TWI445786B - Adhesive composition for masking tape for mold underfill process and masking tape using the same - Google Patents

Adhesive composition for masking tape for mold underfill process and masking tape using the same Download PDF

Info

Publication number
TWI445786B
TWI445786B TW101101984A TW101101984A TWI445786B TW I445786 B TWI445786 B TW I445786B TW 101101984 A TW101101984 A TW 101101984A TW 101101984 A TW101101984 A TW 101101984A TW I445786 B TWI445786 B TW I445786B
Authority
TW
Taiwan
Prior art keywords
weight
masking tape
parts
resin
energy ray
Prior art date
Application number
TW101101984A
Other languages
Chinese (zh)
Other versions
TW201315786A (en
Inventor
Yeon Soo Kim
Ki Jeong Moon
Kyong Yeon Jeon
Original Assignee
Toray Advanced Mat Korea Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toray Advanced Mat Korea Inc filed Critical Toray Advanced Mat Korea Inc
Publication of TW201315786A publication Critical patent/TW201315786A/en
Application granted granted Critical
Publication of TWI445786B publication Critical patent/TWI445786B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H01L21/565—Moulds
    • H01L21/566—Release layers for moulds, e.g. release layers, layers against residue during moulding
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation
    • H01L2924/1815—Shape
    • H01L2924/1816—Exposing the passive side of the semiconductor or solid-state body
    • H01L2924/18161—Exposing the passive side of the semiconductor or solid-state body of a flip chip

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Wire Bonding (AREA)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)

Description

用於模壓底膠充填製程之遮蔽膠帶黏著劑合成物及使用此種黏著劑合成物之遮蔽膠帶Masking tape adhesive composition for molding underfill filling process and masking tape using the same

本發明有關一種用於模壓底膠充填製程之遮蔽膠帶黏著劑合成物及使用此種黏著劑合成物之遮蔽膠帶；尤其有關一種用於模壓底膠充填製程之黏著劑合成物，其包括一能量射線固化型矽酮樹脂，其可防止殘膠留在印刷電路板(PCB)的表面上，也可防止污漬留在任何類型之環氧模塑料(EMC)表面上；本發明亦有關使用此種黏著劑合成物製成之遮蔽膠帶。The invention relates to a masking tape adhesive composition for molding a primer filling process and a masking tape using the same; in particular, an adhesive composition for molding a primer filling process, which comprises an energy a radiation curable indolinone resin that prevents residual glue from remaining on the surface of a printed circuit board (PCB) and also prevents stains from remaining on any type of epoxy molding compound (EMC) surface; the present invention also relates to the use of such Masking tape made of adhesive composition.

近年來對於增加行動電話訊號處理及記憶能量的需求，加上降低行動電話尺寸與成本的壓力，驅使層疊封裝(POP)結構的發展，以期在縮減的安裝面積內具有提升的記憶體密度與效能。此種層疊封裝結構的底層包括一種晶粒外露式覆晶封裝(DEFCP)法，因為其中以晶片作為接地。然後，進行一項用以防裂與散熱的模壓底膠充填(MUF)製程，其中係使用一種黏性膠帶覆蓋晶片。In recent years, the need to increase mobile phone signal processing and memory energy, coupled with the pressure to reduce the size and cost of mobile phones, has driven the development of package-on-package (POP) structures with an increased memory density and performance in a reduced installation area. . The underlayer of such a package structure includes a die exposed flip chip package (DEFCP) method in which a wafer is used as a ground. Then, a molding primer filling (MUF) process for cracking and heat dissipation is performed, in which a wafer is covered with an adhesive tape.

本案申請人先前曾提出一種用於晶粒外露式覆晶封裝法之模壓底膠充填製程黏性膠帶(韓國專利申請案第10-2011-0005902號)。為了克服模具被習知聚對苯二甲酸乙二酯(PET)薄膜基片污染的相關問題，上述專利申請案提出一種結構，其包括一種低聚物遷移減少的聚萘二甲酸乙二醇酯(PEN)薄膜基片，及一種具有優異離型性與耐熱性的丙烯酸膠離型層。所述丙烯酸膠離型層由於具有高表面硬度，所以它具有優異的離型性。然而，丙烯酸膠離型層易受刮傷，因此在模壓底膠充填製程期間會被模具尖銳的角隅割斷；而從黏膠層割斷的碎片會移轉到位於模具下方的印刷電路板表面，造成不利。此外，使用各種不同類型的環氧模塑料進行模壓底膠充填製程時，會於環氧模塑料成型後在特定類型的環氧模塑料表面上留下污漬。The applicant of the present application has previously proposed a molded base adhesive filling process adhesive tape for a die exposed flip chip packaging method (Korean Patent Application No. 10-2011-0005902). In order to overcome the problems associated with conventional polyethylene terephthalate (PET) film substrate contamination, the above patent application proposes a structure comprising a polyethylene naphthalate having reduced oligomer migration (PEN). A film substrate, and an acrylic adhesive release layer having excellent release properties and heat resistance. The acrylic adhesive release layer has excellent mold release property because of its high surface hardness. However, the acrylic release layer is susceptible to scratching and is therefore severed by the sharp corners of the mold during the molding underfill process; the debris cut from the adhesive layer is transferred to the surface of the printed circuit board below the mold. Causes disadvantage. In addition, when using a variety of different types of epoxy molding compounds for the molding underfill process, stains are left on the surface of a particular type of epoxy molding after the molding of the epoxy molding compound.

因此，本案發明人發現一種改良的丙烯酸膠離型層，其具有可控制的表面硬度並包括一種特定類型的固化劑，不會在印刷電路板表面留下殘膠，也不會在任何類型的環氧模塑料表面產生污漬；同時，包括此種丙烯酸膠離型層的黏性遮蔽膠帶用於晶粒外露式覆晶封裝法之模壓底膠充填製程時不會污染模具；藉此完成本發明。Accordingly, the inventors have discovered an improved acrylic release layer that has a controlled surface hardness and includes a specific type of curing agent that does not leave residual glue on the surface of the printed circuit board and does not exist in any type. The surface of the epoxy molding compound is stained; at the same time, the adhesive masking tape including the acrylic adhesive release layer is used for the die-casting filling process of the die-exposed flip chip packaging method without contaminating the mold; thereby completing the present invention .

因此，鑒於先前技術中發生的問題，特此提出本發明。本發明之一目的在於提供一種用於模壓底膠充填製程之遮蔽膠帶黏著劑合成物，其包括一能量射線固化型低聚物樹脂及一能量射線固化型矽酮樹脂，此等樹脂可防止在印刷電路板表面上留下殘膠並可防止黏著劑合成物在任何環氧模塑料(EMC)的表面上留下污漬。Therefore, the present invention has been made in view of the problems occurring in the prior art. An object of the present invention is to provide a masking tape adhesive composition for molding a primer filling process, which comprises an energy ray-curable oligomer resin and an energy ray-curable fluorenone resin, which can prevent Residual glue remains on the surface of the printed circuit board and prevents the adhesive composition from leaving stains on the surface of any epoxy molding compound (EMC).

本發明另一目的在於提供一種使用上述黏著劑合成物製作的遮蔽膠帶。Another object of the present invention is to provide a masking tape produced using the above adhesive composition.

為達以上目的，本發明提供一種用於模壓底膠充填製程之遮蔽膠帶黏著劑合成物，此種黏著劑合成物包括：(a)100重量份之丙烯酸系共聚物；(b)1～20重量份之熱固化劑；(c)5～40重量份之能量射線固化型聚氨酯樹脂；(d)0.1～5重量份之能量射線固化型矽酮樹脂；及(e)一能量射線引發劑。To achieve the above object, the present invention provides a masking tape adhesive composition for molding a primer filling process, the adhesive composition comprising: (a) 100 parts by weight of an acrylic copolymer; (b) 1-20 Parts by weight of the heat curing agent; (c) 5 to 40 parts by weight of the energy ray-curable polyurethane resin; (d) 0.1 to 5 parts by weight of the energy ray-curable fluorenone resin; and (e) an energy ray initiator.

本發明中使用的能量射線固化型聚氨酯樹脂較佳選自以下群組中的一或多種：脂肪族雙官能聚氨酯丙烯酸酯、脂肪族三官能聚氨酯丙烯酸酯、脂肪族六官能聚氨酯丙烯酸酯、芳香族雙官能聚氨酯丙烯酸酯、芳香族三官能聚氨酯丙烯酸酯、及芳香族六官能聚氨酯丙烯酸酯。The energy ray-curable polyurethane resin used in the present invention is preferably selected from one or more of the group consisting of aliphatic difunctional urethane acrylate, aliphatic trifunctional urethane acrylate, aliphatic hexafunctional urethane acrylate, aromatic Bifunctional urethane acrylate, aromatic trifunctional urethane acrylate, and aromatic hexafunctional urethane acrylate.

本發明中使用的能量射線固化型矽酮樹脂較佳選自以下群組中的一或多種：矽酮二丙烯酸酯、矽酮六丙烯酸酯、矽酮聚酯丙烯酸酯、矽酮聚氨酯丙烯酸酯、及矽酮聚氨酯甲基丙烯酸甲酯。The energy ray-curable fluorenone resin used in the present invention is preferably selected from one or more of the group consisting of fluorenone diacrylate, fluorenone hexaacrylate, fluorenone polyester acrylate, anthrone urethane acrylate, And anthrone urethane methyl methacrylate.

本發明中使用的熱固化劑，較佳是一種以三聚氰胺為基料的熱固化劑。The heat curing agent used in the present invention is preferably a heat curing agent based on melamine.

在另一層面中，本發明提供一種用於模壓底膠充填製程之遮蔽膠帶，其包括：一耐熱薄膜基片；一抗靜電層，設於耐熱薄膜基片的一側或兩側；及一黏膠層，設於抗靜電層上。In another aspect, the present invention provides a masking tape for molding a primer filling process, comprising: a heat-resistant film substrate; an antistatic layer disposed on one side or both sides of the heat-resistant film substrate; The adhesive layer is disposed on the antistatic layer.

在本發明之遮蔽膠帶中，所述耐熱薄膜基片較佳選自以下群組中之任何一種：聚酰亞胺薄膜(PI)、聚對苯二甲酸乙二酯薄膜(PET)、聚萘二甲酸乙二醇酯薄膜(PEN)、及聚丁烯對苯二甲酸酯薄膜(PBT)。In the masking tape of the present invention, the heat-resistant film substrate is preferably selected from any one of the group consisting of polyimide film (PI), polyethylene terephthalate film (PET), and polynaphthalene. Ethylene glycol dicarboxylate film (PEN), and polybutylene terephthalate film (PBT).

製造所述黏膠層的黏著劑合成物較佳包括：(a)100重量份之丙烯酸系共聚物；(b)1～20重量份之熱固化劑；(c)5～40重量份之能量射線固化型聚氨酯樹脂；(d)0.1～5重量份之能量射線固化型矽酮樹脂；及(e)一能量射線引發劑。The adhesive composition for producing the adhesive layer preferably comprises: (a) 100 parts by weight of an acrylic copolymer; (b) 1 to 20 parts by weight of a heat curing agent; (c) 5 to 40 parts by weight of energy. a radiation curable urethane resin; (d) 0.1 to 5 parts by weight of an energy ray-curable fluorenone resin; and (e) an energy ray initiator.

所述黏膠層在室溫下對拋光後矽晶圓之黏著強度為50gf/inch(克力/英吋)或更低。The adhesive layer has an adhesive strength of 50 gf/inch (grams/inch) or less to the polished wafer after polishing at room temperature.

所述黏膠層之表面電阻為1011Ω/□(歐姆/平方)或更低。The surface resistance of the adhesive layer is 1011 Ω/□ (ohm/square) or less.

配合以下詳細說明及附圖，可以更加瞭解本發明上述及其他目的、特徵及優點。The above and other objects, features and advantages of the present invention will become more <RTIgt;

根據本發明用於模壓底膠充填(MUF)製程之遮蔽膠帶黏著劑合成物包括：(a)一丙烯酸系共聚物；(b)一熱固化劑；(c)一能量射線固化型聚氨酯樹脂；(d)一能量射線固化型矽酮樹脂；及(e)一能量射線引發劑。以下詳細說明此種合成物之每一組成份。The masking tape adhesive composition for use in a molded underfill (MUF) process according to the present invention comprises: (a) an acrylic copolymer; (b) a heat curing agent; (c) an energy ray curable polyurethane resin; (d) an energy ray-curable fluorenone resin; and (e) an energy ray initiator. Each component of such a composition is described in detail below.

1.黏著劑合成物Adhesive composition 1-1　丙烯酸系共聚物1-1 Acrylic copolymer

模壓底膠充填製程之遮蔽膠帶黏著劑合成物中的丙烯酸系共聚物樹脂是一種分子中無雙鍵之飽和聚合物，其優點在於具有優異的抗氧化性也因此具有優異的耐候性；並可視所需的物理特性而定，經由改變聚合物之組成或導入一個官能基而輕易改性。本文中使用「丙烯酸系共聚物樹脂」一詞係指一種包含多種單體之共聚物；所述單體包括丙烯酸及/或甲基丙烯酸，或其各種衍生物。所述丙烯酸系共聚物樹脂較佳是包含多種單體之共聚物，所述單體包括選自以下群組中的一種或多種：甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸異戊酯、甲基丙烯酸n-己酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸異辛酯、甲基丙烯酸異壬酯、甲基丙烯酸癸酯、甲基丙烯酸十二烷酯、及甲基丙烯酸烷酯。The acrylic copolymer resin in the masking tape adhesive composition of the molded base adhesive filling process is a saturated polymer having no double bond in the molecule, and has the advantages of excellent oxidation resistance and therefore excellent weather resistance; Depending on the physical properties required, it can be easily modified by changing the composition of the polymer or introducing a functional group. The term "acrylic copolymer resin" as used herein refers to a copolymer comprising a plurality of monomers; the monomers comprising acrylic acid and/or methacrylic acid, or various derivatives thereof. The acrylic copolymer resin is preferably a copolymer comprising a plurality of monomers including one or more selected from the group consisting of methyl methacrylate, ethyl methacrylate, and methacrylic acid. Ester, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate, isodecyl methacrylate, decyl methacrylate, methacrylic acid Dodecyl ester, and alkyl methacrylate.

本發明中使用的丙烯酸系共聚物其重均分子量較佳為100,000～1,500,000，更佳為500,000～1,000,000。倘若丙烯酸系共聚物之重均分子量低於100,000，使用所述黏著劑合成物塗佈而獲得的黏膠層會有不良的內聚力，因此所述黏著劑合成物於膠帶剝除後可能會留在晶片上受等離子體激活之等離子體活化表面。倘若重均分子量高於1,500,000，共聚物在溶劑中的可溶性會下降，使其難以形成均勻的塗佈層，而且共聚物的熱固化性及能量射線固化性也會降低，使樹脂成份留在晶片表面上。The acrylic copolymer used in the present invention preferably has a weight average molecular weight of from 100,000 to 1,500,000, more preferably from 500,000 to 1,000,000. If the weight average molecular weight of the acrylic copolymer is less than 100,000, the adhesive layer obtained by coating with the adhesive composition may have poor cohesive force, and thus the adhesive composition may remain after tape stripping. A plasma activated plasma on the wafer activates the surface. If the weight average molecular weight is higher than 1,500,000, the solubility of the copolymer in the solvent is lowered, making it difficult to form a uniform coating layer, and the thermal curability and energy ray curability of the copolymer are also lowered, leaving the resin component on the wafer. On the surface.

1-2　熱固化劑1-2 heat curing agent

本發明黏著劑合成物中的熱固化劑係用以交聯丙烯酸系共聚物。供此目的之固化劑特定實例包括以三聚氰胺為基料、以聚氮丙啶為基料、及以芳基異氰酸酯為基料的熱固化劑。The heat curing agent in the adhesive composition of the present invention is used to crosslink the acrylic copolymer. Specific examples of the curing agent for this purpose include a melamine-based, polyaziridine-based, and aryl isocyanate-based heat curing agent.

以三聚氰胺為基料的熱固化劑實例包括正丁基化三聚氰胺、異丁基化三聚氰胺、及正丁基化三聚氰胺-苯代三聚氰胺。Examples of melamine-based thermal curing agents include n-butylated melamine, isobutylated melamine, and n-butylated melamine-benzoguanamine.

以聚氮丙啶為基料的熱固化劑實例包括丙烯亞胺(氮丙啶)、三(2-甲基-1-氮丙啶)氧化膦等。Examples of the heat curing agent based on polyaziridine include propylene imine (aziridine), tris(2-methyl-1-aziridine) phosphine oxide, and the like.

以芳基異氰酸酯為基料的熱固化劑實例包括二苯基甲烷二異氰酸酯(MDI)、甲苯二異氰酸酯(TDI)等。Examples of the thermosetting agent based on aryl isocyanate include diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), and the like.

本發明中較佳是使用以三聚氰胺為基料的熱固化劑。以三聚氰胺為基料的熱固化劑其特徵在於加熱時會起反應並形成交聯的結構，視使用的份量而定。以異氰酸酯為基料的熱固化劑其特徵在於具有優異的反應性，所以甚至在室溫下也可以起反應。此外，以聚氮丙啶為基料的熱固化劑利於在低溫固化，因此固化時間縮短，但通常成本昂貴。In the present invention, it is preferred to use a melamine-based heat curing agent. The melamine-based thermal curing agent is characterized in that it reacts upon heating and forms a crosslinked structure, depending on the amount used. The isocyanate-based heat curing agent is characterized by excellent reactivity, so that it can react even at room temperature. In addition, a polyaziridine-based thermal curing agent facilitates curing at a low temperature, so the curing time is shortened, but it is usually expensive.

以100重量份的丙烯酸系共聚物為基準時，所使用的熱固化劑份量，較佳為1～20重量份，更佳是1～15重量份。以100重量份的丙烯酸系共聚物為基準時，所使用的熱固化劑份量，較佳為1～15重量份，更佳是1～10重量份。倘若熱固化劑的含量低於1重量份，丙烯酸系共聚物將無法充分交聯，由於以此種黏著劑合成物製成的塗佈層其內聚力低，因此會有殘膠留在基片表面上；倘若熱固化劑的含量高於20重量份，丙烯酸系共聚物將過度交聯，所產生的黏膠塗佈層表面硬度會增加，所以黏膠層容易斷裂。The amount of the thermosetting agent to be used is preferably from 1 to 20 parts by weight, more preferably from 1 to 15 parts by weight, based on 100 parts by weight of the acrylic copolymer. The amount of the thermosetting agent to be used is preferably from 1 to 15 parts by weight, more preferably from 1 to 10 parts by weight, based on 100 parts by weight of the acrylic copolymer. If the content of the heat curing agent is less than 1 part by weight, the acrylic copolymer will not be sufficiently crosslinked, and since the coating layer made of such an adhesive composition has low cohesive force, residual glue remains on the surface of the substrate. If the content of the heat curing agent is more than 20 parts by weight, the acrylic copolymer will be excessively crosslinked, and the surface hardness of the resulting adhesive coating layer will increase, so that the adhesive layer is easily broken.

熱固化劑可與一種以有機酸為基料之熱固化促進劑配合使用來加速固化。供此目的之有機酸基料熱固化促進劑實例包括苯酐、四氫苯酐、甲基四氫苯酐、六氫苯酐、甲基納迪克酸酐等。倘若使用熱固化促進劑，以100重量份的丙烯酸系共聚物為基準時，其使用份量應少於15重量份，較佳少於10重量份。倘若熱固化促進劑的含量高於15重量份，所產生的黏膠塗佈層表面硬度會增加，造成諸如黏膠層斷裂的現象，類似熱固化劑含量太高時的情況。The heat curing agent can be used in combination with a thermal curing accelerator based on an organic acid to accelerate the curing. Examples of the organic acid binder thermal curing accelerator for this purpose include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl nadic anhydride, and the like. If a heat curing accelerator is used, it should be used in an amount of less than 15 parts by weight, preferably less than 10 parts by weight, based on 100 parts by weight of the acrylic copolymer. If the content of the heat curing accelerator is more than 15 parts by weight, the surface hardness of the resulting adhesive coating layer may increase, causing a phenomenon such as breakage of the adhesive layer, similarly when the content of the heat curing agent is too high.

1-3　能量射線固化型樹脂1-3 energy ray curing resin

能量射線固化型樹脂這種組成份，當其分子鏈受到諸如紫外線(UV)、電子束(EB)、放射性射線等強能量射線照射而產生自由基時，會形成交聯。此種黏著劑合成物中包含的光引發劑會吸收波長200～400nm的紫外線而成為有反應性，然後與樹脂的主要組成單體起反應形成一種聚合物，同時使樹脂固化。當紫外線固化型樹脂內包含的光引發劑接收紫外線時，會啟動一種光致聚合作用，使樹脂的主要組成單體及低聚物瞬間固化而形成一種聚合物。The component of the energy ray-curable resin forms crosslinks when its molecular chain is irradiated with strong energy rays such as ultraviolet rays (UV), electron beams (EB), and radioactive rays to generate radicals. The photoinitiator contained in such an adhesive composition absorbs ultraviolet rays having a wavelength of 200 to 400 nm to become reactive, and then reacts with a main constituent monomer of the resin to form a polymer while curing the resin. When the photoinitiator contained in the ultraviolet curable resin receives ultraviolet rays, a photopolymerization is initiated to instantaneously cure the main constituent monomers and oligomers of the resin to form a polymer.

能量射線固化型樹脂依其聚合作用型態可分成自由基聚合型樹脂、自由基加成聚合型樹脂、及陽離子聚合型樹脂。自由基聚合型樹脂包括以丙烯酸酯為基料之樹脂；自由基加成聚合型樹脂包括聚烯/聚硫醇樹脂與雜環螺烷樹脂；陽離子聚合型樹脂包括環氧樹脂與乙烯基醚。較佳是使用以丙烯酸酯為基料之反應性低聚物。以丙烯酸酯為基料之反應性低聚物，其實例包括環氧丙烯酸酯、聚氨酯丙烯酸酯、聚酯丙烯酸酯、矽酮丙烯酸酯等。本發明中係使用聚氨酯丙烯酸酯與矽酮丙烯酸酯的混合物。此種樹脂與能量射線引發劑起反應而形成一種半互穿聚合物網狀(IPN)結構。The energy ray-curable resin can be classified into a radical polymerization type resin, a radical addition polymerization type resin, and a cationic polymerization type resin depending on the polymerization mode. The radical polymerizable resin includes an acrylate-based resin; the radical addition polymerizable resin includes a polyolefin/polythiol resin and a heterocyclic spiro resin; and the cationically polymerizable resin includes an epoxy resin and a vinyl ether. It is preferred to use an acrylate-based reactive oligomer. An acrylate-based reactive oligomer, and examples thereof include epoxy acrylate, urethane acrylate, polyester acrylate, fluorenone acrylate, and the like. In the present invention, a mixture of urethane acrylate and anthrone acrylate is used. This resin reacts with the energy ray initiator to form a semi-interpenetrating polymer network (IPN) structure.

1-3-1　能量射線固化型聚氨酯樹脂1-3-1 Energy ray curing polyurethane resin

能量射線固化型聚氨酯樹脂係用於對黏著劑合成物提供優異的耐熱性。能量射線固化型聚氨酯樹脂的實例包括脂肪族雙官能聚氨酯丙烯酸酯、脂肪族三官能聚氨酯丙烯酸酯、脂肪族六官能聚氨酯丙烯酸酯、芳香族雙官能聚氨酯丙烯酸酯、芳香族三官能聚氨酯丙烯酸酯、芳香族六官能聚氨酯丙烯酸酯等。The energy ray-curable polyurethane resin is used to provide excellent heat resistance to an adhesive composition. Examples of the energy ray-curable polyurethane resin include aliphatic difunctional urethane acrylate, aliphatic trifunctional urethane acrylate, aliphatic hexafunctional urethane acrylate, aromatic difunctional urethane acrylate, aromatic trifunctional urethane acrylate, and aromatic Group of hexafunctional urethane acrylates and the like.

以100重量份的丙烯酸系共聚物為基準時，所使用的能量射線固化型聚氨酯樹脂份量為5～40重量份，較佳是5～35重量份。倘若射線固化型聚氨酯樹脂的含量低於5重量份，丙烯酸系共聚物將無法充分交聯，由於以此種黏著劑合成物製成的塗佈層其內聚力低，因此會有殘膠留在基面上；倘若射線固化型聚氨酯樹脂的含量高於40重量份，由於所產生的黏膠層表面硬度高而易受刮傷並可能被模具角隅割斷，類似先前技術的黏膠層。The amount of the energy ray-curable polyurethane resin to be used is 5 to 40 parts by weight, preferably 5 to 35 parts by weight, based on 100 parts by weight of the acrylic copolymer. If the content of the radiation-curable polyurethane resin is less than 5 parts by weight, the acrylic copolymer may not be sufficiently crosslinked, and since the coating layer made of such an adhesive composition has low cohesive force, residual rubber remains in the base. If the content of the radiation-curable urethane resin is more than 40 parts by weight, the surface of the adhesive layer which is produced is high in hardness and is easily scratched and may be cut by the corner of the mold, similar to the adhesive layer of the prior art.

1-3-2　能量射線固化型矽酮樹脂1-3-2 Energy ray-curable fluorenone resin

能量射線固化型矽酮樹脂係用於對黏著劑合成物提供優異的離型特性。能量射線固化型矽酮樹脂的實例包括矽酮二丙烯酸酯、矽酮六丙烯酸酯、矽酮聚酯丙烯酸酯、矽酮聚氨酯丙烯酸酯、矽酮聚氨酯甲基丙烯酸甲酯等。The energy ray-curable fluorenone resin is used to provide excellent release characteristics to the adhesive composition. Examples of the energy ray-curable fluorenone resin include fluorenone diacrylate, fluorenone hexaacrylate, fluorenone polyester acrylate, anthrone urethane acrylate, anthrone urethane methyl methacrylate, and the like.

以100重量份的丙烯酸系共聚物為基準時，所使用的能量射線固化型矽酮樹脂份量較佳為0.1～5重量份，更佳是1～5重量份。倘若射線固化型矽酮樹脂的含量低於0.1重量份，丙烯酸系共聚物將無法充分交聯，由於以此種黏著劑合成物製成的塗佈層其內聚力低，因此會有殘膠留在基面上。反之，倘若射線固化型矽酮樹脂的含量高於5重量份，由於所產生的黏膠層表面硬度高而易受刮傷並可能被模具角隅割斷，類似先前技術的黏膠層。The amount of the energy ray-curable fluorenone resin to be used is preferably from 0.1 to 5 parts by weight, more preferably from 1 to 5 parts by weight, based on 100 parts by weight of the acryl-based copolymer. If the content of the radiation-curable fluorenone resin is less than 0.1 parts by weight, the acrylic copolymer may not be sufficiently crosslinked, and since the coating layer made of such an adhesive composition has low cohesive force, residual glue remains. On the base. On the other hand, if the content of the radiation-curable fluorenone resin is more than 5 parts by weight, the surface of the adhesive layer which is produced is high in hardness and is easily scratched and may be cut by the corner of the mold, similar to the adhesive layer of the prior art.

1-5　能量射線引發劑1-5 energy ray initiator

能量射線引發劑的功能是吸收紫外線能量來啟動光致聚合作用。供此目的之能量射線引發劑實例包括二甲基苄基酮、羥基環乙基苯基丙酮、羥基二甲基苯乙酮、甲基[4-甲硫基苯基]-2-嗎啉丙酮、4-苄基-4-甲基二酚基硫化物、異丙基硫雜蒽酮、2-氯代硫雜蒽酮、4-二甲氨基苯甲酸乙酯、對二甲氨基苯甲酸異辛酯、二苯甲酮、4-甲基二苯甲酮、原苯甲酸三甲酯、苯甲酰甲酸甲酯、4-苯基二苯甲酮、(2,4,6-三甲基苯甲酰基)二苯基氧化膦、2-羥基-1,2-二苯基乙酮等。The function of the energy ray initiator is to absorb ultraviolet energy to initiate photopolymerization. Examples of energy ray initiators for this purpose include dimethylbenzyl ketone, hydroxycycloethyl phenyl ketone, hydroxy dimethyl acetophenone, methyl [4-methylthiophenyl]-2-morpholinone , 4-benzyl-4-methyldiphenolsulfide, isopropylthioxanthone, 2-chlorothionidone, ethyl 4-dimethylaminobenzoate, p-dimethylaminobenzoic acid Octyl ester, benzophenone, 4-methylbenzophenone, trimethyl orthobenzoate, methyl benzoylformate, 4-phenylbenzophenone, (2,4,6-trimethyl Benzoyl)diphenylphosphine oxide, 2-hydroxy-1,2-diphenylethanone, and the like.

以100重量份的丙烯酸系共聚物為基準時，所使用的能量射線引發劑份量為1～15重量份，較佳是1～10重量份。倘若，以100重量份的丙烯酸系共聚物為基準，能量射線引發劑的用量低於1重量份時，能量射線固化型樹脂無法充分固化；倘若其用量高於15重量份時，能量射線引發劑未起反應的部份會像殘膠一般留下而污染半導體封裝。The amount of the energy ray initiator to be used is 1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the acrylic copolymer. If the amount of the energy ray initiator is less than 1 part by weight based on 100 parts by weight of the acrylic copolymer, the energy ray-curable resin may not be sufficiently cured; if the amount is more than 15 parts by weight, the energy ray initiator The unreacted portion will remain as a residual glue and contaminate the semiconductor package.

1-6　其他添加劑1-6 other additives

此外，除上述的組成份之外，本發明之黏著劑合成物可進一步包括若干添加劑，例如溶劑、光敏劑、抗氧化劑及流平劑。Further, in addition to the above components, the adhesive composition of the present invention may further comprise a plurality of additives such as a solvent, a photosensitizer, an antioxidant, and a leveling agent.

2.遮蔽膠帶2. Masking tape

以下請參照第一圖說明包括本發明黏著劑合成物的遮蔽膠帶。第一圖為一概要斷面圖，顯示一種包括本發明黏著劑合成物並用於模壓底膠充填(MUF)製程之遮蔽膠帶。請參照第一圖，遮蔽膠帶10包括：一耐熱薄膜基片11；一抗靜電層12或12’，設於耐熱薄膜基片11的一側或兩側；及一黏膠層13，設於抗靜電層12或12’上。Hereinafter, a masking tape including the adhesive composition of the present invention will be described with reference to the first drawing. The first figure is a schematic cross-sectional view showing a masking tape comprising the adhesive composition of the present invention and used in a molding underfill (MUF) process. Referring to the first figure, the masking tape 10 includes: a heat-resistant film substrate 11; an antistatic layer 12 or 12' disposed on one side or both sides of the heat-resistant film substrate 11; and an adhesive layer 13 disposed on Antistatic layer 12 or 12'.

2-1　耐熱薄膜基片2-1 heat-resistant film substrate

耐熱薄膜基片的實例可包括多種聚酯薄膜，例如聚酰亞胺薄膜(PI)、聚對苯二甲酸乙二酯薄膜(PET)、聚萘二甲酸乙二醇酯薄膜(PEN)、及聚丁烯對苯二甲酸酯薄膜(PBT)。薄膜基片的厚度通常為10～100μm(微米)，較佳為10～50μm，更佳為25～50μm。此外，薄膜基片可接受習知的物理或化學表面處理，諸如消光、電暈放電、底層處理及交聯，以便增加對抗靜電層及/或黏膠層的黏著力並增加維護。Examples of the heat-resistant film substrate may include various polyester films such as polyimide film (PI), polyethylene terephthalate film (PET), polyethylene naphthalate film (PEN), and Polybutylene terephthalate film (PBT). The thickness of the film substrate is usually from 10 to 100 μm (micrometer), preferably from 10 to 50 μm, more preferably from 25 to 50 μm. In addition, the film substrate can be subjected to conventional physical or chemical surface treatments such as matting, corona discharge, underlayer treatment, and crosslinking to increase adhesion to the antistatic layer and/or the adhesive layer and to increase maintenance.

2-2　抗靜電層2-2 antistatic layer

此外，抗靜電層係設於薄膜基片的一側或兩側。此一導電層可使用顯示抗靜電特性的塗層材料製作，例如表面活性劑或導電聚合物。用以製作所述導電層的導電聚合物，較佳具有低表面電阻與低表面電位，對濕氣較不敏感，並顯示永久抗靜電性能。通常用於抗靜電塗層的聚合物包括聚苯胺、聚吡咯、聚噻吩等。此外，也可使用它們的衍生物。為了方便將此種導電塗層溶液塗到薄膜基片的表面，可將塗層溶液混合一結合劑。本發明中可使用的結合劑實例包括導電丙烯酸樹脂、聚氨酯樹脂、酯化樹脂、醚樹脂、環氧樹脂、酰胺樹脂、酰亞胺樹脂、及苯乙烯樹脂。抗靜電層的敷設厚度較佳為0.01～1μm。倘若抗靜電層的敷設厚度低於0.1μm，將無法展現所需的抗靜電特性；倘若其敷設厚度高於1μm，則會展現非必要的高抗靜電性能而且不利於成本，因為導電聚合物價格昂貴；此外會使黏膠層不易敷設到導電層上。Further, the antistatic layer is provided on one side or both sides of the film substrate. The conductive layer can be made of a coating material exhibiting antistatic properties, such as a surfactant or a conductive polymer. The conductive polymer used to form the conductive layer preferably has a low surface resistance and a low surface potential, is less sensitive to moisture, and exhibits permanent antistatic properties. Polymers commonly used in antistatic coatings include polyaniline, polypyrrole, polythiophene, and the like. In addition, derivatives thereof can also be used. In order to facilitate application of such a conductive coating solution to the surface of the film substrate, the coating solution may be mixed with a binder. Examples of the binder which can be used in the present invention include a conductive acrylic resin, a polyurethane resin, an esterified resin, an ether resin, an epoxy resin, an amide resin, an imide resin, and a styrene resin. The thickness of the antistatic layer to be applied is preferably 0.01 to 1 μm. If the thickness of the antistatic layer is less than 0.1 μm, the required antistatic properties will not be exhibited; if the thickness is more than 1 μm, it will exhibit non-essential high antistatic properties and be disadvantageous because of the price of the conductive polymer. Expensive; in addition, the adhesive layer is not easy to lay on the conductive layer.

2-3　黏膠層2-3 adhesive layer

設於抗靜電層上的黏膠層，其組成如上所述。The adhesive layer provided on the antistatic layer has the composition as described above.

同時，黏膠層的厚度較佳為2～30μm。倘若黏膠層的厚度低於2μm，由於黏結面的公差，會使成型特性劣化。反之，倘若厚度高於30μm，利用紫外線固化黏膠層時將難以達到順利固化，所以使黏膠層的物理特性劣化且對模壓底膠充填製程中的施壓與應力抗性低弱。At the same time, the thickness of the adhesive layer is preferably from 2 to 30 μm. If the thickness of the adhesive layer is less than 2 μm, the molding properties are deteriorated due to the tolerance of the bonding surface. On the other hand, if the thickness is higher than 30 μm, it is difficult to achieve smooth curing by curing the adhesive layer with ultraviolet rays, so that the physical properties of the adhesive layer are deteriorated and the resistance to stress and stress in the molding underfill filling process is weak.

黏膠層在室溫下對拋光後矽晶圓表面的黏著強度較佳為50gf/inch(克力/英吋)或更低，更佳為30gf/inch或更低。倘若黏膠層的黏著力高於50gf/inch，在模壓底膠充填製程中，晶片的等離子體活化表面上會發生殘膠。The adhesion strength of the adhesive layer to the surface of the polished wafer after polishing at room temperature is preferably 50 gf/inch or less, more preferably 30 gf/inch or less. If the adhesion of the adhesive layer is higher than 50 gf/inch, residual glue will occur on the plasma activated surface of the wafer during the molding underfill process.

黏膠層的表面電阻為1011Ω/□(甌姆/平方)或更低。倘若黏膠層的表面電阻高於1011Ω/□，模壓底膠充填製程中會發生靜電失效，使產生的封裝降低或損失電氣性能。The surface resistance of the adhesive layer is 1011 Ω / □ (瓯 / square) or lower. If the surface resistance of the adhesive layer is higher than 1011 Ω / □, electrostatic failure will occur in the molding underfill filling process, resulting in reduced package or loss of electrical performance.

3.模壓底膠充填(MUF)製程3. Molded primer filling (MUF) process

進行模壓底膠充填製程時，係使用一種絕緣樹脂保護層疊封裝(PoP)的底層，以使晶片作為接地的表面外露。第二圖中顯示模壓底膠充填製程。In the mold underfill process, an underlying resin (PoP) underlayer is protected with an insulating resin to expose the wafer as a grounded surface. The second figure shows the molding primer filling process.

1)薄膜敷設製程1) Film laying process

模壓底膠充填製程是於上模14與下模15之間進行的，製程溫度為175℃，其中使用真空將耐熱薄膜基片11敷設到上模14。倘若薄膜的抗張強度太低，薄膜可能被撕破，而且薄膜伸長率太低，使薄膜無法緊密黏到模具內的模穴。在本發明中用作薄膜基片的聚萘二甲酸乙二醇酯(PEN)薄膜，其抗張強度為15kg/mm2 (公斤/平方公厘)或更高，其伸長率為80%或更高，因此可以完好地敷設到模具上。The molding underfill filling process is performed between the upper mold 14 and the lower mold 15, and the process temperature is 175 ° C, wherein the heat-resistant film substrate 11 is applied to the upper mold 14 using a vacuum. If the tensile strength of the film is too low, the film may be torn and the film elongation is too low, so that the film does not adhere tightly to the cavity in the mold. The polyethylene naphthalate (PEN) film used as a film substrate in the present invention has a tensile strength of 15 kg/mm 2 (kg/cm 2 ) or more and an elongation of 80% or It is higher so it can be applied to the mold perfectly.

2)底膠充填製程2) Underfill filling process

薄膜敷設到上模之後，將上模14降低，使其與下模15結合，同時用一種環氧模塑料(EMC)19包封晶片17，並用黏膠層13遮蔽晶片表面。After the film is applied to the upper mold, the upper mold 14 is lowered to be bonded to the lower mold 15, while the wafer 17 is covered with an epoxy molding compound (EMC) 19, and the surface of the wafer is covered with the adhesive layer 13.

其中，倘若黏膠層的黏著力不足，環氧模塑料19會滲入晶片17的表面，產生模塑溢料。根據本發明之耐熱性丙烯酸黏膠層13可防止模塑溢料，因為它由具有優異耐熱性與黏著力的丙烯酸系共聚物構成。Among them, if the adhesiveness of the adhesive layer is insufficient, the epoxy molding compound 19 will infiltrate into the surface of the wafer 17, resulting in molding flash. The heat-resistant acrylic adhesive layer 13 according to the present invention can prevent molding flash because it is composed of an acrylic copolymer having excellent heat resistance and adhesion.

3)薄膜移除製程3) Film removal process

底膠充填製程之後，將上模14升高，同時從晶片17的表面及固化的環氧模塑料(EMC)19的表面移除耐熱薄膜基片11。After the underfill filling process, the upper mold 14 is raised while the heat-resistant film substrate 11 is removed from the surface of the wafer 17 and the surface of the cured epoxy molding compound (EMC) 19.

其中，倘若黏膠層13的離型性不足，耐熱薄膜基片11將無法輕易移除並會在環氧模塑料或晶片17的表面上留下殘膠。根據本發明之耐熱性丙烯酸的黏膠層13，其特性在於可讓薄膜輕易移除，因為它包括展現優異離型特性的能量射線固化型矽酮丙烯酸酯。Among them, if the release property of the adhesive layer 13 is insufficient, the heat-resistant film substrate 11 will not be easily removed and will leave a residue on the surface of the epoxy molding compound or the wafer 17. The heat-resistant acrylic adhesive layer 13 according to the present invention is characterized in that the film can be easily removed because it includes an energy ray-curable fluorenone acrylate exhibiting excellent release characteristics.

以下參照若干實例與比較實例進一步詳細說明本發明之結構與效用。然而須理解的是，此等實例僅供舉例說明之用，而不應視為限制本發明之範圍。The structure and utility of the present invention are further described in detail below with reference to a number of examples and comparative examples. However, it is to be understood that the examples are for illustrative purposes only and are not intended to limit the scope of the invention.

[實例1][Example 1]

將100重量份(以固體為基準)的一種丙烯酸系共聚物(Samwon出品之AT5100)加入600重量份之醋酸乙酯(EA)並攪拌一小時，然後在其中加入25重量份(以固體為基準)之能量射線固化型低聚物樹脂之脂肪族聚氨酯丙烯酸酯(Nippon Synthetic Chemical Industry之UV7600B80)，2重量份(以固體為基準)之矽酮六丙烯酸酯(CYTEC出品之EB1360)，及1重量份以膦為基料之光引發劑(CYTEC出品之DAROCUR TPO)，並將混合物攪拌一小時。然後在其中加入5重量份(以固體為基準)以三聚氰胺為基料的熱固化劑(Samwon出品之SM-20)及3重量份(以固體為基準)以有機酸為基料的熱固化促進劑(Samwon出品之A-20)，並將混合物攪拌一小時。將產生的黏著劑合成物敷設到厚度38μm的聚萘二甲酸乙二醇酯(PEN)薄膜一側，敷設厚度約10μm，其中，該PEN薄膜的兩側皆已敷設一種表面電阻為105Ω/□之抗靜電塗層。讓敷設的塗層合成物在150℃下乾燥5分鐘(熱固化)，並使用一紫外線輻射裝置以大約500W之紫外光輻射以使之固化，藉此製出一遮蔽膠帶。100 parts by weight (on a solids basis) of an acrylic copolymer (AT5100 from Samwon) was added to 600 parts by weight of ethyl acetate (EA) and stirred for one hour, and then 25 parts by weight (based on solids) was added thereto. An aliphatic urethane acrylate of energy ray-curable oligomer resin (UV7600B80 from Nippon Synthetic Chemical Industry), 2 parts by weight (on a solids basis) of ketone hexaacrylate (EB1360 from CYTEC), and 1 weight A phosphine-based photoinitiator (DAROCUR TPO from CYTEC) was dispensed and the mixture was stirred for one hour. Then, 5 parts by weight (on a solids basis) of a melamine-based heat curing agent (SM-20 from Samwon) and 3 parts by weight (on a solid basis) based on an organic acid-based heat curing promotion were added thereto. The agent (A-20 from Samwon) was stirred and the mixture was stirred for one hour. The resulting adhesive composition was applied to a polyethylene naphthalate (PEN) film having a thickness of 38 μm, and a thickness of about 10 μm was applied, wherein a surface resistance of 105 Ω/□ was applied to both sides of the PEN film. Antistatic coating. The applied coating composition was dried at 150 ° C for 5 minutes (thermal curing), and cured by ultraviolet light irradiation of about 500 W using an ultraviolet irradiation device, thereby producing a masking tape.

[實例2][Example 2]

將100重量份(以固體為基準)的一種丙烯酸系共聚物(Samwon出品之AT5100)加入600重量份之醋酸乙酯(EA)並攪拌一小時，然後在其中加入25重量份(以固體為基準)之能量射線固化型低聚物樹脂之脂肪族聚氨酯丙烯酸酯(Nippon Synthetic Chemical Industry之UV7600B80)，4重量份(以固體為基準)之矽酮六丙烯酸酯(CYTEC出品之EB1360)，及1重量份以膦為基料之光引發劑(CYTEC出品之DAROCUR TPO)，並將混合物攪拌一小時。然後在其中加入5重量份(以固體為基準)以三聚氰胺為基料的熱固化劑(Samwon出品之SM-20)及3重量份(以固體為基準)以有機酸為基料的熱固化促進劑(Samwon出品之A-20)，並將混合物攪拌一小時。將產生的黏著劑合成物敷設到厚度38μm的聚萘二甲酸乙二醇酯(PEN)薄膜上，敷設厚度約10μm，其中，該PEN薄膜的兩側皆已敷設一種表面電阻為105Ω/□之抗靜電塗層。讓敷設的塗層合成物在150℃下乾燥5分鐘，並使用能量射線固化之，藉此製出一遮蔽膠帶。100 parts by weight (on a solids basis) of an acrylic copolymer (AT5100 from Samwon) was added to 600 parts by weight of ethyl acetate (EA) and stirred for one hour, and then 25 parts by weight (based on solids) was added thereto. An aliphatic urethane acrylate of energy ray-curable oligomer resin (UV7600B80 from Nippon Synthetic Chemical Industry), 4 parts by weight (on a solids basis) of ketone hexaacrylate (EB1360 from CYTEC), and 1 weight A phosphine-based photoinitiator (DAROCUR TPO from CYTEC) was dispensed and the mixture was stirred for one hour. Then, 5 parts by weight (on a solids basis) of a melamine-based heat curing agent (SM-20 from Samwon) and 3 parts by weight (on a solid basis) based on an organic acid-based heat curing promotion were added thereto. The agent (A-20 from Samwon) was stirred and the mixture was stirred for one hour. The resulting adhesive composition was applied to a polyethylene naphthalate (PEN) film having a thickness of 38 μm and a thickness of about 10 μm was applied, wherein a surface resistance of 105 Ω/□ was applied to both sides of the PEN film. Antistatic coating. The applied coating composition was dried at 150 ° C for 5 minutes and cured using energy rays to thereby produce a masking tape.

[實例3][Example 3]

將100重量份(以固體為基準)的一種丙烯酸系共聚物(Samwon出品之AT5100)加入600重量份之醋酸乙酯(EA)並攪拌一小時，然後在其中加入25重量份(以固體為基準)之能量射線固化型低聚物樹脂之脂肪族聚氨酯丙烯酸酯(Nippon Synthetic Chemical Industry之UV7600B80)，2重量份(以固體為基準)之矽酮六丙烯酸酯(CYTEC出品之EB1360)，及1重量份以膦為基料之光引發劑(CYTEC出品之DAROCUR TPO)，並將混合物攪拌一小時。然後在其中加入3重量份(以固體為基準)以三聚氰胺為基料的熱固化劑(Samwon出品之SM-20)及1重量份(以固體為基準)以有機酸為基料的熱固化促進劑(Samwon出品之A-20)，並將混合物攪拌一小時。將產生的黏著劑合成物敷設到厚度38μm的聚萘二甲酸乙二醇酯(PEN)薄膜上，敷設厚度約10μm，其中，該PEN薄膜的兩側皆已敷設一種表面電阻為105Ω/□之抗靜電塗層。讓敷設的塗層合成物在150℃下乾燥5分鐘，並使用一紫外線輻射裝置以大約500W之紫外光輻射以使之固化，藉此製出一遮蔽膠帶。100 parts by weight (on a solids basis) of an acrylic copolymer (AT5100 from Samwon) was added to 600 parts by weight of ethyl acetate (EA) and stirred for one hour, and then 25 parts by weight (based on solids) was added thereto. An aliphatic urethane acrylate of energy ray-curable oligomer resin (UV7600B80 from Nippon Synthetic Chemical Industry), 2 parts by weight (on a solids basis) of ketone hexaacrylate (EB1360 from CYTEC), and 1 weight A phosphine-based photoinitiator (DAROCUR TPO from CYTEC) was dispensed and the mixture was stirred for one hour. Then, 3 parts by weight (on a solids basis) of a melamine-based heat curing agent (SM-20 produced by Samwon) and 1 part by weight (on a solid basis) based on an organic acid-based thermal curing promotion were added thereto. The agent (A-20 from Samwon) was stirred and the mixture was stirred for one hour. The resulting adhesive composition was applied to a polyethylene naphthalate (PEN) film having a thickness of 38 μm and a thickness of about 10 μm was applied, wherein a surface resistance of 105 Ω/□ was applied to both sides of the PEN film. Antistatic coating. The applied coating composition was dried at 150 ° C for 5 minutes and cured by ultraviolet radiation of about 500 W using an ultraviolet radiation device to thereby produce a masking tape.

[實例4][Example 4]

將100重量份(以固體為基準)的一種丙烯酸系共聚物(Samwon出品之AT5100)加入600重量份之醋酸乙酯(EA)並攪拌一小時，然後在其中加入25重量份(以固體為基準)之能量射線固化型低聚物樹脂之脂肪族聚氨酯丙烯酸酯(Nippon Synthetic Chemical Industry之UV7600B80)，1重量份(以固體為基準)之矽酮六丙烯酸酯(CYTEC出品之EB1360)，及1重量份以膦為基料之光引發劑(CYTEC出品之DAROCUR TPO)，並將混合物攪拌一小時。然後在其中加入5重量份(以固體為基準)以三聚氰胺為基料的熱固化劑(Samwon出品之SM-20)及3重量份(以固體為基準)以有機酸為基料的熱固化促進劑(Samwon出品之A-20)，並將混合物攪拌一小時。將產生的黏著劑合成物敷設到厚度38μm的聚萘二甲酸乙二醇酯(PEN)薄膜上，敷設厚度約10μm，其中，該PEN薄膜的兩側皆已敷設一種表面電阻為105Ω/□之抗靜電塗層。讓敷設的塗層合成物在150℃下乾燥5分鐘，並使用一紫外線輻射裝置以大約500W之紫外光輻射以使之固化，藉此製出一遮蔽膠帶。100 parts by weight (on a solids basis) of an acrylic copolymer (AT5100 from Samwon) was added to 600 parts by weight of ethyl acetate (EA) and stirred for one hour, and then 25 parts by weight (based on solids) was added thereto. An aliphatic urethane acrylate of energy ray-curable oligomer resin (UV7600B80 from Nippon Synthetic Chemical Industry), 1 part by weight (based on solids) of ketone hexaacrylate (EB1360 from CYTEC), and 1 weight A phosphine-based photoinitiator (DAROCUR TPO from CYTEC) was dispensed and the mixture was stirred for one hour. Then, 5 parts by weight (on a solids basis) of a melamine-based heat curing agent (SM-20 from Samwon) and 3 parts by weight (on a solid basis) based on an organic acid-based heat curing promotion were added thereto. The agent (A-20 from Samwon) was stirred and the mixture was stirred for one hour. The resulting adhesive composition was applied to a polyethylene naphthalate (PEN) film having a thickness of 38 μm and a thickness of about 10 μm was applied, wherein a surface resistance of 105 Ω/□ was applied to both sides of the PEN film. Antistatic coating. The applied coating composition was dried at 150 ° C for 5 minutes and cured by ultraviolet radiation of about 500 W using an ultraviolet radiation device to thereby produce a masking tape.

[實例5][Example 5]

將100重量份(以固體為基準)的一種丙烯酸系共聚物(Samwon出品之AT5100)加入600重量份之醋酸乙酯(EA)並攪拌一小時，然後在其中加入25重量份(以固體為基準)之能量射線固化型低聚物樹脂之脂肪族聚氨酯丙烯酸酯(Nippon Synthetic Chemical Industry之UV7600B80)，5重量份(以固體為基準)之矽酮六丙烯酸酯(CYTEC出品之EB1360)，及1重量份以膦為基料之光引發劑(CYTEC出品之DAROCUR TPO)，並將混合物攪拌一小時。然後在其中加入5重量份(以固體為基準)以三聚氰胺為基料的熱固化劑(Samwon出品之SM-20)及3重量份(以固體為基準)以有機酸為基料的熱固化促進劑(Samwon出品之A-20)，並將混合物攪拌一小時。將產生的黏著劑合成物敷設到厚度38μm的聚萘二甲酸乙二醇酯(PEN)薄膜上，敷設厚度約10μm，其中，該PEN薄膜的兩側皆已敷設一種表面電阻為105Ω/□之抗靜電塗層。讓敷設的塗層合成物在150℃下乾燥5分鐘，並使用一紫外線輻射裝置以大約500W之紫外光輻射以使之固化，藉此製出一遮蔽膠帶。100 parts by weight (on a solids basis) of an acrylic copolymer (AT5100 from Samwon) was added to 600 parts by weight of ethyl acetate (EA) and stirred for one hour, and then 25 parts by weight (based on solids) was added thereto. ) an aliphatic urethane acrylate of energy ray-curable oligomer resin (UV 7600B80 from Nippon Synthetic Chemical Industry), 5 parts by weight (based on solids) of ketone hexaacrylate (EB1360 from CYTEC), and 1 weight A phosphine-based photoinitiator (DAROCUR TPO from CYTEC) was dispensed and the mixture was stirred for one hour. Then, 5 parts by weight (on a solids basis) of a melamine-based heat curing agent (SM-20 from Samwon) and 3 parts by weight (on a solid basis) based on an organic acid-based heat curing promotion were added thereto. The agent (A-20 from Samwon) was stirred and the mixture was stirred for one hour. The resulting adhesive composition was applied to a polyethylene naphthalate (PEN) film having a thickness of 38 μm and a thickness of about 10 μm was applied, wherein a surface resistance of 105 Ω/□ was applied to both sides of the PEN film. Antistatic coating. The applied coating composition was dried at 150 ° C for 5 minutes and cured by ultraviolet radiation of about 500 W using an ultraviolet radiation device to thereby produce a masking tape.

[比較實例1][Comparative Example 1]

將100重量份(以固體為基準)的一種丙烯酸系共聚物(Samwon出品之AT5100)加入600重量份之醋酸乙酯(EA)並攪拌一小時，然後在其中加入25重量份(以固體為基準)之能量射線固化型低聚物樹脂之脂肪族聚氨酯丙烯酸酯(Nippon Synthetic Chemical Industry之UV7600B80)，10重量份(以固體為基準)之矽酮六丙烯酸酯(CYTEC出品之EB1360)，及1重量份以膦為基料之光引發劑(CYTEC出品之DAROCUR TPO)，並將混合物攪拌一小時。然後在其中加入5重量份(以固體為基準)以三聚氰胺為基料的熱固化劑(Samwon出品之SM-20)及3重量份(以固體為基準)以有機酸為基料的熱固化促進劑(Samwon出品之A-20)，並將混合物攪拌一小時。將產生的黏著劑合成物敷設到厚度38μm的聚萘二甲酸乙二醇酯(PEN)薄膜上，敷設厚度約10μm，其中，該PEN薄膜的兩側皆已敷設一種表面電阻為105Ω/□之抗靜電塗層。讓敷設的塗層合成物在150℃下乾燥5分鐘，並使用一紫外線輻射裝置以大約500W之紫外光輻射以使之固化，藉此製出一遮蔽膠帶。100 parts by weight (on a solids basis) of an acrylic copolymer (AT5100 from Samwon) was added to 600 parts by weight of ethyl acetate (EA) and stirred for one hour, and then 25 parts by weight (based on solids) was added thereto. An aliphatic urethane acrylate of energy ray-curable oligomer resin (UV7600B80 from Nippon Synthetic Chemical Industry), 10 parts by weight (on a solids basis) of ketone hexaacrylate (EB1360 from CYTEC), and 1 weight A phosphine-based photoinitiator (DAROCUR TPO from CYTEC) was dispensed and the mixture was stirred for one hour. Then, 5 parts by weight (on a solids basis) of a melamine-based heat curing agent (SM-20 from Samwon) and 3 parts by weight (on a solid basis) based on an organic acid-based heat curing promotion were added thereto. The agent (A-20 from Samwon) was stirred and the mixture was stirred for one hour. The resulting adhesive composition was applied to a polyethylene naphthalate (PEN) film having a thickness of 38 μm and a thickness of about 10 μm was applied, wherein a surface resistance of 105 Ω/□ was applied to both sides of the PEN film. Antistatic coating. The applied coating composition was dried at 150 ° C for 5 minutes and cured by ultraviolet radiation of about 500 W using an ultraviolet radiation device to thereby produce a masking tape.

[比較實例2][Comparative Example 2]

將100重量份(以固體為基準)的一種丙烯酸系共聚物(Samwon出品之AT5100)加入600重量份之醋酸乙酯(EA)並攪拌一小時，然後在其中加入25重量份(以固體為基準)之能量射線固化型低聚物樹脂之脂肪族聚氨酯丙烯酸酯(Nippon Synthetic Chemical Industry之UV7600B80)，3重量份(以固體為基準)之矽酮六丙烯酸酯(CYTEC出品之EB1360)，及1重量份以膦為基料之光引發劑(CYTEC出品之DAROCUR TPO)，並將混合物攪拌一小時。然後在其中加入3重量份(以固體為基準)以異氰酸酯為基料的熱固化劑(Dow Corning出品之CE138)，並將混合物攪拌一小時。將產生的黏著劑合成物敷設到厚度38μm的聚萘二甲酸乙二醇酯(PEN)薄膜上，敷設厚度約10μm，其中，該PEN薄膜的兩側皆已敷設一種表面電阻為105Ω/□之抗靜電塗層。讓敷設的塗層合成物在150℃下乾燥5分鐘，並使用一紫外線輻射裝置以大約500W之紫外光輻射以使之固化，藉此製出一遮蔽膠帶。100 parts by weight (on a solids basis) of an acrylic copolymer (AT5100 from Samwon) was added to 600 parts by weight of ethyl acetate (EA) and stirred for one hour, and then 25 parts by weight (based on solids) was added thereto. ) an aliphatic urethane acrylate of energy ray-curable oligomer resin (UV 7600B80 from Nippon Synthetic Chemical Industry), 3 parts by weight (based on solids) of ketone hexaacrylate (EB1360 from CYTEC), and 1 weight A phosphine-based photoinitiator (DAROCUR TPO from CYTEC) was dispensed and the mixture was stirred for one hour. Then, 3 parts by weight (on a solids basis) of an isocyanate-based heat curing agent (CE138 of Dow Corning) was added thereto, and the mixture was stirred for one hour. The resulting adhesive composition was applied to a polyethylene naphthalate (PEN) film having a thickness of 38 μm and a thickness of about 10 μm was applied, wherein a surface resistance of 105 Ω/□ was applied to both sides of the PEN film. Antistatic coating. The applied coating composition was dried at 150 ° C for 5 minutes and cured by ultraviolet radiation of about 500 W using an ultraviolet radiation device to thereby produce a masking tape.

[比較實例3][Comparative Example 3]

將100重量份(以固體為基準)的一種丙烯酸系共聚物(Samwon出品之AT5100)加入600重量份之醋酸乙酯(EA)並攪拌一小時，然後在其中加入25重量份(以固體為基準)之能量射線固化型低聚物樹脂之脂肪族聚氨酯丙烯酸酯(Nippon Synthetic Chemical Industry之UV7600B80)，及1重量份以膦為基料之光引發劑(CYTEC出品之DAROCUR TPO)，並將混合物攪拌一小時。然後在其中加入5重量份(以固體為基準)以三聚氰胺為基料的熱固化劑(Samwon出品之SM-20)及3重量份(以固體為基準)以有機酸為基料的熱固化促進劑(Samwon出品之A-20)，並將混合物攪拌一小時。將產生的黏著劑合成物敷設到厚度38μm的聚萘二甲酸乙二醇酯(PEN)薄膜上，敷設厚度約10μm，其中，該PEN薄膜的兩側皆已敷設一種表面電阻為105Ω/□之抗靜電塗層。讓敷設的塗層合成物在150℃下乾燥5分鐘，並使用一紫外線輻射裝置以大約500W之紫外光輻射以使之固化，藉此製出一遮蔽膠帶。100 parts by weight (on a solids basis) of an acrylic copolymer (AT5100 from Samwon) was added to 600 parts by weight of ethyl acetate (EA) and stirred for one hour, and then 25 parts by weight (based on solids) was added thereto. An aliphatic urethane acrylate of energy ray-curable oligomer resin (UV7600B80 from Nippon Synthetic Chemical Industry), and 1 part by weight of a phosphine-based photoinitiator (DAROCUR TPO from CYTEC), and the mixture is stirred One hour. Then, 5 parts by weight (on a solids basis) of a melamine-based heat curing agent (SM-20 from Samwon) and 3 parts by weight (on a solid basis) based on an organic acid-based heat curing promotion were added thereto. The agent (A-20 from Samwon) was stirred and the mixture was stirred for one hour. The resulting adhesive composition was applied to a polyethylene naphthalate (PEN) film having a thickness of 38 μm and a thickness of about 10 μm was applied, wherein a surface resistance of 105 Ω/□ was applied to both sides of the PEN film. Antistatic coating. The applied coating composition was dried at 150 ° C for 5 minutes and cured by ultraviolet radiation of about 500 W using an ultraviolet radiation device to thereby produce a masking tape.

[比較實例4][Comparative Example 4]

將100重量份(以固體為基準)的一種丙烯酸系共聚物(Samwon出品之AT5100)加入600重量份之醋酸乙酯(EA)並攪拌一小時，然後在其中加入25重量份(以固體為基準)之能量射線固化型低聚物樹脂之脂肪族聚氨酯丙烯酸酯(Nippon Synthetic Chemical Industry之UV7600B80)，2重量份(以固體為基準)之矽酮六丙烯酸酯(CYTEC出品之EB1360)，及1重量份以膦為基料之光引發劑(CYTEC出品之DAROCUR TPO)，並將混合物攪拌一小時。然後在其中加入5重量份(以固體為基準)以三聚氰胺為基料的熱固化劑(Samwon出品之SM-20)及3重量份(以固體為基準)以有機酸為基料的熱固化促進劑(Samwon出品之A-20)，並將混合物攪拌一小時。將產生的黏著劑合成物敷設到厚度38μm的聚萘二甲酸乙二醇酯(PEN)薄膜上，敷設厚度約10μm，其中，該PEN薄膜的兩側皆已敷設一種表面電阻為109Ω/□之抗靜電塗層。讓敷設的塗層合成物在150℃下乾燥5分鐘，並使用一紫外線輻射裝置以大約500W之紫外光輻射以使之固化，藉此製出一遮蔽膠帶。100 parts by weight (on a solids basis) of an acrylic copolymer (AT5100 from Samwon) was added to 600 parts by weight of ethyl acetate (EA) and stirred for one hour, and then 25 parts by weight (based on solids) was added thereto. An aliphatic urethane acrylate of energy ray-curable oligomer resin (UV7600B80 from Nippon Synthetic Chemical Industry), 2 parts by weight (on a solids basis) of ketone hexaacrylate (EB1360 from CYTEC), and 1 weight A phosphine-based photoinitiator (DAROCUR TPO from CYTEC) was dispensed and the mixture was stirred for one hour. Then, 5 parts by weight (on a solids basis) of a melamine-based heat curing agent (SM-20 from Samwon) and 3 parts by weight (on a solid basis) based on an organic acid-based heat curing promotion were added thereto. The agent (A-20 from Samwon) was stirred and the mixture was stirred for one hour. The resulting adhesive composition was applied to a polyethylene naphthalate (PEN) film having a thickness of 38 μm and a thickness of about 10 μm was applied, wherein a surface resistance of 109 Ω/□ was applied to both sides of the PEN film. Antistatic coating. The applied coating composition was dried at 150 ° C for 5 minutes and cured by ultraviolet radiation of about 500 W using an ultraviolet radiation device to thereby produce a masking tape.

[測試][test]

對上述各實例及比較實例中製出的晶粒外露式覆晶封裝(DEFCPs)製造用模壓底膠充填製程遮蔽膠帶，進行物理特性測試。選擇測試的特性項目時，係為了確認各實例的黏膠層與先前技術黏膠層比較時，具有增進的特徵。The mold-adhesive filling process masking tape for the manufacture of the die exposed flip chip package (DEFCPs) produced in the above examples and comparative examples was tested for physical properties. When selecting the characteristic item to be tested, it is an enhanced feature in order to confirm that the adhesive layer of each example is compared with the prior art adhesive layer.

1.印刷電路板(PCB)上的殘膠1. Residual glue on printed circuit board (PCB)

將每一黏膠薄膜敷設到一印刷電路板上，並於黏膠薄膜上放置一具有尖銳邊緣的模件。然後在一包括上、下板且溫度為175℃之熱壓機內，以700MPa(兆帕)的壓力壓縮所產生的薄膜。然後，使用顯微鏡觀察是否有黏膠層的殘膠留在印刷電路板上。並根據以下標準評定印刷電路板上的殘膠情況：良(O)表示未觀察到殘膠；不良(X)表示觀察到殘膠。Each adhesive film is applied to a printed circuit board, and a module having sharp edges is placed on the adhesive film. The resulting film was then compressed at a pressure of 700 MPa (MPa) in a hot press comprising upper and lower plates and at a temperature of 175 °C. Then, use a microscope to see if any of the adhesive layer of the adhesive layer remains on the printed circuit board. The residual rubber on the printed circuit board was evaluated according to the following criteria: good (O) indicates that no residue was observed; and poor (X) indicates that residual glue was observed.

2.環氧模塑料(EMC)沾污及離型特性2. Epoxy molding compound (EMC) staining and release characteristics

將環氧模塑料丸粒放在每一黏膠薄膜上，然後在一包括上、下板且溫度為175℃之熱壓機內，以700MPa(兆帕)的壓力進行模壓。並根據以下標準評定環氧模塑料上的污漬：良(O)表示模壓後的環氧模塑料表面是清潔的；不良(X)表示發生污漬或環氧模塑料滲入黏膠層。黏膠薄膜之離型特性也根據以下標準評定之：良(O)表示即便使用小力即可輕易移除黏膠薄膜而且未在模壓後的環氧模塑料表面上留下殘膠；不良(X)表示發生殘膠抑或無法輕易移除薄膜。表一顯示評定時使用的環氧模塑料類型及特性。An epoxy molding compound pellet was placed on each of the adhesive films, and then molded at a pressure of 700 MPa (MPa) in a hot press including the upper and lower plates at a temperature of 175 °C. The stain on the epoxy molding compound was evaluated according to the following criteria: good (O) indicates that the surface of the molded epoxy molding compound was clean; defective (X) indicates that stains or epoxy molding compound penetrated into the adhesive layer. The release characteristics of the adhesive film are also evaluated according to the following criteria: good (O) means that the adhesive film can be easily removed even with a small force and no residual glue remains on the surface of the molded epoxy molding compound; X) indicates that residual glue is occurring or the film cannot be easily removed. Table 1 shows the types and characteristics of the epoxy molding compound used in the evaluation.

3.黏著強度3. Adhesion strength

將每一黏膠薄膜沿縱長方向切成寬1”(英吋)×長15cm(公分)的尺寸，然後在室溫下使用2公斤的滾筒往復滾動二次，將黏膠薄膜層壓在一拋光的晶圓上。然後使用萬能測試機(UTM)在每分鐘300公厘(300mm/min)的速度下量測180。之剝離強度。Each adhesive film is cut into a width of 1" (inch) × 15cm (cm) in the longitudinal direction, and then reciprocally rolled twice at room temperature using a 2 kg roller to laminate the adhesive film On a polished wafer, the peel strength of 180 was measured using a universal testing machine (UTM) at a speed of 300 mm (300 mm/min) per minute.

4.表面電阻4. Surface resistance

使用一表面電阻計(Advantest出品之R8340A)在100伏特(V)之外加電壓下量測黏膠薄膜之表面電阻。The surface resistance of the adhesive film was measured using a surface resistance meter (R8340A from Advantest) under a voltage of 100 volts (V).

從以上表二可以看出，實例1至5滿足所有主要的要求特性。然而，在比較實例1中使用過量的以矽酮為基料的低聚物，雖然其他特性良好，但由於黏膠薄膜表面高度固化，所以印刷電路板上發生殘膠。在比較實例2中使用以異氰酸酯為基料的熱固化劑，流動性不良的Panasonic EXC14CE650U EMC滲入過度固化的黏膠層而使環氧模塑料(EMC)表面上發生污漬。以異氰酸酯為基料的固化劑具高度反應性，所以即便在室溫下也會起反應，但其過度固化而導致表面硬度增加。因此，流動性良好的環氧模塑料易於側向展開而不會滲入黏膠層；但是流動性不良的環氧模塑料與高表面硬度的黏膠層接觸時，易於滲入黏膠層，所以環氧模塑料表面上會發生污漬。基於這個原因，除比較實例2之外，在其他各實例與比較實例中，均同時使用以三聚氰胺為基料的熱固化劑(它會形成交聯的結構，視其添加量而定)及用來增加反應性的熱固化促進劑，以防黏著劑合成物過度固化並控制黏膠層的表面硬度，因此所有類型的環氧模塑料表面上都未發生污漬。在比較實例3中未使用以矽酮為基料的低聚物，不易從環氧模塑料移除遮蔽膠帶，且其黏著強度為100gf。比較實例4中，係在聚萘二甲酸乙二醇酯(PEN)薄膜上敷設表面電阻為109Ω/□之抗靜電塗層，其黏膠表面之表面電阻為1014Ω/□，指示它沒有抗靜電特性。As can be seen from Table 2 above, Examples 1 through 5 meet all of the major required characteristics. However, in Comparative Example 1, an excessive amount of an anthrone-based oligomer was used, and although other characteristics were good, since the surface of the adhesive film was highly cured, residual glue occurred on the printed circuit board. In Comparative Example 2, an isocyanate-based thermosetting agent was used, and a poorly fluid Panasonic EXC14CE650U EMC penetrated the over-cured adhesive layer to cause stain on the surface of the epoxy molding compound (EMC). The isocyanate-based curing agent is highly reactive, so it reacts even at room temperature, but it is excessively cured to cause an increase in surface hardness. Therefore, the epoxy molding compound with good fluidity is easy to spread laterally without penetrating into the adhesive layer; however, the epoxy molding compound having poor fluidity easily penetrates into the adhesive layer when it comes into contact with the adhesive layer of high surface hardness, so the ring Stains can occur on the surface of the oxygen molding compound. For this reason, in addition to Comparative Example 2, in each of the other examples and comparative examples, a melamine-based thermal curing agent (which forms a crosslinked structure depending on the amount of addition) and To increase the reactive thermal curing accelerator to prevent over-curing of the adhesive composition and to control the surface hardness of the adhesive layer, so that no stains appear on the surface of all types of epoxy molding compound. In Comparative Example 3, an anthrone-based oligomer was not used, and it was difficult to remove the masking tape from the epoxy molding compound, and the adhesive strength was 100 gf. In Comparative Example 4, an antistatic coating having a surface resistance of 109 Ω/□ was applied to a polyethylene naphthalate (PEN) film, and the surface resistance of the adhesive surface was 1014 Ω/□, indicating that it had no antistatic property. characteristic.

如上所述，本發明提供用於模壓底膠充填製程之遮蔽膠帶黏著劑合成物及包括此種黏著劑合成物之遮蔽膠帶。根據本發明之遮蔽膠帶包括改進的丙烯酸膠離型層，其可克服先前技術丙烯酸膠離型層會在印刷電路板表面留下殘膠及在任何類型環氧模塑料表面留下污漬的問題。由於本發明之遮蔽膠帶不會在印刷電路板表面留下殘膠，因此它可減少製程瑕疵率。此外，由於它不會在所有類型的環氧模塑料表面留下污漬，因此可以在模壓底膠充填製程中敷設到各種不同類型的環氧模塑料上。As described above, the present invention provides a masking tape adhesive composition for molding a primer filling process and a masking tape comprising such an adhesive composition. Masking tapes in accordance with the present invention include an improved acrylic release layer that overcomes the problems of prior art acrylic release layers that leave residual glue on the surface of the printed circuit board and leave stains on the surface of any type of epoxy molding compound. Since the masking tape of the present invention does not leave a residue on the surface of the printed circuit board, it can reduce the process throughput. In addition, since it does not leave stains on all types of epoxy molding compounds, it can be applied to a variety of different types of epoxy molding compounds in a molding primer filling process.

雖然以上舉例說明本發明若干較佳實施例，但是此類技術領域內的專技人士當可理解，該等實施例可作各種不同的修改、增添與替代而不脫離所附申請專利範圍中揭示的本發明範圍與精神。While the above is a preferred embodiment of the invention, it will be understood by those skilled in the art that The scope and spirit of the invention.

10．．．遮蔽膠帶10. . . Masking tape

11．．．耐熱薄膜基片11. . . Heat resistant film substrate

12,12’．．．抗靜電層12,12’. . . Antistatic layer

13．．．黏膠層13. . . Adhesive layer

14．．．上模14. . . Upper mold

15．．．下模15. . . Lower die

17．．．晶片17. . . Wafer

19．．．環氧模塑料(EMC)19. . . Epoxy molding compound (EMC)

第一圖：顯示使用本發明黏著劑合成物之模壓底膠充填製程遮蔽膠帶的大略斷面圖。First: A schematic cross-sectional view showing a masking primer filling process masking tape using the adhesive composition of the present invention.

第二圖：顯示本發明遮蔽膠帶應用於晶粒外露式覆晶封裝法之模壓底膠充填製程時的製造流程圖。The second figure shows the manufacturing flow chart of the masking tape of the present invention applied to the mold underfill filling process of the die exposed flip chip packaging method.

10．．．遮蔽膠帶10. . . Masking tape

11．．．耐熱薄膜基片11. . . Heat resistant film substrate

12,12’．．．抗靜電層12,12’. . . Antistatic layer

13．．．黏膠層13. . . Adhesive layer

Claims (8)

一種用於模壓底膠充填(MUF)製程之遮蔽膠帶黏著劑合成物，係包括：(a)　100重量份之丙烯酸系共聚物；(b)　1～20重量份之熱固化劑；(c)　5～40重量份之能量射線固化型聚氨酯樹脂；(d)　0.1～5重量份之能量射線固化型矽酮樹脂；以及(e)　一能量射線引發劑。A masking tape adhesive composition for a molding underfill (MUF) process comprising: (a) 100 parts by weight of an acrylic copolymer; (b) 1 to 20 parts by weight of a heat curing agent; (c) 5 to 40 parts by weight of the energy ray-curable urethane resin; (d) 0.1 to 5 parts by weight of the energy ray-curable fluorenone resin; and (e) an energy ray initiator. 如申請專利範圍第1項所述之用於模壓底膠充填(MUF)製程之遮蔽膠帶黏著劑合成物，其中所述能量射線固化型聚氨酯樹脂係選自以下群組中的一或多種：脂肪族雙官能聚氨酯丙烯酸酯、脂肪族三官能聚氨酯丙烯酸酯、脂肪族六官能聚氨酯丙烯酸酯、芳香族雙官能聚氨酯丙烯酸酯、芳香族三官能聚氨酯丙烯酸酯、及芳香族六官能聚氨酯丙烯酸酯。The masking tape adhesive composition for use in a molding underfill (MUF) process according to claim 1, wherein the energy ray-curable polyurethane resin is selected from one or more of the group consisting of: fat Family of bifunctional urethane acrylates, aliphatic trifunctional urethane acrylates, aliphatic hexafunctional urethane acrylates, aromatic difunctional urethane acrylates, aromatic trifunctional urethane acrylates, and aromatic hexafunctional urethane acrylates. 如申請專利範圍第1項所述之用於模壓底膠充填(MUF)製程之遮蔽膠帶黏著劑合成物，其中所述能量射線固化型矽酮樹脂係選自以下群組中的一或多種：矽酮二丙烯酸酯、矽酮六丙烯酸酯、矽酮聚酯丙烯酸酯、矽酮聚氨酯丙烯酸酯、及矽酮聚氨酯甲基丙烯酸甲酯。The masking tape adhesive composition for use in a molding primer filling (MUF) process according to claim 1, wherein the energy ray-curable indolinone resin is selected from one or more of the following groups: Anthrone diacrylate, anthrone hexaacrylate, anthrone polyester acrylate, anthrone urethane acrylate, and anthrone urethane methyl methacrylate. 如申請專利範圍第1項所述之用於模壓底膠充填(MUF)製程之遮蔽膠帶黏著劑合成物，其中所述熱固化劑是一種以三聚氰胺為基料的熱固化劑。A masking tape adhesive composition for use in a molding underfill (MUF) process according to claim 1, wherein the heat curing agent is a melamine-based heat curing agent. 一種用於模壓底膠充填製程之遮蔽膠帶，係包括：一耐熱薄膜基片；一抗靜電層，設於耐熱薄膜基片的一側或兩側；以及一黏膠層，設於抗靜電層上；所述黏膠層係由申請專利範圍第1項之黏著劑合成物形成的。A masking tape for molding a primer filling process, comprising: a heat-resistant film substrate; an antistatic layer disposed on one side or both sides of the heat-resistant film substrate; and an adhesive layer disposed on the antistatic layer The adhesive layer is formed by the adhesive composition of claim 1 of the patent application. 如申請專利範圍第5項所述用於模壓底膠充填製程之遮蔽膠帶，其中所述之耐熱薄膜基片係選自以下群組中之任何一種：聚酰亞胺薄膜(PI)、聚對苯二甲酸乙二酯薄膜(PET)、聚萘二甲酸乙二醇酯薄膜(PEN)、及聚丁烯對苯二甲酸酯薄膜(PBT)。The masking tape for molding a primer filling process according to claim 5, wherein the heat-resistant film substrate is selected from any one of the group consisting of polyimide film (PI), poly pair Ethylene phthalate film (PET), polyethylene naphthalate film (PEN), and polybutylene terephthalate film (PBT). 如申請專利範圍第5項所述所述用於模壓底膠充填製程之遮蔽膠帶，其中所述黏膠層在室溫下對拋光後矽晶圓之黏著強度為50gf/inch或更低。The masking tape for molding a primer filling process according to claim 5, wherein the adhesive layer has an adhesive strength of 50 gf/inch or less to the polished wafer at room temperature. 如申請專利範圍第5項所述用於模壓底膠充填製程之遮蔽膠帶，其中所述黏膠層之表面電阻為1011Ω/□或更低。The masking tape for molding a primer filling process according to claim 5, wherein the adhesive layer has a surface resistance of 1011 Ω/□ or less.
TW101101984A 2011-10-07 2012-01-18 Adhesive composition for masking tape for mold underfill process and masking tape using the same TWI445786B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020110102320A KR101209552B1 (en) 2011-10-07 2011-10-07 Adhesive composition for masking tape for mold underfill process and masking tape using the same

Publications (2)

Publication Number Publication Date
TW201315786A TW201315786A (en) 2013-04-16
TWI445786B true TWI445786B (en) 2014-07-21

Family

ID=47907127

Family Applications (1)

Application Number Title Priority Date Filing Date
TW101101984A TWI445786B (en) 2011-10-07 2012-01-18 Adhesive composition for masking tape for mold underfill process and masking tape using the same

Country Status (3)

Country Link
JP (1) JP5548711B2 (en)
KR (1) KR101209552B1 (en)
TW (1) TWI445786B (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2015133630A1 (en) 2014-03-07 2017-04-06 旭硝子株式会社 Release film, method for producing the same, and method for producing semiconductor package
WO2016002026A1 (en) 2014-07-02 2016-01-07 日立化成株式会社 Photosensitive refractive index-adjusting transfer film
WO2016013587A1 (en) 2014-07-24 2016-01-28 日立化成株式会社 Photosensitive resin composition, photosensitive film, pattern substrate, photosensitive conductive film, and conductive pattern substrate
JP6605846B2 (en) * 2015-06-03 2019-11-13 日東電工株式会社 Masking adhesive tape
KR20180063106A (en) 2015-09-30 2018-06-11 히타치가세이가부시끼가이샤 Transfer-type photosensitive film for refractive-index modulation
JP6767763B2 (en) * 2016-03-29 2020-10-14 三井化学東セロ株式会社 A mold release film for a process that has an excellent appearance of a molded product, its application, and a method for manufacturing a resin-sealed semiconductor using the same.
US20190144726A1 (en) * 2016-05-13 2019-05-16 3M Innovative Properties Company Thermally stable siloxane-based protection film
WO2018021051A1 (en) * 2016-07-28 2018-02-01 日東電工株式会社 Separator-covered reinforcing film
JP2018161448A (en) * 2017-03-27 2018-10-18 日本絨氈株式会社 Tile carpet
CN112250818A (en) * 2020-09-27 2021-01-22 长春一汽富维东阳汽车塑料零部件有限公司 Recyclable water-based polyurethane shielding material and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005166904A (en) * 2003-12-02 2005-06-23 Hitachi Chem Co Ltd Mold releasing sheet for semiconductor mold
KR101359748B1 (en) * 2007-10-16 2014-02-06 덴끼 가가꾸 고교 가부시키가이샤 Pressure-sensitive adhesive, pressure-sensitive adhesive sheet, multilayered pressure-sensitive adhesive sheet, and process for producing electronic part
JP2011253833A (en) * 2008-09-29 2011-12-15 Denki Kagaku Kogyo Kk Method of manufacturing semiconductor member and adhesive tape
JP2010263041A (en) * 2009-05-01 2010-11-18 Nitto Denko Corp Dicing tape with die attach film, and method of manufacturing semiconductor apparatus

Also Published As

Publication number Publication date
JP2013084873A (en) 2013-05-09
KR101209552B1 (en) 2012-12-06
TW201315786A (en) 2013-04-16
JP5548711B2 (en) 2014-07-16

Similar Documents

Publication Publication Date Title
TWI445786B (en) Adhesive composition for masking tape for mold underfill process and masking tape using the same
KR102042598B1 (en) Surface protective sheet
TWI506688B (en) Method of applying pressure-sensitive adhesive sheet for semiconductor wafer protection and pressure-sensitive adhesive sheet for semiconductor wafer protection for use in the application method
KR101392441B1 (en) Adhesive composition for masking tape of mold underfill process and masking tape using the same
TW201920558A (en) Reinforced film
TWI753851B (en) Adhesive sheet for semiconductor processing
KR101089631B1 (en) Multilayer adhesive film for semiconductor package
KR100894173B1 (en) Mulitlayer adhesive film for semiconductor package
JP2008280520A (en) Pressure-sensitive adhesive tape for fixing semiconductor
JP2009138026A (en) Energy ray-curable chip protecting film
CN111670231B (en) Film-like adhesive and sheet for semiconductor processing
CN103081068A (en) Film for semiconductor device and semiconductor device
TWI770371B (en) Die bonding film, dicing die bonding sheet, and method for producing semiconductor chip
JP5607401B2 (en) Antistatic type semiconductor processing adhesive tape
KR20150058242A (en) Back grinding sheet
JP5942321B2 (en) Adhesive composition for masking tape in mold underfill process and masking tape using the same
JP6461892B2 (en) Surface protection sheet
JP2010278297A (en) Adhesive tape for fixing semiconductor and method of manufacturing the same
US10224230B2 (en) Surface protective sheet
US11482441B2 (en) Method for manufacturing semiconductor device by backgrinding semiconductor wafer using an adhesive film
TWI715652B (en) Film for forming protective film and composite sheet for forming protective film
JPWO2018083987A1 (en) Stealth dicing adhesive sheet
EP2927952B1 (en) Sheet for forming resin film for chips and method for manufacturing semiconductor device
JP6717484B2 (en) Adhesive sheet
JP6719694B1 (en) Dicing sheet for plasma dicing

Legal Events

Date Code Title Description
MM4A Annulment or lapse of patent due to non-payment of fees