TWI577563B - A composite sheet for forming a pressure-sensitive adhesive sheet and a protective film and a method for manufacturing a wafer having a protective film - Google Patents

A composite sheet for forming a pressure-sensitive adhesive sheet and a protective film and a method for manufacturing a wafer having a protective film Download PDF

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TWI577563B
TWI577563B TW102118182A TW102118182A TWI577563B TW I577563 B TWI577563 B TW I577563B TW 102118182 A TW102118182 A TW 102118182A TW 102118182 A TW102118182 A TW 102118182A TW I577563 B TWI577563 B TW I577563B
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protective film
film
forming
sheet
wafer
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TW201437035A (en
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Naoya Saiki
Daisuke Yamamoto
Ken Takano
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Lintec Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H01L21/561—Batch processing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L21/6836—Wafer tapes, e.g. grinding or dicing support tapes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H01L23/3157—Partial encapsulation or coating
    • H01L23/3171—Partial encapsulation or coating the coating being directly applied to the semiconductor body, e.g. passivation layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/544—Marks applied to semiconductor devices or parts, e.g. registration marks, alignment structures, wafer maps
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • 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
    • H01L2221/68377—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 with parts of the auxiliary support remaining in the finished device
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2223/00—Details relating to semiconductor or other solid state devices covered by the group H01L23/00
    • H01L2223/544—Marks applied to semiconductor devices or parts
    • H01L2223/54433—Marks applied to semiconductor devices or parts containing identification or tracking information
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2223/00—Details relating to semiconductor or other solid state devices covered by the group H01L23/00
    • H01L2223/544—Marks applied to semiconductor devices or parts
    • H01L2223/54473—Marks applied to semiconductor devices or parts for use after dicing
    • H01L2223/54486—Located on package parts, e.g. encapsulation, leads, package substrate
    • 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
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/27—Manufacturing methods
    • H01L2224/27001—Involving a temporary auxiliary member not forming part of the manufacturing apparatus, e.g. removable or sacrificial coating, film or substrate
    • H01L2224/27003—Involving a temporary auxiliary member not forming part of the manufacturing apparatus, e.g. removable or sacrificial coating, film or substrate for holding or transferring the layer preform
    • 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
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/27—Manufacturing methods
    • H01L2224/273—Manufacturing methods by local deposition of the material of the layer connector
    • H01L2224/2733—Manufacturing methods by local deposition of the material of the layer connector in solid form
    • H01L2224/27334—Manufacturing methods by local deposition of the material of the layer connector in solid form using preformed layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—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
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/27—Manufacturing methods
    • 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
    • H01L2924/30—Technical effects
    • H01L2924/301—Electrical effects
    • H01L2924/3025—Electromagnetic shielding

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Dicing (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Description

黏著板片與保護膜形成用複合板片以及具有保護膜之晶片的製造方法 Composite sheet for forming adhesive sheet and protective film, and method for manufacturing wafer having protective film

本發明係關於包括保護膜形成用複合板片之保護膜形成用複合板片-剝離板片層積體、該層積體之捲取體、以及由該層積體所得之保護膜形成用複合板片。再者，在於本說明書成為「板片」之用語的概念，係包含成為「帶」的用語之概念以及成為「薄膜」的用語之概念者。 The present invention relates to a composite sheet for forming a protective film comprising a protective film, a release sheet laminate, a wound body of the laminate, and a composite for forming a protective film obtained from the laminate. Plate. In addition, this specification is a concept of the term "plate", and includes the concept of a term "belt" and the concept of a term "film".

近年，使用所謂被稱為面朝下(face down)方式之構裝法進行之半導體裝置。在於面朝下方式，使用於電路面上具有凸塊等的電極之半導體晶片，該電極與配線基板接合。因此，與晶片的電路面為相反側的面(晶片背面)露在外面。 In recent years, a semiconductor device called a face down method has been used. In a face-down manner, a semiconductor wafer having electrodes having bumps or the like on a circuit surface is bonded to the wiring substrate. Therefore, the surface (the wafer back surface) on the opposite side to the circuit surface of the wafer is exposed to the outside.

於專利文獻1揭示有一種切割帶一體型半導體背面用薄膜，其係兼具用於保護該露在外面的晶片背面之保護膜形成用薄膜，與使用於提供晶片的半導體晶圓之切割步驟之切割板片之層狀體，於基材上具有放射線硬化型之黏著劑層之切割帶，及具有設於該黏著劑層上之覆晶片型半導體背面用薄膜之切割帶一體型半導體背面用薄膜，上述黏著劑層係藉由放射線照射預先硬化者。 Patent Document 1 discloses a film for dicing tape-integrated semiconductor back surface, which is a film for protecting a protective film formed on the back surface of a wafer exposed to the outside, and a cutting step for a semiconductor wafer for supplying a wafer. a dicing body for cutting a sheet, a dicing tape having a radiation-curable adhesive layer on a substrate, and a dicing tape-integrated semiconductor back surface film having a film for a wafer-type semiconductor back surface provided on the adhesive layer The above adhesive layer is pre-hardened by radiation irradiation.

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

[專利文獻1]日本特開2011-228451號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-228451

但是，揭示於專利文獻1之切割帶一體型半導體背面用薄膜，具有如下的問題。即，上述薄膜(即，保護膜形成用複合板片)之黏著劑層，由於以放射線照射預先硬化，故對覆晶片型半導體背面用薄膜(即，保護膜形成用薄膜)之黏著性變低。此係，於實施半導體晶圓等的板狀的被加工構件的切割步驟之後，將藉由該切割而得之晶片拾取時，雖可貢獻於保護膜形成用薄膜與黏著劑層之間的剝離變容易，但另一方面，於被加工構件的切割步驟中，保護膜形成用薄膜或以該等形成之保護膜(在於本說明書，有將保護膜形成用薄膜及保護膜總稱為「保護膜等」之情形。)與黏著劑層之間容易發生剝離，有保護膜形成用薄膜之一部分飛散(以下，亦稱為「薄膜飛散」。)之情形。 However, the film for dicing tape-integrated semiconductor back surface disclosed in Patent Document 1 has the following problems. In other words, since the adhesive layer of the film (that is, the composite sheet for forming a protective film) is preliminarily cured by radiation, the adhesion to the film for covering the wafer-type semiconductor back surface (that is, the film for forming a protective film) is low. . In this case, after the dicing step of the plate-shaped workpiece to be processed such as a semiconductor wafer, the wafer obtained by the dicing can be contributed to the peeling between the film for forming a protective film and the adhesive layer. On the other hand, in the dicing step of the member to be processed, the film for forming a protective film or the protective film formed by the film (in the present specification, the film for forming a protective film and the protective film are collectively referred to as a "protective film". In the case of the film, the peeling layer is likely to be peeled off, and a part of the film for forming a protective film is scattered (hereinafter also referred to as "film scattering").

本發明之課題係在於提供包括抑制上述薄膜飛散之問題之發生之保護膜形成用複合板片之保護膜形成用複合板片-剝離板片層積體、由該層積體之捲取體、該層積體所得之保護膜形成用複合板片、及使用上述層積體之具有保護膜之晶片的製造方法。再者，在於本說明書，所謂保護膜形成用複合板片，係指包括基材及層積於基材的一方之面之黏著劑層之黏著板片，及層積於黏著板片之黏著劑層側之面之保護膜形成 用薄膜之層積體。 An object of the present invention is to provide a composite sheet-peeling sheet laminate for forming a protective film comprising a composite sheet for forming a protective film which inhibits the occurrence of the problem of scattering of the film, a wound body of the laminate, A composite sheet for forming a protective film obtained by the laminate, and a method for producing a wafer having a protective film using the laminate. In the present specification, the composite sheet for forming a protective film refers to an adhesive sheet including a substrate and an adhesive layer laminated on one surface of the substrate, and an adhesive laminated on the adhesive sheet. Protective film formation on the side of the layer side A laminate of films is used.

為達成上述目的，本發明者們研究的結果，發現成為薄膜飛散的對象之保護膜等的個片，係在於保護膜等，位於接近其外周的部分(周緣部)之情形為多。特別是保護膜等之中，沒有貼附於半導體晶圓等的被加工構件，於切割步驟時位於保護膜等的主面露出之區域(在於本說明書，亦稱為「露出區域」。)之保護膜等的個片容易發生薄膜飛散之見識。基於該見識進一步研究的結果，得到藉由使保護膜形成用薄膜之主面之全面接於被加工構件地，設定保護膜形成用薄膜之主面之形狀，可減低發生露出區域而發生薄膜飛散的可能性之見識。 In order to achieve the above-mentioned object, the present inventors have found that a sheet of a protective film or the like which is a target of scattering of a film is a protective film or the like, and is located in a portion (peripheral portion) close to the outer periphery thereof. In particular, among the protective film and the like, there is no member to be processed attached to a semiconductor wafer or the like, and is exposed in a region where the main surface of the protective film or the like is exposed during the dicing step (also referred to as "exposed region" in the present specification). Sheets such as protective films are prone to the phenomenon of film scattering. As a result of further investigation, it is found that the shape of the main surface of the film for forming a protective film is set by integrally connecting the main surface of the film for forming a protective film to the member to be processed, and the occurrence of film scattering can be reduced by reducing the occurrence of the exposed region. The insight of the possibilities.

基於該見識所完成之本發明，第1，提供一種保護膜形成用複合板片-剝離板片層積體，其包括：剝離板片；及保護膜形成用複合板片，層積於上述剝離板片之剝離面上，上述保護膜形成用複合板片，包括：基材；黏著板片，其包括層積於上述基材之一方的主面之黏著劑層；及保護膜形成用薄膜，其係層積於上述黏著板片之上述黏著劑層側之主面之至少一部分的區域，藉由硬化可形成保護膜，使上述保護膜形成用複合板片之上述保護膜形成用薄膜側之主面與上述剝離板片之剝離面相貼合，上述保護膜形成用複合板片係層積於上述剝離板片，在於上述保護膜形成用複合板片之上述保護膜形成用薄膜側之主面，於使用時應貼附於被加工構件之區域之加工用區域，相當於與上述保護膜形成用薄膜之上述剝離面相對之主面之全區域，或包含該主面之全區域(發明1)。 According to the present invention, the first aspect of the invention provides a composite sheet-peeling sheet laminate for forming a protective film, comprising: a release sheet; and a composite sheet for forming a protective film, which is laminated on the peeling a composite sheet for forming a protective film, comprising: a substrate; an adhesive sheet comprising an adhesive layer laminated on one main surface of the substrate; and a film for forming a protective film, A layer formed on the film side of the protective film for forming the composite sheet for forming a protective film by forming a protective film by laminating at least a part of the main surface of the adhesive sheet on the side of the adhesive layer. The main surface is bonded to the peeling surface of the peeling sheet, and the composite sheet for forming a protective film is laminated on the peeling sheet, and the main surface of the film for forming the protective film is formed on the composite sheet for forming a protective film. a processing region to be attached to a region of the member to be processed at the time of use, corresponding to the entire region of the main surface facing the peeling surface of the film for forming a protective film, or the entire region including the main surface 1).

在於上述發明(發明1)，其中上述保護膜形成用薄膜與上述剝離面相對之主面之外周，與上述加工用區域之外周，以平面視之離間距離，以0mm以上10mm以下為佳(發明2)。 According to the invention of the first aspect of the invention, the outer surface of the main surface of the film for forming a protective film and the outer surface of the processing surface is preferably 0 mm or more and 10 mm or less in the outer periphery of the processing region. 2).

在於上述發明(發明1、2)，其中使上述保護膜形成用複合板片所具有的上述保護膜形成用薄膜硬化形成保護膜時，上述黏著板片對上述保護膜之黏著力以0.5N/25mm以下為佳(發明3)。 In the above invention (Inventions 1 and 2), when the protective film forming film of the composite sheet for protective film formation is cured to form a protective film, the adhesion of the adhesive sheet to the protective film is 0.5 N/ 25 mm or less is preferable (Invention 3).

在於上述發明(發明1至3)，其中上述黏著板片對上述保護膜形成用薄膜之黏著力以0.5N/25mm以下為佳(發明4)。 In the above invention (Inventions 1 to 3), the adhesion of the adhesive sheet to the film for forming a protective film is preferably 0.5 N/25 mm or less (Invention 4).

在於上述發明(發明1至4)，其中上述黏著板片之上述黏著劑層側之主面之上述保護膜形成用薄膜貼附之區域，由能量線硬化型黏著劑之硬化物所組成之黏著劑之面所組成為佳(發明5)。 In the above-mentioned invention (Inventions 1 to 4), the adhesive film sheet is adhered to the surface of the protective film forming main surface of the adhesive layer side, and is adhered by a hardened material of an energy ray-curable adhesive. The composition of the agent is preferred (Invention 5).

在於上述發明(發明1至5)，其中上述保護膜形成用薄膜含有填充材，上述保護膜形成用薄膜之填充材的含量，作為佔上述保護膜形成用薄膜之全固形份之質量的比例，以30質量%以上80質量%以下為佳(發明6)。 In the above-mentioned invention (Inventions 1 to 5), the film for forming a protective film contains a filler, and the content of the filler of the film for forming a protective film is a ratio of the mass of the entire solid portion of the film for forming a protective film. It is preferably 30% by mass or more and 80% by mass or less (Invention 6).

本發明，第2，提供一種保護膜形成用複合板片，其係由上述發明(發明1至6)之保護膜形成用複合板片-剝離板片層積體，剝離上述剝離板片而成(發明7)。 According to a second aspect of the invention, there is provided a composite sheet for forming a protective film, comprising the composite sheet-peeling sheet laminate for forming a protective film according to the invention (Inventions 1 to 6), wherein the peeling sheet is peeled off. (Invention 7).

本發明，第3，提供一種具有保護膜之晶片的製造方法，其特徵在於：由上述發明(發明1至6)之保護膜形成用 複合板片-剝離板片層積體，剝離上述保護膜形成用複合板片，使上述保護膜形成用薄膜的一方的主面外露，藉由在被加工構件的一面，將上述剝離之保護膜形成用複合板片，使上述保護膜形成用薄膜之上述外露之一方的主面全體，以上述加工構件之一面覆蓋地貼附，得到包括上述保護膜形成用複合板片與上述被加工構件之第一層積構造體，使含於上述第一層積構造體之上述保護膜形成用複合板片之上述保護膜形成用薄膜硬化，得到具有依序層積上述黏著板片、上述保護膜及上述被加工構件之部分之第二層積構造體，將上述第二層積構造體，由上述黏著板片側與相反側切割，將上述被加工構件與上述保護膜一起個片化，得到具有上述保護膜之個片與該個片附著在一方的面之晶片所組成之具有保護膜之晶片之複數，層積於上述黏著板片上之部分之第三層積構造體，將上述第三層積構造體所具有之上述複數具有保護膜之晶片，個別拾取得到上述具有保護膜之晶片(發明8)。 According to a third aspect of the invention, there is provided a method for producing a wafer having a protective film, comprising: a protective film formed by the invention (Inventions 1 to 6) In the composite sheet-peeling sheet laminate, the composite sheet for forming a protective film is peeled off, and one main surface of the film for forming a protective film is exposed, and the peeling protective film is formed on one surface of the member to be processed. The composite sheet is formed, and the entire main surface of the protective film forming film is attached to one surface of the processed member, and the composite sheet for forming a protective film and the member to be processed are obtained. The first laminated structure is obtained by curing the protective film forming film of the composite sheet for forming a protective film formed in the first laminated structure, thereby obtaining the adhesive sheet, the protective film, and the like. a second laminated structure of the part to be processed, wherein the second laminated structure is cut from the side of the adhesive sheet and the opposite side, and the workpiece is formed into a sheet together with the protective film. a plurality of wafers of the protective film and a wafer having a protective film composed of the wafers attached to one of the wafers, and a third portion of the laminated film on the adhesive sheet In the laminated structure, the plurality of wafers having the protective film included in the third laminated structure are individually picked up and obtained on the wafer having the protective film (Invention 8).

本發明，第4，提供一種具有保護膜之晶片的製造方法，其特徵在於：由上述發明(發明1至6)之保護膜形成用複合板片-剝離板片層積體，剝離上述保護膜形成用複合板片，使上述保護膜形成用薄膜的一方的主面外露，藉由在被加工構件的一面，將上述剝離之保護膜形成用複合板片，使上述保護膜形成用薄膜之上述外露之一方的主面全體，以上述加工構件之一面覆蓋地貼附，得到包括上述保護膜形成用複合板片與上述被加工構件之第一層積構造體，將上述第一層積構造體，由上述黏著板片側與相反側切割將上述被加工構件與上述 保護膜形成用薄膜一起個片化，得到具有上述保護膜形成用薄膜之個片與該個片附著於一方的面之晶片所組成之具有保護膜形成用薄膜之晶片之複數，層積於上述黏著板片上之部分之第四層積構造體，使上述第四層積構造體所包括之上述具有保護膜形成用薄膜之晶片之上述保護膜形成用薄膜之個片硬化，將上述具有保護膜形成用薄膜之晶片作為上述具有保護膜之晶片，將上述黏著板片上的上述複數具有保護膜之晶片個別拾取得到上述具有保護膜之晶片(發明9)。 According to a fourth aspect of the invention, there is provided a method for producing a wafer having a protective film, comprising: a composite sheet-peeling sheet laminate for forming a protective film according to the invention (Inventions 1 to 6), and the protective film is peeled off In the composite sheet for forming, the main surface of the film for forming a protective film is exposed, and the composite sheet for forming a protective film to be peeled off is formed on one surface of the member to be processed. The entire main surface of one of the exposed surfaces is attached to one surface of the processed member, and a first laminated structure including the composite sheet for forming a protective film and the member to be processed is obtained, and the first laminated structure is obtained. Cutting the above-mentioned processed member from the side of the adhesive sheet and the opposite side The film for forming a protective film is formed into a plurality of sheets, and a plurality of wafers having a film for forming a protective film and a wafer having a film adhered to one surface of the film are laminated, and the film is laminated on the film. a fourth laminated structure on a portion of the above-mentioned fourth laminated structure, wherein the protective film forming film of the film having the protective film forming film is cured, and the protective film is cured A wafer for forming a film is used as the wafer having the protective film, and the plurality of wafers having the protective film on the adhesive sheet are individually picked up and obtained on the wafer having the protective film (Invention 9).

本發明，於第5，提供一種具有保護膜之晶片的製造方法，其特徵在於：由上述發明(發明1至6)之保護膜形成用複合板片-剝離板片層積體，剝離上述保護膜形成用複合板片，使上述保護膜形成用薄膜的一方的主面外露，藉由在被加工構件的一面，將上述剝離之保護膜形成用複合板片，使上述保護膜形成用薄膜之上述外露之一方的主面全體，以上述加工構件之一面覆蓋地貼附，得到包括上述保護膜形成用複合板片與上述被加工構件之第一層積構造體，將上述第一層積構造體，由上述黏著板片側與相反側切割將上述被加工構件與上述保護膜形成用薄膜一起個片化，得到具有上述保護膜形成用薄膜之個片與該個片附著於一方的面之晶片所組成之具有保護膜形成用薄膜之晶片之複數，層積於上述黏著板片上之部分之第四層積構造體，上述第四層積構造體所包括之上述複數具有保護膜形成用薄膜之晶片，個別拾取，使藉由上述拾取所得之上述具有保護膜形成用薄膜之晶片之上述保護膜形成用薄膜之個片硬化，將上述具有保護膜形成用薄膜之晶片作為上述具 有保護膜之晶片(發明10)。 According to a fifth aspect of the invention, there is provided a method for producing a wafer having a protective film, characterized in that the composite sheet-peeling sheet laminate for forming a protective film according to the invention (Inventions 1 to 6) is peeled off from the above-mentioned protection. In the composite sheet for film formation, one of the main surfaces of the film for forming a protective film is exposed, and the composite sheet for forming a protective film to be peeled off is formed on one surface of the member to be processed, and the film for forming a protective film is formed. The entire main surface of one of the exposed surfaces is attached to one surface of the processed member, and a first laminated structure including the composite sheet for forming a protective film and the member to be processed is obtained, and the first laminated structure is obtained. The film is formed by cutting the film to be processed and the film for forming a protective film together, and the film having the film for forming a protective film and the wafer on which the film is attached to one surface is obtained. a fourth laminated structure in which a plurality of wafers having a film for forming a protective film are formed, a portion laminated on the adhesive sheet, and a fourth laminated structure The wafer having the film for forming a protective film is individually picked up, and the sheet for the protective film forming film of the film having the protective film forming film obtained by the pick-up is cured, and the protective film is formed. Film of the film as the above A wafer with a protective film (Invention 10).

在於上述發明(發明10)，其中對上述第一層積構造體及上述第四層積構造體之任意一個，由上述黏著板片側照射雷射光進行標印，將上述具有保護膜形成用薄膜之晶片所包括之上述保護膜形成用薄膜作為具有標記之保護膜形成用薄膜為佳(發明11)。 According to a third aspect of the invention, the first laminated structure and the fourth laminated structure are irradiated with laser light by the side of the adhesive sheet, and the film for forming a protective film is used. The film for forming a protective film included in the wafer is preferably a film for forming a protective film having a mark (Invention 11).

在於上述發明(發明1、2)，上述黏著板片，包括層積於其上述黏著劑層側之主面之一部分的區域之界面接著調整層，上述保護膜形成用薄膜，亦可層積在接於其一方的主面的全面在於上述界面接著調整層與上述黏著層之主面之相反側之主面。此時，與上述界面接著調整層之上述黏著層面相對之主面相反側之主面，亦可包含沒有層積上述保護膜形成用薄膜之區域。或者，上述保護膜形成用複合板片，亦可進一步包括：夾具接著層，其係層積在位於上述黏著板片之上述黏著劑層側之主面沒有層積上述接面接著調整層之區域之外周的區域。 According to the invention (Inventions 1 and 2), the adhesive sheet includes an interface layer in a region of a portion of the main surface on the side of the adhesive layer, and the protective film forming film may be laminated on the adhesive film. The main surface of one of the main faces is the main surface of the interface opposite to the main surface of the adhesive layer. In this case, the main surface opposite to the main surface facing the adhesion layer of the interface subsequent adjustment layer may include a region where the film for forming a protective film is not laminated. Alternatively, the composite sheet for forming a protective film may further include: a jig adhesive layer laminated on a main surface of the adhesive sheet on the side of the adhesive layer side where the joint surface and the adjustment layer are not laminated Outside the area.

在於上述發明(發明1、2)，亦可進一步包括：夾具接著層，其係層積在位於上述黏著板片之上述黏著劑層側之主面之一部分的區域，對該主面之上述加工用區域之外周的區域。 The invention (Inventions 1 and 2) may further include: a jig adhesive layer laminated on a portion of the main surface of the adhesive sheet on the side of the adhesive layer, the processing of the main surface Use the area outside the area.

在於上述發明(發明6)，上述基材含有填充材，上述保護膜形成用薄膜所含有的填充材佔上述保護膜形成用薄膜之全固形份的質量的比例，較上述基材所含有的填充材佔上述基材的全固形份的質量的比例更多為佳。 According to a sixth aspect of the invention, the substrate includes a filler, and the filler contained in the film for forming a protective film accounts for the mass of the total solid content of the film for forming a protective film, and is more than the filler contained in the substrate. The proportion of the material in the total solid content of the above substrate is more preferably.

本發明，亦提供一種捲取體，其係將關於上述發明(發明1至6)之保護膜形成用複合板片-剝離板片層積體之上述剝離板片之長邊方向捲收而得。 The present invention also provides a wound body obtained by winding the longitudinal direction of the peeling sheet of the composite sheet-peeling sheet laminate for protective film formation of the invention (Inventions 1 to 6). .

在於上述發明(發明8)，亦可對上述第一層積構造體、上述第二層積構造體及上述第三層積構造體之任一，由上述黏著板片側照射雷射光進行標記，將上述具有保護膜之晶片所包括的上述保護膜作為具有標記之保護膜。或者，亦可對由上述第三層積構造體拾取而得之具有上述保護膜之晶片之上述保護膜之與上述晶片相對之主面之相反側之主面照射雷射光，將上述保護膜作為具有標記之保護膜。 In the above invention (Invention 8), any one of the first laminated structure, the second laminated structure, and the third laminated structure may be marked by irradiating laser light to the side of the adhesive sheet, and The above protective film included in the wafer having the protective film is used as a protective film having a mark. Alternatively, the main surface of the protective film of the wafer having the protective film obtained by the third laminate structure opposite to the main surface facing the wafer may be irradiated with laser light, and the protective film may be used as the protective film. A protective film with a mark.

在於上述發明(發明9)，亦可對上述第一層積構造體及上述第四層積構造體之任一，由上述黏著板片側照射雷射光進行標記，將上述保護形成用薄膜晶片所包括之上述保護形成用薄膜作為具有標記之保護形成用薄膜。或者，亦可對在於上述具有保護膜之晶片之上述保護膜與上述晶片相面之主面之相反側之主面照射雷射光，將上述保護膜作為具有標記之保護膜。 In the above invention (Invention 9), any one of the first laminated structure and the fourth laminated structure may be marked by irradiating laser light onto the adhesive sheet side, and the protective formation thin film may be included The above-mentioned film for protective formation is used as a film for protective formation having a mark. Alternatively, the main surface of the protective film on the wafer having the protective film on the opposite side to the main surface of the wafer may be irradiated with laser light, and the protective film may be used as a protective film having a mark.

在於上述發明(發明10)，亦可對上述具有保護形成用薄膜之晶片或上述具有保護膜之晶片之與上述晶片側之相反側之主面，不經由上述黏著板片照射雷射光，將上述具有保護膜之晶片作成包括附有標記之保護膜之晶片。 According to the invention (Invention 10), the main surface opposite to the wafer side of the wafer having the protective forming film or the wafer having the protective film may be irradiated with laser light without passing through the adhesive sheet. A wafer having a protective film is formed into a wafer including a protective film with a mark.

關於本發明之保護膜形成用複合板片-剝離板片層積體所包括之保護膜形成用複合板片之保護膜形成用薄膜側 之主面，於使用時應貼附於被加工構件之區域之加工用區域，由於包含保護膜形成用薄膜之與剝離面相對之主面，故在於切割加工時，於保護膜等不容易發生露出之區域。因此，可減低起因於位於露出區域之保護膜形成用薄膜之薄膜飛散的可能性。此外，藉由將關於本發明之保護膜形成用複合板片-剝離板片層積體所包括之保護膜形成用複合板片，用於作為切割板片，可以高生產性製造品質優良的具有保護膜之晶片。 The composite film sheet for forming a protective film of the present invention - the film side for forming a protective film for forming a composite sheet for forming a protective film The main surface of the film to be processed is attached to the processing region in the region of the member to be processed. Since the main surface of the film for forming a protective film and the peeling surface is included, it is not likely to occur in the protective film or the like during the cutting process. The exposed area. Therefore, the possibility of scattering of the film due to the film for forming a protective film in the exposed region can be reduced. In addition, the composite sheet for forming a protective film comprising the composite sheet-peeling sheet laminate for forming a protective film of the present invention can be used as a dicing sheet, and can be manufactured with high productivity and excellent quality. A wafer of protective film.

【發明內容】 [Summary of the Invention]

以下，說明關於本發明之實施形態。 Hereinafter, embodiments of the present invention will be described.

1.保護膜形成用複合板片-剝離板片層積體 1. Composite sheet for protective film formation - peeled sheet laminate

如第1圖所示，關於本發明之一實施形態之保護膜形成用複合板片-剝離板片層積體(以下，亦稱為「PR層積體」。)100，包括：剝離板片20及保護膜形成用複合板片10，保護膜形成用複合板片10，係使其保護膜形成用薄膜4側之主面10A與剝離板片20之剝離面20A相對地層積剝離板片20。 As shown in Fig. 1, a composite sheet-peel sheet laminate (hereinafter also referred to as "PR laminate") 100 for forming a protective film according to an embodiment of the present invention includes a peeling sheet. 20 and the composite sheet 10 for forming a protective film, and the composite sheet 10 for forming a protective film, the main surface 10A on the side of the protective film forming film 4 and the peeling surface 20A of the peeling sheet 20 are laminated to peel the sheet 20 .

如第2圖所示，保護膜形成用複合板片10，包括：黏著板片1，其包括基材2、及層積於基材2之一方的主面2A之黏著劑層3；及保護膜形成用薄膜4，其係層積於黏著板片1之黏著劑層3側之主面1A之一部分之區域1a，可藉由硬化形成保護膜。 As shown in Fig. 2, the composite sheet 10 for forming a protective film comprises: an adhesive sheet 1, comprising a substrate 2, and an adhesive layer 3 laminated on the main surface 2A of one of the substrates 2; and protection The film forming film 4 is laminated on the region 1a of a portion of the main surface 1A on the side of the adhesive layer 3 of the adhesive sheet 1, and a protective film can be formed by curing.

以下，說明構成PR層積體100之各要素。 Hereinafter, each element constituting the PR laminate 100 will be described.

(1)黏著板片 (1) Adhesive sheet

關於本實施形態之黏著板片1，係作為包括黏著板片1及層積於黏著板片1之黏著劑層3側之主面1A之一部分之區域1a之保護膜形成用薄膜4之保護膜形成用複合板片10之構成要素之一，例如可使用於切割具有板狀的形狀之被加工構件W時者。 The adhesive sheet 1 of the present embodiment is a protective film for the protective film forming film 4 including the adhesive sheet 1 and the region 1a of one portion of the main surface 1A laminated on the adhesive layer 3 side of the adhesive sheet 1. One of the constituent elements of the composite sheet 10 for forming can be used, for example, for cutting a workpiece W having a plate shape.

(1-1)基材 (1-1) Substrate

關於本實施形態之黏著板片1之基材2，只要在切割步驟之後所進行之擴展步驟等不破斷，該構成材料並無特別限定，通常係以樹脂系的材料作為主材之薄膜所構成。該薄膜之具體例，可舉乙烯-醋酸乙烯酯共聚物薄膜、乙烯-(甲基)丙烯酸共聚物薄膜、乙烯-(甲基)丙烯酸酯共聚物薄膜等之乙烯系共聚合薄膜；低密度聚乙烯(LDPE)薄膜、直鏈低密度聚乙烯(LLDPE)薄膜、高密度聚乙烯(HDPE)薄膜等之聚乙烯薄膜、聚丙烯薄膜、聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、乙烯-降冰片烯共聚物薄膜、降冰片烯樹脂薄膜等的聚烯烴系薄膜；聚氯乙烯薄膜、氯乙烯共聚物薄膜等的聚氯乙烯系薄膜；聚對苯二甲酸乙二醇酯薄膜、聚對苯二甲酸丁二醇酯薄膜等的聚酯系薄膜；聚氨酯薄膜；聚醯亞胺薄膜；聚苯乙烯薄膜；聚碳酸酯薄膜；氟樹脂薄膜等。此外，亦可使用該等的架橋薄膜、離聚物樹脂等之變性薄膜。上述基材2可由該等的1種所組成之薄膜，亦可進一步組合2種以上之層積薄膜。再者，於本說明書之「(甲基)丙烯酸」，係指丙烯酸及甲基丙烯酸之雙方之意思。關於其他類似的用語亦相同。 The base material 2 of the pressure-sensitive adhesive sheet 1 of the present embodiment is not particularly limited as long as the expansion step or the like after the cutting step is not broken, and is usually composed of a film made of a resin-based material as a main material. . Specific examples of the film include an ethylene-vinyl acetate copolymer film, an ethylene-(meth)acrylic copolymer film, an ethylene-(meth)acrylate copolymer film, and the like, and a low-density polymerization. Polyethylene film, polypropylene film, polybutylene film, polybutadiene film, polymethyl pentene, such as ethylene (LDPE) film, linear low density polyethylene (LLDPE) film, high density polyethylene (HDPE) film, etc. a polyolefin film such as an ene film, an ethylene-norbornene copolymer film or a norbornene resin film; a polyvinyl chloride film such as a polyvinyl chloride film or a vinyl chloride copolymer film; and polyethylene terephthalate A polyester film such as an ester film or a polybutylene terephthalate film; a polyurethane film; a polyimide film; a polystyrene film; a polycarbonate film; a fluororesin film. Further, a denatured film such as a bridge film or an ionomer resin may be used. The base material 2 may be a film composed of one of these, and two or more laminated films may be further combined. In addition, "(meth)acrylic acid" in this specification means the both sides of an acrylic acid and methacrylic acid. The same is true for other similar terms.

使用關於本實施形態之保護膜形成用複合板片10所形成之具有保護膜之晶片(細節將於後述。)係以雷射標記之具有標記保護膜之晶片時，用於雷射標記之雷射係透過基材2照射時，基材2以雷射光的穿透性優良者為佳。用於雷射標記之雷射的種類並無特別限定。可例示例如，具有532nm、1064nm等的波長之雷射。構成如此之基材2之薄膜，可例示乙烯系共 聚合薄膜、聚烯烴系薄膜、聚氯乙烯系薄膜等。 A wafer having a protective film formed by the composite sheet 10 for forming a protective film of the present embodiment (details will be described later) is a laser for marking a protective film, and is used for a laser marking. When the radiation is transmitted through the substrate 2, the substrate 2 is preferably excellent in penetration of laser light. The type of laser used for the laser mark is not particularly limited. For example, a laser having a wavelength of 532 nm, 1064 nm or the like can be exemplified. The film constituting the substrate 2 can be exemplified by a vinyl group. A polymeric film, a polyolefin-based film, a polyvinyl chloride-based film, or the like.

構成基材2之薄膜，以包括乙烯系共聚合薄膜及聚烯烴系薄膜之至少一種為佳。 The film constituting the substrate 2 preferably contains at least one of a vinyl copolymer film and a polyolefin film.

乙烯系共聚合薄膜，可藉由改變共聚合比等，容易地將其機械特性控制於廣泛的範圍。因此，包括乙烯系共聚合薄膜之基材2係將關於本實施形態之保護膜形成用複合板片10使用於作為切割板片時，容易滿足作為切割板片之基材所要求之機械特性。此外，乙烯系共聚合薄膜對黏著劑層3之密著性相對較高，故使用關於本實施形態之保護膜形成用複合板片10作為切割板片時，於基材2與黏著劑層3之界面不容易發生剝離。 The ethylene-based copolymer film can easily control its mechanical properties in a wide range by changing the copolymerization ratio and the like. Therefore, when the composite sheet 10 for forming a protective film of the present embodiment is used as a dicing sheet, it is easy to satisfy the mechanical properties required as a substrate of the dicing sheet. Further, since the ethylene-based copolymerized film has a relatively high adhesion to the adhesive layer 3, when the composite sheet 10 for forming a protective film of the present embodiment is used as a dicing sheet, the substrate 2 and the adhesive layer 3 are used. The interface is not prone to peeling.

乙烯系共聚合薄膜及聚烯烴系薄膜，由於對作為切割板片之特性帶來不良影響的成分(例如，以聚氯乙烯系薄膜等，含於該薄膜之可塑劑由基材2轉移到黏著劑層3，進一步分佈在黏著劑層3與基材2相對之側之相反側之面，而有降低黏著劑層3對被著體之黏著性之情形。)的含量少，故不容易發生黏著劑層3對被著體之黏著性等的問題。即，乙烯系共聚合薄膜及聚烯烴系薄膜之化學穩定性優良。 In the ethylene-based copolymer film and the polyolefin-based film, a component which adversely affects the characteristics of the dicing sheet (for example, a polyvinyl chloride-based film or the like, the plasticizer contained in the film is transferred from the substrate 2 to the adhesive. The agent layer 3 is further distributed on the opposite side of the side opposite to the side of the adhesive layer 3, and has a reduced adhesiveness of the adhesive layer 3 to the object. The problem of adhesion of the adhesive layer 3 to the object to be adhered. That is, the ethylene-based copolymer film and the polyolefin-based film are excellent in chemical stability.

基材2，於以上述樹脂系材料作為主材之薄膜內，含有顏料、難燃劑、可塑劑、帶電防止劑、潤滑劑、填充劑等的各種添加劑。顏料，可舉例如，二氧化鈦、碳黑等。此外，填充劑，可例示例如三聚氰胺樹脂等之有機系材料，如氣相法二氧化矽等之無機系材料及鎳粒子等之金屬系材料。如此之添加劑之含量，並無特別限定，應保留在基材2可發揮所期望的功能(進行雷射標記時雷射光的穿透性亦包含於該功能。)，不 失去平滑性及柔軟性的範圍。 The base material 2 contains various additives such as a pigment, a flame retardant, a plasticizer, a charge preventing agent, a lubricant, a filler, and the like in the film containing the resin-based material as a main material. The pigment may, for example, be titanium dioxide, carbon black or the like. Further, the filler may, for example, be an organic material such as a melamine resin, an inorganic material such as a vapor phase cerium oxide or a metal material such as nickel particles. The content of such an additive is not particularly limited, and it should be retained in the substrate 2 to exhibit a desired function (the penetration of laser light is also included in the function when performing laser marking). Loss of range of smoothness and softness.

使用紫外線作為照射黏著劑層3之能量線時，基材2對紫外線具有穿透性為佳。使用電子線作為照射黏著劑層3之能量線時，基材2對電子線具有穿透性為佳。 When ultraviolet rays are used as the energy ray for irradiating the adhesive layer 3, the substrate 2 preferably has transparency to ultraviolet rays. When the electron beam is used as the energy ray for irradiating the adhesive layer 3, the substrate 2 is preferably penetrating to the electron beam.

此外，於基材2與黏著劑層3相對之主面(以下、亦稱為「基材相對面」。)2A，存在有選自由羧基、以及其離子及鹽所組成之群之1種或2種以上之成分為佳。在於基材2之上述成分與關於黏著劑層3之成分(可例示構成黏著劑層3之成分及架橋劑(γ)等使用於形成黏著劑層3時使用的成分。)藉由化學性相互作用，可降低在該等之間發生剝離的可能性。於基材相對面2A存在如此之成分之具體的手法並無特別限定。亦可例如，將基材2本身，作為例如以乙烯-(甲基)丙烯酸共聚物薄膜、離聚物樹脂薄膜等，使成為構成基材2之材料之樹脂具有選自由羧基、及由其離子及鹽所組成之群之1種或2種以上者。於基材相對面2A存在上述成分之別的手法，基材2係例如為聚烯烴系薄膜，而對基材相對面2A側施以電暈處理，或設底漆層亦可。此外，於基材2之基材相對面2A之相反側之面，只要可發揮所期望的功能，亦可設有各種塗膜。 Further, in the main surface (hereinafter, also referred to as "substrate opposing surface") 2A of the substrate 2 and the adhesive layer 3, there is one selected from the group consisting of a carboxyl group and an ion and a salt thereof. Two or more components are preferred. The components of the substrate 2 and the components of the adhesive layer 3 (the components used for forming the adhesive layer 3 and the bridging agent (γ) and the like used in forming the adhesive layer 3 are exemplified). The effect is to reduce the possibility of peeling between the two. The specific method of presenting such a component on the opposite surface 2A of the substrate is not particularly limited. For example, the substrate 2 itself may be, for example, an ethylene-(meth)acrylic copolymer film or an ionomer resin film, and the resin constituting the material of the substrate 2 may be selected from a carboxyl group and an ion thereof. And one or more of the group consisting of salts. The base material 2 may be a polyolefin-based film, for example, a polyolefin-based film may be applied to the substrate-facing surface 2A, and a corona treatment may be applied to the substrate-facing surface 2A side, or a primer layer may be provided. Further, various coating films may be provided on the surface opposite to the substrate facing surface 2A of the substrate 2 as long as a desired function can be exhibited.

基材2的厚度，只要不會發生在切割步驟被切斷或在擴展步驟或拾取步驟破斷等異常，並無特別限定。以20μm以上450μm以下為佳，以25μm以上400μm以下更佳，以50μm以上350μm以下的範圍特別佳。 The thickness of the substrate 2 is not particularly limited as long as it does not cause an abnormality such as cutting in the cutting step or breaking in the expanding step or the picking step. It is preferably 20 μm or more and 450 μm or less, more preferably 25 μm or more and 400 μm or less, and particularly preferably 50 μm or more and 350 μm or less.

在於本實施形態之基材2之破斷伸度，於23℃、相對濕度50%所測定之值，以100%以上為佳，特別是以200% 以上1000%以下為佳。在此，破斷伸度，係遵照JIS K7161：1994(ISO 527-1 993)之拉伸試驗，試驗片破斷時之試驗片之長度對原來的長度之伸長率。上述破斷伸度為100%以上之基材2，於擴展步驟時不容易破斷，而容易將切斷被加工構件W所形成之晶片離間者。 The breaking elongation of the substrate 2 of the present embodiment is preferably 100% or more, particularly 200%, at a value measured at 23 ° C and a relative humidity of 50%. Above 1000% is preferred. Here, the breaking elongation is a tensile test in accordance with JIS K7161:1994 (ISO 527-1 993), and the elongation of the length of the test piece when the test piece is broken is the original length. The base material 2 having a breaking elongation of 100% or more is not easily broken during the expansion step, and it is easy to cut off the wafer formed by the workpiece W.

此外，在於本實施形態之基材2之25%變形時拉伸應力以5N/10mm以上15N/10mm以下為佳，最大拉伸應力以15MPa以上50MPa以下為佳。在此，25%變形時拉伸應力及最大拉伸應力，係以遵照JIS K7161：1994之試驗所測定。25%變形時拉伸應力未滿5N/10mm，或最大拉伸應力未滿15MPa，則將保護膜形成用複合板片10貼附於被著構件W之後，固定於環形框等的夾具時，有因基材2柔軟而發生鬆弛之虞，該鬆弛有成為輸送錯誤之原因。另一方面，25%變形時之拉伸應力超過15N/10mm，或最大拉伸應力超過50MPa，則有於擴展步驟時容易發生黏著板片1由環形框等的夾具剝落等之問題之虞。再者，上述破斷伸度，係指25%變形時之拉伸應力、最大拉伸應力係對基材2之原卷之長條方向測定之值。 Further, in the case of 25% deformation of the substrate 2 of the present embodiment, the tensile stress is preferably 5 N/10 mm or more and 15 N/10 mm or less, and the maximum tensile stress is preferably 15 MPa or more and 50 MPa or less. Here, the tensile stress and the maximum tensile stress at 25% deformation were measured in accordance with the test in accordance with JIS K7161:1994. When the tensile stress is less than 5 N/10 mm at the time of 25% deformation, or the maximum tensile stress is less than 15 MPa, the composite sheet 10 for forming a protective film is attached to the member W, and is fixed to a jig such as a ring frame. There is a possibility that the substrate 2 is slack due to the softness of the substrate 2, and this slack is a cause of a conveyance error. On the other hand, when the tensile stress at the time of 25% deformation exceeds 15 N/10 mm, or the maximum tensile stress exceeds 50 MPa, there is a problem in that the adhesive sheet 1 is peeled off by a jig such as a ring frame during the expansion step. In addition, the above-mentioned breaking elongation means the value measured by the tensile stress and the maximum tensile stress at the time of 25% deformation, and the longitudinal direction of the original roll of the base material 2.

(1-2)黏著劑層 (1-2) Adhesive layer

關於本實施形態之黏著板片1之黏著劑層3，可藉由先前習知之各種黏著劑組成物形成而得。作為如此之黏著劑組成物，並無任何限定，可使用例如橡膠系、丙烯酸系、矽酮系、聚乙烯基醚等的黏著劑組成物。此外，亦可使用能量線硬化型或加熱發泡型、水膨潤型的黏著劑組成物。 The adhesive layer 3 of the adhesive sheet 1 of the present embodiment can be formed by various conventional adhesive compositions. The adhesive composition is not particularly limited, and an adhesive composition such as a rubber-based, acrylic-based, anthrone-based or polyvinyl ether-based adhesive can be used. Further, an energy ray-curing type or a heat-foaming type or water-swellable type of adhesive composition can also be used.

關於本實施形態之黏著板片1所包括之黏著劑層 3，亦有由含有藉由能量線的照射產生聚合反應之成分，構成能量線聚合型黏著劑組成物之情形。作為該聚合之能量線，可例示X射線、紫外線等的電磁波、電子線等。該等的能量線之中，以設置設備所需的成本低，工作性亦優良的紫外線為佳。 The adhesive layer included in the adhesive sheet 1 of the present embodiment 3. There is also a case where a component containing a polymerization reaction by irradiation with an energy ray constitutes an energy ray-polymerizable adhesive composition. Examples of the energy ray of the polymerization include electromagnetic waves such as X-rays and ultraviolet rays, and electron beams. Among these energy lines, ultraviolet rays having a low cost required for setting up the equipment and excellent workability are preferred.

作為可藉由紫外線聚合之黏著劑組成物之一例，可舉以下說明之丙烯酸系聚合物(α)及能量線聚合性化合物(β)、以及按照必要含有架橋劑(γ)等之黏著劑組成物。 Examples of the adhesive composition which can be polymerized by ultraviolet light include an acrylic polymer (α) and an energy ray polymerizable compound (β) described below, and an adhesive agent such as a bridging agent (γ) as necessary. Things.

(1-2-1)丙烯酸系聚合物(α) (1-2-1) Acrylic polymer (α)

用於形成關於本實施形態之黏著劑層3之黏著劑組成物之一例，含有烯酸系聚合物(α)。在由該這黏著劑組成物形成之黏著劑層3，丙烯酸系聚合物(α)亦有至少其一部分與後述之架橋劑(γ)進行架橋反應作為架橋物含有之情形。 An example of the adhesive composition for forming the pressure-sensitive adhesive layer 3 of the present embodiment contains an olefinic polymer (α). In the adhesive layer 3 formed of the adhesive composition, at least a part of the acrylic polymer (α) is bridged with a bridging agent (γ) to be described later as a bridging material.

丙烯酸系聚合物(α)，可使用先前習知之丙烯酸系聚合物。丙烯酸系聚合物(α)之重量平均分子量(Mw)，由用於形成上述黏著劑層3之黏著劑組成物或對此加入溶劑而得之組成物所組成之塗佈液(在於本說明書，將該等塗佈液總稱為「黏著層形成用塗佈液」。)之塗佈時之造膜性的觀點，以1萬以上200萬以下為佳，以10萬以上150萬以下更佳。此外，丙烯酸系聚合物(α)之玻璃轉移溫度Tg，以-70℃以上30℃以下為佳，進一步以-60℃以上20℃以下的範圍為佳。玻璃轉移溫度，係以Fox式計算。 As the acrylic polymer (α), a conventionally known acrylic polymer can be used. a weight average molecular weight (Mw) of the acrylic polymer (α), a coating liquid composed of an adhesive composition for forming the above-mentioned adhesive layer 3 or a composition obtained by adding a solvent thereto (in the present specification, The coating liquid is collectively referred to as "coating liquid for forming an adhesive layer". The film forming property at the time of coating is preferably 10,000 or more and 2,000,000 or less, more preferably 100,000 or more and 1.5 million or less. Further, the glass transition temperature Tg of the acrylic polymer (α) is preferably -70 ° C or more and 30 ° C or less, and more preferably -60 ° C or more and 20 ° C or less. The glass transition temperature is calculated in the Fox formula.

上述丙烯酸系聚合物(α)，可為1種丙烯酸系單體所形成之單獨聚合物，亦可為複數種丙烯酸系單體所形成之共聚物，亦可為1種或複數種丙烯酸系單體與丙烯酸系單體以外 的單體所形成之共聚物。成為丙烯酸系單體之化合物之具體種類並無特別限定，具體例可舉，(甲基)丙烯酸、依康酸、(甲基)丙烯酸酯、其衍生物(丙烯腈等)。 The acrylic polymer (α) may be a single polymer formed of one type of acrylic monomer, or may be a copolymer of a plurality of acrylic monomers, or may be one or more acrylic monomers. Body and acrylic monomer The copolymer formed by the monomer. The specific type of the compound to be an acrylic monomer is not particularly limited, and specific examples thereof include (meth)acrylic acid, itaconic acid, (meth)acrylate, and derivatives thereof (acrylonitrile).

關於(甲基)丙烯酸酯，進一步表示具體例，則可舉(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2-乙基己酯等的具有鏈狀骨架之(甲基)丙烯酸酯；(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸四氫糠酯、醯亞胺丙烯酸酯等的環狀骨架之(甲基)丙烯酸酯；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯等的具有羥基之丙烯酸酯等的(甲基)丙烯酸酯；(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸N-甲基胺基乙酯等的具有羥基以外的反應性官能基之(甲基)丙烯酸酯。此外，丙烯酸系單體以外的單體，可例示乙烯、降冰片烯等的烯烴、醋酸乙烯酯、苯乙烯等。再者，丙烯酸系單體為(甲基)丙烯酸烷基酯時，該烷基之碳數以1~18的範圍為佳。 Further, specific examples of the (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. (meth) acrylate having a chain skeleton such as 2-ethylhexyl acrylate; cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, ( a (meth) acrylate of a cyclic skeleton such as dicyclopentanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate or quinone acrylate; 2-hydroxyethyl (meth) acrylate; (meth)acrylate such as hydroxy acrylate such as 2-hydroxypropyl acrylate; (meth) acrylate such as glycidyl (meth)acrylate or N-methylaminoethyl (meth)acrylate A (meth) acrylate other than a reactive functional group. Further, examples of the monomer other than the acrylic monomer include an olefin such as ethylene or norbornene, vinyl acetate, and styrene. Further, when the acrylic monomer is an alkyl (meth)acrylate, the carbon number of the alkyl group is preferably in the range of 1 to 18.

用於形成關於本實施形態之黏著劑層3之黏著劑組成物，含有如後所述之可與丙烯酸系聚合物(α)架橋之架橋劑(γ)時，丙烯酸系聚合物(α)所具有的反應性官能基的種類並無特別限定，根據架橋劑(γ)的種類等適宜決定即可。例如，架橋劑(γ)為聚異氰酸酯化合物時，作為丙烯酸系聚合物(α)所有的反應性官能基，可例示羥基、羧基、胺基等。該等之中，架橋劑(γ)為聚異氰酸酯化合物時，使用與異氰酸酯基之反應性高的羥基作為反應性官能基為佳。對丙烯酸系聚合物(α)導入羥基作 為反應性官能基之方法，並無特別限定。作為一例，可舉丙烯酸系聚合物(α)係2-羥基乙基(甲基)丙烯酸酯等於骨架含有基於具有羥基之丙烯酸酯的構成單位之情形。 When the adhesive composition for forming the adhesive layer 3 of the present embodiment contains a bridging agent (γ) which can be bridged with an acrylic polymer (α) as described later, the acrylic polymer (α) The type of the reactive functional group to be provided is not particularly limited, and may be appropriately determined depending on the type of the bridging agent (γ). For example, when the bridging agent (γ) is a polyisocyanate compound, examples of the reactive functional group of the acrylic polymer (α) include a hydroxyl group, a carboxyl group, an amine group and the like. Among these, when the bridging agent (γ) is a polyisocyanate compound, a hydroxyl group having high reactivity with an isocyanate group is preferably used as the reactive functional group. Introducing hydroxyl groups into the acrylic polymer (α) The method of being a reactive functional group is not particularly limited. As an example, the acrylic polymer (α)-based 2-hydroxyethyl (meth) acrylate may be equal to the case where the skeleton contains a constituent unit based on a hydroxy group-containing acrylate.

丙烯酸系聚合物(α)具有反應性官能基時，以用於形成丙烯酸系聚合物(α)之單體換算，對全單體之反應性官能基之質量比例，以1質量%以上20質量%以下程度為佳，以2質量%以上10質量%以下更佳。 When the acrylic polymer (α) has a reactive functional group, the mass ratio of the reactive monomer to the all monomer is from 1% by mass to 20% in terms of the monomer used to form the acrylic polymer (α). The degree below % is preferably 2% by mass or more and 10% by mass or less.

(1-2-2)能量線聚合性化合物(β) (1-2-2) Energy ray polymerizable compound (β)

用於形成關於本實施形態之黏著劑層3之黏著劑組成物所含有之能量線聚合性化合物(β)，只要是具有能量線聚合性基，可受紫外線、電子線等的能量線的照射而聚合反應，具體的構成並無特別限定。藉由聚合能量線聚合性化合物(β)可使黏著劑層3之保護膜形成用薄膜4的黏著性降低。 The energy ray polymerizable compound (β) contained in the adhesive composition for forming the pressure-sensitive adhesive layer 3 of the present embodiment can be irradiated with energy rays such as ultraviolet rays or electron beams as long as it has an energy ray polymerizable group. The specific constitution of the polymerization reaction is not particularly limited. The adhesiveness of the film 4 for forming a protective film of the adhesive layer 3 can be lowered by polymerizing the energy ray polymerizable compound (β).

能量線聚合性基的種類並無特別限定。其具體例，可舉乙烯基、(甲基)丙烯醯基等的乙烯性不飽和鍵結之官能基等。黏著劑組成物含有架橋劑(γ)時，由減少架橋劑(γ)進行架橋反應的部位與功能性重複的可能性的觀點，能量線聚合性基以具有乙烯性不飽和鍵結之官能基為佳，其中，由照射能量線時之反應性高的觀點，以(甲基)丙烯醯基更佳。 The type of the energy ray polymerizable group is not particularly limited. Specific examples thereof include a functional group such as a vinyl group or an ethylenically unsaturated bond such as a (meth)acryl fluorenyl group. When the adhesive composition contains a bridging agent (γ), the energy ray-polymerizable group has a functional group having an ethylenically unsaturated bond from the viewpoint of reducing the possibility of bridging reaction of the bridging agent (γ) and the possibility of functional repetition. Preferably, the (meth) acrylonitrile group is more preferable from the viewpoint of high reactivity when irradiating the energy ray.

能量線聚合性化合物(β)之分子量並無特別限定。其分子量過小時，在於黏著劑組成物或黏著劑層3之製造過程，有該化合物揮發之虞，此時會降低黏著劑層3之組成穩定性。因此，能量線聚合性化合物(β)之分子量，以重量平均分子量(Mw)，以100以上為佳，以200以上更佳，以300以上特別 佳。 The molecular weight of the energy ray polymerizable compound (β) is not particularly limited. When the molecular weight is too small, it is in the manufacturing process of the adhesive composition or the adhesive layer 3, and the compound is volatilized, and the composition stability of the adhesive layer 3 is lowered. Therefore, the molecular weight of the energy ray polymerizable compound (β) is preferably 100 or more in terms of weight average molecular weight (Mw), more preferably 200 or more, and 300 or more. good.

能量線聚合性化合物(β)之至少一部分，分子量以重量平均分子量(Mw)，以4,000以下為佳。作為如此之能量線聚合性化合物(β)，可例示選自由具有能量線聚合性基之單官能單體及多官能單體及該等單體的寡聚物之群之1種或2種以上所組成之化合物。 At least a part of the energy ray polymerizable compound (β) preferably has a molecular weight of 4,000 or less by weight average molecular weight (Mw). As such an energy ray-polymerizable compound (β), one or more selected from the group consisting of a monofunctional monomer having an energy ray polymerizable group, a polyfunctional monomer, and an oligomer of the monomers can be exemplified. The compound consisting of.

上述化合物之具體組成，並無特別限定。作為上述化合物之具體例，可舉三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、三(甲基)丙烯酸異戊四醇酯、五(甲基)丙烯酸二異戊四醇基單羥基酯、六(甲基)丙烯酸二異戊四醇酯、二(甲基)丙烯酸1,4-丁二醇酯、二(甲基)丙烯酸1,6-己二醇酯等的具有鏈狀骨架之(甲基)丙烯酸烷基酯；二環戊二烯基二甲氧基二(甲基)丙烯酸酯、異冰片基(甲基)丙烯酸酯等的具有環狀骨架之(甲基)丙烯酸烷基酯；聚乙二醇二(甲基)丙烯酸酯、寡聚酯(甲基)丙烯酸酯、尿烷(甲基)丙烯酸酯寡聚物、環氧基變性(甲基)丙烯酸酯、聚醚(甲基)丙烯酸酯、依康酸寡聚物等的丙烯酸酯系化合物等。該等之中，丙烯酸酯系化合物由於對丙烯酸系聚合物(α)之相溶性高而佳。 The specific composition of the above compound is not particularly limited. Specific examples of the above compound include trimethylolpropane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, pentaerythritol tris(meth)acrylate, and five (a) Diisoprenyl alcohol monohydroxy ester, diisopentyl hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate, di(meth)acrylic acid 1,6 - an alkyl (meth) acrylate having a chain skeleton such as hexanediol; dicyclopentadienyl dimethoxy bis(meth) acrylate or isobornyl (meth) acrylate; Alkyl (meth)acrylate having a cyclic skeleton; polyethylene glycol di(meth)acrylate, oligoester (meth)acrylate, urethane (meth)acrylate oligomer, epoxy An acrylate-based compound such as a conjugated (meth) acrylate, a polyether (meth) acrylate or an isoconic acid oligomer. Among these, the acrylate compound is preferred because it has high compatibility with the acrylic polymer (α).

能量線聚合性化合物(β)於一分子中具有的能量線聚合性基之數量並無限定，以複數為佳，以3以上更佳，以5以上特別佳。 The number of the energy ray polymerizable groups of the energy ray polymerizable compound (β) in one molecule is not limited, and is preferably plural, more preferably 3 or more, and particularly preferably 5 or more.

用於形成關於本實施形態之黏著劑層3之黏著劑組成物含有的能量線聚合性化合物(β)含量，對丙烯酸系聚合物(α)100質量部，以50質量部分以上300質量部以下為佳，以 75質量部分以上150質量部以下更佳。再者，在於本說明書，表示各成分之含量之「質量部」係指固形份之量。藉由使能量線聚合性化合物(β)之含量在於如此之範圍，可充分確保能量線照射之後的黏著劑層3對保護膜形成用薄膜4之黏著性，與能量線照射前之黏著劑層3對保護膜形成用薄膜4之黏著性之差。 The content of the energy ray polymerizable compound (β) contained in the adhesive composition of the adhesive layer 3 of the present embodiment is 50 parts by mass or more and 300 parts by mass or less for the acrylic polymer (α) 100 parts by mass. Better, to More than 75 mass parts and more than 150 mass parts are better. In the present specification, the "mass portion" indicating the content of each component means the amount of the solid portion. By setting the content of the energy ray polymerizable compound (β) in such a range, the adhesion of the adhesive layer 3 to the protective film forming film 4 after the energy ray irradiation and the adhesive layer before the energy ray irradiation can be sufficiently ensured. The difference in adhesion between the three films 4 for forming a protective film.

能量線聚合性化合物(β)之其他的例，可舉能量線聚合性化合物(β)為丙烯酸系聚合物，於主鏈或側鏈具有能量線聚合線基之構成單位者之情形。此時，由於能量線聚合性化合物(β)具有作為丙烯酸系聚合物(α)之性質，故可簡化用於形成黏著劑層3之組成物之組成，有容易控制在於黏著劑層3之能量線聚合性基之存在密度等之優點。 In another example of the energy ray polymerizable compound (β), the energy ray polymerizable compound (β) is an acrylic polymer, and the main chain or the side chain has a constituent unit of an energy ray polymerization line group. In this case, since the energy ray polymerizable compound (β) has a property as an acrylic polymer (α), the composition of the composition for forming the adhesive layer 3 can be simplified, and the energy of the adhesive layer 3 can be easily controlled. The advantages of the existence density of the linear polymerizable group and the like.

具有如上所述之丙烯酸系聚合物(α)之性質之能量線聚合性化合物(β)，例如可藉由如下方法調製。可藉由使基於含有羥基、羧基、胺基、取代胺基、環氧基等的官能基之(甲基)丙烯酸酯之構成單位及基於(甲基)丙烯酸烷基酯之構成單位而成之共聚物之丙烯酸系聚合物，與於1分子內具有可與上述官能基反應之官能基及能量線聚合性基(例如有乙烯性雙鍵鍵結之基)之化合物反應，對上述丙烯酸系聚合物加成能量線聚合性基。 The energy ray polymerizable compound (β) having the properties of the acrylic polymer (α) as described above can be prepared, for example, by the following method. It can be formed by a constituent unit of a (meth) acrylate based on a functional group containing a hydroxyl group, a carboxyl group, an amine group, a substituted amine group, an epoxy group or the like and a constituent unit based on an alkyl (meth) acrylate. The acrylic polymer of the copolymer reacts with a compound having a functional group reactive with the above functional group and an energy ray polymerizable group (for example, a group having an ethylenic double bond bond) in one molecule, and the above acrylic polymerization Addition of an energy ray polymerizable group.

使能量線聚合性化合物(β)硬化之能量線，可舉電離輻射線，即X射線、紫外線、電子線等。該等之中，以照射設備相對較容易導入之紫外線為佳。 The energy rays for curing the energy ray polymerizable compound (β) include ionizing radiation, that is, X-rays, ultraviolet rays, electron beams, and the like. Among these, it is preferred that the ultraviolet light is relatively easily introduced by the irradiation device.

使用紫外線作為電離輻射線時，由操作的容易度 使用包含波長200~380nm程度之紫外線之近紫外線即可。紫外線量，只要按照能量線聚合性化合物(β)之種類或黏著劑層3之厚度適宜選擇即可，通常為50~500mJ/cm2左右，以100~450mJ/cm2為佳，以200~400mJ/cm2更佳。此外，紫外線照度，通常為50~500mW/cm2左右，以100~450mW/cm2為佳，以200~400mW/cm2更佳。紫外線源，並無特別限制，可使用例如高壓水銀燈、金屬鹵素燈、UVLED等。 When ultraviolet rays are used as the ionizing radiation, it is sufficient to use near-ultraviolet rays including ultraviolet rays having a wavelength of about 200 to 380 nm from the ease of handling. Amount of ultraviolet light, as long as the energy ray polymerizable compound according to the thickness (beta]), or of the kind of the adhesive agent layer 3 is appropriately selected, generally 50 ~ 500mJ / cm 2, and at 100 ~ 450mJ / cm 2 preferably, 200 to 400 mJ/cm 2 is more preferable. Further, the intensity of ultraviolet, generally 50 ~ 500mW / cm 2, and at 100 ~ 450mW / cm 2 preferably, to 200 ~ 400mW / cm 2 more preferably. The ultraviolet source is not particularly limited, and for example, a high pressure mercury lamp, a metal halide lamp, a UV LED, or the like can be used.

使用電子線作為電離輻射線時，關於其加速電壓，只要按照能量線聚合性化合物(β)之種類或黏著劑層3之厚度適宜選定即可，通常加速電壓以10~1,000kV程度為佳。此外，照射劑量，只要設定於能量線聚合性化合物(β)適當地硬化之範圍即可，通常於10~1,000krad的範圍選定。電子線源並無特別限制，例如柯克考羅夫特-華登(Cockcroft-Walton)型、范德格拉夫(Van-de-Graaff)型、共振變壓器型、絕緣芯變壓器型或直線型、Dynamitron型、高頻波型等的各種電子線加速器。 When the electron beam is used as the ionizing radiation, the acceleration voltage is preferably selected in accordance with the type of the energy ray polymerizable compound (β) or the thickness of the adhesive layer 3, and the acceleration voltage is usually preferably from 10 to 1,000 kV. In addition, the irradiation dose is set to a range in which the energy ray polymerizable compound (β) is appropriately cured, and is usually selected in the range of 10 to 1,000 krad. There are no special restrictions on the source of the electron, such as the Cockcroft-Walton type, the Van-de-Graaff type, the resonant transformer type, the insulated core transformer type or the linear type. Various electron line accelerators such as Dynamitron type and high frequency wave type.

(1-2-3)架橋劑(γ) (1-2-3) bridging agent (γ)

用於形成關於本實施形態之黏著劑層3之黏著劑組成物，如上所述，亦可含有可與丙烯酸系聚合物(α)反應之架橋劑(γ)。此時，關於本實施形態之黏著劑層3，含有藉由丙烯酸系聚合物(α)與架橋劑(γ)之架橋反應所得之架橋物。 The adhesive composition for forming the adhesive layer 3 of the present embodiment may contain a bridging agent (?) which can react with the acrylic polymer (?) as described above. At this time, the adhesive layer 3 of the present embodiment contains a bridge material obtained by bridging reaction of the acrylic polymer (α) and the bridging agent (γ).

架橋劑(γ)之種類，可舉例如，環氧系化合物、異氰酸酯系化合物、金屬螯合物系化合物、氮丙啶系化合物等的聚醯亞胺化合物、三聚氰胺樹脂、尿素樹脂、二醛類、羥甲基聚合物、金屬烷氧化合物、金屬鹽等。該等之中，由容易控制 架橋反應等的理由，架橋劑(γ)以聚異氰酸酯化合物為佳。 The type of the bridging agent (γ) may, for example, be an epoxy compound, an isocyanate compound, a metal chelate compound, a polyaziridine compound such as an aziridine compound, a melamine resin, a urea resin, or a dialdehyde. , a methylol polymer, a metal alkoxide, a metal salt, and the like. Among these, it is easy to control For the reason of bridging reaction or the like, the bridging agent (γ) is preferably a polyisocyanate compound.

在此，稍微詳細地說明關於聚異氰酸酯化合物。聚異氰酸酯化合物係於1分子具有2個異氰酸酯基之化合物，可舉例如甲苯基二異氰酸酯、二苯基二異氰酸酯、二甲苯基二異氰酸酯等的芳香族聚異氰酸酯；二環己基甲烷-4,4'-二異氰酸酯、二環庚烷三異氰酸酯、亞環戊基二異氰酸酯、亞環己烯二異氰酸酯、甲基亞環己基二異氰酸酯、加氫亞二甲苯基二異氰酸酯等的脂環式異氰酸酯化合物；六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、賴氨酸二異氰酸酯等的具有鏈狀骨架之異氰酸酯。 Here, the polyisocyanate compound will be described in some detail. The polyisocyanate compound is a compound having two isocyanate groups per molecule, and examples thereof include aromatic polyisocyanates such as tolyl diisocyanate, diphenyl diisocyanate, and xylyl diisocyanate; and dicyclohexylmethane-4, 4' - an alicyclic isocyanate compound such as diisocyanate, dicycloheptane triisocyanate, cyclopentylene diisocyanate, cyclohexene diisocyanate, methyl cyclohexylene diisocyanate or hydrogenated xylylene diisocyanate; An isocyanate having a chain skeleton such as methylene diisocyanate, trimethylhexamethylene diisocyanate or lysine diisocyanate.

此外，亦可使用該等化合物之雙縮脲體、異氰脲酸酯體，或該等的化合物，與乙二醇、三甲醇基丙烷、蓖麻油等的非芳香族性低分子活性氫含有化合物之反應物之加成物等的變性體。上述聚異氰酸酯化合物，可以1種，亦可以複數種。 Further, a biuret or isocyanurate of these compounds or a compound thereof may be used, and a non-aromatic low molecular active hydrogen such as ethylene glycol, trimethylolpropane or castor oil may be contained. A denatured product such as an adduct of a reactant of a compound. The polyisocyanate compound may be used singly or in combination of plural kinds.

關於本實施形態之黏著劑層3，具有基於丙烯酸系聚合物(α)與架橋劑(γ)之架橋物時，可藉由調整含於黏著劑層3之架橋物之架橋密度，可調整黏著劑層3之照射前儲存彈性模數等的特性。該架橋密度，可藉由改變用於形成黏著劑層3之組成物之架橋劑(γ)之含量而調整。具體而言，藉由使用於形成黏著劑層3之黏著劑組成物之架橋劑(γ)之含量，對丙烯酸系聚合物(α)100質量部，以5質量部以上，可容易將黏著劑層3之照射前儲存彈性模數等控制於適當的範圍。由提高該控制性的觀點，架橋劑(γ)之含量，對丙烯酸系聚合物(α)100質量部， 以10質量部以上更佳，以20質量部以上特別佳。架橋劑(γ)之含量的上限，並無特別限定，含量過高時，由於有難以將黏著劑層3之黏著性控制於後述之範圍之情形，故對丙烯酸系聚合物(α)100質量部，以50質量部以下為佳，以40質量部以下更佳。 When the adhesive layer 3 of the present embodiment has a bridging material based on an acrylic polymer (α) and a bridging agent (γ), the bridge density of the bridging material contained in the adhesive layer 3 can be adjusted to adjust the adhesion. The characteristics of the elastic modulus and the like are stored before the irradiation of the agent layer 3. The bridging density can be adjusted by changing the content of the bridging agent (γ) used to form the composition of the adhesive layer 3. Specifically, the amount of the bridging agent (γ) used for forming the adhesive composition of the adhesive layer 3 can be easily made to the mass portion of the acrylic polymer (α) by at least 5 parts by mass. The storage modulus before the irradiation of the layer 3 is controlled to an appropriate range. From the viewpoint of improving the controllability, the content of the bridging agent (γ) is 100 parts by mass for the acrylic polymer (α). It is more preferably 10 parts by mass or more, and particularly preferably 20 parts by mass or more. The upper limit of the content of the bridging agent (γ) is not particularly limited. When the content is too high, it is difficult to control the adhesion of the adhesive layer 3 to the range described later, so the quality of the acrylic polymer (α) 100 is 100. The part is preferably 50 parts by mass or less, and more preferably 40 parts by mass or less.

用於形成關於本實施形態之黏著劑層3之黏著劑組成物含有架橋劑(γ)時，按照該架橋劑(γ)之種類等，含有適當的架橋促進劑為佳。例如，架橋劑(γ)為聚異氰酸酯化合物時，用於形成黏著劑層3之黏著劑組成物含有有機錫化合物等的有機金屬化合物系之架橋促進劑為佳。 When the binder composition for forming the pressure-sensitive adhesive layer 3 of the present embodiment contains a bridging agent (γ), it is preferred to contain an appropriate bridging promoter in accordance with the type of the bridging agent (γ). For example, when the bridging agent (γ) is a polyisocyanate compound, it is preferred that the adhesive composition for forming the adhesive layer 3 contains an organometallic compound-based bridging promoter such as an organic tin compound.

(1-2-4)其他的成分 (1-2-4) Other ingredients

用於形成關於本實施形態之黏著板片1所包括之黏著劑層3之黏著劑組成物，除了上述成分，亦可含有儲存彈性模數調整劑、光聚合起始劑、染料及顏料等的著色材料、難燃劑、填充劑等的各種添加劑。 The adhesive composition for forming the adhesive layer 3 included in the adhesive sheet 1 of the present embodiment may contain, in addition to the above components, a storage elastic modulus adjuster, a photopolymerization initiator, a dye, a pigment, and the like. Various additives such as coloring materials, flame retardants, fillers, and the like.

作為儲存彈性模數調整劑，可例示黏著賦予樹脂或長鏈烷基丙烯酸酯寡聚物等。儲存彈性模數調整劑之含量，由穩定地發揮其功能的觀點，對丙烯酸系聚合物(α)100質量部，以50質量部以上為佳，以75質量部以上更佳，以100質量部以上特別佳。此外，為將含於黏著劑層3之黏著劑之凝聚性維持在適切的程度，儲存彈性模數調整劑的含量，對丙烯酸系聚合物(α)100質量部，以500質量部以下為佳，以400質量部以下更佳，以350質量部以下特別佳。 As the storage elastic modulus adjuster, an adhesion-imparting resin, a long-chain alkyl acrylate oligomer, or the like can be exemplified. The content of the elastic modulus adjusting agent is preferably 50 parts by mass or more, more preferably 75 parts by mass or more, and 100 parts by mass, from the viewpoint of stably exhibiting the function of the acrylic polymer (α). The above is especially good. In addition, in order to maintain the cohesiveness of the adhesive contained in the adhesive layer 3 to an appropriate extent, the content of the elastic modulus adjusting agent is preferably 100 parts by mass or less based on 100 parts by mass of the acrylic polymer (α). It is preferably 400 mass parts or less, and is particularly preferably 350 mass parts or less.

在於儲存彈性模數調整劑含有黏著賦予樹脂時， 該黏著賦予樹脂之種類並無特別限定。聚合松香酯、酯化松香酯及不均化松香酯以及該等之加氫樹脂等的松香酯系的黏著賦予樹脂，亦可為α-蒎烯樹脂等的萜烯系的黏著賦予樹脂、亦可為烴樹脂等的石油系樹脂。或者，亦可為香豆酮樹脂、烷基．酚樹脂、二甲苯樹脂等的芳香族系黏著賦予樹脂。 When the storage elastic modulus adjuster contains an adhesive-imparting resin, The type of the adhesion-imparting resin is not particularly limited. The rosin ester-based adhesion-providing resin such as a polymerized rosin ester, an esterified rosin ester, a heterogeneous rosin ester, or the like, or a hydrogenated resin, may be a terpene-based adhesion-imparting resin such as an α-pinene resin. It may be a petroleum resin such as a hydrocarbon resin. Alternatively, it may be a coumarone resin or an alkyl group. An aromatic-based adhesion-providing resin such as a phenol resin or a xylene resin.

藉由組合使用該等相異種類的黏著賦予樹脂，可提高儲存彈性模數調整劑對丙烯酸系聚合物(α)之相溶性，有可得較佳的特性之情形。其一例，可舉用於形成黏著劑層3之黏著劑組成物，含有聚合松香酯(C1)作為儲存彈性模數調整劑的同時，含有加氫松香酯(C2)及烴樹脂(C3)之少一方之情形。含有上述黏著賦予樹脂時，用於形成黏著劑層3之組成物之聚合松香酯(C1)之含量，對丙烯酸系聚合物(α)100質量部，以20質量部以下為佳，以5質量部分以上18質量部分以下更佳，以7質量部分以上15質量部特別佳。用於形成黏著劑層3之黏著劑組成物之加氫松香酯(C2)之含量及烴樹脂(C3)之含量之總和，由提高含於黏著劑層3之黏著劑之凝聚性的觀點，對丙烯酸系聚合物(α)100質量部，以50質量部以上為佳，以70質量部分以上200質量部以下更佳，以90質量部分以上170質量部以下特別佳。 By using these different types of adhesion-imparting resins in combination, it is possible to improve the compatibility of the storage elastic modulus adjusting agent with the acrylic polymer (α), and it is possible to obtain better characteristics. An example of this is an adhesive composition for forming the adhesive layer 3, which contains a polymerized rosin ester (C1) as a storage elastic modulus adjuster, and contains a hydrogenated rosin ester (C2) and a hydrocarbon resin (C3). The situation of one less party. When the adhesion-imparting resin is contained, the content of the polymerized rosin ester (C1) for forming the composition of the adhesive layer 3 is preferably 20 parts by mass or less, and preferably 5 parts by mass for the acrylic polymer (α) 100 parts by mass. Some of the above 18 mass parts are more preferable, and the mass parts of 7 mass parts or more are particularly excellent. The sum of the content of the hydrogenated rosin ester (C2) and the content of the hydrocarbon resin (C3) of the adhesive composition for forming the adhesive layer 3 is improved from the viewpoint of improving the cohesiveness of the adhesive contained in the adhesive layer 3. The mass portion of the acrylic polymer (α) is preferably 50 parts by mass or more, more preferably 70 parts by mass or more and 200 parts by mass or less, and particularly preferably 90 parts by mass or more and 170 parts by mass or less.

長鏈烷基丙烯酸酯寡聚物，係碳數4以上18以下左右之烷基(甲基)丙烯酸酯聚合而成之寡聚物，烷基部分的具體的構成，並無特別限定。用於形成該寡聚物之單體之具體例，可舉丙烯酸丁酯。 The long-chain alkyl acrylate oligomer is an oligomer obtained by polymerizing an alkyl (meth) acrylate having a carbon number of 4 or more and 18 or less, and the specific structure of the alkyl moiety is not particularly limited. Specific examples of the monomer for forming the oligomer include butyl acrylate.

光聚合起始劑，可舉安息香化合物、苯乙酮化合 物、醯基膦氧化物化合物、二茂鈦化合物、噻吨酮化合物、過氧化物化合物等的光起始劑、胺或醌等的光增感劑等，具體而言，可例示1-羥基環己基苯酮、安息香、安息香甲醚、安息香乙醚、安息香異丙醚、苄基二苯基硫醚、四甲基秋蘭姆單硫化物、苯偶醯異丁腈、二苄基、聯乙醯、β-氯蒽醌、2,4,6-三甲基苯甲醯基二苯基氧化膦等。使用紫外線作為能量線時，藉由調合光聚合起始劑，可減少照射時間，照射量。 Photopolymerization initiator, which can be a benzoin compound or an acetophenone compound a photoinitiator such as a thiol phosphine oxide compound, a titanocene compound, a thioxanthone compound or a peroxide compound, a photo sensitizer such as an amine or hydrazine, etc., specifically, a 1-hydroxy group is exemplified. Cyclohexyl benzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl diphenyl sulfide, tetramethyl thiuram monosulfide, benzoin isobutyronitrile, dibenzyl, biphenyl Anthracene, β-chloropurine, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, and the like. When ultraviolet rays are used as the energy ray, the irradiation time and the amount of irradiation can be reduced by blending the photopolymerization initiator.

(1-2-5)厚度 (1-2-5) thickness

關於本實施形態之切割片1所包括之黏著劑層3之厚度，並無特別限定。以適當地維持黏著劑層3對被著體(保護膜形成用薄膜4、夾具等)之黏著性的觀點，黏著劑層3之厚度，以1μm以上為佳，以2μm以上更佳，以3μm以上特別佳。另一方面，減低於切割步驟中發生晶片缺陷的可能性的觀點，黏著劑層3之厚度，以100μm以下為佳，以80μm以下更佳，以50μm以下特別佳。 The thickness of the adhesive layer 3 included in the dicing sheet 1 of the present embodiment is not particularly limited. The thickness of the adhesive layer 3 is preferably 1 μm or more, more preferably 2 μm or more, and 3 μm from the viewpoint of appropriately maintaining the adhesion of the adhesive layer 3 to the object (the protective film forming film 4, the jig, etc.). The above is especially good. On the other hand, from the viewpoint of reducing the possibility of occurrence of wafer defects in the dicing step, the thickness of the adhesive layer 3 is preferably 100 μm or less, more preferably 80 μm or less, and particularly preferably 50 μm or less.

(2)保護膜形成用薄膜 (2) Film for forming a protective film

如第2圖所示，關於本實施形態之PR層積體100所包括之保護膜形成用薄膜4，係層積於上述的黏著板片1之黏著劑層3側之主面1A之一部分的區域1a，成為構成保護膜形成用複合板片10之1要素。 As shown in Fig. 2, the film 4 for forming a protective film included in the PR laminate 100 of the present embodiment is laminated on one of the main faces 1A on the side of the adhesive layer 3 of the above-mentioned adhesive sheet 1. The region 1a is one element constituting the composite sheet 10 for forming a protective film.

以下，詳細地說明關於保護膜形成用薄膜4。 Hereinafter, the film 4 for forming a protective film will be described in detail.

保護膜形成用薄膜4，發揮以下的功能作為基本功能。 The film 4 for forming a protective film exhibits the following functions as a basic function.

(功能1)可形成保護被加工構件W之層積有保護膜形成用薄 膜4之表面之保護膜。 (Function 1) It is possible to form a protective film forming thin layer which is laminated to protect the workpiece W A protective film on the surface of the film 4.

(功能2)保護膜形成用薄膜4或由此形成之保護膜(保護膜等)配置於被加工構件W與黏著板片1之間，供於切割步驟時，不容易發生被加工構件W與保護膜等之間的剝離及保護膜等與黏著板片1之間的剝離。 (Function 2) The protective film forming film 4 or the protective film (protective film or the like) formed thereby is disposed between the workpiece W and the adhesive sheet 1 and is not easily liable to be processed when the cutting step is performed. Peeling between the protective film and the like, and peeling between the protective film and the like and the adhesive sheet 1.

(功能3)在於切割步驟後進行之拾取步驟，保護膜等與黏著板片1之間的剝離較於被加工構件W與保護膜等之間的剝離優先發生。 (Function 3) In the pickup step performed after the cutting step, peeling between the protective film and the like and the adhesive sheet 1 takes place preferentially with respect to peeling between the workpiece W and the protective film or the like.

(功能4)藉由對與保護膜之被加工構件W相對之面之相反側之面，以雷射標記等進行刻印，可形成具有視認性優良的標記之保護膜。 (Function 4) By marking the surface opposite to the surface facing the workpiece W of the protective film by laser marking or the like, a protective film having a mark having excellent visibility can be formed.

(2-1)以平面視之形狀 (2-1) in the shape of a plane view

關於本實施形態之PR層積體100所包括之保護膜形成用薄膜4，以平面視之形狀具有如下的特徵。即，如第3圖所示，在於保護膜形成用複合板片10之保護膜形成用薄膜4側之主面10A，於使用時應貼附於被加工構件W之區域之加工用區域10a，與在於保護膜形成用薄膜4之剝離板片20之剝離面20A相對之主面(在於本說明書，亦稱為「薄膜主面」。)4A之全區域相等或包含該薄膜主面4A之全區域。換言之，加工用區域10a覆蓋薄膜主面4A的全區域地，設定保護膜形成用薄膜4之平面視形狀。 The film 4 for forming a protective film included in the PR laminate 100 of the present embodiment has the following features in a plan view. In other words, as shown in Fig. 3, the main surface 10A on the side of the protective film forming film 4 of the composite sheet 10 for protective film formation is attached to the processing region 10a in the region of the workpiece W during use. The entire surface of the main surface facing the peeling surface 20A of the peeling sheet 20 of the protective film forming film 4 (also referred to as "the main surface of the film" in the present specification) is equal to or includes the entire main surface 4A of the film. region. In other words, the processing region 10a covers the entire area of the film main surface 4A, and the planar shape of the film for forming a protective film 4 is set.

由於加工用區域10a與薄膜主面4A具有上述的關係，於切割加工時，於薄膜主面4A，並不會發生沒有以被加工構件W覆蓋而露出的區域。因此，不容易發生起因於位在 露出區域之保護膜等之薄膜飛散。 Since the processing region 10a and the film main surface 4A have the above-described relationship, the film main surface 4A does not have a region that is not covered by the workpiece W during the cutting process. Therefore, it is not easy to cause the cause to be in The film of the protective film or the like in the exposed area is scattered.

薄膜主面4A之外周，與加工用區域10a之外周在平面視之離間距離d，以0mm以上10mm以下為佳。離間距離d在於該這範圍，則貼附保護膜形成用複合板片10之加工構件W之保護膜形成用複合板片10側之面之中，由於保護膜形成用薄膜4沒有貼著於加工構件W的區域的面積不大，故可減低在切割加工時，發生位於該區域之加工構件W之個片，而帶來該個片飛散之晶片飛散的可能性。 The outer circumference of the main surface 4A of the film is preferably from 0 mm to 10 mm in a plane-distance distance d from the outer periphery of the processing region 10a. In the above-mentioned range, the protective film forming film 4 is not attached to the surface of the composite sheet 10 on the side of the protective film forming of the processed member W of the composite sheet 10 for forming a protective film. Since the area of the region of the member W is not large, it is possible to reduce the occurrence of a sheet of the processed member W located in the region during the dicing process, and the possibility of scattering of the wafer in which the sheet scatters.

以下，用於保護膜形成用薄膜4係將用於形成此之組成物(在於本說明書，亦稱為「保護膜形成用組成物」。)硬化而得者，具體而言，以具有(1)板片形狀維持性、(2)初期黏著性、及(3)硬化性之薄膜之情形為具體例，說明保護膜形成用薄膜4之組成等。 In the following, the film for forming a protective film 4 is obtained by curing the composition for forming the composition (also referred to as "the composition for forming a protective film" in the present specification), and specifically has (1) The case of the shape of the sheet, the (2) initial adhesion, and the (3) curable film are specific examples, and the composition of the film 4 for forming a protective film will be described.

(2-2)組成 (2-2) Composition

對保護膜形成用薄膜4，可藉由添加膠合劑成分賦予(1)板片形狀維持性及(3)硬化性，膠合劑成分，可使用含有聚合物成分(A)及硬化性成分(B)之第1膠合劑成分或含有兼具(A)成分及(B)成分之性質之硬化性聚合物成分(AB)之第2膠合劑成分。 The film 4 for forming a protective film can be provided with (1) sheet shape maintenance property and (3) hardenability, and a binder component, and a polymer component (A) and a curable component (B) can be used by adding a binder component. The first binder component or the second binder component containing the curable polymer component (AB) having the properties of the components (A) and (B).

再者，直到保護膜形成用薄膜4硬化之間為將被著體假黏之功能之(2)初期黏著性，亦可為感壓接著性，亦可係藉由熱而軟化接著之性質。(2)初期接著性，通常可藉由調整膠合劑成分之諸特性，或後述之無機填充劑等的填充材(C)之調合量等控制。 Further, the (2) initial adhesion property between the curing of the film for forming a protective film is a function of the pseudo-adhesion of the object, and it may be a pressure-sensitive adhesive property, or may be softened by heat. (2) The initial adhesion property can be controlled by adjusting the properties of the binder component or the blending amount of the filler (C) such as an inorganic filler to be described later.

(第1膠合劑成分) (1st binder component)

第1膠合劑成分，藉由含有聚合物成分(A)與硬化性成分 (B)，對保護膜形成用薄膜4賦予(1)板片形狀維持性與(3)硬化性。再者，第1膠合劑成分，與第2膠合劑成分區別的權宜上，並不含有硬化性聚合物成分(AB)。 The first binder component contains the polymer component (A) and the curable component (B) The film 4 for protective film formation is provided with (1) sheet shape maintenance property and (3) hardenability. Further, the first binder component does not contain the curable polymer component (AB) as it is different from the second binder component.

(A)聚合物成分 (A) polymer component

聚合物成分(A)，係對保護膜形成用薄膜4賦予(1)板片形狀維持性為主要目的而添加於保護膜形成用薄膜4。 The polymer component (A) is added to the protective film formation film 4 for the purpose of imparting (1) sheet shape maintenance to the film 4 for forming a protective film.

為達成上述目的，聚合物成分(A)之重量平均分子量(Mw)，通常係20,000以上，以20,000~3,000,000是為佳。重量平均分子量(Mw)之值，係以凝膠滲透層析法(GPC法)(聚苯乙烯標準)測定時之值。以如此之方法的測定，例如，於TOSO公司製之高速GPC裝置「HLC-8120GPC」，高速管柱「TSK gurd column HXL-H」、「TSK Gel GMHXL」、「TSK Gel G2000 HXL」(以上，均為TOSO公司製)以此順序連接者，以管柱溫度：40℃、送液速度：1.0mL/分的條件，偵測器以示差折射率計進行。 In order to achieve the above object, the weight average molecular weight (Mw) of the polymer component (A) is usually 20,000 or more, preferably 20,000 to 3,000,000. The value of the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC method) (polystyrene standard). In the measurement by such a method, for example, the high-speed GPC device "HLC-8120GPC" manufactured by TOSO, "TSK gurd column H XL -H", "TSK Gel GMH XL ", "TSK Gel G2000 H XL " (The above are all manufactured by TOSO Co., Ltd.) In this order, the detector was carried out with a differential refractometer under the conditions of a column temperature of 40 ° C and a liquid feeding rate of 1.0 mL / min.

再者，與後述之硬化性聚合物(AB)區別的權宜上，聚合物成分(A)並不具有後述之硬化功能官能基。 Further, in the case of being distinguished from the curable polymer (AB) to be described later, the polymer component (A) does not have a curing functional group to be described later.

聚合物成分(A)，可使用丙烯酸系聚合物、聚酯、苯氧基樹脂(與後述之硬化性聚合物(AB)區別的權宜上，限於不具有環氧基者。)、聚碳酸酯、聚醚、聚氨脂、聚矽氧烷、橡膠系聚合物等。此外，該等2種以上鍵結者，例如，可為具有羥基之丙烯酸系聚合物之丙烯酸多元醇，與於分子末端具有異氰酸酯基之尿烷預聚合物反應而得之丙烯酸尿烷樹脂等。再者，亦可包含2種以上所鍵結之聚合物，將該等組合2種以上使用。 The polymer component (A) can be an acrylic polymer, a polyester, or a phenoxy resin (except for the difference from the curable polymer (AB) described later, and is limited to those having no epoxy group). , polyether, polyurethane, polyoxyalkylene, rubber-based polymers, and the like. Further, the two or more types of bonds may be, for example, an acrylic polyol having an acrylic polymer having a hydroxyl group, an acrylic urethane resin obtained by reacting with a urethane prepolymer having an isocyanate group at a molecular terminal. Further, two or more kinds of the bonded polymers may be contained, and two or more types may be used in combination.

(A1)丙烯酸系聚合物 (A1) acrylic polymer

聚合物成分(A)，可良好地使用丙烯酸系聚合物(A1)。丙烯酸系聚合物(A1)之玻璃轉移溫度(Tg)，以-60~50℃為佳，以-50~40℃更佳，進一步以-40~30℃的範圍為佳。丙烯酸系聚合物(A1)之玻璃轉移溫度過高則有保護膜形成用薄膜4之探頭黏力值有降低的趨勢，此外，黏著性在硬化後有下降的趨勢。因此，丙烯酸系聚合物(A1)之玻璃轉移溫度(Tg)，以-40~-5℃的範圍特別佳。 As the polymer component (A), the acrylic polymer (A1) can be preferably used. The glass transition temperature (Tg) of the acrylic polymer (A1) is preferably -60 to 50 ° C, more preferably -50 to 40 ° C, and further preferably in the range of -40 to 30 ° C. When the glass transition temperature of the acrylic polymer (A1) is too high, the probe adhesion value of the protective film forming film 4 tends to decrease, and the adhesiveness tends to decrease after hardening. Therefore, the glass transition temperature (Tg) of the acrylic polymer (A1) is particularly preferably in the range of -40 to -5 °C.

丙烯酸系聚合物(A1)之重量平均分子量，以100,000~1,500,000為佳。丙烯酸系聚合物(A1)之重量平均分子量過高則保護膜形成用薄膜4探頭黏力值有降低的趨勢，此外，黏著性在硬化後有下降的趨勢。因此，丙烯酸系聚合物(A1)之重量平均分子量以600,000~1,200,000更佳。 The weight average molecular weight of the acrylic polymer (A1) is preferably from 100,000 to 1,500,000. When the weight average molecular weight of the acrylic polymer (A1) is too high, the viscosity of the probe film 4 for protective film formation tends to decrease, and the adhesiveness tends to decrease after hardening. Therefore, the weight average molecular weight of the acrylic polymer (A1) is more preferably from 600,000 to 1,200,000.

丙烯酸系聚合物(A1)，至少於構成之單體，包含(甲基)丙烯酸酯。 The acrylic polymer (A1) contains at least a (meth) acrylate, at least a constituent monomer.

(甲基)丙烯酸酯，可舉烷基之碳數為1~18之烷基(甲基)丙烯酸酯，具體而言，(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2-乙基己酯等；具有環狀骨架的(甲基)丙烯酸酯，具體可舉(甲基)丙烯酸環烷酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧乙基酯、醯亞胺(甲基)丙烯酸酯。此外，可例示作為後述之具有以熱反應之官能基之單體、具有羥基之單體、具有羧基之單體、具有胺基之單體之中，可例示(甲基)丙烯酸酯。 The (meth) acrylate may, for example, be an alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms, specifically, methyl (meth) acrylate or ethyl (meth) acrylate. Base) propyl acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc.; (meth) acrylate having a cyclic skeleton, specifically, cycloalkyl (meth) acrylate Benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopenteneoxy (meth)acrylate Base ester, quinone imine (meth) acrylate. In addition, (meth)acrylate can be exemplified as a monomer having a functional group which is thermally reactive, a monomer having a hydroxyl group, a monomer having a carboxyl group, and a monomer having an amine group, which will be described later.

構成丙烯酸系聚合物(A1)之單體，可使用具有羥基之單體。藉由使用如此之單體，於丙烯酸系聚合物(A1)導入羥基，保護膜形成用薄膜4另外含有能量線硬化性成分(B2)時，可提升此與丙烯酸系聚合物(A1)之相溶性。具有羥基之單體，可舉(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯等的具有羥基之(甲基)丙烯酸酯；N-羥甲基(甲基)丙烯醯胺等。 As the monomer constituting the acrylic polymer (A1), a monomer having a hydroxyl group can be used. When the hydroxyl group is introduced into the acrylic polymer (A1) by using such a monomer, and the protective film forming film 4 additionally contains the energy ray-curable component (B2), the phase with the acrylic polymer (A1) can be enhanced. Solubility. The monomer having a hydroxyl group may be a (meth) acrylate having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; N-hydroxymethyl (methyl) Acrylamide and the like.

構成丙烯酸系聚合物(A1)之單體，亦可使用具有羧基之單體。藉由使用如此之單體，於丙烯酸系聚合物(A1)導入羧基，保護膜形成用薄膜4另外含有能量線硬化性成分(B2)時，可提升此與丙烯酸系聚合物(A1)之相溶性。具有羧基之單體，可舉(甲基)丙烯酸、馬來酸、富馬酸、依康酸等。作為後述之硬化性成分(B)，使用環氧系熱硬化性成分時，由於羧基與環氧系熱硬化性成分中的環氧基會反應，故具有羧基之單體之使用量較少為佳。 As the monomer constituting the acrylic polymer (A1), a monomer having a carboxyl group can also be used. When the carboxyl group is introduced into the acrylic polymer (A1) by using such a monomer, and the protective film forming film 4 additionally contains the energy ray-curable component (B2), the phase of the acrylic polymer (A1) can be enhanced. Solubility. The monomer having a carboxyl group may, for example, be (meth)acrylic acid, maleic acid, fumaric acid or itaconic acid. When an epoxy-based thermosetting component is used as the curable component (B) to be described later, since the carboxyl group reacts with the epoxy group in the epoxy-based thermosetting component, the amount of the monomer having a carboxyl group is small. good.

構成丙烯酸系聚合物(A1)之單體，亦可使用具有胺基之單體。如此之單體，可舉單乙基胺基(甲基)丙烯酸酯等之具有胺基之丙烯酸酯等。 As the monomer constituting the acrylic polymer (A1), a monomer having an amine group can also be used. Examples of such a monomer include an acrylate having an amine group such as monoethylamino (meth) acrylate.

作為構成丙烯酸系聚合物(A1)之單體，此外亦可使用醋酸乙烯酯、苯乙烯、乙烯、α-烯烴等。 As the monomer constituting the acrylic polymer (A1), vinyl acetate, styrene, ethylene, an α-olefin or the like can also be used.

丙烯酸系聚合物(A1)亦可架橋。架橋，係架橋前之丙烯酸系聚合物(A1)具有羥基等的架橋性官能基，藉由在保護膜形成用組成物中添加架橋劑，使架橋性官能基與架橋劑所具有的官能基反應而進行。藉由將丙烯酸系聚合物(A1)架橋，可調節保護膜形成用薄膜4之凝聚力。 The acrylic polymer (A1) can also be bridged. In the bridging, the acrylic polymer (A1) in front of the bridging bridge has a bridging functional group such as a hydroxyl group, and a bridging agent is added to the protective film forming composition to react the bridging functional group with the functional group of the bridging agent. And proceed. The bridging force of the film 4 for forming a protective film can be adjusted by bridging the acrylic polymer (A1).

架橋劑，可舉有機多價異氰酸酯化合物、有機多價醯亞胺化合物等。 The bridging agent may, for example, be an organic polyvalent isocyanate compound or an organic polyvalent quinone imine compound.

有機多價異氰酸酯化合物，可舉芳香族多價異氰酸酯化合物、脂肪族多價異氰酸酯化合物、脂環族多價異氰酸酯化合物及該等有機多價異氰酸酯化合物之三聚物、及使該等有機多價異氰酸酯化合物與多元醇化合物反應而得之末端異氰酸酯尿烷預聚合物等。 The organic polyvalent isocyanate compound may, for example, be an aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, an alicyclic polyvalent isocyanate compound, a terpolymer of the organic polyvalent isocyanate compound, and the organic polyvalent isocyanate. A terminal isocyanate urethane prepolymer obtained by reacting a compound with a polyol compound.

有機多價異氰酸酯化合物，具體可舉2,4-亞甲苯基異氰酸酯、2,6-亞甲苯基異氰酸酯、1,3-亞甲苯基二異氰酸酯、1,4-二甲苯二異氰酸酯、二苯甲烷-4,4'-二異氰酸酯、二苯甲烷-2,4'-二異氰酸酯、3-甲基二苯甲烷二異氰酸酯、六亞甲基異氰酸酯、異佛爾酮二異氰酸酯、二環己基甲烷-4,4'-二異氰酸酯、二環己基甲烷-2,4'-二異氰酸酯、三羥甲基丙烷加成亞甲苯基二異氰酸酯及賴氨酸異氰酸酯。 The organic polyvalent isocyanate compound may specifically be 2,4-tolyl isocyanate, 2,6-tolyl isocyanate, 1,3-tolyl diisocyanate, 1,4-xylene diisocyanate or diphenylmethane- 4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene isocyanate, isophorone diisocyanate, dicyclohexylmethane-4, 4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, trimethylolpropane plus tolylene diisocyanate and lysine isocyanate.

有機多價亞胺化合物，具體而言N,N'-二苯甲烷-4,4'-雙(1-氮丙啶基羧基醯胺)、三羥甲基丙烷-三-β-氮丙啶基丙酸酯、四羥甲基甲烷-三-β-氮丙啶基丙酸酯及N,N'-甲苯-2,4-雙(1-氮丙啶基羧基醯胺)三亞乙基三聚氰胺等。 Organic polyvalent imine compounds, in particular N,N'-diphenylmethane-4,4'-bis(1-aziridinylcarboxyguanamine), trimethylolpropane-tri-beta-aziridine Propionate, tetramethylolmethane-tri-beta-aziridine propionate and N,N'-toluene-2,4-bis(1-aziridinecarboxycarboxylamine)triethylene melamine Wait.

架橋劑，對架橋前之丙烯酸系聚合物(A1)100質量部，通常為0.01~20質量部，以0.1~10質量部為佳，以0.5~5質量部之比例使用更佳。 The bridging agent is usually 0.01 to 20 parts by mass of the acrylic polymer (A1) before bridging, preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass.

在於本發明，構成保護膜形成用薄膜4之成分之含量之態樣，以聚合物成分(A)之含量作為基準決定時，聚合物成分(A)為架橋之丙烯酸系聚合物時，作為其基準之含量， 係架橋前之丙烯酸系聚合物之含量。 In the present invention, when the content of the component constituting the film for forming a protective film 4 is determined based on the content of the polymer component (A), when the polymer component (A) is a bridging acrylic polymer, The content of the benchmark, The content of the acrylic polymer in front of the bridge.

(A2)非丙烯酸系樹脂 (A2) non-acrylic resin

此外，作為聚合物成分(A)，亦可使用選自由聚酯、苯氧基樹脂(為與後述之硬化性聚合物(AB)區別的權宜上，限於不具有環氧基者。)、聚碳酸酯、聚醚、聚氨脂、聚矽氧烷、橡膠系聚合物或該等的2種以上鍵結者之非丙烯酸系樹脂(A2)之1種單獨或組合2種以上使用。如此之樹脂，以重量平均分子量為20,000~100,000者為佳，以20,000~80,000者更佳。 Further, as the polymer component (A), a polyester or a phenoxy resin (which is distinguished from a curable polymer (AB) to be described later, and is not limited to having no epoxy group) may be used. One type or a combination of two or more types of a non-acrylic resin (A2), which is a carbonate, a polyether, a polyurethane, a polysiloxane, a rubber-based polymer, or a combination of two or more of these. Such a resin is preferably a weight average molecular weight of 20,000 to 100,000, more preferably 20,000 to 80,000.

非丙烯酸系樹脂(A2)之玻璃轉移溫度，以-30~150℃為佳，以-20~120℃的範圍更佳。 The glass transition temperature of the non-acrylic resin (A2) is preferably -30 to 150 ° C, more preferably -20 to 120 ° C.

將非丙烯酸系樹脂(A2)與上述丙烯酸系聚合物(A1)並用時，非丙烯酸系樹脂(A2)之含量並無特別限定。在以非丙烯酸系樹脂(A2)與丙烯酸系聚合物(A1)之質量比(A2：A1)，通常為1：99~60：40，以1：99~30：70的範圍為佳。 When the non-acrylic resin (A2) and the acrylic polymer (A1) are used in combination, the content of the non-acrylic resin (A2) is not particularly limited. The mass ratio (A2: A1) of the non-acrylic resin (A2) to the acrylic polymer (A1) is usually from 1:99 to 60:40, preferably from 1:99 to 30:70.

(B)硬化性成分 (B) hardening ingredients

硬化性成分(B)，係以賦予保護膜形成用薄膜4硬化性為主要目的而添加於保護膜形成用薄膜4。硬化性成分(B)，可使用熱硬化性成分(B1)或能量線硬化性成分(B2)。此外，亦可組合該等使用。熱硬化性成分(B1)，係含有至少可藉由加熱而反應之官能基之化合物。此外，能量線硬化性成分(B2)，含有可藉由能量線照射而反應之官能基之化合物(B21)，受到紫外線、電子線等的能量線的照射會聚合硬化。該等硬化性成分所具有的官能基相互反應，形成三維網狀構造而實現硬化。硬化性成分(B)，由於與聚合物成分(A)組合使用，故由抑制保護膜形成 用組成物之黏度，提升其操作性等的觀點，通常其重量平均分子量(Mw)係10,000以下，以100~10,000為佳。 The curable component (B) is added to the film for protective film formation 4 for the main purpose of imparting the curability of the film 4 for forming a protective film. As the curable component (B), a thermosetting component (B1) or an energy ray-curable component (B2) can be used. In addition, these uses can also be combined. The thermosetting component (B1) is a compound containing a functional group which can be at least reacted by heating. Further, the energy ray-curable component (B2) contains a compound (B21) which is a functional group reactive by irradiation with an energy ray, and is polymerized and cured by irradiation with an energy ray such as an ultraviolet ray or an electron beam. The functional groups of the curable components react with each other to form a three-dimensional network structure to achieve hardening. The curable component (B) is formed by inhibiting the protective film by being used in combination with the polymer component (A). From the viewpoint of the viscosity of the composition and the operability thereof, the weight average molecular weight (Mw) is usually 10,000 or less, preferably 100 to 10,000.

(B1)熱硬化性成分 (B1) thermosetting component

作為熱硬化性成分，例如以環氧系熱硬化性成分為佳。 As the thermosetting component, for example, an epoxy thermosetting component is preferred.

環氧系熱硬化性成分係包含具有環氧基之化合物(B11)，使用組合具有環氧基之化合物(B11)與熱硬化劑(B12)者為佳。 The epoxy thermosetting component contains a compound (B11) having an epoxy group, and a compound (B11) having an epoxy group and a thermal curing agent (B12) are preferably used.

(B11)具有環氧基之化合物 (B11) a compound having an epoxy group

具有環氧基之化合物(B11)(以下，有稱為「環氧化合物(B11)」之情形。)，可使用先前習知者。具體而言，可舉多官能系環氧樹脂、雙酚A縮水甘油醚或其加氫物、鄰甲酚酚醛環氧樹脂、二環戊二烯型環氧樹脂、聯苯型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、亞苯基骨架型環氧樹脂等，於分子中具有2官能以上之環氧化合物。該等可以1種單獨或組合2種以上使用。 The compound (B11) having an epoxy group (hereinafter referred to as "epoxy compound (B11)") can be used. Specific examples thereof include a polyfunctional epoxy resin, bisphenol A glycidyl ether or a hydrogenated product thereof, an o-cresol novolac epoxy resin, a dicyclopentadiene epoxy resin, and a biphenyl epoxy resin. A bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenylene skeleton type epoxy resin, etc., and a bifunctional or more epoxy compound in a molecule. These may be used alone or in combination of two or more.

使用環氧化合物(B11)時，於保護膜形成用薄膜4，對聚合物成分(A)100質量部，以1~1,500質量部包含環氧化合物(B11)為佳，以3~1,200質量部更佳。環氧化合物(B11)較少，則有降低在於保護膜形成用薄膜4之硬化後之黏著性的趨勢。此外，作為環氧化合物(B11)，僅使用在於常溫為固體者時，當環氧化合物(B11)較少，即相對地聚合物成分(A)較多時，有使保護膜形成用薄膜4之探頭黏性值上升的趨勢。再者，常溫係指25℃，以下相同。 When the epoxy resin (B11) is used, the film 4 for protective film formation preferably contains the epoxy compound (B11) in an amount of 1 to 1,500 parts by mass in 100 parts by mass of the polymer component (A), and is preferably 3 to 1,200 parts by mass. Better. When the amount of the epoxy compound (B11) is small, there is a tendency that the adhesion of the film 4 for forming a protective film after curing is lowered. In addition, when the epoxy compound (B11) is used only when the room temperature is solid, when the epoxy compound (B11) is small, that is, when the amount of the polymer component (A) is relatively large, the film for forming a protective film 4 is used. The tendency of the probe viscosity value to rise. Further, the normal temperature means 25 ° C, and the same applies hereinafter.

由於有如此趨勢，作為環氧化合物(B11)，僅使用在於常溫為固體者時，對聚合物成分(A)100質量部，以70~150 質量部包含環氧化合物(B11)特別佳。 Since there is such a tendency, when the epoxy compound (B11) is used only when the room temperature is solid, the polymer component (A) is 100 parts by mass, 70 to 150. The mass portion containing an epoxy compound (B11) is particularly preferred.

(B12)熱硬化劑 (B12) Thermal hardener

熱硬化劑(B12)，對環氧化合物(B11)作用作為硬化劑。較佳的熱硬化劑，可舉於1分子中具有2個以上可與環氧基反應之官能基之化合物。其官能基，可舉酚性羥基、醇性羥基、胺基、羧基及酸酐等。該等之中，較佳的可舉酚性羥基、胺基、酸酐等，進一步較佳的可舉酚性羥基、胺基。 The heat hardener (B12) acts as a hardener for the epoxy compound (B11). A preferred thermosetting agent is a compound having two or more functional groups reactive with an epoxy group in one molecule. The functional group may, for example, be a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group or an acid anhydride. Among these, a phenolic hydroxyl group, an amine group, an acid anhydride, etc. are preferable, and a phenolic hydroxyl group and an amine group are further preferable.

酚系硬化劑的具體例，可舉多官能系酚樹脂、聯苯、酚醛型酚樹脂、環戊二烯系酚樹脂、新酚型酚樹脂、烷基酚樹脂。胺系硬化劑之具體例，可舉DICY(雙氰胺)。該等可以1種單獨或混合2種以上使用。 Specific examples of the phenolic curing agent include polyfunctional phenol resins, biphenyls, novolac phenol resins, cyclopentadiene phenol resins, neophenol phenol resins, and alkylphenol resins. Specific examples of the amine-based curing agent include DICY (dicyandiamide). These may be used alone or in combination of two or more.

熱硬化劑(B12)之含量，對環氧化合物(B11)100質量部，以0.1~500質量部為佳，以1~200質量部更佳。熱硬化劑之含量少，則在於硬化後之黏著性有下降的趨勢。 The content of the thermal curing agent (B12) is preferably 0.1 to 500 parts by mass, and more preferably 1 to 200 parts by mass, based on 100 parts by mass of the epoxy compound (B11). When the content of the heat hardener is small, the adhesiveness after hardening tends to decrease.

(B13)硬化促進劑 (B13) hardening accelerator

亦可將硬化促進劑(B13)，用於調整保護膜形成用薄膜4之熱硬化速度。硬化促進劑(B13)，特別是可良好地使用於作為熱硬化性成分(B1)使用環氧系熱硬化性成分之情形。 The hardening accelerator (B13) can also be used to adjust the heat hardening rate of the film 4 for forming a protective film. In particular, the hardening accelerator (B13) can be suitably used in the case where an epoxy-based thermosetting component is used as the thermosetting component (B1).

較佳的硬化促進劑，可舉三亞乙基二胺、苄基二甲基胺、三乙醇胺、二甲基胺基乙醇、三(二甲基胺基甲基)酚等之3級胺類；2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑等的咪唑類；三丁基膦、二苯基膦、三苯基膦等的有機膦類；四苯基鏻四苯基硼酸酯、三苯基鏻四苯基硼酸酯等的四苯基硼 酸鹽等。該等可以1種單獨或混合2種以上使用。 Preferred hardening accelerators include tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethylimidazole; organophosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine; tetraphenylphosphonium tetraphenyl borate; triphenylsulfonium tetraphenyl borate Tetraphenyl boron Acid salt, etc. These may be used alone or in combination of two or more.

硬化促進劑(B13)，對環氧化合物(B11)及熱硬化劑(B12)之共計量100質量部，包含0.01~10質量部為佳，以0.1~1質量部之量更佳。藉由將硬化促進劑(B13)以上述範圍的量含有，即使曝於高溫度高濕度下，亦可具有優良的黏著性，即使曝於嚴酷的回火條件之情形，亦可達成很高的可靠度。藉由添加硬化促進劑(B13)，可提升保護膜形成用薄膜4的硬化之後的黏著性。如此之作用，硬化促進劑(B13)之含量越多越強。 The curing accelerator (B13) is preferably a total of 100 parts by mass of the epoxy compound (B11) and the thermosetting agent (B12), preferably 0.01 to 10 parts by mass, more preferably 0.1 to 1 part by mass. By containing the hardening accelerator (B13) in the above range, it can have excellent adhesion even when exposed to high temperature and high humidity, and can be achieved even under severe tempering conditions. Reliability. By adding a hardening accelerator (B13), the adhesiveness after hardening of the film for protective film formation 4 can be improved. As such, the more the content of the hardening accelerator (B13), the stronger.

(B2)能量線硬化性成分 (B2) energy line hardening component

藉由保護膜形成用薄膜4含有能量線硬化性成分，無需進行多量的能量與需要長時間的熱硬化步驟而使保護膜形成用薄膜4硬化。藉此，可圖謀製造成本的降低。 The film for protective film formation 4 contains the energy ray-curable component, and the film for protective film formation 4 is hardened without performing a large amount of energy and a heat hardening step which requires a long time. Thereby, the manufacturing cost can be reduced.

能量線硬化性成分，可單獨使用具有以能量線照射而反應之官能基之化合物(B21)，使用具有以能量線照射而反應之官能基之化合物(B21)與光聚合起始劑(B22)之組合者為佳。 As the energy ray-curable component, a compound (B21) having a functional group reactive by irradiation with an energy ray can be used alone, and a compound (B21) having a functional group reactive by irradiation with an energy ray and a photopolymerization initiator (B22) can be used. The combination is better.

(B21)具有以能量線照射而反應之官能基之化合物 (B21) a compound having a functional group which is irradiated by an energy ray

具有以能量線照射而反應之官能基之化合物(B21)(以下，有稱為「能量線反應性化合物(B21)」之情形。)，具體可舉三羥甲基丙烷三丙烯酸酯、異戊四醇三丙烯酸酯、異戊四醇四丙烯酸酯、二異戊四醇單羥基五丙烯酸酯、二異戊四醇六丙烯酸酯或1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯等地丙烯酸酯系化合物，此外，亦可舉，寡聚酯丙烯酸酯、尿烷丙烯酸酯系寡聚物、環氧基丙烯酸酯、聚醚丙烯酸酯及依康酸寡聚物等 之丙烯酸酯系化合物，而分子量相對較低者。如此之化合物，係於分子內至少具有1個聚合性雙鍵鍵結。 A compound (B21) having a functional group which is reacted by irradiation with an energy ray (hereinafter referred to as "energy ray-reactive compound (B21)"), specifically, trimethylolpropane triacrylate and isoprene Tetraol triacrylate, isoamyl alcohol tetraacrylate, diisopentaerythritol monohydroxy pentaacrylate, diisopentyl alcohol hexaacrylate or 1,4-butanediol diacrylate, 1,6-hexyl An acrylate-based compound such as a diol diacrylate, and an oligoester acrylate, a urethane acrylate oligomer, an epoxy acrylate, a polyether acrylate, and an econic acid oligomer Wait Acrylate based compound with relatively low molecular weight. Such a compound has at least one polymerizable double bond in the molecule.

使用能量線反應性化合物(B21)時，於保護膜形成用薄膜4，對聚合物成分(A)100質量部，包含1~1,500質量部能量線反應性化合物(B21)為佳，以3~1,200質量部更佳。 When the energy ray-reactive compound (B21) is used, the protective film-forming film 4 preferably contains 1 to 1,500 parts by mass of the energy-ray reactive compound (B21) in 100 parts by mass of the polymer component (A), and 3~ 1,200 mass parts are better.

(B22)光聚合起始劑 (B22) Photopolymerization initiator

藉由在能量線反應性化合物(B21)組合光聚合起始劑(B22)，可使聚合硬化時間變短，以及可減少光線照射量。 By combining the photopolymerization initiator (B22) with the energy ray-reactive compound (B21), the polymerization hardening time can be shortened, and the amount of light irradiation can be reduced.

如此之光聚合起始劑(B22)，具體二苯甲酮、苯乙酮、安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚、安息香苯甲酸、安息香苯甲酸甲酯、安息香二甲基酮、2,4-二乙基噻吨酮、α-羥基環己基苯基酮、苄基二苯基硫醚、四甲基秋蘭姆單硫醚、偶氮二異丁腈、二苯基乙二酮、二苄基甲酮、丁二酮、1,2-二苯基甲烷、2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮、2,4,6-三甲基苄基二苯基氧化膦及及β-氯蒽醌等。光聚合起始劑(B22)可以1種單獨或組合2種以上。 Such a photopolymerization initiator (B22), specifically benzophenone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin benzoate, Benzoin dimethyl ketone, 2,4-diethyl thioxanthone, α-hydroxycyclohexyl phenyl ketone, benzyl diphenyl sulfide, tetramethyl thiuram monosulfide, azobisisobutyronitrile , diphenylethylenedione, dibenzyl ketone, butanedione, 1,2-diphenylmethane, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)benzene Acetone, 2,4,6-trimethylbenzyldiphenylphosphine oxide and β-chloropurine. The photopolymerization initiator (B22) may be used alone or in combination of two or more.

光聚合起始劑(B22)之調合比例，對能量線反應性化合物(B21)100質量部，含有0.1~10質量部為佳，以1~5質量部更佳。光聚合起始劑(B22)之調合比例未滿0.1質量部，則有光聚合不足而無法得到滿足的硬化性之情形，超過10質量部則有則生成不參予光聚合之殘留物，而成為異常之原因之情形。 The blending ratio of the photopolymerization initiator (B22) is preferably 0.1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the energy ray-reactive compound (B21). When the blending ratio of the photopolymerization initiator (B22) is less than 0.1 part by mass, there is a case where the photopolymerization is insufficient and the curability is not satisfied, and if it exceeds 10 parts, the residue which does not participate in photopolymerization is formed. The situation that becomes the cause of the abnormality.

(第2膠合劑成分) (2nd adhesive component)

第2之膠合劑成分，藉由含有硬化性聚合物成分(AB)，可對 保護膜形成用薄膜4賦予(1)板片形狀維持性及(3)硬化性。 The second binder component can be obtained by containing a curable polymer component (AB). The film for protective film formation 4 is provided with (1) sheet shape maintenance property and (3) hardenability.

(AB)硬化性聚合物成分 (AB) hardenable polymer component

硬化性聚合物成分，係具有硬化功能官能基之聚合物。硬化功能官能基，係可互相反應構成三維網狀構造的官能基，可舉藉由加熱反應之官能基，或以能量線反應之官能基。 The curable polymer component is a polymer having a functional group that hardens. The hardening functional functional groups are functional groups which can react with each other to form a three-dimensional network structure, and may be a functional group which is heated by a reaction or a functional group which reacts with an energy ray.

硬化功能官能基，可加成於成為硬化性聚合物(AB)之骨格之連續構造之單位中，亦可加成於末端。硬化功能官能基加成於成為硬化性聚合物成分(AB)之骨格之連續構造之單位中時，硬化功能官能基可加成於側鏈，亦可直接加成於主鏈。硬化性聚合物成分(AB)之重量平均分子量(Mw)，由達成對保護膜形成用薄膜4賦予(1)板片形狀維持性的目的的觀點，通常為20,000以上。 The hardening functional group may be added to the unit of the continuous structure which becomes the skeleton of the hardening polymer (AB), or may be added to the terminal. When the hardening functional group is added to a unit which is a continuous structure of the skeleton of the curable polymer component (AB), the hardening functional group may be added to the side chain or may be directly added to the main chain. The weight average molecular weight (Mw) of the curable polymer component (AB) is usually 20,000 or more from the viewpoint of imparting (1) sheet shape shape retention property to the film 4 for forming a protective film.

藉由加熱反應之官能基，可舉環氧基。具有環氧基之硬化性聚合物成分(AB)，可舉高分子量的含有環氧基之化合物，或具有環氧基之苯氧基樹脂。高分子量的含有環氧基之化合物，可舉例如日本特開2001-261789所揭示者。 The epoxy group can be mentioned by heating the functional group of the reaction. The epoxy group-containing curable polymer component (AB) may, for example, be a high molecular weight epoxy group-containing compound or an epoxy group-containing phenoxy resin. The high molecular weight compound containing an epoxy group is disclosed, for example, in JP-A-2001-261789.

此外，亦可係與上述丙烯酸系聚合物(A1)同樣的聚合物，作為單體，使用具有環氧基之單體所聚合者(含有環氧基之丙烯酸系聚合物)。作為如此之單體，可舉例如，(甲基)丙烯酸酯縮水甘油酯等具有縮水甘油基之(甲基)丙烯酸酯。 Further, a polymer similar to the above acrylic polymer (A1) may be used, and a monomer having an epoxy group (acrylic polymer containing an epoxy group) may be used as a monomer. As such a monomer, a (meth) acrylate having a glycidyl group such as (meth) acrylate glycidyl ester can be mentioned.

使用含有環氧基之丙烯酸系聚合物時，其較佳的態樣與丙烯酸系聚合物(A1)相同。 When an acrylic polymer containing an epoxy group is used, the preferred embodiment is the same as that of the acrylic polymer (A1).

使用具有環氧基之硬化性聚合物成分(AB)時，與使用環氧系熱硬化性成分作為硬化性成分(B)之情形同樣地， 亦可並用熱硬化劑(B12)、及硬化促進劑(B13)。 When a curable polymer component (AB) having an epoxy group is used, similarly to the case where an epoxy thermosetting component is used as the curable component (B), A thermosetting agent (B12) and a hardening accelerator (B13) may also be used in combination.

藉由能量線反應之官能基，可舉(甲基)丙烯醯基。具有藉由能量線反應之官能基之硬化性聚合物成分(AB)，可使用具有聚醚丙烯酸酯等的聚合構造之丙烯酸酯系化合物之高分子量者。 The functional group based on the energy ray reaction may, for example, be a (meth) acrylonitrile group. As the curable polymer component (AB) having a functional group reactive by an energy ray, a high molecular weight of an acrylate-based compound having a polymerization structure such as a polyether acrylate can be used.

此外，亦可使用例如，使側鏈具有羥基等的官能基X之原料聚合物，與具有可與官能基X反應之官能基Y(例如，官能基X為羥基時，以異氰酸酯基等)及藉由能量線照射反應之官能基之低分子化合物反應而調製之聚合物。 Further, for example, a base polymer having a functional group X such as a hydroxyl group in a side chain and a functional group Y capable of reacting with the functional group X (for example, an isocyanate group when the functional group X is a hydroxyl group) may be used. A polymer prepared by reacting a low molecular compound of a functional group of a reaction with an energy ray.

在於此種情形，原料聚合物相當於上述丙烯酸系聚合物(A)時，其原料聚合物之較佳的態樣與丙烯酸系聚合物(A)相同。 In this case, when the base polymer corresponds to the acrylic polymer (A), the preferred aspect of the base polymer is the same as that of the acrylic polymer (A).

使用具有藉由能量線反應之官能基之硬化性聚合物成分(AB)時，與使用能量線硬化性成分(B2)之情形同樣地，亦可並用光聚合起始劑(B22)。 When a curable polymer component (AB) having a functional group reactive by an energy ray is used, a photopolymerization initiator (B22) may be used in combination as in the case of using the energy ray-curable component (B2).

第2膠合劑成分，可與硬化性聚合物成分(AB)一併，含有上述聚合物成分(A)或硬化性成分(B)。 The second binder component may contain the polymer component (A) or the curable component (B) together with the curable polymer component (AB).

於保護膜形成用薄膜4，於膠合劑成分之外，亦可含有以下成分。 The film 4 for forming a protective film may contain the following components in addition to the binder component.

(C)填充材 (C) filler

保護膜形成用薄膜4，亦可含有無機填充劑等的填充材(C)。以下，以填充材(C)為無機填充劑之情形作為具體例說明。藉由將無機填充劑作為填充材(C)調合於保護膜形成用薄膜4，可調整保護膜在硬化後的膨脹係數，藉由使硬化後的保護膜的熱 膨脹係數對被加工構件W最佳化，可提升由半導體裝置等被加工構件W所形成之製品(以下，有簡稱為「製品」之情形。)之可靠度。此外，亦可減低硬化後的保護膜之吸濕性。 The film 4 for forming a protective film may contain a filler (C) such as an inorganic filler. Hereinafter, the case where the filler (C) is an inorganic filler will be described as a specific example. By blending the inorganic filler as the filler (C) in the film for forming a protective film 4, the expansion coefficient of the protective film after curing can be adjusted by the heat of the cured protective film. The expansion coefficient is optimized for the workpiece W, and the reliability of the product formed by the workpiece W such as a semiconductor device (hereinafter, simply referred to as "product") can be improved. In addition, the hygroscopicity of the cured protective film can also be reduced.

再者，藉由對保護膜施以雷射標記，於雷射光所削去的部分作為填充材(C)之無機填充劑露出，會使反射光擴散而呈現接近白色的顏色。藉此，保護膜形成用薄膜4含有後述之著色劑(D)時，可得雷射標記部分與其他的部分之對比差，使印字明顯的效果。 Further, by applying a laser mark to the protective film, the portion scraped off by the laser light is exposed as an inorganic filler of the filler (C), and the reflected light is diffused to exhibit a color close to white. As a result, when the protective film forming film 4 contains a coloring agent (D) to be described later, it is possible to obtain a contrast difference between the laser marking portion and the other portions, and to make the printing effect remarkable.

較佳的無機填充劑，可舉二氧化矽、氧化鋁、滑石、碳酸鈣、氧化鈦、氧化鐵、碳化矽、氮化硼等的粉末、將該等球形化之珠、單晶纖維及玻璃纖維等。該等之中，以二氧化矽填充劑及氧化鋁填充劑為佳。作為上述填充材(C)之無機填充劑，可以單獨或混合2種以上使用。 Preferred inorganic fillers include powders of cerium oxide, aluminum oxide, talc, calcium carbonate, titanium oxide, iron oxide, cerium carbide, boron nitride, etc., spheroidized beads, single crystal fibers, and glass. Fiber, etc. Among these, a cerium oxide filler and an alumina filler are preferred. The inorganic filler of the above-mentioned filler (C) may be used alone or in combination of two or more.

無機填充劑等的填充材(C)之含量並無特別限定。考慮該含量過多時，會降低對被加工構件W之接著性，過少時有難以得到藉由含有無機填充劑提升標記部分的確認性的效果，及填充材(C)之組成適宜設定即可。通常，構成保護膜形成用薄膜4佔全固形份之質量之比例，填充材(C)之含量以30~80質量%為佳，以50~80質量%更佳，以60~80質量%特別佳。此外，基材1含有如無機填充劑之填充材(C)時，保護膜形成用薄膜4所含有的填充材(C)之保護膜形成用薄膜4佔全固形份之質量所占的比例，較基材2所含有之填充材佔基材2之全固形份之質量比更多為佳。 The content of the filler (C) such as an inorganic filler is not particularly limited. When the content is too large, the adhesion to the member W to be processed is lowered, and when the amount is too small, it is difficult to obtain the effect of confirming the marked portion by the inorganic filler, and the composition of the filler (C) may be appropriately set. In general, the ratio of the thickness of the film 4 for forming a protective film to the total solid content is preferably 30 to 80% by mass, more preferably 50 to 80% by mass, and particularly preferably 60 to 80% by mass. good. In addition, when the base material 1 contains a filler (C) such as an inorganic filler, the protective film forming film 4 of the filler (C) contained in the protective film forming film 4 accounts for the proportion of the total solid content. The mass ratio of the filler contained in the substrate 2 to the total solid content of the substrate 2 is preferably more.

(D)著色劑 (D) colorant

於保護膜形成用薄膜4，可調合著色劑(D)。藉由調合著色劑，將半導體裝置等的產品組入機器等時，可防止配置於製品的周圍之裝置所產生的紅外線等造成錯誤動作。此外，藉由雷射標記等的手段對保護膜進行刻印時，有使文字、記號等的標記容易辨識的效果。即，形成保護膜之製品(半導體裝置或半導體晶片等)，於保護膜的表面通常以雷射標記法(以雷射光削去保護膜表面進行印字的方法)印型號等，藉由保護膜含有著色劑(D)，可充分得到保護膜以雷射光削去的部分與並非如此之部分的對比差，而提升視認性。 In the film 4 for forming a protective film, the coloring agent (D) can be adjusted. When a product such as a semiconductor device is incorporated into a machine or the like by blending a coloring agent, it is possible to prevent an erroneous operation such as infrared rays generated by a device disposed around the product. Further, when the protective film is imprinted by means such as a laser mark or the like, there is an effect that the marks of characters, symbols, and the like are easily recognized. That is, a product (semiconductor device, semiconductor wafer, or the like) that forms a protective film is usually printed on the surface of the protective film by a laser marking method (a method of printing the surface of the protective film by laser light), and the protective film contains The coloring agent (D) can sufficiently obtain a contrast difference between a portion of the protective film which is removed by laser light and a portion which is not so, and enhance visibility.

作為著色劑，可使用有機或無機的顏料及染料。該等之中，由電磁波或紅外線遮蔽性的觀點以黑色顏料為佳。作為黑色顏料，可使用碳黑、氧化鐵、二氧化錳、苯胺黑、活性炭等，並不限定於該等。由提高半導體裝置等的製品之可靠度的觀點，以碳黑特別佳。著色劑(D)，可使用1種單獨，亦可組合2種以上使用。 As the colorant, organic or inorganic pigments and dyes can be used. Among these, a black pigment is preferred from the viewpoint of electromagnetic wave or infrared shielding. As the black pigment, carbon black, iron oxide, manganese dioxide, aniline black, activated carbon or the like can be used, and it is not limited thereto. From the viewpoint of improving the reliability of a product such as a semiconductor device, carbon black is particularly preferable. The coloring agent (D) may be used alone or in combination of two or more.

著色劑(D)之調合量，對構成保護膜形成用薄膜4之全固形份份100質量部，以0.1~35質量部為佳，以0.5~25質量部更佳，以1~15質量部特別佳。 The blending amount of the coloring agent (D) is preferably 0.1 to 35 parts by mass, and more preferably 0.5 to 25 parts by mass, and 1 to 15 parts by mass of the total solid portion of the film 4 for forming the protective film. Especially good.

(E)偶合劑 (E) coupling agent

亦可將具有與無機物反應之官能基及有機官能基反應之官能基之偶合劑(E)，使用於提升保護膜形成用薄膜對被著體之接著性、密著性及/或保護膜之凝聚性。此外，藉由使用偶合劑(E)，不損及硬化保護膜形成用薄膜4而得之保護膜之耐熱性，而提升其耐水性。如此之偶合劑，可舉鈦酸酯系偶合劑、 鋁酸酯系偶合劑、矽烷偶合劑等。該等之中，以矽烷偶合劑為佳。 The coupling agent (E) having a functional group reactive with a functional group and an organic functional group reactive with an inorganic substance may be used for improving the adhesion, adhesion, and/or protective film of the film for forming a protective film to the object. Cohesion. Further, by using the coupling agent (E), the heat resistance of the protective film obtained by curing the film 4 for forming a protective film is not impaired, and the water resistance thereof is improved. Such a coupling agent may be a titanate coupling agent, Aluminate coupling agent, decane coupling agent, and the like. Among these, a decane coupling agent is preferred.

矽烷偶合劑，可良好地使用與其有機官能基反應之官能基，與聚合物成分(A)、硬化性成分(B)、硬化性聚合物成分(AB)等所具有的官能基反應之基之矽烷偶合劑。 The decane coupling agent can suitably use a functional group reactive with an organic functional group, and reacts with a functional group possessed by the polymer component (A), the curable component (B), and the curable polymer component (AB). Decane coupling agent.

如此之矽烷偶合劑矽烷偶合劑，可舉γ-縮水甘油基丙基三甲氧基矽烷、γ-縮水甘油基丙基甲基二乙氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-(甲基丙烯醯氧丙基)三甲氧基矽烷、γ-胺基丙基三甲氧基矽烷、N-6-(胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-6-(胺基乙基)-γ-胺基丙基甲基二乙氧基矽烷、N-苯基胺基丙基三甲氧基矽烷、γ-丙基三乙氧基矽烷、γ-胇基丙基三甲氧基矽烷γ-胇基丙基甲基二甲氧基矽烷、雙(3-三乙氧基矽基丙基)四硫化物、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯三甲氧基矽烷、乙烯三乙酸基矽烷、咪唑矽烷等。該等可以1種單獨或混合2種以上使用。 Such a decane coupling agent decane coupling agent may, for example, be γ-glycidylpropyltrimethoxydecane, γ-glycidylpropylmethyldiethoxysilane or β-(3,4-epoxycyclohexyl). Ethyltrimethoxydecane, γ-(methacryloxypropyl)trimethoxydecane, γ-aminopropyltrimethoxydecane, N-6-(aminoethyl)-γ-aminopropyl Trimethoxy decane, N-6-(aminoethyl)-γ-aminopropylmethyldiethoxydecane, N-phenylaminopropyltrimethoxydecane, γ-propyltriethyl Oxydecane, γ-mercaptopropyltrimethoxydecane γ-mercaptopropylmethyldimethoxydecane, bis(3-triethoxydecylpropyl)tetrasulfide, methyltrimethoxy Decane, methyl triethoxy decane, ethylene trimethoxy decane, ethylene triacetoxy decane, imidazolium, and the like. These may be used alone or in combination of two or more.

矽烷偶合劑，對聚合物成分(A)、硬化性成分(B)及硬化性聚合物成分(AB)之共計100質量部，通常為0.1~20質量部，以0.2~10質量部為佳，以0.3~5質量部的比例包含更佳。矽烷偶合劑之含量未滿0.1質量部，則有無法得到上述效果的可能性，超過20質量部，則有成為脫氣之原因的可能性。 The decane coupling agent is preferably 0.1 to 20 parts by mass in total of 100 parts by mass of the polymer component (A), the curable component (B), and the curable polymer component (AB), and preferably 0.2 to 10 parts by mass. It is preferably included in a ratio of 0.3 to 5 mass parts. When the content of the decane coupling agent is less than 0.1 part by mass, the above effect may not be obtained, and if it exceeds 20 parts by mass, there is a possibility of degassing.

(F)剝離劑 (F) stripper

為調整保護膜形成用薄膜4對被加工構件W之面之密著性或黏著劑層3之密著性，亦可添加剝離劑。剝離劑，可舉聚二甲基矽氧烷、聚苯基甲基矽氧烷、聚二苯基矽氧烷等的矽酮化 合物或氟化合物。 In order to adjust the adhesion of the film 4 for forming a protective film to the surface of the member W to be processed or the adhesion of the adhesive layer 3, a release agent may be added. The release agent may be an oxime ketone of polydimethyl siloxane, polyphenyl methyl siloxane or polydiphenyl siloxane. Compound or fluorine compound.

該等之中，以矽酮化合物為佳，作為側鏈具有包含芳香環之基之有機聚矽氧烷，且在於25℃之動黏度以50~100,000mm2/s者更佳。聚矽氧烷、-Si(X)2-O-表示之單位構造(X係表示側鏈)複數連接的化合物，該單位構造之數量並無特別限定，通常為3以上。藉由單位構造數量的增減，可控制上述動黏度之值。 Among these, an anthrone compound is preferred as the organopolyoxane having a side group containing an aromatic ring, and the dynamic viscosity at 25 ° C is preferably from 50 to 100,000 mm 2 /s. The compound structure represented by polyoxyalkylene or -Si(X) 2 -O- (the X system represents a side chain) is a plurality of compounds, and the number of the unit structures is not particularly limited, but is usually 3 or more. The value of the dynamic viscosity can be controlled by increasing or decreasing the number of unit structures.

矽酮化合物，藉由有機聚矽氧烷之矽氧烷部分降低與支持體的密著力的同時，藉由在側鏈具有上述含有芳香環之基，脂溶性高，與保護膜形成用組成物中的其他成分的相溶性高。此外，保護膜形成用組成物中的硬化成分(B)，構成成分具有芳香環之情形較多，如此之情形可藉由矽酮化合物之上述含有芳香環之基使互相的相溶性更加提升。 The fluorenone compound has a high fat solubility and a composition for forming a protective film by having the above-mentioned aromatic ring-containing group in the side chain, while reducing the adhesion to the support by the oxoxane portion of the organic polyoxyalkylene. The other components in the mixture have high compatibility. Further, in the cured component (B) in the composition for forming a protective film, the constituent component has a large number of aromatic rings, and in this case, the mutual compatibility of the fluorenone compound can be further improved by the above-mentioned aromatic ring-containing group.

上述含有芳香環之基係含有芳香環之官能基，其例，可舉苯基、芳烷基。在此，所謂芳烷基，係指烷基部為直鏈狀或分枝鏈狀，烷基部之碳數以1~5為佳，以1~3更佳，芳基部之碳數以6~10為佳，以6之芳烷基更佳。烷基之較佳例，可舉，苄基、苯乙基、苯丙基、苯異丙基。上述含有芳香環之基，以芳烷基為佳。 The base containing an aromatic ring contains a functional group of an aromatic ring, and examples thereof include a phenyl group and an aralkyl group. Here, the aralkyl group means that the alkyl group is linear or branched, and the number of carbon atoms in the alkyl group is preferably from 1 to 5, more preferably from 1 to 3, and the carbon number of the aryl moiety is from 6 to 10. Preferably, the aralkyl group of 6 is better. Preferable examples of the alkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, and a phenylisopropyl group. The above aromatic group-containing group is preferably an aralkyl group.

(G)泛用添加劑 (G) general purpose additives

保護膜形成用薄膜4，於上述以外，亦可按照必要調合各種添加劑。各種添加劑，可舉平滑劑、可塑劑、帶電防止劑、氧化防止劑、離子捕捉劑、除氣劑、鏈移動劑等。 The film 4 for forming a protective film may be blended with various additives as necessary in addition to the above. Examples of the various additives include a smoothing agent, a plasticizer, a charge preventing agent, an oxidation preventing agent, an ion scavenger, a deaerator, and a chain shifting agent.

(2-3)厚度 (2-3) Thickness

保護膜形成用薄膜4之厚度，並無特別限定。通常，以3μm以上300μm以下的範圍為佳，由保護膜形成用薄膜4所形成之保護膜可適當地作用的觀點，提高生產性的觀點，提高經濟性的觀點等，保護膜形成用薄膜4之厚度，以5μm以上250μm以下更佳，以7μm以上200μm以下特別佳。 The thickness of the film 4 for forming a protective film is not particularly limited. In the range of 3 μm or more and 300 μm or less, the protective film formed of the film 4 for forming a protective film can be suitably used, and the viewpoint of productivity can be improved, and the film for protective film formation can be improved. The thickness is preferably 5 μm or more and 250 μm or less, and particularly preferably 7 μm or more and 200 μm or less.

(3)界面接著調整層 (3) interface and then adjust the layer

如第4圖所示關於本實施形態之PR層積體100所包括的黏著板片1，可包括層積於黏著板片1之黏著劑層3側之主面1A之一部分的區域1b之界面接著調整層5。 The adhesive sheet 1 included in the PR laminate 100 of the present embodiment as shown in Fig. 4 may include an interface of a region 1b laminated on a portion of the main surface 1A of the adhesive layer 3 on the side of the adhesive sheet 1. Layer 5 is then adjusted.

界面接著調整層5，可為既定的薄膜，亦可為是界面接著調整黏著劑層。界面接著調整黏著劑層，係對能量線硬化性的黏著劑預先進行能量線照射使之硬化者為佳。此外，界面接著調整層5，亦可為黏著劑層3之一部分，與其他的部分性質不同地處理者。可為例如，黏著劑層3係由含有上述丙烯酸系聚合物(α)等之黏著劑組成物所形成者，用於進行包含於黏著劑組成物之成分之聚合反應而照射之能量線之照射量相對較多，故聚合反應之進行程度相對較高，結果使黏著性降低的部分。或者，亦可係與黏著劑層3之基材2相對之面之相反側之面之一區域，較其他的區域更粗面化，結果使黏著性降低者。 The interface is then adjusted to layer 5, which may be a predetermined film, or may be an interface followed by an adjustment of the adhesive layer. The interface is then adjusted to the adhesive layer, and it is preferred that the energy ray-curable adhesive is previously irradiated with energy rays to harden it. Further, the interface is followed by the adjustment layer 5, which may also be a part of the adhesive layer 3, which is different from the other parts. For example, the adhesive layer 3 may be formed by an adhesive composition containing the above acrylic polymer (α) or the like, and may be used for irradiation of an energy ray irradiated by a polymerization reaction of a component contained in the adhesive composition. The amount of the polymerization reaction is relatively high, so that the degree of progress of the polymerization reaction is relatively high, and as a result, the adhesion is lowered. Alternatively, one of the faces on the opposite side to the surface facing the base material 2 of the adhesive layer 3 may be rougher than the other regions, and as a result, the adhesiveness may be lowered.

界面接著調整層5與保護膜形成用薄膜4之配置關係如下。即，保護膜形成用薄膜4，係與上述薄膜主面4A之相反側與黏著板片1相對之主面4B之全面，接於界面接著調整層5之與黏著層3相面之主面5B之相反側之主面5A地層積。與界面接著調整層5之黏著層3相面之主面5B與相反 側之主面5A，亦可包含沒有層積保護膜形成用薄膜4的區域。如此地以平面視，界面接著調整層5之主面與保護膜形成用薄膜4之主面相等或較保護膜形成用薄膜4之主面大地，設定界面接著調整層5之主面與保護膜形成用薄膜4之主面，則在於PR層積體100之製造步驟，將黏著板片1與保護膜形成用薄膜4貼合之作業時，可使保護膜形成用薄膜4對黏著板片1之貼合容許寬度變寬，可容易製造PR層積體100。 The arrangement relationship between the interface subsequent adjustment layer 5 and the protective film forming film 4 is as follows. In other words, the film 4 for forming a protective film is integrated with the main surface 4B opposite to the main surface 4A of the film and the main surface 4B facing the adhesive sheet 1, and is connected to the main surface 5B of the interface subsequent to the adhesion layer 3 of the adjustment layer 5. The main surface 5A on the opposite side is layered. The main surface 5B opposite to the adhesive layer 3 of the interface subsequent adjustment layer 5 is opposite The main surface 5A of the side may include a region where the film 4 for forming a protective film is not laminated. In this manner, the main surface of the interface subsequent adjustment layer 5 is equal to or larger than the main surface of the protective film forming film 4, and the interface is then adjusted to the main surface of the layer 5 and the protective film. The main surface of the film for forming the film 4 is a manufacturing step of the PR layered body 100. When the adhesive sheet 1 and the film 4 for forming a protective film are bonded together, the film for forming the protective film 4 can be bonded to the sheet 1 The bonding width is widened, and the PR laminate 100 can be easily manufactured.

(4)夾具接著層 (4) Fixture layer

關於本實施形態之PR層積體100所包括之保護膜形成用複合板片10，係如第5圖所示，亦可進一步包括夾具接著層6，其係層積在保護膜形成用複合板片10之保護膜形成用薄膜4側之主面10A之一部分的區域，位於上述加工用區域10a之外周區域10b。夾具接著層6，係用於將環形框等的夾具固定於黏著板片1者。夾具接著層，可採用具有芯材之兩面黏著板片，或黏著劑之單層所組成之層。 The composite sheet 10 for forming a protective film included in the PR laminate 100 of the present embodiment may further include a jig adhesive layer 6 which is laminated on the composite sheet for forming a protective film, as shown in Fig. 5 . A region of a portion of the main surface 10A on the side of the film 4 for forming a protective film of the sheet 10 is located in the outer peripheral region 10b of the processing region 10a. The jig attachment layer 6 is used to fix a jig such as a ring frame to the adhesive sheet 1. The jig adhesive layer may be a layer composed of a double-sided adhesive sheet having a core material or a single layer of an adhesive.

如上所述，黏著板片1包括界面接著調整層5時，如第6圖所示，夾具接著層6，層積於保護膜形成用複合板片10之保護膜形成用薄膜4側之主面10A之一部分的區域，位在設有黏著板片1之黏著劑層3側之主面1A之界面接著調整層5之區域1b之外周的區域10c為佳。藉由為如此之配置，可減低夾具接著層6發生由黏著板片1剝離之異常的可能性。 As described above, when the adhesive sheet 1 includes the interface-adjusting layer 5, as shown in Fig. 6, the jig-attached layer 6 is laminated on the main surface of the protective film forming film 4 on the composite sheet 10 for forming a protective film. The region of one of the portions 10A is preferably located at the interface of the main surface 1A on the side of the adhesive layer 3 on which the adhesive sheet 1 is provided, and the region 10c outside the region 1b of the adjustment layer 5. With such a configuration, the possibility that the jig-attach layer 6 is peeled off by the adhesive sheet 1 can be reduced.

(5)黏著板片對保護膜形成用薄膜之黏著性 (5) Adhesion of the adhesive sheet to the film for forming a protective film

關於本實施形態之PR層積體100所備之黏著板片1對保護膜形成用薄膜4之黏著力(在於本說明書，亦稱為「硬化前黏 著力」。)，以0.5N/25mm以下為佳，以0.3N/25mm以下更佳，以0.2N/25mm以下特別佳。下限值通常為0.01N/25mm程度。該硬化前黏著力低時，以保護膜形成用薄膜4之個片附著的狀態將被加工構件W之晶片由黏著板片1拾取時，優先在保護膜形成用薄膜4與黏著板片1之界面發生剝離，而不容易發生拾取不良。 The adhesion of the adhesive sheet 1 prepared in the PR laminate 100 of the present embodiment to the film 4 for forming a protective film (in the present specification, also referred to as "pre-hardening adhesion" Focus on it." It is preferably 0.5 N/25 mm or less, more preferably 0.3 N/25 mm or less, and particularly preferably 0.2 N/25 mm or less. The lower limit is usually about 0.01 N/25 mm. When the adhesion of the film for protective film formation 4 is picked up by the adhesive sheet 1 in a state in which the film of the film for protective film 4 is adhered, the film for protective film formation 4 and the adhesive sheet 1 are preferable. The interface is peeled off, and it is not easy to pick up badly.

使關於本實施形態之PR層積體100所包括之保護膜形成用複合板片10之保護膜形成用薄膜4硬化形成保護膜時，黏著板片1對保護膜之黏著力(在於本說明書，亦稱為「硬化後黏著力」。)，以0.5N/25mm以下為佳，以0.3N/25mm以下更佳，以0.2N/25mm以下特別佳。下限值通常為0.01N/25mm程度。該硬化後黏著力低時，以附著保護膜的狀態，將被加工構件W的晶片由黏著板片1拾取時，優先在保護膜與黏著板片1之界面發生剝離，而不容易發生拾取不良。 When the protective film forming film 4 of the composite film sheet 10 for protective film formation included in the PR laminate 100 of the present embodiment is cured to form a protective film, the adhesion of the adhesive sheet 1 to the protective film (in the present specification, Also known as "adhesive strength after hardening".), preferably 0.5 N/25 mm or less, more preferably 0.3 N/25 mm or less, and particularly preferably 0.2 N/25 mm or less. The lower limit is usually about 0.01 N/25 mm. When the adhesive strength after hardening is low, when the wafer of the workpiece W is picked up by the adhesive sheet 1 in a state in which the protective film is adhered, peeling occurs preferentially at the interface between the protective film and the adhesive sheet 1, and picking failure is unlikely to occur. .

關於本實施形態之PR層積體100之黏著板片1之黏著劑層3側之主面1A之保護膜形成用薄膜4所貼著之區域1a，由能量線硬化型黏著劑之硬化物所組成之接著劑表面組成為佳。於此種情形，黏著劑層3對保護膜形成用薄膜4或由此形成之保護膜(保護膜等)之黏著性容易變低。因此，將附著保護膜等的狀態的被加工構件W的晶片由黏著板片1拾取時，優先在保護膜等與黏著板片1之界面發生剝離，而不容易發生拾取不良。 In the region 1a of the protective film forming film 4 on the main surface 1A of the adhesive layer 3 on the side of the adhesive layer 3 of the PR laminate 100 of the present embodiment, the cured product of the energy ray-curable adhesive is used. The surface composition of the composition of the adhesive is preferred. In this case, the adhesion of the adhesive layer 3 to the protective film forming film 4 or the protective film (protective film or the like) formed thereby tends to be low. Therefore, when the wafer of the workpiece W to which the protective film or the like is attached is picked up by the adhesive sheet 1, the peeling of the interface between the protective film and the like and the adhesive sheet 1 is preferentially caused, and picking failure is less likely to occur.

(6)剝離板片 (6) peeling sheet

關於本實施形態之PR層積體100所包括之保護膜形成用複 合板片10，如第1圖所記載，於其保護膜形成用薄膜4側之表面10A，貼合剝離板片20之剝離方面20A。剝離板片20之構成為任意，可例示將塑膠薄膜以剝離劑等剝離處理者。塑膠薄膜之具體例，可舉聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯等的聚酯薄膜，或聚丙烯或聚乙烯等的聚烯烴薄膜。剝離劑，可使用矽酮系、氟系、長鏈烷基系等，該等之中，以可得廉價而穩定的性能之矽酮系為佳。剝離片20的厚度，並無特別限制，通常為20μm以上250μm以下的程度。 The protective film formation included in the PR laminate 100 of the present embodiment is complex As shown in Fig. 1, the slat sheet 10 is bonded to the peeling surface 20A of the peeling sheet 20 on the surface 10A on the side of the film 4 for protective film formation. The configuration of the peeling sheet 20 is arbitrary, and the plastic film may be peeled off by a release agent or the like. Specific examples of the plastic film include a polyester film such as polyethylene terephthalate, polybutylene terephthalate or polyethylene naphthalate, or polypropylene or polyethylene. Polyolefin film. As the release agent, an anthrone type, a fluorine type, a long-chain alkyl type or the like can be used, and among these, an anthrone which is inexpensive and stable can be preferably used. The thickness of the release sheet 20 is not particularly limited, but is usually about 20 μm or more and 250 μm or less.

關於本實施形態之PR層積體100所包括之剝離板片20之具體形狀，並無限定。如第7圖所示，剝離板片20亦可為長條體。於此種情形，保護膜形成用複合板片10，亦可在剝離板片20之剝離面20A上，互相離間且於剝離板片20之長條方向複數配置。PR層積體100具有該構成時，藉由將PR層積體100向長條方向輸送，可持續將複數的保護膜形成用複合板片10對一定的場所供給。因此，可將由PR層積體100剝離保護膜形成用複合板片10，貼附於被著構件W之作業在一定的場所反覆實施，可提升使用PR層積體100時之工作效率。 The specific shape of the peeling sheet 20 included in the PR laminate 100 of the present embodiment is not limited. As shown in Fig. 7, the peeling sheet 20 may also be an elongated body. In this case, the composite sheet 10 for forming a protective film may be disposed on the peeling surface 20A of the peeling sheet 20 so as to be spaced apart from each other and in the longitudinal direction of the peeling sheet 20. When the PR laminate 100 has such a configuration, the PR laminate 100 is conveyed in the longitudinal direction, and the plurality of composite film sheets 10 for forming a protective film can be continuously supplied to a predetermined place. Therefore, the composite sheet 10 for forming a protective film can be peeled off from the PR laminate 100, and the work attached to the member W can be repeated at a predetermined place, and the work efficiency when the PR laminate 100 is used can be improved.

2. PR層積體之捲取體 2. PR laminate body

關於本實施形態之PR層積體100，由如上所述之長條體組成時，於長條方向捲收成捲取體之形態，由保管的容易性的觀點為佳。如第8圖所示PR層積體100之捲取體，係長條的PR層積體100捲收於芯材C周圍者。 When the PR laminate 100 of the present embodiment is composed of the elongated body as described above, the wound body is wound up in the longitudinal direction, and it is preferable from the viewpoint of easiness of storage. As shown in Fig. 8, the wound body of the PR laminate 100 is wound around the core material C by the long PR laminate 100.

捲取體的形態之PR層積體100，於使用時向長條 方向送出，由接近送出側端部之保護膜形成用複合板片10依序由剝離板片20剝離，貼附於被加工構件W(以及按照必要環形框等的夾具)，供於切割步驟。未提高該貼附時之作業性的觀點，加工用區域10a包含薄膜主面4A之全區域，即，薄膜主面4A之外周，與加工用區域10a之外周以平面視之離間距離d以超過0mm為佳。 The PR layered body 100 of the form of the take-up body is long to the strip when in use The composite sheet 10 for protective film formation which is close to the delivery side end portion is peeled off from the peeling sheet 20 in this order, and is attached to the workpiece W (and a jig such as a necessary ring frame) for the cutting step. The working area 10a includes the entire area of the main surface 4A of the film, that is, the outer circumference of the main surface 4A of the film, and the distance d between the outer circumference of the processing area 10a and the outer surface of the processing area 10a exceeds the viewpoint of the workability at the time of attachment. 0mm is preferred.

3.保護膜形成用複合板片 3. Composite sheet for protective film formation

關於本實施形態之保護膜形成用複合板片10，係由關於上述本實施形態之PR層積體100所包括之剝離板片20，剝離保護膜形成用複合板片10而得。該剝離，通常，係使用剝離裝置進行，該剝離作業與，剝離而得之保護膜形成用複合板片10對被加工構件W之貼附作業大多連續地進行。 The composite sheet 10 for forming a protective film of the present embodiment is obtained by peeling off the release sheet 20 included in the PR laminate 100 of the present embodiment and peeling off the composite sheet 10 for forming a protective film. This peeling is usually carried out by using a peeling device, and the peeling operation and the peeling of the composite sheet 10 for forming a protective film to the workpiece W are often continuously performed.

4. PR層積體之製造方法 4. PR laminate body manufacturing method

關於本實施形態之PR層積體100之製造方法，並無特別限定，將構成此之層狀體適宜層積即可。以下，作為關於本實施形態的PR層積體100之製造方法之一例，說明個別準備包含黏著板片1及保護膜形成用薄膜4之層積體，由此製造PR層積體100之情形。 The method for producing the PR laminate 100 of the present embodiment is not particularly limited, and the layered body constituting the layered body may be appropriately laminated. In the following, as an example of the method for producing the PR laminate 100 of the present embodiment, a case where the PR laminate 11 is produced by separately preparing a laminate including the adhesive sheet 1 and the protective film formation film 4 will be described.

(1)黏著板片之原卷之製造方法 (1) Manufacturing method of original roll of adhesive sheet

黏著板片1之原卷之製造方法，只要可將黏著劑層3層積於基材2之一面，詳細的方法並無特別限定。舉一例，則可將上述黏著層形成用塗佈液，於基材2之一面上，藉由模具塗佈機、淋幕塗佈機、噴霧塗佈機、狹縫塗佈機、刮刀塗佈機等將該塗層液塗佈形成塗膜，藉由使該一面上的塗膜乾燥，形成黏著劑 層3。黏著層形成用塗佈液，只要可進行塗佈，其性狀並無特別限定，有將用於形成黏著劑層3之成分作為溶質含有之情形，亦有作為分散質含有之情形。 The method for producing the original roll of the adhesive sheet 1 is not particularly limited as long as the adhesive layer 3 can be laminated on one surface of the substrate 2. As an example, the coating liquid for forming an adhesive layer may be applied to one surface of the substrate 2 by a die coater, a curtain coater, a spray coater, a slit coater, or a doctor blade. The coating liquid is applied to form a coating film, and the coating film on the one side is dried to form an adhesive. Layer 3. The coating liquid for forming an adhesive layer is not particularly limited as long as it can be applied, and the component for forming the adhesive layer 3 may be contained as a solute, or may be contained as a dispersoid.

黏著層形成用塗佈液含有架橋劑(γ)時，藉由改變上述乾燥條件(溫度、時間等)，或者另外設置加熱處理，使塗膜內的丙烯酸系聚合物(α)與架橋劑(γ)進行架橋反應，於黏著劑層3內以所期望的存在密度形成架橋構造即可。為使該架橋反應充分進行，亦可藉由上述方法等將黏著劑層3層積於基材2之後，將所得黏著板片1，進行例如於23℃、相對濕度50%之環境靜置數日之熟成。。 When the coating liquid for forming an adhesive layer contains a bridging agent (γ), the acrylic polymer (α) and the bridging agent in the coating film are changed by changing the drying conditions (temperature, time, etc.) or separately by heat treatment. γ) The bridging reaction may be carried out to form a bridging structure in the adhesive layer 3 at a desired density of existence. In order to sufficiently carry out the bridging reaction, the adhesive sheet 3 may be laminated on the substrate 2 by the above-described method, and the resulting adhesive sheet 1 may be subjected to an environmental standing number of, for example, 23 ° C and a relative humidity of 50%. The day is ripe. .

作為關於本實施形態之黏著板片1之原卷之製造方法之別的一例，準備如上所述之剝離板片20之剝離板片，將上述黏著層形成用塗佈液塗佈於該剝離面上形成塗膜，將此乾燥形成黏著劑層3與剝離片所組成之層積體，將在於該層積體之黏著劑層3與剝離片相對之側之相反側之面黏貼於基材2之一面，得到黏著板片1之原卷與剝離板片20之層積體。在於該層積體之剝離板片，可迅速地剝離亦可保護黏著劑層3，直到在黏著板片1之原卷之黏著劑層3側之面1A形成保護膜形成用薄膜4。 In another example of the method for producing the original roll of the adhesive sheet 1 of the present embodiment, the peeling sheet of the peeling sheet 20 as described above is prepared, and the coating liquid for forming an adhesive layer is applied to the peeling surface. A coating film is formed thereon, and this is dried to form a laminate composed of the adhesive layer 3 and the release sheet, and the surface on the opposite side of the side opposite to the side opposite to the release sheet of the laminate is adhered to the substrate 2 On one side, a laminate of the original roll of the adhesive sheet 1 and the release sheet 20 is obtained. The peeling sheet of the laminate can be quickly peeled off or the adhesive layer 3 can be protected until the film 4 for forming a protective film is formed on the surface 1A of the original layer of the adhesive sheet 1 on the side of the adhesive layer 3.

如此所得之黏著板片1之原卷，可以此狀態作為完成品，亦可藉由對黏著板片1之原卷之黏著劑層3進行能量線照射等使包含於黏著劑層3之成分進行聚合反應。在於本說明書，亦有將包括如此之進行聚合反應之黏著劑層3之黏著板片1之原卷稱為「照射後黏著板片之原卷」知情行。 The original roll of the adhesive sheet 1 thus obtained can be used as a finished product in this state, and the components contained in the adhesive layer 3 can be subjected to energy ray irradiation or the like to the adhesive layer 3 of the original roll of the adhesive sheet 1. Polymerization. In the present specification, the original roll of the adhesive sheet 1 including the adhesive layer 3 subjected to the polymerization reaction is also referred to as "the original roll of the adhered sheet after irradiation".

亦可於黏著板片1之原卷之黏著劑層3側之表面1A，層積界面接著調整層5或夾具接著層6。該層積方法的具體例，可舉於黏著板片1之原卷之黏著劑層3側之表面1A，層積賦予界面接著調整層5或夾具接著層6之層狀體，由層狀體側進行半切，切斷該層狀體，將層狀體之不需要的部分去除，得到界面接著調整層5或夾具接著層6之方法。或者，將賦予界面接著調整層5或夾具接著層6之層狀體，層積於剝離板片之剝離面，由該剝離板片與該層狀體之層積體之層狀體側，進行半切切斷該層狀體，去除層狀體之不需要的部分，將作為如此所得進行形狀加工之層狀體之界面接著調整層5或夾具接著層6，與剝離板片之層積體之層狀體側之面，與黏著板片1之原卷之黏著劑層3側之面1A貼合，將上述剝離板片剝離之方法。 It is also possible to adhere the surface 1A of the adhesive layer 3 side of the original roll of the sheet 1, and then laminate the layer 5 or the jig to the layer 6. Specific examples of the lamination method include a surface 1A on the side of the adhesive layer 3 of the original roll of the adhesive sheet 1, and a layered body in which the interface is provided next to the adjustment layer 5 or the jig bonding layer 6, and the layered body is formed. The side is half-cut, the layered body is cut, and the unnecessary portion of the layered body is removed to obtain a method of interfacially adjusting the layer 5 or the jig subsequent layer 6. Alternatively, the layered body of the interface layer 5 or the jig bonding layer 6 is applied to the interface, and laminated on the peeling surface of the peeling sheet, and the layered body side of the layered body of the peeling sheet and the layered body is formed. The layered body is cut by half cutting, and the unnecessary portion of the layered body is removed, and the interface of the layered body thus obtained is subjected to the adjustment layer 5 or the jig back layer 6, and the laminated body of the peeled sheet. The surface on the side of the layered body is bonded to the surface 1A on the side of the adhesive layer 3 of the original roll of the adhesive sheet 1, and the peeling sheet is peeled off.

(2)保護膜形成用薄膜之製造方法 (2) Manufacturing method of film for forming a protective film

另外，準備用於形成保護膜形成用薄膜之組成物之保護膜形成用組成物，將該保護膜形成用組成物塗佈於剝離板片20之剝離面上形成塗膜，將所得塗膜乾燥作為保護膜形成用薄膜4，於該保護膜形成用薄膜4露出的面，貼合其他的剝離板片之剝離面，形成保護膜形成用薄膜4以2片剝離板片挾持之層積體。其次，將該層積體由其他的剝離板片側，切斷其他的剝離板片及保護膜形成用薄膜4地做半切將不需要的部分(其他的剝離板片之一部分及保護膜形成用薄膜4之一部分)去除，使保護膜形成用薄膜4之薄膜主面4A之形狀，對應於黏著板片1之原卷之黏著劑層3側之主面1A之一部分的區域1a的形 狀。如此地得到於剝離板片20之剝離面上，層積保護膜形成用薄膜4，於該薄膜4進一步層積其他的剝離板片而得之層積體。 In addition, a protective film forming composition for forming a composition for forming a film for protective film is prepared, and the protective film forming composition is applied onto a peeling surface of the peeling sheet 20 to form a coating film, and the resulting coating film is dried. As the film for forming a protective film 4, the peeling surface of the other peeling sheet is bonded to the surface on which the protective film forming film 4 is exposed, and a laminated body in which the protective film forming film 4 is held by two peeling sheets is formed. Then, the laminate is cut off from the other peeling sheet side, and the other peeling sheet and the protective film forming film 4 are cut into a half-cut unnecessary portion (a part of the other peeling sheet and a film for forming a protective film) The shape of the film main surface 4A of the film 4 for protective film formation is removed, and corresponds to the shape of the region 1a of a portion of the main surface 1A of the adhesive layer 3 side of the original roll of the adhesive sheet 1. shape. In this manner, a film 4 for forming a protective film is laminated on the release surface of the release sheet 20, and a laminate of the other release sheets is further laminated on the film 4.

(3)PR層積體之製作 (3) Production of PR laminate

由如此所得之層積體將其他的剝離板片剝離，得到由剝離板片20及加工為既定形狀之保護膜形成用薄膜4所組成之層積體，將在於該層積体之保護膜形成用薄膜4側之面，與黏著板片(亦有為照射後黏著板片之情形。)1之原卷之黏著劑層3側之表面1A貼合。 The other peeling sheet is peeled off from the laminate obtained in this way, and a laminated body composed of the peeling sheet 20 and the protective film forming film 4 processed into a predetermined shape is obtained, and the protective film of the laminated body is formed. The surface on the side of the film 4 is bonded to the surface 1A on the side of the adhesive layer 3 of the original roll of the adhesive sheet (also in the case where the sheet is adhered after irradiation).

將藉由該貼合所得，具有依序層積剝離板片20、保護膜形成用薄膜4及黏著板片1之原卷的部分之層積體，由黏著板片1之原卷之基材2側半切，將黏著板片1切斷去除不需要的部分(黏著板片1之一部分)，可得加工為既定形狀之保護膜形成用複合板片10層積於剝離板片20上而城之PR層積體100。 A laminated body having a portion in which the laminated sheet 20, the protective film forming film 4, and the original sheet of the adhesive sheet 1 are sequentially laminated, and the original roll of the bonded sheet 1 is obtained by the bonding. The two sides are half-cut, and the adhesive sheet 1 is cut to remove an unnecessary portion (a part of the adhesive sheet 1), and a composite sheet 10 for forming a protective film formed into a predetermined shape can be laminated on the peeling sheet 20 The PR laminate 100.

5.具有保護膜之晶片的製造方法 5. Method for manufacturing wafer with protective film

以下，說明使用捲取體形態的PR層積體100之具有保護膜之晶片的製造方法。 Hereinafter, a method of manufacturing a wafer having a protective film of the PR laminate 100 in the form of a take-up body will be described.

首先，將捲取體形態的PR層積體100送出，由保護膜形成用複合板片10將剝離板片20剝離，將保護膜形成用複合板片10之保護膜形成用薄膜4側之面10A之加工用區域10a，貼附於被加工構件W之一面。在此，加工用區域10a，係由薄膜主面4A所組成之區域，及以平面視較該區域之外周更外側的位置，由黏著劑層3之面及界面接著調整層5之面之 至少一方所組成之的區域(在於本說明書，亦稱為「外周區域」。)所構成。與該外周區域相對之被加工構件W之一面的區域，亦可接於外周區域，亦可沒有接觸。與外周區域相對之被加工構件W之一面之區域與外周區域接觸時，可為該區域全部與外周區域接觸，亦可係該區域的一部分與外周區域接觸。再者，與外周區域相對之被加工構件W之一面之區域的全部與外周區域接觸，則保護膜形成用薄膜4成以被加工構件W與黏著板片1密封的狀態。 First, the PR laminate 100 in the form of a wound body is sent out, and the release sheet 20 is peeled off by the composite sheet 10 for forming a protective film, and the surface of the film 4 for protective film formation of the composite sheet 10 for forming a protective film is formed. The processing region 10a of 10A is attached to one surface of the workpiece W. Here, the processing region 10a is a region composed of the main surface 4A of the film, and a position outside the periphery of the region in a plan view, and the surface of the adhesive layer 3 and the interface are then adjusted to the surface of the layer 5. The area composed of at least one of them (also referred to as "outer perimeter area" in this specification). The area of one side of the workpiece W facing the outer peripheral area may be connected to the outer peripheral area or may not be in contact. When the area of one surface of the workpiece W facing the outer peripheral area is in contact with the outer peripheral area, all of the area may be in contact with the outer peripheral area, or a part of the area may be in contact with the outer peripheral area. In addition, all of the regions of the surface of the workpiece W that are opposed to the outer peripheral region are in contact with the outer peripheral region, and the film for forming a protective film 4 is in a state in which the workpiece W and the adhesive sheet 1 are sealed.

被加工構件W之種類，並無特別限定，通常，係矽晶圓等的半導體基板，沒有形成電路之側之面，即，背面成為被著面。按照必要，亦可將環形框等的夾具，配置在位於保護膜形成用複合板片10之保護膜形成用薄膜4側之面之加工用區域10a之外周的區域10b。此時．，保護膜形成用複合板片10包括夾具接著層6時，於夾具接著層6之與黏著劑層3相對之面及相反側之面，使其一方的面貼著地，配置夾具。 The type of the member to be processed W is not particularly limited. Usually, the semiconductor substrate such as a wafer is not surfaced on the side where the circuit is formed, that is, the back surface is faced. If necessary, the jig of a ring frame or the like may be disposed in a region 10b on the outer periphery of the processing region 10a on the side of the film 4 for protective film formation of the composite sheet 10 for protective film formation. at this time. When the composite sheet 10 for forming a protective film includes the jig-attached layer 6, a jig is placed on the surface of the jig-attached layer 6 facing the adhesive layer 3 and on the opposite side, and one surface is placed on the surface.

其次，被加工構件W與保護膜形成用複合板片10之層積構造體(亦有進一步具有夾具之情形。)，載置、固定於進行切割加工之切割台上。此時，藉由使保護膜形成用複合板片10之基材2側之面接於切割台地載置，可使保護膜形成用複合板片10作用作為切割板片。在於本說明書，將該切割台上的層積構造體稱為「第一層積構造體」。 Next, the laminated structure of the workpiece W and the composite sheet 10 for forming a protective film (which may have a jig further) is placed and fixed on a cutting table for cutting. At this time, the surface of the base material 2 side of the composite sheet 10 for protective film formation is placed on the cutting table, and the composite sheet 10 for forming a protective film can be used as a dicing sheet. In the present specification, the laminated structure on the cutting table is referred to as a "first laminated structure".

以下，列記用於由第一層積構造體，得到由來自被加工構件W之晶片與層積於為該晶片之一方的主面之保護膜所組成之具有保護膜之晶片、及於其保護膜施以標記之具有 標記保護膜之晶片之複數方法。 Hereinafter, the wafer having the protective film composed of the wafer from the workpiece W and the protective film laminated on the main surface of the wafer is obtained and protected by the first laminate structure. Membrane A plurality of methods of marking a wafer of a protective film.

(方法1) (method 1)

首先，使包含於第一層積構造體之保護膜形成用複合板片10之保護膜形成用薄膜4硬化，得到具有黏著板片1、保護膜以及被加工構件W以此順序層積之部分之第二層積構造體。其次，將如此所得之第二層積構造體，由黏著板片1側之相反側做切割，將被加工構件W與保護膜一起個片化，得到複數保護膜之個片及該個片附著於一方的面之晶片所組成之具有保護膜之晶片，層積於黏著板片1上之部分之第三層積構造體。接著，個別將第三層積構造體所具有的複數具有保護膜之晶片拾取得到具有保護膜之晶片。 First, the film 4 for protective film formation of the composite sheet 10 for protective film formation of the first laminated structure is cured, and a portion having the adhesive sheet 1, the protective film, and the processed member W laminated in this order is obtained. The second layered structure. Next, the second laminated structure thus obtained is cut from the opposite side of the side of the adhesive sheet 1, and the member W and the protective film are sliced together to obtain a sheet of the plurality of protective films and the attached sheet. A wafer having a protective film composed of a wafer on one side, and a third laminated structure laminated on a portion of the adhesive sheet 1. Next, the plurality of wafers having the protective film of the third laminate structure are individually picked up and taken up to the wafer having the protective film.

在此，關於上述第一層積構造體、第二層積構造體及第三層積構造體之任一，由黏著板片1側照射雷射光進行標記，將具有保護膜之晶片所包括之保護膜作為具有標記之保護膜，則可藉由上述方法，得到具有標記保護膜之晶片。 Here, the first laminated structure, the second laminated structure, and the third laminated structure are irradiated with laser light by the side of the adhesive sheet 1, and the wafer including the protective film is included. As a protective film having a mark, a wafer having a mark protective film can be obtained by the above method.

或者，由第三層積構造體拾取而得之具有保護膜之晶片之保護膜與晶片相對之主面與相反側之主面，不經由黏著板片1，藉由雷射光照射，亦可得保護膜係具有標記之保護膜，之具有標記保護膜之晶片。 Alternatively, the main surface of the protective film of the wafer having the protective film picked up by the third laminated structure and the main surface opposite to the wafer and the main surface on the opposite side may be irradiated by laser light without passing through the adhesive sheet 1. The protective film has a labeled protective film having a wafer with a protective film.

(方法2) (Method 2)

首先，將第一層積構造體，由與黏著板片1側之相反側切割，將被加工構件W與保護膜形成用薄膜4一起個片化，得到複數保護膜形成用薄膜4之個片與該個片附著於一方的面之晶片所組成之具有保護膜形成用薄膜之晶片，層積於黏著板片1上 之部分之第四層積構造體。其次，使如此所得之第四層積構造體所包括之具有保護膜形成用薄膜之晶片之保護膜形成用薄膜4之個片硬化，將具有保護膜形成用薄膜之晶片作成具有保護膜之晶片。在於本說明書，將該等具有保護膜之晶片與黏著板片1所組成之構造體，亦稱為第五層積構造體。接著，個別將黏著板片1上之複數具有保護膜之晶片拾取得到具有保護膜之晶片。 First, the first laminate structure is cut from the side opposite to the side of the adhesive sheet 1, and the workpiece W and the film for forming a protective film 4 are formed together to obtain a sheet of the film 4 for forming a plurality of protective films. A wafer having a film for forming a protective film composed of a wafer on which one of the sheets is attached to one surface is laminated on the adhesive sheet 1 Part of the fourth layered structure. Then, the sheet of the protective film forming film 4 of the wafer having the film for protective film formation included in the thus obtained fourth laminate structure is cured, and the wafer having the film for forming a protective film is formed into a wafer having a protective film. . In the present specification, the structure including the protective film-forming wafer and the adhesive sheet 1 is also referred to as a fifth laminated structure. Next, the plurality of wafers having the protective film on the adhesive sheet 1 are individually picked up to obtain a wafer having a protective film.

在此，對第一層積構造體及第四層積構造體之任一，由黏著板片1側照射雷射光進行標記，則具有保護膜形成用薄膜之晶片所包括之保護膜形成用薄膜4之個片成為具有標記之保護膜形成用薄膜，可得具有標記保護膜之晶片。 Here, any one of the first laminated structure and the fourth laminated structure is formed by irradiating laser light to the side of the adhesive sheet 1 to form a film for forming a protective film including a film for forming a protective film. Each of the four sheets is a film for forming a protective film having a mark, and a wafer having a label protective film can be obtained.

關於上述第五層積構造體，由黏著板片1側照射雷射光進行標記，將具有保護膜之晶片所包括之保護膜作為具有標記保護膜，則關於第五層積構造體之複數具有保護膜之晶片，分別成為具有標記保護膜之晶片。藉由將該複數具有標記保護膜之晶片，個別拾取，得到具有標記保護膜之晶片。 In the fifth laminated structure, the laser beam is irradiated with the laser beam on the side of the adhesive sheet 1, and the protective film included in the wafer having the protective film is provided with a protective film for the fifth laminated structure. The wafers of the film are respectively wafers having a marking protective film. The wafer having the marking protective film is obtained by individually picking up the wafer having the marking protective film.

在於藉由上述方法所製造之具有保護膜之晶片之保護膜與晶片相對之主面之相反側之主面，不經由黏著板片1照射雷射光，將保護膜作成具有標記之保護膜，亦可得到具有標記保護膜之晶片。 In the main surface opposite to the main surface of the protective film of the wafer having the protective film produced by the above method, the protective film is formed as a protective film having a mark, without irradiating the laser light through the adhesive sheet 1. A wafer having a marking protective film can be obtained.

(方法3) (Method 3)

首先，與方法2同樣地，將第一層積構造體，由黏著板片1側之相反側切割，將被加工構件W與保護膜形成用薄膜4一起個片化，得到複數保護膜形成用薄膜4之個片及該個片附著 於一方之面之晶片所組成之具有保護膜形成用薄膜之晶片，層積於黏著板片1上之部分之第四層積構造體。其次，個別將第四層積構造體所包括之複數具有保護膜形成用薄膜之晶片拾取。使藉由該拾取所得之具有保護膜形成用薄膜之晶片之保護膜形成用薄膜之個片硬化，將具有保護膜形成用薄膜之晶片作成具有保護膜之晶片。 First, in the same manner as in the method 2, the first laminated structure is cut from the opposite side to the side of the adhesive sheet 1, and the workpiece W and the protective film forming film 4 are formed together to form a plurality of protective films. The film of the film 4 and the piece of the film are attached A wafer having a film for forming a protective film composed of a wafer on one side, and a fourth layered structure in a portion laminated on the adhesive sheet 1. Next, the wafer including the film for forming a protective film included in the fourth laminate structure is individually picked up. The sheet of the film for protective film formation of the wafer having the film for protective film formation obtained by the pick-up is cured, and the wafer having the film for forming a protective film is formed into a wafer having a protective film.

在此，對第一層積構造體及第四層積構造體之任一，由黏著板片1側照射雷射光進行標記，則具有保護膜形成用薄膜之晶片所包括之保護膜形成用薄膜4之個片成為具有標記保護膜形成用薄膜，可得具有標記保護膜之晶片。 Here, any one of the first laminated structure and the fourth laminated structure is formed by irradiating laser light to the side of the adhesive sheet 1 to form a film for forming a protective film including a film for forming a protective film. Each of the four sheets is a film having a marking protective film, and a wafer having a marking protective film can be obtained.

或者，於拾取而個別化之具有保護膜形成用薄膜之晶片或具有保護膜之晶片之晶片側之主面之相反側之主面，不經由黏著板片1照射雷射光進行標記，亦可將具有保護膜之晶片作為具有標記保護膜之晶片而得。 Alternatively, the main surface opposite to the main surface on the wafer side of the wafer having the protective film forming film or the wafer having the protective film which is picked up and individualized may be marked without irradiating the laser light through the adhesive sheet 1 A wafer having a protective film is obtained as a wafer having a label protective film.

根據本實施形態之具有保護膜之晶片的製造方法，用於由第二層積構造體製造第三層積構造體而進行之切割步驟(方法1)，及用於由第一層積構造體製造第四層積構造體而進行之切割步驟(方法2、3)，不容易發生薄膜飛散。附著飛散之薄膜之晶片，亦有作為不良品在此階段被排除之情形，但是根據本實施形態之製造方法，由於不容易發生薄膜飛散，故在將被加工構件W分割成複數晶片的切割步驟，良率不容易降低。因此，關於本實施形態之製造方法所得之具有保護膜之晶片，容易成為成本上有利者。此外，因飛散之薄膜而使晶片污染的可能性亦被減低，故關於本實施形態之製造方法所得之 具有保護膜之晶片之品質優良。 A method for producing a wafer having a protective film according to the present embodiment, a cutting step (method 1) for producing a third laminated structure from a second laminated structure, and a first laminated structure The cutting step (methods 2, 3) performed by producing the fourth layered structure is less likely to cause film scattering. The wafer to which the scattered film is attached may be excluded as a defective product at this stage. However, according to the manufacturing method of the present embodiment, since the film is not easily scattered, the cutting step of dividing the workpiece W into a plurality of wafers is performed. The yield is not easy to reduce. Therefore, the wafer having the protective film obtained by the production method of the present embodiment is likely to be cost-effective. Further, since the possibility of contamination of the wafer due to the scattered film is also reduced, the manufacturing method of the embodiment is obtained. The wafer with the protective film is of excellent quality.

以上所說明之實施形態，係為容易理解本發明而記載者，並非限定本發明而記載者。因此，揭示於上述實施形態之各要素，係亦包含屬於本發明知技術性範圍之所有設計變更及均等物之趣旨。 The embodiments described above are described for easy understanding of the present invention, and are not intended to limit the present invention. Therefore, the various elements of the above-described embodiments are intended to encompass all design changes and equivalents of the technical scope of the invention.

1‧‧‧黏著板片 1‧‧‧Adhesive sheets

1A‧‧‧黏著板片1之黏著劑層3側之主面 1A‧‧‧Main surface of the adhesive layer 3 side of the adhesive sheet 1

1a‧‧‧黏著板片1之黏著劑層3側之主面1A之一部分的區域而層積保護膜形成用薄膜4之區域 1a‧‧‧A region where a portion of the protective film forming film 4 is laminated by adhering to a portion of the main surface 1A of the adhesive layer 3 side of the sheet 1

2‧‧‧基材 2‧‧‧Substrate

2A‧‧‧基材2與黏著劑層3相對之主面(基材相對面) 2A‧‧‧ The main surface of the substrate 2 opposite to the adhesive layer 3 (opposite side of the substrate)

3‧‧‧黏著劑層 3‧‧‧Adhesive layer

4‧‧‧保護膜形成用薄膜 4‧‧‧film for protective film formation

4A‧‧‧保護膜形成用薄膜4之剝離板片20與剝離面20A相對之主面(薄膜主面) 4A‧‧‧ The main surface (the main surface of the film) of the peeling sheet 20 of the film 4 for forming a protective film and the peeling surface 20A

5‧‧‧界面接著調整層 5‧‧‧ interface followed by adjustment layer

6‧‧‧夾具接著層 6‧‧ ‧ fixture layer

10‧‧‧保護膜形成用複合板片 10‧‧‧Composite sheet for protective film formation

10A‧‧‧保護膜形成用複合板片10之保護膜形成用薄膜4側之主面 10A‧‧‧Main surface of the film 4 for protective film formation of the composite sheet 10 for protective film formation

10a‧‧‧加工用區域 10a‧‧‧Processing area

10b‧‧‧位於保護膜形成用複合板片10之保護膜形成用薄膜4側之面之加工用區域10a之外周的區域 10b‧‧‧A region outside the processing region 10a on the side of the film 4 for protective film formation of the composite sheet 10 for protective film formation

10c‧‧‧保護膜形成用複合板片10之保護膜形成用薄膜4側之主面10A的一部分區域，位在設有黏著板片1之黏著劑層3側之主面1A之界面接著調整層5之區域1b之外周的區域 10c‧‧ A part of the main surface 10A of the protective film forming film 4 on the side of the protective film forming composite sheet 10 is placed on the interface of the main surface 1A on the side of the adhesive layer 3 on which the adhesive sheet 1 is provided, and then adjusted. The area outside the area 1b of layer 5

20‧‧‧剝離板片 20‧‧‧ peeling sheet

20A‧‧‧剝離板片20之剝離面 20A‧‧‧ peeling surface of peeling sheet 20

100‧‧‧保護膜形成用複合板片-剝離板片層積體(PR層積體) 100‧‧‧Composite sheet for protective film formation-release sheet laminate (PR laminate)

D‧‧‧離間距離 D‧‧‧Distance distance

W‧‧‧被加工構件 W‧‧‧Processed components

第1圖係關於本發明之一實施形態之保護膜形成用複合板片-剝離板片層積體之示意剖面圖。 Fig. 1 is a schematic cross-sectional view showing a composite sheet-peeling sheet laminate for forming a protective film according to an embodiment of the present invention.

第2圖係關於本發明之一實施形態之保護膜形成用複合板片之示意剖面圖。 Fig. 2 is a schematic cross-sectional view showing a composite sheet for forming a protective film according to an embodiment of the present invention.

第3圖係表示第1圖所示之保護膜形成用複合板片-剝離板片層積體之保護膜形成用複合板片貼附於被加工構件W而成之層積體，(a)示意剖面圖及(b)示意立體圖。 3 is a laminate in which a composite sheet for forming a protective film for forming a composite sheet-peeling sheet laminate of the protective film formation shown in Fig. 1 is attached to a member W to be processed, (a) Schematic cross-sectional view and (b) schematic perspective view.

第4圖係關於本發明之一實施形態，包括設有界面接著調整層之黏著板片之保護膜形成用複合板片之示意剖面圖。 Fig. 4 is a schematic cross-sectional view showing a composite sheet for forming a protective film which is provided with an adhesive sheet having an interface and an adjustment layer, according to an embodiment of the present invention.

第5圖係關於本發明之一實施形態，包括夾具接著層的保護膜形成用複合板片之示意剖面圖。 Fig. 5 is a schematic cross-sectional view showing a composite sheet for forming a protective film including a jig adhesive layer according to an embodiment of the present invention.

第6圖係關於本發明之一實施形態，包括設有界面接著調整層之黏著板片及夾具接著層之保護膜形成用複合板片之示意剖面圖。 Fig. 6 is a schematic cross-sectional view showing an embodiment of the present invention, comprising a composite sheet for forming a protective film which is provided with an adhesive sheet of an interface subsequent adjustment layer and a bonding layer of a jig.

第7圖係關於本發明之一實施形態之保護膜形成用複合板 片-剝離板片層積體之示意立體圖。 Figure 7 is a composite sheet for forming a protective film according to an embodiment of the present invention. A schematic perspective view of a sheet-peeled sheet laminate.

第8圖係表示關於本發明之一實施形態，將捲取體的形態的保護膜形成用複合板片-剝離板片層積體的一部分送出的狀態之示意立體圖。 Fig. 8 is a schematic perspective view showing a state in which a part of the composite sheet-peeling sheet laminate for forming a protective film is taken out in the embodiment of the present invention.

以下，藉由實施例等進一步具體說明本發明，惟本發明之範圍並非限定於該等實施例等。 Hereinafter, the present invention will be specifically described by way of Examples and the like, but the scope of the present invention is not limited to the Examples and the like.

〔實施例1〕 [Example 1]

<保護膜形成用薄膜> <film for forming protective film>

如下製作由保護膜形成用組成物形成之保護膜形成用薄膜以2片剝離板片挾持而得之層積體(以下，亦稱為「保護膜形成用薄膜層積體」。)。準備由丙烯酸系聚合物(將丙烯酸丁酯55質量部、甲基丙烯酸甲酯15質量部、甲基丙烯酸縮水甘油酯20質量部、丙烯酸2-羥基乙酯10質量部共聚合而成之重量平均分子量90萬，玻璃轉移溫度-28℃之共聚物)所組成之膠合劑高分子100質量部、環氧樹脂之混合物(液狀雙酚A型環氧樹脂(分子量約370，環氧當量180~200g/eq)60質量部、固形雙酚A型環氧樹脂(分子量約1,600，環氧當量800~900g/eq)10質量部、鄰甲酚酚酸型環氧樹脂(分子量約1,500~1,800，環氧當量210~230g/eq)30質量部)所組成之熱硬化性成分100質量部、熱活性潛在性環氧樹脂硬化劑(雙氰胺2.4質量部、2-苯基-4,5-二羥基甲基咪唑(四國化成工業公司製，2PHZ)2.4質量部)、碳黑(平均粒徑28nm)10質量部、溶融石英填充劑(平均粒 徑8μm)288質量部、合成二氧化矽填充劑(平均粒徑0.5μm)32質量部及稀釋劑所組成，用於形成保護膜形成用薄膜之調合物。 In the following, a laminate obtained by sandwiching two sheets of a release sheet (hereinafter also referred to as "film laminate for forming a protective film") is prepared by forming a film for forming a protective film formed of a composition for forming a protective film. Prepared by an acrylic polymer (a mass average of 55 parts by mass of butyl acrylate, 15 parts by mass of methyl methacrylate, 20 parts by mass of glycidyl methacrylate, and 10 parts by mass of 2-hydroxyethyl acrylate) a polymer of 100 parts by mass of a binder polymer having a molecular weight of 900,000 and a glass transition temperature of -28 ° C, and a mixture of epoxy resins (liquid bisphenol A type epoxy resin (molecular weight of about 370, epoxy equivalent 180~) 200 g/eq) 60 parts by mass, solid bisphenol A type epoxy resin (molecular weight: about 1,600, epoxy equivalent: 800 to 900 g/eq), 10 parts by mass, o-cresol novolac type epoxy resin (molecular weight: about 1,500 to 1,800, Epoxy equivalent 210~230g/eq) 30 parts by mass) Thermosetting component composed of 100 parts by mass, thermal active latent epoxy resin hardener (dicyandiamide 2.4 mass part, 2-phenyl-4,5- Dihydroxymethylimidazole (2PHZ, manufactured by Shikoku Chemicals Co., Ltd.), 2.4 parts by mass), carbon black (average particle size: 28 nm), 10 parts by mass, molten quartz filler (average particle) A 2.8 mass portion having a diameter of 8 μm, a synthetic cerium oxide filler (average particle diameter: 0.5 μm), 32 parts by mass, and a diluent, and used to form a blend of a film for forming a protective film.

將上述用於形成保護膜形成用薄膜之調合物，塗佈於剝離板片之剝離面上，將所得塗膜乾燥(溫度100℃，1分鐘)，得到厚度20μm之保護膜形成用薄膜與剝離板片之層積體。於該層積體之保護膜形成用薄膜側之面，貼附其他的剝離板片之剝離面，得到保護膜形成用薄膜層積體。 The above-mentioned composition for forming a film for forming a protective film was applied onto a release surface of a release sheet, and the obtained coating film was dried (temperature: 100 ° C, 1 minute) to obtain a film for forming a protective film having a thickness of 20 μm and peeled off. A laminate of sheets. On the side of the film side for forming a protective film of the laminate, the release surface of another release sheet was attached to obtain a film laminate for forming a protective film.

<基材> <Substrate>

作為黏著板片的基材，使用厚度100μm之聚丙烯薄膜(三菱樹脂公司製，CT265)。 As a base material of the adhesive sheet, a polypropylene film (CT265, manufactured by Mitsubishi Plastics Co., Ltd.) having a thickness of 100 μm was used.

<黏著劑> <adhesive>

作為用於形成黏著板片之黏著劑層之黏著劑組成物，於丙烯酸高分子(2-乙基己基丙烯酸酯/醋酸乙烯酯/羥基乙基丙烯酸酯=45/40/15(質量比)，重量平均分子量=約50萬)，使甲基丙烯醯氧乙基丙烯酸酯反應80%當量(對丙烯酸聚合物100質量部為16質量部)之能量線硬化型高分子100質量部，調合光聚合起始劑(Ciba．Speciality．Chemicals公司製，IRGACURE(註冊商標)184)3.5質量部、及異氰酸酯化合物(東洋墨水製造公司製，BHS-8515)1.07質量部(均以固形分換算之調合比)，得到黏著劑組成物A1。 As an adhesive composition for forming an adhesive layer of an adhesive sheet, in an acrylic polymer (2-ethylhexyl acrylate/vinyl acetate/hydroxyethyl acrylate = 45/40/15 (mass ratio), Weight average molecular weight = about 500,000), 100 parts by weight of methacryloyloxyethyl acrylate (100 parts by mass for 100 parts by mass of acrylic polymer), 100 mass parts of energy ray-curable polymer, photopolymerization Starting material (manufactured by Ciba.Speciality. Chemicals, IRGACURE (registered trademark) 184) 3.5 mass parts, and isocyanate compound (BHS-8515, manufactured by Toyo Ink Co., Ltd.), 1.07 mass parts (all blending ratios in terms of solid content) , the adhesive composition A1 was obtained.

<黏著板片之原卷之製作> <Production of the original roll of the adhesive sheet>

將上述黏著劑組成物所組成之黏著劑層形成用組成物，塗佈於剝離板片(LINTEC公司製，SP-PET3811，厚度38μm)之剝離 面，使乾燥後的塗佈量成10g/m2，以100℃乾燥1分鐘。將所得剝離板片與黏著劑層之層積體之黏著劑層側之主面，與基材之一方的主面貼合得到黏著板片之原卷。由該黏著板片之原卷之基材側之主面，作為能量線將紫外線(主波長365nm)照射(紫線照度：230mW/cm2，紫外輻射劑量：190mJ/cm2)得到照射後黏著板片之原卷。 The composition for forming an adhesive layer composed of the above-mentioned adhesive composition was applied to a release surface of a release sheet (SP-PET3811, manufactured by LINTEC Co., Ltd., thickness: 38 μm), and the coating amount after drying was 10 g/m. 2 , dry at 100 ° C for 1 minute. The main surface of the layer on the side of the adhesive layer of the laminate of the obtained release sheet and the adhesive layer was bonded to one main surface of the substrate to obtain an original roll of the adhesive sheet. The main surface of the substrate from the original roll of the adhesive side of the sheet, as the energy ray an ultraviolet ray (main wavelength 365nm) irradiation (illuminance purple line: 230mW / cm 2, UV radiation dose: 190mJ / cm 2) obtained after irradiation adhesion The original volume of the plate.

<保護膜形成用複合板片之製作> <Production of composite sheet for forming a protective film>

由保護膜形成用薄膜層積體之一方的剝離板片側，留下另一方的剝離板片進行半切將保護膜形成用薄膜及一方的剝離板片切斷，沖模出與被加工構件之矽晶圓(直徑8英寸)相等之直徑之圓形之後，將沖模之形狀的部分以外的保護膜形成用薄膜及一方的剝離板片去除，得到保護膜形成用薄膜及一方的剝離板片均沖模成圓形而層積於另一方的剝離板片上之層積體。 On the side of the peeling sheet which is one of the film laminates for forming a protective film, the other peeling sheet is left to be half-cut, and the film for forming a protective film and one peeling sheet are cut, and the twin is cut out from the member to be processed. After a circular shape having a diameter of 8 inches in diameter, the film for forming a protective film other than the portion of the shape of the die and one of the peeling sheets are removed, and the film for forming a protective film and one of the peeling sheets are each die-molded. A laminate which is rounded and laminated on the other peeling sheet.

由該層積體將沖模之一方的剝離板片剝離，使保護膜形成用薄膜之主面露出。將貼著於照射後黏著板片之原卷之剝離板片剝離，於露出之照射後黏著板片之原卷之黏著劑層側之主面，貼附上述層積體之保護膜形成用薄膜之主面。 The peeling sheet of one of the dies is peeled off from the laminate, and the main surface of the film for forming a protective film is exposed. The peeling sheet adhered to the original roll of the adhesive sheet after the irradiation is peeled off, and the protective film forming film of the laminate is attached to the main surface of the original layer on the adhesive layer side of the original sheet after the exposure. The main face.

由藉由上述貼附所得，包括剝離板片、保護膜形成用薄膜、黏著劑層及基材以此順序配置之部分之層積體之基材側，進行切割形成與保護膜形成用薄膜同心而直徑270mm之圓形之切割線，將基材及黏著劑層切斷。切斷線之外側之不需要的部分(基材的一部分及黏著劑層的一部分)去除，於直徑270mm之圓形照射後黏著板片上，以同心的位置層積直徑8英寸之保護膜形成用薄膜，進一步得到剝離板片貼著於保護膜 形成用薄膜上而成之PR層積體。 The substrate side of the laminate including the release sheet, the film for forming a protective film, the adhesive layer, and the substrate in this order, which is obtained by the above-described attachment, is cut and formed concentrically with the film for forming a protective film. A circular cutting line having a diameter of 270 mm cuts the substrate and the adhesive layer. The unnecessary portion (a part of the substrate and a part of the adhesive layer) on the outer side of the cutting line is removed, and is adhered to the sheet after a circular irradiation of 270 mm in diameter, and a protective film having a diameter of 8 inches is laminated at a concentric position. Film, further obtained by peeling the sheet against the protective film A PR laminate formed on the film for formation.

〔實施例2〕 [Example 2]

將用於實施例1進行保護膜形成用薄膜層積體之半切之沖模變更，將沖模後之保護膜形成用薄膜之形狀較直徑8英寸小1mm之圓形以外，以與實施例1同樣的操作，得到PR層積體。再者，於如此所得之PR層積體之離間距離d為0.5mm。 The die which was used for the half-cutting of the film laminate for forming a protective film in the first embodiment was changed, and the shape of the film for forming a protective film after the die was a circle having a diameter of 1 mm and a diameter of 1 mm, and the same as in the first embodiment. Operation to obtain a PR laminate. Further, the distance d between the PR laminates thus obtained was 0.5 mm.

〔比較例1〕 [Comparative Example 1]

將用於實施例1進行保護膜形成用薄膜層積體之半切之沖模變更，將沖模後之保護膜形成用薄膜之形狀較直徑8英寸小5mm之圓形以外，以與實施例1同樣的操作，得到PR層積體。再者，即使將由如此所得之PR層積體所得之保護膜形成用複合板片貼附於8英寸的矽晶圓，實貼區域無法將保護膜形成用薄膜之主面之全區域覆蓋，必然會產生由保護膜形成用薄膜之主面之外周平均寬度2.5mm之環狀的露出區域。 The die which was used for the half-cut of the film laminate for forming a protective film was changed in the same manner as in the first embodiment except that the shape of the film for forming a protective film after the die was a circle having a diameter of 5 mm and a diameter of 5 mm. Operation to obtain a PR laminate. In addition, even if the composite sheet for forming a protective film obtained by the PR laminate obtained in this manner is attached to an 8-inch tantalum wafer, the solid region cannot cover the entire surface of the main surface of the film for forming a protective film, which is inevitable. An annular exposed region having an average outer circumference of 2.5 mm from the main surface of the film for forming a protective film was produced.

〔試驗例1〕<黏著力的測定> [Test Example 1] <Measurement of adhesion>

(1)保護膜形成用薄膜之硬化前黏著力(未硬化品之黏著力)之測定 (1) Determination of adhesion before curing of the film for forming a protective film (adhesion of uncured product)

藉由由實施例及比較例之PR層積體之剝離板片剝離，得到保護膜形成用複合板片。將所得保護膜形成用複合板片，包含保護膜形成用薄膜地材切成25mm×100mm的大小，得到試驗片。將試驗片之保護膜形成用薄膜側的面貼附於2000號研磨的矽晶圓之研磨面。該貼附時之溫度設定為70℃。接著，使用泛用的拉張試驗機，遵照JIS Z0237：2000的方法，對矽晶圓與試驗片所組成之層積構造體，以剝離角度180°進行由晶圓與保 護膜形成用薄膜所組成之層積體剝離黏著板片之試驗，將測定之黏著力之最大值，作為關於該試驗片之硬化前黏著力。 The composite sheet for protective film formation was obtained by peeling off the peeling sheets of the PR laminate of the examples and the comparative examples. The obtained composite sheet for forming a protective film and a film containing the film for forming a protective film were cut into a size of 25 mm × 100 mm to obtain a test piece. The surface on the side of the film for forming a protective film of the test piece was attached to the polished surface of the No. 2000 polished ruthenium wafer. The temperature at the time of attachment was set to 70 °C. Next, using a general-purpose tensile tester, according to the method of JIS Z0237:2000, the laminated structure composed of the tantalum wafer and the test piece is subjected to wafer and protection at a peeling angle of 180°. The laminate of the film for forming a film was peeled off from the adhesive sheet, and the maximum value of the adhesion was measured as the adhesion before curing of the test piece.

(2)保護膜形成用薄膜之硬化後黏著力(硬化品之黏著力)之測定 (2) Determination of adhesion after hardening of the film for forming a protective film (adhesion of hardened product)

藉由由實施例及比較例之PR層積體之剝離板片剝離，得到保護膜形成用複合板片。將所得保護膜形成用複合板片，包含保護膜形成用薄膜地材切成25mm×100mm的大小，得到試驗片。將試驗片之保護膜形成用薄膜側的面貼附於2000號研磨的矽晶圓之研磨面。該貼附時之溫度設定為70℃。接著，將矽晶圓與試驗片所組成之層積構造體，於維持在130℃烘箱內加熱2小時，將試驗片所包括之保護膜形成用薄膜硬化，得到於矽晶圓上，層積保護膜，進一步於其上層積黏著板片而成之層積構造體。之後，使用泛用的拉張試驗機，遵照JIS Z0237：2000的方法，對矽晶圓與試驗片所組成之層積構造體，以剝離角度180°進行由晶圓與保護膜形成用薄膜所組成之層積體剝離黏著板片之試驗，將測定之黏著力之最大值，作為關於該試驗片之硬化後黏著力。 The composite sheet for protective film formation was obtained by peeling off the peeling sheets of the PR laminate of the examples and the comparative examples. The obtained composite sheet for forming a protective film and a film containing the film for forming a protective film were cut into a size of 25 mm × 100 mm to obtain a test piece. The surface on the side of the film for forming a protective film of the test piece was attached to the polished surface of the No. 2000 polished ruthenium wafer. The temperature at the time of attachment was set to 70 °C. Then, the laminated structure composed of the tantalum wafer and the test piece was heated in an oven maintained at 130 ° C for 2 hours, and the film for forming a protective film included in the test piece was cured to obtain a laminate on the wafer, and laminated. The protective film further has a laminated structure in which a sheet is laminated thereon. After that, using a general-purpose tensile tester, the laminated structure composed of the tantalum wafer and the test piece was subjected to a film for forming a wafer and a protective film at a peeling angle of 180° in accordance with the method of JIS Z0237:2000. In the test of the laminated body in which the laminated body was peeled off, the maximum value of the adhesion was measured as the adhesion after hardening of the test piece.

〔試驗例2〕<薄膜飛散的評估> [Test Example 2] <Evaluation of film scattering>

(1)未硬化品之評估 (1) Evaluation of unhardened products

藉由由實施例及比較例之PR層積體之剝離板片剝離而得之保護膜形成用複合板片之保護膜形成用薄膜側之面，使用貼膜機(LINTEC公司製，Adwill RAD2500)，貼附在以2000號研磨之矽晶圓(150mm徑，厚度100μm)之研磨面及晶圓切割用環形 框。貼附時之設定溫度為70℃，以矽晶圓與保護膜形成用薄膜位於同心地進行貼附。 The film side of the protective film for forming a composite sheet for protective film formation obtained by peeling off the peeling sheet of the PR laminate of the examples and the comparative examples, using a film coater (Adwill RAD 2500, manufactured by LINTEC Co., Ltd.) Attached to the polished surface of the No. 2000 polished wafer (150 mm diameter, thickness 100 μm) and the wafer cutting ring frame. The set temperature at the time of attachment was 70 ° C, and the wafer was placed concentrically with the film for forming a protective film.

其次，使用切割裝置(DISCO公司製，DFD651)切割成10mm×10mm之晶片尺寸。切割時之切入量，對基材切入20μm。 Next, a wafer size of 10 mm × 10 mm was cut using a cutting device (DFD651, manufactured by DISCO Corporation). The amount of cut at the time of cutting was cut into a substrate of 20 μm.

以目視觀察切割後之保護膜形成用薄膜之個片之飛散狀態，以如下基準評估。將評估結果示於第1表。 The scattering state of the sheets of the film for forming a protective film after the dicing was visually observed and evaluated on the following basis. The evaluation results are shown in the first table.

A：並未確認到保護膜形成用薄膜之個片飛散 A: It was not confirmed that the film for forming a protective film was scattered.

B：可確認到保護膜形成用薄膜之個片飛散 B: It can be confirmed that the film for forming a protective film is scattered

(2)硬化品的評估 (2) Evaluation of hardened products

與上述方法相同，將保護膜形成用薄膜貼附於矽晶片及環形框之後，將矽晶圓、環形框、及貼附於該等之保護膜形成用複合板片所組成之層積構造體，於維持在130℃之烘箱內加熱2小時，使該積構造體所包括之保護膜形成用薄膜硬化作成保護膜者，進行切割。然後，以目視觀察切割後之保護膜之個片飛散狀態，以如下基準評估。將評估結果示於第1表。 In the same manner as the above-described method, after the film for forming a protective film is attached to the tantalum wafer and the ring frame, the tantalum wafer, the ring frame, and the laminated structure composed of the composite sheet for forming a protective film are attached. The film was heated in an oven maintained at 130 ° C for 2 hours, and the film for forming a protective film included in the product structure was cured to form a protective film, and the film was cut. Then, the sheet scattering state of the cut protective film was visually observed and evaluated on the following basis. The evaluation results are shown in the first table.

A：並未確認到保護膜形成用薄膜之個片飛散 A: It was not confirmed that the film for forming a protective film was scattered.

B：可確認到保護膜形成用薄膜之個片飛散 B: It can be confirmed that the film for forming a protective film is scattered

〔試驗例3〕<拾取適應性之評估> [Test Example 3] <Evaluation of Picking Adaptability>

對將試驗例1所記載的切割步驟所得，經由保護膜形成用薄膜之個片或保護膜之個片附著晶片之黏著板片，使用晶粒接合機(CANON MACHINERY製，BESTEM-D02)，以8mm四方4針配置的針頭，以凸起速度10mm/秒，凸起高度0.5mm凸起， 進行晶片的拾取。對50個晶片進行該拾取試驗，數黏著層與保護膜形成用薄膜的界面或黏著層與保護膜的界面適當地發生剝離，可以具有保護膜形成用薄膜之晶片或具有保護膜之晶片拾取之晶片數，求對試驗數(50)之比例作為拾取率(單位：%)。將評估結果示於第1表。再者，於第1表，關於有保護膜形成用薄膜附著之晶片表示為「未硬化品」，關於有保護膜附著之晶片表示為「硬化品」。 In the dicing step described in the test example 1, the sheet of the protective film-forming film or the sheet of the protective film was attached to the adhesive sheet of the wafer, and a die bonder (BESTEM-D02, manufactured by CANON MACHINERY) was used. The needle of 8mm square 4 needle configuration has a convex speed of 10mm/sec and a convex height of 0.5mm. Pick up the wafer. The pick-up test is performed on 50 wafers, and the interface between the number of adhesive layers and the film for forming a protective film or the interface between the adhesive layer and the protective film is appropriately peeled off, and the wafer having the film for forming a protective film or the wafer having the protective film can be picked up. The number of wafers was calculated as the ratio of the number of trials (50) as the pickup ratio (unit: %). The evaluation results are shown in the first table. In the first table, the wafer to which the film for protective film formation is attached is shown as "uncured product", and the wafer to which the protective film is attached is shown as "cured product".

由第1表可知，由滿足本發明之條件之實施例之PR層積體所得之保護膜形成用複合板片，於切割步驟及拾取步驟之任一均不容易發生異常。 As is clear from the first table, the composite sheet for forming a protective film obtained from the PR laminate of the examples satisfying the conditions of the present invention is less likely to be abnormal in any of the cutting step and the picking step.

【產業上的可利性】[Industry profitability]

由關於本發明之PR層積體所得之保護膜形成用複合板片，可良好地使用於作為由半導體晶圓等的板狀被加工構件得到具有保護膜之晶片之板片。 The composite sheet for forming a protective film obtained from the PR laminate of the present invention can be suitably used as a sheet obtained by obtaining a wafer having a protective film from a plate-shaped member to be processed such as a semiconductor wafer.

4‧‧‧保護膜形成用薄膜 4‧‧‧film for protective film formation

10‧‧‧保護膜形成用複合板片 10‧‧‧Composite sheet for protective film formation

10A‧‧‧保護膜形成用複合板片10之保護膜形成用薄膜4側之主面 10A‧‧‧Main surface of the film 4 for protective film formation of the composite sheet 10 for protective film formation

20‧‧‧剝離板片 20‧‧‧ peeling sheet

20A‧‧‧剝離板片20之剝離面 20A‧‧‧ peeling surface of peeling sheet 20

100‧‧‧保護膜形成用複合板片-剝離板片層積體(PR層積體) 100‧‧‧Composite sheet for protective film formation-release sheet laminate (PR laminate)

Claims (11)

一種保護膜形成用複合板片-剝離板片層積體，包括：剝離板片；及保護膜形成用複合板片，層積於上述剝離板片之剝離面上，其特徵在於：上述保護膜形成用複合板片，包括：基材；黏著板片，其包括層積於上述基材之一方的主面之黏著劑層；及保護膜形成用薄膜，其係層積於上述黏著板片之上述黏著劑層側之主面之至少一部分的區域，藉由硬化可形成保護膜，使上述保護膜形成用複合板片之上述保護膜形成用薄膜側之主面與上述剝離板片之剝離面相對地，上述保護膜形成用複合板片係層積於上述剝離板片，在於上述保護膜形成用複合板片之上述保護膜形成用薄膜側之主面，於使用時應貼附於被加工構件之區域之加工用區域，相當於與上述保護膜形成用薄膜之上述剝離面相對之主面之全區域，或包含該主面之全區域。 A composite sheet-peeling sheet laminate for forming a protective film, comprising: a peeling sheet; and a composite sheet for forming a protective film, laminated on a peeling surface of the peeling sheet, characterized in that: the protective film a composite sheet for forming, comprising: a substrate; an adhesive sheet comprising an adhesive layer laminated on a main surface of one of the substrates; and a film for forming a protective film laminated on the adhesive sheet The at least a part of the main surface of the adhesive layer side is formed by curing to form a protective film, and the main surface of the protective film forming film surface of the protective film forming composite sheet and the peeling surface of the peeling sheet are formed. In contrast, the composite sheet for forming a protective film is laminated on the peeling sheet, and the main surface of the film for forming a protective film of the composite sheet for forming a protective film is attached to the processed surface during use. The processing region in the region of the member corresponds to the entire region of the main surface facing the peeling surface of the film for forming a protective film, or the entire region including the main surface. 根據申請專利範圍第1項之保護膜形成用複合板片-剝離板片層積體，其中上述保護膜形成用薄膜與上述剝離面相對之主面之外周，與上述加工用區域之外周，以平面視之離間距離，係0mm以上10mm以下。 A composite sheet-peeling sheet laminate for forming a protective film according to the first aspect of the invention, wherein the film for forming a protective film and the outer surface of the main surface facing the peeling surface and the outer periphery of the processing region are The distance between the planes is 0mm or more and 10mm or less. 根據申請專利範圍第1項之保護膜形成用複合板片-剝離板片層積體，其中使上述保護膜形成用複合板片所具有的上述保護膜形成用薄膜硬化形成保護膜時，上述黏著板片對上述保護膜之黏著力為0.5N/25mm以下。 The composite sheet-peeling sheet laminate according to the first aspect of the invention, wherein the protective film forming film of the protective film forming composite sheet is cured to form a protective film, the adhesive layer The adhesion of the sheet to the above protective film is 0.5 N/25 mm or less. 根據申請專利範圍第1項之保護膜形成用複合板片-剝離板片層積體，其中上述黏著板片對上述保護膜形成用薄膜之黏著力為0.5N/25mm以下。 The composite sheet-peeling sheet laminate for protective film formation according to the first aspect of the invention, wherein the adhesive sheet has an adhesive force to the protective film forming film of 0.5 N/25 mm or less. 根據申請專利範圍第1項之保護膜形成用複合板片-剝離板片層積體，其中上述黏著板片之上述黏著劑層側之主面之上述保護膜形成用薄膜貼附之區域，係由能量線硬化型黏著劑之硬化物所組成之黏著劑之面所組成。 The composite sheet-peeling sheet laminate according to the first aspect of the invention, wherein the adhesive sheet is adhered to the main surface of the adhesive layer on the side of the adhesive layer. It consists of the surface of the adhesive composed of the hardened material of the energy ray-curable adhesive. 根據申請專利範圍第1項之保護膜形成用複合板片-剝離板片層積體，其中上述保護膜形成用薄膜含有填充材，上述保護膜形成用薄膜之填充材的含量，作為佔上述保護膜形成用薄膜之全固形份之質量的比例，為30質量%以上80質量%以下。 The composite sheet-peeling sheet laminate for protective film formation according to the first aspect of the invention, wherein the protective film forming film contains a filler, and the content of the filler for forming the protective film is as described above. The ratio of the mass of the total solid content of the film for film formation is 30% by mass or more and 80% by mass or less. 一種保護膜形成用複合板片，由申請專利範圍第1至6項中任一項所記載的保護膜形成用複合板片-剝離板片層積體，剝離上述剝離板片而成。 A composite sheet for forming a protective film, which is obtained by peeling the peeled sheet from the composite sheet-peeling sheet laminate according to any one of the first to sixth aspects of the invention. 一種具有保護膜之晶片的製造方法，其特徵在於：由申請專利範圍第1至6項中任一項所記載的保護膜形成用複合板片-剝離板片層積體，剝離上述保護膜形成用複合板片，使上述保護膜形成用薄膜的一方的主面外露，藉由在被加工構件的一面，將上述剝離之保護膜形成用複合板片，使上述保護膜形成用薄膜之上述外露之一方的主面全體，以上述加工構件之一面覆蓋地貼附，得到包括上述保護膜形成用複合板片與上述被加工構件之第一層積構造體， 使含於上述第一層積構造體之上述保護膜形成用複合板片之上述保護膜形成用薄膜硬化，得到具有依序層積上述黏著板片、上述保護膜及上述被加工構件之部分之第二層積構造體，將上述第二層積構造體，由上述黏著板片側與相反側切割，將上述被加工構件與上述保護膜一起個片化，得到具有上述保護膜之個片與該個片附著在一方的面之晶片所組成之具有保護膜之晶片之複數，層積於上述黏著板片上之部分之第三層積構造體，將上述第三層積構造體所具有之上述複數具有保護膜之晶片，個別拾取得到上述具有保護膜之晶片。 A method for producing a wafer having a protective film, which is characterized in that the composite sheet-peeling sheet laminate for forming a protective film according to any one of claims 1 to 6 is peeled off to form the protective film. In the composite sheet, the main surface of the film for forming a protective film is exposed, and the peeled protective film forming composite sheet is peeled off on one surface of the workpiece to expose the film for forming the protective film. The entire main surface of one of the main surfaces is attached to the surface of the processed member, and the first laminated structure including the composite sheet for forming a protective film and the member to be processed is obtained. The film for forming a protective film of the composite sheet for forming a protective film to be formed in the first laminate structure is cured to obtain a portion in which the adhesive sheet, the protective film, and the member to be processed are sequentially laminated. In the second laminate structure, the second laminate structure is cut from the side of the adhesive sheet and the opposite side, and the workpiece is formed into a sheet together with the protective film to obtain a sheet having the protective film. a third laminated structure in which a plurality of wafers having a protective film are laminated on a wafer having one surface and a portion laminated on the adhesive sheet, and the plural number of the third laminated structure The wafer having the protective film is individually picked up to obtain the above wafer having the protective film. 一種具有保護膜之晶片的製造方法，其特徵在於：由申請專利範圍第1至6項中任一項所記載的保護膜形成用複合板片-剝離板片層積體，剝離上述保護膜形成用複合板片，使上述保護膜形成用薄膜的一方的主面外露，藉由在被加工構件的一面，將上述剝離之保護膜形成用複合板片，使上述保護膜形成用薄膜之上述外露之一方的主面全體，以上述加工構件之一面覆蓋地貼附，得到包括上述保護膜形成用複合板片與上述被加工構件之第一層積構造體，將上述第一層積構造體，由上述黏著板片側與相反側切割將上述被加工構件與上述保護膜形成用薄膜一起個片化，得到具有上述保護膜形成用薄膜之個片與該個片附著於一方的面之晶片所組成之具有保護膜形成用薄膜之晶片之複 數，層積於上述黏著板片上之部分之第四層積構造體，使上述第四層積構造體所包括之上述具有保護膜形成用薄膜之晶片之上述保護膜形成用薄膜之個片硬化，將上述具有保護膜形成用薄膜之晶片作為上述具有保護膜之晶片，將上述黏著板片上的上述複數具有保護膜之晶片個別拾取得到上述具有保護膜之晶片。 A method for producing a wafer having a protective film, which is characterized in that the composite sheet-peeling sheet laminate for forming a protective film according to any one of claims 1 to 6 is peeled off to form the protective film. In the composite sheet, the main surface of the film for forming a protective film is exposed, and the peeled protective film forming composite sheet is peeled off on one surface of the workpiece to expose the film for forming the protective film. One of the main surfaces of the entire surface is attached to the surface of the processed member, and the first laminated structure including the composite sheet for forming a protective film and the member to be processed is obtained. The film-formed member and the film for protective film formation are formed by dicing the film on the side of the adhesive sheet and the film on the opposite side to form a film having the film for forming a protective film and a wafer on which the sheet is adhered to one surface. A wafer having a film for forming a protective film a fourth laminated structure in which a portion of the protective film forming film of the film having a protective film is included in the fourth laminated structure is hardened by a fourth laminated structure which is laminated on the adhesive sheet The wafer having the film for forming a protective film is used as the wafer having the protective film, and the plurality of wafers having the protective film on the adhesive sheet are individually picked up and obtained on the wafer having the protective film. 一種具有保護膜之晶片的製造方法，其特徵在於：由申請專利範圍第1至6項中任一項所記載的保護膜形成用複合板片-剝離板片層積體，剝離上述保護膜形成用複合板片，使上述保護膜形成用薄膜的一方的主面外露，藉由在被加工構件的一面，將上述剝離之保護膜形成用複合板片，使上述保護膜形成用薄膜之上述外露之一方的主面全體，以上述加工構件之一面覆蓋地貼附，得到包括上述保護膜形成用複合板片與上述被加工構件之第一層積構造體，將上述第一層積構造體，由上述黏著板片側與相反側切割將上述被加工構件與上述保護膜形成用薄膜一起個片化，得到具有上述保護膜形成用薄膜之個片與該個片附著於一方的面之晶片所組成之具有保護膜形成用薄膜之晶片之複數，層積於上述黏著板片上之部分之第四層積構造體，上述第四層積構造體所包括之上述複數具有保護膜形成用薄膜之晶片，個別拾取，使藉由上述拾取所得之上述具有保護膜形成用薄膜之晶片之上述保護膜形成用薄膜之個片硬化，將上述具有保護膜 形成用薄膜之晶片作為上述具有保護膜之晶片。 A method for producing a wafer having a protective film, which is characterized in that the composite sheet-peeling sheet laminate for forming a protective film according to any one of claims 1 to 6 is peeled off to form the protective film. In the composite sheet, the main surface of the film for forming a protective film is exposed, and the peeled protective film forming composite sheet is peeled off on one surface of the workpiece to expose the film for forming the protective film. One of the main surfaces of the entire surface is attached to the surface of the processed member, and the first laminated structure including the composite sheet for forming a protective film and the member to be processed is obtained. The film-formed member and the film for protective film formation are formed by dicing the film on the side of the adhesive sheet and the film on the opposite side to form a film having the film for forming a protective film and a wafer on which the sheet is adhered to one surface. a fourth laminated structure in which a plurality of wafers having a film for forming a protective film are laminated on a portion of the adhesive sheet, and the fourth laminated structure includes Of the complex wafer having a protective film is formed of a thin film, individual pickup, so that the pickup obtained by the above-described protective film is formed above the protective film is formed with a hardened film of the wafer with a sheet of film, the protective film having the above-described A wafer for forming a film is used as the above wafer having a protective film. 根據申請專利範圍第10項之具有保護膜之晶片的製造方法，其中對上述第一層積構造體及上述第四層積構造體之任意一個，由上述黏著板片側照射雷射光進行標印，將上述具有保護膜形成用薄膜之晶片所包括之上述保護膜形成用薄膜作為具有標記之保護膜形成用薄膜。 The method for producing a wafer having a protective film according to claim 10, wherein the one of the first laminated structure and the fourth laminated structure is irradiated with laser light by the adhesive sheet side. The film for forming a protective film included in the wafer having the film for forming a protective film is used as a film for forming a protective film having a mark.
TW102118182A 2013-03-26 2013-05-23 A composite sheet for forming a pressure-sensitive adhesive sheet and a protective film and a method for manufacturing a wafer having a protective film TWI577563B (en)

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