JP2001264964A - Photosensitive thick film composition, electronic parts and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive thick film composition which is excellent in shelf stability and can stably e developed. SOLUTION: The photosensitive thick film composition comprises (A) a photosensitive organic component containing an organic binder having an acidic functional group, (B) an inorganic component containing polyvalent metal oxides such as borosilicate glass and (C) a polyhydric alcohol having plural alcoholic hydroxyl groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive thick film composition containing a photosensitive organic component and an inorganic component as main components, an electronic component using the photosensitive thick film composition, and a method for manufacturing the electronic component. The present invention relates to an electronic device provided.

[0002]

2. Description of the Related Art In recent years, the performance of various electronic devices such as mobile communication terminal devices and computers has been remarkably improved. In particular, the speed of information processing and the miniaturization of devices have been drastically advanced. . The electronic components supporting such electronic devices are also strictly required to be reduced in size and density, and three-dimensional electrode patterns, miniaturization, and higher precision are being promoted.

Generally, in a laminated electronic component, a via hole is formed to electrically connect between layers. In a laminated electronic component by a so-called thick film printing method, a via hole is formed by: (1) an organic vehicle; Is mixed with a glass powder to prepare an insulating paste. (2) The insulating paste is printed on the base to form a coating film having via holes. (3) Fill the via holes with conductive paste. (4) firing the coating film and the conductor paste; It is formed by such a method.

However, in this type of laminated electronic component, the patterning of the via hole is usually performed by screen printing of an insulating paste. For this reason, in the coating film after the screen printing, bleeding or blurring due to the paste viscosity, the roughness of the screen mesh, or the like is liable to occur, and the formation of via holes having a diameter of about 100 μm was the limit.

On the other hand, for example, Japanese Patent Laid-Open No. 6-283
No. 846 discloses that a photosensitive insulating paste is prepared by adding and mixing a photosensitive organic component such as a photopolymerizable monomer and a photopolymerization initiator to an insulating paste containing glass as a main component. A method is disclosed in which after coating, a desired via hole is formed by exposure processing and development processing. As described above, since the photolithography method using the photosensitive insulating paste is a patterning method using the exposure processing and the development processing, fine via holes can be formed with high precision.

[0006]

In recent years, in a photolithography method using a photosensitive insulating paste, development with water or alkali has been desired in consideration of the environment. An organic binder having an acidic functional group such as a carboxyl group is introduced into the components.

However, as a glass powder, a polyvalent metal oxide having a valence of 2 or more (for example, SiO ₂ -B
i ₂ O ₃ in the case of using the -B ₂ O ₃ based glass), photosensitive solute portion of the insulating paste polyvalent metal ions is eluted, this polyvalent metal ion, an acidic functional group of the organic binder (organic binder Of the photosensitive insulating paste, and the gelation of the photosensitive insulating paste proceeds. When the photosensitive insulating paste is gelled, not only is it difficult to apply the paste, but even if it can be applied, the developing process becomes unstable.

In order to prevent the photosensitive paste from gelling, Japanese Patent Application Laid-Open No. 9-218509 discloses a method of using a phosphorus-containing compound such as phosphoric acid, and Japanese Patent Application Laid-Open No. 9-218508 discloses an azole structure such as benzotriazole. A method of adding each compound is disclosed.
However, these methods only slightly increase the time required for the photosensitive paste to gel, and are not excellent in long-term storage stability.

Japanese Patent Application Laid-Open No. H10-171107 discloses a method in which 3-methyl-3-methoxybutanol is contained in a photosensitive paste. However, 3-methyl-3-methoxybutanol is liable to volatilize from the coating film when the coating film is dried with the photosensitive paste, so that the dried coating film gels,
In particular, during the development, the unexposed portions may not elute in the developer.

The present invention has been made in view of the above-mentioned circumstances, and has as its object to provide a photosensitive organic component containing an organic binder having an acidic functional group and a polyvalent compound having a valence of 2 or more. Provided is a photosensitive thick film composition comprising a mixture with an inorganic component containing a metal compound, which suppresses gelation and can form various patterns such as via holes with high precision and fineness. It is in. Another object of the present invention is to provide a small and highly reliable electronic component having various patterns of fine and high precision, and furthermore, to provide an electronic device which has achieved miniaturization and high reliability. is there.

[0011]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventor has found that a photosensitive organic component containing an organic binder having an acidic functional group and a polyvalent metal compound are contained. It has been found that gelling can be sufficiently suppressed by adding a polyhydric alcohol having a plurality of alcoholic hydroxyl groups to a photosensitive thick film composition containing an inorganic component.

That is, the present invention comprises (A) a photosensitive organic component containing an organic binder having an acidic functional group, (B) an inorganic component containing a polyvalent metal compound, and (C) a plurality of alcoholic hydroxyl groups. And a polyhydric alcohol having the same.

According to the photosensitive thick film composition of the present invention, since it contains a polyhydric alcohol having a plurality of alcoholic hydroxyl groups, it can be used in any of a paste state before coating and a coating state after coating and drying. Also, the gelation can be sufficiently suppressed, and various patterns such as via holes can be formed finely and with high precision.

This is because the alcoholic hydroxyl group (—OH) in the polyhydric alcohol has a remarkably strong bond with the polyvalent metal ion as compared with the acidic functional group (eg, carboxyl group) of the organic binder. The polyvalent metal ion eluted in the solution portion of the photosensitive thick film composition reacts with the polyhydric alcohol prior to the anion of the organic binder to form an ionic cross-link between the anion of the organic binder and the polyvalent metal ion, thereby causing the ionic crosslinking. This is due to preventing formation of a dimensional network.

The present invention also provides an electronic component comprising a layer obtained by firing the photosensitive thick film composition of the present invention, and further provides an electronic device provided with the electronic component. is there.

That is, according to the electronic component of the present invention, the insulator layer, the dielectric layer, the resistor layer, the magnetic layer and the like can be patterned finely and with high precision based on the photolithography method. In addition, small and highly reliable electronic components having various patterns with high precision can be obtained.
An electronic device provided with this can be downsized and highly reliable.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the photosensitive thick film composition of the present invention will be described in more detail.

In the photosensitive thick film composition of the present invention, polyhydric alcohols include methylene glycol, ethylene glycol, propylene glycol, butylene glycol, pentamethylene glycol, hexamethylene glycol, heptanediol, octanediol, nonanediol, and decane. Diol, diethylene glycol, dipropylene glycol, glycerin, butanetriol,
Aliphatic polyhydric alcohols such as pentanetriol, hexanetriol, heptanetriol, butanetetrol, and glycitol; carboxyl-containing polyhydric alcohols such as gluconic acid; aromatic polyhydric alcohols such as guaiacol; and low molecular weight polyvinyl alcohol Polymeric polyhydric alcohols and the like can be mentioned.

In particular, the polyhydric alcohol is preferably one having two or more and six or less alcoholic hydroxyl groups in one molecule, that is, a dihydric to hexahydric alcohol. Propylene glycol, trimethylene glycol, butylene glycol, tetramethylene glycol, pentamethylene glycol, butenediol, hexamethylene glycol, heptanediol, octanediol, nonanediol,
Decanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, etc., trihydric alcohols such as glycerin, hexanetriol, heptanetriol, etc., quaternary alcohols such as threitol, erythritol, etc. Hexahydric alcohols such as xylitol, ribitol and adonitol include glucitol, mannitol, iditol, talitol, galactitol, malitol and the like. In addition, perseitol, bolemitol, etc. can also be used as a heptavalent alcohol.

Glucitol, which is a hexahydric alcohol, easily forms a complex with the polyvalent metal ion contained in the polyvalent metal compound in the inorganic component, and the acidic functional group of the organic binder is bonded to the polyvalent metal ion. This is particularly desirable because it sufficiently suppresses the occurrence. Further, if the polyhydric alcohol completely disappears before the exposure / development and at the time of the drying treatment, the ability to prevent gelation of the dried coating film is reduced, so that stable development treatment cannot be performed. Therefore, the polyhydric alcohol should have a boiling point of 17 to leave a slight amount of polyhydric alcohol in the dried coating film and to perform stable development.
It is desirable that the temperature is 8 ° C. or higher. A polyhydric alcohol having a boiling point of 178 ° C. or higher or a solid at room temperature can be a useful additive (gelling inhibitor) from that point as well.

In the photosensitive thick film composition of the present invention, when the polyhydric alcohol is liquid at room temperature, the polyhydric alcohol is contained in a weight ratio of 0.1 to 5 times the inorganic component. It is desirable to have been. If the ratio is less than 0.1 times, it is difficult to sufficiently prevent gelation. On the other hand, when the ratio exceeds 5 times, the viscosity of the photosensitive thick film composition decreases, and the coating property may be deteriorated.

Alternatively, when the polyhydric alcohol is solid at room temperature, it preferably occupies 0.01% by weight or more and 20% by weight or less of the total amount of the polyhydric alcohol and the inorganic component. . If the proportion is less than 0.01% by weight, it is difficult to sufficiently prevent gelation. On the other hand, when the proportion exceeds 20% by weight, the viscosity of the photosensitive thick film composition increases, and its preparation and coating film formation become difficult.

In the photosensitive thick film composition of the present invention, it is desirable that the inorganic component accounts for 30% or more and 90% or less in volume fraction. If the volume fraction is less than 30%, the volume shrinkage during firing may increase. On the other hand, when the volume fraction exceeds 90%, the strength of the coating film may decrease. In the present invention, the volume fraction of the inorganic component is represented by (volume of the inorganic component of the photosensitive thick film composition) /
(Volume of the solid content of the photosensitive thick film composition). Here, the solid content of the photosensitive thick film composition is a component that does not disappear by drying before exposure and development, and includes an organic binder in addition to an inorganic component and a conductive metal component. Further, when a solid alcohol at room temperature is selected as the polyhydric alcohol, it does not disappear by ordinary drying treatment, which corresponds to this. Further, the volume fraction of the conductive metal component has the same meaning.

In the photosensitive thick film composition of the present invention, the inorganic component is a powdery inorganic component (that is, an inorganic powder).
In particular, glass powder or ceramic powder is desirable. Further, the average particle size of the inorganic powder (D
50) is 0.1 to 0.1 because the light amount necessary for the exposure processing is minimized and the development processing can be stably performed.
It is desirable that the thickness be 10 μm. If the average particle size of the inorganic powder is less than 0.1 μm, the exposure sensitivity tends to decrease and the required amount of exposure light tends to increase. On the other hand, if the average particle size exceeds 10 μm, the resolution due to coarse particles is reduced during development. Degradation may occur.

As the glass powder, a known glass powder such as a borosilicate glass powder can be used, and the ceramic powder may be a dielectric ceramic powder, an insulator ceramic powder, a dielectric ceramic powder, a magnetic ceramic powder, or the like. Various ceramic powders can be used. In particular,
Ag and C, like crystallized glass ceramic powder, glass composite ceramic powder and non-glass ceramic powder
A low-temperature sintered ceramic powder which can be co-fired with a low melting point metal such as u is desirable.

The inorganic components such as glass powder and ceramic powder include B, Pb, Zn, Bi, Al, Mg, Ca,
Ba, Ti, Sr, Zr, Mn, Co, Ni, Fe,
It may be a polyvalent metal compound containing at least one polyvalent metal ion selected from the group consisting of Y, Nb, La and Ru. That is, when the inorganic component in the photosensitive thick film composition is a polyvalent metal compound, polyvalent metal ions are eluted in the solute portion, and this reacts with an acidic functional group (particularly a carboxyl group) of the organic binder to cause gelation. However, if a polyhydric alcohol is contained in the composition according to the present invention, this prevents the reaction between the polyvalent metal ion and the anion of the organic binder, and can suppress the gelation.

Specifically, as the glass powder, SiO 2
₂ -PbO system, SiO ₂ -ZnO system, SiO ₂ -Bi ₂ O ₃
System, SiO ₂ -K ₂ O system, SiO ₂ -Na ₂ O system, SiO ₂
—PbO—B ₂ O ₃ system, SiO ₂ —ZnO—B ₂ O ₃ system, S
_{iO 2 -Bi 2 O 3 -B 2} O 3 _{system, SiO 2 -K 2 O-B} 2 O 3
And an amorphous glass powder such as a SiO ₂ —Na ₂ O—B ₂ O ₃ system.

As the ceramic powder, Al, B
a, Ti, Sr, Pb, Zr, Mn, Co, Ni, F
oxides, borides, nitrides of at least one polyvalent metal selected from the group consisting of e, Y, Nb, La and Ru;
A silicide or the like can be used. More specifically, an insulating ceramic powder composed of Al ₂ O ₃ or ZrO _2, a dielectric ceramic powder composed of BaTiO ₃ or the like, a ferrite powder composed of nickel zinc ferrite, nickel zinc copper ferrite, etc., RuO ₂ , Pb ₂ Ru ₂ O ₇ , B
A high-resistance ceramic powder made of i ₂ Ru ₂ O ₇ , a composite oxide of Mn, Co, Ni, or the like, a piezoelectric ceramic powder made of PZT, or the like can be used.

That is, in the photosensitive thick film composition of the present invention, if an insulating ceramic powder or a glass powder is used as an inorganic component, an insulating photosensitive thick film composition can be prepared. Can be used to prepare a dielectric photosensitive thick film composition, a high-resistance ceramic powder can be used to prepare a high-resistance photosensitive thick-film composition, and a piezoelectric ceramic powder can be used to prepare a piezoelectric photosensitive thick-film composition. .

In the photosensitive thick film composition of the present invention, the organic binder is preferably an acrylic copolymer having a carboxyl group in a side chain. Such an organic binder is useful as a photosensitive organic binder, and can be developed with an alkaline or aqueous developer.
When the organic binder is an acrylic copolymer having a carboxyl group in a side chain, and the inorganic component includes the above-described glass powder or ceramic powder, the ionic cross-linking is performed.
Although a three-dimensional network is particularly easily formed, the formation of a three-dimensional network (i.e., gelation) due to the ionic crosslinking can be effectively suppressed by including such a polyhydric alcohol in such a system.

The organic binder containing an 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. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, vinyl acetic acid, and anhydrides thereof.
On the other hand, examples of the ethylenically unsaturated compound include acrylates such as methyl acrylate and ethyl acrylate, methacrylates such as methyl methacrylate and ethyl methacrylate, and fumarate esters such as monoethyl fumarate. Further, as the acrylic copolymer, a copolymer having an unsaturated bond introduced in the following form may be used. (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 present invention, the photosensitive organic component is
It contains a photopolymerizable monomer (a monomer having a reactive functional group), a photopolymerization initiator, an organic solvent, and the like, in addition to an organic binder having an acidic functional group. Specifically, (1) a mixture of a monomer or oligomer having a reactive functional group such as an unsaturated group and a photoradical generator such as an aromatic carbonyl compound; (2) a condensate of an aromatic diazonium compound and formaldehyde; (3) a mixture 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. Of these, a mixture of a monomer or oligomer having a reactive functional group such as an unsaturated group and a photoradical generator such as an aromatic carbonyl compound is particularly desirable.

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, and isodecyl. 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 Acrylate, ethoxylated bisphenol A diacrylate, Poxylated neopentyl glycol diacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glyceryl triacrylate, pentaerythritol tetra Acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hydroxypentaacrylate, ethoxylated pentaerythritol tetraacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate DOO, tetraethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,3
-Butylene glycol dimethacrylate, ethoxylated bisphenol A dimethacrylate, trimethylolpropane trimethacrylate and the like.

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.

It is desirable that the photosensitive organic component contains an ultraviolet absorber. By including an ultraviolet absorber, it is possible to improve the absorptivity of the exposure light beam, and at the same time, it is possible to suppress exposure failure due to light scattering. Examples of the ultraviolet absorber include an azo red pigment and an amine red dye.

The photosensitive thick film composition of 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 the like. Can be added. In addition, the photosensitive thick film composition of the present invention may be a paste composition (that is, a photosensitive paste), but may be a slurry composition.

Next, the electronic component of the present invention will be described by taking a chip inductor as an example.

As shown in FIGS. 1 and 2, the chip inductor 1 according to the present embodiment is made of a photosensitive thick film composition (here, a photosensitive insulating paste) on an insulating substrate 2a such as alumina. It has a laminated structure in which an insulator layer 2b, an insulator layer 2c, an insulator layer 2d, and an insulator layer 2e are sequentially laminated. In the chip inductor 1, external electrodes 3a and 3b are formed on side surfaces of a base 2 including an insulating substrate 2a and insulator layers 2b to 2e, and a spiral internal electrode 4a is formed inside the base 2. 4b, 4c
And 4d, respectively.

That is, inside the base 2, spiral internal electrodes 4a, 4b, 4 forming a coil pattern are formed.
c and 4d are provided between the insulating substrate 2a and the insulating layer 2b, between the insulating layers 2b and 2c, between the insulating layers 2c and 2d, and between the insulating layers 2d and 2e, respectively. The internal electrode 4a provided between the insulator layers 2a-2b is the external electrode 3a and the internal electrode 4d provided between the insulator layers 2d-2e.
Are connected to the external electrodes 3b, respectively.

Further, the internal electrode 4a provided between the insulating substrate 2a and the insulating layer 2b is provided between the insulating layers 2b-2c via via holes 5b formed in the insulating layer 2b. The internal electrode 4b is electrically connected to the internal electrode 4b.
And the internal electrode 4d are electrically connected via insulator layers 2c and via holes 5c and 5d formed in the insulator layer 2d, respectively.

The insulating layers 2b to 2d are formed by applying the photosensitive insulating paste according to the present invention, forming a coating film, drying, exposing, developing, and baking to form a via having a fine and good processed shape. Holes 5b, 5c and 5
d is formed. That is, a highly reliable chip inductor 1 having a fine and high-precision electrode pattern and achieving miniaturization and high density is obtained.

Next, an example of a method for manufacturing the chip inductor 1 will be described.

As shown in FIG. 2, first, a photosensitive conductor paste containing Ag or the like as a main component is applied on an insulating substrate 2a made of alumina or the like. Is formed. continue,
For example, the internal electrodes 4a are formed on the insulating substrate 2a by firing in air at 850 ° C. for about 1 hour. Incidentally, as the photosensitive conductive paste, for example, Fordel K37
14 (manufactured by DuPont) or the like can be used. In addition, as the coating method, any method such as a screen printing method, a spin coating method, and a doctor blade method may be used. However,
The conductor pattern serving as the internal electrode 4a may be formed using a normal conductor paste according to a screen printing method, a patterning method using a photoresist, or the like.

Next, a photosensitive insulating paste according to the present invention is applied on the insulating substrate 2a so as to cover the internal electrodes 4a, thereby forming an insulating coating film. Then, after this coating film is dried, for example, a diameter of 50 μm is passed through a photomask.
The via hole pattern is exposed. Thereafter, an unnecessary portion is removed by performing a developing process, and further baked at a predetermined temperature, for example, in the air for a predetermined time to form an insulator layer 2b having a via hole. Here, as a method of applying the photosensitive insulating paste, any method such as a screen printing method, a spin coating method, and a doctor blade method may be used. Incidentally, the coating film is, for example, 40 to 100 ° C., 10 minutes to
Dry for 2 hours. Thereafter, a conductive material is filled into the via hole formed in the insulator layer 2b and dried, and then a via hole 5b connecting one end of the internal electrode 4a and one end of the internal electrode 4b is formed.

Then, a spiral internal electrode 4b is formed on the insulator layer 2b in the same manner as described above. Further, in the same procedure, an insulating layer 2c having a via hole 5c, an internal electrode 4c, an insulating layer 2d having a via hole 5d, and an internal electrode 4d are sequentially formed, and then the internal electrode 4d is formed on the insulating layer 2d. A normal insulating paste or a photosensitive insulating paste according to the present invention is applied so as to cover the coating film, and a coating film is formed. The body layer 2e is formed.

Thereafter, the insulating substrate 2a, the insulating layer 2
By providing the external electrodes 3a and 3b to the base 2 made of b, 2c, 2d and 2e, the chip inductor 1 having a laminated structure having a coil pattern of spiral internal electrodes is completed.

According to the above-described manufacturing method, the insulating layer 2
Since the photosensitive insulating paste according to the present invention is used to provide b, 2c, and 2d, fine via holes 5b, 5c, and 5d are formed in each of the insulator layers with a good processing shape.
Can be formed with high precision. That is, since the photosensitive insulating paste according to the present invention is less deteriorated with time and has excellent storage stability, it suppresses bleeding or the like caused by the viscosity deterioration, and has a diameter of less than 150 μm, particularly a diameter of 50 μm or less. Via holes can be formed with high precision. In addition, since the development process in the photolithography method can be stably performed, via holes can be formed finely and with high precision, and a small, highly reliable chip inductor excellent in high frequency characteristics and the like can be manufactured.

Further, since the above-described chip inductor is small, high-performance and highly reliable, it is considered that its function is sufficiently exhibited by using it for noise removal in mobile communication terminals and computers, for example. At the same time, a small and lightweight electronic device having high reliability can be realized.

Although the electronic component of the present invention has been described above with respect to a chip inductor, the electronic component of the present invention is not limited to this. For example, a three-dimensional internal component such as a multilayer ceramic capacitor or a multilayer LC filter may be used. In addition to electronic components with electrodes, VCO (Voltage Controlled Osc)
It may be a functional module such as an illator or a PLL (Phase Locked Loop), or a ceramic multilayer substrate or a hybrid IC for mounting a semiconductor device.

The photosensitive thick film composition of the present invention can be used in the preparation of a ceramic green sheet having photosensitivity by preparing a slurry in addition to the above-mentioned photosensitive insulating paste. In addition, the photosensitive thick film composition of the present invention can be used for forming an arbitrary insulator pattern, a dielectric pattern, a resistor pattern, and a magnetic pattern other than the formation of via holes. In other words, if the inorganic component in the photosensitive thick film composition is an insulating inorganic component, the fired film becomes an insulator pattern, and if the inorganic component is a dielectric inorganic component, it becomes a dielectric pattern or a high-resistance inorganic component. If a resistor pattern or a magnetic inorganic component is used, a magnetic pattern can be formed, and these can be processed finely and with high precision.

[0051]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to specific embodiments. Example 1 After mixing various components having the following compositions and amounts, kneading was performed by a three-roll mill to obtain a photosensitive insulating paste shown in Table 1 below. <Glass Powder> SiO ₂ —K ₂ O—B ₂ O ₃ based glass powder (borate content 17
%): 5.0 g <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 <Reactive functional group-containing monomer> Trimethylolpropane triacrylate: 1.0 g <Photopolymerization initiator> 2-methyl-1- [4- (methylthio) phenyl] -2
-Morpholinopropan-1-one (photopolymerization initiator A): 0.4 g 2,4-diethylthioxanthone (photopolymerization initiator B):
0.1 g <Organic solvent> Ethyl carbitol acetate: 4.0 g <Polyhydric alcohol> Glucitol (hexahydric alcohol): 0.1 g Further, the photosensitive insulating paste of this example was applied onto an alumina insulating substrate by a spin coater. Apply and apply this at 100 ° C
For 1 hour to form a 30 μm thick coating film. After leaving the obtained coating film for a predetermined period, an exposure treatment was performed. In the exposure processing, the via hole diameter = 50
The irradiation was performed by irradiation with a light beam (exposure amount: 250 mJ / cm ² ) from a high-pressure mercury lamp through a mask on which a (μmφ) pattern was drawn.

Further, an unsintered insulator layer having via hole holes (via hole diameter: 50 μmφ) was formed on an alumina insulating substrate by performing development processing using an aqueous solution of sodium carbonate. Then, this is fired in air at 850 ° C. to form a via hole (via hole diameter: 80 μm).
mφ). Examples 2 to 10 In the same manner as in Example 1, a photosensitive insulating paste having the composition shown in Table 1 below was produced. Note that pentamethylene glycol in Example 2 is a dihydric alcohol, glycerin in Example 3 is a trihydric alcohol, erythritol in Example 4 is a tetrahydric alcohol, and xylitol in Example 5 is a pentahydric alcohol. The mannitol of Example 6 is a hexahydric alcohol. Example 7
3-methoxy-3-methylbutanol is a monohydric alcohol.

[0053]

[Table 1]

Then, with respect to the photosensitive insulating pastes of Examples 1 to 10, immediately after preparation in air at a temperature of 20 ° C., 1 day, 3 days, 1 week, and 1 month, the preservation state ( Storage stability) was measured. The evaluation results are shown in Table 2 below. In addition, "o" in the following Table 2 means that the photosensitive insulating paste was not gelled at each predetermined time point, and the coating film formation and pattern processing were successfully performed. In addition, "x" in the table means that the photosensitive insulating paste was gelled and a coating film could not be formed, or an unexposed portion was not eluted in the developing solution and a pattern could not be formed. .

[0055]

[Table 2]

As a result, the photosensitive insulating pastes of Examples 1 to 6 containing dihydric to hexahydric alcohols did not gel at any time. That is, immediately after the production, one day, three days, one week, and one month after, the application on the alumina insulating substrate by the spin coater and the patterning by the photolithography method could be performed.

On the other hand, when additives other than the polyhydric alcohol are contained as in Examples 8 to 10, one day after the preparation of the paste, the paste gels and a coating film cannot be formed. Alternatively, the unexposed portion no longer elutes in the developer,
Pattern formation failed. Also, as in Example 7, 3
In those containing -methoxy-3-methylbutanol, gelation did not occur immediately after the preparation, 1 day, 3 days, 1 week, and 1 month, and the coating was performed on the insulating substrate by a spin coater. Although it could be carried out stably, at the time of exposure treatment after the coating film was dried, unexposed portions did not elute in the developing solution, and a pattern could not be formed. Examples 11 to 16 The amount of glucitol added was changed as shown in Table 3 below,
A photosensitive insulating paste was produced in the same manner as in Example 1. Glucitol is a hexahydric alcohol that is solid at room temperature (25 ° C.). In Table 3, “Ratio” in the column of additives indicates the weight ratio of glucitol in the total amount of glass powder and glucitol. .

[0058]

[Table 3]

As described above, for the photosensitive insulating pastes of Examples 11 to 16, in the same manner as in Example 1, the via hole diameter = 50.
(Μmφ) pattern formation was attempted. Then, the storage stability of each photosensitive insulating paste was evaluated in the same manner as in Example 1. In addition, paste applicability of each photosensitive insulating paste was evaluated.

In Table 3 below, “下 記” in the column of storage stability indicates that the photosensitive insulating paste was not gelled at each time point, and that the coating film formation and pattern processing were successfully performed. means. In addition, “△” in the column of storage stability means that after the photosensitive insulating paste coating film was formed, the unexposed portion hardly eluted in the developing solution, and it was difficult to form a pattern. In addition, "○" in the column of paste applicability
Indicates that the difference between the target film thickness and the actual film thickness was ± 0.5 μm or less, and “△” indicates that the difference between the target film thickness and the actual film thickness exceeded ± 0.5 μm. Means that

[0061]

[Table 4]

As can be seen from Table 4, Example 13 in which the polyhydric alcohol accounts for 0.01 to 20% by weight of the total amount of glucitol and glass powder in the photosensitive insulating paste.
According to the photosensitive insulating pastes of Examples 15 to 15, the storage stability over a long period of time was excellent, and the unexposed portions were easily eluted into the developing solution to form via holes having good shape. .

On the other hand, when the amount of glucitol added is small, as in the photosensitive insulating pastes of Examples 11 to 12, one week or one month after the paste preparation, although a coating film was formed, The unexposed portions are less likely to elute into the developer, and pattern formation tends to be more difficult. On the other hand, when the added amount of glucitol is too large, as in the photosensitive insulating paste of Example 16, the storage stability of the paste is excellent, but the viscosity tends to be too high and the paste applicability tends to be slightly lowered. Examples 17 to 22 Photosensitive insulating pastes were prepared in the same manner as in Example 1, except that the amount of pentamethylene glycol added was changed as shown in Table 4 below. Note that pentamethylene glycol is at room temperature (25
° C) and is a liquid dihydric alcohol. In Table 5, the “proportion” in the column of additives indicates the weight ratio of pentamethylene glycol to glass powder.

[0064]

[Table 5]

As described above, the photosensitive insulating pastes of Examples 17 to 22 were processed in the same manner as in Example 1 so that the via hole diameter = 50.
(Μmφ) pattern formation was attempted. And about each photosensitive insulating paste, like Example 11-Example 16,
The storage stability and paste applicability were evaluated. The evaluation results are shown in Table 6 below.

[0066]

[Table 6]

As can be seen from Table 6, Examples 19 to 21 in which the amount of pentamethylene glycol added was 0.1 to 5 times by weight the glass powder in the photosensitive insulating paste.
According to the photosensitive insulating paste described above, storage stability was excellent over a long period of time, and the unexposed portion was easily eluted into the developing solution to form a via hole with good shape.

On the other hand, when the amount of pentamethylene glycol added is small as in the photosensitive insulating pastes of Examples 17 and 18, a film can be formed one week or one month after the preparation of the paste. However, there was a tendency that unexposed portions were less likely to elute into the developer, making pattern formation difficult. On the other hand, when the addition amount of pentamethylene glycol is too large, as in the photosensitive insulating paste of Example 22, the storage stability of the paste is excellent, but the viscosity tends to be too low and the paste applicability tends to decrease. Was.

As described above, the photosensitive insulating paste obtained by mixing the photosensitive organic component containing the organic binder having an acidic functional group and the inorganic powder containing the polyvalent metal oxide is added with a predetermined amount of divalent to
If it contains a hexahydric alcohol, the gelation of the paste was sufficiently suppressed in both the paste state before application and the coating state after drying for a long time, and fine via holes could be formed with high precision. . In particular, the stability of the coating film was high, and the development processing in the photolithography method could be performed stably.

[0070]

According to the photosensitive thick film composition of the present invention,
In the photosensitive thick film composition containing (A) a photosensitive organic component containing an organic binder having an acidic functional group, and (B) an inorganic component containing a polyvalent metal compound, (C) having a plurality of alcoholic hydroxyl groups Since it contains a polyhydric alcohol, it can sufficiently suppress gelation in both the paste state before coating and the coated film state after coating and drying, and based on photolithography, such as via holes Can be formed finely and with high precision.

Further, according to the electronic component of the present invention, the insulator layer, the dielectric layer, the resistor layer, the magnetic layer, and the like can be finely and precisely patterned based on the photolithography method. Small and highly reliable electronic components having various patterns with high precision can be achieved.

Further, according to the electronic device of the present invention, since small and highly reliable electronic parts having various patterns of fine and high precision are provided, various electronic devices such as mobile communication equipment and computers are provided. Smaller size and higher reliability can be achieved.

[Brief description of the drawings]

FIG. 1 is a schematic perspective view of a chip inductor according to the present embodiment.

FIG. 2 is a schematic exploded perspective view of the chip inductor.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Chip inductor 2a, 2b, 2c, 2d, 2e ... Insulator layer 3a, 3b ... External electrode 4a, 4b, 4c, 4d ... Internal electrode 5b, 5c, 5d ... Via hole

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA02 AA04 AA08 AB15 AB16 AB17 AC01 AD01 BA03 BC14 BC34 BC43 BD03 BD23 CB13 CB42 CB43 CC08 CC20 FA28 FA29

Claims (11)

[Claims] 1. A photosensitive organic component containing an organic binder having an acidic functional group, (B) an inorganic component containing a polyvalent metal compound, and (C) a polyvalent compound having a plurality of alcoholic hydroxyl groups. A photosensitive thick film composition comprising an alcohol. 2. The photosensitive thick film composition according to claim 1, wherein the polyhydric alcohol is a polyhydric alcohol having 2 to 6 alcoholic hydroxyl groups. 3. The polyhydric alcohol is liquid at room temperature and is contained in a weight ratio of 0.1 to 5 times the inorganic component. Item 3. The photosensitive thick film composition according to Item 1 or 2. 4. The polyhydric alcohol is solid at room temperature and accounts for 0.01% by weight or more and 20% by weight or less of the total amount of the polyhydric alcohol and the inorganic component. The photosensitive thick film composition according to claim 1, wherein: 5. The photosensitive thick film composition according to claim 1, wherein the inorganic component occupies a volume fraction of 30% or more and 90% or less. 6. The method according to claim 1, wherein the inorganic component comprises glass powder or ceramic powder.
A photosensitive thick film composition according to any one of the above. 7. The polyvalent metal compound is B, Pb, Z
n, Bi, Al, Mg, Ca, Ba, Ti, Sr, Z
r, Mn, Co, Ni, Fe, Y, Nb, La and R
The photosensitive thick film composition according to any one of claims 1 to 6, comprising at least one kind of polyvalent metal ion selected from the group consisting of u. 8. The photosensitive thick film composition according to claim 1, wherein the organic binder is an acrylic copolymer having a carboxyl group in a side chain. 9. An electronic component having a layer obtained by firing the photosensitive thick film composition according to claim 1. Description: 10. The method according to claim 1, wherein the layer is at least one functional layer selected from the group consisting of an insulator layer, a dielectric layer, a resistor layer, and a magnetic layer, which has been subjected to via hole processing. The electronic component according to claim 9, wherein: 11. An electronic device comprising the electronic component according to claim 9.