TWI828881B - Thermoconductive composition and semiconductor device - Google Patents

Thermoconductive composition and semiconductor device Download PDF

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TWI828881B
TWI828881B TW109108757A TW109108757A TWI828881B TW I828881 B TWI828881 B TW I828881B TW 109108757 A TW109108757 A TW 109108757A TW 109108757 A TW109108757 A TW 109108757A TW I828881 B TWI828881 B TW I828881B
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conductive composition
thermally conductive
resin
particles
heat
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TW202045680A (en
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渡部直輝
高本真
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日商住友電木股份有限公司
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Abstract

本發明的導熱性組成物為含有金屬粒子、黏合劑樹脂及單體，且藉由熱處理使金屬粒子發生燒結而形成粒子連結結構者，在將導熱率設為λ（W/mK），且將25℃的儲存彈性模數設為E（GPa）時，λ及E滿足0.35≤λ/（E2 ）。The thermally conductive composition of the present invention contains metal particles, a binder resin and a monomer, and the metal particles are sintered by heat treatment to form a particle connected structure. When the thermal conductivity is λ (W/mK), and When the storage elastic modulus at 25°C is set to E (GPa), λ and E satisfy 0.35≤λ/(E 2 ).

Description

導熱性組成物及半導體裝置Thermal conductive compositions and semiconductor devices

本發明係有關一種導熱性組成物及半導體裝置。 The present invention relates to a thermally conductive composition and a semiconductor device.

迄今為止，在導熱性組成物中進行了各種開發。作為該等技術，例如，已知專利文獻1、專利文獻2中所記載之技術。 Hitherto, various developments have been made in thermally conductive compositions. As such technologies, for example, the technologies described in Patent Document 1 and Patent Document 2 are known.

在專利文獻1中記載了一種含有(甲基)丙烯酸酯化合物、自由基起始劑、銀微粒、銀粉及溶劑之半導體接著用熱硬化型樹脂組成物(專利文獻1的技術方案1)。具有如下記載：能夠藉由加熱至200℃之銀微粒來實現半導體元件和金屬基板的接合(0001、0007段等)。 Patent Document 1 describes a thermosetting resin composition for semiconductor adhesion containing a (meth)acrylate compound, a radical initiator, silver particles, silver powder, and a solvent (Technical Aspect 1 of Patent Document 1). There is a description that the semiconductor element and the metal substrate can be joined by silver particles heated to 200°C (paragraphs 0001, 0007, etc.).

另一方面，在專利文獻2中記載了一種含有環氧樹脂、硬化劑、硬化促進劑、稀釋劑、銀粉之樹脂漿料組成物(專利文獻2的表1)。具有如下記載：能夠使樹脂漿料組成物在150℃條件下硬化，並藉由環氧樹脂等硬化物來接著半導體元件和支持構件(0038段等)。 On the other hand, Patent Document 2 describes a resin slurry composition containing an epoxy resin, a hardener, a hardening accelerator, a diluent, and silver powder (Table 1 of Patent Document 2). There is a description that the resin slurry composition can be cured at 150° C. and the semiconductor element and the supporting member can be bonded with a cured product such as epoxy resin (paragraph 0038, etc.).

專利文獻1：日本特開2014-74132號公報 Patent Document 1: Japanese Patent Application Publication No. 2014-74132

專利文獻2：日本特開2000-239616號公報 Patent Document 2: Japanese Patent Application Publication No. 2000-239616

然而，本發明人進行研究之結果，明確了：在上述專利文獻1、 專利文獻2中所記載之組成物中，在熱循環特性及散熱性的方面具有改善的餘地。 However, as a result of research conducted by the present inventor, it was clarified that in the above-mentioned Patent Document 1, The composition described in Patent Document 2 has room for improvement in thermal cycle characteristics and heat dissipation properties.

本發明人進一步進行研究之結果，發現了：在將導熱性組成物用於接著半導體元件和支持基材之情形下，藉由適當地控制導熱性組成物的導熱率和儲存彈性模數，能夠提高半導體裝置的熱循環特性。 As a result of further research, the inventors found that when a thermally conductive composition is used to bond a semiconductor element and a supporting base material, by appropriately controlling the thermal conductivity and storage elastic modulus of the thermally conductive composition, it is possible to Improve thermal cycle characteristics of semiconductor devices.

然而，藉由經加熱處理之銀粒子的接合來接著半導體元件和支持基材之類型(以下，稱為燒結型。)可提高導熱率，但是相反地儲存彈性模數變高，熱循環特性有可能會下降。 However, the type in which the semiconductor element and the supporting base material are bonded by the bonding of heat-treated silver particles (hereinafter referred to as the sintered type.) can improve the thermal conductivity, but conversely, the storage elastic modulus becomes high, and the thermal cycle characteristics deteriorate. May drop.

另一方面，藉由經硬化處理之環氧樹脂等硬化成分來接著半導體元件和支持基材之類型(以下，稱為黏合劑型。)可將儲存彈性模數抑制為較低，但是相反地導熱率下降，散熱性有可能會下降。 On the other hand, a type in which a semiconductor element and a supporting base material are bonded to each other using a hardening component such as hardened epoxy resin (hereinafter referred to as an adhesive type) can suppress the storage elastic modulus to a low level, but conversely conducts heat. rate decreases, heat dissipation may decrease.

亦即，關於迄今為止的燒結型、黏合劑型，高導熱率和低儲存彈性模數顯示權衡關係，尚未充分研究兼顧導熱率的提高及儲存彈性模數的下降。 That is, with regard to conventional sintered and adhesive types, high thermal conductivity and low storage elastic modulus show a trade-off relationship, and sufficient research has not yet been conducted on balancing the improvement in thermal conductivity and the decrease in storage elastic modulus.

基於該種見解進一步進行深入研究之結果，明確了：藉由同時使用燒結型和黏合劑型，並且適當地選擇金屬粒子，能夠提高導熱率的同時降低儲存彈性模數，並且藉由將導熱率設為λ(W/mK)且將儲存彈性模數設為E(GPa)時的λ/(E2)作為指標來應用，能夠穩定地評價熱循環特性。 As a result of further in-depth research based on this insight, it was clarified that by using both the sintered type and the adhesive type, and appropriately selecting metal particles, the thermal conductivity can be increased while the storage elastic modulus can be reduced, and by setting the thermal conductivity When λ (W/mK) is λ (W/mK) and the storage elastic modulus is E (GPa), λ/(E 2 ) can be used as an index to stably evaluate the thermal cycle characteristics.

進一步進行研究之結果，發現：藉由適當地選擇作為該指標之λ/(E2)的數值範圍，並將該種導熱性組成物用於半導體元件和支持基材的接著，能夠提高半導體裝置的熱循環特性及散熱性，從而完成了本發明。 As a result of further research, it was found that by appropriately selecting the numerical range of λ/(E 2 ) as the index and using this thermally conductive composition for the bonding of the semiconductor element and the supporting base material, the semiconductor device can be improved. Thermal cycle characteristics and heat dissipation properties, thereby completing the present invention.

依據本發明，提供一種導熱性組成物，其含有：金屬粒子；黏合劑樹脂；及單體， 藉由熱處理使前述金屬粒子發生燒結而形成粒子連結結構，使用該導熱性組成物，依據下述步驟A測量之導熱率λ(W/mK)和依據下述步驟B測量之25℃的儲存彈性模數E(GPa)滿足下述式(I)。 According to the present invention, a thermally conductive composition is provided, which contains: metal particles; binder resin; and monomer, The aforementioned metal particles are sintered by heat treatment to form a particle connected structure. Using this thermally conductive composition, the thermal conductivity λ (W/mK) measured according to the following step A and the storage elasticity at 25°C measured according to the following step B are Modulus E (GPa) satisfies the following formula (I).

Figure 109108757-A0305-02-0005-9
Figure 109108757-A0305-02-0005-9

(步驟A) (Step A)

花費60分鐘將該導熱性組成物從30℃升溫至200℃，接著以200℃熱處理120分鐘，獲得厚度為1mm的熱處理體。對於所獲得之熱處理體，使用雷射閃光法，測量25℃時的導熱率λ(W/mK)。 The thermal conductive composition was heated from 30° C. to 200° C. for 60 minutes, and then heat-treated at 200° C. for 120 minutes to obtain a heat-treated body with a thickness of 1 mm. For the obtained heat-treated body, the thermal conductivity λ (W/mK) at 25° C. was measured using the laser flash method.

(步驟B) (Step B)

花費60分鐘將該導熱性組成物從30℃升溫至200℃，接著以200℃熱處理120分鐘而獲得熱處理體。對於所獲得之熱處理體，使用頻率1Hz時的動態黏彈性測量(DMA)，測量25℃時的儲存彈性模數E(MPa)。 The thermal conductive composition was heated from 30° C. to 200° C. for 60 minutes, and then heat-treated at 200° C. for 120 minutes to obtain a heat-treated body. For the obtained heat-treated body, the storage elastic modulus E (MPa) at 25°C was measured using dynamic viscoelasticity measurement (DMA) at a frequency of 1 Hz.

又，依據本發明，提供一種半導體裝置，其具備：基材；及半導體元件，其經由對上述導熱性組成物進行熱處理而獲得之接著層裝載於前述基材上。 Furthermore, according to the present invention, there is provided a semiconductor device including: a base material; and a semiconductor element in which an adhesive layer obtained by heat-treating the thermally conductive composition is mounted on the base material.

依據本發明，提供一種熱循環特性及散熱性優異的導熱性組成物及使用了其之半導體裝置。 According to the present invention, a thermally conductive composition excellent in thermal cycle characteristics and heat dissipation properties and a semiconductor device using the same are provided.

100:半導體裝置 100:Semiconductor device

10:接著層 10: Next layer

20:半導體元件 20:Semiconductor components

30:基材 30:Substrate

32:晶片墊 32:wafer pad

34:外引線 34:Outer lead

40:接合線 40:Joining wire

50:密封樹脂 50:Sealing resin

52:焊球 52: Solder ball

關於上述之目的及其他目的、特徵及優點，藉由在以下敘述之較佳的實施形態及其附帶之以下圖式而變得更明確。 The above objects and other objects, features and advantages will become clearer by the preferred embodiments described below and the accompanying drawings below.

[圖1]係表示本實施形態之電子裝置的一例之剖面圖。 [Fig. 1] is a cross-sectional view showing an example of the electronic device according to this embodiment.

[圖2]係表示本實施形態之電子裝置的一例之剖面圖。 [Fig. 2] is a cross-sectional view showing an example of the electronic device according to this embodiment.

以下，利用圖式，對本發明的實施形態進行說明。另外，在所有圖式中，對相同的構成要件標註相同的符號，並適當地省略說明。又，圖係概略圖，與實際尺寸比率不一致。 Hereinafter, embodiments of the present invention will be described using drawings. In addition, in all the drawings, the same components are denoted by the same symbols, and descriptions thereof are appropriately omitted. In addition, the drawing is a schematic diagram and does not match the actual size ratio.

對本實施形態的導熱性組成物的概要進行說明。 An outline of the thermally conductive composition of this embodiment will be described.

本實施形態的導熱性組成物為含有金屬粒子、黏合劑樹脂及單體，且藉由熱處理使金屬粒子發生燒結而形成粒子連結結構者。 The thermally conductive composition of this embodiment contains metal particles, a binder resin, and a monomer, and the metal particles are sintered by heat treatment to form a particle-connected structure.

在該導熱性組成物中，在將依據下述步驟A測量之導熱率設為λ(W/mK)，且將依據下述步驟B測量之25℃的儲存彈性模數設為E(GPa)時，λ及E滿足下述式(I)。 In this thermally conductive composition, let the thermal conductivity measured according to the following step A be λ (W/mK), and let the storage elastic modulus at 25°C measured according to the following step B be E (GPa) When , λ and E satisfy the following formula (I).

Figure 109108757-A0305-02-0006-1
Figure 109108757-A0305-02-0006-1

(步驟A) (Step A)

花費60分鐘將該導熱性組成物從30℃升溫至200℃，接著以200℃熱處理120分鐘，獲得厚度為1mm的熱處理體。對於所獲得之熱處理體，使用雷射閃光法，測量25℃時的導熱率λ(W/mK)。 The thermal conductive composition was heated from 30° C. to 200° C. for 60 minutes, and then heat-treated at 200° C. for 120 minutes to obtain a heat-treated body with a thickness of 1 mm. For the obtained heat-treated body, the thermal conductivity λ (W/mK) at 25° C. was measured using the laser flash method.

(步驟B) (Step B)

花費60分鐘將該導熱性組成物從30℃升溫至200℃，接著以200℃熱處理120分鐘而獲得熱處理體。對於所獲得之熱處理體，使用頻率1Hz時的動態黏彈性測量(DMA)，測量25℃時的儲存彈性模數E(MPa)。 The thermal conductive composition was heated from 30° C. to 200° C. for 60 minutes, and then heat-treated at 200° C. for 120 minutes to obtain a heat-treated body. For the obtained heat-treated body, the storage elastic modulus E (MPa) at 25°C was measured using dynamic viscoelasticity measurement (DMA) at a frequency of 1 Hz.

依據本發明人的見解，發現：藉由同時使用上述燒結型和黏合劑型，並且適當地選擇金屬粒子，能夠提高導熱率的同時降低儲存彈性模數。雖然 詳細機制尚不清楚，但是認為：由於使導熱性組成物硬化而成之接著層形成有金屬粒子的粒子連結結構(燒結結構)，因此導熱率比黏合劑型高，殘留有黏合劑樹脂等樹脂成分，因此儲存彈性模數比燒結型低。進而，認為：藉由使用金屬被覆在樹脂粒子的表面上之金屬塗層樹脂粒子作為金屬粒子，能夠抑制金屬粒子的燒結性的下降的同時適當地降低儲存彈性模數。 Based on the findings of the present inventors, it was found that by using both the sintered type and the binder type as described above and appropriately selecting metal particles, the thermal conductivity can be increased while the storage elastic modulus can be reduced. although The detailed mechanism is not yet clear, but it is thought that since the adhesive layer formed by hardening the thermally conductive composition has a particle connection structure (sintered structure) of metal particles, the thermal conductivity is higher than that of the adhesive type, and resin components such as adhesive resin remain. , so the storage elastic modulus is lower than that of the sintered type. Furthermore, it is considered that by using metal-coated resin particles in which metal coats the surface of the resin particles as metal particles, the storage elastic modulus can be appropriately reduced while suppressing the decrease in sinterability of the metal particles.

另外，該接著層能夠藉由金屬粒子的接合、黏合劑樹脂來接著半導體元件和支持基材，因此能夠實現良好的密接性。 In addition, this bonding layer can bond the semiconductor element and the supporting base material through the bonding of metal particles and the binder resin, so it can achieve good adhesion.

進而，依據本發明人的見解，明確了：藉由將導熱率設為λ(W/mK)且將儲存彈性模數設為E(GPa)時的λ/(E2)作為指標來應用，能夠穩定地評價熱循環特性。進一步進行研究之結果，發現了：藉由將作為該指標之λ/(E2)設為下限值以上，將該種導熱性組成物用於半導體元件和支持基材的接著，藉此能夠提高半導體裝置的熱循環特性。 Furthermore, based on the findings of the present inventors, it was clarified that by applying λ/(E 2 ) when the thermal conductivity is λ (W/mK) and the storage elastic modulus is E (GPa) as an index, Enables stable evaluation of thermal cycle characteristics. As a result of further research, it was found that by setting λ/(E 2 ) as the index to be equal to or higher than the lower limit value, this thermally conductive composition can be used for the bonding of semiconductor elements and supporting base materials. Improve thermal cycle characteristics of semiconductor devices.

上述λ/(E2)的下限為0.35以上，較佳為0.37以上，更佳為0.40以上。藉此，能夠提高熱循環特性。另一方面，上述λ/(E2)的上限例如可以為3.0以下、2.0以下、1.5以下。 The lower limit of λ/(E 2 ) is 0.35 or more, preferably 0.37 or more, more preferably 0.40 or more. Thereby, thermal cycle characteristics can be improved. On the other hand, the upper limit of λ/(E 2 ) may be, for example, 3.0 or less, 2.0 or less, or 1.5 or less.

又，在25℃條件下厚度方向上的上述導熱性組成物的熱處理體的導熱率的下限例如為10W/mK以上，較佳為15W/mK以上，更佳為20W/mK以上。藉此，能夠實現使用了上述導熱性組成物之接著層的高散熱性。另一方面，上述導熱性組成物的熱處理體的導熱率的上限例如可以為200W/mK以下，亦可以為150W/mK以下。 In addition, the lower limit of the thermal conductivity of the heat-treated body of the thermal conductive composition in the thickness direction under 25° C. is, for example, 10 W/mK or more, preferably 15 W/mK or more, and more preferably 20 W/mK or more. Thereby, it is possible to achieve high heat dissipation properties of the adhesive layer using the thermally conductive composition. On the other hand, the upper limit of the thermal conductivity of the heat-treated body of the thermally conductive composition may be, for example, 200 W/mK or less, or may be 150 W/mK or less.

又，儲存彈性模數E(GPa)的上限例如為15.0GPa以下，較佳為8.5GPa以下，更佳為7.0GPa以下。藉此，能夠進一步提高熱循環特性。上述儲存彈性模數E(GPa)的下限並無特別限定，但是例如可以為0.1GPa以上，亦可以為0.5GPa以上。 Moreover, the upper limit of the storage elastic modulus E (GPa) is, for example, 15.0 GPa or less, preferably 8.5 GPa or less, more preferably 7.0 GPa or less. Thereby, the thermal cycle characteristics can be further improved. The lower limit of the storage elastic modulus E (GPa) is not particularly limited, but may be, for example, 0.1 GPa or more, or may be 0.5 GPa or more.

又，相對於藉由下述步驟獲得之熱處理體100質量%，該藉由下述步驟獲得之熱處理體中的樹脂含量例如為10質量%以上且30質量%以下，較佳為12質量%以上29質量%以下。藉由設在該種數值範圍內，能夠實現儲存彈性模數及導熱率的平衡。 Moreover, the resin content in the heat-treated body obtained by the following step is, for example, 10 mass% or more and 30 mass% or less, preferably 12 mass% or more, relative to 100 mass% of the heat-treated body obtained by the following step. 29% by mass or less. By setting it within this numerical range, a balance between storage elastic modulus and thermal conductivity can be achieved.

(步驟) (step)

花費60分鐘將該導熱性組成物從30℃升溫至200℃，接著以200℃熱處理120分鐘而獲得熱處理體。 The thermal conductive composition was heated from 30° C. to 200° C. for 60 minutes, and then heat-treated at 200° C. for 120 minutes to obtain a heat-treated body.

樹脂含量能夠藉由測量所獲得之熱處理體的重量並從該重量中減去所含有之銀的重量來計算。 The resin content can be calculated by measuring the weight of the obtained heat-treated body and subtracting the weight of the contained silver from the weight.

對於樹脂含量的對象之樹脂成分，可舉出源自黏合劑樹脂之樹脂成分、源自金屬塗層樹脂粒子之樹脂成分，可以包含該等中的任一者或兩者。 Examples of the resin component targeted by the resin content include a resin component derived from a binder resin and a resin component derived from metal coating resin particles, and any one or both of these may be included.

本實施形態中，例如藉由適當地選擇導熱性組成物中所含有之各成分的種類、摻合量、導熱性組成物的製備方法等，能夠控制上述λ/(E2)、λ及樹脂的殘留量。該等中，作為用於將上述λ/(E2)、λ及樹脂的殘留量設在所期望的數值範圍內的要件，例如可舉出：同時使用燒結型組成系和黏合劑型組成系；及適當地選擇金屬塗層樹脂粒子的使用、其粒徑/含量等金屬粒子等。 In this embodiment, the above-mentioned λ/(E 2 ), λ and resin can be controlled, for example, by appropriately selecting the types and blending amounts of each component contained in the thermally conductive composition, the preparation method of the thermally conductive composition, etc. the residual amount. Among these, requirements for setting the above λ/(E 2 ), λ, and the residual amount of the resin within a desired numerical range include, for example, the simultaneous use of a sintered composition system and a binder type composition system; And appropriately select the use of metal coating resin particles, their particle size/content, etc. Metal particles.

本實施形態的導熱性組成物能夠用於各種用途，但是能夠適用於要求半導體元件等電子零件的散熱性和接著性之用途。具體而言，導熱性組成物介於半導體元件等電子零件與引線框等金屬構件之間，能夠用於形成用於接著該等之接著層。該接著層由導熱性組成物的熱處理體構成。 The thermally conductive composition of this embodiment can be used in various applications, but can be suitably used in applications requiring heat dissipation and adhesion of electronic components such as semiconductor elements. Specifically, the thermally conductive composition is interposed between electronic components such as semiconductor elements and metal members such as lead frames, and can be used to form an adhesive layer for bonding them. The adhesive layer is composed of a heat-treated body of a thermally conductive composition.

依據本實施形態，藉由使用由上述導熱性組成物的熱處理體構成之接著層，能夠提高半導體裝置中的熱循環特性。又，能夠實現半導體元件的高散熱性。能夠穩定地實現該高散熱性。 According to this embodiment, the thermal cycle characteristics in the semiconductor device can be improved by using an adhesive layer composed of a heat-treated body of the thermally conductive composition. In addition, high heat dissipation properties of the semiconductor element can be achieved. This high heat dissipation performance can be stably achieved.

以下，對本實施形態的導熱性組成物的各成分進行詳細敘述。 Hereinafter, each component of the thermally conductive composition of this embodiment will be described in detail.

本實施形態的導熱性組成物含有上述金屬粒子、黏合劑樹脂及單體。 The thermally conductive composition of this embodiment contains the above-mentioned metal particles, a binder resin, and a monomer.

雖然詳細機制尚不清楚，但是認為：若因加熱而單體揮發而組成物的體積收縮，則在金屬粒子彼此靠近之方向上施加應力，金屬粒子彼此的界面消失，形成金屬粒子的連結結構。又，認為：在該種金屬粒子燒結時，黏合劑樹脂、或者黏合劑樹脂與硬化劑或單體等的樹脂硬化物殘留於連結結構的內部或外圍。又，還認為：藉由硬化反應而產生如複數個金屬粒子凝聚之力。 Although the detailed mechanism is not yet clear, it is thought that when the monomer is volatilized due to heating and the volume of the composition shrinks, stress is applied in the direction in which the metal particles approach each other, and the interface between the metal particles disappears, forming a connected structure of the metal particles. Furthermore, it is considered that when such metal particles are sintered, the binder resin, or a cured resin product of the binder resin and a hardener or a monomer, remains inside or on the periphery of the connecting structure. Furthermore, it is also thought that the hardening reaction generates a force such as the aggregation of multiple metal particles.

藉由使上述導熱性組成物硬化，能夠實現含有「金屬粒子的粒子連結結構」和「由黏合劑樹脂、其硬化物、金屬塗層樹脂粒子中的樹脂粒子等構成之樹脂成分」之接著層。 By curing the thermally conductive composition, an adhesive layer containing "a particle connection structure of metal particles" and "a resin component composed of a binder resin, its cured product, resin particles in metal coating resin particles, etc." can be realized .

(金屬粒子) (metal particles)

本實施形態的導熱性組成物含有金屬粒子。該金屬粒子能夠藉由熱處理發生燒結而形成粒子連結結構(燒結結構)。 The thermally conductive composition of this embodiment contains metal particles. The metal particles can be sintered by heat treatment to form a particle-connected structure (sintered structure).

上述金屬粒子能夠使用金屬塗層樹脂粒子、由金屬構成之粒子等。上述金屬粒子能夠包含金屬塗層樹脂粒子及由金屬構成之粒子中的任一者，但是包含兩者為更佳。 As the metal particles, metal-coated resin particles, particles made of metal, etc. can be used. The metal particles may include either metal-coated resin particles or particles made of metal, but it is more preferable to include both.

藉由使用上述金屬塗層樹脂粒子，能夠抑制金屬粒子的燒結性的下降的同時適當地降低儲存彈性模數。藉由使用上述由金屬構成之粒子，能夠提高金屬粒子的燒結性的同時適當地提高導熱率。 By using the metal-coated resin particles, it is possible to appropriately reduce the storage elastic modulus while suppressing a decrease in the sinterability of the metal particles. By using the above-described particles made of metal, the sinterability of the metal particles can be improved and the thermal conductivity can be appropriately increased.

上述金屬塗層樹脂粒子由樹脂粒子和形成於樹脂粒子的表面上之金屬構成。亦即，上述金屬塗層樹脂粒子可以為金屬層被覆樹脂粒子的表面而得之粒子。 The metal-coated resin particles are composed of resin particles and metal formed on the surface of the resin particles. That is, the metal-coated resin particles may be particles in which the surface of the resin particles is coated with a metal layer.

本說明書中，金屬層被覆樹脂粒子的表面係指金屬層覆蓋樹脂粒子的表面的至少一部分區域之狀態，並不限於覆蓋樹脂粒子的整個表面之態樣， 例如，可以包含金屬層局部覆蓋表面之態樣、覆蓋從特定的剖面觀察時的整個表面之態樣。 In this specification, the surface of a resin particle covered with a metal layer refers to the state in which the metal layer covers at least a part of the surface of the resin particle, and is not limited to the state in which the entire surface of the resin particle is covered. For example, the metal layer may include a state in which the surface is partially covered or a state in which the metal layer covers the entire surface when viewed from a specific cross-section.

其中，就導熱性的觀點而言，金屬層覆蓋從特定的剖面觀察時的整個表面為較佳，覆蓋粒子的整個表面為進一步較佳。 Among them, from the viewpoint of thermal conductivity, it is preferable that the metal layer covers the entire surface when viewed from a specific cross section, and it is further preferable that the metal layer covers the entire surface of the particles.

上述金屬塗層樹脂粒子中的金屬例如能夠包含選自由銀、金、鎳、錫組成的群中之一種以上。可以將該等單獨使用，亦可以組合2種以上來使用。或者，可以使用以該等金屬為主要成分之合金。其中，就燒結性、導熱性的觀點而言，能夠使用銀。 The metal in the metal-coated resin particles may include, for example, one or more types selected from the group consisting of silver, gold, nickel, and tin. These may be used individually or in combination of 2 or more types. Alternatively, alloys containing these metals as main components may be used. Among them, silver can be used from the viewpoint of sintering properties and thermal conductivity.

關於構成上述金屬塗層樹脂粒子中的樹脂粒子(芯樹脂粒子)之樹脂材料，例如，可舉出聚矽氧、丙烯酸、苯酚、聚苯乙烯、三聚氰胺、聚醯胺、聚四氟乙烯等。可以將該等單獨使用，亦可以組合2種以上來使用。能夠由使用了該等之聚合物構成樹脂粒子。聚合物可以為均聚物，亦可以為以該等為主要成分之共聚物。 Examples of the resin material constituting the resin particles (core resin particles) in the metal-coated resin particles include polysilicone, acrylic, phenol, polystyrene, melamine, polyamide, polytetrafluoroethylene, and the like. These may be used individually or in combination of 2 or more types. Resin particles can be formed using these polymers. The polymer may be a homopolymer or a copolymer containing these as main components.

就彈性特性、耐熱性的觀點而言，上述樹脂粒子可以使用聚矽氧樹脂粒子、丙烯酸樹脂粒子。 From the viewpoint of elastic properties and heat resistance, polysilicone resin particles and acrylic resin particles can be used as the resin particles.

上述聚矽氧樹脂粒子可以為由藉由使甲基氯矽烷、三甲基三氯矽烷、二甲基二氯矽烷等有機氯矽烷聚合而獲得之有機聚矽氧烷構成之粒子，亦可以為以使該有機聚矽氧烷進一步三維交聯而成之結構為基本骨架之聚矽氧樹脂粒子。 The polysiloxane resin particles may be particles composed of organopolysiloxane obtained by polymerizing organochlorosilane such as methyl chlorosilane, trimethyltrichlorosilane, and dimethyldichlorosilane, or may be The basic skeleton of the polysiloxane resin particles is a structure formed by further three-dimensional cross-linking of the organopolysiloxane.

又，能夠在聚矽氧樹脂粒子的結構中導入各種官能基，作為能夠導入之官能基，可舉出環氧基、胺基、甲氧基、苯基、羧基、羥基、烷基、乙烯基、巰基等，但是並不限定於該等。 In addition, various functional groups can be introduced into the structure of polysilicone resin particles. Examples of the functional groups that can be introduced include epoxy group, amino group, methoxy group, phenyl group, carboxyl group, hydroxyl group, alkyl group, and vinyl group. , mercapto group, etc., but are not limited to these.

另外，本實施形態中，可以在不損害特性之範圍內在該聚矽氧樹脂粒子中添加其他低應力改質劑。作為能夠同時使用之其他低應力改質劑，可舉出丁二烯苯 乙烯橡膠、丁二烯丙烯腈橡膠、聚胺酯(poly urethane)橡膠、聚異戊二烯橡膠、丙烯酸橡膠、氟橡膠、液態有機聚矽氧烷、液態聚丁二烯等液態合成橡膠等，但是並不限定於該等。 In addition, in this embodiment, other low-stress modifiers may be added to the polysilicone resin particles within a range that does not impair the characteristics. Examples of other low-stress modifiers that can be used simultaneously include butadiene benzene Liquid synthetic rubbers such as ethylene rubber, butadiene acrylonitrile rubber, polyurethane rubber, polyisoprene rubber, acrylic rubber, fluorine rubber, liquid organopolysiloxane, liquid polybutadiene, etc., but are not Not limited to these.

上述樹脂粒子的形狀並無特別限定，可以為球形，但是亦可以為除了球形以外的不同形狀、例如扁平狀、板狀、針狀。在將金屬塗層樹脂粒子的形狀形成為球形之情形下，所使用之樹脂粒子的形狀亦係球形為較佳。另外，如上所述，球形並不限於完全的圓球，還包括如橢圓之接近球形之形狀、在表面具有若干個凹凸之形狀等。 The shape of the above-mentioned resin particles is not particularly limited and may be spherical, but may also be different shapes other than spherical, for example, flat, plate-shaped, or needle-shaped. When the shape of the metal coating resin particles is formed into a spherical shape, it is preferable that the shape of the resin particles used is also spherical. In addition, as mentioned above, the spherical shape is not limited to a complete sphere, but also includes a shape close to a sphere such as an ellipse, a shape having several concavities and convexities on the surface, and the like.

上述金屬塗層樹脂粒子的比重的下限例如為2以上，2.5以上為較佳，3以上為進一步較佳。藉此，能夠進一步提高作為接著層的導熱性、導電性。又，上述金屬塗層樹脂粒子的比重的上限例如為10以下，9以下為較佳，8以下為進一步較佳。藉此，能夠提高粒子的分散性。上述比重可以為包含金屬塗層樹脂粒子和由金屬構成之粒子之金屬粒子的比重。 The lower limit of the specific gravity of the metal coating resin particles is, for example, 2 or more, preferably 2.5 or more, and more preferably 3 or more. Thereby, the thermal conductivity and electrical conductivity as an adhesive layer can be further improved. Furthermore, the upper limit of the specific gravity of the metal coating resin particles is, for example, 10 or less, preferably 9 or less, and further preferably 8 or less. Thereby, the dispersibility of the particles can be improved. The specific gravity may be the specific gravity of metal particles including metal-coated resin particles and particles made of metal.

上述金屬塗層樹脂粒子可以為單分散系粒子，亦可以為多分散系粒子。又，在粒徑頻率分布中，上述金屬塗層樹脂粒子可以具有1個峰，亦可以具有2個以上的複數個峰。 The metal coating resin particles may be monodisperse particles or polydisperse particles. Furthermore, in the particle size frequency distribution, the metal coating resin particles may have one peak, or may have a plurality of two or more peaks.

上述由金屬構成之粒子可以為由1種或2種以上的金屬材料構成之粒子，芯部分和表層部分可以由相同或不同種類的金屬材料構成。金屬材料例如能夠包含選自由銀、金及銅組成的群中之一種以上。可以將該等單獨使用，亦可以組合2種以上來使用。或者，可以使用以該等金屬為主要成分之合金。其中，就燒結性、導熱性的觀點而言，能夠使用銀。 The above-mentioned particles made of metal may be made of one or more than two kinds of metal materials, and the core part and the surface part may be made of the same or different kinds of metal materials. The metal material can include, for example, one or more types selected from the group consisting of silver, gold, and copper. These may be used individually or in combination of 2 or more types. Alternatively, alloys containing these metals as main components may be used. Among them, silver can be used from the viewpoint of sintering properties and thermal conductivity.

上述由金屬構成之粒子的形狀例如可以為球形，亦可以為片(flake)狀。上述由金屬構成之粒子能夠包含球形粒子及片狀粒子中的任一者或兩者。 The shape of the particles made of metal may be, for example, a spherical shape or a flake shape. The particles made of metal may include any one or both of spherical particles and flaky particles.

關於上述金屬粒子的一態樣，作為上述金屬塗層樹脂粒子包含銀塗層聚矽氧樹脂粒子及作為由金屬構成之粒子包含銀粒子。 In one aspect of the metal particles, the metal-coated resin particles include silver-coated silicone resin particles and the particles made of metal include silver particles.

除了銀塗層聚矽氧樹脂粒子以外，就彈性特性的觀點而言，還可以使用銀塗層丙烯酸樹脂粒子。除了銀粒子以外，例如為了促進燒結或低成本化等目的而還能夠同時使用金粒子、銅粒子等含有除了銀以外的金屬成分之粒子。 In addition to silver-coated silicone resin particles, silver-coated acrylic resin particles can also be used from the viewpoint of elastic properties. In addition to silver particles, particles containing metal components other than silver, such as gold particles and copper particles, can also be used for the purpose of promoting sintering or reducing costs.

上述金屬塗層樹脂粒子的平均粒徑D50的下限例如可以為0.5μm以上，較佳為1.5μm以上，更佳為2.0μm以上。藉此，能夠降低儲存彈性模數。另一方面，上述金屬塗層樹脂粒子的平均粒徑D50的上限例如可以為20μm以下，亦可以為15μm以下，還可以為10μm以下。藉此，能夠提高導熱性。上述金屬塗層樹脂粒子的平均粒徑D50可以用作銀塗層聚矽氧樹脂粒子、銀塗層丙烯酸樹脂粒子的平均粒徑D50。 The lower limit of the average particle diameter D 50 of the metal coating resin particles may be, for example, 0.5 μm or more, preferably 1.5 μm or more, and more preferably 2.0 μm or more. Thereby, the storage elastic modulus can be reduced. On the other hand, the upper limit of the average particle diameter D 50 of the metal coating resin particles may be, for example, 20 μm or less, 15 μm or less, or 10 μm or less. Thereby, thermal conductivity can be improved. The average particle diameter D 50 of the metal-coated resin particles can be used as the average particle diameter D 50 of the silver-coated silicone resin particles and the silver-coated acrylic resin particles.

上述由金屬構成之粒子的平均粒徑D50的下限例如為0.8μm以上，較佳為1.0μm以上，更佳為1.2μm以上。藉此，能夠提高導熱性。另一方面，上述由金屬構成之粒子的平均粒徑D50的上限例如為7.0μm以下，較佳為5.0μm以下，更佳為4.0μm以下。藉此，能夠提高金屬粒子之間的燒結性。又，能夠實現提高燒結的均勻性。上述由金屬構成之粒子的平均粒徑D50可以用作銀粒子的平均粒徑D50。 The lower limit of the average particle diameter D 50 of the metal particles is, for example, 0.8 μm or more, preferably 1.0 μm or more, and more preferably 1.2 μm or more. Thereby, thermal conductivity can be improved. On the other hand, the upper limit of the average particle diameter D 50 of the particles made of metal is, for example, 7.0 μm or less, preferably 5.0 μm or less, and more preferably 4.0 μm or less. This can improve the sinterability between metal particles. In addition, the uniformity of sintering can be improved. The average particle diameter D 50 of the particles made of metal can be used as the average particle diameter D 50 of the silver particles.

另外，金屬粒子的平均粒徑D50例如能夠藉由使用Sysmex Corporation製造的流動式粒子像分析裝置FPIA(註冊商標)-3000進行粒子圖像測量來確定。更具體而言，能夠藉由使用上述裝置測量體積基準的中值粒徑來確定金屬粒子的粒徑。 In addition, the average particle diameter D 50 of the metal particles can be determined, for example, by particle image measurement using a flow particle image analyzer FPIA (registered trademark)-3000 manufactured by Sysmex Corporation. More specifically, the particle diameter of the metal particles can be determined by measuring the volume-based median diameter using the above-mentioned device.

相對於金屬粒子整體(100質量%)，上述金屬塗層樹脂粒子的含量例如為1質量%~50質量%，較佳為3質量%~45質量%，更佳為5質量%~40質量%。藉由設為上述下限值以上，能夠降低儲存彈性模數。藉由設為上述上限值 以下，能夠提高導熱率。 The content of the above-mentioned metal coating resin particles is, for example, 1 mass% to 50 mass%, preferably 3 mass% to 45 mass%, more preferably 5 mass% to 40 mass%, relative to the entire metal particles (100 mass%). . By setting it to the above lower limit value or more, the storage elastic modulus can be reduced. By setting it to the upper limit value above The thermal conductivity can be improved as follows.

相對於導熱性組成物整體(100質量%)，上述金屬粒子的含量為1質量%~98質量%，較佳為30質量%~95質量%，更佳為50質量%~90質量%。藉由設為上述下限值以上，能夠提高導熱性。藉由設為上述上限值以下，能夠提高塗佈性、黏貼時的作業性。 The content of the above-mentioned metal particles is 1 mass% to 98 mass%, preferably 30 mass% to 95 mass%, and more preferably 50 mass% to 90 mass% relative to the entire thermal conductive composition (100 mass%). By setting it as above the said lower limit value, thermal conductivity can be improved. By setting it below the above-mentioned upper limit, it is possible to improve coatability and workability during adhesion.

本說明書中，關於「~」，只要無特別說明，則表示包含上限值和下限值。 In this manual, "~" means that the upper limit and lower limit are included unless otherwise specified.

(黏合劑樹脂) (Binder resin)

上述導熱性組成物含有黏合劑樹脂。 The thermally conductive composition contains a binder resin.

上述黏合劑樹脂能夠包含選自由環氧樹脂、丙烯酸樹脂及烯丙基樹脂組成的群中之1種以上。可以將該等單獨使用，亦可以組合2種以上來使用。 The above-mentioned binder resin can contain one or more types selected from the group consisting of epoxy resin, acrylic resin, and allyl resin. These may be used individually or in combination of 2 or more types.

作為上述黏合劑樹脂，具體而言，能夠舉出：丙烯酸低聚物、丙烯酸聚合物等丙烯酸樹脂；環氧低聚物、環氧聚合物等環氧樹脂；烯丙基低聚物、烯丙基聚合物等烯丙基樹脂等。可以將該等單獨使用，亦可以組合2種以上來使用。 Specific examples of the binder resin include: acrylic resins such as acrylic oligomers and acrylic polymers; epoxy resins such as epoxy oligomers and epoxy polymers; allyl oligomers, allyl Based polymers such as allyl resin, etc. These may be used individually or in combination of 2 or more types.

另外，將重量平均分子量小於1萬者設為低聚物，且將重量平均分子量為1萬以上者設為聚合物。 In addition, those having a weight average molecular weight of less than 10,000 are termed oligomers, and those having a weight average molecular weight of 10,000 or more are termed polymers.

作為上述環氧樹脂，可以使用在分子內具有2個以上的環氧基之環氧樹脂。該環氧樹脂在25℃條件下可以為液態。藉此，能夠提高導熱性組成物的處理性。又，能夠適當地調節其硬化收縮。 As the above-mentioned epoxy resin, an epoxy resin having two or more epoxy groups in the molecule can be used. The epoxy resin can be liquid at 25°C. This can improve the handleability of the thermally conductive composition. In addition, the hardening shrinkage can be appropriately adjusted.

關於上述環氧樹脂的具體例，例如，可舉出三酚甲烷型環氧樹脂；氫化雙酚A型液態環氧樹脂；雙酚-F-二環氧丙基醚等雙酚F型液態環氧樹脂；鄰甲酚酚醛清漆型環氧樹脂等。可以將該等單獨使用，亦可以組合2種以上來使用。 Specific examples of the above-mentioned epoxy resin include, for example, trisphenolmethane type epoxy resin; hydrogenated bisphenol A type liquid epoxy resin; bisphenol F-type liquid epoxy resin such as bisphenol-F-diepoxypropyl ether; Oxygen resin; o-cresol novolak type epoxy resin, etc. These may be used individually or in combination of 2 or more types.

其中，可以使用氫化雙酚A型液態環氧樹脂或雙酚F型液態環氧樹脂。作為雙酚F型液態環氧樹脂，例如，能夠使用雙酚-F-二環氧丙基醚。 Among them, hydrogenated bisphenol A type liquid epoxy resin or bisphenol F type liquid epoxy resin can be used. As the bisphenol F-type liquid epoxy resin, for example, bisphenol-F-diglycidyl ether can be used.

作為上述丙烯酸樹脂，可以使用在分子內具有2個以上的丙烯酸基之丙烯酸樹脂。該丙烯酸樹脂在25℃條件下可以為液態。 As the acrylic resin, an acrylic resin having two or more acrylic groups in the molecule can be used. The acrylic resin can be liquid at 25°C.

作為上述丙烯酸樹脂，具體而言，能夠使用使丙烯酸單體(共)聚合而得者。在此，作為(共)聚合的方法，並無限定，能夠使用溶液聚合等、使用一般的聚合起始劑及鏈轉移劑之公知的方法。 Specifically, as the acrylic resin, one obtained by (co)polymerizing an acrylic monomer can be used. Here, the (co)polymerization method is not limited, and a known method using a general polymerization initiator and a chain transfer agent, such as solution polymerization, can be used.

作為上述烯丙基樹脂，可以使用在1個分子內具有2個以上的烯丙基之烯丙基樹脂。該烯丙基樹脂在25℃條件下可以為液態。 As the allyl resin, an allyl resin having two or more allyl groups in one molecule can be used. The allyl resin can be liquid at 25°C.

作為上述烯丙基樹脂，具體而言，可舉出藉由使二羧酸、烯丙醇及具備烯丙基之化合物進行反應而獲得之烯丙酯樹脂。 Specific examples of the allyl resin include allyl ester resins obtained by reacting dicarboxylic acid, allyl alcohol, and a compound having an allyl group.

在此，作為上述二羧酸，具體而言，可舉出草酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、順丁烯二酸、反丁烯二酸、酞酸、四氫酞酸、六氫酞酸等。又，作為具備上述烯丙基之化合物，具體而言，可舉出具備烯丙基之聚醚、聚酯、聚碳酸酯、聚丙烯酸酯、聚甲基丙烯酸酯、聚丁二烯、丁二烯丙烯腈共聚物等。 Here, specific examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, etc. Furthermore, specific examples of the compound having an allyl group include polyether, polyester, polycarbonate, polyacrylate, polymethacrylate, polybutadiene, and butylene having an allyl group. Allyl acrylonitrile copolymer, etc.

相對於導熱性組成物100質量份，上述黏合劑樹脂的含量的下限例如為1質量份以上，較佳為2質量份以上，更佳為3質量份以上。藉此，能夠提高與被接著體的密接性。另一方面，相對於導熱性組成物100質量份，上述黏合劑樹脂的含量的上限例如為15質量份以下，較佳為12質量份以下，更佳為10質量份以下。藉此，能夠抑制導熱性的下降。 The lower limit of the content of the binder resin is, for example, 1 part by mass or more, preferably 2 parts by mass or more, and more preferably 3 parts by mass or more based on 100 parts by mass of the thermally conductive composition. This can improve the adhesion with the adherend. On the other hand, the upper limit of the content of the binder resin is, for example, 15 parts by mass or less, preferably 12 parts by mass or less, and more preferably 10 parts by mass or less based on 100 parts by mass of the thermally conductive composition. Thereby, it is possible to suppress a decrease in thermal conductivity.

(單體) (single)

上述導熱性組成物含有單體。 The thermally conductive composition contains a monomer.

關於上述單體，能夠包含選自由二醇單體、丙烯酸單體、環氧單體及順丁烯二醯亞胺單體組成的群中之一種或兩種以上。可以將該等單獨使用，亦可以組合2種以上來使用。 The above-mentioned monomer may contain one or two or more types selected from the group consisting of a glycol monomer, an acrylic monomer, an epoxy monomer, and a maleimine monomer. These may be used individually or in combination of 2 or more types.

藉由使用上述單體，能夠調節進行了加熱處理時之上述導熱性組成物的揮發狀態。又，藉由適當地選擇與黏合劑樹脂、硬化劑的組合，可以使上述單體與該等進行硬化反應，調節硬化收縮狀態。 By using the above-mentioned monomer, it is possible to adjust the volatilization state of the above-mentioned thermally conductive composition when heat treatment is performed. In addition, by appropriately selecting the combination with the binder resin and hardener, the above-mentioned monomer can undergo a curing reaction with these to adjust the curing shrinkage state.

作為上述二醇單體，具體而言，可舉出：在分子中具備2個羥基，且該2個羥基與分別不同的碳原子鍵結之二元醇；該二元醇與2個以上的醇縮合而得之化合物；該醇縮合而得之化合物的羥基中的氫原子被碳數1以上且30以下的有機基取代而成為烷氧基者等。 Specific examples of the glycol monomer include: a glycol having two hydroxyl groups in the molecule, and the two hydroxyl groups are bonded to different carbon atoms; and a glycol with two or more hydroxyl groups. A compound obtained by condensation of alcohol; a compound obtained by condensation of alcohol in which the hydrogen atom in the hydroxyl group is substituted with an organic group having 1 to 30 carbon atoms to form an alkoxy group, etc.

作為上述二醇單體，具體而言，可舉出乙二醇、乙二醇單甲醚、乙二醇單乙醚、乙二醇單正丙醚、乙二醇單異丙醚、乙二醇單正丁醚、乙二醇單異丁醚、乙二醇單己醚、乙二醇單2-乙基己醚、乙二醇單烯丙基醚、乙二醇單苯基醚、乙二醇單苄基醚、二乙二醇、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單正丙醚、二乙二醇單異丙醚、二乙二醇單正丁醚、二乙二醇單異丁醚、二乙二醇單己醚、二乙二醇單2-乙基己醚、二乙二醇單苄基醚、三乙二醇、三乙二醇單甲醚、三乙二醇單乙醚、三乙二醇單正丁醚、四乙二醇、四乙二醇單甲醚、四乙二醇單乙醚、四乙二醇單正丁醚、丙二醇、丙二醇單甲醚、丙二醇單乙醚、丙二醇單正丙醚、丙二醇單異丙醚、丙二醇單正丁醚、丙二醇單苯基醚、二丙二醇、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單正丙醚、二丙二醇單正丁醚、三丙二醇、三丙二醇單甲醚、三丙二醇單乙醚、三丙二醇單正丁醚等。可以將該等單獨使用，亦可以組合2種以上來使用。其中，就揮發性的觀點而言，能夠使用三丙二醇單正丁醚或乙二醇單乙酸正丁酯。 Specific examples of the glycol monomer include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, and ethylene glycol. Mono-n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monoallyl ether, ethylene glycol monophenyl ether, ethylene glycol Alcohol monobenzyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n Butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono2-ethylhexyl ether, diethylene glycol monobenzyl ether, triethylene glycol, triethylene glycol Monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol mono-n-butyl ether, tetraethylene glycol, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol mono-n-butyl ether, propylene glycol , propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono n-butyl ether, propylene glycol monophenyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mono-n-butyl ether, etc. These may be used individually or in combination of 2 or more types. Among them, from the viewpoint of volatility, tripropylene glycol mono-n-butyl ether or ethylene glycol mono-n-butyl acetate can be used.

作為上述二醇單體的沸點的下限，例如，100℃以上為較佳，130℃以上為更佳，150℃以上為進一步較佳，170℃以上為進一步較佳，190℃以上為特佳。又，作為二醇單體的沸點的上限，例如，可以為400℃以下，亦可以為350℃以下。 The lower limit of the boiling point of the glycol monomer is, for example, preferably 100°C or higher, more preferably 130°C or higher, further preferably 150°C or higher, further preferably 170°C or higher, and particularly preferably 190°C or higher. Furthermore, the upper limit of the boiling point of the glycol monomer may be, for example, 400°C or lower, or 350°C or lower.

另外，二醇單體的沸點表示大氣壓下(101.3kPa)的沸點。 In addition, the boiling point of the glycol monomer indicates the boiling point at atmospheric pressure (101.3 kPa).

作為上述丙烯酸單體，可舉出在分子中具備(甲基)丙烯酸基之單體。 Examples of the acrylic monomer include monomers having a (meth)acrylic acid group in the molecule.

在此，(甲基)丙烯酸基表示丙烯酸基及甲基丙烯酸基。 Here, (meth)acrylic acid group means an acrylic acid group and a methacrylic acid group.

上述丙烯酸單體可以為在分子中僅具備1個(甲基)丙烯酸基之單官能丙烯酸單體，亦可以為在分子中具備2個以上的(甲基)丙烯酸基之多官能丙烯酸單體。 The acrylic monomer may be a monofunctional acrylic monomer having only one (meth)acrylic acid group in the molecule, or a polyfunctional acrylic monomer having two or more (meth)acrylic acid groups in the molecule.

作為上述單官能丙烯酸單體，具體而言，可舉出(甲基)丙烯酸2-苯氧乙酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸正月桂酯、(甲基)丙烯酸正十三烷基酯、(甲基)丙烯酸正硬脂酯、(甲基)丙烯酸異硬脂酯、乙氧基二乙二醇(甲基)丙烯酸酯、丁氧基二乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、2-乙基己基二乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基二丙二醇(甲基)丙烯酸酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧乙酯、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、壬基酚環氧乙烷改質(甲基)丙烯酸酯、苯基苯酚環氧乙烷改質(甲基)丙烯酸酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸二乙胺基乙酯、(甲基)丙烯酸二甲胺基乙酯四級化合物、(甲基)丙烯酸環氧丙酯、新戊二醇(甲基)丙烯酸苯甲酸酯、1,4-環己烷二甲醇單(甲基)丙烯酸酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸2-羥丁酯、(甲基)丙烯酸2-羥基-3-苯氧丙酯、2-(甲基)丙烯醯氧乙基丁二酸、2-(甲基)丙烯醯氧乙基六氫酞酸、2-(甲基)丙烯醯氧乙基酞酸、2-(甲基)丙烯醯氧乙基-2-羥乙基酞酸及2-(甲基)丙 烯醯氧乙基酸性磷酸酯等。 Specific examples of the monofunctional acrylic monomer include 2-phenoxyethyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and iso(meth)acrylate. Butyl ester, tertiary butyl (meth)acrylate, isopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-laurel (meth)acrylate Ester, n-tridecyl (meth)acrylate, n-stearyl (meth)acrylate, isostearyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, butoxy Diethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 2-ethylhexyl diethylene glycol (meth)acrylate, methoxy polyethylene glycol ( Meth)acrylate, methoxydipropylene glycol (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid Phenoxyethyl ester, phenoxydiethylene glycol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, nonylphenol ethylene oxide modified (meth)acrylate, benzene Phenol ethylene oxide modified (meth)acrylate, isocamphenyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, (meth)acrylate Dimethylaminoethyl acrylate quaternary compound, glycidyl (meth)acrylate, neopentyl glycol (meth)acrylate benzoate, 1,4-cyclohexanedimethanol mono(methyl )Acrylates, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxy (meth)acrylate Propyl ester, 2-(meth)acryloxyethyl succinic acid, 2-(meth)acryloxyethyl hexahydrophthalic acid, 2-(meth)acryloxyethyl phthalic acid, 2- (Meth)acryloyloxyethyl-2-hydroxyethylphthalic acid and 2-(methyl)propanol Enyloxyethyl acid phosphate, etc.

作為多官能丙烯酸單體，具體而言，可舉出乙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、丙氧基化雙酚A二(甲基)丙烯酸酯、己烷-1,6-二醇雙(2-(甲基)丙烯酸甲酯)、4,4’-異亞丙基二苯酚二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,6-雙((甲基)丙烯醯氧基)-2,2,3,3,4,4,5,5-八氟己烷、1,4-雙((甲基)丙烯醯氧基)丁烷、1,6-雙((甲基)丙烯醯氧基)己烷、三乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、N,N’-二(甲基)丙烯醯基乙二胺、N,N’-(1,2-二羥基乙烯)雙(甲基)丙烯醯胺或1,4-雙((甲基)丙烯醯基)哌

Figure 109108757-A0305-02-0017-6
等。 Specific examples of the polyfunctional acrylic monomer include ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and propoxylated bisphenol A di(meth)acrylate. Acrylate, hexane-1,6-diol bis(methyl 2-(meth)acrylate), 4,4'-isopropylidenediphenol di(meth)acrylate, 1,3-butanediol Alcohol di(meth)acrylate, 1,6-bis((meth)acryloxy)-2,2,3,3,4,4,5,5-octafluorohexane, 1,4- Bis((meth)acryloxy)butane, 1,6-bis((meth)acryloxy)hexane, triethylene glycol di(meth)acrylate, neopentyl glycol di( Meth)acrylate, neopentyl glycol di(meth)acrylate, N,N'-di(meth)acryloethylenediamine, N,N'-(1,2-dihydroxyethylene)bis (Meth)acrylamide or 1,4-bis((meth)acrylamide)piper
Figure 109108757-A0305-02-0017-6
wait.

作為丙烯酸單體，可以單獨使用單官能丙烯酸單體或多官能丙烯酸單體，亦可以同時使用單官能丙烯酸單體及多官能丙烯酸單體。作為丙烯酸單體，例如，單獨使用多官能丙烯酸單體為較佳。 As the acrylic monomer, a monofunctional acrylic monomer or a multifunctional acrylic monomer may be used alone, or a monofunctional acrylic monomer and a multifunctional acrylic monomer may be used together. As the acrylic monomer, for example, it is preferable to use a polyfunctional acrylic monomer alone.

上述環氧單體為在分子中具備環氧基之單體。 The above-mentioned epoxy monomer is a monomer having an epoxy group in the molecule.

上述環氧單體可以為在分子中僅具備1個環氧基之單官能環氧單體，亦可以為在分子中具備2個以上的環氧基之多官能環氧單體。 The above-mentioned epoxy monomer may be a monofunctional epoxy monomer having only one epoxy group in the molecule, or a polyfunctional epoxy monomer having two or more epoxy groups in the molecule.

作為上述單官能環氧單體，具體而言，可舉出4-三級丁基苯基環氧丙基醚、間甲苯酚基環氧丙基醚、對甲苯酚基環氧丙基醚、苯基環氧丙基醚、甲苯酚基環氧丙基醚等。 Specific examples of the monofunctional epoxy monomer include 4-tertiary butylphenyl glycidyl ether, m-cresolyl glycidyl ether, and p-cresolyl glycidyl ether. Phenyl glycidyl ether, cresolyl glycidyl ether, etc.

作為上述多官能環氧單體，具體而言，可舉出：雙酚A、雙酚F、聯苯酚等雙酚化合物或該等的衍生物；氫化雙酚A、氫化雙酚F、氫化聯苯酚、環己烷二醇、環己烷二甲醇、環己烷二乙醇等具有脂環結構之二醇或該等的衍生物；使丁二醇、己二醇、辛二醇、壬二醇、癸二醇等脂肪族二醇或該等的衍生物等環氧化而得之2官能者；具有三羥基苯基甲烷骨架、胺基苯酚骨架之3官能者；使酚醛清漆樹脂、甲酚酚醛清漆樹脂、苯酚芳烷基樹脂、聯苯芳烷基樹脂、萘酚 芳烷基樹脂等環氧化而得之多官能者等。 Specific examples of the polyfunctional epoxy monomer include: bisphenol compounds such as bisphenol A, bisphenol F, and biphenol or their derivatives; hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol Phenol, cyclohexanediol, cyclohexanedimethanol, cyclohexanediethanol and other glycols with alicyclic structures or their derivatives; make butanediol, hexanediol, octanediol, nonanediol Bifunctional ones obtained by epoxidation of aliphatic diols such as , decanediol or their derivatives; trifunctional ones having trihydroxyphenylmethane skeleton and aminophenol skeleton; making novolac resin, cresol novolac Varnish resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol Polyfunctional ones obtained by epoxidation of aralkyl resins, etc.

上述順丁烯二醯亞胺單體為在分子中具備順丁烯二醯亞胺環之單體。 The above-mentioned maleimine monomer is a monomer having a maleimine ring in the molecule.

上述順丁烯二醯亞胺單體可以為在分子中僅具備1個順丁烯二醯亞胺環之單官能順丁烯二醯亞胺單體，亦可以為在分子中具備2個以上的順丁烯二醯亞胺環之多官能順丁烯二醯亞胺單體。 The above-mentioned maleimine monomer may be a monofunctional maleimine monomer having only one maleimine ring in the molecule, or it may be a monofunctional maleimine monomer having two or more maleimine rings in the molecule. Polyfunctional maleimine monomer of maleimine ring.

作為上述順丁烯二醯亞胺單體，具體而言，可舉出聚四亞甲基醚二醇-二(2-順丁烯二醯亞胺乙酸酯)等。 Specific examples of the maleimide monomer include polytetramethylene ether glycol-bis(2-maleimide acetate) and the like.

相對於導熱性組成物100質量份，上述單體的含量的下限例如為0.5質量份以上，較佳為1.0質量份以上，更佳為2.0質量份以上。另一方面，相對於導熱性組成物100質量份，上述單體的含量的上限例如為10質量份以下，較佳為7質量份以下，更佳為5質量份以下。 The lower limit of the content of the above monomer is, for example, 0.5 parts by mass or more, preferably 1.0 parts by mass or more, and more preferably 2.0 parts by mass or more, based on 100 parts by mass of the thermally conductive composition. On the other hand, the upper limit of the content of the above-mentioned monomer is, for example, 10 parts by mass or less, preferably 7 parts by mass or less, and more preferably 5 parts by mass or less based on 100 parts by mass of the thermally conductive composition.

(硬化劑) (hardener)

依需要，上述導熱性組成物可以含有硬化劑。 If necessary, the thermally conductive composition may contain a hardener.

上述硬化劑具有與單體、黏合劑樹脂中的官能基進行反應之反應性基團。反應性基團例如可以使用環氧基、順丁烯二醯亞胺基、羥基等與官能基進行反應者。 The above-mentioned hardener has a reactive group that reacts with the functional groups in the monomer and binder resin. Examples of reactive groups include those that react with functional groups such as epoxy groups, maleimide groups, and hydroxyl groups.

具體而言，在單體包含環氧單體或/和黏合劑樹脂包含環氧樹脂之情形下，可以使用酚樹脂系硬化劑或咪唑系硬化劑作為上述硬化劑。 Specifically, when the monomer contains an epoxy monomer or/and the binder resin contains an epoxy resin, a phenol resin-based hardener or an imidazole-based hardener can be used as the hardener.

作為上述酚樹脂系硬化劑，具體而言，可舉出酚醛清漆樹脂、甲酚酚醛清漆樹脂、雙酚酚醛清漆樹脂、苯酚-聯苯酚醛清漆樹脂等酚醛清漆型酚樹脂；聚乙烯苯酚；三苯甲烷型酚樹脂等多官能型酚樹脂；萜烯改質酚樹脂、二環戊二烯改質酚樹脂等改質酚樹脂；具有伸苯基骨架和/或聯伸苯基骨架之苯酚芳烷基樹脂、具有伸苯基和/或聯伸苯基骨架之萘酚芳烷基樹脂等苯酚芳烷基型 酚樹脂；雙酚A、雙酚F(二羥基二苯甲烷)等雙酚化合物(具有雙酚F骨架之酚樹脂)；4,4’-聯苯酚等具有聯伸苯基骨架之化合物等。可以將該等單獨使用，亦可以組合2種以上來使用。 Specific examples of the phenolic resin-based hardener include novolak-type phenolic resins such as novolac resin, cresol novolak resin, bisphenol novolac resin, and phenol-biphenyl novolac resin; polyvinylphenol; Multifunctional phenol resins such as phenylmethane-type phenol resin; modified phenol resins such as terpene-modified phenol resin and dicyclopentadiene-modified phenol resin; phenol aromatics with phenyl skeleton and/or dicyclopentadiene skeleton Phenol aralkyl type such as alkyl resin, naphthol aralkyl resin with phenyl and/or diphenyl skeleton Phenol resin; bisphenol compounds such as bisphenol A and bisphenol F (dihydroxydiphenylmethane) (phenol resins with bisphenol F skeleton); compounds with diextended phenyl skeleton such as 4,4’-biphenol, etc. These may be used individually or in combination of 2 or more types.

其中，可以使用苯酚芳烷基樹脂，作為苯酚芳烷基樹脂，可以使用苯酚、對伸茬二甲醚縮聚物。 Among them, phenol aralkyl resin can be used, and as the phenol aralkyl resin, phenol or p-dimethyl ether condensation polymer can be used.

作為咪唑系硬化劑，具體而言，可舉出2-苯基-1H-咪唑-4,5-二甲醇、2-苯基-4-甲基-5-羥甲基咪唑、2-甲基咪唑、2-苯基咪唑、2,4-二胺-6-[2-甲基咪唑基-(1)]-乙基-對稱三

Figure 109108757-A0305-02-0019-4
、2-十一基咪唑、2-十七基咪唑、2,4-二胺-6-[2-甲基咪唑基-(1)]-乙基-對稱三
Figure 109108757-A0305-02-0019-5
異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物、2-甲基咪唑異三聚氰酸加成物、1,2,4-苯三甲酸1-氰基乙基-2-苯基咪唑鎓、1,2,4-苯三甲酸1-氰基乙基-2-十一基咪唑鎓等。可以將該等單獨使用，亦可以組合2種以上來使用。 Specific examples of the imidazole-based curing agent include 2-phenyl-1H-imidazole-4,5-dimethanol, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2-methyl Imidazole, 2-phenylimidazole, 2,4-diamine-6-[2-methylimidazolyl-(1)]-ethyl-symmetric tris
Figure 109108757-A0305-02-0019-4
, 2-Undecylimidazole, 2-Heptadecanylimidazole, 2,4-diamine-6-[2-methylimidazolyl-(1)]-ethyl-symmetric tris
Figure 109108757-A0305-02-0019-5
Isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 1,2,4-benzenetricarboxylic acid 1-cyano Ethyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium 1,2,4-benzenetricarboxylate, etc. These may be used individually or in combination of 2 or more types.

相對於導熱性組成物中的上述黏合劑樹脂100質量份，上述硬化劑的含量例如可以為5質量份~50質量份，亦可以為20質量份~40質量份。 The content of the hardener may be, for example, 5 to 50 parts by mass, or 20 to 40 parts by mass relative to 100 parts by mass of the binder resin in the thermally conductive composition.

又，相對於導熱性組成物中的環氧樹脂100質量份或環氧樹脂及環氧單體的總計100質量份，上述硬化劑的含量例如可以為1質量份~40質量份，亦可以為10質量份~35質量份。 Moreover, the content of the above-mentioned hardening agent may be, for example, 1 to 40 parts by mass relative to 100 parts by mass of the epoxy resin or 100 parts by mass of the total of the epoxy resin and the epoxy monomer in the thermally conductive composition. 10 parts by mass to 35 parts by mass.

(自由基聚合起始劑) (Radical polymerization initiator)

上述導熱性組成物可以含有自由基聚合起始劑。 The thermally conductive composition may contain a radical polymerization initiator.

作為上述自由基聚合起始劑，能夠使用偶氮化合物、過氧化物等。 As the radical polymerization initiator, azo compounds, peroxides, etc. can be used.

作為上述過氧化物，具體而言，可舉出雙(1-苯基-1-甲基乙基)過氧化物、1,1-雙(1,1-二甲基乙基過氧)環己烷、甲基乙基酮過氧化物、環己烷過氧化物、乙醯丙酮過氧化物、1,1-二(三級己基過氧)環己烷、1,1-二(三級丁基過氧)-2-甲基環己烷、1,1-二(三級丁基過氧)環己烷、2,2-二(三級丁基過 氧)丁烷、正丁基-4,4-二(三級丁基過氧)戊酸酯、2,2-二(4,4-二(三級丁基過氧)環己烷)丙烷、對甲烷氫過氧化物、二異丙基苯氫過氧化物、1,1,3,3-四甲基丁基氫過氧化物、異丙苯氫過氧化物、三級丁基氫過氧化物、二(2-三級丁基過氧異丙基)苯、二異丙苯基過氧化物、2,5-二甲基-2,5-二(三級丁基過氧)己烷、三級丁基異丙苯基過氧化物、二-三級丁基過氧化物、2,5-二甲基2,5-二(三級丁基過氧)己烷、二異丁基過氧化物、二(3,5,5-三甲基己醯基)過氧化物、二月桂基過氧化物、二(3-甲基苯甲醯基)過氧化物、苯甲醯基(3-甲基苯甲醯基)過氧化物、二苯甲醯基過氧化物、二(4-甲基苯甲醯基)過氧化物、二正丙基過氧二碳酸酯、二異丙基過氧二碳酸酯、二(2-乙基己基)過氧二碳酸酯、二-二級丁基過氧二碳酸酯、異丙苯基過氧新癸酸酯、1,1,3,3-四甲基丁基過氧新癸酸酯、三級己基新癸酸酯、三級丁基過氧新庚酸酯、三級己基過氧新戊酸酯、1,1,3,3-四甲基丁基過氧-2-乙基己酸酯、2,5-二甲基-2,5-二(2-二乙基己醯基過氧)己烷、三級丁基過氧-2-乙基己酸酯、三級己基過氧異丙基單碳酸酯、三級丁基過氧順丁烯二酸、三級丁基過氧3,5,5-三甲基己酸酯、三級丁基過氧異丙基單碳酸酯、三級丁基過氧-2-乙基己基單碳酸酯、三級己基過氧苯甲酸酯、2,5-二甲基-2,5-二(苯甲醯基過氧)己烷、三級丁基過氧丙酮酸酯、三級過氧-3-甲基苯甲酸酯、過氧苯甲酸三級丁酯、三級丁基過氧烯丙基單碳酸酯、3,3’，4,4’-四(三級丁基過氧羥基)二苯基酮等。可以將該等單獨使用，亦可以組合2種以上來使用。 Specific examples of the peroxide include bis(1-phenyl-1-methylethyl)peroxide and 1,1-bis(1,1-dimethylethylperoxy)cyclohexane. Hexane, methyl ethyl ketone peroxide, cyclohexane peroxide, acetylacetone peroxide, 1,1-di(tertiary hexylperoxy)cyclohexane, 1,1-di(tertiary hexylperoxy) Butylperoxy)-2-methylcyclohexane, 1,1-bis(tertiary butylperoxy)cyclohexane, 2,2-bis(tertiary butylperoxy)cyclohexane Oxy)butane, n-butyl-4,4-di(tertiary butylperoxy)valerate, 2,2-bis(4,4-di(tertiary butylperoxy)cyclohexane)propane , p-methane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tertiary butyl hydroperoxide Oxide, di(2-tertiary butylperoxyisopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(tertiary butylperoxy)hexane alkane, tertiary butylcumyl peroxide, di-tertiary butyl peroxide, 2,5-dimethyl 2,5-di(tertiary butylperoxy)hexane, diisobutyl methyl peroxide, di(3,5,5-trimethylhexyl) peroxide, dilauryl peroxide, bis(3-methylbenzoyl) peroxide, benzyl peroxide (3-methylbenzoyl) peroxide, dibenzoyl peroxide, di(4-methylbenzoyl) peroxide, di-n-propyl peroxydicarbonate, diiso Propyl peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, di-secondary butylperoxydicarbonate, cumyl peroxyneodecanoate, 1,1,3 ,3-Tetramethylbutylperoxyneodecanoate, tertiary hexylperoxyneodecanate, tertiary butylperoxyneoheptanoate, tertiary hexylperoxyneopentanoate, 1,1,3, 3-Tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-diethylhexylperoxy)hexane, tertiary butyl Peroxy-2-ethylhexanoate, tertiary hexylperoxyisopropylmonocarbonate, tertiary butylperoxymaleic acid, tertiary butylperoxy 3,5,5-trimethyl Caproate, tertiary butylperoxyisopropyl monocarbonate, tertiary butylperoxy-2-ethylhexylmonocarbonate, tertiary hexylperoxybenzoate, 2,5-dimethyl -2,5-Di(benzoylperoxy)hexane, tertiary butyl peroxypyruvate, tertiary peroxy-3-methylbenzoate, tertiary butyl peroxybenzoate, Tertiary butylperoxyallyl monocarbonate, 3,3',4,4'-tetrakis(tertiary butylperoxyhydroxy)diphenylketone, etc. These may be used individually or in combination of 2 or more types.

(硬化促進劑) (hardening accelerator)

上述導熱性組成物可以含有硬化促進劑。 The thermally conductive composition may contain a hardening accelerator.

上述硬化促進劑能夠促進黏合劑樹脂或單體與硬化劑的反應。 The above-mentioned hardening accelerator can promote the reaction between the binder resin or monomer and the hardener.

作為上述硬化促進劑，具體而言，可舉出：有機膦、四取代鏻化合物、磷酸酯甜菜鹼(phosphobetaine)化合物、膦化合物和醌化合物的加成物、鏻化合物和矽烷化合物的加成物等含有磷原子之化合物；二氰二胺、1,8-二吖雙 環[5.4.0]十一烯-7、苄基二甲胺等脒基、三級胺；上述脒基或上述三級胺的四級銨鹽等含有氮原子之化合物等。可以將該等單獨使用，亦可以組合2種以上來使用。 Specific examples of the hardening accelerator include organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds. and other compounds containing phosphorus atoms; dicyandiamide, 1,8-dioxadine bis Cycl[5.4.0]undecene-7, benzyldimethylamine and other amidine groups and tertiary amines; compounds containing nitrogen atoms such as the above-mentioned amidine groups or quaternary ammonium salts of the above-mentioned tertiary amines, etc. These may be used individually or in combination of 2 or more types.

(矽烷耦合劑) (silica coupling agent)

上述導熱性組成物可以含有矽烷耦合劑。 The thermally conductive composition may contain a silane coupling agent.

上述矽烷耦合劑能夠提高使用了導熱性組成物之密接層與基材或半導體元件的密接性。 The silane coupling agent can improve the adhesiveness between an adhesive layer using a thermally conductive composition and a base material or semiconductor element.

作為上述矽烷耦合劑，具體而言，能夠使用：乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷等乙烯基矽烷；2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷等環氧矽烷；對苯乙烯基三甲氧基矽烷等苯乙烯基矽烷；3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷等甲基丙烯醯基矽烷；甲基丙烯酸3-(三甲氧基矽基)丙酯、3-丙烯醯氧基丙基三甲氧基矽烷等丙烯酸矽烷；N-2-(胺基乙基)-3-胺丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺丙基三甲氧基矽烷、3-胺丙基三甲氧基矽烷、3-胺丙基三乙氧基矽烷、3-三乙氧基矽基-N-(1,3-二甲基-亞丁基)丙胺、N-苯基-γ-胺丙基三甲氧基矽烷等胺基矽烷；三聚異氰酸酯矽烷；烷基矽烷；3-脲基丙基三烷氧基矽烷等脲基矽烷；3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷等巰基矽烷；3-異氰酸酯丙基三乙氧基矽烷等異氰酸酯矽烷等。可以將該等單獨使用，亦可以組合2種以上來使用。 As the above-mentioned silane coupling agent, specifically, vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane can be used , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-epoxy Epoxysilanes such as propoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; styrylsilanes such as p-styryltrimethoxysilane; 3-methyl Acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldiethoxysilane Methacryloxysilane such as acryloyloxypropyltriethoxysilane; acrylic silanes such as 3-(trimethoxysilyl)propyl methacrylate and 3-acrylyloxypropyltrimethoxysilane ; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane Trimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilane-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-γ-amine Aminosilane such as propyltrimethoxysilane; isocyanatesilane; alkylsilane; ureidosilane such as 3-ureidopropyltrialkoxysilane; 3-mercaptopropylmethyldimethoxysilane, 3 -Mercaptosilanes such as mercaptopropyltrimethoxysilane; isocyanate silanes such as 3-isocyanatepropyltriethoxysilane, etc. These may be used individually or in combination of 2 or more types.

(塑化劑) (Plasticizer)

上述導熱性組成物可以含有塑化劑。藉由添加塑化劑，能夠實現低應力化。 The thermally conductive composition may contain a plasticizer. By adding a plasticizer, stress reduction can be achieved.

作為上述塑化劑，具體而言，能夠舉出聚矽氧油、聚矽氧橡膠等聚矽氧化合物；聚丁二烯順丁烯二酸酐加成物等聚丁二烯化合物；丙烯腈丁二烯共聚化合物等。可以將該等單獨使用，亦可以組合2種以上來使用。 Specific examples of the plasticizer include polysilicone compounds such as polysilicone oil and polysilicone rubber; polybutadiene compounds such as polybutadiene maleic anhydride adduct; and acrylonitrile butadiene. Diene copolymer compounds, etc. These may be used individually or in combination of 2 or more types.

(其他成分) (other ingredients)

除了上述之成分以外，依需要，上述導熱性組成物還可以含有其他成分。作為其他成分，例如，可舉出溶劑。 In addition to the above-mentioned components, the thermally conductive composition may also contain other components if necessary. Examples of other components include solvents.

作為上述溶劑，並無特別限定，但是例如可舉出乙醇、丙醇、丁醇、戊醇、己醇、庚醇、辛醇、壬醇、癸醇、乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單丙醚、丙二醇單丁醚、甲基甲氧基丁醇、α-萜品醇、β-萜品醇、己二醇、苄醇、2-苯乙醇、異棕櫚醇、異硬脂醇、月桂醇、乙二醇、丙二醇、丁基丙三醇或丙三醇等醇類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮、二丙酮醇(4-羥基-4-甲基-2-戊酮)、2-辛酮、異佛爾酮(3,5,5-三甲基-2-環己烯-1-酮)或二異丁基酮(2,6-二甲基-4-庚酮)等酮類；乙酸乙酯、乙酸丁酯、酞酸二乙酯、酞酸二丁酯、乙醯氧基乙烷、丁酸甲酯、己酸甲酯、辛酸甲酯、癸酸甲酯、乙酸甲賽璐蘇、乙二醇單丁醚乙酸酯、丙二醇單甲醚乙酸酯、1,2-二乙醯氧基乙烷、磷酸三丁酯、磷酸三甲苯酯或磷酸三戊酯等酯類；四氫呋喃、二丙醚、乙二醇二甲醚、乙二醇二乙醚、乙二醇二丁醚、丙二醇二甲醚、乙氧基乙醚、1,2-雙(2-二乙氧基)乙烷或1,2-雙(2-甲氧基乙氧基)乙烷等醚類；乙酸2-(2丁氧基乙氧基)乙烷等酯醚類；2-(2-甲氧基乙氧基)乙醇等醚醇類、甲苯、二甲苯、正烷烴、異烷烴、十二基苯、松節油、煤油或輕油等烴類；乙腈或丙腈等腈類；乙醯胺或N,N-二甲基甲醯胺等醯胺類；低分子量的揮發性矽油或揮發性有機改質矽油等矽油類。可以將該等單獨使用，亦可以組合2種以上來使用。 The solvent is not particularly limited, but examples thereof include ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, ethylene glycol monomethyl ether, and ethylene glycol. Monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, methyl methoxy butanol, α-terpineol, Acetone , methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), 2-octanone, isophorone (3,5 ,5-trimethyl-2-cyclohexen-1-one) or diisobutyl ketone (2,6-dimethyl-4-heptanone) and other ketones; ethyl acetate, butyl acetate, phthalate Diethyl acid, dibutyl phthalate, acetyloxyethane, methyl butyrate, methyl caproate, methyl octanoate, methyl decanoate, methylcellulosine acetate, ethylene glycol monobutyl ether Acid esters, propylene glycol monomethyl ether acetate, 1,2-diethyloxyethane, tributyl phosphate, tricresyl phosphate or tripentyl phosphate and other esters; tetrahydrofuran, dipropyl ether, ethylene glycol Dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, ethoxyethyl ether, 1,2-bis(2-diethoxy)ethane or 1,2-bis(2 Ethers such as -methoxyethoxy)ethane; ester ethers such as 2-(2butoxyethoxy)ethane acetate; ether alcohols such as 2-(2-methoxyethoxy)ethanol , toluene, xylene, n-alkanes, isoalkane, dodecylbenzene, turpentine, kerosene or light oil and other hydrocarbons; nitriles such as acetonitrile or propionitrile; acetamide or N,N-dimethylformamide, etc. Amides; silicone oils such as low molecular weight volatile silicone oil or volatile organic modified silicone oil. These may be used individually or in combination of 2 or more types.

藉由使用上述溶劑，能夠控制上述導熱性組成物的流動性，例如， 能夠提高糊狀的上述導熱性組成物的作業性。又，藉由加熱時的收縮能夠促進燒結。溶劑中，使用沸點相對高的溶劑、較佳為使用沸點高於硬化溫度的溶劑，藉此能夠抑制在對導熱性組成物進行熱處理而獲得之接著層中產生孔隙。該高沸點溶劑的沸點例如可以為180℃~450℃，亦可以為200℃~400℃。 By using the above solvent, the fluidity of the above thermally conductive composition can be controlled, for example, The workability of the thermally conductive composition in paste form can be improved. In addition, sintering can be accelerated by shrinkage during heating. Among the solvents, a solvent with a relatively high boiling point, preferably a solvent with a boiling point higher than the curing temperature, can be used to suppress the generation of pores in the adhesive layer obtained by heat-treating the thermally conductive composition. The boiling point of the high-boiling point solvent may be, for example, 180°C to 450°C, or 200°C to 400°C.

以下，對本實施形態的導熱性組成物之製造方法進行說明。 Hereinafter, a method for manufacturing the thermally conductive composition of this embodiment will be described.

作為上述導熱性組成物之製造方法，可使用混合上述之原料成分之方法。對於混合，能夠使用公知的方法，但是例如，能夠使用3根輥、混合器等。 As a method of producing the thermally conductive composition, a method of mixing the above raw material components can be used. For mixing, a known method can be used, but for example, three rollers, a mixer, etc. can be used.

另外，對於所獲得之混合物，可以進一步進行消泡。關於消泡，例如，可以在真空下靜置混合物。 In addition, the obtained mixture may be further defoamed. Regarding defoaming, for example, the mixture can be left to stand under vacuum.

(半導體裝置) (semiconductor device)

對本實施形態的半導體裝置進行說明。 The semiconductor device of this embodiment will be described.

上述半導體裝置具備：基材；及半導體元件，其經由對上述導熱性組成物進行熱處理而獲得之接著層裝載於基材上。藉由使用散熱性、密接性優異的接著層，能夠實現可靠性優異的半導體裝置。 The above-mentioned semiconductor device includes: a base material; and a semiconductor element in which an adhesive layer obtained by heat-treating the above-mentioned thermally conductive composition is mounted on the base material. By using an adhesive layer that is excellent in heat dissipation and adhesion, a semiconductor device with excellent reliability can be realized.

又，上述接著層能夠應用於各種被接著體。作為被接著體，具體而言，可舉出：IC、LSI等半導體元件；引線框、BGA基板、安裝基板、半導體晶片等基材；散熱器、散熱片等散熱構件等。 In addition, the above-described adhesive layer can be applied to various adherends. Specific examples of the adherend include: semiconductor elements such as ICs and LSIs; base materials such as lead frames, BGA substrates, mounting substrates, and semiconductor wafers; and heat dissipation members such as heat sinks and heat sinks.

以下，對使用了本實施形態的導熱性組成物之半導體裝置的一例進行說明。 Hereinafter, an example of a semiconductor device using the thermally conductive composition of this embodiment will be described.

圖1係表示本實施形態之半導體裝置的一例之剖面圖。 FIG. 1 is a cross-sectional view showing an example of the semiconductor device according to this embodiment.

本實施形態之半導體裝置100具備：基材30；及半導體元件20，其經由作為導熱性組成物的熱處理體之接著層10(晶片黏著材)裝載於基材30上。 The semiconductor device 100 of this embodiment includes a base material 30 and a semiconductor element 20 mounted on the base material 30 via an adhesive layer 10 (wafer adhesive material) which is a heat-treated body of a thermally conductive composition.

半導體元件20和基材30例如經由接合線(bonding wire)40等電連接。又，半導體元件20例如由密封樹脂50密封。 The semiconductor element 20 and the base material 30 are electrically connected via, for example, a bonding wire 40 or the like. Moreover, the semiconductor element 20 is sealed with the sealing resin 50, for example.

上述接著層10的厚度的下限例如係5μm以上為較佳，10μm以上為更佳，20μm以上為進一步較佳。藉此，能夠提高導熱性組成物的熱處理體的熱容量，並能夠提高散熱性。 The lower limit of the thickness of the adhesive layer 10 is, for example, preferably 5 μm or more, more preferably 10 μm or more, and still more preferably 20 μm or more. This can increase the heat capacity of the heat-treated body of the thermally conductive composition and improve the heat dissipation properties.

又，接著層10的厚度的上限例如可以設為100μm以下，亦可以設為50μm以下。 Furthermore, the upper limit of the thickness of the adhesive layer 10 may be, for example, 100 μm or less, or may be 50 μm or less.

圖1中，基材30例如為引線框。此時，半導體元件20經由接著層10裝載於晶片墊32或基材30上。又，半導體元件20例如經由接合線40與外引線34(基材30)電連接。 In FIG. 1 , the base material 30 is, for example, a lead frame. At this time, the semiconductor element 20 is mounted on the wafer pad 32 or the base material 30 via the adhesive layer 10 . Furthermore, the semiconductor element 20 is electrically connected to the outer lead 34 (base material 30 ) via, for example, the bonding wire 40 .

作為引線框之基材30例如由42合金、Cu框架構成。 The base material 30 as the lead frame is made of, for example, 42 alloy or Cu frame.

基材30可以為有機基板、陶瓷基板。作為有機基板，例如由環氧樹脂、氰酸酯樹脂、順丁烯二醯亞胺樹脂等構成者為較佳。 The substrate 30 may be an organic substrate or a ceramic substrate. The organic substrate is preferably made of, for example, epoxy resin, cyanate ester resin, maleimide resin, or the like.

另外，基材30的表面例如可以由銀、金等金屬被覆。藉此，能夠提高接著層10和基材30的接著性。 In addition, the surface of the base material 30 may be coated with a metal such as silver or gold. Thereby, the adhesiveness between the adhesive layer 10 and the base material 30 can be improved.

圖2係圖1的變形例，且係表示本實施形態之半導體裝置100的一例之剖面圖。 FIG. 2 is a modification of FIG. 1 and is a cross-sectional view showing an example of the semiconductor device 100 of this embodiment.

本變形例之半導體裝置100中，基材30例如為中介層(interposer)。在作為中介層之基材30中與裝載有半導體元件20之一面相反的一側的另一面例如形成複數個焊球52。此時，半導體裝置100經由焊球52與其他配線基板連接。 In the semiconductor device 100 of this modification, the base material 30 is, for example, an interposer. For example, a plurality of solder balls 52 are formed on the other surface of the base material 30 serving as the interposer, which is opposite to the surface on which the semiconductor element 20 is mounted. At this time, the semiconductor device 100 is connected to other wiring boards via the solder balls 52 .

(半導體裝置之製造方法) (Method for manufacturing semiconductor device)

對本實施形態之半導體裝置之製造方法的一例進行說明。 An example of the manufacturing method of the semiconductor device according to this embodiment will be described.

首先，將導熱性組成物塗佈於基材30上，接著，在其上配置半導體元件20。亦即，依次積層基材30、導熱性組成物、半導體元件20。作為塗佈導熱性組成物之方法，並無限定，但是具體而言，能夠使用滴塗法(dispensing)、印刷法、噴墨法等。 First, the thermally conductive composition is coated on the base material 30, and then the semiconductor element 20 is arranged thereon. That is, the base material 30, the thermal conductive composition, and the semiconductor element 20 are laminated in this order. The method of applying the thermally conductive composition is not limited, but specifically, dispensing, printing, inkjet, etc. can be used.

接著，藉由使導熱性組成物預硬化及後硬化，將導熱性組成物設為熱處理體(硬化物)。藉由預硬化及後硬化等熱處理而導熱性組成物中的銀粒子凝聚，在接著層10中形成複數個銀粒子彼此的界面消失而成之導熱層。藉此，經由接著層10，接著基材30和半導體元件20。接著，使用接合線40，將半導體元件20和基材30電連接。接著，用密封樹脂50密封半導體元件20。藉此，能夠製造半導體裝置。 Next, the thermally conductive composition is pre-hardened and post-hardened to prepare the thermally conductive composition into a heat-treated body (hardened product). The silver particles in the thermally conductive composition are aggregated by heat treatment such as pre-hardening and post-hardening, and a thermally conductive layer is formed in the adhesive layer 10 in which the interfaces between the plurality of silver particles disappear. Thereby, the base material 30 and the semiconductor element 20 are bonded via the adhesive layer 10 . Next, the semiconductor element 20 and the base material 30 are electrically connected using the bonding wire 40 . Next, the semiconductor element 20 is sealed with the sealing resin 50 . Thereby, a semiconductor device can be manufactured.

以上，對本發明的實施形態進行了敘述，但是該等為本發明的示例，能夠使用除了上述以外的各種構成。又，本發明並不限定於上述實施形態，能夠實現本發明的目的之範圍內的變形、改良等包含在本發明中。 The embodiments of the present invention have been described above. However, these are examples of the present invention, and various configurations other than the above can be used. In addition, the present invention is not limited to the above-described embodiment, and modifications, improvements, etc. within the scope that can achieve the object of the present invention are included in the present invention.

〔實施例〕 [Example]

以下，參照實施例對本發明進行詳細說明，但是本發明不受該等實施例的記載之任何限定。 Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited in any way by the description of these Examples.

<導熱性組成物> <Thermal conductive composition>

依據下述表1中所示之摻合量，混合各原料成分，獲得了清漆。 Each raw material component was mixed according to the blending amount shown in Table 1 below, and a varnish was obtained.

依據下述表1中所示之摻合量，摻合所獲得之清漆、溶劑、金屬粒子，在常溫，使用三輥研磨機進行混煉，製作了糊狀的導熱性組成物。 The obtained varnish, solvent, and metal particles were blended according to the blending amounts shown in Table 1 below, and kneaded using a three-roller mill at normal temperature to prepare a paste-like thermal conductive composition.

以下，示出表1的原料成分的資訊。 The information on the raw material components in Table 1 is shown below.

(黏合劑樹脂) (Binder resin)

˙環氧樹脂1：雙酚F型液態環氧樹脂(Nippon Kayaku Co.,Ltd.製造，RE-303S) ˙Epoxy resin 1: Bisphenol F type liquid epoxy resin (manufactured by Nippon Kayaku Co., Ltd., RE-303S)

(硬化劑) (hardener)

˙硬化劑1：具有雙酚F骨架之酚樹脂(在室溫25℃時為固態，DIC Corporation製造，DIC-BPF) ˙Hardening agent 1: Phenol resin with bisphenol F skeleton (solid at room temperature 25°C, manufactured by DIC Corporation, DIC-BPF)

(丙烯酸粒子) (Acrylic particles)

˙丙烯酸粒子1：甲基丙烯酸系樹脂粒子(SEKISUI PLASTICS CO.,LTD.製造，IBM-2) ˙Acrylic particles 1: Methacrylic resin particles (manufactured by SEKISUI PLASTICS CO., LTD., IBM-2)

(單體) (single)

˙丙烯酸單體1：甲基丙烯酸2-苯氧乙酯(KYOEISHA CHEMICAL Co.,LTD.製造，Light Ester PO) ˙Acrylic monomer 1: 2-phenoxyethyl methacrylate (manufactured by KYOEISHA CHEMICAL Co., LTD., Light Ester PO)

˙丙烯酸單體2：1,4-環己烷二甲醇單丙烯酸酯(Mitsubishi Chemical Corporation.製造，CHDMMA) ˙Acrylic monomer 2: 1,4-cyclohexanedimethanol monoacrylate (manufactured by Mitsubishi Chemical Corporation, CHDMMA)

˙丙烯酸單體3：乙二醇二甲基丙烯酸酯(KYOEISHA CHEMICAL Co.,LTD.製造，Light Ester EG) ˙Acrylic monomer 3: Ethylene glycol dimethacrylate (manufactured by KYOEISHA CHEMICAL Co., LTD., Light Ester EG)

(塑化劑) (Plasticizer)

˙塑化劑1：烯丙基樹脂(KANTO CHEMICAL CO.,INC.製造，1,2-環己烷二羧酸雙(2-丙烯基)和丙烷-1,2-二醇的聚合物) ˙Plasticizer 1: Allyl resin (manufactured by KANTO CHEMICAL CO., INC., polymer of 1,2-cyclohexanedicarboxylic acid bis(2-propenyl) and propane-1,2-diol)

(矽烷耦合劑) (silica coupling agent)

˙矽烷耦合劑1：甲基丙烯酸3-(三甲氧基矽基)丙酯(Shin-Etsu Chemica.Co.,Ltd.製造，KBM-503P) ˙Silane coupling agent 1: 3-(trimethoxysilyl)propyl methacrylate (manufactured by Shin-Etsu Chemica.Co., Ltd., KBM-503P)

˙矽烷耦合劑2：3-環氧丙氧基丙基三甲氧基矽烷(Shin-Etsu Chemica.Co.,Ltd.製造，KBM-403E) ˙Silane coupling agent 2: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemica.Co., Ltd., KBM-403E)

(硬化促進劑) (hardening accelerator)

˙咪唑硬化劑1：2-苯基-1H-咪唑-4,5-二甲醇(SHIKOKU CHEMICALS CORPORATION.製造，2PHZ-PW) ˙Imidazole hardener 1: 2-phenyl-1H-imidazole-4,5-dimethanol (manufactured by SHIKOKU CHEMICALS CORPORATION., 2PHZ-PW)

(聚合起始劑) (polymerization initiator)

˙自由基聚合起始劑1：二異丙苯基過氧化物(Kayaku Akzo Corporation製造，Perkadox BC) ˙Radical polymerization initiator 1: dicumyl peroxide (manufactured by Kayaku Akzo Corporation, Perkadox BC)

(溶劑) (solvent)

˙溶劑1：丁基丙三醇(BFTG) ˙Solvent 1: Butylglycerol (BFTG)

(金屬粒子) (metal particles)

˙銀粒子1：銀粉(DOWA HIGHTECH CO.,LTD.製造，AG-DSB-114，球形，D50：1μm) ˙Silver particles 1: Silver powder (manufactured by DOWA HIGHTECH CO., LTD., AG-DSB-114, spherical, D 50 : 1 μm)

˙銀粒子2：銀粉(Fukuda Metal Foil & Powder Co.,Ltd.製造，HKD-16，片狀，D50：2μm) ˙Silver particles 2: Silver powder (manufactured by Fukuda Metal Foil & Powder Co., Ltd., HKD-16, flake, D 50 : 2 μm)

˙銀塗層樹脂粒子1：鍍銀聚矽氧樹脂粒子(Mitsubishi Materials Corporation製造，耐熱2μm產品，球形，D50：2μm，比重：4.3，銀的重量比率為80wt%，樹脂的重量比率為20wt%) ˙Silver-coated resin particles 1: Silver-coated polysiloxane resin particles (manufactured by Mitsubishi Materials Corporation, heat-resistant 2 μm product, spherical shape, D 50 : 2 μm, specific gravity: 4.3, silver weight ratio is 80wt%, resin weight ratio is 20wt %)

˙銀塗層樹脂粒子2：鍍銀聚矽氧樹脂粒子(Mitsubishi Materials Corporation製造，耐熱/表面處理2μm產品，球形，D50：2μm，比重：4.3，銀的重量比率為80wt%，樹脂的重量比率為20wt%) ˙Silver-coated resin particles 2: Silver-coated polysiloxane resin particles (manufactured by Mitsubishi Materials Corporation, heat-resistant/surface-treated 2 μm product, spherical shape, D 50 : 2 μm, specific gravity: 4.3, silver weight ratio: 80wt%, resin weight Ratio is 20wt%)

˙銀塗層樹脂粒子3：鍍銀聚矽氧樹脂粒子(Mitsubishi Materials Corporation製造，耐熱/表面處理4μm產品，球形，D50：4μm，比重：3.8，銀的重量比率為75wt%，樹脂的重量比率為25wt%) ˙Silver-coated resin particles 3: Silver-coated polysiloxane resin particles (manufactured by Mitsubishi Materials Corporation, heat-resistant/surface-treated 4μm product, spherical shape, D50 : 4μm, specific gravity: 3.8, silver weight ratio is 75wt%, resin weight Ratio is 25wt%)

˙銀塗層樹脂粒子4：鍍銀聚矽氧樹脂粒子(Mitsubishi Materials Corporation製造，耐熱/表面處理10μm產品，球形，D50：10μm，比重：2.3，銀的重量比率為50wt%，樹脂的重量比率為50wt%) ˙Silver-coated resin particles 4: Silver-coated polysilicone resin particles (manufactured by Mitsubishi Materials Corporation, heat-resistant/surface-treated 10 μm product, spherical shape, D 50 : 10 μm, specific gravity: 2.3, silver weight ratio is 50wt%, resin weight Ratio is 50wt%)

˙銀塗層樹脂粒子5：鍍銀丙烯酸樹脂粒子(SANNO Co.,Ltd.製造，SANSILVER-8D，球形，D50：8μm，單分散粒子，比重：2.4，銀的重量比率為50wt%，樹脂的重量比率為50wt%) ˙Silver-coated resin particles 5: Silver-coated acrylic resin particles (manufactured by SANNO Co., Ltd., SANSILVER-8D, spherical, D 50 : 8 μm, monodisperse particles, specific gravity: 2.4, silver weight ratio is 50wt%, resin The weight ratio is 50wt%)

Figure 109108757-A0305-02-0028-2
Figure 109108757-A0305-02-0028-2

使用所獲得之導熱性組成物，測量下述物性，並評價了評價項目。 Using the obtained thermally conductive composition, the following physical properties were measured, and the evaluation items were evaluated.

(導熱率) (thermal conductivity)

花費60分鐘將所獲得之導熱性組成物從30℃升溫至200℃，接著以200℃熱處理120分鐘，獲得了厚度為1mm的熱處理體。 The obtained thermally conductive composition was heated from 30°C to 200°C for 60 minutes, and then heat-treated at 200°C for 120 minutes to obtain a heat-treated body with a thickness of 1 mm.

接著，使用雷射閃光法，測量了熱處理體的厚度方向的熱擴散係數α。另外，測量溫度設為25℃。 Next, the thermal diffusion coefficient α in the thickness direction of the heat-treated body was measured using the laser flash method. In addition, the measurement temperature is set to 25°C.

進而，藉由示差掃描熱量(Differential scanning calorimetry：DSC)測量來測量比熱Cp，並依照JIS-K-6911測量了密度ρ。使用該等值，基於以下式，計算了導熱率λ。 Furthermore, the specific heat Cp was measured by differential scanning calorimetry (DSC) measurement, and the density ρ was measured in accordance with JIS-K-6911. Using this equivalent value, the thermal conductivity λ was calculated based on the following equation.

將評價結果示於下述表2中。另外，單位為W/(m˙K)。 The evaluation results are shown in Table 2 below. In addition, the unit is W/(m˙K).

導熱率λ[W/(m˙K)]=α[m2/sec]×Cp[J/kg˙K]×ρ[g/cm3] Thermal conductivity λ[W/(m˙K)]=α[m 2 /sec]×Cp[J/kg˙K]×ρ[g/cm 3 ]

(儲存彈性模數) (Storage elastic modulus)

花費60分鐘將所獲得之導熱性組成物從30℃升溫至200℃，接著以200℃熱處理120分鐘而獲得了熱處理體。對於所獲得之熱處理體，使用測量裝置(Hitachi High-Tech Science Corporation.製造，DMS6100)，藉由頻率1Hz時的動態黏彈性測量(DMA)，測量了25℃時的儲存彈性模數E(MPa)。 The temperature of the obtained thermally conductive composition was raised from 30°C to 200°C over 60 minutes, and then heat-treated at 200°C for 120 minutes to obtain a heat-treated body. For the obtained heat-treated body, the storage elastic modulus E (MPa) at 25°C was measured by dynamic viscoelasticity measurement (DMA) at a frequency of 1 Hz using a measuring device (DMS6100 manufactured by Hitachi High-Tech Science Corporation). ).

(粒子連結結構的觀察) (Observation of particle connection structure)

準備了銅引線框和矽晶片(長度2mm×寬度2mm，厚度為0.35mm)。接著，將所獲得之導熱性組成物塗佈於矽晶片上，以使塗佈厚度成為25±10μm，並在其上配置了銅引線框。製作了依次積層矽晶片、導熱性組成物、銅引線框而成之積層體。 A copper lead frame and a silicon wafer (length 2 mm × width 2 mm, thickness 0.35 mm) were prepared. Next, the obtained thermally conductive composition was coated on the silicon wafer so that the coating thickness became 25±10 μm, and a copper lead frame was placed on the silicon wafer. A laminated body in which a silicon wafer, a thermally conductive composition, and a copper lead frame were laminated in this order was produced.

接著，花費60分鐘將所獲得之積層體在大氣下從30℃升溫至200℃，接著在200℃條件下進行120分鐘的熱處理，並使積層體中的導熱性組成物進行了硬化。 Next, the obtained laminated body was heated from 30°C to 200°C in the air for 60 minutes, and then heat-treated at 200°C for 120 minutes to harden the thermally conductive composition in the laminated body.

接著，使用掃描型電子顯微鏡(SEM)，觀察積層體中的導熱性組成物的熱 處理體的剖面，並評價了其狀態。 Next, a scanning electron microscope (SEM) was used to observe the thermal conductivity of the thermally conductive composition in the laminate. Sections of the body were processed and their condition evaluated.

實施例1~實施例7中，均確認到形成有銀粒子連結結構。又，在剖面圖像中，還確認到：在銀粒子連結結構中包含複數個大致圓形的樹脂粒子，該樹脂粒子的表面中的金屬層(銀層)與銀粒子連結結構連結。進而，確認到：黏合劑樹脂的硬化物在銀粒子連結結構內部中存在於除了銀以外的部分，以覆蓋銀。 In all of Examples 1 to 7, it was confirmed that the silver particle connection structure was formed. Furthermore, in the cross-sectional image, it was also confirmed that the silver particle connection structure includes a plurality of substantially circular resin particles, and the metal layer (silver layer) on the surface of the resin particles is connected to the silver particle connection structure. Furthermore, it was confirmed that the cured material of the binder resin was present in the portions other than the silver inside the silver particle connection structure to cover the silver.

(樹脂含量) (resin content)

花費60分鐘將所獲得之導熱性組成物從30℃升溫至200℃，接著以200℃熱處理120分鐘而獲得了熱處理體。在所獲得之熱處理體中，以下述方式測量了黏合劑樹脂及源自銀塗層樹脂粒子之樹脂成分。將熱處理體中之樹脂成分的含量設為樹脂含量(質量%) The temperature of the obtained thermally conductive composition was raised from 30°C to 200°C over 60 minutes, and then heat-treated at 200°C for 120 minutes to obtain a heat-treated body. In the obtained heat-treated body, the binder resin and the resin components derived from the silver coating resin particles were measured in the following manner. Let the content of the resin component in the heat-treated body be the resin content (mass %)

樹脂含量藉由測量所獲得之熱處理體的重量並從該重量中減去所含有之銀的重量來計算。 The resin content was calculated by measuring the weight of the obtained heat-treated body and subtracting the weight of the contained silver from the weight.

(溫度循環試驗) (Temperature cycle test)

將所獲得之導熱性組成物塗佈於表面鍍銀的基板上，從上裝載3.5×3.5mm的矽晶片(僅在比較例1中表面鍍銀，除此以外未鍍覆)，並花費60分鐘從30℃升溫至200℃，接著在200℃條件下進行120分鐘的熱處理而使其硬化/接合。 The obtained thermally conductive composition was coated on a silver-plated substrate, and a 3.5×3.5 mm silicon wafer was loaded from the top (only in Comparative Example 1, the surface was silver-plated, and otherwise unplated), and spent 60 The temperature was raised from 30°C to 200°C in 1 minute, and then heat treated at 200°C for 120 minutes to harden/join.

用密封材料EME-G700ML-C(Sumitomo Bakelite Co.,Ltd.製造)密封接合之後的矽晶片/基板，而獲得了樣品。 The bonded silicon wafer/substrate was sealed with a sealing material EME-G700ML-C (manufactured by Sumitomo Bakelite Co., Ltd.) to obtain a sample.

將所獲得之樣品放入85℃/60%RH的高溫高濕槽中，處理168小時，然後進行了260℃的回焊處理。 The obtained sample was placed in a high-temperature and high-humidity tank at 85°C/60%RH, treated for 168 hours, and then reflowed at 260°C.

將回焊處理之後的樣品投入到溫度循環試驗機TSA-72ES(ESPEC CORP.製造)中，將在150℃條件下10分鐘→在25℃條件下10分鐘→在-65℃條件下10分鐘→在25℃條件下10分鐘設為1個循環，進行了2000個循環處理。 Put the sample after the reflow process into the temperature cycle testing machine TSA-72ES (manufactured by ESPEC CORP.), and test it at 150°C for 10 minutes → 25°C for 10 minutes → -65°C for 10 minutes → One cycle was set to 10 minutes at 25°C, and 2,000 cycles were performed.

然後，藉由SAT(超音波探傷)確認了有無剝離。 Then, the presence or absence of peeling was confirmed by SAT (ultrasonic flaw detection).

表1中，將沒有剝離者標記為○，將具有剝離者標記為×。 In Table 1, those without peeling are marked as ○, and those with peeling are marked as ×.

(比較例2) (Comparative example 2)

混合塑化劑(聚丁二烯順丁烯二酸酐加成物，Cray Valley公司製造，RICOBOND1731)2.43質量份、丙烯酸樹脂(丙烯酸系聚合物，TOAGOSEI CO.,LTD.製造，UG4035)4.38質量份、烯丙基樹脂(1,2-環己烷二羧酸雙(2-丙烯基)和丙烷-1,2-二醇的聚合物，KANTO CHEMICAL CO.,INC.製造)6.57質量份、硬化促進劑(二氰二胺衍生物，ADEKA CORPORATION製造，EH-3636AS)0.05質量份、丙烯酸單體(1.6己二醇二甲基丙烯酸酯，KYOEISHA CHEMICAL Co.,LTD.製造，Light Ester 1.6HX)2.92質量份、丙烯酸單體(甲基丙烯酸2-苯氧乙酯，KYOEISHA CHEMICAL Co.,LTD.製造，Light Ester PO)8.03質量份、耦合劑(甲基丙烯酸3-(三甲氧基矽基)丙酯，Shin-Etsu Chemica.Co.,Ltd.製造，KBM-503P)0.12質量份、耦合劑(3-環氧丙氧基丙基三甲氧基矽烷，Shin-Etsu Chemica.Co.,Ltd.製造，KBM-403E)0.24質量份、聚合起始劑(1,1-雙(1,1-二甲基乙基過氧)環己烷、NOF CORPORATION.製造，PERHEXA C(S))0.24質量份，獲得了清漆。 Mixed plasticizer (polybutadiene maleic anhydride adduct, manufactured by Cray Valley Co., Ltd., RICOBOND1731) 2.43 parts by mass, acrylic resin (acrylic polymer, manufactured by TOAGOSEI CO., LTD., UG4035) 4.38 parts by mass , allyl resin (polymer of 1,2-cyclohexanedicarboxylic acid bis(2-propenyl) and propane-1,2-diol, manufactured by KANTO CHEMICAL CO., INC.) 6.57 parts by mass, hardened Accelerator (dicyandiamine derivative, manufactured by ADEKA CORPORATION, EH-3636AS) 0.05 parts by mass, acrylic monomer (1.6 hexanediol dimethacrylate, manufactured by KYOEISHA CHEMICAL Co., LTD., Light Ester 1.6HX) 2.92 parts by mass, acrylic monomer (2-phenoxyethyl methacrylate, manufactured by KYOEISHA CHEMICAL Co., LTD., Light Ester PO) 8.03 parts by mass, coupling agent (3-(trimethoxysilyl methacrylate)) Propyl ester, manufactured by Shin-Etsu Chemica.Co., Ltd., KBM-503P) 0.12 parts by mass, coupling agent (3-glycidoxypropyltrimethoxysilane, Shin-Etsu Chemica.Co., Ltd. Manufactured by KBM-403E) 0.24 parts by mass, polymerization initiator (1,1-bis(1,1-dimethylethylperoxy)cyclohexane, manufactured by NOF CORPORATION., PERHEXA C(S)) 0.24 parts by mass parts, the varnish was obtained.

向所獲得之清漆中摻合銀粉(DOWA HIGHTECH CO.,LTD.製造，AG-DSB-114，球形，D50：1μm)75.00質量份，並在常溫使用三輥研磨機進行混煉，製作了糊狀的導熱性組成物。 75.00 parts by mass of silver powder (manufactured by DOWA HIGHTECH CO., LTD., AG-DSB-114, spherical, D 50 : 1 μm) was mixed with the obtained varnish, and kneaded using a three-roller mill at normal temperature to produce Pasty thermally conductive composition.

藉由上述測量方法獲得之導熱率(λ)為1W/m˙K，且25℃條件下的儲存彈性模數(E)為3GPa。所計算出之λ/(E2)為0.11。 The thermal conductivity (λ) obtained by the above measurement method is 1W/m˙K, and the storage elastic modulus (E) at 25°C is 3GPa. The calculated λ/(E 2 ) is 0.11.

發現：與比較例2相比，藉由使用實施例1~實施例7的導熱性組成物，能夠降低半導體封裝的不良產生率。 It was found that compared with Comparative Example 2, by using the thermal conductive compositions of Examples 1 to 7, the defective rate of semiconductor packages can be reduced.

實施例1~實施例7的導熱性組成物中示出溫度循環性較比較例1 優異，且散熱性較比較例2優異。藉由使用該種實施例的導熱性組成物，能夠實現穩定地發揮高散熱性且使用時耐久性優異的半導體裝置。 The thermally conductive compositions of Examples 1 to 7 showed better temperature cyclic properties than those of Comparative Example 1 Excellent, and the heat dissipation performance is better than that of Comparative Example 2. By using the thermally conductive composition of this embodiment, a semiconductor device that stably exhibits high heat dissipation and has excellent durability during use can be realized.

本申請主張基於2019年3月20日申請之日本專利申請2019-052707號之優先權，並將其揭示的全部內容援用於此。 This application claims priority based on Japanese Patent Application No. 2019-052707 filed on March 20, 2019, and the entire disclosure of this application is incorporated by reference.

100:半導體裝置 100:Semiconductor device

10:接著層 10: Next layer

20:半導體元件 20:Semiconductor components

30:基材 30:Substrate

32:晶片墊 32:wafer pad

34:外引線 34:Outer lead

40:接合線(bonding wire) 40:bonding wire

50:密封樹脂 50:Sealing resin

Claims (16)

一種導熱性組成物，其含有：金屬粒子；黏合劑樹脂；及單體，藉由熱處理使前述金屬粒子發生燒結而形成粒子連結結構，相對於該導熱性組成物100質量份，前述黏合劑樹脂的含量為1質量份以上且15質量份以下，相對於該導熱性組成物100質量份，前述單體的含量為0.5質量份以上且10質量份以下，前述金屬粒子包含金屬塗層樹脂粒子及由金屬構成之粒子，使用該導熱性組成物，依據下述步驟A測量之導熱率λ(W/mK)和依據下述步驟B測量之25℃的儲存彈性模數E(GPa)滿足下述式(I)，
Figure 109108757-A0305-02-0033-8
 (步驟A)花費60分鐘將該導熱性組成物從30℃升溫至200℃，接著以200℃熱處理120分鐘，獲得厚度為1mm的熱處理體，對於所獲得之熱處理體，使用雷射閃光法，測量25℃時的導熱率λ(W/mK)，(步驟B)花費60分鐘將該導熱性組成物從30℃升溫至200℃，接著以200℃熱處理120分鐘而獲得熱處理體，對於所獲得之熱處理體，使用頻率1Hz時的動態黏彈性測量(DMA)，測量25℃時的儲存彈性模數E(MPa)。 A thermally conductive composition, which contains: metal particles; a binder resin; and a monomer. The aforementioned metal particles are sintered by heat treatment to form a particle connected structure. The aforementioned binder resin is 100 parts by mass of the thermally conductive composition. The content of the aforementioned monomer is 1 mass part or more and 15 mass parts or less, relative to 100 mass parts of the thermal conductive composition, the content of the aforementioned monomer is 0.5 mass part or more and 10 mass parts or less, and the aforementioned metal particles include metal coating resin particles and Particles made of metal, using this thermally conductive composition, the thermal conductivity λ (W/mK) measured according to the following step A and the storage elastic modulus E (GPa) at 25°C measured according to the following step B satisfy the following: Formula (I),
Figure 109108757-A0305-02-0033-8
 (Step A) The thermally conductive composition is heated from 30°C to 200°C for 60 minutes, and then heat-treated at 200°C for 120 minutes to obtain a heat-treated body with a thickness of 1 mm. The laser flash method is used for the heat-treated body obtained. The thermal conductivity λ (W/mK) at 25°C is measured. (Step B) The thermal conductivity composition is heated from 30°C to 200°C for 60 minutes, and then heat-treated at 200°C for 120 minutes to obtain a heat-treated body. For the obtained For the heat-treated body, use dynamic viscoelasticity measurement (DMA) at a frequency of 1Hz to measure the storage elastic modulus E (MPa) at 25°C. 如請求項1之導熱性組成物，其中，相對於藉由下述步驟獲得之熱處理體100質量%，該藉由下述步驟獲得之熱處理體中的樹脂含量為10質量%以上且30質量%以下，(步驟)花費60分鐘將該導熱性組成物從30℃升溫至200℃，接著以200℃熱處理120分鐘而獲得熱處理體。 The thermally conductive composition of Claim 1, wherein the resin content in the heat-treated body obtained by the following steps is 10 mass% or more and 30 mass% with respect to 100 mass% of the heat-treated body obtained by the following steps. Next, (step) the thermally conductive composition was heated from 30°C to 200°C for 60 minutes, and then heat-treated at 200°C for 120 minutes to obtain a heat-treated body. 如請求項1之導熱性組成物，其中，前述金屬粒子包含由選自由銀、金及銅組成的群中之一種以上的金屬材料構成之粒子。 The thermally conductive composition of claim 1, wherein the metal particles include particles composed of one or more metal materials selected from the group consisting of silver, gold, and copper. 如請求項1之導熱性組成物，其中，前述黏合劑樹脂包含選自由環氧樹脂、丙烯酸樹脂及烯丙基樹脂組成的群中之1種以上。 The thermally conductive composition according to claim 1, wherein the binder resin includes at least one selected from the group consisting of epoxy resin, acrylic resin and allyl resin. 如請求項1之導熱性組成物，其含有硬化劑。 The thermally conductive composition of claim 1, which contains a hardener. 如請求項5之導熱性組成物，其中，前述硬化劑包含酚樹脂系硬化劑或咪唑系硬化劑。 The thermally conductive composition according to claim 5, wherein the hardener includes a phenolic resin hardener or an imidazole hardener. 如請求項1之導熱性組成物，其中，前述單體包含選自由二醇單體、丙烯酸單體、環氧單體及順丁烯二醯亞胺單體組成的群中之一種以上。 The thermally conductive composition of claim 1, wherein the aforementioned monomers include at least one selected from the group consisting of glycol monomers, acrylic acid monomers, epoxy monomers and maleimide monomers. 如請求項1之導熱性組成物，其含有自由基聚合起始劑。 The thermally conductive composition of claim 1, which contains a radical polymerization initiator. 如請求項1之導熱性組成物，其含有矽烷耦合劑。 The thermally conductive composition of claim 1, which contains a silane coupling agent. 如請求項1之導熱性組成物，其含有塑化劑。 Such as the thermal conductive composition of claim 1, which contains a plasticizer. 如請求項1至10中任一項之導熱性組成物，其中，前述金屬塗層樹脂粒子的比重為2以上且10以下。 The thermally conductive composition according to any one of claims 1 to 10, wherein the specific gravity of the metal coating resin particles is 2 or more and 10 or less. 如請求項1至10中任一項之導熱性組成物，其中，前述金屬塗層樹脂粒子的平均粒徑D50為0.5μm以上且20μm以下。 The thermally conductive composition according to any one of claims 1 to 10, wherein the average particle diameter D 50 of the metal coating resin particles is 0.5 μm or more and 20 μm or less. 如請求項1至10中任一項之導熱性組成物，其中，在金屬粒子100質量%中，前述金屬塗層樹脂粒子的含量為1質量%以上且50質量%以下。 The thermally conductive composition according to any one of claims 1 to 10, wherein the content of the metal coating resin particles in 100 mass% of the metal particles is 1 mass% or more and 50 mass% or less. 如請求項1至10中任一項之導熱性組成物，其中，構成前述金屬塗層樹脂粒子中的樹脂粒子之樹脂材料包含選自由聚矽氧、丙烯酸、苯酚、聚苯乙烯、三聚氰胺、聚醯胺及聚四氟乙烯組成的群中之一種或兩種以上。 The thermally conductive composition according to any one of claims 1 to 10, wherein the resin material constituting the resin particles in the metal coating resin particles includes a resin material selected from the group consisting of polysiloxane, acrylic acid, phenol, polystyrene, melamine, and polyethylene. One or more of the group consisting of amide and polytetrafluoroethylene. 如請求項1之導熱性組成物，其含有溶劑。 The thermally conductive composition of claim 1, which contains a solvent. 一種半導體裝置，其具備： 基材；及半導體元件，其經由對請求項1至15中任一項之導熱性組成物進行熱處理而獲得之接著層裝載於前述基材上。 A semiconductor device having: A base material; and a semiconductor element in which an adhesive layer obtained by heat-treating the thermally conductive composition according to any one of claims 1 to 15 is loaded on the aforementioned base material.
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