TWI493011B - Die cutting with an adhesive film, and a method for manufacturing a cut sheet - Google Patents

Die cutting with an adhesive film, and a method for manufacturing a cut sheet Download PDF

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TWI493011B
TWI493011B TW100107168A TW100107168A TWI493011B TW I493011 B TWI493011 B TW I493011B TW 100107168 A TW100107168 A TW 100107168A TW 100107168 A TW100107168 A TW 100107168A TW I493011 B TWI493011 B TW I493011B
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radiation
meth
hydroxyl group
die
adhesive film
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TW100107168A
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TW201204799A (en
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Yasuaki Okumura
Keigo Sato
Yoshiyuki Nagataki
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Sugawara Ind
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Dicing (AREA)
  • Adhesive Tapes (AREA)

Description

模切(die cutting)用黏著薄膜，及切斷片之製造方法Adhesive film for die cutting, and manufacturing method of the cut piece

本發明關於模切用黏著薄膜，及切斷片之製造方法。特別地，本發明關於模切用黏著薄膜之黏著劑層所用的輻射線硬化性黏著劑組成物之改良。The present invention relates to an adhesive film for die cutting and a method for producing the cut sheet. In particular, the present invention relates to an improvement of a radiation curable adhesive composition for an adhesive layer of an adhesive film for die cutting.

以往，半導體晶圓或半導體封裝的半導體關聯材料等，係使用旋轉刀等的切斷刀來切斷，而分離成小片的半導體元件或IC零件。例如，以矽、鍺、鎵-砷等為材料的半導體晶圓，係以大直徑的狀態製造後，進行背面研削處理(背景處理)直到成為指定的厚度為止，更且視需要可施予背面處理(蝕刻處理、拋光處理等)。其次，將半導體晶圓切斷分離(模切)成元件小片，移到其後的步驟。於此製程中，進行將半導體晶圓預先黏貼於模切用黏著薄膜之安裝步驟、以該黏著薄膜黏貼於半導體晶圓的狀態下將半導體晶圓模切成半導體元件小片之模切步驟、洗淨步驟、擴展步驟、拾取步驟等的各種步驟。而且，於上述拾取步驟中，採用使模切用黏著薄膜成為某一程度的張拉狀態，以點狀或線狀舉起所拾取的半導體元件下部之模切用黏著薄膜，在助長該半導體元件與模切用黏著薄膜之剝離的狀態下，藉由自上部的真空吸附等，拾取半導體元件之方式。Conventionally, a semiconductor-related material such as a semiconductor wafer or a semiconductor package is cut by a cutting blade such as a rotary blade to be separated into small pieces of a semiconductor element or an IC component. For example, a semiconductor wafer made of yttrium, lanthanum, gallium-arsenic or the like is manufactured in a large-diameter state, and then subjected to back grinding processing (background processing) until it reaches a predetermined thickness, and can be applied as needed. Processing (etching treatment, polishing treatment, etc.). Next, the semiconductor wafer is cut (separated) into small pieces and moved to the subsequent steps. In the process of the present invention, a step of attaching a semiconductor wafer to an adhesive film for die-cutting, a die-cutting step of die-cutting a semiconductor wafer into a semiconductor device in a state in which the adhesive film is adhered to the semiconductor wafer, and a step of washing Various steps of the net step, the expansion step, the picking step, and the like. Further, in the above-described pickup step, the die-cut adhesive film is stretched to a certain extent, and the die-bonding adhesive film of the lower portion of the semiconductor element picked up is lifted in a dot shape or a line shape to promote the semiconductor component. In a state in which it is peeled off from the die-bonding adhesive film, the semiconductor element is picked up by vacuum suction or the like from the upper portion.

上述模切用黏著薄膜一般具有在塑膠薄膜等的基材上形成含有黏著劑組成物的黏著劑層之構成。於製造半導體元件時，對模切用黏著薄膜，為了抑制在模切步驟中半導體元件自黏著薄膜脫離飛散，要求在模切時即使施加洗淨水的水壓，半導體元件也不會自黏著薄膜剝離的程度之高黏著力，另一方面，於拾取步驟的剝離時，要求黏著劑層具有不破壞半導體晶圓的程度之低黏著力的輕剝離性。The above-mentioned adhesive film for die-cutting generally has a structure in which an adhesive layer containing an adhesive composition is formed on a substrate such as a plastic film. In the manufacture of a semiconductor element, in order to suppress the scattering of the semiconductor element from the adhesive film in the die-cutting step, it is required that the semiconductor element does not adhere to the film even when the water pressure of the cleaning water is applied during the die-cutting process. The degree of peeling is high, and on the other hand, at the time of peeling of the pick-up step, the adhesive layer is required to have a light peeling property with a low adhesion to a degree that does not damage the semiconductor wafer.

作為滿足如上述之特性的模切用黏著薄膜，廣用一種在輻射線透過性的基材上，形成有由所謂的摻合型輻射線硬化性黏著劑組成物所成的黏著劑層之模切用黏著薄膜，該黏著劑組成物含有：導入有羥基等的官能基之基礎聚合物，與在分子內具有能與上述羥基反應的官能基及輻射線反應性之碳-碳雙鍵的輻射線反應性化合物反應而得之(甲基)丙烯酸系聚合物，以及為了促進輻射線所致的硬化，多官能單體或多官能寡聚物等之低分子量多官能聚合性化合物(例如專利文獻1)。於此種模切用黏著薄膜中，在輻射線所致的硬化前，由於輻射線硬化性黏著劑組成物具有高的黏著力，而在模切步驟中可抑制半導體元件的脫離飛散。又，若對黏著劑層照射輻射線，由於輻射線硬化性黏著劑組成物硬化而黏著力降低，故在拾取步驟中可自模切用黏著薄膜容易地剝離半導體元件。As an adhesive film for die-cutting which satisfies the above characteristics, a radiation-transmissive substrate is widely used to form an adhesive layer formed of a so-called blended radiation curable adhesive composition. An adhesive film comprising: a base polymer having a functional group introduced with a hydroxyl group or the like, and a radiation having a functional group reactive with the hydroxyl group and a radiation-reactive carbon-carbon double bond in the molecule; A (meth)acrylic polymer obtained by reacting a linear reactive compound, and a low molecular weight polyfunctional polymerizable compound such as a polyfunctional monomer or a polyfunctional oligomer for promoting hardening by radiation (for example, Patent Literature) 1). In such an adhesive film for die cutting, since the radiation curable adhesive composition has a high adhesive force before hardening by radiation, the detachment of the semiconductor element can be suppressed in the die cutting step. Further, when the adhesive layer is irradiated with radiation, the radiation curable adhesive composition is hardened and the adhesive force is lowered. Therefore, in the pickup step, the semiconductor element can be easily peeled off from the die-cut adhesive film.

還有，近年來於半導體製程中，以防止半導體晶圓的薄膜化(例如100μm以下)所造成的破損為目的，在背面研削處理後，或背面研削處理及背面處理結束後，多在短時間內將模切用黏著薄膜黏貼於半導體晶圓。於如此的背面研削處理後，或背面研削處理及背面處理後，在短時間內將模切用黏著薄膜黏貼於薄膜的半導體晶圓時，半導體晶圓與黏著劑層的黏著力變高，輻射線所致的硬化後之剝離變困難，發生拾取性降低的問題。推測此係因為在半導體晶圓之已進行背面研削處理或背面處理的處理面中，自然氧化膜未在半導體晶圓的全面上充分形成，半導體晶圓的表面係成為未氧化狀態的活性原子(例如矽原子等)存在的活性面，因此若於此活性面上黏貼模切用黏著薄膜，則未氧化狀態的活性原子與黏著劑層的輻射線硬化性黏著劑組成物接觸，在未氧化狀態的活性原子與輻射線硬化性黏著劑組成物之間發生化學鍵結。In recent years, in the semiconductor manufacturing process, in order to prevent breakage of the semiconductor wafer by thin film formation (for example, 100 μm or less), after the back grinding process, or the back grinding process and the back surface process, it is often in a short time. The inner die-cutting is adhered to the semiconductor wafer with an adhesive film. After such a back grinding process, or a back grinding process and a back surface process, when the die-cut adhesive film is adhered to the thin film semiconductor wafer in a short time, the adhesion between the semiconductor wafer and the adhesive layer is increased, and the radiation is increased. The peeling after hardening by the wire becomes difficult, and the problem of the pickup property is lowered. It is presumed that since the natural oxide film is not sufficiently formed on the entire surface of the semiconductor wafer in the processing surface of the semiconductor wafer which has been subjected to the back grinding process or the back surface process, the surface of the semiconductor wafer is an active atom in an unoxidized state ( For example, a ruthenium atom or the like exists on the active surface. Therefore, if the adhesive film for die-cutting is adhered to the active surface, the active atoms in the unoxidized state are in contact with the radiation-curable adhesive composition of the adhesive layer, and are in an unoxidized state. A chemical bond occurs between the active atom and the radiation curable adhesive composition.

如專利文獻1的摻合型輻射線硬化性黏著劑組成物，茲認為若將輻射線照射於黏著劑層，則不僅具有輻射線反應性碳-碳雙鍵的(甲基)丙烯酸系聚合物彼此，而且(甲基)丙烯酸系聚合物亦與低分子量多官能聚合性化合物反應，故於輻射線的硬化後可使黏著力降低，即使對於如上述具有活性面之被加工物也可適用。As the blended radiation curable adhesive composition of Patent Document 1, it is considered that if the radiation is irradiated to the adhesive layer, not only the (meth)acrylic polymer having a radiation-reactive carbon-carbon double bond is used. Further, since the (meth)acrylic polymer is also reacted with the low molecular weight polyfunctional polymerizable compound, the adhesion can be lowered after the radiation is cured, and it can be applied to the workpiece having the active surface as described above.

然而，依照本發明者等的檢討可明知，則即使使用含有如上述的低分子量多官能聚合性化合物之輻射線硬化性黏著劑組成物，若將具有活性面的半導體晶圓模切，而拾取半導體元件時，也不充分改善拾取性。茲認為此係因為輻射線硬化性黏著劑組成物的主成分(甲基)丙烯酸系聚合物與活性面的強鍵結所造成。又，若大量地使用低分子量多官能聚合性化合物，則輻射線硬化性黏著劑組成物中的游離低分子量成分增加，輻射線的硬化前之黏著力降低。特別地，於模切步驟中，雖然在SUS等金屬製或樹脂製之環框上黏貼黏著劑層，但含有低分子量多官能聚合性化合物的輻射線硬化性黏著劑組成物係對此等環框有黏著力低之問題。However, according to the review by the inventors of the present invention, it is known that even if a radiation curable adhesive composition containing the low molecular weight polyfunctional polymerizable compound as described above is used, the semiconductor wafer having the active surface is die-cut and picked up. In the case of a semiconductor element, the pickup property is not sufficiently improved. It is considered that this is caused by the strong bonding of the main component (meth)acrylic polymer of the radiation curable adhesive composition to the active surface. Further, when a low molecular weight polyfunctional polymerizable compound is used in a large amount, the free low molecular weight component in the radiation curable adhesive composition increases, and the adhesive force before curing of the radiation is lowered. In particular, in the die-cutting step, the adhesive layer is adhered to a ring made of metal or resin such as SUS, but the radiation curable adhesive composition containing a low molecular weight polyfunctional polymerizable compound is such a ring. The frame has a problem of low adhesion.

又，於半導體元件的製造中，要求在模切時於半導體元件的背面或側面不發生碎裂(晶片破碎)。若發生如此的碎裂，則半導體元件本身的彎曲強度降低，而且空氣容易捲入所密封的IC封裝內，變容易發生封裝裂紋。此碎裂係肇因於模切時切斷刀導致半導體元件振動，半導體元件發生位置偏移或凸起。因此，期望一種模切用黏著薄膜，即使在模切時施加切斷刀所致的振動，也具可有減低半導體元件的位置偏移之高內聚力之黏著劑層。Further, in the manufacture of a semiconductor element, it is required that no chipping (wafer breakdown) occurs on the back surface or the side surface of the semiconductor element during die cutting. When such a chipping occurs, the bending strength of the semiconductor element itself is lowered, and air is easily caught in the sealed IC package, and package cracking easily occurs. This chipping system causes the semiconductor element to vibrate due to the cutting of the blade during die cutting, and the semiconductor element is displaced or raised. Therefore, an adhesive film for die cutting is desired, and an adhesive layer capable of reducing the high cohesive force of the positional deviation of the semiconductor element can be obtained even if the vibration caused by the cutting blade is applied during die cutting.

當提高如上述含有(甲基)丙烯酸系聚合物的輻射線硬化性黏著劑組成物之內聚力時，藉由使用交聯劑來三次元交聯(甲基)丙烯酸系聚合物，則有效於提高輻射線硬化性黏著劑組成物的保持力。因此，於專利文獻1中，亦使用一種輻射線硬化性黏著劑組成物，其含有(甲基)丙烯酸系聚合物，與在分子內具有能與(甲基)丙烯酸系聚合物所具有的羥基進行交聯反應的異氰酸酯基或環氧基等官能基之交聯劑。When the cohesive force of the radiation curable adhesive composition containing the (meth)acrylic polymer as described above is increased, the (meth)acrylic polymer is three-dimensionally crosslinked by using a crosslinking agent, thereby effectively improving The retention of the radiation curable adhesive composition. Therefore, Patent Document 1 also uses a radiation curable adhesive composition containing a (meth)acrylic polymer and having a hydroxyl group which is compatible with a (meth)acrylic polymer in the molecule. A crosslinking agent of a functional group such as an isocyanate group or an epoxy group which is subjected to a crosslinking reaction.

然而，如此地在分子內具有輻射線反應性碳-碳雙鍵之(甲基)丙烯酸系聚合物之合成時，從必須使已導入基礎聚合物中的羥基與輻射線反應性化合物之官能基反應來看，僅增多交聯劑的含量，若交聯劑與(甲基)丙烯酸系聚合物反應的羥基少，則(甲基)丙烯酸系聚合物與交聯劑之間的交聯反應也不充分發生，而僅增加低分子量成分，不僅得不到高保持力，而且切斷片上的糊污染變多，有污染性劣化的問題。However, in the synthesis of a (meth)acrylic polymer having a radiation-reactive carbon-carbon double bond in the molecule, the functional group of the hydroxyl group and the radiation-reactive compound which have been introduced into the base polymer must be made. In the reaction, only the content of the crosslinking agent is increased, and if the crosslinking agent reacts with the (meth)acrylic polymer, the crosslinking reaction between the (meth)acrylic polymer and the crosslinking agent is also Inadequate occurrence, and only the addition of the low molecular weight component, not only does not obtain high holding power, but also causes a large amount of paste contamination on the cut piece, which causes a problem of contamination deterioration.

[先前技術文獻][Previous Technical Literature] [專利文獻][Patent Literature]

[專利文獻1]特開2007-220694號公報[Patent Document 1] JP-A-2007-220694

本發明係為了解決上述問題而完成者，本發明之目的在於提供一種模切用黏著薄膜，其具備含有輻射線硬化性黏著劑組成物的黏著劑層，在藉由輻射線所致的硬化前，對於半導體晶圓等的被加工物及環框具有高黏著力及高保持力，同時在藉由輻射線所致的硬化後，即使對於具有活性面的被加工物也具有優異的輕剝離性及低污染性，以及提供一種製造方法，其藉由使用上述模切用黏著薄膜，而在模切步驟中可抑制半導體元件等的切斷片之脫離飛散，同時抑制切斷片的振動，減低碎裂，在拾取步驟的糊污染少，而且容易剝離模切用黏著薄膜與切斷片。The present invention has been made to solve the above problems, and an object of the present invention is to provide an adhesive film for die cutting comprising an adhesive layer containing a radiation curable adhesive composition before curing by radiation. It has high adhesion and high holding power for workpieces and ring frames such as semiconductor wafers, and has excellent light peelability even for workpieces having active surfaces after hardening by radiation. And a low-pollution property, and a manufacturing method for suppressing detachment of a cut piece of a semiconductor element or the like in the die-cutting step by using the above-mentioned die-cut adhesive film, and suppressing vibration of the cut piece and reducing chipping The paste in the picking step is less contaminated, and the adhesive film and the cut piece for die cutting are easily peeled off.

本發明係一種模切用黏著薄膜，其係具備基材，與在前述基材上之含有輻射線硬化性黏著組成物的黏著層之模切用黏著薄膜，其中前述輻射線硬化性黏著劑組成物含有：使至少具有含烷基的(甲基)丙烯酸系單體及含羥基的(甲基)丙烯酸系單體當作共聚合單體成分，而且具有9.6(cal/cm3 )1/2 以上、10.0(cal/cm3 )1/2 以下的溶解度參數之基礎聚合物，與在分子內具有能與經由前述含羥基的(甲基)丙烯酸系單體導入基礎聚合物中的羥基反應的第1官能基及輻射線反應性碳-碳雙鍵之輻射線反應性化合物進行反應而得之(甲基)丙烯酸系聚合物，及對於100質量份的前述(甲基)丙烯酸系聚合物而言，0.3～2.7質量份的在分子內具有能與前述羥基進行交聯反應的第2官能基之交聯劑；前述含羥基的(甲基)丙烯酸系單體、前述輻射線反應性化合物及前述交聯劑，係以經由前述含羥基的(甲基)丙烯酸系單體導入基礎聚合物中的羥基之莫耳質量為前述輻射線反應性化合物的第1官能基及前述交聯劑的第2官能基之合計莫耳量以上，每1g輻射線硬化性黏著劑組成物中的交聯反應後之殘存羥基濃度為0.08mmol以下，每1g輻射線硬化性黏著劑組成物中的經由前述輻射線反應性化合物導入(甲基)丙烯酸系聚合物中的輻射線反應性碳-碳雙鍵濃度為0.42mmol以上、0.84mmol以下而配合。The present invention relates to an adhesive film for die cutting, which comprises a substrate, and an adhesive film for die-cutting of an adhesive layer containing a radiation curable adhesive composition on the substrate, wherein the radiation curable adhesive is composed of The composition contains: a (meth)acrylic monomer having at least an alkyl group and a hydroxyl group-containing (meth)acrylic monomer as a copolymerization monomer component, and having 9.6 (cal/cm 3 ) 1/2 The base polymer having a solubility parameter of 10.0 (cal/cm 3 ) 1/2 or less and the reaction with a hydroxyl group introduced into the base polymer via the hydroxyl group-containing (meth)acrylic monomer are contained in the molecule. a (meth)acrylic polymer obtained by reacting a radiation-reactive compound of a first functional group and a radiation-reactive carbon-carbon double bond, and 100 parts by mass of the (meth)acrylic polymer 0.3 to 2.7 parts by mass of a crosslinking agent having a second functional group capable of crosslinking reaction with the hydroxyl group in the molecule; the hydroxyl group-containing (meth)acrylic monomer, the radiation reactive compound, and The aforementioned crosslinking agent is via the aforementioned hydroxyl group The molar mass of the hydroxyl group introduced into the base polymer of the (meth)acrylic monomer is equal to or greater than the total amount of the first functional group of the radiation-reactive compound and the second functional group of the crosslinking agent. The residual hydroxyl group concentration after the crosslinking reaction in the radiation curable adhesive composition of 1 g is 0.08 mmol or less, and the (meth)acrylic acid is introduced into the radiation curable adhesive composition per gram via the radiation reactive compound. The concentration of the radiation-reactive carbon-carbon double bond in the polymer is 0.42 mmol or more and 0.84 mmol or less.

上述輻射線硬化性黏著劑組成物，由於含有一種使用具有9.6(cal/cm3 )1/2 以上、10.0(cal/cm3 )1/2 以下的溶解度參數之基礎聚合物所得之(甲基)丙烯酸系聚合物，故所得之(甲基)丙烯酸系聚合物係極性部位少，而且極性部位容易被隱蔽，結果可抑制活性原子與極性部位的結合，可充分減低輻射線所致的硬化後之黏著力。The radiation curable adhesive composition is obtained by using a base polymer having a solubility parameter of 9.6 (cal/cm 3 ) 1/2 or more and 10.0 (cal/cm 3 ) 1/2 or less. Since the obtained (meth)acrylic polymer has a small number of polar sites and the polar portion is easily concealed, the binding of the active atom to the polar portion can be suppressed, and the hardening by the radiation can be sufficiently reduced. Adhesion.

又，上述輻射線硬化性黏著劑組成物，為了提高輻射線所致的硬化前之保持力，雖然含有一定量的在分子內具有能與經由含羥基的(甲基)丙烯酸系單體導入基礎聚合物中的羥基進行交聯反應的第2官能基之交聯劑，但由於以使經由該含羥基的(甲基)丙烯酸系單體導入基礎聚合物中的羥基之莫耳量成為輻射線反應性化合物的第1官能基及交聯劑的第2官能基之合計莫耳量以上的方式，配合含羥基的(甲基)丙烯酸系單體、輻射線反應性化合物及交聯劑，故即使使基礎聚合物與輻射線反應性化合物反應而導入輻射線反應碳-碳雙鍵後，也可在(甲基)丙烯酸系聚合物中確保可與交聯劑交聯反應的羥基。結果，可得到輻射線硬化性黏著劑組成物中的游離低分子量成分變少，於輻射線所致的硬化前，對於半導體晶圓或金屬製構件具有高的黏著力，同時具有高保持力，於輻射線所致的硬化後，具有低污染性的輻射線硬化性黏著劑組成物。Further, the radiation curable adhesive composition has a certain amount of intramolecular energy and can be introduced into the base via a hydroxyl group-containing (meth)acrylic monomer in order to increase the retention force before hardening due to radiation. a crosslinking agent of a second functional group in which a hydroxyl group in the polymer undergoes a crosslinking reaction, but the amount of the hydroxyl group of the hydroxyl group introduced into the base polymer via the hydroxyl group-containing (meth)acrylic monomer is irradiated The hydroxyl group-containing (meth)acrylic monomer, the radiation-reactive compound, and the crosslinking agent are blended in such a manner that the total amount of the first functional group of the reactive compound and the second functional group of the crosslinking agent is more than the molar amount. Even after the base polymer is reacted with the radiation-reactive compound to introduce a radiation-reactive carbon-carbon double bond, a hydroxyl group which can be crosslinked with the crosslinking agent can be secured in the (meth)acrylic polymer. As a result, the free low molecular weight component in the radiation curable adhesive composition can be reduced, and the semiconductor wafer or the metal member has high adhesion and high retention force before curing due to radiation. A radiation-curable adhesive composition having low contamination after hardening by radiation.

再者，於上述輻射線硬化性黏著劑組成物中，由於以每1g輻射線硬化性黏著劑組成物中的交聯反應後之殘存羥基濃度成為0.08mmol以下的方式，配合含羥基的(甲基)丙烯酸系單體、輻射線反應性化合物及交聯劑，故即使經由含羥基的(甲基)丙烯酸系單體導入基礎聚合物中的羥基之莫耳量為輻射線反應性化合物的第1官能基及交聯劑的第2官能基之合計莫耳量以上，交聯反應後的輻射線硬化性黏著劑組成物全體中的殘存羥基也少，因此即使對於具有活性面的被加工物，也可充分減低輻射線的照射所致的硬化後之黏著力。Further, in the radiation-curable adhesive composition, the hydroxyl group-containing content is added so that the residual hydroxyl group concentration after the crosslinking reaction in the composition of the radiation curable adhesive composition per gram is 0.08 mmol or less. The acrylic monomer, the radiation reactive compound, and the crosslinking agent, so that the amount of the hydroxyl group of the hydroxyl group introduced into the base polymer via the hydroxyl group-containing (meth)acrylic monomer is the first of the radiation reactive compound. Since the total amount of the second functional groups of the monofunctional group and the crosslinking agent is not more than the molar amount, and the residual hydroxyl group in the entire radiation curable adhesive composition after the crosslinking reaction is small, even for the workpiece having the active surface It can also fully reduce the adhesion after hardening caused by radiation exposure.

而且，於上述輻射線硬化性黏著劑組成物中，由於以每1g輻射線硬化性黏著劑組成物中的經由前述輻射線反應性化合物導入(甲基)丙烯酸系聚合物中的輻射線反應性碳-碳雙鍵濃度成為0.42mmol以上、0.84mmol以下的方式，配合含羥基的(甲基)丙烯酸系單體、輻射線反應性化合物及交聯劑，故即使不使用會使輻射線所致的硬化前之黏著力或保持力或降低的多官能單體或多官能寡聚物等之低分子量多官能聚合性化合物，也可充分降低輻射線所致的硬化後之黏著力。Further, in the radiation curable adhesive composition, radiation reactivity into the (meth)acrylic polymer via the radiation-reactive compound per 1 g of the radiation curable adhesive composition is obtained. When the carbon-carbon double bond concentration is 0.42 mmol or more and 0.84 mmol or less, a hydroxyl group-containing (meth)acrylic monomer, a radiation-reactive compound, and a crosslinking agent are blended, so that radiation may be caused by not using it. The low-molecular-weight polyfunctional polymerizable compound such as a polyfunctional monomer or a polyfunctional oligomer which is adhered or retained before hardening can also sufficiently reduce the adhesion after hardening due to radiation.

再者，本說明書中的(甲基)丙烯酸係意味丙烯酸或甲基丙烯酸。Further, the (meth)acrylic acid in the present specification means acrylic acid or methacrylic acid.

上述輻射線硬化性黏著劑組成物較佳為實質上不含有低分子量多官能聚合性化合物。若藉由上述模切用黏著薄膜，可得到於輻射線所致的硬化前具有高黏著力及高保持力的模切用黏著薄膜。The radiation curable adhesive composition preferably contains substantially no low molecular weight polyfunctional polymerizable compound. According to the above-mentioned die-bonding adhesive film, an adhesive film for die-cutting which has high adhesion and high holding power before curing due to radiation can be obtained.

而且，本發明係一種切斷片之製造方法，其係：於被加工物的一面於被加工物的一面貼上上述記載的模切用黏著薄膜，將貼有前述模切用黏著薄膜的被加工物切斷而分離成切斷片，對貼於前述切斷片的黏著劑層，照射輻射線以使得前述黏著劑層的黏著力降低，由前述黏著力已降低的模切用黏著薄膜來拾取前述切斷片。Further, the present invention provides a method of producing a cut sheet in which the adhesive film for die cutting described above is attached to one surface of a workpiece, and the adhesive film for die cutting is processed. The material is cut into a cut piece, and the adhesive layer attached to the cut piece is irradiated with radiation to reduce the adhesive force of the adhesive layer, and the die-cut adhesive film having the reduced adhesive force is used to pick up the cut. Fragment.

尤其在被加工物為具有活性面的半導體晶圓時，上述切斷片之製造方法係有效。In particular, when the workpiece is a semiconductor wafer having an active surface, the method of manufacturing the cut sheet is effective.

若藉由上述製造方法，由於模切用黏著薄膜含有上述輻射線硬化性黏著劑組成物，故有模切步驟中，可減低切斷片的脫離飛散，同時可抑制切斷片的振動，減低碎裂。而且即使使用具有活性面的被加工物時，在拾取步驟中也可減低糊污染，同時可容易地剝離模切用黏著薄膜與切斷片。According to the above manufacturing method, since the adhesive film for die-cutting contains the radiation curable adhesive composition, the die-cutting step can reduce the detachment of the cut piece and suppress the vibration of the cut piece and reduce the chipping. . Further, even when a workpiece having an active surface is used, paste contamination can be reduced in the pick-up step, and the die-cut adhesive film and the cut sheet can be easily peeled off.

如以上，依照本發明，可提供一種模切用黏著薄膜，其在輻射線所致的硬化前具有高黏著力及高保持力，在輻射線所致的硬化後，即使對於具有活性面的被加工物，也具有低的黏著力。因此在模切步驟中，可減低切斷片的脫離飛散，同時可抑制切斷片的振動，可減低碎裂。又，於拾取步驟中，即使對於具有活性面的半導體晶圓等被加工物，也可自模切用黏著薄膜容易地剝離切斷片，同時可減低切斷片上的糊污染。As described above, according to the present invention, it is possible to provide an adhesive film for die cutting which has high adhesion and high holding force before hardening by radiation, and after hardening by radiation, even for an active surface The processed material also has low adhesion. Therefore, in the die-cutting step, the detachment of the cut piece can be reduced, and the vibration of the cut piece can be suppressed, and the chipping can be reduced. Further, in the pick-up step, even for a workpiece such as a semiconductor wafer having an active surface, the cut sheet can be easily peeled off from the die-cut adhesive film, and the paste contamination on the cut sheet can be reduced.

實施發明的形態Form of implementing the invention

如前述，於具有活性面的半導體晶圓上貼附由含有導入有輻射線反應性碳-碳雙鍵的(甲基)丙烯酸系聚合物之輻射線硬化性黏著劑組成物所成的黏著劑層時，即使照射輻射線，黏著力也不充分降低，由黏著劑層剝離半導體元件係變困難，拾取性容易降低。推測此係因為活性面中的未氧化狀態之活性原子與(甲基)丙烯酸系聚合物所具有的酯基或羥基等的極性部位接觸，於此等之間發生化學鍵結。即，於具有輻射線反應性碳-碳雙鍵的(甲基)丙烯酸系聚合物之合成時，必須將黏著成分之含烷基的(甲基)丙烯酸系單體，與至少具有用於導入能與輻射線反應性化合物或交聯劑的官能基反應之羥基之含羥基的(甲基)丙烯酸系單體的共聚合單體成分聚合，首先合成在末端或側鏈具有酯基或羥基的基礎聚合物，使具有能與導入此基礎聚合物中的羥基反應之官能基的輻射線反應性化合物與基礎聚合物反應。因此，茲認為(甲基)丙烯酸系聚合物不僅具有酯基，而且在(甲基)丙烯酸系聚合物中，由於輻射線反應性化合物的官能基及交聯劑的官能基係有未反應的羥基殘存之情況，此等極性部位係與活性原子形成化學鍵結。As described above, an adhesive made of a radiation curable adhesive composition containing a (meth)acrylic polymer having a radiation-reactive carbon-carbon double bond introduced thereto is attached to a semiconductor wafer having an active surface. In the case of the layer, even if the radiation is irradiated, the adhesive force is not sufficiently lowered, and it is difficult to peel off the semiconductor element from the adhesive layer, and the pick-up property is liable to lower. It is presumed that the active atom in the unoxidized state in the active surface is in contact with a polar portion such as an ester group or a hydroxyl group of the (meth)acrylic polymer, and chemical bonding occurs therebetween. That is, in the synthesis of a (meth)acrylic polymer having a radiation-reactive carbon-carbon double bond, it is necessary to have an alkyl group-containing (meth)acrylic monomer having an adhesive component and at least have been introduced for introduction. The copolymerizable monomer component of the hydroxyl group-containing (meth)acrylic monomer capable of reacting with the functional group of the radiation reactive compound or the crosslinking agent is first synthesized to have an ester group or a hydroxyl group at the terminal or side chain. The base polymer reacts a radiation-reactive compound having a functional group reactive with a hydroxyl group introduced into the base polymer with a base polymer. Therefore, it is considered that the (meth)acrylic polymer not only has an ester group, but also in the (meth)acrylic polymer, since the functional group of the radiation-reactive compound and the functional group of the crosslinking agent are unreacted In the case where a hydroxyl group remains, these polar sites form a chemical bond with the active atom.

本發明者等為了藉由輻射線的照射來降低具有活性面的半導體晶圓上所貼附的模切用黏著薄膜之黏著力，從儘可能抑制如此上述的極性部位與活性原子之鍵結者係有效的觀點來看，首先檢討輻射線硬化性黏著劑組成物的主成分之(甲基)丙烯酸系聚合物的特性，結果發現若構成(甲基)丙烯酸系聚合物的基礎聚合物之溶解度參數為9.6(cal/cm3 )1/2 以上、10.0(cal/cm3 )1/2 以下，則得到在輻射線所致的硬化前具有高黏著力，在輻射線所致的硬化後具有輕剝離性的輻射線硬化性黏著劑組成物。In order to reduce the adhesion of the die-bonding adhesive film attached to the semiconductor wafer having the active surface by irradiation with radiation, the inventors of the present invention suppress the bonding of the above-mentioned polar portion and the active atom as much as possible. From the viewpoint of effectiveness, the properties of the (meth)acrylic polymer which is the main component of the radiation curable adhesive composition are first reviewed, and as a result, it is found that the solubility of the base polymer constituting the (meth)acrylic polymer is found. When the parameter is 9.6 (cal/cm 3 ) 1/2 or more and 10.0 (cal/cm 3 ) 1/2 or less, it is highly adhesive before the hardening by radiation, and has a hardening effect after radiation. A lightly exfoliating radiation curable adhesive composition.

即，茲認輻射線所致的硬化後之具有活性面的半導體晶圓與黏著劑層之高黏著力，係活性原子與(甲基)丙烯酸系聚合物所具有的極性部位之鍵結而造成者，溶解度參數的降低係意味極性的減少，若使用具有低溶解度參數的基礎聚合物，則可降低所得之(甲基)丙烯酸系聚合物所具有的極性部位之數目。又，於含有烷基的(甲基)丙烯酸系單體中，由於烷基鏈愈長則溶解度參數愈降低，故可藉由長鏈的烷基來隱蔽極性部位。藉此，可減少活性原子與極性部位的鍵結。另一方面，溶解度參數若過低，則導入輻射線反應性的碳-碳雙鍵用之基礎聚合物中的羥基係減少。因此，輻射線反應性碳-碳雙鍵對(甲基)丙烯酸系聚合物的導入量變少，照射輻射線時的硬化性降低。又，於為了使(甲基)丙烯酸系聚合物交聯而使用交聯劑時，與該交聯劑反應的羥基等之極性基變少，未反應成分在黏著劑層中殘存，輻射線所致的硬化前之黏著力降低，或糊污染變容易發生。That is, it is recognized that the high adhesion of the semiconductor wafer having the active surface and the adhesive layer after hardening by the radiation is caused by the bonding of the active atoms and the polar portions of the (meth)acrylic polymer. The decrease in the solubility parameter means a decrease in polarity, and if a base polymer having a low solubility parameter is used, the number of polar portions of the obtained (meth)acrylic polymer can be reduced. Further, in the (meth)acrylic monomer having an alkyl group, the longer the alkyl chain is, the more the solubility parameter is lowered, so that the polar portion can be concealed by the long-chain alkyl group. Thereby, the bonding of the active atom to the polar portion can be reduced. On the other hand, if the solubility parameter is too low, the hydroxyl group in the base polymer for introducing a radiation-reactive carbon-carbon double bond is reduced. Therefore, the amount of introduction of the radiation-reactive carbon-carbon double bond pair (meth)acrylic polymer is small, and the hardenability at the time of irradiation with radiation is lowered. In addition, when a crosslinking agent is used for crosslinking a (meth)acrylic polymer, a polar group such as a hydroxyl group reacted with the crosslinking agent is small, and an unreacted component remains in the adhesive layer, and the radiation is The adhesion before hardening is reduced, or paste contamination is likely to occur.

於本實施形態中，基礎聚合物的溶解度參數係可由構成共聚物的基礎聚合物之各(甲基)丙烯酸系單體的溶解度參數與莫耳比之積來求得。例如，當基礎聚合物由X、Y的2種類之(甲基)丙烯酸系單體所構成時，相對於為了合成基礎聚合物所用的各(甲基)丙烯酸系單體之共聚合單體成分全量而言的含量若為x質量%、y質量%，分子量若為Mx、My，則各(甲基)丙烯酸系單體的莫耳比Cx、Cy係以x/Mx、y/My表示，基礎聚合物的莫耳比C係以x/Mx+y/My表示。因此，各(甲基)丙烯酸系單體的溶解度參數若為SPx(cal/cm3 )1/2 、SPy(cal/cm3 )1/2 ，則基礎聚合物的溶解度參數SP(cal/cm3 )1/2 係可經由下式(1)求得。In the present embodiment, the solubility parameter of the base polymer can be determined from the product of the solubility parameter of each (meth)acrylic monomer constituting the base polymer of the copolymer and the molar ratio. For example, when the base polymer is composed of two kinds of (meth)acrylic monomers of X and Y, the copolymerized monomer component of each (meth)acrylic monomer used for synthesizing the base polymer is used. When the content of the total amount is x% by mass or y mass%, and the molecular weight is Mx or My, the molar ratios Cx and Cy of each (meth)acrylic monomer are represented by x/Mx and y/My. The molar ratio C of the base polymer is represented by x/Mx+y/My. Therefore, if the solubility parameter of each (meth)acrylic monomer is SPx(cal/cm 3 ) 1/2 and SPy(cal/cm 3 ) 1/2 , the solubility parameter of the base polymer SP (cal/cm) 3 ) The 1/2 system can be obtained by the following formula (1).

SP=[(X×SPx/Mx)+(y×SPy/My)]×(1/C)　(1)SP=[(X×SPx/Mx)+(y×SPy/My)]×(1/C) (1)

再者，已知各(甲基)丙烯酸系單體的溶解度參數係由分子構造計算而求得，本說明書中的(甲基)丙烯酸系單體之溶解度參數係意味經由Fedors的方法(原崎勇次著，「塗料的基礎科學」，第3章，35頁，1977年，槙書店發行)所得之在25℃的值。Further, it is known that the solubility parameter of each (meth)acrylic monomer is determined by molecular structure calculation, and the solubility parameter of the (meth)acrylic monomer in the present specification means a method via Fedors (original time) The value of the "Basic Science of Coatings", Chapter 3, page 35, 1977, issued by the bookstore, at 25 °C.

其次，為了提高模切用黏著薄膜的輕剝離性，必須提高輻射線硬化性黏著劑組成物全體的硬化性。此時，若僅要求輻射線所致的硬化後之黏著力的降低，則除了如摻合型之導入有輻射線反應性碳-碳雙鍵的(甲基)丙烯酸系聚合物以外，亦考慮使用多官能單體或多官能寡聚物等之低分子量多官能聚合性化合物。然而，即使使用此等低分子量多官能聚合性化合物，當使用具有活性面的被加工物時，拾取性也不會提高，另一方面，由於使用低分子量多官能聚合性化合物而輻射線所致的硬化前之黏著力及保持力會降低。為了使輻射線所致的硬化前之高黏著力與輻射線所致的硬化後之低黏著力並存，亦考慮增加在(甲基)丙烯酸系聚合物本身中導入的輻射線反應性碳-碳雙鍵，但於本實施形態的(甲基)丙烯酸系聚合物中，輻射線反應性碳-碳雙鍵係藉由使經由含羥基的(甲基)丙烯酸系單體導入基礎聚合物中的羥基，與輻射線反應性化合物的官能基反應，而導入至(甲基)丙烯酸系聚合物中。因此，當導入基礎聚合物中的羥基之大部分係使用於輻射線反應性碳-碳雙鍵的導入時，使(甲基)丙烯酸系聚合物與一定量的交聯劑進行交聯反應用的羥基係變少，保持力會降低，或污染性劣化。另一方面，輻射線反應性碳-碳雙鍵的導入量若過少，則即使藉由輻射線的照射，(甲基)丙烯酸系聚合物也不充分硬化，無法充分減低輻射線所致的硬化後之黏著力。再者，即使增加導入基礎聚合物中的羥基量，當少量使用輻射線反應性化合物或交聯劑時，大量的羥基也殘存在(甲基)丙烯酸系聚合物中。結果，即使使用上述具有低溶解度參數的(甲基)丙烯酸系聚合物，殘存羥基與活性原子也鍵結，輻射線所致的硬化後之黏著力不會充分降低，或由於不充分地形成三次元交聯構造，輻射線所致的硬化前之保持力降低。Next, in order to improve the light peeling property of the adhesive film for die-cutting, it is necessary to improve the hardenability of the entire radiation curable adhesive composition. In this case, if only the decrease in the adhesive force after hardening due to the radiation is required, it is considered in addition to the (meth)acrylic polymer into which the radiation-reactive carbon-carbon double bond is introduced, such as a blend type. A low molecular weight polyfunctional polymerizable compound such as a polyfunctional monomer or a polyfunctional oligomer is used. However, even when such a low molecular weight polyfunctional polymerizable compound is used, the pick-up property is not improved when a workpiece having an active surface is used, and on the other hand, radiation is caused by the use of a low molecular weight polyfunctional polymerizable compound. The adhesion and retention before hardening will decrease. In order to coexist the high adhesion force before hardening due to radiation and the low adhesion after hardening due to radiation, it is also considered to increase the radiation-reactive carbon-carbon introduced in the (meth)acrylic polymer itself. a double bond, but in the (meth)acrylic polymer of the present embodiment, the radiation-reactive carbon-carbon double bond is introduced into the base polymer via a hydroxyl group-containing (meth)acrylic monomer. The hydroxyl group is reacted with a functional group of the radiation-reactive compound to be introduced into the (meth)acrylic polymer. Therefore, when most of the hydroxyl groups introduced into the base polymer are used for the introduction of the radiation-reactive carbon-carbon double bond, the (meth)acrylic polymer is crosslinked with a certain amount of the crosslinking agent. The hydroxy group is reduced, the holding power is lowered, or the pollution is deteriorated. On the other hand, if the amount of introduction of the radiation-reactive carbon-carbon double bond is too small, the (meth)acrylic polymer is not sufficiently cured even by irradiation with radiation, and the hardening due to radiation cannot be sufficiently reduced. After the adhesion. Further, even if the amount of the hydroxyl group introduced into the base polymer is increased, when a radiation-reactive compound or a crosslinking agent is used in a small amount, a large amount of hydroxyl groups remain in the (meth)acrylic polymer. As a result, even if the above (meth)acrylic polymer having a low solubility parameter is used, the residual hydroxyl group is bonded to the active atom, the adhesion after hardening due to radiation is not sufficiently lowered, or is insufficiently formed three times. The meta-crosslinking structure reduces the retention force before hardening due to radiation.

因此，為了謀求輻射線所致的硬化前之高黏著力及高保持力，以及輻射線所致的硬化後之低黏著力及低污染性之並存，必須考慮經由含羥基的(甲基)丙烯酸系單體導入基礎聚合物中的羥基量，經由與該羥基的反應而導入(甲基)丙烯酸系聚合物中的輻射線反應性碳-碳雙鍵量，與該羥基交聯反應的交聯劑之含量，及交聯反應後殘存的羥基量。Therefore, in order to achieve high adhesion and high retention force before hardening due to radiation, and low adhesion and low pollution after hardening due to radiation, it is necessary to consider the passage of hydroxyl-containing (meth)acrylic acid. The amount of the hydroxyl group introduced into the base polymer, and the amount of the radiation-reactive carbon-carbon double bond introduced into the (meth)acrylic polymer via the reaction with the hydroxyl group, and crosslinking with the hydroxyl group crosslinking reaction The content of the agent and the amount of hydroxyl groups remaining after the crosslinking reaction.

從如此的觀點來看，檢討輻射線硬化性黏著劑組成物全體之構成，結果為了提高輻射線所致的硬化前之保持力，若藉由使用一定量的在分子內具有能與經由含羥基的(甲基)丙烯酸系單體導入基礎聚合物中的羥基交聯反應之第2官能基的交聯劑，更且使經由含羥基的(甲基)丙烯酸系單體導入基礎聚合物中的羥基之莫耳量成為輻射線反應性化合物的第1官能基及交聯劑的第2官能基之合計莫耳量以上，則可使導入基礎聚合物中的羥基與輻射線反應性化合物的第1官能基反應，同時由於即使使基礎聚合物與輻射線反應性化合物反應而導入輻射線反應碳-碳雙鍵後，與交聯劑可交聯反應的羥基也殘留在(甲基)丙烯酸系聚合物中，故可使該羥基與交聯劑的第2官能基反應。結果，輻射線硬化性黏著劑組成物中的游離低分子量成分變少，於輻射線所致的硬化前對半導體晶圓或金屬製構件具有高黏著力，同時具有高保持力，即使在輻射線所致的硬化後，也可得到具有低污染性的輻射線硬化性黏著劑組成物。From such a viewpoint, the composition of the entire composition of the radiation curable adhesive is reviewed, and as a result, in order to increase the retention force before hardening due to radiation, if a certain amount of energy is contained in the molecule, The (meth)acrylic monomer is introduced into the second functional group crosslinking agent of the hydroxyl group crosslinking reaction in the base polymer, and further introduced into the base polymer via the hydroxyl group-containing (meth)acrylic monomer. When the molar amount of the hydroxyl group is equal to or greater than the total amount of the first functional group of the radiation-reactive compound and the second functional group of the crosslinking agent, the hydroxyl group and the radiation-reactive compound introduced into the base polymer can be introduced. The 1-functional group reacts, and at the same time, the hydroxyl group which crosslinks with the crosslinking agent remains in the (meth)acrylic acid system even after the radiation reaction carbon-carbon double bond is introduced by reacting the base polymer with the radiation-reactive compound. In the polymer, the hydroxyl group can be reacted with the second functional group of the crosslinking agent. As a result, the free low molecular weight component in the radiation curable adhesive composition is reduced, and has high adhesion to the semiconductor wafer or the metal member before curing due to radiation, and has high holding power even in the radiation. After the resulting hardening, a radiation curable adhesive composition having low contamination can also be obtained.

另一方面，相對於輻射線反應性化合物的第1官能基及交聯劑的第2官能基之合計莫耳量，若羥基的莫耳量過度地多，則交聯反應後的殘存羥基濃度變高，由於殘存羥基與活性原子的鍵結，即使在輻射線所致的硬化後，黏著力也不充分降低，輕剝離性變差。然而，若每1g輻射線硬化性黏著劑組成物中的交聯反應後之殘存羥基濃度為0.08mmol以下，則即使經由含羥基的(甲基)丙烯酸系單體導入基礎聚合物中的羥基之莫耳量為輻射線反應性化合物的第1官能基及交聯劑的第2官能基之合計莫耳量以上，輻射線硬化性黏著劑組成物全體中的殘存羥基也少，所以即使對於具有活性面的被加工物，也可充分減低輻射線所致的硬化後之黏著力。因此，殘存羥基濃度較佳為儘可能地低，較佳為0mmol。再者，由交聯反應後的輻射線硬化性黏著劑組成物來確認殘存羥基濃度時，可藉由測定輻射線硬化性黏著劑組成物的羥值，而算出殘存羥基濃度。On the other hand, when the molar amount of the first functional group of the radiation-reactive compound and the second functional group of the crosslinking agent is excessive, if the amount of hydroxyl groups is excessively large, the residual hydroxyl group concentration after the crosslinking reaction When the residual hydroxyl group is bonded to the active atom, the adhesion is not sufficiently lowered even after hardening by radiation, and the light peeling property is deteriorated. However, if the residual hydroxyl group concentration after the crosslinking reaction per 1 g of the radiation curable adhesive composition is 0.08 mmol or less, the hydroxyl group in the base polymer is introduced through the hydroxyl group-containing (meth)acrylic monomer. The molar amount is not less than the total amount of the first functional group of the radiation-reactive compound and the second functional group of the crosslinking agent, and the residual hydroxyl group in the entire radiation-curable adhesive composition is small, so even if it has The processed object on the active surface can also sufficiently reduce the adhesion after hardening due to radiation. Therefore, the residual hydroxyl group concentration is preferably as low as possible, preferably 0 mmol. In addition, when the residual hydroxyl group concentration is confirmed from the radiation curable adhesive composition after the crosslinking reaction, the residual hydroxyl group concentration can be calculated by measuring the hydroxyl value of the radiation curable adhesive composition.

再者，經由輻射線反應性化合物導入(甲基)丙烯酸系聚合物中的輻射線反應性碳-碳雙鍵濃度，若每1g輻射線硬化性黏著劑組成物中為0.42mmol以上、0.84mmol以下，較佳為0.42mmol以上、0.69mmol以下，則可不使用使輻射線所致的硬化前之黏著力及保持力降低的多官能單體或多官能寡聚物等之低分子量多官能聚合性化合物，而可充分減低輻射線所致的硬化後之黏著力。每1g輻射線硬化性黏著劑組成物中的輻射線反應性碳-碳雙鍵濃度若未達0.42mmol，則輻射線硬化性黏著劑組成物中的輻射線反應性碳-碳雙鍵少，輻射線所致的硬化後之黏著力不充分降低。另一方面，每1g輻射線硬化性黏著劑組成物中的輻射線反應性碳-碳雙鍵濃度若比0.84mmol還多，則無法確保使交聯劑與(甲基)丙烯酸系聚合物交聯反應用的羥基，保持力降低下或污染性劣化。再者，於確認輻射線硬化性黏著劑組成物中的輻射線反應性碳-碳雙鍵濃度時，藉由測定輻射線硬化性黏著劑組成物之碘價，可算出輻射線反應性碳-碳雙鍵濃度。In addition, the concentration of the radiation-reactive carbon-carbon double bond in the (meth)acrylic polymer introduced into the (meth)acrylic polymer via the radiation-reactive compound is 0.42 mmol or more and 0.84 mmol per 1 g of the radiation curable adhesive composition. In the following, it is preferably 0.42 mmol or more and 0.69 mmol or less, and low molecular weight polyfunctional polymerizable property such as a polyfunctional monomer or a polyfunctional oligomer which does not cause adhesion and curing force before curing due to radiation can be used. The compound can sufficiently reduce the adhesion after hardening caused by radiation. If the concentration of the radiation-reactive carbon-carbon double bond in the composition of the radiation curable adhesive of 1 g is less than 0.42 mmol, the radiation-reactive carbon-carbon double bond in the radiation curable adhesive composition is small. The adhesion after hardening due to radiation is not sufficiently reduced. On the other hand, if the concentration of the radiation-reactive carbon-carbon double bond per gram of the radiation curable adhesive composition is more than 0.84 mmol, it is impossible to ensure that the crosslinking agent is bonded to the (meth)acrylic polymer. The hydroxyl group for the coupling reaction has a reduced holding power or a deteriorated contamination. Further, when the concentration of the radiation-reactive carbon-carbon double bond in the radiation curable adhesive composition is confirmed, the radiation-reactive carbon can be calculated by measuring the iodine value of the radiation curable adhesive composition - Carbon double bond concentration.

其次，具體說明構成本實施形態的輻射線硬化性黏著劑組成物之各成分，及使用其的模切用黏著薄膜與切斷片之製造方法。Next, the components constituting the radiation curable adhesive composition of the present embodiment, and the adhesive film for die cutting and the method for producing the cut sheet using the same will be specifically described.

本實施形態中，基礎聚合物係至少含有不具羥基等極性基之含烷基的(甲基)丙烯酸系單體與含羥基的(甲基)丙烯酸系單體當作共聚合單體成分。作為含烷基的(甲基)丙烯酸系單體，使用具有碳數2以上、較佳8以上之直鏈或支鏈烷基之含烷基的(甲基)丙烯酸系單體。特別地，若基礎聚合物僅含有具碳數8以上的直鏈或支鏈烷基之含烷基的(甲基)丙烯酸系單體與含羥基的(甲基)丙烯酸系單體當作共聚合單體成分，則(甲基)丙烯酸系聚合物的極性部位係被長鏈的烷基所隱蔽，因此可抑制酯基與活性原子的接觸。In the present embodiment, the base polymer contains at least an alkyl group-containing (meth)acrylic monomer having no polar group such as a hydroxyl group and a hydroxyl group-containing (meth)acrylic monomer as a copolymerization monomer component. As the alkyl group-containing (meth)acrylic monomer, an alkyl group-containing (meth)acrylic monomer having a linear or branched alkyl group having 2 or more carbon atoms, preferably 8 or more is used. In particular, if the base polymer contains only a linear or branched alkyl group having a carbon number of 8 or more, the alkyl group-containing (meth)acrylic monomer is co-linked with a hydroxyl group-containing (meth)acrylic monomer. When the monomer component is polymerized, the polar portion of the (meth)acrylic polymer is concealed by the long-chain alkyl group, so that the contact between the ester group and the active atom can be suppressed.

作為含烷基的(甲基)丙烯酸系單體，具體地例如可舉出(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一酯、(甲基)丙烯酸十二酯、(甲基)丙烯酸十三酯、(甲基)丙烯酸十四酯、(甲基)丙烯酸十五酯、(甲基)丙烯酸十六酯、(甲基)丙烯酸十七酯、(甲基)丙烯酸十八酯等的(甲基)丙烯酸酯。此等可為單獨或或複數使用。再者，含烷基的(甲基)丙烯酸系單體之烷基數係愈長鏈則極性部位愈被隱蔽而較佳，但若考慮市場的取得可能性，烷基數較佳為18以下，更佳為12以下。於此等之中，較佳為由含有碳數8的直鏈或支鏈烷基之(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯及(甲基)丙烯酸2-乙基己酯所成之群中選出的1種，更佳為(甲基)丙烯酸2-乙基己酯。Specific examples of the alkyl group-containing (meth)acrylic monomer include ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, (A) Heptyl acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, isophthalic acid (meth) acrylate Ester, decyl (meth) acrylate, isodecyl (meth) acrylate, eleven (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, (methyl) A (meth) acrylate such as tetradecyl acrylate, penta(meth) acrylate, hexadecyl (meth) acrylate, heptadecylate (meth) acrylate or octadecyl (meth) acrylate. These may be used singly or in plural. Further, the longer the number of alkyl groups of the alkyl group-containing (meth)acrylic monomer, the more the polar portion is concealed, and the number of alkyl groups is preferably 18 or less, and more preferably 18 or less. Good for 12 or less. Among them, preferred are octyl (meth)acrylate, isooctyl (meth)acrylate and 2-ethylhexyl (meth)acrylate containing a linear or branched alkyl group having 8 carbon atoms. One selected from the group consisting of esters is more preferably 2-ethylhexyl (meth)acrylate.

作為含羥基的(甲基)丙烯酸系單體，具體地例如可舉出(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯等。此等可為單獨或或複數使用。Specific examples of the hydroxyl group-containing (meth)acrylic monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Ester, 6-hydroxyhexyl (meth)acrylate, and the like. These may be used singly or in plural.

對於構成基礎聚合物的共聚合單體成分全量，含有烷基的(甲基)丙烯酸系單體之含量較佳為87.5～93.5質量%，含羥基的(甲基)丙烯酸系單體之含量較佳為6.5～12.5質量%。特別地，更佳為對於共聚合單體成分全量，含有80.0～93.5質量%的具有碳數8以上的直鏈或支鏈烷基之含烷基的(甲基)丙烯酸系單體之基礎聚合物。若含烷基的(甲基)丙烯酸系單體之含量過少，而含羥基的(甲基)丙烯酸系單體的含量過多，則基礎聚合物的溶解度參數變過高，殘存羥基濃度變高，即使藉由輻射線所致的硬化，也無法充分減低黏著力，結果輕剝離性變差。另一方面，若含烷基的(甲基)丙烯酸系單體之含量過多，而含羥基的(甲基)丙烯酸系單體之含量過少，則導入基礎聚合物中的羥基量變少，結果用於與輻射線反應性化合物反應而將輻射線反應性碳-碳雙鍵導入(甲基)丙烯酸系聚合物中所必要的羥基係減少，硬化性降低。又，為了提高硬化性，若增加輻射線反應性碳-碳雙鍵的導入量，則與交聯劑反應的羥基變少，保持力降低。The content of the alkyl group-containing (meth)acrylic monomer is preferably from 87.5 to 99.5% by mass, and the content of the hydroxyl group-containing (meth)acrylic monomer is more than the total amount of the copolymerized monomer component constituting the base polymer. Preferably, it is 6.5 to 12.5 mass%. In particular, it is more preferred to carry out a base polymerization of an alkyl group-containing (meth)acrylic monomer having a linear or branched alkyl group having 8 or more carbon atoms and containing 80.0 to 99.5% by mass of the total amount of the monomer component. Things. When the content of the alkyl group-containing (meth)acrylic monomer is too small and the content of the hydroxyl group-containing (meth)acrylic monomer is too large, the solubility parameter of the base polymer becomes too high, and the residual hydroxyl group concentration becomes high. Even if the hardening by the radiation is performed, the adhesive force cannot be sufficiently reduced, and as a result, the light peelability is deteriorated. On the other hand, when the content of the alkyl group-containing (meth)acrylic monomer is too large and the content of the hydroxyl group-containing (meth)acrylic monomer is too small, the amount of the hydroxyl group introduced into the base polymer is small, and as a result, The hydroxy group necessary for introducing a radiation-reactive carbon-carbon double bond into the (meth)acrylic polymer by reacting with the radiation-reactive compound reduces the hardenability. Further, in order to increase the curability, when the introduction amount of the radiation-reactive carbon-carbon double bond is increased, the hydroxyl group which reacts with the crosslinking agent decreases, and the holding power decreases.

以內聚力及耐熱性等為目的，基礎聚合物視需要亦可含有其它共聚合單體成分。作為如此其它的共聚合單體成分，具體地例如可舉出(甲基)丙烯酸環氧丙酯等之含環氧基的單體；(甲基)丙烯酸、伊康酸、馬來酸、富馬酸、巴豆酸、異巴豆酸等之含羧基的單體；馬來酸酐、伊康酸酐等之含酸酐基的單體(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥甲基丙烷(甲基)丙烯醯胺、N-甲氧基甲基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺等之醯胺系單體；(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸第三丁基胺基乙酯等之含胺基的單體；(甲基)丙烯腈等之含氰基的單體；乙烯、丙烯、異戊二烯、丁二烯、異丁烯等的烯烴系單體；苯乙烯、α-甲基苯乙烯、乙烯基甲苯等之苯乙烯系單體；醋酸乙烯酯、丙酸乙烯酯等之乙烯基酯系單體；甲基乙烯基醚、乙基乙烯基醚等之乙烯基醚系單體；氯乙烯、偏二氯乙烯等之含鹵素原子的單體；(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等之含烷氧基的單體；N-乙烯基-2-吡咯啶酮、N-甲基乙烯基吡咯啶酮、N-乙烯基吡啶、N-乙烯基哌啶酮、N-乙烯基嘧啶、N-乙烯基哌、N-乙烯基吡、N-乙烯基吡咯、N-乙烯基咪唑、N-乙烯基唑、N-乙烯基嗎啉、N-乙烯基己內醯胺、N-(甲基)丙烯醯基嗎啉等之具有含氮原子的環之單體。又，於共聚合單體成分中，以交聯等為目的，視需要亦可使用多官能性單體。再者，作為共聚合單體成分，視需要亦可使用乙烯-醋酸乙烯酯共聚物或醋酸乙烯酯聚合物等。此等其它共聚合單體成分係可為單獨或複數使用。惟，為了得到具有上述溶解度參數的基礎聚合物，含羥基的(甲基)丙烯酸系單體以外之具有極性基的含極性基之(甲基)丙烯酸系單體的含量較佳為儘可能地少。For the purpose of cohesion and heat resistance, the base polymer may contain other copolymerized monomer components as needed. Specific examples of the other copolymerizable monomer component include an epoxy group-containing monomer such as glycidyl (meth)acrylate; (meth)acrylic acid, itaconic acid, maleic acid, and rich. a carboxyl group-containing monomer such as horse acid, crotonic acid or isocrotonic acid; an acid anhydride group-containing monomer (meth) acrylamide, maleic anhydride, oriconic anhydride, etc., N,N-dimethyl (methyl) ) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxy A guanamine monomer such as a (meth) acrylamide or an N-butoxymethyl (meth) acrylamide; an aminoethyl (meth) acrylate or a N, N-(meth) acrylate An amine group-containing monomer such as dimethylaminoethyl ester or (t-butylaminoethyl (meth)acrylate; a cyano group-containing monomer such as (meth)acrylonitrile; ethylene, propylene, and the like An olefin monomer such as pentadiene, butadiene or isobutylene; a styrene monomer such as styrene, α-methylstyrene or vinyltoluene; or a vinyl ester such as vinyl acetate or vinyl propionate. Monomer; methyl vinyl ether, ethyl vinyl ether a vinyl ether-based monomer; a halogen atom-containing monomer such as vinyl chloride or vinylidene chloride; an alkoxy group such as methoxyethyl (meth)acrylate or ethoxyethyl (meth)acrylate Monomers; N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinyl Piper N-vinylpyrene , N-vinylpyrrole, N-vinylimidazole, N-vinyl A monomer having a ring containing a nitrogen atom such as azole, N-vinylmorpholine, N-vinylcaprolactam, N-(methyl)propenylmorpholine or the like. Further, in the copolymerization monomer component, a polyfunctional monomer may be used as needed for crosslinking or the like. Further, as the copolymerization monomer component, an ethylene-vinyl acetate copolymer or a vinyl acetate polymer or the like may be used as needed. These other copolymerized monomer components may be used singly or in plural. However, in order to obtain the base polymer having the above solubility parameter, the content of the polar group-containing (meth)acrylic monomer having a polar group other than the hydroxyl group-containing (meth)acrylic monomer is preferably as much as possible. less.

作為合成基礎聚合物用的聚合方法，可舉出習知的溶液聚合法、乳化聚合法、塊狀聚合法、懸浮聚合法等，於此等之中，較佳為共聚合單體成分的聚合均勻進行之溶液聚合法。作為進行溶液聚合時的有機溶劑，具體地例如可舉出酮系、酯系、醇系、芳香族系的有機溶劑。此等有機溶劑可為單獨或複數使用。於此等之中，較佳為甲苯、醋酸乙酯、異丙醇、苯甲基溶纖劑、乙基溶纖劑、丙酮、甲基乙基酮等之一般對基礎聚合物為良溶劑者，較佳為具有60～120℃的沸點之有機溶劑。又，作為聚合引發劑，可舉出α,α’-偶氮雙異丁腈等的偶氮雙系，苯甲醯過氧化物等的有機過氧化物系等之自由基發生劑。於聚合時，視需要亦可使用觸媒、聚合抑制劑等。Examples of the polymerization method for the synthetic base polymer include a conventional solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, and the like. Among them, polymerization of a copolymerized monomer component is preferred. A homogeneous solution polymerization method. Specific examples of the organic solvent to be used in the solution polymerization include a ketone system, an ester system, an alcohol system, and an aromatic organic solvent. These organic solvents may be used singly or in plural. Among these, it is preferred that the base polymer is a good solvent for toluene, ethyl acetate, isopropanol, benzyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone or the like. It is preferably an organic solvent having a boiling point of 60 to 120 °C. In addition, examples of the polymerization initiator include an azobis system such as α,α'-azobisisobutyronitrile, and a radical generator such as an organic peroxide system such as benzamidine peroxide. At the time of polymerization, a catalyst, a polymerization inhibitor, or the like may be used as needed.

本實施形態的(甲基)丙烯酸系聚合物，係可藉由使如上述所得之基礎聚合物，與在分子內具有能經由羥基(甲基)丙烯酸系單體導入基礎聚合物中的羥基反應之第1官能基及輻射線反應性碳-碳雙鍵的輻射線反應性化合物進行反應，在側鏈及/或末端導入輻射線反應性碳-碳雙鍵而合成。The (meth)acrylic polymer of the present embodiment can be reacted with a hydroxyl group which can be introduced into a base polymer via a hydroxyl group (meth)acrylic monomer by a base polymer obtained as described above. The radiation-reactive compound of the first functional group and the radiation-reactive carbon-carbon double bond is reacted, and a radiation-reactive carbon-carbon double bond is introduced into the side chain and/or the terminal to synthesize it.

作為輻射線反應性化合物，具體地例如可舉出(甲基)丙烯酸、桂皮酸、伊康酸、富馬酸、苯二甲酸等之含羧基的單體，(甲基)丙烯酸異氰酸酯乙酯等之含異氰酸酯基的單體，(甲基)丙烯酸環氧丙酯等之含環氧基的單體，(甲基)丙烯酸胺基乙酯等之含胺基的單體等。此等輻射線反應性化合物係可為單獨或複數使用。於此等之中，較佳為具有與羥基的反應性優異之異氰酸酯基當作第1官能基之含異氰酸酯基的單體。Specific examples of the radiation-reactive compound include a carboxyl group-containing monomer such as (meth)acrylic acid, cinnamic acid, itaconic acid, fumaric acid, or phthalic acid, and (meth)acrylic acid isocyanate ethyl ester. Examples of the isocyanate group-containing monomer, the epoxy group-containing monomer such as glycidyl (meth)acrylate, and the amine group-containing monomer such as aminoethyl (meth)acrylate. These radiation reactive compounds may be used singly or in combination. Among these, an isocyanate group-containing monomer having an isocyanate group having excellent reactivity with a hydroxyl group as a first functional group is preferred.

輻射線反應性化合物，由於係以經由前述含羥基的(甲基)丙烯酸系單體導入基礎聚合物中的羥基之莫耳量成為輻射線反應性化合物的第1官能基及交聯劑的第2官能基之合計莫耳量以上，輻射線硬化性黏著劑組成物中的交聯反應後之殘存羥基濃度，及輻射線反應性碳-碳雙鍵濃度成為指定範圍之含量而使用，故必須考慮構成基礎聚合物之含羥基的(甲基)丙烯酸系單體及交聯劑之含量，但較佳的輻射線反應性化合物之含量的範圍，係相對於基礎聚合物100質量份而言為7～15質量份，更佳為7～12質量份。輻射線反應性化合物的含量若過少，則輻射線反應性碳-碳雙鍵濃度減少，硬化性降低。輻射線反應性化合物的含量若過多，則硬化性飽和，另一方面，與交聯劑反應的羥基變少，輻射線所致的硬化前之保持力降低。又，未反應的低分子量成分增加，輻射線所致的硬化前之黏著力降低，或輻射線所致的硬化後之污染性劣化。再者，延伸後，變容易發生黏著劑層自基材剝離的界面剝離，切斷片的拾取會變困難。The radiation-reactive compound is a first functional group and a crosslinking agent of the radiation-reactive compound, because the molar amount of the hydroxyl group introduced into the base polymer through the hydroxyl group-containing (meth)acrylic monomer is The total amount of the two functional groups is more than the molar amount, and the residual hydroxyl group concentration after the crosslinking reaction in the radiation curable adhesive composition and the concentration of the radiation-reactive carbon-carbon double bond are used in the specified range, so it is necessary to use The content of the hydroxyl group-containing (meth)acrylic monomer and the crosslinking agent constituting the base polymer is considered, but the range of the content of the radiation-reactive compound is preferably 100 parts by mass relative to the base polymer. 7 to 15 parts by mass, more preferably 7 to 12 parts by mass. When the content of the radiation-reactive compound is too small, the concentration of the radiation-reactive carbon-carbon double bond decreases, and the hardenability decreases. When the content of the radiation-reactive compound is too large, the curability is saturated, and on the other hand, the hydroxyl group which reacts with the crosslinking agent decreases, and the holding power before curing due to radiation is lowered. Further, the unreacted low molecular weight component is increased, the adhesion before curing due to radiation is lowered, or the contamination due to radiation is deteriorated after hardening. Further, after the stretching, the interface of the adhesive layer peeling off from the substrate is likely to be peeled off, and the picking up of the cut piece becomes difficult.

作為合成(甲基)丙烯酸系聚合物的方法，可舉出在維持碳-碳雙鍵的輻射線反應性之狀態下，使基礎聚合物與輻射線反應性化合物進行縮合反應或加成反應之方法。於此等反應中，較佳為以維持碳-碳雙鍵的輻射線反應性之方式，使用聚合抑制劑。作為如此的聚合抑制劑，較佳為氫醌‧單甲基醚等的醌系聚合抑制劑。聚合抑制劑之量係沒有特別的限制，相對於基礎聚合物與輻射線反應性化合物之合計量而言，通常為0.01～0.1質量份。As a method of synthesizing a (meth)acrylic polymer, a condensation reaction or an addition reaction of a base polymer and a radiation-reactive compound can be carried out while maintaining the radiation reactivity of a carbon-carbon double bond. method. In such reactions, it is preferred to use a polymerization inhibitor in such a manner as to maintain the radiation reactivity of the carbon-carbon double bond. As such a polymerization inhibitor, a quinone polymerization inhibitor such as hydroquinone or monomethyl ether is preferred. The amount of the polymerization inhibitor is not particularly limited, and is usually 0.01 to 0.1 parts by mass based on the total amount of the base polymer and the radiation-reactive compound.

如上述所得之(甲基)丙烯酸系聚合物的重量平均分子量較佳為30萬～200萬，更佳為40萬～150萬。重量平均分子量若未達30萬，則在切斷片容易發生糊污染。另一方面，重量平均分子量若大於200萬，則在合成時及塗佈時輻射線硬化性黏著劑組成物會膠化。再者，於本說明書中，重量平均分子量係意味藉由GPC(凝膠滲透層析術)所測定之聚苯乙烯換算重量平均分子量(溶劑：四氫呋喃)。The weight average molecular weight of the (meth)acrylic polymer obtained as described above is preferably from 300,000 to 2,000,000, more preferably from 400,000 to 1,500,000. If the weight average molecular weight is less than 300,000, paste contamination is likely to occur in the cut piece. On the other hand, if the weight average molecular weight is more than 2,000,000, the radiation curable adhesive composition will gel at the time of synthesis and coating. Further, in the present specification, the weight average molecular weight means a polystyrene-equivalent weight average molecular weight (solvent: tetrahydrofuran) measured by GPC (gel permeation chromatography).

本實施形態的輻射線硬化性黏著劑組成物，係含有如上述所得之(甲基)丙烯酸系聚合物，連同在分子內具有能與經由羥基(甲基)丙烯酸系單體導入基礎聚合物中的羥基進行交聯反應的第2官能基之交聯劑。藉由使用如此的交聯劑，可形成三次元交聯構造，可提高輻射線硬化性黏著劑組成物的內聚力，可得到高保持力的輻射線硬化性黏著劑組成物。The radiation curable adhesive composition of the present embodiment contains the (meth)acrylic polymer obtained as described above, together with the ability to introduce into the base polymer via a hydroxyl (meth)acrylic monomer in the molecule. The hydroxyl group is a crosslinking agent of the second functional group which undergoes a crosslinking reaction. By using such a crosslinking agent, a three-dimensional crosslinked structure can be formed, the cohesive force of the radiation curable adhesive composition can be improved, and a radiation curable adhesive composition having high holding power can be obtained.

作為交聯劑，具體地例如可舉出聚異氰酸酯系交聯劑、環氧系交聯劑、氮雜環丙烷系交聯劑、蜜胺樹脂系交聯劑、尿素樹脂系交聯劑、酸酐化合物系交聯劑、聚胺系交聯劑、含羧基的聚合物系交聯劑等。此等交聯劑係可為單獨或或複數使用。於此等之中，較佳為具有以與羥基的反應性優異之異氰酸酯基當作第2官能基的聚異氰酸酯系交聯劑。Specific examples of the crosslinking agent include a polyisocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a melamine resin crosslinking agent, a urea resin crosslinking agent, and an acid anhydride. The compound is a crosslinking agent, a polyamine crosslinking agent, a carboxyl group-containing polymer crosslinking agent, and the like. These crosslinking agents may be used singly or in combination. Among these, a polyisocyanate-based crosslinking agent having an isocyanate group having excellent reactivity with a hydroxyl group as a second functional group is preferable.

相對於(甲基)丙烯酸系聚合物100質量份而言，交聯劑的含量為0.3～2.7質量份，較佳為0.3～1.3質量份，而且與輻射線反應性化合物同樣地，以使經由羥基(甲基)丙烯酸系單體導入基礎聚合物中的羥基之莫耳量成為輻射線反應性化合物的第1官能基及交聯劑的第2官能基之合計莫耳量以上，輻射線硬化性黏著劑組成物中的交聯反應後之殘存羥基濃度，及輻射線反應性碳-碳雙鍵濃度成為指定範圍之配合量使用。交聯劑的含量若過少，則輻射線所致的硬化前之保持力降低。另一方面，交聯劑的含量若過多，則於使用具有一定量的輻射線反應性碳-碳雙鍵之(甲基)丙烯酸系聚合物的本實施形態之輻射線硬化性黏著劑組成物中，與羥基未反應的游離交聯劑係變多，輻射線所致的硬化前之黏著力降低，或輻射線所致的硬化後之污染性劣化。The content of the crosslinking agent is from 0.3 to 2.7 parts by mass, preferably from 0.3 to 1.3 parts by mass, based on 100 parts by mass of the (meth)acrylic polymer, and similarly to the radiation-reactive compound, The molar amount of the hydroxyl group introduced into the base polymer of the hydroxy(meth)acrylic monomer is equal to or greater than the total amount of the first functional group of the radiation-reactive compound and the second functional group of the crosslinking agent, and radiation hardening The residual hydroxyl group concentration after the crosslinking reaction in the adhesive composition and the concentration of the radiation-reactive carbon-carbon double bond are used in the specified range. If the content of the crosslinking agent is too small, the holding power before curing due to radiation is lowered. On the other hand, if the content of the crosslinking agent is too large, the radiation curable adhesive composition of the present embodiment using a (meth)acrylic polymer having a certain amount of radiation-reactive carbon-carbon double bonds is used. Among them, the amount of the free crosslinking agent which is not reacted with the hydroxyl group increases, the adhesion before the hardening due to the radiation is lowered, or the contamination due to the radiation is deteriorated after the hardening.

使(甲基)丙烯酸系聚合物與交聯劑進行交聯反應用的處理，係可在常溫下進行，為了促進交聯反應，也可在加溫下進行。於加溫時，溫度較佳為30～100℃。又，為了防止水分所致的交聯劑之惰性化，交聯處理較佳為在50%RH以下的低濕環境下進行。The treatment for crosslinking the (meth)acrylic polymer and the crosslinking agent can be carried out at normal temperature, and can be carried out under heating in order to promote the crosslinking reaction. When heating, the temperature is preferably from 30 to 100 °C. Further, in order to prevent inertization of the crosslinking agent by moisture, the crosslinking treatment is preferably carried out in a low-humidity environment of 50% RH or less.

本實施形態的輻射線硬化性黏著劑組成物，當使用紫外線作為輻射線時，亦可更含有光聚合引發劑。作為如此的光聚合引發劑，具體地例如可舉出苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻丙基醚、苯偶姻異丙基醚、苯偶姻異丁基醚等的苯偶姻烷基醚系引發劑；二苯基酮、苯甲醯基苯甲酸、3,3’-二甲基-4-甲氧基二苯基酮、聚乙烯基二苯基酮等的二苯基酮系引發劑；α-羥基環己基苯基酮、4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮、α-羥基-α,α’-二甲基苯乙酮、甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、2-甲基-1-[4-(甲硫基)-苯基]-2-嗎啉基丙烷-1等之芳香族酮系引發劑；苄基二甲基縮酮等之芳香族縮酮系引發劑；噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2-乙基噻噸酮、2-異丙基噻噸酮、2-十二基噻噸酮、2,4-二氯噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等之噻噸酮系引發劑；苯偶醯等之苯偶醯系引發劑；苯偶姻等之苯偶姻系引發劑；2-甲基-2-羥基苯丙酮等之α-乙酮醇系化合物；2-萘磺醯氯等之芳香族磺醯氯系化合物；1-苯酮-1,1-丙二酮-2-(鄰乙氧基羰基)肟等之光活性肟系化合物；樟腦醌系化合物；鹵化酮系化合物；醯基膦氧化物系化合物；醯基亞膦酸酯系化合物等。此等可為單獨或複數使用。相對於(甲基)丙烯酸系聚合物100質量份而言，光聚合引發劑的配合量較佳為0.01～5質量份。In the radiation curable adhesive composition of the present embodiment, when ultraviolet rays are used as the radiation, the photopolymerization initiator may be further contained. Specific examples of such a photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Benzoyl alkyl ether initiator; diphenyl ketone, benzhydryl benzoic acid, 3,3'-dimethyl-4-methoxydiphenyl ketone, polyvinyl diphenyl ketone Diphenyl ketone initiator; α-hydroxycyclohexyl phenyl ketone, 4-(2-hydroxyethoxy)phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α '-Dimethylacetophenone, methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl- An aromatic ketone initiator such as 1-[4-(methylthio)-phenyl]-2-morpholinylpropane-1; an aromatic ketal initiator such as benzyldimethylketal; Tons of ketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-dodecylthioxanthone, 2,4-dichloro a thioxanthone-based initiator such as thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone or 2,4-diisopropylthioxanthone; benzoin, etc. Benzoin initiator; benzoin An initiator; an α-ethyl ketone alcohol compound such as 2-methyl-2-hydroxypropiophenone; an aromatic sulfonium chloride compound such as 2-naphthalene sulfonium chloride; 1-benzophenone-1, 1-propene A photoactive oxime compound such as diketone-2-(o-ethoxycarbonyl)anthracene; a camphorquinone compound; a halogenated ketone compound; a mercaptophosphine oxide compound; a mercaptophosphinate compound. These may be used singly or in plural. The amount of the photopolymerization initiator to be added is preferably from 0.01 to 5 parts by mass based on 100 parts by mass of the (meth)acrylic polymer.

本實施形態的輻射線硬化性黏著劑組成物，只要含有上述(甲基)丙烯酸系聚合物及交聯劑，則以其它特性的改善為目的，視需要亦可更含有增黏劑、防老化劑、填充劑、著色劑、難燃劑、抗靜電劑、軟化劑、紫外線吸收劑、抗氧化劑、可塑劑、界面活性劑等眾所周知的添加劑。惟，具有輻射線反應性碳-碳雙鍵的多官能單體或多官能寡聚物等之低分子量多官能聚合性化合物(例如分子量或重量平均分子量為3,000以下)較佳為儘可能地少，更佳為實質上不含有。本實施形態的輻射線硬化性黏著劑組成物若含有如此的低分子量成分，則輻射線所致的硬化前的黏著力及保持力容易降低，而且拾取性容易劣化。再者，於(甲基)丙烯酸系單體或輻射線反應性化合物的工業製品中，當低分子量多官能聚合性化合物無可避免地混入時。如此無可避免地混入之低分子量多官能聚合性化合物的量，相對於輻射線硬化性黏著劑組成物全量而言通常為1質量%以下。The radiation-curable adhesive composition of the present embodiment contains the above-mentioned (meth)acrylic polymer and a crosslinking agent, and is intended to improve other properties, and may further contain a tackifier or an anti-aging agent as needed. Well-known additives such as agents, fillers, colorants, flame retardants, antistatic agents, softeners, ultraviolet absorbers, antioxidants, plasticizers, surfactants, and the like. However, a low molecular weight polyfunctional polymerizable compound such as a polyfunctional monomer or a polyfunctional oligomer having a radiation-reactive carbon-carbon double bond (for example, a molecular weight or a weight average molecular weight of 3,000 or less) is preferably as small as possible. More preferably, it does not contain substantially. When such a low molecular weight component is contained in the radiation curable adhesive composition of the present embodiment, the adhesive force and the holding power before curing due to radiation are likely to be lowered, and the pickup property is likely to be deteriorated. Further, in an industrial product of a (meth)acrylic monomer or a radiation-reactive compound, when a low molecular weight polyfunctional polymerizable compound is inevitably mixed. The amount of the low molecular weight polyfunctional polymerizable compound which is inevitably mixed in the amount of the radiation curable adhesive composition is usually 1% by mass or less based on the total amount of the radiation curable adhesive composition.

本實施形態的模切用黏著薄膜，係可藉由眾所周知的方法在基材的至少一面上塗佈上述輻射線硬化性黏著劑組成物而製造。又，使用後述的隔片時，亦可在隔片的一面上塗佈輻射線硬化性黏著劑組成物後，在黏著劑層上貼合基材。作為基材，只要是具有至少部分地穿透輻射線(X射線、紫外線、電子射線等)之特性的基材，則可沒有特別限制地使用。作為如此的基材，可舉出塑膠製、金屬製、紙製等的基材，於此等之中，較佳為塑膠製基材。作為如此的塑膠製基材，具體地例如可舉出由聚烯烴系樹脂(低密度聚乙烯、直鏈狀聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、無規共聚合聚丙烯、嵌段共聚合聚丙烯、均聚丙烯、聚丁烯、聚甲基戊烯等)、乙烯-醋酸乙烯酯共聚物、離子聚合物系樹脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物(無規共聚物、交替共聚物等)、乙烯-丁烯共聚物、乙烯-己烯共聚物、聚胺甲酸酯系樹脂、聚酯系樹脂(聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸丁二酯等)、聚醯亞胺系樹脂、聚醯胺系樹脂、聚醚酮系樹脂、聚醚系樹脂、聚醚碸系樹脂、聚苯乙烯系樹脂(聚苯乙烯等)、聚氯乙烯系樹脂、聚偏二氯乙烯系樹脂、聚乙烯基醇系樹脂、聚醋酸乙烯酯系樹脂、氯乙烯-醋酸乙烯酯共聚物、聚碳酸酯系樹脂、氟系樹脂、聚矽氧系樹脂、纖維素系樹脂、或此等樹脂的交聯體等構成材料所成的基材。此等構成材料係可為單獨或複數使用。上述構成材料視需要亦可具有官能基。又，機能性單體或改質性單體亦可接枝於構成材料。再者，塑膠製基材的表面，為了提高與鄰接層的密接性，亦可施予眾所周知的表面處理方法。作為如此的表面處理，具體的地例如可舉出電暈放電處理、臭氧暴露處理、高壓電擊暴露處理、離子化輻射線處理等。又，亦可對基材施予底塗劑的塗覆處理、底層處理、消光處理、交聯處理等。The adhesive film for die cutting of the present embodiment can be produced by applying the above-mentioned radiation curable adhesive composition to at least one surface of a substrate by a known method. Further, when a separator to be described later is used, a radiation curable adhesive composition may be applied to one surface of the separator, and then the substrate may be bonded to the adhesive layer. The substrate is not particularly limited as long as it has a property of at least partially penetrating radiation (X-rays, ultraviolet rays, electron beams, etc.). Examples of such a substrate include substrates made of plastic, metal, paper, and the like. Among them, a base material made of plastic is preferable. Specific examples of such a plastic substrate include polyolefin resin (low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, and random Polymerized polypropylene, block copolymerized polypropylene, homopolypropylene, polybutene, polymethylpentene, etc., ethylene-vinyl acetate copolymer, ionic polymer resin, ethylene-(meth)acrylic acid copolymer , ethylene-(meth) acrylate copolymer (random copolymer, alternating copolymer, etc.), ethylene-butene copolymer, ethylene-hexene copolymer, polyurethane resin, polyester resin ( Polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, etc., polyamidene resin, polyamine resin, poly Ether ketone resin, polyether resin, polyether oxime resin, polystyrene resin (polystyrene, etc.), polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, poly Vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, polycarbonate resin, fluorine system Constituent material of butter, polyethylene oxide-based silicon resin, cellulose resin, or the like such crosslinked resin into the substrate. These constituent materials may be used singly or in plural. The above constituent material may have a functional group as needed. Further, the functional monomer or the modified monomer may be grafted to the constituent material. Further, in order to improve the adhesion to the adjacent layer on the surface of the plastic substrate, a well-known surface treatment method can be applied. Specific examples of such surface treatment include corona discharge treatment, ozone exposure treatment, high-voltage electric shock exposure treatment, ionizing radiation treatment, and the like. Further, a coating treatment, a primer treatment, a matting treatment, a crosslinking treatment, and the like of the primer may be applied to the substrate.

基材係可具有單層的形態，也可具有層合的形態。又，於基材中，視需要例如亦可含有填充劑、難燃劑、防老化劑、抗靜電劑、軟化劑、紫外線吸收劑、抗氧化劑、可塑劑、界面活性劑等眾所周知的添加劑。基材的厚度係沒有特別的限制，較佳為10～300μm，更佳為30～200μm。The substrate may have a single layer form or a laminated form. Further, in the substrate, for example, a well-known additive such as a filler, a flame retardant, an anti-aging agent, an antistatic agent, a softener, an ultraviolet absorber, an antioxidant, a plasticizer, or a surfactant may be contained. The thickness of the substrate is not particularly limited, but is preferably 10 to 300 μm, more preferably 30 to 200 μm.

黏著劑層的厚度係沒有特別的限制，較佳為4～20μm。黏著劑層的厚度若為4μm以上，則在模切時可將半導體晶圓等的被加工物確實地保持在模切用黏著薄膜。又，於模切步驟中由於半導體晶圓等的被加工物振動，故若振動幅度大，則在半導體元件等的切斷片容易發生碎裂。然而，黏著劑層的厚度若為20μm以下，則可抑制模切時所發生的振動之振動幅度的過度變大。The thickness of the adhesive layer is not particularly limited, but is preferably 4 to 20 μm. When the thickness of the adhesive layer is 4 μm or more, the workpiece such as a semiconductor wafer can be surely held in the die-bonding adhesive film during die cutting. Further, in the die-cutting step, the workpiece such as the semiconductor wafer vibrates. Therefore, when the vibration amplitude is large, the cut piece of the semiconductor element or the like is likely to be broken. However, when the thickness of the adhesive layer is 20 μm or less, it is possible to suppress an excessive increase in the vibration amplitude of the vibration generated during die cutting.

使用半導體晶圓(矽鏡面晶圓)當作被加工物時，黏著劑層之輻射線所致的硬化前對半導體晶圓(矽鏡面晶圓)的黏著力(剝離角度：180°，牽引速度：300mm/分鐘，溫度：23±3℃)較佳為0.5(N/10mm寬)以上，更佳為1.0(N/10mm寬)以上。輻射線所致的硬化前之黏著力若為0.5(N/10mm寬)以上，則可充分抑制或防止模切步驟中的半導體元件之脫離飛散。黏著劑層之輻射線所致的硬化後對半導體晶圓(矽鏡面晶圓)的黏著力(剝離角度：180°，牽引速度：300mm/分鐘，溫度：23±3℃)較佳為0.15(N/10mm寬)以下，更佳為未達0.10(N/10mm寬)。若為輻射線所致的硬化後具有如此低的黏著力之黏著劑層，則拾取不良係少，而且亦可減低糊殘渣(黏著劑成分的殘存)。When using a semiconductor wafer (mirror wafer) as a workpiece, the adhesion of the adhesive layer to the semiconductor wafer (the mirror wafer) before hardening (peeling angle: 180°, traction speed) : 300 mm / min, temperature: 23 ± 3 ° C) is preferably 0.5 (N/10 mm width) or more, more preferably 1.0 (N/10 mm width) or more. If the adhesion force before hardening due to radiation is 0.5 (N/10 mm width) or more, the detachment of the semiconductor element in the die cutting step can be sufficiently suppressed or prevented. The adhesion to the semiconductor wafer (the mirror surface wafer) after hardening by the radiation layer of the adhesive layer (peeling angle: 180°, traction speed: 300 mm/min, temperature: 23±3 ° C) is preferably 0.15 ( Below N/10 mm width), more preferably less than 0.10 (N/10 mm width). In the case of an adhesive layer having such a low adhesive force after hardening due to radiation, there are few pick-up defects, and the paste residue (residue of the adhesive component) can be reduced.

又，黏著劑層之輻射線所致的硬化前對SUS製的金屬製構件之黏著力(試驗板：JIS G 4305中規定的SUS304(BA)板，剝離角度=180°，牽引速度：300mm/分鐘，溫度：23±3℃)較佳為0.4(N/10mm寬)以上。輻射線所致的硬化前之黏著力若為0.4(N/10mm寬)以上，則可將環框強固地固定於黏著劑層，可充分抑制或防止模切步驟中的半導體元件之脫離飛散。Further, the adhesion to the metal member made of SUS before curing due to the radiation of the adhesive layer (test plate: SUS304 (BA) plate specified in JIS G 4305, peeling angle = 180°, pulling speed: 300 mm/ Minutes, temperature: 23 ± 3 ° C) is preferably 0.4 (N/10 mm width) or more. When the adhesive force before hardening due to radiation is 0.4 (N/10 mm width) or more, the ring frame can be strongly fixed to the adhesive layer, and the scattering and scattering of the semiconductor element in the die cutting step can be sufficiently suppressed or prevented.

再者，黏著劑層之輻射線所致的硬化前之保持力(試驗板：JIS G 4305中規定的SUS304(BA)板，貼合面積：25mm×25mm，荷重：1.0kg，溫度：60℃，濕度：50%RH，保持時間：1星期)，以根據JIS Z 0237所測定的偏移量表示，較佳為未達0.1mm。輻射線所致的硬化前之保持力若未達0.1mm，則可充分抑制模切步驟中的半導體元件之振動，可進一步減低碎裂。Furthermore, the holding force before hardening due to the radiation of the adhesive layer (test plate: SUS304 (BA) plate specified in JIS G 4305, bonding area: 25 mm × 25 mm, load: 1.0 kg, temperature: 60 ° C Humidity: 50% RH, holding time: 1 week), expressed as an offset amount measured according to JIS Z 0237, preferably less than 0.1 mm. If the holding force before hardening due to radiation is less than 0.1 mm, the vibration of the semiconductor element in the die cutting step can be sufficiently suppressed, and the chipping can be further reduced.

圖1係顯示本實施形態的模切用黏著薄膜之構成的一例之截面示意圖。如圖1中所示，本實施形態的模切用黏著薄膜1係具有在基材2的一面上形成有含上述輻射線硬化性黏著劑組成物的黏著劑層3之構成。又，如圖1中所示，於黏著劑層3上，視需要亦可設置隔片4。隔片4係沒有特別的限制，可使用眾所周知的隔片。作為如此的隔片4之構成材料，具體地例如可舉出紙類；聚乙烯、聚丙烯、聚對苯二甲酸乙二酯等的合成樹脂等。又，對隔片4的表面，為了提高黏著劑層3的剝離性，視需要亦可施予聚矽氧處理、長鏈烷基處理、氟處理等的處理。隔片4的厚度係沒有特別的限制，通常為10～200μm。黏著劑層3係可為1層，也可為2層以上。再者，於圖1中，雖然黏著劑層3係僅設置在基材2的單面，但在基材2的兩面亦可設置黏著劑層3。又，雖然未圖示，但按照使用形態，代替隔片4，亦可有基材2的另一面上形成其它黏著劑層或脫模處理層等。作為形成其它黏著劑層用的黏著劑組成物，具體地例如可使用含有丙烯酸系黏著劑、橡膠系黏著劑、胺甲酸酯系黏著劑、聚矽氧系黏著劑、聚酯系黏著劑、聚醯胺系黏著劑、環氧系黏著劑、乙烯基烷基醚系黏著劑、氟系黏著劑等眾所周知的黏著劑之黏著劑組成物。再者，上述基材之另一面上所形成的黏著劑組成物，視需要亦可含有各種添加劑、輻射線硬化性成分或發泡劑等。又，作為形成脫模處理層用的脫模處理劑(剝離劑)，具體地例如可使用聚矽氧系脫模處理劑、長鏈烷基系脫模處理劑、氟系脫模處理劑等眾所周知的脫模處理劑。模切用黏著薄膜亦可具有捲繞成捲筒狀的形態或寬廣薄片所層合的形態。又，也可為經切斷加工成指定尺寸的薄片狀或膠帶狀之形態。Fig. 1 is a schematic cross-sectional view showing an example of a structure of an adhesive film for die cutting according to the embodiment. As shown in Fig. 1, the die-cut adhesive film 1 of the present embodiment has a structure in which an adhesive layer 3 containing the radiation curable adhesive composition is formed on one surface of a substrate 2. Further, as shown in Fig. 1, on the adhesive layer 3, a spacer 4 may be provided as needed. The spacer 4 is not particularly limited, and a well-known spacer can be used. Specific examples of the constituent material of the separator 4 include papers; synthetic resins such as polyethylene, polypropylene, and polyethylene terephthalate. Further, in order to improve the peeling property of the adhesive layer 3 on the surface of the separator 4, a treatment such as polyfluorination treatment, long-chain alkyl treatment, or fluorine treatment may be applied as needed. The thickness of the separator 4 is not particularly limited and is usually 10 to 200 μm. The adhesive layer 3 may be one layer or two or more layers. Further, in FIG. 1, although the adhesive layer 3 is provided only on one side of the substrate 2, the adhesive layer 3 may be provided on both surfaces of the substrate 2. Further, although not shown, in place of the spacer 4, another adhesive layer, a release treatment layer, or the like may be formed on the other surface of the substrate 2 depending on the form of use. As the adhesive composition for forming another adhesive layer, specifically, for example, an acrylic adhesive, a rubber adhesive, an urethane adhesive, a polyoxygen adhesive, a polyester adhesive, or the like may be used. An adhesive composition of a well-known adhesive such as a polyamide-based adhesive, an epoxy-based adhesive, a vinyl alkyl ether-based adhesive, or a fluorine-based adhesive. Further, the adhesive composition formed on the other surface of the substrate may contain various additives, a radiation curable component, a foaming agent, and the like as needed. In addition, as a mold release treatment agent (release agent) for forming a release treatment layer, for example, a polyfluorene-based release treatment agent, a long-chain alkyl-based release treatment agent, a fluorine-based release treatment agent, or the like can be used. A well-known release treatment agent. The die-cut adhesive film may have a form in which it is wound into a roll shape or a laminate of a wide sheet. Further, it may be in the form of a sheet or a tape which is cut into a predetermined size.

本實施形態的模切用黏著薄膜係可使用於將被加工物模切而製造切斷片之情況。作為如此的被加工物，具體地例如可舉出半導體晶圓、半導體封裝、玻璃、陶瓷等。此等被加工物係由矽系化合物、鍺系化合物、鎵-砷化合物等的化合物所構成，藉由背面研削處理(背景)等，而在所露出的面上有未氧化狀態的活性矽原子(Si)、未氧化狀態的活性鍺原子(Ge)、未氧化狀態的活性鎵原子(Ga)等之未氧化狀態的活性原子以多數存在。因此，為了模切具有如此的活性原子之被加工物，若將模切用黏著薄膜貼於被加工物，則黏著劑層中作為主成分所含有的(甲基)丙烯酸系聚合物之極性部位與活性原子鍵結合，即使在輻射線所致的硬化後也顯高的黏著力，切斷片與模切用黏著薄膜的剝離係變困難。然而，若藉由本實施形態的模切用黏著薄膜，則即使在具有活性面的被加工物上貼附模切用黏著薄膜，於自模切用黏著薄膜剝離切斷片之際，也與貼附時間沒有關係，可藉由輻射線的照射來充分減低對活性面的黏著力，可容易地剝離切斷片。The adhesive film for die cutting of the present embodiment can be used for die-cutting a workpiece to produce a cut piece. Specific examples of such a workpiece include a semiconductor wafer, a semiconductor package, glass, ceramics, and the like. These processed materials are composed of a compound such as a lanthanoid compound, a lanthanoid compound, or a gallium-arsenic compound, and have an active ruthenium atom in an unoxidized state on the exposed surface by a back grinding process (background) or the like. (Si), an active ruthenium atom (Ge) in an unoxidized state, and an active atom in an unoxidized state such as an unoxidized active gallium atom (Ga) exist in a large amount. Therefore, in order to die-cut a workpiece having such an active atom, if a die-cut adhesive film is attached to a workpiece, the polar portion of the (meth)acrylic polymer contained as a main component in the adhesive layer is formed. In combination with the active atom bond, even after the hardening by the radiation, the adhesion is high, and the peeling of the cut piece and the die-cut adhesive film becomes difficult. However, according to the adhesive film for die-cutting of the present embodiment, the die-bonding adhesive film is attached to the workpiece having the active surface, and the cut-off film is peeled off from the die-cut adhesive film. The time does not matter, and the adhesion to the active surface can be sufficiently reduced by the irradiation of the radiation, and the cut piece can be easily peeled off.

於本實施形態中，作為將被加工物模切而製造切斷片之方法，可適宜使用至少具有以下步驟的製造方法：於被加工物的一面貼上模切用黏著薄膜之安裝步驟，將貼有模切用黏著薄膜的被加工物切斷而分離成切斷片之模切步驟，及對貼於切斷片的黏著劑層照射輻射線以使黏著劑層的黏著力降低，由黏著力已降低的模切用黏著薄膜來拾取切斷片之拾取步驟。In the present embodiment, as a method of producing a cut piece by die-cutting a workpiece, a production method having at least the following steps can be suitably used: a step of attaching a die-cut adhesive film to one surface of the workpiece, and attaching The die-cutting step of cutting the workpiece by the die-cut film into a cut piece, and irradiating the adhesive layer attached to the cut piece with radiation to lower the adhesive force of the adhesive layer, and the adhesive force is lowered The die cutting uses an adhesive film to pick up the picking step of the cut piece.

於被加工物的一面貼上模切用黏著薄膜之安裝步驟中，通常於環框的一面及半導體晶圓等的被加工物之一面與黏著劑層的一面成接觸的形態，疊合此等，藉由壓黏輥等所所周知的押壓手段來押壓此，而在被加工物貼上模切用黏著薄膜。又，在可加壓的容器(例如高壓釜等)中，於與前述同樣的形態下疊合被加工物與模切用黏著薄膜，藉由將容器內加壓，亦可在被加工物貼上模切用黏著薄膜。再者，亦可於減壓室(真空室)內，與上述加壓所致貼上之情況同樣地，在被加工物貼上模切用黏著薄膜。In the step of attaching the adhesive film for die-cutting to one side of the workpiece, the surface of the ring frame and one surface of the workpiece such as a semiconductor wafer are usually in contact with one surface of the adhesive layer, and these are superimposed. This is pressed by a pressing means known by a pressure-sensitive adhesive roll or the like, and an adhesive film for die-cutting is attached to the workpiece. Further, in a pressurizable container (for example, an autoclave or the like), the workpiece and the die-bonding adhesive film are laminated in the same manner as described above, and by pressurizing the container, the workpiece can be attached. The upper die is cut with an adhesive film. In addition, in the decompression chamber (vacuum chamber), an adhesive film for die-cutting can be attached to the workpiece in the same manner as in the case of the above-described pressurization.

其次，於模切步驟中，藉由刀片等的模切手段來模切貼在模切用黏著薄膜上的半導體晶圓等被加工物，以製造被加工物的切斷片。於如此的模切步驟中，通常為了摩擦熱的去除或防止切斷層的附著，而一邊對貼有模切用黏著薄膜的半導體晶圓等被加工物供應洗淨水，一邊以高速旋轉的刀片將被加工物切斷成指定的尺寸。因此，由於切斷刀而切斷片振動，容易發生碎裂，但本實施形態的模切用黏著薄膜之黏著劑層中所用的輻射線硬化性黏著劑組成物由於具有高黏著力及高保持力，故可減低模切用切斷片自黏著薄膜的脫離飛散，可減低碎裂。模切裝置係沒有特別的限定，可使用習知者。再者，按照需要，在模切步驟後亦可進行洗淨步驟、擴展步驟等。Then, in the die-cutting step, a workpiece such as a semiconductor wafer attached to the die-bonding adhesive film is die-cut by a die-cutting means such as a blade to produce a cut piece of the workpiece. In the above-described die-cutting step, the blade is rotated at a high speed while supplying the washing water to the workpiece such as the semiconductor wafer to which the die-bonding adhesive film is attached, in order to remove the frictional heat or prevent the adhesion of the cut layer. Cut the workpiece into the specified size. Therefore, the sheet is vibrated by the cutting blade, and the chipping is likely to occur. However, the radiation curable adhesive composition used in the adhesive layer of the adhesive film for die cutting of the present embodiment has high adhesion and high holding power. Therefore, the detachment of the cut piece from the die-cut film can be reduced, and the chipping can be reduced. The die cutting device is not particularly limited, and a conventional one can be used. Further, a washing step, an expanding step, and the like may be performed after the die cutting step as needed.

於拾取步驟中，藉由對模切用黏著薄膜的黏著劑層照射輻射線，而使黏著劑層的黏著力降低後，自模切用黏著薄膜拾取切斷片。作為輻射線，例如可舉出X射線、電子射線、紫外線等。於此等之中，較佳為紫外線。照射輻射線之際的照射強度或照射時間等各種條件係沒有特別的限定，可適宜設定。拾取方法係沒有特別的限定，可採用習知的各種拾取方法。例如，可舉出藉由針自模切用黏著薄膜側將各個切斷片頂起，藉由拾取裝置來拾取所頂起的切斷片之方法等。本實施形態的模切用黏著薄膜，由於可藉由輻射線的照射來充分降低黏著力，故即使使用具有活性面的被加工物時，也在如上述的拾取步驟中，可自模切用黏著薄膜容易地剝離切斷片，可減低黏著劑成分對剝離後的切斷片之附著。In the pick-up step, the adhesive layer of the adhesive film for die-cutting is irradiated with radiation, whereby the adhesive force of the adhesive layer is lowered, and the cut piece is picked up by the adhesive film from the die-cutting. Examples of the radiation include X-rays, electron beams, and ultraviolet rays. Among these, ultraviolet rays are preferred. Various conditions such as the irradiation intensity or the irradiation time when the radiation is irradiated are not particularly limited, and can be appropriately set. The picking method is not particularly limited, and various picking methods can be employed. For example, a method in which each of the cut pieces is lifted up by the needle from the die-bonding film side, and the cut piece is picked up by the pick-up device can be cited. Since the adhesive film for die-cutting of the present embodiment can sufficiently reduce the adhesive force by irradiation with radiation, even when a workpiece having an active surface is used, it can be used for die-cutting as in the above-described pick-up step. The adhesive film easily peels off the cut piece, and the adhesion of the adhesive component to the cut piece after peeling can be reduced.

以下，藉由實施例更詳細說明實施例，惟本發明不受此等實施例所限定。再者，於以下中，「份」係意味「質量份」。Hereinafter, the examples are explained in more detail by way of examples, but the invention is not limited by the examples. In addition, in the following, "parts" means "parts by mass".

[實施例][Examples] ＜(甲基)丙烯酸系聚合物之合成＞<Synthesis of (meth)acrylic polymer>

作為共聚合單體成分，準備具有碳數2的直鏈烷基之丙烯酸乙酯[溶解度參數(SP值，以下同樣)：10.2(cal/cm3 )1/2 ，分子量：100.12]、具有碳數8的支鏈烷基之丙烯酸2-乙基己酯[SP值：9.2(cal/cm3 )1/2 ，分子量：184.28]、具有碳數18的直鏈烷基之丙烯酸十八酯[SP值：9.0(cal/cm3 )1/2 ，分子量：324.54]、及具有羥基的丙烯酸2-羥基乙酯[SP值：13.3(cal/cm3 )1/2 ，分子量：116.12]。以表1及2中所示的各配合量混合此等共聚合單體成分，進行溶液自由基聚合而合成各基礎聚合物(溶劑：醋酸乙酯)。於聚合時，藉由GPC進行共聚合單體成分的反應追蹤，於共聚合單體成分消失的時間點結束聚合。As the copolymerization monomer component, ethyl acrylate having a linear alkyl group having 2 carbon atoms was prepared [solubility parameter (SP value, the same applies hereinafter): 10.2 (cal/cm 3 ) 1/2 , molecular weight: 100.12], with carbon Number 8-branched alkyl 2-ethylhexyl acrylate [SP value: 9.2 (cal/cm 3 ) 1/2 , molecular weight: 184.28], octadecyl acrylate having a linear alkyl group having a carbon number of 18 [ SP value: 9.0 (cal/cm 3 ) 1/2 , molecular weight: 324.54], and 2-hydroxyethyl acrylate having a hydroxyl group [SP value: 13.3 (cal/cm 3 ) 1/2 , molecular weight: 116.12]. These copolymerized monomer components were mixed at the respective amounts shown in Tables 1 and 2, and solution radical polymerization was carried out to synthesize each base polymer (solvent: ethyl acetate). At the time of polymerization, the reaction of the monomer component by copolymerization was carried out by GPC, and the polymerization was terminated at the time when the copolymerization monomer component disappeared.

其次，對於此各基礎聚合物，以表1及2中所示的各配合量使作為輻射線反應性化合物的具有異氰酸酯基與輻射線反應性碳-碳雙鍵的甲基丙烯酸2-異氰酸酯乙酯(第1官能基：異氰酸酯基，第1官能基數：1個/1分子，分子量：155.15)反應，而合成各(甲基)丙烯酸系聚合物。再者，於上述反應時，使用0.05份的氫醌‧單甲基醚作為聚合抑制劑。藉由GPC(溶劑：四氫呋喃)測定所合成的各(甲基)丙烯酸系聚合物之重量平均分子量，結果為50萬～80萬。Next, for each of the base polymers, 2-isocyanate methacrylate having an isocyanate group and a radiation-reactive carbon-carbon double bond as a radiation-reactive compound was used in each of the amounts shown in Tables 1 and 2. Each of the (meth)acrylic polymers was synthesized by reacting an ester (first functional group: isocyanate group, number of first functional groups: 1 / 1 molecule, molecular weight: 155.5). Further, in the above reaction, 0.05 part of hydroquinone monomethyl ether was used as a polymerization inhibitor. The weight average molecular weight of each (meth)acrylic polymer synthesized by GPC (solvent: tetrahydrofuran) was measured and found to be 500,000 to 800,000.

＜模切用黏著薄膜之製作＞<Production of adhesive film for die cutting>

混合如上述所得之各(甲基)丙烯酸系聚合物、作為交聯劑的表1及2中所示之各配合量的聚異氰酸酯化合物(日本聚胺甲酸酯公司製，商品名：Colonate L，第2官能基：異氰酸酯基，第2官能基數：3個/1分子，分子量：656.64)、0.5份作為光聚合引發劑的1-羥基環己基苯基酮(Ciba特殊化學品公司製，商品名：Irgacure 184)，以調製各輻射線硬化性黏著劑組成物。再者，於比較例7中，調製以表2中所示的配合量更添加有作為多官能單體的三羥甲基丙烷三丙烯酸酯(官能基數：3個/1分子，分子量：296.32)之輻射線硬化性黏著劑組成物。Each of the (meth)acrylic polymers obtained as described above and the polyisocyanate compound of each compounding amount shown in Tables 1 and 2 as a crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd., trade name: Colonate L) , a second functional group: an isocyanate group, a second functional group: 3 / 1 molecule, a molecular weight: 656.64), and 0.5 part of a 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator (manufactured by Ciba Specialty Chemicals Co., Ltd., Name: Irgacure 184) to prepare each radiation curable adhesive composition. Further, in Comparative Example 7, the addition of trimethylolpropane triacrylate as a polyfunctional monomer was further added in the amount shown in Table 2 (number of functional groups: 3 / 1 molecule, molecular weight: 296.32) Radiation hardenable adhesive composition.

其次，將上述所得之各輻射線硬化性黏著劑組成物，以成為表1及2中所示厚度的方式，塗佈在聚對苯二甲酸乙二酯製隔片(厚度：38μm)上，形成黏著劑層後，在100℃、50%RH的環境下加熱乾燥3分鐘。然後，於黏著劑層上貼合單面施有電暈放電處理的聚烯烴製薄膜(厚度：100μm)。將所貼合的試料在40℃、50%RH的恆溫槽中保存72小時，進行交聯處理，以製作各模切用黏著薄膜。Next, each of the radiation curable adhesive compositions obtained above was applied to a polyethylene terephthalate separator (thickness: 38 μm) so as to have the thickness shown in Tables 1 and 2. After the adhesive layer was formed, it was dried by heating at 100 ° C and 50% RH for 3 minutes. Then, a polyolefin film (thickness: 100 μm) which was subjected to corona discharge treatment on one side was attached to the pressure-sensitive adhesive layer. The sample to be bonded was stored in a thermostat bath at 40° C. and 50% RH for 72 hours, and subjected to a crosslinking treatment to prepare an adhesive film for die cutting.

使用如上述所製作的各模切用黏著薄膜，進行以下的評價。表1及2中一併顯示各輻射線硬化性黏著劑組成物的組成、基礎聚合物的溶解度參數、基礎聚合物的羥基之莫耳量與第1官能基及第2官能基的合計莫耳量之差、殘存羥基濃度、輻射線反應性碳-碳雙鍵濃度以及評價結果。再者，比較例7的輻射線硬化性黏著劑組成物中之輻射線反應性碳-碳雙鍵濃度，係以輻射線反應性化合物及多官能單體所具有的輻射線反應性碳-碳雙鍵之合計量為基礎的值。The following evaluation was performed using each of the die-bonding adhesive films produced as described above. Tables 1 and 2 together show the composition of each radiation curable adhesive composition, the solubility parameter of the base polymer, the molar amount of the hydroxyl group of the base polymer, and the total number of the first functional group and the second functional group. The difference in amount, the residual hydroxyl group concentration, the radiation-reactive carbon-carbon double bond concentration, and the evaluation results. Further, the radiation-reactive carbon-carbon double bond concentration in the radiation curable adhesive composition of Comparative Example 7 is a radiation-reactive carbon-carbon possessed by a radiation-reactive compound and a polyfunctional monomer. The total value of the double bond is based on the measurement.

[評價][Evaluation] (輻射線所致的硬化前對SUS的黏著力)(Adhesion to SUS before hardening due to radiation)

將經切斷成25mm寬的長方形狀之模切用黏著薄膜，於23℃的環境下貼合於SUS304(BA)板上，將此在室溫環境下靜置30分鐘以製作測定試料。測定此測定試料的黏著力，用以下的基準評價硬化前的黏著力。黏著力的測定條件係剝離角度180°、剝離速度300mm/分鐘、溫度23±3℃。The adhesive film for die-cutting, which was cut into a rectangular shape of 25 mm in width, was bonded to a SUS304 (BA) plate in an environment of 23 ° C, and allowed to stand at room temperature for 30 minutes to prepare a measurement sample. The adhesion of the measurement sample was measured, and the adhesion before curing was evaluated by the following criteria. The measurement conditions of the adhesive force were a peeling angle of 180°, a peeling speed of 300 mm/min, and a temperature of 23±3°C.

○：黏著力的測定值為0.4N/10mm以上○: The measured value of the adhesive force is 0.4 N/10 mm or more.

△：黏著力的測定值未達0.4N/10mm△: The measured value of the adhesive force is less than 0.4 N/10 mm

×：由於內聚破壞而無法測定黏著力×: adhesion cannot be measured due to cohesive failure

(輻射線所致的硬化前對半導體晶圓的黏著力)(Adhesion to semiconductor wafer before hardening due to radiation)

將經切斷成25mm寬的長方形狀之模切用黏著薄膜，於23℃的環境下貼合於鏡面研磨處理後立即的5吋矽鏡面晶圓上，將此在室溫環境下靜置30分鐘以製作測定試料。測定此測定試料的黏著力，用以下的基準評價硬化前的黏著力。黏著力的測定條件係剝離角度180°、剝離速度300mm/分鐘、溫度23±3℃。The adhesive film which was cut into a rectangular shape of 25 mm in width was attached to a 5 吋矽 mirror wafer immediately after the mirror polishing treatment in an environment of 23 ° C, and was allowed to stand at room temperature. Minutes to make a test sample. The adhesion of the measurement sample was measured, and the adhesion before curing was evaluated by the following criteria. The measurement conditions of the adhesive force were a peeling angle of 180°, a peeling speed of 300 mm/min, and a temperature of 23±3°C.

○：黏著力的測定值為1.0N/10mm以上○: The measured value of the adhesive force is 1.0 N/10 mm or more.

△：黏著力的測定值為0.5N/10mm以上、未達1.0N/10mm△: The measured value of the adhesive force is 0.5 N/10 mm or more and less than 1.0 N/10 mm.

×：黏著力的測定值未達0.5N/10mm，或由於內聚破壞而無法測定黏著力×: The measured value of the adhesive force is less than 0.5 N/10 mm, or the adhesion cannot be measured due to cohesive failure.

(輻射線所致的硬化前之保持力)(Retention force before hardening due to radiation)

於經切斷成25mm寬的長方形狀之模切用黏著薄膜上，裱褙聚酯薄膜(19μm厚)後，於23℃的環境下將模切用黏著薄膜貼合於SUS304(BA)板上(貼合面積：25mm×25mm)。將此貼合的試料在室溫環境下靜置30分鐘，以製作測定試料測定試料。對此測定試料，在溫度60℃、濕度50%RH的環境下，施予1星期、1.0kg的荷重後，測定偏移量，用以下的基準評價保持力。The die-cut adhesive film was bonded to a SUS304 (BA) plate at 23 ° C after being cut into a 25 mm-wide rectangular die-cut adhesive film and rubbing a polyester film (19 μm thick). Fit area: 25mm × 25mm). The sample to be bonded was allowed to stand in a room temperature environment for 30 minutes to prepare a measurement sample measurement sample. The measurement sample was subjected to a load of 1 week and 1.0 kg in an environment of a temperature of 60 ° C and a humidity of 50% RH, and then the amount of the measurement was measured, and the retention was evaluated by the following criteria.

○：1星期經過後，偏移量未達0.1mm○: After 1 week, the offset is less than 0.1mm

×：1星期經過後，偏移量為0.1mm以上，或薄膜落下×: After 1 week, the offset is 0.1 mm or more, or the film falls.

(輻射線所致的硬化後對半導體晶圓的黏著力)(adhesion to the semiconductor wafer after hardening due to radiation)

製作與輻射線所致的硬化前之黏著力的測定中所用的測定試料同樣的測定試料。自此測定試料的模切用黏著薄膜之基材側照射紫外線(照射強度：300mJ/cm2 )，與上述輻射線所致的硬化前之黏著力同樣地測定照射後的黏著力，用以下的基準評價硬化後的黏著力。The measurement sample similar to the measurement sample used for the measurement of the adhesive force before hardening by radiation was produced. The base material side of the die-cut adhesive film for the die-cutting test was irradiated with ultraviolet rays (irradiation intensity: 300 mJ/cm 2 ), and the adhesion after the irradiation was measured in the same manner as the adhesion before the curing by the radiation. The benchmark evaluates the adhesion after hardening.

○：黏著力的測定值未達0.1N/10mm○: The measured value of the adhesion is less than 0.1 N/10 mm

△：黏著力的測定值為0.1N/10mm以上、0.15N/10mm以下△: The measured value of the adhesive force is 0.1 N/10 mm or more and 0.15 N/10 mm or less.

×：黏著力的測定值超過0.15N/10mm×: The measured value of the adhesive force exceeds 0.15 N/10 mm

(拾取性)(pickup)

鏡面研磨處理厚度100μm的5吋矽鏡面晶圓後，立即在23℃的環境下於研磨面貼上模切用黏著薄膜。一邊對貼有此黏著薄膜的晶圓供應洗淨水，一邊將晶圓全切割(full cut)成10mm×10mm的大小。After mirror-polishing a 5-inch mirror wafer having a thickness of 100 μm, an adhesive film for die-cutting was attached to the polished surface immediately at 23 ° C. The wafer was fully cut into a size of 10 mm × 10 mm while supplying the washing water to the wafer to which the adhesive film was attached.

其次，自模切用黏著薄膜的基材側照射紫外線(照射強度：300mJ/cm2 )後，自基材側用5支針將經模切的1個半導體元件頂起500μm的高度，使用筒夾來拾取所頂起的半導體元件。測定此半導體元件之拾取所需要的力(拾取力)，求得10個半導體元件的拾取力之平均值，用以下的基準評價拾取性。Next, after irradiating ultraviolet rays (irradiation intensity: 300 mJ/cm 2 ) from the substrate side of the adhesive film, the die-cut one semiconductor element was lifted by a height of 500 μm from the substrate side with five pins, and the tube was used. Clip to pick up the topped semiconductor component. The force (pickup force) required for picking up the semiconductor element was measured, and the average value of the pickup power of the ten semiconductor elements was determined, and the pickup property was evaluated by the following criteria.

○：拾取力的平均值為1.5N以下○: The average value of the pickup force is 1.5 N or less

△：拾取力的平均值為超過1.5N、2.0N以下△: The average value of the pickup force is more than 1.5N and 2.0N or less.

×：拾取力的平均值超過2.0N×: The average value of the pickup force exceeds 2.0N

(碎裂)(fragmentation)

鏡面研磨處理厚度100μm的5吋矽鏡面晶圓後，立即在23℃的環境下於研磨面貼上模切用黏著薄膜。一邊對貼有此黏著薄膜的晶圓供應洗淨水，一邊將晶圓全切割成10mm×10mm的大小。After mirror-polishing a 5-inch mirror wafer having a thickness of 100 μm, an adhesive film for die-cutting was attached to the polished surface immediately at 23 ° C. The wafer was completely cut into a size of 10 mm × 10 mm while supplying the washing water to the wafer to which the adhesive film was attached.

其次，自模切用黏著薄膜的基材側照射紫外線(照射強度：300mJ/cm2 )，擴展後，自黏著薄膜剝離半導體元件，拾取。由所拾取的半導體元件之中任意選擇5個，藉由顯微鏡觀察各邊的背面碎裂，用以下的基準評價碎裂。Next, ultraviolet light (irradiation intensity: 300 mJ/cm 2 ) was irradiated from the substrate side of the adhesive film by die-cutting, and after expanding, the semiconductor element was peeled off from the adhesive film and picked up. Five of the semiconductor elements picked up were arbitrarily selected, and the back surface of each side was observed by a microscope, and the chipping was evaluated by the following criteria.

○：全部半導體元件的碎裂之最大尺寸為15μm以下○: The maximum size of chipping of all semiconductor elements is 15 μm or less

×：至少1個半導體元件的碎裂之最大尺寸超過15μm×: The maximum size of the fragmentation of at least one semiconductor element exceeds 15 μm

(污染性)(pollution)

於潔淨室(潔淨度：等級100)內，將模切用黏著薄膜貼合於6吋的矽鏡面晶圓，在室溫環境下靜置30分鐘後，自模切用黏著薄膜的基材側照射紫外線(照射強度：300mJ/cm2 )。將此試料在23℃50%RH環境下保存30日後，自晶圓剝離模切用黏著薄膜，藉由雷射表面檢查裝置(株式會社日立高科技公司製，LS-6000)來觀測剝離後的晶圓面，用以下的基準評價污染性。In the clean room (cleanliness: grade 100), the die-cut adhesive film is attached to a 6-inch enamel mirror wafer, and after standing at room temperature for 30 minutes, the substrate side of the adhesive film is self-cut. Irradiated with ultraviolet rays (irradiation intensity: 300 mJ/cm 2 ). After the sample was stored in a 50° RH environment at 23° C. for 30 days, the adhesive film for die-cutting was peeled off from the wafer, and the peeled surface was observed by a laser surface inspection apparatus (LS-6000, manufactured by Hitachi High-Technologies Corporation). On the wafer surface, the pollution was evaluated by the following criteria.

○：污染物的總數未達2,000○: The total number of pollutants is less than 2,000

×：污染物的總數為2,000以上×: The total number of pollutants is 2,000 or more

如上述表中所示，可知使用實施例的輻射線硬化性黏著劑組成物之模切用黏著薄膜，係在輻射線所致的硬化前具有高黏著力及高保持力，同時在輻射線所致的硬化後具有低黏著力。因此，可知使用此等模切用黏著薄膜時，拾取不良的發生少，而且切斷片上糊污染少。再者，可知所得之半導體元件的碎裂亦少。As shown in the above table, it is understood that the die-bonding adhesive film using the radiation curable adhesive composition of the embodiment has high adhesion and high holding power before hardening by radiation, and is also in the radiation line. The resulting hardening has a low adhesion. Therefore, it has been found that when such an adhesive film for die cutting is used, the occurrence of pickup failure is small, and the paste on the cut sheet is less contaminated. Further, it is understood that the obtained semiconductor element has less chipping.

相對於此，可知使用由含有溶解度參數過高或過低的基礎聚合物所得之(甲基)丙烯酸系聚合物的輻射線硬化性黏著劑組成物之模切用黏著薄膜，係即使在輻射線所致的硬化後也具有高黏著力，因此拾取性差。茲認為此係因為若基礎聚合物的溶解度參數過高，則(甲基)丙烯酸系聚合物的極性部位係不被烷基所充分隱蔽，極性部位與活性原子變容易接觸。另一方面，茲認為因為使用具有過低的溶解度參數之基礎聚合物時，導入基礎聚合物中的羥基量係降低，可導入(甲基)丙烯酸系聚合物中的輻射線反應性碳-碳雙鍵濃度降低。On the other hand, it is known that the adhesive film for die-cutting using a radiation curable adhesive composition containing a (meth)acrylic polymer obtained by using a base polymer having a too high or too low solubility parameter is even in radiation. The resulting hardening also has a high adhesion, so the pick-up property is poor. It is considered that if the solubility parameter of the base polymer is too high, the polar portion of the (meth)acrylic polymer is not sufficiently concealed by the alkyl group, and the polar portion and the active atom are easily contacted. On the other hand, it is considered that when a base polymer having an excessively low solubility parameter is used, the amount of hydroxyl groups introduced into the base polymer is lowered, and radiation-reactive carbon-carbon in the (meth)acrylic polymer can be introduced. The concentration of the double bond is lowered.

又，可知使用殘存羥基濃度過高的輻射線硬化性黏著劑組成物之模切用黏著薄膜，即使在輻射線所致的硬化後也具有高黏著力，因此拾取性差。茲認為此係因為具有活性面的半導體晶圓與殘存羥基變容易鍵結，結果即使(甲基)丙烯酸系聚合物具有一定量的輻射線反應性碳-碳雙鍵，黏著力也難以降低。Moreover, it is understood that the die-bonding adhesive film using the radiation curable adhesive composition having a too high residual hydroxyl group concentration has high adhesion even after curing due to radiation, and thus has poor pick-up property. It is considered that this is because the semiconductor wafer having the active surface is easily bonded to the residual hydroxyl group, and as a result, even if the (meth)acrylic polymer has a certain amount of radiation-reactive carbon-carbon double bond, the adhesion is hard to be lowered.

再者，可知使用交聯劑的含量過少的輻射線硬化性黏著劑組成物之模切用黏著薄膜，係保持力低，發生碎裂。另一方面，即使輻射線反應性碳-碳雙鍵濃度為一定範圍，若交聯劑的含量過多，則輻射線反應性化合物的第1官能基及交聯劑的第2官能基之合計莫耳量也變得比導入基礎聚合物中的羥基之莫耳量還多，輻射線所致的硬化前的黏著力降低，同時污染性劣化。又，即使交聯劑的含量為一定範圍，為了提高硬化性，在(甲基)丙烯酸系聚合物中導入輻射線反應性碳-碳雙鍵，以使得輻射線反應性化合物的第1官能基及交聯劑的第2官能基之合計莫耳量也變得比導入基礎聚合物中的羥基之莫耳量還多的程度為止時，不僅輻射線所致的硬化前的保持力降低，而且污染性亦劣化。In addition, it is known that the adhesive film for die-cutting using a radiation curable adhesive composition having a too small content of a crosslinking agent has a low holding power and is cracked. On the other hand, even if the concentration of the radiation-reactive carbon-carbon double bond is within a certain range, if the content of the crosslinking agent is too large, the total of the first functional group of the radiation-reactive compound and the second functional group of the crosslinking agent The amount of the ear also becomes larger than the amount of the hydroxyl group introduced into the base polymer, and the adhesion before the hardening due to the radiation is lowered, and the contamination is deteriorated. Further, even if the content of the crosslinking agent is within a certain range, in order to improve the curability, a radiation-reactive carbon-carbon double bond is introduced into the (meth)acrylic polymer to make the first functional group of the radiation-reactive compound. When the total molar amount of the second functional group of the crosslinking agent is also increased to a greater extent than the amount of the hydroxyl group introduced into the base polymer, not only the holding force before curing due to radiation but also the lowering force is lowered. Pollution is also degraded.

而且，可知使用多官能單體來增加輻射線硬化性黏著劑組成物中的輻射線反應性碳-碳雙鍵濃度時，輻射線所致的硬化後之黏著力雖然降低，但拾取性倒是若干降低，而且輻射線所致的硬化前之黏著力及保持力降低。茲認為此係因為藉由使用低分子量多官能聚合性化合物，輻射線硬化性黏著劑組成物變成軟質，而且阻礙(甲基)丙烯酸系聚合物與交聯劑的交聯反應。Moreover, it is known that when a polyfunctional monomer is used to increase the concentration of the radiation-reactive carbon-carbon double bond in the radiation curable adhesive composition, although the adhesion after hardening due to radiation is lowered, the pick-up property is somewhat Reduced, and the adhesion and retention of the pre-hardening due to radiation are reduced. It is considered that this is because the radiation curable adhesive composition becomes soft by using a low molecular weight polyfunctional polymerizable compound, and the crosslinking reaction of the (meth)acrylic polymer and the crosslinking agent is inhibited.

1．．．模切用黏著薄膜1. . . Die-cut adhesive film

2．．．基材2. . . Substrate

3．．．黏著劑層3. . . Adhesive layer

4．．．隔片4. . . bead

圖1係顯示本發明的實施形態之模切用黏著薄膜之一例的截面示意圖。Fig. 1 is a schematic cross-sectional view showing an example of an adhesive film for die cutting according to an embodiment of the present invention.

1．．．模切用黏著薄膜1. . . Die-cut adhesive film

2．．．基材2. . . Substrate

3．．．黏著劑層3. . . Adhesive layer

4．．．隔片4. . . bead

Claims (4)

一種模切用黏著薄膜，其係具備基材，與在前述基材上之含有輻射線硬化性黏著組成物的黏著層之模切用黏著薄膜，其中前述輻射線硬化性黏著劑組成物含有：使至少具有含烷基的(甲基)丙烯酸系單體及含羥基的(甲基)丙烯酸系單體當作共聚合單體成分，而且具有9.6(cal/cm3 )1/2 以上、10.0(cal/cm3 )1/2 以下的溶解度參數之基礎聚合物，與在分子內具有能與經由前述含羥基的(甲基)丙烯酸系單體導入基礎聚合物中的羥基反應的第1官能基及輻射線反應性碳-碳雙鍵之輻射線反應性化合物進行反應而得之(甲基)丙烯酸系聚合物，及對於前述(甲基)丙烯酸系聚合物，在分子內具有能與前述羥基進行交聯反應的第2官能基之交聯劑：前述含羥基的(甲基)丙烯酸系單體、前述輻射線反應性化合物及前述交聯劑，係以經由前述含羥基的(甲基)丙烯酸系單體導入基礎聚合物中的羥基之莫耳質量為前述輻射線反應性化合物的第1官能基及前述交聯劑的第2官能基之合計莫耳量以上，每1g輻射線硬化性黏著劑組成物中的交聯反應後之殘存羥基濃度為0.08mmol以下，每1g輻射線硬化性黏著劑組成物中的經由前述輻射線反應性化合物導入(甲基)丙烯酸系聚合物中的輻射線反應性碳-碳雙鍵濃度為0.42mmol以上、0.8mmol以下而配合。An adhesive film for die cutting, comprising: a base material, and an adhesive film for die-cutting of an adhesive layer containing a radiation curable adhesive composition on the substrate, wherein the radiation curable adhesive composition comprises: The (meth)acrylic monomer having at least an alkyl group and the hydroxyl group-containing (meth)acrylic monomer are used as a copolymerization monomer component, and have 9.6 (cal/cm 3 ) 1/2 or more and 10.0. (cal/cm 3 ) a base polymer having a solubility parameter of 1/2 or less, and a first functional group having a reactivity with a hydroxyl group introduced into the base polymer via the hydroxyl group-containing (meth)acrylic monomer in the molecule a (meth)acrylic polymer obtained by reacting a radiation-reactive compound having a radiation-reactive carbon-carbon double bond, and having the same ability in the molecule as described above for the (meth)acrylic polymer a crosslinking agent of a second functional group in which a hydroxyl group undergoes a crosslinking reaction: the hydroxyl group-containing (meth)acrylic monomer, the radiation-reactive compound, and the crosslinking agent are via a hydroxyl group-containing (methyl group) ) acrylic monomer is introduced into the base polymer The molar mass of the hydroxyl group is equal to or greater than the total amount of the first functional group of the radiation-reactive compound and the second functional group of the crosslinking agent, and the crosslinking reaction per 1 g of the radiation curable adhesive composition The residual hydroxyl group concentration is 0.08 mmol or less, and the concentration of the radiation-reactive carbon-carbon double bond introduced into the (meth)acrylic polymer via the radiation-reactive compound per 1 g of the radiation curable adhesive composition is 0.42 mmol or more and 0.8 mmol or less are blended. 如申請專利範圍第1項之模切用黏著薄膜，其中前述輻射線硬化性黏著劑組成物係實質上不含有低分子量多官能聚合性化合物。An adhesive film for die cutting according to the first aspect of the invention, wherein the radiation curable adhesive composition is substantially free of a low molecular weight polyfunctional polymerizable compound. 一種切斷片之製造方法，其係：於被加工物的一面貼上如申請專利範圍第1或2項之模切用黏著薄膜，將貼有前述模切用黏著薄膜的被加工物切斷而分離成切斷片，對貼於前述切斷片的黏著劑層，照射輻射線以使得前述黏著劑層的黏著力降低，由前述黏著力已降低的模切用黏著薄膜來拾取前述切斷片。A method for producing a cut piece, which is obtained by attaching an adhesive film for die cutting according to the first or second aspect of the patent application to one side of the workpiece, and cutting the workpiece to which the adhesive film for die cutting is attached. The cut piece is separated, and the adhesive layer attached to the cut piece is irradiated with radiation so that the adhesive force of the adhesive layer is lowered, and the cut piece is picked up by the die-cut adhesive film whose adhesive force has been lowered. 如申請專利範圍第3項之切斷片之製造方法，其中前述被加工物係具有活性面的半導體晶圓。The method of manufacturing a cut piece according to the third aspect of the invention, wherein the workpiece is a semiconductor wafer having an active surface.
TW100107168A 2010-04-28 2011-03-03 Die cutting with an adhesive film, and a method for manufacturing a cut sheet TWI493011B (en)

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