TWI731964B - Complex sheet for forming protective film - Google Patents

Complex sheet for forming protective film Download PDF

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TWI731964B
TWI731964B TW106113626A TW106113626A TWI731964B TW I731964 B TWI731964 B TW I731964B TW 106113626 A TW106113626 A TW 106113626A TW 106113626 A TW106113626 A TW 106113626A TW I731964 B TWI731964 B TW I731964B
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protective film
forming
film
meth
mass
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TW201741421A (en
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佐藤明德
稻男洋一
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日商琳得科股份有限公司
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    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • 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
    • 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
    • H01L23/00—Details of semiconductor or other solid state devices
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/72—Cured, e.g. vulcanised, cross-linked

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Dicing (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Physical Vapour Deposition (AREA)
  • Inorganic Insulating Materials (AREA)

Abstract

To provide a complex sheet for forming protective film comprise a film for forming protective film that is energy radiation-curing, can produce a protective film on the back surface of a semiconductor wafer or a semiconductor chip, and has a good suitability for dicing. A complex sheet for forming protective film 1A of the present invention comprise a film for forming protective film 13 that is energy radiation-curing on the supporting sheet 10, wherein the adhesive force between the protective film and the supporting sheet 10 is 100 mN/25mm or more and 2000 mN/25mm or less, when a film for forming protective film 13 is cured to form a protective film by irradiation with the energy ray.

Description

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

本發明係關於一種保護膜形成用複合片。 The present invention relates to a composite sheet for forming a protective film.

本申請案主張基於2016年4月28日在日本提出申請之日本專利特願2016-092032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. 2016-092032 filed in Japan on April 28, 2016, and the content of the application is incorporated herein.

近年來，業界使用稱為所謂倒裝(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，有時半導體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 the circuit surface is used, and the aforementioned electrodes are joined to the substrate. Therefore, the back surface of the semiconductor wafer opposite to the circuit surface may be exposed.

有時於該裸露之半導體晶片的背面，形成含有有機材料之樹脂膜作為保護膜，從而以附有保護膜的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半導體晶片產生龜裂。 Sometimes a resin film containing an organic material is formed as a protective film on the backside of the exposed semiconductor chip, so as to be incorporated into a semiconductor device in the form of a semiconductor chip with a protective film. The protective film is used to prevent the semiconductor chip from cracking after the dicing step or packaging.

為了形成此種保護膜，例如使用於支持片上具備用以形成保護膜之保護膜形成用膜之保護膜形成用複合片。保 護膜形成用複合片中，可使保護膜形成用膜藉由硬化而形成保護膜，進而可利用支持片作為切割片，從而可製成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。 In order to form such a protective film, the composite sheet for protective film formation provided with the film for protective film formation for forming a protective film on a support sheet, for example is used. Protect In the protective film forming composite sheet, the protective film forming film can be cured to form a protective film, and the support sheet can be used as a dicing sheet to form a protective film in which the protective film forming film and the dicing sheet are integrated Composite sheet for formation.

作為此種保護膜形成用複合片，例如此前主要利用具備熱硬化性之保護膜形成用膜之保護膜形成用複合片，前述熱硬化性之保護膜形成用膜藉由利用加熱進行硬化而形成保護膜。該情形時，例如，於半導體晶圓的背面(與電極形成面為相反側的面)，藉由熱硬化性之保護膜形成用膜，貼附保護膜形成用複合片後，藉由加熱使保護膜形成用膜硬化而成為保護膜，藉由切割將半導體晶圓連同保護膜一起分割而製成半導體晶片。然後，將半導體晶片保持貼附有該保護膜之狀態不變，自支持片拉離而進行拾取。 As such a composite sheet for forming a protective film, for example, heretofore, a composite sheet for forming a protective film is mainly used with a thermally curable protective film forming film. The thermally curable protective film forming film is formed by curing by heating. Protective film. In this case, for example, on the back surface of the semiconductor wafer (the surface opposite to the electrode formation surface), a thermally curable protective film formation film is applied, and then the protective film formation composite sheet is attached by heating. The protective film forming film is cured to become a protective film, and the semiconductor wafer is divided together with the protective film by dicing to produce a semiconductor wafer. Then, the semiconductor wafer is kept in the state where the protective film is attached, and is pulled away from the supporting sheet to be picked up.

但是，熱硬化性之保護膜形成用膜之加熱硬化通常需要數小時左右之長時間，因此期望縮短硬化時間。針對上述情況，業界正研究將可藉由照射紫外線等能量線而硬化之保護膜形成用膜用於形成保護膜。例如，揭示有：形成於剝離膜上之能量線硬化型保護膜(參照專利文獻1)；可形成高硬度且對半導體晶片之密接性優異之保護膜之能量線硬化型晶片保護用膜(參照專利文獻2)。 However, heating and curing of a film for forming a thermosetting protective film usually takes a long time of about several hours, and therefore it is desired to shorten the curing time. In response to the above situation, the industry is studying the use of a protective film forming film that can be cured by irradiating energy rays such as ultraviolet rays for forming a protective film. For example, there are disclosed: an energy ray hardening type protective film formed on a release film (refer to Patent Document 1); an energy ray hardening type wafer protective film that can form a protective film with high hardness and excellent adhesion to semiconductor wafers (refer to Patent Document 2).

[先前技術文獻] [Prior Technical Literature]

[專利文獻] [Patent Literature]

專利文獻1：日本專利第5144433號公報。 Patent Document 1: Japanese Patent No. 5144433.

專利文獻2：日本專利特開2010-031183號公報。 Patent Document 2: Japanese Patent Laid-Open No. 2010-031183.

但是，於使用專利文獻1中所揭示之能量線硬化型保護膜形成用膜、或者專利文獻2中所揭示之能量線硬化型晶片保護用膜之情形時，存在如下課題：照射紫外線等能量線，使膜硬化而成為保護膜後，使用切割刀片進行切割時，保護膜與支持片剝離，由此導致背面具備保護膜之半導體晶片自支持片飛散，或切削水向保護膜與支持片之間浸入。 However, when the energy-ray-curable protective film formation film disclosed in Patent Document 1 or the energy-ray-curable wafer protection film disclosed in Patent Document 2 is used, there is the following problem: irradiation of energy rays such as ultraviolet rays After hardening the film to become a protective film, when cutting with a dicing blade, the protective film is peeled from the support sheet, which causes the semiconductor wafer with the protective film on the back to scatter from the support sheet, or the cutting water flows between the protective film and the support sheet immersion.

因此，本發明提供一種保護膜形成用複合片，具備能量線硬化性之保護膜形成用膜，該保護膜形成用膜可於半導體晶圓或半導體晶片的背面形成保護膜，具有良好的切割適性。 Therefore, the present invention provides a composite sheet for forming a protective film, a film for forming a protective film with energy ray curability. The film for forming a protective film can form a protective film on the back of a semiconductor wafer or semiconductor wafer, and has good dicing adaptability. .

為了解決上述課題，本發明提供一種保護膜形成用複合片，於支持片上具備能量線硬化性之保護膜形成用膜，前述保護膜形成用膜被照射能量線而成為保護膜時，前述 保護膜與前述支持片之間的黏著力為100mN/25mm至2000mN/25mm。 In order to solve the above-mentioned problems, the present invention provides a composite sheet for forming a protective film, a film for forming a protective film having energy ray curability on a support sheet, and when the film for forming a protective film is irradiated with energy rays to become a protective film, The adhesive force between the protective film and the aforementioned supporting sheet is 100 mN/25 mm to 2000 mN/25 mm.

本發明之保護膜形成用複合片中，較佳為前述支持片具有黏著劑層，且前述保護膜形成用膜與前述黏著劑層直接接觸。 In the composite sheet for forming a protective film of the present invention, it is preferable that the support sheet has an adhesive layer, and the film for forming a protective film is in direct contact with the adhesive layer.

本發明之保護膜形成用複合片較佳為進而前述黏著劑層為非能量線硬化性。 In the composite sheet for forming a protective film of the present invention, it is preferable that the adhesive layer is non-energy-ray curable.

根據本發明，提供一種保護膜形成用複合片，具備能量線硬化性之保護膜形成用膜，該保護膜形成用膜可於半導體晶圓或半導體晶片的背面形成保護膜，具有良好的切割適性。 According to the present invention, there is provided a composite sheet for forming a protective film, a film for forming a protective film with energy ray curability. The film for forming a protective film can form a protective film on the back of a semiconductor wafer or a semiconductor wafer, and has good dicing suitability .

1A、1B、1C、1D、1E‧‧‧保護膜形成用複合片 1A, 1B, 1C, 1D, 1E‧‧‧Composite sheet for forming protective film

10‧‧‧支持片 10‧‧‧Support film

10a‧‧‧支持片的表面 10a‧‧‧Support the surface of the film

11‧‧‧基材 11‧‧‧Substrate

11a‧‧‧基材的表面 11a‧‧‧The surface of the 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‧‧‧Film for forming protective film

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

15‧‧‧剝離膜 15‧‧‧Peeling film

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

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

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

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

圖3係以示意方式表示本發明之保護膜形成用複合片的又一實施形態之剖面圖。 Fig. 3 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention.

圖4係以示意方式表示本發明之保護膜形成用複合片的又一實施形態之剖面圖。 Fig. 4 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention.

圖5係以示意方式表示本發明之保護膜形成用複合片 的又一實施形態之剖面圖。 Fig. 5 schematically shows the composite sheet for forming a protective film of the present invention A cross-sectional view of another embodiment of.

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

本發明之保護膜形成用複合片於支持片上具備能量線硬化性之保護膜形成用膜，前述保護膜形成用膜被照射能量線而成為保護膜時，前述保護膜與前述支持片之間的黏著力為100mN/25mm至2000mN/25mm。 The composite sheet for forming a protective film of the present invention has a film for forming a protective film having energy ray curability on a support sheet, and when the film for forming a protective film is irradiated with energy rays to become a protective film, the gap between the protective film and the support sheet is The adhesion is from 100mN/25mm to 2000mN/25mm.

再者，本說明書中，所謂「保護膜形成用膜」，意指硬化前的保護膜形成用膜，所謂「保護膜」，意指保護膜形成用膜硬化後之膜。 In addition, in this specification, the "protective film formation film" means the protective film formation film before curing, and the "protective film" means the protective film formation film after curing.

前述保護膜形成用膜藉由照射能量線進行硬化而成為保護膜。該保護膜用以對半導體晶圓或半導體晶片的背面(與電極形成面為相反側的面)進行保護。保護膜形成用膜為軟質，可容易地貼附於貼附對象物。並且，藉由保護膜與前述支持片之間的黏著力成為100mN/25mm至2000mN/25mm，本發明之保護膜形成用複合片具有良好的切割適性。更具體而言，將半導體晶圓連同保護膜一起藉由切割刀片切割時，保護膜與支持片之剝離得到抑制，例如背面具備保護膜之半導體晶片(附有保護膜的半導體晶片)自支持片之飛散得到抑制，可防止切削水向保護膜與支持片之間浸入。 The film for forming a protective film is cured by irradiation with energy rays to become a protective film. The protective film is used to protect the semiconductor wafer or the back surface (the surface opposite to the electrode formation surface) of the semiconductor wafer. The protective film forming film is soft and can be easily attached to an object to be attached. In addition, as the adhesive force between the protective film and the aforementioned support sheet becomes 100 mN/25mm to 2000 mN/25mm, the composite sheet for forming a protective film of the present invention has good cutting adaptability. More specifically, when the semiconductor wafer and the protective film are diced by a dicing blade, the peeling of the protective film and the support sheet is suppressed. For example, a semiconductor wafer with a protective film on the back side (semiconductor wafer with a protective film) self-supporting sheet The scattering is suppressed and cutting water can be prevented from entering between the protective film and the support sheet.

另外，本發明之保護膜形成用複合片中，前述保護膜 形成用膜為能量線硬化性，藉此相較於具備熱硬化性之保護膜形成用膜之先前之保護膜形成用複合片之情形，可藉由短時間之硬化而形成保護膜。 In addition, in the composite sheet for forming a protective film of the present invention, the protective film The formation film is energy ray curable, so that the protective film can be formed by curing in a short time compared to the previous composite sheet for protective film formation of the protective film formation film with thermosetting properties.

本發明中，所謂「能量線」，意指具有能量量子的電磁波或帶電粒子束，作為該能量線的示例，可列舉紫外線、放射線、電子束等。 In the present invention, the term "energy rays" means electromagnetic waves or charged particle beams having energy quantum, and examples of the energy rays include ultraviolet rays, radiation rays, electron beams, and the like.

紫外線例如可藉由使用高壓水銀燈、Fusion H型燈、氙氣燈、黑光燈或LED(Light Emitting Diode；發光二極體)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。 The ultraviolet light can be irradiated by using a high-pressure mercury lamp, a Fusion H-type lamp, a xenon lamp, a black light lamp, or an LED (Light Emitting Diode) lamp as an ultraviolet source, for example. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like.

本發明中，所謂「能量線硬化性」，意指藉由照射能量線而硬化之性質，所謂「非能量線硬化性」，意指即便照射能量線亦不硬化之性質。 In the present invention, the "energy ray curability" refers to the property of curing by irradiation with energy rays, and the "non-energy ray curability" refers to the property of not curing even if energy rays are irradiated.

作為本發明之保護膜形成用複合片之使用對象之半導體晶圓或半導體晶片的厚度並無特別限定，就獲得更顯著的本發明之效果而言，較佳為30μm至1000μm，更佳為100μm至300μm。 The thickness of the semiconductor wafer or semiconductor wafer used as the object of the composite sheet for forming a protective film of the present invention is not particularly limited, but in terms of obtaining more significant effects of the present invention, it is preferably 30 μm to 1000 μm, more preferably 100 μm To 300μm.

以下，對本發明之構成進行詳細說明。 Hereinafter, the structure of the present invention will be described in detail.

◎支持片 ◎Support film

前述支持片可由1層(單層)構成，亦可由2層以上之多層構成。於支持片由多層構成之情形時，該等多層的構 成材料及厚度可相互相同亦可不同，只要無損本發明之效果，則該等多層之組合並無特別限定。 The aforementioned support sheet may be composed of one layer (single layer), or may be composed of multiple layers of two or more layers. When the support sheet is composed of multiple layers, the multiple layers The forming materials and thicknesses may be the same or different from each other, and the combination of the layers is not particularly limited as long as the effect of the present invention is not impaired.

再者，本說明書中，不限於支持片之情形，所謂「多層可相互相同亦可不同」，意指「可全部層相同，亦可全部層皆不同，還可僅一部分層相同」，進而所謂「多層相互不同」，意指「各層之構成材料及厚度之至少一者相互不同」。 Furthermore, in this specification, it is not limited to the case of supporting sheets. The so-called "multilayers may be the same or different from each other" means "all layers may be the same, or all layers may be different, and only a part of the layers may be the same." "Multilayers are different from each other" means "at least one of the constituent materials and thickness of each layer is different from each other."

作為較佳的支持片，例如可列舉：於基材上以直接接觸之方式積層黏著劑層而成之支持片、於基材上經由中間層積層黏著劑層而成之支持片、僅由基材構成之支持片等。 As a preferable support sheet, for example, a support sheet formed by laminating an adhesive layer on a substrate in direct contact, a support sheet formed by laminating an adhesive layer on a substrate via an intermediate layer, and a support sheet composed of only the base Supporting pieces of material composition, etc.

以下，按照上述支持片之每個種類，一面參照圖式一面說明本發明之保護膜形成用複合片之示例。再者，以下之說明中所使用之圖中，為了易於理解本發明之特徵，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。 Hereinafter, an example of the composite sheet for forming a protective film of the present invention will be described with reference to the drawings for each type of the above-mentioned support sheet. Furthermore, in the drawings used in the following description, in order to make it easier to understand the features of the present invention and for convenience, the main parts are sometimes enlarged and shown, and they are not limited to the size ratio of each component being the same as the actual ones. .

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

此處所示之保護膜形成用複合片1A於基材11上具備黏著劑層12，於黏著劑層12上具備保護膜形成用膜13。支持片10為基材11及黏著劑層12之積層體，換言 之，保護膜形成用複合片1A具有於支持片10的一表面10a上積層有保護膜形成用膜13之構成。另外，保護膜形成用複合片1A進而於保護膜形成用膜13上具備剝離膜15。 The composite sheet 1A for forming a protective film shown here includes an adhesive layer 12 on a base material 11 and a protective film forming film 13 on the adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12, in other words In addition, the composite sheet 1A for forming a protective film has a structure in which a film 13 for forming a protective film is laminated on one surface 10 a of the support sheet 10. In addition, the composite sheet 1A for forming a protective film further includes a release film 15 on the film 13 for forming a protective film.

「剝離膜」係具有剝離功能之膜，具體而言，係指為了保護貼附於半導體晶圓之前的保護膜形成用膜，而黏附於保護膜形成用膜的表面之膜，作業時將該剝離膜剝離而使用。 "Release film" is a film with a peeling function. Specifically, it refers to a film that adheres to the surface of the protective film formation film in order to protect the protective film formation film before being attached to the semiconductor wafer. The peeling film is peeled off and used.

保護膜形成用複合片1A中，於基材11的一表面11a積層有黏著劑層12，於黏著劑層12的表面12a的整個面積層有保護膜形成用膜13，於保護膜形成用膜13的表面13a的一部分，亦即周緣部附近的區域積層有治具用接著劑層16，於保護膜形成用膜13的表面13a中未積層治具用接著劑層16之面及治具用接著劑層16的表面16a(上表面及側面)積層有剝離膜15。 In the composite sheet 1A for forming a protective film, an adhesive layer 12 is laminated on one surface 11a of a base material 11, a protective film forming film 13 is layered on the entire surface 12a of the adhesive layer 12, and a protective film forming film A part of the surface 13a of 13, that is, the area near the peripheral edge, is laminated with an adhesive layer 16 for jigs. On the surface 13a of the protective film forming film 13 where the adhesive layer 16 for jigs is not laminated, and for jigs A release film 15 is laminated on the surface 16a (upper surface and side surface) of the adhesive layer 16.

保護膜形成用複合片1A中，硬化後之保護膜形成用膜13(亦即保護膜)與支持片10之間的黏著力，換言之保護膜與黏著劑層12之間的黏著力為100mN/25mm至2000mN/25mm。 In the protective film forming composite sheet 1A, the adhesive force between the cured protective film forming film 13 (that is, the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the adhesive layer 12 is 100 mN/ 25mm to 2000mN/25mm.

治具用接著劑層16例如可為含有接著劑成分之單層結構，亦可為於成為芯材之片的雙面積層有含有接著劑成 分之層之多層結構。 The adhesive layer 16 for jigs may have, for example, a single-layer structure containing adhesive components, or a double-area layer of a sheet that becomes a core material may have an adhesive-containing composition. The multi-layer structure is divided into layers.

圖1所示之保護膜形成用複合片1A係以下述方式使用，亦即，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，進而，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 1A for forming a protective film shown in FIG. 1 is used in the following manner, that is, with the release film 15 removed, a semiconductor wafer (not shown in the figure) is attached to the surface 13a of the film 13 for forming a protective film ), and further, the upper surface of the surface 16a of the jig adhesive layer 16 is attached to a jig such as a ring frame.

圖2係以示意方式表示本發明之保護膜形成用複合片的另一實施形態之剖面圖。再者，圖2以後之圖中，對於與既已說明之圖所示相同的構成要素，標附與該已說明之圖之情形相同的符號，並省略該符號的詳細說明。 Fig. 2 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention. In addition, in the figures following FIG. 2, for the same constituent elements as those shown in the previously described figures, the same symbols as in the previously described figures are attached, and detailed descriptions of the symbols are omitted.

關於此處所示之保護膜形成用複合片1B，除不具備治具用接著劑層16之方面以外，與圖1所示之保護膜形成用複合片1A相同。亦即，保護膜形成用複合片1B中，於基材11的一表面11a積層有黏著劑層12，於黏著劑層12的表面12a的整個面積層有保護膜形成用膜13，於保護膜形成用膜13的表面13a的整個面積層有剝離膜15。 The composite sheet 1B for forming a protective film shown here is the same as the composite sheet 1A for forming a protective film shown in FIG. 1 except that it does not include the adhesive layer 16 for jigs. That is, in the composite sheet 1B for forming a protective film, an adhesive layer 12 is laminated on one surface 11a of the base material 11, and a protective film forming film 13 is layered on the entire surface 12a of the adhesive layer 12. The release film 15 is layered on the entire surface 13a of the forming film 13.

圖2所示之保護膜形成用複合片1B係以下述方式使用，亦即，在移除剝離膜15之狀態下，於保護膜形成用膜13的表面13a中的中央側的一部分區域貼附半導體晶圓(省略圖示)的背面，進而，將保護膜形成用膜13的周 緣部附近的區域貼附於環狀框等治具。 The composite sheet 1B for forming a protective film shown in FIG. 2 is used in a state where the release film 15 is removed and attached to a part of the area on the central side of the surface 13a of the film 13 for forming a protective film The back surface of the semiconductor wafer (not shown), and the protective film formation film 13 The area near the edge is attached to a jig such as a ring frame.

圖3係以示意方式表示本發明之保護膜形成用複合片的又一實施形態之剖面圖。 Fig. 3 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention.

關於此處所示之保護膜形成用複合片1C，除不具備黏著劑層12之方面以外，與圖1所示之保護膜形成用複合片1A相同。亦即，保護膜形成用複合片1C中，支持片10僅由基材11構成。並且，於基材11的一表面11a(支持片10的一表面10a)積層有保護膜形成用膜13，於保護膜形成用膜13的表面13a的一部分，亦即周緣部附近的區域積層有治具用接著劑層16，於保護膜形成用膜13的表面13a中未積層治具用接著劑層16之面及治具用接著劑層16的表面16a(上表面及側面)積層有剝離膜15。 The composite sheet 1C for forming a protective film shown here is the same as the composite sheet 1A for forming a protective film shown in FIG. 1 except that the adhesive layer 12 is not provided. That is, in the composite sheet 1C for forming a protective film, the support sheet 10 is composed of only the base material 11. In addition, a protective film forming film 13 is laminated on one surface 11a of the substrate 11 (one surface 10a of the support sheet 10), and a portion of the surface 13a of the protective film forming film 13, that is, a region near the peripheral edge is laminated The adhesive layer 16 for jigs is peeled off on the surface 13a of the protective film forming film 13 where the adhesive layer 16 for jigs is not laminated and the surface 16a (upper surface and side surfaces) of the adhesive layer 16 for jigs膜15。 Film 15.

保護膜形成用複合片1C中，硬化後之保護膜形成用膜13(亦即保護膜)與支持片10之間的黏著力，換言之保護膜與基材11之間的黏著力為100mN/25mm至2000mN/25mm。 In the protective film forming composite sheet 1C, the adhesive force between the cured protective film forming film 13 (that is, the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the base material 11 is 100mN/25mm To 2000mN/25mm.

圖3所示之保護膜形成用複合片1C係以下述方式使用，亦即，與圖1所示之保護膜形成用複合片1A同樣地，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，進而，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 1C for forming a protective film shown in FIG. 3 is used in the following manner, that is, in the same manner as the composite sheet 1A for forming a protective film shown in FIG. The surface 13a of the forming film 13 is attached to the back surface of a semiconductor wafer (not shown), and the upper surface of the surface 16a of the adhesive layer 16 for jig is attached to a jig such as a ring frame.

圖4係以示意方式表示本發明之保護膜形成用複合片的又一實施形態之剖面圖。 Fig. 4 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention.

關於此處所示之保護膜形成用複合片1D，除不具備治具用接著劑層16之方面以外，與圖3所示之保護膜形成用複合片1C相同。亦即，保護膜形成用複合片1D中，於基材11的一表面11a積層有保護膜形成用膜13，於保護膜形成用膜13的表面13a的整個面積層有剝離膜15。 The composite sheet 1D for forming a protective film shown here is the same as the composite sheet 1C for forming a protective film shown in FIG. 3 except that it does not include the adhesive layer 16 for jigs. That is, in the composite sheet 1D for forming a protective film, the film 13 for forming a protective film is laminated on one surface 11a of the base material 11, and a release film 15 is layered on the entire surface 13a of the film 13 for forming a protective film.

圖4所示之保護膜形成用複合片1D係以下述方式使用，亦即，與圖2所示之保護膜形成用複合片1B同樣地，在移除剝離膜15之狀態下，於保護膜形成用膜13的表面13a中的中央側的一部分區域貼附半導體晶圓(省略圖示)的背面，進而，將保護膜形成用膜13的周緣部附近的區域貼附於環狀框等治具。 The composite sheet 1D for forming a protective film shown in FIG. 4 is used in the following manner, that is, in the same manner as the composite sheet 1B for forming a protective film shown in FIG. A part of the area on the central side of the surface 13a of the forming film 13 is attached to the back surface of the semiconductor wafer (not shown), and the area near the peripheral edge of the protective film forming film 13 is attached to a ring frame or the like. With.

圖5係以示意方式表示本發明之保護膜形成用複合片的又一實施形態之剖面圖。 Fig. 5 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention.

關於此處所示之保護膜形成用複合片1E，除保護膜形成用膜之形狀不同之方面以外，與圖2所示之保護膜形成用複合片1B相同。亦即，保護膜形成用複合片1E於基材11上具備黏著劑層12，於黏著劑層12上具備保護膜形成用膜23。支持片10為基材11及黏著劑層12之積層體，換言之，保護膜形成用複合片1E具有於支持片10 的一表面10a上積層有保護膜形成用膜23之構成。另外，保護膜形成用複合片1E進而於保護膜形成用膜23上具備剝離膜15。 The composite sheet 1E for forming a protective film shown here is the same as the composite sheet 1B for forming a protective film shown in FIG. 2 except that the shape of the film for forming a protective film is different. That is, the composite sheet 1E for forming a protective film is provided with the adhesive layer 12 on the base material 11, and the film 23 for protective film formation is provided on the adhesive layer 12. The support sheet 10 is a laminate of the base material 11 and the adhesive layer 12. In other words, the composite sheet 1E for forming a protective film is provided in the support sheet 10 A structure in which a protective film forming film 23 is laminated on one surface 10a. In addition, the composite sheet 1E for forming a protective film further includes a release film 15 on the film 23 for forming a protective film.

保護膜形成用複合片1E中，於基材11的一表面11a積層有黏著劑層12，於黏著劑層12的表面12a的一部分，亦即中央側的區域積層有保護膜形成用膜23。並且，於黏著劑層12的表面12a中未積層保護膜形成用膜23之面及保護膜形成用膜23的表面23a(上表面及側面)上積層有剝離膜15。 In the composite sheet 1E for forming a protective film, an adhesive layer 12 is laminated on one surface 11a of the base material 11, and a protective film forming film 23 is laminated on a part of the surface 12a of the adhesive layer 12, that is, on the central area. In addition, a release film 15 is laminated on the surface 12a of the adhesive layer 12 on which the protective film forming film 23 is not laminated and the surface 23a (upper surface and side surface) of the protective film forming film 23.

自上方往下俯視保護膜形成用複合片1E時，保護膜形成用膜23的表面積小於黏著劑層12，例如具有圓形狀等形狀。 When the composite sheet 1E for forming a protective film is viewed from above, the surface area of the film 23 for forming a protective film is smaller than that of the adhesive layer 12, for example, it has a circular shape or the like.

保護膜形成用複合片1E中，硬化後之保護膜形成用膜23(亦即保護膜)與支持片10之間的黏著力，換言之保護膜與黏著劑層12之間的黏著力為100mN/25mm至2000mN/25mm。 In the protective film forming composite sheet 1E, the adhesive force between the cured protective film forming film 23 (that is, the protective film) and the support sheet 10, in other words, the adhesive force between the protective film and the adhesive layer 12 is 100 mN/ 25mm to 2000mN/25mm.

圖5所示之保護膜形成用複合片1E係以下述方式使用，亦即，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，進而，將黏著劑層12的表面12a中未積層保護膜形成用膜 23之面貼附於環狀框等治具。 The composite sheet 1E for forming a protective film shown in FIG. 5 is used in the following manner, that is, with the release film 15 removed, a semiconductor wafer (not shown in the figure) is attached to the surface 23a of the protective film forming film 23 ), and further, the protective film forming film is not laminated on the surface 12a of the adhesive layer 12 The surface of 23 is attached to the ring frame and other fixtures.

再者，圖5所示之保護膜形成用複合片1E中，於黏著劑層12的表面12a中未積層保護膜形成用膜23之面，亦可與圖1及圖3所示同樣地，積層治具用接著劑層(省略圖示)。具備此種治具用接著劑層之保護膜形成用複合片1E係以下述方式使用，亦即，與圖1及圖3所示之保護膜形成用複合片同樣地，將治具用接著劑層的表面貼附於環狀框等治具。 Furthermore, in the composite sheet 1E for forming a protective film shown in FIG. 5, the surface 12a of the adhesive layer 12 on which the film 23 for forming a protective film is not laminated may be the same as that shown in FIGS. 1 and 3. Adhesive layer for laminated jigs (not shown). The composite sheet 1E for forming a protective film provided with such an adhesive layer for jigs is used in the following manner, that is, the same as the composite sheet for forming a protective film shown in FIGS. 1 and 3, the adhesive for jigs The surface of the layer is attached to a jig such as a ring frame.

如此，本發明之保護膜形成用複合片中，無論支持片及保護膜形成用膜為何種形態，均可具備治具用接著劑層。但是，通常，如圖1及圖3所示，作為具備治具用接著劑層之本發明之保護膜形成用複合片，較佳為於保護膜形成用膜上具備治具用接著劑層。 In this way, the composite sheet for forming a protective film of the present invention can be provided with an adhesive layer for jigs regardless of the form of the support sheet and the film for forming a protective film. However, generally, as shown in FIG. 1 and FIG. 3, as the composite sheet for protective film formation of this invention provided with the adhesive layer for jigs, it is preferable to provide the adhesive layer for jigs on the film for protective film formation.

本發明之保護膜形成用複合片並不限定於圖1至圖5所示之保護膜形成用複合片，在無損本發明之效果之範圍內，亦可變更或刪除圖1至圖5所示之保護膜形成用複合片的一部分構成，或者對前文所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 as shown in FIGS. 1 to 5, and the ones shown in FIGS. 1 to 5 may be changed or deleted within the range that does not impair the effects of the present invention. A part of the composite sheet for forming a protective film, or another structure is added to the composite sheet for forming a protective film described above.

例如，圖3及圖4所示之保護膜形成用複合片中，亦可於基材11與保護膜形成用膜13之間設置中間層。可根 據目的選擇任意中間層作為中間層。 For example, in the composite sheet for forming a protective film shown in FIGS. 3 and 4, an intermediate layer may be provided between the base material 11 and the film 13 for forming a protective film. Can root Choose any intermediate layer as the intermediate layer according to the purpose.

另外，圖1、圖2、及圖5所示之保護膜形成用複合片中，亦可於基材11與黏著劑層12之間設置中間層。亦即，本發明之保護膜形成用複合片中，支持片亦可由基材、中間層、及黏著劑層依序積層而成。此處所稱的中間層與圖3及圖4所示之保護膜形成用複合片中可設置之中間層相同。 In addition, in the composite sheet for forming a protective film shown in FIGS. 1, 2, and 5, an intermediate layer may be provided between the base material 11 and the adhesive layer 12. That is, in the composite sheet for forming a protective film of the present invention, the support sheet may be formed by sequentially layering a base material, an intermediate layer, and an adhesive layer. The intermediate layer referred to here is the same as the intermediate layer that can be provided in the composite sheet for forming a protective film shown in FIGS. 3 and 4.

另外，圖1至圖5所示之保護膜形成用複合片中，可將前述中間層以外之層設置於任意部位。 In addition, in the composite sheet for forming a protective film shown in FIGS. 1 to 5, a layer other than the aforementioned intermediate layer may be provided at any position.

另外，本發明之保護膜形成用複合片中，亦可於剝離膜和與該剝離膜直接接觸之層之間產生一部分間隙。 In addition, in the composite sheet for forming a protective film of the present invention, a part of a gap may be formed between the release film and the layer directly in contact with the release film.

另外，本發明之保護膜形成用複合片中，各層之大小或形狀可根據目的任意調節。 In addition, in the composite sheet for forming a protective film of the present invention, the size or shape of each layer can be arbitrarily adjusted according to the purpose.

本發明之保護膜形成用複合片中，如後述般，較佳為黏著劑層等支持片中的與保護膜形成用膜直接接觸之層為非能量線硬化性。此種保護膜形成用複合片可使背面具備保護膜之半導體晶片更容易地切割。 In the composite sheet for forming a protective film of the present invention, as described later, it is preferable that the layer directly in contact with the film for forming a protective film in a support sheet such as an adhesive layer is non-energy ray curable. Such a composite sheet for forming a protective film can make it easier to cut a semiconductor wafer with a protective film on the back surface.

支持片可為透明，亦可為不透明，還可根據目的而著色。 The support sheet can be transparent or opaque, and can be colored according to the purpose.

其中，保護膜形成用膜具有能量線硬化性之本發明中，支持片較佳為使能量線透過。 Among them, in the present invention in which the film for forming a protective film has energy ray curability, the support sheet preferably allows energy ray to pass through.

例如，支持片中，波長375nm之光之透過率較佳為30%以上，更佳為50%以上，尤佳為70%以上。藉由前述光之透過率為此種範圍，經由支持片對保護膜形成用膜照射能量線(紫外線)時，保護膜形成用膜之硬化度進一步提高。 For example, in the support sheet, the transmittance of light with a wavelength of 375 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. With the aforementioned light transmittance in this range, when energy rays (ultraviolet rays) are irradiated to the protective film forming film through the support sheet, the degree of curing of the protective film forming film is further improved.

另一方面，支持片中，波長375nm之光之透過率的上限值並無特別限定，例如可設為95%。 On the other hand, in the support sheet, the upper limit of the transmittance of light with a wavelength of 375 nm is not particularly limited, and it can be set to 95%, for example.

另外，支持片中，波長532nm之光之透過率較佳為30%以上，更佳為50%以上，尤佳為70%以上。藉由前述光之透過率為此種範圍，經由支持片對保護膜形成用膜或保護膜照射雷射光而於該等進行印字時，可更清晰地進行印字。 In addition, in the support sheet, the transmittance of light with a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. With the aforementioned light transmittance in this range, the protective film forming film or the protective film is irradiated with laser light through the support sheet, and when printing is performed thereon, printing can be performed more clearly.

另一方面，支持片中，波長532nm之光之透過率的上限值並無特別限定，例如可設為95%。 On the other hand, in the support sheet, the upper limit of the transmittance of light with a wavelength of 532 nm is not particularly limited, and it can be set to 95%, for example.

另外，支持片中，波長1064nm之光之透過率較佳為30%以上，更佳為50%以上，尤佳為70%以上。藉由前述光之透過率為此種範圍，經由支持片對保護膜形成用膜或保護膜照射雷射光而於該等進行印字時，可更清晰地進行印字。 In addition, in the support sheet, the transmittance of light with a wavelength of 1064 nm is preferably 30% or more, more preferably 50% or more, and particularly preferably 70% or more. With the aforementioned light transmittance in this range, the protective film forming film or the protective film is irradiated with laser light through the support sheet, and when printing is performed thereon, printing can be performed more clearly.

另一方面，支持片中，波長1064nm之光之透過率的上限值並無特別限定，例如可設為95%。 On the other hand, in the support sheet, the upper limit of the transmittance of light with a wavelength of 1064 nm is not particularly limited, and may be set to 95%, for example.

其次，對構成支持片之各層，進行更詳細的說明。 Next, the layers constituting the support sheet will be described in more detail.

○基材 ○Substrate

前述基材為片狀或膜狀，作為前述基材的構成材料，例如可列舉各種樹脂。 The substrate is in a sheet shape or a film shape, and as a constituent material of the substrate, various resins can be cited, for example.

作為前述樹脂，例如可列舉：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)等聚乙烯；聚丙烯、聚丁烯、聚丁二烯、聚甲基戊烯、冰片烯樹脂等聚乙烯以外的聚烯烴；乙烯-乙酸乙烯酯共聚物、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物、乙烯-冰片烯共聚物等乙烯系共聚物(使用乙烯作為單體而獲得之共聚物)；聚氯乙烯、氯乙烯共聚物等氯乙烯系樹脂(使用氯乙烯作為單體而獲得之樹脂)；聚苯乙烯；聚環烯烴；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、聚間苯二甲酸乙二酯、聚2,6-萘二羧酸乙二酯、全部結構單元具有芳香族環式基之全芳香族聚酯等聚酯；2種以上之前述聚酯之共聚物；聚(甲基)丙烯酸酯；聚胺基甲酸酯；聚丙烯酸胺基甲酸酯；聚醯亞胺；聚醯胺；聚碳酸酯；氟樹脂；聚縮醛；改質聚苯醚；聚苯硫醚；聚碸；聚醚酮等。 Examples of the aforementioned resin include polyethylenes such as low density polyethylene (LDPE; low density polyethylene), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE; high density polyethylene); Polyolefins other than polyethylene such as polypropylene, polybutene, polybutadiene, polymethylpentene, and bornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-( Vinyl copolymers such as meth)acrylate copolymers and ethylene-bornene copolymers (copolymers obtained by using ethylene as a monomer); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (using vinyl chloride as a monomer) Resin obtained from monomer); polystyrene; polycyclic olefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate , Polyethylene 2,6-naphthalene dicarboxylate, fully aromatic polyester with all structural units having aromatic cyclic groups and other polyesters; copolymers of two or more of the aforementioned polyesters; poly(meth)acrylic acid Ester; Polyurethane; Polyacrylic urethane; Polyimide; Polyamide; Polycarbonate; Fluorine resin; Polyacetal; Modified polyphenylene ether; Polyphenylene sulfide; Polyurethane ; Polyether ketone and so on.

另外，作為前述樹脂，例如亦可列舉前述聚酯與前述聚酯以外的樹脂之混合物等聚合物合金。前述聚酯與前述聚酯以外的樹脂之聚合物合金較佳為聚酯以外的樹脂之量為相對較少量。 Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and resin other than the said polyester, can also be mentioned, for example. The polymer alloy of the aforementioned polyester and the aforementioned resin other than the polyester preferably has a relatively small amount of the resin other than the polyester.

另外，作為前述樹脂，例如亦可列舉：前文所例示之前述樹脂之1種或2種以上交聯而成之交聯樹脂；使用前文所例示之前述樹脂之1種或2種以上之離子聚合物等改質樹脂。 In addition, as the aforementioned resin, for example, a cross-linked resin obtained by cross-linking one or more of the aforementioned resins as exemplified above; and ionic polymerization using one or more of the aforementioned resins exemplified in the foregoing Modified resin such as materials.

再者，本說明書中，「(甲基)丙烯酸」的概念係包括「丙烯酸」及「甲基丙烯酸」兩者。關於與(甲基)丙烯酸類似之用語亦相同。 Furthermore, in this specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid.

構成基材之樹脂可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 The resin constituting the base material may be only one type, or two or more types. In the case of two or more types, the combination and ratio can be arbitrarily selected.

基材可由1層(單層)構成，亦可由2層以上之多層構成，於由多層構成之情形時，該等多層可相互相同亦可不同，該等多層之組合並無特別限定。 The substrate may be composed of one layer (single layer), or two or more layers. When it is composed of multiple layers, the multiple layers may be the same or different from each other, and the combination of the multiple layers is not particularly limited.

基材的厚度較佳為50μm至300μm，更佳為60μm至100μm。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。 The thickness of the substrate is preferably 50 μm to 300 μm, more preferably 60 μm to 100 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 the semiconductor wafer or the semiconductor wafer are further improved.

此處，所謂「基材的厚度」，意指基材整體的厚度，例如，所謂由多層構成之基材的厚度，意指構成基材之全部層的合計厚度。再者，作為基材的厚度的測定方法，例如可列舉以下方法等：於任意的5個部位，使用接觸式厚 度計，測定厚度，算出測定值之平均。 Here, the "thickness of the base material" means the thickness of the entire base material. For example, the thickness of the base material composed of multiple layers means the total thickness of all the layers constituting the base material. In addition, as a method of measuring the thickness of the substrate, for example, the following method can be cited: a contact type thickness is used at any 5 locations Measure the thickness with a degree meter, and calculate the average of the measured values.

基材較佳為厚度精度高，亦即，較佳為厚度不均與部位無關地皆被抑制。上述之構成材料中，作為可用於構成此種厚度精度高的基材之材料，例如可列舉：聚乙烯、聚乙烯以外的聚烯烴、聚對苯二甲酸乙二酯、乙烯-乙酸乙烯酯共聚物等。 The base material preferably has a high thickness accuracy, that is, it is preferable that the thickness unevenness is suppressed regardless of the location. Among the above-mentioned constituent materials, examples of materials that can be used to construct such a substrate with high thickness precision include polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymers. Things and so on.

基材中，除前述樹脂等主要構成材料以外，亦可含有填充材料、著色劑、抗靜電劑、抗氧化劑、有機潤滑劑、觸媒、軟化劑(塑化劑)等公知的各種添加劑。 The base material may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers) in addition to the aforementioned main constituent materials such as resins.

基材的光學特性滿足前文所說明之支持片的光學特性即可。亦即，基材可為透明，亦可為不透明，還可根據目的而著色，也可蒸鍍其他層。 The optical properties of the substrate may satisfy the optical properties of the support sheet described above. That is, the substrate may be transparent or opaque, and may be colored according to the purpose, and other layers may be vapor-deposited.

並且，保護膜形成用膜具有能量線硬化性之本發明中，基材較佳為使能量線透過。 Furthermore, in the present invention in which the film for forming a protective film has energy ray curability, it is preferable that the base material transmits energy rays.

基材的表面亦可經實施以下處理以提高與設置於該基材上之黏著劑層等其他層之密接性：利用噴砂處理、溶劑處理等之凹凸化處理；或者電暈放電處理、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。 The surface of the substrate can also be subjected to the following treatments to improve the adhesion with other layers such as the adhesive layer provided on the substrate: using sandblasting treatment, solvent treatment, etc. concave-convex treatment; or corona discharge treatment, electron beam Irradiation treatment, plasma treatment, ozone/ultraviolet radiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments.

另外，基材的表面亦可經實施底塗處理。 In addition, the surface of the substrate may also be subjected to primer treatment.

另外，基材亦可具有抗靜電塗層或以下用途之層等：將保護膜形成用複合片重疊保存時，防止基材接著於其他片或基材接著於吸附台。 In addition, the substrate may also have an antistatic coating or a layer for the following purposes: when the composite sheet for forming a protective film is stacked and stored, the substrate is prevented from being attached to other sheets or the substrate is attached to the suction table.

該等之中，就抑制因切割時刀片摩擦而導致基材產生斷片之方面而言，基材尤佳為表面經實施電子束照射處理。 Among them, in terms of preventing fragmentation of the substrate due to the friction of the blade during cutting, it is particularly preferable that the surface of the substrate is subjected to electron beam irradiation treatment.

基材可利用公知的方法進行製造。例如，含有樹脂之基材可藉由使含有前述樹脂之樹脂組成物成形而進行製造。 The base material can be manufactured by a well-known method. For example, a resin-containing substrate can be manufactured by molding a resin composition containing the aforementioned resin.

○黏著劑層 ○Adhesive layer

前述黏著劑層為片狀或膜狀，含有黏著劑。 The aforementioned adhesive layer is in the form of a sheet or film and contains an adhesive.

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、環氧系樹脂、聚乙烯醚、聚碳酸酯、酯系樹脂等黏著性樹脂，較佳為丙烯酸系樹脂。 Examples of the aforementioned adhesive include: acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin, etc. The resin is preferably an acrylic resin.

再者，本發明中，「黏著性樹脂」的概念係包括具有黏著性之樹脂及具有接著性之樹脂兩者，例如不僅包含本身具有黏著性之樹脂，亦包含藉由與添加劑等其他成分併用而顯示黏著性之樹脂、或者藉由存在熱或水等觸發劑而顯示接著性之樹脂等。 Furthermore, in the present invention, the concept of "adhesive resin" includes both adhesive resins and adhesive resins. For example, it includes not only resins with adhesive properties, but also the use of other ingredients such as additives. And resins that exhibit adhesiveness, or resins that exhibit adhesiveness by the presence of a trigger such as heat or water.

黏著劑層可由1層(單層)構成，亦可由2層以上之多層構成，於由多層構成之情形時，該等多層可相互相同亦可不同，該等多層之組合並無特別限定。 The adhesive layer may be composed of one layer (single layer) or two or more layers. In the case of being composed of multiple layers, the layers may be the same or different from each other, and the combination of the layers is not particularly limited.

黏著劑層的厚度較佳為1μm至100μm，更佳為1μm至60μm，尤佳為1μm至30μm。 The thickness of the adhesive layer is preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, and particularly preferably 1 μm to 30 μm.

此處，所謂「黏著劑層的厚度」，意指黏著劑層整體的厚度，例如，所謂由多層構成之黏著劑層的厚度，意指構成黏著劑層之全部層的合計厚度。再者，作為黏著劑層的厚度的測定方法，例如可列舉以下方法等：於任意的5個部位，使用接觸式厚度計，測定厚度，算出測定值之平均。 Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer. For example, the thickness of the adhesive layer composed of multiple layers means the total thickness of all layers constituting the adhesive layer. In addition, as a measuring method of the thickness of an adhesive layer, the following method etc. are mentioned, for example: The thickness is measured using a contact thickness meter at arbitrary 5 places, and the average of measured values is calculated.

黏著劑層的光學特性滿足前文所說明之支持片的光學特性即可。亦即，黏著劑層可為透明，亦可為不透明，還可根據目的而著色。 The optical properties of the adhesive layer may satisfy the optical properties of the support sheet described above. That is, the adhesive layer may be transparent or opaque, and may be colored according to the purpose.

並且，保護膜形成用膜具有能量線硬化性之本發明中，黏著劑層較佳為使能量線透過。 Furthermore, in the present invention in which the film for forming a protective film has energy ray curability, the adhesive layer preferably allows energy ray to pass through.

黏著劑層可使用能量線硬化性黏著劑而形成，亦可使用非能量線硬化性黏著劑而形成。使用能量線硬化性之黏著劑所形成之黏著劑層可容易地調節硬化前及硬化後的物性。 The adhesive layer can be formed using an energy ray-curable adhesive or may be formed using a non-energy ray-curable adhesive. The adhesive layer formed by the energy-ray curable adhesive can easily adjust the physical properties before and after curing.

<<黏著劑組成物>> <<Adhesive composition>>

黏著劑層可使用含有黏著劑之黏著劑組成物而形成。例如，於黏著劑層之形成對象面塗敷黏著劑組成物，視需要使之乾燥，藉此可於目標部位形成黏著劑層。關於黏著劑層的更具體的形成方法，與其他層的形成方法一起，隨後詳細地進行說明。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 containing an adhesive. For example, the adhesive composition is coated on the surface to be formed of the adhesive layer, and dried if necessary, thereby forming the adhesive layer on the target site. A more specific method of forming the adhesive layer will be described in detail later together with the method of forming other layers. The content ratio of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the content ratio of the aforementioned components in the adhesive layer. Furthermore, in this specification, the term "normal temperature" means a temperature that is not particularly cold or particularly hot, that is, a normal temperature, for example, a temperature of 15°C to 25°C.

利用公知的方法塗敷黏著劑組成物即可，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 adhesive composition can be applied by a known method. For example, methods using the following various coaters can be cited: air knife coater, knife coater, bar coater, gravure coater, roll coater Cloth machine, roll knife coater, curtain coater, die coater, knife coater, screen coater, wire rod coater, contact coater, etc.

黏著劑組成物的乾燥條件並無特別限定，於黏著劑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 adhesive composition are not particularly limited. In the case where the adhesive composition contains the solvent described later, it is preferable to heat and dry. In this case, it is preferably at 70°C to 130°C for 10 seconds to 5 seconds. Dry in minutes.

於黏著劑層為能量線硬化性之情形時，作為含有能量線硬化性黏著劑之黏著劑組成物，亦即能量線硬化性之黏 著劑組成物，例如可列舉以下黏著劑組成物等：黏著劑組成物(I-1)，含有非能量線硬化性之黏著性樹脂(I-1a)(以下，有時簡稱為「黏著性樹脂(I-1a)」)、及能量線硬化性化合物；黏著劑組成物(I-2)，含有能量線硬化性之黏著性樹脂(I-2a)(以下，有時簡稱為「黏著性樹脂(I-2a)」)，該黏著性樹脂(I-2a)於非能量線硬化性之黏著性樹脂(I-1a)的側鏈導入有不飽和基；黏著劑組成物(I-3)，含有前述黏著性樹脂(I-2a)、及能量線硬化性化合物。 When the adhesive layer is energy ray curable, it is used as an adhesive composition containing energy ray curable adhesive, that is, energy ray curable adhesive The adhesive composition includes, for example, the following adhesive composition: adhesive composition (I-1) containing non-energy-ray curable adhesive resin (I-1a) (hereinafter, sometimes referred to as "adhesive Resin (I-1a)"), and energy-ray curable compound; Adhesive composition (I-2), containing energy-ray-curable adhesive resin (I-2a) (hereinafter, sometimes referred to as "adhesive Resin (I-2a)”), the adhesive resin (I-2a) has an unsaturated group introduced into the side chain of the non-energy-ray curable adhesive resin (I-1a); adhesive composition (I-3 ), containing the aforementioned adhesive resin (I-2a) and an energy ray curable compound.

<黏著劑組成物(I-1)> <Adhesive composition (I-1)>

如上所述，前述黏著劑組成物(I-1)含有非能量線硬化性之黏著性樹脂(I-1a)、及能量線硬化性化合物。 As described above, the aforementioned adhesive composition (I-1) contains a non-energy-ray-curable adhesive resin (I-1a) and an energy-ray-curable compound.

[黏著性樹脂(I-1a)] [Adhesive resin (I-1a)]

前述黏著性樹脂(I-1a)較佳為丙烯酸系樹脂。 The aforementioned adhesive resin (I-1a) is preferably an acrylic resin.

作為前述丙烯酸系樹脂，例如可列舉：至少具有源自(甲基)丙烯酸烷基酯之結構單元之丙烯酸系聚合物。 As said acrylic resin, the acrylic polymer which has at least the structural unit derived from alkyl (meth)acrylate is mentioned, for example.

前述丙烯酸系樹脂所具有之結構單元可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 The structural unit possessed by the aforementioned acrylic resin may be only one type or two or more types, and when there are two or more types, the combinations and ratios can be arbitrarily selected.

作為前述(甲基)丙烯酸烷基酯，例如可列舉：構成烷基酯之烷基的碳數為1至20之(甲基)丙烯酸烷基酯，前述烷基較佳為直鏈狀或支鏈狀。 Examples of the aforementioned (meth)acrylic acid alkyl esters include: (meth)acrylic acid alkyl esters having 1 to 20 carbon atoms in the alkyl group constituting the alkyl ester, and the aforementioned alkyl group is preferably linear or branched. Chain-like.

作為(甲基)丙烯酸烷基酯，更具體而言，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)、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯等。 As the alkyl (meth)acrylate, more specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate Ester, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate Base) 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 ester (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), (meth) Nonadecyl acrylate, eicosyl (meth)acrylate, etc.

就黏著劑層的黏著力提高之方面而言，前述丙烯酸系聚合物較佳為具有源自前述烷基的碳數為2以上之(甲基)丙烯酸烷基酯之結構單元。並且，就黏著劑層的黏著力進一步提高之方面而言，前述烷基的碳數較佳為2至12，更佳為4至8。另外，前述烷基的碳數為4以上之(甲基)丙烯酸烷基酯較佳為丙烯酸烷基酯。 In terms of improving the adhesive force of the adhesive layer, the acrylic polymer preferably has a structural unit derived from an alkyl (meth)acrylate having a carbon number of 2 or more derived from the alkyl group. In addition, in terms of further improving the adhesive force of the adhesive layer, the carbon number of the aforementioned alkyl group is preferably 2-12, more preferably 4-8. In addition, the alkyl (meth)acrylate whose alkyl group has 4 or more carbon atoms is preferably an alkyl acrylate.

前述丙烯酸系聚合物中，較佳為除源自(甲基)丙烯酸 烷基酯之結構單元以外，進而具有源自含官能基之單體之結構單元。 Among the aforementioned acrylic polymers, those derived from (meth)acrylic acid are preferably In addition to the structural unit of the alkyl ester, it further has a structural unit derived from a monomer containing a functional group.

作為前述含官能基之單體，例如可列舉以下單體，該單體可藉由前述官能基與後述之交聯劑反應而成為交聯的起點，或者可藉由前述官能基與後述之含不飽和基之化合物中的不飽和基反應，而於丙烯酸系聚合物的側鏈導入不飽和基。 As the aforementioned functional group-containing monomers, for example, the following monomers can be exemplified, which can be the starting point of crosslinking by reacting the aforementioned functional group with the crosslinking agent described later, or can be formed by the aforementioned functional group and the aforementioned The unsaturated group in the unsaturated group reacts, and the unsaturated group is introduced into the side chain of the acrylic polymer.

作為含官能基之單體中的前述官能基，例如可列舉：羥基、羧基、胺基、環氧基等。 Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxyl group, an amino group, and an epoxy group.

亦即，作為含官能基之單體，例如可列舉：含羥基之單體、含羧基之單體、含胺基之單體、含環氧基之單體等。 That is, as a monomer containing a functional group, for example, a monomer containing a hydroxyl group, a monomer containing a carboxyl group, a monomer containing an amine group, a monomer containing an epoxy group, and the like are listed.

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-containing monomer include: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxymethyl (meth)acrylate Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; vinyl alcohol, Non-(meth)acrylic unsaturated alcohols such as allyl alcohol (unsaturated alcohols that do not have a (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)；反丁烯二酸、衣康酸、順丁烯二酸、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之酐；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 aforementioned carboxyl group-containing monomer include: ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, etc. Acid, maleic acid, citraconic acid Ethylene unsaturated dicarboxylic acids (dicarboxylic acids with ethylenic unsaturated bonds); anhydrides of the aforementioned ethylenic unsaturated dicarboxylic acids; carboxyalkyl (meth)acrylates such as 2-carboxyethyl methacrylate Wait.

含官能基之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 functional group-containing monomer is preferably a hydroxyl group-containing monomer or a carboxyl group-containing monomer, and more preferably a hydroxyl group-containing monomer.

構成前述丙烯酸系聚合物之含官能基之單體可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 The functional group-containing monomer constituting the aforementioned acrylic polymer may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

前述丙烯酸系聚合物中，源自含官能基之單體之結構單元的含量相對於結構單元的總量，較佳為1質量%至29質量%，更佳為2質量%至25質量%，尤佳為3質量%至20質量%。 In the aforementioned acrylic polymer, the content of the structural unit derived from the functional group-containing monomer relative to the total amount of the structural unit is preferably 1% to 29% by mass, more preferably 2% to 25% by mass, Particularly preferably, it is 3% by mass to 20% by mass.

前述丙烯酸系聚合物中，亦可除源自(甲基)丙烯酸烷基酯之結構單元、及源自含官能基之單體之結構單元以外，進而具有源自其他單體之結構單元。 The aforementioned acrylic polymer may have a structural unit derived from another monomer in addition to a structural unit derived from an alkyl (meth)acrylate and a structural unit derived from a functional group-containing monomer.

前述其他單體只要能夠與(甲基)丙烯酸烷基酯等共聚合，則並無特別限定。 The aforementioned other monomers are not particularly limited as long as they can be copolymerized with alkyl (meth)acrylate and the like.

作為前述其他單體，例如可列舉：苯乙烯、α-甲基苯乙烯、乙烯基甲苯、甲酸乙烯酯、乙酸乙烯酯、丙烯腈、丙烯醯胺等。 Examples of the aforementioned other monomers include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide, and the like.

構成前述丙烯酸系聚合物之前述其他單體可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 The aforementioned other monomers constituting the aforementioned acrylic polymer may be only one type or two or more types, and when there are two or more types, the combinations and ratios thereof can be arbitrarily selected.

前述丙烯酸系聚合物可用作上述之非能量線硬化性之黏著性樹脂(I-1a)。 The aforementioned acrylic polymer can be used as the aforementioned non-energy-ray-curable adhesive resin (I-1a).

另一方面，使前述丙烯酸系聚合物中的官能基與具有能量線聚合性不飽和基(能量線聚合性基)之含不飽和基之化合物反應而成之化合物可用作上述之能量線硬化性之黏著性樹脂(I-2a)。 On the other hand, a compound obtained by reacting a functional group in the aforementioned acrylic polymer with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group (energy ray polymerizable group) can be used as the aforementioned energy ray hardening Adhesive resin (I-2a).

黏著劑組成物(I-1)所含有之黏著性樹脂(I-1a)可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 Adhesive resin (I-1a) contained in the adhesive composition (I-1) may be only one type, or two or more types. In the case of two or more types, the combination and ratio can be arbitrary select.

黏著劑組成物(I-1)中，黏著性樹脂(I-1a)的含量相對於黏著劑組成物(I-1)的總質量，較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為15質量%至90質量%。 In the adhesive composition (I-1), the content of the adhesive resin (I-1a) relative to the total mass of the adhesive composition (I-1) is preferably 5% to 99% by mass, more preferably 10% by mass to 95% by mass, particularly preferably 15% by mass to 90% by mass.

[能量線硬化性化合物] [Energy ray hardening compound]

作為黏著劑組成物(I-1)所含有之前述能量線硬化性化合物，可列舉具有能量線聚合性不飽和基且可藉由照射 能量線而硬化之單體或低聚物。 Examples of the aforementioned energy-ray curable compound contained in the adhesive composition (I-1) include an energy-ray polymerizable unsaturated group and can be irradiated A monomer or oligomer hardened by energy rays.

能量線硬化性化合物中，作為單體，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇(甲基)丙烯酸酯、季戊四醇四(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(甲基)丙烯酸酯等多元(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲酸酯；聚酯(甲基)丙烯酸酯；聚醚(甲基)丙烯酸酯；環氧(甲基)丙烯酸酯等。 Among the energy ray curable compounds, examples of monomers include trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, (Meth)acrylates such as acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate, etc.; (meth)acrylic urethane Acid ester; polyester (meth)acrylate; polyether (meth)acrylate; epoxy (meth)acrylate, etc.

能量線硬化性化合物中，作為低聚物，例如可列舉：上述所例示之單體進行聚合而成之低聚物等。 Among the energy ray curable compounds, examples of the oligomer include oligomers obtained by polymerizing the monomers exemplified above.

就分子量相對較大，不易使黏著劑層的儲存彈性率降低之方面而言，能量線硬化性化合物較佳為(甲基)丙烯酸胺基甲酸酯、(甲基)丙烯酸胺基甲酸酯低聚物。 The energy ray curable compound is preferably (meth)acrylate urethane or (meth)acrylate urethane in terms of its relatively large molecular weight and it is difficult to reduce the storage elastic modulus of the adhesive layer. Oligomer.

黏著劑組成物(I-1)所含有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，該等之組合及比率可任意選擇。 The aforementioned energy ray curable compound contained in the adhesive composition (I-1) may be only one type or two or more types, and when there are two or more types, the combination and ratio can be arbitrarily selected.

前述黏著劑組成物(I-1)中，前述能量線硬化性化合物的含量相對於黏著劑組成物(I-1)的總質量，較佳為1質量%至95質量%，更佳為5質量%至90質量%，尤佳為10質量%至85質量%。 In the adhesive composition (I-1), the content of the energy ray curable compound relative to the total mass of the adhesive composition (I-1) is preferably 1% to 95% by mass, more preferably 5 Mass% to 90% by mass, particularly preferably 10% to 85% by mass.

[交聯劑] [Crosslinking agent]

於使用除源自(甲基)丙烯酸烷基酯之結構單元以外，進而具有源自含官能基之單體之結構單元之前述丙烯酸系聚合物作為黏著性樹脂(I-1a)之情形時，黏著劑組成物(I-1)較佳為進而含有交聯劑。 When using the aforementioned acrylic polymer having structural units derived from functional group-containing monomers in addition to the structural units derived from alkyl (meth)acrylates as the adhesive resin (I-1a), The adhesive composition (I-1) preferably further contains a crosslinking agent.

前述交聯劑例如與前述官能基反應而使黏著性樹脂(I-1a)彼此進行交聯。 The crosslinking agent reacts with the functional group, for example, to crosslink the adhesive resins (I-1a).

作為交聯劑，例如可列舉：甲苯二異氰酸酯、六亞甲基二異氰酸酯、苯二甲基二異氰酸酯、該等二異氰酸酯之加合物等異氰酸酯系交聯劑(具有異氰酸酯基之交聯劑)；乙二醇縮水甘油醚等環氧系交聯劑(具有縮水甘油基之交聯劑)；六[1-(2-甲基)-氮丙啶基]三膦三嗪等氮丙啶系交聯劑(具有氮丙啶基之交聯劑)；鋁螯合物等金屬螯合物系交聯劑(具有金屬螯合物結構之交聯劑)；異氰脲酸酯系交聯劑(具有異氰脲酸骨架之交聯劑)等。 Examples of the crosslinking agent include isocyanate-based crosslinking agents (crosslinking agents having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates. ; Epoxy crosslinking agents such as ethylene glycol glycidyl ether (crosslinking agents with glycidyl groups); aziridine series such as hexa[1-(2-methyl)-aziridinyl] triphosphine triazine Cross-linking agent (cross-linking agent with aziridin group); metal chelate-based cross-linking agent such as aluminum chelate (cross-linking agent with metal chelate structure); isocyanurate-based cross-linking agent (Crosslinking agent with isocyanuric acid skeleton) and so on.

就提高黏著劑的凝聚力而提高黏著劑層的黏著力之方面、及容易獲取等方面而言，交聯劑較佳為異氰酸酯系交聯劑。 The crosslinking agent is preferably an isocyanate-based crosslinking agent in terms of enhancing the cohesive force of the adhesive and enhancing the adhesive force of the adhesive layer, and easy availability.

黏著劑組成物(I-1)所含有之交聯劑可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 The crosslinking agent contained in the adhesive composition (I-1) may be only one type or two or more types. When there are two or more types, the combination and ratio can be arbitrarily selected.

前述黏著劑組成物(I-1)中，交聯劑的含量相對於黏著 性樹脂(I-1a)的含量100質量份，較佳為0.01質量份至50質量份，更佳為0.1質量份至20質量份，尤佳為0.3質量份至15質量份。 In the aforementioned adhesive composition (I-1), the content of the crosslinking agent is relative to the adhesive The content of the resin (I-1a) is 100 parts by mass, preferably 0.01 parts by mass to 50 parts by mass, more preferably 0.1 parts by mass to 20 parts by mass, and particularly preferably 0.3 parts by mass to 15 parts by mass.

[光聚合起始劑] [Photopolymerization initiator]

黏著劑組成物(I-1)亦可進而含有光聚合起始劑。對於含有光聚合起始劑之黏著劑組成物(I-1)，即便照射紫外線等相對較低能量之能量線，亦充分地進行硬化反應。 The adhesive composition (I-1) may further contain a photopolymerization initiator. For the adhesive composition (I-1) containing a photopolymerization initiator, even if it is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction proceeds sufficiently.

作為前述光聚合起始劑，例如可列舉：安息香、安息香甲醚、安息香***、安息香異丙醚、安息香異丁醚、安息香苯甲酸、安息香苯甲酸甲酯、安息香二甲基縮酮等安息香化合物；苯乙酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等苯乙酮化合物；雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦等醯基氧化膦化合物；苄基苯基硫化物、一硫化四甲基秋蘭姆等硫化物化合物；1-羥基環己基苯基酮等α-酮醇化合物；偶氮雙異丁腈等偶氮化合物；二茂鈦等二茂鈦化合物；噻噸酮等噻噸酮化合物；過氧化物化合物；二乙醯等二酮化合物；苯偶醯；二苯偶醯；二苯甲酮；2,4-二乙基噻噸酮；1,2-二苯基甲烷；2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮；2-氯蒽醌等。 Examples of the aforementioned photopolymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal. ; Acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc. Ketone compounds; bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl phosphine oxide and other phosphine oxide compounds; benzyl Sulfide compounds such as phenyl sulfide and tetramethylthiuram monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; Titanocene compounds; thioxanthone compounds such as thioxanthone; peroxide compounds; diacetone compounds such as diacetin; benzophenone; benzophenone; benzophenone; 2,4-diethylthioxanthone ; 1,2-Diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] acetone; 2-chloroanthraquinone and the like.

另外，作為前述光聚合起始劑，例如亦可使用1-氯蒽醌等醌化合物；胺等光增感劑等。 In addition, as the aforementioned photopolymerization initiator, for example, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines, and the like can also be used.

黏著劑組成物(I-1)所含有之光聚合起始劑可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 The photopolymerization initiator contained in the adhesive composition (I-1) may be only one type or two or more types. When there are two or more types, the combination and ratio can be arbitrarily selected.

黏著劑組成物(I-1)中，光聚合起始劑的含量相對於前述能量線硬化性化合物的含量100質量份，較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, and more preferably 0.03 to 20 parts by mass relative to the content of the aforementioned energy ray curable compound 100 parts by mass 10 parts by mass, particularly preferably 0.05 to 5 parts by mass.

[其他添加劑] [Other additives]

黏著劑組成物(I-1)中，在無損本發明之效果之範圍內，亦可含有不屬於上述之任一種成分之其他添加劑。 The adhesive composition (I-1) may contain other additives that do not belong to any of the above-mentioned components within a range that does not impair the effects of the present invention.

作為前述其他添加劑，例如可列舉：抗靜電劑、抗氧化劑、軟化劑(塑化劑)、填充材料(填料)、防鏽劑、著色劑(顏料、染料)、增感劑、黏著賦予劑、反應延遲劑、交聯促進劑(觸媒)等公知的添加劑。 Examples of the aforementioned other additives include: antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, adhesion-imparting agents, Known additives such as reaction delay agents and crosslinking accelerators (catalysts).

再者，所謂反應延遲劑，例如抑制因混入至黏著劑組成物(I-1)中之觸媒之作用而導致保存中之黏著劑組成物(I-1)中進行目的外的交聯反應。作為反應延遲劑，例如可列舉藉由針對觸媒之螯合物而形成螯合物錯合物之化合物，更具體而言，可列舉：於1分子中具有2個以上之羰基(-C(=O)-)之化合物。 Furthermore, the so-called reaction delay agent, for example, inhibits the non-target crosslinking reaction in the adhesive composition (I-1) during storage due to the action of the catalyst mixed in the adhesive composition (I-1) . As the reaction delay agent, for example, a compound that forms a chelate complex by a chelate against a catalyst can be cited. More specifically, it can include: having two or more carbonyl groups (-C( =O)-) Compounds.

黏著劑組成物(I-1)所含有之其他添加劑可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 The other additives contained in the adhesive composition (I-1) may be only one type or two or more types, and when there are two or more types, the combinations and ratios can be arbitrarily selected.

黏著劑組成物(I-1)中，其他添加劑的含量並無特別限定，根據該其他添加劑的種類適宜選擇即可。 The content of other additives in the adhesive composition (I-1) is not particularly limited, and may be appropriately selected according to the type of the other additives.

[溶劑] [Solvent]

黏著劑組成物(I-1)亦可含有溶劑。黏著劑組成物(I-1)藉由含有溶劑，對塗敷對象面之塗敷適性提高。 The adhesive composition (I-1) may also contain a solvent. The adhesive composition (I-1) contains a solvent to improve the coating suitability of the coating target surface.

前述溶劑較佳為有機溶劑，作為前述有機溶劑，例如可列舉：甲基乙基酮、丙酮等酮；乙酸乙酯等酯(羧酸酯)；四氫呋喃、二噁烷等醚；環己烷、正己烷等脂肪族烴；甲苯、二甲苯等芳香族烴；1-丙醇、2-丙醇等醇等。 The aforementioned solvent is preferably an organic solvent. Examples of the aforementioned organic solvent include: ketones such as methyl ethyl ketone and acetone; esters (carboxylic acid esters) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; cyclohexane, Aliphatic hydrocarbons such as n-hexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol.

作為前述溶劑，例如，可將製造黏著性樹脂(I-1a)時所使用之溶劑不自黏著性樹脂(I-1a)中去除而直接於黏著劑組成物(I-1)中使用，亦可於製造黏著劑組成物(I-1)時另行添加與製造黏著性樹脂(I-1a)時所使用之溶劑相同種類或不同種類之溶劑。 As the aforementioned solvent, for example, the solvent used in the production of the adhesive resin (I-1a) can be used directly in the adhesive composition (I-1) without being removed from the adhesive resin (I-1a). The same type of solvent or a different type of solvent can be added when manufacturing the adhesive composition (I-1) as the solvent used when manufacturing the adhesive resin (I-1a).

黏著劑組成物(I-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，該等之組合及比率可 任意選擇。 The solvent contained in the adhesive composition (I-1) may be only one type or two or more types. In the case of two or more types, the combination and ratio may be Arbitrary choice.

黏著劑組成物(I-1)中，溶劑的含量並無特別限定，適宜調節即可。 In the adhesive composition (I-1), the content of the solvent is not particularly limited, and may be adjusted appropriately.

<黏著劑組成物(I-2)> <Adhesive composition (I-2)>

如上所述，前述黏著劑組成物(I-2)含有能量線硬化性之黏著性樹脂(I-2a)，該黏著性樹脂(I-2a)於非能量線硬化性之黏著性樹脂(I-1a)的側鏈導入有不飽和基。 As mentioned above, the aforementioned adhesive composition (I-2) contains an energy-ray-curable adhesive resin (I-2a), and the adhesive resin (I-2a) is mixed with a non-energy-ray-curable adhesive resin (I-2a). An unsaturated group is introduced into the side chain of -1a).

[黏著性樹脂(I-2a)] [Adhesive resin (I-2a)]

前述黏著性樹脂(I-2a)例如藉由使黏著性樹脂(I-1a)中的官能基與具有能量線聚合性不飽和基之含不飽和基之化合物反應而獲得。 The aforementioned adhesive resin (I-2a) is obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy-ray polymerizable unsaturated group.

前述含不飽和基之化合物除具有前述能量線聚合性不飽和基以外，進而具有以下基，該基藉由與黏著性樹脂(I-1a)中的官能基反應，可與黏著性樹脂(I-1a)鍵結。 In addition to the aforementioned energy-ray polymerizable unsaturated group, the aforementioned unsaturated group-containing compound further has the following group, which reacts with the functional group in the adhesive resin (I-1a) to react with the adhesive resin (I-1a) -1a) Bonding.

作為前述能量線聚合性不飽和基，例如可列舉：(甲基)丙烯醯基、乙烯基(次乙基)、烯丙基(2-丙烯基)等，較佳為(甲基)丙烯醯基。 Examples of the energy ray polymerizable unsaturated group include (meth)acrylic acid group, vinyl (ethylene group), allyl group (2-propenyl group), etc., and (meth)acrylic acid group is preferred. base.

作為可與黏著性樹脂(I-1a)中的官能基鍵結之基，例如可列舉：可與羥基或胺基鍵結之異氰酸酯基及縮水甘油基、以及可與羧基或環氧基鍵結之羥基及胺基等。 Examples of groups that can be bonded to the functional groups in the adhesive resin (I-1a) include: isocyanate groups and glycidyl groups that can be bonded to hydroxyl groups or amino groups, and carboxyl groups or epoxy groups that can be bonded The hydroxyl and amino groups, etc.

作為前述含不飽和基之化合物，例如可列舉：異氰酸(甲基)丙烯醯氧基乙酯、(甲基)丙烯醯基異氰酸酯、(甲基)丙烯酸縮水甘油酯等。 Examples of the aforementioned unsaturated group-containing compound include (meth)acryloxyethyl isocyanate, (meth)acryloyl isocyanate, glycidyl (meth)acrylate, and the like.

黏著劑組成物(I-2)所含有之黏著性樹脂(I-2a)可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 Adhesive resin (I-2a) contained in the adhesive composition (I-2) may be only one type, or two or more types. In the case of two or more types, the combination and ratio can be arbitrary select.

黏著劑組成物(I-2)中，黏著性樹脂(I-2a)的含量相對於黏著劑組成物(I-2)的總質量，較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為10質量%至90質量%。 In the adhesive composition (I-2), the content of the adhesive resin (I-2a) relative to the total mass of the adhesive composition (I-2) is preferably 5% to 99% by mass, more preferably 10% by mass to 95% by mass, particularly preferably 10% by mass to 90% by mass.

[交聯劑] [Crosslinking agent]

於使用例如與黏著性樹脂(I-1a)中相同的具有源自含官能基之單體之結構單元之前述丙烯酸系聚合物作為黏著性樹脂(I-2a)之情形時，黏著劑組成物(I-2)亦可進而含有交聯劑。 When using, for example, the aforementioned acrylic polymer having the same structural unit derived from a functional group-containing monomer as the adhesive resin (I-1a) as the adhesive resin (I-2a), the adhesive composition (I-2) You may further contain a crosslinking agent.

作為黏著劑組成物(I-2)中的前述交聯劑，可列舉與黏著劑組成物(I-1)中的交聯劑相同的化合物。 Examples of the crosslinking agent in the adhesive composition (I-2) include the same compounds as the crosslinking agent in the adhesive composition (I-1).

黏著劑組成物(I-2)所含有之交聯劑可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率 可任意選擇。 The crosslinking agent contained in the adhesive composition (I-2) 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 chosen arbitrarily.

前述黏著劑組成物(I-2)中，交聯劑的含量相對於黏著性樹脂(I-2a)的含量100質量份，較佳為0.01質量份至25質量份，更佳為0.05質量份至20質量份，尤佳為0.1質量份至15質量份。 In the aforementioned adhesive composition (I-2), the content of the crosslinking agent relative to the content of the adhesive resin (I-2a) is 100 parts by mass, preferably 0.01 to 25 parts by mass, more preferably 0.05 parts by mass To 20 parts by mass, particularly preferably 0.1 to 15 parts by mass.

[光聚合起始劑] [Photopolymerization initiator]

黏著劑組成物(I-2)亦可進而含有光聚合起始劑。對於含有光聚合起始劑之黏著劑組成物(I-2)，即便照射紫外線等相對較低能量之能量線，亦充分地進行硬化反應。 The adhesive composition (I-2) may further contain a photopolymerization initiator. For the adhesive composition (I-2) containing a photopolymerization initiator, even if it is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction proceeds sufficiently.

作為黏著劑組成物(I-2)中的前述光聚合起始劑，可列舉與黏著劑組成物(I-1)中的光聚合起始劑相同的化合物。 Examples of the photopolymerization initiator in the adhesive composition (I-2) include the same compounds as the photopolymerization initiator in the adhesive composition (I-1).

黏著劑組成物(I-2)所含有之光聚合起始劑可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 The photopolymerization initiator contained in the adhesive composition (I-2) may be only one type, or two or more types. When there are two or more types, the combination and ratio can be arbitrarily selected.

黏著劑組成物(I-2)中，光聚合起始劑的含量相對於黏著性樹脂(I-2a)的含量100質量份，較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 In the adhesive composition (I-2), the content of the photopolymerization initiator relative to the content of the adhesive resin (I-2a) is 100 parts by mass, preferably 0.01 to 20 parts by mass, more preferably 0.03 parts by mass Parts to 10 parts by mass, more preferably 0.05 parts by mass to 5 parts by mass.

[其他添加劑] [Other additives]

黏著劑組成物(I-2)中，在無損本發明之效果之範圍內，亦可含有不屬於上述之任一種成分之其他添加劑。 The adhesive composition (I-2) may contain other additives that do not belong to any of the above-mentioned components within a range that does not impair the effects of the present invention.

作為黏著劑組成物(I-2)中的前述其他添加劑，可列舉與黏著劑組成物(I-1)中的其他添加劑相同的化合物。 Examples of the aforementioned other additives in the adhesive composition (I-2) include the same compounds as the other additives in the adhesive composition (I-1).

黏著劑組成物(I-2)所含有之其他添加劑可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 The other additives contained in the adhesive composition (I-2) may be only one type, or two or more types. In the case of two or more types, the combinations and ratios can be arbitrarily selected.

黏著劑組成物(I-2)中，其他添加劑的含量並無特別限定，根據該其他添加劑的種類適宜選擇即可。 The content of other additives in the adhesive composition (I-2) is not particularly limited, and may be appropriately selected according to the type of the other additives.

[溶劑] [Solvent]

以與黏著劑組成物(I-1)之情形相同之目的，黏著劑組成物(I-2)亦可含有溶劑。 For the same purpose as in the case of the adhesive composition (I-1), the adhesive composition (I-2) may also contain a solvent.

作為黏著劑組成物(I-2)中的前述溶劑，可列舉與黏著劑組成物(I-1)中的溶劑相同的溶劑。 Examples of the aforementioned solvent in the adhesive composition (I-2) include the same solvents as the solvent in the adhesive composition (I-1).

黏著劑組成物(I-2)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，該等之組合及比率可任意選擇。 The solvent contained in the adhesive composition (I-2) may be only one type, or two or more types. In the case of two or more types, the combination and ratio can be arbitrarily selected.

黏著劑組成物(I-2)中，溶劑的含量並無特別限定，適宜調節即可。 In the adhesive composition (I-2), the content of the solvent is not particularly limited, and may be adjusted appropriately.

<黏著劑組成物(I-3)> <Adhesive composition (I-3)>

如上所述，前述黏著劑組成物(I-3)含有前述黏著性樹 脂(I-2a)、及能量線硬化性化合物。 As described above, the adhesive composition (I-3) contains the adhesive tree Fat (I-2a), and energy ray hardening compound.

黏著劑組成物(I-3)中，黏著性樹脂(I-2a)的含量相對於黏著劑組成物(I-3)的總質量，較佳為5質量%至99質量%，更佳為10質量%至95質量%，尤佳為15質量%至90質量%。 In the adhesive composition (I-3), the content of the adhesive resin (I-2a) relative to the total mass of the adhesive composition (I-3) is preferably 5% to 99% by mass, more preferably 10% by mass to 95% by mass, particularly preferably 15% by mass to 90% by mass.

[能量線硬化性化合物] [Energy ray hardening compound]

作為黏著劑組成物(I-3)所含有之前述能量線硬化性化合物，可列舉具有能量線聚合性不飽和基且可藉由照射能量線而硬化之單體及低聚物，可列舉與黏著劑組成物(I-1)所含有之能量線硬化性化合物相同的化合物。 Examples of the aforementioned energy ray curable compound contained in the adhesive composition (I-3) include monomers and oligomers that have energy ray polymerizable unsaturated groups and can be cured by energy ray irradiation, including The same compound as the energy ray curable compound contained in the adhesive composition (I-1).

黏著劑組成物(I-3)所含有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，該等之組合及比率可任意選擇。 The aforementioned energy ray curable compound contained in the adhesive composition (I-3) may be only one type, or two or more types. When there are two or more types, the combination and ratio can be arbitrarily selected.

前述黏著劑組成物(I-3)中，前述能量線硬化性化合物的含量相對於黏著性樹脂(I-2a)的含量100質量份，較佳為0.01質量份至300質量份，更佳為0.03質量份至200質量份，尤佳為0.05質量份至100質量份。 In the aforementioned adhesive composition (I-3), the content of the aforementioned energy ray curable compound relative to the content of the adhesive resin (I-2a) is 100 parts by mass, preferably 0.01 to 300 parts by mass, more preferably 0.03 parts by mass to 200 parts by mass, particularly preferably 0.05 parts by mass to 100 parts by mass.

[光聚合起始劑] [Photopolymerization initiator]

黏著劑組成物(I-3)亦可進而含有光聚合起始劑。對於含有光聚合起始劑之黏著劑組成物(I-3)，即便照射紫外線 等相對較低能量之能量線，亦充分地進行硬化反應。 The adhesive composition (I-3) may further contain a photopolymerization initiator. For the adhesive composition (I-3) containing a photopolymerization initiator, even if it is irradiated with ultraviolet rays And other relatively low-energy energy lines, also fully carry out the hardening reaction.

作為黏著劑組成物(I-3)中的前述光聚合起始劑，可列舉與黏著劑組成物(I-1)中的光聚合起始劑相同的化合物。 Examples of the aforementioned photopolymerization initiator in the adhesive composition (I-3) include the same compounds as the photopolymerization initiator in the adhesive composition (I-1).

黏著劑組成物(I-3)所含有之光聚合起始劑可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 The photopolymerization initiator contained in the adhesive composition (I-3) may be only one type, or two or more types. When there are two or more types, the combination and ratio can be arbitrarily selected.

黏著劑組成物(I-3)中，光聚合起始劑的含量相對於黏著性樹脂(I-2a)及前述能量線硬化性化合物的總含量100質量份，較佳為0.01質量份至20質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 In the adhesive composition (I-3), the content of the photopolymerization initiator is 100 parts by mass relative to the total content of the adhesive resin (I-2a) and the aforementioned energy ray curable compound, preferably 0.01 to 20 parts by mass Parts by mass, more preferably 0.03 parts by mass to 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

[其他添加劑] [Other additives]

黏著劑組成物(I-3)中，在無損本發明之效果之範圍內，亦可含有不屬於上述之任一種成分之其他添加劑。 The adhesive composition (I-3) may contain other additives that do not belong to any of the above-mentioned components within a range that does not impair the effects of the present invention.

作為前述其他添加劑，可列舉與黏著劑組成物(I-1)中的其他添加劑相同的化合物。 Examples of the aforementioned other additives include the same compounds as the other additives in the adhesive composition (I-1).

黏著劑組成物(I-3)所含有之其他添加劑可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 The other additives contained in the adhesive composition (I-3) may be only one type, or two or more types. In the case of two or more types, the combinations and ratios can be arbitrarily selected.

黏著劑組成物(I-3)中，其他添加劑的含量並無特別限定，根據該其他添加劑的種類適宜選擇即可。 The content of other additives in the adhesive composition (I-3) is not particularly limited, and may be appropriately selected according to the type of the other additives.

[溶劑] [Solvent]

以與黏著劑組成物(I-1)之情形相同之目的，黏著劑組成物(I-3)亦可含有溶劑。 For the same purpose as in the case of the adhesive composition (I-1), the adhesive composition (I-3) may also contain a solvent.

作為黏著劑組成物(I-3)中的前述溶劑，可列舉與黏著劑組成物(I-1)中的溶劑相同的溶劑。 Examples of the aforementioned solvent in the adhesive composition (I-3) include the same solvents as the solvent in the adhesive composition (I-1).

黏著劑組成物(I-3)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，該等之組合及比率可任意選擇。 The solvent contained in the adhesive composition (I-3) may be only one type, or two or more types. In the case of two or more types, the combination and ratio can be arbitrarily selected.

黏著劑組成物(I-3)中，溶劑的含量並無特別限定，適宜調節即可。 In the adhesive composition (I-3), the content of the solvent is not particularly limited, and may be adjusted appropriately.

<黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物> <Adhesive composition (I-1) to adhesive composition other than adhesive composition (I-3)>

前文主要對黏著劑組成物(I-1)、黏著劑組成物(I-2)及黏著劑組成物(I-3)進行了說明，但對於該等3種黏著劑組成物以外之全部黏著劑組成物(本說明書中，稱為「黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物」)，亦可同樣地使用作為該等的含有成分所說明之成分。 The previous article mainly explained the adhesive composition (I-1), the adhesive composition (I-2), and the adhesive composition (I-3), but for all the adhesives except for these three types of adhesive compositions Agent composition (in this specification, referred to as "adhesive composition (I-1) to adhesive composition other than adhesive composition (I-3)"), it can also be used in the same way as these containing components The ingredients stated.

作為黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物，除能量線硬化性之黏著劑組成物以外，亦可列舉非能量線硬化性之黏著劑組成物。 As the adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3), in addition to the energy-ray-curable adhesive composition, non-energy-ray-curable adhesives can also be cited Composition.

作為非能量線硬化性之黏著劑組成物，例如可列舉：含有丙烯酸系樹脂、胺基甲酸酯系樹脂、橡膠系樹脂、聚矽氧系樹脂、環氧系樹脂、聚乙烯醚、聚碳酸酯、酯系樹脂等非能量線硬化性之黏著性樹脂(I-1a)之黏著劑組成物(I-4)，較佳為含有丙烯酸系樹脂之黏著劑組成物。 Examples of non-energy-ray curable adhesive compositions include acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, and polycarbonates. The adhesive composition (I-4) of the non-energy-ray curable adhesive resin (I-1a) such as ester and ester resin is preferably an adhesive composition containing acrylic resin.

黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物較佳為含有1種或2種以上之交聯劑，該交聯劑的含量可設為與上述之黏著劑組成物(I-1)等情形相同。 The adhesive composition other than the adhesive composition (I-1) to the adhesive composition (I-3) preferably contains one or more crosslinking agents, and the content of the crosslinking agent can be set to The adhesive composition (I-1) mentioned above is the same.

<黏著劑組成物(I-4)> <Adhesive composition (I-4)>

作為較佳的黏著劑組成物(I-4)，例如可列舉：含有前述黏著性樹脂(I-1a)、及交聯劑之黏著劑組成物。 As a preferable adhesive composition (I-4), the adhesive composition containing the said adhesive resin (I-1a) and a crosslinking agent is mentioned, for example.

[黏著性樹脂(I-1a)] [Adhesive resin (I-1a)]

作為黏著劑組成物(I-4)中的黏著性樹脂(I-1a)，可列舉與黏著劑組成物(I-1)中的黏著性樹脂(I-1a)相同的黏著性樹脂。 Examples of the adhesive resin (I-1a) in the adhesive composition (I-4) include the same adhesive resins as the adhesive resin (I-1a) in the adhesive composition (I-1).

黏著劑組成物(I-4)所含有之黏著性樹脂(I-1a)可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 Adhesive resin (I-1a) contained in the adhesive composition (I-4) may be only one type or two or more types. In the case of two or more types, the combination and ratio can be arbitrary select.

黏著劑組成物(I-4)中，黏著性樹脂(I-1a)的含量相對於黏著劑組成物(I-4)的總質量，較佳為5質量%至99質 量%，更佳為10質量%至95質量%，尤佳為15質量%至90質量%。 In the adhesive composition (I-4), the content of the adhesive resin (I-1a) relative to the total mass of the adhesive composition (I-4) is preferably 5 mass% to 99 mass The amount% is more preferably 10% by mass to 95% by mass, and particularly preferably 15% by mass to 90% by mass.

[交聯劑] [Crosslinking agent]

於使用除源自(甲基)丙烯酸烷基酯之結構單元以外，進而具有源自含官能基之單體之結構單元之前述丙烯酸系聚合物作為黏著性樹脂(I-1a)之情形時，黏著劑組成物(I-4)較佳為進而含有交聯劑。 When using the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from alkyl (meth)acrylate as the adhesive resin (I-1a), The adhesive composition (I-4) preferably further contains a crosslinking agent.

作為黏著劑組成物(I-4)中的交聯劑，可列舉與黏著劑組成物(I-1)中的交聯劑相同的化合物。 Examples of the crosslinking agent in the adhesive composition (I-4) include the same compounds as the crosslinking agent in the adhesive composition (I-1).

黏著劑組成物(I-4)所含有之交聯劑可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 The crosslinking agent contained in the adhesive composition (I-4) may be only one type or two or more types. When there are two or more types, the combination and ratio can be arbitrarily selected.

前述黏著劑組成物(I-4)中，交聯劑的含量相對於黏著性樹脂(I-1a)的含量100質量份，較佳為0.01質量份至50質量份，更佳為0.1質量份至20質量份，尤佳為0.3質量份至15質量份。 In the aforementioned adhesive composition (I-4), the content of the crosslinking agent relative to the content of the adhesive resin (I-1a) is 100 parts by mass, preferably 0.01 to 50 parts by mass, more preferably 0.1 part by mass To 20 parts by mass, particularly preferably 0.3 to 15 parts by mass.

[其他添加劑] [Other additives]

黏著劑組成物(I-4)中，在無損本發明之效果之範圍內，亦可含有不屬於上述之任一種成分之其他添加劑。 The adhesive composition (I-4) may contain other additives that do not belong to any of the above-mentioned components within a range that does not impair the effects of the present invention.

作為前述其他添加劑，可列舉與黏著劑組成物(I-1) 中的其他添加劑相同的化合物。 Examples of the aforementioned other additives include adhesive composition (I-1) The other additives in the same compound.

黏著劑組成物(I-4)所含有之其他添加劑可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 The other additives contained in the adhesive composition (I-4) may be only one type or two or more types, and when there are two or more types, the combinations and ratios can be arbitrarily selected.

黏著劑組成物(I-4)中，其他添加劑的含量並無特別限定，根據該其他添加劑的種類適宜選擇即可。 The content of other additives in the adhesive composition (I-4) is not particularly limited, and may be appropriately selected according to the type of the other additives.

[溶劑] [Solvent]

以與黏著劑組成物(I-1)之情形相同之目的，黏著劑組成物(I-4)亦可含有溶劑。 For the same purpose as in the case of the adhesive composition (I-1), the adhesive composition (I-4) may also contain a solvent.

作為黏著劑組成物(I-4)中的前述溶劑，可列舉與黏著劑組成物(I-1)中的溶劑相同的溶劑。 Examples of the aforementioned solvent in the adhesive composition (I-4) include the same solvents as the solvent in the adhesive composition (I-1).

黏著劑組成物(I-4)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，該等之組合及比率可任意選擇。 The solvent contained in the adhesive composition (I-4) may be only one type, or two or more types. In the case of two or more types, the combination and ratio can be arbitrarily selected.

黏著劑組成物(I-4)中，溶劑的含量並無特別限定，適宜調節即可。 In the adhesive composition (I-4), the content of the solvent is not particularly limited, and may be adjusted appropriately.

本發明之保護膜形成用複合片中，黏著劑層較佳為非能量線硬化性。原因在於，若黏著劑層為能量線硬化性，則有時無法抑制於藉由照射能量線而使保護膜形成用膜硬化時，黏著劑層亦同時硬化。若黏著劑層與保護膜形成用膜同時硬化，則有時硬化後之保護膜形成用膜及黏著劑 層於該等之界面黏附至無法剝離之程度。該情形時，難以將背面具備硬化後之保護膜形成用膜，亦即保護膜之半導體晶片(本說明書中，有時稱為「附有保護膜的半導體晶片」)，自具備硬化後之黏著劑層之支持片剝離，無法正常拾取附有保護膜的半導體晶片。藉由本發明中的支持片中的黏著劑層設為非能量線硬化性，可確實地避免此種不良情況，從而可更容易地拾取附有保護膜的半導體晶片。 In the composite sheet for forming a protective film of the present invention, the adhesive layer is preferably non-energy ray curable. The reason is that if the adhesive layer is energy-ray curable, it may not be possible to prevent the adhesive layer from being cured at the same time when the film for forming a protective film is cured by irradiation of energy rays. If the adhesive layer and the protective film formation film are cured at the same time, sometimes the cured protective film formation film and adhesive The layer adheres to the interface to the extent that it cannot be peeled off. In this case, it is difficult to provide a hardened protective film forming film on the back side, that is, a semiconductor chip with a protective film (in this specification, sometimes referred to as a "semiconductor chip with protective film"), since it has a hardened adhesive The support sheet of the agent layer is peeled off, and the semiconductor wafer with the protective film cannot be picked up normally. By setting the adhesive layer in the support sheet of the present invention to be non-energy-ray curable, such a problem can be reliably avoided, and the semiconductor wafer with the protective film can be picked up more easily.

本文對黏著劑層為非能量線硬化性之情形之效果進行了說明，但即便支持片中的與保護膜形成用膜直接接觸之層為黏著劑層以外之層，只要該層為非能量線硬化性，則亦發揮同樣的效果。 This article describes the effect of the case where the adhesive layer is non-energy-ray curable. However, even if the layer directly in contact with the protective film forming film in the support sheet is a layer other than the adhesive layer, as long as the layer is non-energy-ray Hardenability also exerts the same effect.

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

黏著劑組成物(I-1)至黏著劑組成物(I-3)、或黏著劑組成物(I-4)等黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物藉由將前述黏著劑及視需要之前述黏著劑以外之成分等用以構成黏著劑組成物之各成分加以調配而獲得。 Adhesive composition (I-1) to adhesive composition (I-3), or adhesive composition (I-4) and other adhesive composition (I-1) to adhesive composition (I-3) The adhesive composition other than that is obtained by blending the adhesive and components other than the adhesive if necessary, etc., to constitute the adhesive composition.

調配各成分時的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 when 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，亦即，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，亦即，不將溶劑以 外的任一種調配成分預先稀釋而將溶劑與該等調配成分混合。 When a solvent is used, it can be used in the following manner, that is, mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance; it can also be used in the following manner, that is, without The solvent is Any other formulation ingredients are diluted in advance, and the solvent is mixed with the formulation 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；使用混合機而進行混合之方法；施加超音波而進行混合之方法等。 The method of mixing each component during compounding is not particularly limited, and it can be appropriately selected from the following 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. Methods of mixing, 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，則並無特別限定，適宜調節即可，溫度較佳為15℃至30℃。 Regarding the temperature and time when each component is added and mixed, as long as it does not deteriorate each compounding component, it is not particularly limited and may be adjusted appropriately, and the temperature is preferably 15°C to 30°C.

◎保護膜形成用膜 ◎Film for forming protective film

本發明中，保護膜形成用膜硬化而獲得之保護膜與支持片之間的黏著力為100mN/25mm至2000mN/25mm，更佳為300mN/25mm至1900mN/25mm。藉由前述黏著力為前述下限值以上，將半導體晶圓連同保護膜一起藉由切割刀片切割時，保護膜與支持片之剝離得到抑制，例如，背面具備保護膜之半導體晶片(附有保護膜的半導體晶片)自支持片之飛散得到抑制，可防止切削水向保護膜與支持片之間浸入。另外，藉由前述黏著力為前述上限值以下，拾取附有保護膜的半導體晶片時，半導體晶片之破裂及缺損得到抑制。如此，藉由前述黏著力為特定範圍內，保護膜形成用複合片具有良好的切割適性及拾取適性。 In the present invention, the adhesive force between the protective film obtained by curing the protective film forming film and the support sheet is 100 mN/25mm to 2000 mN/25mm, more preferably 300 mN/25mm to 1900 mN/25mm. With the aforementioned adhesive force being above the aforementioned lower limit, when the semiconductor wafer and the protective film are diced by a dicing blade, the peeling of the protective film and the support sheet is suppressed. For example, a semiconductor chip with a protective film on the back side (with protection The scattering of the film (semiconductor wafer) from the support sheet is suppressed, and cutting water can be prevented from entering between the protective film and the support sheet. In addition, since the above-mentioned adhesive force is below the above-mentioned upper limit value, when picking up the semiconductor wafer with the protective film, cracks and defects of the semiconductor wafer are suppressed. In this way, by having the aforementioned adhesive force within a specific range, the composite sheet for forming a protective film has good cutting suitability and picking suitability.

再者，本發明中，即便於保護膜形成用膜硬化後，只 要仍維持支持片及保護膜形成用膜之硬化物(換言之，支持片及保護膜)之積層結構，則仍將該積層結構體稱為「保護膜形成用複合片」。 Furthermore, in the present invention, even after the protective film formation film is cured, only To maintain the laminated structure of the support sheet and the cured product of the protective film formation film (in other words, the support sheet and the protective film), the laminated structure is still referred to as a "composite sheet for protective film formation."

保護膜與支持片之間的黏著力可利用以下之方法進行測定。 The adhesion between the protective film and the support sheet can be measured by the following method.

亦即，將寬度為25mm且長度為任意之保護膜形成用複合片藉由該保護膜形成用複合片之保護膜形成用膜貼附於被接著體。 That is, a composite sheet for forming a protective film having a width of 25 mm and an arbitrary length is attached to the adherend through the film for forming a protective film of the composite sheet for forming a protective film.

繼而，照射能量線而使保護膜形成用膜硬化，形成保護膜後，自貼附於被接著體之該保護膜，將支持片以剝離速度300mm/min剝離。此時的剝離係設為以下所謂180°剝離：以保護膜及支持片相互接觸之面彼此成為180°之角度之方式，使支持片沿該支持片的長度方向(保護膜形成用複合片的長度方向)剝離。並且，測定該180°剝離時的荷重(剝離力)，將該荷重(剝離力)的測定值設為前述黏著力(mN/25mm)。 Then, energy rays were irradiated to harden the protective film forming film, and after the protective film was formed, the support sheet was peeled from the protective film attached to the adherend at a peeling speed of 300 mm/min. The peeling system at this time is the following so-called 180° peeling: the support sheet is moved along the length direction of the support sheet so that the contact surfaces of the protective film and the support sheet are at an angle of 180°. Length direction) peel off. Then, the load (peel force) at the time of 180° peeling was measured, and the measured value of the load (peel force) was used as the aforementioned adhesive force (mN/25mm).

供於測定之保護膜形成用複合片的長度只要為可穩定地檢測出黏著力之範圍，則並無特別限定，較佳為100mm至300mm。另外，較佳為於測定時，使保護膜形成用複合片成為貼附於被接著體之狀態，使保護膜形成用複合片的貼附狀態穩定化。 The length of the composite sheet for forming a protective film used for the measurement is not particularly limited as long as it is a range in which the adhesive force can be stably detected, and it is preferably 100 mm to 300 mm. In addition, it is preferable to make the composite sheet for forming a protective film in a state of being attached to the adherend during the measurement, so that the attached state of the composite sheet for forming a protective film is stabilized.

本發明中，保護膜形成用膜與前述支持片之間的黏著力並無特別限定，例如可為80mN/25mm以上等，較佳為100mN/25mm以上，更佳為150mN/25mm以上，尤佳為200mN/25mm以上。藉由前述黏著力為100mN/25mm以上，容易將保護膜與支持片之間的黏著力調節為上述範圍。 In the present invention, the adhesive force between the protective film forming film and the aforementioned support sheet is not particularly limited. For example, it can be 80mN/25mm or more, preferably 100mN/25mm or more, more preferably 150mN/25mm or more, and more preferably It is 200mN/25mm or more. With the aforementioned adhesive force of 100 mN/25 mm or more, it is easy to adjust the adhesive force between the protective film and the support sheet to the above-mentioned range.

另一方面，保護膜形成用膜與前述支持片之間的黏著力的上限值並無特別限定，例如可設為10000mN/25mm、5000mN/25mm、3000mN/25mm等之任一者。但是，該等為一例。 On the other hand, the upper limit of the adhesive force between the protective film formation film and the support sheet is not particularly limited, and for example, it can be any of 10000mN/25mm, 5000mN/25mm, 3000mN/25mm, etc. However, this is just one example.

關於保護膜形成用膜與支持片之間的黏著力，除不藉由照射能量線而使供於測定之保護膜形成用膜硬化之方面以外，可利用與上述之保護膜與支持片之間的黏著力相同的方法進行測定。 Regarding the adhesive force between the protective film formation film and the support sheet, the protective film formation film used for measurement is not cured by the energy ray irradiation, and can be used between the protective film and the support sheet mentioned above. The adhesion is measured in the same way.

關於上述之保護膜與支持片之間的黏著力、及保護膜形成用膜與支持片之間的黏著力，例如可藉由調節保護膜形成用膜的含有成分的種類及量、支持片中的設置保護膜形成用膜之層的構成材料、該層的表面狀態等而適宜調節。 Regarding the above-mentioned adhesive force between the protective film and the supporting sheet, and the adhesive force between the protective film forming film and the supporting sheet, for example, the types and amounts of components contained in the protective film forming film can be adjusted, and the supporting sheet The constituent materials of the layer in which the protective film forming film is provided, the surface state of the layer, etc. are appropriately adjusted.

例如，保護膜形成用膜的含有成分的種類及量可藉由後述之保護膜形成用組成物的含有成分的種類及量進行 調節。並且，藉由調節保護膜形成用組成物的含有成分中，例如不具有能量線硬化性基之聚合物(b)的種類及含量、填充材料(d)的含量、或交聯劑(f)的含量，可更容易地調節保護膜或保護膜形成用膜與支持片之間的黏著力。 For example, the type and amount of components contained in the film for forming a protective film can be determined by the types and amounts of components contained in the composition for forming a protective film described later. adjust. In addition, by adjusting the components contained in the composition for forming a protective film, for example, the type and content of the polymer (b) that does not have an energy-ray curable group, the content of the filler (d), or the crosslinking agent (f) The content of, can more easily adjust the adhesion between the protective film or the protective film forming film and the support sheet.

另外，例如，於支持片中的設置保護膜形成用膜之層為黏著劑層之情形時，該層的構成材料可藉由調節黏著劑層的含有成分的種類及量而適宜調節。並且，黏著劑層的含有成分的種類及量可藉由上述黏著劑組成物的含有成分的種類及量而調節。並且，藉由調節黏著劑組成物的含有成分中，例如黏著性樹脂的種類及含量，可更容易地調節保護膜或保護膜形成用膜與支持片(黏著劑層)之間的黏著力。 In addition, for example, when the layer provided with the protective film forming film in the support sheet is an adhesive layer, the constituent material of the layer can be appropriately adjusted by adjusting the types and amounts of components contained in the adhesive layer. In addition, the types and amounts of the components contained in the adhesive layer can be adjusted by the types and amounts of the components contained in the adhesive composition. In addition, by adjusting the contained components of the adhesive composition, for example, the type and content of the adhesive resin, the adhesive force between the protective film or the protective film forming film and the support sheet (adhesive layer) can be adjusted more easily.

另一方面，於支持片中的設置保護膜形成用膜之層為基材之情形時，保護膜或保護膜形成用膜與支持片之間的黏著力，除基材的構成材料以外，亦可利用基材的表面狀態進行調節。並且，基材的表面狀態例如可藉由實施前文作為提高基材與其他層之密接性之處理所列舉之表面處理而進行調節，亦即，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；底塗處理等任一處理。 On the other hand, when the layer provided with the protective film forming film in the support sheet is the base material, the adhesive force between the protective film or the protective film forming film and the support sheet is not only the constituent material of the base material, but also The surface condition of the substrate can be used to adjust. In addition, the surface condition of the substrate can be adjusted by, for example, performing the surface treatment listed above as the treatment to improve the adhesion between the substrate and other layers, that is, the unevenness treatment by sandblasting, solvent treatment, etc.; Corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments; any treatment such as primer treatment.

保護膜形成用膜可列舉：具有能量線硬化性，例如含 有能量線硬化性成分(a)之保護膜形成用膜。 Examples of films for forming protective films include: having energy ray curability, such as containing A film for forming a protective film with 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。 The energy ray curable component (a) is preferably uncured, preferably has adhesiveness, and more preferably is uncured and has adhesiveness.

保護膜形成用膜可僅為1層(單層)，亦可為2層以上之多層，於為多層之情形時，該等多層可相互相同亦可不同，該等多層之組合並無特別限定。 The protective film formation film may be only one layer (single layer), or multiple layers of two or more layers. In the case of multiple layers, the multiple layers may be the same or different from each other, and the combination of the multiple layers is not particularly limited .

保護膜形成用膜的厚度較佳為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，可形成保護能力更高的保護膜。另外，藉由保護膜形成用膜的厚度為前述上限值以下，可抑制厚度過厚。 The thickness of the protective film formation film 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 protective film forming film is more than the aforementioned lower limit, a protective film with higher protective ability can be formed. In addition, since the thickness of the film for forming a protective film is not more than the aforementioned upper limit value, it is possible to suppress excessive thickness.

此處，所謂「保護膜形成用膜的厚度」，意指保護膜形成用膜整體的厚度，例如，所謂由多層構成之保護膜形成用膜的厚度，意指構成保護膜形成用膜之全部層的合計厚度。再者，作為保護膜形成用膜的厚度的測定方法，例如可列舉以下方法等：於任意的5個部位，使用接觸式厚度計，測定厚度，算出測定值之平均。 Here, the "thickness of the protective film formation film" means the thickness of the entire protective film formation film. For example, the thickness of the protective film formation film composed of multiple layers means the entirety of the protective film formation film The total thickness of the layer. In addition, as a method for measuring the thickness of the protective film forming film, for example, the following method can be cited: the thickness is measured at any 5 locations using a contact thickness meter, and the average of the measured values is calculated.

關於使保護膜形成用膜硬化而形成保護膜時的硬化條件，只要保護膜成為充分發揮該保護膜的功能之程度的硬化度，則並無特別限定，根據保護膜形成用膜的種類適宜選擇即可。 Regarding the curing conditions when the protective film forming film is cured to form the protective film, as long as the protective film has a degree of curing sufficient to fully exhibit the function of the protective film, there are no particular restrictions, and it is appropriately selected according to the type of the protective film forming film That's it.

例如，保護膜形成用膜之硬化時，能量線之照度較佳為4mW/cm2至280mW/cm2。並且，前述硬化時，能量線之光量較佳為3mJ/cm2至1000mJ/cm2。 For example, when the film for forming a protective film is cured, the illuminance of the energy ray is preferably 4 mW/cm 2 to 280 mW/cm 2 . In addition, during the aforementioned curing, the amount of light of the energy ray is preferably 3 mJ/cm 2 to 1000 mJ/cm 2 .

<<保護膜形成用組成物>> <<Protective film forming composition>>

保護膜形成用膜可使用含有該保護膜形成用膜的構成材料之保護膜形成用組成物而形成。例如，於保護膜形成用膜之形成對象面塗敷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保護膜形成用膜。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」，如前文所說明。 The film for protective film formation can be formed using the composition for protective film formation containing the constituent material of the film for protective film formation. For example, by coating the protective film forming composition on the surface to be formed of the protective film forming film, and drying it as necessary, the protective film forming film can be formed on the target site. The content ratio of the components that do not vaporize at room temperature in the protective film formation composition is usually the same as the content ratio of the aforementioned components in the protective film formation film. Here, the so-called "normal temperature" is as explained above.

利用公知的方法塗敷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 a protective film may be applied by a known method, for example, methods using various coating machines such as air knife coater, knife coater, bar coater, gravure coater, roll Type coater, roll knife coater, curtain coater, die coater, knife coater, screen coater, wire-wound bar coater, contact coater, etc.

保護膜形成用組成物的乾燥條件並無特別限定，於保護膜形成用組成物含有後述之溶劑之情形時，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 a protective film are not particularly limited. When the composition for forming a protective film contains a solvent described later, it is preferably heat-dried. In this case, it is preferably, for example, 70°C to 130°C. And dry under the condition of 10 seconds to 5 minutes.

<保護膜形成用組成物(IV-1)> <Composition for forming protective film (IV-1)>

作為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)之保護膜形成用組成物(IV-1)等。 As the protective film forming composition, for example, the protective film forming composition (IV-1) containing the aforementioned energy ray curable component (a) can be cited.

[能量線硬化性成分(a)] [Energy ray curable component (a)]

能量線硬化性成分(a)係藉由照射能量線而硬化之成分，該成分用以對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 that is cured by irradiation with energy rays, and the component is used to impart film-forming properties, flexibility, or the like to the film for forming a protective film.

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)可至少一部分藉由後述之交聯劑(f)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). The aforementioned polymer (a1) may be crosslinked at least partially by the crosslinking agent (f) described later, or may not be crosslinked.

再者，本說明書中，所謂重量平均分子量，只要無特別說明，則意指藉由凝膠滲透層析(GPC；Gel Permeation Chromatography)法所測定之聚苯乙烯換算值。 In addition, in this specification, the weight average molecular weight means the polystyrene conversion value measured by the gel permeation chromatography (GPC; Gel Permeation Chromatography) method, unless otherwise specified.

(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) with energy ray curable base and 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)係丙烯酸系聚合物(a11)與能量線硬化性化合物(a12)聚合而成，前述丙烯酸系聚合物(a11)具有可與其他化合物所具有之基反應之官能 基，前述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 acrylic resin (a1-1), and the acrylic resin (a1-1) is an acrylic polymer (a11). ) Is polymerized with an energy-ray curable compound (a12), the aforementioned acrylic polymer (a11) has a function that can react with groups possessed by other compounds The energy-ray-curable compound (a12) has an energy-ray-curable group such as a group that reacts with the aforementioned functional group and an energy-ray-curable double bond.

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 groups that can react with groups possessed by other compounds include hydroxyl groups, carboxyl groups, amino groups, and substituted amino groups (one or two hydrogen atoms of the amino group are substituted with groups other than hydrogen atoms. Group), epoxy group and the like. However, in terms of preventing corrosion of a semiconductor wafer or a circuit of a semiconductor wafer, the aforementioned functional group is preferably a group other than a carboxyl group.

該等之中，前述官能基較佳為羥基。 Among them, 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，亦可為除該等單體以外，進而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。 The acrylic polymer (a11) having a functional group may be, for example, a polymer obtained by copolymerizing the acrylic monomer having a functional group and the acrylic monomer having no functional group, and it may also be a polymer obtained by copolymerizing the acrylic monomer having a functional group and the acrylic monomer having no functional group. In addition to these monomers, a polymer obtained by copolymerizing monomers other than acrylic monomers (non-acrylic 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 aforementioned acrylic monomer having a functional group include: hydroxyl group-containing monomers, carboxyl group-containing monomers, amine group-containing monomers, substituted amine group-containing monomers, epoxy group-containing monomers, etc. .

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。 As the aforementioned hydroxyl-containing monomers, for example, (meth)acrylic acid can be cited Hydroxymethyl, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylate (Meth)acrylic acid hydroxyalkyl esters such as 3-hydroxybutyl acrylate and 4-hydroxybutyl (meth)acrylate; non-(meth)acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol (without (Meth) unsaturated alcohol with acryloyl skeleton) and so on.

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 aforementioned carboxyl group-containing monomer include: ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having ethylenically unsaturated bonds) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, Maleic acid, citraconic acid and other ethylenically unsaturated dicarboxylic acids (dicarboxylic acids with ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. (formula Group) carboxyalkyl acrylate and the like.

具有前述官能基之丙烯酸系單體較佳為含羥基之單體或含羧基之單體，更佳為含羥基之單體。 The acrylic monomer having the aforementioned functional group is preferably a hydroxyl group-containing monomer or 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，該等之組合及比率可任意選擇。 The aforementioned acrylic monomer having a functional group that constitutes the aforementioned 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 can be arbitrarily selected .

作為前述不具有官能基之丙烯酸系單體，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。 As the aforementioned acrylic monomer having no functional group, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (Meth) n-butyl acrylate, (A Base) isobutyl acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, 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), tridecyl (meth)acrylate, ( Myristyl meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (palmityl (meth)acrylate) , Heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. The alkyl group constituting the alkyl ester is a chain with a carbon number of 1 to 18 Structure of alkyl (meth)acrylate, etc.

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。 In addition, as the aforementioned acrylic monomer having no functional group, for example, methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, and ethoxymethyl (meth)acrylate can also be cited. (Meth)acrylates containing alkoxyalkyl groups such as ethoxyethyl (meth)acrylate; those containing aryl (meth)acrylates such as phenyl(meth)acrylate, etc., have aromatic groups (Meth)acrylate; non-crosslinkable (meth)acrylamide and its derivatives; (meth)acrylic acid N,N-dimethylaminoethyl, (meth)acrylic acid N,N- Non-crosslinkable (meth)acrylates with tertiary amino groups such as dimethylaminopropyl.

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，該等之組合及比率可任意選擇。 The aforementioned acrylic monomer having no functional group constituting the aforementioned acrylic polymer (a11) may be only one type, or two or more types, in which case it may be more than two types. In the above situation, these combinations and ratios can 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 aforementioned 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，該等之組合及比率可任意選擇。 The aforementioned non-acrylic monomer constituting the aforementioned acrylic polymer (a11) may be only one type or two or more types. In the case of two or more types, these combinations and ratios can be arbitrarily selected.

前述丙烯酸系聚合物(a11)中，由具有前述官能基之丙烯酸系單體衍生之結構單元之量相對於構成該丙烯酸系聚合物(a11)之結構單元之總質」量的比例(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 aforementioned acrylic polymer (a11), the ratio (content) of the amount of structural units derived from the acrylic monomer having the aforementioned functional group to the total mass of the structural units constituting the acrylic polymer (a11) It is preferably 0.1% by mass to 50% by mass, more preferably 1% by mass to 40% by mass, and particularly preferably 3% by mass to 30% by mass. With the aforementioned ratio in this range, the energy-ray-curable group in the acrylic resin (a1-1) obtained by copolymerization of the aforementioned acrylic polymer (a11) and the aforementioned energy-ray-curable compound (a12) The content of is easily adjusted to a better range for the degree of hardening of the protective film.

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，該等之組合及比率可任意選擇。 The acrylic polymer (a11) constituting the 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 can be arbitrarily selected .

保護膜形成用組成物(IV-1)中，丙烯酸系樹脂(a1-1)的含量相對於保護膜形成用組成物(IV-1)的總質量，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 protective film forming composition (IV-1), the content of the acrylic resin (a1-1) is preferably relative to the total mass of the protective film forming composition (IV-1) It is 1% by mass to 40% by mass, more preferably 2% by mass to 30% by mass, and particularly preferably 3% by mass to 20% by mass.

‧能量線硬化性化合物(a12) ‧Energy ray hardening 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 isocyanate groups, epoxy groups, and carboxyl groups as those that can be combined with the aforementioned acrylic polymer (a11). The functional group reaction group more preferably has 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3個。 The aforementioned energy-ray-curable compound (a12) preferably has 1 to 5 of the aforementioned energy-ray-curable group in one molecule, and more preferably has 1 to 3.

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-methacryloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, and methacrylic acid Isocyanate, allyl isocyanate, 1,1-(bisacryloxymethyl) ethyl isocyanate; by the reaction of a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth)acrylate Acrylic monoisocyanate compound obtained; Acrylic monoisocyanate compound obtained by reaction of diisocyanate compound or polyisocyanate compound, polyol compound and hydroxyethyl (meth)acrylate Wait.

該等之中，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 them, the energy ray curable compound (a12) is preferably 2-methacryloxyethyl 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，該等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 may be arbitrary select.

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%。藉由前述含量比例為此種範圍，由硬化所形成之保護膜的接著力變得更大。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%, and particularly preferably 50 mol% to 100 mol%. When the aforementioned content ratio is in this range, the adhesive force of the protective film formed by curing becomes greater. In addition, when the energy ray curable compound (a12) is a monofunctional (having one group in one molecule) compound, the upper limit of the ratio of the content becomes 100 mol%, but it is less than the 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 100,000 to 2,000,000, more preferably 300,000 to 1,500,000.

於前述聚合物(a1)的至少一部分藉由交聯劑(f)進行 交聯之情形時，前述聚合物(a1)可使不符合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(f)反應之基之單體進行聚合，在與上述交聯劑(f)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。 At least a part of the aforementioned polymer (a1) is carried out by a crosslinking agent (f) In the case of cross-linking, the aforementioned polymer (a1) can polymerize any monomer that does not meet the above description and constitutes the aforementioned acrylic polymer (a11) and has a group reactive with the cross-linking agent (f) Cross-linking is performed in the group reactive with the above-mentioned cross-linking agent (f), and cross-linking may be performed in the group derived from the energy-beam curable compound (a12) which reacts with the aforementioned functional group.

保護膜形成用組成物(IV-1)及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，該等之組合及比率可任意選擇。 The aforementioned polymer (a1) contained in the protective film forming composition (IV-1) and the protective film forming film may be only one type or two or more types. In the case of two or more types, these The combination and ratio can be chosen arbitrarily.

(具有能量線硬化性基且分子量為100至80000之化合物(a2)) (Compound (a2) with energy ray hardening group and 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 possessed by the compound (a2) having an energy-ray-curable group and a molecular weight of 100 to 80,000 include a group containing an energy-ray-curable double bond, and as a preferable group, (former) Base) Acrylic, vinyl and the like.

若前述化合物(a2)滿足上述條件，則並無特別限定，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。 If the aforementioned compound (a2) satisfies the above conditions, it is not particularly limited. Examples include low molecular weight compounds having energy ray curable groups, epoxy resins having energy ray curable groups, and phenol resins having energy ray curable groups. Wait.

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。 Among the aforementioned compounds (a2), as the low molecular weight compound having an energy ray-curable group, for example, a polyfunctional monomer or oligomer can be cited, and preferred It is an acrylate-based compound having 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(三環癸烷二羥甲基二(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。 Examples of the acrylate-based compound include: 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, and propoxylated ethoxy Bisphenol A bis(meth)acrylate, 2,2-bis[4-((meth)acryloyloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A bis(methyl) )Acrylate, 2,2-bis[4-((meth)acryloyloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloyloxy) Ethoxy) phenyl] 茀, 2,2-bis[4-((meth) propylene oxypolypropoxy) phenyl] propane, tricyclodecane dimethanol di(meth)acrylate (three Cyclodecane dimethylol 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, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth) Acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((methyl) ) Allyloxyethoxy) phenyl) propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-bis( 2-functional (meth)acrylates such as meth)acryloxypropane; tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone modified isocyanuric acid Tris-(2-(meth)acryloyloxyethyl) ester, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth) Acrylate, di-trimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, Dipentaerythritol hexa(A Multifunctional (meth)acrylates such as (meth)acrylate; Multifunctional (meth)acrylate oligomers such as (meth)acrylate urethane 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「日本專利特開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(h)之樹脂，但本發明中視作前述化合物(a2)。 In the aforementioned compound (a2), as an epoxy resin having an energy ray curable group and a phenol resin having an energy ray curable group, for example, the paragraph 0043 in "Japanese Patent Laid-Open No. 2013-194102" can be used. Recorded resin. Such resin also corresponds to the resin constituting the thermosetting component (h) described later, but is regarded as the aforementioned compound (a2) in the present invention.

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

保護膜形成用組成物(IV-1)及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，該等之組合及比率可任意選擇。 The above-mentioned compound (a2) contained in the protective film forming composition (IV-1) and the protective film forming film may be only one type or two or more types. In the case of two or more types, these compounds (a2) The combination and ratio can be chosen arbitrarily.

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

於保護膜形成用組成物(IV-1)及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，較佳為進而亦含有不具有能量線硬化性基之聚合物(b)。 When the protective film formation composition (IV-1) and the protective film formation film contain the aforementioned compound (a2) as the aforementioned energy ray curable component (a), it is preferable to further contain the non-energy ray curable component Base polymer (b).

前述聚合物(b)可至少一部分藉由交聯劑(f)進行交聯，亦可不進行交聯。 The aforementioned polymer (b) may be cross-linked at least partially by the cross-linking agent (f), or may not be cross-linked.

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、聚乙烯醇(PVA)、丁醛樹脂、聚酯胺基甲酸酯樹脂等。 Examples of the polymer (b) that does not have an energy-ray curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, and acrylic urethane resins. , Polyvinyl alcohol (PVA), butyral resin, polyester urethane resin, etc.

該等之中，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 well-known polymer, for example, it may be a homopolymer of one type of acrylic monomer, or a copolymer of two or more types of acrylic monomers, or may be one type 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」，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 containing glycidyl groups. (Methyl)acrylate, hydroxyl-containing (meth)acrylate, substituted amine-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 aforementioned alkyl (meth)acrylate include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( N-Butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary 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, (meth)acrylate Base) decyl acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate, (meth) Base) tetradecyl acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (palmityl (meth)acrylate), Heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. The alkyl group constituting the alkyl ester is a chain structure with a carbon number of 1 to 18 The (meth) acrylate alkyl ester and so on.

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 a cyclic skeleton include cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentyl (meth)acrylate; (meth) ) Aralkyl (meth)acrylates such as benzyl acrylate; cycloalkenyl (meth)acrylates such as dicyclopentenyl (meth)acrylate; dicyclopentenyloxyethyl (meth)acrylate, etc. (Meth) acrylate cycloalkenyloxy alkyl 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。 As said glycidyl group-containing (meth)acrylate, glycidyl (meth)acrylate etc. are mentioned, for example.

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-containing (meth)acrylates include: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth) ) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, (meth)propylene Acid 4-hydroxybutyl ester and so on.

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。 Examples of the aforementioned substituted amino group-containing (meth)acrylate include N-methylaminoethyl (meth)acrylate and the like.

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。 Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; styrene.

作為至少一部分藉由交聯劑(f)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(f)反應之聚合物。 Examples of the polymer (b) that is at least partly cross-linked by the cross-linking agent (f) and does not have the aforementioned energy-ray curable group include: the reactive functional group in the aforementioned polymer (b) and the cross-linking agent (f) Reactive polymer.

前述反應性官能基根據交聯劑(f)之種類等適宜選擇即可，並無特別限定。例如，於交聯劑(f)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，該等之中，較佳為與異氰酸酯基之反應性高之羥基。另外，於交聯劑(f)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，該等之中，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 aforementioned reactive functional group may be appropriately selected according to the kind of crosslinking agent (f), etc., and is not particularly limited. For example, when the crosslinking agent (f) is a polyisocyanate compound, as the aforementioned reactive functional group, a hydroxyl group, a carboxyl group, an amino group, etc. can be mentioned. Among these, one having high reactivity with an isocyanate group is preferred. Hydroxy. In addition, when the crosslinking agent (f) is an epoxy-based compound, as the aforementioned reactive functional group, a carboxyl group, an amino group, an amide group, etc. can be cited. Among these, a combination with an epoxy group is preferred. Highly reactive carboxyl group. However, in terms of preventing corrosion of the semiconductor wafer or the circuit of the semiconductor wafer, the aforementioned 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 curable group, the polymer obtained by polymerizing at least the monomer which has the said reactive functional group is mentioned, for example. Acrylic polymer In the case of (b-1), any one or both of the aforementioned acrylic monomers and non-acrylic monomers listed as the monomers constituting the acrylic polymer (b-1) are used having the aforementioned reaction Monomers with functional groups are sufficient. For example, as the aforementioned polymer (b) having a hydroxyl group as a reactive functional group, for example, a polymer obtained by polymerizing a hydroxyl-containing (meth)acrylate may be mentioned. A polymer obtained by polymerizing a monomer in which one or more hydrogen atoms in the aforementioned acrylic monomer or non-acrylic monomer is substituted with the aforementioned reactive functional group.

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25質量%，更佳為2質量%至20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 the reactive functional group relative to the total amount of the structural unit constituting the polymer (b) It is preferably 1% by mass to 25% by mass, more preferably 2% by mass to 20% by mass. When the aforementioned ratio is in such a range, the degree of crosslinking in the aforementioned polymer (b) 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。 In terms of better film forming properties of the protective film forming composition (IV-1), the weight average molecular weight (Mw) of the polymer (b) that does not have an energy ray curable group is preferably 10,000 to 2,000,000, More preferably, it is 100,000 to 1,500,000.

保護膜形成用組成物(IV-1)及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，該等之組合及比率 可任意選擇。 The composition for forming protective film (IV-1) and the polymer (b) having no energy ray curable group contained in the film for forming protective film may be only one type, or two or more types, or two types In the above situation, the combination and ratio Can be chosen arbitrarily.

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，較佳為亦進而含有不具有能量線硬化性基之聚合物(b)，該情形時，亦較佳為進而含有前述(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 aforementioned polymer (a1) and aforementioned compound (a2) can be cited. In addition, when the protective film forming composition (IV-1) contains the aforementioned compound (a2), it is preferable to further contain a polymer (b) that does not have an energy-ray curable group. In this case, it is also more It is preferable to further contain the aforementioned (a1). In addition, the composition (IV-1) for forming a protective film may not contain the compound (a2), and may also contain the polymer (a1) and the polymer (b) that does not have an energy ray curable group.

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 protective film forming composition (IV-1) contains the aforementioned polymer (a1), the aforementioned compound (a2), and the polymer (b) without an energy-ray curable group, the protective film forming composition ( In IV-1), the content of the aforementioned compound (a2) is 100 parts by mass relative to the total content of the aforementioned polymer (a1) and the polymer (b) without an energy-ray curable group, preferably 10 parts by mass to 400 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)的合計含量相對於溶劑以外的成分的總含量之比例(亦即，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)較佳為5質量%至90質量%，更佳為10質量%至80質量%，尤佳為15質量%至70 質量%。藉由前述合計含量的比例為此種範圍，保護膜形成用膜的能量線硬化性變得更良好。 In the protective film forming composition (IV-1), the ratio of the total content of the aforementioned energy-ray curable component (a) and polymer (b) without energy-ray curable group to the total content of components other than the solvent (That is, the total content of the aforementioned energy ray curable component (a) and the polymer (b) not having an energy ray curable group in the film for forming a protective film) is preferably 5 to 90% by mass, and more It is preferably 10% by mass to 80% by mass, and particularly preferably 15% by mass to 70% by mass quality%. When the ratio of the aforementioned total content is in this range, the energy ray curability of the protective film formation film becomes more favorable.

於保護膜形成用組成物(IV-1)含有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)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中，前述聚合物(b)的含量相對於能量線硬化性成分(a)的含量100質量份，較佳為3質量份至160質量份，更佳為6質量份至130質量份。藉由前述聚合物(b)的前述含量為此種範圍，保護膜形成用膜的能量線硬化性變得更良好。 When the protective film forming composition (IV-1) contains the aforementioned energy ray curable component (a) and the polymer (b) without an energy ray curable group, the protective film forming composition (IV-1) ) And the protective film forming film, the content of the aforementioned polymer (b) relative to 100 parts by mass of the energy ray curable component (a), preferably 3 parts by mass to 160 parts by mass, more preferably 6 parts by mass To 130 parts by mass. When the content of the polymer (b) is in this range, the energy ray curability of the protective film forming film becomes more favorable.

保護膜形成用組成物(IV-1)中，除能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)以外，亦可根據目的含有選自由光聚合起始劑(c)、填充材料(d)、偶合劑(e)、交聯劑(f)、著色劑(g)、熱硬化性成分(h)、及通用添加劑(z)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(a)及熱硬化性成分(h)之保護膜形成用組成物(IV-1)，所形成之保護膜形成用膜藉由加熱而對被接著體之接著力提高，由該保護膜形成用膜形成之保護膜的強度亦提高。 In the composition (IV-1) for forming a protective film, in addition to the energy ray curable component (a) and the polymer (b) without an energy ray curable group, it may also contain a photopolymerization initiator according to the purpose (c), filler (d), coupling agent (e), crosslinking agent (f), coloring agent (g), thermosetting component (h), and general additives (z) in the group consisting of One kind or two or more kinds. For example, by using the protective film forming composition (IV-1) containing the aforementioned energy ray curable component (a) and thermosetting component (h), the formed protective film forming film is heated against the substrate The adhesive force of the adhering body is improved, and the strength of the protective film formed of the protective film forming film is also improved.

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

作為光聚合起始劑(c)，例如可列舉：安息香、安息香甲醚、安息香***、安息香異丙醚、安息香異丁醚、安 息香苯甲酸、安息香苯甲酸甲酯、安息香二甲基縮酮等安息香化合物；苯乙酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等苯乙酮化合物；雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦等醯基氧化膦化合物；芣基苯基硫化物、一硫化四甲基秋蘭姆等硫化物化合物；1-羥基環己基苯基酮等α-酮醇化合物；偶氮雙異丁腈等偶氮化合物；二茂鈦等二茂鈦化合物；噻噸酮等噻噸酮化合物；二苯甲酮、2-(二甲基胺基)-1-(4-嗎啉基苯基)-2-苄基-1-丁酮、乙酮，1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)等二苯甲酮化合物；過氧化物化合物；二乙醯等二酮化合物；苯偶醯；二苯偶醯；2,4-二乙基噻噸酮；1,2-二苯基甲烷；2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮；2-氯蒽醌等。 As the photopolymerization initiator (c), for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin Benzoin compounds such as benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-di Acetophenone compounds such as methoxy-1,2-diphenylethane-1-one; bis(2,4,6-trimethylbenzyl)phenyl phosphine oxide, 2,4,6- Phosphine oxide compounds such as trimethylbenzyl diphenyl phosphine oxide; Sulfide compounds such as fluorinyl phenyl sulfide and tetramethylthiuram monosulfide; 1-hydroxycyclohexyl phenyl ketone and other α- Keto alcohol compounds; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone compounds such as thioxanthone; benzophenone, 2-(dimethylamino)-1- (4-morpholinylphenyl)-2-benzyl-1-butanone, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3 -Yl]-,1-(O-acetyloxime) and other benzophenone compounds; peroxide compounds; diketone compounds such as diacetin; benzidine; diphenylacetone; 2,4-diethyl Thioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] acetone; 2-chloroanthraquinone, etc.

另外，作為光聚合起始劑(c)，例如亦可使用1-氯蒽醌等醌化合物；胺等光增感劑等。 In addition, as the photopolymerization initiator (c), for example, quinone compounds such as 1-chloroanthraquinone; photosensitizers such as amines, and the like can also be used.

保護膜形成用組成物(IV-1)所含有之光聚合起始劑(c)可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 The photopolymerization initiator (c) contained in the protective film forming composition (IV-1) may be only one type, or two or more types. In the case of two or more types, the combination and ratio Can be chosen arbitrarily.

於使用光聚合起始劑(c)之情形時，保護膜形成用組成物(IV-1)中，光聚合起始劑(c)的含量相對於能量線硬化性化合物(a)的含量100質量份，較佳為0.01質量份至20 質量份，更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 In the case of using the photopolymerization initiator (c), in the protective film forming composition (IV-1), the content of the photopolymerization initiator (c) is relative to the content of the energy ray curable compound (a) 100 Parts by mass, preferably 0.01 parts by mass to 20 parts by mass Parts by mass, more preferably 0.03 parts by mass to 10 parts by mass, particularly preferably 0.05 parts by mass to 5 parts by mass.

[填充材料(d)] [Filling material (d)]

藉由保護膜形成用膜含有填充材料(d)，保護膜形成用膜硬化而獲得之保護膜容易調整熱膨脹係數，使該熱膨脹係數對於保護膜之形成對象物而言最佳化，藉此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，藉由保護膜形成用膜含有填充材料(d)，可降低保護膜的吸濕率，或提高散熱性。 When the protective film forming film contains the filler (d), the protective film obtained by curing the protective film forming film can easily adjust the thermal expansion coefficient and optimize the thermal expansion coefficient for the object to be formed of the protective film. The reliability of the package obtained by the composite sheet for forming a protective film is further improved. In addition, when the protective film forming film contains the filler (d), the moisture absorption rate of the protective film can be reduced, or the heat dissipation can be improved.

作為填充材料(d)，例如可列舉由導熱性材料構成之材料。 As the filler (d), for example, a material composed of a thermally conductive material can be cited.

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 filling material (d) may be any one of an organic filling material and an inorganic filling material, preferably an inorganic filling material.

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；將該等無機填充材料球形化而成之珠粒；該等無機填充材料的表面改質品；該等無機填充材料的單晶纖維；玻璃纖維等。 As a preferable inorganic filler, for example, powders such as silica, alumina, talc, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, boron nitride, etc. can be cited; these inorganic fillers are formed by spheronization The beads; the surface modification products of the inorganic fillers; the single crystal fibers of the inorganic fillers; glass fibers, etc.

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

填充材料(d)的平均粒徑並無特別限定，較佳為0.01μm至20μm，更佳為0.1μm至15μm，尤佳為0.3μm 至10μm。藉由填充材料(d)的平均粒徑為此種範圍，可維持對保護膜之形成對象物之接著性，並且可抑制保護膜之光之透過率之降低。 The average particle size of the filler (d) is not particularly limited, but is preferably 0.01 μm to 20 μm, more preferably 0.1 μm to 15 μm, and particularly preferably 0.3 μm To 10μm. When the average particle size of the filler (d) is in this range, the adhesion to the object to be formed of the protective film can be maintained, and the decrease in the light transmittance of the protective film can be suppressed.

再者，本說明書中，所謂「平均粒徑」，只要無特別說明，則意指藉由雷射繞射散射法所求出之粒度分佈曲線中累計值50%下的粒徑(D50)之值。 In addition, in this specification, the "average particle size", unless otherwise specified, means the particle size (D 50 ) at 50% of the cumulative value in the particle size distribution curve obtained by the laser diffraction scattering method The value.

保護膜形成用組成物(IV-1)及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，該等之組合及比率可任意選擇。 The protective film forming composition (IV-1) and the protective film forming film may contain only one type of filler (d), or two or more types. In the case of two or more types, these fillers (d) The combination and ratio can be chosen arbitrarily.

於使用填充材料(d)之情形時，保護膜形成用組成物(IV-1)中，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(亦即，保護膜形成用膜中的填充材料(d)的含量)較佳為5質量%至83質量%，更佳為7質量%至78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 protective film forming composition (IV-1), the ratio of the content of the filler (d) to the total content of all components other than the solvent (that is, the protective film is formed) The content of the filler (d) in the film) is preferably 5 to 83% by mass, more preferably 7 to 78% by mass. When the content of the filler (d) is in this range, it is easier to adjust the above-mentioned coefficient of thermal expansion.

[偶合劑(e)] [Coupling agent (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偶合劑作為偶合劑(e)，可提高保護膜形成用膜對被接著體之接著性及密接性。另外，藉由使用偶合劑(e)，保護膜形成用膜硬化而獲得之保護膜無損耐熱性而耐水性提高。 By using a coupling agent having a functional group capable of reacting with an inorganic compound or an organic compound as the coupling agent (e), the adhesion and adhesion of the protective film forming film to the adherend can be improved. In addition, by using the coupling agent (e), the protective film obtained by curing the protective film forming film does not impair heat resistance and improves water resistance.

偶合劑(e)較佳為具有可與能量線硬化性成分(a)、不具有能量線硬化性基之聚合物(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 the functional group possessed by the energy-ray curable component (a), polymer (b) without an energy-ray curable group, etc., more preferably 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。 As a preferred silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethyl Oxyoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl Diethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethyl Oxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, ethylene Trimethoxysilane, vinyl triacetoxysilane, imidazole silane, etc.

保護膜形成用組成物(IV-1)及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，該等之組合及比率可任意選擇。 The protective film forming composition (IV-1) and the protective film forming film may contain only one type of coupling agent (e), or two or more types. In the case of two or more types, these The combination and ratio can be chosen arbitrarily.

於使用偶合劑(e)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中，偶合劑(e)的含量相對於能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的 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)所帶來之效果：填充材料(d)於樹脂中的分散性提高等，或保護膜形成用膜與被接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，可進一步抑制產生逸氣。 When the coupling agent (e) is used, in the protective film forming composition (IV-1) and the protective film forming film, the content of the coupling agent (e) is relative to the energy ray curable component (a) and does not have Energy ray-curable polymer (b) The total content is 100 parts by mass, preferably 0.03 parts by mass to 20 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass, and particularly preferably 0.1 parts by mass to 5 parts by mass. When the aforementioned content of the coupling agent (e) is above the aforementioned lower limit, the following more significant effects brought about by the use of the coupling agent (e) can be obtained: the dispersibility of the filler (d) in the resin is improved, etc., Or the adhesion between the protective film forming film and the adherend is improved. In addition, when the aforementioned content of the coupling agent (e) is not more than the aforementioned upper limit, the generation of outgassing can be further suppressed.

[交聯劑(f)] [Crosslinker (f)]

藉由使用交聯劑(f)，使上述之能量線硬化性成分(a)或不具有能量線硬化性基之聚合物(b)進行交聯，可調節保護膜形成用膜的初期接著力及凝聚力。 By using a crosslinking agent (f) to crosslink the above-mentioned energy ray curable component (a) or polymer (b) without an energy ray curable group, the initial adhesive force of the protective film formation film can be adjusted And cohesion.

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 polyisocyanate compounds, organic polyimine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), and aziridine crosslinking Agent (crosslinking agent with aziridinyl group) and the like.

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，有時將該等化合物統一簡稱為「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之化合物之反應物，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」，意指具有胺基甲酸酯鍵，並且於分子末端部具有異氰酸酯基之預聚物。 Examples of the aforementioned 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.") ; The aforementioned aromatic polyvalent isocyanate compound and other trimers, isocyanurate bodies and adducts; the aforementioned aromatic polyvalent isocyanate compound, etc. and polyol compound The terminal isocyanate urethane prepolymer obtained by the reaction, etc. The aforementioned "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound, or alicyclic polyisocyanate compound, which contains ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, or castor oil. The reactant of the low-molecular-weight active hydrogen compound, as an example of the aforementioned adduct, includes the xylylene diisocyanate adduct of trimethylolpropane described below, and the like. In addition, the term "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.

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 the aforementioned organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate Isocyanate; 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 trimethylolpropane, added toluene diisocyanate, Compounds of any one or more of hexamethylene diisocyanate and xylylene 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 the aforementioned organic polyimine compound, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridinemethamide), trimethylolpropane-tri-β-nitrogen Propidinyl propionate, tetramethylolmethane-tris-β-aziridinyl propionic acid Ester, N,N'-toluene-2,4-bis(1-aziridine methamide) triethylene 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，作為能量線硬化性成分(a)或不具有能量線硬化性基之聚合物(b)，較佳為使用含羥基之聚合物。於交聯劑(f)具有異氰酸酯基，能量線硬化性成分(a)或不具有能量線硬化性基之聚合物(b)具有羥基之情形時，藉由交聯劑(f)與能量線硬化性成分(a)或不具有能量線硬化性基之聚合物(b)之反應，可將交聯結構簡便地導入至保護膜形成用膜中。 When an organic polyisocyanate compound is used as the crosslinking agent (f), it is preferable to use a hydroxyl-containing polymer as the energy-ray curable component (a) or polymer (b) that does not have an energy-ray curable group . When the crosslinking agent (f) has an isocyanate group and the energy ray curable component (a) or the polymer (b) without an energy ray curable group has a hydroxyl group, the crosslinking agent (f) and the energy ray The reaction of the curable component (a) or the polymer (b) that does not have an energy-ray curable group can easily introduce a cross-linked structure into the protective film forming film.

保護膜形成用組成物(IV-1)及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，該等之組合及比率可任意選擇。 The composition for forming a protective film (IV-1) and the crosslinking agent (f) contained in the film for forming a protective film may be only one type or two or more types. In the case of two or more types, these The combination and ratio can be chosen arbitrarily.

於使用交聯劑(f)之情形時，保護膜形成用組成物(IV-1)中，交聯劑(f)的含量相對於能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的總含量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)所帶來之效果。另外，藉由交聯劑(f)的前述含量為前述上限值以下，可抑制交聯劑(f)之過量使用。 In the case of using the crosslinking agent (f), the content of the crosslinking agent (f) in the protective film forming composition (IV-1) is relative to the energy ray curable component (a) and does not have energy ray curability The total content of the base polymer (b) is 100 parts by mass, preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, and particularly preferably 0.5 parts by mass to 5 parts by mass. When the aforementioned content of the cross-linking agent (f) is more than the aforementioned lower limit, a more significant effect brought about by the use of the cross-linking agent (f) can be obtained. In addition, since the aforementioned content of the crosslinking agent (f) is not more than the aforementioned upper limit, the excessive use of the crosslinking agent (f) can be suppressed.

[著色劑(g)] [Colorant (g)]

作為著色劑(g)，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 (g), well-known coloring agents, such as an inorganic type pigment, an organic type pigment, an organic type dye, etc. 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、偶氮系色素、縮合偶氮系色素、靛藍系色素、紫環酮(perinone)系色素、苝系色素、二噁嗪系色素、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 aforementioned organic pigments and organic dyes include: ammonium-based pigments, cyanine-based pigments, merocyanine-based pigments, croconium-based pigments, squalilium-based pigments, and azulenium-based pigments. Pigments, polymethine pigments, naphthoquinone pigments, pyrylium pigments, phthalocyanine pigments, naphthalocyanine pigments, naphthalene lactam pigments, azo pigments, condensed azo pigments, indigo Pigments, perinone pigments, perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole pigments, Thioindigo dyes, metal complex dyes (metal complex salt dyes), dithiol metal complex dyes, indoxyphenol dyes, triallylmethane dyes, anthraquinone dyes, naphthol Pigments, methine azo pigments, benzimidazolone pigments, pyranthrone pigments, threne pigments, etc.

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 aforementioned inorganic pigments include carbon black, cobalt pigments, iron pigments, chromium pigments, titanium pigments, vanadium pigments, zirconium pigments, molybdenum pigments, ruthenium pigments, platinum pigments, ITO (Indium Tin Oxide; Indium Tin Oxide) pigments, ATO (Antimony Tin Oxide; Antimony Tin Oxide) pigments, etc.

保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之著色劑(g)可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 The coloring agent (g) contained in the protective film forming composition (IV-1) and the protective film forming film may be only one type or two or more types. In the case of two or more types, the coloring agent (g) The combination and ratio can be chosen arbitrarily.

於使用著色劑(g)之情形時，保護膜形成用膜中的著色劑(g)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，藉由調節保護膜形成用膜中的著色劑(g)的含量，調節保護膜的透光性，可調節印字視認性。該情形時，保護膜形成用組成物(IV-1)中，著色劑(g)的含量相對於溶劑以外的全部成分的總含量之比例(亦即，保護膜形成用膜中的著色劑(g)的含量)較佳為0.1質量%至10質量%，更佳為0.4質量%至7.5質量%，尤佳為0.8質量%至5質量%。藉由著色劑(g)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(g)所帶來之效果。另外，藉由著色劑(g)的前述含量為前述上限值以下，可抑制著色劑(g)之過量使用。 In the case of using a coloring agent (g), the content of the coloring agent (g) in the film for forming a protective film may be appropriately adjusted according to the purpose. For example, the protective film is sometimes printed by laser irradiation, and by adjusting the content of the coloring agent (g) in the protective film forming film, the light transmittance of the protective film can be adjusted, and the visibility of printing can be adjusted. In this case, in the protective film forming composition (IV-1), the content of the colorant (g) is the ratio of the total content of all components other than the solvent (that is, the coloring agent in the protective film forming film ( The content of g)) is preferably 0.1% by mass to 10% by mass, more preferably 0.4% by mass to 7.5% by mass, and particularly preferably 0.8% by mass to 5% by mass. When the aforementioned content of the colorant (g) is at least the aforementioned lower limit value, a more significant effect due to the use of the colorant (g) can be obtained. In addition, since the aforementioned content of the colorant (g) is not more than the aforementioned upper limit, the excessive use of the colorant (g) can be suppressed.

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

保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之熱硬化性成分(h)可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 The thermosetting component (h) contained in the protective film forming composition (IV-1) and the protective film forming film may be only one type or two or more types. In the case of two or more types, the The combination and ratio can be selected arbitrarily.

作為熱硬化性成分(h)，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 (h), for example, epoxy-based thermosetting resin, thermosetting polyimide, polyurethane, unsaturated polyester, The silicone resin or the like is preferably an epoxy-based thermosetting resin.

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

環氧系熱硬化性樹脂係由環氧樹脂(h1)及熱硬化劑(h2)構成。 The epoxy-based thermosetting resin system is composed of an epoxy resin (h1) and a thermosetting agent (h2).

保護膜形成用組成物(IV-1)及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，該等之組合及比率可任意選擇。 The epoxy-based thermosetting resin contained in the protective film forming composition (IV-1) and the protective film forming film may be one type or two or more types. In the case of two or more types, the The combination and ratio can be selected arbitrarily.

‧環氧樹脂(h1) ‧Epoxy resin (h1)

作為環氧樹脂(h1)，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 the epoxy resin (h1), well-known epoxy resins can be cited, for example, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, ortho-cresol novolac epoxy Resins, dicyclopentadiene type epoxy resins, biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenylene skeleton type epoxy resins and other epoxy resins with more than two functions Compound.

作為環氧樹脂(h1)，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 (h1), an epoxy resin having an unsaturated hydrocarbon group can also be used. Epoxy resins with unsaturated hydrocarbon groups have higher compatibility with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of the package obtained by using the composite sheet for forming a protective film is improved.

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。 Examples of epoxy resins having unsaturated hydrocarbon groups include: It can be a compound obtained by replacing part of epoxy groups of epoxy resin with groups having unsaturated hydrocarbon groups. Such a compound is obtained, for example, by performing an addition reaction of (meth)acrylic acid or a derivative thereof 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：於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。 In addition, as an epoxy resin having an unsaturated hydrocarbon group, for example, a compound in which a group having an unsaturated hydrocarbon group is directly bonded to an aromatic ring constituting the epoxy resin or the like can be cited.

不飽和烴基為具有聚合性之不飽和基，作為該不飽和烴基的具體例，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. Specific examples of the unsaturated hydrocarbon group include ethylene (vinyl), 2-propenyl (allyl), (meth)acrylic, The (meth)acrylamido group, etc., is preferably an acrylamido group.

環氧樹脂(h1)的數量平均分子量並無特別限定，就保護膜形成用膜的硬化性、以及保護膜的強度及耐熱性之方面而言，較佳為300至30000，更佳為400至10000，尤佳為500至3000。 The number average molecular weight of the epoxy resin (h1) is not particularly limited. In terms of the curability of the protective film forming film, and the strength and heat resistance of the protective film, it is preferably 300 to 30,000, more preferably 400 to 10,000, preferably 500 to 3,000.

本說明書中，所謂「數量平均分子量」，只要無特別說明，則意指藉由凝膠滲透層析(GPC)法所測定且以標準聚苯乙烯換算之值表示之數量平均分子量。 In this specification, the "number average molecular weight", unless otherwise specified, means the number average molecular weight measured by the gel permeation chromatography (GPC) method and expressed in terms of standard polystyrene conversion.

環氧樹脂(h1)的環氧當量較佳為100g/eq至1000g/eq，更佳為150g/eq至800g/eq。 The epoxy equivalent of the epoxy resin (h1) is preferably 100 g/eq to 1000 g/eq, more preferably 150 g/eq to 800 g/eq.

本說明書中，所謂「環氧當量」，意指包含1克當量的環氧基之環氧化合物的克數(g/eq)，可依據JIS K 7236：2001之方法進行測定。 In this specification, the "epoxy equivalent" means the number of grams (g/eq) of the epoxy compound containing 1 gram equivalent of epoxy group, which can be measured in accordance with the method of JIS K 7236:2001.

環氧樹脂(h1)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，該等之組合及比率可任意選擇。 The epoxy resin (h1) may be used singly, or two or more types may be used in combination. When two or more types are used in combination, these combinations and ratios can be arbitrarily selected.

‧熱硬化劑(h2) ‧Thermal hardener (h2)

熱硬化劑(h2)發揮作為針對環氧樹脂(h1)之硬化劑的功能。 The thermal hardener (h2) functions as a hardener for the epoxy resin (h1).

作為熱硬化劑(h2)，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 (h2), the compound which has 2 or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. As the aforementioned functional group, for example, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, a group formed by an anhydride of an acid group, etc. are mentioned, preferably a phenolic hydroxyl group, an amino group, or an acid group formed by an anhydride The formed group is more preferably a phenolic hydroxyl group or an amino group.

熱硬化劑(h2)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 (h2), as phenolic curing agents having phenolic hydroxyl groups, for example, polyfunctional phenol resins, biphenols, novolac type phenol resins, dicyclopentadiene phenol resins, and aralkylphenols can be cited Resin etc.

熱硬化劑(h2)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 the thermosetting agent (h2), as an amine-based curing agent having an amine group, for example, dicyandiamine (hereinafter, abbreviated as "DICY") and the like can be cited.

熱硬化劑(h2)亦可具有不飽和烴基。 The thermal hardener (h2) may also have an unsaturated hydrocarbon group.

作為具有不飽和烴基之熱硬化劑(h2)，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。 As the thermosetting agent (h2) having an unsaturated hydrocarbon group, for example, a compound in which a part of the hydroxyl group of a phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a group having an unsaturated hydrocarbon group is directly bonded to the aromatic ring of the phenol resin Compounds and so on.

熱硬化劑(h2)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 (h2) is the same as the unsaturated hydrocarbon group in the aforementioned epoxy resin having an unsaturated hydrocarbon group.

於使用酚系硬化劑作為熱硬化劑(h2)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(h2)較佳為軟化點或玻璃轉移溫度高的酚系硬化劑。 When a phenolic hardener is used as the thermosetting agent (h2), in terms of improving the peelability of the protective film from the supporting sheet, the thermosetting agent (h2) is preferably a phenol with a high softening point or glass transition temperature. Department of hardener.

熱硬化劑(h2)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 (h2), for example, the number average molecular weight of resin components such as polyfunctional phenol resin, novolak type phenol resin, dicyclopentadiene phenol resin, and aralkylphenol resin is preferably 300 to 30,000, and more It is preferably 400 to 10,000, particularly preferably 500 to 3,000.

熱硬化劑(h2)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 (h2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamine is not particularly limited, and for example, it is preferably 60 to 500.

熱硬化劑(h2)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，該等之組合及比率可任意選擇。 The thermosetting agent (h2) may be used singly, or two or more types may be used in combination. When two or more types are used in combination, these combinations and ratios can be arbitrarily selected.

於使用熱硬化性成分(h)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中，熱硬化劑(h2)的含量相對於環氧樹脂(h1)的含量100質量份，較佳為0.01質量份至20質量份。 In the case of using the thermosetting component (h), in the protective film forming composition (IV-1) and the protective film forming film, the content of the thermosetting agent (h2) is relative to the content of the epoxy resin (h1) 100 parts by mass, preferably 0.01 parts by mass to 20 parts by mass.

於使用熱硬化性成分(h)之情形時，保護膜形成用組 成物(IV-1)及保護膜形成用膜中，熱硬化性成分(h)的含量(例如，環氧樹脂(h1)及熱硬化劑(h2)的總含量)相對於不具有能量線硬化性基之聚合物(b)的含量100質量份，較佳為1質量份至500質量份。 When the thermosetting component (h) is used, the protective film formation group In the finished product (IV-1) and the film for forming a protective film, the content of the thermosetting component (h) (for example, the total content of the epoxy resin (h1) and the thermosetting agent (h2)) relative to the non-energy ray The content of the polymer (b) of the curable base is 100 parts by mass, preferably 1 part by mass to 500 parts by mass.

[通用添加劑(z)] [General additives (z)]

通用添加劑(z)可為公知的通用添加劑，可根據目的而任意選擇，並無特別限定，作為較佳的通用添加劑，例如可列舉：塑化劑、抗靜電劑、抗氧化劑、吸氣劑等。 The general-purpose additives (z) can be known general-purpose additives, and can be arbitrarily selected according to the purpose, and are not particularly limited. Preferred general-purpose additives include, for example, plasticizers, antistatic agents, antioxidants, getters, etc. .

保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之通用添加劑(z)可僅為1種，亦可為2種以上，於為2種以上之情形時，該等之組合及比率可任意選擇。 The protective film forming composition (IV-1) and the general additive (z) contained in the protective film forming film may be only one type or two or more types. In the case of two or more types, these The combination and ratio can be chosen arbitrarily.

於使用通用添加劑(z)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中的通用添加劑(z)的含量並無特別限定，根據目的適宜選擇即可。 When a general-purpose additive (z) is used, the content of the general-purpose additive (z) in the protective film forming composition (IV-1) and the protective film forming 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(IV-1)較佳為進而含有溶劑。含有溶劑之保護膜形成用組成物(IV-1)的操作性良好。 The composition (IV-1) for forming a protective film preferably further contains a solvent. The solvent-containing protective film forming composition (IV-1) has good operability.

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. Preferred examples of the aforementioned solvent include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), 1 -Alcohols such as butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; dimethylformamide, N-methyl Pyrrolidone and other amides (compounds with amide bonds) and the like.

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，於為2種以上之情形時，該等之組合及比率可任意選擇。 The solvent contained in the composition (IV-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 can be arbitrarily selected.

就可將保護膜形成用組成物(IV-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(IV-1)所含有之溶劑較佳為甲基乙基酮、甲苯或乙酸乙酯等。 The solvent contained in the protective film forming composition (IV-1) is preferably methyl ethyl ketone in terms of allowing the components contained in the protective film forming composition (IV-1) to be more uniformly mixed. , Toluene or ethyl acetate, etc.

<<保護膜形成用組成物的製造方法>> <<Production method of protective film forming composition>>

保護膜形成用組成物(IV-1)等保護膜形成用組成物係藉由將用以構成該保護膜形成用組成物之各成分加以調配而獲得。 The composition for protective film formation, such as the composition for protective film formation (IV-1), is obtained by mixing each component which comprises this composition for protective film formation.

調配各成分時的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 when 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，亦即，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，亦即，不將溶劑以外的任一種調配成分預先稀釋而將溶劑與該等調配成分混合。 When a solvent is used, it can be used in the following manner, that is, mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance; it can also be used in the following manner, that is, without Any preparation component other than the solvent is diluted in advance, and the solvent is mixed with the preparation component.

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 each component during compounding is not particularly limited, and can be appropriately selected from the following known methods: a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer; mixing by applying ultrasonic waves The method and so on.

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，則並無特別限定，適宜調節即可，溫度較佳為15℃至30℃。 Regarding the temperature and time when each component is added and mixed, as long as it does not deteriorate each compounding component, it is not particularly limited and may be adjusted appropriately, and the temperature is preferably 15°C to 30°C.

與本發明之保護膜形成用複合片同樣地，作為貼附於半導體晶圓或半導體晶片中的與電路面為相反側的背面，且於支持片上具備顯示接著性之層之複合片，有切晶黏晶片。 As with the composite sheet for forming a protective film of the present invention, as a composite sheet attached to a semiconductor wafer or a semiconductor wafer on the back side opposite to the circuit surface, and having a layer showing adhesiveness on a support sheet, there are cuts Crystal-bonded wafers.

但是，切晶黏晶片所具備之接著劑層發揮以下功能，亦即，與半導體晶片一起自支持片拾取後，將該半導體晶片安裝於基板、引線框架、或其他半導體晶片等時，作為接著劑之功能。另一方面，關於本發明之保護膜形成用複合片中的保護膜形成用膜，就與半導體晶片一起自支持片拾取之方面而言，與前述接著劑層相同，但最終藉由硬化而成為保護膜，具有保護經貼附之半導體晶片的背面之功能。如此，本發明中的保護膜形成用膜的用途與切晶黏晶片中的接著劑層不同，當然所要求之性能亦不同。並且，反映該用途之差異，通常，若與切晶黏晶片中的接著劑層進行比較，則保護膜形成用膜存在較硬且不易拾取之傾向。因此，通常難以將切晶黏晶片中的接著劑層直接轉用作保護膜形成用複合片中的保護膜形成用膜。本發明之保護膜形成用複合片具備能量線硬化性之保護膜形成用膜，關於附有保護膜的半導體晶片的拾取適性，空前之極其優異。 However, the adhesive layer of the dicing die has the following function, that is, when the semiconductor wafer is picked up from the support sheet together with the semiconductor wafer, it is used as an adhesive when the semiconductor wafer is mounted on a substrate, a lead frame, or other semiconductor wafers, etc. The function. On the other hand, the film for forming a protective film in the composite sheet for forming a protective film of the present invention is the same as the aforementioned adhesive layer in terms of picking up from the support sheet together with the semiconductor wafer, but is finally cured by curing. The protective film has the function of protecting the back surface of the attached semiconductor chip. In this way, the application of the protective film forming film in the present invention is different from that of the adhesive layer in the dicing die, and of course the required performance is also different. In addition, reflecting the difference in the application, generally, when compared with the adhesive layer in the dicing die, the protective film formation film tends to be harder and difficult to pick up. Therefore, it is generally difficult to directly transfer the adhesive layer in the diced die-bonded wafer to the protective film formation film in the protective film formation composite sheet. The composite sheet for forming a protective film of the present invention is a film for forming a protective film having energy ray curability, and the pick-up suitability of a semiconductor wafer with a protective film is unprecedentedly excellent.

本發明之一態樣中，本發明之保護膜形成用複合片具有黏著劑層，該黏著劑層含有丙烯酸系聚合物(重量平均分子量：600000)(90質量份至110質量份，較佳為100質量份)、及3官能苯二甲基二異氰酸酯系交聯劑(10.0質量份至11.4質量份，較佳為10.7質量份)，前述丙烯酸系聚合物係丙烯酸-2-乙基己酯(31質量份至41質量份，較佳為36質量份)、丙烯酸丁酯(54質量份至64質量份，較佳為59質量份)、及丙烯酸-2-羥基乙酯(3質量份至7質量份，較佳為5質量份)進行共聚合而成。 In one aspect of the present invention, the composite sheet for forming a protective film of the present invention has an adhesive layer containing an acrylic polymer (weight average molecular weight: 600,000) (90 parts by mass to 110 parts by mass, preferably 100 parts by mass), and a trifunctional xylylene diisocyanate-based crosslinking agent (10.0 parts by mass to 11.4 parts by mass, preferably 10.7 parts by mass), the aforementioned acrylic polymer-based 2-ethylhexyl acrylate ( 31 parts by mass to 41 parts by mass, preferably 36 parts by mass), butyl acrylate (54 parts by mass to 64 parts by mass, preferably 59 parts by mass), and 2-hydroxyethyl acrylate (3 parts by mass to 7 parts by mass) Parts by mass, preferably 5 parts by mass) through copolymerization.

另外，本發明之一態樣中，本發明之保護膜形成用複合片具有黏著劑層，該黏著劑層含有丙烯酸系聚合物(重量平均分子量：800000)(90質量份至110質量份，較佳為100質量份)、及3官能苯二甲基二異氰酸酯系交聯劑(0.3質量份至0.7質量份，較佳為0.5質量份)，前述丙烯酸系聚合物係丙烯酸丁酯(90質量份至100質量份，較佳為95質量份)及丙烯酸-2-羥基乙酯(3質量份至7質量份，較佳為5質量份)進行共聚合而成。 In addition, in one aspect of the present invention, the composite sheet for forming a protective film of the present invention has an adhesive layer containing an acrylic polymer (weight average molecular weight: 800,000) (90 parts by mass to 110 parts by mass, more than Preferably 100 parts by mass), and a trifunctional xylylene diisocyanate crosslinking agent (0.3 parts by mass to 0.7 parts by mass, preferably 0.5 parts by mass), the aforementioned acrylic polymer-based butyl acrylate (90 parts by mass) To 100 parts by mass, preferably 95 parts by mass) and 2-hydroxyethyl acrylate (3 parts by mass to 7 parts by mass, preferably 5 parts by mass) are copolymerized.

另外，本發明之一態樣中，本發明之保護膜形成用複合片具有黏著劑層，該黏著劑層含有側鏈具有甲基丙烯醯氧基之能量線硬化性丙烯酸系聚合物(重量平均分子量：600000)(90質量份至110質量份，較佳為100質量份)、 作為光聚合起始劑之1-羥基-環己基-苯基-酮(0.1質量份至0.5質量份，較佳為0.3質量份)、及作為交聯劑之甲苯二異氰酸酯系交聯劑(0.1質量份至0.3質量份，較佳為0.2質量份)，前述能量線硬化性丙烯酸系聚合物係使丙烯酸-2-乙基己酯(50質量份至70質量份，較佳為60質量份)、丙烯酸甲酯(20質量份至40質量份，較佳為30質量份)、及丙烯酸-2-羥基乙酯(8質量份至12質量份，較佳為10質量份)進行共聚合而成之丙烯酸系聚合物，與異氰酸2-甲基丙烯醯氧基乙酯(相對於前述丙烯酸系共聚物中的源自丙烯酸-2-羥基乙酯之羥基的總莫耳數，異氰酸2-甲基丙烯醯氧基乙酯中的異氰酸酯基的總莫耳數成為0.8倍之量)反應而獲得。 In addition, in one aspect of the present invention, the composite sheet for forming a protective film of the present invention has an adhesive layer containing an energy-ray curable acrylic polymer having a methacryloxy group in its side chain (weight average Molecular weight: 600,000) (90 parts by mass to 110 parts by mass, preferably 100 parts by mass), 1-hydroxy-cyclohexyl-phenyl-ketone (0.1 parts by mass to 0.5 parts by mass, preferably 0.3 parts by mass) as a photopolymerization initiator, and toluene diisocyanate-based crosslinking agent (0.1 parts by mass) as a crosslinking agent Parts by mass to 0.3 parts by mass, preferably 0.2 parts by mass), the aforementioned energy ray curable acrylic polymer is 2-ethylhexyl acrylate (50 parts by mass to 70 parts by mass, preferably 60 parts by mass) , Methyl acrylate (20 parts by mass to 40 parts by mass, preferably 30 parts by mass), and 2-hydroxyethyl acrylate (8 parts by mass to 12 parts by mass, preferably 10 parts by mass) are copolymerized The acrylic polymer, and 2-methacryloxyethyl isocyanate (relative to the total number of moles of hydroxyl groups derived from 2-hydroxyethyl acrylate in the aforementioned acrylic copolymer, isocyanic acid The total molar number of isocyanate groups in 2-methacryloxyethyl is 0.8 times) to obtain the reaction.

◇保護膜形成用複合片的製造方法 ◇Method for manufacturing composite sheet for forming protective film

本發明之保護膜形成用複合片可藉由將上述各層以成為對應的位置關係之方式依序積層而製造。各層之形成方法如前文所說明。 The composite sheet for forming a protective film of the present invention can be manufactured by sequentially stacking the above-mentioned layers so as to have a corresponding positional relationship. The formation method of each layer is as described above.

例如，製造支持片時，於基材上積層黏著劑層之情形時，於基材上塗敷上述之黏著劑組成物，視需要使之乾燥即可。 For example, in the case of laminating an adhesive layer on a substrate when manufacturing a support sheet, the above-mentioned adhesive composition may be coated on the substrate and dried if necessary.

另一方面，例如，於已積層於基材上之黏著劑層上進而積層保護膜形成用膜之情形時，可於黏著劑層上塗敷保護膜形成用組成物，直接形成保護膜形成用膜。保護膜形 成用膜以外之層亦可使用用以形成該層之組成物，利用同樣的方法，於黏著劑層上積層該層。如此，於使用任一種組成物，形成連續之2層之積層結構之情形時，可於由前述組成物形成之層上，進而塗敷組成物而新形成層。但是，較佳為藉由下述方式而形成連續之2層之積層結構，亦即，於另一剝離膜上，使用前述組成物，預先形成該等2層中後積層之層，將該已形成之層中的與和前述剝離膜接觸之側為相反側的露出面，與既已形成之其餘層的露出面貼合。此時，前述組成物較佳為塗敷於剝離膜的剝離處理面。形成積層結構後，視需要移除剝離膜即可。 On the other hand, for example, when the protective film forming film is laminated on the adhesive layer already laminated on the base material, the protective film forming composition can be coated on the adhesive layer to directly form the protective film forming film . Protective film shape Layers other than the used film can also use the composition used to form the layer, and use the same method to laminate the layer on the adhesive layer. In this way, when any composition is used to form a continuous two-layer laminated structure, the layer formed of the aforementioned composition can be coated with the composition to form a new layer. However, it is preferable to form a continuous two-layer laminated structure by using the aforementioned composition on another release film to pre-form the second laminated layer of the two layers, and then Among the formed layers, the exposed surface on the opposite side to the side in contact with the release film is bonded to the exposed surface of the remaining layer that has already been formed. In this case, the aforementioned composition is preferably applied to the release-treated surface of the release film. After the build-up structure is formed, the release film can be removed as necessary.

例如，於製造於基材上積層黏著劑層，於前述黏著劑層上積層保護膜形成用膜而成之保護膜形成用複合片(支持片為基材及黏著劑層之積層物之保護膜形成用複合片)之情形時，於基材上塗敷黏著劑組成物，視需要使之乾燥，藉此於基材上預先積層黏著劑層，另行於剝離膜上塗敷保護膜形成用組成物，視需要使之乾燥，藉此於剝離膜上預先形成保護膜形成用膜。然後，將該保護膜形成用膜的露出面與已積層於基材上之黏著劑層的露出面貼合，於黏著劑層上積層保護膜形成用膜，藉此獲得保護膜形成用複合片。 For example, in the manufacture of a composite sheet for forming a protective film formed by laminating an adhesive layer on a base material and laminating a protective film forming film on the aforementioned adhesive layer (the support sheet is a protective film for the laminate of the base material and the adhesive layer In the case of forming a composite sheet), apply the adhesive composition on the substrate and dry it as necessary, thereby preliminarily laminating the adhesive layer on the substrate, and separately coating the protective film forming composition on the release film, If necessary, it is dried to form a protective film forming film on the release film in advance. Then, the exposed surface of the protective film forming film is bonded to the exposed surface of the adhesive layer laminated on the substrate, and the protective film forming film is laminated on the adhesive layer, thereby obtaining a composite sheet for forming a protective film .

再者，於基材上積層黏著劑層之情形時，如上所述，亦可代替於基材上塗敷黏著劑組成物之方法，於剝離膜上 塗敷黏著劑組成物，視需要使之乾燥，藉此於剝離膜上預先形成黏著劑層，將該層的露出面與基材的一表面貼合，藉此於基材上積層黏著劑層。 Furthermore, when the adhesive layer is laminated on the substrate, as described above, it can also replace the method of applying the adhesive composition on the substrate, and apply it on the release film. Apply the adhesive composition and dry it if necessary, thereby forming an adhesive layer on the release film in advance, and attaching the exposed surface of the layer to a surface of the substrate, thereby depositing an adhesive layer on the substrate .

任一種方法中，均於形成目標積層結構後的任意時間點移除剝離膜即可。 In either method, it is sufficient to remove the release film at any point after the target build-up structure is formed.

如此，構成保護膜形成用複合片之基材以外的層均可利用以下方法積層，亦即，預先形成於剝離膜上，再貼合於目標層的表面，因此視需要適宜選擇採用此種步驟之層，製造保護膜形成用複合片即可。 In this way, all layers other than the base material constituting the protective film forming composite sheet can be laminated by the following method, that is, preliminarily formed on the release film, and then bonded to the surface of the target layer. Therefore, this step can be appropriately selected and adopted as needed. It is sufficient to manufacture a composite sheet for forming a protective film.

再者，保護膜形成用複合片通常以如下狀態保管，亦即，於該保護膜形成用複合片中的與支持片為相反側的最表層(例如，保護膜形成用膜)的表面貼合有剝離膜之狀態。因此，亦可藉由下述方式而獲得保護膜形成用複合片，亦即，於該剝離膜(較佳為該剝離膜的剝離處理面)上，塗敷保護膜形成用組成物等用以形成構成最表層之層之組成物，視需要使之乾燥，藉此於剝離膜上預先形成構成最表層之層，於該層中的與和剝離膜接觸之側為相反側的露出面上，利用上述任一種方法積層其餘各層，不移除剝離膜而保持貼合狀態不變。 In addition, the composite sheet for forming a protective film is usually stored in a state in which the composite sheet for forming a protective film is bonded to the surface of the outermost layer (for example, the film for forming a protective film) on the side opposite to the supporting sheet in the composite sheet for forming a protective film There is a state of peeling film. Therefore, a composite sheet for forming a protective film can also be obtained by coating the release film (preferably the release-treated surface of the release film) with a protective film forming composition, etc. The composition that forms the layer that constitutes the outermost layer is dried as necessary to form a layer that constitutes the outermost layer on the release film in advance, and the exposed side of the layer that is in contact with the release film is the opposite side. Use any of the above methods to laminate the remaining layers without removing the release film and keep the attached state unchanged.

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

本發明之保護膜形成用複合片例如可利用以下所示 之方法使用。 The composite sheet for forming a protective film of the present invention can be used, for example, as shown below The method is used.

亦即，將保護膜形成用複合片藉由該保護膜形成用複合片之保護膜形成用膜貼附於半導體晶圓的背面(與電極形成面為相反側的面)。繼而，對保護膜形成用膜照射能量線，使保護膜形成用膜硬化而成為保護膜。繼而，藉由切割，將半導體晶圓連同保護膜一起分割而製成半導體晶片。然後，將半導體晶片，保持貼附有該保護膜之狀態(亦即，以附有保護膜的半導體晶片之形式)，自支持片拉離而進行拾取。 That is, the composite sheet for protective film formation is attached to the back surface of the semiconductor wafer (the surface opposite to the electrode formation surface) through the protective film formation film of the composite sheet for protective film formation. Then, the film for protective film formation is irradiated with energy rays to harden the film for protective film formation to become a protective film. Then, by dicing, the semiconductor wafer and the protective film are divided together to form a semiconductor wafer. Then, the semiconductor wafer is kept in a state where the protective film is attached (that is, in the form of a semiconductor wafer with a protective film), and is pulled away from the support sheet to be picked up.

以下，利用與先前法相同的方法，將所獲得之附有保護膜的半導體晶片的半導體晶片倒裝晶片連接於基板的電路面後，藉此製成半導體封裝。然後，使用該半導體封裝，製作目標半導體裝置即可。 Hereinafter, using the same method as the previous method, the obtained semiconductor wafer of the semiconductor wafer with a protective film is flip-chip connected to the circuit surface of the substrate, thereby forming a semiconductor package. Then, the semiconductor package can be used to manufacture the target semiconductor device.

[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 through specific embodiments. However, the present invention is not limited at all by the examples shown below.

以下表示用於製造保護膜形成用組成物之成分。 The components used to manufacture the protective film forming composition are shown below.

‧能量線硬化性成分 ‧Energy ray hardening ingredients

(a2)-1：三環癸烷二羥甲基二丙烯酸酯(日本化藥公司製造之「KAYARAD R-684」，2官能紫外線硬化性化合物，分子量304)。 (a2)-1: Tricyclodecane dimethylol diacrylate ("KAYARAD R-684" manufactured by Nippon Kayaku Co., Ltd., a bifunctional ultraviolet curable compound, molecular weight 304).

‧不具有能量線硬化性基之聚合物 ‧Polymer without energy ray hardening base

(b)-1：使丙烯酸丁酯(以下，簡稱為「BA」)(10質量份)、丙烯酸甲酯(以下，簡稱為「MA」)(70質量份)、甲基丙烯酸縮水甘油酯(以下，簡稱為「GMA」)(5質量份)及丙烯酸-2-羥基乙酯(以下，簡稱為「HEA」)(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300000，玻璃轉移溫度-1℃)。 (b)-1: Make butyl acrylate (hereinafter referred to as "BA") (10 parts by mass), methyl acrylate (hereinafter referred to as "MA") (70 parts by mass), and glycidyl methacrylate ( Hereinafter, referred to as "GMA") (5 parts by mass) and 2-hydroxyethyl acrylate (hereinafter referred to as "HEA") (15 parts by mass) copolymerized acrylic resin (weight average molecular weight 300,000, Glass transition temperature -1°C).

‧光聚合起始劑 ‧Photopolymerization initiator

(c)-1：2-(二甲基胺基)-1-(4-嗎啉基苯基)-2-苄基-1-丁酮(BASF公司製造之「Irgacure369」)。 (c)-1: 2-(Dimethylamino)-1-(4-morpholinylphenyl)-2-benzyl-1-butanone ("Irgacure369" manufactured by BASF Corporation).

(c)-2：乙酮，1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)(BASF公司製造之「IrgacureOXE02」)。 (c)-2: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime ) ("IrgacureOXE02" manufactured by BASF Company).

‧填充材料 ‧Filler

(d)-1：二氧化矽填料(溶融石英填料，平均粒徑8μm)。 (d)-1: Silica filler (fused silica filler, average particle size 8μm).

‧偶合劑 ‧Coupling agent

(e)-1：3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學工業公司製造之「KBM-503」，矽烷偶合劑)。 (e)-1: 3-methacryloxypropyltrimethoxysilane ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent).

‧著色劑 ‧Colorant

(g)-1：將酞菁系藍色色素(Pigment Blue 15：3)32質量份、異吲哚啉酮系黃色色素(Pigment Yellow 139)18質量份、及蒽醌系紅色色素(Pigment Red 177)50質量份進行混合，以前述3種色素的合計量/苯乙烯丙烯酸樹脂量=1/3(質量比)之方式進行顏料化而獲得之顏料。 (g)-1: 32 parts by mass of phthalocyanine-based blue pigment (Pigment Blue 15: 3), 18 parts by mass of isoindolinone-based yellow pigment (Pigment Yellow 139), and anthraquinone-based red pigment (Pigment Red 177) A pigment obtained by mixing 50 parts by mass, and pigmenting so that the total amount of the aforementioned 3 kinds of pigments/the amount of styrene acrylic resin=1/3 (mass ratio).

[實施例1] [Example 1]

<保護膜形成用複合片之製造> <Manufacturing of Composite Sheet for Forming Protective Film>

(保護膜形成用組成物(IV-1)之製造) (Manufacturing of protective film forming composition (IV-1))

使能量線硬化性成分(a2)-1(20質量份)、聚合物(b)-1(22質量份)、光聚合起始劑(c)-1(0.3質量份)、光聚合起始劑(c)-2(0.3質量份)、填充材料(d)-1(56質量份)、偶合劑(e)-1(0.4質量份)、及著色劑(g)-1(2質量份)，溶解或分散於甲基乙基酮中，於23℃下進行攪拌，藉此製備固形物成分濃度為50質量%之保護膜形成用組成物(IV-1)。 Make energy ray curable component (a2)-1 (20 parts by mass), polymer (b)-1 (22 parts by mass), photopolymerization initiator (c)-1 (0.3 parts by mass), photopolymerization starter Agent (c)-2 (0.3 parts by mass), filler (d)-1 (56 parts by mass), coupling agent (e)-1 (0.4 parts by mass), and coloring agent (g)-1 (2 parts by mass) ), dissolved or dispersed in methyl ethyl ketone, and stirred at 23°C to prepare a protective film forming composition (IV-1) having a solid content of 50% by mass.

(黏著劑組成物(I-4)之製造) (Manufacturing of Adhesive Composition (I-4))

製備固形物成分濃度為30質量%之非能量線硬化性之黏著劑組成物(I-4)，該黏著劑組成物(I-4)含有丙烯酸系聚合物(100質量份，固形物成分)、及3官能苯二甲基二異氰酸酯系交聯劑(三井武田化學公司製造之「Takenate D110N」)(10.7質量份，固形物成分)，進而含有作為溶劑之甲基乙基酮。前述丙烯酸系聚合物係使丙烯酸-2-乙基己酯(以下，簡稱為「2EHA」)(36質量份)、BA(59質量份)、及HEA(5質量份)進行共聚合而成，且重量平均分子量為600000。 A non-energy-ray-curable adhesive composition (I-4) with a solid content concentration of 30% by mass was prepared, and the adhesive composition (I-4) contained an acrylic polymer (100 parts by mass, solid content) , And a trifunctional xylylene diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (10.7 parts by mass, solid content), and further contains methyl ethyl ketone as a solvent. The aforementioned acrylic polymer is obtained by copolymerizing 2-ethylhexyl acrylate (hereinafter referred to as "2EHA") (36 parts by mass), BA (59 parts by mass), and HEA (5 parts by mass), And the weight average molecular weight is 600,000.

(支持片之製造) (Support film manufacturing)

於聚對苯二甲酸乙二酯製膜的單面經聚矽氧處理進 行剝離處理之剝離膜(Lintec公司製造之「SP-PET381031」，厚度38μm)的前述剝離處理面，塗敷上述所獲得之黏著劑組成物(I-4)，於120℃下加熱乾燥2分鐘，藉此形成厚度10μm之非能量線硬化性之黏著劑層。 The single side of the polyethylene terephthalate film is treated with silicone Apply the adhesive composition (I-4) obtained above on the peeling surface of the peeling film ("SP-PET381031" manufactured by Lintec, thickness 38μm) of peeling treatment, and heat and dry at 120°C for 2 minutes , Thereby forming a non-energy ray-curable adhesive layer with a thickness of 10 μm.

繼而，於該黏著劑層的露出面貼合作為基材之聚丙烯系膜(楊氏率400MPa，厚度80μm)，藉此獲得於前述基材的一表面上具備前述黏著劑層之支持片(10)-1。 Then, a polypropylene film (Young's rate 400MPa, thickness 80μm) as a base material was pasted on the exposed surface of the adhesive layer, thereby obtaining a support sheet with the adhesive layer on one surface of the base material ( 10)-1.

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

於聚對苯二甲酸乙二酯製膜的單面經聚矽氧處理進行剝離處理之剝離膜(Lintec公司製造之「SP-PET381031」，厚度38μm)的前述剝離處理面，藉由刀式塗佈機塗敷上述所獲得之保護膜形成用組成物(IV-1)，於100℃下乾燥2分鐘，藉此製作厚度25μm之能量線硬化性之保護膜形成用膜(13)-1。 On one side of the polyethylene terephthalate film, the peeling film (SP-PET381031 made by Lintec, thickness 38μm) that was peeled off by silicone treatment was applied to the peeling surface by knife coating. The protective film forming composition (IV-1) obtained above was coated with a cloth machine and dried at 100° C. for 2 minutes to produce an energy ray curable protective film forming film (13)-1 with a thickness of 25 μm.

繼而，自上述所獲得之支持片(10)-1中的黏著劑層移除剝離膜，於該黏著劑層的露出面貼合上述所獲得之保護膜形成用膜(13)-1的露出面，製作基材、黏著劑層、保護膜形成用膜(13)-1及剝離膜於該等的厚度方向上依序積層而成之保護膜形成用複合片。所獲得之保護膜形成用複合片之構成示於表1。 Then, the release film is removed from the adhesive layer in the support sheet (10)-1 obtained above, and the exposed surface of the adhesive layer is attached to the exposed surface of the protective film forming film (13)-1 obtained above On the surface, a composite sheet for forming a protective film is produced in which a substrate, an adhesive layer, a film for forming a protective film (13)-1, and a release film are sequentially laminated in the thickness direction. Table 1 shows the composition of the obtained composite sheet for forming a protective film.

<保護膜形成用複合片之評價> <Evaluation of Composite Sheet for Forming Protective Film>

(保護膜與支持片之間的黏著力) (Adhesion between protective film and support sheet)

將上述所獲得之保護膜形成用複合片裁斷成25mm×140mm之大小，自保護膜形成用複合片移除剝離膜，使保護膜形成用膜(13)-1的一表面露出，作為硬化前試片。另一方面，準備於SUS(stainless steel，不鏽鋼)製支持板(70mm×150mm)的表面貼合有雙面黏著帶之試片。然後，使用貼合機(Fuji公司製造之「LAMIPACKER LPD3214」)，將硬化前試片之保護膜形成用膜(13)-1的露出面貼附於支持板上的前述雙面黏著帶，藉此於支持板經由雙面黏著帶貼附硬化前試片。 The protective film forming composite sheet obtained above was cut into a size of 25mm×140mm, and the release film was removed from the protective film forming composite sheet to expose one surface of the protective film forming film (13)-1 as the pre-curing Audition. On the other hand, a test piece with a double-sided adhesive tape attached to the surface of a support plate (70mm×150mm) made of SUS (stainless steel) was prepared. Then, using a laminating machine ("LAMIPACKER LPD3214" manufactured by Fuji), the exposed surface of the protective film forming film (13)-1 of the test piece before curing was attached to the aforementioned double-sided adhesive tape on the support plate. The test piece before hardening is attached to the support board via a double-sided adhesive tape.

繼而，使用紫外線照射裝置(Lintec公司製造之「RAD2000m/8」)，於照度195mW/cm2、光量170mJ/cm2之條件下，對硬化前試片照射紫外線，藉此使保護膜形成用膜(13)-1硬化，獲得硬化後試片。 Then, the ultraviolet irradiation device (manufactured by the Lintec Company "RAD2000m / 8") at an illuminance 195mW / cm 2, light quantity of 170mJ / cm condition 2, the irradiating ultraviolet test piece before the hardening, whereby the protective film formation film (13)-1 Hardened to obtain a hardened test piece.

繼而，使用精密萬能試驗機(島津製作所製造之「Autograph AG-IS」)，進行下述拉伸試驗，亦即，於剝離角度180°、測定溫度23℃、拉伸速度300mm/min之條件下，將支持片(10)-1(硬化後之黏著劑層與基材之積層物)自保護膜形成用膜(13)-1硬化而成之保護膜剝離，測定此時的荷重(剝離力)，設為保護膜形成用膜(13)-1硬化而成之保護膜與支持片(10)-1之間的黏著力。結果示於表1。 Then, using a precision universal testing machine ("Autograph AG-IS" manufactured by Shimadzu Corporation), the following tensile test was performed, that is, under the conditions of a peeling angle of 180°, a measurement temperature of 23°C, and a tensile speed of 300 mm/min , Peel the support sheet (10)-1 (the laminate of the cured adhesive layer and the base material) from the protective film cured by the protective film forming film (13)-1, and measure the load (peeling force) ), set as the adhesive force between the protective film formed by curing the protective film forming film (13)-1 and the support sheet (10)-1. The results are shown in Table 1.

(切割時矽晶片之飛散之抑制) (Suppression of the scattering of silicon chips during cutting)

將上述所獲得之保護膜形成用複合片，藉由該保護膜形成用複合片的保護膜形成用膜(13)-1，貼附於6吋矽晶圓(厚度100μm)之#2000研磨面，進而將該片固定於環狀框，靜置30分鐘。 The composite sheet for forming a protective film obtained above was attached to the #2000 polished surface of a 6-inch silicon wafer (thickness 100μm) using the protective film forming film (13)-1 of the composite sheet for forming a protective film , And then fix the sheet to the ring frame and let it stand for 30 minutes.

繼而，使用紫外線照射裝置(Lintec公司製造之「RAD2000m/8」)，於照度195mW/cm2、光量170mJ/cm2之條件下，自支持片(10)-1側對保護膜形成用複合片照射紫外線，藉此使保護膜形成用膜(13)-1硬化，成為保護膜。 Then, the ultraviolet irradiation device (manufactured by the Lintec Company "RAD2000m / 8") at an illuminance 195mW / cm 2, light quantity of 170mJ / cm condition 2, the self-supporting sheet (10) -1-side protective film of the composite sheet is formed By irradiating ultraviolet rays, the film (13)-1 for forming a protective film is cured to become a protective film.

繼而，使用切割刀片，將矽晶圓連同保護膜一起切割而單片化，獲得5mm×5mm之矽晶片。此時，目視確認有無矽晶片自支持片之飛散，將完全無矽晶片之飛散之情形判定為「○」，將有少許矽晶片之飛散之情形判定為「×」，對切割適性進行評價。結果示於表1。表1中的「晶片之飛散之抑制」一欄之記載為相應的結果。 Then, using a dicing blade, the silicon wafer together with the protective film are cut and singulated to obtain a 5mm×5mm silicon wafer. At this time, visually confirm whether there is any scattering of silicon wafers from the supporting sheet, judge that there is no scattering of silicon wafers as "○", and judge that there is a little scattering of silicon wafers as "×", and evaluate the dicing suitability. The results are shown in Table 1. The entry in the column of "Suppression of chip scattering" in Table 1 is the corresponding result.

(切割時切削水之浸入之抑制) (Suppression of cutting water immersion during cutting)

將上述所獲得之保護膜形成用複合片，藉由該保護膜形成用複合片之保護膜形成用膜(13)-1，貼附於6吋矽晶圓(厚度100μm)之#2000研磨面，進而將該片固定於環狀框，靜置30分鐘。 The composite sheet for forming a protective film obtained above is attached to the #2000 polished surface of a 6-inch silicon wafer (thickness 100μm) by using the protective film forming film (13)-1 of the composite sheet for forming a protective film , And then fix the piece to the ring frame and let it stand for 30 minutes.

繼而，使用紫外線照射裝置(Lintec公司製造之「RAD2000m/8」)，於照度195mW/cm2、光量170mJ/cm2之條件下，自支持片(10)-1側對保護膜形成用複合片照射紫外線，藉此使保護膜形成用膜(13)-1硬化，成為保護膜。 Then, the ultraviolet irradiation device (manufactured by the Lintec Company "RAD2000m / 8") at an illuminance 195mW / cm 2, light quantity of 170mJ / cm condition 2, the self-supporting sheet (10) -1-side protective film of the composite sheet is formed By irradiating ultraviolet rays, the film (13)-1 for forming a protective film is cured to become a protective film.

繼而，使用切割刀片，將矽晶圓連同保護膜一起切割而進行單片化，獲得5mm×5mm之矽晶片。此時，目視確認有無切削水之浸入，將完全無切削水之浸入之情形判定為「○」，將有少許切削水之浸入之情形判定為「×」，對切割適性進行評價。結果示於表1。表1中的「切削水之浸入之抑制」一欄之記載為相應的結果。 Then, a dicing blade is used to cut the silicon wafer together with the protective film to be singulated to obtain a 5mm×5mm silicon wafer. At this time, visually confirm whether there is cutting water intrusion, and judge the case where there is no cutting water intrusion as "○", and the case where there is little cutting water intrusion as "×", and evaluate the cutting suitability. The results are shown in Table 1. The entry in the column of "inhibition of cutting water immersion" in Table 1 is the corresponding result.

(拾取時矽晶片之剝離之評價) (Evaluation of the peeling of silicon wafer during pickup)

將上述所獲得之保護膜形成用複合片，藉由該保護膜形成用複合片之保護膜形成用膜(13)-1，貼附於6吋矽晶圓(厚度100μm)之#2000研磨面，進而將該片固定於環狀框，靜置30分鐘。 The composite sheet for forming a protective film obtained above is attached to the #2000 polished surface of a 6-inch silicon wafer (thickness 100μm) by using the protective film forming film (13)-1 of the composite sheet for forming a protective film , And then fix the piece to the ring frame and let it stand for 30 minutes.

繼而，使用紫外線照射裝置(Lintec公司製造之「RAD2000m/8」)，於照度195mW/cm2、光量170mJ/cm2之條件下，自支持片(10)-1側對保護膜形成用複合片照射紫外線，藉此使保護膜形成用膜(13)-1硬化，成為保護膜。 Then, the ultraviolet irradiation device (manufactured by the Lintec Company "RAD2000m / 8") at an illuminance 195mW / cm 2, light quantity of 170mJ / cm condition 2, the self-supporting sheet (10) -1-side protective film of the composite sheet is formed By irradiating ultraviolet rays, the film (13)-1 for forming a protective film is cured to become a protective film.

繼而，使用切割刀片，將矽晶圓連同保護膜一起切割而單片化，獲得5mm×5mm之矽晶片。 Then, using a dicing blade, the silicon wafer together with the protective film are cut and singulated to obtain a 5mm×5mm silicon wafer.

繼而，使用黏晶機(Canon Machinery公司製造之「BESTEM-D02」)，拾取20個附有保護膜之矽晶片。此時，目視確認有無晶片之剝離，將能夠剝離(拾取)之情形判定為「○」，將有少許無法剝離(拾取)之情形判定為「×」，對拾取適性進行評價。結果示於表1。表1中的「晶片之剝離」一欄之記載為相應的結果。 Then, a die bonder ("BESTEM-D02" manufactured by Canon Machinery) was used to pick up 20 silicon wafers with protective films. At this time, visually confirm whether there is peeling of the wafer, and judge whether peeling (pick up) is possible as "○", and if there is a little unpeelable (pick up), judge as "×", and evaluate the pick-up suitability. The results are shown in Table 1. The entry in the column of "chip peeling" in Table 1 is the corresponding result.

[實施例2] [Example 2]

<保護膜形成用複合片之製造> <Manufacturing of Composite Sheet for Forming Protective Film>

(黏著劑組成物(I-4)之製造) (Manufacturing of Adhesive Composition (I-4))

製備固形物成分濃度為30質量%之非能量線硬化性之黏著劑組成物(I-4)，該黏著劑組成物(I-4)含有丙烯酸系聚合物(100質量份，固形物成分)、及3官能苯二甲基二異氰酸酯系交聯劑(三井武田化學公司製造之「Takenate D110N」)(0.5質量份，固形物成分)，進而含有作為溶劑之甲基乙基酮。前述丙烯酸系聚合物係使BA(95質量份)及HEA(5質量份)進行共聚合而成，且重量平均分子量為800000。 A non-energy-ray-curable adhesive composition (I-4) with a solid content concentration of 30% by mass was prepared, and the adhesive composition (I-4) contained an acrylic polymer (100 parts by mass, solid content) , And a trifunctional xylylene diisocyanate-based crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (0.5 parts by mass, solid content), and further contains methyl ethyl ketone as a solvent. The aforementioned acrylic polymer is formed by copolymerizing BA (95 parts by mass) and HEA (5 parts by mass), and has a weight average molecular weight of 800,000.

(支持片之製造) (Support film manufacturing)

使用上述所獲得之黏著劑組成物(I-4)，除此方面以外，利用與實施例1相同的方法，於基材上形成厚度10μm之非能量線硬化性之黏著劑層，製作支持片(10)-2。 Using the adhesive composition (I-4) obtained above, except for this point, the same method as in Example 1 was used to form a non-energy ray-curable adhesive layer with a thickness of 10 μm on the substrate to produce a support sheet (10)-2.

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

使用上述所獲得之支持片(10)-2代替支持片(10)-1，除此方面以外，利用與實施例1相同的方法製造保護膜形成用複合片。所獲得之保護膜形成用複合片之構成示於表1。 The support sheet (10)-2 obtained above was used instead of the support sheet (10)-1, except for this point, the same method as in Example 1 was used to produce a composite sheet for forming a protective film. Table 1 shows the composition of the obtained composite sheet for forming a protective film.

<保護膜形成用複合片之評價> <Evaluation of Composite Sheet for Forming Protective Film>

針對上述所獲得之保護膜形成用複合片，利用與實施例1相同的方法進行評價。結果示於表1。 The composite sheet for forming a protective film obtained above was evaluated by the same method as in Example 1. The results are shown in Table 1.

[實施例3] [Example 3]

<保護膜形成用複合片之製造> <Manufacturing of Composite Sheet for Forming Protective Film>

(黏著劑組成物(I-2)之製造) (Manufacturing of Adhesive Composition (I-2))

製備固形物成分濃度為30質量%之能量線硬化性之黏著劑組成物(I-2)，該黏著劑組成物(I-2)含有丙烯酸系聚合物(100質量份，固形物成分)、光聚合起始劑(1-羥基-環己基-苯基-酮，BASF公司製造之「Irgacure184」)(0.3質量份，固形物成分)及甲苯二異氰酸酯系交聯劑(Nippon Polyurethane公司製造之「Coronate L」)(0.2質量份，固形物成分)，進而含有作為溶劑之甲基乙基酮。前述丙烯酸系聚合物係以下述方式獲得之於側鏈具有甲基丙烯醯氧基且重量平均分子量為600000之能量線硬化性丙烯酸系聚合物，亦即，使2EHA(60質量份)、丙烯酸甲酯(MA)(30質量份)、及HEA(10質量份)進行共聚合而成之丙烯酸系共聚物，與異氰酸2-甲基丙烯醯氧基乙酯(相對於前述丙烯酸系共聚物中的源自HEA之羥基的總莫耳數，異氰酸2-甲基丙烯醯氧基乙酯中的異氰酸酯基的總莫耳數成為0.8倍之量)反應。 An energy-ray curable adhesive composition (I-2) with a solid content concentration of 30% by mass was prepared. The adhesive composition (I-2) contained an acrylic polymer (100 parts by mass, solid content), Photopolymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, "Irgacure184" manufactured by BASF) (0.3 parts by mass, solid content) and toluene diisocyanate crosslinking agent (manufactured by Nippon Polyurethane) Coronate L”) (0.2 parts by mass, solid content), and further contains methyl ethyl ketone as a solvent. The aforementioned acrylic polymer is an energy ray curable acrylic polymer having a methacryloxy group in the side chain and having a weight average molecular weight of 600,000, which is obtained by making 2EHA (60 parts by mass), acrylic methyl Acrylic copolymer of ester (MA) (30 parts by mass) and HEA (10 parts by mass) copolymerized with 2-methacryloxyethyl isocyanate (relative to the aforementioned acrylic copolymer The total moles of the hydroxyl groups derived from HEA in, and the total moles of isocyanate groups in 2-methacryloxyethyl isocyanate becomes 0.8 times the amount).

(支持片之製造) (Support film manufacturing)

使用上述所獲得之黏著劑組成物(I-2)，除此方面以外，利用與實施例1相同的方法，於基材上形成厚度10μm之能量線硬化性之黏著劑層，製作支持片(10)-3。 Using the adhesive composition (I-2) obtained above, except for this point, the same method as in Example 1 was used to form an energy ray curable adhesive layer with a thickness of 10 μm on a substrate to produce a support sheet ( 10)-3.

使用上述所獲得之支持片(10)-3代替支持片(10)-1，除此方面以外，利用與實施例1相同的方法，製造保護膜形成用複合片。所獲得之保護膜形成用複合片之構成示於表1。 The support sheet (10)-3 obtained above was used instead of the support sheet (10)-1, except for this point, the same method as in Example 1 was used to produce a composite sheet for forming a protective film. Table 1 shows the composition of the obtained composite sheet for forming a protective film.

<保護膜形成用複合片之評價> <Evaluation of Composite Sheet for Forming Protective Film>

針對上述所獲得之保護膜形成用複合片，利用與實施例1相同的方法進行評價。結果示於表1。 The composite sheet for forming a protective film obtained above was evaluated by the same method as in Example 1. The results are shown in Table 1.

[比較例1] [Comparative Example 1]

<保護膜形成用複合片之製造> <Manufacturing of Composite Sheet for Forming Protective Film>

(黏著劑組成物之製造) (Manufacture of adhesive composition)

製備固形物成分濃度為30質量%之能量線硬化性之黏著劑組成物，該黏著劑組成物含有丙烯酸系聚合物(100質量份，固形物成分)、六亞甲基二異氰酸酯系交聯劑(Nippon Polyurethane公司製造之「Coronate HL」)(9質量份，固形物成分)、及光聚合起始劑(寡聚[2-羥基-2-甲基-1-(4-(1-甲基乙烯基)苯基)丙酮]，DKSH公司製造之「KIP-150」)(3質量份，固形物成分)，進而含有作為溶劑之甲基乙基酮。前述丙烯酸系聚合物係以下述方式獲得 之於側鏈具有甲基丙烯醯氧基且重量平均分子量為600000之能量線硬化性丙烯酸系聚合物，亦即，使甲基丙烯酸-2-乙酯(2EMA)(70質量份)、及HEA(30質量份)進行共聚合而成之丙烯酸系共聚物，與異氰酸2-甲基丙烯醯氧基乙酯(相對於前述丙烯酸系共聚物中的源自HEA之羥基的總莫耳數，異氰酸2-甲基丙烯醯氧基乙酯中的異氰酸酯基的總莫耳數成為0.7倍之量)反應。 An energy-ray curable adhesive composition with a solid content concentration of 30% by mass was prepared, the adhesive composition containing an acrylic polymer (100 parts by mass, solid content) and a hexamethylene diisocyanate-based crosslinking agent ("Coronate HL" manufactured by Nippon Polyurethane) (9 parts by mass, solid content), and a photopolymerization initiator (oligo[2-hydroxy-2-methyl-1-(4-(1-methyl Vinyl) phenyl) acetone], "KIP-150" manufactured by DKSH) (3 parts by mass, solid content), and further contains methyl ethyl ketone as a solvent. The aforementioned acrylic polymer is obtained in the following manner An energy-ray curable acrylic polymer having a methacryloxy group in the side chain and a weight average molecular weight of 600,000, that is, 2-ethyl methacrylate (2EMA) (70 parts by mass), and HEA (30 parts by mass) copolymerized acrylic copolymer with 2-methacryloxyethyl isocyanate (relative to the total number of moles of HEA-derived hydroxyl groups in the aforementioned acrylic copolymer , The total molar number of isocyanate groups in 2-methacryloxyethyl isocyanate becomes 0.7 times).

(支持片之製造) (Support film manufacturing)

使用上述所獲得之能量線硬化性之黏著劑組成物代替黏著劑組成物(I-4)，除此方面以外，利用與實施例1相同的方法，製作於基材上具備厚度10μm之非能量線硬化性之黏著劑層之支持片(10)-4。 The energy-ray curable adhesive composition obtained above was used instead of the adhesive composition (I-4). Except for this point, the same method as in Example 1 was used to fabricate a non-energy with a thickness of 10μm on a substrate Support sheet (10)-4 for linear hardening adhesive layer.

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

使用上述所獲得之支持片(10)-4代替支持片(10)-1，除此方面以外，利用與實施例1相同的方法，製造保護膜形成用複合片。所獲得之保護膜形成用複合片之構成示於表1。 The support sheet (10)-4 obtained above was used instead of the support sheet (10)-1. Except for this point, the same method as in Example 1 was used to produce a composite sheet for forming a protective film. Table 1 shows the composition of the obtained composite sheet for forming a protective film.

<保護膜形成用複合片之製造及評價> <Production and Evaluation of Composite Sheets for Forming Protective Films>

針對上述所獲得之保護膜形成用複合片，利用與實施例1相同的方法進行評價。結果示於表1。再者，表1中的評價結果一欄記載為「-」時，意指保護膜形成用複合 片無法實施該評價。 The composite sheet for forming a protective film obtained above was evaluated by the same method as in Example 1. The results are shown in Table 1. In addition, when the evaluation result column in Table 1 is described as "-", it means a composite for forming a protective film The film could not implement the evaluation.

[比較例2] [Comparative Example 2]

<保護膜形成用複合片之製造> <Manufacturing of Composite Sheet for Forming Protective Film>

(黏著劑組成物之製造) (Manufacture of adhesive composition)

製備固形物成分濃度為30質量%之能量線硬化性之黏著劑組成物，該黏著劑組成物含有丙烯酸系聚合物(100質量份，固形物成分)、及甲苯二異氰酸酯系交聯劑(Nippon Polyurethane公司製造之「Coronate L」)(0.2質量份，固形物成分)，進而含有作為溶劑之甲基乙基酮。前述丙烯酸系聚合物係使BA(91質量份)及丙烯酸(AA)(9質量份)進行共聚合而成，且重量平均分子量為600000。 An energy-ray curable adhesive composition with a solid content concentration of 30% by mass was prepared. The adhesive composition contained an acrylic polymer (100 parts by mass, solid content) and a toluene diisocyanate-based crosslinking agent (Nippon Polyurethane company "Coronate L") (0.2 parts by mass, solid content), and further contains methyl ethyl ketone as a solvent. The aforementioned acrylic polymer is obtained by copolymerizing BA (91 parts by mass) and acrylic acid (AA) (9 parts by mass), and has a weight average molecular weight of 600,000.

(支持片之製造) (Support film manufacturing)

使用上述所獲得之丙烯酸系共聚物，除此方面以外，利用與實施例1相同的方法，製作於基材上具備厚度10μm之非能量線硬化性之黏著劑層之支持片(10)-5。 Using the acrylic copolymer obtained above, except for this point, the same method as in Example 1 was used to produce a support sheet (10)-5 having a non-energy ray-curable adhesive layer with a thickness of 10 μm on a substrate. .

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

使用上述所獲得之支持片(10)-5代替支持片(10)-1，除此方面以外，利用與實施例1相同的方法製造保護膜形成用複合片。所獲得之保護膜形成用複合片之構成示於表1。 The support sheet (10)-5 obtained above was used instead of the support sheet (10)-1. Except for this point, the same method as in Example 1 was used to produce a composite sheet for forming a protective film. Table 1 shows the composition of the obtained composite sheet for forming a protective film.

<保護膜形成用複合片之評價> <Evaluation of Composite Sheet for Forming Protective Film>

針對上述所獲得之保護膜形成用複合片，利用與實施例1相同的方法進行評價。結果示於表1。 The composite sheet for forming a protective film obtained above was evaluated by the same method as in Example 1. The results are shown in Table 1.

Figure 106113626-A0202-12-0097-1
Figure 106113626-A0202-12-0097-1

根據上述結果可明確，於使用實施例1至實施例3之保護膜形成用複合片之情形時，保護膜與支持片之間的黏著力為100mN/25mm至2000mN/25mm之範圍內，切割時矽晶片之飛散及切削水之浸入得到抑制，亦未見其他不良情況，切割適性優異。並且，於使用實施例1至實施例3之保護膜形成用複合片之情形時，保護膜與支持片之間的黏著力為100mN/25mm至2000mN/25mm之範圍內，拾取時可將矽晶片自支持片剝離，拾取適性亦優異。 From the above results, it is clear that when the composite sheet for forming a protective film of Example 1 to Example 3 is used, the adhesive force between the protective film and the support sheet is within the range of 100mN/25mm to 2000mN/25mm. The scattering of silicon wafers and the immersion of cutting water are suppressed, and no other defects are seen, and the cutting suitability is excellent. In addition, when using the composite sheet for forming the protective film of Example 1 to Example 3, the adhesive force between the protective film and the support sheet is within the range of 100mN/25mm to 2000mN/25mm, and the silicon wafer can be removed during pickup. The self-supporting sheet peels off and the pick-up suitability is also excellent.

相對於此，於使用比較例1之保護膜形成用複合片之情形時，保護膜與支持片之間的黏著力為未達100mN/25mm之範圍，前述黏著力小，切割時矽晶片之飛散及切削水之浸入未得到抑制，切割適性差。 In contrast, when the composite sheet for forming a protective film of Comparative Example 1 is used, the adhesive force between the protective film and the support sheet is less than 100mN/25mm, and the aforementioned adhesive force is small, and the silicon wafer scatters during dicing. And the penetration of cutting water is not suppressed, and the cutting suitability is poor.

另一方面，於使用比較例2之保護膜形成用複合片之情形時，保護膜與支持片之間的黏著力超過2000mN/25mm，前述黏著力大，切割適性優異，但拾取時無法將矽晶片自支持片剝離，拾取適性差。推測於使用比較例2之保護膜形成用複合片之情形時，該片具備與實施例1至實施例3之保護膜形成用複合片相同的保護膜形成用膜，但支持片中的黏著劑層為強黏著性，保護膜與支持片之間的黏著力並非適當值。 On the other hand, when the composite sheet for forming a protective film of Comparative Example 2 was used, the adhesive force between the protective film and the support sheet exceeded 2000mN/25mm. The wafer is peeled from the supporting sheet, and the pick-up suitability is poor. It is assumed that when the composite sheet for forming a protective film of Comparative Example 2 is used, the sheet is provided with the same film for forming a protective film as the composite sheet for forming a protective film of Examples 1 to 3, but supporting the adhesive in the sheet The layer is highly adhesive, and the adhesive force between the protective film and the support sheet is not an appropriate value.

(產業可利用性) (Industrial availability)

本發明可用於製造半導體裝置。 The present invention can be used to manufacture semiconductor devices.

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

10‧‧‧支持片 10‧‧‧Support film

10a‧‧‧支持片的表面 10a‧‧‧Support the surface of the film

11‧‧‧基材 11‧‧‧Substrate

11a‧‧‧基材的表面 11a‧‧‧The surface of the 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 protective film forming film

15‧‧‧剝離膜 15‧‧‧Peeling film

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

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

Claims (3)

一種保護膜形成用複合片，於支持片上具備能量線硬化性之保護膜形成用膜；前述保護膜形成用膜被照射能量線而成為保護膜時，前述保護膜與前述支持片之間的黏著力為1000mN/25mm至2000mN/25mm；前述支持片具有黏著劑層，且前述保護膜形成用膜與前述黏著劑層直接接觸。 A composite sheet for forming a protective film, a film for forming a protective film with energy ray curability on a support sheet; when the film for forming a protective film is irradiated with energy rays to become a protective film, the adhesion between the protective film and the support sheet The force is 1000 mN/25mm to 2000 mN/25mm; the support sheet has an adhesive layer, and the protective film forming film is in direct contact with the adhesive layer. 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非能量線硬化性。 The composite sheet for forming a protective film according to claim 1, wherein the adhesive layer is non-energy ray curable. 一種保護膜形成用複合片，於支持片上具備能量線硬化性之保護膜形成用膜；前述保護膜形成用膜被照射能量線而成為保護膜時，前述保護膜與前述支持片之間的黏著力為100mN/25mm至2000mN/25mm；前述支持片具有黏著劑層，且前述保護膜形成用膜與前述黏著劑層直接接觸；前述黏著劑層為非能量線硬化性；形成前述黏著劑層之黏著劑組成物中，不包括加熱發泡型或是水膨潤型的黏著劑組成物。 A composite sheet for forming a protective film, a film for forming a protective film with energy ray curability on a support sheet; when the film for forming a protective film is irradiated with energy rays to become a protective film, the adhesion between the protective film and the support sheet The force is 100mN/25mm to 2000mN/25mm; the support sheet has an adhesive layer, and the protective film forming film is in direct contact with the adhesive layer; the adhesive layer is non-energy-ray curable; the adhesive layer is formed The adhesive composition does not include heating foaming or water swelling adhesive compositions.
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