TW202313804A - Resin sheet - Google Patents

Resin sheet Download PDF

Info

Publication number
TW202313804A
TW202313804A TW111126805A TW111126805A TW202313804A TW 202313804 A TW202313804 A TW 202313804A TW 111126805 A TW111126805 A TW 111126805A TW 111126805 A TW111126805 A TW 111126805A TW 202313804 A TW202313804 A TW 202313804A
Authority
TW
Taiwan
Prior art keywords
resin
resin sheet
maleimide
aforementioned
thermally conductive
Prior art date
Application number
TW111126805A
Other languages
Chinese (zh)
Inventor
渡邉康貴
上村和恵
Original Assignee
日商琳得科股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商琳得科股份有限公司 filed Critical 日商琳得科股份有限公司
Publication of TW202313804A publication Critical patent/TW202313804A/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

This resin sheet is formed from a resin composition containing a resin component (A) and a thermally conductive filler (C). The resin component (A) contains: a maleimide resin; and one or more types of the thermally conductive filler (C). If n denotes the number of types of the thermally conductive filler (C), the relative critical fill ratio of the thermally conductive filler(s) (C), which is represented by numerical formula (F1), is 0.95-1.26. (Relative critical fill ratio)= numerical formula (F1): (V1/CV1)+(V2/CV2)+...+(Vn/CVn). Vn is the volume fill ratio of the nth thermally conductive filler among the thermally conductive fillers (C); and CVn is the critical volume fill ratio of the nth thermally conductive filler among the thermally conductive fillers (C).

Description

樹脂薄片Resin flakes

本發明係關於樹脂薄片。This invention relates to resin sheets.

於使用在功率半導體之樹脂薄片，正研究摻合氧化鋁等之高熱傳導性的材料。文獻1(日本特開2017-160440號公報)中提案有將含有氧化鋁填料之環氧樹脂組成物的薄片狀成形體之樹脂薄片適用在功率半導體裝置。 然而，當適用在假定200℃以上之高溫動作的功率半導體元件，文獻1所記載之樹脂組成物耐熱性無法說是充分。又，亦有熱傳導性之進一步提昇、與將樹脂薄片強固地接著在被著體的課題。 For resin sheets used in power semiconductors, materials with high thermal conductivity such as alumina are being blended. Document 1 (Japanese Unexamined Patent Application Publication No. 2017-160440) proposes to apply a resin sheet of a sheet-shaped molding of an epoxy resin composition containing an alumina filler to a power semiconductor device. However, the heat resistance of the resin composition described in Document 1 cannot be said to be sufficient when applied to a power semiconductor element assumed to operate at a high temperature of 200°C or higher. In addition, there are also problems of further improving thermal conductivity and firmly adhering the resin sheet to the substrate.

本發明以提供一種可提昇熱傳導性及接著性之樹脂薄片作為目的。 根據本發明之一態樣，提供以下所示之樹脂薄片。 [1] 一種樹脂薄片，其係由含有(A)樹脂成分及(C)熱傳導性填料的樹脂組成物所形成之樹脂薄片，其特徵為前述(A)樹脂成分含有馬來醯亞胺樹脂，且含有1種類或2種類以上前述(C)熱傳導性填料， 將前述(C)熱傳導性填料的種類之數定為n時，下述數式(F1)表示之前述(C)熱傳導性填料的對臨界填充量比為0.95以上1.26以下。

Figure 02_image001
V n：前述(C)熱傳導性填料當中之第n種類之熱傳導性填料的體積填充率 CV n：前述(C)熱傳導性填料當中之第n種類之熱傳導性填料的臨界體積填充率 [2] 如[1]所記載之樹脂薄片，其中，前述CV n之值係藉由下述測定方法所測定。 (CV n之值的測定方法) 調製將各熱傳導性填料的體積填充率以1%刻紋變化之樹脂組成物，並使用此等之樹脂組成物，分別製作樹脂薄片，接著，將此等之樹脂薄片的表面以雷射顯微鏡觀察(觀察面積：1mm×1mm)，確認短軸20μm以上且長軸20μm以上的大小之空隙的有無，從體積填充率低之樹脂薄片依序觀察時，將較首次確認2個以上之空隙的樹脂薄片之體積填充率更小1%之值定為CV n之值。 [3] 如[1]或[2]所記載之樹脂薄片，其中，前述樹脂組成物進一步含有(C1)氮化硼粒子。 [4] 如[1]或[2]所記載之樹脂薄片，其中，前述樹脂組成物進一步含有(C2)氧化鋁粒子。 [5] 如[1]至[4]中任一項所記載之樹脂薄片，其中，前述(A)樹脂成分含有(A1)第1馬來醯亞胺樹脂，且前述(A1)第1馬來醯亞胺樹脂係於1分子中具有2個以上之馬來醯亞胺基，且連結至少1對之2個馬來醯亞胺基的鍵結基係於主鏈具有4個以上之亞甲基的馬來醯亞胺樹脂。 [6] 如[1]至[5]中任一項所記載之樹脂薄片，其中，較佳為前述(A)樹脂成分進一步含有(A2)第2馬來醯亞胺樹脂。前述(A2)第2馬來醯亞胺樹脂係與(A1)第1馬來醯亞胺樹脂，化學構造不同之馬來醯亞胺樹脂。 [7] 如[6]所記載之樹脂薄片，其中，前述(A2)第2馬來醯亞胺樹脂係於1分子中包含2個以上之馬來醯亞胺基及2個以上之伸苯基的馬來醯亞胺樹脂。 [8] 如[1]至[7]中任一項所記載之樹脂薄片，其中，前述樹脂組成物進一步含有(B)密著性賦予劑。 [9] 如[8]所記載之樹脂薄片，其中，前述(B)密著性賦予劑含有(B1)具有三嗪骨架之化合物。 [10] 如[9]所記載之樹脂薄片，其中，前述(B1)具有三嗪骨架之化合物係於1分子中具有鹼性基，且具有三嗪骨架之化合物。 [11] 如[9]或[10]所記載之樹脂薄片，其中，前述(B1)具有三嗪骨架之化合物係於1分子中具有三嗪骨架及咪唑構造之化合物。 [12] 如[8]至[11]中任一項所記載之樹脂薄片，其中，前述(B)密著性賦予劑含有(B2)耦合劑。 [13] 如[1]至[12]中任一項所記載之樹脂薄片，其中，前述(A)樹脂成分進一步含有(A3)烯丙基樹脂。 [14] 如[1]至[13]中任一項所記載之樹脂薄片，其係使用在密封半導體元件，或者使用在介在前述半導體元件與其他電子零件之間。 [15] 如[1]至[13]中任一項所記載之樹脂薄片，其係使用在介在散熱片與電子零件之間。 [16] 如[1]至[13]中任一項所記載之樹脂薄片，其係使用在密封使用化合物半導體之半導體元件，或者使用在介在使用前述化合物半導體之半導體元件與其他電子零件之間。 根據本發明之一態樣，可提供一種可提昇熱傳導性及接著性之樹脂薄片。 The object of the present invention is to provide a resin sheet capable of improving thermal conductivity and adhesiveness. According to one aspect of the present invention, a resin sheet shown below is provided. [1] A resin sheet, which is a resin sheet formed of a resin composition containing (A) a resin component and (C) a thermally conductive filler, wherein the (A) resin component contains a maleimide resin, and contains one or more types of the above-mentioned (C) heat-conductive filler, and when the number of types of the above-mentioned (C) heat-conductive filler is defined as n, the amount of the above-mentioned (C) heat-conductive filler represented by the following formula (F1) The ratio to the critical filling amount is not less than 0.95 and not more than 1.26.
Figure 02_image001
V n : volume filling rate of the nth type of thermally conductive filler among the aforementioned (C) thermally conductive fillers CV n : critical volume filling rate of the nth type of thermally conductive filler among the aforementioned (C) thermally conductive fillers[2] The resin sheet described in [1], wherein the value of the aforementioned CV n is measured by the following measurement method. (Measurement method of CV n value) Resin compositions in which the volume filling rate of each thermally conductive filler was varied by 1% were prepared, and using these resin compositions, resin sheets were produced respectively, and then these Observe the surface of the resin flakes with a laser microscope (observation area: 1mm×1mm), and confirm the presence or absence of voids with a size of more than 20 μm in the short axis and 20 μm in the long axis. The value of the volume filling rate of the resin sheet with more than 2 voids confirmed for the first time is 1% smaller as the value of CV n . [3] The resin sheet according to [1] or [2], wherein the resin composition further contains (C1) boron nitride particles. [4] The resin sheet according to [1] or [2], wherein the resin composition further contains (C2) alumina particles. [5] The resin sheet according to any one of [1] to [4], wherein the (A) resin component contains (A1) the first maleimide resin, and the (A1) first maleimide resin is The aleimide resin has two or more maleimide groups in one molecule, and the bonding group connecting at least one pair of two maleimide groups has four or more imide groups in the main chain. Methyl maleimide resin. [6] The resin sheet according to any one of [1] to [5], wherein the (A) resin component preferably further contains (A2) a second maleimide resin. The aforementioned (A2) second maleimide resin is a maleimide resin having a different chemical structure from the (A1) first maleimide resin. [7] The resin sheet according to [6], wherein the second maleimide resin (A2) contains two or more maleimide groups and two or more phenylene groups in one molecule. based maleimide resin. [8] The resin sheet according to any one of [1] to [7], wherein the resin composition further contains (B) an adhesion imparting agent. [9] The resin sheet according to [8], wherein the (B) adhesion imparting agent contains (B1) a compound having a triazine skeleton. [10] The resin sheet according to [9], wherein the compound having a triazine skeleton (B1) is a compound having a basic group in one molecule and having a triazine skeleton. [11] The resin sheet according to [9] or [10], wherein the compound having a triazine skeleton (B1) is a compound having a triazine skeleton and an imidazole structure in one molecule. [12] The resin sheet according to any one of [8] to [11], wherein the (B) adhesion imparting agent contains (B2) a coupling agent. [13] The resin sheet according to any one of [1] to [12], wherein the (A) resin component further contains (A3) an allyl resin. [14] The resin sheet described in any one of [1] to [13], which is used to seal a semiconductor element, or used between the aforementioned semiconductor element and other electronic parts. [15] The resin sheet described in any one of [1] to [13], which is used between a heat sink and an electronic component. [16] The resin sheet described in any one of [1] to [13], which is used to seal a semiconductor device using a compound semiconductor, or used between a semiconductor device using the compound semiconductor and other electronic parts . According to an aspect of the present invention, a resin sheet capable of improving thermal conductivity and adhesiveness can be provided.

[樹脂組成物] 首先，針對用以形成有關本實施形態之樹脂薄片的樹脂組成物進行說明。 有關本實施形態之樹脂組成物含有(A)樹脂成分。有關本實施形態之(A)樹脂成分含有馬來醯亞胺樹脂。又，有關本實施形態之(A)樹脂成分較佳為含有(A1)第1馬來醯亞胺樹脂。 ((A)樹脂成分) (A)樹脂成分(以下，有單稱為「(A)」的情況)具有控制彈性率或玻璃轉移點等之樹脂組成物的物性之性質。在本實施形態之(A)樹脂成分如前述，較佳為含有(A1)第1馬來醯亞胺樹脂(以下，有單稱為「(A1)」的情況)。 (A1)第1馬來醯亞胺樹脂 在本實施形態之(A1)第1馬來醯亞胺樹脂係於1分子中具有2個以上之馬來醯亞胺基，且連結至少1對之2個馬來醯亞胺基的鍵結基係於主鏈具有4個以上之亞甲基的馬來醯亞胺樹脂。 於此，連結2個馬來醯亞胺基的鍵結基從硬化物之柔軟性的觀點來看，較佳為於主鏈具有6個以上之亞甲基，更佳為於主鏈具有8個以上之亞甲基，特佳為於主鏈具有10以上之亞甲基。又，此等之亞甲基更佳為連結，而成為碳數4以上之伸烷基。在此伸烷基，至少1個之-CH 2-可被 -CH 2-O-或-O-CH 2-取代。 又，連結2個馬來醯亞胺基的鍵結基從硬化物之柔軟性的觀點來看，較佳為具有1個以上之側鏈。作為此側鏈，可列舉烷基及烷氧基等。進而，有2個以上之側鏈的情況下，側鏈可彼此鍵結，形成脂環構造。 藉由此(A1)的使用，可兼備樹脂薄片的耐熱性與接著性。又，(A1)使用其他馬來醯亞胺樹脂時之相溶性亦高。 在本實施形態之(A1)第1馬來醯亞胺樹脂從硬化物之柔軟性及耐熱性的觀點來看，較佳為下述一般式(1)表示。

Figure 02_image003
在前述一般式(1)，n 1為0以上之整數，較佳為1以上10以下之整數，更佳為1以上5以下之整數。又，n 1之平均值較佳為0.5以上5以下，更佳為1以上2以下。 L 1及L 2分別獨立為碳數4以上之取代或是無取代之伸烷基，在此伸烷基，至少1個之-CH 2-可被-CH 2-O-或 -O-CH 2-取代。此伸烷基之碳數從硬化物之柔軟性的觀點來看，較佳為6以上，更佳為8以上，特佳為10以上30以下。又，取代伸烷基之氫時，取代基為碳數1以上14以下之烷基或碳數1以上14以下之烷氧基。進而，此等之取代基可彼此鍵結，而形成脂環構造或雜環構造。 X 1分別獨立為不具有碳數4以上之取代或是無取代之伸烷基(包含至少1個之-CH 2-被-CH 2-O-或-O-CH 2-取代者)之基，進而，較佳為具有鄰苯二甲醯亞胺基之2價之基。尚，鄰苯二甲醯亞胺基中亦包含衍生自鄰苯二甲醯亞胺之基。作為X 1，具體而言，例如可列舉下述構造式(2)、下述一般式(3)或下述一般式(4)表示之基。
Figure 02_image005
Figure 02_image007
Figure 02_image009
在前述一般式(3)，R 1及R 2分別獨立為氫、甲基或乙基，較佳為甲基。 作為在本實施形態之前述一般式(1)表示之馬來醯亞胺樹脂，具體而言，例如可列舉下述一般式(5)、下述一般式(6)或下述一般式(7)表示之化合物。
Figure 02_image011
Figure 02_image013
Figure 02_image015
在前述一般式(5)，n 2為1以上5以下之整數。 在前述一般式(6)，n 3為1以上5以下之整數。又，n之平均值為1以上2以下。 在前述一般式(7)，n 4為1以上5以下之整數。又，n之平均值為1以上2以下。 作為前述一般式(5)表示之馬來醯亞胺樹脂的製品，可列舉Designer Molecules Inc.公司製之「BMI-3000」等。 作為前述一般式(6)表示之馬來醯亞胺樹脂的製品，可列舉Designer Molecules Inc.公司製之「BMI-1700」等。 作為前述一般式(7)表示之馬來醯亞胺樹脂的製品，可列舉Designer Molecules Inc.公司製之「BMI-1500」等。 在本實施形態，馬來醯亞胺樹脂中之(A1)的含量以馬來醯亞胺樹脂之固體成分的全量基準(亦即，將排除溶媒之馬來醯亞胺樹脂之不揮發分的量定為100質量%時)，較佳為10質量%以上，更佳為20質量%以上，特佳為50質量%以上。藉由馬來醯亞胺樹脂中之(A1)的含量為這般的範圍，使得在樹脂薄片中之熱傳導性填料量的進一步增量變可能。馬來醯亞胺樹脂中之(A1)的含量之上限值以馬來醯亞胺樹脂之固體成分的全量基準，較佳為100質量%以下，更佳為85質量%以下，再更佳為75質量%以下。 (A2)第2馬來醯亞胺樹脂 在本實施形態之樹脂組成物所含有之(A)樹脂成分，從提昇樹脂薄片的硬化物在250℃之儲藏彈性率E’的觀點來看，進一步作為(A2)，可含有與前述(A1)第1馬來醯亞胺樹脂，化學構造不同之第2馬來醯亞胺樹脂。在本實施形態之(A2)第2馬來醯亞胺樹脂(以下，有單稱為「(A2)」的情況)，若為與前述(A1)第1馬來醯亞胺樹脂化學構造不同者，且於1分子中包含2個以上之馬來醯亞胺基的馬來醯亞胺樹脂，則並未特別限定。亦即，(A2)第2馬來醯亞胺樹脂係於1分子中具有2個以上之馬來醯亞胺基，且連結任2個之馬來醯亞胺基的鍵結基亦於主鏈不具有4個以上之亞甲基的馬來醯亞胺樹脂。藉由樹脂薄片含有(A2)，提昇樹脂薄片的硬化後之凝聚性。因此，可防止起因於硬化後之樹脂薄片之凝聚破壞的接著性低下。 在本實施形態之(A2)第2馬來醯亞胺樹脂，從耐熱性的觀點來看，較佳為例如包含苯環，更佳為於苯環包含連結馬來醯亞胺基之構造。又，馬來醯亞胺化合物較佳為具備2個以上於苯環連結馬來醯亞胺基之構造體。 在本實施形態之(A2)第2馬來醯亞胺樹脂，較佳為於1分子中包含2個以上之馬來醯亞胺基及2個以上之伸苯基，較佳為於1分子中包含2個以上之馬來醯亞胺基及1個以上之聯苯基骨架之馬來醯亞胺樹脂(以下，有單稱為「聯苯基馬來醯亞胺樹脂」的情況)。 在本實施形態之(A2)第2馬來醯亞胺樹脂，從耐熱性及接著性的觀點來看，較佳為下述一般式(8)表示。
Figure 02_image017
在前述一般式(8)，n 5及n 6分別獨立為1以上2以下之整數，更佳為1。惟，n 5及n 6的合計為3以下。 R 3及R 4分別獨立為碳數1以上6以下之烷基，較佳為碳數1以上3以下之烷基，更佳為甲基。複數之R 3彼此相同或彼等相異。複數之R 4彼此相同或彼等相異。 n 7及n 8分別獨立為0以上4以下之整數，較佳為0以上2以下之整數，更佳為0。 n 9為1以上之整數，n 9之平均值較佳為1以上10以下，更佳為1以上5以下，再更佳為1以上3以下。 作為在本實施形態之前述一般式(8)表示之馬來醯亞胺樹脂，例如可列舉下述一般式(9)表示之化合物。
Figure 02_image019
在前述一般式(9)，n 9係與前述一般式(8)之n 9相同。 作為前述一般式(9)表示之馬來醯亞胺樹脂的製品，可列舉日本化藥股份有限公司製之「MIR-3000」等。 又，在本實施形態之(A2)第2馬來醯亞胺樹脂，為於1分子中包含2個以上之馬來醯亞胺基及2個以上之伸苯基的馬來醯亞胺樹脂亦佳。從提高對溶劑的溶解性，且提昇薄片形成性的觀點來看，較佳為於伸苯基上具有取代基。作為取代基，例如可列舉甲基及乙基等之烷基及伸烷基等。 又，在本實施形態之(A2)第2馬來醯亞胺樹脂從薄片形成性的觀點來看，較佳為於馬來醯亞胺基與伸苯基之間具有醚鍵之馬來醯亞胺樹脂。 前述於1分子中包含2個以上之馬來醯亞胺基及2個以上之伸苯基的馬來醯亞胺樹脂，例如下述一般式(10)表示。
Figure 02_image021
在前述一般式(10)，R 5、R 6、R 7及R 8分別獨立為氫原子或碳數1以上6以下之烷基，L 3為碳數1以上3以下之伸烷基，L 4及L 5分別獨立為碳數1以上2以下之伸烷基或碳數6以上10以下之伸芳基，n 10及n 11分別獨立為0或1。惟，L 3、L 4及L 5當中，為伸烷基者之碳數的合計為3以下。 在本實施形態，(A)中之馬來醯亞胺樹脂((A1)及(A2)的合計)的含量，以(A)之固體成分的全量基準(亦即，將排除溶媒之(A)之不揮發分的量定為100質量%時)，較佳為60質量%以上，更佳為65質量%以上，特佳為70質量%以上。(A)中之馬來醯亞胺樹脂的含量之上限值以(A)之固體成分的全量基準，較佳為97質量%以下，更佳為95質量%以下，再更佳為92.5質量%以下。藉由(A)中之馬來醯亞胺樹脂的含量為這般的範圍，可更加提昇有關本實施形態之樹脂薄片的硬化後之耐熱性。 (A3)烯丙基樹脂 在本實施形態之樹脂組成物所含有之(A)樹脂成分，較佳為進一步含有(A3)烯丙基樹脂。(A3)烯丙基樹脂(以下，有單稱為「(A3)」的情況)較佳為於常溫為液體。藉由(A)樹脂成分包含烯丙基樹脂，降低有關本實施形態之樹脂薄片的反應溫度，並且提昇樹脂薄片的硬化後之剝離強變更為容易。 在本實施形態，(A3)烯丙基樹脂相對於馬來醯亞胺樹脂的合計量(A1+A2)之質量比(馬來醯亞胺樹脂的合計量(A1+A2)/(A3))，較佳為1.5以上，更佳為3以上，特佳為5以上。 又，若質量比(馬來醯亞胺樹脂的合計量(A1+A2)/ (A3))為上述範圍，適當調整樹脂薄片的複數黏度η，並確保對被著體之適用時之樹脂薄片的流動性，並且實現樹脂薄片的硬化後之耐熱性之進一步提昇。進而，若質量比(馬來醯亞胺樹脂的合計量(A1+A2)/(A3))為上述範圍，亦抑制來自樹脂薄片之烯丙基樹脂的滲出。尚，質量比(馬來醯亞胺樹脂的合計量(A1+A2)/(A3))之上限值並未特別限制。例如，質量比(馬來醯亞胺樹脂的合計量(A1+A2)/ (A3))若為50以下即可，較佳為25以下，更佳為15以下，特佳為10以下。 在本實施形態之(A3)烯丙基樹脂若為具有烯丙基之樹脂，則並未特別限定。在本實施形態之(A3)烯丙基樹脂，較佳為例如於1分子中包含2個以上之烯丙基之烯丙基樹脂。 又，此(A3)烯丙基樹脂較佳為具有芳香環。進而，在此前述(A3)烯丙基樹脂之烯丙基，較佳為直接鍵結在芳香環。又，此(A3)烯丙基樹脂較佳為具有羥基，且此羥基直接鍵結在芳香環。 在本實施形態之烯丙基樹脂，可列舉下述一般式(11)表示者。
Figure 02_image023
在前述一般式(11)，R 9及R 10分別獨立為烷基，較佳為碳數1～10之烷基，更佳為碳數1～4之烷基，再更佳為選自由甲基及乙基所成之群組中之烷基。 在前述一般式(11)，n 12為1以上4以下，較佳為1以上3以下，更佳為1以上2以下。又，在前述一般式(11)表示之烯丙基樹脂中，較佳為n 12為1之成分的比率為90mol%以上。 作為在本實施形態之(A3)烯丙基樹脂，較佳為前述一般式(11)表示之烯丙基酚樹脂。前述一般式(11)表示之化合物當中，較佳為具有於苯基之4位具有羥基之4-羥基苯基。又，前述一般式(11)表示之化合物當中，較佳為於苯基之3位或5位具有烯丙基。又，前述一般式(11)表示之化合物當中，較佳為於烯丙基之鄰位具有羥基。進而，前述一般式(11)表示之化合物當中，特佳為二烯丙基雙酚A(2,2-雙(3-烯丙基-4-羥基苯基)丙烷)。此等之烯丙基樹脂可1種單獨使用，或組合2種以上使用。 藉由使用前述之(A1)、(A2)及(A3)作為(A)樹脂成分，受到加熱時，進行三次元網狀化，可得到具有所期望物性之樹脂硬化物。 (A4)其他樹脂成分 本實施形態之(A)樹脂成分在只要不損害本發明之目的，於(A1)、(A2)及(A3)以外，可含有(A4)其他樹脂成分(以下，有單稱為「(A4)」的情況)。 作為(A4)其他樹脂成分，可列舉(A1)、(A2)及(A3)以外的熱硬化性樹脂、熱塑性樹脂或交聯劑等。 藉由使用(A4)其他樹脂成分，可提昇樹脂薄片的硬化後之剝離強度、與(A1)、(A2)、(A3)或其他成分接合，提昇樹脂薄片的耐熱性，或者提昇樹脂薄片的操作性或薄片形成性。 作為前述熱硬化性樹脂，例如可列舉酚樹脂、環氧樹脂、苯并惡嗪樹脂、氰酸酯樹脂及三聚氰胺樹脂等。此等之熱硬化性樹脂可1種單獨使用，或組合2種以上使用。藉由使用熱硬化性樹脂作為(A4)，可進一步提昇樹脂薄片的硬化後之剝離強度，且可提昇耐熱性。惟，從高耐熱性的觀點來看，較佳為(A)樹脂成分實質上未包含環氧樹脂。 作為前述熱塑性樹脂，以將硬化前之樹脂薄片的複數黏度調整在所期望範圍變容易，並提昇樹脂薄片的操作性及薄片形成性作為目的，可無論脂肪族化合物或芳香族化合物廣泛選定。熱塑性樹脂較佳為例如選自由苯氧基樹脂、丙烯酸樹脂、甲基丙烯酸樹脂、聚酯樹脂、胺基甲酸酯樹脂，及聚醯胺醯亞胺樹脂所成之群組中之至少任一種之樹脂，從耐熱性的觀點來看，更佳為選自由苯氧基樹脂及聚醯胺醯亞胺樹脂所成之群組中之至少任一種之樹脂。尚，聚酯樹脂較佳為全芳香族聚酯樹脂。又，作為聚醯胺醯亞胺樹脂，從提昇樹脂薄片之柔軟性的觀點來看，較佳為橡膠變性之聚醯胺醯亞胺樹脂。熱塑性樹脂可1種單獨使用，或組合2種以上使用。 作為苯氧基樹脂，較佳為具有選自由雙酚A骨架(以下，有將雙酚A稱為「BisA」的情況)、雙酚F骨架(以下，有將雙酚F稱為「BisF」的情況)、聯苯基骨架及萘骨架所成之群組中之1種以上之骨架的苯氧基樹脂，更佳為具有雙酚A骨架及雙酚F骨架之苯氧基樹脂。 熱塑性樹脂的重量平均分子量(Mw)，從將樹脂薄片的複數黏度調整在所期望範圍變容易的觀點來看，較佳為10,000以上1,000,000以下，更佳為15,000以上800,000以下，再更佳為20,000以上500,000以下。在本說明書之重量平均分子量係藉由凝膠滲透層析(Gel Permeation Chromatography；GPC)法所測定之標準聚苯乙烯換算值。 在本實施形態，使用熱塑性樹脂作為(A4)時，其含量以樹脂組成物之固體成分的全量基準(亦即，將排除溶媒之樹脂組成物之不揮發分的全量定為100質量%時)，較佳為1.5質量%以上，更佳為2質量%以上。樹脂組成物的含量之上限值較佳為50質量%以下，更佳為30質量%以下，特佳為15質量%以下。藉由將熱塑性樹脂的含量定為上述範圍，可賦予造膜性，並可容易將樹脂組成物成形成薄片狀。 熱塑性樹脂由於具有接合(A1)、(A2)、(A3)或其他成分之機能，故可具有官能基。如此，熱塑性樹脂具有官能基時，可具有熱塑性，亦可一併具有熱硬化性。 作為前述之交聯劑，例如可列舉有機多價異氰酸酯化合物等。交聯劑可1種單獨使用，或組合2種以上使用。藉由使用交聯劑，可與(A1)、(A2)、(A3)或其他成分接合，提昇樹脂薄片的操作性、薄片形成性、耐熱性，或者可調節樹脂薄片之硬化前的初期接著性及凝聚性。 作為有機多價異氰酸酯化合物，例如可列舉芳香族多價異氰酸酯化合物、脂肪族多價異氰酸酯化合物、脂環族多價異氰酸酯化合物，及此等之多價異氰酸酯化合物之三聚物，以及使此等多價異氰酸酯化合物與多元醇化合物進行反應所得之末端異氰酸酯胺基甲酸酯預聚物等。 作為有機多價異氰酸酯化合物之進一步具體的例，例如可列舉2,4-甲伸苯基二異氰酸酯、2,6-甲伸苯基二異氰酸酯、1,3-二伸甲苯二異氰酸酯、1,4-二伸甲苯二異氰酸酯、二苯基甲烷-4,4’-二異氰酸酯、二苯基甲烷-2,4’-二異氰酸酯、3-甲基二苯基甲烷二異氰酸酯、六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、二環己基甲烷-4,4’-二異氰酸酯、二環己基甲烷-2,4’-二異氰酸酯及離胺酸異氰酸酯等。有機多價異氰酸酯化合物可1種單獨使用，或組合2種以上使用。 使用如上述之交聯劑時，交聯劑的含量相對於前述之(A1)、(A2)及(A3)的合計量100質量份，較佳為0.01質量份以上，更佳為0.1質量份以上。交聯劑的含量之上限值較佳為12質量份以下，更佳為10質量份以下。 在本實施形態，樹脂組成物中之(A)樹脂成分的含量，以樹脂組成物之固體成分的全量基準(亦即，將排除溶媒之樹脂組成物之不揮發分的全量定為100質量%時)，較佳為2質量%以上，更佳為5質量%以上，特佳為10質量%以上。又，(A)樹脂成分的含量之上限值較佳為75質量%以下，更佳為60質量%以下，特佳為40質量%以下。 藉由(A)樹脂成分的含量為上述範圍內，可提昇樹脂薄片的操作性、薄片形狀維持性及樹脂組成物的耐熱性。 (B)密著性賦予劑 在本實施形態，樹脂組成物較佳為進一步包含(B)密著性賦予劑(以下，有單稱為「(B)」的情況)。藉由此(B)密著性賦予劑，可進一步提昇樹脂組成物之硬化後的剝離強度。 作為(B)密著性賦予劑，例如可列舉(B1)具有三嗪骨架之化合物或(B2)耦合劑。 (B1)具有三嗪骨架之化合物 作為(B1)具有三嗪骨架之化合物(以下，有單稱為「(B1)」的情況場)，較佳為如以下之化合物。亦即，(B1)較佳為於1分子中具有鹼性基，且具有三嗪骨架之化合物，更佳為於1分子中具有含氮雜環，且具有三嗪骨架之化合物，較佳為於1分子中具有三嗪骨架及咪唑構造之化合物。 作為具有三嗪骨架及咪唑構造之化合物，例如可列舉下述一般式(12)表示之化合物。
Figure 02_image025
在前述一般式(12)，R 11及R 12分別獨立為氫原子、碳數1以上20以下之烷基、羥基甲基或苯基，較佳為氫原子或碳數1以上10以下之烷基，更佳為氫原子或碳數1以上3以下之烷基。R 13為氫原子、碳數1以上20以下之烷基、苯基或烯丙基，較佳為碳數1以上10以下之烷基，更佳為碳數1以上3以下之烷基。L 6為碳數1以上5以下之伸烷基，較佳為碳數2以上4以下之伸烷基，更佳為乙烯基。 作為在本實施形態之具有三嗪骨架之咪唑化合物，具體而言，可列舉2,4-二胺基-6-[2-(2-甲基-1-咪唑基)乙基]-1,3,5-三嗪、2,4-二胺基-6-[2-(2-乙基-4-甲基-1-咪唑基)乙基]-1,3,5-三嗪，及2,4-二胺基-6-[2-(2-十一烷基-1-咪唑基)乙基]-1,3,5-三嗪等。此等之化合物當中，從樹脂組成物及樹脂薄片之剝離強度及反應溫度的觀點來看，較佳為2,4-二胺基-6-[2-(2-甲基-1-咪唑基)乙基]-1,3,5-三嗪，或2,4-二胺基-6-[2-(2-乙基-4-甲基-1-咪唑基)乙基]-1,3,5-三嗪。 (B2)耦合劑 作為(B2)耦合劑(以下，有單稱為「(B2)」的情況)，較佳為如以下之化合物。 (B2)耦合劑較佳為具有與前述之(A)樹脂成分所包含之化合物所具有之官能基進行反應之基。藉由使用(B2)耦合劑，提昇樹脂薄片的硬化物與被著體之間的剝離強度。 作為(B2)耦合劑，從其操作的容易性來看，較佳為矽烷系(矽烷耦合劑)。(B2)耦合劑可1種單獨使用，或組合2種以上使用。 作為矽烷耦合劑，可列舉具有胺基之矽烷耦合劑、具有巰基之矽烷耦合劑，及具有環氧基之矽烷耦合劑等。 作為具有胺基之矽烷耦合劑，可列舉3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-胺基丙基二甲氧基甲基矽烷、3-胺基丙基二乙氧基甲基矽烷、[3-(N,N-二甲基胺基)丙基]三甲氧基矽烷、[3-(苯基胺基)丙基]三甲氧基矽烷等。 作為具有巰基之矽烷耦合劑，可列舉3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-巰基丙基二甲氧基甲基矽烷等。 作為具有環氧基之矽烷耦合劑，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甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷等。 此等之化合物當中，從樹脂組成物及樹脂薄片之剝離強度的觀點來看，更佳為具有環氧基之矽烷耦合劑，再更佳為3-縮水甘油氧基丙基三甲氧基矽烷。 (B)密著性賦予劑相對於(A)與(B)的合計含量100質量份，較佳為(B)的合計含量0.1質量份以上，更佳為0.5質量份以上，再更佳為1.0質量份以上。又，較佳為15質量份以下，更佳為12質量份以下，再更佳為8質量份以下。藉由定為這般的範圍，可提昇樹脂薄片的硬化物與被著體之間的剝離強度。 (B)密著性賦予劑更佳為併用(B1)具有三嗪骨架之化合物、與(B2)耦合劑。藉由併用，可進一步提昇樹脂組成物之硬化後的剝離強度。 使用(B1)具有三嗪骨架之化合物作為(B)密著性賦予劑時，相對於(A)與(B)的合計含量100質量份，(B1)的含量較佳為0.1質量份以上，更佳為0.5質量份以上，再更佳為1.0質量份以上。又，較佳為15質量份以下，更佳為12質量份以下，再更佳為8質量份以下。藉由定為這般的範圍，提昇樹脂薄片的硬化物與被著體之間的剝離強度。 使用(B2)耦合劑作為(B)密著性賦予劑時，相對於(A)與(B)的合計含量100質量份，較佳為(B2)的含量為0.05質量份以上，更佳為0.10質量份以上，再更佳為0.50質量份以上。又，較佳為10質量份以下，更佳為8質量份以下，再更佳為5質量份以下。藉由定為這般的範圍，提昇樹脂薄片的硬化物與被著體之間的剝離強度。 (C)熱傳導性填料 在本實施形態，樹脂組成物除了(A)及(B)之外，包含(C)熱傳導性填料(以下，有單稱為「(C)」的情況)。藉由此(C)，可提昇樹脂組成物之熱特性及機械性特性之至少一者。 作為(C)熱傳導性填料，可列舉氮化硼粒子及氧化鋁粒子等。此等當中，(C1)氮化硼粒子(以下，有單稱為「(C1)」的情況)，及(C2)氧化鋁粒子(以下，有單稱為「(C2)」的情況)，從提昇樹脂薄片之熱擴散率的觀點來看，較佳。 (C)熱傳導性填料可1種單獨使用，或組合2種以上使用。又，(C)熱傳導性填料可經表面處理。 (C)熱傳導性填料的平均粒徑並未特別限制。(C1)氮化硼粒子之平均粒徑以d50之值，較佳為0.1μm以上，更佳為0.2μm以上，再更佳為0.3μm以上。又，(C1)氮化硼粒子之平均粒徑之上限值較佳為30μm以下，更佳為20μm以下，再更佳為15μm以下。 又，(C2)氧化鋁粒子之平均粒徑以d50之值，較佳為3μm以上，更佳為4μm以上。又，(C2)氧化鋁粒子之平均粒徑之上限值較佳為50μm以下，更佳為35μm以下，再更佳為25μm以下。 尚，(C)熱傳導性填料可於粒度分布具有複數個峰值。此時，判斷為混合有每峰值不同之種類的(C)熱傳導性填料。例如，於粒度分布有3個峰值的情況下，可判斷為混合有3種類之(C)熱傳導性填料。 在本說明書之(C)熱傳導性填料的平均粒徑，定為藉由動態光散射法所測定之值。 樹脂組成物中之(C1)氮化硼粒子及(C2)氧化鋁粒子的含量的合計，以樹脂組成物之固體成分的全量基準(亦即，將排除溶媒之樹脂組成物之不揮發分的全量定為100質量%時)，較佳為50質量%以上，更佳為65質量%以上，再更佳為70質量%以上，特佳為75質量%以上。藉由將樹脂組成物中之(C1)及(C2)的含量的合計定為上述下限以上，可提昇樹脂薄片的熱擴散率。 又，此含量的合計的上限值較佳為90質量%以下，更佳為88質量%以下，再更佳為86質量%以下，特佳為84質量%以下。藉由將樹脂組成物中之(C1)及(C2)的含量的合計定為上述上限以下，可提昇樹脂薄片的熱擴散率。 樹脂組成物含有(C1)氮化硼粒子及(C2)氧化鋁粒子兩者時，樹脂組成物中之(C1)氮化硼粒子與(C2)氧化鋁粒子的質量比，將(C2)氧化鋁粒子的質量定為1時，較佳為(C1)氮化硼粒子的質量為0.1以上，更佳為0.2以上。藉由將質量比定為上述下限以上，可提昇樹脂薄片的熱擴散率。 又，上述之樹脂組成物含有(C1)氮化硼粒子及(C2)氧化鋁粒子兩者時，樹脂組成物中之(C1)氮化硼粒子與(C2)氧化鋁粒子的質量比之上限值較佳為0.75以下，更佳為0.6以下。藉由將質量比定為上述上限以下，可提昇樹脂薄片的熱硬化後之剝離強度。 樹脂組成物中之(C)熱傳導性填料的含量，以樹脂組成物之固體成分的全量基準(亦即，將排除溶媒之樹脂組成物之不揮發分的全量定為100質量%時)，較佳為50質量%以上，更佳為65質量%以上，再更佳為70質量%以上，特佳為75質量%以上。藉由將樹脂組成物中之(C)熱傳導性填料的含量定為上述下限以上，可提昇樹脂薄片的熱擴散率。 又，(C)熱傳導性填料的含量之上限值較佳為90質量%以下，更佳為88質量%以下，再更佳為86質量%以下，特佳為84質量%以下。藉由將樹脂組成物中之(C)熱傳導性填料的含量定為上述上限以下，可提昇樹脂薄片的熱硬化後之剝離強度。 (D)硬化觸媒 於有關本實施形態之樹脂薄片，樹脂組成物包含樹脂成分時，在只要不損害本發明之目的，可進一步含有(D)硬化觸媒。藉此，使得有效果地進行樹脂成分的硬化反應變可能，使得良好地硬化樹脂薄片變可能。作為硬化觸媒之例，可列舉咪唑系硬化觸媒、胺系硬化觸媒、磷系硬化觸媒、三唑系硬化觸媒、噻唑系硬化觸媒、自由基聚合起始劑等。 作為咪唑系硬化觸媒之具體例，可列舉2-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-乙基-4-甲基咪唑、1-苄基-2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-苯基咪唑、1,2-二甲基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-十一烷基咪唑、1-氰基乙基-2-苯基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑及2-苯基-4,5-二(羥基甲基)咪唑等，從反應性的觀點來看，較佳為使用2-乙基-4-甲基咪唑。尚，作為前述之(B)密著性賦予劑，使用具有三嗪骨架及咪唑構造之化合物時，亦可用作硬化觸媒。 作為胺系硬化觸媒之具體例，可列舉1,8-二氮雜聯環[5,4,0]十一烯-7(DBU)、1,4-二氮雜聯環[2.2.2]辛烷，及N,N-二甲基苄基胺三乙基胺等之第三級胺化合物。 作為磷系硬化觸媒之具體例，可列舉三苯基膦、三丁基膦、三(p-甲基苯基)膦及三(壬基苯基)膦等。 作為三唑系硬化觸媒之具體例，可列舉苯并三唑系化合物等。 作為噻唑系硬化觸媒之具體例，可列舉苯并噻唑系化合物等。 作為自由基聚合起始劑之具體例，可列舉過氧化物及偶氮化合物等。 此等之(D)硬化觸媒可1種單獨使用，或組合2種以上使用。使用(D)硬化觸媒時，此等之含量將(A)的合計含量定為100質量份時，較佳為15質量份以下，更佳為12質量份以下，特佳為8質量份以下。 (E)其他成分 在本實施形態，樹脂組成物在只要不損害本發明之目的，可進一步包含(E)其他成分。作為(E)其他成分，例如可列舉選自由著色材料、消泡劑、整平劑、紫外線吸收劑、發泡劑、抗氧化劑、阻燃劑、離子阱劑及離子捕捉劑所成之群組中之至少任一種成分。 此等之(E)其他成分可1種單獨使用，或組合2種以上使用。使用(E)其他成分時，此等之含量將(A)的合計含量定為100質量份時，較佳為10質量份，更佳為5質量份以下。 在本實施形態，樹脂薄片藉由塗工形成的情況下，樹脂組成物較佳為包含溶媒。作為溶媒，除了甲苯、乙酸乙酯、甲基乙基酮等之一般的溶媒之外，亦可列舉環己酮(沸點：155.6℃)、二甲基甲醯胺(沸點：153℃)、二甲基亞碸(沸點：189.0℃)、乙二醇之醚類(溶纖劑)(沸點：120～310℃程度)，及鄰-二甲苯(沸點：144.4℃)等之高沸點溶媒等。 [樹脂薄片] 有關本實施形態之樹脂薄片係由前述之有關本實施形態之樹脂組成物所形成。 樹脂薄片從使用在半導體元件的密封或介在半導體元件與其他電子零件之間時之對貼附之被著體的凹凸之跟隨性等之觀點來看，較佳為僅由有關本實施形態之樹脂組成物所構成。亦即，樹脂薄片例如如預浸料般，以並非如組合樹脂組成物與纖維薄片者等之複合材料較佳。 在有關本實施形態之樹脂薄片，將(C)熱傳導性填料的種類之數定為n時，下述數式(F1)表示之(C)熱傳導性填料的對臨界填充量比有必要為0.95以上1.26以下。
Figure 02_image027
V n：(C)熱傳導性填料當中之第n種類之熱傳導性填料的體積填充率 CV n：(C)熱傳導性填料當中之第n種類之熱傳導性填料的臨界體積填充率 尚，更具體說明數式(F1)時，對臨界填充量比係n為1的情況下，以下述數式(F1-1)表示。
Figure 02_image029
n為2的情況下，以下述數式(F1-2)表示。
Figure 02_image031
n為3的情況下，以下述數式(F1-3)表示。
Figure 02_image033
對臨界填充量比未滿0.95時，導致熱傳導性降低。另一方面，對臨界填充量比超過1.26時，產生樹脂薄片之空隙，對接著性產生不良影響。又，從同樣的觀點來看，對臨界填充量比較佳為1以上，更佳為1.04以上，特佳為1.1以上。又，對臨界填充量比之上限值較佳為1.25以下，更佳為1.23以下，特佳為1.2以下。 上述之V n之值可如以下般進行而算出。 亦即，從樹脂組成物中之第n種類之(C)熱傳導性填料的含量、與其比重，算出第n種類之(C)熱傳導性填料所佔有之填料體積。又，從樹脂組成物中之(C)的含量及有機成分((C)以外之成分)的含量、與該等之比重，算出樹脂組成物所佔有之組成物體積。 而且，藉由下述數式(F2)，算出V n之值。 V n=(第n種類之填料體積)/(組成物體積)×100･･･(F2) 上述之CV n之值可如以下般進行來測定。 亦即，調製將各熱傳導性填料的體積填充率以1%刻紋變化之樹脂組成物(尚，此樹脂組成物係由第n種類之熱傳導性填料及有機成分所構成)，並使用此等之樹脂組成物，分別製作樹脂薄片。接著，將此等之樹脂薄片的表面以雷射顯微鏡觀察(觀察面積：1mm×1mm)，確認短軸20μm以上且長軸20μm以上的大小之空隙的有無(參照圖2及圖3)。尚，於圖2(B)及圖3(B)所觀察之黑色部分有空隙。於圖2(B)及圖3(B)，由於既已超過臨界體積填充率，觀察到為數眾多之空隙。 從體積填充率低之樹脂薄片依序觀察時，將較首次確認2個以上之空隙的樹脂薄片之體積填充率更小1%之值定為CV n之值。 在有關本實施形態之樹脂薄片，較佳為(C)之填料體積填充率為50%以上65%以下。 填料體積填充率若為50%以上，可進一步提昇熱傳導性。另一方面，填料體積填充率若為65%以下，可提昇樹脂薄片的接著性。又，從同樣的觀點來看，填料體積填充率較佳為52%以上，更佳為55%以上。又，填料體積填充率之上限值較佳為64%以下，更佳為62%以下。 填料體積填充率可如以下般進行而算出。 亦即，從樹脂組成物中之(C)的含量、與該等之比重，算出(C)所佔有之填料體積。尚，(C)由n種類之(C)熱傳導性填料所構成時，從第1種類之(C)熱傳導性填料所佔有之填料體積，至第n種類之(C)熱傳導性填料所佔有之填料體積為止的合計為填料體積。又，從樹脂組成物中之(C)的含量及有機成分((C)以外之成分)的含量、與該等之比重，算出樹脂組成物所佔有之組成物體積。尚，氮化硼粒子、氧化鋁粒子及有機成分的比重係如上述。 而且，藉由下述數式(F3)，算出(C)之填料體積填充率。 (填料體積填充率)=(填料體積)/(組成物體積)×100･･･(F3) 有關本實施形態之樹脂薄片的熱硬化後之熱擴散率有必要為1.0×10 -6m 2/s以上，較佳為1.1×10 -6m 2/s以上，更佳為1.2×10 -6m 2/s以上，再更佳為1.3×10 -6m 2/s以上，又再更佳為1.35×10 -6m 2/s以上，特佳為1.5×10 -6m 2/s以上。又，熱硬化後之熱擴散率之上限值較佳為1×10 -5m 2/s以下，更佳為8×10 -6m 2/s以下，再更佳為5×10 -6m 2/s以下，又再更佳為4×10 -6m 2/s以下，特佳為3×10 -6m 2/s以下。 藉由樹脂薄片的熱硬化後之熱擴散率為這般的範圍，可得到具有高熱傳導性之硬化物。樹脂薄片的熱硬化後之熱擴散率係藉由後述之實施例所記載之方法所得之特性值。 又，有關本實施形態之樹脂薄片的熱硬化後之剝離強度較佳為超過2.0N/10mm，更佳為3.0N/10mm以上，再更佳為5.0N/10mm以上，特佳為6.0N/10mm以上。又，熱硬化後之剝離強度之上限值更佳為50N/10mm以下，再更佳為40N/10mm以下。 有關本實施形態之樹脂薄片的熱硬化後之剝離強度若超過2.0N/10mm，將樹脂薄片作為密封材使用的情況下，對於被著物，可維持高接著性。 有關本實施形態之樹脂薄片的熱硬化後之剝離強度，例如藉由調整使用在樹脂組成物之成分的種類(尤其是硬化促進劑的種類)及摻合量，可調整至上述範圍。 尚，有關本實施形態之樹脂薄片的熱硬化後之剝離強度使用後述的測定方法，藉由於熱硬化後之樹脂薄片與被著物之間，進行剝離角度90度之剝離試驗求出。具體而言，如實施例之記載，作成試驗片，進行剝離試驗。 在有關本實施形態之樹脂薄片，藉由薄片化樹脂組成物，對被著體之適用變簡便，尤其是被著體為大面積時之適用變簡便。 若樹脂組成物為薄片狀，由於預先形成相對於密封步驟後之形狀為適合的形狀，僅適用，可作為保持某程度的均一性之密封材供給。又，若樹脂組成物為薄片狀，操作性優異。 薄片化樹脂組成物之方法，可採用以往公知之薄片化的方法，並未特別限定。從容易得到薄樹脂薄片的觀點來看，樹脂薄片較佳為樹脂組成物之塗膜。樹脂組成物的塗膜之樹脂薄片，可藉由包含塗佈前述樹脂組成物之步驟的製造方法獲得。 於此，作為塗佈方法，並未特別限定，可使用公知之方法。又，於塗佈後如有必要可進行乾燥。針對乾燥條件，若為未硬化前述樹脂組成物的條件，則並未特別限定。 有關本實施形態之樹脂薄片可為帶狀之薄片，亦可以捲繞成輥狀的狀態提供。捲繞成輥狀之有關本實施形態之樹脂薄片，可進行從輥拉出並切斷成所期望尺寸等來使用。 有關本實施形態之樹脂薄片的厚度，例如較佳為10μm以上，更佳為20μm以上，再更佳為30μm以上。又，該厚度較佳為200μm以下，更佳為150μm以下，再更佳為120μm以下。又，樹脂薄片為樹脂組成物的塗膜的情況下，薄化樹脂薄片容易，有關本實施形態之樹脂薄片的厚度較佳為100μm以下，更佳為80μm以下，再更佳為60μm以下。 (熱硬化條件) 在有關本實施形態之樹脂薄片的熱硬化條件中，加熱溫度較佳為50℃以上，更佳為100℃以上，再更佳為130℃以上，又再更佳為160℃以上。又，加熱溫度之上限值較佳為300℃以下，更佳為250℃以下，再更佳為230℃以下，又再更佳為210℃以下。 在有關本實施形態之樹脂薄片的熱硬化條件中，加熱時間較佳為10分鐘以上，更佳為20分鐘以上。又，加熱時間之上限值較佳為10小時以下，更佳為7小時以下。 藉由在樹脂薄片的熱硬化條件為上述之範圍，可實現於低溫及短時間之樹脂薄片的熱硬化。 [層合體] 圖1中顯示有關本實施形態之層合體1之剖面概略圖。 本實施形態之層合體1具有：第一剝離材2、與第二剝離材4、與設置在第一剝離材2及第二剝離材4之間的樹脂薄片3。樹脂薄片3為有關本實施形態之樹脂薄片。 第一剝離材2及第二剝離材4較佳為具有剝離性，於相對於第一剝離材2之樹脂薄片3之剝離力與相對於第二剝離材4之樹脂薄片3之剝離力有差異。第一剝離材2及第二剝離材4之材質並未特別限定。相對於第一剝離材2之剝離力P1之第二剝離材4之剝離力P2之比(P2/P1)較佳為0.02≦P2/P1＜1或1＜P2/P1≦50。 第一剝離材2及第二剝離材4，除了例如剝離材本身為有剝離性之構件之外，亦可為實施剝離處理之構件或層合剝離劑層之構件等。未對第一剝離材2及第二剝離材4實施剝離處理時，作為第一剝離材2及第二剝離材4之材質，例如可列舉烯烴系樹脂、氟樹脂等。 第一剝離材2及第二剝離材4可成為具備：剝離基材、與於剝離基材之上塗佈剝離劑而形成之剝離劑層的剝離材。藉由成為具備剝離基材與剝離劑層之剝離材，使得操作變容易。又，第一剝離材2及第二剝離材4可僅於剝離基材的單面具備剝離劑層，亦可於剝離基材的兩面具備剝離劑層。 作為剝離基材，例如可列舉紙基材、於此紙基材層壓聚乙烯等之熱塑性樹脂的層壓紙及塑膠薄膜等。作為紙基材，例如可列舉玻璃紙、銅版紙及鑄塗紙等。作為塑膠薄膜，例如可列舉聚酯薄膜(例如聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯及聚萘二甲酸乙二酯等)，以及聚烯烴薄膜(例如聚丙烯及聚乙烯等)等。此等當中，較佳為聚酯薄膜。 作為剝離劑，例如可列舉以聚矽氧樹脂構成之聚矽氧系剝離劑；聚乙烯胺基甲酸酯(Carbamate)，及烷基尿素衍生物等之以含有長鏈烷基之化合物構成的含有長鏈烷基之化合物系剝離劑；以醇酸樹脂(例如，不轉化性醇酸樹脂及轉化性醇酸樹脂等)構成之醇酸樹脂系剝離劑；烯烴樹脂(例如聚乙烯(例如高密度聚乙烯、低密度聚乙烯及直鏈狀低密度聚乙烯等)、等規立構構造，或具有間規立構構造之丙烯單獨聚合物，及以丙烯-α-烯烴共聚物等之結晶性聚丙烯樹脂等)構成之烯烴樹脂系剝離劑；以天然橡膠及合成橡膠(例如，丁二烯橡膠、異戊二烯橡膠、苯乙烯-丁二烯橡膠、甲基甲基丙烯酸酯-丁二烯橡膠及丙烯腈-丁二烯橡膠等)等之橡膠構成之橡膠系剝離劑；以及以(甲基)丙烯酸酯系共聚物等之丙烯酸樹脂構成之丙烯酸樹脂系剝離劑等之各種剝離劑，可將此等以1種單獨或組合2種以上使用。此等當中，較佳為醇酸樹脂系剝離劑。尤其是作為樹脂薄片3所包含之樹脂組成物的(B)黏結劑成分，使用苯氧基樹脂的情況下，採用一般的聚矽氧系剝離劑時，由於有導致剝離材於樹脂薄片3之使用前未故意剝離之虞，故較佳為使用醇酸樹脂系剝離劑。 第一剝離材2及第二剝離材4的厚度並未特別限定。通常為1μm以上500μm以下，較佳為3μm以上100μm以下。 剝離劑層的厚度並未特別限定。塗佈包含剝離劑之溶液，形成剝離劑層時，剝離劑層的厚度較佳為0.01μm以上3μm以下，更佳為0.03μm以上1μm以下。 層合體1之製造方法並未特別限定。例如，層合體1係經由如以下之步驟製造。首先，於第一剝離材2之上塗佈樹脂組成物，而形成塗膜。接著，使此塗膜乾燥，形成樹脂薄片3。接著，藉由將樹脂薄片3、與第二剝離材4以常溫貼合，而得到層合體1。尚，此情況下，第一剝離材2與第二剝離材4之剝離材的種類相同的情況下，第二剝離材4之剝離力P2相對於第一剝離材2之剝離力P1之比(P2/P1)，成為P2/P1＜1之可能性高，第一剝離材2與第二剝離材4之剝離材即使為異種者，藉由塗佈樹脂組成物為第一剝離材2，有縮小P2/P1之值的傾向。 [本實施形態的效果] 根據有關本實施形態之樹脂薄片及層合體，亦提昇耐熱性優異之樹脂薄片的熱硬化後之熱傳導性，可進一步提昇熱硬化後之接著性。 如上述，有關本實施形態之樹脂薄片可適合使用在功率半導體元件。換言之，在有關本實施形態之半導體裝置，半導體元件較佳為功率半導體元件。功率半導體元件亦假定於200℃以上之高溫的動作。使用在具有功率半導體元件之半導體裝置的材料中要求耐熱性。有關本實施形態之樹脂薄片由於耐熱性優異，在半導體裝置，適合使用在：使用在被覆功率半導體元件，或者介在功率半導體元件與其他構件之間。又，有關本實施形態之樹脂薄片較佳為一次適用在複數個半導體元件。例如，若樹脂組成物為薄片狀，可使用在於設置複數個間隙之框架的每個間隙，相對於配置半導體元件之構造體，適用樹脂薄片，並一次密封框架與半導體元件之所謂面板級封裝。 又，半導體元件的密封可為用以保護倒裝晶片型之元件的背面之被覆。一般的保護薄片中，遮斷從元件所產生之熱，並相對導致於在元件積聚熱，藉由將有關本實施形態之樹脂薄片作為倒裝晶片型之元件的背面保護薄片使用，可有效率地耗散從元件所產生之熱。 又，有關本實施形態之樹脂薄片由於熱硬化後之熱傳導性優異，故可將從功率半導體元件所產生之熱有效率地傳送至散熱片等。亦即，有關本實施形態之樹脂薄片由於耐熱性及熱傳導性優異，故可使用在密封假定200℃以上之高溫動作的功率半導體元件，或介在功率半導體元件與其他電子零件之間，將從功率半導體元件所產生之熱傳導至散熱片等之能力優異。 如上述，有關本實施形態之樹脂薄片可適合使用在使用化合物半導體之半導體元件。換言之，在有關本實施形態之半導體裝置，半導體元件較佳為使用化合物半導體之半導體元件。使用化合物半導體之半導體元件由於具有與矽半導體元件不同之特性，故較佳為使用在功率半導體元件、基地局部用高輸出裝置、傳感器、檢測器及蕭特基二極體等之用途。於此等之用途，亦著重在使用化合物半導體之半導體元件的耐熱性，本實施形態之樹脂薄片由於耐熱性優異，適合與使用化合物半導體之半導體元件組合來使用。又，有關本實施形態之樹脂薄片由於熱硬化後之熱傳導性優異，可將從使用化合物半導體之半導體元件所產生之熱有效率地傳導至散熱片等。 又，有關本實施形態之樹脂薄片較佳為使用在密封使用化合物半導體之半導體元件。或有關本實施形態之樹脂薄片，較佳為使用在介在使用化合物半導體之半導體元件與其他電子零件之間。作為其他電子零件，例如可列舉印刷配線基板及引線框架等。 矽半導體元件的動作溫度之上限由於為175℃左右，故較佳為使用功率半導體元件中使用可高溫動作之化合物半導體之半導體元件。作為化合物半導體，可列舉碳化矽、氮化鎵、氮化鋁鎵、氧化鎵、鎵砷等，較佳為碳化矽、氮化鎵、氮化鋁鎵及氧化鎵之任1種以上。 有關本實施形態之樹脂薄片由於耐熱性及熱傳導性優異，故可使用在密封使用假定200℃以上之高溫動作的化合物半導體之半導體元件，或介在使用化合物半導體之半導體元件與其他電子零件之間，將從此等之功率半導體元件所產生之熱傳導至散熱片等之能力優異。 [實施形態的變形] 本發明並非被限定於前述實施形態，於可達成本發明之目的的範圍的變形或改良等，包含在本發明。 於前述實施形態，雖針對具有第一剝離材、與第二剝離材、與設置在第一剝離材及第二剝離材之間的樹脂薄片之層合體進行說明，但其他亦可為僅於樹脂薄片之一側的面具有剝離材之層合體。 又，於前述半導體裝置之實施形態，雖針對半導體密封用途進行說明，但本發明之樹脂薄片其他亦可作為電路基板用絕緣材料(例如，硬質印刷配線板材料、可撓性配線基板用材料，及堆積基板用層間絕緣材料等)、堆積用接著薄膜，以及接著劑等使用。 實施例以下，列舉實施例，進一步詳細說明本發明。本發明並非因此等實施例而被任何限定。 [實施例及比較例] [樹脂組成物的調製] 在表1所示之摻合比例(質量%(固體成分換算的比例))，藉由將各成分溶解或分散在溶媒，調製有關實施例1～3以及比較例1～3之樹脂組成物。尚，將在實施例及比較例之(A)、(B)及(C)的含量示於表1。 使用在樹脂組成物的調製之材料係如以下。 (A)樹脂成分 ･第1馬來醯亞胺樹脂-1：長鏈烷基型馬來醯亞胺樹脂(在溫度25℃為固體、前述一般式(5)表示之馬來醯亞胺樹脂) ･第1馬來醯亞胺樹脂-2：長鏈烷基型馬來醯亞胺樹脂(在溫度25℃為液狀、前述一般式(7)表示之馬來醯亞胺樹脂) ･第2馬來醯亞胺樹脂：具有聯苯基之馬來醯亞胺樹脂(前述一般式(9)表示之馬來醯亞胺樹脂、日本化藥股份有限公司製「MIR-3000」) ･烯丙基樹脂：二烯丙基雙酚A(大和化成工業股份有限公司製「DABPA」) (B)密著性賦予劑 ･具有三嗪骨架之化合物(三嗪化合物)：2,4-二胺基-6-[2-(2-乙基-4-甲基-1-咪唑基)乙基]-1,3,5-三嗪(四國化成工業股份有限公司製「2E4MZ-A」) ･耦合劑：3-縮水甘油氧基丙基三乙氧基矽烷 (C)熱傳導性填料 ･氧化鋁粒子：(昭和電工股份有限公司製「CB-A20S」、平均粒徑(d50)：20μm) ･氮化硼粒子-1：(昭和電工股份有限公司製「UHP-2」、平均粒徑(d50)：11μm) ･氮化硼粒子-2：(昭和電工股份有限公司製「UHP-S2」、平均粒徑(d50)：0.7μm) [包含樹脂薄片之層合體的製作] 於第一剝離材(設置從醇酸樹脂系剝離劑所形成之剝離層的聚對苯二甲酸乙二酯薄膜、厚度38μm)上，以刀塗機塗佈樹脂清漆(於環己酮溶解樹脂組成物所調製之塗佈用溶液、固體成分濃度定為72質量%)，於90℃乾燥1分鐘及於115℃乾燥1分鐘。乾燥後之樹脂組成物的厚度係如表1所示。剛從乾燥爐取出後，將乾燥後之樹脂組成物、與第二剝離材(設置從聚矽氧系剝離劑所形成之剝離層的聚對苯二甲酸乙二酯薄膜、厚度38μm)於常溫層合，並製作依第一剝離材、由樹脂組成物所構成之樹脂薄片，及第二剝離材順序層合之層合體。 ＜樹脂薄片之物性確認及評估＞ [樹脂薄片之填料體積填充率] 從樹脂組成物中之(C)的含量、與該等之比重，算出(C)所佔有之填料體積。尚，於本實施例等，由於使用氧化鋁粒子、氮化硼粒子-1及氮化硼粒子-2之3種類的(C)，氧化鋁粒子所佔有之填料體積、與氮化硼粒子-1所佔有之填料體積、與氮化硼粒子-2所佔有之填料體積的合計為填料體積。又，從樹脂組成物中之(C)的含量及有機成分((A)與(B)的合計)的含量、與該等之比重，算出樹脂組成物所佔有之組成物體積。尚，氮化硼粒子之比重定為2.27，氧化鋁粒子之比重定為3.9。又，有機成分之比重定為1.2。 而且，藉由下述數式(F3)，算出(C)之填料體積填充率(全填料的體積填充率的合計)。將所得之結果示於表1。 (填料體積填充率)=(填料體積)/(組成物體積)×100･･･(F3) [樹脂薄片之對臨界填充量比] 將下述數式(F1)表示之(C)熱傳導性填料的對臨界填充量比藉由下述的測定或計算求出。將所得之結果示於表1。
Figure 02_image035
V n：(C)熱傳導性填料當中之第n種類之熱傳導性填料的體積填充率 CV n：(C)熱傳導性填料當中之第n種類之熱傳導性填料的臨界體積填充率 尚，於本實施例等，由於使用氧化鋁粒子、氮化硼粒子-1及氮化硼粒子-2之3種類的(C)，具體而言，可藉由下述數式(F1-3)算出。
Figure 02_image037
V 1：氧化鋁粒子之體積填充率 CV 1：氧化鋁粒子之臨界體積填充率 V 2：氮化硼粒子-1之體積填充率 CV 2：氮化硼粒子-1之臨界體積填充率 V 3：氮化硼粒子-2之體積填充率 CV 3：氮化硼粒子-2之臨界體積填充率 上述之V n之值如以下般進行而算出。 亦即，從樹脂組成物中之第n種類之(C)熱傳導性填料的含量、與其比重，算出第n種類之(C)熱傳導性填料所佔有之填料體積。又，從樹脂組成物中之(C)的含量及有機成分((C)之外的成分)的含量、與該等之比重，算出樹脂組成物所佔有之組成物體積。尚，氮化硼粒子、氧化鋁粒子及有機成分之比重係如上述。 而且，藉由下述數式(F2)，算出V n之值。 V n=(第n種類之填料體積)/(組成物體積)×100･･･(F2) 上述之CV n之值如以下般進行來測定。 亦即，調製將各熱傳導性填料的體積填充率以1%刻紋變化之樹脂組成物(尚，此樹脂組成物係由第n種類之熱傳導性填料及有機成分所構成)，並使用此等之樹脂組成物，分別製作樹脂薄片。接著，將此等之樹脂薄片的表面以雷射顯微鏡(KEYENCE股份有限公司製、製品名「VK-9500」)觀察(觀察面積：1mm×1mm)，確認短軸20μm以上且長軸20μm以上的大小之空隙的有無。 從體積填充率低之樹脂薄片依序觀察時，將較首次確認2個以上之空隙的樹脂薄片之體積填充率更小1%之值定為CV n之值。 尚，CV n之值針對氧化鋁粒子、氮化硼粒子-1及氮化硼粒子-2之個別進行測定。 在氧化鋁粒子之臨界體積填充率的測定，將樹脂薄片的表面以雷射顯微鏡觀察的照片示於圖2A及圖2B。於圖2A之氧化鋁粒子的體積填充率為65%，於圖2B之氧化鋁粒子的體積填充率為75%。 在氮化硼粒子-1之臨界體積填充率的測定，將樹脂薄片的表面以雷射顯微鏡觀察的照片示於圖3A及圖3B。於圖3A之氮化硼粒子的體積填充率為30%，於圖3B之氮化硼粒子的體積填充率為40%。 測定的結果，CV 1(氧化鋁粒子之臨界體積填充率)為72%，CV 2(氮化硼粒子-1之臨界體積填充率)為35%，CV 3(氮化硼粒子-2之臨界體積填充率)為37%。 [樹脂薄片的厚度] 使用TECLOCK股份有限公司製之定壓厚度測定器(型號：「PG-02J」、標準規格：依據JIS K6783、Z1702、Z1709)測定。將所得之結果示於表1。 [在樹脂薄片的熱硬化後之熱擴散率的測定] 將樹脂薄片以厚度成為200μm的方式貼合，在溫度200℃，以4小時的熱硬化條件進行硬化，作為試料。尚，層合體之第一剝離材及第二剝離材於貼合之過程適當去除。針對此試料，使用熱擴散率測定裝置(ai-Phase股份有限公司製「ai-Phase Mobile 1」)，藉由溫度波法，測定熱擴散率。將所得之結果示於表1。 [剝離強度的測定] 於銅板(JIS-C1220P規格、厚度400μm)，藉由將在所得之層合體的樹脂薄片之一側的面以層壓溫度130℃進行減壓壓接來貼合(層壓裝置：Nikko Materialals股份有限公司製「V-130」；條件：到達壓力100Pa、加壓力0.3MPa、時間30秒)，接著，於樹脂薄片之另一側的面，藉由將銅箔(大小50mm×10mm、厚度150μm、JIS H 3100規格)以與上述相同條件進行減壓壓接來貼合。尚，在層合體之樹脂薄片之第二剝離材及第一剝離材分別於貼合在Si晶圓及銅板之前剝離。然後，在溫度200℃，以4小時的熱硬化條件，使樹脂薄片硬化，作為試料。針對此試料，使用拉伸試驗機(島津製作所股份有限公司製「AUTOGRAPH AG-IS」)，以剝離速度50mm/分鐘、剝離角度90度的條件，從硬化銅箔後之樹脂薄片剝離，測定銅箔與硬化後之樹脂薄片的剝離強度(單位：N/10mm)。測定係於25℃、相對濕度50%的環境下進行。將所得之結果示於表1。尚，比較例1之試料由於接著性過低，剝離強度的測定無法進行，故判定為「NG」。
Figure 02_image039
從表1所示之結果即可清楚明白，瞭解到在於實施例1～3所得之樹脂薄片，對臨界填充量比為0.95以上1.26以下之範圍內，剝離強度高，又，熱硬化後之熱擴散率高。 [Resin Composition] First, the resin composition for forming the resin sheet according to the present embodiment will be described. The resin composition concerning this embodiment contains (A) resin component. The (A) resin component in this embodiment contains a maleimide resin. Moreover, it is preferable that (A) resin component concerning this embodiment contains (A1) 1st maleimide resin. ((A) Resin Component) (A) The resin component (hereinafter, sometimes simply referred to as "(A)") has the property of controlling the physical properties of the resin composition such as elastic modulus and glass transition point. The (A) resin component in this embodiment preferably contains (A1) the first maleimide resin (hereinafter, may be simply referred to as "(A1)") as described above. (A1) The first maleimide resin The (A1) first maleimide resin in this embodiment has two or more maleimide groups in one molecule, and at least one pair of them is linked. The bonding group of two maleimide groups is a maleimide resin having four or more methylene groups in the main chain. Here, the linking group connecting two maleimide groups preferably has 6 or more methylene groups in the main chain, and more preferably has 8 methylene groups in the main chain from the viewpoint of flexibility of the cured product. More than one methylene group, particularly preferably ten or more methylene groups in the main chain. Moreover, these methylene groups are more preferably linked to form an alkylene group having 4 or more carbon atoms. In the alkylene group, at least one -CH 2 - may be substituted by -CH 2 -O- or -O-CH 2 -. Also, the linking group linking two maleimide groups preferably has one or more side chains from the viewpoint of flexibility of the cured product. As this side chain, an alkyl group, an alkoxy group, etc. are mentioned. Furthermore, when there are two or more side chains, the side chains may be bonded to each other to form an alicyclic structure. By using this (A1), the heat resistance and adhesiveness of a resin sheet can be compatible. Also, (A1) has high compatibility when other maleimide resins are used. The (A1) first maleimide resin in this embodiment is preferably represented by the following general formula (1) from the viewpoint of the flexibility and heat resistance of the cured product.
Figure 02_image003
In the aforementioned general formula (1), n 1 is an integer of 0 or more, preferably an integer of 1 or more and 10 or less, more preferably an integer of 1 or more and 5 or less. Also, the average value of n 1 is preferably from 0.5 to 5, more preferably from 1 to 2. L 1 and L 2 are each independently a substituted or unsubstituted alkylene group with 4 or more carbon atoms. In the alkylene group, at least one -CH 2 - can be replaced by -CH 2 -O- or -O-CH 2 - Replace. The carbon number of the alkylene group is preferably 6 or more, more preferably 8 or more, and particularly preferably 10 or more and 30 or less from the viewpoint of flexibility of the cured product. Also, when substituting the hydrogen of an alkylene group, the substituent is an alkyl group having 1 to 14 carbon atoms or an alkoxy group having 1 to 14 carbon atoms. Furthermore, these substituents may be bonded to each other to form an alicyclic structure or a heterocyclic structure. X 1 are independently unsubstituted or unsubstituted alkylene groups (including at least one -CH 2 - substituted by -CH 2 -O- or -O-CH 2 -) with a carbon number of 4 or more , and further, a divalent group having a phthalimide group is preferable. Furthermore, the phthalimide group also includes a group derived from phthalimide. Specific examples of X 1 include groups represented by the following structural formula (2), the following general formula (3) or the following general formula (4).
Figure 02_image005
Figure 02_image007
Figure 02_image009
In the aforementioned general formula (3), R 1 and R 2 are independently hydrogen, methyl or ethyl, preferably methyl. As the maleimide resin represented by the aforementioned general formula (1) in this embodiment, specifically, for example, the following general formula (5), the following general formula (6) or the following general formula (7) can be mentioned. ) represented by the compound.
Figure 02_image011
Figure 02_image013
Figure 02_image015
In the aforementioned general formula (5), n 2 is an integer ranging from 1 to 5. In the aforementioned general formula (6), n 3 is an integer ranging from 1 to 5. Moreover, the average value of n is 1-2. In the aforementioned general formula (7), n 4 is an integer ranging from 1 to 5. Moreover, the average value of n is 1-2. Examples of products of the maleimide resin represented by the general formula (5) include "BMI-3000" manufactured by Designer Molecules Inc., and the like. Examples of products of the maleimide resin represented by the general formula (6) include "BMI-1700" manufactured by Designer Molecules Inc., and the like. Examples of products of the maleimide resin represented by the general formula (7) include "BMI-1500" manufactured by Designer Molecules Inc., and the like. In this embodiment, the content of (A1) in the maleimide resin is based on the total amount of the solid content of the maleimide resin (that is, the non-volatile content of the maleimide resin that excludes the solvent) 100% by mass), preferably at least 10% by mass, more preferably at least 20% by mass, particularly preferably at least 50% by mass. With the content of (A1) in the maleimide resin in such a range, further increase in the amount of the thermally conductive filler in the resin sheet becomes possible. The upper limit of the content of (A1) in the maleimide resin is based on the total amount of the solid content of the maleimide resin, preferably 100% by mass or less, more preferably 85% by mass or less, and even more preferably 75% by mass or less. (A2) Second maleimide resin The (A) resin component contained in the resin composition of the present embodiment further improves the storage modulus E' of the cured product of the resin sheet at 250°C. (A2) may contain a second maleimide resin having a different chemical structure from the first maleimide resin (A1) above. In the (A2) second maleimide resin of this embodiment (hereinafter, sometimes simply referred to as "(A2)"), if the chemical structure is different from that of the aforementioned (A1) first maleimide resin Moreover, the maleimide resin which contains two or more maleimide groups in 1 molecule is not specifically limited. That is, (A2) the second maleimide resin has two or more maleimide groups in one molecule, and the linking group connecting any two maleimide groups is also in the main body. A maleimide resin whose chain does not have more than 4 methylene groups. Containing (A2) in the resin sheet improves the cohesiveness of the resin sheet after curing. Therefore, it is possible to prevent the decrease in adhesiveness caused by cohesive failure of the cured resin sheet. The (A2) second maleimide resin in this embodiment preferably includes, for example, a benzene ring from the viewpoint of heat resistance, and more preferably has a structure including a maleimide group linked to the benzene ring. Also, the maleimide compound preferably has a structure in which two or more maleimide groups are linked to the benzene ring. The (A2) second maleimide resin in this embodiment preferably contains two or more maleimide groups and two or more phenylene groups in one molecule, and preferably contains two or more phenylene groups in one molecule. Maleimide resins containing two or more maleimide groups and one or more biphenyl skeletons (hereinafter, may be simply referred to as "biphenylmaleimide resins"). The (A2) second maleimide resin in this embodiment is preferably represented by the following general formula (8) from the viewpoint of heat resistance and adhesiveness.
Figure 02_image017
In the aforementioned general formula (8), n 5 and n 6 are each independently an integer ranging from 1 to 2, more preferably 1. However, the total of n 5 and n 6 is 3 or less. R 3 and R 4 are each independently an alkyl group with 1 to 6 carbons, preferably an alkyl group with 1 to 3 carbons, more preferably a methyl group. The plural R 3 are the same as each other or they are different. The plural R 4 are the same as each other or they are different. n 7 and n 8 are each independently an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0. n 9 is an integer of 1 or more, and the average value of n 9 is preferably from 1 to 10, more preferably from 1 to 5, and still more preferably from 1 to 3. Examples of the maleimide resin represented by the general formula (8) in this embodiment include compounds represented by the following general formula (9).
Figure 02_image019
In the aforementioned general formula (9), n 9 is the same as n 9 in the aforementioned general formula (8). Examples of products of the maleimide resin represented by the general formula (9) include "MIR-3000" manufactured by Nippon Kayaku Co., Ltd., and the like. Also, (A2) the second maleimide resin in this embodiment is a maleimide resin containing two or more maleimide groups and two or more phenylene groups in one molecule. Also good. It is preferable to have a substituent on the phenylene group from the viewpoint of improving solubility in solvents and improving sheet formability. As a substituent, an alkyl group, such as a methyl group and an ethyl group, an alkylene group, etc. are mentioned, for example. In addition, the (A2) second maleimide resin in this embodiment is preferably maleimide having an ether bond between the maleimide group and the phenylene group from the viewpoint of sheet formability. imide resin. The aforementioned maleimide resin containing two or more maleimide groups and two or more phenylene groups in one molecule is represented by, for example, the following general formula (10).
Figure 02_image021
In the aforementioned general formula (10), R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom or an alkyl group with 1 to 6 carbons, L 3 is an alkylene group with 1 to 3 carbons, and L 4 and L 5 are each independently an alkylene group with 1 to 2 carbon atoms or an arylylene group with 6 to 10 carbon atoms, and n 10 and n 11 are independently 0 or 1. However, among L 3 , L 4 and L 5 , the total number of carbon atoms of the alkylene group is 3 or less. In this embodiment, the content of the maleimide resin (the total of (A1) and (A2)) in (A) is based on the total amount of the solid content of (A) (that is, the amount of (A) that excludes the solvent When the amount of non-volatile matter in ) is 100% by mass), it is preferably at least 60% by mass, more preferably at least 65% by mass, and most preferably at least 70% by mass. The upper limit of the maleimide resin content in (A) is based on the total amount of solid content in (A), preferably 97% by mass or less, more preferably 95% by mass or less, still more preferably 92.5% by mass %the following. When content of the maleimide resin in (A) is such a range, the heat resistance after hardening of the resin sheet concerning this embodiment can be improved more. (A3) Allyl resin It is preferable that (A) resin component contained in the resin composition of this embodiment further contains (A3) allyl resin. (A3) The allyl resin (hereinafter, may be simply referred to as "(A3)") is preferably liquid at room temperature. Since the (A) resin component contains the allyl resin, the reaction temperature of the resin sheet according to the present embodiment is lowered, and the peeling strength after curing of the resin sheet is improved to be easily changed. In this embodiment, the mass ratio of (A3) allyl resin to the total amount of maleimide resin (A1+A2) (total amount of maleimide resin (A1+A2)/(A3) ), preferably 1.5 or more, more preferably 3 or more, particularly preferably 5 or more. Also, if the mass ratio (total amount of maleimide resin (A1+A2)/(A3)) is within the above range, properly adjust the complex viscosity η of the resin sheet, and ensure the resin sheet when it is applied to the substrate Fluidity, and to further improve the heat resistance of the resin sheet after hardening. Furthermore, if the mass ratio (total amount (A1+A2)/(A3) of the maleimide resin) is within the above range, bleeding of the allyl resin from the resin sheet is also suppressed. Also, the upper limit of the mass ratio (total amount of maleimide resin (A1+A2)/(A3)) is not particularly limited. For example, the mass ratio (total amount of maleimide resin (A1+A2)/(A3)) may be 50 or less, preferably 25 or less, more preferably 15 or less, most preferably 10 or less. The (A3) allyl resin in this embodiment will not be specifically limited if it is resin which has an allyl group. The (A3) allyl resin in this embodiment is preferably, for example, an allyl resin containing two or more allyl groups in 1 molecule. Moreover, this (A3) allyl resin preferably has an aromatic ring. Furthermore, the allyl group of the aforementioned (A3) allyl resin is preferably directly bonded to the aromatic ring. Moreover, it is preferable that this (A3) allyl resin has a hydroxyl group, and this hydroxyl group is directly bonded to an aromatic ring. The allyl resin in this embodiment is represented by following general formula (11).
Figure 02_image023
In the aforementioned general formula (11), R 9 and R 10 are each independently an alkyl group, preferably an alkyl group with 1 to 10 carbons, more preferably an alkyl group with 1 to 4 carbons, and more preferably an alkyl group selected from the group consisting of Alkyl in the group formed by radical and ethyl. In the aforementioned general formula (11), n 12 is from 1 to 4, preferably from 1 to 3, more preferably from 1 to 2. Also, in the allyl resin represented by the aforementioned general formula (11), it is preferable that the ratio of the component whose n 12 is 1 is 90 mol % or more. As (A3) allyl resin in this embodiment, the allylphenol resin represented by the said general formula (11) is preferable. Among the compounds represented by the aforementioned general formula (11), preferred is a 4-hydroxyphenyl group having a hydroxyl group at the 4-position of the phenyl group. Also, among the compounds represented by the aforementioned general formula (11), it is preferable to have an allyl group at the 3- or 5-position of the phenyl group. Moreover, among the compounds represented by the aforementioned general formula (11), it is preferable to have a hydroxyl group at the ortho-position of the allyl group. Furthermore, among the compounds represented by the aforementioned general formula (11), diallyl bisphenol A (2,2-bis(3-allyl-4-hydroxyphenyl)propane) is particularly preferred. These allyl resins may be used alone or in combination of two or more. By using the aforementioned (A1), (A2) and (A3) as the (A) resin component, three-dimensional reticulation proceeds when heated, and a cured resin having desired physical properties can be obtained. (A4) Other resin components The (A) resin component of the present embodiment may contain (A4) other resin components (hereinafter, referred to simply as "(A4)"). (A4) Other resin components include thermosetting resins other than (A1), (A2) and (A3), thermoplastic resins, crosslinking agents, and the like. By using (A4) other resin components, the peel strength of the resin sheet after hardening can be improved, and the heat resistance of the resin sheet can be improved by bonding with (A1), (A2), (A3) or other components, or the resin sheet can be improved. Handling or sheet forming. As said thermosetting resin, a phenol resin, an epoxy resin, a benzoxazine resin, a cyanate resin, a melamine resin, etc. are mentioned, for example. These thermosetting resins may be used alone or in combination of two or more. By using a thermosetting resin as (A4), the peel strength after hardening of a resin sheet can be improved more, and heat resistance can be improved. However, it is preferable that (A) resin component does not contain an epoxy resin substantially from a viewpoint of high heat resistance. As the aforementioned thermoplastic resin, it is possible to select from a wide range of aliphatic or aromatic compounds for the purpose of making it easy to adjust the complex viscosity of the resin sheet before hardening to a desired range, and improving the handleability and sheet formability of the resin sheet. The thermoplastic resin is preferably at least any one selected from the group consisting of phenoxy resins, acrylic resins, methacrylic resins, polyester resins, urethane resins, and polyamideimide resins. The resin is more preferably at least one resin selected from the group consisting of phenoxy resins and polyamideimide resins from the viewpoint of heat resistance. Furthermore, the polyester resin is preferably a wholly aromatic polyester resin. Also, as the polyamideimide resin, from the viewpoint of improving the flexibility of the resin sheet, a rubber-modified polyamideimide resin is preferable. The thermoplastic resins may be used alone or in combination of two or more. As the phenoxy resin, it is preferable to have a skeleton selected from bisphenol A (hereinafter, bisphenol A may be referred to as "BisA"), a bisphenol F skeleton (hereinafter, bisphenol F may be referred to as "BisF"). case), a phenoxy resin having at least one skeleton in the group consisting of a biphenyl skeleton and a naphthalene skeleton, more preferably a phenoxy resin having a bisphenol A skeleton and a bisphenol F skeleton. The weight average molecular weight (Mw) of the thermoplastic resin is preferably from 10,000 to 1,000,000, more preferably from 15,000 to 800,000, and still more preferably from 20,000, from the viewpoint of making it easy to adjust the complex viscosity of the resin sheet to a desired range. Above 500,000 and below. The weight average molecular weight in this specification is the standard polystyrene conversion value measured by the gel permeation chromatography (Gel Permeation Chromatography; GPC) method. In this embodiment, when a thermoplastic resin is used as (A4), its content is based on the total amount of the solid content of the resin composition (that is, when the total amount of the non-volatile matter of the resin composition excluding the solvent is defined as 100% by mass) , preferably at least 1.5% by mass, more preferably at least 2% by mass. The upper limit of the content of the resin composition is preferably at most 50% by mass, more preferably at most 30% by mass, and most preferably at most 15% by mass. By setting the content of the thermoplastic resin within the above-mentioned range, film-forming properties can be imparted, and the resin composition can be easily formed into a sheet shape. The thermoplastic resin may have a functional group because it has the function of bonding (A1), (A2), (A3) or other components. In this way, when a thermoplastic resin has a functional group, it may have thermoplasticity, and may also have thermosetting properties. As said crosslinking agent, an organic polyvalent isocyanate compound etc. are mentioned, for example. A crosslinking agent can be used individually by 1 type, or in combination of 2 or more types. By using a cross-linking agent, it can be bonded with (A1), (A2), (A3) or other components to improve the handleability, sheet formability, and heat resistance of the resin sheet, or to adjust the initial adhesion of the resin sheet before curing. sex and cohesion. Examples of the organic polyvalent isocyanate compound include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, trimers of these polyvalent isocyanate compounds, and combinations of these polyvalent isocyanate compounds. Terminal isocyanate urethane prepolymers obtained by reacting valent isocyanate compounds with polyol compounds, etc. As further specific examples of organic polyvalent isocyanate compounds, for example, 2,4-mylene diisocyanate, 2,6-mylene diisocyanate, 1,3-xylene diisocyanate, 1,4 -Xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate , isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate and lysine isocyanate, etc. The organic polyvalent isocyanate compound may be used alone or in combination of two or more. When using the above-mentioned cross-linking agent, the content of the cross-linking agent is preferably 0.01 mass part or more, more preferably 0.1 mass part with respect to 100 mass parts of the total amount of the above-mentioned (A1), (A2) and (A3). above. The upper limit of the content of the crosslinking agent is preferably at most 12 parts by mass, more preferably at most 10 parts by mass. In this embodiment, the content of the (A) resin component in the resin composition is based on the total amount of the solid content of the resin composition (that is, the total amount of the non-volatile matter of the resin composition excluding the solvent is set as 100 mass % ), preferably at least 2% by mass, more preferably at least 5% by mass, particularly preferably at least 10% by mass. Moreover, the upper limit of the content of the (A) resin component is preferably at most 75% by mass, more preferably at most 60% by mass, particularly preferably at most 40% by mass. When the content of the (A) resin component is within the above range, the handleability of the resin sheet, the sheet shape maintenance property, and the heat resistance of the resin composition can be improved. (B) Adhesive Imparting Agent In this embodiment, it is preferable that the resin composition further contains (B) an adhesive imparting agent (hereinafter, it may be simply referred to as "(B)"). With this (B) adhesion imparting agent, the peeling strength after hardening of a resin composition can be improved further. As (B) adhesiveness imparting agent, the compound which has (B1) triazine frame|skeleton, or (B2) coupling agent is mentioned, for example. (B1) Compound having a triazine skeleton As (B1) a compound having a triazine skeleton (hereinafter, sometimes simply referred to as "(B1)"), the following compounds are preferable. That is, (B1) is preferably a compound having a basic group in one molecule and a triazine skeleton, more preferably a compound having a nitrogen-containing heterocycle in one molecule and a triazine skeleton, more preferably A compound having a triazine skeleton and an imidazole structure in one molecule. As a compound which has a triazine skeleton and an imidazole structure, the compound represented by following general formula (12) is mentioned, for example.
Figure 02_image025
In the aforementioned general formula (12), R 11 and R 12 are each independently a hydrogen atom, an alkyl group with 1 to 20 carbons, a hydroxymethyl group or a phenyl group, preferably a hydrogen atom or an alkane with 1 to 10 carbons. group, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R 13 is a hydrogen atom, an alkyl group with 1 to 20 carbons, phenyl or allyl, preferably an alkyl group with 1 to 10 carbons, more preferably an alkyl group with 1 to 3 carbons. L 6 is an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms, and more preferably a vinyl group. As the imidazole compound having a triazine skeleton in this embodiment, specifically, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1, 3,5-triazine, 2,4-diamino-6-[2-(2-ethyl-4-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, and 2,4-diamino-6-[2-(2-undecyl-1-imidazolyl)ethyl]-1,3,5-triazine and the like. Among these compounds, 2,4-diamino-6-[2-(2-methyl-1-imidazolyl) is preferred from the viewpoint of the peel strength of the resin composition and the resin sheet and the reaction temperature. )ethyl]-1,3,5-triazine, or 2,4-diamino-6-[2-(2-ethyl-4-methyl-1-imidazolyl)ethyl]-1, 3,5-Triazine. (B2) Coupling agent As (B2) coupling agent (hereinafter, sometimes simply referred to as "(B2)"), the following compounds are preferable. (B2) The coupling agent preferably has a group that reacts with the functional group contained in the compound contained in the aforementioned (A) resin component. By using the (B2) coupling agent, the peeling strength between the cured product of the resin sheet and the object to be adhered is improved. As the (B2) coupling agent, silane-based (silane coupling agent) is preferable from the viewpoint of the ease of handling. (B2) The coupling agents may be used alone or in combination of two or more. Examples of the silane coupling agent include silane coupling agents having an amino group, silane coupling agents having a mercapto group, and silane coupling agents having an epoxy group. As the silane coupling agent having an amino group, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyltrimethoxysilane, Aminopropyldiethoxymethylsilane, [3-(N,N-Dimethylamino)propyl]trimethoxysilane, [3-(Phenylamino)propyl]trimethoxysilane wait. Examples of the silane coupling agent having a mercapto group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropyldimethoxymethylsilane. Examples of silane coupling agents having epoxy groups include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyl Methoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. Among these compounds, from the viewpoint of the peel strength of the resin composition and the resin sheet, a silane coupling agent having an epoxy group is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. (B) The total content of (B) the adhesion imparting agent is 0.1 mass parts or more with respect to 100 mass parts of total content of (A) and (B), Preferably it is 0.1 mass parts or more of (B), More preferably, it is 0.5 mass parts or more, More preferably, it is 1.0 parts by mass or more. Moreover, it is preferably at most 15 parts by mass, more preferably at most 12 parts by mass, and still more preferably at most 8 parts by mass. By setting it as such a range, the peeling strength between the hardened|cured material of a resin sheet, and a to-be-attached body can be improved. (B) It is more preferable to use (B1) the compound which has a triazine frame|skeleton, and (B2) coupling agent together as an adhesiveness imparting agent. By using them in combination, the peel strength after hardening of the resin composition can be further improved. When using (B1) a compound having a triazine skeleton as the (B) adhesion imparting agent, the content of (B1) is preferably 0.1 parts by mass or more based on 100 parts by mass of the total content of (A) and (B), More preferably, it is 0.5 mass part or more, More preferably, it is 1.0 mass part or more. Moreover, it is preferably at most 15 parts by mass, more preferably at most 12 parts by mass, and still more preferably at most 8 parts by mass. By setting it in such a range, the peeling strength between the hardened|hardened resin sheet and a to-be-attached body improves. When using the (B2) coupling agent as the (B) adhesion imparting agent, the content of (B2) is preferably 0.05 mass parts or more with respect to 100 mass parts of the total content of (A) and (B), more preferably 0.10 parts by mass or more, more preferably 0.50 parts by mass or more. Moreover, it is preferably at most 10 parts by mass, more preferably at most 8 parts by mass, and still more preferably at most 5 parts by mass. By setting it in such a range, the peeling strength between the hardened|hardened resin sheet and a to-be-attached body improves. (C) Thermally conductive filler In this embodiment, the resin composition contains (C) a thermally conductive filler (hereinafter, may be simply referred to as "(C)") in addition to (A) and (B). According to this (C), at least one of the thermal characteristic and mechanical characteristic of a resin composition can be improved. Examples of the (C) thermally conductive filler include boron nitride particles, alumina particles, and the like. Among these, (C1) boron nitride particles (hereinafter, may be referred to simply as "(C1)"), and (C2) alumina particles (hereinafter, may be referred to simply as "(C2)"), It is preferable from the viewpoint of increasing the thermal diffusivity of the resin sheet. (C) The thermally conductive filler may be used alone or in combination of two or more. Also, (C) the thermally conductive filler may be surface-treated. (C) The average particle diameter of the thermally conductive filler is not particularly limited. (C1) The average particle size of the boron nitride particles is preferably at least 0.1 μm, more preferably at least 0.2 μm, and still more preferably at least 0.3 μm, as a value of d50. Also, the upper limit of the average particle size of the (C1) boron nitride particles is preferably at most 30 μm, more preferably at most 20 μm, and still more preferably at most 15 μm. Also, the average particle diameter of the alumina particles (C2) is preferably at least 3 μm, more preferably at least 4 μm, as a value of d50. Also, the upper limit of the average particle size of the (C2) alumina particles is preferably at most 50 μm, more preferably at most 35 μm, even more preferably at most 25 μm. Also, (C) the thermally conductive filler may have a plurality of peaks in the particle size distribution. At this time, it was judged that the (C) thermally conductive filler of a different type was mixed for every peak value. For example, when there are three peaks in the particle size distribution, it can be judged that three types of (C) thermally conductive fillers are mixed. The (C) average particle size of the thermally conductive filler in this specification is defined as a value measured by a dynamic light scattering method. The total content of (C1) boron nitride particles and (C2) alumina particles in the resin composition is based on the total amount of the solid content of the resin composition (that is, the non-volatile content of the resin composition excluding the solvent When the total amount is 100% by mass), preferably at least 50% by mass, more preferably at least 65% by mass, more preferably at least 70% by mass, particularly preferably at least 75% by mass. The heat diffusivity of a resin sheet can be raised by making the total of content of (C1) and (C2) in a resin composition more than the said minimum. Moreover, the upper limit of the sum of these contents is preferably at most 90% by mass, more preferably at most 88% by mass, still more preferably at most 86% by mass, and most preferably at most 84% by mass. The heat diffusivity of a resin sheet can be raised by making the total of content of (C1) and (C2) in a resin composition below the said upper limit. When the resin composition contains both (C1) boron nitride particles and (C2) alumina particles, the mass ratio of (C1) boron nitride particles to (C2) alumina particles in the resin composition is such that (C2) is oxidized When the mass of the aluminum particles is 1, the mass of the (C1) boron nitride particles is preferably 0.1 or more, more preferably 0.2 or more. By making mass ratio more than the said minimum, the thermal diffusivity of a resin sheet can be raised. Also, when the above-mentioned resin composition contains both (C1) boron nitride particles and (C2) alumina particles, the mass ratio of (C1) boron nitride particles to (C2) alumina particles in the resin composition is more than The limit value is preferably at most 0.75, more preferably at most 0.6. By making mass ratio below the said upper limit, the peeling strength after the thermosetting of a resin sheet can be improved. The content of (C) thermally conductive filler in the resin composition is based on the total amount of the solid content of the resin composition (that is, when the total amount of non-volatile matter in the resin composition excluding the solvent is set as 100% by mass), compared with Preferably it is at least 50% by mass, more preferably at least 65% by mass, still more preferably at least 70% by mass, and most preferably at least 75% by mass. By making content of the (C) thermally conductive filler in a resin composition more than the said minimum, the thermal diffusivity of a resin sheet can be raised. Also, the upper limit of the content of (C) the thermally conductive filler is preferably at most 90% by mass, more preferably at most 88% by mass, still more preferably at most 86% by mass, particularly preferably at most 84% by mass. By making content of (C) thermally conductive filler in a resin composition below the said upper limit, the peeling strength after the thermosetting of a resin sheet can be improved. (D) Curing catalyst In the resin sheet according to the present embodiment, when the resin composition contains a resin component, a (D) curing catalyst may be further contained as long as the object of the present invention is not impaired. Thereby, it becomes possible to efficiently progress the hardening reaction of the resin component, and it becomes possible to harden the resin sheet favorably. Examples of the curing catalyst include imidazole-based curing catalysts, amine-based curing catalysts, phosphorus-based curing catalysts, triazole-based curing catalysts, thiazole-based curing catalysts, and radical polymerization initiators. Specific examples of imidazole-based hardening catalysts include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl- 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl- 2-Methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenyl For imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2-phenyl-4,5-bis(hydroxymethyl)imidazole, it is preferable to use 2 -Ethyl-4-methylimidazole. Furthermore, when a compound having a triazine skeleton and an imidazole structure is used as the aforementioned (B) adhesion imparting agent, it can also be used as a curing catalyst. Specific examples of amine-based hardening catalysts include 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1,4-diazabicyclo[2.2.2 ]octane, and N,N-dimethylbenzylamine triethylamine and other tertiary amine compounds. Specific examples of the phosphorus-based curing catalyst include triphenylphosphine, tributylphosphine, tri(p-methylphenyl)phosphine, and tri(nonylphenyl)phosphine. Specific examples of the triazole-based curing catalyst include benzotriazole-based compounds and the like. Specific examples of the thiazole-based curing catalyst include benzothiazole-based compounds and the like. Specific examples of the radical polymerization initiator include peroxides, azo compounds, and the like. These (D) hardening catalysts can be used individually by 1 type, or in combination of 2 or more types. When (D) hardening catalyst is used, when the total content of (A) is 100 parts by mass, it is preferably not more than 15 parts by mass, more preferably not more than 12 parts by mass, most preferably not more than 8 parts by mass . (E) Other components In this embodiment, the resin composition may further contain (E) other components as long as the object of this invention is not impaired. (E) Other components include, for example, those selected from the group consisting of coloring materials, antifoaming agents, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, ion trapping agents, and ion trapping agents. at least one of the ingredients. These (E) other components can be used individually by 1 type, or in combination of 2 or more types. When (E) other components are used, when these content makes total content of (A) 100 mass parts, Preferably it is 10 mass parts, More preferably, it is 5 mass parts or less. In the present embodiment, when the resin sheet is formed by coating, the resin composition preferably contains a solvent. As the solvent, in addition to general solvents such as toluene, ethyl acetate, and methyl ethyl ketone, cyclohexanone (boiling point: 155.6° C.), dimethylformamide (boiling point: 153° C.), High boiling point solvents such as methylsulfone (boiling point: 189.0°C), ethylene glycol ethers (cellosolve) (boiling point: around 120-310°C), ortho-xylene (boiling point: 144.4°C), etc. [Resin Sheet] The resin sheet of this embodiment is formed from the aforementioned resin composition of this embodiment. The resin sheet is preferably made of only the resin related to this embodiment from the viewpoint of conformability to unevenness of an attached substrate when it is used to seal a semiconductor element or interposed between a semiconductor element and other electronic parts. composed of components. That is, the resin sheet is preferably a composite material such as a prepreg rather than a composite material such as a combination of a resin composition and a fiber sheet. In the resin sheet of this embodiment, when the number of types of (C) thermally conductive fillers is defined as n, the ratio of (C) thermally conductive fillers represented by the following formula (F1) to the critical filling amount must be 0.95. The above is below 1.26.
Figure 02_image027
V n : the volume filling rate of the nth type of thermally conductive filler among (C) thermally conductive fillers CV n : the critical volume filling rate of the nth type of thermally conductive filler among (C) thermally conductive fillers, more specifically In the formula (F1), when the critical filling amount ratio n is 1, it is represented by the following formula (F1-1).
Figure 02_image029
When n is 2, it represents with the following numerical formula (F1-2).
Figure 02_image031
When n is 3, it represents with the following numerical formula (F1-3).
Figure 02_image033
When the ratio to the critical filling amount is less than 0.95, the thermal conductivity decreases. On the other hand, when the ratio of the critical filling amount exceeds 1.26, voids in the resin sheet are generated, which adversely affects the adhesiveness. Also, from the same viewpoint, the critical filling amount is preferably at least 1, more preferably at least 1.04, and most preferably at least 1.1. Also, the upper limit of the ratio to the critical filling amount is preferably at most 1.25, more preferably at most 1.23, and most preferably at most 1.2. The above-mentioned value of V n can be calculated as follows. That is, the filler volume occupied by the nth type (C) thermally conductive filler is calculated from the content of the nth type (C) thermally conductive filler in the resin composition and its specific gravity. Also, the composition volume occupied by the resin composition was calculated from the content of (C) and the content of organic components (components other than (C)) in the resin composition, and their specific gravity. And, the value of V n is calculated by the following formula (F2). V n = (filler volume of the nth type)/(composition volume)×100･･･(F2) The value of the above CV n can be measured as follows. That is, prepare a resin composition in which the volume filling rate of each thermally conductive filler is varied by 1% (this resin composition is composed of the nth type of thermally conductive filler and an organic component), and use these For the resin composition, make resin sheets separately. Next, the surface of these resin sheets was observed with a laser microscope (observation area: 1mm x 1mm), and the presence or absence of voids with a minor axis of 20 μm or more and a major axis of 20 μm or more was confirmed (see FIGS. 2 and 3 ). Still, there are gaps in the black parts observed in Fig. 2(B) and Fig. 3(B). In FIG. 2(B) and FIG. 3(B), since the critical volume filling rate has been exceeded, a large number of voids are observed. When observing sequentially from resin sheets with low volume filling ratios, a value 1% smaller than the volume filling ratio of the resin sheet with two or more voids confirmed for the first time was defined as the value of CV n . In the resin sheet related to this embodiment, the filler volume filling rate of (C) is preferably not less than 50% and not more than 65%. If the filler volume filling rate is more than 50%, the thermal conductivity can be further improved. On the other hand, if the filler volume filling rate is below 65%, the adhesiveness of the resin sheet can be improved. Also, from the same viewpoint, the filler volume filling rate is preferably at least 52%, more preferably at least 55%. Also, the upper limit of the filler volume filling rate is preferably 64% or less, more preferably 62% or less. The filler volume filling rate can be calculated as follows. That is, the filler volume occupied by (C) is calculated from the content of (C) in the resin composition and the specific gravity thereof. Also, when (C) is composed of n types of (C) thermally conductive fillers, from the filler volume occupied by the first type of (C) thermally conductive filler to the volume occupied by the nth type of (C) thermally conductive filler The total up to the filler volume is the filler volume. Also, the composition volume occupied by the resin composition was calculated from the content of (C) and the content of organic components (components other than (C)) in the resin composition, and their specific gravity. Also, the specific gravity of boron nitride particles, alumina particles and organic components is as above. And, the filler volume filling rate of (C) was calculated by the following formula (F3). (filler volume filling rate)=(filler volume)/(composition volume)×100･･･(F3) The thermal diffusivity of the resin sheet related to this embodiment after thermosetting must be 1.0×10 -6 m 2 /s or more, preferably 1.1×10 -6 m 2 /s or more, more preferably 1.2×10 -6 m 2 /s or more, more preferably 1.3×10 -6 m 2 /s or more, and still more It is preferably at least 1.35×10 -6 m 2 /s, and particularly preferably at least 1.5×10 -6 m 2 /s. Also, the upper limit of thermal diffusivity after thermosetting is preferably at most 1×10 -5 m 2 /s, more preferably at most 8×10 -6 m 2 /s, still more preferably at most 5×10 -6 m 2 /s or less, more preferably 4×10 -6 m 2 /s or less, most preferably 3×10 -6 m 2 /s or less. With the thermal diffusivity of the resin sheet after thermosetting within such a range, a cured product having high thermal conductivity can be obtained. The thermal diffusivity of the resin sheet after thermosetting is a characteristic value obtained by the method described in the examples described later. Also, the peel strength after thermosetting of the resin sheet related to this embodiment is preferably more than 2.0N/10mm, more preferably 3.0N/10mm or more, more preferably 5.0N/10mm or more, and most preferably 6.0N/10mm or more. More than 10mm. Moreover, the upper limit of the peel strength after thermosetting is more preferably 50 N/10 mm or less, and still more preferably 40 N/10 mm or less. If the peel strength after thermosetting of the resin sheet according to this embodiment exceeds 2.0 N/10mm, when the resin sheet is used as a sealing material, high adhesiveness can be maintained for the substrate. The peel strength after thermosetting of the resin sheet of this embodiment can be adjusted to the above-mentioned range by adjusting the types (particularly types of hardening accelerators) and blending amounts of components used in the resin composition, for example. Furthermore, the peel strength after thermosetting of the resin sheet according to this embodiment was obtained by performing a peeling test at a peeling angle of 90 degrees between the resin sheet after thermosetting and the object to be adhered using the measuring method described later. Specifically, as described in the Examples, a test piece was prepared and a peeling test was performed. In the resin sheet according to this embodiment, application to a substrate is facilitated by thinning the resin composition, especially when the substrate has a large area. If the resin composition is in the form of a sheet, since it is preliminarily formed into a shape suitable for the shape after the sealing step, it is only suitable and can be supplied as a sealing material that maintains a certain degree of uniformity. In addition, when the resin composition is in the form of flakes, the handleability is excellent. The method for exfoliating the resin composition may be a conventionally known exfoliating method, and is not particularly limited. From the viewpoint of easily obtaining a thin resin sheet, the resin sheet is preferably a coating film of a resin composition. The resin sheet of the coating film of the resin composition can be obtained by a production method including the step of coating the aforementioned resin composition. Here, it does not specifically limit as a coating method, A well-known method can be used. In addition, after coating, drying may be performed if necessary. The drying conditions are not particularly limited as long as the aforementioned resin composition is not cured. The resin sheet according to this embodiment may be a belt-shaped sheet, or may be provided in a roll-shaped state. The resin sheet according to the present embodiment wound into a roll can be used by pulling out from the roll and cutting it into a desired size. The thickness of the resin sheet in this embodiment is, for example, preferably at least 10 μm, more preferably at least 20 μm, and still more preferably at least 30 μm. Also, the thickness is preferably not more than 200 μm, more preferably not more than 150 μm, and still more preferably not more than 120 μm. In addition, when the resin sheet is a coating film of a resin composition, thinning of the resin sheet is easy, and the thickness of the resin sheet according to this embodiment is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less. (Thermosetting conditions) In the thermosetting conditions of the resin sheet according to this embodiment, the heating temperature is preferably at least 50°C, more preferably at least 100°C, still more preferably at least 130°C, and still more preferably at least 160°C. above. Also, the upper limit of the heating temperature is preferably at most 300°C, more preferably at most 250°C, still more preferably at most 230°C, and still more preferably at most 210°C. In the thermosetting conditions of the resin sheet according to this embodiment, the heating time is preferably at least 10 minutes, more preferably at least 20 minutes. Also, the upper limit of the heating time is preferably at most 10 hours, more preferably at most 7 hours. When the thermosetting conditions of the resin sheet are within the above-mentioned range, thermosetting of the resin sheet at low temperature and in a short time can be realized. [Laminate] Fig. 1 shows a schematic cross-sectional view of a laminate 1 according to the present embodiment. The laminated body 1 of this embodiment has the 1st release material 2, the 2nd release material 4, and the resin sheet 3 provided between the 1st release material 2 and the 2nd release material 4. The resin sheet 3 is the resin sheet related to this embodiment. The first release material 2 and the second release material 4 are preferably releasable, and there is a difference between the release force of the resin sheet 3 relative to the first release material 2 and the release force of the resin sheet 3 relative to the second release material 4 . The materials of the first release material 2 and the second release material 4 are not particularly limited. The ratio (P2/P1) of the peel force P2 of the second release material 4 to the peel force P1 of the first release material 2 is preferably 0.02≦P2/P1<1 or 1<P2/P1≦50. The first release material 2 and the second release material 4 may be, for example, a member subjected to a release treatment or a member laminated with a release agent layer, in addition to the release material itself being a releasable member. When the first release material 2 and the second release material 4 are not subjected to the release treatment, the material of the first release material 2 and the second release material 4 includes, for example, olefin-based resins, fluororesins, and the like. The first release material 2 and the second release material 4 may be a release material including a release base material and a release agent layer formed by coating a release agent on the release base material. Handling is facilitated by being a release material having a release base material and a release agent layer. Moreover, the 1st release material 2 and the 2nd release material 4 may be equipped with the release agent layer only in the one surface of a release base material, and may be provided with the release agent layer on both surfaces of a release base material. Examples of the release base include paper bases, laminated papers and plastic films in which thermoplastic resins such as polyethylene are laminated on the paper bases. As a paper base material, cellophane, coated paper, cast-coated paper, etc. are mentioned, for example. Examples of plastic films include polyester films (such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, etc.), and polyolefin films (such as polypropylene and polyethylene vinyl, etc.) etc. Among these, a polyester film is preferable. Examples of release agents include silicone-based release agents composed of silicone resins; polyvinyl urethane (Carbamate), and alkyl urea derivatives, which are composed of compounds containing long-chain alkyl groups. Compound-based release agents containing long-chain alkyl groups; alkyd resin-based release agents composed of alkyd resins (such as non-transforming alkyd resins and converted alkyd resins, etc.); olefin resins (such as polyethylene (such as high high-density polyethylene, low-density polyethylene and linear low-density polyethylene, etc.), isotactic structure, or a single polymer of propylene with a syndiotactic structure, and crystals of propylene-α-olefin copolymers, etc. Olefin resin-based release agent composed of permanent polypropylene resin, etc.); natural rubber and synthetic rubber (such as butadiene rubber, isoprene rubber, styrene-butadiene rubber, methyl methacrylate-butadiene rubber) Various release agents such as rubber-based release agents composed of rubber such as diene rubber and acrylonitrile-butadiene rubber; and acrylic resin-based release agents composed of acrylic resins such as (meth)acrylate copolymers , These may be used alone or in combination of two or more. Among them, an alkyd resin-based release agent is preferable. In particular, when a phenoxy resin is used as the (B) binder component of the resin composition contained in the resin sheet 3, when a general silicone-based release agent is used, the release material may be attached to the resin sheet 3. There is no risk of deliberate peeling before use, so it is preferable to use an alkyd resin-based peeling agent. The thicknesses of the first release material 2 and the second release material 4 are not particularly limited. Usually, it is not less than 1 μm and not more than 500 μm, preferably not less than 3 μm and not more than 100 μm. The thickness of the release agent layer is not particularly limited. When a solution containing a release agent is applied to form a release agent layer, the thickness of the release agent layer is preferably from 0.01 μm to 3 μm, more preferably from 0.03 μm to 1 μm. The method for producing the laminate 1 is not particularly limited. For example, the laminated body 1 is produced through the following steps. First, the resin composition is coated on the first release material 2 to form a coating film. Next, this coating film is dried to form a resin sheet 3 . Next, the laminated body 1 was obtained by bonding the resin sheet 3 and the 2nd release material 4 together at room temperature. In this case, when the first release material 2 and the second release material 4 are of the same type, the ratio of the release force P2 of the second release material 4 to the release force P1 of the first release material 2 ( P2/P1), the possibility of becoming P2/P1<1 is high, even if the release materials of the first release material 2 and the second release material 4 are of different types, by coating the resin composition as the first release material 2, there is Tendency to shrink the value of P2/P1. [Effects of the present embodiment] According to the resin sheet and the laminated body of the present embodiment, the thermal conductivity of the resin sheet excellent in heat resistance after thermosetting can also be improved, and the adhesiveness after thermosetting can be further improved. As described above, the resin sheet according to this embodiment can be suitably used for power semiconductor devices. In other words, in the semiconductor device according to this embodiment, the semiconductor element is preferably a power semiconductor element. Power semiconductor devices are also assumed to operate at high temperatures above 200°C. Heat resistance is required for materials used in semiconductor devices having power semiconductor elements. Since the resin sheet according to this embodiment has excellent heat resistance, it is suitable for use in semiconductor devices: it is used to cover power semiconductor elements, or to be interposed between power semiconductor elements and other components. Moreover, it is preferable that the resin sheet concerning this embodiment is applied to several semiconductor elements at once. For example, if the resin composition is in the form of a sheet, a so-called panel-level package can be used to seal the frame and the semiconductor element at once by applying the resin sheet to each gap of the frame provided with a plurality of gaps, and applying the resin sheet to the structure in which the semiconductor element is placed. Also, the sealing of the semiconductor element may be coating for protecting the back surface of the flip-chip type element. In a general protective sheet, heat generated from the device is blocked and heat is relatively accumulated in the device. By using the resin sheet related to this embodiment as a backside protection sheet of a flip-chip type device, it is possible to efficiently to dissipate the heat generated from the components. Furthermore, since the resin sheet according to this embodiment has excellent thermal conductivity after thermosetting, heat generated from the power semiconductor element can be efficiently transferred to the heat sink or the like. That is, since the resin sheet according to this embodiment is excellent in heat resistance and thermal conductivity, it can be used to seal a power semiconductor element that operates at a high temperature of 200°C or higher, or to be interposed between a power semiconductor element and other electronic parts to transfer power from Excellent ability to conduct heat generated by semiconductor elements to heat sinks and the like. As described above, the resin sheet according to this embodiment can be suitably used for semiconductor elements using compound semiconductors. In other words, in the semiconductor device according to this embodiment, the semiconductor element is preferably a semiconductor element using a compound semiconductor. Semiconductor elements using compound semiconductors have different characteristics from silicon semiconductor elements, so they are preferably used in power semiconductor elements, high-output devices for local use in base stations, sensors, detectors, and Schottky diodes. In these applications, the heat resistance of semiconductor elements using compound semiconductors is also important. The resin sheet of this embodiment is excellent in heat resistance and is suitable for use in combination with semiconductor elements using compound semiconductors. Furthermore, since the resin sheet according to this embodiment has excellent thermal conductivity after thermosetting, it can efficiently conduct heat generated from a semiconductor element using a compound semiconductor to a heat sink or the like. Also, the resin sheet according to this embodiment is preferably used for sealing a semiconductor element using a compound semiconductor. Or the resin sheet according to this embodiment is preferably used between a semiconductor element using a compound semiconductor and other electronic parts. As another electronic component, a printed wiring board, a lead frame, etc. are mentioned, for example. Since the upper limit of the operating temperature of the silicon semiconductor element is about 175°C, it is preferable to use a semiconductor element that uses a compound semiconductor that can operate at a high temperature among power semiconductor elements. Examples of compound semiconductors include silicon carbide, gallium nitride, aluminum gallium nitride, gallium oxide, gallium arsenic, and the like, preferably one or more of silicon carbide, gallium nitride, aluminum gallium nitride, and gallium oxide. The resin sheet according to this embodiment is excellent in heat resistance and thermal conductivity, so it can be used to seal a semiconductor element using a compound semiconductor operating at a high temperature assumed to be 200°C or higher, or to intervene between a semiconductor element using a compound semiconductor and other electronic parts, Excellent ability to conduct heat generated from these power semiconductor elements to heat sinks and the like. [Modifications of Embodiments] The present invention is not limited to the aforementioned embodiments, and modifications, improvements, and the like within the scope of achieving the object of the present invention are included in the present invention. In the above-mentioned embodiment, although the laminated body having the first release material, the second release material, and the resin sheet disposed between the first release material and the second release material is described, the other may be only the resin sheet. One side of the sheet has a laminate of release materials. Also, in the embodiment of the aforementioned semiconductor device, although the semiconductor sealing application is described, the resin sheet of the present invention can also be used as an insulating material for a circuit board (for example, a material for a hard printed wiring board, a material for a flexible wiring board, and interlayer insulation materials for stacking substrates, etc.), adhesive films for stacking, and adhesives. EXAMPLES Hereafter, an Example is given and this invention is demonstrated in more detail. The present invention is not limited by these embodiments. [Examples and Comparative Examples] [Preparation of Resin Composition] In the blending ratio shown in Table 1 (% by mass (ratio in terms of solid content)), each component was dissolved or dispersed in a solvent to prepare related examples. 1-3 and the resin compositions of Comparative Examples 1-3. Also, the contents of (A), (B) and (C) in Examples and Comparative Examples are shown in Table 1. The materials used in the preparation of the resin composition are as follows. (A) Resin component 1st maleimide resin-1: long-chain alkyl type maleimide resin (maleimide resin represented by the general formula (5) above which is solid at a temperature of 25°C ) ･First maleimide resin-2: long-chain alkyl type maleimide resin (maleimide resin represented by the aforementioned general formula (7) which is liquid at a temperature of 25°C) ･No. 2 Maleimide resin: maleimide resin having a biphenyl group (maleimide resin represented by general formula (9) above, "MIR-3000" manufactured by Nippon Kayaku Co., Ltd.) ･ene Propyl resin: Diallyl bisphenol A ("DABPA" manufactured by Daiwa Chemical Industry Co., Ltd.) (B) Adhesion Imparting Agent・Compound having a triazine skeleton (triazine compound): 2,4-diamine Ethyl-6-[2-(2-ethyl-4-methyl-1-imidazolyl)ethyl]-1,3,5-triazine ("2E4MZ-A" manufactured by Shikoku Chemical Industry Co., Ltd.) ･Coupling agent: 3-glycidoxypropyltriethoxysilane (C) Thermally conductive filler ･Alumina particles: ("CB-A20S" manufactured by Showa Denko Co., Ltd., average particle size (d50): 20μm) ･Boron Nitride Particle-1: ("UHP-2" manufactured by Showa Denko Co., Ltd., average particle size (d50): 11μm) ･Boron Nitride Particle-2: ("UHP-S2" manufactured by Showa Denko Co., Ltd. , average particle size (d50): 0.7 μm) [Preparation of a laminate including a resin sheet] On the first release material (polyethylene terephthalate film with a release layer formed from an alkyd resin release agent) , thickness 38μm), coated resin varnish (coating solution prepared by dissolving the resin composition in cyclohexanone, the solid content concentration is set to 72% by mass) with a knife coater, dried at 90°C for 1 minute and dried at 115°C °C for 1 minute. The thickness of the resin composition after drying is shown in Table 1. Immediately after taking it out of the drying oven, place the dried resin composition and the second release material (polyethylene terephthalate film with a release layer formed from a silicone release agent, thickness 38 μm) at room temperature Laminating, and making a laminated body in which the first release material, the resin sheet made of the resin composition, and the second release material are laminated in sequence. <Confirmation and evaluation of physical properties of resin flakes> [Filler volume filling rate of resin flakes] Calculate the filler volume occupied by (C) from the content of (C) in the resin composition and their specific gravity. Still, in this embodiment etc., since the three types (C) of alumina particles, boron nitride particles-1 and boron nitride particles-2 are used, the filler volume occupied by alumina particles and boron nitride particles- The sum of the filler volume occupied by 1 and the filler volume occupied by boron nitride particles-2 is the filler volume. Also, the composition volume occupied by the resin composition was calculated from the content of (C) and the content of the organic component (total of (A) and (B)) in the resin composition, and their specific gravity. In addition, the specific gravity of boron nitride particles was set at 2.27, and the specific gravity of alumina particles was set at 3.9. In addition, the specific gravity of the organic component was set to 1.2. Then, the filler volume filling rate (the sum of the volume filling rates of all fillers) of (C) was calculated by the following formula (F3). Table 1 shows the obtained results. (Filler Volume Filling Ratio)=(Filler Volume)/(Composition Volume)×100･･･(F3) [Critical Filling Ratio of Resin Flakes] (C) Thermal conductivity represented by the following formula (F1) The ratio of the filler to the critical filling amount is determined by the following measurement or calculation. Table 1 shows the obtained results.
Figure 02_image035
V n : the volume filling rate of the nth type of thermally conductive filler among (C) thermally conductive fillers CV n : the critical volume filling rate of the nth type of thermally conductive filler among (C) thermally conductive fillers, in this implementation For example, since three kinds of (C) of alumina particles, boron nitride particles-1, and boron nitride particles-2 are used, it can be specifically calculated by the following formula (F1-3).
Figure 02_image037
V 1 : Volume filling ratio of alumina particles CV 1 : Critical volume filling ratio of alumina particles V 2 : Volume filling ratio of boron nitride particles-1 CV 2 : Critical volume filling ratio of boron nitride particles-1 V 3 : Volume filling ratio of boron nitride particles-2 CV 3 : Critical volume filling ratio of boron nitride particles-2 The above-mentioned value of V n was calculated as follows. That is, the filler volume occupied by the nth type (C) thermally conductive filler is calculated from the content of the nth type (C) thermally conductive filler in the resin composition and its specific gravity. Also, the composition volume occupied by the resin composition was calculated from the content of (C) and the content of organic components (components other than (C)) in the resin composition, and their specific gravity. Also, the specific gravity of boron nitride particles, alumina particles and organic components is as above. And, the value of V n is calculated by the following formula (F2). V n =(filler volume of nth type)/(composition volume)×100･･･(F2) The above-mentioned value of CV n is measured as follows. That is, prepare a resin composition in which the volume filling rate of each thermally conductive filler is varied by 1% (this resin composition is composed of the nth type of thermally conductive filler and an organic component), and use these For the resin composition, make resin sheets separately. Next, the surface of these resin sheets was observed with a laser microscope (manufactured by KEYENCE Co., Ltd., product name "VK-9500") (observation area: 1mm x 1mm), and it was confirmed that the short axis was 20 μm or more and the long axis was 20 μm or more. The presence or absence of gaps in size. When observing sequentially from resin sheets with low volume filling ratios, a value 1% smaller than the volume filling ratio of the resin sheet with two or more voids confirmed for the first time was defined as the value of CV n . Also, the value of CV n was measured for each of the alumina particles, the boron nitride particles-1, and the boron nitride particles-2. In the measurement of the critical volume filling factor of alumina particles, the photographs of the surface of the resin sheet observed with a laser microscope are shown in FIGS. 2A and 2B . The volume filling rate of the alumina particles in FIG. 2A is 65%, and the volume filling rate of the alumina particles in FIG. 2B is 75%. In the measurement of the critical volume filling factor of the boron nitride particle-1, photographs of the surface of the resin sheet observed with a laser microscope are shown in FIGS. 3A and 3B . The volume filling rate of the boron nitride particles in FIG. 3A is 30%, and the volume filling rate of the boron nitride particles in FIG. 3B is 40%. As a result of the measurement, CV 1 (critical volume filling rate of alumina particles) was 72%, CV 2 (critical volume filling rate of boron nitride particles-1) was 35%, and CV 3 (critical volume filling rate of boron nitride particles-2 Volume filling rate) is 37%. [Thickness of resin sheet] Measured using a constant pressure thickness measuring device manufactured by TECLOCK Co., Ltd. (model: "PG-02J", standard specifications: in accordance with JIS K6783, Z1702, Z1709). Table 1 shows the obtained results. [Measurement of Thermal Diffusivity of Resin Sheets After Thermosetting] Resin sheets were laminated so as to have a thickness of 200 μm, and cured at a temperature of 200° C. under thermosetting conditions for 4 hours to prepare samples. Furthermore, the first release material and the second release material of the laminate are properly removed during the bonding process. With respect to this sample, thermal diffusivity was measured by a temperature wave method using a thermal diffusivity measuring device ("ai-Phase Mobile 1" manufactured by ai-Phase Co., Ltd.). Table 1 shows the obtained results. [Measurement of Peeling Strength] On a copper plate (JIS-C1220P standard, thickness 400 μm), bond one side of the resin sheet of the obtained laminate under reduced pressure at a lamination temperature of 130° C. Pressing device: "V-130" manufactured by Nikko Materials Co., Ltd.; conditions: reaching pressure 100Pa, pressurizing pressure 0.3MPa, time 30 seconds), then, on the other side of the resin sheet, copper foil (size 50 mm x 10 mm, thickness 150 μm, JIS H 3100 standard) are bonded under reduced pressure under the same conditions as above. Furthermore, the second peeling material and the first peeling material of the resin sheet of the laminate were peeled off before bonding to the Si wafer and the copper plate, respectively. Thereafter, the resin sheet was cured at a temperature of 200° C. under thermosetting conditions for 4 hours, and used as a sample. For this sample, using a tensile tester ("AUTOGRAPH AG-IS" manufactured by Shimadzu Corporation), under the conditions of a peeling speed of 50 mm/min and a peeling angle of 90 degrees, the copper foil was peeled from the resin sheet after hardening the copper foil, and the copper was measured. Peel strength between the foil and the cured resin sheet (unit: N/10mm). The measurement was carried out at 25°C and 50% relative humidity. Table 1 shows the obtained results. Also, the sample of Comparative Example 1 was judged as "NG" because the adhesiveness was too low and the peel strength could not be measured.
Figure 02_image039
It is clear from the results shown in Table 1 that the peel strength of the resin sheets obtained in Examples 1 to 3 is within the range of 0.95 to 1.26 with respect to the critical filling amount ratio, and the heat resistance after thermosetting is high. The diffusion rate is high.

1:層合體 2:第一剝離材 3:樹脂薄片 4:第二剝離材 1:Laminate 2: The first peeling material 3: Resin flakes 4: Second peeling material

[圖1]為有關本實施形態之層合體的剖面概略圖。 [圖2A]為為了臨界體積填充率的測定，將樹脂薄片(含有氧化鋁粒子)的表面以雷射顯微鏡觀察之照片(於圖2A之氧化鋁粒子的體積填充率為65%)。 [圖2B]為為了臨界體積填充率的測定，將樹脂薄片(含有氧化鋁粒子)的表面以雷射顯微鏡觀察之照片(於圖2B之氧化鋁粒子的體積填充率為75%)。 [圖3A]為為了臨界體積填充率的測定，將樹脂薄片(含有氮化硼粒子)的表面以雷射顯微鏡觀察之照片(於圖3A之氮化硼粒子的體積填充率為30%)。 [圖3B]為為了臨界體積填充率的測定，將樹脂薄片(含有氮化硼粒子)的表面以雷射顯微鏡觀察之照片(於圖3B之氮化硼粒子的體積填充率為40%)。 [ Fig. 1 ] is a schematic cross-sectional view of a laminate according to this embodiment. [FIG. 2A] is a photo of the surface of a resin sheet (containing alumina particles) observed with a laser microscope for the measurement of the critical volume filling ratio (the volume filling ratio of the alumina particles in FIG. 2A is 65%). [FIG. 2B] is a photo of the surface of the resin sheet (containing alumina particles) observed with a laser microscope for the measurement of the critical volume filling ratio (the volume filling ratio of the alumina particles in FIG. 2B is 75%). [FIG. 3A] is a photograph of observing the surface of a resin sheet (containing boron nitride particles) with a laser microscope for the measurement of critical volume filling ratio (the volume filling ratio of boron nitride particles in FIG. 3A is 30%). [ FIG. 3B ] is a photograph of observing the surface of a resin sheet (containing boron nitride particles) with a laser microscope for the measurement of the critical volume filling rate (the volume filling rate of the boron nitride particles in FIG. 3B is 40%).

1:層合體 1:Laminate

2:第一剝離材 2: The first peeling material

3:樹脂薄片 3: Resin flakes

4:第二剝離材 4: Second peeling material

Claims (16)

一種樹脂薄片，其係由含有(A)樹脂成分及(C)熱傳導性填料的樹脂組成物所形成之樹脂薄片，其特徵為 前述(A)樹脂成分含有馬來醯亞胺樹脂， 且含有1種類或2種類以上前述(C)熱傳導性填料， 將前述(C)熱傳導性填料的種類之數定為n時，下述數式(F1)表示之前述(C)熱傳導性填料的對臨界填充量比為0.95以上1.26以下，
Figure 03_image001
V n：前述(C)熱傳導性填料當中之第n種類之熱傳導性填料的體積填充率 CV n：前述(C)熱傳導性填料當中之第n種類之熱傳導性填料的臨界體積填充率。 A resin sheet, which is a resin sheet formed of a resin composition containing (A) a resin component and (C) a thermally conductive filler, characterized in that the aforementioned (A) resin component contains a maleimide resin, and contains 1 When the number of the above-mentioned (C) heat-conductive fillers is one or more than two kinds, when the number of types of the above-mentioned (C) heat-conductive fillers is set to n, the critical filling of the above-mentioned (C) heat-conductive fillers represented by the following formula (F1) The quantity ratio is more than 0.95 and less than 1.26,
Figure 03_image001
V n : volume filling rate of the nth type of thermally conductive filler among the aforementioned (C) thermally conductive fillers CV n : critical volume filling rate of the nth type of thermally conductive filler among the aforementioned (C) thermally conductive fillers. 如請求項1之樹脂薄片，其中， 前述CV n之值係藉由下述測定方法測定， (CV n之值的測定方法) 調製將各熱傳導性填料的體積填充率以1%刻紋變化之樹脂組成物，並使用此等之樹脂組成物，分別製作樹脂薄片，接著，將此等之樹脂薄片的表面以雷射顯微鏡觀察(觀察面積：1mm×1mm)，確認短軸20μm以上且長軸20μm以上的大小之空隙的有無，從體積填充率低之樹脂薄片依序觀察時，將較首次確認2個以上之空隙的樹脂薄片之體積填充率更小1%之值定為CV n之值。 The resin sheet according to claim 1, wherein the value of the aforementioned CV n is measured by the following measurement method, (Measurement method of the value of CV n ) prepared by changing the volume filling rate of each thermally conductive filler by 1% of the groove Resin composition, and use these resin compositions to make resin sheets respectively, then observe the surface of these resin sheets with a laser microscope (observation area: 1mm×1mm), confirm that the short axis is more than 20μm and the long axis When the presence or absence of voids with a size of 20 μm or more is observed sequentially from resin sheets with low volume filling ratios, the value 1% smaller than the volume filling ratio of the resin sheet with 2 or more voids confirmed for the first time is defined as the value of CV n . 如請求項1之樹脂薄片，其中， 前述樹脂組成物進一步含有(C1)氮化硼粒子。 Such as the resin sheet of claim 1, wherein, The aforementioned resin composition further contains (C1) boron nitride particles. 如請求項1之樹脂薄片，其中， 前述樹脂組成物進一步含有(C2)氧化鋁粒子。 Such as the resin sheet of claim 1, wherein, The aforementioned resin composition further contains (C2) alumina particles. 如請求項1之樹脂薄片，其中， 前述(A)樹脂成分含有(A1)第1馬來醯亞胺樹脂， 且前述(A1)第1馬來醯亞胺樹脂係於1分子中具有2個以上之馬來醯亞胺基，連結至少1對之2個馬來醯亞胺基的鍵結基於主鏈具有4個以上之亞甲基的馬來醯亞胺樹脂。 Such as the resin sheet of claim 1, wherein, The aforementioned (A) resin component contains (A1) the first maleimide resin, And the above-mentioned (A1) first maleimide resin has two or more maleimide groups in one molecule, and the linkage of at least one pair of two maleimide groups is based on the main chain having Maleimide resin with more than 4 methylene groups. 如請求項1之樹脂薄片，其中， 前述(A)樹脂成分進一步含有(A2)第2馬來醯亞胺樹脂， 前述(A2)第2馬來醯亞胺樹脂係與(A1)第1馬來醯亞胺樹脂，化學構造不同之馬來醯亞胺樹脂。 Such as the resin sheet of claim 1, wherein, Said (A) resin component further contains (A2) the 2nd maleimide resin, The aforementioned (A2) second maleimide resin is a maleimide resin having a different chemical structure from the (A1) first maleimide resin. 如請求項6之樹脂薄片，其中， 前述(A2)第2馬來醯亞胺樹脂係於1分子中包含2個以上之馬來醯亞胺基及2個以上之伸苯基的馬來醯亞胺樹脂。 Such as the resin sheet of claim 6, wherein, The aforementioned (A2) second maleimide resin is a maleimide resin containing two or more maleimide groups and two or more phenylene groups in one molecule. 請求項1之樹脂薄片，其中， 前述樹脂組成物進一步含有(B)密著性賦予劑。 The resin sheet of claim 1, wherein, The aforementioned resin composition further contains (B) an adhesiveness imparting agent. 請求項8之樹脂薄片，其中， 前述(B)密著性賦予劑含有(B1)具有三嗪骨架之化合物。 The resin sheet of claim 8, wherein, The said (B) adhesiveness imparting agent contains (B1) the compound which has a triazine frame|skeleton. 請求項9之樹脂薄片，其中， 前述(B1)具有三嗪骨架之化合物係於1分子中具有鹼性基，且具有三嗪骨架之化合物。 The resin sheet of claim 9, wherein, Said (B1) compound which has a triazine skeleton is a compound which has a basic group in 1 molecule, and has a triazine skeleton. 如請求項9之樹脂薄片，其中， 前述(B1)具有三嗪骨架之化合物係於1分子中具有三嗪骨架及咪唑構造之化合物。 Such as the resin sheet of claim 9, wherein, The aforementioned (B1) compound having a triazine skeleton is a compound having a triazine skeleton and an imidazole structure in one molecule. 如請求項8之樹脂薄片，其中， 前述(B)密著性賦予劑含有(B2)耦合劑。 Such as the resin sheet of claim 8, wherein, The said (B) adhesiveness imparting agent contains (B2) coupling agent. 如請求項1之樹脂薄片，其中， 前述(A)樹脂成分進一步含有(A3)烯丙基樹脂。 Such as the resin sheet of claim 1, wherein, Said (A) resin component contains (A3) allyl resin further. 如請求項1至請求項13中任一項之樹脂薄片，其係使用在密封半導體元件，或者使用在介在前述半導體元件與其他電子零件之間。The resin sheet according to any one of claim 1 to claim 13 is used to seal a semiconductor element, or to be used between the aforementioned semiconductor element and other electronic parts. 如請求項1至請求項13中任一項之樹脂薄片，其係使用在介在散熱片與電子零件之間。The resin sheet according to any one of claim 1 to claim 13 is used between a heat sink and an electronic component. 如請求項1至請求項13中任一項之樹脂薄片，其係使用在密封使用化合物半導體之半導體元件，或者使用在介在使用前述化合物半導體之半導體元件與其他電子零件之間。The resin sheet according to any one of claims 1 to 13 is used to seal a semiconductor element using a compound semiconductor, or used between the semiconductor element using the compound semiconductor and other electronic parts.
TW111126805A 2021-07-20 2022-07-18 Resin sheet TW202313804A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021119526 2021-07-20
JP2021-119526 2021-07-20

Publications (1)

Publication Number Publication Date
TW202313804A true TW202313804A (en) 2023-04-01

Family

ID=84979226

Family Applications (1)

Application Number Title Priority Date Filing Date
TW111126805A TW202313804A (en) 2021-07-20 2022-07-18 Resin sheet

Country Status (2)

Country Link
TW (1) TW202313804A (en)
WO (1) WO2023002874A1 (en)

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06132433A (en) * 1992-10-20 1994-05-13 Fujitsu Ltd Resin composition for radiating fin for cooling of semiconductor device
JP3937494B2 (en) * 1997-02-24 2007-06-27 住友化学株式会社 Alumina-filled resin or rubber composition
JP5665846B2 (en) * 2010-03-10 2015-02-04 新日鉄住金化学株式会社 Thermally conductive polyimide film and thermal conductive laminate using the same
EP3035397B1 (en) * 2013-09-25 2018-04-11 Lintec Corporation Heat-conductive adhesive sheet, manufacturing method for same, and electronic device using same
JP6421448B2 (en) * 2014-05-09 2018-11-14 Dic株式会社 Composite particle, method for producing the same, and resin composition
JP6748967B2 (en) * 2016-11-30 2020-09-02 パナソニックＩｐマネジメント株式会社 Sheet-shaped thermosetting resin composition, and resin sheet, module component, power device and coil component using the same
JP7122622B2 (en) * 2018-05-31 2022-08-22 パナソニックＩｐマネジメント株式会社 Resin composition, insulation sheet and printed wiring board
JP6871960B2 (en) * 2018-09-26 2021-05-19 株式会社Kri Method of modifying the surface of the base material
JP7066654B2 (en) * 2019-04-10 2022-05-13 信越化学工業株式会社 Composition for low-dielectric heat-dissipating film and low-dielectric heat-dissipating film
US20230064310A1 (en) * 2020-01-16 2023-03-02 Lintec Corporation Resin sheet
JP2021152101A (en) * 2020-03-24 2021-09-30 三菱マテリアル株式会社 Insulation film, metal base substrate and metal base substrate production method
JP7468841B2 (en) * 2020-09-01 2024-04-16 三笠産業株式会社 Inorganic filler, boron nitride composition, method for producing inorganic filler, and method for producing boron nitride composition
JP2022052765A (en) * 2020-09-23 2022-04-04 積水化学工業株式会社 Heat-dissipating resin composition for protective films, protective film, and electronic component

Also Published As

Publication number Publication date
WO2023002874A1 (en) 2023-01-26

Similar Documents

Publication Publication Date Title
TWI386473B (en) Hot-melt silicone adhesive
TWI787242B (en) Resin composition and resin sheet
WO2021145415A1 (en) Resin sheet
WO2020196070A1 (en) Resin sheet
TWI758489B (en) Resin composition and resin sheet
TW202313804A (en) Resin sheet
WO2021039687A1 (en) Resin composition and resin sheet
CN112513142B (en) Resin sheet and laminate
WO2022210187A1 (en) Resin sheet
CN115279836B (en) Resin composition and resin sheet
WO2021117796A1 (en) Resin composition and resin sheet
JP2024075810A (en) Resin Sheet
TW202334349A (en) Resin composition for flexible device, film-like adhesive for flexible device, adhesive sheet for flexible device, and method for manufacturing flexible device