JPWO2018021439A1 - Ceramic green sheet and coated sheet - Google Patents

Abstract

An object of the present invention is to provide a ceramic green sheet which is excellent in adhesion at the time of pressure bonding and in which delamination hardly occurs. A coated sheet obtained by applying an arbitrary conductive paste to a ceramic green sheet is excellent in adhesion at the time of pressure bonding, and provides a ceramic green sheet in which delamination hardly occurs. This is the ratio of the detected Ba + ion intensity to the detected Ti + ion intensity when performing secondary ion analysis with a time-of-flight secondary ion analyzer on at least one side of the ceramic green sheet (Ba + ion A ceramic green sheet in which the strength of () / (Ti + ion strength) satisfies 20 <(Ba + ion strength) / (Ti + ion strength) <1000.

Description

  The present invention relates to a ceramic green sheet which is excellent in adhesion at the time of pressure bonding and in which dimensional change at the time of pressure bonding is small. Furthermore, the present invention relates to a coated sheet which is excellent in adhesiveness at the time of pressure bonding.

  Various polymers have been proposed because polyvinyl acetal is a unique film having both a hydrophilic hydroxyl group and a hydrophobic acetal group, as it can provide a tough film.

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

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

  In addition, polyvinyl acetal is also used as a binder for conductive paste used in the production of multilayer ceramic capacitors and the like. In the step of forming the electrode layer, a method of directly forming the electrode layer on the ceramic green sheet by printing, an electrode layer is formed on the carrier film by printing or the like, and the electrode layer is heated from the carrier film to the ceramic green sheet There is a method of transferring by press.

  Here, the laminated ceramic capacitor is a chip type ceramic capacitor in which a dielectric such as titanium oxide or barium titanate and an internal electrode are stacked in multiple layers. Such a multilayer ceramic capacitor is obtained, for example, by stacking a plurality of conductive green sheets coated with conductive paste to be internal electrodes by screen printing or the like, and heat pressing them to obtain a laminate, and then heating the laminate. Then, the binder is decomposed and removed (degreased) and can be manufactured by firing. In some cases, ceramic green sheets in which a circuit is not formed by conductive paste may be laminated. Among them, barium titanate is widely used in multilayer ceramic capacitors because it is a high dielectric.

  In recent years, with the multifunctionalization and miniaturization of electronic devices, a multilayer ceramic capacitor is required to have a large capacity and a miniaturization. Attempts have been made to meet these requirements by reducing the thickness of the ceramic green sheets and further laminating the layers of the multilayer ceramic capacitor. For example, as a method of making a thin film, as a ceramic powder used for a ceramic green sheet, one having a fine particle diameter of 0.5 μm or less is used, and a thin film such as 5 μm or less on a peelable support Attempts have been made to coat it.

  On the other hand, when making a laminated ceramic capacitor, if the pressure bonding is strengthened in the step of temporarily pressing the ceramic green sheet, the ceramic green sheet and the conductor layer will be deformed, making it difficult to achieve high precision required for the laminated ceramic component Met. On the other hand, when the pressure bonding is weakened, in the conventional manufacturing method, the adhesion between the ceramic green sheets or between the ceramic green sheets and the conductor layer is weak, and the upper and lower ceramic green sheets or ceramic green sheets may not adhere to the electrode layer. . If such an adhesion failure occurs, there is a problem that a cutting failure due to displacement of the bonding surface, defects such as delamination occur after firing the ceramic laminate, and the reliability of the parts is lowered. Moreover, when an excess plasticizer is mix | blended in order to improve adhesiveness, it deform | transformed at the time of pressure bonding, and there existed a problem that it was difficult to obtain a desired lamination sheet.

  As an attempt to solve the above problems, for example, Patent Document 1 describes using a ceramic slurry containing a phthalic acid plasticizer and a glycol plasticizer and / or an amino alcohol plasticizer. Patent Document 2 describes a ceramic paste which has a high plasticizing effect and contains appropriate volatility. Patent Document 3 describes a manufacturing method in which a film is subjected to surface treatment using an atmospheric plasma device to improve adhesion.

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

  However, as described above, the particle size of barium titanate is being minimized for film thinning. When ceramic powder with a fine particle size is used, the packing density and the surface area increase, so the surface of barium titanate can not be covered sufficiently, and barium titanate itself is present on the surface of the ceramic green sheet. In order to laminate thin films of ceramic green sheets in multiple layers due to poor adhesion between layers and multilayer ceramic capacitors further, if resin decomposition proceeds at once during degreasing, delamination occurs called delamination, as described above, resulting in parts Reliability may be reduced.

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

  Another object of the present invention is to provide a coated sheet having excellent adhesion at the time of pressure bonding, which is obtained by coating an arbitrary conductive paste on the ceramic green sheet of the present invention.

  Another object of the present invention is to provide a ceramic green sheet and a coated sheet which are less likely to cause delamination when the ceramic green sheet and / or the coated sheet of the present invention are laminated to produce a sintered body.

（式中、Ｒ１およびＲ４は、それぞれ独立してエーテル結合を少なくとも一つ有する有機基を表す。Ｒ２は、炭素数１〜２０の分岐を有してもよいアルキレン基を表す。Ｒ３は、炭素数１〜４の分岐を有してもよいアルキレン基を表す。ｍは０〜５の整数を表す。）で表される有機化合物（Ｂ）を少なくとも含む、［１］のセラミックグリーンシート；
［３］有機化合物（Ｂ）の酸価が５ｍｇＫＯＨ／ｇ以下である、［２］のセラミックグリーンシート；［４］Ｒ１および／またはＲ４がそれぞれ独立して、化学式（２）：

（式中、Ｒ５は炭素数１〜１０の分岐を有してもよいアルキル基を表す。Ｒ６は炭素数１〜１０の分岐を有してもよいアルキレン基を表す。Ｒ７は炭素数１〜４のアルキレン基を表す。ｎは０〜２の整数を表す。）で表されるエーテル結合を少なくとも一つ有する有機基である、［２］または［３］のセラミックグリーンシート；
［５］バインダー樹脂（Ａ）１００質量部に対して、有機化合物（Ｂ）を１〜６０質量部含有する、［２］〜［４］のいずれかのセラミックグリーンシート；
［６］バインダー樹脂（Ａ）が、ポリビニルアセタールおよび（メタ）アクリル樹脂からなる群より選ばれる少なくとも１種を含む、［２］〜［５］のいずれかのセラミックグリーンシート；
［７］バインダー樹脂（Ａ）がポリビニルアセタールを含み、該ポリビニルアセタールは、アセタール化度が５０〜８５モル％であり、ビニルエステル単量体単位の含有量が０．１〜２０モル％であり、粘度平均重合度が２００〜５０００である、［６］のセラミックグリーンシート；
［８］チタン酸バリウムを含み、チタン酸バリウム１００質量部に対して、バインダー樹脂（Ａ）を３〜２０質量部含有する、［２］〜［７］のいずれかのセラミックグリーンシート。；
［９］［１］〜［８］のいずれかのセラミックグリーンシートの少なくとも一方の面に、導電ペーストを乾燥させた層を配置してなる塗工シート；
［１０］セラミックグリーンシートの少なくとも一部にプラズマ処理が施された、［９］の塗工シート；
［１１］塗工シートの表面の少なくとも一部にプラズマ処理が施された、［９］または［１０］の塗工シート；
を提供することにより達成される。According to the invention said object is
[1] The ratio of the detected Ba + ion intensity to the detected Ti + ion intensity when performing secondary ion analysis with a time-of-flight secondary ion analyzer on at least one side of the ceramic green sheet A ceramic green sheet in which (Intensity of Ba + ion) / (Intensity of Ti + ion) satisfies 20 <(Intensity of Ba + ion) / (Intensity of Ti + ion) <1000;
[2] A binder resin (A) having a hydroxyl group in the molecule, and a chemical formula (1):

(Wherein, R 1 and R 4 each independently represent an organic group having at least one ether bond. R 2 represents an alkylene group having 1 to 20 carbon atoms which may have a branch. R 3 represents carbon) The ceramic green sheet according to [1], which at least contains the organic compound (B) represented by the formula: m represents an integer of 0 to 5).
[3] The ceramic green sheet of [2], wherein the acid value of the organic compound (B) is 5 mg KOH / g or less; [4] R 1 and / or R 4 are each independently a chemical formula (2):

(Wherein, R 5 represents an alkyl group which may have a C 1 to C 10 branched chain. R 6 represents an alkylene group which may have a C 1 to C 10 branched chain. R 7 has a carbon number 1 to 1 A ceramic green sheet of [2] or [3] which is an organic group having at least one ether bond represented by: n represents an integer of 0 to 2;
[5] The ceramic green sheet according to any one of [2] to [4], containing 1 to 60 parts by mass of the organic compound (B) relative to 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) contains at least one selected from the group consisting of polyvinyl acetal and (meth) acrylic resin;
[7] The binder resin (A) contains a polyvinyl acetal, and the polyvinyl acetal has a degree of acetalization of 50 to 85 mol%, and a content of vinyl ester monomer units of 0.1 to 20 mol%. A ceramic green sheet according to [6], having a viscosity average polymerization degree of 200 to 5,000;
[8] The 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) with respect to 100 parts by mass of barium titanate. ;
[9] A coated sheet obtained by arranging a layer obtained by drying a conductive paste on at least one surface of the ceramic green sheet according to any one of [1] to [8];
[10] The coated sheet of [9], wherein at least a part of the ceramic green sheet is plasma-treated;
[11] The coated sheet of [9] or [10], wherein at least a part of the surface of the coated sheet is subjected to plasma treatment;
Is achieved by providing

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

  Moreover, when the ceramic green sheet and / or the coating sheet of this invention are laminated | stacked and a sintered body is produced, the ceramic green sheet and coating sheet which delamination does not produce easily can be provided.

  In the ceramic green sheet of the present invention, when the bonded surface of the ceramic green sheet is subjected to secondary ion analysis with a time-of-flight secondary ion analyzer, the Ba + ion relative to the strength of Ti + ion detected as a cation The present invention relates to a ceramic green sheet in which the ratio of strength satisfies 20 <(strength of Ba + ions) / (strength of Ti + ions) <1000.

[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 referred to as "binder resin (A)") include polyvinyl acetal, polyvinyl alcohol, (meth) acrylic resin having a hydroxyl group, and polyacrylic acid And polyalkylene oxides. Among them, polyvinyl acetal or a (meth) acrylic resin having a hydroxyl group is preferable, and polyvinyl acetal is more preferable, in terms of the dispersibility of the inorganic compound and the flexibility and adhesiveness of the ceramic green sheet and the coating sheet.

(Polyvinyl acetal)
When the polyvinyl acetal is contained in the binder resin (A), 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, and 50% by mass The content is more preferably 70% by mass or more, and most preferably 100% by mass.

  The acetalization degree of the polyvinyl acetal is preferably 50 mol% or more, more preferably 55 mol% or more, still more preferably 60 mol% or more, and particularly preferably 65 mol% or more . The degree of acetalization of the polyvinyl acetal is preferably 85 mol% or less, more preferably 82 mol% or less, still more preferably 78 mol% or less, particularly preferably 75 mol% or less preferable. The degree of acetalization represents the ratio of acetalized vinyl alcohol monomer units to all the monomer units constituting the polyvinyl acetal. When the degree of acetalization exceeds 85 mol%, the efficiency of the acetalization reaction tends to decrease.

  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, and further preferably 0.5 mol% or more. Preferably, it is 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, and 13 mol% or less Is particularly preferred. When the content of the vinyl ester monomer unit is less than 0.1 mol%, undissolved polyvinyl alcohol may be formed when dissolving polyvinyl alcohol in a solvent for acetalization, which is obtained The quality of polyvinyl acetal tends to be degraded.

  The content of the vinyl alcohol monomer unit of the polyvinyl acetal is preferably 15% by mole or more, and more preferably 25% by mole 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 still more 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 20 mol% It is preferable that it is the following and it is more preferable that it is 10 mol% or less.

により求めることができる。ＰＶＡの粘度平均重合度と、それをアセタール化して得られるポリビニルアセタールの粘度平均重合度とは、実質的に同じである。The viscosity average polymerization degree of the polyvinyl acetal is preferably 200 or more, and more preferably 5,000 or less. A more preferable range will be described later. In addition, the viscosity average polymerization degree of the polyvinyl acetal contained in binder resin (A) is a raw material polyvinyl alcohol (It may abbreviate as "PVA" hereafter) measured based on JIS K 6726: 1994. It is expressed by viscosity average degree of polymerization. That is, after re-saponifying PVA to a degree of saponification of 99.5 mol% or more and purifying it, the intrinsic viscosity [η] (l / g) measured in water at 30 ° C., the formula (I):

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

(Method for producing polyvinyl acetal)
The polyvinyl acetal is usually produced by acetalizing PVA.

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

  When the saponification degree of raw material PVA exceeds 99.9 mol%, PVA may not be able to be manufactured stably. The degree of saponification of PVA is measured in accordance with JIS K 6726: 1994.

  The raw material PVA can be obtained by a conventionally known method, that is, by polymerizing a vinyl ester monomer and saponifying the obtained polymer. As a method of polymerizing a vinyl ester monomer, conventionally known methods such as solution polymerization method, bulk polymerization method, suspension polymerization method, and emulsion polymerization method can be applied. As the polymerization initiator, an azo-based initiator, a peroxide-based initiator, a redox-based initiator, and the like are appropriately selected according to the polymerization method. As the saponification reaction, alcoholysis, hydrolysis and the like using a conventionally known alkali catalyst or acid catalyst can be applied, and among them, a saponification reaction using methanol as a solvent and a caustic soda (NaOH) catalyst is simple and most preferable.

  Examples of the vinyl ester-based monomer include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl laurate and palmitate. Examples thereof include vinyl acid, vinyl stearate, vinyl oleate and vinyl benzoate, with vinyl acetate being particularly preferable.

  Moreover, when polymerizing the said vinyl-ester type monomer, it can also be copolymerized with another monomer in the range which does not impair the meaning of this invention. Therefore, polyvinyl alcohol in the present invention is a concept including a polymer composed of vinyl alcohol units and other monomer units. Examples of other monomers include, for example, α-olefins such as ethylene, propylene, n-butene and i-butene; acrylic acid and salts thereof; methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic Acrylic esters such as i-propyl acid, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc. methacrylic acid and salts thereof; methacrylic Methyl acrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate Methacrylic acid esters such as Ryl amide, N-methyl acrylamide, N-ethyl acrylamide, N, N- dimethyl acrylamide, diacetone acrylamide, acrylamidopropane sulfonic acid and its salts, acrylamidopropyl dimethyl amine and its acid salt or quaternary salt, N-methylol acrylamide and its salt Acrylamide derivatives such as derivatives; methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, methacrylamide propane sulfonic acid and salts thereof, methacrylamidopropyldimethylamine and acid salts or quaternary salts thereof, N-methylol methacrylamide and Methacrylamide derivatives such as derivatives thereof; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n -Vinyl ethers such as butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether and stearyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride and vinyl fluoride; vinylidene chloride and fluorine Vinylidene halides such as vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; maleic acid and its salts, esters or anhydrides; vinylsilyl compounds such as vinyltrimethoxysilane; and isopropenyl acetate. These monomers are usually used in a proportion of less than 10 mol% with respect to the vinyl ester monomer.

  When the other monomer unit is an α-olefin unit, the preferable lower limit of the content is 1 mol%, and the preferable upper limit is 20 mol%. When the content of the α-olefin unit is less than 1 mol%, the effect of containing the α-olefin becomes insufficient, and when it exceeds 20 mol%, the hydrophobicity of the obtained polyvinyl acetal becomes too strong and ceramic powder is obtained. The dispersibility of the polyvinyl alcohol resin is reduced, and the solubility of the raw material polyvinyl alcohol resin is reduced, which makes the acetalization reaction difficult.

  In the present invention, the acid catalyst used for the acetalization reaction is not particularly limited, and any of an organic acid and an inorganic acid can be used. For example, acetic acid, p-toluenesulfonic acid, nitric acid, sulfuric acid, hydrochloric acid and the like can be mentioned. Among these, hydrochloric acid, sulfuric acid and nitric acid are preferably used. In general, when nitric acid is used, the reaction rate of the acetalization reaction is increased, and productivity improvement can be expected, but the particles of polyvinyl acetal to be obtained tend to be coarse and the variation between batches tends to be large. In particular, hydrochloric acid is preferred as the acid catalyst used for the acetalization reaction.

  Although the aldehyde used for acetalization reaction is not specifically limited, Aldehyde which has a well-known hydrocarbon group is mentioned. The aldehyde having a hydrocarbon group is, as an aliphatic aldehyde, formaldehyde (including paraformaldehyde), acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, hexyl aldehyde, 2-ethylbutyraldehyde, Pivalaldehyde, octyl aldehyde, 2-ethylhexyl aldehyde, nonyl aldehyde, decyl aldehyde, dodecyl aldehyde etc., and as alicyclic aldehyde, cyclopentane aldehyde, methyl cyclopentane aldehyde, dimethyl cyclopentane aldehyde, cyclohexane aldehyde, methyl cyclohexane aldehyde , Dimethylcyclohexane aldehyde, cyclohexane acetaldehyde etc., cyclic unsaturated alde As cyclopentanaldehyde, cyclohexene aldehyde and the like, and as the aromatic or unsaturated bond-containing aldehyde, benzaldehyde, methyl benzaldehyde, dimethyl benzaldehyde, methoxy benzaldehyde, phenylacetaldehyde, phenylpropyl aldehyde, cumin aldehyde, naphthylaldehyde, anthraaldehyde, etc. Cinnamaldehyde, crotonaldehyde, acrolein aldehyde, 7-octene-1-al and the like, and heterocyclic aldehydes include furfural aldehyde, methyl furfural aldehyde 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-butyraldehyde is particularly preferably used. In the present invention, polyvinyl acetals obtained by using two or more aldehydes in combination can also be used.

  As the aldehyde used for the acetalization reaction, aldehydes other than hydrocarbons 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 aldehydes having an amino group as a functional group include aminoacetaldehyde, dimethylaminoacetaldehyde, diethylaminoacetaldehyde, aminopropionaldehyde, dimethylaminopropionaldehyde, aminobutyraldehyde, aminopentylaldehyde, aminobenzaldehyde, dimethylaminobenzaldehyde, ethylmethylaminobenzaldehyde, Diethylamino benzaldehyde, pyrrolidinyl acetaldehyde, piperidyl acetaldehyde, pyridyl acetaldehyde and the like can be mentioned, and aminobutyraldehyde is preferable from the viewpoint of productivity.

  Examples of aldehydes having an ester group as a functional group include methyl glyoxylate, ethyl glyoxylate, methyl formylacetate, ethyl formylacetate, methyl 3-formylpropionate, ethyl 3-formylpropionate, methyl 5-formylpentanoate, Ethyl formylpentanoate and the like can be mentioned.

  As aldehydes having a carbonyl group as a functional group, glyoxylic acid and its metal salt or ammonium salt, 2-formylacetic acid and its metal salt or ammonium salt, 3-formylpropionic acid and its metal salt or ammonium salt, 5-formylpentane Acid and its metal salt or ammonium salt, 4-formyl phenoxy acetic acid and its metal salt or ammonium salt, 2-carboxybenzaldehyde and its metal salt or ammonium salt, 4-carboxybenzaldehyde and its metal salt or ammonium salt, 2,4- Dicarboxy benzaldehyde and its metal salt or ammonium salt may, for example, be mentioned.

  Examples of aldehydes having a vinyl group as a functional group include acrolein and the like.

  In addition, heterocyclic aldehyde, aldehyde having an amide group, aldehyde having a hydroxyl group, aldehyde having a sulfonic acid group, aldehyde having a phosphoric acid group, cyano group, a nitro group or quaternary ammonium within a range not impairing the characteristics of the present invention. An aldehyde having a salt or the like, an 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, as a (meth) acrylic resin having a hydroxyl group, a (meth) acrylic monomer having a hydroxyl group and a (meth) acrylic monomer having no hydroxyl group Copolymers of the following can be used. As a (meth) acrylic monomer having a hydroxyl group, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate Acrylates such as polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polyethylene glycol-polypropylene glycol monoacrylate, polyethylene glycol-polytetramethylene glycol monoacrylate, polypropylene glycol-polytetramethylene glycol monoacrylate; 2-hydroxyethyl methacrylate, 2- Hydroxypropyl methacrylate, 3-hydroxy Ropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol-polypropylene glycol monomethacrylate, polyethylene glycol-polytetramethylene glycol mono Examples include methacrylates and methacrylates such as polypropylene glycol-polytetramethylene glycol monomethacrylate. Among them, methacrylates having a hydroxyl group are preferable from the viewpoint of sinterability, and specifically, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, and polypropylene glycol monomethacrylate are preferable.

  Moreover, as a (meth) acrylic monomer having no hydroxyl group, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n -Acrylates such as hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, isodecyl acrylate, isoboronyl acrylate, tetrahydrofuryl acrylate etc; ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl Methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate Rate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, isodecyl methacrylate, isobornyl methacrylate, methacrylates such as tetrahydrofuryl methacrylate. Among them, methacrylate is preferable from the viewpoint of sinterability, and specifically, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n- Preferred are 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, and 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, residual carbon after sintering may be increased. The content of the segment derived from the (meth) acrylic monomer having a hydroxyl group is preferably 1% by mass or more. When the content of the segment derived from the (meth) acrylic monomer having a hydroxyl group is less than 1% by mass, the compatibility with the polyvinyl acetal resin is deteriorated when used as the binder resin (A) together with the polyvinyl acetal resin Sometimes.

(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 using 2 or more types together, the mixture etc. of polyvinyl acetal and other binder resin (A) can be used. When mixing polyvinyl acetal and other binder resin (A), for example, it is preferable that mass ratio of polyvinyl acetal and other binder resin (A) is 5/95 or more, and is 10/90 or more. More preferable. Further, 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 other binder resin (A), the (meth) acrylic resin which has a hydroxyl group is preferable.

  In the ceramic green sheet of the present invention, in addition to the binder resin (A), a binder resin having no hydroxyl group in the molecule may be contained within the range not impairing the effects of the present invention. When using binder resin which does not have a hydroxyl group in the molecule, the ratio is preferably 0.01 parts by mass or more with respect to 100 parts by mass of binder resin (A), and 0.1 parts by mass or more More preferable. The proportion of the binder resin having no hydroxyl group in the molecule is preferably 80 parts by mass or less and more preferably 50 parts by mass or less with respect to 100 parts by mass of the binder resin (A).

で示される有機化合物（Ｂ）を含有する。化学式（１）中のＲ２は、炭素数１〜２０の分岐を有してもよいアルキレン基を表す。Ｒ２の炭素数は、１５以下であることが好ましく、１０以下であることがより好ましく、８以下であることがさらに好ましい。また、Ｒ２の炭素数は、２以上であることが好ましく、３以上であることがより好ましく、４以上であることがさらに好ましい。Ｒ２の炭素数が上記範囲外であると、有機化合物（Ｂ）とバインダー樹脂（Ａ）との相溶性が悪くなり、セラミックスラリーの保存安定性、セラミックグリーンシートの接着性が低下する傾向にある。Ｒ３は、炭素数１〜４の分岐を有してもよいアルキレン基を表す。Ｒ３の炭素数は、３以下であることが好ましく、２以下であることがより好ましい。Ｒ２およびＲ３は直鎖構造であってもよく、分岐を有していてもよいが、Ｒ２およびＲ３はそれぞれ独立して直鎖構造であることが好ましい。[Organic Compound (B)]
In the ceramic green sheet of the present invention, the chemical formula (1):

The organic compound (B) shown by these is contained. R 2 in the chemical 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, and still more preferably 8 or less. The carbon number of R2 is preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more. If the carbon number of R2 is out of the above range, the compatibility between the organic compound (B) and the binder resin (A) tends to deteriorate, and the storage stability of the ceramic slurry and the adhesiveness of the ceramic green sheet tend to decrease. . R3 represents an alkylene group having 1 to 4 carbon atoms which may have a branch. The carbon number of R3 is preferably 3 or less, more preferably 2 or less. R2 and R3 may have a linear structure or may have a branch, but it is preferable that R2 and R3 each independently have a linear structure.

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

で示されるエーテル結合を少なくとも一つ有する有機基であることが、バインダー樹脂（Ａ）との相溶性の観点で好ましい。R1 and R4 are each independently an organic group having at least one ether bond. R1 and R4 may each independently have a plurality of ether bonds. R1 and R4 are preferably each independently a hydrocarbon group having at least one ether bond. R1 and R4 may be different or identical. Each of R 1 and R 4 has a chemical formula (2):

It is preferable from the viewpoint of compatibility with the binder resin (A) that it is an organic group having at least one ether bond shown by

  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, and still more preferably 4 or less. When the carbon number of R5 exceeds the above range, the compatibility between the organic compound (B) and the binder resin (A) is deteriorated, and the adhesiveness tends to be lowered. R6 represents an alkylene group which may have 1 to 10 carbon atoms and a branch. The carbon number of R 6 is preferably 8 or less, more preferably 6 or less, and still more preferably 4 or less. When the carbon number of R6 exceeds the above range, the compatibility between the organic compound (B) and the binder resin (A) is deteriorated, and the adhesiveness of the ceramic green sheet tends to be lowered. R7 represents an alkylene group which may have 1 to 4 carbon atoms and may be branched. The carbon number of R 7 is preferably 3 or less, more preferably 2 or less. R6 and R7 may be each independently a linear structure, or may have a branch. R6 and R7 preferably have a linear structure. The plurality of R 7 may be the same or different.

  n is an integer of 0 to 2; n is preferably 0 or 1, and more preferably 0. If n exceeds the above range, the boiling point of the organic compound (B) may be high, 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, and 0.5 mg KOH / g or less Is particularly preferred. As described above, when the above range is satisfied, it is preferable from the viewpoint of reducing the delamination due to the rapid decomposition at the time of degreasing and also from the viewpoint of reducing the corrosiveness of the process. The acid value of the organic compound (B) is high due to the formation of a carboxylic acid by deesterification during storage or the residual carboxylic acid remaining during the production of the organic compound (B).

  200 or more are preferable and, as for the molecular weight of an organic compound (B), 250 or more are more preferable. If the molecular weight is less than the above range, it may be highly volatile, volatilize during sheet drying, and may not exhibit sufficient adhesiveness. The molecular weight of the organic compound (B) used in the present invention is preferably 500 or less, more preferably 400 or less. When the molecular weight is larger than the above range, the viscosity of the organic compound (B) tends to be high or it solidifies, and the compatibility with the resin tends to decrease.

  As a structure of an organic compound (B), what does not contain a hydroxyl group in a molecule | numerator is preferable. When the organic compound (B) contains a hydroxyl group, the action at the interface at the time of pressure bonding tends to be reduced, and sufficient adhesiveness may not be obtained.

  As the organic compound (B), for example, bis (2-butoxyethyl) adipate, bis (2-methoxyethyl) adipate, bis (2-ethoxyethyl) adipate, bis [2- (2-butoxy) adipate Ethoxy) ethyl], bis (3-methoxy-3-methylbutyl) adipate, bis (2-methoxyethyl) sebacate, bis (2-methoxyethyl) diglycolate, and the like. Among them, bis (2-butoxyethyl) adipate and bis (2-methoxyethyl) adipate are preferable from the viewpoint of excellent storage stability of the ceramic slurry, excellent adhesion of the ceramic green sheet, and appropriate strength retention.

[Organic solvent (C)]
The ceramic green sheet of the present invention is obtained, for example, by drying a ceramic slurry containing a binder resin (A), an organic compound (B), an organic solvent (C) and an inorganic compound (D) to form a sheet. Can. The organic solvent (C) may be appropriately selected depending on the purpose and application, and examples thereof include alcohols such as methanol, ethanol, isopropanol, n-propanol and butanol; cellosolve such as methyl cellosolve and butyl cellosolve; Ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as toluene and xylene; halogen based hydrocarbons such as dichloromethane and chloroform; esters such as ethyl acetate and methyl acetate; menthene, menthene, menthene, myrcene, α-pinene, α- Terpinene, γ-Terpinene, limonene, perillyl acetate, menthyl acetate, carbyl acetate, dihydrocarbyl acetate, perillyl alcohol, dihydroterpineol acetate, terpineol acetate, dihydroterpineol, ter Nyloxyethanol, dihydroterpinyloxyethanol, terpinyl methyl ether, dihydroterpinyl methyl ether, dihydroterpinyl propionate, isobonyl acetate, isobonyl propionate, isobonyl butyrate, isobonyl isonyl ester Butyrate, novir acetate, octyl acetate, dimethyl octyl acetate, butyl carbitol acetate, acetoxy-methoxyethoxy-cyclohexanol acetate, dihydrocarbeol, 2-ethylhexyl glycol, benzyl glycol, phenyl propylene glycol, methyl decaline, amyl benzene, cumene And cymene, 1,1-diisopropylhexane, citronellol and the like. Among them, alcohols such as methanol, ethanol, isopropanol, n-propanol and butanol; cell solves such as methyl cell sorb and butyl cell sorb; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as toluene and xylene; Halogenated hydrocarbons, esters such as ethyl acetate and methyl acetate are preferably used. These may be used alone or in combination of two or more. Furthermore, butanol, ethanol, toluene, ethyl acetate, or a mixed solvent thereof is more preferable from the viewpoint 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, and more preferably 5 parts by mass or more with respect to 100 parts by mass of ceramic powder described later. More preferably, it is 10 parts by mass or more. When the content of the organic solvent (C) is below the above range, the viscosity of the ceramic slurry tends to be too high, and the kneadability tends to be reduced. The content of the organic solvent (C) is more preferably 200 parts by mass or less and still more preferably 150 parts by mass or less with respect to 100 parts by mass of the ceramic powder. When the content of the organic solvent (C) exceeds the above range, the viscosity of the ceramic slurry becomes too low, and the handling property at the time of forming the ceramic green sheet tends to be deteriorated.

[Inorganic compound (D)]
The ceramic green sheet of the present invention contains at least barium titanate as the inorganic compound (D), but other inorganic compounds (D) can be used. Other inorganic compounds (D) include, for example, glass powder, ceramic powder, phosphor fine particles, silicon oxide and the like according to the purpose and application. These inorganic compounds (D) can be suitably used in combination of 2 or more types.

Examples of the glass powder include glass powder such as bismuth oxide glass, silicate glass, lead glass, zinc glass, boron glass, CaO-Al ₂ O ₃ -SiO ₂ system, MgO-Al ₂ O ₃ -SiO ₂ Glass powder of various silicon oxides such as ₂ series, LiO ₂ -Al ₂ O ₃ -SiO ₂ series, etc. may be mentioned.

  The ceramic powder includes not only barium titanate but also powders of metal or nonmetal oxides, carbides, nitrides, borides or sulfides used in the production of ceramics. Specific examples thereof include Li, K, Mg, B, Al, Si, Cu, Ca, Sr, Ba, Zn, Cd, Ga, In, Y, lanthanoids, actinoids, Ti, Zr, Hf, Bi, V, Nb And oxides such as Ta, W, Mn, Fe, Co, Ni, carbides, nitrides, borides, sulfides and the like.

[Ceramic green sheet]
In the ceramic green sheet, the content of the binder resin (A) with respect to the ceramic powder varies depending on the purpose of use of the ceramic green sheet, but in general, the content is preferably 3 parts by mass or more with respect to 100 parts by mass of barium titanate. More preferably, it is 5 parts by mass or more. The content of the binder resin (A) is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less, with respect to 100 parts by mass of barium titanate. If the content of the binder resin (A) is less than 3 parts by mass with respect to 100 parts by mass of barium titanate, adhesion failure and insufficient strength of the obtained ceramic green sheet may be obtained. When the amount of binder resin (A) used exceeds 20 parts by mass, the density of barium titanate in the ceramic green sheet decreases, which causes deterioration of the quality of the final product multilayer ceramic capacitor, and volatilization during sintering. It may be a cause of delamination due to the increase of components and shrinkage of the fired 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%, a large amount of water is sucked during storage of the ceramic green sheet, so delamination May be the cause of On the other hand, when the degree of acetalization of polyvinyl acetal exceeds 85 mol%, the content of hydroxyl groups (vinyl alcohol monomer units) in the polyvinyl acetal decreases, and the adhesiveness of the ceramic green sheet and the dimensional stability at the time of pressure bonding decrease. Tend to When the degree of acetalization of the polyvinyl acetal is within the above-described preferable range, the adhesiveness at the time of pressure bonding of the obtained ceramic green sheet tends to be more excellent.

  When 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. If the content exceeds 20 mol%, the amount of carbon residue tends to increase in the obtained ceramic molded article. Furthermore, the flexibility of the obtained ceramic green sheet tends to be high, and the strength of the ceramic green sheet tends to decrease.

  When polyvinyl acetal is contained as the binder resin (A) contained in the ceramic green sheet, the preferable range of the viscosity average degree of polymerization of the polyvinyl acetal is as described above, but the viscosity average degree of polymerization does not reach 200. May reduce the strength of the resulting ceramic green sheet. The viscosity average polymerization degree of the polyvinyl acetal is preferably 300 or more, more preferably 500 or more, and still more preferably 800 or more. On the other hand, when the viscosity average polymerization degree of polyvinyl acetal exceeds 5000, the viscosity of the ceramic slurry prepared at the time of manufacturing a ceramic green sheet may become high too much, and productivity may fall. The viscosity average polymerization degree of the polyvinyl acetal is preferably 4500 or less, more preferably 4000 or less, and still more preferably 3500 or less. In addition, from the viewpoint of making the dimensional stability of the ceramic green sheet at pressure bonding further excellent, the viscosity average polymerization degree of the polyvinyl acetal is preferably 1400 or more, and more preferably 1500 or more.

  When polyvinyl acetal is contained as the binder resin (A) contained in the ceramic green sheet, the preferred range of the degree of saponification of the raw material PVA is as described above, but if the degree of saponification of the raw material PVA is less than 80 mol%, The strength of the ceramic green sheet containing polyvinyl acetal may be reduced.

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

  Although content of the organic compound (B) in the said ceramic green sheet is not specifically limited, It is preferable that it is 1 mass part or more with respect to 100 mass parts of binder resin (A), and it is more preferable that it is 5 mass parts or more. And 10 parts by mass or more. When content of an organic compound (B) becomes less than the said range, it may become a cause of the adhesion failure of the ceramic green sheet obtained. The content of the organic compound (B) is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and still 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 tends to decrease, and the dimensional stability at the time of pressure bonding tends to decrease.

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

When a plasticizer is added, the mass ratio of the total of the plasticizer and the organic compound (B) to the binder resin (A) (the total of the mass of the plasticizer and the organic compound (B) / binder resin (A) in the ceramic green sheet The mass) of is preferably 0.01 or more, more preferably 0.05 or more. The mass ratio is preferably 2 or less, more preferably 1.5 or less.

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

As a suitable method of forming a ceramic green sheet, a 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, so-called sheet forming The law is mentioned.

In addition to the binder resin (A), the organic compound (B), and the ceramic powder, the ceramic green sheet may, if necessary, be a peptizing agent, an adhesion promoter, and a dispersing agent, as long as not departing from the spirit of the present invention. A tackifier, a storage stabilizer, an antifoamer, a thermal decomposition accelerator, an antioxidant, a surfactant, a lubricant, an adhesion improver, and other conventionally known additives may be included. Moreover, as long as the effects of the present invention are not impaired, resins 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, detected Ba + ion relative to the intensity of Ti + ion detected. The ratio of the strength of (Ba + ion strength) / (Ti + ion strength) is a ceramic green sheet satisfying 20 <(Ba + ion strength) / (Ti + ion strength) <1000. 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 pressure bonding and which is also small in dimensional change at the time of pressure bonding. In addition, when (Ba + ion strength) / (Ti + ion strength) falls within the above range, rapid firing of the binder component from the laminate can be suppressed when the ceramic green sheet is fired, and the lamination is performed. The delamination at the time of production of the ceramic capacitor is suppressed.

  The (intensity of Ba + ion) / (intensity of Ti + ion) is preferably greater than 100, and more preferably greater than 150. Further, (Intensity of Ba + ion) / (Intensity of Ti + ion) is preferably smaller than 700, and more preferably smaller than 500.

  By performing TOF-SIMS analysis on the ceramic green sheet, Ba + ions and Ti + ions measured as secondary ions are derived from Ba atoms and Ti atoms in barium titanate used as ceramic powder. A method of obtaining a ceramic green sheet in which (Intensity of Ba + ion) / (Intensity of Ti + ion) falls within the above range when TOF-SIMS analysis is carried out is not particularly limited. The method of producing a ceramic green sheet using the ceramic slurry which contains the organic compound (B) shown, and used barium titanate as ceramic powder, and performs plasma processing is mention | raise | lifted.

By the way, when the content of the organic compound (B) and the organic compound (plasticizer) other than the organic compound (B) in the ceramic green sheet is decreased, the ceramic green sheet becomes hard and the dimensional stability at the time of pressure bonding is improved. On the other hand, the adhesion at the time of crimping tends to decrease. Therefore, it is generally difficult to achieve both dimensional stability and adhesion. In the present invention, the content of the organic compound (B) or an organic compound (plasticizer) other than the organic compound (B) is set by setting (Intensity of Ba + ion) / (Intensity of Ti + ion) within the above range. Even when the amount is reduced, it is possible to obtain a ceramic green sheet excellent in not only the dimensional stability at the time of pressure bonding but also the adhesion at the time of pressure bonding.

The ceramic green sheet of the present invention is suitably used as a material of various electronic parts. In particular, they are suitably used as materials for chip-type multilayer capacitors and circuit boards for IC chips. These are manufactured by forming an electrode on a ceramic green sheet, stacking, pressing and firing.

As a method for producing a ceramic green sheet, for example, after a ceramic slurry is applied on a support film subjected to single-sided mold release treatment, a method of drying the organic solvent (C) and forming it into a sheet can be mentioned. . For coating 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.

As a support film used when manufacturing a ceramic green sheet, what consists of resin which has heat resistance and solvent resistance, and has flexibility is preferable. The support film is made of a flexible resin, so that the ceramic slurry is coated on the support film, and the obtained film on which the ceramic green sheet is formed is stored in a rolled state, and it is necessary. Can be supplied according to.

  The resin constituting the support film is not particularly limited, and examples thereof include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, fluorine-containing resin such as polyvinyl chloride, polytetrafluoroethylene, nylon, cellulose and the like. . The thickness of the support film is not particularly limited, and is preferably 20 μm or more, and more preferably 100 μm or less. Moreover, it is preferable that the mold release process is given to the surface of a support film. By performing the mold release treatment on the surface of the support film, the peeling operation of the support film can be easily performed in the transfer step. As a preferable specific example of a support film, a silicone coat PET film is mentioned.

  The thickness of the ceramic green sheet can not be generally defined because it varies depending on the purpose of use, but is preferably 0.1 μm or more, and more preferably 300 μm or less. In addition, the drying temperature when drying the coating film formed on the carrier film is different depending on the thickness of the ceramic green sheet, etc., so this can not be generally defined, but is preferably 25 ° C. or higher And 200 ° C. or less.

[Coated sheet]
A preferred embodiment of the present invention is a coated sheet obtained by applying a conductive paste on the surface of the above-described ceramic green sheet of the present invention. When used in combination with the ceramic green sheet of the present invention, the conductive paste may be a commonly used conductive paste.

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

[TOF-SIMS analysis]
The TOF-SIMS analysis is a measurement method that can scan the surface of the measurement object and observe the distribution state of the components contained in the measurement object. For example, the 50 to 500 μm square area of the surface of the measurement object is divided into minute areas of 0.1 to 3 μm square, the primary ion is irradiated, and secondary ions that fly out from this minute area are observed. Identification of the type of component in the micro area and the intensity of the secondary ion can be measured. This minute area is called a primary ion irradiation point. This minute area is called a primary ion irradiation point. The ratio of the intensity of Ba + ion to the intensity of Ti + ion (intensity of Ba + ion) / (intensity of Ti + ion) is a value obtained by dividing the intensity of Ba + by the intensity of Ti + secondary ion.

  When plasma treatment is performed on the surface of the ceramic green sheet, the surface state of the ceramic green sheet may change depending on the storage state after the plasma irradiation, so the surface measurement by TOF-SIMS analysis is after the plasma irradiation It is preferable to do it promptly. The time from plasma irradiation to surface measurement by TOF-SIMS analysis is preferably within 12 hours, more preferably within 3 hours, still more preferably within 1 hour, and immediately after plasma irradiation It is most preferred to make a measurement. When analyzing the sheet after applying the conductive paste, the surface analysis is performed on the portion of the ceramic green sheet which is not coated with the conductive paste among the surfaces to which the conductive paste is applied.

  Moreover, in order to suppress that the component of the surface of a ceramic green sheet volatilizes during the measurement by TOF-SIMS analysis, for example, after cooling to -100 degreeC--200 degreeC, under vacuum, TOF-SIMS analysis is carried out. Is preferred.

Plasma treatment
In the ceramic green sheet of the present invention, it is preferable that at least a part of at least one surface of the ceramic green sheet is subjected to plasma treatment. That is, in the production thereof, it is preferable to include a step of subjecting at least one surface of the front surface or the back surface of the ceramic green sheet to plasma treatment. The ceramic green sheet thus obtained is also a preferred embodiment of the present invention. Plasma treatment is performed on at least one surface of the front surface or the back surface of the ceramic green sheet, and lamination is performed so that the plasma-treated surface is in contact with the surface of the other ceramic green sheet. The laminate thus obtained has better adhesion than in the case of producing a laminate using a ceramic green sheet whose surface has not been subjected to plasma treatment.

  Further, the coated sheet of the present invention is preferably in a state in which at least a part of at least one surface of the coated sheet surface is subjected to plasma treatment. That is, in the production thereof, it is preferable to include the step of subjecting at least one surface of the coated sheet surface to plasma treatment. Plasma treatment may be applied to at least a part of at least one surface of the surface of the coated sheet, and a method of applying plasma treatment to the ceramic green sheet before applying the conductive paste, or applying the conductive paste to the ceramic green sheet It can be obtained by any method of plasma treatment to the coated sheet after processing.

  The surface of the coated sheet on which the conductive paste has been applied is subjected to plasma treatment, and is laminated such that the plasma-treated side is in contact with one surface of another coated sheet. The laminate thus obtained exhibits better adhesion than in the case of producing a laminate using a coated sheet whose surface has not been subjected to plasma treatment.

  The surface to which the plasma treatment is applied may be the surface coated with the conductive paste (conductive paste surface), the back surface of the coated sheet (ceramic green sheet surface), or the front and back surfaces of the coated sheet. When a plurality of coated sheets are stacked to produce a laminated ceramic capacitor, the conductive paste surface may be subjected to plasma treatment, and may be laminated such that this surface is in contact with the ceramic green sheet surface of another coated sheet. The laminate thus obtained exhibits good adhesion.

  In addition, plasma treatment may be performed on the surface of the ceramic green sheet, and lamination may be performed such that this surface is in contact with the conductive paste surface of the other coated sheet. The laminate thus obtained also exhibits good adhesion. As the coating sheet in this case, a coating sheet obtained by coating a conductive paste generally used on the surface of the ceramic green sheet of the present invention is suitably used. Furthermore, the surface or back surface of the coated sheet is subjected to plasma treatment, and lamination is performed such that the surface subjected to the plasma treatment is in contact with the ceramic green sheet surface or the conductive paste surface of the other coated sheet. The laminate thus obtained also exhibits good adhesion.

  Alternatively, plasma treatment may be performed on the ceramic green sheet, and the conductive paste may be applied to the plasma-treated surface. It laminates | stacks so that the surface where the plasma processing was performed and the electrically conductive paste was coated and the single side | surface of another coated sheet may contact | connect. The laminate thus obtained exhibits better adhesion than in the case where a laminate is produced using a coated sheet whose surface has not been subjected to plasma treatment. As the coating sheet in this case, a coating sheet obtained by coating a conductive paste generally used on the surface of the ceramic green sheet of the present invention is suitably used.

  The ceramic green sheet is a laminate in which the ceramic green sheet is plasma-treated and the surface to which plasma treatment is applied is coated with the conductive paste and one side of the ceramic green sheet not subjected to plasma treatment is in contact with each other. The surface of the ceramic green sheet is compared when the adhesion is compared between the surface coated with the conductive paste and the surface coated with the plasma processing of the ceramic green sheet without the plasma processing. The latter, which has a large area of the surface treated with plasma, shows better adhesion. Similarly, after applying the conductive paste on one side of the ceramic green sheet, laminating is performed so that the coated side when the coated side is subjected to plasma treatment and one side of the ceramic green sheet not subjected to plasma treatment are in contact with each other. The adhesion is compared between the laminated body and the laminated body laminated so that the surface on which the conductive paste is applied and the surface on which the ceramic green sheet is plasma-treated, without plasma treatment on the ceramic green sheet. In the case where the surface area of the ceramic green sheet is plasma treated on the surface is larger, the latter shows better adhesion.

  The method of plasma treatment used in the present invention is not particularly limited, and examples thereof include treatments such as low pressure plasma, high pressure plasma, corona discharge treatment, atmospheric pressure plasma and the like. As the treatment method, any suitable treatment method can be used as long as the nature of the present invention is not impaired, but the low pressure plasma needs to be applied under vacuum, making in-line production difficult. Since the corona treatment has high energy, the surface shape may change or the treated surface may become unexpectedly uniform. On the other hand, atmospheric pressure plasma treatment does not have to be performed in a vacuum state, and energy can be selected to be high or low. Atmospheric pressure plasma is particularly preferable as the processing method from the viewpoint of productivity and performance.

  Various atmospheric pressure plasma apparatuses can be used for atmospheric pressure plasma processing. As the atmospheric pressure plasma apparatus, any apparatus can be used, but various modified examples can be selected according to the purpose of use. For example, a device capable of generating a low temperature plasma by intermittently discharging while passing an inert gas at a pressure near atmospheric pressure between the electrodes covered with a dielectric is preferable. The "pressure near the atmospheric pressure" in the "atmospheric pressure plasma" in the present invention refers to a range of 70 kPa or more and 130 kPa or less, preferably 90 kPa or more and 110 kPa or less. The temperature and the humidity at the time of performing the atmospheric pressure plasma treatment are not particularly limited and may be changed as appropriate, but it is preferable to perform the atmospheric pressure plasma treatment at normal temperature and normal humidity.

  As discharge gas used at the time of generation of atmospheric pressure plasma, any gas of nitrogen, oxygen, hydrogen, carbon dioxide, helium, and argon, or a mixed gas of two or more of them can be used. It is preferable to use inert gases such as noble gases such as He and Ar, or nitrogen gas, and rare gases such as Ar or He are particularly preferable. For example, when using a mixed gas of nitrogen gas and air, it is preferable to supply nitrogen gas at a flow rate of 10 L / min or more and 500 L / min or less. Moreover, it is 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 plasma using an atmospheric pressure plasma device, 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, and more preferably 2 mm or more. The inter-electrode distance is preferably 10 mm or less, more preferably 5 mm or less.

  For example, the ceramic green sheet is moved by moving the ceramic green sheet in a direction perpendicular to the plasma irradiation direction while maintaining the surface of the ceramic green sheet to be subjected to plasma processing perpendicular to the plasma irradiation direction. Plasma treatment can be performed. The time during which the ceramic green sheet passes under the irradiation port is preferably 0.1 seconds or more, and more preferably 0.5 seconds or more. Moreover, it is preferable that it is 40 seconds or less, and it is more preferable that it is 20 seconds or less. Note that the area immediately below the irradiation port may also be in a plasma atmosphere.

  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 (intensity of Ba + ion) / (intensity of Ti + ion) becomes less than 20. Or, it tends to be larger than 1000.

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. In the following Examples and Comparative Examples, "degree of polymerization" means "viscosity average degree of polymerization". Moreover, in the following examples and comparative examples, the "ceramic green sheet" means the part which does not contain the polyester film which is a support film.

[Evaluation method]
(1. Measurement of polyvinyl acetal)
The content (mol%) of vinyl acetate monomer units, the degree of acetalization (mol%) and the content (mol%) of vinyl alcohol monomer units of polyvinyl acetals used in Examples and Comparative Examples are JIS K 6728: It measured according to 1977. The viscosity average polymerization degree of polyvinyl acetal was shown by the viscosity average polymerization degree of PVA of the raw material measured based on JISK6726: 1994.

(2. Measurement of acid value of organic compounds)
The acid value of the organic compound used in Examples and Comparative Examples was measured in accordance with JIS K 6728: 1977. More specifically, about 1 g of each organic compound was placed in a stoppered Erlenmeyer flask and dissolved by adding 30 ml of ethyl alcohol. Phenolphthalein was used as an indicator, the obtained solution was titrated using N / 50 potassium hydroxide, and the titrated amount up to the point of maintaining a slight red color for 30 seconds or more was designated as a (mL). Separately from this, the same titration was performed on 30 ml of ethyl alcohol, and the titration amount up to the point at which the slight red color was maintained was b (mL), and the acid value was calculated by the following formula (II).

(3. TOF-SIMS analysis of ceramic green sheet surface)
In order to suppress volatilization of components on the surface of the ceramic green sheet during measurement, time-of-flight secondary ion mass spectrometry (TOF-SIMS) was performed for cooling measurement. After atmospheric pressure plasma treatment is performed on the surface of the ceramic green sheet obtained in the production example, the ceramic green sheet is cooled to -150 ° C., and then, under vacuum, immediately after time-of-flight secondary ion mass spectrometry (TOF-) The analysis by SIMS was performed. The time-of-flight secondary ion mass spectrometer (TOF-SIMS) used ION-TOF company TOF-SIMS5. A bismuth cluster ion source (Bi3 ++) was used as the primary ion source, the current value was 0.2 picoampere, the acceleration voltage was 25 kilovolts, and the measurement mode was high mass resolution normal mode (bunching mode). An arbitrary 500 μm × 500 μm of the flat surface of the ceramic green sheet (one of the widest surfaces of the ceramic green sheet) is a measurement area, the measurement area is divided into 128 × 128 pixels, and the irradiation mode of the ion beam is random. The measurement area was scanned in raster mode, and the number of scans was 64. The intensity of Ti + ion and the intensity of Ba + ion were calculated from the mass spectrum obtained by the measurement, and the ratio of the intensity of Ba + ion to the intensity of Ti + ion 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 measurement of the surface analysis after the plasma irradiation was performed immediately after the plasma irradiation.

(Adhesive evaluation of the ceramic green sheet)
Using a heat press, laminating ceramic green sheets used in the examples and comparative examples under atmospheric pressure plasma processing under the following conditions and ceramic green sheets used in the examples and comparative examples not subjected to atmospheric pressure plasma processing The thermocompression-bonding test was done on condition of the following. At this time, lamination was performed so that the surface subjected to atmospheric pressure plasma treatment was in contact with the surface not subjected to atmospheric pressure plasma treatment of the other ceramic green sheets, to obtain a laminate.

<Plasma irradiation>
The ceramic green sheets (on polyester film) used in the examples and comparative examples were cut into a size of 10 cm × 10 cm together with the polyester film. After peeling the ceramic green sheet from the polyester film, nitrogen gas has a flow rate of 150 L / min and dry pure air has a flow rate of 0.5 L at normal temperature and normal humidity using an atmospheric pressure plasma apparatus on the surface of the ceramic green sheet. / Min using mixed gas, voltage between electrodes 11 kV, distance between electrodes 2 mm, sample (ceramic green sheet) moving speed 10 mm / s, time for ceramic green sheet to pass just under the irradiation opening of 2 cm width for 2 seconds The atmospheric pressure plasma treatment was performed under the conditions (10 seconds for the entire 10 cm × 10 cm ceramic green sheet).

<Heat pressing conditions>
Press temperature 45 ° C
Pressure 1MPa
Time 5 seconds

The resulting laminate was cut into 5 mm × 5 mm, and 100 pieces were optionally extracted. The adhesive surface of the laminate optionally extracted was visually observed, and the adhesion between the ceramic green sheets was evaluated in the following five grades.
A: No delamination was observed at all and it was firmly adhered.
(Number of laminates with delamination / arbitrary laminate = 0/100)
B: Delamination was slightly observed, but adhered firmly.
(Number of laminates with delamination / arbitrary laminate = 1 to 100/100)
C: Delamination was partially observed, but adhered.
(Number of laminates with delamination / arbitrary laminate = 11 to 30/100)
D: A considerable amount of delamination was observed and showed almost no adhesion.
(Number of laminates with delamination / arbitrary laminate = 31 to 99/100)
E: It did not show adhesion.
(Number of laminates with delamination / arbitrary laminate = 100/100)

(4-2. Evaluation of adhesion of coated sheet)
The adhesion was evaluated according to the method described in “4-1. Evaluation of adhesion of ceramic green sheet” except that the coated sheets used in Examples and Comparative Examples were used instead of the ceramic green sheet. At this time, atmospheric pressure plasma treatment is performed on the surface to which the conductive paste is applied, and the surface subjected to atmospheric pressure plasma treatment is the surface of the other coated sheet not subjected to atmospheric pressure plasma treatment (conductive paste is applied (Layers) in contact with each other.

(Evaluation of dimensional stability of 5-1. Ceramic green sheet)
The ceramic green sheet having a film thickness of 2 μm after drying (air drying at normal temperature for 1 hour, then drying at 80 ° C. for 2 hours and then 120 ° C. for 2 hours in a hot air dryer) used in Examples and Comparative Examples The same plasma treatment was applied. This sheet was cut into 5 cm squares, and after stacking two sheets, pressing was performed at 45 ° C. (press pressure: 3 MPa), and the deformation ratio (area after pressing / area before pressing × 100) was determined. At this time, it laminated | stacked so that the surface by which atmospheric pressure plasma processing was carried out may contact | connect the surface which is not the atmospheric pressure plasma processing of another ceramic green sheet.
A: Sheet deformation rate is less than 2% B: Sheet deformation rate is 2% or more and less than 4% C: Sheet deformation rate is evaluated in three stages of 4% or more.

(5-2. Evaluation of dimensional stability of coated sheet)
The dimensional stability was evaluated in the same manner as in “5-1. Evaluation of dimensional stability of ceramic green sheet” except that coated sheets used in Examples and Comparative Examples were used instead of the ceramic green sheet. At this time, atmospheric pressure plasma treatment is performed on the surface to which the conductive paste is applied, and the surface subjected to atmospheric pressure plasma treatment is the surface of the other coated sheet not subjected to atmospheric pressure plasma treatment (conductive paste is applied (Layers) in contact with each other.

(Delamination evaluation of fired body in ceramic green sheet laminate)
One hundred pieces of the ceramic green sheets (on a polyester film) used in Examples and Comparative Examples were cut into 10 cm square and prepared. After peeling the cut ceramic green sheet from the polyester film, the surface was subjected to atmospheric pressure plasma treatment in the same manner as in “4-1. Evaluation of adhesion of ceramic green sheet” on each side, and the surface was subjected to atmospheric pressure plasma treatment A stack of ceramic green sheets was obtained by stacking 100 sheets so that the surfaces not subjected to atmospheric pressure plasma treatment overlap each other. Subsequently, heat pressing was performed for 10 minutes at a temperature of 70 ° C. and a pressure of 150 kg / cm ² to obtain a laminate. The obtained laminate is cut into 5 mm × 5 mm, 100 pieces are optionally extracted from the cut laminate, heated to 400 ° C. at a heating rate of 15 ° C./min in a nitrogen atmosphere, and maintained for 5 hours Further, the temperature was raised to 1350 ° C. at a temperature rising rate of 5 ° C./min, and held for 10 hours to obtain a ceramic fired body.

After cooling the obtained fired body to normal temperature, the cross section of the fired body was observed with an electron microscope, and the presence or absence of delamination between the ceramic layers was evaluated in the following four steps.
A: There is no delamination.
(Number of sintered fired bodies / optional fired body = 0 to 2/100)
B: Slight delamination is observed.
(Number of sintered fired bodies / optional fired body = 3 to 7/100)
C: There is some delamination.
(Number of sintered fired body / optional fired body = 8 to 20/100)
D: There are many delaminations.
(Number of sintered fired bodies / optional fired body = 21 to 100/100)

(De-lamination evaluation of fired body in coated sheet laminate)
One hundred sheets obtained by cutting a coated sheet into 10 cm squares were prepared, which were used in Examples and Comparative Examples. The surface coated with the conductive paste is subjected to atmospheric pressure plasma treatment by the same method as “4-2. Evaluation of adhesion of coated sheet”, and the surface subjected to atmospheric pressure plasma treatment and the surface not subjected to atmospheric pressure plasma treatment 100 stacked one on top of the other to obtain a laminate of coated sheets. Subsequently, heat pressing was performed for 10 minutes at a temperature of 70 ° C. and a pressure of 150 kg / cm ² to obtain a laminate. The obtained laminate is cut into 5 mm × 5 mm, 100 pieces are optionally extracted from the cut laminate, heated to 400 ° C. at a heating rate of 15 ° C./min in a nitrogen atmosphere, and maintained for 5 hours Further, the temperature was raised to 1350 ° C. at a temperature rising rate of 5 ° C./min, and held for 10 hours to obtain a ceramic fired body.

The obtained fired body was cooled to normal temperature, then a cross section of the fired body was observed with 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: There is no delamination.
(Number of sintered fired bodies / optional fired body = 0 to 2/100)
B: Slight delamination is observed.
(Number of sintered fired bodies / optional fired body = 3 to 7/100)
C: There is some delamination.
(Number of sintered fired body / optional fired body = 8 to 20/100)
D: There are many delaminations.
(Number of sintered fired bodies / optional fired body = 21 to 100/100)

[Binder resin (A)]
Synthesis Example 1
In a 10-liter glass container equipped with a reflux condenser, a thermometer, and an electric stirrer, 7280 g of ion-exchanged water, a polymerization degree of 1700, and a polyvinyl alcohol having a degree of hydrolysis of 98.4 mol% (hereinafter referred to as PVA-1 ) Was charged (PVA concentration: 9.0% by mass), and the content was heated to 95 ° C. to completely dissolve PVA. Next, after gradually cooling to 10 ° C. over about 30 minutes while stirring the contents at 120 rpm, 400 g of n-butyraldehyde and 830 mL of 20 mass% hydrochloric acid are added to the container, and the butyralization reaction is performed for 150 minutes went. Thereafter, the temperature was raised to 70 ° C. over 90 minutes, held at 70 ° C. for 120 minutes, and cooled to room temperature. The precipitated resin was washed with ion exchanged water and then neutralized by adding an excess amount of aqueous sodium hydroxide solution. Subsequently, the resin was re-washed with ion exchange water and then dried to obtain polyvinyl butyral (PVB-1).

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

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

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

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

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

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

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

Synthesis Example 9
As shown in Table 1, instead of PVA-1, 70/30 mass ratio of PVA having a degree of polymerization of 2400 and a degree of saponification of 98.8 mol% and a degree of polymerization of 500 and a degree of PVA of 98.8 mol% for a degree of hydrolysis of 98.8 mol% In the same manner as in Synthesis Example 1 except that 399 g of n-butyraldehyde was used, polyvinyl butyral (PVB-9) was obtained.

Synthesis Example 10
In Synthetic Example 1, polyvinyl butyral (PVB-10) was synthesized in the same manner as in Synthetic Example 1 except that acetalization was carried out using isobutyraldehyde instead of butyralization using n-butyraldehyde. Obtained.

Synthesis Example 11
The same operations as in Synthesis Example 1 are carried out except that acetaldehyde and n-butyraldehyde are used in a weight ratio of 100/64 instead of butyralization using n-butyraldehyde in Synthesis Example 1. It went and obtained polyvinyl butyral (PVB-11).

  About PVB-1 to PVB-11, the degree of polymerization, the content of vinyl acetate monomer units, the degree of butyralization and the vinyl alcohol monomer units according to the method described in the above-mentioned evaluation method “1. Measurement of polyvinyl acetal”. Content was measured. The measurement results are shown in Table 1.

[Production of ceramic green sheet]
(Production Example 1)
<Preparation of Inorganic Compound Dispersion Solvent>
After adding 10 parts by mass of PVB-1 to a mixed solvent of 30 parts by mass of toluene and 30 parts by mass of ethanol, the mixture is stirred to dissolve PVB-1 and 100 parts by mass of bis (2-butoxyethyl) adipate is added to the solution. It added so that it might become 38 mass parts with respect to PVB-1 of a part, and it stirred, and prepared the inorganic compound dispersion solvent.

<Production of ceramic slurry>
15 parts by mass of toluene and 15 parts by mass of ethanol are added to 100 parts by mass of barium titanate (“BT-02”, manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter 0.2 μm), and mixed in a ball mill for 15 hours to disperse ceramic I got a liquid. Then, the said inorganic compound dispersion solvent was added to the dispersion liquid of the said ceramic so that PVB-1 might be 7.5 mass parts with respect to 100 mass parts of ceramics, and it mixed in a ball mill for 24 hours, and obtained ceramic slurry.

<Manufacturing of ceramic green sheets>
The obtained ceramic slurry is coated on a release-treated polyester film using a bar coater such that the dry film thickness is 2 to 3 μm, air-dried at room temperature for 1 hour, and then using a hot air dryer. It was dried at 80 ° C. for 2 hours and then at 120 ° C. for 2 hours to obtain a ceramic green sheet GS-1 on a 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 produced in the same manner as in Production Example 1 except that the organic compounds shown in Table 2-1 were used instead of bis (2-butoxyethyl) adipate.

(Production Examples 15 to 18)
Ceramic green sheets GS-15 to GS in the same manner as in Production Example 1 except that bis (2-butoxyethyl) adipate was added to the binder resin (A) at a ratio shown in Table 2-2. -18 was produced.

(Production Examples 19 to 21)
Ceramic green sheets GS-19 to GS-21 were prepared 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 shown in Table 2-2 were used. Made.

Production Example 22
As shown in Table 2-2, 19 parts by mass of bis (2-butoxyethyl) adipate and 19 parts by mass of triethylene glycol di 2-ethylhexanoate were added to 100 parts by mass of PVB-1. The ceramic green sheet GS-22 was produced by the method similar to manufacture example 1.

(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 bis (2-butoxyethyl) adipate having different acid values was used. . The acid values of the bis (2-butoxyethyl) adipates used in Production Examples 23 to 25 are different from each other because the content of the acid component derived from adipic acid is different.

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

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

  With respect to the obtained ceramic green sheets GS-A to GS-I, according to the method described in the above-mentioned evaluation method “2. Measurement of the acid value of the organic compound”, the acid value of the organic compound used at the time of producing each ceramic green sheet Was measured. Table 3 shows the measurement results.

  With respect to the obtained ceramic green sheets GS-1 to GS-25 and GS-A to GS-I, respective ceramic green sheets were produced according to the method described in the above-mentioned evaluation method "2. Measurement of acid value of organic compound". The acid value of the organic compound used sometimes was measured. The measurement results are shown in Table 2-1, Table 2-2 and Table 3.

[Production of conductive paste, coated sheet and laminate]
(Preparation Example 1)
<Production of conductive paste>
Ethyl cellulose (Dow Chemical Co., STD-45) and dihydroterpinyl acetate were added to a 2 L separable flask equipped with a stirrer, condenser, thermometer, water bath and nitrogen gas inlet.

  Next, nickel powder ("NFP 201", manufactured by JFE Minerals Co., Ltd.) is mixed as a conductive powder, and 20 parts by mass of commercially available barium titanate powder having an average particle diameter of 0.1 μm is added to the nickel powder. The conductive paste was obtained by passing this roll several times. In addition, the composition ratio in the conductive paste was prepared so that the binder resin (A) was 3% by mass, nickel powder was 50% by mass, barium titanate was 10% by mass, and others were organic solvents to obtain the conductive paste .

<Production of coated sheet>
The ceramic green sheet GS-1 obtained in Production Example 1 is cut into a size of 10 cm × 10 cm, and the atmospheric pressure plasma treatment is performed according to the method described in the evaluation method “4-1. Adhesion evaluation of ceramic green sheet”. Applied. The conductive paste described above is screen-printed on a surface to which atmospheric pressure plasma treatment has been applied by a screen printer (DP-320 manufactured by Neurong Precision Industrial Co., Ltd.) and dried at 120 ° C. for 1 hour. A conductive paste film was formed with a distance (margin) of 2.5 mm and a film thickness of 2 μm to obtain a coated sheet TS-1.

(Production Example 2)
The ceramic green sheet GS-1 obtained in Production Example 1 is cut into a size of 10 cm × 10 cm, and the above-described conductive paste is screen-printed by a screen printer (DP-320 manufactured by Neurong Precision Industries, Ltd.), 120 By drying at 1 ° C. for 1 hour, a conductive paste film of 10 mm square, a distance between pastes (margin) of 2.5 mm, and a film thickness of 2 μm was formed. The surface on which the conductive paste film was formed was subjected to atmospheric pressure plasma treatment in accordance with the method described in the evaluation method “4-1. Evaluation of adhesion of ceramic green sheet” to obtain a coated sheet TS-2.

(Preparation 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.

  Table 4 shows TS-1 to TS-3.

[Example]
(Examples 1 to 25)
About the dimensional stability at the time of pressure bonding of the ceramic green sheet, the adhesiveness of the ceramic green sheet, and the delamination of the sintered body obtained using the ceramic green sheet for each of the ceramic green sheets GS-1 to GS-25, Evaluation was performed according to the method described in the said evaluation method. The evaluation results are shown in Table 5.

(Example 26)
According to the method described in the above evaluation method, evaluation of dimensional stability at pressure bonding of TS-1, adhesion of TS-1 and delamination of a fired body obtained using TS-1 was performed. The evaluation results are shown in Table 5.

(Example 27)
About coated sheet TS-2, it evaluated according to the method described in the said evaluation method about the dimensional stability at the time of pressure bonding of TS-2, and the adhesiveness of TS-2. The evaluation results are shown in Table 7.

[Comparative example]
(Comparative Examples 1 to 9)
About each of the ceramic green sheets GS-A to GS-I, the dimensional stability of the ceramic green sheets upon pressure bonding, the adhesiveness of the ceramic green sheets, and the delamination of the fired body obtained using the ceramic green sheets, Evaluation was performed according to the method described in the said evaluation method. The evaluation results are shown in Table 6.

(Comparative example 10)
The evaluation was performed according to the method described in the above evaluation method 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. At this time, the ratio of the intensity of Ba + ions to the intensity of Ti + ions on the surface of the ceramic green sheet was 1064. The evaluation results are shown in Table 6.

(Comparative example 11)
About coated sheet TS-3, it evaluated according to the method described in the said evaluation method about the dimensional stability at the time of pressure bonding of TS-3, and the adhesiveness of TS-3. The evaluation results are shown in Table 7.

Claims (11)

  This is the ratio of the detected Ba + ion intensity to the detected Ti + ion intensity when performing secondary ion analysis with a time-of-flight secondary ion analyzer on at least one side of the ceramic green sheet (Ba + ion A ceramic green sheet in which the strength of () / (Ti + ion strength) satisfies 20 <(Ba + ion strength) / (Ti + ion strength) <1000. A binder resin (A) having a hydroxyl group in the molecule, and a chemical formula (1):

(Wherein, R 1 and R 4 each independently represent an organic group having at least one ether bond. R 2 represents an alkylene group having 1 to 20 carbon atoms which may have a branch. R 3 represents carbon) The ceramic green sheet according to claim 1, which contains at least the organic compound (B) represented by the following formula (4): m represents an integer of 0 to 5). .   The ceramic green sheet according to claim 2, wherein the acid value of the organic compound (B) is 5 mgKOH / g or less. Each of R 1 and / or R 4 independently has a chemical formula (2):

(Wherein, R 5 represents an alkyl group which may have a C 1 to C 10 branched chain. R 6 represents an alkylene group which may have a C 1 to C 10 branched chain. R 7 has a carbon number 1 to 1 The ceramic green sheet according to claim 2 or 3, which is an organic group having at least one ether bond represented by (4) which represents an alkylene group of 4. n represents an integer of 0 to 2.   The ceramic green sheet according to any one of claims 2 to 4, which contains 1 to 60 parts by mass of the organic compound (B) with respect 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) contains at least one selected from the group consisting of polyvinyl acetal and (meth) acrylic resin.   The binder resin (A) contains a polyvinyl acetal, the polyvinyl acetal has an acetalization degree of 50 to 85 mol%, a content of vinyl ester monomer units of 0.1 to 20 mol%, and a viscosity average The ceramic green sheet according to claim 6, having a degree of polymerization of 200 to 5,000.   The ceramic green sheet according to any one of claims 2 to 7, comprising barium titanate and containing 3 to 20 parts by mass of the binder resin (A) with respect to 100 parts by mass of barium titanate.   The coated sheet which arrange | positions the layer which dried the electrically conductive paste on the at least one surface of the ceramic green sheet in any one of Claims 1-8.   The coated sheet according to claim 9, wherein at least a part of the ceramic green sheet is subjected to plasma treatment.   The coated sheet according to claim 9 or 10, wherein at least a part of the surface of the coated sheet is plasma-treated.