TWI764885B - Complex sheet for forming protective film - Google Patents

Complex sheet for forming protective film Download PDF

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TWI764885B
TWI764885B TW106104893A TW106104893A TWI764885B TW I764885 B TWI764885 B TW I764885B TW 106104893 A TW106104893 A TW 106104893A TW 106104893 A TW106104893 A TW 106104893A TW I764885 B TWI764885 B TW I764885B
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protective film
forming
film
meth
acrylate
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TW106104893A
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TW201801916A (en
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佐伯尚哉
佐佐木遼
米山裕之
山本大輔
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日商琳得科股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/406—Bright, glossy, shiny surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68327—Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support used during dicing or grinding

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Adhesive Tapes (AREA)
  • Dicing (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

A complex sheet for forming protective film including a support sheet, a protective film-forming film provided on a surface of the support sheet on one side, and a coating layer provided on a surface of the support sheet opposite to the side where the protective film-forming film is provided, wherein a gloss value of a surface of the coating film opposite to the side on which the protective film-forming film is provided is 32 to 95.

Description

保護膜形成用複合片 Composite sheet for protective film formation

本發明係關於一種保護膜形成用複合片，用以於半導體晶片的背面形成保護膜。 The present invention relates to a composite sheet for forming a protective film for forming a protective film on the back surface of a semiconductor wafer.

本申請案主張基於2016年3月4日在日本提出申請之日本特願2016-042690號的優先權，並將該申請案的內容引用至本文中。 This application claims priority based on Japanese Patent Application No. 2016-042690 for which it applied in Japan on March 4, 2016, and the content of the application is incorporated herein by reference.

近年來，業界使用稱為所謂的倒裝(face down)方式之安裝方法製造半導體裝置。倒裝方式中，使用於電路面上具有凸塊等電極之半導體晶片，將前述電極與基板接合。因此，有時晶片中的與電路面為相反側的背面裸露。 In recent years, the industry has used a mounting method called a so-called face down method to manufacture semiconductor devices. In the flip-chip method, a semiconductor wafer having electrodes such as bumps on a circuit surface is used, and the electrodes are bonded to a substrate. Therefore, the back surface of the wafer on the opposite side to the circuit surface may be exposed.

有時於該裸露之晶片背面形成由有機材料構成之樹脂膜作為保護膜，以附有保護膜之半導體晶片之形式組入至半導體裝置中。保護膜係用以防止在切割步驟或封裝之後晶片產生龜裂。 In some cases, a resin film composed of an organic material is formed on the backside of the bare wafer as a protective film, and is incorporated into a semiconductor device in the form of a semiconductor wafer with a protective film. The protective film is used to prevent chip cracking after the dicing step or packaging.

形成此種保護膜時，使用於支持片上具備保護膜形成用膜之保護膜形成用複合片。作為前述支持片，例如使用樹脂製基材或基材及黏著劑層等之積層結構體，有時亦對前述基材之保護膜形成用膜或黏著劑層等之積層面進行表面處理。前述保護膜形成用複合片中，保護膜形成用膜具有形成保護膜之功能，並且支持片能夠發揮作為切割片(dicing sheet)之功能，可謂為保護膜形成用膜與切割片形成為一體之保護膜形成用複合片。 When forming such a protective film, the composite sheet for protective film formation provided with the film for protective film formation on a support sheet is used. As the above-mentioned support sheet, for example, a resin base material or a laminated structure of a base material and an adhesive layer is used, and the laminated layer such as a film for forming a protective film or an adhesive layer of the above-mentioned base material may also be surface-treated. In the aforementioned composite sheet for forming a protective film, the film for forming a protective film has a function of forming a protective film, and the support sheet can function as a dicing sheet, so it can be said that the film for forming a protective film and the dicing sheet are integrally formed. A composite sheet for forming a protective film.

通常，用於支持片之加工前之前述基材的單面或雙面具有凹凸形狀。原因在於，若不具有此種凹凸形狀，則將基材捲取成輥時，基材彼此之接觸面黏附而產生黏連(blocking)，因而使用困難。若基材彼此之接觸面中至少一者具有凹凸形狀，則接觸面的面積變小，因此黏連得到抑制。 Usually, the single side or both sides of the aforementioned base material before processing for a support sheet have a concavo-convex shape. The reason is that if the base material does not have such a concave-convex shape, when the base material is wound into a roll, the contact surfaces of the base materials adhere to each other to cause blocking, which makes it difficult to use. When at least one of the contact surfaces of the substrates has a concavo-convex shape, the area of the contact surface becomes small, and thus blocking is suppressed.

典型而言，使用此種具有凹凸面之基材之以往之保護膜形成用複合片具有如圖4所示之構成。圖4係以示意方式表示以往之保護膜形成用複合片的一例之剖視圖。再者，以下之說明所使用之圖式中，例如為了易於理解保護膜形成用複合片之特徵，方便起見，有時將成為主要部分之部分放大表示，而並不限於各構成要素的尺寸比率等與實際相同。 Typically, the conventional composite sheet for protective film formation using such a base material having an uneven surface has a structure as shown in FIG. 4 . FIG. 4 is a cross-sectional view schematically showing an example of a conventional composite sheet for forming a protective film. In addition, in the drawings used in the following description, for example, in order to facilitate the understanding of the characteristics of the composite sheet for forming a protective film, the part that is the main part is sometimes shown enlarged for convenience, and is not limited to the size of each component. The ratios etc. are the same as the actual ones.

此處所示之以往之保護膜形成用複合片9於支持片90上具備保護膜形成用膜13，支持片90由基材91及黏著劑層12之積層結構體構成，於黏著劑層12上具備保護膜形成用膜13。保護膜形成用膜13藉由硬化而成為保護膜。保護膜形成用複合片9進一步於保護膜形成用膜13上具備剝離膜15，於使用保護膜形成用複合片9時將剝離膜15移除。保護膜形成用複合片9中，支持片90中的與具備保護膜形成用膜13之面(表面)90a為相反側的面(背面)90b成為凹凸面，亦即基材91中的與具備黏著劑層12之面(表面)91a為相反側的面(背面)91b成為凹凸面。保護膜形成用複合片9藉由如此般使基材91的背面91b成為凹凸面，在捲取成輥時，基材91的背面91b與剝離膜15的露出面(表面)15a之黏附亦即黏連得到抑制。 The conventional composite sheet 9 for forming a protective film shown here is provided with a film 13 for forming a protective film on a support sheet 90. The support sheet 90 is composed of a laminated structure of a base material 91 and an adhesive layer 12. The film 13 for protective film formation is provided thereon. The film 13 for protective film formation becomes a protective film by hardening. The composite sheet 9 for protective film formation is further provided with the peeling film 15 on the film 13 for protective film formation, and when using the composite sheet 9 for protective film formation, the peeling film 15 is removed. In the composite sheet 9 for forming a protective film, the surface (back surface) 90b on the opposite side to the surface (surface) 90a provided with the film 13 for forming a protective film in the support sheet 90 is a concavo-convex surface, that is, the surface (back surface) 90b in the base material 91 and the The surface (front surface) 91a of the adhesive layer 12 is the surface (back surface) 91b on the opposite side, which becomes a concavo-convex surface. In the composite sheet 9 for forming a protective film, by forming the back surface 91b of the base material 91 as a concave and convex surface in this way, when the back surface 91b of the base material 91 is wound into a roll, the adhesion of the back surface 91b of the base material 91 and the exposed surface (surface) 15a of the release film 15 is ie Adhesion is inhibited.

另一方面，對於保護膜形成用複合片，有時對由保護膜形成用膜形成之保護膜之支持片側的面，藉由照射雷射光進行印字(以下，有時稱為「雷射印字」)。雷射印字時，自支持片的形成有保護膜之側的相反側照射。此時，例如於保護膜形成用複合片9之情形時，自基材91的背面91b側透過支持片90對保護膜照射雷射光，但由於基材91的背面91b為凹凸面，故而於該凹凸面上光會發生漫反射，而存在雷射印字不清晰之問題。 On the other hand, in the composite sheet for forming a protective film, the surface on the support sheet side of the protective film formed of the film for forming a protective film may be printed by irradiating laser light (hereinafter, sometimes referred to as "laser printing"). ). At the time of laser printing, irradiation is performed from the side opposite to the side where the protective film of the support sheet is formed. At this time, for example, in the case of the composite sheet 9 for forming a protective film, the protective film is irradiated with laser light through the support sheet 90 from the back surface 91b side of the base material 91. However, since the back surface 91b of the base material 91 is an uneven surface, the The light on the concave and convex surface will be diffusely reflected, and there is a problem that the laser printing is not clear.

作為可防止此種光之漫反射之保護膜形成用複合片，已知有具有如圖5所示之構成之保護膜形成用複合片8(參照例如專利文獻1)。 As a composite sheet for forming a protective film that can prevent such diffuse reflection of light, a composite sheet 8 for forming a protective film having a structure as shown in FIG. 5 is known (see, for example, Patent Document 1).

圖5係以示意方式表示以往之保護膜形成用複合片的另一例之剖視圖。 FIG. 5 is a cross-sectional view schematically showing another example of a conventional composite sheet for forming a protective film.

此處所示之以往之保護膜形成用複合片8係與保護膜形成用複合片9同樣地，於支持片80上具備保護膜形成用膜13，支持片80由基材81及黏著劑層12之積層結構體構成，於黏著劑層12上具備保護膜形成用膜13。但是，支持片80中，基材81的凹凸面之配置與支持片90中的基材91相反。亦即，保護膜形成用複合片8中，基材81中的具備黏著劑層12的面(表面)81a成為凹凸面，基材81中的與表面81a為相反側的面(背面)81b成為平滑面。支持片80中的基材81、保護膜形成用膜13及剝離膜15分別與支持片90中的基材91、保護膜形成用膜13及剝離膜15相同。 The conventional composite sheet 8 for forming a protective film shown here is provided with the film 13 for forming a protective film on a support sheet 80, which is composed of a base material 81 and an adhesive layer, similarly to the composite sheet 9 for forming a protective film. The layered structure structure of 12 includes a film 13 for forming a protective film on the adhesive layer 12 . However, in the support sheet 80 , the arrangement of the uneven surface of the base material 81 is opposite to that of the base material 91 in the support sheet 90 . That is, in the composite sheet 8 for forming a protective film, the surface (surface) 81a of the base material 81 provided with the adhesive layer 12 becomes the uneven surface, and the surface (back surface) 81b of the base material 81 on the opposite side to the surface 81a becomes smooth surface. The base material 81 , the protective film-forming film 13 , and the release film 15 in the support sheet 80 are the same as the base material 91 , the protective film-forming film 13 , and the release film 15 in the support sheet 90 , respectively.

但是，於保護膜形成用複合片8之情形時，基材81的背面81b成為平滑面，亦即支持片80中的與具備黏著劑層12之面(表面)80a為相反側的面(背面)80b成為平滑面，將保護膜形成用複合片8捲取成輥時，無法抑制基材81的背面81b與剝離膜15的露出面(表面)15a之黏附亦即黏連。若產生黏連，則會於保護膜形成用複合片8產生褶 皺，將保護膜形成用複合片8自輥捲出時，剝離膜15自保護膜形成用膜13剝離。再者，於基材81的表面81a上，為了消除凹凸形狀，黏著劑層12必須具有充分的厚度。若黏著劑層12的厚度不充分，則存在如下問題：反映基材81的凹凸形狀而使保護膜形成用膜13之支持片80側的面(背面)13b具有凹凸形狀，由此種保護膜形成用膜13形成之保護膜之支持片側的面所被施加之雷射印字不清晰。 However, in the case of the composite sheet 8 for forming a protective film, the back surface 81b of the base material 81 is a smooth surface, that is, the surface (back surface) on the opposite side to the surface (surface) 80a provided with the adhesive layer 12 in the support sheet 80 ) 80b becomes a smooth surface, and when the composite sheet 8 for forming a protective film is wound into a roll, the back surface 81b of the base material 81 and the exposed surface (surface) 15a of the release film 15 cannot be prevented from adhering, ie, blocking. When blocking occurs, wrinkles will occur in the composite sheet 8 for forming a protective film. When the composite sheet 8 for forming a protective film is wrinkled and unrolled from a roll, the release film 15 is peeled off from the film 13 for forming a protective film. Furthermore, on the surface 81a of the base material 81, the adhesive layer 12 must have a sufficient thickness in order to eliminate the uneven shape. If the thickness of the adhesive layer 12 is insufficient, there is a problem in that the surface (back surface) 13b of the protective film-forming film 13 on the support sheet 80 side has a concavo-convex shape reflecting the concavo-convex shape of the base material 81 . The laser print applied to the surface on the support sheet side of the protective film formed of the film 13 for forming is not clear.

[先前技術文獻] [Prior Art Literature]

[專利文獻] [Patent Literature]

專利文獻1：日本特許第5432853號公報。 Patent Document 1: Japanese Patent No. 5432853.

如此，實際情況是以往並不存在可兼顧抑制黏連與對保護膜之清晰的雷射印字之保護膜形成用複合片。 In this way, the actual situation is that there has not been a composite sheet for forming a protective film that can achieve both blocking suppression and clear laser printing on the protective film.

本發明係鑒於上述情況而完成，課題在於提供一種保護膜形成用複合片，用以於半導體晶片的背面形成保護膜，並且該保護膜形成用複合片可抑制黏連，且可對保護膜清晰地進行雷射印字。 The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a composite sheet for forming a protective film for forming a protective film on the back surface of a semiconductor wafer, which can suppress blocking and clear the protective film. laser printing.

本發明的一形態如下所述。 One aspect of the present invention is as follows.

(1)本發明之一實施形態中，提供一種保護膜形成用複合片，係於支持片的一表面上具備保護膜形成用膜，並於前述支持片中的與具備前述保護膜形成用膜之側為相反側的表面上具備塗層，且前述塗層中的與和前述支持片接觸之側為相反側的表面的光澤值為32至95。 (1) In one embodiment of the present invention, there is provided a composite sheet for forming a protective film comprising a film for forming a protective film on one surface of a support sheet, and the film for forming a protective film is provided on one surface of the supporting sheet with the film for forming a protective film. The surface on the opposite side is provided with a coating layer, and the gloss value of the surface on the opposite side from the side in contact with the support sheet in the coating layer is 32 to 95.

(2)於前述(1)之保護膜形成用複合片中，其中使用進一步於前述保護膜形成用膜上具備剝離膜之前述保護膜形成用複合片，利用下述方法測定之前述剝離膜的剝離力可為10mN/50mm以下。 (2) In the composite sheet for forming a protective film according to (1), in which the composite sheet for forming a protective film further comprising a release film on the film for forming a protective film is used, the amount of the release film measured by the following method The peel force may be 10 mN/50 mm or less.

(剝離膜的剝離力的測定方法) (Measuring method of peeling force of peeling film)

將於保護膜形成用膜上具備剝離膜且寬度50mm、長度100mm之前述保護膜形成用複合片，以前述塗層全部朝向相同方向且前述塗層的合計厚度成為10μm至60μm之方式重疊複數片，藉此製成第一最外層為塗層且第二最外層為剝離膜之積層體，將前述積層體以於前述保護膜形成用複合片的積層方向上施加980.665mN之力之狀態於40℃下靜置3天後，將於前述積層方向上距離前述第一最外層之塗層最近之剝離膜於剝離速度300mm/分鐘、剝離角度180°之條件下自鄰接之塗層剝離，測定此時的剝離力。 A plurality of composite sheets for forming a protective film having a release film on the film for forming a protective film and having a width of 50 mm and a length of 100 mm are stacked so that the coating layers are all oriented in the same direction and the total thickness of the coating layers is 10 μm to 60 μm. , thereby making a laminate in which the first outermost layer is a coating layer and the second outermost layer is a release film. After standing at ℃ for 3 days, the peeling film closest to the coating of the first outermost layer in the lamination direction was peeled off from the adjacent coating under the conditions of peeling speed of 300 mm/min and peeling angle of 180°, and measured this. peeling force.

(3)於前述(1)或(2)之保護膜形成用複合片中，其中亦可為前述支持片由基材及黏著劑層積層而成，前述保護膜 形成用複合片由前述塗層、基材、黏著劑層及保護膜形成用膜依序積層而成。 (3) In the above-mentioned composite sheet for forming a protective film of (1) or (2), the above-mentioned support sheet may be formed by laminating a base material and an adhesive, and the above-mentioned protective film may be The composite sheet for formation is formed by laminating the coating layer, the base material, the adhesive layer, and the film for forming a protective film in this order.

(4)於前述(3)之保護膜形成用複合片中，其中前述黏著劑層亦可為能量線硬化性或非能量線硬化性之層。 (4) In the composite sheet for protective film formation of the said (3), the said adhesive layer may be an energy ray curable or a non-energy ray curable layer.

(5)於前述(1)至(4)中任一項之保護膜形成用複合片中，其中前述保護膜形成用膜可為熱硬化性或能量線硬化性之膜。 (5) In the composite sheet for forming a protective film according to any one of (1) to (4), the film for forming a protective film may be a thermosetting film or an energy ray curable film.

根據本發明，提供一種保護膜形成用複合片，用以於半導體晶片的背面形成保護膜，並且該保護膜形成用複合片可抑制黏連，且可對保護膜清晰地進行雷射印字。 According to the present invention, there is provided a composite sheet for forming a protective film for forming a protective film on the back surface of a semiconductor wafer, which can suppress blocking and can clearly laser-print the protective film.

1、2、8、9‧‧‧保護膜形成用複合片 1, 2, 8, 9‧‧‧Composite sheet for forming protective film

10、80、90‧‧‧支持片 10, 80, 90‧‧‧Support Sheet

10a、80a、90a‧‧‧支持片的表面 10a, 80a, 90a‧‧‧Surface of support sheet

10b、80b、90b‧‧‧支持片的背面 10b, 80b, 90b‧‧‧Back side of support sheet

11、81、91‧‧‧基材 11, 81, 91‧‧‧Substrate

11a、81a、91a‧‧‧基材的表面 11a, 81a, 91a‧‧‧Substrate surface

11b、81b、91b‧‧‧基材的背面 11b, 81b, 91b‧‧‧ backside of substrate

12‧‧‧黏著劑層 12‧‧‧Adhesive layer

12a‧‧‧黏著劑層的表面 12a‧‧‧The surface of the adhesive layer

13、23‧‧‧保護膜形成用膜 13, 23‧‧‧Protective film forming film

13a、23a‧‧‧保護膜形成用膜的表面 13a, 23a‧‧‧The surface of the film for forming a protective film

13b‧‧‧保護膜形成用膜的背面 13b‧‧‧Back surface of protective film forming film

14‧‧‧塗層 14‧‧‧Coating

14a‧‧‧塗層的表面 14a‧‧‧Coated surface

14b‧‧‧塗層的背面 14b‧‧‧Coated backside

15‧‧‧剝離膜 15‧‧‧Peeling film

15a‧‧‧剝離膜的表面 15a‧‧‧Surface of release film

16‧‧‧治具用接著劑層 16‧‧‧Adhesive layer for jig

16a‧‧‧治具用接著劑層的表面 16a‧‧‧The surface of the adhesive layer for the jig

121‧‧‧黏著劑層的曲面狀的周緣部 121‧‧‧The curved peripheral edge of the adhesive layer

122‧‧‧黏著劑層的平面狀的周緣部 122‧‧‧Flat peripheral part of the adhesive layer

d1、d2‧‧‧直徑 d 1 , d 2 ‧‧‧diameter

w1、w2‧‧‧寬度 w 1 , w 2 ‧‧‧Width

圖1係以示意方式表示本發明之一實施形態之保護膜形成用複合片的一實施形態之剖視圖。 FIG. 1 is a cross-sectional view schematically showing an embodiment of a composite sheet for forming a protective film according to an embodiment of the present invention.

圖2係以示意方式表示本發明之一實施形態之保護膜形成用複合片的另一實施形態之剖視圖。 2 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film according to one embodiment of the present invention.

圖3係表示實施例中所製造之保護膜形成用複合片之俯視圖。 FIG. 3 is a plan view showing the composite sheet for forming a protective film produced in the Example.

圖4係以示意方式表示以往之保護膜形成用複合片的一例之剖視圖。 FIG. 4 is a cross-sectional view schematically showing an example of a conventional composite sheet for forming a protective film.

圖5係以示意方式表示以往之保護膜形成用複合片的另一例之剖視圖。 FIG. 5 is a cross-sectional view schematically showing another example of a conventional composite sheet for forming a protective film.

◎保護膜形成用複合片 ◎Composite sheet for forming protective film

本實施形態之保護膜形成用複合片係於支持片的一表面上具備保護膜形成用膜，並於前述支持片中的與具備前述保護膜形成用膜之側為相反側的表面上具備塗層，且前述塗層中的與和前述支持片接觸之側為相反側的表面的光澤值為32至95。 The composite sheet for forming a protective film of the present embodiment is provided with a film for forming a protective film on one surface of a support sheet, and includes a coating on the surface of the supporting sheet on the opposite side to the side on which the film for forming a protective film is provided. layer, and the gloss value of the surface of the coating layer on the opposite side from the side in contact with the support sheet is 32 to 95.

前述保護膜形成用複合片藉由前述塗層中的與和前述支持片接觸之側為相反側的表面的光澤值為如上所述之特定範圍內，對保護膜形成用膜硬化後的保護膜，自塗層側照射雷射光時，雷射光有效且穩定地到達保護膜，因此可對保護膜清晰地進行雷射印字。 The above-mentioned protective film-forming composite sheet has a gloss value of the surface on the opposite side with the side in contact with the above-mentioned support sheet in the above-mentioned coating. , When the laser light is irradiated from the coating side, the laser light reaches the protective film effectively and stably, so the protective film can be clearly laser printed.

另外，前述保護膜形成用複合片藉由具備具有易滑性及抗靜電性之前述塗層，藉此在捲取成輥時，黏連得到抑制。 Moreover, when the said composite sheet for protective film formation is provided with the said coating layer which has easy slipperiness and antistatic property, when it winds up into a roll, blocking is suppressed.

再者，本說明書中，前述保護膜形成用複合片中，藉由加熱或照射能量線而使保護膜形成用膜硬化成保護膜之片，亦只要可維持前述支持片及保護膜之積層結構，即稱為保護膜形成用複合片。另外，前述保護膜形成用複合片中，前述支持片為基材及黏著劑層之積層結構體之情形時，使黏著劑層硬化後之片，亦只要可維持前述基材、黏 著劑層之硬化物、及保護膜形成用膜或保護膜之積層結構，即稱為保護膜形成用複合片。 Furthermore, in this specification, in the composite sheet for forming a protective film, the film for forming a protective film is cured into a protective film by heating or irradiating energy rays, as long as the laminated structure of the supporting sheet and the protective film can be maintained. , which is called a composite sheet for forming a protective film. In addition, in the composite sheet for forming a protective film, in the case where the support sheet is a laminated structure of a base material and an adhesive layer, the sheet after curing the adhesive layer can also maintain the base material, adhesive The cured product of the adhesive layer, and the film for forming a protective film or the laminated structure of the protective film is called a composite sheet for forming a protective film.

圖1係以示意方式表示本發明之一實施形態之保護膜形成用複合片的一實施形態之剖視圖。 FIG. 1 is a cross-sectional view schematically showing an embodiment of a composite sheet for forming a protective film according to an embodiment of the present invention.

此處所示之保護膜形成用複合片1係具備於支持片10的一表面10a上具備保護膜形成用膜13，於支持片10的另一表面(背面)10b上具備塗層14。再者，支持片10由基材11及黏著劑層12積層而成，於基材11的一表面11a上具備黏著劑層12，於基材11的另一表面(背面)11b上具備塗層14，於黏著劑層12上具備保護膜形成用膜13。另外，保護膜形成用複合片1進一步於保護膜形成用膜13上具備剝離膜15，使用保護膜形成用複合片1時將剝離膜15移除。保護膜形成用膜13藉由硬化而成為保護膜。 The composite sheet 1 for protective film formation shown here is provided with the film 13 for protective film formation on one surface 10a of the support sheet 10, and the coating layer 14 is provided on the other surface (back surface) 10b of the support sheet 10. Furthermore, the support sheet 10 is formed by laminating a substrate 11 and an adhesive layer 12 , and has an adhesive layer 12 on one surface 11 a of the substrate 11 and a coating layer on the other surface (back) 11 b of the substrate 11 . 14. The film 13 for forming a protective film is provided on the adhesive layer 12 . Further, the composite sheet 1 for forming a protective film further includes a release film 15 on the film 13 for forming a protective film, and the release film 15 is removed when the composite sheet 1 for forming a protective film is used. The film 13 for protective film formation becomes a protective film by hardening.

保護膜形成用複合片1中，黏著劑層12積層於基材11的前述表面11a上，保護膜形成用膜13積層於黏著劑層12的表面12a的一部分。並且，於黏著劑層12的表面12a中未積層保護膜形成用膜13的露出面、及保護膜形成用膜13的表面13a(上表面及側面)上積層有剝離膜15。 In the composite sheet 1 for protective film formation, the adhesive layer 12 is laminated on the aforementioned surface 11 a of the base material 11 , and the film 13 for protective film formation is laminated on a part of the surface 12 a of the adhesive layer 12 . In addition, the release film 15 is laminated on the exposed surface of the surface 12a of the adhesive layer 12 where the film for forming a protective film 13 is not laminated, and on the surface 13a (upper surface and side surface) of the film 13 for forming a protective film 13 .

再者，於剝離膜15與黏著劑層12的表面12a或保護膜形成用膜13的表面13a之間亦可存在空隙部。例如， 保護膜形成用膜13的側面、或黏著劑層12的表面12a中保護膜形成用膜13的附近區域係容易產生前述空隙部。 In addition, a void part may exist between the peeling film 15 and the surface 12a of the adhesive layer 12 or the surface 13a of the film 13 for protective film formation. E.g, The above-mentioned void portion is likely to be generated in the side surface of the film 13 for forming a protective film or the region in the vicinity of the film 13 for forming a protective film on the surface 12a of the adhesive layer 12 .

保護膜形成用複合片1中，塗層14中的與和支持片10(基材11)接觸之面(表面)14a為相反側的面(背面)14b的光澤值為32至95。藉此，可對保護膜清晰地進行雷射印字。 In the composite sheet 1 for forming a protective film, the surface (surface) 14b of the coating layer 14 which is in contact with the support sheet 10 (substrate 11 ) has a gloss value of 32 to 95 on the opposite side (back surface) 14b. Thereby, the protective film can be clearly laser-printed.

再者，本實施形態中，所謂「塗層的表面的光澤值」，只要無特別說明，則意指以下述方式獲得之值：依據JIS K 7105，自塗層中之支持片側的相反側測定塗層的表面的20°鏡面光澤度。 In addition, in the present embodiment, the so-called "gloss value of the surface of the coating layer", unless otherwise specified, means the value obtained as follows: according to JIS K 7105, measured from the side opposite to the support sheet side in the coating layer 20° specular gloss of the coated surface.

另外，保護膜形成用複合片1具備塗層14，藉此即便於捲取成輥之情形時，基材11的前述背面11b與剝離膜15的露出面(表面)15a之黏附亦即黏連得到抑制。 In addition, the composite sheet 1 for forming a protective film is provided with the coating layer 14, whereby even when the back surface 11b of the base material 11 and the exposed surface (surface) 15a of the release film 15 are adhered, ie, adhered, even when wound into a roll be suppressed.

保護膜形成用複合片1中，支持片10中的與具備保護膜形成用膜13之面(表面)10a為相反側的面(背面)10b，亦即基材11中的與具備黏著劑層12之面(表面)11a為相反側的面(背面)11b係於此處成為平滑度低的凹凸面，但亦可為平滑面。於對由保護膜形成用膜13形成之保護膜(省略圖示)進行雷射印字之情形時，對保護膜之支持片10側的面，自塗層14側照射雷射光。此時，支持片10的前述背面10b(基材11的前述背面11b)為凹凸面及平滑面之 任一者時，塗層14均被覆該面，因此塗層14中的與和支持片10(基材11)接觸之面(表面)14a為相反側的面(背面)14b的平滑度高，該面(背面)14b的表面粗糙度Ra小，藉此可抑制雷射光於塗層14發生漫反射，從而可對保護膜清晰地進行雷射印字。 In the composite sheet 1 for forming a protective film, the surface (back surface) 10b on the opposite side to the surface (surface) 10a provided with the film 13 for forming a protective film in the support sheet 10, that is, the surface (back surface) 10b provided with the adhesive layer in the base material 11. The surface (front surface) 11a of 12 is the surface (back surface) 11b on the opposite side, which is a concavo-convex surface with low smoothness, but may be a smooth surface. When laser-printing is performed on the protective film (not shown) formed of the protective film-forming film 13 , the surface of the protective film on the support sheet 10 side is irradiated with laser light from the coating layer 14 side. At this time, the back surface 10b of the support sheet 10 (the back surface 11b of the base material 11 ) is the difference between the uneven surface and the smooth surface. In either case, the coating layer 14 covers the surface, so that the surface (surface) 14a of the coating layer 14 that is in contact with the support sheet 10 (the base material 11) is the opposite side (back surface) 14b has high smoothness, The surface roughness Ra of the surface (back surface) 14b is small, whereby the diffuse reflection of the laser light on the coating layer 14 can be suppressed, so that the protective film can be clearly laser-printed.

再者，本說明書中，所謂「表面粗糙度Ra」，只要無特別說明，則意指JIS B0601：2001中規定的所謂的算術平均粗糙度。 In addition, in this specification, the "surface roughness Ra" means the so-called arithmetic mean roughness defined in JIS B0601:2001 unless otherwise specified.

保護膜形成用複合片1中，基材11的表面11a於此處成為平滑面，但亦可為平滑度低的凹凸面。但是，如後所述，就更容易抑制於基材11的表面11a與黏著劑層之間產生空隙部，使保護膜形成用複合片1具有較佳特性之方面而言，較佳為基材11的表面11a為平滑面。 In the composite sheet 1 for protective film formation, although the surface 11a of the base material 11 becomes a smooth surface here, it may be an uneven surface with low smoothness. However, as will be described later, the base material is preferable in that it is easier to suppress the generation of voids between the surface 11a of the base material 11 and the adhesive layer, and the composite sheet 1 for forming a protective film has preferable properties. The surface 11a of 11 is a smooth surface.

圖1所示之保護膜形成用複合片1係以下述方式使用：在移除剝離膜15之狀態下，於保護膜形成用膜13的表面13a貼附半導體晶圓(省略圖示)的背面，再將黏著劑層12的表面12a中未積層保護膜形成用膜13之露出面貼附於環狀框等治具。 The composite sheet 1 for forming a protective film shown in FIG. 1 is used by attaching the back surface of a semiconductor wafer (not shown) to the surface 13a of the film 13 for forming a protective film with the release film 15 removed. Then, the exposed surface of the surface 12a of the adhesive layer 12 on which the protective film forming film 13 is not laminated is attached to a jig such as a ring frame.

圖2係以示意方式表示本發明之一實施形態之保護膜形成用複合片的另一實施形態之剖視圖。再者，圖2 中，對與圖1所示相同的要素，標附與圖1之情形相同的元件符號，並省略該元件符號的詳細說明。於圖2以後的圖中亦相同。 2 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film according to one embodiment of the present invention. Again, Figure 2 Among them, the same elements as those shown in FIG. 1 are denoted by the same reference numerals as in the case of FIG. 1 , and the detailed description of the reference numerals is omitted. The same applies to the figures after FIG. 2 .

關於此處所示之保護膜形成用複合片2，於黏著劑層12的表面12a的整個表面積層有保護膜形成用膜23，於保護膜形成用膜23的表面23a的一部分積層有治具用接著劑層16，於保護膜形成用膜23的表面23a中未積層治具用接著劑層16之露出面、及治具用接著劑層16的表面16a(上表面及側面)上積層有剝離膜15，除這些方面以外，與圖1所示之保護膜形成用複合片1相同。 Regarding the composite sheet 2 for forming a protective film shown here, the film 23 for forming a protective film is layered on the entire surface area of the surface 12a of the adhesive layer 12, and a jig is laminated on a part of the surface 23a of the film 23 for forming a protective film. Using the adhesive layer 16, on the surface 23a of the protective film forming film 23, the exposed surface of the adhesive layer 16 for jig is not laminated, and the surface 16a (upper surface and side surface) of the adhesive layer 16 for jig is laminated on the surface 16a (the upper surface and the side surface). The release film 15 is the same as the composite sheet 1 for forming a protective film shown in FIG. 1 except for these points.

再者，於剝離膜15與保護膜形成用膜23的表面23a或治具用接著劑層16的表面16a之間亦可存在空隙部。例如，治具用接著劑層16的側面、保護膜形成用膜23的表面23a中治具用接著劑層16的附近區域係容易產生前述空隙部。 In addition, a void part may exist between the peeling film 15 and the surface 23a of the film 23 for protective film formation, or the surface 16a of the adhesive agent layer 16 for jigs. For example, in the side surface of the adhesive layer 16 for a jig and the surface 23a of the film 23 for forming a protective film, the area near the adhesive layer 16 for a jig is likely to generate the aforementioned voids.

保護膜形成用複合片2中，亦與保護膜形成用複合片1之情形同樣地，塗層14中的與和支持片10(基材11)接觸之面(表面)14a為相反側的面(背面)14b的光澤值為32至95。因此，可對由保護膜形成用膜23形成之保護膜清晰地進行雷射印字。 In the composite sheet 2 for forming a protective film, as in the case of the composite sheet 1 for forming a protective film, the surface (surface) 14a of the coating layer 14 that is in contact with the support sheet 10 (substrate 11 ) is the surface on the opposite side The gloss value of (back surface) 14b is 32 to 95. Therefore, the protective film formed of the protective film forming film 23 can be clearly laser-printed.

另外，保護膜形成用複合片2藉由具備塗層14，即便於捲取成輥之情形時亦可抑制黏連。 Moreover, since the composite sheet 2 for protective film formation is provided with the coating layer 14, blocking can be suppressed even when it winds up into a roll.

圖2所示之保護膜形成用複合片2係以下述方式使用：在移除剝離膜15之狀態下，於保護膜形成用膜23的表面23a貼附半導體晶圓(省略圖示)的背面，再將治具用接著劑層16的表面16a中的上表面貼附於環狀框等治具。 The composite sheet 2 for forming a protective film shown in FIG. 2 is used by attaching the back surface of a semiconductor wafer (not shown) to the surface 23a of the film 23 for forming a protective film with the release film 15 removed. Then, the upper surface of the surface 16a of the adhesive layer 16 for a jig is attached to a jig such as an annular frame.

本發明之保護膜形成用複合片並不限定於圖1至圖2所示的保護膜形成用複合片，在無損本發明的功效之範圍內，亦可將圖1至圖2所示之保護膜形成用複合片的一部分構成變更或刪除，或者對此前說明之保護膜形成用複合片進一步追加其他構成。 The composite sheet for forming a protective film of the present invention is not limited to the composite sheet for forming a protective film shown in FIGS. 1 to 2 , and the protective film shown in FIGS. A part of the structure of the composite sheet for film formation is changed or deleted, or another structure is further added to the composite sheet for protective film formation described above.

以下，對本發明之一實施形態之保護膜形成用複合片的各構成，進行更詳細的說明。 Hereinafter, each structure of the composite sheet for protective film formation which concerns on one Embodiment of this invention is demonstrated in detail.

○支持片 ○ Support sheet

前述支持片只要能夠設置前述保護膜形成用膜，即無特別限定，例如可列舉：用以防止於保護膜形成用膜的表面附著灰塵等之剝離片、及發揮用以於切割步驟等中對保護膜形成用膜的表面進行保護之切割片等作用之片。 The above-mentioned support sheet is not particularly limited as long as the above-mentioned protective film-forming film can be provided. For example, it can be enumerated: in order to prevent the peeling sheet of dust etc. from adhering to the surface of the protective film-forming film, and to play a role in the cutting process, etc. A sheet for functions such as a dicing sheet for protecting the surface of a film for forming a protective film.

作為較佳的前述支持片，可列舉：半導體晶圓之加工用片之領域中通常所使用之僅由基材構成之支持片、以及由基材及黏著劑層積層而成之支持片等。 Preferable examples of the above-mentioned support sheet include those generally used in the field of semiconductor wafer processing sheets consisting of only a base material, and a support sheet formed by laminating a base material and an adhesive.

支持片可由一層(單層)構成，亦可由兩層以上之複數層構成。於支持片由複數層構成之情形時，這些複數層相互可相同亦可不同。亦即，可全部層相同，亦可全部層皆不同，還可僅一部分層相同。並且，於複數層相互不同之情形時，這些複數層之組合並無特別限定。此處，所謂複數層相互不同，意指各層的材質及厚度的至少一者相互不同。 The support sheet may be constituted by one layer (single layer), or may be constituted by plural layers of two or more layers. When the support sheet is composed of plural layers, these plural layers may be the same or different from each other. That is, all the layers may be the same, all the layers may be different, or only a part of the layers may be the same. In addition, when the plural layers are different from each other, the combination of these plural layers is not particularly limited. Here, that a plurality of layers are different from each other means that at least one of the material and thickness of each layer is different from each other.

支持片的厚度根據目的適宜選擇即可，就可對前述保護膜形成用複合片賦予充分的可撓性，對半導體晶圓之貼附性良好之方面而言，較佳為10μm至500μm，更佳為20μm至350μm，尤佳為30μm至200μm。 The thickness of the support sheet may be appropriately selected according to the purpose, and is preferably 10 μm to 500 μm in terms of imparting sufficient flexibility to the composite sheet for forming a protective film and good adhesion to a semiconductor wafer, and more It is preferably 20 μm to 350 μm, particularly preferably 30 μm to 200 μm.

此處，所謂「支持片的厚度」意指構成支持片之各層的合計厚度，例如於由基材及黏著劑層積層而成之支持片之情形時，意指基材的厚度及黏著劑層的厚度的合計值。 Here, the so-called "thickness of the support sheet" means the total thickness of each layer constituting the support sheet, for example, in the case of a support sheet formed by laminating a base material and an adhesive, it means the thickness of the base material and the adhesive layer the total thickness of .

再者，支持片可至少一面成為凹凸面，關於支持片的厚度，於支持片的該凹凸面中包含凸部之部位中，將該凸部的頂端作為一起點而算出即可。 Furthermore, at least one surface of the support sheet may be a concave-convex surface, and the thickness of the support sheet may be calculated by taking the tip of the convex portion as a common point in the portion including the convex portion on the concave-convex surface of the support sheet.

‧基材 ‧Substrate

前述基材的材質較佳為各種樹脂，作為該樹脂的具體例，可列舉：聚乙烯(低密度聚乙烯(LDPE；Low-density Polyethylene)、直鏈低密度聚乙烯(LLDPE；Linear Low-density Polyethylene)、高密度聚乙烯(HDPE；High-density Polyethylene等))、聚丙烯、乙烯-丙烯共聚物、聚丁烯、聚丁二烯、聚甲基戊烯、聚氯乙烯、氯乙烯共聚物、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯、聚胺基甲酸酯、聚丙烯酸胺基甲酸酯、聚醯亞胺、乙烯-乙酸乙烯酯共聚物、離子聚合物樹脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物、聚苯乙烯、聚碳酸酯、氟樹脂、這些任一樹脂之氫化物、改質物、交聯物或共聚物等。再者，本說明書中，「(甲基)丙烯酸」的概念包括「丙烯酸」及「甲基丙烯酸」兩者。 The material of the aforementioned base material is preferably various resins, and specific examples of the resins include polyethylene (low-density polyethylene (LDPE; Low-density Polyethylene), linear low-density polyethylene (LLDPE; Linear). Low-density Polyethylene), high-density polyethylene (HDPE; High-density Polyethylene, etc.), polypropylene, ethylene-propylene copolymer, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, chlorine Ethylene Copolymer, Polyethylene Terephthalate, Polyethylene Naphthalate, Polybutylene Terephthalate, Polyurethane, Polyurethane Acrylate, Polyimide, Ethylene-vinyl acetate copolymer, ionomer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, polystyrene, polycarbonate, fluororesin, any of these resins Hydrogenated products, modified products, cross-linked products or copolymers, etc. In addition, in this specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid".

於支持片由基材及黏著劑層等其他層積層而成之情形時，基材的厚度可根據目的適宜選擇，較佳為15μm至300μm，更佳為20μm至200μm。藉由基材的厚度為此種範圍，前述保護膜形成用複合片的可撓性、及對半導體晶圓或半導體晶片之貼附性進一步提高。 When the support sheet is formed by laminating the base material and other layers such as an adhesive layer, the thickness of the base material can be appropriately selected according to the purpose, preferably 15 μm to 300 μm, more preferably 20 μm to 200 μm. When the thickness of the base material is in such a range, the flexibility of the composite sheet for forming a protective film and the adhesion to a semiconductor wafer or a semiconductor chip are further improved.

基材可由一層(單層)構成，亦可由兩層以上之複數層構成。於基材由複數層構成之情形時，這些複數層相互可相同亦可不同。此處，所謂「複數層相互可相同亦可不同」意指與上述支持片之情形相同之含義。 The base material may be constituted by one layer (single layer), or may be constituted by plural layers of two or more layers. When the base material is composed of plural layers, these plural layers may be the same or different from each other. Here, "a plurality of layers may be the same or different from each other" means the same meaning as in the case of the above-mentioned support sheet.

於基材由複數層構成之情形時，各層的合計厚度可為上述較佳的基材的厚度。 When the base material is composed of a plurality of layers, the total thickness of each layer may be the thickness of the above-mentioned preferred base material.

基材中的具備黏著劑層的面(表面)的表面粗糙度Ra較佳為0.001μm至0.1μm，更佳為0.005μm至0.08μm，尤佳為0.01μm至0.04μm。藉由基材表面的前述表面粗糙度Ra為前述上限值以下，可對保護膜更清晰地進行雷射印字。 The surface roughness Ra of the surface (surface) provided with the adhesive layer in the base material is preferably 0.001 μm to 0.1 μm, more preferably 0.005 μm to 0.08 μm, particularly preferably 0.01 μm to 0.04 μm. When the surface roughness Ra of the surface of the base material is equal to or less than the upper limit value, the protective film can be more clearly laser-printed.

基材表面的前述表面粗糙度Ra例如可藉由基材之成形條件或表面處理條件等進行調節。 The aforementioned surface roughness Ra of the substrate surface can be adjusted, for example, by the molding conditions or surface treatment conditions of the substrate.

再者，作為藉由切割將半導體晶圓單片化為半導體晶片之方法，例如可列舉利用以下切割之方法：使用刀片切入半導體晶圓之刀片切割、藉由雷射照射切入半導體晶圓之雷射切割、或藉由吹送包含研磨劑之水切入半導體晶圓之水切割等。 Further, as a method of singulating a semiconductor wafer into semiconductor wafers by dicing, for example, a method of using the following dicing methods: blade dicing for cutting into the semiconductor wafer with a blade, and laser cutting for cutting into the semiconductor wafer by laser irradiation are exemplified. jet dicing, or water dicing by blowing water containing abrasives into semiconductor wafers, etc.

另一方面，作為將半導體晶圓單片化為半導體晶片之方法，除利用這些切割之方法以外，亦可列舉以下方法：以聚焦於設定於半導體晶圓內部之焦點之方式，照射紅外區域之雷射光，於半導體晶圓內部形成改質層後，對該半導體晶圓施加力，藉此於形成前述改質層之部位，將半導體晶圓分割、單片化。 On the other hand, as a method of singulating a semiconductor wafer into a semiconductor wafer, in addition to these methods of dicing, a method of irradiating the infrared region so as to focus on a focal point set inside the semiconductor wafer may be exemplified. After the laser light forms a modified layer inside the semiconductor wafer, it exerts force on the semiconductor wafer, thereby dividing and singulating the semiconductor wafer at the portion where the modified layer is formed.

於基材表面的前述表面粗糙度Ra為例如0.01μm至0.2μm之情形時，具備此種基材之保護膜形成用複合片較佳為於在上述半導體晶圓內部形成改質層並將半導體晶圓單片化時使用。 When the surface roughness Ra of the surface of the base material is, for example, 0.01 μm to 0.2 μm, the composite sheet for forming a protective film provided with such a base material is preferably formed by forming a modified layer inside the above-mentioned semiconductor wafer and forming a semiconductor wafer. Used for wafer singulation.

另一方面，基材中的與具備黏著劑層之面(表面)為相反側的面(背面)的表面粗糙度Ra，換言之支持片中的與具備保護膜形成用膜之面(表面)為相反側的面(背面)的表面粗糙度Ra較佳為0.001μm至4μm，更佳為0.005μm至3.7μm，進一步較佳為0.01μm至3.4μm，尤佳為0.02μm至3.1μm。藉由基材背面的前述表面粗糙度Ra為前述上限值以下，可更容易地減少塗層中的與和支持片接觸之側為相反側的表面的表面粗糙度Ra，從而更容易對保護膜清晰進行雷射印字。 On the other hand, the surface roughness Ra of the surface (back surface) opposite to the surface (surface) provided with the adhesive layer in the substrate, in other words, the surface (surface) provided with the protective film forming film in the support sheet is The surface roughness Ra of the opposite side (back surface) is preferably 0.001 μm to 4 μm, more preferably 0.005 μm to 3.7 μm, further preferably 0.01 μm to 3.4 μm, particularly preferably 0.02 μm to 3.1 μm. When the surface roughness Ra of the back surface of the substrate is below the upper limit value, the surface roughness Ra of the surface on the opposite side from the side in contact with the support sheet in the coating layer can be more easily reduced, thereby making it easier to protect. The film is clearly laser printed.

基材背面的前述表面粗糙度Ra例如可藉由基材之成形條件或表面處理條件等進行調節。 The aforementioned surface roughness Ra of the back surface of the substrate can be adjusted, for example, by the molding conditions or surface treatment conditions of the substrate.

作為基材的材質之樹脂亦可經交聯。 The resin used as the material of the base material may also be cross-linked.

另外，作為基材的材質之樹脂可藉由熱塑性樹脂之擠出形成而經片化，亦可經延伸，或亦可藉由硬化性樹脂利用公知手段之薄層化及硬化而經片化。 In addition, the resin as the material of the base material may be formed into a sheet by extrusion of a thermoplastic resin, or may be formed into a sheet by stretching, or may be formed into a sheet by thinning and curing of a curable resin by a known method.

另外，基材可經著色，亦可被實施印刷。 In addition, the substrate may be colored or printed.

就耐熱性優異，且藉由具有適度的柔軟性而具有延伸適性，拾取適性亦良好之方面而言，基材較佳為含有聚丙烯。 It is preferable that the base material contains polypropylene because it is excellent in heat resistance, and has a suitable stretchability and a good pick-up property by having moderate flexibility.

含有聚丙烯之基材例如可為僅由聚丙烯構成之單層或複數層之基材，亦可為聚丙烯層與除聚丙烯以外的樹脂層積層而成之複數層之基材。 The polypropylene-containing substrate may be, for example, a single-layer or plural-layer substrate composed of polypropylene alone, or a plural-layer substrate in which a polypropylene layer and a resin other than polypropylene are laminated.

於保護膜形成用膜為熱硬化性之情形時，藉由基材具有耐熱性，可抑制基材之由熱引起之劣化，可有效抑制於半導體裝置的製造製程中產生不良情況。 When the film for forming a protective film is thermosetting, since the base material has heat resistance, the heat-induced deterioration of the base material can be suppressed, and the occurrence of defects in the manufacturing process of the semiconductor device can be effectively suppressed.

為了提高基材與設置於該基材上之黏著劑層或保護膜形成用膜之接著性，亦可對基材表面實施利用噴砂處理、溶劑處理等之凹凸化處理、電暈放電處理、電子束照射處理、電漿處理、臭氧/紫外線照射處理、火焰處理、鉻酸處理、熱風處理等氧化處理等。另外，亦可對基材表面進行底塗(primer)處理。 In order to improve the adhesion between the base material and the adhesive layer or protective film-forming film provided on the base material, the surface of the base material may be subjected to roughening treatment by sandblasting, solvent treatment, etc., corona discharge treatment, electronic Beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, oxidation treatment such as hot air treatment, etc. In addition, a primer treatment may be performed on the surface of the substrate.

‧黏著劑層 ‧Adhesive layer

前述黏著劑層可適宜使用公知的黏著劑層。 As the above-mentioned adhesive layer, a known adhesive layer can be suitably used.

黏著劑層可使用黏著劑組成物而形成，該黏著劑組成物用以構成該黏著劑層，且含有黏著劑等各種成分。黏著劑組成物中的常溫下不會氣化的成分彼此的含量比率通常與黏著劑層中的前述成分彼此的含量比率相同。再者，本說明書中，所謂「常溫」意指不特別冷或特別熱的溫度，亦即平常的溫度，例如可列舉15℃至25℃之溫度等。 The adhesive layer can be formed using an adhesive composition, which constitutes the adhesive layer and contains various components such as an adhesive. The content ratio of components that do not vaporize at room temperature in the adhesive composition is usually the same as the content ratio of the above-mentioned components in the adhesive layer. In addition, in this specification, "normal temperature" means the temperature which is not particularly cold or particularly hot, that is, a normal temperature, for example, a temperature of 15°C to 25°C, and the like.

黏著劑層的厚度可根據目的適宜選擇，較佳為1μm至100μm，更佳為2μm至80μm，尤佳為3μm至50μm。 The thickness of the adhesive layer can be appropriately selected according to the purpose, and is preferably 1 μm to 100 μm, more preferably 2 μm to 80 μm, and particularly preferably 3 μm to 50 μm.

黏著劑層可由一層(單層)構成，亦可由兩層以上之複 數層構成。於黏著劑層由複數層構成之情形時，這些複數層相互可相同亦可不同。此處，所謂「複數層相互可相同亦可不同」意指與上述支持片之情形相同之含義。 The adhesive layer can be composed of one layer (single layer), or it can also be composed of two or more layers. composed of several layers. When the adhesive layer is composed of plural layers, these plural layers may be the same or different from each other. Here, "a plurality of layers may be the same or different from each other" means the same meaning as in the case of the above-mentioned support sheet.

於黏著劑層由複數層構成之情形時，各層的合計厚度可為上述較佳的黏著劑層的厚度。 When the adhesive layer is composed of a plurality of layers, the total thickness of each layer may be the thickness of the above-mentioned preferred adhesive layer.

作為前述黏著劑，例如可列舉：丙烯酸系樹脂、胺基甲酸酯系樹脂、橡膠系樹脂、聚矽氧系樹脂、乙烯醚系樹脂等黏著性樹脂，於著眼於該樹脂的功能之情形時，例如可列舉能量線硬化性樹脂等。 Examples of the above-mentioned adhesive include adhesive resins such as acrylic resins, urethane resins, rubber-based resins, polysiloxane-based resins, and vinyl ether-based resins. In the case of focusing on the functions of the resins For example, energy ray curable resin etc. are mentioned.

再者，本說明書中，所謂「能量線」意指具有能量量子之電磁波或帶電粒子束，作為該能量線的示例，可列舉紫外線、電子束等。紫外線例如可藉由使用高壓水銀燈、融合(fusion)H型燈或氙氣燈等作為紫外線源進行照射。電子束可照射藉由電子束加速器等產生之電子束。 In addition, in this specification, an "energy ray" means an electromagnetic wave or a charged particle beam which has an energy quantum, and an ultraviolet-ray, an electron beam, etc. are mentioned as an example of this energy ray. The ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion H-type lamp, a xenon lamp, or the like as an ultraviolet source. The electron beam may be irradiated with an electron beam generated by an electron beam accelerator or the like.

作為前述能量線硬化性樹脂，例如可列舉具有(甲基)丙烯醯基、乙烯基等聚合性基之樹脂。 As said energy ray curable resin, resin which has a polymerizable group, such as a (meth)acryloyl group and a vinyl group, is mentioned, for example.

前述黏著性樹脂較佳為丙烯酸系樹脂，更佳為包含源自(甲基)丙烯酸酯之結構單元之(甲基)丙烯酸酯共聚物。 The aforementioned adhesive resin is preferably an acrylic resin, more preferably a (meth)acrylate copolymer containing a structural unit derived from a (meth)acrylate.

關於前述黏著劑層係於含有能量線硬化性樹脂等藉由照射能量線而聚合之成分之情形時，成為能量線硬化性，藉由照射能量線使該黏著劑層之黏著性降低，而容易 拾取後述附有保護膜之半導體晶片。此種黏著劑層例如可使用含有藉由照射能量線而聚合之成分之各種黏著劑組成物而形成。 When the above-mentioned adhesive layer contains a component polymerized by irradiation with energy ray, such as an energy ray-curable resin, it becomes energy ray-curable, and the adhesiveness of the adhesive layer is reduced by irradiating the energy ray, and it is easy to The semiconductor wafer with a protective film mentioned later is picked up. Such an adhesive layer can be formed using, for example, various adhesive compositions containing components polymerized by energy ray irradiation.

<<黏著劑組成物>> <<Adhesive composition>>

作為較佳的前述黏著劑組成物，可列舉含有藉由照射能量線而聚合之成分之黏著劑組成物，作為此種黏著劑組成物，例如可列舉：含有丙烯酸系樹脂及能量線聚合性化合物之黏著劑組成物(以下，有時簡稱為「黏著劑組成物(i)」)；含有丙烯酸系樹脂及異氰酸酯系交聯劑之黏著劑組成物(以下，有時簡稱為「黏著劑組成物(ii)」)等，前述丙烯酸系樹脂係具有羥基且於側鏈具有聚合性基之丙烯酸系樹脂(例如，具有羥基且經由胺基甲酸酯鍵而於側鏈具有聚合性基之丙烯酸系樹脂)。 Preferable examples of the adhesive composition include those containing components polymerized by irradiation with energy rays. Examples of such adhesive compositions include acrylic resins and energy ray polymerizable compounds. The adhesive composition (hereinafter, sometimes referred to as "adhesive composition (i)"); the adhesive composition containing acrylic resin and isocyanate crosslinking agent (hereinafter, sometimes referred to as "adhesive composition (i)"); (ii)"), etc., the aforementioned acrylic resin is an acrylic resin having a hydroxyl group and a polymerizable group in the side chain (for example, an acrylic resin having a hydroxyl group and having a polymerizable group in the side chain via a urethane bond) resin).

<黏著劑組成物(i)> <Adhesive composition (i)>

黏著劑組成物(i)含有前述丙烯酸系樹脂及能量線聚合性化合物作為必需成分。 The adhesive composition (i) contains the aforementioned acrylic resin and the energy ray polymerizable compound as essential components.

以下，對各成分進行說明。 Hereinafter, each component will be described.

[丙烯酸系樹脂] [acrylic resin]

作為黏著劑組成物(i)中較佳的前述丙烯酸系樹脂，例如可列舉：使(甲基)丙烯酸酯與視需要使用之除(甲基)丙 烯酸酯以外的單體作為單體進行聚合而獲得之(甲基)丙烯酸酯共聚物。 As the aforementioned acrylic resin preferable in the adhesive composition (i), for example, (meth)acrylic acid ester and (meth)acrylic acid which is optionally used can be mentioned. A (meth)acrylate copolymer obtained by polymerizing monomers other than alkenoate as a monomer.

作為前述(甲基)丙烯酸酯，例如可列舉：(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)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯((甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯((甲基)丙烯酸肉豆蔻酯)、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯((甲基)丙烯酸棕櫚酯)、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯((甲基)丙烯酸硬脂酯)、(甲基)丙烯酸異十八烷基酯((甲基)丙烯酸異硬脂酯)等構成烷基酯之烷基為碳數為1至18之鏈狀結構之(甲基)丙烯酸烷基酯；(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊酯等(甲基)丙烯酸環烷基酯；(甲基)丙烯酸苄酯等(甲基)丙烯酸芳烷基酯；(甲基)丙烯酸二環戊烯酯等(甲基)丙烯酸環烯基酯；(甲基)丙烯酸二環戊烯氧基乙酯等(甲基)丙烯酸環烯氧基烷基酯；(甲基)丙烯醯亞胺；(甲基)丙烯酸縮水甘油酯等含縮水甘油基之(甲基)丙烯酸酯；(甲基)丙烯酸羥基甲酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2- 羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等含羥基之(甲基)丙烯酸酯等。 As said (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylic acid are mentioned, for example Amyl ester, hexyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ( n-nonyl meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate ((meth)acrylate ) lauryl acrylate), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, ( Cetyl meth)acrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate) , isostearyl (meth)acrylate (isostearyl (meth)acrylate), etc. The alkyl group constituting the alkyl ester is a (meth)acrylate alkyl group with a chain structure with a carbon number of 1 to 18 (Meth) cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate; (meth)acrylate aralkyl esters such as benzyl (meth)acrylate; ( (Meth) cycloalkenyl acrylates such as dicyclopentenyl meth)acrylate; (meth) cycloalkenyloxyalkyl acrylates such as dicyclopentenyloxyethyl (meth)acrylate; ) Acrylimide; Glycidyl (meth)acrylate and other glycidyl-containing (meth)acrylates; (meth)acrylate hydroxymethyl, (meth)acrylate 2-hydroxyethyl, (meth)acrylate ) 2-hydroxypropyl acrylate, 3-hydroxypropyl (meth)acrylate, 2-(meth)acrylate Hydroxybutyl, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyl-containing (meth)acrylates.

作為前述(甲基)丙烯酸酯以外的單體，例如可列舉：(甲基)丙烯酸、衣康酸、乙酸乙烯酯、丙烯腈、苯乙烯、N-羥甲基丙烯醯胺等。 As a monomer other than the said (meth)acrylate, (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylol acrylamide etc. are mentioned, for example.

構成丙烯酸系樹脂之前述(甲基)丙烯酸酯、除前述(甲基)丙烯酸酯以外的單體等各種單體均可僅為1種，亦可為2種以上。 Various monomers, such as the said (meth)acrylate and monomers other than the said (meth)acrylate which comprise an acrylic resin, may be only 1 type, and may be 2 or more types.

黏著劑組成物(i)所含有之丙烯酸系樹脂可僅為1種，亦可為2種以上。 The acrylic resin contained in the adhesive composition (i) may be only one type or two or more types.

黏著劑組成物(i)中的丙烯酸系樹脂的含量相對於黏著劑組成物(i)中的溶劑以外的全部含有成分的總量，較佳為40質量%至99質量%，更佳為50質量%至91質量%。 The content of the acrylic resin in the adhesive composition (i) is preferably 40% by mass to 99% by mass, more preferably 50% by mass relative to the total amount of all components other than the solvent in the adhesive composition (i) mass % to 91 mass %.

[能量線聚合性化合物] [Energy ray polymerizable compound]

前述能量線聚合性化合物係藉由照射能量線進行聚合而硬化之化合物，作為該化合物的示例，可列舉於分子內具有能量線硬化性雙鍵等能量線聚合性基之化合物。 The aforementioned energy ray polymerizable compound is a compound that is polymerized and cured by irradiation with energy rays, and examples of the compound include compounds having an energy ray polymerizable group such as an energy ray-curable double bond in the molecule.

作為前述能量線聚合性化合物，例如可列舉具有能量線聚合性基之低分子量化合物(單官能或多官能的單體及低聚物)，更具體而言，可列舉：三羥甲基丙烷三丙烯酸酯、四羥甲基甲烷四丙烯酸酯、季戊四醇三丙烯酸酯、二季戊四醇單羥基五丙烯酸酯、二季戊四醇六丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯等丙烯酸酯；二環戊二烯二甲氧基二丙烯酸酯等含環狀脂肪族骨架之丙烯酸酯；聚乙二醇二丙烯酸酯、寡酯丙烯酸酯、丙烯酸胺基甲酸酯低聚物、環氧改性丙烯酸酯、聚醚丙烯酸酯、衣康酸低聚物等丙烯酸酯系化合物等。 Examples of the energy ray polymerizable compound include low-molecular-weight compounds (monofunctional or polyfunctional monomers and oligomers) having an energy ray polymerizable group, and more specifically, trimethylolpropane trimethylolide Acrylates, tetramethylolmethane tetraacrylate, pentaerythritol triacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol hexaacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate Acrylates such as acrylates; acrylates containing cyclic aliphatic skeletons such as dicyclopentadiene dimethoxydiacrylate; polyethylene glycol diacrylates, oligoester acrylates, acrylic urethane oligomers acrylic compounds, epoxy-modified acrylates, polyether acrylates, itaconic acid oligomers, etc.

前述能量線聚合性化合物的分子量較佳為100至30000，更佳為300至10000。 The molecular weight of the energy ray polymerizable compound is preferably from 100 to 30,000, more preferably from 300 to 10,000.

黏著劑組成物(i)所含有之能量線聚合性化合物可僅為1種，亦可為2種以上。 The energy ray polymerizable compound contained in the adhesive composition (i) may be only one type or two or more types.

黏著劑組成物(i)中的能量線聚合性化合物的含量相對於前述丙烯酸系樹脂的含量100質量份，較佳為1質量份至125質量份，更佳為10質量份至125質量份。 The content of the energy ray polymerizable compound in the adhesive composition (i) is preferably 1 to 125 parts by mass, more preferably 10 to 125 parts by mass relative to 100 parts by mass of the content of the acrylic resin.

[光聚合起始劑] [Photopolymerization initiator]

黏著劑組成物(i)除前述丙烯酸系樹脂及能量線聚合性化合物以外，亦可含有光聚合起始劑。 The adhesive composition (i) may contain a photopolymerization initiator in addition to the aforementioned acrylic resin and the energy ray polymerizable compound.

前述光聚合起始劑可為公知的光聚合起始劑，具體而言，例如可列舉：4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮、α-羥基-α,α'-二甲基苯乙酮、2-甲基-2-羥基苯丙酮、1-羥基環己基苯基酮、2-羥-1-{4-[4-(2-羥基-2-甲基-丙醯基)-苄基]苯基}-2-甲基-丙烷-1-酮等α-酮醇系化合物；甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎福林(morpholine)基丙烷-1-酮等苯乙酮系化合物；安息香乙醚、安息香異丙醚、大茴香偶姻甲醚等安息香醚系化合物；苯偶醯二甲基縮酮等縮酮系化合物；2-萘磺醯氯等芳香族磺醯氯系化合物；1-苯酮-1,1-丙二酮-2-(鄰乙氧基羰基)肟等光活性肟系化合物；二苯甲酮、苯甲醯苯甲酸、3,3'-二甲基-4-甲氧基二苯甲酮等二苯甲酮系化合物；噻噸酮(thioxanthone)、2-氯噻噸酮、2-甲基噻噸酮、2,4-二甲基噻噸酮、異丙基噻噸酮、2,4-二氯噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等噻噸酮系化合物；樟腦醌；鹵代酮；醯基氧化膦；醯基膦酸鹽/酯等。 The aforementioned photopolymerization initiator may be a known photopolymerization initiator, and specific examples thereof include 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, α- Hydroxy-α,α'-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-1-{4-[4-(2-hydroxy -2-Methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one and other α-keto alcohol compounds; methoxyacetophenone, 2,2-dimethoxy yl-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine Acetophenone-based compounds such as propane-1-one; benzoin ether-based compounds such as benzoin ethyl ether, benzoin isopropyl ether, anisin methyl ether, etc.; ketal-based compounds such as benzoin dimethyl ketal; 2-naphthalenesulfonic acid Aromatic sulfonic acid chloride-based compounds such as acyl chloride; photoactive oxime-based compounds such as 1-benzophenone-1,1-propanedione-2-(o-ethoxycarbonyl) oxime; benzophenone, benzylbenzene Formic acid, 3,3'-dimethyl-4-methoxybenzophenone and other benzophenone-based compounds; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-Dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Isothioxanthone compounds; camphorquinone; halogenated ketones; acyl phosphine oxide; acyl phosphonates/esters, etc.

黏著劑組成物(i)所含有之光聚合起始劑可僅為1種，亦可為2種以上。 The photopolymerization initiator contained in the adhesive composition (i) may be only one type or two or more types.

於使用光聚合起始劑之情形時，黏著劑組成物(i)中的光聚合起始劑的含量相對於前述能量線聚合性化合物的含量100質量份，較佳為0.1質量份至10質量份，更佳 為1質量份至5質量份。藉由光聚合起始劑的前述含量為前述下限值以上，可獲得充分的由使用光聚合起始劑所帶來之功效。另外，藉由光聚合起始劑的前述含量為前述上限值以下，可抑制由過量的光聚合起始劑產生副生成分，從而使黏著劑層更良好地進行硬化。 In the case of using a photopolymerization initiator, the content of the photopolymerization initiator in the adhesive composition (i) is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the energy ray polymerizable compound content portion, better It is 1 mass part to 5 mass parts. When the said content of a photopolymerization initiator is more than the said lower limit, sufficient effect by using a photopolymerization initiator can be obtained. Moreover, since the said content of a photoinitiator is below the said upper limit, generation|occurrence|production of a by-product from an excess photoinitiator can be suppressed, and hardening of an adhesive bond layer can be performed more favorably.

[交聯劑] [Crosslinking agent]

黏著劑組成物(i)除前述丙烯酸系樹脂及能量線聚合性化合物以外，亦可含有交聯劑。 The adhesive composition (i) may contain a crosslinking agent in addition to the aforementioned acrylic resin and the energy ray polymerizable compound.

作為前述交聯劑，例如可列舉：有機多元異氰酸酯化合物、有機多元亞胺化合物等。 As said crosslinking agent, an organic polyvalent isocyanate compound, an organic polyvalent imine compound, etc. are mentioned, for example.

作為前述有機多元異氰酸酯化合物，例如可列舉：芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物、脂環族多元異氰酸酯化合物及這些化合物的三聚物、異氰脲酸酯體及加合物；使前述芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物或脂環族多元異氰酸酯化合物與多元醇化合物反應而獲得之末端異氰酸酯胺基甲酸酯預聚物等。前述加合物意指前述芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物或脂環族多元異氰酸酯化合物，與乙二醇、丙二醇、新戊二醇、三羥甲基丙烷或蓖麻油等含低分子活性氫化合物之反應物。 Examples of the organic polyvalent isocyanate compound include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, and trimers, isocyanurates, and adducts of these compounds; An aromatic polyvalent isocyanate compound, an aliphatic polyvalent isocyanate compound, or an alicyclic polyvalent isocyanate compound and a polyol compound are reacted with a terminal isocyanate urethane prepolymer, and the like. The aforementioned adduct means the aforementioned aromatic polyvalent isocyanate compound, aliphatic polyvalent isocyanate compound or alicyclic polyvalent isocyanate compound, which is mixed with ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil and other low molecular weight compounds. Reactants for active hydrogen compounds.

作為前述有機多元異氰酸酯化合物，更具體而言，例如可列舉：2,4-甲苯二異氰酸酯；2,6-甲苯二異氰酸酯；1,3-苯二甲基二異氰酸酯；1,4-二甲苯二異氰酸酯；二苯基甲烷-4,4'-二異氰酸酯；二苯基甲烷-2,4'-二異氰酸酯；3-甲基二苯基甲烷二異氰酸酯；六亞甲基二異氰酸酯；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；對三羥甲基丙烷等多元醇的全部或一部分羥基，加成甲苯二異氰酸酯及六亞甲基二異氰酸酯的任一者或兩者而成之化合物；離胺酸二異氰酸酯等。 As said organic polyvalent isocyanate compound, more specifically, 2, 4- toluene diisocyanate; 2, 6- toluene diisocyanate; 1, 3- xylylene diisocyanate; 1, 4- xylene diisocyanate are mentioned, for example Isocyanates; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophorone Diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; All or part of the hydroxyl groups of polyols such as p-trimethylolpropane, added with toluene diisocyanate and Compounds of either or both of hexamethylene diisocyanate; lysine diisocyanate, etc.

作為前述有機多元亞胺化合物，例如可列舉：N,N'-二苯基甲烷-4,4'-雙(1-氮丙啶甲醯胺)、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、N,N'-甲苯-2,4-雙(1-氮丙啶甲醯胺)三伸乙基三聚氰胺等。 As said organic polyvalent imine compound, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-nitrogen Propidyl propionate, tetramethylolmethane-tri-beta-aziridinyl propionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide) tris-ethyl melamine, etc.

於使用異氰酸酯化合物作為交聯劑之情形時，作為丙烯酸系樹脂，較佳為使用含羥基之聚合物。於交聯劑具有異氰酸酯基且丙烯酸系樹脂具有羥基之情形時，可藉由這些異氰酸酯基與羥基之反應，而將交聯結構簡便地導入至黏著劑層中。 When an isocyanate compound is used as a crosslinking agent, it is preferable to use a hydroxyl-containing polymer as an acrylic resin. When the crosslinking agent has an isocyanate group and the acrylic resin has a hydroxyl group, the crosslinked structure can be easily introduced into the adhesive layer by the reaction between these isocyanate groups and the hydroxyl group.

黏著劑組成物(i)所含有之交聯劑可僅為1種，亦可為2種以上。 The crosslinking agent contained in the adhesive composition (i) may be only one type or two or more types.

於使用交聯劑之情形時，黏著劑組成物(i)中的交聯劑的含量相對於前述丙烯酸系樹脂的含量100質量份，較佳為0.01質量份至20質量份，更佳為0.1質量份至16質量份。 In the case of using a crosslinking agent, the content of the crosslinking agent in the adhesive composition (i) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the content of the aforementioned acrylic resin, more preferably 0.1 parts by mass to 16 parts by mass.

[溶劑] [solvent]

黏著劑組成物(i)較佳為除前述丙烯酸系樹脂及能量線聚合性化合物以外，進一步含有溶劑。 The adhesive composition (i) preferably further contains a solvent in addition to the aforementioned acrylic resin and the energy ray polymerizable compound.

前述溶劑並無特別限定，作為較佳的前述溶劑，例如可列舉：甲苯、二甲苯等烴；甲醇、乙醇、2-丙醇、異丁醇(2-甲基丙烷-1-醇)、1-丁醇等醇；乙酸乙酯等酯；丙酮、甲基乙基酮等酮；四氫呋喃等醚；二甲基甲醯胺、N-甲基吡咯啶酮等醯胺(具有醯胺鍵之化合物)等。 The aforementioned solvent is not particularly limited, and preferable examples of the aforementioned solvent include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), 1 - Alcohols such as butanol; Esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran; )Wait.

黏著劑組成物(i)所含有之溶劑可僅為1種，亦可為2種以上。 The solvent contained in the adhesive composition (i) may be only one type or two or more types.

黏著劑組成物(i)含有溶劑之情形時，溶劑的含量較佳為40質量%至90質量%，更佳為50質量%至80質量%。 When the adhesive composition (i) contains a solvent, the content of the solvent is preferably 40 to 90 mass %, more preferably 50 to 80 mass %.

[其他成分] [other ingredients]

黏著劑組成物(i)中，除前述丙烯酸系樹脂及能量線聚合性化合物以外，亦可在無損本發明的功效之範圍內，含有不屬於前述光聚合起始劑、交聯劑及溶劑之其他成分。 In the adhesive composition (i), in addition to the aforementioned acrylic resin and the energy ray polymerizable compound, it may also contain other substances not belonging to the aforementioned photopolymerization initiator, crosslinking agent and solvent within the scope of impairing the effect of the present invention. other ingredients.

前述其他成分可為公知的成分，可根據目的任意選擇，並無特別限定，作為較佳的其他成分，例如可列舉：染料、顏料、抗劣化劑、抗靜電劑、阻燃劑、聚矽氧化合物、鏈轉移劑等各種添加劑。 The above-mentioned other components may be known components, and can be arbitrarily selected according to the purpose without particular limitation. Examples of preferable other components include: dyes, pigments, anti-deterioration agents, antistatic agents, flame retardants, polysiloxanes Various additives such as compounds and chain transfer agents.

黏著劑組成物(i)所含有之前述其他成分可僅為1種，亦可為2種以上。 The said other component contained in an adhesive composition (i) may be only 1 type, and may be 2 or more types.

<黏著劑組成物(ii)> <Adhesive composition (ii)>

黏著劑組成物(ii)含有丙烯酸系樹脂及異氰酸酯系交聯劑作為必需成分，前述丙烯酸系樹脂係具有羥基且於側鏈具有聚合性基之丙烯酸系樹脂(例如，具有羥基且經由胺基甲酸酯鍵而於側鏈具有聚合性基之丙烯酸系樹脂)。 The adhesive composition (ii) contains, as essential components, an acrylic resin and an isocyanate-based crosslinking agent, and the aforementioned acrylic resin is an acrylic resin having a hydroxyl group and a polymerizable group in the side chain (for example, having a hydroxyl group and passing through an aminomethyl group) Acrylic resins having a polymerizable group in the side chain with an acid ester bond).

於使用黏著劑組成物(ii)之情形時，藉由丙烯酸系樹脂於側鏈具有聚合性基，相較於如黏著劑組成物(i)之情形般，使用能量線聚合性化合物，藉由照射能量線進行聚合反應之情形而言，因聚合反應(硬化)後的黏著劑層的黏著性降低而自被黏著體之剝離性提高，附有保護膜之半導體晶片之拾取性提高。 In the case of using the adhesive composition (ii), since the acrylic resin has a polymerizable group in the side chain, compared with the case of the adhesive composition (i), the energy ray polymerizable compound is used by When the polymerization reaction is performed by irradiating the energy ray, the adhesiveness of the adhesive layer after the polymerization reaction (curing) is reduced, the peelability from the adherend is improved, and the pick-up property of the semiconductor wafer with the protective film is improved.

再者，本說明書中，關於黏著劑組成物(ii)中的「丙烯酸系樹脂」之記載，只要無特別說明，則意指「於側鏈具有聚合性基之丙烯酸系樹脂」。 In addition, in this specification, the description of "acrylic resin" in the adhesive composition (ii) means "acrylic resin having a polymerizable group in a side chain" unless otherwise specified.

[丙烯酸系樹脂] [acrylic resin]

作為上述之於側鏈具有聚合性基之丙烯酸系樹脂，例如可列舉以下述方式獲得之丙烯酸系樹脂：使作為單體之不具有羥基之不含烴基之(甲基)丙烯酸酯，與具有羥基之含羥基之(甲基)丙烯酸酯等含羥基之化合物進行共聚合，而獲得含羥基之共聚物，使所獲得之含羥基之共聚物的羥基，與具有異氰酸酯基及聚合性基之化合物的異氰酸酯基進行反應，而形成胺基甲酸酯鍵，從而獲得丙烯酸系樹脂。 As the acrylic resin having a polymerizable group in the side chain, for example, an acrylic resin obtained by combining a (meth)acrylate having no hydroxyl group as a monomer and a hydrocarbon group-free (meth)acrylate having a hydroxyl group, and A hydroxyl-containing compound such as a hydroxyl-containing (meth)acrylate is copolymerized to obtain a hydroxyl-containing copolymer, so that the hydroxyl group of the obtained hydroxyl-containing copolymer and the compound having an isocyanate group and a polymerizable group are The isocyanate group reacts to form a urethane bond, thereby obtaining an acrylic resin.

作為前述不含羥基之(甲基)丙烯酸酯，例如可列舉：黏著劑組成物(i)中的(甲基)丙烯酸酯中除含羥基之(甲基)丙烯酸酯以外的(甲基)丙烯酸酯。 As said hydroxyl group-free (meth)acrylate, for example, among the (meth)acrylates in the adhesive composition (i), (meth)acrylic acid other than the hydroxyl group-containing (meth)acrylate can be mentioned. ester.

另外，作為前述含羥基之化合物，可列舉：與黏著劑組成物(i)中的含羥基之(甲基)丙烯酸酯相同之化合物。 Moreover, as said hydroxyl-containing compound, the compound similar to the hydroxyl-containing (meth)acrylate in an adhesive composition (i) is mentioned.

構成前述丙烯酸系樹脂之不含羥基之(甲基)丙烯酸酯及含羥基之化合物可分別僅為1種，亦可為2種以上。 The hydroxyl group-free (meth)acrylate and the hydroxyl group-containing compound constituting the above-mentioned acrylic resin may be only one type, respectively, or two or more types may be used.

作為前述具有異氰酸酯基及聚合性基之化合物，例如可列舉：異氰酸2-甲基丙烯醯氧基乙酯等含異氰酸酯基之(甲基)丙烯酸酯等。 As a compound which has the said isocyanate group and a polymerizable group, isocyanate group-containing (meth)acrylates, such as 2-methacryloyloxyethyl isocyanate, are mentioned, for example.

構成前述丙烯酸系樹脂之前述具有異氰酸酯基及聚合性基之化合物可僅為1種，亦可為2種以上。 The compound which has the said isocyanate group and a polymerizable group which comprises the said acrylic resin may be only 1 type, and may be 2 or more types.

黏著劑組成物(ii)所含有之丙烯酸系樹脂可僅為1種，亦可為2種以上。 The acrylic resin contained in the adhesive composition (ii) may be only one type or two or more types.

黏著劑組成物(ii)中的丙烯酸系樹脂的含量相對於黏著劑組成物(ii)中的溶劑以外的全部含有成分的總量，較佳為80質量%至99質量%，更佳為90質量%至97質量%。 The content of the acrylic resin in the adhesive composition (ii) is preferably 80% by mass to 99% by mass, more preferably 90% by mass relative to the total amount of all components other than the solvent in the adhesive composition (ii) mass % to 97 mass %.

[異氰酸酯系交聯劑] [Isocyanate based crosslinking agent]

作為前述異氰酸酯系交聯劑，例如可列舉：與黏著劑組成物(i)中的作為交聯劑之前述有機多元異氰酸酯化合物相同之化合物。 As said isocyanate type crosslinking agent, the same compound as the said organic polyvalent isocyanate compound which is a crosslinking agent in an adhesive composition (i) is mentioned, for example.

黏著劑組成物(ii)所含有之異氰酸酯系交聯劑可僅為1種，亦可為2種以上。 Only one type of isocyanate-based crosslinking agent contained in the adhesive composition (ii) may be used, or two or more types may be used.

黏著劑組成物(ii)中的異氰酸酯系交聯劑所具有之異氰酸酯基的莫耳數相對於黏著劑組成物(ii)中的丙烯酸系樹脂所具有之羥基的莫耳數，較佳為0.2倍至3倍。藉由異氰酸酯基的前述莫耳數為前述下限值以上，因硬化後的黏著劑層的黏著性降低而自被黏著體之剝離性提高，附有保護膜之半導體晶片之拾取性提高。另外，藉由異氰酸酯基的前述莫耳數為前述上限值以下，可進一步抑制因異氰酸酯系交聯劑彼此之反應而產生副產物。 The molar number of isocyanate groups in the isocyanate-based crosslinking agent in the adhesive composition (ii) is preferably 0.2 relative to the molar number of hydroxyl groups in the acrylic resin in the adhesive composition (ii) times to 3 times. Since the said molar number of an isocyanate group is more than the said lower limit, the adhesiveness of the adhesive layer after hardening falls, the peelability from a to-be-adhered body improves, and the pick-up property of the semiconductor wafer with a protective film improves. Moreover, by the said molar number of an isocyanate group being below the said upper limit, generation|occurrence|production of a by-product by the reaction of isocyanate type crosslinking agents can be suppressed further.

黏著劑組成物(ii)中的異氰酸酯系交聯劑的含量以異氰酸酯基的莫耳數成為如上所述之範圍之方式適宜調節即可，但較佳為滿足此種條件，並且相對於丙烯酸系樹脂的含量100質量份，為0.01質量份至20質量份，更佳為0.1質量份至15質量份，尤佳為0.3質量份至12質量份。 The content of the isocyanate-based crosslinking agent in the adhesive composition (ii) may be appropriately adjusted so that the number of moles of isocyanate groups falls within the above-mentioned range, but it is preferable to satisfy such a condition, and relative to the acrylic acid-based crosslinking agent. The content of the resin is 0.01 to 20 parts by mass per 100 parts by mass, more preferably 0.1 to 15 parts by mass, and particularly preferably 0.3 to 12 parts by mass.

[光聚合起始劑] [Photopolymerization initiator]

黏著劑組成物(ii)中，除前述丙烯酸系樹脂及異氰酸酯系交聯劑以外，亦可含有光聚合起始劑。 The adhesive composition (ii) may contain a photopolymerization initiator in addition to the aforementioned acrylic resin and isocyanate-based crosslinking agent.

作為前述光聚合起始劑，例如可列舉與黏著劑組成物(i)之情形相同之光聚合起始劑。 As said photoinitiator, the photoinitiator similar to the case of an adhesive composition (i) is mentioned, for example.

黏著劑組成物(ii)所含有之光聚合起始劑可僅為1種，亦可為2種以上。 The photopolymerization initiator contained in the adhesive composition (ii) may be only one type or two or more types.

於使用光聚合起始劑之情形時，黏著劑組成物(ii)中的光聚合起始劑的含量相對於丙烯酸系樹脂的含量100質量份，較佳為0.05質量份至20質量份。 In the case of using a photopolymerization initiator, the content of the photopolymerization initiator in the adhesive composition (ii) is preferably 0.05 to 20 parts by mass relative to 100 parts by mass of the content of the acrylic resin.

藉由光聚合起始劑的前述含量為前述下限值以上，可獲得充分的由使用光聚合起始劑所帶來之功效。另外，藉由光聚合起始劑的前述含量為前述上限值以下，可抑制由過量的光聚合起始劑產生副生成分，從而使黏著劑層更良好地進行硬化。 When the said content of a photopolymerization initiator is more than the said lower limit, sufficient effect by using a photopolymerization initiator can be obtained. Moreover, since the said content of a photoinitiator is below the said upper limit, generation|occurrence|production of a by-product from an excess photoinitiator can be suppressed, and hardening of an adhesive bond layer can be performed more favorably.

[溶劑] [solvent]

黏著劑組成物(ii)較佳為除前述丙烯酸系樹脂及異氰酸酯系交聯劑以外，進一步含有溶劑。 The adhesive composition (ii) preferably further contains a solvent in addition to the aforementioned acrylic resin and isocyanate-based crosslinking agent.

作為前述溶劑，例如可列舉與黏著劑組成物(i)之情形相同之溶劑。 As said solvent, the thing similar to the case of an adhesive composition (i) is mentioned, for example.

黏著劑組成物(ii)所含有之溶劑可僅為1種，亦可為2種以上。 The solvent contained in the adhesive composition (ii) may be only one type or two or more types.

黏著劑組成物(ii)含有溶劑之情形時，溶劑的含量較佳為40質量%至90質量%，更佳為50質量%至80質量%。 When the adhesive composition (ii) contains a solvent, the content of the solvent is preferably 40 to 90 mass %, more preferably 50 to 80 mass %.

[其他成分] [other ingredients]

黏著劑組成物(ii)中，除前述丙烯酸系樹脂及異氰酸酯系交聯劑以外，亦可在無損本發明的功效之範圍內，含有不屬於前述光聚合起始劑及溶劑之其他成分。 In addition to the aforementioned acrylic resin and isocyanate-based crosslinking agent, the adhesive composition (ii) may also contain other components that do not belong to the aforementioned photopolymerization initiator and solvent within the scope of impairing the effect of the present invention.

作為前述其他成分，例如可列舉與黏著劑組成物(i)之情形相同之成分。 As said other component, the thing similar to the case of an adhesive composition (i) is mentioned, for example.

黏著劑組成物(ii)所含有之前述其他成分可僅為1種，亦可為2種以上。 The said other component contained in an adhesive composition (ii) may be only 1 type, and may be 2 or more types.

至此，對含有藉由照射能量線而聚合之成分之黏著劑組成物進行了說明，但形成黏著劑層時，亦可使用不含藉由照射能量線而聚合之成分之黏著劑組成物。亦即，黏著劑層亦可為不具有能量線硬化性之非能量線硬化性之層。 Heretofore, the adhesive composition containing the component polymerized by irradiation with energy ray has been described, but when forming the adhesive layer, an adhesive composition containing no component polymerized by irradiation with energy ray can also be used. That is, the adhesive layer may be a non-energy ray sclerosing layer which does not have energy ray sclerosis.

作為較佳的此種非能量線硬化性黏著劑組成物，例如可列舉含有丙烯酸系樹脂及交聯劑之黏著劑組成物(以下，有時簡稱為「黏著劑組成物(iii)」)等，亦可含有溶劑、不屬於溶劑之其他成分等任意成分。 As such a preferable non-energy ray-curable adhesive composition, for example, an adhesive composition containing an acrylic resin and a crosslinking agent (hereinafter, may be simply referred to as "adhesive composition (iii)"), etc. , and may contain optional components such as solvents and other components that are not solvents.

<黏著劑組成物(iii)> <Adhesive composition (iii)>

黏著劑組成物(iii)所含有之前述丙烯酸系樹脂、交聯劑、溶劑及其他成分均與黏著劑組成物(i)中的這些成分相同。 The aforementioned acrylic resin, crosslinking agent, solvent and other components contained in the adhesive composition (iii) are the same as those in the adhesive composition (i).

黏著劑組成物(iii)中的丙烯酸系樹脂的含量相對於黏著劑組成物(iii)中的溶劑以外的全部含有成分的總量，較佳為40質量%至99質量%，更佳為50質量%至93質量%。 The content of the acrylic resin in the adhesive composition (iii) is preferably 40% by mass to 99% by mass, more preferably 50% by mass relative to the total amount of all components other than the solvent in the adhesive composition (iii) mass % to 93 mass %.

黏著劑組成物(iii)中的交聯劑的含量相對於丙烯酸系樹脂的含量100質量份，較佳為3質量份至30質量份，更佳為5質量份至25質量份。 The content of the crosslinking agent in the adhesive composition (iii) is preferably 3 to 30 parts by mass, more preferably 5 to 25 parts by mass, relative to 100 parts by mass of the content of the acrylic resin.

黏著劑組成物(iii)除上述方面以外，與黏著劑組成物(i)相同。 The adhesive composition (iii) is the same as the adhesive composition (i) except for the above-mentioned aspects.

<<黏著劑組成物的製造方法>> <<Manufacturing method of adhesive composition>>

黏著劑組成物(i)至黏著劑組成物(iii)等前述黏著劑組成物可藉由下述方式而獲得：將前述黏著劑、視需要之除 前述黏著劑以外的成分等用以構成各黏著劑組成物之成分加以調配。 The aforementioned adhesive compositions such as the adhesive composition (i) to the adhesive composition (iii) can be obtained by the following methods: Components other than the above-mentioned adhesive are prepared for the components constituting each adhesive composition.

調配各成分時之添加順序並無特別限定，亦可同時添加2種以上之成分。 The order of addition at the time of preparing each component is not particularly limited, and two or more components may be added at the same time.

調配時混合各成分之方法並無特別限定，自以下公知的方法中適宜選擇即可：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機進行混合之方法；施加超音波進行混合之方法等。 The method of mixing the components during preparation is not particularly limited, and may be appropriately selected from the following well-known methods: a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, and a method of applying ultrasonic waves for mixing method etc.

關於添加及混合各成分時的溫度及時間，只要不會使各調配成分劣化，即無特別限定，適宜調節即可，溫度較佳為15℃至30℃。 The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounded component is not degraded, and may be appropriately adjusted, and the temperature is preferably 15°C to 30°C.

○保護膜形成用膜 ○ Film for protective film formation

前述保護膜形成用膜可為熱硬化性及能量線硬化性之任一種。保護膜形成用膜經由硬化而最終成為耐衝擊性高的保護膜。該保護膜例如防止切割步驟以後之半導體晶片中產生龜裂。 The film for forming a protective film may be any of thermosetting properties and energy ray curing properties. The film for protective film formation finally becomes a protective film with high impact resistance by hardening. The protective film prevents, for example, cracks from occurring in the semiconductor wafer after the dicing step.

保護膜形成用膜可使用後述之熱硬化性保護膜形成用組成物或能量線硬化性保護膜形成用組成物(以下，有時將這些統稱為「保護膜形成用組成物」)而形成。 The film for forming a protective film can be formed using a composition for forming a thermosetting protective film or a composition for forming an energy ray curable protective film (hereinafter, these may be collectively referred to as a "composition for forming a protective film") to be described later.

保護膜形成用膜可僅為一層(單層)，亦可為兩層以上之複數層，於為複數層之情形時，這些複數層相互可相同亦可不同，這些複數層之組合並無特別限定。 The film for forming a protective film may be only one layer (single layer), or it may be a plurality of layers of two or more layers. In the case of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.

保護膜形成用膜的厚度並無特別限定，較佳為1μm至100μm，更佳為5μm至75μm，尤佳為5μm至50μm。藉由保護膜形成用膜的厚度為前述下限值以上，對作為被黏著體之半導體晶圓及半導體晶片之接著力變得更大。另外，藉由保護膜形成用膜的厚度為前述上限值以下，在拾取半導體晶片時，利用剪切力可將作為硬化物之保護膜更容易地切斷。 The thickness of the film for forming a protective film is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 5 μm to 75 μm, and particularly preferably 5 μm to 50 μm. When the thickness of the film for protective film formation is more than the said lower limit, the adhesive force with respect to the semiconductor wafer and the semiconductor chip which are to-be-adhered bodies becomes large. Moreover, when the thickness of the film for protective film formation is below the said upper limit, when picking up a semiconductor wafer, the protective film which is a cured product can be cut|disconnected more easily by shearing force.

‧熱硬化性保護膜形成用膜 ‧Film for forming thermosetting protective film

作為較佳的熱硬化性保護膜形成用膜，例如可列舉含有聚合物成分(A)及熱硬化性成分(B)之膜。聚合物成分(A)係被視為聚合性化合物進行聚合反應而形成之成分。另外，熱硬化性成分(B)係可將熱作為反應之觸發(trigger)而進行硬化(聚合)反應之成分。再者，本實施形態中，聚合反應中亦包括縮聚反應。 As a preferable film for thermosetting protective film formation, the film containing a polymer component (A) and a thermosetting component (B) is mentioned, for example. The polymer component (A) is regarded as a component formed by a polymerization reaction of a polymerizable compound. Moreover, a thermosetting component (B) is a component which can perform a hardening (polymerization) reaction using heat as a trigger of a reaction. In addition, in this embodiment, a polycondensation reaction is also included in a polymerization reaction.

<<熱硬化性保護膜形成用組成物>> <<The composition for forming a thermosetting protective film>>

熱硬化性保護膜形成用膜可使用含有該熱硬化性保護膜形成用膜的構成材料之熱硬化性保護膜形成用組成物而形成。例如，於熱硬化性保護膜形成用膜之形成對象面塗敷熱硬化性保護膜形成用組成物，視需要使之乾燥，藉此可於目標部位形成熱硬化性保護膜形成用膜。熱硬化性保護膜形成用組成物中的常溫下不會氣化的成分彼此 的含量比率通常與熱硬化性保護膜形成用膜中的前述成分彼此的含量比率相同。此處，所謂「常溫」係如上文所說明。 The film for thermosetting protective film formation can be formed using the composition for thermosetting protective film formation containing the constituent material of the film for thermosetting protective film formation. For example, the film for thermosetting protective film formation can be formed in a target site|part by apply|coating the composition for thermosetting protective film formation to the formation object surface of the film for thermosetting protective film formation, and drying as needed. Components that do not vaporize at room temperature in the composition for forming a thermosetting protective film The content ratio of is usually the same as the content ratio of the aforementioned components in the film for forming a thermosetting protective film. Here, the so-called "normal temperature" is as described above.

利用公知的方法塗敷熱硬化性保護膜形成用組成物即可，例如可列舉使用以下各種塗佈機之方法：氣刀塗佈機、刮刀塗佈機、棒式塗佈機、凹版塗佈機、輥式塗佈機、輥刀塗佈機、簾幕式塗佈機、模具塗佈機、刀式塗佈機、絲網塗佈機、繞線(meyer)棒式塗佈機、接觸式塗佈機等。 What is necessary is just to apply|coat the composition for thermosetting protective film formation by a well-known method, for example, the method using the following various coaters is mentioned: Air knife coater, knife coater, bar coater, gravure coater machine, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, meyer bar coater, contact coating machine, etc.

熱硬化性保護膜形成用組成物的乾燥條件並無特別限定，於熱硬化性保護膜形成用組成物含有後述溶劑之情形時，較佳為進行加熱乾燥；該情形時，例如較佳為於70℃至130℃且10秒至5分鐘之條件下進行乾燥。 The drying conditions of the composition for forming a thermosetting protective film are not particularly limited, and when the composition for forming a thermosetting protective film contains a solvent to be described later, it is preferable to perform heat drying; Dry at 70°C to 130°C for 10 seconds to 5 minutes.

<保護膜形成用組成物(III-1)> <The composition for forming a protective film (III-1)>

作為熱硬化性保護膜形成用組成物，例如可列舉含有聚合物成分(A)及熱硬化性成分(B)之熱硬化性保護膜形成用組成物(III-1)(本說明書中，有時簡稱為「保護膜形成用組成物(III-1)」)等。 Examples of the composition for forming a thermosetting protective film include a composition (III-1) for forming a thermosetting protective film containing a polymer component (A) and a thermosetting component (B) (in this specification, there are It is abbreviated as "the composition for forming a protective film (III-1)") and the like.

[聚合物成分(A)] [Polymer component (A)]

聚合物成分(A)係用以對熱硬化性保護膜形成用膜賦予造膜性或可撓性等之聚合物化合物。 The polymer component (A) is a polymer compound for imparting film-forming properties, flexibility, and the like to the film for forming a thermosetting protective film.

保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜所含有之聚合物成分(A)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The polymer component (A) contained in the composition (III-1) for forming a protective film and the film for forming a thermosetting protective film may be only one type or two or more types; in the case of two or more types , the combination and ratio of these can be arbitrarily selected.

作為聚合物成分(A)，例如可列舉：丙烯酸系樹脂(具有(甲基)丙烯醯基之樹脂)、聚酯、胺基甲酸酯系樹脂(具有胺基甲酸酯鍵之樹脂)、丙烯酸胺基甲酸酯樹脂、聚矽氧系樹脂(具有矽氧烷鍵之樹脂)、橡膠系樹脂(具有橡膠結構之樹脂)、苯氧基樹脂、熱硬化性聚醯亞胺等，較佳為丙烯酸系樹脂。 As the polymer component (A), for example, acrylic resins (resins having a (meth)acryloyl group), polyesters, urethane resins (resins having urethane bonds), Acrylic urethane resin, polysiloxane-based resin (resin with siloxane bond), rubber-based resin (resin with rubber structure), phenoxy resin, thermosetting polyimide, etc., preferably It is acrylic resin.

作為聚合物成分(A)中的前述丙烯酸系樹脂，可列舉公知的丙烯酸系聚合物。 As said acrylic resin in a polymer component (A), a well-known acrylic polymer is mentioned.

丙烯酸系樹脂的重量平均分子量(Mw)較佳為10000至2000000，更佳為100000至1500000。藉由丙烯酸系樹脂的重量平均分子量為前述下限值以上，熱硬化性保護膜形成用膜的形狀穩定性(保管時的經時穩定性)提高。另外，藉由丙烯酸系樹脂的重量平均分子量為前述上限值以下，熱硬化性保護膜形成用膜變得易於追隨被黏著體的凹凸面，可進一步抑制於被黏著體與熱硬化性保護膜形成用膜之間產生孔隙(void)等。 The weight average molecular weight (Mw) of the acrylic resin is preferably from 10,000 to 2,000,000, more preferably from 100,000 to 1,500,000. The shape stability (time-dependent stability at the time of storage) of the film for thermosetting protective film formation improves by the weight average molecular weight of an acrylic resin being more than the said lower limit. In addition, when the weight-average molecular weight of the acrylic resin is equal to or less than the above-mentioned upper limit, the film for forming a thermosetting protective film can easily follow the uneven surface of the adherend, and the adherence and the thermosetting protective film can be further restrained. A void or the like is generated between the films for formation.

丙烯酸系樹脂的玻璃轉移溫度(Tg)較佳為-60℃至70℃，更佳為-30℃至50℃。藉由丙烯酸系樹脂的Tg為前 述下限值以上，可抑制保護膜與支持片之接著力，支持片之剝離性提高。另外，藉由丙烯酸系樹脂的Tg為前述上限值以下，熱硬化性保護膜形成用膜及保護膜與被黏著體之接著力提高。 The glass transition temperature (Tg) of the acrylic resin is preferably -60°C to 70°C, more preferably -30°C to 50°C. By the Tg of acrylic resin as the former More than the said lower limit, the adhesive force of a protective film and a support sheet can be suppressed, and the peelability of a support sheet improves. Moreover, since the Tg of an acrylic resin is below the said upper limit, the adhesive force of the film for thermosetting protective film formation, a protective film, and a to-be-adhered body improves.

作為丙烯酸系樹脂，例如可列舉：1種或2種以上之(甲基)丙烯酸酯之聚合物；選自(甲基)丙烯酸、衣康酸、乙酸乙烯酯、丙烯腈、苯乙烯及N-羥甲基丙烯醯胺等中之2種以上之單體之共聚物等。 Examples of acrylic resins include polymers of one or more (meth)acrylates; polymers selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N- Copolymers of two or more monomers, such as methylol acrylamide, etc.

作為構成丙烯酸系樹脂之前述(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯((甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯((甲基)丙烯酸肉豆蔻酯)、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯((甲基)丙烯酸棕櫚酯)、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯((甲基)丙烯酸硬脂酯)等構成烷基酯之烷基為碳數為1至18之鏈狀結構之 (甲基)丙烯酸烷基酯；(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊酯等(甲基)丙烯酸環烷基酯；(甲基)丙烯酸苄酯等(甲基)丙烯酸芳烷基酯；(甲基)丙烯酸二環戊烯酯等(甲基)丙烯酸環烯基酯；(甲基)丙烯酸二環戊烯氧基乙酯等(甲基)丙烯酸環烯氧基烷基酯；(甲基)丙烯醯亞胺；(甲基)丙烯酸縮水甘油酯等含縮水甘油基之(甲基)丙烯酸酯；(甲基)丙烯酸羥基甲酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等含羥基之(甲基)丙烯酸酯；(甲基)丙烯酸N-甲基胺基乙酯等含取代胺基之(甲基)丙烯酸酯等。此處，所謂「取代胺基」，意指胺基之1個或2個氫原子被氫原子以外的基取代而成之基。 As said (meth)acrylate which comprises an acrylic resin, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate are mentioned, for example ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate (methyl)hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-octyl (meth)acrylate Nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate) , tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, ten (meth)acrylate Hexaalkyl esters (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. constitute alkyl esters The alkyl group is one of the chain structure with carbon number from 1 to 18. Alkyl (meth)acrylate; (meth)cycloalkyl (meth)acrylate such as isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate; (meth)acrylate such as benzyl (meth)acrylate Aralkyl acrylates; (meth) cycloalkenyl acrylates such as dicyclopentenyl acrylate; (meth) cycloalkenyl acrylates such as dicyclopentenyloxyethyl (meth)acrylate Alkyl ester; (meth)acrylimide; (meth)acrylate and other glycidyl group-containing (meth)acrylates; (meth)acrylate hydroxymethyl, (meth)acrylate 2- Hydroxyethyl, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, (meth)acrylate (meth)acrylates containing hydroxyl groups such as 4-hydroxybutyl acrylate; (meth)acrylates containing substituted amino groups such as N-methylaminoethyl (meth)acrylates. Here, the "substituted amino group" means a group in which one or two hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom.

丙烯酸系樹脂例如除前述(甲基)丙烯酸酯以外，亦可為使選自(甲基)丙烯酸、衣康酸、乙酸乙烯酯、丙烯腈、苯乙烯及N-羥甲基丙烯醯胺等中的1種或2種以上之單體進行共聚合而成之樹脂。 For example, the acrylic resin may be selected from the group consisting of (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, N-methylol acrylamide, and the like in addition to the aforementioned (meth)acrylate. A resin obtained by copolymerizing one or two or more monomers.

構成丙烯酸系樹脂之單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 Only one kind of monomers constituting the acrylic resin may be used, or two or more kinds thereof may be sufficient; in the case of two or more kinds, the combination and ratio of these may be arbitrarily selected.

丙烯酸系樹脂亦可具有乙烯基、(甲基)丙烯醯基、胺基、羥基、羧基、異氰酸酯基等可與其他化合物鍵結之官能基。丙烯酸系樹脂中的前述官能基可經由後述交聯劑(F)與其他化合物鍵結，亦可不經由交聯劑(F)與其他化合物直接鍵結。藉由使丙烯酸系樹脂經由前述官能基與其他化合物鍵結，有使用保護膜形成用複合片所獲得之封裝的可靠性提高之傾向。 The acrylic resin may also have functional groups that can bond with other compounds, such as vinyl groups, (meth)acryloyl groups, amine groups, hydroxyl groups, carboxyl groups, and isocyanate groups. The functional group in the acrylic resin may be bonded to other compounds via the crosslinking agent (F) described later, or may be directly bonded to other compounds without the crosslinking agent (F). There exists a tendency for the reliability of the package obtained using the composite sheet for protective film formation to improve by making an acrylic resin couple|bond with another compound via the said functional group.

本實施形態中，作為聚合物成分(A)，亦可將丙烯酸系樹脂以外的熱塑性樹脂(以下，有時僅簡稱為「熱塑性樹脂」)與丙烯酸系樹脂併用。 In the present embodiment, as the polymer component (A), a thermoplastic resin other than the acrylic resin (hereinafter, only abbreviated as "thermoplastic resin" in some cases) may be used together with the acrylic resin.

藉由使用前述熱塑性樹脂，有時保護膜自支持片之剝離性提高，或熱硬化性保護膜形成用膜變得易於追隨被黏著體的凹凸面，從而可進一步抑制於被黏著體與熱硬化性保護膜形成用膜之間產生孔隙等。 By using the above-mentioned thermoplastic resin, the peelability of the protective film from the support sheet may be improved, or the film for forming a thermosetting protective film may easily follow the uneven surface of the adherend, thereby further suppressing the adherence and thermosetting. Pores, etc. are generated between the films for forming a protective film.

前述熱塑性樹脂的重量平均分子量較佳為1000至100000，更佳為3000至80000。 The weight average molecular weight of the aforementioned thermoplastic resin is preferably 1,000 to 100,000, more preferably 3,000 to 80,000.

前述熱塑性樹脂的玻璃轉移溫度(Tg)較佳為-30℃至150℃，更佳為-20℃至120℃。 The glass transition temperature (Tg) of the aforementioned thermoplastic resin is preferably -30°C to 150°C, more preferably -20°C to 120°C.

作為前述熱塑性樹脂，例如可列舉：聚酯、聚胺基甲酸酯、苯氧基樹脂、聚丁烯、聚丁二烯、聚苯乙烯等。 As said thermoplastic resin, a polyester, a polyurethane, a phenoxy resin, a polybutene, a polybutadiene, a polystyrene etc. are mentioned, for example.

保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜所含有之前述熱塑性樹脂可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The above-mentioned thermoplastic resin contained in the composition for forming a protective film (III-1) and the film for forming a thermosetting protective film may be only one kind or two or more kinds; Combinations and ratios can be arbitrarily selected.

保護膜形成用組成物(III-1)中，無論聚合物成分(A)之種類如何，聚合物成分(A)的含量(亦即，熱硬化性保護膜形成用膜中的聚合物成分(A)的含量)相對於溶劑以外的全部成分的總含量之比例均較佳為5質量%至50質量%，更佳為10質量%至40質量%，尤佳為15質量%至35質量%。 In the composition for forming a protective film (III-1), irrespective of the type of the polymer component (A), the content of the polymer component (A) (that is, the polymer component in the film for forming a thermosetting protective film ( The ratio of the content of A) to the total content of all components other than the solvent is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 35% by mass .

聚合物成分(A)有時亦符合熱硬化性成分(B)。本實施形態中，於保護膜形成用組成物(III-1)含有此種符合聚合物成分(A)及熱硬化性成分(B)之兩者之成分之情形時，保護膜形成用組成物(III-1)可視為含有聚合物成分(A)及熱硬化性成分(B)。 The polymer component (A) may also correspond to the thermosetting component (B). In the present embodiment, in the case where the composition (III-1) for forming a protective film contains such a component conforming to both the polymer component (A) and the thermosetting component (B), the composition for forming a protective film (III-1) (III-1) can be regarded as containing the polymer component (A) and the thermosetting component (B).

[熱硬化性成分(B)] [Thermosetting component (B)]

熱硬化性成分(B)係用以使熱硬化性保護膜形成用膜硬化而形成硬質之保護膜之成分。 The thermosetting component (B) is a component for forming a hard protective film by hardening the film for thermosetting protective film formation.

保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜所含有之熱硬化性成分(B)可僅為1種，亦可為2種以 上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The composition (III-1) for forming a protective film and the thermosetting component (B) contained in the film for forming a thermosetting protective film may be one type or two or more. above; in the case of two or more types, the combination and ratio of these can be arbitrarily selected.

作為熱硬化性成分(B)，例如可列舉：環氧系熱硬化性樹脂、熱硬化性聚醯亞胺、聚胺基甲酸酯、不飽和聚酯、聚矽氧樹脂等，較佳為環氧系熱硬化性樹脂。 As the thermosetting component (B), for example, epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, polysiloxane resins, etc. may be mentioned, and preferably Epoxy thermosetting resin.

(環氧系熱硬化性樹脂) (Epoxy thermosetting resin)

環氧系熱硬化性樹脂由環氧樹脂(B1)及熱硬化劑(B2)構成。 The epoxy-based thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2).

保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜所含有之環氧系熱硬化性樹脂可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The epoxy-based thermosetting resin contained in the composition (III-1) for forming a protective film and the film for forming a thermosetting protective film may be only one type or two or more types; in the case of two or more types , the combination and ratio of these can be arbitrarily selected.

‧環氧樹脂(B1) ‧Epoxy resin (B1)

作為環氧樹脂(B1)，可列舉公知的環氧樹脂，例如可列舉：多官能系環氧樹脂、聯苯化合物、雙酚A二縮水甘油醚及其氫化物、鄰甲酚酚醛清漆環氧樹脂、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、伸苯基骨架型環氧樹脂等2官能以上之環氧化合物。 As epoxy resin (B1), well-known epoxy resins are mentioned, for example, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, o-cresol novolak epoxy resins are mentioned. Resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, etc. compound.

作為環氧樹脂(B1)，亦可使用具有不飽和烴基之環氧樹脂。具有不飽和烴基之環氧樹脂相較於不具有不飽和烴基之環氧樹脂而言，與丙烯酸系樹脂之相容性較高。因此，藉由使用具有不飽和烴基之環氧樹脂，使用保護膜形成用複合片所獲得之封裝的可靠性提高。 As the epoxy resin (B1), an epoxy resin having an unsaturated hydrocarbon group can also be used. The epoxy resin having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin than the epoxy resin having no unsaturated hydrocarbon group. Therefore, by using the epoxy resin which has an unsaturated hydrocarbon group, the reliability of the package obtained using the composite sheet for protective film formation improves.

作為具有不飽和烴基之環氧樹脂，例如可列舉：多官能系環氧樹脂的一部分環氧基更換為具有不飽和烴基之基而成之化合物。此種化合物例如藉由使(甲基)丙烯酸或其衍生物與環氧基進行加成反應而獲得。 As an epoxy resin which has an unsaturated hydrocarbon group, the compound which replaced some epoxy groups of a polyfunctional epoxy resin with the group which has an unsaturated hydrocarbon group is mentioned, for example. Such a compound is obtained, for example, by subjecting (meth)acrylic acid or a derivative thereof to an addition reaction with an epoxy group.

另外，作為具有不飽和烴基之環氧樹脂，例如可列舉：構成環氧樹脂之芳香環等上直接鍵結有具有不飽和烴基之基之化合物等。 Moreover, as an epoxy resin which has an unsaturated hydrocarbon group, the compound etc. which the group which has an unsaturated hydrocarbon group couple|bonded directly with the aromatic ring etc. which comprise an epoxy resin are mentioned, for example.

不飽和烴基為具有聚合性之不飽和基，作為該不飽和烴基之具體例，可列舉：次乙基(乙烯基)、2-丙烯基(烯丙基)、(甲基)丙烯醯基、(甲基)丙烯醯胺基等，較佳為丙烯醯基。 The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples of the unsaturated hydrocarbon group include ethylene (vinyl), 2-propenyl (allyl), (meth)acryloyl, A (meth)acrylamido group or the like is preferably an acrylamide group.

再者，本說明書中，所謂「衍生物」意指原本之化合物的1個以上的氫原子被氫原子以外的基(取代基)取代而成之化合物。 In addition, in this specification, the "derivative" means a compound in which one or more hydrogen atoms of the original compound are substituted by groups (substituents) other than hydrogen atoms.

環氧樹脂(B1)的數量平均分子量並無特別限定，就熱硬化性保護膜形成用膜的硬化性、以及硬化後的保護膜的強度及耐熱性之方面而言，較佳為300至30000，更佳為 300至10000，尤佳為300至3000。 The number average molecular weight of the epoxy resin (B1) is not particularly limited, but is preferably 300 to 30,000 in terms of the curability of the film for forming a thermosetting protective film, and the strength and heat resistance of the protective film after curing. , more preferably 300 to 10,000, preferably 300 to 3,000.

環氧樹脂(B1)的環氧當量較佳為100g/eq至1100g/eq，更佳為150g/eq至1000g/eq。 The epoxy equivalent of the epoxy resin (B1) is preferably from 100 g/eq to 1100 g/eq, more preferably from 150 g/eq to 1000 g/eq.

環氧樹脂(B1)可單獨使用1種，亦可併用2種以上，於併用2種以上之情形時，這些之組合及比率可任意選擇。 One type of epoxy resin (B1) may be used alone, or two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio of these can be arbitrarily selected.

‧熱硬化劑(B2) ‧Thermosetting agent (B2)

熱硬化劑(B2)發揮針對環氧樹脂(B1)之硬化劑的功能。 The thermosetting agent (B2) functions as a curing agent for the epoxy resin (B1).

作為熱硬化劑(B2)，例如可列舉：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。作為前述官能基，例如可列舉：酚性羥基、醇性羥基、胺基、羧基、酸基經酐化而成之基等，較佳為酚性羥基、胺基、或酸基經酐化而成之基，更佳為酚性羥基或胺基。 As a thermosetting agent (B2), the compound which has two or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, and an acid group formed by an anhydride, and preferably a phenolic hydroxyl group, an amino group, or an acid group formed by an anhydride. The base formed is more preferably a phenolic hydroxyl group or an amine group.

熱硬化劑(B2)中，作為具有酚性羥基之酚系硬化劑，例如可列舉：多官能酚樹脂、聯苯酚、酚醛清漆型酚樹脂、二環戊二烯系酚樹脂、芳烷基酚樹脂等。 Among the thermosetting agents (B2), examples of the phenol-based curing agent having a phenolic hydroxyl group include polyfunctional phenol resins, biphenols, novolak-type phenol resins, dicyclopentadiene-based phenol resins, and aralkylphenols. resin, etc.

熱硬化劑(B2)中，作為具有胺基之胺系硬化劑，例如可列舉：二氰二胺(以下，有時簡稱為「DICY」)等。 In a thermosetting agent (B2), as an amine type hardening agent which has an amine group, dicyandiamine (it may be abbreviated as "DICY" hereafter) etc. are mentioned, for example.

熱硬化劑(B2)亦可具有不飽和烴基。 The thermal hardener (B2) may have an unsaturated hydrocarbon group.

作為具有不飽和烴基之熱硬化劑(B2)，例如可列舉：酚樹脂的一部分羥基被具有不飽和烴基之基取代而成之化合物、酚樹脂的芳香環上直接鍵結具有不飽和烴基之基而成之化合物等。 Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include a compound in which a part of the hydroxyl groups of a phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a group having an unsaturated hydrocarbon group directly bonded to the aromatic ring of the phenol resin. Compounds, etc.

熱硬化劑(B2)中的前述不飽和烴基與上述之具有不飽和烴基之環氧樹脂中的不飽和烴基相同。 The aforementioned unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.

於使用酚系硬化劑作為熱硬化劑(B2)之情形時，就保護膜自支持片之剝離性提高之方面而言，熱硬化劑(B2)較佳為軟化點或玻璃轉移溫度高的酚系硬化劑。 In the case of using a phenol-based hardener as the thermal hardener (B2), the thermal hardener (B2) is preferably a phenol having a high softening point or glass transition temperature from the viewpoint of improving the peelability of the protective film from the support sheet. System hardener.

熱硬化劑(B2)較佳為在常溫下為固體，且對環氧樹脂(B1)不顯示硬化活性；另一方面，藉由加熱而溶解，且對環氧樹脂(B1)顯示硬化活性之熱硬化劑(以下，有時簡稱為「熱活性潛伏性環氧樹脂硬化劑」)。 The thermosetting agent (B2) is preferably solid at room temperature and exhibits no hardening activity to the epoxy resin (B1); on the other hand, it dissolves by heating and exhibits a hardening activity to the epoxy resin (B1). Thermosetting agent (Hereinafter, it may be abbreviated as "thermally active latent epoxy resin curing agent").

前述熱活性潛伏性環氧樹脂硬化劑在常溫下於熱硬化性保護膜形成用膜中穩定地分散於環氧樹脂(B1)中，但藉由加熱與環氧樹脂(B1)相容，且與環氧樹脂(B1)反應。藉由使用前述熱活性潛伏性環氧樹脂硬化劑，保護膜形成用複合片的保存穩定性顯著提高。例如，可抑制該硬化劑自保護膜形成用膜向鄰接之支持片轉移，可有效抑制熱硬化性保護膜形成用膜的熱硬化性降低。並且，熱硬化性保護膜形成用膜藉由加熱而熱硬化度變得更高，故而後述之附有保護膜之半導體晶片的拾取性進一步提高。 The aforementioned thermally active latent epoxy resin hardener is stably dispersed in the epoxy resin (B1) in the film for thermosetting protective film formation at room temperature, but is compatible with the epoxy resin (B1) by heating, and Reacts with epoxy resin (B1). The storage stability of the composite sheet for protective film formation is remarkably improved by using the said thermally active latent epoxy resin hardener. For example, the transfer of the curing agent from the film for forming a protective film to the adjacent support sheet can be suppressed, and the reduction in the thermosetting properties of the film for forming a thermosetting protective film can be effectively suppressed. Moreover, since the film for thermosetting protective film formation becomes high thermosetting degree by heating, the pick-up property of the semiconductor wafer with a protective film mentioned later improves further.

作為前述熱活性潛伏性環氧樹脂硬化劑，例如可列舉：鎓鹽、二元酸醯肼、二氰二胺、硬化劑的胺加成物等。 As said thermally active latent epoxy resin hardener, an onium salt, a dibasic acid hydrazide, dicyandiamine, an amine adduct of a hardener, etc. are mentioned, for example.

熱硬化劑(B2)中，例如多官能酚樹脂、酚醛清漆型酚樹脂、二環戊二烯系酚樹脂、芳烷基酚樹脂等樹脂成分的數量平均分子量較佳為300至30000，更佳為400至10000，尤佳為500至3000。 In the thermosetting agent (B2), the number average molecular weight of resin components such as polyfunctional phenol resin, novolak-type phenol resin, dicyclopentadiene-based phenol resin, aralkylphenol resin, etc. is preferably 300 to 30,000, more preferably 400 to 10,000, more preferably 500 to 3,000.

熱硬化劑(B2)中，例如聯苯酚、二氰二胺等非樹脂成分的分子量並無特別限定，例如較佳為60至500。 In the thermosetting agent (B2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamine is not particularly limited, but is preferably 60 to 500, for example.

熱硬化劑(B2)可單獨使用1種，亦可併用2種以上，於併用2種以上之情形時，這些之組合及比率可任意選擇。 A thermosetting agent (B2) may be used individually by 1 type, and may use 2 or more types together, and when using 2 or more types together, the combination and ratio of these can be selected arbitrarily.

保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜中，熱硬化劑(B2)的含量相對於環氧樹脂(B1)的含量100質量份，較佳為0.1質量份至500質量份，更佳為1質量份至200質量份。藉由熱硬化劑(B2)的前述含量為前述下限值以上，熱硬化性保護膜形成用膜更易於進行硬化。另外，藉由熱硬化劑(B2)的前述含量為前述上限值以下，熱硬化性保護膜形成用膜的吸濕率降低，使用保護膜形成用複合片所獲得之封裝的可靠性進一步提高。 In the composition (III-1) for forming a protective film and the film for forming a thermosetting protective film, the content of the thermosetting agent (B2) is preferably 0.1 part by mass relative to 100 parts by mass of the content of the epoxy resin (B1). to 500 parts by mass, more preferably 1 to 200 parts by mass. When the said content of a thermosetting agent (B2) is more than the said lower limit, the film for thermosetting protective film formation becomes more easy to harden. Moreover, when the said content of the thermosetting agent (B2) is below the said upper limit, the moisture absorption rate of the film for thermosetting protective film formation falls, and the reliability of the package obtained using the composite sheet for protective film formation is further improved .

保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜中，熱硬化性成分(B)的含量(例如，環氧樹脂(B1)及熱硬化劑(B2)的總含量)相對於聚合物成分(A)的含量100質量份，較佳為1質量份至100質量份，更佳為1.5質量份至85質量份，尤佳為2質量份至70質量份。藉由熱硬化性成分(B)的前述含量為此種範圍，保護膜與支持片之接著力得到抑制，支持片之剝離性提高。 In the composition (III-1) for forming a protective film and the film for forming a thermosetting protective film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2) ) relative to 100 parts by mass of the content of the polymer component (A), preferably 1 to 100 parts by mass, more preferably 1.5 to 85 parts by mass, particularly preferably 2 to 70 parts by mass. When the said content of a thermosetting component (B) is such a range, the adhesive force of a protective film and a support sheet is suppressed, and the peelability of a support sheet improves.

[硬化促進劑(C)] [Hardening accelerator (C)]

保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜亦可含有硬化促進劑(C)。硬化促進劑(C)係用以調整保護膜形成用組成物(III-1)的硬化速度之成分。 The composition (III-1) for forming a protective film and the film for forming a thermosetting protective film may contain a curing accelerator (C). The curing accelerator (C) is a component for adjusting the curing rate of the protective film-forming composition (III-1).

作為較佳的硬化促進劑(C)，例如可列舉：三乙二胺、苄基二甲胺、三乙醇胺、二甲胺基乙醇、三(二甲胺基甲基)苯酚等三級胺；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-羥基甲基咪唑等咪唑類(1個以上之氫原子被氫原子以外的基取代而成之咪唑)；三丁基膦、二苯基膦、三苯基膦等有機膦類(1個以上之氫原子被有機基取代而成之膦)；四苯基硼酸四苯基鏻、四苯基硼酸三苯基膦等四苯基硼鹽等。 As preferable hardening accelerator (C), for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, etc. can be mentioned; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethylimidazole (imidazoles in which one or more hydrogen atoms are substituted by groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (one or more A phosphine in which a hydrogen atom is replaced by an organic group); tetraphenyl boron salts such as tetraphenyl phosphonium tetraphenyl borate, triphenyl phosphine tetraphenyl borate, etc.

保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜所含有之硬化促進劑(C)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The composition for forming a protective film (III-1) and the curing accelerator (C) contained in the film for forming a thermosetting protective film may be only one type or two or more types; in the case of two or more types , the combination and ratio of these can be arbitrarily selected.

於使用硬化促進劑(C)之情形時，保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜中，硬化促進劑(C)的含量相對於熱硬化性成分(B)的含量100質量份，較佳為0.01質量份至10質量份，更佳為0.1質量份至5質量份。藉由硬化促進劑(C)的前述含量為前述下限值以上，可獲得顯著的由使用硬化促進劑(C)所帶來之功效。另外，藉由硬化促進劑(C)的含量為前述上限值以下，例如抑制高極性的硬化促進劑(C)於高溫、高濕度條件下在熱硬化性保護膜形成用膜中向與被黏著體之接著界面側轉移而偏析之功效變高，從而使用保護膜形成用複合片所獲得之封裝的可靠性進一步提高。 When the curing accelerator (C) is used, in the composition for forming a protective film (III-1) and the film for forming a thermosetting protective film, the content of the curing accelerator (C) is relative to the thermosetting component (B) ) content of 100 parts by mass, preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass. When the said content of a hardening accelerator (C) is more than the said lower limit, the remarkable effect by using a hardening accelerator (C) can be obtained. In addition, when the content of the curing accelerator (C) is below the above-mentioned upper limit value, for example, the highly polar curing accelerator (C) is suppressed from reacting with the film for forming a thermosetting protective film under high temperature and high humidity conditions. The effect of the adhesive body being transferred to the interface side and segregating becomes high, and the reliability of the package obtained by using the composite sheet for forming a protective film is further improved.

[填充材料(D)] [filler (D)]

保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜亦可含有填充材料(D)。藉由熱硬化性保護膜形成用膜含有填充材料(D)，使熱硬化性保護膜形成用膜硬化而獲得之保護膜變得容易調整熱膨脹係數，藉由使該熱膨脹係數對於保護膜之形成對象物而言最適宜，使用保護膜形成用複合片所獲得之封裝的可靠性進一步提高。另外，藉由 熱硬化性保護膜形成用膜含有填充材料(D)，亦可降低保護膜的吸濕率，或提高散熱性。 The composition (III-1) for forming a protective film and the film for forming a thermosetting protective film may contain a filler (D). When the film for forming a thermosetting protective film contains the filler (D), the protective film obtained by curing the film for forming a thermosetting protective film becomes easy to adjust the coefficient of thermal expansion, and by making the coefficient of thermal expansion affect the formation of the protective film It is most suitable for the object, and the reliability of the package obtained by using the composite sheet for forming a protective film is further improved. In addition, by The film for thermosetting protective film formation contains a filler (D), and can also reduce the moisture absorption rate of a protective film, or improve heat dissipation.

填充材料(D)可為有機填充材料及無機填充材料之任一者，較佳為無機填充材料。 The filler (D) may be any one of an organic filler and an inorganic filler, preferably an inorganic filler.

作為較佳的無機填充材料，例如可列舉：二氧化矽、氧化鋁、滑石、碳酸鈣、鈦白、鐵丹、碳化矽、氮化硼等的粉末；將這些無機填充材料球形化而成之珠粒；這些無機填充材料的表面改質品；這些無機填充材料的單晶纖維；玻璃纖維等。 As preferred inorganic fillers, for example, powders of silica, alumina, talc, calcium carbonate, titanium dioxide, iron dan, silicon carbide, boron nitride, etc. can be mentioned; these inorganic fillers are spherical Beads; surface modification products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc.

這些之中，無機填充材料較佳為二氧化矽或氧化鋁。 Among these, the inorganic filler is preferably silica or alumina.

保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜所含有之填充材料(D)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The filler (D) contained in the composition (III-1) for forming a protective film and the film for forming a thermosetting protective film may be only one type or two or more types; in the case of two or more types, the The combination and ratio of these can be arbitrarily selected.

於使用填充材料(D)之情形時，保護膜形成用組成物(III-1)中，填充材料(D)的含量(亦即，熱硬化性保護膜形成用膜中的填充材料(D)的含量)相對於溶劑以外的全部成分的總含量之比例較佳為5質量%至80質量%，更佳為7質量%至60質量%。藉由填充材料(D)的含量為此種範圍，更容易調整上述熱膨脹係數。 When the filler (D) is used, in the composition (III-1) for forming a protective film, the content of the filler (D) (that is, the filler (D) in the film for forming a thermosetting protective film) The ratio of the content) to the total content of all components other than the solvent is preferably 5 to 80% by mass, more preferably 7 to 60% by mass. When the content of the filler (D) is in such a range, it becomes easier to adjust the thermal expansion coefficient.

[偶合劑(E)] [Coupling agent (E)]

保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜亦可含有偶合劑(E)。藉由使用具有可與無機化合物或有機化合物反應之官能基之化合物作為偶合劑(E)，可提高熱硬化性保護膜形成用膜對被黏著體之接著性及密接性。另外，藉由使用偶合劑(E)，使熱硬化性保護膜形成用膜硬化而獲得之保護膜不損害耐熱性而耐水性提高。 The composition (III-1) for forming a protective film and the film for forming a thermosetting protective film may contain a coupling agent (E). By using the compound which has a functional group which can react with an inorganic compound or an organic compound as a coupling agent (E), the adhesiveness and adhesiveness of the film for thermosetting protective film formation with respect to a to-be-adhered body can be improved. Moreover, by using a coupling agent (E), the water resistance improves without impairing the heat resistance of the protective film obtained by hardening the film for thermosetting protective film formation.

偶合劑(E)較佳為具有可與聚合物成分(A)、熱硬化性成分(B)等所具有之官能基反應之官能基之化合物，更佳為矽烷偶合劑。 The coupling agent (E) is preferably a compound having a functional group capable of reacting with functional groups possessed by the polymer component (A), the thermosetting component (B), and the like, and is more preferably a silane coupling agent.

作為較佳的前述矽烷偶合劑，例如可列舉：3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基甲基二乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基甲基二乙氧基矽烷、3-(苯基胺基)丙基三甲氧基矽烷、3-苯胺基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、雙(3-三乙氧基矽烷基丙基)四硫化物、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、咪唑矽烷等。 Examples of preferable silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyl Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethyl Oxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl Diethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane Oxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, ethylene trimethoxysilane, vinyltriacetoxysilane, imidazolylsilane, etc.

保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜所含有之偶合劑(E)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The coupling agent (E) contained in the composition (III-1) for forming a protective film and the film for forming a thermosetting protective film may be only one type or two or more types; in the case of two or more types, the The combination and ratio of these can be arbitrarily selected.

於使用偶合劑(E)之情形時，保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜中，偶合劑(E)的含量相對於聚合物成分(A)及熱硬化性成分(B)的總含量100質量份，較佳為0.03質量份至20質量份，更佳為0.05質量份至10質量份，尤佳為0.1質量份至5質量份。藉由偶合劑(E)的前述含量為前述下限值以上，可獲得更顯著的以下由使用偶合劑(E)所帶來之功效：填充材料(D)於樹脂中之分散性提高，或熱硬化性保護膜形成用膜與被黏著體之接著性提高等。另外，藉由偶合劑(E)的前述含量為前述上限值以下，可更進一步抑制產生逸氣。 In the case of using the coupling agent (E), in the composition for forming a protective film (III-1) and the film for forming a thermosetting protective film, the content of the coupling agent (E) is relative to the polymer component (A) and the heat The total content of the curable component (B) is 100 parts by mass, preferably 0.03 to 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass. By the above-mentioned content of the coupling agent (E) being more than the above-mentioned lower limit value, the following effect brought about by the use of the coupling agent (E) can be obtained more significantly: the dispersibility of the filler (D) in the resin is improved, or The adhesion between the film for forming a thermosetting protective film and the adherend is improved, etc. Moreover, when the said content of a coupling agent (E) is below the said upper limit, generation|occurrence|production of outgas can be suppressed further.

[交聯劑(F)] [Crosslinker (F)]

於使用具有可與其他化合物鍵結之官能基，例如乙烯基、(甲基)丙烯醯基、胺基、羥基、羧基、異氰酸酯基等之上述丙烯酸系樹脂等作為聚合物成分(A)之情形時，保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜亦可含有交聯劑(F)，該交聯劑(F)係用以使前述官能基與其他化合物鍵結而進行交聯。藉由使用交聯劑(F)進行交聯，可調節熱硬化性保護膜形成用膜的初期接著力及凝聚力。 In the case of using the above-mentioned acrylic resins having functional groups that can bond with other compounds, such as vinyl groups, (meth)acryloyl groups, amine groups, hydroxyl groups, carboxyl groups, isocyanate groups, etc., as the polymer component (A) In this case, the composition for forming a protective film (III-1) and the film for forming a thermosetting protective film may contain a crosslinking agent (F) for bonding the above-mentioned functional groups to other compounds. junction and cross-linking. The initial adhesion force and cohesion force of the film for thermosetting protective film formation can be adjusted by crosslinking using the crosslinking agent (F).

作為交聯劑(F)，例如可列舉：有機多元異氰酸酯化合物、有機多元亞胺化合物、金屬螯合物系交聯劑(具有金屬螯合物結構之交聯劑)、氮丙啶系交聯劑(具有氮丙啶基之交聯劑)等。 Examples of the crosslinking agent (F) include organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate-based crosslinking agents (crosslinking agents having a metal chelate structure), and aziridine-based crosslinking agents. agent (crosslinking agent with aziridine group), etc.

作為前述有機多元異氰酸酯化合物，例如可列舉：芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物及脂環族多元異氰酸酯化合物(以下，有時將這些化合物統一簡稱為「芳香族多元異氰酸酯化合物等」)；前述芳香族多元異氰酸酯化合物等的三聚物、異氰脲酸酯體及加合物；使前述芳香族多元異氰酸酯化合物等與多元醇化合物反應而獲得之末端異氰酸酯胺基甲酸酯預聚物等。前述「加合物」意指前述芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物或脂環族多元異氰酸酯化合物，與乙二醇、丙二醇、新戊二醇、三羥甲基丙烷或蓖麻油等含低分子活性氫化合物之反應物，作為前述加合物的示例，可列舉如後述之三羥甲基丙烷之苯二甲基二異氰酸酯加成物等。另外，所謂「末端異氰酸酯胺基甲酸酯預聚物」係如上文所說明。 Examples of the organic polyvalent isocyanate compound include: aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyvalent isocyanate compounds, etc."); Trimers, isocyanurate compounds, and adducts of the aforementioned aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers, etc. obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc. with a polyol compound, etc. . The aforementioned "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound, which is mixed with ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, etc. As an example of the above-mentioned adduct as the reactant of the low-molecular-weight active hydrogen compound, a xylylene diisocyanate adduct of trimethylolpropane, which will be described later, and the like are mentioned. In addition, the so-called "terminated isocyanate urethane prepolymer" is as described above.

作為前述有機多元異氰酸酯化合物，更具體而言，例如可列舉：2,4-甲苯二異氰酸酯；2,6-甲苯二異氰酸酯；1,3-苯二甲基二異氰酸酯；1,4-二甲苯二異氰酸酯；二苯基甲烷-4,4'-二異氰酸酯；二苯基甲烷-2,4'-二異氰酸酯； 3-甲基二苯基甲烷二異氰酸酯；六亞甲基二異氰酸酯；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；對三羥甲基丙烷等多元醇的全部或一部分羥基，加成甲苯二異氰酸酯、六亞甲基二異氰酸酯及苯二甲基二異氰酸酯的任1種或2種以上而成之化合物；離胺酸二異氰酸酯等。 As said organic polyvalent isocyanate compound, more specifically, 2, 4- toluene diisocyanate; 2, 6- toluene diisocyanate; 1, 3- xylylene diisocyanate; 1, 4- xylene diisocyanate are mentioned, for example Isocyanate; Diphenylmethane-4,4'-diisocyanate; Diphenylmethane-2,4'-diisocyanate; 3-Methyldiphenylmethane diisocyanate; Hexamethylene diisocyanate; Isophorone diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate ; Compounds obtained by adding any one or more of toluene diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate to all or part of the hydroxyl groups of polyols such as trimethylolpropane; lysine Acid diisocyanate, etc.

作為前述有機多元亞胺化合物，例如可列舉：N,N'-二苯基甲烷-4,4'-雙(1-氮丙啶甲醯胺)、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、N,N'-甲苯-2,4-雙(1-氮丙啶甲醯胺)三伸乙基三聚氰胺等。 As said organic polyvalent imine compound, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridinecarboxamide), trimethylolpropane-tri-β-nitrogen Propidyl propionate, tetramethylolmethane-tri-beta-aziridinyl propionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide) tris-ethyl melamine, etc.

於使用有機多元異氰酸酯化合物作為交聯劑(F)之情形時，作為聚合物成分(A)，較佳為使用含羥基之聚合物。於交聯劑(F)具有異氰酸酯基，聚合物成分(A)具有羥基之情形時，藉由交聯劑(F)與聚合物成分(A)之反應，可將交聯結構簡便地導入至熱硬化性保護膜形成用膜中。 When an organic polyvalent isocyanate compound is used as the crosslinking agent (F), it is preferable to use a hydroxyl group-containing polymer as the polymer component (A). When the crosslinking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the crosslinking structure can be easily introduced to the In the film for thermosetting protective film formation.

保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜所含有之交聯劑(F)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The crosslinking agent (F) contained in the composition (III-1) for forming a protective film and the film for forming a thermosetting protective film may be only one type or two or more types; in the case of two or more types , the combination and ratio of these can be arbitrarily selected.

於使用交聯劑(F)之情形時，保護膜形成用組成物 (III-1)中，交聯劑(F)的含量相對於聚合物成分(A)的含量100質量份，較佳為0.01質量份至20質量份，更佳為0.1質量份至10質量份，尤佳為0.5質量份至5質量份。藉由交聯劑(F)的前述含量為前述下限值以上，可獲得更顯著的由使用交聯劑(F)所帶來之功效。另外，藉由交聯劑(F)的前述含量為前述上限值以下，可抑制熱硬化性保護膜形成用膜與支持片之接著力或熱硬化性保護膜形成用膜與半導體晶圓或半導體晶片之接著力過度降低。 In the case of using a crosslinking agent (F), the composition for forming a protective film In (III-1), the content of the crosslinking agent (F) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the content of the polymer component (A). , particularly preferably 0.5 to 5 parts by mass. When the said content of a crosslinking agent (F) is more than the said lower limit, the effect by using a crosslinking agent (F) is more remarkable. Moreover, since the said content of the crosslinking agent (F) is below the said upper limit, the adhesive force of the film for thermosetting protective film formation and the support sheet, or the film for thermosetting protective film formation and the semiconductor wafer or the The adhesion of the semiconductor wafer is excessively reduced.

本實施形態中，即便不使用交聯劑(F)，亦可充分地獲得本發明的功效。 In the present embodiment, even if the crosslinking agent (F) is not used, the effect of the present invention can be sufficiently obtained.

[能量線硬化性樹脂(G)] [Energy beam curable resin (G)]

保護膜形成用組成物(III-1)亦可含有能量線硬化性樹脂(G)。熱硬化性保護膜形成用膜藉由含有能量線硬化性樹脂(G)，可藉由照射能量線而改變特性。 The composition (III-1) for forming a protective film may contain an energy ray curable resin (G). Since the film for thermosetting protective film formation contains an energy ray curable resin (G), it can change a characteristic by irradiating an energy ray.

能量線硬化性樹脂(G)係使能量線硬化性化合物進行聚合(硬化)而獲得。 The energy ray curable resin (G) is obtained by polymerizing (hardening) an energy ray curable compound.

作為前述能量線硬化性化合物，例如可列舉分子內具有至少1個聚合性雙鍵之化合物，較佳為具有(甲基)丙烯醯基之丙烯酸酯系化合物。 As said energy-beam curable compound, the compound which has at least 1 polymerizable double bond in a molecule|numerator is mentioned, for example, Preferably it is an acrylate type compound which has a (meth)acryloyl group.

作為前述丙烯酸酯系化合物，例如可列舉：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、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯等含鏈狀脂肪族骨架之(甲基)丙烯酸酯；二(甲基)丙烯酸二環戊酯等含環狀脂肪族骨架之(甲基)丙烯酸酯；聚乙二醇二(甲基)丙烯酸酯等聚伸烷基二醇(甲基)丙烯酸酯；寡酯(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲酸酯低聚物；環氧改性(甲基)丙烯酸酯；前述聚伸烷基二醇(甲基)丙烯酸酯以外的聚醚(甲基)丙烯酸酯；衣康酸低聚物等。 As said acrylate type compound, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylic acid are mentioned, for example ester, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol dimethacrylate (Meth)acrylate, 1,6-hexanediol di(meth)acrylate, etc. (meth)acrylate containing chain aliphatic skeleton; Dicyclopentyl di(meth)acrylate, etc. (Meth)acrylate of aliphatic skeleton; Polyalkylene glycol (meth)acrylate such as polyethylene glycol di(meth)acrylate; Oligoester (meth)acrylate; (Meth)acrylic acid Urethane oligomers; Epoxy modified (meth)acrylates; Polyether (meth)acrylates other than the aforementioned polyalkylene glycol (meth)acrylates; Itaconic acid oligomers Wait.

前述能量線硬化性化合物的重量平均分子量較佳為100至30000，更佳為300至10000。 The weight average molecular weight of the aforementioned energy ray curable compound is preferably from 100 to 30,000, more preferably from 300 to 10,000.

用於聚合之前述能量線硬化性化合物可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 Only one type of the above-mentioned energy ray-curable compound used for polymerization may be used, or two or more types may be sufficient; in the case of two or more types, the combination and ratio of these may be arbitrarily selected.

保護膜形成用組成物(III-1)所含有之能量線硬化性樹脂(G)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The energy ray curable resin (G) contained in the composition (III-1) for forming a protective film may be only one type or two or more types; in the case of two or more types, the combination and ratio of these may be Arbitrary choice.

保護膜形成用組成物(III-1)中，能量線硬化性樹脂(G)的含量較佳為1質量%至95質量%，更佳為2質量%至90質量%，尤佳為3質量%至85質量%。 In the composition (III-1) for forming a protective film, the content of the energy ray-curable resin (G) is preferably 1 to 95% by mass, more preferably 2 to 90% by mass, particularly preferably 3% by mass % to 85% by mass.

[光聚合起始劑(H)] [Photopolymerization initiator (H)]

於保護膜形成用組成物(III-1)含有能量線硬化性樹脂(G)之情形時，為了使能量線硬化性樹脂(G)高效率地進行聚合反應，亦可含有光聚合起始劑(H)。 When the protective film-forming composition (III-1) contains the energy ray-curable resin (G), a photopolymerization initiator may be contained in order to allow the energy ray-curable resin (G) to efficiently carry out the polymerization reaction (H).

作為保護膜形成用組成物(III-1)中的光聚合起始劑(H)，可列舉與黏著劑組成物(ii)中的光聚合起始劑相同之化合物。 As the photopolymerization initiator (H) in the composition (III-1) for forming a protective film, the same compound as the photopolymerization initiator in the adhesive composition (ii) can be mentioned.

保護膜形成用組成物(III-1)所含有之光聚合起始劑(H)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The photopolymerization initiator (H) contained in the composition (III-1) for forming a protective film may be only one type or two or more types; in the case of two or more types, the combination and ratio of these may be Arbitrary choice.

於使用光聚合起始劑(H)之情形時，保護膜形成用組成物(III-1)中，光聚合起始劑(H)的含量相對於能量線硬化性樹脂(G)的含量100質量份，較佳為0.1質量份至20質量份，更佳為1質量份至10質量份，尤佳為2質量份至5質量份。 In the case of using a photopolymerization initiator (H), in the protective film-forming composition (III-1), the content of the photopolymerization initiator (H) is 100 relative to the content of the energy ray-curable resin (G) The mass part is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, particularly preferably 2 to 5 parts by mass.

[著色劑(I)] [Colorant (I)]

保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜亦可含有著色劑(I)。 The composition (III-1) for forming a protective film and the film for forming a thermosetting protective film may contain a colorant (I).

作為著色劑(I)，例如可列舉：無機系顏料、有機系顏料、有機系染料等公知的著色劑。 As a coloring agent (I), well-known coloring agents, such as an inorganic type pigment, an organic type pigment, and an organic type dye, are mentioned, for example.

作為前述有機系顏料及有機系染料，例如可列舉：銨系色素、花青系色素、部花青系色素、克酮鎓(croconium)系色素、方酸鎓(squalilium)系色素、薁鎓系色素、聚次甲基系色素、萘醌系色素、吡喃鎓系色素、酞菁系色素、萘酞菁系色素、萘內醯胺系色素、偶氮色素、縮合偶氮色素、靛藍系色素、紫環酮(perinone)系色素、苝系色素、二噁烷(dioxane)系色素、喹吖啶酮系色素、異吲哚啉酮系色素、喹啉黃(quinophthalone)系色素、吡咯系色素、硫代靛藍系色素、金屬錯合物系色素(金屬錯鹽染料)、二硫醇金屬錯合物系色素、吲哚酚系色素、三烯丙基甲烷系色素、蒽醌系色素、萘酚系色素、次甲基偶氮系色素、苯并咪唑酮系色素、皮蒽酮系色素及士林(threne)系色素等。 Examples of the organic pigments and organic dyes include ammonium-based dyes, cyanine-based dyes, merocyanine-based dyes, croconium-based dyes, squalilium-based dyes, and azulium-based dyes. Pigments, polymethine based pigments, naphthoquinone based pigments, pyrylium based pigments, phthalocyanine based pigments, naphthalocyanine based pigments, naphthalamide based pigments, azo pigments, condensed azo pigments, indigo based pigments , Perinone dyes, perylene dyes, dioxane dyes, quinacridone dyes, isoindolinone dyes, quinophthalone dyes, pyrrole dyes , thioindigo-based dyes, metal complex dyes (metal salt dyes), dithiol metal complex dyes, indoxyl dyes, triallylmethane dyes, anthraquinone dyes, naphthalene Phenol-based dyes, methine azo-based dyes, benzimidazolone-based dyes, picanthrone-based dyes, threne-based dyes, and the like.

作為前述無機系顏料，例如可列舉：碳黑、鈷系色素、鐵系色素、鉻系色素、鈦系色素、釩系色素、鋯系色素、鉬系色素、釕系色素、鉑系色素、ITO(Indium Tin Oxide；氧化銦錫)系色素、ATO(Antimony Tin Oxide；氧化銻錫)系色素等。 Examples of the inorganic pigments include carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, and ITO. (Indium Tin Oxide; indium tin oxide)-based dye, ATO (Antimony Tin Oxide; antimony tin oxide)-based dye, and the like.

保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜所含有之著色劑(I)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The coloring agent (I) contained in the composition (III-1) for forming a protective film and the film for forming a thermosetting protective film may be only one kind or two or more kinds; in the case of two or more kinds, The combination and ratio of these can be arbitrarily selected.

於使用著色劑(I)之情形時，熱硬化性保護膜形成用膜中的著色劑(I)的含量根據目的適宜調節即可。例如，有時藉由雷射照射對保護膜實施印字，藉由調節熱硬化性保護膜形成用膜中的著色劑(I)的含量，調節保護膜的透光性，可調節印字視認性。另外，藉由調節熱硬化性保護膜形成用膜中的著色劑(I)的含量，可提高保護膜的設計性，亦可使得半導體晶圓的背面的研削痕跡不易見。若考慮這一方面，則保護膜形成用組成物(III-1)中，著色劑(I)的含量(亦即，熱硬化性保護膜形成用膜中的著色劑(I)的含量)相對於溶劑以外的全部成分的總含量之比例較佳為0.1質量%至10質量%，更佳為0.1質量%至7.5質量%，尤佳為0.1質量%至5質量%。藉由著色劑(I)的前述含量為前述下限值以上，可獲得更顯著的由使用著色劑(I)所帶來之功效。另外，藉由著色劑(I)的前述含量為前述上限值以下，可抑制熱硬化性保護膜形成用膜的透光性過度降低。 When using a coloring agent (I), content of the coloring agent (I) in the film for thermosetting protective film formation may be adjusted suitably according to the objective. For example, printing may be performed on the protective film by laser irradiation, and by adjusting the content of the colorant (I) in the film for forming a thermosetting protective film, the light transmittance of the protective film may be adjusted, and the visibility of the printing may be adjusted. In addition, by adjusting the content of the colorant (I) in the film for forming a thermosetting protective film, the designability of the protective film can be improved, and the grinding traces on the back surface of the semiconductor wafer can be made less visible. Considering this aspect, in the composition (III-1) for forming a protective film, the content of the coloring agent (I) (that is, the content of the coloring agent (I) in the film for forming a thermosetting protective film) is relatively The ratio of the total content of all components other than the solvent is preferably 0.1 to 10% by mass, more preferably 0.1 to 7.5% by mass, and still more preferably 0.1 to 5% by mass. When the aforementioned content of the colorant (I) is more than the aforementioned lower limit value, a more significant effect by using the colorant (I) can be obtained. Moreover, when the said content of a coloring agent (I) is below the said upper limit, it can suppress that the light transmittance of the film for thermosetting protective film formation falls too much.

[通用添加劑(J)] [General Additives (J)]

保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜中，亦可在無損本發明的功效之範圍內，含有通用添加劑(J)。 The composition for forming a protective film (III-1) and the film for forming a thermosetting protective film may contain a general-purpose additive (J) within a range that does not impair the effect of the present invention.

通用添加劑(J)可為公知的添加劑，可根據目的任意選擇，並無特別限定，作為較佳的通用添加劑(J)，例如可列舉：塑化劑、抗靜電劑、抗氧化劑、吸氣劑(gettering agent)等。 The general-purpose additive (J) may be a known additive, and can be arbitrarily selected according to the purpose without particular limitation. As the preferred general-purpose additive (J), for example, a plasticizer, an antistatic agent, an antioxidant, and a getter can be mentioned. (gettering agent), etc.

保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜所含有之通用添加劑(I)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The general additive (I) contained in the composition (III-1) for forming a protective film and the film for forming a thermosetting protective film may be only one kind or two or more kinds; in the case of two or more kinds, the The combination and ratio of these can be arbitrarily selected.

保護膜形成用組成物(III-1)及熱硬化性保護膜形成用膜中的通用添加劑(I)的含量並無特別限定，根據目的適宜選擇即可。 The content of the general-purpose additive (I) in the composition (III-1) for forming a protective film and the film for forming a thermosetting protective film is not particularly limited, and may be appropriately selected according to the purpose.

[溶劑] [solvent]

保護膜形成用組成物(III-1)較佳為進一步含有溶劑。含有溶劑之保護膜形成用組成物(III-1)的操作性良好。 The protective film-forming composition (III-1) preferably further contains a solvent. The solvent-containing composition for forming a protective film (III-1) has good handleability.

前述溶劑並無特別限定，作為較佳的前述溶劑，例如可列舉：甲苯、二甲苯等烴；甲醇、乙醇、2-丙醇、異丁醇(2-甲基丙烷-1-醇)、1-丁醇等醇；乙酸乙酯、乙酸丁酯等酯；丙酮、甲基乙基酮等酮；四氫呋喃等醚；二甲基甲醯胺、N-甲基吡咯啶酮等醯胺(具有醯胺鍵之化合物)等。 The aforementioned solvent is not particularly limited, and preferable examples of the aforementioned solvent include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), 1 - alcohols such as butanol; esters such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amine bond compound) and so on.

保護膜形成用組成物(III-1)所含有之溶劑可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The solvent contained in the composition (III-1) for forming a protective film may be only one type or two or more types, and in the case of two or more types, the combination and ratio of these may be arbitrarily selected.

就可使保護膜形成用組成物(III-1)中的含有成分更均勻地混合之方面而言，保護膜形成用組成物(III-1)所含有之溶劑較佳為甲基乙基酮等。 The solvent contained in the composition for forming a protective film (III-1) is preferably methyl ethyl ketone, since the components contained in the composition for forming a protective film (III-1) can be mixed more uniformly Wait.

<<熱硬化性保護膜形成用組成物的製造方法>> <<The manufacturing method of the composition for thermosetting protective film formation>>

保護膜形成用組成物(III-1)等熱硬化性保護膜形成用組成物藉由調配用以構成該組成物之各成分而獲得。 The composition for forming a thermosetting protective film, such as the composition for forming a protective film (III-1), is obtained by blending each component constituting the composition.

調配各成分時之添加順序並無特別限定，亦可同時添加2種以上之成分。 The order of addition at the time of preparing each component is not particularly limited, and two or more components may be added at the same time.

於使用溶劑之情形時，可藉由下述方式使用：將溶劑與溶劑以外的任一種調配成分混合而將該調配成分預先稀釋；亦可藉由下述方式使用：不將溶劑以外的任一種調配成分預先稀釋而將溶劑與這些調配成分混合。 In the case of using a solvent, it can be used by mixing the solvent with any preparation component other than the solvent and diluting the preparation component in advance; it can also be used in the following way: not using any preparation component other than the solvent The formulating ingredients are pre-diluted and the solvent is mixed with these formulating ingredients.

調配時混合各成分之方法並無特別限定，自以下公知的方法中適宜選擇即可：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機進行混合之方法；施加超音波進行混合之方法等。 The method of mixing the components during the preparation is not particularly limited, and may be appropriately selected from the following well-known methods: a method of mixing by rotating a stirring bar or a stirring blade, a method of mixing using a mixer, and a method of applying ultrasonic waves for mixing method etc.

關於添加及混合各成分時的溫度及時間，只要不使各調配成分劣化，即無特別限定，適宜調節即可，溫度較佳為15℃至30℃。 The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounded component is not degraded, and may be appropriately adjusted, and the temperature is preferably 15°C to 30°C.

‧能量線硬化性保護膜形成用膜 ‧Film for forming energy ray curable protective film

能量線硬化性保護膜形成用膜含有能量線硬化性成分(a)。 The film for energy ray curable protective film formation contains an energy ray curable component (a).

能量線硬化性成分(a)較佳為未硬化，較佳為具有黏著性，更佳為未硬化且具有黏著性。此處，所謂「能量線」及「能量線硬化性」係如上文所說明。 The energy ray curable component (a) is preferably uncured, preferably has adhesiveness, and is more preferably uncured and has adhesiveness. Here, the so-called "energy ray" and "energy ray sclerosis" are as described above.

<<能量線硬化性保護膜形成用組成物>> <<The composition for forming an energy ray curable protective film>>

能量線硬化性保護膜形成用膜可使用含有該膜的構成材料之能量線硬化性保護膜形成用組成物而形成。例如，於能量線硬化性保護膜形成用膜之形成對象面塗敷能量線硬化性保護膜形成用組成物，視需要使之乾燥，藉此可於目標部位形成能量線硬化性保護膜形成用膜。能量線硬化性保護膜形成用組成物中的常溫下不會氣化的成分彼此的含量比率通常與能量線硬化性保護膜形成用膜中的前述成分彼此的含量比率相同。此處，所謂「常溫」係如上文所說明。 The film for energy ray curable protective film formation can be formed using the composition for energy ray curable protective film formation containing the constituent material of the film. For example, the composition for forming an energy ray curable protective film can be applied to the surface to be formed of the film for forming an energy ray curable protective film, and then dried if necessary, whereby the composition for forming an energy ray curable protective film can be formed at the target site. membrane. The content ratio of the components which do not vaporize at normal temperature in the composition for energy ray curable protective film formation is usually the same as the content ratio of the aforementioned components in the film for energy ray curable protective film formation. Here, the so-called "normal temperature" is as described above.

利用公知的方法塗敷能量線硬化性保護膜形成用組成物即可，例如可列舉使用以下各種塗佈機之方法：氣刀塗佈機、刮刀塗佈機、棒式塗佈機、凹版塗佈機、輥式塗佈機、輥刀塗佈機、簾幕式塗佈機、模具塗佈機、刀式塗佈機、絲網塗佈機、繞線棒式塗佈機、接觸式塗佈機等。 The composition for forming an energy ray-curable protective film may be applied by a known method, and examples thereof include methods using the following various coaters: air knife coater, blade coater, bar coater, gravure coater Cloth machine, roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, wire rod coater, contact coater Cloth machine, etc.

能量線硬化性保護膜形成用組成物的乾燥條件並無特別限定，於能量線硬化性保護膜形成用組成物含有後述 溶劑之情形時，較佳為進行加熱乾燥，該情形時，較佳為於例如70℃至130℃且10秒至5分鐘之條件下進行乾燥。 The drying conditions of the composition for forming an energy ray curable protective film are not particularly limited, and the composition for forming an energy ray curable protective film contains the composition described later. In the case of a solvent, drying by heating is preferably performed, and in this case, drying is preferably performed under the conditions of, for example, 70° C. to 130° C. for 10 seconds to 5 minutes.

<保護膜形成用組成物(IV-1)> <Protection film-forming composition (IV-1)>

作為能量線硬化性保護膜形成用組成物，例如可列舉含有前述能量線硬化性成分(a)之能量線硬化性保護膜形成用組成物(IV-1)(本說明書中，有時僅簡稱為「保護膜形成用組成物(IV-1)」)等。 Examples of the energy-ray-curable protective film-forming composition include the energy-ray-curable protective film-forming composition (IV-1) (in this specification, it may be simply abbreviated as the energy ray curable component (a)), for example. "Protection film-forming composition (IV-1)") and the like.

[能量線硬化性成分(a)] [energy ray sclerosing component (a)]

能量線硬化性成分(a)係藉由照射能量線而化之成分，該成分用以對能量線硬化性保護膜形成用膜賦予造膜性或可撓性等。 The energy ray-curable component (a) is a component converted by irradiation with energy rays, and this component is used to impart film-forming properties, flexibility, and the like to the film for energy ray-curable protective film formation.

作為能量線硬化性成分(a)，例如可列舉：具有能量線硬化性基且重量平均分子量為80000至2000000之聚合物(a1)、及具有能量線硬化性基且分子量為100至80000之化合物(a2)。前述聚合物(a1)可該聚合物的至少一部分藉由交聯劑進行交聯，亦可不進行交聯。 Examples of the energy ray curable component (a) include a polymer (a1) having an energy ray curable group and a weight average molecular weight of 80,000 to 2,000,000, and a compound having an energy ray curable group and a molecular weight of 100 to 80,000. (a2). At least a part of the said polymer (a1) may be crosslinked by a crosslinking agent, and may not be crosslinked.

(具有能量線硬化性基且重量平均分子量為80000至2000000之聚合物(a1)) (Polymer (a1) having an energy ray hardening group and having a weight average molecular weight of 80,000 to 2,000,000)

作為具有能量線硬化性基且重量平均分子量為80000至2000000之聚合物(a1)，例如可列舉丙烯酸系樹脂(a1-1)，該丙烯酸系樹脂(a1-1)係使丙烯酸系聚合物(a11) 與能量線硬化性化合物(a12)進行加成反應而成，該丙烯酸系聚合物(a11)具有可與其他化合物所具有之基反應之官能基，該能量線硬化性化合物(a12)具有與前述官能基反應之基及能量線硬化性雙鍵等能量線硬化性基。 Examples of the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000 include an acrylic resin (a1-1) which is an acrylic polymer (a1-1). a11) Formed by addition reaction with an energy ray curable compound (a12), the acrylic polymer (a11) having a functional group reactive with a group of other compounds, the energy ray curable compound (a12) having the same Energy ray hardening groups such as functional groups reacting groups and energy ray hardening double bonds.

作為可與其他化合物所具有之基反應之前述官能基，例如可列舉：羥基、羧基、胺基、取代胺基(胺基的1個或2個氫原子被氫原子以外的基取代而成之基)、環氧基等。但是，就防止半導體晶圓或半導體晶片等的電路腐蝕之方面而言，前述官能基較佳為羧基以外的基。 Examples of the functional group that can react with groups contained in other compounds include a hydroxyl group, a carboxyl group, an amino group, and a substituted amino group (a group in which one or two hydrogen atoms of the amino group are substituted with a group other than a hydrogen atom). group), epoxy group, etc. However, it is preferable that the said functional group is a group other than a carboxyl group from the viewpoint of preventing circuit corrosion of a semiconductor wafer, a semiconductor wafer, or the like.

這些之中，前述官能基較佳為羥基。 Among these, the aforementioned functional group is preferably a hydroxyl group.

‧具有官能基之丙烯酸系聚合物(a11) ‧Acrylic polymer with functional group (a11)

前述具有官能基之丙烯酸系聚合物(a11)例如可列舉：使前述具有官能基之丙烯酸系單體與前述不具有官能基之丙烯酸系單體進行共聚合而成之聚合物，亦可為除這些單體以外，進一步使丙烯酸系單體以外的單體(非丙烯酸系單體)進行共聚合而成之聚合物。 Examples of the functional group-containing acrylic polymer (a11) include, for example, a polymer obtained by copolymerizing the functional group-containing acrylic monomer and the non-functional group-containing acrylic monomer. A polymer obtained by copolymerizing monomers other than acrylic monomers (non-acrylic monomers) in addition to these monomers.

另外，前述丙烯酸系聚合物(a11)可為無規共聚物，亦可為嵌段共聚物。 In addition, the aforementioned acrylic polymer (a11) may be a random copolymer or a block copolymer.

作為前述具有官能基之丙烯酸系單體，例如可列舉：含羥基之單體、含羧基之單體、含胺基之單體、含取代胺基之單體、含環氧基之單體等。 Examples of the functional group-containing acrylic monomer include hydroxyl group-containing monomers, carboxyl group-containing monomers, amine group-containing monomers, substituted amino group-containing monomers, epoxy group-containing monomers, and the like .

作為前述含羥基之單體，例如可列舉：(甲基)丙烯酸羥基甲酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等(甲基)丙烯酸羥基烷基酯；乙烯醇、烯丙醇等非(甲基)丙烯酸系不飽和醇(不具有(甲基)丙烯醯基骨架之不飽和醇)等。 Examples of the hydroxyl group-containing monomer include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. Hydroxyalkyl (meth)acrylates such as hydroxypropyl, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols such as allyl alcohol (unsaturated alcohols having no (meth)acryloyl skeleton), and the like.

作為前述含羧基之單體，例如可列舉：(甲基)丙烯酸、丁烯酸等乙烯性不飽和單羧酸(具有乙烯性不飽和鍵之單羧酸)；富馬酸、衣康酸、馬來酸、檸康酸等乙烯性不飽和二羧酸(具有乙烯性不飽和鍵之二羧酸)；前述乙烯性不飽和二羧酸的酐；甲基丙烯酸2-羧基乙酯等(甲基)丙烯酸羧基烷基酯等。 Examples of the carboxyl group-containing monomer include ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, Ethylenically unsaturated dicarboxylic acids (dicarboxylic acids with ethylenically unsaturated bonds) such as maleic acid and citraconic acid; anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. (methyl methacrylate) base) carboxyalkyl acrylate, etc.

前述具有官能基之丙烯酸系單體較佳為含羥基之單體、含羧基之單體，更佳為含羥基之單體。 The aforementioned acrylic monomer having a functional group is preferably a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.

構成前述丙烯酸系聚合物(a11)之前述具有官能基之丙烯酸系單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The functional group-containing acrylic monomer constituting the acrylic polymer (a11) may be only one type or two or more types; in the case of two or more types, the combination and ratio of these may be arbitrarily selected.

作為前述不具有官能基之丙烯酸系單體，例如，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯((甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯((甲基)丙烯酸肉豆蔻酯)、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯((甲基)丙烯酸棕櫚酯)、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯((甲基)丙烯酸硬脂酯)等構成烷基酯之烷基為碳數為1至18之鏈狀結構之(甲基)丙烯酸烷基酯等。 Examples of the acrylic monomer having no functional group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate (methyl)hexyl acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-octyl (meth)acrylate Nonyl ester, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate) , tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, ten (meth)acrylate Hexaalkyl esters (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. constitute alkyl esters The alkyl group is an alkyl (meth)acrylate having a chain structure of 1 to 18 carbon atoms.

另外，作為前述不具有官能基之丙烯酸系單體，例如亦可列舉：(甲基)丙烯酸甲氧基甲酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基甲酯、(甲基)丙烯酸乙氧基乙酯等含烷氧基烷基之(甲基)丙烯酸酯；包含(甲基)丙烯酸苯酯等(甲基)丙烯酸芳基酯等之具有芳香族基之(甲基)丙烯酸酯；非交聯性的(甲基)丙烯醯胺及其衍生物；(甲基)丙烯酸N,N-二甲胺基乙酯、(甲基)丙烯酸N,N-二甲胺基丙酯等非交聯性的具有三級胺基之(甲基)丙烯酸酯等。 Moreover, as an acryl-type monomer which does not have the said functional group, (meth)acrylate methoxymethyl, (meth)acrylate methoxyethyl, (meth)acrylate ethoxymethyl can also be mentioned, for example. (meth)acrylates containing alkoxyalkyl groups such as ethoxyethyl (meth)acrylates; aromatic groups containing aryl (meth)acrylates such as phenyl (meth)acrylates (meth)acrylate; non-crosslinkable (meth)acrylamide and its derivatives; (meth)acrylate N,N-dimethylaminoethyl ester, (meth)acrylate N,N- Non-crosslinkable (meth)acrylates having tertiary amine groups, such as dimethylaminopropyl ester, etc.

構成前述丙烯酸系聚合物(a11)之前述不具有官能基之丙烯酸系單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The acryl-based monomer that does not have a functional group constituting the acryl-based polymer (a11) may be only one type or two or more types; in the case of two or more types, the combination and ratio of these may be arbitrarily selected .

作為前述非丙烯酸系單體，例如可列舉：乙烯、降冰片烯等烯烴；乙酸乙烯酯；苯乙烯等。 Examples of the non-acrylic monomers include olefins such as ethylene and norbornene; vinyl acetate; styrene and the like.

構成前述丙烯酸系聚合物(a11)之前述非丙烯酸系單體可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The said non-acrylic-type monomer which comprises the said acrylic polymer (a11) may be only 1 type, and may be 2 or more types; In the case of 2 or more types, the combination and ratio of these can be selected arbitrarily.

前述丙烯酸系聚合物(a11)中，由前述具有官能基之丙烯酸系單體衍生之結構單元的量相對於構成該丙烯酸系聚合物(a11)之結構單元的全部量之比例(含量)較佳為0.1質量%至50質量%，更佳為1質量%至40質量%，尤佳為3質量%至30質量%。藉由前述比例為此種範圍，可將藉由前述丙烯酸系聚合物(a11)與前述能量線硬化性化合物(a12)之共聚合所獲得之前述丙烯酸系樹脂(a1-1)中能量線硬化性基的含量容易地調節為使保護膜的硬化程度較佳之範圍。 In the acrylic polymer (a11), the ratio (content) of the amount of the structural units derived from the functional group-containing acrylic monomer to the total amount of the structural units constituting the acrylic polymer (a11) is preferable It is 0.1 mass % to 50 mass %, More preferably, it is 1 mass % to 40 mass %, Especially preferably, it is 3 mass % to 30 mass %. By setting the ratio in this range, the acrylic resin (a1-1) obtained by the copolymerization of the acrylic polymer (a11) and the energy ray curable compound (a12) can be energy ray hardened The content of the radicals can be easily adjusted to a range in which the degree of hardening of the protective film is preferable.

構成前述丙烯酸系樹脂(a1-1)之前述丙烯酸系聚合物(a11)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The said acrylic polymer (a11) which comprises the said acrylic resin (a1-1) may be only 1 type, and may be 2 or more types; In the case of 2 or more types, the combination and ratio of these can be selected arbitrarily.

保護膜形成用組成物(IV-1)中，丙烯酸系樹脂(a1-1)的含量較佳為1質量%至40質量%，更佳為2質量%至30質量%，尤佳為3質量%至20質量%。 In the composition (IV-1) for forming a protective film, the content of the acrylic resin (a1-1) is preferably 1 to 40 mass %, more preferably 2 to 30 mass %, particularly preferably 3 mass % % to 20% by mass.

‧能量線硬化性化合物(a12) ‧Energy ray curable compound (a12)

前述能量線硬化性化合物(a12)較佳為具有選自由異氰酸酯基、環氧基及羧基所組成之群組中的1種或2種以上作為可與前述丙烯酸系聚合物(a11)所具有之官能基反應之基，更佳為具有異氰酸酯基作為前述基。於前述能量線硬化性化合物(a12)例如具有異氰酸酯基作為前述基之情形時，該異氰酸酯基與前述具有羥基作為官能基之丙烯酸系聚合物(a11)的該羥基容易反應。 The aforementioned energy ray-curable compound (a12) preferably has one or more selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group as a compound that the aforementioned acrylic polymer (a11) has. More preferably, the functional group reacts with an isocyanate group as the aforementioned group. When the energy ray-curable compound (a12) has, for example, an isocyanate group as the group, the isocyanate group easily reacts with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as a functional group.

前述能量線硬化性化合物(a12)較佳為於1分子中具有1個至5個前述能量線硬化性基，更佳為具有1個至2個前述能量線硬化性基。 It is preferable that the said energy ray hardening compound (a12) has 1 to 5 said energy ray hardening groups in 1 molecule, More preferably, it has 1 to 2 said energy ray hardening groups.

作為前述能量線硬化性化合物(a12)，例如可列舉：異氰酸2-甲基丙烯醯氧基乙酯、間-異丙烯基-α,α-二甲基苄基異氰酸酯、甲基丙烯醯基異氰酸酯、異氰酸烯丙酯、異氰酸1,1-(雙丙烯醯氧基甲基)乙酯；藉由二異氰酸酯化合物或多異氰酸酯化合物與(甲基)丙烯酸羥基乙酯之反應而獲得之丙烯醯基單異氰酸酯化合物；藉由二異氰酸酯 化合物或多異氰酸酯化合物、多元醇化合物及(甲基)丙烯酸羥基乙酯之反應而獲得之丙烯醯基單異氰酸酯化合物等。 Examples of the energy ray curable compound (a12) include 2-methacryloyloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and methacryloyl isocyanate. diisocyanate, allyl isocyanate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate; by reaction of diisocyanate compound or polyisocyanate compound with hydroxyethyl (meth)acrylate Acryloyl monoisocyanate compound obtained; by diisocyanate Compounds or polyisocyanate compounds, polyol compounds and hydroxyethyl (meth)acrylate obtained by the reaction of acrylyl monoisocyanate compounds and the like.

這些之中，前述能量線硬化性化合物(a12)較佳為異氰酸2-甲基丙烯醯氧基乙酯。 Among these, it is preferable that the said energy ray curable compound (a12) is 2-methacryloyloxyethyl isocyanate.

構成前述丙烯酸系樹脂(a1-1)之前述能量線硬化性化合物(a12)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The aforementioned energy ray-curable compound (a12) constituting the aforementioned acrylic resin (a1-1) may be only one type or two or more types; in the case of two or more types, the combination and ratio of these may be arbitrarily selected .

前述丙烯酸系樹脂(a1-1)中，源自前述能量線硬化性化合物(a12)之能量線硬化性基的含量相對於源自前述丙烯酸系聚合物(a11)之前述官能基的含量之比例較佳為20莫耳%至120莫耳%，更佳為35莫耳%至100莫耳%，尤佳為50莫耳%至100莫耳%。藉由前述含量之比例為此種範圍，硬化後的保護膜的接著力進一步變大。再者，於前述能量線硬化性化合物(a12)為一官能(於1分子中具有1個前述基)化合物之情形時，前述含量之比例的上限值成為100莫耳%，但於前述能量線硬化性化合物(a12)為多官能(於1分子中具有2個以上前述基)化合物之情形時，前述含量之比例的上限值有時超過100莫耳%。 In the acrylic resin (a1-1), the ratio of the content of the energy ray curable group derived from the energy ray curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) It is preferably 20 mol% to 120 mol%, more preferably 35 mol% to 100 mol%, particularly preferably 50 mol% to 100 mol%. When the ratio of the said content is in such a range, the adhesive force of the protective film after hardening becomes further large. Furthermore, in the case where the energy ray-curable compound (a12) is a monofunctional (having one of the aforementioned groups in 1 molecule) compound, the upper limit of the ratio of the aforementioned content is 100 mol%, but in the aforementioned energy When the linear curable compound (a12) is a polyfunctional (having two or more of the aforementioned groups in one molecule) compound, the upper limit of the ratio of the aforementioned content may exceed 100 mol %.

前述聚合物(a1)的重量平均分子量(Mw)較佳為100000至2000000，更佳為300000至1500000。 The weight average molecular weight (Mw) of the aforementioned polymer (a1) is preferably from 100,000 to 2,000,000, more preferably from 300,000 to 1,500,000.

此處，所謂「重量平均分子量」係如上文所說明。 Here, the so-called "weight average molecular weight" is as described above.

於前述聚合物(a1)的至少一部分藉由交聯劑進行交聯之情形時，前述聚合物(a1)可使不屬於上述說明之構成前述丙烯酸系聚合物(a11)之任一單體且具有與交聯劑反應之基之單體進行聚合，在前述與交聯劑反應之基中進行交聯，亦可在源自前述能量線硬化性化合物(a12)之與前述官能基反應之基中進行交聯。 When at least a part of the above-mentioned polymer (a1) is cross-linked by a cross-linking agent, the above-mentioned polymer (a1) may be any monomer constituting the above-mentioned acrylic polymer (a11) other than those described above and The monomer having a group reactive with the crosslinking agent is polymerized, and the crosslinking is performed in the group reactive with the crosslinking agent, or the group derived from the energy ray curable compound (a12) and the functional group reactive with the above-mentioned can also be carried out. cross-linking.

保護膜形成用組成物(IV-1)及能量線硬化性保護膜形成用膜所含有之前述聚合物(a1)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The above-mentioned polymer (a1) contained in the composition (IV-1) for forming a protective film and the film for forming an energy ray-curable protective film may be only one type or two or more types; in the case of two or more types , the combination and ratio of these can be arbitrarily selected.

(具有能量線硬化性基且分子量為100至80000之化合物(a2)) (Compound (a2) having an energy ray hardening group and having a molecular weight of 100 to 80,000)

作為具有能量線硬化性基且分子量為100至80000之化合物(a2)所具有之能量線硬化性基，可列舉包含能量線硬化性雙鍵之基；作為較佳的該基，可列舉(甲基)丙烯醯基、乙烯基等。 Examples of the energy-ray-curable group of the compound (a2) having an energy-ray-curable group and a molecular weight of 100 to 80,000 include groups containing an energy-ray-curable double bond; base) acrylyl, vinyl, etc.

若前述化合物(a2)滿足上述條件，即無特別限定，可列舉：具有能量線硬化性基之低分子量化合物、具有能量 線硬化性基之環氧樹脂、具有能量線硬化性基之酚樹脂等。 The compound (a2) is not particularly limited as long as it satisfies the above-mentioned conditions, and examples thereof include a low molecular weight compound having an energy ray curable group, a compound having an energy Epoxy resin with a line curable group, phenol resin with an energy line curable group, etc.

前述化合物(a2)中，作為具有能量線硬化性基之低分子量化合物，例如可列舉多官能之單體或低聚物等，較佳為具有(甲基)丙烯醯基之丙烯酸酯系化合物。 In the said compound (a2), as a low molecular weight compound which has an energy ray hardening group, a polyfunctional monomer, an oligomer, etc. are mentioned, for example, Preferably it is an acrylate type compound which has a (meth)acryloyl group.

作為前述丙烯酸酯系化合物，例如可列舉：甲基丙烯酸2-羥基-3-(甲基)丙烯醯氧基丙酯、聚乙二醇二(甲基)丙烯酸酯、丙氧基化乙氧基化雙酚A二(甲基)丙烯酸酯、2,2-雙[4-((甲基)丙烯醯氧基聚乙氧基)苯基]丙烷、乙氧基化雙酚A二(甲基)丙烯酸酯、2,2-雙[4-((甲基)丙烯醯氧基二乙氧基)苯基]丙烷、9,9-雙[4-(2-(甲基)丙烯醯氧基乙氧基)苯基]茀、2,2-雙[4-((甲基)丙烯醯氧基聚丙氧基)苯基]丙烷、三環癸烷二甲醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、聚丁二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、2,2-雙[4-((甲基)丙烯醯氧基乙氧基)苯基]丙烷、新戊二醇二(甲基)丙烯酸酯、乙氧基化聚丙二醇二(甲基)丙烯酸酯、2-羥基-1,3-二(甲基)丙烯醯氧基丙烷等2官能(甲基)丙烯酸酯；異氰脲酸三(2-(甲基)丙烯醯氧基乙基)酯、ε-己內酯改性異氰脲酸三-(2-(甲基)丙烯醯氧基乙基)酯、乙氧基化甘油三(甲 基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、乙氧基化季戊四醇四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇聚(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等多官能(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲酸酯低聚物等多官能(甲基)丙烯酸酯低聚物等。 As said acrylate type compound, for example, 2-hydroxy-3-(meth)acryloyloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxy bisphenol A di(meth)acrylate, 2,2-bis[4-((meth)acrylooxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(methyl) ) acrylate, 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxy) ethoxy) phenyl] stilbene, 2,2-bis[4-((meth)acryloyloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate, 1 ,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate ) acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol Alcohol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acrylooxyethoxy)phenyl]propane, neopentyl glycol Bifunctional (meth)acrylates such as alcohol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acrylooxypropane, etc. ; Tris-(2-(meth)acryloyloxyethyl) isocyanurate, ε-caprolactone-modified tris-(2-(meth)acryloyloxyethyl) isocyanurate , ethoxylated glycerol tri(methyl) base) acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate base) acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate and other polyfunctional (meth)acrylates; (meth)acrylate amino group Polyfunctional (meth)acrylate oligomers such as formate oligomers, etc.

前述化合物(a2)中，作為具有能量線硬化性基之環氧樹脂、具有能量線硬化性基之酚樹脂，例如可使用「日本特開2013-194102號公報」中的段落0043等中所記載之樹脂。此種樹脂亦符合構成後述之熱硬化性成分之樹脂，但本實施形態中視作前述化合物(a2)。 Among the above-mentioned compounds (a2), as the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group, for example, those described in paragraph 0043 of "Japanese Unexamined Patent Application Publication No. 2013-194102" can be used. of resin. Although such resin also corresponds to the resin which comprises the thermosetting component mentioned later, in this embodiment, it is regarded as said compound (a2).

前述化合物(a2)的重量平均分子量較佳為100至30000，更佳為300至10000。 The weight average molecular weight of the aforementioned compound (a2) is preferably from 100 to 30,000, more preferably from 300 to 10,000.

保護膜形成用組成物(IV-1)及能量線硬化性保護膜形成用膜所含有之前述化合物(a2)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The above-mentioned compound (a2) contained in the composition (IV-1) for forming a protective film and the film for forming an energy ray-curable protective film may be only one type or two or more types; in the case of two or more types , the combination and ratio of these can be arbitrarily selected.

[不具有能量線硬化性基之聚合物(b)] [Polymer (b) without energy ray curable group]

於保護膜形成用組成物(IV-1)及能量線硬化性保護膜形成用膜含有前述化合物(a2)作為前述能量線硬化性成 分(a)之情形時，較佳為亦進一步含有不具有能量線硬化性基之聚合物(b)。 The composition (IV-1) for forming a protective film and the film for forming an energy ray curable protective film contain the compound (a2) as the energy ray curable composition. In the case of (a), it is preferable to further contain the polymer (b) which does not have an energy ray curable group.

前述聚合物(b)可至少一部分藉由交聯劑進行交聯，亦可不進行交聯。 At least a part of the said polymer (b) may be crosslinked by a crosslinking agent, and may not be crosslinked.

作為不具有能量線硬化性基之聚合物(b)，例如可列舉：丙烯酸系聚合物、苯氧基樹脂、胺基甲酸酯樹脂、聚酯、橡膠系樹脂、丙烯酸胺基甲酸酯樹脂等。 Examples of the polymer (b) not having an energy ray curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, and acrylic urethane resins. Wait.

這些之中，前述聚合物(b)較佳為丙烯酸系聚合物(以下，有時簡稱為「丙烯酸系聚合物(b-1)」)。 Among these, the aforementioned polymer (b) is preferably an acrylic polymer (hereinafter, abbreviated as "acrylic polymer (b-1)" in some cases).

丙烯酸系聚合物(b-1)可為公知的聚合物，例如可為1種丙烯酸系單體的均聚物，亦可為2種以上丙烯酸系單體的共聚物，還可為1種或2種以上丙烯酸系單體與1種或2種以上除丙烯酸系單體以外的單體(非丙烯酸系單體)之共聚物。 The acrylic polymer (b-1) may be a known polymer, for example, a homopolymer of one acrylic monomer, a copolymer of two or more acrylic monomers, or a single or A copolymer of two or more acrylic monomers and one or more monomers (non-acrylic monomers) other than acrylic monomers.

作為構成丙烯酸系聚合物(b-1)之前述丙烯酸系單體，例如可列舉：(甲基)丙烯酸烷基酯、具有環狀骨架之(甲基)丙烯酸酯、含縮水甘油基之(甲基)丙烯酸酯、含羥基之(甲基)丙烯酸酯、含取代胺基之(甲基)丙烯酸酯等。此處，所謂「取代胺基」係如上文所說明。 Examples of the aforementioned acrylic monomers constituting the acrylic polymer (b-1) include alkyl (meth)acrylates, (meth)acrylates having a cyclic skeleton, and (meth)acrylates having a glycidyl group. group) acrylate, hydroxyl group-containing (meth)acrylate, substituted amine group-containing (meth)acrylate, etc. Here, the so-called "substituted amino group" is as described above.

作為前述(甲基)丙烯酸烷基酯，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯((甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯((甲基)丙烯酸肉豆蔻酯)、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯((甲基)丙烯酸棕櫚酯)、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯((甲基)丙烯酸硬脂酯)等構成烷基酯之烷基為碳數為1至18之鏈狀結構之(甲基)丙烯酸烷基酯等。 Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate n-butyl meth)acrylate, isobutyl (meth)acrylate, 2nd butyl (meth)acrylate, 3rd butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylic acid Hexyl ester, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, Isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), (meth)acrylate base) tridecyl acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, hexadecyl (meth)acrylate Ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. It is a (meth)acrylic acid alkyl ester of a chain structure with a carbon number of 1 to 18, and the like.

作為前述具有環狀骨架之(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊酯等(甲基)丙烯酸環烷基酯；(甲基)丙烯酸苄酯等(甲基)丙烯酸芳烷基酯；(甲基)丙烯酸二環戊烯酯等(甲基)丙烯酸環烯基酯；(甲基)丙烯酸二環戊烯氧基乙酯等(甲基)丙烯酸環烯氧基烷基酯等。 Examples of (meth)acrylates having the aforementioned cyclic skeleton include cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate; ) Aralkyl acrylates such as benzyl acrylate; (meth) cycloalkenyl acrylates such as dicyclopentenyl (meth)acrylate; Dicyclopentenyloxyethyl (meth)acrylate, etc. (Meth)acrylic acid cycloalkenyloxyalkyl ester and the like.

作為前述含縮水甘油基之(甲基)丙烯酸酯，例如可列 舉(甲基)丙烯酸縮水甘油酯等。 Examples of the aforementioned glycidyl group-containing (meth)acrylate include, for example, Glycidyl (meth)acrylate etc. are mentioned.

作為前述含羥基之(甲基)丙烯酸酯，例如可列舉：(甲基)丙烯酸羥基甲酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等。 Examples of the hydroxyl group-containing (meth)acrylate include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylate ) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and the like.

作為前述含取代胺基之(甲基)丙烯酸酯，例如可列舉(甲基)丙烯酸N-甲基胺基乙酯等。 As said substituted amino group containing (meth)acrylate, (meth)acrylate N-methylaminoethyl etc. are mentioned, for example.

作為構成丙烯酸系聚合物(b-1)之前述非丙烯酸系單體，例如可列舉：乙烯、降冰片烯等烯烴；乙酸乙烯酯；苯乙烯等。 As said non-acrylic-type monomer which comprises an acrylic-type polymer (b-1), olefin, such as ethylene and norbornene; vinyl acetate; styrene, etc. are mentioned, for example.

作為至少一部分藉由交聯劑進行交聯且不具有前述能量線硬化性基之聚合物(b)，例如可列舉：前述聚合物(b)中的反應性官能基與交聯劑反應之聚合物。 Examples of the polymer (b) that is at least partially cross-linked by a cross-linking agent and does not have the above-mentioned energy ray-curable group include polymerization in which the reactive functional group in the above-mentioned polymer (b) reacts with a cross-linking agent. thing.

前述反應性官能基根據交聯劑之種類等適宜選擇即可，並無特別限定。例如，於交聯劑為多異氰酸酯化合物之情形時，作為前述反應性官能基，可列舉羥基、羧基、胺基等，這些之中，較佳為與異氰酸酯基之反應性高之羥基。另外，於交聯劑為環氧系化合物之情形時，作為前述反應性官能基，可列舉羧基、胺基、醯胺基等，這些之中，較佳為與環氧基之反應性高之羧基。但是，就防止半導體 晶圓或半導體晶片的電路腐蝕之方面而言，前述反應性官能基較佳為羧基以外的基。 The reactive functional group may be appropriately selected according to the type of the crosslinking agent and the like, and is not particularly limited. For example, when the crosslinking agent is a polyisocyanate compound, the reactive functional group includes a hydroxyl group, a carboxyl group, an amine group, and the like, and among these, a hydroxyl group having high reactivity with an isocyanate group is preferred. In addition, when the crosslinking agent is an epoxy-based compound, examples of the reactive functional group include a carboxyl group, an amino group, an amide group, and the like, and among these, the one with high reactivity with an epoxy group is preferred. carboxyl. However, to prevent semiconductors In terms of circuit etching of wafers or semiconductor chips, the reactive functional group is preferably a group other than a carboxyl group.

作為具有前述反應性官能基且不具有能量線硬化性基之聚合物(b)，例如可列舉：至少使具有前述反應性官能基之單體進行聚合而獲得之聚合物。於丙烯酸系聚合物(b-1)之情形時，作為構成該丙烯酸系聚合物(b-1)之單體所列舉之前述丙烯酸系單體及非丙烯酸系單體的任一者或兩者，使用具有前述反應性官能基之單體即可。例如，作為具有羥基作為反應性官能基之前述聚合物(b)，例如可列舉使含羥基之(甲基)丙烯酸酯進行聚合而獲得之聚合物，除此以外，亦可列舉使上文所列舉之前述丙烯酸系單體或非丙烯酸系單體中1個或2個以上氫原子被前述反應性官能基取代而成之單體進行聚合而獲得之聚合物。 As a polymer (b) which has the said reactive functional group and does not have an energy ray hardening group, the polymer obtained by polymerizing at least the monomer which has the said reactive functional group is mentioned, for example. In the case of the acrylic polymer (b-1), either or both of the aforementioned acrylic monomers and non-acrylic monomers listed as the monomers constituting the acrylic polymer (b-1) , the monomer with the aforementioned reactive functional group can be used. For example, as the polymer (b) having a hydroxyl group as a reactive functional group, for example, a polymer obtained by polymerizing a hydroxyl group-containing (meth)acrylate can be mentioned. A polymer obtained by polymerizing a monomer in which one or two or more hydrogen atoms of the aforementioned acrylic monomers or non-acrylic monomers are substituted with the aforementioned reactive functional groups.

具有反應性官能基之前述聚合物(b)中，由具有反應性官能基之單體衍生之結構單元的量相對於構成該聚合物(b)之結構單元的全部量之比例(含量)較佳為1質量%至20質量%，更佳為2質量%至10質量%。藉由前述比例為此種範圍，前述聚合物(b)中，交聯程度成為更佳的範圍。 In the aforementioned polymer (b) having a reactive functional group, the ratio (content) of the amount of the structural unit derived from the monomer having a reactive functional group to the total amount of the structural units constituting the polymer (b) is relatively Preferably it is 1 mass % - 20 mass %, More preferably, it is 2 mass % - 10 mass %. Since the said ratio is such a range, in the said polymer (b), the degree of crosslinking becomes a more preferable range.

就保護膜形成用組成物(IV-1)的造膜性更良好之方面而言，不具有能量線硬化性基之聚合物(b)的重量平均分子量(Mw)較佳為10000至2000000，更佳為100000至 1500000。此處，所謂「重量平均分子量」係如上文所說明。 The weight average molecular weight (Mw) of the polymer (b) not having an energy ray-curable group is preferably from 10,000 to 2,000,000 in terms of better film-forming properties of the protective film-forming composition (IV-1), More preferably 100000 to 1500000. Here, the so-called "weight average molecular weight" is as described above.

保護膜形成用組成物(IV-1)及能量線硬化性保護膜形成用膜所含有之不具有能量線硬化性基之聚合物(b)可僅為1種，亦可為2種以上；於為2種以上之情形時，這些之組合及比率可任意選擇。 The composition for forming a protective film (IV-1) and the film for forming an energy ray curable protective film may contain only one polymer (b) without an energy ray curable group, or two or more kinds; In the case of two or more types, the combination and ratio of these can be arbitrarily selected.

作為保護膜形成用組成物(IV-1)，可列舉含有前述聚合物(a1)及前述化合物(a2)的任一者或兩者之組成物。並且，於保護膜形成用組成物(IV-1)含有前述化合物(a2)之情形時，較佳為亦進一步含有不具有能量線硬化性基之聚合物(b)，該情形時，亦較佳為進一步含有前述(a1)。另外，保護膜形成用組成物(IV-1)亦可不含有前述化合物(a2)，且一併含有前述聚合物(a1)及不具有能量線硬化性基之聚合物(b)。 As the composition (IV-1) for forming a protective film, a composition containing either or both of the above-mentioned polymer (a1) and the above-mentioned compound (a2) can be mentioned. In addition, when the composition (IV-1) for forming a protective film contains the aforementioned compound (a2), it is preferable to further contain a polymer (b) having no energy ray curable group, and in this case, it is also preferable It is preferable to further contain the said (a1). Moreover, the composition (IV-1) for forming a protective film may not contain the said compound (a2), and may contain the said polymer (a1) and the polymer (b) which does not have an energy ray curable group together.

於保護膜形成用組成物(IV-1)含有前述聚合物(a1)、前述化合物(a2)及不具有能量線硬化性基之聚合物(b)之情形時，保護膜形成用組成物(IV-1)中，前述化合物(a2)的含量相對於前述聚合物(a1)及不具有能量線硬化性基之聚合物(b)的總含量100質量份，較佳為10質量份至400質量份，更佳為30質量份至350質量份。 When the composition (IV-1) for forming a protective film contains the polymer (a1), the compound (a2), and the polymer (b) without an energy ray curable group, the composition for forming a protective film ( In IV-1), the content of the aforementioned compound (a2) is preferably 10 to 400 parts by mass relative to 100 parts by mass of the total content of the aforementioned polymer (a1) and the polymer (b) having no energy ray hardening group parts by mass, more preferably 30 parts by mass to 350 parts by mass.

保護膜形成用組成物(IV-1)中，前述能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的合計含量(亦即，能量線硬化性保護膜形成用膜中的前述能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的合計含量)相對於溶劑以外的成分的總含量之比例較佳為5質量%至90質量%，更佳為10質量%至80質量%，尤佳為20質量%至70質量%。藉由能量線硬化性成分的含量的前述比例為此種範圍，能量線硬化性保護膜形成用膜的能量線硬化性變得更良好。 In the composition (IV-1) for forming a protective film, the total content of the energy ray curable component (a) and the polymer (b) having no energy ray curable group (that is, the energy ray curable protective film forming The ratio of the total content of the aforementioned energy ray-curable component (a) and the polymer (b) having no energy ray-curable group) to the total content of components other than the solvent in the film is preferably 5% by mass to 90% by mass. The mass % is more preferably 10 to 80 mass %, particularly preferably 20 to 70 mass %. When the said ratio of content of an energy ray curable component is such a range, the energy ray curability of the film for energy ray curable protective film formation becomes more favorable.

保護膜形成用組成物(IV-1)中，除前述能量線硬化性成分以外，亦可根據目的而含有選自由熱硬化性成分、光聚合起始劑、填充材料、偶合劑、交聯劑、著色劑及通用添加劑所組成之群組中的1種或2種以上。例如，藉由使用含有前述能量線硬化性成分及熱硬化性成分之保護膜形成用組成物(IV-1)，所形成之能量線硬化性保護膜形成用膜藉由加熱而對被黏著體之接著力提高，由該能量線硬化性保護膜形成用膜形成之保護膜的強度亦提高。 The composition (IV-1) for forming a protective film may contain, in addition to the above-mentioned energy ray curable component, a thermosetting component, a photopolymerization initiator, a filler, a coupling agent, and a crosslinking agent according to the purpose. , one or more of the group consisting of colorants and general additives. For example, by using the composition for forming a protective film (IV-1) containing the energy ray curable component and the thermosetting component, the formed film for forming an energy ray curable protective film is heated to the adherend. The adhesive force is improved, and the intensity|strength of the protective film formed from this film for energy-beam curable protective film formation is also improved.

作為保護膜形成用組成物(IV-1)中的前述熱硬化性成分、光聚合起始劑、填充材料、偶合劑、交聯劑、著色劑及通用添加劑，可列舉：分別與保護膜形成用組成物(III-1)中的熱硬化性成分(B)、光聚合起始劑(H)、填充材料(D)、 偶合劑(E)、交聯劑(F)、著色劑(I)及通用添加劑(J)相同之化合物。 Examples of the above-mentioned thermosetting components, photopolymerization initiators, fillers, coupling agents, crosslinking agents, colorants, and general additives in the composition (IV-1) for forming a protective film include: Thermosetting component (B), photopolymerization initiator (H), filler (D), Coupling agent (E), crosslinking agent (F), colorant (I) and general additive (J) are the same compounds.

保護膜形成用組成物(IV-1)中，前述熱硬化性成分、光聚合起始劑、填充材料、偶合劑、交聯劑、著色劑及通用添加劑可分別單獨使用1種，亦可併用2種以上，於併用2種以上之情形時，這些之組合及比率可任意選擇。 In the composition (IV-1) for forming a protective film, the aforementioned thermosetting components, photopolymerization initiators, fillers, coupling agents, crosslinking agents, colorants and general additives may be used alone or in combination. When two or more types are used in combination, the combination and ratio of these can be arbitrarily selected.

保護膜形成用組成物(IV-1)中的前述熱硬化性成分、光聚合起始劑、填充材料、偶合劑、交聯劑、著色劑及通用添加劑的含量根據目的適宜調節即可，並無特別限定。 The contents of the aforementioned thermosetting components, photopolymerization initiators, fillers, coupling agents, crosslinking agents, colorants and general additives in the composition (IV-1) for forming a protective film may be appropriately adjusted according to the purpose, and There is no particular limitation.

就藉由稀釋而使該組成物的操作性提高而言，保護膜形成用組成物(IV-1)較佳為進一步含有溶劑。 It is preferable that the composition for protective film formation (IV-1) further contains a solvent in order to improve the handleability of this composition by dilution.

作為保護膜形成用組成物(IV-1)所含有之溶劑，例如可列舉與保護膜形成用組成物(III-1)中的溶劑相同之溶劑。 As a solvent contained in the composition (IV-1) for forming a protective film, for example, the same solvent as the solvent in the composition (III-1) for forming a protective film can be mentioned.

保護膜形成用組成物(IV-1)所含有之溶劑可僅為1種，亦可為2種以上。 The solvent contained in the composition (IV-1) for forming a protective film may be only one type or two or more types.

<<能量線硬化性保護膜形成用組成物的製造方法>> <<The manufacturing method of the composition for energy ray curable protective film forming>>

保護膜形成用組成物(IV-1)等能量線硬化性保護膜形成用組成物可藉由調配用以構成該組成物之各成分而獲得。 The composition for energy ray-curable protective film formation, such as the composition for protective film formation (IV-1), can be obtained by mixing each component which comprises this composition.

調配各成分時之添加順序並無特別限定，亦可同時添 加2種以上之成分。 The order of addition of the ingredients is not particularly limited, and they may be added at the same time. Add 2 or more ingredients.

於使用溶劑之情形時，可藉由下述方式使用：將溶劑與溶劑以外的任一種調配成分混合而將該調配成分預先稀釋；亦可藉由下述方式使用：不將溶劑以外的任一種調配成分預先稀釋而將溶劑與這些調配成分混合。 In the case of using a solvent, it can be used by mixing the solvent with any preparation component other than the solvent and diluting the preparation component in advance; it can also be used in the following way: not using any preparation component other than the solvent The formulating ingredients are pre-diluted and the solvent is mixed with these formulating ingredients.

調配時混合各成分之方法並無特別限定，自以下公知的方法中適宜選擇即可：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機進行混合之方法；施加超音波進行混合之方法等。 The method of mixing the components during the preparation is not particularly limited, and may be appropriately selected from the following well-known methods: a method of mixing by rotating a stirring bar or a stirring blade, a method of mixing using a mixer, and a method of applying ultrasonic waves for mixing method etc.

關於添加及混合各成分時的溫度及時間，只要不使各調配成分劣化，即無特別限定，適宜調節即可，溫度較佳為15℃至30℃。 The temperature and time at the time of adding and mixing each component are not particularly limited as long as each compounded component is not degraded, and may be appropriately adjusted, and the temperature is preferably 15°C to 30°C.

○塗層 ○Coating

關於前述塗層，只要該塗層中的與和支持片接觸之側為相反側的表面的光澤值為32至95，即無特別限定。 The aforementioned coating layer is not particularly limited as long as the gloss value of the surface of the coating layer on the side opposite to the side in contact with the support sheet is 32 to 95.

作為較佳的塗層，例如較佳為含有藉由照射能量線進行硬化而獲得之硬化物之塗層，較佳為使含有藉由照射能量線進行聚合之能量線聚合性化合物之塗佈組成物硬化而獲得之塗層。 As a preferable coating layer, for example, a coating composition containing a cured product obtained by curing by irradiation with energy rays is preferable, and a coating composition containing an energy-ray polymerizable compound polymerized by irradiation with energy rays is preferable. A coating obtained by hardening the material.

並且，前述能量線聚合性化合物較佳為(甲基)丙烯酸或其衍生物。 Further, the energy ray polymerizable compound is preferably (meth)acrylic acid or a derivative thereof.

前述保護膜形成用複合片不僅具有形成用以保護切割所得之半導體晶片的背面之功能，例如亦可兼具作為切割半導體晶圓時之切割片之功能。並且，切割半導體晶圓時，有時將貼附有保護膜形成用複合片之半導體晶圓延伸；該情形時，要求保護膜形成用複合片具有適度的柔軟性。為了對保護膜形成用複合片賦予適度的柔軟性，例如有時選擇聚丙烯等柔軟的樹脂作為構成前述支持片之材質。另一方面，此種柔軟的樹脂等有時因加熱而變形或產生褶皺。因此，塗層可謂較理想為使成為原料之組成物藉由照射能量線進行硬化，並非進行熱硬化而形成。 The above-mentioned composite sheet for forming a protective film not only has the function of being formed to protect the back surface of the semiconductor wafer obtained by dicing, but also has the function of, for example, a dicing sheet when dicing the semiconductor wafer. In addition, when a semiconductor wafer is diced, the semiconductor wafer to which the composite sheet for forming a protective film is attached may be stretched; in this case, the composite sheet for forming a protective film is required to have moderate flexibility. In order to impart moderate flexibility to the composite sheet for forming a protective film, for example, a flexible resin such as polypropylene may be selected as a material constituting the support sheet. On the other hand, such a soft resin or the like may be deformed or wrinkled by heating. Therefore, it can be said that the coating layer is preferably formed by curing the composition used as the raw material by irradiating energy rays, not by thermal curing.

前述塗層的厚度並無特別限定，較佳為0.1μm至20μm，更佳為0.4μm至15μm，尤佳為0.8μm至10μm。藉由塗層的厚度為前述下限值以上，塗層中的與和前述支持片接觸之側為相反側的表面的表面粗糙度Ra變得更容易降低，進一步抑制前述保護膜形成用複合片之黏連之功效變得更高。另外，藉由塗層的厚度為前述上限值以下，經由前述片藉由紅外線相機等檢測貼附前述保護膜形成用複合片後的半導體晶圓的狀態時，可獲取更清晰的檢測圖像，進一步可更容易地伴隨延伸切割半導體晶圓。 The thickness of the aforementioned coating layer is not particularly limited, but is preferably 0.1 μm to 20 μm, more preferably 0.4 μm to 15 μm, and particularly preferably 0.8 μm to 10 μm. By the thickness of the coating being more than the aforementioned lower limit value, the surface roughness Ra of the surface on the opposite side to the side in contact with the aforementioned support sheet in the coating becomes easier to reduce, further suppressing the aforementioned protective film forming composite sheet The effect of adhesion becomes higher. In addition, when the thickness of the coating layer is equal to or less than the upper limit value, a clearer inspection image can be obtained when the state of the semiconductor wafer to which the composite sheet for forming a protective film is attached is detected by an infrared camera or the like through the sheet. , which further makes it easier to dicing the semiconductor wafer along with the extension.

再者，由於塗層如上所述般被覆支持片的凹凸面，故而與支持片之接觸面可成為凹凸面；關於塗層的厚度，於塗層的該凹凸面中包含凸部之部位中，將該凸部的頂端作為一起點而算出即可。 Furthermore, because the coating covers the concave-convex surface of the supporting sheet as described above, the contact surface with the supporting sheet can become the concave-convex surface; about the thickness of the coating, in the position of the convex portion in this concave-convex surface of the coating, The tip of the convex portion may be calculated as a common point.

前述塗層中的與和前述支持片接觸之側為相反側的表面的表面粗糙度Ra較佳為0.5μm以下，更佳為0.4μm以下，進一步較佳為0.3μm以下，尤佳為0.2μm以下。藉由塗層的前述表面粗糙度Ra為前述上限值以下，可對保護膜更清晰地進行雷射印字。 The surface roughness Ra of the surface on the opposite side to the side in contact with the support sheet in the coating layer is preferably 0.5 μm or less, more preferably 0.4 μm or less, further preferably 0.3 μm or less, particularly preferably 0.2 μm the following. When the surface roughness Ra of the coating layer is equal to or less than the upper limit value, the protective film can be more clearly laser-printed.

另外，前述塗層中的與和前述支持片接觸之側為相反側的表面的表面粗糙度Ra的下限值並無特別限定，例如可設為0.005μm等。 In addition, the lower limit value of the surface roughness Ra of the surface on the opposite side to the side in contact with the support sheet in the coating layer is not particularly limited, and can be set to, for example, 0.005 μm or the like.

塗層的前述表面粗糙度Ra例如可藉由支持片中的具備塗層之側的表面的表面粗糙度Ra、塗層的厚度、用以形成塗層之後述塗佈組成物之塗敷方法等進行調節。 The aforementioned surface roughness Ra of the coating layer can be determined, for example, by the surface roughness Ra of the surface on the side with the coating layer in the support sheet, the thickness of the coating layer, the coating method of the coating composition described later for forming the coating layer, and the like. Make adjustments.

關於前述塗層，[塗層的厚度(μm)]/[支持片中的具備塗層之側的表面的表面粗糙度Ra(μm)]之值較佳為0.1至30，更佳為0.3至20，尤佳為0.5至10。藉由前述值為前述下限值以上，塗層中的與和前述支持片接觸之側為相反側的表面的表面粗糙度Ra變得更小，可對保護膜更清晰地進行雷射印字，進一步，抑制前述保護膜形成用複合片之黏連之功效變得更高。另外，藉由前述值為前述上限值以下，可避免塗層的厚度過厚。 Regarding the aforementioned coating layer, the value of [the thickness of the coating layer (μm)]/[the surface roughness Ra (μm) of the surface on the side having the coating layer in the support sheet] is preferably from 0.1 to 30, more preferably from 0.3 to 30. 20, preferably 0.5 to 10. With the aforementioned value being above the aforementioned lower limit value, the surface roughness Ra of the surface on the opposite side to the side in contact with the aforementioned support sheet in the coating becomes smaller, and the protective film can be more clearly laser-printed, Furthermore, the effect of suppressing the blocking of the composite sheet for forming a protective film becomes higher. Moreover, since the said value is below the said upper limit, the thickness of a coating layer can be prevented from becoming too thick.

前述塗層中的與和前述支持片接觸之側(前述支持片側)為相反側的表面的光澤值為32至95，較佳為40至90， 更佳為45至85。藉由塗層的前述光澤值為此種範圍，可對保護膜更清晰地進行雷射印字。進一步，藉由塗層的前述光澤值為前述下限值以上，經由前述片藉由紅外線相機等檢測貼附前述保護膜形成用複合片後的半導體晶圓的狀態時，可獲取更清晰的檢測圖像。並且，藉由塗層的前述光澤值為前述上限值以下，同樣地檢測半導體晶圓的狀態時，可抑制塗層發亮之現象，更容易利用紅外線相機等視認檢測圖像。 The gloss value of the surface of the opposite side is 32 to 95, preferably 40 to 90, with the side in contact with the aforementioned support sheet (the aforementioned support sheet side) in the aforementioned coating, More preferably, it is 45 to 85. When the aforementioned gloss value of the coating layer is in this range, the protective film can be more clearly laser-printed. Further, when the gloss value of the coating layer is equal to or greater than the lower limit value, when the state of the semiconductor wafer to which the composite sheet for forming a protective film is attached is detected by an infrared camera or the like through the sheet, a clearer detection can be obtained. image. In addition, when the gloss value of the coating layer is equal to or less than the upper limit value, when the state of the semiconductor wafer is similarly detected, the coating layer can be suppressed from shining, and the inspection image can be more easily recognized by an infrared camera or the like.

保護膜形成用複合片的自前述塗層側的霧度的測定值較佳為47%以下，更佳為1%至47%，進一步較佳為2%至40%，尤佳為3%至30%。藉由保護膜形成用複合片的前述霧度為前述上限值以下，可抑制光之散射，從而可對保護膜更清晰地進行雷射印字。另外，經由前述片藉由紅外線相機等檢測貼附前述保護膜形成用複合片後的半導體晶圓的狀態時，可獲取更清晰的檢測圖像。此處，所謂保護膜形成用複合片的前述霧度的測定值，意指針對保護膜形成用複合片，自前述塗層中的與和前述支持片接觸之側為相反側的表面的方向測定之霧度值。 The measured value of the haze from the coating side of the composite sheet for forming a protective film is preferably 47% or less, more preferably 1% to 47%, further preferably 2% to 40%, particularly preferably 3% to 40%. 30%. Since the said haze of the composite sheet for protective film formation is below the said upper limit, scattering of light can be suppressed, and a protective film can be laser-printed more clearly. Further, when the state of the semiconductor wafer to which the composite sheet for forming a protective film is attached is detected by an infrared camera or the like via the sheet, a clearer inspection image can be obtained. Here, the measured value of the haze of the composite sheet for forming a protective film means that the composite sheet for forming a protective film is measured from the direction of the surface on the opposite side of the coating layer that is in contact with the support sheet. the haze value.

再者，前述霧度係依據JIS K 7136進行測定而獲得之值。 In addition, the said haze is the value obtained by measuring based on JISK7136.

前述塗層的光澤值等各種特性例如可藉由塗層的厚度、用以形成塗層之後述塗佈組成物的含有成分等進行調節。 Various properties such as the gloss value of the coating layer can be adjusted by, for example, the thickness of the coating layer, the components contained in the coating composition described later for forming the coating layer, and the like.

保護膜形成用複合片的自前述塗層側的霧度的測定值例如可藉由塗層或支持片等構成保護膜形成用複合片之各層的厚度、用以形成這些各層之組成物(例如，後述塗佈組成物)的含有成分等進行調節。 The measured value of the haze from the coating side of the composite sheet for forming a protective film can be determined by, for example, the thickness of each layer constituting the composite sheet for forming a protective film by a coating layer, a support sheet, or the like, and the composition for forming these layers (for example, , the components contained in the coating composition, which will be described later, are adjusted.

<<塗佈組成物>> <<Coating composition>>

前述塗佈組成物較佳為含有二氧化矽溶膠及鍵結有含自由基聚合性不飽和基之有機化合物之二氧化矽微粒子中的任一者或兩者(α)(以下，有時簡稱為「成分(α)」)、以及選自由多官能性丙烯酸酯系單體及丙烯酸酯系預聚物所組成之群組中的1種以上(β)(以下，有時簡稱為「成分(β)」)。 The coating composition is preferably one or both (α) (hereinafter, sometimes abbreviated as abbreviated as SiO 2 sol) and silica fine particles bound with an organic compound containing a radically polymerizable unsaturated group. "component (α)"), and at least one (β) selected from the group consisting of a polyfunctional acrylate-based monomer and an acrylate-based prepolymer (hereinafter, sometimes abbreviated as "component ( β)").

[成分(α)] [Ingredient (α)]

前述成分(α)使前述塗層的折射率降低，並且使前述保護膜形成用複合片的硬化收縮性及熱濕收縮性降低，從而抑制因這些收縮而導致保護膜形成用複合片中產生捲曲。 The component (α) reduces the refractive index of the coating layer and reduces the curing shrinkage and heat-moisture shrinkage of the composite sheet for forming a protective film, thereby suppressing the occurrence of curling in the composite sheet for forming a protective film due to these shrinkages .

作為成分(α)中的二氧化矽溶膠，例如可列舉膠體二氧化矽，該膠體二氧化矽係二氧化矽微粒子於醇、源自乙 二醇之醚(溶纖劑)等有機溶劑中以膠體(colloid)狀態懸浮而成，懸浮之前述二氧化矽微粒子的平均粒徑較佳為0.001μm至1μm，更佳為0.03μm至0.05μm。 As the silica sol in the component (α), for example, colloidal silica can be mentioned, and the colloidal silica-based silica fine particles are derived from alcohol, It is formed by suspending in an organic solvent such as glycol ether (cellosolve) in a colloid state. The average particle size of the suspended silica particles is preferably 0.001 μm to 1 μm, more preferably 0.03 μm to 0.05 μm .

成分(α)中的鍵結有含自由基聚合性不飽和基之有機化合物之二氧化矽微粒子藉由照射能量線而進行交聯及硬化。 The silica fine particles in which the radically polymerizable unsaturated group-containing organic compound is bonded in the component (α) are cross-linked and cured by irradiation with energy rays.

作為前述鍵結有含自由基聚合性不飽和基之有機化合物之二氧化矽微粒子，例如可列舉存在於二氧化矽微粒子的表面之矽烷醇基與含自由基聚合性不飽和基之有機化合物中的官能基反應而成之粒子，該二氧化矽微粒子的平均粒徑較佳為0.005μm至1μm。含自由基聚合性不飽和基之有機化合物中的前述官能基只要可與二氧化矽微粒子中的前述矽烷醇基反應，即無特別限定。 Examples of the silica fine particles to which the radically polymerizable unsaturated group-containing organic compound is bound include, for example, silanol groups and radically polymerizable unsaturated group-containing organic compounds present on the surface of the silica fine particles. The particles formed by the reaction of the functional groups of the silica particles, the average particle size of the silica particles is preferably 0.005 μm to 1 μm. The functional group in the radically polymerizable unsaturated group-containing organic compound is not particularly limited as long as it can react with the silanol group in the silica fine particle.

作為具有前述官能基之含自由基聚合性不飽和基之有機化合物，例如可列舉下述通式(1)所表示之化合物等。 As a radical polymerizable unsaturated group containing organic compound which has the said functional group, the compound etc. which are represented by following general formula (1) are mentioned, for example.

Figure 106104893-A0202-12-0084-1
Figure 106104893-A0202-12-0084-1

(式中，R1為氫原子或甲基；R2為鹵素原子或下述式(2a)至式(2f)中的任一者所表示之基) (In the formula, R 1 is a hydrogen atom or a methyl group; R 2 is a halogen atom or a group represented by any one of the following formulae (2a) to (2f))

Figure 106104893-A0202-12-0085-2
Figure 106104893-A0202-12-0085-2

作為R2中的前述鹵素原子，例如可列舉：氯原子、溴原子、碘原子等。 As said halogen atom in R< 2 >, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.

作為較佳的前述含自由基聚合性不飽和基之有機化合物，例如可列舉：(甲基)丙烯酸、(甲基)丙烯醯氯、(甲基)丙烯酸2-異氰酸酯基乙酯、(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸2,3-亞胺基丙酯、(甲基)丙烯酸2-羥基乙酯、(3-(甲基)丙烯醯氧基丙基)三甲氧基矽烷等。 Examples of preferable radical-polymerizable unsaturated group-containing organic compounds include (meth)acrylic acid, (meth)acryloyl chloride, 2-isocyanatoethyl (meth)acrylate, (meth)acrylic acid, and (meth)acrylic acid. ) glycidyl acrylate, 2,3-iminopropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (3-(meth)acryloyloxypropyl)trimethoxysilane Wait.

本實施形態中，前述含自由基聚合性不飽和基之有機化合物可單獨使用1種，亦可併用2種以上。 In the present embodiment, the radically polymerizable unsaturated group-containing organic compound may be used alone or in combination of two or more.

成分(α)中，二氧化矽溶膠、及鍵結有含自由基聚合性不飽和基之有機化合物之二氧化矽微粒子可分別僅為1種，亦可為2種以上。 In the component (α), the silica sol and the silica fine particles bound with the radically polymerizable unsaturated group-containing organic compound may each be only one type or two or more types.

作為成分(α)，可僅使用二氧化矽溶膠，亦可僅使用前述鍵結有含自由基聚合性不飽和基之有機化合物之二氧化矽微粒子，還可併用二氧化矽溶膠及前述鍵結有含自由基聚合性不飽和基之有機化合物之二氧化矽微粒子。 As the component (α), only silica sol may be used, only the above-mentioned silica fine particles bound with an organic compound containing a radically polymerizable unsaturated group may be used, or a combination of silica sol and the above-mentioned bonding may be used. Silica microparticles containing organic compounds containing radically polymerizable unsaturated groups.

前述塗佈組成物中的成分(α)的含量較佳為根據前述支持片的折射率進行選擇，通常較佳為使前述塗層中的源自成分(α)之二氧化矽的含量成為20質量%至60質量%之量。藉由二氧化矽的前述含量為前述下限值以上，使塗層的折射率降低之功效、及抑制前述保護膜形成用複合片中產生捲曲之功效變得更高。另外，藉由二氧化矽的前述含量為前述上限值以下，更容易形成塗層，並且抑制塗層硬度降低之功效變得更高。 The content of the component (α) in the aforementioned coating composition is preferably selected according to the refractive index of the aforementioned support sheet, and usually the content of the silicon dioxide derived from the component (α) in the aforementioned coating layer is preferably 20 Mass % to 60 mass %. When the said content of silicon dioxide is more than the said lower limit, the effect of reducing the refractive index of a coating layer, and the effect of suppressing the generation|occurence|production of curl in the said composite sheet for protective film formation become high. In addition, by the above-mentioned content of silicon dioxide being equal to or less than the above-mentioned upper limit value, it becomes easier to form a coating layer, and the effect of suppressing a decrease in the hardness of the coating layer becomes higher.

就上述塗層的折射率、形成容易性及硬度、以及抑制保護膜形成用複合片中產生捲曲之性質變得更良好而言，塗層中的源自成分(α)之二氧化矽的含量更佳為20質量%至45質量%。 The refractive index, ease of formation and hardness of the above-mentioned coating layer, and the property of suppressing the occurrence of curling in the composite sheet for forming a protective film are improved, and the content of the silicon dioxide derived from the component (α) in the coating layer More preferably, it is 20 mass % to 45 mass %.

[成分(β)] [Ingredient (β)]

前述成分(β)為形成前述塗層之主要的光硬化性成分。 The said component (β) is the main photocurable component which forms the said coating layer.

前述成分(β)中的多官能性丙烯酸酯系單體只要為於1分子中具有2個以上(甲基)丙烯醯基之(甲基)丙烯酸衍生物，即無特別限定。 The polyfunctional acrylate-based monomer in the component (β) is not particularly limited as long as it is a (meth)acrylic acid derivative having two or more (meth)acryloyl groups in one molecule.

作為較佳的前述多官能性丙烯酸酯系單體，例如可列舉：1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、羥基特戊酸新戊二醇二(甲基)丙烯酸酯、二(甲基)丙烯酸二環戊酯、己內酯改性二(甲基)丙烯酸二環戊烯酯、環氧乙烷改性磷酸二(甲基)丙烯酸酯、烯丙基化環己基二(甲基)丙烯酸酯、異氰脲酸酯二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、丙酸改性二季戊四醇三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、環氧丙烷改性三羥甲基丙烷三(甲基)丙烯酸酯、異氰脲酸三(丙烯醯氧基乙基)酯、二季戊四醇五(甲基)丙烯酸酯、丙酸改性二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、己內酯改性二季戊四醇六(甲基)丙烯酸酯等。 As a preferable said polyfunctional acrylate type monomer, for example, 1, 4- butanediol di(meth)acrylate, 1, 6-hexanediol di(meth)acrylate, neopentyl Glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, dicyclopentyl di(meth)acrylate, hexamethylene Lactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate Di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate ) acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, tris(acrylooxyethyl) isocyanurate, dipentaerythritol penta(meth)acrylate, propionic acid modified Sexual dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, etc.

前述成分(β)中的丙烯酸酯系預聚物只要為利用(甲基)丙烯酸酯而具有光硬化性之聚合物或低聚物，即無特別限定。 The acrylate-based prepolymer in the aforementioned component (β) is not particularly limited as long as it is a polymer or oligomer having photocurability using (meth)acrylate.

作為較佳的前述丙烯酸酯系預聚物，例如可列舉：聚酯丙烯酸酯系預聚物、環氧丙烯酸酯系預聚物、丙烯酸胺基甲酸酯系預聚物、多元醇丙烯酸酯系預聚物等。 Examples of preferable acrylate-based prepolymers include polyester acrylate-based prepolymers, epoxy acrylate-based prepolymers, acrylic urethane-based prepolymers, and polyol acrylate-based prepolymers. prepolymer, etc.

作為前述聚酯丙烯酸酯系預聚物，例如可列舉藉由下述方式而獲得之預聚物：藉由多元羧酸與多元醇之縮合反應而獲得於分子的兩末端具有羥基之聚酯低聚物，利用(甲基)丙烯酸將所獲得之聚酯低聚物的羥基酯化；使多元羧酸與環氧烷進行加成反應而獲得低聚物，利用(甲基)丙烯酸將所獲得之低聚物的末端的羥基酯化。 As said polyester acrylate-based prepolymer, for example, a prepolymer obtained by a condensation reaction of a polyvalent carboxylic acid and a polyhydric alcohol can be mentioned: a polyester oligomer having hydroxyl groups at both ends of the molecule is obtained The hydroxyl group of the obtained polyester oligomer is esterified with (meth)acrylic acid; the oligomer is obtained by addition reaction of polyvalent carboxylic acid and alkylene oxide, and the obtained oligomer is obtained with (meth)acrylic acid The terminal hydroxyl esterification of the oligomer.

作為前述環氧丙烯酸酯系預聚物，例如可列舉藉由下述方式而獲得之預聚物：使相對較低分子量的雙酚型環氧樹脂或酚醛清漆型環氧樹脂的環氧乙烷環(oxirane ring)與(甲基)丙烯酸反應而進行酯化。 As said epoxy acrylate type prepolymer, the prepolymer obtained by, for example, a relatively low molecular weight bisphenol-type epoxy resin or a novolac-type epoxy resin of ethylene oxide can be mentioned. A ring (oxirane ring) reacts with (meth)acrylic acid and is esterified.

作為前述丙烯酸胺基甲酸酯系預聚物，例如可列舉藉由下述方式而獲得之預聚物：藉由聚醚多元醇或聚酯多元醇與多異氰酸酯之反應而獲得聚胺基甲酸酯低聚物，利用(甲基)丙烯酸將所獲得之聚胺基甲酸酯低聚物酯化。 Examples of the aforementioned acrylic urethane-based prepolymer include prepolymers obtained by reacting polyether polyol or polyester polyol with polyisocyanate to obtain polyurethane The obtained polyurethane oligomer was esterified with (meth)acrylic acid.

作為前述多元醇丙烯酸酯系預聚物，例如可列舉藉由下述方式而獲得之預聚物：利用(甲基)丙烯酸將聚醚多元醇的羥基酯化。 As said polyol acrylate type prepolymer, the prepolymer obtained by esterifying the hydroxyl group of a polyether polyol with (meth)acrylic acid is mentioned, for example.

成分(β)中，前述多官能性丙烯酸酯系單體及丙烯酸酯系預聚物可分別僅為1種，亦可為2種以上。 In the component (β), each of the multifunctional acrylate-based monomer and the acrylate-based prepolymer may be only one type, or two or more types may be used.

作為成分(β)，可僅使用前述多官能性丙烯酸酯系單體，亦可僅使用前述丙烯酸酯系預聚物，還可併用前述多官能性丙烯酸酯系單體及丙烯酸酯系預聚物。 As the component (β), only the above-described polyfunctional acrylate-based monomer may be used, only the above-described acrylate-based prepolymer may be used, or the above-described polyfunctional acrylate-based monomer and acrylate-based prepolymer may be used in combination .

[溶劑] [solvent]

前述塗佈組成物較佳為除成分(α)及成分(β)以外進一步含有溶劑。藉由塗佈組成物含有溶劑，如後所述，可更容易地將塗佈組成物塗敷及乾燥，而形成用以形成塗層之塗膜。 In addition to the component (α) and the component (β), the coating composition preferably further contains a solvent. When the coating composition contains a solvent, as will be described later, the coating composition can be more easily applied and dried to form a coating film for forming a coating layer.

前述溶劑可單獨使用1種，亦可併用2種以上。 The said solvent may be used individually by 1 type, and may use 2 or more types together.

作為前述溶劑，例如可列舉：己烷、庚烷、環己烷等脂肪族烴；甲苯、二甲苯等芳香族烴；二氯甲烷、二氯乙烷等鹵代烴；甲醇、乙醇、丙醇、丁醇、1-甲氧基-2-丙醇等醇；丙酮、甲基乙基酮、2-戊酮、異佛爾酮、環己酮等酮；乙酸乙酯、乙酸丁酯等酯；2-乙氧基乙醇(乙基溶纖劑)等溶纖劑等。 Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane and dichloroethane; methanol, ethanol, and propanol. , butanol, 1-methoxy-2-propanol and other alcohols; acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone and other ketones; ethyl acetate, butyl acetate and other esters ; 2-ethoxyethanol (ethyl cellosolve) and other cellosolves.

[任意成分] [optional ingredient]

前述塗佈組成物中，除成分(α)及成分(β)以外，亦可在無損本發明的功效之範圍內，含有單官能性丙烯酸酯系單體、光聚合起始劑、光增感劑、聚合抑制劑、交聯劑、抗氧化劑、紫外線吸收劑、光穩定劑、調平劑、消泡劑等各種任意成分。 In addition to the component (α) and the component (β), the aforementioned coating composition may contain a monofunctional acrylate-based monomer, a photopolymerization initiator, a photosensitizer within the range that does not impair the effect of the present invention. Various optional ingredients such as agents, polymerization inhibitors, cross-linking agents, antioxidants, ultraviolet absorbers, light stabilizers, leveling agents, and antifoaming agents.

前述任意成分可單獨使用1種，亦可併用2種以上。 The said arbitrary components may be used individually by 1 type, and may use 2 or more types together.

(單官能性丙烯酸酯系單體) (Monofunctional Acrylate Monomer)

作為任意成分之前述單官能性丙烯酸酯系單體為光硬化性成分，只要為於1分子中僅具有1個(甲基)丙烯醯基之(甲基)丙烯酸衍生物，即無特別限定。 The monofunctional acrylate-based monomer as an optional component is a photocurable component, and is not particularly limited as long as it is a (meth)acrylic derivative having only one (meth)acryloyl group in one molecule.

作為較佳的前述單官能性丙烯酸酯系單體，例如可列舉：(甲基)丙烯酸環己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸十二烷基酯((甲基)丙烯酸月桂酯)、(甲基)丙烯酸十八烷基酯((甲基)丙烯酸硬脂酯)、(甲基)丙烯酸異冰片酯等。 As a preferable said monofunctional acrylate type monomer, for example, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate ( (lauryl (meth)acrylate), octadecyl (meth)acrylate (stearyl (meth)acrylate), isobornyl (meth)acrylate, and the like.

(光聚合起始劑) (photopolymerization initiator)

作為任意成分之前述光聚合起始劑可列舉：針對自由基聚合以往所使用之公知的光聚合起始劑。 As said photoinitiator of an arbitrary component, the well-known photoinitiator conventionally used for radical polymerization is mentioned.

作為較佳的前述光聚合起始劑，例如可列舉：苯乙酮系化合物、二苯甲酮系化合物、烷基胺基二苯甲酮系化合物、苯偶醯系化合物、安息香系化合物、安息香醚系化合物、苯偶醯二甲基縮酮系化合物、苯甲醯苯甲酸酯系化合物、α-醯基肟酯系化合物等芳基酮系光聚合起始劑；硫醚系化合物、噻噸酮系化合物等含硫系光聚合起始劑；醯基二芳基氧化膦等醯基氧化膦系化合物；蒽醌系化合物等。 Examples of preferable photopolymerization initiators include acetophenone-based compounds, benzophenone-based compounds, alkylaminobenzophenone-based compounds, benzoin-based compounds, benzoin-based compounds, and benzoin Aryl ketone-based photopolymerization initiators such as ether-based compounds, benzil dimethyl ketal-based compounds, benzyl benzoate-based compounds, and α-acyl oxime ester-based compounds; Sulfur-containing photopolymerization initiators such as xanthone-based compounds; acyl phosphine oxide-based compounds such as acyl diaryl phosphine oxide; anthraquinone-based compounds, and the like.

再者，於藉由照射電子束使前述塗佈組成物硬化之情形時，無需光聚合起始劑。 Furthermore, in the case where the coating composition is cured by irradiating an electron beam, a photopolymerization initiator is not required.

前述塗佈組成物中，光聚合起始劑的含量相對於光硬化性成分的總含量100質量份，較佳為0.2質量份至10質量份，更佳為0.5質量份至7質量份。 In the aforementioned coating composition, the content of the photopolymerization initiator is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 7 parts by mass relative to 100 parts by mass of the total content of the photocurable components.

(光增感劑) (photosensitizer)

作為前述光增感劑，例如可列舉：三級胺類、對二甲胺基苯甲酸酯、硫醇系增感劑等。 As said photosensitizer, a tertiary amine, p-dimethylaminobenzoate, a thiol-type sensitizer etc. are mentioned, for example.

前述塗佈組成物中，光增感劑的含量相對於光硬化性成分的總含量100質量份，較佳為1質量份至20質量份，更佳為2質量份至10質量份。 In the aforementioned coating composition, the content of the photosensitizer is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass relative to 100 parts by mass of the total content of the photocurable components.

(抗氧化劑、紫外線吸收劑、光穩定劑) (Antioxidants, UV Absorbers, Light Stabilizers)

前述抗氧化劑、紫外線吸收劑及光穩定劑可為公知的化合物，但較佳為於分子內具有(甲基)丙烯醯基等之反應型的抗氧化劑、紫外線吸收劑及光穩定劑。這些抗氧化劑、紫外線吸收劑及光穩定劑鍵結於藉由照射能量線而形成之聚合物鏈上，因此可抑制隨時間經過自硬化層逸散，從而長期發揮這些成分的功能。 The aforementioned antioxidants, ultraviolet absorbers and light stabilizers may be known compounds, but are preferably reactive antioxidants, ultraviolet absorbers, and light stabilizers having a (meth)acryloyl group or the like in the molecule. These antioxidants, ultraviolet absorbers, and light stabilizers are bonded to polymer chains formed by irradiating energy rays, so that they can be prevented from dissipating through the self-hardening layer over time, thereby exhibiting the functions of these components for a long period of time.

前述塗佈組成物較佳為含有二氧化矽溶膠作為成分(α)，更佳為含有以膠體狀態懸浮之二氧化矽微粒子的平均粒徑為0.03μm至0.05μm之二氧化矽溶膠。 The coating composition preferably contains silica sol as the component (α), and more preferably contains silica sol having an average particle diameter of 0.03 μm to 0.05 μm suspended in a colloidal state.

藉由前述塗層含有此種二氧化矽溶膠，抑制前述保護膜形成用複合片之黏連之功效變得更高。並且，前述塗層中，此種二氧化矽溶膠在與支持片側為相反側的表面或其附近區域，較其他區域更多地存在而偏集存在，藉此抑制前述保護膜形成用複合片之黏連之功效變得更高。前述塗層中，為了使二氧化矽溶膠等含有成分偏集存在，調節前述塗佈組成物之塗敷條件即可。 By containing such a silica sol in the coating layer, the effect of suppressing the blocking of the composite sheet for forming a protective film becomes higher. In addition, in the above-mentioned coating, the silica sol is more present and segregated on the surface opposite to the support sheet side or in the vicinity thereof than other areas, thereby suppressing the above-mentioned protective film forming composite sheet. The effect of adhesion has become higher. In the coating layer, the coating conditions of the coating composition may be adjusted in order to make the components such as silica sol exist in a segregated manner.

<<塗佈組成物的製造方法>> <<Manufacturing method of coating composition>>

塗佈組成物例如可藉由下述方式而獲得：將成分(α)及成分(β)等能量線聚合性化合物、及視需要的這些能量線聚合性化合物以外的成分等用以構成塗佈組成物之各成分加以調配。塗佈組成物例如可利用除調配成分不同之方面以外與上述黏著劑組成物之情形相同之方法獲得。 The coating composition can be obtained, for example, by using energy ray polymerizable compounds such as the component (α) and the component (β), and if necessary components other than these energy ray polymerizable compounds to constitute the coating composition. The components of the composition are adjusted. The coating composition can be obtained, for example, by the same method as in the case of the above-mentioned adhesive composition except that the composition is different.

於使用溶劑之情形時，可藉由下述方式使用：將溶劑與溶劑以外的任一種調配成分混合而將該調配成分預先稀釋；亦可藉由下述方式使用：不將溶劑以外的任一種調配成分預先稀釋而將溶劑與這些調配成分混合。 In the case of using a solvent, it can be used by mixing the solvent with any preparation component other than the solvent and diluting the preparation component in advance; it can also be used in the following way: not using any preparation component other than the solvent The formulating ingredients are pre-diluted and the solvent is mixed with these formulating ingredients.

塗佈組成物中的溶劑以外的成分可溶解，亦可不溶解而分散。並且，關於塗佈組成物中的各成分的濃度或黏度，只要使得塗佈組成物能夠塗敷，即無特別限定。 Components other than the solvent in the coating composition may be dissolved or dispersed without being dissolved. In addition, the concentration and viscosity of each component in the coating composition are not particularly limited as long as the coating composition can be applied.

◎保護膜形成用複合片的製造方法 ◎Manufacturing method of the composite sheet for protective film formation

本實施形態之保護膜形成用複合片可藉由下述方式而製造：使用前述保護膜形成用組成物形成保護膜形成用膜，使用前述塗佈組成物形成塗層，依序積層塗層、支持片及保護膜形成用膜。 The composite sheet for forming a protective film according to the present embodiment can be produced by forming a film for forming a protective film using the composition for forming a protective film, forming a coating layer using the coating composition, and sequentially laminating the coating layer, A film for forming a support sheet and a protective film.

於支持片由複數層構成之情形時，只要積層這些多個層而製作支持片即可。例如，於支持片由基材及黏著劑層積層而成之情形時，只要使用前述黏著劑組成物形成黏著劑層即可。 When the support sheet is composed of a plurality of layers, the support sheet may be produced by laminating these multiple layers. For example, when the support sheet is formed by laminating a base material and an adhesive, the adhesive layer may be formed using the above-mentioned adhesive composition.

構成保護膜形成用複合片之各層(塗層、支持片、保護膜形成用膜)的形成順序並無特別限定。進一步，由組成物形成這些各層時，可於保護膜形成用複合片之狀態下鄰接之層的表面上直接形成，亦可另行使用剝離膜(剝離片)而於該剝離膜(剝離片)的表面上形成，再將該形成層貼合於保護膜形成用複合片之狀態下鄰接之層的表面。但是，於支持片中的與具備保護膜形成用膜之面(表面)為相反側的面(背面)為凹凸面之情形時，為了抑制於塗層與支持片的凹凸面(背面)之間產生空隙部，較佳為於支持片的凹凸面直接塗敷塗佈組成物而形成塗層。 The formation order of each layer (coating layer, a support sheet, and the film for protective film formation) which comprises the composite sheet for protective film formation is not specifically limited. Furthermore, when these layers are formed from the composition, they may be directly formed on the surfaces of the adjacent layers in the state of the composite sheet for forming a protective film, or a release film (release sheet) may be used separately, and a release film (release sheet) may be used separately on the surface of the release film (release sheet). It is formed on the surface, and this forming layer is bonded to the surface of the adjacent layer in the state of the composite sheet for forming a protective film. However, when the surface (back surface) on the opposite side to the surface (front surface) provided with the protective film forming film in the support sheet is a concave and convex surface, in order to suppress the uneven surface (back surface) between the coating layer and the support sheet It is preferable to form a coating layer by directly applying the coating composition on the uneven surface of the support sheet to generate voids.

以下，對保護膜形成用複合片的較佳製造方法的一例進行說明。 Hereinafter, an example of a preferable manufacturing method of the composite sheet for protective film formation is demonstrated.

塗層較佳為藉由下述方式而形成：於支持片的凹凸面(圖1及圖2中為支持片10的背面10b，亦即基材11的背面11b)塗敷塗佈組成物並使之乾燥，且視需要使所形成之塗膜硬化。 The coating is preferably formed by applying the coating composition on the concave-convex surface of the support sheet (the back side 10b of the support sheet 10 in FIG. 1 and FIG. 2 , that is, the back side 11b of the base material 11 ), and It is dried, and if necessary, the formed coating film is hardened.

利用公知的方法向對象面塗敷塗佈組成物即可，例如可列舉使用以下各種塗佈機之方法：氣刀塗佈機、刮刀塗佈機、棒式塗佈機、凹版塗佈機、輥式塗佈機、輥刀塗佈機、簾幕式塗佈機、模具塗佈機、刀式塗佈機、絲網塗佈機、繞線棒式塗佈機、接觸式塗佈機等。 The coating composition may be applied to the target surface by a known method, for example, methods using the following various coaters: air knife coater, knife coater, bar coater, gravure coater, Roll coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, wire rod coater, contact coater, etc. .

於將塗佈組成物塗敷於支持片的凹凸面之情形時，較佳為抑制於塗層與支持片的凹凸面之間產生空隙部。藉由抑制前述空隙部之產生，可抑制於塗層與支持片的凹凸面之交界處光發生漫反射，從而可對保護膜的表面更清晰地進行雷射印字。 When the coating composition is applied to the uneven surface of the support sheet, it is preferable to suppress the generation of voids between the coating layer and the uneven surface of the support sheet. By suppressing the generation of the aforementioned voids, diffuse reflection of light at the interface between the coating layer and the concave-convex surface of the support sheet can be suppressed, so that the surface of the protective film can be more clearly laser-printed.

為了抑制前述空隙部之產生，例如較佳為使用黏度小的塗佈組成物。另外，含有能量線聚合性化合物之塗佈組成物通常適於抑制前述空隙部之產生。 In order to suppress the generation of the aforementioned voids, it is preferable to use, for example, a coating composition with a low viscosity. In addition, the coating composition containing the energy ray polymerizable compound is generally suitable for suppressing the generation of the aforementioned voids.

塗佈組成物之乾燥條件並無特別限定，但塗佈組成物較佳為進行加熱乾燥，該情形時，例如較佳為於70℃至130℃且0.5分鐘至5分鐘之條件下進行乾燥。 The drying conditions of the coating composition are not particularly limited, but the coating composition is preferably dried by heating. In this case, for example, drying is preferably performed under the conditions of 70°C to 130°C for 0.5 minutes to 5 minutes.

由塗佈組成物形成之塗膜之硬化條件並無特別限定，利用公知的方法進行即可。 The curing conditions of the coating film formed from the coating composition are not particularly limited, and may be performed by a known method.

於藉由照射能量線進行硬化之情形時，例如當照射紫外線時，使用高壓水銀燈、融合H型燈或氙氣燈作為紫外線源，將照射量設為較佳為100mJ/cm2至500mJ/cm2而進行照射即可。另一方面，當照射電子束時，藉由電子束加速器等產生電子束，將照射量設為較佳為150kV至350kV而進行照射即可。其中，較佳為藉由照射紫外線而形成塗層。 In the case of curing by irradiating energy rays, for example, when irradiating ultraviolet rays, a high-pressure mercury lamp, a fusion H-type lamp, or a xenon lamp is used as an ultraviolet source, and the irradiation amount is preferably set to 100mJ/cm 2 to 500mJ/cm 2 And it can be irradiated. On the other hand, when an electron beam is irradiated, an electron beam may be generated by an electron beam accelerator or the like, and the irradiation may be performed by setting the irradiation amount to preferably 150 kV to 350 kV. Among them, it is preferable to form a coating layer by irradiating ultraviolet rays.

於支持片例如由基材及黏著劑層積層而成之情形時，黏著劑層可於具備塗層之基材的表面(圖1及圖2中為基材11的表面11a)直接塗敷黏著劑組成物而形成。但是，通常較佳為採用以下預先另行形成黏著劑層，並將該黏著劑層貼合於基材的表面之方法：例如於剝離片的剝離處理面塗敷黏著劑組成物並使之乾燥，藉此形成黏著劑層，將所形成之黏著劑層貼合於基材的表面，並將前述剝離片移除等。 For example, when the support sheet is formed by laminating a substrate and an adhesive, the adhesive layer can be directly applied and adhered to the surface of the substrate with the coating (the surface 11a of the substrate 11 in FIG. 1 and FIG. 2 ). formed by the composition of the agent. However, it is usually preferable to use the following method of separately forming an adhesive layer in advance and attaching the adhesive layer to the surface of the base material: for example, coating the adhesive composition on the peeling-treated surface of the release sheet and drying it, Thereby, an adhesive layer is formed, the formed adhesive layer is attached to the surface of the substrate, and the aforementioned release sheet is removed.

可利用與塗佈組成物之情形相同之方法，向對象面塗敷黏著劑組成物。 The adhesive composition can be applied to the object surface by the same method as in the case of applying the composition.

所塗敷之黏著劑組成物可藉由進行加熱而交聯，該利用加熱之交聯亦可與乾燥一起進行。加熱條件例如可設為100℃至130℃且1分鐘至5分鐘，但並不限定於此。 The applied adhesive composition may be cross-linked by heating, and the cross-linking by heating may be performed together with drying. The heating conditions can be set to, for example, 100° C. to 130° C. for 1 minute to 5 minutes, but are not limited thereto.

於支持片僅由基材構成等由一層(單層)構成之情形、及例如支持片由基材及黏著劑層積層而成等由複數層構成之情形中的任一情形時，均可於具備塗層之支持片的表面(圖1及圖2中為支持片10的表面10a，亦即黏著劑層12的表面12a)直接塗敷保護膜形成用組成物，形成保護膜形成用膜。但是，通常較佳為與上述黏著劑層之情形同樣地採用以下預先另行形成保護膜形成用膜，並將該保護膜形成用膜貼合於支持片的表面之方法：於剝離片的剝離處理面塗敷保護膜形成用組成物並使之乾燥，藉此形成保護膜形成用膜，將所形成之保護膜形成用膜貼合於支持片的表面，視需要將前述剝離片移除等。 In any of the cases where the support sheet is composed of only one layer (single layer), such as the case where the support sheet is composed of a base material and an adhesive layer, and the case where the support sheet is composed of a plurality of layers, such as lamination of a base material and an adhesive The surface of the support sheet provided with the coating (the surface 10a of the support sheet 10 in FIG. 1 and FIG. 2, that is, the surface 12a of the adhesive layer 12) is directly coated with the composition for forming a protective film to form a film for forming a protective film. However, as in the case of the above-mentioned pressure-sensitive adhesive layer, it is generally preferable to employ the following method of separately forming a film for forming a protective film in advance and attaching the film for forming a protective film to the surface of the support sheet: peeling treatment on a peeling sheet The composition for forming a protective film is top-coated and dried to form a film for forming a protective film, the formed film for forming a protective film is bonded to the surface of the support sheet, and the release sheet is removed if necessary.

利用與塗佈組成物之情形相同之方法，向對象面塗敷保護膜形成用組成物。 The composition for forming a protective film is applied to the target surface by the same method as in the case of applying the composition.

保護膜形成用組成物之乾燥條件並無特別限定，可利用與塗佈組成物之情形相同之方法進行乾燥。 The drying conditions of the composition for forming a protective film are not particularly limited, and drying can be performed by the same method as in the case of coating the composition.

於支持片由基材及黏著劑層積層而成之情形時，本實施形態之保護膜形成用複合片亦可利用上述方法以外的方法進行製造。例如，亦可藉由下述方式而製造保護膜形 成用複合片：使用前述黏著劑組成物形成黏著劑層，使用前述保護膜形成用組成物形成保護膜形成用膜後，重疊這些黏著劑層及保護膜形成用膜而製成積層體，於該積層體的前述黏著劑層的表面(黏著劑層的未設置保護膜形成用膜的面)貼合具備塗層之基材的表面(圖1及圖2中為基材11的表面11a)。 When the support sheet is formed by laminating a base material and an adhesive, the composite sheet for forming a protective film of the present embodiment can also be produced by a method other than the above-mentioned method. For example, a protective film shape can also be produced in the following manner A composite sheet for forming: an adhesive layer is formed using the above-mentioned adhesive composition, and a protective film-forming film is formed using the above-mentioned protective film-forming composition. The surface of the adhesive layer of this laminate (the surface of the adhesive layer on which the film for forming a protective film is not provided) is bonded to the surface of the substrate provided with the coating layer (surface 11a of the substrate 11 in FIGS. 1 and 2 ) .

該情形時之黏著劑層及保護膜形成用膜之形成條件與上述方法之情形相同。 In this case, the formation conditions of the adhesive layer and the film for forming a protective film are the same as those of the above-mentioned method.

於支持片中的與具備保護膜形成用膜之面(表面)為相反側的面(背面)為平滑面而並非凹凸面之情形時，本實施形態之保護膜形成用複合片亦可利用上述方法以外的方法進行製造。例如，亦可藉由下述方式而製造保護膜形成用複合片，亦即，使用前述塗佈組成物形成塗層，將該塗層貼合於支持片的平滑面，藉此製成積層體；另一方面，使用前述保護膜形成用組成物預先形成保護膜形成用膜，將該保護膜形成用膜貼合於前述積層體中的支持片的露出面(支持片中的未設置塗層之面)。亦可藉由下述方式而製造保護膜形成用複合片，亦即，另行預先形成之塗層及保護膜形成用膜對支持片之貼合順序亦可與上述相反，於支持片的一表面貼合保護膜形成用膜後，於支持片的另一表面(支持片中的未設置保護膜形成用膜之面)貼合塗層。 In the case where the surface (back surface) opposite to the surface (surface) with the film for forming a protective film in the support sheet is a smooth surface and not a concave-convex surface, the composite sheet for forming a protective film of the present embodiment can also utilize the above-mentioned Manufactured by a method other than the method. For example, a composite sheet for forming a protective film may be produced by forming a coating layer using the above-mentioned coating composition, and attaching the coating layer to the smooth surface of the support sheet to obtain a laminate. On the other hand, use the aforementioned protective film forming composition to form a protective film forming film in advance, this protective film forming film is attached to the exposed surface of the support sheet in the aforementioned laminate (the coating is not provided in the support sheet) face). The composite sheet for forming a protective film can also be manufactured in the following manner, that is, the order of lamination of the pre-formed coating layer and the film for forming a protective film to the supporting sheet can also be opposite to the above, on one surface of the supporting sheet. After bonding the film for protective film formation, the coating layer is bonded to the other surface of the support sheet (the surface of the support sheet on which the film for protective film formation is not provided).

另外，亦可藉由下述方式而製造保護膜形成用複合片，亦即，於支持片的一表面，使用前述保護膜形成用組成物形成保護膜形成用膜；另一方面，使用前述塗佈組成物預先形成塗層，將該塗層貼合於前述支持片的露出面(支持片中的未設置保護膜形成用膜之面)。 Alternatively, a composite sheet for forming a protective film may be produced by forming a film for forming a protective film on one surface of a support sheet using the composition for forming a protective film; on the other hand, using the coating The cloth composition is formed with a coating layer in advance, and the coating layer is attached to the exposed surface of the support sheet (the surface of the support sheet on which the film for forming a protective film is not provided).

這些情形的塗層及保護膜形成用膜的形成條件與上述方法之情形相同。 The coating layer and the formation conditions of the film for protective film formation in these cases are the same as the case of the above-mentioned method.

例如，於製造如圖1所示之保護膜形成用複合片，即自上方往下俯視保護膜形成用複合片時，保護膜形成用膜的表面積小於黏著劑層的表面積之保護膜形成用複合片之情形時，上述製造方法中，將預先切成預定之大小及形狀之保護膜形成用膜設置於黏著劑層上即可。 For example, when manufacturing the composite sheet for forming a protective film as shown in FIG. 1, that is, when the composite sheet for forming a protective film is viewed from above, the surface area of the film for forming a protective film is smaller than the surface area of the adhesive layer. In the case of a sheet, in the above-mentioned manufacturing method, a film for forming a protective film cut in advance to a predetermined size and shape may be provided on the adhesive layer.

◎保護膜形成用複合片的使用方法 ◎How to use the composite sheet for forming a protective film

本實施形態之保護膜形成用複合片的使用方法例如如下所示。 The usage method of the composite sheet for protective film formation of this embodiment is as follows, for example.

首先，對保護膜形成用膜為熱硬化性之情形時之保護膜形成用複合片的使用方法進行說明。 First, the usage method of the composite sheet for protective film formation when the film for protective film formation is thermosetting is demonstrated.

該情形時，首先，於保護膜形成用複合片之保護膜形成用膜貼附半導體晶圓的背面，並且將保護膜形成用複合片固定於切割裝置。 In this case, first, the back surface of the semiconductor wafer is attached to the film for forming a protective film of the composite sheet for forming a protective film, and the composite sheet for forming a protective film is fixed to a dicing device.

繼而，藉由加熱使保護膜形成用膜硬化而製成保護膜。於半導體晶圓的表面(電極形成面)貼附有背面研磨帶 之情形時，通常將該背面研磨帶自半導體晶圓移除後形成保護膜。 Next, the film for protective film formation is hardened by heating, and it is set as a protective film. A back grinding tape is attached to the surface (electrode formation surface) of the semiconductor wafer In this case, the back grinding tape is usually removed from the semiconductor wafer to form a protective film.

繼而，切割半導體晶圓而製成半導體晶片。在形成保護膜起至進行切割之期間，可自保護膜形成用複合片的塗層側對保護膜照射雷射光，對保護膜的表面進行印字。該情形時，如上文所說明，藉由塗層中的與和支持片接觸之側為相反側的面(背面)的光澤值為如上所述之特定範圍內，可對保護膜清晰地進行雷射印字。 Next, the semiconductor wafer is diced to produce a semiconductor wafer. During the period from the formation of the protective film to the dicing, the protective film may be irradiated with laser light from the coating side of the composite sheet for forming a protective film to print on the surface of the protective film. In this case, as explained above, when the gloss value of the surface (back surface) on the opposite side to the side in contact with the support sheet in the coating layer is within the above-mentioned specific range, the protective film can be clearly irradiated. Shot printing.

另外，針對進行切割之前的半導體晶圓或進行切割而獲得之半導體晶片，有時藉由紅外線相機等自前述半導體晶圓或半導體晶片的背面(貼附有保護膜形成用複合片之面)側進行觀察，藉此檢測狀態。例如，當為半導體晶片時，有時檢測該半導體晶片有無缺口或裂紋等破損。 In addition, with respect to the semiconductor wafer before dicing or the semiconductor wafer obtained by dicing, an infrared camera or the like may be used from the back surface (surface to which the composite sheet for forming a protective film is attached) of the semiconductor wafer or the semiconductor wafer. An observation is made to detect the state. For example, in the case of a semiconductor wafer, the presence or absence of breakage, such as a chip or a crack, may be detected in the semiconductor wafer.

另一方面，本實施形態之附保護膜之半導體晶片中，如上所述，塗層中的與和支持片接觸之側為相反側的面(背面)的光澤值為如上所述之特定範圍內，進一步，抑制於塗層與支持片的前述背面之間產生空隙部。因此，自塗層側經由保護膜形成用複合片，藉由紅外線相機等觀察半導體晶圓或半導體晶片時，可獲取清晰的檢測圖像，因此可高精度地進行檢測。 On the other hand, in the semiconductor wafer with the protective film of the present embodiment, as described above, the gloss value of the surface (back surface) opposite to the side in contact with the support sheet in the coating layer is within the specific range as described above. , and further, the formation of voids between the coating layer and the back surface of the support sheet is suppressed. Therefore, when a semiconductor wafer or a semiconductor wafer is observed with an infrared camera or the like from the coating side through the composite sheet for forming a protective film, a clear inspection image can be obtained, so that the inspection can be performed with high accuracy.

繼而，自支持片，將半導體晶片與貼附於該半導體晶片的背面之保護膜一起剝離而進行拾取，藉此獲得附有保護膜之半導體晶片。例如，於支持片由基材及黏著劑層積層而成，且前述黏著劑層為能量線硬化性之情形時，藉由照射能量線而使黏著劑層硬化，自該硬化後的黏著劑層，將半導體晶片與貼附於該半導體晶片的背面之保護膜一起拾取，藉此更容易地獲得附有保護膜之半導體晶片。 Then, from the support sheet, the semiconductor wafer is peeled off together with the protective film attached to the back surface of the semiconductor wafer and picked up, thereby obtaining a semiconductor wafer with a protective film. For example, when the support sheet is formed by laminating a base material and an adhesive, and the adhesive layer is energy ray curable, the adhesive layer is cured by irradiating the energy ray, and the cured adhesive layer is , pick up the semiconductor wafer together with the protective film attached to the backside of the semiconductor wafer, thereby more easily obtaining the semiconductor wafer with the protective film.

例如，於使用圖1所示之保護膜形成用複合片1之情形時，於保護膜形成用複合片1的保護膜形成用膜13貼附半導體晶圓的背面，並且將露出之支持片10(黏著劑層12)貼附於環狀框等切割用治具(省略圖示)，從而將保護膜形成用複合片1固定於切割裝置。繼而，使保護膜形成用膜13硬化而製成保護膜後，對保護膜進行雷射印字，繼而進行切割，視需要藉由照射能量線，而使黏著劑層12的除貼附於前述治具之部位以外的區域硬化，然後拾取附有保護膜之半導體晶片即可。如此，於使用黏著劑層12為能量線硬化性之保護膜形成用複合片1之情形時，必須以不使保護膜形成用複合片1自前述治具剝離且不使黏著劑層12的特定區域硬化之方式進行調節。另一方面，於使用保護膜形成用複合片1之情形時，無需另行設置將用以將該保護膜形成用複合片1貼附於前述治具之構成。 For example, when the composite sheet 1 for forming a protective film shown in FIG. 1 is used, the back surface of the semiconductor wafer is attached to the film 13 for forming a protective film of the composite sheet 1 for forming a protective film, and the exposed support sheet 10 is attached to the back surface of the semiconductor wafer. The (adhesive layer 12 ) is attached to a dicing jig (not shown) such as an annular frame, and the composite sheet 1 for forming a protective film is fixed to a dicing device. Next, after curing the protective film-forming film 13 to form a protective film, the protective film is laser-printed and then cut, and the adhesive layer 12 is adhered to the aforementioned treatment by irradiating energy rays as necessary. The area other than the part of the tool is hardened, and then the semiconductor wafer with the protective film can be picked up. In this way, when the composite sheet 1 for forming a protective film having the adhesive layer 12 having energy ray curability is used, it is necessary to prevent the composite sheet 1 for forming a protective film from peeling off the jig and to prevent the specific adhesive layer 12 from being peeled off. Area hardening is adjusted. On the other hand, when using the composite sheet 1 for protective film formation, there is no need to separately provide a structure for attaching the composite sheet 1 for protective film formation to the aforementioned jig.

相對於此，於使用圖2所示之保護膜形成用複合片2之情形時，於保護膜形成用複合片2之保護膜形成用膜23貼附半導體晶圓的背面，並且將治具用接著劑層16貼附於環狀框等切割用治具(省略圖示)，從而將保護膜形成用複合片2固定於切割裝置。繼而，使保護膜形成用膜23硬化而製成保護膜後，對保護膜進行雷射印字，繼而進行切割，視需要藉由照射能量線而使黏著劑層12硬化，然後拾取附有保護膜之半導體晶片即可。如此，於使用黏著劑層12為能量線硬化性之保護膜形成用複合片2之情形時，與使用保護膜形成用複合片1之情形不同，無需以不使黏著劑層12的特定區域硬化之方式進行調節。另一方面，與保護膜形成用複合片1不同，保護膜形成用複合片2必須具備治具用接著劑層16。藉由具備治具用接著劑層16，黏著劑層12可根據目的選擇範圍廣泛的組成。 On the other hand, when the composite sheet 2 for protective film formation shown in FIG. 2 is used, the back surface of the semiconductor wafer is adhered to the film 23 for protective film formation of the composite sheet 2 for protective film formation, and a jig is used for The adhesive layer 16 is attached to a dicing jig (not shown) such as an annular frame, and the composite sheet 2 for forming a protective film is fixed to the dicing device. Next, after hardening the film 23 for protective film formation to make a protective film, the protective film is laser-printed, then diced, and the adhesive layer 12 is cured by irradiating energy rays as necessary, and then the protective film is picked up. The semiconductor chip can be used. In this way, when the composite sheet 2 for forming a protective film having the adhesive layer 12 having energy ray curability is used, unlike the case where the composite sheet 1 for forming a protective film is used, it is not necessary to prevent a specific region of the adhesive layer 12 from being cured. way to adjust. On the other hand, unlike the composite sheet 1 for protective film formation, the composite sheet 2 for protective film formation must be provided with the adhesive agent layer 16 for jigs. By having the adhesive layer 16 for a jig, the adhesive layer 12 can have a wide range of compositions selected according to the purpose.

其次，對保護膜形成用膜為能量線硬化性之情形時之保護膜形成用複合片的使用方法進行說明。 Next, the usage method of the composite sheet for protective film formation when the film for protective film formation is energy ray curability is demonstrated.

該情形時，首先，與上述保護膜形成用膜為熱硬化性之情形同樣地，於保護膜形成用複合片之保護膜形成用膜貼附半導體晶圓的背面，並且將保護膜形成用複合片固定於切割裝置。 In this case, first, similarly to the case where the film for forming a protective film is thermosetting, the back surface of the semiconductor wafer is adhered to the film for forming a protective film of the composite sheet for forming a protective film, and the composite sheet for forming a protective film is laminated. The sheet is fixed to the cutting device.

繼而，藉由照射能量線使保護膜形成用膜硬化而製成保護膜。於半導體晶圓的表面(電極形成面)貼附有背面研 磨帶之情形時，通常將該背面研磨帶自半導體晶圓移除後形成保護膜。 Next, the film for protective film formation is hardened by irradiating an energy ray, and a protective film is produced. A backside surface is attached to the surface (electrode formation surface) of the semiconductor wafer. In the case of tape grinding, the back grinding tape is usually removed from the semiconductor wafer to form a protective film.

繼而，切割半導體晶圓而製成半導體晶片。在形成保護膜起至進行切割之期間，可自保護膜形成用複合片的塗層側對保護膜照射雷射光，對保護膜的表面進行印字。自該印字起至切割為止這一過程可與上述保護膜形成用膜為熱硬化性之情形同樣地進行，與該情形同樣地，可對保護膜清晰地進行雷射印字，可藉由紅外線相機等高精度地進行檢測。 Next, the semiconductor wafer is diced to produce a semiconductor wafer. During the period from the formation of the protective film to the dicing, the protective film may be irradiated with laser light from the coating side of the composite sheet for forming a protective film to print on the surface of the protective film. The process from this printing to cutting can be carried out in the same manner as in the case where the above-mentioned film for forming a protective film is thermosetting, and similarly to this case, the protective film can be clearly laser-printed, and it is possible to use an infrared camera detection with high accuracy.

繼而，自支持片，將半導體晶片與貼附於該半導體晶片的背面之保護膜一起剝離而進行拾取，藉此獲得附有保護膜之半導體晶片。 Then, from the support sheet, the semiconductor wafer is peeled off together with the protective film attached to the back surface of the semiconductor wafer and picked up, thereby obtaining a semiconductor wafer with a protective film.

該方法例如於以下情形時尤佳：使用支持片由基材及黏著劑層積層而成，且前述黏著劑層為非能量線硬化性之複合片作為保護膜形成用複合片。再者，此處對藉由照射能量線使保護膜形成用膜硬化後，切割半導體晶圓，拾取附有保護膜之半導體晶片之情形進行了說明，但於前述黏著劑層為非能量線硬化性之情形時，可在拾取半導體晶片之前的任一階段，藉由照射能量線使保護膜形成用膜硬化。 This method is particularly preferable when, for example, a support sheet is formed by laminating a base material and an adhesive, and the adhesive layer is a non-energy ray-curable composite sheet as a protective film-forming composite sheet. In addition, the case where the film for forming a protective film is cured by irradiating the energy ray, the semiconductor wafer is diced, and the semiconductor wafer with the protective film is picked up has been described, but the above-mentioned adhesive layer is non-energy ray curing. In the case of nature, the film for protective film formation can be hardened by irradiating an energy ray at any stage before picking up a semiconductor wafer.

例如，於使用支持片由基材及黏著劑層積層而成，且 前述黏著劑層為能量線硬化性之保護膜形成用複合片之情形時，較佳為以下說明之方法。 For example, when a support sheet is used to laminate a substrate and an adhesive, and In the case where the adhesive layer is an energy ray-curable composite sheet for forming a protective film, the method described below is preferred.

亦即，首先，與上述情形同樣地，於保護膜形成用複合片的保護膜形成用膜貼附半導體晶圓的背面，並且將保護膜形成用複合片固定於切割裝置。 That is, first, similarly to the above-mentioned case, the back surface of the semiconductor wafer is attached to the film for forming a protective film of the composite sheet for forming a protective film, and the composite sheet for forming a protective film is fixed to a dicing device.

繼而，自保護膜形成用複合片的塗層側對保護膜照射雷射光，對保護膜的表面進行印字，進一步切割半導體晶圓而製成半導體晶片。自該印字起至切割為止這一過程可與上述保護膜形成用膜為熱硬化性之情形同樣地進行，與該情形同樣地，可對保護膜清晰地進行雷射印字，可藉由紅外線相機等高精度地進行檢測。 Next, the protective film is irradiated with laser light from the coating side of the composite sheet for protective film formation, the surface of the protective film is printed, and the semiconductor wafer is further cut to form a semiconductor wafer. The process from this printing to cutting can be carried out in the same manner as in the case where the above-mentioned film for forming a protective film is thermosetting, and similarly to this case, the protective film can be clearly laser-printed, and it is possible to use an infrared camera detection with high accuracy.

繼而，藉由照射能量線使保護膜形成用膜硬化而製成保護膜，並且使黏著劑層硬化，自該硬化後的黏著劑層，將半導體晶片與貼附於該半導體晶片的背面之保護膜一起拾取，藉此獲得附有保護膜之半導體晶片。 Next, the film for forming a protective film is hardened by irradiating energy rays to form a protective film, and the adhesive layer is hardened, and from the hardened adhesive layer, the semiconductor chip and the back surface attached to the semiconductor chip are protected. The films are picked up together, whereby a semiconductor wafer with a protective film is obtained.

另一方面，於捲取長條的保護膜形成用複合片之情形時，通常使用於保護膜形成用膜的露出面上積層有剝離膜(圖1及圖2中為剝離膜15)之狀態之保護膜形成用複合片。並且，本實施形態之保護膜形成用複合片無論為何種構成(例如為圖1所示之保護膜形成用複合片1及圖2所示之保護膜形成用複合片2之任一者)，隨著將保護膜形成用複合片捲取成輥狀，依序積層有塗層、支持片、保護 膜形成用膜及剝離膜之積層單元均沿輥的徑向依次層疊。結果為，在輥的徑向上相互接觸之積層單元彼此之間，成為一積層單元的剝離膜的表面(與設置有保護膜形成用膜之側為相反側的面)，與另一積層單元的塗層的背面(與和基材接觸之側為相反側的面)接觸、擠壓之狀態，保護膜形成用複合片之輥直接以該狀態進行保存。但是，藉由設置有塗層，可抑制於積層單元彼此之間這些剝離膜及塗層之黏附，因此本實施形態之保護膜形成用複合片之黏連得到抑制。 On the other hand, when winding a long composite sheet for protective film formation, it is usually used in a state where a release film (release film 15 in FIGS. 1 and 2 ) is laminated on the exposed surface of the film for protective film formation. The protective film forming composite sheet. Moreover, regardless of the structure of the composite sheet for forming a protective film of the present embodiment (for example, any one of the composite sheet 1 for forming a protective film shown in FIG. 1 and the composite sheet 2 for forming a protective film shown in FIG. 2 ), As the composite sheet for forming a protective film is wound into a roll shape, a coating layer, a support sheet, and a protective film are laminated in this order. All the lamination units of the film for film formation and the release film are sequentially laminated in the radial direction of the roll. As a result, the surface of the release film (the surface on the opposite side to the side on which the film for forming a protective film is provided) of one laminate unit and the surface of the release film of the other laminate unit, which are in contact with each other in the radial direction of the roll, become The back surface of the coating layer (the surface opposite to the side in contact with the base material) is in contact and pressed, and the roller of the composite sheet for forming a protective film is stored in this state as it is. However, by providing the coating layer, the adhesion of these release films and the coating layer between the lamination units can be suppressed, so that the adhesion of the composite sheet for forming a protective film of the present embodiment is suppressed.

使用於前述保護膜形成用膜上具備剝離膜之前述保護膜形成用複合片，利用下述方法測定之前述剝離膜的剝離力較佳為10mN/50mm以下，更佳為7.5mN/50mm以下，尤佳為5mN/50mm以下。 Using the composite sheet for forming a protective film provided with a release film on the film for forming a protective film, the peeling force of the release film measured by the following method is preferably 10 mN/50 mm or less, more preferably 7.5 mN/50 mm or less, It is especially preferable that it is 5 mN/50mm or less.

(剝離膜的剝離力的測定方法) (Measuring method of peeling force of peeling film)

將於保護膜形成用膜上具備剝離膜之狀態且寬度50mm、長度100mm之本實施形態之保護膜形成用複合片，以塗層全部朝向相同方向且塗層的合計厚度成為10μm至60μm之方式重疊複數片，藉此製成第一最外層為塗層且第二最外層為剝離膜之積層體，將該積層體以於保護膜形成用複合片的積層方向上施加980.665mN(亦即100gf)之力(外力)之狀態於40℃下靜置3天後，將於前述積層方向上距離前述第一最外層之塗層最近之剝離膜，於剝離速度300mm/分鐘、剝離角度180°之條件下，自鄰接 之塗層(於前述積層方向上距離前述第一最外層之塗層最近之塗層)剝離，測定此時的剝離力。再者，此處重疊複數片之保護膜形成用複合片全部為相同構成。另外，重疊之保護膜形成用複合片的片數較佳為10片。根據此種剝離膜的剝離力，可確認本實施形態之保護膜形成用複合片的抑制黏連之功效(耐黏連性)的高低。 The composite sheet for forming a protective film of this embodiment with a state of having a release film on the film for forming a protective film and having a width of 50 mm and a length of 100 mm, the coating layers are all oriented in the same direction and the total thickness of the coating layers is 10 μm to 60 μm. A plurality of sheets are overlapped to form a laminate in which the first outermost layer is a coating layer and the second outermost layer is a release film, and 980.665mN (that is, 100gf) is applied to the laminate in the lamination direction of the protective film-forming composite sheet. After standing at 40°C for 3 days in the state of ) force (external force), the peeling film closest to the first outermost coating layer in the lamination direction is peeled at a peeling speed of 300mm/min and a peeling angle of 180°. condition, self-adjacency The coating layer (the coating layer closest to the coating layer of the first outermost layer in the above-mentioned lamination direction) was peeled off, and the peeling force at this time was measured. In addition, here, the composite sheet for protective film formation which laminated|stacked a plurality of sheets all has the same structure. Moreover, it is preferable that the number of sheets of the composite sheet for protective film formation to overlap is 10 sheets. From the peeling force of such a peeling film, the level of the blocking-suppressing effect (blocking resistance) of the composite sheet for protective film formation of this embodiment can be confirmed.

[實施例] [Example]

以下，藉由具體的實施例對本發明進行更詳細的說明。但是，本發明並不受以下所示之實施例之任何限定。 Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited at all by the examples shown below.

<保護膜形成用複合片之製造> <Manufacture of the composite sheet for protective film formation>

[實施例1] [Example 1]

製造圖1所示之構成之保護膜形成用複合片。該保護膜形成用複合片之俯視圖示於圖3。更具體而言，如下所述。 The composite sheet for protective film formation of the structure shown in FIG. 1 was manufactured. A plan view of the composite sheet for forming a protective film is shown in FIG. 3 . More specifically, it is as follows.

[第1積層體之製造] [Manufacture of the first laminate]

(熱硬化性保護膜形成用組成物之製備) (Preparation of composition for forming thermosetting protective film)

將下述成分以下述量(固形物成分)進行調配，進一步調配甲基乙基酮，獲得固形物成分濃度為51質量%之保護膜形成用組成物(III-1)。 The following components were prepared in the following amounts (solid content), and methyl ethyl ketone was further prepared to obtain a composition (III-1) for forming a protective film having a solid content concentration of 51% by mass.

(聚合物成分(A)) (polymer component (A))

(A)-1：使丙烯酸正丁酯10質量份、丙烯酸甲酯70質量份、甲基丙烯酸縮水甘油酯5質量份及丙烯酸2-羥基乙酯15質量份進行共聚合而成之丙烯酸系樹脂(重量平均分子量400000，玻璃轉移溫度-1℃)150質量份。 (A)-1: Acrylic resin obtained by copolymerizing 10 parts by mass of n-butyl acrylate, 70 parts by mass of methyl acrylate, 5 parts by mass of glycidyl methacrylate, and 15 parts by mass of 2-hydroxyethyl acrylate (weight average molecular weight 400,000, glass transition temperature -1°C) 150 parts by mass.

(熱硬化性成分(B)) (Thermosetting component (B))

‧環氧樹脂(B1) ‧Epoxy resin (B1)

(B1)-1：雙酚A型環氧樹脂(三菱化學公司製造之「JER828」，環氧當量183g/eq至194g/eq，分子量370)60質量份。 (B1)-1: bisphenol A epoxy resin ("JER828" by Mitsubishi Chemical Corporation, epoxy equivalent 183 g/eq to 194 g/eq, molecular weight 370) 60 parts by mass.

(B1)-2：雙酚A型環氧樹脂(三菱化學公司製造之「JER1055」，環氧當量800g/eq至900g/eq，分子量1600)10質量份。 (B1)-2: 10 parts by mass of bisphenol A epoxy resin (“JER1055” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 800 g/eq to 900 g/eq, molecular weight 1600).

(B1)-3：二環戊二烯型環氧樹脂(DIC公司製造之「Epiclon HP-7200HH」，環氧當量274g/eq至286g/eq)30質量份。 (B1)-3: Dicyclopentadiene-type epoxy resin ("Epiclon HP-7200HH" by DIC Corporation, epoxy equivalent 274g/eq-286g/eq) 30 mass parts.

‧熱硬化劑(B2) ‧Thermosetting agent (B2)

(B2)-1：二氰二胺(固體分散型潛伏性硬化劑，ADEKA公司製造之「Adeka Hardener EH-3636AS」，活性氫量21g/eq)2質量份。 (B2)-1: Dicyandiamide (solid dispersion type latent hardener, "Adeka Hardener EH-3636AS" manufactured by ADEKA, active hydrogen amount 21 g/eq) 2 parts by mass.

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

(C)-1：2-苯基-4,5-二羥基甲基咪唑(四國化成工業公司製造之「Curezol 2PHZ」)2質量份。 (C)-1: 2 parts by mass of 2-phenyl-4,5-dihydroxymethylimidazole (“Curezol 2PHZ” manufactured by Shikoku Chemical Industry Co., Ltd.).

(填充材料(D)) (filler (D))

(D)-1：二氧化矽填料(Admatechs公司之 「SC2050MA」，利用環氧系化合物進行了表面修飾，平均粒徑0.5μm)320質量份。 (D)-1: Silica filler (Admatechs "SC2050MA", surface-modified with an epoxy compound, average particle size 0.5 μm) 320 parts by mass.

(偶合劑(E)) (Coupling Agent (E))

(E)-1：γ-縮水甘油氧基丙基三甲氧基矽烷(矽烷偶合劑，信越化學工業公司製造之「KBM403」，甲氧基當量12.7mmol/g，分子量236.3)0.4質量份。 (E)-1: γ-glycidyloxypropyltrimethoxysilane (silane coupling agent, "KBM403" manufactured by Shin-Etsu Chemical Co., Ltd., methoxyl equivalent 12.7 mmol/g, molecular weight 236.3) 0.4 part by mass.

(著色劑(I)) (Colorant (I))

(I)-1：碳黑(顏料，三菱化學公司製造之「MA600B」，平均粒徑28nm)1.2質量份。 (I)-1: 1.2 parts by mass of carbon black (pigment, "MA600B" manufactured by Mitsubishi Chemical Corporation, average particle size: 28 nm).

(保護膜形成用膜之形成、第1積層體之製造) (Formation of the film for protective film formation, production of the first laminate)

使用刀式塗佈機，於第1剝離膜(Lintec公司製造之「SP-P502010＊」，厚度50μm)的剝離處理面上，塗佈上述獲得之保護膜形成用組成物(III-1)，於120℃下乾燥2分鐘，形成保護膜形成用膜(厚度25μm)。 Using a knife coater, the protective film-forming composition (III-1) obtained above was applied on the peeling-treated surface of the first peeling film (“SP-P502010*” manufactured by Lintec Corporation, thickness 50 μm), It dried at 120 degreeC for 2 minutes, and formed the film for protective film formation (thickness 25 micrometers).

繼而，於該保護膜形成用膜中的與設置有第1剝離膜之面為相反側的面，貼合第2剝離膜(Lintec公司製造之「SP-PET381031C」，厚度38μm)的剝離處理面，獲得第1剝離膜、保護膜形成用膜及第2剝離膜依序積層而成之長條的積層體。繼而，將該長條的積層體捲取成輥後，將該積層體裁斷為在該積層體的寬度方向(圖3所示之保護膜形成用複合片1中以符號w1表示之寬度之方向)上為300mm之大小。 Next, the peeling treatment surface of the second peeling film (“SP-PET381031C” manufactured by Lintec, thickness 38 μm) was bonded to the surface on the opposite side of the surface on which the first peeling film was provided in the film for forming a protective film. , to obtain a long layered body in which the first release film, the film for protective film formation, and the second release film were laminated in this order. Next, after the long layered product is wound into a roll, the layered product is cut into the width direction of the layered product (the width indicated by the symbol w 1 in the composite sheet 1 for forming a protective film shown in FIG. 3 ). direction) is 300mm in size.

然後，針對該裁斷之積層體，於該積層體的寬度方向中央部，自第2剝離膜側，對第2剝離膜及保護膜形成用膜，一起以描繪出俯視下直徑220mm之圓形之方式進行切入切口之半切(half cut)。再者，本說明書中積層體之「俯視」意指自積層體的積層方向上方往下看該積層體。然後，以僅使利用該半切所形成之圓形部分殘留之方式，將第2剝離膜及保護膜形成用膜自前述積層體去除，藉此獲得於第1剝離膜的剝離處理面上依序積層俯視下為圓形的保護膜形成用膜及第2剝離膜而成之第1積層體。該第1積層體中的圓形的保護膜形成用膜相當於圖3所示之保護膜形成用複合片1中直徑d1為220mm之圓形的保護膜形成用膜13。 Then, with respect to the cut laminate, from the side of the second peeling film, the second peeling film and the film for protective film formation were drawn together in a circular shape with a diameter of 220 mm in plan view at the center portion in the width direction of the laminate. A half cut of the incision is performed in this way. In addition, the "planar view" of the laminated body in this specification means seeing the laminated body downward from the upper direction of the lamination direction of the laminated body. Then, the second release film and the film for forming a protective film are removed from the above-mentioned laminated body so that only the circular portion formed by the half cut remains, to obtain sequentially on the release-treated surface of the first release film. The 1st laminated body which laminated|stacked the film for protective film formation which are circular in plan view, and a 2nd peeling film. The circular film for forming a protective film in the first laminate corresponds to the film 13 for forming a protective film having a diameter d1 of 220 mm in the composite sheet 1 for forming a protective film shown in FIG. 3 .

(塗佈組成物之製備) (Preparation of coating composition)

於二氧化矽溶膠分散於2-乙氧基乙醇(乙基溶纖劑)中而成之分散液(觸媒化成工業公司製造之「OSCAL1632」，二氧化矽溶膠之粒徑30nm至50nm，固形物成分濃度30質量%)150質量份中，調配由丙烯酸胺基甲酸酯及多官能性丙烯酸酯單體構成之硬塗劑(荒川化學工業公司製造之「BEAMSET 575CB」，固形物成分濃度100質量%，含有光聚合起始劑)100質量份，獲得塗佈組成物(固形物成分濃度30質量%)。 Dispersion liquid (“OSCAL1632” manufactured by Catalytic Chemical Industry Co., Ltd.) in which silica sol is dispersed in 2-ethoxyethanol (ethyl cellosolve), the particle size of silica sol is 30nm to 50nm, solid A hard coat agent (“BEAMSET 575CB” manufactured by Arakawa Chemical Industry Co., Ltd., manufactured by Arakawa Chemical Industry Co., Ltd., solid content concentration 100 % by mass, containing a photopolymerization initiator) 100 parts by mass to obtain a coating composition (solid content concentration: 30 mass %).

(塗層之形成) (Formation of coating)

繼而，使用繞線棒式塗佈機，於凹凸面的表面粗糙度Ra為0.4μm，且與該凹凸面為相反側之面的表面粗糙度Ra為0.02μm之聚丙烯製基材(厚度100μm，熔點140℃至160℃)的前述凹凸面，塗佈上述獲得之塗佈組成物，於80℃下乾燥1分鐘後，以約230mJ/cm2之光量照射紫外線而使乾燥後的塗膜硬化，形成塗層(厚度3μm)。 Next, using a wire bar coater, the surface roughness Ra on the uneven surface was 0.4 μm, and the surface roughness Ra of the surface opposite to the uneven surface was 0.02 μm. The polypropylene base material (thickness 100 μm) , the aforementioned uneven surface with a melting point of 140°C to 160°C) is coated with the coating composition obtained above, dried at 80°C for 1 minute, and then irradiated with ultraviolet rays at a light intensity of about 230mJ/cm 2 to harden the dried coating film , forming a coating (thickness 3 μm).

(黏著劑組成物之製備) (Preparation of Adhesive Composition)

調配(甲基)丙烯酸烷基酯共聚物100質量份、及芳香族系多異氰酸酯化合物(交聯劑，三井化學公司製造之「Takenate D110N」)10質量份(固形物成分)，進一步調配甲基乙基酮，獲得固形物成分濃度為30質量%之黏著劑組成物(iii)。 100 parts by mass of alkyl (meth)acrylate copolymer and 10 parts by mass (solid content) of an aromatic polyisocyanate compound (crosslinking agent, "Takenate D110N" manufactured by Mitsui Chemicals Co., Ltd.) were prepared, and a methyl group was further prepared. Ethyl ketone was used to obtain an adhesive composition (iii) having a solid content concentration of 30% by mass.

前述(甲基)丙烯酸烷基酯共聚物係使丙烯酸正丁酯40質量份、丙烯酸2-乙基己基55質量份及丙烯酸2-羥基乙酯5質量份進行共聚合而成之重量平均分子量600000之丙烯酸系樹脂。 The above-mentioned alkyl (meth)acrylate copolymer is obtained by copolymerizing 40 parts by mass of n-butyl acrylate, 55 parts by mass of 2-ethylhexyl acrylate, and 5 parts by mass of 2-hydroxyethyl acrylate and having a weight average molecular weight of 600,000 of acrylic resin.

(黏著劑層(支持片)之形成、第2積層體之製造) (Formation of the adhesive layer (support sheet), production of the second laminate)

使用刀式塗佈機，於單面藉由形成聚矽氧系剝離劑層進行剝離處理，且厚度38μm之由聚對苯二甲酸乙二酯製膜構成之第3剝離膜(Lintec公司製造之「SP-PET381031C」)的前述剝離處理面，塗佈上述獲得之黏著劑組成物(iii)並使之乾燥，形成黏著劑層(厚度5μm)。 Using a knife coater, peeling treatment was performed by forming a polysiloxane-based release agent layer on one side, and the third release film (manufactured by Lintec Co., Ltd.) was made of polyethylene terephthalate with a thickness of 38 μm. "SP-PET381031C") was coated with the adhesive composition (iii) obtained above and dried to form an adhesive layer (thickness 5 μm).

繼而，對形成有塗層之上述基材中的與凹凸面為相反側的面進行電暈處理後，於該電暈處理面貼合上述黏著劑層，從而獲得塗層、基材、黏著劑層及第3剝離膜依序積層且包含支持片之長條的第2積層體。 Then, after corona treatment is performed on the surface of the substrate on which the coating layer is formed on the opposite side to the uneven surface, the adhesive layer is bonded to the corona treated surface to obtain a coating layer, a substrate, and an adhesive. A layer and a 3rd peeling film are laminated|stacked in this order, and the elongate 2nd laminated body containing a support sheet is included.

繼而，將該長條的第2積層體捲取成輥後，將該第2積層體裁斷為在該第2積層體的寬度方向(圖3所示之保護膜形成用複合片1中以符號w1表示之寬度之方向)上為300mm之大小。 Next, after winding this long 2nd laminated body into a roll, this 2nd laminated body is cut|disconnected so that the width direction of this 2nd laminated body (in the composite sheet 1 for protective film formation shown in FIG. The direction of the width represented by w1) is 300mm in size.

(保護膜形成用複合片之製造) (Manufacture of a composite sheet for forming a protective film)

自上述獲得之第1積層體移除第2剝離膜，使圓形的保護膜形成用膜露出。另外，自上述獲得之第2積層體移除第3剝離膜，使黏著劑層露出。然後，將上述保護膜形成用膜的露出面貼合於該黏著劑層的露出面，藉此獲得相當於塗層、基材、黏著劑層、保護膜形成用膜及第1剝離膜依序積層而成之保護膜形成用複合片之第3積層體。 The 2nd peeling film was removed from the 1st laminated body obtained above, and the film for protective film formation of a circular shape was exposed. Moreover, the 3rd peeling film was removed from the 2nd laminated body obtained above, and the adhesive layer was exposed. Then, by bonding the exposed surface of the film for forming a protective film to the exposed surface of the adhesive layer, a coating layer, a base material, an adhesive layer, a film for forming a protective film, and a first release film are obtained in this order. The third laminate of the laminated protective film-forming composite sheet.

針對上述獲得之第3積層體，自塗層側，對塗層、基材及黏著劑層之全部，以描繪出俯視下直徑270mm之圓形之方式進行切出切口之半切。該半切中，以俯視下直徑270mm之前述圓相對於保護膜形成用膜所形成之直徑220mm之圓成為同心圓之方式，對塗層、基材及黏著劑層之全部切出切口。 For the third layered product obtained above, from the coating side, half-cutting was performed to cut out the entire coating layer, the base material and the adhesive layer so as to draw a circle with a diameter of 270 mm in plan view. In this half-cut, the above-mentioned circle with a diameter of 270 mm in plan view was concentric with the circle with a diameter of 220 mm formed by the film for forming a protective film, and the entire coating layer, base material and adhesive layer were cut out.

繼而，以於俯視下，相對於上述直徑270mm之圓，於與該圓之徑向外側相距20mm之位置，描繪出在第3積層體的寬度方向(圖3所示之保護膜形成用複合片1中以符號w1表示之寬度之方向)上對向之一對圓弧之方式，自塗層側，對塗層、基材及黏著劑層之全部進行切出切口之半切。 Then, with respect to the circle having a diameter of 270 mm, in a plan view, at a position 20 mm away from the radially outer side of the circle, the width direction of the third laminate (the composite sheet for forming a protective film shown in FIG. 3 ) is drawn. In 1, the width direction indicated by the symbol w 1 ) is opposite to a pair of circular arcs, from the coating side, the coating, the substrate and the adhesive layer are all cut out and half-cut.

相當於該一對圓弧之切口形成圖3所示之保護膜形成用複合片1中以符號121表示之黏著劑層的曲面狀的周緣部。並且，直徑270mm之圓與前述圓弧之間之距離(20mm)相當於圖3所示之保護膜形成用複合片1中的符號w2。 The notches corresponding to the pair of arcs form the curved peripheral edge portion of the adhesive layer indicated by reference numeral 121 in the composite sheet 1 for forming a protective film shown in FIG. 3 . In addition, the distance (20 mm) between the circle with a diameter of 270 mm and the aforementioned circular arc corresponds to the symbol w 2 in the composite sheet 1 for forming a protective film shown in FIG. 3 .

於第3積層體的長度方向(相對於圖3所示之保護膜形成用複合片1中以符號w1表示之寬度之方向正交之方向)上的多個部位，進行此種描繪出2個同心圓及一對圓弧之上述半切，以描繪出2條俯視下於相鄰部位之間將圓弧彼此於前述長度方向上連結之直線之方式，自塗層側，對塗層、基材及黏著劑層之全部進行切出切口之半切。相當於該2條直線之切口形成圖3所示之保護膜形成用複合片1中以符號122表示之黏著劑層的平面狀的周緣部122。 This kind of drawing 2 is performed at a plurality of locations in the longitudinal direction of the third laminate (the direction orthogonal to the width direction indicated by the symbol w 1 in the composite sheet 1 for forming a protective film shown in FIG. 3 ). The above-mentioned half-cuts of two concentric circles and a pair of circular arcs are used to draw two straight lines connecting the circular arcs in the aforementioned longitudinal direction between adjacent parts in plan view. The entire material and the adhesive layer are half-cut to cut out the incision. The notches corresponding to the two straight lines form the planar peripheral edge portion 122 of the adhesive layer indicated by the reference numeral 122 in the composite sheet 1 for forming a protective film shown in FIG. 3 .

繼而，將俯視下上述之直徑270mm之圓與一對圓弧之間之部分、及將上述之圓弧彼此連結之2條直線所夾持之部分中的塗層、基材及黏著劑層移除，藉此獲得圖1及圖3所示之保護膜形成用複合片。該保護膜形成用複合 片中的圓形的黏著劑層(支持片)相當於圖3中直徑d2為270mm之圓形的黏著劑層12(支持片10)。另外，該保護膜形成用複合片中的第1剝離膜相當於圖3中的剝離膜15。 Then, the coating layer, the base material and the adhesive layer in the part between the above-mentioned circle with a diameter of 270 mm and a pair of arcs, and the part sandwiched by the two straight lines connecting the above-mentioned arcs to each other in plan view were moved. Thereby, the composite sheet for protective film formation shown in FIG. 1 and FIG. 3 was obtained. The circular adhesive layer (support sheet) in the composite sheet for forming a protective film corresponds to the circular adhesive layer 12 (support sheet 10 ) having a diameter d 2 of 270 mm in FIG. 3 . In addition, the 1st release film in this composite sheet for protective film formation corresponds to the release film 15 in FIG. 3 .

[實施例2] [Example 2]

如表1所示，使用凹凸面的表面粗糙度Ra為1μm而並非0.4μm之基材，除該方面以外，利用與實施例1相同之方法，獲得保護膜形成用複合片。 As shown in Table 1, a composite sheet for forming a protective film was obtained by the same method as in Example 1, except that the surface roughness Ra of the uneven surface was 1 μm instead of 0.4 μm.

[實施例3] [Example 3]

如表1所示，使用凹凸面的表面粗糙度Ra為1μm而並非0.4μm之基材，且將塗層的厚度設為1μm代替3μm，除該方面以外，利用與實施例1相同之方法，獲得保護膜形成用複合片。 As shown in Table 1, the same method as in Example 1 was used except that the surface roughness Ra of the uneven surface was 1 μm instead of 0.4 μm, and the thickness of the coating layer was 1 μm instead of 3 μm. A composite sheet for forming a protective film was obtained.

[實施例4] [Example 4]

如表1所示，將塗層的厚度設為1μm代替3μm，除該方面以外，利用與實施例1相同之方法，獲得保護膜形成用複合片。 As shown in Table 1, except that the thickness of the coating layer was 1 μm instead of 3 μm, the same method as in Example 1 was used to obtain a composite sheet for forming a protective film.

[實施例5] [Example 5]

如表1所示，使用凹凸面的表面粗糙度Ra為1μm而並非0.4μm之基材，且將塗層的厚度設為6μm代替 3μm，除該方面以外，利用與實施例1相同之方法，獲得保護膜形成用複合片。 As shown in Table 1, the base material with the surface roughness Ra of the concave-convex surface was 1 μm instead of 0.4 μm, and the thickness of the coating layer was 6 μm instead A composite sheet for forming a protective film was obtained by the same method as in Example 1 except for this point of 3 μm.

[實施例6] [Example 6]

如表1所示，使用凹凸面的表面粗糙度Ra為3μm而並非0.4μm之基材，且將塗層的厚度設為6μm代替3μm，除該方面以外，利用與實施例1相同之方法，獲得保護膜形成用複合片。 As shown in Table 1, the same method as in Example 1 was used except that the surface roughness Ra of the uneven surface was 3 μm instead of 0.4 μm, and the thickness of the coating layer was 6 μm instead of 3 μm. A composite sheet for forming a protective film was obtained.

[比較例1] [Comparative Example 1]

如表1所示，使用凹凸面的表面粗糙度Ra為1μm而並非0.4μm之基材，且不形成塗層，除該方面以外，利用與實施例1相同之方法，獲得保護膜形成用複合片。 As shown in Table 1, except that the surface roughness Ra of the concavo-convex surface was 1 μm instead of 0.4 μm, and the coating layer was not formed, the same method as in Example 1 was used to obtain a composite for forming a protective film. piece.

[比較例2] [Comparative Example 2]

如表1所示，以凹凸面朝向相反側、亦即黏著劑層側(內側)之方式配置基材，且不形成塗層(亦即，設為圖5所示之以往之構成)，除該方面以外，利用與實施例1相同之方法，獲得保護膜形成用複合片。 As shown in Table 1, the base material is arranged so that the uneven surface faces the opposite side, that is, the adhesive layer side (inner side), and the coating layer is not formed (that is, the conventional structure shown in FIG. 5 is used), except Except this point, by the same method as Example 1, the composite sheet for protective film formation was obtained.

[比較例3] [Comparative Example 3]

如表1所示，使用凹凸面的表面粗糙度Ra為1μm而並非0.4μm之基材，以凹凸面朝向相反側、亦即黏著劑層側(內側)之方式配置該基材，且不形成塗層(亦即，設 為圖5所示之以往之構成)，除該方面以外，利用與實施例1相同之方法，獲得保護膜形成用複合片。 As shown in Table 1, a base material having a surface roughness Ra of 1 μm, not 0.4 μm, of the uneven surface was used, and the base material was arranged so that the uneven surface faced the opposite side, that is, the adhesive layer side (inner side), and did not form coating (that is, It is the conventional structure shown in FIG. 5), except for this point, by the method similar to Example 1, the composite sheet for protective film formation was obtained.

[比較例4] [Comparative Example 4]

使用以固形物成分計相同量的利用環氧基進行了表面修飾之球狀二氧化矽(Admatechs公司製造之「SC2050MA」，平均粒徑0.5μm)，代替二氧化矽溶膠分散於2-乙氧基乙醇中而成之分散液，除該方面以外，利用與實施例1相同之方法，製備塗佈組成物。 Spherical silica (“SC2050MA” manufactured by Admatechs, average particle size: 0.5 μm) surface-modified with epoxy groups was used in the same amount in terms of solid content, instead of silica sol and dispersed in 2-ethoxy A coating composition was prepared by the same method as in Example 1 except for the dispersion liquid prepared in ethanol.

並且，使用該塗佈組成物，除該方面以外，利用與實施例1相同之方法，獲得保護膜形成用複合片。 And using this coating composition, except this point, by the method similar to Example 1, the composite sheet for protective film formation was obtained.

所獲得之保護膜形成用複合片中，基材側最表面的表面粗糙度Ra如表1所示為0.8μm。 In the obtained composite sheet for forming a protective film, as shown in Table 1, the surface roughness Ra of the outermost surface on the substrate side was 0.8 μm.

<保護膜形成用複合片之評價> <Evaluation of the composite sheet for protective film formation>

[雷射印字性] [Laser printability]

上述獲得之各實施例及比較例之保護膜形成用複合片中，將第1剝離膜移除，使用貼附裝置(Lintec公司製造之「RAD-2700F/12」)，將黏著劑層貼附於不銹鋼製環狀框，並且將保護膜形成用膜貼附於加熱至70℃之矽晶圓(外徑8吋，厚度100μm)的背面。 In the composite sheet for forming a protective film of each of the Examples and Comparative Examples obtained above, the first release film was removed, and an adhesive layer was attached using an attaching device (“RAD-2700F/12” manufactured by Lintec Corporation). A film for forming a protective film was attached to the back surface of a silicon wafer (outer diameter 8 inches, thickness 100 μm) heated to 70° C. in a stainless steel ring frame.

繼而，將保護膜形成用膜於130℃下進行2小時加熱處理，藉此使保護膜形成用膜熱硬化而形成保護膜。 Next, the film for protective film formation was heat-processed at 130 degreeC for 2 hours, and the film for protective film formation was thermally hardened, and a protective film was formed.

繼而，使用印字裝置(KEYENCE公司製造之 「VK9700」)，於輸出0.6W、頻率40kHz、掃描速度100mm/秒之條件下，自基材側對保護膜照射波長532nm之雷射光，按照下述之2個圖案(圖案1、圖案2)對保護膜進行雷射印字。 Then, using a printing device (manufactured by KEYENCE Corporation) "VK9700"), under the conditions of output 0.6W, frequency 40kHz, scanning speed 100mm/sec, irradiate the protective film with laser light with wavelength of 532nm from the substrate side, according to the following two patterns (pattern 1, pattern 2) Laser print on the protective film.

(圖案) (pattern)

圖案1：文字尺寸0.4mm×0.5mm，文字間隔0.3mm，文字數20。 Pattern 1: The character size is 0.4mm×0.5mm, the character interval is 0.3mm, and the number of characters is 20.

圖案2：文字尺寸0.2mm×0.5mm，文字間隔0.3mm，文字數20。 Pattern 2: The character size is 0.2mm×0.5mm, the character interval is 0.3mm, and the number of characters is 20.

繼而，對利用上述雷射印字形成於保護膜之文字，依據下述基準評價自基材側之視認性(雷射印字性)。結果示於表1。 Next, regarding the characters formed on the protective film by the above-mentioned laser printing, the visibility (laser printing property) from the base material side was evaluated according to the following criteria. The results are shown in Table 1.

(評價基準) (Evaluation Criteria)

A：圖案1及圖案2之全部文字清晰，可無問題地讀出圖案1及圖案2之文字。 A: All the characters of pattern 1 and pattern 2 are clear, and the characters of pattern 1 and pattern 2 can be read without problems.

B：圖案2中至少一部分文字不清晰，但圖案1中全部文字清晰，可無問題地讀出圖案1之文字。 B: At least a part of the characters in the pattern 2 is not clear, but all the characters in the pattern 1 are clear, and the characters in the pattern 1 can be read without problems.

C：圖案1及圖案2之任一者中，均至少一部分文字不清晰。 C: In any of pattern 1 and pattern 2, at least a part of characters are unclear.

[耐黏連性(1)] [Blocking Resistance (1)]

將上述獲得之各實施例及比較例之保護膜形成用複合片，以10m之長度捲取於3吋直徑之 ABS(Acrylonitrile-Butadiene-Styrene；丙烯腈-丁二烯-苯乙烯)樹脂製芯材，直接以該狀態於室溫下靜置3天。 The above-obtained composite sheets for forming protective films of each of the Examples and Comparative Examples were wound into a 3-inch diameter sheet with a length of 10 m. The core material made of ABS (Acrylonitrile-Butadiene-Styrene; acrylonitrile-butadiene-styrene) resin was left to stand at room temperature for 3 days as it was.

繼而，針對實施例1至實施例5之保護膜形成用複合片，嘗試捲出依序積層有塗層、基材、黏著劑層、保護膜形成用膜及第1剝離膜之積層單元10個份，針對比較例1至比較例3之保護膜形成用複合片，由於不存在塗層，故而嘗試捲出依序積層有基材、黏著劑層、保護膜形成用膜及第1剝離膜之積層單元10個份，此時，評價捲取時相互接觸之保護膜形成用複合片之接觸部彼此是否黏附，並且於存在黏附之情形時對黏附之程度依據下述基準進行評價。結果示於表1。 Next, with respect to the composite sheets for forming a protective film of Examples 1 to 5, an attempt was made to roll out 10 lamination units in which the coating layer, the base material, the adhesive layer, the film for forming a protective film, and the first release film were laminated in this order. For the composite sheets for forming a protective film from Comparative Examples 1 to 3, since there is no coating layer, an attempt was made to roll out the composite sheet in which the base material, the adhesive layer, the film for forming a protective film and the first release film were laminated in this order. For 10 lamination units, at this time, it was evaluated whether or not the contact parts of the protective film-forming composite sheets that were in contact with each other during winding were adhered to each other, and when there was adhesion, the degree of adhesion was evaluated according to the following criteria. The results are shown in Table 1.

(評價基準) (Evaluation Criteria)

A：完全未確認到前述接觸部彼此之黏附。 A: Adhesion of the aforementioned contact portions to each other was not confirmed at all.

B：確認到前述接觸部彼此之輕度之黏附，但可無問題地捲出保護膜形成用複合片。 B: Slight adhesion of the above-mentioned contact portions was confirmed, but the composite sheet for forming a protective film could be rolled out without any problem.

C：前述接觸部彼此一部分完全黏附，捲出保護膜形成用複合片時，第1剝離膜自黏著劑層剝離。 C: A part of the said contact part adhered completely, and when the composite sheet for protective film formation was rolled out, the 1st peeling film was peeled from an adhesive bond layer.

[耐黏連性(2)] [Blocking Resistance (2)]

以成為寬度50mm、長度100mm之大小之帶之方式，切取上述獲得之各實施例及比較例之保護膜形成用複合片。再者，切取時，使該帶的長度方向與黏著劑組成物的塗佈方向一致。 The composite sheet for forming a protective film of each of the Examples and Comparative Examples obtained above was cut out so as to be a tape having a width of 50 mm and a length of 100 mm. In addition, when cutting, the longitudinal direction of this tape was made to correspond to the application direction of the adhesive composition.

準備如此獲得之帶10片，積層這些帶而製成試片。此時，於實施例1至實施例5之情形時，均以塗層朝上之方式積層前述帶。並且，於比較例1至比較例3之情形時，由於不存在塗層，故而均以基材朝上之方式積層前述帶。繼而，將該試片夾入2片玻璃板(寬度75mm、長度15mm、厚度5mm)，將這些玻璃板與試片之積層物整體以一玻璃板作為最下層載置於預定部位，於另一最上層之玻璃板上載置鉛錘，對前述試片進行加壓。此時，前述帶的積層方向上施加於前述試片之力為980.665mN(亦即100gf)。以該狀態將這些玻璃板與試片之積層物整體於濕熱促進器(ESPEC公司製造)內於40℃下保管3天，對前述試片進行加熱加壓促進試驗。 Ten pieces of the thus obtained tapes were prepared, and these tapes were laminated to prepare test pieces. At this time, in the case of Examples 1 to 5, the aforementioned tapes were laminated with the coating layer facing upward. In addition, in the case of Comparative Example 1 to Comparative Example 3, since there is no coating layer, the aforementioned tapes are all laminated with the substrate facing upward. Next, this test piece was sandwiched between two glass plates (width 75 mm, length 15 mm, thickness 5 mm), and the entire laminate of these glass plates and test pieces was placed on a predetermined position with one glass plate as the lowermost layer, and placed on the other. A plumb weight was placed on the uppermost glass plate to pressurize the test piece. At this time, the force applied to the test piece in the lamination direction of the tape was 980.665 mN (ie, 100 gf). In this state, the entire laminate of these glass plates and test pieces was stored in a moist heat accelerator (manufactured by ESPEC) at 40° C. for 3 days, and the above-mentioned test pieces were subjected to a heat and pressure acceleration test.

繼而，自濕熱促進器中取出前述試片，將最下層之第1剝離膜(最下層之與玻璃板接觸之第1剝離膜)及與該第1剝離膜鄰接之保護膜形成用膜移除，將露出之黏著劑層經由雙面黏著帶貼合於支持板，藉此將加熱加壓促進試驗後自前述試片僅移除最下層之第1剝離膜及與該第1剝離膜鄰接之保護膜形成用膜所得之試片固定於前述支持板。 Then, the test piece was taken out from the moist heat accelerator, and the first release film of the lowermost layer (the first release film of the lowermost layer in contact with the glass plate) and the film for forming a protective film adjacent to the first release film were removed. , the exposed adhesive layer is attached to the support plate through the double-sided adhesive tape, thereby removing only the first release film of the lowermost layer and the first release film adjacent to the first release film from the test piece after the heating and pressure acceleration test. The test piece obtained by the film for protective film formation was fixed to the said support plate.

繼而，於實施例1至實施例5之情形時，將上述固定物中，距離前述支持板最遠之最上層之由塗層、基材、黏著劑層及保護膜形成用膜構成之積層物移除，使用拉伸試驗機，將露出之第1剝離膜於剝離速度300mm/分鐘、剝離角度180°之條件下自鄰接之塗層剝離，測定此時之剝離 力。於比較例1至比較例3之情形時，將上述固定物中，距離前述支持板最遠之最上層之由基材、黏著劑層及保護膜形成用膜構成之積層物移除，使用拉伸試驗機，將露出之第1剝離膜，於剝離速度300mm/分鐘、剝離角度180°之條件下，自鄰接之基材剝離，測定此時之剝離力。將如此獲得之第1剝離膜之剝離力之測定值作為保護膜形成用複合片之耐黏連性之指標。 Then, in the case of Example 1 to Example 5, the above-mentioned fixed material, the uppermost layer farthest from the above-mentioned support plate, is composed of the coating layer, the base material, the adhesive layer and the protective film forming film. Remove, use a tensile tester, peel the exposed first release film from the adjacent coating under the conditions of a peeling speed of 300 mm/min and a peeling angle of 180°, and measure the peeling at this time. force. In the case of Comparative Examples 1 to 3, the laminates consisting of the base material, the adhesive layer and the protective film forming film in the uppermost layer farthest from the above-mentioned support plate were removed from the above-mentioned fixed material, and the layer was removed using a pulling method. A tensile tester was used to peel the exposed first release film from the adjacent substrate under the conditions of a peeling speed of 300 mm/min and a peeling angle of 180°, and the peeling force at this time was measured. The measured value of the peeling force of the first peeling film thus obtained was used as an index of the blocking resistance of the composite sheet for forming a protective film.

再者，於欲測定之第1剝離膜之剝離力足夠小之情形時，自濕熱促進器中取出前述試片，於自該試片如上所述般將與最下層之第1剝離膜(最下層之與玻璃板接觸之第1剝離膜)鄰接之保護膜形成用膜移除時，存在作為剝離力之測定對象之第1剝離膜首先自與該第1剝離膜鄰接之層(於實施例1至實施例5之情形時為塗層，於比較例1至比較例3之情形時為基材)剝離之情況。該情形時，自濕熱促進器中取出前述試片，自該試片移除最下層之第1剝離膜後，不移除與該第1剝離膜鄰接之保護膜形成用膜，將該保護膜形成用膜經由雙面黏著帶貼合於支持板，藉此將自前述試片僅移除最下層之第1剝離膜所得之試片固定於前述支持板，針對該固定物，與上述同樣地測定第1剝離膜之剝離力。 Furthermore, when the peeling force of the first peeling film to be measured is sufficiently small, the test piece is taken out from the moist heat accelerator, and the first peeling film (most When the protective film forming film adjacent to the first release film in contact with the glass plate of the lower layer is removed, the first release film that is the measurement object of the release force is first removed from the layer adjacent to the first release film (in Example 1). In the case of 1 to Example 5, it is a coating layer, and in the case of Comparative Example 1 to Comparative Example 3, it is a case of peeling off. In this case, the test piece is taken out from the moist heat accelerator, and after the first release film of the lowermost layer is removed from the test piece, the protective film forming film adjacent to the first release film is not removed, and the protective film is not removed. The film for forming is attached to the support plate via a double-sided adhesive tape, whereby the test piece obtained by removing only the first release film of the lowermost layer from the test piece is fixed to the support plate, and the same as above for the fixing object The peeling force of the first peeling film was measured.

結果示於表1。 The results are shown in Table 1.

[基材側最表面的表面粗糙度Ra] [Surface roughness Ra of the outermost surface on the substrate side]

針對上述所獲得之各實施例及比較例之保護膜形成用複合片，使用接觸式表面粗糙度計(Mitutoyo公司製造之「SURFTEST SV-3000」)，將臨界值λ c設為0.8mm，將評價長度Ln設為4mm，依據JIS B0601：2001測定基材側最表面，亦即，塗層中的與基材側為相反側的面的表面粗糙度Ra。結果示於表1。表1中，針對比較例1至比較例3之保護膜形成用複合片，記載與上述基材的黏著劑層側為相反側的面的表面粗糙度Ra作為基材側最表面的表面粗糙度Ra。 For the protective film-forming composite sheets of the respective Examples and Comparative Examples obtained above, using a contact surface roughness meter (“SURFTEST SV-3000” manufactured by Mitutoyo Corporation), the critical value λ c was set to 0.8 mm, and the The evaluation length Ln was set to 4 mm, and the outermost surface on the base material side, that is, the surface roughness Ra of the surface opposite to the base material side in the coating layer was measured according to JIS B0601:2001. The results are shown in Table 1. In Table 1, for the composite sheets for forming a protective film of Comparative Examples 1 to 3, the surface roughness Ra of the surface opposite to the adhesive layer side of the above-mentioned base material is described as the surface roughness of the outermost surface on the base material side Ra.

[塗層的表面的光澤值] [Gloss value of the coated surface]

針對上述所獲得之各實施例及比較例之保護膜形成用複合片，使用光澤計(日本電色公司製造之光澤計「VG 2000」)，依據JIS K 7105，自塗層的基材側的相反側，測定塗層的表面的20°鏡面光澤度，將該測定值設為塗層的表面的光澤值。結果示於表1。 The composite sheet for forming a protective film of each of the above-obtained Examples and Comparative Examples was obtained from a glossmeter (Glossmeter "VG 2000" manufactured by Nippon Denshoku Co., Ltd.) in accordance with JIS K 7105. On the other side, the 20° specular gloss of the surface of the coating layer was measured, and the measured value was set as the gloss value of the surface of the coating layer. The results are shown in Table 1.

[自塗層側之霧度之測定值] [Measured value of haze from coating side]

針對上述所獲得之各實施例及比較例之保護膜形成用複合片，使用測霧計(日本電色工業公司製造之「NDH-2000」)，依據JIS K 7136，自塗層側測定霧度。結果示於表1。 The haze was measured from the coating side in accordance with JIS K 7136 using a haze meter (“NDH-2000” manufactured by Nippon Denshoku Kogyo Co., Ltd.) for the protective film-forming composite sheets of the respective Examples and Comparative Examples obtained above. . The results are shown in Table 1.

[表1]

Figure 106104893-A0202-12-0120-3
[Table 1]
Figure 106104893-A0202-12-0120-3

實施例1至實施例6之保護膜形成用複合片藉由在基材側之最外層具備塗層，且該塗層的表面的光澤值為特定範圍內，雷射印字性及耐黏連性均良好。 The composite sheets for forming protective films of Examples 1 to 6 are provided with a coating on the outermost layer on the substrate side, and the gloss value of the surface of the coating is within a specific range, and the laser printing properties and blocking resistance are improved. All are good.

尤其是，實施例1、實施例2、實施例4及實施例5之保護膜形成用複合片相較於實施例3及實施例6之保護膜形成用複合片而言，雷射印字性優異，推測原因在於，實施例1、實施例2、實施例4及實施例5之保護膜形成用複合片中，塗層的表面的光澤值略大，成為更適宜的範圍內。 In particular, the composite sheets for forming a protective film of Example 1, Example 2, Example 4, and Example 5 were excellent in laser printability compared to the composite sheets for forming a protective film of Examples 3 and 6 , the reason is presumed that in the composite sheets for forming a protective film of Example 1, Example 2, Example 4 and Example 5, the gloss value of the surface of the coating layer was slightly larger, which was within a more suitable range.

另外，實施例1至實施例4之保護膜形成用複合片相 較於實施例5及實施例6之保護膜形成用複合片而言，耐黏連性優異，推測原因在於，實施例1至實施例4之保護膜形成用複合片的塗層的厚度較薄。 In addition, the composite sheets for forming protective films of Examples 1 to 4 were Compared with the composite sheets for forming a protective film of Examples 5 and 6, the blocking resistance is superior, and the reason is presumed that the thickness of the coating layer of the composite sheets for forming a protective film of Examples 1 to 4 is thinner. .

再者，關於實施例1至實施例6之保護膜形成用複合片，於基材與黏著劑層之間均未確認到空隙部。 In addition, regarding the composite sheet for protective film formation of Example 1 to Example 6, the void part was not confirmed between the base material and the adhesive bond layer.

相對於此，比較例1之保護膜形成用複合片與圖4所示之保護膜形成用複合片同樣地，基材中的與具備黏著劑層之側的面(表面)為相反側的面(背面)為凹凸面，且亦不具備塗層，藉此雖然耐黏連性優異，但雷射印字性差。 On the other hand, the composite sheet for forming a protective film of Comparative Example 1 is the same as the composite sheet for forming a protective film shown in FIG. 4 , and the surface (surface) on the side provided with the adhesive layer in the base material is the surface on the opposite side The (back surface) is a concave-convex surface and does not have a coating layer, so although it is excellent in blocking resistance, it is poor in laser printability.

比較例2之保護膜形成用複合片與圖5所示之保護膜形成用複合片同樣地，基材中的與具備黏著劑層之側的面(表面)為相反側的面(背面)為平滑面，且亦不具備塗層，藉此雖然雷射印字性良好，但耐黏連性差。比較例3之保護膜形成用複合片亦具有與比較例2之保護膜形成用複合片相同之構成，但不僅耐黏連性差，雷射印字性亦差。推測原因在於，基材中的具備黏著劑層之側的面(表面)為凹凸面，且該凹凸面的表面粗糙度Ra大於比較例2之保護膜形成用複合片的表面粗糙度Ra。推測比較例3中，由於前述凹凸面的表面粗糙度Ra大，故而凹凸面的形狀亦反映於保護膜的表面，保護膜的表面的凹凸程度大於比較例2之情形，藉此光之漫反射更大，雷射印字性更差。進一步推測，比較例2及比較例3之保護膜形成用複合片 均於基材的凹凸面與黏著劑層之間存在空隙部，但由於比較例3相較於比較例2而言凹凸面的表面粗糙度Ra大，故而空隙部變大，因此比較例3相較於比較例2而言光之漫反射更大，雷射印字性更差。 The composite sheet for forming a protective film of Comparative Example 2 is similar to the composite sheet for forming a protective film shown in FIG. 5 , and the surface (back surface) on the opposite side to the surface (surface) on the side provided with the adhesive layer in the base material is: It has a smooth surface and does not have a coating, so although the laser printing is good, the blocking resistance is poor. The composite sheet for forming a protective film of Comparative Example 3 also had the same structure as the composite sheet for forming a protective film of Comparative Example 2, but not only poor blocking resistance but also poor laser printability. The reason is presumed that the surface (surface) on the side with the adhesive layer in the base material is an uneven surface, and the surface roughness Ra of the uneven surface is larger than the surface roughness Ra of the composite sheet for forming a protective film of Comparative Example 2. It is presumed that in Comparative Example 3, since the surface roughness Ra of the uneven surface is large, the shape of the uneven surface is also reflected on the surface of the protective film, and the degree of unevenness on the surface of the protective film is larger than that of Comparative Example 2, thereby diffuse reflection of light Larger and less laser printable. It is further presumed that the composite sheet for forming a protective film of Comparative Example 2 and Comparative Example 3 There are voids between the uneven surface of the base material and the adhesive layer in all cases, but since the surface roughness Ra of the uneven surface of Comparative Example 3 is larger than that of Comparative Example 2, the voids become larger, so Comparative Example 3 phase Compared with Comparative Example 2, the diffuse reflection of light is larger, and the laser printing property is worse.

比較例4之保護膜形成用複合片與實施例1之保護膜形成用複合片同樣地，基材中的與具備黏著劑層之側的面(表面)為相反側的面(背面)為凹凸面，且亦具備塗層，耐黏連性優異，但雷射印字性差。推測原因在於，比較例4之保護膜形成用複合片中，塗層的表面的光澤值小，不在適宜的範圍內。 The composite sheet for forming a protective film of Comparative Example 4 is the same as the composite sheet for forming a protective film of Example 1, and the surface (back surface) on the opposite side to the surface (surface) on the side provided with the adhesive layer in the base material is uneven. Surface, and also has a coating, excellent blocking resistance, but poor laser printing. The reason is presumably that in the composite sheet for forming a protective film of Comparative Example 4, the gloss value of the surface of the coating layer was small and not within a suitable range.

(產業可利用性) (Industrial Availability)

本發明可用於製造背面由保護膜保護之半導體晶片等。 The present invention can be used to manufacture semiconductor wafers and the like whose back surfaces are protected by a protective film.

1‧‧‧保護膜形成用複合片 1‧‧‧Composite sheet for forming protective film

10‧‧‧支持片 10‧‧‧Support Sheet

10a‧‧‧支持片的表面 10a‧‧‧Surface of support sheet

10b‧‧‧支持片的背面 10b‧‧‧Back side of support sheet

11‧‧‧基材 11‧‧‧Substrate

11a‧‧‧基材的表面 11a‧‧‧Substrate surface

11b‧‧‧基材的背面 11b‧‧‧Backside of substrate

12‧‧‧黏著劑層 12‧‧‧Adhesive layer

12a‧‧‧黏著劑層的表面 12a‧‧‧The surface of the adhesive layer

13‧‧‧保護膜形成用膜 13‧‧‧Film for forming protective film

13a‧‧‧保護膜形成用膜的表面 13a‧‧‧The surface of the film for forming a protective film

14‧‧‧塗層 14‧‧‧Coating

14a‧‧‧塗層的表面 14a‧‧‧Coated surface

14b‧‧‧塗層的背面 14b‧‧‧Coated backside

15‧‧‧剝離膜 15‧‧‧Peeling film

15a‧‧‧剝離膜的表面 15a‧‧‧Surface of release film

Claims (5)

一種保護膜形成用複合片，係於支持片的一表面上具備保護膜形成用膜，並於前述支持片中的與具備前述保護膜形成用膜之側為相反側的表面上具備塗層；前述支持片由基材及黏著劑層積層而成；前述保護膜形成用複合片由前述塗層、基材、黏著劑層及保護膜形成用膜依序積層而成；前述基材之具備有黏著劑層的面為平滑面，表面粗糙度Ra為0.001μm至0.1μm；前述塗層中的與前述支持片接觸之側為相反側的表面的光澤值為32至95。 A composite sheet for forming a protective film is provided with a film for forming a protective film on a surface of the support sheet, and a coating is provided on the surface of the opposite side with the side having the film for forming the aforementioned protective film in the aforementioned support sheet; The above-mentioned support sheet is formed by laminating a base material and an adhesive; the above-mentioned composite sheet for forming a protective film is formed by laminating the above-mentioned coating layer, a base material, an adhesive layer and a film for forming a protective film in sequence; the above-mentioned base material is provided with The surface of the adhesive layer is a smooth surface, and the surface roughness Ra is 0.001 μm to 0.1 μm; the gloss value of the surface on the opposite side in contact with the support sheet in the coating layer is 32 to 95. 如請求項1所記載之保護膜形成用複合片，其中使用進一步於前述保護膜形成用膜上具備剝離膜之前述保護膜形成用複合片，利用下述方法測定之前述剝離膜的剝離力為10mN/50mm以下；前述剝離膜的剝離力的測定方法如下：將於保護膜形成用膜上具備剝離膜且寬度50mm、長度100mm之前述保護膜形成用複合片以前述塗層全部朝向相同方向且前述塗層的合計厚度成為10μm至60μm之方式重疊複數片，藉此製成第一最外層為塗層且第二最外層為剝離膜之積層體，將前述積層體以於前述保護膜形成用複合片的積層方向上施加980.665mN之力之狀態於40℃下靜置3天後，將於前述積層方向上距離前述第一最外層之塗層 最近之剝離膜於剝離速度300mm/分鐘、剝離角度180°之條件下自鄰接之塗層剝離，測定此時的剝離力。 The composite sheet for forming a protective film according to claim 1, wherein the composite sheet for forming a protective film further comprising a peeling film on the film for forming a protective film is used, and the peeling force of the peeling film measured by the following method is: 10mN/50mm or less; the method for measuring the peeling force of the aforementioned peeling film is as follows: the aforementioned composite sheet for forming a protective film with a peeling film having a width of 50 mm and a length of 100 mm is provided with a peeling film on the film for forming a protective film, with the aforementioned coating layers all oriented in the same direction and A plurality of sheets are stacked so that the total thickness of the coating layers is 10 μm to 60 μm, thereby forming a layered product in which the first outermost layer is a coating layer and the second outermost layer is a release film, and the layered body is used for forming the protective film. After the composite sheet was left to stand at 40°C for 3 days with a force of 980.665 mN applied in the lamination direction, the coating layer in the lamination direction from the first outermost layer was removed. The latest peeling film was peeled off from the adjacent coating layer under the conditions of a peeling speed of 300 mm/min and a peeling angle of 180°, and the peeling force at that time was measured. 如請求項1所記載之保護膜形成用複合片，其中[塗層的厚度(μm)]/[支持片中的具備塗層之側的表面的表面粗糙度Ra(μm)]之值為0.5至10。 The composite sheet for forming a protective film according to claim 1, wherein the value of [the thickness of the coating layer (μm)]/[the surface roughness Ra (μm) of the surface on the side having the coating layer in the support sheet] is 0.5 to 10. 如請求項1所記載之保護膜形成用複合片，其中前述黏著劑層為能量線硬化性或非能量線硬化性之層。 The composite sheet for forming a protective film according to claim 1, wherein the adhesive layer is an energy ray curable or non-energy ray curable layer. 如請求項1至4中任一項所記載之保護膜形成用複合片，其中前述保護膜形成用膜為熱硬化性或能量線硬化性之膜。 The composite sheet for forming a protective film according to any one of claims 1 to 4, wherein the film for forming a protective film is a thermosetting or energy ray-curable film.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201213486A (en) * 2010-07-30 2012-04-01 Nitto Denko Corp Dicing tape-integrated film for semiconductor back surface and method for producing the film, and method for producing semiconductor device
CN105009277A (en) * 2013-03-19 2015-10-28 琳得科株式会社 Film for forming protection film

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1370415B1 (en) * 2001-02-26 2013-08-07 Treofan Germany GmbH & Co.KG Laser-markable laminate
JP4762671B2 (en) * 2005-10-26 2011-08-31 古河電気工業株式会社 Dicing tape and semiconductor wafer dicing method
KR101035297B1 (en) * 2006-09-27 2011-05-19 후지쯔 세미컨덕터 가부시키가이샤 Method for manufacturing semiconductor device
JP5391158B2 (en) * 2010-06-30 2014-01-15 古河電気工業株式会社 Wafer sticking adhesive sheet and wafer processing method using the same
JP5583724B2 (en) * 2012-09-20 2014-09-03 リンテック株式会社 Laser dicing sheet-peeling sheet laminate, laser dicing sheet and chip body manufacturing method
JP6059499B2 (en) * 2012-10-05 2017-01-11 リンテック株式会社 Surface protection sheet
TWI647295B (en) * 2012-10-05 2019-01-11 日商琳得科股份有限公司 Method for manufacturing cut sheet and wafer with protective film forming layer
WO2014155756A1 (en) * 2013-03-26 2014-10-02 リンテック株式会社 Adhesive sheet, composite sheet for forming protective film, and method for manufacturing chip with protective film
JP6405556B2 (en) * 2013-07-31 2018-10-17 リンテック株式会社 Protective film forming film, protective film forming sheet and inspection method
KR102356171B1 (en) * 2014-03-24 2022-01-26 린텍 가부시키가이샤 Protection membrane forming film, protection membrane forming utilization sheet, production method and inspection method for workpiece or processed product, workpiece determined as adequate product, and processed product determined as adequate product
JP6334223B2 (en) * 2014-03-26 2018-05-30 リンテック株式会社 Adhesive sheet
JP5823591B1 (en) * 2014-10-01 2015-11-25 古河電気工業株式会社 Adhesive tape for protecting semiconductor wafer surface and method for processing semiconductor wafer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201213486A (en) * 2010-07-30 2012-04-01 Nitto Denko Corp Dicing tape-integrated film for semiconductor back surface and method for producing the film, and method for producing semiconductor device
CN105009277A (en) * 2013-03-19 2015-10-28 琳得科株式会社 Film for forming protection film

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