TW202106831A - Adhesive tape - Google Patents
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- TW202106831A TW202106831A TW109109607A TW109109607A TW202106831A TW 202106831 A TW202106831 A TW 202106831A TW 109109607 A TW109109607 A TW 109109607A TW 109109607 A TW109109607 A TW 109109607A TW 202106831 A TW202106831 A TW 202106831A
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- 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]
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- 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
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- 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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- 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
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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
- H01L21/02—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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
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- 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
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- 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
- C09J2301/312—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 parameters being the characterizing feature
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- 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
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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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
- H01L2224/01—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
- H01L2224/16135—Disposition the bump connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip
- H01L2224/16145—Disposition the bump connector connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip the bodies being stacked
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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
- H01L2224/81—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 bump connector
Abstract
Description
本發明係關於一種黏著帶。The present invention relates to an adhesive tape.
於半導體晶片之製造步驟中，為了使晶圓或半導體晶片加工時之處理容易，且防止破損而使用黏著帶。例如，於將自高純度之單晶矽等切出之厚膜晶圓研磨至規定厚度而製成薄膜晶圓之情形時，在使黏著帶貼合於厚膜晶圓後進行研磨。In the manufacturing steps of semiconductor wafers, adhesive tapes are used in order to facilitate the handling of wafers or semiconductor wafers during processing and prevent breakage. For example, when a thick film wafer cut from a high-purity single crystal silicon or the like is polished to a predetermined thickness to make a thin film wafer, the adhesive tape is attached to the thick film wafer and then polished.
對於用於此種黏著帶之接著劑組成物，要求可於加工步驟中牢固地固定晶圓或半導體晶片等被接著體之程度之高接著性，並且可於步驟結束後不損傷晶圓或半導體晶片等被接著體而剝離（以下，亦稱為「高接著易剝離」）。 作為實現高接著易剝離之接著劑組成物，於專利文獻1中揭示有一種黏著帶，其使用藉由照射紫外線等光進行硬化而黏著力降低之光硬化型黏著劑。藉由使用光硬化型黏著劑作為黏著劑，可於加工步驟中確實地固定被接著體，並且可藉由照射紫外線等而容易地進行剝離。 [先前技術文獻] [專利文獻]For the adhesive composition used for this kind of adhesive tape, it is required to have a high degree of adhesion that can firmly fix the wafer or semiconductor chip to be bonded during the processing step, and can not damage the wafer or semiconductor after the step is completed The wafer and the like are peeled off by the bonded body (hereinafter, also referred to as "high adhesion and easy peeling"). As an adhesive composition that achieves high adhesion and easy peeling, Patent Document 1 discloses an adhesive tape that uses a photocurable adhesive that is cured by irradiating light such as ultraviolet rays to reduce the adhesive force. By using a light-curing adhesive as an adhesive, the adherend can be securely fixed in the processing step, and it can be easily peeled off by irradiating ultraviolet rays or the like. [Prior Technical Literature] [Patent Literature]
專利文獻1：日本特開平5-32946號公報Patent Document 1: Japanese Patent Laid-Open No. 5-32946
[發明所欲解決之課題][The problem to be solved by the invention]
近年來，由於半導體製品之薄化、小型化，逐漸開始製造於晶圓上積層有多個半導體晶片之半導體元件，半導體晶片係藉由熱壓接合而積層。此處，將表示熱壓接合之情況之示意圖示於圖1。如圖1所示，於熱壓接合中，將半導體晶片3積層在經由黏著帶1固定於玻璃板等之晶圓2上。半導體晶片3藉由施加熱及載重而與下層之半導體晶片連接，藉由重複該步驟而不斷地積層半導體晶片。
於此種熱壓接合中，為了晶片彼此或晶片與晶圓間之接合，多以260℃左右之高溫及高壓來謀求壓接，此時，黏著帶於厚度方向上被強烈地壓縮。於使用以往之黏著帶之情形時，在被施以熱及載重時，於半導體晶片積層部位之外緣部中，剪切方向之應力施加於黏著帶1與晶圓2之界面，從而於該界面產生剝離。若黏著帶之一部分剝離，則黏著帶變得不平坦，因此無法正常地積層半導體晶片，或無法進行積層。因此，於熱壓接合中，要求一種除了具備以往之高接著易剝離功能以外，亦具備260℃左右之耐熱性與不會因熱及壓力而剝離之性能的黏著帶。
又，作為積層時之另一個課題，可列舉晶圓2之黏著帶1側之面所形成之銲點凸塊4因熱壓接時之壓力而造成之變形。於使用以往之黏著帶之情形時，晶圓2與黏著帶1之間之密接弱，因此存在於壓接時晶圓2移動，此時埋入於黏著劑層中之銲點凸塊4發生變形之情形。若銲點凸塊4發生變形，則會於黏著帶剝離後之製程中產生接合不良，或因外觀不良而成為不良品。因此，對於暫時固定時所使用之黏著帶，同時亦要求抑制熱壓接時之凸塊變形。In recent years, due to the thinning and miniaturization of semiconductor products, semiconductor devices with multiple semiconductor chips stacked on a wafer have gradually begun to be manufactured. The semiconductor chips are laminated by thermocompression bonding. Here, a schematic diagram showing the state of thermocompression bonding is shown in FIG. 1. As shown in FIG. 1, in the thermocompression bonding, a
本發明之目的在於提供一種黏著帶，該黏著帶即便在用於伴隨著高溫及載重之步驟之情形時亦不會自被接著體剝離，且於剝離時可容易地進行剝離，進而亦可抑制銲點凸塊之變形。又，本發明之目的在於提供一種使用該黏著帶之半導體元件之製造方法。 [解決課題之技術手段]The object of the present invention is to provide an adhesive tape that does not peel off from the adherend even when used in a process accompanied by high temperature and load, and can be easily peeled off during peeling, thereby suppressing Deformation of solder bumps. Moreover, the object of the present invention is to provide a method of manufacturing a semiconductor device using the adhesive tape. [Technical means to solve the problem]
本發明係一種黏著帶，其依序積層有黏著劑層A、基材膜及黏著劑層B；將上述黏著劑層A貼附於矽晶圓晶片，將上述黏著劑層B貼附於玻璃板，自黏著帶之上述黏著劑層B側之面向上述黏著劑層A照射3000 mJ/cm2 之紫外線，於240℃加熱處理10分鐘後之對於矽晶圓晶片之晶片剪切強度為3 N/9 mm2 以上；將上述黏著劑層A貼附於矽晶圓，自上述黏著劑層B側之面向上述黏著劑層A照射3000 mJ/cm2 之紫外線，於200℃加熱處理1小時後之對於矽晶圓之180°剝離強度為0.1 N/inch以上0.3 N/inch以下；將上述黏著劑層B貼附於玻璃板，對上述黏著劑層A照射3000 mJ/cm2 之紫外線後，藉由SAICAS測定所測定出之距離上述黏著劑層A之表層部10 μm的部分中之水平載重強度為0.06 N/mm以上。 以下，對本發明進行詳細說明。The present invention is an adhesive tape, which is sequentially laminated with an adhesive layer A, a base film and an adhesive layer B; the adhesive layer A is attached to the silicon wafer chip, and the adhesive layer B is attached to the glass Board, from the adhesive layer B side of the adhesive tape facing the adhesive layer A, irradiate 3000 mJ/cm 2 of ultraviolet rays, heat treatment at 240 ℃ for 10 minutes, the wafer shear strength to the silicon wafer is 3 N /9 mm 2 or more; Attach the adhesive layer A to the silicon wafer, and irradiate the adhesive layer A with 3000 mJ/cm 2 of ultraviolet rays from the side of the adhesive layer B to the adhesive layer A, and heat treatment at 200°C for 1 hour The 180° peel strength for silicon wafers is 0.1 N/inch or more and 0.3 N/inch or less; the adhesive layer B is attached to the glass plate, and the adhesive layer A is irradiated with 3000 mJ/cm 2 of ultraviolet rays, The horizontal load strength in a portion 10 μm away from the surface layer portion of the adhesive layer A measured by SAICAS measurement is 0.06 N/mm or more. Hereinafter, the present invention will be described in detail.
本發明之黏著帶依序積層有黏著劑層A、基材膜及黏著劑層B。 關於本發明之黏著帶，將上述黏著劑層A貼附於矽晶圓晶片，將上述黏著劑層B貼附於玻璃板，自黏著帶之上述黏著劑層B側之面向上述黏著劑層A照射3000 mJ/cm2 之紫外線，於240℃加熱處理10分鐘後之對於矽晶圓晶片之晶片剪切強度為3 N/9 mm2 以上。 藉由黏著帶之黏著劑層之至少單面滿足上述範圍之晶片剪切強度及下述180°剝離強度及由SAICAS測定所測出之水平載重強度，黏著帶亦不易因伴隨著高溫及載重之處理而剝離，且可抑制糊劑殘留於被接著體及凸塊之變形。The adhesive tape of the present invention is sequentially laminated with an adhesive layer A, a base film and an adhesive layer B. With regard to the adhesive tape of the present invention, the adhesive layer A is attached to a silicon wafer, and the adhesive layer B is attached to a glass plate, from the adhesive layer B side of the adhesive tape facing the adhesive layer A After irradiating 3000 mJ/cm 2 of ultraviolet rays and heating treatment at 240°C for 10 minutes, the wafer shear strength for silicon wafers is 3 N/9 mm 2 or more. The adhesive layer of the adhesive tape meets the chip shear strength of the above range on at least one side, the following 180° peel strength and the horizontal load strength measured by SAICAS, the adhesive tape is not easily affected by high temperature and load. It can be peeled off by processing, and the deformation of the paste remaining on the bonded body and bumps can be suppressed.
所謂晶片剪切強度，係測定半導體晶片之接合強度之方法之一，當於橫方向上對藉由接合材而接合於晶圓或基板等上之半導體晶片施加力時，可測定半導體晶片與晶圓或基板之接合面被破壞時之力。 於本發明中，用作測量黏著帶與矽晶圓晶片之剪切方向之密接性的指標，具體而言自橫方向朝著接合於黏著帶上之矽晶圓晶片施加力，測定矽晶圓晶片剝離時之強度。若上述晶片剪切強度高，則針對朝向剪切方向之應力之密接性提高，對於壓縮時在晶片壓接部位之外緣部中施加於黏著帶與晶圓之界面之剪切方向的載重，亦難以剝離，因此結果為於施加熱及載重時不易產生晶圓與黏著帶之間之剝離。就提高黏著帶與矽晶圓之剪切方向之密接性的觀點而言，上述晶片剪切強度較佳為4 N/9 mm2 以上，更佳為4.5 N/9 mm2 以上，進而較佳為5.5 N/9 mm2 以上。上述晶片剪切強度之上限並無特別限定，就使用後更容易剝離之觀點而言，較佳為10 N/9 mm2 以下。上述晶片剪切強度可藉由黏著劑之種類、矽酮或氟化合物之含量進行調節。 再者，更具體而言，上述晶片剪切強度可藉由以下之方法進行測定。The so-called chip shear strength is one of the methods of measuring the bonding strength of semiconductor chips. When a force is applied to a semiconductor chip that is bonded to a wafer or a substrate by a bonding material in the lateral direction, the semiconductor chip and the crystal can be measured. The force when the joint surface of the circle or the substrate is broken. In the present invention, it is used as an index for measuring the adhesion between the adhesive tape and the silicon wafer in the shear direction, specifically, applying a force from the lateral direction to the silicon wafer bonded to the adhesive tape to measure the silicon wafer The strength when the wafer is peeled off. If the above-mentioned chip shear strength is high, the adhesion to the stress in the shear direction is improved. For the load in the shear direction applied to the interface between the adhesive tape and the wafer at the outer edge of the chip crimping portion during compression, It is also difficult to peel off, so the result is that it is not easy to peel off between the wafer and the adhesive tape when heat and load are applied. From the viewpoint of improving the adhesion between the adhesive tape and the silicon wafer in the shear direction, the above-mentioned chip shear strength is preferably 4 N/9 mm 2 or more, more preferably 4.5 N/9 mm 2 or more, and even more preferable It is 5.5 N/9 mm 2 or more. The upper limit of the wafer shear strength is not particularly limited, but from the viewpoint of easier peeling after use, it is preferably 10 N/9 mm 2 or less. The above-mentioned chip shear strength can be adjusted by the type of adhesive and the content of silicone or fluorine compound. Furthermore, more specifically, the above-mentioned wafer shear strength can be measured by the following method.
將切成3 cm×4 cm且兩面由脫模膜保護之黏著帶之黏著劑層B側的脫模膜剝離，使黏著劑層B與載玻片（S9112，松浪硝子工業公司製造）貼合。將該黏著帶與玻璃之積層體之黏著劑層A側的脫模膜剝離，將3 mm×3 mm、3 mm厚且表面粗糙度＜0.1 μm之單晶矽晶圓晶片置於黏著帶之黏著劑層A，以載置台溫度20℃、壓接頭溫度20℃、接合壓力3 N進行接合。繼而，使用高壓水銀UV照射機，自黏著帶之黏著劑層B側朝向黏著劑層A照射405 nm之紫外線，且以黏著劑層A之基材側相反之側之表面的照射量成為3000 mJ/cm2 之方式進行照射。之後，於240℃進行10分鐘加熱處理。於加熱處理後，將矽晶圓晶片於室溫下放置冷卻，使用黏結強度試驗機（4000PXY，Nordson-Advanced-Technology公司製造，萬能型），於25℃、50%RH下向矽晶圓晶片之整個側面施加相對於晶片之側面垂直方向之力，測定使矽晶圓晶片移動時之最大載重，將其設為晶片剪切強度。Peel off the release film on the adhesive layer B side of the adhesive tape cut into 3 cm×4 cm and both sides are protected by the release film, so that the adhesive layer B is attached to the glass slide (S9112, manufactured by Songnang Glass Industry Co., Ltd.) . The adhesive tape and the release film on the side of the adhesive layer A of the glass laminate are peeled off, and a 3 mm×3 mm, 3 mm thick monocrystalline silicon wafer with a surface roughness of <0.1 μm is placed on the adhesive tape Adhesive layer A was bonded at a mounting table temperature of 20°C, a pressure joint temperature of 20°C, and a bonding pressure of 3N. Then, using a high-pressure mercury UV irradiator, 405 nm ultraviolet rays were irradiated from the adhesive layer B side of the adhesive tape toward the adhesive layer A, and the irradiation amount of the surface on the side opposite to the substrate side of the adhesive layer A became 3000 mJ /cm 2 for irradiation. After that, heat treatment was performed at 240°C for 10 minutes. After the heat treatment, the silicon wafer is placed at room temperature to cool, and the bonding strength tester (4000PXY, manufactured by Nordson-Advanced-Technology, universal type) is used to transfer the silicon wafer at 25°C and 50%RH The entire side of the wafer is applied with a force perpendicular to the side of the wafer to measure the maximum load when the silicon wafer is moved, and set it as the wafer shear strength.
關於本發明之黏著帶，將上述黏著劑層A貼附於矽晶圓，自上述黏著劑層B側之面向上述黏著劑層A照射3000 mJ/cm2 之紫外線，於200℃加熱處理1小時後之對於矽晶圓之180°剝離強度為0.1 N/inch以上且0.3 N/inch以下。 藉由黏著帶為上述範圍之180°剝離強度，可利用充分之黏著力保護被接著體，並且可於使用後容易地剝離。又，由於可獲得半導體晶片與黏著帶間之充分之密接性，故而可抑制凸塊之變形。就提高與被接著體之黏著力而使黏著帶更難剝離之觀點而言，上述180°剝離強度較佳為0.11 N/inch以上，更佳為0.13 N/inch以上，進而較佳為0.15 N/inch以上。又，就使用後更容易剝離，抑制糊劑殘留之觀點而言，上述180°剝離強度更佳為0.25 N/inch以下，進而較佳為0.2 N/inch以下。上述180°剝離強度可藉由黏著劑層之種類、所添加之填料、無機填充劑、微粒子成分或胺酯化合物、具有矽酮或氟化合物等脫模性成分之添加劑等之含量進行調節。 再者，更具體而言，上述180°剝離強度可藉由以下之方法進行測定。Regarding the adhesive tape of the present invention, the adhesive layer A is attached to a silicon wafer, and the adhesive layer A is irradiated with 3000 mJ/cm 2 of ultraviolet rays from the side of the adhesive layer B to the surface of the adhesive layer A, and heated at 200°C for 1 hour The subsequent 180° peel strength for silicon wafers is 0.1 N/inch or more and 0.3 N/inch or less. With the 180° peel strength of the adhesive tape in the above range, sufficient adhesive force can be used to protect the adherend, and it can be easily peeled off after use. In addition, since sufficient adhesion between the semiconductor chip and the adhesive tape can be obtained, the deformation of the bumps can be suppressed. From the viewpoint of improving the adhesion with the adherend and making the adhesive tape more difficult to peel off, the above-mentioned 180° peel strength is preferably 0.11 N/inch or more, more preferably 0.13 N/inch or more, and even more preferably 0.15 N /inch or more. In addition, from the viewpoint of easier peeling after use and suppression of paste residue, the above-mentioned 180° peel strength is more preferably 0.25 N/inch or less, and more preferably 0.2 N/inch or less. The above-mentioned 180° peel strength can be adjusted by the type of adhesive layer, the added filler, inorganic filler, particulate component or urethane compound, and the content of additives with mold release components such as silicone or fluorine compound. Furthermore, more specifically, the above-mentioned 180° peel strength can be measured by the following method.
將黏著帶之黏著劑層A側之脫模膜剝離，將8英吋、厚度0.75 mm、表面粗糙度＜0.1 μm之單晶矽晶圓置於黏著帶之黏著劑層A，利用2 kg之橡膠輥於矽晶圓上往返滾動一次，藉此使其等貼合。於貼合後在常溫下靜置20分鐘後，將黏著劑層B側之脫模膜剝離，繼而，使用高壓水銀UV照射機，自黏著帶之黏著劑層B側朝向黏著劑層A照射405 nm之紫外線，且以黏著劑層A之基材側相反之側之表面的照射量成為3000 mJ/cm2 之方式進行照射。之後，於200℃進行1小時加熱處理。針對加熱處理後之黏著帶，依據JIS Z0237，以剝離速度300 mm/分鐘進行180°方向之拉伸試驗，測定對於矽晶圓之180°剝離強度。The release film on the adhesive layer A side of the adhesive tape was peeled off, and an 8-inch single crystal silicon wafer with a thickness of 0.75 mm and a surface roughness <0.1 μm was placed on the adhesive layer A of the adhesive tape, using 2 kg The rubber roller rolls back and forth on the silicon wafer once to bond it together. After lamination, let it stand at room temperature for 20 minutes, peel off the release film on the side of the adhesive layer B, and then use a high-pressure mercury UV irradiation machine to irradiate 405 from the side of the adhesive layer B of the adhesive tape toward the adhesive layer A. It is irradiated so that the irradiation amount of the surface on the side opposite to the substrate side of the adhesive layer A becomes 3000 mJ/cm 2 with ultraviolet rays of nm. After that, heat treatment was performed at 200°C for 1 hour. For the adhesive tape after heat treatment, according to JIS Z0237, a 180° direction tensile test was carried out at a peeling speed of 300 mm/min to measure the 180° peel strength of the silicon wafer.
關於本發明之黏著帶，將上述黏著劑層B貼附於玻璃板，對上述黏著劑層A照射3000 mJ/cm2 之紫外線後，藉由SAICAS測定所測定出之距離上述黏著劑層A之表層部10 μm的部分中之水平載重強度為0.06 N/mm以上。 所謂SAICAS法，稱為Surface And Interfacial Cutting Anaylsis System（表面與界面切割分析系統）法，係利用鋒利之切刀自表層部低速切削材料之評估法。藉由使用SAICAS法，可測定於切削黏著劑層之表面時施加於切刀之水平力及垂直力。 藉由黏著劑層A之水平載重強度為上述範圍，黏著劑層之強度提高，自被接著體剝離時之糊劑不易碎裂，因此可抑制糊劑殘留於被接著體。就提高黏著劑層之強度而抑制糊劑殘留之觀點而言，上述水平載重強度較佳為0.07 N/mm以上，更佳為0.075 N/mm以上，進而較佳為0.08 N/mm以上。上述水平載重強度之上限並無特別限定，就抑制黏著劑層變脆之觀點而言，較佳為0.2 N/mm以下。上述水平載重強度可藉由黏著劑之種類、所添加之填料、無機填充劑、微粒子成分或胺酯化合物、具有脫模性成分之添加劑等之含量進行調節。 再者，具體而言，上述水平載重強度可藉由如下之方法進行測定。With regard to the adhesive tape of the present invention, the adhesive layer B is attached to a glass plate, the adhesive layer A is irradiated with 3000 mJ/cm 2 of ultraviolet rays, and the distance measured by SAICAS is measured. The horizontal load strength of the 10 μm surface layer portion is 0.06 N/mm or more. The so-called SAICAS method is called the Surface And Interfacial Cutting Anaylsis System (surface and interface cutting analysis system) method, which uses a sharp cutter to cut materials from the surface at low speed. By using the SAICAS method, the horizontal and vertical force applied to the cutter when cutting the surface of the adhesive layer can be measured. When the horizontal load-bearing strength of the adhesive layer A is in the above range, the strength of the adhesive layer is improved, and the paste is not easily broken when peeled from the adherend, so that the paste can be prevented from remaining on the adherend. From the viewpoint of increasing the strength of the adhesive layer and suppressing paste residue, the horizontal load strength is preferably 0.07 N/mm or more, more preferably 0.075 N/mm or more, and still more preferably 0.08 N/mm or more. The upper limit of the horizontal load strength is not particularly limited, but from the viewpoint of suppressing brittleness of the adhesive layer, it is preferably 0.2 N/mm or less. The above-mentioned horizontal load strength can be adjusted by the type of adhesive, the content of fillers, inorganic fillers, particulate components or urethane compounds, and additives with mold release components. Furthermore, specifically, the above-mentioned horizontal load strength can be measured by the following method.
將切成3 cm×4 cm且兩面由脫模膜保護之黏著帶之黏著劑層B側的脫模膜剝離，使黏著劑層B與載玻片（S9112，松浪硝子工業公司製造）貼合而獲得測定用樣品。貼合係藉由使2 kg之輥於黏著帶之黏著劑層A側之面上往返滾動1次而進行。繼而，將所獲得之樣品之黏著劑層A側的脫模膜剝離，使用高壓水銀UV照射機，以黏著劑層A之基材側相反之側之表面的照度成為3000 mJ/cm2 之方式自黏著劑層A側照射405 nm之紫外光。之後，使用表面、界面物性解析裝置（SAICAS DN-20，Daipla-Wintes公司製造），於25℃、50%RH、紫外光截止之條件下測定黏著帶之黏著劑層A之水平力及垂直力。切刀使用單晶金剛石製之寬度1 mm、傾角40°、餘隙角10°之刀，切削條件設為恆定速度模式下水平方向5 μm/秒、垂直方向0.5 μm/秒。將水平載重為0.002 N以上之點設為切刀接觸到黏著劑層A表面之點，之後於垂直方向上10 μm之深度範圍測定水平載重強度。Peel off the release film on the adhesive layer B side of the adhesive tape cut into 3 cm×4 cm and both sides are protected by the release film, so that the adhesive layer B is attached to the glass slide (S9112, manufactured by Songnang Glass Industry Co., Ltd.) A sample for measurement is obtained. The bonding was performed by rolling a 2 kg roller on the side of the adhesive layer A of the adhesive tape once and back. Then, the release film on the adhesive layer A side of the obtained sample was peeled off, and a high-pressure mercury UV irradiation machine was used to set the illuminance on the surface opposite to the substrate side of the adhesive layer A to 3000 mJ/cm 2 Irradiate 405 nm ultraviolet light from the adhesive layer A side. After that, use the surface and interface property analysis device (SAICAS DN-20, manufactured by Daipla-Wintes) to measure the horizontal force and vertical force of the adhesive layer A of the adhesive tape under the conditions of 25°C, 50%RH, and UV cut-off. . The cutter is made of single crystal diamond with a width of 1 mm, an inclination angle of 40°, and a clearance angle of 10°. The cutting conditions are set to 5 μm/sec in the horizontal direction and 0.5 μm/sec in the vertical direction in the constant speed mode. The point where the horizontal load is 0.002 N or more is set as the point where the cutter touches the surface of the adhesive layer A, and then the horizontal load strength is measured at a depth of 10 μm in the vertical direction.
構成上述黏著劑層A之黏著劑成分，若滿足上述晶片剪切強度、180°剝離強度及水平載重強度之範圍，則並無特別限定，就容易滿足該等之範圍而言，較佳為於分子內具有自由基聚合性不飽和鍵之黏著劑成分。構成上述黏著劑層A之黏著劑成分更佳包含於分子內具有自由基聚合性不飽和鍵之(甲基)丙烯酸烷基酯系聚合性聚合物。 上述聚合性聚合物例如可藉由如下方式獲得：預先合成於分子內具有官能基之(甲基)丙烯酸系聚合物（以下，稱為含官能基之(甲基)丙烯酸系聚合物），使其與於分子內具有與上述官能基反應之官能基及自由基聚合性不飽和鍵之化合物（以下，稱為含官能基之不飽和化合物）反應。The adhesive component constituting the adhesive layer A is not particularly limited as long as it satisfies the ranges of the above-mentioned chip shear strength, 180° peel strength and horizontal load strength. As long as these ranges are easily satisfied, it is preferably An adhesive component with radically polymerizable unsaturated bonds in the molecule. It is more preferable that the adhesive component constituting the adhesive layer A includes an alkyl (meth)acrylate polymerizable polymer having a radically polymerizable unsaturated bond in the molecule. The above-mentioned polymerizable polymer can be obtained, for example, by pre-synthesizing a (meth)acrylic polymer having a functional group in the molecule (hereinafter referred to as a functional group-containing (meth)acrylic polymer), and making It reacts with a compound having a functional group that reacts with the above-mentioned functional group and a radically polymerizable unsaturated bond in the molecule (hereinafter referred to as a functional group-containing unsaturated compound).
上述含官能基之(甲基)丙烯酸系聚合物可藉由如下方式獲得：利用常規方法，使烷基之碳數通常為2～18之範圍之丙烯酸烷基酯及/或甲基丙烯酸烷基酯、含官能基之單體、及進而視需要可與該等共聚之其他改質用單體共聚。上述含官能基之(甲基)丙烯酸系聚合物之重量平均分子量通常為20萬～200萬左右。 再者，於本說明書中，重量平均分子量通常可藉由GPC法決定，例如可於管柱溫度40℃使用THF作為溶出液，使用Waters公司製造之HSPgel HR MB-M 6.0×150 mm作為管柱，根據聚苯乙烯標準進行決定。The above-mentioned functional group-containing (meth)acrylic polymer can be obtained by using a conventional method to make the alkyl acrylate and/or methacrylate alkyl with the carbon number of the alkyl group usually in the range of 2-18 Ester, functional group-containing monomers, and, if necessary, can be copolymerized with these copolymerized monomers for modification. The weight average molecular weight of the functional group-containing (meth)acrylic polymer is usually about 200,000 to 2 million. Furthermore, in this specification, the weight average molecular weight can usually be determined by the GPC method. For example, THF can be used as the eluent at the column temperature of 40℃, and the HSPgel HR MB-M 6.0×150 mm manufactured by Waters can be used as the column. , Make a decision based on polystyrene standards.
作為上述含官能基之單體，例如可列舉含羧基之單體、含羥基之單體、含環氧基之單體、含異氰酸基之單體、含胺基之單體等。作為上述含羧基之單體，可列舉丙烯酸、甲基丙烯酸等。作為上述含羥基之單體，可列舉丙烯酸羥基乙酯、甲基丙烯酸羥基乙酯等。作為上述含環氧基之單體，可列舉丙烯酸環氧丙基酯、甲基丙烯酸環氧丙基酯等。作為上述含異氰酸基之單體，可列舉丙烯酸異氰酸基乙酯、甲基丙烯酸異氰酸基乙酯等。作為上述含胺基之單體，可列舉丙烯酸胺基乙酯、甲基丙烯酸胺基乙酯等。Examples of the above-mentioned functional group-containing monomers include carboxyl group-containing monomers, hydroxyl group-containing monomers, epoxy group-containing monomers, isocyanate group-containing monomers, and amine group-containing monomers. Examples of the above-mentioned carboxyl group-containing monomer include acrylic acid, methacrylic acid, and the like. As the above-mentioned hydroxyl group-containing monomer, hydroxyethyl acrylate, hydroxyethyl methacrylate, and the like can be mentioned. Examples of the epoxy group-containing monomer include glycidyl acrylate, glycidyl methacrylate, and the like. Examples of the above-mentioned isocyanate group-containing monomer include isocyanatoethyl acrylate, isocyanatoethyl methacrylate, and the like. Examples of the above-mentioned amine group-containing monomer include aminoethyl acrylate, aminoethyl methacrylate, and the like.
作為上述可共聚之其他改質用單體，例如可列舉乙酸乙烯酯、丙烯腈、苯乙烯等一般用於(甲基)丙烯酸系聚合物之各種單體。As the aforementioned other copolymerizable monomers for modification, for example, various monomers generally used for (meth)acrylic polymers such as vinyl acetate, acrylonitrile, and styrene can be cited.
作為與上述含官能基之(甲基)丙烯酸系聚合物反應的含官能基之不飽和化合物，可根據上述含官能基之(甲基)丙烯酸系聚合物之官能基，使用與上述含官能基之單體相同者。例如，於上述含官能基之(甲基)丙烯酸系聚合物之官能基為羧基之情形時，使用含環氧基之單體或含異氰酸基之單體。於該官能基為羥基之情形時，使用含異氰酸基之單體。於該官能基為環氧基之情形時，使用含羧基之單體或丙烯醯胺等含醯胺基之單體。於該官能基為胺基之情形時，使用含環氧基之單體。As the functional group-containing unsaturated compound that reacts with the above-mentioned functional group-containing (meth)acrylic polymer, the above-mentioned functional group-containing (meth)acrylic polymer may be used according to the functional group of the above-mentioned functional group-containing (meth)acrylic polymer. The monomers are the same. For example, when the functional group of the aforementioned functional group-containing (meth)acrylic polymer is a carboxyl group, an epoxy group-containing monomer or an isocyanate group-containing monomer is used. When the functional group is a hydroxyl group, an isocyanate group-containing monomer is used. When the functional group is an epoxy group, a carboxyl group-containing monomer or an amide group-containing monomer such as acrylamide is used. When the functional group is an amino group, an epoxy group-containing monomer is used.
構成上述黏著劑層A之黏著劑成分，較佳為於將羥值及酸值分別設為XmgKOH/mg、YmgKOH/mg時，X＋Y≧10。 藉由上述黏著劑成分之羥值及酸值滿足上述關係式，黏著劑成分之凝聚力提高，黏著劑層A更不易斷裂，因此即便為施加了熱及載重之情形時，亦可使黏著帶不易剝離。又，藉由滿足上述關係式，亦可容易地滿足上述水平載重及晶片剪切強度。就進而使黏著帶不易剝離之觀點、以及控制上述水平載重及晶片剪切強度之觀點而言，上述X＋Y更佳為30以上，進而較佳為50以上。上述X＋Y之上限並無特別限定，就抑制因黏著劑層之極性提高而產生接著增強從而導致之糊劑殘留的觀點而言，較佳為70以下，更佳為65以下。再者，上述羥值及酸值例如可藉由上述含官能基之單體之量進行調節。The adhesive component constituting the adhesive layer A is preferably X+Y≧10 when the hydroxyl value and acid value are XmgKOH/mg and YmgKOH/mg, respectively. Since the hydroxyl value and acid value of the adhesive components satisfy the above relational expressions, the cohesive force of the adhesive components is increased, and the adhesive layer A is less likely to break. Therefore, even when heat and load are applied, the adhesive tape can be made difficult Peel off. In addition, by satisfying the above-mentioned relational expression, the above-mentioned horizontal load and wafer shear strength can also be easily satisfied. From the viewpoint of further preventing the adhesive tape from peeling off and the viewpoint of controlling the horizontal load and the chip shear strength, the above-mentioned X+Y is more preferably 30 or more, and more preferably 50 or more. The upper limit of the above X+Y is not particularly limited, but from the viewpoint of suppressing paste residue due to the increase in the polarity of the adhesive layer and subsequent reinforcement, it is preferably 70 or less, and more preferably 65 or less. Furthermore, the above-mentioned hydroxyl value and acid value can be adjusted by, for example, the amount of the above-mentioned functional group-containing monomer.
構成上述黏著劑層A之黏著劑成分，較佳為自由基聚合性不飽和鍵之量為0.2 meq/g以上且2 meq/g以下。 藉由黏著劑成分之自由基聚合性不飽和鍵之量為上述範圍，可容易地滿足上述晶片剪切強度、180°剝離強度及水平載重強度之範圍。就更容易地滿足上述晶片剪切強度、180°剝離強度及水平載重強度之範圍之觀點而言，上述自由基聚合性不飽和鍵之量更佳為0.3 meq/g以上，進而較佳為0.5 meq/g以上，且較佳為1.5 meq/g以下，進而較佳為1 meq/g以下。上述自由基聚合性不飽和鍵之量，例如可藉由上述含官能基之不飽和化合物之量進行調節。The adhesive component constituting the adhesive layer A preferably has an amount of radically polymerizable unsaturated bonds of 0.2 meq/g or more and 2 meq/g or less. Since the amount of radically polymerizable unsaturated bonds of the adhesive component is in the above range, the above ranges of chip shear strength, 180° peel strength and horizontal load strength can be easily satisfied. From the viewpoint of more easily satisfying the ranges of the aforementioned wafer shear strength, 180° peel strength, and horizontal load strength, the amount of the radically polymerizable unsaturated bond is more preferably 0.3 meq/g or more, and more preferably 0.5 Meq/g or more, preferably 1.5 meq/g or less, and more preferably 1 meq/g or less. The amount of the aforementioned radically polymerizable unsaturated bond can be adjusted by, for example, the amount of the aforementioned functional group-containing unsaturated compound.
上述黏著劑成分之羥值、酸值可藉由依據JIS K0070，進行黏著劑成分之溶液之滴定試驗而測定。關於不飽和鍵量，可藉由將根據JIS K0070計算出之碘值之值除以碘之原子量126.9，以meq/g之形式計算出。The hydroxyl value and acid value of the above-mentioned adhesive component can be measured by performing a titration test of a solution of the adhesive component in accordance with JIS K0070. The amount of unsaturated bonds can be calculated in the form of meq/g by dividing the value of the iodine value calculated according to JIS K0070 by the atomic weight of iodine, 126.9.
上述黏著劑層A較佳含有聚合起始劑。 將上述聚合性聚合物及聚合起始劑用於上述黏著劑層A，使上述黏著劑層A硬化，藉此可容易地滿足上述晶片剪切強度、180°剝離強度及水平載重強度之範圍。作為上述聚合起始劑，可列舉光聚合起始劑、熱聚合起始劑等。其中，就可容易地進行硬化，且對於被接著體之損害亦較小而言，較佳為光聚合起始劑。The adhesive layer A preferably contains a polymerization initiator. The above-mentioned polymerizable polymer and polymerization initiator are used for the above-mentioned adhesive layer A to harden the above-mentioned adhesive layer A, thereby easily satisfying the ranges of the above-mentioned wafer shear strength, 180° peel strength and horizontal load strength. As said polymerization initiator, a photopolymerization initiator, a thermal polymerization initiator, etc. are mentioned. Among them, a photopolymerization initiator is preferred in terms of easy curing and less damage to the adherend.
上述光聚合起始劑，例如可列舉藉由照射200～410 nm波長之紫外線而活化者。作為此種光聚合起始劑，例如可列舉苯乙酮衍生物化合物、安息香醚系化合物、縮酮衍生物化合物、氧化膦衍生物化合物、雙(η5-環戊二烯基)二茂鈦衍生物化合物、二苯甲酮、米其勒酮、氯9-氧硫𠮿
作為上述熱聚合起始劑，可列舉藉由熱而分解，並產生使聚合硬化開始之活性自由基者。具體而言，例如可列舉雙異苯丙基過氧化物、二第三丁基過氧化物、過氧苯甲酸第三丁酯、第三丁基氫過氧化物、過氧化苯甲醯、異丙苯氫過氧化物、氫過氧化二異丙基苯、氫過氧化對薄荷烷等。 於該等熱聚合起始劑中，作為市售者，並無特別限定，例如宜為PERBUTYL D、PERBUTYL H、PERBUTYL P、PERMENTA H（以上均為日油公司製造）等。該等熱聚合起始劑可單獨使用，亦可併用2種以上。Examples of the thermal polymerization initiator include those that decompose by heat and generate active radicals that initiate polymerization and hardening. Specifically, for example, bis-isophenylpropyl peroxide, di-tertiary butyl peroxide, tertiary butyl peroxybenzoate, tertiary butyl hydroperoxide, benzyl peroxide, isopropyl Propylene benzene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, etc. Among these thermal polymerization initiators, commercially available ones are not particularly limited. For example, PERBUTYL D, PERBUTYL H, PERBUTYL P, PERMENTA H (all manufactured by NOF Corporation) and the like are suitable. These thermal polymerization initiators may be used alone or in combination of two or more kinds.
上述黏著劑層A亦可含有自由基聚合性之多官能低聚物或單體。 藉由上述黏著劑層A含有自由基聚合性之多官能低聚物或單體，紫外線硬化性提高。上述多官能低聚物或單體較佳為重量平均分子量為1萬以下者，更佳為其重量平均分子量為5000以下，且分子內之自由基聚合性不飽和鍵之數量為2～20個者，以高效率地實現由照射紫外線所產生之黏著劑層之三維網狀化。The above-mentioned adhesive layer A may contain a radically polymerizable polyfunctional oligomer or monomer. When the adhesive layer A contains a radically polymerizable polyfunctional oligomer or monomer, the ultraviolet curability is improved. The above-mentioned polyfunctional oligomer or monomer preferably has a weight average molecular weight of 10,000 or less, and more preferably has a weight average molecular weight of 5,000 or less, and the number of radically polymerizable unsaturated bonds in the molecule is 2-20. Moreover, the three-dimensional network of the adhesive layer produced by ultraviolet irradiation can be realized with high efficiency.
上述多官能低聚物或單體，例如可列舉三羥甲基丙烷三丙烯酸酯、四羥甲基甲烷四丙烯酸酯、新戊四醇三丙烯酸酯、新戊四醇四丙烯酸酯、二新戊四醇單羥基五丙烯酸酯、二新戊四醇六丙烯酸酯或同上述之甲基丙烯酸酯類等。此外，可列舉1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、市售之寡酯丙烯酸酯、同上述之甲基丙烯酸酯類等。該等多官能低聚物或單體可單獨使用，亦可併用2種以上。The above-mentioned polyfunctional oligomers or monomers include, for example, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, neopentylerythritol triacrylate, neopentylerythritol tetraacrylate, and dineopentyl Tetraol monohydroxy pentaacrylate, dineopentaerythritol hexaacrylate or the same methacrylates as mentioned above, etc. In addition, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, commercially available oligoester acrylates, and the same methacrylates as mentioned above can be mentioned. Wait. These polyfunctional oligomers or monomers may be used alone, or two or more of them may be used in combination.
上述黏著劑層A較佳含有交聯劑。 藉由上述黏著劑層A含有交聯劑，可提高上述黏著劑成分之凝聚力。作為上述交聯劑，例如可列舉異氰酸酯系交聯劑、環氧系交聯劑等。其中，就可進一步提高剝離性能而言，較佳為異氰酸酯系交聯劑。The above-mentioned adhesive layer A preferably contains a crosslinking agent. Since the adhesive layer A contains a crosslinking agent, the cohesive force of the adhesive components can be improved. As said crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, etc. are mentioned, for example. Among them, an isocyanate-based crosslinking agent is preferred in terms of further improving the peeling performance.
上述交聯劑之含量並無特別限定，相對於黏著劑成分100重量份，較佳之下限為0.01重量份，更佳之下限為0.1重量份，且較佳之上限為10重量份，更佳之上限為5重量份。藉由上述交聯劑之含量為上述範圍，可使黏著劑成分適度地交聯，維持高黏著力並進一步提高黏著劑成分之凝聚力。The content of the crosslinking agent is not particularly limited. Relative to 100 parts by weight of the adhesive component, the lower limit is preferably 0.01 parts by weight, the lower limit is more preferably 0.1 parts by weight, and the upper limit is preferably 10 parts by weight, and the upper limit is more preferably 5 parts by weight. Parts by weight. When the content of the above-mentioned cross-linking agent is in the above-mentioned range, the adhesive components can be appropriately cross-linked, maintaining high adhesive force, and further improving the cohesive force of the adhesive components.
上述黏著劑層A較佳含有脫模性成分，更佳含有具有可與上述黏著劑成分交聯之官能基的矽酮或氟化合物（以下，亦僅稱為矽酮或氟化合物）作為脫模性成分。 藉由上述黏著劑層A含有矽酮或氟化合物，而於黏著劑層A與被接著體之界面滲出矽酮或氟化合物，因此可於處理結束後容易且無糊劑殘留地將黏著帶剝離。又，藉由上述矽酮或氟化合物具有可與上述黏著劑成分交聯之官能基，矽酮或氟化合物與黏著劑成分發生化學反應或經由交聯劑等被取入至黏著劑成分中，因此可抑制由矽酮或氟化合物附著於被接著體所產生之污染。 上述矽酮或氟化合物中之可交聯之官能價例如為2～6價，較佳為2～4價，更佳為2價。 可與上述黏著劑成分交聯之官能基，可根據黏著劑成分所含之官能基適宜決定，例如於黏著劑成分含有(甲基)丙烯酸烷基酯系聚合性聚合物之情形時，選擇可與(甲基)丙烯醯基（acryl group）交聯之官能基。上述可與(甲基)丙烯醯基交聯之官能基為具有不飽和雙鍵之官能基，具體而言，例如選擇含有乙烯基、(甲基)丙烯醯基、烯丙基、馬來亞醯胺基等之矽酮或氟化合物。作為可與上述黏著劑成分交聯之官能基，除了上述可與(甲基)丙烯醯基交聯之官能基以外，例如亦可列舉羥基、羧基、環氧基等。其中，於上述黏著劑層A為硬化型之情形時，就於進行硬化反應的同時，矽酮或氟化合物與黏著劑成分發生化學反應而被取入至黏著劑成分中而言，較佳為具有不飽和雙鍵之官能基。 作為上述矽酮或氟化合物，例如可列舉矽酮二丙烯酸酯、氟丙烯酸酯等。The adhesive layer A preferably contains a mold-releasing component, and more preferably contains a silicone or fluorine compound (hereinafter, also only referred to as silicone or fluorine compound) having a functional group that can be cross-linked with the adhesive component as a mold release Sexual component. Since the adhesive layer A contains silicone or fluorine compound, the silicone or fluorine compound oozes out of the interface between the adhesive layer A and the adherend, so the adhesive tape can be peeled off easily and without any paste remaining after the treatment. . In addition, since the silicone or fluorine compound has a functional group that can be crosslinked with the adhesive component, the silicone or fluorine compound chemically reacts with the adhesive component or is taken into the adhesive component through a crosslinking agent, etc. Therefore, the pollution caused by the adhesion of silicone or fluorine compounds to the adherend can be suppressed. The crosslinkable functional valence in the aforementioned silicone or fluorine compound is, for example, 2 to 6 valence, preferably 2 to 4 valence, and more preferably divalence. The functional group that can be cross-linked with the above-mentioned adhesive component can be appropriately determined according to the functional group contained in the adhesive component. For example, when the adhesive component contains an alkyl (meth)acrylate polymerizable polymer, it can be selected. Functional group cross-linked with (meth)acryl group. The functional group that can be crosslinked with the (meth)acryloyl group is a functional group having an unsaturated double bond. Specifically, for example, it is selected to contain a vinyl group, a (meth)acryloyl group, an allyl group, or a maleinide group. Silicone or fluorine compounds such as amide groups. As the functional group that can be crosslinked with the adhesive component, in addition to the functional group that can be crosslinked with the (meth)acryloyl group, for example, a hydroxyl group, a carboxyl group, an epoxy group, etc. can also be cited. Among them, when the adhesive layer A is a hardening type, the silicone or fluorine compound chemically reacts with the adhesive component while the curing reaction proceeds and is taken into the adhesive component, preferably Functional groups with unsaturated double bonds. As said silicone or fluorine compound, silicone diacrylate, fluoroacrylate, etc. are mentioned, for example.
關於上述黏著劑層A中之上述矽酮或氟化合物之含量，較佳之下限為2重量%，更佳之下限為5重量%，進而較佳之下限為10重量%，且較佳之上限為40重量%，更佳之上限為35重量%，進而較佳之上限為30重量%。 藉由上述矽酮或氟化合物之含量為上述範圍，可進一步無糊劑殘留地將被接著體剝離。Regarding the content of the silicone or fluorine compound in the adhesive layer A, the lower limit is preferably 2% by weight, the lower limit is more preferably 5% by weight, the lower limit is still more preferably 10% by weight, and the upper limit is preferably 40% by weight. , A more preferable upper limit is 35% by weight, and a more preferable upper limit is 30% by weight. When the content of the silicone or fluorine compound is in the above range, the adherend can be peeled off without leaving a paste.
上述黏著劑層A較佳含有具有可與上述黏著劑成分交聯之官能基的胺酯化合物（以下，亦僅稱為胺酯化合物）。藉由上述黏著劑層A含有胺酯化合物，可使黏著帶之柔軟性提高，從而使所獲得之黏著帶不易碎裂。又，藉由胺酯化合物具有可與上述黏著劑成分交聯之官能基，胺酯化合物與黏著劑成分發生化學反應或經由交聯劑等被取入至黏著劑成分中，因此可抑制由胺酯化合物附著於被接著體所產生之污染。作為可與上述黏著劑成分交聯之官能基，可列舉和具有可與上述黏著劑成分交聯之官能基的矽酮或氟化合物相同者。作為上述胺酯化合物，例如可列舉胺酯丙烯酸酯。The adhesive layer A preferably contains a urethane compound having a functional group that can be cross-linked with the adhesive component (hereinafter, also referred to only as an urethane compound). Since the adhesive layer A contains a urethane compound, the flexibility of the adhesive tape can be improved, so that the obtained adhesive tape is not easily broken. In addition, since the amine ester compound has a functional group that can be cross-linked with the adhesive component, the amine ester compound chemically reacts with the adhesive component or is taken into the adhesive component via a cross-linking agent. Contamination caused by the attachment of the ester compound to the adherend. As the functional group that can be crosslinked with the above-mentioned adhesive component, the same silicone or fluorine compound having a functional group that can be crosslinked with the above-mentioned adhesive component can be mentioned. As said amine ester compound, urethane acrylate is mentioned, for example.
關於上述黏著劑層A中之上述胺酯化合物之含量，較佳之上限為20重量%，更佳之上限為15重量%，進而較佳之上限為10重量%。藉由上述胺酯化合物之含量為上述範圍，可製成耐熱性及糊劑殘留抑制性能更為優異之黏著帶。上述胺酯化合物之含量之下限並無特別限定，就使黏著帶更不易碎裂且抑制糊劑殘留之觀點而言，較佳為1重量%。Regarding the content of the urethane compound in the adhesive layer A, a preferable upper limit is 20% by weight, a more preferable upper limit is 15% by weight, and a more preferable upper limit is 10% by weight. When the content of the urethane compound is in the above range, an adhesive tape with more excellent heat resistance and paste residue suppression performance can be produced. The lower limit of the content of the urethane compound is not particularly limited, but from the viewpoint of making the adhesive tape less likely to break and suppressing the residue of the paste, it is preferably 1% by weight.
上述黏著劑層A亦可含有發煙二氧化矽（fumed silica）等無機填料、塑化劑、樹脂、界面活性劑、蠟、微粒子填充劑等公知之添加劑。上述添加劑可單獨使用，亦可組合使用2種以上。The adhesive layer A may also contain well-known additives such as fumed silica and other inorganic fillers, plasticizers, resins, surfactants, waxes, and particulate fillers. The above-mentioned additives may be used alone or in combination of two or more kinds.
於上述黏著劑層A含有無機填料（發煙二氧化矽等）之情形時，就易將水平載重調整至上述範圍內之觀點而言，其含量相對於黏著劑成分100重量%，較佳為3重量%以上，更佳為12重量%以上，且較佳為24重量%以下，更佳為18重量%以下。In the case where the adhesive layer A contains an inorganic filler (fuming silica, etc.), from the viewpoint of easy adjustment of the horizontal load within the above range, its content relative to 100% by weight of the adhesive component is preferably 3% by weight or more, more preferably 12% by weight or more, and preferably 24% by weight or less, more preferably 18% by weight or less.
上述黏著劑層A較佳為3000 mJ/cm2 之紫外線照射後之23℃的拉伸強度為1.0 MPa以上。 藉由上述黏著劑層A之紫外線照射後之拉伸強度為上述範圍，可使所獲得之黏著帶更不易碎裂，又，可進一步抑制糊劑殘留之產生。進而，可將上述水平載重控制於上述範圍。就使黏著帶更不易碎裂且抑制糊劑殘留之觀點而言，上述拉伸強度更佳為1.2 MPa以上，進而較佳為1.5 MPa以上。上述拉伸強度之上限並無特別限定，就黏著力之觀點而言，較佳為6 MPa以下。The adhesive layer A preferably has a tensile strength of 1.0 MPa or more at 23° C. after irradiation with ultraviolet rays of 3000 mJ/cm 2. When the tensile strength of the adhesive layer A after ultraviolet irradiation is in the above range, the obtained adhesive tape can be made less likely to be broken, and the generation of paste residue can be further suppressed. Furthermore, the above-mentioned horizontal load can be controlled within the above-mentioned range. From the viewpoint of making the adhesive tape less likely to break and suppressing paste residue, the above-mentioned tensile strength is more preferably 1.2 MPa or more, and more preferably 1.5 MPa or more. The upper limit of the aforementioned tensile strength is not particularly limited, but from the viewpoint of adhesive strength, it is preferably 6 MPa or less.
再者，上述拉伸強度可藉由依據JIS K 7161之方法進行測定。 具體而言，例如使用高分子計器公司製造之沖切刀「拉伸1號型啞鈴狀」等，以長邊與製造時之行進方向一致之方式將上述黏著劑層A沖切成為啞鈴狀，從而製作試片。針對所獲得之試片，例如使用島津製作所公司製造之「Autograph AGS-X」等，以拉伸速度100 mm/min進行測定，並使試片斷裂。根據斷裂點處之強度計算出拉伸強度。Furthermore, the above-mentioned tensile strength can be measured by a method based on JIS K 7161. Specifically, for example, using a punching knife "stretched No. 1 dumbbell shape" manufactured by Polymer Meters, etc., the adhesive layer A is punched into a dumbbell shape so that the long side is consistent with the direction of travel at the time of manufacturing. Thus, a test piece was produced. For the obtained test piece, for example, using "Autograph AGS-X" manufactured by Shimadzu Corporation, etc., the measurement is performed at a tensile speed of 100 mm/min, and the test piece is broken. The tensile strength is calculated based on the strength at the breaking point.
上述黏著劑層A較佳為3000 mJ/cm2 之紫外線照射後之260℃之拉伸彈性模數為1.0×106 Pa以上。 藉由上述黏著劑層A之紫外線照射後之拉伸彈性模數為上述範圍，所獲得之黏著帶對載重之耐久性提高，可使被接著體更不易損傷，進而易將上述水平載重及晶片剪切強度控制於上述範圍內。就使被接著體更不易損傷之觀點而言，上述拉伸彈性模數更佳為5×106 Pa以上，進而較佳為1×107 Pa以上。上述拉伸彈性模數之上限並無特別限定，就黏著力之觀點而言，較佳為30×106 Pa以下。The above-mentioned adhesive layer A preferably has a tensile elastic modulus of 1.0×10 6 Pa or more at 260° C. after irradiation of 3000 mJ/cm 2 of ultraviolet rays. When the tensile elastic modulus of the adhesive layer A after ultraviolet irradiation is in the above range, the durability of the obtained adhesive tape against the load is improved, the adherend is less likely to be damaged, and the above-mentioned horizontal load and chip The shear strength is controlled within the above range. From the viewpoint of making the adherend more difficult to damage, the above-mentioned tensile modulus of elasticity is more preferably 5×10 6 Pa or more, and still more preferably 1×10 7 Pa or more. The upper limit of the tensile elastic modulus is not particularly limited, but from the viewpoint of adhesive force, it is preferably 30×10 6 Pa or less.
再者，上述拉伸彈性模數可藉由以下之方法進行測定。 針對黏著劑層A之單層樣品，以長邊與製造時之行進方向一致之方式使用沖切刀進行沖切，藉此製作5 mm×35 mm之試片。將所獲得之試片浸漬於液態氮而冷卻至-50℃，之後，使用黏彈性譜儀（例如DVA-200，IT Meter and Control公司製造等），於定速升溫拉伸模式、升溫速度10℃/分鐘、頻率10 Hz之條件下升溫至300℃，測定儲存彈性模數。根據所獲得之儲存彈性模數之結果，將260℃之儲存彈性模數作為上述拉伸彈性模數。Furthermore, the above-mentioned tensile elastic modulus can be measured by the following method. For the single-layer sample of the adhesive layer A, punch with a punching knife in a way that the long side is consistent with the direction of travel at the time of manufacture, thereby making a 5 mm×35 mm test piece. The obtained test piece was immersed in liquid nitrogen and cooled to -50°C. After that, a viscoelastic spectrometer (such as DVA-200, manufactured by IT Meter and Control, etc.) was used in a constant-rate heating and stretching mode at a heating rate of 10 Under the condition of ℃/min and frequency of 10 Hz, the temperature is raised to 300℃, and the storage elastic modulus is measured. According to the result of the obtained storage elastic modulus, the storage elastic modulus at 260°C is taken as the above-mentioned tensile elastic modulus.
上述黏著劑層A之厚度並無特別限定，下限較佳為1 μm，上限較佳為200 μm。若上述黏著劑層A之厚度為上述範圍，則可藉由充分之黏著力保護被接著體，進而亦可抑制剝離時之糊劑殘留。上述黏著劑層A之厚度更佳之下限為10 μm，更佳之上限為100 μm。The thickness of the adhesive layer A is not particularly limited, and the lower limit is preferably 1 μm, and the upper limit is preferably 200 μm. If the thickness of the adhesive layer A is in the above-mentioned range, the adherend can be protected with sufficient adhesive force, and furthermore, the paste residue at the time of peeling can be suppressed. The lower limit of the thickness of the adhesive layer A is more preferably 10 μm, and the upper limit is more preferably 100 μm.
關於上述黏著劑層B，若上述黏著劑層A可滿足上述晶片剪切強度及180°剝離強度之範圍，則並無特別限定，可與上述黏著劑層A相同，亦可不同。又，上述黏著劑層B可為硬化型，亦可為非硬化型。作為構成上述黏著劑層B之黏著劑，例如可列舉橡膠系黏著劑、丙烯酸系黏著劑、乙烯基烷基醚系黏著劑、矽酮系黏著劑、聚酯系黏著劑、聚醯胺系黏著劑、胺酯系黏著劑、苯乙烯-二烯嵌段共聚物系黏著劑等。又，上述黏著劑成分之構造並無特別限定，可為無規共聚物，亦可為嵌段共聚物。Regarding the above-mentioned adhesive layer B, if the above-mentioned adhesive layer A can satisfy the ranges of the above-mentioned wafer shear strength and 180° peel strength, it is not particularly limited, and may be the same as or different from the above-mentioned adhesive layer A. In addition, the above-mentioned adhesive layer B may be a hardening type or a non-hardening type. Examples of the adhesive constituting the adhesive layer B include rubber adhesives, acrylic adhesives, vinyl alkyl ether adhesives, silicone adhesives, polyester adhesives, and polyamide adhesives. Agents, urethane-based adhesives, styrene-diene block copolymer-based adhesives, etc. Moreover, the structure of the said adhesive component is not specifically limited, It may be a random copolymer, and may be a block copolymer.
關於上述黏著劑層B，就上述黏著劑層A易滿足上述晶片剪切強度及180°剝離強度之範圍而言，較佳為405 nm之紫外線透射率為1%以上。上述紫外線透射率更佳為10%以上，進而較佳為15%以上，尤佳為50%以上。藉由上述紫外線透射率為該等下限以上，即便不使用光敏劑，於上述黏著劑層A為紫外線硬化型之情形時，亦可使上述黏著劑層A充分地硬化。上述紫外線透射率之上限並無特別限定，愈高愈佳，通常為100%以下。Regarding the adhesive layer B, as the adhesive layer A easily satisfies the range of the wafer shear strength and 180° peel strength, the ultraviolet transmittance at 405 nm is preferably 1% or more. The above-mentioned ultraviolet transmittance is more preferably 10% or more, still more preferably 15% or more, and particularly preferably 50% or more. Since the ultraviolet transmittance is more than the lower limit, even if a photosensitizer is not used, when the adhesive layer A is an ultraviolet curable type, the adhesive layer A can be cured sufficiently. The upper limit of the ultraviolet transmittance is not particularly limited, the higher the better, and it is usually 100% or less.
上述黏著劑層B之厚度並無特別限定，較佳為較佳之下限為5 μm，更佳之下限為10 μm，且較佳之上限為100 μm，更佳之上限為60 μm。若上黏著劑層B之厚度為上述範圍，則可藉由充分之黏著力與支持體等進行接著，從而將被接著體確實地固定。The thickness of the adhesive layer B is not particularly limited, and the lower limit is preferably 5 μm, the lower limit is more preferably 10 μm, the upper limit is preferably 100 μm, and the upper limit is 60 μm. If the thickness of the upper adhesive layer B is in the above-mentioned range, the adherend can be adhered to the support body with sufficient adhesive force, and the adherend can be reliably fixed.
關於構成上述基材膜之材料，若上述黏著劑層A可滿足上述晶片剪切強度及180°剝離強度之範圍，則並無特別限定，可為有機材料，亦可為無機材料，但較佳為具有耐熱性之材料。作為耐熱性之有機材料，例如可列舉：聚對酞酸乙二酯、聚萘二甲酸乙二酯、聚縮醛、聚醯胺、聚碳酸酯、聚苯醚、聚對酞酸丁二酯、超高分子量聚乙烯、間規聚苯乙烯、聚芳酯、聚碸、聚醚碸、聚伸苯硫、聚醚醚酮、聚醯亞胺、聚醚醯亞胺、氟樹脂、液晶聚合物等。其中，就耐熱性優異而言，較佳為聚萘二甲酸乙二酯。又，作為耐熱性之無機材料，可列舉薄板玻璃等。Regarding the material constituting the substrate film, if the adhesive layer A can satisfy the ranges of the wafer shear strength and the 180° peel strength, it is not particularly limited. It may be an organic material or an inorganic material, but it is preferably It is a heat-resistant material. Examples of heat-resistant organic materials include polyethylene terephthalate, polyethylene naphthalate, polyacetal, polyamide, polycarbonate, polyphenylene ether, and polybutylene terephthalate. , Ultra-high molecular weight polyethylene, syndiotactic polystyrene, polyarylate, polyether, polyether sulfide, polyphenylene sulfide, polyether ether ketone, polyimide, polyether imide, fluororesin, liquid crystal polymerization Things and so on. Among them, in terms of excellent heat resistance, polyethylene naphthalate is preferred. In addition, as heat-resistant inorganic materials, sheet glass and the like can be cited.
關於上述基材膜，就上述黏著劑層A易滿足上述晶片剪切強度及180°剝離強度之範圍而言，較佳為405 nm之紫外線透射率為1%以上。上述紫外線透射率更佳為10%以上，進而較佳為15%以上，尤佳為50%以上。藉由上述紫外線透射率為該等下限以上，即便不使用光敏劑，於上述黏著劑層A為紫外線硬化型之情形時，亦可使上述黏著劑層A充分地硬化。上述紫外線透射率之上限並無特別限定，愈高愈佳，通常為100%以下。Regarding the above-mentioned base film, since the above-mentioned adhesive layer A easily satisfies the ranges of the above-mentioned wafer shear strength and 180° peel strength, it is preferable that the ultraviolet transmittance of 405 nm is 1% or more. The above-mentioned ultraviolet transmittance is more preferably 10% or more, still more preferably 15% or more, and particularly preferably 50% or more. Since the ultraviolet transmittance is more than the lower limit, even if a photosensitizer is not used, when the adhesive layer A is an ultraviolet curable type, the adhesive layer A can be cured sufficiently. The upper limit of the ultraviolet transmittance is not particularly limited, the higher the better, and it is usually 100% or less.
上述基材膜之形狀並無特別限定，例如可列舉片狀、具有網狀構造之片狀、開孔之片狀等。又，上述基材亦可為經實施噴砂處理或表面電暈處理等提高與黏著劑之密接力之處理、或者濺鍍膜形成或導電膜蒸鍍等賦予導電性之處理等之基材。The shape of the above-mentioned base film is not particularly limited, and examples thereof include a sheet shape, a sheet shape having a mesh structure, and an open sheet shape. In addition, the above-mentioned base material may be a base material that has been subjected to treatment to improve adhesion with the adhesive, such as sandblasting treatment or surface corona treatment, or treatment to impart conductivity such as sputtering film formation or conductive film vapor deposition.
上述基材膜之厚度並無特別限定，較佳之下限為5 μm，較佳之上限為100 μm。若上述基材膜之厚度為該範圍內，則可製成具有適度之塑性，且處理性優異之黏著帶。上述基材膜之厚度更佳之下限為10 μm，更佳之上限為50 μm。The thickness of the aforementioned substrate film is not particularly limited, and the preferred lower limit is 5 μm, and the preferred upper limit is 100 μm. If the thickness of the base film is within this range, an adhesive tape having moderate plasticity and excellent handling properties can be produced. The lower limit of the thickness of the substrate film is more preferably 10 μm, and the upper limit is more preferably 50 μm.
本發明之黏著帶亦可於上述基材膜與上述黏著劑層A之間、或上述基材膜與上述黏著劑層B之間具有錨固層。 若於上述基材膜與上述黏著劑層之間具有錨固層，則於上述黏著劑層含有矽酮或氟化合物之情形時，可抑制矽酮或氟化合物滲出於基材膜側而導致黏著劑層自基材膜剝離。The adhesive tape of the present invention may have an anchor layer between the base film and the adhesive layer A, or between the base film and the adhesive layer B. If there is an anchor layer between the base film and the adhesive layer, when the adhesive layer contains silicone or fluorine compound, the silicone or fluorine compound can be prevented from permeating out of the base film side to cause the adhesive The layer is peeled from the base film.
作為上述錨固層，例如可列舉丙烯酸系黏著劑、胺酯系黏著劑等。其中，就錨固性能優異而言，較佳為丙烯酸系黏著劑。Examples of the anchor layer include acrylic adhesives and urethane adhesives. Among them, in terms of excellent anchoring performance, an acrylic adhesive is preferred.
上述錨固層亦可視需要含有無機填充劑、熱穩定劑、抗氧化劑、抗靜電劑、塑化劑、樹脂、界面活性劑、蠟等公知之添加劑。該等添加劑可單獨使用，亦可組合多種使用。The anchor layer may optionally contain well-known additives such as inorganic fillers, heat stabilizers, antioxidants, antistatic agents, plasticizers, resins, surfactants, waxes and the like. These additives can be used alone or in combination of multiple types.
上述錨固層之厚度並無特別限定，較佳之下限為1 μm，較佳之上限為30 μm。若上述錨固層之厚度為該範圍內，則可進一步提高上述錨固層側之黏著劑層與基材膜之錨固力。就進一步提高上述錨固層側之黏著劑層與基材膜之錨固力的觀點而言，上述錨固層之厚度更佳之下限為3 μm，更佳之上限為10 μm。The thickness of the anchor layer is not particularly limited, and the preferred lower limit is 1 μm, and the preferred upper limit is 30 μm. If the thickness of the anchor layer is within this range, the anchoring force between the adhesive layer on the anchor layer side and the base film can be further improved. From the viewpoint of further improving the anchoring force between the adhesive layer on the anchoring layer side and the substrate film, the thickness of the anchoring layer has a more preferable lower limit of 3 μm, and a more preferable upper limit of 10 μm.
關於本發明之黏著帶，就上述黏著劑層A易滿足上述晶片剪切強度及180°剝離強度之範圍而言，405 nm之紫外線透射率較佳為1%以上。上述紫外線透射率更佳為10%以上，進而較佳為15%以上。藉由上述紫外線透射率為該等下限以上，即便不使用光敏劑，於上述黏著劑層A為紫外線硬化型之情形時，亦可使上述黏著劑層A充分地硬化。上述紫外線透射率之上限並無特別限定，愈高愈佳，通常為100%以下。 再者，紫外線透射率可使用分光光度計（U-3900，日立製作所公司製造、或其等效產品）進行測定。Regarding the adhesive tape of the present invention, as far as the adhesive layer A easily satisfies the range of the chip shear strength and the 180° peel strength, the ultraviolet transmittance at 405 nm is preferably 1% or more. The ultraviolet transmittance is more preferably 10% or more, and still more preferably 15% or more. Since the ultraviolet transmittance is more than the lower limit, even if a photosensitizer is not used, when the adhesive layer A is an ultraviolet curable type, the adhesive layer A can be cured sufficiently. The upper limit of the ultraviolet transmittance is not particularly limited, the higher the better, and it is usually 100% or less. Furthermore, the ultraviolet transmittance can be measured using a spectrophotometer (U-3900, manufactured by Hitachi, Ltd., or its equivalent).
製造本發明之黏著帶之方法並無特別限定，可使用以往公知之方法。例如可藉由如下方法進行製造：將含有黏著劑成分、矽酮或氟化合物、胺酯化合物等之溶液塗佈於經實施脫模處理之膜上，使其乾燥而形成黏著劑層A，並利用相同之方法於另一個經實施脫模處理之膜上形成黏著劑層B，之後分別使黏著劑層A及黏著劑層B貼合於基材膜之兩面。The method of manufacturing the adhesive tape of the present invention is not particularly limited, and conventionally known methods can be used. For example, it can be manufactured by the following method: coating a solution containing adhesive components, silicone or fluorine compounds, urethane compounds, etc. on a film subjected to mold release treatment, and drying to form the adhesive layer A, and Use the same method to form the adhesive layer B on another film that has been subjected to mold release treatment, and then attach the adhesive layer A and the adhesive layer B to both sides of the base film, respectively.
本發明之黏著帶之用途並無特別限定，可尤佳地用作具有伴隨著高溫及載重之製造步驟之電子基板或半導體晶片、顯示材用面板零件等電子零件之製造時的保護帶。 又，用以製造此種電子零件之本發明之黏著帶亦為本發明之一。尤其是，本發明之黏著帶可較佳地用於含有於280℃短時間（例如90秒以下，典型地為1～20秒）地加熱之熱壓接合步驟等之電子零件的製造。 作為可使用本發明之黏著帶的半導體元件製造方法，更具體而言，例如可列舉一種半導體元件之製造方法，其具有經由本發明之黏著帶將晶圓固定於支持體上之步驟及藉由熱壓接合將半導體晶片積層於該晶圓上之步驟。又，此種半導體元件之製造方法亦為本發明之一。The use of the adhesive tape of the present invention is not particularly limited, and it can be particularly preferably used as a protective tape in the manufacture of electronic components such as electronic substrates or semiconductor chips, panel parts for display materials, etc., which have manufacturing steps accompanied by high temperature and load. In addition, the adhesive tape of the present invention used to manufacture such electronic parts is also one of the present inventions. In particular, the adhesive tape of the present invention can be preferably used in the manufacture of electronic parts including a thermocompression bonding step heated at 280°C for a short time (for example, less than 90 seconds, typically 1 to 20 seconds). As a method for manufacturing a semiconductor device that can use the adhesive tape of the present invention, more specifically, for example, a method for manufacturing a semiconductor device can be cited, which has a step of fixing a wafer on a support through the adhesive tape of the present invention and by The step of laminating semiconductor wafers on the wafer by thermocompression bonding. Moreover, the manufacturing method of such a semiconductor device is also one of the present invention.
於上述固定晶圓之步驟中，經由本發明之黏著帶將晶圓固定於支持體上之方法並無特別限定，較佳為使上述黏著劑層A與矽晶圓等晶圓貼合，並使另一上述黏著劑層B與玻璃等支持體貼合之方法。In the step of fixing the wafer, the method of fixing the wafer on the support via the adhesive tape of the present invention is not particularly limited. Preferably, the adhesive layer A is bonded to the wafer such as silicon wafer, and Another method of bonding the above-mentioned adhesive layer B to a support such as glass.
於上述藉由熱壓接合而積層半導體晶片之步驟中，可重複進行熱壓接合，亦可重複進行於280℃短時間（例如90秒以下，典型地為1～20秒）地加熱之熱壓接合等，從而積層多個半導體晶片。In the above step of laminating semiconductor wafers by thermocompression bonding, thermocompression bonding can be repeated, or thermocompression heated at 280°C for a short time (for example, less than 90 seconds, typically 1-20 seconds) Bonding, etc., to laminate a plurality of semiconductor wafers.
於本發明之半導體元件製造方法中，於上述固定晶圓之步驟後，亦可於進行了其他步驟後再進行上述藉由熱壓接合而積層半導體晶片之步驟。作為上述其他步驟，例如可列舉藉由背面研磨而將晶圓薄化之步驟、晶圓級之模塑步驟等。於本發明之半導體元件製造方法中，進而可於上述藉由熱壓接合而積層半導體晶片之步驟後，進行自上述支持體或者自上述晶圓，或自兩者剝離黏著帶之步驟。In the semiconductor device manufacturing method of the present invention, after the above-mentioned step of fixing the wafer, the above-mentioned step of laminating semiconductor wafers by thermocompression bonding may be performed after other steps are performed. As the above-mentioned other steps, for example, a step of thinning a wafer by back grinding, a wafer-level molding step, and the like can be cited. In the semiconductor device manufacturing method of the present invention, after the step of laminating the semiconductor wafer by thermocompression bonding, the step of peeling the adhesive tape from the support, the wafer, or both may be performed.
上述支持體並無特別限定，例如可列舉玻璃、聚醯亞胺膜、玻璃環氧基板等。 [發明之效果]The said support body is not specifically limited, For example, glass, a polyimide film, a glass epoxy substrate, etc. are mentioned. [Effects of Invention]
若根據本發明，可提供一種黏著帶，該黏著帶即便在用於伴隨著高溫及載重之步驟之情形時，亦不會自被接著體剝離，且於剝離時可容易地進行剝離，進而亦可抑制銲點凸塊之變形。又，若根據本發明，可提供一種使用該黏著帶之半導體元件之製造方法。According to the present invention, it is possible to provide an adhesive tape, which does not peel from the adherend even when used in a process accompanied by high temperature and load, and can be easily peeled during peeling, and furthermore It can suppress the deformation of the solder bumps. Moreover, according to the present invention, a method for manufacturing a semiconductor device using the adhesive tape can be provided.
以下，列舉實施例，進一步詳細說明本發明之態樣，但本發明並不限於該等實施例。Hereinafter, examples are listed to further illustrate the aspects of the present invention, but the present invention is not limited to these examples.
（黏著劑成分A之合成） 準備具備溫度計、攪拌機、冷卻管之反應器。向該反應器內添加作為(甲基)丙烯酸烷基酯之丙烯酸2-乙基己酯94重量份、作為含官能基之單體之甲基丙烯酸羥基乙酯6重量份、月桂硫醇0.01重量份、及乙酸乙酯80重量份後，對反應器進行加熱而開始回流。繼而，向上述反應器內添加1,1-雙(第三己基過氧化)-3,3,5-三甲基環己烷0.01重量份作為聚合起始劑，於回流下開始聚合。其次，於自聚合開始起1小時後及2小時後，亦各添加0.01重量份之1,1-雙(第三己基過氧化)-3,3,5-三甲基環己烷，進而，於自聚合開始起4小時後，添加0.05重量份之過氧三甲基乙酸第三己酯，使聚合反應繼續。然後，於自聚合開始起8小時後，獲得固形物成分55重量%、重量平均分子量60萬之含官能基之(甲基)丙烯酸系聚合物之乙酸乙酯溶液。 相對於所獲得之含有含官能基之(甲基)丙烯酸系聚合物之乙酸乙酯溶液的樹脂固形物成分100重量份，添加作為含官能基之不飽和化合物之甲基丙烯酸2-異氰酸基乙酯3.5重量份並使其反應，獲得黏著劑成分A。(Synthesis of adhesive component A) Prepare a reactor equipped with a thermometer, agitator, and cooling tube. To the reactor were added 94 parts by weight of 2-ethylhexyl acrylate as alkyl (meth)acrylate, 6 parts by weight of hydroxyethyl methacrylate as a monomer containing functional groups, and 0.01 parts by weight of lauryl mercaptan. After 80 parts by weight of ethyl acetate and 80 parts by weight of ethyl acetate, the reactor was heated to start reflux. Then, 0.01 parts by weight of 1,1-bis(tertiary hexylperoxy)-3,3,5-trimethylcyclohexane was added as a polymerization initiator to the above-mentioned reactor, and the polymerization was started under reflux. Next, after 1 hour and 2 hours from the start of the polymerization, 0.01 parts by weight of 1,1-bis(tertiary hexylperoxy)-3,3,5-trimethylcyclohexane were also added, and further, After 4 hours from the start of the polymerization, 0.05 parts by weight of the third hexyl peroxytrimethylacetate was added to continue the polymerization reaction. Then, after 8 hours from the start of the polymerization, an ethyl acetate solution of a functional group-containing (meth)acrylic polymer with a solid content of 55% by weight and a weight average molecular weight of 600,000 was obtained. To 100 parts by weight of the resin solid content of the ethyl acetate solution containing the functional group-containing (meth)acrylic polymer, methacrylic acid 2-isocyanate is added as a functional group-containing unsaturated compound 3.5 parts by weight of ethyl ester was reacted to obtain adhesive component A.
（黏著劑成分B～K之合成） 將組成設為如表1所記載，除此以外，以與黏著劑成分A相同之方式獲得黏著劑成分B～K。(Synthesis of adhesive components B～K) Except that the composition was as described in Table 1, the adhesive components B to K were obtained in the same manner as the adhesive component A.
（黏著劑成分A～K之酸值＋羥值之測定） 依據JIS K0070進行黏著劑成分之溶液之滴定試驗，藉此測定黏著劑成分之羥值及酸值，並計算出酸值＋羥值。(Measurement of acid value of adhesive components A～K + hydroxyl value) According to JIS K0070, the titration test of the solution of the adhesive component is carried out to determine the hydroxyl value and acid value of the adhesive component, and calculate the acid value + hydroxyl value.
[表1]
（實施例1） 相對於所獲得之黏著劑成分A之乙酸乙酯溶液的樹脂固形物成分100重量份，混合填料3重量份、胺酯化合物10重量份、脫模劑20重量份、光聚合起始劑1重量份、交聯劑0.2重量份，獲得構成黏著劑層A之黏著劑之乙酸乙酯溶液。 又，相對於所獲得之黏著劑成分A之樹脂固形物成分100重量份，混合填料3重量份、胺酯化合物20重量份、脫模劑10重量份、光聚合起始劑1重量份、交聯劑1.0重量份，獲得構成黏著劑層B之黏著劑之乙酸乙酯溶液。 利用刮刀，以乾燥皮膜之厚度成為100 μm之方式，將構成黏著劑層A之黏著劑之乙酸乙酯溶液塗佈於表面經實施脫模處理之聚對酞酸乙二酯膜之脫模處理面上，並使其於110℃加熱乾燥5分鐘，獲得黏著劑層A。 另一方面，利用刮刀，以乾燥皮膜之厚度成為20 μm之方式，將構成黏著劑層B之黏著劑之乙酸乙酯溶液塗佈於另一表面經實施脫模處理之聚對酞酸乙二酯膜之脫模處理面上，並使其於110℃加熱乾燥5分鐘，獲得黏著劑層B。 作為基材，準備兩面經實施電暈處理之50 μm之聚萘二甲酸乙二酯（PEN）膜，並分別使黏著劑層A及黏著劑層B貼合於PEN膜之兩面，獲得黏著帶。再者，填料、胺酯化合物、脫模劑、光聚合起始劑使用以下產品。 填料：REOLOSIL MT-10，德山公司製造 胺酯化合物：胺酯丙烯酸酯，UN-5500，根上工業公司製造 脫模劑：矽酮二丙烯酸酯，EBECRYL 350，大賽璐湛新公司製造 光聚合起始劑：Esacure One，Nihon SiberHegner公司製造 交聯劑：異氰酸酯系交聯劑，Coronate L，日本聚氨酯工業公司製造(Example 1) With respect to 100 parts by weight of the resin solid content of the ethyl acetate solution of the adhesive component A obtained, 3 parts by weight of filler, 10 parts by weight of urethane compound, 20 parts by weight of release agent, and 1 part by weight of photopolymerization initiator are mixed Parts and 0.2 parts by weight of the crosslinking agent to obtain the ethyl acetate solution of the adhesive constituting the adhesive layer A. In addition, with respect to 100 parts by weight of the resin solid component of the obtained adhesive component A, 3 parts by weight of filler, 20 parts by weight of urethane compound, 10 parts by weight of release agent, 1 part by weight of photopolymerization initiator, and 1.0 parts by weight of the coupling agent was used to obtain an ethyl acetate solution of the adhesive constituting the adhesive layer B. Using a doctor blade, apply the ethyl acetate solution of the adhesive that constitutes the adhesive layer A to the surface so that the thickness of the dry film becomes 100 μm. The release treatment of the polyethylene terephthalate film is carried out. It was heated and dried at 110°C for 5 minutes to obtain an adhesive layer A. On the other hand, using a doctor blade, apply the ethyl acetate solution of the adhesive that constitutes the adhesive layer B to the other surface of the polyethylene terephthalate that has undergone a mold release treatment so that the thickness of the dried film becomes 20 μm. The release-treated surface of the ester film was heated and dried at 110°C for 5 minutes to obtain an adhesive layer B. As a substrate, prepare a 50 μm polyethylene naphthalate (PEN) film with corona treatment on both sides, and attach the adhesive layer A and the adhesive layer B to both sides of the PEN film to obtain an adhesive tape . In addition, the following products were used for the filler, urethane compound, mold release agent, and photopolymerization initiator. Packing: REOLOSIL MT-10, manufactured by Tokuyama Corporation Amino ester compound: Amino ester acrylate, UN-5500, manufactured by Negami Industry Co., Ltd. Release agent: Silicone diacrylate, EBECRYL 350, manufactured by Daicel Zhanxin Photopolymerization initiator: Esacure One, manufactured by Nihon SiberHegner Cross-linking agent: isocyanate-based cross-linking agent, Coronaate L, manufactured by Nippon Polyurethane Industry Co., Ltd.
（實施例2～16、比較例1～10） 將黏著劑層A之組成設為如表2、3所示，除此以外，以與實施例1相同之方式獲得黏著帶。再者，關於實施例10、比較例8、9，使用以下產品作為脫模劑。 脫模劑：矽丙烯酸酯，RAD2250，Evonik Japan公司製造 又，關於實施例16，使用以下產品作為脫模劑。 脫模劑：矽酮改質丙烯酸聚合物，8BS-9000，大成精細化工公司製造(Examples 2-16, Comparative Examples 1-10) The composition of the adhesive layer A was set as shown in Tables 2 and 3, except that the adhesive tape was obtained in the same manner as in Example 1. In addition, regarding Example 10 and Comparative Examples 8, 9, the following products were used as mold release agents. Release agent: Silicon acrylate, RAD2250, manufactured by Evonik Japan In addition, regarding Example 16, the following products were used as mold release agents. Release agent: Silicone modified acrylic polymer, 8BS-9000, manufactured by Dacheng Fine Chemical Co., Ltd.
＜物性＞ 針對實施例及比較例中獲得之黏著帶，進行了以下之測定。將結果示於表2、3。＜Properties＞ With respect to the adhesive tapes obtained in the examples and comparative examples, the following measurements were performed. The results are shown in Tables 2 and 3.
（晶片剪切強度之測定） 將切成3 cm×4 cm且兩面由脫模膜保護之黏著帶之黏著劑層B側的脫模膜剝離，使黏著劑層B與載玻片（S9112，松浪硝子工業公司製造）貼合。將該黏著帶與玻璃之積層體之黏著劑層A側的脫模膜剝離，將3 mm×3 mm、3 mm厚且表面粗糙度＜0.1 μm之單晶矽晶圓晶片置於黏著帶之黏著劑層A，於載置台溫度20℃、壓接頭溫度20℃、接合壓力3 N進行接合。繼而，使用高壓水銀UV照射機，自黏著帶之黏著劑層B側朝向黏著劑層A照射405 nm之紫外線，且以黏著劑層A之基材側相反之側之表面的照射量成為3000 mJ/cm2 之方式進行照射。之後，於240℃進行10分鐘加熱處理。於加熱處理後，使矽晶圓晶片於室溫下放置冷卻，使用黏結強度試驗機（4000PXY，Nordson-Advanced-Technology公司製造，萬能型），於25℃、50%RH下向矽晶圓晶片之整個側面施加相對於晶片之側面垂直方向之力，測定使矽晶圓晶片移動時之最大載重，將其設為晶片剪切強度。(Measurement of wafer shear strength) The release film on the adhesive layer B side of the adhesive tape cut into 3 cm×4 cm and both sides protected by the release film is peeled off, so that the adhesive layer B and the glass slide (S9112, Made by Songlang Glass Industry Co., Ltd.) lamination. The adhesive tape and the release film on the side of the adhesive layer A of the glass laminate are peeled off, and a 3 mm×3 mm, 3 mm thick monocrystalline silicon wafer with a surface roughness of <0.1 μm is placed on the adhesive tape Adhesive layer A was bonded at a mounting table temperature of 20°C, a crimping temperature of 20°C, and a bonding pressure of 3 N. Then, using a high-pressure mercury UV irradiator, 405 nm ultraviolet rays were irradiated from the adhesive layer B side of the adhesive tape toward the adhesive layer A, and the irradiation amount of the surface on the side opposite to the substrate side of the adhesive layer A became 3000 mJ /cm 2 for irradiation. After that, heat treatment was performed at 240°C for 10 minutes. After the heat treatment, the silicon wafer is placed at room temperature to cool, and the bonding strength tester (4000PXY, manufactured by Nordson-Advanced-Technology, universal type) is used to transfer the silicon wafer at 25°C and 50%RH The entire side of the wafer is applied with a force perpendicular to the side of the wafer to measure the maximum load when the silicon wafer is moved, and set it as the wafer shear strength.
（180°剝離強度之測定） 將黏著帶之黏著劑層A側之脫模膜剝離，將8英吋、厚度0.75 mm、表面粗糙度＜0.1 μm之單晶矽晶圓置於黏著帶之黏著劑層A，利用2 kg之橡膠輥於矽晶圓上往返滾動一次，藉此使其等貼合。於貼合後在常溫靜置20分鐘，之後將黏著劑層B側之脫模膜剝離，繼而，使用高壓水銀UV照射機，自黏著帶之黏著劑層B側向黏著劑層A照射405 nm之紫外線，且以黏著劑層A之基材側相反之側之表面的照射量成為3000 mJ/cm2 之方式進行照射。之後，於200℃進行1小時加熱處理。針對加熱處理後之黏著帶，依據JIS Z0237，以剝離速度300 mm/分鐘進行180°方向之拉伸試驗，測定對於矽晶圓之180°剝離強度。(Measurement of 180° peel strength) Peel the release film on the side A of the adhesive layer of the adhesive tape, and place an 8-inch single crystal silicon wafer with a thickness of 0.75 mm and surface roughness <0.1 μm on the adhesive tape for adhesion Agent layer A uses a 2 kg rubber roller to roll back and forth on the silicon wafer once to bond it together. After bonding, let it stand at room temperature for 20 minutes, then peel off the release film on the side of the adhesive layer B, and then use a high-pressure mercury UV irradiation machine to irradiate 405 nm from the side of the adhesive layer B of the adhesive tape to the adhesive layer A The ultraviolet rays are irradiated so that the irradiation amount of the surface on the side opposite to the substrate side of the adhesive layer A becomes 3000 mJ/cm 2 . After that, heat treatment was performed at 200°C for 1 hour. For the adhesive tape after heat treatment, according to JIS Z0237, a 180° direction tensile test was carried out at a peeling speed of 300 mm/min to measure the 180° peel strength of the silicon wafer.
（水平載重強度之測定） 將切成3 cm×4 cm且兩面由脫模膜保護之黏著帶之黏著劑層B側的脫模膜剝離，使黏著劑層B與載玻片（S9112，松浪硝子工業公司製造）貼合，獲得測定用樣品。貼合係藉由使2 kg之輥於黏著帶之黏著劑層A側之面上往返滾動一次而進行。繼而，將所獲得之樣品之黏著劑層A側之脫模膜剝離，使用高壓水銀UV照射機，以黏著劑層A之基材側相反之側之表面的照度成為3000 mJ/cm2 之方式自黏著劑層A側照射405 nm之紫外光。之後，使用表面、界面物性解析裝置（SAICAS DN-20，Daipla-Wintes公司製造），於25℃、50%RH、紫外光截止之條件下測定黏著帶之黏著劑層A之水平力及垂直力。切刀使用單晶金剛石製之寬度1 mm、傾角40°、餘隙角10°之刀，切削條件設為恆定速度模式下水平方向5 μm/秒、垂直方向0.5 μm/秒。將水平載重為0.002 N以上之點設為切刀接觸到黏著劑層A表面之點，之後於垂直方向上10 μm之深度範圍測定水平載重強度。(Measurement of horizontal load strength) The release film of the adhesive layer B side of the adhesive tape cut into 3 cm×4 cm and both sides protected by the release film is peeled off, so that the adhesive layer B and the glass slide (S9112, Songlang) (Manufactured by Glass Industry Co., Ltd.) to obtain a sample for measurement. The bonding is performed by rolling a 2 kg roller on the side of the adhesive layer A of the adhesive tape once and back. Then, the release film on the adhesive layer A side of the obtained sample was peeled off, and a high-pressure mercury UV irradiation machine was used to set the illuminance on the surface of the adhesive layer A opposite to the substrate side to 3000 mJ/cm 2 Irradiate 405 nm ultraviolet light from the adhesive layer A side. After that, use the surface and interface property analysis device (SAICAS DN-20, manufactured by Daipla-Wintes) to measure the horizontal force and vertical force of the adhesive layer A of the adhesive tape under the conditions of 25°C, 50%RH, and UV cut-off. . The cutter is made of single crystal diamond with a width of 1 mm, an inclination angle of 40°, and a clearance angle of 10°. The cutting conditions are set to 5 μm/sec in the horizontal direction and 0.5 μm/sec in the vertical direction in the constant speed mode. The point where the horizontal load is 0.002 N or more is set as the point where the cutter touches the surface of the adhesive layer A, and then the horizontal load strength is measured at a depth of 10 μm in the vertical direction.
（拉伸強度之測定） 藉由上述方法製作僅由黏著劑層A所構成之測定用樣品。繼而，使用高分子計器公司製造之沖切刀「拉伸1號型啞鈴狀」，以長邊與製造時之行進方向一致之方式將上述黏著劑層A沖切成為啞鈴狀，從而製作試片。針對所獲得之試片，使用島津製作所公司製造之「Autograph AGS-X」，以拉伸速度100 mm/min進行測定，並使試片斷裂。根據斷裂時之強度計算出拉伸強度。(Determination of tensile strength) A sample for measurement composed of only the adhesive layer A was prepared by the above method. Then, using a punching knife "stretched No. 1 dumbbell shape" manufactured by Polymer Meter Co., the adhesive layer A was punched into a dumbbell shape with the long side consistent with the direction of travel at the time of manufacture, thereby making a test piece . For the obtained test piece, the "Autograph AGS-X" manufactured by Shimadzu Corporation was used for measurement at a tensile speed of 100 mm/min, and the test piece was broken. The tensile strength is calculated based on the strength at break.
（拉伸彈性模數之測定） 藉由上述方法僅製作黏著劑層A，針對所獲得之黏著劑層A，使用高壓水銀紫外線照射機，以照度成為3000 mJ/cm2 之方式照射405 nm之紫外線，獲得紫外線硬化後之黏著劑層A之單層樣品。繼而，以長邊與製造時之行進方向一致之方式使用沖切刀進行沖切，藉此製作5 mm×35 mm之試片。將所獲得之試片浸漬於液態氮而冷卻至-50℃，之後，使用黏彈性譜儀（DVΑ-200，IT Meter and Control公司製造），於定速升溫拉伸模式、升溫速度10℃/分鐘、頻率10 Hz之條件下升溫至300℃，測定儲存彈性模數。測定此時之260℃之儲存彈性模數（E'）之值。(Measurement of tensile modulus of elasticity) Only the adhesive layer A is produced by the above method. For the obtained adhesive layer A, a high-pressure mercury ultraviolet irradiation machine is used to irradiate 405 nm with an illuminance of 3000 mJ/cm 2 UV-cured single-layer sample of adhesive layer A was obtained. Then, a punching knife was used for punching in such a way that the long side was the same as the direction of travel at the time of manufacturing, to produce a 5 mm×35 mm test piece. The obtained test piece was immersed in liquid nitrogen and cooled to -50°C. After that, a viscoelastic spectrometer (DVΑ-200, manufactured by IT Meter and Control) was used to increase the temperature in a constant-rate heating and stretching mode at a heating rate of 10°C/ The temperature is raised to 300℃ under the condition of 10 Hz and 10 Hz, and the storage elastic modulus is measured. Measure the value of the storage elastic modulus (E') at 260°C at this time.
（紫外線透射率之測定） 使用分光光度計（U-3900，日立製作所公司製造），測定黏著帶之紫外線透射率。更具體而言，於800～200 nm之區域中以掃描速度300 nm/min、狹縫間隔4 nm進行測定，從而測定405 nm之透射率。(Measurement of UV transmittance) Using a spectrophotometer (U-3900, manufactured by Hitachi, Ltd.), measure the UV transmittance of the adhesive tape. More specifically, the measurement is performed in a region of 800 to 200 nm at a scanning speed of 300 nm/min and a slit interval of 4 nm to measure the transmittance at 405 nm.
＜評估＞ 針對實施例及比較例中獲得之黏著帶，藉由以下之方法進行評估。將結果示於表2、3。＜Evaluation＞ The adhesive tapes obtained in the examples and comparative examples were evaluated by the following methods. The results are shown in Tables 2 and 3.
（積層步驟之評估） 將切斷成直徑20 cm之圓形之黏著帶的黏著劑A層側貼附於直徑20 cm、50 μm厚、表面粗糙度＜0.1 μm之矽晶圓。繼而，將黏著帶之黏著劑B層側貼附於直徑20 cm、厚度0.6 mm之玻璃晶圓（Tempax，SCHOTT公司製造）。於貼附後，於藉由濾波器截止365 nm以下之波長之狀態下，以對黏著劑層A之照射量成為3000 mJ/cm2 之方式自玻璃晶圓面側照射405 nm之波長之紫外光，使黏著劑層A、B交聯、硬化。將所獲得之矽晶圓/黏著帶/玻璃晶圓之積層體於設定為200℃之烘箱中使玻璃面為下方而靜置1小時，從而進行加熱處理。使用倒裝晶片接合器（FC6000、芝浦機械電子裝置公司製造），將50 μm厚之晶圓積層於加熱處理後恢復至常溫之樣品。具體而言，以矽晶圓面成為上方之方式使其吸附於設定為80℃之SUS載置台上，使用壓接頭尺寸10 mm×10 mm之陶瓷工具，積層9.8 mm×9.8 mm、50 μm厚、表面粗糙度＜0.1 μm且附帶25 μm厚之接合膜之單晶矽薄晶圓晶片。將積層時之壓接頭之溫度設為310℃，將壓力設為300 N，將積層時間設為90秒。 於進行上述積層步驟時，將可積層8段上述薄晶圓晶片之情形設為「◎」，將可積層1段，但於第2段以後於矽晶圓與黏著帶之間產生剝離之情形設為「〇」，將1段亦無法積層之情形設為「×」，以此對積層步驟進行評估。(Evaluation of the lamination process) The adhesive A layer side of the adhesive tape cut into a circle with a diameter of 20 cm is attached to a silicon wafer with a diameter of 20 cm, a thickness of 50 μm, and a surface roughness of <0.1 μm. Then, the adhesive B layer side of the adhesive tape was attached to a glass wafer (Tempax, manufactured by SCHOTT) with a diameter of 20 cm and a thickness of 0.6 mm. After attaching, irradiate ultraviolet rays with a wavelength of 405 nm from the side of the glass wafer so that the irradiation amount to the adhesive layer A becomes 3000 mJ/cm 2 in a state where the wavelength below 365 nm is cut off by the filter Light cross-links and hardens the adhesive layers A and B. The obtained laminated body of the silicon wafer/adhesive tape/glass wafer was placed in an oven set at 200° C. with the glass surface facing downward for 1 hour to perform heat treatment. Use a flip chip bonder (FC6000, manufactured by Shibaura Mechatronics Co., Ltd.) to laminate 50 μm-thick wafers to samples that are restored to room temperature after heat treatment. Specifically, the silicon wafer is adsorbed onto a SUS table set at 80℃ with the silicon wafer surface facing upwards. A ceramic tool with a pressure joint size of 10 mm×10 mm is used, and the stack is 9.8 mm×9.8 mm and 50 μm thick. , Single crystal silicon thin wafer with surface roughness <0.1 μm and 25 μm thick bonding film. Set the temperature of the pressure joint during lamination to 310°C, the pressure to 300 N, and the lamination time to 90 seconds. When performing the above layering step, set the case where 8 stages of the above thin wafer can be layered to "◎", set 1 stage to be layered, but peeling occurs between the silicon wafer and the adhesive tape after the second stage Set it to "〇", and set the case where 1 stage cannot be layered to "×" to evaluate the layering step.
（剝離性之評估）
將黏著帶之黏著劑層A側之面貼附於附凸塊之晶圓（凸塊直徑
（凸塊之變形性之評估）
將黏著帶之黏著劑層A側之面貼附於附凸塊之晶圓（凸塊直徑
[表2]
[表3]
若根據本發明，可提供一種黏著帶，該黏著帶即便在用於伴隨著高溫及載重之步驟之情形時亦不會自被接著體剝離，且於剝離時可容易地進行剝離，進而亦可抑制銲點凸塊之變形。又，若根據本發明，可提供一種使用該黏著帶之半導體元件之製造方法。According to the present invention, it is possible to provide an adhesive tape, which does not peel from the adherend even when used in a process accompanied by high temperature and load, and can be easily peeled during peeling, and furthermore Suppress the deformation of the solder bumps. Moreover, according to the present invention, a method for manufacturing a semiconductor device using the adhesive tape can be provided.
1:黏著帶 2:晶圓 3:半導體晶片 4:銲點凸塊1: Adhesive tape 2: Wafer 3: Semiconductor wafer 4: Solder bump
[圖1]係表示熱壓接合之情況之示意圖。[Figure 1] is a schematic diagram showing the state of thermocompression bonding.
Claims (9)
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| JP2601956B2 (en) | 1991-07-31 | 1997-04-23 | リンテック株式会社 | Removable adhesive polymer |
| JP4404526B2 (en) * | 2002-07-11 | 2010-01-27 | 積水化学工業株式会社 | Adhesive material, single-sided adhesive tape and double-sided adhesive tape |
| JP2005197630A (en) * | 2003-12-09 | 2005-07-21 | Sekisui Chem Co Ltd | Method of manufacturing ic chip |
| EP1783820A1 (en) * | 2004-08-02 | 2007-05-09 | Sekisui Chemical Co., Ltd. | Process for producing ic chip |
| JP2006228985A (en) * | 2005-02-17 | 2006-08-31 | Sekisui Chem Co Ltd | Process for producing ic chip |
| KR101386367B1 (en) * | 2007-12-12 | 2014-04-16 | 세키스이가가쿠 고교가부시키가이샤 | Two-sided adhesive tape for semiconductor processing and tape for semiconductor processing |
| JP2009146974A (en) * | 2007-12-12 | 2009-07-02 | Sekisui Chem Co Ltd | Double-sided adhesive tape for semiconductor processing |
| JP2013231159A (en) * | 2012-04-06 | 2013-11-14 | Sekisui Chem Co Ltd | Adhesive composition, adhesive tape, and method for processing wafer |
| JP2014172278A (en) * | 2013-03-08 | 2014-09-22 | Dic Corp | Thermal transfer film, method for manufacturing the same, and method for manufacturing decorative article using the same |
| JP5718515B1 (en) * | 2014-01-23 | 2015-05-13 | 古河電気工業株式会社 | Adhesive tape for protecting semiconductor wafer surface and method for processing semiconductor wafer |
| JP6572043B2 (en) * | 2015-07-24 | 2019-09-04 | 積水化学工業株式会社 | Semiconductor wafer protection film |
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