型酚樹脂相對於酚系硬化劑的總質量的含有率較佳為60質量%～95質量%，更佳為65質量%～90質量%。From the viewpoint of the reflow resistance of the curable resin composition of the first aspect, when the phenolic curing agent contains an aralkyl type phenol resin, the ratio of the aralkyl type phenol resin to the phenolic curing agent is The content of the total mass is preferably from 60% by mass to 95% by mass, more preferably from 65% by mass to 90% by mass.

就第一態樣的硬化性樹脂組成物的耐回焊性的觀點而言，於酚系硬化劑包含酚醛清漆型酚樹脂的情況下，酚醛清漆型酚樹脂相對於酚系硬化劑的總質量的含有率較佳為5質量%～40質量%，更佳為10質量%～30質量%。From the viewpoint of the reflow resistance of the curable resin composition of the first aspect, when the phenolic hardener contains a novolak-type phenolic resin, the total mass of the novolac-type phenolic resin relative to the phenolic hardener The content of is preferably from 5% by mass to 40% by mass, more preferably from 10% by mass to 30% by mass.

（各種添加材）第一態樣的硬化性樹脂組成物除所述成分以外，亦可含有硬化促進劑、無機填充劑、偶合劑、應力緩和劑、脫模劑、著色劑、阻燃劑、離子交換體、環氧樹脂以外的樹脂、酚系硬化劑以外的硬化劑等各種添加材。硬化性樹脂組成物除以下例示的添加材以外，視需要亦可含有該技術領域中眾所周知的各種添加材。 (various additives) The curable resin composition of the first aspect may contain, in addition to the above-mentioned components, a curing accelerator, an inorganic filler, a coupling agent, a stress relieving agent, a release agent, a colorant, a flame retardant, an ion exchanger, a ring Various additives such as resins other than epoxy resins and hardeners other than phenolic hardeners. The curable resin composition may contain various additives well-known in the technical field as needed, in addition to the additives exemplified below.

（硬化促進劑）第一態樣的硬化性樹脂組成物亦可含有硬化促進劑。硬化促進劑的種類並無特別限制，可根據環氧樹脂的種類、硬化性樹脂組成物的所期望的特性等來選擇。 (hardening accelerator) The curable resin composition of the first aspect may also contain a curing accelerator. The type of curing accelerator is not particularly limited, and can be selected according to the type of epoxy resin, desired properties of the curable resin composition, and the like.

就硬化性及流動性的觀點而言，硬化促進劑較佳為含有鏻化合物。作為鏻化合物，具體而言，可列舉：三苯基膦、二苯基(對甲苯)膦、三(烷基苯基)膦、三(烷氧基苯基)膦、三(烷基-烷氧基苯基)膦、三(二烷基苯基)膦、三(三烷基苯基)膦、三(四烷基苯基)膦、三(二烷氧基苯基)膦、三(三烷氧基苯基)膦、三(四烷氧基苯基)膦、三烷基膦、二烷基芳基膦、烷基二芳基膦等三級膦；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、重氮苯基甲烷等具有π鍵的化合物加成而形成的具有分子內極化的化合物；於使三級膦與4-溴苯酚、3-溴苯酚、2-溴苯酚、4-氯苯酚、3-氯苯酚、2-氯苯酚、4-碘苯酚、3-碘苯酚、2-碘苯酚、4-溴-2-甲基苯酚、4-溴-3-甲基苯酚、4-溴-2,6-二甲基苯酚、4-溴-3,5-二甲基苯酚、4-溴-2,6-二-第三丁基苯酚、4-氯-1-萘酚、1-溴-2-萘酚、6-溴-2-萘酚、4-溴-4'-羥基聯苯等鹵化酚化合物反應後經過脫鹵化氫的步驟而獲得的具有分子內極化的化合物；四苯基鏻等四取代鏻與四-對甲苯硼酸酯等四取代硼酸酯的鹽；四取代鏻與自酚化合物脫離質子後的陰離子的鹽、四取代鏻與自羧酸化合物脫離質子後的陰離子的鹽等。From the viewpoint of curability and fluidity, the curing accelerator preferably contains a phosphonium compound. Specific examples of the phosphonium compound include triphenylphosphine, diphenyl(p-toluene)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkyl-alkane) Oxyphenyl)phosphine, Tris(dialkylphenyl)phosphine, Tris(trialkylphenyl)phosphine, Tris(tetraalkylphenyl)phosphine, Tris(dialkoxyphenyl)phosphine, Tris( Tertiary phosphines such as trialkoxyphenyl)phosphine, tri(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine; maleic anhydride, 1,4 -Benzoquinone, 2,5-methylbenzoquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methanol Quinone compounds such as base-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and compounds with π bonds such as diazophenylmethane A compound with intramolecular polarization; used to make tri-level phosphine and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4- Iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo- 3,5-Dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthalene Compounds with intramolecular polarization obtained after the reaction of halogenated phenolic compounds such as phenol and 4-bromo-4'-hydroxybiphenyl through the step of dehydrohalogenation; four-substituted phosphonium such as tetraphenylphosphonium and tetra-p-tolueneboronic acid Salts of tetrasubstituted borate esters such as esters; salts of tetrasubstituted phosphonium and anions deprotonated from phenolic compounds, salts of tetrasubstituted phosphonium and anions deprotonated from carboxylic acid compounds, and the like.

所述鏻化合物較佳為包含下述通式（I-1）所表示的化合物（以下，亦稱為特定硬化促進劑）。The phosphonium compound preferably includes a compound represented by the following general formula (I-1) (hereinafter also referred to as a specific hardening accelerator).

[化20]

[chemical 20]

式（I-1）中，R ¹～R ³各自獨立地為碳數1～18的烴基，R ¹～R ³中的兩個以上可相互鍵結而形成環狀結構，R ⁴～R ⁷各自獨立地為氫原子、羥基或碳數1～18的有機基，R ⁴～R ⁷中的兩個以上可相互鍵結而形成環狀結構。 In formula (I-1), R ¹ to R ³ are each independently a hydrocarbon group with 1 to 18 carbons, two or more of R ¹ to R ³ may be bonded to each other to form a ring structure, and R ⁴ to R ⁷ Each is independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 18 carbon atoms, and two or more of R ⁴ to R ⁷ may be bonded to each other to form a ring structure.

作為通式（I-1）的R ¹～R ³所記載的「碳數1～18的烴基」包含碳數為1～18的脂肪族烴基及碳數為6～18的芳香族烴基。 The "hydrocarbon group having 1 to 18 carbons" described as R ¹ to R ³ of the general formula (I-1) includes an aliphatic hydrocarbon group having 1 to 18 carbons and an aromatic hydrocarbon group having 6 to 18 carbons.

就流動性的觀點而言，碳數1～18的脂肪族烴基較佳為碳數1～8，更佳為2～6，進而佳為4～6。The aliphatic hydrocarbon group having 1 to 18 carbons is preferably from 1 to 8 carbons, more preferably from 2 to 6 carbons, and still more preferably from 4 to 6 carbons, from the viewpoint of fluidity.

碳數1～18的脂肪族烴基可為碳數1～18的直鏈或分支狀的脂肪族烴基，亦可為碳數3～18的脂環式烴基。就容易製造的觀點而言，較佳為直鏈或分支狀的脂肪族烴基。The aliphatic hydrocarbon group having 1 to 18 carbons may be a linear or branched aliphatic hydrocarbon group having 1 to 18 carbons, or an alicyclic hydrocarbon group having 3 to 18 carbons. From the viewpoint of ease of production, a straight-chain or branched aliphatic hydrocarbon group is preferred.

作為碳數1～18的直鏈或分支狀的脂肪族烴基，具體而言，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、戊基、己基、辛基、癸基、十二烷基等烷基、烯丙基、乙烯基等。直鏈或分支狀的脂肪族烴基可具有取代基，亦可不具有取代基。作為取代基，可列舉：甲氧基、乙氧基、正丁氧基、第三丁氧基等烷氧基、苯基、萘基等芳基、羥基、胺基、鹵素原子等。直鏈或分支狀的脂肪族烴基可具有兩個以上的取代基，此時的取代基可相同亦可不同。於直鏈或分支狀的脂肪族烴基具有取代基的情況下，脂肪族烴基與取代基中所含的碳數的合計較佳為1～18。就硬化性的觀點而言，較佳為未經取代的烷基，更佳為碳數1～8的未經取代的烷基，進而佳為正丁基、異丁基、正戊基、正己基及正辛基。Examples of straight-chain or branched aliphatic hydrocarbon groups having 1 to 18 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and second-butyl. , tertiary butyl, pentyl, hexyl, octyl, decyl, dodecyl and other alkyl, allyl, vinyl, etc. A straight-chain or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include alkoxy groups such as methoxy, ethoxy, n-butoxy, and tert-butoxy, aryl groups such as phenyl and naphthyl, hydroxyl groups, amino groups, and halogen atoms. A linear or branched aliphatic hydrocarbon group may have two or more substituents, and the substituents may be the same or different in this case. When the linear or branched aliphatic hydrocarbon group has a substituent, the total number of carbon atoms contained in the aliphatic hydrocarbon group and the substituent is preferably 1-18. From the viewpoint of hardenability, an unsubstituted alkyl group is preferred, an unsubstituted alkyl group having 1 to 8 carbon atoms is more preferred, and n-butyl, isobutyl, n-pentyl, and n-hexyl are further preferred. base and n-octyl.

作為碳數3～18的脂環式烴基，具體而言，可列舉：環戊基、環己基、環庚基等環烷基、環戊烯基、環己烯基等環烯基等。脂環式烴基可具有取代基，亦可不具有取代基。作為取代基，可列舉：甲基、乙基、正丁基、第三丁基等烷基、甲氧基、乙氧基、正丁氧基、第三丁氧基等烷氧基、苯基、萘基等芳基、羥基、胺基、鹵素原子等。脂環式烴基可具有兩個以上的取代基，此時的取代基可相同亦可不同。於脂環式烴基具有取代基的情況下，脂環式烴基與取代基中所含的碳數的合計較佳為3～18。於脂環式烴基具有取代基的情況下，取代基的位置並無特別限定。就硬化性的觀點而言，較佳為未經取代的環烷基，更佳為碳數4～10的未經取代的環烷基，進而佳為環己基、環戊基及環庚基。Specific examples of the alicyclic hydrocarbon group having 3 to 18 carbon atoms include cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl, and cycloalkenyl groups such as cyclopentenyl and cyclohexenyl. The alicyclic hydrocarbon group may or may not have a substituent. Examples of substituents include alkyl groups such as methyl, ethyl, n-butyl, and tert-butyl, alkoxy groups such as methoxy, ethoxy, n-butoxy, and tert-butoxy, and phenyl groups. , naphthyl and other aryl groups, hydroxyl groups, amino groups, halogen atoms, etc. The alicyclic hydrocarbon group may have two or more substituents, and the substituents in this case may be the same or different. When the alicyclic hydrocarbon group has a substituent, the total number of carbon atoms contained in the alicyclic hydrocarbon group and the substituent is preferably 3-18. When the alicyclic hydrocarbon group has a substituent, the position of the substituent is not particularly limited. From the viewpoint of hardenability, unsubstituted cycloalkyl is preferred, unsubstituted cycloalkyl having 4 to 10 carbon atoms is more preferred, and cyclohexyl, cyclopentyl and cycloheptyl are further preferred.

碳數為6～18的芳香族烴基較佳為碳數6～14，更佳為6～10。芳香族烴基可具有取代基，亦可不具有取代基。作為取代基，可列舉：甲基、乙基、正丁基、第三丁基等烷基、甲氧基、乙氧基、正丁氧基、第三丁氧基等烷氧基、苯基、萘基等芳基、羥基、胺基、鹵素原子等。芳香族烴基可具有兩個以上的取代基，此時的取代基可相同亦可不同。於芳香族烴基具有取代基的情況下，芳香族烴基與取代基中所含的碳數的合計較佳為6～18。於芳香族烴基具有取代基的情況下，取代基的位置並無特別限定。The aromatic hydrocarbon group having 6-18 carbon atoms is preferably 6-14 carbon atoms, more preferably 6-10 carbon atoms. The aromatic hydrocarbon group may or may not have a substituent. Examples of substituents include alkyl groups such as methyl, ethyl, n-butyl, and tert-butyl, alkoxy groups such as methoxy, ethoxy, n-butoxy, and tert-butoxy, and phenyl groups. , naphthyl and other aryl groups, hydroxyl groups, amino groups, halogen atoms, etc. The aromatic hydrocarbon group may have two or more substituents, and the substituents in this case may be the same or different. When the aromatic hydrocarbon group has a substituent, the total number of carbon atoms contained in the aromatic hydrocarbon group and the substituent is preferably 6-18. When the aromatic hydrocarbon group has a substituent, the position of the substituent is not particularly limited.

作為碳數為6～18的芳香族烴基，具體而言，可列舉：苯基、1-萘基、2-萘基、甲苯基、二甲基苯基、乙基苯基、丁基苯基、第三丁基苯基、甲氧基苯基、乙氧基苯基、正丁氧基苯基、第三丁氧基苯基等。該些芳香族烴基中的取代基的位置可為鄰位、間位及對位中的任一種。就流動性的觀點而言，較佳為未經取代且碳數為6～12或包含取代基的碳數為6～12的芳基，更佳為未經取代且碳數為6～10或包含取代基的碳數為6～10的芳基，進而佳為苯基、對甲苯基及對甲氧基苯基。Specific examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms include: phenyl, 1-naphthyl, 2-naphthyl, tolyl, dimethylphenyl, ethylphenyl, butylphenyl , tertiary butylphenyl, methoxyphenyl, ethoxyphenyl, n-butoxyphenyl, tertiary butoxyphenyl, etc. The positions of the substituents in these aromatic hydrocarbon groups may be any of ortho, meta and para. From the viewpoint of fluidity, unsubstituted aryl groups having 6 to 12 carbon atoms or substituents are preferred, and unsubstituted aryl groups having 6 to 10 carbon atoms are more preferred. The aryl group having 6 to 10 carbon atoms including substituents is more preferably phenyl, p-tolyl and p-methoxyphenyl.

作為通式（I-1）的R ¹～R ³所記載的用語「R ¹～R ³中的兩個以上可相互鍵結而形成環狀結構」是指R ¹～R ³中的2個或3個鍵結，整體成為一個二價或三價烴基的情況。作為此時的R ¹～R ³的例子，可列舉：可與磷原子鍵結而形成環狀結構的伸乙基、伸丙基、伸丁基、伸戊基、伸己基等伸烷基、伸乙炔基、伸丙炔基、伸丁炔基等伸烯基、亞甲基伸苯基等伸芳烷基、伸苯基、伸萘基、伸蒽基等伸芳基等、可與磷原子鍵結而形成環狀結構的取代基。該些取代基亦可進一步經烷基、烷氧基、芳基、芳氧基、胺基、羥基、鹵素原子等取代。 The term "two or more of R ¹ to R ³ may be bonded to each other to form a ring structure" described as R ¹ to R ³ of the general formula (I-1) means that two of R ¹ to R ³ Or three bonds, the whole becomes a divalent or trivalent hydrocarbon group. Examples of R ¹ to R ³ in this case include alkylene groups such as ethylidene, propylidene, butylene, pentylene, and hexylene that can form a ring structure by bonding with a phosphorus atom, Ethynyl, propynyl, butynyl and other alkenyl groups, methylene phenylene and other arylene groups, phenylene, naphthylene, anthracenyl and other aryl groups, etc., can be combined with phosphorus A substituent in which atoms are bonded to form a ring structure. These substituents may also be further substituted by alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms and the like.

作為所述通式（I-1）中的R ⁴～R ⁷所記載的「碳數1～18的有機基」是指包含碳數為1～18且可經取代亦可未經取代的脂肪族烴基、芳香族烴基、脂肪族烴氧基、芳香族烴氧基、醯基、烴氧基羰基、以及醯氧基。 The "organic group having 1 to 18 carbon atoms" described as R ⁴ to R ⁷ in the general formula (I-1) refers to a fatty group having 1 to 18 carbon atoms which may be substituted or not. Aromatic hydrocarbyl, aromatic hydrocarbyl, aliphatic hydrocarbyloxy, aromatic hydrocarbyloxy, acyl, alkoxycarbonyl, and acyloxy.

作為所述脂肪族烴基及芳香族烴基的例子，可列舉作為R ¹～R ³所表示的脂肪族烴基及芳香族烴基的例子於上文敘述的基。 Examples of the aliphatic hydrocarbon group and aromatic hydrocarbon group include those described above as examples of the aliphatic hydrocarbon group and aromatic hydrocarbon group represented by R ¹ to R ³ .

作為所述脂肪族烴氧基，可列舉：甲氧基、乙氧基、丙氧基、異丙氧基、正丁氧基、2-丁氧基、第三丁氧基、環丙氧基、環己氧基、環戊氧基、烯丙氧基、乙烯氧基等所述脂肪族烴基上鍵結有氧原子的結構的氧基；該些脂肪族烴氧基進一步被烷基、烷氧基、芳基、芳氧基、胺基、羥基、鹵素原子等取代的基等。Examples of the aliphatic hydrocarbonoxy group include: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, cyclopropoxy , cyclohexyloxy, cyclopentyloxy, allyloxy, ethyleneoxy and other aliphatic hydrocarbon groups bonded with oxygen atom structures; A group substituted with an oxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom, or the like.

作為所述芳香族烴氧基，可列舉：苯氧基、甲基苯氧基、乙基苯氧基、甲氧基苯氧基、丁氧基苯氧基、苯氧基苯氧基等所述芳香族烴基上鍵結有氧原子的結構的氧基；該些芳香族烴氧基進一步被烷基、烷氧基、芳基、芳氧基、胺基、鹵素原子等取代的基等。Examples of the aromatic hydrocarbonoxy group include: phenoxy, methylphenoxy, ethylphenoxy, methoxyphenoxy, butoxyphenoxy, phenoxyphenoxy, etc. Oxygen groups with oxygen atoms bonded to the above-mentioned aromatic hydrocarbon groups; groups in which these aromatic hydrocarbon groups are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc.

作為所述醯基，可列舉：甲醯基、乙醯基、乙基羰基、丁醯基、環己基羰基、烯丙基羰基等脂肪族烴羰基、苯基羰基、甲基苯基羰基等芳香族烴羰基等；該些脂肪族烴羰基或芳香族烴羰基進一步被烷基、烷氧基、芳基、芳氧基、胺基、鹵素原子等取代的基等。Examples of the acyl group include aliphatic hydrocarbon carbonyls such as formyl, acetyl, ethylcarbonyl, butyryl, cyclohexylcarbonyl, and allylcarbonyl, and aromatic hydrocarbons such as phenylcarbonyl and methylphenylcarbonyl. carbonyl, etc.; these aliphatic hydrocarbon carbonyls or aromatic hydrocarbon carbonyls are further substituted with alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, halogen atoms, etc., etc.

作為所述烴氧羰基，可列舉：甲氧基羰基、乙氧基羰基、丁氧基羰基、烯丙氧基羰基、環己基氧基羰基等脂肪族烴氧羰基、苯氧基羰基、甲基苯氧基羰基等芳香族烴氧羰基、該些脂肪族烴羰氧基或芳香族烴羰氧基進一步被烷基、烷氧基、芳基、芳氧基、胺基、鹵素原子等取代的基等。Examples of the alkoxycarbonyl group include aliphatic alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, allyloxycarbonyl, and cyclohexyloxycarbonyl, phenoxycarbonyl, methyl Aromatic hydrocarbon oxycarbonyl groups such as phenoxycarbonyl, these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups further substituted by alkyl, alkoxy, aryl, aryloxy, amino, halogen atoms, etc. Base etc.

作為所述醯氧基，可列舉：甲基羰氧基、乙基羰氧基、丁基羰氧基、烯丙基羰氧基、環己基羰氧基等脂肪族烴羰氧基、苯基羰氧基、甲基苯基羰氧基等芳香族烴羰氧基、該些脂肪族烴羰氧基或芳香族烴羰氧基進一步被烷基、烷氧基、芳基、芳氧基、胺基、鹵素原子等取代的基等。Examples of the acyloxy group include aliphatic hydrocarbon carbonyloxy groups such as methylcarbonyloxy, ethylcarbonyloxy, butylcarbonyloxy, allylcarbonyloxy, and cyclohexylcarbonyloxy; phenyl Carbonyloxy, methylphenylcarbonyloxy and other aromatic hydrocarbon carbonyloxy, these aliphatic hydrocarbon carbonyl or aromatic hydrocarbon carbonyloxy are further replaced by alkyl, alkoxy, aryl, aryloxy, Amino groups, groups substituted with halogen atoms, etc.

作為所述通式（I-1）的R ⁴～R ⁷所記載的用語「R ⁴～R ⁷中的兩個以上可相互鍵結而形成環狀結構」是指2個～4個R ⁴～R ⁷鍵結，作為整體可形成一個2價～4價的有機基。作為此時的R ⁴～R ⁷，可列舉：伸乙基、伸丙基、伸丁基、伸戊基、伸己基等伸烷基、伸乙炔基、伸丙炔基、伸丁炔基等伸烯基、亞甲基伸苯基等伸芳烷基、伸苯基、伸萘基、伸蒽基等伸芳基等可形成環狀結構的取代基、該些的氧基或雙氧基等。該些取代基亦可進一步經烷基、烷氧基、芳基、芳氧基、胺基、羥基、鹵素原子等取代。 The term "two or more of R ⁴ to R ⁷ may be bonded to each other to form a ring structure" described as R ⁴ to R ⁷ in the general formula (I-1) means that 2 to 4 R ⁴ ～R ⁷ is bonded, and as a whole, it can form a 2-4 valent organic group. Examples of R ⁴ to R ⁷ in this case include alkylene groups such as ethylidene, propylene, butyl, pentylene, and hexylene, ethynyl, propynyl, butynyl, etc. Arylene groups such as alkenylene, methylene phenylene, etc., arylene groups such as phenylene, naphthylene, anthracenyl, etc., substituents that can form a ring structure, and oxy or dioxy groups of these wait. These substituents may also be further substituted by alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, hydroxyl groups, halogen atoms and the like.

作為所述通式（I-1）的R ⁴～R ⁷，並無特別限定。例如較佳為各自獨立地選自氫原子、羥基、經取代或未經取代的烷基、經取代或未經取代的芳基、經取代或未經取代的烷氧基、或經取代或未經取代的芳氧基。其中，就原料的獲取容易性的觀點而言，較佳為氫原子、羥基、未經取代或經選自由烷基及烷氧基所組成的群組中的至少一種取代的芳基、或者鏈狀或環狀的烷基。作為未經取代或經選自由烷基及烷氧基所組成的群組中的至少一種取代的芳基，可列舉：苯基、對甲苯基、間甲苯基、鄰甲苯基、對甲氧基苯基等。作為鏈狀或環狀的烷基，可列舉：甲基、乙基、正丙基、異丙基、正丁基、2-丁基、第三丁基、辛基、環己基等。就硬化性的觀點而言，較佳為R ⁴～R ⁷全部為氫原子的情況、或者R ⁴～R ⁷中的至少一個為羥基、其餘全部為氫原子的情況。 R ⁴ to R ⁷ in the general formula (I-1) are not particularly limited. For example, preferably each independently selected from a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted Substituted aryloxy. Among them, from the viewpoint of easy acquisition of raw materials, hydrogen atoms, hydroxyl groups, unsubstituted or substituted aryl groups selected from the group consisting of alkyl groups and alkoxy groups, or chain Shaped or cyclic alkyl. Examples of unsubstituted or substituted aryl groups selected from the group consisting of alkyl groups and alkoxy groups include: phenyl, p-tolyl, m-tolyl, o-tolyl, and p-methoxy Phenyl, etc. Examples of chain or cyclic alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, octyl, and cyclohexyl. From the viewpoint of curability, it is preferable that all of R ⁴ to R ⁷ are hydrogen atoms, or that at least one of R ⁴ to R ⁷ is a hydroxyl group and the rest are all hydrogen atoms.

於通式（I-1）中，更佳為R ¹～R ³中的2個以上為碳數1～18的烷基或碳數3～18的環烷基，R ⁴～R ⁷全部為氫原子或至少一個為羥基，其餘全部為氫原子。進而佳為R ¹～R ³中的全部為碳數1～18的烷基或碳數3～18的環烷基，R ⁴～R ⁷全部為氫原子或至少一個為羥基，其餘全部為氫原子。 In the general formula (I-1), more than two of R ¹ to R ³ are alkyl groups with 1 to 18 carbons or cycloalkyl groups with 3 to 18 carbons, and R ⁴ to R ⁷ are all Hydrogen atoms or at least one is a hydroxyl group, and all the others are hydrogen atoms. More preferably, all of R ¹ to R ³ are alkyl groups having 1 to 18 carbons or cycloalkyl groups having 3 to 18 carbons, all of R ⁴ to R ⁷ are hydrogen atoms or at least one is hydroxyl, and the rest are all hydrogen atom.

就快速硬化性的觀點而言，特定硬化促進劑較佳為包含下述通式（I-2）所表示的化合物。From the viewpoint of rapid hardening, the specific hardening accelerator preferably contains a compound represented by the following general formula (I-2).

[化21]

[chem 21]

式（I-2）中，R ¹～R ³各自獨立地為碳數1～18的烴基，R ¹～R ³中的兩個以上可相互鍵結而形成環狀結構，R ⁴～R ⁶各自獨立地為氫原子或碳數1～18的有機基，R ⁴～R ⁶中的兩個以上可相互鍵結而形成環狀結構。 In formula (I-2), R ¹ to R ³ are each independently a hydrocarbon group with 1 to 18 carbons, two or more of R ¹ to R ³ may be bonded to each other to form a ring structure, and R ⁴ to R ⁶ Each is independently a hydrogen atom or an organic group having 1 to 18 carbons, and two or more of R ⁴ to R ⁶ may be bonded to each other to form a ring structure.

通式（I-2）中的R ¹～R ⁶的具體例分別與通式（I-1）中的R ¹～R ⁶的具體例相同，較佳範圍亦相同。 The specific examples of R ¹ to R ⁶ in the general formula (I-2) are the same as the specific examples of R ¹ to R ⁶ in the general formula (I-1), and the preferred ranges are also the same.

特定硬化促進劑例如可作為第三膦化合物與醌化合物的加成物而獲得。作為第三膦化合物，具體而言，可列舉：三苯基膦、三丁基膦、二丁基苯基膦、丁基二苯基膦、乙基二苯基膦、三苯基膦、三(4-甲基苯基)膦、三(4-乙基苯基)膦、三(4-正丙基苯基)膦、三(4-正丁基苯基)膦、三(異丙基苯基)膦、三(第三丁基苯基)膦、三(2,4-二甲基苯基)膦、三(2,6-二甲基苯基)膦、三(2,4,6-三甲基苯基)膦、三(2,6-二甲基-4-乙氧基苯基)膦、三(4-甲氧基苯基)膦、三(4-乙氧基苯基)膦等。就成形性的觀點而言，較佳為三苯基膦及三丁基膦。 The specific hardening accelerator is available, for example, as an adduct of a third phosphine compound and a quinone compound. As the third phosphine compound, specifically, triphenylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, triphenylphosphine, (4-methylphenyl)phosphine, tris(4-ethylphenyl)phosphine, tris(4-n-propylphenyl)phosphine, tris(4-n-butylphenyl)phosphine, tris(isopropylphenyl)phosphine Phenyl)phosphine, tri(tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,6-dimethylphenyl)phosphine, tri(2,4, 6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl) base) phosphine, etc. From the viewpoint of moldability, triphenylphosphine and tributylphosphine are preferable.

作為醌化合物，具體而言，可列舉：1,2-苯醌、1,4-苯醌、聯苯醌、1,4-萘醌、蒽醌等。就耐濕性與保存穩定性的觀點而言，較佳為1,4-苯醌。Specific examples of the quinone compound include 1,2-benzoquinone, 1,4-benzoquinone, diphenoquinone, 1,4-naphthoquinone, and anthraquinone. From the viewpoint of moisture resistance and storage stability, 1,4-benzoquinone is preferable.

作為特定硬化促進劑的具體例，可列舉：三苯基膦與1,4-苯醌的加成反應產物、三正丁基膦與1,4-苯醌的加成反應產物、三環己基膦與1,4-苯醌的加成反應產物、二環己基苯基膦與1,4-苯醌的加成反應產物、環己基二苯基膦與1,4-苯醌的加成反應產物、三異丁基膦與1,4-苯醌的加成反應產物、三環戊基膦與1,4-苯醌的加成反應產物等。Specific examples of specific hardening accelerators include: addition reaction products of triphenylphosphine and 1,4-benzoquinone, addition reaction products of tri-n-butylphosphine and 1,4-benzoquinone, tricyclohexyl Addition reaction product of phosphine and 1,4-benzoquinone, addition reaction product of dicyclohexylphenylphosphine and 1,4-benzoquinone, addition reaction product of cyclohexyldiphenylphosphine and 1,4-benzoquinone Products, addition reaction products of triisobutylphosphine and 1,4-benzoquinone, addition reaction products of tricyclopentylphosphine and 1,4-benzoquinone, etc.

硬化性樹脂組成物亦可含有鏻化合物以外的硬化促進劑。作為鏻化合物以外的硬化促進劑，具體而言，可列舉：1,5-二氮雜雙環[4.3.0]壬烯-5（1,5-Diazabicyclo[4.3.0]nonene-5，DBN）、1,8-二氮雜雙環[5.4.0]十一烯-7（1,8-Diazabicyclo[5.4.0]undecene-7，DBU）等二氮雜雙環烯烴、2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-十七烷基咪唑等環狀脒化合物；所述環狀脒化合物的衍生物；所述環狀脒化合物或其衍生物的苯酚酚醛清漆鹽；於該些化合物上加成馬來酸酐、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、重氮苯基甲烷等具有π鍵的化合物而形成的具有分子內極化的化合物；DBU的四苯基硼酸鹽、DBN的四苯基硼酸鹽、2-乙基-4-甲基咪唑的四苯基硼酸鹽、N-甲基嗎啉的四苯基硼酸鹽等環狀脒鎓化合物；吡啶、三乙胺、三乙二胺、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；所述三級胺化合物的衍生物；乙酸四正丁基銨、磷酸四正丁基銨、乙酸四乙基銨、苯甲酸四正己基銨、氫氧化四丙基銨等銨鹽化合物等。 The curable resin composition may contain a curing accelerator other than the phosphonium compound. Examples of hardening accelerators other than phosphonium compounds include, specifically, 1,5-diazabicyclo[4.3.0]nonene-5 (1,5-Diazabicyclo[4.3.0]nonene-5, DBN) , 1,8-diazabicyclo[5.4.0]undecene-7 (1,8-Diazabicyclo[5.4.0]undecene-7, DBU) and other diazabicycloalkenes, 2-methylimidazole, 2 - Cyclic amidine compounds such as phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; derivatives of the cyclic amidine compound; derivatives of the cyclic amidine compound or its derivative Phenol novolac salts; addition of maleic anhydride, 1,4-benzoquinone, 2,5-methylbenzoquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6 -Dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4 - Compounds with intramolecular polarization formed by quinone compounds such as benzoquinone and compounds with π bonds such as diazophenylmethane; tetraphenyl borate of DBU, tetraphenyl borate of DBN, 2-ethyl- Cyclic amidinium compounds such as tetraphenyl borate of 4-methylimidazole and tetraphenyl borate of N-methylmorpholine; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, tri Tertiary amine compounds such as ethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; derivatives of the tertiary amine compounds; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, Ammonium salt compounds such as tetraethylammonium acetate, tetra-n-hexylammonium benzoate, and tetrapropylammonium hydroxide.

於硬化性樹脂組成物含有特定硬化促進劑作為硬化促進劑的情況下，特定硬化促進劑的含有率較佳為硬化促進劑整體的30質量%以上，更佳為50質量%以上，進而佳為70質量%以上。When the curable resin composition contains a specific hardening accelerator as the hardening accelerator, the content of the specific hardening accelerator is preferably at least 30% by mass of the entire hardening accelerator, more preferably at least 50% by mass, and still more preferably More than 70% by mass.

於硬化性樹脂組成物含有硬化促進劑的情況下，相對於樹脂成分100質量份，硬化促進劑的量較佳為0.1質量份～30質量份，更佳為1質量份～15質量份。若硬化促進劑的量相對於樹脂成分100質量份而為0.1質量份以上，則有短時間內良好地硬化的傾向。若硬化促進劑的量相對於樹脂成分100質量份而為30質量份以下，則有硬化速度不會過快而可獲得良好的成形品的傾向。When the curable resin composition contains a hardening accelerator, the amount of the hardening accelerator is preferably 0.1 to 30 parts by mass, more preferably 1 to 15 parts by mass, based on 100 parts by mass of the resin component. When the quantity of a hardening accelerator is 0.1 mass parts or more with respect to 100 mass parts of resin components, it exists in the tendency to harden favorably in a short time. When the amount of the hardening accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, a good molded article tends to be obtained without the hardening rate being too fast.

（無機填充材）第一態樣的硬化性樹脂組成物亦可含有無機填充材。藉由硬化性樹脂組成物含有無機填充材，而有硬化性樹脂組成物的吸濕性減低，硬化狀態下的強度提高的傾向。於將硬化性樹脂組成物用作半導體封裝的密封材的情況下，較佳為含有無機填充材。 (inorganic filler) The curable resin composition of the first aspect may contain an inorganic filler. When the curable resin composition contains the inorganic filler, the hygroscopicity of the curable resin composition decreases and the strength in the cured state tends to increase. When using a curable resin composition as a sealing material for a semiconductor package, it is preferable to contain an inorganic filler.

無機填充材的種類並無特別限制。具體而言，可列舉：球狀二氧化矽、晶體二氧化矽等二氧化矽、玻璃、氧化鋁、碳酸鈣、矽酸鋯、矽酸鈣、氮化矽、氮化鋁、氮化硼、氧化鈹、氧化鋯、鋯石、鎂橄欖石、塊滑石、尖晶石、富鋁紅柱石、氧化鈦、滑石、黏土、雲母等無機材料。亦可使用具有阻燃效果的無機填充材。作為具有阻燃效果的無機填充材，可列舉：氫氧化鋁、氫氧化鎂、鎂與鋅的複合氫氧化物等複合金屬氫氧化物、硼酸鋅等。其中，就線膨脹係數減少的觀點而言，較佳為球狀二氧化矽，就高導熱性的觀點而言，較佳為氧化鋁。無機填充材可單獨使用一種，亦可將兩種以上組合而使用。作為無機填充材的狀態，可列舉：粉末、將粉末球形化的顆粒、纖維等。無機填充材可單獨使用一種，亦可將兩種以上組合而使用。 The type of inorganic filler is not particularly limited. Specifically, silica such as spherical silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, Inorganic materials such as beryllium oxide, zirconia, zircon, forsterite, steatite, spinel, mullite, titanium oxide, talc, clay, and mica. Inorganic fillers having a flame retardant effect can also be used. Examples of the inorganic filler having a flame-retardant effect include composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and composite hydroxides of magnesium and zinc, zinc borate, and the like. Among these, spherical silica is preferable from the viewpoint of decreasing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity. An inorganic filler may be used individually by 1 type, and may use it in combination of 2 or more types. Examples of the state of the inorganic filler include powder, spheroidized particles, fibers, and the like. An inorganic filler may be used individually by 1 type, and may use it in combination of 2 or more types.

無機填充材的形狀並無特別限制，可列舉：粉狀、球狀、纖維狀等形狀。就硬化性樹脂組成物的成形時的流動性及模具磨損性的方面而言，較佳為球狀。The shape of the inorganic filler is not particularly limited, and examples thereof include powdery, spherical, and fibrous shapes. The curable resin composition is preferably spherical in terms of fluidity during molding and die wearability.

無機填充材的平均粒子徑並無特別限制。就硬化性樹脂組成物的黏度、填充性等的平衡的觀點而言，無機填充材的體積平均粒子徑較佳為0.1 μm～50 μm，更佳為0.3 μm～30 μm，進而佳為0.5 μm～25 μm。無機填充材的平均粒子徑可藉由雷射繞射散射法粒度分佈測定裝置而作為體積平均粒子徑（D50）來測定。體積平均粒子徑可利用公知的方法來進行測定。作為一例，使用有機溶劑、硝酸、王水等自硬化性樹脂組成物或樹脂硬化物中萃取無機填充材，利用超音波分散機等充分地分散而製備分散液。可使用該分散液，並根據利用雷射繞射散射法粒度分佈測定裝置而測定的體積基準的粒度分佈來測定無機填充材的體積平均粒子徑。或者，可將樹脂硬化物埋入至透明的環氧樹脂等中，進行研磨而獲得剖面，根據利用掃描式電子顯微鏡觀察所獲得的剖面而獲得的體積基準的粒度分佈來測定無機填充材的體積平均粒子徑。進而，亦可藉由如下方式來測定：使用聚焦離子束（Focused Ion Beam，FIB）裝置（聚焦離子束掃描式電子顯微鏡（Scanning Electron Microscope，SEM））等連續進行樹脂硬化物的二維的剖面觀察，並進行三維結構分析。 The average particle size of the inorganic filler is not particularly limited. From the viewpoint of the balance of the viscosity and fillability of the curable resin composition, the volume average particle size of the inorganic filler is preferably 0.1 μm to 50 μm, more preferably 0.3 μm to 30 μm, and still more preferably 0.5 μm ~25 μm. The average particle diameter of the inorganic filler can be measured as a volume average particle diameter (D50) with a laser diffraction scattering method particle size distribution measuring device. The volume average particle diameter can be measured by a known method. As an example, the inorganic filler is extracted from the curable resin composition or resin cured product using an organic solvent, nitric acid, aqua regia, etc., and is sufficiently dispersed by an ultrasonic disperser to prepare a dispersion liquid. Using this dispersion liquid, the volume average particle diameter of the inorganic filler can be measured from the volume-based particle size distribution measured by a particle size distribution measuring device for the laser diffraction scattering method. Alternatively, the resin cured product may be embedded in transparent epoxy resin, etc., ground to obtain a cross-section, and the volume of the inorganic filler may be measured from the volume-based particle size distribution obtained by observing the obtained cross-section with a scanning electron microscope. average particle size. Furthermore, it can also be measured by continuously performing a two-dimensional cross-section of the cured resin using a focused ion beam (Focused Ion Beam, FIB) device (focused ion beam scanning electron microscope (Scanning Electron Microscope, SEM)) or the like. Observe and perform three-dimensional structural analysis.

於硬化性樹脂組成物含有無機填充材的情況下，無機填充材的含有率並無特別限制。較佳為硬化性樹脂組成物整體的30質量%～90質量%，更佳為35質量%～80質量%，進而佳為40質量%～70質量%。若無機填充材的含有率為硬化性樹脂組成物整體的30質量%以上，則有樹脂硬化物的熱膨脹係數、熱傳導率、彈性係數等特性進一步提高的傾向。若無機填充材的含有率為硬化性樹脂組成物整體的90質量%以下，則有硬化性樹脂組成物的黏度上升得到抑制，流動性進一步提高而成形性變得更良好的傾向。 When the curable resin composition contains an inorganic filler, the content rate of the inorganic filler is not particularly limited. Preferably it is 30 mass % - 90 mass % of the whole curable resin composition, More preferably, it is 35 mass % - 80 mass %, More preferably, it is 40 mass % - 70 mass %. When the content of the inorganic filler is 30% by mass or more of the curable resin composition as a whole, properties such as thermal expansion coefficient, thermal conductivity, and modulus of elasticity of the cured resin tend to be further improved. When the content of the inorganic filler is 90% by mass or less of the curable resin composition as a whole, the viscosity increase of the curable resin composition is suppressed, the fluidity is further improved, and the formability tends to be better.

（偶合劑）第一態樣的硬化性樹脂組成物亦可含有偶合劑。偶合劑的種類並無特別限制，可使用公知的偶合劑。作為偶合劑，可列舉矽烷偶合劑、鈦偶合劑等。偶合劑可單獨使用一種，亦可併用兩種以上。 (coupling agent) The curable resin composition of the first aspect may also contain a coupling agent. The type of coupling agent is not particularly limited, and known coupling agents can be used. As a coupling agent, a silane coupling agent, a titanium coupling agent, etc. are mentioned. One type of coupling agent may be used alone, or two or more types may be used in combination.

矽烷偶合劑只要為所述直鏈狀聚矽氧烷化合物以外的化合物，則並無特別限定，可列舉：3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-(2-胺基乙基)胺基丙基三甲氧基矽烷、3-(2-胺基乙基)胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-脲基丙基三乙氧基矽烷、辛烯基三甲氧基矽烷、縮水甘油氧基辛基三甲氧基矽烷、甲基丙烯醯氧基辛基三甲氧基矽烷等。The silane coupling agent is not particularly limited as long as it is a compound other than the linear polysiloxane compound, and examples thereof include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, Ethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)amino Propyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl Triethoxysilane, 3-ureidopropyltriethoxysilane, octenyltrimethoxysilane, glycidyloxyoctyltrimethoxysilane, methacryloxyoctyltrimethoxysilane, etc. .

作為鈦偶合劑，可列舉：異丙基三異硬脂醯基鈦酸酯、異丙基三(焦磷酸二辛基酯)鈦酸酯、異丙基三(N-胺基乙基-胺基乙基)鈦酸酯、四辛基雙(亞磷酸二-十三烷基酯)鈦酸酯、四(2,2-二烯丙氧基甲基-1-丁基)雙(亞磷酸二-十三烷基酯)鈦酸酯、雙(焦磷酸二辛基酯)氧基乙酸酯鈦酸酯、雙(焦磷酸二辛基酯)伸乙基鈦酸酯、異丙基三辛醯基鈦酸酯、異丙基二甲基丙烯酸異硬脂醯基鈦酸酯、異丙基三-十二烷基苯磺醯基鈦酸酯、異丙基異硬脂醯基二丙烯酸鈦酸酯、異丙基三(磷酸二辛基酯)鈦酸酯、異丙基三枯基苯基鈦酸酯、四異丙基雙(亞磷酸二辛基酯)鈦酸酯等。Examples of titanium coupling agents include: isopropyl triisostearyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tris(N-aminoethyl-amine Ethyl) titanate, tetraoctyl bis (di-tridecyl phosphite) titanate, tetrakis (2,2-diallyloxymethyl-1-butyl) bis (phosphite Di-tridecyl) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylidene titanate, isopropyl tri Octyl titanate, Isopropyl isostearyl titanate dimethacrylate, Isopropyl tri-dodecylbenzenesulfonyl titanate, Isopropyl isostearyl diacrylate titanate ester, isopropyl tris(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis(dioctyl phosphite) titanate, etc.

所述偶合劑中，就耐回焊性的觀點而言，第一態樣的硬化性樹脂組成物較佳為含有3-胺基丙基三甲氧基矽烷及3-縮水甘油氧基丙基三甲氧基矽烷的至少一者。Among the coupling agents, from the viewpoint of reflow resistance, the curable resin composition of the first aspect preferably contains 3-aminopropyltrimethoxysilane and 3-glycidyloxypropyltrimethoxysilane at least one of oxysilanes.

於硬化性樹脂組成物含有偶合劑的情況下，就環氧樹脂與無機填充材的界面的接著性的觀點而言，相對於硬化性樹脂組成物中所含有的無機填充材100質量份，偶合劑的含量較佳為0.001質量份～10質量份，更佳為0.01質量份～8質量份，進而佳為0.05質量份～5質量份。When the curable resin composition contains a coupling agent, from the viewpoint of the adhesiveness of the interface between the epoxy resin and the inorganic filler, with respect to 100 parts by mass of the inorganic filler contained in the curable resin composition, occasionally The content of the mixture is preferably from 0.001 to 10 parts by mass, more preferably from 0.01 to 8 parts by mass, and still more preferably from 0.05 to 5 parts by mass.

（應力緩和劑）第一態樣的硬化性樹脂組成物亦可含有矽酮油、矽酮橡膠粒子等應力緩和劑。藉由硬化性樹脂組成物含有應力緩和劑，可進一步減低封裝的翹曲變形及封裝裂紋的產生。作為應力緩和劑，可列舉通常所使用的公知的應力緩和劑（可撓劑）。具體而言，作為應力緩和劑，可列舉：矽酮系、苯乙烯系、烯烴系、胺基甲酸酯系、聚酯系、聚醚系、聚醯胺系、聚丁二烯系等熱塑性彈性體、天然橡膠（natural rubber，NR）、丙烯腈-丁二烯共聚物（acrylonitrile butadiene rubber，NBR）、丙烯酸橡膠、胺基甲酸酯橡膠、矽酮粉末等橡膠粒子、甲基丙烯酸甲酯-苯乙烯-丁二烯共聚物（methyl methacrylate butadiene styrene，MBS）、甲基丙烯酸甲酯-矽酮共聚物、甲基丙烯酸甲酯-丙烯酸丁酯共聚物等具有核-殼結構的橡膠粒子等。應力緩和劑可單獨使用一種，亦可將兩種以上組合而使用。其中，較佳為矽酮系應力緩和劑。作為矽酮系應力緩和劑，可列舉：具有環氧基者、具有胺基者、將該些進行聚醚改質而成者等。 (stress reliever) The curable resin composition of the first aspect may also contain stress relieving agents such as silicone oil and silicone rubber particles. Since the curable resin composition contains a stress relieving agent, warpage of the package and generation of package cracks can be further reduced. Examples of the stress relieving agent include commonly used known stress relieving agents (flexibility agents). Specifically, examples of stress relieving agents include silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based thermoplastics. Elastomer, natural rubber (NR), acrylonitrile butadiene copolymer (NBR), acrylic rubber, urethane rubber, rubber particles such as silicone powder, methyl methacrylate -Rubber particles with a core-shell structure, such as methyl methacrylate butadiene styrene (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer, etc. . The stress relieving agent may be used alone or in combination of two or more. Among them, silicone-based stress relieving agents are preferred. Examples of the silicone-based stress relieving agent include those having an epoxy group, those having an amine group, and those obtained by modifying these with polyether.

於硬化性樹脂組成物含有應力緩和劑的情況下，相對於硬化性樹脂組成物中所含有的環氧樹脂100質量份，應力緩和劑的含量較佳為0.1質量份～30質量份，更佳為1質量份～5質量份。When the curable resin composition contains a stress relieving agent, the content of the stress relieving agent is preferably 0.1 to 30 parts by mass, more preferably 100 parts by mass of the epoxy resin contained in the curable resin composition. It is 1 mass part - 5 mass parts.

（脫模劑）於在成形時使用模具的情況下，就與模具的脫模性的觀點而言，第一態樣的硬化性樹脂組成物亦可含有脫模劑。脫模劑並無特別限制，可使用先前公知者。作為脫模劑，可列舉：棕櫚蠟（carnauba wax）、二十八酸、硬脂酸等高級脂肪酸、高級脂肪酸金屬鹽、二十八酸酯等酯系蠟、氧化聚乙烯、非氧化聚乙烯等聚烯烴系蠟等。脫模劑可單獨使用一種，亦可將兩種以上組合而使用。 (release agent) When a mold is used for molding, the curable resin composition of the first aspect may contain a mold release agent from the viewpoint of releasability from the mold. The release agent is not particularly limited, and a previously known one can be used. Examples of the release agent include carnauba wax, higher fatty acids such as behenic acid and stearic acid, higher fatty acid metal salts, ester waxes such as behenic acid esters, oxidized polyethylene, and non-oxidized polyethylene. and other polyolefin waxes. A mold release agent may be used individually by 1 type, and may use it in combination of 2 or more types.

於第一態樣的硬化性樹脂組成物含有脫模劑的情況下，相對於硬化性樹脂組成物中所含有的環氧樹脂100質量份，脫模劑的含量較佳為0.01質量份～15質量份，更佳為0.1質量份～10質量份。若脫模劑的量相對於樹脂成分100質量份而為0.01質量份以上，則有可充分獲得脫模性的傾向。若為15質量份以下，則有可獲得更良好的脫模性的傾向。When the curable resin composition of the first aspect contains a release agent, the content of the release agent is preferably 0.01 parts by mass to 15 parts by mass relative to 100 parts by mass of the epoxy resin contained in the curable resin composition. parts by mass, more preferably 0.1 parts by mass to 10 parts by mass. When the quantity of a mold release agent is 0.01 mass parts or more with respect to 100 mass parts of resin components, it exists in the tendency for sufficient mold release property to be acquired. If it is 15 parts by mass or less, better releasability tends to be obtained.

（著色劑）第一態樣的硬化性樹脂組成物亦可含有著色劑。作為著色劑，可列舉：碳黑、有機染料、有機顏料、氧化鈦、鉛丹、氧化鐵等公知的著色劑。著色劑的含量可根據目的等來適當選擇。著色劑可單獨使用一種，亦可將兩種以上組合而使用。 (Colorant) The curable resin composition of the first aspect may contain a colorant. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and iron oxide. The content of the colorant can be appropriately selected according to the purpose and the like. A coloring agent may be used individually by 1 type, and may use it in combination of 2 or more types.

於硬化性樹脂組成物含有著色劑的情況下，著色劑的含有率較佳為0.01質量%～5質量%，更佳為0.05質量%～3質量%，進而佳為0.01質量%～1質量%。When the curable resin composition contains a colorant, the content of the colorant is preferably from 0.01% by mass to 5% by mass, more preferably from 0.05% by mass to 3% by mass, still more preferably from 0.01% by mass to 1% by mass .

（阻燃劑）第一態樣的硬化性樹脂組成物亦可含有阻燃劑。阻燃劑並無特別限制，可使用先前公知者。作為阻燃劑，可列舉包含鹵素原子、銻原子、氮原子或磷原子的有機化合物或無機化合物、金屬氫氧化物等。阻燃劑可單獨使用一種，亦可將兩種以上組合而使用。 (flame retardant) The curable resin composition of the first aspect may contain a flame retardant. The flame retardant is not particularly limited, and known ones can be used. Examples of the flame retardant include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, metal hydroxides, and the like. A flame retardant may be used individually by 1 type, and may use it in combination of 2 or more types.

於第一態樣的硬化性樹脂組成物含有阻燃劑的情況下，阻燃劑的含量只要為對於獲得所期望的阻燃效果而言充分的量，則並無特別限制。相對於硬化性樹脂組成物中所含有的環氧樹脂100質量份，阻燃劑的含量較佳為1質量份～300質量份，更佳為2質量份～150質量份。When the curable resin composition of the first aspect contains a flame retardant, the content of the flame retardant is not particularly limited as long as it is an amount sufficient to obtain a desired flame retardant effect. The content of the flame retardant is preferably from 1 to 300 parts by mass, more preferably from 2 to 150 parts by mass, based on 100 parts by mass of the epoxy resin contained in the curable resin composition.

（離子交換體）第一態樣的硬化性樹脂組成物亦可含有離子交換體。於將硬化性樹脂組成物用作半導體封裝的密封材的情況下，就提高包括被密封的元件的電子零件裝置的耐濕性及高溫放置特性的觀點而言，較佳為含有離子交換體。離子交換體並無特別限制，可使用先前公知者。具體而言，可列舉水滑石化合物、以及含有選自由鎂、鋁、鈦、鋯及鉍所組成的群組中的至少一種元素的氫氧化物等。離子交換體可單獨使用一種，亦可將兩種以上組合而使用。具體而言，作為離子交換體，可列舉下述通式（A）所表示的水滑石。 (ion exchanger) The curable resin composition of the first aspect may contain an ion exchanger. When the curable resin composition is used as a sealing material for a semiconductor package, it is preferable to contain an ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of an electronic component device including a sealed element. The ion exchanger is not particularly limited, and previously known ones can be used. Specifically, hydrotalcite compounds, hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth, and the like are exemplified. An ion exchanger may be used individually by 1 type, and may use it in combination of 2 or more types. Specifically, the hydrotalcite represented by the following general formula (A) is mentioned as an ion exchanger.

Mg _(1-X)Al _X(OH) ₂(CO ₃) _X/2·mH ₂O ･･････（A）（0＜X≦0.5，m為正數） Mg _(1-X) Al _X (OH) ₂ (CO ₃ ) _X/2 mH ₂ O ･･･････（A）（0＜X≦0.5，m is a positive number）

於第一態樣的硬化性樹脂組成物含有離子交換體的情況下，離子交換體的含量只要為對於捕捉鹵素離子等離子而言充分的量，則並無特別限制。相對於硬化性樹脂組成物中所含有的環氧樹脂100質量份，離子交換體的含量較佳為0.1質量份～30質量份，更佳為1質量份～5質量份。When the curable resin composition of the first aspect contains an ion exchanger, the content of the ion exchanger is not particularly limited as long as it is an amount sufficient to capture halogen ion plasma. The content of the ion exchanger is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin contained in the curable resin composition, more preferably 1 to 5 parts by mass.

（環氧樹脂以外的樹脂）第一態樣的硬化性樹脂組成物亦可含有環氧樹脂以外的樹脂。環氧樹脂以外的樹脂的種類並無特別限制，可自通常用作硬化性樹脂組成物的成分者中選擇。環氧樹脂以外的樹脂可單獨使用一種，亦可將兩種以上組合而使用。 (Resins other than epoxy resins) The curable resin composition of the first aspect may contain resins other than epoxy resins. The types of resins other than epoxy resins are not particularly limited, and can be selected from those generally used as components of curable resin compositions. Resins other than epoxy resins may be used alone or in combination of two or more.

以下記載環氧樹脂以外的樹脂的具體例，但並不限定於該些。作為環氧樹脂以外的樹脂，可列舉：硫醇樹脂、脲樹脂、三聚氰胺樹脂、胺基甲酸酯樹脂、矽酮樹脂、馬來醯亞胺樹脂、不飽和聚酯樹脂等。 Although the specific example of resin other than an epoxy resin is described below, it is not limited to these. Examples of resins other than epoxy resins include thiol resins, urea resins, melamine resins, urethane resins, silicone resins, maleimide resins, and unsaturated polyester resins.

（酚系硬化劑以外的硬化劑）第一態樣的硬化性樹脂組成物亦可含有酚系硬化劑以外的硬化劑。酚系硬化劑以外的硬化劑的種類並無特別限制，可自通常用作硬化性樹脂組成物的成分者中選擇。酚系硬化劑以外的硬化劑可單獨使用一種，亦可將兩種以上組合而使用。 (hardeners other than phenolic hardeners) The curable resin composition of the first aspect may contain a curing agent other than the phenolic curing agent. The type of curing agent other than the phenolic curing agent is not particularly limited, and can be selected from those generally used as components of curable resin compositions. The curing agents other than the phenolic curing agent may be used alone or in combination of two or more.

以下記載酚系硬化劑以外的硬化劑的具體例，但並不限定於該些。作為酚系硬化劑以外的硬化劑，可列舉：胺系硬化劑、酸酐系硬化劑、聚硫醇系硬化劑、聚胺基醯胺系硬化劑、異氰酸酯系硬化劑、嵌段異氰酸酯系硬化劑等。 Specific examples of curing agents other than phenolic curing agents are described below, but are not limited thereto. Examples of hardeners other than phenolic hardeners include amine hardeners, acid anhydride hardeners, polythiol hardeners, polyaminoamide hardeners, isocyanate hardeners, and blocked isocyanate hardeners. wait.

於酚系硬化劑以外的硬化劑包含胺系硬化劑的情況下，胺系硬化劑的活性氫當量並無特別限制。就耐回焊性、成形性、電可靠性等各種特性平衡的觀點而言，較佳為10 g/eq～1000 g/eq，更佳為30 g/eq～500 g/eq。胺系硬化劑的活性氫當量是指基於依據JIS K 7237：1995測定所得的胺價而算出的值。 When the curing agent other than the phenolic curing agent includes an amine curing agent, the active hydrogen equivalent of the amine curing agent is not particularly limited. From the viewpoint of the balance of various properties such as reflow resistance, formability, and electrical reliability, it is preferably 10 g/eq to 1000 g/eq, and more preferably 30 g/eq to 500 g/eq. The active hydrogen equivalent of the amine curing agent is a value calculated based on the amine value measured in accordance with JIS K 7237:1995.

於硬化性樹脂組成物含有酚系硬化劑以外的硬化劑的情況下，酚系硬化劑以外的硬化劑相對於硬化性樹脂組成物的總質量的含有率並無特別限定，較佳為2質量%～35質量%，更佳為5質量%～30質量%。When the curable resin composition contains a curing agent other than the phenolic curing agent, the content of the curing agent other than the phenolic curing agent with respect to the total mass of the curable resin composition is not particularly limited, but is preferably 2 mass % to 35% by mass, more preferably 5% to 30% by mass.

[第一態樣的硬化性樹脂組成物的製造方法] 硬化性樹脂組成物的製造方法並無特別限制。作為通常的方法，可列舉如下方法：於藉由混合機等將規定調配量的成分充分混合後，藉由混合輥、擠出機等來進行熔融混練，進行冷卻並加以粉碎。更具體而言，例如可列舉如下方法：將規定量的所述成分均勻地攪拌及混合，利用預先加熱為70℃～140℃的捏合機、輥、擠壓機等進行混練並冷卻，進行粉碎。 [Method for Producing Curable Resin Composition of First Aspect] The method for producing the curable resin composition is not particularly limited. As a usual method, after fully mixing the components of a predetermined preparation amount with a mixer etc., melt kneading with a mixing roll, an extruder etc., cooling and pulverization are mentioned. More specifically, for example, a method of uniformly stirring and mixing predetermined amounts of the above-mentioned components, kneading and cooling with a kneader, roll, extruder, etc. previously heated at 70°C to 140°C, and pulverizing .

硬化性樹脂組成物較佳為於25℃下為固體。於硬化性樹脂組成物於25℃下為固體的情況下，硬化性樹脂組成物的形狀並無特別限制，可列舉粉狀、粒狀、小片狀等。就操作性的觀點而言，硬化性樹脂組成物為小片狀時的尺寸及質量較佳為成為與封裝的成形條件相符的尺寸及質量。The curable resin composition is preferably solid at 25°C. When the curable resin composition is solid at 25° C., the shape of the curable resin composition is not particularly limited, and examples thereof include powder, granule, and flake. From the standpoint of handling, it is preferable that the size and quality of the curable resin composition be in the shape of a pellet so that the size and quality match the molding conditions of the package.

＜第二態樣的硬化性樹脂組成物＞第二態樣的硬化性樹脂組成物中，於藉由對硬化性樹脂組成物的樹脂硬化物進行動態黏彈性測定而獲得的縱軸為tanδ及橫軸為30℃～260℃的溫度的圖表中，70℃、80℃及90℃各溫度下的tanδ值的合計超過0.600。 <The curable resin composition of the second aspect> In the curable resin composition of the second aspect, the graph obtained by measuring the dynamic viscoelasticity of the resin cured product of the curable resin composition is tan δ on the vertical axis and temperature from 30°C to 260°C on the horizontal axis Among them, the sum of the tanδ values at each temperature of 70°C, 80°C, and 90°C exceeded 0.600.

第二態樣的硬化性樹脂組成物具有優異的耐回焊性。The curable resin composition of the second aspect has excellent reflow resistance.

藉由第二態樣的硬化性樹脂組成物而起到所述效果的理由並不明確，但推測如下。The reason why the above effect is exhibited by the curable resin composition of the second aspect is not clear, but it is estimated as follows.

根據第二態樣的硬化性樹脂組成物，有回焊時所產生的樹脂硬化物的內部應力得到緩和的傾向，所述第二態樣的硬化性樹脂組成物中，於藉由對硬化性樹脂組成物的樹脂硬化物進行動態黏彈性測定而獲得的縱軸為tanδ及橫軸為30℃～260℃的溫度的圖表中，70℃、80℃及90℃各溫度下的tanδ值的合計超過0.600。其結果，硬化性樹脂組成物的樹脂硬化物與支撐構件的接著性提高，因此推測具有優異的耐回焊性。根據本揭示的硬化性樹脂組成物，即便於利用溫度85℃、相對濕度85%、168小時的條件（相當於MSL等級1）的加熱加濕後，亦顯示出優異的耐回焊性，此情況令人吃驚。 According to the curable resin composition of the second aspect, the internal stress of the cured resin produced during reflow tends to be relaxed. The sum of the tanδ values at each temperature of 70°C, 80°C, and 90°C in a graph of tanδ on the vertical axis and temperature from 30°C to 260°C on the horizontal axis obtained by dynamic viscoelasticity measurement of the hardened resin of the resin composition over 0.600. As a result, the cured resin product of the curable resin composition has improved adhesiveness to the support member, and thus is presumed to have excellent reflow resistance. According to the curable resin composition of the present disclosure, even after heating and humidifying under conditions of temperature 85°C, relative humidity 85%, and 168 hours (equivalent to MSL level 1), it also shows excellent reflow resistance. The situation is surprising.

就第二態樣的硬化性樹脂組成物的耐回焊性的觀點而言，70℃、80℃及90℃各溫度下的tanδ值的合計較佳為超過0.700。70℃、80℃及90℃各溫度下的tanδ值的合計的上限值並無特別限定，例如可設為2.0以下。From the viewpoint of the reflow resistance of the curable resin composition of the second aspect, the sum of the tanδ values at each temperature of 70°C, 80°C, and 90°C is preferably more than 0.700. 70°C, 80°C, and 90°C The upper limit of the sum of the tan δ values at each temperature in °C is not particularly limited, and may be, for example, 2.0 or less.

就第二態樣的硬化性樹脂組成物的耐回焊性的觀點而言，tanδ成為最大時的溫度較佳為未滿120℃，更佳為未滿110℃。tanδ成為最大時的溫度的下限值並無特別限定，例如可設為50℃以上。From the viewpoint of the reflow resistance of the curable resin composition of the second aspect, the temperature at which tan δ becomes the maximum is preferably less than 120°C, more preferably less than 110°C. The lower limit of the temperature at which tan δ becomes maximum is not particularly limited, and may be set to, for example, 50° C. or higher.

就第二態樣的硬化性樹脂組成物的耐回焊性的觀點而言，tanδ的最大值較佳為超過0.400，更佳為超過0.410。tanδ的最大值的上限值並無特別限定，例如可設為1.0以下。From the viewpoint of the reflow resistance of the curable resin composition of the second aspect, the maximum value of tan δ is preferably more than 0.400, more preferably more than 0.410. The upper limit of the maximum value of tan δ is not particularly limited, and may be, for example, 1.0 or less.

就第二態樣的硬化性樹脂組成物的耐回焊性的觀點而言，220℃、230℃、240℃及250℃各溫度下的tanδ值的合計較佳為超過0.400。220℃、230℃、240℃及250℃各溫度下的tanδ值的合計的上限值並無特別限定，例如可設為2.0以下。From the viewpoint of the reflow resistance of the curable resin composition of the second aspect, the sum of the tanδ values at each temperature of 220°C, 230°C, 240°C and 250°C is preferably more than 0.400. 220°C, 230°C The upper limit of the sum of the tan δ values at each temperature of °C, 240°C, and 250°C is not particularly limited, and may be, for example, 2.0 or less.

就第二態樣的硬化性樹脂組成物的耐回焊性的觀點而言，於將tanδ的最大值設為100時，tanδ成為最大時的溫度-10℃的至少任一溫度下的tanδ值較佳為超過60，更佳為超過63，進而佳為超過65。From the viewpoint of the reflow resistance of the curable resin composition of the second aspect, when the maximum value of tan δ is set to 100, the tan δ value at least any one of the temperature at which tan δ becomes maximum - 10°C It is preferably more than 60, more preferably more than 63, and still more preferably more than 65.

就耐回焊性的觀點而言，藉由對硬化性樹脂組成物的樹脂硬化物進行動態黏彈性測定而求出的260℃下的貯存黏彈性較佳為450 MPa以下，更佳為435 MPa以下，進而佳為420 MPa以下。貯存彈性係數的下限值並無特別限定，例如可設為150 MPa以上。From the viewpoint of reflow resistance, the storage viscoelasticity at 260°C obtained by measuring the dynamic viscoelasticity of the resin cured product of the curable resin composition is preferably 450 MPa or less, more preferably 435 MPa below, more preferably below 420 MPa. The lower limit of the storage elastic coefficient is not particularly limited, and may be set to, for example, 150 MPa or more.

就對支撐構件的追隨性的觀點而言，藉由熱機械分析測定而求出的第二態樣的硬化性樹脂組成物的樹脂硬化物於未滿玻璃轉移溫度的溫度下的熱膨脹係數（CTE1）較佳為15 ppm/℃以下，更佳為13 ppm/℃以下，進而佳為10 ppm/℃以下。熱膨脹係數的下限值並無特別限定，例如可設為3 ppm/℃。就與支撐構件的接著性的觀點而言，玻璃轉移溫度以上的溫度下的熱膨脹係數（CTE2）較佳為10 ppm/℃～45 ppm/℃，更佳為12 ppm/℃～40 ppm/℃，進而佳為15 ppm/℃～38 ppm/℃。 From the viewpoint of followability to the supporting member, the thermal expansion coefficient (CTE1 ) is preferably at most 15 ppm/°C, more preferably at most 13 ppm/°C, still more preferably at most 10 ppm/°C. The lower limit of the coefficient of thermal expansion is not particularly limited, and may be 3 ppm/°C, for example. From the viewpoint of adhesion to the support member, the coefficient of thermal expansion (CTE2) at a temperature above the glass transition temperature is preferably 10 ppm/°C to 45 ppm/°C, more preferably 12 ppm/°C to 40 ppm/°C , and more preferably 15 ppm/°C to 38 ppm/°C.

就耐回焊性的觀點而言，第二態樣的硬化性樹脂組成物較佳為以酚系硬化劑的酚性羥基相對於環氧樹脂的環氧基的當量比0.5以上且未滿1.0含有環氧樹脂及酚系硬化劑。From the viewpoint of reflow resistance, the curable resin composition of the second aspect is preferably such that the equivalent ratio of the phenolic hydroxyl group of the phenolic curing agent to the epoxy group of the epoxy resin is 0.5 or more and less than 1.0 Contains epoxy resin and phenolic hardener.

關於第二態樣的硬化性樹脂組成物可含有的各種材料及第二態樣的硬化性樹脂組成物的製造方法，由於與第一態樣的硬化性樹脂組成物相同，因此此處省略記載。The various materials that can be contained in the curable resin composition of the second aspect and the production method of the curable resin composition of the second aspect are the same as those of the curable resin composition of the first aspect, so descriptions are omitted here. .

[硬化性樹脂組成物的用途] 第一態樣的硬化性樹脂組成物及第二態樣的硬化性樹脂組成物的用途並無特別限制，例如可作為電子零件裝置的密封材而用於各種安裝技術。另外，硬化性樹脂組成物可用於各種模組用樹脂成形體、馬達用樹脂成形體、車載用樹脂成形體、電子電路用保護材用密封材等樹脂組成物理想的是具有良好的流動性及硬化性的各種用途。 [Applications of Curable Resin Composition] The applications of the curable resin composition of the first aspect and the curable resin composition of the second aspect are not particularly limited. For example, they can be used in various mounting techniques as a sealing material for electronic component devices. In addition, the curable resin composition can be used in various resin molded products for modules, resin molded products for motors, automotive resin molded products, and sealing materials for electronic circuit protection materials. Ideally, the resin composition has good fluidity and Various uses of sclerosing properties.

[電子零件裝置] 本揭示的電子零件裝置包括元件以及將元件密封的第一態樣的硬化性樹脂組成物或第二態樣的硬化性樹脂組成物的樹脂硬化物。 [electronic parts device] The electronic component device of the present disclosure includes an element and a cured resin composition of the curable resin composition of the first aspect or the curable resin composition of the second aspect that seals the element.

電子零件裝置可包括供元件搭載的支撐構件。作為支撐構件，可列舉：引線框架、配線完畢的載帶、配線板、玻璃、矽晶圓、有機基板等。所述支撐構件中，就與所述硬化性樹脂組成物的樹脂硬化物的接著性的觀點而言，較佳為引線框架。 The electronic component device may include a support member on which components are mounted. Examples of the supporting member include a lead frame, a wired carrier tape, a wiring board, glass, a silicon wafer, an organic substrate, and the like. Among the support members, a lead frame is preferable from the viewpoint of adhesion to the resin cured product of the curable resin composition.

引線框架的表面可經粗面化，亦可未經粗面化，就製造成本的觀點而言，較佳為未粗面化引線框架，就接著性的觀點而言，較佳為粗面化引線框架。粗面化方法並無特別限定，可列舉：鹼處理、矽烷偶合處理、砂墊層處理、電漿處理、電暈放電處理等。 The surface of the lead frame may or may not be roughened, but from the viewpoint of manufacturing cost, a non-roughened lead frame is preferred, and a roughened one is preferred from the viewpoint of adhesion lead frame. The roughening method is not particularly limited, and examples thereof include alkali treatment, silane coupling treatment, sand cushion treatment, plasma treatment, and corona discharge treatment.

引線框架可於表面的至少一部分包括包含Au、Pd及Ni的至少一種的鍍敷層。另外，所述鍍敷層可為單層，亦可為多層。作為多層的鍍敷層，可列舉自引線框架側起積層有鍍Ni層、鍍Pd層及鍍Au層的三層結構的鍍敷層等。作為所述三層結構的引線框架，例如可列舉對被稱為PPF（預鍍引線框架（Pre Plating Lead Flame））的銅引線框架實施了Ni-Pd-Au鍍敷的引線框架。 The lead frame may include a plating layer including at least one of Au, Pd and Ni on at least a part of the surface. In addition, the plating layer may be a single layer or multiple layers. As a multilayer plating layer, a plating layer of a three-layer structure in which a Ni plating layer, a Pd plating layer, and an Au plating layer are laminated from the lead frame side, etc. are mentioned. As the lead frame of the three-layer structure, for example, a lead frame obtained by plating Ni-Pd-Au on a copper lead frame called PPF (Pre Plating Lead Flame).

鍍敷層的厚度並無特別限定，較佳為5 μm以下，更佳為4 μm以下，進而佳為3 μm以下。The thickness of the plating layer is not particularly limited, but is preferably not more than 5 μm, more preferably not more than 4 μm, and still more preferably not more than 3 μm.

作為電子零件裝置所包括的元件，例如可列舉：矽晶片、電晶體、二極體、閘流體等主動元件；電容器、電阻體、線圈等被動元件等。Examples of elements included in the electronic component device include active elements such as silicon wafers, transistors, diodes, and thyristors; passive elements such as capacitors, resistors, and coils, and the like.

作為電子零件裝置的具體結構，可列舉以下結構，但並不限定於該些。（1）雙列直插式封裝（Dual Inline Package，DIP）、塑膠引線晶片載體（Plastic Leaded Chip Carrier，PLCC）、四方扁平封裝（Quad Flat Package，QFP）、小外型封裝（Small Outline Package，SOP）、小外型J-引線封裝（Small Outline J-lead Package，SOJ）、薄小外型封裝（Thin Small Outline Package，TSOP）、薄型四方扁平封裝（Thin Quad Flat Package，TQFP）等通常的樹脂密封型IC，其具有於將元件固定於引線框架上且使用打線接合、凸塊等連接接合墊等元件的端子部與引線部後，使用硬化性樹脂組成物進行密封的結構；（2）載帶封裝（Tape Carrier Package，TCP），其具有使用硬化性樹脂組成物對利用凸塊連接於載帶上的元件進行密封的結構；（3）基板覆晶（Chip On Board，COB）模組、混合IC、多晶模組等，其具有使用硬化性樹脂組成物對利用打線接合、倒裝晶片接合、焊料等連接於支撐構件上所形成的配線上的元件進行密封的結構；（4）球柵陣列（Ball Grid Array，BGA）、晶片尺寸封裝（Chip Size Package，CSP）、多晶片封裝（Multi Chip Package，MCP）、系統封裝（System in a Package，SiP）等，其具有於背面形成配線板連接用端子的支撐構件的表面上搭載元件，並使用凸塊或打線接合將元件與支撐構件上所形成的配線連接後，使用硬化性樹脂組成物將元件密封的結構。 Although the following structures are mentioned as a specific structure of an electronic component apparatus, it is not limited to these. (1) Dual Inline Package (DIP), Plastic Leaded Chip Carrier (PLCC), Quad Flat Package (QFP), Small Outline Package, SOP), Small Outline J-lead Package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (Thin Quad Flat Package, TQFP) and other common Resin-sealed ICs having a structure in which the components are sealed with a curable resin composition after the components are fixed on the lead frame and the terminals and lead parts of the components such as bonding pads are connected using wire bonding or bumps; (2) Tape Carrier Package (TCP), which has a structure that uses a curable resin composition to seal components connected to the carrier tape by bumps; (3) Chip On Board (COB) modules, hybrid ICs, polycrystalline modules, etc., which use hardening resin compositions to connect to supporting members by wire bonding, flip chip bonding, solder, etc. The structure in which the components on the formed wiring are sealed; (4) Ball grid array (Ball Grid Array, BGA), chip size package (Chip Size Package, CSP), multi-chip package (Multi Chip Package, MCP), system package (System in a Package, SiP), etc., which have A structure in which components are mounted on the surface of a support member with wiring board connection terminals formed on the back surface, connected to wiring formed on the support member using bumps or wire bonding, and sealed with a curable resin composition.

使用硬化性樹脂組成物將元件密封的方法並無特別限定，能夠應用公知的方法。作為密封方法，例如通常為低壓轉移成形，亦可使用噴射成形、壓縮成形、澆注等。 [實施例] The method of sealing the element using the curable resin composition is not particularly limited, and known methods can be applied. As a sealing method, for example, low-pressure transfer molding is generally used, but injection molding, compression molding, casting, and the like can also be used. [Example]

以下，藉由實施例對本揭示進行具體說明，但本揭示並不限定於該些實施例。另外，只要無特別說明，則表中的數值是指「質量份」。Hereinafter, the present disclosure will be specifically described with examples, but the present disclosure is not limited to these examples. In addition, unless otherwise specified, the numerical value in a table|surface means a "mass part."

（實施例1～實施例7及比較例1～比較例3）將表1所示的配方的材料預混合（乾式摻合）後，利用雙軸輥（輥表面溫度：約80℃）混練約15分鐘，進行冷卻並加以粉碎，從而製造粉末狀的硬化性樹脂組成物。 (Example 1 to Example 7 and Comparative Example 1 to Comparative Example 3) After pre-mixing (dry blending) the ingredients of the formulation shown in Table 1, kneading with a twin-screw roll (roll surface temperature: about 80°C) for about 15 minutes, cooling and pulverizing to produce a powdery curable resin Composition.

表1中的材料的詳細情況如以下所述。再者，表1中的酚系硬化劑的酚性羥基相對於環氧樹脂的環氧基的當量比是藉由所述方法來求出。The details of the materials in Table 1 are as follows. In addition, the equivalent ratio of the phenolic hydroxyl group of the phenolic hardening|curing agent in Table 1 with respect to the epoxy group of an epoxy resin was calculated|required by the said method.

·環氧樹脂A：具有下述結構單元的共聚合型環氧樹脂、環氧當量250 g/eq、150℃下的熔融黏度0.7 dPa·s、Mn 350～600Epoxy resin A: Copolymerized epoxy resin with the following structural units, epoxy equivalent 250 g/eq, melt viscosity at 150°C 0.7 dPa·s, Mn 350-600

[化22]

[chem 22]

·環氧樹脂B：聯苯型環氧樹脂、環氧當量196 g/eq、軟化點106℃、三菱化學股份有限公司製造、商品名「YX-4000H」、Mn 350 ·環氧樹脂C：聯苯芳烷基型環氧樹脂、環氧當量284 g/eq ・Epoxy resin B: biphenyl type epoxy resin, epoxy equivalent 196 g/eq, softening point 106°C, manufactured by Mitsubishi Chemical Corporation, brand name "YX-4000H", Mn 350 Epoxy resin C: biphenyl aralkyl type epoxy resin, epoxy equivalent 284 g/eq

·酚系硬化劑A：芳烷基型酚樹脂、羥基當量106 g/eq ·酚系硬化劑B：三苯基甲烷型酚樹脂、羥基當量95 g/eq ·酚系硬化劑C：芳烷基型酚樹脂、羥基當量203 g/eq ·酚系硬化劑D：三聚氰胺改質酚樹脂、羥基當量120 g/eq、軟化點：90℃ ·酚系硬化劑E：三嗪型酚樹脂、2-[4-[(2-羥基-3-(2'-乙基)己基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、巴斯夫（BASF）公司、商品名「帝奴彬（Tinuvin）（註冊商標）405」 ·酚系硬化劑F：酚醛清漆型酚樹脂、羥基當量223 g/eq ·酚系硬化劑G：酚醛清漆型酚樹脂、羥基當量156 g/eq ・Phenolic hardener A: aralkyl type phenolic resin, hydroxyl equivalent 106 g/eq ・Phenolic hardener B: triphenylmethane type phenolic resin, hydroxyl equivalent 95 g/eq · Phenolic Hardener C: Aralkyl type phenolic resin, hydroxyl equivalent 203 g/eq ・Phenolic hardener D: Melamine-modified phenolic resin, hydroxyl equivalent 120 g/eq, softening point: 90°C ・Phenolic hardener E: triazine type phenolic resin, 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6- Bis(2,4-dimethylphenyl)-1,3,5-triazine, BASF Corporation, trade name "Tinuvin (registered trademark) 405" ・Phenolic hardener F: novolac type phenolic resin, hydroxyl equivalent 223 g/eq ・Phenolic hardener G: novolac type phenolic resin, hydroxyl equivalent 156 g/eq

·硬化促進劑：三苯基膦與1,4-苯醌的加成反應產物Hardening accelerator: addition reaction product of triphenylphosphine and 1,4-benzoquinone

·偶合劑A：3-胺基丙基三甲氧基矽烷 ·偶合劑B：3-縮水甘油氧基丙基三甲氧基矽烷 ·偶合劑C：直鏈狀聚矽氧烷、熔點：-70℃、環氧當量120 g/eq～150 g/eq ·偶合劑D：四硫醚二-三乙氧基矽烷 ·Coupling agent A: 3-Aminopropyltrimethoxysilane Coupling agent B: 3-glycidyloxypropyltrimethoxysilane ·Coupling agent C: linear polysiloxane, melting point: -70°C, epoxy equivalent 120 g/eq～150 g/eq Coupling agent D: Tetrasulfide bis-triethoxysilane

·應力緩和劑A：環氧改質矽酮樹脂 ·應力緩和劑B：含茚的共聚物 ·應力緩和劑C：含苯基的矽酮樹脂 Stress relieving agent A: Epoxy modified silicone resin ・Stress relieving agent B: indene-containing copolymer Stress relieving agent C: phenyl-containing silicone resin

·無機填充劑A：平均粒子徑為19.4 μm的二氧化矽填料 ·無機填充劑B：平均粒子徑為0.6 μm的二氧化矽填料 ·無機填充劑C：平均粒子徑為50 nm以下的二氧化矽填料 ·無機填充劑D：平均粒子徑為1.2 μm的包含鎂及鋅的金屬氫氧化物・Inorganic filler A: Silica filler with an average particle diameter of 19.4 μm ・Inorganic filler B: Silica filler with an average particle size of 0.6 μm ・Inorganic filler C: Silica filler with an average particle diameter of 50 nm or less ・Inorganic filler D: Metal hydroxide containing magnesium and zinc with an average particle diameter of 1.2 μm

＜＜硬化性樹脂組成物的評價＞＞藉由下述特性試驗來評價實施例及比較例中所製造的硬化性樹脂組成物的特性。將評價結果示於表1中。再者，關於使用硬化性樹脂組成物的樹脂硬化物的製作，只要無明確記載，則是藉由如下方式來進行：利用轉移成形機於模具溫度175℃、成形壓力8.3 MPa、硬化時間120秒的條件下進行成形後，於175℃、5小時的條件下進行後硬化。＜＜Evaluation of Curable Resin Composition＞＞ The properties of the curable resin compositions produced in Examples and Comparative Examples were evaluated by the following property tests. The evaluation results are shown in Table 1. Furthermore, regarding the production of cured resins using curable resin compositions, as long as there is no clear description, it is carried out by using a transfer molding machine at a mold temperature of 175°C, a molding pressure of 8.3 MPa, and a curing time of 120 seconds. After forming under the conditions of 175°C and 5 hours, post-hardening is carried out.

＜耐回焊性評價＞針對於5.2 mm×4.1 mm的模墊上搭載有3.2 mm×2.2 mm×0.37 mm的矽晶片的28針的小外型（Small Outline，SO）封裝（引線框架材質：銅合金、Ni-Pd-Au鍍敷處理品），使用硬化性樹脂組成物進行成形，繼而，於175℃、5小時的條件下進行後硬化。藉由目視而確認到所獲得的成形品的外部無裂紋，並藉由超音波探傷裝置（日立製作所股份有限公司製造、FS-200）而確認到內部無剝離產生。將成形品於125℃下乾燥12小時後，於溫度85℃、相對濕度85%的條件下加濕168小時。之後，依據JEDEC的規定，將溫度條件設定為260℃，於同一溫度下進行3次回焊處理，藉由目視來觀察封裝外部有無裂紋，並藉由超音波探傷裝置來觀察封裝內部有無剝離產生。以產生裂紋及剝離的任一者的封裝數相對於試驗封裝數的比例來評價耐回焊性。將評價結果歸納於表1中。（評價基準） A：裂紋及剝離的產生為0% B：裂紋及剝離的產生超過0%、未滿60% C：裂紋及剝離的產生為60%以上且未滿100% D：裂紋及剝離的產生為100% ＜Evaluation of reflow resistance＞ A 28-pin Small Outline (SO) package with a 3.2 mm x 2.2 mm x 0.37 mm silicon chip mounted on a 5.2 mm x 4.1 mm die pad (lead frame material: copper alloy, Ni-Pd-Au Plated product) is molded using a curable resin composition, and then post-cured at 175°C for 5 hours. It was confirmed visually that there was no external crack of the obtained molded product, and it was confirmed that no internal peeling occurred with an ultrasonic flaw detector (manufactured by Hitachi, Ltd., FS-200). After the molded product was dried at 125°C for 12 hours, it was humidified for 168 hours at a temperature of 85°C and a relative humidity of 85%. Afterwards, according to the JEDEC regulations, the temperature condition was set to 260°C, and the reflow process was performed three times at the same temperature. The external cracks of the package were visually observed, and the internal package was observed for peeling by an ultrasonic flaw detection device. Reflow resistance was evaluated by the ratio of the number of packages in which either cracks or peeling occurred to the number of test packages. The evaluation results are summarized in Table 1. (evaluation criteria) A: The occurrence of cracks and peeling is 0% B: The occurrence of cracks and peeling exceeds 0% and is less than 60% C: The occurrence of cracks and peeling is 60% or more and less than 100% D: The occurrence of cracks and peeling is 100%

＜tanδ及貯存彈性係數的測定＞基於所述條件，來製作所述實施例及比較例中所獲得的硬化性樹脂組成物的樹脂硬化物。樹脂硬化物設為具有短邊5 mm、長邊50 mm、厚度2 mm的長方形形狀的樹脂硬化物。針對所述樹脂硬化物，於試驗模式：3點彎曲模式、測定溫度：25℃～330℃、升溫速度：10℃/分鐘、試驗頻率：1 Hz的條件下實施動態黏彈性測定，根據所獲得的圖表（縱軸：tanδ、橫軸：溫度）來求出貯存黏彈性的值並歸納於表1中。另外，根據所述圖表來求出（1）tanδ成為最大時的溫度（玻璃轉移溫度）、（2）玻璃轉移溫度下的tanδ值、（3）220℃、230℃、240℃及250℃各溫度下的tanδ值的合計（表1中，記載為tanδ合計220℃～250℃）、（4）70℃、80℃及90℃各溫度下的tanδ值的合計（表1中，記載為tanδ合計70℃～90℃）及（5）於將玻璃轉移溫度下的tanδ值設為100時的較玻璃轉移溫度低10度的溫度下的tanδ值（表1中，記載為tanδ比），並歸納於表1中。 <Measurement of tanδ and storage elastic coefficient> Based on the conditions described above, cured resins of the curable resin compositions obtained in the Examples and Comparative Examples were prepared. The cured resin product was made into a rectangular resin cured product having a short side of 5 mm, a long side of 50 mm, and a thickness of 2 mm. For the cured resin, the dynamic viscoelasticity measurement was carried out under the conditions of test mode: 3-point bending mode, measurement temperature: 25°C-330°C, heating rate: 10°C/min, test frequency: 1 Hz, and according to the obtained The graph (vertical axis: tanδ, horizontal axis: temperature) was used to obtain the value of storage viscoelasticity and summarized in Table 1. In addition, (1) the temperature at which tan δ becomes maximum (glass transition temperature), (2) the tan δ value at the glass transition temperature, and (3) each of 220°C, 230°C, 240°C, and 250°C were obtained from the graph. The total of tanδ values at the temperature (in Table 1, it is described as tanδ total 220°C to 250°C), (4) the total of tanδ values at each temperature of 70°C, 80°C, and 90°C (in Table 1, it is described as tanδ 70°C to 90°C in total), and (5) the tanδ value at a temperature 10 degrees lower than the glass transition temperature when the tanδ value at the glass transition temperature is set to 100 (in Table 1, it is described as the tanδ ratio), and Summarized in Table 1.

＜熱膨脹係數（CTE1）的測定＞基於所述條件，來製作所述實施例及比較例中所獲得的硬化性樹脂組成物的樹脂硬化物。樹脂硬化物設為φ4 mm×20 mm的樹脂硬化物。繼而，基於JIS K 7197：2012，並藉由熱機械分析法而於10℃～30℃的範圍內求出將樹脂硬化物的應變相對於溫度繪圖時的切線的傾斜率。將測定結果歸納於表1中。再者，試驗荷重設為15 g，升溫速度設為5℃/分鐘來進行測定。另外，於線膨脹係數的測定中使用精工儀器（Seiko Instruments）股份有限公司製造的TMA高精度二試樣熱分析裝置（裝置名SS6100）。 <Measurement of Coefficient of Thermal Expansion (CTE1)> Based on the conditions described above, cured resins of the curable resin compositions obtained in the Examples and Comparative Examples were prepared. The cured resin was made into a cured resin of φ4 mm×20 mm. Next, based on JIS K 7197:2012, the inclination of the tangent line when the strain of the resin hardened|cured material was plotted with respect to temperature was calculated|required by the thermomechanical analysis method in the range of 10 degreeC - 30 degreeC. The measurement results are summarized in Table 1. In addition, the test load was set to 15 g, and the temperature increase rate was set to 5° C./min, and the measurement was performed. In addition, for the measurement of the coefficient of linear expansion, a TMA high-precision two-sample thermal analyzer (device name SS6100) manufactured by Seiko Instruments Co., Ltd. was used.

＜吸水率的測定＞基於所述條件，來製作所述實施例及比較例中所獲得的硬化性樹脂組成物的樹脂硬化物。樹脂硬化物設為具有短邊5.1 mm、長邊20 mm、厚度2 mm的長方形形狀的硬化物。繼而，於溫度85℃、相對濕度85%的條件下將所述樹脂硬化物靜置168小時。測定靜置後的樹脂硬化物的質量（g），並求出相對於靜置前的樹脂硬化物的質量（g）的增加率（%）。將結果歸納於表1中。＜Measurement of Water Absorption＞ Based on the conditions described above, cured resins of the curable resin compositions obtained in the Examples and Comparative Examples were produced. The cured resin was made into a rectangular cured product having a short side of 5.1 mm, a long side of 20 mm, and a thickness of 2 mm. Then, the cured resin was left to stand for 168 hours at a temperature of 85° C. and a relative humidity of 85%. The mass (g) of the resin cured product after standing was measured, and the increase rate (%) with respect to the mass (g) of the resin cured product before standing was calculated|required. Summarize the results in Table 1.

＜流動性評價（螺旋流動）＞使用依據EMMI-1-66的螺旋流動測定用模具，於模具溫度180℃、成形壓力6.9 MPa、硬化時間90秒的條件下將實施例及比較例中所獲得的硬化性樹脂組成物成形並求出流動距離（cm）。將測定結果歸納於表1中。＜Evaluation of fluidity (spiral flow)＞ The curable resin compositions obtained in the Examples and Comparative Examples were molded under the conditions of a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds using a mold for measuring spiral flow according to EMMI-1-66, and obtained Out flow distance (cm). The measurement results are summarized in Table 1.

[表1] 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 比較例1 比較例2 比較例3 環氧樹脂 A 70 70 70 70 70 70 70 - 70 70 B 30 30 30 30 30 30 30 70 30 30 C - - - - - - - 30 - - 酚系硬化劑 A 47.3 39.5 47.3 41.5 41.5 41.5 41.5 - - - B - - - - - - - - 42.5 30.4 C - - - - - - - - - 13 D - 3 - 3 3 3 3 6 3 3 E - 10 - 10 10 10 10 10 - 10 F 8 8 8 5.5 5.5 5.5 5.5 33.6 - 7.8 G - - - - - - - 42.8 - - 硬化促進劑 5 5 5 5 5 5 4.5 5 5.3 5.8 偶合劑 A 3 12 9 3 1 3 1 3 3.1 3 B 3 - - 4.5 1.5 4.5 1.5 4.5 3.1 4.5 C - - - - 5 - 5 - - - D - - - - - - - 1 - - 應力緩和劑 A - - 20 20 - 20 20 - 20 - B - - - - - - - 10 - 30 C 20 20 - - - - - - - - 無機填充劑 A 1387 1462 1588 1619 1469 1367 1451 1686 1063 1657 B - - - - - 152 161 - - - C - - - - - - - 10 - - D - - - - - - - 6 - - 脫模劑（蠟） 1 1 1 1 1 1 1 1 1 1 著色劑（碳黑） 3 3 3 4 4 3.5 3.5 3.1 3.3 4 離子交換體（水滑石化合物） 3 3 3 3 3 3 3 3 3 3 耐回焊性評價 A A A A B B B D D D （1）玻璃轉移溫度（℃） 105 98 102 86 86 86 83 102 112 125 （2）玻璃轉移溫度下的tanδ值 0.413 0.477 0.417 0.639 0.603 0.623 0.609 0.379 0.677 0.408 （3）tanδ合計220℃～250℃ 0.401 0.428 0.422 0.488 0.473 0.446 0.433 0.427 0.302 0.527 （4）tanδ合計70℃～90℃ 0.767 0.899 0.737 1.346 1.309 1.435 1.416 0.516 0.163 0.123 （5）tanδ比 97 88 95 66 71 80 67 75 57 87 貯存彈性係數（MPa） 355 349 417 338 359 293 320 172 372 615 酚系硬化劑的酚性羥基相對於環氧樹脂的環氧基的當量比 0.7 0.7 0.7 0.7 0.7 0.7 0.7 1 1 1 熱膨脹係數（CTE1）測定（ppm/℃） 9 9 9 10 10 11 11 7 10 6 吸水率的測定（%） 0.18 0.19 0.18 0.19 0.20 0.21 0.21 0.18 0.25 0.16 流動性評價（cm） 97 84 66 65 61 74 56 91 137 64 [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative example 1 Comparative example 2 Comparative example 3 epoxy resin A 70 70 70 70 70 70 70 - 70 70 B 30 30 30 30 30 30 30 70 30 30 C - - - - - - - 30 - - Phenolic hardener A 47.3 39.5 47.3 41.5 41.5 41.5 41.5 - - - B - - - - - - - - 42.5 30.4 C - - - - - - - - - 13 D. - 3 - 3 3 3 3 6 3 3 E. - 10 - 10 10 10 10 10 - 10 f 8 8 8 5.5 5.5 5.5 5.5 33.6 - 7.8 G - - - - - - - 42.8 - - hardening accelerator 5 5 5 5 5 5 4.5 5 5.3 5.8 Coupler A 3 12 9 3 1 3 1 3 3.1 3 B 3 - - 4.5 1.5 4.5 1.5 4.5 3.1 4.5 C - - - - 5 - 5 - - - D. - - - - - - - 1 - - stress reliever A - - 20 20 - 20 20 - 20 - B - - - - - - - 10 - 30 C 20 20 - - - - - - - - Inorganic filler A 1387 1462 1588 1619 1469 1367 1451 1686 1063 1657 B - - - - - 152 161 - - - C - - - - - - - 10 - - D. - - - - - - - 6 - - Release agent (wax) 1 1 1 1 1 1 1 1 1 1 Colorant (carbon black) 3 3 3 4 4 3.5 3.5 3.1 3.3 4 Ion exchanger (hydrotalcite compound) 3 3 3 3 3 3 3 3 3 3 Reflow Resistance Evaluation A A A A B B B D. D. D. (1) Glass transition temperature (°C) 105 98 102 86 86 86 83 102 112 125 (2) tanδ value at glass transition temperature 0.413 0.477 0.417 0.639 0.603 0.623 0.609 0.379 0.677 0.408 (3) The sum of tanδ is 220℃～250℃ 0.401 0.428 0.422 0.488 0.473 0.446 0.433 0.427 0.302 0.527 (4) The sum of tanδ is 70°C to 90°C 0.767 0.899 0.737 1.346 1.309 1.435 1.416 0.516 0.163 0.123 (5) Tanδ ratio 97 88 95 66 71 80 67 75 57 87 Storage elastic coefficient (MPa) 355 349 417 338 359 293 320 172 372 615 The equivalent ratio of the phenolic hydroxyl group of the phenolic hardener to the epoxy group of the epoxy resin 0.7 0.7 0.7 0.7 0.7 0.7 0.7 1 1 1 Coefficient of thermal expansion (CTE1) measurement (ppm/℃) 9 9 9 10 10 11 11 7 10 6 Determination of water absorption (%) 0.18 0.19 0.18 0.19 0.20 0.21 0.21 0.18 0.25 0.16 Mobility evaluation (cm) 97 84 66 65 61 74 56 91 137 64

根據歸納於表1中的結果而可知：與比較例中所獲得的硬化性樹脂組成物相比，實施例中所獲得的硬化性樹脂組成物的耐回焊性優異。From the results summarized in Table 1, it can be seen that the curable resin compositions obtained in Examples are superior in reflow resistance compared to the curable resin compositions obtained in Comparative Examples.

於2021年8月30日提出申請的日本專利申請案2021-140407號的揭示的全部內容藉由參照而併入至本說明書中。本說明書中所記載的所有文獻、專利申請案、及技術規格是與具體且分別記載各個文獻、專利申請案及技術規格藉由參照而併入的情況相同程度地藉由參照而併入至本說明書中。The entire disclosure of Japanese Patent Application No. 2021-140407 for which it applied on August 30, 2021 is incorporated in this specification by reference. All documents, patent applications, and technical specifications described in this specification are incorporated by reference to the same extent as if each individual document, patent application, and technical specification was specifically and individually stated to be incorporated by reference. in the manual.

無none

Claims

一種硬化性樹脂組成物，於藉由對硬化性樹脂組成物的樹脂硬化物進行動態黏彈性測定而獲得的將縱軸設為tanδ且將橫軸設為30℃～260℃的溫度的圖表中，（1）tanδ成為最大的溫度未滿120℃，（2）tanδ的最大值超過0.400，且（3）220℃、230℃、240℃及250℃各溫度下的tanδ值的合計超過0.400。A curable resin composition, in a graph in which the vertical axis is tan δ and the horizontal axis is temperature from 30°C to 260°C, obtained by measuring the dynamic viscoelasticity of a cured resin product of the curable resin composition , (1) The temperature at which tan δ becomes maximum is less than 120°C, (2) The maximum value of tan δ exceeds 0.400, and (3) The sum of the tan δ values at each temperature of 220°C, 230°C, 240°C, and 250°C exceeds 0.400.

一種硬化性樹脂組成物，於藉由對硬化性樹脂組成物的樹脂硬化物進行動態黏彈性測定而獲得的將縱軸設為tanδ且將橫軸設為30℃～260℃的溫度的圖表中，70℃、80℃及90℃各溫度下的tanδ值的合計超過0.600。A curable resin composition, in a graph in which the vertical axis is tan δ and the horizontal axis is temperature from 30°C to 260°C, obtained by measuring the dynamic viscoelasticity of a cured resin product of the curable resin composition , the sum of the tanδ values at each temperature of 70°C, 80°C, and 90°C exceeded 0.600.

如請求項1或請求項2所述的硬化性樹脂組成物，其中，於將所述圖表中的tanδ的最大值設為100時，tanδ成為最大的溫度-10℃的至少任一溫度下的tanδ值超過60。The curable resin composition according to claim 1 or claim 2, wherein when the maximum value of tan δ in the graph is set to 100, the temperature at which tan δ becomes maximum -10°C is at least any temperature The tan δ value exceeds 60.

如請求項1或請求項2所述的硬化性樹脂組成物，其中，藉由對硬化性樹脂組成物的樹脂硬化物進行動態黏彈性測定而求出的260℃下的貯存黏彈性為450 MPa以下。The curable resin composition according to claim 1 or claim 2, wherein the storage viscoelasticity at 260° C. obtained by measuring the dynamic viscoelasticity of the cured resin of the curable resin composition is 450 MPa the following.

如請求項1或請求項2所述的硬化性樹脂組成物，其中，以酚系硬化劑的酚性羥基相對於環氧樹脂的環氧基的當量比0.5以上且未滿1.0含有所述環氧樹脂及所述酚系硬化劑。The curable resin composition according to claim 1 or claim 2, wherein the ring is contained at an equivalent ratio of phenolic hydroxyl groups of the phenolic curing agent to epoxy groups of the epoxy resin of 0.5 or more and less than 1.0. Oxygen resin and the phenolic hardener.

一種電子零件裝置，包括元件以及將所述元件密封的如請求項1或請求項2所述的硬化性樹脂組成物的樹脂硬化物。An electronic component device comprising an element and a cured resin product of the curable resin composition according to claim 1 or claim 2 sealing the element.

如請求項6所述的電子零件裝置，更包括支撐構件，所述支撐構件於其中一面上搭載所述元件。The electronic component device according to claim 6, further comprising a support member on which the element is mounted on one surface.