WO2016018191A1 - Composition électroconductrice à base de résine époxyde - Google Patents

Composition électroconductrice à base de résine époxyde Download PDF

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Publication number
WO2016018191A1
WO2016018191A1 PCT/SG2015/000131 SG2015000131W WO2016018191A1 WO 2016018191 A1 WO2016018191 A1 WO 2016018191A1 SG 2015000131 W SG2015000131 W SG 2015000131W WO 2016018191 A1 WO2016018191 A1 WO 2016018191A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrically conductive
conductive composition
lactone
epoxy resins
delta
Prior art date
Application number
PCT/SG2015/000131
Other languages
English (en)
Inventor
Hans-Werner Hagedorn
Yvonne LÖWER
Tanja Dickel
Katja Stenger
Ling Xin YONG
Keng Wei TEO
Sebastian Fritzsche
Michael Schäfer
Original Assignee
Heraeus Deutschland GmbH & Co. KG
Heraeus Materials Singapore Pte., Ltd.
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 Heraeus Deutschland GmbH & Co. KG, Heraeus Materials Singapore Pte., Ltd. filed Critical Heraeus Deutschland GmbH & Co. KG
Publication of WO2016018191A1 publication Critical patent/WO2016018191A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • 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
    • 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
    • C08K2003/0806—Silver

Definitions

  • the present invention relates to an electrically conductive composition especially for use as a hardenable electrically conductive adhesive.
  • Electronic devices require electrically conductive connections to active and passive components.
  • Electrically conductive adhesives are used in a variety of applications to attach bare dies and other electronic components such as resistors or condensators to a substrate, for example lead frames, printed circuit boards/flexible electronics, ceramic substrates (e.g. LTCC) or DCBs and the like. Such devices are for example used for communication (e.g. mobile phones, tablets, computer), power conversion (e.g. power electronic modules), lighting (e.g. LED) or the like.
  • a number of requirements for an electrically conductive adhesive in these applications. It should be mechanically compliant and highly conductive. Low processing temperatures and compatibility with a wide range of substrates are required. Further requirements include elasticity and flexibility, biocompatibility, stable physical and chemical properties, good temperature stability, low price and so on,
  • thermal conductivity is of major importance in some applications, especially if it is used to bind for example heat sinks to electronic components.
  • some of known conductive adhesives have a good bulk thermal conductivity, they show limited thermal conductivity when used. It is believed that at least some of these problems are related to an insufficient contact between the electrically conductive adhesive and the electronic component or the substrate.
  • the inventive solution is an electrically conductive composition
  • the electrically conductive composition of the invention is a hardenable (curable, crosslinkable) composition.
  • the metal containing particles (a) of the invention are electrically conductive particles.
  • Such particles include well-known metal particles which comprise or consist of silver, aluminum, copper, tin, nickel or alloys thereof.
  • further suitable metal containing particles comprise inorganic particles which are metal coated with for example silver, aluminum, copper, tin, nickel or alloys thereof.
  • metal coated metal particles e.g. silver coated copper particles may be used.
  • different metal containing particles may be combined together and used as a mixture.
  • a suitable proportion of metal containing particles lies in the range of 25 to 95 wt.-% (weight-%) of the electrically conductive composition of the invention.
  • the proportion of metal containing particles is at least 30 wt.- % or at least 35 wt.-% or at least 50 wt.-% of the electrically conductive composition.
  • a proportion of metal containing particles of up to 93 or up to 92 wt.-% of the electrically conductive composition is preferred.
  • a preferred proportion of metal containing particles is in the range of 70 to 93 wt.-% of the electrically conductive composition, for other types of the electrically conductive composition it is in the order of 30 to 70 wt.-%.
  • the metal containing particles may have any shape. Flakes and spherical parti- cles are preferred.
  • An average particle size (d50) of the metal containing particles in the range of 1 to 15 m is preferred.
  • the term "average particle size” shall mean the average primary particle size (mean particle diameter, d50) determined by means of laser diffraction; d50 is the particle size where 50 wt.-% of all particles have a larger particle size and 50 wt.-% have a smaller particle size.
  • Laser diffraction measurements can be carried out making use of a particle size analyzer, for example, a Mastersizer 3000 from Malvern.
  • Component (b) of the electrically conductive composition is at least one epoxy resin.
  • Preferred epoxy resins are bisphenol A epoxy resins, bisphenol A/F epoxy resins, bisphenol F epoxy resins, novolac epoxy resins, aliphatic epoxy resins, cycloaliphatic epoxy resins and cyclosiloxane epoxy resins.
  • suitable bisphenol A epoxy resins include Araldite® GY 279 as well as QuatrexTM 1010 commercially available from Huntsman or D.E.R.TM 331 as well as D.E.R.TM 732 commercially available from Dow Chemical.
  • suitable bisphenol A F epoxy resins include Araldite® GY 891 , Araldite® PY 302-2 and Araldite® PY 3483 commercially available from Huntsman.
  • suitable bisphenol F epoxy resins include Araldite® GY 281 commercially available from Huntsman and D.E.R.TM 354 commercially available from Dow Chemical.
  • Suitable novolac epoxy resin is D.E.NTM 431 commercially available from Dow Chemical.
  • suitable cycloaliphatic epoxy resins include JER YX8000 commercially available from Mitsubishi Chemical and EPONEXTM Resin 1510 commercially available from Momentive Specialty Chemicals.
  • CS-697 commercially available from Designer Molecules Inc..
  • a suitable total proportion of the at least one epoxy resin is in the range of 3 to 30 wt.-% of the electrically conductive composition of the invention with a preferred range of 5 to .15 wt.-%. In some embodiments the total proportion of the at least one epoxy resin is at least 7 wt.-% or at least 9 wt.-% or at least 11 wt.-%. In some embodiments the total proportion of the at least one epoxy resin is up to 14 wt.-% or up to 12 wt.-%.
  • a preferred total proportion of the at least one epoxy resin is in the range of 5 to 7 wt.-% of the electrically conductive composition, for other types of the electrically conductive composition it is in the range of 8 to 12 wt.-%.
  • the electrically conductive composition of the invention comprises a component (c), i.e. at least one hardener for the at least one epoxy resin.
  • Preferred hardeners are hardeners having at least 2 reactive groups in one molecule, preferably wherein each reactive group contains at least one heteroatom having at least one free electron pair.
  • the hardener comprises an unsaturated ring system and/or nitrogen heteroatoms with a free electron pair. Suitable hardeners for epoxy resins are known in the art.
  • Examples include pyra- zine and dicyandiamide, both commercially available from Sigma Aldrich.
  • Other examples are Curezol® 2MZ-H, 2MZ-CN, 2PZ, C17Z, 2E4MZ, 2E4MZ-CN or C2MZH from Shikoku Chemical.
  • a suitable total proportion of the at least one hardener is in the range of 0.05 to 3 wt.-% of the electrically conductive composition of the invention with a preferred range of 0.05 to 1 wt.-%.
  • Component (d) of the electrically conductive composition of the invention is a lac- - tone or a mixture of lactones.
  • a lactone is a cyclic ester that can be seen as the condensation product of an OH group and a COOH group.
  • the lactone ring of the at least one lactone of component (d) comprises 3 to 7 or 4 to 6 carbon atoms.
  • a lactone may be used having 4 or 5 ring carbon atoms, in other embodiments the lactone ring may have 6 or 7 carbon atoms.
  • the at least one lactone (d) is a saturated lactone, especially a gamma-lactone, a delta-lactone or an epsilon-lactone.
  • the at least one lactone (d) has a melting tempera- ture below 50 °C; most preferably it is a liquid.
  • Preferred lactones for use according to the invention are delta-valerolactone, del- ta-hexalactone, delta-nonalactone, delta-decalactone, delta-undecalactone, gamma-butyrolactone, gamma-hexalactone, gamma-heptalactone, gamma- octalactone, epsilon-caprolactone, epsilon-octalactone, epsilon-nonalactone and mixtures thereof.
  • a suitable total proportion of the at least one lactone is in the range of 0.5 to 10 wt.-% of the electrically conductive composition of the invention, with a proportion of 0.5 to 5 wt.-% being preferred.
  • the total proportion of the at least one lactone is at least 1 wt.-% or at least 2 wt.-% or at least 3 wt.-%.
  • the upper limit of the at least one lactone is 7 wt.-% or 5 wt.-% or 3 wt.-%.
  • the electrically conductive composition of the invention may comprise one or more further components (e) in a total proportion of, for example, 0 to 10 wt.-% of the electrically conductive composition of the invention.
  • the further components (e) may be selected from the group consisting of diluents, electrically non-conductive particles and other additives. Examples of other additives include Theological modifiers and surface- active agents.
  • diluents compounds are considered which may be readily but not necessarily volatile at room temperature; preferred diluents are ethers, esters, carboxylic acids and ketones.
  • the proportion of diluents is less than 10 wt.-%, preferably less than 5 wt.-% and more preferred less than 3 wt.-% or less than 1 wt.- % of the electrically conductive composition of the invention.
  • Inorganic particles are preferably used as electrically non-conductive particles.
  • Such electrically non-conductive inorganic particles or fillers may be selected for example from silica, aluminosilicates, aluminum oxide, zirconia, silicon dioxide, titanium dioxide and the like.
  • the proportion of the electrically non- conductive particles is less than 10 wt.-%, preferably less than 5 wt.-% and more preferred less than 3 wt.-% of the electrically conductive composition of the invention.
  • the proportion of additives like rheological modifiers and surface- active agents is less than 5 wt.-%, preferably less than 3 wt.-% of the electrically conductive composition of the invention, In preferred embodiments, the electrically conductive composition of the invention does not comprise glass frit or at least not more than 1 wt.-% of glass frit.
  • the viscosity of the electrically conductive composition of the invention is in the range of 4 to 45 mPa-s, most preferably 8 to 35 mPa-s, measured in accordance with DIN 53018 (at 23 °C, CSR-measurement, cone-plate system, shear rate of 50 rounds per second).
  • the electrically conductive composition of the invention can be produced by mix- ing components (a) to (d) and, optionally, one or more components (e).
  • a further embodiment of the invention is an assembly comprising a substrate, the electrically conductive composition of the invention and an electronic component, i.e. the electrically conductive composition of the invention is located between the substrate and the electronic component.
  • substrates include those mentioned above, while examples of electronic components include the above mentioned bare dies, resistors and condensators.
  • the composition is hardened by heating.
  • Hardening conditions may be for example 5 to 60 minutes at an object temperature in the range of for example 60 to 200 °C, preferably 80 to 80 °C or 100 to 160 °C. It may be expedient to let said hardening precede by a heating-up phase of for example 5 to 60 minutes until reaching the object temperature.
  • a further embodiment of the invention is a hardened composition obtainable by hardening the hardenable electrically conductive composition of the present invention. Therefore, also an assembly, wherein the electrically conductive composition of the present invention is in a hardened state is part of the invention.
  • a further embodiment of the invention is an assembly comprising a substrate, the hardened electrically conductive composition of the invention and an electronic component.
  • the hardened electrically conductive composition of the invention serves as an electrically conductive adhesive and is therefore located between the substrate and the electronic component.
  • a further embodiment of the invention is the use of the electrically conductive composition of the invention as a hardenable electrically conductive adhesive, in particular in electronic applications.
  • the embodiments and advantages of the invention are further explained by the following non-limiting examples.
  • delta-valerolactone tech. (Sigma Aldrich)
  • cresol monoglycidyl ether (Sigma Aldrich)
  • the thermal diffusivity was measured by the laser flash measurement (LFA) ac- cording to DIN/EN 821/2.
  • the required amounts of epoxy resin and hardener were transfered to a beaker. and mixed with a spatula. Lactones and diluents were added and mixed with the spatula. Metal containing particles were added and mixed carefully with the spatula, followed by mixing with a paddle mixer at 300 to 400 U/min for 5 min.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Conductive Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Une composition électroconductrice comprend (a) des particules contenant du métal, (b) au moins une résine époxyde, (c) au moins un durcisseur pour l'au moins une résine époxyde, et (d) au moins une lactone.
PCT/SG2015/000131 2014-07-29 2015-06-19 Composition électroconductrice à base de résine époxyde WO2016018191A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SG10201404443QA SG10201404443QA (en) 2014-07-29 2014-07-29 Conductive composition
SG10201404443Q 2014-07-29

Publications (1)

Publication Number Publication Date
WO2016018191A1 true WO2016018191A1 (fr) 2016-02-04

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Application Number Title Priority Date Filing Date
PCT/SG2015/000131 WO2016018191A1 (fr) 2014-07-29 2015-06-19 Composition électroconductrice à base de résine époxyde

Country Status (3)

Country Link
SG (1) SG10201404443QA (fr)
TW (1) TW201614676A (fr)
WO (1) WO2016018191A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017066563A1 (fr) * 2015-10-15 2017-04-20 Henkel IP & Holding GmbH Utilisation de nickel et d'alliages contenant du nickel en tant que charges conductrices dans des formulations adhésives
CN112371150A (zh) * 2020-10-26 2021-02-19 厦门大学 镍铝双金属氮碳掺杂催化剂及其制备方法和其催化乙酰丙酸加氢制备γ-戊内酯的应用
US11414542B2 (en) * 2017-09-25 2022-08-16 Hexion Inc. Impregnation resin mixture

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5920371A (ja) * 1982-07-27 1984-02-02 Toyo Ink Mfg Co Ltd 導電性接着剤
JPS59130004A (ja) * 1983-01-18 1984-07-26 三井東圧化学株式会社 銀ペ−スト
CN101792627A (zh) * 2010-03-10 2010-08-04 彩虹集团公司 一种屏蔽导电油墨及其制备方法
KR20100113763A (ko) * 2009-04-14 2010-10-22 엘지이노텍 주식회사 스크린 프린팅이 가능한 반도체 패키징용 접착 페이스트

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5920371A (ja) * 1982-07-27 1984-02-02 Toyo Ink Mfg Co Ltd 導電性接着剤
JPS59130004A (ja) * 1983-01-18 1984-07-26 三井東圧化学株式会社 銀ペ−スト
KR20100113763A (ko) * 2009-04-14 2010-10-22 엘지이노텍 주식회사 스크린 프린팅이 가능한 반도체 패키징용 접착 페이스트
CN101792627A (zh) * 2010-03-10 2010-08-04 彩虹集团公司 一种屏蔽导电油墨及其制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE CAPLUS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 21 July 1984 (1984-07-21), XP002744994, Database accession no. 1984:424715 *
DATABASE CAPLUS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 26 January 1985 (1985-01-26), XP002744995, Database accession no. 1985:38018 *
F.M.SMITS: "Measurement of Sheet Resistivities with the Four-Point Probe", THE BELL SYSTEM TECHNICAL JOURNAL, May 1958 (1958-05-01), pages 711 - 718, XP009033160, Retrieved from the Internet <URL:http://en.wikipedia.org/wiki/Sheet_resistance>

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017066563A1 (fr) * 2015-10-15 2017-04-20 Henkel IP & Holding GmbH Utilisation de nickel et d'alliages contenant du nickel en tant que charges conductrices dans des formulations adhésives
US11414542B2 (en) * 2017-09-25 2022-08-16 Hexion Inc. Impregnation resin mixture
CN112371150A (zh) * 2020-10-26 2021-02-19 厦门大学 镍铝双金属氮碳掺杂催化剂及其制备方法和其催化乙酰丙酸加氢制备γ-戊内酯的应用

Also Published As

Publication number Publication date
SG10201404443QA (en) 2016-02-26
TW201614676A (en) 2016-04-16

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