JP2001155543A - Paste composition, electronic parts and ceramic green sheet and method of manufacturing multilayer ceramic board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a paste composition inhibiting gelatinization, and superior in the storage stability. SOLUTION: In this paste composition prepared by mixing an organic binder including an organic high molecular compound having an acid functional group, and the inorganic powder including polyvalent metal or its compound, a compound having an amide structure is further included. An amide position in the compound having the amide structure exhibits a remarkably high bonding strength with the polyvalent metallic ion in comparison with the acid functional group (in particular, carboxyl group) of the organic binder, whereby the polyvalent metallic ion and the compound having the amide structure eluted into a solution part of the paste composition are reacted first, and inhibit the ionic crosslinking of an anion of the organic high molecular compound and the polyvalent metallic ion as well as the formation of its three-dimensional network, which inhibits the gelatinization. A photosensitive organic component is further preferably included for the patterning by lithographic technique.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paste composition and a ceramic green sheet containing an inorganic powder, an electronic component manufactured using the same, and a method for manufacturing a multilayer ceramic substrate. Alternatively, the present invention relates to an improvement for suppressing gelation in a slurry for obtaining a ceramic green sheet.

[0002]

2. Description of the Related Art In a circuit board built in an electronic device such as a portable terminal device or a computer, in order to exhibit a function as the circuit board, a conductive film or via-hole conductor patterned in the substrate is required. It is necessary to form a wiring conductor. Moreover, in recent years, with high-density and high-speed signal transmission of high-frequency electronic devices, wiring conductors such as conductor films and via-hole conductors in circuit boards provided in these electronic devices have become fine and highly accurate. Is required.

In a high-frequency electronic component such as a circuit board provided in the above-described high-frequency electronic device, a conductive film is generally formed by using a conductive metal powder made of a polyvalent metal such as iron or copper, an organic binder and an organic solvent. A method has been used in which a conductive paste mixed with an organic vehicle is used, applied on an insulating substrate in a desired pattern, dried, and fired.

Here, the formation of the patterned conductor film is usually performed by a screen printing method. In the case of the conductor film formed by this method, the wiring width and the pitch between the wirings are reduced. Is limited to about 50 μm.

On the other hand, Japanese Patent Application Laid-Open Nos. Hei 5-287221 and Hei 8-227153 propose a method of forming a fine thick film wiring by a photolithography technique using a photosensitive conductive paste. . In this method, a photosensitive conductive paste comprising a conductive metal powder, an acrylic copolymer having a carboxyl group and an ethylenically unsaturated group in a side chain, a photoreactive compound, a photopolymerization initiator and the like is placed on an insulating substrate. Is applied, dried, and then patterned based on a photolithography technique.

[0006] On the other hand, via-hole conductors are generally formed by printing an insulator paste composition obtained by mixing an insulating inorganic powder such as glass in an organic vehicle through a predetermined screen mask. After forming an insulating paste film having a through-hole formed therein, a conductive paste composition is filled in the through-hole for a via hole, and the conductive paste composition is baked.

However, according to the above-mentioned method, the diameter is at most 2 due to bleeding or blurring caused by screen printing.
The limit is to make a through hole for a via hole of 00 μm.

On the other hand, JP-A-6-283846 discloses a photosensitive paste composition obtained by further mixing a photosensitive organic component with an insulating paste composition, and using a photolithography technique. A method of forming a fine via hole for a via hole has been proposed.

Further, in order to increase the number of functions, density and performance of a multilayer ceramic substrate typified by a substrate for a high-frequency module and a substrate for a hybrid IC, it is necessary to provide wiring at a high density. Is valid. In particular, in the case of a multilayer ceramic substrate, the incorporation of high-precision passive components in the multilayer ceramic substrate is also effective for achieving more functions, higher density, and higher performance.

As described above, a method for manufacturing a multilayer ceramic substrate incorporating passive components is described in, for example, JP-A-9-92983. In this gazette, in order to manufacture a multilayer ceramic substrate having built-in passive components such as inductors and capacitors, a multilayer ceramic substrate is manufactured using a plurality of types of ceramic green sheets having various characteristics such as insulation, dielectric properties, and magnetism. A method of partially forming an inductor or a capacitor therein is disclosed.

Further, in order to increase the functionality, density, and performance of the multilayer ceramic substrate, it is necessary to provide fine via-hole conductors in the above-described ceramic green sheet as necessary. As a method of forming a through-hole for providing a via-hole conductor in a ceramic green sheet, a method of punching out with a mold has been generally used.

However, in the punching method described above,
In order to process the ceramic green sheet by applying a mechanical load, even if the through hole is to be made smaller, the diameter is limited to at most about 100 μm.

On the other hand, as a method of forming a through hole for a finer via hole, for example, Japanese Patent Laid-Open No. Hei 10-279364 discloses a method of forming a through hole for a via hole by photolithography. Have been. In this method, a photosensitive ceramic green sheet is prepared by forming a photosensitive slurry formed by mixing a photosensitive resin and a ceramic powder into a sheet, and using an actinic ray such as ultraviolet light through a photomask. Through a process of performing a development process after the exposure, a fine through hole for a via hole is formed.

[0014]

In recent years, in photolithography technology using a photosensitive paste or a photosensitive slurry, it has been desired that development with water or an aqueous alkaline solution is possible in consideration of the environment.

Therefore, in a photosensitive paste or a photosensitive slurry, an organic binder containing an organic polymer compound having an acidic functional group such as a carboxyl group or a hydroxyl group capable of releasing protons is introduced into a side chain. I have.

However, in order to prepare a photosensitive paste or a photosensitive slurry, a polyvalent metal such as a glass powder or a ceramic powder or an oxide thereof is added to an organic binder containing an organic polymer compound having an acidic functional group as described above. Is added, a polyvalent metal ion eluted from such a powder and an anion of an organic polymer compound generated after proton release are ion-crosslinked to form a three-dimensional network, thereby forming a gel. It has been found that the transformation occurs.

The non-uniform paste or slurry in which gelation has occurred has low workability, so that it can be applied with an appropriate pattern, formed into a sheet with a uniform thickness,
Further, it is difficult to form a fine through-hole. In addition, there arises a problem that development of the applied photosensitive paste film becomes unstable. Also, when an electronic component such as a ceramic substrate is to be manufactured using a ceramic green sheet formed with a non-uniform slurry, cracks may occur during firing, and as a result, the electronic component such as a ceramic substrate that is mechanically fragile is consequently produced. Only parts can be obtained.

As a method for preventing gelation, for example, in JP-A-9-218509, a phosphorus-containing compound such as phosphoric acid, and in JP-A-9-218508, a compound having an azole structure such as benzotriazole is used. JP-A-9-222723 discloses that an organic compound having a carboxyl group such as acetic acid is contained in a photosensitive paste as a gelling inhibitor.

However, these methods only slightly increase the time required for the photosensitive paste to gel, so that the practical difficulty of the photosensitive paste has not been substantially solved.

JP-A-10-171107 discloses that gelation can be prevented by using 3-methyl-3-methoxybutanol as an organic solvent. However, since the boiling point of 3-methyl-3-methoxybutanol is as low as 174 ° C., the organic solvent component is completely evaporated when the photosensitive paste after application is dried, and the effect of preventing gelation is lost. As a result, even in a paste in a dry state, a phenomenon similar to gelation, that is, a phenomenon in which a three-dimensional network is formed by ionic cross-linking and a substantial molecular weight is increased, and an unexposed portion is eluted into the developer. Problems such as disappearance may occur.

Some of the various problems described above are peculiar to the photosensitive paste or the photosensitive slurry. Except for such peculiar problems, the photosensitive paste or the photosensitive slurry has an acidic functional group. This applies to pastes or slurries containing an organic binder containing an organic polymer compound in general.

An object of the present invention is to solve the above-mentioned problem.

A more specific object of the present invention is to form a layer having a functional material film such as a fine and thick conductor film or a via-hole conductor having high adhesion to a substrate and further suppressing gelation. And to provide a paste composition having excellent storage stability.

Another object of the present invention is to provide an electronic component such as a circuit board having a functional material film or layer formed using the paste composition as described above. is there.

Still another object of the present invention is to provide a ceramic green sheet excellent in uniformity and workability by suppressing gelation of a slurry.

Still another more specific object of the present invention is to provide an electronic component such as a mechanically strong ceramic substrate constituted by using a ceramic green sheet as described above. .

Still another more specific object of the present invention is implemented using the ceramic green sheet as described above, and provided with a conductor film and a via-hole conductor in a high-density and fine pattern. An object of the present invention is to provide a method for manufacturing a multilayer ceramic substrate.

[0028]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the anion of the organic binder containing the organic polymer compound having an acidic functional group and the polyvalent compound are contained in the solution. The present inventors have found that gelation can be effectively suppressed by adding a compound having an amide structure to a system in which metal ions are eluted, and have accomplished the present invention.

First, the present invention is directed to a paste composition. The paste composition includes an organic binder containing an organic polymer compound having an acidic functional group, an inorganic powder containing a polyvalent metal or a compound thereof, and a compound having an amide structure.

The above-mentioned inorganic powder may be a conductive metal powder or a mixture of a conductive metal powder and a glass powder containing a polyvalent metal or a compound thereof.
Or it may be a ceramic powder. As the conductive metal powder, for example, a powder containing at least one selected from the group consisting of gold, silver, copper, platinum, aluminum, palladium, nickel, molybdenum and tungsten is used.

The present invention is also directed to an electronic component comprising a base and a functional material film obtained by applying the paste composition as described above on the base and then firing the paste.

The present invention is also directed to an electronic component having a layer obtained by firing the above-described paste composition.

According to the paste composition of the present invention,
Since it contains a compound having an amide structure, it is possible to sufficiently suppress the progress of gelation in both the paste state before coating and the coated state after coating and drying, and also achieves close contact with the substrate. With high power, various wiring conductors such as conductor films and via-hole conductors can be formed finely and with high precision.
As a result, it is possible to obtain an electronic component such as a circuit board that can sufficiently achieve high-density wiring and high-speed signal transmission.

The suppression of the above-mentioned gelation is caused by the fact that the amide site in the compound having an amide structure is formed by an acidic functional group (particularly a carboxyl group) of the organic polymer compound contained in the organic binder.
The binding force with polyvalent metal ions is remarkably strong,
Therefore, the polyvalent metal ion eluted in the solution portion of the paste composition and the compound having the amide structure react first, and the ionic cross-linking between the anion of the organic polymer compound and the polyvalent metal ion and its three-dimensional network are performed. This is due to preventing formation.

The present invention is further directed to a ceramic green sheet. The ceramic green sheet includes an organic binder containing an organic polymer compound having an acidic functional group, a ceramic powder containing a polyvalent metal, and / or
Alternatively, the slurry is obtained by forming a slurry containing glass powder and a compound having an amide structure into a sheet.

Examples of the above-mentioned ceramic powder and / or glass powder include boron, barium, magnesium, aluminum, calcium, lead, bismuth, and the like.
At least one selected from the group consisting of copper, zinc, zirconium, niobium, chromium, strontium and titanium
Those containing various polyvalent metals and / or oxides thereof are used.

The present invention is also directed to an electronic component including a ceramic layer formed by firing the above-described ceramic green sheet.

Further, the present invention is also directed to a method for manufacturing a multilayer ceramic substrate, which is performed using the above-described ceramic green sheet. The method for manufacturing a multilayer ceramic substrate includes a step of preparing a plurality of ceramic green sheets according to the present invention, a step of providing through holes in specific ones of the ceramic green sheets, and applying a conductive paste in the through holes. Forming a via film conductor by applying a conductive paste on the ceramic green sheet so as to be connected to the via hole conductor, and forming the ceramic green sheet on which the via hole conductor is formed. It is characterized by comprising a step of producing a raw laminate by laminating a plurality of ceramic green sheets including the above, and a step of firing the raw laminate.

Also in such a ceramic green sheet, the compound having an amide structure contained in the slurry prepared for molding the ceramic green sheet performs the same action as in the case of the paste composition described above, and the gelation proceeds. Is sufficiently suppressed.

In the present invention, as the compound having an amide structure, a monoamide compound or a fatty acid amide is preferably used. When a fatty acid amide is used, preferably, a saturated fatty acid amide is used.

In the present invention, the compound having an amide structure is used in an amount of from 0.03% by weight in a slurry for a paste composition or a ceramic green sheet.
It is preferred to contain 0.5% by weight.

In the present invention, the slurry for the paste composition or the ceramic green sheet preferably further contains a photosensitive organic component.

As described above, when the paste composition contains a photosensitive organic component and the present invention is directed to an electronic component as described above, the paste composition is applied to a substrate, and photolithography is performed. By patterning using a technique and then firing, a functional material film having a desired pattern can be formed.

In the case where the slurry contains a photosensitive organic component and the present invention is directed to the method for manufacturing a multilayer ceramic substrate as described above, the ceramic green sheet is formed on the ceramic green sheet by photolithography. Through holes can be provided.

In the present invention, the organic polymer having an acidic functional group is preferably an acrylic copolymer having a carboxyl group in a side chain.

In the present invention, the slurry for the paste composition or the ceramic green sheet preferably further contains a monol compound.

In the present invention, the slurry for the paste composition or the ceramic green sheet is
The organic binder preferably further contains an anion-adsorbing substance having a property of adsorbing anions of the organic polymer compound contained in the organic binder.

Further, in the present invention, the slurry for the paste composition or the ceramic green sheet is:
Further, it is preferable to include a thixotropic agent.

[0049]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a slurry for a paste composition or a ceramic green sheet according to the present invention will be described in more detail with reference to preferred embodiments thereof.

In the paste composition or slurry according to the present invention, as the compound having an amide structure, a monoamide compound having only one amide moiety is preferably used. In the case of a compound having two or more amide moieties, the compound does not gel if the compound has a sufficiently low molecular weight, but if the compound has a molecular weight of 1000 or more, the compound has a polyvalent metal ion depending on the amide moiety in the compound. This is because a three-dimensional network of the compound and the compound may be formed and gelled.

Further, as a compound having an amide structure,
Fatty acid amide compounds can be suitably used. This is because, when an electron-donating group is adjacent to a site where a polyvalent metal is bonded, the bonding force between the site and the polyvalent metal ion is strengthened. This is because, in the fatty acid amide compound adjacent to the site, the bonding force between the polyvalent metal ion and the amide site is extremely increased by this mechanism.

The above fatty acid amide is particularly preferably a saturated fatty acid amide. This is because, when the aliphatic hydrocarbon chain adjacent to the amide site is a saturated aliphatic hydrocarbon chain, the electron donating property to the amide site becomes higher because there is no electron withdrawal due to conjugation.

Compounds having such an amide structure include, for example, acetic acid amide, butyric acid amide, propionic acid amide, valeric acid amide, hexanoic acid amide, heptyl acid amide, octanoic acid amide, decanoic acid amide, nonanoic acid amide, Stearamide, oleamide, erucamide and the like.

As a method of including the compound having an amide structure in a paste composition or a slurry, a method of simply mixing the compound into the paste composition or a slurry,
There is a method of coating the surface of the inorganic powder or the surface of the ceramic powder / glass powder. As a method of coating the latter powder surface, a solution in which a compound having an amide structure is dissolved in an appropriate organic solvent is prepared, and the powder is added to the solution, and the solution is stirred. There is a method of removing the residue by filtration and drying the residue.

The amount of the compound having an amide structure in the paste composition or slurry is preferably 0.0
Desirably, it is 3% by weight to 0.5% by weight. 0.0
If the amount is less than 3% by weight, gelation cannot be effectively prevented. On the other hand, if the amount exceeds 0.5% by weight, the paste composition is applied to an appropriate substrate, or the slurry is formed into a sheet on an appropriate substrate. When molding the paste composition or slurry, the surface tension of the paste composition or slurry with respect to the substrate increases, making it difficult to apply the paste composition uniformly on the substrate or to produce a uniform ceramic green sheet. It is because it becomes.

In the paste composition according to the present invention, as the inorganic powder contained therein, conductive metal powder, a mixture of conductive metal powder and glass powder, or glass powder and / or ceramic powder is used. .

As the above-mentioned glass powder, a known glass powder such as a borosilicate glass powder can be used. Also,
Glass powder, in particular, SiO ₂ -PbO-based, SiO ₂ -
ZnO-based, SiO ₂ -Bi ₂ O ₃ system, SiO ₂ -K ₂ O
System, SiO ₂ -Na ₂ O-based, SiO ₂ -PbO-B ₂ O
₃ system, SiO ₂ -ZnO-B ₂ O ₃ system, SiO ₂ -Bi
₂ O ₃ —B ₂ O ₃ system, SiO ₂ —K ₂ O—B ₂ O ₃ system,
It may include a polyvalent metal oxide having a valence of 2 or more, such as a SiO ₂ —Na ₂ O—B ₂ O ₃ system.

As the above-mentioned ceramic powder, a known ceramic powder of a crystallized glass type, a glass composite type, or a non-glass type can be used. Further, the ceramic powder may be a ceramic powder containing a polyvalent metal compound having a valence of 2 or more.

Examples of the ceramic containing the above-mentioned polyvalent metal compound include Al, Ba, Ti, Sr, Pb, and Z.
r, Mn, Co, Ni, Fe, Y, Nb, La and R
oxides, borides, nitrides or silicides of at least one polyvalent metal selected from the group consisting of u.

As the above-mentioned conductive metal powder, for example, a powder containing at least one selected from the group consisting of gold, silver, copper, platinum, aluminum, palladium, nickel, molybdenum, and tungsten can be used.

In particular, when a conductive metal powder containing copper, aluminum, palladium, nickel, molybdenum, tungsten or a mixture thereof, which is a polyvalent metal, is used, the ion and acidic functional group due to the polyvalent metal are converted. It is possible to effectively suppress ionic cross-linking of the organic polymer compound having an anion with an anion and formation of a three-dimensional network.

That is, in the paste composition according to the present invention, when the metal constituting the conductive metal powder is a polyvalent metal having a valence of 2 or more, the glass powder or the ceramic powder has a valence of 2 or more. In the case of a compound containing a polyvalent metal having, or in the case of both, a polyvalent metal ion eluted in a solution and an organic polymer compound having an acidic functional group such as a carboxyl group Of the paste composition and the formation of a three-dimensional network can be suppressed, and gelation of the paste composition can be effectively suppressed.

Regarding the slurry for ceramic green sheets according to the present invention, the ceramic powder and / or glass powder contained therein contains boron, barium, magnesium, aluminum, calcium, lead,
Bismuth, copper, zinc, zirconium, niobium, chromium,
The powder is preferably a powder containing at least one polyvalent metal selected from the group consisting of strontium and titanium or an oxide thereof.

More specifically, the above-described glass powder or
Is a ceramic powder, SiO_Two-PbO-based, SiO
_Two-ZnO-based, SiO_Two-Bi_TwoO_ThreeSystem, SiO_Two-K
_TwoO-based, SiO_Two-Na_TwoO-based, SiO_Two-PbO-B
_TwoO_ThreeSystem, SiO_Two-ZnO-B_TwoO_ThreeSystem, SiO_Two−
Bi_TwoO_Three-B_TwoO_ThreeSystem, SiO_Two-K_TwoOB_TwoO _Three
System, SiO_Two-Na_TwoOB_TwoO_ThreeVarious material systems such as systems
Can be used.

In particular, B, Ba, Mg, Al, Ca, P
When the polyvalent metal ion of b, Bi, Cu, Zn, Zr, Nb, Cr, Sr or Ti elutes into the slurry, the anion of the organic polymer compound having an acidic functional group such as a carboxyl group and the polyvalent metal ion Is liable to cause gelation due to ionic cross-linking. Therefore, it is of great significance that, according to the present invention, a compound having an amide structure is contained in the slurry and the gelation can be effectively suppressed.

It is preferable that the slurry for the ceramic green sheet contains crystallized glass powder or a mixed powder of glass and ceramic. This makes it possible to sinter the ceramic green sheet at a low temperature. By sintering the ceramic green sheet at a low temperature in this way, a low-melting metal such as silver or copper having a small specific resistance for the wiring conductor can be obtained. This is because a conductor containing such a low melting point metal can be used, and simultaneous sintering with a conductor containing such a low melting point metal is possible.

The ceramic green sheet according to the present invention includes (1) an insulating ceramic powder, an organic binder, and a slurry obtained by mixing an inorganic powder such as a glass powder; Ceramic green sheets, (2) magnetic ceramic green sheets formed by mixing a slurry obtained by mixing a magnetic ceramic powder, an organic binder, and an inorganic powder such as a glass powder into a sheet, or (3) a dielectric ceramic green sheet. There are various types of dielectric ceramic green sheets and the like, each of which is formed by molding a slurry obtained by mixing a body ceramic powder, an organic binder, and an inorganic powder such as a glass powder into a sheet, and the like. As a ceramic powder having such various characteristics, a conventionally known ceramic material for a ceramic green sheet can be used.

The organic binder contained in the paste composition or the slurry for the ceramic green sheet according to the present invention may further comprise an organic polymer as an additional component as long as it contains an organic polymer compound having an acidic functional group. Or an organic solvent or the like. As the organic polymer, polyvinyl alcohol, polyvinyl butyral, a methacrylate polymer, an acrylate polymer, an acrylate-methacrylate copolymer, or the like can be used.

It is desirable that the slurry for the paste composition or the ceramic green sheet according to the present invention contains a photosensitive organic component. by this,
A photosensitive paste composition or a photosensitive ceramic green sheet can be provided.

Since the photosensitive paste composition thus constituted contains a compound having an amide structure, sufficient gelation is obtained in both the paste state before coating and the coating state after coating and drying. In addition to improving the stability, the developing process in the photolithography technology can be stably performed, and the functional material film such as a conductor film having various patterns of fine and thick films can be adhered to the substrate with good adhesion. It can be formed in a state.

According to the photosensitive ceramic green sheet, it is possible to suppress the gelling of the slurry for forming the ceramic green sheet and obtain a ceramic green sheet excellent in dispersibility and workability. Fine and high-precision via holes for via holes can be easily formed in the sheet by photolithography.

The photosensitive organic component is a conventionally known photopolymerizable or photo-modified compound, and includes, for example, (1) a monomer or oligomer having a reactive functional group such as an unsaturated group; A mixture with a photoradical generator such as an aromatic carbonyl compound, (2) a so-called diazo resin such as a condensate of an aromatic bisazide and formaldehyde, (3)
Mixtures of an addition polymerizable compound such as an epoxy compound and a photoacid generator such as a diallyl iodonium salt, and (4) a naphthoquinonediazide compound.

Among these, particularly preferred is a mixture of a monomer or oligomer having a reactive functional group such as an unsaturated group and a photo radical generator such as an aromatic carbonyl compound.

Examples of the reactive functional group-containing monomer / oligomer include hexanediol triacrylate, tripropylene glycol triacrylate, trimethylolpropane triacrylate, stearyl acrylate, tetrahydrofurfuryl acrylate, lauryl acrylate, 2-phenoxyethyl acrylate, Decyl acrylate, isooctyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated nonylphenol acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate,
Tetraethylene glycol diacrylate, triethylene glycol diacrylate, ethoxylated bisphenol A diacrylate, propoxylated neopentyl glycol diacrylate, tris (2-hydroxyethyl)
Isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hydroxypentaacrylate,
Ethoxylated pentaerythritol tetraacrylate,
Tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexane Diol dimethacrylate, neopentyl glycol dimethacrylate, 1,
Examples include 3-butylene glycol dimethacrylate, ethoxylated bisphenol A dimethacrylate, and trimethylolpropane trimethacrylate.

Examples of the photo-radical generator include benzyl, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-benzoyl-4'-methyldiphenyl sulfide, and benzyl dimethyl. Ketal, 2-n-butoxy-
4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, 2-dimethylaminoethylbenzoate, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate 3,3′-dimethyl-4-methoxybenzophenone, 2,4-dimethylthioxanthone, 1-
(4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-
Diphenylethan-1-one, hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-
Phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4
-(Methylthio) phenyl] -2-morpholinopropan-1-one, methylbenzoyl formate, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -1-butanone, bis (2,6-dimethoxybenzoyl) -2,4,
4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and the like.

The organic polymer contained in the organic binder in the paste composition according to the present invention or the organic binder in the slurry for the ceramic green sheet is an acrylic copolymer having a carboxyl group in a side chain. Desirably. Such an organic polymer compound is also useful as a photosensitive organic binder, and is easily dissolved in an alkaline or aqueous developer, so that the paste film or the ceramic green sheet can be easily developed. Since the development accuracy is improved, a finer pattern and a through hole for a via hole can be formed.

When the organic high molecular compound is an acrylic copolymer having a carboxyl group in the side chain, the anion of the copolymer and the polyvalent metal ion eluted into the solution undergo ionic crosslinking. And a three-dimensional network is easily formed. Therefore, according to the present invention, it is of great significance that a compound having an amide structure can be contained in such a system to effectively suppress the gelation.

The acrylic copolymer having a carboxyl group in the side chain can be produced, for example, by copolymerizing an unsaturated carboxylic acid and an ethylenically unsaturated compound.

As the above-mentioned unsaturated carboxylic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, vinyl acetic acid and anhydrides thereof can be used.

On the other hand, as the ethylenically unsaturated compound,
Acrylic esters such as methyl acrylate and ethyl acrylate, methacrylic esters such as methyl methacrylate and ethyl methacrylate, and fumaric esters such as monoethyl fumarate can be used.

The acrylic copolymer may have an unsaturated bond introduced in the following form. (1) To the carboxyl group on the side chain of the acrylic copolymer,
An acrylic monomer having a functional group such as an epoxy group capable of reacting with the monomer is added. (2) After reacting an unsaturated monocarboxylic acid with an acrylic copolymer in which an epoxy group is introduced instead of a carboxyl group in a side chain, a saturated or unsaturated polycarboxylic anhydride is further introduced. thing.

In the paste composition or slurry for ceramic green sheets according to the present invention, a monol compound having only one hydroxyl group can be further added. In the paste composition or slurry according to the present invention, when a monol compound is added instead of the compound having an amide structure, gelation is prevented for a certain period of time. By adding a compound having a structure, the period in which gelation can be prevented can be drastically extended, and a highly uniform paste composition or slurry can be obtained.

Examples of the monol compound include 1-octyl alcohol, 2-octyl alcohol, nonyl alcohol, decyl alcohol, 1-methylcyclohexanol, trimethylcyclohexanol, ethylene glycol monoacetate, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether,
Diethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monovinyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, ethylene glycol isoamyl ether, ethylene glycol phenyl ether, ethylene glycol benzyl ether , Trimethylhexanol, tetrahydrofurfuryl alcohol, cresol, butyl lactate, benzyl alcohol,
Hydroxyethyl acrylate, phenethyl alcohol, mercaptobutanol, hydroxyethyl methacrylate, hydroxyethylpiperazine, cyclohexanone oxime, hydroxymethoxyallylbenzene, hydroxymethoxybenzaldehyde, hydroxymethylpiperazine, hydroxypropionitrile, hydroxyacetonaphthone, hydroxybenzaldehyde, hydroxyacetophenone, Hydroxybenzimidazole, phenylphenol, hydroxybenzoic acid, hydroxybenzophenone, benzoin, thymol, hydroxymethoxybenzoic acid, hydroxymethylbenzoic acid, hydroxymethylpyrone, hydroxynaphthoic acid, hydroxynaphthoquinone, hydroxynorbornenedicarboximide, hydroxypheni Acid, hydroxyphenyl glycine, hydroxyphthalimide, hydroxypivalic acid neopentyl glycol ester, hydroxy propiophenone, hydroxystearic acid, hydroxy succinic acid imide, hydroxy toluyl acid, and pentaerythritol diacrylate monostearate, and the like.

Further, in the paste composition or slurry according to the present invention, an anion-adsorbing substance having a property of adsorbing anions of the organic polymer compound can be further added. In the paste composition or slurry according to the present invention, even when an anion-adsorbing substance is added instead of the compound having an amide structure, gelation is prevented for a certain period of time.
By adding a compound having an amide structure, the period during which gelation can be prevented can be drastically extended, and a highly uniform paste composition or slurry can be obtained.

The anion-adsorbing substance has an average particle size of 0.1.
It is desirable that the fine particles have a particle size of 01 to 50 μm. When the particles have such a particle size, the anion-adsorbing substance can efficiently adsorb the anion of the organic polymer compound.

The anion-adsorbing substance may be in the form of inorganic fine particles or organic fine particles.

As the above-mentioned inorganic fine particles, hydroxyapatite, hydrotalcite, zirconium phosphate, antimony hydrate and the like are preferred.

As the organic fine particles, an anion exchange resin or the like can be used. For example, (1) a copolymer of divinylbenzene and acrylate, methacrylate or acrylonitrile is used as a base material for primary, secondary, 3
Primary or secondary, tertiary or quaternary amino groups based on a copolymer of trivinylbenzene and acrylate, methacrylate or acrylonitrile as a parent, wherein a primary or secondary amino group is introduced as an ion exchange group; Wherein (3) a copolymer of trimethylolpropane trimethacrylate and acrylate, methacrylate or acrylonitrile is used as a base,
A polymer having a primary, secondary, tertiary or quaternary amino group introduced as an ion exchange group, and (4) a copolymer of ethylene glycol dimethacrylate and acrylate, methacrylate or acrylonitrile,
And a secondary, tertiary or quaternary amino group introduced as an ion exchange group.

Further, a thixotropic agent can be further added to the paste composition or slurry according to the present invention. In the paste composition or slurry according to the present invention, when a thixotropic agent is added instead of the compound having an amide structure, gelation is prevented for a certain period of time. By adding the compound, the period in which gelation can be prevented can be drastically extended, and a highly uniform paste composition or slurry can be obtained.

The content of the above-mentioned thixotropic agent is preferably 0.1 to the total amount of the photosensitive paste composition or slurry.
001 to 30% by weight, more preferably 0.1 to 10% by weight. If the amount is less than 0.001% by weight, it is difficult to sufficiently suppress the gelation, while if the amount exceeds 30% by weight, the viscosity of the paste is too high to use.

As the thixotropic agent, those generally referred to as “thickening / sagging / settling preventive”, “sagging / settling preventive” or “pigment wetting / dispersing / settling preventive” can be used. Can be used.

Examples of the “thickening / sagging / settling preventive” include:
Vegetable polymerized oil, polyether / ester type surfactant,
Examples include hydrogenated castor oil, a mixture of hydrogenated castor oil and amide, and fatty acid amide wax.

[0093] Further, as the "sagging / settling preventing agent",
Special fatty acid type, sulfate type / anionic type surfactant, polyethylene oxide type, a mixture of polyethylene oxide type and amide type and the like can be used.

Examples of the "pigment wetting / dispersion / precipitation inhibitor" include fatty acid-based polycarboxylic acids, amine salts of high molecular polyesters, polyether / ester type anionic surfactants, and long-chain amines of high molecular weight polycarboxylic acids. Salts, salts of long-chain polyaminoamides and high-molecular-weight polyesters, salts of long-chain polyaminoamides and phosphoric acid, specially-modified polyamide-based, phosphate-based surfactants, and amide amine salts of high-molecular-weight polyester acids can be used.

The paste composition or slurry according to the present invention may further contain, if necessary, a storage stabilizer such as a polymerization inhibitor, an antioxidant, a dye, a pigment, an antifoaming agent, a surfactant, and an ultraviolet ray. An absorbent or the like may be appropriately added.

The paste composition or slurry according to the present invention can be used for producing various electronic parts such as circuit boards such as multilayer ceramic substrates and chip parts such as multilayer circuit elements. Electronic components for high frequency circuits such as chip capacitors and chip LC filters, VCO (Voltage Controlled Oscillator) and PL
It can be used to manufacture multilayer ceramic substrates for high frequency modules such as L (Phase Locked Loop), piezoelectric components, and the like.

Next, the paste composition according to the present invention comprises:
Some embodiments applied for manufacturing the electronic component as described above will be described more specifically.

When the paste composition according to the present invention is applied to an appropriate substrate by a method such as a screen printing method, a paste film can be formed in a desired pattern.

In this case, when the photosensitive paste composition is used, the composition is applied to an appropriate substrate by a method such as a screen printing method or a spin coating method, dried, exposed and developed. , For the paste film,
It is possible to give a fine pattern which cannot be obtained by the conventional screen printing method, for example, has a width and a pitch of 50 μm or less. In addition, the above-mentioned drying is specifically, 40
１００100 ° C. for 10 minutes to 2 hours.

Therefore, for example, a paste film of the paste composition according to the present invention is formed on a ceramic green sheet in a desired pattern as described above, and then subjected to a heat treatment such as firing to obtain a thick film. An electronic component, such as a circuit board or a circuit element, including the functional material film constituted by the above can be manufactured.

In this case, a paste film according to the present invention is applied on a support such as a polyethylene terephthalate (PET) film in a desired pattern to form a paste film. A method of performing thermal transfer on a sheet may be employed.

In forming a paste film of the paste composition according to the present invention on a ceramic green sheet or a support in a desired pattern,
As described above, when a photosensitive paste composition is used, it is applied by a method such as a screen printing method or a spin coating method, and then dried and then exposed and developed to form a desired pattern. What is necessary is just to give to a paste film.

As described above, in particular, when the paste composition according to the present invention is used as the photosensitive paste composition, the development processing in the photolithography technique can be stably performed. In this case, a wiring conductor essential for the semiconductor device can be formed in a fine and thick film, and a small-sized circuit board or circuit element excellent in high-frequency characteristics can be manufactured. Accordingly, it is possible to sufficiently cope with high-density and high-speed signals of high-frequency chip electronic components such as chip inductors and chip multilayer capacitors.

The above-mentioned ceramic green sheet for forming a paste film of the paste composition according to the present invention is usually formed by forming a slurry obtained by mixing a ceramic powder and an organic vehicle into a sheet. Further, glass powder may be further mixed.

Examples of the above ceramic powder include insulating ceramic powder such as Al ₂ O ₃ and BaTiO 3.
Ferrite powders such as dielectric ceramic powders such as ₃ , nickel zinc ferrite, nickel zinc copper ferrite, etc.,
RuO ₂ , Pb ₂ Ru ₂ O ₇ , Bi ₂ Ru ₂ O ₇ , Mn
Conductive ceramic powder such as Co / Ni composite oxide,
A piezoelectric ceramic powder such as PZT can be appropriately selected and used.

As will be described in detail in an embodiment relating to a method of manufacturing a multilayer ceramic substrate described later,
By mixing a photosensitive organic component into an organic vehicle contained in a slurry for obtaining a ceramic green sheet, a photosensitive ceramic green sheet is used, and a fine via hole is formed by photolithography technology. May be formed in advance.

Next, a preferred embodiment of a method for manufacturing a multilayer ceramic substrate according to the present invention will be described with reference to FIG.

The multilayer ceramic substrate 1 shown in FIG. 1 has insulating layers 2, 3, 4, 5, 6 and 7 and dielectric layers 8 and 9
And a laminated structure comprising: The multilayer ceramic substrate 1 also has various internal conductor films 10 and via-hole conductors 11 formed inside, and some external conductor films 12 formed on the outer surface.

With the specific internal conductor film 10 and via hole conductor 11 described above, a capacitor element C, a coil element L, a strip line, and the like are formed inside the multilayer ceramic substrate 1.

A chip component 13 such as a chip capacitor, a thick-film resistor 14, a semiconductor IC 15 and the like are provided on one main surface of the multilayer ceramic substrate 1. Via-hole conductor 11
And is electrically connected to a specific internal conductor film 10 through.

The multilayer ceramic substrate 1 is, for example,
It can be manufactured as follows.

First, a glass powder and a ceramic powder, an organic polymer compound having an acidic functional group and an organic binder containing a photosensitive organic component, and a compound having an amide structure are mixed to provide a photosensitive insulating material. A slurry for a ceramic green sheet is prepared. Similarly, a slurry for a dielectric ceramic green sheet provided with photosensitivity is prepared.

Next, each of the obtained slurries is formed into a sheet by a doctor blade method or the like.
To produce a photosensitive insulating ceramic green sheet and a photosensitive dielectric ceramic green sheet.

Next, a conductor paste serving as the internal conductor film 10 for forming the capacitor element C, the coil element L and the like is printed in a predetermined pattern on a specific one of the ceramic green sheets thus produced. And so on.

Also, via hole conductors 11 are provided for specific ceramic green sheets. Therefore, first, for example, a diameter of 50 μm
After exposing the pattern for the via hole through hole, and then performing a development process with an alkaline aqueous solution to remove unnecessary portions, the via hole through hole is formed, and then the conductor is inserted into the via hole through hole. Filling the paste is performed.

Next, a plurality of ceramic green sheets including the ceramic green sheet provided with the internal conductor film 10 and / or the via-hole conductor 11 are stacked, pressed and fired at a predetermined temperature.

Next, after the external conductor film 12 is formed in a predetermined pattern, the chip component 13, the semiconductor IC 1
5 is mounted and the thick film resistor 14 is printed, whereby the target multilayer ceramic substrate 1 is completed.

According to the method for manufacturing the multilayer ceramic substrate 1 described above, the insulator layers 2 to 7 are formed by the photosensitive insulator ceramic green sheets according to the present invention. 9 can be formed by the photosensitive insulator ceramic green sheets according to the present invention.

Therefore, fine via-hole conductors 11 can be easily formed with high precision in these insulator layers 2 to 7 and dielectric layers 8 and 9.

That is, according to the photosensitive ceramic green sheet of the present invention, there is little change in viscosity over time due to gelation and excellent workability, so that printing bleeding and the like due to viscosity deterioration are suppressed. A conductor paste film for the internal conductor film 10 can be formed with high precision, and extremely fine via-holes having a diameter of, for example, less than 150 μm, particularly 50 μm or less can be formed with high precision. In addition, since the components of the slurry are uniformly dispersed, after sintering, the insulating layers 2 to 7 and the dielectric layers 8 and 9 having high density and excellent strength can be obtained.

Therefore, the obtained multilayer ceramic substrate 1
In this case, the wiring conductors such as the internal conductor film 10 and the via-hole conductor 11 can be arranged with high density and high accuracy, and excellent mechanical and electrical characteristics can be realized.

In the above-described manufacturing method, the photosensitive ceramic green sheets according to the present invention were used to form the insulator layers 2 to 7 and the dielectric layers 8 and 9. One of the body layers may be formed of a photosensitive ceramic green sheet, and the other may be formed of a non-photosensitive ceramic green sheet.

In the method for manufacturing a multilayer ceramic substrate as described above, a multilayer ceramic substrate having a magnetic layer is obtained by using a magnetic ceramic green sheet containing a magnetic ceramic powder prepared according to the present invention. You may. For example, in FIG. 1, when the insulator layer 5 is replaced with a magnetic layer, the inductance of the coil element L can be further increased by the coil-patterned internal conductor film 10 formed in association with the magnetic layer. it can.

Further, in the above-described method for manufacturing the multilayer ceramic substrate 1, the inner conductor film 10 and the outer conductor film 12
For forming the paste, the above-described paste composition according to the present invention may be used. That is, a paste film made of the paste composition according to the present invention is formed by the method described above.
If a desired pattern is formed on each ceramic green sheet, this paste film gives the internal conductor film 10 in the multilayer ceramic substrate 1. Further, after firing, if a paste film made of the paste composition according to the present invention is formed on the surface of the multilayer ceramic substrate 1 in a desired pattern by the above-described method,
The external conductor film 12 is provided by the paste film.

The method for manufacturing a multilayer ceramic substrate as described above can be applied to a method for manufacturing an electronic component such as a multilayer circuit element.

Further, in order to manufacture a multilayer ceramic substrate or a multilayer circuit element, as described above, instead of a method of laminating a plurality of ceramic green sheets on which desired internal conductor films 10 and via-hole conductors 11 are formed, as described above. After forming a conductive film on a substrate, a support, or the like using the paste composition according to the present invention, a mixture containing an appropriate functional material and an organic binder is applied, and if necessary, a via hole is formed. By repeatedly forming a conductor with the paste composition according to the present invention, a laminated structure is produced, and a heat treatment such as firing is performed on the laminated structure to produce a multilayer circuit board or a multilayer circuit element. You can also.

As the above-mentioned functional material, a ceramic powder, a material obtained by adding a glass powder to the powder, or a powder made of a conductive metal such as copper or silver can be used in some cases.

Hereinafter, the structure and effects of the present invention will be described more specifically with reference to experimental examples.

[0129]

[Experimental Example 1] First, in Experimental Example 1, a paste composition according to the present invention will be described.

The paste compositions according to Examples 1 to 13 below were prepared.

Example 1 After mixing the various components of the following composition and amount, the mixture was kneaded with a three-roll mill to obtain a photosensitive paste composition.

<Organic Binder> A copolymer having a copolymerization ratio of methacrylic acid / methyl methacrylate of 25/75 by weight (weight average molecular weight = 50,
000): 2.0 g <Conductive metal powder> Copper powder (average particle diameter 3 μm): 15.0 g <Reactive functional group-containing monomer> Trimethylolpropane triacrylate: 1.0 g <Photopolymerization initiator> 2-methyl -1- [4- (methylthio) phenyl] -2
-Morpholinopropan-1-one: 0.4 g 2,4-diethylthioxanthone: 0.1 g <organic solvent> tyl carbitol acetate: 4.0 g <compound having an amide structure> stearamide: 0.01 g <ultraviolet light Absorbent> Azo-based red pigment: 0.1 g Example 2 A photosensitive paste composition was prepared in the same manner as in Example 1 except that stearamide was not added.

Example 3 Phosphoric acid 0.1 instead of 0.01 g of stearamide
A photosensitive paste composition was prepared in the same manner as in Example 1 except that g was added.

Example 4 The procedure of Example 1 was repeated, except that 0.02 g of benzotriazole was added instead of 0.01 g of stearamide.
A photosensitive paste composition was prepared.

Example 5 1.0 g of acetic acid instead of 0.01 g of stearamide
A photosensitive paste composition was prepared in the same manner as in Example 1 except that was added.

Example 6 A photosensitive paste composition was prepared in the same manner as in Example 1 except that 3-methoxy-3-methylbutanol was used instead of stearic acid amide.

Example 7 Instead of 15.0 g of copper powder, 12.0 g of silver powder (average particle size: 3 μm) was used as the conductive metal powder, and SiO ₂ —PbO—B ₂ O ₃ glass powder (borane) was used as glass powder. A photosensitive paste composition was prepared in the same manner as in Example 1, except that 0.9 g of an acid content of 17% by weight and an average particle size of 3 μm was added.

Example 8 A photosensitive paste composition was prepared in the same manner as in Example 7, except that no stearamide was added.

Example 9 Phosphoric acid 0.1 instead of 0.01 g of stearic acid amide
A photosensitive paste composition was prepared in the same manner as in Example 7 except that g was added.

Example 10 The procedure of Example 7 was repeated, except that 0.02 g of benzotriazole was added instead of 0.01 g of stearamide.
A photosensitive paste composition was prepared.

Example 11 1.0 g of acetic acid instead of 0.01 g of stearamide
A photosensitive paste composition was prepared in the same manner as in Example 7, except that was added.

Example 12 A photosensitive paste composition was prepared in the same manner as in Example 7 except that 3-methoxy-3-methylbutanol was used instead of stearamide.

Example 13 Without adding conductive metal powder, SiO ₂ was used as glass powder.
-PbO-B ₂ O ₃ based glass powder (boric acid content 17 wt%, average particle size 3 [mu] m) SiO in place of 0.9 g ₂ -
K ₂ O-B ₂ O ₃ based glass powder (boric acid content 17%, average particle size 3 [mu] m), except that the addition of 5.0 g, all Example 7
In the same manner as in the above, a photosensitive paste composition was prepared.

Example 14 A photosensitive paste composition was prepared in the same manner as in Example 13 except that stearamide was not added.

Example 15 Phosphoric acid 0.1 instead of 0.01 g of stearamide
A photosensitive paste composition was prepared in the same manner as in Example 13 except that g was added.

Example 16 A photosensitive paste composition was prepared in the same manner as in Example 13 except that 0.02 g of benzotriazole was added instead of 0.01 g of stearamide.

Example 17 1.0 g of acetic acid instead of 0.01 g of stearamide
A photosensitive paste composition was prepared in the same manner as in Example 13 except that was added.

Example 18 A photosensitive paste composition was prepared in the same manner as in Example 13, except that 3-methoxy-3-methylbutanol was used instead of stearamide.

Example 19 A photosensitive paste composition was prepared in the same manner as in Example 13, except that 5.0 g of nickel zinc copper ferrite was added as an inorganic powder without adding glass powder.

Example 20 A photosensitive paste composition was prepared in the same manner as in Example 19 except that no stearamide was added.

Example 21 Phosphoric acid 0.1 instead of 0.01 g of stearamide
A photosensitive paste composition was prepared in the same manner as in Example 19 except that g was added.

Example 22 A photosensitive paste composition was prepared in the same manner as in Example 19 except that 0.02 g of benzotriazole was added instead of 0.01 g of stearamide.

Example 23 1.0 g of acetic acid instead of 0.01 g of stearamide
A photosensitive paste composition was prepared in the same manner as in Example 19 except that was added.

Example 24 A photosensitive paste composition was prepared in the same manner as in Example 19 except that 3-methoxy-3-methylbutanol was used instead of stearamide.

Example 25 Instead of 5.0 g of nickel zinc copper ferrite, 3.0 g of SiO ₂ —PbO—B ₂ O ₃ based glass powder (borate content: 17%) and RuO ₂ (resistor) were used as the inorganic powder.
A photosensitive paste composition was prepared in the same manner as in Example 19, except that 2.0 g of the mixture was added.

Example 26 A photosensitive paste composition was prepared in the same manner as in Example 25 except that stearamide was not added.

Example 27 Phosphoric acid 0.1 instead of 0.01 g of stearamide
A photosensitive paste composition was prepared in the same manner as in Example 25 except that g was added.

Example 28 A photosensitive paste composition was prepared in the same manner as in Example 25 except that 0.02 g of benzotriazole was added instead of 0.01 g of stearamide.

Example 29 1.0 g of acetic acid instead of 0.01 g of stearamide
A photosensitive paste composition was prepared in the same manner as in Example 25 except that was added.

Example 30 A photosensitive paste composition was prepared in the same manner as in Example 25 except that 3-methoxy-3-methylbutanol was used instead of stearamide.

Next, each of the photosensitive paste compositions of Examples 1 and 7 was applied on an alumina insulating substrate by a spin coater, and each of them was dried at 100 ° C. for 1 hour to form a 20 μm thick coating film. Was formed. Next, after the obtained coating film was left for 24 hours, an exposure treatment was performed. Here, line / space (L / S) = 20/20 (μm)
Through a mask on which the pattern (1) was drawn, a light of a high-pressure mercury lamp was applied at an exposure of 250 mJ / cm ² . Thereafter, by performing the current processing image with an aqueous solution of sodium carbonate, a pattern of L / S = 20/20 (μm) could be obtained. And after degreasing, 900
° C., and calcined in an N ₂ atmosphere, L / S = 10/30 (μ
The conductor pattern of m) could be formed.

Further, the photosensitive paste composition of Example 13 was
According to the same method as in Examples 1 and 7 described above, coating and drying were performed to form a coating film having a thickness of 20 μm. Then, the obtained coating film was left for 24 hours, and then exposed to light.
By developing, L / S = 20/20 (μ
m) was formed. And this is 850 ° C,
By firing in air, an insulator pattern of L / S = 10/30 (μm) was obtained.

Also, the photosensitive paste composition of Example 19 was
According to the same method as in Examples 1 and 7 described above, coating and drying were performed to form a coating film having a thickness of 20 μm. Next, after the obtained coating film was left for 24 hours, an exposure treatment was performed. Here, a light beam of a high-pressure mercury lamp was irradiated at an exposure amount of 250 mJ / cm ² through a mask on which a pattern for a through hole for a via hole having a diameter of 20 μm was drawn. Subsequently, a development treatment using an aqueous solution of sodium carbonate was performed to form a through hole for a via hole having a diameter of 20 μm. Furthermore, the via-hole through-hole was filled with the conductor paste composition, and then fired at 950 ° C. in air to form a via-hole conductor having a diameter of 30 μm.

The photosensitive paste composition of Example 25 was applied on an alumina insulating substrate by a spin coater method, and dried at 100 ° C. for 1 hour to form a 30 μm thick coating film. Next, after the obtained coating film was left for 24 hours, an exposure treatment was performed. Here, light from a high-pressure mercury lamp was applied at an exposure of 250 mJ / cm ² through a mask on which a 30 μm square pattern was drawn.
Thereafter, a cubic structure having a size of 30 μm × 30 μm × 30 μm was obtained by performing development processing with an aqueous solution of sodium carbonate. Then, this was fired at 850 ° C. in the air to obtain a resistor of 20 μm × 20 μm × 20 μm. When the electrical resistance of this resistor was measured, it was 16
kΩ.

The photosensitive paste compositions of Examples 1, 7, 13, 19, and 25 were subjected to a temperature of 20 ° C.
In the air, immediately after preparation, 1 day, 3 days, 1 week, 1 month, 2 months, 3 months, 4 months, 5 months and 6 months Was evaluated.
As a result, the photosensitive paste compositions according to these examples were not gelled at any time. That is,
Immediately after fabrication, 1 day, 3 days, 1 week, 1 month, 2 months, 3 months, 4 months, 5 months, and 6 months, apply on the insulating substrate by a spin coater And a pattern can be formed by photolithography.

On the other hand, Examples 2 to 6, Examples 8 to 12, and Examples 14 to 1
8, the storage stability of each of the photosensitive paste compositions of Examples 20 to 24 and Examples 26 to 30 was evaluated under the same conditions as described above.

The results of these evaluations are shown in Table 1 below. In addition, "o" in Table 1 means that the photosensitive paste composition was not gelled and was in a coatable state. In addition, “x” means that the photosensitive paste composition was gelled and was in a state where application was impossible.

[0168]

[Table 1]

From Table 1, Examples 2 to 6, Examples 8 to 12, and Example 14
-18, Examples 20-24, and Examples 26-30,
A photosensitive paste composition containing no compound having an amide structure or a photosensitive paste composition containing an anti-gelling agent other than a compound having an amide structure can prevent gelation immediately after the preparation and have good stability. As shown, Examples 6, 12, 1
It can be seen that gelling began to occur over time except for the photosensitive paste compositions of 8, 24 and 30.

For each of the photosensitive paste compositions of Examples 6, 12 and 18, a pattern formation of L / S = 20/20 (μm) was performed in the same manner as in Examples 1, 7 and 13. Tried. Further, the photosensitive paste composition of Example 24 had a diameter of 20 μm in the same manner as in Example 19.
Of via-hole conductors. Further, for the photosensitive paste composition of Example 30, the production of a resistor of 20 μm × 20 μm × 20 μm was attempted in the same manner as in Example 25. The stability of the coating film of each of the photosensitive paste compositions of Example 6, Example 12, Example 18, Example 24, and Example 30 at the time of development was evaluated.

Table 2 below shows the evaluation results of the photosensitive paste compositions of Examples 6, 12, 12, 18, 24, and 30 described above. Examples 1, 7, 7, 13, 19 and Example 25
Are shown together with the evaluation results of the respective photosensitive paste compositions. In Table 2, “○” means that the unexposed portion was eluted in the developing solution and the pattern was successfully formed. Further, “△” in Table 2 means that although the unexposed portion was partially eluted in the developer, the pattern could not be sufficiently formed, and “×” indicates that the unexposed portion was in the developer. , Which means that pattern formation was not possible.

[0172]

[Table 2]

According to Table 2, according to each of the photosensitive paste compositions according to Examples 1, 7, 13, 13, 19, and 25 containing the compound having an amide structure, the unexposed portion was easily eluted into the developing solution. As a result, it was found that a pattern having excellent shape was formed.

On the other hand, when the anti-gelling agent is 3-methoxy-3-methylbutanol as in Examples 6, 12, 12, 18, and 30, the unexposed area is sufficient for the developing solution. And a pattern having good shape could not be formed. This is due to the fact that 3-methoxy-3-methylbutanol evaporates from the coating film during the drying treatment after the application of the photosensitive paste composition, and the ability to prevent gelation has deteriorated with time. Seem.

Further, paste compositions according to the following Examples 31 to 36 were prepared.

Example 31 The procedure of Example 1 was repeated, except that stearic acid amide was not added, the amount of ethyl carbitol acetate was changed to 1.0 g, and 4.0 g of dipropylene glycol monomethyl ether was added as a monol compound. A photosensitive paste composition was prepared.

Example 32 Example 3 except that 0.01 g of stearamide was added.
In the same manner as in Example 1, a photosensitive paste composition was prepared.

Example 33 Example 1 was repeated except that 0.1 g of hydroxyapatite (average particle size: 5 μm) was added without adding stearamide.
In the same manner as in the above, a photosensitive paste composition was prepared.

Example 34 Example 3 except that 0.01 g of stearamide was added.
In the same manner as in 3, a photosensitive paste composition was prepared.

Example 35 A photosensitive paste composition was prepared in the same manner as in Example 1, except that 0.1 g of a thixotropic agent (Disparon 305, manufactured by Kusumoto Chemicals, hydrogenated castor oil) was added without adding stearic acid amide. Was prepared.

Example 36 Example 3 except that 0.01 g of stearamide was added.
In the same manner as in 5, a photosensitive paste composition was prepared.

As described above, the storage stability of each of the photosensitive paste compositions of Examples 31 to 36 was evaluated. The photosensitive paste composition was stored at 20 ° C. in the air. The evaluation results are shown in Table 3 below. In Table 3, “○” and “×” mean the same as “○” and “×” shown in Table 1, respectively.

[0183]

[Table 3]

From Table 3, it can be seen that even when the photosensitive paste composition does not contain any compound having an amide structure as in Examples 31, 33 and 35, the monool compound, hydroxyapatite, or thixotropic agent is used. If it is contained, gelation was prevented and good stability was exhibited for up to two months from its production, but it can be seen that gelation began to occur over time.

On the other hand, Example 32, Example 34 and Example 3
As shown in 6, each of the photosensitive paste compositions to which stearic acid amide is further added as a compound having an amide structure prevents gelation for up to 12 months from the preparation thereof and exhibits good stability. It can be seen that the paste stability can be dramatically improved by adding a compound having the same.

Also, paste compositions according to the following Examples 37 and 38 were prepared.

Example 37 As a compound having an amide structure, a copolymer of methacrylic acid / methyl methacrylate / acrylic amide (a copolymer having a copolymerization ratio of 25/70/5 by weight) was used in place of 0.01 g of stearamide. Polymer, weight average molecular weight = 5
000) A photosensitive paste composition was prepared in the same manner as in Example 1 except that 0.1 g was added.

Example 38 A photosensitive paste composition was prepared in the same manner as in Example 1 except that 0.1 g of acrylamide was added instead of 0.01 g of stearamide as a compound having an amide structure.

The storage stability of each of the photosensitive paste compositions of Examples 37 and 38 was evaluated as described above. The photosensitive paste composition was stored at 20 ° C. in the air. The evaluation results are shown in Table 4 below together with the evaluation results of the photosensitive paste composition according to Example 1. In Table 4,
“O” and “X” are “○” shown in Table 1, respectively.
And the same as "x".

[0190]

[Table 4]

From Table 4, as shown in Example 37, the photosensitive paste composition containing no monoamide compound as a compound having an amide structure shows good stability by preventing gelation for two months from the preparation. However, it can be seen that gelation began to occur over time.

Also, as in Example 38, the photosensitive paste composition containing no saturated fatty acid amide as a compound having an amide structure exhibited good stability by preventing gelation for three months from its production. However, it can be seen that gelation began to occur over time.

Also, a paste composition according to Example 39 below was prepared.

Example 39 1.0 g of trimethylolpropane triacrylate, 2
-Methyl-1- [4- (methylthio) phenyl] -2-
A paste composition was prepared in the same manner as in Example 1, except that 0.4 g of morpholinopropan-1-one and 0.1 g of 2,4-diethylthioxanthone were not added.

Next, a pattern was formed on the alumina insulating substrate by the screen printing method using the paste composition of Example 39, and this was dried at 100 ° C. for 1 hour.
A pattern of / S = 100/100 (μm) was formed.
Next, after leaving this alumina insulating substrate for 24 hours, it is baked at 900 ° C. in an N ₂ atmosphere to obtain an L / S = 80.
/ 120 (μm) was formed.

Further, with respect to the paste composition of Example 39,
In the air at a temperature of 20 ° C., immediately after production, 1 day, 3 days
One week and one month later, the state of storage at each time point was evaluated.
As a result, the paste composition according to Example 39 was not gelled at any time. That is, it was possible to form a coating film on the substrate by screen printing immediately after the production, 1 day, 3 days, 1 week, and 1 month.

Further, paste compositions according to the following Examples 40 to 44 were prepared.

Example 40 A photosensitive paste composition was prepared in the same manner as in Example 1, except that the amount of stearamide was changed so that the proportion of stearamide in the paste composition was 0.02% by weight. A product was made.

Example 41 A photosensitive paste composition was prepared in the same manner as in Example 1 except that the amount of stearamide was changed so that the proportion of stearamide in the paste composition was 0.03% by weight. A product was made.

Example 42 A photosensitive paste composition was prepared in the same manner as in Example 1 except that the addition amount of stearamide was changed so that the proportion of stearamide in the paste composition was 0.4% by weight. A product was made.

Example 43 A photosensitive paste composition was prepared in the same manner as in Example 1 except that the amount of stearamide was changed so that the proportion of stearamide in the paste composition was 0.5% by weight. A product was made.

Example 44 A photosensitive paste composition was prepared in the same manner as in Example 1, except that the amount of stearamide was changed so that the proportion of stearamide in the paste composition was 0.6% by weight. A product was made.

As described above, the storage stability at each time point immediately after the preparation of the photosensitive paste compositions of Examples 40 to 44, 1 day, 3 days, 1 week, 2 weeks, 3 weeks, and 1 month was determined. evaluated. The storage of the photosensitive paste composition was performed at 20 ° C.
Performed in air. The evaluation results are shown in Table 5 below together with the evaluation results of the photosensitive paste composition according to Example 1. In Table 5, “○” and “×” mean the same as “○” and “×” shown in Table 1, respectively.

[0204]

[Table 5]

Referring to Table 5, as in Examples 41 to 44,
The photosensitive paste composition in which the content of the compound having an amide structure has a content of 0.03% by weight or more can be obtained by any of 1 day, 3 days, 1 week, 2 weeks, 3 weeks, and 1 month immediately after preparation. At this time, the gel was not gelled, and at any of these times, it was possible to perform the coating on the insulating substrate by the spin coater and to form the pattern by the photolithography technique.

On the other hand, as shown in Example 40, the photosensitive paste composition in which the content of the compound having an amide structure is less than 0.03% by weight is shown in Table 5 from the point of gelling two weeks after immediately after the preparation. It shows that the gelation was prevented and good stability was exhibited, but gelation began to occur over time.

Further, uniform applicability of each of the photosensitive paste compositions of Examples 40 to 44 was evaluated. Here, the uniform applicability is
The paste composition was evaluated with uniform applicability when applied on a polyethylene terephthalate film using a doctor blade method.

The evaluation results are shown in Table 6 below together with the evaluation results of the photosensitive paste composition according to Example 1. In Table 6, “○” means that the photosensitive paste composition had a low surface tension and could be uniformly applied. In addition, "x" means that the photosensitive paste composition had a high surface tension and could not be uniformly applied.

[0209]

[Table 6]

From Table 6, according to the photosensitive paste compositions of Examples 1 and 40 to 43 in which the content of the compound having an amide structure is 0.5% by weight or less, the surface tension of the photosensitive paste composition is reduced. It can be seen that the coating was weak and uniform.

On the other hand, as in Example 44, in the case of a photosensitive paste composition in which the content of the compound having an amide structure is more than 0.5% by weight, the surface tension of the photosensitive paste composition is high and the photosensitive paste composition is uniform. It could be seen that the coating could not be applied.

[0212]

[Experimental Example 2] Next, in Experimental Example 2, a ceramic green sheet according to the present invention will be described.

The following Examples 1 to 3 and Comparative Example 1
Each of the ceramic green sheets according to Nos. 1 to 3 was produced.

Example 1 (Insulator ceramic green sheet) 37.3 g of borosilicate glass powder, 24.3 g of alumina powder
5. 9 g, carboxyl group-containing acrylic organic binder
A slurry obtained by mixing 2 g, 3.1 g of ethanol, and 0.01 g of stearamide was formed into a sheet by a doctor blade method, and further dried at 100 ° C. to form an insulating ceramic green sheet having a sheet thickness of 30 μm. I got a sheet.

Example 2 (Dielectric Ceramic Green Sheet) 6.2 g of borosilicate glass powder, 5 barium titanate
A slurry obtained by mixing 6.0 g, 6.2 g of a carboxyl group-containing acrylic organic binder, 3.1 g of ethanol, and 0.01 g of stearamide was formed into a sheet by a doctor blade method, and further 100 ° C.
To obtain a dielectric ceramic green sheet having a sheet thickness of 30 μm.

Example 3 (Magnetic Ceramic Green Sheet) 6.2 g of borosilicate glass powder, 56.0 g of nickel zinc ferrite, 6.2 g of a carboxyl group-containing acrylic organic binder, 3.1 g of ethanol, and stearamide The slurry obtained by mixing 0.01 g was formed into a sheet by a doctor blade method,
To obtain a magnetic ceramic green sheet having a sheet thickness of 30 μm.

Comparative Example 1 (Insulating Ceramic Green Sheet) The same slurry as in Example 1 except that stearic acid amide was not mixed was formed into a sheet by a doctor blade method, and further dried at 100 ° C. to obtain a sheet thickness. 30
A μm insulating ceramic green sheet was obtained.

Comparative Example 2 (Dielectric Ceramic Green Sheet) The same slurry as in Example 2 except that stearic acid amide was not mixed was formed into a sheet by a doctor blade method, and further dried at 100 ° C. to obtain a sheet thickness. 30
A μm dielectric ceramic green sheet was obtained.

Comparative Example 3 (Magnetic Ceramic Green Sheet) The same slurry as in Example 3 except that stearic acid amide was not mixed was formed into a sheet by a doctor blade method, dried at 100 ° C., and dried to a sheet thickness of 30 μm. Was obtained.

Examples 1 to 3 and Comparative Examples 1 to 3
After degreasing each ceramic green sheet, 900
Calcination was carried out in air at ℃. Then, the transverse strength and density of the obtained fired ceramic substrate (sintered body) were measured. The measurement results are shown in Table 7 below.

[0221]

[Table 7]

From Table 7, it can be seen that the insulating ceramic green sheets, dielectric ceramic green sheets and magnetic ceramic green sheets according to Examples 1 to 3 are excellent in the balance between the transverse rupture strength and the density and have a large strength. It can be seen that the characteristics are excellent.

On the other hand, since the various ceramic green sheets according to Comparative Examples 1 to 3 do not contain stearic acid amide, which is a compound having an amide structure, the bending strength is low or the sintered substrate Has become less dense. This means that the slurry for ceramic green sheets became non-uniform due to gelation.

Further, as described below, photosensitive ceramic green sheets according to Examples 4 to 6 and Comparative Examples 4 to 6 provided with photosensitivity were produced.

Example 4 (Photosensitive Insulator Ceramic Green Sheet) Borosilicate glass powder 37.3 g, alumina powder
5. 9 g, carboxyl group-containing acrylic organic binder
2 g, ethanol 3.1 g, trimethylolpropane triacrylate 3.0 g, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1
1.2 g, 2,4-diethylthioxanthone 0.1 g.
A slurry obtained by mixing 3 g and 0.01 g of stearamide was formed into a sheet by a doctor blade method, and further dried at 100 ° C. to obtain a photosensitive insulator ceramic green sheet having a sheet thickness of 30 μm. Was.

Example 5 (Photosensitive dielectric ceramic green sheet) 6.2 g of borosilicate glass powder, barium titanate 5
6.0 g, carboxyl group-containing acrylic organic binder 6.2 g, ethanol 3.1 g, trimethylolpropane triacrylate 3.0 g, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholinopropan-1-one 1.2 g, 2,4-diethylthioxanthone 0.3 g, and a slurry obtained by mixing stearamide 0.01 g were subjected to a doctor blade method. The sheet was formed into a sheet and dried at 100 ° C. to obtain a photosensitive dielectric ceramic green sheet having a sheet thickness of 30 μm.

Example 6 (Photosensitive magnetic ceramic green sheet) 6.2 g of borosilicate glass powder, 56.0 g of nickel zinc ferrite, 6.2 g of acrylic organic binder containing a carboxyl group, 3.1 g of ethanol, trimethylolpropane 3.0 g of triacrylate, 2-methyl-1-
[4- (methylthio) phenyl] -2-morpholinopropan-1-one 1.2 g, 2,4-diethylthioxanthone 0.3 g, and stearamide 0.01
g was mixed and formed into a sheet by a doctor blade method, and dried at 100 ° C. to obtain a photosensitive magnetic ceramic green sheet having a sheet thickness of 30 μm.

Comparative Example 4 (Photosensitive Insulator Ceramic Green Sheet) The same slurry as in Example 4 except that stearic acid amide was not mixed was formed into a sheet by a doctor blade method, and further dried at 100 ° C. Sheet thickness 30
A μm photosensitive insulator ceramic green sheet was obtained.

Comparative Example 5 (Photosensitive Dielectric Ceramic Green Sheet) The same slurry as in Example 5 except that stearic acid amide was not mixed was formed into a sheet by a doctor blade method, and further dried at 100 ° C. Sheet thickness 30
A photosensitive dielectric ceramic green sheet of μm was obtained.

Comparative Example 6 (Photosensitive Magnetic Ceramic Green Sheet) The same slurry as in Example 6 except that stearic acid amide was not mixed was formed into a sheet by a doctor blade method, and dried at 100 ° C. to obtain a sheet. A 30 μm thick photosensitive magnetic ceramic green sheet was obtained.

As described above, Examples 4 to 6 and Comparative Examples 4 to 6
Was irradiated with a light of a high-pressure mercury lamp at an exposure of 250 mJ / cm ² through a mask on which a pattern for a through hole for a via hole having a diameter of 30 μm was drawn. Subsequently, by performing development with an aqueous solution of sodium carbonate, a through hole for a via hole having a diameter of 30 μm was formed. Then, a conductive material is filled into the via-hole and degreased.
Fired in air.

[0232] The bending strength and density of the obtained fired ceramic substrate were measured. The measurement results are shown in Table 8 below.

[0233]

[Table 8]

From Table 8, it can be seen that the insulating ceramic green sheets, dielectric ceramic green sheets and magnetic ceramic green sheets according to Examples 4 to 6 are all excellent in the balance between the bending strength and the density and have the strength. It can be seen that they are large and have excellent substrate characteristics. Table 8
Although not shown, the via hole conductor was also excellent in shape.

On the other hand, since the various ceramic green sheets according to Comparative Examples 4 to 6 do not contain stearic acid amide, which is a compound having an amide structure, the bending strength is low or the density of the sintered substrate is low. Has become smaller. Further, the shape of the via hole was bad. This means that the dispersibility of the slurry for ceramic green sheets was reduced due to gelation and became non-uniform.

As described above, by including a compound having an amide structure such as stearic acid amide in the slurry for ceramic green sheets, gelation does not progress and a uniform slurry can be obtained. Ceramic green sheets made from the slurry show excellent workability with respect to the formation of via-hole conductors and conductor films.Furthermore, cracks do not occur even after firing, and as a result, a mechanically strong ceramic substrate can be obtained. did it.

Further, photosensitive ceramic green sheets according to Examples 7 and 8 were produced using compounds other than stearamide as compounds having an amide structure contained in the slurry in Example 4.

Example 7 In the slurry, as a compound having an amide structure, a copolymer of methacrylic acid / methyl methacrylate / acrylic amide (copolymerization ratio was 25/70 by weight) instead of 0.01 g of stearamide was used. A ceramic green sheet was produced in the same manner as in Example 4 except that 0.1 g of a copolymer (weight ratio: 5,000) was added.

Example 8 In a slurry, as a compound having an amide structure, instead of 0.01 g of stearamide, 0.1 g of acrylic acid amide was used.
A ceramic green sheet was produced in the same manner as in Example 4 except that 1 g was added.

Each of the ceramic green sheets according to Examples 7 and 8 was exposed and developed in the same manner as in Examples 4 to 6 and Comparative Examples 4 to 6 to obtain a diameter of 30 μm. Then, a via material was filled with a conductive material, degreased, and then baked at 900 ° C. in air.

The bending strength and density of the fired ceramic substrate were measured. The measurement results are shown in Table 9 below together with the measurement results of Example 4.

[0242]

[Table 9]

From Table 9, it is found that the ceramic green sheet according to Example 4 is different from Examples 7 and 8 in that the compound having an amide structure includes a monoamide compound and a saturated fatty acid amide stearamide. Therefore, it can be seen that, as compared with the cases of Examples 7 and 8, the balance between the bending strength and the density is excellent, the strength is large, and the substrate characteristics are excellent. Although not shown in Table 9, the via hole conductor was also excellent in shape.

Further, the following ceramic green sheets according to Examples 7 to 9 and Comparative Examples 9 to 11 were produced.

Comparative Example 7 0.5 g of dipropylene glycol monomethyl ether was used as a monol compound without adding stearic acid amide.
A ceramic green sheet was produced in the same manner as in Example 4 except that was added.

Example 9 A ceramic green sheet was prepared in the same manner as in Comparative Example 7, except that 0.01 g of stearamide was added.

Comparative Example 8 A ceramic green sheet was produced in the same manner as in Example 4, except that 0.1 g of hydroxyapatite (average particle size: 5 μm) was added without adding stearic acid amide.

Example 10 A ceramic green sheet was produced in the same manner as in Comparative Example 8, except that 0.01 g of stearamide was added.

Comparative Example 9 A ceramic green sheet was prepared in the same manner as in Example 4, except that 0.1 g of a thixotropic agent (Disparon 305, manufactured by Kusumoto Kasei Co., Ltd .: hydrogenated castor oil) was added without adding stearic acid amide. Was prepared.

Example 11 A ceramic green sheet was produced in the same manner as in Comparative Example 9 except that 0.01 g of stearamide was added.

As described above, Examples 9 to 11 and Comparative Examples 7 to
9 was exposed and developed in the same manner as in Examples 4 to 6 and Comparative Examples 4 to 6 to obtain a diameter of 30 cm.
After forming a through hole for a via hole of μm, and filling the via hole with a conductive material and degreased,
It was fired at 900 ° C. in air.

[0252] The bending strength and density of the obtained fired ceramic substrate were measured. The measurement results are shown in Table 10 below.
Shown in

[0253]

[Table 10]

From Table 10, each of the ceramic green sheets according to Examples 9 to 11 differs from Comparative Examples 7 to 9 in that it contains stearamide as a compound having an amide structure. It can also be seen that the steel sheet also has an excellent balance between the bending strength and the density, has a large strength, and has excellent substrate characteristics. Further, although not shown in Table 10, in the case of Examples 9 to 11, the shape of the via-hole conductor was also excellent.

[0255]

According to the paste composition of the present invention, an organic binder containing an organic polymer compound having an acidic functional group and a polyvalent metal or an inorganic powder containing the compound are mixed. In addition, since a compound having an amide structure is contained, when this is applied to an appropriate substrate, the occurrence of gelation is sufficiently suppressed in both the paste state before application and the coating state after application and drying. In addition, it is possible to easily form a functional material film such as a fine and thick conductive film having high adhesion to the substrate.

In particular, when the paste composition according to the present invention further contains a photosensitive organic component, as described above,
In both the paste state before coating and the coating state after coating and drying, not only the occurrence of gelation can be sufficiently suppressed, but also development processing by photolithography technology can be stably performed, and therefore, extremely With a fine pattern, a thick functional material film can be easily formed with high precision.

According to the electronic component constituted by using the paste composition as described above, the functional material film having a desired pattern is formed on the base by the paste composition according to the present invention. In addition to increasing the adhesion of the functional material film to the substrate, various fine and thick patterns can be applied to the functional material film. An electronic component such as a circuit board that achieves wiring and high-speed signal can be obtained.

In the ceramic green sheet according to the present invention, the slurry for obtaining the ceramic green sheet includes an organic binder containing an organic polymer compound having an acidic functional group, and a ceramic powder and / or a polyvalent metal-containing powder. Since it contains a glass powder and a compound having an amide structure, the gelation of this slurry is suppressed, so that the molding of the ceramic green sheet can be smoothly performed and the obtained ceramic green sheet can be uniformly formed. And it can be excellent in workability.

In particular, according to the photosensitive ceramic green sheet containing a photosensitive organic component, a through hole for a via hole can be formed finely and with high precision by photolithography, and the conductive film can be miniaturized. A ceramic green sheet that can be sufficiently used can be obtained.

According to the electronic component having the ceramic layer formed by firing the ceramic green sheet as described above, the ceramic layer can have high strength and high density.

Further, according to the method for manufacturing a multilayer ceramic substrate according to the present invention, since the above-described ceramic green sheet which is uniform and excellent in workability is used, wiring conductors such as via-hole conductors and conductor films can be used. A multilayer ceramic substrate that can be formed densely and finely and that is mechanically robust and highly reliable can be obtained.

When a photosensitive ceramic green sheet containing a photosensitive organic component is used in the above-described method for manufacturing a multilayer ceramic substrate, it is easier to form via holes for via holes with fine and high precision by photolithography. This can contribute to further increase in the density and miniaturization of the wiring conductor.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a multilayer ceramic substrate 1 obtained by a manufacturing method according to an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Multilayer ceramic substrate 2-7 Insulator layer 8, 9 Dielectric layer 10 Inner conductor film 11 Via hole conductor 12 Outer conductor film

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05K 3/46 H05K 3/46 H C04B 35/00 J F term (Reference) 4G030 AA07 AA08 AA09 AA10 AA16 AA17 AA20 AA22 AA31 AA32. AA43 BB01 CC18 DD02 DD13 DD34 DD45 EE24 EE29 FF18 FF35 GG03 GG04 GG06 GG08 HH11 HH21 5G301 DA02 DA03 DA04 DA05 DA06 DA10 DA11 DA12 DA14 DA22 DA32 DA34 DA42 DA51 DD01

Claims (30)

[Claims] 1. A paste composition comprising: an organic binder containing an organic polymer compound having an acidic functional group; an inorganic powder containing a polyvalent metal or a compound thereof; and a compound having an amide structure. 2. The paste composition according to claim 1, wherein the compound having an amide structure is a monoamide compound. 3. The paste composition according to claim 1, wherein the compound having an amide structure is a fatty acid amide. 4. The paste composition according to claim 3, wherein the compound having an amide structure is a saturated fatty acid amide. 5. The paste composition according to claim 1, wherein the compound having an amide structure is contained in the paste composition at 0.03% by weight to 0.5% by weight. 6. The method according to claim 1, further comprising a photosensitive organic component.
6. The paste composition according to any one of claims 1 to 5. 7. The paste composition according to claim 1, wherein the organic polymer compound having an acidic functional group is an acrylic copolymer having a carboxyl group in a side chain. 8. The paste composition according to claim 1, wherein the inorganic powder is a conductive metal powder or a mixture of a conductive metal powder and a glass powder containing a polyvalent metal or a compound thereof. object. 9. The conductive metal powder according to claim 8, wherein the conductive metal powder is a powder containing at least one selected from the group consisting of gold, silver, copper, platinum, aluminum, palladium, nickel, molybdenum and tungsten. Paste composition. 10. The paste composition according to claim 1, wherein the inorganic powder is a glass powder and / or a ceramic powder containing a polyvalent metal or a compound thereof. 11. The paste composition according to claim 1, further comprising a monol compound. 12. An anion-adsorbing substance having a property of adsorbing anions of the organic polymer compound,
The paste composition according to any one of claims 1 to 11. 13. The paste composition according to claim 1, further comprising a thixotropic agent. 14. An electronic component comprising: a base; and a functional material film obtained by applying the paste composition according to claim 1 on the base and then firing the paste. 15. A substrate, and a functional material film obtained by applying the paste composition according to claim 6 on the substrate, patterning the paste composition by using a photolithography technique, and then firing the functional material film. , Electronic components. 16. An electronic component comprising a layer obtained by firing the paste composition according to claim 1. Description: 17. A slurry containing an organic binder containing an organic polymer compound having an acidic functional group, a ceramic powder and / or a glass powder containing a polyvalent metal, and a compound having an amide structure are formed into a sheet shape. The ceramic green sheet obtained by doing. 18. The ceramic green sheet according to claim 17, wherein the compound having an amide structure is a monoamide compound. 19. The ceramic green sheet according to claim 17, wherein the compound having an amide structure is a fatty acid amide. 20. The ceramic green sheet according to claim 19, wherein the compound having an amide structure is a saturated fatty acid amide. 21. The ceramic green sheet according to claim 17, wherein the compound having an amide structure is contained in the slurry in an amount of 0.03% by weight to 0.5% by weight. 22. The ceramic green sheet according to claim 17, wherein the organic polymer compound having an acidic functional group is an acrylic copolymer having a carboxyl group in a side chain. 23. The ceramic powder and / or glass powder is at least one selected from the group consisting of boron, barium, magnesium, aluminum, calcium, lead, bismuth, copper, zinc, zirconium, niobium, chromium, strontium and titanium. The ceramic green sheet according to any one of claims 17 to 22, comprising a polyvalent metal and / or an oxide thereof. 24. The ceramic green sheet according to claim 17, wherein the slurry further contains a photosensitive organic component. 25. The ceramic green sheet according to claim 17, wherein the slurry further contains a monol compound. 26. The ceramic green sheet according to claim 17, wherein the slurry further contains an anion-adsorbing substance having a property of adsorbing anions of the organic polymer compound. 27. The ceramic green sheet according to claim 17, wherein the slurry further contains a thixotropic agent. 28. An electronic component comprising a ceramic layer formed by firing the ceramic green sheet according to claim 17. 29. A step of preparing a plurality of ceramic green sheets according to claim 17, a step of providing a through hole in a specific one of the ceramic green sheets, and a conductive paste in the through hole. Forming a conductive film by applying a conductive paste on the ceramic green sheet so as to be connected to the via-hole conductor; and A method for manufacturing a multilayer ceramic substrate, comprising: a step of forming a green laminate by laminating a plurality of ceramic green sheets including the formed ceramic green sheet; and a step of firing the green laminate. 30. A step of preparing a plurality of ceramic green sheets according to claim 24, a step of providing a through hole in a specific one of the ceramic green sheets by using a photolithography technique, and a conductor in the through hole. Forming a via-hole conductor by applying a paste; forming a conductive film by applying a conductive paste on the ceramic green sheet so as to be connected to the via-hole conductor; Forming a green laminate by laminating a plurality of the ceramic green sheets including the ceramic green sheets on which the ceramic green sheets are formed; and firing the green laminate, a method for manufacturing a multilayer ceramic substrate. .