TW201728640A - Kit for heat-curable resin film and second protective film forming film, heat-curable resin film, sheet for forming first protective film, and method of forming first protective film for conductive wafer - Google Patents

Kit for heat-curable resin film and second protective film forming film, heat-curable resin film, sheet for forming first protective film, and method of forming first protective film for conductive wafer Download PDF

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TW201728640A
TW201728640A TW105135532A TW105135532A TW201728640A TW 201728640 A TW201728640 A TW 201728640A TW 105135532 A TW105135532 A TW 105135532A TW 105135532 A TW105135532 A TW 105135532A TW 201728640 A TW201728640 A TW 201728640A
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film
protective film
thermosetting resin
forming
resin film
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TWI638845B (en
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山岸正憲
佐藤明德
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琳得科股份有限公司
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—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
    • H01L23/3135—Double encapsulation or coating and encapsulation

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Laminated Bodies (AREA)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
  • Dicing (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides a kit for a heat-curable resin film and a second protective film forming film, a heat-curable resin film, a sheet for forming a first protective film, and a method of forming the first protective film for a conductive wafer, wherein a heat-curable resin film 1 and a second protective film-forming film 2 include at least a heat-curable component, the exothermic onset temperature of the heat-curable resin film 1 measured by differential scanning calorimetry is that of the second protective film-forming film 2 or greater, the exothermic peak temperature of the heat-curable resin film 1 and the second protective film-forming film 2 is 100 to 200 DEG C, and the difference between the exothermic peak temperature of the heat-curable resin film 1 and that of the second protective film-forming film 2 is less than 35 DEG C.

Description

熱固化性樹脂膜與第二保護膜形成膜的組件、熱固化性樹脂膜、第一保護膜形成用片以及半導體晶圓用第一保護膜的形成方法 Module for forming film of thermosetting resin film and second protective film, thermosetting resin film, sheet for forming first protective film, and method for forming first protective film for semiconductor wafer

本發明係關於一種熱固化性樹脂膜與第二保護膜形成膜的組件、熱固化性樹脂膜、具備該熱固化性樹脂膜之第一保護膜形成用片、以及半導體晶圓用第一保護膜的形成方法。 The present invention relates to a thermosetting resin film and a second protective film forming film assembly, a thermosetting resin film, a first protective film forming sheet including the thermosetting resin film, and a first protection for a semiconductor wafer A method of forming a film.

本申請案係基於2015年11月4日於日本提出申請的日本專利申請案2015-217097號並主張其優先權，將其內容援用至本文中。 The present application is based on Japanese Patent Application No. 2015-217097, filed on Jan.

先前，於將MPU(Microprocessing Unit；微處理單元)或閘陣列(gate array)等中所用的多引腳之LSI(Large Scale Integration；大規模積體電路)封裝(package)安裝於 印刷配線基板之情形時，一直採用覆晶安裝方法，該覆晶安裝方法係使用在其連接墊部形成有由共晶焊料、高溫焊料、金等構成之凸狀電極(凸塊)者作為半導體晶片，藉由所謂面朝下(face down)方式使該些凸塊面向晶片搭載用基板上的對應的端子部並使其接觸，進行熔融/擴散接合。 Previously, a multi-pin LSI (Large Scale Integration) package used in an MPU (Micro Processing Unit) or a gate array was mounted on a package. In the case of printing a wiring board, a flip chip mounting method is employed in which a bump electrode (bump) composed of eutectic solder, high-temperature solder, gold, or the like is formed as a semiconductor in the connection pad portion. The wafers are brought into contact with the corresponding terminal portions on the wafer mounting substrate by a so-called face down method, and are subjected to fusion/diffusion bonding.

此種安裝方法中所用的半導體晶片例如係藉由以下方式而獲得：對在電路面形成有凸塊之半導體晶圓的與電路面為相反側之面進行研磨，或進行切割(dicing)而單片化。於獲得此種半導體晶片的過程中，通常為了保護半導體晶圓的電路面及凸塊，而將熱固化性樹脂膜貼附於凸塊形成面，使該膜固化，由此於凸塊形成面形成保護膜。作為此種熱固化性樹脂膜，廣泛地利用含有藉由加熱而固化之熱固化性成分者。另外，作為具備此種熱固化性樹脂膜之保護膜形成用片，已揭示有於前述膜積層具有特定的熱彈性模數之熱塑性樹脂層，進而於前述熱塑性樹脂層上之最上層積層於25℃下為非塑性的熱塑性樹脂層而成者(例如參照專利文獻1)。根據專利文獻1，該保護膜形成用片可謂保護膜之凸塊填充性、晶圓加工性、樹脂密封後的電性連接可靠性等優異。 The semiconductor wafer used in such a mounting method is obtained, for example, by grinding or dicing a surface of a semiconductor wafer having bumps formed on a circuit surface opposite to a circuit surface. Slice. In order to protect the circuit surface and the bump of the semiconductor wafer, the thermosetting resin film is attached to the bump forming surface to cure the film, thereby forming the bump surface. A protective film is formed. As such a thermosetting resin film, those containing a thermosetting component which is cured by heating are widely used. Further, as a sheet for forming a protective film having such a thermosetting resin film, a thermoplastic resin layer having a specific thermoelastic modulus in the film layer is disclosed, and the uppermost layer on the thermoplastic resin layer is further laminated. A thermoplastic resin layer which is not plastic at ° C (see, for example, Patent Document 1). According to Patent Document 1, the sheet for forming a protective film is excellent in bump filling property of the protective film, wafer processability, electrical connection reliability after resin sealing, and the like.

[先前技術文獻] [Previous Technical Literature]

[專利文獻] [Patent Literature]

專利文獻1：日本專利特開2005-028734號公報。 Patent Document 1: Japanese Patent Laid-Open Publication No. 2005-028734.

另一方面，於使用如上所述之具備熱固化性樹脂膜之保護膜形成用片製造半導體晶片時，有時於使熱固化性樹脂膜加熱固化而於半導體晶圓的凸塊形成面形成保護膜之過程中，半導體晶圓產生翹曲(參照圖6)。圖6中，藉由將熱固化性樹脂膜加熱固化而於形成有凸塊151之表面105a形成了保護膜101a的半導體晶圓105中，以外周端部105b朝向上方之方向而產生翹曲。可認為此種半導體晶圓105之翹曲係由於以下原因而產生：於熱固化性樹脂膜於半導體晶圓105的表面105a固化時，因收縮等而產生的應力F1導致半導體晶圓變形。 On the other hand, when a semiconductor wafer is produced using the sheet for forming a protective film having the thermosetting resin film as described above, the thermosetting resin film may be heated and cured to form a protective layer on the bump forming surface of the semiconductor wafer. During the film process, the semiconductor wafer is warped (see Fig. 6). In the semiconductor wafer 105 in which the protective film 101a is formed on the surface 105a on which the bumps 151 are formed by heating and curing the thermosetting resin film, the outer peripheral end portion 105b is warped in the upward direction. It is considered that the warpage of the semiconductor wafer 105 occurs when the thermosetting resin film is cured on the surface 105a of the semiconductor wafer 105, and the stress F1 due to shrinkage or the like causes the semiconductor wafer to be deformed.

若如此般於半導體晶圓中產生翹曲，則例如藉由真空裝置吸引半導體晶圓時產生空氣洩漏，故存在以下問題：於採用真空方式之搬送機構的半導體晶片的製造工序等中，無法搬送半導體晶圓。 When warpage occurs in the semiconductor wafer, the air leakage occurs when the semiconductor wafer is sucked by the vacuum device. Therefore, there is a problem that the semiconductor wafer cannot be transported in the manufacturing process of the semiconductor wafer using the vacuum transfer mechanism. Semiconductor wafers.

本發明係鑒於上述課題而成，其目的在於提供一種於半導體晶圓的凸塊形成面形成第一保護膜時，可抑制該半導體晶圓中產生翹曲的熱固化性樹脂膜與第二保護膜形成膜的組件、熱固化性樹脂膜、第一保護膜形成用片以及半導體晶圓用第一保護膜的形成方法。 The present invention has been made in view of the above problems, and it is an object of the invention to provide a thermosetting resin film and a second protection capable of suppressing warpage in a semiconductor wafer when a first protective film is formed on a bump forming surface of a semiconductor wafer. A module for forming a film, a thermosetting resin film, a sheet for forming a first protective film, and a method for forming a first protective film for a semiconductor wafer.

本發明者等人為了解決上述課題而潛心反復實驗研究。結果發現，藉由使貼附於半導體晶圓的凸塊形成面之熱固化性樹脂膜、與貼附於半導體晶圓的背面、亦即半導體晶圓的與形成有電路及凸塊之面為相反側的面的第二保護膜形成層(第二保護膜形成膜)之間的發熱起始溫度及發熱峰溫度、進而線膨脹係數的關係最適化，於將熱固化性樹脂膜加熱固化時，因收縮等而賦予至半導體晶圓之應力受到背面保護片的加熱固化時的應力的矯正，從而完成了本發明。 The inventors of the present invention have deliberately repeated experimental research in order to solve the above problems. As a result, it has been found that the thermosetting resin film attached to the bump forming surface of the semiconductor wafer and the surface on which the semiconductor wafer is attached to the back surface of the semiconductor wafer, that is, the surface on which the circuit and the bump are formed are The relationship between the heat generation onset temperature, the heat generation peak temperature, and the linear expansion coefficient between the second protective film formation layer (second protective film formation film) on the opposite side surface is optimized, and when the thermosetting resin film is cured by heating The stress applied to the semiconductor wafer due to shrinkage or the like is corrected by the stress at the time of heat curing of the back surface protective sheet, and completed the present invention.

亦即，本發明提供一種熱固化性樹脂膜與第二保護膜形成膜的組件，係貼附於半導體晶圓而使用，且係用於形成將半導體晶圓的複數個凸塊予以保護之第一保護膜；並且前述熱固化性樹脂膜與第二保護膜形成膜的組件包含用以藉由貼附於前述半導體晶圓的具有複數個凸塊之表面並進行加熱固化而於前述表面形成第一保護膜之熱固化性樹脂膜、及半導體晶圓的第二保護膜形成膜；前述熱固化性樹脂膜及前述第二保護膜形成膜分別至少含有熱固化性成分；前述熱固化過度性樹脂膜的藉由示差掃描熱量分析(DSC；Differential Scanning Calorimetry)法所測定之發熱起始溫度為前述第二保護膜形成膜的藉由示差掃描熱量分析法所測定之發熱起始溫度以上；進而，前述 熱固化性樹脂膜及前述第二保護膜形成膜的藉由示差掃描熱量分析法所測定之發熱峰溫度分別為100℃至200℃；前述熱固化性樹脂膜與前述第二保護膜形成膜的前述發熱峰溫度之差小於35℃。 That is, the present invention provides a module for forming a film of a thermosetting resin film and a second protective film, which is used by being attached to a semiconductor wafer, and is used for forming a plurality of bumps for protecting a semiconductor wafer. a protective film; and the assembly of the thermosetting resin film and the second protective film forming film includes a surface formed on the surface by a surface having a plurality of bumps attached to the semiconductor wafer and heat-cured a thermosetting resin film of a protective film and a second protective film forming film of a semiconductor wafer; the thermosetting resin film and the second protective film forming film each containing at least a thermosetting component; and the thermosetting excessive resin The heat generation onset temperature of the film measured by differential scanning calorimetry (DSC) is higher than the onset temperature of the second protective film forming film by differential scanning calorimetry; The foregoing The heat-generating resin film and the second protective film forming film have a heat-generating peak temperature of 100 ° C to 200 ° C as measured by differential scanning calorimetry, respectively; and the thermosetting resin film and the second protective film form a film. The difference in the aforementioned exothermic peak temperatures is less than 35 °C.

本發明之熱固化性樹脂膜與第二保護膜形成膜的組件較佳為於上述構成中，前述熱固化性樹脂膜的線膨脹係數(CTE；Coefficicient of Thermal Expansion)為5×10-6/℃至80×10-6/℃，且與前述第二保護膜形成膜的線膨脹係數之差小於35×10-6/℃。 In the above configuration, the thermosetting resin film of the present invention and the second protective film forming film are preferably the same, and the coefficient of thermal expansion (CTE; Coefficicient of Thermal Expansion) of the thermosetting resin film is 5 × 10 -6 / °C to 80 × 10 -6 / ° C, and the difference in linear expansion coefficient of the film formed with the aforementioned second protective film is less than 35 × 10 -6 / ° C.

本發明之熱固化性樹脂膜與第二保護膜形成膜的組件亦可於上述構成中，前述熱固化性樹脂膜係以於第一支持片的一方的表面上具備第一保護膜形成用片之形式而包含於前述熱固化性樹脂膜與第二保護膜形成膜的組件中，並且前述第二保護膜形成膜以於第二支持片的一方的表面上具備第二保護膜形成用片之形式而包含於前述熱固化性樹脂膜與第二保護膜形成膜的組件中。 In the above-described configuration, the thermosetting resin film of the present invention may be provided with a first protective film forming sheet on one surface of the first support sheet. In the form of the thermosetting resin film and the second protective film forming film, the second protective film forming film is provided with a second protective film forming sheet on one surface of the second supporting sheet. The form is included in the assembly of the aforementioned thermosetting resin film and the second protective film forming film.

另外，本發明提供一種熱固化性樹脂膜，係為了藉由貼附於半導體晶圓的具有複數個凸塊之表面並進行加熱固化而於前述表面形成第一保護膜，而與半導體晶圓的第二保護膜形成膜組合使用；並且前述熱固化性樹脂膜及前述第二保護膜形成膜分別至少含有熱固化性成分；前述熱 固化性樹脂膜的藉由示差掃描熱量分析法所測定之發熱起始溫度為前述第二保護膜形成膜的藉由示差掃描熱量分析法所測定之發熱起始溫度以上；進而，前述熱固化性樹脂膜及前述第二保護膜形成膜的藉由示差掃描熱量分析法所測定之發熱峰溫度分別為100℃至200℃；前述熱固化性樹脂膜與前述第二保護膜形成膜的前述發熱峰溫度之差小於35℃。 Further, the present invention provides a thermosetting resin film for forming a first protective film on the surface by attaching to a surface of a semiconductor wafer having a plurality of bumps and performing heat curing, and the semiconductor wafer a second protective film forming film is used in combination; and the thermosetting resin film and the second protective film forming film each contain at least a thermosetting component; the heat The heat generation starting temperature of the curable resin film measured by the differential scanning calorimetry method is equal to or higher than the heat generation starting temperature measured by differential scanning calorimetry of the second protective film forming film; further, the heat curing property The heat generating peak temperature of the resin film and the second protective film forming film measured by differential scanning calorimetry is 100 ° C to 200 ° C; the aforementioned heat generating peak of the thermosetting resin film and the second protective film forming film The difference in temperature is less than 35 °C.

本發明的熱固化性樹脂膜較佳為於上述構成中以如下形式使用：前述熱固化性樹脂膜的線膨脹係數為5×10-6/℃至80×10-6/℃，且與前述第二保護膜形成膜的線膨脹係數之差小於35×10-6/℃。 The thermosetting resin film of the present invention is preferably used in the above configuration in which the coefficient of linear expansion of the thermosetting resin film is from 5 × 10 -6 / ° C to 80 × 10 -6 / ° C, and The difference in linear expansion coefficient of the second protective film forming film is less than 35 × 10 -6 /°C.

另外，本發明提供一種第一保護膜形成用片，係於第一支持片的一方的表面上具備上述構成之熱固化性樹脂膜。 Moreover, the present invention provides a sheet for forming a first protective film, which comprises a thermosetting resin film having the above-described configuration on one surface of the first support sheet.

另外，本發明提供一種半導體晶圓用第一保護膜的形成方法，係於半導體晶圓的具有電路及複數個凸塊之表面形成保護該複數個凸塊之第一保護膜；並且包括：積層步驟，於在背面側貼附有第二保護膜形成膜之前述半導體晶圓的表面，以覆蓋前述複數個凸塊之方式貼附熱固化性樹脂膜，由此形成將前述第二保護膜形成膜、前述半導體晶圓及前述熱固化性樹脂膜依序積層而成的積層體；以及固 化步驟，將前述積層體加熱，由此使前述複數個凸塊貫穿前述熱固化性樹脂膜，以將前述複數個凸塊各自之間填埋的方式使前述熱固化性樹脂膜加熱固化，由此於前述半導體晶圓的表面形成前述第一保護膜；並且，前述熱固化性樹脂膜的藉由示差掃描熱量分析法所測定之發熱起始溫度為前述第二保護膜形成膜的藉由示差掃描熱量分析法所測定之發熱起始溫度以上；進而，前述熱固化性樹脂膜及前述第二保護膜形成膜的藉由示差掃描熱量分析法所測定之發熱峰溫度分別為100℃至200℃；前述熱固化性樹脂膜與前述第二保護膜形成膜的前述發熱峰溫度之差為小於35℃之關係。 In addition, the present invention provides a method for forming a first protective film for a semiconductor wafer, comprising: forming a first protective film for protecting the plurality of bumps on a surface of the semiconductor wafer having the circuit and the plurality of bumps; and comprising: laminating a step of attaching a surface of the semiconductor wafer to which the second protective film forming film is attached on the back side, and attaching the thermosetting resin film so as to cover the plurality of bumps, thereby forming the second protective film a laminate in which a film, the semiconductor wafer, and the thermosetting resin film are sequentially laminated; and a solid In the step of heating, the plurality of bumps are passed through the thermosetting resin film, and the thermosetting resin film is heated and solidified so as to fill the plurality of bumps. The first protective film is formed on the surface of the semiconductor wafer; and the heat-generating starting temperature of the thermosetting resin film measured by differential scanning calorimetry is the difference of the second protective film forming film. The heat generation temperature of the thermosetting resin film and the second protective film forming film measured by the differential scanning calorimetry method is 100 ° C to 200 ° C, respectively. The difference between the heat-generating peak temperature of the thermosetting resin film and the second protective film forming film is less than 35 °C.

再者，所謂本發明中所說明之示差掃描熱量分析法，係指藉由測量基準物質與被測定物之間的熱量之差，而測定被測定物的發熱起始溫度等先前以來進行之熱分析方法。 In addition, the differential scanning calorimetry method described in the present invention refers to measuring the heat generation temperature of the object to be measured, etc., by measuring the difference in heat between the reference substance and the object to be measured. Analytical method.

根據本發明之熱固化性樹脂膜與第二保護膜形成膜的組件、熱固化性樹脂膜、具備該熱固化性樹脂膜之第一保護膜形成用片，藉由使貼附於半導體晶圓的表面之熱固化性樹脂膜、與貼附於背面之第二保護膜形成膜之間的發熱起始溫度及發熱峰溫度的關係最適化，使因熱固化性樹脂膜加熱固化時之收縮等而賦予至半導體晶圓之應力受 到第二保護膜形成膜的加熱固化時之應力的矯正。藉此，可抑制半導體晶圓中產生翹曲，而可製造可靠性優異之半導體封裝。 The thermosetting resin film and the second protective film forming film assembly, the thermosetting resin film, and the first protective film forming sheet including the thermosetting resin film according to the present invention are attached to the semiconductor wafer The relationship between the heat-generating resin film and the heat-generating peak temperature between the surface of the thermosetting resin film and the second protective film forming film attached to the back surface is optimized, and the shrinkage of the thermosetting resin film during heat curing is performed. The stress imparted to the semiconductor wafer is affected by Correction of stress at the time of heat curing of the second protective film forming film. Thereby, warpage can be suppressed in the semiconductor wafer, and a semiconductor package excellent in reliability can be manufactured.

另外，根據本發明之半導體晶圓用第一保護膜的形成方法，與上述同樣地，其係將半導體晶圓的表面側之熱固化性樹脂膜、與背面側之第二保護膜形成膜之間的發熱起始溫度及發熱峰溫度之關係最適化的方法，故可於在半導體晶圓的表面形成第一保護膜之固化步驟中，抑制半導體晶圓中產生翹曲，與上述同樣地可製造可靠性優異之半導體封裝。 Further, in the method of forming the first protective film for a semiconductor wafer according to the present invention, the thermosetting resin film on the surface side of the semiconductor wafer and the second protective film on the back side are formed into a film in the same manner as described above. The method of optimizing the relationship between the onset temperature of the heat generation and the peak of the exothermic peak can suppress the occurrence of warpage in the semiconductor wafer in the curing step of forming the first protective film on the surface of the semiconductor wafer, and can be suppressed in the same manner as described above. Manufacturing semiconductor packages with excellent reliability.

1‧‧‧熱固化性樹脂膜 1‧‧‧Hot Curable Resin Film

1a‧‧‧第一保護膜 1a‧‧‧First protective film

101a‧‧‧保護膜 101a‧‧‧Protective film

1A、1B、1C‧‧‧第一保護膜形成用片 1A, 1B, 1C‧‧‧ first protective film forming sheet

11、11A、11B‧‧‧第一支持片 11, 11A, 11B‧‧‧ first support tablets

11a‧‧‧一方的表面(第一支持片) 11a‧‧‧ Surface of the party (first support piece)

12‧‧‧第一基材 12‧‧‧First substrate

12a‧‧‧表面(第一基材) 12a‧‧‧ surface (first substrate)

13‧‧‧第一黏著劑層 13‧‧‧First adhesive layer

13a‧‧‧表面(第一黏著劑層) 13a‧‧‧Surface (first adhesive layer)

14‧‧‧第一中間層 14‧‧‧First intermediate layer

2‧‧‧第二保護膜形成膜 2‧‧‧Second protective film forming film

2a‧‧‧第二保護膜 2a‧‧‧Second protective film

2A‧‧‧第二保護膜形成用片 2A‧‧‧Second protective film forming sheet

21‧‧‧第二支持片 21‧‧‧Second Support

21a‧‧‧一方的表面(第二支持片21) 21a‧‧‧ Surface of one side (second support piece 21)

5、105‧‧‧半導體晶圓 5, 105‧‧‧ semiconductor wafer

5a‧‧‧表面(凸塊形成面、電路面) 5a‧‧‧ Surface (bump forming surface, circuit surface)

5b‧‧‧背面 5b‧‧‧Back

5c‧‧‧端部 5c‧‧‧ end

105a‧‧‧凸塊之表面 105a‧‧‧Bump surface

105b‧‧‧外周端部 105b‧‧‧ peripheral end

10‧‧‧熱固化性樹脂膜與第二保護膜形 成膜的組件(膜組件) 10‧‧‧Thermal curable resin film and second protective film shape Film forming component (membrane component)

50‧‧‧積層體 50‧‧‧Layered body

51、151‧‧‧凸塊 51, 151‧‧ ‧ bumps

51a‧‧‧表面(凸塊的表面) 51a‧‧‧Surface (surface of the bump)

60‧‧‧切割膠帶 60‧‧‧Cut Tape

60a‧‧‧上表面(切割膠帶) 60a‧‧‧Upper surface (cutting tape)

F1、F2‧‧‧應力 F1, F2‧‧‧ stress

圖1A係示意性地表示使用本發明之熱固化性樹脂膜與第二保護膜形成膜的組件，於半導體晶圓的凸塊形成面形成第一保護膜之工序的一例之剖面圖，且係表示於半導體晶圓之背面側貼著第二保護膜形成膜，並且於凸塊形成面上貼著熱固化性樹脂膜而形成積層體之狀態之圖。 1A is a cross-sectional view showing an example of a step of forming a first protective film on a bump forming surface of a semiconductor wafer by using a thermosetting resin film of the present invention and a second protective film forming film, and A state in which a second protective film forming film is adhered to the back surface side of the semiconductor wafer, and a layered body is formed by laminating a thermosetting resin film on the bump forming surface.

圖1B係示意性地表示使用本發明之熱固化性樹脂膜與第二保護膜形成膜的組件，於半導體晶圓的凸塊形成面形成第一保護膜之工序的一例之剖面圖，且係表示藉由切割膠帶將圖1A中所得之積層體安裝於省略圖示之晶圓切割用環形框架的工序之圖。 1B is a cross-sectional view showing an example of a step of forming a first protective film on a bump forming surface of a semiconductor wafer by using a thermosetting resin film of the present invention and a second protective film forming film, and The process of attaching the laminated body obtained in FIG. 1A to a ring-shaped frame for wafer dicing (not shown) by a dicing tape is shown.

圖1C係示意性地表示使用本發明之熱固化性樹脂膜與第二保護膜形成膜的組件，於半導體晶圓的凸塊形成面形成第一保護膜之工序的一例之剖面圖，且係表示使熱固化性樹脂膜加熱固化而形成第一保護膜，並且使第二保護膜形成膜加熱固化而形成第二保護膜之狀態之圖。 1C is a cross-sectional view showing an example of a step of forming a first protective film on a bump forming surface of a semiconductor wafer by using a thermosetting resin film of the present invention and a second protective film forming film, and A state in which a thermosetting resin film is heated and cured to form a first protective film, and a second protective film forming film is heated and solidified to form a second protective film.

圖1D係示意性地表示使用本發明之熱固化性樹脂膜與第二保護膜形成膜的組件，於半導體晶圓的凸塊形成面形成第一保護膜之工序的一例之剖面圖，且係表示將形成有第一保護膜及第二保護膜之半導體晶圓以晶片單位進行切割處理後，將經分割成晶片單位之半導體晶圓自省略圖示之晶圓切割用環形框架取下，並且去除切割膠帶的工序之圖。 1D is a cross-sectional view showing an example of a step of forming a first protective film on a bump forming surface of a semiconductor wafer by using a thermosetting resin film of the present invention and a second protective film forming film, and The semiconductor wafer in which the first protective film and the second protective film are formed is diced in wafer units, and the semiconductor wafer divided into wafer units is removed from the wafer cutting annular frame (not shown), and A diagram of the process of removing the dicing tape.

圖2係示意性地表示本發明之熱固化性樹脂膜及第一保護膜形成用片之層結構的一例之剖面圖。 Fig. 2 is a cross-sectional view showing an example of a layer structure of a thermosetting resin film and a sheet for forming a first protective film of the present invention.

圖3係示意性地表示本發明之熱固化性樹脂膜及第一保護膜形成用片之層結構的其他例之剖面圖。 Fig. 3 is a cross-sectional view showing another example of the layer structure of the thermosetting resin film and the first protective film forming sheet of the present invention.

圖4係示意性地表示本發明之熱固化性樹脂膜及第一保護膜形成用片之層結構的其他例之剖面圖。 Fig. 4 is a cross-sectional view showing another example of the layer structure of the thermosetting resin film and the first protective film forming sheet of the present invention.

圖5係示意性地表示本發明之熱固化性樹脂膜與第二保護膜形成膜的組件所具備之第二保護膜形成膜及第二保護膜形成用片的一例之剖面圖。 FIG. 5 is a cross-sectional view showing an example of a second protective film forming film and a second protective film forming sheet which are provided in the assembly of the thermosetting resin film and the second protective film forming film of the present invention.

圖6係表示使用先前之熱固化性樹脂膜於半導體晶圓的凸塊形成面形成保護膜後，將半導體晶圓自晶圓切割用環形框架取下之狀態之圖。 6 is a view showing a state in which a semiconductor wafer is removed from a wafer cutting annular frame after a protective film is formed on a bump forming surface of a semiconductor wafer using a conventional thermosetting resin film.

以下，對於本發明之熱固化性樹脂膜與第二保護膜形成膜的組件、熱固化性樹脂膜、第一保護膜形成用片以及半導體晶圓用第一保護膜的形成方法之實施形態，視需要參照圖1A至圖1D及圖2至圖5所示之本發明圖以及圖6所示之先前圖，並且加以詳細說明。圖1A至圖1D係示意性地表示使用本發明之熱固化性樹脂膜與第二保護膜形成膜的組件，於半導體晶圓的凸塊形成面形成第一保護膜，並且於背面側形成第二保護膜之工序的一例之剖面圖，圖2至圖4係分別示意性地表示熱固化性樹脂膜及第一保護膜形成用片之層結構的各例之剖面圖。另外，圖5係示意性地表示熱固化性樹脂膜與第二保護膜形成膜的組件所具備之第二保護膜形成膜及第二保護膜形成用片的一例之剖面圖。另外，圖6係表示使用先前之熱固化性樹脂膜於半導體晶圓的凸塊形成面形成第一保護膜之例之圖。再者，關於以下之說明中所用之圖，有時為了容易地理解本發明之特徵，為方便起見而將成為要部之部分放大表示，有時各構成要素的尺寸比率等與實際不同。另外，本說明書中，有時將上述「膜」稱為「層」。 In the embodiment of the method for forming a film of a thermosetting resin film and a second protective film of the present invention, a thermosetting resin film, a sheet for forming a first protective film, and a method for forming a first protective film for a semiconductor wafer, The drawings of the present invention shown in FIGS. 1A to 1D and FIGS. 2 to 5 and the previous drawings shown in FIG. 6 are referred to as needed and described in detail. 1A to 1D are diagrams schematically showing a module for forming a film using a thermosetting resin film of the present invention and a second protective film, forming a first protective film on a bump forming surface of a semiconductor wafer, and forming a first surface on the back side FIG. 2 to FIG. 4 are cross-sectional views each showing a schematic example of a layer structure of a thermosetting resin film and a first protective film forming sheet, respectively. In addition, FIG. 5 is a cross-sectional view showing an example of a second protective film forming film and a second protective film forming sheet which are provided in the assembly of the thermosetting resin film and the second protective film forming film. In addition, FIG. 6 is a view showing an example in which a first protective film is formed on a bump forming surface of a semiconductor wafer using a conventional thermosetting resin film. In the drawings used in the following description, in order to facilitate the understanding of the features of the present invention, the parts which become the main parts are enlarged for the sake of convenience, and the dimensional ratios of the respective constituent elements may be different from the actual ones. In addition, in this specification, the above-mentioned "film" may be called "layer".

如圖1A至圖1D所示，本發明之熱固化性樹脂膜與第二保護膜形成膜的組件10(以下有時僅簡稱為膜組件10)係用於形成保護半導體晶圓5的複數個凸塊51之第一 保護膜1a，係包含貼著於半導體晶圓5的凸塊形成面(表面)5a之熱固化性樹脂膜1、及貼著於半導體晶圓5的背面5b側之第二保護膜形成膜2而構成。亦即，膜組件10係於在半導體晶圓5形成第一保護膜1a時貼附於半導體晶圓5而使用。 As shown in FIG. 1A to FIG. 1D, the thermosetting resin film of the present invention and the second protective film forming film assembly 10 (hereinafter sometimes simply referred to as the film module 10) are used to form a plurality of protective semiconductor wafers 5. First of the bumps 51 The protective film 1a includes a thermosetting resin film 1 attached to the bump forming surface (surface) 5a of the semiconductor wafer 5, and a second protective film forming film 2 attached to the back surface 5b side of the semiconductor wafer 5. And constitute. That is, the film module 10 is used by being attached to the semiconductor wafer 5 when the semiconductor wafer 5 is formed with the first protective film 1a.

另外，圖2至圖4中亦例示之本發明之熱固化性樹脂膜1如上述般構成膜組件10，由至少含有熱固化性成分之膜所構成。而且，本發明之熱固化性樹脂膜1係與貼著於半導體晶圓5的背面5b側之第二保護膜形成膜2組合使用而構成上述膜組件10。另外，構成膜組件10之第二保護膜形成膜2亦與熱固化性樹脂膜1同樣地由至少含有熱固化性成分之膜所構成。 In addition, the thermosetting resin film 1 of the present invention, which is exemplified in the above, is configured as described above, and is composed of a film containing at least a thermosetting component. Further, the thermosetting resin film 1 of the present invention is used in combination with the second protective film forming film 2 attached to the back surface 5b side of the semiconductor wafer 5 to constitute the film module 10. In addition, the second protective film forming film 2 constituting the film module 10 is also composed of a film containing at least a thermosetting component, similarly to the thermosetting resin film 1.

另外，如圖2所示，本發明之第一保護膜形成用片1A係於支持片11的一方的表面11a上具備上述熱固化性樹脂膜1。亦即，第一保護膜形成用片1A係於將上述熱固化性樹脂膜1貼著於半導體晶圓5上之前，例如於以製品封裝之形式搬運熱固化性樹脂膜1、或者於工序內搬運熱固化性樹脂膜1時，藉由支持片11而穩定地支持、保護熱固化性樹脂膜1。 In addition, as shown in FIG. 2, the first protective film forming sheet 1A of the present invention includes the thermosetting resin film 1 on one surface 11a of the support sheet 11. In other words, the first protective film forming sheet 1A is used to transport the thermosetting resin film 1 in the form of a product package, for example, before the thermosetting resin film 1 is placed on the semiconductor wafer 5. When the thermosetting resin film 1 is conveyed, the thermosetting resin film 1 is stably supported and protected by the support sheet 11.

亦即，本發明之膜組件10、及第一保護膜形成用片1A均係含有本發明之熱固化性樹脂膜1而構成。 In other words, both the membrane module 10 of the present invention and the first protective film forming sheet 1A are composed of the thermosetting resin film 1 of the present invention.

以下，對本發明之熱固化性樹脂膜與第二保護膜形成膜的組件10、熱固化性樹脂膜1及第一保護膜形成用片1A之構成依序加以詳述。 Hereinafter, the components of the thermosetting resin film and the second protective film forming film of the present invention, the thermosetting resin film 1 and the first protective film forming sheet 1A will be described in detail.

<<熱固化性樹脂膜與第二保護膜形成膜的組件(膜組件)>> <<Component (Film Module) Forming Film of Thermosetting Resin Film and Second Protective Film>>

如上所述，圖1A及圖1B所例示般之本發明之膜組件10係用於形成保護半導體晶圓5的複數個凸塊5之第一保護膜1a(參照圖1C及圖1D)。 As described above, the film module 10 of the present invention as illustrated in FIGS. 1A and 1B is for forming the first protective film 1a for protecting the plurality of bumps 5 of the semiconductor wafer 5 (see FIGS. 1C and 1D).

更詳細而言，膜組件10係包含熱固化性樹脂膜1及第二保護膜形成膜2而概略構成，上述熱固化性樹脂膜1係用於藉由貼附於圖1A至圖1D中所示般之半導體晶圓5的具有複數個凸塊51之表面(本實施形態中，有時亦稱為「電路面」或「凸塊形成面」)5a並進行加熱固化，而於表面5a形成第一保護膜1a，上述第二保護膜形成膜2係貼附於半導體晶圓5的背面5b側。另外，該等熱固化性樹脂膜1及第二保護膜形成膜2之成分組成係分別設定為至少含有熱固化性成分。 More specifically, the film module 10 is configured by including the thermosetting resin film 1 and the second protective film forming film 2, and the thermosetting resin film 1 is used for attaching to FIGS. 1A to 1D. The surface of the semiconductor wafer 5 having a plurality of bumps 51 (also referred to as "circuit surface" or "bump forming surface" in the present embodiment) 5a is heated and solidified to form a surface 5a. The first protective film 1a and the second protective film forming film 2 are attached to the back surface 5b side of the semiconductor wafer 5. In addition, the component compositions of the thermosetting resin film 1 and the second protective film forming film 2 are each set to contain at least a thermosetting component.

本發明之膜組件10所具備之熱固化性樹脂膜1係貼附於半導體晶圓5的具有凸塊51之表面5a而使用。而且，貼附後之熱固化性樹脂膜1藉由加熱而流動性增大，以覆蓋凸塊51之方式於複數個凸塊51間擴展而與表面 (電路面)5a密接，並且一邊覆蓋凸塊51的表面51a、特別是半導體晶圓5的表面5a的附近部位一邊填埋凸塊51。該狀態之熱固化性樹脂膜1進一步藉由加熱而熱固化，最終形成第一保護膜1a，於表面5a中以密接於凸塊51的表面51a之狀態保護該凸塊51。關於貼附熱固化性樹脂膜1後之半導體晶圓5，例如將與成為電路面之表面5a為相反側的面(背面5b)研磨後，去掉第一支持片(參照圖2所示之第一保護膜形成用片1A所具備之支持片11)。繼而，藉由熱固化性樹脂膜1之加熱而進行凸塊51的填埋及第一保護膜1a之形成，最終以具備該第一保護膜1a之狀態組入至省略圖示之半導體裝置中。 The thermosetting resin film 1 included in the film module 10 of the present invention is used by being attached to the surface 5a of the semiconductor wafer 5 having the bumps 51. Further, the thermosetting resin film 1 after the adhesion is increased in fluidity by heating, and spreads between the plurality of bumps 51 and the surface so as to cover the bumps 51. The (circuit surface) 5a is in close contact with each other, and the bump 51 is filled while covering the surface 51a of the bump 51, particularly the vicinity of the surface 5a of the semiconductor wafer 5. The thermosetting resin film 1 in this state is further thermally cured by heating to finally form the first protective film 1a, and the bump 51 is protected in a state in which the surface 5a is in close contact with the surface 51a of the bump 51. The semiconductor wafer 5 to which the thermosetting resin film 1 is attached is polished, for example, by polishing a surface (back surface 5b) opposite to the surface 5a of the circuit surface, and then removing the first support sheet (see FIG. A support sheet 11) provided in the sheet 1A for protective film formation. Then, the filling of the bumps 51 and the formation of the first protective film 1a are performed by heating of the thermosetting resin film 1, and finally, the first protective film 1a is incorporated in a semiconductor device (not shown). .

作為圖1A至圖1D所示之半導體晶圓5的電路面之表面5a上設有複數個凸塊51。凸塊51具有藉由平面將球之一部分切去而成的形狀，相當於該被切去而露出的部位之平面與半導體晶圓5的表面5a接觸。 A plurality of bumps 51 are provided on the surface 5a of the circuit surface of the semiconductor wafer 5 shown in FIGS. 1A to 1D. The bump 51 has a shape in which one portion of the ball is cut by a plane, and corresponds to a plane of the portion which is cut out and exposed, and is in contact with the surface 5a of the semiconductor wafer 5.

第一保護膜1a係使用本發明之熱固化性樹脂膜1而形成，將半導體晶圓5的表面5a被覆，進而將凸塊51中的上頂及其附近以外之表面51a被覆。如此，第一保護膜1a與凸塊51的表面51a中的凸塊51的上頂及其附近以外之區域密接，並且與半導體晶圓5的表面(電路面)5a亦密接而填埋凸塊51。再者，於圖1A及圖1B所示之例中，作為凸塊而示出了前述般的大致球狀之形狀(藉由平面將球的一部分切去而成的形狀)者，但可利用由本發明之固 化性樹脂膜1所形成之第一保護膜1a保護之凸塊的形狀不限定於此。例如亦可列舉如下凸塊作為較佳形狀之凸塊：將圖1A及圖1B中所示般之大致球狀的形狀之凸塊於高度方向(圖1A及圖1B中為相對於半導體晶圓5的表面5a而正交之方向)拉伸而成的形狀、亦即大致長球狀之旋轉橢圓體的形狀(藉由平面將長球狀之旋轉橢圓體的包含長軸方向的一端之部位切去而成的形狀)之凸塊；或將上述般的大致球狀的形狀於高度方向壓扁而成的形狀、亦即大致扁球狀之旋轉橢圓體的形狀(藉由平面將扁球狀之旋轉橢圓體的包含短軸方向的一端之部位切去而成的形狀)之凸塊。另外，藉由本發明之固化性樹脂膜1所形成之第一保護膜1a亦可應用於其他任何形狀之凸塊，尤其於凸塊之形狀為上述般的球狀或包含橢圓等的球狀之情形時，可顯著地獲得保護半導體晶圓的表面及凸塊之功效。 The first protective film 1a is formed by using the thermosetting resin film 1 of the present invention, and covers the surface 5a of the semiconductor wafer 5, and further covers the upper surface of the bump 51 and the surface 51a other than the vicinity thereof. In this manner, the first protective film 1a is in close contact with the upper top of the bump 51 in the surface 51a of the bump 51 and a region other than the vicinity thereof, and is also in close contact with the surface (circuit surface) 5a of the semiconductor wafer 5 to fill the bump. 51. Further, in the example shown in FIG. 1A and FIG. 1B, the above-described substantially spherical shape (a shape obtained by cutting a part of a ball by a plane) is shown as a bump, but it can be utilized. Solid by the invention The shape of the bump protected by the first protective film 1a formed of the chemical resin film 1 is not limited thereto. For example, the bumps may be exemplified as bumps of a preferred shape: the bumps of the substantially spherical shape as shown in FIGS. 1A and 1B are oriented in the height direction (FIG. 1A and FIG. 1B are relative to the semiconductor wafer). a shape obtained by stretching the surface 5a and the direction perpendicular to the surface 5, that is, a shape of a substantially long spherical ellipsoid (a portion including a long axis direction of the long spheroidal ellipsoid by a plane) a bump formed by cutting out the shape; or a shape in which the substantially spherical shape as described above is flattened in the height direction, that is, a shape of a substantially spheroidal spheroid (a flat spherical shape by a plane) A bump of a shape of a portion of the ellipsoid that is cut at one end in the direction of the minor axis. Further, the first protective film 1a formed by the curable resin film 1 of the present invention can also be applied to bumps of any other shape, in particular, the shape of the bumps is spherical as described above or spherical having an ellipse or the like. In the case, the effect of protecting the surface and bumps of the semiconductor wafer can be remarkably obtained.

而且，本發明之膜組件10係設定為如下構成：作為熱固化性樹脂膜1，藉由示差掃描熱量分析法所測定之發熱起始溫度為同樣地藉由示差掃描熱量分析法所測定之第二保護膜形成膜2的發熱起始溫度以上。 Further, the membrane module 10 of the present invention has a configuration in which the heat generation starting temperature measured by the differential scanning calorimetry method is the same as that determined by the differential scanning calorimetry method as the thermosetting resin film 1. The second protective film forming film 2 has a heat generation starting temperature or higher.

另外，膜組件10係設定為如下構成：熱固化性樹脂膜1及第二保護膜形成膜2的藉由示差掃描熱量分析法所測定之發熱峰溫度分別為100℃至200℃，熱固化性樹脂膜1與第二保護膜形成膜2的發熱峰溫度之差小於 35℃。進而，膜組件10可設定為如下構成：熱固化性樹脂膜1的線膨脹係數為5(×10-6/℃)至80(×10-6/℃)，且與第二保護膜形成膜2的線膨脹係數之差小於35(×10-6/℃)。 In addition, the film module 10 is configured such that the heat-generating peak temperature of the thermosetting resin film 1 and the second protective film forming film 2 measured by differential scanning calorimetry is 100 ° C to 200 ° C, respectively, and thermosetting property. The difference in the exothermic peak temperature between the resin film 1 and the second protective film forming film 2 is less than 35 °C. Further, the film module 10 can be configured such that the coefficient of linear expansion of the thermosetting resin film 1 is 5 (×10 -6 /° C.) to 80 (×10 -6 /° C.), and a film is formed with the second protective film. The difference between the linear expansion coefficients of 2 is less than 35 (×10 -6 /°C).

對於本發明之膜組件10而言，藉由如上所述般使貼附於半導體晶圓5的表面5a的熱固化性樹脂膜1的發熱起始溫度與貼附於半導體晶圓5的背面5b側之第二保護膜形成膜的發熱起始溫度相同，或為較其更高之溫度，因將熱固化性樹脂膜1加熱固化而形成第一保護膜1a時的收縮等而賦予至半導體晶圓5之應力受到將第二保護膜形成膜2加熱固化而形成第二保護膜時的收縮等所致之應力的矯正。進而，本發明中，將熱固化性樹脂膜1及第二保護膜形成膜2的發熱峰溫度設為100℃至200℃，而且將該等各膜的發熱峰溫度之差設為小於35℃，藉此與上述同樣地獲得以下作用：使因將熱固化性樹脂膜1加熱固化時的收縮等而賦予至半導體晶圓5之應力受到因將第二保護膜形成膜2加熱固化時的收縮等而產生之應力的矯正。 In the film module 10 of the present invention, the heat generation starting temperature of the thermosetting resin film 1 attached to the surface 5a of the semiconductor wafer 5 and the back surface 5b attached to the semiconductor wafer 5 are adhered as described above. The second protective film forming film on the side has the same heat generation starting temperature, or a temperature higher than this, and is imparted to the semiconductor crystal by shrinkage or the like when the thermosetting resin film 1 is cured by heating to form the first protective film 1a. The stress of the circle 5 is corrected by the stress caused by shrinkage or the like when the second protective film forming film 2 is heated and solidified to form the second protective film. Furthermore, in the present invention, the exothermic peak temperature of the thermosetting resin film 1 and the second protective film forming film 2 is set to 100 ° C to 200 ° C, and the difference in the exothermic peak temperatures of the respective films is set to be less than 35 ° C. In the same manner as described above, the stress applied to the semiconductor wafer 5 due to shrinkage or the like during heat curing of the thermosetting resin film 1 is caused by shrinkage when the second protective film forming film 2 is cured by heating. Correction of the stress generated by the equalization.

另外，本發明中可採用如下構成：將熱固化性樹脂膜1與第二保護膜形成膜2之間的發熱起始溫度及發熱峰溫度的關係設為上述範圍，而且，進而熱固化性樹脂膜1的線膨脹係數為5(×10-6/℃)至80(×10-6/℃)，且與第二保護膜形成膜2的線膨脹係數之差小於35(×10-6/℃)。藉此 與上述同樣地獲得以下作用：將熱固化性樹脂膜1加熱固化時賦予至半導體晶圓5之應力受到將第二保護膜形成膜2加熱固化時之應力的矯正。 In the present invention, the relationship between the heat generation onset temperature and the exothermic peak temperature between the thermosetting resin film 1 and the second protective film formation film 2 is set to the above range, and further, the thermosetting resin is further provided. The linear expansion coefficient of the film 1 is 5 (×10 -6 /° C.) to 80 (×10 -6 /° C.), and the difference in linear expansion coefficient of the film 2 formed with the second protective film is less than 35 (×10 -6 / °C). In the same manner as described above, the stress applied to the semiconductor wafer 5 when the thermosetting resin film 1 is heated and cured is corrected by the stress when the second protective film forming film 2 is cured by heating.

根據本發明之膜組件10，藉由如上所述之賦予至半導體晶圓5之應力的矯正作用，可抑制包含半導體晶圓5之積層體中產生翹曲，故可製造可靠性優異之半導體封裝。 According to the film module 10 of the present invention, since the warpage applied to the laminated body including the semiconductor wafer 5 can be suppressed by the correction effect of the stress applied to the semiconductor wafer 5 as described above, the semiconductor package excellent in reliability can be manufactured. .

更詳細而言，如圖1C中所示，由於將熱固化性樹脂膜1加熱固化時的收縮等，而於半導體晶圓5的端部5c朝向圖中的上方之方向、亦即被拉向熱固化性樹脂膜1側之方向產生應力F1。 More specifically, as shown in FIG. 1C, the end portion 5c of the semiconductor wafer 5 is directed toward the upper direction in the drawing, that is, pulled, due to shrinkage or the like during heat curing of the thermosetting resin film 1. The stress F1 is generated in the direction of the side of the thermosetting resin film 1.

另一方面，本發明中，採用如上所述之發熱起始溫度、發熱峰溫度及線膨脹係數之關係，由此於半導體晶圓5之加熱時，相較於熱固化性樹脂膜1之固化，而更早地開始第二保護膜形成膜2之固化。藉此，對於半導體晶圓5，自賦予由熱固化性樹脂膜1的加熱固化所致之應力F1之前階段開始，賦予半導體晶圓5的端部5c朝向圖1C中的下方之方向、亦即被拉向第二保護膜形成膜2側之方向的應力F2。如此，於對半導體晶圓5賦予應力F1之前，賦予與該應力F1為相反方向之應力F2，由此成為取得了該等應力F1、F2之平衡的抵消(矯正)關係，故可抑制半導體晶圓5中產生翹曲。 On the other hand, in the present invention, the relationship between the heat generation onset temperature, the exothermic peak temperature, and the coefficient of linear expansion as described above is employed, whereby the semiconductor wafer 5 is cured as compared with the thermosetting resin film 1 when it is heated. The curing of the second protective film forming film 2 is started earlier. In this way, the semiconductor wafer 5 is supplied to the end portion 5c of the semiconductor wafer 5 in a direction toward the lower side in FIG. 1C from the stage before the stress F1 due to heat curing of the thermosetting resin film 1 is applied, that is, The stress F2 pulled in the direction of the second protective film forming film 2 side. In this way, before the stress F1 is applied to the semiconductor wafer 5, the stress F2 in the opposite direction to the stress F1 is applied, whereby the offset (correction) relationship in which the stresses F1 and F2 are balanced is obtained, so that the semiconductor crystal can be suppressed. Warp is generated in the circle 5.

另外，根據本發明，熱固化性樹脂膜1的發熱起始溫度為第二保護膜形成膜2的發熱起始溫度以上，進而兩膜的發熱峰溫度為100℃至200℃，且兩膜的發熱峰溫度之差小於35℃，進而兩膜的線膨脹係數之差小於35(×10-6/℃)，藉此即便於將膜組件10長期間於室溫下保管之情形時，亦可抑制熱固化性樹脂膜1進行固化反應。亦即，可抑制熱固化性樹脂膜1所含之固化觸媒因經時變化而使得開始溫度降低而進行固化反應之情況。藉此，例如即便於使用經長期間保管之膜組件10於半導體晶圓5的表面5a形成第一保護膜1a之情形時，亦獲得如下的顯著功效：與上述同樣地矯正於將熱固化性樹脂膜1加熱固化時賦予至半導體晶圓5之應力，抑制半導體晶圓5中產生翹曲。 Further, according to the present invention, the heat generation starting temperature of the thermosetting resin film 1 is higher than the heat generation starting temperature of the second protective film forming film 2, and further, the heat generation peak temperatures of the two films are 100 ° C to 200 ° C, and the two films are The difference in the temperature of the exothermic peak is less than 35 ° C, and the difference in the coefficient of linear expansion of the two films is less than 35 (×10 -6 /° C.), so that even when the membrane module 10 is stored at room temperature for a long period of time, The thermosetting resin film 1 is suppressed from undergoing a curing reaction. In other words, it is possible to suppress the curing reaction of the curing catalyst contained in the thermosetting resin film 1 by causing a decrease in the temperature at the start of the curing reaction. Thus, for example, even when the first protective film 1a is formed on the surface 5a of the semiconductor wafer 5 by using the film module 10 stored for a long period of time, the following remarkable effects are obtained: the heat curing property is corrected in the same manner as described above. The stress applied to the semiconductor wafer 5 at the time of heat curing of the resin film 1 suppresses warpage in the semiconductor wafer 5.

再者，本發明中，就更顯著地獲得上述作用功效之觀點而言，更佳為熱固化性樹脂膜1及第二保護膜形成膜2的發熱峰溫度為120℃至200℃，尤佳為130℃至200℃，最佳為185℃至200℃。同樣地，熱固化性樹脂膜1與第二保護膜形成膜2的發熱峰溫度之差更佳為0℃至30℃，尤佳為0℃至25℃。 Further, in the present invention, it is more preferable that the heat-generating peak temperature of the thermosetting resin film 1 and the second protective film forming film 2 is from 120 ° C to 200 ° C from the viewpoint of obtaining the above-mentioned effects more significantly. It is from 130 ° C to 200 ° C, preferably from 185 ° C to 200 ° C. Similarly, the difference in the exothermic peak temperature between the thermosetting resin film 1 and the second protective film forming film 2 is preferably from 0 ° C to 30 ° C, particularly preferably from 0 ° C to 25 ° C.

作為測定上述熱固化性樹脂膜1的發熱起始溫度及發熱峰溫度之方法，可無特別限制地採用先前公知之使用示差掃描熱量分析(DSC)裝置之測定方法。 As a method of measuring the heat generation onset temperature and the exothermic peak temperature of the thermosetting resin film 1, a previously known measurement method using a differential scanning calorimetry (DSC) apparatus can be employed without particular limitation.

另外，如上所述，本發明之膜組件10採用如下構成：熱固化性樹脂膜1的線膨脹係數為5(×10-6/℃)至80(×10-6/℃)，且與第二保護膜形成膜2的線膨脹係數之差小於35(×10-6/℃)，並且該第二保護膜形成膜2的線膨脹係數與熱固化性樹脂膜1的線膨脹係數相同，或較其更小。本發明中，使熱固化性樹脂膜1與第二保護膜形成膜2之間的發熱起始溫度及發熱峰溫度的關係最適化，而且，進而使熱固化性樹脂膜1的線膨脹係數的範圍及熱固化性樹脂膜1與第二保護膜形成膜2的線膨脹係數之差最適化，藉此獲得更有效地矯正因將熱固化性樹脂膜1加熱固化時的收縮等而賦予至半導體晶圓5之應力的作用。因此，更顯著地獲得抑制半導體晶圓5中產生翹曲之功效。 Further, as described above, the film module 10 of the present invention has a configuration in which the coefficient of linear expansion of the thermosetting resin film 1 is 5 (×10 -6 /° C.) to 80 (×10 -6 /° C.), and The difference in linear expansion coefficient of the second protective film forming film 2 is less than 35 (×10 -6 /° C.), and the linear expansion coefficient of the second protective film forming film 2 is the same as the linear expansion coefficient of the thermosetting resin film 1, or It is smaller than it. In the present invention, the relationship between the heat generation onset temperature and the exothermic peak temperature between the thermosetting resin film 1 and the second protective film formation film 2 is optimized, and the coefficient of linear expansion of the thermosetting resin film 1 is further increased. The range and the difference in linear expansion coefficient between the thermosetting resin film 1 and the second protective film forming film 2 are optimized, thereby obtaining more effective correction for imparting shrinkage to the semiconductor when the thermosetting resin film 1 is cured by heating or the like. The effect of the stress on the wafer 5. Therefore, the effect of suppressing occurrence of warpage in the semiconductor wafer 5 is more significantly obtained.

再者，本發明中，就更顯著地獲得上述作用功效之觀點而言，更佳為熱固化性樹脂膜1的線膨脹係數為5(×10-6/℃)至60(×10-6/℃)，尤佳為5(×10-6/℃)至50(×10-6/℃)。另外，關於第二保護膜形成膜2的線膨脹係數，亦較佳為與上述熱固化性樹脂膜1的線膨脹係數為相同範圍。同樣地，熱固化性樹脂膜1與第二保護膜形成膜2的線膨脹係數之差更佳為0(×10-6/℃)以上、小於30(×10-6/℃)，尤佳為0(×10-6/℃)以上、小於25(×10-6/℃)。 Further, in the present invention, it is more preferable that the coefficient of linear expansion of the thermosetting resin film 1 is 5 (×10 -6 /°C) to 60 (×10 -6 ) from the viewpoint of obtaining the above-mentioned effects more significantly. /°C), particularly preferably 5 (×10 -6 /°C) to 50 (×10 -6 /°C). In addition, the linear expansion coefficient of the second protective film forming film 2 is also preferably in the same range as the linear expansion coefficient of the thermosetting resin film 1. Similarly, the difference in linear expansion coefficient between the thermosetting resin film 1 and the second protective film forming film 2 is preferably 0 (×10 -6 /° C.) or more and less than 30 (×10 -6 /° C.), particularly preferably It is 0 (×10 -6 /°C) or more and less than 25 (×10 -6 /°C).

作為測定上述熱固化性樹脂膜1的熱膨脹係數(CTE；coefficient of thermal expansion)之方法，可無特別限制地採用先前公知之使用熱機械分析(TMA；thermomechanical analyzer)裝置之測定方法。 As a method of measuring the coefficient of thermal expansion (CTE) of the thermosetting resin film 1, a previously known measurement method using a thermomechanical analyzer (TMA) can be employed without particular limitation.

如上所述之各膜的發熱起始溫度、發熱峰溫度及線膨脹係數可藉由調整後述固化觸媒的組成或含量而最適化。 The heat generation onset temperature, the exothermic peak temperature, and the linear expansion coefficient of each of the films described above can be optimized by adjusting the composition or content of the curing catalyst to be described later.

另外，作為固化後之第一保護膜1a的厚度，並無特別限定，只要一面考慮半導體晶圓5的表面5a或凸塊51的保護能力一面設定總體的平均厚度即可。固化後之第一保護膜1a的厚度例如較佳為1μm至100μm左右，更佳為設為5μm至75μm左右，最佳為設為5μm至50μm左右。固化後之第一保護膜1a的厚度例如可根據藉由掃描式電子顯微鏡的圖像分析等測定多處的厚度所得之平均值而求出。 Further, the thickness of the first protective film 1a after curing is not particularly limited, and the total average thickness may be set in consideration of the protective ability of the surface 5a of the semiconductor wafer 5 or the bumps 51. The thickness of the first protective film 1a after curing is, for example, preferably from about 1 μm to about 100 μm, more preferably from about 5 μm to about 75 μm, and most preferably from about 5 μm to about 50 μm. The thickness of the first protective film 1a after curing can be determined, for example, from an average value obtained by measuring a plurality of thicknesses by image analysis by a scanning electron microscope or the like.

此處，圖6中示意性地表示藉由使用先前之熱固化性樹脂膜的方法於半導體晶圓105的作為凸塊形成面之表面105a形成保護膜101a之狀態的剖面。如圖6所示，於使用先前之構成之熱固化性樹脂膜，且熱固化性樹脂膜、與貼著於半導體晶圓105的背面105b側之第二保護膜形成膜102之間的發熱起始溫度及發熱峰溫度未經最適化的構成之情形時，由於因半導體晶圓105的表面105a中 熱固化性樹脂膜固化時的收縮等而產生之應力F1(參照圖1C及圖1D)，半導體晶圓105容易變形而翹曲。 Here, FIG. 6 is a cross-sectional view schematically showing a state in which the protective film 101a is formed on the surface 105a of the semiconductor wafer 105 as the bump forming surface by the method of using the conventional thermosetting resin film. As shown in FIG. 6, the heat generation between the thermosetting resin film and the second protective film forming film 102 on the side of the back surface 105b of the semiconductor wafer 105 is used. When the initial temperature and the exothermic peak temperature are not optimized, since the surface of the semiconductor wafer 105 is in the 105a The stress F1 (see FIGS. 1C and 1D) generated by shrinkage or the like during curing of the thermosetting resin film is likely to be warped and deformed by the semiconductor wafer 105.

如圖6所示，於半導體晶圓105中產生了翹曲之情形時，例如存在以下問題：於藉由採用真空方式之搬送機構吸引半導體晶圓105時產生空氣洩漏，故於半導體晶片的製造工序等中無法搬送半導體晶圓105。 As shown in FIG. 6, when warpage occurs in the semiconductor wafer 105, for example, there is a problem in that air leakage occurs when the semiconductor wafer 105 is attracted by a vacuum transfer mechanism, so that semiconductor wafer fabrication is performed. The semiconductor wafer 105 cannot be transferred in a process or the like.

相對於此，根據本發明之膜組件10，如上所述，使熱固化性樹脂膜1與第二保護膜形成膜2之間的發熱起始溫度及發熱峰溫度的關係最適化，由此獲得賦予至半導體晶圓5之應力的矯正作用，可抑制半導體晶圓5中產生翹曲。 On the other hand, according to the membrane module 10 of the present invention, the relationship between the heat generation onset temperature and the exothermic peak temperature between the thermosetting resin film 1 and the second protective film formation film 2 is optimized as described above, thereby obtaining The correction effect of the stress applied to the semiconductor wafer 5 suppresses warpage in the semiconductor wafer 5.

<<半導體晶圓用第一保護膜的形成方法>> <<Method of Forming First Protective Film for Semiconductor Wafer>>

本發明之半導體晶圓用第一保護膜的形成方法如圖1A至圖1D所示，為於半導體晶圓5的具有複數個凸塊51之表面5a形成用以保護該等複數個凸塊51之第一保護膜1a的方法。本發明之半導體晶圓用第一保護膜的形成方法例如係使用具有上述構成之本發明之膜組件10、熱固化性樹脂膜1或第一保護膜形成用片1A，於半導體晶圓5的表面5a形成第一保護膜1a。本發明之半導體晶圓用第一保護膜的形成方法係大致構成為包括積層步驟及固化步驟，上述積層步驟中係形成將第二保護膜形成膜2、半導體晶圓5及熱固化性樹脂膜1依序積層而成之積 層體50，上述固化步驟係於半導體晶圓5的表面5a形成第一保護膜1a。 As shown in FIG. 1A to FIG. 1D, the first protective film for a semiconductor wafer of the present invention is formed on the surface 5a of the semiconductor wafer 5 having a plurality of bumps 51 for protecting the plurality of bumps 51. The method of the first protective film 1a. In the method of forming the first protective film for a semiconductor wafer of the present invention, for example, the film module 10 of the present invention having the above-described configuration, the thermosetting resin film 1 or the first protective film forming sheet 1A are used in the semiconductor wafer 5. The surface 5a forms the first protective film 1a. The method for forming a first protective film for a semiconductor wafer according to the present invention is basically configured to include a stacking step and a curing step, and the second protective film forming film 2, the semiconductor wafer 5, and the thermosetting resin film are formed in the stacking step. 1 product of sequential stacking In the layer body 50, the curing step is performed on the surface 5a of the semiconductor wafer 5 to form the first protective film 1a.

如圖1A所示，於積層步驟中，首先於半導體晶圓5的與形成有電路及凸塊51之表面5a為相反側的面、亦即背面5b側貼著第二保護膜形成膜2。進而，於積層步驟中，如圖1A所示，於在背面5b側貼附有第二保護膜形成膜2之半導體晶圓5的表面5a，以覆蓋複數個凸塊51之方式貼附熱固化性樹脂膜1，藉此形成將第二保護膜形成膜2、半導體晶圓5及熱固化性樹脂膜1依序積層而成之積層體50。此時，關於第二保護膜形成膜2的露出表面，設定為貼著有圖1A中省略圖示之切割膠帶之狀態。 As shown in FIG. 1A, in the lamination step, first, the second protective film forming film 2 is adhered to the surface of the semiconductor wafer 5 opposite to the surface 5a on which the circuit and the bump 51 is formed, that is, the back surface 5b side. Further, in the laminating step, as shown in FIG. 1A, the surface 5a of the semiconductor wafer 5 to which the second protective film forming film 2 is attached on the back surface 5b side is attached to the plurality of bumps 51 to be thermally cured. The resin film 1 forms a layered body 50 in which the second protective film forming film 2, the semiconductor wafer 5, and the thermosetting resin film 1 are sequentially laminated. At this time, the exposed surface of the second protective film forming film 2 is set to be in a state in which the dicing tape (not shown) in FIG. 1A is attached.

然後，如圖1B所示，使用切割膠帶60將積層體50固定於省略圖示之晶圓切割用環形框架上。此時，雖省略詳細之圖示，但可將切割膠帶60的上表面60a貼著於第二保護膜形成膜2，藉由切割膠帶60的黏著面(與第二保護膜形成膜2的外側周邊部相對應)，將積層體50(參照圖1A)貼著固定於省略圖示之環形框架。 Then, as shown in FIG. 1B, the laminated body 50 is fixed to the ring frame for wafer dicing (not shown) by using the dicing tape 60. In this case, although the detailed illustration is omitted, the upper surface 60a of the dicing tape 60 may be attached to the second protective film forming film 2 by the adhesive surface of the dicing tape 60 (the outer side of the film 2 is formed with the second protective film). In the peripheral portion, the laminated body 50 (see FIG. 1A) is attached to and fixed to an annular frame (not shown).

繼而，如圖1C所示，於固化步驟中，對上述積層步驟中所得之積層體50(參照圖1A)例如使用先前公知之加壓加熱固化裝置一面加壓一面加熱。藉此，於固化步驟中，使複數個凸塊51貫穿熱固化性樹脂膜1，以將複數 個凸塊51各自之間填埋之方式使熱固化性樹脂膜1加熱固化，於半導體晶圓5的表面5a形成第一保護膜1a。另外，與此同時，使第二保護膜形成膜2固化，由此於半導體晶圓5的背面5b上形成第二保護膜2a。 Then, as shown in FIG. 1C, in the curing step, the layered body 50 (see FIG. 1A) obtained in the above-described layering step is heated while being pressurized, for example, using a conventionally known pressure-heat curing device. Thereby, in the curing step, a plurality of bumps 51 are inserted through the thermosetting resin film 1 to The bumps 51 are filled with each other to heat and cure the thermosetting resin film 1, and the first protective film 1a is formed on the surface 5a of the semiconductor wafer 5. At the same time, the second protective film forming film 2 is cured, whereby the second protective film 2a is formed on the back surface 5b of the semiconductor wafer 5.

繼而，雖省略詳細之圖示，但藉由切割處理將於各面形成有第一保護膜1a及第二保護膜2a之半導體晶圓5切成晶片單位後，如圖1D所示，一面去除切割膠帶60，一面自省略圖示之環形框架剝離而取下。 Then, although the detailed illustration is omitted, the semiconductor wafer 5 in which the first protective film 1a and the second protective film 2a are formed on each surface is cut into wafer units by a dicing process, and then removed as shown in FIG. 1D. The dicing tape 60 is peeled off from the annular frame (not shown) and removed.

本發明之半導體晶圓用第一保護膜的形成方法中，與上述同樣地使用藉由示差掃描熱量分析法所測定之發熱起始溫度與第二保護膜形成膜2的發熱起始溫度相同或較其更高者作為熱固化性樹脂膜1，進而採用經設定為如下關係之條件：熱固化性樹脂膜1及第二保護膜形成膜2的藉由示差掃描熱量分析法所測定之發熱峰溫度為100℃至200℃，且熱固化性樹脂膜1與第二保護膜形成膜2的發熱峰溫度之差小於35℃。另外，進而於本發明之半導體晶圓用第一保護膜的形成方法中可採用以下條件：熱固化性樹脂膜1的線膨脹係數為5(×10-6/℃)至80(×10-6/℃)，熱固化性樹脂膜1與第二保護膜形成膜2的線膨脹係數之差小於35(×10-6/℃)。 In the method for forming a first protective film for a semiconductor wafer according to the present invention, the heat generation onset temperature measured by the differential scanning calorimetry method is the same as or the same as the heat generation onset temperature of the second protective film forming film 2, or the like. The higher temperature is the thermosetting resin film 1, and the conditions are set as follows: the heat-generating peak of the thermosetting resin film 1 and the second protective film forming film 2 measured by differential scanning calorimetry The temperature is from 100 ° C to 200 ° C, and the difference in the exothermic peak temperature between the thermosetting resin film 1 and the second protective film forming film 2 is less than 35 ° C. Further, in the method of forming the first protective film for a semiconductor wafer of the present invention, the following conditions can be employed: the coefficient of linear expansion of the thermosetting resin film 1 is 5 (×10 -6 /° C.) to 80 (×10 − 6 / ° C), the difference in linear expansion coefficient between the thermosetting resin film 1 and the second protective film forming film 2 is less than 35 (×10 -6 /°C).

根據本發明之第一保護膜1a的形成方法，由於其與上述同樣地，為於半導體晶圓5的表面5a側之熱固化性樹脂膜1、與背面5b側的第二保護膜形成膜2之間的發熱起始溫度及發熱峰溫度的關係經最適化之條件下，於半導體晶圓5的表面5a形成第一保護膜1a之方法，故可於固化步驟中抑制半導體晶圓中產生翹曲。藉此，與上述同樣地可製造可靠性優異之半導體封裝。 According to the method of forming the first protective film 1a of the present invention, the film 2 is formed on the surface 5a side of the semiconductor wafer 5 and the second protective film 2 on the back surface 5b side. The method of forming the first protective film 1a on the surface 5a of the semiconductor wafer 5 under the condition that the relationship between the heat generation onset temperature and the exothermic peak temperature is optimized, so that the warpage in the semiconductor wafer can be suppressed in the curing step. song. Thereby, a semiconductor package excellent in reliability can be manufactured in the same manner as described above.

藉由加熱使本發明之熱固化性樹脂膜1軟化及固化時之加熱溫度只要根據熱固化性樹脂膜1的構成成分等而適切調節即可，並無特別限定，例如較佳為60℃至200℃。 The heating temperature when the thermosetting resin film 1 of the present invention is softened and cured by heating is appropriately adjusted according to the constituent components of the thermosetting resin film 1 and the like, and is not particularly limited. For example, it is preferably 60 ° C to 200 ° C.

以下，對本發明之各構成要素加以更詳細說明。 Hereinafter, each constituent element of the present invention will be described in more detail.

<<第一保護膜形成用片>> <<First protective film forming sheet>>

具有上述構成之本發明之膜組件10可採用以下構成：熱固化性樹脂膜1以於第一支持片11的一方的表面11a上具備第一保護膜形成用片1A之形式而包含於膜組件10中。 The membrane module 10 of the present invention having the above-described configuration may be configured such that the thermosetting resin film 1 is included in the membrane module in the form of the first protective film forming sheet 1A on one surface 11a of the first support sheet 11. 10 in.

以下，對第一保護膜形成用片1A及其所含之熱固化性樹脂膜1之各構成加以詳述。 Hereinafter, each configuration of the first protective film forming sheet 1A and the thermosetting resin film 1 contained therein will be described in detail.

<第一支持片> <first support sheet>

第一保護膜形成用片1A所具備之第一支持片11可由一層(單層)所構成，亦可由兩層以上之複數層所構成。於第一支持片11由複數層所構成之情形時，該等複數層之構成材料及厚度可彼此相同亦可不同，該等複數層的組合只要不損及本發明之功效，則並無特別限定。 The first support sheet 11 included in the first protective film forming sheet 1A may be composed of one layer (single layer) or may be composed of a plurality of layers of two or more layers. In the case where the first support sheet 11 is composed of a plurality of layers, the constituent materials and thicknesses of the plurality of layers may be the same or different, and the combination of the plurality of layers is not particularly long as long as the effect of the present invention is not impaired. limited.

再者，於本實施形態中，不限於第一支持片之情形，所謂「複數層可彼此相同亦可不同」，係指「可使所有的層相同，亦可使所有的層不同，亦可僅使一部分層相同」，進而所謂「複數層彼此不同」，係指「各層的構成材料及厚度的至少一者彼此不同」。 Furthermore, in the present embodiment, the present invention is not limited to the case of the first support sheet, and the phrase "the plurality of layers may be the same or different from each other" means "all layers may be the same, or all layers may be different. Only a part of the layers are the same, and the term "the plural layers are different from each other" means that "at least one of the constituent materials and the thickness of each layer are different from each other".

作為較佳之第一支持片11，可列舉：於第一基材上積層第一黏著劑層而成者、於第一基材上積層第一中間層並於第一中間層上積層第一黏著劑層而成者、僅由第一基材所構成者等。 As a preferred first support sheet 11, a first adhesive layer is laminated on the first substrate, a first intermediate layer is laminated on the first substrate, and a first adhesive layer is laminated on the first intermediate layer. The agent layer is formed only by the first substrate.

依此種第一支持片的種類，一面參照圖2至圖4一面對本發明之第一保護膜形成用片的例子進行說明。 An example of the first protective film forming sheet of the present invention will be described with reference to FIGS. 2 to 4 in accordance with the type of the first supporting sheet.

圖2係示意性地表示本發明之第一保護膜形成用片的一例之剖面圖。圖2所示之第一保護膜形成用片1A係使用於第一基材12上積層第一黏著劑層13而成者作為第一支持片11。亦即，第一保護膜形成用片1A係於第一基材12上具備第一黏著劑層13，於第一黏著劑層13上具 備含有熱固化性成分之熱固化性樹脂膜1而構成。第一支持片11為第一基材12及第一黏著劑層13之積層體，於第一支持片11的一方的表面11a上、亦即第一黏著劑層13的一方的表面13a上設有熱固化性樹脂膜1。 Fig. 2 is a cross-sectional view schematically showing an example of a sheet for forming a first protective film of the present invention. The first protective film forming sheet 1A shown in FIG. 2 is used as a first support sheet 11 in which a first adhesive layer 13 is laminated on a first base material 12. That is, the first protective film forming sheet 1A is provided with the first adhesive layer 13 on the first substrate 12, and is provided on the first adhesive layer 13 The thermosetting resin film 1 containing a thermosetting component is provided. The first support sheet 11 is a laminate of the first base material 12 and the first adhesive layer 13, and is provided on one surface 11a of the first support sheet 11, that is, on one surface 13a of the first adhesive layer 13. There is a thermosetting resin film 1.

第一保護膜形成用片1A中，熱固化性樹脂膜1係如上所述般貼著於半導體晶圓的凸塊形成面而使用，且係與貼附於半導體晶圓的背面之第二保護膜形成膜之間，發熱起始溫度及發熱峰溫度、進而線膨脹係數的關係經最適化而成。 In the first protective film forming sheet 1A, the thermosetting resin film 1 is applied to the bump forming surface of the semiconductor wafer as described above, and is attached to the second surface of the semiconductor wafer. The relationship between the heat generation onset temperature, the exothermic peak temperature, and the linear expansion coefficient between the film formation films is optimized.

圖3係示意性地表示本發明之第一保護膜形成用片的其他例之剖面圖。再者，圖3中，對與圖2中所示者相同之構成要素標注與圖2之情形相同的符號，省略其詳細說明，圖4中亦相同。 Fig. 3 is a cross-sectional view schematically showing another example of the first protective film forming sheet of the present invention. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals as those in FIG. 2, and the detailed description thereof is omitted, and the same applies to FIG.

圖3所示之第一保護膜形成用片1B係使用於第一基材上積層第一中間層並於第一中間層上積層第一黏著劑層而成者作為第一支持片。亦即，第一保護膜形成用片1B係於第一基材12上具備第一中間層14，於第一中間層14上具備第一黏著劑層13，於第一黏著劑層13上具備熱固化性樹脂膜1而構成。第一支持片11A係將第一基材12、第一中間層14及第一黏著劑層13依序積層而成之積層體，於第一支持片11A的一方的表面11a上、亦即第一黏著劑層13的一方的表面13a上設有熱固化性樹脂膜1。 The first protective film forming sheet 1B shown in FIG. 3 is used as a first support sheet by laminating a first intermediate layer on a first substrate and laminating a first adhesive layer on the first intermediate layer. In other words, the first protective film forming sheet 1B includes the first intermediate layer 14 on the first base material 12, the first adhesive layer 13 on the first intermediate layer 14, and the first adhesive layer 13 on the first adhesive layer 13. The thermosetting resin film 1 is comprised. The first support sheet 11A is a laminate in which the first base material 12, the first intermediate layer 14, and the first adhesive layer 13 are sequentially laminated, and is formed on one surface 11a of the first support sheet 11A. A thermosetting resin film 1 is provided on one surface 13a of one adhesive layer 13.

換言之，第一保護膜形成用片1B係於圖2所示之第一保護膜形成用片1A中，於第一基材12與第一黏著劑層13之間進一步具備第一中間層14。 In other words, the first protective film forming sheet 1B is attached to the first protective film forming sheet 1A shown in FIG. 2, and further includes a first intermediate layer 14 between the first base material 12 and the first adhesive layer 13.

第一保護膜形成用片1B中，熱固化性樹脂膜1係如上所述般貼著於半導體晶圓的凸塊形成面而使用，且係與貼附於半導體晶圓的背面上之第二保護膜形成膜之間，發熱起始溫度及發熱峰溫度、進而線膨脹係數的關係經最適化而成。 In the first protective film forming sheet 1B, the thermosetting resin film 1 is applied to the bump forming surface of the semiconductor wafer as described above, and is attached to the second surface of the semiconductor wafer. Between the protective film forming films, the relationship between the heat generation onset temperature, the exothermic peak temperature, and the linear expansion coefficient is optimized.

圖4係示意性地表示本發明之第一保護膜形成用片的進而其他例之剖面圖。 Fig. 4 is a cross-sectional view showing still another example of the first protective film forming sheet of the present invention.

圖4所示之第一保護膜形成用片1C係使用僅由第一基材所構成者作為第一支持片。亦即，第一保護膜形成用片1C係於第一基材12上具備熱固化性樹脂膜1而構成。第一支持片11B係僅由第一基材12構成，於第一支持片11B的一方的表面11a上、亦即第一基材12的一方的表面12a上直接接觸而設有熱固化性樹脂膜1。 The first protective film forming sheet 1C shown in Fig. 4 uses a first support sheet as the first support sheet. In other words, the first protective film forming sheet 1C is formed by providing the thermosetting resin film 1 on the first base material 12. The first support sheet 11B is composed only of the first base material 12, and is provided with a thermosetting resin directly on one surface 11a of the first support sheet 11B, that is, on one surface 12a of the first base material 12. Membrane 1.

換言之，第一保護膜形成用片1C係於圖2所示之第一保護膜形成用片1A中將第一黏著劑層13去除掉而成。 In other words, the first protective film forming sheet 1C is obtained by removing the first adhesive layer 13 from the first protective film forming sheet 1A shown in FIG. 2 .

第一保護膜形成用片1C中，熱固化性樹脂膜1係如上所述般貼著於半導體晶圓的凸塊形成面而使用，且係與貼附於半導體晶圓的背面之第二保護膜形成膜2之間的發熱起始溫度及發熱峰溫度、進而線膨脹係數的關係經最適化而成。 In the first protective film forming sheet 1C, the thermosetting resin film 1 is used by being attached to the bump forming surface of the semiconductor wafer as described above, and is attached to the second surface of the semiconductor wafer. The relationship between the heat generation onset temperature, the exothermic peak temperature, and the linear expansion coefficient between the film formation films 2 is optimized.

以下，對第一支持片之各構成加以詳述。 Hereinafter, each configuration of the first support sheet will be described in detail.

[第一基材] [first substrate]

第一支持片所具備之第一基材為片狀或膜狀者，作為其構成材料，例如可列舉以下之各種樹脂。 The first base material provided in the first support sheet is in the form of a sheet or a film, and examples of the constituent material thereof include the following various resins.

作為構成第一基材之樹脂，例如可列舉：低密度聚乙烯(LDPE；Low Density Polyethylene)、直鏈低密度聚乙烯(LLDPE；Linear Low Density Polyethylene)、高密度聚乙烯(HDPE；High Density Polyethylene)等聚乙烯；聚丙烯、聚丁烯、聚丁二烯、聚甲基戊烯、降莰烯樹脂等聚乙烯以外之聚烯烴；乙烯-乙酸乙烯酯共聚物、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物、乙烯-降莰烯共聚物等乙烯系共聚物(使用乙烯作為單體所得之共聚物)；聚氯乙烯、氯乙烯共聚物等氯乙烯系樹脂(使用氯乙烯作為單體所得之樹脂)；聚苯乙烯；聚環烯烴；聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯、聚間苯二甲酸丁二酯、聚2,6-萘二甲酸乙二酯、所有結構單元具有芳香族環式基之全芳香族聚酯等聚酯；兩種以上之前述聚酯之共聚物；聚(甲基)丙烯酸酯；聚胺基甲酸酯；聚丙烯酸胺基甲酸酯；聚醯亞胺；聚醯胺；聚碳酸酯；氟樹脂；聚縮醛；改質聚苯醚；聚苯硫醚；聚碸；聚醚酮等。 Examples of the resin constituting the first substrate include low density polyethylene (LDPE; Low Density Polyethylene), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE; High Density Polyethylene). Polyethylene, polyethylene other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid Vinyl copolymers such as copolymers, ethylene-(meth)acrylate copolymers and ethylene-norbornene copolymers (copolymers obtained by using ethylene as a monomer); vinyl chlorides such as polyvinyl chloride and vinyl chloride copolymers Resin (resin obtained using vinyl chloride as a monomer); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-m-phenylene a polyester such as butylene dicarboxylate, polyethylene 2,6-naphthalenedicarboxylate, a polyester such as a wholly aromatic polyester having an aromatic ring group; a copolymer of two or more of the foregoing polyesters; Methyl) acrylate; polyurethane; polypropylene Acid urethane; polyimide; polyamides; polycarbonates; fluorine resin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; polysulfone; polyether ketone.

另外，作為前述樹脂，例如亦可列舉前述聚酯與除此以外的樹脂之混合物等聚合物合金。前述聚酯與除此以外 的樹脂之聚合物合金較佳為聚酯以外的樹脂的量為相對較少之量。 In addition, as the resin, for example, a polymer alloy such as a mixture of the above polyester and a resin other than the above may be mentioned. The aforementioned polyester and other than The polymer alloy of the resin is preferably a relatively small amount of the resin other than the polyester.

另外，作為前述樹脂，例如亦可列舉：到此為止所例示之前述樹脂的一種或兩種以上進行交聯而成的交聯樹脂；使用到此為止所例示之前述樹脂的一種或兩種以上之離子聚合物等改質樹脂。 In addition, as the resin, for example, a crosslinked resin obtained by crosslinking one or two or more kinds of the resins exemplified so far, and one or more of the above-exemplified resins may be used. A modified resin such as an ionic polymer.

再者，本實施形態中，所謂「(甲基)丙烯酸」，係指包含「丙烯酸」及「甲基丙烯酸」兩者之概念。關於與(甲基)丙烯酸類似的用語亦相同，例如所謂「(甲基)丙烯酸酯」，係包含「丙烯酸酯」及「甲基丙烯酸酯」兩者之概念，所謂「(甲基)丙烯醯基」，係包含「丙烯醯基」及「甲基丙烯醯基」兩者之概念。 In the present embodiment, "(meth)acrylic acid" means a concept including both "acrylic acid" and "methacrylic acid". The term "(meth)acrylate" is similar to that of (meth)acrylic acid. For example, "(meth)acrylate" includes the concept of "acrylate" and "methacrylate". The term "base" includes the concepts of both "acryloyl group" and "methacryloyl group".

構成第一基材之樹脂可僅為一種亦可為兩種以上。於構成第一基材之樹脂為兩種以上之情形時，該等的組合及比率可任意地選擇。 The resin constituting the first substrate may be one type or two or more types. When the resin constituting the first substrate is two or more kinds, the combinations and ratios can be arbitrarily selected.

第一基材可僅為一層(單層)，亦可為兩層以上之複數層。於第一基材為複數層之情形時，該等複數層可彼此相同亦可不同，該等複數層的組合並無特別限定。 The first substrate may be only one layer (single layer), or may be a plurality of layers of two or more layers. In the case where the first substrate is a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.

第一基材的厚度較佳為5μm至1000μm，更佳為10μm至500μm，進而佳為15μm至300μm，尤佳為20μm至150μm。 The thickness of the first substrate is preferably from 5 μm to 1000 μm, more preferably from 10 μm to 500 μm, still more preferably from 15 μm to 300 μm, still more preferably from 20 μm to 150 μm.

此處所謂「第一基材的厚度」，係指第一基材總體的厚度，例如所謂由複數層所構成之第一基材的厚度，係指構成第一基材之所有層的合計厚度。 Here, the "thickness of the first base material" means the thickness of the entire first base material, for example, the thickness of the first base material composed of a plurality of layers, and the total thickness of all the layers constituting the first base material. .

第一基材較佳為厚度的精度較高者、亦即與部位無關而厚度之偏差得到抑制者。上述構成材料中，作為可用於構成此種厚度的精度較高之第一基材之材料，例如可列舉：聚乙烯、聚乙烯以外之聚烯烴、聚對苯二甲酸乙二酯、乙烯-乙酸乙烯酯共聚物等。 The first substrate preferably has a higher precision of thickness, that is, a deviation from the thickness regardless of the portion. Among the above-mentioned constituent materials, examples of the material of the first base material which can be used for forming such a high-precision thickness include polyolefins other than polyethylene and polyethylene, polyethylene terephthalate, and ethylene-acetic acid. Vinyl ester copolymer and the like.

第一基材除了前述樹脂等主要構成材料以外，可含有填充材料、著色劑、抗靜電劑、抗氧化劑、有機潤滑劑、觸媒、軟化劑(塑化劑)等公知之各種添加劑。 The first base material may contain various additives such as a filler, a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and a softener (plasticizer) in addition to the main constituent materials such as the resin.

第一基材可為透明，亦可為不透明，亦可根據目的而著色，或亦可蒸鍍有其他層。 The first substrate may be transparent or opaque, may be colored according to the purpose, or may be vapor deposited with other layers.

另外，於後述第一黏著劑層或固化性樹脂層具有能量線固化性之情形時，第一基材較佳為使能量線透過。 Further, when the first adhesive layer or the curable resin layer has energy ray curability, the first substrate preferably transmits energy rays.

第一基材可利用公知之方法製造。例如，含有樹脂之第一基材可藉由將含有前述樹脂之樹脂組成物成形而製造。 The first substrate can be produced by a known method. For example, the first substrate containing a resin can be produced by molding a resin composition containing the above resin.

[第一黏著劑層] [First Adhesive Layer]

第一黏著劑層為片狀或膜狀，含有黏著劑。 The first adhesive layer is in the form of a sheet or a film and contains an adhesive.

作為前述黏著劑，例如可列舉：丙烯酸系樹脂(由具有(甲基)丙烯醯基之樹脂所構成之黏著劑)、胺基甲酸酯系樹脂(由具有胺基甲酸酯鍵之樹脂所構成之黏著劑)、橡膠系樹脂(由具有橡膠結構之樹脂所構成之黏著劑)、矽酮系樹脂(由具有矽氧烷鍵之樹脂所構成之黏著劑)、環氧系樹脂(由具有環氧基之樹脂所構成之黏著劑)、聚乙烯醚、聚碳酸酯等黏著性樹脂，較佳為丙烯酸系樹脂。 Examples of the pressure-sensitive adhesive include an acrylic resin (an adhesive composed of a resin having a (meth)acryl fluorenyl group) and a urethane resin (a resin having a urethane bond). Adhesive), a rubber-based resin (an adhesive composed of a resin having a rubber structure), an anthrone-based resin (an adhesive composed of a resin having a siloxane coupling), and an epoxy resin (having An adhesive resin such as an epoxy group resin, or an adhesive resin such as polyvinyl ether or polycarbonate is preferably an acrylic resin.

再者，本發明中，所謂「黏著性樹脂」，係包含具有黏著性之樹脂、與具有接著性之樹脂兩者的概念，例如不僅為樹脂自身具有黏著性者，亦包含藉由與添加劑等其他成分並用而顯示出黏著性之樹脂、或者藉由熱或水等觸發(trigger)之存在而顯示出接著性之樹脂等。 In the present invention, the term "adhesive resin" includes both a resin having adhesiveness and a resin having adhesiveness. For example, not only the resin itself but also an additive, etc. A resin which exhibits adhesiveness in combination with other components, or a resin which exhibits adhesiveness by the presence of a trigger such as heat or water.

第一黏著劑層可僅為一層(單層)，亦可為兩層以上之複數層。於第一黏著劑層為複數層之情形時，該等複數層可彼此相同亦可不同，該等複數層的組合並無特別限定。 The first adhesive layer may be only one layer (single layer), or may be a plurality of layers of two or more layers. In the case where the first adhesive layer is a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.

第一黏著劑層的厚度較佳為1μm至1000μm，更佳為5μm至500μm，尤佳為10μm至100μm。 The thickness of the first adhesive layer is preferably from 1 μm to 1000 μm, more preferably from 5 μm to 500 μm, still more preferably from 10 μm to 100 μm.

此處所謂「第一黏著劑層的厚度」，係指第一黏著劑層總體的厚度，例如所謂由複數層所構成之第一黏著劑層的厚度，係指構成第一黏著劑層之所有層的合計厚度。 The term "thickness of the first adhesive layer" as used herein means the thickness of the first adhesive layer as a whole, for example, the thickness of the first adhesive layer composed of a plurality of layers, which means that all of the first adhesive layers are formed. The total thickness of the layers.

第一黏著劑層可使用能量線固化性黏著劑而形成，亦可使用非能量線固化性黏著劑而形成。使用能量線固化性的黏著劑而形成之第一黏著劑層可容易地調節固化前及固化後的物性。 The first adhesive layer can be formed using an energy ray-curable adhesive, or can be formed using a non-energy ray-curable adhesive. The first adhesive layer formed using the energy ray-curable adhesive can easily adjust the physical properties before and after curing.

本發明中所謂「能量線」，係指電磁波或帶電粒子束中具有能量量子者，作為其例子，可列舉紫外線、電子束等。 In the present invention, the term "energy line" means an energy quantum in an electromagnetic wave or a charged particle beam, and examples thereof include ultraviolet rays, electron beams, and the like.

紫外線例如可藉由使用高壓水銀燈、融合H燈(husion H lamp)、氙氣燈或LED(Light Emitting Diode；發光二極體)等作為紫外線源而照射。關於電子束，可照射藉由電子束加速器等所產生者。 The ultraviolet light can be irradiated, for example, by using a high pressure mercury lamp, a husion H lamp, a xenon lamp, or an LED (Light Emitting Diode) as an ultraviolet source. Regarding the electron beam, it can be irradiated by an electron beam accelerator or the like.

本發明中所謂「能量線固化性」，係指藉由照射能量線而固化之性質，所謂「非能量線固化性」，係指即便照射能量線亦不固化之性質。 In the present invention, the term "energy ray curability" refers to a property of curing by irradiation with an energy ray. The term "non-energy ray curability" means a property that does not cure even when irradiated with an energy ray.

{{第一黏著劑組成物}} {{first adhesive composition}}

第一黏著劑層可使用含有黏著劑之第一黏著劑組成物而形成。例如藉由在第一黏著劑層之形成對象面塗敷第 一黏著劑組成物，視需要進行乾燥，可於目標部位形成第一黏著劑層。關於第一黏著劑層的更具體的形成方法，將與其他層的形成方法一併於後文中詳細說明。關於第一黏著劑組成物中的於常溫下不氣化之成分彼此的含量的比率，通常與第一黏著劑層的前述成分彼此的含量的比率相同。再者，本實施形態中，所謂「常溫」，係指不特別冷或熱之溫度、亦即平常之溫度，例如可列舉15℃至25℃之溫度等。 The first adhesive layer can be formed using a first adhesive composition containing an adhesive. For example, by coating the surface of the first adhesive layer An adhesive composition, which is dried as needed, forms a first adhesive layer at the target site. A more specific method of forming the first adhesive layer will be described in detail later together with the formation method of the other layers. The ratio of the content of the components which are not vaporized at normal temperature in the first adhesive composition is usually the same as the ratio of the contents of the aforementioned components of the first adhesive layer. In the present embodiment, the term "normal temperature" means a temperature which is not particularly cold or hot, that is, a normal temperature, and examples thereof include a temperature of 15 ° C to 25 ° C.

第一黏著劑組成物之塗敷只要利用公知之方法進行即可，例如可列舉：使用氣刀塗佈機、刮刀塗佈機、棒式塗佈機、凹版塗佈機、輥式塗佈機、輥刀塗佈機、簾幕式塗佈機、模式塗佈機、刀片塗佈機、網版塗佈機、線棒塗佈機及吻合式塗佈機等各種塗佈機之方法。 The application of the first adhesive composition may be carried out by a known method, and examples thereof include an air knife coater, a knife coater, a bar coater, a gravure coater, and a roll coater. A method of various coaters such as a roll coater, a curtain coater, a pattern coater, a blade coater, a screen coater, a bar coater, and a staple coater.

第一黏著劑組成物的乾燥條件並無特別限定，於第一黏著劑組成物含有後述溶劑之情形時，較佳為進行加熱乾燥，於該情形時，例如較佳為於70℃至130℃且10秒至5分鐘之條件下進行乾燥。 The drying condition of the first adhesive composition is not particularly limited. When the first adhesive composition contains a solvent to be described later, it is preferably heated and dried. In this case, for example, it is preferably at 70 ° C to 130 ° C. Drying is carried out for 10 seconds to 5 minutes.

於第一黏著劑層為能量線固化性之情形時，作為含有能量線固化性黏著劑之第一黏著劑組成物、亦即能量線固化性的第一黏著劑組成物，例如可列舉如下黏著劑組成物等：第一黏著劑組成物(I-1)，其含有非能量線固化性的黏 著性樹脂(I-1a)(以下有時簡稱為「黏著性樹脂(I-1a)」)、及能量線固化性化合物；第一黏著劑組成物(I-2)，其含有於非能量線固化性的黏著性樹脂(I-1a)的側鏈中導入有不飽和基之能量線固化性的黏著性樹脂(I-2a)(以下有時簡稱為「黏著性樹脂(I-2a)」)；以及第一黏著劑組成物(I-3)，其含有前述黏著性樹脂(I-2a)、及能量線固化性低分子化合物。 When the first adhesive layer is in the form of energy ray curability, the first adhesive composition containing the energy ray-curable adhesive, that is, the energy ray-curable first adhesive composition, for example, the following adhesives Agent composition, etc.: first adhesive composition (I-1), which contains non-energy line curable adhesive The resin (I-1a) (hereinafter sometimes referred to simply as "adhesive resin (I-1a)") and the energy ray-curable compound; the first adhesive composition (I-2), which is contained in the non-energy An energy ray-curable adhesive resin (I-2a) having an unsaturated group introduced into the side chain of the line-curable adhesive resin (I-1a) (hereinafter sometimes referred to as "adhesive resin (I-2a)" And a first adhesive composition (I-3) containing the above-mentioned adhesive resin (I-2a) and an energy ray-curable low molecular compound.

{第一黏著劑組成物(I-1)} {First Adhesive Composition (I-1)}

如上所述，第一黏著劑組成物(I-1)含有非能量線固化性之黏著性樹脂(I-1a)、及能量線固化性化合物。 As described above, the first adhesive composition (I-1) contains a non-energy ray-curable adhesive resin (I-1a) and an energy ray-curable compound.

(黏著性樹脂(I-1a)) (Adhesive resin (I-1a))

前述黏著性樹脂(I-1a)較佳為丙烯酸系樹脂。 The adhesive resin (I-1a) is preferably an acrylic resin.

作為前述丙烯酸系樹脂，例如可列舉至少具有源自(甲基)丙烯酸烷基酯之結構單元的丙烯酸系聚合物。 The acrylic resin may, for example, be an acrylic polymer having at least a structural unit derived from an alkyl (meth)acrylate.

前述丙烯酸系樹脂所具有之結構單元可僅為一種亦可為兩種以上。於前述丙烯酸系樹脂所具有之結構單元為兩種以上之情形時，該等的組合及比率可任意地選擇。 The structural unit of the acrylic resin may be one type or two or more types. When the structural unit of the acrylic resin is two or more types, the combinations and ratios can be arbitrarily selected.

作為前述(甲基)丙烯酸烷基酯，例如可列舉構成烷基酯之烷基的碳數為1至20者，前述烷基較佳為直鏈狀或分支鏈狀。 The alkyl (meth)acrylate may, for example, be an alkyl group constituting the alkyl ester having 1 to 20 carbon atoms, and the alkyl group is preferably a linear or branched chain.

作為(甲基)丙烯酸烷基酯，更具體可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯((甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯((甲基)丙烯酸肉豆蔻酯)、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯((甲基)丙烯酸棕櫚酯)、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯((甲基)丙烯酸硬脂酯)、(甲基)丙烯酸十九烷基酯及(甲基)丙烯酸二十烷基酯等。 Specific examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. N-butyl methacrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Hexyl ester, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, Isodecyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), (A) Tridecyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, cetyl (meth) acrylate Ester (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), (meth) acrylate 19 Alkyl esters and eicosyl (meth)acrylate Esters and the like.

就第一黏著劑層的黏著力提高之方面而言，前述丙烯酸系聚合物較佳為具有源自前述烷基的碳數為4以上之(甲基)丙烯酸烷基酯的結構單元。而且，就第一黏著劑層的黏著力進一步提高之方面而言，前述烷基的碳數較佳為4至12，更佳為4至8。另外，前述烷基的碳數為4以上之(甲基)丙烯酸烷基酯較佳為丙烯酸烷基酯。 The acrylic polymer is preferably a structural unit having an alkyl (meth)acrylate having a carbon number of 4 or more derived from the alkyl group, in terms of improving the adhesion of the first adhesive layer. Further, the alkyl group preferably has a carbon number of 4 to 12, more preferably 4 to 8, in terms of further improving the adhesion of the first adhesive layer. Further, the alkyl (meth)acrylate having a carbon number of 4 or more in the alkyl group is preferably an alkyl acrylate.

前述丙烯酸系聚合物較佳為除了源自(甲基)丙烯酸烷基酯之結構單元以外，進一步具有源自含官能基之單體 之結構單元。 The acrylic polymer preferably further has a monomer derived from a functional group in addition to a structural unit derived from an alkyl (meth)acrylate. The structural unit.

作為前述含官能基之單體，例如可列舉：藉由前述官能基與後述交聯劑反應而成為交聯的起點，或前述官能基與含不飽和基之化合物中的不飽和基反應，由此可於丙烯酸系聚合物的側鏈中導入不飽和基者。 Examples of the functional group-containing monomer include a starting point for crosslinking by reaction of the functional group with a crosslinking agent described later, or a reaction of the functional group with an unsaturated group in the unsaturated group-containing compound. This can introduce an unsaturated group into the side chain of the acrylic polymer.

作為含官能基之單體中的前述官能基，例如可列舉羥基、羧基、胺基、環氧基等。 Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxyl group, an amine group, and an epoxy group.

亦即，作為含官能基之單體，例如可列舉含羥基之單體、含羧基之單體、含胺基之單體及含環氧基之單體等。 That is, examples of the functional group-containing monomer include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amine group-containing monomer, and an epoxy group-containing monomer.

作為前述含羥基之單體，例如可列舉：(甲基)丙烯酸羥基甲酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等(甲基)丙烯酸羥基烷基酯；乙烯醇、烯丙醇等非(甲基)丙烯酸系不飽和醇(不具有(甲基)丙烯醯基骨架之不飽和醇)等。 Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid 3- Hydroxypropyl ester, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; hydroxyalkyl (meth)acrylate; vinyl alcohol, A non-(meth)acrylic unsaturated alcohol such as allyl alcohol (an unsaturated alcohol having no (meth) acrylonitrile skeleton) or the like.

作為前述含羧基之單體，例如可列舉：(甲基)丙烯酸、丁烯酸等乙烯性不飽和單羧酸(具有乙烯性不飽和鍵之單羧酸)；富馬酸、衣康酸、馬來酸、檸康酸等乙烯性不飽和二羧酸(具有乙烯性不飽和鍵之二羧酸)；前述乙烯 性不飽和二羧酸的酐；甲基丙烯酸2-羧基乙酯等(甲基)丙烯酸羧基烷基酯等。 Examples of the carboxyl group-containing monomer include an ethylenically unsaturated monocarboxylic acid (monocarboxylic acid having an ethylenically unsaturated bond) such as (meth)acrylic acid or crotonic acid; fumaric acid and itaconic acid; Ethylene unsaturated dicarboxylic acid such as maleic acid or citraconic acid (dicarboxylic acid having an ethylenically unsaturated bond); An anhydride of a dicarboxylic acid; a carboxyalkyl (meth)acrylate such as 2-carboxyethyl methacrylate;

含官能基之單體較佳為含羥基之單體、含羧基之單體，更佳為含羥基之單體。 The functional group-containing monomer is preferably a hydroxyl group-containing monomer, a carboxyl group-containing monomer, more preferably a hydroxyl group-containing monomer.

構成前述丙烯酸系聚合物之含官能基之單體可僅為一種亦可為兩種以上。於構成前述丙烯酸系聚合物之含官能基之單體為兩種以上之情形時，該等的組合及比率可任意地選擇。 The functional group-containing monomer constituting the acrylic polymer may be one type or two or more types. When the number of the functional group-containing monomers constituting the acrylic polymer is two or more, the combinations and ratios can be arbitrarily selected.

前述丙烯酸系聚合物中，相對於結構單元的總質量，源自含官能基之單體之結構單元的含量較佳為1質量%至35質量%，更佳為3質量%至32質量%，尤佳為5質量%至30質量%。 In the acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably from 1% by mass to 35% by mass, more preferably from 3% by mass to 32% by mass, based on the total mass of the structural unit. More preferably, it is 5 mass% to 30 mass%.

前述丙烯酸系聚合物亦可除了源自(甲基)丙烯酸烷基酯之結構單元及源自含官能基之單體之結構單元以外，進一步具有源自其他單體之結構單元。 The acrylic polymer may further have a structural unit derived from another monomer in addition to the structural unit derived from the alkyl (meth)acrylate and the structural unit derived from the functional group-containing monomer.

前述其他單體只要可與(甲基)丙烯酸烷基酯等共聚合，則並無特別限定。 The other monomer is not particularly limited as long as it can be copolymerized with an alkyl (meth)acrylate or the like.

作為前述其他單體，例如可列舉：苯乙烯、α-甲基苯乙烯、乙烯基甲苯、甲酸乙烯酯、乙酸乙烯酯、丙烯腈及丙烯醯胺等。 Examples of the other monomer include styrene, α-methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.

構成前述丙烯酸系聚合物之前述其他單體可僅為一種亦可為兩種以上。於構成前述丙烯酸系聚合物之前述其他單體為兩種以上之情形時，該等的組合及比率可任意地選擇。 The other monomers constituting the acrylic polymer may be one type or two or more types. When two or more of the other monomers constituting the acrylic polymer are used, the combinations and ratios may be arbitrarily selected.

前述丙烯酸系聚合物可用作上述非能量線固化性的黏著性樹脂(I-1a)。 The acrylic polymer can be used as the above non-energy ray curable adhesive resin (I-1a).

另一方面，使具有能量線聚合性不飽和基(能量線聚合性基)之含不飽和基之化合物與前述丙烯酸系聚合物中的官能基反應而成者可用作上述能量線固化性的黏著性樹脂(I-2a)。 On the other hand, a compound containing an unsaturated group having an energy ray polymerizable unsaturated group (energy ray polymerizable group) and a functional group in the acrylic polymer can be used as the energy ray curability. Adhesive resin (I-2a).

再者，本發明中所謂「能量線聚合性」，係指藉由照射能量線而聚合之性質。 In the present invention, the term "energy ray polymerizability" refers to a property of being polymerized by irradiation of an energy ray.

第一黏著劑組成物(I-1)所含有之黏著性樹脂(I-1a)可僅為一種亦可為兩種以上。於第一黏著劑組成物(I-1)所含有之黏著性樹脂(I-1a)為兩種以上之情形時，該等的組合及比率可任意地選擇。 The adhesive resin (I-1a) contained in the first adhesive composition (I-1) may be one type or two or more types. When the adhesive resin (I-1a) contained in the first adhesive composition (I-1) is two or more kinds, the combinations and ratios can be arbitrarily selected.

第一黏著劑組成物(I-1)中，相對於第一黏著劑組成物(I-1)的總質量，黏著性樹脂(I-1a)的含量較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為15質量%至90質量%。 In the first adhesive composition (I-1), the content of the adhesive resin (I-1a) is preferably from 5% by mass to 99% by mass based on the total mass of the first adhesive composition (I-1). More preferably, it is 10 mass% to 95 mass%, and particularly preferably 15 mass% to 90 mass%.

(能量線固化性化合物) (energy ray curable compound)

作為第一黏著劑組成物(I-1)所含有之前述能量線固化性化合物，可列舉具有能量線聚合性不飽和基且可藉由能量線的照射而固化之單體或寡聚物。 The energy ray-curable compound contained in the first adhesive composition (I-1) includes a monomer or oligomer which has an energy ray polymerizable unsaturated group and can be cured by irradiation with an energy ray.

能量線固化性化合物中，作為單體，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇(甲基)丙烯酸酯等多元(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲酸酯；聚酯(甲基)丙烯酸酯；聚醚(甲基)丙烯酸酯；環氧(甲基)丙烯酸酯等。 In the energy ray-curable compound, examples of the monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol VI (A). Poly(meth)acrylates such as acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate; amine (meth)acrylate Ester; polyester (meth) acrylate; polyether (meth) acrylate; epoxy (meth) acrylate, and the like.

能量線固化性化合物中，作為寡聚物，例如可列舉前述所例示之單體聚合而成之寡聚物等。 In the energy ray-curable compound, examples of the oligomer include an oligomer obtained by polymerizing the above-exemplified monomers.

就分子量相對較大、不易使第一黏著劑層的儲存彈性模數降低之方面而言，能量線固化性化合物較佳為(甲基)丙烯酸胺基甲酸酯、(甲基)丙烯酸胺基甲酸酯寡聚物。 The energy ray-curable compound is preferably a (meth)acrylic acid urethane or a (meth)acrylic acid amine group in terms of a relatively large molecular weight and a tendency to lower the storage elastic modulus of the first adhesive layer. Formate oligomer.

第一黏著劑組成物(I-1)所含有之前述能量線固化性化合物可僅為一種亦可為兩種以上。於第一黏著劑組成物(I-1)所含有之前述能量線固化性化合物為兩種以上之情形時，該等的組合及比率可任意地選擇。 The energy ray-curable compound contained in the first adhesive composition (I-1) may be one type or two or more types. When the energy ray-curable compound contained in the first adhesive composition (I-1) is two or more kinds, the combinations and ratios can be arbitrarily selected.

第一黏著劑組成物(I-1)中，相對於第一黏著劑組成物(I-1)的總質量，前述能量線固化性化合物的含量較佳為1質量%至95質量%，更佳為5質量%至90質量%，尤佳為10質量%至85質量%。 In the first adhesive composition (I-1), the content of the energy ray-curable compound is preferably from 1% by mass to 95% by mass based on the total mass of the first adhesive composition (I-1). It is preferably from 5% by mass to 90% by mass, particularly preferably from 10% by mass to 85% by mass.

(交聯劑) (crosslinking agent)

於使用除了源自(甲基)丙烯酸烷基酯之結構單元以外進一步具有源自含官能基之單體之結構單元的前述丙烯酸系聚合物作為黏著性樹脂(I-1a)之情形時，第一黏著劑組成物(I-1)較佳為進一步含有交聯劑。 When the acrylic polymer having a structural unit derived from a functional group-containing monomer is further used as the adhesive resin (I-1a) in addition to the structural unit derived from the alkyl (meth)acrylate, An adhesive composition (I-1) preferably further contains a crosslinking agent.

前述交聯劑例如與前述官能基反應，將黏著性樹脂(I-1a)彼此交聯。 The crosslinking agent reacts with the aforementioned functional group, for example, to crosslink the adhesive resin (I-1a) with each other.

作為交聯劑，例如可列舉：甲苯二異氰酸酯、六亞甲基二異氰酸酯、二甲苯二異氰酸酯、該等二異氰酸酯之加合物等異氰酸酯系交聯劑(具有異氰酸酯基之交聯劑)；乙二醇縮水甘油醚等環氧系交聯劑(具有縮水甘油基之交聯劑)；六[1-(2-甲基)-氮丙啶基]三磷雜三嗪等氮丙啶系交聯劑(具有氮丙啶基之交聯劑)；鋁螯合物等金屬螯合物系交聯劑(具有金屬螯合物結構之交聯劑)；異三聚氰酸酯系交聯劑(具有異三聚氰酸骨架之交聯劑)等。 Examples of the crosslinking agent include isocyanate crosslinking agents (crosslinking agents having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, and adducts of such diisocyanates; An epoxy-based crosslinking agent such as a glycol glycidyl ether (a crosslinking agent having a glycidyl group); an aziridine-based crosslinking such as hexa[1-(2-methyl)-aziridine]triphosphorazine A crosslinking agent (a crosslinking agent having an aziridine group); a metal chelate crosslinking agent such as an aluminum chelate compound (a crosslinking agent having a metal chelate structure); an isocyanurate crosslinking agent (crosslinking agent having a hetero-cyanuric acid skeleton) or the like.

就使黏著劑的凝聚力提高而使第一黏著劑層的黏著力提高之方面、及獲取容易等方面而言，交聯劑較佳為異氰酸酯系交聯劑。 The crosslinking agent is preferably an isocyanate crosslinking agent in terms of improving the cohesive force of the adhesive, improving the adhesion of the first adhesive layer, and facilitating the acquisition.

第一黏著劑組成物(I-1)所含有之交聯劑可僅為一種亦可為兩種以上，於為兩種以上之情形時，該等的組合及比率可任意地選擇。 The crosslinking agent contained in the first adhesive composition (I-1) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

第一黏著劑組成物(I-1)中，相對於黏著性樹脂(I-1a)的含量100質量份，交聯劑的含量較佳為0.01質量份至50質量份，更佳為0.1質量份至20質量份，尤佳為1質量份至10質量份。 In the first adhesive composition (I-1), the content of the crosslinking agent is preferably from 0.01 part by mass to 50 parts by mass, more preferably 0.1% by mass based on 100 parts by mass of the adhesive resin (I-1a). The portion is preferably 20 parts by mass, particularly preferably 1 part by mass to 10 parts by mass.

(光聚合起始劑) (photopolymerization initiator)

第一黏著劑組成物(I-1)亦可進一步含有光聚合起始劑。含有光聚合起始劑之第一黏著劑組成物(I-1)即便照射紫外線等能量相對較低的能量線，亦充分進行固化反應。 The first adhesive composition (I-1) may further contain a photopolymerization initiator. The first adhesive composition (I-1) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with an energy line having a relatively low energy such as ultraviolet rays.

作為前述光聚合起始劑，例如可列舉：安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚、安息香苯甲酸、安息香苯甲酸甲酯、安息香二甲基縮酮等安息香化合物；苯乙酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等苯乙酮化合物；雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦等醯基氧化膦化合物；苄基苯基硫醚、四甲基一硫化秋蘭姆等硫醚化合物；1-羥基環己基苯基酮等α-酮醇化合物；偶氮雙異丁腈等偶氮化合物；二茂鐵等二 茂鐵化合物；噻噸酮等噻噸酮化合物；過氧化物化合物；二乙醯等二酮化合物；苯偶醯、二苯偶醯、二苯甲酮、2,4-二乙基噻噸酮、1,2-二苯基甲烷、2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮、2-氯蒽醌等。 Examples of the photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. Acetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. a ketone compound; a fluorenylphosphine oxide compound such as bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide or 2,4,6-trimethylbenzimidyldiphenylphosphine oxide; a thioether compound such as phenyl thioether or thiuram monosulfide; an α-keto alcohol compound such as 1-hydroxycyclohexyl phenyl ketone; an azo compound such as azobisisobutyronitrile; ferrocene; Ferrocene compound; thioxanthone compound such as thioxanthone; peroxide compound; diketone compound such as diethyl hydrazine; benzoin, diphenyl fluorene, benzophenone, 2,4-diethyl thioxanthone 1,2-diphenylmethane, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone, 2-chloroindole, and the like.

另外，作為前述光聚合起始劑，例如亦可使用：1-氯蒽醌等醌化合物；胺等光增感劑等。 In addition, as the photopolymerization initiator, for example, an anthracene compound such as 1-chloroindole or a photosensitizer such as an amine can be used.

第一黏著劑組成物(I-1)所含有之光聚合起始劑可僅為一種亦可為兩種以上。於第一黏著劑組成物(I-1)所含有之光聚合起始劑為兩種以上之情形時，該等的組合及比率可任意地選擇。 The photopolymerization initiator contained in the first adhesive composition (I-1) may be one type or two or more types. When the photopolymerization initiator contained in the first adhesive composition (I-1) is two or more kinds, the combinations and ratios can be arbitrarily selected.

於第一黏著劑組成物(I-1)中，相對於前述能量線固化性化合物的含量100質量份，光聚合起始劑的含量較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 In the first adhesive composition (I-1), the content of the photopolymerization initiator is preferably from 0.01 part by mass to 20 parts by mass, more preferably 0.03, based on 100 parts by mass of the content of the energy ray-curable compound. The mass fraction is preferably 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

(其他添加劑) (other additives)

第一黏著劑組成物(I-1)亦可於不損及本發明之功效的範圍內，含有亦不相當於上述任一成分之其他添加劑。 The first adhesive composition (I-1) may also contain other additives which are not equivalent to any of the above components, within a range not detracting from the effects of the present invention.

作為前述其他添加劑，例如可列舉：抗靜電劑、抗氧化劑、軟化劑(塑化劑)、填充劑(填料)、防銹劑、著色劑(顏料、染料)、增感劑、增黏劑、反應延遲劑及交聯促進劑(觸媒)等公知之添加劑。 Examples of the other additives include an antistatic agent, an antioxidant, a softener (plasticizer), a filler (filler), a rust preventive, a colorant (pigment, dye), a sensitizer, a tackifier, and the like. A known additive such as a reaction retarder and a crosslinking accelerator (catalyst).

再者，所謂反應延遲劑，例如係藉由混入至第一黏著劑組成物(I-1)中之觸媒的作用，而於保存中之第一黏著劑組成物(I-1)中抑制並非目標的交聯反應進行者。作為反應延遲劑，例如可列舉藉由針對觸媒之螯合物而形成螯合錯合物者，更具體可列舉一分子中具有兩個以上之羰基(-C(=O)-)者。 Further, the reaction retardant is inhibited in the first adhesive composition (I-1) during storage by, for example, the action of the catalyst mixed in the first adhesive composition (I-1). It is not the target of the cross-linking reaction. The reaction retardation agent may, for example, be a chelate complex formed by a chelate against a catalyst, and more specifically, a one having two or more carbonyl groups (-C(=O)-) in one molecule.

第一黏著劑組成物(I-1)所含有之其他添加劑可僅為一種亦可為兩種以上。於第一黏著劑組成物(I-1)所含有之其他添加劑為兩種以上之情形時，該等的組合及比率可任意地選擇。 The other additives contained in the first adhesive composition (I-1) may be one type or two or more types. When two or more other additives are contained in the first adhesive composition (I-1), the combinations and ratios can be arbitrarily selected.

第一黏著劑組成物(I-1)中，其他添加劑的含量並無特別限定，只要根據其種類而適切選擇即可。 In the first adhesive composition (I-1), the content of the other additives is not particularly limited, and may be appropriately selected depending on the type thereof.

(溶劑) (solvent)

第一黏著劑組成物(I-1)亦可含有溶劑。藉由第一黏著劑組成物(I-1)含有溶劑，對塗敷對象面之塗敷適性提高。 The first adhesive composition (I-1) may also contain a solvent. When the first adhesive composition (I-1) contains a solvent, the coating suitability to the surface to be coated is improved.

前述溶劑較佳為有機溶劑，作為前述有機溶劑，例如可列舉：甲基乙基酮、丙酮等酮；乙酸乙酯等酯(羧酸酯)；四氫呋喃、二噁烷(dioxane)等醚；環己烷、正己烷等脂肪族烴；甲苯、二甲苯等芳香族烴；1-丙醇、2-丙醇等醇等。 The solvent is preferably an organic solvent, and examples of the organic solvent include a ketone such as methyl ethyl ketone or acetone; an ester such as ethyl acetate (carboxylate); an ether such as tetrahydrofuran or dioxane; and a ring; An aliphatic hydrocarbon such as hexane or n-hexane; an aromatic hydrocarbon such as toluene or xylene; an alcohol such as 1-propanol or 2-propanol; or the like.

作為前述溶劑，例如可不將製造黏著性樹脂(I-1a)時所用者自黏著性樹脂(I-1a)中去除，而直接於第一黏著劑組成物(I-1)中使用，亦可於製造第一黏著劑組成物(I-1)時另行添加種類與製造黏著性樹脂(I-1a)時所用者相同或不同之溶劑。 The solvent can be used as the solvent (I-1a), and can be used in the first adhesive composition (I-1), for example, without using the adhesive resin (I-1a). When the first adhesive composition (I-1) is produced, a solvent which is the same as or different from that used in the production of the adhesive resin (I-1a) is separately added.

第一黏著劑組成物(I-1)所含有之溶劑可僅為一種亦可為兩種以上。於第一黏著劑組成物(I-1)所含有之溶劑為兩種以上之情形時，該等的組合及比率可任意地選擇。 The solvent contained in the first adhesive composition (I-1) may be one type or two or more types. When the solvent contained in the first adhesive composition (I-1) is two or more kinds, the combinations and ratios can be arbitrarily selected.

第一黏著劑組成物(I-1)中，溶劑的含量並無特別限定，只要適切調節即可。 In the first adhesive composition (I-1), the content of the solvent is not particularly limited, and may be appropriately adjusted.

{第一黏著劑組成物(I-2)} {First Adhesive Composition (I-2)}

如上所述，前述第一黏著劑組成物(I-2)含有於非能量線固化性的黏著性樹脂(I-1a)的側鏈導入有不飽和基之能量線固化性的黏著性樹脂(I-2a)。 As described above, the first adhesive composition (I-2) contains an energy ray-curable adhesive resin having an unsaturated group introduced into the side chain of the non-energy ray-curable adhesive resin (I-1a) ( I-2a).

(黏著性樹脂(I-2a)) (Adhesive resin (I-2a))

前述黏著性樹脂(I-2a)例如可藉由使具有能量線聚合性不飽和基之含不飽和基之化合物與黏著性樹脂(I-1a)中的官能基反應而獲得。 The above-mentioned adhesive resin (I-2a) can be obtained, for example, by reacting a compound containing an unsaturated group having an energy ray polymerizable unsaturated group with a functional group in the adhesive resin (I-1a).

前述含不飽和基之化合物為除了前述能量線聚合性不飽和基以外，進一步具有藉由與黏著性樹脂(I-1a)中的官能基反應而可與黏著性樹脂(I-1a)鍵結之基團的化合物。 The unsaturated group-containing compound is further bonded to the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a) in addition to the above-mentioned energy ray polymerizable unsaturated group. a compound of the group.

作為前述能量線聚合性不飽和基，例如可列舉(甲基)丙烯醯基、乙烯基(ethenyl)及烯丙基(2-丙烯基)等，較佳為(甲基)丙烯醯基。 Examples of the energy ray polymerizable unsaturated group include a (meth) acryl fluorenyl group, an ethenyl group, and an allyl group (2-propenyl group), and a (meth) acrylonitrile group is preferable.

作為可與黏著性樹脂(I-1a)中的官能基鍵結之基團，例如可列舉：可與羥基或胺基鍵結之異氰酸酯基及縮水甘油基、以及可與羧基或環氧基鍵結之羥基及胺基等。 Examples of the group bondable to the functional group in the adhesive resin (I-1a) include an isocyanate group and a glycidyl group which may be bonded to a hydroxyl group or an amine group, and a bond with a carboxyl group or an epoxy group. The hydroxyl group and the amine group of the knot.

作為前述含不飽和基之化合物，例如可列舉：(甲基)丙烯醯氧基乙基異氰酸酯、(甲基)丙烯醯基異氰酸酯及(甲基)丙烯酸縮水甘油酯等。 Examples of the unsaturated group-containing compound include (meth)acryloxyethyl isocyanate, (meth)acryl decyl isocyanate, and (meth)acrylic acid glycidyl ester.

第一黏著劑組成物(I-2)所含有之黏著性樹脂(I-2a)可僅為一種亦可為兩種以上。於第一黏著劑組成物(I-2)所含有之黏著性樹脂(I-2a)為兩種以上之情形時，該等的組合及比率可任意地選擇。 The adhesive resin (I-2a) contained in the first adhesive composition (I-2) may be one type or two or more types. When the adhesive resin (I-2a) contained in the first adhesive composition (I-2) is two or more kinds, the combinations and ratios can be arbitrarily selected.

第一黏著劑組成物(I-2)中，相對於第一黏著劑組成物(I-2)的總質量，黏著性樹脂(I-2a)的含量較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為10質量%至90質量%。 In the first adhesive composition (I-2), the content of the adhesive resin (I-2a) is preferably from 5% by mass to 99% by mass based on the total mass of the first adhesive composition (I-2). More preferably, it is 10 mass% to 95 mass%, and particularly preferably 10 mass% to 90 mass%.

(交聯劑) (crosslinking agent)

例如於使用與黏著性樹脂(I-1a)中者相同的具有源自含官能基之單體之結構單元的前述丙烯酸系聚合物作為黏著性樹脂(I-2a)之情形時，第一黏著劑組成物(I-2)亦可進一步含有交聯劑。 For example, when the same acrylic polymer having a structural unit derived from a functional group-containing monomer is used as the adhesive resin (I-2a) as in the adhesive resin (I-1a), the first adhesive is used. The agent composition (I-2) may further contain a crosslinking agent.

作為第一黏著劑組成物(I-2)中的前述交聯劑，可列舉與第一黏著劑組成物(I-1)中的交聯劑相同者。 The crosslinking agent in the first adhesive composition (I-2) may be the same as the crosslinking agent in the first adhesive composition (I-1).

第一黏著劑組成物(I-2)所含有之交聯劑可僅為一種亦可為兩種以上。於第一黏著劑組成物(I-2)所含有之交聯劑為兩種以上之情形時，該等的組合及比率可任意地選擇。 The crosslinking agent contained in the first adhesive composition (I-2) may be one type or two or more types. When the crosslinking agent contained in the first adhesive composition (I-2) is two or more kinds, the combinations and ratios can be arbitrarily selected.

第一黏著劑組成物(I-2)中，相對於黏著性樹脂(I-2a)的含量100質量份，交聯劑的含量較佳為0.01質量份至50質量份，更佳為0.1質量份至20質量份，尤佳為1質量份至10質量份。 In the first adhesive composition (I-2), the content of the crosslinking agent is preferably from 0.01 part by mass to 50 parts by mass, more preferably 0.1% by mass based on 100 parts by mass of the adhesive resin (I-2a). The portion is preferably 20 parts by mass, particularly preferably 1 part by mass to 10 parts by mass.

(光聚合起始劑) (photopolymerization initiator)

第一黏著劑組成物(I-2)亦可進一步含有光聚合起始劑。含有光聚合起始劑之第一黏著劑組成物(I-2)即便照射紫外線等能量相對較低的能量線，亦充分進行固化反應。 The first adhesive composition (I-2) may further contain a photopolymerization initiator. The first adhesive composition (I-2) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with an energy line having a relatively low energy such as ultraviolet rays.

作為第一黏著劑組成物(I-2)中的前述光聚合起始劑，可列舉與第一黏著劑組成物(I-1)中的光聚合起始劑相同者。 The photopolymerization initiator in the first adhesive composition (I-2) is the same as the photopolymerization initiator in the first adhesive composition (I-1).

第一黏著劑組成物(I-2)所含有之光聚合起始劑可僅為一種亦可為兩種以上。於第一黏著劑組成物(I-2)所含有之光聚合起始劑為兩種以上之情形時，該等的組合及比率可任意地選擇。 The photopolymerization initiator contained in the first adhesive composition (I-2) may be one type or two or more types. When the photopolymerization initiator contained in the first adhesive composition (I-2) is two or more kinds, the combinations and ratios can be arbitrarily selected.

第一黏著劑組成物(I-2)中，相對於黏著性樹脂(I-2a)的含量100質量份，光聚合起始劑的含量較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 In the first adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 parts by mass to 20 parts by mass, more preferably 100 parts by mass based on the content of the adhesive resin (I-2a). From 0.03 parts by mass to 10 parts by mass, particularly preferably from 0.05 parts by mass to 5 parts by mass.

(其他添加劑) (other additives)

第一黏著劑組成物(I-2)亦可於不損及本發明之功效的範圍內，含有亦不相當於上述任一成分之其他添加劑。 The first adhesive composition (I-2) may also contain other additives which are not equivalent to any of the above components, within a range not detracting from the effects of the present invention.

作為第一黏著劑組成物(I-2)中的前述其他添加劑，可列舉與第一黏著劑組成物(I-1)中的其他添加劑相同者。 The other additives mentioned in the first adhesive composition (I-2) are the same as those of the other additives in the first adhesive composition (I-1).

第一黏著劑組成物(I-2)所含有之其他添加劑可僅為一種亦可為兩種以上。於第一黏著劑組成物(I-2)所含有之其他添加劑為兩種以上之情形時，該等的組合及比率可任意地選擇。 The other additives contained in the first adhesive composition (I-2) may be one type or two or more types. When two or more other additives are contained in the first adhesive composition (I-2), the combinations and ratios can be arbitrarily selected.

第一黏著劑組成物(I-2)中，其他添加劑的含量並無特別限定，只要根據其種類而適切選擇即可。 In the first adhesive composition (I-2), the content of the other additives is not particularly limited, and may be appropriately selected depending on the type thereof.

(溶劑) (solvent)

第一黏著劑組成物(I-2)亦能以與第一黏著劑組成物(I-1)之情形相同之目的而含有溶劑。 The first adhesive composition (I-2) can also contain a solvent for the same purpose as in the case of the first adhesive composition (I-1).

作為第一黏著劑組成物(I-2)中的前述溶劑，可列舉與第一黏著劑組成物(I-1)中的溶劑相同者。 The solvent in the first adhesive composition (I-2) is the same as the solvent in the first adhesive composition (I-1).

第一黏著劑組成物(I-2)所含有之溶劑可僅為一種亦可為兩種以上，於為兩種以上之情形時，該等的組合及比率可任意地選擇。 The solvent contained in the first adhesive composition (I-2) may be one type or two or more types. When two or more types are used, the combinations and ratios may be arbitrarily selected.

第一黏著劑組成物(I-2)中，溶劑的含量並無特別限定，只要適切調節即可。 In the first adhesive composition (I-2), the content of the solvent is not particularly limited, and may be appropriately adjusted.

{第一黏著劑組成物(I-3)} {First Adhesive Composition (I-3)}

如上所述，第一黏著劑組成物(I-3)含有前述黏著性樹脂(I-2a)、及能量線固化性低分子化合物。 As described above, the first adhesive composition (I-3) contains the above-mentioned adhesive resin (I-2a) and an energy ray-curable low molecular compound.

第一黏著劑組成物(I-3)中，相對於第一黏著劑組成物(I-3)的總質量，黏著性樹脂(I-2a)的含量較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為15質量%至90質量%。 In the first adhesive composition (I-3), the content of the adhesive resin (I-2a) is preferably from 5% by mass to 99% by mass based on the total mass of the first adhesive composition (I-3). More preferably, it is 10 mass% to 95 mass%, and particularly preferably 15 mass% to 90 mass%.

(能量線固化性低分子化合物) (energy ray curable low molecular compound)

作為第一黏著劑組成物(I-3)所含有之前述能量線固化性低分子化合物，可列舉具有能量線聚合性不飽和基且可藉由能量線的照射而固化之單體及寡聚物，且可列舉與第一黏著劑組成物(I-1)所含有之能量線固化性化合物相同者。 The energy ray-curable low molecular compound contained in the first adhesive composition (I-3) includes monomers and oligomers which have an energy ray polymerizable unsaturated group and can be cured by irradiation with an energy ray. The same as the energy ray-curable compound contained in the first adhesive composition (I-1).

第一黏著劑組成物(I-3)所含有之前述能量線固化性低分子化合物可僅為一種亦可為兩種以上。於第一黏著劑組成物(I-3)所含有之前述能量線固化性低分子化合物為兩種以上之情形時，該等的組合及比率可任意地選擇。 The energy ray-curable low molecular compound contained in the first adhesive composition (I-3) may be one type or two or more types. When the energy ray-curable low molecular compound contained in the first adhesive composition (I-3) is two or more kinds, the combinations and ratios can be arbitrarily selected.

第一黏著劑組成物(I-3)中，相對於黏著性樹脂(I-2a)的含量100質量份，前述能量線固化性低分子化合物的含量較佳為0.01質量份至300質量份，更佳為0.03質量份至200質量份，尤佳為0.05質量份至100質量份。 In the first adhesive composition (I-3), the content of the energy ray-curable low molecular compound is preferably from 0.01 part by mass to 300 parts by mass based on 100 parts by mass of the content of the adhesive resin (I-2a). It is more preferably 0.03 parts by mass to 200 parts by mass, particularly preferably 0.05 parts by mass to 100 parts by mass.

(光聚合起始劑) (photopolymerization initiator)

第一黏著劑組成物(I-3)亦可進一步含有光聚合起始劑。含有光聚合起始劑之第一黏著劑組成物(I-3)即便照射紫外線等能量相對較低的能量線，亦充分進行固化反應。 The first adhesive composition (I-3) may further contain a photopolymerization initiator. The first adhesive composition (I-3) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when irradiated with an energy line having a relatively low energy such as ultraviolet rays.

作為第一黏著劑組成物(I-3)中的前述光聚合起始劑，可列舉與第一黏著劑組成物(I-1)中的光聚合起始劑相同者。 The photopolymerization initiator in the first adhesive composition (I-3) is the same as the photopolymerization initiator in the first adhesive composition (I-1).

第一黏著劑組成物(I-3)所含有之光聚合起始劑可僅為一種亦可為兩種以上。於第一黏著劑組成物(I-3)中的前述光聚合起始劑為兩種以上之情形時，該等的組合及比率可任意地選擇。 The photopolymerization initiator contained in the first adhesive composition (I-3) may be one type or two or more types. When the photopolymerization initiator in the first adhesive composition (I-3) is two or more kinds, the combinations and ratios can be arbitrarily selected.

第一黏著劑組成物(I-3)中，相對於黏著性樹脂(I-2a)及前述能量線固化性低分子化合物的總含量100質量份，光聚合起始劑的含量較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 In the first adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 with respect to 100 parts by mass of the total content of the adhesive resin (I-2a) and the energy ray-curable low molecular compound. The mass fraction is 20 parts by mass, more preferably 0.03 parts by mass to 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

(其他添加劑) (other additives)

第一黏著劑組成物(I-3)亦可於不損及本發明之功效的範圍內，含有亦不相當於上述任一成分之其他添加劑。 The first adhesive composition (I-3) may also contain other additives which are not equivalent to any of the above components, within a range not detracting from the effects of the present invention.

作為前述其他添加劑，可列舉與第一黏著劑組成物(I-1)中的其他添加劑相同者。 The other additives mentioned above are the same as the other additives in the first adhesive composition (I-1).

第一黏著劑組成物(I-3)所含有之其他添加劑可僅為一種亦可為兩種以上。於第一黏著劑組成物(I-3)所含有之其他添加劑為兩種以上之情形時，該等的組合及比率可任意地選擇。 The other additives contained in the first adhesive composition (I-3) may be one type or two or more types. When two or more other additives are contained in the first adhesive composition (I-3), the combinations and ratios can be arbitrarily selected.

第一黏著劑組成物(I-3)中，其他添加劑的含量並無特別限定，只要根據其種類而適切選擇即可。 In the first adhesive composition (I-3), the content of the other additives is not particularly limited, and may be appropriately selected depending on the type thereof.

(溶劑) (solvent)

第一黏著劑組成物(I-3)亦能以與第一黏著劑組成物(I-1)之情形相同之目的而含有溶劑。 The first adhesive composition (I-3) can also contain a solvent for the same purpose as in the case of the first adhesive composition (I-1).

作為第一黏著劑組成物(I-3)中的前述溶劑，可列舉與第一黏著劑組成物(I-1)中的溶劑相同者。 The solvent in the first adhesive composition (I-3) is the same as the solvent in the first adhesive composition (I-1).

第一黏著劑組成物(I-3)所含有之溶劑可僅為一種亦可為兩種以上。於第一黏著劑組成物(I-3)所含有之溶劑為兩種以上之情形時，該等的組合及比率可任意地選擇。 The solvent contained in the first adhesive composition (I-3) may be one type or two or more types. When the solvent contained in the first adhesive composition (I-3) is two or more kinds, the combinations and ratios can be arbitrarily selected.

第一黏著劑組成物(I-3)中，溶劑的含量並無特別限定，只要適切調節即可。 In the first adhesive composition (I-3), the content of the solvent is not particularly limited, and may be appropriately adjusted.

{第一黏著劑組成物(I-1)至第一黏著劑組成物(I-3)以外之第一黏著劑組成物} {First Adhesive Composition (I-1) to First Adhesive Composition Other than First Adhesive Composition (I-3)}

到此為止，主要對第一黏著劑組成物(I-1)、第一黏著劑組成物(I-2)及第一黏著劑組成物(I-3)進行了說明，但作為該等之含有成分而說明者於該等三種第一黏著劑組成物以外之所有第一黏著劑組成物(本實施形態中，稱為「第一黏著劑組成物(I-1)至第一黏著劑組成物(I-3)以外之第一黏著劑組成物」)中亦可同樣地使用。 Heretofore, the first adhesive composition (I-1), the first adhesive composition (I-2), and the first adhesive composition (I-3) have been mainly described, but as such All of the first adhesive compositions other than the three first adhesive compositions are included in the composition (in the present embodiment, the first adhesive composition (I-1) to the first adhesive composition The same can be used in the first adhesive composition other than the substance (I-3).

作為第一黏著劑組成物(I-1)至第一黏著劑組成物(I-3)以外之第一黏著劑組成物，除了能量線固化性的第一黏著劑組成物以外，亦可列舉非能量線固化性的第一黏著劑組成物。 The first adhesive composition other than the first adhesive composition (I-1) to the first adhesive composition (I-3) may be enumerated in addition to the energy ray-curable first adhesive composition. A non-energy line curable first adhesive composition.

作為非能量線固化性的第一黏著劑組成物，例如可列舉：含有丙烯酸系樹脂(具有(甲基)丙烯醯基之樹脂)、胺基甲酸酯系樹脂(具有胺基甲酸酯鍵之樹脂)、橡膠系樹脂(具有橡膠結構之樹脂)、矽酮系樹脂(具有矽氧烷鍵之樹脂)、環氧系樹脂(具有環氧基之樹脂)、聚乙烯醚或聚碳酸酯等黏著性樹脂者，較佳為含有丙烯酸系樹脂者。 Examples of the non-energy ray curable first adhesive composition include an acrylic resin (resin having a (meth) acrylonitrile group) and an urethane resin (having a urethane bond). Resin), rubber-based resin (resin having a rubber structure), anthrone-based resin (resin having a siloxane coupling), epoxy resin (a resin having an epoxy group), polyvinyl ether or polycarbonate The adhesive resin is preferably one containing an acrylic resin.

第一黏著劑組成物(I-1)至第一黏著劑組成物(I-3)以外之第一黏著劑組成物較佳為含有一種或兩種以上之交聯劑，其含量可設定為與上述第一黏著劑組成物(I-1)等情形相同。 The first adhesive composition other than the first adhesive composition (I-1) to the first adhesive composition (I-3) preferably contains one or two or more kinds of crosslinking agents, and the content thereof can be set to It is the same as the above-described first adhesive composition (I-1).

<第一黏著劑組成物的製造方法> <Method for Producing First Adhesive Composition>

第一黏著劑組成物(I-1)至第一黏著劑組成物(I-3)等前述第一黏著劑組成物可藉由將前述黏著劑、及視需要的前述黏著劑以外之成分等用以構成第一黏著劑組成物之各成分調配而獲得。 The first adhesive composition such as the first adhesive composition (I-1) to the first adhesive composition (I-3) may be composed of the above-mentioned adhesive, and optionally the above-mentioned adhesive. It is obtained by formulating the components constituting the first adhesive composition.

各成分的調配時之添加順序並無特別限定，亦可同時添加兩種以上之成分。 The order of addition of each component at the time of preparation is not particularly limited, and two or more components may be simultaneously added.

於使用溶劑之情形時，可藉由以下方式使用：將溶劑與溶劑以外的任一調配成分混合而將該調配成分預先稀釋；或者不將溶劑以外的任一調配成分預先稀釋，而將溶劑與該等調配成分混合。 When a solvent is used, it can be used by mixing a solvent with any compounding component other than the solvent to pre-dilute the compounding component, or by pre-diluting any of the formulating components other than the solvent, and These formulated ingredients are mixed.

於調配時混合各成分之方法並無特別限定，只要自如 下方法等公知之方法中適切選擇即可：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機進行混合之方法；施加超音波進行混合之方法。 There is no particular limitation on the method of mixing the ingredients during the preparation, as long as it is free A suitable method such as the following method may be selected as follows: a method of mixing by stirring a stirring bar or a stirring blade, a method of mixing using a mixer, and a method of applying ultrasonic waves for mixing.

關於各成分之添加以及混合時之溫度及時間，只要各調配成分不劣化則並無特別限定，只要適切調節即可，溫度較佳為15℃至30℃。 The temperature and time during the addition of each component and the mixing time are not particularly limited as long as the respective components do not deteriorate, and the temperature is preferably 15 ° C to 30 ° C as long as it is appropriately adjusted.

[第一中間層] [First intermediate layer]

前述第一中間層為片狀或膜狀，其構成材料只要根據目的而適切選擇即可，並無特別限定。 The first intermediate layer is in the form of a sheet or a film, and the constituent material is not particularly limited as long as it is appropriately selected according to the purpose.

例如於為了抑制存在於半導體表面之凸塊的形狀反映於覆蓋半導體表面之第一保護膜而導致第一保護膜變形的情況時，作為前述第一中間層的較佳構成材料，就進一步提高第一中間層的貼附性之方面而言，可列舉(甲基)丙烯酸胺基甲酸酯等。 For example, when the shape of the bump existing on the surface of the semiconductor is reflected on the first protective film covering the surface of the semiconductor to cause deformation of the first protective film, the preferred constituent material of the first intermediate layer is further improved. Examples of the adhesion of an intermediate layer include (meth)acrylic acid urethane and the like.

第一中間層可僅為一層(單層)，亦可為兩層以上之複數層。於第一中間層為複數層之情形時，該等複數層可彼此相同亦可不同，該等複數層的組合並無特別限定。 The first intermediate layer may be only one layer (single layer), or may be a plurality of layers of two or more layers. In the case where the first intermediate layer is a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.

第一中間層的厚度可根據成為保護對象之半導體表面的凸塊的高度而適切調節，就亦可容易地吸收高度相對較高之凸塊的影響之方面而言，較佳為50μm至600μm，更佳為70μm至500μm，尤佳為80μm至400μm。 The thickness of the first intermediate layer can be appropriately adjusted according to the height of the bump of the semiconductor surface to be protected, and it is also preferably 50 μm to 600 μm in terms of easily absorbing the influence of the bump having a relatively high height. More preferably, it is 70 μm to 500 μm, and particularly preferably 80 μm to 400 μm.

此處所謂「第一中間層的厚度」，係指第一中間層總體的厚度，例如所謂由複數層所構成之第一中間層的厚度，係指構成第一中間層之所有層的合計厚度。 Here, the "thickness of the first intermediate layer" means the thickness of the entire first intermediate layer, for example, the thickness of the first intermediate layer composed of a plurality of layers, and the total thickness of all the layers constituting the first intermediate layer. .

{{第一中間層形成用組成物}} {{First intermediate layer forming composition}}

第一中間層可使用含有其構成材料之第一中間層形成用組成物而形成。例如於第一中間層之形成對象面塗敷第一中間層形成用組成物，視需要進行乾燥，或藉由能量線之照射進行固化，由此可於目標部位形成第一中間層。關於第一中間層的更具體的形成方法，將連同其他層的形成方法一起於後文中詳細說明。關於第一中間層形成用組成物中的於常溫下不氣化之成分彼此的含量的比率，通常與第一中間層的前述成分彼此的含量的比率相同。此處所謂「常溫」如上文中所說明。 The first intermediate layer can be formed using a composition for forming a first intermediate layer containing a constituent material thereof. For example, the first intermediate layer forming composition is applied to the formation target surface of the first intermediate layer, dried as necessary, or cured by irradiation with an energy ray, whereby the first intermediate layer can be formed at the target portion. A more specific method of forming the first intermediate layer will be described in detail later together with the formation method of the other layers. The ratio of the content of the components which are not vaporized at normal temperature in the composition for forming the first intermediate layer is usually the same as the ratio of the content of the components of the first intermediate layer. The term "normal temperature" as used herein is as explained above.

第一中間層形成用組成物之塗敷只要利用公知之方法進行即可，例如可列舉：使用氣刀塗佈機、刮刀塗佈機、棒式塗佈機、凹版塗佈機、輥式塗佈機、輥刀塗佈機、簾幕式塗佈機、模式塗佈機、刀片塗佈機、網版塗佈機、線棒塗佈機及吻合式塗佈機等各種塗佈機之方法。 The application of the first intermediate layer forming composition may be carried out by a known method, and examples thereof include an air knife coater, a knife coater, a bar coater, a gravure coater, and a roll coat. Method of various coating machines such as cloth machine, roll coater, curtain coater, pattern coater, blade coater, screen coater, wire bar coater and staple coater .

第一中間層形成用組成物的乾燥條件並無特別限定，於第一中間層形成用組成物含有後述溶劑之情形時， 較佳為進行加熱乾燥，於該情形時，例如較佳為於70℃至130℃且10秒至5分鐘之條件下乾燥。 The drying condition of the first intermediate layer-forming composition is not particularly limited, and when the first intermediate layer-forming composition contains a solvent to be described later, It is preferred to carry out heat drying, and in this case, for example, it is preferably dried at 70 ° C to 130 ° C for 10 seconds to 5 minutes.

於第一中間層形成用組成物具有能量線固化性之情形時，較佳為於乾燥後，進一步藉由能量線之照射而進行固化。 When the composition for forming the first intermediate layer has energy ray curability, it is preferably cured by irradiation with an energy ray after drying.

作為第一中間層形成用組成物，例如可列舉含有(甲基)丙烯酸胺基甲酸酯之第一中間層形成用組成物(II-1)等。 The first intermediate layer-forming composition (II-1) or the like containing (meth)acrylic acid urethane is exemplified as the first intermediate layer-forming composition.

{第一中間層形成用組成物(II-1)} {First intermediate layer forming composition (II-1)}

如上所述，第一中間層形成用組成物(II-1)含有(甲基)丙烯酸胺基甲酸酯。 As described above, the first intermediate layer-forming composition (II-1) contains a (meth)acrylic acid urethane.

((甲基)丙烯酸胺基甲酸酯) ((meth)acrylic acid urethane)

(甲基)丙烯酸胺基甲酸酯為一分子中至少具有(甲基)丙烯醯基及胺基甲酸酯鍵之化合物，具有能量線聚合性。 The (meth)acrylic acid urethane is a compound having at least a (meth)acrylonyl group and a urethane bond in one molecule, and has energy ray polymerizability.

(甲基)丙烯酸胺基甲酸酯可為單官能者(一分子中僅具有一個(甲基)丙烯醯基者)，亦可為二官能以上者(一分子中具有兩個以上之(甲基)丙烯醯基者)、亦即多官能者，較佳為至少使用單官能者。 The (meth)acrylic acid urethane may be monofunctional (having only one (meth) acrylonitrile group in one molecule), or may be difunctional or more (more than two in one molecule) Any of those which are polyfunctional, preferably at least monofunctional.

作為第一中間層形成用組成物所含有之前述(甲基)丙烯酸胺基甲酸酯，例如可列舉：使多元醇化合物與多元 異氰酸酯化合物反應而獲得末端異氰酸酯胺基甲酸酯預聚物，進一步使具有羥基及(甲基)丙烯醯基之(甲基)丙烯酸系化合物與前述末端異氰酸酯胺基甲酸酯預聚物進行反應所得者。此處所謂「末端異氰酸酯胺基甲酸酯預聚物」，係指具有胺基甲酸酯鍵，並且於分子的末端部具有異氰酸酯基之預聚物。 The (meth)acrylic acid urethane contained in the first intermediate layer forming composition may, for example, be a polyol compound and a polyhydric compound. The isocyanate compound is reacted to obtain a terminal isocyanate urethane prepolymer, and a (meth)acrylic compound having a hydroxyl group and a (meth)acrylinyl group is further reacted with the terminal isocyanate urethane prepolymer. The winner. The term "terminal isocyanate urethane prepolymer" as used herein refers to a prepolymer having a urethane bond and having an isocyanate group at a terminal portion of the molecule.

第一中間層形成用組成物(II-1)所含有之(甲基)丙烯酸胺基甲酸酯可僅為一種亦可為兩種以上。於第一中間層形成用組成物(II-1)所含有之(甲基)丙烯酸胺基甲酸酯為兩種以上之情形時，該等的組合及比率可任意地選擇。 The (meth)acrylic acid urethane contained in the first intermediate layer-forming composition (II-1) may be one type or two or more types. When the (meth)acrylic acid urethane contained in the first intermediate layer forming composition (II-1) is two or more kinds, the combinations and ratios can be arbitrarily selected.

(A)多元醇化合物 (A) polyol compound

前述多元醇化合物只要為一分子中具有兩個以上之羥基之化合物，則並無特別限定。 The polyol compound is not particularly limited as long as it is a compound having two or more hydroxyl groups in one molecule.

前述多元醇化合物可單獨使用一種亦可並用兩種以上。於並用兩種以上作為前述多元醇化合物之情形時，該等的組合及比率可任意地選擇。 The above polyol compounds may be used alone or in combination of two or more. When two or more kinds of the above polyol compounds are used in combination, the combinations and ratios can be arbitrarily selected.

作為前述多元醇化合物，例如可列舉：伸烷基二醇、聚醚型多元醇、聚酯型多元醇、聚碳酸酯型多元醇等。 Examples of the polyol compound include an alkylene glycol, a polyether polyol, a polyester polyol, and a polycarbonate polyol.

前述多元醇化合物可為二官能之二醇、三官能之三醇、四官能以上之多元醇等的任一種，就獲取容易且通用性及反應性等優異之方面而言，較佳為二醇。 The polyol compound may be any of a difunctional diol, a trifunctional triol, and a tetrafunctional or higher polyhydric alcohol, and is preferably a diol in terms of availability, versatility, and reactivity. .

．聚醚型多元醇 . Polyether polyol

前述聚醚型多元醇並無特別限定，較佳為聚醚型二醇，作為前述聚醚型二醇，例如可列舉下述通式(1)所表示之化合物。 The polyether polyol is not particularly limited, and is preferably a polyether diol. Examples of the polyether diol include a compound represented by the following formula (1).

(其中，上述(1)式中，n為2以上之整數；R為二價烴基，複數個R可彼此相同亦可不同。) (In the above formula (1), n is an integer of 2 or more; R is a divalent hydrocarbon group, and a plurality of R may be the same or different from each other.)

上述(1)式中，n表示通式「-R-O-」所表示之基團的重複單元數，只要為2以上之整數則並無特別限定。其中，n較佳為10至250，更佳為25至205，尤佳為40至185。 In the above formula (1), n represents the number of repeating units of the group represented by the formula "-R-O-", and is not particularly limited as long as it is an integer of 2 or more. Wherein n is preferably from 10 to 250, more preferably from 25 to 205, still more preferably from 40 to 185.

上述(1)式中，R只要為二價烴基則並無特別限定，較佳為伸烷基，更佳為碳數1至6之伸烷基，進而佳為伸乙基、伸丙基或四亞甲基，尤佳為伸丙基或四亞甲基。 In the above formula (1), R is not particularly limited as long as it is a divalent hydrocarbon group, and is preferably an alkylene group, more preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an exoethyl group or a propyl group. Tetramethylene, especially preferably propyl or tetramethylene.

上述(1)式所表示之化合物較佳為聚乙二醇、聚丙二醇或聚四亞甲基二醇，更佳為聚丙二醇或聚四亞甲基二醇。 The compound represented by the above formula (1) is preferably polyethylene glycol, polypropylene glycol or polytetramethylene glycol, more preferably polypropylene glycol or polytetramethylene glycol.

藉由使前述聚醚型二醇與前述多元異氰酸酯化合物反應，可獲得具有下述通式(1a)所表示之醚鍵部者作為前述末端異氰酸酯胺基甲酸酯預聚物。而且，藉由使用此種前述末端異氰酸酯胺基甲酸酯預聚物，前述(甲基)丙烯酸胺基甲酸酯成為具有前述醚鍵部者、亦即具有由前述聚醚型二醇所衍生之結構單元者。 By reacting the above polyether diol with the above polyvalent isocyanate compound, an ether bond having the ether bond represented by the following formula (1a) can be obtained as the terminal isocyanate urethane prepolymer. Further, by using such a terminal isocyanate urethane prepolymer, the (meth)acrylic acid urethane is a member having the above ether bond, that is, having a polyether diol derived therefrom. The structural unit.

(其中，上述(1a)式中，R及n與前述相同。) (In the above formula (1a), R and n are the same as described above.)

．聚酯型多元醇 . Polyester polyol

前述聚酯型多元醇並無特別限定，例如可列舉藉由使用多元酸或其衍生物進行酯化反應而獲得者。再者，本實施形態中所謂「衍生物」，只要無特別說明，則係指原本的化合物的一個以上之基團經除此以外之基團(取代基)取代而成者。此處所謂「基團」，不僅為複數個原子鍵結而成的原子團，亦包含一個原子。 The polyester polyol is not particularly limited, and examples thereof include those obtained by subjecting an esterification reaction using a polybasic acid or a derivative thereof. In addition, the "derivative" in this embodiment means that one or more groups of the original compound are substituted with a group other than the other group (substituent) unless otherwise specified. Here, the "group" is not only an atomic group in which a plurality of atoms are bonded, but also an atom.

作為前述多元酸及其衍生物，可列舉通常被用作聚酯的製造原料之多元酸及其衍生物。 Examples of the polybasic acid and the derivative thereof include polybasic acids and derivatives thereof which are generally used as a raw material for the production of polyester.

作為前述多元酸，例如可列舉飽和脂肪族多元酸、不飽和脂肪族多元酸、芳香族多元酸等，亦可使用相當於該等之任一者的二聚酸。 Examples of the polybasic acid include a saturated aliphatic polybasic acid, an unsaturated aliphatic polybasic acid, and an aromatic polybasic acid, and a dimer acid corresponding to any of these may be used.

作為前述飽和脂肪族多元酸，例如可列舉：草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸及癸二酸等飽和脂肪族二元酸等。 Examples of the saturated aliphatic polybasic acid include saturated aliphatic binary compounds such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, and sebacic acid. Acid, etc.

作為前述不飽和脂肪族多元酸，例如可列舉：馬來酸、富馬酸等不飽和脂肪族二元酸等。 Examples of the unsaturated aliphatic polybasic acid include unsaturated aliphatic dibasic acids such as maleic acid and fumaric acid.

作為前述芳香族多元酸，例如可列舉：鄰苯二甲酸、間苯二甲酸、對苯二甲酸、2,6-萘二甲酸等芳香族二元酸；偏苯三甲酸等芳香族三元酸；均苯四甲酸等芳香族四元酸等。 Examples of the aromatic polybasic acid include aromatic dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, and 2,6-naphthalene dicarboxylic acid; and aromatic tribasic acids such as trimellitic acid. An aromatic tetrabasic acid such as pyromellitic acid.

作為前述多元酸的衍生物，例如可列舉：上述飽和脂肪族多元酸、不飽和脂肪族多元酸及芳香族多元酸的酸酐、以及氫化二聚酸等。 Examples of the derivative of the polybasic acid include an acid anhydride of the above saturated aliphatic polybasic acid, an unsaturated aliphatic polybasic acid, and an aromatic polybasic acid, and a hydrogenated dimer acid.

前述多元酸或其衍生物均可單獨使用一種亦可並用兩種以上。於並用兩種以上作為前述多元酸或其衍生物之情形時，該等的組合及比率可任意地選擇。 The polybasic acid or a derivative thereof may be used alone or in combination of two or more. When two or more kinds are used in combination as the polybasic acid or a derivative thereof, the combinations and ratios can be arbitrarily selected.

就適於形成具有適度之硬度的塗膜之方面而言，前述多元酸較佳為芳香族多元酸。 The polybasic acid is preferably an aromatic polybasic acid in terms of being suitable for forming a coating film having a moderate hardness.

於用以獲得聚酯型多元醇之酯化反應中，視需要亦可使用公知之觸媒。 In the esterification reaction for obtaining a polyester polyol, a known catalyst can also be used as needed.

作為前述觸媒，例如可列舉：氧化二丁基錫、辛酸亞錫等錫化合物；鈦酸四丁酯、鈦酸四丙酯等烷氧基鈦等。 Examples of the catalyst include tin compounds such as dibutyltin oxide and stannous ocyanate; titanium alkoxides such as tetrabutyl titanate and tetrapropyl titanate; and the like.

．聚碳酸酯型多元醇 . Polycarbonate polyol

聚碳酸酯型多元醇並無特別限定，例如可列舉：使和上述(1)式所表示之化合物相同的二醇與碳酸伸烷基酯反應而獲得者等。 The polycarbonate-type polyol is not particularly limited, and examples thereof include those obtained by reacting a diol which is the same as the compound represented by the above formula (1) with an alkylene carbonate.

此處，二醇及碳酸伸烷基酯均可單獨使用一種亦可並用兩種以上。於並用兩種以上作為二醇及碳酸伸烷基酯之情形時，該等的組合及比率可任意地選擇。 Here, the diol and the alkyl carbonate may be used alone or in combination of two or more. When two or more kinds of diols and alkylene carbonates are used in combination, the combinations and ratios can be arbitrarily selected.

前述多元醇化合物的根據羥基值所算出之數量平均分子量較佳為1000至10000，更佳為2000至9000，尤佳為3000至7000。藉由前述數量平均分子量為1000以上，胺基甲酸酯鍵的過度生成得到抑制，第一中間層的黏彈性特性之控制變得更容易。另外，藉由前述數量平均分子量為10000以下，第一中間層的過度軟化得到抑制。 The number average molecular weight of the polyol compound calculated based on the hydroxyl value is preferably from 1,000 to 10,000, more preferably from 2,000 to 9000, still more preferably from 3,000 to 7,000. When the number average molecular weight is 1000 or more, excessive formation of a urethane bond is suppressed, and control of the viscoelastic property of the first intermediate layer becomes easier. Further, by the aforementioned number average molecular weight being 10,000 or less, excessive softening of the first intermediate layer is suppressed.

所謂多元醇化合物的根據羥基值所算出之前述數量平均分子量，係由下述式所算出之值。 The number average molecular weight calculated from the hydroxyl value of the polyol compound is a value calculated by the following formula.

[多元醇化合物的數量平均分子量]=[多元醇化合物的官能基數]×56.11×1000/[多元醇化合物的羥基值(單位：mgKOH/g)] [A number average molecular weight of the polyol compound] = [number of functional groups of the polyol compound] × 56.11 × 1000 / [hydroxy group value of the polyol compound (unit: mgKOH / g)]

前述多元醇化合物較佳為聚醚型多元醇，更佳為聚醚型二醇。 The above polyol compound is preferably a polyether polyol, more preferably a polyether diol.

(B)多元異氰酸酯化合物 (B) Polyisocyanate compound

與多元醇化合物反應的前述多元異氰酸酯化合物只要具有兩個以上之異氰酸酯基，則並無特別限定。 The polyvalent isocyanate compound to be reacted with the polyol compound is not particularly limited as long as it has two or more isocyanate groups.

多元異氰酸酯化合物可單獨使用一種亦可並用兩種以上。於並用兩種以上作為多元異氰酸酯化合物之情形時，該等的組合及比率可任意地選擇。 The polyisocyanate compound may be used alone or in combination of two or more. When two or more kinds of polyisocyanate compounds are used in combination, the combinations and ratios can be arbitrarily selected.

作為前述多元異氰酸酯化合物，例如可列舉：四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯等鏈狀脂肪族二異氰酸酯；異佛爾酮二異氰酸酯、降莰烷二異氰酸酯、二環己基甲烷-4,4'-二異氰酸酯、二環己基甲烷-2,4'-二異氰酸酯、ω,ω'-二異氰酸酯二甲基環己烷等環狀脂肪族二異氰酸酯；4,4'-二苯基甲烷二異氰酸酯、甲苯二異氰酸酯、二甲苯二異氰酸酯、聯甲苯胺二異氰酸酯、四亞甲基二甲苯二異氰酸酯、萘-1,5-二異氰酸酯等芳香族二異氰酸酯等。 Examples of the polyvalent isocyanate compound include chain aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; isophorone diisocyanate and hail Cyclic aliphatic diisocyanate such as alkane diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, ω,ω'-diisocyanate dimethylcyclohexane 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, tolidine diisocyanate, tetramethylene xylene diisocyanate, naphthalene-1,5-diisocyanate and other aromatic diisocyanates Wait.

該等之中，就處理性之方面而言，多元異氰酸酯化合物較佳為異佛爾酮二異氰酸酯、六亞甲基二異氰酸酯或二甲苯二異氰酸酯。 Among these, the polyisocyanate compound is preferably isophorone diisocyanate, hexamethylene diisocyanate or xylene diisocyanate in terms of handleability.

(C)(甲基)丙烯酸系化合物 (C) (meth)acrylic compound

與前述末端異氰酸酯胺基甲酸酯預聚物反應之前述(甲基)丙烯酸系化合物只要為一分子中至少具有羥基及(甲基)丙烯醯基之化合物，則並無特別限定。 The (meth)acrylic compound which is reacted with the terminal isocyanate urethane prepolymer is not particularly limited as long as it has at least a hydroxyl group and a (meth)acrylinyl group in one molecule.

前述(甲基)丙烯酸系化合物可單獨使用一種亦可並用兩種以上。於並用兩種以上作為前述(甲基)丙烯酸系化合物之情形時，該等的組合及比率可任意地選擇。 The (meth)acrylic compound may be used alone or in combination of two or more. When two or more kinds of the (meth)acrylic compound are used in combination, the combinations and ratios can be arbitrarily selected.

作為前述(甲基)丙烯酸系化合物，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸4-羥基環己酯、(甲基)丙烯酸5-羥基環辛酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、季戊四醇三(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯等含羥基之(甲基)丙烯酸酯；N-羥甲基(甲基)丙烯醯胺等含羥基之(甲基)丙烯醯胺；使(甲基)丙烯酸與乙烯醇、乙烯基苯酚或雙酚A二縮水甘油醚反應而獲得之反應物等。 Examples of the (meth)acrylic compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (methyl). ) 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 5-hydroxy (meth) acrylate Cyclooctyl ester, 2-hydroxy-3-phenoxypropyl (meth) acrylate, pentaerythritol tri(meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate a hydroxyl group-containing (meth) acrylate such as an ester; a hydroxyl group-containing (meth) acrylamide such as N-methylol (meth) acrylamide; or a (meth)acrylic acid with vinyl alcohol or vinyl phenol or The reactant obtained by the reaction of bisphenol A diglycidyl ether and the like.

該等之中，前述(甲基)丙烯酸系化合物較佳為含羥基之(甲基)丙烯酸酯，更佳為含羥基之(甲基)丙烯酸烷基酯，尤佳為(甲基)丙烯酸2-羥基乙酯。 Among these, the (meth)acrylic compound is preferably a hydroxyl group-containing (meth)acrylate, more preferably a hydroxyl group-containing (meth)acrylic acid alkyl ester, and particularly preferably (meth)acrylic acid 2 - hydroxyethyl ester.

前述末端異氰酸酯胺基甲酸酯預聚物與前述(甲基)丙烯酸系化合物之反應視需要可使用溶劑、觸媒等而進行。 The reaction of the terminal isocyanate urethane prepolymer and the (meth)acrylic compound can be carried out by using a solvent, a catalyst or the like as necessary.

使前述末端異氰酸酯胺基甲酸酯預聚物與前述(甲基)丙烯酸系化合物反應時之條件只要適切調節即可，例如反應溫度較佳為60℃至100℃，反應時間較佳為1小時至4小時。 The conditions for reacting the terminal isocyanate urethane prepolymer with the (meth)acrylic compound may be appropriately adjusted, for example, the reaction temperature is preferably from 60 ° C to 100 ° C, and the reaction time is preferably one hour. Up to 4 hours.

前述(甲基)丙烯酸胺基甲酸酯可為寡聚物、聚合物、以及寡聚物及聚合物之混合物的任一種，較佳為寡聚物。 The aforementioned (meth)acrylic acid urethane may be any of an oligomer, a polymer, and a mixture of an oligomer and a polymer, and is preferably an oligomer.

例如，前述(甲基)丙烯酸胺基甲酸酯的重量平均分子量較佳為1000至100000，更佳為3000至80000，尤佳為5000至65000。藉由前述重量平均分子量為1000以上，於(甲基)丙烯酸胺基甲酸酯與後述聚合性單體之聚合物中，由於源自(甲基)丙烯酸胺基甲酸酯之結構彼此的分子力，而容易實現第一中間層的硬度之最適化。 For example, the weight average molecular weight of the aforementioned (meth)acrylic acid urethane is preferably from 1,000 to 100,000, more preferably from 3,000 to 80,000, still more preferably from 5,000 to 65,000. By the weight average molecular weight of 1,000 or more, in the polymer of the (meth)acrylic acid urethane and the polymerizable monomer described later, the molecules derived from the structure of the (meth)acrylic acid urethane are Force, and it is easy to optimize the hardness of the first intermediate layer.

再者，本實施形態中，所謂重量平均分子量只要無特別說明，則為藉由凝膠滲透層析(GPC；Gel Permeation Chromatography)法所測定之聚苯乙烯換算值。 In the present embodiment, the weight average molecular weight is a polystyrene equivalent value measured by a gel permeation chromatography (GPC) method unless otherwise specified.

(聚合性單體) (polymerizable monomer)

就使製膜性進一步提高之方面而言，第一中間層形成用組成物(II-1)亦可除了前述(甲基)丙烯酸胺基甲酸酯以外，含有聚合性單體。 In the aspect of further improving the film-forming property, the first intermediate layer-forming composition (II-1) may contain a polymerizable monomer in addition to the (meth)acrylic acid urethane.

前述聚合性單體較佳為將具有能量線聚合性且重量平均分子量為1000以上之寡聚物及聚合物除外，且為一分子中具有至少一個(甲基)丙烯醯基之化合物。 The polymerizable monomer is preferably a compound having at least one (meth) acrylonitrile group in one molecule, except for an oligomer and a polymer having energy ray polymerizability and a weight average molecular weight of 1,000 or more.

作為前述聚合性單體，例如可列舉：構成烷基酯之烷基係碳數為1至30且鏈狀者之(甲基)丙烯酸烷基酯；具有羥基、醯胺基、胺基或環氧基等官能基之含官能基之(甲基)丙烯酸系化合物；具有脂肪族環式基之(甲基)丙烯酸酯；具有芳香族烴基之(甲基)丙烯酸酯；具有雜環式基之(甲基)丙烯酸酯；具有乙烯基之化合物；具有烯丙基之化合物等。 The polymerizable monomer may, for example, be an alkyl (meth)acrylate having an alkyl group having 1 to 30 carbon atoms and having a chain shape; and having a hydroxyl group, a mercaptoamine group, an amine group or a ring. (meth)acrylic compound containing a functional group such as an oxy group; (meth) acrylate having an aliphatic cyclic group; (meth) acrylate having an aromatic hydrocarbon group; having a heterocyclic group (Meth) acrylate; a compound having a vinyl group; a compound having an allyl group; and the like.

作為具有碳數為1至30之鏈狀烷基之前述(甲基)丙烯酸烷基酯，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯((甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯((甲基)丙烯酸肉豆蔻酯)、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯((甲基)丙烯酸棕 櫚酯)、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯(亦稱為(甲基)丙烯酸硬脂酯)、(甲基)丙烯酸異十八烷基酯((甲基)丙烯酸異硬脂酯)、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯等。 Examples of the alkyl (meth)acrylate having a chain alkyl group having 1 to 30 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid. Propyl ester, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, Amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl hexyl ester, n-decyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate Ester (lauryl (meth)acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), (meth)acrylic acid fifteen Alkyl ester, cetyl (meth) acrylate ((meth) acrylate brown Palmate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (also known as stearyl (meth)acrylate), isostearyl (meth)acrylate (isostearyl (meth)acrylate), nonadecyl (meth)acrylate, eicosyl (meth)acrylate, and the like.

作為前述含官能基之(甲基)丙烯酸衍生物，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等含羥基之(甲基)丙烯酸酯；(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥甲基丙烷(甲基)丙烯醯胺、N-甲氧基甲基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺等(甲基)丙烯醯胺及其衍生物；具有胺基之(甲基)丙烯酸酯(以下有時稱為「含胺基之(甲基)丙烯酸酯」)；具有胺基的一個氫原子經氫原子以外之基團取代而成的單取代胺基之(甲基)丙烯酸酯(以下有時稱為「含單取代胺基之(甲基)丙烯酸酯」)；具有胺基的兩個氫原子經氫原子以外之基團取代而成的二取代胺基之(甲基)丙烯酸酯(以下有時稱為「含二取代胺基之(甲基)丙烯酸酯」)；(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸甲基縮水甘油酯等具有環氧基之(甲基)丙烯酸酯(以下有時稱為「含環氧基之(甲基)丙烯酸酯」)等。 Examples of the functional group-containing (meth)acrylic acid derivative include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. a hydroxyl group-containing (meth) acrylate such as 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate; (meth) acrylonitrile Amine, N,N-dimethyl(meth)acrylamide, N-butyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-methylolpropane (A) (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, etc. (meth) acrylamide and its derivatives; a (meth) acrylate (hereinafter sometimes referred to as "amino group-containing (meth) acrylate"); a monosubstituted amino group having a hydrogen atom of an amine group substituted with a group other than a hydrogen atom (meth) acrylate (hereinafter sometimes referred to as "monosubstituted amino group-containing (meth) acrylate"); disubstituted with two hydrogen atoms having an amine group substituted with a group other than a hydrogen atom Amino (meth) acrylate (hereinafter sometimes referred to as "(di)amino group-containing (meth) acrylate"); (meth) acrylate (meth) acrylate (meth) acrylate (meth) acrylate (meth) acrylate (meth) acrylate (meth) acrylate (meth) acrylate (meth) acrylate (meth) acrylate (meth) acrylate It is called "epoxy group-containing (meth) acrylate").

此處，所謂「含胺基之(甲基)丙烯酸酯」，係指(甲基)丙烯酸酯的一個或兩個以上之氫原子經胺基(-NH2)取代而成的化合物。同樣地，所謂「含單取代胺基之(甲基)丙烯酸酯」，係指(甲基)丙烯酸酯的一個或兩個以上之氫原子經單取代胺基取代而成的化合物，所謂「含二取代胺基之(甲基)丙烯酸酯」，係指(甲基)丙烯酸酯的一個或兩個以上之氫原子經二取代胺基取代而成的化合物。 Here, the "amino group-containing (meth) acrylate" means a compound in which one or two or more hydrogen atoms of a (meth) acrylate are substituted with an amine group (-NH 2 ). Similarly, the term "monosubstituted amino group-containing (meth) acrylate" refers to a compound in which one or two or more hydrogen atoms of a (meth) acrylate are substituted with a monosubstituted amino group, so-called "including The disubstituted amino group (meth) acrylate refers to a compound in which one or two or more hydrogen atoms of a (meth) acrylate are substituted with a disubstituted amino group.

作為「單取代胺基」及「二取代胺基」中的取代氫原子的氫原子以外之基團(亦即取代基)，例如可列舉烷基等。 Examples of the group other than the hydrogen atom of the substituted hydrogen atom in the "monosubstituted amine group" and the "disubstituted amine group" (that is, the substituent) include an alkyl group and the like.

作為前述具有脂肪族環式基之(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸環己酯及(甲基)丙烯酸金剛烷基酯等。 Examples of the (meth) acrylate having an aliphatic cyclic group include isodecyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. Dicyclopentenyloxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, adamantyl (meth)acrylate, and the like.

作為前述具有芳香族烴基之(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸苯基羥基丙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯等。 Examples of the (meth) acrylate having an aromatic hydrocarbon group include phenylhydroxypropyl (meth)acrylate, benzyl (meth)acrylate, and 2-hydroxy-3-phenoxy (meth)acrylate. Propyl ester and the like.

前述具有雜環式基之(甲基)丙烯酸酯中的雜環式基可為芳香族雜環式基及脂肪族雜環式基的任一種。 The heterocyclic group in the (meth) acrylate having a heterocyclic group may be any of an aromatic heterocyclic group and an aliphatic heterocyclic group.

作為前述具有雜環式基之(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸四氫糠酯、(甲基)丙烯醯基嗎啉等。 Examples of the (meth) acrylate having a heterocyclic group include tetrahydrofurfuryl (meth) acrylate and (meth) acryl hydrazino morpholine.

作為前述具有乙烯基之化合物，例如可列舉：苯乙烯、羥基乙基乙烯醚、羥基丁基乙烯醚、N-乙烯基甲醯胺、N-乙烯基吡咯啶酮、N-乙烯基己內醯胺等。 Examples of the compound having a vinyl group include styrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-vinylformamide, N-vinylpyrrolidone, and N-vinyl caprolactone. Amines, etc.

作為前述具有烯丙基之化合物，例如可列舉烯丙基縮水甘油醚等。 Examples of the compound having an allyl group include allyl glycidyl ether and the like.

就與前述(甲基)丙烯酸胺基甲酸酯之相容性良好之方面而言，前述聚合性單體較佳為具有體積相對較大之基團，作為此種聚合性單體，可列舉：具有脂肪族環式基之(甲基)丙烯酸酯、具有芳香族烴基之(甲基)丙烯酸酯、具有雜環式基之(甲基)丙烯酸酯，更佳為具有脂肪族環式基之(甲基)丙烯酸酯。 The polymerizable monomer is preferably a group having a relatively large volume in terms of compatibility with the (meth)acrylic acid urethane, and examples of such a polymerizable monomer include : (meth) acrylate having an aliphatic cyclic group, (meth) acrylate having an aromatic hydrocarbon group, (meth) acrylate having a heterocyclic group, and more preferably having an aliphatic cyclic group (Meth) acrylate.

第一中間層形成用組成物(II-1)所含有之聚合性單體可僅為一種亦可為兩種以上。於第一中間層形成用組成物(II-1)所含有之聚合性單體為兩種以上之情形時，該等的組合及比率可任意地選擇。 The polymerizable monomer contained in the first intermediate layer-forming composition (II-1) may be one type or two or more types. When the polymerizable monomer contained in the first intermediate layer-forming composition (II-1) is two or more kinds, the combinations and ratios can be arbitrarily selected.

第一中間層形成用組成物(II-1)中，相對於第一中間層形成用組成物(II-1)的總質量，聚合性單體的含量較佳為10質量%至99質量%，更佳為15質量%至95質量%， 進而佳為20質量%至90質量%，尤佳為25質量%至80質量%。 In the first intermediate layer-forming composition (II-1), the content of the polymerizable monomer is preferably from 10% by mass to 99% by mass based on the total mass of the first intermediate layer-forming composition (II-1). More preferably, it is 15% by mass to 95% by mass. Further, it is preferably from 20% by mass to 90% by mass, particularly preferably from 25% by mass to 80% by mass.

(光聚合起始劑) (photopolymerization initiator)

第一中間層形成用組成物(II-1)亦可除了前述(甲基)丙烯酸胺基甲酸酯及聚合性單體以外，含有光聚合起始劑。含有光聚合起始劑之第一中間層形成用組成物(II-1)即便照射紫外線等能量相對較低的能量線，亦充分進行固化反應。 The first intermediate layer-forming composition (II-1) may contain a photopolymerization initiator in addition to the (meth)acrylic acid urethane and the polymerizable monomer. The first intermediate layer-forming composition (II-1) containing a photopolymerization initiator sufficiently undergoes a curing reaction even when an energy line having a relatively low energy such as ultraviolet rays is irradiated.

作為第一中間層形成用組成物(II-1)中的光聚合起始劑，可列舉與第一黏著劑組成物(I-1)中的光聚合起始劑相同者。 The photopolymerization initiator in the first intermediate layer-forming composition (II-1) is the same as the photopolymerization initiator in the first adhesive composition (I-1).

第一中間層形成用組成物(II-1)所含有之光聚合起始劑可僅為一種亦可為兩種以上。於第一中間層形成用組成物(II-1)所含有之光聚合起始劑為兩種以上之情形時，該等的組合及比率可任意地選擇。 The photopolymerization initiator contained in the first intermediate layer-forming composition (II-1) may be one type or two or more types. When the photopolymerization initiator contained in the first intermediate layer-forming composition (II-1) is two or more kinds, the combinations and ratios can be arbitrarily selected.

第一中間層形成用組成物(II-1)中，相對於前述(甲基)丙烯酸胺基甲酸酯及聚合性單體的總含量100質量份，光聚合起始劑的含量較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 In the first intermediate layer-forming composition (II-1), the content of the photopolymerization initiator is preferably 100 parts by mass based on the total content of the (meth)acrylic acid urethane and the polymerizable monomer. From 0.01 part by mass to 20 parts by mass, more preferably from 0.03 part by mass to 10 parts by mass, even more preferably from 0.05 part by mass to 5 parts by mass.

((甲基)丙烯酸胺基甲酸酯以外之樹脂成分) (Resin component other than (meth)acrylic acid urethane)

第一中間層形成用組成物(II-1)亦可於不損及本發明之功效的範圍內，含有前述(甲基)丙烯酸胺基甲酸酯以外之樹脂成分。 The first intermediate layer-forming composition (II-1) may contain a resin component other than the above-mentioned (meth)acrylic acid urethane, within a range not impairing the effects of the present invention.

前述樹脂成分之種類、及其於第一中間層形成用組成物(II-1)中的含量只要根據目的而適切選擇即可，並無特別限定。 The type of the resin component and the content in the first intermediate layer-forming composition (II-1) are not particularly limited as long as they are appropriately selected depending on the purpose.

(其他添加劑) (other additives)

第一中間層形成用組成物(II-1)亦可於不損及本發明之功效的範圍內，含有不相當於上述任一成分之其他添加劑。 The first intermediate layer-forming composition (II-1) may contain other additives which are not equivalent to any of the above components, within a range not impairing the effects of the present invention.

作為前述其他添加劑，例如可列舉：交聯劑、抗靜電劑、抗氧化劑、鏈轉移劑、軟化劑(塑化劑)、填充劑、防銹劑及著色劑(顏料、染料)等公知之添加劑。 Examples of the other additives include known additives such as a crosslinking agent, an antistatic agent, an antioxidant, a chain transfer agent, a softener (plasticizer), a filler, a rust preventive, and a color former (pigment, dye). .

例如作為前述鏈轉移劑，可列舉一分子中具有至少一個硫醇基(巰基)之硫醇化合物。 For example, as the chain transfer agent, a thiol compound having at least one thiol group (fluorenyl group) in one molecule can be cited.

作為前述硫醇化合物，例如可列舉：壬基硫醇、1-十二烷硫醇、1,2-乙二硫醇、1,3-丙二硫醇、三嗪硫醇、三嗪二硫醇、三嗪三硫醇、1,2,3-丙三硫醇、四乙二醇-雙(3-巰基丙酸酯)、三羥甲基丙烷三(3-巰基丙酸酯)、季戊四醇四(3-巰基丙酸酯)、季戊四醇四巰基乙酸酯、二季 戊四醇六(3-巰基丙酸酯)、三[(3-巰基丙醯氧基)-乙基]-異三聚氰酸酯、1,4-雙(3-巰基丁醯氧基)丁烷、季戊四醇四(3-巰基丁酸酯)、1,3,5-三(3-巰基丁氧基乙基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮等。 Examples of the thiol compound include mercapto mercaptan, 1-dodecanethiol, 1,2-ethanedithiol, 1,3-propanedithiol, triazinethiol, and triazine disulfide. Alcohol, triazine trithiol, 1,2,3-propanetrithiol, tetraethylene glycol-bis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol Tetrakis(3-mercaptopropionate), pentaerythritol tetradecyl acetate, second season Pentaerythritol hexa(3-mercaptopropionate), tris[(3-mercaptopropoxy)-ethyl]-isocyanate, 1,4-bis(3-mercaptobutyloxy) Butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-trione and the like.

第一中間層形成用組成物(II-1)所含有之其他添加劑可僅為一種亦可為兩種以上。於第一中間層形成用組成物(II-1)所含有之其他添加劑為兩種以上之情形時，該等的組合及比率可任意地選擇。 The other additives contained in the first intermediate layer-forming composition (II-1) may be one type or two or more types. When two or more other additives are contained in the first intermediate layer-forming composition (II-1), the combinations and ratios can be arbitrarily selected.

第一中間層形成用組成物(II-1)中，其他添加劑的含量並無特別限定，只要根據其種類而適切選擇即可。 In the first intermediate layer-forming composition (II-1), the content of the other additives is not particularly limited, and may be appropriately selected depending on the type thereof.

(溶劑) (solvent)

第一中間層形成用組成物(II-1)亦可含有溶劑。第一中間層形成用組成物(II-1)藉由含有溶劑，對塗敷對象面之塗敷適性提高。 The first intermediate layer-forming composition (II-1) may further contain a solvent. The composition (II-1) for forming the first intermediate layer improves the coating suitability to the surface to be coated by containing a solvent.

{{第一中間層形成用組成物的製造方法}} {{Manufacturing method of the composition for forming the first intermediate layer}}

第一中間層形成用組成物(II-1)等第一中間層形成用組成物係藉由將用以構成該組成物之各成分調配而獲得。 The first intermediate layer forming composition such as the first intermediate layer forming composition (II-1) is obtained by blending the respective components constituting the composition.

各成分之調配時的添加順序並無特別限定，亦可同時添加兩種以上之成分。 The order of addition of the components is not particularly limited, and two or more components may be added at the same time.

於使用溶劑之情形時，可藉由以下方式使用：將溶劑與溶劑以外之任一調配成分混合而將該調配成分預先稀釋；或不將溶劑以外之任一調配成分預先稀釋，而將溶劑與該等調配成分混合。 When a solvent is used, it can be used by mixing a solvent with any of the components other than the solvent to pre-dilute the formulation; or not pre-diluting any of the components other than the solvent, and These formulated ingredients are mixed.

於調配時混合各成分之方法並無特別限定，只要自如下方法等公知之方法中適切選擇即可：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機進行混合之方法；施加超音波進行混合之方法。 The method of mixing the components at the time of blending is not particularly limited, and may be appropriately selected from a known method such as the following method: a method in which a stirrer or a stirring blade is rotated and mixed; a method in which mixing is performed using a mixer; Ultrasonic method of mixing.

關於各成分之添加以及混合時之溫度及時間，只要各調配成分不劣化則並無特別限定，只要適切調節即可，溫度較佳為15℃至30℃。 The temperature and time during the addition of each component and the mixing time are not particularly limited as long as the respective components do not deteriorate, and the temperature is preferably 15 ° C to 30 ° C as long as it is appropriately adjusted.

<熱固化性樹脂膜> <Thermosetting resin film>

本發明之熱固化性樹脂膜1包含熱固化性樹脂組成物，如上所述，係用以保護半導體晶圓5的表面(電路面)5a、及設於該表面5a上之複數個凸塊51的膜，藉由熱固化而形成第一保護膜1a。 The thermosetting resin film 1 of the present invention comprises a thermosetting resin composition, as described above, for protecting the surface (circuit surface) 5a of the semiconductor wafer 5, and a plurality of bumps 51 provided on the surface 5a. The film is formed by heat curing to form the first protective film 1a.

藉由使用本發明之熱固化性樹脂膜1形成第一保護膜1a，半導體晶圓5的表面(電路面)5a、及凸塊51的表面5a附近之部位、亦即基部經第一保護膜1a充分地保護。 The first protective film 1a is formed by using the thermosetting resin film 1 of the present invention, and the surface (circuit surface) 5a of the semiconductor wafer 5 and the portion near the surface 5a of the bump 51, that is, the base portion is subjected to the first protective film. 1a is fully protected.

如上所述，本發明之熱固化性樹脂膜1的藉由示差掃描熱量分析法所測定之發熱起始溫度為第二保護膜形成膜2的發熱起始溫度以上。進而，熱固化性樹脂膜1係以 發熱峰溫度為100℃至200℃，且該熱固化性樹脂膜1與第二保護膜形成膜2的發熱峰溫度之差成為小於35℃之方式構成。 As described above, the heat generation starting temperature of the thermosetting resin film 1 of the present invention measured by the differential scanning calorimetry method is equal to or higher than the heat generation starting temperature of the second protective film forming film 2. Further, the thermosetting resin film 1 is The exothermic temperature is 100° C. to 200° C., and the difference between the exothermic peak temperatures of the thermosetting resin film 1 and the second protective film forming film 2 is less than 35° C.

另外，進而熱固化性樹脂膜1能以如下方式構成：線膨脹係數為5(×10-6/℃)至80(×10-6/℃)，且與第二保護膜形成膜2的線膨脹係數之差成為小於35(×10-6/℃)。 Further, the thermosetting resin film 1 can be configured in such a manner that the coefficient of linear expansion is 5 (×10 -6 /° C.) to 80 (×10 -6 /° C.), and the line of the film 2 is formed with the second protective film. The difference in expansion coefficient becomes less than 35 (×10 -6 /°C).

熱固化性樹脂膜1可使用含有其構成材料之熱固化性樹脂組成物而形成。該熱固化性樹脂組成物至少含有熱固化性成分。 The thermosetting resin film 1 can be formed using a thermosetting resin composition containing a constituent material thereof. The thermosetting resin composition contains at least a thermosetting component.

因此，熱固化性樹脂膜1的藉由示差掃描熱量分析法所測定之發熱起始溫度、發熱峰溫度及線膨脹係數可藉由調節熱固化性樹脂組成物的含有成分的種類及量之任一者或兩者而調節。 Therefore, the heat generation start temperature, the heat generation peak temperature, and the linear expansion coefficient of the thermosetting resin film 1 measured by the differential scanning calorimetry can be adjusted by adjusting the type and amount of the components of the thermosetting resin composition. Adjusted by one or both.

關於熱固化性樹脂組成物及其製造方法，將於下文中加以詳細說明。 The thermosetting resin composition and a method for producing the same will be described in detail below.

例如藉由增減熱固化性樹脂組成物的含有成分中特別是熱固化性成分於前述組成物中之含量，可將熱固化性樹脂膜1的發熱起始溫度及發熱峰溫度、進而線膨脹係數調節至較佳範圍內。 For example, by increasing or decreasing the content of the thermosetting resin composition, particularly the thermosetting component in the composition, the heat generation starting temperature and the exothermic peak temperature of the thermosetting resin film 1 can be linearly expanded. The coefficient is adjusted to a preferred range.

作為較佳之熱固化性樹脂膜1，例如可列舉含有聚合物成分(A)及熱固化性成分(B)者。聚合物成分(A)係被視 為聚合性化合物進行聚合反應而形成之成分。另外，熱固化性成分(B)為能以熱作為反應之觸發而進行固化(聚合)反應之成分。再者，本發明中，於聚合反應中亦包括縮聚反應。 The preferred thermosetting resin film 1 includes, for example, a polymer component (A) and a thermosetting component (B). Polymer component (A) is regarded as A component formed by conducting a polymerization reaction of a polymerizable compound. Further, the thermosetting component (B) is a component capable of undergoing a curing (polymerization) reaction with heat as a trigger for the reaction. Further, in the present invention, a polycondensation reaction is also included in the polymerization reaction.

熱固化性樹脂膜1可僅由一層(單層)構成，亦可由兩層以上之複數層構成。於熱固化性樹脂膜1為複數層之情形時，該等複數層可彼此相同亦可不同，該等複數層的組合並無特別限定。 The thermosetting resin film 1 may be composed of only one layer (single layer) or may be composed of a plurality of layers of two or more layers. When the thermosetting resin film 1 is a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.

於熱固化性樹脂膜1為複數層之情形時，只要構成熱固化性樹脂膜1之所有層滿足上述發熱起始溫度及發熱峰溫度的條件即可。 When the thermosetting resin film 1 is a plurality of layers, the conditions of the heat generation starting temperature and the exothermic peak temperature may be satisfied for all the layers constituting the thermosetting resin film 1.

熱固化性樹脂膜1的厚度並無特別限定，例如較佳為1μm至100μm，更佳為5μm至75μm，尤佳為5μm至50μm。藉由熱固化性樹脂膜1的厚度為上述下限值以上，可形成保護能力更高之第一保護膜1a。 The thickness of the thermosetting resin film 1 is not particularly limited, and is, for example, preferably 1 μm to 100 μm, more preferably 5 μm to 75 μm, still more preferably 5 μm to 50 μm. When the thickness of the thermosetting resin film 1 is at least the above lower limit value, the first protective film 1a having higher protection ability can be formed.

此處所謂「熱固化性樹脂膜的厚度」，係指熱固化性樹脂膜1總體的厚度，例如所謂由複數層所構成之熱固化性樹脂膜1的厚度，係指構成熱固化性樹脂膜1之所有層的合計厚度。 Here, the "thickness of the thermosetting resin film" means the thickness of the entire thermosetting resin film 1, for example, the thickness of the thermosetting resin film 1 composed of a plurality of layers, and means that the thermosetting resin film is formed. The total thickness of all layers of 1.

[熱固化性樹脂組成物] [Thermal curable resin composition]

熱固化性樹脂膜1可使用含有其構成材料之熱固化 性樹脂組成物、亦即至少含有熱固化性成分之熱固化性樹脂組成物而形成。例如於熱固化性樹脂膜1之形成對象面塗敷熱固化性樹脂組成物，視需要進行乾燥，藉此可於目標部位形成熱固化性樹脂膜1。關於熱固化性樹脂組成物中的於常溫下不氣化之成分彼此的含量的比率，通常與熱固化性樹脂膜1的前述成分彼此的含量的比率相同。此處所謂「常溫」如上文中所說明。 The thermosetting resin film 1 can be thermally cured using a constituent material thereof. The resin composition is formed of a thermosetting resin composition containing at least a thermosetting component. For example, a thermosetting resin composition is applied to the target surface of the thermosetting resin film 1 and dried as necessary, whereby the thermosetting resin film 1 can be formed at the target portion. The ratio of the content of the components which are not vaporized at normal temperature in the thermosetting resin composition is usually the same as the ratio of the components of the thermosetting resin film 1 to the content of the components. The term "normal temperature" as used herein is as explained above.

熱固化性樹脂組成物之塗敷只要利用公知之方法進行即可，例如可列舉：使用氣刀塗佈機、刮刀塗佈機、棒式塗佈機、凹版塗佈機、輥式塗佈機、輥刀塗佈機、簾幕式塗佈機、模式塗佈機、刀片塗佈機、網版塗佈機、線棒塗佈機及吻合式塗佈機等各種塗佈機之方法。 The application of the thermosetting resin composition may be carried out by a known method, and examples thereof include an air knife coater, a knife coater, a bar coater, a gravure coater, and a roll coater. A method of various coaters such as a roll coater, a curtain coater, a pattern coater, a blade coater, a screen coater, a bar coater, and a staple coater.

熱固化性樹脂組成物的乾燥條件並無特別限定，於熱固化性樹脂組成物含有後述溶劑之情形時，較佳為進行加熱乾燥，於該情形時，例如較佳為於70℃至130℃且10秒至5分鐘之條件下進行乾燥。 The drying condition of the thermosetting resin composition is not particularly limited. When the thermosetting resin composition contains a solvent to be described later, it is preferably heated and dried. In this case, for example, it is preferably at 70 ° C to 130 ° C. Drying is carried out for 10 seconds to 5 minutes.

{熱固化性樹脂組成物(III-1)} {Thermal curable resin composition (III-1)}

作為熱固化性樹脂組成物，例如可列舉含有聚合物成分(A)及熱固化性成分(B)之熱固化性樹脂組成物(III-1)等。 Examples of the thermosetting resin composition include a thermosetting resin composition (III-1) containing a polymer component (A) and a thermosetting component (B).

(聚合物成分(A)) (polymer component (A))

聚合物成分(A)為用以對熱固化性樹脂膜1賦予造膜性或可撓性等之聚合物化合物。 The polymer component (A) is a polymer compound for imparting film-forming property or flexibility to the thermosetting resin film 1.

熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1所含有之聚合物成分(A)可僅為一種亦可為兩種以上。於熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1所含有之聚合物成分(A)為兩種以上之情形時，該等的組合及比率可任意地選擇。 The polymer component (A) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 may be one type or two or more types. When the polymer component (III) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 is two or more types, the combinations and ratios can be arbitrarily selected.

作為聚合物成分(A)，例如可列舉：丙烯酸系樹脂(具有(甲基)丙烯醯基之樹脂)、聚酯、胺基甲酸酯系樹脂(具有胺基甲酸酯鍵之樹脂)、丙烯酸胺基甲酸酯樹脂、矽酮系樹脂(具有矽氧烷鍵之樹脂)、橡膠系樹脂(具有橡膠結構之樹脂)、苯氧基樹脂及熱固化性聚醯亞胺等，較佳為丙烯酸系樹脂。 Examples of the polymer component (A) include an acrylic resin (a resin having a (meth)acrylonitrile group), a polyester, and a urethane resin (a resin having a urethane bond). An urethane urethane resin, an oxime ketone resin (a resin having a decane bond), a rubber resin (a resin having a rubber structure), a phenoxy resin, and a thermosetting polyimide, preferably Acrylic resin.

作為聚合物成分(A)的前述丙烯酸系樹脂，可列舉公知之丙烯酸系聚合物。 The acrylic resin as the polymer component (A) includes a known acrylic polymer.

丙烯酸系樹脂的重量平均分子量(Mw)較佳為10000至2000000，更佳為100000至1500000。藉由丙烯酸系樹脂的重量平均分子量為上述下限值以上，熱固化性樹脂膜1的形狀穩定性(保管時的經時穩定性)提高。另外，藉由丙烯酸系樹脂的重量平均分子量為上述上限值以下，熱固化性樹脂膜1容易追隨被接著體的凹凸面，例如可獲得進 一步抑制於被接著體與熱固化性樹脂膜1之間產生空隙等的功效。 The weight average molecular weight (Mw) of the acrylic resin is preferably from 10,000 to 2,000,000, more preferably from 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin is at least the above lower limit value, the shape stability (chronological stability during storage) of the thermosetting resin film 1 is improved. In addition, when the weight average molecular weight of the acrylic resin is at most the above upper limit value, the thermosetting resin film 1 easily follows the uneven surface of the adherend, and for example, it can be obtained. The effect of generating a void or the like between the adherend and the thermosetting resin film 1 is suppressed in one step.

丙烯酸系樹脂的玻璃轉移溫度(Tg)較佳為-60℃至70℃，更佳為-30℃至50℃。藉由丙烯酸系樹脂的Tg為上述下限值以上，而抑制第一保護膜1a與第一支持片的接著力，第一支持片的剝離性提高。另外，藉由丙烯酸系樹脂的Tg為上述上限值以下，熱固化性樹脂膜1及第一保護膜1a與被接著體的接著力提高。 The glass transition temperature (Tg) of the acrylic resin is preferably from -60 ° C to 70 ° C, more preferably from -30 ° C to 50 ° C. When the Tg of the acrylic resin is at least the above lower limit value, the adhesion between the first protective film 1a and the first support sheet is suppressed, and the peelability of the first support sheet is improved. In addition, when the Tg of the acrylic resin is not more than the above upper limit, the adhesion between the thermosetting resin film 1 and the first protective film 1a and the adherend is improved.

作為丙烯酸系樹脂，例如可列舉：一種或兩種以上之(甲基)丙烯酸酯的聚合物；選自(甲基)丙烯酸、衣康酸、乙酸乙烯酯、丙烯腈、苯乙烯及N-羥甲基丙烯醯胺等中的兩種以上之單體的共聚物等。 Examples of the acrylic resin include a polymer of one or two or more (meth) acrylates selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-hydroxyl. A copolymer of two or more kinds of monomers such as methacrylamide or the like.

作為構成丙烯酸系樹脂之前述(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯((甲基)丙烯酸月桂 酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯((甲基)丙烯酸肉豆蔻酯)、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯((甲基)丙烯酸棕櫚酯)、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯((甲基)丙烯酸硬脂酯)等構成烷基酯之烷基係碳數為1至18之鏈狀結構的(甲基)丙烯酸烷基酯；(甲基)丙烯酸異莰酯、(甲基)丙烯酸二環戊酯等(甲基)丙烯酸環烷基酯；(甲基)丙烯酸苄酯等(甲基)丙烯酸芳烷基酯；(甲基)丙烯酸二環戊烯酯等(甲基)丙烯酸環烯基酯；(甲基)丙烯酸二環戊烯氧基乙酯等(甲基)丙烯酸環烯氧基烷基酯；(甲基)丙烯醯亞胺；(甲基)丙烯酸縮水甘油酯等含縮水甘油基之(甲基)丙烯酸酯；(甲基)丙烯酸羥基甲酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等含羥基之(甲基)丙烯酸酯；(甲基)丙烯酸N-甲基胺基乙酯等含經取代之胺基之(甲基)丙烯酸酯等。此處所謂「經取代之胺基」，係指胺基的一個或兩個之氫原子經氫原子以外之基團取代而成的基團。 Examples of the (meth) acrylate constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, (A) Ethyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid Anthracene ester, isodecyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauric (meth)acrylate Ester), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, (methyl) Cetyl acrylate (palmityl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate) The alkyl group of the base ester is an alkyl (meth)acrylate having a chain structure of 1 to 18; an isodecyl (meth)acrylate or a (meth)acrylic acid such as dicyclopentanyl (meth)acrylate. a cycloalkyl ester; an arylalkyl (meth)acrylate such as benzyl (meth)acrylate; a cycloalkylenyl (meth)acrylate such as dicyclopentenyl (meth)acrylate; (meth)acrylic acid cycloalkyloxyalkyl ester such as cyclopentenyloxyethyl ester; (meth) acrylonitrile imine; glycidyl group-containing (meth) acrylate such as glycidyl (meth)acrylate ; hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-(meth) acrylate Hydroxybutyl ester, 3-hydroxybutyl (meth)acrylate a hydroxyl group-containing (meth) acrylate such as 4-hydroxybutyl (meth)acrylate; a (meth) acrylate having a substituted amino group such as N-methylaminoethyl (meth)acrylate; . The term "substituted amino group" as used herein means a group in which one or two hydrogen atoms of an amine group are substituted with a group other than a hydrogen atom.

丙烯酸系樹脂例如除了前述(甲基)丙烯酸酯以外，亦可為選自(甲基)丙烯酸、衣康酸、乙酸乙烯酯、丙烯腈、苯乙烯及N-羥甲基丙烯醯胺等中的一種或兩種以上之單體進行共聚合而成者。 The acrylic resin may be selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylol acrylamide, etc., in addition to the above (meth) acrylate. One or two or more monomers are copolymerized.

構成丙烯酸系樹脂之單體可僅為一種亦可為兩種以上。於構成丙烯酸系樹脂之單體為兩種以上之情形時，該等的組合及比率可任意地選擇。 The monomers constituting the acrylic resin may be one type or two or more types. When two or more monomers constituting the acrylic resin are used, the combinations and ratios can be arbitrarily selected.

丙烯酸系樹脂例如亦可具有乙烯基、(甲基)丙烯醯基、胺基、羥基、羧基、異氰酸酯基等可與其他化合物鍵結之官能基。丙烯酸系樹脂的前述官能基可經由後述交聯劑(F)而與其他化合物鍵結，亦可不經由交聯劑(F)而與其他化合物直接鍵結。藉由丙烯酸系樹脂藉由前述官能基而與其他化合物鍵結，有使用熱固化性樹脂膜1所得之封裝的可靠性提高之傾向。 The acrylic resin may have a functional group which may be bonded to another compound such as a vinyl group, a (meth)acryl fluorenyl group, an amine group, a hydroxyl group, a carboxyl group or an isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a crosslinking agent (F) to be described later, or may be directly bonded to another compound without passing through the crosslinking agent (F). When the acrylic resin is bonded to another compound by the functional group, the reliability of the package obtained by using the thermosetting resin film 1 tends to be improved.

本發明中，作為聚合物成分(A)，可不使用丙烯酸系樹脂而將丙烯酸系樹脂以外之熱塑性樹脂(以下，有時僅簡稱為「熱塑性樹脂」)單獨使用，亦可將該熱塑性樹脂與丙烯酸系樹脂並用。藉由使用前述熱塑性樹脂，有時第一保護膜1a自第一支持片11之剝離性提高，或熱固化性樹脂膜1容易追隨被接著體的凹凸面，而進一步抑制於被接著體與熱固化性樹脂膜1之間產生空隙等。 In the present invention, as the polymer component (A), a thermoplastic resin other than the acrylic resin (hereinafter sometimes simply referred to as "thermoplastic resin") may be used alone without using an acrylic resin, and the thermoplastic resin and acrylic acid may be used. Resin and use. By using the thermoplastic resin, the peeling property of the first protective film 1a from the first support sheet 11 may be improved, or the thermosetting resin film 1 may easily follow the uneven surface of the adherend, thereby further suppressing the adherend and heat. A void or the like is generated between the curable resin films 1.

前述熱塑性樹脂的重量平均分子量較佳為1000至100000，更佳為3000至80000。 The weight average molecular weight of the aforementioned thermoplastic resin is preferably from 1,000 to 100,000, more preferably from 3,000 to 80,000.

前述熱塑性樹脂的玻璃轉移溫度(Tg)較佳為-30℃至 150℃，更佳為-20℃至120℃。再者，玻璃轉移溫度(Tg)可藉由上述示差掃描熱量分析法來測定。 The glass transition temperature (Tg) of the aforementioned thermoplastic resin is preferably -30 ° C to 150 ° C, more preferably -20 ° C to 120 ° C. Further, the glass transition temperature (Tg) can be measured by the above differential scanning calorimetry.

作為前述熱塑性樹脂，例如可列舉聚酯、聚胺基甲酸酯、苯氧基樹脂、聚丁烯、聚丁二烯及聚苯乙烯等。 Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, and polystyrene.

熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1所含有之前述熱塑性樹脂可僅為一種亦可為兩種以上。於熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1所含有之前述熱塑性樹脂為兩種以上之情形時，該等的組合及比率可任意地選擇。 The thermoplastic resin contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 may be one type or two or more types. When the thermoplastic resin contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 is two or more kinds, the combinations and ratios can be arbitrarily selected.

於熱固化性樹脂組成物(III-1)中，聚合物成分(A)的含量相對於溶劑以外之所有成分的總含量之比例(亦即熱固化性樹脂膜1的聚合物成分(A)的含量)係與聚合物成分(A)的種類無關地較佳為5質量%至85質量%，更佳為5質量%至80質量%。 In the thermosetting resin composition (III-1), the ratio of the content of the polymer component (A) to the total content of all components other than the solvent (that is, the polymer component (A) of the thermosetting resin film 1) The content is preferably from 5% by mass to 85% by mass, and more preferably from 5% by mass to 80% by mass, irrespective of the kind of the polymer component (A).

聚合物成分(A)有時亦相當於熱固化性成分(B)。本發明中，於熱固化性樹脂組成物(III-1)含有相當於此種聚合物成分(A)及熱固化性成分(B)兩者之成分之情形時，視為熱固化性樹脂組成物(III-1)含有聚合物成分(A)及熱固化性成分(B)。 The polymer component (A) sometimes also corresponds to the thermosetting component (B). In the present invention, when the thermosetting resin composition (III-1) contains a component corresponding to both the polymer component (A) and the thermosetting component (B), it is considered to be a thermosetting resin composition. The substance (III-1) contains a polymer component (A) and a thermosetting component (B).

(熱固化性成分(B)) (thermosetting component (B))

熱固化性成分(B)為用以使熱固化性樹脂膜1固化而形成硬質之第一保護膜1a的成分。 The thermosetting component (B) is a component for curing the thermosetting resin film 1 to form a hard first protective film 1a.

熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1所含有之熱固化性成分(B)可僅為一種亦可為兩種以上。於熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1所含有之熱固化性成分(B)為兩種以上之情形時，該等的組合及比率可任意地選擇。 The thermosetting component (III-1) and the thermosetting resin film 1 contained in the thermosetting resin film 1 may be one type or two or more types. When the thermosetting resin composition (III-1) and the thermosetting resin film 1 contain two or more types of thermosetting components (B), the combinations and ratios can be arbitrarily selected.

作為熱固化性成分(B)，例如可列舉：環氧系熱固化性樹脂、熱固化性聚醯亞胺、聚胺基甲酸酯、不飽和聚酯及矽酮樹脂等，較佳為環氧系熱固化性樹脂。 Examples of the thermosetting component (B) include an epoxy-based thermosetting resin, a thermosetting polyimide, a polyurethane, an unsaturated polyester, and an anthrone resin, and preferably a ring. Oxygen-based thermosetting resin.

(A)環氧系熱固化性樹脂 (A) epoxy-based thermosetting resin

環氧系熱固化性樹脂係由環氧樹脂(B1)及熱固化劑(B2)所構成。 The epoxy-based thermosetting resin is composed of an epoxy resin (B1) and a heat curing agent (B2).

熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1所含有之環氧系熱固化性樹脂可僅為一種亦可為兩種以上。於熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1所含有之環氧系熱固化性樹脂為兩種以上之情形時，該等的組合及比率可任意地選擇。 The epoxy-based thermosetting resin contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 may be one type or two or more types. When the epoxy-based thermosetting resin contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 is two or more types, the combinations and ratios can be arbitrarily selected.

．環氧樹脂(B1) . Epoxy resin (B1)

作為環氧樹脂(B1)，可列舉公知之環氧樹脂，例如可 列舉：多官能系環氧樹脂、聯苯化合物、雙酚A二縮水甘油醚及其氫化物、鄰甲酚酚醛清漆環氧樹脂、二環戊二烯型環氧樹脂、聯苯型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、及伸苯基骨架型環氧樹脂等、二官能以上之環氧化合物。 As the epoxy resin (B1), a known epoxy resin can be mentioned, for example, Listed: polyfunctional epoxy resin, biphenyl compound, bisphenol A diglycidyl ether and its hydride, o-cresol novolac epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin A bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a phenyl group-type epoxy resin, and a difunctional or higher epoxy compound.

作為環氧樹脂(B1)，亦可使用具有不飽和烴基之環氧樹脂。具有不飽和烴基之環氧樹脂與不具有不飽和烴基之環氧樹脂相比，與丙烯酸系樹脂之相容性較高。因此，藉由使用具有不飽和烴基之環氧樹脂，使用熱固化性樹脂膜所得之封裝的可靠性提高。 As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can also be used. The epoxy resin having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin than the epoxy resin having no unsaturated hydrocarbon group. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the thermosetting resin film is improved.

作為具有不飽和烴基之環氧樹脂，例如可列舉：將多官能系環氧樹脂的環氧基的一部分變換成具有不飽和烴基之基團而成的化合物。此種化合物例如可藉由使(甲基)丙烯酸或其衍生物對環氧基進行加成反應而獲得。 Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound obtained by converting a part of an epoxy group of a polyfunctional epoxy resin into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by subjecting an epoxy group to an addition reaction of (meth)acrylic acid or a derivative thereof.

另外，作為具有不飽和烴基之環氧樹脂，例如可列舉：具有不飽和烴基之基團直接鍵結於構成環氧樹脂之芳香環等而成的化合物等。 In addition, examples of the epoxy resin having an unsaturated hydrocarbon group include a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring constituting an epoxy resin or the like.

不飽和烴基為具有聚合性之不飽和基，作為其具體例，可列舉：乙烯基(ethenyl)、2-丙烯基(烯丙基)、(甲基)丙烯醯基、(甲基)丙烯醯胺基等，較佳為丙烯醯基。 The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples thereof include ethenyl, 2-propenyl (allyl), (meth)acrylonitrile, and (meth)acryl oxime. An amine group or the like is preferably an acrylonitrile group.

環氧樹脂(B1)的數量平均分子量並無特別限定，就熱 固化性樹脂膜1的固化性、以及固化後的第一保護膜1a的強度及耐熱性之方面而言，較佳為300至30000，更佳為400至10000，尤佳為500至3000。再者，環氧樹脂(B1)的數量平均分子量可藉由先前公知之凝膠滲透層析(GPC)法(苯乙烯標準)來測定。 The number average molecular weight of the epoxy resin (B1) is not particularly limited, and it is hot. The curability of the curable resin film 1 and the strength and heat resistance of the first protective film 1a after curing are preferably from 300 to 30,000, more preferably from 400 to 10,000, still more preferably from 500 to 3,000. Further, the number average molecular weight of the epoxy resin (B1) can be determined by a previously known gel permeation chromatography (GPC) method (styrene standard).

環氧樹脂(B1)的環氧當量較佳為100g/eq至1000g/eq，更佳為300g/eq至800g/eq。再者，環氧樹脂(B1)的環氧當量可利用依據JIS(Japanese Industrial Standards；日本工業標準)K7236：2001之方法來測定。 The epoxy equivalent of the epoxy resin (B1) is preferably from 100 g/eq to 1000 g/eq, more preferably from 300 g/eq to 800 g/eq. Further, the epoxy equivalent of the epoxy resin (B1) can be measured by a method in accordance with JIS (Japanese Industrial Standards) K7236:2001.

環氧樹脂(B1)可單獨使用一種亦可並用兩種以上，於並用兩種以上之情形時，該等的組合及比率可任意地選擇。 The epoxy resin (B1) may be used alone or in combination of two or more. When two or more kinds are used in combination, the combinations and ratios may be arbitrarily selected.

．熱固化劑(B2) . Heat curing agent (B2)

熱固化劑(B2)作為對環氧樹脂(B1)之固化劑而發揮功能。 The heat curing agent (B2) functions as a curing agent for the epoxy resin (B1).

作為熱固化劑(B2)，例如可列舉一分子中具有兩個以上之可與環氧基反應之官能基的化合物。作為前述官能基，例如可列舉：酚性羥基、醇性羥基、胺基、羧基、酸基經酐化而成之基團等，較佳為酚性羥基、胺基或酸基經酐化而成之基團，更佳為酚性羥基或胺基。 The thermosetting agent (B2) may, for example, be a compound having two or more functional groups reactive with an epoxy group in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group, and a group in which an acid group is anhydride-formed. Preferably, the phenolic hydroxyl group, the amine group or the acid group is anhydride-treated. The group formed is more preferably a phenolic hydroxyl group or an amine group.

熱固化劑(B2)中，作為具有酚性羥基之酚系固化劑， 例如可列舉：多官能酚樹脂、聯苯酚、酚醛清漆型酚樹脂、二環戊二烯系酚樹脂及芳烷基酚樹脂等。 In the heat curing agent (B2), as a phenolic curing agent having a phenolic hydroxyl group, For example, a polyfunctional phenol resin, a biphenol, a novolak type phenol resin, a dicyclopentadiene type phenol resin, an aralkyl phenol resin, etc. are mentioned.

熱固化劑(B2)中，作為具有胺基之胺系固化劑，例如可列舉二氰基二醯胺(以下有時簡稱為「DICY」)等。 In the thermosetting agent (B2), examples of the amine-based curing agent having an amine group include dicyanodicimide (hereinafter sometimes abbreviated as "DICY").

熱固化劑(B2)亦可具有不飽和烴基。 The heat curing agent (B2) may also have an unsaturated hydrocarbon group.

作為具有不飽和烴基之熱固化劑(B2)，例如可列舉：酚樹脂的一部分羥基經具有不飽和烴基之基團取代而成的化合物，具有不飽和烴基之基團直接鍵結於酚樹脂的芳香環而成的化合物等。 The thermosetting agent (B2) having an unsaturated hydrocarbon group may, for example, be a compound in which a part of a hydroxyl group of a phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a group having an unsaturated hydrocarbon group is directly bonded to a phenol resin. A compound made of an aromatic ring.

熱固化劑(B2)中的前述不飽和烴基與上述具有不飽和烴基之環氧樹脂中的不飽和烴基相同。 The aforementioned unsaturated hydrocarbon group in the heat curing agent (B2) is the same as the unsaturated hydrocarbon group in the above epoxy resin having an unsaturated hydrocarbon group.

於使用酚系固化劑作為熱固化劑(B2)之情形時，就第一保護膜1a自第一支持片之剝離性提高之方面而言，較佳為熱固化劑(B2)的軟化點或玻璃轉移溫度高。 In the case where a phenolic curing agent is used as the thermosetting agent (B2), the softening point of the thermosetting agent (B2) is preferably in terms of improving the peeling property of the first protective film 1a from the first supporting sheet or The glass transfer temperature is high.

熱固化劑(B2)中，例如多官能酚樹脂、酚醛清漆型酚樹脂、二環戊二烯系酚樹脂、芳烷基酚樹脂等樹脂成分的數量平均分子量較佳為300至30000，更佳為400至10000，尤佳為500至3000。再者，關於上述數量平均分子量，亦可藉由先前公知之凝膠滲透層析(GPC)法(苯乙烯標準)來測定。 In the thermosetting agent (B2), for example, the number average molecular weight of the resin component such as a polyfunctional phenol resin, a novolac type phenol resin, a dicyclopentadiene phenol resin, or an aralkyl phenol resin is preferably from 300 to 30,000, more preferably It is 400 to 10,000, and particularly preferably 500 to 3,000. Further, the above number average molecular weight can also be determined by a previously known gel permeation chromatography (GPC) method (styrene standard).

熱固化劑(B2)中，例如聯苯酚、二氰基二醯胺等非樹 脂成分的分子量並無特別限定，例如較佳為60至500。 In the heat curing agent (B2), for example, non-tree such as biphenol or dicyanodiamine The molecular weight of the lipid component is not particularly limited, and is, for example, preferably from 60 to 500.

熱固化劑(B2)可單獨使用一種亦可並用兩種以上。於並用兩種以上作為熱固化劑(B2)之情形時，該等的組合及比率可任意地選擇。 The heat curing agent (B2) may be used alone or in combination of two or more. When two or more types are used in combination as the heat curing agent (B2), the combinations and ratios can be arbitrarily selected.

熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1中，相對於環氧樹脂(B1)的含量100質量份，熱固化劑(B2)的含量較佳為0.1質量份至500質量份，更佳為1質量份至200質量份。藉由熱固化劑(B2)的含量為上述下限值以上，更容易進行熱固化性樹脂膜1的固化。另外，藉由熱固化劑(B2)的含量為上述上限值以下，而降低熱固化性樹脂膜1的吸濕率，使用熱固化性樹脂膜1所得之封裝的可靠性進一步提高。 In the thermosetting resin composition (III-1) and the thermosetting resin film 1, the content of the thermosetting agent (B2) is preferably from 0.1 part by mass to 500 parts by mass based on 100 parts by mass of the epoxy resin (B1). The parts by mass are more preferably from 1 part by mass to 200 parts by mass. When the content of the thermosetting agent (B2) is at least the above lower limit value, the curing of the thermosetting resin film 1 is more easily performed. In addition, when the content of the thermosetting agent (B2) is at most the above upper limit value, the moisture absorption rate of the thermosetting resin film 1 is lowered, and the reliability of the package obtained by using the thermosetting resin film 1 is further improved.

熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1中，相對於聚合物成分(A)的含量100質量份，熱固化性成分(B)的含量(例如環氧樹脂(B1)及熱固化劑(B2)的總含量)較佳為50質量份至1000質量份，更佳為100質量份至900質量份，尤佳為150質量份至800質量份。藉由熱固化性成分(B)的前述含量為此種範圍，而抑制第一保護膜1a與第一支持片的接著力，提高第一支持片的剝離性。 In the thermosetting resin composition (III-1) and the thermosetting resin film 1, the content of the thermosetting component (B) is 100 parts by mass based on the content of the polymer component (A) (for example, epoxy resin (B1) The total content of the heat curing agent (B2) is preferably from 50 parts by mass to 1000 parts by mass, more preferably from 100 parts by mass to 900 parts by mass, still more preferably from 150 parts by mass to 800 parts by mass. When the content of the thermosetting component (B) is within such a range, the adhesion between the first protective film 1a and the first support sheet is suppressed, and the peelability of the first support sheet is improved.

(固化促進劑(C)) (curing accelerator (C))

熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1亦可含有固化促進劑(C)。固化促進劑(C)為用以調整熱固化性樹脂組成物(III-1)的固化速度之成分。 The thermosetting resin composition (III-1) and the thermosetting resin film 1 may further contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing speed of the thermosetting resin composition (III-1).

作為較佳之固化促進劑(C)，例如可列舉：三伸乙基二胺、苄基二甲基胺、三乙醇胺、二甲基胺基乙醇、三(二甲基胺基甲基)苯酚等三級胺；2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑等咪唑類(一個以上之氫原子經氫原子以外之基團取代的咪唑)；三丁基膦、二苯基膦、三苯基膦等有機膦類(一個以上之氫原子經有機基取代的膦)；四苯基鏻四苯基硼酸鹽、三苯基膦四苯基硼酸鹽等四苯基硼鹽等。 Preferred examples of the curing accelerator (C) include tri-ethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol. Tertiary amine; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl An imidazole such as a 5-hydroxymethylimidazole (an imidazole in which one or more hydrogen atoms are substituted by a group other than a hydrogen atom); an organic phosphine such as tributylphosphine, diphenylphosphine or triphenylphosphine (more than one) a phosphine in which a hydrogen atom is substituted with an organic group; a tetraphenylborate such as tetraphenylphosphonium tetraphenylborate or triphenylphosphine tetraphenylborate; and the like.

熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1所含有之固化促進劑(C)可僅為一種亦可為兩種以上。於熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1所含有之固化促進劑(C)為兩種以上之情形時，該等的組合及比率可任意地選擇。 The curing accelerator (C) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 may be one type or two or more types. When the curing accelerator (C) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 is two or more types, the combinations and ratios can be arbitrarily selected.

於使用固化促進劑(C)之情形時，於熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1中，相對於熱固化性成分(B)的含量100質量份，固化促進劑(C)的含量較佳為0.01質量份至10質量份，更佳為0.1質量份至5質量份。藉由固化促進劑(C)的含量為上述下限值以上，可更顯著地 獲得由使用固化促進劑(C)所帶來之功效。另外，藉由固化促進劑(C)的含量為上述上限值以下，例如抑制高極性之固化促進劑(C)於高溫、高濕度條件下於熱固化性樹脂膜1中移動至與被接著體的接著界面側而偏析的功效提高，使用熱固化性樹脂膜1所得之封裝的可靠性進一步提高。 When the curing accelerator (C) is used, in the thermosetting resin composition (III-1) and the thermosetting resin film 1, the curing is promoted with respect to 100 parts by mass of the content of the thermosetting component (B). The content of the agent (C) is preferably from 0.01 part by mass to 10 parts by mass, more preferably from 0.1 part by mass to 5 parts by mass. When the content of the curing accelerator (C) is at least the above lower limit value, it is more remarkable The effect brought about by the use of the curing accelerator (C) is obtained. In addition, when the content of the curing accelerator (C) is equal to or less than the above upper limit, for example, the curing accelerator (C) having high polarity is prevented from moving to and from the thermosetting resin film 1 under high temperature and high humidity conditions. The effect of segregation on the interface side of the body is improved, and the reliability of the package obtained by using the thermosetting resin film 1 is further improved.

(填充材料(D)) (filling material (D))

熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1亦可含有填充材料(D)。藉由熱固化性樹脂膜1含有填充材料(D)，將熱固化性樹脂膜1固化所得之第一保護膜1a容易將熱膨脹係數調整至上述範圍內，藉由對第一保護膜1a之形成對象物進行該熱膨脹係數之最適化，使用熱固化性樹脂膜所得之封裝的可靠性進一步提高。另外，藉由熱固化性樹脂膜1含有填充材料(D)，亦可降低第一保護膜1a的吸濕率，或提高散熱性。 The thermosetting resin composition (III-1) and the thermosetting resin film 1 may further contain a filler (D). When the thermosetting resin film 1 contains the filler (D), the first protective film 1a obtained by curing the thermosetting resin film 1 is easily adjusted to have the thermal expansion coefficient within the above range, and the first protective film 1a is formed. The object is optimized for the coefficient of thermal expansion, and the reliability of the package obtained by using the thermosetting resin film is further improved. In addition, when the thermosetting resin film 1 contains the filler (D), the moisture absorption rate of the first protective film 1a or the heat dissipation property can be improved.

填充材料(D)可為有機填充材料及無機填充材料的任一種，較佳為無機填充材料。 The filler (D) may be any of an organic filler and an inorganic filler, and is preferably an inorganic filler.

作為較佳之無機填充材料，例如可列舉：二氧化矽、氧化鋁、滑石、碳酸鈣、鈦白、鐵丹、碳化矽、氮化硼等的粉末；將該等無機填充材料製成球形而成之珠粒；該等無機填充材料的表面改質品；該等無機填充材料的單晶纖維；玻璃纖維等。 Examples of preferred inorganic fillers include powders of cerium oxide, aluminum oxide, talc, calcium carbonate, titanium white, iron oxide, tantalum carbide, and boron nitride; and the inorganic fillers are spherical. Beads; surface modifiers of such inorganic fillers; single crystal fibers of such inorganic fillers; glass fibers, and the like.

該等中，無機填充材料較佳為二氧化矽或氧化鋁。 Among these, the inorganic filler is preferably cerium oxide or aluminum oxide.

熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1所含有之填充材料(D)可僅為一種亦可為兩種以上。於熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1所含有之填充材料(D)為兩種以上之情形時，該等的組合及比率可任意地選擇。 The filler (D) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 may be one type or two or more types. When the filler (D) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 is two or more types, the combinations and ratios can be arbitrarily selected.

於使用填充材料(D)之情形時，於熱固化性樹脂組成物(III-1)中，填充材料(D)的含量相對於溶劑以外之所有成分的總含量之比例(亦即熱固化性樹脂膜1的填充材料(D)的含量)較佳為5質量%至80質量%，更佳為7質量%至60質量%。藉由填充材料(D)的含量為此種範圍，上述熱膨脹係數之調整變得更容易。 In the case of using the filler (D), in the thermosetting resin composition (III-1), the ratio of the content of the filler (D) to the total content of all components other than the solvent (that is, thermosetting property) The content of the filler (D) of the resin film 1 is preferably from 5% by mass to 80% by mass, more preferably from 7% by mass to 60% by mass. By the content of the filler (D) being such a range, the adjustment of the above thermal expansion coefficient becomes easier.

(偶合劑(E)) (coupler (E))

熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1亦可含有偶合劑(E)。藉由使用具有可與無機化合物或有機化合物反應之官能基者作為偶合劑(E)，可使熱固化性樹脂膜1對被接著體之接著性及密接性提高。另外，藉由使用偶合劑(E)，將熱固化性樹脂膜1固化所得之第一保護膜1a於不損及耐熱性之情況下，耐水性提高。 The thermosetting resin composition (III-1) and the thermosetting resin film 1 may further contain a coupling agent (E). By using a functional group capable of reacting with an inorganic compound or an organic compound as a coupling agent (E), the adhesion and adhesion of the thermosetting resin film 1 to the adherend can be improved. In addition, the first protective film 1a obtained by curing the thermosetting resin film 1 by using the coupling agent (E) improves the water resistance without impairing heat resistance.

偶合劑(E)較佳為具有可與聚合物成分(A)、熱固化性 成分(B)等所具有的官能基反應之官能基的化合物，更佳為矽烷偶合劑。 The coupling agent (E) preferably has a polymerizable component (A) and is thermally curable. The compound having a functional group reactive with a functional group such as the component (B) is more preferably a decane coupling agent.

作為較佳之前述矽烷偶合劑，例如可列舉：3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基甲基二乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基甲基二乙氧基矽烷、3-(苯基胺基)丙基三甲氧基矽烷、3-苯胺基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、雙(3-三乙氧基矽烷基丙基)四硫化物、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙醯氧基矽烷及咪唑矽烷等。 Preferred examples of the decane coupling agent include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, and 3-glycidoxypropyl III. Ethoxy decane, 3-glycidoxymethyl diethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxy Baseline, 3-aminopropyltrimethoxydecane, 3-(2-aminoethylamino)propyltrimethoxydecane, 3-(2-aminoethylamino)propylmethyldi Ethoxy decane, 3-(phenylamino)propyltrimethoxydecane, 3-anilinopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, 3-mercaptopropyltrimethoxy Baseline, 3-mercaptopropylmethyldimethoxydecane, bis(3-triethoxydecylpropyl)tetrasulfide, methyltrimethoxydecane, methyltriethoxydecane, vinyl Trimethoxy decane, vinyl triethoxy decane, imidazolium, and the like.

熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1所含有之偶合劑(E)可僅為一種亦可為兩種以上。於熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1所含有之偶合劑(E)為兩種以上之情形時，該等的組合及比率可任意地選擇。 The coupling agent (E) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 may be one type or two or more types. When the coupler (E) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 is two or more types, the combinations and ratios can be arbitrarily selected.

於使用偶合劑(E)之情形時，於熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1中，相對於聚合物成分(A)及熱固化性成分(B)的總含量100質量份，偶合劑(E)的含量較佳為0.03質量份至20質量份，更佳為0.05質量份至10 質量份，尤佳為0.1質量份至5質量份。藉由偶合劑(E)的含量為上述下限值以上，而更顯著地獲得填充材料(D)於樹脂中之分散性的提高、或熱固化性樹脂膜1與被接著體的接著性的提高等由使用偶合劑(E)所帶來之功效。另外，藉由偶合劑(E)的含量為上述上限值以下，而進一步抑制逸氣的產生。 In the case of using the coupling agent (E), the total of the polymer component (A) and the thermosetting component (B) in the thermosetting resin composition (III-1) and the thermosetting resin film 1 The content of the coupling agent (E) is preferably from 0.03 parts by mass to 20 parts by mass, more preferably from 0.05 parts by mass to 10 parts by mass per 100 parts by mass. The part by mass is particularly preferably from 0.1 part by mass to 5 parts by mass. When the content of the coupling agent (E) is at least the above lower limit value, the dispersibility of the filler (D) in the resin or the adhesion of the thermosetting resin film 1 to the adherend is more remarkably obtained. Improve the efficacy brought about by the use of the coupling agent (E). Further, the content of the coupling agent (E) is equal to or less than the above upper limit value, and generation of outgas is further suppressed.

(交聯劑(F)) (crosslinking agent (F))

於使用上述丙烯酸系樹脂等具有可與其他化合物鍵結之乙烯基、(甲基)丙烯醯基、胺基、羥基、羧基、異氰酸酯基等官能基者作為聚合物成分(A)之情形時，熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1亦可含有用以使前述官能基與其他化合物鍵結並進行交聯之交聯劑(F)。藉由使用交聯劑(F)進行交聯，可調節熱固化性樹脂膜1的初期接著力及凝集力。 When a functional group such as a vinyl group, a (meth) acrylonitrile group, an amine group, a hydroxyl group, a carboxyl group or an isocyanate group which can be bonded to another compound such as the above acrylic resin is used as the polymer component (A), The thermosetting resin composition (III-1) and the thermosetting resin film 1 may further contain a crosslinking agent (F) for bonding and crosslinking the aforementioned functional group with another compound. The initial adhesion and the cohesive force of the thermosetting resin film 1 can be adjusted by crosslinking using the crosslinking agent (F).

作為交聯劑(F)，例如可列舉：有機多元異氰酸酯化合物、有機多元亞胺化合物、金屬螯合物系交聯劑(具有金屬螯合物結構之交聯劑)、氮丙啶系交聯劑(具有氮丙啶基之交聯劑)等。 Examples of the crosslinking agent (F) include an organic polyvalent isocyanate compound, an organic polyimine compound, a metal chelate crosslinking agent (a crosslinking agent having a metal chelate structure), and an aziridine crosslinking. A reagent (a cross-linking agent having an aziridine group) or the like.

作為前述有機多元異氰酸酯化合物，例如可列舉：芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物及脂環族多元異氰酸酯化合物(以下有時將該等化合物統一 簡稱為「芳香族多元異氰酸酯化合物等」)；前述芳香族多元異氰酸酯化合物等的三聚物、異三聚氰酸酯體及加合物；使前述芳香族多元異氰酸酯化合物等與多元醇化合物反應所得之末端異氰酸酯胺基甲酸酯預聚物等。前述「加合物」係指前述芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物或脂環族多元異氰酸酯化合物與乙二醇、丙二醇、新戊二醇、三羥甲基丙烷或蓖麻油等含低分子活性氫之化合物的反應物，作為其例子，可列舉後述般之三羥甲基丙烷之二甲苯二異氰酸酯加成物等。另外所謂「末端異氰酸酯胺基甲酸酯預聚物」如上文中所說明。 Examples of the organic polyvalent isocyanate compound include an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, and an alicyclic polyisocyanate compound (hereinafter, these compounds may be unified) It is simply referred to as "aromatic polyisocyanate compound or the like"); a trimer such as an aromatic polyisocyanate compound, an isocyanurate or an adduct; and the aromatic polyisocyanate compound and the like are reacted with a polyol compound. A terminal isocyanate urethane prepolymer or the like. The term "adduct" means a low content of the above aromatic polyvalent isocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. The reaction product of the compound of the molecularly active hydrogen may, for example, be a xylene diisocyanate adduct of trimethylolpropane described later. Further, the "terminal isocyanate urethane prepolymer" is as described above.

作為前述有機多元異氰酸酯化合物，更具體而言，例如可列舉：2,4-甲苯二異氰酸酯；2,6-甲苯二異氰酸酯；1,3-二甲苯二異氰酸酯；1,4-二甲苯二異氰酸酯；二苯基甲烷-4,4'-二異氰酸酯；二苯基甲烷-2,4'-二異氰酸酯；3-甲基二苯基甲烷二異氰酸酯；六亞甲基二異氰酸酯；異佛爾酮二異氰酸酯；二環己基甲烷-4,4'-二異氰酸酯；二環己基甲烷-2,4'-二異氰酸酯；於三羥甲基丙烷等多元醇之全部或一部分羥基加成甲苯二異氰酸酯、六亞甲基二異氰酸酯及二甲苯二異氰酸酯的任一種或兩種以上而成之化合物；離胺酸二異氰酸酯等。 More specifically, the organic polyvalent isocyanate compound may, for example, be 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylene diisocyanate; 1,4-xylene diisocyanate; Diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate Dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; addition of toluene diisocyanate or hexamethylene to all or a part of hydroxyl groups of polyols such as trimethylolpropane A compound obtained by any one or two or more kinds of a diisocyanate and a xylene diisocyanate; an isocyanuric acid diisocyanate or the like.

作為前述有機多元亞胺化合物，例如可列舉：N,N'-二苯基甲烷-4,4'-雙(1-氮丙啶羧基醯胺)、三羥甲基丙烷- 三-β-氮丙啶基丙酸酯、四羥甲基甲烷-三-β-氮丙啶基丙酸酯、N,N'-甲苯-2,4-雙(1-氮丙啶羧基醯胺)三伸乙基三聚氰胺等。 The organic polyimine compound may, for example, be N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxyguanamine) or trimethylolpropane- Tri-β-aziridine propionate, tetramethylolmethane-tri-β-aziridine propionate, N,N'-toluene-2,4-bis(1-aziridinecarboxyl Amine) tri-ethyl melamine and the like.

於使用有機多元異氰酸酯化合物作為交聯劑(F)之情形時，作為聚合物成分(A)，較佳為使用含羥基之聚合物。於交聯劑(F)具有異氰酸酯基，且聚合物成分(A)具有羥基之情形時，藉由交聯劑(F)與聚合物成分(A)之反應，可於熱固化性樹脂膜1中導入交聯結構。 In the case where an organic polyvalent isocyanate compound is used as the crosslinking agent (F), as the polymer component (A), a hydroxyl group-containing polymer is preferably used. When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the crosslinking reaction (F) and the polymer component (A) can be reacted to form the thermosetting resin film 1 Introduce a cross-linked structure.

熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1所含有之交聯劑(F)可僅為一種亦可為兩種以上。於熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1所含有之交聯劑(F)為兩種以上之情形時，該等的組合及比率可任意地選擇。 The crosslinking agent (F) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 may be one type or two or more types. When the crosslinking agent (F) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 is two or more types, the combinations and ratios can be arbitrarily selected.

於使用交聯劑(F)之情形時，於熱固化性樹脂組成物(III-1)中，相對於聚合物成分(A)的含量100質量份，交聯劑(F)的含量較佳為0.01質量份至20質量份，更佳為0.1質量份至10質量份，尤佳為0.5質量份至5質量份。藉由交聯劑(F)的前述含量為前述下限值以上，而更顯著地獲得由使用交聯劑(F)所帶來之功效。另外，藉由使交聯劑(F)的前述含量為前述上限值以下，而抑制過度使用交聯劑(F)。 In the case of using the crosslinking agent (F), in the thermosetting resin composition (III-1), the content of the crosslinking agent (F) is preferably 100 parts by mass based on the content of the polymer component (A). It is from 0.01 part by mass to 20 parts by mass, more preferably from 0.1 part by mass to 10 parts by mass, even more preferably from 0.5 part by mass to 5 parts by mass. When the content of the crosslinking agent (F) is at least the above lower limit value, the effect by the use of the crosslinking agent (F) is more remarkably obtained. In addition, when the content of the crosslinking agent (F) is at most the above upper limit value, excessive use of the crosslinking agent (F) is suppressed.

(通用添加劑(I)) (General Additives (I))

熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1亦可於不損及本發明之功效之範圍內，含有通用添加劑(I)。 The thermosetting resin composition (III-1) and the thermosetting resin film 1 may contain the general-purpose additive (I) within a range not impairing the effects of the present invention.

通用添加劑(I)可為公知者，可根據目的而任意地選擇，並無特別限定，作為較佳者，例如可列舉：塑化劑、抗靜電劑、抗氧化劑、著色劑(染料、顏料)、收氣劑(gettering agent)等。 The general-purpose additive (I) can be arbitrarily selected according to the purpose, and is not particularly limited. Preferred examples thereof include a plasticizer, an antistatic agent, an antioxidant, and a colorant (dye, pigment). , gettering agent, etc.

熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1所含有之通用添加劑(I)可僅為一種亦可為兩種以上。於熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1所含有之通用添加劑(I)為兩種以上之情形時，該等的組合及比率可任意地選擇。 The general-purpose additive (I) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 may be one type or two or more types. When the general-purpose additive (I) contained in the thermosetting resin composition (III-1) and the thermosetting resin film 1 is two or more types, the combinations and ratios can be arbitrarily selected.

熱固化性樹脂組成物(III-1)及熱固化性樹脂膜1的通用添加劑(I)的含量並無特別限定，只要根據目的而適切選擇即可。 The content of the general additive (I) of the thermosetting resin composition (III-1) and the thermosetting resin film 1 is not particularly limited, and may be appropriately selected depending on the purpose.

(溶劑) (solvent)

熱固化性樹脂組成物(III-1)較佳為進一步含有溶劑。含有溶劑之熱固化性樹脂組成物(III-1)係處理性變良好。 The thermosetting resin composition (III-1) preferably further contains a solvent. The thermosetting resin composition (III-1) containing a solvent is excellent in handleability.

前述溶劑並無特別限定，作為較佳者，例如可列舉：甲苯、二甲苯等烴；甲醇、乙醇、2-丙醇、異丁醇(2-甲基丙烷-1-醇)、1-丁醇等醇；乙酸乙酯等酯；丙酮、甲基乙 基酮等酮；四氫呋喃等醚；二甲基甲醯胺、N-甲基吡咯啶酮等醯胺(具有醯胺鍵之化合物)等。 The solvent is not particularly limited, and examples thereof include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), and 1-butyl. Alcohols such as alcohol; esters such as ethyl acetate; acetone, methyl ethyl Ketones such as ketones; ethers such as tetrahydrofuran; decylamines (compounds having a guanamine bond) such as dimethylformamide and N-methylpyrrolidone.

熱固化性樹脂組成物(III-1)所含有之溶劑可僅為一種亦可為兩種以上。於熱固化性樹脂組成物(III-1)所含有之溶劑為兩種以上之情形時，該等的組合及比率可任意地選擇。 The solvent contained in the thermosetting resin composition (III-1) may be one type or two or more types. When the solvent contained in the thermosetting resin composition (III-1) is two or more kinds, the combinations and ratios can be arbitrarily selected.

就可將熱固化性樹脂組成物(III-1)中的含有成分更均勻地混合之方面而言，熱固化性樹脂組成物(III-1)所含有之溶劑較佳為甲基乙基酮等。 The solvent contained in the thermosetting resin composition (III-1) is preferably methyl ethyl ketone in terms of more uniformly mixing the components contained in the thermosetting resin composition (III-1). Wait.

{{熱固化性樹脂組成物的製造方法}} {{Manufacturing method of thermosetting resin composition}}

熱固化性樹脂組成物(III-1)等熱固化性樹脂組成物可藉由將構成該組成物之各成分調配而獲得。 A thermosetting resin composition such as the thermosetting resin composition (III-1) can be obtained by blending the components constituting the composition.

各成分之調配時的添加順序並無特別限定，亦可同時添加兩種以上之成分。 The order of addition of the components is not particularly limited, and two or more components may be added at the same time.

於使用溶劑之情形時，可藉由以下方式使用：將溶劑與溶劑以外之任一調配成分混合而將該調配成分預先稀釋；或者不將溶劑以外之任一調配成分預先稀釋，而將溶劑與該等調配成分混合。 When a solvent is used, it can be used by mixing a solvent with any of the components other than the solvent to pre-dilute the formulation; or not pre-diluting any of the components other than the solvent, and These formulated ingredients are mixed.

於調配時混合各成分的方法並無特別限定，可自如下方法等公知之方法中適切選擇：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機進行混合之方法；施加超音波進行混合之方法等。 The method of mixing the components at the time of blending is not particularly limited, and can be appropriately selected from a known method such as a method in which a stirrer or a stirring blade is rotated and mixed; a method of mixing using a mixer; and applying ultrasonic waves The method of mixing, etc.

關於各成分之添加以及混合時的溫度及時間，只要各調配成分不劣化則並無特別限定，只要適切調節即可，溫度較佳為15℃至30℃。 The temperature and time during the addition and mixing of the respective components are not particularly limited as long as the respective components do not deteriorate, and the temperature is preferably from 15 ° C to 30 ° C as long as it is appropriately adjusted.

<第一保護膜形成用片的製造方法> <Method for Producing First Protective Film Forming Sheet>

第一保護膜形成用片1A可藉由將上述各層以成為對應之位置關係之方式依序積層而製造。各層的形成方法如上文中所說明。 The first protective film forming sheet 1A can be produced by sequentially laminating the above layers in a corresponding positional relationship. The formation method of each layer is as described above.

例如於製造第一支持片11時，於在第一基材上積層第一黏著劑層或第一中間層之情形時，藉由在第一基材上塗敷上述第一黏著劑組成物或第一中間層形成用組成物，視需要進行乾燥，或照射能量線，可積層第一黏著劑層或第一中間層。 For example, when the first support sheet 11 is manufactured, when the first adhesive layer or the first intermediate layer is laminated on the first substrate, the first adhesive composition or the first adhesive is applied on the first substrate. A composition for forming an intermediate layer, which is dried as needed or irradiated with an energy ray, may be laminated with the first adhesive layer or the first intermediate layer.

另一方面，例如於在已積層於第一基材上之第一黏著劑層上進一步積層熱固化性樹脂膜之情形時，可於第一黏著劑層上塗敷熱固化性樹脂組成物或能量線固化性保護膜形成用組成物，直接形成熱固化性樹脂膜。同樣地，於在已積層於第一基材上之第一中間層上進一步積層第一黏著劑層之情形時，可於第一中間層上塗敷第一黏著劑組成物，直接形成第一黏著劑層。如此，於使用任一組成物形成連續兩層之積層結構之情形時，可於由前述組成物所形成之層上進一步塗敷組成物而新形成層。其中，較佳為於其他剝離膜上使用前述組成物預先形成該等兩層中的 後積層之層，將該經形成之層的與和前述剝離膜接觸之側為相反側的露出面與已形成之其餘層的露出面貼合，由此形成連續兩層之積層結構。此時，前述組成物較佳為塗敷於剝離膜的剝離處理面。剝離膜只要於形成積層結構後視需要而去除即可。 On the other hand, for example, when a thermosetting resin film is further laminated on the first adhesive layer which has been laminated on the first substrate, a thermosetting resin composition or energy may be applied to the first adhesive layer. A composition for forming a curable protective film directly forms a thermosetting resin film. Similarly, when the first adhesive layer is further laminated on the first intermediate layer which has been laminated on the first substrate, the first adhesive composition may be applied on the first intermediate layer to directly form the first adhesive. Agent layer. As described above, in the case where a laminate structure of two consecutive layers is formed using any of the compositions, the composition can be further coated on the layer formed of the above composition to newly form a layer. Wherein, it is preferred to use the foregoing composition on the other release film to form the two layers in advance. The layer of the post-layer is bonded to the exposed surface of the formed layer on the side opposite to the side in contact with the release film, and the exposed surface of the remaining layer formed, thereby forming a laminated structure of two consecutive layers. In this case, the composition is preferably applied to the release-treated surface of the release film. The release film may be removed as needed after forming a laminated structure.

例如於製造於第一基材上積層第一黏著劑層，於前述第一黏著劑層上積層固化性樹脂層而成之第一保護膜形成用片(第一支持片11為第一基材及第一黏著劑層之積層物的第一保護膜形成用片)1A之情形時，首先於第一基材上塗敷第一黏著劑組成物，視需要進行乾燥，或照射能量線，由此於第一基材上預先積層第一黏著劑層。另外，另於剝離膜上塗敷熱固化性樹脂組成物或能量線固化性保護膜形成用組成物，視需要進行乾燥，由此於剝離膜上預先形成含有熱固化性成分之熱固化性樹脂膜1。繼而，將該熱固化性樹脂膜1的露出面與已積層於第一基材上之第一黏著劑層的露出面貼合，將熱固化性樹脂膜1積層於第一黏著劑層上，由此可獲得第一保護膜形成用片1A。 For example, a first protective film forming sheet in which a first adhesive layer is laminated on a first substrate and a curable resin layer is laminated on the first adhesive layer (the first support sheet 11 is a first substrate) In the case of the first protective film forming sheet 1A of the laminate of the first adhesive layer, first, the first adhesive composition is applied onto the first substrate, and if necessary, dried or irradiated with an energy ray. A first adhesive layer is preliminarily laminated on the first substrate. In addition, a thermosetting resin composition or a composition for forming an energy ray-curable protective film is applied to the release film, and if necessary, a thermosetting resin film containing a thermosetting component is formed on the release film in advance. 1. Then, the exposed surface of the thermosetting resin film 1 is bonded to the exposed surface of the first adhesive layer laminated on the first substrate, and the thermosetting resin film 1 is laminated on the first adhesive layer. Thus, the first protective film forming sheet 1A can be obtained.

另外，例如於製造於第一基材上積層第一中間層，於前述第一中間層上積層第一黏著劑層而成之第一支持片11之情形時，首先於第一基材上塗敷第一中間層形成用組成物，視需要進行乾燥，或照射能量線，由此於第一基材上預先積層第一中間層。另外，另於剝離膜上塗敷第一黏著劑組成物，視需要進行乾燥，由此於剝離膜上預先形 成第一黏著劑層。繼而，將該第一黏著劑層的露出面與已積層於第一基材上之第一中間層的露出面貼合，將第一黏著劑層積層於第一中間層上，由此可獲得第一支持片11。於該情形時，例如進一步另於剝離膜上塗敷熱固化性樹脂組成物或能量線固化性保護膜形成用組成物，視需要進行乾燥，由此於剝離膜上預先形成含有熱固化性成分之熱固化性樹脂膜1。繼而，將該熱固化性樹脂膜1的露出面與已積層於第一中間層上之第一黏著劑層的露出面貼合，將熱固化性樹脂膜1積層於第一黏著劑層上，由此可獲得第一保護膜形成用片1A。 Further, for example, in the case where the first intermediate layer is laminated on the first substrate, and the first support sheet 11 is formed by laminating the first adhesive layer on the first intermediate layer, first coating on the first substrate The first intermediate layer forming composition is dried as needed or irradiated with an energy ray to thereby laminate a first intermediate layer on the first substrate. Further, the first adhesive composition is applied to the release film, and dried as needed, thereby preliminarily forming on the release film. Into the first adhesive layer. Then, the exposed surface of the first adhesive layer is bonded to the exposed surface of the first intermediate layer laminated on the first substrate, and the first adhesive is laminated on the first intermediate layer, thereby obtaining The first support sheet 11. In this case, for example, a thermosetting resin composition or an energy ray-curable protective film-forming composition is applied to the release film, and if necessary, dried to form a thermosetting component on the release film. Thermosetting resin film 1. Then, the exposed surface of the thermosetting resin film 1 is bonded to the exposed surface of the first adhesive layer laminated on the first intermediate layer, and the thermosetting resin film 1 is laminated on the first adhesive layer. Thus, the first protective film forming sheet 1A can be obtained.

再者，於在第一基材上積層第一黏著劑層或第一中間層之情形時，亦可代替如上所述般於第一基材上塗敷第一黏著劑組成物或第一中間層形成用組成物之方法，而於剝離膜上塗敷第一黏著劑組成物或第一中間層形成用組成物，視需要進行乾燥，或照射能量線，由此於剝離膜上預先形成第一黏著劑層或第一中間層，將該等層的露出面與第一基材的一方的表面貼合，由此將第一黏著劑層或第一中間層積層於基材上。 Furthermore, in the case where the first adhesive layer or the first intermediate layer is laminated on the first substrate, the first adhesive composition or the first intermediate layer may be applied on the first substrate instead of the above. A method of forming a composition, and applying a first adhesive composition or a first intermediate layer forming composition to the release film, drying or irradiating an energy ray as needed, thereby forming a first adhesive on the release film in advance The first adhesive layer or the first intermediate layer is laminated on the substrate by bonding the exposed surface of the layers to one surface of the first substrate.

於任一方法中，剝離膜只要以形成目標積層結構之後的任意時序而去除即可。 In any of the methods, the release film may be removed at any timing after the formation of the target laminate structure.

如此，構成第一保護膜形成用片1A之第一基材以外的層均可利用預先形成於剝離膜上、並貼合於目標層的表 面之方法而積層，故只要視需要適切選擇採用此種工序之層而製造第一保護膜形成用片1A即可。 In this manner, the layer other than the first base material constituting the first protective film forming sheet 1A can be formed by being formed on the release film in advance and attached to the target layer. In the case of the surface layer, the first protective film forming sheet 1A can be produced by appropriately selecting a layer using such a step as needed.

再者，第一保護膜形成用片1A通常係以於其之與第一支持片11為相反側之最表層(例如熱固化性樹脂膜1)的表面貼合有剝離膜之狀態而保管。因此，於該剝離膜(較佳為其剝離處理面)上塗敷熱固化性樹脂組成物或能量線固化性保護膜形成用組成物等用以形成構成最表層之層的組成物，視需要進行乾燥，由此於剝離膜上預先形成構成最表層之層，於該層的與和剝離膜接觸之側為相反側的露出面上利用上述任一方法積層其餘各層，不將剝離膜去除而保持貼合之狀態，由此亦可獲得第一保護膜形成用片1A。 In addition, the first protective film forming sheet 1A is usually stored in a state in which a peeling film is bonded to the surface of the outermost layer (for example, the thermosetting resin film 1) on the opposite side of the first support sheet 11. Therefore, a composition for forming a layer forming the outermost layer, such as a composition for forming a thermosetting resin composition or an energy ray-curable protective film, or the like, is applied to the release film (preferably as a release-treated surface), if necessary. After drying, the layer constituting the outermost layer is formed in advance on the release film, and the remaining layers are laminated on the exposed surface of the layer opposite to the side in contact with the release film by any of the above methods, and the release film is not removed. In the bonded state, the first protective film forming sheet 1A can also be obtained.

<第二保護膜形成膜及第二保護膜形成用片> <Second protective film forming film and second protective film forming sheet>

本發明中，除了上述第一保護膜形成用片1A以外，如圖5所示，可進一步採用第二保護膜形成膜2以於第二支持片21的一方的表面21a上具備第二保護膜形成用片2A之形式而包含於膜組件10(參照圖1A等)中之構成。 In the present invention, in addition to the first protective film forming sheet 1A, as shown in FIG. 5, the second protective film forming film 2 may be further used to provide a second protective film on one surface 21a of the second supporting sheet 21. The formation of the sheet 2A is included in the film assembly 10 (see FIG. 1A and the like).

作為第二支持片21，並無特別限定，可採用具有與如上所述之第一保護膜形成用片1A、第一保護膜形成用片1B、第一保護膜形成用片1C所具備之第一支持片11、第一支持片11A、第一支持片11B相同之材料及厚度者。 亦即，圖5中雖省略詳細之圖示，但作為第二支持片21，亦可採用第二保護膜形成膜2於第一基材上直接接觸之構成者，或者，亦可採用於第一基材與第二保護膜形成膜2之間進一步設有第一中間層或第一黏著劑層者。 The second support sheet 21 is not particularly limited, and the first protective film forming sheet 1A, the first protective film forming sheet 1B, and the first protective film forming sheet 1C may be used. The material and thickness of the support sheet 11, the first support sheet 11A, and the first support sheet 11B are the same. That is, although the detailed illustration is omitted in FIG. 5, as the second support sheet 21, the second protective film forming film 2 may be directly contacted on the first substrate, or may be used in the first A first intermediate layer or a first adhesive layer is further provided between a substrate and the second protective film forming film 2.

如上所述，第二保護膜形成膜2係用以形成保護半導體晶圓5的背面5b側之第二保護膜2a的膜，與熱固化性樹脂膜1同樣地至少含有熱固化性成分而構成。而且，可採用由與如上所述之熱固化性樹脂膜1相同之組成物所構成者作為第二保護膜形成膜2。 As described above, the second protective film forming film 2 is formed to form a film that protects the second protective film 2a on the back surface 5b side of the semiconductor wafer 5, and contains at least a thermosetting component in the same manner as the thermosetting resin film 1. . Further, as the second protective film forming film 2, a member composed of the same composition as the thermosetting resin film 1 described above can be used.

另外，作為第二保護膜形成膜2，可設為進一步含有著色劑之構成。 Further, the second protective film forming film 2 may have a configuration in which a coloring agent is further contained.

作為此種著色劑，可使用有機或無機之顏料及染料。 As such a coloring agent, organic or inorganic pigments and dyes can be used.

作為染料，例如可使用酸性染料、反應染料、直接染料、分散染料、陽離子染料等任意之染料。 As the dye, for example, any dye such as an acid dye, a reactive dye, a direct dye, a disperse dye, or a cationic dye can be used.

另外，作為顏料，並無特別限制，可自公知之顏料中適切選擇而使用。 Further, the pigment is not particularly limited, and can be appropriately selected from known pigments and used.

該等中，就電磁波或紅外線的遮蔽性良好，且可進一步提高雷射標記法之辨識性之觀點而言，較佳為使用黑色顏料。 Among these, it is preferable to use a black pigment from the viewpoint of good shielding properties of electromagnetic waves or infrared rays and further improving the visibility of the laser marking method.

作為黑色顏料，例如可列舉：碳黑、氧化鐵、二氧化錳、苯胺黑、活性炭等，就可提高半導體晶片之可靠性之觀點而言，較佳為碳黑。 Examples of the black pigment include carbon black, iron oxide, manganese dioxide, nigrosine, and activated carbon. From the viewpoint of improving the reliability of the semiconductor wafer, carbon black is preferred.

再者，該等著色劑可單獨使用或組合使用兩種以上。 Further, these colorants may be used alone or in combination of two or more.

相對於形成第二保護膜形成膜2之組成物的總質量(100質量%)，第二保護膜形成膜2中的著色劑的含量較佳為0.01質量%至30質量%，更佳為0.05質量%至25質量%，進而佳為0.1質量%至15質量%，進而更佳為0.15質量%至5質量%。 The content of the coloring agent in the second protective film forming film 2 is preferably from 0.01% by mass to 30% by mass, more preferably 0.05, based on the total mass (100% by mass) of the composition forming the second protective film forming film 2. The mass% is 25% by mass, and more preferably 0.1% by mass to 15% by mass, and still more preferably 0.15% by mass to 5% by mass.

再者，作為第二保護膜形成膜2的厚度，亦只要設定為與如上所述之熱固化性樹脂膜1相同程度即可。 In addition, the thickness of the second protective film forming film 2 may be set to be the same as that of the thermosetting resin film 1 described above.

<<作用功效>> <<Efficacy>>

如以上所說明，根據本發明之熱固化性樹脂膜與第二保護膜形成膜的組件、熱固化性樹脂膜、具備該熱固化性樹脂膜之第一保護膜形成用片，藉由使貼附於半導體晶圓的表面之熱固化性樹脂膜、與貼附於背面之第二保護膜形成膜之間的發熱起始溫度及發熱峰溫度的關係最適化，使因將熱固化性樹脂膜加熱固化時的收縮等而賦予至半導體晶圓之應力受到將第二保護膜形成膜加熱固化時之應力的矯正。藉此，可抑制半導體晶圓中產生翹曲，可製造可靠性優異之半導體封裝。 As described above, the thermosetting resin film of the present invention and the second protective film forming film assembly, the thermosetting resin film, and the first protective film forming sheet having the thermosetting resin film are provided by the paste. The relationship between the heat-generating resin film and the heat-generating peak temperature between the thermosetting resin film attached to the surface of the semiconductor wafer and the second protective film forming film attached to the back surface is optimized, and the thermosetting resin film is used. The stress applied to the semiconductor wafer during shrinkage or the like at the time of heat curing is corrected by the stress when the second protective film forming film is cured by heating. Thereby, warpage can be suppressed in the semiconductor wafer, and a semiconductor package excellent in reliability can be manufactured.

進而，根據本發明之半導體晶圓用第一保護膜的形成方法，與上述同樣地，其為半導體晶圓的表面側之熱固化 性樹脂膜、與背面側的第二保護膜形成膜之間的發熱起始溫度及發熱峰溫度的關係經最適化之方法，故可於在半導體晶圓的表面形成保護膜之固化步驟中，抑制半導體晶圓中產生翹曲，與上述同樣地，可製造可靠性優異之半導體封裝。 Further, according to the method of forming the first protective film for a semiconductor wafer of the present invention, in the same manner as described above, it is a heat curing of the surface side of the semiconductor wafer. The relationship between the heat generation onset temperature and the exothermic peak temperature between the resin film and the second protective film forming film on the back side is optimized, so that the curing step of forming a protective film on the surface of the semiconductor wafer can be performed. It is possible to suppress warpage in the semiconductor wafer, and it is possible to manufacture a semiconductor package having excellent reliability as described above.

再者，本發明之熱固化性樹脂膜與第二保護膜形成膜的組件例如可採用以下之構成。 Further, the module for forming a film of the thermosetting resin film and the second protective film of the present invention may have the following constitution, for example.

亦即，本發明之熱固化性樹脂膜與第二保護膜形成膜的組件可設定為如下構成：熱固化性樹脂膜1的藉由示差掃描熱量分析法所測定之發熱起始溫度為第二保護膜形成膜2的藉由示差掃描熱量分析法所測定之發熱起始溫度以上，更且，熱固化性樹脂膜1及第二保護膜形成膜2的藉由示差掃描熱量分析法所測定之發熱峰溫度分別為185℃至200℃，熱固化性樹脂膜1與第二保護膜形成膜2的發熱峰溫度之差為0℃至10℃之範圍。 In other words, the thermosetting resin film of the present invention and the second protective film forming film may be configured as follows: the heat-starting temperature of the thermosetting resin film 1 measured by the differential scanning calorimetry is second. The heat-generating starting temperature of the protective film forming film 2 measured by the differential scanning calorimetry method is more than, and the thermosetting resin film 1 and the second protective film forming film 2 are measured by differential scanning calorimetry. The exothermic peak temperature is 185 ° C to 200 ° C, and the difference between the exothermic peak temperatures of the thermosetting resin film 1 and the second protective film forming film 2 is in the range of 0 ° C to 10 ° C.

另外，本發明之熱固化性樹脂膜1與第二保護膜形成膜2的組件可採用如下構成：熱固化性樹脂膜1的線膨脹係數為47(×10-6/℃)至80(×10-6/℃)之範圍，且與第二保護膜形成膜2的線膨脹係數之差為3(×10-6/℃)至30(×10-6/℃)之範圍。 Further, the assembly of the thermosetting resin film 1 and the second protective film forming film 2 of the present invention may be configured such that the coefficient of linear expansion of the thermosetting resin film 1 is 47 (×10 -6 /° C.) to 80 (×). The range of 10 -6 /° C) and the difference in linear expansion coefficient from the second protective film forming film 2 is in the range of 3 (×10 -6 /° C.) to 30 (×10 -6 /° C.).

[實施例] [Examples]

繼而，示出實施例及比較例對本發明加以更具體說 明。再者，本發明之範圍不受本實施例之限制，本發明之熱固化性樹脂膜與第二保護膜形成膜的組件、熱固化性樹脂膜、第一保護膜形成用片及半導體晶圓用第一保護膜的形成方法可於不變更本發明之主旨之範圍內適切變更而實施。 Then, the embodiments and comparative examples are shown to more specifically describe the present invention. Bright. Further, the scope of the present invention is not limited by the present embodiment, and the thermosetting resin film and the second protective film forming film assembly, the thermosetting resin film, the first protective film forming sheet, and the semiconductor wafer of the present invention are not limited. The method of forming the first protective film can be carried out without departing from the scope of the present invention.

以下示出用於製造熱固化性樹脂組成物之成分。 The components for producing a thermosetting resin composition are shown below.

．聚合物成分 . Polymer composition

聚合物成分(A)-1：將丙烯酸丁酯(以下簡稱為「BA」)(55質量份)、丙烯酸甲酯(以下簡稱為「MA」)(10質量份)、甲基丙烯酸縮水甘油酯(以下簡稱為「GMA」)(20質量份)及丙烯酸-2-羥基乙酯(以下簡稱為「HEA」)(15質量份)共聚合而成之丙烯酸系樹脂(重量平均分子量800000，玻璃轉移溫度-28℃)。將各成分之調配比示於下述表1中。 Polymer component (A)-1: butyl acrylate (hereinafter abbreviated as "BA") (55 parts by mass), methyl acrylate (hereinafter abbreviated as "MA") (10 parts by mass), glycidyl methacrylate (hereinafter referred to as "GMA") (20 parts by mass) and acrylic acid 2-hydroxyethyl acrylate (hereinafter referred to as "HEA") (15 parts by mass) copolymerized acrylic resin (weight average molecular weight 800,000, glass transfer) Temperature -28 ° C). The blending ratio of each component is shown in Table 1 below.

．環氧樹脂 . Epoxy resin

環氧樹脂(B1)-1：液狀雙酚F型環氧樹脂(三菱化學公司製造，「YL983U」)。 Epoxy resin (B1)-1: liquid bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation, "YL983U").

環氧樹脂(B1)-2：多官能芳香族型環氧樹脂(日本化藥公司製造，「EPPN-502H」)。 Epoxy Resin (B1)-2: Polyfunctional aromatic epoxy resin (manufactured by Nippon Kayaku Co., Ltd., "EPPN-502H").

環氧樹脂(B1)-3：二環戊二烯型環氧樹脂(DIC公司製造，「EPICLON HP-7200」)。 Epoxy resin (B1)-3: Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, "EPICLON HP-7200").

．熱固化劑 . Heat curing agent

熱固化劑(B2)-1：酚醛清漆型酚樹脂(昭和電工公司製 造，「BRG-556」)。 Heat curing agent (B2)-1: Novolac type phenol resin (made by Showa Denko) Made, "BRG-556").

．固化促進劑 . Curing accelerator

固化促進劑(C)-1：2-苯基-4,5-二羥基甲基咪唑(四國化成工業公司製造，「Curezole 2PHZ-PW」)。 Curing accelerator (C)-1: 2-phenyl-4,5-dihydroxymethylimidazole ("Curezole 2PHZ-PW", manufactured by Shikoku Chemical Industries, Ltd.).

．填充材料 . Filler

填充材料(D)-1：經環氧基修飾之球狀二氧化矽(Admatechs公司製造，「Admanano YA050C-MKK」，平均粒徑0.05μm)。 Filler (D)-1: spherical cerium oxide modified by an epoxy group ("Admanano YA050C-MKK" manufactured by Admatechs Co., Ltd., average particle diameter: 0.05 μm).

．顏料 . pigment

黑色顏料(L)-1：東洋油墨公司製造，「Multirac A-903黑」。 Black pigment (L)-1: manufactured by Toyo Ink Co., Ltd., "Multirac A-903 Black".

[實施例1] [Example 1]

<第一保護膜形成用片(熱固化性樹脂膜)的製造> <Manufacture of Sheet for Forming First Protective Film (Hot Curable Resin Film)>

(熱固化性樹脂組成物的製造) (Manufacture of thermosetting resin composition)

使聚合物成分(A)-1、環氧樹脂(B1)-1、環氧樹脂(B1)-2、環氧樹脂(B1)-3、熱固化劑(B2)-1、固化促進劑(C)-1及填充材料(D)-1以含量相對於溶劑以外之所有成分的總含量之比例成為下述表1所示之值(表1中記載為「含量之比例」)之方式溶解或分散於甲基乙基酮中，於23℃下攪拌，由此獲得固體成分濃度為55質量%之熱固化性樹脂組成物(III-1)作為熱固化性樹脂組成物。再者，下述表1中的含有成分的欄的「-」之記載係指熱固化性樹脂組成物不含該成分。 Polymer component (A)-1, epoxy resin (B1)-1, epoxy resin (B1)-2, epoxy resin (B1)-3, heat curing agent (B2)-1, curing accelerator ( C)-1 and the filler (D)-1 are dissolved in such a manner that the ratio of the content to the total content of all components other than the solvent is as shown in the following Table 1 (the ratio of "content" in Table 1). Or it is disperse|distributed in the methyl ethyl ketone, and it is stirring at 23 degreeC, and the thermosetting resin composition (III-1) of the solid- In addition, the "-" in the column containing a component in the following Table 1 means that the thermosetting resin composition does not contain this component.

(黏著性樹脂(I-2a)的製造) (Manufacture of adhesive resin (I-2a))

將丙烯酸-2-乙基己酯(以下簡稱為「2EHA」)(80質量份)、HEA(20質量份)作為共聚物的原料，進行聚合反應，由此獲得丙烯酸系聚合物。 2-ethylhexyl acrylate (hereinafter abbreviated as "2EHA") (80 parts by mass) and HEA (20 parts by mass) were used as a raw material of the copolymer to carry out a polymerization reaction, thereby obtaining an acrylic polymer.

於該丙烯酸系聚合物中添加2-甲基丙烯醯氧基乙基異氰酸酯(以下簡稱為「MOI」)(22質量份，相對於HEA而為約80mol%)，於空氣氣流中於50℃下進行48小時加成反應，由此獲得目標黏著性樹脂(I-2a)。 To the acrylic polymer, 2-methacryloxyethyl isocyanate (hereinafter abbreviated as "MOI") (22 parts by mass, about 80 mol% based on HEA) was added to the acrylic polymer at 50 ° C in an air stream. A 48-hour addition reaction was carried out, whereby the target adhesive resin (I-2a) was obtained.

(第一黏著劑組成物的製造) (Manufacture of the first adhesive composition)

相對於上述所得之黏著性樹脂(I-2a)(100質量份)，添加三羥甲基丙烷之甲苯二異氰酸酯三聚物加成物(東梭(Tosoh)公司製造，「Coronate L」)(0.5質量份)作為異氰酸酯系交聯劑，於23℃下攪拌，由此獲得固體成分濃度為30質量%之第一黏著劑組成物(I-2)作為第一黏著劑組成物。再者，該「第一黏著劑組成物的製造」中的調配份數全部為固體成分換算值。 To the above-mentioned adhesive resin (I-2a) (100 parts by mass), a toluene diisocyanate trimer adduct of trimethylolpropane (manufactured by Tosoh Co., "Coronate L") was added ( 0.5 parts by mass) was stirred at 23 ° C as an isocyanate crosslinking agent to obtain a first adhesive composition (I-2) having a solid content concentration of 30% by mass as a first adhesive composition. In addition, the number of the preparation parts in the "manufacture of the first adhesive composition" is all a solid content conversion value.

(第一保護膜形成用片的製造) (Manufacture of sheet for forming a first protective film)

於藉由矽酮處理將聚對苯二甲酸乙二酯製膜的單面進行剝離處理所得之剝離膜(Lintec公司製造，「SP-PET381031」，厚度38μm)的前述剝離處理面，塗敷上述所得之第一黏著劑組成物，於120℃下進行2分鐘加 熱乾燥，藉此形成厚度60μ.m之第一黏著劑層。 The peeling treatment surface of the release film ("SP-PET381031", thickness: 38 μm, manufactured by Lintec Co., Ltd.) obtained by peeling off one side of the polyethylene terephthalate film by fluorenone treatment was applied to the above-mentioned peeling treatment surface. The obtained first adhesive composition was added at 120 ° C for 2 minutes. It was thermally dried to thereby form a first adhesive layer having a thickness of 60 μm.

繼而，於該第一黏著劑層的露出面，貼合作為第一基材之將聚烯烴膜(厚度25μm)、接著劑層(厚度2.5μm)、聚對苯二甲酸乙二酯膜(厚度50μm)、接著劑層(厚度2.5μm)及聚烯烴膜(厚度25μm)依序積層而成的厚度105μm之積層膜，藉此獲得第一支持片。 Then, on the exposed surface of the first adhesive layer, the polyolefin film (thickness 25 μm), the adhesive layer (thickness 2.5 μm), and the polyethylene terephthalate film (thickness) adhered to the first substrate. 50 μm), an adhesive layer (thickness: 2.5 μm), and a laminate film of a thickness of 105 μm in which a polyolefin film (thickness: 25 μm) was sequentially laminated, thereby obtaining a first support sheet.

於藉由矽酮處理將聚對苯二甲酸乙二酯製膜的單面進行剝離處理所得之剝離膜(Lintec公司製造，「SP-PET381031」，厚度38μm)的剝離處理面，塗敷上述所得之熱固化性樹脂組成物，於100℃下進行2分鐘乾燥，藉此製作厚度40μm之熱固化性樹脂膜。 The release treatment surface of a release film ("SP-PET381031", thickness: 38 μm, manufactured by Lintec Co., Ltd.) obtained by peeling a single surface of a polyethylene terephthalate film by an oxime treatment was applied to the above-mentioned surface. The thermosetting resin composition was dried at 100 ° C for 2 minutes to prepare a thermosetting resin film having a thickness of 40 μm.

繼而，自上述所得之第一支持片的第一黏著劑層去除剝離膜，於該第一黏著劑層的露出面，貼合上述所得之熱固化性樹脂膜的露出面，獲得將第一基材、第一黏著劑層、熱固化性樹脂膜及剝離膜於該等的厚度方向依序積層而成之第一保護膜形成用片。 Then, the release film is removed from the first adhesive layer of the first support sheet obtained above, and the exposed surface of the thermosetting resin film obtained above is bonded to the exposed surface of the first adhesive layer to obtain the first base. The first protective film forming sheet in which the material, the first adhesive layer, the thermosetting resin film, and the release film are sequentially laminated in the thickness direction.

(第二保護膜形成膜的製造) (Manufacture of second protective film forming film)

使用與上述相同之剝離膜(Lintec公司製造，「SP-PET381031」)，於其剝離處理面塗敷與上述所得之熱固化性樹脂組成物同樣地獲得的下述表2所示之組成之第二保護膜形成膜形成用組成物後，於100℃下進行2 分鐘乾燥，藉此製作厚度40μm之熱固化性樹脂膜(第二保護膜形成膜)。 The peeling film ("SP-PET381031" manufactured by Lintec Co., Ltd.) was used, and the composition shown in the following Table 2 obtained in the same manner as the thermosetting resin composition obtained above was applied to the release treated surface. After the second protective film is formed into a film forming composition, it is carried out at 100 ° C. 2 After drying in a minute, a thermosetting resin film (second protective film forming film) having a thickness of 40 μm was produced.

繼而，使用具有與上述第一支持片相同之構成之第二支持片，自該第二支持片的第一黏著劑層去除剝離膜，於該第一黏著劑層的露出面，貼合上述所得之第二保護膜形成膜的露出面，獲得將第一基材、第一黏著劑層、第二保護膜形成膜及剝離膜於該等的厚度方向依序積層而成之第二保護膜形成用片。 Then, using the second support sheet having the same configuration as the first support sheet, the release film is removed from the first adhesive layer of the second support sheet, and the obtained surface is adhered to the exposed surface of the first adhesive layer. The second protective film forms an exposed surface of the film, and a second protective film formed by sequentially laminating the first base material, the first adhesive layer, the second protective film forming film, and the release film in the thickness direction is obtained. Use tablets.

<熱固化性樹脂膜及第二保護膜形成膜之評價> <Evaluation of Thermosetting Resin Film and Second Protective Film Forming Film>

(各膜的發熱峰溫度以及線膨脹係數之測定) (Measurement of the exothermic peak temperature and coefficient of linear expansion of each film)

使用上述所得之熱固化性樹脂組成物，除了其塗敷量不同之方面以外，利用與上述第一保護膜形成用片的製造時相同之方法製作厚度50μm之熱固化性樹脂膜，使其積層10層，製作厚度500μm之熱固化性樹脂膜。 A thermosetting resin film having a thickness of 50 μm was produced by the same method as in the production of the first protective film-forming sheet, except that the coating amount of the thermosetting resin composition obtained above was different. In 10 layers, a thermosetting resin film having a thickness of 500 μm was produced.

另外，同樣地使用上述所得之第二保護膜形成膜形成用組成物，除了其塗敷量不同之方面以外，利用與上述第二保護膜形成膜的製造時相同的方法製作厚度50μm之由熱固化性樹脂構成之第二保護膜形成膜，使其積層10層，製作厚度500μm之第二保護膜形成膜。 In addition, the second protective film forming film-forming composition obtained as described above was used in the same manner as in the production of the second protective film forming film, and the heat of 50 μm in thickness was produced. A second protective film formed of a curable resin was formed into a film, and 10 layers were laminated to form a second protective film forming film having a thickness of 500 μm.

繼而，由該熱固化性樹脂膜製作評價用試樣，使用先前公知之示差掃描熱量分析裝置來測定發熱峰溫度。 Then, a sample for evaluation was prepared from the thermosetting resin film, and the peak of the exothermic peak was measured using a conventionally known differential scanning calorimeter.

同樣地，由熱固化性樹脂膜製作評價用試樣，於依據JIS K 7197之條件下，使用先前公知之熱機械分析(TMA；Thermo Mechanical Analysis)裝置測定熱膨脹係數(CTE α1)。 Similarly, a sample for evaluation was prepared from a thermosetting resin film, and the coefficient of thermal expansion (CTE α1) was measured using a previously known thermomechanical analysis (TMA) device in accordance with JIS K 7197.

將該等各試驗之測定結果示於下述表3中。 The measurement results of the respective tests are shown in Table 3 below.

如下述表3所示，於實施例1中，可確認熱固化性樹脂膜及第二保護膜形成膜的發熱峰溫度均為185℃，在本發明所規定之範圍內。另外，實施例1中，可確認熱固化性樹脂膜的線膨脹係數為47(×10-6/℃)，第二保護膜形成膜的線膨脹係數為50(×10-6/℃)，在本發明所規定之範圍內。 As shown in the following Table 3, in the first embodiment, it was confirmed that the heat-generating resin film and the second protective film-forming film had a heat-generating peak temperature of 185 ° C, which is within the range defined by the present invention. Further, in Example 1, it was confirmed that the linear expansion coefficient of the thermosetting resin film was 47 (×10 -6 /° C.), and the coefficient of linear expansion of the second protective film forming film was 50 (×10 -6 /° C.). Within the scope of the invention.

<保護膜形成後之半導體晶圓之評價> <Evaluation of semiconductor wafer after formation of protective film>

(熱固化性樹脂膜固化而形成第一保護膜後之翹曲之確認) (Confirmation of warpage after curing of the thermosetting resin film to form the first protective film)

使用上述所得之熱固化性樹脂膜(熱固化性樹脂膜與第二保護膜形成膜的組件)，於半導體晶圓的凸塊形成面形成第一保護膜，並且於背面形成第二保護膜。 Using the thermosetting resin film (the assembly of the thermosetting resin film and the second protective film forming film) obtained above, a first protective film is formed on the bump forming surface of the semiconductor wafer, and a second protective film is formed on the back surface.

亦即，首先於表面具備複數個凸塊之半導體晶圓的背面側貼著第二保護膜形成膜，並且於表面側貼著第一保護膜形成用片，製作將第二保護膜形成膜、半導體晶圓、第一保護膜形成用片(熱固化性樹脂膜)依序積層而成之積層體。另外，此時，作為第二保護膜形成膜，使用在與貼 著於半導體晶圓的背面之面為相反側的面貼著有切割膠帶者。 In other words, first, a second protective film forming film is adhered to the back surface side of the semiconductor wafer having a plurality of bumps on the surface thereof, and a first protective film forming film is attached to the front surface side to form a second protective film forming film. The semiconductor wafer and the first protective film forming sheet (thermosetting resin film) are laminated in a layered manner. In addition, at this time, as a second protective film forming film, it is used in and attached. The surface on the opposite side of the semiconductor wafer is attached to the surface on the opposite side with the dicing tape.

繼而，使用貼著於第二保護膜形成膜之切割膠帶，將切割膠帶貼著於晶圓切割用環形框架，由此將積層體(半導體晶圓)固定於環形框架上，並且自第一保護膜形成用片剝離支持片。 Then, using a dicing tape attached to the second protective film forming film, the dicing tape is attached to the ring frame for wafer dicing, thereby fixing the laminated body (semiconductor wafer) to the ring frame, and the first protection The film forming sheet peels off the support sheet.

繼而，使用加壓加熱固化裝置(Lintec公司製造，「RAD-9100」)，對於經固定於晶圓切割用環形框架之半導體晶圓上的熱固化性樹脂膜，一面施加0.5MPa之壓力一面於設定溫度180℃下加熱1小時，使熱固化性樹脂膜軟化後，使其固化而形成第一保護膜。另外，與此同時，使第二保護膜形成膜軟化後，使其固化，藉此形成第二保護膜。 Then, using a pressure heating and curing device ("RAD-9100" manufactured by Lintec Co., Ltd.), the thermosetting resin film fixed on the semiconductor wafer of the ring frame for wafer dicing is applied with a pressure of 0.5 MPa. After heating at a set temperature of 180 ° C for 1 hour, the thermosetting resin film was softened and then cured to form a first protective film. Further, at the same time, the second protective film forming film is softened and then cured to form a second protective film.

繼而，藉由切割處理將各面形成有第一保護膜及第二保護膜之半導體晶圓切成晶片單位後，將經分割成晶片單位之半導體晶圓一面去除切割膠帶一面自環形框架剝離而取下。 Then, the semiconductor wafer in which the first protective film and the second protective film are formed on each surface is cut into wafer units by a dicing process, and the semiconductor wafer divided into wafer units is peeled off from the ring frame while removing the dicing tape. Take it down.

繼而，目測確認第一保護膜及第二保護膜形成後之半導體晶圓的翹曲之產生之有無，並且目測確認半導體晶圓的端部之翹曲的方向(朝向熱固化性樹脂膜側或第二保護 膜形成膜側之哪一個)。將其結果示於下述表3中。 Then, the presence or absence of warpage of the semiconductor wafer after the formation of the first protective film and the second protective film was visually observed, and the direction of warpage of the end portion of the semiconductor wafer was visually confirmed (toward the side of the thermosetting resin film or Second protection Which one of the film formation film side). The results are shown in Table 3 below.

如下述表3所示，使用具有本發明之構成之膜組件於半導體晶圓的凸塊形成面形成第一保護膜(於背面形成第二保護膜)之實施例1中，可確認使熱固化性樹脂膜固化而形成第一保護膜後未產生翹曲。 As shown in the following Table 3, in Example 1 in which the film assembly having the constitution of the present invention was used to form the first protective film on the bump forming surface of the semiconductor wafer (the second protective film was formed on the back surface), it was confirmed that the film was thermally cured. The resin film was cured to form no warp after the formation of the first protective film.

[實施例2、實施例3] [Example 2, Example 3]

除了如下述表1所示般設定熱固化性樹脂組成物組成之方面以外，與實施例1同樣地製造含有第一保護膜形成用片及第二保護膜形成膜之實施例2、實施例3之膜組件，與上述同樣地評價，將其結果示於下述表3中。 Example 2 and Example 3 containing the first protective film forming sheet and the second protective film forming film were produced in the same manner as in Example 1 except that the composition of the thermosetting resin composition was set as shown in the following Table 1. The membrane module was evaluated in the same manner as above, and the results are shown in Table 3 below.

如下述表3所示，實施例2、實施例3中，亦與實施例1之情形同樣地，可確認熱固化性樹脂膜及第二保護膜形成膜的發熱峰溫度均為185℃或195℃，在本發明所規定之範圍內。同樣地可確認，實施例2中，熱固化性樹脂膜的線膨脹係數為47(×10-6/℃)，第二保護膜形成膜的線膨脹係數為50(×10-6/℃)，實施例3中，熱固化性樹脂膜的線膨脹係數為80(×10-6/℃)，第二保護膜形成膜的線膨脹係數為50(×10-6/℃)，在本發明所規定之範圍內。 As shown in the following Table 3, in the same manner as in the case of Example 1, it was confirmed that the heat-generating peak temperature of the thermosetting resin film and the second protective film forming film was 185 ° C or 195. °C, within the scope of the invention. Similarly, in Example 2, the coefficient of linear expansion of the thermosetting resin film was 47 (×10 -6 /° C.), and the coefficient of linear expansion of the film formed of the second protective film was 50 (×10 -6 /° C.). In the third embodiment, the coefficient of linear expansion of the thermosetting resin film is 80 (×10 -6 /° C.), and the coefficient of linear expansion of the second protective film forming film is 50 (×10 -6 /° C.), in the present invention. Within the specified range.

而且，如下述表3所示，使用具有本發明之構成之膜組件於半導體晶圓的凸塊形成面形成第一保護膜(於背面 形成第二保護膜)之實施例2、實施例3中，亦與實施例1同樣地，可確認使熱固化性樹脂膜固化而形成第一保護膜後未產生翹曲。 Further, as shown in Table 3 below, a first protective film is formed on the bump forming surface of the semiconductor wafer using the film assembly having the constitution of the present invention (on the back side) In Example 2 and Example 3 in which the second protective film was formed, in the same manner as in Example 1, it was confirmed that the thermosetting resin film was cured to form a first protective film, and warpage did not occur.

<第一保護膜形成用片的製造及評價> <Manufacture and Evaluation of First Protective Film Forming Sheet>

[比較例1、比較例2、參考例1、參考例2] [Comparative Example 1, Comparative Example 2, Reference Example 1, Reference Example 2]

除了如表1所示般設定熱固化性樹脂組成物組成之方面以外，與實施例1同樣地製造包含第一保護膜形成用片及第二保護膜形成膜的比較例1、比較例2之膜組件，與上述同樣地評價，將其結果示於下述表3中。 A comparative example 1 and a comparative example 2 including the first protective film forming sheet and the second protective film forming film were produced in the same manner as in Example 1 except that the composition of the thermosetting resin composition was set as shown in Table 1. The membrane module was evaluated in the same manner as above, and the results are shown in Table 3 below.

另外，本實驗中，不將第二保護膜形成膜貼著於半導體晶圓，而僅將熱固化性樹脂膜貼著於半導體晶圓並進行加熱固化，製作形成有第一保護膜之參考例1之試樣，並且不進行使用熱固化性樹脂膜之第一保護膜之形成，而僅將第二保護膜形成膜貼著於半導體晶圓並進行加熱固化，製作形成有第二保護膜之參考例2之試樣，與實施例同樣地評價，將其結果示於下述表3中。 Further, in this experiment, the second protective film forming film was not attached to the semiconductor wafer, and only the thermosetting resin film was stuck on the semiconductor wafer and heat-cured to prepare a reference example in which the first protective film was formed. The sample of 1 is not formed by using the first protective film using the thermosetting resin film, and only the second protective film forming film is adhered to the semiconductor wafer and heat-cured to form a second protective film. The sample of Reference Example 2 was evaluated in the same manner as in the examples, and the results are shown in Table 3 below.

如下述表3所示，比較例1之試樣係熱固化性樹脂膜的熱膨脹係數超過本發明的請求項2、請求項4所規定之上限，另外，熱固化性樹脂膜與第二保護膜形成膜之間的熱膨脹係數之差亦超過上限值。因此，比較例1中，以半導體晶圓的端部朝向凸塊形成面側(第一保護膜形成面側)之方式產生了翹曲。 As shown in the following Table 3, the thermal expansion coefficient of the sample-based thermosetting resin film of Comparative Example 1 exceeds the upper limit defined in the claims 2 and 4 of the present invention, and the thermosetting resin film and the second protective film are provided. The difference in thermal expansion coefficient between the formed films also exceeds the upper limit. Therefore, in Comparative Example 1, warpage occurred in such a manner that the end portion of the semiconductor wafer faces the bump forming surface side (the first protective film forming surface side).

另外，比較例2之試樣係熱固化性樹脂膜的發熱峰溫度超過本發明所規定之上限值，另外，熱固化性樹脂膜與第二保護膜形成膜之間的發熱峰溫度之差亦超過上限值。因此，比較例2中，以半導體晶圓的端部朝向凸塊形成面側(第一保護膜形成面側)之方式產生了翹曲。 In addition, the exothermic peak temperature of the sample-based thermosetting resin film of Comparative Example 2 exceeds the upper limit value defined by the present invention, and the difference in exothermic peak temperature between the thermosetting resin film and the second protective film forming film Also exceeds the upper limit. Therefore, in Comparative Example 2, warping occurred in such a manner that the end portion of the semiconductor wafer faces the bump forming surface side (the first protective film forming surface side).

再者，如下述表3所示，不將第二保護膜形成膜貼著於半導體晶圓而僅形成有第一保護膜之參考例1之試樣以半導體晶圓的端部朝向凸塊形成面側之方式產生了翹曲。 Further, as shown in the following Table 3, the sample of Reference Example 1 in which only the first protective film was formed without adhering the second protective film forming film to the semiconductor wafer was formed such that the end portion of the semiconductor wafer was formed toward the bump. The way of the face side produces warpage.

另外，不進行第一保護膜之形成而僅將第二保護膜形成膜貼著於半導體晶圓並進行加熱而僅形成有第二保護膜之參考例2之試樣以半導體晶圓的端部朝向背面側(第二保護膜形成膜側)之方式產生了翹曲。 In addition, the sample of Reference Example 2 in which only the second protective film is formed is adhered to the semiconductor wafer without heating the first protective film forming film, and the end portion of the semiconductor wafer is formed. Warpage is generated in such a manner as to face the back side (the second protective film forms the film side).

由以上所說明之實施例之結果可知，，藉由如本發明所規定般使貼附於半導體晶圓的表面之熱固化性樹脂膜、與貼附於背面之第二保護膜形成膜之間的發熱起始溫度及發熱峰溫度的關係最適化，而可抑制半導體晶圓中產生翹曲，可製造可靠性優異之半導體封裝。 As is apparent from the results of the examples described above, the thermosetting resin film attached to the surface of the semiconductor wafer and the second protective film formed on the back surface are formed between the films as defined in the present invention. The relationship between the heat generation start temperature and the heat generation peak temperature is optimized, and warpage can be suppressed in the semiconductor wafer, and a semiconductor package excellent in reliability can be manufactured.

(產業可利用性) (industry availability)

本發明可用於製造於覆晶安裝方法中使用的於連接墊部具有凸塊之半導體晶片等。 The present invention can be used for manufacturing a semiconductor wafer or the like having bumps in a connection pad portion used in a flip chip mounting method.

1‧‧‧熱固化性樹脂膜 1‧‧‧Hot Curable Resin Film

2‧‧‧第二保護膜形成膜 2‧‧‧Second protective film forming film

5‧‧‧半導體晶圓 5‧‧‧Semiconductor wafer

5a‧‧‧表面(凸塊形成面、電路面) 5a‧‧‧ Surface (bump forming surface, circuit surface)

5b‧‧‧背面 5b‧‧‧Back

10‧‧‧熱固化性樹脂膜與第二保護膜形成膜的組件(膜組件) 10‧‧‧The component of the film formed by the thermosetting resin film and the second protective film (membrane module)

50‧‧‧積層體 50‧‧‧Layered body

51‧‧‧凸塊 51‧‧‧Bumps

51a‧‧‧表面(凸塊的表面) 51a‧‧‧Surface (surface of the bump)

Claims (7)

一種熱固化性樹脂膜與第二保護膜形成膜的組件，係貼附於半導體晶圓而使用，且係用於形成將半導體晶圓的複數個凸塊予以保護之第一保護膜；並且，前述熱固化性樹脂膜與第二保護膜形成膜的組件包含熱固化性樹脂膜、及半導體晶圓的第二保護膜形成膜，前述熱固化性樹脂膜係用於藉由貼附於前述半導體晶圓的具有複數個凸塊之表面並進行加熱固化，而於前述表面形成第一保護膜；前述熱固化性樹脂膜及前述第二保護膜形成膜分別至少含有熱固化性成分；前述熱固化性樹脂膜的藉由示差掃描熱量分析法所測定之發熱起始溫度為前述第二保護膜形成膜的藉由示差掃描熱量分析法所測定之發熱起始溫度以上；並且，前述熱固化性樹脂膜及前述第二保護膜形成膜的藉由示差掃描熱量分析法所測定之發熱峰溫度分別為100℃至200℃，前述熱固化性樹脂膜與前述第二保護膜形成膜之前述發熱峰溫度的差小於35℃。 A thermosetting resin film and a second protective film forming film assembly are attached to a semiconductor wafer and used to form a first protective film that protects a plurality of bumps of the semiconductor wafer; The thermosetting resin film and the second protective film forming film assembly include a thermosetting resin film and a second protective film forming film of a semiconductor wafer, and the thermosetting resin film is used for attaching to the semiconductor a surface of the plurality of bumps on the wafer and heat-cured to form a first protective film on the surface; the thermosetting resin film and the second protective film forming film respectively contain at least a thermosetting component; the heat curing The heat generation starting temperature of the resin film measured by differential scanning calorimetry is higher than the heat generation starting temperature measured by differential scanning calorimetry of the second protective film forming film; and the aforementioned thermosetting resin The heat generating peak temperature of the film and the second protective film forming film measured by differential scanning calorimetry is 100 ° C to 200 ° C, respectively, and the aforementioned thermosetting resin film The difference between the second protective film is formed of the exothermic peak temperature of the film is less than 35 ℃. 如請求項1所記載之熱固化性樹脂膜與第二保護膜形成膜的組件，其中前述熱固化性樹脂膜的線膨脹係數為5×10-6/℃至80×10-6/℃，且與前述第二保護膜形成膜的線膨脹係數之差小於35×10-6/℃。 The module for forming a film of the thermosetting resin film and the second protective film according to claim 1, wherein the thermosetting resin film has a linear expansion coefficient of from 5 × 10 -6 / ° C to 80 × 10 -6 / ° C, And the difference between the linear expansion coefficients of the film formed by the second protective film is less than 35 × 10 -6 / °C. 如請求項1或2所記載之熱固化性樹脂膜與第二保護膜形成膜的組件，其中，前述熱固化性樹脂膜係以於第一支持片的一方的表面上具備第一保護膜形成用片之形式而包含於前述熱固化性樹脂膜與第二保護膜形成膜的組件中，並且前述第二保護膜形成膜以於第二支持片的一方的表面上具備第二保護膜形成用片之形式而包含於前述熱固化性樹脂膜與第二保護膜形成膜的組件中。 The thermosetting resin film according to claim 1 or 2, wherein the thermosetting resin film is provided with a first protective film on one surface of the first support sheet. The second protective film forming film is provided in the assembly of the thermosetting resin film and the second protective film forming film in the form of a sheet, and the second protective film forming film is provided on the surface of the second supporting sheet. The sheet form is included in the assembly of the thermosetting resin film and the second protective film forming film. 一種熱固化性樹脂膜，係貼附於半導體晶圓而使用，且係為了藉由貼附於半導體晶圓的具有複數個凸塊之表面並進行加熱固化而於前述表面形成第一保護膜，而與半導體晶圓的第二保護膜形成膜組合使用；前述熱固化性樹脂膜及前述第二保護膜形成膜分別至少含有熱固化性成分；前述熱固化性樹脂膜的藉由示差掃描熱量分析法所測定之發熱起始溫度為前述第二保護膜形成膜的藉由示差掃描熱量分析法所測定之發熱起始溫度以上；並且，前述熱固化性樹脂膜及前述第二保護膜形成膜的藉由示差掃描熱量分析法所測定之發熱峰溫度分別為100℃至200℃，前述熱固化性樹脂膜與前述第二保護膜形成膜的前述發熱峰溫度之差小於35℃。 A thermosetting resin film which is used by being attached to a semiconductor wafer and which is formed on the surface by a surface having a plurality of bumps attached to a semiconductor wafer and cured by heating, And the second protective film forming film of the semiconductor wafer is used in combination; the thermosetting resin film and the second protective film forming film each contain at least a thermosetting component; and the thermosetting resin film is analyzed by differential scanning calorimetry The heat generation onset temperature measured by the method is equal to or higher than the heat generation onset temperature measured by differential scanning calorimetry of the second protective film forming film; and the heat curable resin film and the second protective film are formed into a film. The exothermic peak temperature measured by differential scanning calorimetry is 100 ° C to 200 ° C, and the difference between the heat-generating resin film and the heat-generating peak temperature of the second protective film forming film is less than 35 ° C. 如請求項4所記載之熱固化性樹脂膜，其中進而以如下形式使用：前述熱固化性樹脂膜的線膨脹係數為5×10-6/℃至80×10-6/℃，且與前述第二保護膜形成膜的線膨脹係數之差小於35×10-6/℃。 The thermosetting resin film according to claim 4, wherein the thermosetting resin film has a coefficient of linear expansion of from 5 × 10 -6 / ° C to 80 × 10 -6 / ° C, and is as described above The difference in linear expansion coefficient of the second protective film forming film is less than 35 × 10 -6 /°C. 一種第一保護膜形成用片，係於第一支持片的一方的表面上具備如請求項4或請求項5所記載之熱固化性樹脂膜。 A sheet for forming a first protective film, comprising a thermosetting resin film according to claim 4 or claim 5, on one surface of the first support sheet. 一種半導體晶圓用第一保護膜的形成方法，係於半導體晶圓的具有電路及複數個凸塊之表面形成保護該複數個凸塊之第一保護膜；前述半導體晶圓用第一保護膜的形成方法包括：積層步驟，於背面側貼附有第二保護膜形成膜之前述半導體晶圓的表面，以覆蓋前述複數個凸塊之方式貼附熱固化性樹脂膜，由此形成將前述第二保護膜形成膜、前述半導體晶圓及前述熱固化性樹脂膜依序積層而成之積層體；以及固化步驟，藉由將前述積層體加熱，而使前述複數個凸塊貫穿前述熱固化性樹脂膜，以填埋前述複數個凸塊各自之間之方式使前述熱固化性樹脂膜加熱固化，由此於前述半導體晶圓的表面形成前述第一保護膜；前述熱固化性樹脂膜的藉由示差掃描熱量分析法所測定之發熱起始溫度為前述第二保護膜形成膜 的藉由示差掃描熱量分析法所測定的發熱起始溫度以上；並且，前述熱固化性樹脂膜及前述第二保護膜形成膜的藉由示差掃描熱量分析法所測定之發熱峰溫度分別為100℃至200℃，前述熱固化性樹脂膜與前述第二保護膜形成膜的前述發熱峰溫度之差為小於35℃之關係。 A method for forming a first protective film for a semiconductor wafer is formed on a surface of a semiconductor wafer having a circuit and a plurality of bumps to form a first protective film for protecting the plurality of bumps; and the first protective film for the semiconductor wafer The method of forming the surface of the semiconductor wafer to which the second protective film forming film is attached on the back side, and attaching the thermosetting resin film so as to cover the plurality of bumps, thereby forming the aforementioned a second protective film forming film, a laminated body in which the semiconductor wafer and the thermosetting resin film are sequentially laminated; and a curing step of heating the laminated body to penetrate the plurality of bumps through the heat curing The first resin film is formed on the surface of the semiconductor wafer by heat-hardening the thermosetting resin film so as to fill the plurality of bumps, and the thermosetting resin film is formed on the surface of the semiconductor wafer. The heat generation onset temperature measured by differential scanning calorimetry is the aforementioned second protective film forming film The heat-generating peak temperature measured by the differential scanning calorimetry method is higher than the heat generation starting temperature; and the heat-generating peak temperature of the thermosetting resin film and the second protective film forming film measured by the differential scanning calorimetry method is 100, respectively. The difference between the heat-generating peak temperature of the thermosetting resin film and the second protective film forming film is less than 35 ° C at a temperature of from ° C to 200 ° C.
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