TWI566282B - Cut the adhesive sheet - Google Patents
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- TWI566282B TWI566282B TW101126559A TW101126559A TWI566282B TW I566282 B TWI566282 B TW I566282B TW 101126559 A TW101126559 A TW 101126559A TW 101126559 A TW101126559 A TW 101126559A TW I566282 B TWI566282 B TW I566282B
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- 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
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
- H01L24/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
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- 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
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67132—Apparatus for placing on an insulating substrate, e.g. tape
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- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
- H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/27—Manufacturing methods
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
- H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
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- 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
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/8319—Arrangement of the layer connectors prior to mounting
- H01L2224/83191—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body
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- 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
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- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Dicing (AREA)
- Die Bonding (AREA)
Description
本發明關於適用於半導體元件(半導體晶片)黏結於有機基板或連結框(link frame)的晶粒墊(die pad)或其他半導體晶片之步驟以及切割半導體晶圓做成半導體晶片使半導體晶片晶粒黏結於被黏接部之步驟的切割黏結片(dicing-die bonding sheet)。 The present invention relates to a step of applying a semiconductor device (semiconductor wafer) to a die pad or other semiconductor wafer of an organic substrate or a link frame, and cutting the semiconductor wafer to form a semiconductor wafer to make the semiconductor wafer die A dicing-die bonding sheet bonded to the step of being bonded.
矽、硼化鍺等的半導體晶圓以大直徑的狀態被製造。半導體晶圓在被切斷(dicing)成小片元件(半導體晶片)後，移至下一步驟的晶粒黏結(die bonding)步驟。此時，半導體晶圓以預先黏貼於接著片的狀態進行切割、洗淨、乾燥、延展及提取各步驟後，移送至下一步驟之晶粒黏結步驟。 Semiconductor wafers such as tantalum or tantalum boride are manufactured in a large diameter state. After the semiconductor wafer is diced into small pieces (semiconductor wafer), it is moved to the die bonding step of the next step. At this time, the semiconductor wafer is diced, washed, dried, stretched, and extracted in a state of being adhered to the adhesive sheet in advance, and then transferred to the die bonding step of the next step.
這些步驟之中，為了簡化提取步驟及晶粒黏結步驟的流程，而對於同時兼具晶圓固定機能與晶粒黏結機能的切割黏結片有多種提案(例如專利文獻1)。專利文獻1揭示之黏接片，可進行所謂的直接黏結(direct die bonding)，省略晶粒黏接用黏接劑的塗佈步驟。例如藉由使用上述的黏接片可得到具有黏接劑層的半導體晶片，使得有機基板與晶片之間、導線架(lead frame)與晶片之間、晶片與晶片之間等可直接黏結。如此的黏接片的黏接劑層具有流動性，達到晶圓固定機能與晶粒接著機能。 Among these steps, in order to simplify the flow of the extraction step and the die bonding step, there are various proposals for a dicing bonded sheet having both a wafer fixing function and a die bonding function (for example, Patent Document 1). In the adhesive sheet disclosed in Patent Document 1, so-called direct die bonding can be performed, and the coating step of the die bonding adhesive can be omitted. For example, a semiconductor wafer having an adhesive layer can be obtained by using the above-mentioned adhesive sheet, so that the organic substrate and the wafer, the lead frame and the wafer, and the wafer and the wafer can be directly bonded. The adhesive layer of such a bonding sheet has fluidity to achieve the function of the wafer fixing function and the die.
近年來，在半導體裝置製造步驟之時，晶片內面的黏 接劑層收縮，因而使晶片端部附近的有機基板等的被接著體與晶片之間產生空隙。一旦被接著體與晶片之間產生空隙，在半導體裝置製造步驟的模具樹脂封裝步驟時，模具樹脂無法充分進入空隙而發生空隙，使得半導體裝置的信賴性降低。 In recent years, at the time of the semiconductor device manufacturing step, the inner surface of the wafer is sticky. Since the adhesive layer shrinks, a void is formed between the adherend of the organic substrate or the like in the vicinity of the end portion of the wafer and the wafer. When a void is formed between the adherend and the wafer, the mold resin does not sufficiently enter the void to form a void during the mold resin encapsulation step of the semiconductor device manufacturing step, so that the reliability of the semiconductor device is lowered.
又當製造在半導體晶片上更以中間為接著劑層層積半導體晶片的多段堆疊的半導體裝置的情形時，因晶片之間的接著劑層收縮而曝露出下段的晶片表面。在模具樹脂封裝步驟時，因模具樹脂所含的矽填充物，會損害曝露出的晶片表面，而使半導體裝置的信賴性降低。 Further, in the case of manufacturing a multi-segment stacked semiconductor device in which a semiconductor wafer is laminated on a semiconductor wafer and an intermediate layer is laminated, the wafer surface of the lower stage is exposed by shrinkage of the adhesive layer between the wafers. At the time of the mold resin encapsulation step, the surface of the exposed wafer is damaged by the ruthenium filler contained in the mold resin, and the reliability of the semiconductor device is lowered.
此半導體裝置的信賴性降低會因半導體晶片的高密度化或半導體晶片的層積數增加而變得更明顯。 The decrease in the reliability of the semiconductor device is more conspicuous due to the higher density of the semiconductor wafer or the increase in the number of layers of the semiconductor wafer.
【專利文獻1】特開2007-314603號公報 [Patent Document 1] JP-A-2007-314603
本發明人等潛心檢討的結果，了解接著劑層的收縮在半導體裝置製造步驟的切割步驟中發生。亦即，如第1及2圖所示，切割步驟時，以切割刀5將半導體晶圓4或接著劑層2完全切斷，但是基材1以未完全切斷的範圍切入。此時，半導體晶圓4的切口(切割後切斷的部分6)鄰接的基材，即對應半導體晶片3端部部分的基材向接著劑層側變形。因為基材的變形，對應半導體晶片3的接著劑層從 接著劑層端部向內部方向的應力作用，使得接著劑層收縮。 As a result of intensive review by the present inventors, it is understood that shrinkage of the adhesive layer occurs in the cutting step of the semiconductor device manufacturing step. That is, as shown in Figs. 1 and 2, in the dicing step, the semiconductor wafer 4 or the adhesive layer 2 is completely cut by the dicing blade 5, but the substrate 1 is cut in a range that is not completely cut. At this time, the substrate adjacent to the slit (the portion 6 cut after cutting) of the semiconductor wafer 4, that is, the substrate corresponding to the end portion of the semiconductor wafer 3 is deformed toward the adhesive layer side. Because of the deformation of the substrate, the adhesive layer corresponding to the semiconductor wafer 3 is The stress in the inner direction of the end of the layer then acts to shrink the adhesive layer.
本發明之課題在於提供具有可抑制切割步驟時伴隨基材變形的接著劑層收縮之接著劑層之切割黏結片。 An object of the present invention is to provide a cut-and-bonded sheet having an adhesive layer capable of suppressing shrinkage of an adhesive layer accompanying deformation of a substrate in a dicing step.
本發明之要旨如下。 The gist of the present invention is as follows.
(1)於基材上層積接著劑層之切割黏結片，上述接著劑層在硬化前的狀態下，80℃的儲存彈性率為50,000~5,000,000Pa，且在80℃環境下施以20%扭曲應力120秒後的應力緩和率為30~90%。 (1) A dicing adhesive sheet in which an adhesive layer is laminated on a substrate, and the above-mentioned adhesive layer has a storage elastic modulus of 50,000 to 5,000,000 Pa at 80 ° C in a state before hardening, and a 20% distortion at 80 ° C; The stress relaxation rate after 120 seconds of stress is 30 to 90%.
(2)上述接著劑層在硬化前的狀態下，80℃的tan δ為0.1~0.38之(1)記載之切割黏結片。 (2) The dicing adhesive sheet described in (1) of the above-mentioned adhesive layer in a state before curing, at a tan δ of 80 ° C of 0.1 to 0.38.
(3)上述接著劑層由含有丙烯聚合物(A)及環氧樹脂(B)之接著劑組成物所形成之(1)或(2)記載之切割黏結片。 (3) The above-mentioned adhesive layer is a cut-and-bonded sheet according to (1) or (2) which is formed of an adhesive composition containing a propylene polymer (A) and an epoxy resin (B).
(4)上述丙烯聚合物(A)具有反應性官能基之(3)記載之切割黏結片。 (4) The diculated adhesive sheet according to (3), wherein the propylene polymer (A) has a reactive functional group.
(5)上述丙烯聚合物(A)在該接著劑組合物100質量部中含有10質量部以上之(3)或(4)記載之切割黏結片。 (5) The propylene polymer (A) contains 10 parts by mass or more of the cut-and-bonded sheet described in (3) or (4) in the mass portion of the adhesive composition 100.
(6)上述接著劑組成物含有交聯劑，該交聯劑，相對於上述丙烯聚合物(A)100重量部，含有1~40質量部之(3)~(5)任一記載之切割黏結片。 (6) The above-mentioned adhesive composition contains a crosslinking agent, and the crosslinking agent contains 1 to 40 parts by mass of the propylene polymer (A) in a weight ratio of (3) to (5). Bonding sheet.
(7)上述丙烯聚合物(A)在上述接著劑組成物100質量部中含有高於35質量部，且上述交聯劑，相對於上述丙烯聚合物(A)100質量部，含有5質量部以上、未滿20質量部之(6)記載之切割黏結片。 (7) The propylene polymer (A) contains more than 35 parts by mass in the mass portion of the adhesive composition 100, and the crosslinking agent contains 5 parts by mass with respect to 100 parts by mass of the propylene polymer (A). The cut-and-bonded sheet described in (6) of the above-mentioned 20 parts.
(8)上述丙烯聚合物(A)在上述接著劑組成物100質量部中含有10~35質量部，且上述交聯劑，相對於上述丙烯聚合物(A)100質量部，含有20~35質量部之(6)記載之切割黏結片。 (8) The propylene polymer (A) contains 10 to 35 parts by mass in the mass portion of the adhesive composition 100, and the crosslinking agent contains 20 to 35 with respect to 100 parts by mass of the propylene polymer (A). The cut-and-bonded sheet described in (6) of the quality department.
(9)上述基材包含選自由聚乙烯膜、乙烯甲基丙烯酸共聚物膜、聚丙烯膜所構成的群組中之1種以上(1)~(8)任一記載之切割黏結片。 (9) The base material is one or more selected from the group consisting of a polyethylene film, an ethylene methacrylic acid copolymer film, and a polypropylene film, and the dicing adhesive sheet according to any one of (1) to (8).
根據本發明之切割黏結片，在對應半導體晶圓切割步驟時產生的熱的溫度上下之儲存彈性率及應力緩和率受到控制，因此可抑制切割步驟時基材變形所伴隨的接著劑層的收縮。因此，可製造信賴性高的半導體裝置。 According to the dicing bonded sheet of the present invention, the storage elastic modulus and the stress relaxation ratio above and below the temperature of the heat generated in the step of cutting the semiconductor wafer are controlled, thereby suppressing the shrinkage of the adhesive layer accompanying the deformation of the substrate during the cutting step. . Therefore, a highly reliable semiconductor device can be manufactured.
以下詳細說明本發明切割黏結片。本發明之切割黏結片係於基材上層積接著劑層。 The cut adhesive sheet of the present invention will be described in detail below. The dicing adhesive sheet of the present invention is formed by laminating an adhesive layer on a substrate.
本發明之切割黏結片中的接著劑層(以下簡稱「接著劑層」)在硬化前的狀態下80℃的儲存彈性率為50,000~5,000,000Pa，較佳為65,000~4,000,000 Pa。而且，接著劑層在80℃環境下施以20%扭曲應力120秒後的應力緩和率為30~90%，較佳為40~80%。接著劑層的儲存彈性率在上述範圍者，可抑制在切割步驟時起因於基材變形的應力導致的接著劑的收縮。又接著劑層的應力緩和率在上述範圍者，在後述的提取步驟中，半導體晶片與接著劑層一起從基材剝離，使得對抗接著劑層收縮應力的殘餘應 力難以減少，而使收縮的接著劑恢復至半導體晶片的體積。另一方面，在80℃的儲存彈性率過大、應力緩和率過小的情形中，接著劑層過度變硬，使得半導體晶圓與接著劑層的界面的接著性降低，或使已黏結的被接著體與接著劑層的接著性降低。又在80℃的儲存彈性率過小、應力緩和率過大的情形中，抑制接著劑層的收縮會變得困難。所謂「硬化前的狀態」表示在半導體晶片封裝後進行加熱硬化之前的狀態，不是討論後述的能量線照射而硬化的前後關係。 The adhesive layer in the cut-and-bonded sheet of the present invention (hereinafter referred to as "adhesive layer") has a storage elastic modulus at 80 ° C in a state before curing of 50,000 to 5,000,000 Pa, preferably 65,000 to 4,000,000 Pa. Further, the stress relaxation rate of the adhesive layer after applying a 20% twist stress for 120 seconds in an environment of 80 ° C is 30 to 90%, preferably 40 to 80%. When the storage elastic modulus of the subsequent layer is in the above range, the shrinkage of the adhesive due to the stress of deformation of the substrate during the cutting step can be suppressed. Further, when the stress relaxation rate of the adhesive layer is in the above range, in the extraction step described later, the semiconductor wafer is peeled off from the substrate together with the adhesive layer, so that the residual stress against the adhesive layer of the adhesive layer should be It is difficult to reduce the force and return the contracted adhesive to the volume of the semiconductor wafer. On the other hand, in the case where the storage elastic modulus at 80 ° C is excessively large and the stress relaxation rate is too small, the adhesive layer is excessively hardened, so that the adhesion of the interface between the semiconductor wafer and the adhesive layer is lowered, or the bonded one is continued. The adhesion of the body to the adhesive layer is reduced. Further, in the case where the storage elastic modulus at 80 ° C is too small and the stress relaxation rate is excessively large, it is difficult to suppress shrinkage of the adhesive layer. The "state before hardening" indicates a state before heat-hardening after semiconductor wafer packaging, and is not related to the relationship between the curing by the energy ray irradiation described later.
本發明之接著劑層硬化前的狀態，80℃的tan δ較佳為0.1~0.38，更佳為0.15~0.36。接著劑層的tan δ在上述範圍者，在後述的提取步驟中，半導體晶片與接著劑層一起從基材剝離，使得對抗接著劑層收縮應力的殘餘應力難以減少，而使已收縮的接著劑層容易恢復至半導體晶片的體積。所謂「硬化前的狀態」表示在半導體晶片封裝後進行加熱硬化之前的狀態，不是討論後述的能量線照射而硬化的前後關係。 In the state before the adhesive layer of the present invention is cured, the tan δ at 80 ° C is preferably from 0.1 to 0.38, more preferably from 0.15 to 0.36. When the tan δ of the subsequent layer is in the above range, in the extraction step described later, the semiconductor wafer is peeled off from the substrate together with the adhesive layer, so that it is difficult to reduce the residual stress against the shrinkage stress of the adhesive layer, and the shrinkable adhesive is made. The layer is easily restored to the volume of the semiconductor wafer. The "state before hardening" indicates a state before heat-hardening after semiconductor wafer packaging, and is not related to the relationship between the curing by the energy ray irradiation described later.
本發明之接著劑層較佳由含有丙烯聚合物(A)及環氧樹脂(B)之接著劑組成物所形成。為了改良各種物性，該接著劑組成物可視需要調配其他成份。以下對於這些成分具體說明。 The adhesive layer of the present invention is preferably formed of an adhesive composition containing a propylene polymer (A) and an epoxy resin (B). In order to improve various physical properties, the adhesive composition may be formulated with other ingredients as needed. These components are specifically described below.
丙烯聚合物(A)可使用公知之丙烯聚合物。丙烯聚合物(A)的重量平均分子量(Mw)較佳1萬~200萬，更佳為10萬 ~150萬。丙烯聚合物(A)的Mw過低者，不只儲存彈性率及應力緩和率的值難以調整至上述範圍，而且接著劑層與基材的接著力變高而引起晶片提取不良。丙烯聚合物(A)的Mw過高者，接著劑層無法依循被接著體的凹凸，為空隙等發生的要因。丙烯聚合物(A)的Mw以膠滲透層析法(GPC)所測定的聚苯乙烯換算值。 As the propylene polymer (A), a known propylene polymer can be used. The weight average molecular weight (Mw) of the propylene polymer (A) is preferably from 10,000 to 2,000,000, more preferably 100,000. ~1.5 million. When the Mw of the propylene polymer (A) is too low, it is difficult to adjust the values of the elastic modulus and the stress relaxation ratio to the above range, and the adhesion between the adhesive layer and the substrate becomes high, resulting in poor wafer extraction. When the Mw of the propylene polymer (A) is too high, the adhesive layer cannot follow the irregularities of the adherend, and is a factor that occurs in voids or the like. The Mw of the propylene polymer (A) is a polystyrene-converted value measured by gel permeation chromatography (GPC).
丙烯聚合物(A)的玻璃轉移溫度(Tg)較佳為-40~50℃，更加為-35~45℃。本發明之接著劑層為了顯示設定的儲存彈性率與應力緩和率，較佳為丙烯聚合物(A)的Tg高者。丙烯聚合物(A)的Tg過低者，不只儲存彈性率及應力緩和率的值難以調整至上述範圍，而且接著劑層與基材的接著力變高而引起晶片提取不良。丙烯聚合物(A)的Tg過高者，則固定晶圓的接著力恐怕不足。 The glass transition temperature (Tg) of the propylene polymer (A) is preferably -40 to 50 ° C, more preferably -35 to 45 ° C. The adhesive layer of the present invention is preferably one having a higher Tg of the propylene polymer (A) in order to exhibit a set storage elastic modulus and a stress relaxation ratio. When the Tg of the propylene polymer (A) is too low, it is difficult to adjust the values of the elastic modulus and the stress relaxation ratio to the above range, and the adhesion between the adhesive layer and the substrate becomes high, resulting in poor wafer extraction. If the Tg of the propylene polymer (A) is too high, the adhesion of the fixed wafer may be insufficient.
構成丙烯聚合物(A)的單體例如(甲基)丙烯酸酯及其衍生物。 The monomer constituting the propylene polymer (A) is, for example, (meth) acrylate and a derivative thereof.
具體例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯等的烷基碳數1~18的(甲基)丙烯酸烷基酯；(甲基)丙烯酸環烷酯、(甲基)丙烯酸苯甲酯、異佛爾酮(甲基)丙烯酸酯、二環戊基(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯、二環戊烯基氧乙基(甲基)丙烯酸酯、亞胺(甲基)丙烯酸酯等的具有環狀結構之(甲基)丙烯酸酯；羥甲基(甲基)丙烯酸酯、2-羥乙基(甲基)丙烯酸酯、 2-羥丙基(甲基)丙烯酸酯等的含羥基的(甲基)丙烯酸酯；或丙烯酸、甲基丙烯酸、衣康酸、縮水甘油基丙烯酸酯、縮水甘油基甲基丙烯酸酯等。 Specifically, for example, (meth)acrylic acid alkyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, or the like, alkyl (meth)acrylic acid alkyl group having 1 to 18 carbon atoms Ester; cycloalkyl (meth) acrylate, benzyl (meth) acrylate, isophorone (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (methyl) (meth) acrylate having a cyclic structure such as acrylate, dicyclopentenyloxyethyl (meth) acrylate or imine (meth) acrylate; hydroxymethyl (meth) acrylate 2-hydroxyethyl (meth) acrylate, A hydroxyl group-containing (meth) acrylate such as 2-hydroxypropyl (meth) acrylate; or acrylic acid, methacrylic acid, itaconic acid, glycidyl acrylate, glycidyl methacrylate or the like.
也可與乙酸乙烯酯、丙腈、苯乙烯等共聚合。 It can also be copolymerized with vinyl acetate, propionitrile, styrene or the like.
這些可單獨1種使用，或者2種以上併用。 These may be used alone or in combination of two or more.
使用烷基碳數1~18的(甲基)丙烯酸烷基酯為構成丙烯聚合物(A)的單體的情形中，(甲基)丙烯酸烷基酯的碳數平均較佳為2~6。其中，(甲基)丙烯酸烷基酯的碳數在8左右，(甲基)丙烯酸烷基酯的均聚物的Tg最小，典型的為丙烯酸-2-乙基己酯的均聚物的Tg為-70℃。因此當(甲基)丙烯酸烷基酯的碳數超過6的情形中，難以調整Tg於上述較佳範圍。碳數的平均小於2的情形中，接著劑層的柔軟性喪失，對被接著體的接著性變差。又在碳數超過8的情形中，Tg容易上升，但因為側鏈結晶化的傾向，接著劑層顯示特異的特性，使得儲存彈性率或應力緩和率的控制變得困難。 In the case of using a (meth)acrylic acid alkyl ester having an alkyl carbon number of 1 to 18 as a monomer constituting the propylene polymer (A), the alkyl number of the (meth)acrylic acid alkyl ester is preferably from 2 to 6 on average. . Wherein, the alkyl (meth) acrylate has a carbon number of about 8, and the homopolymer of the (meth) acrylate alkyl ester has the smallest Tg, and is typically a Tg of a homopolymer of 2-ethylhexyl acrylate. It is -70 °C. Therefore, in the case where the carbon number of the alkyl (meth)acrylate exceeds 6, it is difficult to adjust the Tg to the above preferred range. In the case where the average carbon number is less than 2, the flexibility of the adhesive layer is lost, and the adhesion to the adherend is deteriorated. Further, in the case where the carbon number exceeds 8, the Tg tends to increase. However, since the side chain is crystallized, the adhesive layer exhibits specific characteristics, making it difficult to control the storage modulus or the stress relaxation rate.
本發明之丙烯聚合物(A)較佳具有反應性官能基。反應性官能基與構成本發明之接著劑層的接著劑組成物中較佳添加之交聯劑(J)的反應性官能基反應，形成三維網絡結構，使得上述接著劑層的儲存彈性率與應力緩和率容易調整至設定範圍。丙烯聚合物(A)的反應性官能基例如羧基、胺基、環氧基、羥基等，但從容易與交聯劑(J)選擇性反應的觀點，較佳為羥基。反應性官能基係使用上述含羥基之(甲基)丙烯酸酯、丙烯酸等的具有反應性官能基之單體而 構成丙烯聚合物(A)者，可導入丙烯聚合物(A)。 The propylene polymer (A) of the present invention preferably has a reactive functional group. The reactive functional group reacts with a reactive functional group of the preferably added crosslinking agent (J) in the adhesive composition constituting the adhesive layer of the present invention to form a three-dimensional network structure such that the storage elastic modulus of the above adhesive layer is The stress relaxation rate is easily adjusted to the setting range. The reactive functional group of the propylene polymer (A) is, for example, a carboxyl group, an amine group, an epoxy group, a hydroxyl group or the like, but is preferably a hydroxyl group from the viewpoint of being easily reacted selectively with the crosslinking agent (J). The reactive functional group is a monomer having a reactive functional group such as a hydroxyl group-containing (meth) acrylate or acrylic acid. The propylene polymer (A) can be introduced into the propylene polymer (A).
丙烯聚合物(A)，在其構成的全單體中，較佳含有5~30質量%的具有反應性官能基的單體，更佳包含10~25質量%。具有反應性官能基的單體的比例在此範圍者，經後述交聯劑(J)而使丙烯聚合物(A)被有效地交聯，使得上述接著劑層的儲存彈性率與應力緩和率容易調整至設定的範圍。丙烯聚合物(A)的反應官能基(例如羥基)的當量，較佳為交聯劑(J)的反應性官能基(例如異氰酸酯基)當量的0.17~2.0倍。丙烯聚合物(A)的反應性官能基當量與交聯劑(J)的反應性官能基當量的關係為上述範圍者，使得上述接著劑層的儲存彈性率與應力緩和率容易調整至設定的範圍。 The propylene polymer (A) preferably contains 5 to 30% by mass of a monomer having a reactive functional group, more preferably 10 to 25% by mass, based on the total monomer. In the range where the ratio of the monomer having a reactive functional group is in this range, the propylene polymer (A) is effectively crosslinked by the crosslinking agent (J) described later, so that the storage elastic modulus and the stress relaxation rate of the above-mentioned adhesive layer are obtained. Easy to adjust to the set range. The equivalent of the reactive functional group (for example, hydroxyl group) of the propylene polymer (A) is preferably 0.17 to 2.0 times the equivalent of the reactive functional group (for example, isocyanate group) of the crosslinking agent (J). The relationship between the reactive functional group equivalent of the propylene polymer (A) and the reactive functional group equivalent of the crosslinking agent (J) is in the above range, and the storage elastic modulus and the stress relaxation ratio of the adhesive layer are easily adjusted to a set value. range.
在接著劑組成物100質量部中，丙烯聚合物(A)較佳使用10質量部以上的量，更佳使用12.5~70質量部的範圍的量。丙烯聚合物(A)的比例在上述範圍者，對於接著劑層的物性(例如儲存彈性率或應力緩和率)，丙烯聚合物(A)的影響相對變大，藉由變更構成丙烯聚合物(A)的單體，而可容易調整接著劑層的物性。在丙烯聚合物(A)的比例過多的情形，調配其他成份的自由度受限，使得調整接著劑組成物的物性變得困難。 In the mass portion of the adhesive composition 100, the propylene polymer (A) is preferably used in an amount of 10 parts by mass or more, more preferably in an amount ranging from 12.5 to 70 parts by mass. When the ratio of the propylene polymer (A) is in the above range, the influence of the propylene polymer (A) on the physical properties (for example, the storage modulus or the stress relaxation ratio) of the adhesive layer is relatively large, and the propylene polymer is changed by the composition ( The monomer of A) can easily adjust the physical properties of the adhesive layer. In the case where the proportion of the propylene polymer (A) is too large, the degree of freedom in blending other components is limited, making it difficult to adjust the physical properties of the adhesive composition.
也可以側鏈具有能量線聚合性基之(甲基)丙烯酸酯共聚物(含能量線聚合性基之丙烯系聚合物)作為丙烯聚合物(A)使用。含能量線聚合性基之丙烯系聚合物例如使具有官能基之(甲基)丙烯酸酯共聚物與1分子中具有與該官能基 反應之取代基及能量線聚合性基之含聚合性之化合物(含能量線聚合性基之化合物)反應而得者。 A (meth) acrylate copolymer (an ray-based polymer containing an energy ray-polymerizable group) having an energy ray polymerizable group in a side chain may be used as the propylene polymer (A). The propylene-based polymer containing an energy ray polymerizable group has, for example, a (meth) acrylate copolymer having a functional group and the functional group in one molecule. The substituent of the reaction and the polymerizable compound (the compound containing an energy ray polymerizable group) of the energy ray polymerizable group are reacted.
作為具有官能基之(甲基)丙烯酸酯共聚物可使用具有如上述(甲基)丙烯酸酯共聚物之官能基單體(例如含羥基之(甲基)丙烯酸酯等)作為構成單元之(甲基)丙烯酸酯共聚物。 As the (meth) acrylate copolymer having a functional group, a functional group monomer having a (meth) acrylate copolymer as described above (for example, a hydroxyl group-containing (meth) acrylate or the like) can be used as a constituent unit (A) Acrylate copolymer.
含能量線聚合性基之化合物例如甲基丙烯醯氧基乙基異氰酸酯、間異丙烯基-α,α-二甲基苯甲基異氰酸酯、甲基丙烯醯基異氰酸酯、烯丙基異氰酸酯、縮水甘油基(甲基)丙烯酸酯。 The energy ray-polymerizable group-containing compound such as methacryloxyethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, methacryl oxime isocyanate, allyl isocyanate, glycidol Base (meth) acrylate.
具有官能基之(甲基)丙烯酸酯共聚物與含能量線聚合性基之化合物的反應通常在乙酸乙酯等溶液中使用月桂酸二丁基錫等的觸媒，在室溫、常壓下攪拌24小時進行。 The reaction of the functional group-containing (meth) acrylate copolymer and the energy ray-polymerizable group-containing compound is usually carried out in a solution such as ethyl acetate using a catalyst such as dibutyltin laurate, and stirred at room temperature under normal pressure. Hour.
環氧樹脂(B)可使用習知的多種環氧樹脂。環氧樹脂例如雙酚A型環氧樹脂、雙酚F型環氧樹脂、亞苯(phenylene)結構型環氧樹脂、酚醛型環氧樹脂、甲酚醛型環氧樹脂、二環戊二烯型環氧樹脂、聯苯型環氧樹脂、三酚甲烷型環氧樹脂、氮環型環氧樹脂、二苯乙烯(stilbene)型環氧樹脂、縮環芳族烴改性環氧樹脂，或這些的鹵化物等的構造單位中含有2個以上官能基的環氧樹脂。這些環氧樹脂可單獨1種使用，也可2種以上併用。 A variety of conventional epoxy resins can be used for the epoxy resin (B). Epoxy resin such as bisphenol A epoxy resin, bisphenol F epoxy resin, phenylene structural epoxy resin, novolac epoxy resin, cresol novolac epoxy resin, dicyclopentadiene type Epoxy resin, biphenyl type epoxy resin, trisphenol methane type epoxy resin, nitrogen ring type epoxy resin, stilbene type epoxy resin, condensed ring aromatic hydrocarbon modified epoxy resin, or these An epoxy resin containing two or more functional groups in a structural unit such as a halide. These epoxy resins may be used alone or in combination of two or more.
環氧樹脂(B)，在接著劑組成物100質量部中，較佳使用3~90質量部，更佳為5~87.5質量部，再更佳為5~50質 量部的範圍的量。環氧樹脂(B)的比例未滿3質量部者，無法獲得具有充分接著力的接著劑層。又環氧樹脂(B)的比例超過90質量部者，喪失造膜性，接著劑層無法形成片狀而使切割黏接片的製造變得困難。 The epoxy resin (B) is preferably used in an amount of 3 to 90 parts by mass, more preferably 5 to 87.5 parts by mass, and even more preferably 5 to 50 masses in the mass portion of the adhesive composition 100. The amount of the range of the volume. When the ratio of the epoxy resin (B) is less than 3 parts by mass, an adhesive layer having a sufficient adhesion is not obtained. When the ratio of the epoxy resin (B) exceeds 90 parts by mass, the film forming property is lost, and the adhesive layer cannot be formed into a sheet shape, which makes it difficult to manufacture the cut adhesive sheet.
環氧樹脂(B)較佳具有下列結構。 The epoxy resin (B) preferably has the following structure.
R為相同或不同之選自烯烴(alkylene)、聚醚結構、聚丁二烯結構、聚異戊二烯結構之二價基，烷烯或聚醚結構可分別具有側鏈，也可為包含環烷結構之構造。二價基R較佳具有例如-(CH2CH2)-(OCH2CH2)m-、或-(CH(CH3)CH2)-(OCH(CH3)CH2)m-之結構式(m為0~5)的烷烯或醚結構，具體例如乙烯或丙烯之烯烴，或乙烯氧基乙基、二(乙烯氧基)乙基、三(乙烯氧基)乙基、丙烯氧基丙基、二(丙烯氧基)丙基、三(丙烯氧基)丙基等的聚醚結構。 R is the same or different divalent group selected from the group consisting of an alkylene, a polyether structure, a polybutadiene structure, and a polyisoprene structure, and the alkene or polyether structure may have a side chain or may be included, respectively. The structure of the naphthenic structure. The divalent group R preferably has a structure such as -(CH 2 CH 2 )-(OCH 2 CH 2 ) m -, or -(CH(CH 3 )CH 2 )-(OCH(CH 3 )CH 2 ) m - An alkene or ether structure of the formula (m is 0 to 5), specifically, for example, an olefin of ethylene or propylene, or a vinyloxyethyl group, a bis(ethyleneoxy)ethyl group, a tris(ethyleneoxy)ethyl group, a propylene oxide A polyether structure such as a propyl group, a bis(propyleneoxy)propyl group or a tris(propyleneoxy)propyl group.
其他成份例如下列成分。 Other ingredients such as the following ingredients.
熱硬化劑(C)作用為環氧樹脂(B)的硬化劑。熱硬化劑(C)為例如分子中具有2個以上與環氧基反應之官能基的 化合物，此官能基例如酚性羥基、醇性羥基、胺基、羧基、酸酐基等。這些之中，較佳為酚性羥基、胺基及酸酐基，更佳為酚性羥基及胺基。含有具胺基的熱硬化劑(胺系熱硬化劑)之接著劑層，當被接著體為金屬時，因為製作與被接著體的接著界面弱的覆膜，在濕熱條件投入後的接著劑層的接著性大幅降低，但含有具酚性羥基的熱硬化劑(酚系熱硬化劑)的接著劑層的耐濕熱性高，所以在濕熱條件投入後的接著劑層的接著性的下降小。因此，熱硬化劑(C)特別以分子中具有2個以上與環氧基反應之酚性羥基之化合物為佳。 The heat hardener (C) acts as a hardener for the epoxy resin (B). The heat hardener (C) is, for example, a functional group having two or more reactive groups with an epoxy group in a molecule. A compound such as a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group, an acid anhydride group or the like. Among these, a phenolic hydroxyl group, an amine group, and an acid anhydride group are preferable, and a phenolic hydroxyl group and an amine group are more preferable. In the adhesive layer containing a thermosetting agent (amine-based thermosetting agent) having an amine group, when the adherend is a metal, since a film having a weak interface with the adherend is formed, the adhesive is applied after the moist heat condition. The adhesiveness of the layer of the thermal curing agent (phenolic thermosetting agent) having a phenolic hydroxyl group is high, so that the adhesion of the adhesive layer after the application of the hot and cold conditions is small. . Therefore, the thermosetting agent (C) is particularly preferably a compound having two or more phenolic hydroxyl groups reactive with an epoxy group in the molecule.
熱硬化劑(C)的具體例例如多官能系酚樹脂、雙酚、酚醛型酚樹脂、二環戊二烯系酚樹脂、三酚甲烷型酚樹脂、芳烷基酚樹脂等的酚性熱硬化劑；DICY(雙氰胺(dicyandiamide))等的胺系熱硬化劑等。熱硬化劑(C)可單獨1種使用，也可2種以上併用。 Specific examples of the thermosetting agent (C) include phenolic heat such as polyfunctional phenol resin, bisphenol, novolac phenol resin, dicyclopentadiene phenol resin, trisphenol methane phenol resin, and aralkyl phenol resin. A curing agent; an amine-based thermal curing agent such as DICY (dicyandiamide). The heat curing agent (C) may be used alone or in combination of two or more.
本發明之接著劑組成物中，熱硬化劑(C)的含量，相對於環氧樹脂(B)100質量部，通常為0.1~500質量部，較佳為1~200質量部。熱硬化劑(C)的含量低於上述範圍者，接著劑組成物的硬化性不足而無法獲得具有充分接著力之接著劑層。熱硬化劑(C)的含量高於上述範圍者，接著劑組成物的吸濕率增加，半導體封裝的信賴性降低。 In the adhesive composition of the present invention, the content of the thermosetting agent (C) is usually 0.1 to 500 parts by mass, preferably 1 to 200 parts by mass, per 100 parts by mass of the epoxy resin (B). When the content of the heat-hardener (C) is less than the above range, the adhesiveness of the adhesive composition is insufficient to obtain an adhesive layer having a sufficient adhesive force. When the content of the heat hardener (C) is higher than the above range, the moisture absorption rate of the adhesive composition increases, and the reliability of the semiconductor package is lowered.
硬化促進劑(D)用於調整接著劑組成物之硬化速度。硬化促進劑較佳為可促進環氧基與酚性羥基或胺基等反應之 化合物。此化合物具體例如三級胺類、咪唑類、有機膦類、四苯基硼鹽等。 The hardening accelerator (D) is used to adjust the hardening speed of the adhesive composition. The hardening accelerator preferably accelerates the reaction of the epoxy group with a phenolic hydroxyl group or an amine group. Compound. Specific examples of such compounds are tertiary amines, imidazoles, organic phosphines, tetraphenylboron salts and the like.
三級胺類例如三乙胺、苯甲基二甲基胺、三乙醇胺、二甲基胺乙醇、三(二甲基胺基甲基)酚等。 Tertiary amines such as triethylamine, benzyldimethylamine, triethanolamine, dimethylamine ethanol, tris(dimethylaminomethyl)phenol, and the like.
咪唑類例如2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4-甲基-5-羥甲基咪唑、2-苯基-4,5-羥甲基咪唑等。 Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4, 5-hydroxymethylimidazole and the like.
有機膦類例如三丁基膦、二苯基膦、三苯基膦等。 Organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine, and the like.
四苯基硼鹽例如四苯基硼四苯基磷、四苯基硼三苯基膦等。 Tetraphenylboron salts such as tetraphenylboron tetraphenylphosphine, tetraphenylboron triphenylphosphine, and the like.
本發明之接著劑組成物所含之硬化促進劑(D)可為單獨1種，也可為2種以上之組合。 The curing accelerator (D) contained in the adhesive composition of the present invention may be used alone or in combination of two or more.
硬化促進劑(D)，相對於環氧樹脂(B)及熱硬化劑(C)總計100質量部，較佳含有0.1~1.0質量部。硬化促進劑(D)的含量在上述範圍者，具有即使暴露於高溫高濕度下接著劑層也安定的接著性，即使暴露於嚴酷的迴流(reflow)條件也可達成高度封裝信賴性。硬化促進劑(D)的含量未滿0.1質量部者，接著劑層無法得到充分的硬化性，接著劑層無法發揮接著性。硬化促進劑(D)的含量超過1.0質量部者，接著劑層雖可發揮高接著性，但具有高極性的硬化促進劑在高溫高濕度下接著劑層中向接著的界面移動，經由偏析而使封裝信賴性降低。 The hardening accelerator (D) is preferably contained in an amount of 0.1 to 1.0 part by mass based on 100 parts by mass of the epoxy resin (B) and the heat curing agent (C). When the content of the hardening accelerator (D) is in the above range, the adhesive property is stabilized even when exposed to high temperature and high humidity, and high reliability of packaging can be achieved even when exposed to severe reflow conditions. When the content of the hardening accelerator (D) is less than 0.1 mass%, the adhesive layer does not have sufficient curability, and the adhesive layer cannot exhibit adhesion. When the content of the curing accelerator (D) exceeds 1.0 mass, the adhesive layer can exhibit high adhesion, but the curing accelerator having high polarity moves to the subsequent interface in the adhesive layer under high temperature and high humidity, and segregates. Reduce package reliability.
本發明中為了提升接著劑組成物對被接著體的接著力 及密著力，也可使用偶合劑(E)。使用偶合劑(E)者可無損接著劑組成物硬化所得的硬化物之耐熱性，使其耐水性提高。 In the present invention, in order to improve the adhesion of the adhesive composition to the adherend With a close contact, a coupling agent (E) can also be used. When the coupling agent (E) is used, the heat resistance of the cured product obtained by curing the adhesive composition can be impaired, and the water resistance can be improved.
偶合劑(E)較佳使用具有與丙烯聚合物(A)或環氧樹脂(B)所具之官能基反應之基的化合物。偶合劑(E)較佳為矽烷偶合劑。 As the coupling agent (E), a compound having a group reactive with a functional group of the propylene polymer (A) or the epoxy resin (B) is preferably used. The coupling agent (E) is preferably a decane coupling agent.
矽烷偶合劑例如γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷、β-(3,4-環氧基環己基)乙基三甲氧基矽烷、γ-(甲基丙烯醯基丙基)三甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、N-6-(胺乙基)-γ-胺基丙基三甲氧基矽烷、N-6-(胺乙基)-γ-胺丙基甲基二乙氧基矽烷、N-苯基-γ-胺丙基三甲氧基矽烷、γ-脲基丙基三乙氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-巰基丙基甲基二甲氧基矽烷、雙(3-三乙氧基甲矽烷基丙基)四硫化氫、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯三甲氧基矽烷、乙烯三乙醯氧基矽烷、咪唑矽烷等。矽烷偶合劑可單獨1種使用，也可併用2種以上。 A decane coupling agent such as γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane, β-(3,4-epoxycyclohexyl)ethyl Trimethoxydecane, γ-(methacryloylpropyl)trimethoxydecane, γ-aminopropyltrimethoxydecane, N-6-(aminoethyl)-γ-aminopropyltrimethoxy Baseline, N-6-(aminoethyl)-γ-aminopropylmethyldiethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, γ-ureidopropyltriethoxy Baseline, γ-mercaptopropyltrimethoxydecane, γ-mercaptopropylmethyldimethoxydecane, bis(3-triethoxycarbenylpropyl)tetrahydrogen sulfide, methyltrimethoxydecane , methyl triethoxy decane, ethylene trimethoxy decane, ethylene triethoxy decane, imidazolium, and the like. The decane coupling agent may be used alone or in combination of two or more.
偶合劑(E)的含量，相對於丙烯聚合物(A)及環氧樹脂(B)總計100質量部，通常為0.1~20質量部，較佳為0.2~10質量部，更佳為0.3~5質量部。偶合劑(E)的含量未滿0.1質量部者，無法得到上述效果，超過20質量部則成為脫氣(out gas)的原因。 The content of the coupling agent (E) is usually 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass, more preferably 0.3 to 1 part by mass based on 100 parts by mass of the propylene polymer (A) and the epoxy resin (B). 5 quality department. When the content of the coupling agent (E) is less than 0.1 part by mass, the above effect cannot be obtained, and if it exceeds 20 parts by mass, it becomes a cause of out gas.
本發明中接著劑組成物也可調配無機填充材料(F)。藉 由調配無機填充材料(F)於接著劑組成物中可調整該組成物的熱膨脹係數。對半導體晶片、導線架(lead frame)及有機基板硬化後的接著劑層的熱膨脹係數最佳化，可使封裝信賴性更加提升。接著劑層的硬化後的吸濕率也可更為降低。 The adhesive composition of the present invention can also be formulated with an inorganic filler (F). borrow The thermal expansion coefficient of the composition can be adjusted by formulating the inorganic filler (F) in the adhesive composition. The thermal expansion coefficient of the semiconductor wafer, the lead frame, and the adhesive layer after the organic substrate is cured is optimized, and the package reliability can be further improved. The moisture absorption rate after hardening of the layer of the agent can also be further reduced.
無機填充材料(F)例如二氧化矽、氧化鋁、滑石、碳酸鈣、氧化鈦、氧化鐵(III)、碳化矽、氮化硼等粉末、這些球形化的珠、單結晶纖維、玻璃纖維等。這些之中，較佳為二氧化矽填充材及氧化鋁填充材。無機填充材料(F)可單獨1種使用，也可併用2種以上。 Inorganic filler (F) such as ceria, alumina, talc, calcium carbonate, titanium oxide, iron (III) oxide, niobium carbide, boron nitride, etc., spheroidized beads, single crystal fibers, glass fibers, etc. . Among these, a cerium oxide filler and an alumina filler are preferable. The inorganic filler (F) may be used alone or in combination of two or more.
本發明之接著劑組成物中，無機填充材料(F)的含量，在構成接著劑層的接著劑組成物100質量部中，通常為0~80質量部。無機填充材料(F)的含量在此範圍者，接著劑層的硬化後吸濕率可更為降低，且接著劑層中的無機填充材料的比例如果不過大，接著性的損壞少。 In the adhesive composition of the present invention, the content of the inorganic filler (F) is usually from 0 to 80 parts by mass in the mass portion of the adhesive composition 100 constituting the adhesive layer. When the content of the inorganic filler (F) is in this range, the moisture absorption rate of the adhesive layer after curing can be further lowered, and if the ratio of the inorganic filler in the adhesive layer is not too large, the adhesiveness of the adhesiveness is small.
接著劑組成物中也可使用熱可塑性樹脂(G)。熱可塑性樹脂(G)為了保持硬化後接著劑層的可撓性而調配。熱可塑性樹脂(G)較佳為重量平均分子量1000~10萬者，更佳為3000~8萬。藉由含有熱可塑性樹脂(G)，半導體晶片的提取步驟中基材與接著劑層的層間剝離可容易進行，而且可抑制接著劑層依循基板凹凸的空隙等的發生。 A thermoplastic resin (G) can also be used in the subsequent composition. The thermoplastic resin (G) is formulated in order to maintain the flexibility of the adhesive layer after curing. The thermoplastic resin (G) is preferably a weight average molecular weight of 1,000 to 100,000, more preferably 3,000 to 80,000. By including the thermoplastic resin (G), the interlayer peeling of the substrate and the adhesive layer can be easily performed in the extraction step of the semiconductor wafer, and the occurrence of voids or the like in which the adhesive layer follows the unevenness of the substrate can be suppressed.
熱可塑性樹脂(G)的玻璃轉移溫度較佳為-30~150℃更佳為-20~120℃的範圍。熱可塑性樹脂(G)的玻璃轉移溫度 在上述範圍者，容易將80℃的接著劑層的儲存彈性率及應力緩和率調整至上述較佳範圍。熱可塑性樹脂(G)的玻璃轉移溫度過低者，接著劑層與基材的剝離力增大，造成晶片的提取不良，過高則固定晶圓的接著力恐怕不足。 The glass transition temperature of the thermoplastic resin (G) is preferably in the range of -30 to 150 ° C or more preferably -20 to 120 ° C. Glass transition temperature of thermoplastic resin (G) In the above range, it is easy to adjust the storage elastic modulus and the stress relaxation ratio of the adhesive layer at 80 ° C to the above preferred range. When the glass transition temperature of the thermoplastic resin (G) is too low, the peeling force of the adhesive layer and the substrate increases, resulting in poor extraction of the wafer. If the temperature is too high, the adhesion of the fixed wafer may be insufficient.
熱可塑性樹脂(G)例如聚酯樹脂、聚乙烯醇樹脂、聚乙烯丁縮醛、聚氯乙烯、聚苯乙烯、聚醯胺樹脂、纖維素、聚乙烯、聚異丁烯、聚乙烯醚、聚亞胺樹脂、聚苯醚樹脂、聚甲基丙烯酸甲酯、苯乙烯-異戊二烯-苯乙烯嵌段共聚物、苯乙烯-丁二烯-苯乙烯嵌段共聚物等。這些可單獨1種使用，或者混合2種以上使用。 Thermoplastic resin (G) such as polyester resin, polyvinyl alcohol resin, polyvinyl butyral, polyvinyl chloride, polystyrene, polyamide resin, cellulose, polyethylene, polyisobutylene, polyvinyl ether, poly Amine resin, polyphenylene ether resin, polymethyl methacrylate, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene block copolymer, and the like. These may be used alone or in combination of two or more.
熱可塑性樹脂(G)在較室溫高的溫度下使接著劑層的儲存彈性率降低、應力緩和率增加，因此在接著劑層中的調配量為一定量以下為佳。具體為，在構成接著劑層的接著劑組成物100質量部中，較佳為0~35質量部，更佳為1~25質量部。 The thermoplastic resin (G) lowers the storage modulus of the adhesive layer at a temperature higher than room temperature and increases the stress relaxation rate. Therefore, the amount of the adhesive layer in the adhesive layer is preferably a certain amount or less. Specifically, in the mass portion of the adhesive composition 100 constituting the adhesive layer, it is preferably 0 to 35 parts by mass, more preferably 1 to 25 parts by mass.
本發明中的接著劑組成物也可含有能量線聚合性化合物(H)。能量線聚合性化合物(H)經能量線照射而聚合，可使接著劑層的接著力降低。因此，在半導體晶片的提取步驟中，基材與接著劑層的層間剝離容易進行。 The adhesive composition in the present invention may also contain an energy ray polymerizable compound (H). The energy ray polymerizable compound (H) is polymerized by irradiation with an energy ray, and the adhesion of the adhesive layer can be lowered. Therefore, in the extraction step of the semiconductor wafer, the interlayer peeling between the substrate and the adhesive layer is facilitated.
能量線聚合性化合物(H)為受紫外線或電子線等的能量線的照射而聚合、硬化之化合物。能量線聚合性化合物(H)例如分子內具有1個以上的能量線聚合性雙鍵之化合物，例如丙烯酸酯系化合物。 The energy ray polymerizable compound (H) is a compound which is polymerized and hardened by irradiation with an energy ray such as an ultraviolet ray or an electron beam. The energy ray polymerizable compound (H) is, for example, a compound having one or more energy ray polymerizable double bonds in the molecule, for example, an acrylate compound.
丙烯酸酯系化合物例如三甲氧基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇單羥基五丙烯酸酯、二季戊四醇六丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,6-己烷二醇二丙烯酸酯、二環戊二烯二甲氧基二丙烯酸酯、聚乙二醇二丙烯酸酯、寡酯丙烯酸酯、氨酯丙烯酸酯系寡聚物、環氧基改性丙烯酸酯、聚醚丙烯酸酯、衣康酸寡聚物等。 Acrylate-based compounds such as trimethoxypropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butanediol diacrylate, 1, 6-hexanediol diacrylate, dicyclopentadiene dimethoxy diacrylate, polyethylene glycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy modification Acrylate, polyether acrylate, itaconic acid oligomer, and the like.
能量線聚合性化合物(H)的分子量(寡聚物或聚合物的情形的重量平均分子量)通常為約100~30,000，較佳為約300~10,000。本發明之接著劑組成物中，能量線聚合性化合物(H)的含量，在構成接著劑層的接著劑組成物100質量部中，通常為0~40質量部，較佳為1~30質量部，更佳為3~20質量部。能量線聚合性化合物(H)的含量超過上述範圍者，接著劑層對有機基板或導線架等的接著力降低。 The molecular weight of the energy ray polymerizable compound (H) (the weight average molecular weight in the case of an oligomer or a polymer) is usually from about 100 to 30,000, preferably from about 300 to 10,000. In the adhesive composition of the present invention, the content of the energy ray polymerizable compound (H) is usually 0 to 40 parts by mass, preferably 1 to 30 parts by mass in the mass portion of the adhesive composition constituting the adhesive layer. The department is better than the 3~20 quality department. When the content of the energy ray polymerizable compound (H) exceeds the above range, the adhesion of the adhesive layer to an organic substrate or a lead frame or the like is lowered.
本發明之接著劑組成物含有能量線硬化性化合物(H)或上述含能量線聚合性基的丙烯系聚合物的情形時，上述的80℃的儲存彈性率、在80℃環境下施以20%扭曲應力120秒後的應力緩和率、及80℃的tan δ，在接著劑組成物切割前預定進行能量線照射的情形中，表示進行能量線照射而硬化後所測定者，而在切割後預定進行能量線照射的情形中，表示進行能量線照射而硬化前所測定者。這些特性因為會影響起因於切割時基材變形的接著劑層的收縮，因此以切割的時間基準應該可以論述。本發明之接著劑組成物不論能量線聚合性化合物(H)或含能量線聚合性劑的丙 烯系聚合物的含量為何，只要具有上述特性，可達到防止接著劑層收縮的作用效果。 When the adhesive composition of the present invention contains the energy ray-curable compound (H) or the above-mentioned propylene-based polymer containing an energy ray-polymerizable group, the storage elastic modulus at 80 ° C described above is 20 in an environment of 80 ° C. The stress relaxation rate after 120 seconds of the twist stress and the tan δ at 80 ° C are in the case where the energy ray irradiation is scheduled to be performed before the cutting of the adhesive composition, and the measurement is performed after the energy ray irradiation is performed, and after the cutting, In the case where the energy ray irradiation is scheduled to be performed, the person measured before the energy ray irradiation and the curing is performed. These characteristics should be discussed as a time base for cutting because it affects the shrinkage of the adhesive layer resulting from deformation of the substrate during cutting. The adhesive composition of the present invention, regardless of the energy ray polymerizable compound (H) or the energy ray-containing polymerizable agent What is the content of the olefinic polymer, as long as it has the above characteristics, the effect of preventing the shrinkage of the adhesive layer can be achieved.
本發明之接著劑組成物在使用之時，使用上述能量線聚合性化合物(H)的情形中，也可以照射紫外線等的能量線使接著劑層的接著力下降。接著劑組成物中含有光聚合起始劑(I)，可縮短聚合、硬化時間及減少光照量。 In the case where the above-mentioned energy ray polymerizable compound (H) is used in the use of the adhesive composition of the present invention, the energy of the ultraviolet ray or the like may be irradiated to lower the adhesion of the adhesive layer. The photopolymerization initiator (I) is contained in the subsequent composition, which can shorten the polymerization, hardening time, and reduce the amount of light.
光聚合起始劑(I)例如二苯甲酮(benzophenone)、苯乙酮(acetophenone)、苯偶因(benzoin)、苯偶因甲醚(benzoin methyl ether)、苯偶因乙醚(benzoin ethyl ether)、苯偶因異丙醚(benzoin isopropyl ether)、苯偶因異丁醚(benzoin isobutyl ether)、苯偶因苯甲酸、苯偶因苯甲酸甲酯、苯偶因二甲基縮酮(benzoin dimethyl ketal)、2,4-二乙基噻吨酮(2,4-diethyl thioxanthone)、α-羥基環己基苯基酮、苯甲基二苯基硫化物、四甲基秋蘭姆單硫化物(tetramethyl thiuram monosulfide)、偶氮雙異丁腈(azobisisobutylonitrile)、苯偶醯(benzil)、二苯基醚(dibenzyl ether)、2,3-丁二酮(2,3-butanedione)、1,2-二苯甲基甲烷、2,4,6-三甲基苯甲醯基二苯基氧化磷(2,4,6-trimethylb benzoyl diphenyl phosphine oxide)、β-氯化蒽醌(β-chloroanthraquinone)等。光聚合起始劑(I)可單獨1種使用，也可併用2種以上。 Photopolymerization initiator (I) such as benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether ), benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal Dimethyl ketal), 2,4-diethyl thioxanthone, α-hydroxycyclohexyl phenyl ketone, benzyl diphenyl sulfide, tetramethyl thiuram monosulfide (tetramethyl thiuram monosulfide), azobisisobutylonitrile, benzil, dibenzyl ether, 2,3-butanedione, 1,2 -2,4,6-trimethylb benzoyl diphenyl phosphine oxide, β-chloroanthraquinone Wait. The photopolymerization initiator (I) may be used alone or in combination of two or more.
光聚合起始劑(I)的含量理論上由存在於接著劑層的 不飽和鍵結量或其反應性及使用的光聚合起始劑的反應性來決定，但是在複雜的混合物系中不一定容易。一般的指標為，光聚合起始劑(I)的含量，相對於能量線聚合性化合物(H)100質量部，較佳為0.1~10質量部，更佳為1~5質量部。光聚合起始劑(I)的含量低於上述範圍者，光聚合不足，無法得到充足的提取性，超過上述範圍者，則產生未進行光聚合的殘留物，使得接著劑組成物的硬化性不足。 The content of the photopolymerization initiator (I) is theoretically present in the adhesive layer The amount of unsaturated bond or its reactivity and the reactivity of the photopolymerization initiator used are determined, but it is not necessarily easy in a complicated mixture system. In general, the content of the photopolymerization initiator (I) is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the energy ray polymerizable compound (H). When the content of the photopolymerization initiator (I) is less than the above range, photopolymerization is insufficient, and sufficient extractability cannot be obtained. When the content exceeds the above range, a residue which is not photopolymerized is generated, and the adhesive composition is cured. insufficient.
本發明之接著劑層，為了調節其儲存彈性率及應力緩和率，較佳添加交聯劑(J)。交聯劑(J)可例如有機多價異氰酸酯化合物、有機多價亞胺化合物等。 In order to adjust the storage modulus and the stress relaxation rate of the adhesive layer of the present invention, it is preferred to add a crosslinking agent (J). The crosslinking agent (J) may, for example, be an organic polyvalent isocyanate compound, an organic polyvalent imine compound or the like.
有機多價異氰酸酯化合物例如芳族多價異氰酸酯化合物、脂肪族多價異氰酸酯化合物、脂環族多價異氰酸酯化合物、以及這些有機多價異氰酸酯化合物的三聚體、以及這些有機多價異氰酸酯化合物與多元醇化合物反應所得的末端異氰酸酯氨酯預聚物等。 Organic polyvalent isocyanate compounds such as aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, and trimers of these organic polyvalent isocyanate compounds, and these organic polyvalent isocyanate compounds and polyols A terminal isocyanate urethane prepolymer obtained by reacting a compound or the like.
多價有機異氰酸酯化合物更具體例如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、三甲氧基丙烷加成甲苯二異氰酸酯、及賴胺酸異氰酸酯(lysine isocyanate)。 有機多價亞胺化合物的具體例如N,N’-二苯基甲烷-4,4’-雙(1-環乙亞胺羧基醯胺)(N,N’-diphenyl methane-4,4’-bis(1-aziridine carboxyamide))、三甲氧基丙烷-三-β-環乙亞胺基丙酸鹽(trimethylol propane-tri-β-aziridinyl propionate)、四甲氧基甲烷-三-β-環乙亞胺基丙酸鹽(tetramethylol propane-tri-β-aziridinyl propionate)、及N,N’-甲苯-2,4-雙(1-環乙亞胺羧基醯胺)三胺嗪(N,N’-toluene-2,4-bis(1-aziridine carboxyamide)triethylenemelamine)等。 The polyvalent organic isocyanate compound is more specifically, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-dimethylbenzene diisocyanate, diphenylmethane-4,4 '-Diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4, 4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, trimethoxypropane addition toluene diisocyanate, and lysine isocyanate. Specific examples of the organic polyvalent imine compound such as N,N'-diphenylmethane-4,4'-bis(1-cycloethyliminecarboxyguanamine) (N,N'-diphenyl methane-4,4'- Bis(1-aziridine carboxyamide), trimethylol propane-tri-β-aziridinyl propionate, tetramethoxymethane-tri-β-ring B Tetramethylol propane-tri-β-aziridinyl propionate, and N,N'-toluene-2,4-bis(1-cycloethyliminecarboxyguanamine)triamine (N,N' -toluene-2,4-bis(1-aziridine carboxyamide)triethylenemelamine).
交聯劑(J)使用相對於丙烯聚合物(A)100質量部，較佳為1~40質量部的比例，更佳為8~35質量部，再更佳為12~30質量部。交聯劑(J)的調配量在上述範圍者，容易使接著劑層的儲存彈性率及應力緩和率調整至上述較佳範圍。 The crosslinking agent (J) is used in a proportion of 100 parts by mass, preferably 1 to 40 parts by mass, more preferably 8 to 35 parts by mass, still more preferably 12 to 30 parts by mass, based on 100 parts by mass of the propylene polymer (A). When the amount of the crosslinking agent (J) is in the above range, the storage elastic modulus and the stress relaxation ratio of the adhesive layer are easily adjusted to the above preferred range.
而且，交聯劑(J)的調配量與丙烯聚合物(A)的調配量的關係較佳為，丙烯聚合物(A)在接著劑組成物100質量部中含有超過35質量部，且交聯劑(J)相對於丙烯聚合物(A)100質量部含有5質量部以上、未滿20質量部。而且以丙烯聚合物(A)在接著劑組成物100質量部中含有10~35質量部，且交聯劑(J)相對於丙烯聚合物(A)100質量部含有20~35質量部為佳。交聯劑(J)的調配量與丙烯聚合物(A)的調配量的關係在上述範圍者，不論丙烯聚合物(A)的調配量，接著劑層的儲存彈性率及應力緩和率容易調整至上述 較佳範圍。 Further, the relationship between the amount of the crosslinking agent (J) and the amount of the propylene polymer (A) is preferably such that the propylene polymer (A) contains more than 35 parts by mass in the mass portion of the adhesive composition 100, and The crosslinking agent (J) contains 5 parts by mass or more and less than 20 parts by mass with respect to 100 parts by mass of the propylene polymer (A). Further, the propylene polymer (A) is contained in an amount of 10 to 35 parts by mass in the mass portion of the adhesive composition 100, and the crosslinking agent (J) is preferably contained in an amount of 20 to 35 parts by mass based on 100 parts by mass of the propylene polymer (A). . The relationship between the blending amount of the crosslinking agent (J) and the blending amount of the propylene polymer (A) is in the above range, and the storage elastic modulus and the stress relaxation ratio of the adhesive layer can be easily adjusted regardless of the blending amount of the propylene polymer (A). To the above Preferred range.
其他成分除此之外也可添加染料、顏料、劣化防止劑、防帶電劑、難燃劑、矽酮化合物、鍊移動劑、吸除劑(gettering agent)等。 Other components may be added with a dye, a pigment, a deterioration preventive agent, an antistatic agent, a flame retardant, an anthrone compound, a chain shifting agent, a gettering agent, and the like.
本發明之切割黏結片使用由上述各成分所組成之接著劑組成物，在基材上層積接著劑層所製造。接著劑組成物具有感壓接著性及加熱硬化性，在未硬化狀態具有暫時保持各種被接著體的機能。因此，經熱硬化最終可賦予高耐衝擊性的硬化物，接著強度亦優良，即使在嚴酷的高溫高濕條件下也保持充分的接著性。接著劑組成物可由上述各成分以適宜比例混合而得。混合之時，也可以溶劑事先稀釋各成分，也可在混合時添加溶劑。 The cut-and-bonded sheet of the present invention is produced by laminating an adhesive layer on a substrate using an adhesive composition composed of the above respective components. The subsequent composition has pressure-sensitive adhesiveness and heat curability, and has a function of temporarily holding various kinds of adherends in an uncured state. Therefore, it is possible to impart a high impact resistance hardened material by heat hardening, and the strength is also excellent, and sufficient adhesion is maintained even under severe high temperature and high humidity conditions. The composition of the subsequent agent can be obtained by mixing the above components in an appropriate ratio. At the time of mixing, the components may be previously diluted with a solvent, or a solvent may be added during mixing.
本發明之切割黏結片為，由上述接著劑組成物所構成的接著劑層可在基材上剝離。本發明之切割黏結片的形狀，可為帶狀、或適合於基材上使接著劑層接著於被接著體的形狀事先裁斷而擔載的形狀等之形狀。本發明人等潛心檢討的結果，使用具有上述特定物性之接著劑層製作切割黏結片者，不論後述基材種類，發現可抑制切割步驟中起因於基材變形的接著劑層的收縮。 In the dicing adhesive sheet of the present invention, the adhesive layer composed of the above-mentioned adhesive composition can be peeled off on the substrate. The shape of the cut-and-bonded sheet of the present invention may be a strip shape or a shape suitable for the shape of the adhesive layer to be adhered to the shape of the adherend in advance and then carried on the substrate. As a result of the intensive review by the inventors of the present invention, it has been found that the use of the adhesive layer having the specific physical properties as described above can suppress the shrinkage of the adhesive layer caused by the deformation of the substrate in the cutting step regardless of the type of the substrate to be described later.
切割黏結片的基材可使用例如聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、聚氯乙烯膜、氯乙烯共聚物膜、聚乙烯對苯二甲酸酯膜、聚乙烯萘膜、聚丁烯對苯二甲酸酯膜、聚氨酯膜、乙烯乙酸乙烯酯共聚物 膜、離聚物(ionomer)樹脂膜、乙烯-(甲基)丙烯酸共聚物膜、乙烯-(甲基)丙烯酸酯共聚物膜、聚苯乙烯膜、聚碳酸酯膜、聚亞胺膜、氟樹脂膜等的膜。也可使用這些的層積膜。也可使用這些著色的膜。本發明所使用之基材較佳為包含選自聚乙烯膜、乙烯-甲基丙烯酸共聚物膜、聚丙烯膜之中1種以上之基材。 The substrate for cutting the adhesive sheet may be, for example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, or a polyethylene terephthalate film. Dicarboxylate film, polyethylene naphthalene film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate copolymer Membrane, ionomer resin film, ethylene-(meth)acrylic copolymer film, ethylene-(meth)acrylate copolymer film, polystyrene film, polycarbonate film, polyimide film, fluorine A film such as a resin film. These laminated films can also be used. These colored films can also be used. The substrate used in the present invention preferably comprises one or more substrates selected from the group consisting of a polyethylene film, an ethylene-methacrylic acid copolymer film, and a polypropylene film.
本發明之切割黏結片貼附於各種被接著體，被接著體進行需要的加工後，接著劑層黏接於被接著體，自基材剝離。亦即，使用於包含使接著劑層從基材轉印至被接著體的步驟的過程。因此，連接於基材的接著劑層的面的表面張力較佳為40mN/m以下，更佳為37 mN/m以下，再更佳為35 mN/m以下。下限值通常為約25 mN/m。這些表面張力低的基材可經適宜地選擇材質而獲得，或者也可在基材表面塗布剝離劑進行剝離處理而得。 The cut-and-bonded sheet of the present invention is attached to various adherends, and after the desired processing by the adhesive, the adhesive layer is adhered to the adherend and peeled off from the substrate. That is, it is used in a process including a step of transferring an adhesive layer from a substrate to a member to be bonded. Therefore, the surface tension of the surface of the adhesive layer to be bonded to the substrate is preferably 40 mN/m or less, more preferably 37 mN/m or less, still more preferably 35 mN/m or less. The lower limit is typically about 25 mN/m. These base materials having a low surface tension can be obtained by appropriately selecting a material, or can be obtained by applying a release agent to the surface of the substrate and performing a release treatment.
用於基材的剝離處理之剝離劑可使用烷化物(alkide)系、矽(silicone)系、氟系、不飽和聚酯系、聚烯烴系、蠟系等，特別是烷化物系、矽系、氟系的剝離劑具有耐熱性為佳。 As the release agent for the release treatment of the substrate, an alkide system, a silicone system, a fluorine system, an unsaturated polyester system, a polyolefin system, a wax system or the like can be used, and in particular, an alkylate system or a lanthanide system can be used. The fluorine-based release agent is preferably heat-resistant.
為了使用上述剝離劑進行基材表面剝離處理，剝離劑可接使用而無溶劑，或者以溶劑稀釋或乳化，經凹版塗佈(gravia coating)、邊耶塗佈(Meyer coating)、氣刀塗佈、輥塗佈等塗佈，或於常溫或加熱或電子線硬化，以濕層積或乾層積、熱熔融層積、熔融押出層積、共押出加工等形成層積體。 In order to perform the surface peeling treatment of the substrate using the above-mentioned release agent, the release agent may be used without a solvent, or diluted or emulsified with a solvent, by gravia coating, Meyer coating, air knife coating. Coating by roll coating or the like, or hardening at room temperature or heating or electron beam, forming a laminate by wet lamination or dry lamination, hot melt lamination, melt extrusion lamination, co-extrusion processing, or the like.
基材的厚度通常為約10~500μm，較佳為約15~300μm，更佳為約20~250μm。接著劑層的厚度通常為約1~500μm，更佳為約5~300μm，再更佳為約10~150μm。 The thickness of the substrate is usually from about 10 to 500 μm, preferably from about 15 to 300 μm, more preferably from about 20 to 250 μm. The thickness of the subsequent layer is usually from about 1 to 500 μm, more preferably from about 5 to 300 μm, still more preferably from about 10 to 150 μm.
切割黏結片的製造方法沒有特別限制，可在基材上塗佈乾燥構成接著劑層的組成物而製造，或者也可在剝離膜上設置接著劑層使其轉印至上述基材而製造。切割黏結片在使用之前，為保護接著劑層，也可在接著劑層的上面層積剝離膜。該剝離膜使用聚乙烯對苯二甲酸酯膜或聚丙烯膜等的塑膠材料塗佈矽樹脂等的剝離劑。接著劑層的表面外圍部，為了固定連結框等的其他夾具，也可設置其他用途的黏接劑層或黏接帶。 The method for producing the cut-and-bonded sheet is not particularly limited, and it may be produced by coating and drying a composition constituting the adhesive layer on a substrate, or by disposing an adhesive layer on the release film and transferring it to the substrate. The protective film may be laminated on the adhesive layer before the use of the adhesive layer to protect the adhesive layer. The release film is coated with a release agent such as a ruthenium resin using a plastic material such as a polyethylene terephthalate film or a polypropylene film. Further, an adhesive layer or an adhesive tape for other purposes may be provided on the outer peripheral surface of the coating layer in order to fix other jigs such as a connecting frame.
以下對於本發明切割黏結片的利用方法，以該切割黏結片適用於半導體裝置製造的情形為例說明。 Hereinafter, a method of using the dicing adhesive sheet of the present invention will be described by taking a case where the dicing bonding sheet is suitable for the manufacture of a semiconductor device.
使用本發明之切割黏結片的半導體裝置之製造方法，包括將半導體晶圓貼附於上述切割黏結片的接著劑層，切割該半導體晶圓作成半導體晶片，以該半導體晶片內面黏有接著劑層而從基材剝離，在該半導體晶片層積於有機基板或導線架的晶粒墊上或者層積晶片的情形中，藉由該接著劑層而承載於其他半導體晶片上的步驟。 A method of manufacturing a semiconductor device using the dicing bonded sheet of the present invention comprises: attaching a semiconductor wafer to an adhesive layer of the dicing adhesive sheet, and dicing the semiconductor wafer to form a semiconductor wafer, wherein an adhesive is adhered to the inner surface of the semiconductor wafer The layer is peeled off from the substrate, and the semiconductor wafer is carried on the other semiconductor wafer by the adhesive layer in the case where the semiconductor wafer is laminated on the die pad of the organic substrate or the lead frame or in the case of laminating the wafer.
以下詳細說明本發明之半導體裝置的製造方法。 Hereinafter, a method of manufacturing the semiconductor device of the present invention will be described in detail.
本發明之半導體裝置之製造方法中，首先準備表面形成電路、內面研磨削切的半導體晶圓。 In the method of manufacturing a semiconductor device of the present invention, first, a surface forming circuit and a semiconductor wafer whose inner surface is polished and cut are prepared.
半導體晶圓可為矽晶圓，也可為鉮化鎵等的化合物半 導體晶圓。晶圓表面的電路形成可由包含蝕刻法、起離法(lift off)等的習知廣用的方法之各種方法進行。之後研磨削切半導體晶圓電路面的相反面(內面)。研磨削切法沒有特別限制，也可使用磨床(grinder)等的公知手段進行研磨削切。內面研磨削切時，在保護表面電路的電路面上貼上稱為表面保護片的黏接片。內面研磨削切可經由晶圓電路面側(即表面保護片側)以工作盤(chuck table)等固定，以磨床研磨削切未形成電路的內面側。晶圓的研磨削切後的厚度沒有特別限制，但通常為約20~500μm。 The semiconductor wafer can be a germanium wafer or a compound half of gallium antimonide or the like. Conductor wafer. The circuit formation on the wafer surface can be performed by various methods including a well-known method of etching, lift off, and the like. Thereafter, the opposite side (inner surface) of the circuit surface of the semiconductor wafer is ground and cut. The polishing and cutting method is not particularly limited, and the grinding and cutting may be carried out by a known means such as a grinder. When the inner surface is ground and cut, an adhesive sheet called a surface protection sheet is attached to the circuit surface of the surface protection circuit. The inner surface grinding and cutting can be fixed by a chuck table or the like via the wafer circuit surface side (i.e., the surface protection sheet side), and the inner surface side of the circuit which is not formed by the grinding is cut by the grinding machine. The thickness after the polishing of the wafer is not particularly limited, but is usually about 20 to 500 μm.
之後，視需要去除內面研磨削切所產生的破碎層。破碎層的去除可經由化學劑蝕刻或電漿蝕刻等。 Thereafter, the fracture layer produced by the inner surface grinding and cutting is removed as needed. The removal of the fracture layer can be via chemical etching or plasma etching or the like.
之後將連結框及半導體晶圓的內面側載置於本發明之切割黏結片的接著劑層上，輕壓以固定半導體晶圓。接著，在接著劑層中調配有含能量線聚合性基之丙烯系聚合物或能量線聚合性化合物(H)的情形時，對接著劑層從基材側照射能量線，使含能量線聚合性基之丙烯系聚合物或能量線聚合性化合物(H)聚合，增加接著劑層的凝集力，使得接著劑層與基材之間的接著力降低。照射的能量線可例如紫外線(UV)或電子線(EB)等，較佳使用紫外線。之後，使用切割鋸(dicing saw)等的切斷手段，切斷上述的半導體晶圓而獲得半導體晶片。此時切斷深度為半導體晶圓的厚度與接著劑層的厚度總計以及切割鋸的磨耗部分之總和的深度。能量線的照射可在半導體晶圓貼附後或半導體晶片剝離(提取)前的階段進行，例如在切割後進行，也可在下述 延展步驟後進行。而且，能量線照射可分複數次進行。 Thereafter, the bonding frame and the inner surface side of the semiconductor wafer are placed on the adhesive layer of the dicing bonding sheet of the present invention, and lightly pressed to fix the semiconductor wafer. When the propylene polymer or the energy ray polymerizable compound (H) containing the energy ray polymerizable group is blended in the adhesive layer, the energy ray is irradiated from the substrate side to the adhesive layer to polymerize the energy ray-containing polymer. The polymerization of the propylene-based polymer or the energy ray-polymerizable compound (H) increases the cohesive force of the adhesive layer, and the adhesion between the adhesive layer and the substrate is lowered. The energy line to be irradiated may be, for example, ultraviolet (UV) or electron beam (EB), etc., and ultraviolet light is preferably used. Thereafter, the semiconductor wafer is cut by using a cutting means such as a dicing saw to obtain a semiconductor wafer. The cutting depth at this time is the depth of the sum of the thickness of the semiconductor wafer and the thickness of the adhesive layer and the sum of the worn portions of the dicing saw. The irradiation of the energy ray may be performed after the semiconductor wafer is attached or before the semiconductor wafer is detached (extracted), for example, after cutting, or may be as follows After the extension step. Moreover, the energy line illumination can be performed in several times.
之後視需要進行切割黏結片的延展，半導體晶片的間隔擴張，使得半導體晶片的提取變得更容易進行。此時，接著劑層與基材之間發生斷裂，使接著劑層與基材之間的接著力減少。半導體晶片的提取性提升。如此進行半導體晶片的提取，已切斷的接著劑層黏接於半導體晶片內面側而可自基材剝離。 Thereafter, the stretching of the dicing sheet is performed as needed, and the interval of the semiconductor wafer is expanded, so that the extraction of the semiconductor wafer becomes easier. At this time, breakage occurs between the adhesive layer and the substrate, and the adhesion between the adhesive layer and the substrate is reduced. The extraction of semiconductor wafers is improved. The semiconductor wafer is extracted in this manner, and the cut adhesive layer is adhered to the inner surface side of the semiconductor wafer to be peeled off from the substrate.
之後藉由接著劑層使半導體晶片承載於導線架的晶粒墊上或者其他半導體晶片(下段晶片)的表面(以下晶片所承載晶粒墊或下段晶片表面記載為「晶片承載部」)。晶片承載部在半導體晶片承載前加熱或在承載後立即加熱。加熱溫度通常為80~200℃，較佳為100~180℃，加熱時間通常為0.1秒~5分鐘，較佳為0.5秒~3分鐘，承載時的壓力通常為1kPa~200MPa。 Thereafter, the semiconductor wafer is carried on the die pad of the lead frame or the surface of the other semiconductor wafer (lower stage wafer) by the adhesive layer (hereinafter, the die pad or the lower wafer surface carried by the wafer is described as "wafer carrying portion"). The wafer carrier is heated prior to loading of the semiconductor wafer or immediately after loading. The heating temperature is usually 80 to 200 ° C, preferably 100 to 180 ° C, and the heating time is usually 0.1 to 5 minutes, preferably 0.5 to 3 minutes, and the pressure at the time of carrying is usually 1 kPa to 200 MPa.
當半導體晶片承載於晶片搭載部之後，視需要可進行加熱。此時的加熱條件為上述加熱溫度範圍，加熱時間通常為1~180分鐘，較佳為10~120分鐘。 After the semiconductor wafer is carried on the wafer mounting portion, heating may be performed as needed. The heating condition at this time is the above heating temperature range, and the heating time is usually from 1 to 180 minutes, preferably from 10 to 120 minutes.
又，承載後未進行加熱處理而為假接著狀態，可利用封裝製造中通常進行的樹脂密封的加熱使接著劑層硬化。經過這些步驟，接著劑層硬化，半導體晶片與晶片承載部可堅固地接著。接著劑層在晶粒黏結條件下為流動化，因此晶片承載部的凹凸可被充分地埋入，可防止空隙的發生，使得封裝的信賴性增加。 Further, after the load is carried out, the heat treatment is not performed, and the adhesive layer is cured by the heating of the resin seal which is usually performed in the production of the package. Through these steps, the adhesive layer is hardened and the semiconductor wafer and the wafer carrier can be firmly adhered. Then, the agent layer is fluidized under the grain bonding condition, so that the unevenness of the wafer carrying portion can be sufficiently buried, the occurrence of voids can be prevented, and the reliability of the package is increased.
本發明的切割黏結片除上述使用方法以外，也可使用 於半導體化合物、玻離、陶瓷、金屬等的接著。 The cut-and-bonded sheet of the present invention can also be used in addition to the above-mentioned method of use. Followed by semiconductor compounds, glass, ceramics, metals, and the like.
以下藉由實施例說明本發明，但是本發明不限於這些實施例。而且在下述的實施例及比較例之中，[儲存彈性率及tan δ的測定]、[應力緩和率的測定]及[接著劑層的收縮觀察]如以下進行。 The invention is illustrated by the following examples, but the invention is not limited to the examples. Further, in the following examples and comparative examples, [Measurement of storage elastic modulus and tan δ], [Measurement of stress relaxation rate], and [Contraction observation of adhesive layer] were carried out as follows.
硬化前的接著劑層(在比較例1及2中，與後述的接著劑層的收縮觀察試驗相同，為照射紫外線的接著劑層)在80℃的儲存彈性率及tan δ經動態黏彈性裝置(Rheometrix公司製RDAII)，以週波數1Hz測定。 The adhesive layer before curing (in Comparative Examples 1 and 2, the same as the shrinkage observation test of the adhesive layer described later, the adhesive layer irradiated with ultraviolet rays), the storage elastic modulus at 80 ° C and the tan δ dynamic viscoelastic device (RDAII manufactured by Rheometrix Co., Ltd.), measured at a cycle number of 1 Hz.
硬化前的接著劑層(在比較例1及2中，與後述的接著劑層的收縮觀察試驗相同，為照射紫外線的接著劑層)在80℃的應力緩和率，經動態黏彈性裝置(Rheometrix公司製RDAII)，加上20%扭曲應力，測定初期應力A與120秒後的應力B，由下式計算出。 The adhesive layer before curing (in Comparative Examples 1 and 2, the same as the shrinkage observation test of the adhesive layer described later, the adhesive layer irradiated with ultraviolet rays) has a stress relaxation rate at 80 ° C, and is subjected to a dynamic viscoelastic device (Rheometrix). The company's RDAII), plus 20% torsional stress, measures the initial stress A and the stress B after 120 seconds, which is calculated by the following formula.
應力緩和力=(A-B)/A×100(%) Stress relaxation force = (A-B) / A × 100 (%)
使用Disc公司製的DGP8760乾研磨矽晶圓內面(200mm直徑，厚度75μm)。使用貼膜機(Lintec公司製，Adwill(商標)RAD2500 m/8)將切割黏結片貼附於矽晶圓的乾研磨處理面(晶圓內面)，同時固定於連結框(link frame)。又切割黏結片的接著劑層含有能量線聚合性化合物的情形，使 用紫外線照射裝置(Lintec公司製，Adwill(商標)RAD2000)，從該片的基材面照射紫外線(350mW/cm2，190mJ/cm2)。 The inner surface of the wafer (200 mm diameter, thickness 75 μm) was dry-polished using DGP8760 manufactured by Disc Corporation. The dicing adhesive sheet was attached to the dry-polishing surface (inner wafer surface) of the ruthenium wafer using a film coater (Adwill (trademark) RAD2500 m/8, manufactured by Lintec Co., Ltd.), and was fixed to a link frame. In the case where the adhesive layer of the dicing sheet contains the energy ray-polymerizable compound, the surface of the substrate of the sheet is irradiated with ultraviolet rays (350 mW/cm 2 , 190 mJ/ using an ultraviolet irradiation device (Adwill (trademark) RAD2000, manufactured by Lintec Co., Ltd.). Cm 2 ).
之後，使用切割裝置(DISCO公司製，DFD651)，切割成8mm×8mm體積的晶片，將接著片的接著劑層以及晶片從基材剝離，獲得具有接著劑層的晶片。切割時的切入量為對接著片的基材切入20μm。 Thereafter, a wafer having a volume of 8 mm × 8 mm was cut using a dicing apparatus (DFD651, manufactured by DISCO Corporation), and the adhesive layer of the adhesive sheet and the wafer were peeled off from the substrate to obtain a wafer having an adhesive layer. The amount of cut at the time of cutting was 20 μm cut into the substrate of the succeeding sheet.
具有接著劑層的晶片之接著劑層端部的收縮以數位顯微鏡(VHX-1000，Keyence公司製)觀察，端部的接著劑層的收縮以下述基準評估。 The shrinkage of the end of the adhesive layer of the wafer having the adhesive layer was observed with a digital microscope (VHX-1000, manufactured by Keyence), and the shrinkage of the adhesive layer at the end was evaluated on the following basis.
A~未見到收縮。 A~ No shrinkage was seen.
B~晶片端部有超過0μm、未滿10μm的收縮。 B~ The end of the wafer has a shrinkage of more than 0 μm and less than 10 μm.
C~晶片端部有10μm以上的收縮。 The end of the C~ wafer has a shrinkage of 10 μm or more.
構成接著劑的接著劑組成物(a)~(h)的各成分如下述及表1所記載。根據表1的成分及調配量調配各成分，調整接著劑組成物(a)~(h)。 The components of the adhesive compositions (a) to (h) constituting the adhesive are as described below and in Table 1. The components were blended according to the components and the amounts of the ingredients in Table 1, and the adhesive compositions (a) to (h) were adjusted.
(A1)丙烯聚合物：含有丙烯酸丁酯為主成分、且丙烯酸2-乙基己酯為全單體中的15質量%成分之丙烯聚合物(Mw=80萬，Tg=-28℃)。 (A1) A propylene polymer: a propylene polymer containing a butyl acrylate as a main component and 2-ethylhexyl acrylate as a 15% by mass component of the all monomer (Mw = 800,000, Tg = -28 ° C).
(A2)丙烯聚合物：含有丙烯酸甲酯為主成分、且丙烯酸2-乙基己酯為全單體中的15質量%成分之丙烯聚合物(Mw=80萬，T2=37℃)。 (A2) A propylene polymer: a propylene polymer containing a methyl acrylate as a main component and 2-ethylhexyl acrylate as a 15% by mass component of the all monomer (Mw = 800,000, T2 = 37 ° C).
(B)環氧樹脂：有丙烯橡膠微粒分散的雙酚A型液狀環 氧樹脂(日本觸媒公司製BPA328)。 (B) Epoxy resin: bisphenol A type liquid ring dispersed with propylene rubber particles Oxygen resin (BPA328 manufactured by Nippon Shokubai Co., Ltd.).
(C)熱硬化劑：酚醛型酚樹脂(昭和高分子公司製Shonol BRG556)。 (C) Thermosetting agent: a novolac type phenol resin (Shonol BRG556 manufactured by Showa Polymer Co., Ltd.).
(D)硬化促進劑：2-苯基-4,5-二(羥甲基)咪唑(四國化成工業公司製Curezol 2PHz)。 (D) Hardening accelerator: 2-phenyl-4,5-bis(hydroxymethyl)imidazole (Curezol 2PHz manufactured by Shikoku Kasei Kogyo Co., Ltd.).
(E)偶合劑：矽烷偶合劑(三菱化學公司製MKC silicate MSEP2)。 (E) Coupling agent: decane coupling agent (MKC silicate MSEP2 manufactured by Mitsubishi Chemical Corporation).
(F)無機填充材料：矽填充料(Admatechs公司製Admafine SC2050)。 (F) Inorganic filler: 矽 filler (Admafine SC2050, manufactured by Admatechs Co., Ltd.).
(G)熱塑性樹脂：聚酯樹脂(東洋紡織公司製Byron220)。 (G) Thermoplastic resin: Polyester resin (Byron 220 manufactured by Toyobo Co., Ltd.).
(H)能量線聚合性化合物：含二環戊二烯結構之丙烯酸酯(日本化藥公司製Kayarad R684)。 (H) Energy ray polymerizable compound: acrylate containing a dicyclopentadiene structure (Kayarad R684, manufactured by Nippon Kayaku Co., Ltd.).
(I)光聚合起始劑：α-羥基環己基苯基酮(Ciba Spacilty Chemical公司製Irgacure 184)。 (I) Photopolymerization initiator: α-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Spacilty Chemical Co., Ltd.).
(J)交聯劑：三甲氧基丙烷改性甲苯二異氰酸酯(東洋油墨製造公司製BHS-8515)。 (J) Crosslinking agent: Trimethoxypropane modified toluene diisocyanate (BHS-8515, manufactured by Toyo Ink Manufacturing Co., Ltd.).
使用如表1記載之組成的接著劑組成物(a)~(h)。表1中，各成分的數值顯示固形分換算的質量部，本發明中之固形分為溶劑以外的全成分。表1所記載之組成之接著劑組成物(a)~(h)於甲基乙基酮稀釋成固形分濃度為50質量%，在經矽(silicone)處理的剝離膜(Lintec公司製SP-PET381031)上塗布、乾燥成乾燥後厚度為25μm(乾燥 條件：在烤箱100℃，1分鐘)，獲得形成於剝離膜上的接著劑層。之後使接著劑層與表2劑載的基材貼合，將接著劑層轉印於基材上，獲得所欲的切割黏結片。各評估結果如表2所示。 The adhesive compositions (a) to (h) having the compositions shown in Table 1 were used. In Table 1, the numerical values of the respective components show the mass portions converted into solid fractions, and the solids in the present invention are classified into all components other than the solvent. The adhesive composition (a) to (h) of the composition described in Table 1 was diluted with methyl ethyl ketone to have a solid content concentration of 50% by mass, and a silicone-treated release film (SP-made by Lintec) PET381031) coated and dried to a thickness of 25 μm after drying (dry Condition: An adhesive layer formed on the release film was obtained in an oven at 100 ° C for 1 minute. Thereafter, the adhesive layer was bonded to the substrate supported on the surface of Table 2, and the adhesive layer was transferred onto the substrate to obtain a desired diced adhesive sheet. The results of each evaluation are shown in Table 2.
從表2可知，實施例的切割黏結片的接著劑層的收縮觀察評估為良好。因此，實施例的切割黏結片即使在經過嚴酷的溫熱條件及起離(lift off)步驟的情形，接著性或封裝信賴性亦優良。 As is clear from Table 2, the shrinkage observation of the adhesive layer of the cut-and-bonded sheet of the Example was evaluated as good. Therefore, the dicing adhesive sheet of the embodiment is excellent in adhesion or package reliability even in the case of severe warming conditions and lift off steps.
另一方面，比較例之切割黏結片觀察到比實施例大的接著劑層的收縮。因此，比較例的切割黏結片在經過嚴酷的溫熱條件及起離(lift off)步驟的情形，接著性或封裝信賴性差。 On the other hand, the dicing adhesive sheet of the comparative example observed shrinkage of the adhesive layer larger than that of the examples. Therefore, the cut-and-bonded sheet of the comparative example was inferior in the case of the severe warming condition and the lift off step, and the adhesiveness or the package reliability was poor.
10‧‧‧切割黏結片 10‧‧‧ cutting adhesive sheets
1‧‧‧基材 1‧‧‧Substrate
2‧‧‧接著劑層 2‧‧‧ adhesive layer
3‧‧‧半導體晶片 3‧‧‧Semiconductor wafer
4‧‧‧半導體晶圓 4‧‧‧Semiconductor wafer
5‧‧‧切割刀 5‧‧‧Cutting knife
6‧‧‧切口 6‧‧‧Incision
7‧‧‧連結框 7‧‧‧ link box
第1圖為顯示使用切割黏結片的切割步驟之剖面示意圖。 Fig. 1 is a schematic cross-sectional view showing a cutting step using a dicing die.
第2圖為顯示使用習知切割黏結片的切割步驟之剖面示意圖。 Fig. 2 is a schematic cross-sectional view showing a cutting step using a conventional cutting adhesive sheet.
10‧‧‧切割黏結片 10‧‧‧ cutting adhesive sheets
1‧‧‧基材 1‧‧‧Substrate
2‧‧‧接著劑層 2‧‧‧ adhesive layer
4‧‧‧半導體晶圓 4‧‧‧Semiconductor wafer
5‧‧‧切割刀 5‧‧‧Cutting knife
7‧‧‧連結框 7‧‧‧ link box
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| JP2011201167A JP5951207B2 (en) | 2011-09-14 | 2011-09-14 | Dicing die bonding sheet |
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| CN108987294B (en) * | 2018-06-21 | 2021-02-02 | 上海飞骧电子科技有限公司 | Gallium arsenide glue brushing method for passive device for solving problem of glue overflow in packaging |
| US11639410B2 (en) | 2019-12-18 | 2023-05-02 | Shin-Etsu Chemical Co., Ltd. | Heat-curable resin composition and uses thereof |
| JP7298468B2 (en) * | 2019-12-18 | 2023-06-27 | 信越化学工業株式会社 | Thermosetting resin composition and its use |
| CN112341975B (en) * | 2020-11-25 | 2022-03-08 | 中路交科科技股份有限公司 | Second-order epoxy adhesive layer oil, preparation method and application method thereof |
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| US20070141330A1 (en) * | 2004-08-03 | 2007-06-21 | The Furukawa Electric Co., Ltd. | Method of producing a semiconductor device, and wafer-processing tape |
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| US7768141B2 (en) * | 2006-02-14 | 2010-08-03 | Lg Innotek Co., Ltd. | Dicing die attachment film and method for packaging semiconductor using same |
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| JP2010171402A (en) * | 2008-12-24 | 2010-08-05 | Nitto Denko Corp | Thermosetting die-bonding film |
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| US20070141330A1 (en) * | 2004-08-03 | 2007-06-21 | The Furukawa Electric Co., Ltd. | Method of producing a semiconductor device, and wafer-processing tape |
| JP2006261657A (en) * | 2005-02-21 | 2006-09-28 | Nitto Denko Corp | Manufacturing method for semiconductor device |
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