WO2016104232A1 - 導電性ペースト - Google Patents
導電性ペースト Download PDFInfo
- Publication number
- WO2016104232A1 WO2016104232A1 PCT/JP2015/085010 JP2015085010W WO2016104232A1 WO 2016104232 A1 WO2016104232 A1 WO 2016104232A1 JP 2015085010 W JP2015085010 W JP 2015085010W WO 2016104232 A1 WO2016104232 A1 WO 2016104232A1
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- WIPO (PCT)
- Prior art keywords
- conductive paste
- mass
- paste according
- parts
- conductive
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Classifications
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- 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
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- 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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a conductive paste that can be suitably used for forming an electrode of a chip-type electronic component, for example.
- chip-type electronic components such as a chip inductor, a chip capacitor, and a chip resistor are surface-mounted on the substrate.
- Such a chip-type electronic component usually includes a pair of electrodes (referred to as terminal electrodes, external electrodes, or simply electrodes) for electrical connection with a circuit on the substrate.
- this terminal electrode is usually soldered to a circuit on the substrate.
- thermosetting conductive paste containing a conductive resin in a specific ratio.
- Patent Documents 2 and 3 include copper powder, a thermosetting resin, a chelate-forming substance, and a specific alkoxy group-containing modified silicone resin as a conductive paste suitable for conducting the through-hole portion of the substrate.
- a conductive paste is disclosed.
- Patent Document 4 discloses a conductive paint in which copper powder surface-coated with titanate or the like, a specific resol type phenol resin, an amino compound, a chelate layer forming agent, an epoxy resin, and an epoxy polyol are blended at a specific ratio.
- the Patent Document 5 describes a specific adhesive consisting of a specific copper-silver alloy powder and a curable resin composition as a conductive adhesive used for fixing and joining an electronic component on a wiring circuit instead of soldering.
- a conductive adhesive containing a polyvinyl acetal resin, a polyamide resin, and / or a rubber-modified epoxy resin in a conductive resin.
- the chip-type electronic component When a chip-type electronic component is surface-mounted on a substrate, the chip-type electronic component generates heat during use, and the connection between the chip-type electronic component and the substrate is distorted due to the difference in thermal expansion between the chip-type electronic component and the substrate May concentrate and cracks and interfacial debonding may occur at the connection portion. Cracks and interfacial debonding can cause poor conduction at the connection.
- An object of the present invention is to provide a conductive paste suitable for forming an electrode of a chip-type electronic component, which can suppress the occurrence of cracks and surface peeling due to a difference in thermal expansion as described above.
- a conductive paste including a conductive filler, a chelate-forming substance, a phenol resin, and a modified epoxy resin is provided.
- the modified epoxy resin is preferably at least one selected from the group consisting of urethane-modified resins, rubber-modified resins, ethylene oxide-modified resins, propylene oxide-modified resins, fatty acid-modified resins, and urethane rubber-modified resins.
- the total amount of the resin contained in the conductive paste is preferably 11 parts by mass or more and 43 parts by mass or less with respect to 100 parts by mass of the conductive filler.
- the content of the modified epoxy resin based on the total amount of the resin contained in the conductive paste is preferably 13% by mass or more and 60% by mass or less.
- the phenolic resin is preferably a resol type phenolic resin.
- the content of the phenol resin based on the total amount of the resin contained in the conductive paste is 38% by mass or more and 85% by mass or less.
- the chelate-forming substance is one or more compounds selected from the group consisting of a pyridine derivative represented by the formula I (wherein n represents an integer of 2 or more and 8 or less) and 1,10-phenanthroline. preferable.
- the ratio of the chelate-forming substance to 100 parts by mass of the conductive filler is preferably 0.1 parts by mass or more and 2.0 parts by mass or less.
- the conductive paste further contains a boron compound.
- the boron compound is preferably a borate ester compound.
- the boric acid ester compound is preferably a boric acid triester compound.
- the boric acid triester compound preferably has 3 to 54 carbon atoms.
- the conductive paste preferably contains a boron compound in a range of 0.02 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the conductive filler.
- the conductive paste further contains a highly reactive epoxy resin.
- the content of the highly reactive epoxy resin based on the total amount of the resin contained in the conductive paste is preferably 1.4% by mass or more and 9.5% by mass or less.
- the conductive paste further includes a coupling agent.
- the conductive paste preferably contains the coupling agent in the range of 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the conductive filler.
- the conductive paste preferably contains copper powder as the conductive filler.
- the conductive paste preferably contains silver powder as the conductive filler.
- the conductive paste preferably contains silver-coated copper powder as the conductive filler.
- a terminal electrode of a chip-type electronic component at least a part of which is a cured product of the conductive paste.
- a chip-type electronic component including a terminal electrode at least partially made of a cured product of the conductive paste.
- a conductive paste suitable for forming an electrode of a chip-type electronic component that can suppress the occurrence of cracks and surface peeling due to a difference in thermal expansion as described above.
- the conductive paste of the present invention contains at least a conductive filler, a chelate-forming substance, a phenol resin, and a modified epoxy resin.
- a conductive filler used in a known conductive paste particularly a conductive filler used in a known conductive paste used to form a terminal electrode of a chip-type electronic component, is appropriately selected. Can be used.
- metal powder can be used, particularly copper powder, silver powder, or a kind of powder coated with silver (silver coated copper powder) or a mixture of two or more of these powders. Is preferred.
- Copper and silver have low electrical resistivity among metals, and good conductivity of the cured conductive paste can be obtained.
- the surface of the metal powder may be covered with an oxide film.
- the surface of normally available copper powder is covered with an oxide film.
- the particles of the conductive filler can be strongly bonded to each other. Therefore, good conductivity of the cured conductive paste can be obtained.
- the contact resistance between the metal powders can be reduced and the conductivity can be improved by strong pressure bonding.
- the conductive paste of the present invention contains at least a phenol resin and a modified epoxy resin as a resin.
- the resin contained in the conductive paste may be only a phenol resin and a modified epoxy resin, but may contain other resins in addition to these resins.
- the elastic modulus of the cured conductive paste can be adjusted, particularly reduced. Therefore, when the terminal electrode of the chip-type electronic component is formed using a conductive paste, the elastic modulus can be reduced. If such a chip-type electronic component is fixed to the substrate by soldering or the like, the terminal electrode functions as a buffer material, and it is possible to suppress the occurrence of cracks and surface peeling due to the difference in thermal expansion as described above. .
- Modified epoxy resin is an epoxy resin that has been modified to give various performances to an epoxy resin such as a bisphenol A type epoxy resin.
- the epoxy resin modified to have various performances means, for example, one obtained by polymerizing different components in the epoxy resin to partially change the structure of the main chain, or one having a functional group introduced therein.
- those having flexibility are preferable.
- urethane-modified epoxy resin, rubber-modified epoxy resin, ethylene oxide-modified epoxy resin, propylene oxide-modified epoxy resin, fatty acid-modified epoxy resin, urethane rubber-modified epoxy resin, and the like are preferable.
- As the modified epoxy resin a modified epoxy resin having an epoxy equivalent of more than 186 can be used.
- a resol type phenol resin is preferable. Since the resol type phenol resin has a self-reactive functional group, it has an advantage that it can be cured only by heating.
- the resol type phenol resin can be obtained by reacting phenol or a phenol derivative with formaldehyde in the presence of an alkali catalyst.
- phenol derivative examples include alkylphenols such as cresol, xylenol, and t-butylphenol, and phenylphenol and resorcinol.
- Resitop PL-4348 (trade name) manufactured by Gunei Chemical Industry Co., Ltd. can be used.
- the highly reactive epoxy resin refers to a polyfunctional epoxy resin having an epoxy equivalent of 186 or less and two or more epoxy groups in one molecule.
- a suitable fixing strength adheresion strength between a chip-type electrode component in which an electrode is formed using a conductive paste and a substrate
- Examples of the highly reactive epoxy resin include Denacol series (trade names EX212L, EX214L, EX216L, EX321L and EX850L) manufactured by Nagase ChemteX Corporation, and trade names ED-503G and ED-523G manufactured by ADEKA Corporation, Mitsubishi.
- the conductive paste contains other resins (resins other than phenolic resins, modified epoxy resins and highly reactive epoxy resins), other resins used for conductive pastes known as other resins, particularly printed wiring boards Resin used for the well-known electroconductive paste used in order to plan conduction
- electrical_connection of a through hole can be used suitably.
- resins with curing shrinkage that is, thermosetting resins are preferable, and for example, epoxy resins other than modified epoxy resins and highly reactive epoxy resins, and silicone resins can be used.
- a ligand compound capable of chelate bonding to a conductive filler can be used.
- a metal powder in the preparation of a conductive paste It is desirable that it can be dissolved.
- Chelating substances that satisfy this requirement include diamines capable of bidentate coordination, such as ethylenediamine, N- (2-hydroxyethyl) ethylenediamine, trimethylenediamine, 1,2-diaminocyclohexane, and triethylenetetramine.
- Bidentate ligands that utilize ring nitrogen and amino nitrogen such as 2-aminomethylpyridine, purine, adenine, histamine, and 1,3-dione that produces acetylacetonato type bidentate ligands And similar compounds such as acetylacetone, 4,4,4-trifluoro-1-phenyl-1,3-butanedione, hexafluoroacetylacetone, benzoylacetone, dibenzoylmethane, 5,5-dimethyl-1,3- Cyclohexanedione, oxine, 2-methyloxine, oxine 5-sulfonic acid, dimethylglyoxime, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, can also be mentioned and salicylaldehyde.
- ring nitrogen and amino nitrogen such as 2-aminomethylpyridine, purine, adenine, histamine, and 1,3-dione that
- the 1,3-diones that produce the acetylacetonato-type bidentate ligands and similar compounds are keto-enol tautomeric, although the keto body itself is not a chelating agent.
- the anion species generated by releasing protons can function as bidentate ligands of the acetylacetonate type.
- the chelate-forming substance is one or more selected from the group of nitrogen-containing heteroaromatic compounds composed of a pyridine derivative represented by the formula I (wherein n represents an integer of 2 to 8) and 1,10-phenanthroline It is preferable that it is a kind of multidentate ligand compound.
- the pyridine derivative represented by the formula I and 1,10-phenanthroline can efficiently chelate metal ions such as copper ions, and the resulting chelate complex is relatively stable near room temperature.
- the precipitate is washed with hot toluene, water and hot toluene in this order and dried to obtain the desired polypyridine.
- the degree of polymerization n is adjusted by selecting the starting material and the degree of bromination of the brominated pyridine contained.
- the zero-valent nickel complex an equimolar mixture of nickel-1,5-octadiene complex and 1,5-octadiene and triallylphosphine is used.
- n is 2 or 3
- a purified simple compound is commercially available as a reagent.
- n is 4 or more, it is also possible to synthesize compounds having n of 2 or 3 as starting materials.
- the synthesized polypyridine represented by the formula I has a slight distribution of the number of repetitions of the pyridine skeleton when purified to the extent of recrystallization, and shows an average value obtained from the molecular weight distribution.
- n 1 pyridine itself is rarely mixed during precipitation, and only contains those having n of 2 or more. When n is 2 or more, sufficient chelate forming ability is exhibited.
- the solubility in a solvent decreases. When n exceeds 8, the solubility in a solvent becomes poor, and the preparation of a solution required for forming a desired chelate tends to become increasingly difficult.
- the repeating number n of the pyridine skeleton is preferably selected in the range of 2 to 8, More preferably, n is in the range of 2 to 3.
- the conductive paste may contain a boron compound.
- a boron compound in combination with the above components, the storage stability of the conductive paste can be improved.
- the conductive paste may not contain a boron compound.
- the boron compound is preferably a boric acid ester compound, particularly a boric acid triester compound.
- the number of carbon atoms of the boric acid triester compound is preferably from 3 to 54, more preferably from 6 to 30, and even more preferably from 6 to 12, from the viewpoint of availability and / or ease of production.
- boric acid ester compound alkyl or aryl esters of boric acid can be used, and specifically, trimethyl borate, triethyl borate, tributyl borate, tridecyl borate, trioctadecyl borate, triphenyl borate and the like can be used.
- boric acid triester compound having 6 to 12 carbon atoms include triethyl borate, 2-methoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-isopropoxy-4,4, 5,5-tetramethyl-1,3,2-dioxaborolane, 2-isopropoxy-4,4,6-trimethyl-1,3,2-dioxaborinane, tripropyl borate, isopropyl borate, tris (trimethylsilyl) borate, boric acid Mention may be made of tributyl.
- the coupling agent it is preferable to appropriately add a coupling agent effective for the conductive filler (particularly, metal powder such as copper), for example, a silane coupling agent.
- a coupling agent it is easier to obtain a suitable fixing strength (adhesion strength between a chip-type electrode component in which an electrode is formed using a conductive paste and a substrate).
- Preferred coupling agent types are, for example, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, etc. be able to. These have low volatility and low reactivity with resins (especially thermosetting resins).
- a solvent an antifoaming agent, an anti-settling agent, a dispersing agent, and the like can be added to the conductive paste.
- Zinc powder as an antioxidant and resin curing agents can also be used as appropriate.
- a solvent that does not react with the resin (particularly thermosetting resin) and can dissolve the chelate-forming substance can be selected.
- the amount of the resin component (the total amount of resin contained in the conductive paste) with respect to 100 parts by mass of the conductive filler is preferably 11 parts by mass to 43 parts by mass.
- the resin component is 11 parts by mass or more, the shrinkage of the resin component with respect to the entire paste becomes good, and it is easy to obtain a good contact ratio between the conductive fillers, and hence a good paste cured product. It is.
- the resin component is 43 parts by mass or less, the amount of the resin component with respect to the entire paste is in a suitable range, and therefore, it is possible to obtain a good contact rate between conductive fillers, and thus a good paste cured product conductivity. Easy.
- the resin component is more preferably 15 parts by mass or more and more preferably 30 parts by mass or less with respect to 100 parts by mass of the conductive filler.
- the amount is 15 parts by mass or more, it is easy to obtain excellent conductivity of the cured paste by the curing shrinkage force of the resin.
- it is 30 parts by mass or less, it is further easy to secure a contact area between the fillers, and it is easy to obtain excellent conductivity of the cured paste.
- the ratio of the modified epoxy resin in the resin component is preferably 13% by mass to 60% by mass.
- the modified epoxy resin in the resin component is in the range of 13% by mass to 60% by mass, it is easy to lower the elastic modulus of the cured conductive paste, and suitable fixing strength (using conductive paste) Thus, it is easy to obtain a bonding strength between the chip-type electrode component on which the electrode is formed and the substrate.
- the proportion of the phenol resin in the resin component is preferably 38% by mass to 85% by mass.
- it is easy to obtain excellent conductivity of the cured paste by the curing shrinkage force of the resin. Since it is easy to ensure the contact area between fillers as it is 85 mass% or less, it is easy to obtain the electroconductivity of the excellent paste hardened
- the ratio of the highly reactive epoxy resin in the resin component is preferably 1.4% by mass to 9.5% by mass.
- suitable adhesion strength between the chip-type electrode component in which the electrode is formed using the conductive paste and the substrate
- fixing strength it is easier to obtain
- the amount of the chelate-forming substance is preferably 0.1 parts by mass or more and 2.0 parts by mass or less per 100 parts by mass of the conductive filler. When this amount is 0.1 parts by mass or more, it is easy to obtain a good volume resistivity when an electrode is formed using a conductive paste. When this amount is 2.0 parts by mass or less, it is easy to obtain good storage stability of the conductive paste.
- the amount of the boron compound is preferably 0.02 parts by mass or more and preferably 10 parts by mass or less per 100 parts by mass of the conductive filler.
- this amount is 0.02 parts by mass or more, it is easy to obtain good storage stability of the conductive paste.
- this amount is 10 parts by mass or less, it is easy to obtain a good volume resistivity of the cured conductive paste.
- the amount added can be appropriately selected according to the amount of the conductive filler contained in the conductive paste. For example, 0.1 to 10 parts per 100 parts by weight of the conductive filler. It can be determined in consideration of adhesion and the like in the range of mass parts. When the coupling agent is within this range, it is easier to obtain a suitable fixing strength (adhesion strength between a chip-type electrode component in which an electrode is formed using a conductive paste and a substrate).
- the conductive paste contains a boron compound
- a conductive paste excellent in storage stability can be obtained without blending a latent curing agent.
- the conductive paste of the present invention is stable even if it contains a chelate-forming agent that is not a latent curing agent, for example, amines such as a pyridine derivative (for example, a compound represented by Formula I) or 1,10-phenanthroline. Excellent in properties.
- the conductive paste can be prepared by a preparation method known in the field of conductive paste.
- the conductive paste can be prepared by appropriately mixing the components constituting the conductive paste.
- a conductive paste can be prepared by mixing components other than the conductive filler and then adding the conductive filler to the obtained mixture.
- the conductive paste of the present invention can be suitably used for forming terminal electrodes of chip-type electronic components such as chip inductors, chip capacitors, and chip resistors.
- the terminal electrode is obtained by applying a conductive paste to a position where the electrical connection with the inside of the chip-type electronic component is possible (the portion of the chip-type electronic component where the terminal electrode is to be provided), and heating and curing as appropriate. Can be formed.
- the heating temperature can be appropriately determined in consideration of the components used, particularly the curing temperature of the resin.
- the cured product of the conductive paste may be used as the terminal electrode as it is.
- the entire terminal electrode is made of a cured conductive paste.
- the surface of the electrode made of a cured conductive paste can be plated with a metal such as nickel or tin.
- the cured product of the conductive paste functions as a base electrode, and a part of the terminal electrode is formed by the cured product of the conductive paste.
- a configuration similar to that of a known chip-type electronic component can be adopted except that at least a part of the terminal electrode is made of a cured product of the conductive paste.
- the terminal electrode of such a chip type electronic component can be fixed to the substrate by a known method for fixing the chip type electronic component to the substrate, such as soldering.
- Tables 1 and 2 summarize the composition and evaluation results of the conductive filler in each example.
- surface is a mass part.
- the description “5.0.E-05” means “5.0 ⁇ 10 ⁇ 5 ”.
- Real 1 means Example 1
- Rao 1 means Comparative Example 1.
- the materials used are as follows. -Conductive filler copper powder (Mitsui Metal Mining Co., Ltd., trade name: T-22), ⁇ Phenolic resin Resol type phenolic resin having a weight average molecular weight of about 20,000 obtained by reacting phenol and formaldehyde in the presence of an alkali catalyst (manufactured by Gunei Chemical Industry Co., Ltd., trade name: Resitop PL-4348), Modified epoxy resin Urethane modified epoxy resin (manufactured by ADEKA, trade name: EPU-78-13S (epoxy equivalent: 210, two epoxy groups in the molecule)), Rubber-modified epoxy resin (manufactured by ADEKA, trade name: EPR-21 (epoxy equivalent: 200, two epoxy groups in the molecule)), Highly reactive epoxy resin Bifunctional epoxy resin (manufactured by Nagase ChemteX Corporation, trade name: EX-214L (epoxy equivalent: 120, epoxy groups in the molecule: two)), Multi
- a conductive paste was prepared based on the formulation (parts by mass) shown in Table 1 or Table 2. Specifically, first, a material other than the conductive filler was put into a container and stirred using a rotation-revolution stirrer (manufactured by Kurashiki Boseki Co., Ltd.) to prepare a uniform liquid resin composition. Next, a conductive filler was added to the prepared resin composition, and stirring was performed using a rotation-revolution stirrer (manufactured by Kurashiki Boseki Co., Ltd.) to obtain a conductive paste.
- a rotation-revolution stirrer manufactured by Kurashiki Boseki Co., Ltd.
- the conductive paste of the example contains a modified epoxy resin, and the conductive paste of the comparative example does not contain a modified epoxy resin.
- Examples 23 to 26, 28, 47 to 50 and 52 a highly reactive epoxy resin was blended into the conductive paste. Furthermore, in Examples 27 and 51, a coupling agent was blended into the conductive paste.
- the elastic modulus of the cured film was measured in a load-unloading test mode (test force: 100 mN) using a dynamic ultra micro hardness tester (manufactured by Shimadzu Corporation, trade name: DUH-211SR).
- the indenter used was a triangular pan indenter (115 ° ridge angle, Belkovic type).
- the conductive paste was printed on a glass plate in a strip shape having a thickness of 80 ⁇ m and 1 cm ⁇ 5 cm using a metal mask having a thickness of 80 ⁇ m, dried at 80 ° C. for 5 minutes to remove the solvent, and then 210 ° C. 1 Cured in time.
- the volume resistivity test method described in JIS-H-8646 the width, length, and thickness of the formed conductive paste cured film were measured, and the measured resistance value was measured by a four-terminal method. Volume resistivity was measured.
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Abstract
Description
導電性フィラーとして、公知の導電性ペーストに使用される導電性フィラー、特にはチップ型電子部品の端子電極を形成するために使用される公知の導電性ペーストに使用される導電性フィラーを、適宜用いることができる。
本発明の導電性ペーストは、樹脂として、少なくともフェノール樹脂と変性エポキシ樹脂とを含む。導電性ペーストに含まれる樹脂は、フェノール樹脂と変性エポキシ樹脂だけであってもよいが、これら樹脂に加えてその他の樹脂を含んでもよい。
フェノール樹脂に加えて変性エポキシ樹脂を用いることによって、導電性ペースト硬化物の弾性率を調整、特には低下させることができる。したがって、チップ型電子部品の端子電極を、導電性ペーストを用いて形成した場合、その弾性率を低下させることができる。このようなチップ型電子部品を基板にはんだ付け等によって固定すれば、端子電極が言わば緩衝材として機能し、前述のような熱膨張差によるクラックや表面剥離の発生を抑制することが可能となる。
フェノール樹脂は、前述のように、硬化時の収縮率が高い(従って硬化したペーストの導電性が高くなる)。
高反応性エポキシ樹脂とは、エポキシ当量が186以下であって、且つ1分子中にエポキシ基が2つ以上ある多官能のエポキシ樹脂をいう。変性エポキシ樹脂およびフェノール樹脂に加えて高反応性エポキシ樹脂を用いることによって、好適な固着強度(導電性ペーストを用いて電極を形成したチップ型電極部品と基板との固着強度)を得ることがさらに容易である。
導電性ペーストが、その他の樹脂(フェノール樹脂、変性エポキシ樹脂および高反応性エポキシ樹脂以外の樹脂)を含む場合、その他の樹脂として公知の導電性ペーストに使用される樹脂、特にはプリント配線基板のスルーホールの導通を図るために使用される公知の導電性ペーストに使用される樹脂を、適宜用いることができる。その他の樹脂として、硬化収縮を伴う樹脂、すなわち熱硬化性樹脂が好ましく、例えば、変性エポキシ樹脂および高反応性エポキシ樹脂以外のエポキシ樹脂や、シリコーン樹脂を用いることができる。
キレート形成物質として、導電性フィラー(特には金属)に対してキレート結合が可能な配位子化合物が利用でき、特に、導電性ペーストの調製に際し、金属粉に作用させる工程では、有機溶媒中に溶解できることが望ましい。この要件を満たすキレート形成物質として、二座配位が可能なジアミン類、例えば、エチレンジアミン、N-(2-ヒドロキシエチル)エチレンジアミン、トリメチレンジアミン、1,2-ジアミノシクロヘキサン、トリエチレンテトラミンなど、芳香環窒素とアミノ窒素を利用する二座配位子、例えば、2-アミノメチルピリジン、プリン、アデニン、ヒスタミンなど、さらには、アセチルアセトナト型の二座配位子を生成する1,3-ジオン類とその類似化合物、例えば、アセチルアセトン、4,4,4-トリフルオロ-1-フェニル-1,3-ブタンジオン、ヘキサフルオロアセチルアセトン、ベンゾイルアセトン、ジベンゾイルメタン、5,5-ジメチル-1,3-シクロヘキサンジオン、オキシン、2-メチルオキシン、オキシン-5-スルホン酸、ジメチルグリオキシム、1-ニトロソ-2-ナフトール、2-ニトロソ-1-ナフトール、サリチルアルデヒドなどをも挙げることができる。なお、前記アセチルアセトナト型の二座配位子を生成する1,3-ジオン類とその類似化合物は、ケト体自体は、キレート化剤ではないものの、ケト・エノール互変異性をし、エノール体は酸として機能する結果、プロトンを放出し生成するアニオン種はアセチルアセトナト型の二座配位子として機能が可能となる。
導電性ペーストはほう素化合物を含んでもよい。上記成分と組み合わせてほう素化合物を用いることにより、導電性ペーストの保管安定性を向上させることが可能である。ただし、導電性ペーストがほう素化合物を含まなくてもよい。
カップリング剤としては、導電性フィラー(特には、銅などの金属粉)に対して有効なカップリング剤、例えば、シラン系カップリング剤を適宜添加することが好ましい。カップリング剤を用いることにより、好適な固着強度(導電性ペーストを用いて電極を形成したチップ型電極部品と基板との固着強度)を得ることがさらに容易である。
導電性ペーストには、必要に応じて、溶媒、消泡剤、沈降防止剤、分散剤などを適宜加えることができる。酸化防止剤としての亜鉛粉末や、樹脂の硬化剤も適宜用いることができる。
導電性フィラー100質量部に対する樹脂成分の量(導電性ペーストに含まれる樹脂の総量)は11質量部~43質量部が好ましい。樹脂成分が11質量部以上であると、ペースト全体に対する樹脂成分の収縮性が良好となり、良好な導電性フィラー同士の接触率を得ること、したがって良好なペースト硬化物の導電性を得ることが容易である。また、樹脂成分が43質量部以下であると、ペースト全体に対する樹脂成分の量が好適な範囲となり、したがって良好な導電性フィラー同士の接触率、ひいては良好なペースト硬化物の導電性を得ることが容易である。
導電性ペーストの分野で公知の調製方法によって、導電性ペーストを調製することができる。導電性ペーストを構成する各成分を適宜混合することにより、導電性ペーストを調製することができる。例えば導電性フィラー以外の成分を混合し、その後、得られた混合物に導電性フィラーを添加することにより、導電性ペーストを調製することができる。
本発明の導電性ペーストは、チップインダクタ、チップコンデンサ、チップ抵抗などのチップ型電子部品の端子電極を形成するために好適に使用することができる。
・導電性フィラー
銅粉(三井金属鉱業株式会社製、商品名:T-22)、
・フェノール樹脂
フェノールとホルムアルデヒドをアルカリ触媒下で反応して得られる重量平均分子量約20000のレゾール型フェノール樹脂(群栄化学工業株式会社製、商品名:レヂトップPL-4348)、
・変性エポキシ樹脂
ウレタン変性エポキシ樹脂(株式会社ADEKA製、商品名:EPU-78-13S(エポキシ当量:210、分子中のエポキシ基:2つ))、
ゴム変性エポキシ樹脂(株式会社ADEKA製、商品名:EPR-21(エポキシ当量:200、分子中のエポキシ基:2つ))、
・高反応性エポキシ樹脂
2官能エポキシ樹脂(ナガセケムテックス株式会社製、商品名:EX-214L(エポキシ当量:120、分子中のエポキシ基:2つ))、
多官能エポキシ樹脂(三菱化学株式会社製、商品名:jER630(エポキシ当量:100、分子中のエポキシ基:3つ))、
・カップリング剤
シランカップリング剤(モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製、商品名:TSL8350)、
・キレート形成物質
2,2’-ビピリジル(n=2の式Iの化合物)、
1,10-フェナントロリン、
ピリジン化合物(n=4の式Iの化合物)、
ピリジン化合物(n=8の式Iの化合物)、
・ほう素化合物
ほう酸トリメチル、
ほう酸トリエチル、
ほう酸トリブチル、
ほう酸トリデシル、
ほう酸トリオクタデシル、
・溶媒
ブチルセロソルブ。
樹脂の硬化物について弾性率を測定した。前記自転-公転攪拌機を用い、表1もしくは2に示される配合比でフェノール樹脂、変性エポキシ樹脂、高反応性エポキシ樹脂、カップリング剤、キレート形成物質、ほう素化合物と溶剤を混合し、樹脂混合物を得た。この樹脂混合物を、厚さ120μmのメタルマスクを使用して、ガラス板に厚さ120μm、1cm×3cmの短冊状に印刷し、80℃5分で乾燥して溶剤を除去した後、210℃1時間で硬化させた。ダイナミック超微小硬度計(島津製作所製、商品名:DUH-211SR)を用い、負荷-除荷試験モード(試験力:100mN)により硬化膜の弾性率を測定した。圧子は三角すい圧子(稜間角115度、ベルコビッチタイプ)を使用した。
導電性ペーストを、厚さ80μmのメタルマスクを使用して、ガラス板に厚さ80μm、1cm×5cmの短冊状に印刷し、80℃5分で乾燥して溶剤を除去した後、210℃1時間で硬化させた。JIS-H-8646に記載の体積抵抗率試験法に準拠して、形成された導電性ペースト硬化膜の幅、長さ、および厚みを実測し、4端子法にて測定抵抗値を測定し、体積抵抗率を測定した。
導電性ペーストを、厚さ80μmのメタルマスクを使用して、銅板に厚さ80μm、1cm×1cmの短冊状に印刷し、80℃5分で乾燥して溶剤を除去した後、210℃1時間で硬化させた。Snめっき電極付き3216チップ(TOP Line製、商品名:1206P7A-TIN)に接着剤(ヘンケルジャパン株式会社製、商品名:LOCTITE)を塗布し、導電性ペースト硬化膜上に静置し、24時間室温硬化させた。ボンドテスタDage series4000(株式会社アークテック)を用い、ダイシェア強度を測定した。
保管安定性の評価方法に関しては、導電性ペースト調製直後の粘度と、40℃で1日間保管した後の粘度とを粘度計(東機産業株式会社製、商品名:VISCOMETER TV-25)で測定し、保管中に生じた粘度の上昇倍率を算定した。粘度測定は25℃において行った。
Claims (22)
- 導電性フィラーと、キレート形成物質と、フェノール樹脂と、変性エポキシ樹脂と、を含むことを特徴とする、導電性ペースト。
- 変性エポキシ樹脂が、ウレタン変性樹脂、ゴム変性樹脂、エチレンオキサイド変性樹脂、プロピレンオキサイド変性樹脂、脂肪酸変性樹脂、およびウレタンゴム変性樹脂からなる群から選ばれる少なくとも一種であることを特徴とする、請求項1に記載の導電性ペースト。
- 導電性ペーストに含まれる樹脂の総量が、導電性フィラー100質量部に対して11質量部以上43質量部以下であることを特徴とする、請求項1または2に記載の導電性ペースト。
- 導電性ペーストに含まれる樹脂の総量を基準とする変性エポキシ樹脂の含有率が、13質量%以上60質量%以下である、請求項1~3の何れかに記載の導電性ペースト。
- フェノール樹脂が、レゾール型フェノール樹脂であることを特徴とする、請求項1~4の何れかに記載の導電性ペースト。
- 導電性ペーストに含まれる樹脂の総量を基準とするフェノール樹脂の含有率が、38質量%以上85質量%以下である、請求項1~5の何れかに記載の導電性ペースト。
- 導電性フィラー100質量部に対するキレート形成物質の割合が、0.1質量部以上2.0質量部以下であることを特徴とする、請求項1~7の何れかに記載の導電性ペースト。
- ほう素化合物をさらに含むことを特徴とする、請求項1~8の何れかに記載の導電性ペースト。
- ほう素化合物が、ほう酸エステル化合物であることを特徴とする、請求項9記載の導電性ペースト。
- ほう酸エステル化合物が、ほう酸トリエステル化合物であることを特徴とする、請求項10に記載の導電性ペースト。
- ほう酸トリエステル化合物の炭素数が3~54であることを特徴とする、請求項11に記載の導電性ペースト。
- ほう素化合物を、導電性フィラー100質量部当り、0.02質量部以上10質量部以下の範囲で含むことを特徴とする、請求項9~12の何れかに記載の導電性ペースト。
- 高反応性エポキシ樹脂をさらに含むことを特徴とする、請求項1~13の何れかに記載の導電性ペースト。
- 導電性ペーストに含まれる樹脂の総量を基準とする高反応性エポキシ樹脂の含有率が、1.4質量%以上9.5質量%以下である、請求項14に記載の導電性ペースト。
- カップリング剤をさらに含むことを特徴とする、請求項1~15の何れかに記載の導電性ペースト。
- カップリング剤を、導電性フィラー100質量部当り、0.1質量部以上10質量部以下の範囲で含むことを特徴とする、請求項16に記載の導電性ペースト。
- 導電性フィラーとして、銅粉を含むことを特徴とする、請求項1~17の何れかに記載の導電性ペースト。
- 導電性フィラーとして、銀粉を含むことを特徴とする、請求項1~18の何れかに記載の導電性ペースト。
- 導電性フィラーとして、銀コート銅粉を含むことを特徴とする、請求項1~19の何れかに記載の導電性ペースト。
- 少なくとも一部が請求項1~20の何れかに記載される導電性ペーストの硬化物からなる、チップ型電子部品の端子電極。
- 少なくとも一部が請求項1~20の何れかに記載される導電性ペーストの硬化物からなる端子電極を含む、チップ型電子部品。
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WO2021220975A1 (ja) | 2020-05-01 | 2021-11-04 | 昭栄化学工業株式会社 | 電子部品の製造方法 |
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