TW202020094A - Adhesive tape for dicing and method for manufacturing semiconductor chips - Google Patents
Adhesive tape for dicing and method for manufacturing semiconductor chips Download PDFInfo
- Publication number
- TW202020094A TW202020094A TW108125200A TW108125200A TW202020094A TW 202020094 A TW202020094 A TW 202020094A TW 108125200 A TW108125200 A TW 108125200A TW 108125200 A TW108125200 A TW 108125200A TW 202020094 A TW202020094 A TW 202020094A
- Authority
- TW
- Taiwan
- Prior art keywords
- polysiloxane
- adhesive
- adhesive tape
- mass
- adhesive layer
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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]
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Dicing (AREA)
- Led Device Packages (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本發明涉及使用於半導體材料的切割的切割用黏著帶及使用切割用黏著帶的半導體晶片之製造方法,該半導體材料為半導體晶片的材料。The present invention relates to a dicing adhesive tape used for dicing a semiconductor material and a method for manufacturing a semiconductor wafer using the dicing adhesive tape. The semiconductor material is a material of a semiconductor wafer.
歷來,為了製作具有LED(Light Emitting Diode)等之半導體晶片而使用的切割用黏著帶方面,已知具有由丙烯酸系樹脂所成的黏合劑層的黏著帶(專利文獻1參照)。
此外,為了製作具有LED等的半導體晶片而使用的切割用黏著帶方面,已知具有由聚矽氧系樹脂所成的黏著劑層之黏著帶(專利文獻2、專利文獻3參照)。
再者,使用切割用黏著帶而製作半導體晶片的方法方面,已知將黏著帶黏貼於在基板上形成複數個半導體元件的半導體元件基板的基板側,並透過切割機切斷半導體元件基板的方法(專利文獻4參照)。
[先前技術文獻]
[專利文獻]Conventionally, in order to produce an adhesive tape for dicing used for manufacturing semiconductor wafers having LEDs (Light Emitting Diode) and the like, an adhesive tape having an adhesive layer made of acrylic resin has been known (refer to Patent Document 1).
In addition, in order to produce an adhesive tape for dicing used for manufacturing semiconductor wafers including LEDs, an adhesive tape having an adhesive layer made of polysiloxane resin is known (refer to
[專利文獻1]日本特開2013-38408號公報 [專利文獻2]日本特開2015-050216號公報 [專利文獻3]日本特開2016-122812號公報 [專利文獻4]日本特開2005-93503號公報[Patent Document 1] Japanese Patent Application Publication No. 2013-38408 [Patent Document 2] Japanese Unexamined Patent Publication No. 2015-050216 [Patent Document 3] Japanese Patent Laid-Open No. 2016-122812 [Patent Document 4] Japanese Patent Laid-Open No. 2005-93503
[發明所欲解決之問題][Problems to be solved by the invention]
然而,近年來,在製作被透過切割而個片化的半導體晶片的方法方面,已提出一種技術,將黏著帶黏貼於複數個半導體元件被密封樹脂、螢光體等的被覆材所被覆的半導體材料而進行切割,應付所謂晶圓級CSP(晶片級封裝)程序。 如此般,在將黏著帶黏貼於半導體元件為被覆材所被覆的半導體材料的情況下,取決於黏著帶方面的黏著劑層的構成、被覆材的素材等,有時黏著力不足,致使被透過切割而個片化的半導體晶片發生飛散。此外,為了抑制半導體晶片的飛散而設計高的黏著劑層的滾球黏性、黏著力時,在將獲得的半導體晶片從黏著帶剝離之際,有時產生在黏著劑附著於半導體晶片之下殘存的所謂黏劑殘物。However, in recent years, in terms of a method of manufacturing a semiconductor chip that has been diced by dicing, a technique has been proposed that applies an adhesive tape to a plurality of semiconductor elements covered with a coating material such as a sealing resin or a phosphor, The material is cut to meet the so-called wafer-level CSP (wafer-level packaging) process. In this way, when the adhesive tape is adhered to the semiconductor material covered with the semiconductor element as the coating material, depending on the composition of the adhesive layer on the adhesive tape, the material of the coating material, etc., the adhesive force may be insufficient, causing penetration The singulated semiconductor wafer is scattered. In addition, in order to suppress the scattering of the semiconductor wafer, when designing a high adhesive ball layer adhesiveness and adhesive force, when the obtained semiconductor wafer is peeled off from the adhesive tape, the adhesive may sometimes be attached under the semiconductor wafer The remaining so-called adhesive residue.
本發明目的在於提供一種切割用黏著帶及使用其之半導體晶片之製造方法,對於以被覆材被覆的具有複數個半導體元件之半導體材料具有良好的黏著力及附著力,同時在將被透過切割而個片化的半導體晶片剝離的情況下抑制對於半導體晶片之黏劑殘物。 [解決問題之技術手段]An object of the present invention is to provide a method for manufacturing an adhesive tape for dicing and a semiconductor wafer using the same, which has good adhesion and adhesion to a semiconductor material having a plurality of semiconductor elements coated with a coating material, In the case of peeling of the individualized semiconductor wafers, the adhesive residue to the semiconductor wafers is suppressed. [Technical means to solve the problem]
本發明人基於該目的,就切割用黏著帶的黏著劑層銳意檢討的結果,使黏著劑層為在至少包含加成反應型聚矽氧系黏著劑及對於該加成反應型聚矽氧系黏著劑的交聯劑的特定的黏著劑添加感光鉑(Pt)觸媒的構成時,對於具有為被覆材所被覆的複數個半導體元件的半導體材料具有良好的黏著力,同時發現在將被透過切割而個片化的半導體晶片剝離的情況下抑制對於半導體晶片的黏劑殘物,從而創作本發明。 亦即,發現:使切割用黏著帶的黏著劑層為上述構成,使得在將具有為被覆材所被覆的複數個半導體元件的半導體材料分割為複數個半導體晶片之際,由於良好的附著力及黏著力,因而抑制在切割時被個片化的半導體晶片飛散。此外另一方面,在將被透過切割而個片化的半導體晶片從切割用黏著帶剝離之際,將紫外線等的光對黏著劑層照射,從而使黏著劑中的感光鉑(Pt)觸媒被活性化,加成反應型聚矽氧系黏著劑與對於該加成反應型聚矽氧系黏著劑之交聯劑的交聯反應被促進,致使黏著劑的凝聚力變比光照射前大。此結果,黏著劑層的附著力適切降低,再者在保持力試驗中的破壞模式成為「界面破壞」或保持力試驗中成為「不落下」者。藉此,發現從半導體晶片的切割用黏著帶的拾取性變良好,此外抑制對於半導體晶片的黏劑殘物。Based on this objective, the inventors made a rigorous review of the results of the adhesive layer of the adhesive tape for cutting so that the adhesive layer contains at least the addition-reactive polysiloxane-based adhesive and the addition-reactive polysiloxane-based adhesive. Adhesive crosslinking agent When a specific adhesive is added with a photosensitive platinum (Pt) catalyst, it has good adhesion to semiconductor materials with a plurality of semiconductor elements covered by the coating material. In the case where the diced semiconductor wafer is peeled off, the adhesive residue on the semiconductor wafer is suppressed, and the present invention is created. That is, it was found that when the adhesive layer of the dicing adhesive tape is configured as described above, when a semiconductor material having a plurality of semiconductor elements covered with a coating material is divided into a plurality of semiconductor wafers, due to good adhesion and Adhesion, thus suppressing the scattering of individual semiconductor wafers during dicing. On the other hand, when peeling the diced semiconductor wafer from the dicing adhesive tape, the adhesive layer is irradiated with light such as ultraviolet rays to make the photosensitive platinum (Pt) catalyst in the adhesive After being activated, the crosslinking reaction between the addition reaction type silicone adhesive and the crosslinking agent for the addition reaction type silicone adhesive is promoted, so that the cohesive force of the adhesive becomes larger than before light irradiation. As a result, the adhesion of the adhesive layer is appropriately reduced, and the failure mode in the retention test becomes "interfacial failure" or the "non-falling" one in the retention test. With this, it was found that the pick-up property from the dicing adhesive tape for semiconductor wafers was improved, and the adhesive residues on the semiconductor wafers were also suppressed.
本發明的切割用黏著帶為具備基材與層積於該基材的聚矽氧系黏著劑層,並用於將具有為被覆材所被覆的複數個半導體元件的半導體材料分割為複數個半導體晶片之際者,前述聚矽氧系黏著劑層以加成反應型聚矽氧系黏著劑為主劑,包含感光鉑(Pt)觸媒及對於該加成反應型聚矽氧系黏著劑之交聯劑,含於前述聚矽氧系黏著劑層的聚矽氧膠(G)的全質量(Gw)與聚矽氧樹脂(R)的全質量(Rw)的質量比(Gw)/(Rw)為35/65~50/50的範圍,該聚矽氧膠(G)與該聚矽氧樹脂(G)的合計質量中的具有烯基的聚矽氧膠(G1)的含有比率為35質量%以上且50質量%以下的範圍,準據於JIS Z 0237(2009)的黏著特性下符合下述條件(a)~(c)的全部:
(a)對於BA-SUS試驗板之光照射前的黏著力為2.4N/10mm以上且5.5N/10mm以下;
(b)傾斜式滾球黏性試驗(傾斜角30°,溫度23℃,相對濕度50%RH)下的球數的值在使光照射前的球數的值為BN0、使光照射後的球數的值為BN1的情況下,為BN0>BN1的關係;
(c)光照射後的保持力試驗(溫度40℃,相對濕度33%RH,放置時間5000分)下,落下時的破壞現象為前述聚矽氧系黏著劑層與BA-SUS試驗板的界面破壞,或該保持力試驗中不落下。
於此,切割用黏著帶可對複數個前述半導體元件被由聚矽氧樹脂所成的前述被覆材密封的前述半導體材料從該被覆材側進行黏貼而使用。The dicing adhesive tape of the present invention is provided with a base material and a polysilicone-based adhesive layer laminated on the base material, and is used to divide a semiconductor material having a plurality of semiconductor elements covered by a covering material into a plurality of semiconductor wafers On the occasion, the polysiloxane-based adhesive layer uses an addition-reactive polysiloxane-based adhesive as a main agent, including a photosensitive platinum (Pt) catalyst and the intersection of the addition-reactive polysiloxane-based adhesive. Combined agent, the mass ratio (Gw)/(Rw) of the total mass (Gw) of the polysiloxane (G) contained in the polysiloxane adhesive layer to the total mass (Rw) of the polysiloxane resin (R) ) Is in the range of 35/65 to 50/50, and the content ratio of the polysiloxane (G1) having an alkenyl group in the total mass of the polysiloxane (G) and the polysiloxane resin (G) is 35 The range of more than 50% by mass and less than 50% by mass is based on the adhesive properties of JIS Z 0237 (2009) and meets all of the following conditions (a) to (c):
(a) The adhesion to the BA-SUS test plate before light irradiation is 2.4N/10mm or more and 5.5N/10mm or less;
(b) The value of the number of balls in the tilted ball viscosity test (inclination angle 30°, temperature 23°C, relative humidity 50% RH) before the light irradiation is BN0, after light irradiation When the value of the number of balls is BN1, the relationship is BN0>BN1;
(c) Retention test after light irradiation (temperature 40°C, relative humidity 33%RH,
此外,從其他觀點而言時,本發明的切割用黏著帶為具備基材與層積於該基材的聚矽氧系黏著劑層,並用於將具有為被覆材所被覆的複數個半導體元件的半導體材料分割為複數個半導體晶片之際者,前述聚矽氧系黏著劑層以加成反應型聚矽氧系黏著劑與過氧化物固化型聚矽氧系黏著劑的混合物為主劑,包含感光鉑(Pt)觸媒及對於該加成反應型聚矽氧系黏著劑之交聯劑,含於前述聚矽氧系黏著劑層的聚矽氧膠(G)的全質量(Gw)與聚矽氧樹脂(R)的全質量(Rw)的質量比(Gw)/(Rw)為40/60~56/44的範圍,該聚矽氧膠(G)與該聚矽氧樹脂(G)的合計質量中的具有烯基的聚矽氧膠(G1)的含有比率為14質量%以上且42質量%以下的範圍,準據於JIS Z 0237(2009)的黏著特性下符合下述條件(a)~(c)的全部:
(a)對於BA-SUS試驗板之光照射前的黏著力為2.4N/10mm以上且5.5N/10mm以下;
(b)傾斜式滾球黏性試驗(傾斜角30°,溫度23℃,相對濕度50%RH)下的球數的值在使光照射前的球數的值為BN0、使光照射後的球數的值為BN1的情況下,為BN0>BN1的關係;
(c)光照射後的保持力試驗(溫度40℃,相對濕度33%RH,放置時間5000分)下,落下時的破壞現象為前述聚矽氧系黏著劑層與BA-SUS試驗板的界面破壞,或該保持力試驗中不落下。
於此,切割用黏著帶可對複數個前述半導體元件被由聚矽氧樹脂所成的前述被覆材密封的前述半導體材料從該被覆材側進行黏貼而使用。
此外,前述聚矽氧系黏著劑層可進一步包含由過氧化物所成的引發劑。In addition, from other viewpoints, the dicing adhesive tape of the present invention is provided with a base material and a polysiloxane-based adhesive layer laminated on the base material, and is used to cover a plurality of semiconductor elements covered with a coating material When the semiconductor material is divided into a plurality of semiconductor chips, the aforementioned polysiloxane-based adhesive layer is mainly composed of a mixture of an addition-reactive polysiloxane-based adhesive and a peroxide-curable polysiloxane-based adhesive. The total mass (Gw) of the polysiloxane (G) containing the photosensitive platinum (Pt) catalyst and the crosslinking agent for the addition reaction type polysiloxane adhesive, and the polysiloxane adhesive (G) contained in the polysiloxane adhesive layer The mass ratio (Gw)/(Rw) to the total mass (Rw) of the silicone resin (R) is in the range of 40/60 to 56/44. The silicone rubber (G) and the silicone resin ( G) The content ratio of the polysiloxane having an alkenyl group (G1) in the total mass is in the range of 14% by mass or more and 42% by mass or less, which is in accordance with the following adhesive properties under JIS Z 0237 (2009) All of conditions (a) to (c):
(a) The adhesion to the BA-SUS test plate before light irradiation is 2.4N/10mm or more and 5.5N/10mm or less;
(b) The value of the number of balls in the tilted ball viscosity test (inclination angle 30°, temperature 23°C, relative humidity 50% RH) before the light irradiation is BN0, after light irradiation When the value of the number of balls is BN1, the relationship is BN0>BN1;
(c) Retention test after light irradiation (temperature 40°C, relative humidity 33%RH,
此外,從其他觀點而言時,本發明的半導體晶片之製造方法包含:黏貼程序,其為將上述的切割用黏著帶,對以由聚矽氧樹脂所成的密封樹脂而密封的複數個前述半導體元件被形成於基板上的半導體元件基板,從該密封樹脂側進行黏貼者;切斷程序,其為將被黏貼前述切割用黏著帶的前述半導體元件基板,切斷為複數個半導體晶片者;照射程序,其為對前述半導體元件基板的前述切割用黏著帶照射光者;和剝離程序,其為從前述複數個半導體晶片將前述切割用黏著帶剝離者。 [對照先前技術之功效]In addition, from another point of view, the method for manufacturing a semiconductor wafer of the present invention includes: a pasting process which seals the above-mentioned dicing adhesive tape to a plurality of the foregoing sealed with a sealing resin made of polysiloxane resin A semiconductor element substrate on which a semiconductor element is formed on the substrate and pasted from the sealing resin side; a cutting procedure, which is to cut the semiconductor element substrate pasted with the dicing adhesive tape into a plurality of semiconductor wafers; The irradiation procedure is to irradiate the dicing adhesive tape of the semiconductor element substrate with light; and the peeling procedure is to peel the dicing adhesive tape from the plurality of semiconductor wafers. [Comparing the efficacy of the previous technology]
依本發明時,可提供一種切割用黏著帶及使用其之半導體晶片之製造方法,對於複數個半導體元件為被覆材所被覆的半導體材料,於光照射前的階段具有良好的黏著力及附著力,同時在光照射後將被透過切割而個片化的半導體晶片剝離的情況下,具有半導體晶片的良好的拾取性,同時抑制對於半導體晶片之黏劑殘物。According to the present invention, a method for manufacturing an adhesive tape for dicing and a semiconductor wafer using the same can be provided. For a semiconductor material covered by a plurality of semiconductor elements as a coating material, it has good adhesion and adhesion at a stage before light irradiation At the same time, when the semiconductor wafer that has been singulated through dicing is peeled off after light irradiation, it has good pickup properties of the semiconductor wafer while suppressing adhesive residues to the semiconductor wafer.
以下,參照圖式就本發明的實施方式詳細進行說明。
[黏著帶的構成]
圖1為就適用本實施方式之切割用黏著帶1(以下僅稱為黏著帶1)的構成的一例進行繪示的圖。本實施方式的黏著帶1用於例如在具有LED(Light emitting diode)、功率半導體等的半導體元件之半導體晶片之製程中成為半導體晶片的基礎的半導體材料的切割。Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
[Composition of Adhesive Tape]
FIG. 1 is a diagram illustrating an example of the configuration of a dicing adhesive tape 1 (hereinafter simply referred to as an adhesive tape 1) to which this embodiment is applied. The
如示於圖1,黏著帶1具有在基材2上層積作為聚矽氧系黏著劑層的一例的黏著劑層3的構成。
另外,圖式雖省略,惟黏著帶1亦可在基材2與黏著劑層3之間依所需具備為了提高基材2與黏著劑層3的密接性用的錨固塗層。此外,亦可在基材2的表面(與黏著劑層3相向之面的相反側的面),實施表面處理。再者,亦可在黏著劑層3的表面(與基材2相向之面的相反側的面)具備剝離膜。As shown in FIG. 1, the
<基材>
本實施方式的基材2由使紫外線等的光透射的材料構成。基材2的材料方面,只要可使紫外線等的光透射則不特別限定,可使用例如可使紫外線等的光透射的塑膠等。另外,於此,可使紫外線等的光透射非表示紫外線等的光的透射率為100%,只要至少可促進黏著劑層3的後述的感光鉑(Pt)觸媒所致的加成反應型聚矽氧系黏著劑與交聯劑的加成反應的程度的光可透射即可。<Substrate>
The
基材2的材料方面,具體而言可使用聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚苯硫醚、雙軸拉伸聚丙烯、脂肪族聚醯亞胺(透明性聚醯亞胺)、環烯烴、氟系樹脂、聚烯烴樹脂等的樹脂膜。此外,依用途,於基材2方面,例如亦可使用將聚對苯二甲酸乙二酯與聚烯烴樹脂膜進行層疊的複合膜、及將此等複合膜進一步與樹脂膜層疊的複合膜、以共擠出而作成複層的樹脂膜等。
此中,基材2方面,優選上使用以聚對苯二甲酸乙二酯為主成分之材料。For the material of the
<黏著劑層>
本實施方式的黏著劑層3包含硬化型的聚矽氧系黏著劑。具體而言,黏著劑層3在硬化型的聚矽氧系黏著劑方面,包含加成反應型聚矽氧系黏著劑。此外,黏著劑層3在硬化型的聚矽氧系黏著劑方面,除加成反應型聚矽氧系黏著劑以外,亦可包含過氧化物固化型聚矽氧系黏著劑。一般而言,此加成反應型聚矽氧系黏著劑及過氧化物固化型聚矽氧系黏著劑皆包含由有機聚矽氧烷所成的聚矽氧膠(G)與由有機聚矽氧烷所成的聚矽氧樹脂(R)。
以下,以硬化型的聚矽氧系黏著劑方面包含加成反應型聚矽氧系黏著劑的黏著劑層3為第1形態,以硬化型的聚矽氧系黏著劑方面包含加成反應型聚矽氧系黏著劑與過氧化物固化型聚矽氧系黏著劑的黏著劑層3為第2形態,就構成黏著劑層3之各成分詳細進行說明。<Adhesive layer>
The
<第1形態的黏著劑層>
第1形態的黏著劑層3包含加成反應型聚矽氧系黏著劑、和將加成反應型聚矽氧系黏著劑交聯的作為硬化劑的一例的交聯劑。此外,第1形態的黏著劑層3包含透過紫外線等的光的照射予以促進加成反應型聚矽氧系黏著劑與交聯劑的反應的感光鉑(Pt)觸媒。另外,第1形態的黏著劑層3不包含過氧化物固化型聚矽氧系黏著劑。
再者,第1形態的黏著劑層3亦可依所需包含補強填充劑、凝聚力提升劑、著色劑等的其他添加劑。<Adhesive layer of the first form>
The
(加成反應型聚矽氧系黏著劑) 加成反應型聚矽氧系黏著劑雖可使用歷來眾知者,惟一般而言為包含由平均1分子中含有至少2個矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G1)、和由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R1)的黏著劑。於此,由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R1)不含有矽鍵結烯基。(Addition reaction type polysiloxane adhesive) Although addition reaction type polysiloxane-based adhesives can be used, it is generally known to be an organic polymer containing polydimethylsiloxane containing at least two silicon-bonded alkenyl groups in an average of 1 molecule. Adhesive for polysiloxane (G1) made of silicone and polysiloxane resin (R1) made of organic polysiloxane such as polydimethylsiloxane. Here, the polysiloxane resin (R1) made of organic polysiloxane such as polydimethylsiloxane does not contain a silicon-bonded alkenyl group.
以下,就含於加成反應型聚矽氧系黏著劑的由平均1分子中含有至少2個矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G1)、和由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R1)進一步詳細進行說明。 另外,於以下的說明,有時將由平均1分子中含有至少2個矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G1)記載為由含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G1),或僅記載為具有烯基的聚矽氧膠(G1)。The following is a polysilicon composed of an organic polysiloxane such as polydimethylsiloxane containing an average of at least two silicon-bonded alkenyl groups per molecule contained in an addition reaction type polysiloxane-based adhesive. The oxygen gum (G1) and the polysiloxane resin (R1) made of organic polysiloxane such as polydimethylsiloxane are described in further detail. In addition, in the following description, a polysiloxane (G1) made of an organic polysiloxane such as polydimethylsiloxane containing at least two silicon-bonded alkenyl groups in an average molecule may be described as Polysiloxane (G1) made of organic polysiloxane such as polydimethylsiloxane containing silicon-bonded alkenyl group, or simply described as polysiloxane having alkenyl group (G1).
[由含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G1)] 本實施方式中的由含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G1)為使用於加成反應型聚矽氧系黏著劑者即可,亦即為平均1分子中含有至少2個矽鍵結烯基者即可,無特別限定。含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷的分子構造方面,舉例如主鏈部分由二有機矽氧烷單元的重複所成的直鏈狀構造、該分子構造的一部分包含支鏈的構造、支鏈狀構造、或環狀體構造。其中,從紫外線等的光的照射後的黏著劑的機械強度等、物性的點而言,直鏈狀構造的有機聚矽氧烷為優選。[Polysiloxane (G1) made of organic polysiloxane such as polydimethylsiloxane containing silicon-bonded alkenyl group] The polysiloxane (G1) made of an organic polysiloxane such as polydimethylsiloxane containing silicon-bonded alkenyl groups in this embodiment is an addition reaction type polysiloxane-based adhesive It is sufficient if it contains at least two silicon-bonded alkenyl groups per molecule, and it is not particularly limited. The molecular structure of an organic polysiloxane such as polydimethylsiloxane containing a silicon-bonded alkenyl group includes, for example, a linear structure composed of a repeating diorganosiloxane unit in the main chain portion, and the molecule A part of the structure includes a branched structure, a branched structure, or a ring structure. Among them, the organic polysiloxane having a linear structure is preferred from the viewpoints of mechanical strength and the like of the adhesive after irradiation of light such as ultraviolet rays.
由含有矽鍵結烯基的有機聚矽氧烷所成的聚矽氧膠(G1)可為油狀或生膠狀,惟生膠狀為優選。
油狀的情況下,優選上由有機聚矽氧烷所成的聚矽氧膠(G1)的黏度於25℃下為1000mPa・s以上。上述黏度不足1000mPa・s時,存在光照射前後的黏著劑無法發現期望的黏著特性之虞、黏著劑層3與基材2的密接性劣化之虞。
生膠狀的情況下,將由有機聚矽氧烷所成的聚矽氧膠(G1)以甲苯溶解為30質量%的濃度時的黏度在25℃下100000mPa・s以下為優選。上述黏度超過100000mPa・s時,調製黏著劑組成物時的攪拌恐變困難。
另外,上述黏度可使用BM型旋轉黏度計進行測定。The polysiloxane (G1) made of organic polysiloxane containing a silicon-bonded alkenyl group may be oily or raw, but raw rubber is preferred.
In the case of oil, it is preferable that the viscosity of the polysiloxane (G1) made of organic polysiloxane is at least 1000 mPa·s at 25°C. When the viscosity is less than 1000 mPa·s, the adhesive before and after light irradiation may not be able to find the desired adhesive properties, and the adhesiveness between the
由含有矽鍵結烯基的有機聚矽氧烷所成的聚矽氧膠(G1)雖舉例如以下述通式(1)或通式(2)表示者,惟不限定於此等。The polysiloxane (G1) made of an organic polysiloxane containing a silicon-bonded alkenyl group is, for example, represented by the following general formula (1) or general formula (2), but it is not limited thereto.
【化1】…通式(1)【Chemistry 1】 …Formula (1)
【化2】…通式(2)【Chemical 2】 …Formula (2)
於此,於上述通式(1)、通式(2),R1 為彼此獨立不具有脂肪族不飽和結合的1價烴基,X為烯基含有有機基。a為0~3的整數,m為0以上的整數,n為100以上的整數,其中a與m不會同時成為0。m+n是上述有機聚矽氧烷的25℃下的黏度成為1000mPa・s以上的值。Here, in the above general formula (1) and general formula (2), R 1 is a monovalent hydrocarbon group independently having no aliphatic unsaturated bond, and X is an alkenyl group-containing organic group. a is an integer of 0 to 3, m is an integer of 0 or more, and n is an integer of 100 or more, where a and m do not become 0 at the same time. m+n is the value at which the viscosity of the above-mentioned organopolysiloxane at 25° C. becomes 1000 mPa·s or more.
R1 方面,優選上為碳數1~10優選上碳數1~7的不具有脂肪族不飽和結合的1價烴基。舉例如甲基、乙基、丙基、及丁基等的烷基、環己基等的環烷基及苯基、及甲苯基等的芳香基等,尤其甲基或苯基為優選。R 1 is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms and preferably having 1 to 7 carbon atoms, which does not have an aliphatic unsaturated bond. Examples include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, phenyl groups, and aromatic groups such as tolyl groups. In particular, methyl or phenyl groups are preferred.
X方面,碳數2~10的烯基含有有機基為優選。舉例如乙烯基、丙烯基、己烯基、辛烯基、丙烯醯丙基、丙烯醯甲基、甲基丙烯醯丙基、丙烯醯氧基丙基、丙烯醯氧基甲基、甲基丙烯醯氧基丙基、甲基丙烯氧基甲基、環己烯基乙基、及乙烯基氧丙基等。其中,乙烯基、烯丙基等的低級烯基為優選上,從工業上觀點而言,尤其乙烯基為優選。上述烯基的結合位置無特別限定,可為分子鏈末端、分子鏈側鏈或分子鏈末端與分子鏈側鏈雙方。In terms of X, it is preferable that the alkenyl group having 2 to 10 carbon atoms contains an organic group. For example, vinyl, propenyl, hexenyl, octenyl, propenyl propyl, propenyl methyl, methacryl propyl, propenyl oxypropyl, propenyl oxymethyl, methacrylic Acyloxypropyl, methacryloxymethyl, cyclohexenylethyl, vinyloxypropyl, etc. Among them, lower alkenyl groups such as vinyl and allyl are preferred, and vinyl is particularly preferred from an industrial point of view. The binding position of the above alkenyl group is not particularly limited, and may be the molecular chain end, the molecular chain side chain, or both the molecular chain end and the molecular chain side chain.
上述烯基的個數是適切的範圍依含於加成反應型聚矽氧系黏著劑的由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R1)的含量、交聯劑的添加量、其他添加成分的平衡而變,故雖無法一概而言,惟例如對於有機聚矽氧烷的有機基100個,一般而言0.1~3.0個的範圍為優選。然後,在此比率的範圍下,以成為上述的黏度的範圍的方式調整分子量,以平均有機聚矽氧烷1分子中之上述烯基的個數成為至少2個的方式進行調整為優選。上述烯基的個數相對於有機聚矽氧烷的有機基100個不足0.1個時,對黏著帶1照射光之際,黏著劑難硬化,凝聚力難提升。此情況下,無法獲得期望的附著力降低、保持力試驗中的破壞模式,將黏著帶1使用於半導體元件基板等的切割之後,將獲得的半導體晶片等從黏著帶1剝離之際,被個片化的半導體晶片的拾取性恐變差、恐容易於半導體晶片等產生黏劑殘物。另一方面,上述烯基的個數相對於有機聚矽氧烷的有機基100個超過3.0個時,於黏著帶1,設置以氟烷基變性矽氧聚合物進行脫模處理的剝離膜的情況下,對於黏著劑層3之剝離膜的剝離力恐變大。The number of the above alkenyl groups is appropriate, and the range depends on the polysiloxane resin (R1) made of an organic polysiloxane such as polydimethylsiloxane, which is an addition reaction type polysiloxane-based adhesive. The content, the amount of the cross-linking agent added, and the balance of other added components vary, so it is impossible to generalize, but for example, for 100 organic groups of the organopolysiloxane, the range of 0.1 to 3.0 is generally preferred. Then, within the range of this ratio, it is preferable to adjust the molecular weight so as to be within the above-mentioned viscosity range, and to adjust so that the number of the above-mentioned alkenyl groups per molecule of the organic polysiloxane becomes at least two. When the number of the above alkenyl groups is less than 0.1 with respect to 100 organic groups of the organic polysiloxane, when the
[由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R1)]
本實施方式中的由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R1)為具有R2 3
SiO0.5
單元(M單元)及SiO2
單元(Q單元)的有機聚矽氧烷,為稱為所謂MQ樹脂者。此由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R1)基本上在分子內不具有烯基,可使用歷來眾知者。R2
為碳數1~10的1價烴基,舉例上述的在R1
方面例示者。上述有機聚矽氧烷以R2 3
SiO0.5
單元/SiO2
單元的莫耳比成為0.5以上且1.7以下的範圍的方式含有R2 3
SiO0.5
單元及SiO2
單元為優選。R2 3
SiO0.5
單元/SiO2
單元的莫耳比不足0.5時,獲得的黏著劑層3的黏著力、附著力有時降低。另一方面,R2 3
SiO0.5
單元/SiO2
單元的莫耳比超過1.7時,獲得的黏著劑層3的黏著力、保持力有時降低。另外,上述有機聚矽氧烷可具有OH基。該情況下,OH基的含量是優選上相對於上述有機聚矽氧烷的總質量為4.0質量%以下。OH基超過上述上限值時黏著劑的硬化性恐降低。[Polysiloxane resin (R1) made of organic polysiloxane such as polydimethylsiloxane] In this embodiment, it is made of organic polysiloxane such as polydimethylsiloxane. The polysiloxane resin (R1) is an organic polysiloxane having R 2 3 SiO 0.5 units (M units) and SiO 2 units (Q units), and is a so-called MQ resin. The polysiloxane resin (R1) made of organic polysiloxane such as polydimethylsiloxane does not basically have an alkenyl group in the molecule, and it can be used by a publicly known person. R 2 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and exemplified above for R 1 is exemplified. It is preferable that the organic polysiloxane contains R 2 3 SiO 0.5 units and SiO 2 units so that the molar ratio of R 2 3 SiO 0.5 units/SiO 2 units is in the range of 0.5 or more and 1.7 or less. When the molar ratio of R 2 3 SiO 0.5 unit/SiO 2 unit is less than 0.5, the adhesive force and adhesive force of the obtained
上述有機聚矽氧烷可併用2種以上。此外,上述有機聚矽氧烷亦可在不損及本發明的特性的範圍下,具有R2 SiO1.5 單元(T單元)及/或R2 2 SiO單元(D單元)。Two or more of the above organic polysiloxanes can be used in combination. In addition, the above-mentioned organic polysiloxane may have R 2 SiO 1.5 units (T units) and/or R 2 2 SiO units (D units) within a range that does not impair the characteristics of the present invention.
上述的由含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G1)與由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R1)亦可單純混合而使用。此外,由含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G1)方面,含有以上述通式(2)表示的有機聚矽氧烷的情況下,只要不損及本發明的特性,亦可作為將由含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G1)與由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R1)預先予以反應而得的(部分)縮合反應物而使用。The above-mentioned polysiloxane (G1) made of an organic polysiloxane such as polydimethylsiloxane containing a silicon-bonded alkenyl group and an organic polysiloxane such as polydimethylsiloxane The resulting polysiloxane resin (R1) can also be used simply by mixing. In addition, the polysiloxane (G1) made of an organic polysiloxane such as polydimethylsiloxane containing a silicon-bonded alkenyl group contains an organic polysiloxane represented by the above general formula (2) In the case of alkane, as long as the characteristics of the present invention are not impaired, it can also be used as a polysiloxane (G1) composed of an organic polysiloxane such as polydimethylsiloxane containing a silicon-bonded alkenyl group and A polysiloxane resin (R1) made of an organic polysiloxane such as polydimethylsiloxane is used as a (partial) condensation reaction product obtained by reacting in advance.
(含於第1形態的黏著劑層的聚矽氧膠(G)的全質量(Gw)與聚矽氧樹脂(R)的全質量(Rw)的質量比(Gw)/(Rw)、及聚矽氧膠(G)與聚矽氧樹脂(R)的合計質量中的具有烯基的聚矽氧膠(G1)的含有比率)
構成第1形態的黏著劑層3的聚矽氧系黏著劑方面,聚矽氧膠(G)的全質量(Gw)一致於加成反應型聚矽氧系黏著劑中的由含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G1)的質量(G1w)。同樣地,構成第1形態的黏著劑層3的聚矽氧系黏著劑方面,聚矽氧樹脂(R)的全質量(Rw)一致於加成反應型聚矽氧系黏著劑中的由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R1)的質量(R1w)。(The mass ratio (Gw)/(Rw) of the total mass (Gw) of the polysiloxane (G) contained in the adhesive layer of the first form to the total mass (Rw) of the polysiloxane (R), and (The content ratio of polysiloxane (G1) with alkenyl group in the total mass of polysiloxane (G) and polysiloxane resin (R))
In terms of the polysiloxane adhesive constituting the
含於第1形態的黏著劑層3的聚矽氧膠(G)的全質量(Gw)與聚矽氧樹脂(R)的全質量(Rw)的質量比(Gw)/(Rw)(=(G1w)/(R1w))是35/65~50/50的範圍為優選。
此外,此情況下,聚矽氧膠(G)與聚矽氧樹脂(R)的合計質量中的具有烯基的聚矽氧膠(G1)的含有比率{(G1w)/((Gw)+(Rw))}×100當然如同上述優選上為35質量%以上且50質量%以下的範圍。The mass ratio (Gw)/(Rw) of the total mass (Gw) of the polysiloxane (G) contained in the
含於第1形態的黏著劑層3的聚矽氧膠(G)的全質量(Gw)與聚矽氧樹脂(R)的全質量(Rw)的質量比(Gw)/(Rw)、及聚矽氧膠(G)與聚矽氧樹脂(R)的合計質量中的具有烯基的聚矽氧膠(G1)的含有比率不足上述範圍的下限值時,對黏著帶1照射光之際,黏著劑難硬化,凝聚力難提升。此情況下,無法獲得期望的附著力降低、保持力試驗中的破壞模式,將黏著帶1使用於半導體元件基板等的切割之後,將獲得的半導體晶片等從黏著帶1剝離之際,被個片化的半導體晶片的拾取性恐變差、恐容易於半導體晶片等產生黏劑殘物。The mass ratio (Gw)/(Rw) of the total mass (Gw) of the silicone (G) contained in the
另一方面,含於第1形態的黏著劑層3的聚矽氧膠(G)的全質量(Gw)與聚矽氧樹脂(R)的全質量(Rw)的質量比(Gw)/(Rw)、及聚矽氧膠(G)與聚矽氧樹脂(R)的合計質量中的具有烯基的聚矽氧膠(G1)的含有比率超過上述範圍的上限值時,照射光前的黏著劑未硬化的狀態下,由於聚矽氧膠(G)成分使得黏著劑層3變過軟。此情況下,在半導體元件基板等的切割時,切割的振動容易傳至黏著劑層3而振幅變大,例如半導體元件基板恐偏離基準位置。然後,隨此,於被個片化的半導體晶片恐產生削片(切削)、每個半導體晶片恐產生大小的偏差。On the other hand, the mass ratio (Gw) of the total mass (Gw) of the silicone (G) contained in the
相對於此,使含於第1形態的黏著劑層3的聚矽氧膠(G)的全質量(Gw)與聚矽氧樹脂(R)的全質量(Rw)的質量比(Gw)/(Rw)、及聚矽氧膠(G)與聚矽氧樹脂(R)的合計質量中的具有烯基的聚矽氧膠(G1)的含有比率為上述的範圍,從而可實現以下的功效。亦即,於紫外線等的光的照射前的階段,可對未硬化的狀態下的黏著劑層3賦予在切割之際不會發生為切斷片的半導體晶片等的飛散的適切的黏著力及附著力。另一方面,光的照射後黏著劑層3硬化使得凝聚力提升,故獲得期望的附著力的降低、保持力試驗方面的破壞模式。此結果,將黏著帶1使用於半導體元件基板等的切割之後,可實現將獲得的半導體晶片等從黏著帶1剝離之際的良好的拾取性,同時可抑制對於半導體晶片等之黏劑殘物。On the other hand, the mass ratio (Gw) of the total mass (Gw) of the polysiloxane (G) contained in the
此外,本發明的加成反應型聚矽氧系黏著劑方面,亦可使用市售的加成反應型聚矽氧系黏著劑。具體而言,例如信越化學工業株式會社製的KR3700、KR3701、X-40-3237-1、X-40-3240、X-40-3291-1、X-40-3229、X-40-3270、X-40-3306(皆商品名)、邁圖高新材料公司製的TSR1512、TSR1516、XR37-B9204(皆商品名)、道康寧東麗株式會社製的SD4580、SD4584、SD4585、SD4560、SD4564、SD4565、SD4570、SD4574、SD4575、SD4600PFC、SD4593、DC7651ADHESIVE(皆商品名)等的型號中,可使用未內添鉑(Pt)系觸媒及後述的交聯劑的類型。In addition, for the addition reaction type silicone adhesive of the present invention, a commercially available addition reaction type silicone adhesive can also be used. Specifically, for example, KR3700, KR3701, X-40-3237-1, X-40-3240, X-40-3291-1, X-40-3229, X-40-3270, manufactured by Shin-Etsu Chemical Industry Co., Ltd. X-40-3306 (both trade names), TSR1512, TSR1516, XR37-B9204 (both trade names) manufactured by Mitu Hi-Tech Materials Co., Ltd., SD4580, SD4584, SD4585, SD4560, SD4564, SD4565, manufactured by Dow Corning Toray Co., Ltd. For models such as SD4570, SD4574, SD4575, SD4600PFC, SD4593, and DC7651ADHESIVE (all trade names), types of platinum (Pt) catalysts and cross-linking agents described below can be used.
(交聯劑) 交聯劑是為了將含於加成反應型聚矽氧系黏著劑的烯基予以交聯而使用。交聯劑方面,使用1分子中具有至少2個優選上3個以上的矽鍵結氫原子(SiH)的有機聚矽氧烷(有機氫聚矽氧烷)。 作為交聯劑而使用的有機氫聚矽氧烷的分子構造方面,例示如直鏈狀、部分具有支鏈的直鏈狀、支鏈狀、網狀。有機氫聚矽氧烷優選上25℃下的黏度為1~5000mPa・s的範圍。 另外,上述黏度可使用BM型旋轉黏度計進行測定。(Crosslinking agent) The crosslinking agent is used to crosslink the alkenyl group contained in the addition reaction type polysiloxane-based adhesive. For the crosslinking agent, an organic polysiloxane (organic hydrogen polysiloxane) having at least two, preferably three or more silicon-bonded hydrogen atoms (SiH) in one molecule is used. Examples of the molecular structure of the organohydrogenpolysiloxane used as a cross-linking agent include straight chains, linear chains partially branched, branched chains, and nets. The organic hydrogen polysiloxane preferably has a viscosity at 25°C of 1 to 5000 mPa·s. In addition, the above viscosity can be measured using a BM type rotary viscometer.
作為交聯劑而使用的有機氫聚矽氧烷可使用歷來眾知者。例如,此有機氫聚矽氧烷方面,雖舉例以下述通式(3)或通式(4)表示者,惟不限定於此等。The organic hydrogen polysiloxane used as the cross-linking agent can be conventionally known. For example, although this organic hydrogen polysiloxane is exemplified by the following general formula (3) or general formula (4), it is not limited thereto.
【化3】…通式(3)【Chemical 3】 …Formula (3)
【化4】…通式(4)【Chemical 4】 …Formula (4)
於此,於通式(3)、通式(4),R3 為碳數1~10的1價烴基,b為0或1,p及q為整數,該有機氫聚矽氧烷的25℃下的黏度成為1~5000mPa・s之值。r為2以上的整數,s為0以上的整數,且r+s≧3,優選上8≧r+s≧3。有機氫聚矽氧烷可為2種以上的混合物。Here, in the general formula (3) and the general formula (4), R 3 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, b is 0 or 1, p and q are integers, and 25 of the organic hydrogen polysiloxane The viscosity at ℃ becomes a value of 1 to 5000 mPa·s. r is an integer of 2 or more, s is an integer of 0 or more, and r+s≧3, preferably 8≧r+s≧3. Organic hydrogen polysiloxane can be a mixture of two or more.
R3 為碳數1~10優選上碳數1~7的1價烴基。舉例如甲基、乙基、丙基、及丁基等的烷基、環己基等的環烷基、及苯基、及甲苯基等的芳香基、乙烯基及烯丙基等的烯基。尤其,甲基或苯基為優選。R 3 is a monovalent hydrocarbon group having 1 to 10 carbon atoms and preferably 1 to 7 carbon atoms. Examples include alkyl groups such as methyl, ethyl, propyl, and butyl, cycloalkyl groups such as cyclohexyl, aromatic groups such as phenyl and tolyl, and alkenyl groups such as vinyl and allyl. In particular, methyl or phenyl is preferred.
作為第1形態的黏著劑層3中的交聯劑而使用的有機氫聚矽氧烷的含量優選上為對於由含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G1)中的烯基的總量之有機氫聚矽氧烷中的矽鍵結氫原子(SiH)的總量成為0.15mol當量以上且15.0mol當量以下的範圍之量,成為1.0mol當量以上且10.0mol當量以下的範圍之量更優選。The content of the organic hydrogen polysiloxane used as the cross-linking agent in the
有機氫聚矽氧烷的含量不足上述下限值的情況下,對黏著帶1照射光之際,黏著劑難硬化,凝聚力難提升。此情況下,無法獲得期望的附著力降低、保持力試驗中的破壞模式,將黏著帶1使用於半導體元件基板等的切割之後,將獲得的半導體晶片等從黏著帶1剝離之際,被個片化的半導體晶片的拾取性恐變差、恐容易於半導體晶片等產生黏劑殘物。When the content of the organic hydrogen polysiloxane is less than the above lower limit, when the
另一方面,有機氫聚矽氧烷的含量超過上述上限值的情況下,未反應的有機氫聚矽氧烷恐汙染半導體晶片。此外,未反應的有機氫聚矽氧烷中的矽鍵結氫原子(SiH)與空氣中的氧、水分反應而變化為SiOH,黏著劑層3的對於被黏體的黏著力變大,被個片化的半導體晶片的拾取性恐變差。On the other hand, if the content of the organic hydrogen polysiloxane exceeds the above upper limit, unreacted organic hydrogen polysiloxane may contaminate the semiconductor wafer. In addition, the silicon-bonded hydrogen atoms (SiH) in the unreacted organic hydrogen polysiloxane react with oxygen and moisture in the air to change to SiOH, and the adhesive force of the
第1形態的黏著劑層3中的交聯劑的含量如上述般,以對於由含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G1)中的烯基的總量之有機氫聚矽氧烷中的矽鍵結氫原子(SiH)的總量成為上述的範圍內的方式進行調整即可。
符合此範圍的交聯劑的含量方面,雖因交聯劑具有的矽鍵結氫原子(SiH)的個數而不同,惟例如對於加成反應型聚矽氧系黏著劑的固含量100質量份,將交聯劑以固含量成為0.2質量份以上且20.0質量份以下的範圍的方式進行添加即可。The content of the cross-linking agent in the
使對於加成反應型聚矽氧系黏著劑之交聯劑的含量為上述的範圍,使得在將半導體晶片從切割用黏著帶剝離之際,將紫外線等的光對黏著劑層3照射,從而使聚矽氧系黏著劑中的感光鉑(Pt)觸媒被活性化,加成反應型聚矽氧系黏著劑與對於該加成反應型聚矽氧系黏著劑之交聯劑的交聯反應被促進,致使黏著劑的凝聚力變比光照射前大。此結果,黏著劑層3的附著力適切降低,可實現將半導體晶片等從黏著帶1剝離之際的良好的拾取性,同時可抑制對於半導體晶片等之黏劑殘物。The content of the crosslinking agent for the addition reaction type polysiloxane-based adhesive is within the above range, so that when the semiconductor wafer is peeled from the dicing adhesive tape, ultraviolet light or the like is irradiated to the
交聯劑方面,只要為作為加成反應型聚矽氧系黏著劑的交聯劑而使用者即可,亦即只要為在1分子中具有至少2個矽鍵結氫原子(SiH)的有機聚矽氧烷(有機氫聚矽氧烷)即可,無特別限定。具體而言,舉例如信越化學株式會社製的X-92-122(商品名)、道康寧東麗株式會社製的BY24-741(商品名)等。As for the crosslinking agent, as long as it is a crosslinking agent of an addition reaction type polysiloxane-based adhesive, that is, as long as it is an organic having at least two silicon-bonded hydrogen atoms (SiH) in one molecule Polysiloxane (organic hydrogen polysiloxane) is sufficient, and is not particularly limited. Specific examples include X-92-122 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., and BY24-741 (trade name) manufactured by Dow Corning Toray Co., Ltd. and the like.
(感光鉑(Pt)觸媒)
感光鉑(Pt)觸媒用於透過紫外線等的光的照射從而予以促進構成黏著劑層3的加成反應型聚矽氧系黏著劑與交聯劑的加成反應(矽氫化)所致的硬化。可為了予以促進加成反應型聚矽氧系黏著劑與交聯劑的加成反應所致的硬化而使用的光的波長優選上為240nm以上且400nm以下的範圍。
感光鉑(Pt)觸媒方面,從感光性及反應速度良好的觀點而言,優選上使用光活性環戊二烯基鉑(IV)化合物。(Photosensitive platinum (Pt) catalyst)
The photosensitive platinum (Pt) catalyst is used to irradiate light such as ultraviolet rays to promote the addition reaction (hydrosilylation) of the addition reaction type polysiloxane-based adhesive constituting the
此光活性環戊二烯基鉑(IV)化合物方面,非特別限定者,舉例如(環戊二烯)二甲基三甲基甲矽烷基甲基鉑、(環戊二烯)二乙基三甲基甲矽烷基甲基鉑、(環戊二烯)二丙基三甲基甲矽烷基甲基鉑、(環戊二烯)二異丙基三甲基甲矽烷基甲基鉑、(環戊二烯)二烯丙基三甲基甲矽烷基甲基鉑、(環戊二烯)二苄基三甲基甲矽烷基甲基鉑、(環戊二烯)二甲基三乙基甲矽烷基甲基鉑、(環戊二烯)二甲基三丙基甲矽烷基甲基鉑、(環戊二烯)二甲基三異丙基甲矽烷基甲基鉑、(環戊二烯)二甲基三苯基甲矽烷基甲基鉑、(環戊二烯)二甲基二甲基苯基甲矽烷基甲基鉑、(環戊二烯)二甲基甲基二苯基甲矽烷基甲基鉑、(環戊二烯)二甲基二甲基(三甲基甲矽烷氧基)甲矽烷基甲基鉑、(環戊二烯)二甲基二甲基(二甲基乙烯基甲矽烷氧基)甲矽烷基甲基鉑、[(1’-萘基)環戊二烯]三甲基甲矽烷基甲基鉑、[(2’-萘基)環戊二烯]三甲基甲矽烷基甲基鉑、[1-甲基-3-(1’-萘基)環戊二烯]三甲基甲矽烷基甲基鉑、[1-甲基-3-(2’-萘基)環戊二烯]三甲基甲矽烷基甲基鉑、[(4’-聯苯)環戊二烯]三甲基甲矽烷基甲基鉑、[1-(4’-聯苯)-3-甲基環戊二烯]三甲基甲矽烷基甲基鉑、[(9’-菲基)環戊二烯]三甲基甲矽烷基甲基鉑、[1-甲基-3-(9’-菲基)環戊二烯]三甲基甲矽烷基甲基鉑、[1-(2’-蒽基)-3-甲基環戊二烯]三甲基甲矽烷基甲基鉑、[(2’-蒽基)環戊二烯]三甲基甲矽烷基甲基鉑、[(1’-芘基)環戊二烯]三甲基甲矽烷基甲基鉑、[1-甲基-3-(1’-芘基)環戊二烯]三甲基甲矽烷基甲基鉑等。The photoactive cyclopentadienyl platinum (IV) compound is not particularly limited, and examples thereof include (cyclopentadiene) dimethyltrimethylsilylmethyl platinum, (cyclopentadiene) diethyl Trimethylsilylmethylplatinum, (cyclopentadiene) dipropyltrimethylsilylmethylplatinum, (cyclopentadiene) diisopropyltrimethylsilylmethylplatinum, ( (Cyclopentadiene) diallyl trimethylsilyl methyl platinum, (cyclopentadiene) dibenzyl trimethyl silyl methyl platinum, (cyclopentadiene) dimethyl triethyl Silylmethylplatinum, (cyclopentadiene) dimethyltripropylsilylmethylplatinum, (cyclopentadiene) dimethyltriisopropylsilylmethylplatinum, (cyclopentadiene) (Ene) dimethyltriphenylsilylmethylplatinum, (cyclopentadiene) dimethyldimethylphenylsilylmethylplatinum, (cyclopentadiene) dimethylmethyldiphenyl Silylmethyl platinum, (cyclopentadiene) dimethyl dimethyl (trimethylsilyloxy) silyl methyl platinum, (cyclopentadiene) dimethyl dimethyl (dimethyl Vinylvinylsilyloxy)silylmethylplatinum, [(1'-naphthyl)cyclopentadiene] trimethylsilylmethylplatinum, [(2'-naphthyl)cyclopentadiene ]Trimethylsilylmethylplatinum, [1-methyl-3-(1'-naphthyl)cyclopentadiene]trimethylsilylmethylplatinum, [1-methyl-3-( 2'-naphthyl)cyclopentadiene]trimethylsilylmethylplatinum, [(4'-biphenyl)cyclopentadiene]trimethylsilylmethylplatinum,[1-(4' -Biphenyl)-3-methylcyclopentadiene]trimethylsilylmethylplatinum, [(9'-phenanthrene)cyclopentadiene]trimethylsilylmethylplatinum,[1- Methyl-3-(9'-phenanthrene)cyclopentadiene]trimethylsilylmethylplatinum, [1-(2'-anthryl)-3-methylcyclopentadiene]trimethyl Silylmethylplatinum, [(2'-anthracenyl)cyclopentadiene]trimethylsilylmethylplatinum, [(1'-pyrene)cyclopentadiene]trimethylsilylmethyl Platinum, [1-methyl-3-(1'-pyrene)cyclopentadiene]trimethylsilylmethyl platinum, etc.
上述的化合物中的環戊二烯環亦能以利用甲基、氯基、氟基、三甲基甲矽烷基、三乙基甲矽烷基、二甲基苯基甲矽烷基、甲基二苯基矽烷基、三苯基甲矽烷基、苯基、氟苯基、氯苯基、甲氧基、萘基、聯苯、蒽基、芘基、2-苯甲醯萘、噻噸酮、2-氯噻噸酮、2-異丙基噻噸酮、蒽醌、1-氯蒽醌、苯乙酮、二苯甲酮、9,10-二甲基蒽、9,10-二氯蒽及從此等之中選擇的1個以上的基進行置換的環戊二烯環而置換。 此外,於上述的化合物,亦可環戊二烯環被置換為η5-芴基。The cyclopentadiene ring in the above compounds can also use methyl, chloro, fluoro, trimethylsilyl, triethylsilyl, dimethylphenylsilyl, methyldiphenyl Silyl group, triphenylsilyl group, phenyl group, fluorophenyl group, chlorophenyl group, methoxy group, naphthyl group, biphenyl group, anthracenyl group, pyrenyl group, 2-benzylnaphthalene, thioxanthone, 2 -Chlorothioxanthone, 2-isopropylthioxanthone, anthraquinone, 1-chloroanthraquinone, acetophenone, benzophenone, 9,10-dimethylanthracene, 9,10-dichloroanthracene and One or more groups selected from these are substituted with a substituted cyclopentadiene ring. In addition, in the above-mentioned compound, the cyclopentadiene ring may be substituted with η5-fluorenyl.
上述的化合物中的環戊二烯環方面,未被置換者、以1個以上的芳香族有機基進行置換者、以1個以上的脂肪族有機基進行置換者、以1個以上的芳香族有機基與1個以上的脂肪族有機基進行置換者為優選。此外,被環戊二烯環置換的有機基方面,萘基、聯苯、蒽基、菲基及芘基為優選。In terms of the cyclopentadiene ring in the above compounds, those who are not substituted, those substituted with one or more aromatic organic groups, those substituted with one or more aliphatic organic groups, and those substituted with one or more aromatic groups It is preferable that the organic group is substituted with one or more aliphatic organic groups. In addition, naphthyl, biphenyl, anthryl, phenanthryl, and pyrenyl are preferred as the organic group substituted with a cyclopentadiene ring.
第1形態的黏著劑層3中的感光鉑(Pt)觸媒的含量是只要可透過紫外線等的光的照射從而促進加成反應型聚矽氧系黏著劑與交聯劑的加成反應,則無特別限定。第1形態的黏著劑層3中的感光鉑(Pt)觸媒的含量優選上,例如對於加成反應型聚矽氧系黏著劑的固含量100質量份,固含量下為0.1質量份以上且3.0質量份以下的範圍。The content of the photosensitive platinum (Pt) catalyst in the
(凝聚力提升劑)
凝聚力提升劑是為了使黏著劑層3的凝聚力提升而依所需使用。凝聚力提升劑方面,非特別限定者,例如使用多官能硫醇。由多官能硫醇所成的凝聚力提升劑方面,舉例如昭和電工株式會社製的Karenz(註冊商標)MT-PE1、KarenzMT-NR1等。(Cohesion enhancer)
The cohesiveness enhancer is used as needed to improve the cohesiveness of the
其中,多官能硫醇不相容於加成反應型聚矽氧系黏著劑,故要使用多官能硫醇作為凝聚力提升劑,需要使用加成反應型聚矽氧系黏著劑與多官能硫醇的相容劑。相容劑方面,非特別限定者,舉例如為具有巰基的矽烷偶聯劑的信越化學工業株式會社製的KBM-802、KBM-803(皆商品名)、道康寧東麗株式會社製的SH6062(商品名)等。
黏著劑層3方面使用凝聚力提升劑的情況下,凝聚力提升劑的添加量對於加成反應型聚矽氧系黏著劑的固含量100質量份,固含量下6質量份以下的範圍為優選。凝聚力提升劑的添加量對於加成反應型聚矽氧系黏著劑的固含量100質量份在固含量下超過6質量份的情況下,即使添加相容劑,加成反應型聚矽氧系黏著劑與為凝聚力提升劑的多官能硫醇恐相分離。Among them, multifunctional thiol is not compatible with addition reaction type polysiloxane adhesive, so to use multifunctional thiol as cohesiveness enhancer, it is necessary to use addition reaction type polysiloxane adhesive and multifunctional thiol Compatibilizer. In terms of the compatibilizer, those not particularly limited include, for example, KBM-802, KBM-803 (both trade names) manufactured by Shin-Etsu Chemical Co., Ltd. having a silane coupling agent having a mercapto group, and SH6062 (manufactured by Dow Corning Toray Co., Ltd.). Trade name) etc.
When the cohesiveness enhancer is used for the
(補強填充劑)
補強填充劑是為了使黏著劑層3的強度提升而依所需使用。補強填充劑方面,非特別限定者,舉例如日本AEROSIL株式會社製的熱解法二氧化矽(註冊商標)130、熱解法二氧化矽200、熱解法二氧化矽300、Tokuyama株式會社製的REOLOSIL(註冊商標)QS-102、REOLOSILQS-30、DSL.JAPAN株式會社製的CARPLEX(註冊商標)80、PPG製的Hi-Sil(註冊商標)-233-D等。(Reinforcing filler)
The reinforcing filler is used as needed to improve the strength of the
<第2形態的黏著劑層>
第2形態的黏著劑層3除第1形態的黏著劑層3包含的加成反應型聚矽氧系黏著劑、交聯劑及感光鉑(Pt)觸媒以外,包含過氧化物固化型聚矽氧系黏著劑。此外,第2形態的黏著劑層3亦可包含使過氧化物固化型聚矽氧系黏著劑的聚合反應開始的引發劑。再者,第2形態的黏著劑層3如同第1形態的黏著劑層3,亦可依所需包含補強填充劑、凝聚力提升劑、著色劑等的其他添加劑。<Adhesive layer of the second form>
The second embodiment of the
(過氧化物固化型聚矽氧系黏著劑) 過氧化物固化型聚矽氧系黏著劑雖可使用歷來眾知者,惟一般而言為包含由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G2)、和由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R2)的黏著劑。另外,含於過氧化物固化型聚矽氧系黏著劑的由有機聚矽氧烷所成的聚矽氧膠(G2)與含於加成反應型聚矽氧系黏著劑的聚矽氧膠(G1)不同,一般而言,不含有矽鍵結烯基。(Peroxide-curing polysiloxane-based adhesive) Peroxide-curable polysiloxane-based adhesives can be used, but generally speaking, they are polysiloxanes (G2) composed of organic polysiloxanes such as polydimethylsiloxane. , Adhesive of polysiloxane resin (R2) made of organic polysiloxane such as polydimethylsiloxane. In addition, the polysiloxane adhesive (G2) made of organic polysiloxane contained in the peroxide-curing polysiloxane adhesive and the polysiloxane adhesive contained in the addition reaction type polysiloxane adhesive (G1) is different. Generally speaking, it does not contain a silicon-bonded alkenyl group.
以下,就含於過氧化物固化型聚矽氧系黏著劑的由不含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G2)、和由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R2)進一步詳細進行說明。 另外,於以下的說明,有時將由不含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G2)僅記載為由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G2)。The following is a polysiloxane (G2) made of organic polysiloxane such as polydimethylsiloxane which does not contain silicon-bonded alkenyl group, contained in peroxide-curing polysiloxane adhesive (G2) , And polysiloxane resin (R2) made of organic polysiloxane such as polydimethylsiloxane, which will be described in further detail. In addition, in the following description, the polysiloxane (G2) made of an organic polysiloxane such as polydimethylsiloxane that does not contain a silicon-bonded alkenyl group may be described only as polydimethyl Polysiloxane (G2) made of organic polysiloxane such as silicone.
[由不含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G2)] 本實施方式中的由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G2)為使用於過氧化物固化型聚矽氧系黏著劑者即可,亦即為不含有矽鍵結烯基者即可,無特別限定。如此的有機聚矽氧烷的分子構造方面,舉例如主鏈部分由二有機矽氧烷單位的重複所成的直鏈狀構造、該分子構造的一部分包含支鏈的構造、支鏈狀構造或環狀體構造。[Polysiloxane (G2) made of organic polysiloxane such as polydimethylsiloxane that does not contain silicon-bonded alkenyl groups] The polysiloxane (G2) made of organic polysiloxane such as polydimethylsiloxane in this embodiment may be used for peroxide-curing polysiloxane-based adhesives, that is, There is no particular limitation as long as it does not contain a silicon-bonded alkenyl group. The molecular structure of such an organic polysiloxane includes, for example, a linear structure formed by repeating diorganosiloxane units in the main chain portion, a structure in which a part of the molecular structure includes a branched structure, a branched structure, or Ring structure.
由不含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G2)可為油狀或生膠狀,惟生膠狀為優選。
油狀的情況下,由有機聚矽氧烷的所成聚矽氧膠(G2)的黏度優選上於25℃下為1000mPa・s以上。上述黏度不足1000mPa・s時,存在光照射前後的黏著劑無法發現期望的黏著特性之虞、黏著劑層3與基材2的密接性劣化之虞。
生膠狀的情況下,將由有機聚矽氧烷的所成聚矽氧膠(G2),以甲苯溶解為30質量%的濃度時的黏度優選上為25℃下100000mPa・s以下。上述黏度超過100000mPa・s時,調製黏著劑組成物時的攪拌恐變困難。
另外,上述黏度可使用BM型旋轉黏度計進行測定。The polysiloxane (G2) made of an organic polysiloxane such as polydimethylsiloxane that does not contain a silicon-bonded alkenyl group may be in the form of an oil or a raw gum, but the raw gum is preferred.
In the case of oil, the viscosity of the polysiloxane (G2) made of organic polysiloxane is preferably 1000 mPa·s or more at 25°C. When the viscosity is less than 1000 mPa·s, the adhesive before and after light irradiation may not be able to find the desired adhesive properties, and the adhesiveness between the
由不含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G2)例如雖舉例以下述通式(5)或通式(6)表示者,惟不限定於此等。A polysiloxane (G2) made of an organic polysiloxane such as polydimethylsiloxane which does not contain a silicon-bonded alkenyl group is represented by, for example, the following general formula (5) or general formula (6) However, it is not limited to this.
【化5】…通式(5)【Chemical 5】 …Formula (5)
【化6】…通式(6)【Chemical 6】 …Formula (6)
於此,於上述通式(5)、通式(6),R4 為彼此獨立不具有脂肪族不飽和結合的1價烴基,t為100以上的整數,為上述二有機聚矽氧烷的25℃下的黏度成為1000mPa・s以上的值。Here, in the above general formula (5) and general formula (6), R 4 is a monovalent hydrocarbon group independently having no aliphatic unsaturated bond, and t is an integer of 100 or more, which is that of the above diorganopolysiloxane The viscosity at 25°C becomes a value of 1000 mPa·s or more.
R4 方面,優選上為碳數1~10優選上碳數1~7的不具有脂肪族不飽和結合的1價烴基。舉例如甲基、乙基、丙基、及丁基等的烷基、環己基等的環烷基、及苯基、及甲苯基等的芳香基等,尤其甲基為優選。R 4 is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms and preferably having 1 to 7 carbon atoms which does not have an aliphatic unsaturated bond. Examples include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, and aromatic groups such as phenyl groups and tolyl groups. In particular, methyl groups are preferred.
[由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R2)]
本實施方式中的由聚二甲基矽氧烷等的有機聚矽氧烷的所成的聚矽氧樹脂(R2)可使用與使用於上述的加成反應型聚矽氧系黏著劑的由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R1)同樣者。亦即,由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R2)為具有R2 3
SiO0.5
單元(M單元)及SiO2
單元(Q單元)的有機聚矽氧烷,為稱為所謂MQ樹脂者。此由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R1)基本上在分子內不具有烯基,可使用歷來眾知者。R2
為碳數1~10的1價烴基,舉例上述的在R1
方面例示者。上述有機聚矽氧烷是以R2 3
SiO0.5
單元/SiO2
單元的莫耳比成為0.5以上且1.7以下的範圍的方式含有R2 3
SiO0.5
單元及SiO2
單元為優選。R2 3
SiO0.5
單元/SiO2
單元的莫耳比不足0.5時,獲得的黏著劑層3的黏著力、附著力有時降低。另一方面,R2 3
SiO0.5
單元/SiO2
單元的莫耳比超過1.7時,獲得的黏著劑層3的黏著力、保持力有時降低。另外,上述有機聚矽氧烷可具有OH基。該情況下,OH基的含量優選上相對於上述有機聚矽氧烷的總質量為4.0質量%以下。OH基超過上述上限值時黏著劑的硬化性有時降低。[Polysiloxane resin (R2) made of organic polysiloxane such as polydimethylsiloxane] In this embodiment, it is made of organic polysiloxane such as polydimethylsiloxane. The polysiloxane resin (R2) can be the same as the polysiloxane resin (R1) made of organic polysiloxane such as polydimethylsiloxane used in the above addition reaction type polysiloxane adhesive. ) Same. That is, the polysiloxane resin (R2) made of organic polysiloxane such as polydimethylsiloxane is an organic having R 2 3 SiO 0.5 unit (M unit) and SiO 2 unit (Q unit) Polysiloxane is called MQ resin. The polysiloxane resin (R1) made of organic polysiloxane such as polydimethylsiloxane does not basically have an alkenyl group in the molecule, and it can be used by a publicly known person. R 2 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and exemplified above for R 1 is exemplified. It is preferable that the organic polysiloxane contains R 2 3 SiO 0.5 units and SiO 2 units so that the molar ratio of R 2 3 SiO 0.5 units/SiO 2 units becomes 0.5 or more and 1.7 or less. When the molar ratio of R 2 3 SiO 0.5 unit/SiO 2 unit is less than 0.5, the adhesive force and adhesive force of the obtained
本案為了使黏著力為2.4N/10mm以上且5.5N/10mm以下,優選上在由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R2)方面使用MQ樹脂。其中合成MQ樹脂之際的雜質方面,亦可包含R2 SiO1.5 單元(T單元)及/或R2 2 SiO單元(D單元)。In this case, in order to make the adhesive force 2.4N/10mm or more and 5.5N/10mm or less, it is preferable to use MQ resin for the polysiloxane resin (R2) made of organic polysiloxane such as polydimethylsiloxane . Among the impurities when synthesizing the MQ resin, R 2 SiO 1.5 units (T units) and/or R 2 2 SiO units (D units) may also be included.
上述的由不含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G2)與由聚二甲基矽氧烷等的有機聚矽氧烷的所成的聚矽氧樹脂(R2)亦可單純混合而使用。此外,由不含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G2)方面,含有以上述通式(6)表示的有機聚矽氧烷的情況下,只要不損及本發明的特性,亦可作為將由不含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G2)與由聚二甲基矽氧烷等的有機聚矽氧烷的所成的聚矽氧樹脂(R2)預先予以反應而得的(部分)縮合反應物而使用。The above-mentioned polysiloxane (G2) made of an organic polysiloxane such as polydimethylsiloxane that does not contain a silicon-bonded alkenyl group and an organic polysiloxane made of polydimethylsiloxane or the like The polysiloxane resin (R2) made of alkanes can also be used by simply mixing them. In addition, the polysiloxane (G2) made of an organic polysiloxane such as polydimethylsiloxane which does not contain a silicon-bonded alkenyl group contains the organic polysilicon represented by the general formula (6) In the case of oxane, as long as the characteristics of the present invention are not impaired, it can also be used as a polysiloxane (G2) made of an organic polysiloxane such as polydimethylsiloxane which does not contain a silicon-bonded alkenyl group. ) It is used as a (partial) condensation reaction product obtained by reacting a polysiloxane resin (R2) made of an organic polysiloxane such as polydimethylsiloxane in advance.
(含於第2形態的黏著劑層的聚矽氧膠(G)的全質量(Gw)與聚矽氧樹脂(R)的全質量(Rw)的質量比(Gw)/(Rw)、及聚矽氧膠(G)與聚矽氧樹脂(R)的合計質量中的具有烯基的聚矽氧膠(G1)的含有比率)
如上述般,構成第2形態的黏著劑層3的聚矽氧系黏著劑包含加成反應型聚矽氧系黏著劑與過氧化物固化型聚矽氧系黏著劑。因此,構成第2形態的黏著劑層3的聚矽氧系黏著劑方面,聚矽氧膠(G)的全質量(Gw)為加成反應型聚矽氧系黏著劑中的由含有矽鍵結烯基的聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G1)的質量(G1w)、和過氧化物固化型聚矽氧系黏著劑中的不含有矽鍵結烯基的由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧膠(G2)的質量(G2w)的合計質量。此外,構成第2形態的黏著劑層3的聚矽氧系黏著劑方面,聚矽氧樹脂(R)的全質量(Rw)為加成反應型聚矽氧系黏著劑中的由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R1)的質量(R1w)、和過氧化物固化型聚矽氧系黏著劑中的由聚二甲基矽氧烷等的有機聚矽氧烷所成的聚矽氧樹脂(R2)的質量(R2w)的合計質量。(The mass ratio (Gw)/(Rw) of the total mass (Gw) of the polysiloxane (G) contained in the adhesive layer of the second form to the total mass (Rw) of the polysiloxane (R), and (The content ratio of polysiloxane (G1) with alkenyl group in the total mass of polysiloxane (G) and polysiloxane resin (R))
As described above, the polysiloxane-based adhesive constituting the
含於第2形態的黏著劑層3的聚矽氧膠(G)的全質量(Gw)與聚矽氧樹脂(R)的全質量(Rw)的質量比(Gw)/(Rw)(=(G1w+G2w)/(R1w+R2w))優選上為40/60~56/44的範圍。
此外,此情況下,聚矽氧膠(G)與聚矽氧樹脂(R)的合計質量中的具有烯基的聚矽氧膠(G1)的含有比率{(G1w)/((Gw)+(Rw))}×100優選上為14質量%以上且42質量%以下的範圍。The mass ratio (Gw)/(Rw) of the total mass (Gw) of the silicone (G) contained in the
含於第2形態的黏著劑層3的聚矽氧膠(G)的全質量(Gw)與聚矽氧樹脂(R)的全質量(Rw)的質量比(Gw)/(Rw)不足上述範圍的下限值時,黏著劑層3的黏著力、附著力恐降低。此情況下,將黏著帶1用於後述的半導體元件基板、螢光基板等的切割的情況下,為切斷片之半導體晶片等恐飛散。The mass ratio (Gw)/(Rw) of the total mass (Gw) of the silicone (G) contained in the
另一方面,含於第2形態的黏著劑層3的聚矽氧膠(G)的全質量(Gw)與聚矽氧樹脂(R)的全質量(Rw)的質量比(Gw)/(Rw)超過上述範圍之上限值時,加成反應型聚矽氧系黏著劑中的聚矽氧膠(G1)的質量特多的情況下,照射光前的黏著劑未硬化的狀態下,由於聚矽氧膠(G)成分使得黏著劑層3變過軟。此情況下,在半導體元件基板等的切割時,切割的振動容易傳至黏著劑層3而振幅變大,例如半導體元件基板恐偏離基準位置。然後,隨此,於被個片化的半導體晶片恐產生削片(切削)、每個半導體晶片恐產生大小的偏差。
此外,過氧化物固化型聚矽氧系黏著劑中的聚矽氧膠(G2)的質量特多的情況下,引發劑所致的過氧化物固化型聚矽氧系黏著劑的硬化容易進展,黏著劑層3的黏著力、附著力恐降低。此情況下,將黏著帶1用於後述的半導體元件基板、螢光基板等的切割的情況下,為切斷片之半導體晶片等恐飛散。On the other hand, the mass ratio (Gw) of the total mass (Gw) of the silicone (G) contained in the
第2形態的黏著劑層3中的聚矽氧膠(G)與聚矽氧樹脂(R)的合計質量中的具有烯基的聚矽氧膠(G1)的含有比率不足上述範圍的下限值時,對黏著帶1照射光之際,黏著劑難硬化,凝聚力難提升。此情況下,無法獲得期望的附著力降低、保持力試驗中的破壞模式,將黏著帶1使用於半導體元件基板等的切割之後,將獲得的半導體晶片等從黏著帶1剝離之際,被個片化的半導體晶片的拾取性恐變差、恐容易於半導體晶片等產生黏劑殘物。The content ratio of the polysiloxane (G1) having an alkenyl group in the total mass of the polysiloxane (G) and the polysiloxane resin (R) in the
另一方面,第2形態的黏著劑層3中的聚矽氧膠(G)與聚矽氧樹脂(R)的合計質量中的具有烯基的聚矽氧膠(G1)的含有比率超過上述範圍之上限值時,照射光前的黏著劑未硬化的狀態下,由於聚矽氧膠(G)成分使得黏著劑層3變過軟。此情況下,在半導體元件基板等的切割時,切割的振動容易傳至黏著劑層3而振幅變大,例如,半導體元件基板恐偏離基準位置。然後,隨此,於被個片化的半導體晶片恐產生削片(切削)、每個半導體晶片恐產生大小的偏差。On the other hand, the content ratio of the polysiloxane (G1) having an alkenyl group in the total mass of the polysiloxane (G) and the polysiloxane resin (R) in the
第2形態的黏著劑層3中的過氧化物固化型聚矽氧系黏著劑的含量在與加成反應型聚矽氧系黏著劑混合之際,以含於第2形態的黏著劑層的聚矽氧膠(G)的全質量(Gw)與聚矽氧樹脂(R)的全質量(Rw)的質量比(Gw)/(Rw)、及聚矽氧膠(G)與聚矽氧樹脂(R)的合計質量中的具有烯基的聚矽氧膠(G1)的含有比率成為上述的範圍的方式,考量過氧化物固化型聚矽氧系黏著劑的聚矽氧膠(G2)與聚矽氧樹脂(R2)的比率而進行調整即可。
使第2形態的黏著劑層3中的過氧化物聚矽氧系黏著劑的含量為上述的範圍,使得在將黏著帶1用於半導體元件基板、螢光基板等的切割的情況下,可抑制為切斷片的半導體晶片等的飛散、將黏著帶1剝離之際的黏劑殘物。The content of the peroxide-curable polysiloxane-based adhesive in the
此外,本發明的過氧化物固化型聚矽氧系黏著劑方面,亦可使用市售的過氧化物固化型聚矽氧系黏著劑。具體而言,舉例如信越化學工業株式會社製的KR100、KR101-10(皆商品名)、邁圖高新材料公司製的YR3340、YR3286、PSA610-SM、XR37-B6722(皆商品名)、道康寧東麗株式會社製的SH4280、SH4282、SE4200、BY24-717、BY24-715、Q2-7735(皆商品名)等。In addition, in the peroxide-curable silicone adhesive of the present invention, a commercially available peroxide-curable silicone adhesive can also be used. Specifically, for example, KR100, KR101-10 (all brand names) manufactured by Shin-Etsu Chemical Industry Co., Ltd., YR3340, YR3286, PSA610-SM, XR37-B6722 (all brand names) manufactured by Mitu Hi-Tech Materials Co., Ltd., Dow Corning East SH4280, SH4282, SE4200, BY24-717, BY24-715, Q2-7735 (all trade names) manufactured by Rei Corporation.
(引發劑) 引發劑方面,使用過氧化物,更具體而言使用有機過氧化物。作為引發劑而使用的有機過氧化物方面,非特別限定者,舉例如過氧化苯甲醯、過氧化二異丙苯、2,5-二甲基-2,5-二(t-過氧化)己烷、1,1´-二-t-過氧化-3,3,5-三亞甲基環己烷、1,3-二-(t-過氧化)-二異丙苯等,市售品方面,舉例如日油株式會社製的NYPERK40等。(Initiator) For the initiator, peroxides are used, more specifically organic peroxides. The organic peroxide used as an initiator is not particularly limited, and examples thereof include benzoyl peroxide, dicumyl peroxide, and 2,5-dimethyl-2,5-bis(t-peroxide ) Hexane, 1,1´-di-t-peroxy-3,3,5-trimethylenecyclohexane, 1,3-di-(t-peroxy)-dicumyl, etc., commercially available Examples of products include NYPERK40 manufactured by NOF Corporation.
第2形態的黏著劑層3中的引發劑的含量對於過氧化物固化型聚矽氧系黏著劑的固含量100質量份,優選上固含量下為10質量份以下。第2形態的黏著劑層3中的引發劑的含量對於過氧化物固化型聚矽氧系黏著劑的固含量100質量份,固含量下超過10質量份的情況下,於黏著劑層3有時過氧化物固化型聚矽氧系黏著劑的硬化反應恐過度進展。此情況下,黏著劑層3變硬,黏著帶1的黏著力容易變低。然後,將此黏著帶1使用於半導體元件基板等的切割時,在將半導體元件基板等切斷之際,為切斷片的半導體晶片等恐容易從黏著帶1剝離而飛散。The content of the initiator in the
<厚度>
黏著劑層3的厚度優選上為10μm以上且100μm以下的範圍,更優選上為20μm以上且40μm以下的範圍。黏著劑層3的厚度不足10μm的情況下,含於黏著劑層3的聚矽氧系黏著劑的厚度變薄,故黏著帶1的黏著力容易降低。另一方面,黏著劑層3的厚度比100μm厚的情況下,恐容易發生黏著劑層3的聚力失效。然後,將黏著帶1使用於半導體元件基板等的切割之後,將獲得的半導體晶片等從黏著帶1剝離之際,恐容易於半導體晶片等產生黏劑殘物。此外,在半導體元件基板等的切割時,切割的振動容易傳至黏著劑層3而振幅變大,例如半導體元件基板恐偏離基準位置。然後,隨此,於被個片化的半導體晶片恐產生削片(切削)、每個半導體晶片恐產生大小的偏差。<Thickness>
The thickness of the
<錨固塗層>
如上述般,在本實施方式的黏著帶1,亦可依黏著帶1的製造條件、製造後的黏著帶1的使用條件等,在基材2與黏著劑層3之間,設置配合基材2的種類下的錨固塗層,實施電暈處理等的表面處理。藉此,可使基材2與黏著劑層3的密接力改善。<Anchor coating>
As described above, in the
<表面處理>
在基材2的表面(與黏著劑層3相向之面的相反側的面),亦可實施剝離性改良處理等的表面處理。用於基材2的表面處理的處理劑方面,非特別限定者,例如可使用長鏈烷基乙烯基單體聚合物、氟化烷基乙烯基單體聚合物、聚乙烯醇氨基甲酸酯、胺基醇酸系樹脂等的非聚矽氧系的剝離處理劑等。如此的非聚矽氧系的剝離處理劑方面,舉例如IPPOSHA OIL INDUSTRIES株式會社製的PEELOIL1050、PEELOIL1200等。<Surface treatment>
The surface of the base material 2 (the surface on the opposite side to the surface facing the adhesive layer 3) may be subjected to surface treatment such as peelability improvement treatment. The treatment agent used for the surface treatment of the
<剝離膜>
此外,在黏著劑層3的表面(與基材2相向之面的相反側的面),亦可依所需設置剝離膜。剝離膜方面,可使用對紙、聚乙烯、聚丙烯、聚對苯二甲酸乙二酯等的膜實施為了提高與含於黏著劑層3的聚矽氧系黏著劑的脫模性用的剝離處理者。用於剝離膜的剝離處理的材料方面,不特別限定,例如可使用氟烷基變性矽氧聚合物、長鏈烷基乙烯基單體聚合物、胺基醇酸系樹脂等的材料。<Release film>
In addition, a peeling film may be provided on the surface of the adhesive layer 3 (the surface on the side opposite to the surface facing the substrate 2) as required. For the release film, a film such as paper, polyethylene, polypropylene, polyethylene terephthalate, etc. can be used to perform release for improving the releasability with the silicone adhesive contained in the
<黏著帶的厚度>
具有如以上說明的構成的黏著帶1的整體上的厚度優選上為20μm以上且200μm以下的範圍。
黏著帶1的厚度不足20μm的情況下,將黏著帶1用於半導體元件基板等的切割的情況下,有時難以將形成的半導體晶片等從黏著帶1剝離。
另一方面,黏著帶1的厚度超過200μm的情況下,在將黏著帶1黏貼於半導體元件基板等之際,黏著帶1難以追隨形成於半導體元件基板的黏貼面的凹凸。此情況下,黏著帶1與半導體元件基板等的黏合面積變小,在切割之際半導體晶片等恐容易飛散。<Thickness of adhesive tape>
The entire thickness of the
[黏著帶的製造方法]
接著,就本實施方式的黏著帶1的製造方法進行說明。另外,在以下說明的黏著帶1的製造方法為一例,黏著帶1的製造方法不限定於此。
於此,黏著劑層3在硬化型的聚矽氧系黏著劑方面包含加成反應型聚矽氧系黏著劑的第1形態的黏著帶1、和黏著劑層3在硬化型的聚矽氧系黏著劑方面包含加成反應型聚矽氧系黏著劑與過氧化物固化型聚矽氧系黏著劑的第2形態的黏著帶1可透過同樣的製造方法製造。[Manufacturing method of adhesive tape]
Next, a method of manufacturing the
在製造黏著帶1之際,首先,於甲苯、乙酸乙酯等的通用的有機溶劑,使硬化型的聚矽氧系黏著劑及交聯劑等的其他成分溶解,獲得黏著劑溶液。接著,將此黏著劑溶液,在依所需而進行表面處理、錨固塗層的形成後的基材2的表面,使用逗點形刮刀塗布機等塗布為預先設定的厚度。
接著,將塗布黏著劑溶液後的基材2,以60℃~160℃的溫度,加熱數分鐘~數十分鐘程度,從而使黏著劑溶液乾燥硬化,形成黏著劑層3。
透過以上的程序,如示於圖1,獲得在基材2之上層積黏著劑層3的黏著帶1。When manufacturing the
[黏著帶的使用方法]
本實施方式的黏著帶1在具有LED(Light emitting diode)、功率半導體等的半導體元件之半導體晶片之製程中,用於成為半導體晶片的基礎的半導體材料的切割。[How to use the adhesive tape]
The
具體而言,黏著帶1用於獲得將在由樹脂、陶瓷等所成的基板上形成複數個LED元件、功率半導體元件等的半導體元件的半導體元件基板進行切割而被個片化的半導體晶片。於此,在基板上形成複數個半導體元件的半導體元件基板方面,一般而言為了從溫度、濕度等的外部環境保護半導體元件,有時以覆蓋半導體元件的方式設置作為被覆材的一例的密封樹脂。
本實施方式的黏著帶1可優選上特別適用於設置有密封樹脂的半導體元件基板的切割。Specifically, the
為了將設置有密封樹脂的半導體元件基板切斷而獲得複數個半導體晶片用的方法方面,歷來已知例如以下的方法。 首先,從半導體元件基板的基板側黏貼切割用的黏著帶,時透過切割機等將半導體元件基板從形成有半導體元件之側切斷。然後,將透過切斷而形成的個別的半導體晶片從黏著帶剝離,從而獲得複數個半導體晶片。In order to obtain a plurality of semiconductor wafers by cutting a semiconductor element substrate provided with a sealing resin, for example, the following methods have been known. First, the adhesive tape for dicing is stuck from the substrate side of the semiconductor element substrate, and the semiconductor element substrate is cut from the side where the semiconductor element is formed by a dicing machine or the like. Then, the individual semiconductor wafers formed by cutting are peeled from the adhesive tape to obtain a plurality of semiconductor wafers.
然而,如此般從半導體元件基板的基板側黏貼切割用的黏著帶而進行半導體元件基板的切斷的情況下,存在發生在切斷面(半導體晶片的基板側面)產生缺塊的所謂塌邊,或切斷面變粗糙等的課題。 於是,近年來,為了解決如此的課題,已提出以下方法:對半導體元件基板,不僅基板側,亦從形成半導體元件之側,亦即從將半導體元件進行密封的密封樹脂側黏貼切割用的黏著帶,將半導體元件基板進行切斷。However, when the semiconductor element substrate is cut by sticking an adhesive tape for dicing from the substrate side of the semiconductor element substrate in this way, there is a so-called sag that occurs on the cut surface (side surface of the substrate of the semiconductor wafer). Or roughened cut surfaces. Therefore, in recent years, in order to solve such a problem, the following method has been proposed: for the semiconductor element substrate, not only the substrate side, but also the side from which the semiconductor element is formed, that is, the sealing resin that seals the semiconductor element is adhered for cutting The tape cuts the semiconductor element substrate.
於此,LED、功率半導體等的半導體元件用的密封樹脂方面,歷來利用在電氣特性、耐熱性方面優異的環氧樹脂,環氧樹脂在使用於高輸出的LED、功率半導體的情況下,使用於短波長的LED的情況下,或由於半導體晶片的使用環境等,存在容易變色如此的問題。Here, the sealing resins for semiconductor elements such as LEDs and power semiconductors have historically used epoxy resins that are excellent in electrical characteristics and heat resistance. Epoxy resins are used when used in high-output LEDs and power semiconductors. In the case of short-wavelength LEDs, or due to the use environment of semiconductor wafers, etc., there is a problem that they are easily discolored.
相對於此,基於比起環氧樹脂較不易發生熱、光所致的變色如此的理由,近年來,使用聚矽氧樹脂作為LED、功率半導體等的半導體元件用的密封樹脂的情況多。更具體而言,使用官能基方面含有甲基及苯基雙方或一方的聚矽氧樹脂,亦即使用含有甲基的聚矽氧樹脂、含有苯基的聚矽氧樹脂、含有甲基與苯基雙方的聚矽氧樹脂的情況多。On the other hand, for the reason that discoloration due to heat and light is less likely to occur than epoxy resins, in recent years, polysilicone resins are often used as sealing resins for semiconductor elements such as LEDs and power semiconductors. More specifically, a polysiloxane resin containing both or one of methyl and phenyl groups in terms of functional groups is used, that is, a polysiloxane resin containing methyl groups, a polysiloxane resin containing phenyl groups, and a polysiloxane resin containing methyl groups and benzene There are many cases of silicone resin on both sides.
半導體元件的密封樹脂方面使用聚矽氧樹脂,使得可抑制熱、光所致的密封樹脂的變色。 此外,聚矽氧樹脂是透光率高達88%以上(波長400~800nm),折射率高達1.41以上。為此,半導體元件為LED的情況下,密封樹脂方面使用聚矽氧樹脂,從而可有效將來自LED的放射光取出至封裝體的外部。上述的聚矽氧樹脂之中,使用含有苯基的聚矽氧樹脂,使得比起使用含有甲基的聚矽氧樹脂的情況,可達成進一步的放射光的效率化。Silicone resin is used for the sealing resin of the semiconductor element, so that the discoloration of the sealing resin caused by heat and light can be suppressed. In addition, the silicone resin has a light transmittance of over 88% (wavelength 400-800nm) and a refractive index of up to 1.41. For this reason, when the semiconductor element is an LED, silicone resin is used for the sealing resin, so that the radiation light from the LED can be efficiently taken out of the package. Among the above-mentioned polysiloxane resins, the use of a phenyl group-containing polysiloxane resin makes it possible to achieve more efficient light emission than the case of using a methyl group-containing polysiloxane resin.
含有甲基的聚矽氧樹脂方面,非特別限定者,舉例如信越化學工業株式會社製的KER-2300、KER-2460、KER-2500N、KER-2600、KER-2700、KER-2900、X-32-2528、邁圖高新材料公司製的IVS4312、IVS4312、XE14-C2042、IVS4542、IVS4546、IVS4622、IVS4632、IVS4742、IVS4752、IVSG3445、IVSG0810、IVSG5778、XE13-C2479、IVSM4500、道康寧東麗株式會社製的OE-6351、OE-6336、OE-6301等。 含有甲基與苯基的聚矽氧樹脂方面,非特別限定者,舉例如信越化學工業株式會社製KER-6075、KER-6150、KER-6020等。 含有苯基的聚矽氧樹脂方面,非特別限定者,舉例如信越化學工業株式會社製KER-6110、KER-6000、KER-6200、ASP-1111、ASP-1060、ASP-1120、ASP-1050P、邁圖高新材料公司製的XE14-C2508、道康寧東麗株式會社製的OE-6520、OE-6550、OE-6631、OE-6636、OE-6635、OE-6630等。The silicone-containing polysiloxane resins are not particularly limited, for example, KER-2300, KER-2460, KER-2500N, KER-2600, KER-2700, KER-2900, X- manufactured by Shin-Etsu Chemical Co., Ltd. 32-2528, IVS4312, IVS4312, XE14-C2042, IVS4542, IVS4546, IVS4622, IVS4632, IVS4742, IVS4752, IVSG3445, IVSG0810, IVSG5778, XE13-C2479, IVSM4500, Dow Corning Toray Co., Ltd. OE-6351, OE-6336, OE-6301, etc. The silicone resin containing a methyl group and a phenyl group is not particularly limited, and examples thereof include KER-6075, KER-6150, and KER-6020 manufactured by Shin-Etsu Chemical Co., Ltd. As for the silicone resin containing phenyl group, there are no particular limitations, for example, KER-6110, KER-6000, KER-6200, ASP-1111, ASP-1060, ASP-1120, ASP-1050P manufactured by Shin-Etsu Chemical Co., Ltd. , XE14-C2508 manufactured by Maitu High-tech Materials Co., Ltd., OE-6520, OE-6550, OE-6663, OE-6636, OE-6635, OE-6630 manufactured by Dow Corning Toray Co., Ltd.
然而,歷來,為了切斷半導體元件而使用的切割用的黏著帶方面,例如使用黏著劑層由丙烯酸樹脂系的黏著劑所成的黏著帶。 然而,將如此的歷來的黏著帶從半導體元件基板的形成半導體元件之側(密封樹脂側)黏貼而進行半導體元件基板的切割時,例如,密封樹脂與黏著帶的黏著力不充分的情況下,在切割時恐產生半導體晶片飛散等的問題。However, conventionally, for the adhesive tape for dicing used for cutting a semiconductor element, for example, an adhesive tape made of an acrylic adhesive is used as an adhesive layer. However, when such a conventional adhesive tape is pasted from the side of the semiconductor element substrate where the semiconductor element is formed (sealing resin side) to cut the semiconductor element substrate, for example, when the adhesive force between the sealing resin and the adhesive tape is insufficient, During dicing, there may be problems such as the scattering of semiconductor wafers.
尤其,上述的聚矽氧樹脂比起例如歷來作為密封樹脂而使用的環氧樹脂等具有脫模性高的性質。因此,對在密封樹脂方面使用聚矽氧樹脂的半導體元件基板,黏貼例如黏著劑層由丙烯酸樹脂系的黏著劑所成的黏著帶的情況下,為密封樹脂之聚矽氧樹脂與黏著帶的黏合力容易變小。此結果,在半導體元件基板的切割之際較容易發生半導體晶片的飛散等的問題。In particular, the above-mentioned polysiloxane resin has properties of high releasability compared to, for example, epoxy resins that have been conventionally used as sealing resins. Therefore, in the case of a semiconductor device substrate using polysiloxane resin as the sealing resin, for example, when an adhesive tape made of an acrylic resin adhesive is attached to the adhesive tape, it is the polysiloxane resin of the sealing resin and the adhesive tape. The adhesive force tends to decrease. As a result, problems such as scattering of semiconductor wafers are more likely to occur during the dicing of the semiconductor element substrate.
相對於此,本實施方式的黏著帶1是如上述般,黏著劑層3被構成為包含以適切的比率混合聚矽氧膠(G)與聚矽氧樹脂(R)的聚矽氧系黏著劑,使得在進行半導體元件基板的切割的情況下,從由聚矽氧樹脂所成的密封樹脂側進行黏貼而使用的情況下,皆可良好地保持對於半導體元件基板的密封樹脂之黏著力及附著力。然後,比起歷來的黏著帶,在進行半導體元件基板的切割的情況下,可抑制半導體晶片的飛散等的發生。
另一方面,黏著劑層3與上述的聚矽氧系黏著劑一起含有感光鉑(Pt)觸媒及交聯劑,使得照射紫外線等的光從而使聚矽氧系黏著劑中的感光鉑(Pt)觸媒被活性化,加成反應型聚矽氧系黏著劑與對於該加成反應型聚矽氧系黏著劑之交聯劑的交聯反應被促進,致使黏著劑的凝聚力變比光照射前大。此結果,黏著劑層3的附著力適切降低,再者在保持力試驗中的破壞模式成為「界面破壞」或保持力試驗中成為「不落下」者。藉此,可實現將半導體晶片等從黏著帶1剝離之際的良好的拾取性,同時可抑制對於半導體晶片等之黏劑殘物。In contrast, the
以下,就本實施方式的黏著帶1的使用方法及使用本實施方式的黏著帶1的半導體晶片之製造方法,詳細進行說明。圖2(a)~(e)為就使用本實施方式的黏著帶1的半導體晶片之製造方法進行繪示的圖。
另外,此處舉使用黏著帶1而製造具有LED元件作為半導體元件的半導體晶片的情況為例進行說明。此外,在以下說明的方法為黏著帶1的使用方法、及使用黏著帶1的半導體晶片之製造方法的一例,不限定於以下的方法。Hereinafter, a method of using the
在本實施方式,首先例如在由樹脂材料、陶瓷等所成的基板101上,載積複數個半導體元件102,製作半導體元件基板100。另外,半導體元件102為例如LED元件,圖式雖省略,惟例如包含透過通電而發光的發光層等的複數個半導體層被層積而構成,在上部形成電極。
接著,將半導體元件基板100的形成於基板101上的複數個半導體元件,以由聚矽氧系樹脂所成的密封樹脂103密封(密封程序)。另外,在此例中,雖將複數個半導體元件102透過密封樹脂103一起密封,惟亦可將各個半導體元件102透過密封樹脂103個別進行密封。In this embodiment, first, for example, a plurality of
接著,如示於圖2(a),以黏著帶1的黏著劑層3與半導體元件基板100的密封樹脂103相向的方式,將黏著帶1與半導體元件基板100黏貼(黏貼程序)。
接著,如示於圖2(b)、(c),在將黏著帶1與半導體元件基板100黏貼的狀態下,沿著切斷預定線X,將半導體元件基板100透過切割機等切斷(切斷程序)。在此例中,將被黏貼有黏著帶1的半導體元件基板100從基板101側切斷。此外,如示於圖2(c)般,在此例中,進行將半導體元件基板100全部切入於厚度方向的所謂全切割。Next, as shown in FIG. 2( a ), the
接著,如示於圖2(d),對黏貼於半導體元件基板100的黏著帶1,從基材2側照射紫外線(紫外線照射程序)。如上述般,基材2由使紫外線透射的材質構成。因此,對黏著帶1從基材2側照射紫外線,使得紫外線穿透基材2而照射於黏著劑層3。
在本實施方式的黏著帶1方面,由於黏著劑層3具有感光鉑(Pt)觸媒,故紫外線被照射於黏著劑層3,使得促進黏著劑層3中的加成反應型聚矽氧系黏著劑與交聯劑的加成反應。藉此,比起照射紫外線前,黏著劑層3的交聯密度亦即凝聚力上升,黏著劑層3的附著力降低。Next, as shown in FIG. 2(d), the
接著,將透過切斷半導體元件基板100從而形成的半導體晶片200,從黏著帶1剝離(拾取),使得如示於圖2(e),可獲得被個片化的半導體晶片200(剝離程序)。Next, the
如上述般,本實施方式的黏著帶1是黏著劑層3被構成為包含以適切的比率混合聚矽氧膠(G)與聚矽氧樹脂(R)的聚矽氧系黏著劑。藉此,在將黏著帶1使用於切割的情況下,可良好地保持對於半導體元件基板100之黏著帶1的黏著力及附著力。
尤其,近年來,將半導體元件102密封的密封樹脂103方面,使用脫模性高的聚矽氧樹脂的情形多。相對於此,本實施方式的黏著帶1由於具有上述的構成,使得對於由聚矽氧樹脂所成的密封樹脂103仍具有良好的黏著力及附著力。
此結果,本實施方式的黏著帶1在使用於半導體元件基板100的切割的情況下,可抑制半導體晶片200的飛散。As described above, in the
再者,含於本實施方式的黏著帶1的黏著劑層3的聚矽氧系黏著劑一方面如上述般具有與密封樹脂103良好的黏著力,另一方面具有脫模性高的性質。
再且,本實施方式的黏著帶1包含例如透過紫外線等的光的照射因而促進加成反應型聚矽氧系黏著劑與交聯劑的加成反應的感光鉑(Pt)觸媒。然後,切斷程序後,在剝離程序前透過基材2對黏著劑層3照射光,從而可在黏著劑層3予以促進加成反應型聚矽氧系黏著劑與交聯劑的加成反應,提升凝聚力,使黏著劑層3的附著力降低。藉此,於剝離程序,在將透過半導體元件基板100的切割而獲得的半導體晶片200從黏著帶1剝離(拾取)之際,可抑制黏著劑附著於半導體晶片200的所謂黏劑殘物的發生。此外,可實現將半導體晶片200從黏著帶1剝離之際的良好的拾取性。In addition, the polysiloxane adhesive contained in the
另外,在上述,就對在基板上形成複數個半導體元件的半導體元件基板將黏著帶1從密封樹脂側黏貼而進行切割從而獲得被個片化的半導體晶片的方法進行說明。然而,本實施方式的黏著帶1的用途不限定於此。
本實施方式的黏著帶1亦可於例如晶片級封裝LED的製造,用於獲得將複數個LED元件被作為被覆材的一例的螢光體所被覆的半導體材料進行切割而被個片化的晶片級封裝LED。另外,螢光體為螢光材料被分散於樹脂材料、陶瓷等的構材。In addition, in the above, a method of obtaining a singulated semiconductor wafer by dicing the
近年來,伴隨晶片級封裝LED的小型化,具有切割時被個片化的晶片級封裝LED容易飛散的傾向。相對於此,透過使用具有上述的構成的本實施方式的黏著帶1,使得可良好地保持螢光體與黏著劑層3的黏合力,可抑制被個片化的晶片級封裝LED的飛散。
此外,切割後,對黏著劑層3照射紫外線而使附著力降低,使得容易將被從黏著帶1個片化的晶片級封裝LED剝離,同時可抑制對於剝離的晶片級封裝LED之黏劑殘物的產生。
[實施例]In recent years, with the miniaturization of wafer-level packaged LEDs, there has been a tendency for wafer-level packaged LEDs that are divided into pieces at the time of dicing to be easily scattered. On the other hand, by using the
接著,使用實施例及比較例就本發明進一步具體說明。另外,本發明不限定於以下的實施例。Next, the present invention will be further specifically described using Examples and Comparative Examples. In addition, the present invention is not limited to the following examples.
本發明人就黏著劑層3包含加成反應型聚矽氧系黏著劑作為硬化型的聚矽氧系黏著劑的第1形態、及黏著劑層3包含加成反應型聚矽氧系黏著劑與過氧化物固化型聚矽氧系黏著劑作為硬化型的聚矽氧系黏著劑的第2形態,分別使黏著劑層3的成分、各層的厚度等不同而進行黏著帶1的製作,進行所製作的黏著帶1的評價。另外,以下的實施例之中,實施例1~8對應於第1形態,實施例9~15對應於第2形態。
以下,就各實施例及各比較例詳細進行說明。The present inventor has the first aspect that the
1.黏著帶1的製作
(實施例1)
將甲苯、由在分子內具有乙烯矽烷(Vinylsilyl)基作為矽鍵結烯基的有機聚矽氧烷所成的加成反應型聚矽氧系黏著劑(道康寧東麗株式會社製SD4584(商品名)的未添加交聯劑型、固含量濃度60質量%)166.67質量份、和由在分子內具有氫矽烷(Hydrosilyl)基的有機聚矽氧烷所成的交聯劑(道康寧東麗株式會社製BY24-741(商品名)、固含量濃度20質量%)3.30質量份進行混合攪拌。接著,添加以甲苯稀釋為固含量濃度15質量%的感光鉑(Pt)觸媒(Sigma-Aldrich Japan K.K.公司製三甲基(甲基環戊二烯)鉑(IV))的溶液5.33質量份,進行混合攪拌,調整第1形態的黏著劑溶液。
接著,將此黏著劑溶液,塗布於厚度38μm的由聚對苯二甲酸乙二酯(PET)膜所成的基材2上後,以120℃的溫度3分鐘進行加熱,從而形成乾燥後的厚度為20μm的黏著劑層3。藉此,獲得乾燥後的總厚為58μm的黏著帶1。1. Making Adhesive Tape 1
(Example 1)
Addition reaction type polysiloxane-based adhesive composed of toluene and an organic polysiloxane having a vinyl silane (Vinylsilyl) group as a silicon-bonded alkenyl group (SD4584 (trade name, manufactured by Dow Corning Toray Co., Ltd.) ) Without addition of crosslinking agent, solid content concentration of 60% by mass) 166.67 parts by mass, and a crosslinking agent (manufactured by Dow Corning Toray Co., Ltd.) made of organic polysiloxane having a hydrosilyl group in the molecule 3.24 parts by mass of BY24-741 (trade name), solid content concentration 20% by mass) were mixed and stirred. Next, 5.33 parts by mass of a solution of a photosensitive platinum (Pt) catalyst (trimethyl(methylcyclopentadiene) platinum (IV) manufactured by Sigma-Aldrich Japan KK) diluted with toluene to a solid content concentration of 15% by mass was added. , Mix and stir, and adjust the adhesive solution of the first form.
Next, this adhesive solution was applied to a
(實施例2)
於第1形態的黏著劑溶液的調整,使用由在分子內具有乙烯矽烷(Vinylsilyl)基作為矽鍵結烯基的有機聚矽氧烷所成的加成反應型聚矽氧系黏著劑(道康寧東麗株式會社製SD4584(商品名)的未添加交聯劑型、固含量濃度60質量%),使黏著劑層3的乾燥後的厚度為30μm以外,作成如同實施例1,獲得乾燥後的總厚為68μm的黏著帶1。(Example 2)
For the adjustment of the adhesive solution in the first form, an addition reaction type polysiloxane-based adhesive (Dow Corning) composed of an organic polysiloxane having an ethylene silane (Vinylsilyl) group as a silicon-bonded alkenyl group in the molecule is used Toray Co., Ltd. SD4584 (trade name) without addition of crosslinking agent type, solid content concentration of 60% by mass), the thickness of the
(實施例3)
基材2方面,使用厚度12μm的PET膜,使黏著劑層3的乾燥後的厚度為10μm以外,作成如同實施例2,獲得乾燥後的總厚為22μm的黏著帶1。(Example 3)
For the
(實施例4)
於第1形態的黏著劑溶液的調整,使用由在分子內具有乙烯矽烷(Vinylsilyl)基作為矽鍵結烯基的有機聚矽氧烷所成的加成反應型聚矽氧系黏著劑(道康寧東麗株式會社製SD4585(商品名)的未添加交聯劑型、固含量濃度60質量%),基材2方面,使用厚度50μm的PET膜,使黏著劑層3的乾燥後的厚度為40μm以外,作成如同實施例1,獲得乾燥後的總厚為90μm的黏著帶1。(Example 4)
For the adjustment of the adhesive solution in the first form, an addition reaction type polysiloxane-based adhesive (Dow Corning) composed of an organic polysiloxane having an ethylene silane (Vinylsilyl) group as a silicon-bonded alkenyl group in the molecule is used Toray Co., Ltd.'s SD4585 (trade name) (without added crosslinking agent type, solid content concentration 60% by mass), for the
(實施例5)
於第1形態的黏著劑溶液的調整,使交聯劑(道康寧東麗株式會社製BY24-741(商品名)、固含量濃度20質量%)的添加量為1.65質量份以外,作成如同實施例1,獲得乾燥後的總厚為58μm的黏著帶1。(Example 5)
In the adjustment of the adhesive solution of the first aspect, the addition amount of the crosslinking agent (BY24-741 (trade name) manufactured by Dow Corning Toray Co., Ltd., solid content concentration 20% by mass) was 1.65 parts by mass, and was prepared as in the example. 1. Obtain an
(實施例6)
於第1形態的黏著劑溶液的調整,使交聯劑(道康寧東麗株式會社製BY24-741(商品名)、固含量濃度20質量%)的添加量為8.25質量份以外,作成如同實施例1,獲得乾燥後的總厚為58μm的黏著帶1。(Example 6)
In the adjustment of the adhesive solution of the first aspect, the addition amount of the crosslinking agent (by Dow Corning Toray Co., Ltd. BY24-741 (trade name), solid content concentration 20% by mass) was 8.25 parts by mass, and it was prepared as in the example. 1. Obtain an
(實施例7)
於第1形態的黏著劑溶液的調整,使以甲苯稀釋為固含量濃度15質量%的感光鉑(Pt)觸媒(Sigma-Aldrich Japan K.K.公司製三甲基(甲基環戊二烯)鉑(IV))的溶液的添加量為2.00質量份以外,作成如同實施例1,獲得乾燥後的總厚為58μm的黏著帶1。(Example 7)
In the adjustment of the adhesive solution of the first aspect, a photosensitive platinum (Pt) catalyst (manufactured by Sigma-Aldrich Japan KK) trimethyl (methylcyclopentadiene) platinum diluted with toluene to a solid content concentration of 15% by mass (IV)) The addition amount of the solution was 2.00 parts by mass, and it was made as in Example 1 to obtain an
(實施例8)
於第1形態的黏著劑溶液的調整,使以甲苯稀釋為固含量濃度15質量%的感光鉑(Pt)觸媒(Sigma-Aldrich Japan K.K.公司製三甲基(甲基環戊二烯)鉑(IV))的溶液的添加量為20.00質量份以外,作成如同實施例1,獲得乾燥後的總厚為58μm的黏著帶1。(Example 8)
In the adjustment of the adhesive solution of the first aspect, a photosensitive platinum (Pt) catalyst (manufactured by Sigma-Aldrich Japan KK) trimethyl (methylcyclopentadiene) platinum diluted with toluene to a solid content concentration of 15% by mass (IV)) The addition amount of the solution was 20.00 parts by mass, and it was made as in Example 1 to obtain an
(實施例9) 將甲苯、由在分子內具有乙烯矽烷(Vinylsilyl)基作為矽鍵結烯基的有機聚矽氧烷所成的加成反應型聚矽氧系黏著劑(道康寧東麗株式會社製SD4584(商品名)的未添加交聯劑型、固含量濃度60質量%)166.67質量份、和由在分子內具有氫矽烷(Hydrosilyl)基的有機聚矽氧烷所成的交聯劑(道康寧東麗株式會社製BY24-741(商品名)、固含量濃度20質量%)3.30質量份進行混合攪拌。接著,添加以甲苯稀釋為固含量濃度15質量%的感光鉑(Pt)觸媒(Sigma-Aldrich Japan K.K.公司製三甲基(甲基環戊二烯)鉑(IV))的溶液5.33質量份,進行混合攪拌,調製加成反應型聚矽氧系黏著劑溶液。(Example 9) Addition reaction type polysiloxane-based adhesive composed of toluene and an organic polysiloxane having a vinyl silane (Vinylsilyl) group as a silicon-bonded alkenyl group (SD4584 (trade name, manufactured by Dow Corning Toray Co., Ltd.) ) Without addition of crosslinking agent, solid content concentration of 60% by mass) 166.67 parts by mass, and a crosslinking agent (manufactured by Dow Corning Toray Co., Ltd.) made of organic polysiloxane having a hydrosilyl group in the molecule 3.24 parts by mass of BY24-741 (trade name), solid content concentration 20% by mass) were mixed and stirred. Next, 5.33 parts by mass of a solution of a photosensitive platinum (Pt) catalyst (trimethyl(methylcyclopentadiene) platinum (IV) manufactured by Sigma-Aldrich Japan KK) diluted with toluene to a solid content concentration of 15% by mass was added. , Mix and stir to prepare the addition reaction type polysiloxane adhesive solution.
另一方面,將甲苯、由有機聚矽氧烷所成的過氧化物固化型聚矽氧系黏著劑(道康寧東麗株式會社製SH4280(商品名)、固含量濃度60質量%)166.67質量份、和由甲基過氧化苯甲醯所成的引發劑(日油株式會社製NYPERK40(商品名)、固含量濃度40質量%)5.00質量份進行混合攪拌,調製過氧化物固化型聚矽氧系黏著劑溶液。On the other hand, 166.67 parts by mass of toluene and a peroxide-curable polysiloxane-based adhesive made of organic polysiloxane (SH4280 (trade name) manufactured by Dow Corning Toray Co., Ltd., solid content concentration 60% by mass) 、Mixed with 5.00 parts by mass of an initiator (NYPERK40 (trade name) manufactured by NOF Corporation, solid content concentration 40% by mass) made of methylbenzoic acid peroxide, to prepare peroxide-curing polysiloxane Department of adhesive solution.
接著,將獲得的加成反應型聚矽氧系黏著劑溶液與過氧化物固化型聚矽氧系黏著劑溶液進行混合攪拌,調製第2形態的黏著劑溶液。另外,加成反應型聚矽氧系黏著劑溶液與過氧化物固化型聚矽氧系黏著劑溶液的混合比率是以對於加成反應型聚矽氧系黏著劑100質量份(固含量)包含100質量份(固含量)的過氧化物固化型聚矽氧系黏著劑的方式進行調整。
接著,將此黏著劑溶液,塗布於厚度38μm的由聚對苯二甲酸乙二酯(PET)膜所成的基材2上後,以160℃的溫度3分鐘進行加熱,從而形成乾燥後的厚度為20μm的黏著劑層3。藉此,獲得乾燥後的總厚為58μm的黏著帶1。Next, the obtained addition reaction type polysiloxane-based adhesive solution and the peroxide-curing polysiloxane-based adhesive solution are mixed and stirred to prepare a second form of adhesive solution. In addition, the mixing ratio of the addition reaction type silicone adhesive solution and the peroxide curing type silicone adhesive solution is included for 100 parts by mass (solid content) of the addition reaction type silicone adhesive. 100 parts by mass (solid content) of peroxide-curing polysiloxane-based adhesive is adjusted.
Next, this adhesive solution was applied to a
(實施例10)
於第2形態的黏著劑溶液的調整,就加成反應型聚矽氧系黏著劑溶液與過氧化物固化型聚矽氧系黏著劑溶液的混合比率,以對於加成反應型聚矽氧系黏著劑100質量份(固含量)包含63.70質量份(固含量)的過氧化物固化型聚矽氧系黏著劑的方式進行調整以外,作成如同實施例9,獲得乾燥後的總厚為58μm的黏著帶1。(Example 10)
In the adjustment of the adhesive solution in the second form, the mixing ratio of the addition reaction type silicone adhesive solution and the peroxide curing type silicone adhesive solution is 100 parts by mass (solid content) of the adhesive contains 63.70 parts by mass (solid content), except that the method of adjusting the peroxide-curing polysiloxane-based adhesive is adjusted, as in Example 9, a total thickness of 58 μm after drying is obtained
(實施例11)
於第2形態的黏著劑溶液的調整,就加成反應型聚矽氧系黏著劑溶液與過氧化物固化型聚矽氧系黏著劑溶液的混合比率,以對於加成反應型聚矽氧系黏著劑100質量份(固含量)包含150質量份(固含量)的過氧化物固化型聚矽氧系黏著劑的方式進行調整以外,作成如同實施例9,獲得乾燥後的總厚為58μm的黏著帶1。(Example 11)
In the adjustment of the adhesive solution in the second form, the mixing ratio of the addition reaction type silicone adhesive solution and the peroxide curing type silicone adhesive solution is 100 parts by mass of the adhesive (solid content) contains 150 parts by mass (solid content) of the peroxide-curable polysiloxane-based adhesive, except that the method is adjusted, as in Example 9, to obtain a total thickness of 58 μm after drying
(實施例12)
於第2形態的黏著劑溶液的加成反應型聚矽氧系黏著劑溶液的調整,由在分子內具有乙烯矽烷(Vinylsilyl)基作為矽鍵結烯基的有機聚矽氧烷所成的加成反應型聚矽氧系黏著劑方面,使用道康寧東麗株式會社製SD4580(商品名)的未添加交聯劑型(固含量濃度60質量%)以外,作成如同實施例9,獲得乾燥後的總厚為58μm的黏著帶1。(Example 12)
The adjustment of the addition reaction type polysiloxane-based adhesive solution in the second form of the adhesive solution consists of an organic polysiloxane having an ethylene silane (Vinylsilyl) group as a silicon-bonded alkenyl group in the molecule. For the reaction-type polysiloxane-based adhesive, the non-crosslinking agent type (solid content concentration 60% by mass) manufactured by Dow Corning Toray Co., Ltd. SD4580 (trade name) was used, and it was prepared as in Example 9 to obtain the total
(實施例13)
於第2形態的黏著劑溶液的加成反應型聚矽氧系黏著劑溶液的調整,由在分子內具有乙烯矽烷(Vinylsilyl)基作為矽鍵結烯基的有機聚矽氧烷所成的加成反應型聚矽氧系黏著劑方面,使用道康寧東麗株式會社製SD4586(商品名)的未添加交聯劑型(固含量濃度60質量%)以外,作成如同實施例9,獲得乾燥後的總厚為58μm的黏著帶1。(Example 13)
The adjustment of the addition reaction type polysiloxane-based adhesive solution in the second form of the adhesive solution consists of an organic polysiloxane having an ethylene silane (Vinylsilyl) group as a silicon-bonded alkenyl group in the molecule. For the reaction-type polysiloxane-based adhesive, except for the unadded crosslinking agent type (solid content concentration 60% by mass) manufactured by Dow Corning Toray Co., Ltd. SD4586 (trade name), it was prepared as in Example 9 to obtain the total
(實施例14) 將甲苯、由在分子內具有乙烯矽烷(Vinylsilyl)基作為矽鍵結烯基的有機聚矽氧烷所成的加成反應型聚矽氧系黏著劑(道康寧東麗株式會社製SD4585(商品名)的未添加交聯劑型、固含量濃度60質量%)166.67質量份、和由在分子內具有氫矽烷(Hydrosilyl)基的有機聚矽氧烷所成的交聯劑(道康寧東麗株式會社製BY24-741(商品名)、固含量濃度20質量%)3.30質量份進行混合攪拌。接著,添加以甲苯稀釋為固含量濃度15重量%的感光鉑(Pt)觸媒(Sigma-Aldrich Japan K.K.公司製三甲基(甲基環戊二烯)鉑(IV))的溶液5.33質量份,進行混合攪拌,調製加成反應型聚矽氧系黏著劑溶液。(Example 14) Addition reaction type polysiloxane-based adhesive composed of toluene and an organic polysiloxane having a vinyl silane (Vinylsilyl) group as a silicon-bonded alkenyl group (SD4585 (trade name, manufactured by Dow Corning Toray Co., Ltd.) ) Without addition of crosslinking agent, solid content concentration of 60% by mass) 166.67 parts by mass, and a crosslinking agent (manufactured by Dow Corning Toray Co., Ltd.) made of organic polysiloxane having a hydrosilyl group in the molecule 3.24 parts by mass of BY24-741 (trade name), solid content concentration 20% by mass) were mixed and stirred. Next, 5.33 parts by mass of a solution of a photosensitive platinum (Pt) catalyst (trimethyl(methylcyclopentadiene) platinum (IV) manufactured by Sigma-Aldrich Japan KK) diluted with toluene to a solid content concentration of 15% by weight was added. , Mix and stir to prepare the addition reaction type polysiloxane adhesive solution.
另一方面,將甲苯、和由有機聚矽氧烷所成的過氧化物固化型聚矽氧系黏著劑(道康寧東麗株式會社製BY24-717(商品名)、固含量濃度60質量%)166.67質量份進行混合攪拌,調整過氧化物固化型聚矽氧系黏著劑溶液。On the other hand, toluene and a peroxide-curable polysiloxane-based adhesive made of organic polysiloxane (BY24-717 (trade name) manufactured by Dow Corning Toray Co., Ltd., solid content concentration 60% by mass) Mix and stir 166.67 parts by mass to adjust the peroxide-curing polysiloxane-based adhesive solution.
接著,將獲得的加成反應型聚矽氧系黏著劑溶液與過氧化物固化型聚矽氧系黏著劑溶液進行混合攪拌,調製第2形態的黏著劑溶液。另外,加成反應型聚矽氧系黏著劑溶液與過氧化物固化型聚矽氧系黏著劑溶液的混合比率是以對於加成反應型聚矽氧系黏著劑100質量份(固含量)包含20質量份(固含量)的過氧化物固化型聚矽氧系黏著劑的方式進行調整。
接著,將此黏著劑溶液,塗布於厚度38μm的由聚對苯二甲酸乙二酯(PET)膜所成的基材2上後,以160℃度的溫度3分鐘進行加熱,從而形成乾燥後的厚度為20μm的黏著劑層3。藉此,獲得乾燥後的總厚為58μm的黏著帶1。Next, the obtained addition reaction type polysiloxane-based adhesive solution and the peroxide-curing polysiloxane-based adhesive solution are mixed and stirred to prepare a second form of adhesive solution. In addition, the mixing ratio of the addition reaction type silicone adhesive solution and the peroxide curing type silicone adhesive solution is 100 parts by mass (solid content) of the addition reaction type silicone adhesive. 20 parts by mass (solid content) of peroxide-curing polysiloxane-based adhesive is adjusted.
Next, this adhesive solution was applied on a
(實施例15) 首先,作成如同實施例4的第1形態的黏著劑溶液,調整加成反應型聚矽氧系黏著劑溶液。(Example 15) First, an adhesive solution as in the first form of Example 4 was prepared, and the addition reaction type polysiloxane-based adhesive solution was adjusted.
另一方面,將甲苯、由有機聚矽氧烷所成的過氧化物固化型聚矽氧系黏著劑(道康寧東麗株式會社製SE4200(商品名)、固含量濃度40質量%)250.00質量份、和由甲基過氧化苯甲醯所成的引發劑(日油株式會社製NYPERK40(商品名)、固含量濃度40質量%)5.00質量份進行混合攪拌,調製過氧化物固化型聚矽氧系黏著劑溶液。On the other hand, 250.00 parts by mass of toluene, a peroxide-curable polysiloxane-based adhesive made of organic polysiloxane (SE4200 (trade name) manufactured by Dow Corning Toray Co., Ltd., solid content concentration 40% by mass) 、Mixed with 5.00 parts by mass of an initiator (NYPERK40 (trade name) manufactured by NOF Corporation, solid content concentration 40% by mass) made of methylbenzoic acid peroxide, to prepare peroxide-curing polysiloxane Department of adhesive solution.
接著,將獲得的加成反應型聚矽氧系黏著劑溶液與過氧化物固化型聚矽氧系黏著劑溶液進行混合攪拌,調製第2形態的黏著劑溶液。另外,加成反應型聚矽氧系黏著劑溶液與過氧化物固化型聚矽氧系黏著劑溶液的混合比率是以對於加成反應型聚矽氧系黏著劑100質量份(固含量)包含150質量份(固含量)的過氧化物固化型聚矽氧系黏著劑的方式進行調整。
接著,將此黏著劑溶液塗布於厚度125μm的由聚對苯二甲酸乙二酯(PET)膜所成的基材2上後,以160℃的溫度3分鐘進行加熱,從而形成乾燥後的厚度為20μm的黏著劑層3。藉此,獲得乾燥後的總厚為145μm的黏著帶1。Next, the obtained addition reaction type polysiloxane-based adhesive solution and the peroxide-curing polysiloxane-based adhesive solution are mixed and stirred to prepare a second form of adhesive solution. In addition, the mixing ratio of the addition reaction type silicone adhesive solution and the peroxide curing type silicone adhesive solution is included for 100 parts by mass (solid content) of the addition reaction type silicone adhesive. 150 parts by mass (solid content) of peroxide curing polysiloxane-based adhesive is adjusted.
Next, after applying this adhesive solution to the
(比較例1)
代替感光鉑(Pt)觸媒(Sigma-Aldrich Japan K.K.公司製三甲基(甲基環戊二烯)鉑(IV))的溶液,使用鉑金屬系觸媒(道康寧東麗公司製NC-25(商品名)、固含量25質量%)6質量份,使黏著劑層3的乾燥後的厚度為35μm以外,作成如同實施例1,獲得乾燥後的總厚為73μm的黏著帶1。(Comparative example 1)
Instead of a solution of a photosensitive platinum (Pt) catalyst (trimethyl(methylcyclopentadiene) platinum (IV) manufactured by Sigma-Aldrich Japan KK, a platinum metal catalyst (NC-25 manufactured by Dow Corning Toray Corporation) was used (Brand name), solid content 25% by mass) 6 parts by mass, except that the thickness of the
(比較例2)
對實施例1的黏著劑溶液,作為用於加成反應型聚矽氧系黏著劑的聚矽氧樹脂(R3),進一步添加為在兩末端具有矽烷醇基的線性聚有機矽氧烷的邁圖高新材料公司製YF3897(商品名)、固含量100質量%)10.00質量份,使黏著劑層3的乾燥後的厚度為30μm以外,作成如同實施例1,獲得乾燥後的總厚為68μm的黏著帶1。(Comparative example 2)
The adhesive solution of Example 1 was further added as a linear polyorganosiloxane having a silanol group at both ends as a polysiloxane resin (R3) for addition reaction type polysiloxane-based adhesive. Figure YF3897 (trade name) manufactured by Hi-Tech Materials Co., Ltd.,
(比較例3)
由在分子內具有乙烯矽烷(Vinylsilyl)基作為矽鍵結烯基的有機聚矽氧烷所成的加成反應型聚矽氧系黏著劑方面,使用道康寧東麗株式會社製SD4586(商品名)的未添加交聯劑型(固含量濃度60質量%),使黏著劑層3的乾燥後的厚度為40μm以外,作成如同實施例1,獲得乾燥後的總厚為78μm的黏著帶1。(Comparative example 3)
For the addition reaction type polysiloxane-based adhesive composed of an organic polysiloxane having an ethylene silane (Vinylsilyl) group as a silicon-bonded alkenyl group, SD4586 (trade name) manufactured by Dow Corning Toray Co., Ltd. is used. The non-added cross-linking dosage form (solid content concentration 60% by mass) was used to make the thickness of the
(比較例4) 將甲苯、由在分子內具有乙烯矽烷(Vinylsilyl)基作為矽鍵結烯基的有機聚矽氧烷所成的加成反應型聚矽氧系黏著劑(道康寧東麗株式會社製SD4584(商品名)的未添加交聯劑型、固含量濃度60質量%)166.67質量份、和由在分子內具有氫矽烷(Hydrosilyl)基的有機聚矽氧烷所成的交聯劑(道康寧東麗株式會社製BY24-741(商品名)、固含量濃度20質量%)3.30質量份進行混合攪拌。接著,添加鉑金屬系觸媒(道康寧東麗公司製NC-25(商品名)、固含量25質量%)6.00質量份,進行混合攪拌,調製加成反應型聚矽氧系黏著劑溶液。(Comparative example 4) Addition reaction type polysiloxane-based adhesive composed of toluene and an organic polysiloxane having a vinyl silane (Vinylsilyl) group as a silicon-bonded alkenyl group (SD4584 (trade name, manufactured by Dow Corning Toray Co., Ltd.) ) Without addition of crosslinking agent, solid content concentration of 60% by mass) 166.67 parts by mass, and a crosslinking agent (manufactured by Dow Corning Toray Co., Ltd.) made of organic polysiloxane having a hydrosilyl group in the molecule 3.24 parts by mass of BY24-741 (trade name), solid content concentration 20% by mass) were mixed and stirred. Next, 6.00 parts by mass of a platinum metal catalyst (NC-25 (trade name) manufactured by Dow Corning Toray Co., Ltd., solid content 25% by mass) was added, mixed and stirred, and an addition reaction type polysiloxane-based adhesive solution was prepared.
另一方面,作成如同實施例9,調整過氧化物固化型聚矽氧系黏著劑溶液。On the other hand, as in Example 9, the peroxide-curing polysiloxane-based adhesive solution was adjusted.
接著,將獲得的加成反應型聚矽氧系黏著劑溶液與過氧化物固化型聚矽氧系黏著劑溶液進行混合攪拌,調製黏著劑混合溶液。另外,加成反應型聚矽氧系黏著劑溶液與過氧化物固化型聚矽氧系黏著劑溶液的混合比率是以對於加成反應型聚矽氧系黏著劑100質量份(固含量)包含50質量份(固含量)的過氧化物固化型聚矽氧系黏著劑的方式進行調整。
接著,將此黏著劑混合溶液塗布於厚度38μm的由聚對苯二甲酸乙二酯(PET)膜所成的基材2上後,以160℃的溫度3分鐘進行加熱,從而形成乾燥後的厚度為30μm的黏著劑層3。藉此,獲得乾燥後的總厚為68μm的黏著帶1。Next, the obtained addition reaction type polysiloxane-based adhesive solution and the peroxide curing type polysiloxane-based adhesive solution are mixed and stirred to prepare an adhesive mixed solution. In addition, the mixing ratio of the addition reaction type silicone adhesive solution and the peroxide curing type silicone adhesive solution is 100 parts by mass (solid content) of the addition reaction type silicone adhesive. 50 parts by mass (solid content) of peroxide-curing polysiloxane-based adhesive is adjusted.
Next, after applying this adhesive mixture solution to the
(比較例5) 首先,作成如同實施例2的第1形態的黏著劑溶液,調整加成反應型聚矽氧系黏著劑溶液。(Comparative example 5) First, an adhesive solution as in the first form of Example 2 was prepared, and the addition reaction type polysiloxane-based adhesive solution was adjusted.
另一方面,將甲苯、由有機聚矽氧烷所成的過氧化物固化型聚矽氧系黏著劑(道康寧東麗株式會社製BY241-717(商品名)、固含量濃度60質量%)166.67質量份、和由甲基過氧化苯甲醯所成的引發劑(日油株式會社製NYPERK40(商品名)、固含量濃度40質量%)5.00質量份進行混合攪拌,調製過氧化物固化型聚矽氧系黏著劑溶液。On the other hand, toluene, a peroxide-curable polysiloxane-based adhesive made of organic polysiloxane (BY241-717 (trade name) manufactured by Dow Corning Toray Co., Ltd., solid content concentration 60% by mass) 166.67 Mass parts and 5.00 parts by mass of an initiator (NYPERK40 (trade name) manufactured by NOF Corporation, solid content concentration 40% by mass) and an initiator made of methylbenzoyl peroxide are mixed and stirred to prepare a peroxide-curable polymer Silicone adhesive solution.
接著,將獲得的加成反應型聚矽氧系黏著劑溶液與過氧化物固化型聚矽氧系黏著劑溶液進行混合攪拌,調製黏著劑混合溶液。另外,加成反應型聚矽氧系黏著劑溶液與過氧化物固化型聚矽氧系黏著劑溶液的混合比率是以對於加成反應型聚矽氧系黏著劑100質量份(固含量)包含100質量份(固含量)的過氧化物固化型聚矽氧系黏著劑的方式進行調整。
接著,將此黏著劑混合溶液,塗布於厚度38μm的由聚對苯二甲酸乙二酯(PET)膜所成的基材2上後,以160℃的溫度3分鐘進行加熱,從而形成乾燥後的厚度為20μm的黏著劑層3。藉此,獲得乾燥後的總厚為58μm的黏著帶1。Next, the obtained addition reaction type polysiloxane-based adhesive solution and the peroxide curing type polysiloxane-based adhesive solution are mixed and stirred to prepare an adhesive mixed solution. In addition, the mixing ratio of the addition reaction type silicone adhesive solution and the peroxide curing type silicone adhesive solution is included for 100 parts by mass (solid content) of the addition reaction type silicone adhesive. 100 parts by mass (solid content) of peroxide-curing polysiloxane-based adhesive is adjusted.
Next, this adhesive mixed solution was applied to a
(比較例6) 首先,由在分子內具有乙烯矽烷(Vinylsilyl)基作為矽鍵結烯基的有機聚矽氧烷所成的加成反應型聚矽氧系黏著劑方面,使用道康寧東麗株式會社製SD4587(商品名)的未添加交聯劑型(固含量濃度60質量%)以外,作成如同實施例1,調製加成反應型聚矽氧系黏著劑。(Comparative example 6) First, for the addition reaction type polysiloxane-based adhesive composed of an organic polysiloxane having a vinyl silane (Vinylsilyl) group as a silicon-bonded alkenyl group, SD4587 (product of Dow Corning Toray Co., Ltd.) was used. Except for the cross-linking agent type (solid content concentration 60% by mass) without addition, it was prepared as in Example 1, and an addition reaction type polysiloxane-based adhesive was prepared.
另一方面,作成如同實施例15,調製過氧化物固化型聚矽氧系黏著劑溶液。On the other hand, as in Example 15, a peroxide-curing polysiloxane-based adhesive solution was prepared.
接著,將獲得的加成反應型聚矽氧系黏著劑溶液與過氧化物固化型聚矽氧系黏著劑溶液進行混合攪拌,調製黏著劑混合溶液。另外,加成反應型聚矽氧系黏著劑溶液與過氧化物固化型聚矽氧系黏著劑溶液的混合比率是以對於加成反應型聚矽氧系黏著劑100質量份(固含量)包含100質量份(固含量)的過氧化物固化型聚矽氧系黏著劑的方式進行調整。
接著,將此黏著劑混合溶液,塗布於厚度38μm的由聚對苯二甲酸乙二酯(PET)膜所成的基材2上後,以160℃的溫度3分鐘進行加熱,從而形成乾燥後的厚度為20μm的黏著劑層3。藉此,獲得乾燥後的總厚為58μm的黏著帶1。Next, the obtained addition reaction type polysiloxane-based adhesive solution and the peroxide curing type polysiloxane-based adhesive solution are mixed and stirred to prepare an adhesive mixed solution. In addition, the mixing ratio of the addition reaction type silicone adhesive solution and the peroxide curing type silicone adhesive solution is included for 100 parts by mass (solid content) of the addition reaction type silicone adhesive. 100 parts by mass (solid content) of peroxide-curing polysiloxane-based adhesive is adjusted.
Next, this adhesive mixed solution was applied to a
(比較例7) 首先,作成如同比較例2,調整加成反應型聚矽氧系黏著劑溶液。 另一方面,作成如同比較例5,調整過氧化物固化型聚矽氧系黏著劑溶液。(Comparative example 7) First, as in Comparative Example 2, an addition reaction type polysiloxane-based adhesive solution was adjusted. On the other hand, as in Comparative Example 5, a peroxide-curing polysiloxane-based adhesive solution was adjusted.
接著,將獲得的加成反應型聚矽氧系黏著劑溶液與過氧化物固化型聚矽氧系黏著劑溶液進行混合攪拌,調製黏著劑混合溶液。另外,加成反應型聚矽氧系黏著劑與過氧化物固化型聚矽氧系黏著劑的混合比率是以對於加成反應型聚矽氧系黏著劑100質量份(固含量)包含150質量份(固含量)的過氧化物固化型聚矽氧系黏著劑的方式進行調整。
接著,將此黏著劑混合溶液,塗布於厚度38μm的由聚對苯二甲酸乙二酯(PET)膜所成的基材2上後,以160℃的溫度3分鐘進行加熱,從而形成乾燥後的厚度為20μm的黏著劑層3。藉此,獲得乾燥後的總厚為58μm的黏著帶1。Next, the obtained addition reaction type polysiloxane-based adhesive solution and the peroxide curing type polysiloxane-based adhesive solution are mixed and stirred to prepare an adhesive mixed solution. In addition, the mixing ratio of the addition reaction type silicone adhesive and the peroxide curing type silicone adhesive is 150 parts by mass for 100 parts by mass (solid content) of the addition reaction type silicone adhesive. Parts (solid content) of peroxide curing polysiloxane-based adhesive to adjust.
Next, this adhesive mixed solution was applied to a
(比較例8) 首先,作成如同實施例13,調整加成反應型聚矽氧系黏著劑溶液。 另一方面,作成如同比較例6,調整過氧化物固化型聚矽氧系黏著劑溶液。(Comparative Example 8) First, as in Example 13, the addition reaction type polysiloxane-based adhesive solution was adjusted. On the other hand, as in Comparative Example 6, a peroxide-curing polysiloxane-based adhesive solution was adjusted.
接著,將獲得的加成反應型聚矽氧系黏著劑溶液與過氧化物固化型聚矽氧系黏著劑溶液進行混合攪拌,調製黏著劑混合溶液。另外,加成反應型聚矽氧系黏著劑與過氧化物固化型聚矽氧系黏著劑的混合比率是以對於加成反應型聚矽氧系黏著劑100質量份(固含量)包含30質量份(固含量)的過氧化物固化型聚矽氧系黏著劑的方式進行調整。
接著,將此黏著劑混合溶液,塗布於厚度38μm的由聚對苯二甲酸乙二酯(PET)膜所成的基材2上後,以160℃的溫度3分鐘進行加熱,從而形成乾燥後的厚度為20μm的黏著劑層3。藉此,獲得乾燥後的總厚為58μm的黏著帶1。Next, the obtained addition reaction type polysiloxane-based adhesive solution and the peroxide curing type polysiloxane-based adhesive solution are mixed and stirred to prepare an adhesive mixed solution. In addition, the mixing ratio of the addition reaction type silicone adhesive and the peroxide curing type silicone adhesive is 30 parts by mass for 100 parts by mass (solid content) of the addition reaction type silicone adhesive. Parts (solid content) of peroxide curing polysiloxane-based adhesive to adjust.
Next, this adhesive mixed solution was applied to a
將實施例1~15、比較例1~8中的黏著劑層3的各成分的含量、及各層的厚度,示於表1~表3。另外,表1~表3中,將「聚矽氧膠」及「聚矽氧樹脂」的用語,分別省略而記載為「膠」及「樹脂」。The content of each component of the
2.評價方法
接著,就黏著帶1的評價方法進行說明。
(1)黏著力試驗
就以實施例1~15及比較例1~8製作的黏著帶1,準據於記載於黏著帶黏著片試驗方法(JIS Z 0237(2009))的方法,進行對BA-SUS黏著力試驗(剝離黏著力試驗)。
具體而言,將黏著帶1黏貼於進行輝面退火(BA)處理的表面粗糙度(Ra)為50±25nm的不鏽鋼板(SUS304),使質量2000g的輥子以5mm/s的速度往返1次,進行壓接。接著,放置20~40分鐘後,使用拉伸試驗機,對不鏽鋼板往180°方向以5mm/s的速度進行剝離,測定對於研磨SUS板之黏著力。
另外,黏著力試驗是對照射紫外線前的黏著帶1進行。此外,黏著力試驗的結果方面,考量將黏著帶1用於半導體材料的切割的情況下的固定力時,2.4N/10mm以上且5.5N/10mm以下為優選。2. Evaluation method
Next, the evaluation method of the
(2)滾球黏性試驗
(2-1)初始滾球黏性的測定
就以實施例1~15及比較例1~8製作的黏著帶1,準據於記載於黏著帶黏著片試驗方法(JIS Z 0237(2009))的方法,進行滾球黏性試驗。(2) Rolling ball viscosity test
(2-1) Determination of initial ball viscosity
With respect to the
(2-2)UV照射後滾球黏性的測定
將以實施例1~15及比較例1~8製作的個別的黏著帶1的黏著劑層3,黏貼於氟系剝離膜(Nippa株式會社製SS1A,厚度75μm)。接著,從黏著帶1的基材2側照射紫外線,溫度23度、濕度50±5%RH的條件下放置20~40分鐘後,準據於記載於黏著帶黏著片試驗方法(JIS Z 0237(2009))的方法,作成如同初始滾球黏性,進行滾球黏性試驗。
紫外線的照射是使用高壓水銀燈,以波長365nm在累積光量下成為1200mJ/cm2
的方式進行調整而照射。另外,就使累積光量為3000mJ/cm2
的情況下的滾球黏性雖亦同樣地進行測定,惟未見與使累積光量為1200mJ/cm2
的情況的差,故此處係使累積光量為1200mJ/cm2
而進行評價。(2-2) Measurement of roller ball viscosity after UV irradiation The
滾球黏性試驗的結果方面,考量被透過切割而個片化的半導體晶片等的拾取性時,比起初始滾球黏性(球No.),UV照射後滾球黏性(球No.)低為優選。In terms of the results of the ball tack test, when considering the pick-up properties of semiconductor chips, etc. that have been diced by dicing, the ball tack (ball No.) is compared to the initial ball tack (ball No.) after UV irradiation. ) Low is preferred.
(3)保持力試驗
(3-1)初始保持力的測定
就以實施例1~15及比較例1~8製作的黏著帶1,準據於記載於黏著帶黏著片試驗方法(JIS Z 0237(2009))的方法,進行保持力試驗。
具體而言,黏貼於以耐水砂紙進行研磨的不鏽鋼板(SUS304),以施加既定的重量的狀態,溫度40℃、濕度33%RH的條件下進行保持,測定至黏著帶1從不鏽鋼板剝離而落下為止的經過時間(落下時間(分))。再者,觀察黏著帶1從不鏽鋼板剝離之際的破壞模式(黏著劑層3與不鏽鋼板之間的破壞模式為界面破壞或聚力失效)。另外,保持力試驗中的落下時間的測定是進行5000分。此外,示於後述的表4~表6的保持力試驗的結果方面,顯示落下時間(分)及黏著帶1的破壞模式。此外,至5000分為止黏著帶1未剝離(落下)的情況下顯示「保持」。(3) Retention test
(3-1) Measurement of initial retention
Regarding the
(3-2)UV照射後保持力的測定
作成如同記載於上述的UV照射後的滾球黏性的測定的條件,對黏著帶1照射紫外線,放置後,作成如同初始保持力而進行保持力試驗。(3-2) Determination of holding power after UV irradiation
The
(3-3)關於保持力與破壞模式的關係
於此,就黏著帶1的保持力與破壞模式的關係進行說明。圖3為就黏著劑層3中的加成反應型聚矽氧系黏著劑的交聯密度、和黏著帶1的保持力試驗的結果(落下時間)的關係進行繪示的示意圖。
如示於圖3,在黏著帶1方面,隨著黏著劑層3中的加成反應型聚矽氧系黏著劑的交聯密度上升,依保持力試驗之黏著帶1的對於不鏽鋼板的破壞模式變化為[黏著劑層3的聚力失效(落下)]→[保持(不落下)]→[黏著劑層3與不鏽鋼板的界面破壞(落下)]。(3-3) Regarding the relationship between retention and failure mode
Here, the relationship between the holding force of the
此外,如示於圖3,在黏著帶1的破壞模式為聚力失效的區域,黏著帶1的保持力(落下時間)隨著黏著劑層3中的加成反應型聚矽氧系黏著劑的交聯密度上升而上升。
另一方面,如示於圖3,在黏著帶1的破壞模式為界面破壞的區域,黏著帶1的保持力(落下時間)隨著黏著劑層3中的加成反應型聚矽氧系黏著劑的交聯密度上升而降低。此原因推測為,隨著加成反應型聚矽氧系黏著劑的交聯密度上升,黏著劑層3的凝聚力上升,黏著帶1的黏著力降低,結果黏著帶1變得容易從不鏽鋼板剝離而落下。In addition, as shown in FIG. 3, in the region where the failure mode of the
保持力試驗的結果方面,優選上至少UV照射後的破壞模式為保持或界面破壞,更優選上至少UV照射後的破壞模式為界面破壞,再更優選上初始(UV照射前)及UV照射後的破壞模式皆為界面破壞。此外,初始(UV照射前)與UV照射後的破壞模式皆為界面破壞的情況下,比起初始(UV照射前),UV照射後的保持力(落下時間)低為優選。
此情況下,將黏著帶1使用於半導體元件基板等的切割之後,將獲得的半導體晶片等從黏著帶1剝離之際,對黏著帶1照射UV使得在半導體晶片等不易產生黏劑殘物。Regarding the results of the retention test, it is preferable that the failure mode after at least UV irradiation is retention or interface failure, and it is more preferable that the failure mode after at least UV irradiation is interface failure, and still more preferably the initial (before UV irradiation) and after UV irradiation The destruction modes are all interface destruction. In addition, when both the initial (before UV irradiation) and the failure modes after UV irradiation are interface failure, it is preferable that the retention force (fall time) after UV irradiation is lower than the initial (before UV irradiation).
In this case, after the
(4)對聚矽氧樹脂黏劑殘物試驗
就以實施例1~15及比較例1~8製作的黏著帶1,進行對於聚矽氧樹脂的黏劑殘物試驗。
首先,將為LED裝置用聚矽氧樹脂的含有甲基的聚矽氧樹脂(信越化學工業株式會社製KER-2500N(商品名))的A劑與B劑以混合比1:1進行混合而製作混合液。將此混合液塗布於不鏽鋼板,以100℃×1小時、進一步以150℃×2小時的條件予以加熱硬化,製作聚矽氧試片A。
同樣地,將為LED裝置用聚矽氧樹脂的含有苯基的聚矽氧樹脂(信越化學工業株式會社製的KER-6110(商品名))的A劑與B劑以混合比3:7混合而製作混合液。將此混合液,塗布於不鏽鋼板,以100℃×2小時進一步以150℃×5小時的條件予以加熱硬化,製作聚矽氧試片B。(4) Test on residue of polysiloxane resin adhesive
With respect to the
接著,將黏著帶1的黏著劑層3,分別黏貼於聚矽氧試片A、B,使質量2000g的輥子以5mm/s的速度往返1次,進行壓接。接著,作成如同記載於UV照射後的滾球黏性的測定的條件,從黏著帶1的基材2側照射紫外線後,溫度40℃、濕度90%RH的環境下放置120小時。之後,調成室溫,將黏著帶1,對於聚矽氧試片A、B往90°方向以800mm/s~1200mm/s的速度進行剝離,以目視確認對於聚矽氧試片A、B之黏劑殘物。Next, the
(5)對環氧樹脂黏劑殘物試驗
就以實施例1~15及比較例1~8製作的黏著帶1,進行對於環氧樹脂之黏劑殘物試驗。
對由使環氧樹脂浸漬於玻璃布基材的環氧樹脂板(日光化成株式會社製NL-EG-23(商品名))所成的環氧試片,黏貼黏著帶1的黏著劑層3,使質量2000g的輥子以5mm/s的速度d往返1次,進行壓接。接著,作成如同記載於UV照射後的滾球黏性的測定的條件,從黏著帶1的基材2側照射紫外線後,溫度40℃、濕度90%RH的環境下放置120小時。之後,調成室溫,將黏著帶1,對於環氧試片往90°方向以800mm/s~1200mm/s的速度進行剝離,以目視確認對於環氧試片的黏劑殘物。(5) Test on the residue of epoxy resin adhesive
With respect to the
對聚矽氧樹脂黏劑殘物試驗及對環氧樹脂黏劑殘物試驗是依以下的判斷基準進行評價。另外,使A或B的評價為合格。 A:試片的每單元面積100%的範圍內無黏劑殘物 B:試片的每單元面積不足2%的範圍內發現黏劑殘物 C:試片的每單元面積2%以上且不足5%的範圍內發現黏劑殘物 D:試片的每單元面積5%以上的範圍內發現黏劑殘物,或在試片的邊緣部分發現黏劑殘物The silicone resin adhesive residue test and the epoxy resin adhesive residue test are evaluated according to the following criteria. In addition, the evaluation of A or B was passed. A: There is no adhesive residue within 100% of the unit area of the test piece B: Adhesive residue was found within the range of less than 2% of the unit area of the test piece C: Adhesive residue was found in the range of more than 2% and less than 5% per unit area of the test piece D: Adhesive residues are found in the range of more than 5% of the unit area of the test piece, or adhesive residues are found on the edge of the test piece
(6)切割試驗
就以實施例1~15及比較例1~8製作的黏著帶1,進行切割試驗。
具體而言,首先,將模用環氧樹脂(日立化成株式會社製CEL-400ZHF40-W75G(商品名))放入金屬模,以密封壓力50kgf/cm2
(491N/cm2
)、密封材的厚度0.3mm、加熱溫度150℃×300秒的條件予以加熱硬化,製作圓板狀(直徑200mm(8寸))的切割試片。
此外,將黏著帶1的黏著劑層3黏貼於切割用環,切除從環突出的部分後,進一步黏貼於氟系剝離膜(Nippa株式會社製SS1A(商品名)、厚度75μm)。接著,使質量2000g的輥子往返,將黏著帶1與環部分進行壓接。接著,將氟系剝離膜剝離,使切割試片黏貼於環中央部分的黏著劑層,進行壓接。(6) Cutting test The
再者,使用東京精密株式會社製切割裝置(A-WD-100A(商品名)),以DISCO株式會社製的切割刀,將切割試片與黏著帶1一起切斷為10mm×10mm的晶片。此時,就飛散的晶片的個數進行計測,進行切割試驗中的固定力的評價。
接著,對黏貼於個片化為10mm×10mm的晶片的黏著帶1,作成如同記載於UV照射後的滾球黏性的測定的條件,照射紫外線。之後,拾取從黏著帶1個片化的晶片,以目視確認對於晶片的黏劑殘物的有無,進行切割試驗中的黏劑殘物的評價。此外,在拾取晶片之際,就拾取失敗的晶片的個數進行計測,進行切割試驗中的拾取性的評價。Furthermore, using a dicing device (A-WD-100A (trade name)) manufactured by Tokyo Precision Co., Ltd., a dicing blade manufactured by DISCO Co., Ltd. was used to cut the dicing test piece together with the
切割試驗中的固定力是依以下的判斷基準進行評價。另外,使A或B的評價為合格。 A:飛散的晶片的個數為100個中0個 B:飛散的晶片的個數為100個中1個 C:飛散的晶片的個數為100個中2個 D:飛散的晶片的個數為100個中3個以上The fixing force in the cutting test was evaluated according to the following criteria. In addition, the evaluation of A or B was passed. A: The number of scattered chips is 0 out of 100 B: The number of scattered chips is 1 out of 100 C: The number of scattered chips is 2 out of 100 D: The number of scattered chips is more than 3 out of 100
切割試驗中的黏劑殘物是依以下的判斷基準進行評價。另外,使A的評價為合格。 A:於晶片未發現黏劑殘物 D:於晶片發現黏劑殘物,或於晶片之側面發現黏著劑的牽絲The adhesive residue in the cutting test was evaluated according to the following criteria. In addition, the evaluation of A was passed. A: No adhesive residue was found on the wafer D: Adhesive residue found on the wafer, or the filament of the adhesive found on the side of the wafer
切割試驗中的拾取性是依以下的判斷基準進行評價。另外,使A或B的評價為合格。 A:拾取失敗的晶片的個數為100個中0個 B:拾取失敗的晶片的個數為100個中1個 C:拾取失敗的晶片的個數為100個中2個 D:拾取失敗晶片的個數為100個中3個以上The pickability in the cutting test was evaluated according to the following criteria. In addition, the evaluation of A or B was passed. A: The number of wafers that failed to be picked is 0 out of 100 B: The number of failed wafers is 1 out of 100 C: The number of failed wafers is 2 out of 100 D: The number of failed pick-up wafers is more than 3 out of 100
3.試驗結果
關於對於實施例1~15及比較例1~8的黏著帶1的評價結果,示於表4~6。3. Test results
The evaluation results of the
如示於表4~6,與黏著劑層3以加成反應型聚矽氧系黏著劑為主劑且包含感光鉑(Pt)觸媒及對於該加成反應型聚矽氧系黏著劑的交聯劑的第1形態對應的實施例1~8的黏著帶1、及與黏著劑層3以加成反應型聚矽氧系黏著劑與過氧化物固化型聚矽氧系黏著劑的混合物為主劑且包含感光鉑(Pt)觸媒及對於該加成反應型聚矽氧系黏著劑的交聯劑的第2形態對應的實施例9~15的黏著帶1方面,黏著力試驗、滾球黏性試驗、保持力試驗、對聚矽氧樹脂黏劑殘物試驗、對環氧樹脂黏劑殘物試驗、及切割試驗(固定力、黏劑殘物及拾取性)中的任一者皆確證獲得良好的結果。As shown in Tables 4 to 6, with the
藉此,與黏著劑層3以加成反應型聚矽氧系黏著劑為主劑且包含感光鉑(Pt)觸媒及對於該加成反應型聚矽氧系黏著劑的交聯劑的第1形態對應的實施例1~8的黏著帶1、及與黏著劑層3以加成反應型聚矽氧系黏著劑與過氧化物固化型聚矽氧系黏著劑的混合物為主劑且包含感光鉑(Pt)觸媒及對於該加成反應型聚矽氧系黏著劑的交聯劑的第2形態對應的實施例9~15的黏著帶1是確證有用於作為半導體材料的切割用黏著帶,更具體而言用於作為從半導體元件基板的密封樹脂側黏貼而使用於切割的切割用黏著帶。Thereby, the first layer of the addition reaction type polysiloxane-based adhesive with the
相對於此,黏著劑層3不符合第1形態的黏著劑層3的條件的比較例1~3及黏著劑層3不符合第2形態的黏著劑層3的條件的比較例4~8於對聚矽氧樹脂黏劑殘物試驗、對環氧樹脂黏劑殘物試驗及切割試驗(固定力、黏劑殘物及拾取性),確證任一個試驗結果為比實施例1~15差的結果。In contrast, Comparative Examples 1 to 3 where the
具體而言,不包含第1形態的黏著劑層3中的感光鉑(Pt)觸媒的比較例1的黏著帶1方面,儘管包含一般的鉑(Pt)觸媒,在UV照射前後,滾球黏性試驗及保持力試驗的結果方面未見變化,凝聚力的提升不充分,故於對聚矽氧樹脂黏劑殘物試驗及對環氧樹脂黏劑殘物試驗,發現多的黏劑殘物。此外,於切割試驗,亦切割試片的晶片的拾取性差,於晶片發現黏劑殘物。Specifically, the
此外,不包含第2形態的黏著劑層3中的感光鉑(Pt)觸媒的比較例4的黏著帶1方面,亦為與比較例1同樣的結果。In addition, the
再者,聚矽氧膠(G)的全質量(Gw)與聚矽氧樹脂(R)的全質量(Rw)的質量比(Gw)/(Rw)及聚矽氧膠(G)與聚矽氧樹脂(R)的合計質量中的具有烯基的聚矽氧膠(G1)的含有比率分別不足在第1形態的黏著劑層3方面的下限值的比較例2的黏著帶1方面,黏著力高,UV照射前後,滾球黏性試驗及保持力試驗的結果方面變化少,凝聚力提升稍不充分。為此,於對聚矽氧樹脂黏劑殘物試驗及對環氧樹脂黏劑殘物試驗,發現多的黏劑殘物。此外,於切割試驗,亦切割試片的晶片的拾取性差,於晶片表面發現黏劑殘物。Furthermore, the mass ratio (Gw)/(Rw) of the total mass (Gw) of the silicone (G) to the total mass (Rw) of the silicone (R) and the silicone (G) and poly The content ratio of the polysiloxane having an alkenyl group (G1) in the total mass of the silicone resin (R) is less than the lower limit of the
再另外,聚矽氧膠(G)的全質量(Gw)與聚矽氧樹脂(R)的全質量(Rw)的質量比(Gw)/(Rw)及聚矽氧膠(G)與聚矽氧樹脂(R)的合計質量中的具有烯基的聚矽氧膠(G1)的含有比率分別超過第1形態的黏著劑層3方面的上限值的比較例3的黏著帶1方面,UV照射前後,儘管滾球黏性試驗及保持力試驗的結果發生變化,凝聚力提升,黏著力低,故於切割試驗,切割試片的固定力低,發現多的晶片的飛散。另外,於對聚矽氧樹脂黏劑殘物試驗及對環氧樹脂黏劑殘物試驗未發現黏劑殘物。此外,於切割試驗,亦在未飛散的晶片方面,未發現黏劑殘物。In addition, the mass ratio (Gw) of the total mass (Gw) of the polysiloxane (G) to the total mass (Rw) of the polysiloxane (R) and the polysiloxane (G) and poly The
再另外,聚矽氧膠(G)的全質量(Gw)與聚矽氧樹脂(R)的全質量(Rw)的質量比(Gw)/(Rw)不足第2形態的黏著劑層3方面的下限值的比較例5的黏著帶1方面,UV照射前後,儘管滾球黏性試驗及保持力試驗的結果稍微變化,凝聚力提升,仍無法謂之充分,於切割試驗,得知切割試片的晶片的拾取性稍差。另外,於對聚矽氧樹脂黏劑殘物試驗及對環氧樹脂黏劑殘物試驗,黏劑殘物為稍微存在的程度,於切割試驗,可拾取的晶片方面,未發現黏劑殘物。In addition, the mass ratio (Gw)/(Rw) of the total mass (Gw) of the polysiloxane (G) to the total mass (Rw) of the polysiloxane (R) is less than the adhesive layer of the second aspect. For the
再另外,聚矽氧膠(G)的全質量(Gw)與聚矽氧樹脂(R)的全質量(Rw)的質量比(Gw)/(Rw)超過第2形態的黏著劑層3方面的上限值的比較例6的黏著帶1方面,UV照射前後,儘管滾球黏性試驗及保持力試驗的結果發生變化,凝聚力提升,黏著力低,故於切割試驗,切割試片的固定力低,發現多的晶片的飛散。另外,於對聚矽氧樹脂黏劑殘物試驗及對環氧樹脂黏劑殘物試驗未發現黏劑殘物。此外,於切割試驗,亦在未飛散的晶片方面,未發現黏劑殘物。In addition, the mass ratio (Gw)/(Rw) of the total mass (Gw) of the polysiloxane (G) to the total mass (Rw) of the polysiloxane (R) exceeds the adhesive layer of the second aspect in three aspects In the
再另外,聚矽氧膠(G)的全質量(Gw)與聚矽氧樹脂(R)的全質量(Rw)的質量比(Gw)/(Rw)超過第2形態的黏著劑層3方面的上限值,且聚矽氧膠(G)與聚矽氧樹脂(R)的合計質量中的具有烯基的聚矽氧膠(G1)的含有比率不足第2形態的黏著劑層3方面的下限值的比較例7的黏著帶1方面,由於過氧化物固化型聚矽氧黏著劑的硬化的影響使得黏著力高,此外UV照射前後,滾球黏性試驗及保持力試驗的結果方面變化少,凝聚力的進一步的提升稍不充分。為此,於對聚矽氧樹脂黏劑殘物試驗及對環氧樹脂黏劑殘物試驗,發現多的黏劑殘物。此外,於切割試驗,亦切割試片的晶片的拾取性差,於晶片表面發現黏劑殘物。In addition, the mass ratio (Gw)/(Rw) of the total mass (Gw) of the polysiloxane (G) to the total mass (Rw) of the polysiloxane (R) exceeds the adhesive layer of the second aspect in three aspects The upper limit value of the polysiloxane (G) and the polysiloxane resin (R) in the total mass of the polysiloxane (G1) with an alkenyl group content ratio is less than the second form of the
再另外,聚矽氧膠(G)與聚矽氧樹脂(R)的合計質量中的具有烯基的聚矽氧膠(G1)的含有比率超過第2形態的黏著劑層3方面的上限值的比較例8的黏著帶1方面,UV照射前後,儘管滾球黏性試驗及保持力試驗的結果發生變化,凝聚力提升,黏著力低,故於切割試驗,切割試片的固定力低,發現多的晶片的飛散。另外,於對聚矽氧樹脂黏劑殘物試驗及對環氧樹脂黏劑殘物試驗未發現黏劑殘物。此外,於切割試驗,亦在未飛散的晶片方面,未發現黏劑殘物。In addition, the content ratio of the polysiloxane (G1) having an alkenyl group in the total mass of the polysiloxane (G) and the polysiloxane resin (R) exceeds the upper limit of the third aspect of the
1:黏著帶 2:基材 3:黏著劑層 100:半導體元件基板 101:基板 102:半導體元件 103:密封樹脂 200:半導體晶片1: adhesive tape 2: substrate 3: Adhesive layer 100: semiconductor element substrate 101: substrate 102: Semiconductor components 103: Sealing resin 200: semiconductor chip
[圖1]就適用本實施方式之切割用黏著帶的構成的一例進行繪示的圖。 [圖2](a)~(e)為就使用本實施方式的黏著帶之半導體晶片之製造方法進行繪示的圖。 [圖3]就黏著劑層方面的加成反應型聚矽氧系黏著劑的交聯密度、和黏著帶的保持力試驗的結果(落下時間)的關係進行繪示的示意圖。[Fig. 1] A diagram showing an example of a configuration to which the adhesive tape for cutting according to this embodiment is applied. [Fig. 2] (a) to (e) are diagrams illustrating a method of manufacturing a semiconductor wafer using the adhesive tape of this embodiment. [Fig. 3] A schematic diagram showing the relationship between the crosslinking density of the addition reaction type polysiloxane-based adhesive in the adhesive layer and the result (fall time) of the adhesive tape retention test.
1:黏著帶 1: adhesive tape
2:基材 2: substrate
3:黏著劑層 3: Adhesive layer
Claims (6)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018164411 | 2018-09-03 | ||
JP2018-164411 | 2018-09-03 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW202020094A true TW202020094A (en) | 2020-06-01 |
TWI799618B TWI799618B (en) | 2023-04-21 |
Family
ID=69721630
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW108125200A TWI799618B (en) | 2018-09-03 | 2019-07-17 | Adhesive tape for dicing and method of manufacturing semiconductor wafer |
Country Status (5)
Country | Link |
---|---|
JP (2) | JP7374909B2 (en) |
KR (1) | KR102632461B1 (en) |
CN (1) | CN112602172A (en) |
TW (1) | TWI799618B (en) |
WO (1) | WO2020050167A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114846580A (en) * | 2019-12-19 | 2022-08-02 | 麦克赛尔株式会社 | Adhesive tape for dicing and method for manufacturing semiconductor chip |
JPWO2021124724A1 (en) * | 2019-12-20 | 2021-06-24 | ||
KR20230005219A (en) | 2020-04-30 | 2023-01-09 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Method for manufacturing temporary adhesive for wafer processing, wafer laminate and thin wafer |
CN113320036B (en) * | 2021-06-18 | 2024-02-13 | 常州时创能源股份有限公司 | Squaring and cutting process of strip-shaped silicon material and application thereof |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3417230B2 (en) * | 1996-09-25 | 2003-06-16 | 信越化学工業株式会社 | Photocurable liquid silicone rubber composition for mold making |
JP2005093503A (en) | 2003-09-12 | 2005-04-07 | Hitachi Cable Ltd | Dicing method |
JP2013038408A (en) | 2011-07-14 | 2013-02-21 | Nitto Denko Corp | Adhesive tape for fixing semiconductor wafer, method for manufacturing semiconductor chip and adhesive tape with adhesive film |
JP5880399B2 (en) | 2012-11-13 | 2016-03-09 | 信越化学工業株式会社 | Method for producing silicone rubber molding |
JP6168553B2 (en) * | 2013-08-30 | 2017-07-26 | 日立マクセル株式会社 | Dicing adhesive tape and semiconductor chip manufacturing method |
KR20150112851A (en) | 2014-03-28 | 2015-10-07 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Silicone adhesive composition, method for making the same and adhesive film |
JP6395597B2 (en) | 2014-12-25 | 2018-09-26 | マクセルホールディングス株式会社 | Dicing adhesive tape and semiconductor chip manufacturing method |
US9777203B2 (en) * | 2015-06-08 | 2017-10-03 | Momentive Performance Materials | Silicone pressure sensitive adhesive compositions and protective films containing the same |
-
2019
- 2019-07-17 TW TW108125200A patent/TWI799618B/en active
- 2019-08-30 KR KR1020217005574A patent/KR102632461B1/en active IP Right Grant
- 2019-08-30 JP JP2020541187A patent/JP7374909B2/en active Active
- 2019-08-30 WO PCT/JP2019/034126 patent/WO2020050167A1/en active Application Filing
- 2019-08-30 CN CN201980055642.2A patent/CN112602172A/en active Pending
-
2023
- 2023-07-14 JP JP2023115978A patent/JP2023138530A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
JP2023138530A (en) | 2023-10-02 |
KR102632461B1 (en) | 2024-02-02 |
CN112602172A (en) | 2021-04-02 |
JP7374909B2 (en) | 2023-11-07 |
KR20210056334A (en) | 2021-05-18 |
WO2020050167A1 (en) | 2020-03-12 |
TWI799618B (en) | 2023-04-21 |
JPWO2020050167A1 (en) | 2021-08-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TW202020094A (en) | Adhesive tape for dicing and method for manufacturing semiconductor chips | |
WO2021124724A1 (en) | Adhesive tape for dicing and method for producing semiconductor chip | |
US20070218299A1 (en) | Thermosetting composition and film having a layer comprising the composition | |
KR20160114078A (en) | Wafer workpiece, provisional adhesive material for wafer working, and thin wafer manufacturing method | |
TWI631202B (en) | Method for manufacturing dicing adhesive tape and semiconductor wafer | |
KR20050021485A (en) | Silicone-based adhesive sheet, method of bonding a semiconductor chip to a chip attachment component, and a semiconductor device | |
CN108070261B (en) | Heat-curable silicon-oxygen composition, die-bonding material, and optical semiconductor device | |
JP2015073084A (en) | Wavelength conversion sheet, sealed optical semiconductor, and optical semiconductor element device | |
JP2009242605A (en) | Adhesive composition, adhesive sheet, and production method of semiconductor device | |
JP2017163105A (en) | Optical semiconductor device covering sheet, adhesion layer-covering layer-attached optical semiconductor device and manufacturing method thereof, and method for manufacturing adhesion layer-attached optical semiconductor device | |
TW202103954A (en) | Thermally conductive composite tape | |
TWI829732B (en) | Polysilicone adhesive composition and adhesive tape or adhesive film using the same | |
WO2022138341A1 (en) | Integrated dicing die bonding sheet and method for producing semiconductor device | |
WO2021124725A1 (en) | Adhesive tape for dicing, and method for producing semiconductor chip | |
JP7032052B2 (en) | Silicone resin film and its manufacturing method, and semiconductor device manufacturing method | |
JP2016171315A (en) | Adhesive sheet, method for manufacturing adhesive optical semiconductor element and method for manufacturing optical semiconductor device | |
TWI655682B (en) | Adhesive tape for dicing and manufacturing method of semiconductor wafer | |
JP2023052354A (en) | Temporary adhesive material for processing substrate and manufacturing method of laminate | |
TWI840630B (en) | Adhesive tape for dicing and method for manufacturing semiconductor chip | |
JP2012182402A (en) | Dicing/die bonding sheet and method for processing sapphire substrate for led | |
TWI814931B (en) | Method for manufacturing laminate and method for manufacturing substrate | |
JP2013136671A (en) | Silicone resin sheet, cured sheet, light-emitting diode device and method for manufacturing the same | |
WO2016143623A1 (en) | Adhesive sheet, adhesive light semiconductor element production method and optical semiconductor device production method |