JP6732588B2 - Inorganic compound dispersing agent, slurry composition, ceramic green sheet, conductive paste and coating sheet - Google Patents

Description

TECHNICAL FIELD The present invention relates to an inorganic compound-dispersing agent capable of producing a slurry composition having excellent dispersibility and storage stability by dispersing an inorganic compound, and the slurry composition. In addition, when a ceramic green sheet is produced by using it as a ceramic slurry, it is possible to produce a ceramic green sheet which is excellent in adhesiveness during pressure bonding, has little dimensional change during pressure bonding, and is less likely to cause delamination. And a ceramic green sheet. Furthermore, when applied to any ceramic green sheet, in the case of producing a coated sheet, it is excellent in adhesiveness at the time of pressure bonding, and a conductive paste capable of producing a coated sheet in which delamination does not easily occur, and The present invention relates to the coated sheet. Further, when a ceramic green sheet is coated with an arbitrary conductive paste to produce a coated sheet, it is possible to produce a coated sheet which is excellent in adhesiveness at the time of pressure bonding and does not easily cause delamination. The present invention relates to a green sheet and the coated sheet.

Various polymers have been proposed for the polyvinyl acetal, since a tough film can be obtained and the polyvinyl acetal has a unique structure having both a hydrophilic hydroxy group and a hydrophobic acetal group.

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 preferably used in the process of manufacturing a laminated ceramic capacitor or a circuit board of an IC chip, for example. A circuit board of a monolithic ceramic capacitor or an IC chip is manufactured by a method in which an electrode layer is formed on a ceramic green sheet, which are stacked and temporarily pressure-bonded, and after the main pressure-bonding, the electrode and the ceramic are simultaneously fired.

The performance required for a binder for ceramic molding is that a ceramic slurry with excellent dispersibility and storage stability can be obtained, the amount of carbon residue after firing is small, and the adhesiveness during thermocompression bonding is excellent. And so on. When the dispersibility or storage stability of the ceramic slurry is insufficient, the density, smoothness, etc. of the obtained ceramic green sheets may be insufficient, and the adhesiveness between the ceramic green sheets may deteriorate. When the amount of carbon residue in the ceramic molded product after firing is large, the electrical characteristics of the ceramic molded product may become insufficient.

Further, polyvinyl acetal is also used as a binder for a conductive paste used for manufacturing a laminated ceramic capacitor or the like. This electrode layer forming step includes a method of directly forming the electrode layer on the ceramic green sheet by a method of printing the electrode layer and a method of forming the electrode layer on the carrier film by printing or the like, and heating the electrode layer from the carrier film to the ceramic green sheet. It may be transferred by pressing.

The multilayer ceramic capacitor is a chip type ceramic capacitor in which dielectrics such as titanium oxide and barium titanate and internal electrodes are stacked in multiple layers. Such a monolithic ceramic capacitor is formed, for example, by stacking a plurality of ceramic green sheets coated with a conductive paste to be internal electrodes by screen printing or the like, heat-pressing them to obtain a laminate, and then heating the laminate. Then, the binder is decomposed and removed (degreasing), and then baked to be manufactured.

2. Description of the Related Art In recent years, as electronic devices have become more multifunctional and more compact, multilayer ceramic capacitors have been required to have larger capacity and smaller size. Attempts have been made to meet these demands by thinning the ceramic green sheets and further increasing the layers of the laminated ceramic capacitors. For example, as a thinning method, the ceramic powder used for the ceramic green sheet has a fine particle diameter of 0.5 μm or less, and is a thin film of 5 μm or less on a peelable support. Attempts have been made to coat it.

However, when a ceramic powder with a fine particle size is used for thinning, the packing density and surface area of the ceramic powder increase, so the amount of resin in the binder used increases, and along with this, the ceramic green sheet Since the viscosity of the slurry composition for use also increases, coating may be difficult, or defective dispersion of the ceramic powder itself may occur. In addition, the storage stability of the slurry and the dimensional stability of the ceramic green sheet may not be sufficient. Furthermore, as multilayer ceramic multilayer capacitors are laminated with multiple layers of ceramic green sheets, if the resin decomposes rapidly at the time of degreasing, delamination called delamination will occur as described above, and the reliability of parts will deteriorate. I may end up doing it.

There is a limit to the miniaturization of monolithic ceramic capacitors, and in order to increase the capacity of monolithic ceramic capacitors or to miniaturize them while maintaining the capacity, in addition to thinning the ceramic green sheets, multi-layering is also required. .. A monolithic ceramic capacitor is obtained by forming an electrode layer on a ceramic green sheet, and laminating a ceramic green sheet having an electrode layer formed thereon or a ceramic green sheet having no electrode layer formed thereon to form a composite laminated body. ..

However, in the process of temporarily press-bonding the ceramic green sheet when manufacturing the multilayer ceramic capacitor, if the pressure is increased, the ceramic green sheet and the electrode layer are deformed, which makes it difficult to achieve the high precision required for the multilayer ceramic component. there were. On the other hand, if the pressure bonding is weakened, the adhesive strength between the ceramic green sheets or between the ceramic green sheets and the electrode layer is weak in the conventional manufacturing method, and the upper and lower ceramic green sheets or the ceramic green sheet and the electrode layer may not adhere to each other. .. If such a poor adhesion occurs, there is a problem that cutting defects due to the displacement of the bonding surface and defects such as delamination after firing the ceramic laminated body occur, resulting in a decrease in the reliability of the component. In addition, when an excessive amount of plasticizer is added to improve the adhesiveness, it is deformed during pressure bonding, and it is difficult to obtain a desired laminated sheet.

Further, in the step of forming the electrode layer, a method of directly forming the electrode layer on the ceramic green sheet by a method of forming the electrode layer on the carrier film by printing or a method of forming the electrode layer on the carrier film from the carrier film to the ceramic green sheet. It may be transferred by heat pressing.

Even in the process of pressing and transferring the electrode layer from the carrier film to the ceramic green sheet, if the pressure is increased, the electrode layer is deformed and the high precision required for the laminated ceramic component cannot be realized. On the other hand, when the pressure bonding is weakened, in the conventional manufacturing method, the adhesive force between the ceramic green sheet and the electrode layer is weak and the electrode layer and the ceramic green sheet do not adhere to each other. When such a poor adhesion occurs, not only the electrode layer cannot be formed, but also a defect may occur after firing the ceramic laminated body, resulting in a problem that the reliability of the component deteriorates.

As an attempt to solve the above-mentioned problems, for example, in Patent Document 1, by using a ceramic slurry containing a phthalic acid-based plasticizer and a glycol-based plasticizer and/or an aminoalcohol-based plasticizer, slurry preparation workability, It is described that a ceramic green sheet having excellent adhesiveness during thermocompression bonding and excellent mechanical strength can be obtained. Patent Document 2 describes a ceramic paste having a high plasticizing effect and containing a suitable volatility.

Patent Document 3 discloses a step of preparing a plurality of ceramic green sheets containing ceramic powder and an organic binder as essential components, and forming an electrode layer on the surface of at least a part of the plurality of ceramic green sheets. And a step of laminating and firing the plurality of ceramic green sheets, wherein the surface of the laminate formed by laminating the plurality of ceramic green sheets is subjected to a surface treatment with ozone. After that, a manufacturing method of laminating a ceramic green sheet on the surface-treated surface is described.

In Patent Document 4, a polymerizable monomer containing a (meth)acrylic acid ester as a main component is added to an aqueous medium in which a polyvinyl acetal resin is dispersed so that the polyvinyl acetal resin is permeated into the aqueous medium and then polymerized. The binder resin for conductive paste containing the polyvinyl acetal/(meth)acrylic acid ester composite resin obtained by the above is described.

JP, 2001-106580, A JP, 2006-027990, A JP, 2003-95750, A JP, 2005-15654, A

However, Patent Documents 1 and 2 describe ceramic green sheets and ceramic pastes that are composed of a combination of a specific plasticizer or a composition of a combination of a specific plasticizer and a thermoplastic resin. Although there is a description of improving the adhesiveness or mechanical strength of the ceramic green sheet, there are still insufficient points in improving the storage stability of slurries and pastes and improving the quality of capacitors. Patent Document 3 describes a manufacturing method for improving adhesiveness by subjecting a surface of a ceramic green sheet to surface treatment with ozone, but all of them are described only for improving adhesiveness, and storage stability of the conductive paste is described. To improve the quality of the molded product by reducing the amount of carbon residue. If the storage stability of the conductive paste is insufficient, the printability when printing the conductive paste on the surface of the ceramic green sheet is poor, the smoothness of the printed surface is poor, and if the amount of carbon residue is large, The electrical properties of the sintered body may become insufficient. The storage stability of the conductive paste using the binder resin for conductive paste described in Patent Document 4 was insufficient.

The present invention has been made to solve the above problems, and an object of the present invention is to provide an inorganic compound dispersing agent having excellent dispersibility of an inorganic compound.

Another object of the present invention is to provide an inorganic compound dispersing agent, which is excellent in storage stability when the slurry composition is prepared using the inorganic compound dispersing agent.

Further, the present invention provides an inorganic compound dispersing agent having excellent adhesiveness when pressure-bonding the ceramic green sheet when a ceramic green sheet is produced using a slurry composition obtained from the inorganic compound dispersing agent. With the goal.

Further, the present invention is a case where a conductive paste is prepared using a slurry composition obtained from an inorganic compound dispersing agent, and a coating sheet obtained by applying the conductive paste to any ceramic green sheet is prepared. An object of the present invention is to provide an agent for dispersing an inorganic compound, which has excellent adhesiveness during pressure bonding. Further, the present invention is a case where a ceramic green sheet is produced using a slurry composition obtained from an inorganic compound dispersing agent, and a coated sheet obtained by applying any conductive paste to the ceramic green sheet is produced. In addition, it is an object of the present invention to provide an agent for dispersing an inorganic compound, which has excellent adhesiveness during pressure bonding.

Another object of the present invention is to provide a ceramic green sheet or a coated sheet that is less prone to delamination when a ceramic green sheet and/or a coated sheet is laminated to produce a fired body.

Another object of the present invention is to provide an inorganic compound dispersing agent that is less likely to undergo dimensional change during pressure bonding when ceramic green sheets and/or coating sheets obtained by using the inorganic compound dispersing agent are laminated. The purpose is to provide.

（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）および有機溶剤（Ｃ）を含有する樹脂組成物からなる無機化合物分散用剤であって、該無機化合物分散用剤の酸価が５ｍｇＫＯＨ／ｇ以下である無機化合物分散用剤；
［２］有機化合物（Ｂ）の酸価が５ｍｇＫＯＨ／ｇ以下である、［１］の無機化合物分散用剤；
［３］Ｒ１および／またはＲ４がそれぞれ独立して、下記一般式（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、［１］または［２］の無機化合物分散用剤；
［４］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、［１］〜［３］のいずれかの無機化合物分散用剤；
［５］バインダー樹脂（Ａ）が、ポリビニルアセタール、エチルセルロースおよび(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、［１］〜［４］のいずれかの無機化合物分散用剤；
［６］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、［５］の無機化合物分散用剤；
［７］無機化合物（Ｄ）および［１］〜［６］のいずれかの無機化合物分散用剤を含有するスラリー組成物；
［８］分子内に水酸基を有するバインダー樹脂（Ａ）、下記一般式（１）：

（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）、有機溶剤（Ｃ）および無機化合物（Ｄ）を含有する樹脂組成物からなるスラリー組成物；
［９］無機化合物（Ｄ）がセラミック粉体である、［７］または［８］のスラリー組成物；
［１０］前記セラミック粉体１００質量部に対して、有機溶剤（Ｃ）を２〜２００質量部含有する、［９］のスラリー組成物；
［１１］［９］または［１０］のスラリー組成物を用いて作製されたセラミックグリーンシート；
［１２］セラミックグリーンシートの少なくとも片面について、飛行時間型二次イオン分析装置で二次イオン分析を行った場合に、検出されるＴｉ＋イオンの強度に対する、検出されるＢａ＋イオンの強度の比である（Ｂａ＋イオンの強度）／（Ｔｉ＋イオンの強度）が、２０＜（Ｂａ＋イオンの強度）／（Ｔｉ＋イオンの強度）＜１０００を満たす、［１１］のセラミックグリーンシート。
［１３］無機化合物（Ｄ）が導電粉末である、［７］または［８］のスラリー組成物；
［１４］前記導電粉末１００質量部に対して、バインダー樹脂（Ａ）を１〜５０質量部含有する、［１３］のスラリー組成物；
［１５］前記導電粉末１００質量部に対して、有機溶剤（Ｃ）を５〜６００質量部含有する、［１３］または［１４］のスラリー組成物；
［１６］［１３］から［１５］のいずれかのスラリー組成物からなる導電ペースト；
［１７］［１１］または［１２］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；
［１８］［１６］の導電ペーストを乾燥させた層を、セラミックグリーンシートの少なくとも一方の面に配置してなる塗工シート；
［１９］少なくとも一部にプラズマ処理が施された、［１１］または［１２］のセラミックグリーンシート；
［２０］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、［１７］または［１８］の塗工シート； According to the present invention, the above object is
[1] A binder resin (A) having a hydroxyl group in the molecule, the following general formula (1):

(In the formula, R1 and R4 each independently represent an organic group having at least one ether bond. R2 represents an alkylene group having 1 to 20 carbon atoms and optionally having a branch. R3 represents carbon. From the resin composition containing the organic compound (B) and the organic solvent (C) represented by Formula 1 to 4 which may have a branched alkylene group, and m represents an integer of 0 to 5. An inorganic compound dispersing agent, wherein the inorganic compound dispersing agent has an acid value of 5 mgKOH/g or less;
[2] The inorganic compound dispersion agent according to [1], wherein the organic compound (B) has an acid value of 5 mgKOH/g or less;
[3] R1 and/or R4 are each independently the following general formula (2):

(In the formula, R5 represents an alkyl group having 1 to 10 carbon atoms which may have a branch. R6 represents an alkylene group having 1 to 10 carbon atoms which may have a branch. R7 represents 1 to 1 carbon atoms. 4 represents an alkylene group, and n represents an integer of 0 to 2), which is an organic group having at least one ether bond represented by the formula [1] or [2];
[4] The inorganic compound dispersion agent according to any one of [1] to [3], containing 1 to 60 parts by mass of the organic compound (B) with respect to 100 parts by mass of the binder resin (A);
[5] The inorganic compound dispersion agent according to any one of [1] to [4], wherein the binder resin (A) contains at least one selected from the group consisting of polyvinyl acetal, ethyl cellulose and (meth)acrylic resin;
[6] The binder resin (A) contains 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 %. An agent for dispersing an inorganic compound according to [5], which has a viscosity average degree of polymerization of 200 to 5,000;
[7] A slurry composition containing the inorganic compound (D) and the inorganic compound dispersing agent of any one of [1] to [6];
[8] A binder resin (A) having a hydroxyl group in the molecule, the following general formula (1):

(In the formula, R1 and R4 each independently represent an organic group having at least one ether bond. R2 represents an alkylene group having 1 to 20 carbon atoms and optionally having a branch. R3 represents carbon. Represents an alkylene group which may have a branch number of 1 to 4, m represents an integer of 0 to 5), an organic compound (B), an organic solvent (C) and an inorganic compound (D). A slurry composition comprising the resin composition contained;
[9] The slurry composition of [7] or [8], wherein the inorganic compound (D) is a ceramic powder;
[10] The slurry composition of [9], which contains 2 to 200 parts by mass of an organic solvent (C) with respect to 100 parts by mass of the ceramic powder;
[11] A ceramic green sheet produced by using the slurry composition of [9] or [10];
[12] This is the ratio of the detected Ba+ ion intensity to the detected Ti+ ion intensity when secondary ion analysis is performed on at least one side of the ceramic green sheet with a time-of-flight secondary ion analyzer. The ceramic green sheet of [11], wherein (Ba+ ion strength)/(Ti+ ion strength) satisfies 20<(Ba+ ion strength)/(Ti+ ion strength)<1000.
[13] The slurry composition of [7] or [8], wherein the inorganic compound (D) is a conductive powder;
[14] The slurry composition of [13], containing 1 to 50 parts by mass of the binder resin (A) with respect to 100 parts by mass of the conductive powder;
[15] The slurry composition according to [13] or [14], containing 5 to 600 parts by mass of an organic solvent (C) with respect to 100 parts by mass of the conductive powder;
[16] A conductive paste comprising the slurry composition according to any one of [13] to [15];
[17] A coated sheet obtained by arranging a layer obtained by drying a conductive paste on at least one surface of the ceramic green sheet of [11] or [12];
[18] A coated sheet obtained by arranging a layer obtained by drying the conductive paste according to [16] on at least one surface of a ceramic green sheet;
[19] The ceramic green sheet of [11] or [12], at least a part of which is subjected to plasma treatment;
[20] The coated sheet according to [17] or [18], wherein at least a part of the surface of the coated sheet is plasma-treated.

According to the present invention, an inorganic compound dispersing agent having excellent dispersibility of an inorganic compound can be provided.

Further, when a slurry composition is prepared using the inorganic compound dispersing agent of the present invention, it is possible to provide an inorganic compound dispersing agent having excellent storage stability of the slurry composition.

Further, when a ceramic green sheet is produced by using a slurry composition obtained from the inorganic compound dispersing agent of the present invention, it is possible to provide an inorganic compound dispersing agent having excellent adhesiveness when the ceramic green sheet is pressure-bonded.

Further, in the case of producing a conductive paste using the slurry composition obtained by the inorganic compound dispersing agent of the present invention, in the case of producing a coating sheet obtained by applying the conductive paste to any ceramic green sheet, It is possible to provide an agent for dispersing an inorganic compound, which has excellent adhesiveness when a coated sheet is pressure-bonded. Further, when a ceramic green sheet obtained by applying the inorganic compound dispersing agent of the present invention to prepare a coated sheet obtained by coating any conductive paste, an inorganic compound dispersing agent excellent in adhesiveness at the time of pressure bonding is obtained. Can be provided.

Further, when a ceramic green sheet and/or a coating sheet of the present invention is laminated to produce a fired body, it is possible to provide a ceramic green sheet or a coating sheet in which delamination does not easily occur.

Further, according to another object of the present invention, it is possible to provide an agent for dispersing an inorganic compound, which is less likely to cause a dimensional change during pressure bonding when the ceramic green sheet and/or the coating sheet of the present invention are laminated.

（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）および有機溶剤（Ｃ）を含む無機化合物分散用剤であって、該無機化合物分散用剤の酸価が５ｍｇＫＯＨ／ｇ以下である無機化合物分散用剤に関するものである。 The agent for dispersing an inorganic compound of the present invention comprises a binder resin (A) having a hydroxyl group in the molecule, the following general formula (1):

(In the formula, R1 and R4 each independently represent an organic group having at least one ether bond. R2 represents an alkylene group having 1 to 20 carbon atoms and optionally having a branch. R3 represents carbon. Represents an alkylene group which may have a branch number of 1 to 4, m represents an integer of 0 to 5), and an inorganic compound dispersing agent containing an organic compound (B) and an organic solvent (C). The present invention also relates to an inorganic compound dispersing agent having an acid value of 5 mgKOH/g or less.

[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, ethyl cellulose, methyl cellulose, ethyl hydroxyethyl cellulose, polyvinyl alcohol, and a hydroxyl group ( Examples thereof include (meth)acrylic resin, polyacrylic acid, and polyalkylene oxide. Among them, polyvinyl acetal, ethyl cellulose, and a (meth)acrylic resin having a hydroxyl group are preferable in terms of dispersibility of the inorganic compound in the inorganic compound dispersing agent, and flexibility and adhesiveness of the ceramic green sheet or coating sheet, and polyvinyl acetal is preferable. More preferable.

The acid value of the binder resin (A) is preferably 3 mgKOH/g or less, more preferably 2 mgKOH/g or less, further preferably 1 mgKOH/g or less, and 0.8 mgKOH/g or less. Is particularly preferable. When the acid value of the binder resin (A) satisfies the above range, the storage stability of the slurry composition using the inorganic compound dispersing agent is excellent, and a ceramic green sheet is produced using the slurry composition. This is preferable from the viewpoint of reducing delamination in the case of doing so and also from the viewpoint of reducing corrosiveness in the production process.

In the case of using the polyvinyl acetal described below as the binder resin (A), in order to keep the acid value of the polyvinyl acetal at 3 mgKOH/g or less, the aldehydes were first added to the aqueous solution of polyvinyl alcohol as the raw material of the polyvinyl acetal. A method to generate a porous polyvinyl acetal that is easy to wash by adding a catalyst at a low temperature later, improving stirring efficiency, or using a surfactant, and using a water-soluble organic solvent when washing with water after the reaction Method, a method of adding a compound that easily reacts with an acid such as an epoxy compound, a method of dissolving a resin in a solvent and purifying it using a dialysis membrane or the like. Among these, from the viewpoint of process simplification, a method of generating a porous polyvinyl acetal is particularly preferable, and a method of adding a catalyst at a low temperature after first adding an aldehyde to an aqueous solution of polyvinyl alcohol as a raw material is a method. Particularly preferably adopted. The acid value is measured by the method described in JIS K 6728:1977.

(Polyvinyl acetal)
When polyvinyl acetal is contained as 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. It is more preferably at least 70% by mass, particularly preferably at least 70% by mass, and most preferably 100% by mass.

The degree of acetalization of the polyvinyl acetal is preferably 50 mol% or more, more preferably 55 mol% or more, further preferably 60 mol% or more, and particularly preferably 65 mol% or more. .. Further, the degree of acetalization of polyvinyl acetal is preferably 85 mol% or less, more preferably 82 mol% or less, further preferably 78 mol% or less, and particularly preferably 75 mol% or less. preferable.

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, further preferably 0.5 mol% or more. It is preferably 0.7 mol% or more, and 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, further preferably 15 mol% or less, and 13 mol% or less. Is particularly preferable.

The content of the vinyl alcohol monomer unit in the polyvinyl acetal is preferably 15 mol% or more, and more preferably 25 mol% or more. The content of the vinyl alcohol monomer unit in the polyvinyl acetal is preferably 50 mol% or less, more preferably 40 mol% or less, and further preferably 35 mol% or less. Among the vinyl alcohol monomer units in the raw material PVA, those not acetalized remain as vinyl alcohol monomer units in the obtained polyvinyl acetal.

The content of monomer units other than acetalized monomer units, vinyl ester monomer units and vinyl alcohol monomer units in the polyvinyl acetal is preferably 20 mol% or less. More preferably, it is at most mol %.

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 degree of polymerization of the polyvinyl acetal is preferably 200 or more, and preferably 5000 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 the viscosity of the raw material polyvinyl alcohol (hereinafter sometimes abbreviated as “PVA”) measured according to JIS K 6726:1994. It is represented by the average degree of polymerization. That is, after re-saponifying PVA to a saponification degree of 99.5 mol% or more and purifying it, from the intrinsic viscosity [η] (l/g) measured in water at 30°C, the formula (I):

Can be obtained by The viscosity average degree of polymerization of PVA and the viscosity average degree of polymerization 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, further 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, further preferably 99.5 mol% or less, and 99.3 mol% or less. Is most preferable.

When the saponification degree of the raw material PVA exceeds 99.9 mol%, it may be impossible to stably produce PVA. 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 polymerizing a vinyl ester monomer and saponifying the obtained polymer. As a method for polymerizing the vinyl ester-based monomer, a conventionally known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method or an 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 depending on the polymerization method. As the saponification reaction, alcoholysis or hydrolysis using a conventionally known alkali catalyst or acid catalyst can be applied. Among them, the saponification reaction using a caustic soda (NaOH) catalyst with methanol as a solvent 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 palmitine. Examples thereof include vinyl acetate, vinyl stearate, vinyl oleate, and vinyl benzoate, with vinyl acetate being particularly preferred.

Further, when the vinyl ester-based monomer is polymerized, it may be copolymerized with another monomer within a range not impairing the gist 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, α-olefins such as ethylene, propylene, n-butene, i-butene; acrylic acid and salts thereof; methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic. Acrylic acid esters such as i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methacrylic acid and its salts; methacrylic Methyl acid, 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 acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N,N-dimethyl acrylamide, diacetone acrylamide, acrylamidopropanesulfonic acid and its salts, acrylamidopropyldimethylamine and its acid salts or quaternary salts , Acrylamide derivatives such as N-methylolacrylamide and its derivatives; methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidepropanesulfonic acid and its salts, methacrylamidepropyldimethylamine and its acid salts or quaternary salts. , Methacrylamide derivatives such as N-methylol methacrylamide and its derivatives; 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, stearyl. Vinyl ethers such as vinyl 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 the like. 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 α-olefin unit, the content has a preferable lower limit of 1 mol% and a preferable upper limit of 20 mol %. If it is less than 1 mol %, the effect of containing the α-olefin becomes insufficient, and if it exceeds 20 mol %, the hydrophobicity becomes too strong and the dispersibility of the ceramic powder is lowered, or the polyvinyl alcohol resin Since the solubility decreases, the acetalization reaction becomes difficult.

In the present invention, the acid catalyst used in the acetalization reaction is not particularly limited, and either an organic acid or an inorganic acid can be used. For example, acetic acid, paratoluenesulfonic 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. Further, in general, when nitric acid is used, the reaction rate of the acetalization reaction becomes faster, and improvement in productivity can be expected, while the particles of the polyvinyl acetal to be obtained tend to be coarse, and the variation between batches tends to increase. Therefore, hydrochloric acid is particularly preferable.

The aldehyde used in the acetalization reaction is not particularly limited, and examples thereof include known aldehydes having a hydrocarbon group. The aldehyde having a hydrocarbon group is, as an aliphatic aldehyde, formaldehyde (including paraformaldehyde), acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, hexylaldehyde, 2-ethylbutyraldehyde, Pivalaldehyde, octyl aldehyde, 2-ethylhexyl aldehyde, nonyl aldehyde, decyl aldehyde, dodecyl aldehyde, etc., and as alicyclic aldehydes, cyclopentane aldehyde, methyl cyclopentane aldehyde, dimethyl cyclopentane aldehyde, cyclohexane aldehyde, methyl cyclohexane aldehyde , Dimethyl cyclohexane aldehyde, cyclohexane acetaldehyde and the like, cyclic unsaturated aldehydes such as cyclopentene aldehyde and cyclohexene aldehyde, and aromatic or unsaturated bond-containing aldehydes such as benzaldehyde, methylbenzaldehyde, dimethylbenzaldehyde, methoxybenzaldehyde and phenylacetaldehyde. , Phenylpropyl aldehyde, cumin aldehyde, naphthyl aldehyde, anthra aldehyde, cinnam aldehyde, croton aldehyde, acrolein aldehyde, 7-octen-1-al and the like, and heterocyclic aldehydes include furfural aldehyde and methyl furfural aldehyde. 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 preferable. In the present invention, it is also possible to use a polyvinyl acetal obtained by using two or more aldehydes in combination.

As the aldehyde used for the acetalization reaction, an aldehyde other than a hydrocarbon type can 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.

As the aldehyde having an amino group as a functional group, aminoacetaldehyde, dimethylaminoacetaldehyde, diethylaminoacetaldehyde, aminopropionaldehyde, dimethylaminopropionaldehyde, aminobutyraldehyde, aminopentylaldehyde, aminobenzaldehyde, dimethylaminobenzaldehyde, ethylmethylaminobenzaldehyde, Examples thereof include diethylaminobenzaldehyde, pyrrolidylacetaldehyde, piperidylacetaldehyde, and pyridylacetaldehyde, and aminobutyraldehyde is preferable from the viewpoint of productivity.

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

Examples of the aldehyde having a carbonyl group as a functional group include 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, and 5-formylpentane. Acid and its metal salt or ammonium salt, 4-formylphenoxyacetic 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- Examples include dicarboxybenzaldehyde and its metal salts or ammonium salts.

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

Further, as long as the characteristics of the present invention are not impaired, 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, nitro group or quaternary ammonium. Aldehydes having salts and the like, aldehydes having halogen atoms and the like may be used.

((Meth)acrylic resin having 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 are used as the (meth)acrylic resin having a hydroxyl group. Can be used. Examples of the (meth)acrylic monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate and 2,3-dihydroxypropyl acrylate. Acrylate 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-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol-polypropylene glycol monomethacrylate, polyethylene glycol -Methacrylates such as polytetramethylene glycol monomethacrylate and polypropylene glycol-polytetramethylene glycol monomethacrylate. Among them, methacrylate having a hydroxyl group is preferable from the viewpoint of sinterability, and specifically, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, and polypropylene glycol monomethacrylate are preferable.

Examples of the (meth)acrylic monomer having no hydroxyl group include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n. -Acrylate such as hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, isodecyl acrylate, isobornyl acrylate, tetrahydrofuryl acrylate; ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl Methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, isodecyl methacrylate, isobornyl methacrylate, tetrahydrofuryl methacrylate, and other methacrylates can be mentioned. 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-. Hexyl methacrylate, cyclohexyl methacrylate and 2-ethylhexyl methacrylate are preferred.

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. When 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. 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 the binder resin (A) is used together with the polyvinyl acetal resin. Sometimes.

(Other)
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 the polyvinyl acetal and the other binder resin (A) are mixed, for example, the mass ratio of the polyvinyl acetal and the other binder resin (A) is preferably 5/95 or more, more preferably 10/90 or more. .. The mass ratio of 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), ethyl cellulose or a (meth)acrylic resin having a hydroxyl group is preferable, and ethyl cellulose is more preferable. When mixing polyvinyl acetal and ethyl cellulose, the mass ratio of polyvinyl acetal and ethyl cellulose is preferably 5/95 or more, more preferably 10/90 or more. The mass ratio of polyvinyl acetal to ethyl cellulose is preferably 95/5 or less, more preferably 90/10 or less.

In the agent for dispersing an inorganic compound 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 effects 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, and preferably 0.1 parts by mass or more, relative to 100 parts by mass of the binder resin (A). More preferable. Further, 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, relative 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、スラリー組成物の保存安定性、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)]
The inorganic compound dispersion agent of the present invention has the chemical formula (1):

The organic compound (B) represented by R2 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 further preferably 8 or less. The carbon number of R2 is preferably 2 or more, more preferably 3 or more, and further preferably 4 or more. When the carbon number of R2 is out of the above range, the compatibility between the organic compound (B) and the binder resin (A) becomes poor, and the storage stability of the slurry composition and the adhesiveness of the ceramic green sheet tend to be deteriorated. is there. 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, and 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 0-5. m is preferably 2 or less, more preferably 1 or less, and further 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 the same. R1 and R4 are each represented by the chemical formula (2):

The organic group having at least one ether bond represented by is preferable from the viewpoint of compatibility with the binder resin (A).

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 further 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) becomes poor, and the storage stability of the slurry composition and the adhesiveness of the ceramic green sheet tend to be deteriorated. .. R6 represents an alkylene group having 1 to 10 carbon atoms which may have a branch. The carbon number of R6 is preferably 8 or less, more preferably 6 or less, and further 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) becomes poor, and the storage stability of the slurry composition and the adhesiveness of the ceramic green sheet tend to be deteriorated. .. R7 represents an alkylene group having 1 to 4 carbon atoms which may have a branch. The carbon number of R7 is preferably 3 or less, and more preferably 2 or less. R6 and R7 may each independently have a linear structure or may have a branch. R6 and R7 preferably have a linear structure. A plurality of R7 may be the same or different.

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

The acid value of the organic compound (B) is preferably 5 mgKOH/g or less, more preferably 3 mgKOH/g or less, further preferably 1 mgKOH/g or less, and 0.5 mgKOH/g or less. Is particularly preferable. As described above, when the above range is satisfied, from the viewpoint of stability of quality such as viscosity during long-term storage (storage stability) and reduction of delamination due to rapid decomposition during degreasing, It is preferable from the viewpoint of reducing corrosiveness. Here, when the organic compound (B) contains impurities, the acid value including impurities is to be measured.

The molecular weight of the organic compound (B) is preferably 200 or more, more preferably 250 or more. When the molecular weight is less than the above range, the volatility is high, and when the sheet is dried, it volatilizes, and sufficient adhesiveness may not be exhibited. 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 the organic compound (B) is solidified, and the compatibility with the resin tends to be lowered.

The structure of the organic compound (B) is preferably one having no hydroxyl group in the molecule. When the organic compound (B) contains a hydroxyl group, the action at the interface at the time of pressure bonding tends to be lowered, and sufficient adhesiveness may not be obtained.

Examples of the organic compound (B) include bis(2-butoxyethyl) adipate, bis(2-methoxyethyl) adipate, bis(2-ethoxyethyl) adipate, and 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 in terms of excellent storage stability of the slurry composition, excellent adhesiveness of the ceramic green sheet, and moderate strength retention. ..

The content of the organic compound (B) is not particularly limited, but is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and more preferably 10 parts by mass or more with respect to 100 parts by mass of the binder resin (A). Is more preferable. When the content of the organic compound (B) is less than 1 part by mass, the inorganic dispersibility and the storage stability of the slurry composition tend to deteriorate. The content of the organic compound (B) is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 40 parts by mass or less. When the content of the organic compound (B) exceeds 60 parts by mass with respect to 100 parts by mass of the binder resin (A), the strength of the ceramic green sheet obtained from the slurry composition decreases, and the dimensional stability at the time of pressure bonding is reduced. It tends to decrease.

[Organic solvent (C)]
The agent for dispersing an inorganic compound of the present invention contains an organic solvent (C). The organic solvent (C) may be appropriately used depending on its purpose and application, and examples thereof include alcohols such as methanol, ethanol, isopropanol, n-propanol, butanol; and cellsolves 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; menten, menthane, menthone, myrcene, α-pinene, α- Terpinene, γ-terpinene, limonene, perillyl acetate, menthyl acetate, carbyl acetate, dihydrocarbyl acetate, perillyl alcohol, dihydroterpineol acetate, terpineol acetate, dihydroterpineol, terpinyloxyethanol, dihydroterpinyloxyethanol, Terpinyl methyl ether, dihydroterpinyl methyl ether, dihydroterpinyl propionate, isobonyl acetate, isobonyl propionate, isobonyl butyrate, isobonyl isobutyrate, novir acetate, octyl acetate, dimethyl octyl Acetate, butyl carbitol acetate, acetoxy-methoxyethoxy-cyclohexanol acetate, dihydrocarbeol, 2-ethylhexyl glycol, benzyl glycol, phenylpropylene glycol, methyldecalin, amylbenzene, cumene, cymene, 1,1-diisopropylhexane, citronellol Etc.

[Inorganic compound dispersing agent]
In the present application, the "inorganic compound dispersing agent" is a resin composition that functions as a dispersion medium when dispersing an inorganic compound. By preparing in advance as an inorganic compound dispersing agent, it becomes easy to produce a ceramic slurry, a conductive paste, etc., and it becomes possible to shorten the time and simplify the equipment.

The concentration of the binder resin (A) contained in the agent for dispersing an inorganic compound of the present invention is preferably 2% by mass or more, and more preferably 5% by mass or more. If it is less than 2% by mass, it is necessary to concentrate the composition at the time of preparing the slurry, and workability may be deteriorated. Further, the upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less. When the concentration of the binder resin (A) in the composition is more than 50% by mass, the viscosity of the inorganic compound dispersing agent becomes remarkably high, and the viscosity stability during storage and the handling property during handling may deteriorate. is there.

The acid value of the inorganic compound dispersing agent of the present invention is 5 mgKOH/g or less, preferably 3 mgKOH/g or less, and more preferably 1 mgKOH/g or less. When the acid value satisfies the above range, the binder resin (A) contained in the agent for dispersing an inorganic compound is less likely to be decomposed (hydrolyzed, etc.), so that the slurry composition has stable quality such as viscosity during long-term storage. Is preferable from the viewpoint of reducing the delamination due to rapid decomposition during degreasing of the obtained ceramic green sheet, and also from the viewpoint of reducing corrosiveness in the production process. In order to adjust the acid value of the agent for dispersing an inorganic compound of the present invention to the above range, the acid value of the organic compound (B) contained in the agent for dispersing an inorganic compound used in the present invention is lowered in advance, or the binder resin (A The method of lowering the acid value of) is preferable.

（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。）で示される有機化合物（Ｂ）および有機溶剤（Ｃ）を含むスラリー組成物である。 [Slurry composition]
A preferred embodiment of the present invention is a slurry composition comprising an inorganic compound dispersing agent and an inorganic compound (D). Specifically, an inorganic compound, a binder resin (A) having a hydroxyl group in the molecule, the following general formula (1):

(In the formula, R1 and R4 each independently represent an organic group having at least one ether bond. R2 represents an alkylene group having 1 to 20 carbon atoms and optionally having a branch. R3 represents carbon. It represents an alkylene group which may have a branch of the formulas 1 to 4, m represents an integer of 0 to 5), and is a slurry composition containing the organic compound (B) and the organic solvent (C).

[Inorganic compound (D)]
The inorganic compound (D) contained in the slurry composition of the present invention is not particularly limited, and examples thereof include ceramic powder, conductive powder, glass powder, phosphor fine particles, silicon oxide, etc., depending on its purpose and application. To be These can be used alone or in combination of two or more kinds as appropriate.

[Ceramic slurry]
The agent for dispersing an inorganic compound according to the present invention is excellent in dispersibility of ceramic powder and is also excellent in storage stability. Therefore, the slurry composition obtained therefrom can be suitably used as a ceramic slurry. A ceramic green sheet obtained by molding such a ceramic slurry has excellent surface smoothness and sheet strength. Further, the present ceramic green sheet has a small amount of carbon residue after firing. Therefore, when the ceramic slurry of the present invention is used, a high-performance ceramic molded product having a small amount of carbon residue can be obtained. If the dispersibility of the ceramic slurry and the storage stability are lowered, the surface of the ceramic green sheet is roughened, which may adversely affect the adhesiveness of the ceramic green sheet, the subsequent molded product, and the quality after firing.

In the ceramic slurry, the amount of the binder resin (A) with respect to the ceramic powder varies depending on the purpose of use of the ceramic green sheet, but is usually preferably 3 parts by mass or more with respect to 100 parts by mass of the ceramic powder, and 5 parts by mass. More preferably, it is at least part. The amount of the binder resin (A) used 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 the ceramic powder. When the amount of the binder resin (A) used is less than 3 parts by mass with respect to 100 parts by mass of the ceramic powder, the dispersibility of the slurry and the storage stability tend to be poor, and the resulting ceramic green sheet has poor adhesion. , And the strength may be insufficient. When the amount of the binder resin (A) used exceeds 20 parts by mass with respect to 100 parts by mass of the ceramic powder, the density of the ceramic powder in the ceramic green sheet decreases, so that the quality of the laminated ceramic capacitor as the final product is improved. In some cases, it may cause a decrease and further cause delamination due to an increase in volatile components during sintering.

The conditions for the binder resin (A) contained in the ceramic slurry are as described above.

When polyvinyl acetal is contained as the binder resin (A) contained in the ceramic slurry, suitable conditions for the degree of acetalization of polyvinyl acetal are as described above, but when the degree of acetalization is less than 50 mol%, the present invention The storage stability of the ceramic slurry tends to decrease. On the other hand, when the degree of acetalization exceeds 85 mol%, the content of hydroxyl groups (vinyl alcohol monomer units) in polyvinyl acetal decreases, and the strength and adhesiveness of the ceramic green sheet obtained using the ceramic slurry of the present invention are reduced. Also, the dimensional stability during pressure bonding tends to decrease, and the amount of carbon residue in the obtained ceramic molded product tends to increase.

When polyvinyl acetal is contained as the binder resin (A) contained in the ceramic slurry, if the vinyl alcohol monomer unit of the polyvinyl acetal is within the preferable range described above, the dimensional stability of the obtained ceramic green sheet during pressure bonding Tend to be better.

When polyvinyl acetal is contained as the binder resin (A) contained in the ceramic slurry, 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 contained. If the amount exceeds 20 mol %, the storage stability of the ceramic slurry containing the polyvinyl acetal will decrease, and the amount of carbon residue in the resulting ceramic molded article will tend to increase. Further, the flexibility of the sheet is increased, and the strength of the obtained ceramic green sheet tends to be reduced.

When polyvinyl acetal is contained as the binder resin (A) contained in the ceramic slurry, the preferable range of the viscosity average degree of polymerization of the polyvinyl acetal is as described above, but it is obtained when the viscosity average degree of polymerization is less than 200. The strength of the ceramic green sheet may decrease. The viscosity average degree of polymerization is preferably 300 or higher, more preferably 500 or higher, and even more preferably 800 or higher. On the other hand, if the viscosity average degree of polymerization exceeds 5,000, the viscosity of the ceramic slurry prepared when manufacturing the ceramic green sheet may be too high, and the productivity may be lowered. The viscosity average degree of polymerization is preferably 4500 or less, more preferably 4000 or less, still more preferably 3500 or less. In addition, the viscosity average degree of polymerization is preferably 1400 or more, and more preferably 1500 or more, from the viewpoint of further improving the dimensional stability of the ceramic green sheet during pressure bonding.

When polyvinyl acetal is contained as the binder resin (A) contained in the ceramic slurry, the preferable range of the saponification degree of the raw material PVA is as described above, but when the saponification degree of the raw material PVA is less than 80 mol%, The dispersibility of the ceramic slurry containing acetal may decrease.

Suitable conditions for the organic compound (B) contained in the ceramic slurry are as described above.

The content of the organic compound (B) in the ceramic slurry is not particularly limited, but is preferably 1 part by mass or more, more preferably 5 parts by mass or more, relative to 100 parts by mass of the binder resin (A), It is more preferably 10 parts by mass or more. When the content of the organic compound (B) is less than the above range, the dispersibility of the ceramic slurry and the storage stability tend to be poor, and this may cause 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 further preferably 40 parts by mass or less. When 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 during pressure bonding tends to decrease.

The ceramic slurry 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 effects of the present invention and has no problem in compatibility with the binder resin (A). As the plasticizer, a mono- or diester of an oligoalkylene glycol having hydroxyl groups at both ends and 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. Specifically, triethylene glycol-di-2-ethylhexanoate, tetraethylene glycol-di-2-ethylhexanoate, triethylene glycol-di-n-heptanoate, tetraethylene glycol-di-n-heptanoate. Monoester or diester of oligoalkylene glycol having hydroxyl groups at both terminals such as tri- or tetraethylene glycol and carboxylic acid; diester of dicarboxylic acid such as dioctyl phthalate, dibutyl phthalate, dioctyl adipate, dibutyl adipate and alcohol ..

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

As the organic solvent (C) contained in the ceramic slurry, alcohols such as methanol, ethanol, isopropanol, n-propanol, butanol, etc. among the above-mentioned organic solvents (C); cellsolves such as methylcellsolve, butylcellsolve; acetone; , Ketones such as 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. These may be used alone or in combination of two or more. Among them, butanol, ethanol, toluene, ethyl acetate, or a mixed solvent thereof is 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 2 parts by mass or more, more preferably 3 parts by mass or more, and 5 parts by mass with respect to 100 parts by mass of the ceramic powder. It is more preferably at least 10 parts by mass, and particularly preferably at least 10 parts by mass. When the content of the organic solvent (C) is less than the above range, the viscosity of the ceramic slurry tends to be too high and the kneading property tends to be lowered. The content of the organic solvent (C) is more preferably 200 parts by mass or less and even 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 tends to be too low, and the handling property when forming the ceramic green sheet tends to deteriorate. The content of the organic solvent (C) here is, for example, the organic solvent (C) in the inorganic compound dispersing agent, the organic solvent (C) used when the ceramic powder is combined with the inorganic compound dispersing agent, etc. Denotes the total amount of the organic solvent (C) contained in the slurry.

Examples of the ceramic powder contained in the ceramic slurry include powders of metal or non-metal oxides, carbides, nitrides, borides, sulfides and the like used for producing ceramics. Specific examples thereof include Li, K, Mg, B, Al, Si, Cu, Ca, Sr, Ba, Zn, Cd, Ga, In, Y, lanthanoids, actinides, Ti, Zr, Hf, Bi, V, Nb. , Ta, W, Mn, Fe, Co, Ni, and other oxides, carbides, nitrides, borides, sulfides, and the like. These ceramic powders may be used alone or as a mixture of two or more kinds.

The ceramic slurry contains, in addition to the binder resin (A), the organic compound (B), the organic solvent (C), and the ceramic powder, if necessary, a deflocculant, an adhesion agent, and the like, as long as they do not violate the spirit of the present invention. Accelerators, dispersants, tackifiers, storage stabilizers, defoamers, thermal decomposition accelerators, antioxidants, surfactants, lubricants, adhesion improvers, and other conventionally known additives Good. Further, a resin other than the binder resin (A) may be contained as long as the effect of the present invention is not impaired.

The method for producing the ceramic slurry is not particularly limited. For example, it can be manufactured by the following method. A predetermined amount of the organic solvent (C) and additives are added to the ceramic powder to obtain a dispersion liquid of the ceramic powder. Separately, a binder resin is dissolved in an organic solvent (C), the organic compound (B) and, if necessary, an additive are added to the solution, and then stirred to produce a uniform inorganic compound dispersing agent. Then, the above-mentioned inorganic compound dispersing agent is added to the dispersion liquid of the ceramic powder and uniformly dispersed to obtain a ceramic slurry.

Alternatively, the binder resin (A) is dissolved in an organic solvent (C), the organic compound (B) and, if necessary, an additive are added to the solution, and then stirred to produce a uniform inorganic compound dispersion agent. To do. Ceramic powder is added to this inorganic compound dispersing agent and then uniformly dispersed to obtain a ceramic slurry. As a method for dispersing, various methods such as a method using a medium type dispersing machine such as a bead mill, a ball mill, an attritor, a paint shaker and a sand mill, a kneading method, a method using three rolls can be used. At that time, a dispersant containing an ionic group may be used as the dispersant, and an anionic dispersant having a carboxylic acid group, a maleic acid group, a sulfonic acid group, a phosphoric acid group or the like in the molecule is suitable. An anionic dispersant such as "Marialim" (manufactured by NOF CORPORATION) containing no metal ion is preferably used.

[Ceramic Green Sheet] A preferred embodiment of the present invention is a ceramic green sheet obtained by using the ceramic slurry. By using the ceramic slurry of the present invention, it is possible to obtain a ceramic green sheet which is excellent in adhesiveness during pressure bonding and has less dimensional change during pressure bonding. In addition, rapid debinding of the ceramic green sheet laminate during firing is suppressed, and delamination during production of the multilayer ceramic capacitor is suppressed.

When at least one surface of the ceramic green sheet is subjected to secondary ion analysis (TOF-SIMS analysis) with a time-of-flight secondary ion analyzer, the intensity of detected Ba+ ions is different from that of Ti+ ions detected. It is preferable that the ratio of (Ba+ ion strength)/(Ti+ ion strength) be 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 adhesiveness at the time of pressure bonding and has less dimensional change at the time of pressure bonding. When (Ba+ ion strength)/(Ti+ ion strength) is within the above range, when the ceramic green sheet is fired, rapid burnout of the binder component from the laminated body can be suppressed, and the laminated body can be suppressed. Delamination at the time of manufacturing a ceramic capacitor is suppressed.

The (Ba+ ion intensity)/(Ti+ ion intensity) is preferably more than 20, more preferably more than 100, and even more preferably more than 150. Further, (Ba+ ion strength)/(Ti+ ion strength) is preferably larger than 1000, more preferably smaller than 700, and further 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 the ceramic powder. The method for obtaining a ceramic green sheet in which (Ba+ ion strength)/(Ti+ ion strength) is in the above range when a TOF-SIMS analysis is performed is not particularly limited, but, for example, by the chemical formula (1), A method of producing a ceramic green sheet using a ceramic slurry containing the organic compound (B) shown and using barium titanate as the ceramic powder and performing the plasma treatment can be mentioned.

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

The ceramic green sheet of the present invention is suitably used as a material for various electronic components. Particularly, it is preferably used as a material for a chip type multilayer ceramic capacitor, a circuit board of an IC chip, and the like. These are manufactured by forming electrodes on a ceramic green sheet, stacking and pressing the electrodes, and then firing.

Examples of the method for manufacturing the ceramic green sheet include a method in which a ceramic slurry is applied onto a support film that has been subjected to a one-side release treatment, and then the organic solvent (C) is dried to form a sheet. .. A roll coater, a blade coater, a die coater, a squeeze coater, a curtain coater, or the like can be used for coating the ceramic slurry.

As the support film used when producing the ceramic green sheet, one made of a resin having heat resistance and solvent resistance and having flexibility is preferable. Since the supporting film is made of a resin having flexibility, the ceramic slurry is applied onto the supporting film, and the film on which the obtained ceramic green sheet is formed is stored in a roll and is required. 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 resins such as polyfluoroethylene, nylon, and cellulose. .. The thickness of the support film is not particularly limited and is preferably 20 μm or more, and preferably 100 μm or less. Moreover, it is preferable that the surface of the support film is subjected to a release treatment. Since the surface of the support film is subjected to the release treatment, the support film can be easily peeled off in the transfer step. A preferred specific example of the support film is a silicone-coated PET film.

The thickness of the ceramic green sheet varies depending on the purpose of use and cannot be unconditionally specified, but it is preferably 0.1 μm or more, and preferably 300 μm or less. Further, the drying temperature at the time of drying the coating film formed on the carrier film varies depending on the thickness of the ceramic green sheet and the like, and thus cannot be unconditionally specified, but is preferably 25° C. or higher. It is preferably 200° C. or lower.

[TOF-SIMS analysis]
The TOF-SIMS analysis is a measurement method capable of observing the distribution state of components included in the measurement target by scanning the surface of the measurement target. For example, a region of 50 to 500 μm square on the surface of the measurement object is divided into minute regions of 0.1 to 3 μm square, primary ions are irradiated, and secondary ions protruding from this minute region are observed, It is possible to identify the type of the component in the minute region and measure the intensity of the secondary ion. This minute area is called a primary ion irradiation point. The ratio of the intensity of Ba+ ions to the intensity of Ti+ ions (intensity of Ba+ ions)/(intensity of Ti+ ions) is a value obtained by dividing the intensity of Ba+ by the intensity of Ti+ secondary ions.

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 plasma irradiation. Therefore, the surface measurement by TOF-SIMS analysis is performed after plasma irradiation. It is preferable to carry out promptly. The time from plasma irradiation to surface measurement by TOF-SIMS analysis is preferably 12 hours or less, more preferably 3 hours or less, further preferably 1 hour or less, and the surface immediately after plasma irradiation is measured. Most preferably, measurements are taken. In the case of analysis of the coated sheet, the surface analysis of the ceramic green sheet portion of the coated surface is performed.

Moreover, in order to suppress volatilization of components on the surface of the ceramic green sheet during measurement by TOF-SIMS analysis, for example, after cooling to −100° C. to −200° C., TOF-SIMS analysis under vacuum is performed. Is preferably carried out.

[Conductive paste]
The slurry composition of the present invention is also suitably used as a conductive paste. The conductive paste of the present invention contains a conductive powder as a binder resin (A), an organic compound (B) represented by the general formula (1), an organic solvent (C) and an inorganic compound (D).

The inorganic compound dispersing agent of the present invention is excellent in dispersibility of the conductive powder and also excellent in storage stability. Therefore, the slurry composition obtained therefrom can be suitably used as a conductive paste. The conductive paste thus obtained has excellent dispersibility of the conductive powder and excellent storage stability. The printability is excellent when printing on the surface of the ceramic green sheet, and the printed surface becomes smooth. By using the conductive paste, a sintered body having a small amount of carbon residue and less delamination can be obtained. If the storage stability of the conductive paste is reduced, the desired print thickness may not be obtained, or the surface after printing may be roughened, which may adversely affect the electrical characteristics of the sintered body.

The content of the binder resin (A) in the conductive paste is not particularly limited, but is preferably 1 part by mass or more, and more preferably 3 parts by mass or more, relative to 100 parts by mass of the conductive powder. When the content of the binder resin is less than the above range, the film forming property when printing the conductive paste may be insufficient. The content of the binder resin is preferably 50 parts by mass or less, more preferably 25 parts by mass or less, and particularly preferably 10 parts by mass or less. On the other hand, when the content of the binder resin (A) exceeds the above range, the amount of carbon residue in the obtained sintered body may increase.

The conditions for the binder resin (A) contained in the conductive paste are as described above.

The binder resin (A) for the conductive paste preferably contains polyvinyl acetal. The content of polyvinyl acetal in the binder resin (A) for the conductive paste is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more.

When polyvinyl acetal is contained as the binder resin (A) contained in the conductive paste, suitable conditions for the degree of acetalization of polyvinyl acetal are as described above, but when the degree of acetalization is less than 50 mol%, the polyvinyl The storage stability of the conductive paste containing acetal tends to decrease. On the other hand, when the degree of acetalization exceeds 85 mol %, the efficiency of the acetalization reaction is remarkably reduced, the productivity is remarkably deteriorated, and the commerciality tends to be poor. Furthermore, the amount of carbon residue after heating the conductive paste increases, and the electrical properties of the obtained sintered body tend to be insufficient.

When polyvinyl acetal is contained as the binder resin (A) contained in the conductive paste, 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 included. When the amount exceeds 20 mol %, the storage stability of the conductive paste containing the polyvinyl acetal tends to decrease.

When polyvinyl acetal is contained as the binder resin (A) contained in the conductive paste, the suitable range of the viscosity average degree of polymerization of polyvinyl acetal is preferably 200 or more as described above. The viscosity average degree of polymerization is more preferably 250 or more, further preferably 300 or more, and particularly preferably 350 or more. When the viscosity average degree of polymerization is less than the above range, the strength of the coating film formed by applying the conductive paste is lowered, and cracks tend to occur on the surface. On the other hand, the viscosity average degree of polymerization is preferably 5000 or less, more preferably 4500 or less, further preferably 4000 or less, particularly preferably 3500 or less, and most preferably 2500 or less. preferable. When the viscosity average degree of polymerization exceeds the above range, the viscosity of the conductive paste tends to be too high and the printability tends to deteriorate.

When polyvinyl acetal is contained as the binder resin (A) contained in the conductive paste, the preferable range of the saponification degree of the raw material PVA is as described above, but when the saponification degree of the raw material PVA is less than 80 mol%, The dispersibility of the conductive powder in the paste may decrease. In addition, the storage stability of the conductive paste containing polyvinyl acetal may decrease.

Suitable conditions for the organic compound (B) contained in the conductive paste are as described above.

The content of the organic compound (B) in the conductive paste is not particularly limited, but is preferably 1 part by mass or more based on 100 parts by mass of the binder resin. If the amount is less than 1 part by mass with respect to 100 parts by mass of the binder resin, the adhesiveness tends to decrease. The content of the organic compound (B) is preferably 50 parts by mass or less with respect to 100 parts by mass of the binder resin. When the content of the organic compound (B) exceeds 50 parts by mass, the dimensional stability at the time of pressure bonding tends to decrease.

The conductive paste may 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 effects of the present invention and has no problem in compatibility with the binder resin (A). Examples of the plasticizer include those exemplified as the plasticizer used in the ceramic slurry.

The organic solvent (C) contained in the conductive paste is not particularly limited as long as it can dissolve the binder resin (A), and examples thereof include Menten, menthane, menthone, myrcene, α-pinene, α-terpinene, γ. -Terpinene, limonene, perillyl acetate, menthyl acetate, carbyl acetate, dihydrocarbyl acetate, perillyl alcohol, dihydroterpineol acetate, terpineol acetate, dihydroterpineol, terpinyloxyethanol, dihydroterpinyloxyethanol, terpinyl Methyl ether, dihydroterpinyl methyl ether, dihydroterpinyl propionate, isobonyl acetate, isobonyl propionate, isobonyl butyrate, isobonyl isobutyrate, novir acetate, octyl acetate, dimethyl octyl acetate, butyl Carbitol acetate, acetoxy-methoxyethoxy-cyclohexanol acetate, dihydrocarbeol, 2-ethylhexyl glycol, benzyl glycol, phenylpropylene glycol, methyldecalin, amylbenzene, cumene, cymene, 1,1-diisopropylhexane, citronellol and the like. To be These may be used alone or in combination of two or more. Among them, dihydroterpineol acetate, terpineol acetate, terpinyl methyl ether, terpenes not having a highly polar substituent such as a hydroxyl group represented by dihydroterpinyl methyl ether and hydrogenated products thereof are preferable, and particularly a sheet From the viewpoint of attack property, dihydroterpineol acetate is preferable.

The content of the organic solvent (C) in the conductive paste is not particularly limited, but is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more with respect to 100 parts by mass of the conductive powder. The content of the organic solvent (C) in the conductive paste is preferably 600 parts by mass or less, and more preferably 150 parts by mass or less with respect to 100 parts by mass of the conductive powder. If the content of the organic solvent (C) in the conductive paste is out of the above range, the coatability of the conductive paste may be reduced, or it may be difficult to disperse the conductive powder. The content of the organic solvent (C) here is, for example, the organic solvent (C) in the inorganic compound dispersing agent, the organic solvent (C) used when the conductive powder is combined with the inorganic compound dispersing agent, etc. Denotes the total amount of the organic solvent (C) contained in the paste.

As the conductive powder contained in the conductive paste, for example, in addition to powders of highly conductive metals such as nickel, palladium, platinum, gold and silver, powders of alloys of these metals, oxides of these and the like are used. It Further, a metal such as copper or iron, which has good adsorption properties with a carboxyl group, an amino group, an amide group, etc. and is easily oxidized, can be preferably used. These conductive powders may be used alone or in combination of two or more kinds.

The conductive paste is exemplified by the description of the ceramic slurry, in addition to the binder resin (A), the organic compound (B), the organic solvent (C) and the conductive powder, as long as it does not violate the spirit of the present invention. The known additives described above and resins other than the binder resin (A) may be contained.

The conductive paste can be manufactured, for example, by the following method. A binder resin is dissolved in an organic solvent (C), the organic compound (B) and, if necessary, an additive are added to the solution, followed by stirring to produce a uniform inorganic compound dispersing agent. A conductive powder and, if necessary, an additive are added to the agent for dispersing an inorganic compound and then uniformly dispersed to obtain a conductive paste. As a method for dispersing, various methods such as a method using a medium type disperser such as a blender mill, a bead mill, a ball mill, an attritor, a paint shaker and a sand mill, a kneading method and a method using three rolls can be used. At that time, a dispersant containing an ionic group may be used as the dispersant, and an anionic dispersant having a carboxylic acid group, a maleic acid group, a sulfonic acid group, a phosphoric acid group or the like in the molecule is suitable. An anionic dispersant such as "Marialim" (manufactured by NOF CORPORATION) containing no metal ion is preferably used.

[Coating sheet]
A preferred embodiment of the present invention is a coated sheet obtained by coating the surface of the above-mentioned ceramic green sheet of the present invention with a conductive paste. When used in combination with the ceramic green sheet of the present invention, the conductive paste may be the conductive paste of the present invention or any other commonly used conductive paste. Further, another preferred embodiment of the present invention may be a coated sheet obtained by coating the surface of a ceramic green sheet with the conductive paste of the present invention. When the ceramic green sheet is used in combination with the conductive paste of the present invention, it may be the ceramic green sheet of the present invention or any other commonly used ceramic green sheet.

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

[Plasma treatment]
The ceramic green sheet of the present invention is preferably in a state in which at least a part of at least one surface of the ceramic green sheet is subjected to plasma treatment. That is, in the production, it is preferable to include a step of performing plasma treatment on at least one surface of the front surface and the back surface of the ceramic green sheet. The ceramic green sheet thus obtained is also a preferred embodiment of the present invention. At least one of the front and back surfaces of the ceramic green sheet is subjected to plasma treatment, and the ceramic-treated surface and the other ceramic green sheet are laminated so that they are in contact with each other. The laminate thus obtained has good adhesiveness as compared with the case where the laminate is produced by using a ceramic green sheet whose surface is not 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 is subjected to plasma treatment. That is, in the production, it is preferable to include a step of performing plasma treatment on at least one surface of the coated sheet. It suffices that at least a part of at least one surface of the coated sheet is subjected to plasma treatment.A method of performing plasma treatment on the ceramic green sheet before coating the conductive paste or coating the conductive paste on the ceramic green sheet It can be obtained by any of the methods of subjecting the coated sheet after processing to plasma treatment.

The surface of the coated sheet coated with the conductive paste is subjected to plasma treatment, and the plasma-treated surface and one surface of another coating sheet are laminated so as to be in contact with each other. The laminate thus obtained exhibits good adhesiveness as compared with the case where the laminate is produced by using a coated sheet whose surface is not 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 coating sheet (ceramic green sheet surface), or the front and back surfaces of the coating sheet. When a laminated ceramic capacitor is manufactured by stacking a plurality of coated sheets, the surface of the conductive paste can be subjected to plasma treatment and laminated so that this surface is in contact with the ceramic green sheet surface of another coated sheet. The laminate thus obtained exhibits good adhesion.

Alternatively, the surface of the ceramic green sheet may be subjected to plasma treatment, and the ceramic green sheet may be laminated so that this surface is in contact with the surface of the conductive paste of another coating 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, or a conductive sheet of the present invention on the surface of the ceramic green sheet of the present invention. A coated sheet formed by applying a paste is preferably used. Further, the front surface or the back surface of the coated sheet is subjected to plasma treatment, and the plasma treated surface and the ceramic green sheet surface or the conductive paste surface of the other coated sheet are laminated so as to be in contact with each other. The laminate thus obtained also exhibits good adhesion.

Alternatively, the ceramic green sheet may be subjected to plasma treatment, and the plasma-treated surface may be coated with a conductive paste. It is laminated so that the surface that has been subjected to the plasma treatment and coated with the conductive paste is in contact with one surface of another coating sheet. The laminate thus obtained exhibits good adhesiveness as compared with the case where the laminate is produced by using a coated sheet whose surface is not 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, or the conductive paste of the present invention on the surface of the ceramic green sheet of the present invention A coated sheet obtained by coating is preferably used.

The method of plasma treatment used in the present invention is not particularly limited, and examples thereof include low pressure plasma, high pressure plasma, corona discharge treatment, atmospheric pressure plasma and the like. As a processing method, an appropriate processing method can be used as long as the properties of the present invention are not impaired, but the low-pressure plasma needs to be applied in a vacuum state, and in-line production is difficult. Since corona treatment requires high energy, the surface shape may change and the treated surface may become unexpectedly uniform. On the other hand, it is not necessary to perform the atmospheric pressure plasma treatment in a vacuum state, and energy can be selected high or low. From the viewpoint of productivity and performance, atmospheric pressure plasma is particularly preferable as a treatment method.

Various atmospheric pressure plasma devices can be used for the atmospheric pressure plasma treatment. For example, a device capable of generating low-temperature plasma by performing intermittent discharge while passing an inert gas having a pressure near atmospheric pressure between electrodes covered with a dielectric is preferable, and any device can be used, Various modified examples can be selected according to the purpose of use and the like. The “pressure near 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, and preferably 90 kPa or more and 110 kPa or less. The temperature and humidity at the time of performing atmospheric pressure plasma treatment are not particularly limited and can be appropriately changed, but it is preferable to perform atmospheric pressure plasma treatment at room temperature and normal humidity.

As the discharge gas used when generating the atmospheric pressure plasma, any gas of nitrogen, oxygen, hydrogen, carbon dioxide, helium, and argon, or a mixed gas of two or more of these can be used. A rare gas such as He and Ar, which is an inert gas, or a nitrogen gas is preferably used, and a rare gas such as Ar or He is particularly preferable. For example, when a mixed gas of nitrogen gas and air is used, it is preferable to supply the nitrogen gas at a flow rate of 10 L/min or more and 500 L/min or less. Further, 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 the 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, more preferably 2 mm or more. In addition, 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 a direction perpendicular to the plasma irradiation direction while the surface of the ceramic green sheet to be plasma-treated is kept perpendicular to the plasma irradiation direction, Plasma treatment can be performed on the. At this time, the time for which the ceramic green sheet passes immediately below the irradiation port is preferably 0.1 seconds or more, more preferably 0.5 seconds or more. Further, it is preferably 40 seconds or less, and more preferably 20 seconds or less. It should be noted that the area immediately below the irradiation port may also have 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 (Ba+ion intensity)/(Ti+ion intensity) becomes less than 20. Or, it tends to be larger than 1000.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, in the following Examples and Comparative Examples, the "degree of polymerization" means "the viscosity average degree of polymerization". Moreover, in the following Examples and Comparative Examples, the "ceramic green sheet" means a portion that does not include the polyester film that is the supporting 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 acetal used in Examples and Comparative Examples are JIS K 6728: It measured based on 1977. The viscosity average degree of polymerization of polyvinyl acetal is shown by the viscosity average degree of polymerization of the raw material PVA measured according to JIS K 6726:1994.

(2. Measurement of Acid Value of Organic Compound and Inorganic Compound Dispersing Agent)
The acid value of the organic compound and the inorganic compound dispersing agent used in Examples and Comparative Examples was measured according to JIS K 6728:1977. More specifically, about 1 g of each organic compound or each inorganic compound dispersion agent was placed in an Erlenmeyer flask with a stopper, and 30 ml of ethyl alcohol was added and dissolved. Phenolphthalein was used as an indicator, and the obtained solution was titrated with N/50 potassium hydroxide, and the titration amount up to the point of maintaining a slightly crimson color for 30 seconds or more was defined as a (mL). Separately, the same titration was performed on 30 ml of ethyl alcohol, and the titer until the point of maintaining a slightly reddish color was b (mL), and the acid value was calculated by the following mathematical formula (II).

(3. TOF-SIMS analysis of the surface of the ceramic green sheet)
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) performed cooling measurement. After performing the atmospheric pressure plasma treatment on the surface of the ceramic green sheet obtained in Production Example, the ceramic green sheet was cooled to -150°C, and then immediately under vacuum, time-of-flight secondary ion mass spectrometry (TOF- SIMS) analysis was performed. As the time-of-flight secondary ion mass spectrometer (TOF-SIMS), TOF-SIMS5 manufactured by ION-TOF was used. A bismuth cluster ion source (Bi3++) was used as the primary ion source, the current value was 0.2 picoamperes, the accelerating voltage was 25 kilovolts, and the measurement mode was the high mass resolution normal mode (bunching mode). An arbitrary 500 μm×500 μm of the plane of the ceramic green sheet (one of the faces having the largest area of the ceramic green sheet) is set as a measurement region, and the measurement region is divided into 128×128 pixels and the ion beam irradiation mode is random. The measurement area was scanned in the raster mode, and the number of scans was 64. The intensity of Ti+ ions and the intensity of Ba+ ions were calculated from the mass spectrum obtained by the measurement, and the ratio of the intensity of Ba+ ions to the intensity of Ti+ ions was calculated. The results are shown in Table 2-1, Table 2-2 and Table 3. Since the surface state of the sheet after the plasma irradiation may change depending on the storage state, the surface analysis measurement after the plasma irradiation was performed immediately after the plasma irradiation.

(4-1. Storage stability of ceramic slurry)
The storage stability of the ceramic slurries used in Examples and Comparative Examples was evaluated by the ratio of the viscosity η ₀ immediately after the production of the ceramic slurries to the viscosity η ₁ one month after the production. The evaluation criteria are as follows.
Evaluation A: 0.95<η ₁ /η ₀ <1.05
Evaluation B: 0.85<η ₁ /η ₀ ≦0.95 or 1.05≦η ₁ /η ₀ <1.15
Evaluation C: η ₁ /η ₀ ≦0.85 or 1.15≦η ₁ /η ₀

The viscosity of the ceramic slurry was measured under the following measurement conditions using a rotary rheometer (TA INSTRUMENT, ARES G2).

<Measurement conditions>
FLOW SWEEP mode shear rate: 100 (1/sec)
Diameter of rotating disk: 40mm
Rotating disc (upper side): Flat plate Rotating disc (lower side) cone angle: 0.02 rad
Truncation gap: 0.0262mm

(4-2. Storage stability of conductive paste)
The storage stability was evaluated according to the method described in "4-1. Storage stability of ceramic slurry" except that the conductive paste used in Examples and Comparative Examples was used instead of the ceramic slurry.

(5-1. Evaluation of adhesiveness of ceramic green sheet)
Atmospheric pressure plasma treatment under the following conditions, ceramic green sheets used in Examples and Comparative Examples, and ceramic green sheets used in Examples and Comparative Examples not subjected to atmospheric pressure plasma treatment were laminated, and a hot press machine was used. A thermocompression bonding test was performed under the following conditions. At this time, the surface subjected to the atmospheric pressure plasma treatment was laminated so as to contact the surface of the other ceramic green sheet which was not subjected to the atmospheric pressure plasma treatment to obtain a laminated body.

<Plasma irradiation>
The ceramic green sheets (on the polyester film) used in Examples and Comparative Examples were cut together with the polyester film into a size of 10 cm×10 cm. After peeling the ceramic green sheet from the polyester film, nitrogen gas at a flow rate of 150 L/min and dry pure air at a flow rate of 0.5 L are formed on the surface of the ceramic green sheet using an atmospheric pressure plasma device at room temperature and normal humidity. Using a mixed gas/minute, the voltage between electrodes is 11 kV, the distance between electrodes is 2 mm, the moving speed of the sample (ceramic green sheet) is 10 mm/sec, and the time for which the ceramic green sheet passes directly under the irradiation opening of 2 cm in width is 2 seconds. The atmospheric pressure plasma treatment was performed under the condition of (10 seconds for the entire 10 cm×10 cm ceramic green sheet).

<Heat press conditions>
Press temperature 45℃
Pressure 1 MPa
Time 5 seconds

The obtained laminated body was cut into 5 mm×5 mm, and 100 pieces were arbitrarily extracted. The adhesive surface of the arbitrarily selected laminate was visually observed, and the adhesiveness between the ceramic green sheets was evaluated according to the following 5 grades.
A: Delamination was not observed at all, and they were firmly bonded.
(Number of delaminated laminates/Any laminate=0/100)
B: Delamination was slightly observed, but the layers were firmly bonded.
(Number of delaminated laminates/arbitrary laminate=1 to 10/100)
C: Delamination was partially observed, but adhered.
(Number of delaminated laminates/arbitrary laminates=11 to 30/100)
D: Delamination was considerably observed, and almost no adhesiveness was exhibited.
(Number of delaminated laminates/arbitrary laminates=31 to 99/100)
E: No adhesion was shown.
(Number of delaminated laminates/arbitrary laminate=100/100)

(5-2. Adhesion evaluation of coated sheet)
Adhesiveness was evaluated according to the method described in "5-1. Evaluation of adhesiveness of ceramic green sheet" except that the coated sheet used in Examples and Comparative Examples was used instead of the ceramic green sheet. At this time, the atmospheric pressure plasma treatment is performed on the surface coated with the conductive paste, and the surface subjected to the atmospheric pressure plasma treatment is the surface of the other coating sheet which is not subjected to the atmospheric pressure plasma treatment (the conductive paste is coated). It was laminated so that it touched the surface (which was not exposed).

(6-1. Evaluation of dimensional stability of ceramic green sheet)
For the ceramic green sheets having a film thickness of 2 μm after drying (air drying at room temperature for 1 hour, followed by drying at 80° C. for 2 hours and then 120° C. for 2 hours) used in Examples and Comparative Examples, Plasma treatment was performed in the same manner as in. This sheet was cut into 5 cm squares, two sheets were superposed, and then pressed at 45° C. (pressing pressure: 3 MPa) to obtain a deformation rate (area after pressing/area before pressing×100). At this time, the surface treated with the atmospheric pressure plasma was laminated so as to contact the surface of the other ceramic green sheet not treated with the atmospheric pressure plasma.
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 4% or more.

(6-2. Evaluation of dimensional stability of coated sheet)
Dimensional stability was evaluated by the same method as "6-1. Evaluation of dimensional stability of ceramic green sheet" except that the coated sheet used in Examples and Comparative Examples was used instead of the ceramic green sheet. At this time, the atmospheric pressure plasma treatment is performed on the surface coated with the conductive paste, and the surface subjected to the atmospheric pressure plasma treatment is the surface of the other coating sheet which is not subjected to the atmospheric pressure plasma treatment (the conductive paste is coated). It was laminated so that it touched the surface (which was not exposed).

(7-1. Evaluation of delamination of fired body in ceramic green sheet laminate)
100 pieces of 10 cm square ceramic green sheets (on a polyester film) used in Examples and Comparative Examples were prepared. After peeling the cut ceramic green sheet from the polyester film, each side is subjected to atmospheric pressure plasma treatment in the same manner as in "5-1. Evaluation of adhesiveness of ceramic green sheet", and the surface subjected to atmospheric pressure plasma treatment And 100 sheets were stacked so that the surfaces not subjected to the atmospheric pressure plasma treatment were overlapped to obtain a green sheet laminate. Then, the laminate was obtained by thermocompression bonding at a temperature of 70° C. and a pressure of 150 kg/cm ² for 10 minutes. The obtained laminated body was cut into 5 mm×5 mm, 100 pieces were arbitrarily extracted from the cut laminated body, and the temperature was raised to 400° C. at a heating rate of 15° C./min in a nitrogen atmosphere, and after holding for 5 hours Further, the temperature was raised to 1350° C. at a heating rate of 5° C./minute, and the temperature was maintained for 10 hours to obtain a ceramic fired body.

After cooling the obtained fired body to room 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 stages.
A: No delamination.
(Number of delaminated fired bodies/arbitrary fired bodies=0 to 2/100)
B: Delamination is slightly observed.
(Number of delaminated fired bodies/arbitrary fired bodies=3 to 7/100)
C: There is some delamination.
(Number of delaminated fired bodies/arbitrary fired bodies=8 to 20/100)
D: There are many delaminations.
(Number of delaminated fired bodies/arbitrary fired bodies=21 to 100/100)

(7-2. Evaluation of delamination of fired body in coated sheet laminate)
100 pieces of the coated sheet used in Examples and Comparative Examples were cut into 10 cm square pieces, and 100 sheets were prepared. The surface coated with the conductive paste is subjected to the atmospheric pressure plasma treatment in the same manner as in "5-2. Evaluation of adhesiveness of coated sheet", and the surface treated with the atmospheric pressure plasma and the surface not treated with the atmospheric pressure plasma. 100 sheets were stacked so as to overlap with each other to obtain a laminate of coated sheets. Then, the laminate was obtained by thermocompression bonding at a temperature of 70° C. and a pressure of 150 kg/cm ² for 10 minutes. The obtained laminated body was cut into 5 mm×5 mm, 100 pieces were arbitrarily extracted from the cut laminated body, and the temperature was raised to 400° C. at a heating rate of 15° C./min in a nitrogen atmosphere, and after holding for 5 hours Further, the temperature was raised to 1350° C. at a heating rate of 5° C./minute, and the temperature was maintained for 10 hours to obtain a ceramic fired body.

After cooling the obtained fired body to room 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 and between the ceramic layers and the electrode layers was evaluated according to the following four grades.
A: No delamination.
(Number of delaminated fired bodies/arbitrary fired bodies=0 to 2/100)
B: Delamination is slightly observed.
(Number of delaminated fired bodies/arbitrary fired bodies=3 to 7/100)
C: There is some delamination.
(Number of delaminated fired bodies/arbitrary fired bodies=8 to 20/100)
D: There are many delaminations.
(Number of delaminated fired bodies/arbitrary fired bodies=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 Ikari type stirring blade, 7280 g of ion-exchanged water, a polymerization degree of 1700, and a polyvinyl alcohol having a saponification degree of 98.4 mol% (hereinafter referred to as PVA-1). 720 g) (PVA concentration 9.0% by mass), and the content was heated to 95° C. to completely dissolve PVA. Next, the contents were gradually cooled to 10° C. over about 30 minutes while stirring at 120 rpm, and then 400 g of n-butyraldehyde and 830 mL of 20 mass% hydrochloric acid were added to the container, and the butyralization reaction was performed for 150 minutes. went. After that, the temperature was raised to 70° C. over 90 minutes, held at 70° C. for 120 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water, and an excessive amount of sodium hydroxide aqueous solution was added to neutralize the resin. Subsequently, the resin was rewashed with ion-exchanged water and then 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 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. ..

(Synthesis example 3)
Polyvinyl butyral (PVB-3) was obtained in the same manner as in Synthesis Example 1 except that PVA having the degree of polymerization and the degree of saponification shown in Table 1 was used instead of PVA-1 and 388 g of n-butyraldehyde 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 the degree of saponification shown in Table 1 was used instead of PVA-1, and 453 g of n-butyraldehyde was used. ..

(Synthesis example 5)
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)
Polyvinyl butyral (PVB-6) 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 in place of PVA-1, and 398 g of n-butyraldehyde was used. ..

(Synthesis example 7)
Polyvinyl butyral (PVB-7) was obtained in the same manner as in Synthesis Example 1 except that PVA having a degree of polymerization and a degree of saponification shown in Table 1 was used instead of PVA-1, and 405 g of n-butyraldehyde 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 the degree of saponification shown in Table 1 was used instead of PVA-1, and 399 g of n-butyraldehyde was used. ..

(Synthesis example 9)
Instead of PVA-1, as shown in Table 1, PVA having a degree of polymerization of 2400 and a degree of saponification of 98.8 mol% and PVA having a degree of polymerization of 500 and a degree of saponification of 98.8 mol% were used in a mass ratio of 70/30. 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)
Polyvinyl butyral (PVB-10) was prepared in the same manner as in Synthesis Example 1 except that isobutyraldehyde was used for acetalization instead of n-butyraldehyde for butyralization. Obtained.

(Synthesis example 11)
Instead of performing butyralization with n-butyraldehyde in Synthesis Example 1, acetaldehyde and n-butyraldehyde were used at a weight ratio of 100/64 to perform acetalization, and the same operation as in Synthesis Example 1 was performed. It carried out and obtained polyvinyl butyral (PVB-11).

Regarding 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 are measured according to the method described in "1. Measurement of polyvinyl acetal" described above. Was measured. The measurement results are shown in Table 1.

[Manufacture of ceramic green sheets]
(Production Example 1)
<Preparation of Inorganic Compound Dispersing Agent>
After 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, PVB-1 was dissolved by stirring, and 100 parts by mass of bis(2-butoxyethyl) adipate was added to the solution. To 38 parts by mass of PVB-1 was added and stirred to prepare an inorganic compound dispersing agent.

<Production 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 (“BT-02”, manufactured by Sakai Chemical Industry Co., Ltd., average particle size: 0.2 μm), which is a ceramic powder, and mixed in a ball mill for 15 hours. Then, a dispersion liquid of ceramic powder was obtained. Subsequently, the inorganic compound dispersing agent was added to the ceramic powder dispersion so that PVB-1 was 7.5 parts by mass with respect to 100 parts by mass of the ceramic powder, and the mixture was mixed by a ball mill for 24 hours to obtain a ceramic slurry. Got

<Manufacture of ceramic green sheets>
The obtained ceramic slurry was coated on a polyester film subjected to mold release treatment using a bar coater so that the dry film thickness was 2 to 3 μm, air-dried at room temperature for 1 hour, and then dried with 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 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 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 were prepared in the same manner as in Production Example 1 except that bis(2-butoxyethyl) adipate was added to the binder resin (A) in the proportions 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. It was made.

(Production Example 22)
As shown in Table 2-2, except that 19 parts by mass of bis(2-butoxyethyl) adipate and 19 parts by mass of triethylene glycol di2-ethylhexanoate were added to 100 parts by mass of PVB-1. Produced a ceramic green sheet GS-22 in the same manner as in Production Example 1.

(Production Examples 23 to 25)
Ceramic green sheets GS-23 to GS-25 were produced in the same manner as in Production Example 1 except that the organic compounds shown in Table 2-2 were added.

(Production Example 26)
After adding 10 parts by mass of PVB-1 obtained in Production Example 1 to a mixed solvent of 30 parts by mass of toluene and 30 parts by mass of ethanol, PVB-1 was dissolved by stirring, and Table 2-2 was added to the solution. Bis(2-butoxyethyl) adipate shown in is added so as to be 38 parts by mass with respect to 100 parts by mass of PVB-1. 11 parts by weight was added to PVB-1 in parts by mass and stirred to prepare an agent for dispersing an inorganic compound. 15 parts by mass of toluene and 15 parts by mass of ethanol were added to 100 parts by mass of barium titanate (“BT-02”, manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter 0.2 μm) as a ceramic powder, and then 15 hours by a ball mill. The mixture was mixed to obtain a dispersion liquid of ceramic powder. Subsequently, an inorganic compound dispersing agent was added to the ceramic dispersion liquid such that PVB-1 was 7.5 parts by mass with respect to 100 parts by mass of the ceramic, and the mixture was mixed by a ball mill for 24 hours to obtain a ceramic slurry. Further, using the obtained ceramic slurry, a ceramic green sheet GS26 was produced in the same manner as in Production Example 1.

(Production Example 27)
A ceramic green sheet GS-27 was produced in the same manner as in Production Example 26 except that 34 parts by mass of “Marialim AKM-0531” was added to 100 parts by mass of PVB-1.

(Production Example 28)
Using the organic compounds shown in Table 2-2, except that 68 parts by mass of "Marialim AKM-0531" was added to 100 parts by mass of PVB-1, a ceramic green sheet GS- was prepared in the same manner as in Production Example 26. 28 was produced.

(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.

(Production Example J)
A ceramic green sheet GS-J was produced in the same manner as in Production Example 26 except that the amount of "Marialim AKM-0531" added was changed to 79 parts by weight with respect to 100 parts by mass of PVB-1.

(Production Example K)
A ceramic green sheet was produced in the same manner as in Production Example 26, except that the organic compounds shown in Table 3 were used and the addition amount of "Marialim AKM-0531" was changed to 70 parts by weight with respect to 100 parts by mass of PVB-1. GS-K was produced.

Regarding the obtained ceramic green sheets GS-A to GS-K, each of the ceramic green sheets was manufactured according to the method described in the above-mentioned evaluation method “2. Measurement of acid value of organic compound and inorganic compound dispersing agent”. The acid values of the organic compound and the inorganic compound dispersing agent were measured. Table 3 shows the measurement results.

Regarding the obtained ceramic green sheets GS-1 to GS-28 and GS-A to GS-K, according to the method described in the above evaluation method "2. Measurement of acid value of agent for dispersing organic compound and inorganic compound". The acid value of the organic compound and the inorganic compound dispersing agent used at the time of manufacturing each ceramic green sheet 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]
(Production Example 1)
<Preparation of conductive paste>
To a 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath and a nitrogen gas inlet, ethyl cellulose (STD-45 manufactured by Dow Chemical Co.) and dihydroterpinyl acetate were added. Next, nickel powder (“NFP201”, manufactured by JFE Mineral Co., Ltd.) was mixed as a conductive powder, and 20 parts by mass of a commercially available barium titanate powder having an average particle diameter of 0.1 μm was added to the nickel powder, and three powders were added. It was passed through a roll several times to obtain a conductive paste. The composition ratio in the conductive paste was adjusted so that the binder resin (A) was 3% by mass, the nickel powder was 50% by mass, the barium titanate was 10% by mass, and the others were organic solvents.

<Preparation of coated sheet>
The green sheet GS-1 obtained in Production Example 1 was cut into a size of 10 cm×10 cm, and subjected to atmospheric pressure plasma treatment in accordance with the method described in the evaluation method “5-1. Evaluation of adhesiveness of ceramic green sheet”. gave. The above-mentioned conductive paste was screen-printed on the surface subjected to the atmospheric pressure plasma treatment by a screen printing machine (DP-320 manufactured by New Long Precision Co., Ltd.), and dried at 120° C. for 1 hour to form a 10 mm square paste. A conductive paste film having a distance (margin) of 2.5 mm and a film thickness of 2 μm was formed to obtain a coated sheet TS-1.

(Production Example 2)
A coated sheet TS-2 was obtained in the same manner as in Preparation Example 1 except that GS-1 was not subjected to atmospheric pressure plasma treatment.

(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 green sheet GS-1.

(Production Example 4)
PVB-4 and dihydroterpinyl acetate were added to a 2 L separable flask equipped with a stirrer, a cooler, a thermometer, a hot water bath and a nitrogen gas inlet, and 100 parts by mass of bis(2-butoxyethyl) adipate was added. To 20 parts by mass of PVB-4 was added, and the mixture was stirred at a temperature of 80° C. for 4 hours to obtain an inorganic compound dispersion agent. A conductive paste was prepared in the same manner as in Preparation Example 1 using the obtained inorganic compound dispersing agent. Next, using the obtained conductive paste, coating was performed in the same manner as in Preparation Example 1 except that coating was performed on GS-D to obtain a coated sheet TS-4.

(Production Example 5)
An inorganic compound dispersing agent and a conductive paste were produced in the same manner as in Production Example 4 except that 100 parts by mass of ethyl cellulose (STD-45 manufactured by Dow Chemical Co., Ltd.) was used instead of PVB-4. A coated sheet TS-5 was obtained in the same manner as in Production Example 4 except that the obtained conductive paste was used.

[Production Example 6]
Instead of 100 parts by mass of PVB-4, 50 parts by mass of PVB-4 and 50 parts by mass of ethyl cellulose (STD-200, manufactured by Dow Chemical Co.) were used in the same manner as in Preparation Example 4, An inorganic compound dispersing agent and a conductive paste were manufactured. A coated sheet TS-6 was obtained in the same manner as in Production Example 4 except that the obtained conductive paste was used.

[Production Example 7]
Instead of PVB-4, 100 parts by mass of ethyl cellulose (manufactured by Dow Chemical Co., STD-45) was used. Further, instead of bis(2-butoxyethyl) adipate, 20 parts by mass of triethylene glycol di-2-ethylhexanoate was used. An inorganic compound dispersing agent and a conductive paste were produced in the same manner as in Production Example 4, except that the parts were used. A coated sheet TS-7 was obtained in the same manner as in Production Example 4 except that the obtained conductive paste was used.

Table 4-1 shows TS-1 to TS-3.

Regarding the coated sheets TS-4 to TS-7, in the conductive paste used for producing the coated sheet, the evaluation method "2. Acid value of the organic compound and the inorganic compound dispersing agent" was used for the organic compound and the inorganic compound dispersing agent. The acid value was measured according to the method described in "Measurement of". The measurement results are shown in Table 4-2.

[Example]
(Examples 1-28)
For each of the green sheets GS-1 to GS-28, the storage stability of the ceramic slurry before the production of the green sheet, the dimensional stability of the green sheet during pressure bonding, the adhesiveness of the green sheet, and the green sheet were used. The delamination of the obtained fired body was evaluated according to the method described in the above evaluation method. The evaluation results are shown in Table 5.

(Example 29)
The evaluation was performed in the same manner as in Example 1 except that the GS-1 was not subjected to the atmospheric pressure plasma treatment but was subjected to the adhesiveness evaluation during pressure bonding. The evaluation results are shown in Table 5.

(Example 30)
The atmospheric pressure plasma-treated coated sheet TS-1 and the atmospheric pressure plasma-untreated coated sheet TS-1 (that is, the green sheet GS-1 cut into a size of 10 cm×10 cm) were laminated. A thermocompression bonding test was performed in the same manner as in Example 1 except for the above, and the adhesiveness was evaluated. At this time, the surface subjected to the atmospheric pressure plasma treatment was laminated so as to contact the surface of the other coating sheet TS-1 which was not subjected to the atmospheric pressure plasma treatment (the surface which was not coated with the conductive paste). Further, the obtained laminated body PS-1 was evaluated for dimensional stability and delamination of the fired body in the same manner as in Example 1. The evaluation results are shown in Table 5.

(Example 31)
The coated sheet TS-2 was evaluated for the dimensional stability of the TS-2 during pressure bonding and the adhesion of the TS-2 according to the method described in the above evaluation method. The evaluation results are shown in Table 7.

(Examples 32 to 34)
Regarding the coated sheets TS-4 to TS-6, the slurry storage stability of the conductive paste, the dimensional stability of the coated sheet during pressure bonding, the adhesiveness of the coated sheet, and the delamination of the fired body obtained by using Was evaluated according to the method described in the above evaluation method. The evaluation results are shown in Table 8.

[Comparative example]
(Comparative Examples 1 to 11)
For each of the green sheets GS-A to GS-K, the storage stability of the ceramic slurry before the production of the green sheet, the dimensional stability of the green sheet at the time of pressure bonding, the adhesiveness of the green sheet and the green sheet were used. The delamination of the obtained fired body was evaluated according to the method described in the above evaluation method. The evaluation results are shown in Table 6.

(Comparative Example 12)
With respect to the coated sheet TS-3, the dimensional stability of the TS-3 during pressure bonding and the adhesiveness of the TS-3 were evaluated according to the method described in the above evaluation method. The evaluation results are shown in Table 7.

(Comparative Example 13)
Regarding the coated sheet TS-7, the slurry storage stability of the conductive paste, the dimensional stability of the TS-7 during pressure bonding, the adhesion of the TS-7, and the delamination of the fired body obtained by using the TS-7 are described above. The evaluation was performed according to the evaluation method. The evaluation results are shown in Table 8.

Claims (20)

Binder resin (A) having a hydroxyl group in the molecule, the following general formula (1):

(In the formula, R1 and R4 each independently represent an organic group having at least one ether bond. R2 represents an alkylene group having 1 to 20 carbon atoms and optionally having a branch. R3 represents carbon. From the resin composition containing the organic compound (B) and the organic solvent (C) represented by Formula 1 to 4 which may have a branched alkylene group, and m represents an integer of 0 to 5. An inorganic compound dispersing agent according to claim 1, wherein the inorganic compound dispersing agent has an acid value of 5 mgKOH/g or less. The agent for dispersing an inorganic compound according to claim 1, wherein the acid value of the organic compound (B) is 5 mgKOH/g or less. R1 and/or R4 are each independently the following general formula (2):

(In the formula, R5 represents an alkyl group having 1 to 10 carbon atoms which may have a branch. R6 represents an alkylene group having 1 to 10 carbon atoms which may have a branch. R7 represents 1 to 1 carbon atoms. 4 represents an alkylene group, and n represents an integer of 0 to 2), The agent for dispersing an inorganic compound according to claim 1 or 2, which is an organic group having at least one ether bond. The inorganic compound dispersing agent according to any one of claims 1 to 3, 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 agent for dispersing an inorganic compound according to claim 1, wherein the binder resin (A) contains at least one selected from the group consisting of polyvinyl acetal, ethyl cellulose and (meth)acrylic resin. The binder resin (A) contains polyvinyl acetal, and 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 agent for dispersing an inorganic compound according to claim 5, having a degree of polymerization of 200 to 5,000. A slurry composition containing an inorganic compound (D) and the agent for dispersing an inorganic compound according to any one of claims 1 to 6. Binder resin (A) having a hydroxyl group in the molecule, the following general formula (1):

(In the formula, R1 and R4 each independently represent an organic group having at least one ether bond. R2 represents an alkylene group having 1 to 20 carbon atoms and optionally having a branch. R3 represents carbon. Represents an alkylene group which may have a branch number of 1 to 4, m represents an integer of 0 to 5), an organic compound (B), an organic solvent (C) and an inorganic compound (D). A slurry composition comprising the resin composition contained. The slurry composition according to claim 7 or 8, wherein the inorganic compound (D) is a ceramic powder. The slurry composition according to claim 9, which contains 2 to 200 parts by mass of the organic solvent (C) with respect to 100 parts by mass of the ceramic powder. A ceramic green sheet produced using the slurry composition according to claim 9. This is the ratio of the intensity of Ba+ ions detected to the intensity of Ti+ ions detected when secondary ion analysis is performed on at least one side of the ceramic green sheet with a time-of-flight secondary ion analyzer (Ba+ ions). (Strength of Ti)/(strength of Ti+ ion) satisfies 20<(strength of Ba+ ion)/(strength of Ti+ ion)<1000. The slurry composition according to claim 7 or 8, wherein the inorganic compound (D) is a conductive powder. The slurry composition according to claim 13, which contains 1 to 50 parts by mass of the binder resin (A) with respect to 100 parts by mass of the conductive powder. The slurry composition according to claim 13 or 14, which contains 5 to 600 parts by mass of the organic solvent (C) with respect to 100 parts by mass of the conductive powder. A conductive paste comprising the slurry composition according to claim 13. A coated sheet comprising a ceramic green sheet according to claim 11 and a layer of dried conductive paste disposed on at least one surface thereof. A coated sheet obtained by disposing the layer obtained by drying the conductive paste according to claim 16 on at least one surface of a ceramic green sheet. The ceramic green sheet according to claim 11 or 12, at least a part of which is plasma-treated. The coated sheet according to claim 17, wherein at least a part of the surface of the coated sheet is subjected to plasma treatment.