TWI469204B - A polishing method for a semiconductor wafer, and a resin composition and a protective sheet used therefor - Google Patents

A polishing method for a semiconductor wafer, and a resin composition and a protective sheet used therefor Download PDF

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TWI469204B
TWI469204B TW97123071A TW97123071A TWI469204B TW I469204 B TWI469204 B TW I469204B TW 97123071 A TW97123071 A TW 97123071A TW 97123071 A TW97123071 A TW 97123071A TW I469204 B TWI469204 B TW I469204B
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semiconductor wafer
acrylate
meth
polishing
resin composition
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TW97123071A
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TW200917353A (en
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Masanobu Kutsumi
Tomoyuki Kanai
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Denki Kagaku Kogyo Kk
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • 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
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78—Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
    • 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
    • H01L2221/6834—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 to protect an active side of a device or wafer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68381—Details of chemical or physical process used for separating the auxiliary support from a device or wafer
    • H01L2221/68386—Separation by peeling
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01004—Beryllium [Be]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01019—Potassium [K]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/095—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
    • H01L2924/097—Glass-ceramics, e.g. devitrified glass
    • H01L2924/09701—Low temperature co-fired ceramic [LTCC]

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Description

半導體晶圓之研磨方法及使用於其之樹脂組成物及保護薄片Method for polishing semiconductor wafer and resin composition and protective sheet used therefor

本發明係關於一種半導體晶圓研磨方法與使用其而適宜的樹脂組成物及保護薄片或固定用治具。The present invention relates to a semiconductor wafer polishing method and a resin composition and a protective sheet or a fixture for use thereof.

藉由IC卡、行動電話、及PDA(Personal Digital Assistants)等之電子機器的薄型化等，俾於此等電子機器的製造中之研磨技術的重要性被廣泛認知。研磨步驟中係尋求一種可確實地固定被加工物。固定被加工物之方法之一已知有使用黏著薄片之方法(參照專利文獻1)。The importance of the polishing technology in the manufacture of such electronic devices is widely recognized by the thinning of electronic devices such as IC cards, mobile phones, and PDAs (Personal Digital Assistants). In the grinding step, a kind of workpiece which can be surely fixed is sought. One method of fixing a workpiece is known as a method of using an adhesive sheet (see Patent Document 1).

但，若研磨晶圓至很薄，晶圓之強度會降低，故若於晶圓內稍具有缺陷，則產生龜裂，降低良率。為抑制此等之破損，故於半導體晶圓的電路側面形成特定深度的溝後，從背面側進行研磨，分割成晶片狀之方法已被提示(參照專利文獻2)。However, if the wafer is polished to a very small thickness, the strength of the wafer is lowered. Therefore, if there is a slight defect in the wafer, cracks are generated and the yield is lowered. In order to suppress such damage, a method of forming a groove having a certain depth on the side surface of the semiconductor wafer and polishing it from the back side to divide into a wafer shape has been proposed (see Patent Document 2).

製造電子零件時，在其中途步驟中，於矽或鎵－砷等之半導體晶圓上形成電路圖型而成之電子零件集合體、或於平板狀之絕緣基板等形成電路圖型而成之電子零件集合體的情形很多。於半導體晶圓上形成電路圖型而成之電子零件集合體中係於矽晶圖上附30μm左右的電路的晶圓或晶圓尺寸CSP(Chip Size Package)等為代表且具有30~500μm的凸塊者很多。In the case of manufacturing an electronic component, an electronic component assembly in which a circuit pattern is formed on a semiconductor wafer such as tantalum or gallium-arsenic, or an electronic component in which a circuit pattern is formed on a flat insulating substrate or the like in a middle step There are many situations in the assembly. The electronic component assembly in which the circuit pattern is formed on the semiconductor wafer is represented by a wafer or a wafer size CSP (Chip Size Package) having a circuit of about 30 μm on the twin crystal image, and has a convexity of 30 to 500 μm. There are many people in the block.

在使用習知黏著薄片之研磨中，若使用具有30μm以上之凹凸的電子零件集合體，於凹凸之追蹤性不足，於電 子零件集合體施加應力，故有時研磨部產生凹陷或龜裂。In the polishing using the conventional adhesive sheet, if an electronic component assembly having irregularities of 30 μm or more is used, the tracking property of the unevenness is insufficient, and the electricity is insufficient. Since the sub-part assembly is subjected to stress, the polishing portion may be sag or cracked.

對於具有50μm以上之凹凸的電子零件集合體，係考慮於凹凸之追蹤性而使用比較柔軟的基材薄膜之情形很多(參照專利文獻3)，進行研磨，分割成各晶片時，係成為所分割之晶片移動、晶片缺角或拾取不良的原因。In the electronic component assembly having a thickness of 50 μm or more, a relatively soft base film is used in consideration of the tracking property of the unevenness (see Patent Document 3), and the film is divided into individual wafers to be divided. The reason for wafer movement, wafer notch or poor pickup.

為解決前述問題，對於晶圓、光學零件之電路面凹凸之追蹤性為充分存在的材料，且作為研磨時之支撐體而形成具有非常剛性之組成物，含有具特定之(甲基)丙烯酸單體的樹脂之樹脂組成物已被提出(專利文獻4、5)。在專利文獻4、5中係記載著上述樹脂組成物係於背面研磨時之表面保護上很有效，但有關在氧環境下進行硬化係未記載。In order to solve the above problems, the tracking property of the surface roughness of the wafer and the optical component is a sufficient material, and a very rigid composition is formed as a support during polishing, and a specific (meth)acrylic acid is contained. A resin composition of a bulk resin has been proposed (Patent Documents 4 and 5). In Patent Documents 4 and 5, it is described that the resin composition is effective for surface protection during back surface polishing, but it is not described in the case of curing in an oxygen atmosphere.

專利文獻1：特開昭61－010242號公報專利文獻2：特開平05－335411號公報專利文獻3：特許第3773358號公報專利文獻4：國際公開WO2007/004620手冊專利文獻5：國際公開WO2006/100788手冊、Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 100788 manual,

本發明之目的在於提供一種研磨加工時之凹凸追蹤性及分割成各晶片時之晶片保持性優，不產生晶片缺角或拾取不良，而與半導體晶圓之黏著性，剝離性優之構件、加工方法；尤其，目的在於提供一種半導體晶圓的新研磨方法，其係在習知技術中無法對應，且於電路面具有30μm 以上大的凹凸之半導體晶圓背面進行研磨而薄壁化。An object of the present invention is to provide a structure which is excellent in peeling property during polishing processing, excellent in wafer retention property when being divided into wafers, and which does not cause wafer chipping or picking failure, and which has adhesion to a semiconductor wafer and excellent releasability. Processing method; in particular, an object is to provide a new polishing method for a semiconductor wafer which is not compatible in the prior art and has 30 μm on the circuit surface The back surface of the above-mentioned large uneven semiconductor wafer is polished and thinned.

(1)一種半導體晶圓之研磨方法，其特徵在於：半導體晶圓之電路面(表面)側介由可從前述半導體晶圓剝離之樹脂層而設有保護薄片或固定用治具，研磨前述半導體晶圓之背面。(1) A method of polishing a semiconductor wafer, characterized in that a circuit surface (surface) side of a semiconductor wafer is provided with a protective sheet or a fixing jig via a resin layer peelable from the semiconductor wafer, and the foregoing The back side of the semiconductor wafer.

(2)如上述(1)項之半導體晶圓之研磨方法，其中於半導體晶圓之電路面側形成較晶圓厚度更淺之深度的溝，使形成樹脂層之樹脂組成物全面地塗佈，研磨前述半導體晶圓之背面而分割成各個晶片。(2) The method of polishing a semiconductor wafer according to the above item (1), wherein a groove having a shallower depth than a wafer is formed on a circuit surface side of the semiconductor wafer, and the resin composition forming the resin layer is entirely coated. The back surface of the semiconductor wafer is ground and divided into individual wafers.

(3)如上述(1)或(2)項之半導體晶圓之研磨方法，其中於研磨半導體晶圓之背面之後，加熱樹脂層而除去。(3) The method of polishing a semiconductor wafer according to the above (1) or (2), wherein after polishing the back surface of the semiconductor wafer, the resin layer is heated and removed.

(4)如上述(3)項之半導體晶圓之研磨方法，其中至少使樹脂層加熱至40~150℃，以除去樹脂層。(4) The method of polishing a semiconductor wafer according to the above (3), wherein at least the resin layer is heated to 40 to 150 ° C to remove the resin layer.

(5)如上述(1)~(3)項中任一項的半導體晶圓之研磨方法，其中至少使樹脂層接觸於30~100℃之溫水，以除去樹脂層。(5) The method of polishing a semiconductor wafer according to any one of the items (1) to (3), wherein at least the resin layer is brought into contact with warm water of 30 to 100 ° C to remove the resin layer.

(6)如上述(1)~(5)項中任一項的半導體晶圓之研磨方法，其中保護薄片或固定用治具為光透過性，樹脂層為由丙烯酸系樹脂組成物所構成。(6) The method of polishing a semiconductor wafer according to any one of the above (1) to (5), wherein the protective sheet or the fixing jig is light transmissive, and the resin layer is composed of an acrylic resin composition.

(7)如上述(1)~(6)項中任一項的半導體晶圓之研磨方法，其中半導體晶圓為於電路面具有30μm以上1000μm以下之凹凸。(7) The method of polishing a semiconductor wafer according to any one of (1) to (6), wherein the semiconductor wafer has irregularities of 30 μm or more and 1000 μm or less on the circuit surface.

(8)如上述(6)或(7)項之半導體晶圓之研磨方法，其中固定用治具為透過波長365nm之光20%以上者。(8) The method of polishing a semiconductor wafer according to the above (6) or (7), wherein the fixing jig is 20% or more of light having a wavelength of 365 nm.

(9)一種樹脂組成物，其係使用於如上述(1)~(7)項中任一項的半導體晶圓之研磨方法。(9) A resin composition for use in a method of polishing a semiconductor wafer according to any one of the above items (1) to (7).

(10)如上述(9)項之樹脂組成物，其中含有(A)多官能(甲基)丙烯酸酯、(B)單官能(甲基)丙烯酸酯及(C)聚合起始劑，相對於(A)與(B)之合計量100質量份，含有(B)50~97質量份，(C)0.1~20質量份。(10) A resin composition according to the above item (9), which comprises (A) a polyfunctional (meth) acrylate, (B) a monofunctional (meth) acrylate, and (C) a polymerization initiator, with respect to 100 parts by mass of (A) and (B) are contained, and (B) is 50 to 97 parts by mass, and (C) is 0.1 to 20 parts by mass.

(11)如上述(10)項之樹脂組成物，其中前述(A)及(B)皆為疏水性。(11) A resin composition according to the above item (10), wherein the above (A) and (B) are both hydrophobic.

(12)如上述(10)或(11)項之樹脂組成物，其中前述(C)為光聚合起始劑。(12) A resin composition according to the above (10) or (11), wherein the above (C) is a photopolymerization initiator.

(13)一種保護薄片，其係使用於如上述(1)~(7)項中任一項的半導體晶圓之研磨方法。(13) A protective sheet for use in a method of polishing a semiconductor wafer according to any one of the above items (1) to (7).

(14)如上述(13)項之保護薄片，其中含有至少一層以上由乙烯－乙酸乙烯酯所構成之層。(14) A protective sheet according to the above item (13), which contains at least one layer of a layer composed of ethylene-vinyl acetate.

(15)如上述(13)或(14)項之保護薄片，其中於表面具有黏著層。(15) A protective sheet according to the above item (13) or (14), which has an adhesive layer on the surface.

(16)如上述(15)項之保護薄片，其中黏著層為由丙烯酸系樹脂組成物所構成。(16) A protective sheet according to the above item (15), wherein the adhesive layer is composed of an acrylic resin composition.

本發明之半導體晶圓研磨方法與使用其的樹脂組成物係發揮如下效果：於電路面具有30~1000μm進而具有 30~500μm，尤其具有30~50μm之凹凸(凸塊)之半導體晶圓的研磨加工時之凹凸追蹤性及分割成各晶片時之晶片保持性優，不產生晶片缺角或拾取不良，而作業環境上亦優。The semiconductor wafer polishing method of the present invention and the resin composition using the same have an effect of having 30 to 1000 μm on the circuit surface and further having 30 to 500 μm, in particular, a semiconductor wafer having irregularities (bumps) of 30 to 50 μm is excellent in unevenness in polishing processing and excellent in wafer retention when being divided into wafers, and does not cause chipping or picking failure. The environment is also excellent.

用以實施發明之最佳形態The best form for implementing the invention (樹脂層)(resin layer)

本發明之樹脂層係以下詳述之樹脂組成物進行硬化所得到者。本發明所使用之樹脂組成物係進行硬化所得到之樹脂層藉加熱，或藉由有機溶劑或與水之接觸俾容易地從半導體晶圓剝離之性質者，進一步此時宜與保護薄片不剝離者。其中，藉加熱進行剝離者或與水之接觸進行剝離者，皆相較於使用有機溶劑之剝離方法，不須更大的設備，作業環境上亦優，故較宜選擇。The resin layer of the present invention is obtained by curing the resin composition described in detail below. The resin composition used in the present invention is a resin layer obtained by hardening, or is easily peeled off from the semiconductor wafer by an organic solvent or contact with water, and further preferably is not peeled off from the protective sheet at this time. . Among them, the person who peels off by heating or the contact with water, compared with the peeling method using an organic solvent, does not require a larger apparatus, and is also excellent in the working environment, so it is preferable to select.

就前述樹脂組成物而言可舉例如丙烯酸系樹脂組成物，尤其，宜為使(A)多官能(甲基)丙烯酸酯與(B)單官能(甲基)丙烯酸酯適當調配之丙烯酸系樹脂組成物。又，總稱丙烯酸酯及甲基丙烯酸酯為(甲基)丙烯酸酯。The resin composition may, for example, be an acrylic resin composition, and particularly preferably an acrylic resin which is suitably formulated with (A) a polyfunctional (meth) acrylate and (B) a monofunctional (meth) acrylate. Composition. Further, the acrylate and methacrylate are collectively referred to as (meth) acrylate.

(A)多官能(甲基)丙烯酸酯係可使用於寡聚物/聚合物末端或側鏈具有2個以上(甲基)丙烯醯基化之多官能(甲基)丙烯酸酯的寡聚物/聚合物或2個以上之(甲基)丙烯醯基的單體。(A) Polyfunctional (meth) acrylate is an oligomer which can be used for polyfunctional (meth) acrylate having two or more (meth) propylene thiolated at the end of the oligomer/polymer or side chain. / polymer or more than 2 (meth) propylene fluorenyl monomers.

多官能(甲基)丙烯酸酯的寡聚物/聚合物係可舉例如1,2-聚丁二烯末端胺基甲酸酯(甲基)丙烯酸酯(例如日本曹達公司製TE-2000、TEA-1000)、前述氫添加物(例如日 本曹達公司製TEAI－1000)、1,4－聚丁二烯末端胺基甲酸酯(甲基)丙烯酸酯(例如，大阪有機化學公司製BAC－45)、聚異戊二烯末端(甲基)丙烯酸酯、聚酯系胺基甲酸酯(甲基)丙烯酸酯、聚醚系胺基甲酸酯(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、雙酚A型環氧(甲基)丙烯酸酯(例如大阪有機化學公司製Biscote #540、昭和高分子公司製Biscote VR－77)、胺基甲酸酯(甲基)丙烯酸酯(例如日本合成化學公司製UV－3000B)等。The polyfunctional (meth) acrylate oligomer/polymer system may, for example, be a 1,2-polybutadiene terminal urethane (meth) acrylate (for example, TE-2000, TEA, manufactured by Nippon Soda Co., Ltd.) -1000), the aforementioned hydrogen additive (for example, day TEA-1000), 1,4-polybutadiene terminal urethane (meth) acrylate (for example, BAC-45, Osaka Organic Chemical Co., Ltd.), polyisoprene terminal (A) Acrylate, polyester urethane (meth) acrylate, polyether urethane (meth) acrylate, polyester (meth) acrylate, bisphenol A epoxy (Meth) acrylate (for example, Biscote #540 by Osaka Organic Chemical Co., Ltd., Biscote VR-77 by Showa Polymer Co., Ltd.), and urethane (meth) acrylate (for example, UV-3000B manufactured by Nippon Synthetic Chemical Co., Ltd.) Wait.

2官能(甲基)丙烯酸酯單體可舉例如1,3－丁二醇二(甲基)丙烯酸酯、1,4－丁二醇二(甲基)丙烯酸酯、1,6－己二醇二(甲基)丙烯酸酯、1,9－壬二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、二環戊基二(甲基)丙烯酸酯、2－乙基－2－丁基－丙二醇(甲基)丙烯酸酯、新戊二醇改性三羥甲基丙烷二(甲基)丙烯酸酯、硬脂酸改性季戊四醇二丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、2,2－雙(4－(甲基)丙烯醯基二乙氧基苯基)丙烷、2,2－雙(4－(甲基)丙烯醯基丙氧基苯基)丙烷、2,2－雙(4－(甲基)丙烯醯基四乙氧基苯基)丙烷、二環癸基二(甲基)丙烯酸酯等。The bifunctional (meth) acrylate monomer may, for example, be 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate or 1,6-hexanediol. Di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dicyclopentyl di(meth)acrylate, 2-B Base-2-butyl-propylene glycol (meth) acrylate, neopentyl glycol modified trimethylolpropane di(meth) acrylate, stearic acid modified pentaerythritol diacrylate, polypropylene glycol di(methyl) Acrylate, 2,2-bis(4-(methyl)propenyldiethoxyphenyl)propane, 2,2-bis(4-(methyl)propenylpropenyloxyphenyl)propane 2,2-bis(4-(methyl)acrylonitrile-tetraethoxyphenyl)propane, bicyclononyl di(meth)acrylate, and the like.

3官能(甲基)丙烯酸酯單體可舉例如三羥甲基丙烷三(甲基)丙烯酸酯、三[(甲基)丙烯醯氧基乙基]三聚異氰酸酯等。The trifunctional (meth) acrylate monomer may, for example, be trimethylolpropane tri(meth)acrylate or tris[(meth)acryloxyethyl]polyisocyanate.

4官能以上之(甲基)丙烯酸酯單體可舉例如二羥甲基丙烷四(甲基)丙烯酸酯、季戊四醇二丙烯酸酯四(甲基)丙烯酸酯、季戊四醇乙氧基四(甲基)丙烯酸酯、二季戊四醇 五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等。The tetrafunctional or higher (meth) acrylate monomer may, for example, be dimethylolpropane tetra(meth) acrylate, pentaerythritol diacrylate tetra(meth) acrylate, pentaerythritol ethoxy tetra(meth) acrylate. Ester, dipentaerythritol Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

(A)多官能(甲基)丙烯酸酯係更宜為疏水性者。疏水性之多官能(甲基)丙烯酸酯謂不具有羥基之(甲基)丙烯酸酯。如此地，水溶性之情形係研磨加工時樹脂組成物之硬化體進行膨潤俾引起位移，恐加工精度差。即使為親水性，若非其樹脂組成物之硬化體受水而很大膨潤或一部分溶解，即使使用亦無妨。(A) The polyfunctional (meth) acrylate is more preferably hydrophobic. A hydrophobic polyfunctional (meth) acrylate is a (meth) acrylate having no hydroxyl group. As described above, in the case of water solubility, the hardened body of the resin composition at the time of polishing is subjected to swelling and causing displacement, which may result in poor processing accuracy. Even if it is hydrophilic, if the hardened body which is not a resin composition is swollen or partially dissolved by water, it may be used even if it is used.

(A)多官能(甲基)丙烯酸酯之添加量係(A)及後述之(B)單官能(甲基)丙烯酸酯的合計量100質量份中，宜為3~50質量份，更宜為10~30質量份。若為3質量份以上，加熱樹脂組成物之硬化體時可充分助長從被黏物剝離該硬化體之性質(以下，僅稱為「剝離性」)，且可確保呈膜狀剝離樹脂組成物之硬化體。又，若為50質量份以下，亦無初期之黏著性降低之虞。(A) The amount of the polyfunctional (meth) acrylate to be added is preferably from 3 to 50 parts by mass, more preferably from 3 to 50 parts by mass, based on 100 parts by mass of the total of (A) and (B) monofunctional (meth) acrylate described later. It is 10 to 30 parts by mass. When it is 3 parts by mass or more, when the cured body of the resin composition is heated, the property of peeling off the hardened body from the adherend (hereinafter, simply referred to as "peelability") can be sufficiently promoted, and the film-like peeling resin composition can be ensured. Hardened body. Moreover, if it is 50 mass parts or less, there is no fall of the initial adhesiveness.

(B)單官能(甲基)丙烯酸酯的單體可舉例如甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、丙基(甲基)丙烯酸酯、丁基(甲基)丙烯酸酯、2－乙基己基(甲基)丙烯酸酯、異辛基(甲基)丙烯酸酯、異癸基(甲基)丙烯酸酯、月桂基(甲基)丙烯酸酯、硬脂基(甲基)丙烯酸酯、苯基(甲基)丙烯酸酯、環己基(甲基)丙烯酸酯、二環戊基(甲基)丙烯酸酯、二環戊烯基(甲基)丙烯酸酯、二環戊烯氧乙基(甲基)丙烯酸酯、異冰片基(甲基)丙烯酸酯、甲氧基化環癸三烯(甲基)丙烯酸酯、2－羥基乙基(甲基)丙烯酸酯、2－羥基丙基(甲基)丙烯酸酯、3－羥丙基(甲基)丙烯酸酯、4－羥丁基(甲基)丙 烯酸酯、四氫糠基(甲基)丙烯酸酯、2－羥基－3－苯氧基丙基(甲基)丙烯酸酯、縮水甘油基(甲基)丙烯酸酯、己內酯改性四氫糠基(甲基)丙烯酸酯、3－氯－2－羥基丙基(甲基)丙烯酸酯、N,N－二甲基胺基乙基(甲基)丙烯酸酯、N,N－二乙基胺基乙基(甲基)丙烯酸酯、第三丁基胺基乙基(甲基)丙烯酸酯、乙氧基羰基甲基(甲基)丙烯酸酯、酚環氧乙烷改性丙烯酸酯、酚(環氧乙烷2莫耳改性)丙烯酸酯、酚(環氧乙烷4莫耳改性)丙烯酸酯、對枯基酚環氧乙烷改性丙烯酸酯、壬基酚環氧乙烷改性丙烯酸酯、壬基酚(環氧乙烷4莫耳改性)丙烯酸酯、壬基酚(環氧乙烷8莫耳改性)丙烯酸酯、壬基酚(環氧丙烷2.5莫耳改性)丙烯酸酯、2－乙基己基卡必醇丙烯酸酯、環氧乙烷改性酞酸(甲基)丙烯酸酯、環氧乙烷改性琥珀酸(甲基)丙烯酸酯、三氟乙基(甲基)丙烯酸酯、丙烯酸、甲基丙烯酸、馬來酸、富馬酸、ω－羧基－聚己內酯單(甲基)丙烯酸酯、酞酸單羥乙基(甲基)丙烯酸酯、(甲基)丙烯酸酯偶體、β－(甲基)丙烯醯氧乙基氫琥珀酸酯、正(甲基)丙烯醯氧烷基六氫酞醯亞胺、2－(1,2－環六羧基醯亞胺)乙基(甲基)丙烯酸酯等。(B) Monofunctional (meth) acrylate monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (methyl) Acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (methyl) Acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentene oxide Ethyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclotriene (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy propyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (methyl) propyl Ethyl ester, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate, caprolactone modified tetrahydrogen Mercapto (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethyl Aminoethyl (meth) acrylate, tert-butylaminoethyl (meth) acrylate, ethoxycarbonyl methyl (meth) acrylate, phenol oxirane modified acrylate, phenol (Ethylene oxide 2 Moer modified) acrylate, phenol (ethylene oxide 4 molar modified) acrylate, p-cumyl phenol ethylene oxide modified acrylate, nonyl phenol ethylene oxide modified Acrylate, nonylphenol (ethylene oxide 4 molar modified) acrylate, nonylphenol (ethylene oxide 8 molar modified) acrylate, nonyl phenol (propylene oxide 2.5 molar modification Acrylate, 2-ethylhexyl carbitol acrylate, ethylene oxide modified decanoic acid (meth) acrylate, ethylene oxide modified succinic acid (meth) acrylate, trifluoroethyl ( Methyl) acrylate, acrylic acid, methacrylic acid, Maleic acid, fumaric acid, ω-carboxy-polycaprolactone mono(meth) acrylate, monohydroxyethyl (meth) acrylate, (meth) acrylate, β-(A) Acetyl oxiranyl ethyl hydrosuccinate, n-(meth) propylene decyl hexahydro quinone imine, 2-(1,2-cyclohexadecyl quinone imine) ethyl (meth) acrylate Ester and the like.

(B)單官能(甲基)丙烯酸酯係與(A)同樣地，係更宜為疏水性者。水溶性之情形係研磨加工時樹脂組成物之硬化體進行膨潤俾引起位移，恐加工精度差。此處疏水性謂不具有羥基之(甲基)丙烯酸酯。又，即使為親水性，若非其樹脂組成物之硬化體受水而膨潤或一部分溶解，即使使用亦無妨。(B) The monofunctional (meth)acrylate is more preferably hydrophobic as in the case of (A). In the case of water solubility, the hardened body of the resin composition during polishing is subjected to swelling and causing displacement, which may result in poor processing accuracy. Hydrophobic here is a (meth) acrylate having no hydroxyl group. Further, even if it is hydrophilic, if the cured body which is not the resin composition is swollen or partially dissolved by water, it may be used even if it is used.

(B)單官能(甲基)丙烯酸酯之添加量係(A)及(B)的合計量100質量份中，宜為50~97質量份，更宜為70~90質量份。若為50質量份以上，亦無初期之黏著性降低之虞，若為97質量份以下，剝離性良好。The amount of the (B) monofunctional (meth) acrylate to be added is preferably from 50 to 97 parts by mass, more preferably from 70 to 90 parts by mass, per 100 parts by mass of the total of (A) and (B). When the amount is 50 parts by mass or more, the initial tackiness is not lowered, and if it is 97 parts by mass or less, the peeling property is good.

又，於前述(A)及(B)之調配組成物中，倂用(甲基)丙烯醯氧乙基酸磷酸酯、二丁基2－(甲基)丙烯醯氧乙基酸磷酸酯、二辛基2－(甲基)丙烯醯氧乙基磷酸酯、二苯基2－(甲基)丙烯醯氧乙基磷酸酯、(甲基)丙烯醯氧乙基聚乙二醇酸磷酸酯等之具有乙烯基或(甲基)丙烯酸基之磷酸酯，俾可進一步提昇於金屬面之密著性。Further, in the compounding composition of the above (A) and (B), (meth) propylene oxime oxyethyl phosphate, dibutyl 2-(meth) propylene oxy ethate phosphate, Dioctyl 2-(methyl)propene oxiranyl phosphate, diphenyl 2-(methyl) propylene oxiranyl phosphate, (meth) propylene oxirane ethyl polyglycolate Such as having a vinyl or (meth)acrylic acid phosphate, the ruthenium can further enhance the adhesion of the metal surface.

在本發明所使用之(C)聚合起始劑係宜調配用以藉可見光線或紫外線之活性光線增感而促進樹脂組成物之光硬化者，可使用公知之各種光聚合起始劑。具體上係可舉例如二苯甲酮及其衍生物；苯甲基及其衍生物；蒽醌(anthraquinone)及其衍生物；苯偶因、苯偶因甲基醚、苯偶因乙基醚、苯偶因丙基醚、苯偶因異丁基醚、苯甲基二甲基縮酮等之苯偶因衍生物；二乙氧基乙醯苯、4－第三丁基三氯乙醯苯等之乙醯苯衍生物；2－二甲基胺基乙基苯甲酸酯；對二甲基胺基乙基苯甲酸酯；二苯基二硫酸醚；硫雜蒽酮及其衍生物；樟腦醌、7,7－二甲基－2,3－二氧代雙環[2.2.1]庚烷－1－羧酸、7,7－二甲基－2,3－二氧代雙環[2.2.1]庚烷－1－羧基－2－溴乙基酯、7,7－二甲基－2,3－二氧代雙環[2.2.1]庚烷－1－羧基－2－甲基酯、7,7－二甲基－2,3－二氧代雙環[2.2.1]庚烷－1－羧酸氯化物等之樟腦醌衍生物；2－甲基－ 1－[4－(甲基硫)苯基]－2－嗎啉基丙烷－1－酮、2－苯甲基－2－二甲基胺基－1－(4－嗎啉基苯基)－丁酮－1等之α－胺基烷基酚衍生物；苯甲醯基二苯基磷氧化物、2,4,6－三甲基苯甲醯基二苯基磷氧化物、苯甲醯基二乙氧基磷氧化物、2,4,6－三甲基苯甲醯基二甲氧基苯基磷氧化物、2,4,6－三甲基苯甲醯基二乙氧基苯基磷氧化物等之醯基磷氧化物衍生物等。光聚合起始劑係可組合1種或2種以上而使用。The (C) polymerization initiator used in the present invention is preferably formulated to promote photocuring of the resin composition by sensitization of active light rays of visible light or ultraviolet rays, and various known photopolymerization initiators can be used. Specifically, for example, benzophenone and its derivatives; benzyl and its derivatives; anthraquinone and its derivatives; benzoin, benzoin methyl ether, benzoin ethyl ether a benzoin derivative such as benzoin propyl ether, benzoin isobutyl ether or benzyl dimethyl ketal; diethoxyethyl benzene, 4-tert-butyltrichloroethane Ethylene benzene derivative such as benzene; 2-dimethylaminoethyl benzoate; p-dimethylaminoethyl benzoate; diphenyl disulfate ether; thioxanthone and its derivatives Ceramide, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] Heptane-1-carboxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxy-2-methyl a camphor oxime derivative such as a base ester or a 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxylic acid chloride; 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl) - α-aminoalkylphenol derivatives of butanone-1, etc.; benzhydryl diphenylphosphine oxide, 2,4,6-trimethylbenzimidyl diphenylphosphine oxide, benzate Mercapto-diethoxyphosphorus oxide, 2,4,6-trimethylbenzimidyldimethoxyphenylphosphorus oxide, 2,4,6-trimethylbenzhydryldiethoxy a mercaptophosphorus oxide derivative such as phenylphosphorus oxide. The photopolymerization initiator may be used alone or in combination of two or more.

(C)聚合起始劑之添加量係相對於(A)與(B)之合計10質量份宜為0.1~20質量份。更宜為0.5~10質量份。若為0.1質量份以上，可確實地得到硬化促進的效果，在20質量份以下可得到充分的硬化速度。更佳之形態而言，添加(C)0.5質量份以上，不依存於光照射量，可硬化，進而樹脂組成物之硬化體的交聯度變高，就研磨加工時不產生位移等之點或剝離性提高之點而言更佳。The amount of the polymerization initiator (C) is preferably 0.1 to 20 parts by mass based on 10 parts by mass of the total of (A) and (B). More preferably 0.5 to 10 parts by mass. When it is 0.1 part by mass or more, the effect of promoting the hardening can be surely obtained, and a sufficient curing rate can be obtained at 20 parts by mass or less. In a more preferred embodiment, when (C) is added in an amount of 0.5 parts by mass or more, the amount of crosslinking of the cured product of the resin composition is increased without depending on the amount of light irradiation, and the point of displacement or the like is not generated during polishing. Better in terms of improved peelability.

又，於前述(A)、(B)及(C)之調配組成物中，若含有具苯環骨架之化合物，與半導體保護薄片之親和性會提高，使該組成物的硬化體殘留於基材側，只剝離構件，可回收，故可得到作業性優之效果。Further, in the compound composition of the above (A), (B), and (C), when the compound having a benzene ring skeleton is contained, the affinity with the semiconductor protective sheet is improved, and the hardened body of the composition remains on the base. On the side of the material, only the member is peeled off, and it can be recycled, so that the workability is excellent.

在本發明中，亦可於樹脂組成物中含有極性有機溶劑。藉由含有極性有機溶劑，俾樹脂層與溫水接觸而容易地膨脹，可降低黏著強度。In the present invention, a polar organic solvent may also be contained in the resin composition. By containing a polar organic solvent, the tantalum resin layer is easily expanded by contact with warm water, and the adhesion strength can be lowered.

關於極性有機溶劑係其沸點宜為30℃以上200℃以下。選擇沸點為前述範圍內之極性有機溶劑時，係樹脂層與溫水接觸而黏著強度降低之現像可更進一步地確實地顯現 ，故佳。又，如此之極性有機溶劑可舉例如醇、酮、酯等，但若依據發明人之研究結果，其中宜選擇醇。The polar organic solvent preferably has a boiling point of 30 ° C or more and 200 ° C or less. When a polar organic solvent having a boiling point within the above range is selected, the appearance of the resin layer being contacted with warm water and the adhesive strength is lowered can be more clearly exhibited. , so good. Further, examples of such a polar organic solvent include alcohols, ketones, esters, and the like. However, according to the findings of the inventors, it is preferred to select an alcohol.

醇係可舉例如甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第二丁醇、第三丁醇、正戊基醇、異戊醇、2－乙基丁基醇等。進一步，前述醇中，宜沸點為120℃以下之甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第二丁醇、第三丁醇，其中，更宜為之甲醇、乙醇、異丙醇、正丁醇。The alcohol may, for example, be methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, n-pentyl alcohol, isoamyl alcohol, 2-ethylbutyl Alcohol, etc. Further, among the above alcohols, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, and third butanol having a boiling point of 120 ° C or less are preferable, and more preferably methanol. , ethanol, isopropanol, n-butanol.

極性有機溶劑之添加量係相對於(A)與(B)之合計量100質量份，宜為0.5~10質量份。若為0.5質量份以上，可確保剝離性，若為10質量份以下，亦無初期的黏著性降低之虞，樹脂層呈薄膜狀剝離。The amount of the polar organic solvent to be added is preferably 0.5 to 10 parts by mass based on 100 parts by mass of the total of (A) and (B). When it is 0.5 part by mass or more, the peeling property can be ensured, and if it is 10 parts by mass or less, the initial adhesiveness is not lowered, and the resin layer is peeled off in a film form.

在本發明中係亦可含有不溶解於(A)、(B)及(C)之粒狀物質。藉此，樹脂層可保持一定的厚度，故研磨厚精度會提高。In the present invention, it is also possible to contain a particulate substance which is insoluble in (A), (B) and (C). Thereby, the resin layer can maintain a certain thickness, so the polishing thickness accuracy is improved.

不溶解於(A)、(B)及(C)之粒狀物質就材質而言，一般所使用之有機粒子、無機粒子之任一者均無妨。具體上有機粒子可舉例如聚乙烯粒子、聚丙烯粒子、交聯聚甲基丙烯酸甲酯粒子、交聯聚苯乙烯粒子等，無機粒子可舉例如玻璃、二氧化矽、氧化鋁、鈦等之陶瓷粒子。The particulate matter which is not dissolved in (A), (B), and (C) may be any of organic particles and inorganic particles generally used as the material. Specific examples of the organic particles include polyethylene particles, polypropylene particles, crosslinked polymethyl methacrylate particles, and crosslinked polystyrene particles. Examples of the inorganic particles include glass, cerium oxide, aluminum oxide, titanium, and the like. Ceramic particles.

不溶解於(A)、(B)及(C)之粒狀物質係從研磨厚度精度的提昇、亦即，樹脂層之膜厚的控制觀點，宜為球狀，粒徑為一定。The particulate matter which is not dissolved in (A), (B), and (C) is preferably spherical in shape and has a constant particle diameter from the viewpoint of improvement in polishing thickness accuracy, that is, control of the film thickness of the resin layer.

具體上，有機粒子可舉例如藉由甲基丙烯酸甲酯單體 、苯乙烯單體與交聯性單體之公知的乳化聚合法，形成單分散粒子所得到之交聯聚甲基丙烯酸甲酯粒子、交聯苯乙烯粒子等。Specifically, the organic particles may, for example, be a monomer of methyl methacrylate. A well-known emulsion polymerization method of a styrene monomer and a crosslinkable monomer forms crosslinked polymethyl methacrylate particles, crosslinked styrene particles, and the like obtained by monodisperse particles.

無機粒子可舉例如球狀二氧化矽。The inorganic particles may, for example, be spherical cerium oxide.

此等之粒子係粒子的變形少，粒徑的參差不齊所產生之樹脂層的膜厚變均一，故佳，其中，進一步從粒子之沉澱等的貯存安定性或樹脂組成物之反應性觀點，更宜為交聯聚甲基丙烯酸甲酯粒子、交聯聚苯乙烯粒子。Since the particle-based particles have less deformation and the film thickness of the resin layer which is caused by the unevenness of the particle diameter becomes uniform, it is preferable from the viewpoint of storage stability such as precipitation of particles or reactivity of the resin composition. More preferably, it is a crosslinked polymethyl methacrylate particle or a crosslinked polystyrene particle.

樹脂組成物之硬化物的膜厚係依據構件之種類、形狀、大小等，熟悉此技藝者可適當選擇，但不溶解於(A)、(B)及(C)之粒狀物質之粒徑係就粒子之平均粒徑宜為1~300μm，尤宜為10~200μm。若為1μm以上，可確保剝離性，若為300μm以下，加工精度不降低。又，有關前述粒徑的分布宜儘可能地窄。平均粒徑係依雷射繞射式粒度分布測定裝置(島津製作所公司製「SALD－2200」測定。The film thickness of the cured product of the resin composition is appropriately selected by those skilled in the art, but is not dissolved in the particle size of the particulate matter of (A), (B), and (C) depending on the type, shape, size, and the like of the member. The average particle diameter of the particles is preferably from 1 to 300 μm, particularly preferably from 10 to 200 μm. When it is 1 μm or more, the peeling property can be ensured, and if it is 300 μm or less, the processing accuracy does not decrease. Further, the distribution of the aforementioned particle diameter is preferably as narrow as possible. The average particle size was measured by a laser diffraction type particle size distribution measuring apparatus (SALD-2200, manufactured by Shimadzu Corporation).

不溶解於(A)、(B)及(C)之粒狀物質之添加量係相對於(A)及(B)之合計量100質量份宜為0.1~20質量份，尤宜為0.1~10質量份。若為0.1質量份以上樹脂層之膜厚約為一定，若為20質量份以下，亦恐初期之黏著性降低。The amount of the particulate matter not dissolved in (A), (B), and (C) is preferably 0.1 to 20 parts by mass, and particularly preferably 0.1 to 100 parts by mass based on the total amount of (A) and (B). 10 parts by mass. When the film thickness of 0.1 part by mass or more of the resin layer is approximately constant, if it is 20 parts by mass or less, the initial adhesion may be lowered.

本發明之樹脂組成物係無損本發明之目的的範圍，亦可使用一般所使用之丙烯酸橡膠、胺基甲酸酯橡膠、丙烯腈－丁二烯－苯乙烯橡膠等之各種彈性體、無機填充劑、溶劑、增量材、補強材、可塑劑、增黏劑、染料、顏料、阻燃劑、矽烷偶合劑、界面活性劑等之添加量。The resin composition of the present invention is not limited to the object of the present invention, and various elastomers such as acrylic rubber, urethane rubber, acrylonitrile-butadiene-styrene rubber, and the like which are generally used may be used. Addition amount of agent, solvent, extender, reinforcing material, plasticizer, tackifier, dye, pigment, flame retardant, decane coupling agent, surfactant, etc.

本發明之樹脂組成物係為提高其貯存安定性可使用少量之聚合抑制劑。聚合抑制劑係可舉例如甲基氫醌、氫醌、2,2－亞甲基－雙(4－甲基－6－第三丁基酚)、兒茶酚、氫醌單甲基醚、單第三丁基氫醌、2,5－二第三丁基氫醌、對苯醌、2,5－二苯基－對苯醌、2,5－二第三丁基－對苯醌、苦味酸(picric acid)、檸檬酸、吩噻嗪(phenothiazine)、第三丁基兒茶酚、2－丁基－4－羥基茴香醚、2,6－第三丁基－對甲酚等。The resin composition of the present invention can use a small amount of a polymerization inhibitor for improving its storage stability. The polymerization inhibitor may, for example, be methylhydroquinone, hydroquinone, 2,2-methylene-bis(4-methyl-6-tert-butylphenol), catechol, hydroquinone monomethyl ether, Mono-tert-butylhydroquinone, 2,5-di-t-butylhydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-di-t-butyl-p-benzoquinone, Picric acid, citric acid, phenothiazine, tert-butylcatechol, 2-butyl-4-hydroxyanisole, 2,6-t-butyl-p-cresol, and the like.

此等之聚合抑制劑的使用量係相對於(A)及(B)之單體合計量100質量份，宜為0.001~3質量份，更宜為0.01~2質量份。就0.001質量份以上可確保貯存安定性，宜為3質量份以下可得到良好的黏著性，亦無變成未硬化。The amount of the polymerization inhibitor to be used is preferably 0.001 to 3 parts by mass, more preferably 0.01 to 2 parts by mass, per 100 parts by mass of the total of the monomers of (A) and (B). The storage stability can be ensured in an amount of 0.001 part by mass or more, preferably 3 parts by mass or less, and good adhesion is not obtained, and it is not uncured.

由前述樹脂組成物所得到之樹脂層係如前述般，宜藉加熱進行剝離者或與水之接觸進行剝離者。加熱之溫度為40~150℃，宜為50~100℃，更宜為55~80℃，與溫水接觸時的溫水溫度宜為30~100℃，宜為35~80℃，更宜為40~60℃，不須有龐大的設備，而作業上處理很容易，故佳。The resin layer obtained from the resin composition is preferably peeled off by contact with water or by contact with water as described above. The heating temperature is 40~150°C, preferably 50~100°C, more preferably 55~80°C, and the warm water temperature when contacting with warm water is preferably 30~100°C, preferably 35~80°C, more preferably 40~60°C, there is no need for huge equipment, and the handling on the job is very easy, so it is good.

(保護薄片)(protective sheet)

保護薄片係可使用由以往公知之合成樹脂所構成之薄片，亦可使用乙烯－乙酸乙烯酯、聚乙烯、聚丙烯、聚丁烯、聚丁二烯等之聚烯烴類之外，聚氯化乙烯、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚苯乙烯、聚碳酸酯、聚醯亞胺等作為單獨或2種以上的層合薄膜。保護薄片中之基材的厚度宜為50~500μm，更宜為70~250μm。較 500μm厚時係藉因研磨時所施加之荷重，有時晶圓偏移，失去研磨精度，不足50μm時，係於基材薄膜成型時產生針孔或魚眼，因其影響而研磨精度變差。又，樹脂組成物含有丙烯酸系樹脂時等之光硬化性樹脂時，宜選擇保護薄片亦為光透過性者。又，保護薄片係必須於後述之半導體晶圓的背面研磨而滿足強度特性，故至少宜一層以上含有乙烯－乙酸乙烯酯所構成之層。As the protective sheet, a sheet composed of a conventionally known synthetic resin may be used, and a polyolefin such as ethylene-vinyl acetate, polyethylene, polypropylene, polybutene or polybutadiene may be used. Ethylene, polyethylene terephthalate, polyethylene naphthalate, polystyrene, polycarbonate, polyimine, or the like is used as a single or two or more laminated films. The thickness of the substrate in the protective sheet is preferably from 50 to 500 μm, more preferably from 70 to 250 μm. More When the thickness is 500 μm, the load applied during polishing may be offset, and the polishing accuracy may be lost. When the thickness is less than 50 μm, pinholes or fish eyes are formed during the formation of the base film, and the polishing accuracy is deteriorated due to the influence. . When the resin composition contains a photocurable resin such as an acrylic resin, it is preferable to select a protective sheet which is also light-transmitting. Further, since the protective sheet must be polished on the back surface of the semiconductor wafer to be described later to satisfy the strength characteristics, it is preferable that at least one layer or more of a layer composed of ethylene-vinyl acetate is contained.

於保護薄片係亦可使用設有由黏著劑所構成之黏著層，黏著劑係可使用一般感壓型黏著劑、紫外線硬化型黏著劑、加熱硬化型黏著劑等。一般感壓型黏著劑可使用丙烯系、橡膠系、聚矽氧系等之黏著劑。紫外線硬化型黏著劑係於一般感壓型黏著劑調配硬化性化合物及紫外線硬化起始劑者，藉紫外線之照射可調整其黏著力。又，加熱硬化型黏著劑係於一般感壓型黏著劑調配硬化性化合物及加熱硬化起始劑者，可藉加熱以調整其黏著力。其中宜丙烯酸系樹脂組成物所構成之黏著劑。黏著層之厚度宜為3~100μm，更宜為10~50μm。較100μm厚時，因研磨時所施加之荷重，有時晶圓會偏位，研磨精度變差，較3μm薄時，因塗佈時所產生之糊刮具的影響等研磨精度會降低。An adhesive layer made of an adhesive may be used for the protective sheet, and a general pressure-sensitive adhesive, an ultraviolet-curable adhesive, a heat-curing adhesive, or the like may be used as the adhesive. As the pressure-sensitive adhesive, an adhesive such as a propylene-based, rubber-based or polyoxygen-based oxygen-based adhesive can be used. The ultraviolet curable adhesive is a general pressure sensitive adhesive which is formulated with a curable compound and an ultraviolet curing starter, and its adhesion can be adjusted by irradiation with ultraviolet rays. Further, the heat-curing type adhesive is a general pressure-sensitive adhesive which is formulated with a curable compound and a heat-curing initiator, and can be heated to adjust its adhesion. Among them, an adhesive composed of an acrylic resin composition is preferred. The thickness of the adhesive layer is preferably from 3 to 100 μm, more preferably from 10 to 50 μm. When the thickness is 100 μm, the wafer may be misaligned due to the load applied during polishing, and the polishing accuracy may be deteriorated. When the thickness is thinner than 3 μm, the polishing accuracy may be lowered due to the influence of the paste scraper generated during coating.

(固定用治具)(fixed fixture)

固定用治具宜為平滑之材料，亦可使用玻璃、不鏽鋼、鋁、陶瓷、鐵等之金屬板狀體、丙烯酸、聚碳酸酯、ABS、PET、尼龍、胺基甲酸酯、聚醯亞胺、聚烯烴、氯 化乙烯等之樹脂板狀體或厚的樹脂薄膜狀者等作為單獨或2種以上的層合體。The fixing fixture should be a smooth material, or a metal plate, such as glass, stainless steel, aluminum, ceramics, iron, etc., acrylic, polycarbonate, ABS, PET, nylon, urethane, polyphthalate. Amine, polyolefin, chlorine A resin plate-like body such as ethylene or a thick resin film is used as the single or two or more laminates.

固定用治具係宜使365nm之波長透過20%以上者，更宜為50%以上透過者。一般，對樹脂組成物照射365nm波長之光而硬化時，為於特定時間內結束硬化，適當設定光之照射量，以此時之照射光量作為基準，若固定用治具透過365nm波長20%以上者，亦未使樹脂組成物硬化耗費太多時間，為良好。The fixing jig is preferably such that the wavelength of 365 nm is transmitted through 20% or more, and more preferably 50% or more. In general, when the resin composition is irradiated with light having a wavelength of 365 nm and hardened, the amount of light irradiation is appropriately set in order to complete the hardening in a specific time, and the fixing jig is passed through a wavelength of 365 nm or more at a wavelength of 365 nm. However, it does not take too much time to harden the resin composition, which is good.

又，固定用治具之厚度並無特別限定，但宜為100μm~10mm，更宜選擇2~5mm。Further, the thickness of the fixing jig is not particularly limited, but is preferably 100 μm to 10 mm, and more preferably 2 to 5 mm.

又，有關固定用治具等之光的透過量係使用Topcon公司製「UVR－2」，測定使波長365nm之光的入射量為100時之透過量。In addition, the amount of light transmitted by the fixing jig or the like was measured by using "UVR-2" manufactured by Topcon Corporation, and the amount of light when the incident amount of light having a wavelength of 365 nm was 100 was measured.

(半導體晶圓之研磨方法)(Method of grinding semiconductor wafers)

本發明之較佳實施態樣中係保護薄片或固定用治具係預先於半導體晶圓的電路側面形成較其晶圓厚還淺之切割深度的溝，其後，研磨上述半導體晶圓的背面以使半導體晶圓的厚度薄化，同時最後在分割成各晶片之半導體晶圓的背面研磨方法中，可使用來作為電路面之凹凸追蹤性與保護及半導體晶圓的固定手段。In a preferred embodiment of the present invention, the protective sheet or the fixing fixture is formed on the side of the circuit surface of the semiconductor wafer in advance with a shallower depth of the wafer, and then the back surface of the semiconductor wafer is polished. In order to make the thickness of the semiconductor wafer thin, and finally, in the back surface polishing method of the semiconductor wafer divided into the respective wafers, it is possible to use as a means for fixing the unevenness and protection of the circuit surface and the semiconductor wafer.

本發明之較佳實施態樣係具體上可提示由以下之步驟(1)~(5)所構成的半導體晶圓的背面研磨方法。The preferred embodiment of the present invention specifically suggests a backside polishing method for a semiconductor wafer comprising the following steps (1) to (5).

(1)沿著用以區隔半導體晶圓上的電路之直線而切割特定 深度的溝(參照圖1)。(1) cutting specific along a line used to separate circuits on a semiconductor wafer Depth of ditch (see Figure 1).

(2)以被覆前述半導體晶圓的電路面全體之方式，塗佈樹脂組成物(參照圖2)。又，塗佈方法係可採用桿塗、噴槍、旋塗等各式各樣的塗佈形式。(2) A resin composition (see FIG. 2) is applied so as to cover the entire circuit surface of the semiconductor wafer. Further, the coating method can be carried out in various coating forms such as a rod coating, a spray gun, and a spin coating.

(3)於由樹脂組成物所構成之層上貼合保護薄片或固定用治具，照射可見光或紫外線，使光硬化性樹脂層硬化。(3) A protective sheet or a fixing jig is bonded to a layer composed of a resin composition, and visible light or ultraviolet rays are irradiated to cure the photocurable resin layer.

(3’)取代上述(2)及(3)而塗佈樹脂組成物後，照射可見光或紫外線，使由樹脂組成物所構成之層硬化後，貼合保護薄片或固定用治具(參照圖3)。(3') After coating the resin composition in place of the above (2) and (3), irradiating visible light or ultraviolet light to cure the layer composed of the resin composition, and then bonding the protective sheet or the fixing jig (see the figure) 3).

於上述(3)或(3’)中，亦可從保護薄片外側或固定用治具外側施加重而得到均一的厚度精度。In the above (3) or (3'), a uniform thickness accuracy can be obtained by applying weight from the outside of the protective sheet or the outside of the fixing jig.

(4)研磨半導體晶圓之背面至特定的厚度，分割成各個晶片(參照圖4)。(4) The back surface of the semiconductor wafer is polished to a specific thickness and divided into individual wafers (see Fig. 4).

(5)於晶片之研磨面貼合另一黏著膠帶，加熱至40~150℃，或與40~100℃之溫水接觸而從晶片剝離樹脂層或保護薄片或固定用治具(參照圖5)。(5) attaching another adhesive tape to the polished surface of the wafer, heating to 40 to 150 ° C, or contacting the warm water of 40 to 100 ° C to peel off the resin layer or the protective sheet or the fixing fixture from the wafer (refer to FIG. 5) ).

其後，拾取晶片，安裝於特定的基體上。Thereafter, the wafer is picked up and mounted on a specific substrate.

實施例Example

以下藉本發明之實施例更詳細地說明本發明，但不應限定於此等而被解釋。The invention is explained in more detail below by means of examples of the invention, but should not be construed as being limited thereto.

又，各別之實施例、比較例中之樹脂組成物的組成(質量份)、及評估結果等歸納表示於表1、表2中。(實施例 1~1)Further, the composition (parts by mass) of the resin composition in each of the examples and the comparative examples, and the evaluation results are summarized in Tables 1 and 2. (Example 1~1)

(實施例1－1)(Example 1-1) (樹脂組成物)(resin composition)

添加(A)作為多官能(甲基)丙烯酸酯之日本曹達公司製「TE－2000」(1,2－聚丁二烯末端胺基甲酸酯、以下略稱為「TE－2000」)10質量份、二環癸基二丙烯酸酯(日本化藥公司製「KAYARAD R－684」、以下簡稱「R－684」)10質量份、(B)作為單官能(甲基)丙烯酸酯之2－(1,2－環六羰醯亞胺)乙基丙烯酸酯(東亞合成公司製「Aronix M－140」、以下「M－140」)30質量份、二環戊烯氧乙基甲基丙烯酸酯「Rohm & Hass公司製「QM－657」」、以下簡稱「QM」)50質量份、(C)作為聚合起始劑之2－甲基－1－[4－(甲基硫)苯基]－2－嗎啉基丙烷－1－酮(Ciba Specialty Chemicals公司製「IRGACURE 907」、簡稱為以下「IRGACURE 907」)2質量份、及作為聚合抑制劑之2,2－亞甲基－雙(4－甲基－6－第三丁基酚)(以下簡稱為「MDP」)0.1質量份，進行混合而調製樹脂組成物。(A) "TE-2000" (1,2-polybutadiene terminal urethane, hereinafter abbreviated as "TE-2000") manufactured by Japan Soda Co., Ltd. as a polyfunctional (meth) acrylate. Parts by mass, dicyclodecyl diacrylate ("KAYARAD R-684" manufactured by Nippon Kayaku Co., Ltd., hereinafter referred to as "R-684"), 10 parts by mass, (B) as a monofunctional (meth) acrylate 2- (1,2-cyclohexacarbonylimine)ethyl acrylate ("Aronix M-140", "M-140", manufactured by Toagosei Co., Ltd.) 30 parts by mass, dicyclopentene oxyethyl methacrylate 50 parts by mass of "QM-657" manufactured by Rohm & Hass Co., Ltd., hereinafter referred to as "QM", and (C) 2-methyl-1-[4-(methylthio)phenyl group as a polymerization initiator 2-morpholinylpropan-1-one ("IRGACURE 907" manufactured by Ciba Specialty Chemicals Co., Ltd., abbreviated as "IRGACURE 907") 2 parts by mass, and 2,2-methylene-bis (as a polymerization inhibitor) 0.1 parts by mass of 4-methyl-6-tert-butylphenol (hereinafter abbreviated as "MDP") was mixed to prepare a resin composition.

(保護薄片)(protective sheet)

使依據丁基丙烯酸酯80質量%、甲基(甲基)丙烯酸酯19質量%、及2－羥基乙基丙烯酸酯1質量%之共聚物(玻璃轉移點－53.3℃)與2,4－甲苯撐基二異氰酸酯之三羥甲基丙烷的加成體所交聯之黏著劑層合於以乙烯－乙酸乙烯酯作 為主體之160μm厚的薄膜，得到保護薄片。又，藉T模頭共押出法使黏著劑厚度成型為20μm，薄膜全體之厚度為160μm。Copolymer (glass transition point -53.3 ° C) and 2,4-toluene based on 80% by mass of butyl acrylate, 19% by mass of methyl (meth) acrylate, and 1% by mass of 2-hydroxyethyl acrylate An adhesive crosslinked by an adduct of trimethylolpropane of a benzyl diisocyanate is laminated to ethylene-vinyl acetate As a main film of 160 μm thick, a protective sheet was obtained. Further, the thickness of the adhesive was molded to 20 μm by the T-die co-extrusion method, and the thickness of the entire film was 160 μm.

使用前述樹脂組成物與保護薄片，以如下所示之方法實施本發明之研磨方法，進行評估。研磨方法與評估係於氧環境下進行。Using the foregoing resin composition and protective sheet, the grinding method of the present invention was carried out in the following manner for evaluation. The grinding method and evaluation are carried out under an oxygen atmosphere.

(評估方法)(evaluation method) (黏著性)(adhesive)

使直徑8英吋、厚度700μm且100μm之焊塊之矽晶圓貼合於切割膠帶(電化學工業公司製「UHP－1005M3」)，使用切割鋸(Disc公司製「DAD－341」)，以35μm厚之刀片，以切入量300μm、晶片大小3mm2 之條件形成溝。然後，剝離切割膠帶，貼合樹脂組成物及保護片，以出現均一面的方式加重10kg。其後，藉由使用無電極放電燈之Fusion公司製硬化裝置，以365nm波長、2000mJ/cm2 之條件使樹脂組成物硬化。其後，使半導體晶圓的背面使用Disc公司製DFG－850，進行研磨至厚100μm，分割成各個晶片。所分割之晶片的黏著性差，評估晶片飛濺之產生數目，若為不足50個為○，若為51個以上不足100個為△，若為101個以上為×。A silicon wafer having a diameter of 8 inches, a thickness of 700 μm, and a thickness of 100 μm was bonded to a dicing tape ("UHP-1005M3" manufactured by Electrochemical Industries, Inc.), and a dicing saw ("DAD-341" manufactured by Disc Corporation) was used. A 35 μm thick blade was formed with a cut amount of 300 μm and a wafer size of 3 mm 2 . Then, the dicing tape was peeled off, and the resin composition and the protective sheet were bonded, and 10 kg was weighted in such a manner that one side was formed. Thereafter, the resin composition was cured at a wavelength of 365 nm and 2000 mJ/cm 2 by using a curing apparatus manufactured by Fusion Co., Ltd. using an electrodeless discharge lamp. Thereafter, the back surface of the semiconductor wafer was polished to a thickness of 100 μm using DFG-850 manufactured by Disc Co., Ltd., and divided into individual wafers. The number of generated wafer spatters is poor, and the number of wafer spatters is estimated to be less than 50, and if 51 or less, less than 100 are Δ, and 101 or more is ×.

<保持性><retention>

藉與前述相同之方法，進行研磨至厚100μm，分割成 各個晶片。所分割之晶片的黏著性差，晶片偏移時為×，不產生偏移而良好的情形為○。Grinding to a thickness of 100 μm by the same method as described above, and dividing into Individual wafers. The adhesion of the divided wafer is inferior, and when the wafer is shifted, it is ×, and the case where the offset is not generated is good.

<剝離性><peelability>

藉與前述相同之方法，進行研磨至厚100μm，分割成各個晶片。其後於晶片之研磨面貼合黏著膠帶(電化學工業公司製「UHP－110B」)，加溫至60℃，剝離樹脂層及保護薄片。剝離時從樹脂層無法剝離晶片時為×，不順利者可剝離時為△，可順利剝離時為○。The polishing was carried out to a thickness of 100 μm in the same manner as described above, and divided into individual wafers. Thereafter, an adhesive tape ("UHP-110B" manufactured by Electrochemical Industries, Inc.) was attached to the polished surface of the wafer, and the mixture was heated to 60 ° C to peel off the resin layer and the protective sheet. In the case of peeling, when the wafer cannot be peeled off from the resin layer, it is ×, when it is not smooth, it is Δ when it is peeled off, and when it is peeled off smoothly, it is ○.

<黏著強度><adhesion strength>

依據JIS K6850，測定黏著強度。具體上，使用耐熱玻璃(商品名「耐熱Pyrex玻璃」、25mm×25mm×厚2.0mm)作為被黏材。使黏著部位為8mm，以樹脂組成物貼合2片的耐熱玻璃。藉由使用無電極放電燈之Fusion公司製硬化裝置，以365nm之波長的積分光量2000mJ/cm2 條件硬化，製作抗拉剪斷黏著強度試驗片。試驗片係使用萬能試驗機，以溫度23℃、濕度50%的環境下、抗拉速度10mm/分測定抗拉剪斷黏著強度。The adhesion strength was measured in accordance with JIS K6850. Specifically, heat-resistant glass (trade name "heat-resistant Pyrex glass", 25 mm × 25 mm × thickness 2.0 mm) was used as the adherend. Make the adhesive part 8mm Two sheets of heat-resistant glass were bonded to each other with a resin composition. A tensile shear strength test piece was produced by hardening under the condition of an integrated light amount of 2000 mJ/cm 2 at a wavelength of 365 nm by using a curing apparatus manufactured by Fusion Co., Ltd. using an electrodeless discharge lamp. The test piece was subjected to a universal testing machine, and the tensile shear strength was measured at a temperature of 23 ° C and a humidity of 50% at a tensile speed of 10 mm/min.

(實施例1－2~1－8)(Examples 1-2 to 1-8)

在實施例1－1中，除變更樹脂組成物之(A)多官能(甲基)丙烯酸酯與(B)單官能(甲基)丙烯酸酯之比率，變更(C)聚合起始劑之比率以外，其餘係與實施例1－1同樣的操作，進行評估。日本曹達公司製「TE－2000」與二環癸基二丙烯酸酯之比率、2－(1,2－環六羰醯亞胺)乙基丙烯酸酯與二環戊基氧乙基甲基丙烯酸酯之比率係與實施例1－1相同做法。In Example 1-1, the ratio of (C) polyfunctional (meth) acrylate to (B) monofunctional (meth) acrylate was changed, and the ratio of (C) polymerization initiator was changed. The rest were evaluated in the same manner as in Example 1-1. Ratio of "TE-2000" to bicyclodecyl diacrylate manufactured by Japan Soda Co., 2-(1,2-cyclohexacarbonylimine)ethyl acrylate and dicyclopentyloxyethyl methacrylate The ratio is the same as that of Example 1-1.

(比較例1－1)(Comparative Example 1-1)

就比較例而言，在實施例1－1中，只使用習知之黏著薄片而與實施例1－1同樣地操作，進行評估。又，黏著薄片係使用專利文獻3(專利第3773358號公報)的實施例1記載的黏著膠帶，進行晶圓的保持性等之評估。藉由使用JIS－A硬度低之黏著薄片，晶圓的保持性差，研磨精度差，且晶片化時晶片偏移，產生晶片飛濺。又，晶片於黏著薄片側會移動，未順利地剝離。In the comparative example, in the same manner as in Example 1-1, only the conventional adhesive sheet was used and evaluated. In addition, the adhesive sheet described in Example 1 of Patent Document 3 (Patent No. 3773358) was used to evaluate the retention of the wafer and the like. By using an adhesive sheet having a low JIS-A hardness, the retention of the wafer is poor, the polishing precision is poor, and the wafer is displaced during wafer formation, causing wafer spatter. Further, the wafer moves on the side of the adhesive sheet and does not smoothly peel off.

(實施例1－9)(Examples 1-9)

在實施例1－1中，剝離晶片時浸漬於40℃的溫水後，樹脂層附著之保護薄片與晶片可順利地剝離。In Example 1-1, when the wafer was peeled off and immersed in warm water of 40 ° C, the protective sheet to which the resin layer adhered and the wafer were smoothly peeled off.

(實施例1－10)(Examples 1-10) (樹脂組成物)(resin composition)

除添加(A)作為多官能(甲基)丙烯酸酯之日本曹達公司製「TEAI－1000」(1,4－聚丁二烯末端胺基甲酸酯(甲基)丙烯酸酯)20質量份、(B)作為單官能(甲基)丙烯酸酯之丁基(甲基)丙烯酸酯80質量份、(C)作為聚合起始劑之苯偶因乙基醚2質量份、及作為聚合抑制劑之第三丁基兒茶酚0.1質量份，進行混合而調製樹脂組成物以外，其餘係與實施例1－1相同之操作進行評估。In addition to (A) 20 parts by mass of "TEAI-1000" (1,4-polybutadiene terminal urethane (meth) acrylate) manufactured by Japan Soda Co., Ltd. as a polyfunctional (meth) acrylate, (B) 80 parts by mass of butyl (meth) acrylate as a monofunctional (meth) acrylate, (C) 2 parts by mass of benzoin ethyl ether as a polymerization initiator, and as a polymerization inhibitor The same operation as in Example 1-1 was carried out except that 0.1 parts by mass of the third butyl catechol was mixed to prepare a resin composition.

(實施例1－11)(Examples 1-11)

在實施例1－1中，相對於(A)及(B)之合計量100質量份，添加5質量份之粒狀物質(平均粒徑50μm之交聯聚甲基丙烯酸甲酯粒子、根上工業公司製Artpearl GR－200、以下簡稱為「GR－200」)，進行混合而調製樹脂組成物以外，其餘係與實施例1－1同樣的操作，進行評估。樹脂層之膜厚達100μm為一定，研磨厚度精度會提高。剝離性與保持性為○。In Example 1-1, 5 parts by mass of the particulate matter (crosslinked polymethyl methacrylate particles having an average particle diameter of 50 μm, and the root industrial) were added to 100 parts by mass of the total of (A) and (B). The company's Artpearl GR-200 (hereinafter referred to as "GR-200") was mixed and prepared to prepare a resin composition, and the evaluation was carried out in the same manner as in Example 1-1. When the film thickness of the resin layer is 100 μm, the polishing thickness accuracy is improved. Peelability and retention are ○.

(實施例2－1)(Example 2-1) (樹脂組成物)(resin composition)

添加(A)作為多官能(甲基)丙烯酸酯之日本合成化學公司製「UV－3000B」(胺基甲酸酯丙烯酸酯、以下略稱為「UV－3000B」)8質量份、二環癸基二丙烯酸酯(日本化藥公司製「KAYARAD R－684」、以下簡稱「R－684」)12質量份、(B)作為單官能(甲基)丙烯酸酯之2－(1,2－環 六羰醯亞胺)乙基丙烯酸酯(東亞合成公司製「Aronix M－140」、以下「M－140」)30質量份、二環戊烯氧乙基甲基丙烯酸酯「Rohm & Hass公司製「QM－657」」、以下簡稱「QM」)50質量份、(C)作為聚合起始劑之2－甲基－1－[4－(甲基硫)苯基]－2－嗎啉基丙烷－1－酮(Ciba Specialty Chemicals公司製「IRGACURE 907」、簡稱為以下「IRGACURE 907」)2質量份、及作為聚合抑制劑之2,2－亞甲基－雙(4－甲基－6－第三丁基酚)(以下簡稱為「MDP」)0.1質量份，進行混合而調製樹脂組成物。(A) 8 parts by mass of a "UV-3000B" (urethane acrylate, hereinafter abbreviated as "UV-3000B") manufactured by Nippon Synthetic Chemical Co., Ltd., which is a polyfunctional (meth) acrylate, and a bicyclic oxime Dimethacrylate ("KAYARAD R-684" manufactured by Nippon Kayaku Co., Ltd., hereinafter referred to as "R-684") 12 parts by mass, (B) 2-(1,2-ring as monofunctional (meth) acrylate Hexacarbonyl succinimide ethyl acrylate ("Aronix M-140", "M-140", manufactured by Toagosei Co., Ltd.) 30 parts by mass, dicyclopentene oxyethyl methacrylate "Rohm & Hass" "QM-657", hereinafter referred to as "QM") 50 parts by mass, (C) 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl as a polymerization initiator Propane-1-one ("IRGACURE 907" manufactured by Ciba Specialty Chemicals Co., Ltd., abbreviated as "IRGACURE 907") 2 parts by mass, and 2,2-methylene-bis(4-methyl-6) as a polymerization inhibitor 0.1 parts by mass of -t-butylphenol) (hereinafter abbreviated as "MDP") was mixed to prepare a resin composition.

(固定用治具)(fixed fixture)

固定用治具係使用透過波長365nm之光80%之厚的3mm玻璃板。The fixing jig is a 3 mm glass plate which is 80% thick by light having a wavelength of 365 nm.

使用前述樹脂組成物與固定用治具，以下述之方法實施本發明之研磨方法進行評估。Using the above-described resin composition and fixing jig, the grinding method of the present invention was carried out by the following method for evaluation.

(評估方法)(evaluation method) (黏著性)(adhesive)

使直徑8英吋、厚度700μm且100μm之焊塊之矽晶圓貼合於切割膠帶(電化學工業公司製「UHP－1005M3」)，使用切割鋸(Disc公司製「DAD－341」)，以35μm厚之刀片，以切入量300μm、晶片大小3mm2 之條件形成溝。然後，剝離切割膠帶，貼合樹脂組成物及保護片，以出現均一面的方式加重10Kg。其後，藉由使用無電極放電燈之 Fusion公司製硬化裝置，以365nm波長、2000mJ/cm2 之條件使樹脂組成物硬化。其後，使半導體晶圓的背面使用Disc公司製DFG－850，進行研磨至厚100μm，分割成各個晶片。所分割之晶片的黏著性差，評估晶片飛濺之產生數目，若為不足50個為○，若為51個以上不足100個為△，若為101個以上為×。A silicon wafer having a diameter of 8 inches, a thickness of 700 μm, and a thickness of 100 μm was bonded to a dicing tape ("UHP-1005M3" manufactured by Electrochemical Industries, Inc.), and a dicing saw ("DAD-341" manufactured by Disc Corporation) was used. A 35 μm thick blade was formed with a cut amount of 300 μm and a wafer size of 3 mm 2 . Then, the dicing tape was peeled off, and the resin composition and the protective sheet were bonded, and 10 Kg was weighted in such a manner that one side was formed. Thereafter, the resin composition was cured at a wavelength of 365 nm and 2000 mJ/cm 2 by using a curing apparatus manufactured by Fusion Co., Ltd. using an electrodeless discharge lamp. Thereafter, the back surface of the semiconductor wafer was polished to a thickness of 100 μm using DFG-850 manufactured by Disc Co., Ltd., and divided into individual wafers. The number of generated wafer spatters is poor, and the number of wafer spatters is estimated to be less than 50, and if 51 or less, less than 100 are Δ, and 101 or more is ×.

<保持性><retention>

與實施例1－1之評估方法同樣地進行。This was carried out in the same manner as the evaluation method of Example 1-1.

<剝離性><peelability>

與實施例1－1之評估方法同樣地進行。This was carried out in the same manner as the evaluation method of Example 1-1.

(實施例2－2~2－8)(Examples 2-2 to 2-8)

在實施例2－1中，除變更樹脂組成物之(A)多官能(甲基)丙烯酸酯與(B)單官能(甲基)丙烯酸酯之比率，變更(C)聚合起始劑之比率以外，其餘係與實施例2－1同樣的操作，進行評估。日本合成化學公司製「UV－3000B」與二環癸基二丙烯酸酯之比率、2－(1,2－環六羰醯亞胺)乙基丙烯酸酯與二環戊基氧乙基甲基丙烯酸酯之比率係與實施例2－1相同做法。In Example 2-1, the ratio of (C) polyfunctional (meth) acrylate to (B) monofunctional (meth) acrylate was changed, and the ratio of (C) polymerization initiator was changed. The rest was evaluated in the same manner as in Example 2-1. The ratio of "UV-3000B" to bicyclodecyl diacrylate manufactured by Nippon Synthetic Chemical Co., Ltd., 2-(1,2-cyclohexacarbonylimide)ethyl acrylate and dicyclopentyloxyethyl methacrylate The ratio of the ester was the same as that of Example 2-1.

(比較例2－1)(Comparative Example 2-1)

就比較例而言，在實施例2－1中，只使用習知之黏著薄片而與實施例2－1同樣地操作，進行評估。又，黏著薄片係使用專利文獻3(專利第3773358號公報)的實施例1記載的黏著膠帶，進行晶圓的保持性等之評估。藉由使用JIS－A硬度低之黏著薄片，晶圓的保持性差，研磨精度差，且晶片化時晶片偏移，產生晶片飛濺。又，晶片於黏著薄片側會移動，未順利地剝離。In the comparative example, in the same manner as in Example 2-1, only the conventional adhesive sheet was used and evaluated. In addition, the adhesive sheet described in Example 1 of Patent Document 3 (Patent No. 3773358) was used to evaluate the retention of the wafer and the like. By using an adhesive sheet having a low JIS-A hardness, the retention of the wafer is poor, the polishing precision is poor, and the wafer is displaced during wafer formation, causing wafer spatter. Further, the wafer moves on the side of the adhesive sheet and does not smoothly peel off.

(實施例2－9)(Examples 2-9)

在實施例2－1中，剝離晶片時浸漬於40℃的溫水後，樹脂層附著之固定用治具與晶片可順利地剝離。In Example 2-1, when the wafer was peeled off and immersed in warm water of 40 ° C, the fixing jig to which the resin layer adhered and the wafer were smoothly peeled off.

(實施例2－10)(Examples 2-10) (樹脂組成物)(resin composition)

除添加(A)作為多官能(甲基)丙烯酸酯之大阪有機化學公司製「BAC－45」(聚異戊二烯末端(甲基)丙烯酸酯)20質量份、(B)作為單官能(甲基)丙烯酸酯之異冰片基(甲基)丙烯酸酯80質量份、(C)作為聚合起始劑之4－第三丁基三氯乙醯苯2質量份、及作為聚合抑制劑之吩噻嗪0.1質量份，進行混合而調製樹脂組成物以外，其餘係與實施例2－1相同之操作進行評估。In addition to (A) 20 parts by mass of "BAC-45" (polyisoprene terminal (meth) acrylate) manufactured by Osaka Organic Chemical Co., Ltd. as a polyfunctional (meth) acrylate, (B) as a monofunctional ( 80 parts by mass of isobornyl (meth) acrylate of methyl acrylate, (C) 2 parts by mass of 4-tert-butyltrichloroethane benzene as a polymerization initiator, and phenoline as a polymerization inhibitor The same operation as in Example 2-1 was carried out except that 0.1 parts by mass of thiazine was mixed and prepared to prepare a resin composition.

(實施例2－11)(Example 2-11)

在實施例2－1中，相對於(A)及(B)之合計量100質量份，添加5質量份之粒狀物質(平均粒徑50μm之交聯聚甲基丙烯酸甲酯粒子、根上工業公司製Artpearl GR－200、以下簡稱為「GR－200」)，進行混合而調製樹脂組成物以外，其餘係與實施例2－1同樣的操作，進行評估。樹脂層之膜厚達100μm為一定，研磨厚度精度會提高。剝離性與保持性為○。In the example 2-1, 5 parts by mass of the particulate matter (crosslinked polymethyl methacrylate particles having an average particle diameter of 50 μm, and the root industrial) were added to 100 parts by mass of the total of (A) and (B). The company's Artpearl GR-200 (hereinafter referred to as "GR-200") was mixed and prepared to prepare a resin composition, and the evaluation was carried out in the same manner as in Example 2-1. When the film thickness of the resin layer is 100 μm, the polishing thickness accuracy is improved. Peelability and retention are ○.

從實施例之結果可知以下之事情。The following things are known from the results of the examples.

(1)本發明之樹脂組成物係即使氧環境下亦進行硬化，故容易剝離。(1) The resin composition of the present invention is hardened even in an oxygen atmosphere, so that it is easily peeled off.

(2)本發明之樹脂組成物係剝離性、保持性、黏著性均良好。(2) The resin composition of the present invention is excellent in peelability, retention, and adhesion.

產業上之利用可能性Industrial use possibility

本發明係研磨加工時之凹凸追蹤性及分割成各晶片時 之晶片保持性優，不產生晶片缺角或拾取不良，而與半導體晶圓之黏著性，剝離性優之構件、加工方法；可適宜使用於具有電路面高之凹凸的半導體晶圓之背面研磨，故產業上有用。The present invention is characterized by unevenness tracking during polishing and when divided into wafers The wafer has excellent retention, does not cause wafer chipping or picking defects, and has adhesion to a semiconductor wafer, and has excellent peelability and processing method; and can be suitably used for back surface polishing of a semiconductor wafer having a high surface roughness. Therefore, it is useful in industry.

又，2007年6月22日所申請之日本專利申請2007－164934號及2007年6月22日所申請之日本專利申請2007－164951號之說明書、申請專利範圍、圖面及摘要的全內容引用於此，摘錄作為本發明之說明書的揭示。Japanese Patent Application No. 2007-164934, filed on Jun. 22, 2007, and the entire contents of Herein, the excerpt is disclosed as a description of the present invention.

1‧‧‧半導體晶圓1‧‧‧Semiconductor wafer

2‧‧‧凸塊2‧‧‧Bumps

3‧‧‧溝3‧‧‧ditch

4‧‧‧樹脂層4‧‧‧ resin layer

5‧‧‧保護薄片或固定用治具5‧‧‧Protective sheet or fixture

6‧‧‧晶片6‧‧‧ wafer

7‧‧‧黏著膠帶7‧‧‧Adhesive tape

圖1係說明本發明之研磨方法的一實施形態之圖，表示沿著用以區隔電路之直線而研磨特定深度之溝的半導體晶圓。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an embodiment of a polishing method of the present invention, showing a semiconductor wafer in which a groove of a specific depth is polished along a line for dividing a circuit.

圖2係說明本發明之研磨方法的一實施形態之圖，表示於圖1之半導體晶圓的電路面上塗佈樹脂組成物之狀態。Fig. 2 is a view showing an embodiment of a polishing method of the present invention, showing a state in which a resin composition is applied to a circuit surface of the semiconductor wafer of Fig. 1.

圖3係說明本發明之研磨方法的一實施形態之圖，表示於圖2之半導體晶圓的電路面上之樹脂組成物被覆保護薄片或固定用治具之狀態。Fig. 3 is a view showing an embodiment of the polishing method of the present invention, showing a state in which the resin composition on the circuit surface of the semiconductor wafer of Fig. 2 is coated with a protective sheet or a fixture.

圖4係說明本發明之研磨方法的一實施形態之圖，表示研磨圖3之半導體晶圓的背面之狀態。Fig. 4 is a view showing an embodiment of the polishing method of the present invention, showing a state in which the back surface of the semiconductor wafer of Fig. 3 is polished.

圖5係說明本發明之研磨方法的一實施形態之圖，表示於圖4之半導體晶圓的背面貼黏黏著薄片，進行加熱或浸漬於溫水而剝離具有樹脂層之保護薄片的狀態。Fig. 5 is a view showing an embodiment of the polishing method of the present invention, showing a state in which a sheet is adhered to the back surface of the semiconductor wafer of Fig. 4, and heated or immersed in warm water to peel off a protective sheet having a resin layer.

7‧‧‧黏著膠帶7‧‧‧Adhesive tape

Claims (14)

一種半導體晶圓之研磨方法，其特徵係於半導體晶圓之電路面側介由可從前述半導體晶圓剝離之樹脂層而設有保護薄片或固定用治具，研磨前述半導體晶圓之背面，前述樹脂層係由含有(A)選自胺基甲酸酯(甲基)丙烯酸酯及二環戊基二(甲基)丙烯酸酯所構成之群中之至少一種、(B)選自2-(1,2-環六羧基醯亞胺)乙基(甲基)丙烯酸酯、二環戊烯氧乙基(甲基)丙烯酸酯、丁基(甲基)丙烯酸酯及異冰片基(甲基)丙烯酸酯所構成之群中之至少一種及(C)光聚合起始劑之樹脂組成物所構成，相對於(A)與(B)之合計量100質量份，含有(A)10~30質量份，(B)70~90質量份，(C)0.5~10質量份。 A method for polishing a semiconductor wafer, characterized in that a protective sheet or a fixing jig is provided on a circuit surface side of a semiconductor wafer via a resin layer peelable from the semiconductor wafer, and the back surface of the semiconductor wafer is polished. The resin layer is at least one selected from the group consisting of (A) selected from the group consisting of urethane (meth) acrylate and dicyclopentyl bis (meth) acrylate, and (B) is selected from the group consisting of 2- (1,2-cyclohexadecylimine)ethyl (meth) acrylate, dicyclopentene oxyethyl (meth) acrylate, butyl (meth) acrylate and isobornyl (methyl) a resin composition comprising at least one of the group consisting of acrylates and (C) a photopolymerization initiator, and containing (A) 10 to 30 with respect to 100 parts by mass of the total of (A) and (B) Parts by mass, (B) 70 to 90 parts by mass, (C) 0.5 to 10 parts by mass. 如申請專利範圍第1項之半導體晶圓之研磨方法，其中於半導體晶圓之電路面側形成較晶圓厚度更淺之深度的溝，使形成樹脂層之樹脂組成物全面地塗佈，研磨前述半導體晶圓之背面而分割成各個晶片。 The method for polishing a semiconductor wafer according to the first aspect of the invention, wherein a groove having a shallower depth than a wafer is formed on a circuit surface side of the semiconductor wafer, and the resin composition forming the resin layer is entirely coated and ground. The back surface of the semiconductor wafer is divided into individual wafers. 如申請專利範圍第1或2項之半導體晶圓之研磨方法，其中於研磨半導體晶圓之背面之後，加熱樹脂層而除去。 A method of polishing a semiconductor wafer according to claim 1 or 2, wherein after polishing the back surface of the semiconductor wafer, the resin layer is heated and removed. 如申請專利範圍第3項之半導體晶圓之研磨方法，其中至少使樹脂層加熱至40~150℃，以除去樹脂層。 A method of polishing a semiconductor wafer according to claim 3, wherein at least the resin layer is heated to 40 to 150 ° C to remove the resin layer. 如申請專利範圍第3項之半導體晶圓之研磨方法，其中至少使樹脂層接觸於30~100℃之溫水，以除去樹脂層。 A method of polishing a semiconductor wafer according to claim 3, wherein at least the resin layer is brought into contact with warm water of 30 to 100 ° C to remove the resin layer. 如申請專利範圍第1或2項之半導體晶圓之研磨方法，其中保護片或固定用治具為光透過性，樹脂層為由丙烯酸系樹脂組成物所構成。 The method for polishing a semiconductor wafer according to claim 1 or 2, wherein the protective sheet or the fixing jig is light transmissive, and the resin layer is composed of an acrylic resin composition. 如申請專利範圍第1或2項之半導體晶圓之研磨方法，其中半導體晶圓為於電路面具有30μm以上1000μm以下之凹凸。 The method of polishing a semiconductor wafer according to claim 1 or 2, wherein the semiconductor wafer has irregularities of 30 μm or more and 1000 μm or less on the circuit surface. 如申請專利範圍第1或2項之半導體晶圓之研磨方法，其中固定用治具為透過波長365nm之光20%以上者。 A method of polishing a semiconductor wafer according to claim 1 or 2, wherein the fixture is 20% or more of light having a wavelength of 365 nm. 一種樹脂組成物，其係使用於如申請專利範圍第1~7項中任一項的半導體晶圓之研磨方法。 A resin composition for use in a method of polishing a semiconductor wafer according to any one of claims 1 to 7. 如申請專利範圍第9項之樹脂組成物，其中前述(A)及(B)皆為疏水性。 The resin composition of claim 9, wherein the above (A) and (B) are hydrophobic. 一種保護薄片，其係使用於如申請專利範圍第1~7項中任一項的半導體晶圓之研磨方法。 A protective sheet for use in a method of polishing a semiconductor wafer according to any one of claims 1 to 7. 如申請專利範圍第11項之保護薄片，其中含有至少一層以上由乙烯-乙酸乙烯酯所構成之層。 A protective sheet according to claim 11 which contains at least one layer of a layer composed of ethylene-vinyl acetate. 如申請專利範圍第11或12項之保護薄片，其中於表面具有黏著層。 A protective sheet according to claim 11 or 12, which has an adhesive layer on the surface. 如申請專利範圍第13項之保護薄片，其中黏著層為由丙烯酸系樹脂組成物所構成。 The protective sheet of claim 13, wherein the adhesive layer is composed of an acrylic resin composition.
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