TWI683872B - Resin composition - Google Patents

Resin composition Download PDF

Info

Publication number
TWI683872B
TWI683872B TW104132361A TW104132361A TWI683872B TW I683872 B TWI683872 B TW I683872B TW 104132361 A TW104132361 A TW 104132361A TW 104132361 A TW104132361 A TW 104132361A TW I683872 B TWI683872 B TW I683872B
Authority
TW
Taiwan
Prior art keywords
resin composition
meth
acid
patent application
item
Prior art date
Application number
TW104132361A
Other languages
Chinese (zh)
Other versions
TW201619325A (en
Inventor
水村宜司
深澤和樹
Original Assignee
日商納美仕有限公司
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
Application filed by 日商納美仕有限公司 filed Critical 日商納美仕有限公司
Publication of TW201619325A publication Critical patent/TW201619325A/en
Application granted granted Critical
Publication of TWI683872B publication Critical patent/TWI683872B/en

Links

Classifications

    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/38—Thiocarbonic acids; Derivatives thereof, e.g. xanthates ; i.e. compounds containing -X-C(=X)- groups, X being oxygen or sulfur, at least one X being sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of 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
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/495—Lead-frames or other flat leads
    • H01L23/49568—Lead-frames or other flat leads specifically adapted to facilitate heat dissipation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Die Bonding (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The resin composition of this invention is capable of maintaining a proper pot life and meanwhile maintaining conductivity of filler. The resin composition of this invention has an excellent adhesive strength. The resin composition of this invention is capable of suppressing stripping of cured article during high-temperature process. The resin composition of this invention is suitable for being used as die attach paste or adhesive agent for heat-dissipating member.
The resin composition of this invention contains (A) a filler having a conductive material on a surface of an insulating core material, (B) a thermal-setting resin, (C) a curing agent, and (D) a thioether compound. The present invention relates to a die attach paste or an adhesive agent for heat-dissipating member containing the resin composition. The present invention relates to a semiconductor device produce by using the die attach paste or the adhesive agent for heat-dissipating member.

Description

樹脂組成物 Resin composition

本發明係關於樹脂組成物、包含該樹脂組成物的黏晶膏(die attach paste)、以及包含該樹脂組成物的散熱構件用接著劑。又，本發明係關於使用黏晶膏或散熱構件用接著劑所製作的半導體裝置。 The present invention relates to a resin composition, a die attach paste containing the resin composition, and an adhesive for a heat dissipation member containing the resin composition. Moreover, this invention relates to the semiconductor device manufactured using the adhesive bond or the adhesive for heat dissipation members.

半導體裝置的製造中，為了使IC、LSI等與半導體元件與導線架等進行接著，係使用含有熱硬化性樹脂、硬化劑及無機填料之樹脂組成物。或者，為了使散熱構件與半導體元件、導線架等進行接著，係使用含有熱硬化性樹脂、硬化劑及無機填料之樹脂組成物(專利文獻1)。前者已知有黏晶膏。可使用黏晶膏接著半導體元件與支撐構件後，經由打線接合(wire bonding)以及密封的步驟而製造半導體裝置。半導體裝置可於印刷線路基板上進行焊接組裝。對於黏晶膏，係要求發揮優異的接著強度。特別是，要求黏晶膏於打線接合、迴焊之高溫製程中不會有硬化物的剝離。於是，為了防止硬化物的剝離，已知一種使用硫化合物，特別是使用硫醇系化合物之黏晶膏。 In the manufacture of semiconductor devices, in order to bond ICs, LSIs, etc. to semiconductor elements and lead frames, a resin composition containing a thermosetting resin, a curing agent, and an inorganic filler is used. Alternatively, in order to bond the heat dissipation member to the semiconductor element, lead frame, etc., a resin composition containing a thermosetting resin, a curing agent, and an inorganic filler is used (Patent Document 1). The former is known to have viscous crystal paste. After bonding the semiconductor element and the supporting member using the crystal paste, the semiconductor device can be manufactured through the steps of wire bonding and sealing. The semiconductor device can be soldered and assembled on the printed circuit board. For viscous crystal paste, it is required to exert excellent adhesive strength. In particular, it is required that there is no peeling of the hardened material during the high-temperature process of wire bonding and reflow. Therefore, in order to prevent peeling of the hardened material, a viscous crystal paste using a sulfur compound, particularly a thiol-based compound is known.

近年來，為了降低黏晶膏的製造成本，而 使用於絕緣性的芯材塗佈有導電性物質之填料(專利文獻2至5)。該填料被含有於黏晶膏所使用的樹脂組成物中。此種於絕緣性的芯材塗佈有導電性物質之填料，係有當位於表面的導電性物質被侵蝕則導電性下降之課題存在。 In recent years, in order to reduce the manufacturing cost A filler used for an insulating core material coated with a conductive substance (Patent Documents 2 to 5). This filler is contained in the resin composition used for the viscous crystal paste. Such a filler coated with an electrically conductive substance on an insulating core material has a problem that when the electrically conductive substance located on the surface is eroded, the conductivity decreases.

而且，會有因為了防止剝離而添加的硫醇系化合物而導致樹脂組成物的可使用時間(pot life)縮短之課題。 Furthermore, there is a problem that the pot life of the resin composition is shortened due to the thiol-based compound added to prevent peeling.

就半導體元件的支撐構件而言，以往係使用經施行鍍銀等貴金屬鍍覆之導線架、基板。近年來，為了降低製造成本而改成使用銅導線架、銅基板。 As a support member of a semiconductor element, in the past, a lead frame or a substrate plated with precious metal such as silver plating has been used. In recent years, in order to reduce manufacturing costs, copper lead frames and copper substrates have been used.

亦即，黏晶膏等所使用的樹脂組成物中，係要求有效地維持於絕緣性的芯材之表面塗佈有導電性物質之填料的導電性。而且，同時要求適度維持樹脂組成物的可使用時間。又且，要求對包含銅等的基板之接著性優異，同時於高溫製程中無硬化物的剝離。 That is, in the resin composition used for the crystal paste or the like, it is required to effectively maintain the conductivity of the filler coated with the conductive substance on the surface of the insulating core material. In addition, it is required to maintain the usable time of the resin composition at the same time. In addition, it is required to have excellent adhesion to substrates including copper and the like, and at the same time, there is no peeling of the hardened material in the high-temperature process.

[先前技術文獻] [Prior 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 Application Publication No. 2011-086669

[專利文獻2]日本特開2007-250540號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2007-250540

[專利文獻3]日本特開2006-249426號公報 [Patent Document 3] Japanese Unexamined Patent Publication No. 2006-249426

[專利文獻4]日本特開2009-256539號公報 [Patent Document 4] Japanese Patent Laid-Open No. 2009-256539

[專利文獻5]日本特開2002- 8443號公報 [Patent Document 5] Japanese Patent Application Publication No. 2002-8443

本發明係基於上述觀點而成者，目的係提供一種可有效地維持填料的導電性，且維持適度的可使用時間之樹脂組成物。而且，又一目的係提供一種對基板的接著強度優異，且在高溫製程中抑制硬化物的剝離之樹脂組成物。本發明可特別適合使用在支撐構件為銅、樹脂製的基板之情形。 The present invention is based on the above viewpoints, and an object thereof is to provide a resin composition that can effectively maintain the electrical conductivity of a filler and maintain an appropriate usable time. Furthermore, another object is to provide a resin composition which is excellent in adhesive strength to a substrate and suppresses peeling of a cured product in a high-temperature process. The present invention can be particularly suitably used when the supporting member is a copper or resin substrate.

本發明〔1〕係關於一種樹脂組成物，其係包含：(A)於絕緣性的芯材之表面具有導電性物質之填料、(B)熱硬化性樹脂、(C)硬化劑、以及(D)硫醚系化合物。 The present invention [1] relates to a resin composition comprising: (A) a filler having a conductive substance on the surface of an insulating core material, (B) a thermosetting resin, (C) a curing agent, and ( D) Thioether compounds.

本發明〔2〕係關於如本發明〔1〕所述之樹脂組成物，其中，(A)中之導電性物質係由銀、金、銅、鈀及此等的合金所組成群組中選出之至少1種導電性物質。 The present invention [2] relates to the resin composition according to the present invention [1], wherein the conductive substance in (A) is selected from the group consisting of silver, gold, copper, palladium, and these alloys At least one conductive substance.

本發明〔3〕係關於如本發明〔1〕或〔2〕所述之樹脂組成物，其中，(D)係具有二酯結構的硫醚系化合物及/或具有苯環的硫醚系化合物。 The present invention [3] relates to the resin composition according to the present invention [1] or [2], wherein (D) is a thioether compound having a diester structure and/or a thioether compound having a benzene ring .

本發明〔4〕係關於如本發明〔1〕至〔3〕中任一項所述之樹脂組成物，其更包含(E)(E1)沸點為200℃以上的有機酸之金屬鹽，及/或(E2)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。 The present invention [4] relates to the resin composition according to any one of [1] to [3] of the present invention, further comprising (E) (E1) a metal salt of an organic acid having a boiling point of 200° C. or higher, and And/or (E2) a combination of an organic acid having a boiling point of 200° C. or higher and metal particles and/or metal oxide particles.

本發明〔5〕係關於如本發明〔4〕所述之樹 脂組成物，其中，(E1)係由2-乙基己酸、環烷酸及環戊烷羧酸所組成群組中選出之有機酸的金屬鹽，(E2)係由2-乙基己酸、環烷酸及環戊烷羧酸所組成群組中選出之有機酸與金屬粒子及/或金屬氧化物粒子之組合。 The present invention [5] relates to the tree according to the present invention [4] Fat composition, wherein (E1) is a metal salt of an organic acid selected from the group consisting of 2-ethylhexanoic acid, naphthenic acid and cyclopentanecarboxylic acid, (E2) is a 2-ethylhexyl group A combination of organic acid and metal particles and/or metal oxide particles selected from the group consisting of acid, naphthenic acid and cyclopentanecarboxylic acid.

本發明〔6〕係關於如本發明〔5〕所述之樹脂組成物，其中，(E1)中之金屬鹽係由鋅鹽、鈷鹽、鎳鹽、鎂鹽、錳鹽及錫鹽所組成群組中選出之鹽， The present invention [6] relates to the resin composition according to the present invention [5], wherein the metal salt in (E1) is composed of zinc salt, cobalt salt, nickel salt, magnesium salt, manganese salt and tin salt The salt selected in the group,

(E2)中之金屬粒子及/或金屬氧化物粒子係由鋅、鈷、鎳、鎂、錳、錫及此等的氧化物所組成群組中選出之粒子。 The metal particles and/or metal oxide particles in (E2) are particles selected from the group consisting of zinc, cobalt, nickel, magnesium, manganese, tin, and these oxides.

本發明〔7〕係關於如本發明〔1〕至〔6〕中任一項所述之樹脂組成物，其中，相對於(A)至(C)的合計100質量份，(D)為0.05至1.5質量份。 The present invention [7] relates to the resin composition according to any one of the present invention [1] to [6], wherein (D) is 0.05 with respect to a total of 100 parts by mass of (A) to (C) To 1.5 parts by mass.

本發明〔8〕係關於如本發明〔4〕至〔7〕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，(E)為0.1至5質量份。 The present invention [8] relates to the resin composition according to any one of the present invention [4] to [7], wherein (E) is 0.1 with respect to a total of 100 parts by mass of (A) to (E) To 5 parts by mass.

本發明〔9〕係關於一種黏晶膏，其係包含本發明〔1〕至〔8〕中任一項所述之樹脂組成物。 The present invention [9] relates to a viscous crystal paste comprising the resin composition according to any one of the present invention [1] to [8].

本發明〔10〕係關於一種散熱構件用接著劑，其係包含本發明〔1〕至〔8〕中任一項所述之樹脂組成物。 The present invention [10] relates to an adhesive for a heat dissipating member, which comprises the resin composition according to any one of the present invention [1] to [8].

本發明〔11〕係關於一種半導體裝置，其係使用本發明〔9〕所述之黏晶膏、或本發明〔10〕所述之散熱構件用接著劑所製作者。 The present invention [11] relates to a semiconductor device manufactured by using the adhesive paste according to the present invention [9] or the adhesive for a heat dissipating member according to the present invention [10].

本發明〔12〕係關於如本發明〔11〕所述之 半導體裝置，其中，使用了本發明〔9〕所述之黏晶膏、或本發明〔10〕所述之散熱構件用接著劑的表面為銅。 The present invention [12] relates to the invention [11] A semiconductor device in which the surface of the adhesive for heat dissipation member according to the present invention [9] or the adhesive for a heat dissipating member according to the present invention [9] is copper.

本發明之樹脂組成物係包含(A)於絕緣性的芯材之表面具有導電性物質之填料、以及(D)硫醚系化合物。藉此，填料的表面之導電性物質不會被過度地硫化，因而可維持由樹脂組成物硬化而得之硬化物的導電性。 The resin composition of the present invention includes (A) a filler having a conductive substance on the surface of an insulating core material, and (D) a sulfide-based compound. As a result, the conductive material on the surface of the filler is not excessively vulcanized, so that the conductivity of the cured product obtained by curing the resin composition can be maintained.

而且，根據本發明之樹脂組成物，可分解於迴焊等的高溫製程所產生之過氧化氫。過氧化氫係促進硬化物的劣化之物質。所以，本發明之樹脂組成物因抑制了硬化物的劣化，故對支撐構件表面具有優異的接著性。 Furthermore, the resin composition of the present invention can decompose hydrogen peroxide generated in a high-temperature process such as reflow. Hydrogen peroxide is a substance that promotes the deterioration of hardened materials. Therefore, since the resin composition of the present invention suppresses the deterioration of the cured product, it has excellent adhesion to the surface of the support member.

而且，根據本發明之樹脂組成物，係抑制使樹脂組成物硬化而得之硬化物由支撐構件剝離。 Moreover, according to the resin composition of the present invention, the cured product obtained by curing the resin composition is suppressed from being peeled off by the support member.

而且，根據本發明之樹脂組成物，因使用(D)硫醚系化合物而產生結構位阻效應。藉此，抑制了對環氧樹脂等熱硬化性樹脂的反應，故可維持適度的可使用時間。 Furthermore, according to the resin composition of the present invention, the use of (D) a sulfide-based compound causes a structural steric effect. As a result, the reaction to thermosetting resins such as epoxy resins is suppressed, so that an appropriate use time can be maintained.

根據本發明之樹脂組成物，可得到：(1)可維持導電性、(2)可維持適度的可使用時間、(3)接著強度優異、以及(4)於高溫製程中可抑制硬化物的剝離等之效果。所以，本發明之樹脂組成物可適合使用於黏晶膏或散熱構件用接著劑。 According to the resin composition of the present invention, it is possible to obtain: (1) electrical conductivity can be maintained, (2) moderate usable time can be maintained, (3) excellent strength can be maintained, and (4) hardened material can be suppressed in a high-temperature process The effect of peeling etc. Therefore, the resin composition of the present invention can be suitably used as an adhesive for a crystal paste or a heat dissipation member.

特別是，本發明之樹脂組成物的硬化物抑制了因吸濕造成的強度劣化。所以，使用本發明之樹脂組成物所製作的半導體裝置係對吸濕迴焊的耐性優異，可靠 性高。又且，本發明之樹脂組成物即使在支撐構件為銅的情況下，亦可發揮此等效果，故實用性高。 In particular, the cured product of the resin composition of the present invention suppresses deterioration in strength due to moisture absorption. Therefore, the semiconductor device manufactured using the resin composition of the present invention is excellent in resistance to moisture reflow and reliable Sexuality is high. In addition, the resin composition of the present invention can exert such effects even when the supporting member is copper, and therefore has high practicality.

本發明之樹脂組成物係包含：(A)於絕緣性的芯材之表面具有導電性物質之填料、(B)熱硬化性樹脂、(C)硬化劑、以及(D)硫醚系化合物。 The resin composition of the present invention includes: (A) a filler having a conductive substance on the surface of an insulating core material, (B) a thermosetting resin, (C) a curing agent, and (D) a sulfide-based compound.

(A)於絕緣性的芯材之表面具有導電性物質之填料 (A) Filler with conductive substance on the surface of insulating core material

由本發明之樹脂組成物所成之硬化物的導電性，係藉由填料的表面之導電性物質而得。 The conductivity of the hardened product made of the resin composition of the present invention is obtained by the conductive material on the surface of the filler.

絕緣性的芯材之例，可列舉：氧化矽、氧化鋁、氧化鈦、氧化鋯、玻璃、碳化矽、氮化鋁及氮化硼的粒子。絕緣性的芯材較佳為氧化鋁或氧化矽的粒子。 Examples of insulating core materials include particles of silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, glass, silicon carbide, aluminum nitride, and boron nitride. The insulating core material is preferably particles of aluminum oxide or silicon oxide.

本發明之樹脂組成物所使用的填料，係於絕緣性的芯材之表面具有導電性物質。導電性物質較佳係被覆於芯材的表面。 The filler used in the resin composition of the present invention has a conductive substance on the surface of the insulating core material. The conductive substance is preferably coated on the surface of the core material.

導電性物質之例，可列舉標準電極電位為0V以上的金屬或此等的合金。藉由使用標準電極電位為0V以上的金屬，使因後述之(E)所包含的有機酸成分對(A)造成的影響變少。標準電極電位為0V以上的金屬之例， 可列舉：銀、金、銅及鈀。 Examples of the conductive material include metals or alloys having a standard electrode potential of 0 V or higher. By using a metal having a standard electrode potential of 0 V or more, the influence of (A), which is included in (E) described later, on (A) is reduced. Examples of metals with a standard electrode potential of 0V or more, Examples include silver, gold, copper and palladium.

導電性物質較佳係由銀、金、銅、鈀及此等的合金所組成群組中選出之至少1種。導電性物質較佳為銀或包含銀的合金。合金之例可列舉包含由銀、金、銅及鈀所選出之至少1種的合金。合金例如為包含銀及銅的合金、包含銀及錫的合金。 The conductive substance is preferably at least one selected from the group consisting of silver, gold, copper, palladium, and these alloys. The conductive substance is preferably silver or an alloy containing silver. Examples of alloys include alloys containing at least one selected from silver, gold, copper, and palladium. The alloy is, for example, an alloy containing silver and copper, and an alloy containing silver and tin.

於填料的芯材之表面可被覆導電性物質。導電性物質的被覆率並無特別限定，惟較佳係相對於填料全體100質量%為10至70質量%，更佳為20至60質量%。在此所稱之「導電性物質的被覆率」係意指相對於填料整體的質量之導電性物質的質量之比率。 The surface of the core material of the filler can be coated with a conductive substance. The coverage of the conductive material is not particularly limited, but it is preferably 10 to 70% by mass relative to 100% by mass of the entire filler, and more preferably 20 to 60% by mass. The "coverage rate of conductive material" referred to herein means the ratio of the mass of the conductive material relative to the mass of the entire filler.

填料的形狀並無特別限定。填料的形狀之例，可列舉：球狀、鱗片狀等。填料的形狀較佳為鱗片狀。 The shape of the filler is not particularly limited. Examples of the shape of the filler include spherical and scale-like shapes. The shape of the filler is preferably scaly.

填料的平均粒徑較佳為0.05至50μm，更佳為0.1至40μm，又更佳為0.5至25μm。在此，平均粒徑係意指由雷射繞射法所測定的體積基準之中位粒徑。 The average particle size of the filler is preferably 0.05 to 50 μm, more preferably 0.1 to 40 μm, and still more preferably 0.5 to 25 μm. Here, the average particle diameter means the volume-based median diameter measured by the laser diffraction method.

(A)可僅使用1種或併用2種以上。 (A) Only 1 type may be used or 2 or more types may be used together.

(B)熱硬化性樹脂 (B) Thermosetting resin

(B)熱硬化性樹脂並特別限定，惟較佳係在室溫(25℃)為液狀者。熱硬化性樹脂之例，可列舉：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 it is preferably a liquid at room temperature (25°C). Examples of thermosetting resins include epoxy resins, (meth)acrylic resins, and maleimide resins.

環氧樹脂係於分子內具有1個以上的縮水甘油基之化合物。環氧樹脂係可藉由加熱使縮水甘油基反應，形成3維的網狀結構並進行硬化之樹脂。就硬化物特 性的觀點來看，較佳係於1分子中含有2個以上縮水甘油基。 Epoxy resins are compounds that have more than one glycidyl group in the molecule. Epoxy resins are resins that can react with glycidyl groups by heating to form a three-dimensional network structure and harden them. Hardened From a sexual point of view, it is preferable to contain two or more glycidyl groups in one molecule.

環氧樹脂之例可列舉：雙酚A、雙酚F、聯苯酚等雙酚化合物或此等的衍生物(例如環氧烷加成物)，氫化雙酚A、氫化雙酚F、氫化聯苯酚、環己烷二醇、環己烷二甲醇、環己烷二乙醇等具有脂環結構的二醇或此等的衍生物，丁二醇、己二醇、辛二醇、壬二醇、癸二醇等脂肪族二醇或此等的衍生物等經環氧化之2官能性環氧樹脂；具有三羥基苯基甲烷骨架、胺基苯酚骨格之3官能性環氧樹脂；苯酚酚醛清漆樹脂、甲酚酚醛清漆樹脂、苯酚芳烷基樹脂、聯苯基芳烷基樹脂、萘酚芳烷基樹脂等經環氧化之多官能性環氧樹脂，惟不限定於此等。 Examples of the epoxy resin include bisphenol compounds such as bisphenol A, bisphenol F, and biphenol or derivatives thereof (for example, alkylene oxide adducts), hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated Glycols or derivatives of alicyclic structures such as phenol, cyclohexanediol, cyclohexanedimethanol, cyclohexanediethanol, etc., butanediol, hexanediol, octanediol, nonanediol, Epoxy-oxidized 2-functional epoxy resins such as decanediol and other derivatives; 3-functional epoxy resins with trihydroxyphenylmethane skeleton and aminophenol skeleton; phenol novolak resin , Cresol novolak resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin and other epoxidized multifunctional epoxy resins, but not limited to these.

環氧樹脂較佳係在室溫(25℃)為液狀者。環氧樹脂在單獨或混合物的狀態下，以在室溫為液狀者為較佳。亦可使用反應性的稀釋劑使環氧樹脂成為液狀。反應性稀釋劑之例，可列舉：苯基縮水甘油醚、甲苯酚基縮水甘油醚等1官能的芳香族縮水甘油醚類、脂肪族縮水甘油醚類等。 The epoxy resin is preferably liquid at room temperature (25°C). In the state of the epoxy resin alone or in a mixture, it is preferably liquid at room temperature. A reactive diluent can also be used to make the epoxy resin liquid. Examples of the reactive diluent include monofunctional aromatic glycidyl ethers such as phenyl glycidyl ether and cresyl glycidyl ether, and aliphatic glycidyl ethers.

熱硬化性樹脂可使用(甲基)丙烯酸樹脂。(甲基)丙烯酸樹脂可為於分子內具有(甲基)丙烯醯基的化合物。(甲基)丙烯酸樹脂係可藉由使(甲基)丙烯醯基反應而形成3維網狀結構，並進行硬化。(甲基)丙烯酸樹脂之例可列舉：(甲基)丙烯酸甲酯、(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)丙烯酸第三丁 酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十三基酯、(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)丙烯酸二十二基酯、(甲基)丙烯酸-2-乙基己酯、其他的(甲基)丙烯酸烷酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸異莰酯、(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、(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、甲氧基聚伸烷二醇單(甲基)丙烯酸酯、辛氧基聚伸烷二醇單(甲基)丙烯酸酯、月桂氧基聚伸烷二醇單(甲基)丙烯酸酯、硬脂氧基聚伸烷二醇單(甲基)丙烯酸酯、烯丙氧基聚伸烷二醇單(甲基)丙烯酸酯、壬基苯氧基聚伸烷二醇單(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。亦可使用N,N’-亞甲基雙(甲基)丙烯醯胺、N,N’-伸乙基雙(甲基)丙烯醯胺、1,2-二(甲基)丙烯醯胺乙二醇的(甲基)丙烯醯胺。亦可使用正乙烯基-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, (meth)acrylic resin can be used. The (meth)acrylic resin may be a compound having a (meth)acryloyl group in the molecule. The (meth)acrylic resin system can form a three-dimensional network structure by reacting the (meth)acryloyl group and harden it. Examples of (meth)acrylic resins include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylic acid Third Ester, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, (meth) ) Isoamyl acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, other alkyl (meth) acrylates, Cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate Ester, isobornyl (meth)acrylate, glycidyl (meth)acrylate, trimethylolpropane tri(meth)acrylate, zinc mono(meth)acrylate, zinc di(meth)acrylate, ( Dimethylaminoethyl meth)acrylate, diethylaminoethyl (meth)acrylate, neopentyl glycol (meth)acrylate, trifluoroethyl (meth)acrylate, (meth) Acrylic acid-2,2,3,3-tetrafluoropropyl ester, (meth)acrylic acid-2,2,3,3,4,4-hexafluorobutyl ester, (meth)acrylic acid perfluorooctyl ester, (meth Group) Perfluorooctyl ethyl acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexane Glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,10-decanediol di(meth) Group) acrylate, tetramethylene glycol di(meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (methyl ) Acrylate, methoxypolyalkylene glycol mono(meth)acrylate, octoxypolyalkylene glycol mono(meth)acrylate, lauryloxypolyalkylene glycol mono(meth)acrylic acid Ester, stearyloxypolyalkylene glycol mono(meth)acrylate, allyloxypolyalkylene glycol mono(meth)acrylate, nonylphenoxypolyalkylene glycol mono(meth)acrylate ) Acrylate, di(meth)acryloxymethyltricyclodecane, N-(meth)acryloxyethylmaleic Acetyleneimide, N-(meth)acryloyloxyethyl hexahydrophthalimide, N-(meth)acryloyloxyethylphthalimide. N,N'-methylenebis(meth)acrylamide, N,N'-ethylidenebis(meth)acrylamide, 1,2-di(meth)acrylamide ethyl can also be used Glycol (meth)acrylamide. Vinyl compounds such as n-vinyl-2-pyrrolidone, styrene derivatives, and α-methylstyrene derivatives can also be used.

(甲基)丙烯酸樹脂可使用聚(甲基)丙烯酸酯。聚(甲基)丙烯酸酯較佳為(甲基)丙烯酸與(甲基)丙烯酸酯之共聚物、或具有羥基的(甲基)丙烯酸酯與不具極性基的(甲基)丙烯酸酯之共聚物等。 As the (meth)acrylic resin, poly(meth)acrylate can be used. The poly(meth)acrylate is preferably a copolymer of (meth)acrylic acid and (meth)acrylate, or a copolymer of a (meth)acrylate having a hydroxyl group and a (meth)acrylate having no polar group Wait.

(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-環己烷二醇單(甲基)丙烯酸酯、1,3-環己烷二醇單(甲基)丙烯酸酯、1,4-環己烷二醇單(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、單(甲基)丙烯酸甘油酯、二(甲基)丙烯酸甘油酯、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、新戊四醇單(甲基)丙烯酸酯、新戊四醇二(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊二醇單(甲基)丙烯酸酯等具有羥基的(甲基)丙烯酸 酯，此等具有羥基的(甲基)丙烯酸酯與二羧酸或其衍生物反應而得之具有羧基的(甲基)丙烯酸酯等。在此可使用的二羧酸可列舉例如：乙二酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、順丁烯二酸、反丁烯二酸、鄰苯二甲酸、四氫鄰苯二甲酸、六氫鄰苯二甲酸及此等的衍生物。 (Meth)acrylic resin can also be used, for example: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth ) 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,2-cyclohexanediol mono(meth)acrylate, 1,3-cyclohexanediol mono(meth)acrylate, 1,4-cyclohexanediol mono(meth)acrylate, 1,2-cyclohexanedimethanol mono(meth)acrylate , 1,3-cyclohexane dimethanol mono(meth)acrylate, 1,4-cyclohexane dimethanol mono(meth)acrylate, 1,2-cyclohexane diethanol mono(meth)acrylic acid Ester, 1,3-cyclohexanediethanol mono(meth)acrylate, 1,4-cyclohexanediethanol mono(meth)acrylate, glycerol mono(meth)acrylate, di(meth) Glycerol acrylate, trimethylolpropane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, neopentyl alcohol mono(meth)acrylate, neopentyl alcohol di(meth)acrylate ) Acrylic acid ester, neopentyl alcohol tri (meth) acrylate, neopentyl glycol mono (meth) acrylate and other (meth) acrylic acid with hydroxyl group Ester, these (meth)acrylates with hydroxyl groups and dicarboxylic acids or their derivatives are obtained by reacting with carboxyl groups (meth)acrylates. Examples of the dicarboxylic acid that can be used here include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and cis-butyric acid. Adipic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and derivatives thereof.

熱硬化性樹脂可使用馬來醯亞胺樹脂。馬來醯亞胺樹脂係於1分子內包含1個以上的馬來醯亞胺基之化合物。馬來醯亞胺樹脂可藉由加熱使馬來醯亞胺基反應而形成3維的網狀結構，並進行硬化。馬來醯亞胺樹脂之例可列舉：N,N’-(4,4’-二苯基甲烷)雙馬來醯亞胺、雙(3-乙基-5-甲基-4-馬來醯亞胺基苯基)甲烷、2,2-雙[4-(4-馬來醯亞胺基苯氧基)苯基]丙烷等雙馬來醯亞胺樹脂。更佳的馬來醯亞胺樹脂係：藉由二體酸二胺與順丁烯二酸酐的反應而得之化合物，藉由所謂馬來醯亞胺乙酸、馬來醯亞胺己酸之馬來醯亞胺化胺基酸與多元醇的反應而得之化合物。馬來醯亞胺化胺基酸係藉由使馬來酸酐與胺基乙酸或胺基己酸反應而得。多元醇較佳為聚醚多元醇、聚酯多元醇、聚碳酸酯多元醇、聚(甲基)丙烯酸酯多元醇，特佳為不含芳香族環者。馬來醯亞胺基因可與烯丙基反應，故以與烯丙基酯樹脂併用為較佳。烯丙基酯樹脂較佳為脂肪族者，其中，特佳者係藉由環己烷二烯丙基酯與脂肪族多元醇的酯交換而得之化合物。 As the thermosetting resin, maleimide resin can be used. Maleimide resin is a compound containing more than one maleimide group in one molecule. The maleimide resin can react with maleimide groups by heating to form a three-dimensional network structure and harden it. Examples of maleimide resins include N,N'-(4,4'-diphenylmethane) bismaleimide and bis(3-ethyl-5-methyl-4-male Bismaleimide resins such as amidimidophenyl)methane and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane. Better maleimide resin: a compound obtained by the reaction of diacid diamine and maleic anhydride, by the so-called maleimide acetic acid, maleimide caproic acid A compound derived from the reaction of imidate amino acids with polyols. Maleimide imidized amino acids are obtained by reacting maleic anhydride with aminoacetic acid or aminohexanoic acid. The polyol is preferably a polyether polyol, a polyester polyol, a polycarbonate polyol, a poly(meth)acrylate polyol, particularly preferably an aromatic ring-free one. The maleimide gene can react with allyl groups, so it is better to use it together with allyl ester resin. The allyl ester resin is preferably an aliphatic one. Among them, the most preferable one is a compound obtained by transesterification of cyclohexane diallyl ester and an aliphatic polyhydric alcohol.

(C)硬化劑 (C) Hardener

本發明之樹脂組成物係包含硬化劑。硬化劑之例可列舉：脂肪族胺、芳香族胺、二氰二胺(dicyandiamide)、二醯肼化合物、酸酐、苯酚樹脂等。熱硬化性樹脂係使用環氧樹脂時，可適合使用此等硬化劑。 The resin composition of the present invention contains a hardener. Examples of the curing agent include aliphatic amines, aromatic amines, dicyandiamide (dicyandiamide), dihydrazine compounds, acid anhydrides, phenol resins, and the like. When an epoxy resin is used for the thermosetting resin system, these hardeners can be suitably used.

脂肪族胺之例可列舉：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、降莰烯二胺、1,2-二胺基環己烷等脂環式多元胺，N-胺基乙基哌

Figure 104132361-A0202-12-0012-4
、1,4-雙(2-胺基-2-甲基丙基)哌
Figure 104132361-A0202-12-0012-5
等哌
Figure 104132361-A0202-12-0012-6
型多元胺。芳香族胺之例可列舉：二胺基二苯基甲烷、間伸苯基二胺、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)、聚氧化四亞甲基二醇-二-對胺基苯甲酸酯等芳香族多元胺等。 Examples of aliphatic amines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, trimethylhexamethylenediamine, m-xylenediamine, 2-methylpentamethylene Aliphatic polyamines such as diamine, isophorone diamine, 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornene diamine, 1,2-diamine Cycloaliphatic polyamines such as cyclohexane, N-aminoethylpiper
Figure 104132361-A0202-12-0012-4
, 1,4-bis(2-amino-2-methylpropyl)piper
Figure 104132361-A0202-12-0012-5
Isopiper
Figure 104132361-A0202-12-0012-6
Type polyamine. Examples of aromatic amines include: diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis(4-aminobenzoic acid) Ester), aromatic polyamines such as polyoxytetramethylene glycol-di-p-aminobenzoate and the like.

二醯肼化合物之例可列舉：己二酸二醯肼、十二酸二醯肼、間苯二甲酸二醯肼、對羥基苯甲酸二醯肼等羧酸二醯肼等。酸酐之例可列舉：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、十二烯基丁二酸酐、順丁烯二酸酐與聚丁二烯的反應物、順丁烯二酸酐與苯乙烯的共聚物等。就硬化物特性的觀點來看，苯酚樹脂可使用於1分子內具有2個以上的酚性羥基之化合物。較佳的酚性羥基之數量為2至5。若酚性羥基的數量若於此範圍內，就可將樹脂組成物的黏度控制在適當的範圍內。更佳的1分子內之酚性羥基的數量為2個 或3個。此種化合物之例可列舉：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、二羥基二苯基酮、四甲基聯苯酚、亞乙基雙酚、甲基亞乙基雙(甲基苯酚)、亞環己基雙酚、聯苯酚等雙酚類及其衍生物、三(羥基苯基)甲烷、三(羥基苯基)乙烷等3官能的苯酚類及其衍生物、苯酚酚醛清漆、甲酚酚醛清漆等使苯酚類與甲醛反應而得之化合物且主要為雙核體或三核體者及其衍生物等。 Examples of dihydrazide compounds include dihydrazide adipic acid dihydrazide, dodecanoic acid dihydrazide, isophthalic acid dihydrazide, p-hydroxybenzoic acid dihydrazide and the like. Examples of acid anhydrides include: phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, internal methylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, cis The reactant of dianhydride and polybutadiene, the copolymer of maleic anhydride and styrene, etc. From the viewpoint of the characteristics of the cured product, the phenol resin can be used for compounds having two or more phenolic hydroxyl groups in one molecule. The preferred number of phenolic hydroxyl groups is 2 to 5. If the number of phenolic hydroxyl groups 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 1 molecule is 2 Or three. Examples of such compounds include: bisphenol F, bisphenol A, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol S, dihydroxydiphenyl ether, dihydroxy Diphenyl ketone, tetramethyl biphenol, ethylene bisphenol, methyl ethylene bis (methyl phenol), cyclohexyl bisphenol, biphenol and other bisphenols and their derivatives, tri (hydroxybenzene Group) Methane, tris (hydroxyphenyl) ethane and other trifunctional phenols and their derivatives, phenol novolak, cresol novolak and other compounds obtained by reacting phenols with formaldehyde and are mainly dinuclear or trinuclear The body and its derivatives.

硬化劑可使用熱自由基聚合起始劑等聚合起始劑。熱硬化性樹脂係使用(甲基)丙烯酸樹脂時，可適合使用此種硬化劑。聚合起始劑可使用公知者。熱自由基聚合起始劑的具體例可列舉：甲基乙基酮過氧化物、甲基環己酮過氧化物、乙醯乙酸甲酯過氧化物、乙醯丙酮過氧化物、1,1-雙(過氧化第三丁基)3,3,5-三甲基環己烷、1,1-雙(過氧化第三丁基)環己烷、1,1-雙(過氧化第三丁基)3,3,5-三甲基環己烷、1,1-雙(過氧化第三丁基)環己烷、2,2-雙(4,4-二-第三丁基過氧化環己基)丙烷、1,1-雙(過氧化第三丁基)環十二烷、正丁基4,4-雙(過氧化第三丁基)戊酸酯、2,2-雙(過氧化第三丁基)丁烷、1,1-雙(過氧化第三丁基)-2-甲基環己烷、第三丁基過氧化氫、對薄荷烷過氧化氫、1,1,3,3-四甲基丁基過氧化氫、第三己基過氧化氫、二異丙苯基過氧化物、2,5-二甲基-2,5-雙(過氧化第三丁基)己烷、α,α’-雙(過氧化第三丁基)二異丙基苯、第三丁基異丙苯基過氧化物、二-第三丁基過氧化物、2,5-二甲基-2,5-雙(過氧化第 三丁基)己炔-3、異丁醯基過氧化物、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、肉桂酸過氧化物、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-第三丁基環己基)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-第二丁酯、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-第三丁基環己基)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、過氧化新癸酸第三己酯、過氧化新癸酸第三丁酯、過氧化特戊酸第三己酯、過氧化特戊酸第三丁酯、2,5-二甲基-2,5-雙(過氧化2-乙基己醯基)己烷、1,1,3,3-四甲基丁基過氧化-2-乙基己酸酯、1-環己基-1-甲基乙基過氧化-2-乙基己酸酯、過氧化-2-乙基己酸第三丁酯、過氧化-2-乙基己酸第三丁酯、過氧化異丁酸第三丁酯、過氧化順丁烯二酸第三丁酯、過氧化月桂酸第三丁酯、過氧化-3,5,5-三甲基己酸第三丁酯、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、2,5-二甲基-2,5-雙(過氧化苯甲醯基)己烷、過氧化乙酸第三丁酯、過氧化苯甲酸第三丁酯、過氧化-間甲苯甲醯基苯甲酸第三丁酯、過氧化苯甲酸第三丁酯、雙(過氧化第三丁基)間苯二甲酸酯、過氧化烯丙基單碳酸第三丁酯、3,3’,4,4’-四(第三丁基過氧化羰基)二苯基酮等。此等可僅使用1種或併用2種以上。 As the hardener, a polymerization initiator such as a thermal radical polymerization initiator can be used. When a (meth)acrylic resin is used as the thermosetting resin system, such a curing agent can be suitably used. As the polymerization initiator, a known one can be used. Specific examples of the thermal radical polymerization initiator include: methyl ethyl ketone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetone acetone peroxide, 1,1 -Bis (third butyl peroxide) 3,3,5-trimethylcyclohexane, 1,1-bis (third butyl peroxide) cyclohexane, 1,1-bis (third peroxide) Butyl) 3,3,5-trimethylcyclohexane, 1,1-bis (third butyl peroxide) cyclohexane, 2,2-bis (4,4-di-third butyl peroxide Cyclohexyl oxide) propane, 1,1-bis (third butyl peroxide) cyclododecane, n-butyl 4,4-bis (third butyl peroxide) valerate, 2,2-bis( Third butyl peroxide) butane, 1,1-bis(third butyl peroxide)-2-methylcyclohexane, third butyl hydrogen peroxide, p-menthane hydrogen peroxide, 1,1 ,3,3-tetramethylbutyl hydroperoxide, third hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (third butyl peroxide ) Hexane, α,α'-bis (third butyl peroxide) diisopropylbenzene, third butyl cumyl peroxide, di-third butyl peroxide, 2,5- Dimethyl-2,5-bis(peroxide Tributyl)hexyne-3, isobutylamide peroxide, 3,5,5-trimethylhexyl peroxide, octyl peroxide, lauryl peroxide, cinnamic acid peroxide, meta Toluoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, bis(4-third butylcyclohexyl) peroxydicarbonate, di-3-peroxydicarbonate Methoxybutyl ester, di-2-ethylhexyl peroxydicarbonate, di-second butyl peroxydicarbonate, bis(3-methyl-3-methoxybutyl) peroxydicarbonate , Di(4-tert-butylcyclohexyl) peroxydicarbonate, α,α'-bis(neodecanoyl peroxide) diisopropylbenzene, cumene peroxyneodecanoate, peroxide Neodecanoic acid 1,1,3,3,-tetramethylbutyl ester, neodecanoic acid 1-cyclohexyl-1-methyl ethyl ester, neodecanoic acid third hexyl ester, neodecanoic acid peroxide Third butyl ester, third hexyl peroxypivalate, third butyl pervalerate, 2,5-dimethyl-2,5-bis(2-ethylhexyl peroxide) Alkanes, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, peroxy Tert-Butyl-2-ethylhexanoate, tert-butyl 2-ethylhexanoate, tert-butyl isobutyrate, tert-butyl maleate, peroxide Third butyl laurate, third butyl peroxy-3,5,5-trimethylhexanoate, third butyl peroxyisopropyl monocarbonate, third butyl peroxy-2-ethylhexyl monocarbonate Butyl ester, 2,5-dimethyl-2,5-bis(benzyl peroxide) hexane, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, m-toluene peroxide Tertiary butyl benzoate, tertiary butyl peroxybenzoate, bis(tertiary butyl peroxide) isophthalate, tertiary butyl peroxy monocarbonate, 3,3' , 4,4'-tetrakis(third butyl peroxycarbonyl) diphenyl ketone, etc. Only one type may be used or two or more types may be used in combination.

本發明之樹脂組成物可包含硬化促進劑。熱硬化性樹脂係使用環氧樹脂時，硬化促進劑之例可列舉：咪唑類、三苯基膦或四苯基膦的鹽類等。此等之中，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

Figure 104132361-A0202-12-0015-7
之加成物等咪唑化合物。亦可使用改質咪唑化合物。例如可使用環氧基-咪唑加成系化合物、丙烯酸酯-咪唑加成化合物。市售的環氧基-咪唑加成系化合物可列舉例如：Ajinomoto Fine-Techno公司製的「Ajicure PN-23」、同公司製的「Ajicure PN-40」、旭化成公司製的「Novacure HX-3721」、富士化成工業公司製的「Fujicure FX-1000」等。市售的丙烯酸酯-咪唑加成系化合物可列舉例如：ADEKA公司製的「EH2021」等。亦可使用旭化成公司製的「Novacure HX-3088」。 The resin composition of the present invention may contain a hardening accelerator. When an epoxy resin is used as the thermosetting resin, examples of the curing accelerator include imidazoles, triphenylphosphine, or tetraphenylphosphine salts. Among these, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxyl are preferred Methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-C 11 H 23 -imidazole, 2-methylimidazole and 2,4-diamino-6-vinyl tri
Figure 104132361-A0202-12-0015-7
The adducts and other imidazole compounds. Modified imidazole compounds can also be used. For example, an epoxy-imidazole addition compound or an acrylate-imidazole addition compound can be used. Examples of commercially available epoxy-imidazole addition compounds include "Ajicure PN-23" manufactured by Ajinomoto Fine-Techno Corporation, "Ajicure PN-40" manufactured by the same company, and "Novacure HX-3721" manufactured by Asahi Kasei Corporation. ", "Fujicure FX-1000" manufactured by Fuji Chemical Industries, Ltd. Examples of commercially available acrylate-imidazole addition-based compounds include "EH2021" manufactured by ADEKA Corporation. "Novacure HX-3088" manufactured by Asahi Kasei Corporation can also be used.

(B)較佳為環氧樹脂及/或(甲基)丙烯酸樹脂。特佳是併用環氧樹脂與(甲基)丙烯酸樹脂。此時，環氧樹脂與(甲基)丙烯酸樹脂的使用量以質量比例(環氧樹脂：(甲基)丙烯酸樹脂)表示，較佳為95：5至40：60，更佳為90：10至51：49。如此併用環氧樹脂與(甲基)丙烯酸樹脂時，(C)較佳係併用環氧樹脂用的硬化劑與熱自由基聚合起始劑。 (B) is preferably epoxy resin and/or (meth)acrylic resin. Especially good is to use epoxy resin and (meth)acrylic resin together. At this time, the amount of epoxy resin and (meth)acrylic resin used is expressed by mass ratio (epoxy resin: (meth)acrylic resin), preferably 95:5 to 40:60, more preferably 90:10 To 51:49. When using epoxy resin and (meth)acrylic resin together, (C) preferably uses a hardener for epoxy resin and a thermal radical polymerization initiator together.

(D)硫醚系化合物 (D) Thioether compounds

硫醚系化合物較佳為二次抗氧化劑。抗氧化劑一般分 類為一次抗氧化劑(自由基補足劑)與二次抗氧化劑(過氧化物分解劑)。 The thioether-based compound is preferably a secondary antioxidant. Antioxidant general points Classes are primary antioxidants (radical supplements) and secondary antioxidants (peroxide decomposers).

根據本發明之樹脂組成物，係使用(D)硫醚系化合物，藉此使被覆於填料的表面之導電性物質不會過度地硫化，而可維持由樹脂組成物硬化的硬化物之導電性。 According to the resin composition of the present invention, the (D) sulfide-based compound is used, so that the conductive substance coated on the surface of the filler is not excessively vulcanized, and the conductivity of the cured product hardened by the resin composition can be maintained .

又，根據本發明之樹脂組成物，係使用(D)硫醚系化合物，藉此可分解於迴焊等高溫製程所產生之過氧化氫。過氧化氫為促進硬化物的劣化之物質。所以，本發明之樹脂組成物因抑制了硬化物的劣化，故對支撐構件表面具有優異的接著性。 In addition, according to the resin composition of the present invention, (D) a sulfide-based compound is used, whereby hydrogen peroxide generated in a high-temperature process such as reflow can be decomposed. Hydrogen peroxide is a substance that promotes the deterioration of hardened materials. Therefore, since the resin composition of the present invention suppresses the deterioration of the cured product, it has excellent adhesion to the surface of the support member.

而且，根據本發明之樹脂組成物，因使用(D)硫醚系化合物而產生結構立體效應。藉此，抑制了對環氧樹脂等熱硬化性樹脂的反應，故可維持適度的可使用時間。 Furthermore, according to the resin composition of the present invention, the use of (D) a thioether-based compound produces a structural stereoscopic effect. As a result, the reaction to thermosetting resins such as epoxy resins is suppressed, so that an appropriate use time can be maintained.

硫醚系化合物的具體例可列舉：3,3’-硫代二丙酸二月桂酯、3,3’-硫代二丙酸二肉豆蔻酯、3,3’-硫代二丙酸二硬脂酯、3,3’-硫代二丙酸二(十三基)酯等具有二酯結構之硫醚系化合物；如雙(3,5-二-第三丁基-4-羥基苯甲基)硫化物之具有苯環之硫醚系化合物等。此等的硫醚系化合物可僅使用1種或併用2種以上。 Specific examples of the thioether-based compound include: 3,3'-dilauric thiodipropionate, 3,3'-dimyristyl thiodipropionate, 3,3'-thiodipropionate Thioether compounds with diester structure such as stearyl ester, 3,3'-thiodipropionate di(tridecyl) ester; such as bis(3,5-di-tert-butyl-4-hydroxybenzene Thioether compounds having a benzene ring such as methyl) sulfide. These thioether compounds can be used alone or in combination of two or more.

硫醚系化合物較佳係由3,3’-硫代二丙酸二月桂酯、3,3’-硫代二丙酸二肉豆蔻酯、3,3’-硫代二丙酸二硬脂酯、3,3’-硫代二丙酸二(十三基)酯及雙(3,5-二-第三丁基-4-羥基苯甲基)硫化物所組成群組中選出之至少1種硫醚系化合物。 The thioether-based compound is preferably composed of 3,3'-thiodipropionate dilauryl ester, 3,3'-thiodipropionate dimyristate, 3,3'-thiodipropionate distearate At least one selected from the group consisting of esters, di(tridecyl) 3,3'-thiodipropionate and bis(3,5-di-third-butyl-4-hydroxybenzyl) sulfide 1 thioether compound.

(E)(E1)沸點為200℃以上的有機酸之金屬鹽及/或(E2)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 (E) (E1) Metal salts of organic acids with a boiling point above 200°C and/or (E2) Combinations of organic acids with a boiling point above 200°C and metal particles and/or metal oxide particles

(E1)沸點為200℃以上的有機酸之金屬鹽中之有機酸，其沸點為200℃以上。有機酸例如係沸點為200至300℃者。藉由使用沸點為200℃以上的有機酸，可抑制在加熱硬化步驟產生的空隙(void)。沸點為在大氣壓下的數值。 (E1) The organic acid in the metal salt of an organic acid having a boiling point of 200°C or higher has a boiling point of 200°C or higher. Organic acids are, for example, those with a boiling point of 200 to 300°C. By using an organic acid having a boiling point of 200° C. or higher, voids generated in the heat hardening step can be suppressed. The boiling point is the value at atmospheric pressure.

本發明之樹脂組成物表現優異的接著強度，且抑制在高溫製程中硬化物的剝離。根據本發明之樹脂組成物，係使用(D)硫醚系化合物，藉此可將能促進硬化物的劣化之過氧化氫分解。藉由分解過氧化氫，可抑制樹脂組成物硬化後之硬化物的劣化。就其結果而言，本發明之樹脂組成物係對支撐構件表面發揮優異的接著性。在此，於支撐構件表面存在有銅時，(D)硫醚系化合物會使銅硫化。藉由併用(D)硫醚系化合物與(E)，(E)的金屬部分會抑制填料的表面之導電性物質的過度硫化。而且，藉由併用(D)硫醚系化合物與(E)，(E)的金屬部分會抑制支撐構件之基材材料(例如銅)的過度硫化。咸認該結果係因為在支撐構件包含銅時，會抑制樹脂組成物對支撐構件的接著性降低之故。又且，(E)會除去支撐構件表面的阻礙接著性之物質。(D)會將在高溫製程中產生之能促進硬化物劣化的過氧化氫分解。咸認係藉由此等作用來抑制硬化物的剝離。 The resin composition of the present invention exhibits excellent adhesive strength, and suppresses peeling of the cured product in a high-temperature process. According to the resin composition of the present invention, (D) a thioether-based compound is used, whereby hydrogen peroxide that can promote the deterioration of the hardened product can be decomposed. By decomposing hydrogen peroxide, the deterioration of the cured product after the resin composition is cured can be suppressed. As a result, the resin composition of the present invention exhibits excellent adhesion to the surface of the support member. Here, when copper is present on the surface of the support member, (D) the sulfide-based compound vulcanizes the copper. By using (D) a sulfide compound and (E) together, the metal part of (E) suppresses excessive vulcanization of the conductive material on the surface of the filler. Furthermore, by using (D) a thioether compound and (E) together, the metal part of (E) suppresses excessive vulcanization of the base material (for example, copper) of the support member. It is believed that this result is because when the support member contains copper, the decrease in the adhesiveness of the resin composition to the support member is suppressed. Furthermore, (E) removes substances that hinder adhesion on the surface of the support member. (D) Decompose hydrogen peroxide generated during the high-temperature process that can promote the deterioration of the hardened material. Xianxin suppresses the peeling of the hardened material by these actions.

有機酸之例，具體而言可列舉飽和單羧酸等。有機酸較佳係在室溫(25℃)為液狀之飽和單羧酸。飽 和單羧酸例如為分枝或直鏈狀的羧酸。此等的羧酸亦可具有脂環式基(環戊烷殘基、環己烷殘基等)。 Examples of organic acids specifically include saturated monocarboxylic acids. The organic acid is preferably a saturated monocarboxylic acid that is liquid at room temperature (25°C). full The monocarboxylic acid is, for example, a branched or linear carboxylic acid. These carboxylic acids may have an alicyclic group (cyclopentane residue, cyclohexane residue, etc.).

有機酸之例，具體而言可列舉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。而且，係環烷酸等羧酸混合物、且沸點為200℃以上者，亦可作為(E1)中之有機酸使用。有機酸較佳為2-乙基己酸、環戊羧酸、或環烷酸。 Examples of the organic acid specifically include branched saturated monocarboxylic acids such as 2-ethylhexanoic acid and cycloalkane monocarboxylic acids such as cyclopentanecarboxylic acid. Furthermore, a carboxylic acid mixture such as naphthenic acid and a boiling point of 200° C. or higher can also be used as the organic acid in (E1). The organic acid is preferably 2-ethylhexanoic acid, cyclopentanecarboxylic acid, or naphthenic acid.

(E1)沸點為200℃以上的有機酸之金屬鹽中之金屬鹽，例如為標準電極電位未達0V之金屬的鹽。標準電極電位未達0V之金屬之例為：鋅、鈷、鎳、鎂、錳及錫。此等的金屬之鹽之例為：鋅鹽、鈷鹽、鎳鹽、鎂鹽、錳鹽及錫鹽。金屬鹽較佳為鋅鹽或鈷鹽。支撐構件包含銅時，藉由使用銅或離子化傾向較銅更高的金屬之鹽，可防止由支撐構件流出銅。 (E1) The metal salt of the metal salt of an organic acid having a boiling point of 200°C or higher is, for example, a metal salt having a standard electrode potential of less than 0V. Examples of metals whose standard electrode potential does not reach 0V are: zinc, cobalt, nickel, magnesium, manganese, and tin. Examples of salts of these metals are: zinc salt, cobalt salt, nickel salt, magnesium salt, manganese salt and tin salt. The metal salt is preferably a zinc salt or a cobalt salt. When the supporting member contains copper, the copper can be prevented from flowing out of the supporting member by using a salt of copper or a metal having a higher ionization tendency than copper.

(E1)之例可列舉：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、環烷酸鋅、環烷酸鈷、環烷酸鎳、環烷酸鎂、環烷酸錳、環烷酸錫。(E1)較佳為2-乙基己酸鋅、環戊酸鋅、環烷酸鋅、2-乙基己酸鈷、環戊烷酸鈷或環烷酸鈷。 Examples of (E1) include zinc 2-ethylhexanoate, cobalt 2-ethylhexanoate, nickel 2-ethylhexanoate, magnesium 2-ethylhexanoate, manganese 2-ethylhexanoate, 2- Tin ethylhexanoate, zinc cyclopentane carboxylate, cobalt cyclopentane carboxylate, nickel cyclopentane carboxylate, magnesium cyclopentane carboxylate, manganese cyclopentane carboxylate, tin cyclopentane carboxylate, cycloalkane Zinc acid, cobalt naphthenate, nickel naphthenate, magnesium naphthenate, manganese naphthenate, tin naphthenate. (E1) Preferably, it is zinc 2-ethylhexanoate, zinc cyclopentanoate, zinc naphthenate, cobalt 2-ethylhexanoate, cobalt cyclopentanoate or cobalt naphthenate.

(E2)中沸點為200℃以上的有機酸，可使用與(E1)的關係如上所述之有機酸。(E2)中之有機酸較佳為2-乙基己酸、環戊烷羧酸或環烷酸。 (E2) The organic acid having a boiling point of 200° C. or higher can be used as described above in relation to (E1). The organic acid in (E2) is preferably 2-ethylhexanoic acid, cyclopentanecarboxylic acid or naphthenic acid.

(E2)中之金屬粒子之例可列舉標準電極電位未達0V的金屬之粒子。金屬粒子例如為鋅、鈷、鎳、鎂、錳、錫及此等的合金之粒子。合金之例可列舉：包含選自鋅、鈷、鎳、鎂、錳及錫之至少1種合金。合金例如為包含鋅及鋁的合金或黃銅。金屬粒子較佳為鋅粒子、鈷粒子或鋅合金粒子。支撐構件包含銅時，較佳係使用銅或離子化傾向較銅更高的金屬。藉此，可防止由支撐構件流出銅。更進一步，藉由添加錫粒子讓錫犠牲氧化(sacrificial oxide)而保護含銅的支撐構件。藉此，可使接合於支撐構件的模具之剪切強度提升。 Examples of the metal particles in (E2) include metal particles whose standard electrode potential has not reached 0V. The metal particles are, for example, particles of zinc, cobalt, nickel, magnesium, manganese, tin, and alloys thereof. Examples of alloys include at least one alloy selected from zinc, cobalt, nickel, magnesium, manganese, and tin. The alloy is, for example, an alloy containing zinc and aluminum or brass. The metal particles are preferably zinc particles, cobalt particles or zinc alloy particles. When the support member contains copper, it is preferable to use copper or a metal having a higher ionization tendency than copper. By this, copper can be prevented from flowing out of the support member. Furthermore, the support member containing copper is protected by adding tin particles to oxidize sacrificial oxide. Thereby, the shear strength of the mold joined to the support member can be improved.

(E2)中之金屬氧化物粒子，可列舉標準電極電位未達0V的金屬之氧化物粒子。金屬氧化物粒子可列舉例如鋅、鈷、鎳、鎂、錳及錫的氧化物粒子。(E2)中之金屬氧化物粒子較佳為氧化鋅粒子。 The metal oxide particles in (E2) include metal oxide particles having a standard electrode potential of less than 0V. Examples of the metal oxide particles include oxide particles of zinc, cobalt, nickel, magnesium, manganese, and tin. The metal oxide particles in (E2) are preferably zinc oxide particles.

(E2)中之金屬粒子及金屬氧化物粒子的形狀並無特別限定，例如為球狀、鱗片狀等。金屬粒子及金屬氧化物粒子的平均粒徑可為0.05至20μm，較佳為0.05至15μm，更佳為0.1至8μm。在此，平均粒徑係意指由雷射繞射法所測定的體積基準之中徑(median diameter)。 The shapes of the metal particles and metal oxide particles in (E2) are not particularly limited, and they are, for example, spherical or scaly. The average particle diameter of the metal particles and metal oxide particles may be 0.05 to 20 μm, preferably 0.05 to 15 μm, and more preferably 0.1 to 8 μm. Here, the average particle diameter means a volume-based median diameter measured by the laser diffraction method.

(E2)可為沸點為200℃以上的有機酸與金屬粒子之組合，也可為沸點為200℃以上的有機酸與金屬氧化物粒子之組合，亦可為沸點為200℃以上的有機酸與金屬粒子及氧化金屬粒子之組合。 (E2) It may be a combination of an organic acid with a boiling point of 200°C or more and metal particles, or a combination of an organic acid with a boiling point of 200°C or more and metal oxide particles, or an organic acid with a boiling point of 200°C or more Combination of metal particles and metal oxide particles.

(E2)之例，具體而言可列舉：由2-乙基己 酸、環戊烷羧酸及環烷酸中選出之1種以上，與由鋅粒子、鈷粒子、鋅合金粒子及氧化鋅粒子中選出之1種以上之組合。 Examples of (E2) include specifically 2-ethylhexyl A combination of one or more selected from the group consisting of acid, cyclopentanecarboxylic acid, and naphthenic acid, and one or more selected from zinc particles, cobalt particles, zinc alloy particles, and zinc oxide particles.

(E2)中之沸點為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以質量比例(沸點為200℃以上的有機酸：金屬粒子及/或金屬氧化物粒子)表示，較佳為10：90至90：10，更佳為20：80至60：40。 (E2) The organic acid with a boiling point of 200°C or higher, and the amount of metal particles and/or metal oxide particles used in a mass ratio (organic acid with a boiling point of 200°C or higher: metal particles and/or metal oxide particles) It means that it is preferably 10:90 to 90:10, and more preferably 20:80 to 60:40.

(E)可僅使用(E1)或(E2)，或併用(E1)與(E2)。使用(E2)時，易於控制有機酸的量，且於硬化時可抑制有機酸的滲出(bleed)。 (E) Only (E1) or (E2) may be used, or (E1) and (E2) may be used in combination. When (E2) is used, it is easy to control the amount of organic acid, and bleed of organic acid can be suppressed during hardening.

本發明中，相對於(A)至(D)的合計100質量份，(A)可為40至90質量份。就導電性的觀點來看，(A)更佳為55至90質量份，又更佳為60至88質量份。 In the present invention, (A) may be 40 to 90 parts by mass with respect to a total of 100 parts by mass of (A) to (D). From the viewpoint of conductivity, (A) is more preferably 55 to 90 parts by mass, and still more preferably 60 to 88 parts by mass.

相對於(A)至(D)的合計100質量份，(B)可為5至55質量份。就熱硬化性的觀點來看，(B)更佳為5至50質量份，又更佳為10至40質量份。 (B) may be 5 to 55 parts by mass with respect to a total of 100 parts by mass of (A) to (D). From the viewpoint of thermosetting property, (B) is more preferably 5 to 50 parts by mass, and still more preferably 10 to 40 parts by mass.

相對於(A)至(D)的合計100質量份，(C)可為1至50質量份。就硬化性的觀點來看，(C)更佳為2至40質量份，又更佳為2至20質量份。 Relative to 100 parts by mass of (A) to (D), (C) may be 1 to 50 parts by mass. From the viewpoint of curability, (C) is more preferably 2 to 40 parts by mass, and still more preferably 2 to 20 parts by mass.

相對於(A)至(C)的合計100質量份，(D)可為0.05至1.5質量份。就保存安定性與抑制因填料的表面之導電性物質之過度硫化所造成的導電性降低的觀點來看，(D)更佳為0.05至1.0質量份，又更佳為0.05至0.75質量份。 (D) may be 0.05 to 1.5 parts by mass with respect to a total of 100 parts by mass of (A) to (C). From the viewpoints of preservation stability and suppression of conductivity reduction due to excessive vulcanization of the conductive material on the surface of the filler, (D) is more preferably 0.05 to 1.0 part by mass, and still more preferably 0.05 to 0.75 part by mass.

本發明中，(A)至(D)的調配量如前所述。 In the present invention, the blending amounts of (A) to (D) are as described above.

相對於(A)至(E)的合計100質量份，(E)可為0.1至5質量份。就高溫製程中抑制硬化物的剝離之效果的觀點來看，(E)更佳為0.1至2質量份，又更佳為0.1至1質量份。 (E) may be 0.1 to 5 parts by mass with respect to a total of 100 parts by mass of (A) to (E). From the viewpoint of the effect of suppressing the peeling of the hardened material in the high-temperature process, (E) is more preferably 0.1 to 2 parts by mass, and still more preferably 0.1 to 1 part by mass.

(F)其他成分 (F) Other ingredients

本發明之樹脂組成物可含有(F)其他成分。(F)其他成分例如為耦合劑(矽烷耦合劑、鈦耦合劑劑等)、著色劑、消泡劑、界面活性劑、聚合抑制劑等添加劑。 The resin composition of the present invention may contain (F) other components. (F) Other components are additives such as coupling agents (silane coupling agents, titanium coupling agents, etc.), colorants, defoamers, surfactants, polymerization inhibitors and the like.

本發明之樹脂組成物，可藉由混合(A)以外的成分後，使用三輥分散機來混練此等成分，接著添加(A)並均勻地進行混合而調製。 The resin composition of the present invention can be prepared by mixing components other than (A), kneading these components using a three-roll disperser, and then adding (A) and uniformly mixing.

本發明之樹脂組成物可適合使用作為黏晶膏或散熱構件用接著劑。 The resin composition of the present invention can be suitably used as an adhesive for a crystal paste or a heat dissipation member.

具體而言，係於含有本發明之樹脂組成物的黏晶膏、散熱構件用接著劑所適用之導線架、基板等，安裝半導體元件、散熱構件等。接著，加熱黏晶膏、接著劑以使其硬化。藉此，可將半導體元件、散熱構件等接著於導線架、基板等。加熱條件可適當選擇。例如可用100至200℃的峰值溫度來加熱黏晶膏或接著劑。接著，可經由打線接合及密封的步驟製造半導體裝置。藉由將該半導體裝置焊接組裝於印刷線路基板上，可製造各種電子零件。本發明之樹脂組成物的硬化物係接著強度優異，且在高溫製程中硬化物不易剝離。而且，本發明之樹脂組成物的硬化物，在高溫製程中因吸濕所造成的強度劣化係受到抑制。特別是 在支撐構件為銅導線架、銅基板或樹脂基板的情況下，會有效地發揮此等效果。 Specifically, a semiconductor element, a heat dissipation member, and the like are mounted on a lead frame, a substrate, etc. to which a crystal paste containing the resin composition of the present invention and an adhesive for a heat dissipation member are applied. Next, the crystal paste and the adhesive are heated to harden it. Thereby, the semiconductor element, the heat dissipation member, etc. can be attached to the lead frame, the substrate, etc. The heating conditions can be appropriately selected. For example, a peak temperature of 100 to 200°C may be used to heat the viscous paste or adhesive. Next, the semiconductor device can be manufactured through the steps of wire bonding and sealing. By soldering and assembling the semiconductor device on the printed circuit board, various electronic parts can be manufactured. The cured product of the resin composition of the present invention has excellent adhesive strength, and the cured product is not easily peeled off during the high-temperature process. Furthermore, the hardened product of the resin composition of the present invention is suppressed in the strength deterioration caused by moisture absorption during the high-temperature process. especially When the support member is a copper lead frame, a copper substrate, or a resin substrate, these effects are effectively exerted.

(實施例) (Example)

以下，藉由實施例及比較例進一步詳細說明本發明。只要沒有另外聲明，份、%即表示質量份、質量%。本發明並不受此等的實施例所限定。 Hereinafter, the present invention will be described in further detail with examples and comparative examples. As long as there is no other statement, parts and% means mass parts and mass %. The present invention is not limited by these embodiments.

平均粒徑係由雷射繞射法所測定的體積基準之中徑。 The average particle diameter is the volume-based median diameter measured by the laser diffraction method.

實施例所使用的各成分係如以下所示。 The components used in the examples are shown below.

a1：50質量%Ag塗佈氧化鋁粒子(平均粒徑20μm、鍍銀厚度1μm) a1: 50% by mass Ag-coated alumina particles (average particle diameter 20 μm, silver plating thickness 1 μm)

a2：30質量%Ag塗佈氧化鋁粒子(平均粒徑20μm、鍍銀厚度1μm) a2: 30% by mass Ag coated alumina particles (average particle diameter 20 μm, silver plating thickness 1 μm)

a3：錫粒子(平均粒徑5μm) a3: Tin particles (average particle size 5 μm)

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

b2：新戊二醇二甲基丙烯酸酯 b2: neopentyl glycol dimethacrylate

b3：N-丙烯醯氧基乙基六氫鄰苯二甲醯亞胺 b3: N-propylene oxyethyl hexahydrophthalimide

b4：1,6-己二醇縮水甘油醚 b4: 1,6-hexanediol glycidyl ether

b5：環己烷二甲醇二縮水甘油醚 b5: Cyclohexane dimethanol diglycidyl ether

c1：甲酚酚醛清漆樹脂羥基當量=118g/eq軟化點105至115℃ c1: hydroxyl equivalent of cresol novolak resin = 118g/eq softening point 105 to 115℃

c2：Novacure HX3088(Asahi Kasei E-materials公司製、微膠囊化咪唑) c2: Novavacure HX3088 (made by Asahi Kasei E-materials, microencapsulated imidazole)

c3：1,1,3,3-四甲基丁基過氧化2-乙基己酸酯 c3: 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate

d1：3,3’-硫代二丙酸二(十三基)酯 d1: bis(tridecyl) 3,3’-thiodipropionate

d2：雙(3,5-二-第三丁基-4-羥基苯甲基)硫化物 d2: bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide

d3：3,3’-硫代二丙酸二硬脂酯 d3: Distearyl 3,3’-thiodipropionate

d4：2-巰基苯并咪唑 d4: 2-mercaptobenzimidazole

d5：新戊四醇肆(丁酸-3-巰基酯) d5: Neopentaerythritol (butyrate-3-mercaptoester)

e1：2-乙基己酸(沸點228℃) e1: 2-ethylhexanoic acid (boiling point 228℃)

e2：氧化鋅粒子(平均粒徑0.60μm) e2: zinc oxide particles (average particle size 0.60 μm)

e3：2-乙基己酸鋅(鋅含量22質量%) e3: Zinc 2-ethylhexanoate (zinc content 22% by mass)

e4：鋅粒子(平均粒徑3.7μm) e4: Zinc particles (average particle size 3.7 μm)

e5：環烷酸鈷(鈷含量8質量%) e5: Cobalt naphthenate (cobalt content 8% by mass)

e6：雙(2-乙基己酸)鈷(II)(鈷含量8質量%) e6: bis(2-ethylhexanoic acid) cobalt (II) (cobalt content 8% by mass)

e7：環烷酸(沸點200℃以上) e7: Naphthenic acid (boiling point above 200℃)

f1：3-縮水甘油氧基丙基三甲氧基矽烷 f1: 3-glycidoxypropyltrimethoxysilane

f2：雙(三乙氧基矽基丙基)四硫化物 f2: bis(triethoxysilylpropyl) tetrasulfide

將實施例及比較例的樹脂組成物依照以下(1)至(4)的程序進行製造。 The resin compositions of Examples and Comparative Examples were produced according to the following procedures (1) to (4).

(1)將表1至3的b1至b3混合，加熱至成為100℃為止。 (1) Mix b1 to b3 of Tables 1 to 3 and heat until it reaches 100°C.

(2)於上述(1)所得之混合物中添加c1。添加c1後，加熱混合物使c1溶解。c1溶解後，將混合物冷卻至室溫。 (2) Add c1 to the mixture obtained in (1) above. After adding c1, the mixture was heated to dissolve c1. After c1 dissolves, the mixture is cooled to room temperature.

(3)於上述(2)所得之混合物中添加c2、c3及a1至a3以外的成分，使用附攪拌翼的攪拌機來均勻地混合。 (3) Add components other than c2, c3, and a1 to a3 to the mixture obtained in (2) above, and mix uniformly using a mixer with a stirring blade.

(4)更進一步，於上述(3)所得之混合物中添加a1至 a3，並使用3輥分散機使其分散。分散a1至a3後，添加c2及c3，並使用附攪拌翼的攪拌機來均勻地混合，得到樹脂組成物。 (4) Further, add a1 to the mixture obtained in (3) above a3, and use a 3-roll disperser to disperse it. After dispersing a1 to a3, c2 and c3 were added, and the mixture was uniformly mixed using a stirrer with a stirring blade to obtain a resin composition.

表1至3中，評估之項所記載的數值以外之數值係表示質量份。 In Tables 1 to 3, values other than the values described in the evaluation items represent parts by mass.

將實施例及比較例的各樹脂組成物依以下的方式評估。將評估的結果表示於表1至3。 Each resin composition of Examples and Comparative Examples was evaluated in the following manner. The evaluation results are shown in Tables 1 to 3.

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

觀察吸濕處理後的樹脂組成物曝露於高溫時產生的剝離。觀察係依照下述(1)至(5)的程序進行。 Observe the peeling that occurs when the resin composition after the moisture absorption treatment is exposed to high temperature. The observation was performed according to the procedures of (1) to (5) below.

(1)使用實施例及比較例的各樹脂組成物，將3mm×3mm的矽晶片安裝於銅導線架上，得到試驗構件。然後，粍時30分鐘將試驗構件的周圍由室溫升溫至175℃，在175℃保持30分鐘，使樹脂組成物硬化。藉此。將矽晶片接著於銅導線架上。 (1) Using each resin composition of Examples and Comparative Examples, a 3 mm×3 mm silicon wafer was mounted on a copper lead frame to obtain a test member. Then, around 30 minutes, the temperature of the test member was raised from room temperature to 175°C, and held at 175°C for 30 minutes to harden the resin composition. Take this. Attach the silicon wafer to the copper lead frame.

(2)假定晶片為環氧成型模料(epoxy molding compound)所被覆，而使用一般的環氧成型模料之硬化條件(175℃、4小時)對已進行(1)的處理之試驗構件加熱。 (2) Assuming that the wafer is covered with an epoxy molding compound, the hardened conditions (175°C, 4 hours) of the general epoxy molding compound are used to heat the test component that has been treated in (1) .

(3)將已進行(2)的處理之試驗構件浸泡於沸騰的水中2小時。 (3) The test member subjected to the treatment of (2) is immersed in boiling water for 2 hours.

(4)使已進行(3)的處理之試驗構件在水中(使其不為乾燥的狀態)冷卻至室溫。然後，將該試驗構件以迴焊溫度(270℃)加熱。 (4) The test member that has been subjected to the treatment of (3) is cooled to room temperature in water (so that it is not in a dry state). Then, 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來觀察 已進行(4)的處理之試驗構件上的晶片之剝離狀態。具體而言，係從藉由觀察顯微鏡所得之圖像求出相對於晶片面積之接著面積的比率。相對於晶片面積之接著面積為80%以上時，評估為「無剝離」。相對於晶片面積之接著面積未達80%時，則評估為「有剝離」。 (5) Observe using a scanning ultrasonic microscope made by SONIX The peeling state of the wafer on the test member that has been processed in (4). Specifically, the ratio of the adhering area to the wafer area is obtained from the image obtained by the observation microscope. When the bonding area relative to the wafer area is 80% or more, it is evaluated as "no peeling". When the bonding area relative to the wafer area is less than 80%, it is evaluated as "with peeling".

2.可使用時間(pot life)(增黏率) 2. Pot life (viscosity increase rate)

測定所調製的樹脂組成物之初始黏度。具體而言，係使用Brookfield公司製的E型旋轉黏度計HBDV-2 Pro(使用錐板(cone-plate)及轉子(spindle)CP51)，測定在5rpm、25℃之樹脂組成物的黏度(Pa．s)。接著，以同樣的程序來測定在密閉容器的內部以25℃、濕度50%的環境保管48小時後之樹脂組成物的黏度。藉由以下的式算出樹脂組成物的增黏率(%)。 The initial viscosity of the prepared resin composition is measured. Specifically, an E-type rotary viscometer HBDV-2 Pro (using cone-plate and spindle CP51) manufactured by Brookfield was used to measure the viscosity (Pa of the resin composition at 5 rpm and 25°C) .S). Next, the viscosity of the resin composition after storing for 48 hours in an environment of 25° C. and a humidity of 50% in the closed container was measured by the same procedure. The viscosity increase rate (%) of the resin composition was calculated by the following formula.

增黏率(%)=100×(保管48小時後的黏度-初始黏度)/(初始黏度) Viscosity increase rate (%) = 100 × (viscosity after 48 hours of storage-initial viscosity) / (initial viscosity)

以所算出的增黏率為指標，評估樹脂組成物的可使用時間。具體而言，增黏率未達25%時，樹脂組成物的可使用時間足夠長，評估為合格。 Using the calculated viscosity increase rate as an index, the usable time of the resin composition was evaluated. Specifically, when the viscosity increase rate is less than 25%, the usable time of the resin composition is sufficiently long, and the evaluation is passed.

3.電阻率(Ω．m)的測定 3. Determination of resistivity (Ω·m)

測定使所調製的樹脂組成物硬化之硬化物的電阻率(Ω．m)。具體而言，使用樹脂組成物，於寬20mm、長20mm、厚1mm的氧化鋁基板上印刷長71mm、寬1mm、厚20μm的鋸齒形圖案。圖案的印刷係使用200網目之不鏽鋼製的網版。接著，耗時30分鐘將圖案的周圍從室溫升溫至 150℃。接著，將圖案在大氣中以150℃硬化60分鐘，藉此形成外部電極。鋸齒形圖案的厚度係以東京精密公司製的表面粗度形狀測定機(製品名：Surfcom 1400)測定。具體而言，鋸齒形圖案的厚度係在以與圖案交叉的方式配置的6個點之測定值的平均來求出。圖案硬化後，使用LCR測試儀，用4端點法測定圖案的電阻率(Ω．m)。表1至3中係表示所測定的電阻率(×10-3Ω．cm)。電阻率未達10×10-3Ω．cm時，評估為合格。 The resistivity (Ω·m) of the cured product that hardened the prepared resin composition was measured. Specifically, using a resin composition, a zigzag pattern having a length of 71 mm, a width of 1 mm, and a thickness of 20 μm was printed on an alumina substrate having a width of 20 mm, a length of 20 mm, and a thickness of 1 mm. The printing of the pattern uses a 200-mesh stainless steel screen. Next, it took 30 minutes to raise the temperature around the pattern from room temperature to 150°C. Next, the pattern was hardened at 150°C for 60 minutes in the atmosphere, thereby forming an external electrode. The thickness of the zigzag pattern was measured with a surface roughness shape measuring machine (product name: Surfcom 1400) manufactured by Tokyo Precision Co., Ltd. Specifically, the thickness of the zigzag pattern is obtained by averaging the measured values of 6 points arranged so as to cross the pattern. After the pattern is hardened, the resistivity (Ω·m) of the pattern is measured by the 4-terminal method using an LCR tester. Tables 1 to 3 show the measured resistivity (×10 -3 Ω·cm). The resistivity is less than 10×10 -3 Ω. cm, it is evaluated as pass.

4.綜合評估 4. Comprehensive assessment

基於上述1至3的評估，依以下的基準對實施例及比較例的各樹脂組成物進行綜合評估。 Based on the above evaluations 1 to 3, the resin compositions of the examples and comparative examples were comprehensively evaluated according to the following criteria.

○：無剝離、可使用時間為合格、且電阻率為合格時，評估為○。 ○: When there is no peeling, the usable time is acceptable, and the resistivity is acceptable, it is evaluated as ○.

×：有剝離、可使用時間為不合格、或電阻率為不合格時，評估為×。 ×: When peeling occurs, the usable time is unacceptable, or the resistivity is unacceptable, the evaluation is ×.

Figure 104132361-A0202-12-0027-1
Figure 104132361-A0202-12-0027-1

Figure 104132361-A0202-12-0028-2
Figure 104132361-A0202-12-0028-2

Figure 104132361-A0202-12-0029-3
Figure 104132361-A0202-12-0029-3

實施例1至15的樹脂組成物係包含(A)於絕緣性的芯材表面具有導電性物質之填料、以及(D)硫醚系化合物。藉此，填料表面之導電性物質不會被過度地硫化，故可維持由樹脂組成物硬化而得之硬化物的導電性。 The resin composition of Examples 1 to 15 includes (A) a filler having a conductive substance on the surface of an insulating core material, and (D) a sulfide-based compound. As a result, the conductive material on the surface of the filler is not excessively vulcanized, so that the conductivity of the hardened product obtained by hardening the resin composition can be maintained.

而且，根據實施例1至15的樹脂組成物，可分解於迴焊等高溫製程所產生之過氧化氫。過氧化氫為能促進硬化物劣化之物質。所以，實施例1至15的樹脂組成物因抑制了硬化物的劣化，故對支撐構件表面具有優異的接著性。其結果，實施例1至15的樹脂組成物係被評估為「無剝離」。 Furthermore, the resin compositions of Examples 1 to 15 can decompose hydrogen peroxide generated in high-temperature processes such as reflow. Hydrogen peroxide is a substance that can promote the deterioration of hardened materials. Therefore, since the resin compositions of Examples 1 to 15 suppress the deterioration of the cured product, they have excellent adhesion to the surface of the support member. As a result, the resin composition systems of Examples 1 to 15 were evaluated as "without peeling".

又且，根據實施例1至15的樹脂組成物，因使用(D)硫醚系化合物而產生結構位阻效應。藉此，抑制了對環氧樹脂等熱硬化性樹脂的反應，故可維持適度的可使用時間。其結果，實施例1至15的樹脂組成物之可使用時間的評估全部為合格。 Furthermore, according to the resin compositions of Examples 1 to 15, the use of (D) a thioether-based compound causes a structural steric effect. As a result, the reaction to thermosetting resins such as epoxy resins is suppressed, so that an appropriate use time can be maintained. As a result, all the evaluations of the usable time of the resin compositions of Examples 1 to 15 were passed.

根據實施例10至15的樹脂組成物，藉由併用(D)硫醚系化合物與(E)，使(E)的金屬部分抑制填料表面之導電性物質的過度硫化。又，藉由併用(D)硫醚系化合物與(E)，使(E)的金屬部分抑制支撐構件之基材的材料(例如銅)之過度的硫化。其結果，支撐構件包含銅時，係抑制樹脂組成物對支撐構件的接著性降低。 According to the resin compositions of Examples 10 to 15, by using (D) the thioether compound and (E) together, the metal portion of (E) suppresses excessive vulcanization of the conductive substance on the filler surface. In addition, by using (D) a sulfide compound and (E) together, the metal part of (E) suppresses excessive vulcanization of the material (for example, copper) of the base material of the support member. As a result, when the support member contains copper, it is suppressed that the adhesiveness of the resin composition to the support member decreases.

而且，根據實施例10至15的樹脂組成物，藉由併用(D)硫醚系化合物與(E)，(E)會除去支撐構件表面的阻礙接著性之物質。(D)會將在高溫製程中產生之能促進 硬化物的劣化之過氧化氫分解。藉由此等的作用，抑制了硬化物的剝離。其結果，實施例1至15的樹脂組成物係被評估為「無剝離」 In addition, according to the resin compositions of Examples 10 to 15, by using (D) the thioether-based compound together with (E), (E) removes substances that hinder adhesion on the surface of the support member. (D) Will promote the energy generated in the high temperature process Hydrogen peroxide decomposes to the deterioration of hardened materials. By these actions, peeling of the hardened material is suppressed. As a result, the resin composition systems of Examples 1 to 15 were evaluated as "no peeling"

對於實施例1至9的樹脂組成物，其吸濕高溫試驗後的接著面積為80至90%。對於實施例10至15的樹脂組成物，其吸濕高溫試驗後的接著面積為90%以上，係進一步地抑制了剝離。 For the resin compositions of Examples 1 to 9, the area after the moisture absorption high temperature test was 80 to 90%. For the resin compositions of Examples 10 to 15, the area after the moisture absorption high-temperature test was 90% or more, and the peeling was further suppressed.

另一方面，比較例1的樹脂組成物因不含硫醚系化合物，故接著性降低，確認到硬化物的剝離。 On the other hand, since the resin composition of Comparative Example 1 does not contain a sulfide-based compound, the adhesiveness is reduced, and peeling of the cured product is confirmed.

包含硫醇系化合物以代替硫醚系化合物之比較例2及3的樹脂組成物，樹脂組成物硬化後的硬化物之比電阻值增加，導電性下降。 In the resin compositions of Comparative Examples 2 and 3 containing the thiol-based compound instead of the thioether-based compound, the specific resistance value of the cured product after the resin composition was cured increased, and the conductivity decreased.

又，比較例2及3的樹脂組成物之增黏率上升，未維持適度的可使用時間。 In addition, the resin compositions of Comparative Examples 2 and 3 had an increased viscosity increase, and did not maintain an appropriate usable time.

(產業上之可利用性) (Industry availability)

根據本發明，可提供可維持填料的導電性，同時可維持適度的可使用時間之樹脂組成物。而且，可提供對基板的接著強度優異，且在高溫製程中抑制硬化物的剝離之樹脂組成物。 According to the present invention, it is possible to provide a resin composition that can maintain the electrical conductivity of the filler while maintaining an appropriate use time. Furthermore, it is possible to provide a resin composition which is excellent in the adhesive strength to the substrate and suppresses the peeling of the cured product during the high-temperature process.

本發明之樹脂組成物可適合使用作為黏晶膏或散熱構件用接著劑。 The resin composition of the present invention can be suitably used as an adhesive for a crystal paste or a heat dissipation member.

特別是，本發明之樹脂組成物的硬化物抑制了吸濕所造成之強度的劣化。使用本發明之樹脂組成物所製作的半導體裝置係對吸濕迴焊的耐性優異，可靠性高。 In particular, the cured product of the resin composition of the present invention suppresses the deterioration of strength due to moisture absorption. The semiconductor device produced using the resin composition of the present invention has excellent resistance to moisture reflow and high reliability.

本發明之樹脂組成物即使在支撐構件為銅或樹脂的情況下，仍可發揮此等的效果，故實用性高。 The resin composition of the present invention can exert such effects even when the supporting member is copper or resin, and therefore has high practicality.

Claims (13)

一種樹脂組成物，其係包含：(A)於絕緣性的芯材之表面具有導電性物質之填料、(B)熱硬化性樹脂、(C)硬化劑、以及(D)具有二酯結構的硫醚化合物及/或屬於雙(3,5-二-第三丁基-4-羥基苯甲基)硫化物之具有苯環之硫醚系化合物。 A resin composition comprising: (A) a filler having a conductive substance on the surface of an insulating core material, (B) a thermosetting resin, (C) a hardener, and (D) having a diester structure Thioether compounds and/or sulfide compounds with benzene ring which are bis(3,5-di-third-butyl-4-hydroxybenzyl) sulfides. 如申請專利範圍第1項所述之樹脂組成物，其中，(A)中之導電性物質係由銀、金、銅、鈀及此等的合金所組成群組中選出之至少1種導電性物質。 The resin composition as described in item 1 of the patent application scope, wherein the conductive substance in (A) is at least one conductivity selected from the group consisting of silver, gold, copper, palladium and these alloys substance. 如申請專利範圍第1項或第2項所述之樹脂組成物，其更包含(E)(E1)沸點為200℃以上的有機酸之金屬鹽，及/或(E2)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。 The resin composition as described in item 1 or 2 of the patent application scope, which further includes (E) (E1) a metal salt of an organic acid with a boiling point of 200°C or higher, and/or (E2) a boiling point of 200°C or higher Combination of organic acids with metal particles and/or metal oxide particles. 如申請專利範圍第3項所述之樹脂組成物，其中，(E1)係由2-乙基己酸、環烷酸及環戊烷羧酸所組成群組中選出之有機酸的金屬鹽，(E2)係由2-乙基己酸、環烷酸及環戊烷羧酸所組成群組中選出之有機酸與金屬粒子及/或金屬氧化物粒子之組合。 The resin composition as described in item 3 of the patent application, wherein (E1) is a metal salt of an organic acid selected from the group consisting of 2-ethylhexanoic acid, naphthenic acid and cyclopentanecarboxylic acid, (E2) is a combination of organic acid and metal particles and/or metal oxide particles selected from the group consisting of 2-ethylhexanoic acid, naphthenic acid and cyclopentanecarboxylic acid. 如申請專利範圍第4項所述之樹脂組成物，其中，(E1)中之金屬鹽係由鋅鹽、鈷鹽、鎳鹽、鎂鹽、錳鹽及錫鹽所組成群組中選出之鹽，(E2)中之金屬粒子及/或金屬氧化物粒子係由鋅、鈷、 鎳、鎂、錳、錫及此等的氧化物所組成群組中選出之粒子。 The resin composition as described in item 4 of the patent application scope, wherein the metal salt in (E1) is a salt selected from the group consisting of zinc salt, cobalt salt, nickel salt, magnesium salt, manganese salt and tin salt , The metal particles and/or metal oxide particles in (E2) are composed of zinc, cobalt, Particles selected from the group consisting of nickel, magnesium, manganese, tin and these oxides. 如申請專利範圍第1項或第2項所述之樹脂組成物，其中，相對於(A)至(C)的合計100質量份，(D)為0.05至1.5質量份。 The resin composition according to item 1 or 2 of the patent application range, wherein (D) is 0.05 to 1.5 parts by mass with respect to the total of 100 parts by mass of (A) to (C). 如申請專利範圍第3項所述之樹脂組成物，其中，相對於(A)至(E)的合計100質量份，(E)為0.1至5質量份。 The resin composition according to item 3 of the patent application scope, wherein (E) is 0.1 to 5 parts by mass with respect to the total of 100 parts by mass of (A) to (E). 一種黏晶膏，其係包含申請專利範圍第1項或第2項所述之樹脂組成物。 A viscous crystal paste, which contains the resin composition described in item 1 or 2 of the patent application. 一種散熱構件用接著劑，其係包含申請專利範圍第1項或第2項所述之樹脂組成物。 An adhesive for a heat dissipation member, which contains the resin composition described in the first or second patent application. 一種半導體裝置，其係使用申請專利範圍第8項所述之黏晶膏所製作者。 A semiconductor device manufactured by using the viscous crystal paste described in item 8 of the patent application. 一種半導體裝置，其係使用申請專利範圍第9項所述之散熱構件用接著劑所製作者。 A semiconductor device manufactured by using the adhesive for a heat dissipating member described in item 9 of the patent application. 如申請專利範圍第10項所述之半導體裝置，其中，使用了黏晶膏的表面為銅。 The semiconductor device as described in item 10 of the patent application, wherein the surface on which the die-bonding paste is used is copper. 如申請專利範圍第11項所述之半導體裝置，其中，使用了散熱構件用接著劑的表面為銅。 The semiconductor device as described in item 11 of the patent application, wherein the surface using the adhesive for the heat dissipation member is copper.
TW104132361A 2014-10-01 2015-10-01 Resin composition TWI683872B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-203467 2014-10-01
JP2014203467 2014-10-01

Publications (2)

Publication Number Publication Date
TW201619325A TW201619325A (en) 2016-06-01
TWI683872B true TWI683872B (en) 2020-02-01

Family

ID=55630687

Family Applications (1)

Application Number Title Priority Date Filing Date
TW104132361A TWI683872B (en) 2014-10-01 2015-10-01 Resin composition

Country Status (5)

Country Link
JP (1) JPWO2016052664A1 (en)
KR (1) KR102325095B1 (en)
CN (1) CN107075258B (en)
TW (1) TWI683872B (en)
WO (1) WO2016052664A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20240005192A (en) * 2017-03-29 2024-01-11 가부시끼가이샤 레조낙 Adhesive composition and structural body
KR20200143372A (en) * 2018-04-10 2020-12-23 타츠타 전선 주식회사 Conductive paint and manufacturing method of shielding package using the conductive paint

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101636463A (en) * 2007-10-29 2010-01-27 住友电木株式会社 Adhesive composition for semiconductor and semicondutor device produced using the adhesive composition

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001338529A (en) * 2000-05-30 2001-12-07 Togo Seisakusho Corp Conductive resin composition
JP2002008443A (en) 2000-06-26 2002-01-11 Tokuriki Honten Co Ltd Thermal hardening type low resistance conductive paste
US7326369B2 (en) 2005-03-07 2008-02-05 National Starch And Chemical Investment Holding Corporation Low stress conductive adhesive
JP4802667B2 (en) * 2005-11-08 2011-10-26 住友金属鉱山株式会社 Epoxy resin adhesive composition and optical semiconductor adhesive using the same
WO2007074652A1 (en) * 2005-12-26 2007-07-05 Hitachi Chemical Company, Ltd. Adhesive composition, circuit connecting material and connecting structure of circuit member
JP5089885B2 (en) * 2006-01-17 2012-12-05 太陽ホールディングス株式会社 Thermal insulation resin composition and printed wiring board using the same
US20070213429A1 (en) 2006-03-10 2007-09-13 Chih-Min Cheng Anisotropic conductive adhesive
CN101632199B (en) * 2007-05-15 2011-08-31 日立化成工业株式会社 Circuit-connecting material, and connection structure for circuit member
WO2009057530A1 (en) * 2007-10-29 2009-05-07 Sumitomo Bakelite Co., Ltd. Adhesive composition for semiconductor and semicondutor device produced using the adhesive composition
JP5651913B2 (en) 2008-04-21 2015-01-14 スリーボンドファインケミカル株式会社 Conductive resin composition
JP5033046B2 (en) * 2008-04-24 2012-09-26 パナソニック株式会社 Thermosetting resin composition and method for producing the same
CN102177212A (en) * 2008-10-22 2011-09-07 日立化成工业株式会社 Adhesive film
WO2010046996A1 (en) * 2008-10-24 2010-04-29 住友ベークライト株式会社 Adhesive composition for semiconductor and semiconductor device manufactured using the same
JP2011086669A (en) 2009-10-13 2011-04-28 Asahi Kasei E-Materials Corp Die bonding paste and semiconductor device using the same
TWI534256B (en) * 2011-05-16 2016-05-21 Showa Denko Kk Hardened heat dissipation composition
WO2014157175A1 (en) * 2013-03-29 2014-10-02 ナミックス株式会社 Resin composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101636463A (en) * 2007-10-29 2010-01-27 住友电木株式会社 Adhesive composition for semiconductor and semicondutor device produced using the adhesive composition

Also Published As

Publication number Publication date
KR20170062475A (en) 2017-06-07
WO2016052664A1 (en) 2016-04-07
KR102325095B1 (en) 2021-11-11
TW201619325A (en) 2016-06-01
JPWO2016052664A1 (en) 2017-07-13
CN107075258A (en) 2017-08-18
CN107075258B (en) 2020-03-06

Similar Documents

Publication Publication Date Title
CN106133894B (en) Hot curing resin composition, semiconductor device and electrical and electronic parts
JP5761639B2 (en) Adhesive resin composition, cured product thereof, and adhesive film
JP5927177B2 (en) Die bonding agent
JP6770509B2 (en) Resin composition, conductive resin composition, adhesive, conductive adhesive, electrode forming paste, semiconductor device
JP6190653B2 (en) Conductive resin composition and semiconductor device
TWI782928B (en) Heat conductive paste and electronic device
JP6744859B2 (en) Resin composition, conductive resin composition, adhesive, conductive adhesive, electrode forming paste, semiconductor device
JP2016219600A (en) Die attach paste for semiconductor and semiconductor device
JP2015162392A (en) Conductive paste, electric/electronic component, and method of manufacturing the same
JP7100651B2 (en) Paste compositions, semiconductor devices and electrical / electronic components
JP5622267B2 (en) Adhesive resin composition, cured product thereof, and adhesive film
TWI683872B (en) Resin composition
TWI648324B (en) Resin composition
JP6069071B2 (en) Resin composition
JP6106007B2 (en) Resin composition
JP2017050119A (en) Manufacturing method of electric conductive paste and electric conductive paste
JP2016117869A (en) Resin composition for semiconductor adhesion and semiconductor device
JP6134597B2 (en) Die attach agent
JP2020193309A (en) Conductive adhesive and method for using conductive adhesive
JP2008127484A (en) Curing promoter for epoxy resin, epoxy resin composition, and resin composition for electronic material
WO2016059980A1 (en) Liquid epoxy resin composition
TW201628016A (en) Conductive resin composition and semiconductor device