JPWO2018181697A1 - Electrode-forming resin composition, chip-type electronic component, and method of manufacturing the same - Google Patents
Electrode-forming resin composition, chip-type electronic component, and method of manufacturing the same Download PDFInfo
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- 239000011342 resin composition Substances 0.000 title claims abstract description 86
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 229920005989 resin Polymers 0.000 claims abstract description 63
- 239000011347 resin Substances 0.000 claims abstract description 63
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 45
- -1 acrylic ester compound Chemical class 0.000 claims abstract description 33
- 239000010419 fine particle Substances 0.000 claims abstract description 32
- 229910052709 silver Inorganic materials 0.000 claims abstract description 31
- 239000004332 silver Substances 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 29
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 21
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 16
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 18
- 239000000919 ceramic Substances 0.000 claims description 16
- 125000001931 aliphatic group Chemical group 0.000 claims description 15
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 14
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 125000000962 organic group Chemical group 0.000 claims description 11
- 238000007639 printing Methods 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- 230000004580 weight loss Effects 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 238000006735 epoxidation reaction Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 10
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009766 low-temperature sintering Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 238000003618 dip coating Methods 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
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- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- 239000000203 mixture Substances 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
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- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
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- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
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- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
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- 125000006239 protecting group Chemical group 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- VTEYUPDBOLSXCD-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-2-methylcyclohexane Chemical compound CC1CCCCC1(OOC(C)(C)C)OOC(C)(C)C VTEYUPDBOLSXCD-UHFFFAOYSA-N 0.000 description 1
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)(*N(C(C=C1)=O)C1=O)N(C(c(cc1)c2cc1Pc(cc1C(N3*N(C(C=C4)=O)C4=O)=O)ccc1C3=O)=O)C2=O Chemical compound CC(C)(*N(C(C=C1)=O)C1=O)N(C(c(cc1)c2cc1Pc(cc1C(N3*N(C(C=C4)=O)C4=O)=O)ccc1C3=O)=O)C2=O 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 1
- JPNTUZVTAHVHFB-UHFFFAOYSA-N n-ethyl-n-hydroxyprop-2-enamide Chemical compound CCN(O)C(=O)C=C JPNTUZVTAHVHFB-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
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- 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
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
- C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- 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
- C08L63/08—Epoxidised polymerised polyenes
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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
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C1/00—Details
- H01C1/14—Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors
- H01C1/142—Terminals or tapping points or electrodes specially adapted for resistors; Arrangements of terminals or tapping points or electrodes on resistors the terminals or tapping points being coated on the resistive element
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
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- Polymers & Plastics (AREA)
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- Microelectronics & Electronic Packaging (AREA)
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- Manufacturing & Machinery (AREA)
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- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
- Manufacturing Cores, Coils, And Magnets (AREA)
- Coils Or Transformers For Communication (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
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Abstract
接着性や耐湿、耐熱処理後の電気抵抗の安定性などに優れた低温焼結型の電極形成用樹脂組成物を提供する。(A)熱硬化性樹脂と、(B)ラジカル開始剤と、(C)厚さ又は短径が1〜200nmの銀微粒子と、(D)(C)成分以外の平均粒径が2〜20μmの銀粉と、を必須成分とし、(A)熱硬化性樹脂が、(A1)ヒドロキシル基を有する、(メタ)アクリル酸エステル化合物又は(メタ)アクリルアミド化合物、(A2)常温で液状であり、ビスマレイミド樹脂、(A3)エポキシ化ポリブタジエン、を含む電極形成用樹脂組成物。Provided is a low-temperature sintering type electrode forming resin composition having excellent adhesiveness, moisture resistance, and stability of electrical resistance after heat treatment. (A) a thermosetting resin, (B) a radical initiator, (C) silver fine particles having a thickness or a short diameter of 1 to 200 nm, and (D) an average particle diameter other than the component (C) of 2 to 20 μm. (A) a (meth) acrylic ester compound or a (meth) acrylamide compound having a hydroxyl group, and (A2) a liquid at room temperature, A resin composition for forming an electrode, comprising a maleimide resin and (A3) an epoxidized polybutadiene.
Description
本開示は、電極形成用樹脂組成物並びに該電極形成用樹脂組成物を用いて電極形成したチップ型電子部品及びその製造方法に関する。
本開示は、特に、表面実装用チップ型電子部品の外部電極を形成する電極形成用樹脂組成物、それを用いたチップ型電子部品及びその製造方法に関する。The present disclosure relates to a resin composition for forming an electrode, a chip-type electronic component in which an electrode is formed using the resin composition for forming an electrode, and a method for manufacturing the same.
The present disclosure particularly relates to an electrode-forming resin composition for forming external electrodes of a chip-type electronic component for surface mounting, a chip-type electronic component using the same, and a method of manufacturing the same.
チップインダクタ、チップ抵抗、チップ型積層セラミックコンデンサ、チップサーミスタ等のチップ型電子部品は、セラミックス焼結体からなるチップ状素体と、その内部に設けられた内部電極と、この内部電極に導通するように、チップ状素体の両端面に設けられた外部電極とで主に構成され、この外部電極を基板にはんだ付けすることにより実装される。 Chip-type electronic components such as a chip inductor, a chip resistor, a chip-type multilayer ceramic capacitor, and a chip thermistor are electrically connected to a chip-shaped element made of a ceramic sintered body, an internal electrode provided therein, and the internal electrode. As described above, the chip is mainly constituted by external electrodes provided on both end surfaces of the chip-shaped element body, and the external electrodes are mounted on the substrate by soldering.
一般に、外部電極は、封止樹脂で成形したチップの表面に樹脂ペーストを塗布した後、硬化させて下地電極を形成し、さらにめっき処理を行って形成している。 Generally, an external electrode is formed by applying a resin paste to the surface of a chip molded with a sealing resin, curing the resin paste to form a base electrode, and further performing a plating process.
外部電極の形成は、第一の端部の電極形成する部分に樹脂ペーストをディップ法で塗布し、予備乾燥する。次に、外部電極の形成は、第二の電極形成する部分をディップ法で樹脂ペーストを塗布して予備乾燥する。予備乾燥により低温活性の銀微粒子が焼結を開始することにより外部電極の外形形状が形成される。その後、さらに加熱することによって熱硬化樹脂成分を硬化させてメッキ処理のベースとなる外部電極を形成している。 The external electrode is formed by applying a resin paste to a portion of the first end where an electrode is to be formed by a dipping method, and predrying the resin paste. Next, in forming the external electrode, a resin paste is applied to a portion where the second electrode is to be formed by a dipping method, and preliminarily dried. The outer shape of the external electrode is formed by starting the sintering of the low-temperature active silver fine particles by the preliminary drying. Thereafter, the thermosetting resin component is further cured by further heating to form an external electrode serving as a base for plating.
このようなチップ型電子部品において、外部電極は、チップ型電子部品と基板上の電気回路とを接続するためのものであるため、その良否が製品の電気的特性、信頼性、機械的特性等に大きな影響を及ぼす。 In such a chip-type electronic component, since the external electrodes are used to connect the chip-type electronic component and an electric circuit on a substrate, the quality of the external electrode depends on the electrical characteristics, reliability, mechanical characteristics, etc. of the product. Has a great effect on
昨今、様々な製品の電子化が進む中、車載製品にも多くのチップ型電子部品が搭載されるようになってきており、これら電子部品にもこれまで以上の耐環境性能及び高い信頼性が求められるようになってきた。具体的には、耐環境性試験において抵抗値の変化率が小さく安定している電子部品が要求されている。 In recent years, with the progress of computerization of various products, many chip-type electronic components are also being mounted on in-vehicle products, and these electronic components also have higher environmental resistance performance and higher reliability than ever before. It has become required. Specifically, there is a demand for a stable electronic component that has a small rate of change in resistance value in an environmental resistance test.
このため、電極形成用の樹脂ペーストにおいても、接着性、耐湿処理後の電気抵抗の安定性に優れたペーストが要求されてきている。 For this reason, there is a demand for a resin paste for forming an electrode that is excellent in adhesiveness and stability of electric resistance after moisture resistance treatment.
例えば、特許文献1には、Agなどの金属粉末とガラスフリットなどの無機結合材と有機ビヒクルを混練した樹脂ペースト中の金属粉末を焼結させて下地電極を形成する方法が開示されている。特許文献2には、エポキシ樹脂などの熱硬化性樹脂とAgなどの金属粒子を分散させた樹脂ペーストを用いて下地電極を形成する方法が開示されている。 For example, Patent Document 1 discloses a method of forming a base electrode by sintering a metal powder in a resin paste obtained by kneading a metal powder such as Ag, an inorganic binder such as glass frit, and an organic vehicle. Patent Document 2 discloses a method of forming a base electrode using a resin paste in which a thermosetting resin such as an epoxy resin and metal particles such as Ag are dispersed.
ところが、特許文献1の方法では600℃以上の高温での熱処理を行う必要があるため封止材中の樹脂又は導線の自己融着性の被膜などが劣化してしまうおそれがあった。特許文献2の方法では耐湿試験を行うと素体と外部電極の接着強度が劣化し、外部電極が剥離するおそれがあった。 However, in the method of Patent Document 1, it is necessary to perform a heat treatment at a high temperature of 600 ° C. or more, so that the resin in the sealing material or the self-fusing film of the conductive wire may be deteriorated. In the method of Patent Document 2, when a moisture resistance test is performed, the adhesive strength between the element body and the external electrode is deteriorated, and the external electrode may be peeled off.
そこで、焼結温度が250℃以下の金属微粒子を含む樹脂ペーストを用いて、250℃以下の低温で焼成する方法が開示されている(特許文献3)。 Therefore, a method of firing at a low temperature of 250 ° C. or lower using a resin paste containing metal fine particles having a sintering temperature of 250 ° C. or lower has been disclosed (Patent Document 3).
しかしながら、単に金属微粒子を含む樹脂ペーストを用いただけでは、体積抵抗値が高いだけではなく、耐吸湿性試験、耐高温放置試験において高い要求レベル(例えば、抵抗値の変化率が10%以内であること等)に対して十分な信頼性が得られないおそれがあった。 However, simply using a resin paste containing metal fine particles not only has a high volume resistance value, but also has a high required level in a moisture absorption resistance test and a high temperature storage test (for example, the rate of change of the resistance value is within 10%). ) May not be able to obtain sufficient reliability.
そこで、本開示は、接着性、耐湿、耐熱処理後の電気抵抗の安定性などに優れた低温焼結型の電極形成用樹脂組成物を提供する。この電極形成用樹脂組成物は、車載レベルの耐環境性能(超耐湿性、超耐熱性)にも適用可能である。 Accordingly, the present disclosure provides a low-temperature sintering type electrode forming resin composition having excellent adhesiveness, moisture resistance, stability of electric resistance after heat treatment, and the like. This electrode-forming resin composition can be applied to environmental resistance performance (ultra-moisture resistance, ultra-heat resistance) at a vehicle-mounted level.
本開示は、熱硬化性樹脂として、電極形成用樹脂組成物に使用する樹脂を、特定の樹脂を組み合わせたものとすることで、車載レベルの耐環境性能を満足することを見出し、完成するに至ったものである。 The present disclosure has found that, as a thermosetting resin, a resin used in an electrode forming resin composition is a combination of a specific resin, thereby satisfying environmental resistance performance at a vehicle-mounted level. It has been reached.
すなわち、本開示の電極形成用樹脂組成物の一態様は、(A)熱硬化性樹脂と、(B)ラジカル開始剤と、(C)厚さ又は短径が1〜200nmの銀微粒子と、(D)前記(C)成分以外の平均粒径が2〜20μmの銀粉と、を含む電極形成用樹脂組成物であって、
前記(A)熱硬化性樹脂が、(A1)ヒドロキシル基を有する、(メタ)アクリル酸エステル化合物又は(メタ)アクリルアミド化合物、(A2)常温で液状であり、ビスマレイミド樹脂、(A3)エポキシ化ポリブタジエン、を含むことを特徴とする。That is, one embodiment of the electrode-forming resin composition of the present disclosure includes (A) a thermosetting resin, (B) a radical initiator, (C) silver fine particles having a thickness or a minor axis of 1 to 200 nm, (D) a silver powder having an average particle diameter other than the component (C) of 2 to 20 μm, and a resin composition for forming an electrode,
(A) the thermosetting resin is (A1) a (meth) acrylic acid ester compound or a (meth) acrylamide compound having a hydroxyl group, (A2) a liquid at room temperature, a bismaleimide resin, and (A3) epoxidation. And polybutadiene.
また、本開示の一態様は、硬化後生成物に対して1%重量減少温度が280℃以上400℃以下であってもよく、下限が320℃以上であってもよく、下限が340℃以上であってもよく、下限が350℃以上であってもよい。
1%重量減少温度がこの範囲にあると、耐吸湿性試験、耐高温放置試験において抵抗値の変化率が小さく安定した電極形成用樹脂組成物が得られる。
1%重量減少温度は、たとえば電極形成用樹脂組成物中に含まれる成分の種類、配合割合を調整することによって制御することが可能である。
本実施形態においては、たとえば電極形成用樹脂組成物10mgを200℃で1時間硬化した後、窒素雰囲気または空気雰囲気、昇温速度10℃/分の条件でTG/DTA(熱重量/示差熱分析)測定を行うことにより、電極形成用樹脂組成物の1%重量減少温度を測定することができる。In one embodiment of the present disclosure, the 1% weight loss temperature with respect to the cured product may be from 280 ° C to 400 ° C, the lower limit may be 320 ° C or higher, and the lower limit may be 340 ° C or higher. And the lower limit may be 350 ° C. or higher.
When the 1% weight loss temperature is in this range, a stable electrode forming resin composition having a small rate of change in resistance in a moisture absorption resistance test and a high temperature storage test can be obtained.
The 1% weight loss temperature can be controlled, for example, by adjusting the types and blending ratios of the components contained in the electrode-forming resin composition.
In the present embodiment, for example, 10 mg of the resin composition for forming an electrode is cured at 200 ° C. for 1 hour, and then TG / DTA (thermogravimetric / differential thermal analysis) is performed in a nitrogen atmosphere or an air atmosphere at a rate of 10 ° C./min. ) By performing the measurement, the 1% weight loss temperature of the resin composition for electrode formation can be measured.
本開示のチップ型電子部品の一態様は、セラミックス焼結体よりなる直方体形状のチップ型電子部品素体を有するチップ型電子部品である。さらに、前記チップ型電子部品素体の内部に形成された内部電極及び前記チップ型電子部品素体の端面に形成された外部電極の少なくとも1つが、上記電極形成用樹脂組成物の焼結体である。 One embodiment of the chip-type electronic component according to the present disclosure is a chip-type electronic component having a rectangular parallelepiped chip-type electronic component element made of a ceramic sintered body. Further, at least one of an internal electrode formed inside the chip-type electronic component body and an external electrode formed on an end surface of the chip-type electronic component body is a sintered body of the electrode-forming resin composition. is there.
本開示のチップ型電子部品の製造方法の一態様は、セラミック層の表面に、上記電極形成用樹脂組成物を用いて所定の電極パターン層を印刷により形成する。本開示のチップ型電子部品の製造方法の次の工程は、該電極パターン層の上に他のセラミック層を載置し、該他のセラミック層の表面に、上記電極形成用樹脂組成物を用いて所定の電極パターン層を印刷により形成する操作を繰り返して、セラミック層と電極パターン層とを交互に積層する。本開示のチップ型電子部品の製造方法の最後の工程は、得られた積層体を焼結することで、前記電極パターンにより形成された内部電極を有するチップ型電子部品素体とし、該チップ型電子部品素体の端面に外部電極を形成する。 In one embodiment of the method of manufacturing a chip-type electronic component according to the present disclosure, a predetermined electrode pattern layer is formed on a surface of a ceramic layer by using the above-described electrode-forming resin composition by printing. The next step of the method of manufacturing a chip-type electronic component according to the present disclosure includes placing another ceramic layer on the electrode pattern layer, and using the electrode-forming resin composition on the surface of the other ceramic layer. The operation of forming a predetermined electrode pattern layer by printing is repeated to alternately laminate the ceramic layers and the electrode pattern layers. The final step of the method of manufacturing a chip-type electronic component according to the present disclosure is to sinter the obtained laminate to obtain a chip-type electronic component body having internal electrodes formed by the electrode patterns, An external electrode is formed on an end face of the electronic component body.
本開示のチップ型電子部品の製造方法の一態様は、チップ型電子部品素体の端面に、上記電極形成用樹脂組成物を印刷又は浸漬により塗布し、塗布された該電極形成用樹脂組成物を焼結することにより外部電極を形成する。 One embodiment of the method of manufacturing a chip-type electronic component according to the present disclosure is to apply the above-described electrode-forming resin composition to an end surface of a chip-type electronic component body by printing or dipping, and to apply the applied electrode-forming resin composition. Is formed to form an external electrode.
本開示の電極形成用樹脂組成物は、耐吸湿性試験、耐高温放置試験において抵抗値の変化率が小さい。さらに、銀微粒子を配合しているため、低温での焼結が可能であり、得られた焼結体は電子部品の電極形成に適したものである。 The electrode forming resin composition according to the present disclosure has a small rate of change in resistance in a moisture resistance test and a high temperature storage test. Furthermore, since silver fine particles are blended, sintering at a low temperature is possible, and the obtained sintered body is suitable for forming electrodes of electronic components.
また、本開示のチップ型電子部品及びその製造方法によれば、電極を上記電極形成用樹脂組成物を用いて形成しているため、高湿及び高熱環境下でも素体への固着強度が強い電極を有するチップ型電子部品が得られ、信頼性の高い製品となる。 Further, according to the chip-type electronic component and the method of manufacturing the same of the present disclosure, since the electrodes are formed using the electrode-forming resin composition, the bonding strength to the element body is high even under a high humidity and high heat environment. A chip-type electronic component having electrodes is obtained, and the product is highly reliable.
本開示の電極形成用樹脂組成物の一態様は、上記の構成からなり、この開示について一実施形態である電極形成用樹脂組成物を参照しながら、以下、説明する。 One embodiment of the electrode forming resin composition of the present disclosure has the above configuration, and the disclosure will be described below with reference to the electrode forming resin composition according to one embodiment.
本実施形態で使用する(A)熱硬化性樹脂は、複数種の所定の熱硬化性樹脂を組み合わせて使用したものである。この(A)熱硬化性樹脂に使用する樹脂としては、(A1)ヒドロキシル基を有する、(メタ)アクリル酸エステル化合物又は(メタ)アクリルアミド化合物、(A2)常温で液状であり、主鎖に脂肪族炭化水素基を有するビスマレイミド樹脂、及び(A3)ポリブタジエン樹脂、を含んでいる。 The thermosetting resin (A) used in the present embodiment is a combination of a plurality of types of predetermined thermosetting resins. As the resin used for the (A) thermosetting resin, (A1) a (meth) acrylate compound or a (meth) acrylamide compound having a hydroxyl group, (A2) a liquid at room temperature, and a fatty acid in the main chain. A bismaleimide resin having an aromatic group, and (A3) a polybutadiene resin.
本実施形態で使用する(A1)ヒドロキシル基を有する、(メタ)アクリル酸エステル化合物又は(メタ)アクリルアミド化合物は、それぞれ1分子中に1個以上の(メタ)アクリル基を有する(メタ)アクリレート又は(メタ)アクリルアミドであり、かつ、ヒドロキシル基を含有するものである。 The (meth) acrylic acid ester compound or the (meth) acrylamide compound having a hydroxyl group (A1) used in the present embodiment is a (meth) acrylate or a (meth) acrylate having one or more (meth) acryl groups in one molecule. It is (meth) acrylamide and contains a hydroxyl group.
ここで、ヒドロキシル基を有する(メタ)アクリレートは、ポリオール化合物と(メタ)アクリル酸又はその誘導体とを反応させることで得ることが可能である。この反応は、公知の化学反応を使用できる。ヒドロキシル基を有する(メタ)アクリレートは、ポリオール化合物に対し、通常0.5〜5倍モルのアクリル酸エステル又はアクリル酸を使用する。 Here, the (meth) acrylate having a hydroxyl group can be obtained by reacting a polyol compound with (meth) acrylic acid or a derivative thereof. For this reaction, a known chemical reaction can be used. As the (meth) acrylate having a hydroxyl group, an acrylic ester or acrylic acid is usually used in an amount of 0.5 to 5 times the mole of the polyol compound.
また、ヒドロキシル基を有する(メタ)アクリルアミドは、ヒドロキシル基を有するアミン化合物と(メタ)アクリル酸又はその誘導体とを反応させることで得ることが可能である。(メタ)アクリル酸エステルとアミン化合物とを反応させて(メタ)アクリルアミド類を製造する方法は、(メタ)アクリル酸エステルの二重結合が極めて反応性に富むために、アミン、シクロペンタジエン、アルコール等を予め二重結合に保護基として付加させ、アミド化終了後加熱して保護基を脱離させるのが一般的である。 Further, (meth) acrylamide having a hydroxyl group can be obtained by reacting an amine compound having a hydroxyl group with (meth) acrylic acid or a derivative thereof. The method of producing (meth) acrylamides by reacting a (meth) acrylic ester with an amine compound involves the use of amines, cyclopentadiene, alcohols, etc., because the double bond of the (meth) acrylic ester is extremely reactive. Is generally added to the double bond as a protecting group in advance, and after completion of the amidation, heating is performed to remove the protecting group.
そして、この(メタ)アクリル酸エステル化合物又は(メタ)アクリルアミド化合物にヒドロキシル基を含有させることにより、電極形成時において、還元効果による焼結性が促進されると共に、接着性が向上する。 By making the (meth) acrylic acid ester compound or the (meth) acrylamide compound contain a hydroxyl group, sinterability due to a reduction effect is promoted at the time of electrode formation, and adhesion is improved.
また、ここでいうヒドロキシル基は脂肪族炭化水素基の水素原子が置換されたアルコール性の基である。このヒドロキシル基の含有量は、1分子中に1から50個であってもよく、ヒドロキシル基の含有量がこの範囲にあると、硬化過多による焼結性の阻害がなく、焼結性を促進できる。 The hydroxyl group referred to here is an alcoholic group in which a hydrogen atom of an aliphatic hydrocarbon group is substituted. The content of the hydroxyl group may be from 1 to 50 per molecule, and when the content of the hydroxyl group is within this range, sinterability is not hindered by excessive curing and sinterability is promoted. it can.
このような(A1)ヒドロキシル基を有する、(メタ)アクリル酸エステル化合物又は(メタ)アクリルアミド化合物としては、例えば、次の一般式(1)〜(4)で示される化合物が挙げられる。 Examples of the (meth) acrylic ester compound or (meth) acrylamide compound having a hydroxyl group (A1) include compounds represented by the following general formulas (1) to (4).
この(A1)成分の(メタ)アクリル酸エステル化合物又は(メタ)アクリルアミド化合物としては、上記した一般式(1)〜(4)に示した化合物を単独で又は2種以上を組み合わせて使用することができる。なお、一般式(1)及び(2)におけるR2の炭素数は、1〜100であってもよく、1〜36であってもよい。R2の炭素数がこのような範囲にあると硬化過多による焼結性が阻害されない。As the (meth) acrylic ester compound or (meth) acrylamide compound of the component (A1), the compounds represented by the above general formulas (1) to (4) may be used alone or in combination of two or more. Can be. In addition, the carbon number of R 2 in the general formulas (1) and (2) may be 1 to 100 or 1 to 36. When the carbon number of R 2 is in such a range, the sinterability due to excessive curing is not hindered.
本実施形態で使用する(A2)常温で液状であり、主鎖に脂肪族炭化水素基を有するビスマレイミド樹脂は、主鎖に炭素数が1以上の脂肪族炭化水素基を有し、この主鎖が2つのマレイミド基を連結して構成されるものである。ここで、脂肪族炭化水素基は、直鎖状、分枝鎖状及び環状のいずれの形態でもよく、炭素数が6以上であってもよく、炭素数が12以上であってもよく、炭素数が24以上であってもよい。また、この脂肪族炭化水素基は、マレイミド基に直接又は間接に結合できるが、マレイミド基に直接結合してもよい。 The bismaleimide resin (A2) which is liquid at normal temperature and has an aliphatic hydrocarbon group in the main chain used in the present embodiment has an aliphatic hydrocarbon group having 1 or more carbon atoms in the main chain. The chain is formed by connecting two maleimide groups. Here, the aliphatic hydrocarbon group may be any of linear, branched and cyclic, and may have 6 or more carbon atoms, may have 12 or more carbon atoms, The number may be 24 or more. Further, this aliphatic hydrocarbon group can be directly or indirectly bonded to the maleimide group, but may be directly bonded to the maleimide group.
この(A2)成分のマレイミド樹脂は、次の一般式(5)で表される化合物
ここで、Pで表される2価の原子は、O、S等が挙げられ、2価の有機基は、CO、COO、CH2、C(CH3)2、C(CF3)2、S2、SO、SO2等、また、これらの原子又は有機基を少なくとも1つ以上含む有機基が挙げられる。上記した原子又は有機基を含む有機基としては、上記以外の構造として、炭素数1〜3の炭化水素基、ベンゼン環、シクロ環、ウレタン結合等を有するものが挙げられ、その場合のPとして次の化学式で表される基が例示できる。Here, the divalent atom represented by P includes O and S, and the divalent organic group includes CO, COO, CH 2 , C (CH 3 ) 2 , C (CF 3 ) 2 , Examples include S 2 , SO, SO 2 , and an organic group containing at least one of these atoms or organic groups. Examples of the organic group containing an atom or an organic group include those having a hydrocarbon group having 1 to 3 carbon atoms, a benzene ring, a cyclo ring, a urethane bond, and the like as a structure other than the above. A group represented by the following chemical formula can be exemplified.
本実施形態において、(A2)成分のビスマレイミド樹脂として、主鎖に脂肪族炭化水素基を有するビスマレイミド樹脂を用いることが、耐熱性に優れるとともに、低応力で吸湿後の熱時接着強度の良好な電極形成用樹脂組成物が得られる要件の1つである。この特性を有効に得るために、(A2)成分として上記一般式(5)で表されるような脂肪族炭化水素基でイミド延長され、室温で液状のビスマレイミド樹脂を用いることが好ましい。 In the present embodiment, the use of a bismaleimide resin having an aliphatic hydrocarbon group in the main chain as the bismaleimide resin of the component (A2) is excellent in heat resistance, and has low stress and low heat adhesion strength after moisture absorption. This is one of the requirements for obtaining a good electrode-forming resin composition. In order to effectively obtain this property, it is preferable to use a bismaleimide resin which is imide-extended with an aliphatic hydrocarbon group represented by the above general formula (5) and is liquid at room temperature as the component (A2).
この(A2)成分のビスマレイミド樹脂は、ポリスチレン換算による数平均分子量が500以上10000以下であってもよく、500以上5000以下であってもよい。数平均分子量が500未満では、可撓性が低下し、また、耐熱性も低下する。数平均分子量が10000を超えると、組成物調製時の作業性、使用時の作業性が低下する傾向にある。 The bismaleimide resin (A2) may have a number average molecular weight in terms of polystyrene of 500 or more and 10,000 or less, or 500 or more and 5000 or less. If the number average molecular weight is less than 500, the flexibility is lowered and the heat resistance is also lowered. When the number average molecular weight exceeds 10,000, the workability at the time of preparing the composition and the workability at the time of use tend to decrease.
本実施形態で使用される(A3)エポキシ化ポリブタジエンは、ポリブタジエンをエポキシ変性した化合物であり、エポキシ当量が50〜500(g/eq)のエポキシ化ポリブタジエンであってもよい。エポキシ当量が50未満では粘度が増大し、樹脂組成物の作業性が低下する傾向があり、500を超えると熱時の接着強度が低下する傾向がある。なお、エポキシ当量は過塩素酸法により求めたものである。このエポキシ化ポリブタジエンとしては、分子内に水酸基を持つものを使用してもよい。
エポキシ化ポリブタジエンとしては、例えば、株式会社ダイセルより市販されているエポリードPB4700及びGT401(いずれも商品名)、日本曹達株式会社より市販されているJP−100及びJP−200(いずれも商品名)、を使用することができる。この(A3)エポキシ化ポリブタジエンを含むことにより、電極形成用樹脂組成物は、チップ部品端子に対する電極の接着性を向上させることができる。The (A3) epoxidized polybutadiene used in the present embodiment is a compound obtained by modifying polybutadiene by epoxy, and may be an epoxidized polybutadiene having an epoxy equivalent of 50 to 500 (g / eq). If the epoxy equivalent is less than 50, the viscosity tends to increase and the workability of the resin composition tends to decrease. If it exceeds 500, the adhesive strength when heated tends to decrease. The epoxy equivalent was determined by the perchloric acid method. As the epoxidized polybutadiene, those having a hydroxyl group in the molecule may be used.
Examples of the epoxidized polybutadiene include Eporide PB4700 and GT401 (all trade names) commercially available from Daicel Corporation, JP-100 and JP-200 (all trade names) commercially available from Nippon Soda Co., Ltd., Can be used. By containing this (A3) epoxidized polybutadiene, the electrode-forming resin composition can improve the adhesiveness of the electrode to the chip component terminal.
この(A3)エポキシ化ポリブタジエンは、その数平均分子量が500〜10000のものであってもよい。分子量がこの範囲にあると、接着性が良好であり、適正な粘度に制御できることから作業性が良好となる。数平均分子量は、ゲルパーミエーションクロマトグラフィーにより標準ポリスチレンの検量線を利用して測定(以下、GPC法という)した値である。そして、上記説明した(A1)〜(A3)の各成分は、以下のように所定の量を配合するようにして(A)熱硬化性樹脂とすることがあってもよい。
すなわち、本実施形態で使用する(A)熱硬化性樹脂は、(A)熱硬化性樹脂を100質量%としたとき、(A1)ヒドロキシル基を有する、(メタ)アクリル酸エステル化合物又は(メタ)アクリルアミド化合物を0〜75質量%、(A2)常温で液状であり、主鎖に脂肪族炭化水素基を有するビスマレイミド樹脂を10〜90質量%、(A3)エポキシ化ポリブタジエンを10〜90質量%であってもよい。
さらに、(A1)ヒドロキシル基を有する、(メタ)アクリル酸エステル化合物又は(メタ)アクリルアミド化合物は0〜50質量%であってもよい。
さらに、(A1)ヒドロキシル基を有する、(メタ)アクリル酸エステル化合物又は(メタ)アクリルアミド化合物が0質量%であってもよい。(A1)ヒドロキシル基を有する、(メタ)アクリル酸エステル化合物又は(メタ)アクリルアミド化合物が0質量%の場合は、(A3)エポキシ化ポリブタジエンの配合量に対する(A2)常温で液状であり、主鎖に脂肪族炭化水素基を有するビスマレイミド樹脂の配合量の比[(A2)/(A3)]が1以上であってもよい。
(A1)〜(A3)の各成分がこの範囲内にあると、耐熱性、耐湿性及び接着性の良好であり、特に耐環境性の要求レベルが高い車載用途に用いることができる。This (A3) epoxidized polybutadiene may have a number average molecular weight of 500 to 10,000. When the molecular weight is in this range, the adhesiveness is good, and the workability is good because the viscosity can be controlled to an appropriate value. The number average molecular weight is a value measured by gel permeation chromatography using a calibration curve of standard polystyrene (hereinafter, referred to as GPC method). The components (A1) to (A3) described above may be used as the thermosetting resin (A) by mixing a predetermined amount as described below.
That is, the (A) thermosetting resin used in the present embodiment is, when the (A) thermosetting resin is 100% by mass, (A1) a (meth) acrylate compound having a hydroxyl group or (meth) acrylate compound. 0) to 75% by mass of an acrylamide compound, (A2) 10 to 90% by mass of a bismaleimide resin which is liquid at room temperature and has an aliphatic hydrocarbon group in its main chain, and 10 to 90% by mass of (A3) epoxidized polybutadiene. %.
Further, (A1) the (meth) acrylate compound or the (meth) acrylamide compound having a hydroxyl group may be 0 to 50% by mass.
Furthermore, (A1) the hydroxyl group-containing (meth) acrylate compound or (meth) acrylamide compound may be 0% by mass. When (A1) the (meth) acrylic ester compound or the (meth) acrylamide compound having a hydroxyl group is 0% by mass, (A2) a liquid at room temperature with respect to the blending amount of (A3) epoxidized polybutadiene, and the main chain The ratio [(A2) / (A3)] of the bismaleimide resin having an aliphatic hydrocarbon group may be 1 or more.
When each of the components (A1) to (A3) is within this range, heat resistance, moisture resistance, and adhesiveness are good, and it can be used particularly for in-vehicle applications where the required level of environmental resistance is high.
(A1)成分の配合量が75質量%より多いと、電極形成用樹脂組成物の耐熱性・耐湿性に劣ってしまうおそれがある。(A2)成分の配合量が10質量%より少ないと、電極形成用樹脂組成物の耐熱性、耐湿性に劣り、90質量%より多いと、電極形成用樹脂組成物の接着強度が劣ってしまうおそれがある。また、(A3)成分の配合量が10質量%より少ないと、電極形成用樹脂組成物の接着強度が劣り、90質量%より多いと、電極形成用樹脂組成物の未反応成分が残り易くなり接着強度が劣ってしまうおそれがある。 If the amount of the component (A1) is more than 75% by mass, the resin composition for forming an electrode may be inferior in heat resistance and moisture resistance. When the blending amount of the component (A2) is less than 10% by mass, the heat resistance and moisture resistance of the electrode forming resin composition are inferior. When the amount is more than 90% by mass, the adhesive strength of the electrode forming resin composition is inferior. There is a risk. When the amount of the component (A3) is less than 10% by mass, the adhesive strength of the electrode-forming resin composition is poor. When the amount is more than 90% by mass, unreacted components of the electrode-forming resin composition tend to remain. There is a possibility that the adhesive strength is inferior.
なお、この(A)熱硬化性樹脂としては、上記(A1)〜(A3)成分以外の熱硬化性樹脂を用いることもでき、ここで用いることができる熱硬化性樹脂は、例えば、エポキシ樹脂、ビスマレイミド樹脂、ポリブタジエン樹脂、フェノール樹脂等が挙げられる。ただし、(A1)〜(A3)成分以外の熱硬化性樹脂は、(A)熱硬化性樹脂を100質量%としたとき、20質量%以下であってもよく、10質量%以下であってもよい。 As the thermosetting resin (A), a thermosetting resin other than the components (A1) to (A3) can be used. The thermosetting resin used here is, for example, an epoxy resin. , Bismaleimide resin, polybutadiene resin, phenol resin and the like. However, the thermosetting resin other than the components (A1) to (A3) may be 20% by mass or less when the thermosetting resin (A) is 100% by mass, or 10% by mass or less. Is also good.
本実施形態に用いられる(B)ラジカル開始剤は、通常、ラジカル重合に用いられている重合触媒であれば特に限定されずに用いることができる。 The radical initiator (B) used in the present embodiment can be used without any particular limitation as long as it is a polymerization catalyst usually used for radical polymerization.
この(B)ラジカル開始剤としては、急速加熱試験(試料1gを電熱板の上に乗せ、4℃/分で昇温したときの分解開始温度の測定試験)における分解開始温度が40〜140℃となるものであってもよい。分解開始温度が40℃未満であると、接着性熱硬化型樹脂組成物の常温における保存性が不良となるおそれがあり、140℃を超えると硬化時間が極端に長くなる可能性がある。なお、前記分解開始温度は、試料の加熱前の質量に対する1%質量減少時の温度を分解開始温度とする。 The (B) radical initiator has a decomposition start temperature of 40 to 140 ° C. in a rapid heating test (a test for measuring a decomposition start temperature when 1 g of a sample is placed on an electric heating plate and heated at 4 ° C./min). May be as follows. If the decomposition start temperature is lower than 40 ° C., the storage stability of the adhesive thermosetting resin composition at ordinary temperature may be poor, and if it exceeds 140 ° C., the curing time may be extremely long. The decomposition start temperature is defined as the temperature at which the mass of the sample decreases by 1% with respect to the mass before heating.
この条件を満たすラジカル開始剤の具体例としては、例えば、1,1−ビス(t−ブチルパーオキシ)−2−メチルシクロヘキサン、t−ブチルパーオキシネオデカノエート、ジクミルパーオキサイド等が挙げられる。これらは単独で使用しても、硬化性を制御するために2種類以上を混合して使用してもよい。 Specific examples of the radical initiator satisfying this condition include, for example, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, t-butylperoxy neodecanoate, dicumyl peroxide and the like. Can be These may be used alone or in combination of two or more to control curability.
この(B)ラジカル開始剤の配合量は、上記(A)熱硬化性樹脂 100質量部に対して、0.1〜10質量部であってもよい。この配合量が10質量部を超えると、樹脂組成物の粘度の経時変化が大きくなり作業性が低下するおそれがあり、0.1質量部未満では、硬化性が著しく低下する可能性がある。 The compounding amount of the (B) radical initiator may be 0.1 to 10 parts by mass based on 100 parts by mass of the (A) thermosetting resin. If the amount is more than 10 parts by mass, the viscosity of the resin composition may change with time and the workability may be reduced. If the amount is less than 0.1 part by mass, the curability may be significantly reduced.
本実施形態で用いられる(C)銀微粒子は、その厚さ又は短径が1〜200nmの銀微粒子であれば特に限定されずに用いることができる。この(C)銀微粒子の形状は、プレート型、樹枝状、ロッド状、ワイヤー状、球状等が挙げられる。ここで、プレート型ではその厚さが、また樹枝状、ロッド状、ワイヤー状、球状では、その断面直径における最も短い径が上記範囲を満たしていればよい。 The silver fine particles (C) used in the present embodiment can be used without particular limitation as long as the silver fine particles have a thickness or a short diameter of 1 to 200 nm. The shape of the silver fine particles (C) includes a plate type, a dendritic shape, a rod shape, a wire shape, a spherical shape and the like. Here, it is sufficient that the plate type has the thickness, and the dendritic, rod-like, wire-like, and spherical shapes have the shortest diameter in the cross-sectional diameter satisfying the above range.
前記(C)銀微粒子は、プレート型銀微粒子を用いてもよい。このプレート型銀微粒子は、短径方向に積み重なる傾向にあるため、電極形成用樹脂組成物をディップ塗布により電子部品の両端に成膜した際、表面に凹凸が少なく平滑な電極面が得られる利点がある。 The silver fine particles (C) may be plate-type silver fine particles. Since the plate type silver fine particles tend to be stacked in the minor diameter direction, when the electrode forming resin composition is formed on both ends of the electronic component by dip coating, an advantage that a smooth electrode surface with little unevenness on the surface can be obtained. There is.
このプレート型銀微粒子は、中心粒子径が0.3〜15μmであってもよい。本開示の一実施形態は、プレート型銀微粒子の中心粒子径をこの範囲とすることで、樹脂成分への分散性を向上できる。ここで、中心粒子径とは、レーザー回折式粒度分布測定装置で測定して得られた体積基準の粒度分布曲線における50%積算値(50%粒子径)を指す。 The plate-shaped silver fine particles may have a center particle diameter of 0.3 to 15 μm. According to an embodiment of the present disclosure, the dispersibility in the resin component can be improved by setting the center particle diameter of the plate-type silver fine particles in this range. Here, the central particle size refers to a 50% integrated value (50% particle size) in a volume-based particle size distribution curve obtained by measurement with a laser diffraction type particle size distribution measuring device.
また、厚さは10〜200nmであり、さらに10〜100nmであってもよい。この厚さは、透過型電子顕微鏡(TEM)又は走査型電子顕微鏡(SEM)により取得された観察画像をデータ処理することで測定されるものである。さらに、この厚さの平均厚さが上記範囲内であってもよい。この平均厚さは、下記のようにして個数平均厚さとして算出される。 The thickness is 10 to 200 nm, and may be 10 to 100 nm. This thickness is measured by data processing of an observation image acquired by a transmission electron microscope (TEM) or a scanning electron microscope (SEM). Furthermore, the average thickness of this thickness may be within the above range. This average thickness is calculated as a number average thickness as described below.
プレート型銀微粒子の[n+1]個(n+1は、例えば、50から100程度)の観察画像から計測した厚さを厚い方から薄い方へ順番に並べ、その範囲(最大厚さ:x1、最小厚さ:xn+1)をn分割し、それぞれの厚さの区間を、[xj、xj+1](j=1,2,・・・・,n)とする。この場合の分割は対数スケール上での等分割となる。また、対数スケールに基づいてそれぞれの厚さ区間での代表厚さは、下記式で表される。The thickness measured from [n + 1] (n + 1 is, for example, about 50 to 100) observation images of the plate-type silver fine particles are arranged in order from the thicker to the thinner, and the range (maximum thickness: x 1 , minimum) The thickness: x n + 1 ) is divided into n, and the section of each thickness is defined as [x j , x j + 1 ] (j = 1, 2,..., N). The division in this case is an equal division on a logarithmic scale. The representative thickness in each thickness section is represented by the following equation based on the logarithmic scale.
さらにrj(j=1,2,・・・・,n)を、区間[xj、xj+1]に対応する相対量(差分%)とし、全区間の合計を100%とすると、対数スケール上での平均値μは下記式で計算できる。Further, if r j (j = 1, 2,..., N) is a relative amount (difference%) corresponding to the section [x j , x j + 1 ] and the total of all sections is 100%, the logarithmic scale The above average value μ can be calculated by the following equation.
このμは、対数スケール上の数値であり、厚さとしての単位を持たないので、厚さの単位に戻すために10μすなわち10のμ乗を計算する。この10μが個数平均厚さである。Since μ is a numerical value on a logarithmic scale and does not have a unit as the thickness, 10 μ, that is, 10 to the power of μ is calculated to return to the unit of the thickness. This 10 μ is the number average thickness.
また、厚み方向に垂直な方向の長辺が厚みの8〜150倍の範囲内であってもよく、10〜50倍であってもよい。さらに、厚み方向に垂直な方向の短辺が厚みの1〜100倍の範囲内であってもよく、3〜50倍であってもよい。 In addition, the long side in the direction perpendicular to the thickness direction may be in the range of 8 to 150 times the thickness, or may be 10 to 50 times. Further, the short side in the direction perpendicular to the thickness direction may be in the range of 1 to 100 times the thickness, or may be 3 to 50 times.
このプレート型銀微粒子は100〜250℃で自己焼結可能である。このように100〜250℃で自己焼結する銀微粒子を含有することで、熱硬化時に銀微粒子の流動性が向上し、その結果、銀微粒子同士の接点がより多くなる上に、接点の面積が大きくなり、導電性が格段に向上する。自己焼結温度が低いほど焼結性が良好であるため、プレート型銀微粒子の焼結温度は、100〜200℃であってもよい。なお、ここで自己焼結可能であるとは加圧又は添加剤等を加えなくても、融点よりも低い温度での加熱で焼結することをいう。 These plate-shaped silver fine particles can self-sinter at 100 to 250 ° C. By containing the silver fine particles self-sintering at 100 to 250 ° C. in this way, the fluidity of the silver fine particles is improved at the time of thermosetting, and as a result, the number of contacts between the silver fine particles is increased and the area of the contacts is increased. And the conductivity is remarkably improved. Since the lower the self-sintering temperature is, the better the sinterability is, the sintering temperature of the plate-type silver fine particles may be 100 to 200 ° C. Here, "self-sinterable" means sintering by heating at a temperature lower than the melting point without applying pressure or adding an additive or the like.
このような(C)プレート型銀微粒子としては、例えば、トクセン工業株式会社製のM612(商品名;中心粒子径6〜12μm、粒子厚み60〜100nm、融点250℃)、M27(商品名;中心粒子径2〜7μm、粒子厚み60〜100nm、融点200℃)、M13(商品名;中心粒子径1〜3μm、粒子厚み40〜60nm、融点200℃)、N300(商品名;中心粒子径0.3〜0.6μm、粒子厚み50nm以下、融点150℃)などが挙げられる。これらのプレート型銀微粒子は、単独で用いてもよく、組み合わせて用いてもよい。特に、充填率を向上するために、プレート型銀微粒子は、例えば上述のプレート型銀微粒子のうち、M27、M13などの比較的大きな銀微粒子に、N300などの粒径の小さなものを組み合わせて用いてもよい。 Examples of such (C) plate-type silver fine particles include M612 (trade name; center particle diameter: 6 to 12 μm, particle thickness: 60 to 100 nm, melting point: 250 ° C.), M27 (trade name; center) manufactured by Toxen Industries, Ltd. Particle size 2 to 7 μm, particle thickness 60 to 100 nm, melting point 200 ° C.), M13 (trade name; central particle diameter 1 to 3 μm, particle thickness 40 to 60 nm, melting point 200 ° C.), N300 (trade name; 3 to 0.6 μm, a particle thickness of 50 nm or less, and a melting point of 150 ° C.). These plate-shaped silver fine particles may be used alone or in combination. In particular, in order to improve the filling rate, the plate-type silver fine particles are, for example, a combination of relatively large silver fine particles such as M27 and M13 among the above-mentioned plate-type silver fine particles combined with a small particle size such as N300. You may.
(C)プレート型銀微粒子は、粒子厚み200nm以下、タップ密度(TD)3.0〜7.0g/cm3、かつ比表面積(BET)2.0〜6.0m2/gが好ましい。(C) The plate-type silver fine particles preferably have a particle thickness of 200 nm or less, a tap density (TD) of 3.0 to 7.0 g / cm 3 , and a specific surface area (BET) of 2.0 to 6.0 m 2 / g.
本実施形態に用いられる(D)銀粉は、(C)成分以外の銀粉である。
(D)銀粉は、平均粒子径が0.2〜20μmであり、樹脂接着剤中に導電性を付与するために添加される無機充填材としての銀粉であればよい。本実施形態において(D)銀粉のタップ密度は2.0〜7.0g/cm3であってもよい。The silver powder (D) used in the present embodiment is a silver powder other than the component (C).
(D) The silver powder may be any silver powder having an average particle diameter of 0.2 to 20 μm and serving as an inorganic filler added for imparting conductivity to the resin adhesive. In this embodiment, the tap density of the silver powder (D) may be 2.0 to 7.0 g / cm 3 .
このような(D)成分の銀粉を、上記の(C)成分の銀微粒子に加えて添加することで、チップ部品の端子と電極との接合強度をより向上させることができる。また、ここで用いられる銀粒子の形状としては、例えば、フレーク状、樹脂状、ロッド状、ワイヤー状、球状、プレート状等が挙げられる。なお、この(D)成分の銀粉の平均粒子径は、レーザー回折粒度分布測定装置で測定して得られた体積基準の粒度分布曲線における50%積算値(50%粒子径)を指す。 By adding the silver powder of the component (D) to the silver fine particles of the component (C), the bonding strength between the terminal and the electrode of the chip component can be further improved. In addition, examples of the shape of the silver particles used here include a flake shape, a resin shape, a rod shape, a wire shape, a spherical shape, and a plate shape. The average particle diameter of the silver powder of the component (D) refers to a 50% integrated value (50% particle diameter) in a volume-based particle size distribution curve obtained by a laser diffraction particle size distribution analyzer.
なお、これら(C)成分と(D)成分の割合は、(C)成分:(D)成分の質量比が10:90〜50:50であってもよい。(D)成分に対して(C)成分の割合が、少なすぎると焼結性が低下することにより、抵抗値が増加し、多すぎると粘度が大幅に増加し、電子部品への塗布性が損なわれるおそれがある。 In addition, as for the ratio of these (C) component and (D) component, the mass ratio of (C) component: (D) component may be 10:90 to 50:50. If the ratio of the component (C) to the component (D) is too small, the sinterability is reduced, and the resistance value is increased. If the ratio is too large, the viscosity is greatly increased, and the applicability to electronic components is reduced. It may be damaged.
本実施形態の電極形成用樹脂組成物は、上記した(A)〜(D)成分を、この電極形成用樹脂組成物中に、(A)熱硬化性樹脂を1〜15質量%、(B)ラジカル開始剤を(A)熱硬化性樹脂を100質量部に対して0.1〜10質量部、(C)銀微粒子を5〜40質量%、(D)銀粉を50〜90質量%、となるように含有させてもよい。このような配合とすることで、耐熱性、耐湿性、接着性、及び環境耐性が良好となる。 The electrode-forming resin composition of the present embodiment contains the above-mentioned components (A) to (D) in the electrode-forming resin composition, (A) 1 to 15% by mass of a thermosetting resin, (B 0.1) to 10 parts by mass of (A) the thermosetting resin with respect to 100 parts by mass of the radical initiator, (C) 5 to 40% by mass of silver fine particles, (D) 50 to 90% by mass of silver powder, You may make it contain so that it may become. With such a composition, heat resistance, moisture resistance, adhesiveness, and environmental resistance are improved.
本実施形態の電極形成用樹脂組成物は、上記(A)〜(D)の各成分を含むが、それら以外にも必要に応じて、この種の樹脂組成物に一般に配合される、硬化促進剤、ゴム、シリコーン等の低応力化剤、カップリング剤、密着付与剤、チタネートカップリング剤、顔料、染料、消泡剤、界面活性剤、希釈剤等の添加剤を適宜配合することができる。 The resin composition for forming an electrode according to the present embodiment contains the components (A) to (D) described above. In addition to the above components, if necessary, a curing accelerator generally blended with this type of resin composition is used. Agents, rubber, low-stress agents such as silicone, coupling agents, adhesion-imparting agents, titanate coupling agents, pigments, dyes, defoamers, surfactants, diluents, and other additives can be appropriately compounded. .
本実施形態の電極形成用樹脂組成物は、上記(A)〜(D)の各成分、及び必要に応じて配合されるカップリング剤等の添加剤、溶剤等を十分に混合する。
次に、本実施形態の電極形成用樹脂組成物は、混合した樹脂組成物をディスパース、ニーダー、3本ロールミル等により混練処理を行う。最後に、本実施形態の電極形成用樹脂組成物は、混練した樹脂組成物を脱泡することにより、調製することができる。The electrode forming resin composition of the present embodiment sufficiently mixes each of the components (A) to (D), additives such as a coupling agent and the like, and a solvent and the like that are blended as required.
Next, the resin composition for forming an electrode according to the present embodiment is subjected to a kneading treatment of the mixed resin composition by a disperser, a kneader, a three-roll mill, or the like. Finally, the electrode-forming resin composition of the present embodiment can be prepared by defoaming the kneaded resin composition.
このように得られる電極形成用樹脂組成物は、電気・電子部品の電極等を形成する用途に使用でき、そのチクソ比(25℃における、2rpmの粘度と20rpmの粘度の比率)が1.1〜4.5であってもよい。チクソ比が1.1未満であると電子部品製造時のディップ塗布時に糸引きによる作業性の低下を誘引するおそれがあり、チクソ比が4.5を超えるとディップ塗布時に電気・電子部品の外部電極として用いた場合、角立ちが発生し寸法安定性が悪く、いずれの場合も電子部品としての歩留まりが悪化する。 The electrode-forming resin composition thus obtained can be used for forming electrodes of electric / electronic parts and the like, and its thixo ratio (ratio of viscosity at 2 rpm to viscosity at 20 rpm at 25 ° C.) is 1.1. To 4.5. If the thixo ratio is less than 1.1, the workability may be reduced due to stringing at the time of dip coating during the production of electronic components. When used as an electrode, cornering occurs and dimensional stability is poor, and in any case, the yield as an electronic component is deteriorated.
また、電子部品の外部電極として形成される電極形成用樹脂組成物の硬化物の膜厚は5〜100μmであってもよい。膜厚が5μm未満では、意図した部分への塗布性が悪く塗膜均一性に欠けピンホールが発生し、100μm超では硬化時に垂れが発生し、塗膜均一性にかけるおそれがある。 The thickness of the cured product of the electrode-forming resin composition formed as the external electrode of the electronic component may be 5 to 100 μm. When the film thickness is less than 5 μm, the coating property on the intended portion is poor and the coating film lacks uniformity, and pinholes occur. When the film thickness exceeds 100 μm, sagging occurs at the time of curing, which may affect the coating film uniformity.
電子部品の製造工程において、電極形成用樹脂組成物を浸漬塗布する際にスキージによりディップ槽の表面が平坦化されるが、連続作業の効率上、電極形成用樹脂組成物の粘度変化率(増粘率)が200%以下であることが必要とされる。 In the electronic component manufacturing process, the surface of the dipping tank is flattened by a squeegee when dip-coating the electrode-forming resin composition, but the viscosity change rate (increase) of the electrode-forming resin composition is increased due to the efficiency of continuous operation. (Viscosity) is required to be 200% or less.
このようにして得られる本実施形態の電極形成用樹脂組成物は、その硬化物が車載部品レベルの耐環境性能(超耐湿性、超耐熱性)及び高熱伝導性、熱放散性に優れたものとなる。そのため、この電極形成用樹脂組成物を用いて電子部品の内部電極又は外部電極を形成した場合、著しい特性の向上が見られる。例えば、インダクタの外部電極として使用した場合、コイルと直接金属結合をし、かつコイル以外の素体とは樹脂接着力により高い接合力を発現することが可能なため、抵抗値の低減及び車載グレードでの信頼性の向上に寄与することができる。 The resin composition for forming an electrode of the present embodiment thus obtained has a cured product excellent in environmental resistance performance (ultra-moisture resistance, super-heat resistance), high thermal conductivity, and heat dissipation at the level of an in-vehicle component. Becomes Therefore, when an internal electrode or an external electrode of an electronic component is formed using this electrode forming resin composition, a remarkable improvement in characteristics is observed. For example, when used as an external electrode of an inductor, it can be directly metal-bonded to the coil, and can exhibit high bonding strength with the element other than the coil due to the resin adhesive force. Can improve reliability.
次に、本実施形態のチップ型電子部品及びその製造方法について説明する。
本実施形態のチップ型電子部品は、セラミックス焼結体よりなる直方体形状のチップ型電子部品素体を有するチップ型電子部品であって、チップ型電子部品素体の内部に形成された内部電極及びチップ型電子部品素体の端面に形成された外部電極の少なくとも1つが、上記実施形態の電極形成用樹脂組成物の焼結体である。このとき得られる焼結体の体積抵抗率は1×10−4Ω・cm以下であることが好ましい。さらに、体積抵抗率が低いほど電子部品としての特性が上がるため、この体積抵抗率が1×10−5Ω・cm以下であってもよい。体積抵抗率が1×10−4Ω・cmを超えると、十分に焼結されておらず、製品信頼性の悪化を招くおそれがある。Next, a chip-type electronic component and a method of manufacturing the same according to the present embodiment will be described.
The chip-type electronic component of the present embodiment is a chip-type electronic component having a rectangular parallelepiped chip-type electronic component body made of a ceramic sintered body, and includes an internal electrode formed inside the chip-type electronic component body and At least one of the external electrodes formed on the end surface of the chip-type electronic component body is a sintered body of the electrode-forming resin composition of the above embodiment. The sintered body obtained at this time preferably has a volume resistivity of 1 × 10 −4 Ω · cm or less. Further, the lower the volume resistivity, the higher the characteristics as an electronic component. Therefore, the volume resistivity may be 1 × 10 −5 Ω · cm or less. If the volume resistivity exceeds 1 × 10 −4 Ω · cm, sintering is not sufficiently performed, and there is a possibility that product reliability may be deteriorated.
本実施形態のチップ型電子部品の製造にあたっては、セラミック層の表面に、本実施形態の電極形成用樹脂組成物を用いて所定の電極パターン層を印刷により形成する。
本実施形態のチップ型電子部品の製造方法の次の工程は、該電極パターン層の上に他のセラミック層を載置し、該他のセラミック層の表面に、本実施形態の電極形成用樹脂組成物を用いて所定の電極パターン層を印刷により形成する操作を繰り返して、セラミック層と電極パターン層とを交互に積層する。
本実施形態のチップ型電子部品の製造方法の次の工程は、得られた積層体を焼結することで、電極パターンにより形成された内部電極を有するチップ型電子部品素体とする。
本実施形態のチップ型電子部品の製造方法の最後の工程は、該チップ型電子部品素体の端面に外部電極を形成し、チップ型電子部品を得る。このとき、外部電極の形成は、公知の電極形成用の樹脂組成物により実施できるが、本実施形態の電極形成用樹脂組成物を用いてもよい。
本実施形態の他のチップ型電子部品の製造にあたっては、チップ型電子部品素体の端面に、本実施形態の電極形成用樹脂組成物を印刷又は浸漬により塗布し、塗布された該電極形成用樹脂組成物を焼結することにより外部電極を形成し、チップ型電子部品を得る。
このとき、本実施形態において、上記電極形成用樹脂組成物は、従来通りの加熱により焼結でき、さらに、100〜300℃で焼結させても、十分に導電性を確保できる。また、この電極形成用樹脂組成物は、浸漬塗布時の連続作業性が良好で、電極形成を効率的に行うことができる。In manufacturing the chip-type electronic component of the present embodiment, a predetermined electrode pattern layer is formed on the surface of the ceramic layer by printing using the electrode forming resin composition of the present embodiment.
The next step of the method for manufacturing a chip-type electronic component according to the present embodiment is to place another ceramic layer on the electrode pattern layer, and apply the electrode forming resin of the present embodiment on the surface of the other ceramic layer. The operation of forming a predetermined electrode pattern layer by printing using the composition is repeated, and the ceramic layers and the electrode pattern layers are alternately laminated.
In the next step of the method for manufacturing a chip-type electronic component according to the present embodiment, the obtained laminate is sintered to obtain a chip-type electronic component body having internal electrodes formed by electrode patterns.
In the last step of the method of manufacturing a chip-type electronic component according to the present embodiment, an external electrode is formed on an end face of the chip-type electronic component body to obtain a chip-type electronic component. At this time, the external electrode can be formed by using a known resin composition for forming an electrode, but the resin composition for forming an electrode according to the present embodiment may be used.
In manufacturing another chip-type electronic component of the present embodiment, the electrode forming resin composition of the present embodiment is applied to the end surface of the chip-type electronic component body by printing or dipping, and the coated electrode forming An external electrode is formed by sintering the resin composition to obtain a chip-type electronic component.
At this time, in the present embodiment, the resin composition for forming an electrode can be sintered by heating as in the related art, and even when sintered at 100 to 300 ° C., sufficient conductivity can be ensured. In addition, the resin composition for electrode formation has good continuous workability at the time of dip coating, and can efficiently form electrodes.
次に、本実施形態を実施例によりさらに詳細に説明するが、本実施形態はこれらの実施例に何ら限定されるものではない。 Next, the present embodiment will be described in more detail with reference to examples, but the present embodiment is not limited to these examples.
(実施例1〜12、比較例1〜3)
表1〜3の記載の配合に従って各成分を混合し、ロールで混練し、電極形成用樹脂組成物を得た。得られた樹脂組成物を以下の方法で評価した。その結果を表1〜3に併せて示す。なお、実施例及び比較例で用いた材料は、下記の特性を有するものを使用した。(Examples 1 to 12, Comparative Examples 1 to 3)
Each component was mixed according to the composition shown in Tables 1 to 3, and kneaded with a roll to obtain a resin composition for forming an electrode. The obtained resin composition was evaluated by the following method. The results are shown in Tables 1 to 3. The materials used in Examples and Comparative Examples had the following characteristics.
[(A)成分]
(A1)アクリル樹脂:ヒドロキシルエチルアクリルアミド((株)興人製、商品名:HEAA)
(A2)イミド拡張型ビスマレイミド(デジグナーモレキュールズ社製、商品名:BMI−1500;数平均分子量 1500)
(A3)エポキシ化ポリブタジエン樹脂((株)日本曹達製、商品名:JP−200)
[(A´)成分]
エポキシ樹脂:ビスフェノールF型液状エポキシ樹脂(三菱化学(株)製、商品名:YL983U)
フェノール樹脂:ビスフェノールF(本州化学工業(株)製、商品名:ビスフェノールF)[(A) component]
(A1) Acrylic resin: hydroxyl ethyl acrylamide (trade name: HEAA, manufactured by Kojin Co., Ltd.)
(A2) Imide-expanded bismaleimide (trade name: BMI-1500, manufactured by Digigna Moleculars, Inc .; number average molecular weight 1500)
(A3) Epoxidized polybutadiene resin (manufactured by Nippon Soda Co., Ltd., trade name: JP-200)
[(A ') component]
Epoxy resin: bisphenol F type liquid epoxy resin (Mitsubishi Chemical Corporation, trade name: YL983U)
Phenol resin: bisphenol F (manufactured by Honshu Chemical Industry Co., Ltd., trade name: bisphenol F)
[(B)成分]
ラジカル開始剤:ジクミルパーオキサイド(日本油脂(株)製、商品名:パークミルD;急速加熱試験における分解温度:126℃)[Component (B)]
Radical initiator: dicumyl peroxide (manufactured by NOF Corporation, trade name: Parkmill D; decomposition temperature in rapid heating test: 126 ° C.)
[(C)成分]
プレート型銀微粒子(トクセン工業(株)製、商品名:M13;中心粒子径:2μm、厚み:50nm以下)
[(C´)成分]
球状銀微粒子(DOWAエレクトロニクス(株)製、商品名:Ag nano powder−1;平均粒径:20nm)[(C) component]
Plate-type silver fine particles (manufactured by Toxen Industries, Ltd., trade name: M13; central particle diameter: 2 μm, thickness: 50 nm or less)
[(C ') component]
Spherical silver fine particles (manufactured by DOWA Electronics Co., Ltd., trade name: Ag nano powder-1; average particle size: 20 nm)
[(D)成分]
銀粉A(形状:フレーク状、平均粒径:4.0μm、厚さ:0.3μm以上、タップ密度:5.5g/cm3)
銀粉B(形状:フレーク状、平均粒径:3.0μm、厚さ:0.3μm以上、タップ密度:3.8g/cm3)
銀粉C(形状:球状、平均粒径:2.4μm、タップ密度:5.0g/cm3)[(D) component]
Silver powder A (shape: flake shape, average particle size: 4.0 μm, thickness: 0.3 μm or more, tap density: 5.5 g / cm 3 )
Silver powder B (shape: flake shape, average particle size: 3.0 μm, thickness: 0.3 μm or more, tap density: 3.8 g / cm 3 )
Silver powder C (shape: spherical, average particle size: 2.4 μm, tap density: 5.0 g / cm 3 )
[その他の成分]
希釈溶剤:ブチルカルビトール(東京化成工業(株)製)
硬化促進剤:1−ベンジル−2−フェニルイミダゾール(四国化成工業(株)製、商品名:1B2PZ)
添加剤:シランカップリング剤(信越化学工業(株)製、商品名:KBM−503)[Other ingredients]
Diluent solvent: butyl carbitol (manufactured by Tokyo Chemical Industry Co., Ltd.)
Curing accelerator: 1-benzyl-2-phenylimidazole (Shikoku Chemical Industry Co., Ltd., trade name: 1B2PZ)
Additive: silane coupling agent (Shin-Etsu Chemical Co., Ltd., trade name: KBM-503)
<評価方法>
[粘度]
E型粘度計(3°コーン)を用いて、25℃、2rpmでの値を測定した。
[チクソ比]
E型粘度計(3°コーン)を用いて、25℃で、2rpm及び20rpmでの粘度を測定し、2rpmに対する20rpmの粘度の比(2rpmの粘度/20rpmの粘度)をチクソ比とした。<Evaluation method>
[viscosity]
The value was measured at 25 ° C. and 2 rpm using an E-type viscometer (3 ° cone).
[Thixo ratio]
The viscosities at 2 rpm and 20 rpm were measured at 25 ° C. using an E-type viscometer (3 ° cone), and the ratio of the viscosity at 20 rpm to 2 rpm (viscosity at 2 rpm / viscosity at 20 rpm) was defined as the thixo ratio.
[体積抵抗率]
電極形成用樹脂組成物を、ガラス基板(厚み1mm)にスクリーン印刷法により5mm×50mm、厚み30μmに塗布し、200℃、60分で硬化した。得られた配線を製品名「MCP−T600」(三菱化学(株)製)を用い4端子法にて電気抵抗を測定した。[Volume resistivity]
The electrode-forming resin composition was applied to a glass substrate (thickness: 1 mm) to a size of 5 mm × 50 mm and a thickness of 30 μm by a screen printing method, and cured at 200 ° C. for 60 minutes. The electrical resistance of the obtained wiring was measured by a four-terminal method using a product name “MCP-T600” (manufactured by Mitsubishi Chemical Corporation).
[塗布外観]
電極形成用樹脂組成物を、ディップ塗布により、チップ型電子部品素体の両端に成膜し、200℃、60分の加熱硬化を行い、電子部品とした。このとき得られた電子部品で電極形成用樹脂組成物の段差などにより寸法安定性の得られないものをNGとした。寸法安定性が得られるか否かの判断は、電極断面を顕微鏡で観察し、面の凹凸の差が50μm未満を「良」、表面の凹凸の差が50〜100μmを「可」、100μmを超えるものを「不良」と判定した。[Appearance]
The electrode-forming resin composition was formed into a film on both ends of the chip-type electronic component body by dip coating, and heat-cured at 200 ° C. for 60 minutes to obtain an electronic component. The electronic component obtained at this time, whose dimensional stability was not obtained due to a step of the resin composition for forming an electrode or the like, was regarded as NG. Judgment as to whether or not dimensional stability can be obtained is made by observing the electrode cross section with a microscope and determining that the difference between the surface irregularities is less than 50 μm is “good”, the difference between the surface irregularities is 50 to 100 μm “OK”, and 100 μm. Those exceeding these were judged as "poor".
[1%重量減少温度]
各実施例及び各比較例で得られた電極形成用樹脂組成物10mgを200℃で1時間硬化した後、測定装置としてTG/DTA7200熱重量分析装置(エスアイアイ・ナノテクノロジー株式会社製)を使用して、圧縮空気を流しながら、室温(25℃)から600℃の範囲で10℃/分の条件で加熱して、用いた試料の重量が1%減少する温度を測定することにより求めた。
[硬化物吸水率]
膜厚が200μm、大きさが500mm角の硬化物を用いて、初期重量を基準として85℃、85%高温恒湿槽に168時間放置した後の重量を測定することにより求めた。[1% weight loss temperature]
After 10 mg of the resin composition for electrode formation obtained in each of Examples and Comparative Examples was cured at 200 ° C. for 1 hour, a TG / DTA7200 thermogravimetric analyzer (manufactured by SII Nanotechnology Inc.) was used as a measuring device. Then, the sample was heated at a temperature of 10 ° C./min from room temperature (25 ° C.) to 600 ° C. while flowing compressed air, and the temperature at which the weight of the sample used decreased by 1% was measured.
[Water absorption of cured product]
Using a cured product having a thickness of 200 μm and a size of 500 mm square, the weight was determined by measuring the weight after standing in a 85 ° C., 85% high temperature and humidity chamber for 168 hours based on the initial weight.
[固着強度]
電極形成用樹脂組成物を、ディップ塗布により、チップ型電子部品素体の両端に成膜し、200℃、60分の加熱硬化を行った。これにNi及びSnメッキを施し、半田により基板に実装し、電子部品を作成した。この電子部品を20mm/分で横押しでせん断強度を測定し、破壊したときの荷重を固着強度(N)とした。[Adhesion strength]
The electrode-forming resin composition was formed into a film on both ends of the chip-type electronic component body by dip coating, and was heated and cured at 200 ° C. for 60 minutes. This was plated with Ni and Sn, and mounted on a substrate by soldering to produce an electronic component. The shear strength was measured by laterally pushing the electronic component at 20 mm / min, and the load at the time of breaking was defined as the fixing strength (N).
[耐熱通電試験後の抵抗値変化率]
電極形成用樹脂組成物を、ディップ塗布により、チップ型電子部品素体の両端に成膜し、200℃、60分の加熱硬化を行った。これにNi及びSnメッキを施し、半田により基板に実装し、電子部品を作成した。
当該電子部品を恒温槽(温度150℃)に入れ、この状態で通電試験(1A)を実施し、500時間経過後、1000時間経過後、2000時間経過後、3000時間経過後の初期値に対する相対値を算出した。[Resistivity change rate after heat resistance test]
The electrode-forming resin composition was formed into a film on both ends of the chip-type electronic component body by dip coating, and was heated and cured at 200 ° C. for 60 minutes. This was plated with Ni and Sn, and mounted on a substrate by soldering to produce an electronic component.
The electronic component is placed in a thermostat (temperature: 150 ° C.), and an energization test (1A) is performed in this state, and after 500 hours, 1000 hours, 2000 hours, and 3000 hours, relative to the initial values. Values were calculated.
[耐湿通電試験後の抵抗値変化率]
電極形成用樹脂組成物を、ディップ塗布により、チップ型電子部品素体の両端に成膜し、200℃、60分の加熱硬化を行った。これにNi及びSnメッキを施し、半田により基板に実装し、電子部品を作成した。[Resistivity change rate after humidity resistance and current test]
The electrode-forming resin composition was formed into a film on both ends of the chip-type electronic component body by dip coating, and was heated and cured at 200 ° C. for 60 minutes. This was plated with Ni and Sn, and mounted on a substrate by soldering to produce an electronic component.
当該電子部品を恒温恒湿槽(温度85℃、湿度85%)に入れ、この状態で通電試験(1A)を実施し、500時間経過後、1000時間経過後、2000時間経過後、3000時間経過後の初期値に対する相対値を算出した。 The electronic component is placed in a thermo-hygrostat (temperature: 85 ° C., humidity: 85%), and a current test (1 A) is performed in this state. After 500 hours, after 1000 hours, after 2000 hours, after 3000 hours The relative value to the subsequent initial value was calculated.
以上の結果より、本実施形態の電極形成用樹脂組成物を使用した電子部品は、いずれの特性も良好で高信頼性の電子部品が得られることがわかった。 From the above results, it was found that the electronic component using the electrode-forming resin composition of the present embodiment can obtain a highly reliable electronic component having good characteristics.
Claims (10)
前記(A)熱硬化性樹脂が、(A1)ヒドロキシル基を有する、(メタ)アクリル酸エステル化合物又は(メタ)アクリルアミド化合物、(A2)常温で液状であり、ビスマレイミド樹脂、(A3)エポキシ化ポリブタジエン、を含むことを特徴とする電極形成用樹脂組成物。(A) a thermosetting resin, (B) a radical initiator, (C) silver fine particles having a thickness or a minor axis of 1 to 200 nm, and (D) an average particle diameter other than the component (C) of 2 to 2. 20 μm of silver powder, and a resin composition for forming an electrode,
(A) the thermosetting resin is (A1) a (meth) acrylic acid ester compound or a (meth) acrylamide compound having a hydroxyl group, (A2) a liquid at room temperature, a bismaleimide resin, and (A3) epoxidation. A resin composition for forming an electrode, comprising polybutadiene.
の少なくとも1種を含有するアクリル樹脂であることを特徴とする請求項2又は3記載の電極形成用樹脂組成物。The compound (A1) wherein the (meth) acrylate compound or the (meth) acrylamide compound is selected from the following general formulas (1) to (4)
The resin composition for forming an electrode according to claim 2, wherein the resin composition is an acrylic resin containing at least one of the following.
さらに、該電極パターン層の上に他のセラミック層を載置し、該他のセラミック層の表面に、請求項1〜6のいずれか1項記載の電極形成用樹脂組成物を用いて所定の電極パターン層を印刷する操作を繰り返して、セラミック層と電極パターン層とを交互に積層させ、
得られた積層体を焼結することで、前記電極パターンにより形成された内部電極を有するチップ型電子部品素体とし、
該チップ型電子部品素体の端面に外部電極を形成する、ことを特徴とするチップ型電子部品の製造方法。A predetermined electrode pattern layer is printed on the surface of the ceramic layer using the electrode forming resin composition according to any one of claims 1 to 6,
Further, another ceramic layer is placed on the electrode pattern layer, and a predetermined surface is formed on the surface of the other ceramic layer by using the electrode forming resin composition according to any one of claims 1 to 6. Repeat the operation of printing the electrode pattern layer, alternately stack the ceramic layer and the electrode pattern layer,
By sintering the obtained laminate, a chip-type electronic component body having internal electrodes formed by the electrode pattern,
A method for manufacturing a chip-type electronic component, comprising forming an external electrode on an end surface of the chip-type electronic component body.
塗布された該電極形成用樹脂組成物を焼結することにより外部電極を形成する、ことを特徴とするチップ型電子部品の製造方法。Applying the electrode forming resin composition according to any one of claims 1 to 6 to the end surface of the chip-type electronic component body by printing or dipping,
A method for manufacturing a chip-type electronic component, comprising forming an external electrode by sintering the applied resin composition for forming an electrode.
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JP2014145011A (en) * | 2013-01-28 | 2014-08-14 | Hitachi Chemical Co Ltd | Resin paste composition |
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