WO2022168446A1

WO2022168446A1 - Inorganic particle-containing paste, inorganic particle-containing film, and laminate

Info

Publication number: WO2022168446A1
Application number: PCT/JP2021/045897
Authority: WO
Inventors: 準塩田; 友樹吾郷; 信之木南; 明大鶴
Original assignee: 株式会社村田製作所
Priority date: 2021-02-02
Filing date: 2021-12-13
Publication date: 2022-08-11
Also published as: CN116745872A; KR20230128323A; JPWO2022168446A1

Abstract

Provided are: an inorganic particle-containing paste that yields an inorganic particle-containing film that, when laminated, resists the generation, due to the action of, e.g., shear force, of interlayer separation from another layer; an inorganic particle-containing film that can be formed using the inorganic particle-containing paste; and a laminate that contains the inorganic particle-containing film.　The combination of a branched polymer and a dispersing agent is used in an inorganic particle-containing paste comprising a binder resin, inorganic particles, and organic solvent, wherein the branched polymer has a molecular chain that has a main chain comprising a cellulosic polymer and a branch chain comprising an aliphatic polycarbonate or an aliphatic polyester, and the dispersing agent has at least one selected from the group consisting of polyether chains, polyester chains, and polycarbonate chains.

Description

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

The present invention relates to an inorganic particle-containing paste, an inorganic particle-containing film that can be formed using the inorganic particle-containing paste, and a laminate containing the inorganic particle-containing film.

Films containing various inorganic particles are used in various applications. As a method for forming such a film, a method using a paste containing inorganic particles is known. A film containing inorganic particles can be formed by forming a film from a paste containing inorganic particles by a method such as coating or printing, and curing or drying the formed film.

Laminates used to manufacture laminated ceramic electronic components such as laminated ceramic capacitors are known as typical applications of inorganic particle-containing films. In such a laminate, green sheets containing ceramic powder and precursor films of internal electrode layers containing metal particles are usually laminated.

For example, as a conductive paste for forming a conductive sheet that provides internal electrode layers by firing, a conductive paste containing metal particles and ethyl cellulose as a binder resin has been proposed (see Patent Document 1. ). Ethyl cellulose is excellent in solubility in organic solvents and decomposability during firing, and provides a conductive paste with good printing properties.

JP 2018-168238 A

When manufacturing a multilayer ceramic electronic component, a laminate containing a green sheet and a conductive sheet that provides an internal electrode layer by being fired is cut into a predetermined size by a method such as pressure cutting and divided. In some cases, the divided laminate is fired. However, when using a laminate containing a conductive sheet formed using a conductive paste containing ethyl cellulose as a binder resin, when cutting the laminate in a direction perpendicular or substantially perpendicular to the plane direction, There is a problem that delamination easily occurs due to delamination or cohesive failure due to the action of shear force or the like.

The present invention has been made in view of the above problems, and when cutting a laminate obtained by laminating an inorganic particle-containing film into small pieces, the other layers due to the action of shear force etc. An inorganic particle-containing paste that provides an inorganic particle-containing film that is unlikely to cause intra-layer peeling due to delamination or cohesive failure, an inorganic particle-containing film that can be formed using the inorganic particle-containing paste, and the above inorganic particle-containing film. It is an object of the present invention to provide a laminate comprising:

The present inventors found that in an inorganic particle-containing paste containing a binder resin, inorganic particles, and an organic solvent, a molecule having a main chain made of a cellulose polymer and a branch chain made of an aliphatic polycarbonate or an aliphatic polyester We have found that the above problems can be solved by using a combination of a branched polymer having a chain and a dispersant having at least one selected from the group consisting of a polyether chain, a polyester chain, and a polycarbonate chain. I have perfected my invention. More specifically, the present invention provides the following (1) to (3).

(1) comprising a branched polymer, inorganic particles, a dispersant, and an organic solvent;
The molecular chain of the branched polymer has a main chain made of a cellulose polymer and a branch chain made of an aliphatic polycarbonate or an aliphatic polyester,
The branched chain may be linear or branched,
branch chains may be attached to two or more of said main chains to bridge two or more of said main chains;
An inorganic particle-containing paste, wherein the dispersant has at least one selected from the group consisting of polyether chains, polyester chains, and polycarbonate chains.

(2) comprising a branched polymer, inorganic particles, and a dispersant;
The molecular chain of the branched polymer has a main chain made of a cellulose polymer and a branch chain made of an aliphatic polycarbonate or an aliphatic polyester,
The branched chain may be linear or branched,
branch chains may be attached to two or more of said main chains to bridge two or more of said main chains;
An inorganic particle-containing film, wherein the dispersant has at least one selected from the group consisting of polyether chains, polyester chains, and polycarbonate chains.

(3) A laminate in which at least one layer comprises the inorganic particle-containing film according to (2).

According to the present invention, an inorganic particle-containing paste that provides an inorganic particle-containing film that is unlikely to cause delamination from other layers due to the action of shear force or the like when laminated, and a paste that is formed using the inorganic particle-containing paste. It is possible to provide the obtained inorganic particle-containing film and the laminate containing the inorganic particle-containing film described above.

≪Paste containing inorganic particles≫
The inorganic particle-containing paste contains a branched polymer, inorganic particles, a dispersant, and an organic solvent.
A molecular chain of a branched polymer has a main chain and a branch chain. The backbone consists of a cellulosic polymer. The branches consist of aliphatic polycarbonates or aliphatic polyesters. Branches may be straight or branched. A branch may be attached to two or more backbones to bridge two or more backbones.
The dispersant has at least one selected from the group consisting of polyether chains, polyester chains and polycarbonate chains.

In the inorganic particle-containing paste containing inorganic particles and an organic solvent, by using a combination of the branched polymer having the specific structure and the dispersant having a chain having a specific structure, the inorganic particle-containing paste can contain inorganic particles Contains inorganic particles that do not easily cause delamination from other layers due to the action of shear force, etc., or intra-layer delamination due to cohesive failure when the laminate obtained by laminating the containing film is cut into small pieces. Give a membrane.

The essential or optional components that the inorganic particle-containing paste may contain will be described below.

<Branched polymer>
A branched polymer has a main chain and branch chains in its molecular chain. The backbone consists of a cellulosic polymer. The branches consist of aliphatic polycarbonates or aliphatic polyesters.
Branches may be straight or branched. A branch may be attached to two or more backbones to bridge two or more backbones.
By using the above-mentioned branched polymer in combination with a dispersant described later, when cutting the laminate obtained by laminating the inorganic particle-containing film into small pieces, the effect of shear force and the like can be reduced. It is possible to obtain an inorganic particle-containing paste that gives an inorganic particle-containing film that is less likely to cause delamination with the layer of , or intra-layer delamination due to cohesive failure.

In the branched polymer, the graft ratio, which is the ratio of the mass of the branch chains to the mass of the main chain, is not particularly limited as long as the desired effects are not impaired. When a laminate obtained by laminating inorganic particle-containing films formed using an inorganic particle-containing paste is cut into small pieces, delamination due to external force such as shear force or intra-layer delamination due to cohesive failure The graft rate 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, from the viewpoint of easily suppressing the occurrence of .
The graft rate can be determined by nuclear magnetic resonance spectroscopy (NMR analysis).

The mass average molecular weight of the branched polymer is not particularly limited. The weight average molecular weight of the branched polymer is, for example, preferably 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 such a range, mechanical properties such as strength, elongation and toughness and moldability of the branched polymer are good.

The method for producing the main chain, branched chain, and branched polymer will be described below.

(main chain)
Branched polymers have a backbone consisting of a cellulosic polymer. The type of cellulosic polymer is not particularly limited as long as the main chain of the cellulosic polymer has functional groups to which branch chains can be bonded.
Preferred specific examples of cellulosic polymers include cellulose; alkylcelluloses such as methylcellulose, ethylcellulose, n-propylcellulose, isopropylcellulose, n-butylcellulose, tert-butylcellulose, and n-hexylcellulose; hydroxymethylcellulose, hydroxyethylcellulose. hydroxyalkylcelluloses such as, hydroxypropylcellulose, and hydroxybutylcellulose; cellulose esters such as cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate; carboxymethylcellulose, carboxyethylcellulose, and carboxypropyl carboxyalkyl cellulose such as cellulose; cellulose derivatives such as nitrocellulose, aldehyde cellulose, dialdehyde cellulose, and sulfonated cellulose;
A branched polymer may comprise two or more branched polymer molecules having different types of cellulosic polymer backbones.

Cellulose-based polymers are alkyl celluloses, alkyl celluloses, At least one selected from the group consisting of hydroxyalkyl cellulose and cellulose ester is preferred.
Among the above preferred cellulosic polymers, at least one selected from the group consisting of methyl cellulose, ethyl cellulose, cellulose acetate butyrate, cellulose acetate propionate, and cellulose acetate is preferred.

The mass average molecular weight of the cellulose-based polymer is not particularly limited. The mass average molecular weight of the cellulose-based polymer is, for example, 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-based polymer is preferably 1,000,000 or less, more preferably 750,000 or less, even more preferably 500,000 or less.
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 more preferably 10,000 or more and 750,000 or less.

The degree of substitution of the cellulosic polymer is not particularly limited as long as the desired effects are not impaired. The degree of substitution of the cellulosic polymer is preferably 2 or more and 3 or less, typically 2.5.
The degree of substitution of a cellulosic polymer is the total number of hydroxyl groups substituted by groups other than branched chains among all hydroxyl groups in the constituent units of the cellulosic polymer.

(branch chain)
Branched polymers have branches attached to a backbone composed of a cellulosic polymer. The branches consist of aliphatic polycarbonates or aliphatic polyesters. Branches may be straight or branched.
Typically, branches are attached to only one main chain. A branch may be attached to two or more backbones to bridge two or more backbones.

The aliphatic polycarbonate or aliphatic polyester that constitutes the branched chain is not particularly limited, as long as the branched chain can be formed in a state of being bound to the main chain or can be bound to the main chain.
Typical examples of branched chain aliphatic polycarbonates or aliphatic polyesters are given below in the description of methods for producing branched polymers.

(Method for producing branched polymer)
The method for producing the branched polymer is not particularly limited. A graft polymerization method is typically employed. The graft polymerization method can be appropriately selected from various known methods depending on the type of branched chain.

As the graft polymerization method, for example, a ring-opening polymerization method can be adopted. By subjecting a cyclic carbonate compound or a cyclic ester compound such as a lactone to ring-opening polymerization in the presence of a cellulose-based polymer, an aliphatic polycarbonate or an aliphatic polyester is formed as a graft chain on the molecular chain of the cellulose-based polymer. Generate.

For example, propylene carbonate as a cyclic compound gives a branched chain made of polypropylene carbonate. Butylene carbonate as a cyclic compound gives branches consisting of polybutylene carbonate. Cyclohexene carbonate as a cyclic compound gives a branched chain consisting of polycyclohexene carbonate. Trimethylene carbonate as a cyclic compound gives branches consisting of polytrimethylene carbonate. 2,2-dimethyltrimethylene carbonate as a cyclic compound gives branches consisting of poly(2,2-dimethyltrimethylene carbonate).

ε-caprolactone as a cyclic compound gives a branched chain composed of polycaprolactone, which is an aliphatic polyester. L-lactide as a cyclic compound gives L-form polylactic acid, which is an aliphatic polyester, as a branched chain. D-lactide as a cyclic compound gives D-form polylactic acid, which is an aliphatic polyester, as a branched chain. Meso-lactide as a cyclic compound gives a syndiotactic polylactic acid, which is an aliphatic polyester, as a branched chain. β-Propiolactone as a cyclic compound gives D-form poly(3-hydroxypropionic acid), which is an aliphatic polyester, as branched chains. β-butyrolactone as a cyclic compound gives the aliphatic polyester poly(3-hydroxybutyric acid) as branched chains. γ-Butyrolactone as the cyclic compound gives the aliphatic polyester poly(4-hydroxybutyric acid) as branched chains. δ-valerolactone as a cyclic compound gives the aliphatic polyester poly(3-hydroxyvaleric acid) as branched chains. P-dioxanone as a cyclic compound gives poly(p-dioxanone), an aliphatic polyester, as branched chains.

Ring-opening polymerization is typically 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; sodium hydroxide, potassium hydroxide, triethylaluminum, aluminum triisopropoxide, n-butyllithium, titanium tetraisopropoxy metal-containing catalysts such as sodium chloride, titanium tetrachloride, zirconium tetraisopropoxide, tin tetrachloride, sodium stannate, tin octoate, and diethylzinc dibutyltin dilaurate; pyridine, 4-N,N-dimethylaminopyridine, 1,5 ,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBT) and other basic organic compounds; , acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, diphenylphosphoric acid, and phenol; 1,3-bis(2-propyl)-4,5-dimethylimidazol-2-ylidene; , and N-heterocyclic carbenes such as 1,3-diisopropylimidazol-2-ylidene.
A catalyst may be used individually by 1 type, or may be used in combination of 2 or more type.

When carrying out ring-opening polymerization using a cyclic carbonate, it is also preferable to use a co-catalyst together with the catalyst. Specific examples of promoters include N-cyclohexyl-N'-phenylthiourea, N,N'-bis[3,5-bis(trifluoromethyl)phenyl]thiourea, N-[3,5-bis(tri fluoromethyl)phenyl]-N'-cyclohexylthiourea, (-)-sparteine and the like.

The amount of the catalyst that can be used in the ring-opening polymerization is appropriately determined in consideration of the amount of the catalyst used in conventionally known ring-opening polymerization reactions. Typically, the amount of the catalyst used is preferably 0.001 mol or more, more preferably 0.005 mol or more, per 1 mol of the cyclic compound. The amount of the catalyst used is preferably 0.2 mol or less, more preferably 0.1 mol or less, per 1 mol of the cyclic compound.
More specifically, the amount of the catalyst used is preferably 0.001 mol or more and 0.2 mol or less, more preferably 0.005 mol or more and 0.1 mol or less, relative to 1 mol of the cyclic compound.
The amount of promoter used is the same as the amount of catalyst used.

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 inhibit the ring-opening polymerization reaction.
Suitable specific 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 dichloroethane, 1,2-dichloroethane, chlorobenzene, and bromobenzene; ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetrahydrofuran, 2-methyltetrahydrofuran, 1 Ether solvents such as ,4-dioxane, 1,3-dioxolane, and anisole; Ester solvents such as ethyl acetate, n-propyl acetate, and isopropyl acetate; N,N-dimethylformamide, N,N-dimethylacetamide, and amide solvents such as N-methyl-2-pyrrolidone.

The amount of solvent used is not particularly limited as long as the ring-opening polymerization reaction proceeds well. The amount of the solvent used is preferably 100 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the cyclic compound, for example.

Typically, a cellulosic resin, a cyclic compound, a catalyst, and optionally a cocatalyst and/or solvent are charged into a reaction vessel, and the mixture in the reaction vessel is stirred to carry out ring-opening polymerization. is done.

A preferred reaction temperature for ring-opening polymerization varies depending on the cyclic compound, the type of catalyst, the amount of catalyst used, and the like. 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. From the viewpoint of achieving both good yield and suppression of side reactions, the reaction temperature of the ring-opening polymerization is preferably 250° C. or lower, more preferably 200° C. or lower, and even more preferably 150° C. or lower.
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, even more preferably 0° C. or higher and 150° C. or lower.

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

The amount of the cyclic compound used in the ring-opening polymerization is appropriately determined in consideration of the above-mentioned graft ratio.

Another preferred method for producing a branched polymer is a method of copolymerizing a cyclic ether and carbon dioxide in the presence of a cellulosic resin. Such a copolymerization reaction produces branched chains of aliphatic polycarbonate. The cellulosic resin is as described above.

As cyclic ethers, the corresponding cyclic ethers of the branched aliphatic polycarbonates are suitably selected.
Preferred examples of cyclic ethers include ethylene oxide, propylene oxide, trimethylene oxide (oxetane), 3,3-dimethyltrimethylene oxide (3,3-dimethyloxetane), 1,2-butylene oxide and 2,3-butylene oxide. , isobutylene oxide, 1-pentene oxide, 2-pentene oxide, 1-hexene oxide, 1-octene oxide, 1-dodecene oxide, cyclopentene oxide, cyclohexene oxide, styrene oxide, vinylcyclohexane oxide, 3-phenylpropylene oxide, 3 , 3,3-trifluoropropylene oxide, 3-naphthylpropylene oxide, 2-phenoxypropylene oxide, 3-naphthoxypropylene oxide, butadiene monoxide, 3-vinyloxypropylene oxide, and 3-trimethylsilyloxypropylene oxide. .

Among the above cyclic ethers, there are branched polymers that have excellent polymerization reactivity and that easily suppress the occurrence of delamination due to external force when inorganic particle-containing films are laminated using inorganic particle-containing pastes. Ethylene oxide, propylene oxide, trimethylene oxide, and 1,2-butylene oxide are preferred, and ethylene oxide, propylene oxide, and trimethylene oxide are more preferred, as they are available.

An example of an aliphatic polycarbonate produced by copolymerizing a cyclic ether and carbon dioxide is shown below. Ethylene oxide gives polyethylene carbonate. Propylene oxide gives polypropylene carbonate. Trimethylene oxide gives polytrimethylene carbonate.

　The copolymerization of cyclic ether and carbon dioxide is carried out in the presence of a metal catalyst. Preferred examples of metal catalysts include zinc-based catalysts, aluminum-based catalysts, chromium-based catalysts, cobalt-based catalysts, and the like. Among these, zinc-based catalysts and cobalt-based catalysts are preferred because of their high polymerization activity.

Preferred specific examples of zinc-based catalysts include diethylzinc-water-based catalysts, diethylzinc-pyrogallol-based catalysts, bis((2,6-diphenyl)phenoxy)zinc, N-(2,6-diisopropylphenyl)- 3,5-di-tert-butyl salicylaldoiminato zinc, 2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-pentenoic acid acetate, adipine zinc acid, zinc glutarate, and the like.

Preferred specific examples of cobalt-based catalysts include cobalt acetate-acetic acid-based catalysts, N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt acetate, N, N'-bis-(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt pentafluorobenzoate, N,N'-bis-(3,5-di-tert-butylsalicylidene) den)-1,2-cyclohexanediaminocobalt chloride, N,N'-bis-(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt nitrate, N,N'-bis -(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminocobalt 2,4-dinitrophenoxide, tetraphenylporphyrin cobalt chloride, tetraphenylporphyrin cobalt acetate, N,N'-bis[2 -(ethoxycarbonyl)-3-oxobutylidene]-1,2-cyclohexanediaminatocobalt chloride and N,N'-bis[2-(ethoxycarbonyl)-3-oxobutylidene]-1,2-cyclohexanediaminatocobalt penta Fluorobenzoates are mentioned.

A cobalt-based catalyst is preferably used together with a co-catalyst. Specific examples of promoters include pyridine, 4-N,N-dimethylaminopyridine, N-methylimidazole, tetrabutylammonium chloride, tetrabutylammonium acetate, triphenylphosphine, bis(triphenylphosphoranylidene)ammonium chloride, and bis(triphenylphosphoranylidene)ammonium acetate.

The amount of the catalyst that can be used in the copolymerization of the cyclic ether and carbon dioxide is appropriately determined in consideration of the amounts of conventionally known catalysts used for such copolymerization reactions. Typically, the amount of the catalyst used is preferably 0.001 mol or more, more preferably 0.005 mol or more, per 1 mol of the cyclic ether. The amount of the catalyst used is preferably 0.2 mol or less, more preferably 0.1 mol or less, per 1 mol of the cyclic ether.
More specifically, the amount of the catalyst to be used is preferably 0.001 mol or more and 0.2 mol or less, more preferably 0.005 mol or more and 0.1 mol or less, relative to 1 mol of the cyclic ether.
The amount of promoter used is the same as the amount of catalyst used.

Copolymerization of the cyclic ether and 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 inhibit the copolymerization reaction.
Suitable specific 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 dichloroethane, 1,2-dichloroethane, chlorobenzene, and bromobenzene; ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetrahydrofuran, 2-methyltetrahydrofuran, 1 Ether solvents such as ,4-dioxane, 1,3-dioxolane, and anisole; Ester solvents such as ethyl acetate, n-propyl acetate, and isopropyl acetate; N,N-dimethylformamide, N,N-dimethylacetamide, and amide solvents such as N-methyl-2-pyrrolidone.

The amount of solvent used is not particularly limited as long as the copolymerization reaction proceeds well. The amount of the solvent used is preferably 100 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the cyclic ether, for example.

Typically, a cellulose resin, a cyclic ether, a catalyst, and optionally a co-catalyst and/or solvent are charged into a reaction vessel, and then carbon dioxide is injected into the reaction vessel, followed by Copolymerization is carried out by stirring the mixture inside.

The amount of the cyclic ether and carbon dioxide to be used in the copolymerization is appropriately determined in consideration of the above-mentioned graft ratio.
The pressure of carbon dioxide in the reaction vessel during copolymerization is preferably 0.1 MPa or more, more preferably 0.2 MPa or more, more preferably 0.5 MPa as a gauge pressure at the reaction temperature, from the viewpoint of good progress of the reaction. The above is more preferable. The pressure of carbon dioxide in the reaction vessel is preferably 20 MPa or less, more preferably 10 MPa or less, and 5 MPa or less from the viewpoint of work safety and that there is no need to use an expensive pressure-resistant container with high pressure resistance. It can be.
More specifically, the gauge 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.
The copolymerization reaction may be carried out under supercritical conditions of carbon dioxide.

A preferred reaction temperature for copolymerization varies depending on the type of cyclic ether, the type of catalyst, the amount of catalyst used, and the like. Typically, the reaction temperature for copolymerization is preferably 0° C. or higher, more preferably 20° C. or higher, and even more preferably 30° C. or higher. From the viewpoint of achieving both good yield and suppression of side reactions, the reaction temperature for copolymerization is preferably 100° C. or lower, more preferably 80° C. or lower, and even more preferably 60° C. or lower.
In view of the above, 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.

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

When the branch chain is made of an aliphatic polyester obtained by polycondensation of an aliphatic dicarboxylic acid and a glycol such as polyethylene succinate, polyethylene adipate, polybutylene succinate, polybutylene adipate, etc., in the presence of a cellulose resin, the fatty acid A branched polymer can also be produced by copolycondensation of an aliphatic dicarboxylic acid and glycols according to the structure of the family polyester according to a conventional method.

The amount of the branched polymer used in the inorganic particle-containing paste is not particularly limited as long as the desired effect is not impaired.
For example, the ratio of the volume of the branched polymer to the sum of the volume of the branched polymer and the volume of the inorganic particles is preferably 17% by volume or more and 29% by volume or less, and is 19% by volume or more and 27% by volume or less. is more preferred.

<Inorganic particles>
The inorganic particle-containing paste contains inorganic particles. As the inorganic particles, inorganic particles conventionally added to various resin compositions can be used without particular limitation.
Ceramic particles and/or metal particles are typically preferred as inorganic particles.

A suitable example of the inorganic particle-containing film formed using the inorganic particle-containing paste is a conductive sheet containing metal particles and providing an internal electrode layer, which constitutes a laminate useful as a precursor of a laminated ceramic electronic component. and green sheets containing ceramic particles.

Ceramic particles are used as inorganic particles when inorganic particle-containing pastes are used to form green sheets that provide dielectric layers in multilayer ceramic electronic components.
When forming an electrode sheet that provides an internal electrode layer in a multilayer ceramic electronic component using a paste containing inorganic particles, in terms of affinity between the green sheet and the electrode sheet and adhesion between the dielectric layer and the internal electrode layer, The inorganic particles may comprise a combination of metal particles and ceramic particles.

The constituent material of the ceramic particles preferably contains at least one selected from the group consisting of Ba, Ti, Sr, Ca and Zr.
Preferred specific examples of ceramic particles include barium titanate particles, calcium titanate particles, strontium titanate particles, lead zirconate titanate particles, and the like.
As the ceramic particles, one type may be used alone, or two or more types may be used in combination. For example, ceramic particles containing barium titanate particles as a main component and a component containing Ca, Zr, or Sr as an auxiliary component may be used.

The particle size of the ceramic particles is not particularly limited as long as the desired effect is not impaired. The average particle size of the ceramic particles is preferably 3 nm or more and 500 nm or less as an average particle size according to the BET conversion method.

When the inorganic particle-containing paste is used 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.
At least one selected from the group consisting of Ni, Cu, Ag, and Au is preferable as the metal constituting the metal particles.
The average particle size of the metal particles is not particularly limited as long as the desired effects are not impaired. The average particle diameter of the metal particles is preferably 3000 nm or less, more preferably 30 nm or more and 1000 nm or less as an SEM diameter.
The metal particles may contain two or more kinds of metal particles. The metal particles may be particles of an alloy containing two or more metals.

When the inorganic particles include a combination of ceramic particles and metal particles, the mass of the ceramic particles is preferably 4% by mass or more and 25% by mass or less with respect to the mass of the metal particles.

<Dispersant>
The inorganic particle-containing paste contains a dispersant. The dispersant has at least one selected from the group consisting of polyether chains, polyester chains and polycarbonate chains.
Having a polyether chain, a polyester chain, or a polycarbonate chain makes the dispersant more compatible with branched polymers having branches made of aliphatic polycarbonates or aliphatic polyesters.

Polyester chains and polycarbonate chains include polyester chains and polycarbonate chains described as branches of branched polymers.
A polyoxyalkylene chain is preferred as the polyether chain. Preferred examples of polyoxyalkylene chains include polyoxyethylene chains and polyoxypropylene chains.

The dispersant preferably has a hydrophobic group in terms of the dispersing effect. Preferred examples of the hydrophobic group include hydrocarbon groups and fluorinated hydrocarbon groups, with aliphatic hydrocarbon groups and aliphatic fluorinated hydrocarbon groups being more preferred.

The dispersant preferably has an adsorptive group such as a carboxyl group, an amino group, a phosphoric acid group, or a sulfonic acid group that can bond to the surface of the inorganic particles in terms of the dispersing effect.

The molecular weight of the dispersant is not particularly limited as long as the desired effects are not impaired. The dispersant may be a so-called low-molecular-weight compound or a polymer-type dispersant. A polymer-type dispersant is preferable as the dispersant in terms of ease of molecular design to give the dispersant the above-described various functional groups.
Polymer-type dispersants include, for example, (meth)acrylic monomers having hydrophobic chains such as hydrocarbon chains, and (meth)acrylic monomers having hydrophilic chains such as polyether chains, polyester chains, and polycarbonate chains. A (meth)acrylic resin having a comb structure copolymerized with a monomer can be preferably used. Comb-structured (meth)acrylic resins in which the above hydrophobic chains and hydrophilic chains are introduced as side chains into known (meth)acrylic resins are also preferably used as polymer-type dispersants.

The amount of the dispersant to be used is preferably 0.5 mg/m ² to 5 mg/m ² , more preferably 1.0 mg/m ² to 2.5 mg/m ² with respect to the surface area of the particles to be dispersed.

<Other ingredients>
The inorganic particle-containing paste may contain components other than the above components as long as the desired effects are not impaired.
Other components include, for example, at least one additive selected from the group consisting of plasticizers and antistatic agents.
The amount of other ingredients to be used is not particularly limited as long as the desired effects are not impaired. The amount of other components to be used is appropriately determined in consideration of the amounts that can be normally used according to the types of the above additives.

<Organic solvent>
The inorganic particle-containing paste contains an organic solvent. Preferable examples of organic solvents include alkanols such as isopropanol; hydrocarbon-based solvents such as toluene, xylene, and isophorone; terpineol-based solvents such as terpineol and dihydroterpineol; Ester solvents such as pentyl, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, terpineol acetate, and dihydroterpineol acetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, methyl carbitol, Glycol ether solvents such as ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate Glycol ester solvents such as dimethyl carbonate and propylene carbonate; ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl- nitrogen-containing polar organic solvents such as 2-pyrrolidone;

Among these solvents, ethyl acetate, n-butyl acetate, n-pentyl acetate, n-hexyl acetate, n-heptyl acetate, and n-acetate have good affinity for branched polymers and dispersants. Ester solvents such as octyl, terpineol acetate, and dihydroterpineol acetate, and 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 are preferred.

The amount of organic solvent used is not particularly limited as long as the desired effect is not impaired. The amount of the 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 inorganic particle-containing paste.

<<Inorganic particle-containing film>>
The inorganic particle-containing film contains a branched polymer, inorganic particles, and a dispersant. The branched polymer, inorganic particles, and dispersant are all the same as those described above for the inorganic particle-containing paste.
The inorganic particle-containing film can be formed by forming the inorganic particle-containing paste into a film, and then removing at least part of the organic solvent from the inorganic particle-containing paste film.
A method for removing the organic solvent is not particularly limited. For example, the organic solvent is removed by a method such as heating or exposure to a reduced pressure atmosphere.

The inorganic particle-containing film is preferably, for example, a green sheet in which inorganic particles contain ceramic particles and which, when fired, provides a dielectric layer in a multilayer ceramic electronic component.
Such a green sheet can be formed, for example, by a known method such as a die coater sheet method or a doctor blade method. The thickness of the green sheet is preferably 4 μm or less, more preferably 3 μm or less.

As the inorganic particle-containing film, it is also preferable to use a conductive sheet containing inorganic particles containing metal particles and providing an internal electrode layer in a multilayer ceramic electronic component by firing.
The method of forming the conductive sheet is not particularly limited. Preferably, the conductive sheet is formed by printing an inorganic particle-containing paste on the above green sheet. As a printing method, for example, a gravure printing method, a screen printing method, or the like can be applied.
The film thickness of the conductive sheet is preferably 1.5 μm or less, for example.

≪Laminate≫
The laminate includes at least one layer made of the inorganic particle-containing film described above.
As a preferable laminate, a green sheet that provides a dielectric layer by firing and a conductive sheet that provides an internal electrode layer by firing are stacked,
Such laminates, in which the green sheet is the inorganic particle-containing film described above or the conductive sheet is the inorganic particle-containing film described above, are suitably used in the production of multilayer ceramic electronic components.
After firing the laminate, the fired laminate is subjected to various known processes for manufacturing a multilayer ceramic electronic component, thereby obtaining a multilayer ceramic electronic component.
Examples of laminated ceramic electronic components include laminated ceramic capacitors, inductors, piezoelectric elements, and thermistors.

Although the present invention will be described in more detail below with reference to examples, the present invention is not limited to these examples.

[Example 1]
A conductive paste containing Ni particles as inorganic particles was produced.
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 for the preparation of the conductive paste.
As the branched polymer, a resin having a main chain made of ethyl cellulose and a branch chain made of polypropylene carbonate, which is an aliphatic polycarbonate, was used.
As the dispersant, a polymer dispersant having a carboxy group as an adsorptive functional group, a chain aliphatic hydrocarbon group as a hydrophobic group, and a polyoxyethylene group (polyether chain) was used.
Dihydroterpineol acetate, which is an ester solvent, was used as the organic solvent.

(Conductive paste preparation)
40 parts by mass of Ni particles, 4 parts by mass of barium titanate particles, 2 parts by mass of a branched polymer, 0.7 parts by mass of a dispersant, and 53.3 parts by mass of an organic solvent were uniformly mixed. The resulting mixture was roll-dispersed to obtain a conductive paste.

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

(Green sheet preparation)
A dielectric paste was applied onto a PET (polyethylene terephthalate) film by a doctor blade method. After that, the coating film was dried to obtain a green sheet containing ceramic particles. The thickness of the green sheet was adjusted so that the thickness of the dielectric layer after firing was 1.7 μm.

(Conductive sheet preparation)
A conductive paste was screen-printed on the green sheet. The printed conductive paste was dried to obtain a conductive sheet. The conductive paste was printed on the green sheet so as to form a pattern in which the planar dimension of the chip-shaped laminate cut and fired was 3.2 mm×1.6 mm. The thickness of the conductive sheet as the thickness of the metal component alone was 0.4 μm by XRF measurement. The thickness of the conductive sheet immediately after drying was 0.8 μm.

(Laminate manufacturing)
The green sheet provided with the conductive sheet was peeled off from the PET film. 200 peeled sheets were laminated, and the 200 laminated sheets were placed in a mold. The sheets in the mold were pressed and crimped to obtain a laminate. The obtained laminate was cut into a predetermined size by press cutting to obtain a chip-shaped unfired laminate.

(Evaluation of Occurrence of Structural Defects)
For each of 100 unfired laminates on a randomly selected chip, the cut surface was observed with an optical microscope, and delamination between the conductive sheet and the green sheet as structural defects, and cohesion inside the conductive sheet The presence or absence of intralayer peeling due to destruction was confirmed. The number of laminates in which structural defects were observed is shown in Table 1 as the rate of occurrence of structural defects. Based on the number of laminates in which structural defects were observed, occurrence of structural defects was evaluated according to the following criteria.
A: The number of laminates in which structural defects were observed was 0 or 1.
○: The number of laminates in which structural defects were observed is 2 or more and 10 or less.
x: The number of laminates in which structural defects were observed is 11 or more.

[Example 2]
The same test as in Example 1 was performed, except that the branched polymer was changed to a resin having a main chain made of ethyl cellulose and branch chains made of polycaprolactone, which is an aliphatic polyester. Table 1 shows the evaluation results of the occurrence of structural defects.

[Example 3]
The same test as in Example 1 was performed, except that the polyoxyethylene group (polyether chain) of the dispersant was changed to a polycaprolactone group (polyester chain). Table 1 shows the evaluation results of the occurrence of structural defects.

[Example 4]
The same test as in Example 1 was conducted, except that the hydrophilic group of the dispersant was changed to a polypropylene carbonate group (polycarbonate chain). Table 1 shows the evaluation results of the occurrence of structural defects.

[Example 5]
The branched polymer is changed to a resin having a main chain made of ethyl cellulose and a branch chain made of polycaprolactone, which is an aliphatic polyester, and the polyoxyethylene group (polyether chain) of the dispersant is replaced with a polycaprolactone group ( The same test as in Example 1 was performed, except that the polyester chain was changed. Table 1 shows the evaluation results of the occurrence of structural defects.

[Example 6]
A branched polymer is changed to a resin having a main chain made of ethyl cellulose and a branch chain made of polycaprolactone, which is an aliphatic polyester, and a hydrophilic group possessed by a dispersant is changed to a polypropylene carbonate group (polycarbonate chain). The same test as in Example 1 was performed except for the above. Table 1 shows the evaluation results of the occurrence of structural defects.

[Example 7]
The same test as in Example 1 was performed, except that ceramic particles were not used in the preparation of the conductive paste. Table 1 shows the evaluation results of the occurrence of structural defects.

[Example 8]
Except for changing the branched polymer to a resin having a main chain made of ethyl cellulose and branch chains made of polycaprolactone, an aliphatic polyester, and not using ceramic particles in the preparation of the conductive paste, A test similar to that of Example 1 was carried out. Table 1 shows the evaluation results of the occurrence of structural defects.

[Example 9]
The same test as in Example 1 was performed except that the metal particles were changed to Cu particles having an SEM diameter of 500 nm. Table 1 shows the evaluation results of the occurrence of structural defects.

[Example 10]
Except for changing the branched polymer to a resin having a main chain made of ethyl cellulose and a branch chain made of polycaprolactone, which is an aliphatic polyester, and changing the metal particles to Cu particles having an SEM diameter of 500 nm, A test similar to that of Example 1 was carried out. Table 1 shows the evaluation results of the occurrence of structural defects.

[Example 11]
By adjusting the amount of branched polymer and the amount of Ni particles and ceramic particles used, the binder is the ratio of the volume of the binder resin to the sum of the volume of the binder resin and the volume of the inorganic particles in the conductive paste. The same test as in Example 1 was conducted except that the resin volume ratio was changed to 17% by volume. Table 1 shows the evaluation results of the occurrence of structural defects.

[Example 12]
By adjusting the amount of branched polymer and the amount of Ni particles and ceramic particles used, the binder is the ratio of the volume of the binder resin to the sum of the volume of the binder resin and the volume of the inorganic particles in the conductive paste. The same test as in Example 1 was performed, except that the resin volume ratio was changed to 29% by volume. Table 1 shows the evaluation results of the occurrence of structural defects.

[Example 13]
The branched polymer is changed to a resin having a main chain made of ethyl cellulose and a branch chain made of polycaprolactone which is an aliphatic polyester, the amount of the branched polymer used, and the amount of Ni particles and ceramic particles used are changed. By adjusting, the binder resin volume ratio, which is the ratio of the volume of the binder resin to the total of the volume of the binder resin in the conductive paste and the volume of the inorganic particles, is changed to 17% by volume. The same test as in 1 was performed. Table 1 shows the evaluation results of the occurrence of structural defects.

[Example 14]
The branched polymer is changed to a resin having a main chain made of ethyl cellulose and a branch chain made of polycaprolactone which is an aliphatic polyester, the amount of the branched polymer used, and the amount of Ni particles and ceramic particles used are changed. By adjusting, the binder resin volume ratio, which is the ratio of the volume of the binder resin to the total of the volume of the binder resin in the conductive paste and the volume of the inorganic particles, is changed to 29% by volume. The same test as in 1 was performed. Table 1 shows the evaluation results of the occurrence of structural defects.

[Comparative Example 1]
The same test as in Example 1 was performed, except that the branched polymer was changed to ethyl cellulose, which is a linear polymer. Table 1 shows the evaluation results of the occurrence of structural defects.

[Comparative Example 2]
The branched polymer is changed to ethyl cellulose, which is a linear polymer, and the dispersant has a carboxy group, which is an adsorptive functional group, and a chain aliphatic hydrocarbon group, which is a hydrophobic group. The same test as in Example 1 was performed, except that the dispersant was changed to a polymeric dispersant that did not have an ethylene group (polyether chain). Table 1 shows the evaluation results of the occurrence of structural defects.

[Comparative Example 3]
The dispersant is changed to a polymeric dispersant that has a carboxy group, which is an adsorptive functional group, and a chain aliphatic hydrocarbon group, which is a hydrophobic group, but does not have a polyoxyethylene group (polyether chain). Except for this, the same test as in Example 1 was performed. Table 1 shows the evaluation results of the occurrence of structural defects.

[Comparative Example 4]
The branched polymer is changed to a resin having a main chain composed of ethyl cellulose and a branch chain composed of polycaprolactone, which is an aliphatic polyester, and the dispersant is composed of a carboxy group, which is an adsorptive functional group, and a hydrophobic group. The same test as in Example 1 was performed, except that the polymer dispersant was changed to a polymeric dispersant having certain linear aliphatic hydrocarbon groups but no polyoxyethylene groups (polyether chains). Table 1 shows the evaluation results of the occurrence of structural defects.

[Comparative Example 5]
The same test as in Example 1 was performed, except that the branched polymer was changed to a linear polymer, ethyl cellulose, and the hydrophilic group of the dispersant was changed to a polycaprolactone group (polyester chain). Table 1 shows the evaluation results of the occurrence of structural defects.

[Comparative Example 6]
The same test as in Example 1 was performed, except that the branched polymer was changed to a linear polymer, ethyl cellulose, and the hydrophilic group of the dispersant was changed to a polypropylene carbonate group (polycarbonate chain). Table 1 shows the evaluation results of the occurrence of structural defects.

[Comparative Example 7]
The same test as in Example 1 was performed, except that the branched polymer was changed to ethyl cellulose, which is a linear polymer, and ceramic particles were not used in the preparation of the conductive paste. Table 1 shows the evaluation results of the occurrence of structural defects.

[Comparative Example 8]
The same test as in Example 1 was performed, except that the branched polymer was changed to ethyl cellulose, which is a linear polymer, and the metal particles were changed to Cu particles having an SEM diameter of 500 nm. Table 1 shows the evaluation results of the occurrence of structural defects.

[Comparative Example 9]
By changing the branched polymer to ethyl cellulose, which is a linear polymer, and adjusting the amount of ethyl cellulose used and the amount of Ni particles and ceramic particles used, the volume of the binder resin in the conductive paste and the amount of inorganic particles The same test as in Example 1 was performed, except that the binder resin volume ratio, which is the ratio of the binder resin volume to the total volume, was changed to 17% by volume. Table 1 shows the evaluation results of the occurrence of structural defects.

[Comparative Example 10]
By changing the branched polymer to ethyl cellulose, which is a linear polymer, and adjusting the amount of ethyl cellulose used and the amount of Ni particles and ceramic particles used, the volume of the binder resin in the conductive paste and the amount of inorganic particles The same test as in Example 1 was performed, except that the binder resin volume ratio, which is the ratio of the binder resin volume to the total volume, was changed to 29% by volume. Table 1 shows the evaluation results of the occurrence of structural defects.

The specific functional groups in Table 1 below are types of functional groups corresponding to any of polyether chains, polyester chains, and polycarbonate chains.
The binder resin volume ratio is the ratio of the volume of the binder resin to the sum of the volume of the binder resin and the volume of the inorganic particles in the conductive paste.
The abbreviations in the table below are as follows.
EC: ethyl cellulose PCL: polycaprolactone (aliphatic polyester)
PPC: polypropylene carbonate (aliphatic polycarbonate)

According to an embodiment, a branched polymer having a main chain composed of a cellulosic polymer and branch chains composed of an aliphatic polycarbonate or an aliphatic polyester, and a dispersant having hydrophilic chains such as polyether chains are combined. When cutting a laminate containing a conductive sheet formed using a combination of conductive pastes, delamination as a structural defect hardly occurs even if a shearing force is applied when cutting the laminate. I understand.
On the other hand, according to the comparative example, when the binder resin contained in the conductive paste consists only of a main chain made of a cellulose polymer, or when the dispersant does not have a specific hydrophilic chain, when cutting the laminate It can be seen that delamination is likely to occur as a structural defect.

Claims

comprising a branched polymer, inorganic particles, a dispersant, and an organic solvent;
The molecular chain of the branched polymer has a main chain made of a cellulose-based polymer and a branch chain made of an aliphatic polycarbonate or an aliphatic polyester,
The branched chain may be linear or branched,
the branch chains may bind to two or more of the main chains to bridge the two or more main chains;
An inorganic particle-containing paste, wherein the dispersant has at least one selected from the group consisting of polyether chains, polyester chains, and polycarbonate chains.
The inorganic particle-containing paste according to claim 1, wherein the cellulosic polymer contains at least one selected from the group consisting of methyl cellulose, ethyl cellulose, cellulose acetate butyrate, cellulose acetate propionate, and cellulose acetate.
The inorganic particle-containing paste according to claim 1 or 2, wherein the inorganic particles include ceramic particles and/or metal particles.
The composite structure according to claim 3, wherein metal particles are included as the inorganic particles, and the metal constituting the metal particles is at least one selected from the group consisting of Ni, Cu, Ag, and Au.
5. The method according to claim 3 or 4, wherein the ceramic particles are included as the inorganic particles, and the material constituting the ceramic particles includes at least one selected from the group consisting of Ba, Ti, Sr, Ca, and Zr. composite structure.
The inorganic particle-containing paste according to any one of claims 1 to 5, wherein the organic solvent contains an ester solvent.
The ratio of the volume of the branched polymer to the sum of the volume of the branched polymer and the volume of the inorganic particles is 17% by volume or more and 29% by volume or less, according to any one of claims 1 to 6. Paste containing inorganic particles.
comprising a branched polymer, inorganic particles, and a dispersant;
The molecular chain of the branched polymer has a main chain made of a cellulose-based polymer and a branch chain made of an aliphatic polycarbonate or an aliphatic polyester,
The branched chain may be linear or branched,
the branch chains may bind to two or more of the main chains to bridge the two or more main chains;
An inorganic particle-containing film, wherein the dispersant has at least one selected from the group consisting of polyether chains, polyester chains, and polycarbonate chains.
The inorganic particle-containing film according to claim 8, wherein the inorganic particles contain ceramic particles and are a green sheet that provides a dielectric layer in a multilayer ceramic electronic component by firing.
The inorganic particle-containing film according to claim 8, wherein the inorganic particles contain metal particles and are a conductive sheet that provides an internal electrode layer in a multilayer ceramic electronic component by firing.
A laminate in which at least one layer is composed of the inorganic particle-containing film according to claim 8.
A green sheet that provides a dielectric layer by firing and a conductive sheet that provides an internal electrode layer by firing are laminated,
The green sheet is the inorganic particle-containing film according to claim 9, or the conductive sheet is the inorganic particle-containing film according to claim 10,
12. The laminate according to claim 11, which is used for manufacturing a laminated ceramic electronic component.