JP2020057772A - Step absorption paste, resin fine particles for step absorption paste, and manufacturing method of laminated ceramic capacitor - Google Patents

Abstract

To provide a step absorption paste capable of suppressing generation of cracks and non-lamination, having high pore forming property, and capable of manufacturing a ceramic capacitor having excellent characteristics when used as a step absorption paste of an electrode pattern, and further provide resin fine particles for a step absorption paste which has excellent decomposability at low temperature and is capable of manufacturing a high-strength molded article, and a manufacturing method of a laminated ceramic capacitor.SOLUTION: An electrode step absorption paste of a laminated ceramic capacitor includes inorganic particles, a plasticizer, an organic solvent, a binder resin, and organic particles, and the content of the organic fine particles is 1 to 10 parts by weight with respect to 100 parts by weight of the inorganic fine particles, and a volume average particle diameter rof the inorganic fine particles and a volume average particle diameter rof the organic fine particles satisfy 0.8<r/r<1.5.SELECTED DRAWING: None

Description

INDUSTRIAL APPLICABILITY The present invention can suppress generation of cracks and non-lamination, has high porosity, and can be used to manufacture a ceramic capacitor having excellent characteristics when used in a step absorption paste for an electrode pattern. Related to absorbent paste. The present invention also relates to a resin fine particle for a step absorbing paste which has excellent decomposability at a low temperature and can produce a high-strength molded body, and a method for manufacturing a multilayer ceramic capacitor.

A multilayer electronic component such as a multilayer ceramic capacitor is generally manufactured through the following steps.
First, a plasticizer, a dispersant, and the like are added to a solution in which a binder resin such as a polyvinyl butyral resin or a poly (meth) acrylate resin is dissolved in an organic solvent, and then a ceramic raw material powder is added. After mixing and defoaming, a ceramic slurry having a constant viscosity is obtained. Using a doctor blade, a reverse roll coater, or the like, the obtained ceramic slurry is cast onto a support surface such as a release-treated polyethylene terephthalate film or a SUS plate, and volatile matters such as an organic solvent are distilled off by heating or the like. After that, the ceramic green sheet is obtained by peeling from the support.

Then, a plurality of the ceramic green sheets obtained by applying a conductive paste to be the internal electrodes by screen printing or the like on the obtained ceramic green sheets are alternately stacked, and heated and pressed to produce a laminate. Furthermore, after performing a process of thermally decomposing and removing the binder resin component and the like contained in the laminate, a so-called degreasing process, a process of sintering an external electrode on an end surface of a fired ceramic product obtained by firing is performed. Thus, a multilayer ceramic capacitor is obtained.

In recent years, higher capacitance and smaller size of multilayer ceramic capacitors have been demanded. It is necessary to increase the number of laminated internal electrode layers and dielectric layers in order to satisfy the demand for higher capacitance, and to reduce the thickness of the internal electrode layers and dielectric layers in order to satisfy the demand for miniaturization. It has become.

However, when the number of laminated internal electrode layers and dielectric layers is increased, the difference in thickness between the portion to which the internal electrode is applied and the portion to which the internal electrode is not applied is accumulated. There has been a problem that large distortion occurs in the electrode layer. In addition, since the adhesion between the dielectric layers is reduced in portions where the internal electrodes are not applied, structural problems such as cracks and delaminations have occurred during firing.

In order to solve such a problem, a step-absorbing ceramic paste (hereinafter, also referred to as a step-absorbing paste) for absorbing a step is applied to a portion where the internal electrode is not applied, and has a thickness substantially equal to that of the internal electrode layer. A method of forming a step absorption layer has been attempted.

As such a step absorbing paste, Patent Document 1 discloses that the mass of conductive particles per unit area of an electrode pattern, the average particle diameter of ceramic particles, the thickness of an electrode pattern, the thickness of blank ceramic particles per unit area of a blank pattern. A blank paste in which the mass, the average particle size, and the thickness of the blank pattern have a predetermined relationship is disclosed. Patent Literature 1 describes that use of such a blank paste can suppress cracks and non-lamination after firing.

Patent No. 5423977

However, even when the blank paste described in Patent Document 1 is used for manufacturing a multilayer ceramic capacitor, there is a problem that the effect of suppressing cracks and non-lamination is insufficient. In addition, there is a problem that the hole-forming properties are insufficient and the performance of the multilayer ceramic capacitor is deteriorated.

INDUSTRIAL APPLICABILITY The present invention can suppress generation of cracks and non-lamination, has high porosity, and can be used to manufacture a ceramic capacitor having excellent characteristics when used in a step absorption paste for an electrode pattern. It is intended to provide an absorbent paste. Another object of the present invention is to provide a resin fine particle for a step absorbing paste which has excellent decomposability at low temperature and can produce a molded article having high strength, and a method for producing a multilayer ceramic capacitor.

The present invention is a paste for absorbing an electrode step of a multilayer ceramic capacitor, comprising inorganic fine particles, a plasticizer, an organic solvent, a binder resin, and organic fine particles, wherein the content of the organic fine particles is 100 parts by weight of the inorganic fine particles. 1 part by weight to 10 parts by weight, and the volume average particle diameter r _{1 of the} inorganic fine particles and the volume average particle diameter r _{2 of the} organic fine particles satisfy 0.8 <r ₂ / r ₁ <1.5. It is a step absorption paste.
Hereinafter, the present invention will be described in detail.

The present inventors set the content of the organic fine particles in the electrode step absorption paste containing the inorganic fine particles, the plasticizer, the organic solvent, the binder resin and the organic fine particles in a predetermined range, and the volume of the inorganic fine particles and the organic fine particles. It has been found that the use of particles having an average particle diameter satisfying a predetermined relationship can sufficiently suppress the occurrence of cracks and non-lamination. Particularly, as the resin fine particles for the step absorption paste, a (meth) acrylic resin containing a predetermined amount of a predetermined acrylic component is contained, the volume average particle diameter is within a predetermined range, and the volume average particle diameter and terpineol immersion are included. It has been found that a molded article having excellent low-temperature decomposability and high strength can be produced by using a substance having a predetermined relationship with the volume average particle diameter afterwards. As a result, it has been found that, when used as a step-absorbing paste for a multilayer ceramic capacitor, it is excellent in thermal decomposability, can suppress the occurrence of cracks, and can be excellent in pore-forming properties, and completes the present invention. Reached.

The step absorption paste of the present invention is used for absorbing an electrode step of a multilayer ceramic capacitor, and contains inorganic fine particles, a plasticizer, an organic solvent, a binder resin, and organic fine particles.

Examples of the inorganic fine particles include conductive fine particles, magnetic fine particles, ceramic fine particles, and glass fine particles.

The conductive fine particles are not particularly limited as long as they exhibit sufficient conductivity, and examples thereof include powders of nickel, palladium, platinum, gold, silver, copper, and alloys thereof. These conductive fine particles may be used alone or in combination of two or more.

The magnetic fine particles are not particularly limited, for example, manganese zinc ferrite, nickel zinc ferrite, copper zinc ferrite, barium ferrite, ferrites such as strontium ferrite, metal oxides such as chromium oxide, metal magnetic materials such as cobalt, amorphous Magnetic materials and the like can be mentioned. These magnetic fine particles may be used alone or in combination of two or more.

The ceramic fine particles are not particularly limited, and include, for example, fine particles composed of alumina, zirconia, aluminum silicate, titanium oxide, zinc oxide, barium titanate, magnesia, sialon, spinemullite, silicon carbide, silicon nitride, aluminum nitride, and the like. Is mentioned. These ceramic fine particles may be used alone or in combination of two or more.

The glass fine particles are not particularly limited. For example, lead oxide-boron oxide-silicon oxide-calcium oxide glass, zinc oxide-boron oxide-silicon oxide glass, lead oxide-zinc oxide-boron oxide-silicon oxide glass And the like. These glass particles may be used alone or in combination of two or more. Further, aluminum oxide or the like may be used in combination as long as the object of the present invention is not impaired.

The content of the inorganic fine particles in the step absorption paste of the present invention is preferably 10% by weight, more preferably 30% by weight, more preferably 70% by weight, and more preferably 60% by weight.

The volume average particle diameter _{r 1} of the inorganic fine particles is preferably lower limit 100 nm, the desirable upper limit is 1000 nm.
When the volume average particle diameter is within the above range, the surface of the step absorption layer can be flattened.
The volume average particle size can be measured using, for example, a laser diffraction / scattering type particle size distribution measuring device, a transmission electron microscope, a scanning electron microscope, or the like.

In the inorganic fine particles, a preferable upper limit of the maximum particle diameter r ₁ max is 1500 nm, and a more preferable upper limit is 1200 nm.
The maximum particle diameter r ₁ max can be measured using, for example, a laser diffraction / scattering type particle diameter distribution measuring device, a transmission electron microscope, a scanning electron microscope, or the like.

The inorganic fine particles, the _{r 1} and _r 1 preferred lower limit of the ratio _{(r 1} / r 1 max) with max 0.05, more preferred lower limit is 0.08, a preferred upper limit is 1.0, and a more preferred upper limit is 0.9.

The step absorption paste of the present invention contains a plasticizer.
Examples of the plasticizer include di (butoxyethyl) adipate, dibutoxyethoxyethyl adipate, triethylene glycol bis (2-ethylhexanoate), triethylene glycol dihexanoate, tributyl acetyl citrate, and sebacine. Dibutyl acid and the like.
By using these plasticizers, it is possible to reduce the amount of plasticizer added as compared with the case where a normal plasticizer is used.
Among them, it is preferable to use a non-aromatic plasticizer, and it is more preferable to use a component derived from adipic acid, triethylene glycol or citric acid. Note that a plasticizer having an aromatic ring is not preferable because it easily burns to soot.

As the plasticizer, those having an alkyl group having 4 or more carbon atoms are preferable.
The plasticizer contains an alkyl group having 4 or more carbon atoms, thereby suppressing the absorption of water into the plasticizer and preventing the resulting inorganic fine particle dispersed sheet from causing defects such as voids and blisters. can do. In particular, the alkyl group of the plasticizer is preferably located at a molecular terminal.

The plasticizer preferably has a carbon: oxygen ratio of 5: 1 to 3: 1.
By setting the carbon: oxygen ratio in the above range, the combustibility of the plasticizer can be improved, and generation of residual carbon can be prevented. Further, the compatibility with the (meth) acrylic resin can be improved, and a small amount of a plasticizer can exert a plasticizing effect.

The boiling point of the plasticizer is preferably 240 ° C. or more and less than 390 ° C. By setting the boiling point to 240 ° C. or higher, evaporation in the drying step is facilitated, and it is possible to prevent the residue on the molded body. Further, by setting the temperature to be lower than 390 ° C., generation of residual carbon can be prevented. In addition, the said boiling point means the boiling point at normal pressure.

The content of the plasticizer in the step absorption paste of the present invention is not particularly limited, but a preferable lower limit is 0.1% by weight and a preferable upper limit is 3.0% by weight. When the content is within the above range, the firing residue of the plasticizer can be reduced.

The step absorption paste of the present invention contains an organic solvent.
As the organic solvent, for example, toluene, ethyl acetate, butyl acetate, isopropanol, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether , Diethylene glycol monoisobutyl ether, butyl carbitol, butyl carbitol acetate, terpineol, terpineol acetate, dihydroterpineol, dihydroterpineol acetate, texanol, isophorone, butyl lactate, dioctyl phthalate, dioctyl adipate, benzyl alcohol, phenyl propylene glycol, cresol And the like. Among them, terpineol acetate, dihydroterpineol, dihydroterpineol acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, butyl carbitol, butyl carbitol acetate, and texanol are preferable. Further, terpineol, terpineol acetate, dihydroterpineol, and dihydroterpineol acetate are more preferable. These organic solvents may be used alone or in combination of two or more.

The organic solvent preferably has a boiling point of 90 to 260 ° C. When the boiling point is 90 ° C. or higher, the evaporation does not become too fast and the handleability is excellent. By setting the boiling point to 260 ° C. or lower, the strength of the inorganic fine particle dispersed sheet can be improved.

The content of the organic solvent in the step absorption paste of the present invention is not particularly limited, but a preferable lower limit is 10% by weight and a preferable upper limit is 60% by weight. When the content is in the above range, coatability and dispersibility of the inorganic fine particles can be improved.

The resin fine particles for a step absorption paste of the present invention contains a binder resin.
As the binder resin, for example, polyvinyl butyral, polyvinyl acetal resin such as polyvinyl acetoacetal, polyvinyl alcohol resin such as polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, Cellulosic resins such as carboxyethylcellulose, carboxyethylmethylcellulose and cellulose acetate phthalate; (meth) acrylic resins such as (meth) acrylic acid esters; imide resins such as polyamide imide and polyimide; ethylene resins such as polyethylene oxide; Nitrile resins such as polyacrylonitrile and polymethacrylonitrile; Urethane resins such as urethane, polyethylene, polypropylene, polyvinylidene fluoride, polyvinylidene chloride polyvinyl fluoride, vinyl resins such as vinyl acetate, include those containing rubber resin such as styrene-butadiene rubber.
Among them, polyvinyl acetal resin, (meth) acrylic resin, and cellulose resin are preferable.

The polyvinyl acetal resin preferably has at least structural units represented by the following general formulas (1), (2) and (3).

In the formula, R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

In the polyvinyl acetal resin, a preferable lower limit of the content of the vinyl alcohol unit represented by the general formula (1) (hereinafter, also referred to as a hydroxyl group amount) is 17 mol%, and a preferable upper limit is 40 mol%.

In the polyvinyl acetal resin, a preferred lower limit of the content of the acetal unit represented by the general formula (2) (hereinafter, also referred to as an acetal group amount) is 35 mol%, and a preferred upper limit is 80 mol%. If the content of the acetal unit represented by the above general formula (2) is less than 35 mol%, it may become insoluble in the organic solvent used at the time of dissolution, and if it exceeds 80 mol%, the amount of residual hydroxyl groups decreases. The strength of the obtained polyvinyl acetal resin may decrease.
In the present specification, the method for calculating the amount of acetal groups is a method of counting the two acetalized hydroxyl groups since the acetal groups of the polyvinyl acetal resin are obtained by acetalizing two hydroxyl groups. Is used to calculate the mol% of the acetal group amount.

The polyvinyl acetal resin preferably has a ratio (butyral group / acetoacetal group) of a portion acetalized with butyraldehyde to a portion acetalized with acetaldehyde of 0/10 to 8/2. Thereby, the stability of the viscosity of the step absorption paste is improved.

In the polyvinyl acetal resin, a preferable lower limit of the content of the acetyl unit represented by the general formula (3) (hereinafter, also referred to as an acetyl group amount) is 0.1 mol%, and a preferable upper limit is 25 mol%. If it exceeds the above range, the solubility of the raw material polyvinyl alcohol decreases, and the acetalization reaction becomes difficult.

In the polyvinyl acetal resin, a preferable lower limit of the degree of polymerization is 300, and a preferable upper limit is 4000. By setting the degree of polymerization within the above range, the strength of the multilayer ceramic capacitor can be sufficiently improved.

The method of acetalization is not particularly limited, and a conventionally known method can be used. For example, an aqueous solution of polyvinyl alcohol, an alcohol solution, a mixed solution of water / alcohol, and a dimethyl sulfoxide (DMSO) solution in the presence of an acid catalyst And a method of adding various aldehydes therein.

The aldehyde used for the acetalization is not particularly limited, for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, amylaldehyde, hexylaldehyde, heptylaldehyde, 2-ethylhexylaldehyde, cyclohexylaldehyde, furfural, glyoxal, glutaraldehyde, benzaldehyde , 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, β-phenylpropionaldehyde and the like. Above all, it is preferable to use acetaldehyde and butyraldehyde alone, or to use acetaldehyde and butyraldehyde together.

The acid catalyst is not particularly limited, and any of an organic acid and an inorganic acid can be used, and examples thereof include acetic acid, paratoluenesulfonic acid, nitric acid, sulfuric acid, and hydrochloric acid.

In order to stop the acetalization reaction, it is preferable to perform neutralization with an alkali. The alkali is not particularly limited, and includes, for example, sodium hydroxide, potassium hydroxide, ammonia, sodium acetate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and the like.
Before and after the neutralization step, it is preferable to wash the obtained polyvinyl acetal resin using water or the like. In addition, it is more preferable to perform the cleaning with pure water in order to prevent impurities contained in the cleaning water from being mixed.

The step absorption paste of the present invention contains organic fine particles.
The organic fine particles, the lower limit of the volume average particle diameter _{r 2} is 100 nm, the upper limit is 1000 nm.
Be achieved in that a good pore properties of the volume average particle diameter r ₂ is equal to or greater than 100 nm, it is possible to improve the strength of the step absorption layer by a 1000nm or less.
The volume average particle diameter _{r 2} is preferably the lower limit is 150 nm, more preferred lower limit is 200 nm, a preferred upper limit is 900 nm, a more preferred upper limit is 800 nm.
The volume average particle size can be measured using, for example, a laser diffraction / scattering type particle size distribution analyzer, a transmission electron microscope, a scanning electron microscope, or the like.

In the organic fine particles, a preferable upper limit of the maximum particle diameter r ₂ max is 1500 nm, and a more preferable upper limit is 1200 nm.
The maximum particle size r ₂ max can be measured using, for example, a laser diffraction / scattering type particle size distribution measuring device, a transmission electron microscope, a scanning electron microscope, or the like.

In the organic fine particles, a preferable lower limit of the ratio of r ₂ to r ₂ max (r ₂ / r ₂ max) is 0.05, a more preferable lower limit is 0.08, a preferable upper limit is 1.0, and a more preferable upper limit is. 0.9.

In step absorption pastes of the present invention satisfy the relationship of the inorganic volume average particle diameter r1 and _0.8 volume average particle diameter _{r 2} of the organic fine particles of fine particles _{<r 2 / r 1 <1.5} .
By satisfying the above relationship, the surface of the step absorption layer can be smoothed, and the adhesion when the ceramic green sheets are laminated can be improved.
The _r 2 / _{r 1} is more preferred lower limit is 0.9, and a more preferred upper limit thereto is 1.3.

In step absorption pastes of the present invention, the ratio of the maximum particle size _r 1 max and the volume average particle diameter _r 2 max of the organic fine particles of the inorganic fine particles _{(r 2 max / r 1 max} ) is preferably the lower limit is 0.8 The more preferred lower limit is 0.9, the preferred upper limit is 1.5, and the more preferred lower limit is 1.3.

The preferable upper limit of the 10% by weight reduction temperature when the organic fine particles are heated at a temperature rising rate of 5 ° C./min is 230 ° C.
When the above-mentioned 10% by weight reduction temperature is 230 ° C. or less, the firing time for producing a multilayer ceramic capacitor can be shortened.
The lower limit of the 10% by weight temperature is preferably 180 ° C, more preferably 190 ° C, and more preferably 220 ° C.
The 10% by weight reduction temperature can be measured, for example, using a differential thermogravimeter.

When the organic fine particles are heated at a heating rate of 5 ° C./min, the preferred lower limit of the 50% by weight reduction temperature is 190 ° C., the more preferred lower limit is 200 ° C., the preferred upper limit is 300 ° C., and the more preferred upper limit is 280 ° C. It is.
The 50% by weight reduction temperature can be measured, for example, using a differential thermogravimetric device.

The preferable upper limit of the temperature at which the organic fine particles are reduced by 90% by weight when heated at a heating rate of 5 ° C./min is 350 ° C.
When the 90% by weight reduction temperature is 350 ° C. or less, the firing time for producing a multilayer ceramic capacitor can be reduced.
The lower limit of the 90% by weight temperature is preferably 280 ° C, more preferably 300 ° C, and more preferably 340 ° C.
The 90% by weight reduction temperature can be measured, for example, using a differential thermogravimetric device.

The organic fine particles preferably have a heating residue amount of 0.3% by weight or less when heated to 500 ° C. at a temperature rising rate of 5 ° C./min.
When the amount of the heating residue is 0.3% by weight or less, lattice defects do not occur, and a reduction in the useful life of the multilayer ceramic capacitor can be prevented.
A more preferable upper limit of the amount of the heated residue is 0.1% by weight.
The heating residue amount can be calculated from [(weight after heating−weight before heating) / weight before heating] × 100, and can be measured using, for example, a differential thermogravimeter.

The organic fine particles preferably have a weight loss rate of 95% by weight or more when heated at 300 ° C. for 1 hour. When the weight reduction rate at the time of heating at 300 ° C. for 1 hour is 95% by weight or more, extremely high thermal decomposability is achieved, so that pores can be formed before the binder resin is decomposed. Further, the shape of the pores can be maintained without breaking even after the completion of the firing.
A more preferred lower limit is 96% by weight. The preferred upper limit of the weight loss rate when heated at 300 ° C. for one hour is not particularly limited, but is 100% by weight.
The weight loss rate can be calculated from [(weight before heating−weight after heating) / weight before heating] × 100.
The rate of weight loss when heated at 300 ° C. for one hour can be measured using, for example, a differential thermogravimeter.

The organic fine particles preferably have a weight reduction ratio of 98% by weight or more when heated at 350 ° C. for 1 hour. Since the weight reduction rate when heated at 350 ° C. for 1 hour is 98% by weight or more, the composition has extremely high thermal decomposability, so that pores can be formed before the binder resin is decomposed. Further, the shape of the pores can be maintained without breaking even after the completion of the firing. A more preferred lower limit is 99% by weight. The preferred upper limit of the weight loss rate when heated at 350 ° C. for one hour is not particularly limited, but is 100% by weight.
The weight loss rate can be calculated from [(weight before heating−weight after heating) / weight before heating] × 100.
The rate of weight loss when heated at 350 ° C. for one hour can be measured using, for example, a differential thermogravimeter.

The organic fine particles preferably contain a (meth) acrylic resin.
The (meth) acrylic resin contains a segment (component) derived from a polyfunctional (meth) acrylate.
Thereby, a crosslinked structure is formed in the fine particles, and the strength of the molded body can be improved.

The polyfunctional (meth) acrylate means a difunctional or higher (meth) acrylate, for example, a polyfunctional (meth) acrylate having a polyoxyalkylene unit, or a polyhydric alcohol (meth) acryl. Acid esters and the like.
Among them, a polyfunctional (meth) acrylate having a polyoxyalkylene unit is preferable because the low-temperature decomposability can be improved.
In the polyfunctional (meth) acrylic acid ester, the preferred lower limit of the number of carbon atoms in the ester moiety is 2, more preferred lower limit is 3, further preferred lower limit is 6, preferred upper limit is 50, more preferred upper limit is 40, and further preferred upper limit is. 30. In addition, the carbon number of the said ester site | part means the carbon number other than the carbon which comprises a (meth) acryloyl group in a (meth) acrylic acid ester.

The polyfunctional (meth) acrylate having a polyoxyalkylene unit has two or more oxyalkylene units in its molecular structure.
As for the carbon number of the oxyalkylene unit, a preferred lower limit is 1, a more preferred lower limit is 2, a preferred upper limit is 4, and a more preferred upper limit is 3.
Examples of the oxyalkylene unit include an oxyethylene unit, an oxypropylene unit, and an oxybutylene unit. Among them, those having an oxypropylene unit are preferred.

The number of oxyalkylene units contained in the molecular structure of the polyfunctional (meth) acrylate having a polyoxyalkylene unit is preferably 2 as a lower limit, 3 as a lower limit, 14 as an upper limit, and 7 as an upper limit. It is.

The polyfunctional (meth) acrylate having a polyoxyalkylene unit is not particularly limited as long as it is bifunctional or higher (meth) acrylate, and is bifunctional (meth) acrylate, trifunctional (meth) acrylate, and tetrafunctional (meth) acrylate. ) Acrylate and the like can be used. Especially, a bifunctional (meth) acrylate is preferable.

Specific examples of the polyfunctional (meth) acrylate having a polyoxyalkylene unit include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and dipropylene glycol diacrylate. 2 such as (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, di (meth) acrylate of ethylene oxide adduct of bisphenol, and di (meth) acrylate of propylene oxide adduct of bisphenol; And functional (meth) acrylates. In addition, trifunctional (e.g., ethylene oxide-modified glycerol tri (meth) acrylate, propylene oxide-modified glycerol tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, and propylene oxide-modified trimethylolpropane tri (meth) acrylate) (Meth) acrylate and the like. Of these, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate are preferred because the calorific value during thermal decomposition under a nitrogen atmosphere can be further reduced.

Examples of the (meth) acrylic acid ester of the polyhydric alcohol include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth). Acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, glycerin di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol diacrylate monostearate, etc. (Meth) acrylate. Further, trifunctional (meth) acrylates such as pentaerythritol tri (meth) acrylate and trimethylolpropane tri (meth) acrylate may be used. Further, pentafunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate and ditrimethylolpropanetetra (meth) acrylate, and pentafunctional (meth) acrylates such as dipentaerythritol hydroxypenta (meth) acrylate and dipentaerythritol hexaacrylate And the like.
Of these, bifunctional (meth) acrylates and trifunctional (meth) acrylates are preferred, and tripropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, and trimethylolpropane triacrylate are more preferred.

The preferred lower limit of the content of the segment derived from the polyfunctional (meth) acrylate in the (meth) acrylic resin is 20% by weight, and the preferred upper limit is 80% by weight. When the content is 20% by weight or more, the solvent resistance becomes good, and when the content is 80% by weight or less, preferable sinterability can be maintained. A more preferred lower limit is 25% by weight and a more preferred upper limit is 70% by weight.

It is preferable that the (meth) acrylic resin further contains a segment derived from a monofunctional (meth) acrylate.
Examples of the monofunctional (meth) acrylate include hydroxyalkyl (meth) acrylate, alkyl (meth) acrylate, polyalkylene glycol mono (meth) acrylate, mono (meth) acrylate having an alicyclic skeleton, and aromatic Mono (meth) acrylate having a ring skeleton, mono (meth) acrylate having a heterocyclic skeleton, and the like can be given.
Examples of the hydroxyalkyl (meth) acrylate include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
The alkyl (meth) acrylate may have a branched alkyl group or may have a linear alkyl group. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, ethylhexyl (meth) acrylate and the like can be mentioned.
Examples of the polyalkylene glycol mono (meth) acrylate include polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate.
Examples of the mono (meth) acrylate having an alicyclic skeleton include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and the like. .
Examples of the mono (meth) acrylate having an aromatic ring skeleton include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and ethoxylated o-phenylphenol acrylate.
Mono (meth) acrylate acryloylmorpholine having the above heterocyclic skeleton, 2-hydroxyethylacrylamide, N-methylol (meth) acrylamide, N-vinylpyrrolidone, dimethylacrylamide, diethylacrylamide, tetrahydrofurfuryl (meth) acrylate, 2- Acryloyloxyethyl acid phosphate and the like can be mentioned.
The monofunctional (meth) acrylic acid ester preferably has 1 to 18 carbon atoms at the ester site, more preferably 1 to 4 carbon atoms. In addition, the carbon number of the said ester site | part means the carbon number other than the carbon which comprises a (meth) acryloyl group in a (meth) acrylic acid ester.
Among them, alkyl (meth) acrylate is preferable, alkyl (meth) acrylate having 1 to 18 carbon atoms is more preferable, alkyl (meth) acrylate having 1 to 4 carbon atoms is further preferable, and methyl methacrylate, ethyl methacrylate, and butyl methacrylate are used. And isobutyl methacrylate are particularly preferred.
The (meth) acrylic resin may contain a segment derived from the monofunctional (meth) acrylate, and may have only a segment derived from one type of monofunctional (meth) acrylate. It may have a segment derived from two or more monofunctional (meth) acrylates.

When the (meth) acrylic resin contains a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate, the number of carbon atoms in the ester portion of the monofunctional (meth) acrylate and The lower limit of the ratio of the number of carbon atoms in the functional (meth) acrylate to the number of carbon atoms in the ester portion is preferably 0.1, more preferably 0.11, more preferably 5, more preferably 3, and further preferably 0. .8.

When the polyfunctional (meth) acrylate contains a polyfunctional (meth) acrylate having a polyoxyalkylene unit, the number of carbon atoms in the ester portion of the monofunctional (meth) acrylate and The lower limit of the ratio of the number of carbon atoms of the oxyalkylene unit of the functional (meth) acrylate to the preferred lower limit is 0.1, the more preferred lower limit is 0.3, the preferred upper limit is 5, the more preferred upper limit is 3, and the more preferred upper limit is 3. 1.5.

The content of the segment derived from the monofunctional (meth) acrylic acid in the (meth) acrylic resin is preferably 20% by weight, more preferably 30% by weight, more preferably 80% by weight, and more preferably the upper limit. 75% by weight.

The organic fine particles, and the volume average particle diameter _{r 3} after immersion for 24 hours in the volume average particle diameter _{r 2} and terpineol preferably satisfies _{0.8 <r 3 / r 2 <} 1.2.
By satisfying the above relationship, good pore-forming properties can be exhibited without being eluted in the organic solvent.
As for r ₃ / r ₂ , a preferred lower limit is 0.8, a more preferred lower limit is 0.9, a preferred upper limit is 1.2, and a more preferred upper limit is 1.1.
The volume average particle diameter after immersion in terpineol for 24 hours was measured by immersing in terpineol for 24 hours, and then using a laser diffraction / scattering type particle size distribution measuring apparatus for the precipitate obtained using a centrifuge. It can be measured by using a transmission electron microscope, a scanning electron microscope, or the like.

The organic fine particles are, for example, other components such as a polyfunctional (meth) acrylate and a monofunctional (meth) acrylate added as needed, a dispersant, a surfactant, and a polymerization initiator. Can be produced by polymerizing a monomer composition containing
The monomer composition preferably contains 20 to 80% by weight of a polyfunctional (meth) acrylate and 20 to 80% by weight of a monofunctional (meth) acrylate.

Examples of the dispersant include a polyvinyl alcohol-based dispersant.
In addition, examples of the surfactant include an anionic surfactant and a nonionic surfactant.

Examples of the polyvinyl alcohol-based dispersant include polyvinyl alcohol, partially saponified polyvinyl alcohol, and the like.
The polyvinyl alcohol is preferably a polyvinyl alcohol having a degree of polymerization of 300 to 3000 and a degree of saponification of 70 to 99 mol%.
When the polymerization degree is in the above range, the dispersant can be efficiently removed when washing the resin fine particles. The said polymerization degree has a more preferable lower limit of 500, and a more preferable upper limit is 2,600.
When the saponification degree is 70 to 99 mol%, the volume average particle diameter of the acrylic resin fine particles can be set in a suitable range. As for the said saponification degree, a more preferable lower limit is 73 mol% and a more preferable upper limit is 98 mol%.

The anionic surfactant preferably has a polyoxyalkylene skeleton and the counter ion is an ammonium ion.
Examples of the polyoxyalkylene skeleton include a polyoxyethylene skeleton, a polyoxypropylene skeleton, and a polyoxybutylene skeleton.
Examples of the ammonium salt include ammonium polyoxyethylene alkyl ether sulfate, polyoxyethylene styrenated phenyl ether ammonium sulfate, ammonium salt of perfluorooctanoic acid, and ammonium salt of perfluorooctanesulfonic acid. Examples of the ammonium polyoxyethylene alkyl ether sulfate include polyoxyethylene lauryl ether ammonium sulfate and polyoxyethylene oleyl cetyl ether ammonium sulfate.
In addition, among the anionics, those whose counter ion is an alkali metal ion are not desirable. If the counter ion is an alkali metal ion, the sintering residue of the acrylic resin fine particles increases. By using an ion whose counter ion is ammonium ion, the sintering residue of the resin fine particles for the step absorption paste can be reduced.

The nonionic surfactant preferably has a polyoxyalkylene skeleton. Further, the nonionic surfactant preferably has an HLB of 10 to 20.
Examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oxypropylene block polymer, polyethylene glycol fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Examples of the polyoxyalkylene alkyl ether include polyoxyethylene alkyl ether and polyoxyalkylene branched decyl ether.

The preferable lower limit of the content of the dispersant and the surfactant in the monomer composition is 0.1% by weight, and the preferable upper limit is 10% by weight.
When the content of the dispersant and the surfactant is 0.1% by weight or more, coalescence of the fine particles can be suppressed, and the volume average particle diameter can be adjusted to an appropriate range. When the content of the dispersant and the surfactant is 10% by weight or less, an increase in the amount of heat generated when the obtained fine resin particles for a step absorption paste is thermally decomposed can be suppressed.

As the polymerization initiator, for example, organic peroxides such as dialkyl peroxide, diacyl peroxide, ammonium peroxide, peroxyester, and peroxydicarbonate, and azo compounds are preferably used.
Examples of the dialkyl peroxide include methyl ethyl peroxide, di-t-butyl peroxide, dicumyl peroxide and the like.
Examples of the diacyl peroxide include isobutyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and the like.
Examples of the above peroxyester include t-butyl peroxypivalate, t-hexylperoxypivalate, t-butylperoxyneodecanoate, t-hexylperoxyneodecanoate, 1-cyclohexyl-1 -Methylethyl peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, cumyl peroxy neodecanoate [α-cumyl peroxy neodecanoate, etc.], (α , Α-bis-neodecanoylperoxy) diisopropylbenzene and the like.
Examples of the peroxydicarbonate include di-2-butylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-n-propyl-oxydicarbonate, diisopropylperoxydicarbonate, Examples thereof include di (2-ethylethylperoxy) dicarbonate, dimethoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutylperoxy) dicarbonate, and di-s-butylperoxydicarbonate.
Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), and 2,2′-azobis (2,4 -Dimethylvaleronitrile), 1,1'-azobis (1-cyclohexanecarbonitrile) and the like.
Since these organic peroxides and azo compounds are compatible with the above-mentioned monomers, they can be preferably used for suspension polymerization.
On the other hand, it is desirable to use a water-soluble polymerization initiator for emulsion polymerization.
Examples of the water-soluble polymerization initiator include, for example, an acid mixture of an imidazole-based azo compound, a water-soluble azo compound, oxo acids such as potassium persulfate, ammonium persulfate, and sodium persulfate; hydrogen peroxide; peracetic acid; And peroxides such as propionic acid.
Examples of the acid mixture of the imidazole-based azo compound include, for example, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride and 2,2′-azobis [2- (2-imidazoline- 2-yl) propane] sulfatohydrate, 2,2′-azobis (2-methylpropionamidine) dihydrochloride and the like.
Examples of the water-soluble azo compound include 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate and 2,2′-azobis [2- (2-imidazoline-). 2-yl) propane], 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 4,4'-azobis-4-cyanovaleric acid, and the like.
Among them, potassium persulfate, ammonium persulfate, and the like can be preferably used because of low residue.
These polymerization initiators may be used alone or in combination of two or more.

A preferred lower limit of the content of the polymerization initiator in the monomer composition is 0.1% by weight, and a preferred upper limit is 3% by weight.
By setting the content of the polymerization initiator in the above range, the polymerization reaction can be sufficiently advanced.

The method for producing the organic fine particles (polymerization method) is not particularly limited, and examples thereof include a suspension polymerization method and an emulsion polymerization method.

In the polymerization method, a monomer composition containing the polyfunctional (meth) acrylate, a dispersant, and a polymerization initiator is emulsified and dispersed.
Examples of the emulsification and dispersion method include a method of stirring with a high-speed rotary mixer (high-speed rotary emulsifier), a method of stirring with a colloid mill-type device, a method of pulverizing with a high-pressure emulsifier, and polishing with a roll mill-type emulsifier. Examples of the method include a crushing method and a mesh crushing method. Among them, a high-speed rotation type emulsifying apparatus such as a homomixer type, a comb tooth type, and an intermittent jet water flow generating type can be preferably used. Further, an ultrasonic homomixer may be used as the homomixer.

When a suspension polymerization method is used as the above polymerization method, a monomer composition containing the above polyfunctional (meth) acrylate, a dispersant, and a polymerization initiator is prepared, and then poured into water, and the monomer liquid is dropped by a high-speed stirring device. And uniformly dispersed in water.
Further, ultrasonic treatment may be combined with these high-speed stirring devices. By using these powerful emulsifying mixers, the amount of the dispersant added can be reduced. Furthermore, the temperature of the mixture in which the emulsion micelles are uniformly dispersed in water is increased while stirring with a polymerization device equipped with a temperature controller and a stirrer, and the predetermined temperature is maintained for several hours to complete the polymerization of the monomer composition in the emulsion micelles. As a result, fine particles are formed. By drying the obtained fine particle slurry, resin fine particles for a step absorption paste of the present invention can be obtained.
In addition, even when the particle size of the emulsion micelle is small, if the polymerization conditions are not favorable, the particles coalesce and the desired volume average particle size cannot be obtained.

When producing the organic fine particles, the polymerization temperature is preferably set to 50 to 80 ° C. By setting the polymerization temperature to 50 ° C. or higher, the reaction can be appropriately started by the polymerization initiator. By setting the temperature to 80 ° C. or lower, the particles are united during the polymerization, and the volume average particle diameter of the obtained fine particles is reduced. Unnecessarily large size can be prevented.
The drying step is not particularly limited. A method in which a fine particle slurry is applied to equipment and dried in a blowing oven, a method in which the slurry is sprayed in a blowing furnace, and a freeze-drying method can also be preferably used.

(Meth) containing acrylic resin, the (meth) acrylic resin and the polyfunctional (meth) segment derived from an acrylic acid ester (component) containing 20 to 80 wt%, the volume average particle diameter _{r 2} 100 to 1000 nm Wherein the volume average particle diameter r ₂ and the volume average particle diameter r ₃ after immersion in terpineol for 24 hours satisfy 0.8 <r ₃ / r ₂ <1.2. It is one of.

The step absorption paste of the present invention may contain an additive such as a surfactant.
The surfactant is not particularly limited, and examples thereof include a cationic surfactant, an anionic surfactant, and a nonionic surfactant.
The nonionic surfactant is not particularly limited, but is preferably a nonionic surfactant having an HLB value of 10 or more and 20 or less. Here, the HLB value is used as an index indicating the hydrophilicity and lipophilicity of a surfactant, and several calculation methods have been proposed. For example, for an ester-based surfactant, a saponification value is used. Is defined as S, the acid value of the fatty acid constituting the surfactant is defined as A, and the HLB value is defined as 20 (1-S / A). Specifically, a nonionic surfactant having polyethylene oxide in which an alkylene ether is added to a fatty chain is preferable, and specifically, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, and the like are suitably used. Can be The nonionic surfactant has good thermal decomposability, but if added in a large amount, the thermal decomposability of the step absorption paste may be reduced. Therefore, a preferable upper limit of the content is 5% by weight.

The viscosity of the step-absorbing paste of the present invention is not particularly limited, but the preferable lower limit of the viscosity is 0.1 Pa · s, and the preferable upper limit is 20 Pa when measured using a B-type viscometer at 20 rpm at a probe rotation speed of 5 rpm. 100 Pa · s.
By setting the viscosity to 0.1 Pa · s or more, it is possible to maintain a predetermined shape of the obtained step absorption paste after coating by a die coat printing method or the like. In addition, by setting the viscosity to 100 Pa · s or less, it is possible to prevent defects such as the disappearance of the coating mark of the die from occurring, and to achieve excellent printability.

The method for producing the step absorption paste of the present invention is not particularly limited, and includes a conventionally known stirring method. Specifically, for example, inorganic fine particles, a plasticizer, an organic solvent, a binder resin, organic fine particles and if necessary And a method of stirring other components to be added by a three-roll or the like.

The step absorption paste of the present invention can be suitably used, for example, for absorbing a step of an electrode pattern when manufacturing a multilayer ceramic capacitor.
As a method of manufacturing the laminated ceramic capacitor, for example, a plurality of conductive paste and the step absorption paste of the present invention coated on a ceramic green sheet are stacked, and after heating and pressing to obtain a laminate, There is a method of performing a degreasing treatment and then firing.
A method for producing a laminated ceramic capacitor, wherein a laminate obtained by alternately laminating a ceramic green sheet and a conductive paste and a step absorption paste is degreased and fired, wherein a step of producing a ceramic green sheet; A method for producing a multilayer ceramic capacitor, comprising: a step of applying a conductive paste to a green sheet; and a step of applying the step absorption paste of the present invention to a region of the ceramic green sheet where the conductive paste is not applied. Also, this is one of the present invention.

ADVANTAGE OF THE INVENTION According to this invention, generation | occurrence | production of a crack and non-lamination can be suppressed, and it is possible to manufacture a ceramic capacitor having high porosity and excellent characteristics when used for a step absorption paste of an electrode pattern. It is possible to provide a smooth step absorption paste. Further, it is possible to provide a resin fine particle for a step absorbing paste, which has excellent decomposability at low temperature and can produce a high-strength molded body, and a method for producing a multilayer ceramic capacitor.

Hereinafter, embodiments of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples.

(Production Examples 1 to 14)
(Preparation of organic fine particles)
A 1 L separable flask equipped with a stirrer, a thermometer, a nitrogen sealed tube, and a reflux condenser was prepared. After adding 1080 parts by weight of pure water to the flask, predetermined monomers, a polymerization initiator and a dispersant were added as shown in Table 1.

In addition, the following were used as a monomer, a polymerization initiator, and a dispersant.
(monomer)
MMA: Methyl methacrylate, manufactured by Mitsubishi Chemical Corporation, Acryester M
nBMA: n-butyl methacrylate, manufactured by Mitsubishi Chemical Corporation, Acryester B
iBMA: isobutyl methacrylate, manufactured by Mitsubishi Chemical Corporation, Acryester IB
3PG: tripropylene glycol dimethacrylate 9PG: polypropylene glycol dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester 9PG
TMP-T: trimethylolpropane trimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester TMPT
(Polymerization initiator)
Kayaester P-70: tert-butyl peroxypivalate, APS manufactured by Kayaku Nuurion, Inc .: Ammonium persulfate, manufactured by Hishie Chemical Co. (dispersant)
GM-14: partially saponified polyvinyl alcohol, manufactured by Mitsubishi Chemical Corporation, Gohsenol GM-14, degree of polymerization 1400, degree of saponification 87.8 mol%
S-20F: Sodium alkylbenzene sulfonate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen S-20F

Next, using a homomixer, the mixture was mixed at a rotation speed shown in Table 1 for 3 minutes, transferred to a reaction vessel equipped with a stirrer and a jacket, and supplied with a nitrogen gas while stirring at 150 rpm to 70 ° C. under a nitrogen atmosphere. And a polymerization reaction was carried out for about 4 hours to obtain a slurry of polymer particles containing a (meth) acrylate resin. The obtained slurry of polymer particles was spray-dried and pulverized to obtain organic fine particles.

(Examples 1 to 9, Comparative Examples 1 to 7)
(Preparation of step absorption paste)
The binder resin, the organic solvent, and the plasticizer were mixed as shown in Table 2 and stirred to obtain a mixed solution. To the obtained mixed solution, 100 parts by weight of barium titanate having a volume average particle diameter shown in Table 2 and the organic fine particles obtained in the production example shown in Table 2 were added, and mixed by a ball mill for 48 hours to absorb a step difference. A paste was obtained.
As the binder resin, a polyvinyl acetal resin (BM-2, manufactured by Sekisui Chemical Co., Ltd., polymerization degree: 830, hydroxyl group amount: 31 mol%, acetyl group amount: 1 mol%) was used.

(Preparation of ceramic green sheet)
To 20 parts by weight of a polyvinyl acetal resin (manufactured by Sekisui Chemical Co., Ltd., BM-2, degree of polymerization: 830, amount of hydroxyl group: 22% by weight, amount of acetyl group: 3% by weight), add and melt 210 parts by weight of methyl ethyl ketone as an organic solvent. 3 parts by weight of triethyl glycol bis (2-ethylhexanoate) as a plasticizer was added to the resulting resin solution and dissolved by stirring. To the obtained resin composition, 100 parts by weight of barium titanate (volume average particle diameter: 680 nm) as inorganic fine particles was added and mixed by a ball mill for 48 hours to obtain a ceramic slurry composition.
The obtained ceramic slurry composition is applied onto a release-treated polyester film so that the thickness after drying becomes 1 μm, air-dried at room temperature for 1 hour, and further dried at 120 ° C. for 2 hours to obtain a ceramic green. I got a sheet.

(Preparation of conductive paste)
Ethyl cellulose (Ethocel STD100, manufactured by Dow Chemical Company) was dissolved in α-terpineol so that the resin solid content was 12% by weight. The obtained ethyl cellulose solution and nickel powder (NFP201, manufactured by JFE Mineral Co., Ltd.) were mixed and passed through a three-roll mill several times to obtain a conductive paste. The composition was adjusted so that nickel powder was 50% by weight and ethyl cellulose was 6% by weight in the obtained conductive paste.

(Production of multilayer ceramic capacitor)
On one surface of the obtained ceramic green sheet, a conductive paste was applied by screen printing so that the thickness after drying became 1.5 μm, and dried to form a conductive layer. A step absorbing paste was applied by screen printing to a portion of the ceramic green sheet where the conductive layer was not formed so that the thickness after drying became 1.5 μm, and dried to form a step absorbing layer. The ceramic green sheet on which the conductive layer and the step absorption layer were formed was cut into 5 cm squares, 100 sheets were stacked, and heated and pressed at a temperature of 70 ° C. and a pressure of 150 kg / cm 2 for 10 minutes to obtain a laminate. The obtained laminate was heated to 400 ° C. at a temperature rising rate of 3 ° C./min under a nitrogen atmosphere, kept for 5 hours, and then heated to 1350 ° C. at a temperature rising rate of 5 ° C./min. By holding for 10 hours, a multilayer ceramic capacitor was obtained.

(Evaluation method)
The organic fine particles, the step absorption paste and the multilayer ceramic capacitor obtained above were evaluated by the following methods. The results are shown in Tables 1 and 2. In Production Example 12, evaluation was not possible because coalescence of particles occurred during the course of polymerization and a lump was obtained.

(Average particle measurement r ₂ , maximum particle size r ₂ max and r ₂ / r ₂ max)
The slurry of the obtained organic fine particles is diluted and supplied to a laser diffraction / scattering type particle size distribution measuring device (LA-950, manufactured by Horiba, Ltd.) to supply a volume average particle size (r ₂ ) and a maximum particle size (r _2). max) was measured. In _addition, to calculate the r _{2 /} r ₂ max.

(Volume average particle diameter r ₃ after immersion in terpineol)
1 g of the obtained organic fine particles were added to a test tube, 30 g of terpineol was further added, and the mixture was dispersed with a vortex for 10 minutes, and then allowed to stand for 24 hours. Furthermore, after centrifuging at 3000 rpm for 30 minutes with a tabletop centrifuge (Tabletop centrifuge 2420, manufactured by Kubota Corporation), the supernatant was removed to obtain a precipitate. Methanol was added to the obtained precipitate, dispersed by vortex for 5 minutes, and further centrifuged by a tabletop centrifuge to remove the supernatant. After repeating the same operation twice, the obtained precipitate was dried at 70 ° C. for 24 hours to obtain a sample. The volume average particle diameter of the obtained sample was measured using a scanning electron microscope. The fine particles obtained in Production Example 11 swelled to the extent that the particle shape collapsed and particles could not be obtained after drying, so that the volume average particle diameter after immersion could not be measured. Was.

(Thermogravimetric analysis)
The obtained organic fine particles were heated to 500 ° C. while heating at a rate of 5 ° C./min in an air atmosphere using a simultaneous thermogravimetric differential analyzer (TG / DTA6200, manufactured by Seiko Instruments Inc.). Then, the decomposition start temperature, the 10% by weight reduction temperature, and the 90% by weight weight reduction temperature were measured.

(Amount of heating residue)
With respect to the obtained organic fine particles, the weight of the sample before and after heating measured by thermogravimetric analysis was measured, and the heating residue amount was calculated by the following equation.
Heated residue amount (% by weight) = (sample weight after heating / sample weight before heating) × 100

(With or without cracks)
The obtained multilayer ceramic capacitor was cut into a 3 mm square, and a cross section of 100 samples obtained was observed and evaluated according to the following criteria.
〇: No crack was observed.
X: Cracks occurred in one or more samples.

(Non-lamination occurs)
The obtained multilayer ceramic capacitor was cut into a 3 mm square, and a cross section of 100 samples obtained was observed and evaluated according to the following criteria.
：: No lamination was confirmed.
X: Non-lamination occurred in one or more samples.

(Porosity)
The cross section of the obtained multilayer ceramic capacitor was observed with a scanning microscope to confirm the presence or absence of holes. Subsequently, the diameter of 100 holes was measured to determine the coefficient of variation (CV), which was evaluated according to the following criteria.
：: Hole formation was confirmed, and the CV of the hole formation diameter was 20% or less.
〇: Hole formation was confirmed, and the CV of the hole diameter exceeded 20%.
×: No pore formation was confirmed.

ADVANTAGE OF THE INVENTION According to this invention, generation | occurrence | production of a crack and non-lamination can be suppressed, and it is possible to manufacture a ceramic capacitor having high porosity and excellent characteristics when used for a step absorption paste of an electrode pattern. It is possible to provide a smooth step absorption paste. Further, it is possible to provide a resin fine particle for a step absorbing paste, which has excellent decomposability at low temperature and can produce a high-strength molded body, and a method for producing a multilayer ceramic capacitor.

Claims (7)

It is a paste for absorbing the electrode step of the multilayer ceramic capacitor, containing inorganic fine particles, a plasticizer, an organic solvent, a binder resin, and organic fine particles,
The content of the organic fine particles is 1 part by weight to 10 parts by weight based on 100 parts by weight of the inorganic fine particles,
Level difference absorbing paste and satisfies the volume average of the volume average particle diameter _{r 1} of the inorganic fine particles and the organic fine particle size _{r 2} and is _{0.8 <r 2 / r 1 <} 1.5. Organic fine particles, (meth) containing acrylic resin, the (meth) acrylic resin segments derived from the polyfunctional (meth) acrylic acid ester containing 20 to 80 wt%, 100 has a volume average particle diameter r ₂ 2. The volume average particle diameter r ₂ and the volume average particle diameter r ₃ after immersion in terpineol for 24 hours satisfy 0.8 <r ₃ / r ₂ <1.2. The step absorption paste as described. 3. The step absorption paste according to claim 2, wherein the organic fine particles have a 10% by weight reduction temperature of 230 ° C. or less when heated at a temperature rising rate of 5 ° C./min. The step absorption paste according to claim 2, wherein the organic fine particles have a 90% by weight reduction temperature of 350 ° C. or less when heated at a heating rate of 5 ° C./min. 5. The step absorption paste according to claim 2, wherein the organic fine particles have a heating residue amount of 0.3% by weight or less when heated to 500 ° C at a heating rate of 5 ° C / min. (Meth) containing acrylic resin, the (meth) acrylic resin is polyfunctional (meth) the segment derived from an acrylate ester containing 20 to 80 wt%, a volume average particle diameter _{r 2} is 100 to 1000 nm, the volume average particle diameter _{r 2} and terpineol in volume average after immersion for 24 hours particle diameter _{r 3} and is _{0.8 <r 3} / r 2 <level difference absorbing paste resin particles and satisfies 1.2. A method for producing a laminated ceramic capacitor, wherein a laminate obtained by alternately laminating a ceramic green sheet and a conductive paste and a step absorption paste is degreased and fired, wherein a step of producing a ceramic green sheet; 6. A step of applying a conductive paste to a green sheet, and a step of applying the step absorbing paste according to claim 1, 2, 3, 4, or 5 to a region of the ceramic green sheet where the conductive paste is not applied. And a method for manufacturing a multilayer ceramic capacitor.