JP2022186715A - Kit for manufacturing electronic component and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably manufacture an electronic component in which a fine conductive layer is accurately formed.

SOLUTION: A kit for manufacturing an electronic component has a photosensitive glass paste and a photosensitive conductive paste. The photosensitive glass paste contains glass powder and an ultraviolet absorber, and the photosensitive conductive paste contains conductive powder and an ultraviolet absorber. And in the kit for manufacturing an electronic component, both of the ultraviolet absorber in the photosensitive glass paste and the ultraviolet absorber in the photosensitive conductive paste contain azo dye, and the content of the ultraviolet absorber in the photosensitive glass paste is 0.2 mass% or more. With use of the photosensitive glass paste, a glass cured film having precise groove parts can be formed, and with use of the photosensitive conductive paste, photo-curing of the paste adhering to a top surface of the glass cured film can be prevented. And by burning of the glass cured film and a conductive cured film, an electronic component having a precise conductive layer can be manufactured.

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

The present invention relates to an electronic component manufacturing kit. Specifically, it relates to an electronic component manufacturing kit having a photosensitive glass paste for forming a glass layer having a groove of a predetermined width on a substrate surface, and a photosensitive conductive paste for forming a conductive layer in the groove of the glass layer. .

A method of forming a conductive layer of an electronic component using a photosensitive conductive paste containing conductive powder and a photocurable resin is widely known. An example of such a method is a photolithographic method (see Patent Document 1). In this method, first, a photosensitive conductive paste is applied to the surface of a base material, and then the paste is dried to form a filmy body containing conductive powder (conductive filmy body). Next, the conductive film is covered with a photomask having slits (openings) of a predetermined pattern, and a part of the conductive film that is exposed from the slits is irradiated with light. As a result, the photocurable resin is cured to form a cured film (conductive cured film) containing the conductive powder. Next, the unexposed portion (uncured conductive film) shielded by the photomask is removed with a developer. As a result, only the exposed conductive cured film having the predetermined pattern remains on the surface of the substrate, and the desired conductive layer can be formed by baking this.

By the way, in recent years, there has been an increasing demand for miniaturization of electronic components. In order to achieve miniaturization of such electronic components, L/S (line and space), which indicates the dimensional relationship between the line width L of the conductive layer and the width S of the interval (space) between adjacent conductive layers, must be reduced. is required. For example, the L/S of the conductive layers of conventional general electronic components was about 40 μm/40 μm, but in recent years, it is required to form a fine conductive layer with an L/S of less than 30 μm/30 μm. However, if a photomask with small slits is used to form a fine conductive layer, the amount of light supplied to the conductive film in the exposure process is reduced. Light may not reach. In this case, the lower portion of the conductive film is not sufficiently cured and is removed in the developing step, so that a conductive layer having an inverted trapezoidal shape in cross section is formed. The formation of such an inverted trapezoidal conductive layer is called "undercut" and can cause problems such as an increase in the resistance of the electronic component and disconnection of the conductive layer.

As a technique for forming a fine conductive layer without causing such an undercut, a photolithography method using a photosensitive glass paste has been proposed. In this method, first, a photosensitive glass paste is applied to the substrate surface to form a glass film. Next, the glass film is covered with a photomask having slits of a predetermined pattern, and the glass film exposed from the slits is exposed. Next, the uncured glass film is removed with a developer to form a cured glass film having a predetermined pattern of grooves on the substrate surface. Next, a conductive cured film is formed in the grooves of the cured glass film by filling the grooves of the cured glass film with a photosensitive conductive paste and exposing it to light. By firing the cured glass film and the cured conductive film, an electronic component having a glass layer having fine grooves and a conductive layer formed in the grooves of the glass layer can be produced. In this manufacturing technology, a wiring pattern (groove pattern) is formed by exposing a glass film having high light transmittance (transparency), so the slit of the photomask becomes small, and the amount of ultraviolet rays supplied is reduced. Even so, undercut due to poor curing is less likely to occur. Furthermore, it has the advantage that it is not necessary to carry out precise exposure and development when forming a conductive cured film that contains conductive powder and is difficult to be photocured. An example of manufacturing technology using such a photosensitive glass paste is disclosed in Patent Document 2.

Patent No. 6694099 Patent No. 5195432

However, the production method using the photosensitive glass paste still has room for improvement and cannot stably form a precise conductive layer, making it difficult to apply to actual production sites. Specifically, the photosensitive glass paste for forming the cured glass film has a strong light diffusing property and an excessively high light transmittance. It may get lost. In this case, the light-shielding portion covered with the photomask is also photocured, making it impossible to accurately form the desired groove.

SUMMARY OF THE INVENTION The present invention has been made to solve such problems, and an object thereof is to provide a technique for stably manufacturing an electronic component in which a fine conductive layer is accurately formed.

In order to achieve the above object, the technology disclosed herein provides an electronic component manufacturing kit having the following configuration.

The electronic component manufacturing kit disclosed herein includes a photosensitive glass paste (A) for forming a glass layer having grooves of a predetermined width on the substrate surface, and a photosensitive conductive paste for forming a conductive layer in the grooves of the glass layer. (B) and The photosensitive glass paste (A) contains a glass powder (A1), a photocurable resin (A2), and an ultraviolet absorber (A3), and the photosensitive conductive paste (B) contains a conductive powder ( B1), a photocurable resin (B2), and an ultraviolet absorber (B3). In the electronic component manufacturing kit disclosed herein, both the ultraviolet absorber (A3) of the photosensitive glass paste (A) and the ultraviolet absorber (B3) of the photosensitive conductive paste (B) are It contains an azo dye, and the content of the ultraviolet absorber (A3) is 0.2% by mass or more when the total weight of the photosensitive glass paste (A) is 100% by mass.

The technique disclosed herein uses an electronic component manufacturing kit having a photosensitive glass paste (A) and a photosensitive conductive paste (B) to manufacture an electronic component in which a fine conductive layer is accurately formed. Specifically, the photosensitive glass paste (A) uses an ultraviolet absorber (A3) containing an azo dye. As a result, it is possible to prevent scattered light from being generated inside the glass film in the exposure step, and to suppress photocuring of the light-shielding portion. According to the experiments of the present inventors, by adjusting the content of the ultraviolet absorber (A3) containing the azo dye to 0.2% by mass or more, the precision of the cured glass film after development is dramatically improved. is improved, and fine grooves can be clearly formed.

However, even if it is possible to form a cured glass film having the precise grooves, it is difficult to accurately form a fine conductive layer along the precise grooves. The reason is as follows. When applying the photosensitive conductive paste (B) to the inside of the groove, the photosensitive conductive paste (B) is printed on the entire cured glass film having the groove and dried. Therefore, a conductive film-like body obtained by drying the photosensitive conductive paste (B) is also formed on the upper surface of the cured glass film. The conductive film-like material on the upper surface of the glass cured film is removed in the development process by blocking light in the exposure process and making it an unexposed part. However, due to light scattering inside the conductive film-like body irradiated with light in the exposure step, part of the unexposed portion on the cured glass film is photocured, and is not removed in the development step, and remains on the cured glass film. It may remain as a residue. In this case, although precise grooves are formed in the cured glass film, it may be difficult to accurately form a fine conductive layer. On the other hand, in the electronic component manufacturing kit disclosed herein, an ultraviolet absorber (B3) containing an azo dye is also added to the photosensitive conductive paste (B), and the photosensitive conductive paste (B) is made of glass. It prevents photocuring on the cured film.

As described above, the electronic component manufacturing kit disclosed herein comprises a photosensitive glass paste (A) that can dramatically improve the precision of grooves in a cured glass film, and a cured glass film that does not leave residue during development. It is combined with a photosensitive conductive paste (B) that can prevent photocuring on the surface. By using a manufacturing kit having such a configuration, it is possible to stably manufacture an electronic component in which fine conductive layers are accurately formed.

In a preferred embodiment of the electronic component manufacturing kit disclosed herein, the glass powder (A1) contains B ₂ O ₃ —SiO ₂ -based glass containing B ₂ O ₃ and SiO ₂ as main components. Such a B ₂ O ₃ —SiO ₂ -based glass is suitable as a sintering glass, and can form a glass layer with excellent adhesion to the substrate surface.

In the embodiment using the B ₂ O ₃ —SiO ₂ -based glass, the B ₂ O ₃ —SiO ₂ -based glass contains 5 to 20% by mass of B ₂ O ₃ in terms of oxide, Moreover, it preferably contains 20 to 70% by mass of SiO ₂ . This can further improve adhesion to the substrate surface.

In a preferred embodiment of the electronic component manufacturing kit disclosed herein, the content of the glass powder (A1) is 30% by mass or more and 60% by mass when the total weight of the photosensitive glass paste (A) is 100% by mass. % or less. As a result, both the performance of the electronic component and the working efficiency can be favorably achieved.

In a preferred embodiment of the electronic component manufacturing kit disclosed herein, the content of the ultraviolet absorber (A3) is 1.0% by mass when the total weight of the photosensitive glass paste (A) is 100% by mass. It is below. As described above, in order to prevent the generation of scattered light inside the glass film, the photosensitive glass paste (A) should contain 0.2% by mass or more of the ultraviolet absorber (A3). , The upper limit of the content of the ultraviolet absorber (A3) is not particularly limited. However, as the content of the ultraviolet absorber (A3) is increased, there is a tendency that the appropriate exposure time for the glass film-like body becomes longer. Therefore, from the viewpoint of improving production efficiency, the content of the ultraviolet absorber (A3) is preferably 1.0% by mass or less.

In a preferred embodiment of the electronic component manufacturing kit disclosed herein, the azo dye contains at least one selected from yellow dyes and red dyes. As a result, photocuring of the light-shielded glass film can be more reliably prevented.

In a preferred embodiment of the electronic component manufacturing kit disclosed herein, the photosensitive glass paste (A) further contains a photopolymerization initiator (A4). This makes it possible to achieve better photocuring of the glass film.

In a preferred embodiment of the electronic component manufacturing kit disclosed herein, the photosensitive glass paste (A) further contains an organic binder (A5). As a result, the fixability of the glass film-like material to the substrate surface can be improved.

In a preferred embodiment of the electronic component manufacturing kit disclosed herein, the photosensitive glass paste (A) further contains a dispersion medium (A6). This imparts appropriate viscosity and fluidity to the photosensitive glass paste (A), thereby improving the handleability and printability of the paste.

In the embodiment in which the dispersion medium (A6) is added, the dispersion medium (A6) is preferably an organic solvent having a boiling point of 150°C or higher and 250°C or lower. As a result, it is possible to obtain a photosensitive glass paste (A) that has a certain level of paste preservability and that can be easily formed into a glass film.

In a preferred embodiment of the electronic component manufacturing kit disclosed herein, the conductive powder (B1) contains silver-based particles. As a result, it is possible to manufacture an electronic component with an excellent balance between cost and electrical resistance.

In a preferred embodiment of the electronic component manufacturing kit disclosed herein, the content of the conductive powder (B1) in the photosensitive conductive paste (B) is 74% by mass or more. As a result, a dense and thick conductive layer can be formed, and low-resistance electronic components can be manufactured. Although the details will be described later, according to the technology disclosed herein, it is possible to suitably prevent the adverse effects caused by using the photosensitive conductive paste containing the conductive powder at a high concentration as described above.

In a preferred embodiment of the electronic component manufacturing kit disclosed herein, the content of the ultraviolet absorber (B3) is 0.001% by mass or more when the total weight of the photosensitive conductive paste (B) is 100% by mass. It is 0.2% by mass or less. As a result, the lengthening of the exposure time can be suppressed, and the photocuring of the conductive film-like body on the glass cured film can be suitably prevented.

In a preferred embodiment of the electronic component manufacturing kit disclosed herein, the photosensitive conductive paste (B) further contains a photopolymerization initiator (B4). This makes it possible to achieve better photocuring of the glass film.

In a preferred embodiment of the electronic component manufacturing kit disclosed herein, the photosensitive conductive paste (B) further contains an organic binder (B5). As a result, the fixability of the conductive film to the substrate surface can be improved.

In a preferred embodiment of the electronic component manufacturing kit disclosed herein, the photosensitive conductive paste (B) further contains a dispersion medium (B6). This imparts appropriate viscosity and fluidity to the photosensitive conductive paste (B), thereby improving the handleability and printability of the paste.

Moreover, a photosensitive glass paste is provided as another aspect of the technology disclosed herein. This photosensitive glass paste contains a glass powder (A1), a photocurable resin (A2), and an ultraviolet absorber (A3). In the photosensitive glass paste disclosed herein, the ultraviolet absorber (A3) contains an azo dye, and the content of the ultraviolet absorber (A3) is 0.2 when the total weight is 100% by mass. % by mass or more. As described above, by using a photosensitive glass paste having such a configuration, the precision of the cured glass film after development is dramatically improved, and fine grooves can be clearly formed. It can contribute to stable production of electronic components having a conductive layer.

Also, as another aspect of the technology disclosed herein, a composite that is a precursor of an electronic component is provided. Such a composite includes a green sheet that is a precursor of the base material, a glass cured film that is placed on the green sheet and photocured with the photosensitive glass paste (A) having the above configuration, and is placed on the green sheet, The photosensitive conductive paste (B) configured as described above is provided with a conductive cured film that is photocured. In such a composite, grooves having a predetermined pattern are provided in the cured glass film, and the conductive cured film is formed inside the grooves.

Furthermore, as another aspect of the technology disclosed herein, an electronic component after firing is provided. Such an electronic component comprises a base material, a glass layer made of a fired body of the photosensitive glass paste (A) having the above configuration, arranged on the base material surface, and a photosensitive conductive paste having the above configuration ( and a conductive layer made of the sintered body of B). In such an electronic component, grooves having a predetermined pattern are provided in the glass layer, and the conductive layer is formed inside the grooves.

Also, as another aspect of the technology disclosed herein, a method for manufacturing an electronic component is provided. In this electronic component manufacturing method, the electronic component is manufactured using the electronic component manufacturing kit configured as described above. Such a production method includes a step of applying a photosensitive glass paste (A) onto a green sheet, then exposing and developing to form a cured glass film having grooves of a predetermined pattern, and exposing the grooves of the glass layer to light. After filling with the conductive paste (B), a step of forming a conductive cured film by performing exposure and development, and a step of baking the green sheet, the glass cured film and the conductive cured film.

It is sectional drawing explaining printing of the photosensitive glass paste in the manufacturing method of the electronic component which concerns on one Embodiment. FIG. 4 is a cross-sectional view illustrating exposure of a glass film-like body in the method for manufacturing an electronic component according to one embodiment; It is sectional drawing explaining the development of the glass cured film in the manufacturing method of the electronic component which concerns on one Embodiment. It is a sectional view explaining printing of photosensitive conductive paste in a manufacturing method of electronic parts concerning one embodiment. FIG. 4 is a cross-sectional view for explaining exposure of a conductive film-like body in the method for manufacturing an electronic component according to one embodiment; FIG. 4 is a cross-sectional view illustrating development of a conductive cured film in the method for manufacturing an electronic component according to one embodiment; FIG. 4 is a cross-sectional view for explaining the manufacturing procedure of the multilayer chip inductor; FIG. 4 is a cross-sectional view for explaining the manufacturing procedure of the multilayer chip inductor; FIG. 4 is a cross-sectional view for explaining the manufacturing procedure of the multilayer chip inductor; FIG. 4 is a cross-sectional view for explaining the manufacturing procedure of the multilayer chip inductor; FIG. 4 is a cross-sectional view for explaining the manufacturing procedure of the multilayer chip inductor; FIG. 4 is a cross-sectional view for explaining the manufacturing procedure of the multilayer chip inductor; It is an optical micrograph of each sample produced in the test example.

Preferred embodiments of the technology disclosed herein are described below. Matters other than those specifically mentioned in this specification, which are necessary for the implementation of the technology disclosed herein, are based on the technical content taught by this specification and those skilled in the art. can be understood based on general technical common sense. The technology disclosed herein can be implemented based on the content disclosed in this specification and common general technical knowledge in the field. In addition, the notation of "A to B" (A and B are arbitrary numbers) indicating the range in this specification means "preferably larger than A" and "preferably smaller than B" along with the meaning of A or more and B or less. shall include the meaning of

In this specification, the dried photosensitive glass paste is referred to as a "glass film", the photocured glass film is referred to as a "cured glass film", and the cured glass film is fired. This is called a "glass layer". On the other hand, the dried photosensitive conductive paste is called a “conductive film”, the photo-cured conductive film is called a “conductive cured film”, and the fired conductive cured film is called a “conductive film”. layer.

1. Electronic Component Manufacturing Kit First, the electronic component manufacturing kit disclosed herein will be described. As used herein, the term "electronic component manufacturing kit" refers to a combination of a plurality of types of paste compositions used for forming conductive layers of electronic components. The term "paste" as used herein is a term that includes ink and slurry. The electronic component manufacturing kit disclosed herein includes at least a photosensitive glass paste (A) and a photosensitive conductive paste (B). The components of each paste are described below.

<<Photosensitive glass paste (A)>>
The photosensitive glass paste (A) is a paste composition for forming a glass layer having grooves of a predetermined width on the substrate surface. This photosensitive glass paste (A) contains at least a glass powder (A1), a photocurable resin (A2), and an ultraviolet absorber (A3). The components contained in the photosensitive glass paste (A) are described below.

<Glass powder (A1)>
The glass powder (A1) is an inorganic component that remains without being burned off during the firing treatment and forms a glass layer on the substrate surface after firing. Preferred examples of the glass powder (A1) include B ₂ O ₃ —SiO ₂ -based glass containing a boron component (B ₂ O ₃ ) and a silicon component (SiO ₂ ) as main components. By using the photosensitive glass paste (A) containing such a B ₂ O ₃ —SiO ₂ -based glass, a glass layer having excellent fixability to the substrate surface can be formed.

Specifically, the boron component (B ₂ O ₃ ) contributes to increasing the fluidity during firing, so it can improve the fixability of the glass layer to the substrate surface. The proportion of B ₂ O ₃ in the B ₂ O ₃ —SiO ₂ -based glass is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more, in terms of oxide. . By this, the fixability of the glass layer after baking can be improved more suitably. On the other hand, if the content of B ₂ O ₃ is excessive, it may become difficult to maintain the shape of the glass layer during firing. Therefore, the upper limit of the proportion of B ₂ O ₃ in the B ₂ O ₃ —SiO ₂ -based glass is preferably 25% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less. Next, the silicon component (SiO ₂ ) is a component that constitutes the skeleton of the glass layer after firing. SiO ₂ also has the function of improving the fixability to the substrate surface. The proportion of SiO ₂ in the B ₂ O ₃ —SiO ₂ -based glass is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 40% by mass or more, in terms of oxide. This can further improve the fixability to the substrate surface. Moreover, the upper limit of the ratio of SiO ₂ is preferably 80% by mass or less, more preferably 70% by mass or less, and particularly preferably 60% by mass or less. The B ₂ O ₃ —SiO ₂ -based glass may also contain components other than B ₂ O ₃ and SiO ₂ . Such other components include group 2 element oxides (RO: R is Mg, Ca, Sr, Ba, Ra, etc.), aluminum components (Al ₂ O ₃ ), zinc components (ZnO), and the like. By adjusting the content of these other components, it is possible to improve the heat resistance and chemical durability of the glass layer after firing.

The glass composition used for the glass powder (A1) is not limited to the above-described B ₂ O ₃ —SiO ₂ -based glass, and conventionally known glass compositions can be used without particular limitations. Other examples of glass compositions that can be used in the glass powder (A1) include SiO ₂ —RO glass, SiO ₂ —RO—Al ₂ O ₃ glass, SiO ₂ —RO—Y ₂ O ₃ glass, SiO ₂ -RO-B ₂ O ₃ based glass, SiO ₂ -Al ₂ O ₃ based glass, SiO ₂ -ZnO based glass, SiO ₂ -ZrO ₂ based glass, RO based glass, lead based glass, lead lithium based glass, etc. mentioned.

Although the particle size of the glass powder (A1) is not particularly limited, micron size is preferable. For example, considering lot variation during paste production due to agglomeration of the glass powder (A1), the _D50 particle size of the glass powder (A1) is preferably 0.3 μm or more, more preferably 0.7 μm or more, and 1.0 μm. The above are particularly preferred. On the other hand, considering the surface smoothness of the glass layer after drying, the upper limit of the _D50 particle size of the glass powder (A1) is preferably 8 µm or less, more preferably 5 µm or less, and particularly preferably 2 µm or less. The " _D50 particle size" in this specification is a particle size corresponding to an integrated value of 50% from the smaller particle size side in the volume-based particle size distribution based on the laser diffraction/scattering method.

The content of the glass powder (A1) in the photosensitive glass paste (A) is preferably 25% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, and particularly preferably 40% by mass or more. . As a result, the film thickness of the glass layer after baking can be increased, so that the conductive layer formed in the grooves of the glass layer can be easily increased in thickness. As a result, a conductive layer with low resistance can be formed, and the performance of the electronic component can be improved. On the other hand, from the viewpoint of suppressing an increase in paste viscosity and preventing a decrease in work efficiency, the upper limit of the content of the glass powder (A1) is preferably 70% by mass or less, more preferably 65% by mass or less, and 60% by mass. % or less is more preferable, and 55 mass % or less is particularly preferable. In addition, unless otherwise specified, the "content" in this specification refers to the mass ratio (% by mass) when the total weight of the paste is 100% by mass.

<Photocurable resin (A2)>
The photocurable resin (A2) is an organic compound that is cured by a polymerization reaction, a cross-linking reaction, or the like when irradiated with light (ultraviolet rays). As the photocurable resin (A2) in the photosensitive glass paste (A) disclosed herein, conventionally known photocurable resins that can be used in photosensitive pastes can be used without particular limitation. For example, the photocurable resin (A2) may be a photocurable polymer having a relatively high molecular weight (e.g., a weight average molecular weight of 6000 or more), or a relatively low molecular weight (e.g., a weight average molecular weight of 6000) photocurable oligomer. When a photocurable polymer is used as the photocurable resin (A2), fixability of the photosensitive glass paste (A) before photocuring can be improved. Considering the fixability to the substrate surface during printing, the weight average molecular weight Mw of the photocurable resin (A2) is preferably 500 or more, more preferably 750 or more, even more preferably 1000 or more, and 1500 or more. Especially preferred. On the other hand, the upper limit of the weight average molecular weight Mw of the photocurable resin (A2) is preferably 60,000 or less, more preferably 50,000 or less, still more preferably 40,000 or less, and particularly preferably 30,000 or less.

An example of the photocurable resin (A2) includes a (meth)acrylic resin. Since such a (meth)acrylic resin is excellent in followability, flexibility, and durability to a substrate, peeling and breakage of the cured glass film before baking can be suppressed. In addition, "(meth)acrylic resin" is a photocurable resin having a (meth)acryloyl group. Here, the above-mentioned "(meth)acryloyl group" means "methacryloyl group (-C(=O)-C(CH ₃ )=CH ₂ )" and "acryloyl group (-C(=O)-CH=CH ₂ )”. Preferred examples of the (meth)acrylic resin include homopolymers of alkyl (meth)acrylates and copolymers containing alkyl (meth)acrylates as main monomers and copolymerizable sub-monomers in the main monomers. is mentioned. Specific examples of the homopolymer include polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, and the like. Specific examples of the copolymer include, for example, block copolymers containing, as repeating structural units, a methacrylic acid ester polymer and an acrylic acid ester polymer block. Specific examples of methacrylates include methyl methacrylate, propyl methacrylate, n-butyl methacrylate, and t-butyl methacrylate. Specific examples of acrylic acid esters include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, and n-hexyl acrylate. In addition, the above-mentioned "(meth)acrylate" is a term including "methacrylate" and "acrylate". Moreover, from the viewpoint of improving photocurability, the (meth)acrylic resin preferably has a (meth)acryloyl group (preferably an acryloyl group) in its side chain. As the (meth)acrylic resin as described above, commercially available products can be used without particular limitation. As such commercially available (meth)acrylic resins, for example, those manufactured by Nippon Kayaku Co., Ltd., Kyoeisha Chemical Co., Ltd., Shin-Nakamura Chemical Co., Ltd., and Toagosei Co., Ltd. can be used.

Moreover, the content of the photocurable resin (A2) in the photosensitive glass paste (A) is preferably 2% by mass or more, more preferably 4% by mass or more, and particularly preferably 6% by mass or more. This makes it possible to form a cured glass film that is properly fixed on the surface of the substrate with a short exposure time. On the other hand, the upper limit of the content of the photocurable resin (A2) is preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% by mass or less. As a result, photocuring of the light-shielding portion can be reliably prevented, and the precision of the grooves of the cured glass film after development can be further improved.

<Ultraviolet absorber (A3)>
The photosensitive glass paste (A) of the electronic component manufacturing kit disclosed herein contains an azo dye as a UV absorber (A3). Such azo dyes are aromatic compounds in which two organic groups are linked via an azo group (-N=N-). Since such azo dyes have an absorption peak at a wavelength of 10 nm to 500 nm, they can appropriately absorb the scattered ultraviolet light generated inside the glass film. As a result, photocuring of the light-shielding portion of the glass film can be suitably prevented, and fine grooves can be accurately formed in the cured glass film after exposure. Furthermore, since the azo dye is an organic dye, it also has the property of not remaining on the glass layer after baking. As a result, it is possible to prevent deterioration of the performance of the electronic component due to the UV absorber remaining in the glass layer after firing. Examples of the azo dye include oil yellow, oil orange, oil violet, sudan blue, sudan red, sudan II, sudan III, and sudan IV. Among these, a yellow dye (oil yellow), a red dye (Sudan Red), and the like are particularly preferable from the viewpoint of more appropriately absorbing diffused light of ultraviolet rays.

The ultraviolet absorber (A3) of the photosensitive glass paste (A) may contain dyes other than azo dyes. However, considering the deterioration in performance due to the dye remaining in the glass layer after baking, it is preferable to select organic dyes for dyes other than azo dyes. Examples of such organic dyes include aminoketone dyes, xanthene dyes, quinoline dyes, aminoketone dyes, anthraquinone dyes, benzophenone dyes, benzotriazole compounds, diphenylcyanoacrylates, triazines, and p-aminobenzoic acid dyes. dyes and the like. However, from the viewpoint of more appropriately exhibiting the accuracy improvement effect of the azo dye, it is preferable that most of the ultraviolet absorber (A3) is composed of the azo dye. Specifically, the content of the azo dye with respect to the total amount of the ultraviolet absorber (A3) is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and 90% by mass or more. Especially preferred. Further, the ultraviolet absorber (A3) may be entirely an azo dye (the content of the azo dye is 100% by mass).

In the photosensitive glass paste (A) disclosed herein, the content of the ultraviolet absorber (A3) is set at 0.2% by mass or more. According to the studies of the present inventors, by adding 0.2% by mass or more of the ultraviolet absorber (A3) containing the azo dye, the light-shielding portion is reliably prevented from being photocured in the exposure step, and development The precision of the subsequent glass cured film can be significantly improved. From the viewpoint of further improving the precision of the cured glass film, the content of the ultraviolet absorber (A3) is preferably 0.25% by mass or more, more preferably 0.3% by mass or more, and 0.35% by mass. % or more is particularly preferred. On the other hand, the upper limit of the content of the ultraviolet absorber (A3) is not particularly limited, and may be 5% by mass or less, 4% by mass or less, 3% by mass or less, or 2% by mass or less. good. However, if the content of the ultraviolet absorber (A3) is excessively increased, the exposure time required for curing the glass film (formation of the cured glass film) becomes longer, which may cause a decrease in production efficiency. From this point of view, the upper limit of the content of the ultraviolet absorber (A3) is preferably 1.5% by mass or less, more preferably 1% by mass or less, further preferably 0.75% by mass or less, and 0.55% by mass. The following are particularly preferred.

<Photoinitiator (A4)>
The photosensitive glass paste (A) disclosed here may contain a photoinitiator (A4). The photopolymerization initiator (A4) is a component that is decomposed by irradiation with light (eg, ultraviolet rays) to generate active species such as radicals and cations, thereby promoting the polymerization reaction of the photocurable resin (A2). As the photopolymerization initiator (A4), one type alone or a combination of two or more types can be used according to the type of the photocurable resin (A2) among conventionally known ones. . Preferred examples of the photopolymerization initiator (A4) include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)-butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4-diethylthioxanthone, benzophenone etc. The content of the photopolymerization initiator (A4) in the photosensitive glass paste (A) is generally 0.01% by mass to 5% by mass, typically 0.05% by mass to 3% by mass, for example 0.05% by mass to 3% by mass. It is preferably 1% by mass to 2% by mass. This makes it possible to achieve better photocuring of the glass film.

<Organic binder (A5)>
The organic binder (A5) is a non-photosensitive (for example, photocurable) organic compound that enhances the adhesiveness (fixability to the surface of the substrate) between the photosensitive glass paste (A) and the substrate. Say. In other words, as described above, the photocurable resin (A2) such as a photocurable polymer also has the function of improving the fixability to the substrate surface. Therefore, when sufficient fixability can be obtained only with the photocurable resin (A2), the organic binder (A5) may not be added. On the other hand, when a photocurable oligomer is used as the photocurable resin (A2) and other components do not provide sufficient fixability, it is preferable to add an organic binder (A5). Note that the organic binder (A5) is preferably a water-soluble organic compound. This makes it possible to easily remove the uncured glass film-like body in the developing step using an aqueous developer.

A suitable example of the organic binder (A5) is a cellulosic compound. Such cellulosic compounds have a glucose ring, which is a repeating unit of cellulose. By adding the cellulose-based compound, the inorganic component (for example, the glass powder (A1)) and the photocurable resin (A2) become more compatible, and the storage stability of the paste can be improved. In addition, the cellulose-based compound has a plurality of hydroxyl groups on the glucose ring and exhibits good water solubility, so that it can be easily removed with an aqueous developer. The term "cellulosic compound" as used herein includes cellulose, cellulose derivatives, and salts thereof. As such a cellulose-based compound, one of conventionally known compounds can be used alone, or two or more of them can be used in appropriate combination. Preferred examples of cellulosic compounds include hydroxyalkylcelluloses such as hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and hydroxypropylmethylcellulose; alkylcelluloses such as methylcellulose and ethylcellulose; carboxyalkylcelluloses such as carboxymethylcellulose; Also, the organic binder (A5) may contain an organic compound other than the cellulosic compound. Other examples of the organic binder (A5) include acrylic resins, phenolic resins, epoxy resins, polyester resins, polyamide resins, polycarbonate resins, and the like. As the organic binder as described above, commercially available ones can be used without particular limitation. As a commercially available organic binder, for example, those manufactured by Shin-Nakamura Chemical Co., Ltd. and Mitsubishi Chemical Corporation can be used.

Moreover, the content of the organic binder (A5) in the photosensitive glass paste (A) is not particularly limited, and can be appropriately adjusted in consideration of the fixability to the substrate surface. For example, the content of the organic binder (A5) may be 1% by mass or more, 3% by mass or more, or 5% by mass or more. By adding a certain amount or more of the organic binder (A5) in this way, the fixability to the base material surface is improved, and peeling of the glass film-like material before firing can be suitably suppressed. In addition, by including a certain amount or more of water-soluble organic binder, it becomes easy to remove the uncured glass film-like body in the development process, which contributes to shortening the development time. On the other hand, the upper limit of the content of the organic binder (A5) may be 30% by mass or less, 20% by mass or less, or 15% by mass or less. As the content of the organic binder (A5) is reduced, the paste viscosity tends to decrease and the printability on the substrate surface tends to improve.

<Dispersion medium (A6)>
Moreover, the photosensitive glass paste (A) may contain a dispersion medium (A6) for dispersing the components described above. The dispersion medium (A6) is a liquid component that imparts appropriate viscosity and fluidity to the paste and improves handling properties, printability, and the like. In addition, the content of the dispersion medium (A6) in the photosensitive glass paste (A) can be appropriately adjusted in consideration of the viscosity and fluidity of the paste. The content of the dispersion medium (A6) can be approximately 1 to 50% by mass, typically 5 to 40% by mass, for example 10 to 30% by mass. As the dispersion medium (A5), conventionally known liquid components can be used alone or in combination of two or more. For example, as the organic dispersion medium, one type can be used alone, or two or more types can be used in appropriate combination, depending on the type of the photocurable resin, etc., from conventionally known ones. Examples of organic dispersion media include hydrocarbon solvents such as toluene and xylene; glycol solvents such as ethylene glycol, propylene glycol and diethylene glycol; ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (cellosolve) and diethylene glycol. Glycol ether solvents such as monobutyl ether (butyl carbitol), diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether, dipropylene glycol methyl ether acetate, propylene glycol phenyl ether, 3-methyl-3-methoxybutanol; Ester solvents such as 7-trimethyl-2-acetoxy-bicyclo-[2,2,1]-heptane, 2,2,4-trimethyl-1,3-pentadiol monoisobutyrate; terpineol, dihydroterpineol, dihydro alcoholic solvents such as terpinyl propionate and benzyl alcohol; and other organic solvents having a high boiling point such as mineral spirits. The dispersion medium (A6) of the photosensitive glass paste (A) may be selected in consideration of its boiling point. For example, by using an organic solvent having a boiling point of 150° C. or higher, natural evaporation of the dispersion medium (A6) can be prevented, and the preservation stability of the paste can be improved. On the other hand, by using an organic solvent having a boiling point of 250° C. or less, a glass film can be easily formed in a drying treatment after printing.

<Other additive ingredients>
In addition, the photosensitive glass paste (A) may contain components other than the components (A1) to (A6) described above as long as the effect of the technology disclosed herein is not significantly impaired. The other additive component is not particularly limited, and conventionally known additive components can be used singly or in combination of two or more. Such other additive components include polymerization inhibitors, radical scavengers, antioxidants, plasticizers, surfactants, leveling agents, thickeners, dispersants, antifoaming agents, anti-gelling agents, stabilizers, Preservatives and the like are included. Although not particularly limited, the content of such other additive components is generally 5% by mass or less, typically 3% by mass or less, for example 2% by mass or less, preferably 1% by mass or less. good.

<<Photosensitive conductive paste (B)>>
Next, the photosensitive conductive paste (B) of the electronic component manufacturing kit disclosed herein will be described. The photosensitive conductive paste (B) is a paste composition for forming a conductive layer in the grooves of the glass layer formed using the photosensitive glass paste (A). The photosensitive conductive paste (B) contains at least a conductive powder (B1), a photocurable resin (B2), and an ultraviolet absorber (B3). The components contained in the photosensitive conductive paste (B) are described below.

<Conductive powder (B1)>
The conductive powder (B1) is an inorganic component that remains without being burned off during firing and imparts electrical conductivity to the conductive layer. The type of the conductive powder (B1) is not particularly limited, and one of conventionally known conductive materials can be used alone or two or more of them can be used in appropriate combination depending on the application. Preferred examples of the conductive powder (B1) include gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), aluminum (Al), nickel (Ni), ruthenium (Ru ), rhodium (Rh), tungsten (W), iridium (Ir), osmium (Os), and mixtures and alloys thereof. Among these preferred examples, silver-based particles are more preferred. The term “silver-based particles” encompasses all particulate materials containing elemental silver (Ag). Examples of such silver-based particles include simple silver particles, silver alloys, core-shell particles containing a silver component, and the like. Examples of silver alloys include silver-palladium (Ag-Pd), silver-platinum (Ag-Pt), silver-copper (Ag-Cu), and the like. Examples of the core-shell particles include silver-ceramic core-shell particles having a core particle containing elemental silver and a ceramic shell covering the core particle. Since these silver-based particles are relatively inexpensive and have high electrical conductivity, they can contribute to the production of electronic components having an excellent balance between electrical conductivity and cost.

Although it is not particularly limited, as the particle size of the conductive powder (B1) becomes smaller, the filling of the photosensitive conductive paste (B) into the grooves of the hardened glass layer becomes easier, and the conductive layer after baking becomes easier. Density tends to improve. From this point of view, the upper limit of the _D50 particle size of the conductive powder (B1) is preferably 5 µm or less, more preferably 4.5 µm or less, and particularly preferably 4 µm or less. On the other hand, if the particle size of the conductive powder (B1) is too small, coarse particles are likely to form due to agglomeration, and the fillability of the hardened glass layer into the grooves may rather deteriorate. From this point of view, the _D50 particle size of the conductive powder (B1) is preferably 0.1 µm or more, more preferably 0.5 µm or more, and particularly preferably 1 µm or more.

Moreover, it is preferable that the photosensitive conductive paste (B) contains a high-concentration conductive powder (B1). As a result, a dense and thick conductive layer can be formed, and low-resistance electronic components can be manufactured. In general, a paste containing a high-concentration conductive powder (B1) makes it difficult for light to pass through the interior of the conductive film after drying. Curing becomes difficult, and undercuts tend to occur after development. However, according to the technology disclosed herein, it is possible to form a precise conductive layer simply by filling the grooves of the pre-formed glass hardened layer with the photosensitive conductive paste (B), so it is difficult to use with the conventional technology. A paste containing a high concentration of conductive powder (B1) can be used. Specifically, with the technology disclosed herein, the content of the conductive powder (B1) in the photosensitive conductive paste (B) can be 74% by mass or more. Further, from the viewpoint of further reducing the resistance of the electronic component, the content of the conductive powder (B1) is preferably 78% by mass or more, more preferably 79% by mass or more, further preferably 80% by mass or more, and 81% by mass. % or more is particularly preferred. According to the technique disclosed here, a paste containing such a high concentration of conductive powder (B1) can also be used. However, if the concentration of the conductive powder (B1) is increased too much, the fluidity of the paste is greatly reduced, and it may become difficult to fill the grooves of the cured glass film with the photosensitive conductive paste (B) without gaps. have a nature. Therefore, the content of the conductive powder (B1) is preferably 90% by mass or less, more preferably 85% by mass or less.

<Photocurable resin (B2)>
The photosensitive conductive paste (B) also contains a photocurable resin (B2) in the same manner as the photosensitive glass paste (A). The photocurable resin (B2) of the photosensitive conductive paste (B) can be the same type as the photocurable resin (A2) of the photosensitive glass paste (A) described above without particular limitation. , detailed description of the components is omitted.

In addition, from the viewpoint of suitably preventing photocuring of the photosensitive conductive paste (B) adhered onto the cured glass film, the photosensitive conductive paste (B) contains the photocurable resin content of the photosensitive glass paste ( It is preferable that the amount is less than A) to lower the photocurability. Specifically, the content of the photocurable resin (B3) in the photosensitive conductive paste (B) is preferably 15% by mass or less, more preferably 12% by mass or less, further preferably 9% by mass or less, and 6% by mass. % or less is particularly preferred. On the other hand, if insufficient curing occurs in the exposed portion of the conductive film in the exposure step, the conductive film (incompletely cured conductive film) in the groove may be removed in the developing step. From such a viewpoint, the lower limit of the content of the photocurable resin (B3) is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and particularly 3% by mass or more. preferable.

<Ultraviolet absorber (B3)>
In the electronic component manufacturing kit disclosed herein, an ultraviolet absorber (B3) containing an azo dye is also added to the photosensitive conductive paste (B). This can prevent the photosensitive conductive paste (B) (conductive film-like body) from photocuring on the cured glass film and lowering the precision of the conductive layer (conductive cured film). Specifically, in the technology disclosed herein, the photosensitive conductive paste (B) is supplied to the grooves of the cured glass film formed using the photosensitive glass paste (A). In supplying such a photosensitive conductive paste, it is difficult to fill the entire amount of the photosensitive conductive paste only in the grooves of the cured glass film, and the photosensitive conductive paste is applied to the area including the upper surface of the cured glass film by screen printing or the like. It is common to apply. Here, if a photosensitive conductive paste with excellent photocurability is used, even if the photosensitive conductive paste (conductive film-like body) adhering to the upper surface of the cured glass film is shielded from light in the exposure process, scattered light It may be photocured. In this case, even if a precise groove can be formed, the precision of the conductive layer of the electronic component after firing is greatly impaired. On the other hand, the photosensitive conductive paste (B) used in the technique disclosed herein is different from conventional general photosensitive conductive pastes in that the photocurability is reduced by the ultraviolet absorber (B3). . As a result, photocuring of the conductive film-like material adhering to the upper surface of the cured glass film is suitably prevented, and accurate formation of a fine conductive layer is realized.

In addition, if the ultraviolet absorber remains in the conductive layer after baking, it becomes an impurity that causes a decrease in conductivity, etc., making it difficult to manufacture high-performance electronic components. For this reason, in the technology disclosed herein, the UV absorber (B3) on the side of the photosensitive conductive paste (B) exhibits a sufficient curing inhibitory effect even in a small amount, and is easily removed by baking. I use dyes. As for the azo dyes and other organic dyes, the same types as the ultraviolet absorber (A3) of the photosensitive glass paste (A) can be used without particular limitations, so detailed description of the components is omitted.

The photocurability of the photosensitive conductive paste (B) may also vary depending on the type (color) and content of the conductive powder (B1). Therefore, the content of the ultraviolet absorber (B3) in the photosensitive conductive paste (B) is preferably adjusted appropriately according to the type and content of the conductive powder (B1). For example, when 74% by mass of silver-based particles are added as the conductive powder (B1), the content of the ultraviolet absorber (B3) is preferably 0.001% by mass or more. This can sufficiently suppress photocuring of the conductive film on the cured glass film. From the viewpoint of reliably preventing photocuring of the conductive film on the cured glass film, the content of the ultraviolet absorber (B3) in the photosensitive conductive paste (B) should be 0.005% by mass or more. It is preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more. On the other hand, the upper limit of the content of the ultraviolet absorber (B3) in the photosensitive conductive paste (B) is not particularly limited, and may be 1% by mass or less or 0.5% by mass or less. However, if the content of the ultraviolet absorber (B3) is excessively increased, the exposure time may be lengthened and the production efficiency may be lowered. Therefore, the content of the ultraviolet absorber (B3) is preferably 0.2% by mass or less, more preferably 0.15% by mass or less, and particularly preferably 0.1% by mass or less.

<Photoinitiator (B4)>
Further, the photopolymerization initiator (B4) may be added to the photosensitive conductive paste (B) as well as the photosensitive glass paste (A). As the photopolymerization initiator (B4) of the photosensitive conductive paste (B), the same type as the photosensitive glass paste (A) can be used without particular limitation. However, from the viewpoint of appropriately preventing photocuring of the conductive film on the cured glass film, the content of the photopolymerization initiator (B4) in the photosensitive conductive paste (B) is ) is preferably less than the content of the photopolymerization initiator (A4). For example, the content of the photopolymerization initiator (B4) in the photosensitive conductive paste (B) is preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, and 2% by mass or less. Especially preferred. On the other hand, from the viewpoint of realizing better photocuring, the content of the photopolymerization initiator (B4) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and 0.5% by mass. The above is more preferable, and 1% by mass or more is particularly preferable.

<Organic binder (B5)>
As for the organic binder (B5), the same kind of organic binder (A5) as in the photosensitive glass paste (A) can be used without particular limitation. In addition, the performance required for the photosensitive conductive paste (B) of the electronic component manufacturing kit disclosed herein is more important than the fixing property to the substrate surface, and the filling property (paste liquidity) is more important. Therefore, the content of the organic binder (B5) in the photosensitive conductive paste (B) is preferably less than the content of the organic binder (A5) in the photosensitive glass paste (A). Specifically, the content of the organic binder (B5) in the photosensitive conductive paste (B) is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and 7% by mass or less. is particularly preferred. On the other hand, the lower limit of the content of the organic binder (B5) may be 0% by mass (excluding the organic binder (B5)), may be more than 0% by mass, or may be 1% by mass or more. may be 2% by mass or more, or 3% by mass or more.

<Dispersion medium (B6)>
As for the dispersion medium (B6), the same type of dispersion medium (A6) as the dispersion medium (A6) for the photosensitive glass paste (A) can be used without particular limitation. As described above, considering the filling of the grooves with the cured glass film, the photosensitive conductive paste (B) of the electronic component manufacturing kit disclosed herein preferably has high fluidity. For example, the content of the dispersion medium (B6) in the photosensitive conductive paste (B) is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and particularly preferably 7% by mass or more. . On the other hand, the upper limit of the content of the organic binder (B5) in the photosensitive conductive paste (B) may be 30% by mass or less, 20% by mass or less, or 15% by mass or less. may be 12% by mass or less.

<Other additive ingredients>
In addition, the photosensitive conductive paste (B) may contain components other than the components (B1) to (B6) described above as long as the effects of the technology disclosed herein are not significantly impaired. The other additive component is not particularly limited, and conventionally known additive components can be used singly or in combination of two or more. Such other additive components include polymerization inhibitors, radical scavengers, antioxidants, plasticizers, surfactants, leveling agents, dispersants, antifoaming agents, anti-gelling agents, stabilizers, preservatives, and the like. mentioned. Although not particularly limited, the content of such other additive components is generally 5% by mass or less, typically 3% by mass or less, for example 2% by mass or less, preferably 1% by mass or less. good.

≪Summary of electronic component manufacturing kit≫
The configuration of the electronic component manufacturing kit disclosed herein has been described above. In the photosensitive glass paste (A) of the electronic component manufacturing kit having the above configuration, the content of the ultraviolet absorber (A3) containing an azo dye is set to 0.2% by mass or more. As a result, it is possible to prevent the light-shielding portion from being photo-cured by the diffused light inside the glass film-like body, so that it is possible to produce a glass-cured film in which grooves of a predetermined pattern are precisely formed. In the electronic component manufacturing kit disclosed herein, an ultraviolet absorber (B3) containing an azo dye is also added to the photosensitive conductive paste (B). This can suitably prevent the conductive film (dried film of the photosensitive conductive paste (B)) on the cured glass film from being photocured on the cured glass film. As described above, according to the electronic component manufacturing kit disclosed herein, by using a combination of the photosensitive glass paste (A) and the photosensitive conductive paste (B) configured as described above, a glass layer having precise grooves can be obtained. and a conductive layer filled without protruding from the precise grooves of the glass layer. That is, according to the technology disclosed herein, electronic components in which fine conductive layers are accurately formed can be stably manufactured.

In the electronic component manufacturing kit disclosed herein, inorganic components (glass powder (A1), conductive powder (B1)) are added between the photosensitive glass paste (A) and the photosensitive conductive paste (B). Ingredients except for can be made common. In this way, when the components of the two pastes are the same, the fillability of the photosensitive conductive paste (B) into the grooves of the cured glass film can be improved. On the other hand, considering the role of each paste, the components may be different. For example, the photosensitive glass paste (A) tends to emphasize the fixability to the substrate surface, while the photosensitive conductive paste (B) tends to emphasize the fluidity. Therefore, a combination of adding the organic binder (A5) to the photosensitive glass paste (A) and not adding the organic binder (B5) to the photosensitive conductive paste (B) can be employed.

2. Uses of Electronic Component Manufacturing Kit As described above, according to the electronic component manufacturing kit disclosed herein, electronic components having conductive layers with precise patterns can be stably manufactured. Applications of such electronic component manufacturing kits will be described below.

≪Types of electronic components≫
First, the electronic component manufacturing kit disclosed herein can be used to manufacture various electronic components such as inductance components, capacitor components, and multilayer circuit boards. Typical examples of inductance components include high frequency filters, common mode filters, inductors (coils) for high frequency circuits, inductors (coils) for general circuits, high frequency filters, choke coils, and transformers. Further, the shape (structure) of the electronic component is not particularly limited, and may be a surface mounting type, a through-hole mounting type, or the like. Further, the electronic component may be a laminated type in which a plurality of conductive layers are laminated, or may be a thin film type having a single conductive layer.

Further, as an example of the electronic component, there is a ceramic electronic component. In this specification, the term "ceramic electronic component" refers to electronic components in general that use ceramic substrates. Typical examples of ceramic electronic components include high-frequency filters with ceramic substrates, ceramic inductors (coils), ceramic capacitors, low temperature co-fired ceramic substrates (LTCC substrates), and high-temperature fired multilayer ceramic substrates. material (High Temperature Co-fired Ceramics Substrate: HTCC base material) and the like. In addition, examples of the ceramic substrate include amorphous ceramic substrates (glass ceramic substrates) and crystalline (that is, non-glass) ceramic substrates. In the case of using a glass ceramic substrate, the photosensitive glass paste (A) is printed on a carrier sheet such as a PET film in a plate shape and dried, and then the photosensitive glass paste (A) is photocured. The substrate may be formed by using the plate-shaped cured glass film obtained as a green sheet and baking the plate-shaped cured glass film. Crystalline ceramic substrates include zirconium oxide (zirconia), magnesium oxide (magnesia), aluminum oxide (alumina), silicon oxide (silica), titanium oxide (titania), cerium oxide (ceria), yttrium oxide ( yttria), barium titanate, and other oxide materials; cordierite, mullite, forsterite, steatite, sialon, zircon, ferrite, and other complex oxide materials; silicon nitride, aluminum nitride nitride); carbide-based materials such as silicon carbide; hydroxide-based materials such as hydroxyapatite;

≪Manufacturing method of electronic parts≫
Next, an embodiment of an electronic component manufacturing method using the electronic component manufacturing kit disclosed herein will be described. 1 to 6 are cross-sectional views explaining each step of the method for manufacturing an electronic component according to this embodiment. Note that the dimensional relationships (length, width, thickness, etc.) in these drawings do not necessarily reflect the actual dimensional relationships.

<Printing of photosensitive glass paste S10>
As shown in FIG. 1, in the manufacturing method according to the present embodiment, after the photosensitive glass paste (A) having the above configuration is applied (printed) to the surface of the green sheet 10 as the base material, the photosensitive glass paste (A ) to dry. Thereby, the glass film-like body 20 is formed on the green sheet 10 . The drying temperature in this step is suitably about 30° C. to 60° C., and the drying time is suitably about 5 minutes to 20 minutes. As for the raw material and formation procedure of the green sheet 10, conventionally known ones can be adopted without particular limitation, and the detailed description is omitted because the technology disclosed herein is not limited.

<Exposure of glass film S20>
Next, in this embodiment, a photomask M1 having slits M1a of a predetermined pattern is placed on the glass film 20, and a portion of the glass film 20 exposed from the slits M1a is exposed (see FIG. 2). ). As a result, the light-shielding portion of the photomask M1 is maintained as the glass film 20, and the exposed portion immediately below the slit M1a is photocured to become a glass cured film 22. FIG. In this exposure process, an exposure machine that emits light rays (typically ultraviolet rays) in a wavelength range of 10 to 500 nm, for example, an ultraviolet irradiation lamp such as a high-pressure mercury lamp, a metal halide lamp, or a xenon lamp can be used.

Here, in the manufacturing method according to the present embodiment, 0.2% by mass or more of an ultraviolet absorber (A3) containing an azo dye is added to the photosensitive glass paste (A), which is the precursor of the glass filmy body 20. It is As a result, it is possible to prevent the ultraviolet rays from diffusing inside the glass film body 20, and to reliably prevent the light-shielding portion arranged directly under the photomask M1 from being photocured.

<Development of glass cured film S30>
Next, a developer having a predetermined component is supplied onto the green sheet 10 to remove the uncured glass film 20 . As a result, a cured glass film 22 having a predetermined pattern of grooves 24 is developed on the green sheet 10 (see FIG. 3). At this time, in the manufacturing method according to the present embodiment, the light-shielding portion of the photomask M1 is reliably prevented from being photocured in the above-described exposure S20 of the glass film. Therefore, in this step, by removing the uncured glass film 20, a cured glass film 22 in which fine grooves 24 are precisely formed is produced. As the developer in this step, an alkaline aqueous developer or the like can be used. As an example of such an aqueous developer, an aqueous sodium hydroxide solution, an aqueous sodium carbonate solution, or the like can be used. The alkali concentration of these water-based developers may be adjusted to, for example, 0.01 to 0.5% by mass.

<Printing of photosensitive conductive paste S40>
Next, in the manufacturing method according to the present embodiment, the photosensitive conductive paste (B) is printed so as to fill the grooves 24 of the cured glass film 22, and the photosensitive conductive paste (B) is dried. As a result, the conductive film-like body 30 is formed inside the groove 24 of the glass cured film 22 . In addition, the printing means in this step is not particularly limited. For example, as shown in FIG. 4, screen printing is used to print a photosensitive conductive paste (B) on the entire upper surface of the cured glass film 22 .

<Exposure of conductive film S50>
Next, in this step, a photomask M2 having slits M2a of a predetermined pattern is placed on the conductive film 30 (see FIG. 5). Here, in this step, the slit M2a of the photomask M2 is arranged on the conductive film-like body 30 filled in the groove 24, and the region above the glass hardened film 22 is shielded from light by the photomask M2. , to adjust the placement position of the photomask M2. Then, a portion of the conductive film-like body 30 exposed from the slit M2a is exposed. As a result, the conductive film 30 filled in the grooves 24 is photocured to become a conductive cured film 32 .

If light scattering occurs inside the conductive film 30 during the exposure S50 of the conductive film, there is a risk that part of the unexposed portion covered with the photomask M2 will be photocured. In contrast, in the manufacturing method according to the present embodiment, the conductive film 30 is also added with an ultraviolet absorber (B3) containing an azo dye. As a result, the conductive film-like body 30 on the cured glass film 22, which is a light-shielding portion, can be easily maintained in an unexposed state. It can be suitably prevented.

<Development of conductive cured film S60>
Next, in the manufacturing method according to the present embodiment, the uncured conductive film-like body 30 adhering to the glass cured film 22 is removed using a developer having a predetermined component. As a result, a composite 1, which is a precursor of an electronic component, is formed. As shown in FIG. 6, the composite 1 includes a green sheet 10 which is a precursor of a base material, a cured glass film 22 obtained by photocuring a photosensitive glass paste (A), and a photosensitive conductive paste (B). is provided with a photo-cured conductive cured film 32 . In the composite 1, grooves 24 having a predetermined pattern are precisely formed in the cured glass film 22, and a precise conductive cured film 32 filled in the grooves 24 is formed.

By firing the composite 1, the cured glass film 22 is sintered to form a glass layer, and the conductive cured film 32 is sintered to form a conductive layer, thereby producing an electronic component. An electronic component manufactured in this manner has a glass layer having a precise groove and a conductive layer formed along the precision groove. The firing temperature (maximum temperature in the firing process) when firing the composite 1 is preferably about 600.degree. C. to 1000.degree.

≪Manufacturing of Multilayer Chip Inductors≫
In addition, according to the technology disclosed herein, not only thin-film electronic components having a single conductive layer as described above, but also electronic components (multilayer chip inductors) having a plurality of laminated conductive layers can be easily manufactured. . A procedure for manufacturing a multilayer chip inductor will be described below.

When manufacturing the multilayer chip inductor, first, the composite 1 (see FIG. 6) having the glass cured film 22 and the conductive cured film 32 formed on the green sheet 10 is produced according to the procedure described above. Then, as shown in FIG. 7, the photosensitive glass paste (A) is printed so as to cover the upper surfaces of the cured glass film 22 and the conductive cured film 32 of the composite 1, and dried and exposed. As a result, the first layer L1 in which the conductive cured film 32 is covered with the glass cured film 22 is formed.

Next, a via hole 26 is formed in the cured glass film 22 forming the upper surface of the first layer L1 using a conductive drilling machine or the like to expose a portion of the upper surface of the conductive cured film 32 (see FIG. 8). After the via hole 26 is filled with the photosensitive conductive paste (B), drying and exposure are performed. As a result, vias 36 connected to the conductive cured film 32 of the first layer are formed (see FIG. 9). At this time, it is preferable to use a photomask so that only the conductive film (the photosensitive conductive paste (B) after drying) in the via hole 26 is exposed.

Then, the steps of "printing of photosensitive glass paste (A) S10" to "development of cured glass film S30" described above are performed again to form a cured glass film 22 having grooves 24 on the upper surface of the first layer L1. (See FIG. 10). Next, the above-described steps of “printing of photosensitive conductive paste (B) S40” to “development of conductive cured film S60” are performed again to form conductive cured film 32 inside groove 24 of glass cured film 22. (See FIG. 11). Thereby, the second layer L2 having the glass cured film 22 and the conductive cured film 32 is formed on the upper surface of the first layer L1. The conductive cured film 32 of the second layer L2 is connected to the conductive cured film 32 of the first layer L1 via vias .

In manufacturing the multilayer chip inductor, by repeating each of the steps described above, a plurality of layers (in FIG. 12, A layered body 100 comprising a first layer L1 to a fourth layer L4) is produced. Also, in this laminate 100, the conductive cured films 32 of the first layer L1 to the fourth layer L4 are connected via vias . A multilayer chip inductor having precise conductive layers is manufactured by applying a paste for forming external electrodes to the multilayer body 100 and then performing a firing process.

[Test example]
Test examples relating to the technology disclosed herein will be described below. It should be noted that the following description is not intended to limit the technology disclosed herein to those shown in the test examples.

1. Preparation of photosensitive glass paste (1) Sample 1
As sample 1, a photosensitive glass paste was prepared by mixing glass powder, a photocurable resin, a photopolymerization initiator, and a dispersion medium. For sample 1, glass powder (SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ —K ₂ O based glass) having an average particle size of 2 μm was prepared. Also, a urethane acrylate oligomer (polyfunctional urethane (meth)acrylate) was prepared as a photocurable resin. Next, a methylcellulose-based water-soluble resin and a water-soluble acrylic resin (methacrylic acid/methyl methacrylate copolymer) were prepared as organic binders. Furthermore, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one was prepared as a photopolymerization initiator. A mixed solvent of diethylene glycol monoethyl ether acetate and ethylene glycol monobutyl ether was prepared as a dispersion medium. A photosensitive glass paste was prepared by dissolving the glass powder, the photocurable resin, the organic binder, and the photopolymerization initiator prepared above in a dispersion medium. In this sample, the content of the glass powder is 52% by mass, the content of the photocurable resin is 6% by mass, and the content of the organic binder is 13% by mass with respect to the total amount of the photosensitive glass paste (100% by mass). %, the content of the photopolymerization initiator was 3% by mass, and the balance was the mixed solvent.

(2) Samples 2-6
A photosensitive glass paste having the same composition as Sample 1 was prepared, except that an ultraviolet absorber was added. In samples 2 to 6, Oil Yellow (manufactured by Orient Chemical Industry Co., Ltd., model number: Oil Yellow 3G), which is a yellow azo dye, was used as the ultraviolet absorber. Further, Samples 2 to 6 differ in the amount of the oil yellow added. Table 1 shows the oil yellow content (% by mass) in each sample. The increase due to the addition of Oil Yellow was adjusted by reducing the content of the dispersion medium.

(3) Samples 7-8
A photosensitive glass paste having the same composition as Sample 1 was prepared, except that a white dye, benzotriazole (manufactured by ADEKA Corporation, model number: LA-24) was added as an ultraviolet absorber. Note that samples 7 and 8 differ in the amount of benzotriazole added. Table 1 shows the content (% by mass) of benzotriazole in each sample.

2. Evaluation Test In this test, the photosensitive glass pastes of Samples 1 to 8 were used to form a cured glass film having grooves of a predetermined pattern, and the precision of the cured glass film after formation was evaluated. First, in this test, a PET film was used as an object to be printed in order to easily visually evaluate the precision of the cured glass film after formation. Then, using screen printing, the photosensitive glass paste (Samples 1 to 8) was applied on a PET film in a size of 4 cm x 4 cm, and then dried at 45°C for 15 minutes to form a glass film. . Then, after covering the glass film with a photomask having slits of a predetermined pattern, light is irradiated using an exposure machine (illuminance of 50 mJ/cm ² , exposure amount of 100 mJ/cm ² ), and the slits of the photomask are irradiated. was cured to form a cured glass film. The photomask used in this test has L/S (line/space) set to 20 μm/20 μm.

Next, a 0.1% by mass alkaline Na ₂ CO ₃ aqueous solution (developer) is sprayed onto the glass film-like material and the cured glass film on the PET film until the breakpoint (B.P.) +5 seconds is reached. (development process). In addition, the above B. P. The time period until the removal of the glass film-like material from the light-shielding portion by the developer can be visually confirmed. B. in this test. P. was 27 seconds. Then, after removing the glass film material from the light shielding portion, the substrate was washed with pure water and dried at room temperature. Thus, a cured glass film having a predetermined pattern of grooves was formed.

Next, in this test, the glass cured film formed on the PET film was observed with an optical microscope. An optical micrograph of each sample is shown in FIG. Then, in microscopic observation of 20 fields of view, it was evaluated whether or not the groove and the outer edge of the cured glass film were precisely formed. The results of the evaluation are shown in the column of "accuracy evaluation" in Table 1. In addition, the evaluation criteria in this evaluation are as follows.
"Good": In all fields of view, the outer edge of the cured glass film was clearly formed, and adjacent cured glass films were reliably partitioned by grooves.
"Poor": A groove portion was not formed, and an area where adjacent glass cured films were in contact was confirmed.

First, as shown in Table 1 and FIG. 13, in Sample 1, no grooves were formed in the cured glass film after development, and the outer edge of the cured glass film was also formed with a large number of irregularities, which was unclear. It was something. Thus, the reason why a cured glass film reflecting the pattern of the photomask is not formed even though the glass film is covered with a photomask is that scattered light is generated inside the glass film. , because the light reaches the light shielding portion.

Next, as shown in samples 2 to 6, when various amounts of azo dye (oil yellow) were added, when the amount of addition reached 0.2% by mass or more, the glass cured after development. The result was a dramatic improvement in membrane precision. On the other hand, as shown in Samples 7 and 8, when an ultraviolet absorber (benzotriazole) that is not an azo dye is used, even when the amount added is greatly increased, the area where the cured glass films are in contact with each other is It was not possible to form a precise groove. From these experimental results, it was found that a cured glass film having precise grooves can be formed by using a photosensitive glass paste containing 0.2% by mass or more of an ultraviolet absorber containing an azo dye. Then, it is believed that if a photosensitive conductive paste can be applied to the upper surface of such a cured glass film to prevent photocuring of the conductive film-like material on the upper surface of the cured glass film, it is possible to stably manufacture electronic components having a precise conductive layer. be done.

Although the present invention has been described in detail above, these are merely examples, and the present invention can be modified in various ways without departing from the scope of the invention.

REFERENCE SIGNS LIST 1 composite 10 green sheet 20 glass film 22 cured glass film 24 groove 30 conductive film 32 conductive cured film 36 via

Claims (20)

A photosensitive glass paste (A) for forming a glass layer having grooves of a predetermined width on a substrate surface, and a photosensitive conductive paste (B) for forming a conductive layer in the grooves of the glass layer. is a kit,
The photosensitive glass paste (A) contains a glass powder (A1), a photocurable resin (A2), and an ultraviolet absorber (A3),
The photosensitive conductive paste (B) contains a conductive powder (B1), a photocurable resin (B2), and an ultraviolet absorber (B3),
Both the ultraviolet absorber (A3) of the photosensitive glass paste (A) and the ultraviolet absorber (B3) of the photosensitive conductive paste (B) contain an azo dye,
An electronic component manufacturing kit, wherein the content of the ultraviolet absorber (A3) is 0.2% by mass or more when the total weight of the photosensitive glass paste (A) is 100% by mass. 2. The electronic component manufacturing kit according to claim 1, wherein said glass powder (A1) contains B ₂ O ₃ —SiO ₂ -based glass containing B ₂ O ₃ and SiO ₂ as main components. The B ₂ O ₃ —SiO ₂ -based glass contains 5 to 20% by mass of the B ₂ O ₃ and 20 to 70% by mass of the SiO ₂ in terms of oxide-equivalent mass ratio. 3. The electronic component manufacturing kit according to 2. Any one of claims 1 to 3, wherein the content of the glass powder (A1) is 30% by mass or more and 60% by mass or less when the total weight of the photosensitive glass paste (A) is 100% by mass. A kit for manufacturing electronic components according to . The content of the ultraviolet absorber (A3) is 1.0% by mass or less when the total weight of the photosensitive glass paste (A) is 100% by mass, according to any one of claims 1 to 4. A kit for manufacturing electronic components as described. The electronic component manufacturing kit according to any one of claims 1 to 5, wherein the azo dye contains at least one selected from a yellow dye and a red dye. The electronic component manufacturing kit according to any one of claims 1 to 6, wherein the photosensitive glass paste (A) further contains a photopolymerization initiator (A4). The electronic component manufacturing kit according to any one of claims 1 to 7, wherein the photosensitive glass paste (A) further contains an organic binder (A5). The electronic component manufacturing kit according to any one of claims 1 to 8, wherein the photosensitive glass paste (A) further contains a dispersion medium (A6). The electronic component manufacturing kit according to claim 9, wherein the dispersion medium (A6) is an organic solvent having a boiling point of 150°C or higher and 250°C or lower. The electronic component manufacturing kit according to any one of claims 1 to 10, wherein the conductive powder (B1) contains silver-based particles. The electronic component manufacturing kit according to any one of claims 1 to 11, wherein the content of said conductive powder (B1) in said photosensitive conductive paste (B) is 74% by mass or more. Claims 1 to 12, wherein the content of the ultraviolet absorber (B3) is 0.001% by mass or more and 0.2% by mass or less when the total weight of the photosensitive conductive paste (B) is 100% by mass. The electronic component manufacturing kit according to any one of . The electronic component manufacturing kit according to any one of claims 1 to 13, wherein the photosensitive conductive paste (B) further contains a photopolymerization initiator (B4). The electronic component manufacturing kit according to any one of claims 1 to 14, wherein the photosensitive conductive paste (B) further contains an organic binder (B5). The electronic component manufacturing kit according to any one of claims 1 to 15, wherein the photosensitive conductive paste (B) further contains a dispersion medium (B6). A photosensitive glass paste that forms a glass layer having grooves of a predetermined width on a substrate surface,
Glass powder (A1), a photocurable resin (A2), and an ultraviolet absorber (A3),
The ultraviolet absorber (A3) contains an azo dye,
A photosensitive glass paste, wherein the content of the ultraviolet absorber (A3) is 0.2% by mass or more when the total weight is 100% by mass. a green sheet that is a precursor of the base material;
a cured glass film disposed on the green sheet and photocured with the photosensitive glass paste (A) according to any one of claims 1 to 16;
A conductive cured film disposed on the green sheet and photocured with the photosensitive conductive paste (B) according to any one of claims 1 to 16;
with
A composite, wherein grooves of a predetermined pattern are provided in the glass cured film, and the electrically conductive cured film is formed inside the grooves. a substrate;
A glass layer arranged on the surface of the base material and made of a fired body of the photosensitive glass paste (A) according to any one of claims 1 to 16;
A conductive layer disposed on the surface of the base material and made of a fired body of the photosensitive conductive paste (B) according to any one of claims 1 to 16,
A composite, wherein the glass layer is provided with grooves of a predetermined pattern, and the conductive layer is formed inside the grooves. A method for manufacturing an electronic component using the electronic component manufacturing kit according to any one of claims 1 to 16,
A step of applying the photosensitive glass paste (A) onto a green sheet, followed by exposure and development to form a cured glass film having grooves of a predetermined pattern;
A step of forming a conductive cured film by performing exposure and development after filling the grooves of the glass cured film with the photosensitive conductive paste (B);
A method for manufacturing an electronic component, comprising a step of baking the green sheet, the glass cured film, and the conductive cured film.

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