KR100881260B1 - Coating material for thick green sheet, process for producing the same, and process for producing electronic component with the coating material - Google Patents

Abstract

A thick film green sheet coating material capable of applying a thick film relatively, having excellent cutting property (breakable strength) of the sheet formed after application, and having excellent breathability and good handling properties, and a sheet having high adhesive strength, Provided are a method for producing a thick film green sheet coating material, a method for producing a thick film green sheet, a thick film green sheet and an electronic component manufacturing method. In the present invention, as a paint for thick film green sheets having a ceramic powder, a binder resin containing butyral resin as a main component, and a solvent, the solvent has a binder resin in comparison with a good solvent and a good solvent in which the binder resin is well dissolved. A poor solvent with low solubility is included, and a poor solvent is contained in 30 to 60 mass% with respect to the whole solvent. Good solvents are alcohols, poor solvents are toluene, xylene, mineral spirits, benzyl acetate, solvent naphtha and the like.

Description

Thick film green sheet paint, its manufacturing method and manufacturing method of electronic components using the paint {COATING MATERIAL FOR THICK GREEN SHEET, PROCESS FOR PRODUCING THE SAME, AND PROCESS FOR PRODUCING ELECTRONIC COMPONENT WITH THE COATING MATERIAL}

According to the present invention, a thick film which can be applied to a relatively thick film, which is excellent in cutting property (breakable strength) of the sheet formed after application, and which can form a sheet having excellent breathability due to good breathability and high adhesive force The manufacturing method of the paint for green sheets, the paint for thick film green sheets, the manufacturing method of thick film green sheets, the thick film green sheet, and the manufacturing method of an electronic component.

In order to manufacture ceramic electronic components, such as a CR-embedded board | substrate and a laminated ceramic capacitor, normally, the ceramic coating which consists of a ceramic powder, a binder (acrylic resin, butyral resin, etc.), a plasticizer, and an organic solvent (toluene, MEK) is prepared first. . Next, this ceramic coating material is applied onto a PET film using a doctor blade method or the like, heated and dried, and then the PET film is peeled off to obtain a ceramic green sheet. Next, the internal electrodes are printed and dried on the ceramic green sheet, and the stacked ones are cut into chips to form green chips. After firing these green chips, terminal electrodes are formed to form electrons such as multilayer ceramic capacitors. Manufacture parts.

When manufacturing a multilayer ceramic capacitor, the interlayer thickness of the sheet | seat in which an internal electrode is formed is in the range of about 1 micrometer-about 100 micrometers based on the desired capacitance required as a capacitor. In the multilayer ceramic capacitor, a portion where the internal electrode is not formed is formed in the outer portion in the lamination direction of the capacitor chip.

The thickness of the dielectric layer corresponding to the part where this internal electrode is not formed is about several tens of micrometers-several hundred micrometers, and this part is shape | molded using the comparatively thick ceramic green sheet in which the internal electrode was not printed. Since the thickness of the green sheet to which the internal electrodes are printed is relatively thin, when the outer portion is to be molded using this thin green sheet, the number of laminations increases, the number of manufacturing steps increases, leading to an increase in manufacturing cost.

By the way, the larger the number of dielectric layers in a single-chip capacitor, the higher the solid solution amount, and the size of the chip is limited. Therefore, it is necessary to make the dielectric layer thin. The dielectric layer is obtained by wrapping dielectric particles of submicron order with a resin (binder) in a sheet shape and laminating and baking them, and producing a thin green sheet leads to thinning of the dielectric layer.

Moreover, since a thin sheet is weak and easy to be broken, it is proposed by this applicant to employ polyvinyl butyral (PVB) resin as a high-strength binder resin as resin to shape a sheet | seat. As a result, a dielectric green sheet having a thickness of 2 μm or less can be produced and handled without damage.

In addition to the dielectric layer (inner layer) sandwiched between the inner electrode layers in order to obtain a capacitance, the ceramic part used for the multilayer chip capacitor has a cover part (outer layer) which forms the outer side of the chip. While the inner layer is required to be thin as described above, the outer layer needs some thickness to protect the internal structure. In addition, while the physical properties of the sheet required for the inner layer are dense, smooth, and strong, the outer layer is required to have physical properties such as adhesion, air permeability, and cutting property that are more important for handling performance.

Thus, in the outer layer and the inner layer, the required sheet physical properties are so different that they can be said to be exactly opposite. Therefore, it is common that the sheet | seat which satisfy | fills the physical property requested | required of an outer layer as a coating material for the green sheets specialized for an inner layer cannot apply | coat.

Then, the method of changing the composition of resin, adding the additive which supplements the property which resin does not have, etc. is known. For example, in following patent document 1, the sheet physical property is controlled by the blend of resin. Moreover, in following patent document 2, a tackifier is added and the adhesiveness of a sheet is improved.

However, in the method of patent document 1, the composition of binder resin changes with each of the green sheet for inner layers and the green sheet for outer layers. In the debinding process by heating the green chip, the debinding reaction occurs at different timings in the inner layer and the outer layer, which may damage the strength of the chip and lead to damage such as cracks.

Moreover, in the method of patent document 2, since the tackifier enters, it is thought that the adhesiveness of a sheet improves, but since this tackifier is also a kind of resin component, the same problem as patent document 1 is concerned.

Patent Document 1: Japanese Patent Publication No. 2002-104878

Patent Document 2: Japanese Patent Application Laid-Open No. 2000-133547

(Tasks to be solved by the invention)

The present invention has been made in view of such a situation, and the object thereof is relatively thick application of the film, excellent cutting property (breakable strength) of the sheet formed after application, and excellent breathability of the sheet, and excellent handling properties. A method for producing a thick film green sheet, a thick film green sheet, a thick film green sheet, a thick film green sheet, and an electronic component.

(Means to solve the task)

In order to achieve the above object, the paint for thick film green sheets according to the present invention is a paint for thick film green sheets having ceramic powder, a binder resin containing butyral resin as a main component, and a solvent,

The solvent includes a good solvent for dissolving the binder resin satisfactorily, and a poor solvent having low solubility in the binder resin as compared with the good solvent,

The said poor solvent is contained in 30 to 60 mass% with respect to the whole solvent, It is characterized by the above-mentioned.

In the present invention, the poor solvent is defined as a solvent which does not dissolve the binder resin at all, a solvent which dissolves somewhat but little, or a solvent which does not dissolve but swells. On the other hand, a good solvent is a solvent other than a poor solvent, and is a solvent which melt | dissolves binder resin favorably.

Preferably, the poor solvent contains a solvent having a higher boiling point than the good solvent.

Preferably, the good solvent is an alcohol, and the poor solvent includes at least one of toluene, xylene, mineral spirit, benzyl acetate, solvent naphtha, industrial gasoline, kerosene, cyclohexanone, heptanone, and ethylbenzene. As alcohol as a good solvent, methanol, ethanol, propanol, butanol, etc. are illustrated, for example.

In addition, when mineral spirit (MSP) is contained as a poor solvent, it is preferable that mineral spirit alone is contained in more than 7% and less than 15% with respect to the whole solvent. When the addition amount of MSP is too small, there exists a tendency for air permeability to deteriorate, and when there is too much addition amount, the surface smoothness of a sheet | seat will fall and it will become difficult to thicken a film.

In the present invention, a fine powder pigment (ceramic powder) is used without changing the resin and other solid organic components, using the same butyral resin as the binder resin included in the paint for the layered green sheet which enables the dielectric layer to be thinned. ) Can be used to form the green sheet of the thick film. Moreover, the air permeability, cutting property, and adhesiveness of the green sheet formed using the paint for thick film green sheets of this invention improve, and the handling property of a thick film green sheet improves. Therefore, manufacture of a thick film green sheet becomes easy, and manufacture of the electronic component manufactured using a thick film green sheet becomes easy.

Moreover, in this invention, since it becomes possible to manufacture a thick film green sheet, without changing the binder resin and other solid organic components contained in the paint for thin-layered green sheets, control of the debinding process by heating of a green chip is carried out. It becomes easy. That is, in the sheet | seat of the thin-layered green sheet paint which forms an inner layer, and the sheet | seat of the thick film green sheet paint which forms an outer layer, a binder removal reaction occurs at the same timing. For this reason, the intensity | strength of a chip | tip is not impaired and there exists a possibility that it may lead to damage, such as a crack.

In the present invention, the poor solvent is included in the range of 30 to 60 mass%, more preferably 30 to 50 mass%, based on the entire solvent. When the mass% of this poor solvent is too low, the effect of the present invention tends to be low, and when too high, the filtration property deteriorates and the thickness becomes difficult.

Preferably, the butyral resin is a polyvinyl butyral resin, the polymerization degree of the polyvinyl butyral resin is 1000 or more and 1700 or less, the butyralization degree of the resin is greater than 64% and less than 78%, the residual acetyl group The amount is less than 6%.

This polyvinyl butyral resin is the same resin as binder resin contained in the thin-layered green sheet coating material which enables thinning of the dielectric layer, and when it is thinned, it tends to be difficult to obtain sufficient mechanical strength. Moreover, when polymerization degree is too big | large, there exists a tendency for surface roughness in the case of sheet formation to deteriorate. Moreover, when the butyralization degree of polyvinyl butyral resin is too low, there exists a tendency for the solubility to paint to deteriorate, and when too high, there exists a tendency for sheet surface roughness to deteriorate. Moreover, when there is too much residual acetyl group amount, there exists a tendency for sheet surface roughness to deteriorate.

Originally, it is difficult to mold a thick film green sheet using a polyvinyl butyral resin suitable for thinning. However, in this invention, formation of a thick film green sheet is attained by adjusting the solvent composition in paint, using the same thing as polyvinyl butyral resin suitable for thinning as binder resin.

Preferably, the said binder resin is contained in 4-6.5 mass parts with respect to 100 mass parts of said ceramic powders. When the addition amount of this binder resin is too small, there exists a tendency for sufficient adhesive strength not to be taken in the sheet molding process, and when too large, there exists a tendency for the strength of a sheet to be too high.

The manufacturing method of the paint for thick film green sheets which concerns on this invention,

As a method of manufacturing the paint for thick film green sheets described in any one of the above,

To the average particle diameter of the ceramic powder (base material) before dispersing in the thick film green sheet paint, the ceramic powder so that the average particle diameter of the ceramic powder after being dispersed in the thick film green sheet paint is not less than 80%. It characterized in that the grinding.

In the paint for thinning green sheets, in order to enable thinning of the sheet, ceramics are used so that the average particle size of the ceramic powder dispersed in the paint for green sheets becomes a fine particle size of 80% or less with respect to the average particle diameter of the base material. Grind the powder. On the other hand, in the paint for thick film green sheets of the present invention, when the average particle diameter of the ceramic powder to the base material is too small, the density of the sheet becomes high, the adhesiveness becomes poor, the handling properties decrease, and the thick film becomes difficult. Therefore, conventionally, it is necessary to disperse the ceramic powder in the paint so that the ceramic powder is not pulverized finely. For example, it is necessary to strictly control the pulverization level from 100% to 90% and to disperse the ceramic powder in the paint, but this control was difficult. In the present invention, by including the poor solvent as the solvent, up to 80% of the crushing can be allowed, and the process of dispersing the ceramic powder in the coating becomes easy. Moreover, in this invention, the time of the manufacturing process (pigment dispersion and resin kneading | mixing of paint) can be shortened.

The manufacturing method of the thick film green sheet which concerns on this invention,

The process of preparing the paint for thick film green sheets of any one of said description,

It has a process of shape | molding a thick film green sheet using the said thick film green sheet coating material.

The thick film green sheet of the present invention is produced using the paint for thick film green sheet described in any one of the above.

The thick film green sheet according to the present invention is suitable for use in, for example, an outer layer portion of a ceramic chip capacitor (a portion which does not fit into an inner electrode layer and which does not contribute to dielectric properties).

The manufacturing method of the ceramic electronic component of this invention,

The process of preparing the paint for thick film green sheets of any one of said description,

Forming an outer green sheet using the thick film green sheet coating material;

A process of preparing a paint for a layered green sheet containing a binder resin of the same kind as the binder resin contained in the paint for the thick film green sheet;

A step of forming an inner green sheet thinner than the outer green sheet by using the paint for thinning green sheet;

Stacking the inner green sheet through an internal electrode layer to obtain a laminate;

Stacking the outer green sheet on both end surfaces of the laminate in the stacking direction to obtain a green chip;

And firing the green chip.

Preferably, the ceramic powder of the same kind as the ceramic powder used for the said thick film green sheet coating material is used for the said thin-layer green sheet coating material. By using the same kind of ceramic powder, the manufacture of the ceramic electronic component becomes easy.

Preferably, the average particle diameter of the ceramic powder contained in the said thin-layered green sheet coating material is smaller than the average particle diameter of the ceramic powder contained in the said thick film green sheet coating material. By setting it as such a relationship, thinning of an inner green sheet and thickening of an outer green sheet can be satisfied simultaneously.

Preferably, with respect to the average particle diameter of the ceramic powder before dispersing in the paint for thick film green sheet, the ceramic particle after dispersing in the paint for thick film green sheet does not have a particle size of less than 80%. The average particle diameter of the ceramic powder after disperse | distributing to the said thin-layered green sheet paint with respect to the process of grind | pulverizing powder, and the ceramic powder before disperse | distributing to the said thin-layered green sheet paint, The particle diameter of 80% or less Preferably, the ceramic powder is crushed.

By doing in this way, thinning of an inner green sheet and thickening of an outer green sheet can be satisfied simultaneously. In addition, the precise control of the crushing conditions in the step of dispersing the ceramic powder in the paint for thick film green sheet can be alleviated.

1 is a schematic cross-sectional view of a multilayer ceramic capacitor according to one embodiment of the present invention.

FIG. 2 is an essential part cross sectional view of the green sheet used in the manufacturing process of the capacitor shown in FIG. 1. FIG.

3 is an essential part cross-sectional view of the green chip used in the manufacturing process of the capacitor shown in FIG. 1.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated based on embodiment shown in drawing.

First, the whole structure of a multilayer ceramic capacitor is demonstrated as one Embodiment of the electronic component manufactured using the green-sheet coating material (dielectric paste) and green sheet which concerns on this invention.

As shown in FIG. 1, the multilayer ceramic capacitor 1 has a capacitor element body 10 having a structure in which the inner dielectric layers 2 and the inner electrode layers 3 are alternately stacked. At both ends of the capacitor element main body 10, a pair of terminal electrodes 4 which are connected to the internal electrode layers 3 alternately arranged inside the element main body 10 are formed. Although there is no restriction | limiting in particular in the shape of the capacitor element main body 10, Usually, it becomes a rectangular parallelepiped shape. Moreover, there is no restriction | limiting in particular in the dimension, either, What is necessary is just to set it as a suitable dimension according to a use, Usually, length (0.6-5.6 mm, Preferably 0.6-3.2 mm) x side (0.3-5.0 mm, Preferably 0.3-) 1.6 mm) x thickness (0.1-1.9 mm, preferably 0.3-1.6 mm).

The internal electrode layers 3 are laminated so that each side end surface is alternately exposed on the surface of the two end portions of the capacitor element main body 10 facing each other. The pair of terminal electrodes 4 are formed at both ends of the capacitor element main body 10 and are connected to the exposed end faces of the internal electrode layers 3 which are alternately arranged to form a capacitor circuit.

In the capacitor element main body 10, the outer dielectric layer 20 is arrange | positioned at the both outer edge part of the lamination direction of the internal electrode layer 3 and the inner dielectric layer 2, and the inside of the element main body 10 is protected. .

Dielectric Layers (2) and (20)

The composition of the inner dielectric layer 2 and the outer dielectric layer 20 is not particularly limited in the present invention, but is composed of, for example, the following dielectric ceramic composition.

The dielectric ceramic composition of the present embodiment is made of, for example, a dielectric material such as calcium titanate, strontium titanate, and / or barium titanate.

In addition, what is necessary is just to determine suitably all conditions, such as the number of laminated | multilayer and thickness of the inner dielectric layer 2 shown in FIG. 1, according to an objective and a use, In this embodiment, the thickness of the inner dielectric layer 2 is 1 micrometer-50 It is about micrometer, Preferably it is 5 micrometers or less, More preferably, it is thinned to 3 micrometers or less. In addition, the thickness of the outer side dielectric layer 20 is about 100 micrometers-about several hundred micrometers, for example.

Internal Electrode Layer (3)

Although the conductive material contained in the internal electrode layer 3 is not specifically limited, Since the constituent material of the inner dielectric layer 2 has reduction resistance, a nonmetal can be used. As a base metal used as a electrically conductive material, Ni, Cu, Ni alloy, or Cu alloy is preferable. When the main component of the internal electrode layer 3 is Ni, a method of firing at a low oxygen partial pressure (reducing atmosphere) is used so that the dielectric is not reduced. On the other hand, a method is used such that the composition ratio is deviated from the stoichiometric composition so as not to be reduced.

Although the thickness of the internal electrode layer 3 may be suitably determined according to a use etc., it is about 0.5-5 micrometers normally.

Terminal electrode (4)

Although the conductive material contained in the terminal electrode 4 is not specifically limited, Cu, Cu alloy, Ni, Ni alloy, etc. are used normally. Moreover, Ag, Ag-Pd alloy, etc. can also be used, of course. In addition, in this embodiment, inexpensive Ni, Cu, and these alloys can be used.

Although the thickness of a terminal electrode may be suitably determined according to a use etc., it is preferable that it is about 10-50 micrometers normally.

Manufacturing method of laminated ceramic capacitor

Next, the manufacturing method of the multilayer ceramic capacitor which concerns on one Embodiment of this invention is demonstrated.

(1) First, in order to manufacture the ceramic green sheet which constitutes the inner dielectric layer 2 shown in FIG. 1 after firing, a thin layer dielectric paint (paint for thin layer green sheet) is prepared.

The thin dielectric paint is composed of an organic solvent-based paint obtained by kneading a dielectric material (ceramic powder) and an organic vehicle.

As a dielectric material, it can select suitably from various compounds which become a complex oxide and an oxide, for example, carbonate, nitrate, hydroxide, an organometallic compound, etc., and can mix and use. The dielectric material is usually used as a powder having an average particle diameter of 0.1 to 3 µm or less, preferably about 0.4 µm or less. In addition, in order to form a very thin green sheet, it is preferable to use powder finer than the green sheet thickness.

The organic vehicle is obtained by dissolving a binder resin in an organic solvent. As binder resin used for an organic vehicle, in this embodiment, polyvinyl butyral resin is used. The polymerization degree of this polyvinyl butyral resin is 1000 or more and 1700 or less, Preferably it is 1400-1700. Further, the butyralization degree of the resin is larger than 64%, smaller than 78%, preferably larger than 64% and 70% or less, and the amount of residual acetyl groups is less than 6%, preferably 3% or less.

The degree of polymerization of the polyvinyl butyral resin can be measured, for example, by the degree of polymerization of the polyvinyl acetal resin as a raw material. In addition, butyralization degree can be measured based on JISK6728, for example. In addition, the amount of residual acetyl groups can be measured based on JISK6728.

If the degree of polymerization of the polyvinyl butyral resin is too small, for example, when it is thinned down to about 5 µm or less, preferably 3 µm or less, it tends to be difficult to obtain sufficient mechanical strength. Moreover, when polymerization degree is too big | large, there exists a tendency for surface roughness in the case of sheet formation to deteriorate. Moreover, when the butyralization degree of polyvinyl butyral resin is too low, there exists a tendency for the solubility to paint to deteriorate, and when too high, there exists a tendency for sheet surface roughness to deteriorate. Moreover, when there is too much residual acetyl group amount, there exists a tendency for sheet surface roughness to deteriorate.

The organic solvent used for an organic vehicle is not specifically limited, For example, organic solvents, such as a terpineol, alcohol, butyl carbitol, acetone, toluene, are used. In this embodiment, as an organic solvent, Preferably, it contains an alcoholic solvent and an aromatic solvent, The total mass of an alcoholic solvent and an aromatic solvent is 100 mass parts, and an aromatic solvent is 10 mass parts or more. 20 mass parts or less are included. If the content of the aromatic solvent is too small, the sheet surface roughness tends to increase, and if too large, the paint filtration characteristics deteriorate, and the sheet surface roughness also increases and deteriorates.

Examples of the alcohol solvents include methanol, ethanol, propanol, butanol and the like. Toluene, xylene, benzyl acetate, etc. are illustrated as an aromatic solvent.

The binder resin is preferably dissolved and filtered in at least one or more alcoholic solvents of methanol, ethanol, propanol and butanol to form a solution, and is preferably added to the dielectric powder and other components. Binder resin of high polymerization degree is hard to melt | dissolve in a solvent, and there exists a tendency for the dispersibility of coating material to deteriorate by a normal method. In the method of the present embodiment, since the binder resin of high polymerization degree is dissolved in the above good solvent and then ceramic powder and other components are added to the solution, it is possible to improve the coating dispersibility, and It can suppress occurrence. Moreover, in solvents other than the above-mentioned solvent, solid content concentration cannot be raised and there exists a tendency for the time-dependent change of lacquer viscosity to increase.

In the present embodiment, in the dielectric paint, xylene-based resin may be added as binder as well as binder resin. Xylene-based resin is 1.0 mass% or less with respect to 100 mass parts of ceramic powders, More preferably, it is 0.1 or more and 1.0 mass% or less, Especially preferably, it adds in the range of larger than 0.1 and 1.0 mass% or less. When the addition amount of xylene system resin is too small, there exists a tendency for adhesiveness to fall. Moreover, when the addition amount is too large, although adhesiveness improves, the surface roughness of a sheet will become rough, many lamination will become difficult, the tensile strength of a sheet will fall, and there exists a tendency for the handleability of a sheet to fall.

The dielectric paint may contain additives selected from various dispersants, plasticizers, charging agents, dielectrics, glass flits, insulators, and the like, as necessary.

In this embodiment, although it does not specifically limit as a dispersing agent, Preferably, the nonionic dispersing agent of a polyethyleneglycol type | system | group is used, The hydrophilic and lipophilic balance (HLB) value is 5-6. The dispersant is preferably 0.5 parts by mass or more and 1.5 parts by mass or less, and more preferably 0.5 parts by mass or more and 1.0 parts by mass or less with respect to 100 parts by mass of the ceramic powder.

If the HLB is out of the above range, the paint viscosity tends to increase and the sheet surface roughness tends to increase. In addition, in the dispersing agent which is not a polyethyleneglycol nonionic dispersing agent, since coating viscosity increases, sheet surface roughness increases or sheet elongation falls, it is unpreferable.

If the amount of the dispersant is too small, the sheet surface roughness tends to increase, and if too large, the sheet tensile strength and stackability tend to decrease.

In this embodiment, as the plasticizer, dioctyl phthalate is preferably used, and it is preferably 40 parts by mass or more and 70 parts by mass or less, more preferably 40 to 60 parts by mass with respect to 100 parts by mass of the binder resin. have. Dioctyl phthalate is preferable in terms of both sheet strength and sheet elongation as compared with other plasticizers, and is particularly preferable because the peel strength from the support is small and easily peeled off. Moreover, when there is too little content of this plasticizer, sheet elongation will be small and plasticity will tend to become small. Moreover, when there is too much content, a plasticizer will flow out from a sheet | seat, the segregation of a plasticizer with respect to a sheet will arise easily, and there exists a tendency for the dispersibility of a sheet to fall.

In the present embodiment, the dielectric paint contains 1 part by mass or more and 6 parts by mass or less, preferably 1 to 3 parts by mass with respect to 100 parts by mass of the dielectric powder. When the content of water is too small, the change in the paint properties due to moisture absorption becomes large, the paint viscosity tends to increase, and the filtration properties of the paint tend to deteriorate. In addition, when there is too much content of water, paint separation and sedimentation will arise, dispersibility will worsen, and the surface roughness of a sheet | seat tends to deteriorate.

In this embodiment, at least one of hydrocarbon solvent, industrial gasoline, kerosene, and solvent naphtha is preferably 3 parts by mass or more and 15 parts by mass or less, and more preferably 5 parts by mass based on 100 parts by mass of the dielectric powder. It adds at -10 mass parts. By adding these additives, sheet strength and sheet surface roughness can be improved. When the addition amount of these additives is too small, the effect of addition is small, and when there is too much addition amount, there exists a tendency for deteriorating sheet strength and sheet surface roughness on the contrary.

The binder resin is preferably contained in an amount of 5 parts by mass or more and 6.5 parts by mass or less with respect to 100 parts by mass of the dielectric powder. When there is too little content of binder resin, there exists a tendency for sheet strength to fall and also stackability (adhesiveness at the time of lamination) deteriorates. Moreover, when there is too much content of binder resin, segregation of binder resin will arise and dispersibility will tend to worsen, and sheet surface roughness will tend to deteriorate.

In the case where the total volume of the ceramic powder, the binder resin and the plasticizer is 100% by volume, the volume ratio of the dielectric powder is preferably 62.42% or more and 72.69% or less, and more preferably 63.93% or more and 72.69% or less. to be. If the volume ratio is too small, segregation of the binder tends to occur, dispersibility tends to deteriorate, and surface roughness tends to deteriorate. On the other hand, when the volume ratio is too large, sheet strength tends to decrease and stackability tends to deteriorate.

In the present embodiment, the dielectric paint preferably contains a charging aid, and the charging aid is preferably an imidazoline-based charging aid. When the charging assistant is other than an imidazoline-based charging assistant, there is a tendency that the charge removal effect is small and sheet strength, sheet elongation or adhesiveness deteriorates.

The charging aid is contained in an amount of 0.1 parts by mass or more and 0.75 parts by mass or less, and more preferably 0.25 to 0.5 parts by mass with respect to 100 parts by mass of the ceramic powder. When the addition amount of the charging assistant is too small, the effect of the removal of the charge becomes small, and when too large, the surface roughness of the sheet deteriorates and the sheet strength tends to deteriorate. If the effect of electrification removal is small, static electricity is likely to occur when the carrier sheet as a support is peeled from the ceramic green sheet, and problems such as wrinkles are likely to occur in the green sheet.

In order to adjust a dielectric paint, ceramic powder is first disperse | distributed in a slurry by the ball mill etc. (pigment dispersion process). This pigment dispersion process is also a grinding | pulverization process of a ceramic powder (pigment) at the same time, and the progress is also seen by the change of the average particle diameter of a ceramic powder. In the present embodiment, in the pigment dispersion step, the average particle diameter of the ceramic powder after dispersion in the slurry is 80% or less, preferably less than 80% with respect to the average particle diameter of the ceramic powder (base material) before the dispersion in the slurry, The pigment is crushed and dispersed.

Next, a dispersant and other additives are added to and dispersed in a slurry containing the ceramic powder to obtain a dispersion paint (dispersant addition and dispersion step). Finally, binder resin is added and kneaded to this dispersion paint (resin kneading step).

Thus, using the dielectric paint (paint for thin layered green sheet) obtained by the doctor blade method etc., as shown in FIG. 2, it is 0.5-30 micrometers on the carrier sheet 30 as a support body, Preferably it is more preferable. Preferably, the inner green sheet 2a is formed to a thickness of about 0.5 to 10 mu m. The inner green sheet 2a is dried on the carrier sheet 30 after being formed.

The drying temperature of the inner green sheet is preferably 50 to 100 ° C, and the drying time is preferably 1 to 20 minutes. The thickness of the inner green sheet after drying shrinks to a thickness of 5 to 25% compared to before drying. As for the thickness of the inner green sheet 2a after drying, 3 micrometers or less are preferable.

(2) Next, in order to manufacture the ceramic green sheet which comprises the outer dielectric layer 20 shown in FIG. 1 after baking, a thick film dielectric material (paint for thick film green sheet) is prepared.

This thick film dielectric paint is adjusted similarly to the above-mentioned thin layer dielectric paint except for the following.

The thick film dielectric paint is composed of an organic solvent-based paint obtained by kneading a dielectric material (ceramic powder) and an organic vehicle, similarly to a thin layer dielectric paint. The binder resin used for a thick film dielectric paint is the same as that used for a thin layer dielectric paint. The organic solvent used for the organic vehicle of a thick-film dielectric paint contains the good solvent which melt | dissolves binder resin favorably, and the poor solvent which is low solubility with respect to binder resin compared with a good solvent, and a poor solvent is a whole solvent, It is contained in the range of 30-60 mass%. In addition, the poor solvent contains a solvent having a higher boiling point than the good solvent.

A good solvent is alcohol, for example, and a poor solvent contains at least 1 of toluene, xylene, mineral spirit, benzyl acetate, solvent naphtha, industrial gasoline, kerosene, heptanone, and ethylbenzene. Examples of the alcohol as the good solvent include methanol, ethanol, propanol, butanol, and the like.

In addition, when mineral spirit (MSP) is contained as a poor solvent, it is preferable that mineral spirit alone is contained in more than 7% and less than 15% with respect to the whole solvent. When the addition amount of MSP is too small, there exists a tendency for air permeability to deteriorate, and when there is too much addition amount, the surface smoothness of a sheet | seat will fall and it will become difficult to thicken a film.

The poor solvent is contained within the range of 30-60 mass% with respect to the whole solvent, More preferably, it is 30-50 mass%. When the mass% of this poor solvent is too low, the effect of the present invention tends to be low, and when it is high, the filtration characteristics deteriorate and a suitable coating material cannot be obtained on sheet molding.

Preferably, binder resin is contained in 4-6.5 mass parts with respect to 100 mass parts of ceramic powders. When the addition amount of this binder resin is too small, there exists a tendency which cannot take sufficient strength and adhesiveness in sheet shaping | molding and processing, and when too much, there exists a tendency for the intensity | strength of a sheet to become high too much.

In order to adjust a thick-film dielectric paint, ceramic powder is first disperse | distributed in a slurry by the ball mill etc. (pigment dispersion process). This pigment dispersion process is also a grinding | pulverization process of a ceramic powder (pigment) at the same time, and the progress is also seen by the change of the average particle diameter of a ceramic powder. In the present embodiment, in the pigment dispersion step, crushing and dispersion of the pigment so that the average particle diameter of the ceramic powder after dispersion in the slurry is less than 80% with respect to the average particle diameter of the ceramic powder (base material) before the dispersion in the slurry. Is done.

In the thin dielectric paint, the ceramic powder is pulverized so that the average particle diameter of the ceramic powder after dispersing in the slurry becomes a fine particle size of 80% or less with respect to the average particle diameter of the base material. On the other hand, in the thick-film dielectric paint, when the average particle diameter of the ceramic powder with respect to a base material becomes too small, the density of a sheet will become high, adhesiveness will worsen, handling property will fall, and thickening becomes difficult. Therefore, in the past, it was necessary to disperse the ceramic powder in the slurry so that the ceramic powder was not finely ground. For example, it was necessary to strictly control the pulverization level from 100% to 90% and to disperse the ceramic powder in the slurry, but this control was difficult. In this embodiment, up to 80% of grinding | pulverization is permissible by including a poor solvent as a solvent, and the process of disperse | distributing ceramic powder in a slurry becomes easy.

Next, a dispersant and other additives are added to the slurry containing this ceramic powder to disperse | distribute, and a dispersion paint is obtained (dispersant addition and dispersion process). Finally, binder resin is added and kneaded to this dispersion paint (resin kneading step).

By using the thick film dielectric paint (paint for thick film green sheet) obtained in this way, as shown in FIG. 2, on the carrier sheet 30 as a support body, Preferably it is 10-100 micrometers, More preferably, as shown in FIG. Preferably, the outer green sheet 20a is formed to a thickness of about 10 to 30 µm. The outer green sheet 20a is dried after being formed in the carrier sheet 30. The carrier sheet 30 is comprised from PET film etc., for example.

The drying temperature of the outer green sheet is preferably 50 to 100 ° C, and the drying time is preferably 1 to 20 minutes. The thickness of the outer green sheet after drying shrinks to a thickness of 5 to 25% compared to before drying. As for the thickness of the outer green sheet 20a after drying, 10 micrometers or more are preferable. The outer green sheet 20a obtained by peeling off the carrier sheet 30 is a part which comprises the outer dielectric layer 20 shown in FIG.

(3) Next, the inner electrode layer 3 shown in FIG. 1 is formed on one surface of the inner green sheet 2a. Although it does not specifically limit as a formation method of the internal electrode layer 3, The printing method, the thin film method, the transfer method, etc. are illustrated.

Then, as shown in FIG. 3, the inner green sheet 2a in which the internal electrode layer was formed is alternately laminated | stacked, and the outer green sheet 20a is laminated | stacked by the single | mono layer or multiple layers in the outer both ends of the lamination direction.

Next, the laminate obtained in this way is cut into a predetermined laminate size to obtain a green chip 100, and then the binder removal treatment and firing are performed. Then, heat treatment is performed to regenerate the dielectric layers 2 and 20.

Although the binder removal process may be performed under normal conditions, in the case where nonmetals such as Ni and a Ni alloy are used as the conductor material of the internal electrode layer, it is particularly preferable to perform the binder under the following conditions.

Temperature rise rate: 5 to 300 ° C / hour, especially 10 to 50 ° C / hour,

Holding temperature: 200-400 ° C., especially 250-350 ° C.,

Holding time: 0.5-20 hours, especially 1-10 hours,

Atmosphere: Mixed gas of humidified N ₂ and H ₂ .

As for baking conditions, the following conditions are preferable.

Temperature rising rate: 50 to 500 ° C / hour, especially 200 to 300 ° C / hour,

Holding temperature: 1100 to 1300 ° C, especially 1150 to 1250 ° C,

Holding time: 0.5 to 8 hours, especially 1 to 3 hours,

Cooling rate: 50-500 ° C./hour, especially 200-300 ° C./hour,

Atmosphere gas: A mixed gas of humidified N ₂ and H ₂ .

However, it is preferable to carry out oxygen partial pressure in the air atmosphere at the time of baking at 10 <^-2> Pa or less, especially 10 <^{-2> -10 <-10>} Pa. When it exceeds the said range, there exists a tendency for an internal electrode layer to oxidize, and when oxygen partial pressure is too low, the electrode material of an internal electrode layer will abnormally sinter and will tend to be cut off in the middle.

The heat treatment after the calcination is preferably performed at a holding temperature or a maximum temperature as 100 ° C or higher, more preferably 1000 to 1100 ° C. If the holding temperature or the maximum temperature during the heat treatment is less than the above range, the dielectric material has insufficient oxidation, so the insulating resistance life tends to be shortened. If the above range is exceeded, the Ni of the internal electrode is oxidized and the capacity is not only lowered. Reaction with the dielectric substrate tends to shorten the lifetime. The oxygen partial pressure at the time of heat treatment is an oxygen partial pressure higher than the reducing atmosphere at the time of baking, Preferably it is ^10-3 Pa ^- 1Pa, More preferably, it is 10-2 Pa ^- 1Pa. Below the above range, the reoxidation of the dielectric layer 2 is difficult, and when the above range is exceeded, the internal electrode layer 3 tends to oxidize. In addition, as for the heat processing conditions other than that, the following conditions are preferable.

Holding time: 0-6 hours, especially 2-5 hours,

Cooling rate: 50-500 ° C./hour, especially 100-300 ° C./hour,

Atmospheric gas: humidified N ₂ gas.

In addition, N ₂ gas, in order to wet the mixed gas or the like, for example, by using such a wetter. In this case, about 0-75 degreeC of water temperature is preferable. The binder removal treatment, firing, and heat treatment may be performed continuously or independently. In the case of carrying out these continuously, after debinding, the atmosphere is changed without cooling, the temperature is subsequently raised to the holding temperature at the time of baking, firing is performed, and then the cooling is performed to change the atmosphere when the holding temperature of the heat treatment is reached. It is preferable to perform heat treatment. On the other hand, when performed by those independent, in the firing, and after heating under a N ₂ gas or a wet N ₂ gas atmosphere to the holding temperature at the time of binder removal, by changing the atmosphere is preferable to keep the temperature was raised again, and heat treatment After cooling to the holding temperature of, it is preferable to change to N ₂ gas or humidified N ₂ gas atmosphere again and continue cooling. Further, in the heat-treatment, N _2, and Fig. After the temperature was raised to the holding temperature under the gas atmosphere, changing the atmosphere, it may be a N ₂ gas atmosphere in a wet the entire process of the heat treatment.

In the thus-obtained sintered body (element body 10), for example, cross-sectional polishing is performed by barrel polishing, sand blasting, or the like, and the terminal electrode paints are fired to form terminal electrodes 6 and 8. About conditions for firing the coating material for the terminal electrode, for example, it is preferable that in the mixed gas of wet N ₂ and H ₂ to about 600~800 ℃ 10-1 minutes. Then, as necessary, the pad layer is formed by plating or the like on the terminal electrodes 6 and 8. In addition, what is necessary is just to prepare the paint for terminal electrodes similarly to the above-mentioned electrode paint.

The multilayer ceramic capacitor of the present invention manufactured in this manner is mounted on or above a printed board by soldering or the like, and is used for various electronic devices and the like.

In the method for producing a multilayer ceramic capacitor using the dielectric paint (paint for thin-layered green sheet) and the green sheet according to the present embodiment, even a very thin green sheet can be obtained from a support by using a binder resin containing a butyral resin as a main component. It becomes possible to manufacture the laminated green sheet which has the strength which can withstand peeling, and also has favorable adhesiveness and handling property. For example, the thickness of the dielectric layer after firing (green sheet after firing) can be reduced to 5 µm or less, preferably 3 µm or less, and more preferably 2 µm or less. In the thinned green sheet of the present embodiment, since the surface roughness is small, it is also possible to increase the number of laminated layers.

Moreover, in the manufacturing method of the laminated ceramic capacitor which uses the thin-layer dielectric paint (paint for thin-layered green sheet) which concerns on this embodiment, and a green sheet, as a specific kind of dispersing agent, the dispersing agent whose HLB is a specific range is used. For this reason, even a very thin green sheet, for example, about 5 µm or less, has strength that can withstand peeling from a carrier sheet, and also has good adhesiveness and handling property. In addition, the surface roughness of the sheet is small, and the stackability is excellent. For this reason, it becomes easy to laminate | stack many green sheets through an electrode layer.

Moreover, in the manufacturing method of the thick film dielectric paint (paint for thick film green sheet) which concerns on this embodiment, and the laminated ceramic capacitor using this paint, the same bootie as the binder resin contained in the thin-layer dielectric paint which enables thinning of a dielectric layer is possible. A thick film green sheet can be formed using a fine powder (ceramic powder) without changing a resin or other solid organic component using a Lal resin. Moreover, the air permeability, cutting property, and adhesiveness of the green sheet formed using the thick film dielectric paint of this embodiment improve, and the handling property of a thick film green sheet improves. Therefore, manufacture of a thick film green sheet becomes easy, and manufacture of the electronic component manufactured using a thick film green sheet becomes easy.

In addition, in this embodiment, since it becomes possible to manufacture a thick film green sheet without changing the binder resin and other solid organic components contained in a thin dielectric paint, it is easy to control a binder removal process by heating a green chip. Become. That is, in the sheet of the thin layer dielectric paint forming the inner layer and the sheet of the thick film dielectric coating forming the outer layer, the binder removal reaction occurs at the same timing. As a result, the strength of the chip is not impaired, and there is no fear of cracking or the like.

In addition, this invention is not limited to embodiment mentioned above, It can change variously within the scope of this invention.

For example, the method of this invention is not limited to the manufacturing method of a multilayer ceramic capacitor, It is possible to apply also to the manufacturing method of other laminated electronic components.

Example

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated based on further detailed Example, this invention is not limited to these Examples.

Example 1a

Manufacture of paint for thick film green sheet

BaTiO ₃ powder (BT-02 / Sakai Chemical Co., Ltd.) was used as a starting material for ceramic powder. (Ba _0.6 Ca _0.4 ) SiO ₃ : 1.48 parts by mass, Y ₂ O ₃ : 1.01 parts by mass, MgCO ₃ : 0.72% by mass, Cr ₂ O ₃ : 0.13% by mass, and V _{2 based} on 100 parts by mass of this BaTiO ₃ powder. O _5: 0.045 prepared ceramic powder subcomponent additives that are mass%.

Initially, only the minor component additives were mixed in a ball mill and slurried. That is, the subcomponent additive (total amount 8.8 g), ethanol: 6 g, n-propanol: 6 g, xylene: 2 g, and a dispersant (0.1 g) were preliminarily pulverized with a ball mill for 20 hours.

As a binder, 15% lacquer (BH6 manufactured by Sekisui Chemical Co., Ltd. was dissolved in ethanol / n-propanol = 1: 1) of BH6 (polyvinyl butyral resin / PVB) was used. As the dispersant, a polyethylene glycol nonionic dispersant (HLB = 5 to 6) was used.

Next, with respect to BaTiO ₃ : 191.2 g, the preliminary grinding slurry of the subsidiary ingredient additive, 37 g of ethanol, 37 g of n-propanol, 50 g of xylene, 15 g of mineral spirit (MSP), and DOP as a plasticizer component ( Dioctyl phthalate): 6 g of polyethylene glycol-based nonionic dispersant (HLB = 5 to 6) as a dispersant: 1.4 g of BH6 (polyvinyl butyral resin / PVB) and 15% lacquer (BH6 manufactured by Sekisui Chemical Co., Ltd.) Was dissolved in ethanol / n-propanol = 1: 1), and 6 mass% was added as solid content (80 g as lacquer addition amount). Then, this dispersion coating material was mixed in a ball mill for 20 hours to obtain a ceramic coating material (paint for thick film green sheet).

In the production of this ceramic paint, the average particle diameter d50 of the ceramic powder after dispersing in the paint is 80% or more, as shown in Table 1 below, with respect to the average particle diameter of the ceramic powder (base material) before dispersing in the paint. The pigment was crushed and dispersed so as to be%. That is, the average particle diameter d50 of BaTiO ₃ as a base material prior to dispersing the coating material, 0.623㎛ inde, an average particle diameter d50 of the result of the mixing by the ball mill, BaTiO ₃ being the 0.512㎛, was 82.2% for the crushed condition. In addition, an average particle diameter d50 means the average particle diameter in 50% of the total volume of a ceramic powder, For example, it is defined by JISR1629 etc. This particle size was measured by Micro Track HRA manufactured by Nippon Shokuki Co., Ltd.

The degree of polymerization of the polyvinyl butyral resin as the binder resin contained in this ceramic paint was 1400, its butyralization degree was 69% ± 3%, and the residual acetyl group amount was 3 ± 2%. This binder resin is contained in ceramic coating at 6 mass parts with respect to 100 mass parts of ceramic powders (including a ceramic powder subcomponent additive).

In addition, DOP as a plasticizer is contained in a ceramic paint at 50 mass parts with respect to 100 mass parts of binder resins. 0.7 mass part is contained with respect to 100 mass parts of ceramic powders of the polyethyleneglycol type nonionic dispersing agent as a dispersing agent.

In addition, as shown in Table 1, 68.2 mass% of ethanol and n-propanol as a good solvent are contained with respect to the whole solvent, 9.1 mass% of MSP which is a part of a poor solvent is contained in a part of a poor solvent in a coating material. 22.7 mass% of xylene which is a high boiling point solvent is contained. That is, the poor solvent which consists of MSP + xylene is contained 31.8 mass% with respect to the whole solvent.

Table 1 shows the results of examining the filtration characteristics of this ceramic paint. In the evaluation of the filtration characteristics, as a filter, product number No. 5C manufactured by Kiriyama Co., Ltd. and 4 micrometers of holding particle diameters were used, and the time which 150 g of paint passes the 28.26 cm <2> margin area under the pressure of 0.1 Mpa is evaluated. did. The shorter the passage time, the better the filtration characteristics. Excellent filtration characteristics mean that there are few aggregates in the coating material and the binder resin is satisfactorily dissolved. The filtration time was 5 minutes or less, and was judged to be good (O) in the comprehensive judgment. In addition, in Table 1, it determined with the filtration time longer than 5 minutes.

TABLE 1

TABLE 2

Production of green sheet

The thickness of the sheet | seat which can be applied was determined by apply | coating the coating material obtained as mentioned above on the PET film (carrier sheet) as a support film with a wire bar coater, and drying. As shown in Table 1, creation of a 13 micrometer green sheet was possible at the thickness after drying.

Evaluation of the green sheet

About the produced green sheet, as shown in Table 2, 10 micrometers pressure loss was measured, and air permeability was determined. In addition, the tensile strength of the sheet was measured to determine the strength. Moreover, the density (rhog) of the sheet was measured and density determination was performed. Moreover, comprehensive determination was performed based on these determination results.

The 10-micrometer pressure loss was evaluated by measuring the decrease in the pressure through the sheet when the air pressure of 42600 Pa was adjusted so that the flow rate was 1 liter / min over 2.5 cm of two sheets of sheets stacked at a thickness of 5 µm. . In air permeability determination, 29000 Pa or more was judged as good ((circle)), and the other thing was judged as bad (x).

The sheet tensile strength was prepared by using an Instron 5543 tensile tester as a sample of a sheet drilled in a dumbbell shape, and each sample was pulled at a speed of 8 mm / min in tensile strength, and the strength at break (MPa). ) Was calculated and the average value was calculated. Since it is preferable that a thick film green sheet is easily cut | disconnected, the tensile strength of the sheet | seat is 6 MPa or less, and it was judged that it passed (degree) good ((circle)), and judged that it was defect (x).

The density (g / cm <3>) of the sheet was computed from the measured value of the mass and volume of a sheet. When the density of the sheet is larger than 3.3 g / cm 3, the adhesiveness of the sheet is lowered, and the lamination as shown in FIG. 3 becomes difficult. Therefore, when the density is lower than 3.3 g / cm 3, it is judged as good (O). And the other thing was judged as defective (x).

In the comprehensive determination, in the results of the filtration characteristics, the coating thickness determination, the breathability determination, the strength determination, and the density determination, it is determined that all are good (○), and one of them is determined that the defect (×) is determined. It was judged that there was something bad (x). These results are shown in Table 2.

Example 1b

31.8 mass% of xylene and toluene were added with respect to the whole solvent, and the poor solvent which consists of MSP + xylene + toluene was made into 40.9 mass% with respect to the whole solvent instead of xylene which is a high boiling point solvent by a part of poor solvent. A ceramic coating material and a green sheet were produced in the same manner as in Example 1a except for the same determinations. The results are shown in Table 1 and Table 2.

Example 1c

45.5 mass% was added to xylene and toluene with respect to the whole solvent instead of xylene which is a high boiling point solvent which is a part of the poor solvent, and the poor solvent which consists of MSP + xylene + toluene was made into 54.5 mass% with respect to the whole solvent. In the same manner as in Example 1a, a ceramic paint and a green sheet were produced, and the same determination was made. The results are shown in Table 1 and Table 2.

Comparative Example 1a

The average particle diameter d50 of BaTiO ₃ as the base material before dispersing in the paint was 0.608 μm, and as a result of mixing by a ball mill, the average particle diameter d50 of BaTiO ₃ was 0.486 μm, and the ratio of d50 after mixing to the mixing was 79.9%. It is implemented except that MSP and xylene are 6.3 mass% and 14.1 mass% respectively with respect to the whole solvent, and the poor solvent which consists of MSP + xylene is 20.3 mass% with respect to the whole solvent on the basis of the crushing conditions used as the following. In the same manner as in Example 1a, a ceramic paint and a green sheet were produced, and the same determination was made. The results are shown in Table 1 and Table 2.

Comparative Example 1b

A ceramic paint and a green sheet were produced in the same manner as in Example 1a, except that xylene was 18.2 mass% with respect to the whole solvent, and the poor solvent composed of MSP + xylene was 27.3 mass% with respect to the whole solvent. The same determination was made. The results are shown in Table 1 and Table 2.

Comparative Example 1c

A ceramic paint and a green sheet were produced in the same manner as in Example 1a, except that xylene was 54.5 mass% with respect to the whole solvent, and the poor solvent composed of MSP + xylene was 63.6 mass% with respect to the whole solvent. The same determination was made. The results are shown in Table 1 and Table 2.

evaluation

As shown in Table 1 and Table 2, the MSP + high boiling point solvent as the poor solvent is contained within the range of 30 to 60 mass% with respect to the whole solvent, so that the comprehensive determination is good, and a thick film green sheet can be formed. I can confirm that there is. Moreover, it was also confirmed that the air permeability, cutting property, and adhesiveness of the green sheet formed using the paint for thick film green sheets of the present Example were improved, and the handling property of the thick film green sheet was improved. Therefore, it can be confirmed that the manufacture of the thick film green sheet becomes easy, and the manufacture of the electronic component manufactured using the thick film green sheet becomes easy.

In addition, as shown in Table 1 and Table 2, it was confirmed that the mineral spirit alone contained more than 7% and less than 15% of the solvent as a whole. It can also be confirmed that when there is too little addition amount of MSP, air permeability tends to deteriorate.

In addition, as shown in Tables 1 and 2, by including the poor solvent as the solvent, up to 80% of the base material (coating / base material in Table 1) can be allowed, and the ceramic powder is dispersed in the coating material. It can be confirmed that the process to make it becomes easy.

As described above, according to the present invention, application of a relatively thick film is possible, and the sheet formed after application is excellent in cutting property (breakable strength), and the sheet has good air permeability, excellent handling properties, and high adhesive strength. The paint for thick film green sheets which can form a sheet, the manufacturing method of paint for thick film green sheets, the manufacturing method of thick film green sheets, the manufacturing method of thick film green sheets, and an electronic component can be provided.

Claims (12)

As a paint for thick film green sheets for obtaining a green sheet having a thickness of 10 µm or more, comprising a ceramic powder, a binder resin containing a butyral resin, and a solvent, The said solvent contains the good solvent which melt | dissolves the said binder resin favorably, and the poor solvent with low solubility with respect to the said binder resin compared with the said good solvent, The said poor solvent is a whole solvent It is contained in the range of 30-60 mass% with respect to , In the poor solvent, mineral spirits are contained within a range of more than 7% by mass and less than 15% by mass with respect to the whole solvent, The paint for thick film green sheet , wherein the good solvent is alcohol, and the poor solvent contains at least xylene in addition to the mineral spirit . The paint for thick film green sheets according to claim 1, wherein the poor solvent contains a solvent having a higher boiling point than the good solvent. delete The method according to claim 1 or 2, wherein the butyral resin is a polyvinyl butyral resin, the polymerization degree of the polyvinyl butyral resin is 1000 or more and 1700 or less, the butyralization degree of the resin is greater than 64% and less than 78%, A paint for thick film green sheets, wherein the amount of residual acetyl groups is less than 6%. The coating material for thick film green sheets of Claim 1 or 2 in which the said binder resin is contained in 4-6.5 mass parts with respect to 100 mass parts of said ceramic powders. As a method of manufacturing the coating material for thick film green sheets of Claim 1 or 2 , The ceramic powder is pulverized so that the average particle diameter of the ceramic powder dispersed in the thick film green sheet paint before the dispersion into the thick film green sheet paint is not less than 80%. The manufacturing method of the paint for thick film green sheets characterized by the above-mentioned. The process of preparing the paint for thick film green sheets of Claim 1 or 2 , The manufacturing method of the thick film green sheet which has a process of shape | molding a thick film green sheet using the said thick film green sheet coating material. The thick film green sheet manufactured using the coating material for thick film green sheets of Claim 1 or 2 . The process of preparing the paint for thick film green sheets of Claim 1 or 2 , Forming an outer green sheet using the thick film green sheet coating material; A process of preparing a paint for a layered green sheet containing a binder resin of the same kind as the binder resin contained in the paint for the thick film green sheet; A step of forming an inner green sheet thinner than the outer green sheet by using the paint for thinning green sheet; Stacking the inner green sheet through an internal electrode layer to obtain a laminate; Stacking the outer green sheet on both end surfaces of the laminate in the stacking direction to obtain a green chip; The manufacturing method of the ceramic electronic component which has a process of baking the said green chip. The manufacturing method of the ceramic electronic component of Claim 9 in which the said thin-layered green sheet paint contains the same kind of ceramic powder as the ceramic powder contained in the said thick film green-sheet paint. The manufacturing method of the ceramic electronic component of Claim 9 whose average particle diameter of the ceramic powder contained in the said thin-layered green sheet paint is smaller than the average particle diameter of the ceramic powder contained in the said thick film green sheet paint. The said average particle diameter of the ceramic powder after disperse | distributing to the said thick film green sheet coating material with respect to the average particle diameter of the ceramic powder before disperse | distributing to the said thick film green sheet coating material is such that it does not become a particle size of less than 80%. Grinding the ceramic powder, The ceramic powder is pulverized so that the average particle diameter of the ceramic powder after being dispersed in the thin green paint is less than 80% of the average particle diameter of the ceramic powder before being dispersed in the thin green sheet paint. The manufacturing method of the ceramic electronic component which has a process to make.

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