TWI465537B - Non-uv type dicing die bonding film - Google Patents

Non-uv type dicing die bonding film Download PDF

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TWI465537B
TWI465537B TW101148372A TW101148372A TWI465537B TW I465537 B TWI465537 B TW I465537B TW 101148372 A TW101148372 A TW 101148372A TW 101148372 A TW101148372 A TW 101148372A TW I465537 B TWI465537 B TW I465537B
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weight
parts
adhesive layer
acrylate
adhesive
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TW101148372A
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TW201345992A (en
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Kwang Won Seo
Kyoung Lae Cho
Jae Won Choi
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Cheil Ind Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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    • 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
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    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
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    • 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
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    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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    • 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
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer
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    • H01L2224/29001—Core members of the layer connector
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  • Chemical & Material Sciences (AREA)
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Description

非UV型切割晶粒黏合膜Non-UV type cutting grain adhesive film 發明領域Field of invention

本發明有關一種非UV型切割晶粒黏合膜。The invention relates to a non-UV type cutting grain adhesive film.

發明背景Background of the invention

半導體之製造中所使用之切割黏合膜，一般分成需要UV照射之UV型膜以及不需要UV照射之非UV型膜。The dicing adhesive film used in the manufacture of semiconductors is generally classified into a UV type film which requires UV irradiation and a non-UV type film which does not require UV irradiation.

UV型膜在光固化之前，具有極佳的黏著性，因此展現良好的切割特性。然而，為了在切割之後進行拾取製程，UV型膜需要額外的UV曝光，此使得製程變得繁瑣。拾取製程前進行之UV曝曬，在半導體封裝之製造時程中占了大量的時間，且可能會影響半導體封裝之產率，其接著可能會抑制產率的增加。此外，在UV照射期間，當有UV照射失敗時，UV能量無法充份地施於大量安置之晶圓的一些部份，從而導致拾取製程中，從切割膜層(黏著層)分開半導體晶片之製程失敗。The UV type film has excellent adhesion before photocuring, and thus exhibits good cutting characteristics. However, in order to perform a picking process after cutting, the UV type film requires additional UV exposure, which makes the process cumbersome. The UV exposure performed prior to the pick-up process takes a significant amount of time in the manufacturing process of the semiconductor package and may affect the yield of the semiconductor package, which may then inhibit the increase in yield. In addition, during UV irradiation, when UV irradiation fails, UV energy cannot be sufficiently applied to portions of a large number of deposited wafers, thereby causing the semiconductor wafer to be separated from the dicing film layer (adhesive layer) during the pickup process. The process failed.

為了解決此等問題，愈來愈需要有一種能在拾取製程之前，排除UV曝曬之非UV型膜。非UV型膜對環形框架展現良好的黏著性，但對黏合層具低黏著性，因此可在沒有進行分開UV照射製程之情況下，幫助晶片脫離。In order to solve such problems, there is a growing need for a non-UV type film that can eliminate UV exposure before the picking process. The non-UV type film exhibits good adhesion to the ring frame, but has low adhesion to the adhesive layer, so that the wafer can be detached without performing a separate UV irradiation process.

然而，習知非UV型膜由於差的黏著性，而很容易與環形框架分開。基本上，展現差黏著性之非UV型膜，在鋸切製程時，不耐於切割晶圓，其會使對環形框架之黏著性變弱，導致在擴張製程和/或拾取製程中，膜之黏著層與環形框架之間分開。此可能導致拾取性能減低，導致產率減少。However, conventional non-UV type films are easily separated from the annular frame due to poor adhesion. Basically, a non-UV type film exhibiting poor adhesion is not resistant to cutting the wafer during the sawing process, which weakens the adhesion to the annular frame, resulting in a film in the expansion process and/or the picking process. The adhesive layer is separated from the annular frame. This may result in reduced pickup performance, resulting in reduced yield.

為了解決此問題，已有建議黏貼一會展現對欲黏貼之環形框架之部分，具強黏著性之額外分開的膜之方法。然而，此等方法使得半導體製程稍顯繁瑣以及複雜。In order to solve this problem, it has been proposed to adhere a method of exhibiting an additional adhesive film having a strong adhesiveness to a portion of the annular frame to be pasted. However, these methods make the semiconductor process somewhat cumbersome and complicated.

韓國專利案第1019756號中，揭示一個有關非UV型膜之先前技藝之例子。該先前技藝目的在於幫助拾取製程，藉由使UV固化黏著層之一些區域，先經UV曝露之處理，以便適當地調整鋸切時之支持力、對環形框架之黏著性以及拾取製程之脫離力。然而，在此文件中，在進行部分地固化UV固化黏著層之過程中，UV可能照射到黏貼至環形框架之部分，因此降低對環形框架之黏著性。結果，該先前技藝亦具有與此技藝中預固化非UV型膜相同的問題。In Korean Patent No. 1019756, an example of a prior art relating to a non-UV type film is disclosed. The prior art objective is to assist in the picking process by first curing some areas of the UV-cured adhesive layer by UV exposure to properly adjust the support force during sawing, the adhesion to the annular frame, and the force to remove the pick-up process. . However, in this document, during the partial curing of the UV-cured adhesive layer, UV may illuminate the portion adhered to the annular frame, thereby reducing the adhesion to the annular frame. As a result, this prior art also has the same problems as the pre-cured non-UV type films of this art.

發明概要Summary of invention

為了解決此技藝中之此等問題，本發明人研發出一種切割晶粒黏合膜，其與透過後續的製程來強化表現出弱黏著性之切割晶粒黏合膜之黏著性相反，透過黏合膜本身之物理特性，對環形框架展現極佳的黏著性。明確而言，本發明人已研發出一種非UV型切割晶粒黏合膜，其藉由同 時包括特定數量之含羥基基團之丙烯酸酯單體以及聚乙二醇(甲基)丙烯酸酯，而對環形框架展現極佳的黏著性。In order to solve such problems in the art, the inventors have developed a cut grain adhesion film which is opposite to the adhesion of a cut grain adhesion film which exhibits weak adhesion through a subsequent process, through the adhesive film itself. The physical properties give excellent adhesion to the ring frame. Specifically, the inventors have developed a non-UV type dicing die bond film by the same A certain number of hydroxyl group-containing acrylate monomers and polyethylene glycol (meth) acrylate are included to exhibit excellent adhesion to the ring frame.

本發明之一態樣係提供一種非UV型切割晶粒黏合膜，其包括對環形框架展現極佳黏著性之丙烯酸共聚物，以及以該丙烯酸共聚物100重量份為基準，包括20重量份至40重量份之含羥基基團之丙烯酸酯單體以及聚乙二醇(甲基)丙烯酸酯。An aspect of the present invention provides a non-UV type dicing die bonding film comprising an acrylic copolymer exhibiting excellent adhesion to an annular frame, and comprising 20 parts by weight based on 100 parts by weight of the acrylic copolymer 40 parts by weight of a hydroxyl group-containing acrylate monomer and polyethylene glycol (meth) acrylate.

本發明之另一目的係提供一種非UV型切割晶粒黏合膜，其藉由包括一黏著層，抑制因環形框架分離造成之製程缺失以及展現高拾取成功率，該黏著層具有對環形框架之黏著強度(x)為2.5N/25mm或更大，以及對黏合層之黏著強度(y)與對環形框架之黏著強度(x)之比率(y/x)為1.3或更小。Another object of the present invention is to provide a non-UV type dicing die bonding film which comprises a coating layer for suppressing a process defect caused by separation of a ring frame and exhibiting a high picking success rate, the adhesive layer having a pair of annular frames The adhesive strength (x) is 2.5 N/25 mm or more, and the ratio (y/x) of the adhesive strength (y) to the adhesive layer to the adhesive strength (x) to the annular frame is 1.3 or less.

本發明有關一種非UV型切割晶粒黏合膜，其包括特定數量之含羥基基團之丙烯酸酯單體以及聚乙二醇(甲基)丙烯酸酯二者。The present invention relates to a non-UV type dicing die attach film comprising a specific number of hydroxy group-containing acrylate monomers and polyethylene glycol (meth) acrylate.

本發明之一態樣提供一種非UV型切割晶粒黏合膜，其包括丙烯酸共聚物以及熱固化劑，其中以該丙烯酸共聚物100重量份為基準，該丙烯酸共聚物包括：55重量份至95重量份之丙烯酸烷基酯單體；5重量份至30重量份之含羥基基團之丙烯酸酯單體；以及1重量份至15重量份之聚乙二醇(甲基)丙烯酸酯。One aspect of the present invention provides a non-UV type dicing die bonding film comprising an acrylic copolymer and a heat curing agent, wherein the acrylic copolymer comprises: 55 parts by weight to 95 based on 100 parts by weight of the acrylic copolymer Parts by weight of the alkyl acrylate monomer; from 5 parts by weight to 30 parts by weight of the hydroxy group-containing acrylate monomer; and from 1 part by weight to 15 parts by weight of the polyethylene glycol (meth) acrylate.

在一具體例中，以該丙烯酸共聚物100重量份為基準，該非UV型切割晶粒黏合膜可包括總量為20重量份至 40重量份之該含羥基基團之丙烯酸酯單體以及該聚乙二醇(甲基)丙烯酸酯。In a specific example, the non-UV type dicing die bond film may include a total amount of 20 parts by weight based on 100 parts by weight of the acrylic copolymer. 40 parts by weight of the hydroxyl group-containing acrylate monomer and the polyethylene glycol (meth) acrylate.

在一具體例中，該聚乙二醇(甲基)丙烯酸酯可以式1表示： In one embodiment, the polyethylene glycol (meth) acrylate can be represented by Formula 1:

其中n是從2至40之整數。Wherein n is an integer from 2 to 40.

於一具體例中，該丙烯酸共聚物可進一步包括一種包括含磷官能基團之丙烯酸酯單體。In one embodiment, the acrylic copolymer may further comprise an acrylate monomer comprising a phosphorus-containing functional group.

於一具體例中，該包括含磷官能基團之丙烯酸酯單體存在之數量，以該丙烯酸共聚物100重量份為基準，大於0重量份至20重量份。In one embodiment, the acrylate monomer comprising a phosphorus-containing functional group is present in an amount of from greater than 0 parts by weight to 20 parts by weight based on 100 parts by weight of the acrylic copolymer.

於一具體例中，該丙烯酸共聚物可進一步包括一種含環氧基團之丙烯酸酯單體。In one embodiment, the acrylic copolymer may further comprise an epoxy group-containing acrylate monomer.

於一具體例中，該含環氧基團之丙烯酸酯單體存在之數量，以該丙烯酸共聚物100重量份為基準，大於0重量份至10重量份。In one embodiment, the epoxy group-containing acrylate monomer is present in an amount of more than 0 parts by weight to 10 parts by weight based on 100 parts by weight of the acrylic copolymer.

本發明之另一態樣提供一種非UV型切割晶粒黏合膜，其包括：一黏著層，其以丙烯酸共聚物100重量份為基準，含有總量為20重量份至40重量份之含羥基基團之丙烯酸酯單體以及聚乙二醇(甲基)丙烯酸酯以及一黏合層，其疊在該黏著層上，其中該黏著層具有對環形框架之黏著強度(x)為2.5N/25mm或更大，以及對黏合層之黏著強度(y) 與對環形框架之黏著強度(x)之比率(y/x)為1.3或更小。Another aspect of the present invention provides a non-UV type dicing die bonding film comprising: an adhesive layer containing a total of 20 parts by weight to 40 parts by weight of a hydroxyl group based on 100 parts by weight of the acrylic copolymer a acrylate monomer of the group and a polyethylene glycol (meth) acrylate and an adhesive layer laminated on the adhesive layer, wherein the adhesive layer has an adhesion strength (x) to the annular frame of 2.5 N/25 mm Or larger, and adhesion strength to the adhesive layer (y) The ratio (y/x) to the adhesion strength (x) to the annular frame is 1.3 or less.

於一具體例中，該黏著層可具有對環形框架之黏著強度(x)，其大於對黏合層之黏著強度(y)(即，x>y)。In one embodiment, the adhesive layer can have an adhesive strength (x) to the annular frame that is greater than the adhesive strength (y) of the adhesive layer (ie, x>y).

本發明之另外的態樣提供一種半導體元件，其包括一配線基材以及一半導體晶片，其等透過該非UV型晶粒黏合膜之黏合層連接。According to still another aspect of the present invention, a semiconductor device includes a wiring substrate and a semiconductor wafer which are connected through an adhesive layer of the non-UV type die adhesion film.

如本發明之非UV型切割晶粒黏合膜，因該黏合膜本身之物理特性，對環形框架展現極佳的黏著性。The non-UV type dicing die bonding film of the present invention exhibits excellent adhesion to the annular frame due to the physical properties of the bonding film itself.

更特別地，如本發明之非UV型切割晶粒黏合膜，藉由包括特定數量之含羥基基團之丙烯酸酯單體以及聚乙二醇(甲基)丙烯酸酯二者，而對環形框架展現極佳的黏著性。More particularly, the non-UV type dicing die-bonding film of the present invention comprises a ring frame by including a specific number of hydroxy group-containing acrylate monomers and polyethylene glycol (meth) acrylate. Shows excellent adhesion.

如本發明之非UV型切割晶粒黏合膜，藉由包括一黏著層，抑制因環形框架分離造成之製程缺失以及展現高拾取成功率，該黏著層具有對環形框架之黏著強度(x)為2.5N/25mm或更大，以及對黏合層之黏著強度(y)與對環形框架之黏著強度(x)之比率(y/x)為1.3或更小。The non-UV type dicing die-bonding film of the present invention has an adhesive layer having an adhesion strength (x) to the annular frame by including an adhesive layer, suppressing a process defect caused by separation of the annular frame and exhibiting a high picking success rate. The ratio (y/x) of 2.5 N/25 mm or more, and the adhesion strength (y) to the adhesive layer to the adhesion strength (x) to the annular frame is 1.3 or less.

較佳實施例之詳細說明Detailed description of the preferred embodiment

現在將詳細說明本發明之具體例。應了解，下列具體例僅供例示用，任何情況不可解釋為本發明之範疇之限制。Specific examples of the present invention will now be described in detail. It is understood that the following specific examples are for illustrative purposes only and are not to be construed as limiting the scope of the invention.

在此沒有涵蓋之詳細說明係熟悉此技藝之人士能輕易地認知以及領會到的，因此在此省略其之解釋。Detailed descriptions not covered herein are readily recognized and appreciated by those skilled in the art, and thus their explanations are omitted herein.

本發明之一態樣提供一種非UV型切割晶粒黏合膜，其包括丙烯酸共聚物以及熱固化劑，其中以該丙烯酸共聚物100重量份為基準，該丙烯酸共聚物包括55重量份至95重量份之丙烯酸烷基酯單體；5重量份至30重量份之含羥基基團之丙烯酸酯單體；以及1重量份至15重量份之聚乙二醇(甲基)丙烯酸酯。One aspect of the present invention provides a non-UV type dicing die bonding film comprising an acrylic copolymer and a heat curing agent, wherein the acrylic copolymer comprises 55 parts by weight to 95 parts by weight based on 100 parts by weight of the acrylic copolymer. The alkyl acrylate monomer; 5 parts by weight to 30 parts by weight of the hydroxy group-containing acrylate monomer; and 1 part by weight to 15 parts by weight of the polyethylene glycol (meth) acrylate.

在本發明中，可使用此技藝中已知之任何典型的丙烯酸共聚物，此沒有限制。In the present invention, any of the typical acrylic copolymers known in the art can be used without limitation.

該丙烯酸共聚物之例子，包括聚合諸如下列之丙烯酸單體而製得之丙烯酸共聚物：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸氧酯(oxyl(meth)acrylate)、(甲基)丙烯酸十二酯、(甲基)丙烯酸月桂酯以及(甲基)丙烯酸酯之改質物，以及由其改質獲得之(甲基)丙烯酸、醋酸乙烯酯以及丙烯酸單體等等，但不限於此。Examples of the acrylic copolymer include acrylic copolymers obtained by polymerizing an acrylic monomer such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (methyl) ) butyl acrylate, hexyl (meth) acrylate, oxyl (meth) acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, and (meth)acrylic acid The modified product of the ester, and the (meth)acrylic acid, vinyl acetate, acrylic acid monomer and the like obtained by the modification thereof, but are not limited thereto.

丙烯酸或甲基丙烯酸單體之聚合作用，可產生聚丙烯酸酯或甲基丙烯酸酯，其為不含雙鍵之脂族聚合物，且具有極佳的氧化抗性之優點。此外，聚丙烯酸酯或甲基丙烯酸酯具有可根據所欲的物理特性，改變聚合物組成或引入官能基團，進而輕易地改質之優點，以及具有可在低溫、大氣壓力下相對容易製造之優點。The polymerization of acrylic or methacrylic monomers produces polyacrylates or methacrylates which are aliphatic polymers free of double bonds and which have the advantage of excellent oxidation resistance. In addition, polyacrylate or methacrylate has the advantage of changing the polymer composition or introducing a functional group according to desired physical properties, thereby being easily modified, and having relatively easy to manufacture at low temperature and atmospheric pressure. advantage.

在本發明中，可使用此技藝中已知用於聚合丙烯 酸共聚物之任何典型的方法，此沒有限制。In the present invention, it is known to use in the art for polymerizing propylene. Any typical method of acid copolymer is not limited.

當使用溶液聚合方法來聚合丙烯酸共聚物時，較佳地可使用酮類、酯類、醇類或芳族溶劑作為有機溶劑。更佳地使用甲苯、醋酸乙酯、丙酮或甲乙酮。When a solution polymerization method is used to polymerize the acrylic copolymer, a ketone, an ester, an alcohol or an aromatic solvent is preferably used as the organic solvent. More preferably, toluene, ethyl acetate, acetone or methyl ethyl ketone is used.

在本發明中，可使用此技藝中已知之任何丙烯酸烷基酯，此沒有限制。In the present invention, any alkyl acrylate known in the art can be used without limitation.

該丙烯酸烷基酯單體之例子，包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸正丁酯、丙烯酸異丁酯、甲基丙烯酸十八酯、丙烯酸2-乙己酯、丙烯酸異辛酯、甲基丙烯酸己酯或甲基丙烯酸2-乙己酯等等，但不限於此。此等單體可單獨使用或以其之二或多種組合之形式使用。Examples of the alkyl acrylate monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, octadecyl methacrylate, 2-ethylhexyl acrylate, isobutyl acrylate Ethyl ester, hexyl methacrylate or 2-ethylhexyl methacrylate, etc., but is not limited thereto. These monomers may be used singly or in combination of two or more thereof.

在本發明中，該丙烯酸烷基酯單體存在之數量，以該丙烯酸共聚物100重量份為基準，為55重量份至95重量份。在此範圍內，該非UV型切割晶粒黏合膜可展現極佳的黏著性。In the present invention, the alkyl acrylate monomer is present in an amount of from 55 parts by weight to 95 parts by weight based on 100 parts by weight of the acrylic copolymer. Within this range, the non-UV-type cut grain adhesive film exhibits excellent adhesion.

該丙烯酸共聚物較佳地具有重量平均分子量從100,000g/mol至700,000g/mol，更佳地從150,000g/mol至600,000g/mol。在此範圍內，該黏合膜在黏著性以及凝聚力方面具有改善的特性、可防止轉移至被黏物之風險以及具有能夠容易進行聚合作用之黏度。The acrylic copolymer preferably has a weight average molecular weight of from 100,000 g/mol to 700,000 g/mol, more preferably from 150,000 g/mol to 600,000 g/mol. Within this range, the adhesive film has improved properties in terms of adhesion and cohesive force, prevents the risk of transfer to the adherend, and has a viscosity capable of easily performing polymerization.

該丙烯酸共聚物可具有玻璃轉移溫度(Tg)範圍從-30℃至-70℃。The acrylic copolymer may have a glass transition temperature (Tg) ranging from -30 ° C to -70 ° C.

在本發明中，可使用此技藝中已知之任何典型的含羥基基團之丙烯酸酯，此沒有限制。In the present invention, any typical hydroxyl group-containing acrylate known in the art can be used without limitation.

該含羥基基團之丙烯酸酯單體之例子，包括甲基丙烯酸2-羥乙酯、丙烯酸2-羥乙酯、丙烯酸4-羥丁酯、丙烯酸2-羥丙酯或乙烯基己內醯胺等等，但不限於此。此等單體可單獨使用或以其二或多種組合之形式使用。Examples of the hydroxyl group-containing acrylate monomer include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl acrylate or vinyl caprolactam. And so on, but not limited to this. These monomers may be used singly or in combination of two or more thereof.

較佳地使用丙烯酸2-羥乙酯作為該含羥基基團之丙烯酸酯單體。It is preferred to use 2-hydroxyethyl acrylate as the hydroxy group-containing acrylate monomer.

在本發明中使用之聚乙二醇(甲基)丙烯酸酯，具有長的聚乙二醇側鏈，其使二醇官能基團，在切割晶粒黏合膜之製造時，表現在黏合膜之表面上，從而改善對環形框架之黏著性。更特別地，由於長鏈二醇官能基團之存在，得以強化切割晶粒黏合膜以及環形框架間之氫鍵，從而提供對環形框架強的黏著性。The polyethylene glycol (meth) acrylate used in the present invention has a long polyethylene glycol side chain which causes the diol functional group to be exhibited in the adhesive film when the dicing die bond film is manufactured. On the surface, thereby improving the adhesion to the annular frame. More particularly, due to the presence of long chain diol functional groups, the cleavage of the die adhesion film and the hydrogen bonds between the annular frames are enhanced to provide strong adhesion to the annular frame.

該聚乙二醇(甲基)丙烯酸酯可以式1表示： The polyethylene glycol (meth) acrylate can be represented by Formula 1:

其中n較佳地為從2至40之整數，更佳地為從5至20之整數。Wherein n is preferably an integer from 2 to 40, more preferably an integer from 5 to 20.

該聚乙二醇(甲基)丙烯酸酯較佳地具有數量平均分子量從200g/mol至2,000g/mol，更佳地從300g/mol至700g/mol。在此範圍內，該聚乙二醇(甲基)丙烯酸酯可具有充分長的聚乙二醇側鏈，其可強化針對環形框架之氫鍵結合。The polyethylene glycol (meth) acrylate preferably has a number average molecular weight of from 200 g/mol to 2,000 g/mol, more preferably from 300 g/mol to 700 g/mol. Within this range, the polyethylene glycol (meth) acrylate can have sufficiently long polyethylene glycol side chains that enhance hydrogen bonding to the annular framework.

該聚乙二醇(甲基)丙烯酸酯可具有玻璃轉移溫度從 -100℃至150℃。The polyethylene glycol (meth) acrylate can have a glass transition temperature from -100 ° C to 150 ° C.

在本發明中，該含羥基基團之丙烯酸酯單體以及該聚乙二醇(甲基)丙烯酸酯存在之總量，以該丙烯酸共聚物100重量份為基準，為20重量份至40重量份。在此範圍內，該黏合膜對環形框架展現極佳的黏著性。In the present invention, the hydroxyl group-containing acrylate monomer and the polyethylene glycol (meth) acrylate are present in a total amount of from 20 parts by weight to 40 parts by weight based on 100 parts by weight of the acrylic copolymer. Share. Within this range, the adhesive film exhibits excellent adhesion to the annular frame.

在該含羥基基團之丙烯酸酯單體以及該聚乙二醇(甲基)丙烯酸酯中，該含羥基基團之丙烯酸酯單體之數量可大於該聚乙二醇(甲基)丙烯酸酯之數量。In the hydroxyl group-containing acrylate monomer and the polyethylene glycol (meth) acrylate, the amount of the hydroxyl group-containing acrylate monomer may be greater than the polyethylene glycol (meth) acrylate The number.

該含羥基基團之丙烯酸酯單體存在之數量，以該丙烯酸共聚物100重量份為基準，可為5重量份至30重量份。The hydroxyl group-containing acrylate monomer may be present in an amount of 5 parts by weight to 30 parts by weight based on 100 parts by weight of the acrylic copolymer.

該聚乙二醇(甲基)丙烯酸酯存在之數量，以該丙烯酸共聚物100重量份為基準，可為1重量份至15重量份。在此範圍內，該聚乙二醇(甲基)丙烯酸酯可適當的作用，防止過度提高結合劑之玻璃轉移溫度，從而防止諸如切割時對環形框架之黏著性大幅降低、環形框架分離和/或水滲透之問題。The polyethylene glycol (meth) acrylate is present in an amount of from 1 part by weight to 15 parts by weight based on 100 parts by weight of the acrylic copolymer. Within this range, the polyethylene glycol (meth) acrylate acts appropriately to prevent excessively increasing the glass transition temperature of the binder, thereby preventing a large decrease in adhesion to the ring frame such as cutting, separation of the ring frame and/or Or the problem of water penetration.

除了該含羥基基團之丙烯酸酯單體以及該聚乙二醇(甲基)丙烯酸酯外，該丙烯酸共聚物可進一步包括一種丙烯酸酯單體，其包括含磷官能基團和/或含環氧基團之丙烯酸酯單體。In addition to the hydroxyl group-containing acrylate monomer and the polyethylene glycol (meth) acrylate, the acrylic copolymer may further include an acrylate monomer including a phosphorus-containing functional group and/or a ring-containing ring. An acrylate monomer of an oxygen group.

在本發明中，可使用此技藝中已知之任何典型的包括含磷官能基團之丙烯酸酯，此沒有限制。In the present invention, any of the typical acrylates including phosphorus-containing functional groups known in the art can be used without limitation.

該包括含磷官能基團之丙烯酸酯單體，意指一種單體，其具有含磷官能基團，且能夠與含羥基基團之(甲基) 丙烯酸酯和/或含烷基基團之(甲基)丙烯酸酯產生共聚合。The acrylate monomer comprising a phosphorus-containing functional group means a monomer having a phosphorus-containing functional group and capable of reacting with a hydroxyl group-containing (meth) group The acrylate and/or the alkyl group-containing (meth) acrylate is copolymerized.

在一具體例中，該含磷官能基團可以式2或3表示： [式2]-O-P(=O)(OH)2 In one embodiment, the phosphorus-containing functional group can be represented by Formula 2 or 3: [Formula 2]-OP(=O)(OH) 2

[式3]-OP(=O)(OR1 )(OR2 )[Formula 3] -OP(=O)(OR 1 )(OR 2 )

其中R1 以及R2 各自擇自於由下列構成之群組：氫、C1 -C10 烷基基團以及C6 -C20 芳基基團。Wherein R 1 and R 2 are each selected from the group consisting of hydrogen, a C 1 -C 10 alkyl group, and a C 6 -C 20 aryl group.

較佳地，R1 以及R2 各自為氫或C1 -C4 烷基基團。Preferably, R 1 and R 2 are each hydrogen or a C 1 -C 4 alkyl group.

在一具體例中，該包括含磷官能基團之(甲基)丙烯酸酯可以式4表示：[式4]CH2 =CR-C(=O)O-(CH2 )m -O-P(=O)(OR1 )(OR2 )In a specific example, the (meth) acrylate including a phosphorus-containing functional group can be represented by Formula 4: [Formula 4] CH 2 =CR-C(=O)O-(CH 2 ) m -OP(= O) (OR 1 ) (OR 2 )

其中R係-H或-(CH2 )n-CH3 ；n是從0至5之整數；R1 以及R2 彼此各自為擇自於由下列所構成之群組：氫、C1 -C10 烷基基團以及C6 -C20 芳基基團；以及m是從1至10之整數。Wherein R is -H or -(CH 2 )n-CH 3 ; n is an integer from 0 to 5; R 1 and R 2 are each selected from the group consisting of hydrogen, C 1 -C a 10 alkyl group and a C 6 -C 20 aryl group; and m is an integer from 1 to 10.

該包括含磷官能基團之丙烯酸酯單體存在之數量，以該丙烯酸共聚物100重量份為基準，較佳地為0重量份至20重量份，更佳地5重量份至15重量份。The acrylate monomer comprising a phosphorus-containing functional group is present in an amount of preferably from 0 part by weight to 20 parts by weight, more preferably from 5 parts by weight to 15 parts by weight, based on 100 parts by weight of the acryl copolymer.

在本發明中，可使用此技藝中已知之任何典型的含環氧基團之丙烯酸酯。In the present invention, any of the typical epoxy group-containing acrylates known in the art can be used.

該含環氧基團之丙烯酸酯單體之例子，包括甲基丙烯酸縮水甘油酯或丙烯酸縮水甘油酯等等，但不限於 此。此等單體可單獨使用或以其二或多種組合之形式使用。Examples of the epoxy group-containing acrylate monomer include, but are not limited to, glycidyl methacrylate or glycidyl acrylate. this. These monomers may be used singly or in combination of two or more thereof.

較佳地，使用甲基丙烯酸縮水甘油酯作為該含環氧基團之丙烯酸酯單體。Preferably, glycidyl methacrylate is used as the epoxy group-containing acrylate monomer.

該含環氧基團之丙烯酸酯單體存在之數量，以丙烯酸共聚物100重量份為基準，為0重量份至10重量份。The epoxy group-containing acrylate monomer is present in an amount of from 0 part by weight to 10 parts by weight based on 100 parts by weight of the acrylic copolymer.

在本發明中，可使用此技藝中已知之任何典型的熱固化劑，此沒有限制。較佳地，使用異氰酸酯熱固化劑。In the present invention, any of the typical heat curing agents known in the art can be used without limitation. Preferably, an isocyanate thermosetting agent is used.

該異氰酸酯熱固化劑之例子，包括二異氰酸2,4-皮蠅磷、二異氰酸2,6-皮蠅磷、氫化二異氰酸皮蠅磷、二異氰酸1,3-二甲苯酯、二異氰酸1,4-二甲苯酯、二苯甲烷-4,4-二異氰酸酯、二異氰酸根合甲基環己烷、二異氰酸四甲基二甲苯酯、1,5-萘二異氰酸酯、1,6-二異氰酸根合-2,4,4-三甲基-環己烷、1,6-二異氰酸根合-2,4,4-三甲基環己烷、三氯乙烯二異氰酸酯以及三甲醇基丙烷之加成物、二異氰酸二甲苯酯與三甲基醇丙烷之加成物、三苯基甲烷三異氰酸酯以及亞甲基雙二異氰酸酯，但不限於此。此等化合物可單獨使用或以其二或多種組合之形式使用。Examples of the isocyanate thermosetting agent include diisoisocyanate 2,4-picophos, diisocyanate 2,6-picthenium phosphate, hydrogenated diisocyanate, and diisocyanate Xylyl ester, 1,4-dylylene diisocyanate, diphenylmethane-4,4-diisocyanate, diisocyanate methylcyclohexane, tetramethylxylylene diisocyanate, 1 , 5-naphthalene diisocyanate, 1,6-diisocyanato-2,4,4-trimethyl-cyclohexane, 1,6-diisocyanato-2,4,4-trimethyl Addition of cyclohexane, trichloroethylene diisocyanate and trimethylolpropane, addition of ditolyl diisocyanate to trimethylolpropane, triphenylmethane triisocyanate and methylene bis diisocyanate , but not limited to this. These compounds may be used singly or in combination of two or more thereof.

作為熱固化劑，可注意的是商品名AK-75，其是得自AEKYUNG CHEMICAL之異氰酸酯。此係使用醋酸乙酯作為溶劑製得之TDI(二異氰酸甲苯酯)與TMP(三甲基醇丙烷)之加成物。As a heat curing agent, it is noted that the trade name is AK-75, which is an isocyanate available from AEKYUNG CHEMICAL. This is an adduct of TDI (toluene diisocyanate) and TMP (trimethylolpropane) obtained by using ethyl acetate as a solvent.

該熱固化劑存在之數量，以該丙烯酸共聚物100重量份為基準，可為1重量份至15重量份。在此範圍內，該黏著層可維持黏著性，同時防止半導體晶片之製造過程 中，環形框架產生分離以及晶片飛離，從而提高拾取性能。The amount of the heat curing agent present may be from 1 part by weight to 15 parts by weight based on 100 parts by weight of the acrylic copolymer. Within this range, the adhesive layer maintains adhesion while preventing the fabrication process of the semiconductor wafer In the middle, the annular frame produces separation and wafer flying away, thereby improving pickup performance.

如本發明之切割晶粒黏合膜，可包括一黏著層以及一疊在該黏著層上之黏合層。The dicing die attach film of the present invention may comprise an adhesive layer and an adhesive layer stacked on the adhesive layer.

在一具體例中，該黏著層可具有對環形框架之黏著強度(x)為2.5N/25mm或更大，以及對黏合層之黏著強度(y)與對環形框架之黏著強度(x)之比率(y/x)為1.3或更小。在此範圍內，可在不會與環形框架分離之情況下，進行有效的拾取製程。此外，在對黏合層之黏著強度(y)與對環形框架之黏著強度(x)之比率(y/x)大於1.3之情況下，可能會發生拾取製程失敗。即，即使藉由從底部凸出插銷來幫助拾取之情況下，仍無法進行拾取。In a specific example, the adhesive layer may have an adhesion strength (x) to the annular frame of 2.5 N/25 mm or more, and an adhesion strength (y) to the adhesive layer and an adhesion strength (x) to the annular frame. The ratio (y/x) is 1.3 or less. Within this range, an efficient picking process can be performed without being separated from the annular frame. Further, in the case where the ratio (y/x) of the adhesive strength (y) to the adhesive layer to the adhesive strength (x) of the annular frame is greater than 1.3, the picking process failure may occur. That is, even if the pin is protruded from the bottom to help pick up, picking is impossible.

在另一具體例中，該黏著層可具有對環形框架之黏著強度(x)大於對黏合層之黏著強度(y)，即，x>y。In another embodiment, the adhesive layer may have an adhesive strength (x) to the annular frame that is greater than an adhesive strength (y) to the adhesive layer, ie, x>y.

在本發明中，可使用任何由此技藝中已知之組合物以及方法製得之黏合層，此沒有限制。In the present invention, any of the adhesive layers prepared by the compositions and methods known in the art can be used without limitation.

用於製備具有如本發明之切割晶粒黏合膜之黏合層之組成物，可包括聚合物樹脂、環氧樹脂、固化劑、偶合劑、填料以及其它添加物。此等組份之種類以及含量沒有特別限定，可與此技藝中已知者相同。接著，將詳細說明有關如本發明之黏合層之組份之例子。The composition for preparing the adhesive layer having the cut die adhesion film of the present invention may include a polymer resin, an epoxy resin, a curing agent, a coupling agent, a filler, and other additives. The kind and content of these components are not particularly limited and may be the same as those known in the art. Next, an example of a component relating to the adhesive layer of the present invention will be described in detail.

聚合物樹脂Polymer resin

該聚合物樹脂可為此技藝中任何典型地使用之一種，此沒有限制。該聚合物樹脂之例子，可包括聚醯亞胺樹脂、聚苯乙烯樹脂、聚乙烯樹脂、聚酯樹脂、聚醯胺 樹脂、丁二烯橡膠、丙烯酸橡膠、(甲基)丙烯酸樹脂、胺基甲酸酯樹脂、聚醚醯亞胺樹脂、苯氧基樹脂、聚碳酸酯樹脂、聚苯醚樹脂、改質的聚苯醚樹脂以及其等之混合物，但不限於此。The polymer resin can be used in any of the typical applications of the art without limitation. Examples of the polymer resin may include a polyimide resin, a polystyrene resin, a polyethylene resin, a polyester resin, and a polyamine. Resin, butadiene rubber, acrylic rubber, (meth)acrylic resin, urethane resin, polyether phthalimide resin, phenoxy resin, polycarbonate resin, polyphenylene ether resin, modified poly A mixture of phenyl ether resin and the like, but is not limited thereto.

另外，可使用含有官能單體之聚合物。例如，可使用含有諸如下列之官能單體之含環氧基團之(甲基)丙烯酸酯：丙烯酸縮水甘油酯或甲基丙烯酸縮水甘油酯。該含環氧基團之(甲基)丙烯酸酯之例子，可包括(甲基)丙烯酸酯共聚物、丙烯酸橡膠等等。In addition, a polymer containing a functional monomer can be used. For example, an epoxy group-containing (meth) acrylate containing a functional monomer such as the following may be used: glycidyl acrylate or glycidyl methacrylate. Examples of the epoxy group-containing (meth) acrylate may include (meth) acrylate copolymer, acrylic rubber, and the like.

環氧樹脂Epoxy resin

該環氧樹脂可為此技藝中典型地使用之一種，且可包括液態環氧樹脂以及固態環氧樹脂中之至少一種。The epoxy resin can be typically used in the art and can include at least one of a liquid epoxy resin and a solid epoxy resin.

適合的液態環氧樹脂之例子，包括雙酚A類液態環氧樹脂、雙酚F類液態環氧樹脂、三或更高級多官能液態環氧樹脂、橡膠改質的液態環氧樹脂、胺基甲酸酯改質的液態環氧樹脂、丙烯酸改質的液態環氧樹脂以及光敏性液態環氧樹脂，但不限於此。此等液態環氧樹脂可單獨使用或以其混合物之形式使用。Examples of suitable liquid epoxy resins include bisphenol A liquid epoxy resins, bisphenol F liquid epoxy resins, three or higher polyfunctional liquid epoxy resins, rubber modified liquid epoxy resins, and amine groups. The acid ester modified liquid epoxy resin, the acrylic modified liquid epoxy resin, and the photosensitive liquid epoxy resin are not limited thereto. These liquid epoxy resins can be used singly or in the form of a mixture thereof.

該固態環氧樹脂係單或更高級多官能環氧樹脂，其在室溫為固相以或實質上固相。適合的固態環氧樹脂之例子，包括雙酚類環氧樹脂、酚醛類環氧樹脂、鄰甲酚醛類環氧樹脂、多官能環氧樹脂、胺環氧樹脂、雜環環氧樹脂、取代的環氧樹脂、萘基環氧樹脂以及其等之衍生物，但不限於此。The solid epoxy resin is a single or higher polyfunctional epoxy resin which is solid phase or substantially solid phase at room temperature. Examples of suitable solid epoxy resins include bisphenol epoxy resins, phenolic epoxy resins, o-cresol novolac epoxy resins, multifunctional epoxy resins, amine epoxy resins, heterocyclic epoxy resins, substituted Epoxy resin, naphthyl epoxy resin, and derivatives thereof, but are not limited thereto.

市售可得之固態環氧樹脂包括下列。雙酚環氧樹脂之例子包括YD-017H、YD-020、YD020-L、YD-014、YD-014ER、YD-013K、YD-019K、YD-019、YD-017R、YD-017、YD-012、YD-011H、YD-011S、YD-011、YDF-2004以及YDF-2001(Kukdo Chemical Co.,Ltd.)等。酚醛類環氧樹脂包括EPIKOTE 152以及EPIKOTE 154(Yuka Shell Epoxy Co.,Ltd.)；EPPN-201(Nippon Kayaku Co.,Ltd.)；DN-483(Dow Chemical Company)；YDPN-641、YDPN-638A80、YDPN-638、YDPN-637、YDPN-644以及YDPN-631(Kukdo Chemical Co.,Ltd.)等。鄰甲酚醛類環氧樹脂之例子包括YDCN-500-1P、YDCN-500-2P、YDCN-500-4P、YDCN-500-5P、YDCN-500-7P、YDCN-500-8P、YDCN-500-10P、YDCN-500-80P、YDCN-500-80PCA60、YDCN-500-80PBC60、YDCN-500-90P以及YDCN-500-90PA75(Kukdo Chemical Co.,Ltd.)；EOCN-102S、EOCN-103S、EOCN-104S、EOCN-1012、EOCN-1025以及EOCN-1027(Nippon Kayaku Co.,Ltd.)；YDCN-701、YDCN-702、YDCN-703以及YDCN-704(Tohto Kagaku Co.,Ltd.)；Epiclon N-665-EXP(Dainippon Ink and Chemicals,Inc.)等。雙酚醛環氧樹脂之例子包括KBPN-110、KBPN-120以及KBPN-115(Kukdo Chemical Co.,Ltd.)等。多官能環氧樹脂之例子包括Epon 1031S(Yuka Shell Epoxy Co.,Ltd.)；Araldite 0163(Ciba Specialty Chemicals)；Detachol EX-611、Detachol EX-614、Detachol EX-25-12614B、Detachol EX-622、Detachol EX-512、Detachol EX-521、Detachol EX-421、Detachol EX-411以及Detachol EX-321(NAGA Celsius Temperature Kasei Co.,Ltd.)；EP-5200R、KD-1012、EP-5100R、KD-1011、KDT-4400A70、KDT-4400、YH-434L、YH-434以及YH-300(Kukdo Chemical Co.,Ltd.)等。胺環氧樹脂之例子包括EPIKOTE 604(Yuka Shell Epoxy Co.,Ltd.)；YH-434(Tohto Kagaku Co.,Ltd.)；TETRAD-X以及TETRAD-C(Mitsubishi Gas Chemical Company Inc.)；ELM-120(Sumitomo Chemical Industry Co.,Ltd.)等。雜環環氧樹脂之例子包括PT-810(Ciba Specialty Chemicals)。取代的環氧樹脂之例子包括：ERL-4234、ERL-4299、ERL-4221、ERL-4206(UCC Co.,Ltd.)等。萘基環氧樹脂之例子包括：Epiclon HP-4032、Epiclon HP-4032D、Epiclon HP-4700以及Epiclon HP-4701(Dainippon Ink and Chemicals,Inc.)。此等環氧樹脂可單獨或以混合物之形式使用。Commercially available solid epoxy resins include the following. Examples of the bisphenol epoxy resin include YD-017H, YD-020, YD020-L, YD-014, YD-014ER, YD-013K, YD-019K, YD-019, YD-017R, YD-017, YD- 012, YD-011H, YD-011S, YD-011, YDF-2004, and YDF-2001 (Kukdo Chemical Co., Ltd.) and the like. The phenolic epoxy resin includes EPIKOTE 152 and EPIKOTE 154 (Yuka Shell Epoxy Co., Ltd.); EPPN-201 (Nippon Kayaku Co., Ltd.); DN-483 (Dow Chemical Company); YDPN-641, YDPN- 638A80, YDPN-638, YDPN-637, YDPN-644, and YDPN-631 (Kukdo Chemical Co., Ltd.) and the like. Examples of o-cresol novolak epoxy resins include YDCN-500-1P, YDCN-500-2P, YDCN-500-4P, YDCN-500-5P, YDCN-500-7P, YDCN-500-8P, YDCN-500- 10P, YDCN-500-80P, YDCN-500-80PCA60, YDCN-500-80PBC60, YDCN-500-90P and YDCN-500-90PA75 (Kukdo Chemical Co., Ltd.); EOCN-102S, EOCN-103S, EOCN -104S, EOCN-1012, EOCN-1025, and EOCN-1027 (Nippon Kayaku Co., Ltd.); YDCN-701, YDCN-702, YDCN-703, and YDCN-704 (Tohto Kagaku Co., Ltd.); Epiclon N-665-EXP (Dainippon Ink and Chemicals, Inc.) and the like. Examples of the bisphenol aldehyde epoxy resin include KBPN-110, KBPN-120, and KBPN-115 (Kukdo Chemical Co., Ltd.) and the like. Examples of the polyfunctional epoxy resin include Epon 1031S (Yuka Shell Epoxy Co., Ltd.); Araldite 0163 (Ciba Specialty Chemicals); Detachol EX-611, Detachol EX-614, Detachol EX-25-12614B, Detachol EX-622, Detachol EX-512, Detachol EX-521, Detachol EX-421, Detachol EX-411, and Detachol EX-321 (NAGA Celsius Temperature Kasei Co., Ltd.); EP-5200R KD-1012, EP-5100R, KD-1011, KDT-4400A70, KDT-4400, YH-434L, YH-434, and YH-300 (Kukdo Chemical Co., Ltd.) and the like. Examples of the amine epoxy resin include EPIKOTE 604 (Yuka Shell Epoxy Co., Ltd.); YH-434 (Tohto Kagaku Co., Ltd.); TETRAD-X and TETRAD-C (Mitsubishi Gas Chemical Company Inc.); ELM -120 (Sumitomo Chemical Industry Co., Ltd.) and the like. Examples of the heterocyclic epoxy resin include PT-810 (Ciba Specialty Chemicals). Examples of the substituted epoxy resin include: ERL-4234, ERL-4299, ERL-4221, ERL-4206 (UCC Co., Ltd.) and the like. Examples of naphthyl epoxy resins include: Epiclon HP-4032, Epiclon HP-4032D, Epiclon HP-4700, and Epiclon HP-4701 (Dainippon Ink and Chemicals, Inc.). These epoxy resins can be used singly or in the form of a mixture.

固化劑Hardener

該固化劑可為在此技藝中典型地使用者，其沒有限制，且可為酚類固化劑以及胺固化劑。The curing agent can be a user typically employed in the art, which is not limited, and can be a phenolic curing agent and an amine curing agent.

酚類固化樹脂之例子，包括雙酚固化樹脂，諸如雙酚A、雙酚F以及雙酚S；酚醛樹脂；雙酚A線型酚醛樹脂；以及酚類樹脂，諸如新酚樹脂(xylok resins)、鄰甲酚醛樹脂、聯苯樹脂，但不限於此。Examples of the phenolic curable resin include bisphenol curable resins such as bisphenol A, bisphenol F, and bisphenol S; phenolic resins; bisphenol A novolac phenolic resins; and phenolic resins such as xylok resins, O-cresol resin, biphenyl resin, but is not limited thereto.

市售可得之酚類固化樹脂之例子，包括：單純的 酚類固化樹脂，諸如H-1、H-4、HF-1M、HF-3M、HF-4M以及HF-45(Meiwa Plastic Industries Co.,Ltd.)；對二甲苯類固化樹脂，諸如MEH-78004S、MEH-7800SS、MEH-7800S、MEH-7800M、MEH-7800H、MEH-7800HH以及MEH-78003H(Meiwa Plastic Industries Co.,Ltd.)KPH-F3065(Kolon Chemical Co.,Ltd.)；聯苯類固化樹脂，諸如MEH-7851SS、MEH-7851S、MEH7851M、MEH-7851H、MEH-78513H以及MEH-78514H(Meiwa Plastic Industries Co.,Ltd.)以及KPH-F4500(Kolon Chemical Co.,Ltd.)；以及三苯基甲基類固化樹脂，諸如MEH-7500、MEH-75003S、MEH-7500SS、MEH-7500S以及MEH-7500H(Meiwa Plastic Industries Co.,Ltd.)。此等酚類固化劑可單獨使用或以其二或多種混合物之形式使用。Examples of commercially available phenolic curable resins include: Phenolic curing resins such as H-1, H-4, HF-1M, HF-3M, HF-4M, and HF-45 (Meiwa Plastic Industries Co., Ltd.); p-xylene-based curing resins such as MEH- 78004S, MEH-7800SS, MEH-7800S, MEH-7800M, MEH-7800H, MEH-7800HH, and MEH-78003H (Meiwa Plastic Industries Co., Ltd.) KPH-F3065 (Kolon Chemical Co., Ltd.); biphenyl Curing resins such as MEH-7851SS, MEH-7851S, MEH7851M, MEH-7851H, MEH-78513H and MEH-78514H (Meiwa Plastic Industries Co., Ltd.) and KPH-F4500 (Kolon Chemical Co., Ltd.); And a triphenylmethyl-based curing resin such as MEH-7500, MEH-75003S, MEH-7500SS, MEH-7500S, and MEH-7500H (Meiwa Plastic Industries Co., Ltd.). These phenolic curing agents may be used singly or in the form of a mixture of two or more thereof.

固化催化劑Curing catalyst

該固化催化劑係一種可縮短固化時間，以便在半導體製程之過程中完全地固化環氧樹脂。該固化催化劑可為任一種在此技藝中典型地使用者，此沒有限制。該固化催化劑之例子，可包括三聚氰胺、咪唑或三苯基膦類催化劑，但不限於此。市售可得之咪唑類固化催化劑之例子，可包括PN-23以及PN-40(Ajinomoto Co.,Ltd.)；以及2P4MZ、2MA-OK、2MAOK-PW以及2P4 MHZ(Shikoku Chemicals Corp.)。市售可得之三苯基膦類固化催化劑，可包括TPP-K以及TPP-MK(Hokko Chemical Industry Co.,Ltd.)。The curing catalyst is one that shortens the curing time to completely cure the epoxy resin during the semiconductor process. The curing catalyst can be any of the users typically employed in the art, without limitation. Examples of the curing catalyst may include melamine, imidazole or triphenylphosphine catalysts, but are not limited thereto. Examples of commercially available imidazole curing catalysts may include PN-23 and PN-40 (Ajinomoto Co., Ltd.); and 2P4MZ, 2MA-OK, 2MAOK-PW, and 2P4 MHZ (Shikoku Chemicals Corp.). Commercially available triphenylphosphine-based curing catalysts may include TPP-K and TPP-MK (Hokko Chemical Industry Co., Ltd.).

矽烷偶合劑Decane coupling agent

該矽烷偶合劑之作用為黏著促進劑，以便在組成物之摻合期間，透過其間之化學偶合，提高諸如二氧化矽之無機材料與有機材料之表面間的黏著性。The decane coupling agent functions as an adhesion promoter to improve the adhesion between the inorganic material such as cerium oxide and the surface of the organic material during the blending of the composition, through chemical coupling therebetween.

該矽烷偶合劑可為任何此技藝中典型地使用者，此沒有限制。該矽烷偶合劑之例子，可包括含環氧基團之矽烷偶合劑，諸如2-(3,4-環氧環己基)-乙基三甲氧基矽烷、3-環氧丙烷基丙基三甲氧基矽烷以及3-環氧丙烷基丙基三乙氧基矽烷；含胺基團之矽烷偶合劑，諸如N-2-(胺乙基)-3-胺丙基甲基二甲氧基矽烷、N-2-(胺乙基)-3-胺丙基三甲氧基矽烷、N-2-(胺乙基)-3-胺丙基三乙氧基矽烷、3-胺丙基三甲氧基矽烷、3-胺丙基三乙氧基矽烷、3-三乙氧矽基-N-(1,3-二甲亞丁基)丙胺以及N-苯基-3-胺丙基三甲氧基矽烷；含巰基之矽烷偶合劑，諸如3-巰基丙甲基二甲氧基矽烷以及3-巰基丙基三乙氧基矽烷；以及含異氰酸酯之矽烷偶合劑，諸如3-異氰酸丙基三乙氧基矽烷，但不限於此。此等矽烷偶合劑可單獨使用或以其二或多種混合物之形式使用。The decane coupling agent can be any user typically found in the art, and is not limited in this regard. Examples of the decane coupling agent may include an epoxy group-containing decane coupling agent such as 2-(3,4-epoxycyclohexyl)-ethyltrimethoxydecane, 3-epoxypropanepropyltrimethoxy a decane and a 3-epoxypropane propyl triethoxy decane; an amine group-containing decane coupling agent such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxy decane, N-2-(Aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane , 3-aminopropyltriethoxydecane, 3-triethoxyindolyl-N-(1,3-dimethylbutylidene)propylamine, and N-phenyl-3-aminopropyltrimethoxydecane; a mercapto decane coupling agent such as 3-mercaptopropylmethyldimethoxydecane and 3-mercaptopropyltriethoxydecane; and an isocyanate-containing decane coupling agent such as 3-isocyanatopropyltriethoxy Decane, but not limited to this. These decane coupling agents may be used singly or in the form of a mixture of two or more thereof.

填料filler

如本發明之黏著組成物可進一步包括填料，以便藉由提供該組成物觸變特性，而調整該組成物熔融黏度。可使用此技藝中任何典型地使用之類型，此沒有限制。填料可為有機填料或無機填料。無機填料可包括諸如金粉、銀粉、銅粉以及鎳之金屬填料，以及諸如二氧化鋁、氫氧化鋁、氫氧化鎂、碳酸鈉、碳酸鎂、矽酸鈉、矽酸鎂、氧 化鈉、氧化鎂、氧化鋁、氮化鋁、二氧化矽、氮化硼、二氧化鈦、玻璃、氧化鐵、陶瓷等之無機填料。有機填料可為碳基、橡膠基、聚合物基填料等等。雖然填料之形狀與尺寸沒有特別限定，但填料較佳地具球形以及尺寸範圍從500nm至10μm。The adhesive composition according to the present invention may further comprise a filler to adjust the melt viscosity of the composition by providing thixotropic properties of the composition. Any of the types typically used in this art can be used without limitation. The filler may be an organic filler or an inorganic filler. The inorganic filler may include a metal filler such as gold powder, silver powder, copper powder, and nickel, and such as alumina, aluminum hydroxide, magnesium hydroxide, sodium carbonate, magnesium carbonate, sodium citrate, magnesium citrate, oxygen Inorganic fillers such as sodium, magnesia, alumina, aluminum nitride, ceria, boron nitride, titanium dioxide, glass, iron oxide, ceramics, and the like. The organic filler can be a carbon based, rubber based, polymeric based filler, and the like. Although the shape and size of the filler are not particularly limited, the filler is preferably spherical and has a size ranging from 500 nm to 10 μm.

有機溶劑Organic solvents

如本發明之黏著組成物可進一步包括有機溶劑。有機溶劑之作用為降低黏著組成物之黏度，使其易於形成黏著膜。有機溶劑可為任何一種在此技藝中典型使用之有機溶劑，此沒有限制。有機溶劑之例子可包括甲苯、二甲苯、醋酸丙二醇甲醚酯、苯、丙酮、甲基乙基酮、四氫呋喃、二甲基甲醯胺以及環己酮，但不限於此。The adhesive composition according to the present invention may further comprise an organic solvent. The role of the organic solvent is to reduce the viscosity of the adhesive composition, making it easy to form an adhesive film. The organic solvent may be any organic solvent typically used in the art, and is not limited. Examples of the organic solvent may include toluene, xylene, propylene glycol methyl ether acetate, benzene, acetone, methyl ethyl ketone, tetrahydrofuran, dimethylformamide, and cyclohexanone, but are not limited thereto.

其它添加物Other additives

用於如本發明之切割晶粒黏合膜之組成物，可進一步包括添加物，以便吸附離子性雜質以及在吸附離子時提供絕緣可靠度。離子吸附劑可為任何一種在此技藝中典型使用之離子吸附劑，此沒有限制，該離子吸附劑之例子可包括三嗪硫醇化合物、鋯基化合物、銻鉍基化合物以及鎂鋁基化合物，但不限於此。The composition for the dicing die adhesion film of the present invention may further include an additive for adsorbing ionic impurities and providing insulation reliability when adsorbing ions. The ion adsorbent may be any of the ion adsorbents typically used in the art, and is not limited thereto, and examples of the ion adsorbent may include a triazine thiol compound, a zirconium compound, a mercapto compound, and a magnesium aluminum compound. But it is not limited to this.

如本發明之切割晶粒黏合膜可利用任何此技藝中已知之典型方法製造。The diced die attach film of the present invention can be made by any of the typical methods known in the art.

如本發明之切割晶粒黏合膜之製造，不需要特別的裝置或設備，且可利用此技藝中已知任何典型的方法進行。例如，該切割晶粒黏合膜之黏著層可經由下列形成： 將丙烯酸共聚物、聚合起始劑、熱固化劑等等溶於諸如甲基乙基酮或環己酮之溶劑中，接著使用珠磨機充分揉合產物。之後，使用塗佈器，將產物施於經離型處理之聚乙烯對苯二甲酸酯(PET)膜上，接著在100℃烤箱中乾燥2至10分鐘，然後轉移至聚烯烴(PO)膜，如此製得具有適當厚度之黏著膜。之後，使該黏著膜在25~40℃下之烤箱中經歷老化處理，歷時3至7天，藉此提供均一品質之黏著膜。As the fabrication of the cut die adhesion film of the present invention, no special apparatus or equipment is required and can be carried out using any of the typical methods known in the art. For example, the adhesive layer of the diced die adhesion film can be formed by: An acrylic copolymer, a polymerization initiator, a heat curing agent or the like is dissolved in a solvent such as methyl ethyl ketone or cyclohexanone, followed by fully kneading the product using a bead mill. Thereafter, the product is applied to a release treated polyethylene terephthalate (PET) film using an applicator, followed by drying in an oven at 100 ° C for 2 to 10 minutes, and then transferred to a polyolefin (PO). The film is thus formed into an adhesive film having an appropriate thickness. Thereafter, the adhesive film is subjected to an aging treatment in an oven at 25 to 40 ° C for 3 to 7 days, thereby providing a uniform quality adhesive film.

該黏著層較佳地具有厚度範圍從3μm至100μm，更佳地從5μm至30μm。在此範圍內，該黏著層具均一的黏著性，且確保生產該膜之經濟可行性。The adhesive layer preferably has a thickness ranging from 3 μm to 100 μm, more preferably from 5 μm to 30 μm. Within this range, the adhesive layer has a uniform adhesion and ensures the economic viability of producing the film.

如本發明之切割晶粒黏合膜之製造，不需要特別的裝置或設備，且可利用任何此技藝中已知典型的方法進行。As the fabrication of the cut die adhesion film of the present invention, no special apparatus or equipment is required and can be carried out using any of the methods generally known in the art.

該黏合層可用與該黏著層相同之方法製得。The adhesive layer can be produced in the same manner as the adhesive layer.

該黏合層較佳地具有厚度範圍從5μm至200μm，更佳地從10μm至100μm，又更佳地從15μm至60μm。The adhesive layer preferably has a thickness ranging from 5 μm to 200 μm, more preferably from 10 μm to 100 μm, still more preferably from 15 μm to 60 μm.

在此厚度範圍內，該黏合層可防止因不足的PCB(印刷電路板)間隙填充能力，而產生之封膠後孔隙特徵變差(其可能在當該黏合層具有過低厚度之情況下發生)，以及確保生產該膜之經濟可行性。Within this thickness range, the adhesive layer prevents the gap filling ability of the PCB (printed circuit board) from being insufficient, and the void characteristics after sealing are deteriorated (which may occur when the adhesive layer has an excessively low thickness) ), as well as ensuring the economic viability of producing the film.

本發明之另外的態樣提供一種半導體元件，其黏合至如本發明之切割晶粒黏合膜之黏合層。A further aspect of the invention provides a semiconductor component bonded to an adhesive layer of a diced die attach film of the present invention.

該半導體元件包括一配線基材；一黏合膜，其貼至該配線基材之晶片安裝平面；以及一半導體晶片，其安裝在該黏合膜上。該黏合膜意指如本發明之切割晶粒黏合 膜之黏合膜。The semiconductor component includes a wiring substrate; an adhesive film attached to the wafer mounting plane of the wiring substrate; and a semiconductor wafer mounted on the adhesive film. The adhesive film means the cut grain bonding as in the present invention Adhesive film of film.

在本發明中，該配線基材以及半導體晶片各可為任何一種此技藝中典型使用者。In the present invention, the wiring substrate and the semiconductor wafer may each be a typical user of this art.

如本發明之半導體元件可利用任何此技藝中已知典型的方法製成。Semiconductor components such as the present invention can be fabricated using any of the methods generally known in the art.

接著，參照下列範例將使得本發明變得更清楚，且應了解，下列範例僅供例示用，不能限制本發明的範疇，本發明之範疇僅受申請專利範以及其相等物之限制。The present invention will be more apparent from the following examples, and the following examples are intended to be illustrative only and not to limit the scope of the invention.

範例1Example 1 包括含羥基丙烯酸酯單體以及聚乙二醇(甲基)丙烯酸酯之黏著層之製備Preparation of an adhesive layer comprising a hydroxyl group-containing acrylate monomer and polyethylene glycol (meth) acrylate (1)丙烯酸共聚物之製備(1) Preparation of acrylic copolymer

在1L玻璃夾套反應器中先置入368g之醋酸乙酯作為有機溶劑，然後於其中置入138g之2-丙烯酸乙己酯、40g之丙烯酸2-羥乙酯、10g之甲基丙烯酸縮水甘油酯單體以及12g之聚乙二醇甲基丙烯酸酯。In a 1 L glass jacketed reactor, 368 g of ethyl acetate was first placed as an organic solvent, and then 138 g of 2-ethyl hexyl acrylate, 40 g of 2-hydroxyethyl acrylate, and 10 g of glycidyl methacrylate were placed therein. Monomer and 12 g of polyethylene glycol methacrylate.

之後，在反應器上裝上攪拌裝置。在該裝置之一部件上安裝回流冷凝器，在該裝置之另一部件上安裝氮補給線，藉此確保在反應後能夠連續補充氮氣3個小時。藉由連接至能夠控制溫度之夾套蒸餾水循環設備，將反應溫度調整至40℃，同時維持攪拌速度在150rpm下。當反應器內部之溫度維持在40℃下時，引入偶氮二異丁腈以及醋酸乙酯，調整固體含量在30%，如此獲得丙烯酸共聚物。Thereafter, a stirring device was attached to the reactor. A reflux condenser was installed on one of the components of the apparatus, and a nitrogen supply line was attached to another part of the apparatus, thereby ensuring continuous nitrogen gas replenishment for 3 hours after the reaction. The reaction temperature was adjusted to 40 ° C by being connected to a jacketed distilled water circulation apparatus capable of controlling the temperature while maintaining the stirring speed at 150 rpm. When the temperature inside the reactor was maintained at 40 ° C, azobisisobutyronitrile and ethyl acetate were introduced to adjust the solid content to 30%, thus obtaining an acrylic copolymer.

(2)用於切割晶粒黏合膜之黏著層之製備(2) Preparation of an adhesive layer for cutting a grain adhesion film

於以上製得之83.8g之丙烯酸共聚物中，加入25.8g之甲基乙基酮作為溶劑，以及8.8g之異氰酸酯固化劑(AK-75，可得自AEKYUNG CHEMICAL)作為熱固化劑，然後攪拌10分鐘，獲得具固體含量25%之黏著組成物。To 83.8 g of the acrylic copolymer prepared above, 25.8 g of methyl ethyl ketone was added as a solvent, and 8.8 g of an isocyanate curing agent (AK-75, available from AEKYUNG CHEMICAL) was used as a heat curing agent, followed by stirring. After 10 minutes, an adhesive composition having a solid content of 25% was obtained.

之後，利用塗佈器，將該黏著組成物施於離型劑處理的聚乙烯對苯二甲酸酯(PET)膜上，然後在100℃烤箱中乾燥8分鐘，如此該組成物可被轉移至聚烯烴(PO)膜上。之後，使該膜留在烤箱中，於40℃下進行老化，歷時5天，製得20μm厚之用於切割晶粒黏合膜之黏著層。Thereafter, the adhesive composition was applied to a release-treated polyethylene terephthalate (PET) film by an applicator, and then dried in an oven at 100 ° C for 8 minutes, so that the composition could be transferred. Onto the polyolefin (PO) film. Thereafter, the film was left in an oven and aged at 40 ° C for 5 days to obtain a 20 μm thick adhesive layer for cutting the die adhesion film.

範例2Example 2 包括含羥基丙烯酸酯單體以及聚乙二醇(甲基)丙烯酸酯之黏著層之製備Preparation of an adhesive layer comprising a hydroxyl group-containing acrylate monomer and polyethylene glycol (meth) acrylate

用與範例1中相同之方法製備用於切割晶粒黏合膜之黏著層，但添加132g之丙烯酸2-乙己酯以及18g之聚乙二醇甲基丙烯酸酯。An adhesive layer for cutting the die adhesion film was prepared in the same manner as in Example 1, except that 132 g of 2-ethylhexyl acrylate and 18 g of polyethylene glycol methacrylate were added.

範例3Example 3 包括含羥基丙烯酸酯單體以及聚乙二醇(甲基)丙烯酸酯之黏著層之製備Preparation of an adhesive layer comprising a hydroxyl group-containing acrylate monomer and polyethylene glycol (meth) acrylate

用與範例1中相同之方法製備用於切割晶粒黏合膜之黏著層，但添加132g之丙烯酸2-乙己酯以及18g之聚乙二醇甲基丙烯酸酯。An adhesive layer for cutting the die adhesion film was prepared in the same manner as in Example 1, except that 132 g of 2-ethylhexyl acrylate and 18 g of polyethylene glycol methacrylate were added.

範例4Example 4 包括含羥基丙烯酸酯單體、聚乙二醇(甲基)丙烯酸酯以及含磷丙烯酸酯單體之黏著層之製備Preparation of an adhesive layer comprising a hydroxyl group-containing acrylate monomer, a polyethylene glycol (meth) acrylate, and a phosphorus-containing acrylate monomer

用與範例1中相同之方法製備用於切割晶粒黏合膜之黏著層，但添加128g之丙烯酸2-乙己酯、12g之聚乙二醇甲基丙烯酸酯以及20g之包括含磷官能基團之丙烯酸酯單體。An adhesive layer for cutting the die adhesion film was prepared in the same manner as in Example 1, except that 128 g of 2-ethylhexyl acrylate, 12 g of polyethylene glycol methacrylate, and 20 g of a phosphorus-containing functional group were added. Acrylate monomer.

比較例1Comparative example 1 不含聚乙二醇(甲基)丙烯酸酯之黏著層之製備Preparation of adhesive layer without polyethylene glycol (meth) acrylate

用與範例1中相同之方法製備用於切割晶粒黏合膜之黏著層，但添加150g之丙烯酸2-乙己酯，沒有使用聚乙二醇甲基丙烯酸酯。An adhesive layer for cutting the die adhesion film was prepared in the same manner as in Example 1, except that 150 g of 2-ethylhexyl acrylate was added without using polyethylene glycol methacrylate.

比較例2Comparative example 2 不含聚乙二醇(甲基)丙烯酸酯之黏著層之製備Preparation of adhesive layer without polyethylene glycol (meth) acrylate

用與範例1中相同之方法製備用於切割晶粒黏合膜之黏著層，但引入142g之丙烯酸2-乙己酯，使用48g之丙烯酸2-羥乙酯，沒有使用聚乙二醇甲基丙烯酸酯。An adhesive layer for cutting the die adhesion film was prepared in the same manner as in Example 1, but 142 g of 2-ethylhexyl acrylate was introduced, and 48 g of 2-hydroxyethyl acrylate was used without using polyethylene glycol methacrylate. .

表1以及表2總結依照範例1至4以及比較例1與2之丙烯 酸共聚物之組成物(重量份)Table 1 and Table 2 summarize the propylene according to Examples 1 to 4 and Comparative Examples 1 and 2. Composition of acid copolymer (parts by weight)

比較例1Comparative example 1 黏著層與黏合層間之黏著強度之測量Measurement of adhesion strength between adhesive layer and adhesive layer

為測量範例1至4以及比較例1與2中製得之黏著層每一個之黏著強度，依照No.8 of KS-A-01107(黏著帶與黏著板之實驗方法)測量黏著層與黏合層間之剝離力。To measure the adhesion strength of each of the adhesive layers prepared in Examples 1 to 4 and Comparative Examples 1 and 2, the adhesion layer and the adhesive layer were measured in accordance with No. 8 of KS-A-01107 (Experimental Method of Adhesive Tape and Adhesive Plate). Peeling force.

將各黏著層試樣(寬25mm、長250mm)貼至供用於習知切割晶粒黏合膜之黏合層(Cheil Industries)，使用2kg負載輥，以300mm/min之速度前後壓一次。壓製後30分鐘，將試樣轉180°，剝除至約25mm處，然後固定至荷重元10N之拉伸強度測試器之上鉗口，黏合層固定至其下鉗口。之後，使用Instron Series 1X/s Automated Materials Tester-3343，測量該層在300mm/min之拉伸速度下被剝離時之負載。Each of the adhesive layer samples (width 25 mm, length 250 mm) was attached to a bonding layer (Cheil Industries) for conventional cutting of the die adhesion film, and was pressed back and forth at a speed of 300 mm/min using a 2 kg load roller. Thirty minutes after pressing, the sample was rotated 180°, stripped to about 25 mm, and then fixed to the jaws of the tensile strength tester of 10N load, and the adhesive layer was fixed to the lower jaw. Thereafter, the load of the layer when peeled off at a tensile speed of 300 mm/min was measured using an Instron Series 1X/s Automated Materials Tester-3343.

實驗範例2Experimental example 2 黏著層以及環形框架間黏著性之測量Adhesive layer and measurement of adhesion between annular frames

為測量範例1至4以及比較例1與2中製得之各黏著層之黏著強度，依照下列方法測量黏著層以及環形框架間之剝離力。To measure the adhesion strength of each of the adhesive layers prepared in Examples 1 to 4 and Comparative Examples 1 and 2, the peeling force between the adhesive layer and the annular frame was measured in accordance with the following method.

以與實驗範例1相同之方法測量黏著層與環形框架間之剝離力，但該黏著層係貼至環形框架，而不是黏合層。The peeling force between the adhesive layer and the annular frame was measured in the same manner as in Experimental Example 1, but the adhesive layer was attached to the annular frame instead of the adhesive layer.

實驗範例3Experimental example 3

測定在切割時是否會發生水滲透[0103]為測定包括範例1至4以及比較例1與2中製得之各黏著層之切割晶圓黏合膜之切割期間，是否會發生水滲透(測定水是否穿入環形框架與黏著層之間)，在此實驗中製備10個樣本。It is determined whether or not water permeation occurs during cutting [0103] Whether water permeation occurs during the cutting of the cut wafer adhesive film including each of the adhesive layers prepared in Examples 1 to 4 and Comparative Examples 1 and 2 (measurement of water) Whether to penetrate between the annular frame and the adhesive layer, 10 samples were prepared in this experiment.

將習知黏合層(Cheil Industries)放在範例1至4以及比較例1與2中製得之各黏著層上，獲得切割晶粒黏合膜。於該切割晶粒黏合膜上，在60℃下熱壓80μm厚之矽晶圓10秒，之後使用EFD-650(DISCO Company)切割處理成尺寸8.97mm寬x9.715mm高。切割期間，注入水或空氣。A conventional adhesive layer (Cheil Industries) was placed on each of the adhesive layers prepared in Examples 1 to 4 and Comparative Examples 1 and 2 to obtain a cut grain adhesion film. On the diced die adhesion film, a 80 μm thick ruthenium wafer was heat-pressed at 60 ° C for 10 seconds, and then cut into a size of 8.97 mm wide by 9.715 mm high using EFD-650 (DISCO Company). Inject water or air during cutting.

評估水滲透之發生，當所有的樣本沒有顯示出任何水滲透時，評估為“無”，當在樣本之任一個中發現水滲透時，評估為“有”。The occurrence of water infiltration was assessed and evaluated as "None" when all samples did not show any water infiltration, and "Yes" when water infiltration was found in any of the samples.

實驗範例4Experimental example 4 拾取成功率之測定Determination of the success rate of picking

為測定包括範例1至4以及比較例1與2中製得之各黏著層之切割晶粒黏合膜之切割過程後之拾取成功率， 依照下列方法進行實驗。In order to determine the picking success rate after the cutting process of the cut grain bonding film including each of the adhesive layers prepared in Examples 1 to 4 and Comparative Examples 1 and 2, Experiment with the following methods.

使用晶粒黏合器SDB-10M(Mechatronics)，在100個位於矽晶圓之中央部份上之晶片上進行拾取測試，測量成功率(%)。在拾取測試中，測量銷之衝擊(升高之高度)。當能夠在低衝擊下進行拾取時，拾取性能為良好。A pick-up test was performed on 100 wafers on the central portion of the wafer using a die bonder SDB-10M (Mechatronics), and the success rate (%) was measured. In the pick-up test, the impact of the pin (the height of the rise) is measured. When the pickup can be performed under a low impact, the pickup performance is good.

此外，切割後，用肉眼觀察環形框架與黏著層貼合之部分，決定水滲透是否發生。In addition, after cutting, the portion of the annular frame that adheres to the adhesive layer is visually observed to determine whether water penetration has occurred.

表3以及4總結實驗範例1至4之結果。Tables 3 and 4 summarize the results of Experimental Examples 1 to 4.

概略而言，黏著層對黏合層之剝離力與黏著層對環形框架之剝離力間之差超過0.1N/25mm，且對黏合層之剝離力較高。據此，當在無UV照射之情況下對黏合層提供 所欲的剝離力時，亦可能會降低對環形框架之剝離力，從而引起在切割時諸如環形框架分離和/或水滲透之問題。In summary, the difference between the peeling force of the adhesive layer to the adhesive layer and the peeling force of the adhesive layer to the annular frame exceeds 0.1 N/25 mm, and the peeling force to the adhesive layer is high. According to this, when the adhesive layer is provided without UV irradiation The desired peel force may also reduce the peel force on the annular frame, causing problems such as annular frame separation and/or water penetration during cutting.

如表3以及4中所示，可見到依照範例1至4之黏著層顯示，對黏合層之剝離力與對環形框架之剝離力間之比率為1.3或更小，其產生良好的拾取性能，同時在與環形框架沒有產生任何分離以及沒有水滲透之情況下，維持對環形框架之黏著性。As shown in Tables 3 and 4, it can be seen that the adhesive layers according to Examples 1 to 4 show that the ratio of the peeling force to the adhesive layer to the peeling force to the annular frame is 1.3 or less, which produces good pick-up performance. At the same time, the adhesion to the annular frame is maintained without any separation from the annular frame and without water penetration.

結果可見，範例1至4之黏著層，在低衝擊下顯示出比比較例1與2之黏著層好的拾取成功率。As a result, it can be seen that the adhesive layers of Examples 1 to 4 exhibited a better pick-up success rate than the adhesive layers of Comparative Examples 1 and 2 under low impact.

同時，雖然比較例2之黏著層顯示良好的拾取性能，但在切割期間，可見到由於對環形框架之剝離力減少而產生之水滲透。Meanwhile, although the adhesive layer of Comparative Example 2 showed good pick-up performance, water penetration due to a decrease in peeling force to the annular frame was observed during cutting.

雖然上文中描述一些具體例，但對熟悉此技藝之人士而言，此等具體例僅為例示之用途，且在不逸離本發明之技術思想之情況下，可製得各種改質物、變化、改變以及相等具體例。本發明之範疇應僅受所附之申請專利範圍以及其相等物之限制。Although a few specific examples are described above, those skilled in the art will be able to make various modifications and changes without departing from the technical idea of the present invention. , change, and equal specific examples. The scope of the invention should be limited only by the scope of the appended claims and their equivalents.

Claims (11)

一種非UV型切割晶粒黏合膜，其包含丙烯酸共聚物以及熱固化劑，其中該丙烯酸共聚物包含：以該丙烯酸共聚物100重量份為基準，55重量份至95重量份之丙烯酸烷基酯單體；5重量份至30重量份之含羥基基團之丙烯酸酯單體；以及1重量份至15重量份之聚乙二醇(甲基)丙烯酸酯。 A non-UV type dicing die bond film comprising an acrylic copolymer and a heat curing agent, wherein the acrylic copolymer comprises: 55 parts by weight to 95 parts by weight of an alkyl acrylate based on 100 parts by weight of the acrylic copolymer Monomer; 5 parts by weight to 30 parts by weight of the hydroxy group-containing acrylate monomer; and 1 part by weight to 15 parts by weight of the polyethylene glycol (meth) acrylate. 如申請專利範圍第1項之非UV型切割晶粒黏合膜，其中該含羥基基團之丙烯酸酯單體以及該聚乙二醇(甲基)丙烯酸酯存在之總量，以該丙烯酸共聚物100重量份為基準，為20重量份至40重量份。 The non-UV type dicing die-bonding film of claim 1, wherein the hydroxy group-containing acrylate monomer and the polyethylene glycol (meth) acrylate are present in a total amount, the acrylic copolymer It is 20 parts by weight to 40 parts by weight based on 100 parts by weight. 一種非UV型切割晶粒黏合膜，其包含：一黏著層，其含有丙烯酸共聚物；以及一黏合層，其疊在該黏著層上，其中，該丙烯酸共聚物包含含羥基基團之丙烯酸酯單體以及聚乙二醇(甲基)丙烯酸酯；以及其中，該黏著層對環形框架之黏著強度(x)為0.25N/25mm或更大，以及對黏合層之黏著強度(y)與對環形框架之黏著強度(x)之比率(y/x)為大於0至1.3。 A non-UV type dicing die bonding film comprising: an adhesive layer containing an acrylic copolymer; and an adhesive layer superposed on the adhesive layer, wherein the acrylic copolymer comprises a hydroxyl group-containing acrylate a monomer and a polyethylene glycol (meth) acrylate; and wherein the adhesive layer has an adhesion strength (x) to the annular frame of 0.25 N/25 mm or more, and adhesion strength (y) to the adhesive layer The ratio (y/x) of the adhesive strength (x) of the annular frame is greater than 0 to 1.3. 如申請專利範圍第3項之非UV型切割晶粒黏合膜，其中該黏著層對黏合層之黏著強度(y)與對環形框架之黏著強度(x)之比率(y/x)為0.76至1.3。 The non-UV type cutting grain adhesive film of claim 3, wherein the ratio of the adhesion strength (y) of the adhesive layer to the adhesive layer and the adhesion strength (x) to the annular frame (y/x) is 0.76. 1.3. 如申請專利範圍第3項之非UV型切割晶粒黏合膜，其中該黏著層具有對環形框架之黏著強度(x)，大於對黏合層之黏著強度(y)(x>y)。 The non-UV type cutting grain adhesive film according to claim 3, wherein the adhesive layer has an adhesive strength (x) to the annular frame, and is greater than an adhesive strength (y) (x>y) of the adhesive layer. 如申請專利範圍第1至5項中任一項之非UV型切割晶粒黏合膜，其中該聚乙二醇(甲基)丙烯酸酯可以式1表示： 其中n是從2至40之整數。The non-UV type dicing die-bonding film according to any one of claims 1 to 5, wherein the polyethylene glycol (meth) acrylate can be represented by Formula 1: Wherein n is an integer from 2 to 40. 如申請專利範圍第1至5項中任一項之非UV型切割晶粒黏合膜，其中該丙烯酸共聚物進一步包含一包括含磷官能基團之丙烯酸酯單體。 The non-UV type dicing die-bonding film according to any one of claims 1 to 5, wherein the acrylic copolymer further comprises an acrylate monomer comprising a phosphorus-containing functional group. 如申請專利範圍第7項之非UV型切割晶粒黏合膜，其中該包括含磷官能基團之丙烯酸酯單體存在之數量，以該丙烯酸共聚物100重量份為基準，大於0重量份至20重量份。 The non-UV type dicing die-bonding film according to claim 7, wherein the acrylate monomer having a phosphorus-containing functional group is present in an amount of more than 0 parts by weight based on 100 parts by weight of the acrylic copolymer. 20 parts by weight. 如申請專利範圍第1至5項中任一項之非UV型切割晶粒黏合膜，其中該丙烯酸共聚物進一步包含一含環氧基團之丙烯酸酯單體。 The non-UV type dicing die-bonding film according to any one of claims 1 to 5, wherein the acrylic copolymer further comprises an epoxy group-containing acrylate monomer. 如申請專利範圍第9項之非UV型切割晶粒黏合膜，其中該含環氧基團之丙烯酸酯單體存在之數量，以該丙烯酸共聚物100重量份為基準，大於0重量份至10重量份。 The non-UV type dicing die-bonding film according to claim 9, wherein the epoxy group-containing acrylate monomer is present in an amount of more than 0 parts by weight to 10 parts by weight based on 100 parts by weight of the acrylic copolymer. Parts by weight. 一種半導體元件，其包括：一配線基材；一黏合膜，其貼至該配線基材之晶片安裝表面；以及 一半導體晶片，其安裝在該黏合膜上，其中該黏合膜係如申請專利範圍第1或3項之非UV型切割晶粒黏合膜之黏合層。 A semiconductor component comprising: a wiring substrate; an adhesive film attached to a wafer mounting surface of the wiring substrate; A semiconductor wafer mounted on the adhesive film, wherein the adhesive film is an adhesive layer of a non-UV type dicing die bonding film according to claim 1 or 3.
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