TW201507074A - Resin sheet for electronic device sealing and production method for electronic device package - Google Patents

Resin sheet for electronic device sealing and production method for electronic device package Download PDF

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TW201507074A
TW201507074A TW103111070A TW103111070A TW201507074A TW 201507074 A TW201507074 A TW 201507074A TW 103111070 A TW103111070 A TW 103111070A TW 103111070 A TW103111070 A TW 103111070A TW 201507074 A TW201507074 A TW 201507074A
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resin sheet
resin
group
sealing
electronic component
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TW103111070A
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TWI625832B (en
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Eiji Toyoda
yusaku Shimizu
Tsuyoshi Ishizaka
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Nitto Denko Corp
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    • 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
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H01L21/561—Batch processing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/93—Batch processes
    • H01L24/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
    • H01L24/97—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips the devices being connected to a common substrate, e.g. interposer, said common substrate being separable into individual assemblies after connecting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16245—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/93—Batch processes
    • H01L2224/95—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips
    • H01L2224/97—Batch processes at chip-level, i.e. with connecting carried out on a plurality of singulated devices, i.e. on diced chips the devices being connected to a common substrate, e.g. interposer, said common substrate being separable into individual assemblies after connecting
    • 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
    • H01L23/3107—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L24/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/14—Integrated circuits
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/146—Mixed devices
    • H01L2924/1461—MEMS
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/156—Material
    • H01L2924/15786—Material with a principal constituent of the material being a non metallic, non metalloid inorganic material
    • H01L2924/15787—Ceramics, e.g. crystalline carbides, nitrides or oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation
    • H—ELECTRICITY
    • H03—ELECTRONIC CIRCUITRY
    • H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
    • H03H9/00—Networks comprising electromechanical or electro-acoustic devices; Electromechanical resonators
    • H03H9/02—Details
    • H03H9/05—Holders; Supports
    • H03H9/10—Mounting in enclosures

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  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided is a resin sheet in which the sheet thickness is large and the amount of outgas is reduced. The present invention pertains to a resin sheet for electronic device sealing in which the thickness thereof is 100-2000 [mu]m and the amount of gas generated when cured for one hour at 150 DEG C is no more than 500 ppm.

Description

電子元件密封用樹脂薄片及電子元件封裝體之製造方法 Resin sheet for electronic component sealing and method of manufacturing electronic component package 發明領域 Field of invention

本發明有關於電子元件密封用樹脂薄片及電子元件封裝體之製造方法。 The present invention relates to a resin sheet for electronic component sealing and a method of manufacturing the electronic component package.

發明背景 Background of the invention

在電子元件封裝體之製作上，代表性的做法是採用將已固定於基板等的1個或複數個電子元件以密封樹脂密封，並依需要將密封體切割，使之成為電子元件單元之封裝體的順序。而在所述密封樹脂方面，有時使用薄片狀之密封樹脂。 In the manufacture of an electronic component package, a one or a plurality of electronic components fixed to a substrate or the like are sealed with a sealing resin, and the sealing body is cut as necessary to form a package of the electronic component unit. The order of the bodies. On the other hand, in the case of the sealing resin, a sheet-like sealing resin is sometimes used.

例如，在專利文獻1記載著，將清漆塗布在薄膜上，接著使塗布膜乾燥，藉此來形成樹脂薄片。 For example, Patent Document 1 discloses that a varnish is applied onto a film, and then the coating film is dried to form a resin sheet.

先行技術文獻 Advanced technical literature 專利文獻 Patent literature

專利文獻1：日本特開2006-19714號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 2006-19714

發明概要 Summary of invention

在如專利文獻1之樹脂薄片的製作方法(溶劑塗 裝)，調製清漆時會使用溶劑。一旦溶劑殘留在樹脂薄片，溶劑會因熱硬化時或回流焊時的加熱而揮發，導致產生排氣。使溶劑從藉由溶劑塗裝來製作的樹脂薄片充分揮發很難，尤其是在薄片厚度厚的樹脂薄片特別難。 Method for producing a resin sheet as in Patent Document 1 (solvent coating) Packing), solvent is used when varnish is prepared. Once the solvent remains on the resin sheet, the solvent is volatilized by heat hardening or heating during reflow, resulting in exhaust gas. It is difficult to sufficiently evaporate the solvent from the resin sheet produced by solvent coating, and in particular, it is particularly difficult to form a resin sheet having a thick sheet thickness.

本發明以解決前述課題，並提供薄片厚度厚、且排氣量被降低之樹脂薄片為目的。 The present invention has an object of solving the above problems and providing a resin sheet having a thick sheet thickness and a reduced exhaust gas amount.

本發明有關於一種電子元件密封用樹脂薄片，其厚度為100~2000μm，且在150℃下使之硬化1小時後產生的氣體量為500ppm以下。 The present invention relates to a resin sheet for sealing electronic components, which has a thickness of 100 to 2000 μm and a gas amount of 500 ppm or less which is hardened at 150 ° C for 1 hour.

以往，厚度在前述範圍內之樹脂薄片，要降低使其硬化時產生的氣體量是困難的，然本發明之樹脂薄片，其硬化時的排氣量降低，可降低起因於該排氣之電子元件的腐蝕或故障。 Conventionally, it is difficult to reduce the amount of gas generated during hardening of the resin sheet having the thickness within the above range. However, the resin sheet of the present invention has a reduced exhaust gas amount during curing, and can reduce electrons caused by the exhaust gas. Corrosion or malfunction of components.

令前述電子元件密封用樹脂薄片在150℃下硬化1小時所獲得之硬化物，其減少1%重量之溫度宜為260℃以上。若為260℃以上，則樹脂薄片中的揮發成分量降低，可降低回流焊時產生的氣體(排氣)量。 The cured product obtained by curing the resin sheet for electronic component sealing at 150 ° C for 1 hour preferably has a temperature of 1% by weight and is preferably 260 ° C or higher. When it is 260 ° C or more, the amount of volatile components in the resin sheet is lowered, and the amount of gas (exhaust gas) generated during reflow can be reduced.

將前述電子元件密封用樹脂薄片在150℃下硬化1小時所獲得之硬化物，以昇溫速度10℃/分從40℃昇溫到260℃，接著在260℃下加熱1分鐘時，產生的氣體量宜為500ppm以下。以該氣體量為前提下的加熱條件為預想回流焊溫度曲線而定者。該氣體量若為500ppm以下，則可降低在回流焊時產生的氣體(排氣)量。 The amount of gas generated when the cured product obtained by curing the resin sheet for electronic component sealing at 150 ° C for 1 hour is heated from 40 ° C to 260 ° C at a temperature increase rate of 10 ° C /min, and then heated at 260 ° C for 1 minute. It should be 500ppm or less. The heating condition under the premise of the gas amount is determined by the expected reflow soldering temperature curve. When the amount of the gas is 500 ppm or less, the amount of gas (exhaust gas) generated during reflow can be reduced.

本發明又有關於一種電子元件封裝體之製造方法，包含下述步驟：積層步驟，以覆蓋1個或複數個電子元件的方式將前述電子元件密封用樹脂薄片積層在前述電子元件上，及密封體形成步驟，使前述電子元件密封用樹脂薄片硬化來形成密封體。 Further, the present invention relates to a method of manufacturing an electronic component package, comprising the steps of: laminating a resin sheet for sealing an electronic component on the electronic component by covering one or a plurality of electronic components, and sealing In the body forming step, the resin sheet for electronic component sealing is cured to form a sealed body.

11‧‧‧樹脂薄片 11‧‧‧Resin sheet

11a‧‧‧支持體 11a‧‧‧Support

12‧‧‧印刷配線基板 12‧‧‧Printed wiring substrate

13‧‧‧SAW濾波器 13‧‧‧SAW filter

13a‧‧‧突起電極 13a‧‧‧protruding electrode

14‧‧‧中空部分 14‧‧‧ hollow part

15‧‧‧密封體 15‧‧‧ Sealing body

18‧‧‧電子元件封裝體 18‧‧‧Electronic component package

圖1為示意性顯示關於本發明一種實施形態之樹脂薄片的剖面圖。 Fig. 1 is a cross-sectional view schematically showing a resin sheet according to an embodiment of the present invention.

圖2A為示意性顯示關於本發明一種實施形態之電子元件封裝體製造方法之一步驟的圖。 Fig. 2A is a view schematically showing a step of a method of manufacturing an electronic component package according to an embodiment of the present invention.

圖2B為示意性顯示關於本發明一種實施形態之電子元件封裝體製造方法之一步驟的圖。 Fig. 2B is a view schematically showing a step of a method of manufacturing an electronic component package according to an embodiment of the present invention.

圖2C為示意性顯示關於本發明一種實施形態之電子元件封裝體製造方法之一步驟的圖。 Fig. 2C is a view schematically showing a step of a method of manufacturing an electronic component package according to an embodiment of the present invention.

用以實施發明之形態 Form for implementing the invention

以下將舉實施形態來詳細說明本發明，但本發明並非僅侷限於該等實施形態者。 Hereinafter, the present invention will be described in detail by way of embodiments, but the invention is not limited to the embodiments.

[電子元件密封用樹脂薄片] [Resin sheet for electronic component sealing]

圖1為示意性顯示關於本發明一種實施形態之樹脂薄片11的剖面圖。代表性的樹脂薄片11是以積層在聚對苯二甲酸乙二酯(PET)薄膜等支持體11a上的狀態來提供。此外，為易於進行樹脂薄片11的剝離，可在支持體11a施行脫模處理。 Fig. 1 is a cross-sectional view schematically showing a resin sheet 11 according to an embodiment of the present invention. The representative resin sheet 11 is provided in a state of being laminated on a support 11a such as a polyethylene terephthalate (PET) film. Further, in order to facilitate the peeling of the resin sheet 11, the release treatment can be performed on the support 11a.

樹脂薄片11的厚度較厚，具體上為100~2000μm。以往，厚度在前述範圍內之樹脂薄片要降低排氣量是困難的，但樹脂薄片11已降低排氣量。樹脂薄片11的厚度宜為150μm以上。另一方面，樹脂薄片11的厚度宜為1000μm以下。 The thickness of the resin sheet 11 is thick, specifically 100 to 2000 μm. Conventionally, it has been difficult to reduce the amount of exhaust gas in the resin sheet having the thickness within the above range, but the resin sheet 11 has reduced the amount of exhaust gas. The thickness of the resin sheet 11 is preferably 150 μm or more. On the other hand, the thickness of the resin sheet 11 is preferably 1000 μm or less.

令樹脂薄片11在150℃下硬化1小時後產生的氣體(排氣)量為500ppm以下，且宜為300ppm以下。因為是500ppm以下，硬化時的排氣量降低，可降低起因於該排氣之電子元件的腐蝕或故障。另一方面，在150℃下使其硬化1小時後產生之氣體量下限並無特別限定，例如為30ppm以上。 The amount of gas (exhaust gas) generated after the resin sheet 11 is cured at 150 ° C for 1 hour is 500 ppm or less, and preferably 300 ppm or less. Since it is 500 ppm or less, the amount of exhaust gas at the time of hardening is lowered, and corrosion or failure of the electronic component due to the exhaust gas can be reduced. On the other hand, the lower limit of the amount of gas generated after curing at 150 ° C for 1 hour is not particularly limited, and is, for example, 30 ppm or more.

在150℃下使其硬化1小時後產生的氣體量可利用實施例記載的方法測定。 The amount of gas generated after curing at 150 ° C for 1 hour can be measured by the method described in the examples.

令樹脂薄片11在150℃下硬化1小時所獲得之硬化物，其減少1%重量之溫度宜為260℃以上，且以300℃以上為佳。若為260℃以上，則樹脂薄片11中的揮發成分量降低，可降低在回流焊時產生的氣體(排氣)量。令樹脂薄片11在150℃下硬化1小時所獲得之硬化物，其減少1%重量之溫度之上限並無特別限定，例如為500℃以下。 The cured product obtained by curing the resin sheet 11 at 150 ° C for 1 hour preferably has a temperature of 1% by weight or less and preferably 260 ° C or more, and more preferably 300 ° C or more. When it is 260 ° C or more, the amount of volatile components in the resin sheet 11 is lowered, and the amount of gas (exhaust gas) generated during reflow can be reduced. The cured product obtained by curing the resin sheet 11 at 150 ° C for 1 hour is not particularly limited as long as it is reduced by 1% by weight, and is, for example, 500 ° C or lower.

令樹脂薄片11在150℃下硬化1小時所獲得之硬化物，其減少1%重量之溫度，可利用實施例記載的方法測定。 The cured product obtained by curing the resin sheet 11 at 150 ° C for 1 hour was reduced in temperature by 1% by weight, and it can be measured by the method described in the examples.

將樹脂薄片11在150℃下硬化1小時所獲得之硬化物以10℃/分的昇溫速度從40℃昇溫到260℃，接著在260℃下加熱1分鐘時產生的氣體量宜為500ppm以下。以該 氣體量為前提之加熱條件為預想回流焊溫度曲線而定者。該氣體量若為500ppm以下，可降低回流焊時產生的氣體(排氣)量。下限並無特別限定，但為30ppm以上。 The cured product obtained by curing the resin sheet 11 at 150 ° C for 1 hour is heated from 40 ° C to 260 ° C at a temperature increase rate of 10 ° C / minute, and then the amount of gas generated when heated at 260 ° C for 1 minute is preferably 500 ppm or less. With this The heating condition under the premise of the amount of gas is determined by the expected reflow temperature curve. When the amount of the gas is 500 ppm or less, the amount of gas (exhaust gas) generated during reflow can be reduced. The lower limit is not particularly limited, but is 30 ppm or more.

將樹脂薄片11在150℃下硬化1小時所獲得之硬化物以10℃/分的昇溫速度從40℃昇溫到260℃，接著在260℃下加熱1分鐘時產生的氣體量，可利用實施例記載的方法測定。 The amount of gas generated when the cured product obtained by curing the resin sheet 11 at 150 ° C for 1 hour at a temperature increase rate of 10 ° C /min from 40 ° C to 260 ° C, followed by heating at 260 ° C for 1 minute, can be utilized. The method described is measured.

樹脂薄片11的製造方法並無特別限定，但宜為以後述各成分來調製捏合物，並將獲得之捏合物塑性加工成薄片狀的方法。藉此，可不使用溶劑而製作樹脂薄片11，故可降低排氣量。又，為了以溶劑塗裝來製作薄片厚度厚的樹脂薄片11，需要積層複數層的溶劑塗裝製樹脂薄片，但若藉此，將可不積層而製作樹脂薄片11(可一次製作樹脂薄片11)。因此，不會有層間剝離之虞。且薄片厚度的均一性亦可提高。又，相較於積層的情形，因表面積較小，可達成低吸濕化，其結果便是可降低排氣量。 The method for producing the resin sheet 11 is not particularly limited, but a method of preparing a kneaded material for each component described later and plastically processing the obtained kneaded product into a sheet shape is preferred. Thereby, the resin sheet 11 can be produced without using a solvent, so that the amount of exhaust gas can be reduced. In addition, in order to produce a resin sheet 11 having a thick sheet thickness by solvent coating, it is necessary to laminate a plurality of layers of solvent-coated resin sheets. However, the resin sheet 11 can be produced without lamination (the resin sheet 11 can be produced at one time). . Therefore, there will be no detachment between layers. Moreover, the uniformity of the thickness of the sheet can also be improved. Further, in comparison with the case of the laminate, since the surface area is small, low moisture absorption can be achieved, and as a result, the amount of exhaust gas can be reduced.

具體上，是將後述各成分(例如環氧樹脂、酚樹脂、熱塑性樹脂、無機填充材及硬化促進劑等)以混合輥、加壓式捏揉機、擠出機等周知的捏合機來熔融捏合，藉此調製捏合物，並將獲得之捏合物塑性加工成薄片狀。在捏合條件方面，溫度宜為上述各成分的軟化點以上，例如30~150℃，若考慮到環氧樹脂的熱硬化性，則宜為40~140℃，且以60~120℃為佳。時間則為例如1~30分鐘，且宜為5~15分鐘。 Specifically, each component (for example, an epoxy resin, a phenol resin, a thermoplastic resin, an inorganic filler, and a curing accelerator) to be described later is melt-kneaded by a known kneading machine such as a mixing roll, a pressure kneader, or an extruder. Thereby, the kneaded composition is prepared, and the obtained kneaded compound is plastically processed into a flake shape. In terms of kneading conditions, the temperature is preferably at least the softening point of each of the above components, for example, 30 to 150 ° C. When considering the thermosetting property of the epoxy resin, it is preferably 40 to 140 ° C and preferably 60 to 120 ° C. The time is, for example, 1 to 30 minutes, and preferably 5 to 15 minutes.

捏合宜在減壓條件下(減壓環境下)進行。藉此，可除氣同時可防止氣體侵入捏合物，其結果便是可降低排氣量。減壓條件下的壓力宜為0.1kg/cm2以下，且以0.05kg/cm2以下為佳。若為0.1kg/cm2以下，則可良好的降低排氣量。減壓下的壓力下限並無特別限定，例如為1×10-4kg/cm2以上。 Kneading is preferably carried out under reduced pressure (under reduced pressure). Thereby, the gas can be prevented from intruding into the kneaded material at the same time, and as a result, the amount of exhaust gas can be reduced. The pressure under reduced pressure is preferably 0.1 kg/cm 2 or less, and preferably 0.05 kg/cm 2 or less. When it is 0.1 kg/cm 2 or less, the amount of exhaust gas can be favorably lowered. The lower limit of the pressure under reduced pressure is not particularly limited and is, for example, 1 × 10 -4 kg / cm 2 or more.

熔融捏合後的捏合物宜不冷卻而直接在高溫狀態下來塑性加工。在塑性加工方法方面並無特別限制，可舉平板加壓法、T字模擠出法、螺紋模擠出法、輥壓延法、輥捏合法、充氣擠出法、共擠出法、壓光成型法等。在塑性加工溫度方面宜為上述各成分之軟化點以上，且若考慮到環氧樹脂之熱硬化性及成形性，則例如為40~150℃，且宜為50~140℃，又以70~120℃為更佳。 The kneaded product after melt-kneading is preferably subjected to plastic working directly at a high temperature without cooling. The plastic working method is not particularly limited, and may be a flat press method, a T-die extrusion method, a thread die extrusion method, a roll calendering method, a roll kneading method, a pneumatic extrusion method, a co-extrusion method, or a calender molding method. Law and so on. The plastic working temperature is preferably at least the softening point of each of the above components, and considering the thermosetting property and moldability of the epoxy resin, for example, 40 to 150 ° C, and preferably 50 to 140 ° C, and 70 ° 120 ° C is even better.

樹脂薄片11可為單層構造，亦可為積層有2層以上樹脂薄片的多層構造，但從無層間剝離之虞、薄片厚度均一性高、且容易行低吸濕化的理由來看，宜為單層構造。 The resin sheet 11 may have a single-layer structure or a multilayer structure in which two or more layers of resin sheets are laminated. However, it is preferable to remove the interlayer without peeling, the thickness uniformity of the sheet is high, and it is easy to reduce moisture absorption. It is a single layer construction.

接著針對樹脂薄片11的組成做說明。 Next, the composition of the resin sheet 11 will be described.

樹脂薄片11宜含有環氧樹脂及酚樹脂。藉此，可獲得良好的熱硬化性。 The resin sheet 11 preferably contains an epoxy resin and a phenol resin. Thereby, good thermosetting property can be obtained.

在環氧樹脂方面，並無特別限定者。例如可使用三苯甲烷型環氧樹脂、甲酚酚醛型環氧樹脂、聯苯型環氧樹脂、改質雙酚A型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、改質雙酚F型環氧樹脂、二環戊二烯型環 氧樹脂、苯酚酚醛型環氧樹脂、苯氧基樹脂等各種的環氧樹脂。該等環氧樹脂可單獨使用、亦可2種以上併用。 There is no particular limitation on the epoxy resin. For example, a triphenylmethane type epoxy resin, a cresol novolac type epoxy resin, a biphenyl type epoxy resin, a modified bisphenol A type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin can be used. Resin, modified bisphenol F epoxy resin, dicyclopentadiene ring Various epoxy resins such as an oxygen resin, a phenol novolak type epoxy resin, and a phenoxy resin. These epoxy resins may be used singly or in combination of two or more.

從確保環氧樹脂硬化後之靭性及環氧樹脂之反應性的觀點來看，宜為環氧基當量為150~250、軟化點或熔點為50~130℃之在常溫下為固態者，其中，從可靠性的觀點來看，以三苯甲烷型環氧樹脂、甲酚酚醛型環氧樹脂、聯苯型環氧樹脂為佳。 From the viewpoint of ensuring the toughness after curing of the epoxy resin and the reactivity of the epoxy resin, it is preferably a solid having an epoxy group equivalent of 150 to 250, a softening point or a melting point of 50 to 130 ° C at a normal temperature, wherein From the viewpoint of reliability, a triphenylmethane type epoxy resin, a cresol novolac type epoxy resin, and a biphenyl type epoxy resin are preferred.

酚樹脂只要是與環氧樹脂之間會發生硬化反應者，則無特別限定。可使用例如苯酚酚醛樹脂、苯酚芳烷基樹脂、聯苯芳烷基樹脂、二環戊二烯型酚樹脂、甲酚酚醛樹脂、可溶酚醛樹脂等。該等酚樹脂可單獨使用，亦可2種以上併用。 The phenol resin is not particularly limited as long as it undergoes a hardening reaction with the epoxy resin. For example, a phenol novolak resin, a phenol aralkyl resin, a biphenyl aralkyl resin, a dicyclopentadiene type phenol resin, a cresol novolak resin, a resol resin, or the like can be used. These phenol resins may be used singly or in combination of two or more.

作為酚樹脂，從與環氧樹脂之反應性的觀點來看，宜使用羥基當量是70~250、且軟化點為50~110℃者，於此之中，從硬化反應性高的觀點來看，可適宜的使用苯酚酚醛樹脂。又，從可靠性的觀點來看，可適宜的使用如苯酚芳烷基樹脂或聯苯芳烷基樹脂之類低吸濕性者。 As the phenol resin, from the viewpoint of reactivity with an epoxy resin, it is preferred to use a hydroxyl group equivalent of 70 to 250 and a softening point of 50 to 110 ° C. From the viewpoint of high curing reactivity, A phenol novolac resin can be suitably used. Further, from the viewpoint of reliability, a low hygroscopicity such as a phenol aralkyl resin or a biphenyl aralkyl resin can be suitably used.

環氧樹脂與酚樹脂的摻合比例，從硬化反應性的觀點來看，宜以相對於環氧樹脂中的環氧基1當量使酚樹脂中羥基的合計為0.7~1.5當量的方式進行摻合，且以0.9~1.2當量為佳。 The blending ratio of the epoxy resin and the phenol resin is preferably such that the total amount of the hydroxyl groups in the phenol resin is 0.7 to 1.5 equivalents per 1 equivalent of the epoxy group in the epoxy resin from the viewpoint of curing reactivity. It is preferably 0.9 to 1.2 equivalents.

樹脂薄片11中的環氧樹脂及酚樹脂的合計含量宜為2.0重量%以上，且以3.0重量%以上為佳。若為2.0重量%以上，可獲得對電子元件、基板等良好的接著力。樹 脂薄片11中的環氧樹脂及酚樹脂的合計含量宜為20重量%以下，且以10重量%以下為佳。若為20重量%以下，則可將吸濕性抑制得較低。 The total content of the epoxy resin and the phenol resin in the resin sheet 11 is preferably 2.0% by weight or more, and more preferably 3.0% by weight or more. When it is 2.0% by weight or more, good adhesion to an electronic component, a substrate, or the like can be obtained. tree The total content of the epoxy resin and the phenol resin in the grease sheet 11 is preferably 20% by weight or less, and preferably 10% by weight or less. When it is 20% by weight or less, the hygroscopicity can be suppressed to be low.

樹脂薄片11宜含有熱塑性樹脂。藉此，可獲得在未硬化狀態下的操作性、硬化物的低應力性。 The resin sheet 11 preferably contains a thermoplastic resin. Thereby, workability in an uncured state and low stress of a cured product can be obtained.

在熱塑性樹脂方面，可舉天然橡膠、丁基橡膠、異戊二烯橡膠、氯平橡膠、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、聚丁二烯樹脂、聚碳酸酯樹脂、熱塑性聚醯亞胺樹脂、6-尼龍或6,6-尼龍等的聚醯胺樹脂；苯氧基樹脂、丙烯酸樹脂、PBT或PET等的飽和聚酯樹脂；聚醯胺醯亞胺樹脂、氟樹脂、苯乙烯-異丁烯-苯乙烯嵌段共聚物等。該等熱塑性樹脂可以單獨使用，或合併2種以上來使用。於此之中，從低應力性、低吸水性的觀點來看，宜為苯乙烯-異丁烯-苯乙烯嵌段共聚物。 Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, and polybutadiene resin. Polycarbonate resin, polycarbonate resin, thermoplastic polyimide resin, 6-nylon or 6,6-nylon; saturated polyester resin such as phenoxy resin, acrylic resin, PBT or PET; polydecylamine A quinone imine resin, a fluororesin, a styrene-isobutylene-styrene block copolymer, or the like. These thermoplastic resins may be used singly or in combination of two or more. Among them, from the viewpoint of low stress and low water absorption, a styrene-isobutylene-styrene block copolymer is preferred.

樹脂薄片11中之熱塑性樹脂的含量宜為1.0重量%以上，且以1.5重量%以上為佳。若為1.0重量%以上，則可獲得柔軟性、可撓性。樹脂薄片11中之熱塑性樹脂的含量宜為3.5重量%以下，且以3重量%以下為佳。若為3.5重量%以下，則可提高與電子元件或基板的接著性。 The content of the thermoplastic resin in the resin sheet 11 is preferably 1.0% by weight or more, and more preferably 1.5% by weight or more. When it is 1.0% by weight or more, flexibility and flexibility can be obtained. The content of the thermoplastic resin in the resin sheet 11 is preferably 3.5% by weight or less, and preferably 3% by weight or less. When it is 3.5% by weight or less, adhesion to an electronic component or a substrate can be improved.

樹脂薄片11宜含有無機填充材。 The resin sheet 11 preferably contains an inorganic filler.

無機填充材並無特別限定，可使用以往習知的各種填充材，可舉例如石英玻璃、滑石、二氧化矽(熔融二氧化矽或結晶性二氧化矽等)、氧化鋁、氮化鋁、氮化 矽、氮化硼的粉末。該等可單獨使用，亦可2種以上併用。於此之中，從可良好的降低線膨脹係數的理由來看，宜為二氧化矽、氧化鋁，且以二氧化矽為佳。 The inorganic filler is not particularly limited, and various conventional fillers can be used, and examples thereof include quartz glass, talc, cerium oxide (melted cerium oxide or crystalline cerium oxide), alumina, and aluminum nitride. Nitriding A powder of bismuth or boron nitride. These may be used alone or in combination of two or more. Among them, from the viewpoint of a good reduction in the coefficient of linear expansion, it is preferably cerium oxide, aluminum oxide, and preferably cerium oxide.

在二氧化矽方面，宜為二氧化矽粉末，且以熔融二氧化矽粉末為佳。在熔融二氧化矽粉末方面，可舉球狀熔融二氧化矽粉末、破碎熔融二氧化矽粉末，但從流動性的觀點來看，宜為球狀熔融二氧化矽粉末。於此之中，宜為平均粒徑在10~30μm之範圍者，且以在15~25μm之範圍者為佳。 In the case of cerium oxide, cerium oxide powder is preferred, and molten cerium oxide powder is preferred. The molten cerium oxide powder may be a spherical molten cerium oxide powder or a crushed molten cerium oxide powder, but it is preferably a spherical molten cerium oxide powder from the viewpoint of fluidity. Among them, the average particle diameter is preferably in the range of 10 to 30 μm, and preferably in the range of 15 to 25 μm.

此外，平均粒徑，例如可藉由下述方法導出：使用從母群任意提取的試料，並使用雷射繞射散射式粒度分布測定裝置來測定。 Further, the average particle diameter can be derived, for example, by using a sample arbitrarily extracted from a parent group and measuring it using a laser diffraction scattering type particle size distribution measuring apparatus.

樹脂薄片11中之無機填充材的含量宜為70體積%以上，且以74體積%以上為佳。若為70體積%以上，則可將線膨脹係數設計得較低。另一方面，無機填充材的含量宜為90體積%以下，且以85體積%以下為佳。若為90體積%以下，則可獲得良好的柔軟性、流動性、接著性。 The content of the inorganic filler in the resin sheet 11 is preferably 70% by volume or more, and more preferably 74% by volume or more. If it is 70% by volume or more, the coefficient of linear expansion can be designed to be low. On the other hand, the content of the inorganic filler is preferably 90% by volume or less, and preferably 85% by volume or less. When it is 90 vol% or less, good flexibility, fluidity, and adhesion can be obtained.

無機填充材的含量亦可以「重量%」作為單位來說明。典型上，針對二氧化矽的含量係以「重量%」為單位來說明。 The content of the inorganic filler can also be described in terms of "% by weight". Typically, the content of cerium oxide is described in terms of "% by weight".

二氧化矽通常比重為2.2g/cm3，因此二氧化矽含量(重量%)的適宜範圍例如為下者。 The cerium oxide usually has a specific gravity of 2.2 g/cm 3 , and thus a suitable range of the cerium oxide content (% by weight) is, for example, the following.

即，樹脂薄片11中之二氧化矽的含量宜為81重量%以上，且以84重量%以上為佳。樹脂薄片11中之二氧化矽的 含量宜為94重量%以下，且以91重量%以下為佳。 That is, the content of cerium oxide in the resin sheet 11 is preferably 81% by weight or more, and preferably 84% by weight or more. Cerium oxide in the resin sheet 11 The content is preferably 94% by weight or less, and preferably 91% by weight or less.

氧化鋁通常比重為3.9g/cm3，因此氧化鋁含量(重量%)的適宜範圍例如為下者。 The alumina generally has a specific gravity of 3.9 g/cm 3 , and thus a suitable range of the alumina content (% by weight) is, for example, the following.

即，樹脂薄片11中之氧化鋁的含量宜為88重量%以上，且以90重量%以上為佳。樹脂薄片11中之氧化鋁的含量宜為97重量%以下。且以95重量%以下為佳。 That is, the content of the alumina in the resin sheet 11 is preferably 88% by weight or more, and more preferably 90% by weight or more. The content of the alumina in the resin sheet 11 is preferably 97% by weight or less. It is preferably 95% by weight or less.

樹脂薄片11宜含有硬化促進劑。 The resin sheet 11 preferably contains a hardening accelerator.

在硬化促進劑方面，若為使環氧樹脂與酚樹脂進行硬化者則無特別限定，可舉例如三苯基膦、四苯基鏻四苯基硼酸鹽等的有機磷系化合物；2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑等的咪唑系化合物等。於此之中，從硬化反應不會隨捏合時之溫度上昇加劇而可良好製作樹脂薄片11的理由來看，宜為2-苯基-4,5-二羥基甲基咪唑。 In the curing accelerator, the epoxy resin and the phenol resin are not particularly limited, and examples thereof include an organic phosphorus compound such as triphenylphosphine or tetraphenylphosphonium tetraphenylborate; and 2-benzene. An imidazole compound such as benzyl-4,5-dihydroxymethylimidazole or 2-phenyl-4-methyl-5-hydroxymethylimidazole. Among them, 2-phenyl-4,5-dihydroxymethylimidazole is preferred because the curing reaction does not increase as the temperature rises during kneading, and the resin sheet 11 can be favorably produced.

相對於環氧樹脂及酚樹脂之合計100重量份，硬化促進劑的含量宜為0.1~5重量份。 The content of the hardening accelerator is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the total of the epoxy resin and the phenol resin.

樹脂薄片11宜含有阻燃劑成分。藉此，可降低因零件短路或發熱等起火時的燃燒擴大。在阻燃劑成分方面，可使用例如氫氧化鋁、氫氧化鎂、氫氧化鐵、氫氧化鈣、氫氧化錫、錯合化金屬氫氧化物等的各種金屬氫氧化物；膦氮烯系阻燃劑等。於此之中，從在阻燃性、硬化後之強度優異的理由來看，宜為膦氮烯系阻燃劑，且宜為式(1)或式(2)所表示之化合物。 The resin sheet 11 preferably contains a flame retardant component. Thereby, it is possible to reduce the combustion expansion at the time of a fire due to a short circuit or a heat generation of the component. In terms of the flame retardant component, various metal hydroxides such as aluminum hydroxide, magnesium hydroxide, iron hydroxide, calcium hydroxide, tin hydroxide, miscible metal hydroxide, and the like can be used; Burning agent, etc. In the above, from the viewpoint of excellent flame retardancy and strength after curing, a phosphazene-based flame retardant is preferable, and a compound represented by the formula (1) or the formula (2) is preferable.

[化1] [Chemical 1]

(式中，R1及R2相同或相異，表示1價有機基，其具有烷氧基、苯氧基、胺基、羥基、烯丙基、或選自由該等基所構成群組中之至少1種基。x表示3~25的整數。) (wherein R 1 and R 2 are the same or different and each represents a monovalent organic group having an alkoxy group, a phenoxy group, an amine group, a hydroxyl group, an allyl group, or a group selected from the group consisting of the groups; At least one base. x represents an integer from 3 to 25.)

(式中，R3及R5相同或相異，表示1價有機基，其具有烷氧基、苯氧基、胺基、羥基、烯丙基、或選自由該等基所構成群組中之至少1種基。R4表示2價有機基，其具有選自由烷氧基、苯氧基、胺基、羥基及烯丙基所構成群組中之 至少1種基。y表示3~25的整數。z表示3~25的整數。) (wherein R 3 and R 5 are the same or different and each represents a monovalent organic group having an alkoxy group, a phenoxy group, an amine group, a hydroxyl group, an allyl group, or a group selected from the group consisting of the groups; At least one group: R 4 represents a divalent organic group having at least one group selected from the group consisting of an alkoxy group, a phenoxy group, an amine group, a hydroxyl group, and an allyl group. y represents 3 to 25 The integer. z represents an integer from 3 to 25.)

在R1及R2之烷氧基方面，可舉甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、三級丁氧基等。於此之中，宜為碳數4~10的烷氧基。 Examples of the alkoxy group of R 1 and R 2 include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, and a tertiary butoxy group. Among them, an alkoxy group having 4 to 10 carbon atoms is preferable.

在R1及R2的苯氧基方面，可舉例如式(3)所表示的基。 The phenoxy group of R 1 and R 2 may, for example, be a group represented by the formula (3).

(式中，R11表示1價有機基，其具有氫、羥基、烷基、烷氧基、縮水甘油基或選自由該等基所構成群組中之至少1種基。) (wherein R 11 represents a monovalent organic group having hydrogen, a hydroxyl group, an alkyl group, an alkoxy group, a glycidyl group or at least one selected from the group consisting of such groups.)

作為R11的烷基，可舉例如甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、戊基、己基、庚基、2-乙基己基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十八烷基等。作為R11的烷氧基，可舉與R1及R2之烷氧基同樣的基。 The alkyl group of R 11 may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a pentyl group, a hexyl group or a heptyl group. 2-ethylhexyl, octyl, decyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, octadecyl, and the like. The alkoxy group of R 11 may be the same group as the alkoxy group of R 1 and R 2 .

在R1及R2方面，從可以獲得良好之阻燃性、硬化後強度的理由來看，宜為苯氧基，且以式(3)所表示之基為佳。 In the case of R 1 and R 2 , from the viewpoint of obtaining good flame retardancy and strength after hardening, a phenoxy group is preferable, and a group represented by the formula (3) is preferred.

x表示3~25的整數，但從可獲得良好之阻燃性、硬化後強度的理由來看，宜為3~10，且以3~4為佳。 x represents an integer of 3 to 25, but from the viewpoint of obtaining good flame retardancy and strength after hardening, it is preferably 3 to 10, and preferably 3 to 4.

在式(2)中，作為R3及R5之烷氧基，可舉例如甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、三級丁氧基等。於此之中，宜為碳數4~10的烷氧基。 In the formula (2), examples of the alkoxy group of R 3 and R 5 include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a tertiary butoxy group, and the like. . Among them, an alkoxy group having 4 to 10 carbon atoms is preferable.

作為R3及R5之苯氧基，可舉例如前述式(3)所表示之基。 The phenoxy group of R 3 and R 5 may, for example, be a group represented by the above formula (3).

R3及R5中，在具有選自由烷氧基、苯氧基、胺基、羥基及烯丙基所構成群組中之至少1種基的1價有機基方面，並無特別限定。 In R 3 and R 5 , the monovalent organic group having at least one selected from the group consisting of an alkoxy group, a phenoxy group, an amine group, a hydroxyl group, and an allyl group is not particularly limited.

在R3及R5方面，從可獲得良好的阻燃性、硬化後之強度的理由來看，宜為苯氧基，且以式(3)所表示之基為佳。 In the case of R 3 and R 5 , from the viewpoint of obtaining good flame retardancy and strength after hardening, a phenoxy group is preferable, and a group represented by the formula (3) is preferred.

作為R4之2價有機基所具有的烷氧基，可舉例如甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、三級丁氧基等。於此之中，宜為碳數4~10的烷氧基。 The alkoxy group which the divalent organic group of R 4 has may, for example, be a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group or a tertiary butoxy group. Among them, an alkoxy group having 4 to 10 carbon atoms is preferable.

作為R4之2價有機基所具有的苯氧基，可舉例如前述式(3)所表示之基。 The phenoxy group which the divalent organic group of R 4 has may be, for example, a group represented by the above formula (3).

y表示3~25的整數，但從可以獲得良好的阻燃性、硬化後之強度的理由來看，宜為3~10。 y represents an integer of 3 to 25, but it is preferably from 3 to 10 from the viewpoint of obtaining good flame retardancy and strength after hardening.

z表示3~25的整數，但從可以獲得良好的阻燃性、硬化後之強度的理由來看，宜為3~10。 z represents an integer of 3 to 25, but it is preferably from 3 to 10 from the viewpoint of obtaining good flame retardancy and strength after hardening.

從即使少量亦能發揮阻燃效果的觀點來看，膦氮烯系阻燃劑所含之磷元素的含有率宜為12重量%以上。 The content of the phosphorus element contained in the phosphazene-based flame retardant is preferably 12% by weight or more from the viewpoint of exhibiting a flame retarding effect even in a small amount.

在有機成分(除去無機填充材之總成分)100重量%中，阻燃劑成分的含量宜為10重量%以上，且以15重量%以上為佳。若為10重量%以上，則可獲得良好的阻燃性。阻燃劑成分的含量宜為30重量%以下，且以25重量%以下為佳。若為30重量%以下，則硬化物之物性低下(具體而言，是玻璃轉化溫度或高溫樹脂強度等的物性低下)會有減少的傾向。 The content of the flame retardant component is preferably 10% by weight or more, and preferably 15% by weight or more, based on 100% by weight of the organic component (excluding the total component of the inorganic filler). When it is 10% by weight or more, good flame retardancy can be obtained. The content of the flame retardant component is preferably 30% by weight or less, and preferably 25% by weight or less. When it is 30% by weight or less, the physical properties of the cured product are lowered (specifically, the physical properties such as the glass transition temperature or the high-temperature resin strength are lowered).

樹脂薄片11宜含有矽烷偶合劑。在矽烷偶合劑方面並無特別限定，可舉3-環氧丙氧基丙基三甲氧基矽烷等。 The resin sheet 11 preferably contains a decane coupling agent. The decane coupling agent is not particularly limited, and examples thereof include 3-glycidoxypropyltrimethoxydecane.

樹脂薄片11中之矽烷偶合劑的含量宜為0.1~3重量%。若為0.1重量%以上，則可獲得充分的硬化物強度，可降低吸水率。若為3重量%以下，則可將排氣量抑制得較低。 The content of the decane coupling agent in the resin sheet 11 is preferably from 0.1 to 3% by weight. When it is 0.1% by weight or more, sufficient hardened material strength can be obtained, and the water absorption rate can be lowered. When it is 3% by weight or less, the amount of exhaust gas can be kept low.

樹脂薄片11宜含有顏料。在顏料方面並無特別限定，可舉碳黑等。 The resin sheet 11 preferably contains a pigment. The pigment is not particularly limited, and examples thereof include carbon black.

樹脂薄片11中的顏料含量宜為0.1~2重量%。若為0.1重量%以上，則可獲得良好的標記性。若為2重量%以下，則可獲得足夠的硬化物強度。 The pigment content in the resin sheet 11 is preferably from 0.1 to 2% by weight. When it is 0.1% by weight or more, good marking properties can be obtained. If it is 2% by weight or less, sufficient hardened material strength can be obtained.

此外，在樹脂組成物中，除上述之各成分以外，依需要可適宜摻合其他添加劑。 Further, in the resin composition, in addition to the above respective components, other additives may be suitably blended as needed.

樹脂薄片11可使用在SAW(Surface Acoustic Wave)濾波器；壓力感測器、振動感測器等的MEMS(Micro Electro Mechanical Systems)；LSI等的IC(積體電路)、電晶 體等的半導體；電容器；電阻等的電子元件之密封上。於此之中，可適宜使用在必須中空密封之電子元件(具體來說為SAW濾波器、MEMS)的密封上，且特別適宜使用在SAW濾波器的密封上。 The resin sheet 11 can be used in a SAW (Surface Acoustic Wave) filter, a MEMS (Micro Electro Mechanical Systems) such as a pressure sensor or a vibration sensor, an IC (integrated circuit) such as an LSI, or a crystal. Semiconductors such as bulk; capacitors; seals of electronic components such as resistors. Among them, it can be suitably used for sealing of an electronic component (specifically, a SAW filter, MEMS) which is required to be hollow-sealed, and is particularly suitably used for sealing of a SAW filter.

在密封方法方面並無特別限定，可舉例如以覆蓋基板上之電子元件的方式將未硬化的樹脂薄片11積層在基板上，接著使樹脂薄片11硬化來密封的方法等。在基板方面並無特別限定，可舉例如印刷配線基板、陶瓷基板、矽基板、金屬基板等。 The sealing method is not particularly limited, and for example, a method in which an uncured resin sheet 11 is laminated on a substrate so as to cover the electronic component on the substrate, and then the resin sheet 11 is cured and sealed. The substrate is not particularly limited, and examples thereof include a printed wiring board, a ceramic substrate, a tantalum substrate, and a metal substrate.

[電子元件封裝體之製造方法] [Method of Manufacturing Electronic Component Package]

圖2A~2C分別是示意性顯示關於本發明一種實施形態之電子元件封裝體製造方法之一步驟的圖。在本實施形態，是藉由樹脂薄片11來將搭載在印刷配線基板12上之SAW濾波器13中空密封而製作電子元件封裝體。 2A to 2C are views each schematically showing a step of a method of manufacturing an electronic component package according to an embodiment of the present invention. In the present embodiment, the SAW filter 13 mounted on the printed wiring board 12 is hermetically sealed by the resin sheet 11, and an electronic component package is produced.

(SAW濾波器搭載基板準備步驟) (SAW filter mounting substrate preparation step)

SAW濾波器搭載基板準備步驟，是準備搭載有複數個SAW濾波器13的印刷配線基板12(參考圖2A)。SAW濾波器13可藉由習知方法將形成有預定之梳形電極的壓電晶體切割作成單片化而形成。可使用倒裝晶片接合器或晶粒接合器等習知的裝置將SAW濾波器13搭載在印刷配線基板12上。SAW濾波器13與印刷配線基板12是藉由突塊等的突起電極13a形成電性連結。又，在SAW濾波器13與印刷配線基板12之間，為了不阻礙表面彈性波在SAW濾波器表面的傳播，便維持著中空部分14。SAW濾波器13與印刷配線基 板12之間的距離可適宜設定，一般為15~50μm左右。 The SAW filter mounting substrate preparation step is to prepare a printed wiring board 12 on which a plurality of SAW filters 13 are mounted (see FIG. 2A). The SAW filter 13 can be formed by dicing a piezoelectric crystal formed with a predetermined comb-shaped electrode into a single piece by a conventional method. The SAW filter 13 can be mounted on the printed wiring board 12 by a conventional device such as a flip chip bonder or a die bonder. The SAW filter 13 and the printed wiring board 12 are electrically connected by the bump electrodes 13a such as bumps. Further, the hollow portion 14 is maintained between the SAW filter 13 and the printed wiring board 12 so as not to hinder the propagation of the surface acoustic wave on the surface of the SAW filter. SAW filter 13 and printed wiring base The distance between the plates 12 can be appropriately set, and is generally about 15 to 50 μm.

(密封步驟) (sealing step)

在密封步驟，是以覆蓋SAW濾波器13的方式對印刷配線基板12積層樹脂薄片11，並將SAW濾波器13以樹脂薄片11來樹脂密封(參考圖2B)。樹脂薄片11之作用是作為密封樹脂，用以從外界保護SAW濾波器13及附屬於其的要素。 In the sealing step, the resin sheet 11 is laminated on the printed wiring substrate 12 so as to cover the SAW filter 13, and the SAW filter 13 is resin-sealed with the resin sheet 11 (refer to FIG. 2B). The resin sheet 11 functions as a sealing resin for protecting the SAW filter 13 and the elements attached thereto from the outside.

將樹脂薄片11積層在印刷配線基板12上的方法並無特別限定，可利用熱壓或積層機等習知的方法來進行。在熱壓條件方面，溫度例如為40~100℃，且宜為50~90℃；壓力例如為0.1~10MPa，且宜為0.5~8MPa；時間例如為0.3~10分鐘，且宜為0.5~5分鐘。又，若考慮到提升樹脂薄片11對SAW濾波13及印刷配線基板12的密著性及追隨性，宜在減壓條件下(例如0.1~5kPa)行加壓。 The method of laminating the resin sheet 11 on the printed wiring board 12 is not particularly limited, and it can be carried out by a conventional method such as a hot press or a laminator. In terms of hot pressing conditions, the temperature is, for example, 40 to 100 ° C, and preferably 50 to 90 ° C; the pressure is, for example, 0.1 to 10 MPa, and preferably 0.5 to 8 MPa; the time is, for example, 0.3 to 10 minutes, and preferably 0.5 to 5 minute. Moreover, in consideration of the adhesion and followability of the lift resin sheet 11 to the SAW filter 13 and the printed wiring board 12, it is preferable to pressurize under a reduced pressure condition (for example, 0.1 to 5 kPa).

(密封體形成步驟) (sealing body forming step)

在密封體形成步驟，是將樹脂薄片11行熱硬化處理來形成密封體15(參考圖2B)。 In the sealing body forming step, the resin sheet 11 is thermally hardened to form a sealing body 15 (refer to FIG. 2B).

作為熱硬化處理的條件，加熱溫度宜為100℃以上，且以120℃以上為佳。另一方面，加熱溫度的上限宜為200℃以下，且以180℃以下為佳。加熱時間宜為10分鐘以上，且以30分鐘以上為佳。另一方面，加熱時間的上限宜為180分鐘以下，且以120分鐘以下為佳。又，亦可依需要來加壓，且宜為0.1MPa以上、以0.5MPa以上為佳。另一方面，上限宜為10MPa以下，且以5MPa以下為佳。 As a condition of the heat hardening treatment, the heating temperature is preferably 100 ° C or more, and preferably 120 ° C or more. On the other hand, the upper limit of the heating temperature is preferably 200 ° C or lower, and preferably 180 ° C or lower. The heating time is preferably 10 minutes or more, and preferably 30 minutes or more. On the other hand, the upper limit of the heating time is preferably 180 minutes or less, and preferably 120 minutes or less. Further, it may be pressurized as needed, and is preferably 0.1 MPa or more and 0.5 MPa or more. On the other hand, the upper limit is preferably 10 MPa or less, and preferably 5 MPa or less.

(切割步驟) (cutting step)

接下來，亦可進行密封體15的切割(參考圖2C)。藉此，可以獲得以SAW濾波器13為單元的電子元件封裝體18。 Next, the sealing of the sealing body 15 can also be performed (refer to FIG. 2C). Thereby, the electronic component package 18 in which the SAW filter 13 is a unit can be obtained.

(基板安裝步驟) (substrate mounting step)

依需要可進行基板安裝步驟，其係對電子元件封裝體18形成再配線及突塊，並將其安裝在另外之基板(圖無顯示)。在對基板安裝電子元件封裝體18時，可使用倒裝晶片接合器或晶粒接合器等習知的裝置。 The substrate mounting step can be performed as needed, and the electronic component package 18 is formed with rewiring and bumps, and mounted on another substrate (not shown). When the electronic component package 18 is mounted on the substrate, a conventional device such as a flip chip bonder or a die bonder can be used.

實施例 Example

以下舉本發明之適當實施例來詳細說明。但該實施例記載之材料或摻合量等，在無特別限定性的記載之下，並不會將本發明的範圍僅限定在該等所揭。 The following is a detailed description of suitable embodiments of the invention. However, the materials, blending amounts, and the like described in the examples are not intended to limit the scope of the invention to those disclosed herein.

說明關於使用在實施例的成分。 The ingredients used in the examples are explained.

環氧樹脂1：新日鐵化學(股)製的YSLV-80XY(雙酚F型環氧樹脂、環氧當量200g/eq.軟化點80℃) Epoxy Resin 1: YSLV-80XY manufactured by Nippon Steel Chemical Co., Ltd. (bisphenol F epoxy resin, epoxy equivalent 200 g/eq. softening point 80 ° C)

環氧樹脂2：日本化藥(股)製的EPPN-501HY(三苯甲烷型環氧樹脂) Epoxy Resin 2: EPPN-501HY (triphenylmethane type epoxy resin) made by Nippon Kayaku Co., Ltd.

環氧樹脂3：三菱化學(股)製的YL980(雙酚A型環氧樹脂) Epoxy Resin 3: YL980 (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation

酚樹脂1：明和化成社製的MEH-7851-SS(具有聯苯基芳烷基骨架的酚樹脂，羥基當量203g/eq.，軟化點67℃) Phenol Resin 1: MEH-7851-SS (a phenol resin having a biphenyl aralkyl skeleton, a hydroxyl equivalent of 203 g/eq., a softening point of 67 ° C) manufactured by Minghe Chemical Co., Ltd.

酚樹脂2：昭和高分子(股)製的ND564 Phenol Resin 2: ND564 made by Showa Polymer Co., Ltd.

熱塑性樹脂1：Kaneka社製的SIBSTER 072T(苯乙烯-異丁烯-苯乙烯嵌段共聚物) Thermoplastic Resin 1: SIBSTER 072T (styrene-isobutylene-styrene block copolymer) manufactured by Kaneka

熱塑性樹脂2：Nagase ChemteX(股)製的SG-P3 Thermoplastic Resin 2: SG-P3 manufactured by Nagase ChemteX Co., Ltd.

無機填充劑：電氣化學工業社製的FB-9454FC(熔融球狀二氧化矽、平均粒徑20μm) Inorganic filler: FB-9454FC (melt spherical cerium oxide, average particle size 20 μm) manufactured by Denki Kogyo Co., Ltd.

矽烷偶合劑：信越化學社製的KBM-403(3-環氧丙氧基丙基三甲氧基矽烷) Decane coupling agent: KBM-403 (3-glycidoxypropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd.

碳黑：三菱化學社製的#20 Carbon black: #20 from Mitsubishi Chemical Corporation

阻燃劑：伏見製藥所製的FP-100(膦氮烯系阻燃劑：式(4)所表示之化合物) Flame retardant: FP-100 (phosphazene-based flame retardant: compound represented by formula (4)) manufactured by Fushimi Pharmaceutical Co., Ltd.

(式中，m表示3~4的整數。) (where m represents an integer from 3 to 4.)

硬化促進劑1：四國化成工業社製的2PHZ-PW(2-苯基-4,5-二羥基甲基咪唑) Hardening accelerator 1: 2PHZ-PW (2-phenyl-4,5-dihydroxymethylimidazole) manufactured by Shikoku Chemicals Co., Ltd.

硬化促進劑2：北興化學工業社製的TPP-MK(四苯基鏻四-對甲苯硼酸鹽) Hardening accelerator 2: TPP-MK (tetraphenylphosphonium tetra-p-toluene borate) manufactured by Behind Chemical Industry Co., Ltd.

實施例1~3 Example 1~3

遵照表1記載之摻合比來摻合各成分，並利雙軸捏合機在60~120℃、10分鐘、減壓條件下(0.01kg/cm2)熔融捏合來調製捏合物。接著，將獲得之捏合物利用平板加壓法形成薄片狀來製作表1所示之厚度的樹脂薄片。在獲得之樹脂薄片貼附有分隔件。 Each component was blended in accordance with the blending ratios shown in Table 1, and the kneaded product was prepared by melt-kneading at 60 to 120 ° C for 10 minutes under reduced pressure (0.01 kg/cm 2 ) in a biaxial kneader. Next, the obtained kneaded material was formed into a sheet shape by a flat press method to prepare a resin sheet having the thickness shown in Table 1. A separator is attached to the obtained resin sheet.

使用獲得之樹脂薄片來進行下述的評價。結果顯在表1。 The following evaluation was performed using the obtained resin sheet. The results are shown in Table 1.

[排氣量] [discharge]

從未硬化的樹脂薄片切取1cm×1cm×厚度200μm的樣品，並剝下附在樣品上的分隔件。將樣品置入試樣瓶並秤量。之後，以頂隙進樣機(HSS)在150℃、1小時的條件下加熱樣品。將加熱狀態之氣體1ml注入Agilen Technology社製6890GC-MS來測定排氣量。 A sample of 1 cm × 1 cm × 200 μm in thickness was cut out from the unhardened resin sheet, and the separator attached to the sample was peeled off. Place the sample in the vial and weigh it. Thereafter, the sample was heated with a headspace sampler (HSS) at 150 ° C for 1 hour. 1 ml of a gas in a heated state was injected into 6890GC-MS manufactured by Agilent Technology Co., Ltd. to measure the amount of exhaust gas.

[硬化物之減少1%重量的溫度] [The temperature at which the hardened material is reduced by 1% by weight]

從未硬化之樹脂薄片剝下分隔件後，將樹脂薄片在150℃下加熱1小時使其硬化。從硬化物切取約8mg的樣品。利用SII NanoTechnology社製的TG/DTA220，以10℃/min、Air中氣體流量200mg/min，將樣品從室溫加熱到500℃，並分析重量。 After the separator was peeled off from the unhardened resin sheet, the resin sheet was heated at 150 ° C for 1 hour to be hardened. Approximately 8 mg of the sample was cut from the hardened material. The sample was heated from room temperature to 500 ° C at 10 ° C / min, gas flow rate of 200 mg / min in Air using TG / DTA220 manufactured by SII NanoTechnology Co., Ltd., and analyzed for weight.

[硬化物之排氣量] [The amount of hardened material is exhausted]

從未硬化之樹脂薄片切取1cm×1cm×厚度200μm的樣品，並剝下附在樣品上的分隔件。將樣品在150℃下加熱1小時使其硬化。將硬化物置入試樣瓶並秤量。之後，以頂隙進樣機(HSS)加熱硬化物(加熱條件：以10℃/分的昇溫速 度從40℃昇溫到260℃後，在260℃下保持1分鐘)。將加熱狀態的氣體1ml注入Agilen Technology社製的6890GC-MS來測定排氣量。 A sample of 1 cm × 1 cm × 200 μm in thickness was cut out from the unhardened resin sheet, and the separator attached to the sample was peeled off. The sample was hardened by heating at 150 ° C for 1 hour. Place the hardened material into the sample vial and weigh it. After that, the hardened material was heated by a headspace sampler (HSS) (heating conditions: heating rate at 10 ° C / min) The temperature was raised from 40 ° C to 260 ° C and maintained at 260 ° C for 1 minute). 1 ml of a gas in a heated state was injected into 6890GC-MS manufactured by Agilent Technology Co., Ltd. to measure the amount of exhaust gas.

比較例1~2 Comparative example 1~2

遵照表1記載的摻合比來摻合各成分，並於其中添加與各成分總量等量之甲基乙基酮來調製清漆。利用逗號刮塗機(comma coater)將獲得之清漆以乾燥後之厚度為50μm的方式塗裝在厚度50μm之聚酯薄膜A(三菱化學聚酯社製、MRF-50)的剝離處理面上，並使之乾燥。接著，將厚度38μm之聚酯薄膜B(三菱化學聚酯社製、MRF-38)的剝離處理面貼合於乾燥後的清漆上，製成薄膜樹脂薄片。 The components were blended in accordance with the blending ratios shown in Table 1, and methyl ketone was added in an amount equivalent to the total amount of each component to prepare a varnish. The obtained varnish was applied to a release-treated surface of a polyester film A (manufactured by Mitsubishi Chemical Polyester Co., Ltd., MRF-50) having a thickness of 50 μm by a comma coater at a thickness of 50 μm. And let it dry. Then, the release-treated surface of the polyester film B (manufactured by Mitsubishi Chemical Co., Ltd., MRF-38) having a thickness of 38 μm was bonded to the dried varnish to obtain a film resin sheet.

之後，將聚酯薄膜A及聚酯薄膜B適當剝離，同時利用輥積層機積層4片薄膜樹脂薄片，藉此製作厚度200μm的樹脂薄片。 Thereafter, the polyester film A and the polyester film B were appropriately peeled off, and four film resin sheets were laminated by a roll laminator to prepare a resin sheet having a thickness of 200 μm.

使用獲得之樹脂薄片進行上述評價。結果顯示在表1。 The above evaluation was carried out using the obtained resin sheet. The results are shown in Table 1.

11‧‧‧樹脂薄片 11‧‧‧Resin sheet

11a‧‧‧支持體 11a‧‧‧Support

Claims (4)

一種電子元件密封用樹脂薄片，其厚度為100~2000μm，且在150℃下使之硬化1小時後產生的氣體量為500ppm以下。 A resin sheet for sealing an electronic component having a thickness of 100 to 2000 μm and having a hardness of 500 ppm or less after being cured at 150 ° C for 1 hour. 如請求項1之電子元件密封用樹脂薄片，其在150℃下硬化1小時所獲得之硬化物的減少1%重量溫度為260℃以上。 The resin sheet for electronic component sealing of claim 1 which has a 1% by weight reduction of the cured product obtained by curing at 150 ° C for 1 hour is 260 ° C or higher. 如請求項1或2之電子元件密封用樹脂薄片，將其在150℃下硬化1小時所獲得之硬化物，以昇溫速度10℃/分從40℃昇溫到260℃，接著在260℃下加熱1分鐘時，產生的氣體量為500ppm以下。 The resin sheet for electronic component sealing according to claim 1 or 2, which is cured by curing at 150 ° C for 1 hour, is heated from 40 ° C to 260 ° C at a temperature increase rate of 10 ° C / min, and then heated at 260 ° C. At 1 minute, the amount of gas generated was 500 ppm or less. 一種電子元件封裝體的製造方法，包含下述步驟：積層步驟，以覆蓋1個或複數個電子元件的方式將如請求項1至3中任一項之電子元件密封用樹脂薄片積層在前述電子元件上，及密封體形成步驟，使前述電子元件密封用樹脂薄片硬化來形成密封體。 A method of manufacturing an electronic component package, comprising the step of laminating a resin sheet for sealing an electronic component according to any one of claims 1 to 3 in a manner of covering one or a plurality of electronic components In the element and the sealing body forming step, the resin sheet for sealing an electronic component is cured to form a sealing body.
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