JP7274019B1 - Photosensitive glass composition and its use - Google Patents

Abstract

[Problem] To provide a photosensitive glass composition capable of forming a glass layer that has a fine pattern and is suppressed in warpage and peeling from a substrate. A photosensitive glass composition disclosed herein is used for producing a glass layer in an electronic component comprising a glass layer having a groove of a predetermined width and a conductive layer disposed in the groove of the glass layer. The photosensitive glass composition used. The photosensitive glass composition includes at least glass powder, a photocurable resin, a photopolymerization initiator, and an organic dispersion medium. The photocurable resin contains a urethane (meth)acrylate oligomer A having a functionality of 5 or more and a urethane (meth)acrylate oligomer B having a functionality of 2 or less. The mass ratio (A:B) of the pentafunctional or higher urethane (meth)acrylate oligomer A and the difunctional or lower urethane (meth)acrylate oligomer B is 90:10 to 12.5:87.5. [Selection drawing] Fig. 1

Description

The present invention relates to a photosensitive glass composition and its use.

2. Description of the Related Art Electronic components such as multilayer chip inductors are equipped with a circuit board in which a conductive layer having a predetermined pattern is formed on a base material. In recent years, a method of forming a conductive layer of an electronic component as described above using a composition containing a photopolymerizable substance and a conductive material (hereinafter referred to as "photosensitive conductive composition") is widely known. ing. An example of such a technique is a photolithography method (eg, Patent Document 1). In this method, first, a photosensitive conductive composition is applied to the surface of a base material, and then the composition 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, should be further reduced. are required to do so. 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 (exposure amount) to the conductive film decreases in the exposure process. side). In this case, the lower part of the conductive film is not sufficiently hardened and is removed in the developing process, so that a conductive layer having an inverted trapezoidal shape when viewed 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 composition containing a photopolymerizable substance and a glass material (hereinafter referred to as "photosensitive glass composition") is used in combination. A photolithographic method has been proposed. In this method, first, a photosensitive glass composition 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 composition and exposing the composition. 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. Patent Documents 2 to 4 disclose examples of photosensitive compositions used in such manufacturing techniques.

Japanese Patent No. 6694099 Japanese Patent No. 5163687 Japanese Patent No. 5195432 Japanese Patent No. 4719332

By the way, a glass film-like material printed with a photosensitive glass composition has higher light transmittance (transparency) than a conductive film-like material. In such a glass film having high light transmittance, even if the amount of light supplied is reduced by reducing the slit of the photomask in order to form a fine wiring pattern (pattern of the groove) in the exposure process, the above Undercut due to poor curing as described above is less likely to occur. On the other hand, when only a resin having excellent photocurability is used in the photosensitive glass composition, photocuring shrinkage (volumetric shrinkage due to curing) occurs due to the high light transmittance in the exposure process of the glass film. Cheap. For example, when the photosensitive glass compositions of Patent Documents 3 and 4 described above are used, photocuring shrinkage occurs in the exposure process, and warping (curling) may occur in the cured glass film after the exposure process.

Further, in Patent Document 3, forming a via hole to form a conductive pattern of a laminated chip is considered. No consideration has been given to forming a glass layer of Therefore, when attempting to form a glass layer with a fine pattern using the photosensitive glass composition disclosed in Patent Document 3, there is a problem that a part of the glass layer is peeled off during the development process.

The present invention has been made in view of such circumstances, and an object thereof is to provide a photosensitive glass composition capable of forming a glass layer having a fine pattern and being suppressed in warping and peeling from a substrate. to provide. Another object of the present invention is to provide an electronic component including such a glass layer and a conductive layer, and a method for manufacturing the electronic component.

To achieve the above objects, a photosensitive glass composition disclosed herein is provided. The photosensitive glass composition disclosed herein is used for producing the glass layer in an electronic component comprising a glass layer having grooves of a predetermined width and a conductive layer disposed in the grooves of the glass layer. The photosensitive glass composition includes at least glass powder, a photocurable resin, a photopolymerization initiator, and an organic dispersion medium. The photocurable resin contains a urethane (meth)acrylate oligomer A having a functionality of 5 or more and a urethane (meth)acrylate oligomer B having a functionality of 2 or less. The mass ratio (A:B) of the pentafunctional or higher urethane (meth)acrylate oligomer A to the difunctional or lower urethane (meth)acrylate oligomer B is 90:10 to 12.5:87.5.

In the photosensitive glass composition, the penta- or higher functional urethane (meth)acrylate oligomer A having high photocurability and the flexible urethane (meth)acrylate oligomer B having two or less functionality are mixed at a mass ratio as described above. By containing it, it is possible to suitably suppress the photocuring shrinkage caused by the high light transmittance in the exposure process. According to the photosensitive glass composition having such a configuration, a fine pattern can be suitably formed, and in a glass cured film obtained by photocuring the photosensitive glass composition, warping after the exposure process and development Delamination from the substrate during the process can be reduced.

In a preferred embodiment of the photosensitive glass composition disclosed herein, the mass ratio (A:B ) is 82.5:17.5 to 25:75.
According to such a configuration, it is possible to sufficiently reduce warpage and suppress peeling even when the exposure process and the development process are performed under a wider range of conditions.

In a preferred aspect of the photosensitive glass composition disclosed herein, the photocurable resin further contains a (meth)acrylate having a functionality of 2 or less.
According to such a configuration, in the cured glass film obtained by photocuring the photosensitive glass composition, the warpage after the exposure process can be reduced, and the viscosity can also be reduced, so that the above effects can be exhibited more preferably. can be done.

In a preferred aspect of the photosensitive glass composition disclosed herein, the glass powder contains B ₂ O ₃ —SiO ₂ -based glass containing B ₂ O ₃ and SiO ₂ as main components. In this aspect, the B ₂ O ₃ —SiO ₂ -based glass contains 5% by mass or more of B ₂ O _{3 and} 20% by mass in terms of oxide, when the entire glass is 100% by mass. % by mass or less, and 20% by mass or more and 70% by mass or less of SiO ₂ . Further, the proportion of the glass powder is 45% by mass or more and 60% by mass or less when the entire photosensitive glass composition is taken as 100% by mass.
According to the photosensitive glass composition having such a constitution, a glass layer having excellent fixability can be formed.

In a preferred aspect of the photosensitive glass composition disclosed herein, the organic dispersion medium is an organic solvent having a boiling point of 150° C. or higher and 250° C. or lower.
According to such a configuration, the storage stability of the photosensitive glass composition and the handleability of the composition during printing can be improved, and the drying temperature after printing can be kept low.

Further, according to the technology disclosed herein, there is provided an electronic component including a glass layer made of a fired body of the photosensitive glass composition, and a conductive layer disposed in the groove of the glass layer.
A glass layer using the photosensitive glass composition has a fine pattern. Therefore, by forming a conductive layer using such a glass layer, an electronic component having a fine pattern can be realized.

Further, according to the technique disclosed herein, the above-described photosensitive glass composition is applied onto a substrate, exposed, developed, and then baked to obtain a glass layer composed of a baked body of the above-mentioned photosensitive glass composition. A method of manufacturing an electronic component is provided, comprising the step of forming a
According to this manufacturing method, an electronic component having a fine pattern with L/S of 30 μm/30 μm or less can be manufactured with high accuracy.

1 is a cross-sectional view schematically showing the structure of a multilayer chip inductor according to one embodiment; FIG. FIG. 4 is a diagram explaining a manufacturing procedure of a multilayer chip inductor according to one embodiment;

Preferred embodiments of the present invention are described below. Matters other than those specifically mentioned in this specification, which are necessary for carrying out the present invention, can be grasped as design matters by those skilled in the art based on the prior art in the relevant field. The present invention can be implemented based on the contents disclosed in this specification and common general technical knowledge in the field. In this specification, the notation "A to B" indicating a numerical range means "A or more and B or less" unless otherwise specified.

In the present specification, a photosensitive glass composition dried at a temperature below the boiling point of the photocurable resin and the photopolymerization initiator, specifically approximately 200° C. or below, for example, 100° C. or below, is referred to as “glass film-like. A film obtained by photocuring the glass film is called a "cured glass film". And what baked the said glass cured film is called a "glass layer."
Further, in the present specification, a photosensitive conductive composition dried at a temperature below the boiling point of the photocurable resin and the photopolymerization initiator, specifically approximately 200° C. or lower, for example, 100° C. or lower, is referred to as a “conductive film. The photo-curing of the conductive film-like body is called a “conductive cured film”. And what baked the said electrically conductive cured film is called a "conductive layer."
The term "paste" as used herein refers to a mixture in which a part or all of the solid content is dispersed in a solvent, and includes so-called "slurry", "ink", and the like.

1. Photosensitive glass composition The photosensitive glass composition disclosed herein is an electronic component comprising a glass layer having grooves of a predetermined width, and a conductive layer disposed in the grooves of the glass layer. It is the composition used for production. The photosensitive glass composition is typically pasty. Such a photosensitive glass composition contains at least glass powder, a photocurable resin, a photopolymerization initiator, and an organic dispersion medium. Hereinafter, each component will be described in order.

(1) Glass powder Glass powder is a component that remains without being burned off during firing and forms a glass layer after firing. As the glass powder, crystallized glass containing crystals may be used in addition to general amorphous glass. The glass powder is preferably amorphous glass having no crystallized portion. Preferred examples of such glass powder 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 a photosensitive glass composition containing B ₂ O ₃ —SiO ₂ -based glass, it is possible to form a glass layer with excellent fixability to the substrate surface.
In this specification, the term "powder" is a term that includes powder, frit, and the like.

Since the boron component (B ₂ O ₃ ) contributes to increasing the fluidity during firing, it is presumed that the fixability of the glass layer to the base material surface can be improved. 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 3% by mass or more, and more preferably 5% by mass or more in terms of oxide. It is even more preferable to have On the other hand, an excessive proportion of B ₂ O ₃ in the B ₂ O ₃ —SiO ₂ -based glass can make it difficult to maintain the shape of the glass layer during firing. From this point of view, 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 23% by mass or less, more preferably 20% by mass or less in terms of oxide. % by mass or less is more preferable.
A silicon component (SiO ₂ ) is a component that constitutes the skeleton of the glass layer after firing. The proportion of SiO ₂ in the B ₂ O ₃ —SiO ₂ -based glass is preferably 10% by mass or more, more preferably 15% by mass or more, and more preferably 20% by mass or more in terms of oxide. More preferred. On the other hand, the proportion of SiO ₂ in the B ₂ O ₃ —SiO ₂ -based glass is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. .
The B ₂ O ₃ —SiO ₂ -based glass may contain components other than B ₂ O ₃ and SiO ₂ . Examples of such components include oxides of group 2 elements (R represents, for example, Mg, Ca, Zn, Ba, and Sr; the same shall apply hereinafter), aluminum components (Al ₂ O ₃ ), zinc components (ZnO), and the like. be done.

The glass powder is not limited to the B ₂ O ₃ —SiO ₂ -based glass described above, and conventionally known glass compositions can be used without particular limitation. Examples include SiO2-RO glass, _SiO2 -RO- _Al2O3 glass _{, SiO2} -RO- _Y2O3 glass, _SiO2 -RO- _{B2O3 glass} , and _SiO2 - _{Al2 .} Examples include 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, and the like.

The _D50 particle size of the glass powder is not particularly limited, but considering dispersibility etc., it is preferably 0.3 μm or more, more preferably 0.7 μm or more, and 1 μm or more. is more preferred. On the other hand, considering the surface smoothness of the glass layer after drying, the _D50 particle size of the glass powder is preferably 8 μm or less, more preferably 5 μm or less, and even more preferably 2 μm or less. .
In the present specification, " _D50 particle size" refers to 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.

If the proportion of the glass powder in the photosensitive glass composition is too high, the paste viscosity increases, which can lead to a decrease in working efficiency, a decrease in printability, and the like. From this point of view, the proportion of the glass powder in the entire photosensitive glass composition is preferably 60% by mass or less, more preferably 58% by mass or less, even more preferably 56% by mass or less, for example 54% by mass or less. good too. On the other hand, when the proportion of the glass powder in the photosensitive glass composition is low, the printability is improved as the viscosity of the composition decreases, and the shielding in the glass film during photocuring decreases (i.e. Developability is expected to be improved by increasing the gap). Therefore, the proportion of glass powder in the composition can be reduced relatively easily. However, if the proportion of the glass powder in the photosensitive glass composition is too low, the density of the glass in the glass layer will be low, and the film thickness of the conductive layer formed in the grooves of the glass layer may be too thin. . From these points of view, the lower limit of the proportion of the glass powder in the entire photosensitive glass composition is, for example, preferably 35% by mass or more, more preferably 40% by mass or more, and 45% by mass or more. is more preferable, particularly preferably 50% by mass or more, and may be, for example, 52% by mass or more.

(2) Photo-curable resin A photo-curable resin 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 used herein, the term "photocurable resin" includes monomers, oligomers, and polymers. In the photosensitive glass composition disclosed herein, as photocurable resins, pentafunctional or higher urethane (meth)acrylate oligomer A (hereinafter also referred to as "oligomer A") and bifunctional or lower urethane (meth) ) acrylate oligomer B (hereinafter also referred to as “oligomer B”). In a preferred embodiment, the photocurable resin further contains a (meth)acrylate having a functionality of 2 or less.

As used herein, "urethane (meth)acrylate" refers to a compound having a urethane bond (--NH--C(=O)--O--) and a (meth)acryloyl group in one molecule. In the present specification, the term "(meth)acryloyl group" means "methacryloyl group (-C(=O)-C(CH ₃ )=CH ₂ )" and "acryloyl group (-C(=O)- CH═CH ₂ )”. And "(meth)acrylate" is a term including "methacrylate" and "acrylate".
As used herein, the term "urethane (meth)acrylate oligomer" refers to a compound having a urethane bond and a (meth)acryloyl group in the molecule and having a relatively small weight-average molecular weight (Mw) (e.g., weight polymer with an average molecular weight of 10,000 or less).

The pentafunctional or higher urethane (meth)acrylate oligomer A is a polyfunctional urethane (meth)acrylate compound having 5 or more (generally 5 to 15, for example 5 to 10) functional groups in the molecule. When the oligomer A has five or more functional groups, it has high photocurability, and by including the oligomer A, the hardness of the cured glass film can be improved.

The pentafunctional or higher urethane (meth)acrylate oligomer A may be a compound obtained by reacting a (meth)acrylate compound containing a hydroxy group with a polyisocyanate compound. Moreover, it may be a compound obtained by reacting an acrylate compound containing an isocyanate group with a polyol compound. Alternatively, it may be a compound obtained by reacting a (meth)acrylate compound containing a hydroxy group, a polyisocyanate compound, and a polyol compound. Although not particularly limited, the pentafunctional or higher urethane (meth)acrylate oligomer A is reacted with a polyol compound and a polyisocyanate compound to produce a urethane-type precursor having an isocyanate group, and then reacted with the (meth)acrylate compound. can be obtained by

Examples of (meth)acrylate monomers containing a hydroxy group that can be used as raw materials for the oligomer A include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, Acrylate, hydroxyalkyl (meth)acrylate such as 6-hydroxyhexyl (meth)acrylate, 2-hydroxyethyl acryloyl phosphate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) ) acrylate, dipropylene glycol (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-(meth) acryloyloxypropyl ( meth)acrylate, glycerin di(meth)acrylate, 2-hydroxy-3-acryloyl-oxypropyl methacrylate, pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth) Acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol penta(meth)acrylate and the like. These may be used singly or in combination of two or more.

Polyisocyanate compounds include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, pentane diisocyanate, lysine diisocyanate, aliphatic polyisocyanates such as norbornane diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate, cyclohexyldiisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, dicyclohexylmethane diisocyanate; and the like. These may be used singly or in combination of two or more.

The polyol compound may be, for example, a high molecular weight polyol such as polyether polyol or polyester polyol, or a low molecular weight polyol such as triethylene glycol or hexanediol. These may be used singly or in combination of two or more.

In a preferred embodiment, the oligomer A is a pentafunctional or higher aliphatic urethane (meth)acrylate oligomer whose polyisocyanate compound is the above-described aliphatic and/or alicyclic polyisocyanate. These penta- or higher-functional aliphatic urethane (meth)acrylate oligomers have the property of curing more rapidly in the exposure process, and can have higher hardness in glass cured films. Thereby, a glass cured film having a precise pattern can be formed.

The weight average molecular weight (Mw) of the penta- or higher functional urethane (meth)acrylate oligomer A is typically 10,000 or less. The weight average molecular weight (Mw) is, for example, preferably 500 to 10,000, may be 750 to 8,000, or may be 1,000 to 5,000. In addition, in this specification, the weight average molecular weight Mw can be measured by gel permeation chromatography (GPC).

Such penta- or higher-functional urethane (meth)acrylate oligomer A may be prepared by purchasing a commercially available product. Specifically, the product names EBECRYL1290, EBECRYL5129, EBECRYL8301R, KRM8200, KRM8904, and KRM8452 manufactured by Daicel Allnex Co., Ltd.; Nippon Kayaku Co., Ltd. trade names UX-5005, UX-5103, UX-5102D-M20, UX5000, DPHA-40H, Shin-Nakamura Chemical Co., Ltd. trade names UA-1100H, U-6LPA, UA-33H, U-10HA, U-10PA, U-15HA, Miramer PU610, Miramer MU9500 (trade names) manufactured by Toyo Chemicals Co., Ltd., and the like. These may be used individually by 1 type, and may be used in mixture of 2 or more types.

The bifunctional or less urethane (meth)acrylate oligomer B is a urethane (meth)acrylate compound having one or two functional groups in the molecule. Since the oligomer B has two or less functional groups, it exhibits high flexibility and stretchability, so that the workability of the photosensitive glass composition can be improved more than the pentafunctional or higher urethane (meth)acrylate oligomer A. Therefore, by containing the oligomer B, the followability to the substrate during exposure can be improved. Moreover, since the oligomer B has a urethane bond, it is excellent in flexibility and stretchability. Therefore, in a cured glass film obtained by photocuring the photosensitive glass composition, warpage is improved, and the occurrence of cracks can be suitably suppressed.

The oligomer B may be a compound obtained by reacting a (meth)acrylate compound containing a hydroxy group with a polyisocyanate compound. It may also be a compound obtained by reacting a (meth)acrylate compound containing an isocyanate group with a polyol compound. Alternatively, it may be a compound obtained by reacting a (meth)acrylate compound containing a hydroxy group, a polyisocyanate compound, and a polyol compound. Although not particularly limited, for example, the bifunctional or less urethane acrylate oligomer B reacts with a polyol compound and a polyisocyanate compound to produce a urethane-type precursor having an isocyanate group, followed by a hydroxy group and a (meth)acryloyl group. can be obtained by reacting a monofunctional (meth)acrylate compound having

Examples of hydroxyl group-containing monofunctional (meth)acrylate compounds that can be used as starting materials for the oligomer B include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl ( meth)acrylate, 2-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate and the like. These may be used singly or in combination of two or more.

The polyisocyanate compound and the polyol compound can be used without particular limitation to the compounds described above. In one preferred embodiment, the oligomer B is a bifunctional or less aliphatic urethane (meth)acrylate oligomer whose polyisocyanate compound is the above-described aliphatic and/or alicyclic polyisocyanate. Since these bifunctional or less aliphatic urethane (meth)acrylate oligomers can have excellent toughness and flexibility, they can form highly reliable glass layers with improved adhesion to substrates. .

The weight average molecular weight (Mw) of the bifunctional or less urethane (meth)acrylate oligomer B is typically 10,000 or less. The weight average molecular weight (Mw) is, for example, preferably 500 to 10,000, may be 750 to 8,000, or may be 1,000 to 5,000.

Such bifunctional or less urethane (meth)acrylate oligomer B may be prepared by purchasing a commercially available product. Specifically, the product names EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8807, EBECRYL9270, and KRM8191 manufactured by Daicel Allnex Co., Ltd., and the product names UF-8001G and DAUA-16 manufactured by Kyoeisha Science Co., Ltd. 7. Nippon Kayaku Co., Ltd. Company product names UXT-6100, UXF-4002, UXF-4001-M35, UX-0937, UX-8101, UX-6101, UX-4101, UX-3204, Shin-Nakamura Chemical Co., Ltd. product name UA- 4200, UA-160TM, UA-290TM, UA-W2A, UA-4400, UA-122P, U-200PA, trade name Miramer PU240 manufactured by Toyo Chemicals Co., Ltd., and the like. These may be used individually by 1 type, and may be used in mixture of 2 or more types.

In the glass composition disclosed herein, the urethane (meth)acrylate oligomer A having a functionality of 5 or more and the urethane (meth)acrylate oligomer B having a functionality of 2 or less as described above are It is contained so that the ratio (A:B) is from 90:10 to 12.5:87.5. As described above, the oligomer A has excellent photocurability and can exhibit the effect of improving the strength of the glass layer. On the other hand, the oligomer B is excellent in flexibility and can exhibit the effect of improving conformability to the substrate. In the photosensitive glass composition, by including these oligomers A and B in the above-described mass ratio, photocuring shrinkage due to high light transmittance can be suppressed. Therefore, warping in the exposure process and peeling from the base material in the development process can be suitably suppressed.
In one preferred embodiment, the mass ratio (A:B) of oligomer A and oligomer B is 82.5:17.5 to 25:75. In a further preferred aspect, the weight ratio (A:B) of oligomer A and oligomer B is 75:25 to 37.5:62.5. As a result, the above-described effects are exhibited more favorably. For this reason, even when the exposure process is performed under exposure conditions with a larger amount of exposure, warping of the cured glass film after the exposure process is suppressed. Moreover, even when the development process is performed under development conditions in which the developer is supplied for a longer period of time, peeling of the cured glass film from the substrate can be suppressed.

A preferred embodiment of the photosensitive glass composition disclosed herein further contains a (meth)acrylate having a functionality of 2 or less as a photocurable resin. Bifunctional or less (meth)acrylates are (meth)acrylate compounds having one or two acryloyl groups in the molecule. Such a bifunctional or less (meth)acrylate may be, for example, a bifunctional or less (meth)acrylate monomer or a bifunctional or less (meth)acrylate oligomer. Alternatively, it may be a modified bifunctional or less (meth)acrylate. Since the photosensitive glass composition further contains a bifunctional or less (meth)acrylate in addition to the oligomer A and oligomer B described above, the cured glass film obtained by photocuring the photosensitive glass composition can be prevented from warping after the exposure process. , the viscosity of the composition can be reduced. Therefore, even when the proportion of the glass powder in the entire photosensitive glass composition increases, the warpage after the exposure process and the peeling during the development process can be effectively improved. Therefore, an electronic component with a denser glass layer can be realized.

Examples of such bifunctional or less (meth)acrylates include, in addition to the above-described monofunctional (meth)acrylate compounds containing a hydroxy group, tripropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetra Ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexane Diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol diacrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, neopentylglycol hydroxypivalate di(meth)acrylate and the like. These may be used singly or in combination of two or more.

Such bifunctional or less (meth)acrylates may be prepared, for example, by purchasing commercially available products. Specifically, the product names DPGDA, HDDA, TPGDA, and EBECRYL145 manufactured by Daicel Allnex Co., Ltd., and the product names Light Acrylate 1.6HX-A, Light Acrylate NP-A, and Light Acrylate 1.9ND- manufactured by Kyoeisha Science Co., Ltd. A, trade names KAYARADR ^TM HX-220, HX-620, UX-3240 manufactured by Nippon Kayaku Co., Ltd., trade names NK Ester A-HD-N, NK Ester A-NOD-N, NK manufactured by Shin-Nakamura Science Co., Ltd. Ester A-NPG, NK Ester APG-200 and the like. These may be used individually by 1 type, and may be used in mixture of 2 or more types. Among the above, it is preferable to appropriately select and use one having a low viscosity.

The weight average molecular weight (Mw) of the bifunctional or less (meth)acrylate is, for example, preferably 100 to 10,000, may be 150 to 8,000, or may be 200 to 5,000.

In an aspect containing a difunctional or less (meth)acrylate in addition to the oligomer A and the oligomer B, the sum of the pentafunctional or more oligomer A, the difunctional or less oligomer B, and the difunctional or less (meth)acrylate The mass ratio of (A: (B + 2-functional or less (meth)acrylate)) is preferably 90: 10 to 12.5: 87.5, and 82.5: 17.5 to 25: 75 is more preferred, and 75:25 to 37.5:62.5 is even more preferred. By further including a (meth)acrylate having a functionality of 2 or less so as to satisfy this range, it is possible to prevent the viscosity of the photosensitive glass composition from becoming excessively high. As a result, it is possible to form a high-quality cured glass film that has a fine pattern and suitably exhibits the effect of suppressing photocuring shrinkage due to the inclusion of the oligomer A and the oligomer B.

The proportion of the photocurable resin in the entire photosensitive glass composition is preferably approximately 1% by mass or more, preferably 3% by mass or more, and more preferably 6% by mass or more. Thereby, a glass cured film having a predetermined width can be properly formed with a short exposure time. Moreover, the proportion of the photocurable resin in the entire photosensitive glass composition is approximately 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less. Thereby, the precision of the glass cured film can be further improved.

(3) Photoinitiator The photosensitive glass composition disclosed herein contains a photoinitiator. A photopolymerization initiator is a component that is decomposed by irradiation with light energy such as ultraviolet rays to generate active species such as radicals and cations, thereby initiating the polymerization reaction of the photocurable resin. The photopolymerization initiator is not particularly limited, and can be used alone or in combination of two or more of conventionally known ones depending on the type of the photocurable resin. Preferred examples of photopolymerization initiators include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morphol linophenyl)-butanone-1, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2,4-diethylthioxanthone, benzophenone and the like. As the photopolymerization initiator as described above, commercially available products can be used without particular limitation.

Although not particularly limited, the proportion of the photopolymerization initiator in the entire photosensitive glass composition may be approximately 0.1% by mass or more and 5% by mass or less, typically 0.5% by mass. % or more and 3 mass % or less, for example, 1 mass % or more and 2 mass % or less. The ratio of the photopolymerization initiator to 100 parts by mass of the photocurable resin can be, for example, 1 part by mass or more and 50 parts by mass or less, preferably 10 parts by mass or more and 30 parts by mass or less. By setting it as this range, the photocurability of a photosensitive glass composition can fully be exhibited and a glass cured film can be formed stably.

(4) Organic dispersion medium The photosensitive glass composition disclosed herein contains an organic dispersion medium. The organic dispersion medium imparts appropriate viscosity and fluidity to the photosensitive glass composition, thereby improving the handling properties of the photosensitive glass composition and improving the workability of molding the glass layer. is an ingredient. As for the organic dispersion medium, one type can be used alone, or two or more types can be used in combination as appropriate, depending on the types of the photocurable resin and the photopolymerization initiator, among 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) and ethylene glycol monoethyl ether (cellosolve). , diethylene glycol 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 and other glycol ether solvents; 1, Ester solvents such as 7,7-trimethyl-2-acetoxy-bicyclo-[2,2,1]-heptane, 2,2,4-trimethyl-1,3-pentadiol monoisobutyrate; terpineol, dihydroterpineol , dihydroterpinylpropionate, benzyl alcohol, etc.; and other organic solvents having a high boiling point, such as mineral spirits.

Among the organic solvents described above, organic solvents having a boiling point of 150° C. or higher, and organic solvents having a boiling point of 170° C. or higher are preferred from the viewpoint of improving the storage stability of the photosensitive glass composition and the handling properties during the formation of the glass film. Solvents are preferred. As another preferred example, an organic solvent with a boiling point of 250° C. or lower, and more preferably an organic solvent with a boiling point of 220° C. or lower is preferred from the viewpoint of keeping the drying temperature after printing the glass film low. As a result, productivity can be improved and production costs can be reduced.

Further, for example, in the application of forming a glass layer on a ceramic substrate to manufacture a ceramic electronic component, an organic solvent having low permeability to the ceramic green sheet is preferable. Examples of the organic solvent having low permeability to the ceramic green sheet include organic solvents having a sterically bulky structure such as cyclohexyl group and tert-butyl group, and organic solvents having a relatively large molecular weight. Furthermore, for example, the organic solvent having low permeability to the ceramic green sheet as described above and the components contained in the photosensitive glass composition (for example, the photocurable resin and/or the photopolymerization initiator) can be preferably dissolved. It is also preferable to mix it with an organic solvent in an arbitrary ratio and use it as an organic dispersion medium.

Commercially available organic solvents having the properties (boiling point and permeability to ceramic green sheets) as described above include, for example, Dowanol DPM (trademark) (boiling point: 190°C, manufactured by Dow Chemical Company), Dowanol DPMA (trademark ) (boiling point: 209 ° C., manufactured by Dow Chemical Company), Menthanol (boiling point: 207 ° C.), Menthanol P (boiling point: 216 ° C.), Isopar H (boiling point: 176 ° C., manufactured by Kanto Fuel Co., Ltd.), SW-1800 (boiling point: 198°C, manufactured by Maruzen Oil Co., Ltd.) and the like.

The proportion of the organic dispersion medium in the entire photosensitive glass composition is not particularly limited, but is generally 1% by mass to 50% by mass, typically 3% by mass to 30% by mass, for example 5% by mass. It may be up to 20% by mass.

(5) Organic binder As the organic binder, those used in conventionally known photosensitive compositions can be used without particular limitation. For example, one or more of cellulose-based polymers (cellulose derivatives) such as methylcellulose, ethylcellulose, carboxymethylcellulose, and hydroxymethylcellulose, acrylic resins, phenolic resins, alkyd resins, polyvinyl alcohol, polyvinyl acetal (typically, polyvinyl butyral), etc. Two or more kinds can be used. Among them, highly hydrophilic (typically alkali-soluble) organic binders can be preferably used. As a result, the uncured portion can be preferably removed in the etching treatment (typically alkali treatment) described below.
The proportion of the organic binder in the entire photosensitive glass composition is, for example, 0.1% by mass or more and 30% by mass or less, preferably 0.5% by mass or more and 30% by mass or less, more preferably 1% by mass or more. It can be 25% by mass or less.

(6) Other components In addition to the above components, the photosensitive glass composition may contain various additive components as necessary, as long as the effects of the technology disclosed herein are not significantly impaired. . As such an additive component, one or two or more of conventionally known components can be appropriately selected and used. Examples of additive components include inorganic fillers, photosensitizers, polymerization inhibitors (polymerization inhibitors), radical scavengers, antioxidants, UV absorbers, plasticizers, surfactants, leveling agents, and thickeners. agents, dispersants, defoamers, anti-gelling agents, stabilizers, preservatives, pigments and the like. Although not particularly limited, the content of the additive in the entire photosensitive glass composition is generally 5% by mass or less, for example, 3% by mass or less.

As described above, the photosensitive glass composition disclosed herein contains a pentafunctional or higher urethane (meth)acrylate oligomer A and a difunctional or lower urethane (meth)acrylate oligomer B as photocurable resins. The mass ratio (A:B) of these oligomers A and B is adjusted to 90:10 to 12.5:87.5. As a result, the hardness of the pentafunctional or higher urethane (meth)acrylate oligomer and the flexibility of the difunctional or lower urethane (meth)acrylate oligomer are appropriately exhibited, and in the exposure step, the glass film is excessively formed. It suppresses the occurrence of photocuring shrinkage due to photocuring. This makes it possible to suitably form a cured glass film having finely patterned grooves, and to improve warping and peeling from the substrate in the formed cured glass film. By baking such a high-quality cured glass film together with a substrate, it is possible to form a glass layer having grooves with a fine pattern and improved in warpage and peeling from the substrate.

2. Uses of Photosensitive Glass Compositions According to the photosensitive glass compositions disclosed herein, it is possible to form a glass layer with reduced warpage and peeling from a substrate. Therefore, the photosensitive glass composition disclosed herein can be used to manufacture various electronic components such as, for example, 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 thin film type having a single conductive layer, or may be a laminated type having a plurality of conductive layers laminated (see FIG. 1).

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 composition is printed on a carrier sheet such as a PET film in a plate shape and dried, and then the photosensitive glass composition is photocured in a plate shape. The substrate may be formed by using the cured glass film of (1) as a green sheet and baking the plate-like 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;

FIG. 1 is a cross-sectional view schematically showing the structure of a multilayer chip inductor 1. As shown in FIG. The multilayer chip inductor 1 includes a body portion 30 and external electrodes 40 provided on both lateral side portions of the body portion 30 in the left-right direction X. As shown in FIG. The laminated chip inductor 1 has a size of, for example, 1608 shape (1.6 mm×0.8 mm), 2520 shape (2.5 mm×2.0 mm), or the like.
Note that the dimensional relationships (length, width, thickness, etc.) in FIG. 1 do not necessarily reflect the actual dimensional relationships. In addition, symbols X and Y in the drawings represent the left-right direction and the up-down direction, respectively. However, this is only a direction for convenience of explanation.

The body portion 30 has a structure in which the glass layer 14 and the conductive layer 24 are integrated. Glass layer 14 is formed, for example, using a photosensitive glass composition disclosed herein. A conductive layer 24 is arranged between the glass layers 14 in the vertical direction Y. As shown in FIG. The conductive layer 24 is formed using, for example, a composition containing conductive powder (for example, a photosensitive conductive composition). The conductive layers 24 adjacent in the vertical direction Y with the glass layer 14 interposed therebetween are electrically connected through vias 26 provided in the glass layer 14 . As a result, the conductive layer 24 is configured in a three-dimensional spiral shape (helical shape). Both ends of the conductive layer 24 are connected to external electrodes 40 respectively.

Such a multilayer chip inductor 1 can be manufactured, for example, as follows. First, a paste containing a ceramic material, a binder resin and an organic solvent is prepared and supplied onto a carrier sheet to form a ceramic green sheet.

Next, using the photosensitive composition described above, a cured film having a predetermined coil pattern is formed on a predetermined position of the green sheet. As an example, the following process: applying (printing) a photosensitive glass composition onto a green sheet as a base material and drying it to form a glass film-like body that is a dried body of the photosensitive glass composition; 1. Forming step: The glass film is covered with a photomask having a predetermined pattern, and a part of the glass film exposed from the opening is exposed to light to form a cured glass film on the part of the glass film. 1. Exposure step; 1st development step of removing the uncured glass film-like material with a developer to form a cured glass film having predetermined grooves on the substrate; 1st development step; A second forming step of applying (printing) to the grooves of the cured film and drying to form a conductive film-like body, which is a dried body of the photosensitive conductive composition, in the grooves of the glass film-like body; the conductive film-like body; is covered with a photomask having a predetermined pattern, a part of the conductive film-like body exposed from the opening is exposed, and a part of the conductive film-like body is made into a conductive cured film; a second developing step of removing the uncured conductive filmy material with a second developing step; As a result, an unfired glass cured film and a conductive cured film can be formed in the grooves of the unfired glass cured film on the surface of the substrate.

Here, the photosensitive conductive composition is not particularly limited, and conventionally known photosensitive conductive compositions that can be used in manufacturing electronic parts can be used without particular limitation. For example, the photosensitive conductive composition may be a paste-like composition containing conductive powder, a photocurable resin, a photopolymerization initiator, and an organic dispersion medium. Conductive powders include metal carriers such as gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), aluminum (Al), nickel (Ni), and mixtures thereof. and alloys. The photocurable resin is not particularly limited as long as it is an organic compound that is cured by a polymerization reaction, a cross-linking reaction, or the like when irradiated with light (ultraviolet rays). Preferred examples include radically polymerizable monomers having one or more unsaturated bonds such as (meth)acryloyl groups and vinyl groups, and cationic polymerizable monomers having a cyclic structure such as epoxy groups. Further, as the photopolymerization initiator and the organic dispersion medium, the same types as those of the photosensitive glass composition described above can be used without particular limitation, so detailed description thereof will be omitted.
In addition, the photosensitive conductive composition may contain additional components other than the components described above. Such additive components are not particularly limited, and polymerization inhibitors, radical scavengers, antioxidants, plasticizers, surfactants, leveling agents, dispersants, antifoaming agents, anti-gelling agents, stabilizers, Preservatives and the like are included.

In forming a glass cured film and a conductive cured film using the photosensitive glass composition and the photosensitive conductive composition, conventionally known methods can be appropriately used. For example, in the first and second forming steps, the photosensitive glass composition and the photosensitive conductive composition can be applied using various printing methods such as screen printing, a bar coater, and the like. Drying of these photosensitive compositions is preferably carried out at a temperature below the boiling points of the photocurable resin and the photopolymerization initiator, typically 40 to 100°C.

Next, in the first and second exposure steps, a photomask having slits of a predetermined pattern is placed on the glass filmy body, and a part of the glass filmy body (or conductive filmy body) exposed from the slits is exposed. It is implemented by In this exposure process, an exposure machine that emits light rays (typically ultraviolet light) in a wavelength range of 10 nm to 500 nm, for example, an ultraviolet irradiation lamp such as a high-pressure mercury lamp, a metal halide lamp, and a xenon lamp can be used.
The photosensitive glass composition, which is a precursor of the glass film-like material, is prepared by combining a pentafunctional or higher urethane (meth)acrylate oligomer A and a difunctional or lower urethane (meth)acrylate oligomer B in a predetermined manner. Contains by mass ratio. As a result, even when the exposure amount of the exposing machine is set higher than usual, it is possible to form a good cured glass film without peeling or the like. When using the photosensitive glass composition disclosed herein, the exposure dose of the exposing device can be set to, for example, 100 mJ/cm ² to 1000 mJ/cm ² .

In the first and second development steps, an alkaline aqueous developer or the like can be used as the developer. 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 developers may be adjusted to, for example, 0.01 to 0.5 mass %.

FIG. 2 is a diagram schematically showing the laminate 100 before firing. As shown in FIG. 2, by repeating the first forming step to the second developing step described above, the cured glass film 12 having a precise groove on the ceramic substrate 50 and the hardened glass film 12 formed in the groove A laminate 100 having a plurality of layers (first layer L1 to fourth layer L4 in FIG. 2) each including a conductive cured film 22 can be produced. Also, in this laminate 100, the conductive cured films 22 of the first to fourth layers L1 to L4 are connected via vias . The via 26 is formed by forming a via hole in the cured glass film 12 forming the upper surface of the first layer L1 using, for example, a conductive drilling machine, exposing a part of the upper surface of the conductive cured film 22, and exposing the via hole. It can be formed by drying and exposing after filling the electrically conductive composition.

After the paste for forming the external electrodes is applied to the laminate 100, the laminated chip inductor 1 having the precise conductive layers 24 is manufactured by performing a firing process. The firing temperature (maximum temperature in firing treatment) is preferably about 600 to 1000° C., for example. In manufacturing such a laminated chip inductor 1, since the photosensitive glass composition having the above structure is used to form the cured glass film 12, precise patterning with high rectangularity is possible. By applying a photosensitive conductive composition to the glass cured film 12 to form the conductive cured film 22, the conductive cured film 22 having a fine pattern can be formed. Then, by firing these, it is possible to accurately manufacture an electronic component having a fine pattern with L/S of 30 μm/30 μm or less. That is, according to this manufacturing method, even in the case of an electronic component having a fine pattern, an undercut in which the exposed portion of the film-like body is removed in the above-described developing process is suppressed, and a highly reliable electronic component can be obtained. can be manufactured.

[Test example]
Examples of the technology disclosed herein are described below, but the technology disclosed herein is not intended to be limited to those shown in the examples.

<First test>
In this test, photosensitive glass compositions having different compositions were prepared, and the photosensitive glass compositions were printed on substrates. Then, a cured glass film was produced on the substrate by exposing and developing the printed glass film. An evaluation test was conducted to evaluate warpage and peelability of the cured glass film.

1. Preparation of photosensitive glass composition (1) Preparation of each material First, each material contained in the photosensitive glass composition was prepared.
As the glass powder, borosilicate glass (SiO ₂ —B ₂ O ₃ —Al ₂ O ₃ —K ₂ O) was prepared. The average particle size of the glass powder is 2 μm.
As the photocurable resin, the following three types of resin were prepared. As the penta- or higher functional urethane (meth)acrylate oligomer A, a 10-functional aliphatic urethane acrylate oligomer and a penta-functional aliphatic urethane acrylate oligomer were prepared. Also, a difunctional aliphatic urethane acrylate oligomer was prepared as the urethane (meth)acrylate oligomer B having a functionality of 2 or less.
As the photopolymerization initiator, two types of photopolymerization initiators (initiator a and initiator b) were prepared. 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 was prepared as the initiator a. Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide was prepared as the initiator b.
As an organic dispersion medium, a mixed solvent of dipropylene glycol methyl ether acetate (organic solvent a) and dihydroterpineol (organic solvent b) was prepared.
As binders, two types of binders (binder a and binder b) were prepared. A methylcellulose-based water-soluble resin was prepared as the binder a. As the binder b, a water-soluble acrylic resin (methacrylic acid/methyl methacrylate copolymer) was prepared.

(2) Samples 1-14
The glass powder, the photocurable resin, the photopolymerization initiator, and the binder were weighed so that the mass ratios (% by mass) shown in Table 2 were obtained, and dissolved in the organic dispersion medium prepared above. Fourteen photosensitive glass compositions were prepared. The mass ratio (% by mass) shown in Table 2 is based on 100% by mass of the entire photosensitive glass composition. In addition to the components shown in Table 2, Samples 1 to 14 contained a total of 2.1% by mass of an ultraviolet absorber, a sensitizer and a polymerization inhibitor as additional components.

2. Evaluation Test (1) Standard Exposure Conditions In this test, a commercially available PET film was prepared as a substrate. Using screen printing, the photosensitive glass compositions of Samples 1 to 14 were 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 15 µm glass film. bottom. Then, after covering the glass film with a photomask having slits of a predetermined pattern, light was irradiated from an exposure machine under the conditions of an illuminance of 50 mW/cm ² and an exposure amount of 300 mJ/cm ² to form the photomask. A cured glass film was formed by curing the glass film-like body arranged directly under the slit. After that, the cured glass film after the exposure was allowed to stand for 1 hour. The photomask used in this test has L/S (line/space) set to 25 μm/25 μm. In this way, 10 PET films on which the glass film-like body and the glass cured film were formed were produced for each sample.

(2) Overexposure conditions In the same manner as above, the photosensitive glass compositions of Samples 1 to 14 were applied to a PET film in a size of 4 cm × 4 cm using screen printing, and then dried at 45 ° C. for 15 minutes. A 15 μm glass film-like body was formed by doing so. Then, after covering the glass film with a photomask having slits of a predetermined pattern, light was irradiated from an exposure machine under the conditions of an illuminance of 50 mW/cm ² and an exposure amount of 1000 mJ/cm ² to form the photomask. A cured glass film was formed by curing the glass film-like body arranged directly under the slit. After that, the cured glass film after the exposure was allowed to stand for 1 hour. The photomask used in this test has L/S (line/space) set to 25 μm/25 μm. In this way, 10 PET films on which the glass film-like body and the glass cured film were formed were produced for each sample.

(3) Standard development conditions A 0.1% by mass Na ₂ CO ₃ aqueous solution (developer) was applied to the glass film-like body and the glass cured film on the PET film prepared under the above standard exposure conditions, and the break point (B.P. .) +5 seconds was reached. In addition, 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. Then, after removing the glass film material from the light-shielding portion, the substrate was washed with pure water and dried at room temperature. As a result, 10 hardened glass films having a predetermined pattern of grooves on the PET film were produced for each sample.

(4) Excessive development conditions A 0.1% by mass Na ₂ CO ₃ aqueous solution (developer) was applied to the glass film-like body and the glass cured film on the PET film prepared under the above standard exposure conditions, and the break point (B.P. .) +15 seconds was reached. Then, after removing the glass film material from the light-shielding portion, the substrate was washed with pure water and dried at room temperature. As a result, 10 hardened glass films having a predetermined pattern of grooves on the PET film were produced for each sample.

(5) Evaluation of Warpage The warpage of PET films having 10 glass film-like bodies and glass cured films for each sample formed under standard exposure conditions and overexposure conditions was visually evaluated. In the 10 PET films, "◎" indicates a state in which none of the 10 sheets warp under overexposure conditions, "○" indicates a state in which none of the 10 sheets warp under standard exposure conditions, and 1 out of 10 sheets under standard exposure conditions. A state in which 2 sheets were warped was evaluated as "Δ", and a state in which 3 or more out of 10 sheets were warped under standard exposure conditions was evaluated as "×". Table 2 shows the results.

(6) Evaluation of peelability 10 cured glass films for each sample, which were developed under standard development conditions and overdevelopment conditions, were observed with an optical microscope, and the presence or absence of peeling was confirmed from the obtained observation images. In the 10 sheets of the glass cured film, "⊚" indicates that there is no peeling of 10 sheets under excessive development conditions, "○" indicates that there is no peeling of 10 sheets under standard development conditions, and 1 out of 10 sheets under standard exposure conditions. A state in which peeling occurred on ~2 sheets was evaluated as "Δ", and a state in which peeling occurred in 3 or more sheets out of 10 under standard exposure conditions was evaluated as "x". Table 2 shows the results.

(7) Comprehensive Evaluation Comprehensive evaluation was performed according to the criteria shown in Table 1 based on the results of (5) evaluation of warpage and (6) evaluation of peelability.

The cured glass films with the above (7) comprehensive evaluation of “◎”, “○” and “△” are sufficiently suppressed in warping and peeling as precursors of glass layers used in electronic parts. It was determined that In addition, although the samples with the (7) comprehensive evaluation of "Δ" are inferior in yield to the samples with "⊚" and "◯", they sufficiently satisfy the product performance. Table 2 shows the results.

As shown in Table 2, a pentafunctional or higher urethane (meth)acrylate oligomer A and a difunctional or lower urethane (meth)acrylate oligomer B are included as photocurable resins, and the mass ratio of the oligomer A to the oligomer B (A: It can be seen that the glass cured films formed using samples 4 to 12 in which B) is 90:10 to 12.5:87.5 have an overall evaluation of "Δ" or higher.
Therefore, a glass powder, a photocurable resin, a photopolymerization initiator, and an organic dispersion medium are included, and pentafunctional or higher urethane (meth)acrylate oligomer A and difunctional or lower urethane ( By using a photosensitive glass composition containing a meth)acrylate oligomer B and having a mass ratio (A:B) between each oligomer A and the oligomer B of 90:10 to 12.5:87.5, electron As a precursor of a glass layer of a component, a cured glass film with sufficiently reduced warpage and reduced peeling can be produced.

In addition, as shown in Table 2, samples 5 to 11 in which the mass ratio (A:B) of oligomer A and oligomer B was 82.5:17.5 to 25:75 received an overall evaluation of "○". It turns out that it is more than that. Therefore, the photocurable resin includes a urethane (meth)acrylate oligomer A having a functionality of 5 or more and a urethane (meth)acrylate oligomer B having a functionality of 2 or less, and the mass ratio (A:B) of the oligomer A and the oligomer B is A cured glass film produced using a photosensitive glass composition having a ratio of 82.5:17.5 to 25:75 achieves particularly good reductions in warpage and peeling.

<Second test>
In this test, a photosensitive glass composition having a high glass powder mass ratio was prepared, and the photosensitive glass composition was printed on a substrate using the glass composition. Then, a cured glass film was produced on the substrate by exposing and developing the printed glass film.

1. Preparation of photosensitive glass composition As the photocurable resin, in addition to a 10-functional aliphatic urethane acrylate oligomer and a pentafunctional aliphatic urethane acrylate oligomer, a bifunctional acrylic acrylate oligomer is used as a (meth)acrylate having a functionality of 2 or less. prepared. Other materials (glass powder, photopolymerization initiator, organic dispersion medium, binder, etc.) were the same as those used in the first test. These materials were weighed so as to have the mass ratio (mass %) shown in Table 3 and dissolved in the organic dispersion medium prepared above to prepare photosensitive glass compositions of Samples 15 to 20. The mass ratio (% by mass) shown in Table 3 is based on 100% by mass of the entire photosensitive glass composition. In addition to the components shown in Table 3, Samples 15 to 20 contained a total of 1.7% to 2.1% by mass of an ultraviolet absorber, a sensitizer and a polymerization inhibitor as additional components.

2. Evaluation Test In this test, a commercially available PET film was prepared as a substrate. After applying the photosensitive glass compositions of samples 15 to 20 to a size of 4 cm × 4 cm on a PET film using screen printing, follow the same procedure as in the first test, (1) standard exposure conditions ~ ( 4) Excessive development conditions were applied, and (5) evaluation of warpage, (6) evaluation of peelability, and (7) overall evaluation were performed. Table 3 shows the results of each evaluation test. Table 3 also shows the results of sample 8 for comparison.

As shown in Table 3, in the case of samples 15 to 19, in which the mass ratio of the glass powder in the photosensitive glass composition is 60% by mass or less, the overall evaluation is "○" or "⊚". On the other hand, it can be seen that Sample 20, in which the mass ratio of the glass powder is 62% by mass, was evaluated as "Poor" in all of the evaluation of warpage, the evaluation of peelability, and the overall evaluation. Therefore, the mass ratio of the glass powder in the photosensitive glass composition is preferably 60% by mass or less.

Furthermore, when comparing sample 16 and sample 17, even if the mass ratio of the glass powder is the same, by including the bifunctional acrylic acrylate oligomer, the evaluation of warpage, the evaluation of peelability, and the overall evaluation are all "A". It can be seen that Therefore, by including a bifunctional or less (meth)acrylate in addition to the oligomer A and the oligomer B, it is possible to more preferably achieve both the effect of suppressing warpage and the effect of suppressing peeling.

Although specific examples of the present invention have been described in detail above, these are merely examples and do not limit the scope of the claims. The technology described in the claims includes various modifications and changes of the specific examples illustrated above.

12 Glass Hardened Film 14 Glass Layer 22 Conductive Hardened Film 24 Conductive Layer 26 Via 30 Body Part 40 External Electrode 50 Ceramic Substrate 100 Laminate

Claims (9)

a glass layer having a groove with a predetermined width; a conductive layer disposed in the groove of the glass layer;
A photosensitive glass composition used for producing the glass layer in an electronic component comprising
At least glass powder, a photocurable resin, a photopolymerization initiator, an organic dispersion medium,
including
The photocurable resin contains a pentafunctional or higher urethane (meth)acrylate oligomer A and a difunctional or lower urethane (meth)acrylate oligomer B,
The mass ratio (A:B) between the pentafunctional or higher urethane (meth)acrylate oligomer A and the difunctional or lower urethane (meth)acrylate oligomer B is 90:10 to 12.5:87.5. Photosensitive glass composition. The mass ratio (A:B) between the pentafunctional or higher urethane (meth)acrylate oligomer A and the difunctional or lower urethane (meth)acrylate oligomer B is 82.5:17.5 to 25:75. A photosensitive glass composition according to claim 1 . The photosensitive glass composition according to claim 1 or 2, wherein the photocurable resin further contains a (meth)acrylate having a functionality of 2 or less. 4. The photosensitive glass composition according to any one of claims 1 to 3, wherein the glass powder comprises a 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% by mass or more and 20% by mass or less of the B ₂ O ₃ in terms of the mass ratio of oxides when the entire glass is 100% by mass, 5. The photosensitive glass composition according to claim 4, containing 20% by mass or more and 70% by mass or less of said _SiO2 . The photosensitive glass according to any one of claims 1 to 5, wherein the proportion of the glass powder is 45% by mass or more and 60% by mass or less when the total of the photosensitive glass composition is 100% by mass. Composition. The photosensitive glass composition according to any one of claims 1 to 6, wherein the organic dispersion medium is an organic solvent having a boiling point of 150°C or higher and 250°C or lower. A glass layer made of a fired body of the photosensitive glass composition according to any one of claims 1 to 7;
a conductive layer disposed in the groove of the glass layer;
electronic components. The photosensitive glass composition according to any one of claims 1 to 7 is applied onto a substrate, exposed, developed, and then baked to obtain a glass layer comprising a baked body of the photosensitive glass composition. A method of manufacturing an electronic component, comprising the step of forming

Images