Inorganic particle-containing paste, inorganic particle-containing film, and laminate

Abstract

The present application provides: in the case of lamination, a paste containing inorganic particles of a film containing inorganic particles which is less likely to cause interlayer peeling from other layers due to the action of shear force or the like, a film containing inorganic particles which can be formed using the paste containing inorganic particles, and a laminate comprising the above film containing inorganic particles. In the paste containing inorganic particles comprising a binder resin, inorganic particles, and an organic solvent, a branched polymer having a molecular chain provided with a main chain formed of a cellulose-based polymer and a branched chain formed of an aliphatic polycarbonate or an aliphatic polyester, and a dispersant having at least one selected from a polyether chain, a polyester chain, and a polycarbonate chain are used in combination.

Description

Technical Field

[0001] The present invention relates to a paste containing inorganic particles, a membrane containing inorganic particles formed using the paste containing inorganic particles, and a laminate containing the membrane containing the aforementioned inorganic particles. Background Technology

[0002] Membranes containing various inorganic particles are used in a variety of applications. One known method for forming such membranes is using a paste containing inorganic particles. A membrane containing inorganic particles can be formed by applying the paste through coating, printing, or other methods, followed by curing or drying.

[0003] As a surface application of films containing inorganic particles, laminates are known for manufacturing laminated ceramic electronic components such as laminated ceramic capacitors. These laminates typically consist of a green sheet containing ceramic powder and a precursor film containing an internal electrode layer of metal particles.

[0004] For example, as a conductive paste for forming a conductive sheet that provides an internal electrode layer by firing, a conductive paste comprising metal particles and ethyl cellulose as a binder resin has been proposed (see Patent Document 1). Ethyl cellulose exhibits excellent solubility in organic solvents, good decomposition during firing, and provides a conductive paste with good printability.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2018-168238 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] In manufacturing multilayer ceramic electronic components, there are cases where a multilayer containing conductive sheets and green sheets that have been fired to form internal electrode layers is cut into predetermined sizes using methods such as press cutting, and then the cut multilayers are fired. However, when using a multilayer containing conductive sheets, due to the shearing force applied to the cut surface when cutting the multilayer in a direction perpendicular or substantially perpendicular to the surface direction, there is a problem of interlayer delamination and intralayer delamination caused by agglomeration failure. The conductive sheets mentioned above are formed using a conductive paste containing ethyl cellulose as a binder resin.

[0010] The present invention was made in view of the above-mentioned problems, and its object is to provide: an inorganic particle-containing paste that provides an inorganic particle-containing membrane that is not prone to interlayer delamination due to shear force or the like, and is not prone to intralayer delamination due to coagulation failure when the laminate obtained by stacking an inorganic particle-containing membrane is cut into smaller pieces; an inorganic particle-containing membrane formed by using the inorganic particle-containing paste; and a laminate containing the above-mentioned inorganic particle-containing membrane.

[0011] Methods for solving problems

[0012] The inventors have discovered that by combining a branched polymer having a main chain formed of a cellulose polymer and branched chains formed of aliphatic polycarbonate or aliphatic polyester, and a dispersant having at least one selected from polyether chains, polyester chains, and polycarbonate chains, in a paste containing inorganic particles comprising an adhesive resin, inorganic particles, and an organic solvent, the above-mentioned problems can be solved, thereby completing the present invention. More specifically, the present invention provides the following (1) to (3).

[0013] (1) A paste containing inorganic particles, comprising a branched polymer, inorganic particles, a dispersant, and an organic solvent.

[0014] Branched polymers have a main chain formed by cellulose-based polymers and side chains formed by aliphatic polycarbonates or aliphatic polyesters.

[0015] Branches can be straight chains or branched chains.

[0016] The side chain can bond to two or more of the aforementioned main chains to crosslink the two or more main chains.

[0017] The dispersant has at least one selected from polyether chains, polyester chains and polycarbonate chains.

[0018] (2) A membrane containing inorganic particles, comprising a branched polymer, inorganic particles, and a dispersant.

[0019] Branched polymers have a main chain formed by cellulose-based polymers and side chains formed by aliphatic polycarbonates or aliphatic polyesters.

[0020] Branches can be straight chains or branched chains.

[0021] The side chain can bond to two or more of the aforementioned main chains to crosslink the two or more main chains.

[0022] The dispersant has at least one selected from polyether chains, polyester chains and polycarbonate chains.

[0023] (3) A laminate, wherein at least one layer comprises a membrane containing inorganic particles as described in (2).

[0024] Invention Effects

[0025] According to the present invention, it is possible to provide: an inorganic particle-containing paste that provides a membrane containing inorganic particles that is not easily delaminated from other layers due to shear forces or the like when laminated; an inorganic particle-containing membrane formed using the inorganic particle-containing paste; and a laminate containing the aforementioned inorganic particle-containing membrane. Detailed Implementation

[0026] Pastes containing inorganic particles

[0027] Pastes containing inorganic particles include branched polymers, inorganic particles, dispersants, and organic solvents.

[0028] Branched polymers have a main chain and branches. The main chain is formed from cellulose-based polymers. The branches are formed from aliphatic polycarbonates or aliphatic polyesters. The branches can be linear or branched. The branches can bond to two or more main chains, crosslinking them.

[0029] The dispersant has at least one selected from polyether chains, polyester chains and polycarbonate chains.

[0030] In an inorganic particle-containing paste containing inorganic particles and an organic solvent, a branched polymer with a specific structure and a dispersant with a specific chain structure are used in combination. The resulting inorganic particle-containing paste provides a film that is not prone to interlayer delamination due to shear forces or other forces, nor to intralayer delamination due to agglomeration and destruction, when the laminate obtained by stacking inorganic particle-containing films is cut into smaller pieces.

[0031] The following describes the necessary or optional ingredients that a paste containing inorganic particles may contain.

[0032] <Branched Polymers>

[0033] Branched polymers have a main chain and branches in their molecular chain. The main chain is formed from cellulosic polymers. The branches are formed from aliphatic polycarbonates or aliphatic polyesters.

[0034] Branches can be straight or branched. Branches can bond with two or more main chains, thus crosslinking the main chains.

[0035] By combining the above-mentioned branched polymers and the dispersants described later, a paste containing inorganic particles can be obtained. This paste provides a film containing inorganic particles that is not prone to interlayer delamination due to shear forces or other forces, nor to intralayer delamination due to agglomeration damage, when the laminate obtained by stacking the inorganic particle-containing film is cut into smaller pieces.

[0036] In branched polymers, the grafting ratio, i.e., the ratio of the mass of the branch to the mass of the main chain, is not particularly limited within a range that does not impair the desired effect. From the perspective of easily suppressing interlayer delamination caused by external forces such as shear force and easily suppressing intralayer delamination caused by agglomeration failure, the grafting ratio is preferably 10% by mass or more and 400% by mass or less, more preferably 50% by mass or more and 250% by mass or less.

[0037] The grafting rate can be determined by nuclear magnetic resonance spectroscopy (NMR analysis).

[0038] The mass-average molecular weight of the branched polymer is not particularly limited. Preferably, the mass-average molecular weight of the branched polymer is 50,000 or more and 1,000,000 or less, more preferably 100,000 or more and 600,000 or less. When the mass-average molecular weight of the branched polymer is within the above range, the branched polymer exhibits good mechanical properties such as strength, elongation, and toughness, as well as good formability.

[0039] The following describes the manufacturing methods for main-chain, branched, and branched polymers.

[0040] (Main Chain)

[0041] Branched polymers have a backbone formed from cellulose-based polymers. There are no particular limitations on the type of cellulose-based polymer, as long as the backbone has functional groups capable of bonding branches.

[0042] Preferred examples of cellulose-based polymers include cellulose; alkyl celluloses such as methylcellulose, ethylcellulose, n-propylcellulose, isopropylcellulose, n-butylcellulose, tert-butylcellulose, and n-hexylcellulose; hydroxyalkyl celluloses such as hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and hydroxybutylcellulose; cellulose esters such as cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate; carboxyalkyl celluloses such as carboxymethylcellulose, carboxyethylcellulose, and carboxypropylcellulose; and cellulose derivatives such as nitrocellulose, aldehyde cellulose, dialdehyde cellulose, and sulfonated cellulose.

[0043] Branched polymers can contain two or more branched polymer molecules with different types of cellulose-based polymers as the main chain.

[0044] Cellulose polymers are preferably selected from at least one of alkyl cellulose, hydroxyalkyl cellulose and cellulose esters, in order to facilitate the manufacture of branched polymers and to easily suppress interlayer delamination caused by external forces when laminating films containing inorganic particles formed by using pastes containing inorganic particles.

[0045] Among the preferred cellulose polymers described above, at least one is selected from methylcellulose, ethylcellulose, cellulose acetate butyrate, cellulose acetate propionate, and cellulose acetate.

[0046] The mass-average molecular weight of the cellulose polymer is not particularly limited. The mass-average molecular weight of the cellulose polymer is preferably 5,000 or more, more preferably 10,000 or more, and particularly preferably 100,000 or more. The mass-average molecular weight of the cellulose polymer is preferably 1,000,000 or less, more preferably 750,000 or less, and even more preferably 500,000 or less.

[0047] More specifically, the molecular weight of the cellulose polymer is preferably 5,000 or more and 1,000,000 or less, more preferably 10,000 or more and 750,000 or less, and even more preferably 10,000 or more and 750,000 or less.

[0048] The degree of substitution of cellulose polymers is not particularly limited within a range that does not impair the desired effect. The degree of substitution of cellulose polymers is preferably 2 or more and 3 or less, typically 2.5.

[0049] The degree of substitution of cellulose polymers is the total number of hydroxyl groups in the structural units of cellulose polymers that are replaced by groups other than those in the branched chain.

[0050] (Side chain)

[0051] Branched polymers have branches bonded to the main chain formed by cellulose-based polymers. These branches are formed from aliphatic polycarbonates or aliphatic polyesters. The branches can be linear or branched.

[0052] Typically, a branch bonds to only one main chain. A branch can also bond to two or more main chains, thus crosslinking the two or more main chains.

[0053] As long as the branch can be formed in a state of being combined with the main chain, or can be combined with the main chain, there are no particular limitations on the aliphatic polycarbonate or aliphatic polyester that constitute the branch.

[0054] Typical examples of branched aliphatic polycarbonates or aliphatic polyesters are shown in the following description of a method for manufacturing branched polymers.

[0055] (Manufacturing method of branched polymers)

[0056] There are no particular restrictions on the manufacturing methods of branched polymers. Typically, graft polymerization is used. The graft polymerization method can be appropriately selected from a variety of known methods depending on the type of branching.

[0057] As a graft polymerization method, ring-opening polymerization can be used, for example. By ring-opening polymerization of cyclic carbonate compounds, lactones, or other cyclic ester compounds in the presence of a cellulose-based polymer, aliphatic polycarbonates or aliphatic polyesters are generated as graft chains on the molecular chain of the cellulose-based polymer.

[0058] For example, propylene carbonate, as a cyclic compound, has branches formed from polypropylene carbonate. Butylene carbonate, as a cyclic compound, has branches formed from polybutylene carbonate. Cyclohexene carbonate, as a cyclic compound, has branches formed from polycyclohexene carbonate. Trimethylene carbonate, as a cyclic compound, has branches formed from polymethyl methacrylate. 2,2-Dimethyltrimethylene carbonate, as a cyclic compound, has branches formed from poly(2,2-dimethyltrimethylene carbonate).

[0059] ε-Caprolactone, as a cyclic compound, is branched from polycaprolactone, an aliphatic polyester. L-Lylactone, as a cyclic compound, is branched from polylactic acid, the L-form of an aliphatic polyester. D-Lylactone, as a cyclic compound, is branched from polylactic acid, the D-form of an aliphatic polyester. meso-lactone, as a cyclic compound, is branched from polylactic acid, the syndiotactic form of an aliphatic polyester. β-Proprolactone, as a cyclic compound, is branched from poly(3-hydroxypropionic acid), the D-form of an aliphatic polyester. β-Butyrolactone, as a cyclic compound, is branched from poly(3-hydroxybutyric acid), an aliphatic polyester. γ-Butyrolactone, as a cyclic compound, is branched from poly(4-hydroxybutyric acid), an aliphatic polyester. δ-Valactone, as a cyclic compound, is branched from poly(3-hydroxyvalerate), an aliphatic polyester. p-Dioxanone, as a cyclic compound, is given as poly(p-dioxanone) as a branched aliphatic polyester.

[0060] Typically, ring-opening polymerization is carried out in the presence of a catalyst. Specific examples of catalysts that can be used for ring-opening polymerization include alkali metals such as sodium and potassium; metal-containing catalysts such as sodium hydroxide, potassium hydroxide, triethylaluminum, triisopropoxyaluminum, n-butyllithium, tetraisopropoxytitanium, titanium tetrachloride, tetraisopropoxyzirconium, tin tetrachloride, sodium stannate, tin octoate, dibutyltin dilaurate, and diethylzinc; basic organic compounds such as pyridine, 4-N,N-dimethylaminopyridine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBT); acid catalysts such as hydrochloric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, diphenylphosphoric acid, and phenol; and N-heterocyclic carbene compounds such as 1,3-bis(2-propyl)-4,5-dimethylimidazolium-2-ene and 1,3-diisopropylimidazolium-2-ene.

[0061] A catalyst can be used alone or in combination of two or more.

[0062] When using cyclic carbonates for ring-opening polymerization, it is also preferable to use a co-catalyst together with the catalyst. Specific examples of co-catalysts include N-cyclohexyl-N'-phenylthiourea, N,N'-bis[3,5-bis(trifluoromethyl)phenyl]thiourea, N-[3,5-bis(trifluoromethyl)phenyl]-N'-cyclohexylthiourea, and (-)-stigmine.

[0063] The amount of catalyst used for ring-opening polymerization is appropriately determined considering the amount of catalyst used in previously known ring-opening polymerization reactions. Typically, the amount of catalyst used is preferably 0.001 moles or more, more preferably 0.005 moles or more, relative to 1 mole of the cyclic compound. The amount of catalyst used is preferably 0.2 moles or less, more preferably 0.1 moles or less, relative to 1 mole of the cyclic compound.

[0064] More specifically, the amount of catalyst used is preferably 0.001 moles or more and 0.2 moles or less, more preferably 0.005 moles or more and 0.1 moles or less, relative to 1 mole of the cyclic compound.

[0065] The amount of catalyst used is the same as the amount of catalyst used.

[0066] Ring-opening polymerization is preferably carried out in the presence of a solvent. The type of solvent is not particularly limited as long as it does not hinder the ring-opening polymerization reaction.

[0067] Preferred examples of solvents include aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; halogenated hydrocarbon solvents such as dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, chlorobenzene, and bromobenzene; ether solvents such as ethylene glycol dimethyl ether (monoethylene glycol dimethyl ether), diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), triethylene glycol dimethyl ether (triethylene glycol dimethyl ether), tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, and anisole; ester solvents such as ethyl acetate, n-propyl acetate, and isopropyl acetate; and amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

[0068] There is no particular limitation on the amount of solvent used, as long as the ring-opening polymerization reaction proceeds well. For example, the amount of solvent used is preferably 100 parts by mass or more and 1000 parts by mass or less relative to 100 parts by mass of the cyclic compound.

[0069] Typically, ring-opening polymerization is carried out by adding cellulose resin, cyclic compound, catalyst, and co-catalyst and / or solvent as needed into a reaction vessel, stirring the mixture in the reaction vessel.

[0070] The preferred reaction temperature for ring-opening polymerization varies depending on the cyclic compound, the type of catalyst, and the amount of catalyst used. Typically, the reaction temperature for ring-opening polymerization is preferably -80°C or higher, more preferably -40°C or higher, and even more preferably 0°C or higher. In terms of balancing good yield and suppression of side reactions, the reaction temperature for ring-opening polymerization is preferably 250°C or lower, more preferably 200°C or lower, and even more preferably 150°C or lower.

[0071] More specifically, the reaction temperature is preferably -80°C or higher and 250°C or lower, more preferably -40°C or higher and 200°C or lower, and even more preferably 0°C or higher and 150°C or lower.

[0072] The reaction time for ring-opening polymerization varies depending on the type of cyclic compound, the type of catalyst, and the amount of catalyst used. Typically, the reaction time for ring-opening polymerization is preferably more than 1 hour and less than 40 hours.

[0073] The amount of cyclic compound used in ring-opening polymerization should be appropriately determined based on the grafting rate mentioned above.

[0074] Another preferred example of a method for manufacturing branched polymers is the copolymerization of cyclic ethers with carbon dioxide in the presence of a cellulose resin. According to this copolymerization reaction, branches formed from aliphatic polycarbonate are generated. The cellulose resin is as described above.

[0075] As a cyclic ether, the appropriate cyclic ether is selected that corresponds to the aliphatic polycarbonate that serves as the branch.

[0076] Preferred examples of cyclic ethers include ethylene oxide, propylene oxide, trimethylene oxide (oxetane), 3,3-dimethyltrimethylmethylene oxide (3,3-dimethyloxetane), 1,2-epoxybutane, 2,3-epoxybutane, isobutane oxide, 1-pentene oxide, 2-pentene oxide, 1-hexene oxide, 1-octene oxide, 1-decene oxide, cyclopentene oxide, cyclohexene oxide, styrene oxide, vinylcyclohexane oxide, 3-phenylepoxypropane, 3,3,3-trifluoroepoxypropane, 3-naphthylepoxypropane, 2-phenoxypropane, 3-naphthyloxypropane, butadiene monooxide, 3-vinyloxypropane, and 3-trimethylsilyloxypropane.

[0077] Among the aforementioned cyclic ethers, ethylene oxide, propylene oxide, trimethylene oxide, and 1,2-epoxybutane are preferred from the perspective of excellent polymerization reactivity and the ability to obtain branched polymers that are easy to suppress interlayer delamination caused by external forces when laminating films containing inorganic particles formed using pastes containing inorganic particles. Ethylene oxide, propylene oxide, and trimethylene oxide are more preferred.

[0078] The following illustrates an example of an aliphatic polycarbonate produced by copolymerization of a cyclic ether and carbon dioxide. Ethylene oxide gives polyethylene carbonate. Propylene oxide gives polypropylene carbonate. Trimethylene oxide gives polytrimethylene carbonate.

[0079] The copolymerization of cyclic ethers with carbon dioxide is carried out in the presence of a metal catalyst. Preferred examples of metal catalysts include zinc-based, aluminum-based, chromium-based, and cobalt-based catalysts. Among these, zinc-based and cobalt-based catalysts are preferred based on their polymerization activity.

[0080] Preferred examples of zinc-based catalysts include diethylzinc-aqueous catalysts, diethylzinc-pyrogallol catalysts, bis((2,6-diphenyl)phenoxy)zinc, N-(2,6-diisopropylphenyl)-3,5-di-tert-butylsalicylaldehyde imine zinc, 2-((2,6-diisopropylphenyl)amide)-4-((2,6-diisopropylphenyl)imino)-2-pentenoic acid acetate, zinc adipate, and zinc glutarate.

[0081] Preferred specific examples of cobalt-based catalysts include cobalt acetate-acetic acid catalysts, N,N'-bis(3,5-di-tert-butylsalicyl)-1,2-cyclohexanediaminoacetate cobalt, N,N'-bis(3,5-di-tert-butylsalicyl)-1,2-cyclohexanediaminopentafluorobenzoate cobalt, N,N'-bis(3,5-di-tert-butylsalicyl)-1,2-cyclohexanediaminocobalt chloride, and N,N'-bis(3,5-di-tert-butylsalicyl)-1,2-cyclohexanediaminocobalt chloride. Cobalt nitrate of 1,2-cyclohexanediamino, cobalt oxide of 3,5-di-tert-butylsalicyl)-1,2-cyclohexanediamino-2,4-dinitrophenyl, cobalt chloride of tetraphenylporphyrin, cobalt acetate of tetraphenylporphyrin, cobalt chloride of N,N'-bis[2-(ethoxycarbonyl)-3-oxobutylidene]-1,2-cyclohexanediamine, and cobalt pentafluorobenzoate of N,N'-bis[2-(ethoxycarbonyl)-3-oxobutylidene]-1,2-cyclohexanediamine.

[0082] Cobalt-based catalysts are preferably used in conjunction with a co-catalyst. Specific examples of co-catalysts include pyridine, 4-N,N-dimethylaminopyridine, N-methylimidazolium, tetrabutylammonium chloride, tetrabutylammonium acetate, triphenylphosphine, bis(triphenylphosphine)ammonium chloride, and bis(triphenylphosphine)ammonium acetate.

[0083] Regarding the amount of catalyst used in the copolymerization of cyclic ethers and carbon dioxide, it is appropriately determined taking into account the amounts of catalysts known previously for this copolymerization reaction. Typically, the amount of catalyst used is preferably 0.001 moles or more, more preferably 0.005 moles or more, relative to 1 mole of cyclic ether. The amount of catalyst used is preferably 0.2 moles or less, more preferably 0.1 moles or less, relative to 1 mole of cyclic ether.

[0084] More specifically, the amount of catalyst used is preferably 0.001 moles or more and 0.2 moles or less, more preferably 0.005 moles or more and 0.1 moles or less, relative to 1 mole of cyclic ether.

[0085] The amount of catalyst used is the same as the amount of catalyst used.

[0086] The copolymerization of cyclic ethers with carbon dioxide is preferably carried out in the presence of a solvent. The type of solvent is not particularly limited, as long as it does not hinder the copolymerization reaction.

[0087] Preferred examples of solvents include aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; halogenated hydrocarbon solvents such as dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, chlorobenzene, and bromobenzene; ether solvents such as ethylene glycol dimethyl ether (monoethylene glycol dimethyl ether), diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), triethylene glycol dimethyl ether (triethylene glycol dimethyl ether), tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, and anisole; ester solvents such as ethyl acetate, n-propyl acetate, and isopropyl acetate; and amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

[0088] There are no particular limitations on the amount of solvent used, as long as the copolymerization reaction proceeds well. For example, the amount of solvent used is preferably 100 parts by mass or more and 1000 parts by mass or less relative to 100 parts by mass of the cyclic ether.

[0089] Typically, copolymerization is carried out by adding cellulose resin, cyclic ether, catalyst, and co-catalyst and / or solvent as needed into a reaction vessel, pressurizing carbon dioxide into the reaction vessel, and stirring the mixture in the reaction vessel.

[0090] The amount of cyclic ether and carbon dioxide used during copolymerization should be appropriately determined based on the grafting rate mentioned above.

[0091] Regarding the pressure of carbon dioxide inside the reaction vessel during copolymerization, from the perspective of ensuring a good reaction, using a gauge pressure at the reaction temperature, it is preferably 0.1 MPa or more, more preferably 0.2 MPa or more, and even more preferably 0.5 MPa or more. From the perspective of avoiding the need for expensive pressure-resistant vessels with high pressure resistance and ensuring operational safety, the pressure of carbon dioxide inside the reaction vessel is preferably 20 MPa or less, more preferably 10 MPa or less, and may also be 5 MPa or less.

[0092] More specifically, the pressure of carbon dioxide in the reaction solution is preferably 0.1 MPa or more and 20 MPa or less, more preferably 0.2 MPa or more and 10 MPa or less, and even more preferably 0.5 MPa or more and 5 MPa or less, measured by a gauge manometer.

[0093] Copolymerization can also be carried out under supercritical carbon dioxide conditions.

[0094] The preferred reaction temperature for copolymerization varies depending on the type of cyclic ether, the type of catalyst, and the amount of catalyst used. Typically, the copolymerization reaction temperature is preferably 0°C or higher, more preferably 20°C or higher, and even more preferably 30°C or higher. In terms of balancing good yield and suppression of side reactions, the copolymerization reaction temperature is preferably 100°C or lower, more preferably 80°C or lower, and even more preferably 60°C or lower.

[0095] In the above respects, the reaction temperature for copolymerization is preferably 0°C or higher and 100°C or lower, more preferably 20°C or higher and 80°C or lower, and even more preferably 30°C or higher and 60°C or lower.

[0096] The reaction time for copolymerization varies depending on the type of cyclic ether, the type of catalyst, and the amount of catalyst used. Typically, the reaction time for ring-opening polymerization is preferably more than 1 hour and less than 40 hours.

[0097] The amount of cyclic compound used in ring-opening polymerization should be appropriately determined based on the grafting rate mentioned above.

[0098] In the case of aliphatic polyesters whose branches are formed by the condensation polymerization of aliphatic dicarboxylic acids such as polyethylene succinate, polyethylene adipate, polybutylene succinate, and polybutylene adipate with diols, branched polymers can also be manufactured by co-condensation polymerization of aliphatic dicarboxylic acids and diols corresponding to the structure of aliphatic polyesters in the presence of cellulose resins using conventional methods.

[0099] There are no particular restrictions on the amount of branched polymers used in pastes containing inorganic particles, as long as the desired effect is not compromised.

[0100] For example, the ratio of the volume of the branched polymer to the total volume of the inorganic particles is preferably 17% or more and 29% or less, more preferably 19% or more and 27% or less.

[0101] <Inorganic Particles>

[0102] Pastes containing inorganic particles contain inorganic particles. As inorganic particles, those conventionally added to various resin compositions can be used without particular limitation.

[0103] As inorganic particles, ceramic particles and / or metal particles are typically preferred.

[0104] Preferred examples of films containing inorganic particles formed using pastes containing inorganic particles include conductive sheets containing metal particles and providing internal electrode layers, which constitute a useful laminate as a precursor for multilayer ceramic electronic components, or green sheets containing ceramic particles.

[0105] In the case of using a paste containing inorganic particles to form a green sheet of dielectric layer in a laminated ceramic electronic component, the ceramic particles are used as inorganic particles.

[0106] When using a paste containing inorganic particles to form an electrode sheet that provides an internal electrode layer in a stacked ceramic electronic component, the inorganic particles can also be combined to include metal particles and ceramic particles in terms of the affinity between the green sheet and the electrode sheet, and the adhesion between the dielectric layer and the internal electrode layer.

[0107] For ceramic particles, it is preferred that the constituent materials include at least one selected from Ba, Ti, Sr, Ca and Zr.

[0108] Preferred examples of ceramic particles include barium titanate particles, calcium titanate particles, strontium titanate particles, and lead zirconate titanate particles.

[0109] As ceramic particles, one type can be used alone, or two or more types can be used in combination. For example, ceramic particles containing barium titanate particles as the main component and components containing Ca, Zr, or Sr as secondary components can be used.

[0110] There is no particular limitation on the particle size of the ceramic particles as long as it does not impair the desired effect. The average particle size of the ceramic particles, based on the BET conversion algorithm, is preferably 3 nm or more and 500 nm or less.

[0111] When using a paste containing inorganic particles to form a conductive sheet that provides an internal electrode layer in a multilayer ceramic electronic component, metal particles are preferred as the inorganic particles.

[0112] The metal constituting the metal particles is preferably selected from at least one of Ni, Cu, Ag and Au.

[0113] The average particle size of the metal particles is not particularly limited as long as it does not impair the desired effect. The average particle size of the metal particles, measured by SEM diameter, is preferably 3000 nm or less, more preferably 30 nm or more and 1000 nm or less.

[0114] Metal particles can contain two or more metal particles. Metal particles can also be alloy particles containing two or more metals.

[0115] When the inorganic particles consist of ceramic particles and metal particles, the mass of the ceramic particles is preferably 4% or more and 25% or less of the mass of the metal particles.

[0116] <Dispersant>

[0117] Pastes containing inorganic particles include dispersants. The dispersants have at least one selected from polyether chains, polyester chains, and polycarbonate chains.

[0118] By having a polyether chain, polyester chain, or polycarbonate chain, the dispersant is readily compatible with branched polymers having branches formed from aliphatic polycarbonate or aliphatic polyester.

[0119] Examples of polyester chains and polycarbonate chains that have been described as branches of branched polymers include polyester chains and polycarbonate chains.

[0120] As a polyether chain, a polyoxyalkylene chain is preferred. Preferred examples of polyoxyalkylene chains include polyoxyethylene chains and polyoxypropylene chains.

[0121] Regarding the dispersing effect, the dispersant preferably has a hydrophobic group. Preferred examples of hydrophobic groups include hydrocarbon groups, fluorinated hydrocarbon groups, and more preferably aliphatic hydrocarbon groups and aliphatic fluorinated hydrocarbon groups.

[0122] In terms of dispersion effect, the dispersant preferably has adsorption groups such as carboxyl, amino, phosphate, and sulfonic acid groups that can bind to the surface of inorganic particles.

[0123] The molecular weight of the dispersant is not particularly limited within a range that does not impair the desired effect. The dispersant can be a so-called low molecular weight compound or a polymeric dispersant. In terms of the ease with which the dispersant can have the various functional groups described above in its molecular design, polymeric dispersants are preferred as dispersants.

[0124] As a polymeric dispersant, a comb-structured (meth)acrylic resin obtained by copolymerizing a (meth)acrylic monomer having a hydrophobic chain such as a hydrocarbon chain with a (meth)acrylic monomer having a hydrophilic chain such as a polyether chain, polyester chain, or polycarbonate chain is preferably used, for example. A comb-structured (meth)acrylic resin obtained by introducing the aforementioned hydrophobic and hydrophilic chains as side chains into known (meth)acrylic resins is also preferably used as a polymeric dispersant.

[0125] The amount of dispersant used is preferably 0.5 mg / m² relative to the surface area of ​​the particles to be dispersed. 2 ~5mg / m 2 More preferably 1.0 mg / m³ 2 ~2.5mg / m 2 .

[0126] <Other Ingredients>

[0127] For pastes containing inorganic particles, other ingredients besides those mentioned above may be included, as long as the desired effect is not compromised.

[0128] Other components include, for example, at least one additive selected from plasticizers and antistatic agents.

[0129] There are no particular limitations on the amount of other ingredients used, as long as the desired effect is not impaired. The amount of other ingredients used should be appropriately determined by considering the generally usable amounts corresponding to the types of additives mentioned above.

[0130] <Organic Solvents>

[0131] Pastes containing inorganic particles contain organic solvents. Preferred examples of organic solvents include alkanols such as isopropanol; hydrocarbon solvents such as toluene, xylene, and isophorone; terpineol solvents such as terpineol and dihydroterpineol; ester solvents such as ethyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, terpineol acetate, and dihydroterpineol acetate; and ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, methyl carbitol, ethyl carbitol, butyl carbitol, and propylene glycol. Diol ether solvents such as monomethyl ether, dimethyl ethylene glycol, and diethylene glycol; diol ester solvents such as ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and dipropylene glycol monomethyl ether acetate; carbonate solvents such as dimethyl carbonate and propylene carbonate; ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; and nitrogen-containing polar organic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

[0132] Among these solvents, those with good affinity for branched polymers and dispersants are preferably ester solvents such as ethyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, terpineol acetate, and dihydroterpineol acetate, as well as glycol ester solvents such as ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and dipropylene glycol monomethyl ether acetate.

[0133] There are no particular limitations on the amount of organic solvent used, as long as it does not impair the desired effect. The amount of organic solvent used is preferably 60% by volume or more and 97% by volume or less, more preferably 80% by volume or more and 94% by volume or less, relative to the total volume of the paste containing inorganic particles.

[0134] Membranes containing inorganic particles

[0135] Membranes containing inorganic particles comprise branched polymers, inorganic particles, and dispersants. The branched polymers, inorganic particles, and dispersants are as described above regarding pastes containing inorganic particles.

[0136] A membrane containing inorganic particles can be formed by removing at least a portion of the organic solvent from the membrane formed from the paste containing inorganic particles after the paste has been shaped into a membrane.

[0137] There are no particular limitations on the methods for removing organic solvents. For example, organic solvents can be removed by heating or exposure to a reduced pressure atmosphere.

[0138] As a membrane containing inorganic particles, it is preferably a green sheet in which the inorganic particles include ceramic particles and are formed by firing to provide a dielectric layer in a laminated ceramic electronic component.

[0139] The green sheet can be formed by known methods such as die coating or blade coating. The thickness of the green sheet is preferably 4 μm or less, more preferably 3 μm or less.

[0140] As a membrane containing inorganic particles, it is preferable to have inorganic particles including metal particles and to provide a conductive sheet for the internal electrode layer in a stacked ceramic electronic component through firing.

[0141] There are no particular limitations on the method for forming the conductive sheet. Preferably, the conductive sheet is formed by printing a paste containing inorganic particles onto the aforementioned green sheet. For example, gravure printing or screen printing can be used as the printing method.

[0142] The thickness of the conductive sheet is preferably 1.5 μm or less.

[0143] Layered Body

[0144] The laminate comprises at least one layer formed from the aforementioned membrane containing inorganic particles.

[0145] As a preferred laminate, an example is a laminate in which a green sheet having a dielectric layer formed by firing and a conductive sheet having an internal electrode layer formed by firing are laminated. The green sheet is the aforementioned film containing inorganic particles, or the conductive sheet is the aforementioned film containing inorganic particles. This laminate is preferably used for the manufacture of laminated ceramic electronic components.

[0146] After the laminate is fired, it is subjected to various known processing methods for manufacturing laminated ceramic electronic components, thereby obtaining laminated ceramic electronic components.

[0147] Examples of multilayer ceramic electronic components include multilayer ceramic capacitors, inductors, piezoelectric elements, and thermistors.

[0148] Example

[0149] The present invention will be further described in detail below through embodiments, but the present invention is not limited to these embodiments.

[0150] [Example 1]

[0151] Prepare a conductive paste containing Ni particles as inorganic particles.

[0152] In the preparation of the conductive paste, Ni particles with an average SEM diameter of 200 nm and barium titanate particles with a BET diameter of 20 nm were used as inorganic particles.

[0153] As a branched polymer, a resin having a main chain formed of ethyl cellulose and a branch chain formed of polypropylene carbonate, which is an aliphatic polycarbonate, is used.

[0154] As a dispersant, a polymeric dispersant having a carboxyl group as an adsorption functional group, a chain aliphatic hydrocarbon group as a hydrophobic group, and a polyoxyethylene (polyether chain) is used.

[0155] Dihydroterpineol acetate, an ester solvent, is used as an organic solvent.

[0156] (Preparation of conductive paste)

[0157] 40 parts by mass of Ni particles, 4 parts by mass of barium titanate particles, 2 parts by mass of branched polymer, 0.7 parts by mass of dispersant, and 53.3 parts by mass of organic solvent are uniformly mixed. The resulting mixture is then dispersed by roller to obtain a conductive paste.

[0158] (Preparation of dielectric paste)

[0159] 7.2 parts by mass of polypropylene carbonate, an aliphatic polycarbonate, were dissolved in 26 parts by mass of n-butyl acetate and 26 parts by mass of dimethyl carbonate. Polypropylene carbonate has carboxylic acid modified sites in its repeating structure. The proportion of carboxylic acid modified sites is 0.8 mol% of the total structure. To the resulting solution, 40 parts by mass of barium titanate particles (BET equivalent diameter 0.2 μm) as ceramic particles, 0.7 parts by mass of polyethylene glycol as a plasticizer, and 0.1 parts by mass of an antistatic agent were added. Next, the resulting suspension was dispersed in a ball mill for a specified time to obtain a dielectric paste.

[0160] (Preparation of raw slices)

[0161] A dielectric paste is applied to a PET (polyethylene terephthalate) film using a doctor blade method. The coated film is then dried to obtain a green sheet containing ceramic particles. The thickness of the green sheet is adjusted so that the thickness of the dielectric layer after firing is 1.7 μm.

[0162] (Preparation of conductive sheet)

[0163] A conductive paste is screen-printed onto a green sheet. The printed conductive paste is then dried to obtain a conductive sheet. The conductive paste is printed on the green sheet in a pattern that forms a chip-like laminate with a planar dimension of 3.2 mm × 1.6 mm, which is then cut and fired. According to XRF measurements, the thickness of the conductive sheet, which is only composed of metal components, is 0.4 μm. The thickness of the conductive sheet immediately after drying is 0.8 μm.

[0164] (Laminated body manufacturing)

[0165] The conductive sheets are peeled off from the PET film. 200 peeled sheets are stacked and placed into a mold. The sheets are pressed together in the mold to form a laminate. The resulting laminate is then cut to a specified size using a die cutter to obtain a chip-shaped, unburned laminate.

[0166] (Evaluation of the occurrence of structural defects)

[0167] For 100 randomly selected unburned laminates on a chip, the cut surfaces were observed using an optical microscope to confirm the presence of interlayer delamination between the conductive sheet and the green sheet (which are structural defects), as well as intralayer delamination caused by agglomeration failure within the conductive sheet. The number of laminates with observed structural defects was recorded as the occurrence rate of structural defects and is shown in Table 1. Furthermore, based on the number of laminates with observed structural defects, the occurrence of structural defects was evaluated according to the following criteria.

[0168] ◎: The number of stacked bodies with structural defects observed is 0 or 1.

[0169] ○: The number of stacked bodies with structural defects observed is more than 2 and less than 10.

[0170] ×: The number of stacked bodies with structural defects observed is more than 11.

[0171] [Example 2]

[0172] The branched polymer was changed to a resin having a main chain formed of ethyl cellulose and branches formed of polycaprolactone, which is an aliphatic polyester. The same tests as in Example 1 were performed, except as described above. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0173] [Example 3]

[0174] The polyoxyethylene (polyether chain) dispersant was replaced with polycaprolactone (polyester chain), and the same tests as in Example 1 were performed, except as described above. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0175] [Example 4]

[0176] The hydrophilic groups of the dispersant were changed to polypropylene carbonate groups (polycarbonate chains), and the same tests as in Example 1 were performed, except as described above. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0177] [Example 5]

[0178] The branched polymer was changed to a resin having a main chain formed of ethyl cellulose and a branch chain formed of polycaprolactone, which is an aliphatic polyester, and the polyoxyethylene (polyether chain) in the dispersant was changed to polycaprolactone groups (polyester chain). Except as described above, the same tests as in Example 1 were performed. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0179] [Example 6]

[0180] The branched polymer was changed to a resin having a main chain formed of ethyl cellulose and a branch chain formed of polycaprolactone, which is an aliphatic polyester, and the hydrophilic groups of the dispersant were changed to polypropylene carbonate groups (polycarbonate chains). Except as described above, the same tests as in Example 1 were performed. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0181] [Example 7]

[0182] In the preparation of the conductive paste, ceramic particles were not used, and the same tests as in Example 1 were conducted, except as described above. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0183] [Example 8]

[0184] The branched polymer was changed to a resin having a main chain formed of ethyl cellulose and branches formed of polycaprolactone, which is an aliphatic polyester, and ceramic particles were not used in the preparation of the conductive paste. Except as described above, the same tests as in Example 1 were performed. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0185] [Example 9]

[0186] The metal particles were replaced with Cu particles with a SEM diameter of 500 nm, and the same experiments as in Example 1 were conducted, except as described above. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0187] [Example 10]

[0188] The branched polymer was changed to a resin having a main chain formed of ethyl cellulose and branches formed of polycaprolactone, which is an aliphatic polyester, and the metal particles were changed to Cu particles with a SEM diameter of 500 nm. Except as described above, the same tests as in Example 1 were performed. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0189] [Example 11]

[0190] The amount of branched polymer, Ni particles, and ceramic particles used were adjusted, and the volume ratio of the binder resin to the total volume of the binder resin and inorganic particles in the conductive paste, i.e., the binder resin volume ratio, was changed to 17% by volume. Except as described above, the same tests as in Example 1 were conducted. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0191] [Example 12]

[0192] The amount of branched polymer used, as well as the amounts of Ni particles and ceramic particles, were adjusted, and the ratio of the volume of the binder resin to the total volume of the binder resin and inorganic particles in the conductive paste, i.e., the binder resin volume ratio, was changed to 29% by volume. Except as described above, the same tests as in Example 1 were conducted. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0193] [Example 13]

[0194] The branched polymer was changed to a resin having a main chain formed of ethyl cellulose and branches formed of polycaprolactone, which is an aliphatic polyester. The amount of branched polymer used, as well as the amounts of Ni particles and ceramic particles, were adjusted. The volume ratio of the adhesive resin to the total volume of the adhesive resin and inorganic particles in the conductive paste, i.e., the adhesive resin volume percentage, was changed to 17% by volume. Except as described above, the same tests as in Example 1 were performed. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0195] [Example 14]

[0196] The branched polymer was changed to a resin having a main chain formed of ethyl cellulose and branches formed of polycaprolactone, which is an aliphatic polyester. The amount of branched polymer used, as well as the amounts of Ni particles and ceramic particles, were adjusted. The volume ratio of the adhesive resin to the total volume of the adhesive resin and inorganic particles in the conductive paste, i.e., the adhesive resin volume percentage, was changed to 29% by volume. Except as described above, the same tests as in Example 1 were performed. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0197] [Comparative Example 1]

[0198] The branched polymer was replaced with ethyl cellulose, which is a linear polymer, and the same tests as in Example 1 were performed, except as described above. The evaluation results of the structural defects are recorded in Table 1.

[0199] [Comparative Example 2]

[0200] The branched polymer was changed to ethyl cellulose, which is a linear polymer, and the dispersant was changed to a polymeric dispersant that has carboxyl groups as adsorption functional groups and chain aliphatic hydrocarbon groups as hydrophobic groups, but does not have polyoxyethylene (polyether chain). Except as described above, the same tests as in Example 1 were performed. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0201] [Comparative Example 3]

[0202] The dispersant was changed to a polymeric dispersant that has a carboxyl group as an adsorption functional group and a chain-like aliphatic hydrocarbon group as a hydrophobic group, but does not have a polyoxyethylene (polyether chain). Except as described above, the same tests as in Example 1 were performed. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0203] [Comparative Example 4]

[0204] The branched polymer was changed to a resin having a main chain formed of ethyl cellulose and a branch chain formed of polycaprolactone, which is an aliphatic polyester. The dispersant was changed to a polymeric dispersant that, while having carboxyl groups as adsorption functional groups and chain-like aliphatic hydrocarbon groups as hydrophobic groups, did not have polyoxyethylene (polyether chain). Except as described above, the same tests as in Example 1 were performed. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0205] [Comparative Example 5]

[0206] The branched polymer was changed to ethyl cellulose, which is a linear polymer, and the hydrophilic group of the dispersant was changed to polycaprolactone group (polyester chain). Except as described above, the same tests as in Example 1 were performed. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0207] [Comparative Example 6]

[0208] The branched polymer was changed to ethyl cellulose, which is a linear polymer, and the hydrophilic groups of the dispersant were changed to polypropylene carbonate groups (polycarbonate chains). Except as described above, the same tests as in Example 1 were performed. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0209] [Comparative Example 7]

[0210] The branched polymer was replaced with ethyl cellulose, which is a linear polymer, and ceramic particles were not used in the preparation of the conductive paste. Except as described above, the same tests as in Example 1 were performed. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0211] [Comparative Example 8]

[0212] The branched polymer was replaced with ethyl cellulose, which is a linear polymer, and the metal particles were replaced with Cu particles with a SEM diameter of 500 nm. All other than the above, the same tests as in Example 1 were performed. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0213] [Comparative Example 9]

[0214] The branched polymer was changed to ethyl cellulose, which is a linear polymer, and the amount of ethyl cellulose used, as well as the amount of Ni particles and ceramic particles, were adjusted. The volume ratio of the adhesive resin to the total volume of the adhesive resin and inorganic particles in the conductive paste, i.e., the adhesive resin volume percentage, was changed to 17% by volume. Except as described above, the same tests as in Example 1 were conducted. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0215] [Comparative Example 10]

[0216] The branched polymer was changed to ethyl cellulose, which is a linear polymer, and the amount of ethyl cellulose used, as well as the amount of Ni particles and ceramic particles, were adjusted. The volume ratio of the adhesive resin to the total volume of the adhesive resin and inorganic particles in the conductive paste, i.e., the adhesive resin volume percentage, was changed to 29% by volume. Except as described above, the same tests as in Example 1 were conducted. The evaluation results of the occurrence of structural defects are recorded in Table 1.

[0217] The specific functional groups in Table 1 below are the types of functional groups that are equivalent to any one of the polyether chain, polyester chain, and polycarbonate chain.

[0218] The binder resin volume ratio is the ratio of the volume of the binder resin to the total volume of the binder resin and inorganic particles in the conductive paste.

[0219] The abbreviations in the table below are as follows.

[0220] EC: Ethyl cellulose

[0221] PCL: Polycaprolactone (aliphatic polyester)

[0222] PPC: Polypropylene carbonate (aliphatic polycarbonate)

[0223] [Table 1]

[0224]

[0225] As can be seen from the embodiments, when a laminate containing a conductive sheet formed as follows is cut, even if a shear force is applied when the laminate is cut, almost no interlayer delamination as a structural defect occurs. The conductive sheet is formed using a conductive paste that comprises a branched polymer having a main chain formed of a cellulose polymer and a side chain formed of an aliphatic polycarbonate or aliphatic polyester, and a dispersant having a hydrophilic chain such as a polyether chain.

[0226] On the other hand, according to comparative examples, when the adhesive resin contained in the conductive paste contains only a main chain formed by a cellulose polymer or the dispersant does not have a specific hydrophilic chain, interlayer delamination, which is a structural defect, is easily generated when the laminate is cut.

Claims

1. A paste containing inorganic particles, comprising a branched polymer, inorganic particles, a dispersant, and an organic solvent. The branched polymer has a main chain formed by a cellulose-based polymer and branches formed by aliphatic polycarbonate or aliphatic polyester. The branches are selected from straight chains and branched chains. The branch is bonded to only one of the main chains, or the branch is bonded to two or more of the main chains, thus crosslinking the two or more main chains. The dispersant has at least one selected from polyether chains, polyester chains, and polycarbonate chains.

2. The paste containing inorganic particles according to claim 1, wherein, The cellulose-based polymer comprises at least one selected from methylcellulose, ethylcellulose, cellulose acetate butyrate, cellulose acetate propionate, and cellulose acetate.

3. The paste containing inorganic particles according to claim 1 or 2, wherein, The inorganic particles include ceramic particles and / or metal particles.

4. The paste containing inorganic particles according to claim 3, wherein the inorganic particles comprise metal particles, and the metal constituting the metal particles is at least one selected from Ni, Cu, Ag and Au.

5. The paste containing inorganic particles according to claim 3, wherein the ceramic particles are included as the inorganic particles, and the material constituting the ceramic particles comprises at least one selected from Ba, Ti, Sr, Ca and Zr.

6. The paste containing inorganic particles according to claim 1 or 2, wherein, The organic solvent includes ester-based solvents.

7. The paste containing inorganic particles according to claim 1 or 2, wherein, The ratio of the volume of the branched polymer to the total volume of the inorganic particles is 17% to 29% by volume.

8. A membrane containing inorganic particles, comprising a branched polymer, inorganic particles, and a dispersant. The branched polymer has a main chain formed by a cellulose-based polymer and branches formed by aliphatic polycarbonate or aliphatic polyester. The branches are selected from straight chains and branched chains. The branch is bonded to only one of the main chains, or the branch is bonded to two or more of the main chains, thus crosslinking the two or more main chains. The dispersant has at least one selected from polyether chains, polyester chains, and polycarbonate chains.

9. The membrane containing inorganic particles according to claim 8, wherein the inorganic particles comprise ceramic particles and are a green sheet of a dielectric layer in a stacked ceramic electronic component, which is formed by firing.

10. The membrane containing inorganic particles according to claim 8, wherein the inorganic particles include metal particles and are formed by firing to provide a conductive sheet for an internal electrode layer in a stacked ceramic electronic component.

11. A laminate, wherein at least one layer comprises the inorganic particle-containing membrane of claim 8.

12. The laminate according to claim 11, used for manufacturing laminated ceramic electronic components. The laminate includes a green sheet having a dielectric layer formed by firing, and a conductive sheet having an internal electrode layer formed by firing. The green sheet is the inorganic particle-containing membrane as described in claim 9, or The conductive sheet is the inorganic particle-containing membrane as described in claim 10.

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