Composition, method for producing cured product, and cured product

Abstract

Provided are a composition capable of producing a cured product having low volume resistivity, a cured product obtained by curing the composition, and a method for producing a cured product using the aforementioned composition. A composition includes: (A) component: at least one metal particle selected from the group consisting of copper particles and silver particles; (B) component: at least one cashew component selected from the group consisting of cashew oil and cashew oil modified resin; and, (C) component: curing agent. Also provided is a cured product obtained by curing the aforementioned composition. Further, a method for producing a cured product includes: a coating step of coating the aforementioned composition on a substrate; and, a curing step of heating the aforementioned substrate on which the aforementioned composition is coated to cure the aforementioned composition.

Description

Technical Field

[0001] This invention relates to compositions, methods for manufacturing cured products, and cured products. Background Technology

[0002] Compositions containing conductive metals are used as materials in the manufacture of circuit wiring, touch panels, solar cells, sensors, and more. Currently, copper and silver particles, as conductive metals, are of particular interest, and various compositions containing copper or silver particles have been studied.

[0003] For example, Patent Document 1 discloses a copper paste composition containing copper particles, cresol-type phenolic resin, and a vinylphenol polymer. Patent Document 2 discloses a conductive copper paste containing copper particles, cresol-type phenolic resin, epoxy resin, and an organic acid. Patent Document 3 discloses a conductive paste containing silver-coated copper powder and epoxy resin. Patent Document 4 discloses a conductive silver paste containing spherical silver powder and a thermosetting epoxy resin. Patent Document 5 discloses a conductive paste containing silver-coated copper powder and bisphenol F type epoxy resin.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2018-092864

[0007] Patent Document 2: Japanese Patent Application Publication No. 2018-181558

[0008] Patent Document 3: Japanese Patent Application Publication No. 2012-167337

[0009] Patent Document 4: Japanese Patent Application Publication No. 2012-248370

[0010] Patent Document 5: Japanese Patent Application Publication No. 2020-033610 Summary of the Invention

[0011] The problem the invention aims to solve

[0012] However, the cured products obtained by curing the compositions disclosed in Patent Documents 1 to 5 cannot meet the volume resistivity requirements of materials in the field of electronic materials in recent years.

[0013] Therefore, the present invention aims to provide a composition capable of producing a cured material with low volume resistivity. Furthermore, the present invention aims to provide a method for manufacturing a cured material using the above composition, and a cured material obtained by curing the above composition.

[0014] Solution for solving the problem

[0015] The inventors conducted repeated and in-depth research in order to obtain the above-mentioned composition, and as a result, they discovered that by using a composition containing specific components, it is possible to manufacture a cured material with low volume resistivity, thus completing the present invention.

[0016] That is, according to the present invention, a composition is provided comprising: (A) component: at least one metal particle selected from the group consisting of copper particles and silver particles; (B) component: at least one cashew component selected from the group consisting of cashew oil and cashew oil modified resin; and (C) component: curing agent.

[0017] In addition, according to the present invention, a method for manufacturing a cured material is provided, comprising the following steps: a coating step, wherein the above-mentioned composition is coated on a substrate; and a curing step, wherein the substrate coated with the above-mentioned composition is heated to cure the above-mentioned composition.

[0018] Furthermore, according to the present invention, a cured product is provided, which is obtained by curing the above-described composition.

[0019] The effects of the invention

[0020] According to the present invention, a composition capable of producing a cured material with low volume resistivity can be provided. Furthermore, according to the present invention, a method for manufacturing a cured material using the above-described composition, and a cured material obtained by curing the above-described composition, can be provided. Detailed Implementation

[0021] Hereinafter, embodiments of the present invention will be described in detail. A composition of one embodiment of the present invention (hereinafter also referred to as "the composition") is a composition containing (A) component: at least one metal particle selected from the group consisting of copper particles and silver particles (hereinafter also referred to as "(A) component"), (B) component: at least one cashew component selected from the group consisting of cashew oil and cashew oil modified resin (hereinafter also referred to as "(B) component"), and (C) component: a curing agent (hereinafter also referred to as "(C) component") as essential components.

[0022] (A) The composition consists of at least one type of metal particles selected from the group consisting of copper particles and silver particles. There are no particular limitations on the types of copper and silver particles; commonly known copper and silver particles can be used. Copper particles are preferred because they are easy to process, readily available, and inexpensive.

[0023] Furthermore, for the purpose of producing cured products with lower volume resistivity, the average particle size of component (A) is preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm, and even more preferably 1.0 to 5.0 μm. The average particle size of component (A) represents the particle size (D) that constitutes 50% of the total particle size distribution on a volume basis, as measured and calculated using a particle size distribution measuring device based on laser diffraction. 50 It should be noted that, for component (A), if the metal particles have undergone surface treatment with fatty acids, etc. (described later), the average particle size can be obtained by measuring the surface-treated metal particles.

[0024] The shape of component (A) is not particularly limited, and one or more granular, needle-like, flake-like, or similar particles can be used. However, for the purpose of producing a cured product with lower volume resistivity, the composition preferably contains granular component (A). It should be noted that, in this specification, both flaky and plate-like metal particles are included within the flake-like metal particles.

[0025] When metal particles are oxidized by air or other sources, it is preferable to pre-clean the metal particles using an aqueous solution containing an inorganic or organic acid, in order to produce a solidified product with lower volume resistivity. For example, an aqueous solution containing sulfuric acid is preferred as the cleaning solution.

[0026] Furthermore, the metal particles (copper and silver particles) can be surface-treated or untreated. Since the metal particles (copper and silver particles) are highly susceptible to air oxidation, it is preferable to surface-treat the metal particles with fatty acids. Component (A) is preferably metal particles surface-treated with fatty acids. Among the metal particles in component (A) that have undergone fatty acid surface treatment, metal particles surface-treated with stearic acid are even more preferred.

[0027] The content of component (A) in the composition is preferably 50 to 99 parts by mass relative to 100 parts by mass of the total composition (in other words, 50 to 99% by mass based on the total mass of the composition). By having the content of component (A) in the above range, a cured product with excellent thermal stability and adhesion and lower volume resistivity can be manufactured. From this point of view, the content of component (A) in the composition is more preferably 60 to 97 parts by mass relative to 100 parts by mass of the total composition, and even more preferably 70 to 95 parts by mass.

[0028] (B) is at least one cashew ingredient selected from the group consisting of cashew oil and cashew oil-modified resin. Commercially available products may also be used as (B).

[0029] As commercially available cashew oil products, examples by brand name include CX-1000 and No. 930 (manufactured by Cashew Co., Ltd.); CNSL, LB-7000, LB-7250, CD-5L, LB-3025, and LB-3111 (manufactured by Tohoku Chemical). Industries, Ltd. (manufactured); NX-2021, NX-2022, NX-2023, NX-2023D, NX-2024, NX-2025, NX-2026, NX-5285, NX-9001, NX-9001LV, NX-9004, NX-9005, NX-9006, NX-9007, NX-9008, NX-9201, NX-9201LP, NX-9203, NX-9203LP, GX-2503, GX-9002, NC-510, LITE2020, LITE9001, and UltraLITE2023 (all manufactured by Cardolite Corporation); etc. It should be noted that polymerized cashew oil can also be used.

[0030] Examples of cashew oil-modified resins include cashew oil-modified phenolic resins, cashew oil-modified epoxy resins, cashew oil-modified furfural resins, cashew oil-modified benzoxazine resins, urushiol, thitsiol, and laccol. Preferably, the cashew oil-modified resin contains one or more of the above-mentioned resins.

[0031] Commercially available cashew oil-modified phenolic resins include, for example, PSM-9450, PR-150, PR-217, PR-12686, PR-12686E, PR-12687, PR-13349, PR-YR-170, PR-NR-1, and PR-BSN-21 (manufactured by Sumitomo Bakelite Co., Ltd.); No.1321, No.5208, No.5610, and 1200W (manufactured by Cashew Co., Ltd.); A4-1419 (manufactured by DIC Corporation); KG4700G (manufactured by ASAHI YUKIZAICORPORATION); ELP83H, ELPC80, ELPC75, and ELC75 (manufactured by Gun Ei Chemical Industry Co., Ltd.); etc.

[0032] Commercially available products made from cashew oil-modified epoxy resins include, for example, NC-513, NC-513E, NC-514, NC-514S, NC-547, LITE513, LITE513E, and UltraLITE513 (all manufactured by Cardolite Corporation).

[0033] As a commercially available product of cashew oil-modified furfural resin, examples include No. 2529 (Cashew Co., Ltd., manufactured by).

[0034] Commercially available products made from cashew oil-modified benzoxazine resins include, for example, CR-276 (manufactured by Tohoku Chemical Industries, Ltd.).

[0035] (B) Component can be used alone or in combination of two or more. For the purpose of producing a cured product with excellent adhesion and lower volume resistivity, (B) component preferably has an aliphatic hydrocarbon group with 10 to 20 carbon atoms. An aliphatic hydrocarbon group refers to a group composed of non-aromatic carbon and hydrogen, such as alkyl and alkenyl groups. Furthermore, as an alkenyl group, it is not limited to having one carbon-carbon double bond, but also includes groups having two or more carbon-carbon double bonds where the carbon-carbon double bonds are not adjacent, i.e., do not form -C=C=C-. (B) component is more preferably an aliphatic hydrocarbon group with 13 to 17 carbon atoms, even more preferably an aliphatic hydrocarbon group with 15 carbon atoms, and particularly preferably has at least one group selected from the groups shown in the following structural formulas (L-1) to (L-4).

[0036]

[0037] (In the above structural formulas (L-1) to (L-4), * represents an atomic bond.)

[0038] For the purpose of producing cured products with excellent adhesion and lower volume resistivity, cashew oil, cashew oil-modified phenolic resin, cashew oil-modified epoxy resin, cashew oil-modified furfural resin, and cashew oil-modified benzoxazine resin are preferred in component (B). Cashew oil-modified phenolic resin and cashew oil-modified epoxy resin are more preferred. When the composition contains xylene resin or phenolic resin as any of the components described below (D), cashew oil-modified phenolic resin is further preferred as component (B). Furthermore, when the composition contains epoxy resin as any of the components described below (D), cashew oil-modified epoxy resin is further preferred as component (B).

[0039] The content of component (B) in the composition is preferably 0.1 to 15 parts by mass relative to 100 parts by mass of the total composition (in other words, 0.1 to 15% by mass based on the total mass of the composition). By having the content of component (B) in the above range, a cured product with excellent thermal stability and adhesion and lower volume resistivity can be manufactured. From this point of view, the content of component (B) in the composition is more preferably 0.3 to 10 parts by mass relative to 100 parts by mass of the total composition, and even more preferably 0.5 to 7.5 parts by mass.

[0040] (C) is a curing agent. There is no particular limitation on the type of curing agent; any commonly known curing agent may be used. Examples of curing agents include latent curing agents, acid anhydrides, polyamine compounds, polyphenolic compounds, and cationic photoinitiators. The curing agent is the substance that cures component (B), and if the composition also contains component (D) described later, it is also the substance that cures component (D).

[0041] Examples of potential curing agents include dicyandiamide, hydrazides, imidazole compounds, amine adducts, sulfonium salts, onium salts, ketimides, acid anhydrides, and tertiary amines. Using these potential curing agents allows compositions containing additives for curing to become easily operable, single-component, curable compositions, which is therefore preferred.

[0042] Examples of imidazole compounds include 2-methylimidazolium, 2-phenylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 2-phenyl-4-methylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 1-benzyl-2-phenylimidazolium, 1-benzyl-2-methylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 2,4-diamino-6(2'-methylimidazolium(1'))ethyl-triazine, 2,4-diamino-6(2'-undecylimidazolium(1'))ethyl-triazine, and 2,4-diamino-6(2'-undecylimidazolium(1'))ethyl-triazine. Various imidazoles, including 2'-ethyl, 4-methylimidazolium (1'))ethyl-triazine, 2,4-diamino-6-(2'-methylimidazolium (1'))ethyl-triazine isocyanuric acid adduct, 2:3 adduct of 2-methylimidazolium isocyanuric acid, 2-phenylimidazolium isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazolium, 2-phenyl-4-hydroxymethyl-5-methylimidazolium, and 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazolium; and salts of these imidazoles with polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, and oxalic acid. For reasons of curability and storage stability, imidazole compounds having alkyl groups are preferred, with 2-ethyl-4-methylimidazolium and 2-phenyl-4-methyl-5-hydroxymethylimidazolium being particularly preferred. Commercially available examples, by trade name, include 2P4MHZ-PW, 2P4MHZ, and 2E4MZ (all manufactured by SHIKOKUCHEMICALS CORPORATION).

[0043] Examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, succinic anhydride, and 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride.

[0044] Examples of polyamine compounds include aliphatic polyamines such as ethylenediamine, diethylenetriamine, and triethylenetetramine; alicyclic polyamines such as menthanediamine, isophoronediamine, bis(4-amino-3-methylcyclohexyl)methane, bis(aminomethyl)cyclohexane, and 3,9-bis(3-aminopropyl)2,4,8,10-tetraoxaspiro[5,5]undecane; aliphatic polyamines with aromatic rings such as m-phenylenediamine; and aromatic polyamines such as m-phenylenediamine, 2,2-bis(4-aminophenyl)propane, diaminodiphenylmethane, diaminodiphenyl sulfone, α,α-bis(4-aminophenyl)-p-diisopropylbenzene, and 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane.

[0045] Examples of polyphenol compounds include phenolic varnish, o-cresol varnish, tert-butylphenol varnish, dicyclopentadiene cresol, terpene diphenol, terpene di-catechol, 1,1,3-tris(3-tert-butyl-4-hydroxy-6-methylphenyl)butane, butylene bis(3-tert-butyl-4-hydroxy-6-methylphenyl), and 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

[0046] In order to produce a cured product with excellent heat resistance, as component (C), a latent curing agent is preferred, wherein an imidazole compound is even more preferred.

[0047] The content of component (C) in the composition is preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the total composition (in other words, 0.1 to 5% by mass based on the total mass of the composition). For the sake of curability and heat resistance, the content of component (C) in the composition is more preferably 0.3 to 4 parts by mass, and even more preferably 0.5 to 3 parts by mass relative to 100 parts by mass of the total composition.

[0048] A preferred embodiment of the composition of the present invention further comprises component (D): at least one resin selected from the group consisting of xylene resin, phenolic resin, and epoxy resin (excluding component (B) mentioned above; also referred to as "component (D)" in this specification). By combining components (A) to (C) with component (D), a composition capable of producing cured products with excellent adhesion and lower volume resistivity can be obtained. It should be noted that xylene resin refers to a resin having a xylene structure in its structure and its derivatives. Furthermore, phenolic resin refers to a resin having a phenol structure in its structure and its derivatives. Finally, epoxy resin refers to a resin having an epoxy structure in its structure and its derivatives.

[0049] Examples of xylene resins include resol-type xylene resins, alkylphenol-modified xylene resins, phenolic varnish-type xylene resins, polyol-modified xylene resins, and ethylene oxide-modified xylene resins. Among these, resol-type xylene resins are preferred because they can produce cured products with excellent adhesion and lower volume resistivity.

[0050] Commercially available xylene resins can also be used. Examples of commercially available xylene resins include methyl methacrylate (trade names: PR-1440, PR-1440M manufactured by Fudow Company Limited), alkylphenol modified xylene (trade names: GHP-150, HP-120, HP-100, HP-210, HP-70 manufactured by Fudow Company Limited), phenolic varnish type xylene (trade names: NP-100, GP-212, P-100, GP-200, HP-30 manufactured by Fudow Company Limited), polyol modified xylene (trade name: K-100 manufactured by Fudow Company Limited), and ethylene oxide modified xylene (trade name: L5 manufactured by Fudow Company Limited). It should be noted that resins having both xylene and phenolic structures in their structure are preferred for producing cured products with excellent adhesion and lower volume resistivity.

[0051] Examples of phenolic resins include phenolic varnish-type phenolic resins and methyl phenolic resins. Among these, methyl phenolic resins are preferred because they can produce cured products with excellent adhesion and lower volume resistivity.

[0052] Phenolic resins can also be commercially available. Examples of commercially available phenolic resins include powdered phenolic resins (Gun Ei Chemical Industry Co., Ltd., trade names: RESITOP, PGA-4528, PGA-2473, PGA-4704, PGA-4504) and Sumitomo Bakelite Co., Ltd., trade name: SUMILITERESIN. PR-UFC-504, PR-EPN, PR-ACS-100, PR-ACS-150, PR-12687, PR-13355, PR-16382, PR-217, PR-310, PR-311, PR-50064 , PR-50099, PR-50102, PR-50252, PR-50395, PR-50590, PR-50590B, PR-50699, PR-50869, PR-51316, PR-51326B, PR-5 1350B, PR-51510, PR-51541B, PR-51794, PR-51820, PR-51939, PR-53153, PR-53364, PR-53497, PR-53724, PR-53769, PR-53804, PR-54364, PR-54458A, PR-54545, PR-55170, PR-8000, PR-FTZ-1, PR-FTZ-15), flaky phenolic resin (SumitomoBakelite Trade names of Sumitomo Bakelite Co., Ltd.: SUMILITERESIN PR-12686R, PR-13349, PR-50235A, PR-51363F, PR-51494G, PR-51618G, PR-53194, PR-53195, PR-54869, PR-F-110, PR-F-143, PR-F-151F, PR-F-85G, PR-HF-3, PR-HF-6; and liquid phenolic resin (trade name of Sumitomo Bakelite Co., Ltd.: SUMILITERESIN) PR-50087, PR-50607B, PR-50702, PR-50781, PR-51138C, PR-51206, PR-51663, PR-51947A, PR-53123, PR-5333 8. PR-53365, PR-53717, PR-54135, PR-54313, PR-54562, PR-55345, PR-940, PR-9400, PR-967), resol type liquid phenolic resin (Gun Ei ChemicalIndustry Co.,Ltd.Trade names manufactured by: RESITOP PL-4826, PL-2390, PL-4690, PL-3630, PL-4222, PL-4246, PL-2211, PL-3224, PL-4329, PL-5208; Trade names manufactured by Sumitomo Bakelite Co., Ltd.: SUMILITERESIN PR-50273, PR-51206, PR-51781, PR-53056, PR-53311, PR-53416, PR-53570, PR-54387; Particulate phenolic resin (AIR WATER) Trade names manufactured by INC.: Bellpearl, R800, R700, R600, R200, R100, S830, S870, S890, S895, S290, S190; spherical phenolic resins (manufactured by Gun Ei Chemical Industry Co., Ltd., trade names: Marilin GU-200, FM-010, FM-150, HF-008, HF-015, HF-075, HF-300, HF-500, HF-1500); solid phenolic resins (manufactured by Gun Ei Chemical Industry). Co., Ltd. manufactures products under the following trade names: RESITOP PS-2601, PS-2607, PS-2655, PS-2768, PS-2608, PS-4609, PSM-2222, PSK-2320, PS-6132, etc. It should be noted that resins containing xylene and phenolic structures are preferred for manufacturing cured products with excellent adhesion and lower volume resistivity.

[0053] Examples of epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD ​​type epoxy resin, bisphenol A-PO type epoxy resin, phenolic varnish type epoxy resin, cresol phenolic varnish type epoxy resin, glycidylamine type epoxy resin, dicyclopentadiene methacrylate type epoxy resin, urethane modified epoxy resin, rubber modified epoxy resin, and chelate modified epoxy resin. Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene methacrylate type epoxy resin, and chelate modified epoxy resin are preferred for producing cured products with excellent adhesion and lower volume resistivity; dicyclopentadiene methacrylate type epoxy resin and chelate modified epoxy resin are more preferred; and chelate modified epoxy resin is even more preferred. Furthermore, for the purpose of producing cured products with excellent adhesion and lower volume resistivity, the viscosity of the epoxy resin at 25°C is preferably 100 mPa·s or higher.

[0054] Commercially available epoxy resins are also acceptable. Examples of commercially available epoxy resins, listed by trade name, include AER-X8501 (manufactured by Asahi Kasei Corp.), R-301, and YL-980 (manufactured by Mitsubishi Chemical Corporation), which belong to the bisphenol A type; and YDF-170 (manufactured by NIPPON STEELC Chemical & Material Co., Ltd.), which belongs to the bisphenol F type.manufactured by Mitsubishi Chemical Corporation); epoxy resins having glycidyl groups (Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931, Denacol EX-145, Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-711, Denacol EX-721, Oncoat EX-1020, Oncoat EX-1030, Oncoat EX-1040, Oncoat EX-1050, Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, and Oncoat 1012 (manufactured by Nagase ChemteX Corporation), Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, and Epolite 100MF (manufactured by Osaka Gas Chemical Co., Ltd.OGSOL PG-100, OGSOL EG-200, OGSOL EG-210, and OGSOL EG-250 (and above, manufactured by Osaka GasChemical Co., Ltd.), HP4032, HP4032D, and HP4700 (and above, manufactured by DIC Corporation), ESN-475V (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.), 152, 154, 157S70, and YX8800 (and above, manufactured by Mitsubishi Chemical Corporation), ADEKA RESIN EP-4088S, ADEKA RESIN EP-4100, ADEKA RESIN EP-4100G, ADEKA RESIN EP-4100E, ADEKA RESIN EP-4100L, ADEKA RESIN EP-4100TX, ADEKA RESIN EP-4000, ADEKA RESIN EP-4005, ADEKA RESIN EP-4080E, ADEKA RESIN EP-4082HT, ADEKA RESIN EP-4901, ADEKA RESIN EP-4901E, ADEKA RESIN EP-49-10P, ADEKA RESIN EP-49-10P2, and ADEKA RESIN EP-49-23 (all manufactured by ADEKA CORPORATION); EXA-4816 and EXA-4822 (all manufactured by DIC Corporation), which belong to the polyepoxyalkylated bisphenol A type epoxy resins; R-1710 (manufactured by Mitsui Chemicals, Inc.), which belongs to the bisphenol A type epoxy resins; and N-730S (manufactured by DIC Corporation), which belongs to the phenolic varnish type epoxy resins. The following epoxy resins are listed: YDCN-702S (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.) and Quatrex-2010 (manufactured by Dow Chemical Company); YDCN-702S (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.) and EOCN-100 (manufactured by Nippon Kayaku Co., Ltd.) are cresol-phenolic varnish type epoxy resins; EPPN-501 (manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Company), and VG-3010 (manufactured by Mitsui Chemicals, Inc.) are multifunctional epoxy resins.1032S and 1032-H60 (manufactured by Mitsubishi Chemical Corporation); HP-4032 (manufactured by DIC Corporation), which belongs to the naphthalene skeleton epoxy resin category; EHPE-3150, CEL-3000 (manufactured by Daicel Corporation), DME-100 (manufactured by New Japan Chemical Co., Ltd.), and EX-216L (manufactured by Nagase ChemteX Corporation), which belong to the alicyclic epoxy resin category; W-100 (manufactured by New Japan Chemical Co., Ltd.), which belongs to the aliphatic epoxy resin category; ELM-100 (manufactured by SUMITOMO CHEMICAL COMPANY, LIMITED) and YH-434L (manufactured by NIPPON STEEL Chemical & Material), which belong to the amine type epoxy resin category. TETRAD-X, TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.), 630, and 630LSD (manufactured by Mitsubishi Chemical Corporation); Denacol EX-201 (manufactured by Nagase ChemteX Corporation), a resorcinol-type epoxy resin; Denacol EX-211 (manufactured by Nagase ChemteX Corporation), a neopentyl glycol-type epoxy resin; Denacol EX-212 (manufactured by Nagase ChemteX Corporation), a hexanedienyl glycol-type epoxy resin; and the Denacol EX series (EX-810, 811, 850, 851, 821, 830, 832, 841, 861, and above, manufactured by Nagase ChemteX Corporation), a ethylene glycol / propylene glycol-type epoxy resin. (Manufactured by DIC Corporation); EXA-4850-1000 and EXA-4850-150 (and above, manufactured by DIC Corporation), which belong to the vinyl ether type epoxy resins; etc. It should be noted that the epoxy resin diluents that can be used as solvents in component (E) described later are not included in epoxy resins that can be used as component (D).

[0055] The content of component (D) in the composition is preferably 30 parts by mass or less relative to 100 parts by mass of the total composition (in other words, 30% by mass or less based on the total mass of the composition). By having the content of component (D) in the above range, a cured product with excellent adhesion and lower volume resistivity can be manufactured. From this point of view, the content of component (D) in the composition is more preferably 1 to 25 parts by mass relative to 100 parts by mass of the total composition, and even more preferably 5 to 20 parts by mass.

[0056] The composition of one embodiment of the present invention preferably further contains component (E): solvent (hereinafter also referred to as "component (E)"). By combining the aforementioned components (A) to (C) with component (E), a composition capable of producing a cured product with excellent adhesion and lower volume resistivity can be obtained.

[0057] Examples of solvents include alcohol-based solvents, glycol-based solvents, ketone-based solvents, ester-based solvents, ether-based solvents, aliphatic or alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, hydrocarbon solvents containing cyano groups, and epoxy resin diluents. Among these, ester-based solvents or epoxy resin diluents are preferred for producing cured products with excellent adhesion and lower volume resistivity. If the composition contains xylene resin or phenolic resin as component (D) above, it is more preferable to contain an ester-based solvent as component (E). Furthermore, if the composition contains epoxy resin as component (D) above, it is more preferable to contain an epoxy resin diluent as component (E). It should be noted that component (E) is a liquid substance at atmospheric pressure and 25°C. Component (E) is included as a component different from components (A) to (D), and those components (B) to (D) that are liquid are not considered component (E).

[0058] Examples of alcohol-based solvents include methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, 2-butanol, tert-butanol, pentanol, isoamyl alcohol, 2-pentanol, neopentanol, tert-pentanol, hexanol, 2-hexanol, heptanol, 2-heptanol, octanol, 2-ethylhexanol, 2-octanol, cyclopentanol, cyclohexanol, cycloheptanol, methylcyclopentanol, methylcyclohexanol, methylcycloheptanol, benzyl alcohol, ethylene glycol monoacetate, and ethylene glycol. Monoethyl ether, ethylene glycol monophenyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, 2-(2-methoxyethoxy)ethanol, 2-(N,N-dimethylamino)ethanol, and 3-(N,N-dimethylamino)propanol, etc.

[0059] Examples of diol solvents include ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentanediol, isopentanediol (3-methyl-1,3-butanediol), 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,2-octanediol, octanediol (2-ethyl-1,3-hexanediol), 2-butyl-2-ethyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexanediol.

[0060] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl pentyl ketone, cyclohexanone, and methyl cyclohexanone.

[0061] Examples of ester-based solvents include methyl formate, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, tert-amyl acetate, phenyl acetate, methyl propionate, ethyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, sec-butyl propionate, tert-butyl propionate, amyl propionate, isoamyl propionate, tert-amyl propionate, and phenyl propionate. Ester, methyl 2-ethylhexanoate, ethyl 2-ethylhexanoate, propyl 2-ethylhexanoate, isopropyl 2-ethylhexanoate, butyl 2-ethylhexanoate, methyl lactate, ethyl lactate, methyl methoxypropionate, methyl ethoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether Acetates, ethylene glycol monobutyl ether acetate, ethylene glycol monosec-butyl ether acetate, ethylene glycol monoisobutyl ether acetate, ethylene glycol monotert-butyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monosec-butyl ether acetate, propylene glycol monoisobutyl ether acetate, Propylene glycol monotert-butyl ether acetate, butanediol monomethyl ether acetate, butanediol monoethyl ether acetate, butanediol monopropyl ether acetate, butanediol monoisopropyl ether acetate, butanediol monobutyl ether acetate, butanediol monosec-butyl ether acetate, butanediol monoisobutyl ether acetate, butanediol monotert-butyl ether acetate, methyl acetoacetate, ethyl acetoacetate, methyl oxobutyrate, ethyl oxobutyrate, γ-lactone, and δ-lactone, etc.

[0062] Examples of ether solvents include tetrahydrofuran, tetrahydropyran, morpholine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether, diethyl ether, and dioxane.

[0063] Examples of aliphatic or alicyclic hydrocarbon solvents include pentane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, naphthane, and solvent naphtha.

[0064] Examples of aromatic hydrocarbon solvents include benzene, toluene, ethylbenzene, xylene, mesitylene, diethylbenzene, cumene, isobutylbenzene, methyl isopropylbenzene, and tetrahydronaphthalene.

[0065] Examples of hydrocarbon solvents containing cyano groups include 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane, 1,4-dicyanocyclohexane, and 1,4-dicyanobenzene.

[0066] Commercially available products can be used as diluents for epoxy resins. Commercially available epoxy resin diluents include, for example, ADEKA RESIN ED-501, ADEKA RESIN ED-502, ADEKA RESIN ED-502S, ADEKA RESIN ED-509E, ADEKA RESIN ED-509S, ADEKA RESIN ED-529, ADEKA RESIN ED-518, ADEKA RESIN ED-503, ADEKA RESIN ED-503G, ADEKA RESIN ED-506, ADEKA RESIN ED-523T, ADEKA RESIN ED-515, ADEKA RESIN ED-505, ADEKA RESIN ED-505R, ADEKA RESIN ED-508, and ADEKA RESIN ED-512X (all manufactured by ADEKA CORPORATION). For the purpose of producing cured products with excellent adhesion and lower volume resistivity, monofunctional or difunctional epoxy resin diluents are preferred. Furthermore, for the purpose of producing cured products with excellent adhesion and lower volume resistivity, the viscosity of the epoxy resin diluent at 25°C is preferably less than 100 mPa·s.

[0067] The content of component (E) in the composition is preferably 20 parts by mass or less relative to 100 parts by mass of the total composition (in other words, 20% by mass or less based on the total mass of the composition). By having the content of component (E) in the above range, a cured product with excellent adhesion and lower volume resistivity can be manufactured. From this point of view, the content of component (E) in the composition is more preferably 0.5 to 15 parts by mass relative to 100 parts by mass of the total composition, and even more preferably 1 to 12 parts by mass.

[0068] Next, a method for manufacturing a cured product according to one embodiment of the present invention will be described. The method for manufacturing a cured product according to this embodiment includes the following steps: a coating step, in which the above-described composition is coated onto a substrate; and a curing step, in which the substrate coated with the composition is heated to cure the composition. In the curing step, heating the substrate coated with the composition at 50–250°C yields a cured product with better electrical conductivity; therefore, heating at 100–200°C is preferred, and more preferably preferred. Furthermore, in the curing step, to obtain a cured product with high heat resistance, heating the substrate coated with the composition for 1–200 minutes is preferred, and more preferably for 10–60 minutes is preferred. It should be noted that, if necessary, a drying step may also be included before the curing step: maintaining the substrate or the substrate coated with the composition at 50–150°C to allow low-boiling-point components such as organic solvents to evaporate.

[0069] Examples of substrates include resin substrates, glass substrates, and ceramic substrates. Examples of resin substrate materials include polyimide, polyester, aramid, polyethylene terephthalate (PET), and Teflon (registered trademark). Examples of ceramic substrate materials include alumina and alumina-zirconia. Furthermore, examples of glass substrate types include glass epoxy boards and glass / composite substrates.

[0070] In the coating process, methods for applying the composition to a substrate (coating methods) include, for example, spin coating, dip coating, spray coating, mist coating, flow coating, curtain coating, roller coating, air knife coating, bar coating, slot coating, screen printing, gravure printing, offset printing, inkjet printing, and brush coating.

[0071] To achieve the desired film thickness in the cured product, the coating process can be repeated multiple times, up to any other process. For example, the entire process from coating to curing can be repeated multiple times, or the coating and drying processes can be repeated multiple times.

[0072] By curing the composition, a cured product according to one embodiment of the present invention can be obtained. Examples of uses for the cured product of this embodiment include conductive layers, electrode films, and wiring.

[0073] As detailed above, this embodiment can be configured as follows.

[0074] [1] A composition comprising:

[0075] (A) Ingredient: At least one metal particle selected from the group consisting of copper particles and silver particles; (B) Ingredient: At least one cashew ingredient selected from the group consisting of cashew oil and cashew oil modified resin; and (C) Ingredient: Curing agent.

[0076] [2] According to the composition described in [1] above, wherein, relative to the total amount of the composition 100 parts by mass, the content of the aforementioned component (B) is 0.1 to 15 parts by mass and the content of the aforementioned component (C) is 0.1 to 5 parts by mass.

[0077] [3] The composition according to [1] or [2] above further contains component (D): at least one resin selected from the group consisting of xylene resin, phenolic resin and epoxy resin (excluding component (B) above).

[0078] [4] According to the composition described in [3] above, the content of the aforementioned component (D) is 30 parts by mass or less relative to the total amount of the composition, which is 100 parts by mass.

[0079] [5] The composition according to any one of [1] to [4] above further contains (E) component: solvent.

[0080] [6] According to the composition described in [5] above, the content of the aforementioned component (E) is 20 parts by mass or less relative to the total amount of the composition, which is 100 parts by mass.

[0081] [7] The composition according to any one of [1] to [6] above, wherein the aforementioned component (A) is a metal particle that has been surface-treated with fatty acids.

[0082] [8] A method for manufacturing a cured material, comprising the following steps:

[0083] In the coating process, the composition described in any one of [1] to [7] is coated onto the substrate; and,

[0084] In the curing process, the substrate coated with the aforementioned composition is heated to cure the aforementioned composition.

[0085] [9] In the method for manufacturing the cured product according to [8] above, the aforementioned substrate coated with the aforementioned composition is heated at 50 to 250°C for 1 to 200 minutes.

[0086]

[10] A cured product obtained by curing the composition described in any one of [1] to [7] above.

[0087] Example

[0088] The present invention will now be described in further detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples, etc.

[0089] <(A)Component>

[0090] Prepare A-1 and A-2 as shown below as component (A) (metal particles). It should be noted that A-1 and A-2 are prepared by surface treatment with stearic acid followed by drying.

[0091] A-1: Granular copper particles (D) 50 (3.5μm, trade name "1300Y", manufactured by MITSUI MINING & SMELTING CO.,LTD.)

[0092] A-2: Granular silver particles (D) 50 (2.5μm, trade name "SPN20J", manufactured by MITSUI MINING & SMELTING CO.,LTD.)

[0093] <(B) Component>

[0094] Prepare B-1 to B-8 as component (B) (cashew component). Each of B-1 to B-8 has at least one group selected from the groups shown in the aforementioned structural formulas (L-1) to (L-4).

[0095] B-1: Cashew oil (trade name "CX-1000", manufactured by Cashew Co., Ltd.)

[0096] B-2: Cashew oil (trade name "No. 930", manufactured by Cashew Co., Ltd.)

[0097] B-3: Cashew oil modified phenolic resin (trade name "ELP83H", manufactured by Gun Ei Chemical Industry Co., Ltd.)

[0098] B-4: Cashew oil modified phenolic resin (trade name "No. 5208", manufactured by Cashew Co., Ltd.)

[0099] B-5: Cashew oil modified furfural resin (trade name "No. 2529", manufactured by Cashew Co., Ltd.)

[0100] B-6: Cashew oil modified benzoxazine resin (trade name "CR-276", manufactured by Tohoku Chemical Industries, Ltd.)

[0101] B-7: Cashew oil modified epoxy resin (trade name "NC-513E", manufactured by Cardolite Corporation)

[0102] B-8: Cashew oil modified epoxy resin (trade name "NC-547", manufactured by Cardolite Corporation)

[0103] <(C) Ingredients>

[0104] Prepare C-1 and C-2 as shown below as component (C) (curing agent).

[0105] C-1: Imidazole compound (trade name "2P4MHZ-PW", manufactured by SHIKOKU CHEMICALS CORPORATION)

[0106] C-2: Imidazole compound (trade name "2E4MZ", manufactured by SHIKOKU CHEMICALS CORPORATION)

[0107] <(D) component>

[0108] Prepare components (D) (resins) as shown below, D-1 to D-7.

[0109] D-1: Xylene resin (trade name "PR-1440", manufactured by Fudow Company Limited)

[0110] D-2: Phenolic resin (trade name "PL-2211", manufactured by Gun Ei Chemical Industry Co., Ltd.)

[0111] D-3: Epoxy resin (trade name "ADEKA RESIN EP-49-10P", manufactured by ADEKA CORPORATION)

[0112] D-4: Epoxy resin (trade name "ADEKA RESIN EP-49-23", manufactured by ADEKA CORPORATION)

[0113] D-5: Epoxy resin (trade name "ADEKA RESIN EP-4100E", manufactured by ADEKA CORPORATION)

[0114] D-6: Epoxy resin (trade name "ADEKA RESIN EP-4901E", manufactured by ADEKA CORPORATION)

[0115] D-7: Epoxy resin (trade name "ADEKA RESIN EP-4088S", manufactured by ADEKA CORPORATION)

[0116] <(E) component>

[0117] Prepare E-1 and E-2 as shown below as component (E) (solvent).

[0118] E-1: Diethylene glycol monobutyl ether acetate

[0119] E-2: Epoxy resin diluent (trade name "ADEKA RESIN ED-503G", manufactured by ADEKA CORPORATION)

[0120] <Composition>

[0121] (Examples 1-16, Comparative Examples 1-4)

[0122] The components were mixed in such a manner as shown in Table 1 to manufacture the Example Compositions No. 1 to 16 and the Comparative Compositions 1 to 4.

[0123] Table 1

[0124]

[0125] <Manufacturing of solidified product a>

[0126] Using a rod coating method, the examples No. 1 to 16 and the comparative examples 1 to 4 were respectively coated onto a glass substrate to form a thickness of 30 μm (3 cm in length, 3 cm in width). The substrate was then heated and calcined at 200°C for 20 minutes in atmospheric conditions to obtain thin film-like cured products of the examples No. 1a to 16a and comparative examples 1a to 4a.

[0127] <Evaluation of volume resistivity>

[0128] (Evaluation Examples 1-16, Comparative Evaluation Examples 1-4)

[0129] The volume resistivity of cured samples No. 1a to 16a of the Examples and cured samples 1a to 4a of the Comparative Examples was measured using a high-precision resistivity meter (product name "Loresta GP", manufactured by Nittoseiko Analytech Co., Ltd.) according to the 4-probe method. The results are shown in Table 2.

[0130] <Manufacturing of solidified product b>

[0131] Using a rod coating method, the examples compositions No. 1 to 16 and the comparative examples compositions 1 to 4 were respectively coated onto a copper substrate to form a thickness of 30 μm (3 cm in length, 3 cm in width). The substrate was then heated and calcined at 200°C for 20 minutes in atmospheric conditions to obtain thin film-like cured products No. 1b to 16b of the examples and cured products 1b to 4b of the comparative examples.

[0132] <Evaluation of Adhesion> (Cross-cut test, tape peel test)

[0133] Eleven scratches were introduced into the cured products No. 1b to 16b of Examples and the cured products 1b to 4b of Comparative Examples using a cutting knife and a crisscross protector, creating 100 grids. Then, the tape was pressed firmly together, and one end of the tape was peeled off at a 45° angle in one go. The adhesion was evaluated according to the following criteria based on the presence or absence of peeling of the crisscrossed portions. The results are shown in Table 2.

[0134] Evaluation Criteria

[0135] ○: No peeling observed, excellent fit.

[0136] △: Delamination can be seen in 1 to 10 locations, indicating slightly poor adhesion.

[0137] ×: Delamination is visible in more than 11 locations, indicating poor adhesion.

[0138] Table 2

[0139]

[0140] ※oL: Overload (cannot be measured)

[0141] As shown in Table 2, it can be seen that Evaluation Examples 1-16 have lower volume resistivity compared to Comparative Evaluation Examples 1-4, meaning that the cured products of Examples No. 1a-16a have superior conductivity compared to the cured products of Comparative Examples 1a-4a. It can also be seen that among Evaluation Examples 1-16, Evaluation Examples 4, 5, 8, and 12 have even lower volume resistivity, with Evaluation Examples 4, 5, and 8 having particularly low volume resistivity. Therefore, the cured products of Examples No. 4a, 5a, 8a, and 12a have superior conductivity, and the cured products of Examples No. 4a, 5a, and 8a have particularly superior conductivity. Furthermore, it can be seen that even when curing is performed at a relatively high curing temperature of 200°C, cured products exhibiting excellent volume resistivity without thermal decomposition can be obtained. Furthermore, it can be seen that the cured products of Examples No. 1b-16b are cured products with excellent adhesion. From the above, it is evident that the cured products obtained by curing the composition of this embodiment are cured products with excellent adhesion and heat resistance, and high conductivity.

Claims

1. A composition comprising: (A) Composition: Copper particles; (B) Ingredients: At least one cashew ingredient selected from the group consisting of cashew oil and cashew oil-modified resin; and (C) Ingredients: Hardener, Component (A) is copper particles that have been surface-treated with fatty acids. Relative to the total amount of 100 parts by mass of the composition, the content of component (A) is 50 to 99 parts by mass, the content of component (B) is 0.1 to 15 parts by mass, and the content of component (C) is 0.1 to 5 parts by mass.

2. The composition according to claim 1, wherein, It also contains component (D): at least one resin selected from the group consisting of xylene resin, phenolic resin, and epoxy resin, wherein component (D) does not include component (B).

3. The composition according to claim 2, wherein, The content of component (D) is 30 parts by mass or less relative to the total amount of 100 parts by mass of the composition.

4. The composition according to claim 1, wherein, It also contains component (E): solvent.

5. The composition according to claim 4, wherein, The content of component (E) is 20 parts by mass or less relative to the total amount of 100 parts by mass of the composition.

6. A method for manufacturing a cured material, comprising the following steps: The coating process involves coating the composition according to any one of claims 1 to 5 onto a substrate; and, In the curing process, the substrate coated with the composition is heated to cure the composition.

7. The method for manufacturing a cured product according to claim 6, wherein, The substrate coated with the composition is heated at 50-250°C for 1-200 minutes.

8. A cured product obtained by curing the composition according to any one of claims 1 to 5.

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