WO2024014427A1 - Pâte conductrice, composant électronique et condensateur multicouche en céramique - Google Patents

Pâte conductrice, composant électronique et condensateur multicouche en céramique Download PDF

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Publication number
WO2024014427A1
WO2024014427A1 PCT/JP2023/025430 JP2023025430W WO2024014427A1 WO 2024014427 A1 WO2024014427 A1 WO 2024014427A1 JP 2023025430 W JP2023025430 W JP 2023025430W WO 2024014427 A1 WO2024014427 A1 WO 2024014427A1
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Prior art keywords
cellulose
conductive paste
compound
group
polyvinyl acetal
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PCT/JP2023/025430
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English (en)
Japanese (ja)
Inventor
伸寿 鈴木
祐司 奥田
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住友金属鉱山株式会社
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Publication of WO2024014427A1 publication Critical patent/WO2024014427A1/fr

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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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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

Definitions

  • the present invention relates to a conductive paste, an electronic component, and a multilayer ceramic capacitor.
  • Multilayer ceramic capacitors have a structure in which multiple dielectric layers and multiple internal electrode layers are alternately stacked, and by making these dielectric layers and internal electrode layers thinner, they can be made smaller and have higher capacity. can be achieved.
  • a multilayer ceramic capacitor is manufactured, for example, as follows. First, conductive paste for internal electrodes is printed (applied) in a predetermined electrode pattern on the surface of a green sheet containing dielectric powder such as barium titanate (BaTiO 3 ) and binder resin such as polybutyral resin. , and dry to form a dry film. Next, a laminate is formed in which the dry films and green sheets are alternately stacked and heat-pressed to form an integrated state. This laminate is cut, subjected to an organic binder removal treatment in an oxidizing atmosphere or an inert atmosphere, and then fired to obtain fired chips. Next, an external electrode paste is applied to both ends of the fired chip, and after firing, nickel plating or the like is applied to the external electrode surface to obtain a multilayer ceramic capacitor (MLCC).
  • MLCC multilayer ceramic capacitor
  • MLCCs have been required to be even smaller and have a larger capacity.
  • thinner electrode films with excellent density and continuity, and ceramic dielectric materials and their use are required.
  • the dielectric layer used in the prior art attempts are being made to increase the dielectric constant and make the layer thinner, and dielectric layers with a thickness of 1.0 ⁇ m or less have already been put into practical use. It is also desired that the electrode film has a thickness of 1.0 ⁇ m or less.
  • the required characteristics for increasing the size and capacity of MLCCs include suppressing the decrease in insulation resistance under high temperature and high voltage, that is, high reliability.
  • the decrease in insulation resistance is said to be caused by the fact that the surface of the Ni electrode layer sandwiching the dielectric layer becomes uneven during the firing process, and the electric field concentrates on the protrusions.
  • the Ni electrode layer is formed through a process in which the Ni powder is sintered and becomes densified.
  • fine Ni powder sinters quickly the electrode is likely to break off and become spheroidized.
  • the effective electrode area of the Ni electrode layer decreases, leading to a decrease in capacity, and the unevenness on the surface of the Ni electrode layer leads to a decrease in insulation resistance.
  • the following measures 1) and 2) can be considered.
  • butyral resin as the resin can prevent the electrode from peeling off during cutting.
  • cellulose resins such as ethyl cellulose have been mainly used as organic binders, but cellulose resins have high compatibility with various solvents and are effective in imparting the desired rheological properties to conductive pastes.
  • the conductive paste itself does not have much thermoplasticity, it has the disadvantage that the dried part of the conductive paste hardly maintains adhesion to the upper green sheet during thermocompression bonding.
  • the internal electrode paste may contain an organic resin
  • the organic binder resin is preferably a mixture of ethyl cellulose (EC) and polyvinyl butyral (PVB).
  • Ethylcellulose has good solubility in solvents, printability, combustion decomposability, etc., and therefore can be suitably used as a binder for paste for internal electrodes. Further, by using polyvinyl butyral (PVB), which is used for green sheets, as an organic binder resin, it is possible to increase the adhesion strength between the green sheets and the dry film of the paste for internal electrodes.
  • PVB polyvinyl butyral
  • Patent Documents 1 and 2 disclose a conductive paste containing a cellulose resin and a polyvinyl butyral resin as a binder resin, and disclose that the adhesiveness with ceramic green sheets is improved.
  • the two organic binder resins when two different organic binder resins are generally mixed, most of the combinations are incompatible (incompatible). In the case of a combination of two organic binder resins that are incompatible, the two organic binder resins basically do not dissolve and exist independently, so not only will the expected performance not be achieved, but the functionality will often deteriorate significantly. .
  • the resin becomes difficult to dissolve in the solvent, the smoothness of the dried paste film will deteriorate.
  • the resin becomes difficult to dissolve in the solvent, the smoothness of the dried paste film will deteriorate.
  • a typical "sea-island structure" is observed, confirming phase separation.
  • the distribution of inorganic particles (conductive particles, ceramic powder) in the dry film becomes uneven.
  • the combination of organic materials in the paste composition affects the dispersibility of inorganic particles (conductive particles, ceramic powder) in the dry film.
  • the conductive pastes disclosed in Patent Documents 1 and 2 contain polyvinyl butyral resin, the adhesion between the dry film and the green sheet can be improved.
  • these technologies use cellulose resin and polyvinyl butyral resin together, the dispersion of the conductive powder and ceramic powder in the conductive paste is insufficient due to poor compatibility between the two resins. In some cases, the density and smoothness of the dried film of the conductive paste were insufficient. The characteristics of such a dry film cannot be said to be sufficient to cope with the increase in capacitance of multilayer ceramic capacitors in recent years.
  • the present invention provides a conductive paste using fine conductive powder or ceramic powder that has a smooth dry film and is suitable for making multilayer ceramic electronic components smaller and thinner.
  • the object of the present invention is to provide a conductive paste, an electronic component, and a multilayer ceramic capacitor that can form internal electrode layers with excellent adhesion.
  • the conductive paste of the present invention includes a conductive powder, a ceramic powder, a dispersant, a binder resin, and an organic solvent, and the binder resin contains cellulose, polyvinyl acetal, A polymer compound in which a cellulose compound and a polyvinyl acetal compound are bonded by a sulfur atom is included, and the molar ratio of the sulfur atom contained in the polymer compound to the total of the cellulose and the cellulose compound is 0.3 to It is 1.7.
  • the polyvinyl acetal compound is a polyvinyl acetal resin having a thiol group or a vinyl group, and the cellulose derivative has a thiol group
  • the polyvinyl acetal resin may include a vinyl group that reacts with the thiol group, and when the cellulose derivative includes a vinyl group, the polyvinyl acetal resin may include a thiol group that reacts with the vinyl group.
  • the cellulose derivative may be ethylcellulose having a thiol group or a vinyl group
  • the polyvinyl acetal resin may be polyvinyl butyral having a thiol group or a vinyl group.
  • the cellulose compound is a first esterification product obtained by dehydration condensation of a carboxy group of a carboxylic acid having a thiol group or a vinyl group and a hydroxyl group of cellulose, and the polyvinyl acetal compound has a thiol group or a vinyl group.
  • a second esterification reaction product is a dehydration condensation of a carboxy group of a carboxylic acid and a hydroxyl group of polyvinyl acetal, and when the first esterification reaction product has a thiol group, the second esterification reaction product has a vinyl group.
  • the polymer compound has the first esterification reaction product and the second ester It may also be a thiol-ene reaction product with a chemical reaction product.
  • the first esterification reaction product is an esterification reaction product obtained by dehydration condensation of the carboxy group of 3-allyloxypropionic acid and the hydroxyl group of ethyl cellulose
  • the second esterification reaction product is an esterification reaction product obtained by dehydration condensation of the carboxy group of 3-allyloxypropionic acid and the hydroxyl group of ethyl cellulose. It may be an esterification reaction product obtained by dehydration condensation of the group and the hydroxyl group of polyvinyl butyral.
  • the conductive powder may be nickel powder.
  • the number average particle diameter of the conductive powder may be 0.05 ⁇ m or more and 1.0 ⁇ m or less.
  • the ceramic powder may include barium titanate.
  • the number average particle diameter of the ceramic powder may be 0.01 ⁇ m or more and 0.5 ⁇ m or less.
  • the content of the ceramic powder may be 1% by mass or more and 20% by mass or less.
  • the conductive paste of the present invention may be used for internal electrodes of laminated ceramic parts.
  • the electronic component of the present invention is an electronic component formed using the conductive paste of the present invention.
  • the multilayer ceramic capacitor of the present invention has at least a laminate in which a dielectric layer and an internal electrode layer are laminated, and the internal electrode layer is formed using the conductive paste of the present invention.
  • This is a multilayer ceramic capacitor formed using a multilayer ceramic capacitor.
  • the conductive paste of the present invention has excellent dispersibility of conductive powder, and has high surface smoothness in the dried film after application. Further, the electrode pattern of an electronic component such as a multilayer ceramic capacitor formed using the conductive paste of the present invention has excellent adhesion of the conductive paste even when forming a thin electrode.
  • FIG. 1 is a perspective view and a sectional view showing a multilayer ceramic capacitor according to this embodiment. It is a figure which evaluated the adhesiveness with the green sheet of the dry film which printed and dried the conductive paste.
  • the conductive paste of this embodiment includes conductive powder, ceramic powder, dispersant, binder resin, and organic solvent. Each component will be explained in detail below.
  • the conductive powder is not particularly limited, and metal powder can be used, for example, one or more powders selected from Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof. Among these, powders of Ni or alloys thereof are preferred from the viewpoints of conductivity, corrosion resistance, and cost.
  • Ni alloys include alloys of Ni and at least one element selected from the group consisting of Mn, Cr, Co, Al, Fe, Cu, Zn, Ag, Au, Pt, and Pd (Ni alloys). can be used.
  • the Ni content in the Ni alloy is, for example, 50% by mass or more, preferably 80% by mass or more. Further, the Ni powder may contain about several hundred ppm of S in order to suppress rapid gas generation due to partial thermal decomposition of the binder resin during binder removal treatment.
  • the method for producing the conductive powder is not particularly limited, and includes, for example, a method in which chloride vapor is directly precipitated from the gas phase in hydrogen gas, an atomization method from molten metal, a spray pyrolysis method using an aqueous solution, a raw material metal A wet method in which salt is reduced in an aqueous solution can be applied.
  • the number average particle diameter of the conductive powder is not particularly limited, and may be selected depending on the size of the electronic component to be used.
  • the number average particle diameter of the conductive powder is preferably 0.5 ⁇ m or less, and more preferably 0.3 ⁇ m or less, for example, for multilayer ceramic capacitors whose films are becoming increasingly thin. If the average particle size exceeds 0.5 ⁇ m, the surface of the internal electrodes becomes extremely uneven, which may deteriorate the electrical characteristics of the capacitor, which is not preferable.
  • the lower limit of the average particle size of the conductive powder is not particularly limited, but is, for example, 0.03 ⁇ m or more. When the number average particle diameter is smaller than 0.03 ⁇ m, handling becomes extremely difficult.
  • the number average particle diameter of the conductive powder is a value determined from observation using a scanning electron microscope (SEM), and the particle diameter of each of multiple particles is determined from an image observed with a SEM at a magnification of 10,000 times. This is the average value obtained by measuring.
  • SEM scanning electron microscope
  • the content of the conductive powder is preferably 30% by mass or more and less than 70% by mass, more preferably 40% by mass or more and 60% by mass or less, based on the total amount of the conductive paste.
  • the conductivity and dispersibility are excellent.
  • the ceramic powder is not particularly limited, and for example, in the case of a conductive paste for internal electrodes of a multilayer ceramic capacitor, a known ceramic powder is appropriately selected depending on the type of multilayer ceramic capacitor to be applied.
  • the ceramic powder include perovskite oxides containing Ba and Ti, preferably barium titanate (BaTiO 3 ).
  • a ceramic powder containing barium titanate as a main component and an oxide as a subcomponent may be used.
  • oxides include oxides of Mn, Cr, Si, Ca, Ba, Mg, V, W, Ta, Nb, and one or more rare earth elements.
  • a powder having the same composition as the dielectric ceramic powder constituting the green sheet of the multilayer ceramic capacitor may be used as the ceramic powder. This suppresses the occurrence of cracks due to shrinkage mismatch at the interface between the dielectric layer and the internal electrode layer during the sintering process.
  • such ceramic powders include, for example, ZnO, ferrite, PZT, BaO, Al2O3 , Bi2O3 , R (rare earth element) 2O3 , TiO2 , Nd2O3 , etc. Examples include oxides. Note that one type of ceramic powder may be used, or two or more types of ceramic powder may be used.
  • the number average particle diameter of the ceramic powder is, for example, 0.01 ⁇ m or more and 0.5 ⁇ m or less, preferably 0.01 ⁇ m or more and 0.3 ⁇ m or less. Since the number average particle size of the ceramic powder is within the above range, when used as an internal electrode paste, a sufficiently thin and uniform internal electrode can be formed.
  • the number average particle diameter is a value obtained from observation with a scanning electron microscope (SEM), and the particle diameter of each particle is measured from an image observed with a SEM at a magnification of 50,000 times. This is the average value obtained.
  • the content of the ceramic powder is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 30 parts by mass or less, based on 100 parts by mass of the conductive powder.
  • the conductivity and dispersibility are excellent.
  • the content of the ceramic powder is preferably 1% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 20% by mass or less, based on the total amount of the conductive paste.
  • the conductivity and dispersibility are excellent.
  • the binder resin used in the conductive paste of this embodiment includes a polymer compound in which cellulose, polyvinyl acetal, a cellulose compound and a polyvinyl acetal compound are bonded by sulfur atoms, and the sulfur atom contained in the polymer compound is The molar ratio of the cellulose to the total of the cellulose and the cellulose compound is from 0.3 to 1.7.
  • the binder resin used in the conductive paste of this embodiment includes a polymer compound in which a cellulose compound and a polyvinyl acetal compound are combined.
  • the number average molecular weight (Mn) of this polymer compound is preferably 20,000 to 200,000 in terms of standard polystyrene determined by gel permeation chromatography (GPC).
  • the content of the polymer compound in which the cellulose compound and the polyvinyl acetal compound are combined is preferably 1 part by mass or more and 10 parts by mass or less, more preferably 1 part by mass, based on 100 parts by mass of the conductive powder. The amount is 8 parts by mass or less.
  • the dry film obtained from the conductive paste of this embodiment has a smooth surface due to the cellulose compound. It can be provided with adhesive properties to green sheets due to the polyvinyl acetal compound. Furthermore, by providing the polymer compound with a structure of a cellulose compound and a polyvinyl acetal compound, which are not compatible with each other, in the same molecule, poor dispersion of the conductive paste can be solved.
  • the molar ratio of the sulfur atoms contained in the polymer compound to the total of the cellulose and the cellulose compound is 0.5 to 2
  • conventional cellulose and polyvinyl acetal resin may be used in combination as a binder resin.
  • the molar ratio is 0.3 to 1.7, the surface roughness of the dried film and the density of the dried film of the conductive paste are better than that of the conductive paste.
  • the molar ratio of the sulfur atoms contained in the polymer compound to the total of the cellulose and the cellulose polymer compound is 0.3 to 1.7, more preferably 0.5 to 1. It is 5.
  • a polymer compound in which a cellulose compound and a polyvinyl acetal compound are bonded together which can be used in this embodiment, will be explained in more detail.
  • Both cellulose and polyvinyl acetal have hydroxyl groups in their molecules.
  • Cellulose-based compounds are chemically modified with reactive functional groups by introducing functional groups that can react with other compounds to form bonds into the hydroxyl groups of cellulose, while polyvinyl acetal-based polymer compounds have hydroxyl groups that contain other compounds.
  • a polyvinyl acetal compound that can react with the cellulose compound to form a bond has a functional group different from the functional group introduced into the cellulose compound, and is chemically modified with a reactive functional group is prepared. That is, the reactive functional group introduced into the cellulose compound is different from the reactive functional group introduced into the polyvinyl acetal compound.
  • a polymer compound in which the cellulose compound and the polyvinyl acetal compound are bonded can be obtained.
  • a thiol group is introduced into cellulose to make a cellulose-based compound
  • a vinyl group is introduced into a polyvinyl acetal resin to make a polyvinyl acetal-based compound
  • the thiol group and the vinyl group become the presence of a nucleophile.
  • the double bond of the vinyl group and the sulfur atom of the thiol group bond together under conditions that generate radicals.
  • a polymer compound in which a cellulose compound and a polyvinyl acetal compound are bonded can be obtained by utilizing a bonding reaction between a thiol group and a vinyl group.
  • a cellulose-based compound may be obtained by introducing a vinyl group into the hydroxyl group of cellulose, and a thiol group may be introduced into the hydroxyl group of a polyvinyl acetal resin to form a polyvinyl acetal-based compound.
  • the cellulose compound may be a cellulose derivative having a thiol group or a vinyl group
  • the polyvinyl acetal compound may be a polyvinyl acetal resin having a thiol group or a vinyl group.
  • the polyvinyl acetal resin has a vinyl group that reacts with the thiol group
  • the polyvinyl acetal resin has a vinyl group that reacts with the thiol group. It has a thiol group that reacts with.
  • the cellulose-based compound used as the binder resin of the conductive paste of the present embodiment is preferably a chemically modified polymer compound in which the compound is bonded to the hydroxyl group of cellulose, which is a natural polymer. Note that the chemical modification here is different from the chemical modification that introduces a functional group with reactivity as described above.
  • Bonding of the compound to the hydroxyl group of cellulose includes alkyl etherification, esterification, and the like.
  • Celluloses with hydroxyl groups include methyl cellulose, ethyl cellulose, propyl cellulose, butyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose, cellulose acetate (acetyl cellulose, diacetyl cellulose, triacetyl cellulose, etc.), cellulose acetate protein, etc. Examples include pionate, cellulose acetate butyrate, nitrocellulose, and the like. Only one type of cellulose may be used, or two or more types may be used in combination.
  • the conductive paste of the embodiment contains an organic solvent, it is preferable that cellulose is also dissolved in the organic solvent. From the viewpoint of solubility in organic solvents and smoothness of a dried film of the conductive paste, it is more desirable to use ethyl cellulose as the cellulose.
  • the molecular weight of cellulose affects the viscosity of the conductive paste of this embodiment.
  • the number average molecular weight (Mn) of cellulose is preferably 10,000 to 100,000, more preferably 10,000 to 80,000, as calculated by GPC in terms of standard polystyrene.
  • the viscosity of the conductive paste may become low, and if the number average molecular weight of cellulose exceeds 100,000, the viscosity of the conductive paste may become too high.
  • hydroxyl groups in cellulose are chemically modified.
  • the glucose rings constituting cellulose have three hydroxyl groups attached to them, and on average, 0.1 to 1 hydroxyl group per glucose ring of cellulose remains as a hydroxyl group and is not chemically modified. In this way, a reactive functional group is introduced into a hydroxyl group that has not been chemically modified.
  • polyvinyl acetal is usually a polymer composed of vinyl acetal/vinyl alcohol/vinyl acetate monomer units, and can be obtained by saponifying polyvinyl acetate to polyvinyl alcohol, and then acetalizing polyvinyl alcohol.
  • examples include butyralized polyvinyl alcohol (polyvinyl butyral), formalized polyvinyl alcohol (polyvinyl formal), and the like.
  • Polyvinyl acetal may be a commercially available product, and various polyvinyl acetals with different butyralization degrees, formalization degrees, acetyl group weights, hydroxyl group weights, molecular weights, etc. are sold by Sekisui Chemical Co., Ltd., Kuraray Co., Ltd., etc. Only one type of polyvinyl acetal may be used, or two or more types may be used in combination.
  • the polyvinyl acetal is soluble in an organic solvent.
  • the polyvinyl acetal is more preferably polyvinyl butyral because of its high solubility in organic solvents.
  • Polyvinyl acetal affects film strength and solution viscosity depending on its molecular weight. Therefore, the number average molecular weight of the polyvinyl acetal is preferably in the range of 50,000 to 150,000, more preferably in the range of 10,000 to 100,000, as calculated by GPC in terms of standard polystyrene.
  • the solution viscosity will be extremely low, making it difficult to adjust the viscosity of the inorganic particle-containing composition (paste or slurry), and making it difficult to apply and dry the inorganic particle-containing composition. There is a risk that the strength and adhesion of the resulting film will decrease.
  • Polyvinyl acetal has at least one hydroxyl group in one molecule. Generally, polyvinyl acetal has 20 to 40 mol% of hydroxy groups as vinyl alcohol units constituting the polymer. This hydroxyl group is chemically modified by introducing a reactive functional group.
  • a compound having a thiol group or a vinyl group at one end and a carboxyl group at the other end can be used as a compound that reacts with the hydroxyl group of cellulose to chemically modify it.
  • the carboxyl group of the compound undergoes dehydration condensation with the hydroxyl group of the cellulose-based polymer compound to form an ester bond.
  • a method for synthesizing the polymer compound used in this embodiment will be explained.
  • a compound with a functional group that reacts with a hydroxyl group and a functional group that is reactive with other compounds is esterified with the hydroxyl group of cellulose or the hydroxyl group of polyvinyl acetal.
  • functional groups that react with hydroxyl groups include carboxyl groups and hydroxyl groups.
  • the esterification reaction can be carried out using a condensing agent, for example.
  • a condensing agent examples include carbodiimide, diphenylphosphoric azide, and 1-hydroxybenzotriazole. Only one type of condensing agent may be used, or two or more types may be used in combination. Among these, carbodiimide is suitable because it has excellent versatility and reactivity, and allows the reaction to proceed under low temperature conditions and without being affected by moisture in the reaction environment.
  • carbodiimides examples include dicyclohexylcarbodiimide, diisopropylcarbodiimide, N-[3-(dimethylamino)propyl]-N'-ethylcarbodiimide, N-[3-(dimethylamino)propyl]-N'-ethylcarbodiimide methiodade, etc. Can be mentioned. Among them, dicyclohexylcarbodiimide and diisopropylcarbodiimide are preferred from the viewpoint of availability.
  • a base such as dimethylaminopyridine or triethylamine
  • a reaction accelerator in a range of 0.01 mol % to 10 mol % based on the carbodiimide.
  • the etherification reaction can be efficiently carried out by using an alkali metal hydroxide such as KOH or NaOH; or an alkali metal hydride such as NaH or KH as a reaction catalyst.
  • an alkali metal hydroxide such as KOH or NaOH
  • an alkali metal hydride such as NaH or KH
  • cellulose is dissolved in an aprotic solvent such as ethyl acetate, and a compound containing a carboxyl group that forms an ester bond with a hydroxyl group and a vinyl group or thiol group that is a functional group that reacts with other compounds is mixed.
  • an aprotic solvent such as ethyl acetate
  • a compound containing a carboxyl group that forms an ester bond with a hydroxyl group and a vinyl group or thiol group that is a functional group that reacts with other compounds is mixed.
  • a base such as dimethylaminopyridine
  • the polymer compound used in this embodiment has a molar ratio of sulfur atoms to the total of cellulose and cellulose-based compounds of 0.3 to 1.7. Therefore, it is necessary to add 0.3 to 1.7 mol of a compound having a functional group that reacts with other compounds to 1 mol of cellulose.
  • the reaction temperature for synthesizing the cellulose compound is preferably in the range of room temperature to 50°C.
  • the system in which the synthesis reaction of cellulose compounds has been completed consists of unreacted cellulose in which no functional group with a hydroxyl group is reactive with other compounds has been introduced, and cellulose compound in which one reactive functional group has been introduced. A mixture of cellulose-based compounds into which multiple reactive functional groups have been introduced. Although chemical modification is a matter of probability, cellulose compounds in which one hydroxyl group of cellulose is chemically modified are most common. After the synthesis of the cellulose compound is completed, the solvent may be removed by distillation.
  • polyvinyl acetal is dissolved in an aprotic solvent such as ethyl acetate, and a polyvinyl acetal compound is prepared by dissolving polyvinyl acetal in an aprotic solvent such as ethyl acetate, and dissolving the polyvinyl acetal with a carboxyl group that forms an ester bond with a hydroxyl group and a vinyl group or thiol group that is a functional group that reacts with other compounds. It is also preferable to mix the compounds and use a condensing agent and a base such as dimethylaminopyridine as a nucleophile to promote the esterification reaction in a range of 0.01 mol% to 10 mol%.
  • a condensing agent and a base such as dimethylaminopyridine
  • the reaction temperature for chemical modification of the hydroxyl group of polyvinyl acetal is preferably in the range of room temperature to 50°C. After the synthesis of the polyvinyl acetal compound is completed, the solvent may be removed by distillation.
  • the polymer compound used in this embodiment can be obtained by dissolving a cellulose compound and a polyvinyl acetal compound in a solvent, adding a radical generator, and heating the resulting solution. and the thiol group provided on the other side react, and the cellulose-based compound and the polyvinyl acetal-based compound are bonded.
  • the cellulose compound and the polyvinyl acetal compound may be dissolved in a solvent, and a nucleophile such as a base such as an amine may be added and heated.
  • the temperature of the reaction for bonding the cellulose compound and the polyvinyl acetal compound can be selected as appropriate, but is preferably 60° C. or higher.
  • Solvents include conductive paste dihydroterpinyl acetate, isobornyl acetate, isobornyl propinate, isobornyl butyrate and isobornyl isobutyrate, ethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate.
  • Acetate solvents such as terpineol, terpene solvents such as dihydroterpineol can be used. If a solvent used for conductive paste is used as the solvent, a vehicle can be obtained in which the obtained polymer compound is dissolved in the solvent.
  • cellulose resins such as methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, and nitrocellulose
  • butyral resins such as acrylic resins and polyvinyl acetal resins are used. It is also possible to add resins.
  • the molecular weight of the resin that can be added in this way is about 20,000 to 200,000 in GCP.
  • the content of the binder resin is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 6% by mass or less, based on the total amount of the conductive paste.
  • the conductivity and dispersibility are excellent.
  • the cellulose derivative may be ethylcellulose having a thiol group or a vinyl group
  • the polyvinyl acetal resin may be polyvinyl butyral having a thiol group or a vinyl group.
  • the cellulose-based compound may be a first esterification reaction product in which a carboxy group of a carboxylic acid having a thiol group or a vinyl group and a hydroxyl group of cellulose are dehydrated and condensed, and the polyvinyl acetal-based compound is , a second esterification reaction product obtained by dehydration condensation of a carboxy group of a carboxylic acid having a thiol group or a vinyl group and a hydroxyl group of polyvinyl acetal.
  • the second esterification reaction product When the first esterification reaction product includes a thiol group, the second esterification reaction product includes a vinyl group, and when the first esterification reaction product includes a vinyl group, the second esterification reaction product includes a vinyl group.
  • the esterification reaction product may include a thiol group, and the polymer compound may be a thiol-ene reaction product of the first esterification reaction product and the second esterification reaction product.
  • the first esterification reaction product may be an esterification reaction product in which a carboxy group of 3-allyloxypropionic acid and a hydroxyl group of ethyl cellulose undergo dehydration condensation
  • the second esterification reaction product may be an esterification reaction product obtained by dehydration condensation of the carboxy group of 3-mercaptopropionic acid and the hydroxyl group of polyvinyl butyral.
  • Organic solvent is not particularly limited, and any known organic solvent that can dissolve the binder resin can be used.
  • organic solvents include dihydroterpinyl acetate, isobornyl acetate, isobornylpropinate, isobornyl butyrate and isobornyl isobutyrate, ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene Acetate solvents such as glycol monomethyl ether acetate and dipropylene glycol methyl ether acetate, terpene solvents such as terpineol and dihydroterpineol, hydrocarbon solvents such as tridecane, nonane, and cyclohexane, petroleum hydrocarbon solvents such as mineral spirit, etc. can be mentioned.
  • one type of organic solvent may be used, or two or more types may be used.
  • the content of the organic solvent is preferably 40 parts by mass or more and 100 parts by mass or less, more preferably 65 parts by mass or more and 95 parts by mass or less, based on 100 parts by mass of the conductive powder.
  • the conductivity and dispersibility are excellent.
  • the content of the organic solvent is preferably 20% by mass or more and 60% by mass or less, more preferably 35% by mass or more and 55% by mass or less, based on the total amount of the conductive paste.
  • the conductivity and dispersibility are excellent.
  • the conductive paste of this embodiment can contain a dispersant.
  • a dispersant The role of a dispersant is to adsorb to the surface of inorganic powders (conductive powders and ceramic powders) to suppress agglomeration of inorganic powders, and to improve wettability with organic vehicles and disperse them within the conductive paste. That's true.
  • Dispersants include higher fatty acids, acidic dispersants containing polymeric surfactants, cationic dispersants other than acidic dispersants, nonionic dispersants, amphoteric surfactants, and polymeric dispersants. It may also contain agents etc.
  • the dispersant may be selected from one type or a plurality of types, and the content of the conductive paste can be selected appropriately taking into consideration the viscosity, viscosity, long-term storage stability, etc. of the conductive paste. It may be included as long as it does not impede the effects of the invention.
  • the mass average molecular weight of the dispersant is preferably 200 to 100,000. More preferably 300 to 30,000. If the mass average molecular weight is less than 200, the particles may not have sufficient electrostatic repulsion, and the dispersibility and storage stability of the particles may deteriorate.
  • a paste with excellent dispersibility can be obtained by adsorbing the dispersant to the particle surface to form an adsorption layer of the dispersant and imparting electrostatic repulsion or steric repulsion to the particles.
  • the mass average molecular weight is preferably 200 or more.
  • the mass average molecular weight is greater than 100,000, the compatibility with organic vehicles and organic solvents may decrease, particles may aggregate with each other, and dispersibility and storage stability may decrease. Further, a problem arises in that the viscosity of the paste becomes high.
  • the amount of the dispersant added to the conductive metal powder is preferably 0.01 to 5.00 parts by mass, and 0.20 to 2.00 parts by mass per 100 parts by mass of the conductive metal powder. More preferred. If the amount of the dispersant is less than 0.01 part by mass, it tends to be difficult to obtain sufficient dispersibility. On the other hand, if it exceeds 5.00 parts by mass, problems such as poor drying properties and decreased dry film density will occur.
  • the method for manufacturing the conductive paste of this embodiment is not particularly limited, and conventionally known methods can be used.
  • the conductive paste can be produced, for example, by preparing the above-mentioned components and stirring and kneading them using a three-roll mill, a ball mill, a mixer, or the like. At this time, if a dispersant is applied to the surface of the conductive powder in advance, the conductive powder will be sufficiently loosened without agglomerating, and the dispersant will be spread over the surface, making it easier to obtain a uniform conductive paste.
  • the binder resin is dissolved in an organic solvent for a vehicle to prepare an organic vehicle, a conductive powder, a ceramic powder, an organic vehicle, and a dispersant are added to the organic solvent for a paste, and the mixture is stirred and kneaded with a mixer.
  • a conductive paste may also be prepared.
  • the organic solvent for the vehicle in order to improve the compatibility of the organic vehicle, it is preferable to use the same organic solvent for the paste that adjusts the viscosity of the conductive paste.
  • the content of the organic solvent for the vehicle is, for example, 5 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the conductive powder. Further, the content of the organic solvent for the vehicle is preferably 10% by mass or more and 40% by mass or less based on the entire amount of the conductive paste.
  • the surface smoothness of the dry film formed by printing the conductive paste can be evaluated by the surface roughness.
  • the surface roughness of the conductive paste can be measured, for example, by the method described in Examples (method of measuring the arithmetic mean height Sa based on the ISO 25178 standard using Keyence Corporation VK-X120). can be measured.
  • the surface smoothness of the dry film is evaluated by the arithmetic mean height Sa, it is preferable that the value is 0.10 ⁇ m or less.
  • the conductive paste of the present invention can be suitably used for electronic components such as multilayer ceramic capacitors.
  • a multilayer ceramic capacitor has a dielectric layer formed using a green sheet and an internal electrode layer formed using a conductive paste.
  • the dielectric ceramic powder contained in the green sheet and the ceramic powder contained in the conductive paste have the same composition, and for example, barium titanate can be used.
  • the multilayer ceramic capacitor manufactured using the conductive paste of the present embodiment sheet attack and poor peeling of the green sheet are suppressed even when the thickness of the green sheet is, for example, 3 ⁇ m or less.
  • the multilayer ceramic capacitor 1 includes a ceramic laminate 10 in which dielectric layers 12 and internal electrode layers 11 are alternately stacked, and an external electrode 20.
  • a method for manufacturing a multilayer ceramic capacitor 1 using the above conductive paste will be described.
  • a conductive paste is printed on a dielectric layer made of a green sheet and dried to form a dry film.
  • a plurality of dielectric layers having this dry film on the upper surface are laminated and pressure-bonded to obtain a laminate, and then the laminate is baked and integrated to form the internal electrode layer 11 and the dielectric layer.
  • a ceramic laminate 10 is produced in which ceramic laminates 12 and 12 are alternately laminated.
  • a pair of external electrodes 20 are formed at both ends of the ceramic laminate 10, thereby manufacturing the multilayer ceramic capacitor 1. This will be explained in more detail below.
  • a green sheet which is an unfired ceramic sheet made of dielectric material.
  • This green sheet is made of a dielectric layer paste obtained by adding an organic binder such as polyvinyl butyral and a solvent such as terpineol to a predetermined ceramic raw material powder such as barium titanate. Examples include those obtained by applying a sheet onto a film and drying it to remove the solvent.
  • the thickness of the dielectric layer made of green sheets is not particularly limited, but from the viewpoint of the demand for miniaturization of multilayer ceramic capacitors, it is preferably 0.05 ⁇ m or more and 3 ⁇ m or less.
  • a plurality of green sheets are prepared in which the above-mentioned conductive paste is printed (coated) on one side of the green sheet by a known method such as screen printing and dried to form a dry film.
  • the thickness of the conductive paste (dry film) after printing is preferably such that the thickness of the dry film after drying is 1 ⁇ m or less, from the viewpoint of the demand for thinning of the internal electrode layer 11.
  • the green sheet is peeled off from the support film, and the dielectric layer made of the green sheet and the dry film formed on one side of the green sheet are laminated in an alternating manner, and then the laminate is heated and pressurized. get.
  • a configuration may be adopted in which protective green sheets to which no conductive paste is applied are further disposed on both sides of the laminate.
  • the green chip is subjected to binder removal treatment and fired in a reducing atmosphere to produce the ceramic laminate 10.
  • the atmosphere in the binder removal treatment is preferably air or N2 gas atmosphere.
  • the temperature during the binder removal treatment is, for example, 200°C or more and 400°C or less. Further, it is preferable that the holding time at the above temperature during the binder removal treatment is 0.5 hours or more and 24 hours or less.
  • the firing is performed in a reducing atmosphere to suppress oxidation of the metal used for the internal electrode layer, and the temperature when firing the laminate is, for example, 1000°C or more and 1350°C or less, and the firing is The temperature is maintained for a period of, for example, 0.5 hours or more and 8 hours or less.
  • a multilayer ceramic fired body is formed in which a plurality of internal electrode layers 12 and internal electrode layers 11 are alternately stacked. Note that from the viewpoint of increasing reliability by incorporating oxygen into the dielectric layer and suppressing re-oxidation of the internal electrodes, the fired multilayer ceramic fired body may be subjected to an annealing treatment.
  • the multilayer ceramic capacitor 1 is manufactured by providing a pair of external electrodes 20 on the produced multilayer ceramic fired body.
  • the external electrode 20 includes an external electrode layer 21 and a plating layer 22.
  • External electrode layer 21 is electrically connected to internal electrode layer 11 .
  • the material for the external electrode 20 for example, copper, nickel, or an alloy thereof can be suitably used.
  • the electronic component is not limited to the multilayer ceramic capacitor, and may be an electronic component other than the multilayer ceramic capacitor, such as a varistor.
  • conductive powder As the conductive powder, Ni powder (number average particle diameter 0.2 ⁇ m by SEM measurement) was used.
  • ceramic powder As the ceramic powder, barium titanate (BaTiO 3 ; number average particle diameter 0.05 ⁇ m as measured by SEM) was used.
  • binder resin The binder resin was synthesized as follows.
  • Ethyl cellulose (Synthesis of cellulose compound (1a) having a vinyl group) Ethyl cellulose (“Ethocel STD-100" manufactured by Dow Chemical, number average molecular weight Mn (standard polystyrene equivalent value by GPC): 63420, average number of non-etherified hydroxyl groups per glucose ring 0.48) was prepared and dried. I let it happen.
  • the cellulose-based compound (1a) contains a compound in which a vinyl group is introduced into ethylcellulose, as well as unreacted ethylcellulose, but in the examples, a mixture of these is referred to as the cellulose-based compound (1a).
  • polyvinyl butyral compound (1b) contains a mixture of unreacted polyvinyl butyral as well as a compound in which a thiol group has been introduced into polyvinyl butyral. ). The same applies to polyvinyl butyral compounds (2b) and (3b) described later.
  • a polyvinyl butyral compound (2b) was prepared in the same manner as the polyvinyl butyral compound (1b), except that 3-mercaptopropionic acid was added in an amount corresponding to an average of 0.5 or 2 mercaptopropionic acids per molecule of polyvinyl butyral. , (3b) was synthesized.
  • the cellulose compound (1a) and the polyvinyl butyral compound (1b) have the same mol number, and since an average of one thiol group was introduced to one molecule of polyvinyl butyral as described above, the polymer compound 1
  • the molar ratio of the sulfur atoms contained in the cellulose to the total of cellulose and cellulose compounds is 1.
  • Organic vehicle 1 contains 13.5% by mass of polymer compound 1.
  • the polymer compound 1 contains a polymer compound in which a cellulose compound (1a) and a polyvinyl butyral compound (1b) are combined, unreacted ethyl cellulose, and unreacted polyvinyl butyral.
  • Both polymer compound 2 synthesized from cellulose compound (2a) and polyvinyl butyral compound (2b) and polymer compound 3 synthesized from cellulose compound (3a) and polyvinyl butyral compound (3b) are polymers.
  • Organic vehicles 2 and 3 were synthesized in the same manner as Compound 1, and the presence of the -S- bond was confirmed and the number average molecular weight was measured. Note that the content of the polymer compound 2 in the organic vehicle 2 is 13.5% by mass, and the content of the polymer compound 3 in the organic vehicle 3 is 13.5% by mass.
  • polymer compound 2 is a mixture of a polymer compound in which a cellulose compound (2a) and a polyvinyl butyral compound (2b) are combined, unreacted ethyl cellulose, and unreacted polyvinyl butyral. There is. The same applies to polymer compound 3.
  • the cellulose compound (2a) and the polyvinyl butyral compound (2b) have the same mol number, and since an average of 0.5 thiol groups were introduced into one molecule of polyvinyl butyral as described above, the polymer
  • the molar ratio of the sulfur atoms contained in Compound 2 to the total of cellulose and cellulose-based compound is 0.5.
  • the cellulose compound (3a) and the polyvinyl butyral compound (3b) have the same mol number, and since an average of two thiol groups were introduced into one molecule of polyvinyl butyral as described above, the polymer compound 3
  • the molar ratio of the sulfur atoms contained to the total of cellulose and cellulose compounds is 2.
  • Table 1 shows the characteristics of the cellulose compounds (1a) to (1c) and polyvinyl acetal compounds (1b) to (3b) used in polymer compounds 1 to 3.
  • the polymer compound 1 contains unreacted ethyl cellulose and polyvinyl butyral, but in the examples, these The mixture will be referred to as Polymer Compound 1.
  • Polymer Compound 1 The same applies to polymer compounds 2 and 3.
  • Example 1 47% by mass of Ni powder, 4.7% by mass of ceramic powder, 26.67% by mass of organic vehicle 1, 0.4% by mass of anionic dispersant of an amide compound of amino acid and fatty acid (hereinafter referred to as dispersant A), the balance
  • An organic solvent dihydroterpineol was blended in an amount of 21.23% by mass, and the total amount was 100% by mass, and these materials were mixed to prepare a conductive paste.
  • the produced conductive paste was printed and dried as follows, and the surface roughness of the dried film and the adhesion to the green sheet were evaluated. The evaluation results are shown in Table 2 and FIG. 2.
  • the surface roughness Sa (arithmetic mean height) of the produced dry film was measured based on the ISO 25178 standard using a laser microscope (VK-X120 manufactured by Keyence Corporation). The smaller the value of the surface roughness Sa (arithmetic mean height), the smoother the surface of the dried film. In addition, the obtained dried film was observed using SEM.
  • the prepared conductive paste was printed in a 2 cm square pattern on a 2.54 cm (1 inch) square BaTiO 3 dielectric green sheet by adjusting the printer so that the film thickness after printing was 3.6 ⁇ m. After printing, it was dried at 120° C. for 20 minutes to form a dry film of conductive paste on the surface of the green sheet.
  • the dried film of the conductive paste was covered with a BaTiO 3 dielectric green sheet, and the dried film of the conductive paste and the BaTiO 3 dielectric green sheet were thermocompression bonded using a hydrostatic press at 80° C. and 98 MPa to create a laminate.
  • the adhesion between the dry film of the conductive paste and the BaTiO 3 dielectric green sheet was evaluated by measuring the peeling force between the dry film of the conductive paste and the BaTiO 3 dielectric green sheet of the obtained laminate. .
  • This adhesion was measured using a thin film adhesion strength measuring device (Romulus, manufactured by Phototechnica).
  • a thin film adhesion strength measuring device Romulus, manufactured by Phototechnica.
  • an aluminum stud pin coated with epoxy adhesive is vertically glued to the center of the laminate, and the stud pin is vertically Prepare a bonded sample for adhesion evaluation, and evaluate the adhesion between the dry conductive paste film and the BaTiO 3 dielectric green sheet by pulling the stud pin of the sample off the surface of the laminate. did.
  • the evaluation results of adhesion are shown as the results of relative evaluation with the adhesion strength of Comparative Example 2, which will be described later, as 100.
  • Example 2 A conductive paste was prepared and evaluated in the same manner as in Example 1, except that organic vehicle 2 containing polymer compound 2 was used. The results are shown in Table 2.
  • Example 3 A conductive paste was prepared and evaluated in the same manner as in Example 2, except that an anionic dispersant of high-molecular polycarboxylic acid (hereinafter referred to as dispersant B) was used. The results are shown in Table 2 and Figure 2.
  • dispersant B an anionic dispersant of high-molecular polycarboxylic acid
  • Example 1 A conductive paste was prepared and evaluated in the same manner as in Example 1, except that organic vehicle 3 containing polymer compound 3 was used. The results are shown in Table 3.
  • Comparative Example 2 is an example of a conductive paste using a conventionally known combination of ethyl cellulose and polyvinyl butyral resin.
  • Comparative Example 1 has fewer irregularities than Comparative Example 2, which is a conventional example. However, if future miniaturization and thinning of laminated ceramic electronic components are taken into consideration, it can be confirmed that Comparative Example 1 is inferior to Examples 1 and 2 in terms of dry film smoothness.
  • Examples 1 and 3 which have excellent surface roughness Sa, also have better adhesion between the dry conductive paste film and the BaTiO 3 dielectric green sheet than Comparative Example 2.
  • the conductive paste according to this embodiment using finely divided conductive powder or ceramic powder, it is possible to provide a conductive paste that has a smooth dry film and has excellent adhesion. Therefore, it can be particularly suitably used as a raw material for internal electrodes of multilayer ceramic capacitors, which are chip components (electronic components) of electronic devices such as mobile phones and digital devices.
  • Multilayer ceramic capacitor 10 Ceramic laminate 11 Internal electrode layer 12 Dielectric layer 20 External electrode 21 External electrode layer 22 Plating layer

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Abstract

La présente invention concerne : une pâte conductrice faisant appel à une poudre conductrice et à une poudre céramique raffinées pour réduire la taille et l'épaisseur d'un composant électronique multicouche en céramique, et permettant de former une couche d'électrode interne ayant une excellente adhérence, tout en conservant un film sec lisse ; un composant électronique ; et un condensateur multicouche en céramique.　La présente invention concerne une pâte conductrice qui contient une poudre conductrice, une poudre céramique, un dispersant, une résine liante et un solvant organique : la résine liante contenant une cellulose, un acétal de polyvinyle et un composé polymère obtenu par liaison d'un composé cellulosique et d'un composé acétal de polyvinyle au moyen d'atomes de soufre ; le rapport molaire entre les atomes de soufre contenus dans le composé polymère et la somme de la cellulose et du composé cellulosique est compris entre 0,3 et 1,7.
PCT/JP2023/025430 2022-07-11 2023-07-10 Pâte conductrice, composant électronique et condensateur multicouche en céramique WO2024014427A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004186339A (ja) * 2002-12-02 2004-07-02 Shoei Chem Ind Co 積層電子部品の内部電極用導体ペーストおよびそれを用いた積層電子部品
WO2015107811A1 (fr) * 2014-01-17 2015-07-23 昭栄化学工業株式会社 Procédé de production d'une résine liante, procédé de production d'une composition de résine, résine liante, et composition de résine
JP2018184569A (ja) * 2017-04-27 2018-11-22 新中村化学工業株式会社 共重合体及び共重合体組成物
JP2020029479A (ja) * 2018-08-20 2020-02-27 新中村化学工業株式会社 高分子化合物及びそれを含む高分子組成物、並びに無機粒子含有組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004186339A (ja) * 2002-12-02 2004-07-02 Shoei Chem Ind Co 積層電子部品の内部電極用導体ペーストおよびそれを用いた積層電子部品
WO2015107811A1 (fr) * 2014-01-17 2015-07-23 昭栄化学工業株式会社 Procédé de production d'une résine liante, procédé de production d'une composition de résine, résine liante, et composition de résine
JP2018184569A (ja) * 2017-04-27 2018-11-22 新中村化学工業株式会社 共重合体及び共重合体組成物
JP2020029479A (ja) * 2018-08-20 2020-02-27 新中村化学工業株式会社 高分子化合物及びそれを含む高分子組成物、並びに無機粒子含有組成物

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