TW202344601A - Photosensitive glass composition, electronic component, and manufacturing method of electronic component which can form a glass layer in which warping and peeling from a base material are suppressed - Google Patents

Abstract

The present invention relates to a photosensitive glass composition, an electronic component, and a manufacturing method thereof. The present invention provides a photosensitive glass composition that has a fine pattern and can form a glass layer in which warping and peeling from a base material are suppressed. The photosensitive glass composition disclosed herein is a photosensitive glass composition used for producing a glass layer in an electronic component including a glass layer having a groove portion with a predetermined width and a conductive layer arranged in the groove portion of the glass layer. The photosensitive glass composition contains at least glass powder, a photocurable resin, a photopolymerization initiator and an organic dispersion medium. The photocurable resin contains urethane (meth)acrylate oligomer A with five or more functional groups and urethane (meth)acrylate oligomer B with two or less functional groups. The mass ratio (A:B) of the urethane (meth)acrylate oligomer A with five or more functional groups to the urethane (meth)acrylate oligomer B with two or less functional groups is 90:10 to 12.5:87.5.

Description

Photosensitive glass composition, electronic component, and method of manufacturing electronic component

The present invention relates to a photosensitive glass composition, an electronic component, and a method for manufacturing the electronic component.

Electronic components such as multilayer chip inductors include a circuit board in which a conductive layer in 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 a "photosensitive conductive composition") has been widely known. An example of this method is photolithography (for example, Patent Document 1). In this method, first, a photosensitive conductive composition is supplied to the surface of a base material, and then the composition is dried to form a film-like body (conductive film-like body) containing conductive powder. Next, the conductive film-like body is covered with a light mask having slits (openings) in a predetermined pattern, and a portion of the conductive film-like body exposed from the slits is irradiated with light. Thereby, the photocurable resin is hardened, and a cured film (conductive cured film) containing conductive powder is formed. Next, the unexposed portion (unhardened conductive film-like body) shielded by the photomask is removed using a developer. Thereby, only the exposed conductive cured film of a predetermined pattern remains on the surface of the base material. Therefore, by firing this, a desired conductive layer can be formed.

However, in recent years, the demand for miniaturization of electronic components has further increased. In order to realize the miniaturization of this electronic component, it is required to further reduce L/S (line and space), which represents the line width L of the conductive layer and the width S of the space (space) of the adjacent conductive layer. size relationship. For example, in the past, the L/S of the conductive layer of a general electronic component was about 40 μm/40 μm. However, in recent years, it has been required to form a fine conductive layer with an L/S of less than 30 μm/30 μm. However, if a light mask with a small slit is used to form a fine conductive layer, the amount of light (exposure amount) supplied to the conductive film-like body in the exposure step is reduced, so the light may not reach the conductive film-like body. The lower part of the body (substrate side). In this case, the lower part of the conductive film-like body is not sufficiently hardened but is removed in the development step, so that a conductive layer having an inverted trapezoidal shape in cross-section is formed. The formation of such an inverted trapezoid-shaped conductive layer is called "bottom incision" and may cause problems such as increased resistance of electronic components and disconnection of the conductive layer.

As a technique for forming a fine conductive layer without causing such bottom incision, a photolithography method using a composition containing a photopolymerizable substance and a glass material (hereinafter referred to as "photosensitive glass composition") in combination has been proposed . In this method, first, a photosensitive glass composition is supplied to the surface of a base material to form a glass film-like body. Next, the glass film-like body is covered with a photomask having slits of a predetermined pattern, and the glass film-like body exposed from the slits is exposed. Next, the uncured glass film-like body is removed using a developer, and a glass cured film having groove portions of a predetermined pattern is formed on the surface of the base material. Next, the photosensitive conductive composition is filled into the groove portion of the glass cured film and exposed to light, whereby a conductive cured film is formed in the groove portion of the glass cured film. Then, by firing these glass cured films and conductive cured films, 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. department. Patent Documents 2 to 4 disclose examples of photosensitive compositions used in such manufacturing techniques.

[Prior art documents] [Patent Document] [Patent Document 1] Japanese Patent No. 6694099 [Patent Document 2] Japanese Patent No. 5163687 [Patent Document 3] Japanese Patent No. 5195432 [Patent Document 4] Japanese Patent No. 4719332

[Problem to be solved by the invention]

However, the glass film-like body printed with the photosensitive glass composition has higher light transmittance (transparency) than the conductive film-like body. In a glass film-like body with such a high light transmittance, even if the slits of the photomask are made small and the amount of light supplied is reduced in order to form a fine wiring pattern (pattern of the groove portion) in the exposure step, it is not easy to cause the above-mentioned problems. Such hardening is poor and bottom incision occurs. On the other hand, when only a resin with excellent photocurability is used in the photosensitive glass composition, photocuring shrinkage (volume shrinkage due to curing) due to high light transmittance is likely to occur during the exposure step of the glass film-like body. ). For example, when the photosensitive glass compositions of the above-mentioned Patent Documents 3 and 4 are used, photocuring shrinkage may occur during the exposure step, and warping (curling) may occur in the glass cured film after the exposure step.

In addition, Patent Document 3 studies the formation of via holes and the formation of a conductive pattern of a laminated wafer, but does not study the formation of a glass layer with a fine pattern such that L/S is 40 μm/40 μm and L/S is 30 μm/30 μm. Therefore, when the photosensitive glass composition disclosed in Patent Document 3 is used to form a glass layer with a fine pattern, there is a problem that peeling occurs locally during the development step.

The present invention was made in view of this situation, and an object thereof is to provide a photosensitive glass composition that can form a glass layer that has a fine pattern and is suppressed from warping and peeling from a base material. Another object is to provide an electronic component including the glass layer and the conductive layer, and a method for manufacturing the electronic component. [Means to solve the problem]

In order to achieve the above object, the photosensitive glass composition disclosed here is provided. The photosensitive glass composition disclosed here is used for producing the glass layer in an electronic component including a glass layer having a groove portion with a predetermined width and a conductive layer arranged in the groove portion of the glass layer. The photosensitive glass composition contains at least glass powder, photocurable resin, photopolymerization initiator and organic dispersion medium. The photocurable resin includes a urethane (meth)acrylate oligomer A with five or more functions and a urethane (meth)acrylate oligomer B with two or less functions. The mass ratio (A:B) of the above-mentioned urethane (meth)acrylate oligomer A with more than five functions and the above-mentioned urethane (meth)acrylate oligomer B with less than two functions is 90:10~12.5:87.5.

In the photosensitive glass composition, the urethane (meth)acrylate oligomer A having high photocurability with five or more functions and the flexible two-functional or less amine is contained in the mass ratio as described above. Formate (meth)acrylate oligomer B can appropriately suppress photocuring shrinkage due to high light transmittance in the exposure step. According to the photosensitive glass composition having this structure, fine patterns can be formed suitably, and in the glass cured film obtained by photocuring the photosensitive glass composition, warpage after the exposure step and self-radicalization in the development step can be reduced. Peeling from the material.

In one suitable aspect of the photosensitive glass composition disclosed here, the above-mentioned five- or higher-functional urethane (meth)acrylate oligomer A and the above-mentioned two- or lower-functional urethane (meth)acrylate oligomer A ) The mass ratio (A:B) of acrylate oligomer B is 82.5:17.5~25:75.

According to this configuration, even when the exposure step and the development step are performed under wider conditions, sufficient reduction in warpage and suppression of peeling can be achieved. In one suitable aspect of the photosensitive glass composition disclosed here, the photocurable resin further contains a difunctional or lower (meth)acrylate. According to this configuration, in the glass cured film obtained by photocuring the photosensitive glass composition, the warpage after the exposure step can be reduced, and the viscosity can also be reduced. Therefore, the above-mentioned effects can be more appropriately exhibited.

In one suitable aspect of the photosensitive glass composition disclosed here, the glass powder contains B ₂ O ₃ -SiO ₂ based glass containing B ₂ O ₃ and SiO ₂ as main components. In addition, in this mode, when the entire glass is taken as 100 mass %, the B ₂ O ₃ -SiO ₂ based glass contains 5 mass % or more and 20 mass % or less of the above-mentioned B in terms of oxide converted mass ratio. ₂ O ₃ , and contains 20 mass% or more and 70 mass% or less of the above-mentioned SiO ₂ . Moreover, when the whole said photosensitive glass composition is taken as 100 mass %, the proportion of the said glass powder is 45 mass % or more and 60 mass % or less. According to the photosensitive glass composition having this structure, a glass layer excellent in fixability can be formed.

In one suitable aspect of the photosensitive glass composition disclosed here, the organic dispersion medium is an organic solvent with a boiling point of 150° C. or more and 250° C. or less. According to this structure, 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 suppressed to a low level.

Moreover, according to the technology disclosed here, it is possible to provide an electronic component including a glass layer formed of a fired body of the photosensitive glass composition, and a conductive layer arranged in a groove portion of the glass layer. The glass layer obtained using the above-mentioned photosensitive glass composition has a fine pattern. Therefore, by using this glass layer to form a conductive layer, an electronic component having a fine pattern can be realized.

In addition, according to the technology disclosed here, there is provided a method for manufacturing electronic components, which includes the following steps: supplying the above-mentioned photosensitive glass composition to a substrate, exposing and developing it, and then firing it to form a photosensitive glass composition composed of the above-mentioned photosensitive glass composition. A glass layer formed from a fired body of a flexible glass composition. 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 good accuracy.

Hereinafter, suitable embodiments of the present invention will be described. It should be noted that matters other than matters specifically mentioned in this specification and matters necessary for the implementation of the present invention can be understood as design matters by those skilled in the art based on the prior art in the field. The present invention can be implemented based on the contents disclosed in this specification and the technical common sense in the field. In addition, the expression "A~B" which expresses a numerical range in this specification means "above and below B" unless otherwise mentioned.

In addition, in this specification, the photosensitive glass composition obtained by drying at the temperature below the boiling point of a photocurable resin and a photopolymerizable initiator, specifically, approximately 200 degreeC or less, for example, 100 degreeC or less It is called "glass film-like body", and the substance obtained by photohardening the glass film-like body is called "glass cured film". And what is obtained by baking this glass cured film is called "glass layer". In addition, in this specification, the photosensitive conductive composition obtained by drying the photocurable resin and the photopolymerizable initiator at a temperature lower than the boiling point, specifically approximately 200°C or lower, for example, 100°C or lower, is called " "Conductive film-like body", the substance obtained by photocuring the conductive film-like body is called "conductive cured film". And what obtained by baking this conductive cured film is called "conductive layer". It should be noted that the "paste" in this specification refers to a mixture in which part or all of the solid components are dispersed in a solvent, and includes so-called "slurry", "ink", and the like.

1. Photosensitive glass composition The photosensitive glass composition disclosed here is a composition for producing the glass layer in an electronic component including a glass layer having a groove portion with a predetermined width and a conductive layer arranged in the groove portion of the glass layer. Typically, the photosensitive glass composition is in the form of a paste. The photosensitive glass composition contains at least glass powder, photocurable resin, photopolymerization initiator and organic dispersion medium. In the following, each component will be described in order.

(1) Glass powder Glass powder is a component that remains during the firing process without being burned and forms a glass layer after firing. As the glass powder, in addition to general amorphous glass, crystallized glass containing crystals may be used. As the glass powder, amorphous glass having no crystallized portion is preferred. Suitable examples of the 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 excellent in fixability on the surface of the base material. In addition, in this specification, "powder" refers to the term including powder form, glass frit form, etc.

The boron component (B ₂ O ₃ ) helps improve fluidity during firing, so it is presumed that it improves the fixation of the glass layer to the surface of the base material. The proportion of B ₂ O ₃ in the above-mentioned B ₂ O ₃ -SiO ₂ based glass is preferably 1 mass % or more in terms of oxide, more preferably 3 mass % or more, and still more preferably 5 mass % or more. On the other hand, if the proportion of B ₂ O ₃ in the B ₂ O ₃ -SiO ₂ based glass is excessive, it will be 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 mass % or less in terms of oxide, more preferably 23 mass % or less, and still more preferably 20 mass % or less. . In addition, the silicon component (SiO ₂ ) is a component constituting the skeleton of the fired glass layer. The proportion of SiO ₂ in the B ₂ O ₃ -SiO ₂ based glass is preferably 10 mass% or more in terms of oxide, more preferably 15 mass% or more, and still more preferably 20 mass% or more. On the other hand, the proportion of SiO ₂ in the B ₂ O ₃ -SiO ₂ based glass is preferably 80 mass% or less, more preferably 75 mass% or less, and still more preferably 70 mass% or less. In addition, the above _- mentioned _B2O3 - _{SiO2 -} based glass may contain components other than _B2O3 and _SiO2 . Examples of this component include oxides of Group 2 elements (R represents, for example, Mg, Ca, Zn, Ba, and Sr. The same applies below), aluminum components (Al ₂ O ₃ ), zinc components (ZnO), and the like.

As the glass powder, it is not limited to the above-mentioned B ₂ O ₃ -SiO ₂ type glass, and conventionally known glass compositions can be used without particular limitation. Examples 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 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.

The _D50 particle size of the glass powder is not particularly limited, but when dispersibility and the like are taken into consideration, it is preferably 0.3 μm or more, more preferably 0.7 μm or more, and still more preferably 1 μm or more. On the other hand, when the surface smoothness of the dried glass layer is taken into consideration, the _D50 particle diameter of the glass powder is preferably 8 μm or less, more preferably 5 μm or less, and still more preferably 2 μm or less. In this specification, "D ₅₀ particle size" means that in the volume-based particle size distribution based on the laser diffraction/scattering method, the cumulative value from the smaller particle size side is equivalent to 50% particle size.

When the proportion of glass powder in the photosensitive glass composition is too high, the viscosity of the paste increases, which may cause a decrease in work 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 mass% or less, more preferably 58 mass% or less, further preferably 56 mass% or less, and may be, for example, 54 mass%. the following. On the other hand, when the proportion of glass powder in the photosensitive glass composition is low, it is expected that the printability will improve as the viscosity of the composition decreases, and the shielding in the glass film during photocuring will decrease (i.e., gap increases), thereby improving developability. Therefore, the proportion of glass powder in the composition can be relatively easily reduced. However, when the proportion of glass powder in the photosensitive glass composition is too small, the glass density in the glass layer may become low, and the film thickness of the conductive layer formed in the groove portion of the glass layer may become too thin. From these viewpoints, the lower limit of the proportion of glass powder in the entire photosensitive glass composition is, for example, preferably 35 mass % or more, more preferably 40 mass % or more, still more preferably 45 mass % or more, particularly Preferably, it is 50 mass % or more, for example, it can be 52 mass % or more.

(2) Photocurable resin Photocurable resin is an organic compound that undergoes polymerization reaction, cross-linking reaction, etc. and hardens when irradiated with light (ultraviolet rays). In this specification, "photocurable resin" is a term including monomers, oligomers, and polymers. The photosensitive glass composition disclosed here contains, as a photocurable resin, a five- or higher-functional urethane (meth)acrylate oligomer A (hereinafter also referred to as "oligomer A") and Difunctional or less urethane (meth)acrylate oligomer B (hereinafter also referred to as "oligomer B"). Furthermore, in a suitable embodiment, the photocurable resin further contains a difunctional or lower (meth)acrylate.

It should be noted that in this specification, "urethane (meth)acrylate" refers to a molecule having a urethane bond (-NH-C (=O)-O-) and ( Meth)acrylyl compound. In addition, in this specification, "(meth)acrylyl" means "methacrylyl (-C(=O)-C(CH ₃ )=CH ₂ )" and "acrylyl (- C(=O)-CH=CH ₂ )” term. Furthermore, "(meth)acrylate" is a term including "methacrylate" and "acrylate". In addition, in this specification, "urethane (meth)acrylate oligomer" refers to a compound having a urethane bond and a (meth)acrylyl group in the molecule, and is a weight average molecular weight (Mw) Smaller polymers (e.g. polymers with a weight average molecular weight of less than 10,000).

Pentafunctional or higher urethane (meth)acrylate oligomer A is a multifunctional urethane (meth)acrylate oligomer A having 5 or more (roughly 5 to 15, for example, 5 to 10) functional groups in the molecule. Meth)acrylate compounds. The oligomer A has high photocurability by having five or more functional groups, and the hardness of the glass cured film can be increased by including the oligomer A.

The pentafunctional or higher urethane (meth)acrylate oligomer A may be a compound obtained by reacting a hydroxyl-containing (meth)acrylate compound and a polyisocyanate compound. Moreover, a compound obtained by reacting an isocyanate group-containing acrylate compound and a polyol compound may be used. Alternatively, it may be a compound obtained by reacting a hydroxyl-containing (meth)acrylate compound, a polyisocyanate compound, and a polyol compound. There is no particular limitation, but the urethane (meth)acrylate oligomer A having five or more functions can be produced by reacting a polyol compound and a polyisocyanate compound to form a urethane-type precursor having an isocyanate group. Then, the (meth)acrylate compound is reacted to obtain it.

Examples of the hydroxyl-containing (meth)acrylate monomer that can be used as the raw material of the oligomer A include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. Ester, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate and other hydroxyalkyl acrylates; 2-hydroxyethylacrylyl phosphate, 2-(meth)acrylate ) Acryloxyethyl-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)acryloxypropyl (meth)acrylate base) acrylate, glyceryl di(meth)acrylate, 2-hydroxy-3-acrylyl-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, etc. These can be used individually by 1 type or in mixture of 2 or more types.

Examples of the polyisocyanate compound include aromatic compounds such as toluene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate. aliphatic polyisocyanates; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, pentane diisocyanate, lysine diisocyanate, norbornane diisocyanate and other aliphatic polyisocyanates; isophorone diisocyanate, Alicyclic polyisocyanates such as cyclohexyl diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, and dicyclohexylmethane diisocyanate, etc. These can be used individually by 1 type or in mixture of 2 or more types.

Examples of the polyol compound include high molecular weight polyols such as polyether polyol and polyester polyol, and low molecular weight polyols such as triethylene glycol and hexylene glycol. These can be used individually by 1 type or in mixture of 2 or more types.

In a suitable mode, oligomer A is an aliphatic urethane (meth)acrylate oligomer with five or more functions, wherein the polyisocyanate compound is the above-mentioned aliphatic and/or alicyclic polyisocyanate. These five- or higher-functional aliphatic urethane (meth)acrylate oligomers have the property of hardening more quickly in the exposure step, and can have higher hardness in glass cured films. Thereby, a precisely patterned glass cured film can be formed.

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

The urethane (meth)acrylate oligomer A with five or more functions can be prepared by purchasing a commercial product. Specifically, there are the trade names EBECRYL1290, EBECRYL5129, EBECRYL8301R, KRM8200, KRM8904, and KRM8452 manufactured by Daicel Allnex Co., Ltd.; the trade names AH-600, UA-306T, UA-306I, and UA-510H manufactured by Kyorei Society Science Co., Ltd. ; Trade names UX-5005, UX-5103, UX-5102, D-M20, UX5000, DPHA-40H manufactured by Nippon Chemical Co., Ltd.; Trade names UA-1100H, U-6LPA, UA-33H manufactured by Shin-Nakamura Chemical Co., Ltd. , U-10HA, U-10PA, U-15HA; trade names Miramer PU610, Miramer MU9500, etc. manufactured by Toyo Chemical Co., Ltd. These may be used individually by 1 type, and may be used in mixture of 2 or more types.

The difunctional or lower urethane (meth)acrylate oligomer B is a urethane (meth)acrylate compound having one or two functional groups in the molecule. By having two or less functional groups, the oligomer B exhibits high flexibility and stretchability, and therefore can be further improved compared to the urethane (meth)acrylate oligomer A having five or more functions. Improve the processability of photosensitive glass compositions. Therefore, by including the oligomer B, the following properties with respect to the base material during exposure can be improved. In addition, since oligomer B has a urethane bond, flexibility and stretchability are also excellent. Therefore, in the glass cured 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 hydroxyl-containing (meth)acrylate compound and a polyisocyanate compound. Moreover, a compound obtained by reacting an isocyanate group-containing (meth)acrylate compound and a polyol compound may be used. Alternatively, the compound may be a compound obtained by reacting a hydroxyl-containing (meth)acrylate compound, a polyisocyanate compound, and a polyol compound. It is not particularly limited. For example, the urethane acrylate oligomer B having a difunctional or lower function can be produced by reacting a polyol compound and a polyisocyanate compound to form a urethane-type precursor having an isocyanate group. , obtained by reacting a monofunctional (meth)acrylate compound having a hydroxyl group and a (meth)acrylyl group.

Examples of the hydroxyl-containing monofunctional (meth)acrylate compound that can be used as the raw material of the oligomer B include 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate. Ester, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylic acid Ester etc. These can be used individually by 1 type or in mixture of 2 or more types.

The above-mentioned polyisocyanate compounds and polyol compounds can be used without particular limitation. In a suitable mode, oligomer B is a difunctional or lower aliphatic urethane (meth)acrylate oligomer, wherein the polyisocyanate compound is the above-mentioned aliphatic and/or alicyclic polyisocyanate. These bifunctional or less aliphatic urethane (meth)acrylate oligomers have excellent strength, toughness and flexibility, and therefore can form highly reliable glass with improved adhesion to the base material. layer.

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

This difunctional or less urethane (meth)acrylate oligomer B can be prepared by purchasing a commercial product. Specific examples include trade names EBECRYL230, EBECRYL270, EBECRYL4858, EBECRYL8402, EBECRYL8804, EBECRYL8807, EBECRYL9270, and KRM8191 manufactured by Daicel Allnex; trade names UF-8001G and DAUA-167 manufactured by Kyoreisha Scientific Co., Ltd.; and Nippon Kayaku. Trade names of UXT-6100, UXF-4002, UXF-4001-M35, UX-0937, UX-8101, UX-6101, UX-4101, UX-3204 made by the company; trade names of UA-4200 made by Shin-Nakamura Chemical Co., Ltd. , UA-160TM, UA-290TM, UA-W2A, UA-4400, UA-122P, U-200PA; trade name Miramer PU240 manufactured by Toyo Chemical Co., Ltd., etc. These may be used individually by 1 type, and may be used in mixture of 2 or more types.

The glass composition disclosed here contains the above-described pentafunctional or higher urethane such that the mass ratio (A:B) of oligomer A to oligomer B is 90:10 to 12.5:87.5. (Meth)acrylate oligomer A and difunctional or less urethane (meth)acrylate oligomer B. As described above, oligomer A has excellent photocurability and can exhibit an effect of improving the strength of the glass layer. On the other hand, oligomer B has excellent flexibility and can exhibit an effect of improving followability to a base material. By including these oligomers A and oligomers in the above mass ratio in the photosensitive glass composition, photocuring shrinkage resulting from high light transmittance can be suppressed. Therefore, warpage in the exposure step and peeling from the base material in the development step can be appropriately suppressed. In addition, in a suitable method, the mass ratio (A:B) of oligomer A and oligomer B is 82.5:17.5~25:75. Furthermore, in a suitable method, the mass ratio (A:B) of oligomer A and oligomer B is 75:25~37.5:62.5. This enables the above-mentioned effects to be exerted more appropriately. Therefore, even when the exposure step is performed under exposure conditions with a larger exposure amount, the warpage of the glass cured film after the exposure step can be suppressed. In addition, even when the development step is performed under development conditions in which the developer supply time is further extended, peeling of the glass cured film from the base material can be suppressed.

In one suitable aspect of the photosensitive glass composition disclosed here, the photocurable resin further contains a difunctional or lower (meth)acrylate. (Meth)acrylate with less than two functions refers to a (meth)acrylate compound having one or two acryl groups in the molecule. The difunctional or less (meth)acrylate may be, for example, a difunctional or less (meth)acrylate monomer or a difunctional or less (meth)acrylate oligomer. Alternatively, it may be a modified product of this difunctional or lower (meth)acrylate. By making the photosensitive glass composition contain the above-mentioned oligomer A and oligomer B and further containing a difunctional or lower (meth)acrylate, it is possible to reduce the amount of photohardening of the photosensitive glass composition. Warpage after the exposure step in the glass hardened film, viscosity of the composition. Therefore, even when the proportion of the glass powder in the entire photosensitive glass composition is increased, the above-described improvement in warpage after the exposure step and improvement in peeling in the development step can be suitably exhibited. Therefore, electronic components having a higher density glass layer can be realized.

Examples of the difunctional or lower (meth)acrylate include, for example, the above-mentioned monofunctional (meth)acrylate compound containing a hydroxyl group, tripropylene glycol di(meth)acrylate, and triethylene glycol. Di(meth)acrylate, tetraethylene 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-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol diacrylate, new Pentylene glycol hydroxypivalate di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, etc. These can be used individually by 1 type or in mixture of 2 or more types.

This difunctional or lower (meth)acrylate can be prepared, for example, by purchasing a commercial product. Specifically, the trade names of DPGDA, HDDA, TPGDA, and EBECRYL145 manufactured by Daicel Allnex Co., Ltd.; and the trade names of Light Acrylate 1.6HX-A, Light Acrylate NP-A, and Light Acrylate 1.9ND-A manufactured by Kyorei Science Co., Ltd. are listed. ; Trade names KAYARADR ^TM HX-220, HX-620, UX-3240 manufactured by Nippon Chemical Co., Ltd.; Trade names NK ESTER A-HD-N, NK ESTER A-NOD-N, NK ESTER A manufactured by Shin-Nakamura Scientific Co., Ltd. -NPG, NK ESTER APG-200, etc. These may be used individually by 1 type, and may be used in mixture of 2 or more types. It is preferable to appropriately select and use a substance with low viscosity among the above.

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

In an aspect that includes oligomer A and oligomer B and also contains (meth)acrylate with less than two functions, the oligomer A with more than five functions and the oligomer B with less than two functions and the two-functional The total mass ratio of the following (meth)acrylates (A:(B+bifunctional or less (meth)acrylate)) is preferably 90:10~12.5:87.5, more preferably 82.5:17.5~25: 75. A further preferred range is 75:25~37.5:62.5. By further containing a (meth)acrylate having a difunctional or lower functionality so as to satisfy this range, it is possible to suppress the viscosity of the photosensitive glass composition from becoming too high. Thereby, it is possible to form a high-quality glass cured film that has a fine pattern and appropriately exhibits the effect of suppressing photocuring shrinkage by containing the oligomer A and the oligomer B.

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

(3) Photopolymerization initiator The photosensitive glass composition disclosed here contains a photopolymerization initiator. The photopolymerization initiator is a component that is decomposed by irradiation with light energy such as ultraviolet rays to generate active species such as free radicals and cations, thereby initiating the polymerization reaction of the photocurable resin. The photopolymerization initiator is not particularly limited, and depending on the type of photocurable resin and the like, one type of conventionally known substances can be used alone or two or more types can be used in an appropriate combination. Suitable examples of the photopolymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2- Dimethylamino-1-(4-morpholinophenyl)-butanone-1, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 2,4-diethylthioxanthone, benzophenone, etc. In addition, as the above-mentioned photopolymerization initiator, a commercial product can be used without particular limitation.

Although not particularly limited, the proportion of the photopolymerization initiator in the entire photosensitive glass composition can be roughly 0.1 mass % or more and 5 mass % or less. Typically, it can be 0.5 mass % or more and 3 mass %. Below, for example, it may be 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 to 50 parts by mass, preferably 10 to 30 parts by mass. By setting it in this range, the photocurability of the photosensitive glass composition can be fully exerted, and a glass cured film can be stably formed.

(4) Organic dispersion medium The photosensitive glass composition disclosed here contains an organic dispersion medium. The organic dispersion medium is a component that imparts appropriate viscosity and fluidity to the photosensitive glass composition, improves the handleability of the photosensitive glass composition, and improves workability when forming a glass layer. The organic dispersion medium can be used individually by one type from conventionally known ones, or in combination of two or more types appropriately, depending on the type of photocurable resin, photopolymerization initiator, etc. Examples of organic dispersion media include hydrocarbon solvents such as toluene and xylene; glycol solvents such as ethylene glycol, propylene glycol, and diethylene glycol; and ethylene glycol monomethyl ether (methyl cellosolve). ), ethylene glycol monoethyl ether (cellosolve), diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether, dipropylene glycol methyl ether, Propylene glycol methyl ether acetate, propylene glycol phenyl ether, 3-methyl-3-methoxybutanol and other glycol ether solvents; 1,7,7-trimethyl-2-ethyloxy-bicyclo -[2,2,1]-heptane, 2,2,4-trimethyl-1,3-pentadiol monoisobutyrate and other ester solvents; terpineol, dihydroterpineol, propyl Alcoholic solvents such as dihydroterpinate acid and benzyl alcohol; other organic solvents with high boiling points such as mineral spirits.

Among the above-mentioned organic solvents, from the viewpoint of improving the storage stability of the photosensitive glass composition and the handleability during the formation of the glass film-like body, an organic solvent with a boiling point of 150°C or higher is preferred, and a further preferred boiling point is 170°C or higher. of organic solvents. In addition, as another suitable example, from the viewpoint of keeping the drying temperature after printing the glass film-like body low, an organic solvent with a boiling point of 250°C or less is preferred, and an organic solvent with a boiling point of 220°C or less is more preferred. This can improve productivity and reduce production costs.

For example, in the application of forming a glass layer on a ceramic base material to produce ceramic electronic components, an organic solvent with low permeability into the ceramic green sheet is preferred. Examples of organic solvents with low permeability into the ceramic green sheet include organic solvents having a three-dimensionally fluffy structure such as cyclohexyl and tert-butyl groups; and organic solvents with relatively large molecular weights. Furthermore, it is also preferable to combine an organic solvent with low permeability into the ceramic green sheet as described above and a component (for example, a photocurable resin and/or a photopolymerization initiator) that can suitably dissolve the photosensitive glass composition. ) organic solvents are mixed in any proportion and used as organic dispersion media.

Examples of commercially available organic solvents having the above-mentioned properties (boiling point and permeability into ceramic green sheets) include DOWANOL DPM (trademark) (boiling point: 190°C, manufactured by Dow Chemical Co., Ltd.) and DOWANOL DPMA (trademark). (Boiling point: 209°C, manufactured by Dow Chemical Co., Ltd.), 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 ℃, Maruzen Oil Co., Ltd.), etc.

The proportion of the organic dispersion medium in the entire photosensitive glass composition is not particularly limited, but is generally 1 mass % to 50 mass %. Typically, it can be 3 mass % to 30 mass %, for example, it can be 5 mass %. ~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, cellulose-based polymers (cellulose derivatives) such as methylcellulose, ethylcellulose, carboxymethylcellulose, and hydroxymethylcellulose, acrylic resins, phenolic resins, alkyd resins, and polyethylene can be used. One or more types of alcohol, polyvinyl acetal (typically, polyvinyl butyral), etc. Among them, organic binders with high hydrophilicity (typically, alkali solubility) can be preferably used. This allows the unhardened portion to be appropriately removed in the etching process (typically, alkali treatment) described below. The proportion of the organic binder in the entire photosensitive glass composition is, for example, 0.1 mass % or more and 30 mass % or less, preferably 0.5 mass % or more and 30 mass % or less, more preferably 1 mass % or more and 25 mass % or more. mass% or less.

(6) Other ingredients The photosensitive glass composition may further contain various additive components as necessary in addition to the above-mentioned components within a range that does not significantly impair the technical effects disclosed herein. As such additional components, one or two or more types may be appropriately selected from conventionally known substances and used. Examples of additive components include inorganic fillers, photosensitizers, polymerization inhibitors (antipolymerization agents), radical scavengers, antioxidants, ultraviolet absorbers, plasticizers, surfactants, leveling agents, and stabilizers. Thickener, dispersant, defoaming agent, anti-gelling agent, stabilizer, preservative, pigment, etc. Although not particularly limited, the content of the additive in the entire photosensitive glass composition is generally 5 mass % or less, and may be, for example, 3 mass % or less.

As described above, the photosensitive glass composition disclosed here contains the urethane (meth)acrylate oligomer A with five or more functions and the urethane (meth)acrylate oligomer A with two or less functions as the photocurable resin. Ester (meth)acrylate oligomer B. Furthermore, the mass ratio (A:B) of these oligomers A and oligomers B was adjusted to 90:10~12.5:87.5. This appropriately brings out the rigidity of the urethane (meth)acrylate oligomer with five or more functions and the flexibility of the urethane (meth)acrylate oligomer with two or less functions. , suppressing photohardening shrinkage caused by excessive photohardening of the glass film-like body during the exposure step. Thereby, the glass cured film provided with the groove part of a fine pattern can be formed suitably, and the warpage and peeling from a base material in the formed glass cured film can be improved. Furthermore, by firing this high-quality glass cured film together with the base material, it is possible to form a glass layer that has a fine pattern of groove portions and has improved warpage and peeling from the base material.

2. Uses of photosensitive glass compositions According to the photosensitive glass composition disclosed here, it is possible to form a glass layer in which warpage and peeling from the base material are reduced. Therefore, the photosensitive glass composition disclosed here can be used to manufacture various electronic components such as inductor components, capacitor components, and multilayer circuit boards. Typical examples of inductance components include high-frequency filters, general-mode filters, inductors (coils) for high-frequency circuits, inductors (coils) for general circuits, high-frequency filters, chokes, transformers, etc. . In addition, the shape (structure) of the electronic component is not particularly limited, and it may be a surface mounting type, a through-hole mounting type, or the like. In addition, the electronic component may be a thin film type having a single conductive layer or a multilayer type in which a plurality of conductive layers are laminated (see FIG. 1 ).

Examples of the electronic components include ceramic electronic components. In addition, in this specification, "ceramic electronic component" refers to all electronic components obtained using a ceramic base material. Typical examples of ceramic electronic components include high-frequency filters having ceramic substrates, ceramic inductors (coils), ceramic capacitors, and Low Temperature Co-fired Ceramics Substrate (LTCC substrates). ), High Temperature Co-fired Ceramics Substrate (HTCC substrate), etc. Examples of the ceramic base material include amorphous ceramic base materials (glass ceramic base materials), crystalline (that is, non-glass) ceramic base materials, and the like. When a glass ceramic base material is used, the photosensitive glass composition is printed on a carrier sheet such as a PET film in a plate shape and dried, so that the photosensitive glass composition is photocured. The obtained plate-shaped glass cured film is used as a green sheet, and the plate-shaped glass cured film is fired to form a base material. Examples of crystalline ceramic base materials include zirconium oxide (zirconium sand), magnesia (magnesia sand), aluminum oxide (alumina), silica (silica), titanium oxide (titanium white), oxide Cerium (cerium earth), yttrium oxide (yttrium trioxide), barium titanate and other oxide materials; cordierite, mullite, forsterite, talc, sialon, zircon, ferrite and other composites Oxide-based materials; Nitride-based materials such as silicon nitride (silicon nitride) and aluminum nitride (aluminum nitride); Carbide-based materials such as silicon carbide (silicon carbide); Hydroxide-based materials such as hydroxyapatite materials, etc.

FIG. 1 is a cross-sectional view schematically showing the structure of a multilayer chip inductor 1 . The multilayer chip inductor 1 includes a main body 30 and external electrodes 40 provided on both side surfaces of the main body 30 in the left-right direction X. The multilayer chip inductor 1 has sizes such as 1608 shape (1.6mm×0.8mm) and 2520 shape (2.5mm×2.0mm). It should be noted that the dimensional relationships (length, width, thickness, etc.) in Figure 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. Wherein, it is merely a direction for convenience of explanation.

The main body 30 has a structure in which the glass layer 14 and the conductive layer 24 are integrated. The glass layer 14 is formed using, for example, the photosensitive glass composition disclosed here. In the up-down direction Y, the conductive layer 24 is arranged between the glass layers 14 . 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 to each other in the up-down direction Y across the glass layer 14 are electrically connected via the through holes 26 provided in the glass layer 14 . Thereby, the conductive layer 24 is formed into a three-dimensional vortex shape (spiral shape). Both ends of the conductive layer 24 are connected to the external electrodes 40 respectively.

This multilayer chip inductor 1 can be manufactured as follows, for example. 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 above-mentioned photosensitive composition, a cured film having a predetermined coil pattern is formed at a predetermined position of the green sheet. As an example, the first step includes the step of supplying (printing) the photosensitive glass composition onto a green sheet as a base material and drying it to thereby form a glass film-like body that is a dried body of the photosensitive glass composition. Forming step; a first exposure step of covering the glass film-like body with a photomask having a predetermined pattern, exposing a part of the glass film-like body exposed from the opening, and forming a part of the glass film-like body into a glass cured film ; The first development step of removing the unhardened glass film-like body using a developer and forming a glass cured film having predetermined grooves on the base material; supplying (printing) the photosensitive conductive composition to the formed glass cured film and drying the groove portion of the glass film-like body, thereby forming a conductive film-like body as a dry body of the photosensitive conductive composition in the groove portion of the glass film-like body; covering the conductive film-like body with a predetermined pattern The photomask is a second exposure step of exposing a part of the conductive film-like body exposed from the opening to form a part of the conductive film-like body into a conductive cured film; using a developer to remove the uncured conductive film-like body Second development step. Thereby, a glass cured film in an unfired state can be formed on the surface of the base material, and a conductive cured film can be formed in the groove portion of the glass cured film.

Here, the photosensitive conductive composition is not particularly limited, and conventionally known photosensitive conductive compositions that can be used when manufacturing electronic components can be used without particular limitation. For example, the photosensitive conductive composition may be a paste-like composition containing conductive powder, photocurable resin, photopolymerization initiator, and organic dispersion medium. Examples of the conductive powder include carriers of metals such as gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), aluminum (Al), and nickel (Ni); and their Mixtures, alloys, etc. The photocurable resin is not particularly limited as long as it is an organic compound that hardens by polymerization reaction, crosslinking reaction, etc. when irradiated with light (ultraviolet rays). Suitable examples include radically polymerizable monomers having one or more unsaturated bonds such as (meth)acrylyl groups and vinyl groups; and cationically polymerizable monomers having a cyclic structure such as epoxy groups. . In addition, as the photopolymerization initiator and the organic dispersion medium, the same types as those of the above-mentioned photosensitive glass composition can be used without particular limitation, and therefore detailed descriptions are omitted. In addition, the photosensitive conductive composition may contain additive components other than the above-mentioned components. Such additive ingredients are not particularly limited, and examples include polymerization inhibitors, radical scavengers, antioxidants, plasticizers, surfactants, leveling agents, dispersants, defoaming agents, anti-gelling agents, stabilizers, Preservatives, etc.

In addition, when forming a glass cured film and a conductive cured film using the above-mentioned photosensitive glass composition and photosensitive conductive composition, conventionally known methods can be appropriately used. For example, in the first formation step and the second formation step, the photosensitive glass composition and the photosensitive conductive composition can be supplied using various printing methods such as screen printing, a bar coater, or the like. Drying of these photosensitive compositions can be performed at a temperature below the boiling point of the photocurable resin and the photopolymerization initiator, typically at 40 to 100°C.

Next, in the first exposure step and the second exposure step, a photomask having slits of a predetermined pattern is covered on the glass film-like body, and the glass film-like body (or conductive film-like body) exposed from the slits is Part of it is exposed for implementation. In this exposure process, for example, an exposure machine that emits light in the wavelength range of 10 nm to 500 nm (typically ultraviolet light), such as an ultraviolet irradiation lamp such as a high-pressure mercury lamp, a metal halide lamp, and a xenon lamp, can be used. In addition, as mentioned above, the photosensitive glass composition which is the precursor of a glass film-like body contains the pentafunctional or higher-functional urethane (meth)acrylate oligomer A and di- Functional following urethane (meth)acrylate oligomer B. Accordingly, even when the exposure amount of the exposure machine is set higher than usual, a good glass cured film without peeling or the like can be formed. When using the photosensitive glass composition disclosed here, the exposure amount of an exposure machine can be set to the condition of 100mJ/ ^cm2-1000mJ / ^cm2 , for example.

Furthermore, in the first development step and the second development step, an alkaline aqueous developer or the like can be used as the developer. As an example of the aqueous developer, a sodium hydroxide aqueous solution, a sodium carbonate aqueous solution, etc. can be used. In addition, the alkali concentration of these developing solutions can be adjusted to 0.01-0.5 mass %, for example.

FIG. 2 is a diagram schematically showing the laminated body 100 before firing. As shown in FIG. 2 , by repeating the first forming step to the second developing step, a ceramic base material 50 having a plurality of layers (the first layer L1 to the fourth layer L4 in FIG. 2 ) can be produced. The laminated body 100 includes the plurality of layers including a glass cured film 12 having a precision groove portion and a conductive cured film 22 formed in the groove portion. Moreover, in this laminated body 100, the conductive cured film 22 of each layer of the 1st layer L1 - the 4th layer L4 is connected via the through hole 26. It should be noted that the through hole 26 can be formed by, for example, forming a through hole in the glass cured film 12 serving as the upper surface of the first layer L1 using a conductive punch or the like, and exposing a part of the upper surface of the conductive cured film 22. After the photosensitive conductive composition is filled into the through hole, drying and exposure are performed.

After supplying the external electrode forming paste to the above-mentioned laminated body 100, a firing process is performed to manufacture the laminated chip inductor 1 having the precision conductive layer 24. In addition, the firing temperature (the highest temperature in the firing process) is preferably about 600 to 1000°C, for example. In the production of the multilayer chip inductor 1, since the photosensitive glass composition having the above-mentioned structure is used in the formation of the glass cured film 12, precise patterning with high rectangularity can be achieved. By supplying 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. And by firing these, electronic components having fine patterns with L/S of 30 μm/30 μm or less can be manufactured with good accuracy. That is, according to this manufacturing method, even if it is an electronic component having a fine pattern, it is possible to suppress the incision of the bottom of the film-like body from being removed in the above-mentioned development step, and it is possible to manufacture a highly reliable electronic component.

[Test example] Hereinafter, embodiments related to the technology disclosed here will be described, but this does not mean that the technology disclosed here is limited to the content shown in the embodiment.

＜First Test＞ In this test, photosensitive glass compositions with different compositions were prepared, and the photosensitive glass compositions were printed on a base material. Then, the printed glass film-like body is exposed and developed to produce a glass cured film on the base material. Evaluation tests for evaluating warpage and peelability of the glass cured film were conducted.

1. Preparation of photosensitive glass composition (1) Preparation of each material First, each material included in the photosensitive glass composition is prepared. As glass powder, borosilicate glass (SiO ₂ -B ₂ O ₃ -Al ₂ O ₃ -K ₂ O) was prepared. The average particle size of this glass powder is 2 μm. As the photocurable resin, the following three types of resins are prepared. As the urethane (meth)acrylate oligomer A with more than five functions, a decafunctional aliphatic urethane acrylate oligomer and a pentafunctional aliphatic urethane acrylate oligomer are prepared. things. In addition, as the bifunctional or lower urethane (meth)acrylate oligomer B, a bifunctional aliphatic urethane acrylate oligomer was prepared. As a photopolymerization initiator, two types of photopolymerization initiators (initiator a, initiator b) are prepared. As the starting agent a, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 was prepared. As the initiator b, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide is prepared. As an organic dispersion medium, a mixed solvent obtained by mixing dipropylene glycol methyl ether acetate (organic solvent a) and dihydroterpineol (organic solvent b) was prepared. As adhesives, prepare two types of adhesives (adhesive a, adhesive b). As the binder a, a methylcellulose-based water-soluble resin is prepared. As the binder b, a water-soluble acrylic resin (methacrylic acid-methyl methacrylate copolymer) is prepared.

(2) Sample 1~14 The glass powder, photocurable resin, photopolymerization initiator, and binder were weighed so that the mass ratios (mass %) shown in Table 2 are obtained, and dissolved in the organic dispersion medium prepared above to prepare Photosensitive glass compositions of samples 1 to 14. The mass ratio (mass %) shown in Table 2 is a ratio when the entire photosensitive glass composition is 100 mass %. It should be noted that in samples 1 to 14, in addition to the components shown in Table 2, the total content of ultraviolet absorbers, sensitizers and polymerization inhibitors as other added components was 2.1 mass %.

2. Evaluation test (1) Standard exposure conditions In this test, a commercially available PET film was prepared as a base material. 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 to form a 15 μm glass film-like body. Furthermore, a light mask having slits of a predetermined pattern is covered on the glass film-like body, and then light is irradiated using an exposure machine under the conditions of illumination intensity of 50 mW/cm ² and exposure amount of 300 mJ/cm ² , so that the light mask is placed on the The glass film-like body directly under the slit of the mask hardens to form a glass cured film. Thereafter, the exposed glass cured film was left to stand for 1 hour. It should be noted that the L/S (line/space) setting of the light mask used in this experiment was 25 μm/25 μm. In this manner, 10 PET films each having a glass film-like body and a glass cured film formed thereon were produced for each sample.

(2) Overexposure conditions Using screen printing in the same manner as above, apply the photosensitive glass compositions of Samples 1 to 14 on a PET film to a size of 4 cm × 4 cm, and dry at 45°C for 15 minutes to form 15μm glass membrane. Furthermore, a light mask having slits of a predetermined pattern is covered on the glass film-like body, and then light is irradiated using an exposure machine under the conditions of illumination intensity of 50 mW/cm ² and exposure amount of 1000 mJ/cm ² , so that the light is arranged on the The glass film-like body directly under the slit of the mask hardens to form a glass cured film. Thereafter, the exposed glass cured film was left to stand for 1 hour. It should be noted that the L/S (line/space) setting of the light mask used in this experiment was 25 μm/25 μm. In this manner, 10 PET films each having a glass film-like body and a glass cured film formed thereon were produced for each sample.

(3) Standard development conditions Blow a 0.1% by mass Na ₂ CO ₃ aqueous solution (developer) onto the glass film-like body and glass cured film on the PET film produced under the above standard exposure conditions until the breakpoint is reached. , BP) until +5 seconds. In addition, BP refers to the time until it can visually confirm that the glass film-like body of a light-shielding part is removed by the said developer. Then, after removing the glass film-like body in the light-shielding portion, the glass film-like body is washed with pure water and dried at room temperature. Thus, for each sample, 10 pieces of glass cured films having groove portions of a predetermined pattern on the PET film were produced.

(4) Excessive development conditions Blow a 0.1% by mass Na ₂ CO ₃ aqueous solution (developer) onto the glass film-like body and glass cured film on the PET film produced under the above standard exposure conditions until it reaches the breaking point (BP ) +15 seconds. Then, after removing the glass film-like body in the light-shielding portion, the glass film was washed with pure water and dried at room temperature. Thus, for each sample, 10 pieces of glass cured films having groove portions of a predetermined pattern on the PET film were produced.

(5) Evaluation of warpage The warpage of 10 PET films each having a glass film-like body and a glass cured film formed under standard exposure conditions and overexposure conditions for each sample was visually evaluated. For these 10 PET films, the state in which none of the 10 sheets had warpage under overexposure conditions was evaluated as "◎", the state in which none of the 10 sheets had warpage under standard exposure conditions was evaluated as "○", and the state in which none of the 10 pieces had warpage under standard exposure conditions was evaluated as "○". A state in which warpage exists in 1 to 2 out of 10 pieces under standard exposure conditions is evaluated as "Δ", and a state in which warpage occurs in 3 or more out of 10 pieces under standard exposure conditions is evaluated as "×". The results are shown in Table 2.

(6) Evaluation of peelability Ten glass cured films for each sample produced by development under standard development conditions and excessive development conditions were observed with an optical microscope, and the presence or absence of peeling was confirmed based on the obtained observation images. For these 10 glass cured films, the state in which none of the 10 sheets peeled off under excessive development conditions was evaluated as "◎", the state in which none of the 10 sheets peeled off under standard development conditions was evaluated as "○", and the state in which none of the 10 sheets peeled off under standard development conditions was evaluated as "○". A state in which peeling occurs in 1 to 2 out of 10 pieces under standard exposure conditions is evaluated as "Δ", and a state in which peeling occurs in 3 or more out of 10 pieces under standard exposure conditions is evaluated as "×". The results are shown in Table 2.

(7) Comprehensive evaluation Based on the results of the evaluation of (5) warpage and (6) peelability, a comprehensive evaluation was performed based on the standards shown in Table 1.

[Table 1]

It can be judged that the glass cured film whose comprehensive evaluation is "◎", "○" and "Δ" in the above (7) suppresses warping and peeling to a sufficient extent as a precursor of the glass layer used in electronic components. It should be noted that (7) the sample with a comprehensive evaluation of "Δ" has a lower yield than the samples with "◎" and "○", but the product performance is fully satisfactory. The results are shown in Table 2.

[Table 2]

As shown in Table 2, it can be seen that the urethane (meth)acrylate oligomer A containing five or more functionalities and the urethane (meth)acrylate oligomer B containing two or less functionalities is used. The overall evaluation of the glass cured film formed by samples 4 to 12 of photocurable resin and the mass ratio of oligomer A to oligomer B (A:B) is 90:10~12.5:87.5 is "Δ" or above . Therefore, by using a glass powder, a photocurable resin, a photopolymerization initiator, and an organic dispersion medium, the urethane (meth)acrylate oligomer A containing five or more functions and two or less functional urethane (meth)acrylate oligomers is used. Urethane (meth)acrylate oligomer B is used as a photocurable resin. The mass ratio (A:B) of each oligomer A and oligomer B is 90:10~12.5:87.5. By using a flexible glass composition, it is possible to produce a glass cured film that is a precursor of a glass layer for electronic components and achieves sufficient reduction in warpage and peeling.

In addition, as shown in Table 2, it can be seen that the overall evaluation of samples 5 to 11 in which the mass ratio (A:B) of the above-mentioned oligomer A and oligomer B is 82.5:17.5 to 25:75 is "○" or more. Therefore, a photocurable resin containing a urethane (meth)acrylate oligomer A with five or more functions and a urethane (meth)acrylate oligomer B with two functions or less is used, and The glass cured film made from the photosensitive glass composition with a mass ratio (A:B) of oligomer A to oligomer B of 82.5:17.5~25:75 can achieve particularly good reduction in warpage and peeling. reduce.

＜Second Test＞ In this test, a photosensitive glass composition containing a high mass ratio of glass powder was prepared, and the photosensitive glass composition was printed on a base material using this glass composition. And by exposing and developing the printed glass film-like body, a glass cured film is produced on the base material.

1. Preparation of photosensitive glass composition As the photocurable resin, a decafunctional aliphatic urethane acrylate oligomer and a pentafunctional aliphatic urethane acrylate oligomer were prepared. On this basis, as a difunctional or less (methyl ) acrylate, prepare difunctional acryloacrylate oligomer. For each other material (glass powder, photopolymerization initiator, organic dispersion medium, binder, etc.), the same materials as those used in the first test were prepared. 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, thereby preparing photosensitive glass compositions of Samples 15 to 20. The mass ratio (mass %) shown in Table 3 is a ratio when the entire photosensitive glass composition is 100 mass %. It should be noted that in samples 15 to 20, in addition to the components shown in Table 3, as other added components, the total content of ultraviolet absorbers, sensitizers, and polymerization inhibitors is 1.7 mass% to 2.1 mass%. .

2. Evaluation test In this test, a commercially available PET film was prepared as a base material. Use screen printing to coat the photosensitive glass composition of samples 15 to 20 on the PET film to a size of 4cm × 4cm, and follow the same steps as the first test to implement (1) standard exposure conditions ~ (4) over-exposure development conditions, and conduct (5) evaluation of warpage, (6) evaluation of peelability, and (7) comprehensive evaluation. The results of each evaluation test are listed in Table 3. In addition, Table 3 also describes the results of sample 8 for comparison.

[table 3]

As shown in Table 3, it can be seen that in the case of samples 15 to 19 in which the mass ratio of the glass powder in the photosensitive glass composition is 60 mass % or less, the overall evaluation is "○" or "◎". On the other hand, it was found that Sample 20, in which the mass ratio of glass powder was 62 mass %, received "×" in 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 mass % or less.

Furthermore, when Sample 16 and Sample 17 are compared, it can be seen that even if the mass ratio of the glass powder is the same, inclusion of the difunctional acryloacrylate oligomer improves the evaluation of warpage, the evaluation of peelability, and the overall evaluation. All are "◎". Therefore, by further containing a bifunctional or lower (meth)acrylate in addition to oligomer A and oligomer B, both the warpage suppressing effect and the peeling suppressing effect can be more suitably achieved.

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

1: Multilayer chip inductor 12: Glass hardening film 14:Glass layer 22: Conductive hardened film 24:Conductive layer 26:Through hole 30:Main part 40:External electrode 50:Ceramic substrate 100:Laminated body

FIG. 1 is a cross-sectional view schematically showing the structure of a multilayer chip inductor according to one embodiment. FIG. 2 is a diagram explaining the manufacturing steps of the multilayer chip inductor according to one embodiment.

1: Multilayer chip inductor

14:Glass layer

24:Conductive layer

26:Through hole

30:Main part

40:External electrode

Claims (9)

A photosensitive glass composition used for producing the glass layer in an electronic component including a glass layer having a groove portion with a predetermined width and a conductive layer arranged in the groove portion of the glass layer, The photosensitive glass composition at least contains glass powder, photocurable resin, photopolymerization initiator and organic dispersion medium, The photocurable resin includes a urethane (meth)acrylate oligomer A with more than five functions and a urethane (meth)acrylate oligomer B with two functions or less, The mass ratio A:B of the urethane (meth)acrylate oligomer A with more than five functions and the urethane (meth)acrylate oligomer B with less than two functions is 90:10~12.5:87.5. The photosensitive glass composition according to claim 1, wherein the five- or higher-functional urethane (meth)acrylate oligomer A and the two- or lower-functional urethane (meth)acrylate oligomer A are The mass ratio A:B of acrylic oligomer B is 82.5:17.5~25:75. The photosensitive glass composition according to claim 1 or 2, wherein the photocurable resin further contains a difunctional or lower (meth)acrylate. The photosensitive glass composition according to Claim 1 or 2, wherein the glass powder contains B ₂ O ₃ -SiO ₂ based glass having B ₂ O ₃ and SiO ₂ as main components. The photosensitive glass composition according to claim 4, wherein the B ₂ O ₃ -SiO ₂ based glass contains 5 mass % in mass ratio in terms of oxide when the entire glass is taken as 100 mass %. % or more and 20 mass % or less of the B ₂ O ₃ , and contains 20 mass % or more and 70 mass % or less of the SiO ₂ . The photosensitive glass composition according to claim 1 or claim 2, wherein the proportion of the glass powder is 45 mass% or more and 60 mass% when the entire photosensitive glass composition is 100 mass%. mass% or less. The photosensitive glass composition according to claim 1 or claim 2, wherein the organic dispersion medium is an organic solvent with a boiling point of 150°C or more and 250°C or less. An electronic component having: A glass layer formed from a fired body of the photosensitive glass composition according to claim 1 or 2; and A conductive layer arranged in the groove portion of the glass layer. A method of manufacturing electronic components, which includes the following steps: The photosensitive glass composition according to Claim 1 or 2 is supplied onto a base material, exposed and developed, and then fired to form a glass layer composed of a fired body of the photosensitive glass composition. .