TW201443122A - Resin composition - Google Patents

Resin composition Download PDF

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Publication number
TW201443122A
TW201443122A TW103111411A TW103111411A TW201443122A TW 201443122 A TW201443122 A TW 201443122A TW 103111411 A TW103111411 A TW 103111411A TW 103111411 A TW103111411 A TW 103111411A TW 201443122 A TW201443122 A TW 201443122A
Authority
TW
Taiwan
Prior art keywords
resin composition
acid
mass
composition according
meth
Prior art date
Application number
TW103111411A
Other languages
Chinese (zh)
Other versions
TWI648324B (en
Inventor
Katsunori Arai
Bunya Watanabe
Noritsuka Mizumura
Kazuki Fukazawa
Original Assignee
Namics Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2013073408A external-priority patent/JP6106007B2/en
Priority claimed from JP2013073409A external-priority patent/JP6069071B2/en
Application filed by Namics Corp filed Critical Namics Corp
Publication of TW201443122A publication Critical patent/TW201443122A/en
Application granted granted Critical
Publication of TWI648324B publication Critical patent/TWI648324B/en

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    • C—CHEMISTRY; METALLURGY
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    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
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    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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Abstract

Provided is a resin composition which functions an excellent adhesive strength and the peeling of the cured article obtained by a high temperature process is inhibited in the manufacture of semi-conductive device. The present invention is related to a resin composition comprising (A) inorganic filler, (B) thermosetting resin, (C) curing agent, (D) (D1) metal salt of an organic acid having a boiling point above 200 DEG C, and/or (D2) a combination of organic acid having a boiling point above 200 DEG C with a metal particle and /or metal oxide particle, and (E) polysulfide compound, or comprising (A) inorganic filler, (B) thermal-cured resin, (C) curing agent, (D) (D1) metal salt of an organic acid having a boiling point above 200 DEG C, and/or (D2) a combination of organic acid having a boiling point above 200 DEG C with a metal particle and /or metal oxide particle, and (E') preventing agent for secondary oxidation; a die attach paste or an adhesive agent for radiating parts comprising the above resin composition; and a semi-conductive device made by using the above die attach paste or the above adhesive agent for the radiating parts.

Description

樹脂組成物 Resin composition

本發明是有關樹脂組成物，含有該樹脂組成物的黏晶膠(die attach paste)或是放熱構件用的接著劑，使用該黏晶膠或是放熱構件用接著劑而製作的半導體裝置。 The present invention relates to a resin composition, a die attach paste containing the resin composition, or an adhesive for a heat releasing member, and a semiconductor device produced by using the adhesive or an adhesive for a heat releasing member.

半導體裝置的製造中，為了將IC、LSI等半導體元件接著在引線框架等，或是將放熱構件接著在半導體元件、引線框架等，係使用含有熱硬化性樹脂、硬化劑以及無機填充劑的樹脂組成物(專利文獻1)。前述樹脂組成物已知作為黏晶膠，而用此將半導體元件與支撐構件接著，經由打線(wire bonding)得到密封的半導體裝置後，可以將該半導體裝置焊接組裝在印刷配線基板上。黏晶膠被要求發揮優良的接著強度，尤其是被要求在所謂以打線或回焊之高溫製程下硬化物不剝離。近來，有藉由在樹脂組成物中調配多硫化物，以改善接著性或耐回流性，作為黏晶膠或放熱構件用接著劑來使用之提議(參照專利文獻2至3)。 In the manufacture of a semiconductor device, a semiconductor element such as an IC or an LSI is used in a lead frame or the like, or a heat-dissipating member is applied to a semiconductor element or a lead frame, and a resin containing a thermosetting resin, a curing agent, and an inorganic filler is used. Composition (Patent Document 1). The resin composition is known as a die bond, and after the semiconductor element and the support member are used to obtain a sealed semiconductor device by wire bonding, the semiconductor device can be soldered and assembled on the printed wiring substrate. The adhesive is required to exert excellent bonding strength, and in particular, it is required that the cured product does not peel off in a so-called high-temperature process of wire bonding or reflow. Recently, there has been proposed to use a polysulfide in a resin composition to improve adhesion or reflow resistance, and to use it as an adhesive for a pressure-sensitive adhesive or a heat-releasing member (see Patent Documents 2 to 3).

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

[專利文獻1]日本特開2011-086669號公報 [Patent Document 1] Japanese Patent Publication No. 2011-086669

[專利文獻2]日本特開2007-262243號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-262243

[專利文獻3]日本特開2009-191214號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-191214

如上述半導體裝置的製造中，於支撐構件上，一直以來雖是使用經施行鍍銀等鍍覆貴金屬之引線框架或基板，但近年來為了謀求低成本化，變成嘗試使用銅引線框架或銅基板，黏晶膠特別是被要求對銅之接著力優良，且在高溫製程無硬化物剝離。 In the production of the semiconductor device described above, a lead frame or a substrate on which a noble metal is plated with silver or the like is used for the support member. However, in recent years, in order to reduce the cost, an attempt has been made to use a copper lead frame or a copper substrate. In particular, the adhesive is required to have excellent adhesion to copper, and is not peeled off in a high temperature process.

本發明是由上述觀點所作成者，目的在於提供一種發揮優良的接著強度，抑制在高溫製程中硬化物之剝離的樹脂組成物。本發明又一目的在於提供一種在支撐構件為銅時，發揮優良的接著強度，抑制在高溫製程中硬化物之剝離的樹脂組成物。 The present invention has been made in view of the above viewpoints, and an object thereof is to provide a resin composition which exhibits excellent adhesion strength and suppresses peeling of a cured product in a high-temperature process. Still another object of the present invention is to provide a resin composition which exhibits excellent adhesion strength when the support member is made of copper and suppresses peeling of the cured product in a high-temperature process.

本發明，是根據含有(A)無機填充劑、(B)熱硬化性樹脂、(C)硬化劑，與(D)(D1)沸點是在200℃以上的有機酸之金屬鹽，以及/或是(D2)沸點是在200℃以上的有機酸與金屬粒子及/或金屬氧化物粒子之組合 的樹脂組成物中，(D)成分為除去有礙支撐構件表面之接著性的物質，而可具有良好接著性的知識而得者。在此，無機填充劑可以是導電填充劑，也可以是絕緣填充劑，可依用途或性能適當地選擇，可以使用絕緣填充劑。 The present invention is based on a metal salt of an organic acid containing (A) an inorganic filler, (B) a thermosetting resin, (C) a curing agent, and (D) (D1) having a boiling point of 200 ° C or higher, and/or Is (D2) a combination of an organic acid having a boiling point above 200 ° C and metal particles and/or metal oxide particles In the resin composition, the component (D) is obtained by removing the material which hinders the adhesion of the surface of the support member, and has good adhesion. Here, the inorganic filler may be an electrically conductive filler or an insulating filler, and may be appropriately selected depending on the use or performance, and an insulating filler may be used.

本發明[1]是有關一種樹脂組成物，其係含有：(A)無機填充劑、(B)熱硬化性樹脂、(C)硬化劑、(D)(D1)沸點是在200℃以上的有機酸之金屬鹽，以及/或是(D2)沸點是在200℃以上的有機酸與金屬粒子及/或金屬氧化物粒子之組合，與(E)多硫化物。 The present invention [1] relates to a resin composition comprising: (A) an inorganic filler, (B) a thermosetting resin, (C) a curing agent, and (D) (D1) having a boiling point of 200 ° C or higher. The metal salt of an organic acid, and/or (D2) a combination of an organic acid having a boiling point of 200 ° C or higher and metal particles and/or metal oxide particles, and (E) a polysulfide.

如上所述，根據本發明人等的檢討，發現多硫化物的添加雖對貴金屬有用，但對於銅而言，會降低接著性，可能會在高溫製程中發生剝離。此事實的原因之一，是因為多硫化物會使支撐構件表面的銅過度硫化。本發明[1]是考量藉由併用(D)，以(D)的金屬部分抑制銅的過度硫化，結果為避免銅的接著性下降。又，有關接著性，亦發現藉由併用(D)，較單獨使用多硫化物更能提高對貴金屬之接著性。如此之效果，在(A)為導電填充劑之本發明[1]的樹脂組成物很是顯著。另一方面，絕緣填充劑，通常是使用在不需導電性之用途，或以低成本化之目的。從低成本化的觀點來看，比起使用經實施貴金屬的引線框架或基板，係以使用樹脂基板或銅引線框架為佳。 As described above, according to the review by the inventors of the present invention, it has been found that the addition of polysulfide is useful for noble metals, but for copper, the adhesion is lowered, and peeling may occur in a high-temperature process. One of the reasons for this is because polysulfide will excessively vulcanize the copper on the surface of the support member. The present invention [1] considers that by excessively vulcanizing copper with the metal portion of (D) by using (D) in combination, as a result, the adhesion of copper is prevented from decreasing. Further, regarding the adhesion, it has been found that by using (D) in combination, the adhesion to the noble metal can be improved more than the use of the polysulfide alone. As a result, the resin composition of the invention [1] in which (A) is a conductive filler is remarkable. On the other hand, the insulating filler is usually used for the purpose of not requiring electrical conductivity or for the purpose of cost reduction. From the viewpoint of cost reduction, it is preferable to use a resin substrate or a copper lead frame as compared with a lead frame or a substrate on which a noble metal is applied.

本發明[2]是有關本發明[1]的樹脂組成物，其中，(E)是具有選自雙硫鍵、三硫鍵、以及四硫鍵所成群組中的鍵結之化合物。 The invention [2] is the resin composition of the invention [1], wherein (E) is a compound having a bond selected from the group consisting of a disulfide bond, a trisulfide bond, and a tetrasulfide bond.

本發明[3]是有關本發明[2]的樹脂組成物，其中，(E)是具有多硫鍵之矽烷化合物及/或具有多硫鍵之胺化合物。 The invention [3] is a resin composition according to the invention [2], wherein (E) is a decane compound having a polysulfide bond and/or an amine compound having a polysulfide bond.

本發明[4]是有關本發明[1]至[3]中任一項所述之樹脂組成物，其中，相對於(A)至(E)的合計100質量份，(D)是0.05至5質量份；相對於(A)至(E)的合計100質量份，(E)換算成硫量是0.02至2.0質量份。 The resin composition according to any one of the present invention, wherein the (D) is 0.05 to 100 parts by mass of the total of (A) to (E). 5 parts by mass; (E) is converted into a sulfur content of 0.02 to 2.0 parts by mass based on 100 parts by mass of the total of (A) to (E).

本發明[5]是有關本發明[1]至[4]中任一項所述之樹脂組成物，其復含有(F)(甲基)丙烯酸的金屬鹽。 The resin composition according to any one of the inventions [1] to [4] which further comprises (F) a metal salt of (meth)acrylic acid.

又，本發明[6]是一種樹脂組成物，其係含有：(A)無機填充劑、(B)熱硬化性樹脂、(C)硬化劑、(D)(D1)沸點為200℃以上的有機酸之金屬鹽，及/或(D2)沸點為200℃以上的有機酸與金屬粒子及/或金屬氧化物粒子的組合、與(E’)二級抗氧化劑。 Further, the invention [6] is a resin composition containing (A) an inorganic filler, (B) a thermosetting resin, (C) a curing agent, and (D) (D1) having a boiling point of 200 ° C or higher. a metal salt of an organic acid, and/or (D2) a combination of an organic acid having a boiling point of 200 ° C or higher and metal particles and/or metal oxide particles, and (E') a secondary antioxidant.

本發明[6]的樹脂組成物之特徵在於調配(D)(D1)沸點為200℃以上的有機酸之金屬鹽，以及/或(D2)沸點為200℃以上的有機酸與金屬粒子及/或金屬氧化物粒子之組 合、與(E’)二級抗氧化劑。本發明的優良接著強度及抑制在高溫製程的硬化物之剝離，認為是因為(D)會除去有礙支撐構件表面接著性之物質，同時，(E’)會將在高溫製程發生的促進硬化物劣化的氫過氧化物分解，相輔而成。 The resin composition of the invention [6] is characterized in that (D) (D1) a metal salt of an organic acid having a boiling point of 200 ° C or higher, and/or (D2) an organic acid having a boiling point of 200 ° C or more and metal particles and/or Or group of metal oxide particles Combined with (E') secondary antioxidant. The excellent adhesion strength of the present invention and the suppression of the peeling of the cured product at a high temperature process are considered to be because (D) removes substances which hinder the surface adhesion of the support member, and at the same time, (E') promotes hardening at a high temperature process. The hydroperoxide degraded by the substance is decomposed and complemented.

本發明[7]是有關本發明[6]的樹脂組成物，其中，(E’)是硫系二級抗氧化劑及/或磷系二級抗氧化劑。 The invention [7] is the resin composition according to the invention [6], wherein (E') is a sulfur-based secondary antioxidant and/or a phosphorus-based secondary antioxidant.

本發明[8]是有關本發明[7]的樹脂組成物，其中，(E’)是含有硫醇及/或硫醚的硫系二級抗氧化劑。 The invention [8] is the resin composition according to the invention [7], wherein (E') is a sulfur-based secondary antioxidant containing a mercaptan and/or a sulfide.

本發明[9]是有關本發明[6]至[8]中任一項所述之樹脂組成物，其復含有(F’)初級抗氧化劑。 [9] The resin composition according to any one of [6] to [8] which further comprises (F') a primary antioxidant.

本發明[10]是有關本發明[6]至[9]中任一項所述之樹脂組成物，其中，相對於(A)至(D)以及(E’)的合計100質量份，(D)係0.10至5.0質量份，相對於(A)至(D)以及(E’)的合計100質量份，(E’)係0.03至5.0質量份。 The resin composition according to any one of the above [6] to [9], wherein, in relation to the total of 100 parts by mass of (A) to (D) and (E'), D) is 0.10 to 5.0 parts by mass, and (E') is 0.03 to 5.0 parts by mass based on 100 parts by mass of the total of (A) to (D) and (E').

本發明[11]是有關本發明[1]至[10]中任一項所述之樹脂組成物，其中，(A)是導電填充劑。 The resin composition according to any one of the aspects of the present invention, wherein (A) is a conductive filler.

本發明[12]是有關本發明[11]的樹脂組成物，其中，(A)是選自銀、金、銅、鈀以及該等之合金所成群中的粒子。 The invention [12] is the resin composition according to the invention [11], wherein (A) is a particle selected from the group consisting of silver, gold, copper, palladium and alloys thereof.

本發明[13]是有關本發明[1]至[12]中任一項所述之樹脂組成物，其中，(A)是絕緣填充劑。 The resin composition according to any one of the aspects [1] to [12] wherein (A) is an insulating filler.

本發明[14]是有關本發明[1]至[13]中任一項所述之樹脂組成物，其中，(D1)是選自2-乙基己酸、萘酸以及環戊烷羧酸所成群組中的有機酸之金屬鹽，(D2)是選自2-乙基 己酸、萘酸以及環戊烷羧酸所成群組中的有機酸與金屬粒子及/或金屬氧化物粒子的組合。 The resin composition according to any one of the aspects [1] to [13] wherein (D1) is selected from the group consisting of 2-ethylhexanoic acid, naphthoic acid, and cyclopentanecarboxylic acid. The metal salt of the organic acid in the group, (D2) is selected from 2-ethyl A combination of an organic acid in the group of caproic acid, naphthoic acid, and cyclopentanecarboxylic acid with metal particles and/or metal oxide particles.

本發明[15]是有關本發明[14]的樹脂組成物，其中，(D1)中的金屬鹽，係選自鋅鹽、鈷鹽、鎳鹽、鎂鹽、錳鹽以及錫鹽所成群組中的鹽，(D2)中的金屬粒子及/或金屬氧化物粒子，係選自鋅、鈷、鎳、鎂、錳、錫以及該等的氧化物所成群組中的粒子。 The invention [15] is the resin composition of the invention [14], wherein the metal salt in (D1) is selected from the group consisting of a zinc salt, a cobalt salt, a nickel salt, a magnesium salt, a manganese salt and a tin salt. The salt in the group, the metal particles and/or metal oxide particles in (D2) are selected from the group consisting of zinc, cobalt, nickel, magnesium, manganese, tin, and oxides thereof.

本發明[16]是有關一種黏晶膠，其是含有本發明[1]至[15]中任一項所述之樹脂組成物。 The present invention [16] relates to a viscous gel which is a resin composition according to any one of [1] to [15].

本發明[17]是有關一種放熱構件用接著劑，其是含有本發明[1]至[15]中任一項所述之樹脂組成物。 The invention [17] relates to an adhesive composition for a heat releasing member, which is a resin composition according to any one of [1] to [15].

本發明[18]是有關一種半導體裝置，其是使用本發明[16]的黏晶膠，或是本發明[17]的放熱構件用接著劑而製作者。 The invention [18] relates to a semiconductor device which is produced by using the adhesive of the invention [16] or the adhesive for a heat releasing member of the invention [17].

本發明[19]是有關本發明[18]的半導體裝置，其中，施用本發明[16]的黏晶膠、或是本發明[17]的放熱構件用接著劑之表面為銅。 The invention is the semiconductor device according to the invention [18], wherein the surface of the adhesive for applying the adhesive of the invention [16] or the adhesive for the heat releasing member of the invention [17] is copper.

本發明的樹脂組成物可發揮優良的接著強度、抑制在高溫製程中硬化物之剝離，適合作為黏晶膠或是放熱構件用接著劑。尤其，本發明之樹脂組成物的硬化物，係經由吸濕而抑制強度的劣化，使用該等樹脂組成物製作的半導體裝置，係吸濕回流性優良，可靠度高。又，本發明的樹脂組成物即使在支撐構件為銅的情形下，也可 以發揮該等效果，有用性高。 The resin composition of the present invention can exhibit excellent adhesion strength and suppress peeling of a cured product in a high-temperature process, and is suitable as an adhesive for a pressure-sensitive adhesive or a heat-releasing member. In particular, the cured product of the resin composition of the present invention suppresses deterioration of strength by moisture absorption, and the semiconductor device produced using the resin composition is excellent in moisture absorption reflow property and high in reliability. Moreover, the resin composition of the present invention can be used even in the case where the support member is copper. In order to exert these effects, the usefulness is high.

<樹脂組成物> <Resin composition>

第一態樣中，本發明的樹脂組成物是含有：(A)無機填充劑、(B)熱硬化性樹脂、(C)硬化劑、(D)(D1)沸點是200℃以上的有機酸之金屬鹽，及/或(D2)沸點是在200℃以上的有機酸與金屬粒子及/或金屬氧化物粒子之組合，與(E)多硫化物。 In the first aspect, the resin composition of the present invention contains: (A) an inorganic filler, (B) a thermosetting resin, (C) a curing agent, and (D) (D1) an organic acid having a boiling point of 200 ° C or higher. The metal salt and/or (D2) boiling point is a combination of an organic acid at 200 ° C or higher and metal particles and/or metal oxide particles, and (E) a polysulfide.

(A)無機填充劑 (A) inorganic filler

(A)並無特別限定，可以是導電填充劑，也可以是絕緣填充劑，雖可依據用途或性能而適當地選擇，但以導電填充劑為佳。 (A) is not particularly limited, and may be a conductive filler or an insulating filler. Although it may be appropriately selected depending on the use or performance, a conductive filler is preferred.

導電填充劑可以列舉標準電極電位是0V以上的金屬或是該等的合金之金屬粒子。藉由使用標準電極電位是0V以上者，減少(A)因後述的(D)中所含有之有機酸成分所受到的影響。作為標準電極電位為0V以上的金屬，可以列舉：銀、金、銅、鈀。作為導電填充劑，可以列舉：銀、金、銅、鈀以及該等的合金之金屬粒子；至少在表面具備銀、金、銅、鈀以及該等的合金之粒子，可以列舉例 如，經塗佈該等金屬或是合金之無機填充劑。理想的是，銀或是含有銀的合金之粒子，或是在表面具備銀或是含有銀的合金之粒子。作為銀、金、銅、鈀的合金，可以列舉：含有選自銀、金、銅以及鈀中至少1種的合金，例如，銀銅合金、或是銀錫合金。 Examples of the conductive filler include metals having a standard electrode potential of 0 V or more or metal particles of the alloys. When the standard electrode potential is 0 V or more, the influence of (A) the organic acid component contained in (D) described later is reduced. Examples of the metal having a standard electrode potential of 0 V or more include silver, gold, copper, and palladium. Examples of the conductive filler include silver, gold, copper, palladium, and metal particles of the alloys; and at least particles having silver, gold, copper, palladium, and alloys on the surface thereof are exemplified. For example, an inorganic filler of the metal or alloy is coated. It is desirable that the particles of silver or an alloy containing silver or particles of an alloy having silver or silver on the surface. Examples of the alloy of silver, gold, copper, and palladium include an alloy selected from at least one selected from the group consisting of silver, gold, copper, and palladium, for example, a silver-copper alloy or a silver-tin alloy.

作為絕緣填充劑者，可以列舉：氧化矽、氧化鋁、氧化鈦、氧化鋯、玻璃、碳化矽、氮化鋁、氮化硼的粒子，理想的是氧化矽。 Examples of the insulating filler include particles of cerium oxide, aluminum oxide, titanium oxide, zirconium oxide, glass, cerium carbide, aluminum nitride, and boron nitride, and cerium oxide is preferable.

無機填充劑的形狀並無特別限定，可以列舉：球狀、鱗片狀等，理想的是可以使用鱗片狀者。平均粒徑，可以是在0.05至50μm，理想的是0.1至30μm，更理想的是0.5至15μm。在此，平均粒徑是指藉由雷射繞射法測定之體積基準的平均直徑。 The shape of the inorganic filler is not particularly limited, and examples thereof include a spherical shape and a scaly shape. It is preferable to use a scaly shape. The average particle diameter may be from 0.05 to 50 μm, desirably from 0.1 to 30 μm, more desirably from 0.5 to 15 μm. Here, the average particle diameter refers to the average diameter of the volume reference measured by the laser diffraction method.

(A)是可以單獨使用，也可以併用2種以上。 (A) may be used alone or in combination of two or more.

(B)熱硬化性樹脂 (B) Thermosetting resin

(B)熱硬化性樹脂雖是無特別限定，但以在室溫(25℃)下是液狀為佳。作為熱硬化性樹脂，可以列舉：環氧樹脂、(甲基)丙烯酸樹脂、馬來醯亞胺樹脂。 (B) The thermosetting resin is not particularly limited, but is preferably liquid at room temperature (25 ° C). Examples of the thermosetting resin include an epoxy resin, a (meth)acrylic resin, and a maleic imide resin.

環氧樹脂是在分子內有1個以上之縮水甘油基的化合物，可藉由加熱使縮水甘油基反應而形成3維網狀結構，並硬化。從硬化物特性之點而言，縮水甘油基以在1分子中含有2個以上為佳。 The epoxy resin is a compound having one or more glycidyl groups in the molecule, and the glycidyl group can be reacted by heating to form a three-dimensional network structure and hardened. From the viewpoint of the properties of the cured product, the glycidyl group is preferably contained in two or more molecules.

環氧樹脂雖可以列舉：雙酚A、雙酚F、聯酚等雙酚化合物或是該等的衍生物(例如，環氧烷加成物)， 氫化雙酚A、氫化雙酚F、氫化聯酚、環己二醇、環己二甲醇、環己二乙醇等具有脂環結構之二醇或該等的衍生物、丁二醇、己二醇、辛二醇、壬二醇、癸二醇等脂肪族二醇或是將該等的衍生物等環氧化之2官能性環氧樹脂；三羥基苯基甲烷骨架、有胺基酚骨架之3官能性環氧樹脂；將苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、酚芳烷基樹脂、聯苯基芳烷基樹脂、萘醇芳烷基樹脂等環氧化之多官能性環氧樹脂，但並不限定於該等。 Examples of the epoxy resin include bisphenol compounds such as bisphenol A, bisphenol F, and biphenol, or derivatives thereof (for example, alkylene oxide adducts). a diol having an alicyclic structure such as hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated biphenol, cyclohexanediol, cyclohexanedimethanol or cyclohexane diethanol or the like, butanediol, hexanediol An aliphatic diol such as octanediol, decanediol or decanediol or a bifunctional epoxy resin which is epoxidized such as these derivatives; a trihydroxyphenylmethane skeleton and an aminophenol skeleton 3 a functional epoxy resin; an epoxidized polyfunctional epoxy resin such as a phenol novolak resin, a cresol novolak resin, a phenol aralkyl resin, a biphenyl aralkyl resin, or a naphthol aralkyl resin; It is not limited to these.

環氧樹脂以在室溫(25℃)中是液狀者為佳，可以單獨地，或是混合物在室溫中呈液狀。也可以使用反應性的稀釋劑作成液狀，反應性稀釋劑可以列舉：苯基縮水甘油基醚、甲苯酚基縮水甘油基醚等1官能芳香族縮水甘油基醚類、脂肪族縮水甘油基醚類等。 The epoxy resin is preferably liquid at room temperature (25 ° C), and may be used singly or as a mixture at room temperature. A reactive diluent may also be used as the liquid. Examples of the reactive diluent include monofunctional aromatic glycidyl ethers such as phenyl glycidyl ether and cresyl glycidyl ether, and aliphatic glycidyl ethers. Classes, etc.

作為熱硬化性樹脂，可以使用(甲基)丙烯酸樹脂。(甲基)丙烯酸樹脂，可以是在分子內有(甲基)丙烯醯基的化合物，可以藉由(甲基)丙烯醯基進行反應而形成3維網狀結構，並硬化。作為(甲基)丙烯酸樹脂，可以列舉：(甲基)丙烯酸甲酯、基(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十三酯、基(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸山萮酯、(甲基)丙烯酸2-乙基己酯、其他的(甲基)丙烯酸烷基酯；(甲基)丙烯酸環己酯、(甲基)丙烯酸三級丁基環己酯、 (甲基)丙烯酸四氫呋喃酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸縮水甘油酯、三羥甲基丙烷三(甲基)丙烯酸酯、單(甲基)丙烯酸鋅、二(甲基)丙烯酸鋅、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯、新戊二醇(甲基)丙烯酸酯、基(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、(甲基)丙烯酸2,2,3,3,4,4-六氟丁酯、(甲基)丙烯酸全氟辛酯、(甲基)丙烯酸全氟辛基乙酯、乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁醇二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、四亞甲二醇二(甲基)丙烯酸酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸丁氧基乙酯、乙氧基二乙二醇(甲基)丙烯酸酯、甲氧基多烷二醇單(甲基)丙烯酸酯、辛氧基多烷二醇單(甲基)丙烯酸酯、月桂氧基多烷二醇單(甲基)丙烯酸酯、硬脂氧基多烷二醇單(甲基)丙烯酸酯、烯丙氧基多烷二醇單(甲基)丙烯酸酯、壬基苯氧基多烷二醇單(甲基)丙烯酸酯、二(甲基)丙烯醯氧基甲基三環癸烷、N-(甲基)丙烯醯氧基乙基馬來醯亞胺、N-(甲基)丙烯醯氧基乙基六氫鄰苯二甲醯亞胺、N-(甲基)丙烯醯氧基乙基鄰苯二甲醯亞胺。也可以使用：N,N’-亞甲基雙(甲基)丙烯基醯胺、N,N’-伸乙基雙(甲基)丙烯基醯胺、1,2-二(甲基)丙烯基醯胺乙二醇等(甲基)丙烯基醯胺。亦可使用n-乙烯基-2-吡咯啶酮、苯乙烯衍生物、α-甲基苯乙烯衍生物等乙烯基化合 物。 As the thermosetting resin, a (meth)acrylic resin can be used. The (meth)acrylic resin may be a compound having a (meth)acryloyl group in the molecule, and may be reacted by a (meth)acrylonitrile group to form a three-dimensional network structure and hardened. Examples of the (meth)acrylic resin include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and (methyl). Tertiary butyl acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl methacrylate, stearyl (meth) acrylate , isoamyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, other alkyl (meth)acrylate Ester; cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, Tetrahydrofuran (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, trimethylolpropane Tris(meth)acrylate, zinc mono(meth)acrylate, zinc di(meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, Neopentyl glycol (meth) acrylate, trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2, 2, 3 (meth) acrylate ,3,4,4-hexafluorobutyl ester, perfluorooctyl (meth)acrylate, perfluorooctyl (meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(methyl) Acrylate, 1,4-butanoldiol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, (meth)acrylic acid methoxy Ethyl ethyl ester, butoxyethyl (meth)acrylate, ethoxy diethylene glycol (meth) acrylate, methoxy Alkanediol mono(meth)acrylate, octyloxypolyalkylene glycol mono(meth)acrylate, lauryloxypolyalkylene glycol mono(meth)acrylate,stearyloxypolyalkylene glycol single (Meth) acrylate, allyloxy polyalkylene glycol mono (meth) acrylate, nonyl phenoxy polyalkylene glycol mono (meth) acrylate, di(methyl) propylene methoxy group Tricyclodecane, N-(methyl)propenyloxyethylmaleimide, N-(methyl)propenyloxyethylhexahydrophthalimide, N-(A Base) propylene methoxyethyl phthalimide. It is also possible to use: N,N'-methylenebis(meth)propenylamine, N,N'-extended ethylbis(methyl)propenylamine, 1,2-di(methyl)propene (Meth)propenyl decylamine such as hydrazine ethylene glycol. Vinyl compounds such as n-vinyl-2-pyrrolidone, styrene derivatives, and α-methylstyrene derivatives can also be used. Things.

作為(甲基)丙烯酸樹脂，可以使用聚(甲基)丙烯酸酯。作為聚(甲基)丙烯酸酯，係以(甲基)丙烯酸與(甲基)丙烯酸酯之共聚物或是具有羥基的(甲基)丙烯酸酯與無極性基的(甲基)丙烯酸酯的共聚物等為佳。 As the (meth)acrylic resin, poly(meth)acrylate can be used. As a poly(meth) acrylate, a copolymer of (meth)acrylic acid and (meth) acrylate or a copolymer of a (meth) acrylate having a hydroxyl group and a non-polar group (meth) acrylate Things are better.

作為(甲基)丙烯酸樹脂，亦可使用例如：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、1,2-環己二醇單(甲基)丙烯酸酯、1,3-環己二醇單(甲基)丙烯酸酯、1,4-環己二醇單(甲基)丙烯酸酯、1,2-環己烷二甲醇單(甲基)丙烯酸酯、1,3-環己烷二甲醇單(甲基)丙烯酸酯、1,4-環己烷二甲醇單(甲基)丙烯酸酯、1,2-環己烷二乙醇單(甲基)丙烯酸酯、1,3-環己烷二乙醇單(甲基)丙烯酸酯、1,4-環己烷二乙醇單(甲基)丙烯酸酯、甘油單(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、三羥甲基丙烷單(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、季戊四醇單(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、新戊二醇單(甲基)丙烯酸酯等具有羥基之(甲基)丙烯酸酯或該等具有羥基之(甲基)丙烯酸酯與二羧酸或其衍生物反應而可得到之有羧基的(甲基)丙烯酸酯等。在此可使用的二羧酸，例如可以列舉：草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、馬來酸、富馬酸、鄰苯二甲酸、四氫呋喃酸、六氫鄰苯二甲酸以及該等之衍 生物。 As the (meth)acrylic resin, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (methyl) can also be used. 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,2-cyclohexanediol mono(meth)acrylate, 1,3-ring Hexanediol mono(meth)acrylate, 1,4-cyclohexanediol mono(meth)acrylate, 1,2-cyclohexanedimethanol mono(meth)acrylate, 1,3-cyclohexane Alkanediethanol mono(meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 1,2-cyclohexanediethanol mono(meth)acrylate, 1,3-ring Hexane diethanol mono (meth) acrylate, 1,4-cyclohexane diethanol mono (meth) acrylate, glycerol mono (meth) acrylate, glycerol di(meth) acrylate, trishydroxyl Propane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, Neopentyl glycol mono (meth) acrylate or the like having a hydroxyl group (methyl) Acrylate or those having a (meth) acrylate with a dicarboxylic acid or its derivative and the hydroxyl groups of the carboxyl group is obtained (meth) acrylate. Examples of the dicarboxylic acid which can be used herein include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, sebacic acid, and maleic acid. Fumaric acid, phthalic acid, tetrahydrofuranoic acid, hexahydrophthalic acid, and such derivatives biological.

作為熱硬化性樹脂者，可以使用馬來醯亞胺樹脂。馬來醯亞胺樹脂是在1分子內含有1個以上馬來醯亞胺基的化合物，係藉由加熱使馬來醯亞胺基進行反應以形成3維網狀結構，而可硬化。例如，可以列舉：N,N’-(4,4’-二苯基甲烷)雙馬來醯亞胺、雙(3-乙基-5-甲基-4-馬來醯亞胺苯基)甲烷、2,2-雙[4-(4-馬來醯亞胺苯氧基)苯基]丙烷等雙馬來醯亞胺樹脂。更佳的馬來醯亞胺樹脂係：藉由二體酸二胺與馬來酸酐的反應而得到之化合物，藉由所謂馬來醯亞胺醋酸、馬來醯亞胺己酸的馬來醯亞胺化胺基酸與多元醇反應而得到的化合物。馬來醯亞胺化胺基酸，係藉由馬來酸酐與胺基醋酸或是胺基己酸之反應而得到，作為多元醇，是以聚醚多元醇、聚酯多元醇、聚羧酸酯多元醇、聚(甲基)丙烯酸酯多元醇為佳，以不含芳香族環者為特佳。馬來醯亞胺基，因為能與烯丙基反應，故也可以與烯丙酯樹脂併用。烯丙酯樹脂係以脂肪族者為佳，其中特佳者係藉由環己烷二烯丙酯與脂肪族多元醇的酯交換而得之化合物。 As the thermosetting resin, a maleic imine resin can be used. The maleic imine resin is a compound containing one or more maleimine groups in one molecule, and is cured by heating a maleimide group to form a three-dimensional network structure. For example, N,N'-(4,4'-diphenylmethane) bismaleimide, bis(3-ethyl-5-methyl-4-maleimidophenyl) A bismaleimide resin such as methane or 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane. A more preferred maleic imine resin: a compound obtained by the reaction of a dimer acid diamine with maleic anhydride, by the so-called maleic imine acetate, maleic acid, and maleic acid of maleic acid A compound obtained by reacting an imidized amino acid with a polyhydric alcohol. Maleic acid imidized amino acid obtained by the reaction of maleic anhydride with aminoacetic acid or aminocaproic acid. As a polyol, it is a polyether polyol, a polyester polyol, a polycarboxylic acid. The ester polyol and the poly(meth) acrylate polyol are preferred, and those having no aromatic ring are particularly preferred. The maleidinium group can also be used in combination with an allyl ester resin because it can react with an allyl group. The allyl ester resin is preferably an aliphatic one, and a particularly preferred one is a compound obtained by transesterification of a cyclohexane diallyl ester with an aliphatic polyol.

(C)硬化劑 (C) hardener

本發明的組成物含有硬化劑。作為硬化劑，例如可以列舉：脂肪族胺、芳香族胺、二氰基二醯胺、二醯肼化合物、酸酐、酚樹脂等，可以適當地使用於使用環氧樹脂作為熱硬化性樹脂的情形。 The composition of the present invention contains a hardener. Examples of the curing agent include an aliphatic amine, an aromatic amine, a dicyanodiamine, a diterpene compound, an acid anhydride, and a phenol resin, and can be suitably used in the case of using an epoxy resin as a thermosetting resin. .

作為脂肪族胺，可以列舉：二伸乙三胺、三 伸乙四胺、四伸乙五胺、三甲基六亞甲基二胺、間-二甲苯二胺、2-甲基五亞甲基二胺等脂肪族多元胺；異佛酮二胺、1,3-雙胺基甲基環己烷、雙(4-胺基環己基)甲烷、降冰片烯二胺、1,2-二胺基環己烷等脂環式多元胺；N-胺基乙基哌、1,4-雙(2-胺基-2-甲基丙基)哌等哌型多元胺。作為芳香族胺，可以列舉：二胺基二苯基甲烷、間-伸苯二胺、二胺基二苯基碸、二乙基甲苯二胺、三亞甲基雙(4-胺基苯甲酸酯)、聚四亞甲基氧化物-二-對-胺基苯甲酸酯等芳香族多元胺等。 As the aliphatic amine, there may be mentioned diethylenetriamine, triethylenetetramine, tetraethylenepentamine, trimethylhexamethylenediamine, m-xylylenediamine, 2-methylpentamethine Aliphatic polyamines such as bis-diamine; isophorone diamine, 1,3-diaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornene diamine, 1,2-di Alicyclic polyamines such as aminocyclohexane; N-aminoethylpiperine 1,4-bis(2-amino-2-methylpropyl)per Equivalent Type polyamine. Examples of the aromatic amine include diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylphosphonium, diethyltoluenediamine, and trimethylene bis(4-aminobenzoic acid). An aromatic polyamine such as an ester) or a polytetramethylene oxide-di-p-aminobenzoate.

作為二醯肼化合物，可以列舉：己二酸二醯肼、十二酸二醯肼、間苯二甲酸二醯肼、對羥基安息香酸二醯肼等羧酸二醯肼等。作為酸酐，可以列舉：鄰苯二甲酸酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、內亞甲基四氫鄰苯二甲酸酐、十二碳烯琥珀酸酐、馬來酸酐與聚丁二烯的反應物、馬來酸酐與苯乙烯的共聚物等。作為酚樹脂，從硬化物特性之點而言，可以使用在1分子內有2個以上酚性羥基之化合物，理想的酚性羥基數是2至5。酚性羥基的範圍若在此範圍，可以將樹脂組成物的黏度控制在適當的範圍內。更佳為在1分子內的酚性羥基數是2個或3個。作為如此之化合物，可以列舉：雙酚F、雙酚A、雙酚S、四甲基雙酚A、四甲基雙酚F、四甲基雙酚S、二羥基二苯基醚、二羥基二苯甲酮、四甲基聯酚、亞乙基雙酚、甲基亞乙基雙(甲基酚)、環亞己基雙酚、聯酚等雙酚類以及其衍生物；三(羥基苯基)甲烷、三(羥基苯基)乙烷等3官能酚類以及其 衍生物；酚酚醛清漆、甲酚酚醛清漆等酚類與甲醛反應而得之化合物的雙核體或是三核體為主者、以及其之衍生物等。 Examples of the diterpene compound include diammonium adipate, dinonyl dodecanoate, diammonium isophthalate, and dicarboxylic acid dioxime such as p-hydroxybenzoic acid dioxime. Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecene succinic anhydride, and maleic anhydride. A reaction with polybutadiene, a copolymer of maleic anhydride and styrene, and the like. As the phenol resin, a compound having two or more phenolic hydroxyl groups in one molecule can be used from the viewpoint of the properties of the cured product, and the desired number of phenolic hydroxyl groups is from 2 to 5. When the range of the phenolic hydroxyl group is within this range, the viscosity of the resin composition can be controlled within an appropriate range. More preferably, the number of phenolic hydroxyl groups in one molecule is two or three. Examples of such a compound include bisphenol F, bisphenol A, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol S, dihydroxy diphenyl ether, and dihydroxy group. Bisphenols such as benzophenone, tetramethylbiphenol, ethylene bisphenol, methylethylene bis(methylphenol), cyclohexylene bisphenol, biphenol, and derivatives thereof; tris(hydroxybenzene) a trifunctional phenol such as methane or tris(hydroxyphenyl)ethane and a derivative; a dinuclear or a trinuclear compound of a compound obtained by reacting a phenol such as a phenol novolak or a cresol novolak with formaldehyde, and a derivative thereof.

作為硬化劑，可以使用熱自由基聚合起始劑等聚合起始劑，可以適當地使用於使用(甲基)丙烯酸樹脂作為熱硬化性樹脂的情形。聚合起始劑可以使用公知者。熱自由基聚合起始劑的具體例可以列舉：甲基乙基酮過氧化物、甲基環己酮過氧化物、甲基乙醯乙酸酯過氧化物、乙醯丙酮過氧化物、1,1-雙(過氧化三級丁基)3,3,5-三甲基環己烷、1,1-雙(過氧化三級己基)環己烷、1,1-雙(過氧化三級己基)3,3,5-三甲基環己烷、1,1-雙(過氧化三級丁基)環己烷、2,2-雙(4,4-二-三級丁基過氧化環己基)丙烷、1,1-雙(過氧化三級丁基)環十二烷、正丁基4,4-雙(過氧化三級丁基)戊酸酯、2,2-雙(過氧化三級丁基)丁烷、1,1-雙(過氧化三級丁基)-2-甲基環己烷、三級丁基氫過氧化物、對-薄荷烷氫過氧化物、1,1,3,3-四甲基丁基氫過氧化物、三級己基氫過氧化物、二異丙苯基過氧化物、2,5-二甲基-2,5-雙(過氧化三級丁基)己烷、α,α’-雙(過氧化三級丁基)二異丙基苯、三級丁基異丙苯基過氧化物、二-三級丁基過氧化物、2,5-二甲基-2,5-雙(過氧化三級丁基)己炔-3、異丁醯過氧化物、3,5,5-三甲基己醯基過氧化物、辛醯基過氧化物、月桂醯基過氧化物、桂皮酸過氧化物、間-甲苯甲醯基過氧化物、苯甲醯基過氧化物、過氧化二碳酸二異丙酯、過氧化二碳酸雙(4-三級丁基環己基)酯、過氧化二碳酸二-3-甲氧 基丁酯、過氧化二碳酸二-2-乙基己酯、過氧化二碳酸二-二級-丁酯、過氧化二碳酸二(3-甲基-3-甲氧基丁基)酯、過氧化二碳酸二(4-三級丁基環己基)酯、α,α’-雙(過氧化新癸醯基)二異丙基苯、過氧化新癸酸異丙苯酯、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、過氧化新癸酸三級己酯、過氧化新癸酸三級丁酯、過氧化新戊酸三級己酯、過氧化新戊酸三級丁酯、2,5-二甲基-2,5-雙(過氧化2-乙基己醯基)己烷、過氧化-2-乙基己酸1,1,3,3-四甲基丁酯、過氧化-2-乙基己酸1-環己基-1-甲基乙酯、過氧化-2-乙基己酸三級己酯、過氧化-2-乙基己酸三級丁酯、過氧化異丁酸三級丁酯、三級丁基過氧化馬來酸、過氧化月桂酸三級丁酯、過氧化-3,5,5-三甲基己酸三級丁酯、過氧化異丙基單碳酸三級丁酯、過氧化-2-乙基己基單碳酸三級丁酯、2,5-二甲基-2,5-雙(過氧化苯甲醯基)己烷、過氧化乙酸三級丁酯、過氧化苯甲酸三級己酯、過氧化-間-甲苯甲醯基苯甲酸三級丁酯、過氧化苯甲酸三級丁酯、雙(過氧化三級丁基)間苯二甲酸酯、過氧化烯丙基單碳酸三級丁酯、3,3’,4,4’-四(三級丁基過氧化羰基)二苯甲酮等。該等可以單獨使用，也可以併用2種以上。 As the curing agent, a polymerization initiator such as a thermal radical polymerization initiator can be used, and it can be suitably used in the case where a (meth)acrylic resin is used as the thermosetting resin. A known initiator can be used as the polymerization initiator. Specific examples of the thermal radical polymerization initiator include methyl ethyl ketone peroxide, methyl cyclohexanone peroxide, methyl acetonitrile acetate peroxide, acetonitrile acetone peroxide, and 1 , 1-bis(tributyl peroxide) 3,3,5-trimethylcyclohexane, 1,1-bis(tri-hexylperoxy)cyclohexane, 1,1-double (peroxidation III) Grade hexyl) 3,3,5-trimethylcyclohexane, 1,1-bis(tributylbutyl peroxide)cyclohexane, 2,2-bis(4,4-di-tertiary butyl Oxidized cyclohexyl)propane, 1,1-bis(tert-butylperoxy)cyclododecane, n-butyl 4,4-bis(tris-butylperoxy) valerate, 2,2-dual ( Tributyl butyl peroxybutane, 1,1-bis(tributylbutyl peroxide)-2-methylcyclohexane, tertiary butyl hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tertiary hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-double Oxidation of tertiary butyl)hexane, α,α'-bis(tributylperoxy)diisopropylbenzene, tertiary butyl cumyl peroxide, di-tertiary butyl peroxide 2,5-Dimethyl-2,5-bis(tributyl peroxide) Alkyne-3, isobutyl hydrazine peroxide, 3,5,5-trimethylhexyl peroxide, octyl sulfoxide, lauryl peroxide, cinnamic acid peroxide, m-toluidine Base peroxide, benzammonium peroxide, diisopropyl peroxydicarbonate, bis(4-tert-butylcyclohexyl)peroxydicarbonate, di-3-methoxyperoxydicarbonate Butyl ester, di-2-ethylhexyl peroxydicarbonate, di-di-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, Bis(4-tert-butylcyclohexyl) peroxydicarbonate, α,α'-bis(peroxynonyl)diisopropylbenzene, cumene peroxy neodecanoate, new peroxidation 1,1,3,3-tetramethyl butyl citrate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, tertiary hexyl peroxy neodecanoate, tertiary oxidized neodecanoic acid Butyl ester, tertiary hexyl peroxypivalate, tertiary butyl peroxypivalate, 2,5-dimethyl-2,5-bis(2-ethylhexyl)peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, peroxy-2-ethyl Tert-butylhexyl hexanoate, tertiary butyl peroxy-2-ethylhexanoate, tertiary butyl isobutyrate, tertiary butyl peroxymaleic acid, tertiary butyl laurate , tert-butyl peroxy-3,5,5-trimethylhexanoate, butyl peroxy isopropyl monocarbonate, tertiary butyl peroxy-2-ethylhexyl monocarbonate, 2,5 -dimethyl-2,5-double (benzoyl peroxide) hexane, tertiary butyl peroxyacetate, tertiary hexyl peroxybenzoate, tertiary butyl peroxy-m-tolylbenzoic acid, tertiary benzoic acid Butyl ester, bis(tributylbutyl peroxide) isophthalate, butyl peroxybutylene monocarbonate, 3,3',4,4'-tetrakis (tertiary butyl peroxycarbonyl) ) benzophenone and the like. These may be used alone or in combination of two or more.

本發明的組成物，可以含有硬化促進劑，使用環氧樹脂作為熱硬化性樹脂時，可以列舉例如：咪唑類、三苯基膦或是四苯基膦的鹽類等。其中，較佳為2-甲基咪唑、2-乙基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑、2-苯基-4,5-二羥基甲基咪唑、 2-C11H23-咪唑、2-甲基咪唑與2,4-二胺基-6-乙烯基三之加成物等的咪唑化合物。也可以使用改質咪唑化合物，亦可使用環氧基-咪唑加成系化合物或丙烯酸酯-咪唑加成化合物。環氧基-咪唑加成系化合物的市售品，可列舉例如：味之素Fine-Techno公司製之「Amicure PN-23」、同公司製之「Amicure PN-40」、旭化成公司製之「Novacure HX-3721」、富士化成工業公司製之「Fujicure FX-1000」等。丙烯酸酯-咪唑加成系化合物的市售品，可列舉例如：ADEKA公司製之「EH 2021」等。也可以使用旭化成公司製之「Novacure HX-3088」。 The composition of the present invention may contain a curing accelerator. When an epoxy resin is used as the thermosetting resin, for example, a salt of imidazole, triphenylphosphine or tetraphenylphosphine may be mentioned. Among them, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole are preferred. , 2-phenyl-4,5-dihydroxymethylimidazole, 2-C 11 H 23 -imidazole, 2-methylimidazole and 2,4-diamino-6-vinyltriene An imidazole compound such as an adduct. It is also possible to use a modified imidazole compound, or an epoxy-imidazole addition compound or an acrylate-imidazole addition compound. For example, "Amicure PN-23" manufactured by Ajinomoto Fine-Techno Co., Ltd., "Amicure PN-40" manufactured by the company, and "Asahi Kasei Co., Ltd." can be used as a commercial product of the epoxy group-imidazole addition compound. Novacure HX-3721", "Fujicure FX-1000" manufactured by Fuji Kasei Industrial Co., Ltd., etc. The commercially available product of the acrylate-imidazole addition compound is, for example, "EH 2021" manufactured by ADEKA Corporation. "Novacure HX-3088" manufactured by Asahi Kasei Corporation can also be used.

(B)是以環氧樹脂、(甲基)丙烯酸樹脂為佳，以併用環氧樹脂與(甲基)丙烯酸樹脂為更佳。此種情形下，環氧樹脂與(甲基)丙烯酸樹脂的使用量，質量比率(環氧樹脂：(甲基)丙烯酸樹脂)是以95：5至40：60為佳，更佳的是90：10至51：49。如此之併用系統中，(C)係以併用環氧樹脂用的硬化劑與熱自由基聚合起始劑為佳。 (B) It is preferred to use an epoxy resin or a (meth)acrylic resin, and it is more preferable to use an epoxy resin together with a (meth)acrylic resin. In this case, the amount of the epoxy resin and the (meth)acrylic resin to be used and the mass ratio (epoxy resin: (meth)acrylic resin) are preferably 95:5 to 40:60, more preferably 90. : 10 to 51:49. In such a combined system, (C) is preferably a curing agent for a combination of an epoxy resin and a thermal radical polymerization initiator.

(D)(D1)沸點是200℃以上的有機酸之金屬鹽，以及/或是(D2)沸點是200℃以上的有機酸與金屬粒子及/或金屬氧化物粒子之組合 (D) (D1) a metal salt of an organic acid having a boiling point of 200 ° C or higher, and/or a combination of (D2) an organic acid having a boiling point of 200 ° C or more and metal particles and/or metal oxide particles

(D1)沸點是200℃以上的有機酸之金屬鹽中，有機酸的沸點為200℃以上，例如可以列舉沸點是200至300℃的有機酸。藉由使用沸點是200℃以上者，而抑制在加熱硬化步驟的孔洞(void)發生。沸點是在大氣壓下的數值。 (D1) In the metal salt of an organic acid having a boiling point of 200 ° C or higher, the organic acid has a boiling point of 200 ° C or higher, and examples thereof include an organic acid having a boiling point of 200 to 300 ° C. By using a boiling point of 200 ° C or more, the occurrence of voids in the heat hardening step is suppressed. The boiling point is the value at atmospheric pressure.

具體而言，可以列舉飽和單羧酸等，理想的 是在室溫(25℃)中為液狀的飽和單羧酸。飽和單羧酸可以列舉：分枝或是直鏈狀的羧酸，該等亦可具有脂環式基(環戊烷殘基、環己烷殘基等)。 Specifically, a saturated monocarboxylic acid or the like is mentioned, and an ideal one is preferable. It is a saturated monocarboxylic acid which is liquid at room temperature (25 ° C). The saturated monocarboxylic acid may, for example, be a branched or linear carboxylic acid, and these may have an alicyclic group (a cyclopentane residue, a cyclohexane residue or the like).

具體而言，可以列舉：2-乙基己酸等分枝狀飽和單羧酸、環戊烷羧酸等環烷烴單羧酸。又，萘酸等的羧酸混合物而沸點是200℃以上者，也可以使用作為(D1)中之有機酸。理想的是2-乙基己酸、環戊烷羧酸、萘酸。 Specific examples thereof include a cyclohexane hydrocarbon monocarboxylic acid such as a branched saturated monocarboxylic acid such as 2-ethylhexanoic acid or a cyclopentanecarboxylic acid. Further, a carboxylic acid mixture such as naphthoic acid and a boiling point of 200 ° C or higher may be used as the organic acid in (D1). Desirably, 2-ethylhexanoic acid, cyclopentanecarboxylic acid, and naphthoic acid are used.

(D1)沸點是200℃以上的有機酸之金屬鹽中，金屬鹽例如可以列舉標準電極電位為未達0V的金屬之鹽。標準電極電位未達0V的金屬可以列舉鋅、鈷、鎳、鎂、錳、錫，可以列舉該等的金屬鹽(鋅鹽、鈷鹽、鎳鹽、鎂鹽、錳鹽、錫鹽)。理想的是鋅鹽、鈷鹽。支撐構件中，使用銅時，可藉由使用銅或是離子化傾向比銅高者，以防止銅由支撐構件流出。 (D1) The metal salt of the organic acid having a boiling point of 200 ° C or higher, and examples of the metal salt include a salt of a metal having a standard electrode potential of less than 0 V. Examples of the metal having a standard electrode potential of less than 0 V include zinc, cobalt, nickel, magnesium, manganese, and tin, and such metal salts (zinc salts, cobalt salts, nickel salts, magnesium salts, manganese salts, and tin salts) may be mentioned. Ideally, zinc salts and cobalt salts are preferred. In the support member, when copper is used, it is possible to prevent copper from flowing out of the support member by using copper or having a higher ionization tendency than copper.

作為(D1)，可以列舉：2-乙基己酸鋅、2-乙基己酸鈷、2-乙基己酸鎳、2-乙基己酸鎂、2-乙基己酸錳、2-乙基己酸錫、環戊烷羧酸鋅、環戊烷羧酸鈷、環戊烷羧酸鎳、環戊烷羧酸鎂、環戊烷羧酸錳、環戊烷羧酸錫、萘酸鋅、萘酸鈷、萘酸鎳、萘酸鎂、萘酸錳、萘酸錫，理想為2-乙基己酸鋅、環戊酸鋅、萘酸鋅、2-乙基己酸鈷、環戊酸鈷、萘酸鈷。 As (D1), zinc 2-ethylhexanoate, cobalt 2-ethylhexanoate, nickel 2-ethylhexanoate, magnesium 2-ethylhexanoate, manganese 2-ethylhexanoate, 2- Tin ethylhexanoate, zinc cyclopentanecarboxylate, cobalt cyclopentanecarboxylate, nickel cyclopentanecarboxylate, magnesium cyclopentanecarboxylate, manganese cyclopentanecarboxylate, tin cyclopentanecarboxylate, naphthoic acid Zinc, cobalt naphthalate, nickel naphthalate, magnesium naphthalate, manganese naphthalate, tin naphthalate, ideally zinc 2-ethylhexanoate, zinc cyclopentate, zinc naphthalate, cobalt 2-ethylhexanoate, ring Cobalt pentanoate, cobalt naphthalate.

(D2)中，沸點在200℃以上的有機酸，可以使用與在(D1)的關係中列舉之有機酸。理想為2-乙基己酸、環戊烷羧酸、萘酸。 In (D2), the organic acid having a boiling point of 200 ° C or higher can be used as the organic acid listed in the relationship of (D1). Desirably, it is 2-ethylhexanoic acid, cyclopentanecarboxylic acid, and naphthoic acid.

(D2)中，金屬粒子可以列舉標準電極電位未達0V的金屬粒子，例如可以使用鋅、鈷、鎳、鎂、錳、錫以及該等的合金粒子。作為鋅、鈷、鎳、鎂、錳、錫的合金者，可以列舉：選自含有鋅、鈷、鎳、鎂、錳以及錫中之至少1種合金，例如，鋅鋁合金或黃銅。理想為鋅粒子、鈷粒子、鋅合金粒子。在支撐構件使用銅時，可藉由使用銅或是離子化傾向比銅高者，以防止銅從支撐構件流出。又，由於添加錫粒子，能藉由錫的犠牲氧化保護使用銅的支撐構件，故可以提高晶片剪切(die shear)強度。 In (D2), the metal particles may be metal particles having a standard electrode potential of less than 0 V, and for example, zinc, cobalt, nickel, magnesium, manganese, tin, or alloy particles thereof may be used. Examples of the alloy of zinc, cobalt, nickel, magnesium, manganese, and tin include at least one alloy selected from the group consisting of zinc, cobalt, nickel, magnesium, manganese, and tin, and examples thereof include zinc aluminum alloy or brass. It is preferably zinc particles, cobalt particles, and zinc alloy particles. When copper is used as the support member, copper can be prevented from flowing out of the support member by using copper or having a higher ionization tendency than copper. Further, since the tin particles are added, the support member using copper can be protected by the oxidation of tin, so that the die shear strength can be improved.

(D2)中，金屬氧化物粒子可以列舉：標準電極電位未達0V的金屬氧化物的粒子，例如可以列舉：鋅、鈷、鎳、鎂、錳、錫的氧化物粒子。理想為氧化鋅粒子。 In (D2), examples of the metal oxide particles include particles of a metal oxide having a standard electrode potential of less than 0 V, and examples thereof include oxide particles of zinc, cobalt, nickel, magnesium, manganese, and tin. Ideally zinc oxide particles.

(D2)中，金屬粒子及金屬氧化物粒子的形狀並無特別限定，可以列舉：球狀、鱗片狀等。平均粒徑可以是0.05至20μm，理想為0.05至15μm，更理想為0.1至8μm。在此，平均粒徑是藉由雷射繞射法測定之體積基準的平均直徑。 In (D2), the shape of the metal particles and the metal oxide particles is not particularly limited, and examples thereof include a spherical shape and a scaly shape. The average particle diameter may be from 0.05 to 20 μm, desirably from 0.05 to 15 μm, more desirably from 0.1 to 8 μm. Here, the average particle diameter is an average diameter of a volume reference measured by a laser diffraction method.

(D2)也可以是沸點為200℃以上的有機酸與金屬粒子的組合，也可以是沸點為200℃以上的有機酸與金屬氧化物粒子的組合，也可以是沸點為200℃以上的有機酸與金屬粒子與氧化金屬粒子的組合。 (D2) may be a combination of an organic acid having a boiling point of 200 ° C or more and metal particles, or a combination of an organic acid having a boiling point of 200 ° C or higher and metal oxide particles, or an organic acid having a boiling point of 200 ° C or higher. Combined with metal particles and oxidized metal particles.

具體而言，可以列舉：選自2-乙基己酸、環戊烷羧酸以及萘酸中之1種以上，與選自鋅粒子、鈷粒子、鋅合金粒子以及氧化鋅粒子中之1種以上的組合。 Specifically, one or more selected from the group consisting of 2-ethylhexanoic acid, cyclopentanecarboxylic acid, and naphthoic acid, and one selected from the group consisting of zinc particles, cobalt particles, zinc alloy particles, and zinc oxide particles The combination above.

(D2)中，沸點為200℃以上的有機酸、與金屬粒子及/或金屬氧化物粒子的使用量，質量比率(沸點為200℃以上的有機酸：金屬粒子以及/或金屬氧化物粒子)係以10：90至90：10為佳，以20：80至60：40為更佳。 (D2) The amount of the organic acid having a boiling point of 200 ° C or higher, the amount of the metal particles and/or the metal oxide particles used, and the mass ratio (organic acid having a boiling point of 200 ° C or higher: metal particles and/or metal oxide particles) It is preferably from 10:90 to 90:10 and more preferably from 20:80 to 60:40.

作為(D)，可以只使用(D1)，或是只使用(D2)，也可併用(D1)與(D2)。使用(D2)的情形下，係容易控制有機酸的量，在硬化時可以抑制有機酸的溶出(bleed)，而較便利。 As (D), only (D1) or only (D2) may be used, or (D1) and (D2) may be used in combination. In the case of using (D2), it is easy to control the amount of the organic acid, and it is convenient to suppress the bleed of the organic acid at the time of hardening.

(E)多硫化物 (E) polysulfide

第一種態樣中，本發明的組成物是含有(E)多硫化物。(E)只要是具有2個以上硫鍵之化合物，即無特別限定，可以列舉：二硫化物、三硫化物、四硫化物、五硫化物等。藉由將(E)與(D)一同調配，不僅對於貴金屬可以得到良好的接著特性，對於銅也可以得到良好的接著特性。 In the first aspect, the composition of the present invention contains (E) a polysulfide. (E) is not particularly limited as long as it is a compound having two or more sulfur bonds, and examples thereof include disulfide, trisulfide, tetrasulfide, and pentasulfide. By blending (E) with (D), not only good adhesion properties can be obtained for noble metals, but good adhesion properties can also be obtained for copper.

從提高接著性效果之觀點來看，(E)以使用具有多硫鍵之矽烷化合物為佳，可以列舉例如：雙(三甲氧基矽烷基丙基)四硫化物、雙(三乙氧基矽烷基丙基)四硫化物、雙(三丁氧基矽烷基丙基)四硫化物、雙(二甲氧基甲基矽烷基丙基)四硫化物、雙(二乙氧基甲基矽烷基丙基)四硫化物、雙(二丁氧基甲基矽烷基丙基)四硫化物、雙(三甲氧基矽烷基丙基)二硫化物、雙(三乙氧基矽烷基丙基)二硫化物、雙(三丁氧基矽烷基丙基)二硫化物、雙(二甲氧基甲基矽烷基丙基)二硫化物、雙(二乙氧基甲基矽烷基丙基)二硫化物、雙(二丁氧基甲基矽烷基丙基)二硫化物等。 From the viewpoint of improving the adhesion effect, (E) is preferably a decane compound having a polysulfide bond, and examples thereof include bis(trimethoxydecylpropyl)tetrasulfide and bis(triethoxydecane). Propyl) tetrasulfide, bis(tributyloxydecylpropyl) tetrasulfide, bis(dimethoxymethyldecylpropyl) tetrasulfide, bis(diethoxymethyldecyl) Propyl) tetrasulfide, bis(dibutoxymethyldecylpropyl) tetrasulfide, bis(trimethoxydecylpropyl) disulfide, bis(triethoxydecylpropyl)di Sulfide, bis(tributyloxydecylpropyl) disulfide, bis(dimethoxymethyldecylpropyl) disulfide, bis(diethoxymethyldecylpropyl) disulfide , bis(dibutoxymethyl decylpropyl) disulfide, and the like.

由具有(C)硬化劑的功能與(E)多硫化物的兩者功能之點而言，在(B)熱硬化性樹脂中使用環氧化合物時，亦可以適合使用有多硫鍵之胺化合物，例如可以列舉4,4’-二胺基二苯基二硫化物等。 From the point of having both the function of the (C) hardener and the function of (E) polysulfide, when an epoxy compound is used in the (B) thermosetting resin, an amine having a polysulfide bond can also be suitably used. Examples of the compound include 4,4'-diaminodiphenyl disulfide and the like.

(E)可以單獨使用，也可以併用二種以上。 (E) may be used singly or in combination of two or more.

本發明的樹脂組成物中，相對於(A)至(E)的合計100質量份：(A)可以是40至90質量份，較理想的是55至90質量份，更理想的是60至88質量份；(B)可以是5至55質量份，從熱硬化性的觀點來看，較理想的是5至50質量份，更理想的是10至40質量份；(C)可以是1至50質量份，從硬化性的觀點來看，更理想的是2至40質量份，又更理想的是2至20質量份；(D)可以是0.05至5質量份，從抑制高溫製程中的硬化物剝離效果之觀點來看，較理想的是0.1至2質量份，更理想的是0.1至1質量份；(E)可以是0.075至8.5質量份，從防止周邊構件的過度污染之觀點來看，較理想的是0.075至4.5質量份，更理想的是0.075至0.85質量份。換算成硫的量，可以是0.02至2.0質量份，較理想的是0.02至1.0質量份，更理想的是0.02至0.2質量份。 The resin composition of the present invention may be 40 to 90 parts by mass, more preferably 55 to 90 parts by mass, more preferably 60 to 60 parts by mass, based on 100 parts by mass total of (A) to (E). 88 parts by mass; (B) may be 5 to 55 parts by mass, more preferably 5 to 50 parts by mass, more desirably 10 to 40 parts by mass, from the viewpoint of thermosetting property; (C) may be 1 To 50 parts by mass, more preferably 2 to 40 parts by mass, still more preferably 2 to 20 parts by mass, from the viewpoint of hardenability; (D) may be 0.05 to 5 parts by mass from the high-temperature inhibition process From the viewpoint of the peeling effect of the cured product, it is preferably 0.1 to 2 parts by mass, more preferably 0.1 to 1 part by mass; and (E) may be 0.075 to 8.5 parts by mass, from the viewpoint of preventing excessive contamination of peripheral members. In view of the above, it is preferably from 0.075 to 4.5 parts by mass, more preferably from 0.075 to 0.85 parts by mass. The amount converted to sulfur may be 0.02 to 2.0 parts by mass, more preferably 0.02 to 1.0 part by mass, still more desirably 0.02 to 0.2 part by mass.

又，支撐構件不含貴金屬時，(D)與(E)的質量比率((D)：(E))是以50：1至1：10為佳，較理想的是10：1至1：10。另一方面，支撐構件含有貴金屬時，(D)與(E)的質量比率((D)：(E))是以10：1至1：50為佳，以3：1至1：50為更佳。 Further, when the support member does not contain a noble metal, the mass ratio of (D) to (E) ((D): (E)) is preferably 50:1 to 1:10, and more preferably 10:1 to 1: 10. On the other hand, when the support member contains a noble metal, the mass ratio of (D) to (E) ((D): (E)) is preferably from 10:1 to 1:50, and from 3:1 to 1:50. Better.

(F)二丙烯酸酯鋅 (F) zinc diacrylate

本發明的組成物可以含有(F)二丙烯酸酯鋅。藉由調配(F)，可抑制因吸濕造成的在高溫製程中硬化物劣化，以進一步提高接著強度。尤其，在(F)為(B)含有丙烯酸樹脂的情形下，因可以提高晶片剪切強度而為佳。此被認為係因為(F)的丙烯酸酯部分與(B)的(甲基)丙烯基反應，而可以提高硬化物的強度。 The composition of the present invention may contain (F) zinc diacrylate. By blending (F), deterioration of the cured product in the high-temperature process due to moisture absorption can be suppressed to further improve the bonding strength. In particular, in the case where (F) is (B) containing an acrylic resin, it is preferable to increase the shear strength of the wafer. This is considered to be because the acrylate portion of (F) reacts with the (meth) propylene group of (B), and the strength of the cured product can be increased.

相對於(A)至(E)的合計100質量份，(F)可以是0.05至5質量份，較理想的是0.05至2質量份，更理想的是0.1至1質量份。 The (F) may be 0.05 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, and more desirably 0.1 to 1 part by mass, relative to 100 parts by mass of the total of (A) to (E).

本發明的組成物可以含有：抗氧化劑(初級抗氧化劑、二級抗氧化劑)、金屬減活劑、偶合劑(矽烷偶合劑、鈦偶合劑等)、著色劑、消泡劑、界面活性劑、聚合抑制劑等添加劑。 The composition of the present invention may contain: an antioxidant (primary antioxidant, secondary antioxidant), a metal deactivator, a coupling agent (a decane coupling agent, a titanium coupling agent, etc.), a coloring agent, an antifoaming agent, a surfactant, Additives such as polymerization inhibitors.

第二種態樣中，本發明的樹脂組成物是含有：(A)無機填充劑、(B)熱硬化性樹脂、(C)硬化劑、(D)(D1)沸點是在200℃以上的有機酸之金屬鹽，以及/或是(D2)沸點是在200℃以上的有機酸與金屬粒子及/或金屬氧化物粒子的組合、與(E’)二級抗氧化劑。 In the second aspect, the resin composition of the present invention contains: (A) an inorganic filler, (B) a thermosetting resin, (C) a curing agent, and (D) (D1) having a boiling point of 200 ° C or higher. The metal salt of the organic acid, and/or the (D2) boiling point is an organic acid at 200 ° C or higher and a combination of metal particles and/or metal oxide particles, and (E') secondary antioxidant.

關於第二種態樣中之(A)至(D)，包括例示以及理想的例子在內，亦適用上述第一態樣中(A)至(D)的相 關記載。就(A)無機填充劑的平均粒徑而言，也可以使用1至15μm者。 Regarding (A) to (D) in the second aspect, including the exemplified and ideal examples, the phases of (A) to (D) in the first aspect described above are also applicable. Guan records. As the average particle diameter of the (A) inorganic filler, those of 1 to 15 μm can also be used.

(E’)二級抗氧化劑 (E’) secondary antioxidant

第二種態樣中，本發明的組成物含有(E’)二級抗氧化劑。抗氧化劑一般分成初級抗氧化劑(自由基捕捉劑)與二級抗氧化劑(過氧化物分解劑)，而(E’)為二級抗氧化劑，具體可以列舉：硫系二級抗氧化劑、磷系二級抗氧化劑。 In the second aspect, the composition of the present invention contains (E') a secondary antioxidant. Antioxidants are generally classified into primary antioxidants (radical scavengers) and secondary antioxidants (peroxide decomposers), and (E') is a secondary antioxidant. Specific examples thereof include sulfur-based secondary antioxidants and phosphorus systems. Secondary antioxidant.

具體而言，可以列舉：二月桂基-3,3’-硫代二丙酸酯、二(十三基)-3,3’-硫代二丙酸酯、二(肉豆蔻基)-3,3’-硫代二丙酸酯、二硬脂基-3,3’-硫代二丙酸酯、肆-亞甲基-3-月桂基硫代丙酸酯甲烷、二硬脂基-3,3’-甲基-3,3’-硫代二丙酸酯、月桂基硬脂基-3,3’-硫代二丙酸酯、雙[2-甲基-4-(3-n-烷基硫代丙醯氧基)-5-三級丁基苯基]硫化物、β-月桂基硫代丙酸酯、2-巰基苯并咪唑、2-巰基-5-甲基苯并咪唑、硫代三聚氰酸等硫系二級抗氧化劑；參(異癸基)亞磷酸酯、參(十三基)亞磷酸酯、苯基二異辛基亞磷酸酯、苯基二異癸基亞磷酸酯、苯基二(十三基)亞磷酸酯、二苯基異辛基亞磷酸酯、二苯基異癸基亞磷酸酯、二苯基十三烷基亞磷酸酯、膦酸[1,1-二苯基-4,4’-二基雙肆-2,4-雙(1,1-二甲基乙基)苯基]酯、三苯基亞磷酸酯、參(壬基苯基)亞磷酸酯、4,4’-異亞丙基二酚烷基亞磷酸酯、參(2,4-二-三級丁基苯基)亞磷酸酯、參(聯苯基)亞磷酸酯、二硬脂基季戊四醇二亞磷酸酯、二(2,4-二-三級丁基苯基)季戊四醇二亞磷酸酯、二(壬基苯基)季戊四醇二亞磷酸酯、 苯基雙酚A季戊四醇二亞磷酸酯、四(十三基)-4,4’-亞丁基雙(3-甲基-6-三級丁基酚)二亞磷酸酯、六(十三基)-1,1,3-參(2-甲基-4-羥基-5-三級丁基苯基)丁醇三亞磷酸酯、3,5-二-三級丁基-4-羥基苄基磷酸酯二乙基酯、雙(4-三級丁基苯基)磷酸鈉、2,2’-亞甲基-雙(4,6-二-三級丁基苯基)磷酸鈉、1,3-雙(二苯氧基膦醯氧基)苯、3,9-雙(4-壬基苯氧基)-2,4,8,10-四氧雜-3,9-二膦螺[5.5]十一烷、3,9-雙(十八基氧基)-2,4,8,10-四氧雜-3,9-二膦螺[5.5]十一烷、2,4,8,10-肆(1,1-二甲基乙基)-6-[(2-乙基己基)氧]-12H-二苯并[d,g][1,3,2]二氧雜磷雜環辛烷等磷系二級抗氧化劑。 Specific examples include dilauryl-3,3'-thiodipropionate, bis(tridecyl)-3,3'-thiodipropionate, and bis(myristyl)-3. , 3'-thiodipropionate, distearyl-3,3'-thiodipropionate, hydrazine-methylene-3-lauryl thiopropionate methane, distearyl- 3,3'-Methyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, bis[2-methyl-4-(3- N-alkylthiopropoxycarbonyl)-5-tris-butylphenyl]sulfide, β-laurylthiopropionate, 2-mercaptobenzimidazole, 2-mercapto-5-methylbenzene a sulfur-based secondary antioxidant such as imidazole or thiocyanuric acid; ginsengyl phosphite, stilbene (tridecyl) phosphite, phenyl diisooctyl phosphite, phenyl di Isodecyl phosphite, phenyl di(tridecyl) phosphite, diphenyl isooctyl phosphite, diphenylisodecyl phosphite, diphenyltridecyl phosphite, [1,1-diphenyl-4,4'-diylbiguanide-2,4-bis(1,1-dimethylethyl)phenyl]phosphonate, triphenylphosphite, ginseng (nonylphenyl) phosphite, 4,4'-isopropylidenediphenol alkylphosphorus Acid ester, ginseng (2,4-di-tri-butylphenyl) phosphite, bis(biphenyl) phosphite, distearyl pentaerythritol diphosphite, di(2,4-di- Tertiary butylphenyl) pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, Phenyl bisphenol A pentaerythritol diphosphite, tetrakis(tridecyl)-4,4'-butylene bis(3-methyl-6-tertiary butylphenol) diphosphite, six (tridecyl) -1,1,3-glycol(2-methyl-4-hydroxy-5-tert-butylphenyl)butanol triphosphite, 3,5-di-tertiary butyl-4-hydroxybenzyl Diethyl phosphate, sodium bis(4-tributylphenyl)phosphate, sodium 2,2'-methylene-bis(4,6-di-triphenylphenyl)phosphate, 1, 3-bis(diphenoxyphosphoniumoxy)benzene, 3,9-bis(4-mercaptophenoxy)-2,4,8,10-tetraoxa-3,9-diphosphine snail [ 5.5] undecane, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphine spiro[5.5]undecane, 2,4,8 , 10-肆(1,1-dimethylethyl)-6-[(2-ethylhexyl)oxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphorus A phosphorus-based secondary antioxidant such as a heterocyclic octane.

從耐水解性的觀點來看，係以硫系二級抗氧化劑為佳，其中，從抑制高溫製程後的硬化物剝離效果之觀點來看，係以硫醇系及/或硫醚系二級抗氧化劑為佳，具體而言，可以列舉：2-巰基苯并咪唑、2-巰基-5-甲基苯并咪唑、硫代三聚氰酸、二(十三基)-3,3’-硫代二丙酸酯等。 From the viewpoint of hydrolysis resistance, a sulfur-based secondary antioxidant is preferred, and from the viewpoint of suppressing the peeling effect of the cured product after the high-temperature process, the thiol-based and/or thioether-based secondary is used. The antioxidant is preferred, and specific examples thereof include 2-mercaptobenzimidazole, 2-mercapto-5-methylbenzimidazole, thiocyanuric acid, and di(tridecyl)-3,3'- Thiodipropionate and the like.

二級抗氧化劑可以單獨使用，也可以併用二種以上。 The secondary antioxidant may be used singly or in combination of two or more.

本發明的樹脂組成物中，相對於(A)至(D)以及(E’)的合計100質量份：(A)可以是40至90質量份，較理想的是55至90質量份，更理想的是60至88質量份；(B)可以是5至55質量份，從熱硬化性的觀點來看，較理想的是5至50質量份，更理想的是10至40質量份；(C)可以是1至50質量份，從硬化性的觀點來看，較理想的是2至40質量份，更理想的是2至20質量份；(D)可以是0.1 至5質量份，從抑制在高溫製程的硬化物剝離效果之觀點來看，較理想的是0.1至2質量份，更理想的是0.1至1質量份；(E’)可以是0.03至5質量份，從保存安定性的觀點來看，較理想的是0.03至1質量份，更理想的是0.03至0.5質量份。 In the resin composition of the present invention, the total amount of (A) to (D) and (E') may be 40 to 90 parts by mass, more preferably 55 to 90 parts by mass, more preferably, based on 100 parts by mass of (A) to (D) and (E'). It is preferably 60 to 88 parts by mass; (B) may be 5 to 55 parts by mass, and more preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, from the viewpoint of thermosetting property; C) may be 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, more desirably 2 to 20 parts by mass, from the viewpoint of hardenability; (D) may be 0.1 To 5 parts by mass, from the viewpoint of suppressing the peeling effect of the cured product at a high temperature process, it is preferably 0.1 to 2 parts by mass, more desirably 0.1 to 1 part by mass; and (E') may be 0.03 to 5 parts by mass. The portion is preferably from 0.03 to 1 part by mass, more preferably from 0.03 to 0.5 part by mass, from the viewpoint of preservation stability.

(F’)初級抗氧化劑及/或金屬減活劑 (F') primary antioxidant and / or metal deactivator

本發明的組成物可以含有(F’)初級抗氧化劑及/或金屬減活劑，藉此，可以期進一步改善接著強度或進一步抑制在高溫製程的硬化物之剝離。 The composition of the present invention may contain (F') a primary antioxidant and/or a metal deactivator, whereby the subsequent strength may be further improved or the peeling of the cured product at a high temperature process may be further suppressed.

作為初級抗氧化劑，可以列舉：酚系初級抗氧化劑、胺系初級抗氧化劑。 Examples of the primary antioxidant include a phenol-based primary antioxidant and an amine-based primary antioxidant.

具體而言，可以列舉：氫醌、甲氧基氫醌、苯并醌、對-三級丁基兒茶酚、氯醌(chloranil)、2-三級丁基氫醌、2,5-二-三級丁基氫醌、2,6-二-三級丁基酚、2,4-二-三級丁基酚、2-三級丁基甲氧基氫醌、2-三級丁基-4,6-二甲基酚、2,6-二-三級丁基-4-甲基酚、2,6-二-三級丁基-4-乙基酚、2,4,6-三-三級丁基酚、2,6-三級丁基-4-羥基甲基酚、2,6-二-三級丁基-對-甲酚、2,6-二-三級丁基-2-二甲基胺基-對-甲酚、2,5-二-三級丁基氫醌、2,5-二-三級戊基氫醌、n-十八基基-3-(3’,5’-二-三級丁基-4’-羥基苯基)丙酸酯、2,4-雙(n-辛基硫)-6-(4-羥基-3,5-二-三級丁基苯胺基)-1,3,5-三、苯乙烯酸酯酚(stylinate phenol)、α-生育酚、2-三級丁基-6-(3’-三級丁基-5’-甲基-2’-羥基苄基)-4-甲基苯基丙烯酸酯、2-[1-(2-羥基-3,5-二-三級戊基苯 基)乙基]-4,6-二-三級戊基苯基丙烯酸酯、2,2’-亞甲基雙(4-甲基-6-三級丁基酚)、2,2’-亞甲基雙(4-乙基-6-三級丁基酚)、2,2’-亞甲基雙(6-環己基-4-甲基酚)、2,2’-亞甲基雙(6-1-甲基環己基)-對-甲酚、2,2’-亞乙基雙(2,4-二-三級丁基酚)、2,2’-亞丁基雙(2-三級丁基-4-甲基酚)、4,4’-亞甲基雙(2,6-二-三級丁基酚)、4,4’-亞丁基雙(3-甲基-6-三級丁基酚)、1,6-己二醇雙[3-(3,5-二-三級丁基-(4-羥基苯基)]丙酸酯、三乙二醇雙[(3-三級丁基-5-甲基-4-羥基苯基)]丙酸酯、N,N’-雙[3-(3,5-二-三級丁基-4-羥基苯基)丙醯]肼、N,N’-雙[3-(3’,5’-二-三級丁基-4-羥基苯基)丙醯基]六亞甲基二胺、2,2-硫代雙(4-甲基-6-三級丁基酚)、4,4’-硫代雙(3-甲基-6-三級丁基酚)、2,2-硫代二乙烯雙[3-(3,5-二-三級丁基-4-羥基苯基)丙酸酯]、雙[2-三級丁基-4-甲基-6-(3-三級丁基-5-甲基-2-羥基苄基)苯基]對苯二甲酸酯、1,1,3-參(2-甲基-4-羥基-5-三級丁基苯基)丁烷、1,3,5-三甲基-2,4,6-參(3,5-二-三級丁基-4-羥基苄基)苯、參(3,5-二-三級丁基-4-羥基苄基)三聚異氰酸酯、參[2-(3’,5’-二-三級丁基-4’-羥基氫-桂皮醯基氧基)乙基]三聚異氰酸酯、參(4-三級丁基-2,6-二-甲基-3-羥基苄基)三聚異氰酸酯、肆[亞甲基-3-(3’,5’-二-三級丁基-4’-羥基苯基)丙酸酯]甲烷、雙(乙基-3,5-二-三級丁基)-4-羥基苄基磷酸鈣、丙基-3,4,5-三羥基苯羧酸酯、辛基-3,4,5-三羥基苯羧酸酯、十二基-3,4,5-三羥基苯羧酸酯、2,2’-亞甲基雙(4-間-乙基-6-三級丁基酚)、4,4-亞甲基雙(2,6-二-三級丁基酚)、1,1-雙(4-羥基苯基) 環己烷、1,1,3-參(2-甲基-4-羥基-5-三級丁基苯基)丁烷、1,3,5-三甲基-2,4,6-參(3,5-二-三級丁基-4-羥基苄基)苯、3,9-雙[1,1-二甲基-2-{β-(3-三級丁基-4-羥基-5-甲基苯基)丙醯氧基}乙基]-2,4,8,10-四氧雜螺[5,5]十一烷等烷基酚系初級抗氧化劑；烷基化二苯基胺、N,N’-二苯基-對-伸苯二胺、6-乙氧基-2,2,4-三甲基-1,2-二氫喹啉、N-苯基-N'-異丙基-對-苯二胺、N-苯基-1,3-二甲基丁基-對-伸苯二胺、2,2,4-三甲基-1,2-二氫喹啉聚合物、醛醇-α-萘基胺、N-苯基-β-萘基胺、N,N’-二-2-萘基-對-伸苯二胺、4,4’-二辛基二苯基胺等胺系初級抗氧化劑。 Specific examples thereof include hydroquinone, methoxyhydroquinone, benzopyrene, p-tert-butyl catechol, chloranil, 2-tris-butylhydroquinone, 2,5-di - tertiary butyl hydroquinone, 2,6-di-tertiary butyl phenol, 2,4-di-tertiary butyl phenol, 2-tert-butyl butyl methoxyhydroquinone, 2-tributyl butyl-4 ,6-dimethylphenol, 2,6-di-tertiary butyl-4-methylphenol, 2,6-di-tertiary butyl-4-ethylphenol, 2,4,6-tri- Tert-butyl phenol, 2,6-tris-butyl-4-hydroxymethylphenol, 2,6-di-tert-butyl-p-cresol, 2,6-di-tertiary butyl-2 - dimethylamino-p-cresol, 2,5-di-tertiary butyl hydroquinone, 2,5-di-tridecylhydroquinone, n-octadecyl-3-(3' , 5'-di-tertiary butyl-4'-hydroxyphenyl)propionate, 2,4-bis(n-octylsulfanyl)-6-(4-hydroxy-3,5-di-triad Butylanilino)-1,3,5-three , stylinate phenol, α-tocopherol, 2-tert-butyl butyl-6-(3'-tertiary butyl-5'-methyl-2'-hydroxybenzyl)-4- Methyl phenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tri-pentylphenyl)ethyl]-4,6-di-tri-pentyl phenyl acrylate, 2 , 2'-methylenebis(4-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-ethyl-6-tributylphenol), 2,2 '-Methylene bis(6-cyclohexyl-4-methylphenol), 2,2'-methylenebis(6-1-methylcyclohexyl)-p-cresol, 2,2'-Asia Ethyl bis(2,4-di-tertiary butyl phenol), 2,2'-butylene bis(2-tert-butyl-4-methylphenol), 4,4'-methylene bis ( 2,6-di-tertiary butyl phenol), 4,4'-butylene bis(3-methyl-6-tertiary butyl phenol), 1,6-hexanediol bis [3-(3, 5-di-tertiary butyl-(4-hydroxyphenyl)]propionate, triethylene glycol bis[(3-tert-butyl-5-methyl-4-hydroxyphenyl)]propionate , N,N'-bis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propanoid] 肼, N,N'-bis[3-(3',5'-di -Tris-butyl-4-hydroxyphenyl)propanyl]hexamethylenediamine, 2,2-thiobis(4-methyl-6-tertiary butylphenol), 4,4'- Thiobis(3-methyl-6-tertiary butylphenol), 2,2-thiodi Ethylene bis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate], bis[2-tri-butyl-4-methyl-6-(3-tri-butyl) 5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 1,1,3-glycol(2-methyl-4-hydroxy-5-tributylphenyl) Alkane, 1,3,5-trimethyl-2,4,6-parade (3,5-di-tri-butyl-4-hydroxybenzyl)benzene, ginseng (3,5-di-tridecyl) Benzyl-4-hydroxybenzyl)trimeric isocyanate, ginseng [2-(3',5'-di-tert-butyl-4'-hydroxyhydro-cinnamoyloxy)ethyl]trimeric isocyanate, ginseng (4-tertiary butyl-2,6-di-methyl-3-hydroxybenzyl)-polyisocyanate, hydrazine [methylene-3-(3',5'-di-tertiary butyl-4) '-Hydroxyphenyl)propionate]methane, bis(ethyl-3,5-di-tri-butyl)-4-hydroxybenzyl phosphate, propyl-3,4,5-trihydroxybenzoate Acid ester, octyl-3,4,5-trihydroxybenzenecarboxylate, dodecyl-3,4,5-trihydroxybenzenecarboxylate, 2,2'-methylenebis(4-inter) Ethyl-6-tertiary butyl phenol), 4,4-methylenebis(2,6-di-tertiary butyl phenol), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1, 1,3-para (2-methyl-4-hydroxy-5-tributylphenyl) butane, 1,3,5-trimethyl-2,4,6-para (3,5 -di-tertiary butyl-4-hydroxyl Benzyl)benzene, 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy}ethyl Alkylphenol-based primary antioxidants such as -2,4,8,10-tetraoxaspiro[5,5]undecane; alkylated diphenylamine, N,N'-diphenyl-p- Phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N-phenyl-N'-isopropyl-p-phenylenediamine, N- Phenyl-1,3-dimethylbutyl-p-phenylenediamine, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, aldol-α-naphthylamine, An amine-based primary antioxidant such as N-phenyl-β-naphthylamine, N,N'-di-2-naphthyl-p-phenylenediamine or 4,4'-dioctyldiphenylamine.

金屬減活劑可以列舉：三唑系化合物、多元胺化合物、肼系化合物、草酸系化合物、水楊酸系化合物等。作為三唑系化合物的具體例，可以列舉：苯并三唑、3-(N-水楊醯基)胺基-1,2,4-三唑等。多元胺的具體例，可以列舉：3,9-雙[2-(3,5-二胺基-2,4,6-三吖苯基)乙基]-2,4,8,10-四氧雜螺[5.5]十一烷、伸乙二胺-四乙酸、伸乙二胺-四乙酸的鹼金屬(Li、Na、K)鹽、N,N’-二亞水楊基-伸乙二胺、N,N’-二亞水楊基-1,2-伸丙二胺、N,N”-二亞水楊基-N’-甲基-二伸丙三胺、3-水楊醯基胺基-1,2,4-三唑等。 Examples of the metal deactivator include a triazole compound, a polyamine compound, an anthraquinone compound, an oxalic acid compound, and a salicylic acid compound. Specific examples of the triazole-based compound include benzotriazole and 3-(N-salicylidene)amino-1,2,4-triazole. Specific examples of the polyamine include 3,9-bis[2-(3,5-diamino-2,4,6-triphenylphenyl)ethyl]-2,4,8,10-tetra Alkali metal (Li, Na, K) salt of N. oxaspiro[5.5]undecane, ethylenediamine-tetraacetic acid, ethylenediamine-tetraacetic acid, N,N'-diAsian salicyl-Extension B Diamine, N,N'-disalicylidene-1,2-propanediamine, N,N"-disalicylidene-N'-methyl-di-extension propylenetriamine, 3-hydrazone Amino-1,2,4-triazole and the like.

肼系化合物的具體例可以列舉：十亞甲基二羧酸-雙(N’-水楊醯基醯肼)、雙(1-苯基-3-甲基-4-癸基-5-吡唑特)鎳、2-乙氧基-2’-乙基草醯苯胺、5-三級丁基-2-乙氧基-2’-乙基草醯苯胺、N,N-二乙基-N’,N’-二苯基草醯胺、N,N’-二乙基-N,N’-二苯基草醯胺、草酸-雙(苯亞 甲基醯肼)、硫代二丙酸-雙(苯亞甲基醯肼)、間苯二甲酸-雙(2-苯氧基丙醯基醯肼)、雙(水楊醯基肼)、N-亞水楊基-N’-水楊醯基腙、N,N’-雙[3-(3,5-二-三級丁基-4-羥基苯基)丙醯基]肼、參[2-三級丁基-4-硫代(2’-甲基-4’-羥基-5’-三級丁基苯基)-5-甲基苯基]亞磷酸酯、雙[2-三級丁基-4-硫代(2’-甲基-4’-羥基-5’-三級丁基苯基)-5-甲基苯基]-季戊四醇-二亞磷酸酯、肆[2-三級丁基-4-硫代(2’-甲基-4’-羥基-5’-三級丁基苯基)-5-甲基苯基]-1,6-六亞甲基-雙(N-羥基乙基-N-甲基半卡肼)-二亞磷酸酯、肆[2-三級丁基-4-硫代(2’-甲基-4’-羥基-5’-三級丁基苯基)-5-甲基苯基]-1,10-十亞甲基-二-羧酸-二-羥基乙基羰基醯肼-二亞磷酸酯、肆[2-三級丁基-4-硫代(2’-甲基-4’-羥基-5’-三級丁基苯基)-5-甲基苯基]-1,10-十亞甲基-二-羧酸-二-水楊醯基醯肼-二磷酸酯、肆[2-三級丁基-4-硫代(2’-甲基-4’-羥基-5’-三級丁基苯基)-5-甲基苯基]-二(羥基乙基羰基)醯肼-二亞磷酸酯、肆[2-三級丁基-4-硫代(2’-甲基-4’-羥基-5’-三級丁基苯基)-5-甲基苯基]-N,N’-雙(羥基乙基)乙二醯二胺基-二亞磷酸酯、N,N’-雙[2-[3-(3,5-二-三級丁基-4-羥基苯基)丙醯氧基]乙基]乙二醯二胺等。 Specific examples of the lanthanoid compound include: decamethyldicarboxylic acid-bis(N'-salicylidene), bis(1-phenyl-3-methyl-4-indolyl-5-pyrazole) Nickel, 2-ethoxy-2'-ethyloxalin, 5-tert-butyl-2-ethoxy-2'-ethyloxalin, N,N-diethyl-N' , N'-diphenyl oxazamide, N, N'-diethyl-N, N'-diphenyl oxazamide, oxalic acid - bis (benzene Methyl hydrazine), thiodipropionic acid-bis(benzylidene fluorene), isophthalic acid-bis(2-phenoxypropyl fluorenyl), bis(saltyl hydrazine), N- Salicylidene-N'-salicylidene, N,N'-bis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propanyl]anthracene, ginseng [2-three Butyl-4-thio(2'-methyl-4'-hydroxy-5'-tertiary butylphenyl)-5-methylphenyl]phosphite, bis[2-tributyl 4-thio(2'-methyl-4'-hydroxy-5'-tris-butylphenyl)-5-methylphenyl]-pentaerythritol-diphosphite, 肆[2- tertiary butyl 4--4-thio(2'-methyl-4'-hydroxy-5'-tertiary butylphenyl)-5-methylphenyl]-1,6-hexamethylene-bis(N- Hydroxyethyl-N-methylsemicarbazide)-diphosphite, 肆[2-tert-butyl-4-thio(2'-methyl-4'-hydroxy-5'-tertiary butyl Phenyl)-5-methylphenyl]-1,10-decamethylene-di-carboxylic acid-di-hydroxyethylcarbonylphosphonium-diphosphite, 肆[2-tert-butyl-4 - thio(2'-methyl-4'-hydroxy-5'-tertiary butylphenyl)-5-methylphenyl]-1,10-decamethylene-di-carboxylic acid-di- Salicylhydrazine-diphosphate, hydrazine [2-tert-butyl-4-thio (2'-methyl) -4'-hydroxy-5'-tris-butylphenyl)-5-methylphenyl]-bis(hydroxyethylcarbonyl)phosphonium-diphosphite, hydrazine [2-tert-butyl-4 - thio(2'-methyl-4'-hydroxy-5'-tertiary butylphenyl)-5-methylphenyl]-N,N'-bis(hydroxyethyl)ethylenediaminediamine Base-diphosphite, N,N'-bis[2-[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propenyloxy]ethyl]ethylenediamine diamine Wait.

作為(F’)，具體是以酚系初級抗氧化劑、胺系初級抗氧化劑、肼系化合物為佳。 Specifically, (F') is preferably a phenol-based primary antioxidant, an amine-based primary antioxidant, or an anthraquinone-based compound.

相對於(A)至(D)以及(E’)的合計100質量份，(F’)可以是0.05至5.0質量份，從溶出/暈開(bleed out/blooming)的觀點來看，較理想是0.05至1.0質量份， 更理想是0.05至0.5質量份。 (F') may be 0.05 to 5.0 parts by mass with respect to the total of 100 parts by mass of (A) to (D) and (E'), and is preferable from the viewpoint of bleed out/blooming It is 0.05 to 1.0 part by mass, More preferably, it is 0.05 to 0.5 part by mass.

本發明的組成物，可以含有偶合劑(矽烷偶合劑、鈦偶合劑等)、著色劑、消泡劑、界面活性劑、聚合抑制劑等添加劑。 The composition of the present invention may contain additives such as a coupling agent (a decane coupling agent, a titanium coupling agent, etc.), a coloring agent, an antifoaming agent, a surfactant, and a polymerization inhibitor.

<樹脂組成物的調製> <Modulation of Resin Composition>

本發明的樹脂組成物，係可藉由在混合(C)以外的各成分之後，使用3輥分散機來混練，接著添加(C)均勻地混合而調製。 The resin composition of the present invention can be prepared by mixing each component other than (C), followed by kneading using a 3-roll disperser, followed by adding (C) uniformly.

<黏晶膠以及放熱構件用接著劑> <Adhesive and adhesive for heat release member>

本發明的樹脂組成物，可以適合使用作為黏晶膠、放熱構件用接著劑。具體而言，係可將含有本發明的樹脂組成物之黏晶膠或放熱構件用接著劑施用在引線框架或基板等，安裝半導體元件或放熱構件等，並使之加熱硬化，以進行接著。加熱硬化的條件可以適當的選擇，例如可以用100至200℃的峰溫度加熱。接著，經由打線，藉由密封，可以得到半導體裝置。該半導體裝置可在印刷配線基板上焊接組裝，作成各種的電子零件。本發明的樹脂組成物的硬化物，係接著強度優良、在高溫製程中也不易剝離，還能抑制因吸濕造成的在高溫製程的強度劣化。又，支撐構件是銅引線框架或銅基板時，也可以發揮該等的效果，有用性高。 The resin composition of the present invention can be suitably used as an adhesive for a pressure-sensitive adhesive or a heat-releasing member. Specifically, the adhesive or the heat releasing member containing the resin composition of the present invention may be applied to a lead frame or a substrate or the like with an adhesive, and a semiconductor element, a heat releasing member, or the like may be mounted and heat-hardened to be carried out. The conditions of heat hardening can be appropriately selected, and for example, it can be heated at a peak temperature of 100 to 200 °C. Next, a semiconductor device can be obtained by sealing by wire bonding. The semiconductor device can be soldered and assembled on a printed wiring board to form various electronic components. The cured product of the resin composition of the present invention is excellent in strength and is not easily peeled off in a high-temperature process, and can suppress deterioration of strength in a high-temperature process due to moisture absorption. Further, when the support member is a copper lead frame or a copper substrate, these effects can be exhibited, and the usefulness is high.

(實施例) (Example)

以下，藉由實施例進一步詳細說明本發明。份、%若無其他特別限定，即表示質量份、質量%。本發明 並不侷限於該等實施例。 Hereinafter, the present invention will be described in further detail by way of examples. The parts and % are not particularly limited, and represent parts by mass and mass%. this invention It is not limited to the embodiments.

實施例1 Example 1 <例1至19> <Examples 1 to 19>

例1至19中、例1至8、13至19是實施例，例9至12是比較例。 Examples 1 to 19, Examples 1 to 8, and 13 to 19 are examples, and Examples 9 to 12 are comparative examples.

在各例中使用的各成分是如下述。平均粒徑是指藉由雷射繞射法測定之體積基準的平均直徑。 The components used in each of the examples are as follows. The average particle diameter refers to the average diameter of the volume reference measured by the laser diffraction method.

a1：銀粒子(平均粒徑7.3μm) A1: Silver particles (average particle size 7.3 μm)

a2：銀粒子(平均粒徑8.3μm) A2: silver particles (average particle size 8.3 μm)

a3：氧化鋁填充劑銀鍍覆粒子(平均粒徑20μm，銀鍍覆厚度是0.1μm) A3: Alumina filler silver-plated particles (average particle size 20 μm, silver plating thickness 0.1 μm)

b1：雙酚F型環氧樹脂(環氧當量155至163g/eq) B1: bisphenol F type epoxy resin (epoxy equivalent 155 to 163 g/eq)

b2：雙酚A環氧丙烷加成物的聚縮水甘油基醚(環氧當量=320g/eq、羥基當量=1120) B2: polyglycidyl ether of bisphenol A propylene oxide adduct (epoxy equivalent = 320 g/eq, hydroxyl equivalent = 1120)

b3：環己烷二甲醇二縮水甘油基醚 B3: cyclohexane dimethanol diglycidyl ether

b4：新戊二醇二甲基丙烯酸酯 B4: neopentyl glycol dimethacrylate

b5：甘油二甲基丙烯酸酯 B5: glycerol dimethacrylate

c1：甲酚酚醛清漆樹脂(羥基當量=118g/eq軟化點105至115℃) C1: cresol novolac resin (hydroxy equivalent = 118 g / eq softening point 105 to 115 ° C)

c2：二氰基二醯胺 C2: dicyanodiamine

c3：Novacure HX3088(旭化成電子材料公司製，微膠囊化咪唑) C3: Novacure HX3088 (made by Asahi Kasei Electronic Materials Co., Ltd., microencapsulated imidazole)

c4：過氧化2-乙基己酸1,1,3,3-四甲基丁酯 C4: 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate

d1：2-乙基己酸鋅(鋅含量22質量%) D1: zinc 2-ethylhexanoate (zinc content 22% by mass)

d2：萘酸鈷(鈷含量8質量%) D2: cobalt naphthalate (cobalt content 8 mass%)

d3：雙(2-乙基己酸)鈷(II)(鈷含量8質量%) D3: bis(2-ethylhexanoic acid) cobalt (II) (cobalt content 8 mass%)

d4：2-乙基己酸 D4: 2-ethylhexanoic acid

d5：氧化鋅粒子(平均粒徑0.60μm) D5: zinc oxide particles (average particle diameter 0.60 μm)

d6：氧化銅(I)粒子(平均粒徑5μm) D6: copper (I) oxide particles (average particle size 5 μm)

d7：鋅粒子(平均粒徑3.7μm) D7: zinc particles (average particle size 3.7 μm)

d8：錫粒子(平均粒徑5μm) D8: tin particles (average particle size 5 μm)

d9：丙酸(沸點141℃) D9: propionic acid (boiling point 141 ° C)

e1：雙(三乙氧基矽烷基丙基)四硫化物 E1: bis(triethoxydecylpropyl) tetrasulfide

e2：4,4’-二胺基二苯基二硫化物 E2: 4,4'-diaminodiphenyl disulfide

f1：二丙烯酸鋅鹽(Sartomer公司製SR633) F1: zinc diacrylate (SR633, manufactured by Sartomer)

g1：3-縮水甘油氧基丙基三甲氧基矽烷 G1: 3-glycidoxypropyltrimethoxydecane

各個例子的樹脂組成物，係將表1及2的b1至b3混合，加熱到100℃之後，添加c1，加熱溶解後，冷卻到室溫為止，其次添加a1至a3以及c3至c4以外的成分，使用附攪拌翼之攪拌機均勻地混合。又，添加a1至a3，使用3輥分散機使之分散後，添加c3至c4，使用附攪拌翼之攪拌機使之均勻地混合而得到樹脂組成物。 The resin composition of each example is obtained by mixing b1 to b3 of Tables 1 and 2, heating to 100 ° C, adding c1, heating and dissolving, cooling to room temperature, and then adding components other than a1 to a3 and c3 to c4. Use a mixer with a stirring wing to mix evenly. Further, a1 to a3 were added, and after dispersing them using a 3-roll disperser, c3 to c4 were added, and the mixture was uniformly mixed using a stirrer with a stirring blade to obtain a resin composition.

對各個例子的樹脂組成物，進行以下的評估。將結果示於表1以及2中。 The resin composition of each example was subjected to the following evaluation. The results are shown in Tables 1 and 2.

1.晶片剪切強度 Wafer shear strength

吸濕處理前的晶片剪切強度是依下述順序進行。 The wafer shear strength before moisture absorption treatment was carried out in the following order.

將3mm×3mm的矽晶片，使用各個例子的樹脂組成物安裝在銅引線框架或是銀鍍覆銅框架上，由室溫到175℃ 為止昇溫30分鐘，在175℃維持30分鐘，使之接著硬化。對所得到的試料使用晶片剪切測試計(Dage公司製)，測定260℃之熱時晶片剪切強度。 A 3 mm × 3 mm tantalum wafer was mounted on a copper lead frame or a silver plated copper frame using the resin composition of each example, from room temperature to 175 ° C The temperature was raised for 30 minutes, maintained at 175 ° C for 30 minutes, and then hardened. A wafer shear tester (manufactured by Dage Co., Ltd.) was used for the obtained sample, and the wafer shear strength at a heat of 260 ° C was measured.

吸濕處理後的晶片剪切強度是依下述的順序(1)至(2)進行。 The wafer shear strength after moisture absorption treatment was carried out in the following order (1) to (2).

(1)將3mm×3mm的矽晶片，使用各個例子的樹脂組成物安裝在銅引線框架或是銀鍍覆銅框架上，由室溫到175℃為止昇溫30分鐘，在175℃維持30分鐘，使之接著硬化。 (1) A 3 mm × 3 mm tantalum wafer was mounted on a copper lead frame or a silver plated copper frame using a resin composition of each example, and the temperature was raised from room temperature to 175 ° C for 30 minutes and maintained at 175 ° C for 30 minutes. Let it harden.

(2)將得到之試料，在85℃/85%RH的恆溫槽中處理96小時後，迅速地用晶片剪切測試計(Dage公司製)測定260℃的熱時晶片剪切強度。 (2) The obtained sample was treated in a thermostat bath at 85 ° C / 85% RH for 96 hours, and then the wafer shear strength at 260 ° C was measured rapidly using a wafer shear tester (manufactured by Dage Co., Ltd.).

2.硬化後的孔洞 2. Hardened holes

將10mm×10mm的矽晶片，使用各個例子的樹脂組成物安裝在銅引線框架上，由室溫到175℃為止昇溫30分鐘，在175℃維持30分鐘，使之接著硬化。使用SONIX公司製的掃描型超音波顯微鏡觀察得到的試料，由得到的圖像求得孔洞的面積。相對於晶片面積的孔洞面積若未達10%則記成○，若為10%以上則記成×。 A 10 mm × 10 mm tantalum wafer was mounted on a copper lead frame using the resin composition of each example, and the temperature was raised from room temperature to 175 ° C for 30 minutes, and maintained at 175 ° C for 30 minutes, followed by hardening. The sample obtained was observed using a scanning ultrasonic microscope manufactured by SONIX Co., Ltd., and the area of the hole was obtained from the obtained image. If the area of the hole with respect to the area of the wafer is less than 10%, it is recorded as ○, and when it is 10% or more, it is recorded as ×.

3.硬化後的溶出 3. Dissolution after hardening

評估「2.硬化後的孔洞」之後，使用同一個試料，使用光學顯微鏡求得由位在矽晶片周圍之硬化物的最外周至在引線框架表面上滲出的異常部(溶出)之最外周為止的距離，將此距離當作溶出量。在表中記錄溶出量的最大值。 After evaluating "2. Holes after hardening", the same sample was used, and the outermost circumference of the cured product located around the tantalum wafer to the outermost periphery of the abnormal portion (dissolution) oozing on the surface of the lead frame was obtained by an optical microscope. The distance is taken as the amount of dissolution. The maximum amount of dissolution was recorded in the table.

依據對應實施例之例1至8、13至19之各 組成物，係對於銅以及銀之任一者，都可以發揮優良的接著強度，也可以抑制硬化後的孔洞之發生或在高溫製程的硬化物之剝離。 According to the examples 1 to 8, 13 to 19 of the corresponding embodiments The composition can exhibit excellent adhesion strength to either copper or silver, and can also prevent the occurrence of voids after hardening or the peeling of a cured product at a high temperature process.

<例20至42> <Examples 20 to 42>

例20至42之中，例20至26、32至42為實施例，例27至31為比較例。 Among Examples 20 to 42, Examples 20 to 26, 32 to 42 are examples, and Examples 27 to 31 are comparative examples.

實施例使用的各成分如以下所述。 The ingredients used in the examples are as follows.

a1’：銀粒子(平均粒徑7.3μm) A1': silver particles (average particle diameter 7.3 μm)

a2’：銀粒子(平均粒徑8.3μm) A2': silver particles (average particle size 8.3 μm)

a3’：氧化鋁填充劑銀鍍覆粒子(平均粒徑20μm，銀鍍覆厚度0.1μm) A3': alumina filler silver-plated particles (average particle diameter 20 μm, silver plating thickness 0.1 μm)

b1’：雙酚A環氧丙烷加成物的聚縮水甘油基醚(環氧當量=320g/eq，羥基當量=1120) B1': polyglycidyl ether of bisphenol A propylene oxide adduct (epoxy equivalent = 320 g/eq, hydroxyl equivalent = 1120)

b2’：環己烷二甲醇二縮水甘油基醚 B2': cyclohexane dimethanol diglycidyl ether

b3’：雙酚F型環氧樹脂(環氧當量155至163g/eq) B3': bisphenol F type epoxy resin (epoxy equivalent 155 to 163 g/eq)

b4’：新戊二醇二甲基丙烯酸酯 B4': neopentyl glycol dimethacrylate

b5’：N-丙烯醯氧基乙基六氫鄰苯二甲醯亞胺 B5': N-propylene methoxyethyl hexahydrophthalimide

c1’：甲酚酚醛清漆樹脂羥基當量=118g/eq軟化點105至115℃ C1': cresol novolac resin hydroxyl equivalent = 118 g / eq softening point 105 to 115 ° C

c2’：Novacure HX3088(旭化成電子材料公司製，微膠囊化咪唑) C2': Novacure HX3088 (made by Asahi Kasei Electronic Materials Co., Ltd., microencapsulated imidazole)

c3’：二氰基二醯胺 C3': dicyanodiamine

c4’：過氧化2-乙基己酸1,1,3,3-四甲基丁酯 C4': 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate

d1’：2-乙基己酸(沸點228℃) D1': 2-ethylhexanoic acid (boiling point 228 ° C)

d2’：氧化鋅粒子(平均粒徑0.60μm) D2': zinc oxide particles (average particle diameter 0.60 μm)

d3’：2-乙基己酸鋅(鋅含量22質量%) D3': zinc 2-ethylhexanoate (zinc content 22% by mass)

d4’：鋅粒子(平均粒子3.7μm) D4': zinc particles (average particles 3.7 μm)

d5’：萘酸鈷(鈷含量8質量%) D5': cobalt naphthalate (cobalt content 8 mass%)

d6’：雙(2-乙基己酸)鈷(II)(鈷含量8質量%) D6': bis(2-ethylhexanoic acid) cobalt (II) (cobalt content 8 mass%)

d7’：萘酸(沸點200℃以上) D7': naphthoic acid (boiling point above 200 ° C)

d8’：丙酸(沸點141℃) D8': propionic acid (boiling point 141 ° C)

e1’：2-巰基苯并咪唑 E1': 2-mercaptobenzimidazole

e2’：2,4,6-三巰基-均三 E2': 2,4,6-trisyl--three

e3’：二(十三基)-3,3’-硫代二丙酸酯 E3': di(tridecyl)-3,3'-thiodipropionate

f1’：2,2’-亞甲基雙(6-三級丁基-4-乙基-酚) F1': 2,2'-methylenebis(6-tributyl-4-ethyl-phenol)

f2’：N,N’-二-2-萘基-對-伸苯二胺 F2': N,N'-di-2-naphthyl-p-phenylene diamine

f3’：2,3-雙(3-(3,5-二-三級丁基-4-羥基苯基)丙醯基)丙醯肼 F3': 2,3-bis(3-(3,5-di-tri-butyl-4-hydroxyphenyl)propanyl)propanoid

f4’：十亞甲基二羧酸二水楊醯基醯肼 F4': decamethyldicarboxylic acid dihydrated hydrazine

g1’：3-縮水甘油基丙基三甲氧基矽烷 G1': 3-glycidylpropyltrimethoxydecane

g2’：雙(三乙氧基矽烷基丙基)四硫化物 G2': bis(triethoxydecylpropyl) tetrasulfide

各個例子的樹脂組成物，係將表1以及2的b1’至b3’混合，加熱到100℃之後，添加c1’，加熱溶解後，冷卻至室溫為止，其次，添加c2’、c4’以及a1’至a3’以外的成分，使用附攪拌翼的攪拌機均勻地混合。進一步，添加a1’至a3’，使用3輥分散機分散之後，添加c2’、c4’，使用附攪拌翼的攪拌機均勻地混合而得到樹脂組成物。 The resin composition of each example is obtained by mixing b1' to b3' of Tables 1 and 2, heating to 100 ° C, adding c1 ', heating and dissolving, cooling to room temperature, and then adding c2', c4' and The components other than a1' to a3' were uniformly mixed using a stirrer equipped with a stirring blade. Further, a1' to a3' were added, and after dispersing using a 3-roll disperser, c2' and c4' were added, and uniformly mixed with a stirrer equipped with a stirring blade to obtain a resin composition.

對各例的樹脂組成物進行以下的評估。將結果表示在表1以及2中。 The following evaluations were performed on the resin compositions of the respective examples. The results are shown in Tables 1 and 2.

1.吸濕高溫試驗後的剝離 1. Peeling after moisture absorption high temperature test

吸濕處理後曝露在高溫時發生的剝離之觀察，係依下述的順序(1)至(5)進行。 The observation of the peeling which occurred when the moisture absorption treatment was exposed to a high temperature was carried out in the following order (1) to (5).

(1)將3mm×3mm的矽晶片用實施例/比較例的各樹脂組成物安裝在銅引線框架上，由室溫昇175℃為止溫到30分鐘，在175℃維持30分鐘，使之接著硬化。 (1) A 3 mm × 3 mm tantalum wafer was mounted on a copper lead frame using the respective resin compositions of the examples and the comparative examples, and the temperature was raised from 175 ° C to 30 minutes at room temperature, and maintained at 175 ° C for 30 minutes, followed by hardening.

(2)認定其為被覆環氧模塑料(epoxy moulding compound)，藉由一般的環氧模塑料的硬化條件(175℃，4小時)，將已進行(1)的處理之試驗構件加熱。 (2) It was confirmed that it was a coated epoxy molding compound, and the test member which had been subjected to the treatment of (1) was heated by the curing conditions (175 ° C, 4 hours) of a general epoxy molding compound.

(3)將(2)的試驗構件在沸騰水中浸漬2小時。 (3) The test member of (2) was immersed in boiling water for 2 hours.

(4)將(3)的試驗構件在不乾燥狀態(水中)下冷卻到室溫為止。之後，將該試驗構件在回焊溫度(270℃)中加熱。 (4) The test member of (3) is cooled to room temperature in a non-dry state (in water). Thereafter, the test member was heated at a reflow temperature (270 ° C).

(5)使用SONIX公司製的掃描型超音波顯微鏡觀察(4)的試驗構件的剝離狀態，由得到的圖像求得相對於晶片面積之接著面積的比率。 (5) The peeling state of the test member of (4) was observed using a scanning ultrasonic microscope manufactured by SONIX Corporation, and the ratio of the area to the area of the wafer area was determined from the obtained image.

2.硬化後的孔洞 2. Hardened holes

將10mm×10mm的矽晶片使用實施例/比較例的各樹脂組成物安裝在銅引線框架上，由室溫到175℃為止昇溫30分鐘，在175℃中維持30分鑵，使之接著硬化。使用SONIX公司製的掃描型超音波顯微鏡觀察得到的試料，由得到的圖像求得孔洞的面積。相對於晶片的面積，若孔洞的面積未達10%則記成○，若為10%以上則記成×。 Each of the resin compositions of the examples and the comparative examples was mounted on a copper lead frame using a resin composition of 10 mm × 10 mm, and the temperature was raised from room temperature to 175 ° C for 30 minutes, and the can was maintained at 175 ° C for 30 minutes, and then hardened. The sample obtained was observed using a scanning ultrasonic microscope manufactured by SONIX Co., Ltd., and the area of the hole was obtained from the obtained image. The area of the wafer is recorded as ○ when the area of the hole is less than 10%, and is × when it is 10% or more.

相當於本發明的樹脂組成物的例20至26、32至42，係表現可抑制硬化後孔洞、且在吸濕高溫試驗後有良好的接著強度。另一方面，欠缺(D)以及(E’)成分的 例31，在吸濕高溫試驗後接著強度大幅降低，含有(D)但欠缺(E’)的例27、含有(F’)初級抗氧化劑取代(E’)之例28，含有(E’)但欠缺(D)的例29，也是在吸濕高溫試驗後接著強度會下降。(D)中，使用沸點為未達200℃的有機酸之丙酸的例30，係硬化後會產生孔洞，在吸濕高溫試驗後接著強度也會降低。 Examples 20 to 26 and 32 to 42 corresponding to the resin composition of the present invention exhibited that the pores after hardening were suppressed and had good adhesion strength after the moisture absorption high temperature test. On the other hand, lack of (D) and (E’) components In Example 31, after the moisture absorption high temperature test, the strength was greatly lowered, and Example 27 containing (D) but lacking (E') and Example 28 containing (F') primary antioxidant substitution (E') contained (E'). However, in Example 29, which lacks (D), the strength is also lowered after the moisture absorption high temperature test. In (D), in Example 30, which used propionic acid having an organic acid having a boiling point of less than 200 ° C, pores were formed after hardening, and the strength was also lowered after the moisture absorption high temperature test.

[產業上的可利用性] [Industrial availability]

依具本發明的話，可提供發揮優良的接著強度、抑制在高溫製程的硬化物之剝離、適合作為黏晶膠或放熱構件用接著劑的樹脂組成物。尤其，本發明的樹脂組成物的硬化物係抑制因吸濕造成的強度劣化，使用該等所製作的半導體裝置，係吸濕回流性優良、可靠度高。又，本發明的樹脂組成物即使在支撐構件是銅的情形下，也可以發揮該等的效果，有用性高。 According to the present invention, it is possible to provide a resin composition which exhibits excellent adhesion strength, suppresses peeling of a cured product at a high temperature process, and is suitable as an adhesive for a pressure-sensitive adhesive or a heat-releasing member. In particular, the cured product of the resin composition of the present invention suppresses deterioration of strength due to moisture absorption, and the semiconductor device produced by using the semiconductor device has excellent moisture absorption reflow property and high reliability. Moreover, even when the support member is copper, the resin composition of the present invention can exhibit the above effects and has high usefulness.

Claims (19)

一種樹脂組成物，係含有：(A)無機填充劑、(B)熱硬化性樹脂、(C)硬化劑、(D)(D1)沸點為200℃以上的有機酸之金屬鹽，以及/或是(D2)沸點為200℃以上的有機酸與金屬粒子及/或金屬氧化物粒子的組合、與(E)多硫化物。 A resin composition comprising: (A) an inorganic filler, (B) a thermosetting resin, (C) a curing agent, (D) (D1) a metal salt of an organic acid having a boiling point of 200 ° C or more, and/or (D2) A combination of an organic acid having a boiling point of 200 ° C or higher and metal particles and/or metal oxide particles, and (E) a polysulfide. 如申請專利範圍第1項所述之樹脂組成物，其中，(E)是具有選自雙硫鍵、三硫鍵、及四硫鍵所成群組中的鍵結之化合物。 The resin composition according to claim 1, wherein (E) is a compound having a bond selected from the group consisting of a disulfide bond, a trisulfide bond, and a tetrasulfide bond. 如申請專利範圍第2項所述之樹脂組成物，其中，(E)是具有多硫鍵之矽烷化合物及/或具有多硫鍵之胺化合物。 The resin composition according to claim 2, wherein (E) is a decane compound having a polysulfide bond and/or an amine compound having a polysulfide bond. 如申請專利範圍第1至3項中任一項所述之樹脂組成物，其中，相對於(A)至(E)的合計100質量份，(D)是0.05至5質量份；相對於(A)至(E)的合計100質量份，(E)換算成硫的量是0.02至2.0質量份。 The resin composition according to any one of claims 1 to 3, wherein (D) is 0.05 to 5 parts by mass with respect to 100 parts by mass of the total of (A) to (E); A total of 100 parts by mass of A) to (E), and the amount of (E) converted to sulfur is 0.02 to 2.0 parts by mass. 如申請專利範圍第1至4項中任一項所述之樹脂組成物，其復含有(F)(甲基)丙烯酸的金屬鹽。 The resin composition according to any one of claims 1 to 4, which further comprises (F) a metal salt of (meth)acrylic acid. 一種樹脂組成物，其係含有：(A)無機填充劑、(B)熱硬化性樹脂、 (C)硬化劑、(D)(D1)沸點是200℃以上的有機酸之金屬鹽，以及/或是(D2)沸點是200℃以上的有機酸與金屬粒子及/或金屬氧化物粒子的組合、與(E’)二級抗氧化劑。 A resin composition comprising: (A) an inorganic filler, (B) a thermosetting resin, (C) a hardener, (D) (D1) a metal salt of an organic acid having a boiling point of 200 ° C or higher, and/or (D2) an organic acid having a boiling point of 200 ° C or more and metal particles and/or metal oxide particles Combination, with (E') secondary antioxidant. 如申請專利範圍第6項所述之樹脂組成物，其中，(E’)是硫系二級抗氧化劑及/或磷系二級抗氧化劑。 The resin composition according to claim 6, wherein (E') is a sulfur-based secondary antioxidant and/or a phosphorus-based secondary antioxidant. 如申請專利範圍第7項所述之樹脂組成物，其中，(E’)是含有硫醇及/或硫醚之硫系二級抗氧化劑。 The resin composition according to claim 7, wherein (E') is a sulfur-based secondary antioxidant containing a mercaptan and/or a sulfide. 如申請專利範圍第6至8項中任一項所述之樹脂組成物，其復含有(F’)初級抗氧化劑。 The resin composition according to any one of claims 6 to 8, which further comprises (F') a primary antioxidant. 如申請專利範圍第6至9項中任一項所述之樹脂組成物，其中，相對於(A)至(D)以及(E’)的合計100質量份，(D)是0.1至5質量份；相對於(A)至(D)以及(E’)的合計100質量份，(E’)是0.03至5質量份。 The resin composition according to any one of claims 6 to 9, wherein (D) is 0.1 to 5 by mass based on 100 parts by mass of the total of (A) to (D) and (E') (E') is 0.03 to 5 parts by mass with respect to 100 parts by mass of the total of (A) to (D) and (E'). 如申請專利範圍第1至10項中任一項所述之樹脂組成物，其中，(A)是導電填充劑。 The resin composition according to any one of claims 1 to 10, wherein (A) is a conductive filler. 如申請專利範圍第11項所述之樹脂組成物，其中，(A)是選自銀、金、銅、鈀以及該等的合金所成群組中的粒子。 The resin composition according to claim 11, wherein (A) is a particle selected from the group consisting of silver, gold, copper, palladium, and the like. 如申請專利範圍第1至10項中任一項所述之樹脂組成物，其中，(A)是絶緣填充劑。 The resin composition according to any one of claims 1 to 10, wherein (A) is an insulating filler. 如申請專利範圍第1至13項中任一項所述之樹脂組成物，其中，(D1)是選自2-乙基己酸、萘酸以及環戊烷羧 酸所成群組中的有機酸之金屬鹽，(D2)是選自2-乙基己酸、萘酸以及環戊烷羧酸所成群組中的有機酸與金屬粒子及/或金屬氧化物粒子的組合。 The resin composition according to any one of claims 1 to 13, wherein (D1) is selected from the group consisting of 2-ethylhexanoic acid, naphthoic acid, and cyclopentane carboxylate. a metal salt of an organic acid in the group of acids, (D2) is an organic acid and metal particles and/or metal oxide selected from the group consisting of 2-ethylhexanoic acid, naphthoic acid, and cyclopentanecarboxylic acid. A combination of particles. 如申請專利範圍第14項之樹脂組成物，其中，(D1)的金屬鹽係選自鋅鹽、鈷鹽、鎳鹽、鎂鹽、錳鹽、以及錫鹽所成群組中的鹽，(D2)的金屬粒子及/或金屬氧化物粒子係選自鋅、鈷、鎳、鎂、錳、錫以及該等的氧化物所成群組中的粒子。 The resin composition of claim 14, wherein the metal salt of (D1) is selected from the group consisting of a zinc salt, a cobalt salt, a nickel salt, a magnesium salt, a manganese salt, and a tin salt; The metal particles and/or metal oxide particles of D2) are selected from the group consisting of zinc, cobalt, nickel, magnesium, manganese, tin, and oxides thereof. 一種黏晶膠，其係含有申請專利範圍第1至15項中任一項所述之樹脂組成物。 A viscous gel comprising the resin composition according to any one of claims 1 to 15. 一種放熱構件用接著劑，其係含有申請專利範圍第1至15項中任一項所述之樹脂組成物。 An adhesive for a heat releasing member, which comprises the resin composition according to any one of claims 1 to 15. 一種半導體裝置，其係使用申請專利範圍第16項所述之黏晶膠或申請專利範圍第17項所述的放熱構件用接著劑所製成。 A semiconductor device produced by using the adhesive of the above-mentioned Patent Application No. 16 or the adhesive for a heat-releasing member according to Item 17 of the patent application. 如申請專利範圍第18項所述之半導體裝置，其適合使用申請專利範圍第16項所述之黏晶膠或是申請專利範圍第17項所述的放熱構件用接著劑之表面為銅。 The semiconductor device according to claim 18, which is suitable for use as the adhesive of the adhesive of claim 16 or the adhesive for the heat release member according to claim 17 of the invention is copper.
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