TWI771856B - Adhesive composition and structure - Google Patents

Adhesive composition and structure Download PDF

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TWI771856B
TWI771856B TW110100188A TW110100188A TWI771856B TW I771856 B TWI771856 B TW I771856B TW 110100188 A TW110100188 A TW 110100188A TW 110100188 A TW110100188 A TW 110100188A TW I771856 B TWI771856 B TW I771856B
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adhesive composition
mass
circuit
component
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TW202126773A (en
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森尻智樹
伊澤弘行
杜暁黎
岩井慧子
関耕太郎
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日商昭和電工材料股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/14—Structural association of two or more printed circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/20—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by affixing prefabricated conductor pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits

Abstract

一種接著劑組成物，其含有具有下述通式（I）所表示的結構的矽烷化合物。

Figure 110100188-A0101-11-0001-1
（式中，X表示有機基，R1 及R2 分別獨立地表示烷基，m表示0～2的整數，s表示6以上的整數）An adhesive composition containing a silane compound having a structure represented by the following general formula (I).
Figure 110100188-A0101-11-0001-1
(in the formula, X represents an organic group, R 1 and R 2 each independently represent an alkyl group, m represents an integer of 0 to 2, and s represents an integer of 6 or more)

Description

接著劑組成物及結構體Adhesive composition and structure

本發明是有關於一種接著劑組成物及結構體。The present invention relates to an adhesive composition and a structure.

在半導體元件及液晶顯示元件（顯示器顯示元件）中，自先前便以使元件中的各種構件結合為目的而使用各種接著劑。接著劑所要求的特性以接著性為首，覆蓋耐熱性、高溫高濕狀態下的可靠性等多個方面。而且，作為接著中所使用的被黏著體，以印刷配線板、有機基材（例如聚醯亞胺基材）等為首，使用金屬（鈦、銅、鋁等）、具有ITO、IZO、IGZO、SiNx 、SiO2 等多種多樣的表面狀態的基材，需要根據各被黏著體而進行接著劑的分子設計。In semiconductor elements and liquid crystal display elements (display elements), various adhesives have been conventionally used for the purpose of bonding various members in the elements. The properties required for adhesives include adhesiveness, and cover various aspects such as heat resistance and reliability under high temperature and high humidity conditions. Furthermore, as the adherend used in the bonding, metal (titanium, copper, aluminum, etc.), including ITO, IZO, IGZO, For substrates with various surface states such as SiN x and SiO 2 , molecular design of the adhesive is required for each adherend.

在先前，在半導體元件用接著劑或液晶顯示元件用接著劑中使用顯示出高接著性及高可靠性的熱固性樹脂（環氧樹脂、丙烯酸樹脂等）。作為使用環氧樹脂的接著劑的構成成分，一般使用環氧樹脂及潛伏性硬化劑，所述潛伏性硬化劑藉由熱或光而產生對於環氧樹脂具有反應性的陽離子種或陰離子種。潛伏性硬化劑是決定硬化溫度及硬化速度的重要因素，自常溫下的儲存穩定性及加熱時的硬化速度的觀點考慮，可使用各種化合物。在實際的步驟中，例如藉由在溫度為170℃～250℃、10秒～3小時的硬化條件下進行硬化而獲得所期望的接著性。Conventionally, thermosetting resins (epoxy resins, acrylic resins, etc.) exhibiting high adhesiveness and high reliability have been used as adhesives for semiconductor elements or adhesives for liquid crystal display elements. As constituent components of an adhesive using an epoxy resin, an epoxy resin and a latent curing agent that generates a cationic species or an anionic species reactive with the epoxy resin by heat or light are generally used. The latent hardener is an important factor for determining the hardening temperature and the hardening rate, and various compounds can be used from the viewpoints of the storage stability at normal temperature and the hardening rate during heating. In an actual step, for example, desired adhesiveness is obtained by performing hardening under hardening conditions at a temperature of 170° C. to 250° C. for 10 seconds to 3 hours.

而且，近年來存在如下的擔憂：隨著半導體元件的高積體化及液晶顯示元件的高精細化，元件間及配線間的間距狹小化，由於硬化時的熱而對周邊構件造成不良影響。進而，為了低成本化，需要使產量（throughput）提高，要求低溫（90℃～170℃）且短時間（1小時以內、較佳為10秒以內、更佳為5秒以內）的接著，換而言之需要低溫短時間硬化（低溫快速硬化）的接著。已知為了達成該低溫短時間硬化，需要使用活化能（activation energy）低的熱潛伏性觸媒，但非常難以兼具常溫附近的儲存穩定性。Furthermore, in recent years, along with the higher integration of semiconductor elements and the higher definition of liquid crystal display elements, there is a concern that the pitches between elements and wirings are narrowed, and surrounding members are adversely affected by heat during curing. Furthermore, in order to reduce the cost, it is necessary to increase the throughput, and a low temperature (90° C. to 170° C.) and a short time (within 1 hour, preferably within 10 seconds, and more preferably within 5 seconds) are required. In other words, a low-temperature short-time hardening (low-temperature rapid hardening) is required. It is known that in order to achieve this low-temperature and short-time hardening, it is necessary to use a thermally latent catalyst with a low activation energy, but it is very difficult to have storage stability near normal temperature.

因此，近年來開始關注併用(甲基)丙烯酸酯衍生物與作為自由基聚合起始劑的過氧化物的自由基硬化系接著劑、併用環氧樹脂與作為陽離子聚合起始劑的鎓鹽的陽離子硬化系接著劑等。自由基硬化系由於作為反應活性種（active species）的自由基非常富有反應性，因此可短時間硬化，且若為自由基聚合起始劑的分解溫度以下，則過氧化物穩定地存在，因此其是兼顧低溫短時間硬化與儲存穩定性（例如常溫附近的儲存穩定性）的硬化系。陽離子硬化系由於作為反應活性種的鎓鹽富有反應性，因此可短時間硬化，且若為鎓鹽的分解溫度以下，則陽離子種穩定地存在，因此是兼顧低溫短時間硬化與儲存穩定性的硬化系。Therefore, in recent years, attention has been paid to the combination of a (meth)acrylate derivative and a radical curing adhesive that uses a peroxide as a radical polymerization initiator, and an epoxy resin and an onium salt as a cationic polymerization initiator. Cationic hardening adhesive, etc. Radical curing systems can be cured in a short time because radicals as reactive species are very reactive, and peroxides exist stably when the decomposition temperature of the radical polymerization initiator is below the decomposition temperature, so It is a hardening system that combines low-temperature short-time hardening and storage stability (for example, storage stability near normal temperature). Since the onium salt as the reactive species is rich in reactivity, the cationic curing system can be cured in a short time, and when the decomposition temperature of the onium salt is lower than the decomposition temperature of the onium salt, the cationic species exist stably, so it is compatible with low-temperature and short-time curing and storage stability. Hardening system.

另一方面，為了實現與被黏著體牢固地接著，所述接著劑存在使用偶合劑等作為藉由因共價鍵、氫鍵、凡得瓦力產生的疏水性相互作用等而可與被黏著體表面相互作用的低分子量的添加劑的情況。作為偶合劑，例如可使用矽烷偶合劑；含有磷酸基、羧基等的化合物等。特別是於使用硬化後摻入至樹脂的基質的有機官能基（例如環氧基、丙烯醯基、乙烯基等所代表的有機官能基）、及與被黏著體表面相互作用的烷氧基矽烷或偶合劑（例如具有磷酸基等所代表的官能基的偶合劑）的情況下，可更牢固地接著被黏著體與接著劑（例如參照下述專利文獻1）。 [現有技術文獻] [專利文獻]On the other hand, in order to achieve firm adhesion to the adherend, the adhesive agent exists to use a coupling agent or the like as a covalent bond, hydrogen bond, hydrophobic interaction due to Van der Waals force, etc. In the case of low molecular weight additives that interact with the body surface. As the coupling agent, for example, a silane coupling agent; a compound containing a phosphoric acid group, a carboxyl group, or the like can be used. In particular, organic functional groups (such as organic functional groups represented by epoxy groups, acryl groups, vinyl groups, etc.) incorporated into the resin matrix after hardening are used, and alkoxysilanes that interact with the surface of the adherend are used. Or in the case of a coupling agent (for example, a coupling agent having a functional group represented by a phosphoric acid group or the like), the adherend and the adhesive can be more firmly bonded (for example, refer to the following Patent Document 1). [Prior Art Literature] [Patent Literature]

專利文獻1：日本專利特開2013-191625號公報 專利文獻2：國際公開第2009/063827號Patent Document 1: Japanese Patent Laid-Open No. 2013-191625 Patent Document 2: International Publication No. 2009/063827

[發明所欲解決之課題] 然而，對於含有矽烷化合物的接著劑組成物，要求於在85℃85%RH、60℃95%RH等高溫高濕條件下保持的可靠性試驗後具有優異的接著強度。[The problem to be solved by the invention] However, an adhesive composition containing a silane compound is required to have excellent adhesive strength after a reliability test held under high temperature and high humidity conditions such as 85°C 85%RH and 60°C 95%RH.

本發明的目的在於提供於可靠性試驗後具有優異的接著強度的接著劑組成物、及使用其的結構體。 [解決課題之手段]An object of the present invention is to provide an adhesive composition having excellent adhesive strength after a reliability test, and a structure using the same. [Means of Solving Problems]

本發明的接著劑組成物含有具有下述通式（I）所表示的結構的矽烷化合物。 [化1]

Figure 02_image001
（式中，X表示有機基，R1 及R2 分別獨立地表示烷基，m表示0～2的整數，s表示6以上的整數。）The adhesive composition of the present invention contains a silane compound having a structure represented by the following general formula (I). [hua 1]
Figure 02_image001
(In the formula, X represents an organic group, R 1 and R 2 each independently represent an alkyl group, m represents an integer of 0 to 2, and s represents an integer of 6 or more.)

然而，先前存在使用含有如下矽烷化合物的接著劑的情況，所述矽烷化合物具有烷氧基矽烷基與經由伸烷基而鍵結於烷氧基矽烷基的有機基。對此，本發明者發現了有關於此種矽烷化合物的以下見解。即，先前的矽烷化合物中，存在於烷氧基矽烷基的Si與有機基之間的伸烷基的碳數小（例如亞甲基（CH2 ）數短而為3以下）。因此，在烷氧基矽烷基以及有機基中的其中一第一官能基與接著劑的構成成分（樹脂等）及被黏著體中的其中一者進行反應時，烷氧基矽烷基與有機基難以充分地分離，藉此烷氧基矽烷基及有機基中的另一第二官能基的立體自由度低，因此第二官能基與接著劑的構成成分（樹脂等）及被黏著體中的另一者未充分地進行反應，無法充分地發揮作為矽烷化合物的效果。結果，存在無法獲得充分的接著強度，於在85℃85%RH、60℃95%RH等高溫高濕條件下放置的可靠性試驗後接著強度下降等問題。However, there has been a case of using an adhesive containing a silane compound having an alkoxysilyl group and an organic group bonded to the alkoxysilyl group via an alkylene group. In this regard, the present inventors have found the following findings on such silane compounds. That is, in the conventional silane compound, the carbon number of the alkylene group existing between Si of the alkoxysilyl group and the organic group is small (for example, the number of methylene groups (CH 2 ) is short and 3 or less). Therefore, when one of the first functional groups in the alkoxysilyl group and the organic group is reacted with one of the constituents of the adhesive (resin, etc.) and the adherend, the alkoxysilyl group and the organic group It is difficult to separate sufficiently, so that the steric freedom of the alkoxysilyl group and the other second functional group in the organic group is low, so the second functional group and the constituents of the adhesive (resin, etc.) and the adhesive in the adherend are low. On the other hand, the reaction does not proceed sufficiently, and the effect as a silane compound cannot be sufficiently exhibited. As a result, sufficient adhesive strength could not be obtained, and there were problems that the adhesive strength decreased after a reliability test left under high temperature and high humidity conditions such as 85° C. 85% RH and 60° C. 95% RH.

另一方面，本發明的接著劑組成物於可靠性試驗後具有優異的接著強度。另外，對於由各種材質（例如無機物（氧化物、金屬等）、有機物、以及該些的複合物）所構成的被黏著體，本發明的接著劑組成物於可靠性試驗前後均具有優異的接著強度。On the other hand, the adhesive composition of the present invention has excellent adhesive strength after the reliability test. In addition, for adherends composed of various materials (such as inorganic substances (oxides, metals, etc.), organic substances, and composites thereof), the adhesive composition of the present invention has excellent adhesion both before and after the reliability test. strength.

所述有機基X較佳為包含選自由(甲基)丙烯醯基、乙烯基、環氧基、氮原子含有基及硫原子含有基所組成的群組中的至少一種。The organic group X preferably contains at least one selected from the group consisting of a (meth)acryloyl group, a vinyl group, an epoxy group, a nitrogen atom-containing group, and a sulfur atom-containing group.

本發明的接著劑組成物亦可進而含有環氧樹脂、及潛伏性硬化劑。The adhesive composition of the present invention may further contain an epoxy resin and a latent curing agent.

本發明的接著劑組成物亦可進而含有自由基聚合性化合物、及藉由熱或光而產生自由基的硬化物。The adhesive composition of the present invention may further contain a radically polymerizable compound and a cured product that generates radicals by heat or light.

本發明的接著劑組成物亦可進而含有導電粒子。The adhesive composition of the present invention may further contain conductive particles.

本發明的接著劑組成物亦可用於電路連接（電路連接用接著劑組成物）。The adhesive composition of the present invention can also be used for circuit connection (adhesive composition for circuit connection).

本發明的結構體具備所述接著劑組成物或其硬化物。The structure of the present invention includes the adhesive composition or a cured product thereof.

本發明的結構體亦可為如下的實施方式：其具備具有第一電路電極的第一電路構件、具有第二電路電極的第二電路構件、及配置於所述第一電路構件與所述第二電路構件之間的電路連接構件，所述第一電路電極及所述第二電路電極電性連接，所述電路連接構件包含所述接著劑組成物或其硬化物。 [發明的效果]The structure of the present invention may be an embodiment including a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode, and a structure disposed between the first circuit member and the first circuit member. In a circuit connection member between two circuit members, the first circuit electrode and the second circuit electrode are electrically connected, and the circuit connection member includes the adhesive composition or a cured product thereof. [Effect of invention]

藉由本發明可提供於可靠性試驗後具有優異的接著強度的接著劑組成物及使用其的結構體。而且，藉由本發明可提供對於由各種材質所構成的被黏著體，於可靠性試驗前後均具有優異的接著強度的接著劑組成物以及使用其的結構體。According to the present invention, an adhesive composition having excellent adhesive strength after a reliability test and a structure using the same can be provided. Furthermore, the present invention can provide an adhesive composition having an excellent adhesive strength before and after a reliability test, and a structure using the same for an adherend composed of various materials.

藉由本發明可提供接著劑組成物或其硬化物於結構體或其製造中的應用。藉由本發明可提供接著劑組成物或其硬化物於電路連接中的應用。藉由本發明可提供接著劑組成物或其硬化物於電路連接結構體或其製造中的應用。The present invention can provide the application of the adhesive composition or its cured product to a structure or its manufacture. The application of the adhesive composition or its cured product in circuit connection can be provided by the present invention. The present invention can provide the application of the adhesive composition or its cured product to a circuit connection structure or its manufacture.

以下，關於本發明的實施方式而加以說明，但本發明並不受該些實施方式任何限定。Hereinafter, the embodiments of the present invention will be described, but the present invention is not limited to these embodiments at all.

在本說明書中，所謂「(甲基)丙烯酸酯」是表示丙烯酸酯及與其對應的甲基丙烯酸酯的至少一者。在「(甲基)丙烯醯基」、「(甲基)丙烯酸」等其他類似的表現中亦同樣。以下所例示的材料若無特別限制，則可單獨使用一種，亦可組合使用兩種以上。至於組成物中的各成分的含量，在組成物中存在多種相當於各成分的物質的情況下，若無特別說明，則表示組成物中所存在的該多種物質的合計量。使用「～」而表示的數值範圍表示包含「～」的前後所記載的數值而分別作為最小值及最大值的範圍。所謂「A或B」，若包含A及B的任一者即可，亦可包含兩者。所謂「常溫」是表示25℃。In this specification, "(meth)acrylate" means at least one of acrylate and its corresponding methacrylate. The same applies to other similar expressions such as "(meth)acryloyl" and "(meth)acrylic". The materials exemplified below may be used alone or in combination of two or more, unless particularly limited. As for the content of each component in the composition, when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified, the total amount of the plurality of substances present in the composition is indicated. The numerical range represented using "-" represents the range including the numerical values described before and after the "-" as the minimum value and the maximum value, respectively. The term "A or B" may include either one of A and B, and may include both. "Normal temperature" means 25°C.

在本說明書中階段性記載的數值範圍中，某一階段的數值範圍的上限值或下限值亦可置換為其他階段的數值範圍的上限值或下限值。而且，在本說明書中所記載的數值範圍中，該數值範圍的上限值或下限值亦可置換為實施例中所示的值。In the numerical range described in stages in this specification, the upper limit or the lower limit of the numerical range in a certain stage may be replaced with the upper limit or the lower limit of the numerical range in another stage. In addition, in the numerical range described in this specification, the upper limit or the lower limit of this numerical range may be replaced with the value shown in an Example.

本實施方式的接著劑組成物含有具有下述通式（I）所表示的結構的矽烷化合物（以下根據情況稱為「矽烷化合物A」）。根據本實施方式的接著劑組成物，藉由將先前碳數小的伸烷基取代為碳數6以上的伸烷基而烷氧基矽烷基與有機基X容易分離，因此在烷氧基矽烷基及有機基X中的其中一官能基反應後，亦可確保另一官能基的立體自由度，從而顯示出對於各種被黏著體的高接著強度且於可靠性試驗後亦具有充分的接著強度。此種接著劑組成物適宜用作電路連接用接著劑組成物。The adhesive composition of the present embodiment contains a silane compound having a structure represented by the following general formula (I) (hereinafter referred to as "silane compound A" in some cases). According to the adhesive composition of the present embodiment, the alkoxysilyl group and the organic group X are easily separated by substituting an alkylene group having a smaller carbon number with an alkylene group having 6 or more carbon atoms. After the reaction of one of the functional groups in the organic group and the organic group X, the steric freedom of the other functional group can also be ensured, thereby showing high adhesion strength to various adherends and sufficient adhesion strength after reliability tests. . Such an adhesive composition is suitably used as an adhesive composition for circuit connection.

[化2]

Figure 02_image001
（式中，X表示有機基，R1 及R2 分別獨立地表示烷基，m表示0～2的整數，s表示6以上的整數。在R1 多個存在的情況下，各R1 可相互相同亦可不同。在R2 多個存在的情況下，各R2 可相互相同亦可不同。R1 、R2 及Cs H2s 的各個亦可分支）[hua 2]
Figure 02_image001
(in the formula, X represents an organic group, R 1 and R 2 each independently represent an alkyl group, m represents an integer of 0 to 2, and s represents an integer of 6 or more. When more than one R 1 exists, each R 1 may They may be the same or different from each other. When a plurality of R 2 exists, each R 2 may be the same or different from each other. Each of R 1 , R 2 and C s H 2s may be branched)

矽烷化合物A的伸烷基可為直鏈伸烷基以及支鏈伸烷基的任一者。在直鏈伸烷基以及支鏈伸烷基中的烷氧基矽烷基與有機基X之間的碳數相同的情況下，自變得更容易確保立體自由度的觀點考慮，較佳為直鏈伸烷基。在使用具有直鏈伸烷基的矽烷化合物A的情況下，藉由先前短的亞甲基數為6以上，在烷氧基矽烷基及有機基X中的其中一官能基反應後，亦可確保另一官能基的立體自由度，從而顯示出對於各種被黏著體的高接著強度且於可靠性試驗後亦具有充分的接著強度。The alkylene group of the silane compound A may be any of a straight-chain alkylene group and a branched-chain alkylene group. When the number of carbon atoms between the alkoxysilyl group and the organic group X in the straight-chain alkyl group and the branched-chain alkyl group is the same, from the viewpoint of making it easier to secure the steric freedom, straight chain is preferred. chain extension. In the case of using the silane compound A having a straight-chain alkyl group, since the number of methylene groups previously short is 6 or more, after the alkoxysilyl group and one of the functional groups in the organic group X are reacted, it is also possible to The steric degree of freedom of another functional group is ensured, thereby showing high adhesion strength to various adherends and sufficient adhesion strength after reliability test.

作為本實施方式的接著劑組成物的構成成分，例如可列舉：（a）環氧樹脂（以下根據情況稱為「（a）成分）」）、（b）潛伏性硬化劑（環氧樹脂的潛伏性硬化劑。以下根據情況稱為「（b）成分）」）、（c）自由基聚合性化合物（以下根據情況稱為「（c）成分」）、以及（d）藉由熱（加熱）或光（光照射）而產生自由基（遊離自由基）的硬化劑（以下根據情況稱為「（d）成分」）。本實施方式的接著劑組成物的第一實施方式含有（a）成分以及（b）成分。本實施方式的接著劑組成物的第二實施方式含有（c）成分以及（d）成分。本實施方式的接著劑組成物的第三實施方式含有（a）成分、（b）成分、（c）成分以及（d）成分。As the constituent components of the adhesive composition of the present embodiment, for example, (a) epoxy resin (hereinafter referred to as "(a) component)"), (b) latent curing agent (epoxy resin Latent hardener. Hereinafter referred to as "(b) component)"), (c) radically polymerizable compound (hereinafter referred to as "(c) component"), and (d) by heat (heating ) or light (light irradiation) to generate radicals (free radicals) hardeners (hereinafter referred to as "component (d)" in some cases). The first embodiment of the adhesive composition of the present embodiment contains (a) component and (b) component. The second embodiment of the adhesive composition of the present embodiment contains the (c) component and the (d) component. The third embodiment of the adhesive composition of the present embodiment contains (a) component, (b) component, (c) component, and (d) component.

以下對各成分加以說明。Each component is demonstrated below.

（矽烷化合物） 作為具有式（I）所表示的結構的矽烷化合物A的有機基X，可列舉乙烯性不飽和鍵含有基（含有乙烯性不飽和鍵的基）、氮原子含有基（含有氮原子的基）、硫原子含有基（含有硫原子的基）、環氧基等。作為乙烯性不飽和鍵含有基，可列舉(甲基)丙烯醯基、乙烯基、苯乙烯基等。作為氮原子含有基，可列舉胺基、單取代胺基、二取代胺基、異氰酸酯基、咪唑基、脲基、馬來醯亞胺基等。作為單取代胺基，可列舉烷基胺基（甲基胺基等）、苄基胺基、苯基胺基、環烷基胺基（環己基胺基等）等。作為二取代胺基，可列舉非環狀二取代胺基、環狀二取代胺基等。作為非環狀二取代胺基，可列舉二烷基胺基（二甲基胺基等）等。作為環狀二取代胺基，可列舉嗎啉基、哌嗪基等。作為硫原子含有基，可列舉巰基等。環氧基亦可含有於縮水甘油基、縮水甘油氧基等環氧基含有基（含有環氧基的基）中。(甲基)丙烯醯基亦可含有於(甲基)丙烯醯氧基中。(Silane compound) Examples of the organic group X of the silane compound A having the structure represented by the formula (I) include an ethylenically unsaturated bond-containing group (an ethylenically unsaturated bond-containing group) and a nitrogen atom-containing group (a nitrogen atom-containing group) , sulfur atom-containing groups (groups containing sulfur atoms), epoxy groups, etc. As an ethylenically unsaturated bond-containing group, a (meth)acryloyl group, a vinyl group, a styryl group, etc. are mentioned. As the nitrogen atom-containing group, an amino group, a monosubstituted amino group, a disubstituted amino group, an isocyanate group, an imidazolyl group, a urea group, a maleimide group, and the like can be mentioned. Examples of the monosubstituted amino group include alkylamino groups (methylamino groups, etc.), benzylamino groups, phenylamino groups, cycloalkylamino groups (cyclohexylamino groups, etc.), and the like. As a disubstituted amino group, an acyclic disubstituted amino group, a cyclic disubstituted amino group, etc. are mentioned. As an acyclic disubstituted amino group, a dialkylamino group (dimethylamino group etc.) etc. are mentioned. As a cyclic disubstituted amino group, a morpholino group, a piperazinyl group, etc. are mentioned. A mercapto group etc. are mentioned as a sulfur atom containing group. The epoxy group may be contained in an epoxy group-containing group (group containing an epoxy group) such as a glycidyl group and a glycidyloxy group. The (meth)acryloyloxy group may be contained in the (meth)acryloyloxy group.

有機基X較佳為對於矽烷化合物以外的接著劑組成物的成分具有反應性。自進而提高對於矽烷化合物以外的接著劑組成物的成分的反應性的觀點考慮，有機基X較佳為包含選自由(甲基)丙烯醯基、乙烯基、環氧基、氮原子含有基及硫原子含有基所組成的群組中的至少一種。The organic group X preferably has reactivity with the components of the adhesive composition other than the silane compound. From the viewpoint of further improving the reactivity of the components of the adhesive composition other than the silane compound, the organic group X preferably contains a group selected from the group consisting of a (meth)acryloyl group, a vinyl group, an epoxy group, a nitrogen atom-containing group, and The sulfur atom contains at least one of the group consisting of groups.

R1 及R2 的烷基的碳數例如為1～20。作為所述烷基的具體例，可列舉甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基等。作為R1 及R2 ，可使用所述烷基的各結構異構物。自烷氧基矽烷基部分與被黏著體反應時難以成為立體阻礙，進而提高與被黏著體的接著性的觀點考慮，R1 的烷基的碳數較佳為1～10，更佳為1～5。自進而提高與被黏著體的接著性的觀點考慮，R2 的烷基的碳數較佳為1～10，更佳為1～5。The number of carbon atoms in the alkyl group of R 1 and R 2 is, for example, 1 to 20. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, etc. As R 1 and R 2 , each structural isomer of the alkyl group can be used. The number of carbon atoms of the alkyl group of R 1 is preferably 1 to 10, more preferably 1, from the viewpoint that the alkoxysilyl group is unlikely to become a steric hindrance when reacting with the adherend and further improves the adhesion to the adherend. ~5. From the viewpoint of further improving the adhesiveness with the adherend, the number of carbon atoms of the alkyl group of R 2 is preferably 1-10, more preferably 1-5.

m為0～2的整數。自進而提高與被黏著體的接著性的觀點考慮，m較佳為0～1，更佳為0。s為6以上的整數。自擴大有機基X與烷氧基矽烷基的物理距離、提高兩者的官能基的反應性的觀點考慮，s較佳為6～20的整數，更佳為6～10的整數。自同樣的觀點考慮，式（I）中有機基X與烷氧基矽烷基之間的碳鏈（直鏈部分）的碳數較佳為6～20，更佳為6～10。m is an integer of 0-2. From the viewpoint of further improving the adhesiveness with the adherend, m is preferably 0 to 1, more preferably 0. s is an integer of 6 or more. From the viewpoint of increasing the physical distance between the organic group X and the alkoxysilyl group and improving the reactivity of both functional groups, s is preferably an integer of 6-20, more preferably an integer of 6-10. From the same viewpoint, the number of carbon atoms in the carbon chain (linear part) between the organic group X and the alkoxysilyl group in the formula (I) is preferably 6-20, more preferably 6-10.

作為矽烷化合物A，可列舉縮水甘油氧基烷基三烷氧基矽烷、縮水甘油氧基烷基二烷氧基矽烷、(甲基)丙烯醯氧基烷基三烷氧基矽烷、(甲基)丙烯醯氧基二烷基二烷氧基矽烷、烯基三烷氧基矽烷、苯乙烯基烷基三烷氧基矽烷、N-2-(胺基乙基)-8-胺基辛基甲基二甲氧基矽烷、N-2-(胺基乙基)-8-胺基辛基三甲氧基矽烷、3-胺基辛基三甲氧基矽烷、3-胺基辛基三乙氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基亞丁基)辛基胺、N-苯基-8-胺基辛基三甲氧基矽烷、8-脲基辛基三乙氧基矽烷、8-巰基辛基甲基二甲氧基矽烷、8-巰基辛基三甲氧基矽烷、8-異氰酸酯基辛基三甲氧基矽烷、8-異氰酸酯基辛基三乙氧基矽烷等。Examples of the silane compound A include glycidoxyalkyltrialkoxysilane, glycidoxyalkyldialkoxysilane, (meth)acryloyloxyalkyltrialkoxysilane, (methyl) ) acryloxydialkyldialkoxysilane, alkenyltrialkoxysilane, styrylalkyltrialkoxysilane, N-2-(aminoethyl)-8-aminooctyl Methyldimethoxysilane, N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, 3-aminooctyltrimethoxysilane, 3-aminooctyltriethoxy Silane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)octylamine, N-phenyl-8-aminooctyltrimethoxysilane, 8-ureidooctyl Triethoxysilane, 8-mercaptooctylmethyldimethoxysilane, 8-mercaptooctyltrimethoxysilane, 8-isocyanatooctyltrimethoxysilane, 8-isocyanatooctyltriethoxy Silane etc.

作為縮水甘油氧基烷基三烷氧基矽烷，可列舉8-縮水甘油氧基辛基三甲氧基矽烷、8-縮水甘油氧基辛基三乙氧基矽烷等。作為縮水甘油氧基烷基二烷氧基矽烷，可列舉8-縮水甘油氧基辛基甲基二甲氧基矽烷、8-縮水甘油氧基辛基甲基二乙氧基矽烷等。作為(甲基)丙烯醯氧基烷基三甲氧基矽烷，可列舉8-(甲基)丙烯醯氧基辛基三甲氧基矽烷、8-(甲基)丙烯醯氧基辛基三乙氧基矽烷等。作為(甲基)丙烯醯氧基二烷基二烷氧基矽烷，可列舉8-(甲基)丙烯醯氧基辛基甲基二甲氧基矽烷、8-(甲基)丙烯醯氧基辛基甲基二乙氧基矽烷等。作為烯基三烷氧基矽烷，可列舉辛烯基三烷氧基矽烷、辛烯基烷基二烷氧基矽烷等。作為辛烯基三烷氧基矽烷，可列舉7-辛烯基三甲氧基矽烷、7-辛烯基三乙氧基矽烷等。作為辛烯基烷基二烷氧基矽烷，可列舉7-辛烯基甲基二甲氧基矽烷、7-辛烯基甲基二乙氧基矽烷等。作為苯乙烯基烷基三烷氧基矽烷，可列舉對苯乙烯基辛基三甲氧基矽烷等。As a glycidoxyalkyl trialkoxysilane, 8-glycidyloxyoctyltrimethoxysilane, 8-glycidoxyoctyltriethoxysilane, etc. are mentioned. As a glycidoxyalkyl dialkoxysilane, 8-glycidoxyoctylmethyldimethoxysilane, 8-glycidoxyoctylmethyldiethoxysilane, etc. are mentioned. Examples of (meth)acryloyloxyalkyltrimethoxysilane include 8-(meth)acryloyloxyoctyltrimethoxysilane, 8-(meth)acryloyloxyoctyltriethoxy Silane etc. Examples of (meth)acryloyloxydialkyldialkoxysilane include 8-(meth)acryloyloxyoctylmethyldimethoxysilane, 8-(meth)acryloyloxy Octylmethyldiethoxysilane, etc. As an alkenyltrialkoxysilane, an octenyltrialkoxysilane, an octenylalkyldialkoxysilane, etc. are mentioned. As octenyltrialkoxysilane, 7-octenyltrimethoxysilane, 7-octenyltriethoxysilane, etc. are mentioned. As an octenylalkyl dialkoxysilane, 7-octenylmethyldimethoxysilane, 7-octenylmethyldiethoxysilane, etc. are mentioned. Examples of the styrylalkyltrialkoxysilane include p-styryloctyltrimethoxysilane and the like.

矽烷化合物A例如可藉由使有機氯矽烷與醇反應等方法而合成。矽烷化合物A可單獨使用一種，亦可組合使用兩種以上。本實施方式的接著劑組成物亦可進而含有式（I）中s為0～5的矽烷化合物。The silane compound A can be synthesized, for example, by a method such as reacting an organochlorosilane with an alcohol. The silane compound A may be used alone or in combination of two or more. The adhesive composition of the present embodiment may further contain a silane compound in which s is 0 to 5 in formula (I).

自存在被黏著體（電路構件等）與接著劑組成物或其硬化物（電路連接構件等）的界面的接著力進而變強的傾向的觀點考慮，矽烷化合物A的含量較佳的是以接著劑組成物中的接著劑成分（接著劑組成物中的導電粒子以外的固體成分。以下相同）的總質量為基準而言為下述的範圍。矽烷化合物A的含量較佳為0.1質量%以上，更佳為0.25質量%以上，進而較佳為0.5質量%以上。矽烷化合物A的含量較佳為20質量%以下，更佳為10質量%以下，進而較佳為5質量%以下。自該些觀點考慮，矽烷化合物A的含量較佳為0.1質量%～20質量%，更佳為0.25質量%～10質量%，進而較佳為0.5質量%～5質量%。From the viewpoint that the adhesive force at the interface between the adherend (circuit member, etc.) and the adhesive composition or its cured product (circuit connection member, etc.) tends to become stronger, the content of the silane compound A is preferably such that the adhesive The total mass of the adhesive component in the adhesive composition (solid content other than the conductive particles in the adhesive composition. The same applies hereinafter) is within the following range on the basis of the total mass. The content of the silane compound A is preferably 0.1% by mass or more, more preferably 0.25% by mass or more, and still more preferably 0.5% by mass or more. The content of the silane compound A is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less. From these viewpoints, the content of the silane compound A is preferably 0.1% by mass to 20% by mass, more preferably 0.25% by mass to 10% by mass, and still more preferably 0.5% by mass to 5% by mass.

（（a）成分：環氧樹脂） 作為（a）成分，可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、萘型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A型酚醛清漆型環氧樹脂、雙酚F酚醛清漆型環氧樹脂、脂環式環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、乙內醯脲型環氧樹脂、異三聚氰酸酯型環氧樹脂、脂肪族鏈狀環氧樹脂等。（a）成分可經鹵化亦可經氫化。（a）成分可單獨使用一種，亦可組合使用兩種以上。((a) component: epoxy resin) As a component (a), a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a naphthalene type epoxy resin, a phenol novolak type epoxy resin, a cresol novolac type epoxy resin are mentioned. Novolak epoxy resin, bisphenol A novolak epoxy resin, bisphenol F novolak epoxy resin, alicyclic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, Hydantoin type epoxy resin, isocyanurate type epoxy resin, aliphatic chain epoxy resin, etc. The component (a) may be halogenated or hydrogenated. (a) A component may be used individually by 1 type, and may be used in combination of 2 or more types.

自進而提高與被黏著體的接著性的觀點考慮，（a）成分的含量較佳的是以接著劑組成物的接著劑成分的總質量為基準而言為下述的範圍。（a）成分的含量較佳為5質量%以上，更佳為10質量%以上，進而較佳為15質量%以上。（a）成分的含量較佳為90質量%以下，更佳為80質量%以下，進而較佳為70質量%以下。自該些觀點考慮，（a）成分的含量較佳為5質量%～90質量%，更佳為10質量%～80質量%，進而較佳為15質量%～70質量%。From the viewpoint of further improving the adhesiveness with the adherend, the content of the component (a) is preferably in the following range based on the total mass of the adhesive components of the adhesive composition. The content of the component (a) is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more. The content of the component (a) is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less. From these viewpoints, the content of the component (a) is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and still more preferably 15% by mass to 70% by mass.

（（b）成分：潛伏性硬化劑） 作為（b）成分，若可使環氧樹脂硬化，則並無特別限定。作為（b）成分，可列舉可藉由熱或光而產生陰離子種的硬化劑（陰離子聚合性的觸媒型硬化劑等）、可藉由熱或光而產生陽離子種的硬化劑（陽離子聚合性的觸媒型硬化劑等）、加成聚合型硬化劑等。（b）成分可單獨使用一種，亦可組合使用兩種以上。自快速硬化性優異且不需要考慮化學當量的觀點考慮，（b）成分較佳為可藉由熱或光而產生陰離子種或陽離子種的硬化劑，更佳為陰離子聚合性或陽離子聚合性的觸媒型硬化劑。((b) Ingredient: Latent Hardener) As (b) component, if epoxy resin can be hardened, it will not specifically limit. Examples of the component (b) include curing agents capable of generating anionic species by heat or light (anionic polymerizable catalyst-type curing agents, etc.), and curing agents capable of generating cationic species by heat or light (cationic polymerization Catalytic hardener, etc.), addition polymerization hardener, etc. (b) A component may be used individually by 1 type, and may be used in combination of 2 or more types. The (b) component is preferably a curing agent capable of generating anionic species or cationic species by heat or light, more preferably anionic polymerizable or cationic polymerizable, from the viewpoint of being excellent in rapid hardening properties without considering stoichiometry. Catalyst hardener.

作為陰離子聚合性的觸媒型硬化劑，可列舉咪唑系硬化劑、醯肼系硬化劑、三氟化硼-胺錯合物、胺醯亞胺、三級胺類、二胺基順丁烯二腈、三聚氰胺及其衍生物、多胺的鹽、二氰二胺（dicyandiamide）等，亦可使用該些的轉化物。作為陽離子聚合性的觸媒型硬化劑，可列舉重氮鎓鹽、鋶鹽等，亦可使用該些的轉化物。作為加成聚合型硬化劑，可列舉多胺類、聚硫醇類、多酚類、酸酐等。Examples of anionic polymerizable catalyst-type hardeners include imidazole-based hardeners, hydrazide-based hardeners, boron trifluoride-amine complexes, amide imides, tertiary amines, and diamine maleic butenes. Dinitrile, melamine and its derivatives, salts of polyamines, dicyandiamide, etc., and conversion products of these can also be used. As a cationically polymerizable catalyst-type hardener, a diazonium salt, a pernium salt, etc. are mentioned, and the conversion product of these can also be used. As an addition polymerization type hardener, polyamines, polythiols, polyphenols, acid anhydrides, etc. are mentioned.

於使用三級胺類、咪唑系硬化劑等作為陰離子聚合性的觸媒型硬化劑的情況下，可藉由以160℃～200℃左右的中溫進行10秒～數小時左右的加熱而使環氧樹脂硬化。因此，可使使用壽命（usable life）（使用期限（pot life））相較而言變長。In the case of using tertiary amines, imidazole-based hardeners, etc. as an anionic polymerizable catalyst type hardener, it can be cured by heating at a moderate temperature of about 160°C to 200°C for about 10 seconds to several hours. Epoxy hardens. Therefore, usable life (pot life) can be made relatively long.

作為陽離子聚合性的觸媒型硬化劑，例如較佳為可藉由照射能量線而使環氧樹脂硬化的感光性鎓鹽（芳香族重氮鎓鹽、芳香族鋶鹽等）。而且，作為除照射能量線以外藉由熱而進行活性化使環氧樹脂硬化者，可列舉脂肪族鋶鹽等。此種硬化劑因具有快速硬化性而較佳。As a cationically polymerizable catalyst-type hardener, for example, photosensitive onium salts (aromatic diazonium salts, aromatic peronium salts, etc.) that can harden epoxy resins by irradiating energy rays are preferable. Moreover, as what activates and hardens an epoxy resin by heat other than irradiating an energy ray, aliphatic perylene salts etc. are mentioned. Such a hardening agent is preferable because it has rapid hardening properties.

利用高分子物質（聚胺基甲酸酯系、聚酯系等）、金屬（鎳、酮等）薄膜、無機物（矽酸鈣等）等將（b）成分包覆而經微膠囊化的硬化劑可延長使用壽命，因此較佳。Microencapsulated curing by coating the component (b) with a polymer substance (urethane-based, polyester-based, etc.), a metal (nickel, ketone, etc.) film, an inorganic substance (calcium silicate, etc.), etc. It can prolong the service life, so it is better.

自進而提高與被黏著體的接著性的觀點考慮，相對於（a）成分100質量份而言，（b）成分的含量較佳為下述的範圍。（b）成分的含量較佳為10質量份以上，更佳為20質量份以上，進而較佳為30質量份以上。（b）成分的含量較佳為500質量份以下，更佳為100質量份以下，進而較佳為70質量份以下。自該些觀點考慮，（b）成分的含量較佳為10質量份～500質量份，更佳為20質量份～100質量份，進而較佳為30質量份～70質量份。From the viewpoint of further improving the adhesiveness with the adherend, the content of the component (b) is preferably within the following range with respect to 100 parts by mass of the component (a). The content of the component (b) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more. The content of the component (b) is preferably 500 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 70 parts by mass or less. From these viewpoints, the content of the component (b) is preferably 10 parts by mass to 500 parts by mass, more preferably 20 parts by mass to 100 parts by mass, and still more preferably 30 parts by mass to 70 parts by mass.

自進而提高與被黏著體的接著性的觀點考慮，相對於（a）成分與膜形成材料（視需要調配的成分）的合計100質量份而言，（b）成分的含量較佳為下述的範圍。（b）成分的含量較佳為10質量份以上，更佳為20質量份以上，進而較佳為30質量份以上。（b）成分的含量較佳為90質量份以下，更佳為80質量份以下，進而較佳為70質量份以下。自該些觀點考慮，（b）成分的含量較佳為10質量份～90質量份，更佳為20質量份～80質量份，進而較佳為30質量份～90質量份。From the viewpoint of further improving the adhesiveness with the adherend, the content of the component (b) is preferably the following with respect to 100 parts by mass of the total of the component (a) and the film-forming material (component to be prepared as needed) range. The content of the component (b) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more. The content of the component (b) is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and still more preferably 70 parts by mass or less. From these viewpoints, the content of the component (b) is preferably 10 parts by mass to 90 parts by mass, more preferably 20 parts by mass to 80 parts by mass, and still more preferably 30 parts by mass to 90 parts by mass.

（（c）成分：自由基聚合性化合物） （c）成分是具有可自由基聚合的官能基的化合物。作為（c）成分，可列舉(甲基)丙烯酸酯化合物、馬來醯亞胺化合物、檸康醯亞胺樹脂、納迪克醯亞胺樹脂等。所謂「(甲基)丙烯酸酯化合物」是表示具有(甲基)丙烯醯基的化合物。（c）成分可以單體或寡聚物的狀態而使用，亦可將單體與寡聚物併用。（c）成分可單獨使用一種，亦可組合使用兩種以上。((c) Component: radically polymerizable compound) The component (c) is a compound having a radically polymerizable functional group. As (c) component, a (meth)acrylate compound, a maleimide compound, a citraconimide resin, a nadicimide resin, etc. are mentioned. The "(meth)acrylate compound" refers to a compound having a (meth)acryloyl group. The component (c) may be used in the form of a monomer or an oligomer, or a monomer and an oligomer may be used in combination. (c) A component may be used individually by 1 type, and may be used in combination of 2 or more types.

作為(甲基)丙烯酸酯化合物的具體例，可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸異丁酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、2-羥基-1,3-二(甲基)丙烯醯氧基丙烷、2,2-雙[4-((甲基)丙烯醯氧基甲氧基)苯基]丙烷、2,2-雙[4-((甲基)丙烯醯氧基聚乙氧基)苯基]丙烷、(甲基)丙烯酸二環戊烯基酯、(甲基)丙烯酸三環癸基酯、異三聚氰酸三((甲基)丙烯醯氧基乙基)酯、異三聚氰酸EO改質二(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯等。作為(甲基)丙烯酸酯化合物以外的自由基聚合性化合物，例如可適宜地使用專利文獻2（國際公開第2009/063827號）中所記載的化合物。(甲基)丙烯酸酯化合物可單獨使用一種，亦可組合使用兩種以上。Specific examples of the (meth)acrylate compound include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, ethylene glycol Alcohol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, 2-hydroxyl -1,3-bis(meth)acryloyloxypropane, 2,2-bis[4-((meth)acrylooxymethoxy)phenyl]propane, 2,2-bis[4- ((meth)acrylooxypolyethoxy)phenyl]propane, dicyclopentenyl (meth)acrylate, tricyclodecyl (meth)acrylate, tris(() isocyanurate Meth)acryloyloxyethyl)ester, isocyanuric acid EO modified di(meth)acrylate, (meth)acrylate urethane, etc. As a radical polymerizable compound other than a (meth)acrylate compound, the compound described in patent document 2 (International Publication No. 2009/063827), for example, can be used suitably. (Meth)acrylate compound may be used individually by 1 type, and may be used in combination of 2 or more types.

自反應性及應力緩和性優異的觀點考慮，（c）成分較佳為(甲基)丙烯酸酯化合物，更佳為(甲基)丙烯酸胺基甲酸酯。自使耐熱性提高的觀點考慮，較佳的是(甲基)丙烯酸酯化合物具有選自由二環戊烯基、三環癸基及三嗪環所組成的群組中的至少一種取代基。From the viewpoint of being excellent in reactivity and stress relaxation properties, the component (c) is preferably a (meth)acrylate compound, and more preferably a (meth)acrylate urethane. From the viewpoint of improving heat resistance, the (meth)acrylate compound preferably has at least one substituent selected from the group consisting of a dicyclopentenyl group, a tricyclodecyl group, and a triazine ring.

而且，作為（c）成分，較佳為使用具有下述通式（II）所表示的磷酸酯結構的自由基聚合性化合物，更佳為將(甲基)丙烯酸酯化合物等所述自由基聚合性化合物與具有式（II）所表示的磷酸酯結構的自由基聚合性化合物併用。於該些情況下，對於無機物（金屬等）的表面的接著強度提高，因此適於例如電路電極彼此的接著。Furthermore, as the component (c), it is preferable to use a radical polymerizable compound having a phosphoric acid ester structure represented by the following general formula (II), and it is more preferable to use the radical polymerizable compound such as a (meth)acrylate compound. The radically polymerizable compound having a phosphoric acid ester structure represented by formula (II) is used in combination. In these cases, since the bonding strength to the surface of an inorganic substance (metal etc.) improves, it is suitable for bonding of circuit electrodes, for example.

[化3]

Figure 02_image003
[式中，p表示1～3的整數，R表示氫原子或甲基][hua 3]
Figure 02_image003
[In the formula, p represents an integer of 1 to 3, and R represents a hydrogen atom or a methyl group]

所述具有磷酸酯結構的自由基聚合性化合物例如可藉由使無水磷酸與(甲基)丙烯酸-2-羥基乙酯反應而獲得。作為所述具有磷酸酯結構的自由基聚合性化合物的具體例，可列舉磷酸單(2-(甲基)丙烯醯氧基乙基)酯、磷酸二(2-(甲基)丙烯醯氧基乙基)酯等。式（II）所表示的具有磷酸酯結構的自由基聚合性化合物可單獨使用一種，亦可組合使用兩種以上。The radically polymerizable compound having the phosphoric acid ester structure can be obtained, for example, by reacting anhydrous phosphoric acid with 2-hydroxyethyl (meth)acrylate. Specific examples of the radically polymerizable compound having a phosphoric acid ester structure include mono(2-(meth)acryloyloxyethyl) phosphate and di(2-(meth)acryloyloxy phosphate) ethyl) ester, etc. The radically polymerizable compound having a phosphoric acid ester structure represented by formula (II) may be used alone or in combination of two or more.

自進而提高與被黏著體的接著性的觀點考慮，式（II）所表示的具有磷酸酯結構的自由基聚合性化合物的含量較佳為相對於自由基聚合性化合物（相當於自由基聚合性化合物的成分的總量）100質量份而言為0.1質量份～1000質量份，更佳為1質量份～100質量份。自進而提高與被黏著體的接著性的觀點考慮，式（II）所表示的具有磷酸酯結構的自由基聚合性化合物的含量較佳的是相對於自由基聚合性化合物及膜形成材料（視需要使用的成分）的合計100質量份而言為0.01質量份～50質量份，更佳為0.5質量份～10質量份。From the viewpoint of further improving the adhesiveness with the adherend, the content of the radically polymerizable compound having a phosphoric acid ester structure represented by formula (II) is preferably based on the radically polymerizable compound (equivalent to the radically polymerizable compound) The total amount of the components of the compound) is 0.1 part by mass to 1000 parts by mass, more preferably 1 part by mass to 100 parts by mass per 100 parts by mass. From the viewpoint of further improving the adhesion with the adherend, the content of the radically polymerizable compound having a phosphoric acid ester structure represented by formula (II) is preferably relative to the radically polymerizable compound and the film-forming material (depending on It is 0.01 mass part - 50 mass parts with respect to a total of 100 mass parts of components to be used), More preferably, it is 0.5 mass part - 10 mass parts.

所述自由基聚合性化合物亦可含有(甲基)丙烯酸烯丙酯。在這種情況下，(甲基)丙烯酸烯丙酯的含量較佳的是相對於自由基聚合性化合物及膜形成材料（視需要使用的成分）的合計100質量份而言為0.1質量份～10質量份，更佳為0.5質量份～5質量份。The radically polymerizable compound may contain allyl (meth)acrylate. In this case, the content of allyl (meth)acrylate is preferably 0.1 part by mass to 100 parts by mass in total of the radically polymerizable compound and the film-forming material (component used as needed). 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass.

自進而提高與被黏著體的接著性的觀點考慮，（c）成分的含量較佳的是以接著劑組成物的接著劑成分的總質量為基準而言為下述的範圍。（c）成分的含量較佳為10質量%以上，更佳為20質量%以上，進而較佳為30質量%以上。（c）成分的含量較佳為90質量%以下，更佳為80質量%以下，進而較佳為70質量%以下。自該些觀點考慮，（c）成分的含量較佳為10質量%～90質量%，更佳為20質量%～80質量%，進而較佳為30質量%～70質量%。From the viewpoint of further improving the adhesiveness with the adherend, the content of the component (c) is preferably in the following range based on the total mass of the adhesive components of the adhesive composition. The content of the component (c) is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more. The content of the component (c) is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less. From these viewpoints, the content of the component (c) is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and still more preferably 30% by mass to 70% by mass.

（（d）成分：藉由光或熱而產生自由基的硬化劑） 作為（d）成分，可使用（d1）藉由熱而產生遊離自由基的硬化劑（以下根據情況稱為「（d1）成分」）、或（d2）藉由光而產生遊離自由基的硬化劑（以下根據情況稱為「（d2）成分」）。（d1）成分是藉由熱而分解從而產生遊離自由基的硬化劑。作為（d1）成分，可列舉過氧化物（有機過氧化物等）、偶氮系化合物等。自高反應性及提高使用期限的觀點考慮，（d1）成分較佳為10小時半衰期的溫度為40℃以上、且1分鐘半衰期溫度為180℃以下的有機過氧化物，更佳為10小時半衰期的溫度為60℃以上、且1分鐘半衰期溫度為170℃以下的有機過氧化物。(Component (d): hardener that generates radicals by light or heat) As the component (d), (d1) a curing agent that generates free radicals by heat (hereinafter referred to as "component (d1)" in some cases), or (d2) curing agent that generates free radicals by light can be used agent (hereinafter referred to as "(d2) ingredient" as the case may be). The component (d1) is a curing agent that decomposes by heat to generate free radicals. As the component (d1), peroxides (organic peroxides, etc.), azo-based compounds, and the like are exemplified. From the viewpoints of high reactivity and improvement in service life, the component (d1) is preferably an organic peroxide whose 10-hour half-life temperature is 40°C or higher and 1-minute half-life temperature is 180°C or lower, more preferably 10-hour half-life An organic peroxide whose temperature is 60°C or higher and whose 1-minute half-life temperature is 170°C or lower.

作為（d1）成分的具體例，可列舉過氧化二醯基（過氧化苯甲醯基等）、過氧化二碳酸酯、過氧化酯、過氧化縮酮、過氧化二烷基、過氧化氫、矽烷基過氧化物等。Specific examples of the component (d1) include dioxygenyl peroxide (benzyl peroxide, etc.), peroxydicarbonate, peroxyester, peroxyketal, peroxydialkyl, and hydrogen peroxide. , Silane peroxide, etc.

自抑制電極（電路電極等）的腐蝕的觀點考慮，（d1）成分較佳為所含有的氯離子及有機酸的濃度為5000 ppm以下的硬化劑，更佳為在熱分解後所產生的有機酸少的硬化劑。作為此種（d1）成分的具體例，可列舉過氧化酯、過氧化二烷基、過氧化氫、矽烷基過氧化物等，自獲得高反應性的觀點考慮，更佳為過氧化酯。From the viewpoint of suppressing corrosion of electrodes (circuit electrodes, etc.), the component (d1) is preferably a curing agent containing chloride ions and organic acids with a concentration of 5,000 ppm or less, and more preferably organic compounds generated after thermal decomposition. Acid-less hardener. Specific examples of such a component (d1) include peroxyesters, dialkyl peroxides, hydrogen peroxide, silyl peroxides, and the like, and from the viewpoint of obtaining high reactivity, peroxyesters are more preferable.

作為過氧化酯，可列舉過氧化新癸酸枯基酯、過氧化新癸酸-1,1,3,3-四甲基丁酯、過氧化新癸酸-1-環己基-1-甲基乙酯、過氧化新癸酸第三己酯、過氧化特戊酸第三丁酯、過氧化2-乙基己酸-1,1,3,3-四甲基丁酯、2,5-二甲基-2,5-二(2-乙基己醯基過氧基)己烷、過氧化2-乙基己酸-1-環己基-1-甲基乙酯、過氧化2-乙基己酸第三己酯、過氧化2-乙基己酸第三丁酯、過氧化異丁酸第三丁酯、1,1-雙(第三丁基過氧基)環己烷、過氧化異丙基單碳酸第三己酯、過氧化3,5,5-三甲基己酸第三丁酯、過氧化月桂酸第三丁酯、2,5-二甲基-2,5-二(間甲苯甲醯基過氧基)己烷、過氧化異丙基單碳酸第三丁酯、過氧化2-乙基己基單碳酸第三丁酯、過氧基苯甲酸第三己酯、過氧化乙酸第三丁酯等。作為所述過氧化酯以外的（d1）成分，例如可適宜使用專利文獻2（國際公開第2009/063827號）中所記載的化合物。過氧化酯可單獨使用一種，亦可組合使用兩種以上。Examples of the peroxyester include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, and 1-cyclohexyl-1-methyl peroxyneodecanoate Ethyl ethyl ester, 3-hexyl peroxyneodecanoate, 3-butyl peroxypivalate, 2-ethylhexanoic acid-1,1,3,3-tetramethylbutyl peroxide, 2,5 - Dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 2-ethylhexanoic acid-1-cyclohexyl-1-methylethyl peroxide, 2- 3-hexyl ethylhexanoate, 3-butyl 2-ethylhexanoate peroxide, 3-butyl peroxyisobutyrate, 1,1-bis(tert-butylperoxy)cyclohexane, 3,5,5-trimethylhexanoic acid, 3,5,5-trimethylhexanoate, 3,5,5-trimethylhexanoate - bis(m-toluyl peroxy) hexane, 3-butyl peroxyisopropyl monocarbonate, 3-butyl 2-ethylhexyl peroxymonocarbonate, 3-hexyl peroxybenzoate , tert-butyl peroxyacetate, etc. As the component (d1) other than the peroxyester, for example, the compounds described in Patent Document 2 (International Publication No. 2009/063827) can be suitably used. One type of peroxyester may be used alone, or two or more types may be used in combination.

（d2）成分是藉由光而分解，從而產生遊離自由基的硬化劑。作為（d2）成分，可使用藉由照射波長為150 nm～750 nm的光而產生遊離自由基的化合物。作為此種化合物，例如自對於光照射的感度高的觀點考慮，較佳為光引發、光聚合及光硬化（Photoinitiation, Photopolymerization, and Photocuring），J.-P. 富阿西耶（Fouassier），翰思出版社（Hanser Publishers）（1995年）、第17頁～第35頁中所記載的α-乙醯胺基苯酮衍生物及氧化膦衍生物。（d2）成分可單獨使用一種，亦可組合使用兩種以上。亦可將（d2）成分與（d1）成分（所述過氧化物、偶氮化合物等）組合而使用。亦可將（d1）成分或（d2）成分與藉由超音波、電磁波等而產生遊離自由基的硬化劑組合而使用。The component (d2) is a curing agent that decomposes by light to generate free radicals. As the component (d2), a compound that generates free radicals by irradiation with light having a wavelength of 150 nm to 750 nm can be used. As such a compound, for example, from the viewpoint of high sensitivity to light irradiation, preferably photoinitiation, photopolymerization, and photocuring (Photoinitiation, Photopolymerization, and Photocuring), J.-P. Fouassier, The α-acetamidophenone derivatives and phosphine oxide derivatives described in Hanser Publishers (1995), pages 17 to 35. The (d2) component may be used alone or in combination of two or more. (d2) component and (d1) component (the said peroxide, an azo compound, etc.) can also be used in combination. The component (d1) or the component (d2) may be used in combination with a curing agent that generates free radicals by ultrasonic waves, electromagnetic waves, or the like.

（d）成分可根據目標的連接溫度、連接時間、使用期限等而適宜選定。（d）成分可單獨使用一種，亦可組合使用兩種以上。亦可將（d）成分與分解促進劑、分解抑制劑等併用。而且，亦可藉由聚胺基甲酸酯系或聚酯系的高分子物質等包覆（d）成分而進行微膠囊化。微膠囊化的硬化劑可延長使用壽命，因此較佳。The component (d) can be appropriately selected according to the intended connection temperature, connection time, and use period. (d) A component may be used individually by 1 type, and may be used in combination of 2 or more types. The component (d) may be used in combination with a decomposition accelerator, a decomposition inhibitor, or the like. Further, the component (d) may be coated with a polyurethane-based or polyester-based polymer substance or the like to perform microencapsulation. Microencapsulated hardeners are preferred for extended service life.

在連接時間為25秒以下的情況下，自容易獲得充分的反應率的觀點考慮，（d）成分的含量較佳為下述的範圍。相對於（c）成分100質量份而言，（d）成分的含量較佳為0.1質量份以上，更佳為1質量份以上。相對於（c）成分100質量份而言，（d）成分的含量較佳為40質量份以下，更佳為20質量份以下。自該些觀點考慮，相對於（c）成分100質量份而言，（d）成分的含量較佳為0.1質量份～40質量份，更佳為1質量份～20質量份。When the connection time is 25 seconds or less, from the viewpoint of easily obtaining a sufficient reaction rate, the content of the component (d) is preferably within the following range. 0.1 mass part or more is preferable with respect to 100 mass parts of (c) components, and, as for content of (d) component, 1 mass part or more is more preferable. 40 mass parts or less are preferable with respect to 100 mass parts of (c) components, and, as for content of (d) component, 20 mass parts or less are more preferable. From these viewpoints, the content of the component (d) is preferably 0.1 to 40 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the (c) component.

在連接時間為25秒以下的情況下，自容易獲得充分的反應率的觀點考慮，（d）成分的含量較佳為下述的範圍。相對於（c）成分及膜形成材料（視需要使用的成分）的合計100質量份而言，（d）成分的含量較佳為0.1質量份以上，更佳為1質量份以上。相對於（c）成分及膜形成材料（視需要使用的成分）的合計100質量份而言，（d）成分的含量較佳為40質量份以下，更佳為20質量份以下。自該些觀點考慮，相對於（c）成分及膜形成材料（視需要使用的成分）的合計100質量份而言，（d）成分的含量較佳為0.1質量份～40質量份，更佳為1質量份～20質量份。When the connection time is 25 seconds or less, from the viewpoint of easily obtaining a sufficient reaction rate, the content of the component (d) is preferably within the following range. The content of the component (d) is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the total of the component (c) and the film-forming material (component used as needed). The content of the component (d) is preferably 40 parts by mass or less, more preferably 20 parts by mass or less, relative to 100 parts by mass of the total of the component (c) and the film-forming material (component used as needed). From these viewpoints, the content of the component (d) is preferably 0.1 parts by mass to 40 parts by mass, more preferably 100 parts by mass in total of the component (c) and the film-forming material (component used as needed). It is 1 mass part - 20 mass parts.

自容易獲得充分的反應率的觀點考慮，並不限定連接時間的情況的（d）成分的含量較佳為下述的範圍。相對於（c）成分100質量份而言，（d）成分的含量較佳為0.01質量份以上，更佳為0.1質量份以上。相對於（c）成分100質量份而言，（d）成分的含量較佳為30質量份以下，更佳為15質量份以下。自該些觀點考慮，相對於（c）成分100質量份而言，（d）成分的含量較佳為0.01質量份～30質量份，更佳為0.1質量份～15質量份。From the viewpoint of easily obtaining a sufficient reaction rate, when the connection time is not limited, the content of the component (d) is preferably within the following range. 0.01 mass part or more is preferable with respect to 100 mass parts of (c) components, and, as for content of (d) component, 0.1 mass part or more is more preferable. 30 mass parts or less are preferable with respect to 100 mass parts of (c) components, and, as for content of (d) component, 15 mass parts or less are more preferable. From these viewpoints, the content of the component (d) is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 15 parts by mass, relative to 100 parts by mass of the (c) component.

自容易獲得充分的反應率的觀點考慮，並不限定連接時間的情況的（d）成分的含量較佳為下述的範圍。相對於（c）成分及膜形成材料（視需要使用的成分）的合計100質量份而言，（d）成分的含量較佳為0.01質量份以上，更佳為0.1質量份以上。相對於（c）成分及膜形成材料（視需要使用的成分）的合計100質量份而言，（d）成分的含量較佳為30質量份以下，更佳為15質量份以下。自該些觀點考慮，相對於（c）成分及膜形成材料（視需要使用的成分）的合計100質量份而言，（d）成分的含量較佳為0.01質量份～30質量份，更佳為0.1質量份～15質量份。From the viewpoint of easily obtaining a sufficient reaction rate, when the connection time is not limited, the content of the component (d) is preferably within the following range. The content of the component (d) is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, relative to 100 parts by mass of the total of the component (c) and the film-forming material (component used as needed). The content of the component (d) is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, relative to 100 parts by mass of the total of the component (c) and the film-forming material (component used as needed). From these viewpoints, the content of the component (d) is preferably 0.01 parts by mass to 30 parts by mass, more preferably 100 parts by mass in total of the component (c) and the film-forming material (component to be used as needed). It is 0.1 mass part - 15 mass parts.

（膜形成材料） 本實施方式的接著劑組成物亦可視需要而含有膜形成材料。膜形成材料在使液狀的接著劑組成物固形化為膜狀的情況下，可使通常狀態（常溫常壓）下膜的操作性提高，對膜賦予難以裂開、難以破損、難以黏膩等特性。作為膜形成材料，可列舉苯氧樹脂、聚乙烯甲醛、聚苯乙烯、聚乙烯丁醛、聚酯、聚醯胺、二甲苯樹脂、聚胺基甲酸酯等。自接著性、相溶性、耐熱性及機械強度優異的觀點考慮，該些中較佳為苯氧樹脂。膜形成材料可單獨使用一種，亦可組合使用兩種以上。(film forming material) The adhesive composition of this embodiment may contain a film-forming material as needed. The film-forming material can improve the handleability of the film in a normal state (normal temperature and pressure) when the liquid adhesive composition is solidified into a film, and imparts resistance to cracking, breakage, and stickiness to the film. and other characteristics. As a film forming material, phenoxy resin, polyvinyl formaldehyde, polystyrene, polyvinyl butyral, polyester, polyamide, xylene resin, polyurethane, etc. are mentioned. From the viewpoint of being excellent in adhesiveness, compatibility, heat resistance, and mechanical strength, a phenoxy resin is preferable among these. The film-forming material may be used alone or in combination of two or more.

作為苯氧樹脂，例如可列舉藉由使2官能環氧樹脂與2官能酚類進行加成聚合而獲得的樹脂、及藉由使2官能酚類與表鹵醇進行反應直至高分子化而獲得的樹脂。苯氧樹脂例如可藉由1莫耳2官能酚類與0.985莫耳～1.015莫耳表鹵醇在鹼金屬氫氧化物等觸媒的存在下，在非反應性溶劑中、40℃～120℃的溫度下進行反應而獲得。自樹脂的機械特性及熱特性優異的觀點考慮，苯氧樹脂特佳的是將2官能性環氧樹脂與2官能性酚類的調配當量比設為環氧基/酚性羥基=1/0.9～1/1.1，在鹼金屬化合物、有機磷系化合物、環狀胺系化合物等觸媒的存在下，在沸點為120℃以上的有機溶劑（醯胺系、醚系、酮系、內酯系、醇系等）中，在反應固體成分為50質量%以下的條件下加熱至50℃～200℃進行加成聚合反應而獲得。苯氧樹脂可單獨使用一種，亦可組合使用兩種以上。Examples of the phenoxy resin include resins obtained by addition-polymerizing bifunctional epoxy resins and bifunctional phenols, and those obtained by reacting bifunctional phenols with epihalohydrin until polymerized. of resin. Phenoxy resins can be prepared by, for example, 1 mole of bifunctional phenols and 0.985 moles to 1.015 moles of epihalohydrin in the presence of catalysts such as alkali metal hydroxides in a non-reactive solvent at 40°C to 120°C. obtained by reacting at the temperature. From the viewpoint of excellent mechanical properties and thermal properties of the resin, it is particularly preferable for the phenoxy resin to set the blending equivalent ratio of the bifunctional epoxy resin and the bifunctional phenol to epoxy group/phenolic hydroxyl group=1/0.9 ～1/1.1, in the presence of catalysts such as alkali metal compounds, organophosphorus compounds, cyclic amine compounds, etc., in organic solvents (amide, ether, ketone, lactone) with a boiling point of 120°C or higher , alcohol-based, etc.), it is obtained by heating to 50°C to 200°C under the condition that the solid content of the reaction is 50% by mass or less to carry out an addition polymerization reaction. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

作為2官能環氧樹脂，可列舉雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AD型環氧樹脂、雙酚S型環氧樹脂、聯苯二縮水甘油醚、經甲基取代的聯苯二縮水甘油醚等。2官能酚類是具有2個酚性羥基的化合物。作為2官能酚類，可列舉對苯二酚類、雙酚A、雙酚F、雙酚AD、雙酚S、雙酚茀（4,4'-(9-亞茀基)二苯酚等）、經甲基取代的雙酚茀、二羥基聯苯、經甲基取代的二羥基聯苯等雙酚類等。苯氧樹脂亦可經自由基聚合性官能基、或其他反應性化合物改質（例如環氧改質）。Bifunctional epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, biphenyl diglycidyl ether, methyl methacrylate substituted biphenyl diglycidyl ether, etc. Bifunctional phenols are compounds having two phenolic hydroxyl groups. Examples of bifunctional phenols include hydroquinones, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, bisphenol fluoride (4,4'-(9-phenylene)diphenol, etc.) , bisphenols such as methyl-substituted bisphenol fluoride, dihydroxybiphenyl, methyl-substituted dihydroxybiphenyl, etc. Phenoxy resins can also be modified with radically polymerizable functional groups, or other reactive compounds (eg, epoxy modification).

相對於接著劑組成物的接著劑成分100質量份而言，膜形成材料的含量較佳為10質量份～90質量份，更佳為20質量份～60質量份。The content of the film-forming material is preferably 10 to 90 parts by mass, more preferably 20 to 60 parts by mass, relative to 100 parts by mass of the adhesive component of the adhesive composition.

（導電粒子） 本實施方式的接著劑組成物亦可進而含有導電粒子。作為導電粒子的構成材料，可列舉金（Au）、銀（Ag）、鎳（Ni）、銅（Cu）、焊料等金屬、碳等。而且，亦可為以非導電性的樹脂、玻璃、陶瓷、塑膠等為核，於該核上包覆有所述金屬（金屬粒子等）或碳的包覆導電粒子。包覆導電粒子或熱熔融金屬粒子由於加熱加壓而具有變形性，因此在連接時消除電路電極的高度不均一，在連接時與電極的接觸面積增加，因此可靠性提高而較佳。(conductive particles) The adhesive composition of the present embodiment may further contain conductive particles. Examples of the constituent material of the conductive particles include metals such as gold (Au), silver (Ag), nickel (Ni), copper (Cu), and solder, carbon, and the like. In addition, non-conductive resins, glass, ceramics, plastics, etc. are used as cores, and the cores may be coated with the above-mentioned metal (metal particles, etc.) or carbon-coated conductive particles. The coated conductive particles or the hot-melt metal particles have deformability due to heat and pressure, so that the height unevenness of the circuit electrodes is eliminated during connection, and the contact area with the electrodes during connection is increased, so that reliability is improved.

自分散性及導電性優異的觀點考慮，導電粒子的平均粒徑較佳為1 μm～30 μm。導電粒子的平均粒徑例如可使用雷射繞射法等機器分析而測定。自導電性優異的觀點考慮，相對於接著劑組成物的接著劑成分100質量份而言，導電粒子的含量較佳為0.1質量份以上，更佳為1質量份以上。自容易抑制電極（電路電極等）短路的觀點考慮，相對於接著劑組成物的接著劑成分100質量份而言，導電粒子的含量較佳為100質量份以下，更佳為50質量份以下。From the viewpoint of being excellent in self-dispersibility and electrical conductivity, the average particle diameter of the conductive particles is preferably 1 μm to 30 μm. The average particle diameter of the conductive particles can be measured using, for example, machine analysis such as laser diffraction. From the viewpoint of excellent conductivity, the content of the conductive particles is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the adhesive component of the adhesive composition. The content of the conductive particles is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, relative to 100 parts by mass of the adhesive component of the adhesive composition, from the viewpoint of easily suppressing short circuits in electrodes (circuit electrodes, etc.).

（其他成分） 本實施方式的接著劑組成物亦可視需要適宜含有對苯二酚、對苯二酚甲醚類等聚合抑制劑。(other ingredients) The adhesive composition of the present embodiment may suitably contain a polymerization inhibitor such as hydroquinone and hydroquinone methyl ethers as needed.

本實施方式的接著劑組成物亦可進而含有使選自由(甲基)丙烯酸、(甲基)丙烯酸酯及丙烯腈所組成的群組中的至少一種單體成分聚合而獲得的均聚物或共聚物。自應力緩和優異的觀點考慮，較佳的是本實施方式的接著劑組成物含有丙烯酸橡膠等，所述丙烯酸橡膠是使具有縮水甘油醚基的(甲基)丙烯酸縮水甘油酯聚合而獲得的共聚物。自提高接著劑組成物的凝聚力的觀點考慮，所述丙烯酸橡膠的重量平均分子量較佳為20萬以上。The adhesive composition of the present embodiment may further contain a homopolymer or a homopolymer obtained by polymerizing at least one monomer component selected from the group consisting of (meth)acrylic acid, (meth)acrylate, and acrylonitrile. copolymer. From the viewpoint of being excellent in stress relaxation, the adhesive composition of the present embodiment preferably contains an acrylic rubber or the like which is a copolymer obtained by polymerizing glycidyl (meth)acrylate having a glycidyl ether group. thing. From the viewpoint of improving the cohesive force of the adhesive composition, the weight average molecular weight of the acrylic rubber is preferably 200,000 or more.

本實施方式的接著劑組成物亦可含有所述導電粒子的表面包覆有高分子樹脂等的包覆微粒子。在將此種包覆微粒子與所述導電粒子併用的情況下，即使在導電粒子的含量增加的情況下，亦容易抑制由於導電粒子彼此接觸所造成的短路，因此使鄰接的電路電極間的絕緣性提高。可並不使用導電粒子而單獨使用所述包覆微粒子，亦可將包覆微粒子與導電粒子併用。The adhesive composition of the present embodiment may contain coated fine particles in which the surfaces of the conductive particles are coated with a polymer resin or the like. When such coated fine particles are used in combination with the conductive particles, even when the content of the conductive particles is increased, short-circuiting due to contact of the conductive particles with each other is easily suppressed, thereby insulating the adjacent circuit electrodes. Sexual improvement. The coated fine particles may be used alone without using the conductive particles, or the coated fine particles and the conductive particles may be used in combination.

本實施方式的接著劑組成物亦可含有橡膠微粒子、填充劑、軟化劑、促進劑、抗老化劑、著色劑、阻燃化劑、觸變劑、偶合劑、酚樹脂、三聚氰胺樹脂、異氰酸酯類等。本實施方式的接著劑組成物亦可適宜含有密接性改善劑（偶合劑除外）、增黏劑、調平劑、著色劑、耐候性改善劑等添加劑。The adhesive composition of this embodiment may contain rubber fine particles, fillers, softeners, accelerators, antiaging agents, colorants, flame retardants, thixotropic agents, coupling agents, phenol resins, melamine resins, isocyanates Wait. The adhesive composition of the present embodiment may suitably contain additives such as adhesion improvers (excluding coupling agents), tackifiers, levelers, colorants, and weather resistance improvers.

橡膠微粒子較佳為具有導電粒子的平均粒徑的2倍以下的平均粒徑、且在常溫下的儲存彈性模數是導電粒子及接著劑組成物在常溫下的儲存彈性模數的1/2以下的粒子。特別是在橡膠微粒子的材質為矽酮、丙烯酸系乳液（acrylic emulsion）、苯乙烯-丁二烯橡膠（Styrene Butadiene Rubber，SBR）、丁腈橡膠（Nitrile-Butadiene Rubber，NBR）或聚丁二烯橡膠的情況下，橡膠微粒子適宜的是單獨使用或將兩種以上混合使用。三維交聯的橡膠微粒子的耐溶劑性優異，容易分散於接著劑組成物中。The rubber fine particles preferably have an average particle diameter that is not more than twice the average particle diameter of the conductive particles, and the storage elastic modulus at room temperature is 1/2 of the storage elastic modulus of the conductive particles and the adhesive composition at room temperature. the following particles. Especially when the rubber particles are made of silicone, acrylic emulsion, Styrene Butadiene Rubber (SBR), Nitrile-Butadiene Rubber (NBR) or polybutadiene In the case of rubber, the rubber fine particles are preferably used alone or in combination of two or more. The three-dimensionally crosslinked rubber fine particles are excellent in solvent resistance, and are easily dispersed in the adhesive composition.

填充劑可使電路電極間的電氣特性（連接可靠性等）提高。作為填充劑，例如可適宜使用具有導電粒子的平均粒徑的1/2以下的平均粒徑的粒子。在將並不具有導電性的粒子與填充劑併用的情況下，可使用並不具有導電性的粒子的平均粒徑以下的粒子作為填充劑。填充劑的含量較佳的是相對於接著劑組成物的接著劑成分100質量份而言為5質量份～60質量份。藉由使所述含量為60質量份以下，存在更充分地獲得連接可靠性的提高效果的傾向。藉由使所述含量為5質量份以上，存在充分獲得填充劑的添加效果的傾向。The filler can improve electrical properties (connection reliability, etc.) between circuit electrodes. As the filler, for example, particles having an average particle diameter of 1/2 or less of the average particle diameter of the conductive particles can be suitably used. In the case of using non-conductive particles together with a filler, particles having an average particle diameter or less of the non-conductive particles can be used as the filler. The content of the filler is preferably 5 parts by mass to 60 parts by mass with respect to 100 parts by mass of the adhesive component of the adhesive composition. By making the said content 60 mass parts or less, there exists a tendency for the improvement effect of connection reliability to be acquired more fully. By making the said content into 5 mass parts or more, there exists a tendency for the addition effect of a filler to be fully acquired.

本實施方式的接著劑組成物在常溫下為液狀的情況下，可以糊狀而使用。在常溫下為固體的情況下，除了進行加熱而使用以外，亦可使用溶劑而進行糊化。作為可使用的溶劑，若為對於接著劑組成物及添加劑而言並無反應性、且顯示出充分的溶解性的溶劑，則並無特別限制，較佳為在常壓下的沸點為50℃～150℃的溶劑。沸點若為50℃以上，則在常溫下溶劑的揮發性差，因此即使是開放系統亦可使用。沸點若為150℃以下，則容易使溶劑揮發，因此可在接著後獲得良好的可靠性。When the adhesive composition of the present embodiment is in a liquid state at normal temperature, it can be used in a paste state. When it is a solid at normal temperature, it may be gelatinized using a solvent other than heating and using. The usable solvent is not particularly limited as long as it has no reactivity with respect to the adhesive composition and additives and exhibits sufficient solubility, but the boiling point under normal pressure is preferably 50°C ~150°C solvent. If the boiling point is 50° C. or higher, the volatility of the solvent is poor at normal temperature, so it can be used even in an open system. When the boiling point is 150° C. or lower, since the solvent is easily volatilized, good reliability can be obtained after the bonding.

本實施方式的接著劑組成物亦可為膜狀。可視需要將使溶劑等添加於接著劑組成物中等而得的溶液塗佈於氟樹脂膜、聚對苯二甲酸乙二酯膜、剝離性基材（脫模紙等）上，然後將溶劑等除去，藉此獲得膜。而且，在不織布等基材中含浸所述溶液而載置於剝離性基材上之後，藉由將溶劑等除去而可獲得膜。若以膜狀來使用，則自操作性等優異的觀點考慮更加便利。The adhesive composition of the present embodiment may be in the form of a film. If necessary, a solution obtained by adding a solvent, etc. to the adhesive composition is applied to a fluororesin film, a polyethylene terephthalate film, a releasable substrate (release paper, etc.), and then the solvent, etc. removed, thereby obtaining a film. Then, after impregnating a base material such as a nonwoven fabric with the solution and placing it on a releasable base material, a film can be obtained by removing the solvent or the like. When it is used in a film form, it is more convenient from the viewpoint of being excellent in workability and the like.

本實施方式的接著劑組成物可藉由與加熱或光照射一同進行加壓而使其接著。藉由併用加熱及光照射，可進而以低溫短時間進行接著。光照射較佳的是照射150 nm～750 nm的波長區域的光。可使用低壓水銀燈、中壓水銀燈、高壓水銀燈（超高壓水銀燈等）、氙氣燈、金屬鹵素燈等，以0.1 J/cm2 ～10 J/cm2 的照射量進行硬化。加熱溫度並無特別限制，較佳為50℃～170℃的溫度。壓力若為並不對被黏著體造成損傷的範圍，則並無特別限制，較佳為0.1 MPa～10 MPa。較佳為在0.5秒～3小時的範圍進行加熱及加壓。The adhesive composition of the present embodiment can be bonded by applying pressure together with heating or light irradiation. By using heating and light irradiation in combination, the bonding can be further performed at a low temperature for a short period of time. The light irradiation is preferably light in a wavelength region of 150 nm to 750 nm. Curing can be performed using low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps (ultra-high pressure mercury lamps, etc.), xenon lamps, metal halide lamps, etc., with an irradiation dose of 0.1 J/cm 2 to 10 J/cm 2 . The heating temperature is not particularly limited, but is preferably a temperature of 50°C to 170°C. The pressure is not particularly limited as long as it is in a range that does not damage the adherend, but is preferably 0.1 MPa to 10 MPa. It is preferable to heat and pressurize in the range of 0.5 second - 3 hours.

本實施方式的接著劑組成物可作為熱膨脹係數不同的不同種被黏著體的接著劑而使用。具體而言可作為各向異性導電接著劑、銀糊、銀膜等所代表的電路連接材料；晶片尺寸封裝（Chip Scale Package，CSP）用彈性體、CSP用底部填充材料、晶片上引線（Lead on Chip，LOC）膠帶等所代表的半導體元件接著材料等而使用。對於由各種材質（例如無機物（氧化物、金屬等）、有機物、以及該些的複合物）所構成的被黏著體，本實施方式的接著劑組成物於可靠性試驗前後均具有優異的接著強度。The adhesive composition of the present embodiment can be used as an adhesive for different types of adherends having different thermal expansion coefficients. Specifically, it can be used as a circuit connection material represented by anisotropic conductive adhesive, silver paste, silver film, etc.; elastomer for chip scale package (CSP), underfill material for CSP, lead on chip (Lead on chip) On Chip, LOC) tapes, etc. represented by the semiconductor element adhesive materials, etc. are used. For adherends composed of various materials (for example, inorganic substances (oxides, metals, etc.), organic substances, and composites thereof), the adhesive composition of this embodiment has excellent adhesive strength before and after the reliability test .

＜結構體及其製造方法＞ 本實施方式的結構體具備本實施方式的接著劑組成物或其硬化物。本實施方式的結構體例如為電路連接結構體等半導體裝置。作為本實施方式的結構體的一實施方式，電路連接結構體具備具有第一電路電極的第一電路構件、具有第二電路電極的第二電路構件、及配置在第一電路構件與第二電路構件之間的電路連接構件。第一電路構件例如包含第一基板、與配置在該第一基板上的第一電路電極。第二電路構件例如包含第二基板、與配置在該第二基板上的第二電路電極。第一電路電極及第二電路電極相對向且電性連接。電路連接構件包含本實施方式的接著劑組成物或其硬化物。本實施方式的結構體若具備本實施方式的接著劑組成物或其硬化物即可，亦可使用並不具有電路電極的構件（基板等）而代替所述電路連接結構體的電路構件。<Structure and method for manufacturing the same> The structure of this embodiment includes the adhesive composition of this embodiment or a cured product thereof. The structure of the present embodiment is, for example, a semiconductor device such as a circuit connection structure. As an embodiment of the structure of the present embodiment, the circuit connection structure includes a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode, and a circuit connection structure disposed between the first circuit member and the second circuit The circuit between the components connects the components. The first circuit member includes, for example, a first substrate and a first circuit electrode arranged on the first substrate. The second circuit member includes, for example, a second substrate and a second circuit electrode arranged on the second substrate. The first circuit electrode and the second circuit electrode are opposite to each other and are electrically connected. The circuit connection member contains the adhesive composition of the present embodiment or a cured product thereof. The structure of the present embodiment may be provided with the adhesive composition of the present embodiment or a cured product thereof, and a member (substrate or the like) not having a circuit electrode may be used instead of the circuit member of the circuit connection structure.

本實施方式的結構體的製造方法具備使本實施方式的接著劑組成物硬化的步驟。作為本實施方式的結構體的製造方法的一實施方式，電路連接結構體的製造方法具備：配置步驟，在具有第一電路電極的第一電路構件與具有第二電路電極的第二電路構件之間配置本實施方式的接著劑組成物，加熱加壓步驟，對第一電路構件與第二電路構件進行加壓而使第一電路電極與第二電路電極電性連接，且對接著劑組成物進行加熱而使其硬化。在配置步驟中，可以第一電路電極與第二電路電極相對向的方式進行配置。在加熱加壓步驟中，可對第一電路構件與第二電路構件相對向的方向進行加壓。The manufacturing method of the structure of this embodiment includes the step of hardening the adhesive composition of this embodiment. As an embodiment of the method of manufacturing a structure of the present embodiment, the method of manufacturing a circuit-connected structure includes an arranging step of placing between a first circuit member having a first circuit electrode and a second circuit member having a second circuit electrode The adhesive composition of the present embodiment is arranged between, and the heating and pressurizing step is performed to pressurize the first circuit member and the second circuit member to electrically connect the first circuit electrode and the second circuit electrode, and apply pressure to the adhesive composition. It is hardened by heating. In the arranging step, the first circuit electrode and the second circuit electrode may be arranged to face each other. In the heating and pressing step, pressure may be applied in a direction in which the first circuit member and the second circuit member face each other.

以下，使用圖式，關於電路連接結構體及其製造方法加以說明而作為本實施方式的一實施方式。圖1是表示結構體的一實施方式的示意剖面圖。圖1中所示的電路連接結構體100a具備相對向的電路構件（第一電路構件）20及電路構件（第二電路構件）30，在電路構件20與電路構件30之間配置有連接該些構件的電路連接構件10。電路連接構件10包含本實施方式的接著劑組成物的硬化物。Hereinafter, the circuit connection structure and the manufacturing method thereof will be described as one embodiment of the present embodiment using the drawings. FIG. 1 is a schematic cross-sectional view showing an embodiment of a structure. The circuit connection structure 100 a shown in FIG. 1 includes a circuit member (first circuit member) 20 and a circuit member (second circuit member) 30 that face each other, and these are arranged and connected between the circuit member 20 and the circuit member 30 . The circuit of the component connects the component 10 . The circuit connection member 10 contains the hardened|cured material of the adhesive composition of this embodiment.

電路構件20具備基板（第一基板）21與配置在基板21的主表面21a上的電路電極（第一電路電極）22。在基板21的主表面21a上，亦可根據情況配置絕緣層（未圖示）。The circuit member 20 includes a substrate (first substrate) 21 and circuit electrodes (first circuit electrodes) 22 arranged on the main surface 21 a of the substrate 21 . On the main surface 21a of the board|substrate 21, an insulating layer (not shown) may be arrange|positioned according to the situation.

電路構件30具備基板（第二基板）31與配置在基板31的主表面31a上的電路電極（第二電路電極）32。在基板31的主表面31a上，亦可根據情況而配置絕緣層（未圖示）。The circuit member 30 includes a substrate (second substrate) 31 and circuit electrodes (second circuit electrodes) 32 arranged on the main surface 31 a of the substrate 31 . On the main surface 31a of the board|substrate 31, an insulating layer (not shown) may be arrange|positioned in some cases.

電路連接構件10含有絕緣性物質（除導電粒子以外的成分的硬化物）10a及導電粒子10b。導電粒子10b至少配置在相對向的電路電極22與電路電極32之間。在電路連接結構體100a中，電路電極22及電路電極32經由導電粒子10b而電性連接。The circuit connection member 10 contains an insulating substance (hardened product of components other than conductive particles) 10 a and conductive particles 10 b. The conductive particles 10b are arranged at least between the opposing circuit electrodes 22 and the circuit electrodes 32 . In the circuit connection structure 100a, the circuit electrode 22 and the circuit electrode 32 are electrically connected via the conductive particles 10b.

電路構件20及電路構件30具有單個或多個電路電極（連接端子）。作為電路構件20及電路構件30，例如可使用包含需要電性連接的電極的構件。作為電路構件，可使用半導體晶片（IC晶片）、電阻器晶片、電容器晶片等晶片零件；印刷基板、半導體搭載用基板等基板等。作為電路構件20及電路構件30的組合，例如可使用半導體晶片及半導體搭載用基板。作為基板的材質，例如可列舉半導體、玻璃、陶瓷等無機物；聚醯亞胺、聚對苯二甲酸乙二酯、聚碳酸酯、(甲基)丙烯酸樹脂、環狀烯烴樹脂等有機物；玻璃/環氧等的複合物等。基板亦可為塑膠基板。The circuit member 20 and the circuit member 30 have a single or a plurality of circuit electrodes (connection terminals). As the circuit member 20 and the circuit member 30, for example, a member including electrodes to be electrically connected can be used. As the circuit member, wafer parts such as semiconductor wafers (IC wafers), resistor wafers, and capacitor wafers, and substrates such as printed circuit boards and substrates for mounting semiconductors, and the like can be used. As the combination of the circuit member 20 and the circuit member 30 , for example, a semiconductor wafer and a substrate for mounting a semiconductor can be used. Examples of the material of the substrate include inorganic substances such as semiconductors, glass, and ceramics; organic substances such as polyimide, polyethylene terephthalate, polycarbonate, (meth)acrylic resin, and cyclic olefin resin; glass/ Compounds such as epoxy etc. The substrate can also be a plastic substrate.

圖2是表示結構體的另一實施方式的示意剖面圖。圖2所示的電路連接結構體100b除電路連接構件10不含導電粒子10b以外，具有與電路連接結構體100a同樣的構成。在圖2所示的電路連接結構體100b中，電路電極22與電路電極32並不經由導電粒子而直接接觸，從而電性連接。FIG. 2 is a schematic cross-sectional view showing another embodiment of the structure. The circuit connection structure 100b shown in FIG. 2 has the same structure as the circuit connection structure 100a except that the circuit connection member 10 does not contain the conductive particle 10b. In the circuit connection structure 100b shown in FIG. 2, the circuit electrode 22 and the circuit electrode 32 are in direct contact with each other without the conductive particles, and are thus electrically connected.

電路連接結構體100a及電路連接結構體100b例如可藉由以下的方法而製造。首先，在接著劑組成物為糊狀的情況下，塗佈接著劑組成物及進行乾燥，藉此在電路構件20上配置含有接著劑組成物的樹脂層。在接著劑組成物為膜狀的情況下，將膜狀接著劑組成物貼附於電路構件20上，藉此在電路構件20上配置含有接著劑組成物的樹脂層。繼而，以電路電極22與電路電極32對向配置的方式，在電路構件20上所配置的樹脂層上載置電路構件30。其次，對含有接著劑組成物的樹脂層進行加熱處理或光照射，藉此使接著劑組成物硬化而獲得硬化物（電路連接構件10）。藉由以上而獲得電路連接結構體100a及電路連接結構體100b。 [實施例]The circuit connection structure 100a and the circuit connection structure 100b can be manufactured by the following method, for example. First, when the adhesive composition is in the form of a paste, the resin layer containing the adhesive composition is arranged on the circuit member 20 by applying the adhesive composition and drying. When the adhesive composition is in the form of a film, the resin layer containing the adhesive composition is disposed on the circuit member 20 by sticking the film-shaped adhesive composition on the circuit member 20 . Next, the circuit member 30 is placed on the resin layer arranged on the circuit member 20 so that the circuit electrode 22 and the circuit electrode 32 are arranged to face each other. Next, by subjecting the resin layer containing the adhesive composition to heat treatment or light irradiation, the adhesive composition is cured to obtain a cured product (circuit connecting member 10 ). By the above, the circuit connection structure 100a and the circuit connection structure 100b are obtained. [Example]

以下，基於實施例對本發明加以具體的說明，但本發明並不限定於以下的實施例。Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the following examples.

＜膜狀接著劑組成物的製作＞ [實施例1] 自雙酚A型環氧樹脂、與在分子內具有茀環結構的酚化合物（4,4'-(9-亞茀基)-二苯酚）來合成苯氧樹脂。將該苯氧樹脂溶解於甲苯/乙酸乙酯=50/50（質量比）的混合溶液中而製備固體成分40質量%的溶液。其次，作為橡膠成分，準備丙烯酸橡膠（丙烯酸丁酯40質量份-丙烯酸乙酯30質量份-丙烯腈30質量份-甲基丙烯酸縮水甘油酯3質量份的共聚物、重量平均分子量80萬），將該丙烯酸橡膠溶解於甲苯/乙酸乙酯=50/50（質量比）的混合溶液中而製備固體成分15質量%的溶液。而且，準備以質量比34：49：17而含有微膠囊型潛伏性硬化劑（經微膠囊化的胺系硬化劑）、雙酚F型環氧樹脂與萘型環氧樹脂的液狀的含硬化劑的環氧樹脂（環氧當量：202）。而且，作為矽烷化合物，準備8-縮水甘油氧基辛基三甲氧基矽烷（製品名：KBM4803、信越化學工業股份有限公司製造）。<Preparation of film-like adhesive composition> [Example 1] A phenoxy resin is synthesized from a bisphenol A epoxy resin and a phenol compound (4,4'-(9-perylene)-diphenol) having a perylene ring structure in the molecule. This phenoxy resin was melt|dissolved in the mixed solution of toluene/ethyl acetate=50/50 (mass ratio), and the solid content 40 mass % solution was prepared. Next, as a rubber component, an acrylic rubber (copolymer of 40 parts by mass of butyl acrylate-30 parts by mass of ethyl acrylate-30 parts by mass of acrylonitrile-3 parts by mass of glycidyl methacrylate, weight average molecular weight of 800,000) was prepared, This acrylic rubber was dissolved in a mixed solution of toluene/ethyl acetate=50/50 (mass ratio) to prepare a solution with a solid content of 15% by mass. Furthermore, a liquid containing latent curing agent (microencapsulated amine-based curing agent), bisphenol F-type epoxy resin, and naphthalene-type epoxy resin was prepared in a mass ratio of 34:49:17. Epoxy resin for hardener (epoxy equivalent weight: 202). Furthermore, 8-glycidyloxyoctyltrimethoxysilane (product name: KBM4803, manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared as the silane compound.

以苯氧樹脂、丙烯酸橡膠、含硬化劑的環氧樹脂及矽烷化合物的質量比（固體成分）為20：30：47：3的方式調配該些材料而製備清漆A1（接著劑組成物含有液）。進而，製作於以聚苯乙烯為核的粒子表面設置有厚0.2 μm的鎳層的導電粒子A。該導電粒子的平均粒徑為5 μm、比重為2.5。相對於清漆A1的固體成分100質量份而言，調配5質量份的該導電粒子A而製備清漆B1（電路連接材料含有液）。於對單面進行了表面處理的厚50 μm的聚對苯二甲酸乙二酯（PET）膜上，使用塗敷工具塗佈清漆B1後，在70℃下進行3分鐘熱風乾燥，藉此而於PET膜上形成厚度為20 μm的膜狀接著劑組成物。The phenoxy resin, acrylic rubber, hardener-containing epoxy resin, and silane compound were mixed in a mass ratio (solid content) of 20:30:47:3 to prepare Varnish A1 (adhesive composition-containing liquid ). Furthermore, conductive particle A in which a nickel layer having a thickness of 0.2 μm was provided on the surface of the particle having polystyrene as a core was produced. The conductive particles had an average particle diameter of 5 μm and a specific gravity of 2.5. With respect to 100 parts by mass of the solid content of the varnish A1, 5 parts by mass of the conductive particles A were prepared to prepare a varnish B1 (a circuit-connecting material-containing liquid). On a polyethylene terephthalate (PET) film with a thickness of 50 μm that had been surface-treated on one side, the varnish B1 was applied using a coating tool, and then dried with hot air at 70° C. for 3 minutes to obtain A film-like adhesive composition with a thickness of 20 μm was formed on the PET film.

[比較例1] 除代替8-縮水甘油氧基辛基三甲氧基矽烷而使用3-縮水甘油氧基丙基三甲氧基矽烷（製品名：KBM403、信越化學工業股份有限公司製造）作為矽烷化合物以外，與實施例1同樣地進行而製作膜狀接著劑組成物。[Comparative Example 1] 3-glycidoxypropyltrimethoxysilane (product name: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane compound instead of 8-glycidyloxyoctyltrimethoxysilane. 1 A film-like adhesive composition was produced in the same manner.

[實施例2] 將50 g苯氧樹脂（製品名：PKHC、聯合碳化物（Union Carbide）股份有限公司製造、重量平均分子量45000）溶解於甲苯/乙酸乙酯=50/50（質量比）的混合溶液中而製備固體成分40質量%的苯氧樹脂溶液。作為自由基聚合性化合物，使用異三聚氰酸EO改質二丙烯酸酯（製品名：M-215、東亞合成股份有限公司製造）、磷酸-2-(甲基)丙烯醯氧基乙酯（製品名：P-2M、共榮社化學股份有限公司製造）及丙烯酸胺基甲酸酯（製品名：U-2PPA、新中村化學工業股份有限公司製造）。作為矽烷化合物，準備7-辛烯基三甲氧基矽烷（製品名：KBM1083、信越化學工業股份有限公司製造）。作為自由基產生劑，準備過氧化苯甲醯基（製品名：NYPER-BMT-K40、日油股份有限公司製造）。[Example 2] Prepared by dissolving 50 g of phenoxy resin (product name: PKHC, manufactured by Union Carbide Co., Ltd., weight average molecular weight 45,000) in a mixed solution of toluene/ethyl acetate=50/50 (mass ratio). A phenoxy resin solution with a solid content of 40% by mass. As the radical polymerizable compound, isocyanuric acid EO-modified diacrylate (product name: M-215, manufactured by Toagosei Co., Ltd.), 2-(meth)acryloyloxyethyl phosphate ( Product name: P-2M, manufactured by Kyoeisha Chemical Co., Ltd.) and urethane acrylate (product name: U-2PPA, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). As the silane compound, 7-octenyltrimethoxysilane (product name: KBM1083, manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared. As a radical generator, benzyl peroxide (product name: NYPER-BMT-K40, manufactured by NOF Corporation) was prepared.

以苯氧樹脂、異三聚氰酸EO改質二丙烯酸酯、磷酸-2-(甲基)丙烯醯氧基乙酯、丙烯酸胺基甲酸酯、矽烷化合物以及自由基產生劑的質量比（固體成分）為50：19：3：20：3：5的方式調配該些材料而製備清漆B1（接著劑組成物含有液）。進而，相對於清漆B1的固體成分100質量份而言，調配5質量份的導電粒子A而製備清漆B2（電路連接材料含有液）。於對單面進行了表面處理的厚50 μm的聚對苯二甲酸乙二酯（PET）膜上，使用塗敷工具塗佈清漆B2後，在70℃下進行3分鐘熱風乾燥，藉此而於PET膜上形成厚度為20 μm的膜狀接著劑。The mass ratio of phenoxy resin, EO modified diacrylate of isocyanuric acid, 2-(meth)acryloyloxyethyl phosphate, urethane acrylate, silane compound and free radical generator ( These materials were blended so that the solid content) was 50:19:3:20:3:5 to prepare varnish B1 (adhesive composition-containing liquid). Further, 5 parts by mass of the conductive particles A were prepared with respect to 100 parts by mass of the solid content of the varnish B1 to prepare a varnish B2 (circuit-connecting material-containing liquid). On a polyethylene terephthalate (PET) film with a thickness of 50 μm that had been surface-treated on one side, the varnish B2 was applied using a coating tool, and then dried with hot air at 70° C. for 3 minutes. A film-like adhesive with a thickness of 20 μm was formed on the PET film.

[比較例2] 除代替7-辛烯基三甲氧基矽烷而使用乙烯基三甲氧基矽烷（製品名：KBM103、信越化學工業股份有限公司製造）作為矽烷化合物以外，與實施例2同樣地進行而製作膜狀接著劑組成物。[Comparative Example 2] A film-like adhesive was produced in the same manner as in Example 2, except that vinyltrimethoxysilane (product name: KBM103, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane compound instead of 7-octenyltrimethoxysilane. agent composition.

[實施例3] 除代替7-辛烯基三甲氧基矽烷而使用8-甲基丙烯醯氧基辛基三甲氧基矽烷（製品名：KBM5803、信越化學工業股份有限公司製造）作為矽烷化合物以外，與實施例2同樣地進行而製作膜狀接著劑組成物。[Example 3] The same procedure as in Example 2 was performed except that 8-methacryloyloxyoctyltrimethoxysilane (product name: KBM5803, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane compound instead of 7-octenyltrimethoxysilane. In the same manner, a film-like adhesive composition was produced.

[比較例3] 除代替7-辛烯基三甲氧基矽烷而使用3-甲基丙烯醯氧基丙基三甲氧基矽烷（製品名：KBM503、信越化學工業股份有限公司製造）作為矽烷化合物以外，與實施例2同樣地進行而製作膜狀接著劑組成物。[Comparative Example 3] The same procedure as in Example 2 was performed except that 3-methacryloyloxypropyltrimethoxysilane (product name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane compound instead of 7-octenyltrimethoxysilane. In the same manner, a film-like adhesive composition was produced.

＜接著強度的評價＞ 作為第一電路構件，準備具有500根線寬為75 μm、間距為150 μm、厚度為18 μm的銅電路的可撓性電路基板（flexible printed circuit，FPC）。作為第二電路構件，準備形成有0.5 μm的氮化矽（SiNx ）薄層的玻璃（厚0.7mm）。於實施例1～實施例3或比較例1～比較例3的膜狀接著劑組成物介於第一電路構件與第二電路構件之間的狀態下，使用熱壓接裝置（加熱方式：恆溫型、東麗工程股份有限公司製造），在170℃、3 MPa下進行20秒的加熱加壓而以2 mm的寬度連接，製作電路連接結構體（連接體）。<Evaluation of Adhesion Strength> As the first circuit member, a flexible printed circuit (FPC) having 500 copper circuits with a line width of 75 μm, a pitch of 150 μm, and a thickness of 18 μm was prepared. As the second circuit member, glass (thickness 0.7 mm) on which a thin layer of silicon nitride (SiN x ) of 0.5 μm was formed was prepared. A thermocompression bonding apparatus (heating method: constant temperature) was used in a state where the film adhesive compositions of Examples 1 to 3 or Comparative Examples 1 to 3 were interposed between the first circuit member and the second circuit member. type, manufactured by Toray Engineering Co., Ltd.), were heated and pressurized at 170° C. and 3 MPa for 20 seconds, and were connected with a width of 2 mm to produce a circuit connection structure (connector).

關於該電路連接結構體，依據日本工業標準（Japanese Industrial Standards，JIS）Z0237，利用90度剝離法測定接著不久後（所述在170℃、3 MPa下進行20秒的加熱加壓後）的接著強度與在85℃、85%RH的恆溫恆濕槽中放置100小時後的接著強度。此時，接著強度的測定裝置是使用東洋鮑德溫（Toyo Baldwin）股份有限公司製造的滕喜龍（Tensilon）UTM-4（剝離速度為50 mm/min、25℃）。With regard to this circuit connection structure, in accordance with Japanese Industrial Standards (JIS) Z0237, the 90-degree peeling method was used to measure the adhesion immediately after (after heating and pressing at 170° C. and 3 MPa for 20 seconds). Strength and adhesion strength after standing in a constant temperature and humidity tank at 85°C and 85%RH for 100 hours. At this time, the measuring apparatus of the adhesive strength used Tensilon UTM-4 (peeling speed: 50 mm/min, 25° C.) manufactured by Toyo Baldwin Co., Ltd.

將如上所述進行測定的結果示於表1。The results of the measurement as described above are shown in Table 1.

[表1] 評價項目 連接體處理條件 實施例1 實施例2 實施例3 比較例1 比較例2 比較例3 接著強度（N/m） 接著不久後 630 720 830 540 700 760 85℃85%RH 100小時處理後 590 700 850 400 500 550 [Table 1] Evaluation item Linker processing conditions Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Next Strength (N/m) then shortly after 630 720 830 540 700 760 85℃85%RH 100 hours after treatment 590 700 850 400 500 550

根據以上而確認到：實施例1～實施例3的各個與比較例1～比較例3相比較而言，接著不久後的接著強度高，而且，在可靠性試驗（高溫高濕處理）後亦可良好地保持對於基板（無機基板）表面的接著力。From the above, it was confirmed that compared with Comparative Examples 1 to 3, each of Examples 1 to 3 had higher bonding strength immediately after the Adhesion to the surface of the substrate (inorganic substrate) can be maintained well.

10:電路連接構件 10a:絕緣性物質 10b:導電粒子 20:第一電路構件 21:第一基板 21a、31a:主表面 22:第一電路電極 30:第二電路構件 31:第二基板 32:第二電路電極 100a、100b:電路連接結構體10: Circuit connection components 10a: Insulating substances 10b: Conductive particles 20: First circuit component 21: The first substrate 21a, 31a: main surface 22: First circuit electrode 30: Second circuit component 31: Second substrate 32: Second circuit electrode 100a, 100b: circuit connection structure

圖1是表示本發明的結構體的一實施方式的示意性剖面圖。 圖2是表示本發明的結構體的另一實施方式的示意性剖面圖。FIG. 1 is a schematic cross-sectional view showing an embodiment of the structure of the present invention. 2 is a schematic cross-sectional view showing another embodiment of the structure of the present invention.

10:電路連接構件 10: Circuit connection components

10a:絕緣性物質 10a: Insulating substances

10b:導電粒子 10b: Conductive particles

20:第一電路構件 20: First circuit component

21:第一基板 21: The first substrate

21a、31a:主表面 21a, 31a: main surface

22:第一電路電極 22: First circuit electrode

30:第二電路構件 30: Second circuit component

31:第二基板 31: Second substrate

32:第二電路電極 32: Second circuit electrode

100a:電路連接結構體 100a: Circuit connection structure

Claims (11)

一種接著劑組成物，其含有(A)環氧樹脂及潛伏性硬化劑、以及(B)自由基聚合性化合物及藉由熱或光而產生自由基的硬化劑的至少一者、以及具有下述通式(I)所表示的結構的矽烷化合物且為膜狀，含有所述環氧樹脂的情況下，以接著劑組成物的接著劑成分的總質量為基準，所述環氧樹脂的含量為5質量%以上，X-CsH2s-Si〔R1〕m〔OR2]3-m．．．(I)式中，X表示有機基，R1及R2分別獨立地表示烷基，m表示0~2的整數，s表示6以上的整數。 An adhesive composition comprising (A) an epoxy resin and a latent curing agent, and (B) at least one of a radically polymerizable compound and a curing agent that generates radicals by heat or light, and has the following When the silane compound of the structure represented by the general formula (I) is in the form of a film and contains the epoxy resin, the content of the epoxy resin is based on the total mass of the adhesive components of the adhesive composition. 5 mass % or more, XC s H 2s -Si[R 1 ] m [OR 2 ] 3-m . . . In the formula (I), X represents an organic group, R 1 and R 2 each independently represent an alkyl group, m represents an integer of 0 to 2, and s represents an integer of 6 or more. 如請求項1所述的接著劑組成物，其進而含有導電粒子。 The adhesive composition according to claim 1, which further contains conductive particles. 一種接著劑組成物，其含有具有下述通式(I)所表示的結構的矽烷化合物及導電粒子，所述導電粒子為金屬粒子或金屬包覆導電粒子，X-CsH2s-Si〔R1〕m〔OR2]3-m．．．(I)式中，X表示有機基，R1及R2分別獨立地表示烷基，m表示0~2的整數，s表示6以上的整數。 An adhesive composition comprising a silane compound having a structure represented by the following general formula (I) and conductive particles, wherein the conductive particles are metal particles or metal-coated conductive particles, XC s H 2s -Si[R 1 ] m [OR 2 ] 3-m . . . In the formula (I), X represents an organic group, R 1 and R 2 each independently represent an alkyl group, m represents an integer of 0 to 2, and s represents an integer of 6 or more. 如請求項2或請求項3所述的接著劑組成物，其中，相對於接著劑組成物的接著劑成分100質量份而言，導電粒子的含量為100質量份以下。 The adhesive composition according to claim 2 or claim 3, wherein the content of the conductive particles is 100 parts by mass or less with respect to 100 parts by mass of the adhesive component of the adhesive composition. 如請求項1或請求項3所述的接著劑組成物，其中，所述有機基X包含選自由(甲基)丙烯醯基、乙烯基、環氧基、氮原子含有基以及硫原子含有基所組成的群組中的至少一種，所述氮原子含有基為胺基、單取代胺基、二取代胺基、異氰酸酯基、咪唑基、脲基、或馬來醯亞胺基，所述硫原子含有基為巰基。 The adhesive composition according to claim 1 or claim 3, wherein the organic group X contains a group selected from the group consisting of a (meth)acryloyl group, a vinyl group, an epoxy group, a nitrogen atom-containing group, and a sulfur atom-containing group At least one of the group consisting of, the nitrogen atom-containing group is an amine group, a monosubstituted amine group, a disubstituted amine group, an isocyanate group, an imidazole group, a urea group, or a maleimide group, the sulfur The atom-containing group is a mercapto group. 如請求項1或請求項3所述的接著劑組成物，其含有環氧樹脂、及潛伏性硬化劑。 The adhesive composition according to claim 1 or claim 3, comprising an epoxy resin and a latent curing agent. 如請求項1或請求項3所述的接著劑組成物，其含有自由基聚合性化合物、及藉由熱或光而產生自由基的硬化劑。 The adhesive composition according to claim 1 or claim 3, comprising a radically polymerizable compound and a curing agent that generates radicals by heat or light. 如請求項1或請求項3所述的接著劑組成物，其進而含有膜形成材料。 The adhesive composition according to claim 1 or claim 3, which further contains a film-forming material. 如請求項1或請求項3所述的接著劑組成物，其進而含有橡膠成分。 The adhesive composition according to claim 1 or claim 3, which further contains a rubber component. 一種結構體，其具備如請求項1至請求項8中任一項所述的接著劑組成物或其硬化物。 A structure comprising the adhesive composition according to any one of Claims 1 to 8 or a cured product thereof. 一種結構體，其具備具有第一電路電極的第一電路構件、具有第二電路電極且所述第一電路電極與所述第二電路電極對向而配置的第二電路構件、及配置於所述第一電路構件與所述第二電路構件之間的電路連接構件，所述第一電路電極及所述第二電路電極電性連接， 所述電路連接構件包含接著劑組成物或其硬化物，所述接著劑組成物含有具有下述通式(I)所表示的結構的矽烷化合物，X-CsH2s-Si〔R1〕m〔OR2]3-m．．．(I)式中，X表示有機基，R1及R2分別獨立地表示烷基，m表示0~2的整數，s表示6以上的整數。 A structure including a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode, the first circuit electrode and the second circuit electrode being arranged to face the second circuit electrode, and a structure arranged on the A circuit connection member between the first circuit member and the second circuit member, the first circuit electrode and the second circuit electrode are electrically connected, and the circuit connection member includes an adhesive composition or a cured product thereof , the adhesive composition contains a silane compound having a structure represented by the following general formula (I), XC s H 2s -Si[R 1 ] m [OR 2 ] 3-m . . . In the formula (I), X represents an organic group, R 1 and R 2 each independently represent an alkyl group, m represents an integer of 0 to 2, and s represents an integer of 6 or more.
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