TW202332749A

TW202332749A - Curable adhesive sheet

Info

Publication number: TW202332749A
Application number: TW111137135A
Authority: TW
Inventors: 西嶋健太; 樫尾幹広; 泉直史
Original assignee: 日商琳得科股份有限公司
Priority date: 2021-09-30
Filing date: 2022-09-30
Publication date: 2023-08-16
Also published as: WO2023054676A1

Abstract

Provided is a curable adhesive sheet comprising a curable adhesive layer, with which a cured product having a dielectric loss tangent of 0.01 or less at 23 DEG C and at 1 GHz can be formed, and first and second release films between which both sides of the curable adhesive layer are held, wherein: the first and second release films have a resin film and a release layer that is provided on one surface of the resin film, is formed from non-silicone release agent, and contacts a surface of the curable adhesive layer; and the following requirement (I) is satisfied. Requirement (I): the peel force (R1) at the time when the first release film is peeled from the curable adhesive layer at the peeling angle of 180 DEG and at the peel rate of 300 mm/min is not more than 250 mN/50 mm.

Description

硬化性接著片hardening adhesive sheet

本發明係關於一種硬化性接著片。The present invention relates to a curable adhesive sheet.

近年來，伴隨電子機器之小型化、輕量化，正使用可撓性印刷配線板(Flexible Print Circuit；FPC)作為配線構件。FPC例如可對在聚醯亞胺等之絕緣樹脂膜貼合有銅箔的覆銅積層板之銅箔實施蝕刻處理，形成電氣電路而製造。另外，對於此種FPC，係進行下述操作：將具有絕緣性之樹脂基材及接著劑層的蓋層片(coverlay sheet)貼合於形成有電氣電路之銅箔，來保護電氣電路。 In recent years, along with the miniaturization and weight reduction of electronic equipment, flexible printed wiring boards (Flexible Print Circuit; FPC) are being used as wiring members. For example, FPC can be produced by etching the copper foil of a copper-clad laminate in which an insulating resin film such as polyimide is laminated with copper foil to form an electrical circuit. In this type of FPC, a coverlay sheet of an insulating resin base material and an adhesive layer is bonded to a copper foil on which an electrical circuit is formed to protect the electrical circuit.

作為此種蓋層片之一例，於專利文獻1揭示有與熱硬化性接著片有關之發明，該熱硬化性接著片係以含有特定量之苯乙烯系彈性體、於末端具有聚合性基之改質聚苯醚樹脂、環氧樹脂、以及環氧樹脂硬化劑之接著劑組成物所構成之熱硬化性接著層在基材上所形成之熱硬化性接著片。 [先前技術文獻] [專利文獻] As an example of such a cover sheet, Patent Document 1 discloses an invention related to a thermosetting adhesive sheet containing a specific amount of styrene-based elastomer and having a polymerizable group at the terminal. A thermosetting adhesive sheet formed by a thermosetting adhesive layer composed of an adhesive composition of modified polyphenylene ether resin, epoxy resin, and epoxy resin hardener on a base material. [Prior technical literature] [Patent Document]

[專利文獻1]日本特開2019-135280號公報。[Patent Document 1] Japanese Patent Application Publication No. 2019-135280.

[發明所欲解決之課題][Problem to be solved by the invention]

再者，在FPC中，就抑制電子機器之作動不良等弊害的觀點而言，混入異物或污染成分的移轉成為問題。例如，如上述之專利文獻1所記載般的熱硬化性接著片，為了保護熱硬化性接著層的表面之目的，而將具有由聚矽氧系剝離劑所構成之層之聚矽氧系剝離片積層於該熱硬化性接著層上之情形較多。由於聚矽氧系剝離片在使用時容易從熱硬化性接著層剝離且操作性優異，故廣泛地被使用。然而，存在如下問題：聚矽氧系剝離片隨著時間經過導致由聚矽氧系剝離劑所構成之層的矽(Si)成分移轉至硬化性接著層，導致硬化性接著層內的矽成分移轉至作為被黏附體之FPC的表面，可能成為電子機器的作動不良等主因。因此，謀求一種抑制對被黏附體之污染且操作性優異之硬化性接著片。 [用以解決課題之手段] Furthermore, in FPC, from the viewpoint of suppressing harmful effects such as malfunction of electronic equipment, contamination of foreign matter or transfer of contaminants becomes a problem. For example, in the thermosetting adhesive sheet as described in the above-mentioned Patent Document 1, in order to protect the surface of the thermosetting adhesive layer, the polysilicone-based adhesive sheet having a layer composed of a polysilicone-based releasing agent is peeled off. In many cases, sheets are laminated on the thermosetting adhesive layer. Polysilicone-based release sheets are widely used because they are easy to peel off from the thermosetting adhesive layer during use and have excellent workability. However, there is a problem that the silicone (Si) component of the layer composed of the polysiloxane release agent is transferred to the curable adhesive layer over time, causing the silicon in the curable adhesive layer to The components migrate to the surface of the FPC as the adherend, which may cause malfunctions of electronic equipment. Therefore, there is a demand for a curable adhesive sheet that suppresses contamination of an adherend and has excellent workability. [Means used to solve problems]

本發明係提供一種硬化性接著片，具有：能夠形成介電正切為特定值以下之硬化物之硬化性接著劑層、以及挾持該硬化性接著劑層之兩面之第一剝離膜以及第二剝離膜；第一剝離膜以及第二剝離膜係於樹脂膜上具有由非聚矽氧系剝離劑所形成之接觸前述硬化性接著劑層的表面之剝離層；將第一剝離膜自前述硬化性接著劑層剝離時之剝離力被調整為特定值以下。具體而言，作為本發明所提供之一態樣，如以下所示。 [1]一種硬化性接著片，係具有：能夠形成於23℃、1GHz之介電正切為0.01以下的硬化物之硬化性接著劑層、以及挾持該硬化性接著劑層之兩面之第一剝離膜以及第二剝離膜之硬化性接著片；第一剝離膜以及第二剝離膜係具有：樹脂膜、以及於該樹脂膜其中一表面上之由非聚矽氧系剝離劑所形成之接觸前述硬化性接著劑層的表面之剝離層，並滿足下述要件(I)：・要件(I)：將第一剝離膜以剝離角度180°、剝離速度300mm／分鐘自前述硬化性接著劑層進行剝離時之剝離力(R1)為250mN／50mm以下。 [2]如上述[1]所記載之硬化性接著片，進而滿足下述要件(II)：・要件(II)：剝離力(R1)係小於將第二剝離膜以剝離角度180°、剝離速度300mm／分鐘自前述硬化性接著劑層剝離時之剝離力(R2)。 [3]如上述[2]所記載之硬化性接著片，進而滿足下述要件(IIa)：・要件(IIa)：剝離力(R1)與剝離力(R2)之比[(R1)／(R2)]為0.97以下。 [4]如上述[1]至[3]中任一項所記載之硬化性接著片，進而滿足下述要件(III)：・要件(III)：將第二剝離膜以剝離角度180°、剝離速度300mm／分鐘自前述硬化性接著劑層剝離時之剝離力(R2)為300mN／50mm以下。 [5]如上述[1]至[4]中任一項所記載之硬化性接著片，其中用於形成第一剝離膜以及第二剝離膜中至少一者之剝離層的前述非聚矽氧系剝離劑為醇酸系剝離劑。 [6]如上述[1]至[5]中任一項所記載之硬化性接著片，其中前述硬化性接著劑層係由含有黏合劑樹脂(A)之硬化性接著劑組成物所形成之層。 [7]如上述[6]所記載之硬化性接著片，其中前述硬化性接著劑組成物係進而含有聚苯醚樹脂(B)。 [8]如上述[1]至[7]中任一項所記載之硬化性接著片，其中構成第一剝離膜之樹脂膜(1)為有色樹脂膜。 [9]如上述[1]至[8]中任一項所記載之硬化性接著片，其中構成第二剝離膜之樹脂膜(2)係能夠以目視方式來和構成第一剝離膜之樹脂膜(1)做區別。 [發明功效] The present invention provides a curable adhesive sheet having: a curable adhesive layer capable of forming a cured product having a dielectric tangent equal to or less than a specific value; and a first release film and a second release film sandwiching both sides of the curable adhesive layer. film; the first release film and the second release film have a release layer formed of a non-polysilicone release agent on the resin film and in contact with the surface of the curable adhesive layer; the first release film is separated from the curable adhesive layer. The peeling force when peeling off the adhesive layer is adjusted to be below a specific value. Specifically, one aspect provided by the present invention is as follows. [1] A curable adhesive sheet having a curable adhesive layer capable of forming a cured material having a dielectric tangent of 0.01 or less at 23° C. and 1 GHz, and a first peeling layer sandwiching both sides of the curable adhesive layer. The curable adhesive sheet of the film and the second release film; the first release film and the second release film have: a resin film, and a contact formed by a non-polysilicone release agent on one surface of the resin film. The peeling layer on the surface of the curable adhesive layer satisfies the following requirement (I): ・Requirement (I): The first peeling film is removed from the aforementioned curable adhesive layer at a peeling angle of 180° and a peeling speed of 300mm/min. The peeling force (R1) during peeling is 250mN/50mm or less. [2] The curable adhesive sheet as described in the above [1], further satisfying the following requirement (II): ・Requirement (II): The peeling force (R1) is less than the peeling force (R2) when the second release film is peeled off from the curable adhesive layer at a peeling angle of 180° and a peeling speed of 300mm/minute. [3] The curable adhesive sheet as described in the above [2], further satisfying the following requirement (IIa): ・Requirement (IIa): The ratio of peeling force (R1) to peeling force (R2) [(R1)/(R2)] is 0.97 or less. [4] The curable adhesive sheet according to any one of the above [1] to [3], further satisfying the following requirement (III): ・Requirement (III): The peeling force (R2) when peeling the second release film from the curable adhesive layer at a peeling angle of 180° and a peeling speed of 300mm/minute is 300mN/50mm or less. [5] The curable adhesive sheet according to any one of the above [1] to [4], wherein the non-polysiloxane used to form the release layer of at least one of the first release film and the second release film The stripper is an alkyd stripper. [6] The curable adhesive sheet according to any one of the above [1] to [5], wherein the curable adhesive layer is formed of a curable adhesive composition containing a binder resin (A) layer. [7] The curable adhesive sheet according to the above [6], wherein the curable adhesive composition further contains polyphenylene ether resin (B). [8] The curable adhesive sheet according to any one of [1] to [7] above, wherein the resin film (1) constituting the first release film is a colored resin film. [9] The curable adhesive sheet according to any one of [1] to [8] above, wherein the resin film (2) constituting the second release film can be visually combined with the resin constituting the first release film. Membrane (1) makes the difference. [Invention effect]

本發明之合適的一態樣的硬化性接著片係能夠抑制對被黏附體之污染，且於使用時容易除去剝離膜而操作性優異，例如能夠合適適用作為蓋層片。A suitable aspect of the curable adhesive sheet of the present invention is one that can suppress contamination of the adherend, easily remove the release film during use, and has excellent operability. For example, it can be suitably used as a cover sheet.

本說明書所記載之數值範圍係可將上限值及下限值任意組合。例如，於作為數值範圍而記載有「較佳為20至120，更佳為40至90」之情形時，「20至90」之範圍或「40至120」之範圍亦包含於本說明書所記載之數值範圍。另外，例如於作為數值範圍而記載有「較佳為20以上，更佳為40以上，另外，較佳為120以下，更佳為90以下」之情形時，「20至90」之範圍或「40至120」之範圍亦包含於本說明書所記載之數值範圍。再者，作為本說明書所記載之數值範圍，例如「60至100」之記載意指「60以上至100以下」之範圍。進而，可於本說明書所記載之上限值及下限值之規定中，自各自之選項中適當選擇，任意組合而規定下限值至上限值之數值範圍。再者，作為本說明書所記載之較佳態樣而記載的各種要件可組合多個。 The numerical range described in this specification is an upper limit value and a lower limit value that can be combined arbitrarily. For example, when "20 to 120 is preferred, and 40 to 90 is more preferred" is described as a numerical range, the range of "20 to 90" or the range of "40 to 120" is also included in the description of this specification. range of values. For example, when "20 or more is preferred, 40 or more is more preferred, and 120 or less is preferred, and 90 or less is more preferred" is described as the numerical range, the range of "20 to 90" or " The range of "40 to 120" is also included in the numerical range described in this specification. In addition, as the numerical range described in this specification, for example, the description of "60 to 100" means the range of "60 or more and 100 or less". Furthermore, among the upper limit values and lower limit values described in this specification, you can appropriately select from the respective options and arbitrarily combine them to define a numerical range from the lower limit value to the upper limit value. Furthermore, a plurality of various requirements described as preferred aspects described in this specification may be combined.

本說明書中，例如所謂「(甲基)丙烯酸酯」係用作表示「丙烯酸酯」及「甲基丙烯酸酯」兩者之用語，關於其它類似用語亦同樣。本說明書中，所謂硬化性接著劑組成物之「有效成分」，意指硬化性接著劑組成物所含之成分中除了水或有機溶媒之稀釋溶媒以外的成分。 In this specification, for example, "(meth)acrylate" is used as a term to represent both "acrylate" and "methacrylate", and the same applies to other similar terms. In this specification, the "active ingredient" of the curable adhesive composition means components other than water or diluent solvents such as organic solvents among the components contained in the curable adhesive composition.

本說明書中，數量平均分子量(Mn)為藉由凝膠滲透層析(Gel Permeation Chromatography；GPC)法所測定之標準聚苯乙烯換算之值，具體而言為基於實施例所記載之方法測定之值。In this specification, the number average molecular weight (Mn) is a standard polystyrene-converted value measured by the gel permeation chromatography (Gel Permeation Chromatography; GPC) method. Specifically, it is measured based on the method described in the Examples. value.

再者，本說明書中，構成硬化性接著片之各層的厚度係依據JIS　K7130(1999)所測定之值，例如能夠使用定壓厚度測定器(股份有限公司TECLOCK製，製品名「PG-02J」)進行測定。In addition, in this specification, the thickness of each layer constituting the curable adhesive sheet is a value measured in accordance with JIS K7130 (1999). For example, a constant pressure thickness measuring device (manufactured by TECLOCK Co., Ltd., product name "PG-02J") can be used ) is measured.

[硬化性接著片的構成] 圖1係表示本發明之硬化性接著片的構成之一例的該接著片之厚度方向之示意剖面圖。如圖1所示，本發明之硬化性接著片1係具有：硬化性接著劑層10、以及挾持該硬化性接著劑層10的兩面之第一剝離膜21以及第二剝離膜22。硬化性接著劑層10係藉由加以硬化而能夠形成於23℃、1GHz之介電正切為0.01以下的硬化物。另外，第一剝離膜21係具有樹脂膜212、以及於樹脂膜212其中一表面上接觸於硬化性接著劑層10的表面10a之剝離層211。同樣地，關於第二剝離膜22，亦具有樹脂膜222、以及於樹脂膜222其中一表面上接觸於硬化性接著劑層10的表面10b之剝離層221。 [Constitution of the hardening adhesive sheet] FIG. 1 is a schematic cross-sectional view in the thickness direction of the curable adhesive sheet of the present invention, showing an example of the structure of the adhesive sheet. As shown in FIG. 1 , the curable adhesive sheet 1 of the present invention has a curable adhesive layer 10 and a first release film 21 and a second release film 22 sandwiching both sides of the curable adhesive layer 10 . The curable adhesive layer 10 can be cured to form a cured product having a dielectric tangent of 0.01 or less at 23° C. and 1 GHz. In addition, the first release film 21 has a resin film 212 and a release layer 211 that is in contact with the surface 10 a of the curable adhesive layer 10 on one surface of the resin film 212 . Similarly, the second release film 22 also has a resin film 222 and a release layer 221 that is in contact with the surface 10 b of the curable adhesive layer 10 on one surface of the resin film 222 .

第一剝離膜21以及第二剝離膜22所具有之剝離層211、剝離層221係由非聚矽氧系剝離劑所形成之層。由於剝離層211、剝離層221係由非聚矽氧系剝離劑所形成之層，故矽(Si)成分不會移轉至與其接觸之硬化性接著劑層10的表面10a、表面10b上。因此，本發明的硬化性接著片能夠抑制矽成分移轉至被黏附體所導致之污染。 The release layers 211 and 221 of the first release film 21 and the second release film 22 are layers formed of a non-polysilicone release agent. Since the peeling layer 211 and the peeling layer 221 are formed of a non-polysilicone release agent, silicon (Si) components are not transferred to the surfaces 10a and 10b of the curable adhesive layer 10 in contact with them. Therefore, the curable adhesive sheet of the present invention can suppress contamination caused by the transfer of silicon components to the adherend.

其中，本發明之硬化性接著片所具有之硬化性接著劑層之介電正切係低至0.01以下。一般而言，介電正切低之硬化性接著劑層通常係由不具有極性基之成分或是極性小的成分所構成，硬化性接著劑層的表面的極性有偏低的傾向。使用聚矽氧系剝離膜之情形時，在極性低的硬化性接著劑層的表面上積層該剝離膜之後而進行除去時，自硬化性接著劑層的表面剝離性不至於成為問題。然而，使用具有由非聚矽氧系剝離劑所形成之剝離層之剝離膜，並將該剝離膜在極性低的硬化性接著劑層的表面上加以積層之情形時，在將該剝離膜自硬化性接著劑層的表面除去時，會產生剝離性不充分而難以剝除等操作性的問題。 Among them, the dielectric tangent of the curable adhesive layer of the curable adhesive sheet of the present invention is as low as 0.01 or less. Generally speaking, a curable adhesive layer with a low dielectric tangent is usually composed of a component that does not have a polar group or a component with low polarity, and the polarity of the surface of the curable adhesive layer tends to be low. When a polysilicone-based release film is used, the surface releasability of the self-curing adhesive layer does not become a problem when the release film is laminated on the surface of a low-polarity curable adhesive layer and then removed. However, when a release film having a release layer formed of a non-polysilicone release agent is used and the release film is laminated on the surface of a low-polarity curable adhesive layer, the release film is removed from the When the surface of the curable adhesive layer is removed, workability problems arise such as insufficient peelability and difficulty in peeling off.

對於這種難以自硬化性接著劑層的表面剝除剝離膜之操作性的問題，在本發明之硬化性接著片之中，係以滿足下述要件(I)的方式加以調整。・要件(I)：將第一剝離膜以剝離角度180°、剝離速度300mm／分鐘自前述硬化性接著劑層剝離時之剝離力(R1)為250mN／50mm以下。藉由滿足上述要件(I)，在使用時能夠將第一剝離膜自硬化性接著劑層的表面容易地剝離，而作成操作性優異之硬化性接著片。在本發明之一態樣之硬化性接著片中，就上述觀點而言，上述要件(I)所規定之剝離力(R1)為250mN／50mm以下，較佳為200mN／50mm以下，更佳為150mN／50mm以下，又更佳為110mN／50mm以下，進而更佳為90mN／50mm以下，另外，較佳為5mN／50mm以上，更佳為10mN／50mm以上，又更佳為20mN／50mm以上。 Regarding the operability problem of difficulty in peeling off the release film from the surface of the curable adhesive layer, the curable adhesive sheet of the present invention is adjusted so as to satisfy the following requirement (I). ・Requirement (I): The peeling force (R1) when peeling the first release film from the curable adhesive layer at a peeling angle of 180° and a peeling speed of 300mm/minute is 250mN/50mm or less. By satisfying the above requirement (I), the first release film can be easily peeled off from the surface of the curable adhesive layer during use, and a curable adhesive sheet with excellent workability can be produced. In the curable adhesive sheet according to one aspect of the present invention, from the above point of view, the peeling force (R1) specified in the above requirement (I) is 250mN/50mm or less, preferably 200mN/50mm or less, and more preferably 150mN/50mm or less, more preferably 110mN/50mm or less, further preferably 90mN/50mm or less. In addition, 5mN/50mm or more is preferred, 10mN/50mm or more is more preferred, and 20mN/50mm or more is more preferred.

再者，作為以成為上述範圍的方式而調整剝離力(R1)之方法，能夠藉由將構成第一剝離膜之樹脂膜以及形成剝離劑層之剝離劑的種類、以及形成硬化性接著劑層之硬化性接著劑組成物所含有之各成分的種類以及含量進行適合設定而調整。再者，具體的調整方法係於各構成的說明的項目進行詳述。Furthermore, as a method of adjusting the peeling force (R1) so as to fall within the above range, the resin film constituting the first peeling film and the type of release agent forming the release agent layer can be adjusted by forming a curable adhesive layer. The types and contents of each component contained in the curable adhesive composition are appropriately set and adjusted. In addition, the specific adjustment method is described in detail in the description items of each component.

本發明之一態樣之硬化性接著片較佳係滿足上述要件(I)且進而滿足下述要件(II)。・要件(II)：剝離力(R1)係小於將第二剝離膜以剝離角度180°、剝離速度300mm／分鐘自前述硬化性接著劑層剝離時之剝離力(R2)。藉由滿足上述(II)，能夠將第一剝離膜自硬化性接著劑層的表面更容易地剝離，能夠作成操作性更加優異之硬化性接著片。繼而，就上述觀點而言，本發明之一態樣之硬化性接著片更佳係滿足上述要件(I)且進而滿足下述要件(IIa)。・要件(IIa)：剝離力(R1)與剝離力(R2)之比[(R1)／(R2)]為0.97以下。 The curable adhesive sheet according to one aspect of the present invention preferably satisfies the above requirement (I) and further satisfies the following requirement (II). ・Requirement (II): The peeling force (R1) is less than the peeling force (R2) when the second release film is peeled off from the curable adhesive layer at a peeling angle of 180° and a peeling speed of 300mm/min. By satisfying the above (II), the first release film can be peeled off more easily from the surface of the curable adhesive layer, and a curable adhesive sheet with more excellent workability can be produced. Furthermore, from the above viewpoint, the curable adhesive sheet according to one aspect of the present invention more preferably satisfies the above requirement (I) and further satisfies the following requirement (IIa).・Requirement (IIa): The ratio of peeling force (R1) to peeling force (R2) [(R1)/(R2)] is 0.97 or less.

就能夠將第一剝離膜自硬化性接著劑層的表面更容易地剝離，而作成操作性更加優異之硬化性接著片之觀點而言，上述要件(IIa)所規定之剝離力(R1)與剝離力(R2)之比[(R1)／(R2)]為0.97以下，較佳為0.95以下，更佳為0.88以下，又更佳為0.80以下。作為上述要件(IIa)所規定之剝離力(R1)與剝離力(R2)之比[(R1)／(R2)]的下限，並無特別限定，較佳為0.2以上，較佳為0.35以上。From the viewpoint that the first release film can be peeled off more easily from the surface of the curable adhesive layer and a curable adhesive sheet with better workability can be produced, the peeling force (R1) specified in the above requirement (IIa) and The peeling force (R2) ratio [(R1)/(R2)] is 0.97 or less, preferably 0.95 or less, more preferably 0.88 or less, still more preferably 0.80 or less. The lower limit of the ratio [(R1)/(R2)] of the peeling force (R1) and the peeling force (R2) stipulated in the above requirement (IIa) is not particularly limited, but is preferably 0.2 or more, and more preferably 0.35 or more. .

另外，本發明之一態樣之硬化性接著片較佳係滿足上述要件(I)且進而滿足下述要件(III)，更佳係滿足上述要件(I)以及(II)且進而滿足下述要件(III)，又更佳係滿足上述要件(I)以及(IIa)且進而滿足下述要件(III)。・要件(III)：剝離力(R2)為300mN／50mm以下。藉由滿足上述要件(III)，能夠在除去第一剝離膜並將露出表面之硬化性接著劑層貼附於被黏附體之後，第二剝離膜亦可容易地剝離，而作成操作性優異之硬化性接著片。本發明之一態樣之硬化性接著片中，就上述觀點而言，上述要件(I)所規定之剝離力(R1)為300mN／50mm以下，較佳為250mN／50mm以下，更佳為220mN／50mm以下，又更佳為150mN／50mm以下，進而更佳為110mN／50mm以下，另外，較佳為20mN／50mm以上，更佳為30mN／50mm以上，又更佳為40mN／50mm以上。 In addition, the curable adhesive sheet according to one aspect of the present invention preferably satisfies the above requirement (I) and further satisfies the following requirement (III), and more preferably satisfies the above requirements (I) and (II) and further satisfies the following requirement Requirement (III), more preferably, it satisfies the above-mentioned requirements (I) and (IIa) and further satisfies the following requirement (III). ・Requirement (III): Peeling force (R2) is 300mN/50mm or less. By satisfying the above requirement (III), after the first release film is removed and the curable adhesive layer on the exposed surface is attached to the adherend, the second release film can be easily peeled off, resulting in excellent workability. Hardening adhesive sheet. In the curable adhesive sheet according to one aspect of the present invention, from the above point of view, the peeling force (R1) specified in the above requirement (I) is 300mN/50mm or less, preferably 250mN/50mm or less, more preferably 220mN. /50mm or less, more preferably 150mN/50mm or less, still more preferably 110mN/50mm or less. In addition, 20mN/50mm or more is preferred, 30mN/50mm or more is more preferred, and 40mN/50mm or more is more preferred.

再者，關於剝離力(R2)，亦能夠藉由適合設定構成第二剝離膜之樹脂膜以及形成剝離劑層之剝離劑的種類、以及形成硬化性接著劑層之硬化性接著劑組成物所含有之各成分的種類以及含量而進行調整。再者，具體的調整方法係於各構成的說明的項目進行詳述。Furthermore, the peeling force (R2) can also be determined by suitably setting the types of the resin film constituting the second peeling film and the release agent forming the release agent layer, and the curable adhesive composition forming the curable adhesive layer. Adjust the type and content of each ingredient contained. In addition, the specific adjustment method is described in detail in the description items of each component.

另外，本說明書中，剝離力(R1)以及剝離力(R2)意指基於後述之實施例所記載之方法進行測定之值。以下針對構成本發明之一態樣之硬化性接著片之各層以及該層的形成材料加以說明。 In addition, in this specification, peeling force (R1) and peeling force (R2) mean the value measured based on the method described in the Example mentioned later. Each layer constituting the curable adhesive sheet according to one aspect of the present invention and the material forming the layer will be described below.

[第一剝離膜、第二剝離膜] 本發明之一態樣之硬化性接著片所具有之第一剝離膜以及第二剝離膜，只要是具有樹脂膜、以及由非聚矽氧系剝離劑所形成之剝離層之構成即可。 [First release film, second release film] The first release film and the second release film of the curable adhesive sheet according to one aspect of the present invention may be composed of a resin film and a release layer formed of a non-polysilicone release agent.

作為前述樹脂膜所含有之樹脂成分，可列舉例如：聚對苯二甲酸乙二酯樹脂、聚對苯二甲酸丁二酯樹脂、聚萘二甲酸乙二酯樹脂等聚酯系樹脂、聚丙烯樹脂、聚乙烯樹脂等聚烯烴系樹脂、聚碳酸脂樹脂、以及併用這些樹脂成分兩種以上之混合樹脂等。再者，前述樹脂膜除了樹脂成分以外，亦可含有紫外線吸收劑、抗靜電劑、光穩定劑、抗氧化劑、樹脂穩定劑、填充材、著色劑(顔料或染料等)等添加劑。前述樹脂膜亦可作成有色樹脂膜。作為有色樹脂膜，為了著色而亦可為樹脂層經發泡之發泡樹脂膜。再者，該發泡樹脂膜通常為白色且不透明的有色樹脂膜。另外，由含有樹脂成分以及填充材之樹脂組成物所形成之樹脂膜亦由於光的散射致使透明性降低而成為有色樹脂膜。進而，為了著色成為期望之色，亦可為由含有樹脂成分以及期望的著色劑之樹脂組成物所形成之有色樹脂膜。 Examples of the resin component contained in the resin film include polyester-based resins such as polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, and polypropylene. Resins, polyolefin-based resins such as polyethylene resins, polycarbonate resins, and mixed resins using two or more of these resin components. Furthermore, in addition to the resin component, the resin film may also contain additives such as ultraviolet absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, and colorants (pigments, dyes, etc.). The aforementioned resin film may also be made into a colored resin film. The colored resin film may be a foamed resin film in which the resin layer is foamed for coloring. In addition, the foamed resin film is usually a white and opaque colored resin film. In addition, a resin film formed from a resin composition containing a resin component and a filler also has reduced transparency due to light scattering and becomes a colored resin film. Furthermore, in order to color it into a desired color, it may be a colored resin film formed from a resin composition containing a resin component and a desired colorant.

本發明之一態樣之硬化性接著片中，就作成操作性更加優異之硬化性接著片的觀點而言，較佳係構成第一剝離膜之樹脂膜(1)為有色樹脂膜。藉由成為由有色樹脂膜所構成之第一剝離膜，與第二剝離膜之區別變得明確。例如，能夠防止在使用時應剝除第一剝離膜時導致第二剝離膜亦被剝除之誤用，成為操作性更加優異之硬化性接著片。再者，有色樹脂膜亦包含白色的樹脂膜。 In the curable adhesive sheet according to one aspect of the present invention, from the viewpoint of producing a curable adhesive sheet with further excellent workability, it is preferable that the resin film (1) constituting the first release film is a colored resin film. By using the first release film made of a colored resin film, the difference from the second release film becomes clear. For example, when the first release film should be peeled off during use, misuse such that the second release film is also peeled off can be prevented, and the curable adhesive sheet can be provided with more excellent workability. Furthermore, the colored resin film also includes a white resin film.

就與上述同樣的觀點而言，構成第二剝離膜之樹脂膜(2)較佳係能夠以目視方式來和構成第一剝離膜之樹脂膜(1)做區別。作為能夠以目視區別之方法，可列舉如：在將樹脂膜(1)作成有色樹脂膜時，將樹脂膜(2)作成無色透明的樹脂膜之方法、或是亦可為將樹脂膜(2)作成與樹脂膜(1)不同色之透明或是不透明的有色樹脂膜之方法、在樹脂膜(2)的表面加上能夠以目視加以辨識的標識之方法等。在這些方法之中，基於將第一剝離膜剝離並將硬化性接著片貼附於被黏附體之後，經由第二剝離膜來辨識被黏附體的表面的狀態，或是藉由其它光學的手段進行觀察變得容易的觀點，能夠以目視區別之方法較佳係將樹脂膜(1)作成有色樹脂膜時，將樹脂膜(2)作成無色透明的樹脂膜之方法、或是作成與樹脂膜(1)不同色之透明或是不透明的有色樹脂膜之方法，更佳係將樹脂膜(2)作成無色透明的樹脂膜之方法。 From the same viewpoint as above, it is preferable that the resin film (2) constituting the second release film can be visually distinguished from the resin film (1) constituting the first release film. As a method that can be visually distinguished, for example, when the resin film (1) is made into a colored resin film, the resin film (2) is made into a colorless and transparent resin film, or the resin film (2) can be made into a colorless and transparent resin film. ) A method of producing a transparent or opaque colored resin film that is different from the resin film (1), a method of adding a visually identifiable mark on the surface of the resin film (2), etc. Among these methods, after peeling off the first release film and attaching the curable adhesive sheet to the adherend, the state of the surface of the adherend is identified through the second release film, or through other optical means. From the viewpoint of easier observation, a method that enables visual distinction is preferably a method in which the resin film (1) is made into a colored resin film, the resin film (2) is made into a colorless and transparent resin film, or the resin film is made into a colorless and transparent resin film. (1) The method of making transparent or opaque colored resin films of different colors, more preferably, the method of making the resin film (2) into a colorless and transparent resin film.

作為前述剝離層的形成材料之非聚矽氧系剝離劑，可列舉例如：烯烴系剝離劑、異戊二烯系剝離劑、丁二烯系剝離劑等橡膠系彈性體系剝離劑、長鏈烷基系剝離劑、醇酸系剝離劑、氟系剝離劑等。在這些非聚矽氧系剝離劑之中，就調整至滿足上述要件(I)至要件(III)之剝離力(R1)以及剝離力(R2)之觀點而言，用於形成第一剝離膜以及第二剝離膜中至少一者之剝離層之前述非聚矽氧系剝離劑較佳為醇酸系剝離劑，用於形成第一剝離膜以及第二剝離膜的双方的剝離層之前述非聚矽氧系剝離劑更佳為醇酸系剝離劑。 Examples of non-polysilicone release agents that form the release layer include rubber-based elastic release agents such as olefin-based release agents, isoprene-based release agents, butadiene-based release agents, and long-chain alkanes. Base-based stripper, alkyd-based stripper, fluorine-based stripper, etc. Among these non-polysilicone release agents, from the viewpoint of adjusting the release force (R1) and the release force (R2) to satisfy the above-mentioned requirements (I) to (III), it is used to form the first release film. and the release layer of at least one of the second release films. The aforementioned non-polysilicone release agent is preferably an alkyd release agent. The aforementioned non-polysilicone release agent is used to form the release layers of both the first release film and the second release film. The polysilicone-based stripper is more preferably an alkyd-based stripper.

本發明之一態樣之硬化性接著片中，就將剝離力(R1)調整至滿足上述要件(I)之範圍之觀點而言，第一剝離膜的厚度(T1)較佳為10μm以上，更佳為20μm以上，又更佳為30μm以上，另外，較佳為200μm以下，更佳為100μm以下，又更佳為70μm以下，進而更佳為45μm以下。In the curable adhesive sheet according to one aspect of the present invention, from the viewpoint of adjusting the peeling force (R1) to a range that satisfies the above requirement (I), the thickness (T1) of the first peeling film is preferably 10 μm or more. More preferably, it is 20 μm or more, still more preferably, it is 30 μm or more. In addition, it is preferably 200 μm or less, more preferably 100 μm or less, further preferably 70 μm or less, still more preferably 45 μm or less.

本發明之一態樣之硬化性接著片中，就將剝離力(R2)調整至滿足上述要件(III)之範圍之觀點而言，第二剝離膜的厚度(T2)較佳為30μm以上，更佳為35μm以上，另外，較佳為270μm以下，更佳為210μm以下，又更佳為140μm以下。就作成進而滿足上述要件(II)以及要件(IIa)之硬化性接著片之觀點而言，第二剝離膜的厚度(T2)較佳為47μm以上，更佳為55μm以上，又更佳為65μm以上。 In the curable adhesive sheet according to one aspect of the present invention, from the viewpoint of adjusting the peeling force (R2) to a range that satisfies the above requirement (III), the thickness (T2) of the second peeling film is preferably 30 μm or more. More preferably, it is 35 μm or more, more preferably 270 μm or less, more preferably 210 μm or less, still more preferably 140 μm or less. From the viewpoint of producing a curable adhesive sheet that further satisfies the above requirements (II) and (IIa), the thickness (T2) of the second release film is preferably 47 μm or more, more preferably 55 μm or more, and still more preferably 65 μm. above.

本發明之一態樣之硬化性接著片中，就作成調整至滿足上述要件(II)以及要件(IIa)之硬化性接著片之觀點而言，第一剝離膜的厚度(T1)與第二剝離膜的厚度(T2)之比[(T1)／(T2)]較佳為0.15以上，更佳為0.20以上，又更佳為0.25以上，另外，較佳為1.00以下，更佳為0.90以下，又更佳為0.80以下。In the curable adhesive sheet according to one aspect of the present invention, from the viewpoint of producing a curable adhesive sheet adjusted to satisfy the above requirements (II) and (IIa), the thickness (T1) of the first release film and the second release film are The thickness (T2) ratio of the release film [(T1)/(T2)] is preferably 0.15 or more, more preferably 0.20 or more, still more preferably 0.25 or more, and is preferably 1.00 or less, more preferably 0.90 or less. , and preferably below 0.80.

[硬化性接著劑層] 本發明之一態樣之硬化性接著片所具有之硬化性接著劑層係能夠形成於23℃、1GHz之介電正切為0.01以下的硬化物。能夠形成之硬化物之於23℃、1GHz之介電正切為0.01以下，較佳為0.005以下，更佳為0.002以下。另外，該硬化物之於23℃、1GHz之介電正切之下限並無特別限制，較佳為0.00005以上，更佳為0.0001以上。再者，本說明書中，前述硬化物的介電正切意指根據後述之實施例所記載之方法所測定之值。 [Hardening adhesive layer] The curable adhesive layer of the curable adhesive sheet according to one aspect of the present invention can form a cured product having a dielectric tangent of 0.01 or less at 23° C. and 1 GHz. The hardened material that can be formed has a dielectric tangent of 0.01 or less at 23° C. and 1 GHz, preferably 0.005 or less, and more preferably 0.002 or less. In addition, the lower limit of the dielectric tangent of the hardened material at 23° C. and 1 GHz is not particularly limited, but is preferably 0.00005 or more, and more preferably 0.0001 or more. In addition, in this specification, the dielectric tangent of the said hardened material means the value measured based on the method described in the Example mentioned later.

使硬化性接著劑層硬化之方法，亦可為熱硬化法，亦可為光硬化法，能夠依據用途而適合選擇。例如，若為將本發明之一態樣之硬化性接著片作為蓋層片用途而形成用以保護電路基板的硬化物之情形，則較佳為熱硬化法。The method for hardening the curable adhesive layer may be a thermal hardening method or a light hardening method, and can be appropriately selected depending on the use. For example, when the curable adhesive sheet according to one aspect of the present invention is used as a cover sheet to form a cured product for protecting a circuit board, a thermal curing method is preferred.

本發明之一態樣之硬化性接著片中，就形成具有足以保護電路基板之程度的厚度之硬化物之觀點而言，硬化性接著劑層的厚度較佳為3.0μm以上，更佳為5.0μm以上，又更佳為10μm以上，進而更佳為15μm以上，另外，較佳為60μm以下，更佳為45μm以下。In the curable adhesive sheet according to one aspect of the present invention, from the viewpoint of forming a cured product having a thickness sufficient to protect the circuit board, the thickness of the curable adhesive layer is preferably 3.0 μm or more, more preferably 5.0 μm. μm or more, more preferably 10 μm or more, still more preferably 15 μm or more, and more preferably 60 μm or less, more preferably 45 μm or less.

本發明之一態樣之硬化性接著片所具有之硬化性接著劑層，能夠由含有黏合劑樹脂(A)(以下亦稱為「成分(A)」)之硬化性接著劑組成物所形成。本發明之一態樣所使用之前述硬化性接著劑組成物，就作成以滿足上述要件(I)或是要件(III)的方式進行調整之硬化性接著片之觀點、以及作成能夠形成提高接著強度以及低介電特性之硬化物之組成物之觀點而言，較佳係進而含有聚苯醚樹脂(B)(以下亦稱為「成分(B)」)，更佳係含有成分(A)以及成分(B)且進而含有具有兩個以上於末端具有雙鍵之不飽和烴基之多官能性化合物(C)(以下亦稱為「成分(C)」)。另外，本發明之一態樣所使用之硬化性接著劑組成物較佳為進而含有選自陽離子聚合起始劑(D)(以下亦稱為「成分(D)」)、可與成分(A)之前述反應性官能基反應之交聯劑(E)(以下亦稱為「成分(E)」)及矽烷偶合劑(F)(以下亦稱為「成分(F)」)中之一種以上。再者，本發明之一態樣所使用之硬化性接著劑組成物亦可於不損及本發明之效果之範圍，含有這些成分(A)至成分(F)以外之其它添加劑。 The curable adhesive layer of the curable adhesive sheet according to one aspect of the present invention can be formed from a curable adhesive composition containing a binder resin (A) (hereinafter also referred to as "component (A)"). . The above-mentioned curable adhesive composition used in one aspect of the present invention is a curable adhesive sheet adjusted to satisfy the above-mentioned requirement (I) or requirement (III), and can form a curable adhesive sheet that can improve the adhesion. From the viewpoint of the composition of the cured product having strength and low dielectric properties, it is preferable that it further contains polyphenylene ether resin (B) (hereinafter also referred to as "component (B)"), and more preferably it contains component (A) And the component (B) further contains a polyfunctional compound (C) having two or more unsaturated hydrocarbon groups having a double bond at the terminal (hereinafter also referred to as "component (C)"). In addition, the curable adhesive composition used in one aspect of the present invention preferably further contains a cationic polymerization initiator (D) (hereinafter also referred to as "component (D)") and a component (A) selected from the group consisting of: ) one or more of the cross-linking agent (E) (hereinafter also referred to as "component (E)") and the silane coupling agent (F) (hereinafter also referred to as "component (F)") that reacts with the aforementioned reactive functional group . Furthermore, the curable adhesive composition used in one aspect of the present invention may contain additives other than these components (A) to (F) within a range that does not impair the effects of the present invention.

本發明之一態樣所使用之硬化性接著劑組成物中，就以作成滿足上述要件(I)或是要件(III)的方式進行調整之硬化性接著片之觀點而言、以及作成能夠形成提高接著強度以及低介電特性之硬化性接著劑層或是該硬化性接著劑層之硬化物之組成物的觀點而言，相對於該硬化性接著劑組成物的有效成分的總量(100質量%)，成分(A)以及成分(B)的合計含量較佳為50質量%以上，更佳為60質量%以上，又更佳為70質量%以上，進而更佳為75質量%以上，另外，較佳為100質量%以下，更佳為99.90質量%以下，又更佳為99.00質量%以下，進而更佳為95.00質量%以下。The curable adhesive composition used in one aspect of the present invention is capable of forming a curable adhesive sheet adjusted in a manner that satisfies the above requirement (I) or requirement (III). From the viewpoint of improving the adhesive strength and the composition of a curable adhesive layer with low dielectric properties or a cured product of the curable adhesive layer, relative to the total amount of active ingredients of the curable adhesive composition (100 mass %), the total content of component (A) and component (B) is preferably 50 mass % or more, more preferably 60 mass % or more, still more preferably 70 mass % or more, and still more preferably 75 mass % or more, In addition, the content is preferably 100 mass% or less, more preferably 99.90 mass% or less, still more preferably 99.00 mass% or less, and still more preferably 95.00 mass% or less.

就上述觀點而言，本發明之一態樣所使用之硬化性接著劑組成物中，相對於該硬化性接著劑組成物的有效成分的總量(100質量%)，成分(A)、成分(B)、成分(C)、以及成分(D)的合計含量較佳為60質量%以上，更佳為75質量%以上，又更佳為90質量%以上，另外，通常亦可設為100質量%以下、99.70質量%以下、或是90質量%以下。From the above point of view, in the curable adhesive composition used in one aspect of the present invention, the component (A), component The total content of (B), component (C), and component (D) is preferably 60 mass% or more, more preferably 75 mass% or more, still more preferably 90 mass% or more, and it can usually be set to 100 Mass % or less, 99.70 mass % or less, or 90 mass % or less.

就上述觀點而言，本發明之一態樣所使用之硬化性接著劑組成物中，相對於該硬化性接著劑組成物的有效成分的總量(100質量%)，成分(A)、成分(B)、成分(C)、成分(D)、成分(E)、以及成分(F)的合計含量較佳為60質量%以上，更佳為75質量%以上，又更佳為90質量%以上，另外，通常亦可設為100質量%以下、99.70質量%以下、或是90質量%以下。以下，對本發明之一態樣所使用之硬化性接著劑組成物所含有之各成分加以詳細說明。 From the above point of view, in the curable adhesive composition used in one aspect of the present invention, the component (A), component The total content of (B), component (C), component (D), component (E), and component (F) is preferably 60 mass% or more, more preferably 75 mass% or more, still more preferably 90 mass% In addition to the above, the content may generally be 100 mass% or less, 99.70 mass% or less, or 90 mass% or less. Each component contained in the curable adhesive composition used in one aspect of the present invention will be described in detail below.

[成分(A)：黏合劑樹脂] 本發明之一態樣所使用之硬化性接著劑組成物較佳係含有黏合劑樹脂(A)。藉由含有黏合劑樹脂(A)，組成物作成硬化物時之接著強度優異，可形成形狀穩定性良好之硬化性接著劑層。黏合劑樹脂(A)可單獨使用，亦可併用兩種以上。 [Component (A): Binder resin] The curable adhesive composition used in one aspect of the present invention preferably contains a binder resin (A). By containing the binder resin (A), the composition has excellent bonding strength when it is made into a cured product, and can form a curable adhesive layer with good shape stability. The binder resin (A) may be used alone, or two or more types may be used in combination.

本發明之一態樣所使用之硬化性接著劑組成物中，相對於該硬化性接著劑組成物的有效成分的總量(100質量%)，成分(A)的含量較佳為35質量%以上，更佳為45質量%以上，又更佳為55質量%以上，另外，較佳為90質量%以下，更佳為80質量%以下，又更佳為75質量%以下。In the curable adhesive composition used in one aspect of the present invention, the content of component (A) is preferably 35 mass% relative to the total amount of active ingredients (100 mass%) of the curable adhesive composition. Above, 45 mass % or more is more preferred, and 55 mass % or more is more preferred. In addition, 90 mass % or less is more preferred, 80 mass % or less is more preferred, and 75 mass % or less is more preferred.

本發明之一態樣所使用之黏合劑樹脂(A)的數量平均分子量(Mn)，就組成物能夠提高造膜性且形成形狀穩定性良好之硬化性接著劑層之觀點而言，較佳為10,000以上，更佳為25,000以上，又更佳為35,000以上，另外，在將組成物作成溶液的形態之情形時，就成分(A)相對於稀釋溶媒之溶解性良好而成為塗佈性優異之組成物之觀點而言，較佳為150,000以下，更佳為100,000以下，又更佳為70,000以下。The number average molecular weight (Mn) of the binder resin (A) used in one aspect of the present invention is preferable from the viewpoint that the composition can improve film-forming properties and form a curable adhesive layer with good shape stability. It is 10,000 or more, more preferably 25,000 or more, still more preferably 35,000 or more. In addition, when the composition is in the form of a solution, the solubility of component (A) in the dilution solvent is good and the coating property is excellent. From the viewpoint of the composition, it is preferably 150,000 or less, more preferably 100,000 or less, and still more preferably 70,000 or less.

作為黏合劑樹脂(A)，可列舉例如：聚烯烴系樹脂、苯氧基系樹脂、聚醯亞胺系樹脂、聚醯胺醯亞胺系樹脂、聚乙烯縮丁醛系樹脂、聚碳酸酯系樹脂、苯乙烯系樹脂等。這些黏合劑樹脂之中，本發明之一態樣所使用之黏合劑樹脂(A)，就組成物能夠形成於高頻區(例如，1GHz以上)之介電特性優異之硬化物之觀點而言，較佳係含有聚烯烴系樹脂。 Examples of the binder resin (A) include polyolefin-based resin, phenoxy-based resin, polyamide-imide-based resin, polyamide-imide-based resin, polyvinyl butyral-based resin, and polycarbonate. resin, styrenic resin, etc. Among these binder resins, the binder resin (A) used in one aspect of the present invention has a composition capable of forming a cured product having excellent dielectric properties in a high-frequency region (for example, 1 GHz or more). , preferably contains polyolefin resin.

聚烯烴系樹脂只要為具有源自烯烴系單體之構成單元之聚合物即可，可為僅由源自烯烴系單體之構成單元所構成之聚合物，亦可為具有源自烯烴系單體之構成單元以及源自可與烯烴系單體共聚之單體之構成單元之共聚物。The polyolefin-based resin only needs to be a polymer having structural units derived from olefin-based monomers. Copolymers of structural units derived from monomers and monomers copolymerizable with olefinic monomers.

構成聚烯烴系樹脂之烯烴系單體可列舉碳數2以上之α-烯烴，較佳為碳數2至8之α-烯烴，更佳為選自乙烯、丙烯、1-丁烯、異丁烯及1-己烯中的至少一種，進而較佳為選自乙烯及丙烯中的至少一種。這些烯烴系單體可單獨使用，亦可併用兩種以上。 The olefin monomers constituting the polyolefin resin include α-olefins having 2 or more carbon atoms, preferably α-olefins having 2 to 8 carbon atoms, and more preferably selected from the group consisting of ethylene, propylene, 1-butene, isobutylene and At least one kind of 1-hexene, more preferably at least one kind selected from the group consisting of ethylene and propylene. These olefin-based monomers may be used alone, or two or more types may be used in combination.

另外，作為構成聚烯烴系樹脂之可與烯烴系單體共聚之單體，可列舉例如：乙酸乙烯酯、(甲基)丙烯酸酯、苯乙烯等。這些單體可單獨使用，亦可併用兩種以上。本發明之一態樣所使用之聚烯烴系樹脂，具體而言，可列舉如：超低密度聚乙烯(VLDPE)、低密度聚乙烯(LDPE)、中密度聚乙烯(MDPE)、高密度聚乙烯(HDPE)、直鏈狀低密度聚乙烯、聚丙烯(PP)、乙烯-丙烯共聚物、烯烴系彈性體(TPO)、乙烯-乙酸乙烯酯共聚物(EVA)、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物等。 Examples of monomers constituting the polyolefin resin that can be copolymerized with olefin monomers include vinyl acetate, (meth)acrylate, styrene, and the like. These monomers may be used alone, or two or more types may be used in combination. The polyolefin-based resin used in one aspect of the present invention specifically includes ultra-low-density polyethylene (VLDPE), low-density polyethylene (LDPE), medium-density polyethylene (MDPE), and high-density polyethylene. Ethylene (HDPE), linear low-density polyethylene, polypropylene (PP), ethylene-propylene copolymer, olefin elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene-(methyl) Acrylic copolymer, ethylene-(meth)acrylate copolymer, etc.

本發明之一態樣所使用之黏合劑樹脂(A)，就組成物能夠提高造膜性且形成形狀穩定性良好之硬化性接著劑層，並能夠形成提高低介電特性之硬化物，並且使第一剝離膜或是第二剝離膜自硬化性接著劑層剝離時之剝離力降低之觀點而言，較佳係含有具有反應性官能基之黏合劑樹脂，更佳係含有選自具有反應性官能基之聚烯烴系樹脂、以及具有反應性官能基之苯乙烯系樹脂中之一種以上，更佳係至少含有具有反應性官能基之聚烯烴系樹脂(A1)。The binder resin (A) used in one aspect of the present invention can improve film-forming properties and form a curable adhesive layer with good shape stability as a composition, and can form a cured product with improved low dielectric properties, and From the viewpoint of reducing the peeling force when the first release film or the second release film is peeled off from the curable adhesive layer, it is preferable to contain an adhesive resin having a reactive functional group, and more preferably it contains an adhesive resin selected from the group consisting of those having reactive functional groups. At least one of a polyolefin-based resin with a reactive functional group and a styrenic resin with a reactive functional group, and more preferably at least a polyolefin-based resin (A1) having a reactive functional group.

本發明之一態樣所使用之硬化性接著劑組成物中，就組成物能夠形成低介電特性更加優異之硬化物之觀點來看，相對於該硬化性接著劑組成物所含有之成分(A)的總量(100質量%)，聚烯烴系樹脂(A1)的含有比率較佳為50質量%至100質量%、更佳為70質量%至100質量%，又更佳為85質量%至100質量%。In the curable adhesive composition used in one aspect of the present invention, from the viewpoint that the composition can form a cured product with more excellent low dielectric properties, relative to the components contained in the curable adhesive composition ( The total amount of A) (100 mass%), the content ratio of the polyolefin resin (A1) is preferably 50 mass% to 100 mass%, more preferably 70 mass% to 100 mass%, further preferably 85 mass% to 100 mass%.

作為黏合劑樹脂(A)所具有之反應性官能基，例如可列舉：羧基、具有羧酸酐結構之基、具有羧酸酯結構之基、羥基、環氧基、醯胺基、銨基、腈基、胺基、醯亞胺基、異氰酸酯基、乙醯基、硫醇基、碸基、膦醯基、硝基、鹵素原子、烷氧基矽基等。黏合劑樹脂(A)所具有之反應性官能基可僅由單獨一種構成，亦可由兩種以上之組合構成。這些之中，黏合劑樹脂(A)所具有之反應性官能基較佳為選自羧基、具有羧酸酐結構之基、環氧基、醯胺基、銨基、腈基、胺基、醯亞胺基、異氰酸酯基、乙醯基、硫醇基、醚基、硫醚基、碸基、膦醯基、硝基、胺基甲酸酯基、鹵素原子及烷氧基矽基中的基，就組成物能夠形成接著強度更優異的硬化物之觀點、以及使得將第一剝離膜或是第二剝離膜自硬化性接著劑層剝離時之剝離力降低之觀點來看，更佳為選自羧基及具有羧酸酐結構之基中的基，就組成物能夠形成接著強度更優異並且進而低介電特性亦更優異的硬化物之觀點而言，進而較佳為具有羧酸酐結構之基。 Examples of the reactive functional group possessed by the binder resin (A) include a carboxyl group, a group having a carboxylic acid anhydride structure, a group having a carboxylic acid ester structure, a hydroxyl group, an epoxy group, a amide group, an ammonium group, and a nitrile group. group, amine group, acyl imide group, isocyanate group, acetyl group, thiol group, styrene group, phosphonium group, nitro group, halogen atom, alkoxysilyl group, etc. The reactive functional group of the binder resin (A) may be composed of only one type, or may be composed of a combination of two or more types. Among these, the reactive functional group of the binder resin (A) is preferably selected from the group consisting of carboxyl groups, groups having a carboxylic anhydride structure, epoxy groups, amide groups, ammonium groups, nitrile groups, amine groups, and amide groups. Amino group, isocyanate group, acetyl group, thiol group, ether group, thioether group, styrene group, phosphonyl group, nitro group, urethane group, halogen atom and alkoxysilyl group, From the viewpoint that the composition can form a cured product with more excellent adhesive strength and from the viewpoint of reducing the peeling force when peeling the first release film or the second release film from the curable adhesive layer, it is more preferably selected from the group consisting of The group among the carboxyl group and the group having a carboxylic anhydride structure is more preferably a group having a carboxylic acid anhydride structure, from the viewpoint that the composition can form a cured product that has better bonding strength and further has better low dielectric properties.

本發明之一態樣所用之黏合劑樹脂(A)亦可為使用改質劑對成為主鏈之樹脂實施改質處理而導入有上述反應性官能基之改質樹脂。作為具體之改質樹脂，例如可列舉導入有酸基之酸改質樹脂、導入有羥基之樹脂，就組成物能夠形成接著強度更優異的硬化物之觀點、以及使得將第一剝離膜或是第二剝離膜自硬化性接著劑層剝離時之剝離力降低之觀點而言，較佳為導入有酸基之酸改質樹脂，就組成物能夠形成接著強度更優異並且進而低介電特性亦更優異的硬化物之觀點來看，更佳為導入有酸酐結構之酸酐改質樹脂。 The binder resin (A) used in one aspect of the present invention may be a modified resin in which the resin forming the main chain is modified using a modifier to introduce the above-mentioned reactive functional group. Specific modified resins include, for example, acid-modified resins into which acid groups have been introduced, resins into which hydroxyl groups have been introduced, from the viewpoint that the composition can form a cured product with better adhesion strength, and those that allow the first release film or the From the viewpoint of reducing the peeling force when the second release film is peeled off from the curable adhesive layer, it is preferable to introduce an acid-modified resin having an acid group, so that a composition can be formed that has better adhesion strength and further has low dielectric properties. From the viewpoint of a more excellent cured product, an acid anhydride-modified resin into which an acid anhydride structure is introduced is more preferred.

酸改質樹脂或是酸酐改質樹脂(以下亦稱為「不飽和羧酸等」)，可藉由例如使不飽和羧酸等於作為主鏈之樹脂進行反應而導入羧基或是羧酸酐結構進行接枝改質而獲得。將不飽和羧酸等導入樹脂之方法並無特別限制，可列舉例如：在有機過氧化物類或是偶氮腈類等自由基產生劑的存在下，將樹脂與不飽和羧酸等加熱熔融至樹脂的熔點以上而使之反應之方法；或是將樹脂與不飽和羧酸等溶解於有機溶劑之後，在自由基產生劑的存在下，經加熱以及攪拌使之反應之方法等。 Acid-modified resin or acid anhydride-modified resin (hereinafter also referred to as "unsaturated carboxylic acid, etc.") can be produced by, for example, reacting an unsaturated carboxylic acid with a resin serving as the main chain to introduce a carboxyl group or a carboxylic acid anhydride structure. Obtained by graft modification. The method of introducing unsaturated carboxylic acid or the like into the resin is not particularly limited. For example, in the presence of free radical generators such as organic peroxides or azonitriles, the resin and the unsaturated carboxylic acid or the like are heated and melted. A method of reacting the resin to a temperature above the melting point of the resin; or a method of dissolving the resin and unsaturated carboxylic acid in an organic solvent and then heating and stirring in the presence of a free radical generator to react.

作為不飽和羧酸，例如可列舉：馬來酸、富馬酸、伊康酸、檸康酸、戊烯二酸、四氫鄰苯二甲酸、烏頭酸等。作為不飽和羧酸酐，例如可列舉：馬來酸酐、伊康酸酐、戊烯二酸酐、檸康酸酐、烏頭酸酐、降冰片烯二羧酸酐、四氫鄰苯二甲酸酐等。這些不飽和羧酸及不飽和羧酸酐可單獨使用，亦可併用兩種以上。這些之中，就組成物能夠形成接著強度及低介電特性更優異的硬化物之觀點而言，較佳為馬來酸酐。 Examples of the unsaturated carboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, and the like. Examples of unsaturated carboxylic anhydrides include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, and the like. These unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides may be used alone, or two or more types may be used in combination. Among these, maleic anhydride is preferable from the viewpoint that the composition can form a cured product that is more excellent in bonding strength and low dielectric properties.

就組成物能夠形成接著強度及低介電特性更優異的硬化物之觀點而言，相對於樹脂100質量份，與樹脂反應之不飽和羧酸等之添加量較佳為0.1質量份至5質量份，更佳為0.2質量份至3質量份，進而較佳為0.2質量份至1質量份。From the viewpoint that the composition can form a cured product with better adhesion strength and low dielectric properties, the amount of the unsaturated carboxylic acid, etc. added to react with the resin is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the resin. parts, more preferably 0.2 to 3 parts by mass, and still more preferably 0.2 to 1 part by mass.

[成分(B)：聚苯醚樹脂] 本發明之一態樣所使用之硬化性接著劑組成物，就作成以滿足上述要件(I)或是要件(III)的方式進行調整之硬化性接著片之觀點、以及作成能夠形成提高接著強度以及低介電特性之硬化物之組成物之觀點而言，較佳係含有聚苯醚樹脂(B)。再者，聚苯醚樹脂(B)可單獨使用，亦可併用兩種以上。 [Component (B): Polyphenylene ether resin] The curable adhesive composition used in one aspect of the present invention is a curable adhesive sheet that is adjusted to satisfy the above requirement (I) or requirement (III), and is formed so as to improve the bonding strength. From the viewpoint of the composition of the cured material with low dielectric properties, it is preferable to contain polyphenylene ether resin (B). In addition, the polyphenylene ether resin (B) may be used alone, or two or more types may be used in combination.

本發明之一態樣所使用之硬化性接著劑組成物中，相對於成分(A)的總量100質量份，成分(B)的含量較佳為5質量份以上，更佳為12質量份以上，又更佳為17質量份以上，另外，較佳為80質量份以下，更佳為60質量份以下，又更佳為40質量份以下。In the curable adhesive composition used in one aspect of the present invention, the content of component (B) is preferably 5 parts by mass or more, more preferably 12 parts by mass, based on 100 parts by mass of the total amount of component (A). More preferably, it is 17 parts by mass or more, more preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and still more preferably 40 parts by mass or less.

就作成以滿足上述要件(I)或是要件(III)的方式進行調整之硬化性接著片之觀點、以及作成能夠形成提高接著強度以及低介電特性之硬化物之組成物之觀點而言，本發明之一態樣所使用之聚苯醚樹脂(B)的數量平均分子量(Mn)較佳為1500以上，更佳為1700以上，又更佳為1900以上，另外，就在將組成物作成溶液的形態之情形時，成為成分(B)與稀釋溶媒之溶解性良好且塗佈性優異之組成物之觀點而言，較佳為7000以下，更佳為5500以下，又更佳為4000以下。From the viewpoint of producing a curable adhesive sheet adjusted to satisfy the above requirement (I) or requirement (III), and from the perspective of producing a composition capable of forming a cured product with improved adhesive strength and low dielectric properties, The number average molecular weight (Mn) of the polyphenylene ether resin (B) used in one aspect of the present invention is preferably 1,500 or more, more preferably 1,700 or more, still more preferably 1,900 or more. In addition, just before the composition is made In the form of a solution, from the viewpoint of forming a composition with good solubility of component (B) and the dilution solvent and excellent coating properties, it is preferably 7000 or less, more preferably 5500 or less, and still more preferably 4000 or less. .

本發明之一態樣所用之聚苯醚樹脂(B)只要為於主鏈具有下述通式(b-i)及式(b-ii)的至少一者所表示之構成單元之樹脂即可。 [化1] The polyphenylene ether resin (B) used in one aspect of the present invention only needs to be a resin having a structural unit represented by at least one of the following general formula (bi) and formula (b-ii) in the main chain. [Chemical 1]

上述通式(b-i)或式(b-ii)中，R ^a1及R ^a2分別獨立為鹵素原子(氟原子、氯原子、溴原子或碘原子)、碳數1至6之烷基、或苯基，較佳為碳數1至6之烷基，更佳為碳數1至4之烷基，進而較佳為碳數1至3之烷基，進而更佳為甲基或乙基，尤佳為甲基。再者，作為可選擇來作為R ^a1及R ^a2之碳數1至6之烷基，例如可列舉：甲基、乙基、正丙基、異丙基、正丁基、三級丁基、二級丁基、異丁基、正戊基、正己基等。 m1及m2分別獨立為0至4之整數，較佳為0至3之整數，更佳為0至2之整數，進而較佳為2。 In the above general formula (bi) or formula (b-ii), R ^a1 and R ^a2 are each independently a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom), an alkyl group having 1 to 6 carbon atoms, or benzene. The group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, even more preferably an alkyl group having 1 to 3 carbon atoms, even more preferably a methyl or ethyl group, especially Preferably methyl. Furthermore, examples of the alkyl group having 1 to 6 carbon atoms that can be selected as R ^a1 and R ^a2 include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, Secondary butyl, isobutyl, n-pentyl, n-hexyl, etc. m1 and m2 are each independently an integer from 0 to 4, preferably an integer from 0 to 3, more preferably an integer from 0 to 2, and even more preferably 2.

就作成以滿足上述要件(I)或是要件(III)的方式進行調整之硬化性接著片，進而作成能夠形成使低介電特性良好並且使接著強度進一步提高的硬化物之組成物之觀點而言，本發明之一態樣所用之聚苯醚樹脂(B)較佳為具有下述式(b-1)所表示之骨架作為主鏈之樹脂。 [化2] This is from the viewpoint of preparing a curable adhesive sheet adjusted so as to satisfy the above requirement (I) or requirement (III), and further forming a composition capable of forming a cured product having good low dielectric properties and further improving the adhesive strength. In other words, the polyphenylene ether resin (B) used in one aspect of the present invention is preferably a resin having a skeleton represented by the following formula (b-1) as a main chain. [Chemicalization 2]

上述通式(b-1)中，R ^a1及R ^a2以及m1及m2與上述通式(b-i)或式(b-ii)中之定義相同，關於合適之基之種類及數值範圍亦相同。 X為二價之有機基，該有機基之至少一個氫原子亦可經取代基取代。 p1及p2分別獨立為0以上之整數，且p1＋p2為1以上之整數。 *表示與末端基之鍵結位置。 In the above-mentioned general formula (b-1), R ^a1 and R ^a2 and m1 and m2 have the same definitions as in the above-mentioned general formula (bi) or formula (b-ii), and the types and numerical ranges of suitable bases are also the same. X is a divalent organic group, and at least one hydrogen atom of the organic group may also be substituted by a substituent. p1 and p2 are each independently an integer greater than 0, and p1+p2 is an integer greater than 1. *Indicates the bonding position with the terminal group.

作為可選擇來作為X之二價之烴基，例如可列舉：碳數1至20之伸烷基、碳數1至20之氧伸烷基、碳數1至20之伸烯基、成環碳數3至10之伸環烷基、成環碳數3至10之伸環烯基、伸苯基、聯伸苯基、聯三伸苯基、伸萘基及將這些基之兩種以上組合而成之基等。再者，上述伸烷基、氧伸烷基及伸烯基可為直鏈，亦可為支鏈。另外，上述伸烷基、氧伸烷基及伸烯基亦可具有選自鹵素原子、苯基、聯苯基、聯三苯基、萘基及碳數3至10之環烷基中的取代基。再者，上述伸環烷基、伸環烯基、伸苯基、聯伸苯基、聯三伸苯基及伸萘基亦可具有選自鹵素原子、碳數1至6之烷基、碳數1至6之氧烷基及碳數1至6之烯基中的取代基。 Examples of the divalent hydrocarbon group that can be selected as Cycloalkyl groups with 3 to 10 carbon atoms, cycloalkenyl groups with 3 to 10 ring carbon atoms, phenylene groups, biphenylene groups, terphenylene groups, naphthylene groups, and combinations of two or more of these groups The basis of the formation and so on. Furthermore, the above-mentioned alkylene group, oxyalkylene group and alkenylene group may be linear or branched. In addition, the above-mentioned alkylene group, oxyalkylene group and alkenylene group may also have a substitution selected from a halogen atom, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group and a cycloalkyl group having 3 to 10 carbon atoms. base. Furthermore, the above-mentioned cycloalkyl group, cycloalkenyl group, phenylene group, biphenylene group, terphenylene group and naphthylene group may also have a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon monoxide group. Substituents in oxyalkyl groups with 1 to 6 carbon atoms and alkenyl groups with 1 to 6 carbon atoms.

這些之中，就作成以滿足上述要件(I)或是要件(III)的方式進行調整之硬化性接著片、進而作成能夠形成使接著強度進一步提高的硬化物之組成物之觀點而言，X較佳為下述式(b-2)所表示之基。 [化3] Among these, from the viewpoint of producing a curable adhesive sheet adjusted to satisfy the above requirement (I) or requirement (III) and further forming a composition capable of forming a cured product that further improves the adhesive strength, X Preferable is a group represented by the following formula (b-2). [Chemical 3]

上述通式(b-2)中，R ^b1及R ^b2分別獨立為鹵素原子(氟原子、氯原子、溴原子或碘原子)、碳數1至6之烷基、碳數1至6之氧烷基或碳數1至6之烯基，較佳為碳數1至6之烷基，更佳為碳數1至4之烷基，進而較佳為碳數1至3之烷基，進而更佳為甲基或乙基，尤佳為甲基。再者，作為可選擇來作為R ^b1及R ^b2之碳數1至6之烷基，例如可列舉：甲基、乙基、正丙基、異丙基、正丁基、三級丁基、二級丁基、異丁基、正戊基、正己基等。 n1及n2分別獨立為0至4之整數，較佳為0至3之整數，更佳為1至3之整數，進而較佳為3。 In the above general formula (b-2), R ^b1 and R ^b2 are independently a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom), an alkyl group having 1 to 6 carbon atoms, and an oxygen having 1 to 6 carbon atoms. Alkyl group or alkenyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, further preferably an alkyl group having 1 to 3 carbon atoms, and further More preferably, it is methyl or ethyl, especially preferably methyl. Furthermore, examples of alkyl groups having 1 to 6 carbon atoms that can be selected as R ^b1 and R ^b2 include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, Secondary butyl, isobutyl, n-pentyl, n-hexyl, etc. n1 and n2 are each independently an integer from 0 to 4, preferably an integer from 0 to 3, more preferably an integer from 1 to 3, and even more preferably 3.

上述通式(b-2)中，A為單鍵或二價之烴基。作為可選擇來作為A之二價之烴基，例如可列舉：碳數1至20之伸烷基、碳數1至20之氧伸烷基、碳數1至20之伸烯基、成環碳數3至10之伸環烷基或成環碳數3至10之伸環烯基。再者，伸烷基、氧伸烷基及伸烯基可為直鏈，亦可為支鏈。另外，可選擇來作為A之烴基中，亦可具有選自鹵素原子、碳數1至6之烷基、碳數1至6之氧烷基、以及碳數1至6之烯基之取代基。這些之中，就作成以滿足上述要件(I)或是要件(III)的方式進行調整之硬化性接著片、進而作成能夠形成使接著強度進一步提高的硬化物之組成物之觀點而言，A較佳為單鍵或碳數1至20之伸烷基，更佳為單鍵。 In the above general formula (b-2), A is a single bond or a divalent hydrocarbon group. Examples of the divalent hydrocarbon group that can be selected as A include an alkylene group having 1 to 20 carbon atoms, an oxyalkylene group having 1 to 20 carbon atoms, an alkenylene group having 1 to 20 carbon atoms, and a ring-forming carbon group. A cycloalkyl group with 3 to 10 carbon atoms or a cycloalkenyl group with 3 to 10 ring carbon atoms. Furthermore, the alkylene group, oxyalkylene group and alkenylene group may be straight chain or branched chain. In addition, the hydrocarbon group selected as A may also have a substituent selected from a halogen atom, an alkyl group having 1 to 6 carbon atoms, an oxyalkyl group having 1 to 6 carbon atoms, and an alkenyl group having 1 to 6 carbon atoms. . Among these, from the viewpoint of producing a curable adhesive sheet adjusted to satisfy the above requirement (I) or requirement (III), and further forming a composition capable of forming a cured product that further improves the adhesive strength, A A single bond or an alkylene group having 1 to 20 carbon atoms is preferred, and a single bond is more preferred.

就作成以滿足上述要件(I)或是要件(III)的方式進行調整之硬化性接著片、進而作成能夠形成使接著強度進一步提高的硬化物之組成物之觀點而言，本發明之一態樣所用之聚苯醚樹脂(B)更佳為具有下述式(b-3)所表示之骨架作為主鏈之樹脂。 [化4] One aspect of the present invention is an aspect of the present invention from the viewpoint of producing a curable adhesive sheet adjusted so as to satisfy the above requirement (I) or requirement (III) and further forming a composition capable of forming a cured product that further improves the adhesive strength. The polyphenylene ether resin (B) used in this way is more preferably a resin having a skeleton represented by the following formula (b-3) as a main chain. [Chemical 4]

上述通式(b-3)中，R ^a1及R ^a2與上述通式(b-i)或式(b-ii)中之定義相同，關於合適之基之種類及數值範圍亦相同。另外，R ^b1及R ^b2與上述通式(b-2)中之定義相同，關於合適之基之種類及數值範圍亦相同。 p1及p2分別獨立為0以上之整數，且p1＋p2為1以上之整數。 *表示與末端基之鍵結位置。再者，上述通式(b-3)中之R ^a1、R ^a2、R ^b1及R ^b2分別獨立，較佳為碳數1至6之烷基，更佳為碳數1至4之烷基，進而較佳為碳數1至3之烷基，進而更佳為甲基或乙基，尤佳為甲基。 In the above-mentioned general formula (b-3), R ^a1 and R ^a2 have the same definitions as in the above-mentioned general formula (bi) or formula (b-ii), and the types and numerical ranges of suitable groups are also the same. In addition, R ^b1 and R ^b2 have the same definitions as in the above general formula (b-2), and the types and numerical ranges of suitable bases are also the same. p1 and p2 are each independently an integer greater than 0, and p1+p2 is an integer greater than 1. *Indicates the bonding position with the terminal group. Furthermore, R ^a1 , R ^a2 , R ^b1 and R ^b2 in the above general formula (b-3) are each independent, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. , more preferably an alkyl group having 1 to 3 carbon atoms, still more preferably a methyl group or an ethyl group, particularly preferably a methyl group.

本發明之一態樣所使用之聚苯醚樹脂(B)，就作成以滿足上述要件(I)或是要件(III)的方式進行調整之硬化性接著片、進而作成能夠形成進一步提高低介電特性、交聯性、以及耐熱性之硬化物之組成物之觀點而言，較佳係具有乙烯基之聚苯醚樹脂。作為聚苯醚樹脂(B)所具有之乙烯基，亦可如乙烯基苄基、乙烯基萘基等般構成烴系取代基之一部分。亦即，聚苯醚樹脂(B)係乙烯基或含乙烯基之烴基鍵結於聚苯醚骨架而成。 The polyphenylene ether resin (B) used in one aspect of the present invention is a curable adhesive sheet adjusted to satisfy the above requirement (I) or requirement (III), and is further capable of forming a low-dielectric bonding sheet. From the viewpoint of the composition of the cured product with electrical properties, crosslinkability, and heat resistance, polyphenylene ether resin having a vinyl group is preferred. The vinyl group contained in the polyphenylene ether resin (B) may constitute a part of the hydrocarbon-based substituent such as a vinyl benzyl group, a vinyl naphthyl group, or the like. That is, the polyphenylene ether resin (B) is formed by bonding vinyl groups or vinyl-containing hydrocarbon groups to the polyphenylene ether skeleton.

就作成以滿足上述要件(I)或是要件(III)的方式進行調整之硬化性接著片、進而作成能夠形成低介電特性、交聯性、以及耐熱性優異之硬化物之組成物之觀點而言，本發明之一態樣所用之聚苯醚樹脂(B)較佳為於主鏈之兩末端具有乙烯基或含乙烯基之烴基的樹脂。於主鏈之兩末端具有乙烯基或含乙烯基之烴基的聚苯醚樹脂(B)可藉由在形成成為主鏈之聚苯醚骨架後，於兩末端導入乙烯基或含乙烯基之烴基而獲得。具體而言，藉由使二官能酚化合物與單官能酚化合物反應而獲得於兩末端具有酚性羥基之聚合物後，使用4-(氯甲基)苯乙烯將末端酚性羥基加以乙烯基苄基醚化，而可獲得於聚苯醚骨架之兩末端具有乙烯基苄基的聚苯醚樹脂(B)。 The viewpoint is to prepare a curable adhesive sheet that is adjusted to satisfy the above requirement (I) or requirement (III), and to further create a composition capable of forming a cured product with excellent low dielectric properties, crosslinkability, and heat resistance. Specifically, the polyphenylene ether resin (B) used in one aspect of the present invention is preferably a resin having vinyl groups or vinyl-containing hydrocarbon groups at both ends of the main chain. Polyphenylene ether resin (B) having vinyl groups or vinyl-containing hydrocarbon groups at both ends of the main chain can be obtained by introducing vinyl groups or vinyl-containing hydrocarbon groups at both ends after forming a polyphenylene ether skeleton that becomes the main chain. And get. Specifically, after obtaining a polymer having phenolic hydroxyl groups at both ends by reacting a difunctional phenol compound with a monofunctional phenol compound, the terminal phenolic hydroxyl groups are added to vinyl benzyl using 4-(chloromethyl)styrene. By etherifying the polyphenylene ether skeleton, a polyphenylene ether resin (B) having vinyl benzyl groups at both ends of the polyphenylene ether skeleton can be obtained.

本發明之一態樣所用之聚苯醚樹脂(B)較佳為下述通式(b-4)所表示之化合物。 [化5] p1及p2分別獨立為0以上之整數，且p1＋p2為1以上之整數。 The polyphenylene ether resin (B) used in one aspect of the present invention is preferably a compound represented by the following general formula (b-4). [Chemistry 5] p1 and p2 are each independently an integer greater than 0, and p1+p2 is an integer greater than 1.

作為本發明之一態樣所用之聚苯醚樹脂(B)，亦可使用市售品。作為市售品，例如可列舉：三菱瓦斯化學股份有限公司製造之OPE-2St(上述通式(b-4)所表示之化合物)等。As the polyphenylene ether resin (B) used in one aspect of the present invention, a commercially available product can also be used. Examples of commercially available products include OPE-2St (a compound represented by the above general formula (b-4)) manufactured by Mitsubishi Gas Chemical Co., Ltd. and the like.

[成分(C)：多官能性化合物] 本發明之一態樣所使用之硬化性接著劑組成物較佳係含有多官能性化合物(C)，該多官能性化合物(C)具有兩個以上之於末端具雙鍵之不飽和烴基。再者，本發明中之多官能性化合物(C)係將相當於成分(A)及成分(B)之化合物除外。藉由製成含有上述聚苯醚樹脂(B)以及多官能性化合物(C)之組成物，而可形成使低介電特性及接著強度平衡良好地提高的硬化物。尤其多官能性化合物(C)具有兩個以上之前述不飽和烴基，故而藉由在所得之硬化物中形成交聯結構，而可形成使接著強度進一步提高的硬化物。再者，多官能性化合物(C)可單獨使用，亦可併用兩種以上。 [Component (C): Polyfunctional compound] The curable adhesive composition used in one aspect of the present invention preferably contains a polyfunctional compound (C) having two or more unsaturated hydrocarbon groups having double bonds at the terminals. In addition, the polyfunctional compound (C) in the present invention excludes compounds corresponding to the component (A) and the component (B). By forming a composition containing the above-mentioned polyphenylene ether resin (B) and the polyfunctional compound (C), it is possible to form a cured product in which low dielectric properties and bonding strength are improved in a good balance. In particular, since the polyfunctional compound (C) has two or more unsaturated hydrocarbon groups as described above, by forming a cross-linked structure in the obtained cured product, it is possible to form a cured product in which the bonding strength is further improved. In addition, the polyfunctional compound (C) may be used individually or in combination of 2 or more types.

本發明之一態樣所使用之硬化性接著劑組成物中，相對於成分(A)的總量100質量份，就作成能夠形成低介電特性優異之硬化物之組成物且作成提高貼附性之硬化性接著片之觀點而言，成分(C)的含量較佳為10質量份以上，更佳為15質量份以上，又更佳為20質量份以上，另外，由於當成分(C)的含量增加，則剝離力(R1)以及剝離力(R2)有上升的傾向，故就以滿足上述要件(I)或是要件(III)的方式將硬化性接著片進行調整之觀點而言，較佳為80質量份以下，更佳為60質量份以下，又更佳為40質量份以下。The curable adhesive composition used in one aspect of the present invention is a composition capable of forming a cured product excellent in low dielectric properties based on 100 parts by mass of the total amount of component (A) and improving adhesion. From the viewpoint of a durable curable adhesive sheet, the content of component (C) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and still more preferably 20 parts by mass or more. In addition, when component (C) The peeling force (R1) and peeling force (R2) tend to increase as the content of It is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and still more preferably 40 parts by mass or less.

本發明之一態樣所使用之硬化性接著劑組成物中，就作成能夠形成平衡良好地提高低介電特性、接著強度、以及耐熱性之硬化物之組成物之觀點而言，成分(B)與成分(C)之含量比[(B)／(C)]以質量比計算較佳為15／85以上，更佳為30／70以上，另外，較佳為85／15以下，更佳為70／30以下。In the curable adhesive composition used in one aspect of the present invention, from the viewpoint of forming a composition capable of forming a cured product that improves low dielectric properties, adhesive strength, and heat resistance in a well-balanced manner, component (B ) and component (C) content ratio [(B)/(C)] in terms of mass ratio is preferably 15/85 or more, more preferably 30/70 or more, and more preferably 85/15 or less, still more preferably It is below 70/30.

本發明之一態樣所使用之硬化性接著劑組成物中，相對於成分(A)的總量100質量份，就作成以滿足上述要件(I)或是要件(III)的方式進行調整且貼附性優異之硬化性接著片之觀點、以及作成可形成接著強度優異之硬化物之組成物之觀點而言，成分(B)以及成分(C)的合計含量較佳為85質量份以下，更佳為75質量份以下，又更佳為65質量份以下，另外，較佳為15質量份以上，更佳為25質量份以上，又更佳為35質量份以上。The curable adhesive composition used in one aspect of the present invention is adjusted so as to satisfy the above requirement (I) or requirement (III) with respect to 100 parts by mass of the total amount of component (A), and From the viewpoint of creating a curable adhesive sheet with excellent adhesiveness and a composition capable of forming a hardened material with excellent adhesive strength, the total content of component (B) and component (C) is preferably 85 parts by mass or less. More preferably, it is 75 parts by mass or less, further preferably 65 parts by mass or less. In addition, it is more preferably 15 parts by mass or more, more preferably 25 parts by mass or more, and still more preferably 35 parts by mass or more.

本發明之一態樣所用之多官能性化合物(C)所具有的每一個前述不飽和烴基之碳數較佳為2至7，更佳為2至4，又更佳為2至3。另外，作為前述不飽和烴基，例如可列舉：乙烯基、烯丙基、3-丁烯基、4-戊烯基、5-己烯基、異丙烯基、1-甲基-2-丙烯基、乙烯基苄基、乙烯基萘基等。這些之中，多官能性化合物(C)所具有之前述不飽和烴基較佳為烯丙基。 The number of carbon atoms in each of the aforementioned unsaturated hydrocarbon groups of the polyfunctional compound (C) used in one aspect of the present invention is preferably 2 to 7, more preferably 2 to 4, and still more preferably 2 to 3. Examples of the unsaturated hydrocarbon group include vinyl, allyl, 3-butenyl, 4-pentenyl, 5-hexenyl, isopropenyl, and 1-methyl-2-propenyl. , vinyl benzyl, vinyl naphthyl, etc. Among these, the unsaturated hydrocarbon group that the polyfunctional compound (C) has is preferably an allyl group.

本發明之一態樣所用之多官能性化合物(C)所具有的前述不飽和烴基之個數為2以上，但就作成能夠形成使交聯結構適度稀疏而龜裂之產生得到抑制的硬化物之組成物之觀點、以及作成於由硬化性接著劑層形成硬化物之接著步驟中抑制硬化收縮而可減少作為被黏附體之電路基板等板狀構件之翹曲的組成物之觀點而言，較佳為2至4，更佳為2至3，進而較佳為2。The number of the unsaturated hydrocarbon groups of the polyfunctional compound (C) used in one aspect of the present invention is 2 or more, and the cross-linked structure can be appropriately sparse and the occurrence of cracks can be suppressed to form a hardened product. From the viewpoint of the composition, and the viewpoint of creating a composition that suppresses curing shrinkage in the bonding step of forming a cured product from a curable adhesive layer and can reduce warpage of plate-shaped members such as circuit boards as adherends, Preferably it is 2-4, More preferably, it is 2-3, Still more preferably, it is 2.

就作成能夠形成使低介電特性及接著強度進一步平衡良好地提高的硬化物之組成物之觀點而言，本發明之一態樣所用之多官能性化合物(C)較佳為具有兩個以上之前述不飽和烴基並且進而具有飽和烴基之多官能性化合物。就上述觀點而言，本發明之一態樣所用之多官能性化合物(C)所具有的飽和烴基之個數較佳為1至4，更佳為1至2，又更佳為1。 From the viewpoint of forming a composition that can form a cured product that further improves low dielectric properties and bonding strength in a well-balanced manner, the polyfunctional compound (C) used in one aspect of the present invention preferably has two or more A polyfunctional compound having the aforementioned unsaturated hydrocarbon group and further a saturated hydrocarbon group. From the above point of view, the number of saturated hydrocarbon groups in the polyfunctional compound (C) used in one aspect of the present invention is preferably 1 to 4, more preferably 1 to 2, and still more preferably 1.

作為前述飽和烴基，例如可列舉烷基、經烷氧基取代之烷基等。作為前述烷基，例如可列舉：甲基、乙基、正丙基、異丙基、正丁基、三級丁基、二級丁基、異丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十五烷基等。該烷基之碳數較佳為1至20，更佳為4至18，進而較佳為6至16，進而更佳為8至15。 Examples of the saturated hydrocarbon group include an alkyl group, an alkyl group substituted with an alkoxy group, and the like. Examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, secondary butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl base, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, etc. The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 4 to 18, even more preferably from 6 to 16, even more preferably from 8 to 15.

作為前述經烷氧基取代之烷基，例如可列舉：甲氧基甲基、乙氧基甲基、2-甲氧基乙氧基甲基、苄氧基甲基等。該經烷氧基取代之烷基之碳數較佳為2至15，更佳為2至12，進而較佳為3至10。 Examples of the alkoxy-substituted alkyl group include methoxymethyl, ethoxymethyl, 2-methoxyethoxymethyl, benzyloxymethyl, and the like. The carbon number of the alkoxy-substituted alkyl group is preferably 2 to 15, more preferably 2 to 12, and still more preferably 3 to 10.

本發明之一態樣所用之多官能性化合物(C)較佳為包含具有兩個前述不飽和烴基之多官能性化合物(C1)。包含此種具有兩個前述不飽和烴基之多官能性化合物(C1)的組成物係如上文所述，可成為可形成龜裂產生得到抑制而作為被黏附體之電路基板等板狀構件之翹曲得以減少的硬化物之組成物，並且可成為可形成使低介電特性及接著強度進一步提高的硬化物之組成物。就上述觀點而言，多官能性化合物(C1)更佳為具有兩個前述不飽和烴基且具有至少一個飽和烴基之多官能性化合物。 The polyfunctional compound (C) used in one aspect of the present invention preferably contains a polyfunctional compound (C1) having two aforementioned unsaturated hydrocarbon groups. A composition containing such a polyfunctional compound (C1) having two unsaturated hydrocarbon groups as described above can be used as a warp for plate-shaped members such as circuit substrates as adherends by suppressing the formation of cracks. It is possible to obtain a composition that reduces curing and can form a cured product that further improves low dielectric properties and bonding strength. From the above viewpoint, the polyfunctional compound (C1) is more preferably a polyfunctional compound having two of the aforementioned unsaturated hydrocarbon groups and at least one saturated hydrocarbon group.

就上述觀點而言，本發明之一態樣所使用之硬化性接著劑組成物中，相對於該硬化性接著劑組成物所含有之成分(C)的總量(100質量%)，多官能性化合物(C1)的含有比率較佳為50質量%至100質量%、更佳為70質量%至100質量%，又更佳為80質量%至100質量%，進而更佳為90質量%至100質量%。From the above point of view, in the curable adhesive composition used in one aspect of the present invention, the polyfunctional adhesive composition is polyfunctional with respect to the total amount (100 mass %) of the component (C) contained in the curable adhesive composition. The content ratio of the sex compound (C1) is preferably 50 mass% to 100 mass%, more preferably 70 mass% to 100 mass%, further preferably 80 mass% to 100 mass%, and still more preferably 90 mass% to 90 mass% 100% by mass.

本發明之一態樣所用之多官能性化合物(C)較佳為具有雜環骨架之多官能性化合物。藉由包含具有雜環骨架之多官能性化合物，而可作成可形成使低介電特性及接著強度進一步提高的硬化物之組成物。作為具體之雜環骨架，可列舉：異氰脲酸酯骨架或甘脲骨架。 The polyfunctional compound (C) used in one aspect of the present invention is preferably a polyfunctional compound having a heterocyclic skeleton. By including a polyfunctional compound having a heterocyclic skeleton, it is possible to prepare a composition that can form a cured product that further improves low dielectric properties and bonding strength. Specific heterocyclic skeletons include isocyanurate skeleton and glycoluril skeleton.

作為本發明之一態樣所用之多官能性化合物(C)，可列舉：下述通式(c-1)所表示之具有異氰脲酸酯骨架之化合物、下述通式(c-2)所表示之具有甘脲骨架之化合物。 [化6] Examples of the polyfunctional compound (C) used in one aspect of the present invention include a compound having an isocyanurate skeleton represented by the following general formula (c-1), the following general formula (c-2) ) represents a compound with a glycoluril skeleton. [Chemical 6]

前述通式(c-1)中，R ¹¹至R ¹³分別獨立為於末端具雙鍵之不飽和烴基或飽和烴基，R ¹¹至R ¹³的至少兩個為前述不飽和烴基。另外，前述通式(c-2)中，R ²¹至R ²⁶分別獨立為氫原子、於末端具雙鍵之不飽和烴基或飽和烴基，R ²¹至R ²⁶的至少兩個為前述不飽和烴基。可選擇來作為R ¹¹至R ¹³及R ²¹至R ²⁶之不飽和烴基及飽和烴基之具體例示如上文所述，合適之碳數之範圍亦如上文所述。 In the aforementioned general formula (c-1), R ¹¹ to R ¹³ are each independently an unsaturated hydrocarbon group or a saturated hydrocarbon group having a double bond at the end, and at least two of R ¹¹ to R ¹³ are the aforementioned unsaturated hydrocarbon groups. In addition, in the aforementioned general formula (c-2), R ²¹ to R ²⁶ are each independently a hydrogen atom, an unsaturated hydrocarbon group or a saturated hydrocarbon group with a double bond at the terminal, and at least two of R ²¹ to R ²⁶ are the aforementioned unsaturated hydrocarbon groups. . Specific examples of unsaturated hydrocarbon groups and saturated hydrocarbon groups that can be selected as R ¹¹ to R ¹³ and R ²¹ to R ²⁶ are as described above, and the range of suitable carbon numbers is also as described above.

就可成為可形成龜裂產生得到抑制而作為被黏附體之電路基板等板狀構件之翹曲得以減少的硬化物之組成物，並且作成可形成使低介電特性及接著強度進一步提高的硬化物之組成物之觀點而言，本發明之一態樣所用之多官能性化合物(C)較佳為包含前述通式(c-1)所表示之具有異氰脲酸酯骨架之化合物，更佳為包含下述通式(c-11)所表示之具有異氰脲酸酯骨架之化合物(C11)。 [化7] This makes it possible to form a composition that can suppress the generation of cracks and reduce the warpage of plate-shaped members such as circuit boards that are adherends, and can also form a hardened material that can further improve low dielectric properties and bonding strength. From the viewpoint of the composition of the object, the polyfunctional compound (C) used in one aspect of the present invention preferably contains a compound having an isocyanurate skeleton represented by the aforementioned general formula (c-1), and more preferably Preferably, it contains a compound (C11) having an isocyanurate skeleton represented by the following general formula (c-11). [Chemical 7]

上述通式(c-11)中，R ^a為飽和烴基，具體之例示如上文所述。這些之中，R ^a較佳為烷基。該烷基之碳數較佳為1至20，更佳為4至18，進而較佳為6至16，進而更佳為8至15。 In the above general formula (c-11), R ^a is a saturated hydrocarbon group, and specific examples are as described above. Among these, R ^a is preferably an alkyl group. The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 4 to 18, even more preferably from 6 to 16, even more preferably from 8 to 15.

就上述觀點而言，本發明之一態樣所使用之硬化性接著劑組成物中，相對於該硬化性接著劑組成物所含有之成分(C)的總量(100質量%)，化合物(C11)的含有比率較佳為50質量%至100質量%，更佳為70質量%至100質量%，又更佳為80質量%至100質量%，進而更佳為90質量%至100質量%。From the above viewpoint, in the curable adhesive composition used in one aspect of the present invention, the compound ( The content ratio of C11) is preferably 50 mass% to 100 mass%, more preferably 70 mass% to 100 mass%, still more preferably 80 mass% to 100 mass%, still more preferably 90 mass% to 100 mass% .

再者，本發明之一態樣所用之多官能性化合物(C)亦可使用市售品。作為具體之市售品，例如可列舉：L-DAIC(製品名，四國化成工業股份有限公司製造，前述通式(c-11)所表示之化合物)、TAIC(註冊商標)(製品名，三菱化學股份有限公司製造，前述通式(c-1)中之R ¹¹至R ¹³為烯丙基之化合物)、TAG(製品名，四國化成工業股份有限公司製造，前述通式(c-2)所表示之化合物)等。 In addition, commercially available products can also be used as the polyfunctional compound (C) used in one aspect of the present invention. Specific commercial products include, for example, L-DAIC (product name, compound represented by the aforementioned general formula (c-11) manufactured by Shikoku Chemical Industry Co., Ltd.), TAIC (registered trademark) (product name, Manufactured by Mitsubishi Chemical Co., Ltd., a compound in which R ¹¹ to R ¹³ in the aforementioned general formula (c-1) is an allyl group), TAG (product name, manufactured by Shikoku Chemical Industry Co., Ltd., the aforementioned general formula (c- 2) The compounds represented), etc.

本發明之一態樣所使用之多官能性化合物(C)的分子量(式量)，就作成容易形成具有期望的物性之硬化物之組成物之觀點、以及由於成分(C)的分子量越小則剝離力(R1)以及剝離力(R2)越加傾向上升故以滿足上述要件(I)或是要件(III)的方式將硬化性接著片進行調整之觀點而言，較佳為200以上，更佳為230以上，又更佳為270以上，另外，就作成容易形成於常溫易貼附之硬化性接著劑層之組成物之觀點而言，較佳為1000以下，更佳為800以下，又更佳為500以下。The molecular weight (formula weight) of the polyfunctional compound (C) used in one aspect of the present invention is from the viewpoint of forming a composition that easily forms a hardened product with desired physical properties, and because the smaller the molecular weight of the component (C), the smaller Then the peeling force (R1) and the peeling force (R2) tend to increase. Therefore, from the perspective of adjusting the curable adhesive sheet so as to satisfy the above requirement (I) or requirement (III), it is preferably 200 or more. More preferably, it is 230 or more, and still more preferably, it is 270 or more. In addition, from the viewpoint of forming a composition that is easy to form a hardening adhesive layer that is easy to adhere at normal temperature, it is preferably 1,000 or less, and more preferably 800 or less. It is better to be below 500.

本發明之一態樣所用之多官能性化合物(C)之沸點較佳為175℃至350℃，更佳為200℃至300℃。另外，本發明之一態樣所用之多官能性化合物(C)之5%重量減少溫度較佳為175℃至350℃，更佳為200℃至300℃。 The boiling point of the polyfunctional compound (C) used in one aspect of the present invention is preferably 175°C to 350°C, more preferably 200°C to 300°C. In addition, the 5% weight reduction temperature of the polyfunctional compound (C) used in one aspect of the present invention is preferably 175°C to 350°C, more preferably 200°C to 300°C.

另外，就作成能夠形成低介電特性優異的硬化物之組成物、並且作成容易形成於常溫易貼附的硬化性接著劑層之組成物之觀點而言，本發明之一態樣所用之多官能性化合物(C)較佳為於25℃為液體之化合物。再者，於本說明書中，所謂「於25℃為液體之化合物」，係指於25℃具有流動性之化合物，具體而言係指使用E型黏度計於25℃、1.0rpm測定之黏度為2mPa·s至10000mPa·s之化合物。 In addition, from the viewpoint of producing a composition that can form a cured material excellent in low dielectric properties and a composition that can easily form a curable adhesive layer that is easy to adhere at room temperature, one aspect of the present invention is used in many ways. The functional compound (C) is preferably a compound that is liquid at 25°C. Furthermore, in this specification, "a compound that is liquid at 25°C" refers to a compound that is fluid at 25°C. Specifically, it means that the viscosity measured using an E-type viscometer at 25°C and 1.0 rpm is: Compounds from 2mPa·s to 10000mPa·s.

[成分(D)：陽離子聚合起始劑] 本發明之一態樣所使用之硬化性接著劑組成物較佳為進而含有陽離子聚合起始劑(D)。藉由製成含有陽離子聚合起始劑(D)之硬化性接著劑組成物，而能夠充分進行成分(B)及成分(C)成分之聚合反應，提高所形成之硬化性接著劑層之保存穩定性。再者，陽離子聚合起始劑(D)可單獨使用，亦可併用兩種以上。 [Component (D): Cationic polymerization initiator] The curable adhesive composition used in one aspect of the present invention preferably further contains a cationic polymerization initiator (D). By preparing the curable adhesive composition containing the cationic polymerization initiator (D), the polymerization reaction of the component (B) and the component (C) can be fully carried out, and the preservation of the formed curable adhesive layer can be improved. Stability. In addition, the cationic polymerization initiator (D) may be used alone, or two or more types may be used in combination.

本發明之一態樣所使用之硬化性接著劑組成物中，就作成使成分(B)及成分(C)成分之聚合反應充分進行、能夠形成使保存穩定性提高的硬化性接著劑層之組成物之觀點而言，相對於成分(B)及成分(C)之合計量100質量份，成分(D)之含量較佳為0.01質量份以上，更佳為0.05質量份以上，更佳為0.10質量份以上，進而較佳為0.15質量份以上，進而較佳為0.20質量份以上，進而更佳為0.25質量份以上，尤佳為0.30質量份以上，另外，較佳為6.0質量份以下，更佳為5.0質量份以下，更佳為3.0質量份以下，進而較佳為2.0質量份以下，進而較佳為1.5質量份以下，進而更佳為1.0質量份以下，尤佳為0.70質量份以下。The curable adhesive composition used in one aspect of the present invention is such that the polymerization reaction of component (B) and component (C) can fully proceed and a curable adhesive layer with improved storage stability can be formed. From the viewpoint of the composition, the content of component (D) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and more preferably 100 parts by mass or more of the total amount of component (B) and component (C). 0.10 parts by mass or more, more preferably 0.15 parts by mass or more, still more preferably 0.20 parts by mass or more, still more preferably 0.25 parts by mass or more, especially 0.30 parts by mass or more, and preferably 6.0 parts by mass or less, More preferably, it is 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, still more preferably 2.0 parts by mass or less, still more preferably 1.5 parts by mass or less, still more preferably 1.0 parts by mass or less, particularly preferably 0.70 parts by mass or less. .

本發明之一態樣所用之陽離子聚合起始劑(D)可為熱陽離子聚合起始劑，亦可為光陽離子聚合起始劑，就能夠以簡便之步驟進行聚合之觀點而言，較佳為熱陽離子聚合起始劑。The cationic polymerization initiator (D) used in one aspect of the present invention may be a thermal cationic polymerization initiator or a photocationic polymerization initiator. From the viewpoint of enabling polymerization in a simple step, the cationic polymerization initiator (D) is preferred. It is a thermal cationic polymerization initiator.

本發明之一態樣所用之熱陽離子聚合起始劑為可藉由加熱而產生引發聚合之陽離子物種的化合物，例如可列舉：鋶鹽、四級銨鹽、鏻鹽、重氮鎓鹽、錪鹽等。這些熱陽離子聚合起始劑可單獨使用，亦可併用兩種以上。 The thermal cationic polymerization initiator used in one aspect of the present invention is a compound that can generate cationic species that initiate polymerization by heating. Examples include: sulfonium salts, quaternary ammonium salts, phosphonium salts, diazonium salts, and phosphonium salts. Salt etc. These thermal cationic polymerization initiators may be used alone, or two or more types may be used in combination.

作為鋶鹽，例如可列舉：三苯基鋶四氟硼酸鹽、三苯基鋶六氟銻酸鹽、三苯基鋶六氟砷酸鹽、三(4-甲氧基苯基)鋶六氟砷酸鹽、二苯基(4-苯硫基苯基)鋶六氟砷酸鹽等。另外，鋶鹽亦可使用市售品，例如可列舉：Adeka Opton SP-150、Adeka Opton SP-170、Adeka Opton CP-66、Adeka Opton CP-77(以上為艾迪科(ADEKA)股份有限公司製造)；Sun Aid SI-60L、Sun Aid SI-80L、Sun Aid SI-100L、Sun Aid SI-B2A、Sun Aid SI-B3(以上為三新化學工業股份有限公司製造)；CYRACURE UVI-6974、CYRACURE UVI-6990(以上為聯合碳化物(Union Carbide)公司製造)；UVI-508、UVI-509(以上為奇異(General Electric)公司製造)；FC-508、FC-509(以上為明尼蘇達礦業製造(Minnesota Mining and Manufacturing)公司製造)；CD-1010、CD-1011(以上為沙多瑪(Sartomer)公司製造)；CI系列之製品(日本曹達股份有限公司製造)等。 Examples of sulfonium salts include triphenylsonium tetrafluoroborate, triphenylsonium hexafluoroantimonate, triphenylsonium hexafluoroarsenate, and tris(4-methoxyphenyl)sonium hexafluoro Arsenate, diphenyl (4-phenylthiophenyl) hexafluoroarsenate, etc. In addition, commercially available sulfonium salts can also be used, for example: Adeka Opton SP-150, Adeka Opton SP-170, Adeka Opton CP-66, Adeka Opton CP-77 (the above is from ADEKA Co., Ltd. Manufactured); Sun Aid SI-60L, Sun Aid SI-80L, Sun Aid SI-100L, Sun Aid SI-B2A, Sun Aid SI-B3 (the above are manufactured by Sanxin Chemical Industry Co., Ltd.); CYRACURE UVI-6974, CYRACURE UVI-6990 (the above is manufactured by Union Carbide); UVI-508, UVI-509 (the above is manufactured by General Electric); FC-508, FC-509 (the above is manufactured by Minnesota Mining) (manufactured by Minnesota Mining and Manufacturing Company); CD-1010, CD-1011 (the above are manufactured by Sartomer Company); CI series products (manufactured by Japan Soda Co., Ltd.), etc.

作為四級銨鹽，例如可列舉：四丁基銨四氟硼酸鹽、四丁基銨六氟磷酸鹽、四丁基銨氫硫酸鹽、四乙基銨四氟硼酸鹽、四乙基銨對甲苯磺酸鹽、N,N-二甲基-N-苄基苯銨六氟銻酸鹽、N,N-二甲基-N-苄基苯銨四氟硼酸鹽、N,N-二甲基-N-苄基吡啶鎓六氟銻酸鹽、N,N-二乙基-N-苄基三氟甲磺酸鹽、N,N-二甲基-N-(4-甲氧基苄基)吡啶鎓六氟銻酸鹽、N,N-二乙基-N-(4-甲氧基苄基)甲苯銨六氟銻酸鹽等。Examples of quaternary ammonium salts include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrosulfate, tetraethylammonium tetrafluoroborate, and tetraethylammonium tetrafluoroborate. Tosylate, N,N-dimethyl-N-benzylanilinium hexafluoroantimonate, N,N-dimethyl-N-benzylanilinium tetrafluoroborate, N,N-dimethyl -N-Benzylpyridinium hexafluoroantimonate, N,N-diethyl-N-benzyltrifluoromethanesulfonate, N,N-dimethyl-N-(4-methoxybenzyl base)pyridinium hexafluoroantimonate, N,N-diethyl-N-(4-methoxybenzyl)toluidium hexafluoroantimonate, etc.

作為鏻鹽，例如可列舉乙基三苯基鏻六氟銻酸鹽、四丁基鏻六氟銻酸鹽等。Examples of phosphonium salts include ethyltriphenylphosphonium hexafluorantimonate, tetrabutylphosphonium hexafluorantimonate, and the like.

作為重氮鎓鹽，例如可列舉AMERICURE(美國製罐(American Can)公司製造)、ULTRASET(艾迪科公司製造)等。Examples of the diazonium salt include AMERICURE (manufactured by American Can Company), ULTRASET (manufactured by Adico Company), and the like.

作為錪鹽，例如可列舉：二苯基錪鎓六氟砷酸鹽、雙(4-氯苯基)錪鎓六氟砷酸鹽、雙(4-溴苯基)錪鎓六氟砷酸鹽、苯基(4-甲氧基苯基)錪鎓六氟砷酸鹽等。另外，錪鹽亦可使用市售品，例如可列舉：UV-9310C(東芝聚矽氧股份有限公司製造)、Photoinitiator 2074(羅納-普朗克(Rhone-Poulenc)公司製造)、UVE系列之製品(奇異公司製造)、FC系列之製品(明尼蘇達礦業製造公司製造)等。 Examples of iodonium salts include diphenylonium hexafluoroarsenate, bis(4-chlorophenyl)onium hexafluoroarsenate, and bis(4-bromophenyl)onium hexafluoroarsenate. , phenyl (4-methoxyphenyl) quinium hexafluoroarsenate, etc. In addition, commercially available ion salts can also be used, for example, UV-9310C (manufactured by Toshiba Polysilicone Co., Ltd.), Photoinitiator 2074 (manufactured by Rhone-Poulenc), and UVE series products (manufactured by Qiyi Company), FC series products (manufactured by Minnesota Mining Manufacturing Company), etc.

於本發明之一態樣之硬化性接著劑組成物含有陽離子聚合起始劑(D)之情形時，陽離子聚合起始劑(D)之至少一部分亦可為以下述條件進行差示掃描熱量測定所得之放熱波峰之峰頂溫度超過120℃的高溫反應性熱陽離子聚合起始劑。 [差示掃描熱量測定條件] 將調配成為測定對象之陽離子聚合起始劑0.1質量份、雙酚A二縮水甘油醚100質量份、γ-丁內酯0.1質量份而成之混合物作為測定試樣，自30℃至300℃以10℃/分鐘之升溫速度進行差示掃描熱量測定，測定放熱波峰之峰頂溫度。 When the curable adhesive composition according to one aspect of the present invention contains a cationic polymerization initiator (D), at least a part of the cationic polymerization initiator (D) may be subjected to differential scanning calorimetry under the following conditions. It is a high-temperature reactive thermal cationic polymerization initiator whose peak temperature of the exothermic peak exceeds 120°C. [Differential scanning calorimetry conditions] A mixture of 0.1 parts by mass of the cationic polymerization initiator, 100 parts by mass of bisphenol A diglycidyl ether, and 0.1 parts by mass of γ-butyrolactone prepared as the measurement object was used as a measurement sample. Differential scanning calorimetry was performed at a heating rate of 10°C/min to measure the peak temperature of the exothermic wave peak.

作為高溫反應性熱陽離子聚合起始劑之市售品，例如可列舉：Sun Aid SI-B3、Sun Aid SI-B4、Sun Aid SI-B5、Sun Aid SI-150(均為三新化學工業股份有限公司製造)等。Examples of commercially available high-temperature reactive thermal cationic polymerization initiators include: Sun Aid SI-B3, Sun Aid SI-B4, Sun Aid SI-B5, and Sun Aid SI-150 (all manufactured by Sanxin Chemical Industry Co., Ltd. Co., Ltd.), etc.

[陽離子聚合起始劑(D)以外之其它反應性硬化劑] 本發明之一態樣所使用之硬化性接著劑組成物亦可於不損及本發明之效果之範圍含有陽離子聚合起始劑(D)以外之其它反應性硬化劑來代替陽離子聚合起始劑(D)、或與陽離子聚合起始劑(D)一併含有。於本發明之一態樣所使用之硬化性接著劑組成物中，相對於成分(D)之總量100質量份，其它反應性硬化劑之含量亦可設為0質量份至90質量份、0質量份至50質量份、0質量份至40質量份、0質量份至30質量份、0質量份至20質量份、0質量份至10質量份、0質量份至5.0質量份、0質量份至2.0質量份、0質量份至1.0質量份、0質量份至0.10質量份、0質量份至0.010質量份或0質量份至0.0010質量份。另一方面，於本發明之一態樣之硬化性接著劑組成物不含有陽離子聚合起始劑(D)之情形時，相對於成分(B)及成分(C)之合計量100質量份，其它反應性硬化劑之含量亦可設為0.01質量份以上、0.05質量份以上、0.10質量份以上、0.15質量份以上、0.20質量份以上、0.25質量份以上或0.30質量份以上，另外，亦可設為6.0質量份以下、5.0質量份以下、3.0質量份以下、2.0質量份以下、1.5質量份以下、1.0質量份以下或0.70質量份以下。 [Reactive hardeners other than cationic polymerization initiator (D)] The curable adhesive composition used in one aspect of the present invention may also contain other reactive hardeners other than the cationic polymerization initiator (D) in place of the cationic polymerization initiator within a range that does not impair the effects of the present invention. (D), or contained together with the cationic polymerization initiator (D). In the curable adhesive composition used in one aspect of the present invention, the content of other reactive hardeners can also be set to 0 to 90 parts by mass relative to 100 parts by mass of the total amount of component (D). 0 parts by mass to 50 parts by mass, 0 parts by mass to 40 parts by mass, 0 parts by mass to 30 parts by mass, 0 parts by mass to 20 parts by mass, 0 parts by mass to 10 parts by mass, 0 parts by mass to 5.0 parts by mass, 0 parts by mass parts to 2.0 parts by mass, 0 parts by mass to 1.0 parts by mass, 0 parts by mass to 0.10 parts by mass, 0 parts by mass to 0.010 parts by mass, or 0 parts by mass to 0.0010 parts by mass. On the other hand, when the curable adhesive composition according to one aspect of the present invention does not contain the cationic polymerization initiator (D), based on 100 parts by mass of the total amount of the component (B) and the component (C), The content of other reactive hardeners can also be set to 0.01 parts by mass or more, 0.05 parts by mass or more, 0.10 parts by mass or more, 0.15 parts by mass or more, 0.20 parts by mass or more, 0.25 parts by mass or more, or 0.30 parts by mass or more. In addition, it can also be Let it be 6.0 parts by mass or less, 5.0 parts by mass or less, 3.0 parts by mass or less, 2.0 parts by mass or less, 1.5 parts by mass or less, 1.0 parts by mass or less, or 0.70 parts by mass or less.

作為陽離子聚合起始劑(D)以外之反應性硬化劑，例如可列舉：苄基甲基胺、2,4,6-三-二甲基胺基甲基苯酚等胺化合物；2-甲基咪唑、2-乙基-4-甲基咪唑、2-十七烷基咪唑等咪唑化合物；三氟化硼-單乙基胺錯合物、三氟化硼-哌嗪錯合物等路易斯酸；二(過氧化三級丁基)二異丙基苯等過氧化物等。Examples of reactive hardeners other than the cationic polymerization initiator (D) include: amine compounds such as benzylmethylamine and 2,4,6-tris-dimethylaminomethylphenol; 2-methyl Imidazole compounds such as imidazole, 2-ethyl-4-methylimidazole, and 2-heptadecylimidazole; Lewis acids such as boron trifluoride-monoethylamine complex, boron trifluoride-piperazine complex, etc. ; Two (tertiary butyl peroxide) diisopropylbenzene and other peroxides, etc.

[成分(E)：交聯劑] 本發明之一態樣所使用之硬化性接著劑組成物，作為成分(A)而含有具有反應性官能基之黏合劑樹脂之情形時，較佳係進而含有能夠與該反應性官能基反應之交聯劑(E)。藉由作成含有成分(A)與交聯劑(E)之組成物，而能夠形成接著劑成分之滲出抑制效果高之硬化性接著劑層。亦即，於由硬化性接著劑組成物所形成之塗膜來形成硬化性接著劑層之過程中，藉由交聯劑(E)與黏合劑樹脂(A)所具有之前述反應性官能基反應，而能夠於塗膜內形成交聯結構，形成即便受到加熱亦不易流動之硬化性接著劑層。結果，所形成之硬化性接著劑層於貼附於電路基板等被黏附體並硬化而與被黏附體接著之接著步驟中，變得更不易產生接著劑成分自端部滲出之現象。另外，就作成以滿足上述要件(I)以及要件(III)的方式進行調整之硬化性接著片之觀點而言，亦較佳係作成含有交聯劑(E)之組成物。再者，交聯劑(E)可單獨使用，亦可併用兩種以上。 [Ingredient (E): Cross-linking agent] When the curable adhesive composition used in one aspect of the present invention contains an adhesive resin having a reactive functional group as component (A), it is preferable that it further contains an adhesive resin capable of reacting with the reactive functional group. Cross-linking agent (E). By preparing a composition containing component (A) and cross-linking agent (E), it is possible to form a curable adhesive layer having a high bleed-out inhibitory effect of the adhesive component. That is, in the process of forming a curable adhesive layer from a coating film formed of a curable adhesive composition, the cross-linking agent (E) and the binder resin (A) have the aforementioned reactive functional groups. The reaction can form a cross-linked structure in the coating film, forming a hardening adhesive layer that is not easy to flow even when heated. As a result, the formed curable adhesive layer becomes less likely to cause the adhesive components to bleed out from the ends during the bonding step in which it is attached to an adherend such as a circuit board, hardens, and adheres to the adherend. In addition, from the viewpoint of producing a curable adhesive sheet adjusted so as to satisfy the above-mentioned requirements (I) and (III), it is also preferable to produce a composition containing the cross-linking agent (E). In addition, the cross-linking agent (E) may be used alone, or two or more types may be used in combination.

本發明之一態樣所使用之硬化性接著劑組成物中，相對於成分(A)的總量100質量份，成分(E)的含量較佳為0.01質量份以上，更佳為0.03質量份以上，更佳為0.05質量份以上，更佳為0.07質量份以上，又更佳為0.10質量份以上，又更佳為0.15質量份以上，又更佳為0.20質量份以上，進而更佳為0.25質量份以上，尤佳為0.30質量份以上，另外，較佳為10.0質量份以下，更佳為8.0質量份以下，更佳為6.0質量份以下，更佳為5.0質量份以下，又更佳為4.0質量份以下，又更佳為3.0質量份以下，又更佳為2.5質量份以下，進而更佳為2.0質量份以下，尤佳為1.5質量份以下。In the curable adhesive composition used in one aspect of the present invention, the content of component (E) is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass relative to 100 parts by mass of the total amount of component (A). Above, more preferably 0.05 parts by mass or more, more preferably 0.07 parts by mass or more, still more preferably 0.10 parts by mass or more, still more preferably 0.15 parts by mass or more, still more preferably 0.20 parts by mass or more, still more preferably 0.25 Parts by mass or more, more preferably 0.30 parts by mass or more, more preferably 10.0 parts by mass or less, more preferably 8.0 parts by mass or less, more preferably 6.0 parts by mass or less, more preferably 5.0 parts by mass or less, still more preferably 4.0 parts by mass or less, more preferably 3.0 parts by mass or less, still more preferably 2.5 parts by mass or less, still more preferably 2.0 parts by mass or less, particularly preferably 1.5 parts by mass or less.

就作成提高與成分(A)之反應概率、容易形成交聯結構、能夠形成接著劑成分之滲出抑制效果更高的硬化性接著劑層之組成物之觀點而言，本發明之一態樣所用之交聯劑(E)之分子量較佳為1000以下，更佳為800以下，進而較佳為700以下，進而更佳為600以下，尤佳為500以下，另外，就作成藉由形成硬化性接著劑層之乾燥步驟之加熱而以交聯劑(E)可滯留於該硬化性接著劑層內之方式調整，可表現出由添加交聯劑(E)所得之效果之組成物之觀點而言，上述分子量較佳為100以上，更佳為150以上，進而較佳為200以上，進而更佳為250以上，尤佳為300以上。From the viewpoint of creating a composition that increases the probability of reaction with component (A), easily forms a cross-linked structure, and can form a curable adhesive layer with a higher bleed-out inhibitory effect of the adhesive component, one aspect of the present invention is used. The molecular weight of the cross-linking agent (E) is preferably 1000 or less, more preferably 800 or less, further preferably 700 or less, still more preferably 600 or less, particularly preferably 500 or less. The heating of the drying step of the adhesive layer is adjusted so that the cross-linking agent (E) can remain in the curable adhesive layer, and the composition can express the effect obtained by adding the cross-linking agent (E). In other words, the molecular weight is preferably 100 or more, more preferably 150 or more, still more preferably 200 or more, still more preferably 250 or more, and particularly preferably 300 or more.

本發明之一態樣所用之交聯劑(E)係根據成分(A)所具有之反應性官能基之種類而適當選擇，例如可列舉：異氰酸酯系交聯劑、環氧系交聯劑、金屬螯合物系交聯劑、氮丙啶系交聯劑等。這些之中，就儲藏穩定性之觀點而言，本發明之一態樣所用之交聯劑(E)較佳為選自異氰酸酯系交聯劑、環氧系交聯劑及金屬螯合物系交聯劑中之至少一種。另外，就作成能夠形成使低介電特性進一步提高的硬化物之組成物之觀點而言，本發明之一態樣所用之交聯劑(E)較佳為具有異氰脲酸酯骨架之交聯劑。 The cross-linking agent (E) used in one aspect of the present invention is appropriately selected according to the type of reactive functional group possessed by the component (A). Examples thereof include: isocyanate-based cross-linking agent, epoxy-based cross-linking agent, Metal chelate-based cross-linking agents, aziridine-based cross-linking agents, etc. Among these, from the viewpoint of storage stability, the cross-linking agent (E) used in one aspect of the present invention is preferably selected from the group consisting of isocyanate-based cross-linking agents, epoxy-based cross-linking agents, and metal chelate-based cross-linking agents. At least one of the cross-linking agents. In addition, from the viewpoint of forming a composition capable of forming a cured product that further improves low dielectric properties, the cross-linking agent (E) used in one aspect of the present invention is preferably a cross-linking agent having an isocyanurate skeleton. combination agent.

異氰酸酯系交聯劑較佳為於分子內具有兩個以上之異氰酸酯基之化合物，例如可列舉：2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、氫化甲苯二異氰酸酯、氫化二甲苯二異氰酸酯、1,5-五亞甲基二異氰酸酯、1,6-六亞甲基二異氰酸酯、二苯基甲烷-4,4-二異氰酸酯、異佛爾酮二異氰酸酯、1,3-雙(異氰酸基甲基)環己烷、四甲基二甲苯二異氰酸酯、1,5-萘二異氰酸酯、三苯基甲烷三異氰酸酯、及這些聚異氰酸酯化合物與三羥甲基丙烷等多元醇化合物之加合物、這些聚異氰酸酯化合物之縮二脲物或異氰脲酸酯物等。The isocyanate cross-linking agent is preferably a compound having two or more isocyanate groups in the molecule, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate Isocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, diphenylmethane-4,4-diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanurate) Cyanatomethyl)cyclohexane, tetramethylxylene diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, and the addition of these polyisocyanate compounds and polyol compounds such as trimethylolpropane compounds, biuret compounds or isocyanurate compounds of these polyisocyanate compounds.

環氧系交聯劑較佳為於分子內具有兩個以上之環氧基之化合物，例如可列舉：1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、N,N,N’,N’-四縮水甘油基間二甲苯二胺、乙二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、三羥甲基丙烷二縮水甘油醚、二縮水甘油基苯胺、二縮水甘油胺等。The epoxy cross-linking agent is preferably a compound having two or more epoxy groups in the molecule, for example: 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl m-xylylenediamine, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, Diglycidyl aniline, diglycidylamine, etc.

金屬螯合物系交聯劑可列舉：具有作為交聯點發揮功能之金屬離子的螯合化合物。作為該金屬離子，例如可列舉：鋁離子、鋯離子、鈦離子、鋅離子、鐵離子、錫離子等。這些之中，金屬螯合物系交聯劑較佳為鋁螯合化合物，例如可列舉：三(乙醯丙酮)鋁、乙醯丙酮雙(乙醯乙酸乙酯)鋁、二異丙氧基單乙醯乙酸油酯鋁、單異丙氧基雙乙醯乙酸油酯鋁等。 Examples of metal chelate cross-linking agents include chelate compounds having metal ions that function as cross-linking points. Examples of the metal ions include aluminum ions, zirconium ions, titanium ions, zinc ions, iron ions, tin ions, and the like. Among these, the metal chelate cross-linking agent is preferably an aluminum chelate compound, and examples thereof include tris(acetyl acetonate)aluminum, acetyl acetonate bis(ethyl acetate acetate) aluminum, and diisopropoxy Aluminum monoacetate oleyl acetate, monoisopropoxy aluminum bis acetate oleyl acetate, etc.

這些之中，就作成能夠形成接著劑成分之滲出抑制效果更高的硬化性接著劑層之組成物、並且作成能夠形成使低介電特性進一步提高的硬化物之組成物之觀點而言，本發明之一態樣所用之交聯劑(E)較佳為異氰酸酯系交聯劑，更佳為聚異氰酸酯化合物之異氰脲酸酯物，進而較佳為選自1,5-五亞甲基二異氰酸酯之異氰脲酸酯物[1,3,5-三(5-異氰酸酯戊基)-1,3,5-三嗪-2,4,6-三酮]、及1,6-六亞甲基二異氰酸酯之異氰脲酸酯物[1,3,5-三(6-異氰酸酯己基)-1,3,5-三嗪-2,4,6-三酮]中的一種以上。Among these, from the viewpoint of forming a composition that can form a curable adhesive layer with a higher effect of inhibiting the bleeding of adhesive components and forming a composition that can form a cured material that further improves low dielectric properties, this invention The cross-linking agent (E) used in one aspect of the invention is preferably an isocyanate-based cross-linking agent, more preferably an isocyanurate compound of a polyisocyanate compound, and further preferably, it is selected from 1,5-pentamethylene. Isocyanurates of diisocyanates [1,3,5-tris(5-isocyanatopentyl)-1,3,5-triazine-2,4,6-trione], and 1,6-hexane One or more isocyanurates of methylene diisocyanate [1,3,5-tris(6-isocyanatehexyl)-1,3,5-triazine-2,4,6-trione].

[成分(F)：矽烷偶合劑] 本發明之一態樣所使用之硬化性接著劑組成物較佳為進而含有矽烷偶合劑(F)。藉由作成含有矽烷偶合劑之組成物，而能夠形成使接著強度進一步提高的硬化物。再者，矽烷偶合劑(F)可單獨使用，亦可併用兩種以上。 [Component (F): Silane coupling agent] The curable adhesive composition used in one aspect of the present invention preferably further contains a silane coupling agent (F). By forming a composition containing a silane coupling agent, it is possible to form a cured product with further improved bonding strength. In addition, the silane coupling agent (F) may be used alone, or two or more types may be used in combination.

本發明之一態樣所使用之硬化性接著劑組成物中，相對於成分(A)的總量100質量份，成分(F)的含量較佳為0.001質量份以上，更佳為0.005質量份以上，更佳為0.01質量份以上，更佳為0.03質量份以上，又更佳為0.05質量份以上，又更佳為0.07質量份以上，又更佳為0.10質量份以上，進而更佳為0.12質量份以上，尤佳為0.15質量份以上，另外，較佳為6.0質量份以下，更佳為5.0質量份以下，更佳為4.0質量份以下，更佳為3.0質量份以下，又更佳為2.0質量份以下，又更佳為1.5質量份以下，又更佳為1.0質量份以下，進而更佳為0.80質量份以下，尤佳為0.60質量份以下。In the curable adhesive composition used in one aspect of the present invention, the content of component (F) is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass relative to 100 parts by mass of the total amount of component (A). Above, more preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, still more preferably 0.05 parts by mass or more, still more preferably 0.07 parts by mass or more, still more preferably 0.10 parts by mass or more, still more preferably 0.12 More than 0.15 parts by mass, more preferably not less than 0.15 parts by mass, more preferably not more than 6.0 parts by mass, more preferably not more than 5.0 parts by mass, more preferably not more than 4.0 parts by mass, more preferably not more than 3.0 parts by mass, still more preferably 2.0 parts by mass or less, more preferably 1.5 parts by mass or less, still more preferably 1.0 parts by mass or less, still more preferably 0.80 parts by mass or less, particularly preferably 0.60 parts by mass or less.

本發明之一態樣所用之矽烷偶合劑(F)較佳為於分子內具有至少一個烷氧基矽基之有機矽化合物。作為具體之矽烷偶合劑，例如可列舉：3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷等具有(甲基)丙烯醯基之矽烷偶合劑；乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、二甲氧基甲基乙烯基矽烷、二乙氧基甲基乙烯基矽烷、三氯乙烯基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷等具有乙烯基之矽烷偶合劑；2-(3,4-環氧環己基)乙基三甲氧基矽烷、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、8-縮水甘油氧基辛基三甲氧基矽烷等具有環氧基之矽烷偶合劑；對苯乙烯基三甲氧基矽烷、對苯乙烯基三乙氧基矽烷等具有苯乙烯基之矽烷偶合劑；N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽基-N-(1,3-二甲基-亞丁基)丙基胺、N-苯基-3-胺基丙基三甲氧基矽烷、N-(乙烯基苄基)-2-胺基乙基-3-胺基丙基三甲氧基矽烷之鹽酸鹽等具有胺基之矽烷偶合劑；3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷等具有脲基之矽烷偶合劑；3-氯丙基三甲氧基矽烷、3-氯丙基三乙氧基矽烷等具有鹵素原子之矽烷偶合劑；3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷等具有巰基之矽烷偶合劑；雙(三甲氧基矽基丙基)四硫醚、雙(三乙氧基矽基丙基)四硫醚等具有硫醚基之矽烷偶合劑；3-異氰酸酯丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷等具有異氰酸酯基之矽烷偶合劑；烯丙基三氯矽烷、烯丙基三乙氧基矽烷、烯丙基三甲氧基矽烷等具有烯丙基之矽烷偶合劑；3-羥基丙基三甲氧基矽烷、3-羥基丙基三乙氧基矽烷等具有羥基之矽烷偶合劑等。 The silane coupling agent (F) used in one aspect of the present invention is preferably an organosilicon compound having at least one alkoxysilyl group in the molecule. Specific examples of the silane coupling agent include: 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane. Oxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, etc. with (meth)acrylyl groups Silane coupling agent; vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltris(2 -Methoxyethoxy)silane and other silane coupling agents with vinyl groups; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, Silane couplings with epoxy groups such as 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 8-glycidoxyoctyltrimethoxysilane, etc. Mixture; p-styryltrimethoxysilane, p-styryltriethoxysilane and other silane coupling agents with styryl groups; N-(2-aminoethyl)-3-aminopropylmethyldi Methoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, etc. have amine groups Silane coupling agents; 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane and other silane coupling agents with ureido groups; 3-chloropropyltrimethoxysilane, 3-chloropropyl Silane coupling agents with halogen atoms such as triethoxysilane; silane coupling agents with mercapto groups such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; bis(trimethoxy Silane coupling agents with thioether groups such as silicone propyl) tetrasulfide and bis (triethoxysilylpropyl) tetrasulfide; 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethyl Silane coupling agents with isocyanate groups such as oxysilane; silane coupling agents with allyl groups such as allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, etc.; 3-hydroxypropyl Silane coupling agents with hydroxyl groups such as trimethoxysilane and 3-hydroxypropyltriethoxysilane.

[環狀醚化合物] 本發明之一態樣所使用之硬化性接著劑組成物可為進而含有環狀醚化合物之組成物。作為環狀醚化合物，只要為具有環狀醚基之化合物則符合。作為環狀醚基，例如可列舉：環氧乙烷基(環氧基)、環氧丙烷基(氧雜環丁烷基)、四氫呋喃基、四氫吡喃基等。再者，於本說明書中，環氧乙烷基中，包含縮水甘油基、縮水甘油醚基、環氧環己基等具有環氧乙烷結構之基。再者，環狀醚化合物可單獨使用，亦可併用兩種以上。 [Cyclic ether compound] The curable adhesive composition used in one aspect of the present invention may be a composition further containing a cyclic ether compound. The cyclic ether compound is any compound having a cyclic ether group. Examples of the cyclic ether group include an oxirane group (epoxy group), an oxetanyl group (oxetanyl group), a tetrahydrofuranyl group, a tetrahydropyranyl group, and the like. In addition, in this specification, the ethylene oxide group includes groups having an ethylene oxide structure such as a glycidyl group, a glycidyl ether group, and an epoxycyclohexyl group. In addition, the cyclic ether compound may be used alone, or two or more types may be used in combination.

含有環狀醚化合物之組成物具有能夠形成接著強度優異的硬化物之特性，但另一方面，該硬化物之相對介電常數或介電正切之值變大，相較於含有上述(B)成分或(C)成分但不含環狀醚化合物之組成物，低介電特性有更差的傾向。A composition containing a cyclic ether compound has the characteristic of being able to form a cured product with excellent adhesion strength, but on the other hand, the relative permittivity or dielectric tangent value of the cured product becomes larger, compared to a composition containing the above (B) Component or (C) component but does not contain a cyclic ether compound, the low dielectric properties tend to be worse.

本發明之一態樣所使用之硬化性接著劑組成物中，相對於該硬化性接著劑組成物之有效成分之總量(100質量%)，環狀醚化合物之含量亦可為未達5.0質量%、未達3.0質量%、未達1.0質量%、未達0.50質量%、未達0.10質量%、未達0.010質量%、未達0.0010質量%、未達0.00010質量%或未達0.000010質量%。另外，於本發明之一態樣所使用之硬化性接著劑組成物中，相對於該硬化性接著劑組成物所含之成分(A)至成分(C)之合計量100質量份，環狀醚化合物之含量亦可為未達5.0質量份、未達3.0質量份、未達1.0質量份、未達0.50質量份、未達0.10質量份、未達0.010質量份、未達0.0010質量份、未達0.00010質量份或未達0.000010質量份。 In the curable adhesive composition used in one aspect of the present invention, the content of the cyclic ether compound may be less than 5.0 relative to the total amount of active ingredients (100% by mass) of the curable adhesive composition. Mass%, less than 3.0 mass%, less than 1.0 mass%, less than 0.50 mass%, less than 0.10 mass%, less than 0.010 mass%, less than 0.0010 mass%, less than 0.00010 mass%, or less than 0.000010 mass% . In addition, in the curable adhesive composition used in one aspect of the present invention, the ring-shaped The content of the ether compound may also be less than 5.0 parts by mass, less than 3.0 parts by mass, less than 1.0 parts by mass, less than 0.50 parts by mass, less than 0.10 parts by mass, less than 0.010 parts by mass, less than 0.0010 parts by mass, or less. Reaching 0.00010 parts by mass or less than 0.000010 parts by mass.

[無機填充材] 本發明之一態樣所使用之硬化性接著劑組成物可為進而含有無機填充材之組成物，亦可為不含無機填充材之組成物。作為無機填充材，例如可列舉：二氧化矽、氧化鋁、滑石、氫氧化鋁、氫氧化鎂、氧化鈦、雲母、硼酸鋁、硫酸鋇、氮化硼、矽酸鎂石、氧化鋅、氧化鎂、碳酸鈣等。這些無機填充材可單獨使用，亦可併用兩種以上。 [Inorganic filler] The curable adhesive composition used in one aspect of the present invention may be a composition that further contains an inorganic filler, or may be a composition that does not contain an inorganic filler. Examples of the inorganic filler include silica, alumina, talc, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, aluminum borate, barium sulfate, boron nitride, silicate, zinc oxide, oxide Magnesium, calcium carbonate, etc. These inorganic fillers may be used alone, or two or more types may be used in combination.

然而，本發明之一態樣所使用之硬化性接著劑組成物中，無機填充材之含量越少越佳。於本發明之一態樣所使用之硬化性接著劑組成物中，相對於該硬化性接著劑組成物之有效成分之總量(100質量%)，無機填充材之含量亦可設為0質量%至30質量%、0質量%至20質量%、0質量%至10質量%、0質量%至5.0質量%、0質量%至2.0質量%、0質量%至1.0質量%、0質量%至0.1質量%、0質量%至0.01質量%或0質量%至0.001質量%。另外，於本發明之一態樣所使用之硬化性接著劑組成物中，相對於該硬化性接著劑組成物所含之成分(A)至成分(C)之合計量100質量份，無機填充材之含量亦可設為未達50質量份、未達30質量份、未達10質量份、未達5.0質量份、未達1.0質量份、未達0.1質量份、未達0.01質量份、未達0.001質量份或未達0.0001質量份。 However, in the curable adhesive composition used in one aspect of the present invention, the smaller the content of the inorganic filler, the better. In the curable adhesive composition used in one aspect of the present invention, the content of the inorganic filler may be set to 0 mass relative to the total amount of active ingredients (100% by mass) of the curable adhesive composition. % to 30 mass%, 0 mass% to 20 mass%, 0 mass% to 10 mass%, 0 mass% to 5.0 mass%, 0 mass% to 2.0 mass%, 0 mass% to 1.0 mass%, 0 mass% to 0.1% by mass, 0% by mass to 0.01% by mass, or 0% by mass to 0.001% by mass. In addition, in the curable adhesive composition used in one aspect of the present invention, the inorganic filler is included in the curable adhesive composition based on 100 parts by mass of the total amount of the component (A) to the component (C) contained in the curable adhesive composition. The content of the material can also be set to less than 50 parts by mass, less than 30 parts by mass, less than 10 parts by mass, less than 5.0 parts by mass, less than 1.0 parts by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, or less. Reaching 0.001 parts by mass or less than 0.0001 parts by mass.

[其它添加劑] 本發明之一態樣所使用之硬化性接著劑組成物亦可於不妨礙本發明之效果之範圍，含有上述成分以外之其它添加劑。作為其它添加劑，例如可列舉：紫外線吸收劑、抗靜電劑、光穩定劑、抗氧化劑、樹脂穩定劑、顏料、增量劑、軟化劑等。這些添加劑分別可單獨使用，亦可併用兩種以上。再者，這些添加劑之含量可根據添加劑之種類而適當設定。例如，相對於硬化性接著劑組成物所含之成分(A)之總量100質量份，各添加劑之含量亦可設為0.001質量份至30質量份、0.005質量份至20質量份、0.01質量份至10質量份或0.03質量份至5質量份。 [Other additives] The curable adhesive composition used in one aspect of the present invention may also contain additives other than the above-mentioned components within a range that does not hinder the effects of the present invention. Examples of other additives include ultraviolet absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, pigments, extenders, softeners, and the like. These additives may be used individually, or two or more types may be used together. Furthermore, the content of these additives can be appropriately set according to the types of additives. For example, the content of each additive may be 0.001 to 30 parts by mass, 0.005 to 20 parts by mass, or 0.01 parts by mass relative to 100 parts by mass of the total component (A) contained in the curable adhesive composition. parts to 10 parts by mass or 0.03 parts by mass to 5 parts by mass.

[液體之有效成分] 本發明之一態樣所使用之硬化性接著劑組成物較佳為含有於25℃為液體之有效成分。藉由作成含有液體之有效成分的組成物，而能夠提高所形成之硬化性接著劑層之貼附性。 [Active ingredient of liquid] The curable adhesive composition used in one aspect of the present invention preferably contains an active ingredient that is liquid at 25°C. By forming a composition containing a liquid active ingredient, the adhesion of the formed curable adhesive layer can be improved.

本發明之一態樣所使用之硬化性接著劑組成物中，相對於該硬化性接著劑組成物的有效成分的總量(100質量%)，就作成能夠形成貼附性優異之硬化性接著劑層之組成物之觀點而言，於25℃之液體的有效成分的含量較佳為7.0質量%以上，更佳為10質量%以上，又更佳為12質量%以上，另外，由於於25℃之液體的有效成分的含量越多，剝離力(R1)以及剝離力(R2)有上升的傾向，故就以滿足上述要件(I)或是要件(III)的方式將硬化性接著片進行調整之觀點而言，較佳為50質量%以下，更佳為35質量%以下，又更佳為25質量%以下。The curable adhesive composition used in one aspect of the present invention is such that it can form a curable adhesive with excellent adhesion relative to the total amount (100% by mass) of the active ingredients of the curable adhesive composition. From the perspective of the composition of the agent layer, the content of the active ingredient in the liquid at 25°C is preferably 7.0 mass% or more, more preferably 10 mass% or more, and still more preferably 12 mass% or more. In addition, since the content at 25°C The peeling force (R1) and peeling force (R2) tend to increase as the content of the active ingredient of the liquid at ℃ increases. Therefore, the curable adhesive sheet should be processed so as to satisfy the above requirement (I) or requirement (III). From the viewpoint of adjustment, the content is preferably 50 mass% or less, more preferably 35 mass% or less, and still more preferably 25 mass% or less.

再者，就作成能夠形成貼附性優異之硬化性接著劑層之組成物、進而作成更加提高低介電特性以及接著強度之硬化物之組成物之觀點而言，本發明之一態樣所使用之硬化性接著劑組成物所含有之於25℃之液體的有效成分中至少一種較佳為多官能性化合物(C)。本發明之一態樣所使用之硬化性接著劑組成物中，相對於於25℃之液體的有效成分的總量(100質量%)，多官能性化合物(C)的含有比率較佳為70質量%以上，更佳為80質量%以上，又更佳為85質量%以上，另外，通常設為100質量%以下，較佳為99.0質量%以下，更佳為98.0質量%以下。 Furthermore, from the viewpoint of producing a composition that can form a curable adhesive layer with excellent adhesion and thereby produce a cured product that further improves low dielectric properties and bonding strength, one aspect of the present invention involves At least one of the active ingredients of the liquid at 25° C. contained in the curable adhesive composition used is preferably a polyfunctional compound (C). In the curable adhesive composition used in one aspect of the present invention, the content ratio of the polyfunctional compound (C) is preferably 70 relative to the total amount of active ingredients (100% by mass) of the liquid at 25°C. Mass % or more, more preferably 80 mass % or more, still more preferably 85 mass % or more, and usually 100 mass % or less, preferably 99.0 mass % or less, more preferably 98.0 mass % or less.

[稀釋溶媒] 本發明之一態樣所使用之硬化性接著劑組成物亦可進而添加稀釋溶媒而設為溶液之形態。作為本發明之一態樣所用之稀釋溶媒，例如可列舉：苯、甲苯等芳香族烴系溶媒；乙酸乙酯、乙酸丁酯等酯系溶媒；丙酮、甲基乙基酮、甲基異丁基酮等酮系溶媒；正戊烷、正己烷、正庚烷等脂肪族烴系溶媒；環戊烷、環己烷、甲基環己烷等脂環式烴系溶媒等。這些稀釋溶媒可單獨使用，亦可併用兩種以上。再者，這些稀釋溶媒可直接使用在成分(A)或成分(B)等之合成時所使用之溶媒，亦可添加在成分(A)或成分(B)之合成時所使用之溶媒以外的一種以上之溶媒。 [dilution solvent] The curable adhesive composition used in one aspect of the present invention may be in the form of a solution by adding a diluting solvent. Examples of the dilution solvent used in one aspect of the present invention include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, and methyl isobutyl. Ketone solvents such as base ketones; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and n-heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, and methylcyclohexane, etc. These diluting solvents may be used alone, or two or more types may be used in combination. In addition, these diluting solvents may be directly used as the solvent used in the synthesis of component (A) or component (B), etc., or may be added other than the solvent used in the synthesis of component (A) or component (B). More than one solvent.

本發明之一態樣所使用之硬化性接著劑組成物為溶液的形態之情形時，該硬化性接著劑組成物的有效成分濃度係考慮塗佈性等而以成為期望的黏度的方式進行適合設定，相對於該硬化性接著劑組成物的總量(100質量%)，較佳設為3.0質量%以上，更佳亦可設為10質量%以上，另外，較佳為70質量%以下，更佳亦可設為50質量%以下。When the curable adhesive composition used in one aspect of the present invention is in the form of a solution, the active ingredient concentration of the curable adhesive composition is appropriately adjusted so as to have a desired viscosity in consideration of coatability, etc. The setting is preferably 3.0 mass% or more, more preferably 10 mass% or more, and preferably 70 mass% or less, relative to the total amount of the curable adhesive composition (100 mass%). More preferably, it can be set to 50 mass % or less.

[硬化性接著片之製造方法] 作為本發明之一態樣之硬化性接著片之製造方法，可藉由公知之塗佈方法將上述的硬化性接著劑組成物塗佈於第一剝離膜或是第二剝離膜的剝離層上而製造。再者，就使對剝離膜之塗佈性良好之觀點而言，硬化性接著劑組成物較佳係以稀釋溶媒稀釋而設為溶液的形態。 [Method for manufacturing hardening adhesive sheet] As a method for manufacturing a curable adhesive sheet according to one aspect of the present invention, the above-mentioned curable adhesive composition can be coated on the release layer of the first release film or the second release film by a known coating method. And manufacturing. Furthermore, from the viewpoint of improving the coating properties of the release film, the curable adhesive composition is preferably diluted with a diluting solvent and in the form of a solution.

作為將硬化性接著劑組成物塗佈之方法，例如可列舉：旋轉塗佈法、噴霧塗佈法、棒塗法、刀片塗佈法、輥塗法、刮刀塗佈法、模塗法、凹版塗佈法等。Examples of methods for applying the curable adhesive composition include spin coating, spray coating, rod coating, blade coating, roll coating, blade coating, die coating, and gravure coating. Coating method, etc.

較佳為塗佈硬化性接著劑組成物而形成塗膜後，進行乾燥處理。作為乾燥處理方法，例如可列舉：熱風乾燥、熱輥乾燥、紅外線照射等。所形成之塗膜之乾燥條件較佳為於80℃至150℃之溫度加熱30秒鐘至5分鐘(較佳為40秒鐘至3分鐘，更佳為45秒鐘至2分鐘)進行乾燥。可經過該乾燥步驟而於第一剝離膜或是第二剝離膜的剝離層上形成硬化性接著劑層。進而，藉由於所形成之硬化性接著劑層中露出表面之表面上積層另一剝離膜，能夠作成本發明之一態樣之硬化性接著片。再者，就容易獲得滿足要件(II)之硬化性接著片之觀點而言，較佳係於第二剝離膜塗佈硬化性接著劑組成物，並於所形成之硬化性接著劑層中露出表面之表面上積層第一剝離膜。 It is preferable to apply the curable adhesive composition to form a coating film and then perform a drying process. Examples of drying treatment methods include hot air drying, hot roller drying, infrared irradiation, and the like. The drying condition of the formed coating film is preferably heating at a temperature of 80°C to 150°C for 30 seconds to 5 minutes (preferably 40 seconds to 3 minutes, more preferably 45 seconds to 2 minutes) for drying. Through this drying step, a curable adhesive layer can be formed on the release layer of the first release film or the second release film. Furthermore, by laminating another release film on the exposed surface of the formed curable adhesive layer, a curable adhesive sheet according to one aspect of the present invention can be produced. Furthermore, from the viewpoint of easily obtaining a curable adhesive sheet that satisfies requirement (II), it is preferable to apply the curable adhesive composition to the second release film and expose it in the formed curable adhesive layer. A first release film is laminated on the surface.

再者，於用於形成硬化性接著劑層之硬化性接著劑組成物含有交聯劑(E)之情形時，為了完成交聯反應，較佳為經過保持一定期間(例如1天至14天左右)之風乾步驟。Furthermore, when the curable adhesive composition for forming the curable adhesive layer contains a cross-linking agent (E), in order to complete the cross-linking reaction, it is preferable to maintain it for a certain period of time (for example, 1 day to 14 days). (left and right) air drying steps.

[硬化性接著片之使用方法、具硬化物之電路基板之製造方法] 使本發明之一態樣之硬化性接著片所具有的硬化性接著劑層硬化而成之硬化物係接著強度高，另外，高頻區域中之低介電特性亦優異。因此，本發明之一態樣之硬化性接著片可合適地使用於形成要求低介電特性之器件中之構件時，尤其較佳為用作用以保護電路基板之蓋層片。作為電路基板，例如可列舉可撓性印刷配線板(FPC)等。 [How to use curable adhesive sheets, and how to manufacture circuit boards with cured materials] The cured material obtained by hardening the curable adhesive layer of the curable adhesive sheet according to one aspect of the present invention has high adhesive strength and is also excellent in low dielectric properties in a high-frequency region. Therefore, the curable adhesive sheet according to one aspect of the present invention can be suitably used when forming components in devices requiring low dielectric properties, and is particularly preferably used as a cover sheet for protecting a circuit substrate. Examples of the circuit board include a flexible printed wiring board (FPC) and the like.

另外，本發明之一態樣之硬化性接著片所具有的硬化性接著劑層具有上述特性，故而本發明亦可提供下述[1]及[2]。 [1]一種硬化性接著片之使用方法，係具有：接著步驟，將上述本發明之一態樣之硬化性接著片所具有的硬化性接著劑層貼合於電路基板，使硬化性接著劑層硬化而製成硬化物，使該硬化物與前述電路基板接著。 [2]一種具硬化物之電路基板之製造方法，係具有：接著步驟，將上述本發明之一態樣之硬化性接著片所具有的硬化性接著劑層貼合於電路基板，使硬化性接著劑層硬化而製成硬化物，使該硬化物與前述電路基板接著。 In addition, since the curable adhesive layer of the curable adhesive sheet according to one aspect of the present invention has the above characteristics, the present invention can also provide the following [1] and [2]. [1] A method of using a curable adhesive sheet, which includes: a bonding step of bonding the curable adhesive layer of the curable adhesive sheet according to one aspect of the present invention to a circuit substrate, so that the curable adhesive The layer is cured to form a cured product, and the cured product is bonded to the circuit board. [2] A method for manufacturing a circuit board with a hardened material, which includes: a bonding step of bonding the curable adhesive layer of the curable adhesive sheet according to one aspect of the present invention to the circuit board to make the curable The adhesive layer is cured to form a cured product, and the cured product is bonded to the circuit board.

上述[1]及[2]中，作為使硬化性接著劑層硬化而作成硬化物之方法，能夠藉由成分(D)等反應性硬化劑的種類等加以調整，亦可為光硬化法，係根據作為硬化性接著劑層之形成材料的硬化性接著劑組成物所含之成分之種類來選擇。其中，較佳為熱硬化法。進行熱硬化時之加熱溫度較佳為80℃至200℃，更佳為90℃至190℃，進而較佳為100℃至180℃，加熱時間較佳為10分鐘至12小時，更佳為30分鐘至6小時，進而較佳為40分鐘至3小時。另外，於進行熱硬化時，較佳為進行熱壓。作為進行熱壓時之壓力，較佳為0.1MPa至10MPa，更佳為0.5MPa至8.0MPa，進而較佳為1.0MPa至5.0MPa。 In the above-mentioned [1] and [2], the method of hardening the curable adhesive layer to form a hardened product can be adjusted by the type of reactive hardener such as component (D), and may also be a photocuring method. The selection is based on the types of components contained in the curable adhesive composition that is the material for forming the curable adhesive layer. Among them, the thermal hardening method is preferred. The heating temperature during thermal hardening is preferably 80°C to 200°C, more preferably 90°C to 190°C, further preferably 100°C to 180°C, and the heating time is preferably 10 minutes to 12 hours, more preferably 30 minutes to 6 hours, and more preferably 40 minutes to 3 hours. In addition, when performing thermal hardening, it is preferable to perform hot pressing. The pressure during hot pressing is preferably 0.1 MPa to 10 MPa, more preferably 0.5 MPa to 8.0 MPa, further preferably 1.0 MPa to 5.0 MPa.

另外，於藉由光硬化法使硬化性接著劑層硬化之情形，可藉由向該硬化性接著劑層照射紫外線等能量線而製成硬化物。 [實施例] In addition, when the curable adhesive layer is cured by a photocuring method, a cured product can be produced by irradiating the curable adhesive layer with energy rays such as ultraviolet rays. [Example]

以下，列舉實施例對本發明加以更詳細說明。然而，本發明絲毫不限定於以下之實施例。另外，關於各物性值，為藉由以下所示之方法測定之值。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples at all. In addition, each physical property value is a value measured by the method shown below.

[數量平均分子量(Mn)] 使用凝膠滲透層析裝置(東曹股份有限公司製造，製品名「HLC-8320 GPC」)，於下述條件下進行測定，使用藉由標準聚苯乙烯換算所測定之值。 [測定條件] ·管柱：將「TSK gel guard column super H-H」、「TSK gel super HM-H」、「TSK gel super HM-H」及「TSK gel super H2000」依序連結而成(均為東曹股份有限公司製造) ·管柱溫度：40℃ ·展開溶媒：四氫呋喃 ·流速：1.0mL/min [Number average molecular weight (Mn)] A gel permeation chromatography device (manufactured by Tosoh Co., Ltd., product name "HLC-8320 GPC") was used to measure under the following conditions, and the value measured by standard polystyrene conversion was used. [Measurement conditions] ·Column: "TSK gel guard column super H-H", "TSK gel super HM-H", "TSK gel super HM-H" and "TSK gel super H2000" are connected in order (all Tosoh Co., Ltd. manufactured by the company) ·Column temperature: 40℃ ·Developing solvent: tetrahydrofuran ·Flow rate: 1.0mL/min

[剝離力(R1)] 將作為測定對象之硬化性接著片切斷為縱向150m×橫向50mm的大小來製作試驗樣品。繼而，於試驗樣品中之第二剝離膜的硬化性接著劑層接觸面之相反側之面貼附雙面膠帶其中一接著面，並將雙面膠帶的另一接著面重疊於金屬板的表面而加以壓接。然後，於溫度23℃、相對濕度50%的環境下，使用精密萬能試驗機(股份有限公司島津製作所製，製品名「AUTOGRAPH AG-IS」)，將作為剝離力的測定對象之第一剝離膜自固定於金屬板之試驗樣品以剝離角度180°、剝離速度300mm／分鐘的條件下進行剝離，將此時所測定之值設為「剝離力(R1)」。 [Peel strength (R1)] The curable adhesive sheet to be measured was cut into a size of 150 m in the longitudinal direction and 50 mm in the transverse direction to prepare a test sample. Then, attach one of the bonding surfaces of the double-sided tape to the surface opposite to the contact surface of the hardened adhesive layer of the second release film in the test sample, and overlap the other bonding surface of the double-sided tape on the surface of the metal plate And be crimped. Then, in an environment with a temperature of 23°C and a relative humidity of 50%, a precision universal testing machine (manufactured by Shimadzu Corporation, product name "AUTOGRAPH AG-IS") was used to test the first peeling film to be measured for peeling force. The test sample fixed on the metal plate was peeled off at a peeling angle of 180° and a peeling speed of 300mm/min. The value measured at this time was referred to as "peeling force (R1)".

[剝離力(R2)] 由作為測定對象之硬化性接著片除去第一剝離膜，將露出表面之接著面重疊於厚度25μm的聚醯亞胺膜(DU PONT-TORAY股份有限公司製，Kapton 100H)的表面，使用熱層壓機以100℃加以壓接。然後，將硬化性接著片與聚醯亞胺膜一起切斷成縱向150m×橫向50mm的大小來製作試驗樣品。於試驗樣品的聚醯亞胺膜中與積層有硬化性接著劑層之面為相反側之面貼附雙面膠帶其中一接著面，並將雙面膠帶的另一接著面重疊於金屬板的表面而加以壓接。對於該試驗樣品，進行與上述的剝離力(R1)的測定同樣的剝離試驗。亦即，於溫度23℃、相對濕度50%的環境下，使用前述精密萬能試驗機，將作為剝離力的測定對象之第二剝離膜自固定於金屬板之試驗樣品在剝離角度180°、剝離速度300mm／分鐘的條件下進行剝離，將此時所測定之值設為「剝離力(R2)」。 [Peel strength (R2)] The first release film was removed from the curable adhesive sheet to be measured, and the exposed adhesive surface was overlapped on the surface of a polyimide film (Kapton 100H, manufactured by DU PONT-TORAY Co., Ltd.) with a thickness of 25 μm, and a thermal layer was used. The press is pressed at 100°C. Then, the curable adhesive sheet and the polyimide film were cut into a size of 150 m in the longitudinal direction and 50 mm in the transverse direction to prepare a test sample. Attach one of the bonding surfaces of the double-sided tape to the polyimide film of the test sample on the opposite side to the surface where the hardening adhesive layer is laminated, and overlap the other bonding surface of the double-sided tape on the metal plate. surface and crimped. About this test sample, the same peeling test as the measurement of the peeling force (R1) mentioned above was performed. That is, in an environment with a temperature of 23°C and a relative humidity of 50%, using the above-mentioned precision universal testing machine, the second release film to be measured is peeled off from the test sample fixed to the metal plate at a peeling angle of 180°. Peeling was performed at a speed of 300 mm/min, and the value measured at this time was referred to as "peeling force (R2)".

製造例1至製造例2 (1)硬化性接著劑組成物之製備以表1所示之調配量(有效成分比)調配表1所示之成分，溶解於甲苯，以成為預定之有效成分濃度之方式製備硬化性接著劑組成物(1)至硬化性接著劑組成物(2)。用於製備硬化性接著劑組成物(1)至硬化性接著劑組成物(2)之各成分之詳細如下。 [成分(A)：黏合劑樹脂] ·「改質聚烯烴」：含有Mn＝47,000之馬來酸酐改質α-烯烴聚合物(於25℃為固體)之溶液(三井化學股份有限公司製造，製品名「Unistole H-200」)。 [成分(B)：聚苯醚樹脂] ·「聚苯醚樹脂(b1)」：含有Mn＝2,200之乙烯基苄基改質聚苯醚(前述通式(b-4)所表示之化合物，於25℃為固體)之溶液(三菱瓦斯化學股份有限公司製造，製品名「OPE-2St 2200」)。 ·「聚苯醚樹脂(b2)」：含有Mn＝1,200之乙烯基苄基改質聚苯醚(前述通式(b-4)所表示之化合物，於25℃為固體)之溶液(三菱瓦斯化學股份有限公司製造，製品名「OPE-2St 1200」)。 [成分(C)：多官能性化合物] ·「多官能性化合物」：前述通式(c-11)中之R ^a為碳數8至15之烷基的具有異氰脲酸酯骨架之化合物。四國化成工業股份有限公司製造，製品名「L-DAIC」，分子量＝377.27，於25℃為液體。 [成分(D)：陽離子聚合起始劑] ·「熱陽離子聚合起始劑」：熱陽離子聚合起始劑(三新化學工業股份有限公司製造，製品名「Sun Aid SI-B3」)，於25℃為固體。 [成分(E)：交聯劑] ·「異氰酸酯系交聯劑」：1,3,5-三(5-異氰酸酯戊基)-1,3,5-三嗪-2,4,6-三酮(三井化學股份有限公司製造，製品名「Stabio D-370N」)，分子量＝462，於25℃為液體。 [成分(F)：矽烷偶合劑] ·「矽烷偶合劑」：8-縮水甘油氧基辛基三甲氧基矽烷(信越化學工業股份有限公司，製品名「KBM4803」)，於25℃為液體。 Production Example 1 to Production Example 2 (1) Preparation of Curable Adhesive Composition The ingredients shown in Table 1 were prepared in the amounts (active ingredient ratios) shown in Table 1, and dissolved in toluene to obtain a predetermined active ingredient concentration. The curable adhesive composition (1) to the curable adhesive composition (2) are prepared in the following manner. Details of each component used to prepare the curable adhesive composition (1) to the curable adhesive composition (2) are as follows. [Component (A): Binder resin] "Modified polyolefin": A solution containing a maleic anhydride-modified α-olefin polymer (solid at 25°C) containing Mn=47,000 (manufactured by Mitsui Chemicals Co., Ltd., Product name "Unistole H-200"). [Component (B): Polyphenylene ether resin] "Polyphenylene ether resin (b1)": Vinyl benzyl modified polyphenylene ether containing Mn=2,200 (a compound represented by the aforementioned general formula (b-4), It is a solid at 25°C) solution (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name "OPE-2St 2200"). · "Polyphenylene ether resin (b2)": a solution containing vinyl benzyl modified polyphenylene ether (a compound represented by the aforementioned general formula (b-4), solid at 25°C) with Mn=1,200 (Mitsubishi Gas Manufactured by Chemical Co., Ltd., product name "OPE-2St 1200"). [Component (C): Polyfunctional compound] "Polyfunctional compound": a compound having an isocyanurate skeleton in which R ^a in the aforementioned general formula (c-11) is an alkyl group having 8 to 15 carbon atoms. . Manufactured by Shikoku Chemical Industry Co., Ltd., product name "L-DAIC", molecular weight = 377.27, liquid at 25°C. [Component (D): Cationic polymerization initiator] "Thermal cationic polymerization initiator": Thermal cationic polymerization initiator (manufactured by Sanshin Chemical Industry Co., Ltd., product name "Sun Aid SI-B3"), in It is solid at 25℃. [Component (E): Cross-linking agent] "Isocyanate-based cross-linking agent": 1,3,5-tris(5-isocyanatopentyl)-1,3,5-triazine-2,4,6-tris Ketone (manufactured by Mitsui Chemicals Co., Ltd., product name "Stabio D-370N"), molecular weight = 462, liquid at 25°C. [Component (F): Silane coupling agent] "Silane coupling agent": 8-glycidoxyoctyltrimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., product name "KBM4803"), which is liquid at 25°C.

[表1] 接著劑組成物中的各成分的調配量(有效成分比) 成分(A) 成分(B) 成分(C) 成分(D) 成分(E) 成分(F) 改質聚烯烴聚苯醚樹脂(b1) 聚苯醚樹脂(b2) 多官能性化合物熱陽離子聚合起始劑異氰酸酯系交聯劑矽烷偶合劑質量份質量份質量份質量份質量份質量份質量份製造例1 硬化性接著劑組成物(1) 100 25 - 25 0.24 0.5 0.2 製造例2 硬化性接著劑組成物(2) 100 - 25 25 0.24 0.5 0.2 [Table 1] The amount of each component in the adhesive composition (active ingredient ratio) Ingredient(A) Ingredient(B) Ingredients(C) Ingredients(D) Ingredients(E) Ingredients(F) Modified polyolefin Polyphenylene ether resin (b1) Polyphenylene ether resin (b2) polyfunctional compounds Thermal cationic polymerization initiator Isocyanate cross-linking agent Silane coupling agent parts by mass parts by mass parts by mass parts by mass parts by mass parts by mass parts by mass Manufacturing example 1 Hardening adhesive composition (1) 100 25 - 25 0.24 0.5 0.2 Manufacturing example 2 Hardening adhesive composition (2) 100 - 25 25 0.24 0.5 0.2

實施例1至實施例2、比較例1至比較例2 以下的實施例以及比較例所使用之剝離膜以及作為硬化性接著劑層的形成材料之硬化性接著劑組成物係如以下所述。 [第一剝離膜] ・非聚矽氧系剝離膜(1)：製品名「PC38　AL-5」，琳得科股份有限公司製，經發泡而作成白色之聚對苯二甲酸乙二酯(PET)膜上具有由醇酸系剝離劑所形成之剝離層之非聚矽氧系剝離膜，厚度：38μm。 [第二剝離膜] ・非聚矽氧系剝離膜(2)：製品名「SP-PET50　AL-5」，琳得科股份有限公司製，無色的PET膜上具有由醇酸系剝離劑所形成之剝離層之非聚矽氧系剝離膜，厚度：50μm。・非聚矽氧系剝離膜(3)：製品名「SP-PET75　AL-5」，琳得科股份有限公司製，無色的PET膜上具有由醇酸系剝離劑所形成之剝離層之非聚矽氧系剝離膜、厚度：75μm。 [硬化性接著劑層的形成材料] ・硬化性接著劑組成物(1)：製造例1以於表1所記載之組成所製備之硬化性接著劑組成物(1)。・硬化性接著劑組成物(2)：製造例2以於表1所記載之組成所製備之硬化性接著劑組成物(2)。 Example 1 to Example 2, Comparative Example 1 to Comparative Example 2 The release film used in the following Examples and Comparative Examples and the curable adhesive composition as a forming material of the curable adhesive layer are as follows. [First peeling film] ・Non-polysilicone release film (1): Product name "PC38 AL-5", manufactured by Lintec Co., Ltd., foamed to make a white polyethylene terephthalate (PET) film with Non-polysilicone release film with release layer formed of alkyd release agent, thickness: 38μm. [Second peeling film] ・Non-silicone release film (2): Product name "SP-PET50 AL-5", manufactured by Lintec Co., Ltd., a colorless PET film with a release layer formed of an alkyd release agent. Polysilicone release film, thickness: 50μm. ・Non-silicone release film (3): Product name "SP-PET75 AL-5", manufactured by Lintec Co., Ltd., a colorless PET film with a release layer formed of an alkyd release agent. Polysilicone release film, thickness: 75μm. [Materials for forming the hardening adhesive layer] ・Cureable adhesive composition (1): The curable adhesive composition (1) prepared in Production Example 1 with the composition described in Table 1. ・Cureable adhesive composition (2): The curable adhesive composition (2) prepared in Production Example 2 with the composition described in Table 1.

將表1所記載之硬化性接著劑組成物塗佈於表2所記載之第二剝離膜的剝離層上形成塗膜，將該塗膜進行乾燥，形成厚度25μm的硬化性接著劑層。進而，將所形成之硬化性接著劑層中露出表面之表面與表2所記載之第一剝離膜的剝離層進行貼合，製作硬化性接著片。 The curable adhesive composition described in Table 1 was applied on the release layer of the second release film described in Table 2 to form a coating film, and the coating film was dried to form a curable adhesive layer with a thickness of 25 μm. Furthermore, the exposed surface of the formed curable adhesive layer was bonded to the peeling layer of the first release film described in Table 2 to prepare a curable adhesive sheet.

使用所製作之硬化性接著片，以上述的方法測定剝離力(R1)以及剝離力(R2)。結果如表2所記載。另外，根據以下的評價方法，進行使硬化性接著劑層硬化而成之硬化物的介電正切以及第一剝離膜的剝離性的評價。將這些結果示於表2。 Using the curable adhesive sheet produced, the peeling force (R1) and the peeling force (R2) were measured by the above-mentioned method. The results are reported in Table 2. In addition, the dielectric tangent of the cured product obtained by curing the curable adhesive layer and the peelability of the first release film were evaluated according to the following evaluation method. These results are shown in Table 2.

[硬化物的介電正切] 準備多個所製作之硬化性接著片，將多個硬化性接著劑層重疊，形成厚度約1mm的硬化性接著劑層，獲得依第二剝離膜／厚度約1mm的硬化性接著劑層／第一剝離膜此順序積層而成之積層體。繼而，將該積層體於160℃加熱1小時，使硬化性接著劑層硬化而作成硬化物，進而除去第一剝離膜以及第二剝離膜，將所獲得之硬化物當作測定用樣品。對所獲得之該測定樣品，使用RF Impedance Material Analyzer(是德科技(Keysight Technology)公司製，製品名「E4991A」)，測定於23℃、1GHz之硬化物的介電正切。再者，本說明書之中，係將1GHz作為高頻區之一例而採用。 [Dielectric tangent of hardened material] Prepare a plurality of prepared curable adhesive sheets, overlap a plurality of curable adhesive layers to form a curable adhesive layer with a thickness of about 1 mm, and obtain a second release film/curable adhesive layer with a thickness of about 1 mm/first A laminated body is formed by laminating peeling films in this order. Next, the laminated body was heated at 160° C. for 1 hour to harden the curable adhesive layer to prepare a cured product. The first release film and the second release film were further removed, and the obtained cured product was used as a measurement sample. The obtained measurement sample was measured for the dielectric tangent of the hardened material at 23° C. and 1 GHz using an RF Impedance Material Analyzer (manufactured by Keysight Technology, product name “E4991A”). In this specification, 1 GHz is used as an example of a high frequency range.

[第一剝離膜的剝離性的評價] 欲由所製作之硬化性接著片僅剝離第一剝離膜時之易剝離程度係根據下述的基準進行評價。・A：可使第一剝離膜極易進行剝離，在操作性完全沒有問題。・F：在欲剝離第一剝離膜時，導致產生1次以上的重置，在操作性上有問題。 [Evaluation of the peelability of the first release film] The ease of peeling off only the first release film from the curable adhesive sheet produced was evaluated based on the following criteria. ・A: The first release film can be peeled off very easily, and there is no problem with operability at all. ・F: When trying to peel off the first release film, more than one reset occurs, which is a problem in terms of operability.

[表2] 硬化性接著劑層第一剝離膜第二剝離膜 (R1)/(R2) 硬化物的介電正切 23°C、1GHz 第一剝離膜的剝離性的評價種類種類剝離力 (R1) 種類剝離力 (R2) - - mN/50mm - mN/50mm - - 實施例1 硬化性接著劑組成物(1) 非聚矽氧系剝離膜(1) 70 非聚矽氧系剝離膜(2) 83 0.84 0.0008 A 實施例2 硬化性接著劑組成物(1) 非聚矽氧系剝離膜(1) 70 非聚矽氧系剝離膜(3) 92 0.76 0.0008 A 比較例1 硬化性接著劑組成物⑵ 非聚矽氧系剝離膜(1) 330 非聚矽氧系剝離膜(2) 350 0.94 0.0008 F 比較例2 硬化性接著劑組成物(2) 非聚矽氧系剝離膜(1) 330 非聚矽氧系剝離膜(3) 390 0.85 0.0008 F [Table 2] hardening adhesive layer First peel film second release film (R1)/(R2) Dielectric tangent of hardened material 23°C, 1GHz Evaluation of the peelability of the first release film Kind Kind Peeling force (R1) Kind Peeling force (R2) - - mN/50mm - mN/50mm - - Example 1 Hardening adhesive composition (1) Non-polysilicone release film(1) 70 Non-polysilicone release film(2) 83 0.84 0.0008 A Example 2 Hardening adhesive composition (1) Non-polysilicone release film(1) 70 Non-polysilicone release film(3) 92 0.76 0.0008 A Comparative example 1 Hardening adhesive composition⑵ Non-polysilicone release film(1) 330 Non-polysilicone release film(2) 350 0.94 0.0008 F Comparative example 2 Hardening adhesive composition (2) Non-polysilicone release film(1) 330 Non-polysilicone release film(3) 390 0.85 0.0008 F

如表2所示，相較於比較例1至比較例2，在實施例1至實施例2所製作之硬化性接著片中之第一剝離膜易剝離，成為操作性優異之結果。另外，在實施例1至實施例2所製作之硬化性接著片由於使用非聚矽氧系剝離劑，故不會導致聚矽氧成分移轉至被黏附體，能夠抑制對被黏附體之污染。As shown in Table 2, compared with Comparative Examples 1 to 2, the first release film in the curable adhesive sheet produced in Examples 1 to 2 was easy to peel off, resulting in excellent workability. In addition, since the curable adhesive sheet produced in Examples 1 to 2 uses a non-polysilicone release agent, the silicone component will not be transferred to the adherend, and contamination of the adherend can be suppressed. .

1:硬化性接著片 10:硬化性接著劑層 10a、10b:表面 21:第一剝離膜 211:剝離層 212:樹脂膜 22:第二剝離膜 221:剝離層 222:樹脂膜 1: Hardening adhesive sheet 10: Hardening adhesive layer 10a, 10b: Surface 21: First peeling film 211: peeling layer 212: Resin film 22:Second peeling film 221: peeling layer 222: Resin film

[圖1]係表示本發明之硬化性接著片之構成之一例的該接著片之厚度方向之示意剖面圖。[Fig. 1] is a schematic cross-sectional view in the thickness direction of the curable adhesive sheet of the present invention showing an example of the structure of the adhesive sheet.

1:硬化性接著片 1: Hardening adhesive sheet

10:硬化性接著劑層 10: Hardening adhesive layer

10a、10b:表面 10a, 10b: Surface

21:第一剝離膜 21: First peeling film

211:剝離層 211: peeling layer

212:樹脂膜 212: Resin film

22:第二剝離膜 22:Second peeling film

221:剝離層 221: peeling layer

222:樹脂膜 222: Resin film

Claims

一種硬化性接著片，係具有：能夠形成於23℃、1GHz之介電正切為0.01以下的硬化物之硬化性接著劑層、以及挾持該硬化性接著劑層之兩面之第一剝離膜以及第二剝離膜；第一剝離膜以及第二剝離膜係具有：樹脂膜、以及於該樹脂膜其中一表面上之由非聚矽氧系剝離劑所形成之接觸前述硬化性接著劑層的表面之剝離層；並滿足下述要件(I)：・要件(I)：將第一剝離膜以剝離角度180°、剝離速度300mm／分鐘自前述硬化性接著劑層進行剝離時之剝離力(R1)為250mN／50mm以下。 A curable adhesive sheet comprising: a curable adhesive layer capable of forming a cured product with a dielectric tangent of 0.01 or less at 23° C. and 1 GHz; a first release film sandwiching both sides of the curable adhesive layer; and a third release film. Two peeling films; The first release film and the second release film include: a resin film, and a release layer formed of a non-polysilicone release agent on one surface of the resin film and contacting the surface of the curable adhesive layer; And meet the following requirements (I): ・Requirement (I): The peeling force (R1) when peeling the first release film from the curable adhesive layer at a peeling angle of 180° and a peeling speed of 300mm/minute is 250mN/50mm or less.

如請求項1所記載之硬化性接著片，進而滿足下述要件(II)：・要件(II)：剝離力(R1)係小於將第二剝離膜以剝離角度180°、剝離速度300mm／分鐘自前述硬化性接著劑層剝離時之剝離力(R2)。 The curable adhesive sheet as described in claim 1 further satisfies the following requirement (II): ・Requirement (II): The peeling force (R1) is less than the peeling force (R2) when the second release film is peeled off from the curable adhesive layer at a peeling angle of 180° and a peeling speed of 300mm/minute.

如請求項2所記載之硬化性接著片，進而滿足下述要件(IIa)：・要件(IIa)：剝離力(R1)與剝離力(R2)之比[(R1)／(R2)]為0.97以下。 The curable adhesive sheet as described in claim 2 further satisfies the following requirement (IIa): ・Requirement (IIa): The ratio of peeling force (R1) to peeling force (R2) [(R1)/(R2)] is 0.97 or less.

如請求項1至3中任一項所記載之硬化性接著片，進而滿足下述要件(III)：・要件(III)：將第二剝離膜以剝離角度180°、剝離速度300mm／分鐘自前述硬化性接著劑層剝離時之剝離力(R2)為300mN／50mm以下。 The curable adhesive sheet according to any one of claims 1 to 3, further satisfying the following requirement (III): ・Requirement (III): The peeling force (R2) when peeling the second release film from the curable adhesive layer at a peeling angle of 180° and a peeling speed of 300mm/minute is 300mN/50mm or less.

如請求項1至4中任一項所記載之硬化性接著片，其中用於形成第一剝離膜以及第二剝離膜中至少一者之剝離層的前述非聚矽氧系剝離劑為醇酸系剝離劑。The curable adhesive sheet according to any one of claims 1 to 4, wherein the non-polysilicone release agent used to form the release layer of at least one of the first release film and the second release film is an alkyd. It is a stripping agent.

如請求項1至5中任一項所記載之硬化性接著片，其中前述硬化性接著劑層係由含有黏合劑樹脂(A)之硬化性接著劑組成物所形成之層。The curable adhesive sheet according to any one of claims 1 to 5, wherein the curable adhesive layer is a layer formed of a curable adhesive composition containing a binder resin (A).

如請求項6所記載之硬化性接著片，其中前述硬化性接著劑組成物係進而含有聚苯醚樹脂(B)。The curable adhesive sheet according to claim 6, wherein the curable adhesive composition further contains polyphenylene ether resin (B).

如請求項1至7中任一項所記載之硬化性接著片，其中構成第一剝離膜之樹脂膜(1)為有色樹脂膜。The curable adhesive sheet according to any one of claims 1 to 7, wherein the resin film (1) constituting the first release film is a colored resin film.

如請求項1至8中任一項所記載之硬化性接著片，其中構成第二剝離膜之樹脂膜(2)係能夠以目視方式來和構成第一剝離膜之樹脂膜(1)做區別。The curable adhesive sheet according to any one of claims 1 to 8, wherein the resin film (2) constituting the second release film can be visually distinguished from the resin film (1) constituting the first release film. .