TWI586783B - Heat peelable adhesive sheet for use in cutting electronic component and method for cutting electronic component - Google Patents
Heat peelable adhesive sheet for use in cutting electronic component and method for cutting electronic component Download PDFInfo
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- TWI586783B TWI586783B TW101134543A TW101134543A TWI586783B TW I586783 B TWI586783 B TW I586783B TW 101134543 A TW101134543 A TW 101134543A TW 101134543 A TW101134543 A TW 101134543A TW I586783 B TWI586783 B TW I586783B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
- C09J2301/162—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer the carrier being a laminate constituted by plastic layers only
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/412—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of microspheres
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
- C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
- C09J2475/006—Presence of polyurethane in the substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
- H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
- H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
- H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
- H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本發明係關於一種電子零件切斷用加熱剝離型黏著片及電子零件切斷方法。 The present invention relates to a heat-peelable adhesive sheet for cutting an electronic component and a method for cutting an electronic component.
近年來，隨著電子零件或半導體之小型化，業界較先前更加追求被加工物之加工精度。於先前之使用熱剝離型黏著片之加工方法中，黏著劑層較柔軟且較厚，故因由加工時之應力引起之黏著劑之移動而無法獲得充分之加工精度。 In recent years, with the miniaturization of electronic components or semiconductors, the industry has pursued processing precision of processed objects more than before. In the prior art processing method using the heat-peelable adhesive sheet, since the adhesive layer is soft and thick, sufficient processing precision cannot be obtained due to the movement of the adhesive due to the stress during processing.
針對於此，有效的是使黏著劑層變薄，但若使黏著劑層過薄，則因由熱膨脹性微球之粒子導致之黏著劑層表面之凹凸而產生由氣泡等之侵入導致之外觀不良，且無法獲得充分之接著性，從而無法發揮作為固定用黏著片之功能。 In view of this, it is effective to make the adhesive layer thin. However, when the adhesive layer is too thin, irregularities on the surface of the adhesive layer due to particles of the heat-expandable microspheres cause appearance defects caused by the intrusion of bubbles or the like. And it is not possible to obtain sufficient adhesion, so that it cannot function as a fixing adhesive sheet.
因此，如專利文獻1所記載，已知有如下方法：利用於基材上介隔能量線硬化型彈性層而積層含有熱膨脹性微球之熱膨脹性黏著層而成之能量線硬化型熱剝離性黏著片固定電子零件或半導體晶圓，並於加工時藉由使能量線硬化型彈性層硬化而降低加工時之黏著劑之移動，由此提高加工精度，且於加工後藉由加熱剝離容易地回收零件。 Therefore, as described in Patent Document 1, there is known a method in which an energy ray-curing type thermal peeling property in which a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres is laminated on a substrate by an energy ray-curable elastic layer is known. The adhesive sheet fixes an electronic component or a semiconductor wafer, and at the time of processing, the energy ray-curable elastic layer is hardened to reduce the movement of the adhesive during processing, thereby improving the processing precision and easily peeling off by heating after processing. Recycle parts.
專利文獻1：日本專利特開2002-121505號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2002-121505
然而，利用該方法中使用之先前之能量線硬化型熱剝離性黏著片時存在硬化後之能量線硬化型彈性層與基材之密接性並不充分，於能量線硬化型彈性層與基材之間產生部分剝離(固著破壞)之情況，及於被黏著體上產生糊劑殘餘之情況，又，存在由切斷步驟產生之剖面相對於表面並不垂直，無法正確地切割之情況。 However, when the prior energy ray-curable heat-peelable adhesive sheet used in the method is used, the adhesion between the energy-hardening elastic layer and the substrate after curing is insufficient, and the energy ray-curable elastic layer and the substrate are insufficient. In the case where partial peeling (fixation damage) occurs, and the residue of the paste is generated on the adherend, there is a case where the cross section resulting from the cutting step is not perpendicular to the surface and cannot be cut correctly.
本發明者等人對先前之能量線硬化型熱剝離性黏著片之固著剝離進行銳意研究，結果有如下新發現：藉由在黏著劑層及基材之間提高化學親和性之方法及於基材表面形成微細凹凸而增大兩者之接觸面積之方法等通常之黏著片所利用之方法無法有效防止上述固著剝離等。繼而，反覆進行關於可有效地抑制此種黏著片之固著破壞的熱剝離性黏著片之構成之試行錯誤，從而完成本發明。 The inventors of the present invention conducted intensive studies on the fixation and peeling of the previous energy ray-curable heat-peelable adhesive sheet, and as a result, have newly discovered a method of improving chemical affinity between the adhesive layer and the substrate. A method in which a fine contact surface is formed on the surface of the substrate to increase the contact area between the two, such as a method of using a conventional adhesive sheet, cannot effectively prevent the above-described fixation peeling or the like. Then, the trial and error of the constitution of the heat-peelable adhesive sheet which can effectively suppress the fixation damage of such an adhesive sheet is repeatedly performed, and the present invention has been completed.
即，本發明之熱剝離型黏著片係如下者。 That is, the heat-peelable adhesive sheet of the present invention is as follows.
1.一種加熱剝離型黏著片，其特徵在於：其係於基材之至少單側介隔能量線硬化型彈性層而設置含有熱膨脹性微球之熱剝離性黏著劑層而成者，且於上述基材及能量線硬化型彈性層之間配置有有機塗層。 A heat-peelable pressure-sensitive adhesive sheet comprising: a heat-peelable adhesive layer containing at least one side of an insulating layer; and a heat-peelable adhesive layer containing heat-expandable microspheres; An organic coating layer is disposed between the substrate and the energy ray-curable elastic layer.
2.如技術方案1之加熱剝離型黏著片，其中上述有機塗層係由胺基甲酸酯系聚合物形成。 2. The heat-peelable adhesive sheet according to claim 1, wherein the organic coating layer is formed of a urethane-based polymer.
3.如技術方案1或2之加熱剝離型黏著片，其中熱剝離性黏著劑層之厚度為50 μm以下。 3. The heat-peelable adhesive sheet according to claim 1 or 2, wherein the heat-peelable adhesive layer has a thickness of 50 μm or less.
4.如技術方案1至3中任一項之加熱剝離型黏著片，其中能量線硬化型彈性層之厚度為3~150 μm。 4. The heat-peelable adhesive sheet according to any one of claims 1 to 3, wherein the energy ray-curable elastic layer has a thickness of from 3 to 150 μm.
5.一種電子零件之切斷方法，其特徵在於藉由如1至4中任一項之加熱剝離型黏著片將電子零件暫時固定而切斷該電子零件。 A method of cutting an electronic component, characterized in that the electronic component is cut by temporarily fixing the electronic component by the heat-peelable adhesive sheet according to any one of 1 to 4.
根據本發明，可獲得如下黏著片材，即，為提高加工精度而將薄於加熱膨脹性微球之最大粒徑之熱剝離型黏著劑層上產生的由熱膨脹性微球引起之凹凸貼合至硬化前之柔軟之能量線硬化型彈性層上並進行吸收，藉此製造具有良好外觀及表面平滑性之黏著片，其後或者於貼附至被加工物上後，使能量線硬化型彈性層硬化，將柔軟之黏著層(於此情形時為熱剝離型黏著劑)之厚度薄化。進而，藉由使用該黏著片對被加工物進行加工，可高精度地加工小型零件。 According to the present invention, it is possible to obtain an adhesive sheet which is formed by heat-expandable microspheres which is formed on a heat-peelable adhesive layer which is thinner than the maximum particle diameter of the heat-expandable microspheres in order to improve the processing precision. Adhesive sheet having a good appearance and surface smoothness is formed on the soft energy-hardening elastic layer before hardening, thereby making the energy ray-curable elastic after attaching to the workpiece. The layer is hardened to thin the thickness of the soft adhesive layer (in this case, the heat-peelable adhesive). Further, by processing the workpiece using the adhesive sheet, it is possible to process small parts with high precision.
又，根據本發明，可抑制按壓步驟或切斷步驟時之黏著劑之偏移或上捲、碎屑(chipping)，從而可垂直於該被加工物表面進行切斷。 Further, according to the present invention, it is possible to suppress the offset or the unwinding or chipping of the adhesive at the pressing step or the cutting step, and the cutting can be performed perpendicularly to the surface of the workpiece.
且於切斷後，可容易地剝離回收以高精度進行切斷加工而成之切斷片。因此，可明顯提高切斷片之剝離、回收步驟中之操作性及作業性，而且可較大地提高小型或薄層之半導體晶片或積層電容器晶片等切斷片之生產性。 Further, after the cutting, the cut piece obtained by cutting and cutting with high precision can be easily peeled off and recovered. Therefore, the workability and workability in the peeling and recovery steps of the cut piece can be remarkably improved, and the productivity of a cut piece such as a small or thin semiconductor wafer or a multilayer capacitor wafer can be greatly improved.
本發明者為解決上述課題進行銳意研究，結果針對該等 課題，可藉由使用於基材與含有熱膨脹性微球之熱剝離型黏著劑層之間包含能量線硬化型彈性層之黏著片而改善。 The present inventors conducted intensive studies to solve the above problems, and as a result, The problem can be improved by using an adhesive sheet comprising an energy ray-curable elastic layer between a substrate and a heat-peelable adhesive layer containing heat-expandable microspheres.
此外發現，藉由利用使用如下黏著片對被加工物進行加工之加工方法，可高精度地加工小型零件，從而完成本發明，該黏著片係為提高加工精度而將薄於熱膨脹性微球之最大粒徑之熱剝離型黏著劑層上產生的由熱膨脹性微球引起之凹凸貼合至硬化前之柔軟之能量線硬化型彈性層上等，藉此進行積層吸收，從而製造具有良好外觀及表面平滑性之黏著片，其後或於貼附至被加工物上後，使能量線硬化型彈性層硬化，將柔軟之黏著層(於此情形時為熱剝離型黏著劑層)之厚度薄化。 Further, it has been found that the present invention can be completed by processing a small-sized component with high precision by using a processing method for processing a workpiece using the following adhesive sheet, which is thinner than the heat-expandable microsphere for improving the processing precision. The unevenness of the heat-expandable microspheres generated on the heat-dissipative microspheres having the largest particle diameter is bonded to the soft energy ray-curable elastic layer before curing, thereby performing multilayer absorption, thereby producing a good appearance and The surface-smooth adhesive sheet is then hardened by the energy-line-hardening elastic layer after being attached to the workpiece, and the thickness of the soft adhesive layer (in this case, the heat-peelable adhesive layer) is thin. Chemical.
以下，基於圖1對本發明之加熱剝離型黏著片之結構進行說明。 Hereinafter, the structure of the heat-peelable adhesive sheet of the present invention will be described based on Fig. 1 .
本發明之加熱剝離型片材之特徵在於：其係於基材之至少單側介隔能量線硬化型彈性層而設置含有熱膨脹性微球之熱剝離型黏著劑層而成，且於基材與能量線硬化型彈性層之間配置有有機塗層。該能量線硬化型彈性層及該熱剝離型黏著劑層可設置於該基材之單面，亦可設置於兩面。 The heat-peelable sheet of the present invention is characterized in that it is provided on at least one side of the substrate, which is provided with a heat-dissipating adhesive layer containing heat-expandable microspheres, and is provided on the substrate. An organic coating is disposed between the energy ray-hardening elastic layer. The energy ray-curable elastic layer and the heat-peelable adhesive layer may be provided on one side of the substrate or on both sides.
於設置於單面之情形時，亦可於該基材之另一面上形成接著劑層，於加工電子零件時，可將固定有電子零件之包含該熱剝離型黏著劑層之該加熱剝離型黏著片載置於加工裝置之載置台上，藉由該基材之另一面上之接著劑層而固定於載置台上。 In the case of being disposed on one side, an adhesive layer may be formed on the other surface of the substrate, and when the electronic component is processed, the heat-peelable type including the heat-peelable adhesive layer may be fixed to the electronic component. The adhesive sheet is placed on the mounting table of the processing device and fixed to the mounting table by an adhesive layer on the other side of the substrate.
當然，並非必需於基材之另一面上形成該接著劑層，於 此情形時，亦可利用將固定有電子零件之包含該熱剝離型黏著劑層之該加熱剝離型黏著片設置於加工裝置之載置台上的固定機構，例如真空夾盤等進行固定。 Of course, it is not necessary to form the adhesive layer on the other side of the substrate. In this case, the heat-peelable pressure-sensitive adhesive sheet including the heat-peelable pressure-sensitive adhesive layer to which the electronic component is fixed may be fixed to a mounting table of the processing apparatus, for example, a vacuum chuck or the like.
其次，對構成本發明之加熱剝離型黏著片之各層進行闡述。 Next, each layer constituting the heat-peelable adhesive sheet of the present invention will be described.
基材1係成為有機塗層2、能量線硬化型彈性層3等之支持母體者，使用具有不因熱剝離型黏著劑層4之加熱處理而損壞機械物性之程度的耐熱性者。 The base material 1 is a support material such as the organic coating layer 2 and the energy ray-curable elastic layer 3, and heat resistance is used to the extent that the mechanical properties are not damaged by the heat treatment of the heat-peelable pressure-sensitive adhesive layer 4.
作為上述基材1，例如可列舉聚酯、烯烴系樹脂、聚氯乙烯等塑膠膜或片材，但並不限於該等。 The substrate 1 is, for example, a plastic film or a sheet such as a polyester, an olefin resin or a polyvinyl chloride, but is not limited thereto.
基材1較佳為相對於切斷被黏著體時所使用之切割器等切斷機構而具有切斷性。又，當使用軟質聚烯烴膜或片材等具備耐熱性及伸縮性之基材作為基材1時，若於被黏著體之切斷步驟時，切斷刀進入至基材中間，則於其後可擴展基材，故而適用於必需於切斷片間產生間隙之切斷片回收方式。 The base material 1 preferably has a cutting property with respect to a cutting mechanism such as a cutter used when cutting the adherend. In addition, when a substrate having heat resistance and stretchability such as a soft polyolefin film or sheet is used as the substrate 1, when the cutting blade enters the middle of the substrate during the cutting step of the adherend, Since the substrate can be expanded later, it is suitable for a cut piece recovery method in which a gap is required between the cut sheets.
進而，由於使能量線硬化型彈性層3硬化時使用能量線，故而基材1、有機塗層2(或熱剝離型黏著劑層4等)必需由可使特定量以上之能量線透過之材料構成。基材1可為單層亦可為多層體。又，利用下述適當之剝離劑對基材1實施表面處理，於其處理面上形成能量線硬化型彈性層，對所獲得之能量線硬化型熱膨脹性黏著片照射能量線，使該能量線硬化型彈性層硬化後剝離基材1，藉此亦可使該 能量線硬化型熱膨脹性黏著片本身薄層化。 Further, since the energy ray is used to cure the energy ray-curable elastic layer 3, the substrate 1, the organic coating 2 (or the heat-peelable adhesive layer 4, etc.) must be made of a material that can transmit a specific amount or more of energy rays. Composition. The substrate 1 may be a single layer or a multilayer body. Moreover, the base material 1 is subjected to a surface treatment by an appropriate release agent described below, an energy ray-curable elastic layer is formed on the treated surface, and the energy ray-curable heat-expandable pressure-sensitive adhesive sheet obtained is irradiated with an energy ray to make the energy ray After the hardened elastic layer is hardened, the substrate 1 is peeled off, whereby the The energy ray-curable heat-expandable pressure-sensitive adhesive sheet itself is thinned.
基材1之厚度可於無損被黏著體之貼合、被黏著體之切斷、切斷片之剝離、回收等各步驟中之操作性或作業性之範圍內進行適當選擇，通常為500 μm以下，較佳為3~300 μm左右，進而較佳為5~250 μm左右。 The thickness of the substrate 1 can be appropriately selected within the range of operability or workability in the respective steps of adhesion of the adherend, peeling of the adherend, peeling and recovery of the cut piece, and the like, and is usually 500 μm or less. Preferably, it is about 3 to 300 μm, and more preferably about 5 to 250 μm.
為提高與鄰接之層之密接性、保持性等，基材1之表面亦可實施有慣用之表面處理，例如鉻酸處理、臭氧暴露、火焰暴露、高壓電擊暴露、離子化放射線處理等化學或物理處理、利用底塗劑(例如下述黏著物質)進行之塗佈處理等。 In order to improve adhesion to adjacent layers, retention, etc., the surface of the substrate 1 may also be subjected to conventional surface treatment such as chromic acid treatment, ozone exposure, flame exposure, high voltage electric shock exposure, ionizing radiation treatment, etc. Physical treatment, coating treatment using a primer (for example, an adhesive described below), and the like.
有機塗層2必需與基材1良好地密接，且於加熱剝離後能量線硬化型彈性層不會固著破壞。 The organic coating layer 2 must be in good contact with the substrate 1, and the energy ray-curable elastic layer is not fixedly broken after being heated and peeled off.
固著破壞是否產生例如可利用下述實施例所記載之方法進行評價。藉由不產生固著破壞，可介隔有機塗層2更牢固地黏著基材及加熱剝離型黏著劑層，故而於使用本發明之加熱剝離型黏著片時加熱剝離性良好，且可發揮不產生糊劑剝落、即糊劑殘餘之效果。 Whether the fixation failure occurs can be evaluated, for example, by the method described in the following examples. By not causing the anchorage damage, the organic coating layer 2 can be more firmly adhered to the substrate and the peeling-type adhesive layer can be adhered. Therefore, when the heat-peelable pressure-sensitive adhesive sheet of the present invention is used, the heat-peelability is good and can be exhibited. The effect of the peeling of the paste, that is, the residue of the paste, is produced.
有機塗層2只要具有該等特性，則可使用任意材料。 As long as the organic coating 2 has such characteristics, any material can be used.
例如，可使用如文獻(塑膠硬塗材料II，CMC出版，(2004))中所示之各種塗佈材料。其中，較佳為胺基甲酸酯系聚合物。其原因在於，其對基材顯示優異之密接性，且對能量線硬化型彈性層(尤其是硬化後)顯示優異之固著性。尤其是聚丙烯酸胺基甲酸酯及聚酯聚胺基甲酸酯、及 該等之前驅物更佳。該等材料對基材1之塗敷、塗佈較簡便等，具有實用性，工業上可有多種選擇，且可廉價地獲得。 For example, various coating materials as shown in the literature (Plastic Hard Coating Material II, CMC Publishing, (2004)) can be used. Among them, a urethane-based polymer is preferred. This is because it exhibits excellent adhesion to the substrate and exhibits excellent fixing properties to the energy ray-curable elastic layer (especially after hardening). Especially polyacrylic acid urethane and polyester polyurethane, and These precursors are better. These materials are easy to apply and apply to the substrate 1, and are practical, and can be industrially available in various options and can be obtained at low cost.
作為聚丙烯酸胺基甲酸酯及聚酯聚胺基甲酸酯，可使用文獻(塑膠硬塗材料II，P17-21，CMC出版，(2004))及文獻(最新聚胺基甲酸酯材料及應用技術，CMC出版，(2005))中所示之任一者。該等為包含異氰酸酯單體與含醇性羥基之單體(例如含羥基之丙烯酸化合物或含羥基之酯化合物)之反應混合物之聚合物。亦可含有聚胺等鏈延長劑、防老化劑、氧化穩定劑等作為進而之成分。 As polyacrylic acid urethane and polyester polyurethane, literature (plastic hard coating material II, P17-21, CMC Publishing, (2004)) and literature (the latest polyurethane material) can be used. And any of the application techniques, CMC Publishing, (2005)). These are polymers comprising a reaction mixture of an isocyanate monomer and an alcoholic hydroxyl group-containing monomer such as a hydroxyl group-containing acrylic acid compound or a hydroxyl group-containing ester compound. Further, a chain extender such as a polyamine, an anti-aging agent, an oxidation stabilizer or the like may be contained as a further component.
聚丙烯酸胺基甲酸酯及聚酯聚胺基甲酸酯可使用藉由使上述單體反應而製備者，亦可使用作為塗佈材料或油墨、塗料之黏合劑樹脂而大量市售或使用者(參照文獻：最新聚胺基甲酸酯材料及應用技術，P190，CMC出版(2005))。作為上述聚胺基甲酸酯，可列舉大日精化製造之「NB300」、ADEKA製造之「ADEKA Bon-Tighter(註冊商標)」、三井化學製造之「TAKELAC(註冊商標)A/TAKENATE(註冊商標)A」、DIC Graphics製造之「UC Sealer」等市售品。 The polyacrylic acid urethane and the polyester polyurethane may be prepared by reacting the above monomers, or may be commercially available or used as a binder resin for coating materials or inks and coatings. (Reference literature: The latest polyurethane materials and application technology, P190, CMC Publishing (2005)). As the above-mentioned polyurethane, "NB300" manufactured by Daisei Seiki Co., Ltd., "ADEKA Bon-Tighter (registered trademark)" manufactured by ADEKA, and "TAKELAC (registered trademark) A/TAKENATE (registered trademark) manufactured by Mitsui Chemicals Co., Ltd. ) A", a commercial product such as "UC Sealer" manufactured by DIC Graphics.
亦可於上述聚合物中添加色素等，作為油墨印刷於膜層上而使用。此時例如可使用聚胺基甲酸酯系乙酸乙烯酯-氯乙烯共聚物(大日精化公司，NB300)等聚胺基甲酸酯改性樹脂，藉由上述印刷亦可提高黏著片之設計性。 A dye or the like may be added to the above polymer to be used as an ink printed on the film layer. In this case, for example, a polyurethane-modified resin such as a polyurethane-vinyl chloride-vinyl chloride copolymer (Daily Seika Co., Ltd., NB300) can be used, and the design of the adhesive sheet can be improved by the above printing. Sex.
作為尤其是聚丙烯酸胺基甲酸酯及聚酯胺基甲酸酯對基材顯示良好之密接性之理由，可認為在於：以單體形式而 包含之異氰酸酯成分與存在於基材表面之羥基或羧基等極性官能基進行反應而形成牢固之鍵。 The reason why, in particular, polyacrylic acid urethane and polyester urethane exhibit good adhesion to a substrate, it can be considered that it is in a monomer form. The isocyanate component contained therein reacts with a polar functional group such as a hydroxyl group or a carboxyl group present on the surface of the substrate to form a strong bond.
又，作為尤其是於能量線硬化後與能量線硬化型彈性層之固著性提高之理由，推測在於：於紫外線等照射時，生成於胺基甲酸酯鍵附近之自由基種與生成於能量線硬化型彈性層中之自由基種進行反應而形成牢固之鍵(文獻：聚胺基甲酸酯之結構、物性與高功能化及應用展開，p191-194，技術資訊協會(1999))。 Further, the reason why the fixing property of the energy ray-curable elastic layer is improved particularly after the energy ray curing is presumed to be that a radical species formed in the vicinity of the urethane bond is generated during irradiation with ultraviolet rays or the like. The radical species in the energy ray-hardening elastic layer react to form a strong bond (Document: Structure, physical properties, high functionality and application of polyurethane), p191-194, Technical Information Association (1999) .
有機塗層之厚度並無特別限定，例如適宜為0.1~10 μm左右，較佳為0.1~5 μm左右，更佳為0.5~5 μm左右。 The thickness of the organic coating layer is not particularly limited, and is, for example, about 0.1 to 10 μm, preferably about 0.1 to 5 μm, more preferably about 0.5 to 5 μm.
能量線硬化型彈性層3含有用以賦予能量線硬化性之能量線硬化性化合物(或能量線硬化性樹脂)，並且具有於壓接熱剝離型黏著劑層4時可緩和熱膨脹性微球之凹凸之程度的黏彈性(參照圖1之放大圖)。又，能量線硬化型彈性層3較佳為於能量線照射後成為彈性體。就上述觀點而言，能量線硬化型彈性層3較佳為使用經能量線反應性官能基化學改性之母劑(黏著劑)，或由在具有彈性之母劑中調配能量線硬化性化合物(或能量線硬化性樹脂)而成之組合物構成。 The energy ray-curable elastic layer 3 contains an energy ray-curable compound (or an energy ray-curable resin) for imparting energy ray curability, and has a heat-expandable microsphere which can be alleviated when the heat-peelable adhesive layer 4 is pressure-bonded. Viscoelasticity of the degree of unevenness (refer to the enlarged view of Fig. 1). Further, the energy ray-curable elastic layer 3 is preferably an elastic body after being irradiated with an energy ray. From the above viewpoints, the energy ray-curable elastic layer 3 is preferably a mother agent (adhesive) chemically modified with an energy ray-reactive functional group, or an energy ray-curable compound is formulated from a mother agent having elasticity. A composition composed of (or an energy ray-curable resin).
作為上述母劑，例如可使用：天然橡膠或合成橡膠或使用該等之橡膠系黏著劑、聚矽氧橡膠或其黏著劑、包含(甲基)丙烯酸烷基酯[例如(甲基)丙烯酸之甲酯、乙酯、丙酯、異丙脂、丁酯、異丁酯、己酯、辛酯、2-乙基己酯、 異辛酯、異癸酯、十二烷基酯等C1-20烷基酯等]之均聚物或共聚物、或該(甲基)丙烯酸烷基酯與其他單體[例如丙烯酸、甲基丙烯酸、伊康酸、順丁烯二酸、反丁烯二酸、順丁烯二酸酐等含羧基或酸酐基之單體；(甲基)丙烯酸2-羥基乙酯等含羥基之單體；苯乙烯磺酸等含磺酸基之單體；丙烯醯基磷酸2-羥基乙酯等含磷酸基之單體；(甲基)丙烯醯胺等含醯胺基之單體；(甲基)丙烯酸胺基乙酯等含胺基之單體；(甲基)丙烯酸甲氧基乙酯等含烷氧基之單體；N-環己基順丁烯二醯亞胺等含醯亞胺基之單體；乙酸乙烯酯等乙烯酯類；N-乙烯基吡咯烷酮等含乙烯基之雜環化合物；苯乙烯、α-甲基苯乙烯等苯乙烯系單體；丙烯腈等含氰基之單體；(甲基)丙烯酸縮水甘油酯等含環氧基之丙烯酸系單體；乙烯醚等乙烯醚系單體等]之共聚物之丙烯酸系樹脂或其黏著劑、聚胺基甲酸酯系樹脂或其黏著劑、乙烯-乙酸乙烯酯共聚物等具有適當黏彈性之有機黏彈性體。再者，藉由使用與構成下述熱剝離型黏著劑層4之黏著劑相同或同種之成分作為該母劑，可密接性良好地積層能量線硬化型彈性層3及熱剝離型黏著劑層4。較佳為於母劑中含有丙烯酸系黏著劑等黏著物質。母劑可由1種成分構成，亦可由2種以上之成分構成。 As the above-mentioned mother agent, for example, natural rubber or synthetic rubber or a rubber-based adhesive using the above, a polyoxyxylene rubber or an adhesive thereof, and an alkyl (meth)acrylate [for example, (meth)acrylic acid can be used. Methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, hexyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, isodecyl ester, dodecyl ester, etc. C 1- a homopolymer or copolymer of 20 alkyl ester or the like, or the alkyl (meth)acrylate and other monomers [eg, acrylic acid, methacrylic acid, itaconic acid, maleic acid, antibutene) a monomer having a carboxyl group or an acid anhydride group such as an acid or a maleic anhydride; a hydroxyl group-containing monomer such as 2-hydroxyethyl (meth)acrylate; a sulfonic acid group-containing monomer such as styrenesulfonic acid; a monomer containing a phosphate group such as 2-hydroxyethyl phosphate; a monomer containing a mercapto group such as (meth)acrylamide; an amine group-containing monomer such as aminoethyl (meth)acrylate; An alkoxy group-containing monomer such as methoxyethyl acrylate; a quinone imine group-containing monomer such as N-cyclohexylmethyleneimine; a vinyl ester such as vinyl acetate; and N-vinylpyrrolidone a vinyl-containing heterocyclic compound; a styrene monomer such as styrene or α-methylstyrene; a cyano group-containing monomer such as acrylonitrile; an epoxy group-containing acrylic acid such as glycidyl (meth)acrylate; Acrylic resin or a binder thereof, a polyurethane resin or an adhesive thereof, an ethylene-vinyl acetate copolymer, etc. of a copolymer of a monomer; a vinyl ether monomer such as vinyl ether; Elastic organic viscoelastic body. In addition, by using the same or the same kind of component as the adhesive constituting the heat-peelable adhesive layer 4 described below as the mother agent, the energy ray-curable elastic layer 3 and the heat-peelable adhesive layer can be laminated with good adhesion. 4. It is preferred to contain an adhesive such as an acrylic adhesive in the mother agent. The mother agent may be composed of one component or may be composed of two or more components.
作為用於化學改性之能量線反應性官能基，例如可列舉丙烯醯基、甲基丙烯醯基、乙烯基、烯丙基、乙炔基等具有碳-碳多重鍵之官能基等。該等可單獨使用或組合2種以上而使用。該等官能基可藉由能量線之照射使碳-碳多重 鍵斷鍵生成自由基，該自由基成為交聯點而形成三維網狀結構。 Examples of the energy ray-reactive functional group used for the chemical modification include a functional group having a carbon-carbon multiple bond such as an acryloyl group, a methacryl group, a vinyl group, an allyl group or an ethynyl group. These may be used alone or in combination of two or more. The functional groups can be carbon-carbon multiplexed by irradiation of energy rays The bond breaks to generate a radical which becomes a cross-linking point to form a three-dimensional network structure.
其中，(甲基)丙烯醯基對能量線顯示相對較高之反應性，且可自多樣化之丙烯酸系黏著劑中選擇而組合使用等，就反應性、作業性之觀點而言較佳。 Among them, the (meth) acrylonitrile group has a relatively high reactivity with respect to the energy ray, and can be selected from a variety of acryl-based pressure-sensitive adhesives and used in combination, and is preferable from the viewpoint of reactivity and workability.
作為經能量線反應性官能基化學改性之母劑之代表例，可列舉使含有羥基及/或羧基等反應性官能基之單體[例如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸等]與(甲基)丙烯酸烷基酯共聚合而成之含反應性官能基之丙烯酸系聚合物、與分子內具有與上述反應性官能基反應之基(異氰酸酯基、環氧基等)及能量線反應性官能基(丙烯醯基、甲基丙烯醯基等)之化合物[例如(甲基)丙烯醯氧基伸乙基異氰酸酯等]進行反應而獲得之聚合物。 Representative examples of the chemical agent which is chemically modified by the energy ray-reactive functional group include a monomer having a reactive functional group such as a hydroxyl group and/or a carboxyl group [for example, 2-hydroxyethyl (meth)acrylate, (A) Acrylic acid or the like having a reactive functional group copolymerized with an alkyl (meth) acrylate, and a group having an interaction with the above reactive functional group in the molecule (isocyanate group, epoxy group) And a polymer obtained by reacting a compound of an energy ray-reactive functional group (such as (meth) propylene oxime extended ethyl isocyanate).
上述含反應性官能基之丙烯酸系聚合物中的含有反應性官能基之單體之比率相對於所有單體，例如為5~40重量%，較佳為10~30重量%。 The ratio of the reactive functional group-containing monomer in the reactive functional group-containing acrylic polymer is, for example, 5 to 40% by weight, preferably 10 to 30% by weight based on the total of the monomers.
關於分子內具有與上述反應性官能基反應之基及能量線反應性官能基之化合物之使用量，與上述含反應性官能基之丙烯酸系聚合物反應時，相對於含反應性官能基之丙烯酸系聚合物中之反應性官能基(羥基、羧基等)，例如為20~100莫耳%，較佳為40~95莫耳%。又，分子內具有與上述反應性官能基反應之基及能量線反應性官能基之化合物與含反應性官能基之丙烯酸系聚合物中之反應性官能基進行加成反應，為促進包含該加成反應在內之反應，亦可調 配有機錫、有機鋯等有機金屬系化合物或胺系化合物等觸媒。 The amount of the compound having a group reactive with the reactive functional group in the molecule and the energy ray-reactive functional group, and the reactive functional group-containing acrylic acid when reacting with the reactive functional group-containing acrylic polymer The reactive functional group (hydroxyl group, carboxyl group, etc.) in the polymer is, for example, 20 to 100 mol%, preferably 40 to 95 mol%. Further, a compound having a group reactive with the reactive functional group and a reactive functional group in the molecule is subjected to an addition reaction with a reactive functional group in the reactive functional group-containing acrylic polymer, and the addition reaction is included in the promotion. The reaction into the reaction can also be adjusted A catalyst such as an organometallic compound such as organotin or organozirconium or an amine compound is used.
作為用以使能量線硬化型彈性層3進行能量線硬化之能量線硬化性化合物，只要為可藉由可見光、紫外線、電子束等能量線而硬化者，則無特別限定，但較佳為能量線照射後之能量線硬化型彈性層3a之三維網狀化可效率良好地進行者。能量線硬化性化合物可單獨使用1種或組合2種以上而使用。 The energy ray-curable compound for energy-hardening the energy ray-curable elastic layer 3 is not particularly limited as long as it can be cured by energy rays such as visible light, ultraviolet light, or electron beam, but is preferably energy. The three-dimensional network of the energy ray-curable elastic layer 3a after the line irradiation can be efficiently performed. The energy ray-curable compound may be used alone or in combination of two or more.
作為能量線硬化性化合物之具體例，例如可列舉：三羥甲基丙烷三丙烯酸酯、四羥甲基甲烷四丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇單羥基五丙烯酸酯、二季戊四醇六丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、聚乙二醇二丙烯酸酯等。 Specific examples of the energy ray-curable compound include trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol monohydroxypentaacrylate. Dipentaerythritol hexaacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, and the like.
亦可使用能量線硬化性樹脂作為能量線硬化性化合物，作為能量線硬化性樹脂，例如可列舉：於分子末端具有(甲基)丙烯醯基之酯(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯、環氧(甲基)丙烯酸酯、三聚氰胺(甲基)丙烯酸酯、丙烯酸樹脂(甲基)丙烯酸酯、於分子末端具有烯丙基之硫醇-烯加成型樹脂或光陽離子聚合型樹脂、聚桂皮酸乙烯酯等含桂皮醯基之聚合物、經重氮化之胺基酚醛清漆樹脂或丙烯醯胺型聚合物等含感光性反應基之聚合物或含感光性反應基之低聚物等。進而，作為利用高能量線反應之聚合物，可列舉環氧化聚丁二烯、不飽和聚酯、聚甲基丙烯酸縮水甘油酯、聚丙烯醯胺、聚乙烯基矽氧烷等。再者， 於使用能量線硬化性樹脂之情形時，並非必需上述母劑。 An energy ray-curable resin can be used as the energy ray-curable compound, and examples of the energy ray-curable resin include ester (meth) acrylate having a (meth) acrylonitrile group at a molecular terminal, and (meth) Acryl acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, acrylic (meth) acrylate, thiol-ene addition resin having allyl at the molecular end or light a polymer containing a sensitizing reactive group such as a cation-polymerized resin, a cinnamyl group-containing polymer such as a polyvinyl cinnamate-based polymer, a diazotized amino novolac resin or a acrylamide-based polymer or a photosensitive reaction Based on oligomers and the like. Further, examples of the polymer which is reacted by the high energy line include epoxidized polybutadiene, unsaturated polyester, polyglycidyl methacrylate, polypropylene decylamine, polyvinyl decane, and the like. Furthermore, In the case of using an energy ray-curable resin, the above-mentioned mother agent is not necessarily required.
能量線硬化性化合物之調配量例如相對於母劑100重量份為5~500重量份左右，較佳為15~300重量份，進而較佳為20~150重量份左右之範圍。又，若能量線硬化型彈性層3之能量線照射後之動彈性模數於20℃下為剪切儲存彈性模數5×106~1×1010 Pa(頻率為1 Hz，樣品為厚度1.5 mm之膜狀)，則可兼具優異之切斷作業性及加熱剝離性。該儲存彈性模數可藉由適當選擇能量線硬化性化合物之種類或調配量、能量線照射條件等進行調整。 The blending amount of the energy ray-curable compound is, for example, about 5 to 500 parts by weight, preferably 15 to 300 parts by weight, and more preferably about 20 to 150 parts by weight, per 100 parts by weight of the mother agent. Further, if the energy elastic line of the energy ray-curable elastic layer 3 is irradiated, the elastic modulus is a shear storage elastic modulus of 5 × 10 6 to 1 × 10 10 Pa at 20 ° C (the frequency is 1 Hz, and the sample is thickness). With a film shape of 1.5 mm, it has excellent cutting workability and heat peelability. The storage elastic modulus can be adjusted by appropriately selecting the type or amount of the energy ray-curable compound, the energy ray irradiation conditions, and the like.
再者，視需要亦可於使用上述能量線聚合起始劑時併用能量線聚合促進劑。 Further, an energy ray polymerization accelerator may be used in combination with the above energy ray polymerization initiator as needed.
於能量線硬化型彈性層3中，除上述成分以外，亦可視需要調配用以使能量線硬化性化合物硬化之能量線聚合起始劑、及用以於能量線硬化前後獲得適當之黏彈性之熱聚合起始劑、交聯劑、黏著賦予劑、硫化劑等適當之添加劑、以及填充劑、防老化劑、防氧化劑、著色劑。 In the energy ray-curable elastic layer 3, in addition to the above components, an energy ray polymerization initiator for curing the energy ray-curable compound may be optionally disposed, and an appropriate viscoelasticity may be obtained before and after the energy ray hardening. Suitable additives such as a thermal polymerization initiator, a crosslinking agent, an adhesion-imparting agent, and a vulcanizing agent, and a filler, an anti-aging agent, an antioxidant, and a colorant.
作為能量線聚合起始劑，可根據使用之能量線之種類適當選擇公知或慣用之聚合起始劑。 As the energy ray polymerization initiator, a known or customary polymerization initiator can be appropriately selected depending on the type of energy ray used.
於使用紫外線作為能量線進行聚合、硬化之情形時，為進行硬化而包含光聚合起始劑。作為光聚合起始劑，並無特別限定，例如可列舉：安息香甲醚、安息香異丙醚、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等安息香醚；苯甲醚甲醚等取代安息香醚；2,2-二乙氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、1-羥基-環已基-苯基酮等取代苯乙酮；2- 甲基-2-羥基苯丙酮等取代α-酮醇；2-萘磺醯氯等芳香族磺醯氯；1-苯基-1,1-丙二酮-2-(鄰乙氧基羰基)-肟等光活性肟；2,4,6-三甲基苯甲醯基-二苯基-氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等醯基氧化膦等。 When polymerization and hardening are carried out using ultraviolet rays as an energy ray, a photopolymerization initiator is included for curing. The photopolymerization initiator is not particularly limited, and examples thereof include benzoin ether such as benzoin methyl ether, benzoin isopropyl ether, and 2,2-dimethoxy-1,2-diphenylethane-1-one. ; substituted benzoin ether such as anisole methyl ether; 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxy-cyclohexyl-phenyl Ketones and other substituted acetophenones; 2- Substituting α-keto alcohol such as methyl-2-hydroxypropiophenone; aromatic sulfonium chloride such as 2-naphthalenesulfonium chloride; 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl) - 肟, etc. photoactive oxime; 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, etc. Sulfhydryl phosphine oxide and the like.
能量線硬化型彈性層3例如可藉由如下慣用之方法形成：將含有能量線硬化性樹脂、或母劑、能量線聚合性化合物、及能量線聚合起始劑、進而視需要之添加劑、溶劑等之塗佈液塗佈於基材1上之方式；於適當之隔離片(剝離紙等)上塗佈上述塗佈液而形成能量線硬化型彈性層3，將其轉印(移著)至基材1上之方法等。 The energy ray-curable elastic layer 3 can be formed, for example, by a method conventionally used: an energy ray-curable resin, a mother agent, an energy ray polymerizable compound, an energy ray polymerization initiator, an optional additive, and a solvent. The coating liquid is applied to the substrate 1 , and the coating liquid is applied onto a suitable separator (release paper or the like) to form an energy ray-curable elastic layer 3, which is transferred (moved). The method to the substrate 1 and the like.
於使該能量線硬化型彈性層硬化時，擔心產生由氧導致之聚合阻礙之情形時，可於塗佈於隔離片上之胺基甲酸酯聚合物與自由基聚合性單體之混合物上放置經剝離處理之片材而遮斷氧，亦可將基材置於填充有惰性氣體之容器內，降低氧濃度。 When the energy ray-curable elastic layer is hardened, it may be placed on a mixture of a urethane polymer and a radical polymerizable monomer coated on the separator when there is a fear of polymerization inhibition by oxygen. The exfoliated sheet is used to block oxygen, and the substrate may be placed in a container filled with an inert gas to lower the oxygen concentration.
所使用之燈之種類等可根據能量線等之種類或照射而適當選擇，可使用螢光化學燈、黑光燈、殺菌燈等低壓燈，或金屬鹵化物燈、高壓水銀燈等高壓燈等。進而，紫外線等之照射量可根據所要求之能量線硬化型彈性層之特性進行任意設定。 The type of the lamp to be used and the like can be appropriately selected depending on the type of the energy line or the like, and a low-pressure lamp such as a fluorescent chemical lamp, a black light lamp, or a germicidal lamp, or a high-pressure lamp such as a metal halide lamp or a high-pressure mercury lamp can be used. Further, the amount of irradiation of ultraviolet rays or the like can be arbitrarily set according to the characteristics of the required energy ray-curable elastic layer.
就緩和熱剝離型黏著劑層4中所含之熱膨脹性微球之凹凸、防止切斷被黏著體時之由旋轉刀引起之振動等觀點而言，能量線硬化型彈性層3之厚度為3~150 μm左右，較佳為5~150 μm，進而較佳為10~150 μm左右，更佳為15~100 μm左右。 The thickness of the energy ray-curable elastic layer 3 is 3 in terms of relaxing the unevenness of the heat-expandable microspheres contained in the heat-peelable pressure-sensitive adhesive layer 4 and preventing the vibration caused by the rotary blade when the adherend is cut. ~150 μm or so, preferably 5 to 150 μm, further preferably 10 to 150 μm, more preferably 15 to 100 About μm.
熱剝離型黏著劑層4含有用以賦予黏著性之黏著性物質、及用以賦予熱膨脹性之熱膨脹性微球。 The heat-peelable adhesive layer 4 contains an adhesive substance for imparting adhesiveness and a heat-expandable microsphere for imparting thermal expansion property.
熱剝離型黏著劑層4係藉由因熱引起之熱膨脹性微球之發泡，減小接著面積，使剝離變得容易之層。熱膨脹性微球可單獨使用或組合2種以上而使用。熱膨脹性微球之平均粒徑較佳為1 μm~25 μm左右。更佳為5 μm~15 μm，尤佳為10 μm左右。而且，熱膨脹性微球之最大粒徑大於該平均粒徑。 The heat-peelable pressure-sensitive adhesive layer 4 is a layer which is formed by foaming of heat-expandable microspheres due to heat, thereby reducing the adhesion area and facilitating the peeling. The heat-expandable microspheres can be used singly or in combination of two or more. The average particle diameter of the heat-expandable microspheres is preferably from about 1 μm to about 25 μm. More preferably, it is 5 μm to 15 μm, and particularly preferably about 10 μm. Moreover, the maximum particle diameter of the heat-expandable microspheres is larger than the average particle diameter.
作為熱膨脹性微球，可自公知之熱膨脹性微球中進行適當選擇。作為熱膨脹性微球，由於未微膠囊化之熱膨脹性微球有無法穩定地表現良好剝離性之情況，故而可較佳地使用經微膠囊化之熱膨脹性微球。 The heat-expandable microspheres can be appropriately selected from known heat-expandable microspheres. As the heat-expandable microspheres, the heat-expandable microspheres which are not microencapsulated may not stably exhibit good peelability, and thus microencapsulated heat-expandable microspheres can be preferably used.
而且，如圖1之右圖所示之放大圖般，熱剝離型黏著劑層4之表面較理想為平滑而不具有反映所含之熱膨脹性微球之形狀的凹凸。較理想為即便於由於存在較大之熱膨脹性微球而無法於熱剝離性黏著劑層4之層厚度內收納熱膨脹性微球之情形時，亦藉由使該熱膨脹性微球之凸部嵌入至能量線硬化型彈性層之層內而使熱膨脹型黏著層4之表面變得平滑。 Further, as shown in the enlarged view of the right side of Fig. 1, the surface of the heat-peelable adhesive layer 4 is preferably smooth without unevenness reflecting the shape of the thermally expandable microspheres contained therein. It is preferable to embed the convex portion of the heat-expandable microspheres even when the heat-expandable microspheres cannot be accommodated in the layer thickness of the heat-peelable adhesive layer 4 due to the presence of the large heat-expandable microspheres. The surface of the heat-expandable adhesive layer 4 is smoothed into the layer of the energy ray-curable elastic layer.
作為上述黏著性物質，使用於加熱時容許熱膨脹性微球之發泡及/或膨脹，具有不受限之彈性者。因此，可使用先前公知之感壓接著劑(黏著劑)等。作為感壓接著劑，例 如例示有：天然橡膠或各種合成橡膠等橡膠系感壓接著劑；聚矽氧系感壓接著劑；(甲基)丙烯酸烷基酯與可與該酯共聚合之其他不飽和單體之共聚物等丙烯酸系感壓接著劑(例如作為上述能量線硬化型彈性層3之母劑所記載之丙烯酸系黏著劑等)等。又，於熱剝離型黏著劑層4中亦可使用能量線硬化型黏著劑。於此情形時，若能量線照射後之動彈性模數於開始熱膨脹性微球之膨脹之溫度範圍內為剪切儲存彈性模數1×105~5×107 Pa(頻率為1 Hz，樣品為厚度1.5 mm之膜狀)，則可獲得良好之剝離性。 The adhesive material is used for allowing foaming and/or expansion of the heat-expandable microspheres during heating, and has an elastic property without limitation. Therefore, a previously known pressure-sensitive adhesive (adhesive) or the like can be used. Examples of the pressure-sensitive adhesive include rubber-based pressure-sensitive adhesives such as natural rubber and various synthetic rubbers; polyfluorene-based pressure-sensitive adhesives; alkyl (meth)acrylates and other copolymerizable copolymers with the esters. An acrylic pressure-sensitive adhesive such as a copolymer of an unsaturated monomer (for example, an acrylic pressure-sensitive adhesive described as a mother agent for the energy ray-curable elastic layer 3). Further, an energy ray-curable adhesive may be used for the heat-peelable adhesive layer 4. In this case, if the dynamic elastic modulus after the irradiation of the energy ray is within the temperature range in which the expansion of the thermally expandable microspheres is started, the shear storage elastic modulus is 1×10 5 to 5×10 7 Pa (the frequency is 1 Hz, The sample is in the form of a film having a thickness of 1.5 mm, and good peelability can be obtained.
作為熱膨脹性微球，只要例如為使異丁烷、丙烷、戊烷等因加熱而容易氣化膨脹之物質內包於具有彈性之殼內之微球即可。上述殼通常由熱塑性物質、熱熔融性物質、因熱膨脹而破裂之物質等形成。作為形成上述殼之物質，例如可列舉：偏二氯乙烯-丙烯腈共聚物、聚乙烯醇、聚乙烯縮丁醛、聚甲基丙烯酸甲酯、聚丙烯腈、聚偏二氯乙烯、聚碸等。熱膨脹性微球可藉由慣用之方法，例如凝聚法、界面聚合法等而製造。作為熱膨脹性微球，亦可使用例如Matsumoto Microsphere(商品名，松本油脂製藥(股份有限公司)製造)等市售品。 The heat-expandable microspheres may be, for example, a material in which a material which is easily vaporized and expanded by heating such as isobutane, propane or pentane is contained in a shell having elasticity. The above shell is usually formed of a thermoplastic substance, a hot meltable substance, a substance which is broken by thermal expansion, or the like. Examples of the material for forming the above shell include a vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polyfluorene. Wait. The heat-expandable microspheres can be produced by a conventional method such as a coacervation method, an interfacial polymerization method, or the like. Commercially available products such as Matsumoto Microsphere (trade name, manufactured by Matsumoto Oil & Fat Pharmaceutical Co., Ltd.) can be used as the heat-expandable microspheres.
就分散性或薄層形成性等方面而言，熱膨脹性微球之平均粒徑通常為1~80 μm左右，較佳為3~50 μm左右。又，作為熱膨脹性微球，為藉由加熱處理效率良好地降低含有黏著劑之熱剝離型黏著劑層之黏著力，較佳為具有體積膨脹率為5倍以上，尤其為10倍以上仍不破裂之適當之強度 者。再者，於使用於較低之膨脹率下破裂之熱膨脹性微球之情形時、或使用未經微膠囊化之熱膨脹劑之情形時，熱剝離型黏著劑層4與被黏著體之黏著面積無法充分減小，難以獲得良好之剝離性。 The average particle diameter of the heat-expandable microspheres is usually from about 1 to 80 μm, preferably from about 3 to 50 μm, in terms of dispersibility or sheet formation. Further, as the heat-expandable microspheres, it is preferable to reduce the adhesive force of the heat-peelable pressure-sensitive adhesive layer containing the adhesive by heat treatment, and it is preferable to have a volume expansion ratio of 5 times or more, particularly 10 times or more. Appropriate strength of rupture By. Further, in the case of using heat-expandable microspheres which are broken at a lower expansion ratio, or in the case of using a micro-encapsulated thermal expansion agent, the adhesion area of the heat-peelable adhesive layer 4 and the adherend It cannot be sufficiently reduced, and it is difficult to obtain good peelability.
熱膨脹性微球之使用量亦視其種類而不同，相對於構成熱剝離型黏著劑層4之黏著劑基底聚合物100重量份，例如為10~200重量份，較佳為20~125重量份左右。若未達10重量份，則加熱處理後之有效之黏著力降低容易變得不充分，又，若超過200重量份，則容易產生熱剝離型黏著劑層4之凝聚破壞、或能量線硬化型彈性層3與熱剝離型黏著劑層4之界面破壞。 The amount of the heat-expandable microspheres to be used varies depending on the type thereof, and is, for example, 10 to 200 parts by weight, preferably 20 to 125 parts by weight, per 100 parts by weight of the adhesive base polymer constituting the heat-peelable pressure-sensitive adhesive layer 4. about. When the amount is less than 10 parts by weight, the adhesive strength which is effective after the heat treatment is likely to be insufficient, and if it exceeds 200 parts by weight, the heat-peelable adhesive layer 4 is likely to be agglomerated or broken, or the energy ray-curable type. The interface between the elastic layer 3 and the heat-peelable adhesive layer 4 is broken.
於熱剝離型黏著劑層4中，除黏著劑、熱膨脹性微球之外，亦可調配交聯劑(例如異氰酸酯系交聯劑、環氧系交聯劑等)、黏著賦予劑(例如多官能性環氧化合物、或異氰酸酯化合物、氮丙啶化合物、三聚氰胺樹脂、脲樹脂、無水化合物、聚胺、含羧基之聚合物等)、塑化劑、顏料、填充劑、防老化劑、界面活性劑、防帶電劑等適當之添加劑。 In the heat-peelable adhesive layer 4, in addition to the adhesive and the heat-expandable microspheres, a crosslinking agent (for example, an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, or the like) or an adhesion-imparting agent (for example, more) may be blended. Functional epoxy compound, or isocyanate compound, aziridine compound, melamine resin, urea resin, anhydrous compound, polyamine, carboxyl group-containing polymer, etc.), plasticizer, pigment, filler, anti-aging agent, interface activity Suitable additives such as agents and antistatic agents.
熱剝離型黏著劑層4之形成例如可藉由如下等適當之方法而進行：將含有黏著劑、熱膨脹性微球、及視需要之添加劑、溶劑等之塗佈液直接塗佈於能量線硬化型彈性層3上，介隔隔離片5而壓接之方法；將上述塗佈液塗佈於適當之隔離片(剝離紙等)5上，形成熱剝離型黏著劑層4，並將其壓接轉印(移著)至能量線硬化型彈性層3上之方法等。 The formation of the heat-peelable adhesive layer 4 can be carried out, for example, by applying a coating liquid containing an adhesive, heat-expandable microspheres, and, if necessary, additives, solvents, etc., directly to the energy ray hardening. a method of pressure-bonding the spacer layer 5 on the elastic layer 3; applying the coating liquid to a suitable separator (release paper or the like) 5 to form a heat-peelable adhesive layer 4, and pressing it A method of transferring (moving) to the energy ray-curable elastic layer 3 or the like.
該隔離片5為於基材膜之單面根據需要形成剝離劑層而成之片材，亦為保護本發明之加熱剝離型黏著片之表面層，且於使用前為露出加熱剝離型黏著片之表面層而剝離之片材，及成為形成熱剝離型黏著劑層4時之基礎之片材。 The separator 5 is a sheet obtained by forming a release agent layer on one surface of a base film as needed, and also protecting the surface layer of the heat-peelable pressure-sensitive adhesive sheet of the present invention, and exposing the heat-peelable adhesive sheet before use. The sheet which is peeled off by the surface layer, and the sheet which becomes the basis of the heat-peelable adhesive layer 4 is formed.
作為隔離片之基材膜，可使用公知者，例如可自聚醚醚酮、聚醚醯亞胺、聚芳酯、聚萘二甲酸乙二酯、聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、聚氯乙烯膜、氯乙烯共聚物膜、聚對苯二甲酸乙二酯膜、聚對苯二甲酸丁二酯膜、聚胺基甲酸酯膜、乙烯-乙酸乙烯酯共聚物膜、離子聚合物樹脂膜、乙烯-(甲基)丙烯酸共聚物膜、乙烯-(甲基)丙烯酸酯共聚物膜、聚苯乙烯膜、及聚碳酸酯膜等塑膠膜等中進行選擇。 As the substrate film of the separator, a known one can be used, for example, from polyetheretherketone, polyetherimide, polyarylate, polyethylene naphthalate, polyethylene film, polypropylene film, polybutene. Membrane, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyamine base Acid film, ethylene-vinyl acetate copolymer film, ionomer resin film, ethylene-(meth)acrylic copolymer film, ethylene-(meth)acrylate copolymer film, polystyrene film, and polycarbonate It is selected from plastic films such as ester films.
可使用之剝離劑層為根據黏著劑層之樹脂選擇含有經氟化之聚矽氧樹脂系剝離劑、氟樹脂系剝離劑、聚矽氧樹脂系剝離劑、聚乙烯醇系樹脂、聚丙烯系樹脂、長鏈烷基化合物等公知之剝離劑而成之層。 The release agent layer which can be used is selected from the group consisting of a fluorinated polyoxymethylene resin release agent, a fluororesin release agent, a polyoxymethylene resin release agent, a polyvinyl alcohol resin, and a polypropylene system depending on the resin of the adhesive layer. A layer of a known release agent such as a resin or a long-chain alkyl compound.
熱剝離型黏著劑層4之厚度可根據黏著片之使用目的或由加熱引起之黏著力之降低性等適當決定，為提高被加工物之加工性，越薄越好。因此，熱剝離型黏著劑層4之厚度為50 μm以下，較佳為25 μm以下，進而較佳為10 μm以下。若熱剝離型黏著劑層4之厚度為50 μm以下，則黏著劑層之變形量變少，加工性精度提高。進而，於加工電子零件時藉由對該電子零件施加按壓力或剪切力，可使該等力 亦傳遞至熱剝離型黏著劑層4，由於熱剝離型黏著劑層4之厚度較薄，故對抗該施加之力，而使本發明之加熱剝離型黏著片可確實地保持該電子零件。 The thickness of the heat-peelable adhesive layer 4 can be appropriately determined depending on the purpose of use of the adhesive sheet or the decrease in adhesion due to heating, and the thinner the better, in order to improve the workability of the workpiece. Therefore, the thickness of the heat-peelable adhesive layer 4 is 50 μm or less, preferably 25 μm or less, and more preferably 10 μm or less. When the thickness of the heat-peelable pressure-sensitive adhesive layer 4 is 50 μm or less, the amount of deformation of the pressure-sensitive adhesive layer is reduced, and the workability is improved. Further, when the electronic component is processed, the force can be applied by applying a pressing force or a shearing force to the electronic component. It is also transferred to the heat-peelable adhesive layer 4, and since the thickness of the heat-peelable adhesive layer 4 is thin, the heat-peelable adhesive sheet of the present invention can surely hold the electronic component against the force of application.
若熱剝離型黏著劑層4之厚度為50 μm以下，則於加工藉由本發明之加熱剝離型黏著片固定之被加工物時，不會由於切斷刀等加工用構件之按壓力等導致黏著劑層之變形量變大，可防止該被加工物之位置或朝向發生輕微變化，結果可準確地進行加工。 When the thickness of the heat-peelable pressure-sensitive adhesive layer 4 is 50 μm or less, the workpiece to be processed by the heat-peelable pressure-sensitive adhesive sheet of the present invention is not adhered by the pressing force of the processing member such as a cutting blade. The amount of deformation of the agent layer is increased to prevent a slight change in the position or orientation of the workpiece, and as a result, the processing can be performed accurately.
又，較佳為將熱剝離型黏著劑層4之厚度設為1 μm以上，較佳為3 μm以上，進而較佳為5 μm以上。藉由使熱剝離性黏著劑層4之厚度為1 μm以上，可具有能充分固定被黏著體之黏著力，因此例如於切斷時可在不產生晶片飛濺之情況下進行加工。 Further, the thickness of the heat-peelable pressure-sensitive adhesive layer 4 is preferably 1 μm or more, preferably 3 μm or more, and more preferably 5 μm or more. When the thickness of the heat-peelable pressure-sensitive adhesive layer 4 is 1 μm or more, the adhesion of the adherend can be sufficiently fixed. Therefore, for example, the wafer can be processed without being splashed when the wafer is cut.
作為隔離片5，例如可使用包含藉由以聚矽氧系樹脂、丙烯酸長鏈烷基酯系樹脂、氟系樹脂等為代表之剝離劑進行表面塗佈而成之塑膠膜或紙等之基材、或包含聚乙烯或聚丙烯等無極性聚合物之黏著性較小之基材等。 As the separator 5, for example, a plastic film or paper which is surface-coated by a release agent typified by a polyoxymethylene resin, an acrylic long-chain alkyl ester resin, a fluorine resin or the like can be used. A material or a substrate containing a non-polar polymer such as polyethylene or polypropylene which has less adhesion.
如上所述，隔離片5可用作將熱剝離型黏著劑層4壓接轉印(移著)至能量線硬化型彈性層3上時之暫時支持體，及用作供至實際應用之前保護熱剝離型黏著劑層4之保護材。 As described above, the separator 5 can be used as a temporary support when the heat-peelable adhesive layer 4 is pressure-transferred (transferred) onto the energy ray-curable elastic layer 3, and used as a protection for practical use. The protective material of the heat-peelable adhesive layer 4.
再者，能量線硬化型彈性層3及設置於其上之熱剝離型黏著劑層4不僅可形成於基材1之單面，亦可形成於兩面。又，亦可於基材1之一面依序設置能量線硬化型彈性層3及熱剝離型黏著劑層4，並於另一面設置通常之接著劑層。 又，為防止加熱處理時伴隨熱剝離型黏著劑層4之凹凸變形的與被黏著體之接著界面之微細之凝聚破壞，亦可於該熱剝離型黏著劑層4上進而設置黏著層。作為該黏著層之黏著物質，可使用上述熱剝離型黏著劑層4中所記載之黏著劑。就對被黏著體之黏著力之降低乃至喪失之觀點而言，該黏著層之厚度較佳為0.1~8 μm，尤佳為1~5 μm，可藉由以熱膨脹性黏著層4為基準之方法而形成。 Further, the energy ray-curable elastic layer 3 and the heat-peelable pressure-sensitive adhesive layer 4 provided thereon may be formed not only on one surface of the substrate 1, but also on both surfaces. Further, the energy ray-curable elastic layer 3 and the heat-peelable pressure-sensitive adhesive layer 4 may be sequentially disposed on one surface of the substrate 1, and a normal adhesive layer may be provided on the other surface. Moreover, in order to prevent fine cohesive failure of the heat-peelable adhesive layer 4 and the subsequent interface with the adherend, the adhesive layer may be further provided on the heat-peelable adhesive layer 4. As the adhesive substance of the adhesive layer, the adhesive described in the heat-peelable adhesive layer 4 can be used. The thickness of the adhesive layer is preferably from 0.1 to 8 μm, particularly preferably from 1 to 5 μm, from the viewpoint of the reduction or even loss of adhesion of the adherend, which can be based on the heat-expandable adhesive layer 4 Formed by the method.
圖2係表示本發明之加熱剝離型黏著片之其他例之概略剖面圖。於該例中，於基材1之一面上依序積層有有機塗層2、能量線硬化型彈性層3、熱剝離型黏著劑層4及隔離片5，並且於基材1之另一面上積層有接著劑層6及隔離片7。該黏著片於基材1之與形成有能量線硬化型彈性層3及其上之熱剝離型黏著劑層4之面為相反側之面上設置有接著劑層6及隔離片7，僅於該方面與圖1之黏著片不同。 Fig. 2 is a schematic cross-sectional view showing another example of the heat-peelable pressure-sensitive adhesive sheet of the present invention. In this example, an organic coating layer 2, an energy ray-curable elastic layer 3, a heat-peelable adhesive layer 4, and a separator 5 are sequentially laminated on one surface of the substrate 1, and on the other side of the substrate 1. The adhesive layer 6 and the separator 7 are laminated. The adhesive sheet is provided with an adhesive layer 6 and a separator 7 on the surface of the substrate 1 opposite to the surface on which the energy ray-curable elastic layer 3 and the heat-peelable adhesive layer 4 are formed. This aspect is different from the adhesive sheet of FIG.
接著劑層6含有黏著性物質。作為該黏著性物質，可使用與上述熱剝離型黏著劑層4中之黏著性物質(黏著劑)相同者，視需要亦可調配交聯劑(例如異氰酸酯系交聯劑、環氧系交聯劑等)、黏著賦予劑(例如松香衍生物樹脂、聚萜烯樹脂、石油樹脂、油溶性酚樹脂等)、塑化劑、填充劑、防老化劑、界面活性劑等適當之添加劑。然而，不宜使用或添加明顯阻礙使能量線硬化型彈性層3硬化之能量線透過之物質。 The subsequent agent layer 6 contains an adhesive substance. As the adhesive substance, the same as the adhesive substance (adhesive) in the heat-peelable pressure-sensitive adhesive layer 4 may be used, and a crosslinking agent (for example, an isocyanate-based crosslinking agent or an epoxy-based crosslinking) may be blended as needed. Suitable additives such as an agent, an adhesion-imparting agent (for example, a rosin derivative resin, a polydecene resin, a petroleum resin, an oil-soluble phenol resin, etc.), a plasticizer, a filler, an anti-aging agent, and a surfactant. However, it is not preferable to use or add a substance which significantly hinders the passage of the energy ray which hardens the energy ray-curable elastic layer 3.
接著劑層6之厚度可在無損熱剝離型黏著劑層4之對被黏著體之壓接、被黏著體之切斷及切斷片之剝離、回收等中 之操作性等的範圍內進行適當設定，通常為1~50 μm，較佳為3~30 μm左右。 The thickness of the adhesive layer 6 can be used for the pressure-bonding of the adherend by the non-destructive heat-peelable adhesive layer 4, the cutting of the adherend, and the peeling and recovery of the cut piece. The range of operability and the like is appropriately set, and is usually 1 to 50 μm, preferably about 3 to 30 μm.
接著劑層6之形成可藉由以熱剝離型黏著劑層4為基準之方法而進行。作為隔離片7，可使用與上述熱剝離型黏著劑層4上之隔離片5相同者。上述黏著片可藉由利用接著劑層6而固定於基座面上使用。 The formation of the subsequent agent layer 6 can be carried out by a method based on the heat-peelable adhesive layer 4. As the separator 7, the same one as the separator 5 on the above-described heat-peelable adhesive layer 4 can be used. The above adhesive sheet can be used by being fixed to the base surface by using the adhesive layer 6.
於基材1之單面或兩面設置有機塗層2，於其上利用任意機構均勻地塗佈構成上述能量線硬化型彈性層3之硬化前之組合物。繼而，於形成於所獲得之基材之單面上的上述能量線硬化型彈性層3含有反應性溶劑以外之溶劑之情形時，此種溶劑為可藉由乾燥而去除之狀態，使該能量線硬化型彈性層3為藉由能量線進行硬化前之狀態。但是，只要具備充分之流動性，則亦可部分硬化。 The organic coating layer 2 is provided on one surface or both surfaces of the substrate 1, and the composition before curing of the energy ray-curable elastic layer 3 is uniformly applied thereto by any mechanism. Then, when the energy ray-curable elastic layer 3 formed on one surface of the obtained substrate contains a solvent other than a reactive solvent, the solvent is removed by drying to make the energy The wire-curable elastic layer 3 is in a state before being hardened by an energy ray. However, as long as it has sufficient fluidity, it can be partially cured.
另外，於準備之隔離片上形成經塗佈乾燥之熱剝離型黏著劑層4。關於該熱剝離型黏著劑層4，由於含有之熱膨脹性微球未完全地埋入該熱剝離型黏著劑層4中，故而於其表面，即並非隔離片側之面，該熱膨脹性微球之一部分突出於表面而形成凸部。 Further, a coated dry heat-peelable adhesive layer 4 was formed on the prepared separator. In the heat-peelable pressure-sensitive adhesive layer 4, the heat-expandable microspheres are not completely embedded in the heat-peelable pressure-sensitive adhesive layer 4, so that the surface of the heat-dissipating-type pressure-sensitive adhesive layer 4 is not on the side of the separator sheet, and the heat-expandable microspheres are A portion protrudes from the surface to form a convex portion.
其次，於上述硬化前之該能量線硬化型彈性層3之表面，將形成於上述隔離片上之該熱剝離型黏著劑層4以形成有該凸部之表面對準該能量線硬化型彈性層3之表面之方式進行積層，自該基材及該隔離片側相互按壓該能量線硬化型彈性層3及該熱剝離型黏著劑層4，藉此將該凸部埋 入至未硬化之該能量線硬化型彈性層3之內部。 Next, on the surface of the energy ray-curable elastic layer 3 before the hardening, the heat-peelable adhesive layer 4 formed on the separator is aligned with the surface of the heat-curable elastic layer The surface of the layer 3 is laminated, and the energy ray-curable elastic layer 3 and the heat-peelable pressure-sensitive adhesive layer 4 are pressed against each other from the substrate and the spacer side, thereby burying the convex portion The inside of the energy ray-hardening elastic layer 3 which is not hardened is introduced.
其結果，可獲得將該基材1、有機塗層2、未硬化之該能量線硬化型彈性層3、該熱剝離型黏著劑層4及隔離片以此順序積層而成之片材。 As a result, a sheet obtained by laminating the base material 1, the organic coating layer 2, the uncured energy ray-curable elastic layer 3, the heat-peelable pressure-sensitive adhesive layer 4, and the separator in this order can be obtained.
進而，藉由自基材1側及/或隔離片側對該未硬化之該能量線硬化型彈性層3照射能量線而使未硬化之該能量線硬化型彈性層3硬化，藉此可獲得本發明之加熱剝離型黏著片。 Further, the energy ray-curable elastic layer 3 which is not hardened is irradiated with an energy ray from the side of the substrate 1 and/or the separator side to harden the uncured energy ray-curable elastic layer 3, whereby the present invention can be obtained. The invention discloses a heat-peelable adhesive sheet.
該加熱剝離型黏著片之製造方法為於基材1之單面設置能量線硬化型彈性層3及熱剝離型黏著劑層4之方法，當於基材1之兩面設置能量線硬化型彈性層3及熱剝離型黏著劑層4時，可逐次於基材之各單面進行該方法，亦可對基材之兩面同時進行。 The method for producing the heat-peelable pressure-sensitive adhesive sheet is a method in which the energy ray-curable elastic layer 3 and the heat-peelable pressure-sensitive adhesive layer 4 are provided on one surface of the substrate 1, and an energy ray-curable elastic layer is provided on both surfaces of the substrate 1. 3, in the case of the heat-peelable adhesive layer 4, the method may be carried out successively on each side of the substrate, or both sides of the substrate may be simultaneously performed.
又，於基材1之另一面設置接著劑層之情形時，於設置能量線硬化型彈性層3及熱剝離型黏著劑層4之步驟之前後任一階段均可進行該接著劑層之形成。 Further, when the adhesive layer is provided on the other surface of the substrate 1, the formation of the adhesive layer can be performed at any stage before the step of providing the energy ray-curable elastic layer 3 and the heat-peelable adhesive layer 4.
圖3係表示使用本發明之加熱剝離型黏著片之切斷片的製造方法之一例之概略步驟圖。更詳細而言，圖3係將以下一系列步驟以剖面圖形式表示之步驟圖：於圖1之能量線硬化型熱剝離性黏著片(處於剝下隔離片5之狀態者)之熱剝離型黏著劑層4之表面壓接貼合被黏著體(被切斷體)8，視情形藉由能量線9之照射使能量線硬化型彈性層3硬化後，沿切斷線10切斷為特定尺寸而製作切斷片，繼而，藉 由加熱處理使熱剝離型黏著劑層4中之熱膨脹性微球膨脹及發泡，剝離回收切斷片8a。再者，亦可於藉由能量線9之照射使能量線硬化型彈性層3硬化後，於熱剝離型黏著劑層4表面壓接貼合被黏著體(被切斷體)8，並沿切斷線10進行切斷。 Fig. 3 is a schematic process view showing an example of a method for producing a cut piece using the heat-peelable pressure-sensitive adhesive sheet of the present invention. More specifically, FIG. 3 is a step view showing a series of steps in the form of a cross-sectional view: the heat-peeling type of the energy ray-curable heat-peelable adhesive sheet of FIG. 1 (in the state in which the separator 5 is peeled off) The surface of the adhesive layer 4 is pressure-bonded to the adherend (cut object) 8, and the energy ray-curable elastic layer 3 is hardened by irradiation of the energy ray 9 as the case, and is cut along the cutting line 10 to be specific. Make a cut piece of size, and then borrow The heat-expandable microspheres in the heat-peelable pressure-sensitive adhesive layer 4 are expanded and foamed by heat treatment, and the cut piece 8a is peeled off. Further, after the energy ray-curable elastic layer 3 is cured by the irradiation of the energy ray 9, the adherend (the cut body) 8 is pressure-bonded to the surface of the heat-peelable adhesive layer 4, and The cutting line 10 is cut.
又，本發明之加熱剝離型黏著片之用途通常為研磨、開孔等加工步驟，並不限於上述切斷。 Moreover, the use of the heat-peelable pressure-sensitive adhesive sheet of the present invention is usually a processing step such as polishing or opening, and is not limited to the above-described cutting.
於圖3中，1表示基材，3a表示能量線照射後之經硬化之能量線硬化型彈性層，4a表示能量線照射後進而藉由加熱使熱膨脹性微球膨脹後之熱剝離型黏著劑層。 In Fig. 3, 1 denotes a substrate, 3a denotes a hardened energy ray-curable elastic layer after irradiation with an energy ray, and 4a denotes a heat-peelable adhesive which is irradiated with an energy ray and then thermally expanded by heat-expandable microspheres. Floor.
能量線硬化型熱剝離性黏著片之熱剝離型黏著劑層4與被黏著體8之壓接例如可藉由利用橡膠輥、層壓輥、按壓裝置等適當之按壓機構進行壓接處理之方式等而進行。再者，進行壓接處理時，若有必要，亦可根據黏著性物質之類型，於熱膨脹性微球不膨脹之溫度內進行加熱，或者塗佈水或有機溶劑而使黏著性物質活化。 The pressure-bonding adhesive layer 4 of the energy ray-curable heat-peelable adhesive sheet and the adherend 8 can be crimped by, for example, a suitable pressing mechanism such as a rubber roller, a laminating roller, or a pressing device. Wait and proceed. Further, when the pressure bonding treatment is performed, if necessary, heating may be performed at a temperature at which the heat-expandable microspheres do not swell depending on the type of the adhesive substance, or water or an organic solvent may be applied to activate the adhesive substance.
作為能量線9，可使用可見光或紫外線、電子束等。能量線9之照射可藉由適當之方法進行。但是，由於會有熱膨脹性微球因能量線9之照射熱而開始膨脹之情況，故而較理想為儘可能控制為短時間之照射，或藉由對加熱剝離型黏著片進行風冷等而保持為熱膨脹性微球不會開始膨脹之溫度。 As the energy ray 9, visible light or ultraviolet light, an electron beam, or the like can be used. Irradiation of the energy line 9 can be performed by an appropriate method. However, since the thermally expandable microspheres start to swell due to the heat of irradiation of the energy ray 9, it is preferable to control the irradiation as long as possible, or to keep the heat-peelable adhesive sheet air-cooled or the like. It is the temperature at which the heat-expandable microspheres do not start to expand.
被黏著體8之切斷可藉由切割等慣用之切斷步驟進行，例如圖3中由切斷線10所示般，形成有切斷線10。 The cutting of the adherend 8 can be performed by a conventional cutting step such as cutting. For example, as shown by the cutting line 10 in Fig. 3, the cutting line 10 is formed.
加熱條件可根據被黏著體8(或切斷片8a)之表面狀態或耐熱性、熱膨脹性微球之種類、黏著片之耐熱性、被黏著體(被切斷體)之熱容量等進行適當設定，通常之條件為溫度為350℃以下、處理時間為30分鐘以下，尤佳為溫度為80~200℃、處理時間為1秒~15分鐘左右。又，作為加熱方式，可列舉熱風加熱方式、熱板接觸方式、紅外線加熱方式等，並無特別限制。 The heating condition can be appropriately set depending on the surface state or heat resistance of the adherend 8 (or the cut piece 8a), the type of the heat-expandable microsphere, the heat resistance of the adhesive sheet, and the heat capacity of the adherend (the cut body). The usual conditions are a temperature of 350 ° C or less, a treatment time of 30 minutes or less, particularly preferably a temperature of 80 to 200 ° C, and a treatment time of about 1 second to 15 minutes. Further, examples of the heating method include a hot air heating method, a hot plate contact method, and an infrared heating method, and are not particularly limited.
又，於加熱剝離型黏著片之基材1使用具有伸縮性者之情形時，擴展處理例如可藉由使用使片材類二維地擴展時所使用之慣用之擴展機構而進行。 In the case where the base material 1 of the heat-peelable pressure-sensitive adhesive sheet is stretched, the expansion process can be carried out, for example, by using a conventional expansion mechanism used to expand the sheet two-dimensionally.
由於本發明之加熱剝離型黏著片包含含有黏著性物質(黏著劑)之熱剝離型黏著劑層4，故而可牢固地黏著保持被黏著體8，被黏著體8不會由於例如搬送時之振動等而脫落。又，由於熱剝離型黏著劑層4可較薄地形成，且於切斷步驟前藉由照射能量線使能量線硬化型彈性層3硬化，故而與先前之熱膨脹性黏著片相比，可明顯減少切斷步驟時由切斷刀導致之接著劑層之上捲或伴隨接著劑層等之移動產生之碎屑等，並且可切斷為特定尺寸。進而，由於熱剝離型黏著劑層4含有熱膨脹性微球，具有熱膨脹性，故而藉由切斷步驟後之加熱處理使熱膨脹性微球迅速發泡或膨脹，結果如圖3之右圖所示，上述熱剝離型黏著劑層4發生體積變化，於表面形成有凹凸狀之三維結構，與所切斷之切斷片8a之接著面積甚至接著強度明顯降低或喪失。 Since the heat-peelable pressure-sensitive adhesive sheet of the present invention contains the heat-peelable pressure-sensitive adhesive layer 4 containing an adhesive (adhesive), the adherend 8 can be firmly adhered, and the adherend 8 does not vibrate due to, for example, conveyance. Waiting to fall off. Further, since the heat-peelable adhesive layer 4 can be formed thin, and the energy ray-curable elastic layer 3 is hardened by irradiation of energy rays before the cutting step, it can be remarkably reduced as compared with the prior heat-expandable adhesive sheet. The cutting step is caused by the upper layer of the adhesive layer caused by the cutting blade or the debris generated by the movement of the adhesive layer or the like, and can be cut into a specific size. Further, since the heat-peelable pressure-sensitive adhesive layer 4 contains heat-expandable microspheres and has thermal expansion property, the heat-expandable microspheres are rapidly foamed or expanded by heat treatment after the cutting step, and as a result, as shown in the right diagram of FIG. The heat-peelable pressure-sensitive adhesive layer 4 has a volume change, and has a three-dimensional structure having a concavo-convex shape on the surface, and the area of the cut piece 8a to be cut or the subsequent strength is remarkably lowered or lost.
如此，由於由能量線照射引起之能量線硬化型彈性層3 之硬化、及由加熱處理引起之接著強度之明顯降低或喪失，被黏著體8之切斷步驟、切斷片8a之剝離、回收步驟中之操作性及作業性明顯改善，亦可較大地提高生產效率。 Thus, the energy ray-curable elastic layer 3 is caused by the irradiation of the energy rays. The hardening and the subsequent reduction or loss of the strength caused by the heat treatment are markedly improved by the cutting step of the adhesive body 8, the peeling of the cut piece 8a, and the workability and workability in the recovery step, and the production can be greatly improved. effectiveness.
本發明之能量線硬化型熱剝離性黏著片亦可用於永久地接著被黏著體之用途，但適用於要求或期望於特定期間內接著被黏著體，並且於達到接著目的後將該接著狀態解除之用途。作為上述用途之具體例，除半導體晶圓或陶瓷積層片材之固定材以外，可列舉各種電氣裝置、電子裝置、顯示裝置等之組裝步驟中之零件搬送用、暫時固定用等載帶、暫時固定材或固定材、目的在於防止金屬板、塑膠板、玻璃板等之污染損傷之表面保護材或遮蔽材等。尤其可較佳地用於電子零件之製造步驟中，較小或薄層之半導體晶片或積層電容器晶片等之製造步驟等中。 The energy ray-curable heat-peelable adhesive sheet of the present invention can also be used for the purpose of permanently adhering to an adherend, but is suitable for requiring or expecting to be adhered to a certain period of time, and releasing the subsequent state after reaching the next purpose. Use. As a specific example of the above-mentioned application, in addition to the fixing material of the semiconductor wafer or the ceramic laminated sheet, a carrier tape for component transfer, temporary fixing, and the like in various assembly steps of an electric device, an electronic device, and a display device may be mentioned. A fixing material or a fixing material, and a surface protective material or a masking material for preventing contamination of a metal plate, a plastic plate, a glass plate, or the like. In particular, it can be preferably used in a manufacturing step of an electronic component, a manufacturing step of a semiconductor chip or a multilayer capacitor wafer or the like of a small or thin layer.
繼而，基於實施例更詳細地說明本發明。再者，本發明並不受該等例之任何限定。 Next, the present invention will be described in more detail based on examples. Furthermore, the invention is not limited by the examples.
準備PET(polyethylene terephthalate，聚對苯二甲酸乙二酯)膜作為基材。將Toray公司製造之單面經電暈處理之Lumirror S105(厚度為50 μm)用作該PET膜。於該基材之電暈處理面側，將有機塗層以乾燥膜厚成為1~2 μm之方式利用凹版塗佈機進行塗佈並乾燥，獲得附帶有機塗層之基材1。該有機塗層使用淺藍色印刷油墨NB300(大日精化公 司)。再者，NB300中含有聚胺基甲酸酯系乙酸乙烯酯-氯乙烯共聚物作為黏合劑樹脂，藉由IR(infrared radiation，紅外線輻射)確認到可認為是胺基甲酸酯之強度峰值。 A PET (polyethylene terephthalate) film was prepared as a substrate. A single-faced corona-treated Lumirror S105 (thickness 50 μm) manufactured by Toray Corporation was used as the PET film. On the corona-treated surface side of the substrate, the organic coating layer was applied by a gravure coater so that the dried film thickness was 1 to 2 μm, and dried to obtain a substrate 1 with an organic coating. The organic coating uses light blue printing ink NB300 (Dai Ri Jinghua Division). Further, NB300 contained a polyurethane-vinyl acetate-vinyl chloride copolymer as a binder resin, and it was confirmed by IR (infrared radiation) that the intensity peak of the urethane was considered.
準備PET膜作為基材。將Toray公司製造之單面經電暈處理之Lumirror S105(厚度為50 μm)用作該PET膜。於該基材之電暈面處理側，將有機塗層以乾燥膜厚成為1~2 μm之方式利用凹版塗佈機進行塗佈並乾燥，獲得附帶有機塗層之基材2。該有機塗層使用不含淺藍色色素之印刷油墨NB300(大日精化公司)。再者，NB300中含有聚胺基甲酸酯系乙酸乙烯酯-氯乙烯共聚物作為黏合劑樹脂，藉由IR確認到可認為是胺基甲酸酯之強度峰值。 A PET film was prepared as a substrate. A single-faced corona-treated Lumirror S105 (thickness 50 μm) manufactured by Toray Corporation was used as the PET film. On the corona surface side of the substrate, the organic coating layer was applied by a gravure coater so that the dried film thickness was 1 to 2 μm, and dried to obtain a substrate 2 with an organic coating. This organic coating uses a printing ink NB300 (Daily Seiki Co., Ltd.) which does not contain a light blue pigment. Further, NB300 contains a polyurethane-vinyl acetate-vinyl chloride copolymer as a binder resin, and it has been confirmed by IR that it is considered to be a peak of the strength of the urethane.
準備PET膜作為基材。將Toray公司製造之單面經電暈處理之Lumirror S105(厚度為50 μm)用作該PET膜。於該基材之電暈面處理側，將有機塗層以乾燥膜厚成為1~2 μm之方式利用凹版塗佈機進行塗佈並乾燥，獲得附帶有機塗層之基材3。該有機塗層使用作為聚胺基甲酸酯系底塗劑之ADEKA Bon-Tighter U500(ADEKA製造)71重量份與作為異氰酸酯樹脂之Coronate HL(Nippon Polyurethane Industry製造)28重量份之乙酸乙酯溶液。 A PET film was prepared as a substrate. A single-faced corona-treated Lumirror S105 (thickness 50 μm) manufactured by Toray Corporation was used as the PET film. On the corona surface side of the substrate, the organic coating layer was applied by a gravure coater so that the dried film thickness was 1 to 2 μm, and dried to obtain a substrate 3 with an organic coating. The organic coating layer used 71 parts by weight of ADEKA Bon-Tighter U500 (manufactured by Adeka) as a polyurethane coating primer and 28 parts by weight of an ethyl acetate solution of Coronate HL (manufactured by Nippon Polyurethane Industry) as an isocyanate resin. .
投入丙烯酸第三丁酯50.0份、丙烯酸30.0份、丙烯酸丁酯20.0份作為丙烯酸系單體，三羥甲基丙烷三丙烯酸酯1.0 份作為多官能單體，1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮(商品名：Irgacure 2959，Ciba．Specialty．Chemicals(股份有限公司)製造)0.1份作為光聚合起始劑，聚氧丁二醇(分子量為650，三菱化學(股份有限公司)製造)73.4份作為多元醇，及二月桂酸二丁基錫0.05份作為胺基甲酸酯反應觸媒，一面攪拌一面滴加苯二亞甲基異氰酸酯26.6份，於65℃下反應2小時，獲得胺基甲酸酯聚合物-丙烯酸系單體混合物。聚異氰酸酯成分及多元醇成分之使用量為NCO/OH(當量比)=1.25。 50.0 parts of tributyl acrylate, 30.0 parts of acrylic acid, 20.0 parts of butyl acrylate were used as acrylic monomers, trimethylolpropane triacrylate 1.0 As a polyfunctional monomer, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (trade name: Irgacure 2959, Ciba. 0.1 parts of polyoxybutylene glycol (molecular weight: 650, manufactured by Mitsubishi Chemical Corporation), 73.4 parts as a polyhydric alcohol, and dibutyltin dilaurate, manufactured by Specialty Chemicals Co., Ltd. 0.05 parts of a urethane reaction catalyst was added dropwise 26.6 parts of benzodiamethylene isocyanate while stirring, and the mixture was reacted at 65 ° C for 2 hours to obtain a urethane polymer-acrylic monomer mixture. The amount of the polyisocyanate component and the polyol component used was NCO/OH (equivalent ratio) = 1.25.
將獲得之胺基甲酸酯聚合物-丙烯酸系單體混合物以硬化後之厚度成為3~4 μm之方式塗佈於厚度為38 μm之聚對苯二甲酸乙二酯膜(商品名：S-10，Toray公司製造)上。於其上重疊被覆經剝離處理之PET膜(厚度為38 μm)，使用高壓水銀燈將紫外線(照度為163 mW/cm2，光量為2100 mJ/cm2)照射至該被覆之PET膜面上使其硬化，獲得聚對苯二甲酸乙二酯/丙烯酸-胺基甲酸酯積層片材。 The obtained urethane polymer-acrylic monomer mixture was applied to a polyethylene terephthalate film having a thickness of 38 μm in a thickness of 3 to 4 μm after hardening (trade name: S -10, manufactured by Toray). The peeled PET film (thickness: 38 μm) was overlaid thereon, and ultraviolet rays (illuminance of 163 mW/cm 2 and light quantity of 2100 mJ/cm 2 ) were irradiated onto the surface of the coated PET film using a high pressure mercury lamp. It is hardened to obtain a polyethylene terephthalate/acrylic acid-urethane laminated sheet.
準備PET膜作為基材。將Toray公司製造之單面經電暈處理之Lumirror S105(厚度為38 μm)用作該PET膜。於該剛性膜層之電暈面處理側，將有機塗層以乾燥膜厚成為1~2 μm之方式利用凹版塗佈機進行塗佈並乾燥，獲得附帶有機塗層之基材5。該有機塗層使用藍色印刷油墨CVL-PR(DIC Graphics公司製造)。CVL-PR含有含羥基之乙酸乙烯酯-氯乙烯共聚物作為黏合劑樹脂，藉由IR未確認到可認為是胺 基甲酸酯之強度峰值。 A PET film was prepared as a substrate. A one-side corona-treated Lumirror S105 (thickness: 38 μm) manufactured by Toray Co., Ltd. was used as the PET film. On the corona surface side of the rigid film layer, the organic coating layer was applied by a gravure coater so that the dried film thickness was 1 to 2 μm, and dried to obtain a substrate 5 with an organic coating. This organic coating used a blue printing ink CVL-PR (manufactured by DIC Graphics Co., Ltd.). CVL-PR contains a hydroxyl group-containing vinyl acetate-vinyl chloride copolymer as a binder resin, which is not confirmed to be an amine by IR. The peak strength of the carbamate.
準備PET膜作為基材。將Toray公司製造之單面經電暈處理之Lumirror S105(厚度為50 μm)用作該PET膜。於該基材之電暈處理面側，將有機塗層以乾燥膜厚成為1~2 μm之方式利用凹版塗佈機進行塗佈並乾燥，獲得附帶有機塗層之基材6。該有機塗層使用非晶性飽和共聚合聚酯樹脂(商品名：Vylon 200，東洋紡織(股份有限公司)製造)。 A PET film was prepared as a substrate. A single-faced corona-treated Lumirror S105 (thickness 50 μm) manufactured by Toray Corporation was used as the PET film. On the corona-treated surface side of the substrate, the organic coating layer was applied by a gravure coater so that the dried film thickness was 1 to 2 μm, and dried to obtain a substrate 6 with an organic coating. The organic coating layer was an amorphous saturated copolymerized polyester resin (trade name: Vylon 200, manufactured by Toyobo Co., Ltd.).
使於丙烯酸2-乙基己酯：啉丙烯酸酯：丙烯酸2-羥基乙酯=75：25：20(莫耳比)之混合物100重量份中添加有聚合起始劑苄基過氧化物0.2重量份之甲苯溶液進行共聚合，獲得丙烯酸系聚合物(重量平均分子量70萬)。於獲得之上述丙烯酸系聚合物中調配來自丙烯酸2-羥基乙酯之羥基為50莫耳%之甲基丙烯醯氧基異氰酸乙酯(2-異氰酸酯基甲基丙烯酸乙酯)、及相對於上述丙烯酸系聚合物100重量份為0.03重量份之加成反應觸媒二月桂酸二丁基錫，並在空氣環境下使其於50℃下反應24小時，製造側鏈中具有甲基丙烯酸酯基之丙烯酸系聚合物。相對於獲得之丙烯酸系聚合物100重量份，添加3官能丙烯酸系光聚合性單體(三羥甲基丙烷三丙烯酸酯(商品名：Aronix M320，東亞合成(股份有限公司)製造))15重量份、自由基系光聚合起始劑(Irgacure 651，2,2-二甲氧基-1,2-二苯乙烷-1-酮，Ciba-geigy公司製造)1重量份、及異氰酸酯化合物(商品名： Coronate L，Nippon Polyurethane Industry(股份有限公司)製造)1重量份，獲得混合物。 To 2-ethylhexyl acrylate: Oxyl acrylate: a mixture of 2-hydroxyethyl acrylate = 75:25:20 (mole ratio) 100 parts by weight of a polymerization initiator benzyl peroxide added in 0.2 part by weight toluene solution for copolymerization to obtain acrylic acid A polymer (weight average molecular weight of 700,000). To the obtained acrylic polymer, 50 parts by mole of methacryloxyethyl isocyanate (2-isocyanate ethyl methacrylate) derived from a hydroxyl group of 2-hydroxyethyl acrylate, and relative The addition reaction catalyst, dibutyltin dilaurate, was added in an amount of 0.03 part by weight based on 100 parts by weight of the acrylic polymer, and reacted at 50 ° C for 24 hours in an air atmosphere to produce a methacrylate group in the side chain. Acrylic polymer. A trifunctional acryl-based photopolymerizable monomer (trimethylolpropane triacrylate (trade name: Aronix M320, manufactured by Toagosei Co., Ltd.)) was added in an amount of 15 parts by weight based on 100 parts by weight of the obtained acrylic polymer. And a radical photopolymerization initiator (Irgacure 651, 2,2-dimethoxy-1,2-diphenylethane-1-one, manufactured by Ciba-geigy Co., Ltd.), 1 part by weight, and an isocyanate compound ( Trade name: Coronate L, manufactured by Nippon Polyurethane Industry, 1 part by weight, to obtain a mixture.
將獲得之混合物使用模具塗布機，以乾燥膜厚成為30 μm之方式塗佈於經剝離處理之PET膜MRF38(三菱聚酯公司製造)之剝離處理面上。再者，經剝離處理之PET膜MRF38用作隔離片。 The obtained mixture was applied to a release-treated surface of a release-treated PET film MRF38 (manufactured by Mitsubishi Polyester Co., Ltd.) in a dry film thickness of 30 μm using a die coater. Further, the peeled-treated PET film MRF38 was used as a separator.
相對於包含丙烯酸乙酯/丙烯酸2-乙基己酯/丙烯酸2-羥基乙酯(80份/20份/5份)之共聚物聚合物100份，調配「Coronate L」(交聯劑，Nippon Polyurethane Industry公司製造)1份、120℃下發泡膨脹型之熱膨脹性微球「Matsumoto Microsphere F-50D」(熱膨脹性微球，松本油脂製造)30份而製備混合液。將該混合液塗敷於經剝離處理之PET膜MRF38(三菱聚酯公司製造)之剝離處理面上並使其乾燥，獲得10 μm之熱剝離型黏著劑層。 Coronate L (crosslinking agent, Nippon) was formulated with respect to 100 parts of copolymer polymer containing ethyl acrylate/2-ethylhexyl acrylate/2-hydroxyethyl acrylate (80 parts/20 parts/5 parts). A mixture of 30 parts of a heat-expandable microsphere "Matsumoto Microsphere F-50D" (heat-expandable microspheres, manufactured by Matsumoto Oil) having a foam expansion type at 120 ° C was prepared in a batch. The mixture was applied onto a release-treated surface of a release-treated PET film MRF38 (manufactured by Mitsubishi Polyester Co., Ltd.) and dried to obtain a heat-peelable adhesive layer of 10 μm.
於附帶有機塗層之基材1之有機塗層側貼合上述能量線硬化型黏著劑層，繼而貼合上述熱剝離型黏著劑層而製作加熱剝離型黏著片。 The energy ray-curable adhesive layer was bonded to the organic coating layer of the substrate 1 with the organic coating, and then the heat-peelable pressure-sensitive adhesive layer was bonded to each other to form a heat-peelable pressure-sensitive adhesive sheet.
於附帶有機塗層之基材2之有機塗層側貼合上述能量線硬化型黏著劑層，繼而貼合上述熱剝離型黏著劑層而製作加熱剝離型黏著片。 The energy ray-curable adhesive layer was bonded to the organic coating layer of the substrate 2 with the organic coating, and the heat-peelable pressure-sensitive adhesive layer was bonded thereto to form a heat-peelable pressure-sensitive adhesive sheet.
於附帶有機塗層之基材3之有機塗層側貼合上述能量線硬化型黏著劑層，繼而貼合上述熱剝離型黏著劑層而製作加熱剝離型黏著片。 The energy ray-curable adhesive layer was bonded to the organic coating layer of the substrate 3 with the organic coating, and then the heat-peelable pressure-sensitive adhesive layer was bonded to each other to form a heat-peelable pressure-sensitive adhesive sheet.
於附帶有機塗層之基材4之有機塗層側貼合上述能量線硬化型黏著劑層，繼而貼合上述熱剝離型黏著劑層而製作加熱剝離型黏著片。 The energy ray-curable adhesive layer was bonded to the organic coating layer of the substrate 4 with the organic coating, and then the heat-peelable pressure-sensitive adhesive layer was bonded to each other to form a heat-peelable pressure-sensitive adhesive sheet.
於Toray公司製造之PET膜Lumirror S10(厚度為50 μm)上貼合上述能量線硬化型黏著劑層，繼而貼合上述熱剝離型黏著劑層而製作加熱剝離型黏著片。 The above-mentioned energy ray-curable adhesive layer was bonded to a PET film Lumirror S10 (thickness: 50 μm) manufactured by Toray Co., Ltd., and then the heat-peelable adhesive layer was bonded to each other to form a heat-peelable adhesive sheet.
於Toray公司製造之單面經電暈處理之Lumirror S105(厚度為50 μm)上貼合上述能量線硬化型黏著劑層，繼而貼合上述熱剝離型黏著劑層而製作加熱剝離型黏著片。 The above-mentioned energy ray-curable adhesive layer was bonded to a one-side corona-treated Lumirror S105 (thickness: 50 μm) manufactured by Toray, and the heat-peelable adhesive layer was bonded thereto to prepare a heat-peelable adhesive sheet.
於附帶有機塗層之基材5之有機塗層側貼合上述能量線硬化型黏著劑層，繼而貼合上述熱剝離型黏著劑層而製作加熱剝離型黏著片。 The energy ray-curable adhesive layer was bonded to the organic coating side of the substrate 5 with the organic coating, and then the heat-peelable pressure-sensitive adhesive layer was bonded to each other to form a heat-peelable pressure-sensitive adhesive sheet.
於附帶有機塗層之基材6之有機塗層側貼合上述能量線硬化型黏著劑層，繼而貼合上述熱剝離型黏著劑層而製作加熱剝離型黏著片。 The energy ray-curable adhesive layer was bonded to the organic coating side of the substrate 6 with the organic coating, and the heat-peelable pressure-sensitive adhesive layer was bonded thereto to prepare a heat-peelable pressure-sensitive adhesive sheet.
使用日東精機公司製造之UV照射機NEL UM810(高壓水銀燈光源，20 mW/cm2)對獲得之加熱剝離型黏著片進行300 mJ/cm2之紫外線照射，使能量線硬化型彈性層硬化。 The obtained heat-peelable pressure-sensitive adhesive sheet was irradiated with ultraviolet rays of 300 mJ/cm 2 using a UV irradiation machine NEL UM810 (high-pressure mercury lamp light source, 20 mW/cm 2 ) manufactured by Nitto Seiki Co., Ltd. to harden the energy ray-curable elastic layer.
於上述加熱剝離型黏著片之黏著劑面上貼附120 mm×100 mm×厚度0.5 mm之焙燒前之陶瓷片材，全切為0.4 mm×0.2 mm之晶片。其後，於加熱板上進行120℃×3分鐘之加熱處理，冷卻後，使其反轉振動而回收晶片。 A ceramic sheet of 120 mm × 100 mm × 0.5 mm thick was attached to the adhesive surface of the above-mentioned heat-peelable adhesive sheet, and the wafer was cut into 0.4 mm × 0.2 mm. Thereafter, heat treatment was performed on a hot plate at 120 ° C for 3 minutes, and after cooling, the wafer was inverted and vibrated to recover the wafer.
加熱處理後，反轉振動而回收晶片時，對100個晶片中未脫落之晶片數進行計數。 After the heat treatment, when the vibration was reversed and the wafer was collected, the number of wafers that did not fall off in 100 wafers was counted.
使用光學顯微鏡對將陶瓷片材全切並進行有加熱處理之加熱剝離型黏著片之黏著劑面進行觀察，對100個晶片中之糊劑剝落之數量進行計數。該糊劑剝落之程度亦表示晶片表面上之糊劑殘餘之程度。 The adhesive surface of the heat-peelable adhesive sheet in which the ceramic sheet was completely cut and subjected to heat treatment was observed using an optical microscope, and the amount of paste peeling in 100 wafers was counted. The extent to which the paste is peeled off also indicates the extent of paste residue on the surface of the wafer.
採用以下方法求出切斷精度。 The cutting accuracy was obtained by the following method.
利用光學顯微鏡對切斷後之晶片剖面進行觀察，求出剖面相對於陶瓷片材表面之角度，將其作為切斷精度。越接近90°則表示切斷精度越優異。 The cross section of the wafer after the cutting was observed with an optical microscope, and the angle of the cross section with respect to the surface of the ceramic sheet was determined, and this was taken as the cutting precision. The closer to 90°, the more excellent the cutting accuracy.
將上述各實施例及比較例及其結果示於以下表1。 Each of the above examples and comparative examples and the results thereof are shown in Table 1 below.
當使用實施例1~4之加熱剝離型黏著片全切陶瓷片材時，回收獲得之晶片時無未脫落之晶片，加熱剝離性良好。 When the heat-peelable adhesive sheet-cut ceramic sheets of Examples 1 to 4 were used, the wafers obtained were recovered without any wafers that had not fallen off, and the heat-peelability was good.
又，全切後之加熱剝離型黏著片之黏著面上無糊劑剝落。 Further, the adhesive surface of the heat-peelable adhesive sheet after the whole cut was peeled off without a paste.
由該等結果可知，根據本發明，可抑制切斷步驟中之黏著劑之偏移或上捲、碎屑，且於切斷後可容易地剝離回收以高精度切斷加工而成之切斷片。此時，可明顯提高切斷片之剝離、回收步驟中之操作性及作業性，而且可較大地提高精度較高、或者小型或薄層之半導體晶片或積層電容器晶片等切斷片之生產性。 As a result of the above, according to the present invention, it is possible to suppress the offset of the adhesive in the cutting step, the winding up, and the chipping, and it is possible to easily peel off and collect the cut piece which is cut at a high precision after cutting. In this case, the workability and workability in the peeling and recovery steps of the cut piece can be remarkably improved, and the productivity of a cut piece such as a semiconductor wafer or a multilayer capacitor wafer having a high precision or a small or thin layer can be greatly improved.
與此相對，於使用未設置有機塗層之比較例1及2之加熱剝離型黏著片之情形時，加熱剝離性及糊劑剝落均不良。 On the other hand, in the case of using the heat-peelable pressure-sensitive adhesive sheets of Comparative Examples 1 and 2 in which the organic coating layer was not provided, the heat peeling property and the peeling of the paste were both poor.
進而，參考例1及2之加熱剝離型黏著片為採用包含胺基甲酸酯系聚合物以外之材料之層作為有機塗層之例，與比較例1及2同樣地，加熱剝離性及糊劑剝落均不良。 Further, the heat-peelable pressure-sensitive adhesive sheets of Reference Examples 1 and 2 are examples in which a layer containing a material other than the urethane-based polymer is used as an organic coating layer, and similarly to Comparative Examples 1 and 2, the heat-peelability and paste are heated. The agent peeling was poor.
根據該等實施例及比較例、參考例之結果可知，藉由在 本發明之加熱剝離型黏著片中採用包含胺基甲酸酯系聚合物之有機塗層，與非如此之情形相比可獲得明顯之效果。 According to the results of the embodiments, the comparative examples, and the reference examples, In the heat-peelable adhesive sheet of the present invention, an organic coating layer containing a urethane-based polymer is used, and a remarkable effect can be obtained as compared with the case where it is not.
1‧‧‧基材 1‧‧‧Substrate
2‧‧‧有機塗層 2‧‧‧Organic coating
3‧‧‧能量線硬化型彈性層 3‧‧‧Energy line hardening elastic layer
3a‧‧‧能量線照射後之經硬化之彈性層 3a‧‧‧A hardened elastic layer after irradiation with energy rays
4‧‧‧熱剝離型黏著劑層 4‧‧‧Hot peeling adhesive layer
4a‧‧‧加熱處理後之熱剝離型黏著劑層 4a‧‧‧ Heat-treated adhesive layer after heat treatment
5‧‧‧隔離片 5‧‧‧Isolation
6‧‧‧接著劑層 6‧‧‧ adhesive layer
7‧‧‧隔離片 7‧‧‧Isolation film
8‧‧‧被黏著體(被切斷體) 8‧‧‧Adhered body (cut body)
8a‧‧‧切斷片 8a‧‧‧ cut pieces
9‧‧‧能量線 9‧‧‧Energy line
10‧‧‧切斷線 10‧‧‧ cut line
圖1係表示本發明之加熱剝離型黏著片之一例之概略圖。 Fig. 1 is a schematic view showing an example of a heat-peelable pressure-sensitive adhesive sheet of the present invention.
圖2係表示本發明之加熱剝離型黏著片之其他例之概略圖。 Fig. 2 is a schematic view showing another example of the heat-peelable pressure-sensitive adhesive sheet of the present invention.
圖3係表示使用本發明之加熱剝離型黏著片加工電子零件之步驟之概略圖。 Fig. 3 is a schematic view showing a step of processing an electronic component using the heat-peelable adhesive sheet of the present invention.
1‧‧‧基材 1‧‧‧Substrate
2‧‧‧有機塗層 2‧‧‧Organic coating
3‧‧‧能量線硬化型彈性層 3‧‧‧Energy line hardening elastic layer
4‧‧‧熱剝離型黏著劑層 4‧‧‧Hot peeling adhesive layer
5‧‧‧隔離片 5‧‧‧Isolation
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| WO2020196758A1 (en) * | 2019-03-28 | 2020-10-01 | リンテック株式会社 | Pressure-sensitive adhesive sheet, method for producing pressure-sensitive adhesive sheet, and method for producing semiconductor device |
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| JP2022047610A (en) * | 2020-09-14 | 2022-03-25 | 株式会社村田製作所 | Fixing member for cutting electronic component prime field and cutting method of electronic component prime field |
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|---|---|---|---|---|
| TWI291983B (en) * | 2000-10-18 | 2008-01-01 | Nitto Denko Corp | Energy-beam-curable thermal-releasable pressure-sensitive adhesive sheet and method for producing cut pieces using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103827241A (en) | 2014-05-28 |
| JP6000958B2 (en) | 2016-10-05 |
| JPWO2013042698A1 (en) | 2015-03-26 |
| KR101950051B1 (en) | 2019-02-19 |
| TW201319207A (en) | 2013-05-16 |
| WO2013042698A1 (en) | 2013-03-28 |
| KR20140068972A (en) | 2014-06-09 |
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