TWI701276B - Hollow electronic device sealing sheet and hollow electronic device packaging manufacturing method - Google Patents

Hollow electronic device sealing sheet and hollow electronic device packaging manufacturing method Download PDF

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TWI701276B
TWI701276B TW108104649A TW108104649A TWI701276B TW I701276 B TWI701276 B TW I701276B TW 108104649 A TW108104649 A TW 108104649A TW 108104649 A TW108104649 A TW 108104649A TW I701276 B TWI701276 B TW I701276B
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electronic device
hollow
sealing sheet
ion
resin
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TW201920397A (en
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豊田英志
清水祐作
砂原肇
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日商日東電工股份有限公司
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    • H—ELECTRICITY
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    • H01L23/00—Details of semiconductor or other solid state devices
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    • 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
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    • H—ELECTRICITY
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    • 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
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    • 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
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    • 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
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    • 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
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Abstract

本發明係一種中空型電子裝置密封用薄片，其係將中空型電子裝置密封用薄片浸漬於離子交換水50ml中，在121℃、2氣壓下放置20小時之後的離子交換水中之氯化物離子濃度、鈉離子濃度、磷酸離子濃度、及硫酸離子濃度當中的至少1個係低於一定值。 The present invention is a hollow-type electronic device sealing sheet. The hollow-type electronic device sealing sheet is immersed in 50 ml of ion-exchanged water, and the chloride ion concentration in the ion-exchanged water after being placed at 121°C and 2 atmospheric pressure for 20 hours , At least one of sodium ion concentration, phosphate ion concentration, and sulfate ion concentration is below a certain value.

Description

中空型電子裝置密封用薄片及中空型電子裝置封裝之製造方法 Hollow electronic device sealing sheet and hollow electronic device packaging manufacturing method

本發明係關於中空型電子裝置密封用薄片及中空型電子裝置封裝之製造方法。 The present invention relates to a hollow-type electronic device sealing sheet and a manufacturing method of the hollow-type electronic device package.

以往，在將電子裝置與基板之間成為中空結構的中空型電子裝置進行樹脂密封而製作中空型電子裝置封裝時，有時使用薄片狀者作為密封樹脂(例如，參照專利文獻1)。 Conventionally, when a hollow electronic device having a hollow structure between an electronic device and a substrate is resin-sealed to produce a hollow electronic device package, a sheet-shaped one is sometimes used as the sealing resin (for example, refer to Patent Document 1).

[先前技術文獻] [Prior 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 Patent Application Publication No. 2006-19714

於中空型電子裝置封裝中，會有因來自密封所使用之薄片狀的密封樹脂之各種離子性雜質而使中空型電子裝 置受到影響的情況。尤其，於中空型電子裝置封裝中，若離子性雜質從薄片狀的密封樹脂滲出則容易積存於中空空間，恐有受其之影響而使作為中空型電子裝置的特性(例如，作為壓力感測器、振動感測器等使用時之感測特性、作為SAW過濾器等使用時之過濾特性等)無法充分發揮之虞。因此，期望有離子性雜質之含量少的密封樹脂。 In hollow electronic device packaging, the hollow electronic device may be affected by various ionic impurities from the sheet-like sealing resin used for sealing. In particular, in the hollow electronic device package, if the ionic impurities ooze out of the sheet-like sealing resin, they are likely to accumulate in the hollow space, which may be affected by the hollow electronic device's characteristics (for example, as a pressure sensor). The sensor, vibration sensor, etc., the sensing characteristics when used, and the filtering characteristics when used as a SAW filter, etc.) may not be fully utilized. Therefore, a sealing resin with a small content of ionic impurities is desired.

本發明係鑑於上述課題而完成者，其目的為提供一種離子性雜質之滲出量少的中空型電子裝置密封用薄片、及離子性雜質之滲出量少的中空型電子裝置封裝之製造方法。 The present invention was made in view of the above-mentioned problems, and its object is to provide a hollow electronic device sealing sheet with a small amount of ionic impurities and a method for manufacturing a hollow electronic device package with a small amount of ionic impurities.

本發明者們發現藉由採用下述的構成，可解決前述課題，因而完成本發明。 The inventors found that the aforementioned problems can be solved by adopting the following configuration, and completed the present invention.

亦即，本發明係一種中空型電子裝置密封用薄片，其特徵為滿足下述(a)~下述(d)中至少1個。 That is, the present invention is a hollow electronic device sealing sheet characterized by satisfying at least one of the following (a) to (d).

(a)將重量5g之中空型電子裝置密封用薄片浸漬於離子交換水50ml中，在121℃、2氣壓下放置20小時之後的前述離子交換水中之氯化物離子濃度，以質量基準計為低於30ppm、(b)將重量5g之中空型電子裝置密封用薄片浸漬於離子交換水50ml中，在121℃、2氣壓下放置20小時之後的前述離子交換水中之鈉離子濃度，以質量基準計為低於10ppm、 (c)將重量5g之中空型電子裝置密封用薄片浸漬於離子交換水50ml中，在121℃、2氣壓下放置20小時之後的前述離子交換水中之磷酸離子濃度，以質量基準計為低於30ppm、(d)將重量5g之中空型電子裝置密封用薄片浸漬於離子交換水50ml中，在121℃、2氣壓下放置20小時之後的前述離子交換水中之硫酸離子濃度，以質量基準計為低於5ppm。 (a) The concentration of chloride ions in the aforementioned ion-exchanged water after immersing 5 g of hollow electronic device sealing sheet in 50 ml of ion-exchanged water at 121°C and 2 atmospheric pressure for 20 hours is low on a mass basis (B) The sodium ion concentration in the aforementioned ion-exchanged water after immersing 5 g of hollow electronic device sealing sheet in 50 ml of ion-exchanged water in 50 ml of ion-exchanged water at 30 ppm and (b) on a mass basis. To be less than 10ppm, (c) The phosphate ion concentration in the aforementioned ion-exchanged water after immersing 5g of hollow electronic device sealing sheet in 50ml of ion-exchanged water at 121°C and 2 atmospheric pressure for 20 hours, by mass The standard is less than 30 ppm. (d) The concentration of sulfate ions in the aforementioned ion-exchanged water after immersing 5 g of hollow electronic device sealing sheet in 50 ml of ion-exchanged water and leaving it at 121°C and 2 atmospheric pressure for 20 hours, It is less than 5 ppm on a mass basis.

依據本發明之中空型電子裝置密封用薄片，則滿足上述(a)~上述(d)中至少1個。因而，離子性雜質(氯化物離子、鈉離子、磷酸離子(PO4 3-)、及硫酸離子(SO4 2-)中至少1個)之滲出量減少。其結果，使用該中空型電子裝置密封用薄片所製造的中空型電子裝置封裝，係可抑制特性降低，而可提昇製品信賴性。 According to the hollow electronic device sealing sheet of the present invention, at least one of the above (a) to (d) is satisfied. Therefore, the amount of exudation of ionic impurities (at least one of chloride ion, sodium ion, phosphate ion (PO 4 3- ), and sulfate ion (SO 4 2- )) is reduced. As a result, the hollow-type electronic device package manufactured using the hollow-type electronic device sealing sheet can suppress the decrease in characteristics and improve the reliability of the product.

於前述構成中，在厚度250μm時之熱硬化後的透濕度為溫度85℃、濕度85%、168小時之條件下，較佳為500g/m2．24小時以下。 In the aforementioned structure, the moisture permeability after heat curing at a thickness of 250μm is at a temperature of 85°C, a humidity of 85%, and 168 hours, preferably 500g/m 2 . Less than 24 hours.

本發明者們，探究出即使在浸漬於離子交換水時之離子性雜質的滲出量少，若透過中空型電子裝置密封用薄片而到達中空部分的水分多，仍恐有離子性雜質融入此水分中等而流入電子裝置側，使離子性雜質蓄積於電子裝置上之虞。因此，若前述中空型電子裝置密封用薄片在厚度成為250μm時之熱硬化後的透濕度，於溫度85℃、濕度85%、168小時之條件下，為500g/m2．24小時以下，則水分難以從 外部侵入到中空部分。其結果，可抑制離子性雜質融入來自外部的水分而到達電子裝置上。 The inventors have discovered that even if the amount of ionic impurities exuded when immersed in ion-exchange water is small, if there is a large amount of water that reaches the hollow part through the hollow electronic device sealing sheet, there is still a fear that ionic impurities will be incorporated into the water. It may flow into the electronic device side in the medium, causing ionic impurities to accumulate on the electronic device. Therefore, if the thickness of the above-mentioned hollow electronic device sealing sheet is 250μm, the moisture permeability after heat curing is 500g/m 2 under the conditions of a temperature of 85°C and a humidity of 85% for 168 hours. After 24 hours, it is difficult for moisture to penetrate into the hollow part from the outside. As a result, it is possible to prevent ionic impurities from being absorbed by moisture from the outside and reaching the electronic device.

如此一來，除使中空型電子裝置密封用薄片之離子性雜質的滲出量減少以外，亦可藉由降低透濕度，而更提昇使用該中空電子裝置密封用薄片所製造的中空型電子裝置封裝之製品信賴性。另外，將透濕度的評估條件設為溫度85℃、濕度85%、168小時的原因在於，符合在半導體封裝之耐焊錫信賴性試驗(MSL試驗)中最為嚴苛的吸濕條件之Level 1條件。 In this way, in addition to reducing the amount of ionic impurities exuded from the hollow electronic device sealing sheet, the hollow electronic device package manufactured by using the hollow electronic device sealing sheet can also be improved by reducing the moisture permeability. The reliability of products. In addition, the reason why the evaluation conditions of the moisture permeability are set to 85°C, 85% humidity, and 168 hours is that it meets Level 1 conditions of the most severe moisture absorption conditions in the solder resistance reliability test (MSL test) of semiconductor packages. .

另外，於厚度非250μm時，係藉由下述式1換算，而作為在溫度85℃、濕度85%、168小時的條件下之厚度成為250μm時的透濕度。 In addition, when the thickness is not 250 μm, it is converted by the following formula 1 and used as the moisture permeability when the thickness becomes 250 μm under the conditions of temperature 85° C., humidity 85% and 168 hours.

(式1)A-(250-D)×0.101 (Formula 1) A-(250-D)×0.101

(A：透濕度、D：樣品厚度(μm)) (A: moisture permeability, D: sample thickness (μm))

於前述構成中，相對於中空型電子裝置密封用薄片全體，較佳為包含70~90體積%之無機質填充劑。若無機質填充劑之含量相對於中空型電子裝置密封用薄片全體為70體積%以上，則可容易降低透濕度。另一方面，若無機質填充劑之含量相對於中空型電子裝置密封用薄片全體為90體積%以下，則柔軟性、流動性、接著性更良好。 In the aforementioned structure, it is preferable to contain 70 to 90% by volume of the inorganic filler with respect to the entire hollow electronic device sealing sheet. If the content of the inorganic filler is 70% by volume or more with respect to the entire hollow-type electronic device sealing sheet, the moisture permeability can be easily reduced. On the other hand, if the content of the inorganic filler is 90% by volume or less with respect to the entire hollow-type electronic device sealing sheet, the flexibility, fluidity, and adhesiveness are more favorable.

於前述構成中，較佳為含有離子捕捉劑。若含有離子捕捉劑，則可更加抑制離子性雜質到達電子裝置。 In the aforementioned configuration, it is preferable to contain an ion scavenger. If the ion trapping agent is contained, it is possible to further suppress the ionic impurities from reaching the electronic device.

於前述構成中，前述離子捕捉劑，較佳為水滑石 系化合物。水滑石系化合物，係不含有銻等之重金屬而具有離子捕捉性。 In the aforementioned configuration, the aforementioned ion trapping agent is preferably a hydrotalcite-based compound. The hydrotalcite compound does not contain heavy metals such as antimony and has ion-trapping properties.

此外，本發明之中空型電子裝置封裝之製造方法，其特徵為包含：以被覆搭載於基板上之1或複數個中空型電子裝置的方式，將前述記載之中空型電子裝置密封用樹脂薄片層合於前述中空型電子裝置上之層合步驟，以及使前述中空型電子裝置密封用樹脂薄片硬化而形成密封體之密封體形成步驟。 In addition, the method for manufacturing a hollow electronic device package of the present invention is characterized by comprising: covering one or more hollow electronic devices mounted on a substrate, and applying the aforementioned hollow electronic device sealing resin sheet layer A lamination step to be combined on the hollow electronic device, and a sealing body forming step to harden the resin sheet for sealing the hollow electronic device to form a sealed body.

使用前述記載之中空型電子裝置密封用樹脂薄片所製造的中空型電子裝置封裝，係離子性雜質之滲出量少。因而，使用該中空型電子裝置密封用樹脂薄片所製造的中空型電子裝置封裝，係可抑制特性降低，而可提昇製品信賴性。 The hollow electronic device package manufactured using the resin sheet for sealing a hollow electronic device described above has a small amount of exudation of ionic impurities. Therefore, the hollow-type electronic device package manufactured using the resin sheet for sealing the hollow-type electronic device can suppress the degradation of characteristics and improve the reliability of the product.

依據本發明，可提供一種離子性雜質之滲出量少的中空型電子裝置密封用薄片、及離子性雜質之滲出量少的中空型電子裝置封裝之製造方法。 According to the present invention, it is possible to provide a hollow electronic device sealing sheet with a small amount of ionic impurities, and a method for manufacturing a hollow electronic device package with a small amount of ionic impurities.

11‧‧‧中空型電子裝置密封用薄片(密封薄片) 11‧‧‧Hollow electronic device sealing sheet (sealing sheet)

11a‧‧‧支撐體 11a‧‧‧Support

13‧‧‧SAW過濾器 13‧‧‧SAW filter

15‧‧‧密封體 15‧‧‧Seal body

18‧‧‧中空型電子裝置封裝 18‧‧‧Hollow electronic device package

[第1圖]係模式性顯示本發明之一實施形態之中空型電子裝置密封用薄片的剖面圖。 [Figure 1] is a cross-sectional view schematically showing a hollow electronic device sealing sheet according to an embodiment of the present invention.

[第2圖A]係模式性顯示本發明之一實施形態之中空型電子裝置封裝的製造方法之一步驟的圖。 [Fig. 2A] is a diagram schematically showing a step of a method of manufacturing a hollow electronic device package according to an embodiment of the present invention.

[第2圖B]係模式性顯示本發明之一實施形態之中空型電子裝置封裝的製造方法之一步驟的圖。 [Fig. 2B] is a diagram schematically showing one of the steps of a method of manufacturing a hollow electronic device package according to an embodiment of the present invention.

[第2圖C]係模式性顯示本發明之一實施形態之中空型電子裝置封裝的製造方法之一步驟的圖。 [Fig. 2C] is a diagram schematically showing one of the steps of a method of manufacturing a hollow electronic device package according to an embodiment of the present invention.

以下，針對本發明之實施形態，一邊參照圖面一邊進行說明。但，本發明並不僅限定於此等實施形態。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention is not limited to these embodiments.

[中空型電子裝置密封用薄片] [Hollow type electronic device sealing sheet]

第1圖係模式性顯示本發明之一實施形態之中空型電子裝置密封用薄片的剖面圖。中空型電子裝置密封用薄片11(以下，亦稱為「密封用薄片11」)，係代表性地以層合於聚對苯二甲酸乙二酯(PET)薄膜等之支撐體11a上的狀態提供。另外，於支撐體11a，係可為了容易進行密封用薄片11之剝離，而實施脫模處理。 Figure 1 is a cross-sectional view schematically showing a hollow electronic device sealing sheet according to an embodiment of the present invention. Hollow electronic device sealing sheet 11 (hereinafter also referred to as "sealing sheet 11") is typically laminated on a support 11a such as a polyethylene terephthalate (PET) film provide. In addition, the support 11a may be subjected to a mold release process in order to facilitate the peeling of the sealing sheet 11.

密封用薄片11，係滿足下述(a)~下述(d)中至少1個。 The sealing sheet 11 satisfies at least one of the following (a) to (d).

(a)將重量5g之中空型電子裝置密封用薄片浸漬於離子交換水50ml中，在121℃、2氣壓下放置20小時之後的前述離子交換水中之氯化物離子濃度，以質量基準計為低於30ppm、(b)將重量5g之中空型電子裝置密封用薄片浸漬於離子交換水50ml中，在121℃、2氣壓下放置20小時之後的前 述離子交換水中之鈉離子濃度，以質量基準計為低於10ppm、(c)將重量5g之中空型電子裝置密封用薄片浸漬於離子交換水50ml中，在121℃、2氣壓下放置20小時之後的前述離子交換水中之磷酸離子濃度，以質量基準計為低於30ppm、(d)將重量5g之中空型電子裝置密封用薄片浸漬於離子交換水50ml中，在121℃、2氣壓下放置20小時之後的前述離子交換水中之硫酸離子濃度，以質量基準計為低於5ppm。 (a) The concentration of chloride ions in the aforementioned ion-exchanged water after immersing 5 g of hollow electronic device sealing sheet in 50 ml of ion-exchanged water at 121°C and 2 atmospheric pressure for 20 hours is low on a mass basis (B) The sodium ion concentration in the aforementioned ion-exchanged water after immersing 5 g of hollow electronic device sealing sheet in 50 ml of ion-exchanged water in 50 ml of ion-exchanged water at 30 ppm and (b) on a mass basis. To be less than 10ppm, (c) the phosphate ion concentration in the aforementioned ion-exchange water after immersing 5g of hollow electronic device sealing sheet in 50ml of ion-exchanged water at 121°C and 2 atmospheric pressure for 20 hours, by mass The standard is less than 30 ppm. (d) The concentration of sulfate ions in the aforementioned ion-exchanged water after immersing 5 g of hollow electronic device sealing sheet in 50 ml of ion-exchanged water and leaving it at 121°C and 2 atmospheric pressure for 20 hours, It is less than 5 ppm on a mass basis.

密封用薄片11，係由於滿足上述(a)~上述(d)中至少1個，因此離子性雜質(氯化物離子、鈉離子、磷酸離子、及硫酸離子中至少1個)之滲出量減少。其結果，使用該中空型電子裝置密封用薄片11所製造的中空型電子裝置封裝，係可抑制特性降低，而可提昇製品信賴性。用以滿足上述(a)~上述(d)中至少1個的方法，可例舉例如：於製造密封用薄片11時，選擇離子性雜質之含量少的材料，或含有能夠捕捉上述離子性雜質的離子捕捉劑之方法。 Since the sealing sheet 11 satisfies at least one of the above (a) to (d), the amount of exudation of ionic impurities (at least one of chloride ion, sodium ion, phosphate ion, and sulfate ion) is reduced. As a result, the hollow-type electronic device package manufactured using the hollow-type electronic device sealing sheet 11 can suppress the degradation of characteristics and improve the reliability of the product. A method for satisfying at least one of the above (a) to (d), for example, when manufacturing the sealing sheet 11, selecting a material with a small content of ionic impurities, or containing a material that can capture the above ionic impurities The method of ion trapping agent.

前述氯化物離子濃度較佳為低於20ppm。此外，前述氯化物離子濃度雖越小越好，但例如為1ppm以上。 The aforementioned chloride ion concentration is preferably less than 20 ppm. In addition, although the chloride ion concentration is as small as possible, it is, for example, 1 ppm or more.

前述鈉離子濃度較佳為低於7ppm。此外，前述鈉離子濃度雖越小越好，但例如為0.1ppm以上。 The aforementioned sodium ion concentration is preferably less than 7 ppm. In addition, although the sodium ion concentration is as small as possible, it is, for example, 0.1 ppm or more.

前述磷酸離子濃度較佳為低於20ppm。此外，前述磷酸離子濃度雖越小越好，但例如為1ppm以上。 The aforementioned phosphate ion concentration is preferably less than 20 ppm. In addition, the phosphate ion concentration is preferably as small as possible, but it is, for example, 1 ppm or more.

前述硫酸離子濃度較佳為低於3ppm。此外，前述硫酸離子濃度雖越小越好，但例如為0.1ppm以上。 The aforementioned sulfate ion concentration is preferably less than 3 ppm. In addition, the concentration of the aforementioned sulfate ion is preferably as small as possible, but it is, for example, 0.1 ppm or more.

密封用薄片11，在厚度成為250μm時之熱硬化後的透濕度，於溫度85℃、濕度85%、168小時之條件下，以500g/m2．24小時以下為佳，較佳為400g/m2．24小時以下，更佳為300g/m2．24小時以下。此外，前述透濕度雖越小越好，但例如為1g/m2．24小時以上。密封用薄片11在厚度成為250μm時之熱硬化後的透濕度，於溫度85℃、濕度85%、168小時之條件下，若為500g/m2．24小時以下，則水分難以從外部侵入到中空部分。其結果，可抑制離子性雜質融入來自外部的水分而到達電子裝置上。 The moisture permeability of the sealing sheet 11 after heat curing at a thickness of 250 μm is 500 g/m 2 at a temperature of 85°C, a humidity of 85%, and 168 hours. It is preferably less than 24 hours, preferably 400g/m 2 . Less than 24 hours, more preferably 300g/m 2 . Less than 24 hours. In addition, although the aforementioned moisture permeability is as small as possible, it is, for example, 1 g/m 2 . More than 24 hours. When the thickness of the sealing sheet 11 becomes 250 μm, the moisture permeability after heat curing is 500 g/m 2 under the conditions of a temperature of 85°C and a humidity of 85% for 168 hours. After 24 hours, it is difficult for moisture to penetrate into the hollow part from the outside. As a result, it is possible to prevent ionic impurities from being absorbed by moisture from the outside and reaching the electronic device.

如此一來，除使中空型電子裝置密封用薄片之離子性雜質的滲出量減少以外，亦可藉由降低透濕度，而更提昇使用該中空型電子裝置密封用薄片所製造的中空型電子裝置封裝之製品信賴性。 In this way, in addition to reducing the amount of ionic impurities in the hollow electronic device sealing sheet, the hollow electronic device manufactured by using the hollow electronic device sealing sheet can also be improved by reducing the moisture permeability. Reliability of packaged products.

接著，針對密封用薄片11之組成進行說明。 Next, the composition of the sealing sheet 11 will be described.

密封用薄片11，較佳為包含環氧樹脂、及酚樹脂。藉此，可得到良好的熱硬化性。 The sealing sheet 11 preferably contains an epoxy resin and a phenol resin. Thereby, good thermosetting properties can be obtained.

環氧樹脂並無特別限定。可使用例如：三苯基甲烷型環氧樹脂、甲酚酚醛清漆型環氧樹脂、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、酚酚醛清漆型環氧樹脂、苯氧基樹脂等之各種環氧樹脂。此等環氧樹脂係可單獨使用，亦可併用2種以上。 The epoxy resin is not particularly limited. For example: triphenylmethane type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, modified bisphenol A type epoxy resin, bisphenol A type epoxy resin, bisphenol F Type epoxy resin, modified bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, phenol novolak type epoxy resin, phenoxy resin, etc. These epoxy resins may be used alone, or two or more types may be used in combination.

就確保環氧樹脂之硬化後的韌性及環氧樹脂的反應性之觀點而言，以環氧當量150~250，軟化點或熔點為50~130℃之在常溫下為固體者為佳，其中，就信賴性之觀點而言，更佳為三苯基甲烷型環氧樹脂、甲酚酚醛清漆型環氧樹脂、聯苯型環氧樹脂。 From the viewpoint of ensuring the toughness of the epoxy resin after curing and the reactivity of the epoxy resin, the epoxy equivalent 150~250, the softening point or melting point of 50~130℃, which is solid at room temperature is better. From the viewpoint of reliability, triphenylmethane type epoxy resin, cresol novolak type epoxy resin, and biphenyl type epoxy resin are more preferable.

酚樹脂係只要在與環氧樹脂之間產生硬化反應者則無特別限定。例如，使用酚酚醛清漆樹脂、酚芳烷基樹脂、聯苯芳烷基樹脂、二環戊二烯型酚樹脂、甲酚酚醛清漆樹脂、可溶酚醛樹脂等。此等酚樹脂係可單獨使用，亦可併用2種以上。 The phenol resin is not particularly limited as long as it causes a hardening reaction with the epoxy resin. For example, phenol novolak resin, phenol aralkyl resin, biphenyl aralkyl resin, dicyclopentadiene type phenol resin, cresol novolak resin, resol phenol resin, etc. are used. These phenol resins may be used alone, or two or more of them may be used in combination.

酚樹脂，就與環氧樹脂之反應性的觀點而言，以使用羥基當量為70~250，軟化點為50~110℃者為佳，其中就硬化反應性高的觀點而言，可適當使用酚酚醛清漆樹脂。此外，就信賴性的觀點而言，亦可適當使用如同酚芳烷基樹脂或聯苯芳烷基樹脂之類的低吸濕性者。 Phenolic resin, from the viewpoint of reactivity with epoxy resin, it is preferable to use a hydroxyl equivalent of 70 to 250 and a softening point of 50 to 110°C. Among them, from the viewpoint of high curing reactivity, it can be suitably used Phenolic novolac resin. In addition, from the viewpoint of reliability, low hygroscopicity such as phenol aralkyl resin or biphenyl aralkyl resin can also be suitably used.

環氧樹脂與酚樹脂之摻合比例，就硬化反應性的觀點而言，較佳為相對於環氧樹脂中之環氧基1當量，以使酚樹脂中之羥基的合計成為0.7~1.5當量的方式摻合，更佳為0.9~1.2當量。 From the viewpoint of curing reactivity, the blending ratio of epoxy resin and phenol resin is preferably 1 equivalent with respect to epoxy groups in epoxy resin so that the total of hydroxyl groups in phenol resin becomes 0.7 to 1.5 equivalents The blending method is preferably 0.9~1.2 equivalent.

密封用薄片11中之環氧樹脂及酚樹脂的合計含量，較佳為2.0重量%以上，更佳為3.0重量%以上。若為2.0重量%以上，則良好地得到對於電子裝置、基板等之接著力。密封用薄片11中之環氧樹脂及酚樹脂的合計含量，較佳為20重量%以下，更佳為10重量%以下。若為20重量%以 下，則可減低吸濕性。 The total content of the epoxy resin and the phenol resin in the sealing sheet 11 is preferably 2.0% by weight or more, and more preferably 3.0% by weight or more. If it is 2.0% by weight or more, good adhesion to electronic devices, substrates, etc. is obtained. The total content of the epoxy resin and the phenol resin in the sealing sheet 11 is preferably 20% by weight or less, and more preferably 10% by weight or less. If it is 20% by weight or less, the hygroscopicity can be reduced.

密封用薄片11，較佳為包含熱塑性樹脂。藉此，可得到未硬化時之處理性、或硬化物之低應力性。 The sealing sheet 11 preferably contains a thermoplastic resin. Thereby, it is possible to obtain the rationality when it is not hardened, or the low stress of the hardened product.

熱塑性樹脂係可列舉：天然橡膠、丁基橡膠、異戊二烯橡膠、氯丁二烯橡膠、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-耐隆或6,6-耐隆等之聚醯胺樹脂、苯氧基樹脂、丙烯酸樹脂、PET或PBT等之飽和聚酯樹脂、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。此等熱塑性樹脂係可單獨，或將2種以上合併使用。其中，就低應力性、低吸水性的觀點而言，較佳為苯乙烯-異丁烯-苯乙烯嵌段共聚物。 Examples of thermoplastic resins include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, polybutadiene Resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resin such as 6-nylon or 6,6-nylon, phenoxy resin, acrylic resin, saturated polyester resin such as PET or PBT, Polyamide imide resin, fluororesin, styrene-isobutylene-styrene block copolymer, etc. These thermoplastic resins can be used alone 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.

密封用薄片11中之熱塑性樹脂的含量，較佳為1.0重量%以上，更佳為1.5重量%以上。若為1.0重量%以上，則可得到柔軟性、可撓性。密封用薄片11中之熱塑性樹脂的含量，較佳為3.5重量%以下，更佳為3重量%以下。若為3.5重量%以下，則與電子裝置或基板之接著性良好。 The content of the thermoplastic resin in the sealing sheet 11 is preferably 1.0% by weight or more, more preferably 1.5% by weight or more. If it is 1.0% by weight or more, flexibility and flexibility can be obtained. The content of the thermoplastic resin in the sealing sheet 11 is preferably 3.5% by weight or less, more preferably 3% by weight or less. If it is 3.5% by weight or less, the adhesion to the electronic device or the substrate is good.

密封用薄片11，較佳為包含無機質填充劑。 The sealing sheet 11 preferably contains an inorganic filler.

無機質填充劑並無特別限定，可使用以往周知的各種填充劑，可列舉例如：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、氮化硼之粉末。此等係可單獨使用，亦可併用2種以上。其中，就可良好地減低線膨脹係數的理由而言，較佳為二氧化矽、氧化鋁，更佳為二氧化矽。 The inorganic filler is not particularly limited, and various fillers known in the past can be used, such as quartz glass, talc, silica (fused silica or crystalline silica, etc.), alumina, aluminum nitride, Powder of silicon nitride and boron nitride. These systems can be used alone or in combination of two or more types. Among them, for the reason that the coefficient of linear expansion can be reduced satisfactorily, silicon dioxide and aluminum oxide are preferable, and silicon dioxide is more preferable.

二氧化矽，較佳為二氧化矽粉末，更佳為熔融二氧化矽粉末。熔融二氧化矽粉末，雖可列舉球狀熔融二氧化矽粉末、破碎熔融二氧化矽粉末，但就流動性的觀點而言，較佳為球狀熔融二氧化矽粉末。其中，以平均粒徑為10~30μm之範圍者為佳，以15~25μm之範圍者為更佳。 The silicon dioxide is preferably silicon dioxide powder, more preferably fused silicon dioxide powder. The molten silica powder includes spherical molten silica powder and crushed molten silica powder, but from the viewpoint of fluidity, spherical molten silica powder is preferred. Among them, the average particle size is preferably in the range of 10 to 30 μm, and the range is more preferably in the range of 15 to 25 μm.

另外，平均粒徑，例如，可藉由使用從母體所任意萃取出的試料，並使用雷射繞射散亂式粒度分布測定裝置進行測定而導出。 In addition, the average particle size can be derived, for example, by using a sample arbitrarily extracted from the matrix and measuring it with a laser diffraction scattering type particle size distribution measuring device.

密封用薄片11中之無機質填充劑的含量，較佳為相對於密封用薄片11全體，為70~90體積%，更佳為74~85體積%。若前述無機質填充劑的含量，相對於密封用薄片11全體為70體積%以上，則可容易地降低透濕度。另一方面，若前述無機質填充劑的含量相對於密封用薄片11全體為90體積%以下，則柔軟性、流動性、接著性更良好。 The content of the inorganic filler in the sealing sheet 11 is preferably 70 to 90% by volume relative to the entire sealing sheet 11, more preferably 74 to 85% by volume. If the content of the aforementioned inorganic filler is 70% by volume or more with respect to the entire sealing sheet 11, the moisture permeability can be easily reduced. On the other hand, when the content of the aforementioned inorganic filler is 90% by volume or less with respect to the entire sealing sheet 11, the flexibility, fluidity, and adhesiveness are more favorable.

無機質填充劑的含量，亦可以「重量%」為單位進行說明。代表性地針對二氧化矽之含量，以「重量%」為單位進行說明。 The content of the inorganic filler can also be described in units of "% by weight". Representatively, the content of silicon dioxide is explained with "weight%" as the unit.

二氧化矽，由於通常比重為2.2g/cm3，因此二氧化矽的含量(重量%)之適當範圍係如以下所述。 Since silicon dioxide usually has a specific gravity of 2.2 g/cm 3 , the appropriate range of the content (weight %) of silicon dioxide is as follows.

亦即，密封用薄片11中之二氧化矽的含量，較佳為81重量%以上，更佳為84重量%以上。密封用薄片11中之二氧化矽的含量，較佳為94重量%以下，更佳為91重量%以下。 That is, the content of silicon dioxide in the sealing sheet 11 is preferably 81% by weight or more, and more preferably 84% by weight or more. The content of silicon dioxide in the sealing sheet 11 is preferably 94% by weight or less, more preferably 91% by weight or less.

氧化鋁，由於通常比重為3.9g/cm3，因此氧化鋁 的含量(重量%)之適當範圍係如以下所述。 Alumina generally has a specific gravity of 3.9 g/cm 3 , so the appropriate range of the content (% by weight) of alumina is as follows.

亦即，密封用薄片11中之氧化鋁的含量，較佳為88重量%以上，更佳為90重量%以上。密封用薄片11中之氧化鋁的含量，較佳為97重量%以下，更佳為95重量%以下。 That is, the content of alumina in the sealing sheet 11 is preferably 88% by weight or more, and more preferably 90% by weight or more. The content of alumina in the sealing sheet 11 is preferably 97% by weight or less, more preferably 95% by weight or less.

密封用薄片11，較佳為包含離子捕捉劑。若含有離子捕捉劑，則可更加抑制離子性雜質到達電子裝置。 The sealing sheet 11 preferably contains an ion scavenger. If the ion trapping agent is contained, it is possible to further suppress the ionic impurities from reaching the electronic device.

前述離子捕捉劑，可列舉例如：水滑石類化合物、氫氧化鉍、五氧化二銻等。此等係可單獨或2種以上合併使用。其中，就不含有重金屬而具有離子捕捉性的觀點而言，較佳使用水滑石類化合物。 Examples of the aforementioned ion scavenger include hydrotalcite compounds, bismuth hydroxide, and antimony pentoxide. These systems can be used alone or in combination of two or more. Among them, it is preferable to use a hydrotalcite compound from the viewpoint of not containing heavy metals and having ion trapping properties.

前述離子捕捉劑之平均粒徑，就流動性的觀點而言，較佳為0.1~50μm之範圍內。另外，平均粒徑，例如，可藉由使用從母體所任意萃取出的試料，並使用雷射繞射散亂式粒度分布測定裝置進行測定而導出。 The average particle diameter of the aforementioned ion scavenger is preferably in the range of 0.1 to 50 μm from the viewpoint of fluidity. In addition, the average particle size can be derived, for example, by using a sample arbitrarily extracted from the matrix and measuring it with a laser diffraction scattering type particle size distribution measuring device.

前述離子捕捉劑之含有比例，較佳為相對於密封用薄片11全體設定為0.01~2重量%之範圍，特佳為0.01~1重量%。藉由將離子捕捉劑之含有比例設為相對於密封用薄片11全體為0.01重量%以上，可得到充分的離子捕捉性。此外，藉由將離子捕捉劑之含有比例設為相對於密封用薄片11全體為2重量%以下，可抑制成形時之封裝污染。 The content ratio of the aforementioned ion scavenger is preferably set in the range of 0.01 to 2% by weight with respect to the entire sealing sheet 11, and particularly preferably 0.01 to 1% by weight. By setting the content ratio of the ion trapping agent to 0.01% by weight or more with respect to the entire sealing sheet 11, sufficient ion trapping properties can be obtained. In addition, by setting the content of the ion scavenger to be 2% by weight or less with respect to the entire sealing sheet 11, package contamination during molding can be suppressed.

密封用薄片11，較佳為包含硬化促進劑。 The sealing sheet 11 preferably contains a hardening accelerator.

硬化促進劑，係只要使環氧樹脂與酚樹脂之硬化進行者便無特別限定，可列舉例如：三苯基膦、四苯基鏻四苯基硼酸鹽等之有機磷系化合物；2-苯基-4,5-二羥甲基咪 唑、2-苯基-4-甲基-5-羥甲基咪唑等之咪唑系化合物等。其中，基於即使隨著混練時之溫度上昇硬化反應亦不急遽進行，而可良好地製作密封用薄片11的理由，較佳為2-苯基-4,5-二羥甲基咪唑。 The curing accelerator is not particularly limited as long as the curing of epoxy resin and phenol resin proceeds, and examples include organophosphorus compounds such as triphenylphosphine, tetraphenylphosphonium tetraphenyl borate, etc.; 2-benzene Imidazole-based compounds such as methyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole. Among them, because the hardening reaction does not progress rapidly even when the temperature rises during kneading and the sealing sheet 11 can be produced well, 2-phenyl-4,5-dimethylolimidazole is preferred.

硬化促進劑之含量，較佳為相對於環氧樹脂及酚樹脂之合計100重量份為0.1~5重量份。 The content of the hardening accelerator is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total of the epoxy resin and the phenol resin.

密封用薄片11，較佳為包含難燃劑成分。藉此，可減低因零件短路或發熱等而起火時之燃燒擴大。難燃劑組成分，係可使用例如：氫氧化鋁、氫氧化鎂、氫氧化鐵、氫氧化鈣、氫氧化錫、複合化金屬氫氧化物等之各種金屬氫氧化物；磷腈系難燃劑等。 The sealing sheet 11 preferably contains a flame retardant component. In this way, it is possible to reduce the expansion of combustion when a fire ignites due to parts short-circuiting or heat generation. The composition of the flame retardant can be various metal hydroxides such as aluminum hydroxide, magnesium hydroxide, iron hydroxide, calcium hydroxide, tin hydroxide, composite metal hydroxide, etc.; phosphazene-based flame retardant剂 etc.

就即使少量亦發揮難燃效果的觀點而言，磷腈系難燃劑所含有之磷元素的含有率，較佳為12重量%以上。 From the viewpoint of exhibiting a flame retardant effect even in a small amount, the content rate of the phosphorus element contained in the phosphazene-based flame retardant is preferably 12% by weight or more.

密封用薄片11中之難燃劑成分的含量，於全有機成分(無機填料除外)中，較佳為10重量%以上，更佳為15重量%以上。若為10重量%以上，則可良好地得到難燃性。密封用薄片11中之熱塑性樹脂的含量，較佳為30重量%以下，更佳為25重量%以下。若為30重量%以下，則有硬化物之物性降低(具體而言，係玻璃轉移溫度或高溫樹脂強度等之物性的降低)少的傾向。 The content of the flame retardant component in the sealing sheet 11 is preferably 10% by weight or more, more preferably 15% by weight or more in all organic components (excluding inorganic fillers). If it is 10% by weight or more, good flame retardancy can be obtained. The content of the thermoplastic resin in the sealing sheet 11 is preferably 30% by weight or less, more preferably 25% by weight or less. If it is 30% by weight or less, the physical properties of the cured product (specifically, physical properties such as glass transition temperature or high-temperature resin strength) tend to be small.

密封用薄片11，較佳為包含矽烷偶合劑。矽烷偶合劑並無特別限定，可列舉3-環氧丙氧基丙基三甲氧基矽烷等。 The sealing sheet 11 preferably contains a silane coupling agent. The silane coupling agent is not particularly limited, and 3-glycidoxypropyltrimethoxysilane and the like can be mentioned.

密封用薄片11中之矽烷偶合劑的含量，較佳為 0.1~3重量%。若為0.1重量%以上，則可充分得到硬化物的強度而降低吸水率。若為3重量%以下，則可降低排氣量。 The content of the silane coupling agent in the sealing sheet 11 is preferably 0.1 to 3% by weight. If it is 0.1% by weight or more, the strength of the cured product can be sufficiently obtained and the water absorption rate can be reduced. If it is 3% by weight or less, the displacement can be reduced.

密封用薄片11，較佳為包含顏料。顏料並無特別限定，可列舉碳黑等。 The sealing sheet 11 preferably contains a pigment. The pigment is not particularly limited, and carbon black and the like can be mentioned.

密封用薄片11中之顏料的含量，較佳為0.1~2重量%。若為0.1重量%以上，則在以雷射標記等進行標記時得到良好的標記性。若為2重量%以下，則可充分得到硬化物強度。 The content of the pigment in the sealing sheet 11 is preferably 0.1 to 2% by weight. If it is 0.1% by weight or more, good marking properties are obtained when marking with a laser marker or the like. If it is 2% by weight or less, the strength of the cured product can be sufficiently obtained.

另外，於樹脂組成物中，除上述各成分以外，可因應需要而適當摻合其他的添加劑。 In addition, in the resin composition, in addition to the above-mentioned components, other additives may be appropriately blended as needed.

密封用薄片11，雖可為單層結構，亦可為層合了2以上之密封用薄片的多層結構，但基於無層間剝離之虞，且薄片厚的均勻性高，容易降低透濕度的理由，較佳為單層結構。 The sealing sheet 11 may have a single-layer structure or a multilayer structure in which 2 or more sealing sheets are laminated, but because there is no risk of interlayer peeling, the thickness of the sheet is highly uniform, and the moisture permeability is easily reduced. , Preferably a single-layer structure.

密封用薄片11的厚度雖無特別限定，但就作為密封用薄片使用的觀點而言，例如為50μm~2000μm。 The thickness of the sealing sheet 11 is not particularly limited, but from the viewpoint of use as a sealing sheet, it is, for example, 50 μm to 2000 μm.

密封用薄片11之製造方法並無特別限定。可列舉例如：調製用以形成密封用薄片11的樹脂組成物之混練物，將所得到的混練物塑性加工成薄片狀的方法、或將於溶劑中溶解或分散有用以形成密封用薄片11的樹脂組成物者(清漆)塗佈於間隔物等，然後使其乾燥而得到的方法。採用將混練物塑性加工成薄片狀的方法時，由於可不使用溶劑而製作密封用薄片11，因此可抑制中空型電子裝置(例如， SAW過濾器13)因揮發的溶劑而受到影響。 The manufacturing method of the sheet|seat 11 for sealing is not specifically limited. Examples include a method of preparing a kneaded product of the resin composition for forming the sealing sheet 11, plastic processing the obtained kneaded product into a sheet shape, or dissolving or dispersing in a solvent to form the sealing sheet 11 A method in which a resin composition (varnish) is applied to a spacer or the like and then dried. When the method of plastically processing the kneaded product into a sheet shape, since the sealing sheet 11 can be produced without using a solvent, it is possible to prevent the hollow electronic device (for example, the SAW filter 13) from being affected by the volatilized solvent.

具體而言，藉由將後述之各成分以混合輥、加壓式捏合機、擠出機等之周知的混練機進行熔融混練而調製混練物，將所得到的混練物塑性加工成薄片狀。混練條件方面，溫度較佳為上述各成分之軟化點以上，例如為30~150℃，若考慮環氧樹脂之熱硬化性，則較佳為40~140℃，更佳為60~120℃。時間，例如為1~30分鐘，較佳為5~15分鐘。 Specifically, each component described later is melt-kneaded with a well-known kneader such as a mixing roll, a pressure kneader, and an extruder to prepare a kneaded product, and the obtained kneaded product is plastically processed into a flake shape. Regarding the kneading conditions, the temperature is preferably higher than the softening point of each component, for example, 30 to 150°C. Considering the thermosetting properties of the epoxy resin, it is preferably 40 to 140°C, more preferably 60 to 120°C. The time is, for example, 1 to 30 minutes, preferably 5 to 15 minutes.

混練，較佳為在減壓條件下(減壓環境下)進行。藉此，可脫氣，並且可防止氣體侵入混練物。減壓條件下之壓力，較佳為0.1kg/cm2以下，更佳為0.05kg/cm2以下。減壓下之壓力的下限雖無特別限定，但例如1×10-4kg/cm2以上。 Kneading is preferably carried out under reduced pressure conditions (under reduced pressure environment). Thereby, degassing can be achieved and gas can be prevented from entering the kneaded product. The pressure under reduced pressure is preferably 0.1 kg/cm 2 or less, more preferably 0.05 kg/cm 2 or less. Although the lower limit of the pressure under reduced pressure is not particularly limited, it is, for example, 1×10 -4 kg/cm 2 or more.

熔融混練後之混練物，較佳為不進行冷卻而以高溫狀態直接進行塑性加工。塑性加工方法並無特別限制，可列舉平板沖壓法、T模擠出法、螺紋模擠出法、輥軋壓延法、輥軋混練法、充氣擠出法、共擠出法、壓延成形法等等。塑性加工溫度方面，較佳為上述各成分之軟化點以上，若考慮環氧樹脂之熱硬化性及成形性，則例如為40~150℃，較佳為50~140℃，更佳為70~120℃。 The kneaded product after melt-kneading is preferably directly subjected to plastic processing in a high temperature state without cooling. The plastic processing method is not particularly limited, and examples include plate punching method, T die extrusion method, screw die extrusion method, roll calendering method, roll kneading method, inflation extrusion method, co-extrusion method, calender forming method, etc. Wait. In terms of the plastic working temperature, it is preferably above the softening point of each of the above components. Considering the thermosetting and formability of the epoxy resin, it is, for example, 40~150°C, preferably 50~140°C, more preferably 70~ 120°C.

密封用薄片11，係使用於需要中空密封的電子裝置(例如，SAW(Surface Acoustic Wave)過濾器；壓力感測器、振動感測器等之MEMS(Micro Electro Mechanical Systems))之密封。其中，可特別適合使用於SAW過濾器之密封。 The sealing sheet 11 is used for sealing electronic devices (for example, SAW (Surface Acoustic Wave) filters; MEMS (Micro Electro Mechanical Systems) such as pressure sensors, vibration sensors, etc.) that require hollow sealing. Among them, it is particularly suitable for sealing of SAW filters.

密封方法並無特別限定，可利用以往周知的方法進行密封。可列舉例如，以被覆基板上之中空型電子裝置的方式將未硬化之密封用薄片11層合(載置)於基板上，接著，使密封用薄片11硬化而進行密封的方法等。基板並無特別限定，可列舉例如：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 a conventionally known method can be used for sealing. For example, a method in which an uncured sealing sheet 11 is laminated (mounted) on the substrate so as to cover the hollow electronic device on the substrate, and then the sealing sheet 11 is cured and sealed. The substrate is not particularly limited, and examples thereof include printed wiring substrates, ceramic substrates, silicon substrates, and metal substrates.

[中空型電子裝置封裝之製造方法] [Method of manufacturing hollow electronic device package]

第2圖A~第2圖C係分別模式性顯示本發明之一實施形態之中空型電子裝置封裝的製造方法之一步驟的圖。於本實施形態中，藉由密封用薄片11將搭載於印刷配基板12上之作為中空型電子裝置的SAW過濾器13進行中空密封，而製作中空型電子裝置封裝。 2A to 2C are diagrams schematically showing one step of a method of manufacturing a hollow electronic device package according to an embodiment of the present invention. In this embodiment, the SAW filter 13 as a hollow electronic device mounted on the printed circuit board 12 is hollow-sealed by the sealing sheet 11 to produce a hollow electronic device package.

(SAW過濾器搭載基板準備步驟) (Preparation steps for SAW filter mounting board)

於SAW過濾器搭載基板準備步驟中，係準備搭載有複數之SAW過濾器13的印刷配線基板12(參照第2圖A)。SAW過濾器13，係可藉由將形成有特定的梳形電極之壓電結晶以周知的方法進行切割並予以個片化而形成。為了將SAW過濾器13搭載於印刷配線基板12，可使用倒裝晶片接合器或晶粒接合器等之周知的裝置。SAW過濾器13與印刷配線基板12，係透過凸緣等之突起電極13a而電連接。此外，SAW過濾器13與印刷配線基板12之間，係以不阻礙在SAW過濾器表面之表面彈性波的傳送之方式來維持中空部分 14。SAW過濾器13與印刷配線基板12之間的距離係可適當設定，一般而言為15~50μm左右。 In the SAW filter mounting board preparation step, a printed wiring board 12 on which a plurality of SAW filters 13 are mounted is prepared (refer to FIG. 2A). The SAW filter 13 can be formed by cutting a piezoelectric crystal formed with a specific comb-shaped electrode by a known method and dividing it into pieces. In order to mount the SAW filter 13 on the printed wiring board 12, a well-known device such as a flip chip bonder or a die bonder can be used. The SAW filter 13 and the printed wiring board 12 are electrically connected through a bump electrode 13a such as a flange. In addition, between the SAW filter 13 and the printed wiring board 12, the hollow portion 14 is maintained so as not to hinder the transmission of surface acoustic waves on the surface of the SAW filter. The distance between the SAW filter 13 and the printed wiring board 12 can be appropriately set, and is generally about 15-50 μm.

(密封步驟) (Sealing step)

於密封步驟中，以被覆SAW過濾器13的方式將密封用薄片11層合於印刷配線基板12，以密封用薄片11將SAW過濾器13進行樹脂密封(參照第2圖B)。密封用薄片11，係發揮用以保護SAW過濾器13及其附帶要素以免外部環境污染之密封樹脂的功能。 In the sealing step, the sealing sheet 11 is laminated on the printed wiring board 12 to cover the SAW filter 13, and the SAW filter 13 is resin-sealed with the sealing sheet 11 (see FIG. 2B). The sealing sheet 11 functions as a sealing resin to protect the SAW filter 13 and its accompanying elements from external environmental pollution.

將密封用薄片11層合於印刷配線基板12上的方法並無特別限定，可藉由熱加壓或層壓等周知的方法而進行。熱加壓條件方面，溫度例如為40~100℃，較佳為50~90℃，壓力例如為0.1~10MPa，較佳為0.5~8MPa，時間例如為0.3~10分鐘，較佳為0.5~5分鐘。藉此，可得到電子裝置埋入熱硬化性密封用薄片16的電子裝置封裝。此外，若考慮密封用薄片11對於SAW過濾器13及印刷配線基板12之密著性及追隨性的提昇，則較佳為於減壓條件下(例如0.1~5kPa)中進行加壓。 The method of laminating the sealing sheet 11 on the printed wiring board 12 is not particularly limited, and it can be performed by a known method such as heat press or lamination. Regarding hot press conditions, the temperature is, for example, 40~100°C, preferably 50~90°C, the pressure is, for example, 0.1~10MPa, preferably 0.5~8MPa, and the time is, for example, 0.3~10 minutes, preferably 0.5~5. minute. Thereby, an electronic device package in which the thermosetting sealing sheet 16 is embedded in the electronic device can be obtained. In addition, considering the improvement of the adhesion and followability of the sealing sheet 11 to the SAW filter 13 and the printed wiring board 12, it is preferable to pressurize under reduced pressure conditions (for example, 0.1 to 5 kPa).

(密封體形成步驟) (Steps of forming seal body)

於密封體形成步驟中，將密封用薄片11進行熱硬化處理而形成密封體15(參照第2圖B)。 In the sealing body forming step, the sealing sheet 11 is thermally hardened to form the sealing body 15 (see FIG. 2B).

熱硬化處理之條件方面，加熱溫度較佳為100℃以上，更佳為120℃以上。另一方面，加熱溫度之上限較佳為 200℃以下，更佳為180℃以下。加熱時間，較佳為10分鐘以上，更佳為30分鐘以上。另一方面，加熱時間之上限較佳為180分鐘以下，更佳為120分鐘以下。此外，亦可因應需要而進行加壓，較佳為0.1MPa以上，更佳為0.5MPa以上。另一方面，上限較佳為10MPa以下，更佳為5MPa以下。 Regarding the conditions of the thermal hardening treatment, the heating temperature is preferably 100°C or higher, more preferably 120°C or higher. On the other hand, the upper limit of the heating temperature is preferably 200°C or lower, more preferably 180°C or lower. The heating time is preferably 10 minutes or more, more preferably 30 minutes or more. On the other hand, the upper limit of the heating time is preferably 180 minutes or less, more preferably 120 minutes or less. In addition, it can also be pressurized as needed, preferably 0.1 MPa or more, more preferably 0.5 MPa or more. On the other hand, the upper limit is preferably 10 MPa or less, more preferably 5 MPa or less.

(切割步驟) (Cutting step)

接著，可進行密封體15之切割(參照第2圖C)。藉此，可得到SAW過濾器13單元之電子裝置封裝18。 Next, the sealing body 15 can be cut (refer to Fig. 2C). Thereby, the electronic device package 18 of the SAW filter 13 unit can be obtained.

(基板安裝步驟) (Board mounting steps)

可因應需要，進行基板安裝步驟，該步驟係對於電子裝置封裝18形成再配線及凸緣，而將其安裝於另外的基板(未圖示)。為了將電子裝置封裝18安裝於基板，可使用倒裝晶片接合器或晶粒接合器等之周知的裝置。 A substrate mounting step may be performed as needed. This step is to form rewiring and flanges for the electronic device package 18, and then mount them on another substrate (not shown). In order to mount the electronic device package 18 on the substrate, a well-known device such as a flip chip bonder or a die bonder can be used.

[實施例] [Example]

以下，例示性地詳細說明此發明之較佳的實施例。但，此實施例記載的材料或摻合量等，只要無特別限定性的記載，則非為僅將本發明之範圍限定於此等的要旨者。 Hereinafter, a preferred embodiment of this invention will be illustrated in detail. However, the materials, blending amounts, and the like described in the examples are not meant to limit the scope of the present invention to these only, as long as they are not specifically limited.

針對實施例所使用的成分進行說明。 The components used in the examples will be described.

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

酚樹脂：明和化成公司製之MEH-7851-SS(具有聯苯芳 烷基骨架之酚樹脂、羥基當量203g/eq.軟化點67℃) Phenolic resin: MEH-7851-SS manufactured by Meiwa Chemical Co., Ltd. (phenol resin with biphenyl aralkyl skeleton, hydroxyl equivalent 203g/eq. softening point 67℃)

熱塑性樹脂：kaneka公司製之SIBSTER 072T(苯乙基-異丁烯-苯乙烯嵌段共聚物) Thermoplastic resin: SIBSTER 072T (phenethyl-isobutylene-styrene block copolymer) manufactured by Kaneka

離子捕捉劑：協和化學工業公司製之DHT-4A Ion scavenger: DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd.

無機充填劑：電氣化學工業公司製之FB-9454FC(熔融球狀二氧化矽、平均粒徑20μm) Inorganic filler: FB-9454FC (fused spherical silica, average particle size 20μm) manufactured by Denki Chemical Industry Co., Ltd.

矽烷偶合劑：信越化學公司製之KBM-403(3-環氧丙氧基丙基三甲氧基矽烷) Silane coupling agent: KBM-403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.

碳黑：三菱化學公司製之# 20 Carbon black: #20 manufactured by Mitsubishi Chemical Corporation

難燃劑：伏見製藥所製之FP-100(磷腈系難燃劑：以式(4)所表示之化合物) Flame retardant: FP-100 manufactured by Fushimi Pharmaceutical (phosphazene-based flame retardant: a compound represented by formula (4))

Figure 108104649-A0101-12-0019-2
Figure 108104649-A0101-12-0019-2

(式中、m係表示3~4之整數)。 (In the formula, m represents an integer from 3 to 4).

硬化促進劑：四國化成工業公司製之2PHZ-PW(2-苯基-4,5-二羥甲基咪唑) Hardening accelerator: 2PHZ-PW (2-phenyl-4,5-dihydroxymethylimidazole) manufactured by Shikoku Chemical Industry Co., Ltd.

實施例1~2 Examples 1~2

依照表1記載之摻合比，摻合各成分，藉由輥軋混練機 在60~120℃、10分鐘、減壓條件下(0.01kg/cm2)進行熔融混練，而調製出混練物。接著，將所得到的混練物，藉由平板沖壓法，形成為薄片狀，而製作出表1所示之厚度的密封用薄片。 According to the blending ratio described in Table 1, each component was blended and melt-kneaded by a roll kneader at 60 to 120°C for 10 minutes under reduced pressure (0.01 kg/cm 2 ) to prepare a kneaded product. Next, the obtained kneaded product was formed into a sheet shape by a flat plate press method, and a sealing sheet having the thickness shown in Table 1 was produced.

實施例3 Example 3

依照表1記載的摻合，於溶劑(以重量比計，甲基乙基酮(MEK)：甲苯=1：1)中摻合各成分，而得到非溶劑成分濃度90%之塗佈液。 According to the blending described in Table 1, each component was blended in a solvent (weight ratio, methyl ethyl ketone (MEK): toluene = 1:1) to obtain a coating solution with a non-solvent component concentration of 90%.

以使乾燥後的厚度成為50μm的方式，藉由缺角輪塗佈機，將所得到的塗佈液塗佈成厚度50μm之聚酯薄膜A(三菱化學聚酯公司製、MRF-50)之剝離處理面上，使其乾燥。接著，將厚度38μm之聚酯薄膜B(三菱化學聚酯公司製、MRF-38)之剝離處理面貼合於乾燥後的清漆上，而調製出薄膜密封用薄片。 The resulting coating solution was applied to a polyester film A (manufactured by Mitsubishi Chemical Polyester Co., Ltd., MRF-50) with a thickness of 50 μm by a cut-off wheel coater so that the thickness after drying became 50 μm. Peel the treated surface and let it dry. Next, the peeling treatment surface of polyester film B (manufactured by Mitsubishi Chemical Polyester Co., Ltd., MRF-38) having a thickness of 38 μm was bonded to the varnish after drying to prepare a film sealing sheet.

然後，一邊將聚酯薄膜A及聚酯薄膜B適當剝離，一邊藉由輥式層壓機，將5片薄膜密封用薄片進行層合，藉此而製作出厚度250μm之密封用薄片。 Then, while peeling the polyester film A and the polyester film B as appropriate, 5 sheets for film sealing were laminated by a roll laminator to produce a sealing sheet with a thickness of 250 μm.

比較例1 Comparative example 1

依照表1記載之摻合比，摻合各成分，於其中添加與各成分之總量同量的甲基乙基酮，調製出清漆。以使乾燥後的厚度成為50μm的方式，藉由缺角輪塗佈機，將所得到的清漆塗佈於厚度50μm之聚酯薄膜A(三菱化學聚酯公司製、 MRF-50)之剝離處理面上，使其乾燥。接著，將厚度38μm之聚酯薄膜B(三菱化學聚酯公司製、MRF-38)之剝離處理面貼合於乾燥後的清漆上，而調製出薄膜密封用薄片。 According to the blending ratio described in Table 1, each component was blended, and the same amount of methyl ethyl ketone as the total amount of each component was added to prepare a varnish. The varnish obtained was applied to a polyester film A (manufactured by Mitsubishi Chemical Polyester Co., Ltd., MRF-50) with a thickness of 50 μm by a cut-off wheel coater so that the thickness after drying became 50 μm. Surface and let it dry. Next, the peeling treatment surface of polyester film B (manufactured by Mitsubishi Chemical Polyester Co., Ltd., MRF-38) having a thickness of 38 μm was bonded to the varnish after drying to prepare a film sealing sheet.

然後，一邊將聚酯薄膜A及聚酯薄膜B適當剝離，一邊藉由輥式層壓機，將5片薄膜密封用薄片進行層合，藉此而製作出厚度250μm之密封用薄片。 Then, while peeling the polyester film A and the polyester film B as appropriate, 5 sheets for film sealing were laminated by a roll laminator to produce a sealing sheet with a thickness of 250 μm.

使用所得到的密封用薄片進行下述的評估。將結果顯示於表1。 The following evaluation was performed using the obtained sealing sheet. The results are shown in Table 1.

[離子性雜質萃取濃度之測定] [Determination of extraction concentration of ionic impurities]

將實施例、及比較例之密封用薄片分別切取重量5g，裝入直徑58mm、高度37mm之圓柱狀的封閉式Teflon(註冊商標)製容器中，添加離子交換水50ml。其後，在121℃、2氣壓下放置20小時。取出薄膜之後，使用DIONEX公司製、DX320及DX500，測定出離子交換水中之氯化物離子濃度、鈉離子濃度、磷酸離子濃度、及硫酸離子濃度。將結果顯示於表1。 Each of the sealing sheets of the Examples and Comparative Examples was cut into a weight of 5 g, and placed in a cylindrical closed Teflon (registered trademark) container with a diameter of 58 mm and a height of 37 mm, and 50 ml of ion exchange water was added. After that, it was left at 121°C and 2 atmospheres for 20 hours. After the film was taken out, the chloride ion concentration, sodium ion concentration, phosphate ion concentration, and sulfate ion concentration in the ion-exchanged water were measured using DX320 and DX500 manufactured by DIONEX. The results are shown in Table 1.

[透濕度之測定] [Determination of moisture permeability]

使實施例、比較例所製成的密封用薄片熱硬化。熱硬化條件係以150℃進行加熱60分鐘。其後，依據JIS Z 0208(圓筒平板法(cup method))之規定，測定出實施例、比較例所製成的密封用薄片(熱硬化後)之透濕度。 The sealing sheet produced in the Examples and Comparative Examples was thermally cured. The thermal curing conditions are heating at 150°C for 60 minutes. After that, in accordance with JIS Z 0208 (cup method), the moisture permeability of the sealing sheets (after thermal curing) produced in the examples and comparative examples was measured.

測定條件係如下所述。將結果顯示於表1。 The measurement conditions are as follows. The results are shown in Table 1.

(測定條件) (Measurement conditions)

溫度85℃、濕度85%、168小時、密封用薄片的厚度：250μm Temperature 85°C, humidity 85%, 168 hours, thickness of sealing sheet: 250μm

Figure 108104649-A0101-12-0022-3
Figure 108104649-A0101-12-0022-3

11‧‧‧中空型電子裝置密封用薄片(密封薄片) 11‧‧‧Hollow electronic device sealing sheet (sealing sheet)

11a‧‧‧支撐體 11a‧‧‧Support

Claims (5)

一種中空型電子裝置密封用薄片，其包含環氧樹脂、酚樹脂、熱塑性樹脂及無機質填充劑，前述環氧樹脂及前述酚樹脂的合計含量為10重量%以下；前述熱塑性樹脂的含量為1.0重量%以上3.5重量%以下；其中，成為厚度250μm時之熱硬化後的透濕度，係在溫度85℃、濕度85%、168小時的條件下，為500g/m2．24小時以下；其特徵為滿足下述(a)~下述(d)中至少1個，(a)將重量5g之中空型電子裝置密封用薄片浸漬於離子交換水50ml中，在121℃、2氣壓下放置20小時之後的前述離子交換水中之氯化物離子濃度，以質量基準計為低於30ppm；(b)將重量5g之中空型電子裝置密封用薄片浸漬於離子交換水50ml中，在121℃、2氣壓下放置20小時之後的前述離子交換水中之鈉離子濃度，以質量基準計為低於10ppm；(c)將重量5g之中空型電子裝置密封用薄片浸漬於離子交換水50ml中，在121℃、2氣壓下放置20小時之後的前述離子交換水中之磷酸離子濃度，以質量基準計為低於30ppm；(d)將重量5g之中空型電子裝置密封用薄片浸漬於離子交換水50ml中，在121℃、2氣壓下放置20小時之後的前述離子交換水中之硫酸離子濃度，以質量基準計為低於5ppm。 A hollow electronic device sealing sheet, comprising epoxy resin, phenol resin, thermoplastic resin, and inorganic filler, the total content of the epoxy resin and the phenol resin is 10% by weight or less; the content of the thermoplastic resin is 1.0 weight % Above 3.5% by weight; where the moisture permeability after heat curing at a thickness of 250μm is 500g/m 2 at a temperature of 85°C and a humidity of 85% for 168 hours. 24 hours or less; characterized by satisfying at least one of the following (a) to (d) below, (a) immersing the hollow electronic device sealing sheet weighing 5g in 50ml ion-exchanged water at 121℃, 2 The chloride ion concentration in the ion-exchanged water after standing for 20 hours under atmospheric pressure is less than 30 ppm on a mass basis; (b) The hollow electronic device sealing sheet weighing 5 g is immersed in 50 ml of ion-exchanged water. The sodium ion concentration in the aforementioned ion-exchanged water after being placed at 121°C and 2 atmospheres for 20 hours is less than 10 ppm on a mass basis; (c) 5g of hollow electronic device sealing sheet is immersed in 50ml of ion-exchanged water The phosphate ion concentration in the aforementioned ion-exchanged water after being placed at 121°C and 2 atmospheres for 20 hours is less than 30 ppm on a mass basis; (d) 5g of hollow electronic device sealing sheet is immersed in ion-exchange water The concentration of sulfate ions in the aforementioned ion-exchanged water after standing at 121°C and 2 atmospheres for 20 hours in 50 ml is less than 5 ppm on a mass basis. 如請求項1所記載之中空型電子裝置密封用薄片，其中相對於中空型電子裝置密封用薄片全體，含有70~90體積%之無機質填充劑。 The hollow-type electronic device sealing sheet as described in claim 1, wherein the hollow-type electronic device sealing sheet contains 70 to 90% by volume of the inorganic filler. 如請求項1所記載之中空型電子裝置密封用薄片，其係含有離子捕捉劑。 The hollow-type electronic device sealing sheet described in claim 1 contains an ion trapping agent. 如請求項3所記載之中空型電子裝置密封用薄片，其中前述離子捕捉劑係水滑石系化合物。 The hollow-type electronic device sealing sheet described in claim 3, wherein the ion trapping agent is a hydrotalcite-based compound. 一種中空型電子裝置封裝之製造方法，其特徵為包含：以被覆搭載於基板上之1或複數個中空型電子裝置的方式，將如請求項1~4中任一項所記載之中空型電子裝置密封用樹脂薄片層合於前述中空型電子裝置上之層合步驟，以及使前述中空型電子裝置密封用樹脂薄片硬化而形成密封體之密封體形成步驟。 A method for manufacturing a hollow electronic device package, which is characterized by comprising: covering one or a plurality of hollow electronic devices mounted on a substrate, as described in any one of claims 1 to 4, the hollow electronic A lamination step of laminating a resin sheet for sealing a device on the hollow electronic device, and a sealing body forming step of hardening the resin sheet for sealing a hollow electronic device to form a sealed body.
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