JP5567842B2 - Multilayer ceramic electronic component paste - Google Patents

Description

The present invention relates to a paste for a multilayer ceramic electronic component that is excellent in drying property and solubility of a binder resin and can suppress the occurrence of sheet attack. Furthermore, the present invention relates to a multilayer ceramic electronic component using the multilayer ceramic electronic component paste.

Polyvinyl acetal resins are used in various applications because they are excellent in toughness, film-forming properties, dispersibility of inorganic powders such as pigments and organic powders, and adhesion to coated surfaces.
Specific uses of polyvinyl acetal resin include, for example, capacitors, varistors, inductors, piezoelectric elements, thermistors, and the like. Among them, multilayer ceramic capacitors, multilayer ceramic varistors, multilayer ceramic inductors, multilayer ceramic LC components, It is often used as a material for multilayer ceramic electronic components such as multilayer ceramic substrates.

Such a multilayer ceramic electronic component is generally manufactured through the following steps.
First, after adding a plasticizer, a dispersing agent, etc. to a solution in which an organic binder resin such as polyvinyl butyral resin is dissolved in an organic solvent, the ceramic raw material powder is added and mixed uniformly by a ball mill or the like, and has a constant viscosity after defoaming. A ceramic slurry composition is obtained. This slurry composition is cast-molded on a support surface such as a polyethylene terephthalate film or a SUS plate which has been subjected to a release treatment using a doctor blade, a reverse roll coater or the like. This is heated to remove volatile components such as a solvent, and then peeled off from the support to obtain a ceramic green sheet.

Next, on the obtained ceramic green sheet, the electrode layer paste containing a conductive material such as palladium, silver, nickel, or the step absorption ceramic paste for absorbing the step generated by the electrode layer is printed in a predetermined pattern. To do. A plurality of the printed ceramic green sheets obtained are stacked and laminated, and a ceramic green chip is obtained through a press cutting process. And the process of forming an external electrode on the end face of the ceramic fired product obtained by performing the process of pyrolyzing and removing the binder component contained in the obtained ceramic green chip, so-called degreasing process After that, multilayer ceramic electronic parts are manufactured.

On the other hand, multilayer ceramic electronic components have recently been required to be further reduced in size and increased in capacity, and further multilayering and thinning of ceramic green sheets are being studied.
However, with the recent thinning of multilayer ceramic capacitors, in the process of printing the electrode layer paste and the step absorbing ceramic paste, the ceramic green sheet is caused by the solvent contained in the electrode layer paste and the step absorbing ceramic paste. The phenomenon of so-called sheet attack that was eroded occurred. When a sheet attack occurs, problems such as a decrease in the thickness of the ceramic green sheet and a breakage of the ceramic green sheet have occurred.

As a means for solving such a problem of sheet attack, for example, Patent Document 1 and Patent Document 2 include dihydroterpinyl acetate or a mixture of dihydroterpinyl acetate and hydrocarbon as an organic solvent used in the paste. The method used is described. However, when dihydroterpinyl acetate is used as the organic solvent, the volatility during drying is low. Therefore, in a short drying process at a relatively low temperature of 80 ° C. or less, the organic solvent remains and sheet attack occurs. There was a problem. In addition, when using a mixture of dihydroterpinyl acetate and hydrocarbon, the volatility during drying is high, but the volatility at room temperature is high, so the composition ratio is stable when the paste is used for a long time. There was a problem of not doing.

Japanese Patent No. 2976268 JP 2005-026217 A

An object of this invention is to provide the paste for multilayer ceramic electronic components which is excellent in drying property and the solubility of binder resin, and can suppress generation | occurrence | production of a sheet attack. Another object of the present invention is to provide a multilayer ceramic electronic component using the multilayer ceramic electronic component paste.

The present invention is a multilayer ceramic electronic component paste used by coating and drying on a ceramic green sheet, comprising a polyvinyl acetal resin, an organic solvent and an inorganic powder, wherein the polyvinyl acetal resin has a hydroxyl group content Is 24 mol% or less, the organic solvent contains butylene glycol diacetate, and the inorganic powder is a ceramic ceramic component paste that is a ceramic powder .
The present invention is described in detail below.

The present inventors have found that a paste for multilayer ceramic electronic parts containing polyvinyl acetal resin as a binder resin and butylene glycol diacetate as an organic solvent can improve the solubility and drying properties of the binder resin. The present inventors have found that inorganic powder is uniformly dispersed and has excellent printing characteristics. In addition, the inventors have found that the occurrence of sheet attack can be effectively suppressed, and have completed the present invention.

The paste for multilayer ceramic electronic components of the present invention contains a polyvinyl acetal resin.
Since the polyvinyl acetal resin is excellent in adhesiveness with a ceramic green sheet or the like, delamination can be effectively prevented by using the multilayer ceramic electronic component paste of the present invention.
The polyvinyl acetal resin is preferably a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol with an aldehyde.

The polyvinyl alcohol is preferably polyvinyl alcohol obtained by saponifying a polymer of vinyl ester such as vinyl formate, vinyl acetate, vinyl propionate or vinyl pivalate. From the economical viewpoint, the vinyl ester is more preferably vinyl acetate.

The polyvinyl alcohol is also preferably polyvinyl alcohol obtained by saponifying the copolymer of the vinyl ester and the α-olefin. By using the α-olefin, the hydrogen bond strength of the obtained polyvinyl acetal resin is reduced, and as a result, the viscosity stability with time or the printability of the multilayer ceramic electronic component paste of the present invention can be improved. Examples of the α-olefin include ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, hexylene, cyclohexylene, cyclohexylethylene, and cyclohexylpropylene. Of these, ethylene is preferable.
Further, as the polyvinyl alcohol, a terminal-modified polyvinyl alcohol obtained by copolymerization of the vinyl ester and ethylene in the presence of a thiol compound such as thiol acetic acid or mercaptopropionic acid, and then saponification may be used. Good.

When the polyvinyl alcohol is copolymerized, the content of the α-olefin is preferably 1 mol% at a preferable lower limit and 20 mol% at a preferable upper limit. When the content of the α-olefin is less than 1 mol%, the effect of adding the α-olefin may not be obtained. When the content of the α-olefin exceeds 20 mol%, the solubility of the obtained polyvinyl alcohol in water is lowered, so that it becomes difficult to perform the acetalization reaction, or the hydrophobicity of the obtained polyvinyl acetal resin. May become too strong and the solubility in organic solvents may decrease.

The polyvinyl alcohol is also a polyvinyl alcohol obtained by copolymerizing other ethylenically unsaturated monomers in addition to the vinyl ester and the α-olefin within a range not impairing the effects of the present invention. Also good.
Examples of the other ethylenically unsaturated monomers include acrylic acid, methacrylic acid, (anhydrous) fumaric acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, and trimethyl. -(3-acrylamido-3-dimethylpropyl) -ammonium chloride, acrylamido-2-methylpropanesulfonic acid and its sodium salt, ethyl vinyl ether, butyl vinyl ether, N-vinyl pyrrolidone, vinyl chloride, vinyl bromide, vinyl fluoride, Examples include vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, sodium vinyl sulfonate, and sodium allyl sulfonate.

When the polyvinyl alcohol is copolymerized, the content of the other ethylenically unsaturated monomer is preferably 1 mol% at the preferred lower limit and 30 mol% at the preferred upper limit. If the content of the other ethylenically unsaturated monomer is less than 1 mol%, the effect of adding the other ethylenically unsaturated monomer may not be obtained. When content of the said other ethylenically unsaturated monomer exceeds 30 mol%, properties, such as adhesiveness of a polyvinyl acetal resin obtained, coating-film strength, and thermal decomposability, may fall.

The polyvinyl alcohol has a preferred lower limit of the saponification degree of 80 mol%. If the degree of saponification is less than 80 mol%, the solubility of the resulting polyvinyl alcohol in water may be reduced, making it difficult to carry out an acetalization reaction, and the amount of hydroxyl groups in the polyvinyl alcohol. If the amount is small, the acetalization reaction itself may be difficult to proceed.

The polyvinyl alcohol has a preferable lower limit of 300 and a preferable upper limit of 3500 for the degree of polymerization. When the polymerization degree is less than 300, the viscosity of the multilayer ceramic electronic component paste of the present invention may be too low, resulting in a decrease in coatability. If the degree of polymerization exceeds 3500, the solubility of the resulting polyvinyl alcohol in water may decrease, or the viscosity of the aqueous solution may increase, making it difficult to perform the acetalization reaction. Moreover, when the said polymerization degree exceeds 3500, the viscosity of the paste for multilayer ceramic electronic components of this invention may be too high, and coating property may fall.
In this specification, when the polymerization degree of polyvinyl alcohol, which is a raw material before synthesis, is the polymerization degree of polyvinyl acetal resin, and two or more types of polyvinyl alcohol are used as a raw material before synthesis, polyvinyl alcohol to be used is used. The average of the polymerization degree is defined as the polymerization degree of the polyvinyl acetal resin.

The aldehyde is not particularly limited. For example, formaldehyde (including paraformaldehyde), acetaldehyde (including paraacetaldehyde), propionaldehyde, butyraldehyde, amylaldehyde, hexylaldehyde, heptylaldehyde, 2-ethylhexylaldehyde, cyclohexylaldehyde, furfural , Glyoxal, glutaraldehyde, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxyaldehyde, m-hydroxyaldehyde, phenylacetaldehyde, phenylpropionaldehyde. Of these, acetaldehyde and / or butyraldehyde are preferable. These aldehydes may be used alone or in combination of two or more aldehydes.

When a mixture of acetaldehyde and butyraldehyde is used as the aldehyde, the mixing ratio is preferably 5:95 to 75:25.
By being in the said range, the solubility to butylene glycol diacetate becomes higher and storage stability becomes high.

The method for producing the polyvinyl acetal resin is not particularly limited. For example, the polyvinyl alcohol is dissolved in warm water, and in the presence of an acid catalyst, an aldehyde is added and reacted so as to have a desired degree of acetalization. Examples include neutralizing, washing with water and drying.
The acid catalyst is not particularly limited, and may be an organic acid or an inorganic acid. Examples of the acid catalyst include acetic acid, paratoluenesulfonic acid, nitric acid, sulfuric acid, and hydrochloric acid. Moreover, the alkali used for neutralization is not specifically limited, For example, sodium hydroxide, potassium hydroxide, ammonia, sodium acetate, sodium carbonate, sodium hydrogencarbonate, potassium carbonate is mentioned.

The polyvinyl acetal resin has a preferable lower limit of the degree of acetalization of 60 mol% and a preferable upper limit of 80 mol%. If the degree of acetalization is less than 60 mol%, the resulting polyvinyl acetal resin has too strong hydrogen bonding strength, and the paste for multilayer ceramic electronic components of the present invention may not have sufficient printability. Polyvinyl acetal resins having a degree of acetalization exceeding 80 mol% are generally difficult to produce industrially. P.P. J. et al. According to the theoretical calculation of Flory, the preferable upper limit of the degree of acetalization of the polyvinyl acetal resin is 81.6 mol% (see J. Am. Chem. Soc. 61, 1518 (1939)).

The upper limit with the preferable amount of hydroxyl groups of the said polyvinyl acetal resin is 24 mol%. When the amount of the hydroxyl group exceeds 24 mol%, the solubility in an organic solvent may be lowered. A more preferable upper limit of the hydroxyl group content is 23 mol%. In addition, although the minimum with the preferable amount of hydroxyl groups of the said polyvinyl acetal resin is not specifically limited, Generally a polyvinyl acetal resin in which the amount of hydroxyl groups is less than 20 mol% is industrially difficult to manufacture.

In the multilayer ceramic electronic component paste of the present invention, the polyvinyl acetal resin has a preferable lower limit of 1 part by weight and a preferable upper limit of 20 parts by weight with respect to 100 parts by weight of the inorganic powder. When the content of the polyvinyl acetal resin is less than 1 part by weight, the dispersion stability of the multilayer ceramic electronic component paste of the present invention decreases, and the strength or adhesion of the coating film after coating and drying decreases. Sometimes. When the content of the polyvinyl acetal resin exceeds 20 parts by weight, the degreasing property of the multilayer ceramic electronic component paste of the present invention is lowered, or the density of the conductive layer of the obtained fired body is lowered, so that sufficient electrical characteristics are obtained. It may not be obtained.

The multilayer ceramic electronic component paste of the present invention contains butylene glycol diacetate as an organic solvent.
Originally, it is known that polyvinyl acetal resin has relatively high solubility in a mixed solvent of ethanol and toluene. However, such a conductive paste containing a highly volatile solvent is easy to dry at the time of production or coating, and is applied continuously to a large number of substrates through a single screen-making process such as screen printing. In such a case, there is a problem that clogging is likely to occur in the screen-making mesh. In addition, when dihydroterpinyl acetate is used, the volatility during drying is low, and therefore, in a short drying process at a relatively low temperature of 80 ° C. or less, the organic solvent remains and sheet attack occurs. There was a problem.
In the multilayer ceramic electronic component paste of the present invention, by using an organic solvent containing butylene glycol diacetate, it becomes possible to improve the solubility of the polyvinyl acetal resin while making the drying property appropriate, and the sheet attack Therefore, the problems of dryness, resin solubility, and sheet attack, which were problems when using conventional organic solvents, were solved at the same time.

As the butylene glycol diacetate, 1,3-butylene glycol diacetate and 1,4-butylene glycol diacetate are used, and 1,3-butylene glycol diacetate is particularly preferable from the viewpoint of cost.

In the multilayer ceramic electronic component paste of the present invention, the preferable lower limit of the content of butylene glycol diacetate is 7% by weight, and the preferable upper limit is 80% by weight. When the content of the butylene glycol diacetate is less than 7% by weight, it becomes difficult to apply the paste. If the content of the butylene glycol diacetate exceeds 80% by weight, the viscosity of the multilayer ceramic electronic component paste of the present invention may be too low and printability may deteriorate.

The inorganic powder is not particularly limited, and examples thereof include metal powder, conductive powder, ceramic powder, and glass powder.

When a conductive powder is used as the inorganic powder, it can be used as a conductive paste.
The conductive powder is not particularly limited as long as it exhibits sufficient conductivity, and examples thereof include powder made of nickel, palladium, platinum, gold, silver, copper, alloys thereof, and the like. These conductive powders may be used alone or in combination of two or more.

When ceramic powder is used as the inorganic powder, it can be used as a ceramic paste, particularly as a step absorption paste. The ceramic powder is not particularly limited. For example, a powder made of alumina, zirconia, aluminum silicate, titanium oxide, zinc oxide, barium titanate, magnesia, sialon, spinemullite, silicon carbide, silicon nitride, aluminum nitride, or the like. Is mentioned. Especially, it is preferable to consist of the same component as the ceramic powder contained in the ceramic green sheet to be used. These ceramic powders may be used alone or in combination of two or more.

When glass powder is used as the inorganic powder, it can be used as a glass paste. The glass powder is 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. Etc. These glass powders may be used alone or in combination of two or more. Moreover, you may use aluminum oxide etc. together in the range which does not impair the objective of this invention.

When magnetic powder is used as the inorganic powder, it can be used as a magnetic material paste. The magnetic powder is not particularly limited, for example, ferrites such as manganese zinc ferrite, nickel zinc ferrite, copper zinc ferrite, barium ferrite and strontium ferrite, metal oxides such as chromium oxide, metal magnetic materials such as cobalt, amorphous Examples include magnetic materials. These magnetic powders may be used alone or in combination of two or more.

In the multilayer ceramic electronic component paste of the present invention, the content of the inorganic powder is not particularly limited, and may be appropriately adjusted depending on the type and specific gravity of the inorganic powder used, the printing method of the multilayer ceramic electronic component paste of the present invention, and the like. The preferred lower limit is 30% by weight and the preferred upper limit is 80% by weight. If the content of the inorganic powder is less than 30% by weight, the viscosity of the multilayer ceramic electronic component paste of the present invention is low, so that the printability is reduced, or the organic component is large, so the residual organic content after firing is small. May increase. When the content of the inorganic powder exceeds 80% by weight, it may be difficult to disperse the inorganic powder.

Furthermore, the paste for multilayer ceramic electronic components 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 viscosity of the multilayer ceramic electronic component paste of the present invention is not particularly limited. However, when measured at 20 ° C. using a B-type viscometer with the probe rotation speed set to 5 rpm, the preferable lower limit is 0.1 Pa · s. The preferred upper limit is 100 Pa · s. When the viscosity measured as described above is less than 0.1 Pa · s, it becomes difficult for the multilayer ceramic electronic component paste of the present invention to maintain a predetermined shape after coating by a die coat printing method or the like. There is. When the viscosity measured as described above exceeds 100 Pa · s, the printability of the multilayer ceramic electronic component paste of the present invention may deteriorate.

The method for producing the multilayer ceramic electronic component paste of the present invention is not particularly limited. For example, the polyacetal resin, the organic solvent, the inorganic powder, and various additives are conventionally known using a three-roll, bead mill or the like. The method of kneading by a stirring method is mentioned.

The method of applying the multilayer ceramic electronic component paste of the present invention is not particularly limited, and examples thereof include screen printing, die coating printing, offset printing, gravure printing, and inkjet printing.

The multilayer ceramic electronic component paste of the present invention is coated on a ceramic green sheet and dried, then the obtained dried body is laminated, and the laminate obtained by thermocompression bonding is degreased and fired to obtain a laminate. A ceramic electronic component can be suitably manufactured.
Such a multilayer ceramic electronic component is also one aspect of the present invention.

Examples of the multilayer ceramic electronic component include a multilayer ceramic capacitor, a multilayer ceramic varistor, a multilayer ceramic inductor, a multilayer ceramic LC component, and a multilayer ceramic substrate.
As a method for producing the above-mentioned multilayer ceramic capacitor, for example, a multilayer ceramic electronic component paste of the present invention coated on a ceramic green sheet is stacked, heated and pressed to obtain a laminate, and then degreased. A method of forming an external electrode on the end face of the fired body obtained by performing treatment and then firing is exemplified.

As the polyvinyl acetal resin used for the ceramic green sheet, a resin having a hydroxyl group content of 28 mol% or more is preferably used.
When the amount of the hydroxyl group is less than 28 mol%, not only the strength of the ceramic green sheet is lowered, but also partly dissolved in butylene glycol diacetate, so that there is a problem such as sheet breakage due to a so-called sheet attack phenomenon. It may occur.

ADVANTAGE OF THE INVENTION According to this invention, while being excellent in drying property and the solubility of binder resin, the paste for multilayer ceramic electronic components which can suppress generation | occurrence | production of a sheet attack can be provided. Furthermore, according to the present invention, a multilayer ceramic electronic component using the multilayer ceramic electronic component paste can be provided.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
(Preparation of polyvinyl acetal resin for paste)
193 g of modified polyvinyl alcohol having a polymerization degree of 1700, an ethylene content of 10 mol% and a saponification degree of 88 mol% was added to 2900 g of pure water and dissolved by stirring at a temperature of 90 ° C. for about 2 hours. The obtained solution was cooled to 28 ° C., and 20 g of hydrochloric acid having a concentration of 35% by weight and 115 g of a mixture having a weight ratio of n-butyraldehyde and acetaldehyde of 2: 1 were added thereto, and the liquid temperature was lowered to 20 ° C. The acetalization reaction was carried out while maintaining this temperature to precipitate the reaction product. Thereafter, the liquid temperature was kept at 30 ° C. for 5 hours to complete the reaction, and neutralized, washed with water and dried by a conventional method to obtain a white powder of a modified polyvinyl acetal resin. When the obtained polyvinyl acetal resin was dissolved in DMSO-d ₆ (dimethyl sulfoxide) and the degree of acetalization was measured using ¹³ C-NMR (nuclear magnetic resonance spectrum), the degree of acetalization was 67.4 mol. %Met.

(Production of ceramic green sheets)
10 parts by weight of polyvinyl butyral resin (manufactured by Sekisui Chemical Co., Ltd., ESREC B “BM-2”, degree of polymerization 850, hydroxyl group content 30.0 mol%) is added to a mixed solvent of 30 parts by weight of toluene and 15 parts by weight of ethanol. Then, 3 parts by weight of dibutyl phthalate was added as a plasticizer and dissolved by stirring. To the obtained resin solution, 100 parts by weight of barium titanate (“BT-02 (average particle size: 0.2 μm)” manufactured by Sakai Chemical Industry Co., Ltd.) as ceramic powder was added and mixed with a ball mill for 48 hours to obtain a ceramic slurry composition. Got. The obtained ceramic slurry composition was coated on a release-treated polyester (PET) film using a coater so that the thickness after drying was about 3 μm, air-dried at room temperature for 1 hour, and then hot-air dryer At 80 ° C. for 3 hours, followed by drying at 120 ° C. for 2 hours to obtain a ceramic green sheet. When the surface roughness of the obtained ceramic green sheet was measured with a contact-type surface roughness meter “Surfcom 1400D” (manufactured by Tokyo Seimitsu Co., Ltd.), the maximum height Rz (JIS B0601: 2001) was 0.35 μm.

(Production of ceramic paste)
100 parts by weight of barium titanate powder (“BT-02 (average particle diameter 0.2 μm)” manufactured by Sakai Chemical Industry Co., Ltd.) as inorganic powder, modified polyvinyl butyral obtained as binder resin (degree of polymerization 1700, ethylene content 10 mol) %, Saponification degree 88 mol%, hydroxyl group amount 20.6 mol%) 6 parts by weight, 80 parts by weight of 1,3-butylene glycol diacetate as an organic solvent was added and kneaded with three rolls to obtain a ceramic paste. Obtained.

(Ceramic paste coating)
The obtained ceramic paste was applied to each of the two previously obtained ceramic green sheets by screen printing, and then dried at 90 ° C., 20 minutes, 60 ° C. and 10 minutes, respectively. Body 1 and 2 were obtained. A SUS400 mesh plate was used as the screen plate. It was 2 micrometers when the thickness of the obtained ceramic paste layer was measured with the contact-type roughness meter.

(Example 2)
A dried ceramic paste was obtained in the same manner as in Example 1, except that 112 g of a mixture having a weight ratio of n-butyraldehyde and acetaldehyde of 4: 1 was added in preparing the polyvinyl acetal resin for paste. In addition, the amount of hydroxyl groups of the obtained polyvinyl acetal resin for paste was 23.5 mol%.

(Example 3)
A dried ceramic paste was obtained in the same manner as in Example 1 except that 1,4-butylene glycol diacetate was used as the paste solvent.

( Reference Example 4)
A dried ceramic paste was obtained in the same manner as in Example 1 except that 106 g of a mixture having a weight ratio of n-butyraldehyde and acetaldehyde of 2: 1 was added in preparing the polyvinyl acetal resin for paste. In addition, the amount of hydroxyl groups of the obtained polyvinyl acetal resin for paste was 25.6 mol%.

(Comparative Example 1)
A dried ceramic paste was obtained in the same manner as in Example 1 except that dihydroterpinyl acetate was used as the organic solvent for the ceramic paste.

(Comparative Example 2)
A dried ceramic paste was obtained in the same manner as in Example 1 except that a mixed solution of 85% by weight of dihydroterpinyl acetate and 15% by weight of dodecane was used as the organic solvent for the ceramic paste.

(Comparative Example 3)
A dried ceramic paste was obtained in the same manner as in Example 1 except that butyl carbitol acetate (diethylene glycol monobutyl ether acetate) was used as the organic solvent for the ceramic paste.

(Comparative Example 4)
A dried ceramic paste was obtained in the same manner as in Example 1 except that terpineol was used as the organic solvent for the ceramic paste.

(Comparative Example 5)
A dried ceramic paste was obtained in the same manner as in Example 1 except that 1,1-ethylene glycol diacetate was used as the organic solvent for the ceramic paste.

(Comparative Example 6)
A dried ceramic paste was obtained in the same manner as in Example 1 except that 1,2-ethylene glycol diacetate was used as the organic solvent for the ceramic paste.

(Comparative Example 7)
A dried ceramic paste was obtained in the same manner as in Example 1 except that 1,3-propylene glycol diacetate was used as the organic solvent for the ceramic paste.

(Comparative Example 8)
A dried ceramic paste was obtained in the same manner as in Example 1 except that 1,5-pentylene glycol diacetate was used as the organic solvent for the ceramic paste.

(Comparative Example 9)
A dried ceramic paste was obtained in the same manner as in Example 1 except that 1,6-hexylene glycol diacetate was used as the organic solvent for the ceramic paste.

(Comparative Example 10)
A dried ceramic paste was obtained in the same manner as in Example 1 except that 5 parts by weight of ethyl cellulose (STD-100 manufactured by Dow Chemical Company) was used as the resin for the ceramic paste.

(Evaluation)
The ceramic paste and the dried ceramic paste obtained in Examples , Reference Examples and Comparative Examples were evaluated by the following methods.

(1) Sheet attack property 10 portions of the back surface (polyester film surface) of the obtained ceramic paste dried bodies 1 and 2 were observed with a metal microscope (200 times), and the portion of the ceramic green sheet on which the ceramic paste was applied It was confirmed whether or not wrinkles and cracks occurred.
The case in which protrusions due to wrinkles, cracks, and resin swelling were observed was evaluated as x, and the case in which protrusions due to wrinkles, cracks, and resin swelling were not observed was evaluated as o.

(2) Volatility at room temperature 20 ± 0.1 g of the obtained ceramic paste was placed on an aluminum dish having an inner diameter of 7 centimeters and kept for 24 hours without a lid in a room kept at room temperature 23 ° C. and humidity 50%. After 24 hours, the weight was measured again, and when the weight reduction rate of the ceramic paste was 2% or more, x was less than 2%.

(3) Surface roughness Among the obtained ceramic paste dried body, the surface roughness (maximum height Rz) of the ceramic paste coating part was measured with a contact surface roughness meter “Surfcom 1400D” (manufactured by Tokyo Seimitsu Co., Ltd.). did. The obtained maximum height Rz (JIS B0601: 2001) was 2 μm or more, and x was less than 2 μm.

ADVANTAGE OF THE INVENTION According to this invention, while being excellent in drying property and the solubility of binder resin, the paste for multilayer ceramic electronic components which can suppress generation | occurrence | production of a sheet attack can be provided. Furthermore, according to the present invention, a multilayer ceramic electronic component using the multilayer ceramic electronic component paste can be provided.

Claims (3)

A multilayer ceramic electronic component paste used by coating and drying on a ceramic green sheet,
Containing polyvinyl acetal resin, organic solvent and inorganic powder,
The polyvinyl acetal resin has a hydroxyl group content of 24 mol% or less,
The organic solvent contains butylene glycol diacetate,
A paste for multilayer ceramic electronic parts, wherein the inorganic powder is a ceramic powder. 2. The multilayer ceramic electronic component paste according to claim 1, wherein the polyvinyl acetal resin is a modified polyvinyl acetal resin obtained by acetalizing a modified polyvinyl alcohol having an ethylene content of 1 to 20 mol%. The multilayer ceramic electronic component paste according to claim 1, wherein the inorganic powder is the same as the ceramic powder contained in the ceramic green sheet.