KR20190038864A - Ceramic Green Sheet and Coating Sheet - Google Patents

Abstract

[PROBLEMS] To provide a ceramic green sheet excellent in adhesiveness at the time of pressing and hardly causing delamination. Provided is a ceramic green sheet in which a coated sheet obtained by applying an arbitrary conductive paste to a ceramic green sheet is excellent in adhesion at the time of pressing and in which delamination is less likely to occur. (At least one side of the ceramic green sheet), which is the ratio of the intensity of the detected Ba + ions to the intensity of the detected Ti + ions (the intensity of the Ba + ions) in the case of performing the secondary ion analysis with the time- / (Intensity of Ti + ion) satisfies 20 <(intensity of Ba + ion) / (intensity of Ti + ion) <1,000.

Description

Ceramic Green Sheet and Coating Sheet

The present invention relates to a ceramic green sheet excellent in adhesiveness at the time of compression and having little dimensional change upon compression. The present invention also relates to a coated sheet excellent in adhesion at the time of compression.

Polyvinyl acetal has been proposed in various polymers in that a strong film can be obtained, a unique structure having a hydrophilic hydroxy group and a hydrophobic acetal group together.

Among them, polyvinyl butyral is widely used as a binder for ceramic molding, various binders and films.

The ceramic molding binder is used, for example, as a suitable binder for molding in the process of producing a multilayer ceramic capacitor or a circuit board of an IC chip. Among them, it is widely used as a binder used in the production of a ceramic green sheet.

Polyvinyl acetal is also used as a binder for a conductive paste used in the production of multilayer ceramic capacitors and the like. The electrode layer may be formed by a method in which an electrode layer is directly formed on a ceramic green sheet, an electrode layer is formed on the carrier film by printing or the like, and an electrode layer is transferred from the carrier film to the ceramic green sheet by hot pressing There is a way.

Here, the multilayer ceramic capacitor is a chip type ceramic capacitor in which a dielectric such as titanium oxide or barium titanate and an inner electrode are stacked in layers. In such a multilayer ceramic capacitor, for example, a plurality of conductive pastes, which become internal electrodes on the surface of a ceramic green sheet, are applied by screen printing or the like, are piled up and piled up and heated and pressed to obtain a laminate, (Degreasing), followed by firing. In some cases, a ceramic green sheet on which a circuit is not formed by a conductive paste is laminated. Among them, barium titanate is widely used in multilayer ceramic capacitors because of its high dielectric constant.

2. Description of the Related Art In recent years, as electronic equipment has become more versatile and smaller, multilayer ceramic capacitors have been required to have larger capacity and smaller size. Attempts have been made to meet this need by thinning ceramic green sheets or by layering layers of multilayer ceramic capacitors. For example, as a method of making a thin film, a ceramic powder having a fine particle diameter of 0.5 탆 or less is used as a ceramic powder used for a ceramic green sheet, and an attempt is made to coat the ceramic powder on a peelable support in a thin film such as 5 탆 or less .

On the other hand, when the multilayer ceramic capacitor is manufactured, the ceramic green sheet or the conductor layer is deformed when the ceramic green sheet is subjected to pressure bonding in a step of pressing and pressing, thereby making it difficult to achieve high precision required for multilayer ceramic parts. On the other hand, if the compression bonding is weakened, the adhesion between the ceramic green sheets or between the ceramic green sheet and the conductor layer is weak in the conventional manufacturing method, and the upper and lower ceramic green sheets or ceramic green sheets and the electrode layers may not adhere to each other. If such adhesion failure occurs, there is a problem that the cutting failure due to the positional deviation of the bonding surface, defects such as delamination after firing the ceramic multilayer body, and reliability of parts are deteriorated. Further, if an excessive plasticizer is added to improve the adhesiveness, there is a problem that it is difficult to obtain a desired laminated sheet by being deformed upon compression.

As an attempt to solve the above problems, for example, Patent Document 1 discloses the use of a ceramic slurry containing a phthalic acid plasticizer, a glycol plasticizer and / or an amino alcohol plasticizer. Patent Document 2 discloses a ceramic paste having a high plasticizing effect and an appropriate volatility. Patent Document 3 discloses a manufacturing method for improving the adhesiveness by subjecting a film to surface treatment using an atmospheric plasma apparatus.

Japanese Patent Application Laid-Open No. 2001-106580 Japanese Patent Application Laid-Open No. 2006-027990 International Publication No. 2011/046143

However, as described above, the particle diameter of barium titanate has been minimized for thinning. When the ceramic powder having a fine particle diameter is used, the filling density and the surface area are increased, the surface of the barium titanate can not be covered sufficiently, barium titanate itself exists on the surface of the ceramic green sheet, As the ceramic green sheets are laminated in multiple layers in accordance with the multilayer ceramic capacitor, decomposition of the resin at one time during degreasing causes delamination, which is called delamination, as a result of which degradation of the reliability of the components may occur.

The present invention has been made in order to solve the above problems, and its main object is to provide a ceramic green sheet and a coated sheet excellent in adhesion between layers.

Another object of the present invention is to provide a coated sheet which is obtained by applying an optional conductive paste to the ceramic green sheet of the present invention and which has excellent adhesion at the time of compression bonding.

It is a further object to provide a ceramic green sheet and a coated sheet which are less susceptible to delamination when the sintered body is produced by laminating the ceramic green sheets and / or coated sheets of the present invention.

According to the present invention,

[1] When at least one surface of a ceramic green sheet is subjected to secondary ion analysis using a time-of-flight (time-of-flight) secondary ion analyzer, the intensity of detected Ba + (Intensity of Ba + ion) / (intensity of Ti + ion) satisfying 20 <(intensity of Ba + ion) / (intensity of Ti + ion) <1,000.

[2] A resin composition comprising a binder resin (A) having a hydroxyl group in a molecule,

(In the formula 1,

R1 and R4 each independently represent an organic group having at least one ether bond,

R2 is an alkylene group having 1 to 20 carbon atoms which may have a branch,

R3 is an alkylene group which may have a branch having 1 to 4 carbon atoms,

and m is an integer of 0 to 5)

(B) represented by the following formula (1): &quot; (1) &quot;

[3] The ceramic green sheet of [2], wherein the acid value of the organic compound (B) is 5 mg KOH / g or less;

[4] The compound according to [1], wherein R1 and / or R4 are each independently selected from the group consisting of:

(In the formula (2)

R5 is an alkyl group having 1 to 10 carbon atoms which may have a branch,

R6 is an alkylene group having 1 to 10 carbon atoms which may have a branch,

R7 is an alkylene group having 1 to 4 carbon atoms,

and n is an integer of 0 to 2)

A ceramic green sheet of [2] or [3], wherein the ceramic green sheet is an organic group having at least one ether bond,

[5] A ceramic green sheet according to any one of [2] to [4], wherein the ceramic green sheet contains 1 to 60 parts by mass of the organic compound (B) per 100 parts by mass of the binder resin (A).

[6] The ceramic green sheet according to any one of [2] to [5], wherein the binder resin (A) comprises at least one member selected from the group consisting of polyvinyl acetal and (meth) acrylic resin.

The polyvinyl acetal preferably has an acetalization degree of 50 to 85 mol%, a content of a vinyl ester monomer unit of 0.1 to 20 mol%, a viscosity average degree of polymerization 200 to 5,000, the ceramic green sheet of [6];

[8] A ceramic green sheet according to any one of [2] to [7], which contains barium titanate and contains 3 to 20 parts by mass of the binder resin (A) per 100 parts by mass of barium titanate.

[9] A coated sheet comprising a ceramic green sheet of any one of [1] to [8], wherein at least one surface of the ceramic green sheet is provided with a layer on which a conductive paste is dried;

[10] A coated sheet according to [9], wherein at least a part of the ceramic green sheet is subjected to a plasma treatment.

[11] A coated sheet according to [9] or [10], wherein at least a part of the surface of the coated sheet is subjected to a plasma treatment.

&Lt; / RTI &gt;

According to the present invention, it is possible to provide a ceramic green sheet excellent in adhesion at the time of compression bonding.

Further, when the ceramic green sheet and / or the coated sheet of the present invention are laminated to produce a sintered body, a ceramic green sheet and a coated sheet which are less susceptible to delamination can be provided.

In the ceramic green sheet of the present invention, when the secondary ion analysis is performed with respect to the bonding surface of the ceramic green sheet, the strength of the Ba + ion relative to the strength of the Ti + ion detected as the cation (The intensity of Ba + ions) / (the intensity of Ti + ions) < 1,000.

[Binder resin (A) having a hydroxyl group in the molecule]

Examples of the binder resin (A) having a hydroxyl group in the molecule (hereinafter sometimes abbreviated as "binder resin (A)") include polyvinyl acetal, polyvinyl alcohol, (meth) acrylic resin having a hydroxyl group Acrylic acid, polyalkylene oxide, and the like. Of these, polyvinyl acetal or a (meth) acrylic resin having a hydroxyl group is preferable from the viewpoints of the dispersibility of the inorganic compound and the flexibility and adhesion of the ceramic green sheet and the coated sheet, and polyvinyl acetal is more preferable.

(Polyvinyl acetal)

When the binder resin (A) contains polyvinyl acetal, the content of the polyvinyl acetal in the binder resin (A) is preferably 5% by mass or more, more preferably 30% by mass or more, further preferably 50% By mass, particularly preferably 70% by mass or more, most preferably 100% by mass.

The acetylation degree of the polyvinyl acetal is preferably 50 mol% or more, more preferably 55 mol% or more, further preferably 60 mol% or more, particularly preferably 65 mol% or more. The acetalization degree of the polyvinyl acetal is preferably 85 mol% or less, more preferably 82 mol% or less, further preferably 78 mol% or less, particularly preferably 75 mol% or less. The degree of acetalization represents the ratio of the acetalized vinyl alcohol monomer units to the total monomer units constituting the polyvinyl acetal. If the degree of acetalization exceeds 85 mol%, the efficiency of the acetalization reaction tends to be lowered.

The content of the vinyl ester monomer unit of the polyvinyl acetal is preferably 0.1 mol% or more, more preferably 0.3 mol% or more, still more preferably 0.5 mol% or more, particularly preferably 0.7 mol% or more. The content of the vinyl ester monomer unit of the polyvinyl acetal is preferably 20 mol% or less, more preferably 18 mol% or less, still more preferably 15 mol% or less, particularly preferably 13 mol% or less. When the content of the vinyl ester monomer unit is less than 0.1 mol%, when the polyvinyl alcohol is dissolved in the solvent for the acetalization, undecolorized polyvinyl alcohol may be formed, and the quality of the obtained polyvinyl acetal Is lowered.

The content of the vinyl alcohol monomer unit of the polyvinyl acetal is preferably 15 mol% or more, more preferably 25 mol% or more. The content of the vinyl alcohol monomer unit of the polyvinyl acetal is preferably 50 mol% or less, more preferably 40 mol% or less, and further preferably 35 mol% or less.

The content of other monomer units (acetalized monomer units, vinyl ester monomer units, and monomer units other than vinyl alcohol monomer units) in the polyvinyl acetal is preferably 20 mol% or less, and more preferably 10 mol% or less.

The viscosity average degree of polymerization of the polyvinyl acetal is preferably 200 or more, and more preferably 5,000 or less. A more suitable range will be described later. The viscosity average degree of polymerization of the polyvinyl acetal contained in the binder resin (A) is determined by a viscosity average of the polyvinyl alcohol of the raw material (hereinafter sometimes abbreviated as &quot; PVA &quot;) measured in accordance with JIS K 6726: 1994 And the degree of polymerization. Namely, the PVA can be determined from the intrinsic viscosity [?] (L / g) measured in water at 30 占 폚 after the recrystallization and purification of the PVA at 99.5 mol% or more.

[Formula I]

The viscosity average degree of polymerization of PVA and the viscosity average degree of polymerization of the polyvinyl acetal obtained by acetalizing it are substantially the same.

(Production method of polyvinyl acetal)

The polyvinyl acetal is usually prepared by acetalizing PVA.

The saponification degree of the raw PVA is preferably 80 mol% or more, more preferably 82 mol% or more, further preferably 85 mol% or more, and most preferably 87 mol% or more. The saponification degree of the raw PVA is preferably 99.9 mol% or less, more preferably 99.7 mol% or less, still more preferably 99.5 mol% or less, and most preferably 99.3 mol% or less.

When the saponification degree of the raw material PVA exceeds 99.9 mol%, PVA can not be stably produced. The saponification degree of PVA is measured according to JIS K 6726: 1994.

The raw material PVA can be obtained by a conventionally known method, that is, by saponification of a polymer obtained by polymerizing a vinyl ester monomer. As the method of polymerizing the vinyl ester monomer, conventionally known methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization can be applied. As the polymerization initiator, azo-based initiators, peroxide-based initiators, redox-based initiators, and the like are appropriately selected depending on the polymerization method. As the saponification reaction, it is possible to use a conventionally known alkali catalyst or an acid catalyst, such as digester decomposition and hydrolysis. Of these, methanol is used as a solvent and a saponification reaction using a caustic soda (NaOH) desirable.

Examples of the vinyl ester monomer include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caprate, vinyl caprylate, vinyl laurate, Vinyl palmitate, vinyl stearate, vinyl oleate, and vinyl benzoate. Of these, vinyl acetate is particularly preferable.

When the vinyl ester monomer is polymerized, it may be copolymerized with other monomers within the range not impairing the object of the present invention. Therefore, the polyvinyl alcohol in the present invention is a concept including a polymer composed of a vinyl alcohol unit and another monomer unit. Examples of other monomers include, for example,? -Olefins such as ethylene, propylene, n-butene and i-butene; Acrylic acid and its salts; Acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate and octadecyl acrylate; Methacrylic acid and its salts; Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2- Methacrylic acid esters such as ethylhexyl, undecyl methacrylate and octadecyl methacrylate; Acrylamide, N-methylacrylamide, N-ethyl acrylamide, N, N-dimethylacrylamide, diacetone acrylamide, acrylamide propane sulfonic acid and its salts, acrylamidopropyldimethylamine and its acid salts or quaternary salts, Acrylamide derivatives such as N-methylol acrylamide and derivatives thereof; Methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamide propanesulfonic acid and its salts, methacrylamidopropyldimethylamine and its salts or quaternary salts, N-methylol methacrylamide and Methacrylamide derivatives such as derivatives thereof; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether and stearyl vinyl ether Ethers; Nitriles such as acrylonitrile and methacrylonitrile; Vinyl halides such as vinyl chloride and vinyl fluoride; Vinylidene halides such as vinylidene chloride and vinylidene fluoride; Allyl compounds such as allyl acetate and allyl chloride; Maleic acid and its salts, esters or anhydrides; Vinylsilyl compounds such as vinyltrimethoxysilane; Isopropenyl acetate, and isopropenyl acetate. These monomers are usually used in a proportion of less than 10 mol% based on the vinyl ester monomer.

When the other monomer unit is an? -Olefin unit, the lower limit of the content thereof is preferably 1 mol%, and the upper limit thereof is preferably 20 mol%. If the content of the? -olefin unit is less than 1 mol%, the effect of containing the? -olefin becomes insufficient, and if it exceeds 20 mol%, the hydrophobicity of the obtained polyvinyl acetal becomes too strong, The solubility of the polyvinyl alcohol resin as a raw material is lowered, so that the acetalization reaction becomes difficult.

In the present invention, the acid catalyst used in the acetalization reaction is not particularly limited, and any organic acid or inorganic acid can be used. Examples thereof include acetic acid, para-toluenesulfonic acid, nitric acid, sulfuric acid, hydrochloric acid and the like. Of these, hydrochloric acid, sulfuric acid and nitric acid are preferably used. Generally, when nitric acid is used, the reaction rate of the acetalization reaction is increased and productivity is desired to be improved. On the other hand, the polyvinyl acetal particles obtained are likely to be coarse and ununiform among the batches tends to increase Therefore, hydrochloric acid is particularly preferable as the acid catalyst used in the acetalization reaction.

The aldehyde to be used in the acetalization reaction is not particularly limited, but an aldehyde having a known hydrocarbon group can be mentioned. As the aldehyde having a hydrocarbon group, examples of the aliphatic aldehyde include formaldehyde (including paraformaldehyde), acetaldehyde, propionaldehyde, butylaldehyde, isobutylaldehyde, valeraldehyde, isovaleraldehyde, hexylaldehyde, 2-ethylbutylaldehyde Cyclohexane aldehyde, cyclohexane aldehyde, cyclohexane aldehyde, cyclohexane aldehyde, cyclohexane aldehyde, cyclohexane aldehyde, cyclohexane aldehyde, cyclohexane aldehyde, cyclohexane aldehyde, cyclohexane aldehyde, cyclohexane aldehyde, Examples of the cycloaliphatic aldehyde include cyclohexane aldehyde, dimethyl cyclohexane aldehyde and cyclohexane acetaldehyde. Examples of the cyclic unsaturated aldehyde include cyclopentene aldehyde and cyclohexene aldehyde. Examples of aromatic or unsaturated aldehyde include benzaldehyde and methylbenzaldehyde Naphthylaldehyde, anthraldehyde, cinnamaldehyde, crotonaldehyde, acrolein aldehyde and 7-octen-1-al. Examples of the heterocyclic aldehyde include dimethylbenzaldehyde, methoxybenzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, Furfuralaldehyde, methylfurfuralaldehyde, and the like. Among these aldehydes, aldehydes having 1 to 8 carbon atoms are preferable, aldehydes having 4 to 6 carbon atoms are more preferable, and n-butylaldehyde is particularly preferably used. In the present invention, polyvinyl acetal obtained by using two or more aldehydes in combination may be used.

As the aldehyde used in the acetalization reaction, aldehydes other than hydrocarbon-based aldehydes can also be used. For example, an aldehyde having a functional group selected from an amino group, an ester group, a carbonyl group, and a vinyl group may be used.

Examples of the aldehyde having an amino group as a functional group include aminoacetaldehyde, dimethylaminoacetaldehyde, diethylaminoacetaldehyde, aminopropionaldehyde, dimethylaminopropionaldehyde, aminobutylaldehyde, aminopentylaldehyde, dimethylaminobenzaldehyde, dimethylaminobenzaldehyde, ethylmethylamino Benzaldehyde, diethylaminobenzaldehyde, pyrrolidyl acetaldehyde, piperidyl acetaldehyde, pyridylacetaldehyde and the like, and aminobutylaldehyde is preferable from the viewpoint of productivity.

Examples of the aldehyde having an ester group as a functional group include methyl glyoxylate, ethyl glyoxylate, methyl formyl acetate, ethyl formyl acetate, methyl 3-formylpropionate, ethyl 3-formylpropionate, methyl 5-formylpentanoate, -Formylphenylacetate, and the like.

Examples of the aldehyde having a carbonyl group as a functional group include glyoxylic acid and a metal salt or ammonium salt thereof, 2-formyl acetic acid and its metal salt or ammonium salt, 3-formylpropionic acid and its metal salt or ammonium salt, 5-formylpentanoic acid and its metal salt or ammonium salt, 4-formylphenoxyacetic acid and its metal salts or ammonium salts, 2-carboxybenzaldehyde and metal salts or ammonium salts thereof, 4-carboxybenzaldehyde and metal salts or ammonium salts thereof, 2,4-dicarboxybenzaldehyde and metal salts or ammonium salts thereof .

As the aldehyde having a vinyl group as a functional group, acrolein and the like can be mentioned.

Also, within the scope of not impairing the characteristics of the present invention, it is possible to use aldehydes having an aldehyde group, an aldehyde having an amide group, an aldehyde having a hydroxyl group, an aldehyde having a sulfonic acid group, an aldehyde having a phosphoric acid group, a cyano group, a nitro group or a quaternary ammonium salt Aldehyde, aldehyde having a halogen atom, or the like may be used.

((Meth) acrylic resin having a hydroxyl group)

When a (meth) acrylic resin having a hydroxyl group is used as the binder resin (A), for example, a (meth) acrylic monomer having a hydroxyl group and a (meth) acrylic monomer having no hydroxyl group May be used. Examples of the (meth) acrylic monomers having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, Polyethylene glycol-polypropylene glycol monoacrylate, polyethylene glycol-polytetramethylene glycol monoacrylate, polypropylene glycol monoacrylate, polypropylene glycol monoacrylate, polyethylene glycol-polypropylene glycol monoacrylate, Acrylate such as propylene glycol-polytetramethylene glycol monoacrylate; Hydroxybutyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-di Polypropylene glycol monomethacrylate, polyethylene glycol-polypropylene glycol monomethacrylate, polyethylene glycol-polytetramethylene glycol monomethacrylate, polypropylene glycol-poly And methacrylates such as tetramethylene glycol monomethacrylate. Among them, methacrylate having a hydroxyl group in terms of sintering property is preferable, and specifically, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate It is preferable to use acrylate.

Examples of the (meth) acrylic monomers having no hydroxyl group include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, Acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, isodecyl acrylate, isobornyl acrylate, tetrahydrofuryl acrylate, etc. Acrylate; Ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n- Methacrylates such as cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, isodecyl methacrylate, isobornyl methacrylate, and tetrahydrofuryl methacrylate, . Of these, methacrylate is preferable from the viewpoint of sintering property, and specific examples thereof include ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, Isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate and 2-ethylhexyl methacrylate.

The content of the segment derived from the (meth) acrylic monomer having a hydroxyl group in the (meth) acrylic resin is preferably 30% by mass or less, more preferably 20% by mass or less. If the content of the segment derived from the (meth) acrylic monomer having a hydroxyl group exceeds 30% by mass, the residual carbon after sintering may increase. The content of the segment derived from the (meth) acrylic monomer having a hydroxyl group is preferably 1% by mass or more. If the content of the segment derived from the (meth) acrylic monomer having a hydroxyl group is less than 1% by mass, when the compatibility with the polyvinyl acetal resin is poor when used together with the polyvinyl acetal resin as the binder resin (A) .

(Other binder resin (A))

As the binder resin (A), one type may be used alone, or two or more types may be used in combination. When two or more of them are used in combination, a mixture of polyvinyl acetal and other binder resin (A) may be used. When the polyvinyl acetal is mixed with the other binder resin (A), for example, the mass ratio of the polyvinyl acetal to the other binder resin (A) is preferably 5/95 or more, more preferably 10/90 or more. The mass ratio of the polyvinyl acetal to the other binder resin (A) is preferably 95/5 or less, more preferably 90/10 or less. As the other binder resin (A), a (meth) acrylic resin having a hydroxyl group is preferable.

In the ceramic green sheet of the present invention, a binder resin having no hydroxyl group in the molecule may be contained in addition to the binder resin (A) within a range that does not impair the effect of the present invention. When a binder resin having no hydroxyl group in the molecule is used, the proportion thereof is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more based on 100 parts by mass of the binder resin (A). The ratio of the binder resin having no hydroxyl group in the molecule is preferably 80 parts by mass or less, more preferably 50 parts by mass or less, based on 100 parts by mass of the binder resin (A).

[Organic compound (B)]

In the ceramic green sheet of the present invention, the organic compound (B) represented by the general formula (1) is contained.

[Chemical Formula 1]

R2 in the formula (1) represents an alkylene group having 1 to 20 carbon atoms which may have a branch. The carbon number of R2 is preferably 15 or less, more preferably 10 or less, further preferably 8 or less. The carbon number of R 2 is preferably 2 or more, more preferably 3 or more, and further preferably 4 or more. If the carbon number of R2 is out of the above range, the compatibility of the organic compound (B) with the binder resin (A) becomes poor, and the storage stability of the ceramic slurry and the adhesion of the ceramic green sheet tend to be lowered. R3 represents an alkylene group which may have a branch having 1 to 4 carbon atoms. The carbon number of R3 is preferably 3 or less, more preferably 2 or less. R2 and R3 may have a straight chain structure or may have a branch, and R2 and R3 are each preferably independently a straight chain structure.

m is an integer of 0 to 5; m is preferably 2 or less, more preferably 1 or less, and even more preferably 0. If m is larger than the above range, the boiling point of the organic compound (B) becomes high, which may cause delamination during firing.

R1 and R4 each independently represent an organic group having at least one ether bond. R1 and R4 may independently have a plurality of ether bonds. It is preferable that R1 and R4 each independently represent a hydrocarbon group having at least one ether bond. R1 and R4 may be the same or different. Each of R 1 and R 4 is preferably an organic group having at least one ether bond represented by the general formula (2) from the viewpoint of compatibility with the binder resin (A).

(2)

R5 represents an alkyl group having 1 to 10 carbon atoms which may have a branch. The carbon number of R5 is preferably 8 or less, more preferably 6 or less, further preferably 4 or less. When the number of carbon atoms in R5 exceeds the above range, the compatibility of the organic compound (B) with the binder resin (A) is deteriorated and the adhesiveness tends to be lowered. R6 represents an alkylene group having 1 to 10 carbon atoms which may have a branch. The number of carbon atoms of R6 is preferably 8 or less, more preferably 6 or less, still more preferably 4 or less. When the number of carbon atoms of R6 exceeds the above range, the compatibility of the organic compound (B) with the binder resin (A) becomes poor, and the adhesion of the ceramic green sheet tends to be lowered. R7 represents an alkylene group which may have a branch having 1 to 4 carbon atoms. The carbon number of R7 is preferably 3 or less, more preferably 2 or less. R6 and R7 may each independently have a straight chain structure or may have branches. R6 and R7 are preferably straight-chain structures. The plural R &lt; 7 &gt; s may be the same or different.

n is an integer of 0 to 2; n is preferably 0 or 1, more preferably 0. When n exceeds the above range, the boiling point of the organic compound (B) increases, which may cause delamination during firing.

The acid value of the organic compound (B) is preferably 5 mg KOH / g or less, more preferably 3 mg KOH / g or less, still more preferably 1 mg KOH / g or less, particularly preferably 0.5 mg KOH / g or less Do. As described above, when the above range is satisfied, it is preferable from the viewpoint of reduction of delamination due to abrupt decomposition at the time of degreasing and further from the viewpoint of reducing the corrosiveness of the process. The acid value of the organic compound (B) is increased due to the formation of a carboxylic acid by de-esterification during storage or the remaining unreacted carboxylic acid in the production of the organic compound (B).

The molecular weight of the organic compound (B) is preferably 200 or more, more preferably 250 or more. If the molecular weight is less than the above range, the volatility is high and volatilization occurs at the time of drying the sheet, so that sufficient adhesiveness may not be exhibited. The molecular weight of the organic compound (B) used in the present invention is preferably 500 or less, and more preferably 400 or less. If the molecular weight is larger than the above range, the viscosity of the organic compound (B) tends to be increased or solidified, and the compatibility with the resin tends to be lowered.

As the structure of the organic compound (B), it is preferable that the molecule does not contain a hydroxyl group. In the case where the organic compound (B) contains a hydroxyl group, the action at the interface at the time of compression tends to be lowered, so that sufficient adhesiveness may not be obtained.

Examples of the organic compound (B) include adipic acid bis (2-butoxyethyl), adipic acid bis (2-methoxyethyl) adipic acid bis (2-ethoxyethyl) Bis (2-methoxyethoxy) ethyl], adipic acid bis (3-methoxy-3-methylbutyl) Ethoxyethyl), and the like. Among these, from the viewpoint of maintaining the safety of the ceramic slurry, the adhesion of the ceramic green sheet, and maintaining the proper strength, adipic acid bis (2-butoxyethyl) adipate bis (2-methoxy Ethyl) is preferable.

[Organic solvent (C)]

The ceramic green sheet of the present invention is obtained by drying a ceramic slurry containing, for example, a binder resin (A), an organic compound (B), an organic solvent (C) and an inorganic compound (D) have. The organic solvent (C) may be suitably used for its purpose or use, and examples thereof include alcohols such as methanol, ethanol, isopropanol, n-propanol and butanol; Cellosolves such as methyl cellosolve and butyl cellosolve; Ketones such as acetone and methyl ethyl ketone; Aromatic hydrocarbons such as toluene and xylene; Halogenated hydrocarbons such as dichloromethane and chloroform, esters such as ethyl acetate and methyl acetate, aliphatic hydrocarbons such as menthone, menthane, menthone, mulsenene,? -Pinene,? -Terpinene,? -Terpinene, limonene, perlyl acetate, But are not limited to, carvinyl acetate, dihydrocarbyl acetate, peryl alcohol, dihydrotophenol acetate, terpineol acetate, dihydrotophenol, terpinyloxyethanol, dihydroterpinyloxyethanol, terpinyl methyl ether, di Isobornyl acetate, isobutyl acetate, isobutyl acetate, isopropyl acetate, isopropyl acetate, isopropyl acetate, isopropyl acetate, isopropyl acetate, Acetoxy-methoxyethoxy-cyclohexanol acetates, dihydrocarbols, 2-ethylhexyl glycol , Benzyl glycol, phenylpropylene glycol, methyldecalin, amylbenzene, cumene, cymene, 1,1-diisopropylhexane, and citronelol. Of these, alcohols such as methanol, ethanol, isopropanol, n-propanol and butanol; Cellosolves such as methyl cellosolve and butyl cellosolve; Ketones such as acetone and methyl ethyl ketone; Aromatic hydrocarbons such as toluene and xylene; Halogenated hydrocarbons such as dichloromethane and chloroform, and esters such as ethyl acetate and methyl acetate are preferably used. These may be used singly or in combination of two or more. Further, butanol, ethanol, toluene, ethyl acetate, or a mixed solvent thereof is more preferable in terms of volatility and solubility.

The content of the organic solvent (C) in the ceramic slurry is not particularly limited, but is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and more preferably 10 parts by mass or more based on 100 parts by mass of the ceramic powder desirable. When the content of the organic solvent (C) is less than the above range, the viscosity of the ceramic slurry becomes excessively high and the kneadability tends to be lowered. The content of the organic solvent (C) is more preferably 200 parts by mass or less, and further preferably 150 parts by mass or less, based on 100 parts by mass of the ceramic powder. If the content of the organic solvent (C) exceeds the above range, the viscosity of the ceramic slurry is too low, and the handling property when forming the ceramic green sheet tends to be poor.

[Inorganic compound (D)]

The ceramic green sheet of the present invention contains at least barium titanate as the inorganic compound (D), but other inorganic compound (D) can be used. Examples of other inorganic compounds (D) include glass powder, ceramic powder, fluorescent substance fine particles, silicon oxide, and the like depending on the purpose and use. These inorganic compounds (D) can be suitably used in combination of two or more.

Examples of the glass powder include glass powders such as bismuth oxide glass, silicate glass, lead glass, zinc glass and boron glass, CaO-Al ₂ O ₃ -SiO ₂ series, MgO-Al ₂ O ₃ -SiO ₂ , And glass powders of various silicon oxides such as LiO ₂ -Al ₂ O ₃ -SiO ₂ series.

Examples of the ceramic powder include not only barium titanate but also oxides, carbides, nitrides, borides, sulfides and the like of metals or nonmetals used for the production of ceramics. Specific examples thereof include Li, K, Mg, B, Al, Si, Cu, Ca, Sr, Ba, Zn, Cd, Ga, In, Y, lanthanoids, Nb, Ta, W, Mn, Fe, Co and Ni, carbide, nitride, boride and sulfide.

[Ceramic Green Sheet]

In the ceramic green sheet, the content of the binder resin (A) relative to the ceramic powder differs depending on the purpose of use of the ceramic green sheet, but it is usually preferably 3 parts by mass or more based on 100 parts by mass of barium titanate, Or more. The content of the binder resin (A) is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, based on 100 parts by mass of barium titanate. If the content of the binder resin (A) is less than 3 parts by mass based on 100 parts by mass of barium titanate, there is a possibility that the obtained ceramic green sheet is poorly adhered and lacks in strength. When the amount of the binder resin (A) used exceeds 20 parts by mass, the density of barium titanate in the ceramic green sheet is lowered. Therefore, the quality of the multilayer ceramic capacitor as a final product is deteriorated, Which may cause delamination accompanied by shrinkage of the sintered body.

When polyvinyl acetal is contained as the binder resin (A) contained in the ceramic green sheet, if the vinyl alcohol monomer unit of the polyvinyl acetal is less than 50 mol%, it absorbs a large amount of moisture during the storage of the ceramic green sheet, There is a possibility to cause. On the other hand, when the acetylation degree of the polyvinyl acetal exceeds 85 mol%, the content of the hydroxyl group (vinyl alcohol monomer unit) in the polyvinyl acetal is lowered, and the adhesiveness of the ceramic green sheet and the dimensional stability at the time of compression tends to decrease . When the acetalization degree of the polyvinyl acetal is within the above-mentioned preferable range, the obtained ceramic green sheet tends to have better adhesion at the time of pressing.

When the polyvinyl acetal is contained as the binder resin (A) contained in the ceramic green sheet, the preferable range of the content of the vinyl ester monomer unit of the polyvinyl acetal is as described above, but the content of the vinyl ester monomer unit is 20 mol% , The amount of carbon residue tends to increase in the obtained ceramic molded article. Further, the flexibility of the obtained ceramic green sheet becomes high, and the strength of the ceramic green sheet tends to be lowered.

In the case where polyvinyl acetal is contained as the binder resin (A) contained in the ceramic green sheet, the suitable range of the viscosity average degree of polymerization of the polyvinyl acetal is as described above, but if the viscosity average degree of polymerization is less than 200, The strength tends to be lowered. The viscosity average degree of polymerization of the polyvinyl acetal is preferably 300 or more, more preferably 500 or more, and even more preferably 800 or more. On the other hand, when the viscosity average degree of polymerization of the polyvinyl acetal exceeds 5,000, the viscosity of the ceramic slurry prepared at the time of producing the ceramic green sheet becomes excessively high and the productivity may be lowered. The viscosity average degree of polymerization of the polyvinyl acetal is preferably 4,500 or less, more preferably 4,000 or less, and still more preferably 3,500 or less. The viscosity average degree of polymerization of the polyvinyl acetal is preferably 1,400 or more, more preferably 1,500 or more, from the viewpoint of further improving the dimensional stability of the ceramic green sheet at the time of pressing.

In the case where polyvinyl acetal is contained as the binder resin (A) contained in the ceramic green sheet, the preferred range of saponification degree of the raw PVA is as described above. However, if the degree of saponification of the raw PVA is less than 80 mol%, polyvinyl acetal The strength of the ceramic green sheet contained therein may be lowered.

Suitable conditions of the organic compound (B) contained in the ceramic green sheet are as described above.

The content of the organic compound (B) in the ceramic green sheet is not particularly limited, but it is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and more preferably 10 parts by mass or less per 100 parts by mass of the binder resin (A) Or more. When the content of the organic compound (B) is less than the above range, there is a possibility of causing a poor adhesion of the obtained ceramic green sheet. The content of the organic compound (B) is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 40 parts by mass or less. If the content of the organic compound (B) exceeds the above range with respect to 100 parts by mass of the binder resin (A), the strength of the ceramic green sheet is lowered and the dimensional stability at the time of compression tends to be lowered.

The ceramic green sheet may further contain an organic compound other than the organic compound (B) as a plasticizer. Such a plasticizer is not particularly limited as long as it does not impair the effect of the present invention and has no problem in compatibility with the binder resin (A). As the plasticizer, a monoester or diester of an oligoalkylene glycol having a hydroxyl group at both terminals with a carboxylic acid, a diester of a dicarboxylic acid and an alcohol, or the like can be used. These may be used alone or in combination of two or more. Specific examples thereof include triethylene glycol di-2-ethylhexanoate, tetraethylene glycol-di-2-ethylhexanoate, triethylene glycol-di-n-heptanoate, tetraethylene glycol- A monoester or diester of a carboxylic acid and an oligoalkylene glycol having a hydroxyl group at both terminals such as triethylene glycol or tetraethylene glycol such as heptanoate; Diesters of dicarboxylic acids and alcohols such as dioctyl phthalate, dibutyl phthalate, dioctyl adipate and dibutyl adipate.

In the case of adding a plasticizer, the total mass ratio (the mass of the plasticizer and the organic compound (B) / the mass of the binder resin (A)) of the plasticizer and the organic compound (B) to the binder resin More preferably 0.01 or more, and still more preferably 0.05 or more. The mass ratio is preferably 2 or less, more preferably 1.5 or less.

As the ceramic powder other than barium titanate contained in the ceramic green sheet, it is preferable to use the above-mentioned ceramic powder.

As a suitable method for forming the ceramic green sheet, there is a so-called sheet molding method in which ceramic slurry is coated on a carrier film using a blade coater or the like, dried and then released from the carrier film to obtain a ceramic green sheet.

The ceramic green sheet may contain, in addition to the binder resin (A), the organic compound (B) and the ceramic powder, a peptizing agent, an adhesion promoter, a dispersant, a tackifier, A stabilizer, a defoaming agent, a thermal decomposition accelerator, an antioxidant, a surfactant, a lubricant, an adhesion improver, and other conventionally known additives. In addition, as long as the effect of the present invention is not impaired, a resin other than the binder resin (A) may be contained.

In a preferred embodiment of the present invention, when at least one surface of the ceramic green sheet is subjected to secondary ion analysis with a time-of-flight secondary ion analyzer, the ratio of the intensity of the detected Ba + ions to the intensity of the detected Ti + (Intensity of Ba + ion) / (intensity of Ti + ion) satisfy 20 <(intensity of Ba + ion) / (intensity of Ti + ion) <1,000. By using the ceramic green sheet of the present invention, it is possible to obtain a ceramic green sheet which is excellent in adhesion at the time of compression and less in dimensional change upon compression. In addition, when the ceramic green sheet is fired, the sudden loss of the binder component from the laminated body can be suppressed when the ratio of (intensity of Ba + ions) / (intensity of Ti + ions) The delamination at the time of production is suppressed.

(Intensity of Ba + ion) / (intensity of Ti + ion) is preferably larger than 100, more preferably larger than 150. In addition, the (intensity of Ba + ions) / (intensity of Ti + ions) is preferably smaller than 700, more preferably smaller than 500.

The Ba + ions and Ti + ions measured as secondary ions by TOF-SIMS analysis of the ceramic green sheet are derived from Ba atoms and Ti atoms in barium titanate used as the ceramic powder. The method for obtaining a ceramic green sheet in which the strength of (Ba + ion) / (intensity of Ti + ion) is in the above range when TOF-SIMS analysis is performed is not particularly limited, but, for example, (B), and further, a ceramic green sheet is prepared by using a ceramic slurry using barium titanate as a ceramic powder and subjected to a plasma treatment.

However, when the content of the organic compound (B) or the organic compound (plasticizer) other than the organic compound (B) in the ceramic green sheet is decreased, the ceramic green sheet is hardened to improve the dimensional stability at the time of pressing, The adhesiveness of the resin composition tends to be lowered. For this reason, it is generally difficult to achieve both dimensional stability and adhesion. In the present invention, even when the content of the organic compound (B) or the organic compound (plasticizer) other than the organic compound (B) is decreased by setting the (intensity of Ba + ion) / A ceramic green sheet excellent in not only dimensional stability at the time of pressing but also excellent adhesion at the time of pressing can be obtained.

The ceramic green sheet of the present invention is suitably used as a material for various electronic parts. In particular, it is suitably used as a material for a chip-type stacked capacitor and a circuit board of an IC chip. These are produced by forming an electrode on a ceramic green sheet, superimposing and pressing and then firing.

Examples of the method for producing the ceramic green sheet include a method in which a ceramic slurry is coated on a support film subjected to one-side releasing treatment, and then the organic solvent (C) is dried to form a sheet. For application of the ceramic slurry, a roll coater, a blade coater, a die coater, a squeeze coater, a curtain coater, or the like can be used.

The support film used in producing the ceramic green sheet is preferably made of a resin having heat resistance and solvent resistance and having flexibility. The support film is made of a flexible resin so that the ceramic slurry is coated on the support film and the film on which the obtained ceramic green sheet is formed is preserved in a rolled state and can be supplied if necessary.

The resin constituting the support film is not particularly limited and includes, for example, fluororesin such as polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, , Nylon, cellulose, and the like. The thickness of the support film is not particularly limited, and is preferably 20 占 퐉 or more, and preferably 100 占 퐉 or less. It is preferable that the surface of the support film is subjected to a release treatment. Since the releasing treatment is applied to the surface of the supporting film, the releasing operation of the supporting film can be easily performed in the transferring step. As a preferable specific example of the support film, a silicone-coated PET film can be mentioned.

Although the thickness of the ceramic green sheet varies depending on the purpose of use, it can not be collectively specified, but it is preferably 0.1 탆 or more, and preferably 300 탆 or less. The drying temperature at the time of drying the coating film formed on the carrier film differs depending on the thickness of the ceramic green sheet and the like. Therefore, it is preferable that the drying temperature is 25 ° C or higher, and 200 ° C or lower is preferable.

[Coated sheet]

A preferred embodiment of the present invention is a coated sheet obtained by applying a conductive paste to the surface of the above-mentioned ceramic green sheet of the present invention. When the conductive paste is used in combination with the ceramic green sheet of the present invention, it may be a generally used conductive paste.

The method of applying the conductive paste is not particularly limited, and examples thereof include a screen printing method, a die-coat printing method, an offset printing method, a gravure printing method, and an ink-jet printing method. By applying the conductive paste to the surface of the ceramic green sheet, a coated sheet having a conductive paste coating on at least a part of the surface of the ceramic green sheet is obtained.

[TOF-SIMS analysis]

TOF-SIMS analysis is a measurement technique capable of scanning the surface of a measurement object to observe the distribution state of components contained in the measurement object. For example, by dividing a region of 50 to 500 mu m in four directions on the surface of the measurement object into fine regions of 0.1 to 3 mu m in four directions, irradiating primary ions, and observing secondary ions deviating from this minute region, The identification of the kind of the component in the minute region and the intensity of the secondary ion can be measured. This small area is referred to as a primary ion irradiation point. The ratio of the intensity of Ba + ions to the intensity of Ti + ions (the intensity of Ba + ions) / (the intensity of Ti + ions) is a value obtained by dividing the intensity of Ba + by the intensity of Ti + secondary ions.

When the plasma treatment is applied to the surface of the ceramic green sheet, the surface state of the ceramic green sheet may change depending on the preservation state after the plasma irradiation. Therefore, surface measurement by TOF- , It is desirable to perform it quickly. The time from the plasma irradiation to the surface measurement by TOF-SIMS analysis is preferably within 12 hours, more preferably within 3 hours, more preferably within 1 hour, Is most preferable. In the case of analyzing the sheet after the conductive paste is applied, the surface of the ceramic green sheet which is not coated with the conductive paste among the surfaces to which the conductive paste is applied is subjected to surface analysis.

Further, in order to suppress the volatilization of the surface components of the ceramic green sheet during TOF-SIMS analysis, TOF-SIMS analysis is carried out under vacuum, for example, after cooling to -100 to -200 캜 .

[Plasma Treatment]

It is preferable that the ceramic green sheet of the present invention is such that at least a part of at least one surface of the ceramic green sheet is subjected to a plasma treatment. That is, in its production, it is preferable to include a step of applying a plasma treatment to at least one surface of the front surface or back surface of the ceramic green sheet. A ceramic green sheet thus obtained is also a preferred embodiment of the present invention. A plasma treatment is applied to at least one surface of the ceramic green sheet surface or the back surface, and the plasma treated surface and the other ceramic green sheet surface are laminated so as to be in contact with each other. The thus obtained laminate has a good adhesion property as compared with the case where a laminate is produced by using a ceramic green sheet not subjected to a plasma treatment on its surface.

It is preferable that the coated sheet of the present invention is in a state in which at least a part of at least one surface of the surface of the coated sheet is subjected to plasma treatment. That is, in the production thereof, it is preferable to include a step of applying a plasma treatment to at least one surface of the surface of the application sheet. A plasma treatment may be applied to at least a part of at least one surface of the surface of the application sheet. A plasma treatment may be applied to the ceramic green sheet before application of the conductive paste. Alternatively, a plasma treatment may be applied to the application sheet after the conductive paste is applied to the ceramic green sheet. Or a method in which a solvent is added thereto.

Plasma treatment is applied to the surface of the coating sheet coated with the conductive paste, and the plasma-treated surface is laminated so that one side of the other coated sheet is in contact with the surface. The laminate thus obtained exhibits good adhesion as compared with the case where a laminate is produced using a coated sheet having no plasma treatment applied to its surface.

The surface to be subjected to the plasma treatment may be a surface coated with a conductive paste (conductive paste surface), a back surface of a coated sheet (ceramic green sheet surface), or a top surface of a coated sheet. When a plurality of sheets of coated sheets are stacked and stacked to produce a multilayer ceramic capacitor, a plasma treatment may be applied to the conductive paste surface so that the surface of the ceramic green sheet in the other application sheet is in contact with the surface. The laminate thus obtained exhibits good adhesion.

Further, a plasma treatment may be applied to the surface of the ceramic green sheet so that the conductive paste surface of the ceramic green sheet is in contact with the conductive paste surface of another coated sheet. The resulting laminate also exhibits good adhesion. As the coated sheet in this case, a coated sheet formed by applying a conductive paste generally used on the surface of the ceramic green sheet of the present invention is suitably used. Plasma treatment is applied to the front surface or back surface of the coated sheet, and the surface to which the plasma treatment is applied is laminated so that the ceramic green sheet surface or the conductive paste surface in the other coating sheet is in contact with each other. The resulting laminate also exhibits good adhesion.

Further, a plasma treatment may be applied to the ceramic green sheet, and a conductive paste may be applied to the plasma-treated surface. Plasma treatment is applied, and the surface to which the conductive paste is applied is laminated so that one side of the other coated sheet is in contact with the other side. The laminate thus obtained exhibits good adhesion as compared with the case where a laminate is produced by using a coated sheet not subjected to a plasma treatment on its surface. As the coated sheet in this case, a coated sheet formed by applying a conductive paste generally used on the surface of the ceramic green sheet of the present invention is suitably used.

A laminate obtained by laminating a ceramic green sheet with a plasma treatment so that one side of a ceramic green sheet without plasma treatment is in contact with a side to which a conductive paste is applied on a side subjected to plasma treatment and a laminated body in which a ceramic green sheet is laminated without plasma treatment , When the adhesiveness is compared with respect to the laminate obtained by laminating the surface coated with the conductive paste and the surface subjected to the plasma treatment of the ceramic green sheet in contact with each other, the area of the surface of the ceramic green sheet subjected to the plasma treatment is large The latter shows better adhesion. Similarly, a laminate obtained by laminating a ceramic green sheet having one side coated with a conductive paste, a coated side obtained by applying a plasma treatment to a side coated with a conductive paste and one side of a ceramic green sheet not subjected to a plasma treatment, and a ceramic green sheet The surface of the ceramic green sheet coated with the conductive paste is compared with the laminate obtained by laminating the ceramic green sheet so that the surface subjected to the plasma treatment is in contact with the surface of the ceramic green sheet, And the latter having a larger surface area exhibits better adhesion.

The method of the plasma treatment used in the present invention is not particularly limited, and examples thereof include a treatment such as a low-pressure plasma, a high-pressure plasma, a corona discharge treatment, an atmospheric plasma and the like. A suitable treatment method can be used as long as the properties of the present invention are not impaired, but the low-pressure plasma is required to be applied in a vacuum state, which makes it difficult to manufacture in-line. Since the corona treatment becomes high energy, there are cases where the surface shape changes and the treated surface becomes unexpectedly uniform. On the other hand, the atmospheric pressure plasma treatment does not need to be applied in a vacuum state, and energy can be selected at high and low levels. From the viewpoint of productivity and performance, atmospheric plasma is particularly preferable as a treatment method.

For the atmospheric pressure plasma treatment, various atmospheric pressure plasma devices can be used. As the atmospheric pressure plasma apparatus, any apparatus can be used, and various modifications can be selected depending on the purpose of use. For example, an apparatus capable of generating a low-temperature plasma by intermittently discharging an inert gas at a pressure near atmospheric pressure between electrodes covered with a dielectric is preferable. Refers to a range from 70 kPa to 130 kPa, preferably from 90 kPa to 110 kPa in the &quot; atmospheric pressure plasma &quot; in the present invention. The temperature and humidity at the time of performing the atmospheric pressure plasma treatment are not particularly limited and can be appropriately changed, but it is preferable to perform the atmospheric pressure plasma treatment at normal temperature and normal humidity.

As the discharge gas used at the time of generation of the atmospheric plasma, any one of nitrogen, oxygen, hydrogen, carbon dioxide, helium, and argon, or a mixture of two or more of these gases can be used. A dilute gas such as He or Ar which is an inert gas or a nitrogen gas is preferably used and a diluted gas of Ar or He is particularly preferable. For example, when a mixed gas of nitrogen gas and air is used, it is preferable to supply nitrogen gas at a flow rate of 10 L / min or more and 500 L / min or less. It is also preferable to supply dry air at a flow rate of 0.1 L / min or more and 3 L / min or less.

In order to generate a plasma using an atmospheric pressure plasma apparatus, the voltage applied between the electrodes is preferably 5 kv or more, and preferably 15 kv or less. The distance between the electrodes is preferably 1 mm or more, more preferably 2 mm or more. The distance between the electrodes is preferably 10 mm or less, more preferably 5 mm or less.

For example, by moving the ceramic green sheet along the direction perpendicular to the irradiation direction of the plasma while maintaining the state that the surface of the ceramic green sheet to be subjected to the plasma treatment is perpendicular to the irradiation direction of the plasma, The plasma processing can be performed. The time during which the ceramic green sheet passes through directly under the irradiation port is preferably at least 0.1 second, more preferably at least 0.5 second. Further, it is preferably 40 seconds or less, more preferably 20 seconds or less. Further, a plasma atmosphere may also be provided in the vicinity of the under and under the irradiation port.

When the voltage applied between the electrodes, the distance between the electrodes, or the moving speed of the ceramic green sheet is out of the above range, the value of (the intensity of Ba + ions) / (the intensity of Ti + ions) becomes less than 20, There is a tendency.

Example

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. In the following Examples and Comparative Examples, "degree of polymerization" means "viscosity-average degree of polymerization". In the following Examples and Comparative Examples, &quot; ceramic green sheet &quot; means a portion that does not contain a polyester film as a support film.

[Assessment Methods]

(1. Measurement of polyvinyl acetal)

The content (mol%), the degree of acetalization (mol%) and the content (mol%) of the vinyl alcohol monomer units in the polyvinyl acetal used in Examples and Comparative Examples were measured according to JIS K 6728: 1977 Respectively. The viscosity average degree of polymerization of the polyvinyl acetal is represented by the viscosity average degree of polymerization of the PVA of the starting material measured in accordance with JIS K 6727: 1994.

(2. Measurement of acid value of organic compound)

The acid value of the organic compound used in Examples and Comparative Examples was measured according to JIS K 6728: 1977. More specifically, about 1 g of each organic compound was added to an Erlenmeyer flask equipped with a stirrer, and 30 ml of ethyl alcohol was added to dissolve. Phenolphthalein was used as an indicator, and the obtained solution was titrated with N / 50 potassium hydroxide, and the appropriate amount up to the point where the red color was maintained for 30 seconds or more was defined as a (mL). Separately, 30 ml of ethyl alcohol was subjected to the same titration to give an appropriate amount of b (mL) up to the point of keeping the red color, and the acid value was calculated by the following formula II.

[Formula II]

(TOF-SIMS analysis of ceramic green sheet surface)

In order to suppress the volatilization of the surface of the ceramic green sheet surface during the measurement, the time-of-flight secondary ion mass spectrometry (TOF-SIMS) was carried out for cooling measurement. After the surface of the ceramic green sheet obtained in Production Example was subjected to atmospheric pressure plasma treatment, the ceramic green sheet was cooled to -150 ° C, and thereafter, under vacuum, directly by time-of-flight secondary ion mass spectrometry (TOF-SIMS) Analysis. The time-of-flight secondary ion mass spectrometer (TOF-SIMS) was a TOF-SIMS 5 manufactured by ION-TOF. A bismuth cluster ion source (Bi3 + +) was used as the primary ion source, and a current value of 0.2 picomapole and an acceleration voltage of 25 kilovolts were used. In the measurement mode, a high mass resolution normal mode (bunching mode) was selected. 500 占 퐉 x 500 占 퐉 arbitrarily on the plane of the ceramic green sheet (any one of the surfaces having the largest area of the ceramic green sheet) was defined as a measurement region, the measurement region was divided into a measurement range of 128 占 128 pixels, In the irradiation mode, the measurement area was scanned in the random cluster mode, and the number of scans was 64 scans. The intensity of the Ti + ions and the intensity of the Ba + ions were calculated from the mass spectrum obtained by the measurement, and the ratio of the intensity of the Ba + ions to the intensity of the Ti + ions was calculated. The results are shown in Tables 2-1, 2-2, and 3. Since the surface state of the sheet after the plasma irradiation may change depending on the storage state, the surface analysis after the plasma irradiation was measured quickly after the plasma irradiation.

(4-1 Evaluation of adhesion of ceramic green sheet)

The ceramic green sheets used in the examples and comparative examples, which were subjected to the atmospheric pressure plasma treatment under the following conditions, and the ceramic green sheets used in the examples and the comparative examples which were not subjected to the atmospheric pressure plasma treatment, were laminated and heat- And subjected to a thermocompression test under the same conditions. At this time, the surface subjected to the atmospheric pressure plasma treatment was laminated so as to be in contact with the surface of the other ceramic green sheets not subjected to the atmospheric pressure plasma treatment, thereby obtaining a laminate.

<Plasma Investigation>

The ceramic green sheet (on the polyester film) used in Examples and Comparative Examples was cut into a size of 10 cm x 10 cm together with the polyester film. The ceramic green sheet was peeled off from the polyester film, and then the surface of the ceramic green sheet was subjected to a heat treatment at room temperature and normal humidity using an atmospheric pressure plasma apparatus, a nitrogen gas at a flow rate of 150 L / min, The time required for the ceramic green sheet to pass directly under the irradiation port having a width of 2 cm was 2 seconds (10 cm / sec) at a voltage of 11 kV between electrodes, a distance of 2 mm between electrodes, and a moving speed of a sample (ceramic green sheet) 10 seconds with respect to the whole ceramic green sheet of 10 cm).

&Lt; Heat press condition >

Press temperature 45 ℃

Pressure 1 MPa

5 seconds

The obtained laminate was cut into 5 mm x 5 mm, and 100 pieces were arbitrarily extracted. The adhesion surface of the randomly extracted laminate was visually observed, and the adhesion between the ceramic green sheets was evaluated by the following five steps.

A: No delamination was observed at all, and they were strongly adhered.

(The number of laminated layers delaminated / the optional laminated layer = 1/100)

B: A slight interlaminar peeling was confirmed, but it was firmly adhered.

(The number of laminated layers delaminated / the optional laminated layer = 1 to 10/100)

C: The interlaminar peeling was partially confirmed, but it was bonded.

(The number of laminated layers delaminated / the optional laminated layer = 11 to 30/100)

D: The delamination between the layers was confirmed to be considerably large, showing almost no adhesion.

(The number of laminated layers delaminated / the optional laminated layer = 31 to 99/100)

E: No adhesion was observed.

(The number of laminated layers delaminated / the optional laminated layer = 100/100)

(4-2 Evaluation of adhesion of coated sheet)

Other than using a ceramic green sheet, a coated sheet used in Examples and Comparative Examples was used. Evaluation of Adhesion of Ceramic Green Sheet &quot;. At this time, the atmospheric pressure plasma treatment was laminated so that the surface subjected to the atmospheric pressure plasma treatment was in contact with the surface to which the conductive paste had not been applied (the surface not coated with the conductive paste) of the other coated sheet .

(5-1 Evaluation of dimensional stability of ceramic green sheet)

The ceramic green sheet used in Examples and Comparative Examples, having a thickness of 2 mu m after drying (air drying at room temperature for 1 hour, drying with a hot air drier at 80 DEG C for 2 hours, and then 120 DEG C for 2 hours) Treatment. This sheet was cut at 5 cm square and two sheets were superimposed and combined and pressed at 45 ° C (press pressure: 3 MPa) to obtain a strain (area after pressing / area before pressing × 100). At this time, the surface subjected to the atmospheric pressure plasma treatment was laminated so as to be in contact with the surface of the other ceramic green sheets not subjected to the atmospheric pressure plasma treatment.

A: Less than 2% sheet strain

B: Sheet strain is 2% or more and less than 4%

C: Strain more than 4%

.

(5-2 Evaluation of dimensional stability of coated sheet)

Except for using the coated sheet used in the examples and comparative examples in place of the ceramic green sheet, &quot; 5-1. Evaluation of dimensional stability of ceramic green sheet &quot;. At this time, the atmospheric pressure plasma treatment was performed on the surface to which the conductive paste had been applied, and the surface subjected to the atmospheric pressure plasma treatment was laminated so as to be in contact with the surface of the other application sheet not subjected to the atmospheric pressure plasma treatment .

(6-1 Evaluation of delamination of fired bodies in a ceramic green sheet laminate)

100 sheets of the ceramic green sheets (on the polyester film) used in Examples and Comparative Examples were cut at a 10-cm square. The cut ceramic green sheet was peeled off from the polyester film, Evaluation of Adhesion of Ceramic Green Sheet &quot;, 100 sheets were superimposed on the atmospheric pressure plasma treated surface and the atmospheric pressure non-treated surface, and a stack of ceramic green sheets was obtained. Subsequently, the laminate was heated and pressed at a temperature of 70 占 폚 and a pressure of 150 kg / cm2 for 10 minutes to obtain a laminate. The obtained laminate was cut into a size of 5 mm x 5 mm and 100 pieces were arbitrarily extracted from the cut laminate. The laminate was heated to 400 deg. C at a temperature raising rate of 15 deg. C / min under a nitrogen atmosphere, held for 5 hours, The temperature was raised to 1,350 占 폚 at a rate of 5 占 폚 / min and maintained for 10 hours to obtain a ceramic sintered body.

After the obtained fired body was cooled to room temperature, the cross section of the fired body was observed by an electron microscope, and the presence or absence of delamination between the ceramic layers was evaluated in the following four steps.

A: No delamination.

(Number of delaminated sintered bodies / arbitrary sintered body = 0 to 2/100)

B: Some delamination appears.

(Number of delaminated sintered bodies / arbitrary sintered body = 3 to 7/100)

C: There is some delamination.

(Number of delaminated sintered bodies / arbitrary sintered body = 8 to 20/100)

D: There are many delaminations.

(Number of delaminated sintered bodies / arbitrary sintered body = 21 to 100/100)

(6-2 Evaluation of Delamination of Sintered Body in Coated Sheet Laminate)

100 sheets of the coated sheets used in Examples and Comparative Examples were cut at a 10-cm square. On the surface to which the conductive paste is applied, "4-2. Evaluation of Adhesion of Coated Sheet &quot;, and 100 sheets superimposed on the surfaces subjected to the atmospheric pressure plasma treatment and the surfaces not subjected to the atmospheric pressure plasma treatment were piled up to obtain a laminate of the coated sheet. Subsequently, the laminate was heated and pressed at a temperature of 70 占 폚 and a pressure of 150 kg / cm2 for 10 minutes to obtain a laminate. The obtained laminate was cut into a size of 5 mm x 5 mm and 100 pieces were arbitrarily extracted from the cut laminate. The laminate was heated to 400 deg. C at a temperature raising rate of 15 deg. C / min under a nitrogen atmosphere, held for 5 hours, The temperature was raised to 1,350 占 폚 at a rate of 5 占 폚 / min and maintained for 10 hours to obtain a ceramic calcined body.

After the obtained sintered body was cooled to room temperature, the cross section of the sintered body was observed by an electron microscope, and the presence or absence of delamination between the ceramic layers and between the ceramic layer and the electrode layer was evaluated in the following four steps.

A: No delamination.

(Number of delaminated sintered bodies / arbitrary sintered body = 0 to 2/100)

B: Some delamination appears.

(Number of delaminated sintered bodies / arbitrary sintered body = 3 to 7/100)

C: There is some delamination.

(Number of delaminated sintered bodies / arbitrary sintered body = 8 to 20/100)

D: There are many delaminations.

(Number of delaminated sintered bodies / arbitrary sintered body = 21 to 100/100)

[Binder resin (A)]

(Synthesis Example 1)

780 g of ion-exchanged water and 720 g of polyvinyl alcohol (hereinafter referred to as PVA-1) having a polymerization degree of 1,700 and a degree of saponification of 98.4 mol% were introduced into a 10-liter glass container provided with a reflux condenser, a thermometer and an anchor- PVA concentration: 9.0% by mass), and the contents were heated to 95 DEG C to completely dissolve the PVA. Subsequently, the contents were cooled gradually to 10 캜 over about 30 minutes while stirring at 120 rpm, 400 g of n-butylaldehyde and 830 mL of 20% by mass hydrochloric acid were added to the vessel, and the butyralization reaction was carried out for 150 minutes. Thereafter, the temperature was raised to 70 캜 over 90 minutes, maintained at 70 캜 for 120 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and neutralized by adding an excess amount of sodium hydroxide aqueous solution. Subsequently, the resin was washed with ion-exchanged water and dried to obtain polyvinyl butyral (PVB-1).

(Synthesis Example 2)

Polyvinyl butyral (PVB-2) was obtained in the same manner as in Synthesis Example 1 except that PVA having the degree of polymerization and degree of saponification shown in Table 1 was used instead of PVA-1 and 336 g of n-butylaldehyde was used.

(Synthesis Example 3)

Polyvinylbutyral (PVB-3) was obtained in the same manner as in Synthesis Example 1 except that PVA having the degree of polymerization and degree of saponification shown in Table 1 was used instead of PVA-1 and 388 g of n-butylaldehyde was used.

(Synthesis Example 4)

Polyvinyl butyral (PVB-4) was obtained in the same manner as in Synthesis Example 1 except that PVA having the degree of polymerization and degree of saponification shown in Table 1 was used instead of PVA-1 and 453 g of n-butylaldehyde was used.

(Synthesis Example 5)

Polyvinyl butyral (PVB-5) was obtained in the same manner as in Synthesis Example 1 except that PVA having the degree of polymerization and degree of saponification shown in Table 1 was used instead of PVA-1 and 511 g of n-butylaldehyde was used.

(Synthesis Example 6)

Instead of PVA-1, polyvinyl butyral (PVB-6) was obtained in the same manner as in Synthesis Example 1 except that PVA having the degree of polymerization and degree of saponification shown in Table 1 was used and 398 g of n-butylaldehyde was used.

(Synthesis Example 7)

Polyvinyl butyral (PVB-7) was obtained in the same manner as in Synthesis Example 1 except that PVA having the degree of polymerization and degree of saponification shown in Table 1 was used instead of PVA-1 and 405 g of n-butyl aldehyde was used.

(Synthesis Example 8)

Polyvinyl butyral (PVB-8) was obtained in the same manner as in Synthesis Example 1 except that PVA having the degree of polymerization and degree of saponification shown in Table 1 was used instead of PVA-1 and 399 g of n-butyl aldehyde was used.

(Synthesis Example 9)

Instead of PVA-1, PVA having a degree of polymerization of 2,400 and a degree of saponification of 98.9 mol% and PVA having a degree of polymerization of 500 and a degree of saponification of 98.8 mol% were used in a weight ratio of 70/30, and n-butylaldehyde (PVB-9) was obtained in the same manner as in Synthesis Example 1 except that 399 g of polyvinyl butyral was used.

(Synthesis Example 10)

Polyvinylbutyral (PVB-10) was obtained in the same manner as in Synthesis Example 1, except that acetalization was carried out using isobutylaldehyde instead of butyralization using n-butylaldehyde in Synthesis Example 1, &Lt; / RTI &gt;

(Synthesis Example 11)

The procedure of Synthesis Example 1 was repeated, except that acetalization was carried out using acetaldehyde and n-butylaldehyde in a weight ratio of 100/64, instead of butyralization using n-butylaldehyde, Polyvinyl butyral (PVB-11) was obtained.

With regard to PVB-1 to PVB-11, Measurement of polyvinyl acetal ", the polymerization degree, the content of the vinyl acetate monomer unit, the degree of butyralization and the content of the vinyl alcohol monomer unit were measured. The measurement results are shown in Table 1.

[Table 1]

[Production of ceramic green sheet]

(Production Example 1)

<Preparation of Inorganic Compound Dispersing Agent>

10 parts by mass of PVB-1 was added to a mixed solvent of 30 parts by mass of toluene and 30 parts by mass of ethanol, followed by stirring to dissolve PVB-1. To this solution, 100 parts by mass of adipic acid bis (2-butoxyethyl) To 38 parts by mass based on PVB-1, and the mixture was stirred to prepare an inorganic compound dispersing solvent.

&Lt; Preparation of ceramic slurry >

15 parts by mass of toluene and 15 parts by mass of ethanol were added to 100 parts by mass of barium titanate (&quot; BT-02 &quot;, manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter 0.2 탆) and mixed with a ball mill for 15 hours. . Subsequently, the inorganic compound-dispersing solvent was added to the dispersion of ceramics so that 7.5 parts by mass of PVB-1 was added to 100 parts by mass of the ceramic, and the mixture was mixed with a ball mill for 24 hours to obtain a ceramic slurry.

&Lt; Preparation of ceramic green sheet &

The resulting ceramic slurry was applied on a release film of a polyester film using a bar coater so as to have a dry film thickness of 2 to 3 占 퐉, air-dried at room temperature for 1 hour, then heated at 80 占 폚 for 2 hours And dried at 120 ° C for 2 hours to obtain a ceramic green sheet (GS-1) on the polyester film.

(Production Examples 2 to 8)

Ceramic green sheets (GS-2 to GS-8) were produced in the same manner as in Production Example 1 except that PVB-2 to PVB-8 were used instead of PVB-1.

(Production Examples 9 to 14)

Ceramic green sheets (GS-9 to GS-14) were prepared in the same manner as in Production Example 1 except that the organic compounds described in Table 2-1 were used instead of adipic acid bis (2-butoxyethyl).

(Production Examples 15 to 18)

(GS-15 to GS-5) were obtained in the same manner as in Production Example 1, except that adipic acid bis (2-butoxyethyl) was added to the binder resin -18).

(Production Examples 19 to 21)

Production of ceramic green sheets (GS-19 to GS-21) was carried out in the same manner as in Production Example 1 except that PVB-9 to PVB-11 were used instead of PVB-1 and the organic compounds described in Table 2-2 were used Respectively.

(Preparation Example 22)

As shown in Table 2-2, 19 parts by mass of adipic acid bis (2-butoxyethyl) and 19 parts by mass of triethylene glycol di-2-ethylhexanoate were added to 100 parts by mass of PVB-1 A ceramic green sheet (GS-22) was produced in the same manner as in Production Example 1 except for the above.

(Production Examples 23 to 25)

As shown in Table 2-2, ceramic green sheets (GS-23 to GS-25) were produced in the same manner as in Production Example 1 except that adipic acid bis (2-butoxyethyl) Respectively. Further, the acid values of adipic acid bis (2-butoxyethyl) used in Production Examples 23 to 25 are different from each other because the content of acid components derived from adipic acid is different.

(Preparation Examples A to H)

Ceramic green sheets (GS-A to GS-H) were prepared in the same manner as in Production Example 1 except that the organic compounds listed in Table 3 were used instead of adipic acid bis (2-butoxyethyl).

(Preparation Example I)

A ceramic green sheet (GS-I) was produced in the same manner as in Production Example 1, except that adipic acid bis (2-butoxyethyl) was not used as shown in Table 3.

With respect to the obtained ceramic green sheets (GS-A to GS-I), the above evaluation method "2. The acid value of the organic compound used in the production of each ceramic green sheet was measured according to the method described in &quot; Measurement of acid value of organic compound &quot;. Table 3 shows the measurement results.

With respect to the obtained ceramic green sheets (GS-1 to GS-25, GS-A to GS-I) The acid value of the organic compound used in the production of each ceramic green sheet was measured according to the method described in &quot; Measurement of acid value of organic compound &quot;. Table 2-1, Table 2-2 and Table 3 show the measurement results.

[Table 2-1]

[Table 2-2]

[Table 3]

[Production of conductive paste, coated sheet and laminate]

(Production Example 1)

<Production of conductive paste>

Ethyl cellulose (STD-45, manufactured by Dow Chemical Company) and dihydroterephinyl acetate were added to a 2-liter separable flask equipped with a stirrer, a condenser, a thermometer, a hot water bath and a nitrogen gas inlet.

Subsequently, a nickel powder ("NFP201", manufactured by JFE Mineral Co., Ltd.) as a conductive powder was mixed, and 20 parts by mass of commercially available barium titanate powder having an average particle diameter of 0.1 mu m was added to the nickel powder. Several times to obtain a conductive paste. The composition ratio in the conductive paste was adjusted so that the binder resin (A) was 3 mass%, the nickel component was 50 mass%, the barium titanate was 10 mass%, and others were organic solvents to obtain a conductive paste.

<Production of Coated Sheet>

The ceramic green sheet (GS-1) obtained in Production Example 1 was cut into a size of 10 cm x 10 cm, and the above evaluation method "4-1. Evaluation of Adhesion of Ceramic Green Sheet &quot;, atmospheric pressure plasma treatment was applied. The conductive paste was screen-printed on the surface to which the atmospheric pressure plasma treatment was applied by a screen printing machine (DP-320, manufactured by Neunongshim Kogyo K.K.) and dried at 120 DEG C for 1 hour to obtain a 10 mm square, ) 2.5 mm, and a film thickness of 2 탆 was formed to obtain a coated sheet (TS-1).

(Production Example 2)

The ceramic green sheet (GS-1) obtained in Production Example 1 was cut into a size of 10 cm x 10 cm, and the above-mentioned conductive paste was screen-printed by a screen printing machine (DP-320 manufactured by Neunongshim Kogyo K.K.) , And dried at 120 DEG C for 1 hour to form a conductive paste film having a thickness of 10 mm, a paste distance (margin) of 2.5 mm, and a thickness of 2 mu m. On the surface on which the conductive paste film was formed, the above evaluation method "4-1. (TS-2) was obtained by applying atmospheric pressure plasma treatment according to the method described in &quot; Evaluation of Adhesion of Ceramic Green Sheet &quot;.

(Production Example 3)

A coated sheet (TS-3) was obtained in the same manner as in Production Example 2 except that GS-C was used instead of the ceramic green sheet (GS-1).

TS-1 to TS-3 are shown in Table 4.

[Table 4]

[Example]

(Examples 1 to 25)

With respect to each of the ceramic green sheets (GS-1 to GS-25), the dimensional stability at the time of compression of the ceramic green sheets, the adhesiveness of the ceramic green sheets and the delamination of the sintered bodies obtained using the ceramic green sheets The evaluation was carried out according to the method described in the above evaluation method. The evaluation results are shown in Table 5.

(Example 26)

The dimensional stability at the time of compression of TS-1, the adhesive property of TS-1 and the delamination of the sintered body obtained using TS-1 were evaluated according to the method described in the above evaluation method. The evaluation results are shown in Table 5.

(Example 27)

With respect to the coated sheet (TS-2), the dimensional stability at the time of pressing of TS-2 and the adhesive property of TS-2 were evaluated according to the method described in the above evaluation method. The evaluation results are shown in Table 7.

[Comparative Example]

(Comparative Examples 1 to 9)

With respect to each of the ceramic green sheets (GS-A to GS-I), the dimensional stability at the time of pressing of the ceramic green sheets, the adhesiveness of the ceramic green sheets and the delamination of the sintered bodies obtained using the ceramic green sheets , And the evaluation was carried out according to the method described in the above evaluation method. The evaluation results are shown in Table 6.

(Comparative Example 10)

Evaluation was carried out in the same manner as in Example 1 except that the sample moving speed at the time of plasma irradiation was 0.1 mm / sec. The ratio of the intensity of the Ba + ions to the intensity of the Ti + ions on the surface of the ceramic green sheet at this time was 1,064. The evaluation results are shown in Table 6.

(Comparative Example 11)

With respect to the coated sheet (TS-3), the dimensional stability at the time of pressing of TS-3 and the adhesiveness of TS-3 were evaluated according to the method described in the above-mentioned evaluation method. The evaluation results are shown in Table 7.

[Table 5]

[Table 6]

[Table 7]

Claims (11)

When at least one surface of the ceramic green sheet is subjected to secondary ion analysis using a time-of-flight (time-of-flight) secondary ion analyzer, the intensity of the detected Ba + ions (Intensity of Ba + ion) / (intensity of Ti + ion) satisfy 20 <(intensity of Ba + ion) / (intensity of Ti + ion) <1,000. The positive resist composition according to claim 1, wherein the binder resin (A) having a hydroxyl group in the molecule and the binder resin (A)
[Chemical Formula 1]

(In the formula 1,
R1 and R4 each independently represent an organic group having at least one ether bond,
R2 is an alkylene group having 1 to 20 carbon atoms which may have a branch,
R3 is an alkylene group which may have a branch having 1 to 4 carbon atoms,
and m is an integer of 0 to 5)
(B) represented by the following formula (1). The ceramic green sheet according to claim 2, wherein the acid value of the organic compound (B) is 5 mg KOH / g or less. 4. A compound according to claim 2 or 3, wherein R &lt; 1 &gt; and / or R &
(2)

(In the formula (2)
R5 is an alkyl group having 1 to 10 carbon atoms which may have a branch,
R6 is an alkylene group having 1 to 10 carbon atoms which may have a branch,
R7 is an alkylene group having 1 to 4 carbon atoms,
and n is an integer of 0 to 2)
Is an organic group having at least one ether bond. The ceramic green sheet according to any one of claims 2 to 4, wherein the ceramic green sheet contains 1 to 60 parts by mass of the organic compound (B) relative to 100 parts by mass of the binder resin (A). The ceramic green sheet according to any one of claims 2 to 5, wherein the binder resin (A) comprises at least one member selected from the group consisting of polyvinyl acetal and (meth) acrylic resin. The polyvinyl acetal according to claim 6, wherein the binder resin (A) comprises polyvinyl acetal, the acetylation degree of the polyvinyl acetal is 50 to 85 mol%, the content of the vinyl ester monomer unit is 0.1 to 20 mol% A ceramic green sheet having an average degree of polymerization of 200 to 5,000. The ceramic green sheet according to any one of claims 2 to 7, which contains barium titanate and contains 3 to 20 parts by mass of the binder resin (A) per 100 parts by mass of barium titanate. A coated sheet comprising a ceramic green sheet according to any one of claims 1 to 8, wherein at least one surface of the ceramic green sheet is provided with a layer in which a conductive paste is dried. The coated sheet according to claim 9, wherein at least a part of the ceramic green sheet is subjected to a plasma treatment. The coated sheet according to claim 9 or 10, wherein at least a part of the surface of the application sheet is subjected to a plasma treatment.