WO2020066049A1

WO2020066049A1 - Curable resin composition, dry film, cured product, laminated structure, and electronic component

Info

Publication number: WO2020066049A1
Application number: PCT/JP2019/002807
Authority: WO
Inventors: 千穂植田; 知哉工藤; 沙和子嶋田; 岡田　和也
Original assignee: 太陽インキ製造株式会社
Priority date: 2018-09-28
Filing date: 2019-01-28
Publication date: 2020-04-02
Also published as: TW202012162A

Abstract

Provided is a curable resin composition or the like from which it is possible to obtain a cured product that can improve dispersibility of a perovskite-type compound, that has excellent adhesion to a substrate, and that can achieve a high dielectric constant and a low dielectric loss tangent simultaneously. This curable resin composition or the like is characterized by including a curable resin and a perovskite-type compound that is coated with at least one of a hydrous oxide of silicon, a hydrous oxide of aluminum, a hydrous oxide of zirconium, a hydrous oxide of zinc, and a hydrous oxide of titanium.

Description

Curable resin composition, dry film, cured product, laminated structure, and electronic component

<< The present invention relates to a curable resin composition, a dry film, a cured product, a laminated structure, and an electronic component.

(4) The higher the dielectric constant of the substrate material, the smaller the signal propagation wavelength. Therefore, a substrate material with a high relative dielectric constant is desired for miniaturization of a circuit board for an antenna or a power amplifier. In addition, as the frequency increases, the signal transmission loss increases. Therefore, a material having a low dielectric loss tangent that reduces the transmission loss is important. That is, a material that can achieve both a high dielectric constant and a low dielectric loss tangent is required for miniaturization of antennas and power amplifiers.

Generally, a method of reducing the number of polar groups in the resin is used from the viewpoint of electric insulation resistance, and it is difficult to achieve both electric insulation resistance and high dielectric constant with only the resin. In addition, since the dielectric constant of a resin is governed by dipole polarization, a resin having a low dielectric loss tangent generally has a low dielectric constant.

Therefore, in order to achieve both a high dielectric constant and a low dielectric loss tangent, it is effective to highly fill a high dielectric constant inorganic filler such as a perovskite compound such as barium titanate or strontium titanate, or titanium oxide ( For example, Patent Document 1).

On the other hand, with the increase in the density of semiconductors, heat generated from semiconductors tends to increase. In recent years, the number of semiconductor packages mounted on vehicles has increased along with the electrification of automobiles, and in environments exposed to such high temperatures, measures to dissipate heat generated from semiconductors into the air have been taken. Is particularly required. Conventionally, as a heat dissipation measure, for example, providing a heat sink on an IC is known. Further, it is known to use a curable resin composition containing an inorganic filler having a high thermal conductivity as a resist material (for example, Patent Document 2).

JP-A-2003-119379 JP 2010-181825 A

However, when the curable resin composition is filled with a perovskite-type compound or titanium oxide at a high level, a filler having high thermal conductivity is added to the curable resin composition in order to produce a resist having excellent heat dissipation properties and peripheral materials. When filled, there was a problem that the dispersibility was impaired. In addition, the amount of resin covering these fillers (that is, perovskite-type compounds, titanium oxide, and fillers having high thermal conductivity) and the wettability with the substrate are reduced, so that there is a problem of reduced adhesion.

Particularly, in the past, the substrate was roughened to improve the adhesion, but in recent years, due to the problem of transmission loss, the substrate surface tends to be roughened free or a low-roughened surface. It is required to provide adhesion.

Therefore, a first object of the present invention is to improve the dispersibility of a perovskite-type compound, to provide a curable resin composition which is excellent in adhesion to a substrate and which can provide a cured product capable of satisfying both a high dielectric constant and a low dielectric loss tangent. An object of the present invention is to provide a product, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and an electronic component having the cured product.

Further, the second object of the present invention is to improve the dispersibility of titanium oxide, obtain a cured product having excellent adhesion to a substrate, and obtain a cured product that can achieve both a high dielectric constant and a low dielectric loss tangent. Obtained curable resin composition, a dry film having a resin layer obtained from the composition, a cured product of the resin layer of the composition or the dry film, a laminated structure having a resin cured layer composed of the cured product, and Another object of the present invention is to provide an electronic component having the cured product.

Further, a third object of the present invention is to improve the dispersibility of a filler having a high thermal conductivity, and to obtain a curable resin composition which can obtain a cured product that can achieve both high adhesion and a high thermal conductivity to a substrate. An object of the present invention is to provide a dry film having a resin layer obtained from the composition, a cured product of the resin layer of the composition or the dry film, and an electronic component having the cured product.

The present inventors have conducted intensive studies with an eye on surface treatment of perovskite-type compounds to achieve the above object. As a result, the inventors have found that a hydrated oxide of silicon, a hydrated oxide of aluminum, a hydrated oxide of zirconium, a hydrated oxide of zinc, and a hydrated oxide of titanium can be used. By using a coated perovskite-type compound, it was found that the above-mentioned problem could be solved by doing so, and the present invention was completed.

That is, the curable resin composition of the first aspect of the present invention comprises a hydrated oxide of silicon, a hydrated oxide of aluminum, a hydrated oxide of zirconium, a hydrated oxide of zinc, and a hydrated oxide of titanium. A perovskite-type compound coated with at least one of the materials and a curable resin.

は In the curable resin composition of the first aspect of the present invention, it is preferable that the coated perovskite compound is at least 20% by volume based on the total solid content of the composition.

は In the curable resin composition according to the first aspect of the present invention, the coated perovskite compound preferably further has a curable reactive group on the surface.

The dry film according to the first aspect of the present invention has a resin layer obtained by applying the curable resin composition to a film and drying the film.

The cured product of the first aspect of the present invention is obtained by curing the curable resin composition or the resin layer of the dry film.

電子 An electronic component according to a first aspect of the present invention includes the cured product.

本 Further, the present inventors have conducted intensive studies with a focus on the surface treatment of titanium oxide to achieve the above object. As a result, the inventors have found that the hydrated oxide of silicon, the hydrated oxide of aluminum, the hydrated oxide of zirconium, the hydrated oxide of zinc, and the hydrated oxide of titanium It has been found that the above problem can be solved by using titanium oxide particles which are coated with and further have a curable reactive group on the surface, and have completed the present invention.

That is, the curable resin composition of the second aspect of the present invention comprises a hydrated oxide of silicon, a hydrated oxide of aluminum, a hydrated oxide of zirconium, a hydrated oxide of zinc and a hydrated oxide of titanium. A curable resin composition comprising: a titanium oxide particle coated with at least one of a material; and a curable resin, wherein the coated titanium oxide particle has a curable reactive group on the surface. It is characterized by having.

は In the curable resin composition according to the second aspect of the present invention, the coated titanium oxide particles preferably account for 25% by volume or more based on the total solid content of the composition.

は In the curable resin composition of the second aspect of the present invention, the coated titanium oxide particles preferably have an absolute value of zeta potential of 15 mV or more.

は The curable resin composition of the second aspect of the present invention preferably has an acid value of the solid content of the composition of not more than 25 mgKOH / g.

硬化 The curable resin composition of the second aspect of the present invention is preferably applied to a substrate having a dielectric loss tangent at a frequency of 10 GHz of 0.01 or less.

ドライ A dry film according to a second aspect of the present invention is characterized by having a resin layer obtained by applying and drying the curable resin composition on a film.

The cured product of the second aspect of the present invention is obtained by curing the curable resin composition or the resin layer of the dry film.

A laminated structure according to a second aspect of the present invention is a structure including a cured resin layer (A) and a cured resin layer (B) or a substrate (C) in contact with the cured resin layer (A). ,
The resin cured layer (A) is a cured product having a positive zeta potential obtained by curing the curable resin composition or the resin layer of the dry film,
The zeta potential of the resin cured layer (B) or the substrate (C) is negative.

電子 An electronic component according to a second aspect of the present invention includes the cured product or the laminated structure.

本 Further, the inventors of the present invention have conducted intensive studies with an eye on the surface treatment of a filler having high thermal conductivity in order to achieve the above object. As a result, the inventors have found that fillers with high thermal conductivity are hydrated oxides of silicon, hydrated oxides of aluminum, hydrated oxides of zirconium, hydrated oxides of zinc and hydrated oxides of titanium. It has been found that the above problems can be solved by coating with at least one of the above, and the present invention has been completed.

That is, the curable resin composition of the third aspect of the present invention comprises a hydrated oxide of silicon, a hydrated oxide of aluminum, a hydrated oxide of zirconium, a hydrated oxide of zinc and a hydrated oxide of titanium. A filler having a thermal conductivity of at least 15 W / m · k coated with at least one of the materials and a curable resin.

In the curable resin composition according to the third aspect of the present invention, the coated filler having a thermal conductivity of 15 W / m · k or more is 30% by volume or more based on the total solid content of the composition. Is preferred.

は In the curable resin composition according to the third aspect of the present invention, it is preferable that the coated filler having a thermal conductivity of 15 W / mk or more further has a curable reactive group on the surface.

ドライ A dry film according to a third aspect of the present invention has a resin layer obtained by applying the curable resin composition to a film and drying the film.

硬化 The cured product of the third aspect of the present invention is obtained by curing the curable resin composition or the resin layer of the dry film.

電子 An electronic component according to a third aspect of the present invention includes the cured product.

First, according to the present invention, a curable resin composition is obtained, in which the dispersibility of the perovskite compound is improved, the adhesion to the substrate is excellent, and a cured product that can achieve both a high dielectric constant and a low dielectric loss tangent is obtained. Product, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and an electronic component having the cured product.

Secondly, according to the present invention, a curable resin composition is obtained, in which the dispersibility of titanium oxide is improved, the adhesiveness to a substrate is excellent, and a cured product that can achieve both a high dielectric constant and a low dielectric loss tangent is obtained. A dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, a laminated structure having a cured resin layer made of the cured product, and an electron having the cured product Parts can be provided.

Thirdly, according to the present invention, the heat dispersibility of the filler having a high thermal conductivity is improved, and a curable resin composition is obtained, which can provide a cured product that can achieve both adhesion to a substrate and high thermal conductivity. A dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and an electronic component having the cured product can be provided.

FIG. 1 is a schematic sectional view schematically showing one embodiment of a laminated structure of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. In this specification, the term “(meth) acrylate” is a general term for acrylate, methacrylate and mixtures thereof, and the same applies to other similar expressions. Further, in this specification, when a numerical range is expressed by “to”, it means a range including those numerical values (that is,... Or more).

<<< First embodiment of the present invention >>>
The curable resin composition of the first aspect of the present invention comprises a hydrated oxide of silicon, a hydrated oxide of aluminum, a hydrated oxide of zirconium, a hydrated oxide of zinc and a hydrated oxide of titanium. It is characterized by containing a perovskite type compound coated with at least one of them, and a curable resin.

By blending the coated perovskite-type compound, excellent adhesion to the substrate is achieved, and the surface roughness of the substrate is low, and the adhesion is reduced even to a low-profile substrate made of a low-polarity material. It is possible to obtain a cured product having both a high dielectric constant and a low dielectric loss tangent.

The problem of the adhesion is particularly remarkable when the blending amount of the perovskite compound is large, but according to the first aspect of the present invention, when the blending amount of the perovskite compound is large, for example, the solid content of the composition Even when the content is 20% by volume or more based on the total capacity, a cured product having excellent adhesion to the substrate can be obtained. That is, according to the first embodiment of the present invention, it is possible to simultaneously achieve the contradictory characteristics of adhesion to a substrate and high dielectric constant and low dielectric loss tangent due to high filling of a perovskite compound.

In addition, when the perovskite-type compound is filled in a large amount, adhesion to a substrate made of a low-polarity material or a substrate having a roughened-free or low-roughened surface having no anchor effect (so-called low-profile substrate) is particularly deteriorated. As a result, the problem that the adhesion tends to decrease after the HAST treatment occurs. However, in the first embodiment of the present invention, even if the above-described substrate is used, the HAST treatment can be performed by blending the coated perovskite compound. Even after the treatment, a cured product having excellent adhesion can be obtained.

Further, the coated perovskite compound is at least one of a hydrated oxide of silicon, a hydrated oxide of aluminum, a hydrated oxide of zirconia, a hydrated oxide of zinc and a hydrated oxide of titanium. Since the resin is covered with one or more kinds, coarse particles are hardly generated in the curable resin, and the insulation reliability is particularly excellent even when a fine-patterned circuit board is used. In addition, generation of cracks starting from aggregates can also be suppressed.

It is preferable that the coated perovskite compound has a curable reactive group on the surface. In general, when the filler has a curable reactive group on the surface, it is possible to strengthen the bond between the filler and the curable resin, but when the filler is highly filled, while the specific surface area of the filler particles is large, Since the resin content is small, it is easy to cause a portion that is not sufficiently compatible with the curable resin. Particularly, in a HAST (high temperature and high humidity) environment, it becomes a factor of absorbing moisture, and the possibility that the curable reactive group portion is hydrolyzed is increased. . Therefore, the adhesion after HAST is inferior and peeling is likely to occur. Such poor wettability was particularly remarkable when the particle size of the filler was small because the specific surface area of the filler was large and the amount of resin to cover was large. In addition, even when a curable reactive group is directly applied to the surface of the filler, the wettability with the curable resin is insufficient. .

However, in the first embodiment of the present invention, even if the coated perovskite compound has a curable reactive group on the surface, the hydration of silicon is caused between the perovskite compound and the curable reactive group. Since at least one of oxides, hydrated oxides of aluminum, hydrated oxides of zirconium, hydrated oxides of zinc, and hydrated oxides of titanium are interposed, even in a HAST environment It is also confirmed that the decrease in adhesion due to hydrolysis is small. That is, since the wettability with the curable resin can be maintained even after the HAST treatment, an excellent effect that the adhesion is hardly reduced can be obtained. Further, it is possible to improve the physical properties of the cured product due to the curable reactive group, for example, to reduce the CTE.

In the first embodiment of the present invention, the perovskite-type compound has more hydroxyl groups based on the hydrated oxide on the surface thereof, and the curable reactive group can be effectively imparted thereto, so that the melt viscosity can be further reduced. It is preferable to have a curable reactive group on the surface.

(4) Hereinafter, each component contained in the curable resin composition of the first embodiment of the present invention will be described.

[Perovskite compound]
The curable resin composition of the first aspect of the present invention comprises a hydrated oxide of silicon, a hydrated oxide of aluminum, a hydrated oxide of zirconia, a hydrated oxide of zinc and a hydrated oxide of titanium. A perovskite-type compound coated with at least one of them.

Examples of the perovskite-type compound to be coated include barium titanate, calcium titanate, strontium titanate, barium zirconate, calcium zirconate, strontium zirconate, and composite oxides containing these as main components. Among them, it is preferable to use barium titanate, calcium titanate, strontium titanate, calcium zirconate, strontium zirconate, or a composite oxide containing these as a main component. The perovskite compound refers to a compound represented by ABO ₃ (A and B are divalent and tetravalent metal ions, and O is an oxygen ion).

市販 Commercially available perovskite-type compounds include BT-03, CT-03, ST-03, CZ-03, SZ-03, CZ-03, etc., manufactured by Sakai Chemical Industry Co., Ltd.

The method of coating the perovskite compound is not particularly limited, but as a method of coating the perovskite compound with a hydrated oxide of silicon, for example, an aqueous solution of an alkali silicate is added to a water slurry of the perovskite compound to prepare the perovskite compound. By generating silicic acid on the surface and then adding mineral acid to the slurry, silicic acid can be decomposed into hydrated oxides of silicon, and hydrated oxides of silicon can be deposited on the surface of the perovskite-type compound. The amount of the perovskite-type compound in the water slurry is not particularly limited, but is usually 50 to 200 g / l. Next, as the alkali silicate to be added to the water slurry as described above, specifically, sodium silicate, potassium silicate or the like is used, and its concentration is usually 10 to 200 g / l in terms of perovskite type compound. . Hydrochloric acid, nitric acid, sulfuric acid and the like can be used as the mineral acid.

As a method of coating the perovskite compound with a hydrated oxide of aluminum, for example, after adding an aqueous solution of a water-soluble aluminum compound such as sodium aluminate to a water slurry of the perovskite compound, neutralization with an alkali or an acid Thereby, a hydrated oxide of aluminum can be deposited on the surface of the perovskite compound. The amount of the perovskite-type compound in the water slurry is not particularly limited, but usually 30 to 300 g / l is appropriate. As the alkali, sodium hydroxide, potassium hydroxide, ammonia, and as the acid, hydrochloric acid, nitric acid, and the like are used. The amount to be added is an amount by which the water-soluble aluminum compound can form a hydrated oxide of aluminum. Is 7 ± 0.5.

As a method of coating the perovskite compound with a hydrated oxide of zirconium, for example, after adding an aqueous solution of a water-soluble zirconium compound such as zirconium oxychloride to a water slurry of the perovskite compound, neutralization with an alkali or an acid Thereby, a hydrated oxide of zirconium can be deposited on the surface of the perovskite compound. The amount of the perovskite-type compound in the water slurry is not particularly limited, but usually 30 to 300 g / l is appropriate. As the alkali, sodium hydroxide, potassium hydroxide, ammonia or the like is used, and the amount to be added is such that the water-soluble zirconium compound can form a hydrated oxide of zirconium, and the pH is preferably 7 ± 0.5. is there.

As a method of coating the perovskite compound with a hydrated oxide of zinc, for example, after adding an aqueous solution of a water-soluble zinc compound such as zinc sulfate to a water slurry of the perovskite compound, neutralization with an alkali or an acid The hydrated oxide of zinc can be deposited on the surface of the perovskite compound. The amount of the perovskite-type compound in the water slurry is not particularly limited, but usually 30 to 300 g / l is appropriate. As the alkali, sodium hydroxide, potassium hydroxide, ammonia or the like is used, and the amount to be added is such that the water-soluble zinc compound can form a hydrated oxide of zinc, and the pH is preferably 7 ± 0.5. is there.

As a method of coating the perovskite compound with a hydrated oxide of titanium, for example, by adding an aqueous solution of a water-soluble titanium such as titanyl sulfate to a water slurry of the perovskite compound, and neutralizing with an alkali or an acid, A hydrated oxide of titanium can be deposited on the surface of the perovskite compound. The amount of the perovskite-type compound in the water slurry is not particularly limited, but usually 30 to 300 g / l is appropriate. As the acid, hydrochloric acid, nitric acid or the like is used, and the amount to be added is such that the above water-soluble titanium compound can form a hydrated oxide of titanium, and the pH is preferably 7 ± 0.5.

The coating with at least one of a hydrated oxide of silicon, a hydrated oxide of aluminum, a hydrated oxide of zirconium, a hydrated oxide of zinc, and a hydrated oxide of titanium comprises a perovskite compound 100 The hydrated oxide such as silicon is preferably coated with 1 to 40 parts by mass, more preferably 3 to 20 parts by mass, with respect to parts by mass. By coating with 1 part by mass or more, it is possible to obtain a cured product which is more excellent in dispersibility of the perovskite compound in the curable resin and in which the adhesion is less likely to decrease after the HAST treatment.

The coated perovskite compound is preferably a perovskite compound coated with a hydrated oxide of silicon and a hydrated oxide of aluminum. It is preferable that the coated perovskite compound has a coating layer made of a hydrated oxide of silicon and a coating layer made of a hydrated oxide of aluminum in this order. By coating in this manner, it is possible to obtain a cured product which is more excellent in the dispersibility of the perovskite compound in the curable resin and in which the adhesion is less likely to decrease after the HAST treatment. Further, it becomes possible to efficiently adhere the coating layer made of aluminum hydrated oxide, and as an effect thereof, the photoreactivity of the composition can be improved and the sensitivity can be increased. It is presumed that this probably acted as a photocatalyst to promote photosensitivity. This effect is seen not only in hydrated oxides of aluminum but also in metal compounds such as hydrated oxides of zirconia, hydrated oxides of zinc, and hydrated oxides of titanium without increasing the amount of photoreaction initiator. Contributes to plating resistance.

As described above, in the first embodiment of the present invention, even when the surface has a curable reactive group, the adhesiveness after the HAST treatment is excellent, and a strong bond with the curable resin is obtained. Therefore, the physical properties of the cured product can be improved by the curable reactive group. Here, the curable reactive group is not particularly limited as long as it is a group that undergoes a curing reaction with a component (for example, a curable resin or an alkali-soluble resin) blended in the curable resin composition. It may be a thermosetting reactive group. Examples of the photocurable reactive group include a methacryl group, an acrylic group, a vinyl group, and a styryl group. Examples of the thermosetting reactive group include an epoxy group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, an imino group, and oxetanyl. Group, mercapto group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group, oxazoline group and the like. The method for introducing a curable reactive group on the surface of the coated perovskite compound is not particularly limited, and may be introduced using a known and commonly used method, and a surface treating agent having a curable reactive group, for example, a curable The surface of the coated perovskite compound may be treated with a coupling agent having a reactive group as an organic group. As the coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, or the like can be used. Especially, a silane coupling agent is preferable. Further, by treating the surface of the coated perovskite compound, the dispersibility of the perovskite compound can be further improved.

The curable reactive group that the coated perovskite compound has on the surface may be a photocurable reactive group when the curable resin composition of the first aspect of the present invention contains a photocurable resin. Preferably, when a thermosetting resin is contained, it is preferably a thermosetting reactive group.

平均 The coated perovskite compound preferably has an average particle size of 0.01 to 10 μm, more preferably 0.01 to 1 μm. Since the perovskite-type compound has a high refractive index, in the case of a photocurable composition, a smaller average particle diameter is preferable because it is excellent in deep part curability. On the other hand, from the viewpoints of high reflectivity and opacity, a larger average particle diameter is preferable. Further, the maximum particle diameter (D100) is preferably 5 μm or less. A smaller one suppresses sedimentation. Here, in this specification, the average particle diameter of the perovskite compound is an average particle diameter (D50) including not only the particle diameter of the primary particles but also the particle diameter of the secondary particles (aggregates). It is a value of D50 measured by the method. As a measuring device by the laser diffraction method, there is Microtrac @ MT3300EXII manufactured by Nikkiso Co., Ltd.

The average particle diameter of the coated perovskite compound may be adjusted. For example, it is preferable that the compound is preliminarily dispersed by a bead mill or a jet mill. The coated perovskite compound is preferably compounded in a slurry state. By compounding in a slurry state, high dispersion can be easily achieved, aggregation is prevented, and handling is facilitated.

は The coated perovskite compound can be used alone or in combination of two or more. In the first aspect of the present invention, the compounded amount of the coated perovskite compound is large, and it is possible to obtain a cured product excellent in adhesion to a substrate even when the resin component is relatively small. For example, the amount of the coated perovskite compound may be 20% by volume or more, or even 25% by volume or more based on the total solid content of the composition. The dielectric constant can be increased as the amount of the coated perovskite compound increases. Preferably, it is at least 30% by volume. The upper limit is, for example, 60% by volume from the viewpoint of the properties of the cured product and handling. When the average particle size is 0.5 μm or more, it is preferably 35% by volume or more.

Further, as described above, the compounding amount of the coated perovskite-type compound is 30 to 90% by mass in the total solid content of the composition, because the larger the compounding amount, the higher the dielectric constant can be. Is preferred.

<<< second embodiment of the present invention >>>
The curable resin composition of the second aspect of the present invention comprises a hydrated oxide of silicon, a hydrated oxide of aluminum, a hydrated oxide of zirconium, a hydrated oxide of zinc and a hydrated oxide of titanium. A curable resin composition comprising titanium oxide particles coated with at least one of the above and a curable resin, wherein the coated titanium oxide particles have a curable reactive group on the surface. It is characterized by the following.

By blending the coated titanium oxide particles having a curable reactive group on the surface (hereinafter, also simply referred to as “coated titanium oxide particles”), excellent adhesion to the substrate is obtained, and the surface of the substrate is A cured product having a low roughness and a small decrease in adhesion to a low-profile substrate made of a low-polarity material can be obtained. It is preferable that the coated titanium oxide particles are coated with at least a hydrated oxide of aluminum because a decrease in adhesion can be further suppressed.

The problem of the adhesion is particularly remarkable when the blending amount of the titanium oxide particles is large, but according to the second aspect of the present invention, when the blending amount of the coated titanium oxide particles is large, for example, Even if the content is 25% by volume or more based on the total solid content of the composition, a cured product having excellent adhesion to a substrate can be obtained. That is, according to the second aspect of the present invention, it is possible to simultaneously achieve the contradictory properties of adhesion to a substrate and high dielectric constant and low dielectric loss tangent due to high filling of titanium oxide particles.

In addition, when the filling amount of titanium oxide is large, adhesion to a substrate having a roughening free or low roughness surface (so-called low-profile substrate) having no anchor effect or a substrate made of a low-polarity material is deteriorated. Although the problem that the adhesion tends to decrease after the HAST process occurs, in the second embodiment of the present invention, the above-described substrate can be mixed with the HAST process by mixing the coated titanium oxide particles. After that, a cured product having excellent adhesion can be obtained.

Further, the coated titanium oxide particles may be a hydrated oxide of silicon, a hydrated oxide of aluminum, a hydrated oxide of zirconia, a hydrated oxide of zinc, and a hydrated oxide of titanium. Since the resin is covered with one or more kinds, coarse particles are hardly generated in the curable resin, and the insulation reliability is particularly excellent even when a fine-patterned circuit board is used. In addition, generation of cracks starting from aggregates can also be suppressed.

In addition, as described above, generally, when the filler has a curable reactive group on the surface, it is possible to strengthen the bond between the filler and the curable resin. In a severe environment, the adhesion decreased due to hydrolysis and the like.

However, in the second embodiment of the present invention, even if the coated titanium oxide particles have a curable reactive group on the surface, hydration of silicon is caused between the titanium oxide particles and the curable reactive group. Since at least one of oxides, hydrated oxides of aluminum, hydrated oxides of zirconium, hydrated oxides of zinc, and hydrated oxides of titanium are interposed, even in a HAST environment It is also confirmed that the decrease in adhesion due to hydrolysis is small. That is, since the wettability with the curable resin can be maintained even after the HAST treatment, an excellent effect that the adhesion is hardly reduced can be obtained. Further, it is possible to improve the physical properties of the cured product due to the curable reactive group, for example, to reduce the CTE.

Further, in the second aspect of the present invention, the hydroxyl groups based on hydrated oxides are increased on the surface of the titanium oxide particles, and the curable reactive groups are effectively imparted thereto, so that the melt viscosity is further reduced. can do.

酸 The curable resin composition of the second aspect of the present invention may have an acid value at a solid content of 25 mgKOH / g or less, and further may have an acid value of 20 mgKOH / g or less. A higher acid value is advantageous in adhesion since a large amount of hydroxyl groups remain after curing, but from the viewpoint of a low dielectric loss tangent, a lower acid value is preferable. In the present invention, even if the composition system has a low acid value, the adhesion is good by including the coated titanium oxide particles.

[Titanium oxide particles]
The curable resin composition of the second aspect of the present invention comprises a hydrated oxide of silicon, a hydrated oxide of aluminum, a hydrated oxide of zirconia, a hydrated oxide of zinc and a hydrated oxide of titanium. And titanium oxide particles coated with at least one of them. The coated titanium oxide particles further have a curable reactive group on the surface.

The titanium oxide particles to be coated (that is, titanium oxide particles before coating) are not particularly limited, and known and commonly used titanium oxide particles that can be used as an inorganic filler or a white pigment may be used. The titanium oxide may be any one of a rutile type, an anatase type and a ramsdellite type structure. That is, the titanium oxide particles to be coated may be appropriately selected from the viewpoints of reflectance, coloring property, concealing property, moldability and stability, and may be of rutile type or anatase type. Among them, the ramsdellite type titanium oxide is obtained by subjecting the ramsdellite type Li _0.5 TiO ₂ to a lithium desorption treatment by chemical oxidation.

The method of coating the titanium oxide particles is not particularly limited, but examples of a method of coating the titanium oxide particles with a hydrated oxide of silicon include, for example, adding an aqueous alkali silicate solution to a water slurry of the titanium oxide particles to form the titanium oxide particles. By generating silicic acid on the surface and then adding a mineral acid to the slurry, the silicic acid can be decomposed into hydrated oxides of silicon and the hydrated oxides of silicon can be deposited on the surfaces of the titanium oxide particles. The amount of the titanium oxide particles in the water slurry is not particularly limited, but is usually 70 to 150 g / l. Next, as the alkali silicate to be added to the above-mentioned water slurry, specifically, sodium silicate, potassium silicate or the like is used, and its concentration is usually 10 to 200 g / l in terms of titanium oxide particles. . Hydrochloric acid, nitric acid, sulfuric acid and the like can be used as the mineral acid.

As a method of coating titanium oxide particles with a hydrated oxide of aluminum, for example, an aqueous solution of a water-soluble aluminum compound such as sodium aluminate is added to a water slurry of titanium oxide particles, and then neutralized with an alkali or an acid. A hydrated oxide of aluminum can be deposited on the surface of the titanium oxide particles. The amount of the titanium oxide particles in the water slurry is not particularly limited, but usually, 30 to 300 g / l is appropriate. As the alkali, sodium hydroxide, potassium hydroxide, ammonia, and as the acid, hydrochloric acid, nitric acid, and the like are used. The amount to be added is an amount by which the water-soluble aluminum compound can form a hydrated oxide of aluminum. Is 7 ± 0.5.

As a method of coating titanium oxide particles with a hydrated oxide of zirconium, for example, after adding an aqueous solution of a water-soluble zirconium compound such as zirconium oxychloride to a water slurry of titanium oxide particles, neutralization with an alkali or an acid Thereby, the hydrated oxide of zirconium can be deposited on the surface of the titanium oxide particles. The amount of the titanium oxide particles in the water slurry is not particularly limited, but usually, 30 to 300 g / l is appropriate. As the alkali, sodium hydroxide, potassium hydroxide, ammonia or the like is used, and the amount to be added is such that the water-soluble zirconium compound can form a hydrated oxide of zirconium, and the pH is preferably 7 ± 0.5. is there.

As a method of coating titanium oxide particles with a hydrated oxide of zinc, for example, by adding an aqueous solution of a water-soluble zinc compound such as zinc sulfate to a water slurry of titanium oxide particles, and then neutralizing with an alkali or acid. The hydrated oxide of zinc can be deposited on the surface of the titanium oxide particles. The amount of the titanium oxide particles in the water slurry is not particularly limited, but usually, 30 to 300 g / l is appropriate. As the alkali, sodium hydroxide, potassium hydroxide, ammonia or the like is used, and the amount to be added is such that the water-soluble zinc compound can form a hydrated oxide of zinc, and the pH is preferably 7 ± 0.5. is there.

As a method of coating titanium oxide particles with a hydrated oxide of titanium, for example, by adding an aqueous solution of a water-soluble titanium such as titanyl sulfate to a water slurry of titanium oxide particles, and then neutralizing with an alkali or an acid, A hydrated oxide of titanium can be deposited on the surface of the titanium oxide particles. The amount of the titanium oxide particles in the water slurry is not particularly limited, but usually, 30 to 300 g / l is appropriate. As the acid, hydrochloric acid, nitric acid or the like is used, and the amount to be added is such that the above water-soluble titanium compound can form a hydrated oxide of titanium, and the pH is preferably 7 ± 0.5.

The coating with at least one of a hydrated oxide of silicon, a hydrated oxide of aluminum, a hydrated oxide of zirconium, a hydrated oxide of zinc, and a hydrated oxide of titanium is performed using titanium oxide particles 100 The hydrated oxide such as silicon is preferably coated with 1 to 40 parts by mass, more preferably 3 to 20 parts by mass, with respect to parts by mass. By coating with 1 part by mass or more, it is possible to obtain a cured product which is more excellent in dispersibility of the titanium oxide particles in the curable resin and in which the adhesion is less likely to decrease after the HAST treatment.

The coated titanium oxide particles are preferably titanium oxide particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum. The coated titanium oxide particles preferably have a coating layer made of a hydrated oxide of silicon and a coating layer made of a hydrated oxide of aluminum in this order. By coating in this manner, it is possible to obtain a cured product which is more excellent in dispersibility of the titanium oxide particles in the curable resin and in which the adhesion is less likely to decrease after the HAST treatment. Further, it becomes possible to efficiently adhere the coating layer made of aluminum hydrated oxide, and as an effect thereof, the photoreactivity of the composition can be improved and the sensitivity can be increased. It is presumed that this probably acted as a photocatalyst to promote photosensitivity. This effect is seen not only in hydrated oxides of aluminum but also in metal compounds such as hydrated oxides of zirconia, hydrated oxides of zinc, and hydrated oxides of titanium without increasing the amount of photoreaction initiator. Contributes to plating resistance.

As described above, in the present invention, the curable reactive group is not particularly limited as long as it is a group that undergoes a curing reaction with a component (for example, a curable resin or an alkali-soluble resin) blended in the curable resin composition. It may be a photocurable reactive group or a thermosetting reactive group. Examples of the photocurable reactive group include a methacryl group, an acrylic group, a vinyl group, and a styryl group. Examples of the thermosetting reactive group include an epoxy group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, an imino group, and oxetanyl. Group, mercapto group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group, oxazoline group and the like. The method for introducing a curable reactive group on the surface of the coated titanium oxide particles is not particularly limited, and may be introduced using a known and commonly used method, and a surface treatment agent having a curable reactive group, for example, a curable The surface of the coated titanium oxide particles may be treated with a coupling agent having a reactive group as an organic group. As the coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, or the like can be used. Especially, a silane coupling agent is preferable. By treating the surface of the coated titanium oxide particles, the dispersibility of the titanium oxide particles can be further improved.

The curable reactive group that the coated titanium oxide particles have on the surface may be a photocurable reactive group when the curable resin composition of the second aspect of the present invention contains a photocurable resin. Preferably, when a thermosetting resin is contained, it is preferably a thermosetting reactive group.

平均 The average particle diameter of the coated titanium oxide particles is preferably 0.01 to 10 μm, and more preferably 0.01 to 1 μm. Since titanium oxide has a high refractive index, in the case of a photocurable composition, it is preferable that the average particle diameter is small because the composition is excellent in deep part curability. On the other hand, from the viewpoints of high reflectivity and opacity, a larger average particle diameter is preferable. Further, the maximum particle diameter (D100) is preferably 5 μm or less. A smaller one suppresses sedimentation. Here, in this specification, the average particle diameter of the titanium oxide particles is an average particle diameter (D50) including not only the particle diameter of the primary particles but also the particle diameter of the secondary particles (aggregates), and It is a value of D50 measured by the method. As a measuring device by the laser diffraction method, there is Microtrac @ MT3300EXII manufactured by Nikkiso Co., Ltd.

平均 The coated titanium oxide particles may be adjusted in average particle diameter, and for example, are preferably preliminarily dispersed by a bead mill or a jet mill. Further, the coated titanium oxide particles are preferably blended in a slurry state. By blending in a slurry state, high dispersion can be easily achieved, aggregation is prevented, and handling is facilitated.

絶対 It is preferable that the absolute value of the zeta potential of the coated titanium oxide particles is 15 mV or more. The absolute value of the surface potential of titanium oxide is increased, the dispersibility is improved by separating from the isoelectric point, the wettability with the curable resin is improved, and the adhesion to the substrate is further improved by considering the Coulomb force. improves. More preferably, it is 25 mV or more.

Also, each component material of the semiconductor package (such as a low-polarity interlayer insulating material or a sealing material) and the surface of a silicon wafer or a glass substrate wafer often have a negative zeta potential, and from the viewpoint of adhesion to the substrate, The zeta potential of the coated titanium oxide particles is preferably positive. In the second aspect of the present invention, the titanium oxide particles are subjected to a surface treatment so as to increase the positive charge, so that a low-polarity material can be obtained without applying an adhesion promoter (AP: Adhesion @ Promoter) on those substrates. Good adhesion to a low-profile substrate made of (Low @ Df material) or a substrate free from roughening can be obtained.

In particular, when an amine-based compound is contained, Coulomb force acts on the coated titanium oxide particles having a positive zeta potential, and dispersibility of the coated titanium oxide particles in the curable resin composition. This improves the adhesion to a roughening-free substrate or a low-profile substrate. Further, even when the constituent material of the contact target is made of a material containing an amine compound, a cured product having excellent adhesion to the contact target object can be obtained.

は The coated titanium oxide particles can be used alone or in combination of two or more. In the second aspect of the present invention, the compounded amount of the coated titanium oxide particles is large, and it is possible to obtain a cured product having excellent adhesion to the substrate even when the resin component is relatively small. . For example, the compounding amount of the coated titanium oxide particles may be 25% by volume or more, and more preferably 30% by volume or more, based on the total solid content of the composition. The greater the blending amount of the coated titanium oxide particles, the higher the dielectric constant can be. The upper limit is, for example, 50% by volume from the viewpoint of the properties of the cured product and handling. When the average particle size is 0.5 μm or more, it is preferably 35% by volume or more.

The blending amount of the coated titanium oxide particles varies depending on the average particle diameter. As described above, the larger the blending amount, the higher the dielectric constant can be. Therefore, the blending amount is, for example, 30 to 80% by mass. .

<<< 3rd aspect of this invention >>
The curable resin composition of the third aspect of the present invention comprises a hydrated oxide of silicon, a hydrated oxide of aluminum, a hydrated oxide of zirconium, a hydrated oxide of zinc and a hydrated oxide of titanium. A filler having a thermal conductivity of 15 W / m · k or more coated with at least one of them (hereinafter, also referred to as “the coated filler having a high thermal conductivity”) and a curable resin; It is characterized by the following.

By blending the coated high thermal conductivity filler, excellent adhesion to the substrate, and also low surface roughness of the substrate, adhesion to a low-profile substrate made of a low-polarity material A cured product with little decrease can be obtained.

The problem of the adhesion is particularly remarkable when the content of the high thermal conductivity filler is large, but according to the third embodiment of the present invention, the content of the coated high thermal conductivity filler is large. In this case, for example, even if the content is 30% by volume or more based on the total solid content of the composition, a cured product excellent in adhesion to a substrate can be obtained.

In addition, when the filling amount of the filler having a high thermal conductivity is large, adhesion to a substrate having a roughening free or low roughened surface having no anchor effect (a so-called low profile substrate) or a substrate made of a low-polarity material is particularly poor. However, in the third aspect of the present invention, the above-described substrate is mixed by adding the filler having a high thermal conductivity. However, even after the HAST treatment, a cured product having excellent adhesion can be obtained.

Further, the coated high thermal conductivity filler is a hydrated oxide of silicon, a hydrated oxide of aluminum, a hydrated oxide of zirconia, a hydrated oxide of zinc and a hydrated oxide of titanium. Since it is covered with at least one kind, coarse particles are hardly generated in the curable resin, and the insulation reliability is particularly excellent even when a fine-patterned circuit board is used. In addition, generation of cracks starting from aggregates can also be suppressed.

The coated high thermal conductivity filler preferably has a curable reactive group on the surface. As described above, in general, when the filler has a curable reactive group on the surface, it is possible to strengthen the bond between the filler and the curable resin. However, when the filler is highly filled, it is particularly severe such as HAST. Under the environment, the adhesion decreased due to hydrolysis and the like.

However, in the third aspect of the present invention, even if the coated high thermal conductivity filler has a curable reactive group on the surface, between the high thermal conductivity filler and the curable reactive group, Since at least one of a hydrated oxide of silicon, a hydrated oxide of aluminum, a hydrated oxide of zirconium, a hydrated oxide of zinc and a hydrated oxide of titanium is present, It has also been confirmed that even under a HAST environment, a decrease in adhesion due to hydrolysis is small. That is, since the wettability with the curable resin can be maintained even after the HAST treatment, an excellent effect that the adhesion is hardly reduced can be obtained. Further, it is possible to improve the physical properties of the cured product due to the curable reactive group, for example, to reduce the CTE.

In the third embodiment of the present invention, the number of hydroxyl groups based on the hydrated oxide is increased on the surface of the filler having a high thermal conductivity, and the melt viscosity can be further reduced by effectively providing a curable reactive group thereto. Therefore, it is preferable to have a curable reactive group on the surface.

In addition, in the third embodiment of the present invention, when a photosensitive curable resin composition is used, the resolution is improved.

[Filler having a thermal conductivity of 15 W / m · k or more]
The curable resin composition of the third aspect of the present invention comprises a hydrated oxide of silicon, a hydrated oxide of aluminum, a hydrated oxide of zirconia, a hydrated oxide of zinc and a hydrated oxide of titanium. A filler coated with at least one of them and having a thermal conductivity of 15 W / m · k or more is included.

Examples of the filler having a thermal conductivity of 15 W / mk or more include particles such as boron nitride, aluminum nitride, silicon nitride, silicon carbide, magnesium oxide, aluminum oxide, spinel, carbon nanotube, graphene, diamond, and metal powder. Is mentioned. Among these, boron nitride, aluminum nitride, silicon nitride, silicon carbide, magnesium oxide, aluminum oxide, and spinel having insulating properties are preferable.

フィラー The thermal conductivity of the high thermal conductivity filler to be coated is preferably 15 W / m · k or more, more preferably 20 W / m · k or more. The upper limit of the thermal conductivity is not particularly limited, but is usually 500 W / m · k or less.

The method of coating the high thermal conductivity filler is not particularly limited.However, as a method of coating the high thermal conductivity filler with a hydrated oxide of silicon, for example, an aqueous solution of an alkali silicate is added to a water slurry of the high thermal conductivity filler. In addition, silicic acid is generated on the surface of the high thermal conductivity filler, and then the mineral acid is added to the slurry to decompose the silicic acid into hydrated oxides of silicon and to form silicon water on the surface of the high thermal conductivity filler. A hydrated oxide can be deposited. The amount of the filler having a high thermal conductivity in the water slurry is not particularly limited, but is usually 70 to 150 g / l. Next, as the alkali silicate to be added to the above-mentioned water slurry, specifically, sodium silicate, potassium silicate or the like is used, and its concentration is usually 10 to 200 g / l in terms of a filler having a high thermal conductivity. It is. Hydrochloric acid, nitric acid, sulfuric acid and the like can be used as the mineral acid.

As a method of coating the filler having a high thermal conductivity with a hydrated oxide of aluminum, for example, after adding an aqueous solution of a water-soluble aluminum compound such as sodium aluminate to a water slurry of the filler having a high thermal conductivity, an alkali or an acid is used. By neutralizing, hydrated oxide of aluminum can be deposited on the surface of the filler having high thermal conductivity. The amount of the filler having a high thermal conductivity in the water slurry is not particularly limited, but usually, 30 to 300 g / l is appropriate. As the alkali, sodium hydroxide, potassium hydroxide, ammonia, and as the acid, hydrochloric acid, nitric acid, and the like are used, and the amount to be added is an amount by which the water-soluble aluminum compound can form a hydrated oxide of aluminum. Is 7 ± 0.5.

As a method of coating a filler having a high thermal conductivity with a hydrated oxide of zirconium, for example, after adding an aqueous solution of a water-soluble zirconium compound such as zirconium oxychloride to a water slurry of the filler having a high thermal conductivity, an alkali or an acid is used. By neutralization, hydrated oxide of zirconium can be deposited on the surface of the filler having high thermal conductivity. The amount of the filler having a high thermal conductivity in the water slurry is not particularly limited, but usually, 30 to 300 g / l is appropriate. As the alkali, sodium hydroxide, potassium hydroxide, ammonia or the like is used, and the amount to be added is such that the water-soluble zirconium compound can form a hydrated oxide of zirconium, and the pH is preferably 7 ± 0.5. is there.

As a method of coating a filler having a high thermal conductivity with a hydrated oxide of zinc, for example, after adding an aqueous solution of a water-soluble zinc compound such as zinc sulfate to a water slurry of the filler having a high thermal conductivity, the solution is neutralized with an alkali or an acid. By the addition, the hydrated oxide of zinc can be deposited on the surface of the filler having a high thermal conductivity. The amount of the filler having a high thermal conductivity in the water slurry is not particularly limited, but usually, 30 to 300 g / l is appropriate. As the alkali, sodium hydroxide, potassium hydroxide, ammonia or the like is used, and the amount to be added is such that the water-soluble zinc compound can form a hydrated oxide of zinc, and the pH is preferably 7 ± 0.5. is there.

As a method of coating a filler having a high thermal conductivity with a hydrated oxide of titanium, for example, after adding an aqueous solution of a water-soluble titanium such as titanyl sulfate to a water slurry of the filler having a high thermal conductivity, neutralizing with an alkali or an acid By doing so, the hydrated oxide of titanium can be deposited on the surface of the filler having a high thermal conductivity. The amount of the filler having a high thermal conductivity in the water slurry is not particularly limited, but usually, 30 to 300 g / l is appropriate. As the acid, hydrochloric acid, nitric acid or the like is used, and the amount to be added is such that the above water-soluble titanium compound can form a hydrated oxide of titanium, and the pH is preferably 7 ± 0.5.

The coating with at least one of hydrated oxide of silicon, hydrated oxide of aluminum, hydrated oxide of zirconium, hydrated oxide of zinc and hydrated oxide of titanium has high thermal conductivity. The hydrated oxide such as silicon is preferably coated with 1 to 40 parts by mass, more preferably 3 to 20 parts by mass, based on 100 parts by mass of the filler. By coating with 1 part by mass or more, it is possible to obtain a cured product which is more excellent in dispersibility of a filler having a high thermal conductivity in a curable resin and in which the adhesion is less likely to decrease after HAST treatment.

The coated high thermal conductivity filler is preferably a high thermal conductivity filler coated with a hydrated oxide of silicon and a hydrated oxide of aluminum. Further, the coated high thermal conductivity filler preferably has a coating layer made of a hydrated oxide of silicon and a coating layer made of a hydrated oxide of aluminum in this order. By coating as described above, it is possible to obtain a cured product which is excellent in the dispersibility of the filler having a high thermal conductivity in the curable resin and in which the adhesion is less likely to decrease after the HAST treatment. Further, it becomes possible to efficiently adhere the coating layer made of aluminum hydrated oxide, and as an effect thereof, the photoreactivity of the composition can be improved and the sensitivity can be increased. It is presumed that this probably acted as a photocatalyst to promote photosensitivity. This effect is seen not only in hydrated oxides of aluminum but also in metal compounds such as hydrated oxides of zirconia, hydrated oxides of zinc, and hydrated oxides of titanium without increasing the amount of photoreaction initiator. Contributes to plating resistance.

As described above, in the third embodiment of the present invention, even when the surface has a curable reactive group, the adhesiveness after the HAST treatment is excellent, and a strong bond with the curable resin is obtained. Therefore, the physical properties of the cured product can be improved by the curable reactive group. Here, the curable reactive group is not particularly limited as long as it is a group that undergoes a curing reaction with a component (for example, a curable resin or an alkali-soluble resin) blended in the curable resin composition. It may be a thermosetting reactive group. Examples of the photocurable reactive group include a methacryl group, an acrylic group, a vinyl group, and a styryl group. Examples of the thermosetting reactive group include an epoxy group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, an imino group, and oxetanyl. Group, mercapto group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group, oxazoline group and the like. The method for introducing a curable reactive group on the surface of the coated high thermal conductivity filler is not particularly limited, and may be introduced using a known and commonly used method, and a surface treating agent having a curable reactive group, for example, The surface of the coated high thermal conductivity filler may be treated with a coupling agent having a curable reactive group as an organic group. As the coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, or the like can be used. Especially, a silane coupling agent is preferable. Further, by treating the surface of the coated high thermal conductivity filler, the dispersibility of the high thermal conductivity filler can be further improved.

The curable reactive group that the coated high thermal conductivity filler has on the surface is a photocurable reactive group when the curable resin composition of the third aspect of the present invention contains a photocurable resin. When a thermosetting resin is contained, it is preferably a thermosetting reactive group.

The coated high thermal conductivity filler preferably has an average particle size of 0.01 to 10 μm, more preferably 0.01 to 1 μm. Since the filler having a high thermal conductivity has a high refractive index, in the case of a photocurable composition, it is preferable that the average particle diameter is small because the curability in the deep part is excellent. On the other hand, from the viewpoints of thermal conductivity and opacity, it is preferable that the average particle diameter is large. Further, the maximum particle diameter (D100) is preferably 5 μm or less. A smaller one suppresses sedimentation.
Here, in this specification, the average particle diameter of the filler having a high thermal conductivity is an average particle diameter (D50) including not only the particle diameter of the primary particles but also the particle diameter of the secondary particles (aggregates), It is a value of D50 measured by a laser diffraction method. As a measuring apparatus by a laser diffraction method, there is Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd.

(4) The coated high thermal conductivity filler may have an average particle size adjusted, and for example, is preferably preliminarily dispersed by a bead mill or a jet mill. Further, the coated high thermal conductivity filler is preferably compounded in a slurry state. By compounding in a slurry state, high dispersion can be easily achieved, aggregation is prevented, and handling is facilitated.

は The coated high thermal conductivity filler may be used alone or in combination of two or more. In the third aspect of the present invention, it is possible to obtain a cured product having excellent adhesion to the substrate even when the amount of the coated high thermal conductivity filler is large and the resin component is relatively small. For example, the compounding amount of the coated high thermal conductivity filler may be 20% by volume or more, and more preferably 25% by volume or more based on the total solid content of the composition. Preferably, it is at least 30% by volume. As the amount of the coated high thermal conductivity filler increases, the thermal conductivity can be increased. The upper limit is, for example, 60% by volume from the viewpoint of the properties of the cured product and handling. When the average particle size is 0.5 μm or more, it is preferably 35% by volume or more.

As described above, as for the compounding amount of the coated high thermal conductivity filler, the larger the compounding amount, the higher the thermal conductivity can be. Therefore, for example, 30 to 90% in the total solid content of the composition. % By mass.

Hereinafter, the curable resin contained in the curable resin composition of the first to third aspects of the present invention, and each component that can be contained in the curable resin composition of the first to third aspects of the present invention will be described in detail. Will be described.

[Curable resin]
The curable resin compositions according to the first to third aspects of the present invention contain a curable resin. The curable resin used in the first to third aspects of the present invention is a thermosetting resin or a photocurable resin, and may be a mixture thereof. The compounding amount of the curable resin is, for example, 1 to 50% by mass based on the total solid content of the composition.
In the curable resin composition of the first embodiment of the present invention, since the coated perovskite compound has a relatively large refractive index, in the case of an alkali development type, a curable resin having a high ultraviolet absorption rate is used. It is preferred to include. By including a curable resin having a high ultraviolet absorptivity, the resolution can be easily controlled, and the resolution can be improved. Examples of the curable resin having a high ultraviolet absorptivity include those having a plurality of aromatic rings.

(Thermosetting resin)
When the curable resin compositions of the first to third aspects of the present invention contain a thermosetting resin, the heat resistance of the cured product is improved, and the adhesion to the base is improved. Known thermosetting resins such as isocyanate compounds, blocked isocyanate compounds, amino resins, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, epoxy compounds, polyfunctional oxetane compounds, and episulfide resins can be used as the thermosetting resin. . Among these, an epoxy compound, a polyfunctional oxetane compound, a compound having two or more thioether groups in a molecule, that is, an episulfide resin is preferable, and an epoxy compound is more preferable. The thermosetting resin can be used alone or in combination of two or more.

The epoxy compound is a compound having an epoxy group, and any of conventionally known compounds can be used. Examples include a polyfunctional epoxy compound having a plurality of epoxy groups in a molecule. Note that a hydrogenated epoxy compound may be used.

Examples of the polyfunctional epoxy compound include epoxidized vegetable oil; bisphenol A epoxy resin; hydroquinone epoxy resin; bisphenol epoxy resin; thioether epoxy resin; brominated epoxy resin; novolak epoxy resin; biphenol novolak epoxy resin; Type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; trihydroxyphenylmethane type epoxy resin; bixylenol type or biphenol type epoxy resin or a mixture thereof; Bisphenol S type epoxy resin; Bisphenol A novolak type epoxy resin; Tetraphenylolethane type epoxy resin; Heterocyclic epoxy resin; Diglycidide Phthalate resin; tetraglycidyl xylenoylethane resin; naphthalene group-containing epoxy resin; epoxy resin having a dicyclopentadiene skeleton; glycidyl methacrylate copolymer epoxy resin; copolymerized epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; A polybutadiene rubber derivative; a CTBN-modified epoxy resin; and the like, but not limited thereto. These epoxy resins can be used alone or in combination of two or more. Among these, a novolak type epoxy resin, a bisphenol type epoxy resin, a bixylenol type epoxy resin, a biphenol type epoxy resin, a biphenol novolak type epoxy resin, a naphthalene type epoxy resin or a mixture thereof is particularly preferable.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether and 1,4-bis [(3- Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3- Polyfunctional oxetanes such as (oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and their oligomers and copolymers, as well as oxetane alcohol and novolak resins , Poly (p-hydroxystyrene), cardo-type bi Phenols, calixarenes, calix resorcin arenes or etherified products such as the resin having a hydroxyl group such as silsesquioxane and the like. Other examples include a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

化合物 Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin. In addition, an episulfide resin in which an oxygen atom of an epoxy group of a novolak type epoxy resin is replaced with a sulfur atom using a similar synthesis method can also be used.

アミノ Examples of amino resins such as melamine derivatives and benzoguanamine derivatives include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.

ポリ A polyisocyanate compound can be blended as the isocyanate compound. Examples of the polyisocyanate compound include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate and Aromatic polyisocyanates such as 2,4-tolylene isocyanate dimer; aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate; Alicyclic polyisocyanates such as bicycloheptane triisocyanate; and the above-mentioned isocyanate compounds Adducts, biuret body and isocyanurate products thereof.

付加 As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. Examples of the isocyanate compound capable of reacting with the isocyanate blocking agent include the above-described polyisocyanate compounds. Examples of the isocyanate blocking agent include a phenol blocking agent; a lactam blocking agent; an active methylene blocking agent; an alcohol blocking agent; an oxime blocking agent; a mercaptan blocking agent; an acid amide blocking agent; Amine blocking agents; imidazole blocking agents; imine blocking agents and the like.

(Photocurable resin)
The photocurable resin may be any resin that is cured by irradiation with active energy rays and exhibits electrical insulation, and a compound having one or more ethylenically unsaturated groups in the molecule is preferably used. As the compound having an ethylenically unsaturated group, a known and commonly used photosensitive monomer such as a photopolymerizable oligomer or a photopolymerizable vinyl monomer can be used, and a radical polymerizable monomer or a cationic polymerizable monomer may be used. Further, as the photocurable resin, a polymer such as a carboxyl group-containing resin having an ethylenically unsaturated group as described later can be used. The photocurable resin can be used alone or in combination of two or more.

(4) As the photosensitive monomer, a liquid, solid or semi-solid photosensitive (meth) acrylate compound having one or more (meth) acryloyl groups in the molecule at room temperature can be used. The photosensitive (meth) acrylate compound which is liquid at room temperature serves to enhance the photoreactivity of the composition, adjusts the composition to a viscosity suitable for various coating methods, and assists solubility in an alkaline aqueous solution. Also fulfills.

Examples of the photopolymerizable oligomer include unsaturated polyester-based oligomers and (meth) acrylate-based oligomers. Examples of the (meth) acrylate oligomer include epoxy (meth) acrylates such as phenol novolak epoxy (meth) acrylate, cresol novolak epoxy (meth) acrylate, and bisphenol-type epoxy (meth) acrylate, urethane (meth) acrylate, and epoxy urethane (meth). A) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate, and the like.

Examples of the photopolymerizable vinyl monomer include known and common ones, for example, styrene derivatives such as styrene, chlorostyrene and α-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl vinyl ethers such as n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, and triethylene glycol monomethyl vinyl ether; acrylamide; Methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacryl (Meth) acrylamides such as amide and N-butoxymethylacrylamide; allyl compounds such as triallyl isocyanurate, diallyl phthalate and diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate and tetrahydrofurfuryl Esters of (meth) acrylic acid such as (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, and phenoxyethyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and pentaerythritol Hydroxyalkyl (meth) acrylates such as tri (meth) acrylate; alkoxyalkylene such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate Glycol mono (meth) acrylates; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropanetri Alkylene polyol poly (meth) acrylates such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxylated Polyoxyalkylene glycol poly (meth) acrylates such as trimethylolpropane triacrylate and propoxylated trimethylolpropane tri (meth) acrylate ; Poly (meth) acrylates such as hydroxyethyl Viva phosphoric acid neopentyl glycol ester di (meth) acrylate; tris [(meth) acryloxyethyl] isocyanurate rate poly (meth) acrylates such as isocyanurate.

(Alkali-soluble resin)
The curable resin compositions according to the first to third aspects of the present invention may contain an alkali-soluble resin. Examples of the alkali-soluble resin include a compound having two or more phenolic hydroxyl groups, a carboxyl group-containing resin, a compound having a phenolic hydroxyl group and a carboxyl group, and a compound having two or more thiol groups. Above all, it is preferable that the alkali-soluble resin is a carboxyl group-containing resin or a phenol resin because the adhesion to the base is improved. In particular, the alkali-soluble resin is more preferably a carboxyl group-containing resin because of excellent developability. The carboxyl group-containing resin may be a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group or a carboxyl group-containing resin having no ethylenically unsaturated group. As the alkali-soluble resin, one kind can be used alone, or two or more kinds can be used in combination.

具体 Specific examples of the carboxyl group-containing resin include the compounds listed below (which may be oligomers or polymers).

(1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate and isobutylene.

(2) Diisocyanates such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate, and carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarbonate-based polyols and polyether-based A carboxyl group-containing urethane resin obtained by a polyaddition reaction of a diol compound such as a polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, and a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(3) Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate, and polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(4) a diisocyanate and a bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin and biphenol type epoxy resin; (Meth) acrylate or a partial acid anhydride modified product thereof, a carboxyl group-containing urethane resin obtained by a polyaddition reaction of a carboxyl group-containing dialcohol compound and a diol compound.

(5) During the synthesis of the resin of the above (2) or (4), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and a terminal ( (Meth) Acrylated carboxyl group-containing urethane resin.

(6) During the synthesis of the resin (2) or (4), one isocyanate group and one or more (meth) acryloyl groups in a molecule such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. Carboxyl group-containing urethane resin having terminal (meth) acrylated by adding a compound having the same.

(7) A carboxyl group obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to a hydroxyl group present in a side chain. Containing resin.

(8) A carboxyl group-containing resin obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing hydroxyl groups of a bifunctional epoxy resin with epichlorohydrin and adding a dibasic acid anhydride to the resulting hydroxyl groups. .

(9) A carboxyl group-containing polyester resin obtained by reacting a dicarboxylic acid with a polyfunctional oxetane resin and adding a dibasic acid anhydride to a generated primary hydroxyl group.

(10) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide is reacted with an unsaturated group-containing monocarboxylic acid to obtain a reaction product. Carboxyl group-containing resin obtained by reacting a product with a polybasic acid anhydride.

(11) A reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate is reacted with an unsaturated group-containing monocarboxylic acid to obtain a reaction product. A carboxyl group-containing resin obtained by reacting a reaction product with a polybasic acid anhydride.

(12) an epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth) Reaction with an unsaturated group-containing monocarboxylic acid such as acrylic acid, etc., with respect to the alcoholic hydroxyl group of the obtained reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, anhydride A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride such as adipic acid.

(13) In addition to the carboxyl group-containing resin described in the above (1) to (12) and the like, one epoxy group and one or more () in a molecule of glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, etc. A carboxyl group-containing resin obtained by adding a compound having a (meth) acryloyl group.

アルカリ Alkali-soluble resins having at least one of an amide imide structure and an imide structure can also be suitably used.

As the alkali-soluble resin, the following formula (1) or (2):

An amide imide resin having at least one structure represented by and an alkali-soluble functional group can also be suitably used. By including a resin having an imide bond directly bonded to a cyclohexane ring or a benzene ring, a cured product excellent in toughness and heat resistance can be obtained. In particular, the amide imide resin having the structure represented by (1) is excellent in light transmittance, so that the resolution can be improved. The amide imide resin preferably has transparency. For example, the transmittance of light having a wavelength of 365 nm is preferably 70% or more in a 25 μm dry coating film of the amide imide resin.

は The content of the structures of the formulas (1) and (2) in the amide imide resin is preferably from 10 to 70% by mass. By using such a resin, it is possible to obtain a cured product that is excellent in solvent solubility and excellent in heat resistance, physical properties such as tensile strength and elongation, and dimensional stability. Preferably it is 10 to 60% by mass, more preferably 20 to 50% by mass.

As the amide imide resin having the structure represented by the formula (1), particularly, the amide imide resin represented by the formula (3A) or (3B)

(In the formulas (3A) and (3B), R is a monovalent organic group, preferably H, CF ₃ or CH ₃ , X is a direct bond or a divalent organic group, and It is preferable to use a resin having a structure represented by a bond, an alkylene group such as CH ₂ or C (CH ₃ ) ₂ ) because of excellent physical properties such as tensile strength and elongation and dimensional stability. From the viewpoint of solubility and mechanical properties, as the amide imide resin, a resin having a structure of Formulas (3A) and (3B) in an amount of 10 to 100% by mass can be suitably used. More preferably, the content is 20 to 80% by mass.

As the amide imide resin, an amide imide resin containing the structures of formulas (3A) and (3B) in an amount of 5 to 100 mol% can be preferably used from the viewpoint of solubility and mechanical properties. It is more preferably 5 to 98 mol%, further preferably 10 to 98 mol%, and particularly preferably 20 to 80 mol%.

Further, the amide imide resin having the structure represented by the formula (2) is particularly preferably a compound represented by the formula (4A) or (4B)

(In the formulas (4A) and (4B), R is a monovalent organic group, preferably H, CF ₃ or CH ₃ , and X is a direct bond or a divalent organic group. A resin having a structure represented by a bond, preferably an alkylene group such as CH ₂ or C (CH ₃ ) ₂ ) can provide a cured product having excellent mechanical properties such as tensile strength and elongation. Is preferred. From the viewpoint of solubility and mechanical properties, as the amide imide resin, a resin having the structure of formulas (4A) and (4B) in an amount of 10 to 100% by mass can be suitably used. More preferably, the content is 20 to 80% by mass.

アミド As the amide imide resin, an amide imide resin containing the structures of formulas (4A) and (4B) in an amount of 2 to 95 mol% can also be preferably used because of exhibiting good mechanical properties. More preferably, it is 10 to 80 mol%.

The amide imide resin can be obtained by a known method. The amide imide resin having the structure (1) can be obtained, for example, by using a diisocyanate compound having a biphenyl skeleton and cyclohexane polycarboxylic anhydride.

Examples of the diisocyanate compound having a biphenyl skeleton include 4,4′-diisocyanate-3,3′-dimethyl-1,1′-biphenyl and 4,4′-diisocyanate-3,3′-diethyl-1,1′-biphenyl 4,4'-diisocyanate-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-diethyl-1,1'-biphenyl, 4,4'-diisocyanate 3,3′-ditrifluoromethyl-1,1′-biphenyl, 4,4′-diisocyanate-2,2′-ditrifluoromethyl-1,1′-biphenyl and the like. In addition, an aromatic polyisocyanate compound such as diphenylmethane diisocyanate may be used.

Examples of cyclohexanepolycarboxylic anhydride include cyclohexanetricarboxylic anhydride, cyclohexanetetracarboxylic anhydride and the like.

アミド Further, the amide imide resin having the structure (2) can be obtained, for example, by using the diisocyanate compound having the biphenyl skeleton and the aqueous polycarboxylic acid having two acid anhydride groups.

Examples of the aqueous polycarboxylic acid having two acid anhydride groups include pyromellitic dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, diphenylether-3,3', 4,4'-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, biphenyl- 2,2 ', 3,3'-tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1 -Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Dianhydride, a few Bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, ethylene glycol bisanhydro And alkylene glycol bisanhydroxy trimellitate such as trimellitate.

The amide imide resin further has an alkali-soluble functional group in addition to the structures of the above formulas (1) and (2). By having an alkali-soluble functional group, a resin composition capable of alkali development can be obtained. The alkali-soluble functional group includes a carboxyl group, a phenolic hydroxyl group, a sulfo group, and the like, and preferably a carboxyl group.

Specific examples of the amide imide resin include Unidick V-8000 series and Unidick EQG-1170 manufactured by DIC, and SOXR-U manufactured by Nippon Advanced Paper Industry.

Examples of the compound having a phenolic hydroxyl group include a compound having a biphenyl skeleton or a phenylene skeleton or both skeletons, phenol, orthocresol, paracresol, metacresol, 2,3-xylenol, 2,4-xylenol, , 5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, phloroglucinol, etc. And phenolic resins having various skeletons.

Examples of the compound having a phenolic hydroxyl group include phenol novolak resin, alkylphenol volak resin, bisphenol A novolak resin, dicyclopentadiene-type phenol resin, Xylok-type phenol resin, terpene-modified phenol resin, polyvinylphenols, and bisphenol F And known phenol resins such as bisphenol S type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehyde, and condensate of dihydroxynaphthalene and aldehyde.

Commercially available phenolic resins include, for example, HF1H60 (manufactured by Meiwa Kasei Co., Ltd.), phenolite TD-2090, phenolite TD-2131 (manufactured by Dai Nippon Printing Co., Ltd.), Vesmall CZ-256-A (manufactured by DIC), Shoyounol BRG-555, SHYONORU BRG-556 (manufactured by Showa Denko KK), CGR-951 (manufactured by Maruzen Sekiyu KK), and polyvinyl phenol CST70, CST90, S-1P, S-2P (manufactured by Maruzen Sekiyu KK).

(4) The acid value of the alkali-soluble resin is suitably in the range of 40 to 200 mgKOH / g, and more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the alkali-soluble resin is 40 mgKOH / g or more, alkali development becomes easy, and on the other hand, a normal cured product pattern of 200 mgKOH / g or less is easily drawn, which is preferable.

重量 The weight average molecular weight of the alkali-soluble resin varies depending on the resin skeleton, but is preferably in the range of 1,500 to 150,000, more preferably 1,500 to 100,000. When the weight average molecular weight is 1,500 or more, tack-free performance is good, the moisture resistance of the coating film after exposure is good, film loss during development can be suppressed, and a decrease in resolution can be suppressed. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is good and the storage stability is excellent.

配合 The compounding amount of the alkali-soluble resin is, for example, 5 to 50% by mass based on the total solid content of the composition.

(Photoinitiator)
The curable resin composition according to the first to third aspects of the present invention can contain a photoreaction initiator. The photoreaction initiator may be any one that can cure the composition by light irradiation, and may be any one of a photopolymerization initiator that generates radicals by light irradiation and a photobase generator that generates a base by light irradiation. Is preferred. The photoreaction initiator may be a compound that generates both a radical and a base upon irradiation with light. Light irradiation refers to irradiation with ultraviolet light having a wavelength of 350 to 450 nm.

Examples of the photopolymerization initiator include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) -phenylphosphine oxide Bisacylphosphine oxides such as 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyl Monoacylphosphine oxides such as diphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide); 1-hydroxy-cyclohexylphenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propio) Benzyl) phenyl} -2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one and the like; hydroxyacetophenones; benzoin, benzyl, benzoin methyl ether, benzoin ethyl Benzoins such as ether, benzoin n-propyl ether, benzoin isopropyl ether and benzoin n-butyl ether; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4 ' Benzophenones such as -bisdiethylaminobenzophenone; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-di Chloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl ) -Butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl) -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone, etc. Acetophenones; thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone , 2 Anthraquinones such as -methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; ethyl-4 Benzoic acid esters such as -dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate and ethyl p-dimethylbenzoate; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O- Oxime esters such as benzoyl oxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); bis (η5 -2,4-cyclopentadiene 1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- ( Titanocenes such as 1-pyr-1-yl) ethyl) phenyl] titanium; and phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide and the like. One photopolymerization initiator may be used alone, or two or more photopolymerization initiators may be used in combination.

The photobase generator generates one or more basic substances that can function as a catalyst for a thermosetting reaction by changing the molecular structure by irradiation with light such as ultraviolet light or visible light, or by cleaving the molecule. Compound. Examples of the basic substance include a secondary amine and a tertiary amine.

Examples of photobase generators include α-aminoacetophenone compounds, oxime ester compounds, acyloxyimino compounds, N-formylated aromatic amino compounds, N-acylated aromatic amino compounds, nitrobenzyl carbamate compounds, and alkoxyoxybenzyl carbamates And the like. Of these, oxime ester compounds and α-aminoacetophenone compounds are preferable, and oxime ester compounds are more preferable. Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) is more preferred. As the α-aminoacetophenone compound, a compound having two or more nitrogen atoms is particularly preferable. One photobase generator may be used alone, or two or more photobase generators may be used in combination. In addition, examples of the photobase generator include quaternary ammonium salts.

As other photobase generators, WPBG-018 (trade name: 9-anthrylmethyl @ N, N'-diethylcarbamate) and WPBG-027 (trade name: (E) -1- [3-] manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (2-hydroxyphenyl) -2-propenoyl] piperidine), WPBG-082 (trade name: guanidinium 2- (3-benzoylphenyl) propionate), {WPBG-140 (trade name: 1- (anthratioquinoyl) -thylaquinone-yloxy-neoly-xylonyl-e-thylonxyl-thylonxyl-thylonxyl-thylon-xyl-thylon-xyl-thylon-x-yl-thylon-xyl-thylon-xyl- Can also be used.

Further, some of the above-mentioned photopolymerization initiators also function as photobase generators. As a photopolymerization initiator that also functions as a photobase generator, an oxime ester-based photopolymerization initiator and an α-aminoacetophenone-based photopolymerization initiator are preferable.

(4) The compounding amount of the photoreaction initiator is, for example, 0.01 to 30% by mass based on the total solid content of the composition.

(Curing accelerator)
The curable resin compositions of the first to third aspects of the present invention can contain a curing accelerator. Examples of the curing accelerator include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Imidazole derivatives such as (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzyl Examples include amine compounds such as amines, 4-methyl-N, N-dimethylbenzylamine and 4-dimethylaminopyridine; hydrazine compounds such as adipic dihydrazide and sebacic dihydrazide; and phosphorus compounds such as triphenylphosphine. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine / isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used. In addition, a metal-based hardening accelerator may be used, and examples thereof include an organic metal complex or an organic metal salt of a metal such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. And the like, an organic iron complex such as iron (III) acetylacetonate, an organic nickel complex such as nickel (II) acetylacetonate, and an organic manganese complex such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like. As the curing accelerator, a compound that also functions as an adhesion promoter is preferably used in combination with the curing accelerator. As the curing accelerator, one type can be used alone, or two or more types can be used in combination.

配合 The amount of the curing accelerator is, for example, 0.01 to 30% by mass based on the total solid content of the composition.

(Curing agent)
The curable resin compositions of the first to third aspects of the present invention can contain a curing agent. Examples of the curing agent include compounds having a phenolic hydroxyl group, polycarboxylic acids and acid anhydrides thereof, compounds having a cyanate ester group, compounds having a maleimide group, and alicyclic olefin polymers. As the curing agent, one type can be used alone, or two or more types can be used in combination.

Examples of the compound having a phenolic hydroxyl group include phenol novolak resin, alkylphenol novolak resin, bisphenol A novolak resin, dicyclopentadiene-type phenol resin, Xylok-type phenol resin, terpene-modified phenol resin, cresol / naphthol resin, polyvinylphenols, and phenol. Conventionally known resins such as a naphthol resin, a phenol resin having an α-naphthol skeleton, a cresol novolak resin having a triazine skeleton, a biphenylaralkyl-type phenol resin, and a zyloc-type phenol novolak resin can be used.
Among the compounds having a phenolic hydroxyl group, the hydroxyl equivalent is 100 g / eq. The above are preferred. When the hydroxyl equivalent is 100 g / eq. Examples of the compound having a phenolic hydroxyl group include a dicyclopentadiene skeleton phenol novolak resin (GDP series, manufactured by Gunei Chemical Co., Ltd.), a Xyloc phenol novolak resin (MEH-7800, manufactured by Meiwa Kasei Co., Ltd.), and a biphenylaralkyl type. Novolak resin (MEH-7851, manufactured by Meiwa Kasei Co., Ltd.), naphthol aralkyl type curing agent (SN series, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), cresol novolak resin containing a triazine skeleton (LA-3018-50P, manufactured by DIC), containing a triazine skeleton Phenol novolak resin (LA-705N, manufactured by DIC) and the like.

The compound having a cyanate ester group is preferably a compound having two or more cyanate ester groups (—OCN) in one molecule. As the compound having a cyanate ester group, any of conventionally known compounds can be used. Examples of the compound having a cyanate ester group include, for example, phenol novolak type cyanate ester resin, alkylphenol novolak type cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol S type Cyanate ester resins are exemplified. Further, a prepolymer partially triazined may be used.

Commercially available compounds having a cyanate ester group include a phenol novolak-type polyfunctional cyanate ester resin (PT30S, manufactured by Lonza Japan Co., Ltd.), and a prepolymer in which a part or all of bisphenol A dicyanate is triazine-modified into a trimer. (Lonza Japan, BA230S75), dicyclopentadiene structure-containing cyanate ester resin (Lonza Japan, DT-4000, DT-7000) and the like.

The compound having a maleimide group is a compound having a maleimide skeleton, and any of conventionally known compounds can be used. The compound having a maleimide group preferably has two or more maleimide skeletons, such as N, N'-1,3-phenylenedimaleimide, N, N'-1,4-phenylenedimaleimide, N, N'-4. 1,4-diphenylmethanebismaleimide, 1,2-bis (maleimide) ethane, 1,6-bismaleimide-hexane, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 2,2′-bis- [4- (4-maleimidophenoxy) phenyl] propane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, bis ( 3-ethyl-5-methyl-4-maleimidophenyl) methane, bisphenol A diphenylether bismaleimide, polyphenylmethanemale Bromide, and more preferably at least any one kind of diamine condensates with these oligomers and maleimide skeleton. The oligomer is an oligomer obtained by condensing a compound having a maleimide group which is a monomer among the above-described compounds having a maleimide group.

Commercially available compounds having a maleimide group include BMI-1000 (4,4'-diphenylmethane bismaleimide, manufactured by Daiwa Kasei Kogyo), BMI-2300 (phenylmethane bismaleimide, manufactured by Daiwa Kasei Kogyo), BMI- 3000 (m-phenylene bismaleimide, manufactured by Daiwa Kasei Kogyo), BMI-5100 (3,3'-dimethyl-5,5'-dimethyl-4,4'-diphenylmethane bismaleimide, manufactured by Daiwa Kasei Kogyo), BMI -7000 (4-methyl-1,3, -phenylenebismaleimide, manufactured by Daiwa Chemical Industry Co., Ltd.), BMI-TMH ((1,6-bismaleimide-2,2,4-trimethyl) hexane, manufactured by Daiwa Chemical Industry Co., Ltd.) ), MIR-3000 (biphenylaralkyl-type maleimide, manufactured by Nippon Kayaku Co., Ltd.).

硬化 The curable resin composition of the third aspect of the present invention may contain a compound having an active ester group as a curing agent. The compound having an active ester group is preferably a compound having two or more active ester groups in one molecule. The compound having an active ester group can be generally obtained by a condensation reaction between a carboxylic acid compound and a hydroxy compound. Among them, a compound having an active ester group obtained by using a phenol compound or a naphthol compound as the hydroxy compound is preferable. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolak and the like. Further, the compound having an active ester group may be a naphthalene diol alkyl / benzoic acid type.

Examples of commercially available compounds having an active ester group include cyclopentadiene-type diphenol compounds such as HPC8000-65T (manufactured by DIC), HPC8100-65T (manufactured by DIC), and HPC8150-65T (manufactured by DIC). No.

配合 The amount of the curing agent is, for example, 0.01 to 30% by mass based on the total solid content of the composition.

(Thermoplastic resin)
The curable resin compositions according to the first to third aspects of the present invention may further contain a thermoplastic resin in order to improve the mechanical strength of the obtained cured film. Preferably, the thermoplastic resin is soluble in a solvent. When soluble in a solvent, the flexibility is improved when a dry film is formed, and the generation of cracks and powder fall can be suppressed. As the thermoplastic resin, a thermoplastic polyhydroxy polyether resin, a phenoxy resin which is a condensate of epichlorohydrin and various bifunctional phenol compounds, or various acid anhydrides or acid chlorides in which the hydroxyl group of the hydroxy ether portion present in the skeleton is used. Phenoxy resin, polyvinyl acetal resin, polyamide resin, polyamide imide resin, block copolymer, rubber particles, etc. The thermoplastic resins can be used alone or in combination of two or more.

配合 The blending amount of the thermoplastic resin is, for example, 0.01 to 10% by mass based on the total solid content of the composition.

(Flame retardants)
The curable resin compositions of the first to third aspects of the present invention can contain a flame retardant. Known and commonly used flame retardants can be used as the flame retardant, and include phosphoric acid esters and condensed phosphoric acid esters, phosphorus-containing (meth) acrylates, phosphorus-containing compounds having a phenolic hydroxyl group, cyclic phosphazene compounds, phosphazene oligomers, and phosphines. Layered compounds such as phosphorus-containing compounds such as acid metal salts, antimony compounds such as antimony trioxide and antimony pentoxide, halides such as pentabromodiphenyl ether and octabromodiphenyl ether, and metal hydroxides such as aluminum hydroxide and magnesium hydroxide. Hydroxide. Among these, a phosphorus-containing compound is preferable, and a metal phosphinate is more preferable. One type of flame retardant may be used alone, or two or more types may be used in combination.

配合 The compounding amount of the flame retardant is, for example, 0.01 to 10% by mass based on the total solid content of the composition.

(Colorant)
The curable resin compositions of the first to third aspects of the present invention may contain a colorant. As the coloring agent, known coloring agents such as red, blue, green, yellow, black, and white can be used, and any of pigments, dyes, and pigments may be used. However, it is preferable not to contain halogen from the viewpoint of reducing the environmental load and affecting the human body. The coloring agents can be used alone or in combination of two or more.

The compounding amount of the coloring agent is, for example, 0.01 to 10% by mass based on the total solid content of the composition.
In the curable resin composition of the first aspect of the present invention, since the coated perovskite type compound has a relatively large refractive index, in the case of an alkali development type, it contains an ultraviolet absorber such as carbon black. Is preferred. By including an ultraviolet absorber such as carbon black, the resolution can be easily controlled, and the resolution can be improved.

(Organic solvent)
The curable resin compositions of the first to third aspects of the present invention can contain an organic solvent for the purpose of preparing the composition, adjusting the viscosity when applying the composition to a substrate or a carrier film, and the like. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, and propylene glycol monomethyl ether. Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate and tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbine Tall acetate, propylene glycol monomethyl ether acetate, zip Propylene glycol monomethyl ether acetate, esters such as propylene carbonate; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, and petroleum solvents such as solvent naphtha, organic solvents conventionally known can be used. These organic solvents can be used alone or in combination of two or more.

(Other optional components)
Further, the curable resin compositions of the first to third aspects of the present invention may contain other additives commonly used in the field of electronic materials. Other additives include thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, antistatic agents, antioxidants, antioxidants, antibacterial and antifungal agents, defoamers, leveling agents, Viscous agent, adhesion promoter, thixotropy promoter, photoinitiator, sensitizer, organic filler, elastomer, release agent, surface treating agent, dispersant, dispersant, surface modifier, stabilizer, Phosphors and the like.

In addition, the curable resin composition of the first aspect of the present invention contains a known and commonly used inorganic filler other than the coated perovskite compound as long as the effect of the first aspect of the present invention is not impaired. Is also good. Examples of such inorganic fillers include, for example, perovskite compounds other than the coated perovskite compound, silica, Neuburg silicate, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, and synthetic mica. Examples include inorganic fillers such as mica, aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, and zinc white.

Further, the curable resin composition of the second aspect of the present invention may contain a known and commonly used inorganic filler other than the coated silica particles as long as the effect of the second aspect of the present invention is not impaired. Good. Examples of such inorganic fillers include, for example, silica other than the coated silica particles, Neuburg silica, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, and aluminum hydroxide. And inorganic fillers such as barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate and zinc white.

Further, the curable resin composition of the third aspect of the present invention contains a known and commonly used filler other than the coated high thermal conductivity filler, as long as the effect of the third aspect of the present invention is not impaired. You may. As such a filler, for example, a filler having a high thermal conductivity other than the coated high thermal conductivity filler, silica, Neuburg silica, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, Examples include inorganic fillers such as synthetic mica, barium sulfate, barium titanate, non-fibrous glass, hydrotalcite, mineral wool, and calcium silicate.

The curable resin composition of the first to third aspects of the present invention is not particularly limited, and examples thereof include a thermosetting resin composition, a photocurable resin composition, a photocurable thermosetting resin composition, and a photosensitive resin. Any of the thermosetting resin compositions may be used. Further, an alkali developing type may be used, and a negative type or a positive type may be used. Specific examples include a thermosetting resin composition, a photocurable thermosetting resin composition, a photocurable thermosetting resin composition containing a photopolymerization initiator, and a photocurable thermosetting resin containing a photobase generator. Curable resin composition, negative photocurable thermosetting resin composition and positive photosensitive thermosetting resin composition, alkali-developed photocurable thermosetting resin composition, solvent-developed photocurable thermosetting Examples thereof include, but are not limited to, a water-soluble resin composition, a swellable peelable thermosetting resin composition, and a dissolution peelable thermosetting resin composition.

任意 As the optional components contained in the curable resin compositions of the first to third aspects of the present invention, known and commonly used components may be selected in accordance with curability and use.

For example, when the curable resin composition according to the first to third aspects of the present invention is a thermosetting resin composition (containing no photopolymerization initiator), it contains a thermosetting resin. Further, it is preferable to contain a curing accelerator. It is preferable to contain a curing agent. The compounding amount of the thermosetting resin is preferably 1 to 50% by mass based on the total solid content of the composition. The compounding amount of the curing accelerator is preferably 0.01 to 30% by mass based on the total solid content of the composition. The compounding amount of the curing agent is preferably 0.01 to 30% by mass based on the total solid content of the composition.

In the case where the curable resin composition according to the first to third aspects of the present invention is a photocurable thermosetting resin composition, it contains a photocurable resin, a thermosetting resin, and a photoreaction initiator. In the case of an alkali developing type, the photocurable resin may be an alkali-soluble resin, and may further contain an alkali-soluble resin. Further, it is preferable to contain a curing accelerator. The compounding amount of the alkali-soluble resin is preferably 5 to 50% by mass based on the total solid content of the composition. The compounding amount of the thermosetting resin is preferably 1 to 50% by mass based on the total solid content of the composition. The compounding amount of the photocurable resin (excluding the photocurable alkali-soluble resin) is preferably 1 to 50% by mass based on the total solid content of the composition. The compounding amount of the photoreaction initiator is preferably 0.01 to 30% by mass based on the total solid content of the composition. The compounding amount of the curing accelerator is preferably 0.01 to 30% by mass based on the total solid content of the composition.

硬化 The curable resin compositions of the first to third aspects of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-pack or two-pack or more.

The dry film of the first, second or third embodiment of the present invention is provided on a carrier film, respectively, with the curable resin composition of the first, second or third embodiment of the present invention (hereinafter referred to as “the present invention”). (Also abbreviated as "curable resin composition of the invention") and dried. When forming a dry film, first, after adjusting the curable resin composition of the present invention to an appropriate viscosity by diluting with the organic solvent, a comma coater, blade coater, lip coater, rod coater, squeeze coater , A reverse coater, a transfer roll coater, a gravure coater, a spray coater, etc., to apply a uniform thickness on the carrier film. Thereafter, the applied composition is usually dried at a temperature of 40 to 130 ° C. for 1 to 30 minutes to form a resin layer. The thickness of the applied film is not particularly limited, but is generally appropriately selected in a range of 3 to 150 μm, preferably 5 to 60 μm after drying.

プラスチック As the carrier film, a plastic film is used, and for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used. The thickness of the carrier film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 μm. More preferably, it is in the range of 15 to 130 μm.

After forming a resin layer made of the curable resin composition of the present invention on a carrier film, for the purpose of preventing dust from adhering to the surface of the resin layer, further, a cover that can be peeled off on the surface of the resin layer. It is preferable to laminate films. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, surface-treated paper, or the like can be used. The cover film only needs to have a smaller adhesive strength between the resin layer and the carrier film when the cover film is peeled off.

In the present invention, a resin layer may be formed by applying and drying the curable resin composition of the present invention on the cover film, and a carrier film may be laminated on the surface of the resin layer. That is, any of a carrier film and a cover film may be used as a film on which the curable resin composition of the present invention is applied when producing a dry film in the present invention.

プリント As a method for producing a printed wiring board using the curable resin composition of the present invention, a conventionally known method may be used. Taking the case of a photocurable thermosetting resin composition of an alkali development type as an example, for example, the curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using the organic solvent, and the substrate After being applied on the top by a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, a curtain coating method, a spin coating method, or the like, the composition is contained in the composition at a temperature of 60 to 100 ° C. The tack-free resin layer is formed by volatilizing drying (temporary drying) of the organic solvent. In the case of a dry film, a resin layer is formed on a substrate by laminating the resin layer on the substrate such that the resin layer is in contact with the substrate, and then peeling off the carrier film.

As the substrate, in addition to a printed wiring board or a flexible printed wiring board which has been previously formed with a circuit such as copper, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, All grades (FR-4, etc.) copper-clad laminates made of synthetic fiber epoxy, fluorocarbon resin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc. And others, a metal substrate, a polyimide film, a PET film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, a wafer plate, and the like. The circuit may be pre-treated. For example, the circuit may be pre-treated with GliCAP manufactured by Shikoku Chemicals, New Organic AP (Adhesion Promoter) manufactured by Mec, Nova Bond manufactured by Atotech Japan, or the like. The adhesion to a cured film such as a resist may be improved, or a pre-treatment with a rust inhibitor may be performed.

The volatile drying performed after applying the curable resin composition of the present invention may be performed by a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, or the like (using a device equipped with a heat source of an air heating system using steam to dry the inside of the dryer). (A method in which hot air is brought into countercurrent contact or a method in which hot air is blown onto a substrate from a nozzle).

After a resin layer is formed on a printed wiring board, it is selectively exposed to active energy rays through a photomask on which a predetermined pattern is formed, and an unexposed portion is diluted with a dilute alkaline aqueous solution (for example, a 0.3 to 3 mass% aqueous sodium carbonate solution). ) To form a cured product pattern. Further, the cured product is irradiated with active energy rays and then heated and cured (for example, at 100 to 220 ° C.), or heated and cured with active energy rays, or finally cured (final curing) only by heat curing to achieve close contact. A cured film with excellent properties such as properties and hardness is formed.

The exposure machine used for the active energy ray irradiation may be any device equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., and irradiating ultraviolet rays in a range of 350 to 450 nm. Furthermore, a projection exposure apparatus using a projection lens or a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser based on CAD data from a computer) as a maskless exposure that is not in contact with the substrate can also be used. The lamp light source or laser light source of the direct drawing machine may have a maximum wavelength in the range of 350 to 450 nm. The exposure amount for image formation varies depending on the film thickness and the like, but can be generally in the range of 10 to 1000 mJ / cm ² , preferably 20 to 800 mJ / cm ² .

As the developing method, a dipping method, a shower method, a spray method, a brush method, or the like can be used. As a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Aqueous alkali solutions such as ammonia and amines can be used.

The curable resin composition of the first aspect of the present invention is preferably used for forming a cured film on an electronic component, particularly, for forming a cured film on a printed wiring board, and more preferably, It is used for forming a permanent film, and more preferably, for forming a solder resist, an interlayer insulating layer, a coverlay, and a sealing material. Further, it is suitable for forming a printed wiring board requiring a high degree of reliability, for example, a package substrate, particularly a permanent film (particularly a solder resist) for FC-BGA. Further, the curable resin composition of the first aspect of the present invention can be suitably used for a printed wiring board having a wiring pattern even if the surface roughness of the circuit is small, for example, a high-frequency printed wiring board. For example, even when the surface roughness Ra is 0.05 μm or less, particularly 0.03 μm or less, it can be suitably used. It can also be suitably used when a cured film is formed on a low-polarity base material, for example, a base material containing an active ester. Further, it is suitably used for forming a cured film on a wafer or a glass substrate without roughening. Further, the curable resin composition of the first aspect of the present invention is also suitable for forming a cured film on a substrate having a low transmission loss, for example, a substrate having a dielectric loss tangent at a frequency of 10 GHz of 0.01 or less. used. The electronic component may be a use other than the printed wiring board, for example, a passive component such as an inductor.

硬化 The cured product obtained by curing the curable resin composition of the first aspect of the present invention preferably has a dielectric constant of 5 or more, more preferably 10 or more. Further, the dielectric loss tangent is preferably 0.02 or less.

The curable resin composition of the second aspect of the present invention is preferably used for forming a cured film on an electronic component, particularly, for forming a cured film on a printed wiring board, and more preferably, It is used for forming a permanent film, and more preferably, for forming a solder resist, an interlayer insulating layer, a coverlay, and a sealing material. Further, it is suitable for forming a printed wiring board requiring a high degree of reliability, for example, a package substrate, particularly a permanent film (particularly a solder resist) for FC-BGA. Further, the curable resin composition of the second aspect of the present invention can be suitably used for a printed wiring board having a wiring pattern even if the surface roughness of the circuit is small, for example, a printed wiring board for high frequency. For example, even when the surface roughness Ra is 0.05 μm or less, particularly 0.03 μm or less, it can be suitably used. Further, it can also be suitably used when a cured film is formed on a low-polarity substrate, for example, a substrate containing active ester. Further, it is suitably used for forming a cured film on a wafer or a glass substrate without roughening. Further, the curable resin composition of the second aspect of the present invention is also suitably used for forming a cured film on a substrate having a small transmission loss, for example, a substrate having a dielectric loss tangent at a frequency of 10 GHz of 0.01 or less. You. Such a substrate having a low dielectric loss tangent can be manufactured using, for example, an interlayer insulating film (ABF) manufactured by Ajinomoto Co. The electronic component may be a use other than the printed wiring board, for example, a passive component such as an inductor.

The laminated structure according to the second aspect of the present invention is a structure including a resin cured layer (A) and a resin cured layer (B) or a substrate (C) in contact with the resin cured layer (A), The resin cured layer (A) is a cured product having a positive zeta potential obtained from the curable resin composition of the second aspect of the present invention or the resin layer of the dry film of the second aspect of the present invention, The zeta potential of the cured resin layer (B) or the substrate (C) is negative.

As described above, in the second embodiment of the present invention, by performing surface treatment on the titanium oxide particles so as to increase the positive charge, it is possible to suppress a decrease in adhesion, and thus, excellent adhesion between layers is obtained. It is possible to manufacture a laminated structure.

硬化 The curable resin composition of the second aspect of the present invention can be suitably used as a composition for forming a semiconductor package constituent material.

厚 The thicknesses of the cured resin layers (A) and (B) and the substrate (C) in the laminated structure of the second embodiment of the present invention are not particularly limited.

The combination of the resin cured layer (A) and the resin cured layer (B) is not particularly limited. For example, the solder resist 13, the interlayer insulating material 11, and the solder resist included in the laminated structure schematically shown in FIG. 13 and an underfill 16, and a combination of a solder resist 13 and a sealing material 17. In the above combination, any of the resin cured layers (A) and (B) may be used, but the resin cured layer (A) is preferably a solder resist. Here, any one of the interlayer insulating material 11, the solder resist 13, the underfill 16, and the encapsulant 17 is filled with the coated titanium oxide particles having a positive zeta potential, thereby forming a resin cured layer in contact with these. Has good adhesion.

Further, the combination of the resin cured layer (A) and the substrate (C) is not particularly limited. For example, a solder resist (A) 13 and an interlayer insulating material (such as those included in a laminated structure schematically shown in FIG. 1) are used. C) 11, the solder resist (A) 13 and the semiconductor wafer (C) 15, the underfill (A) 16 and the semiconductor wafer (C) 15, and the sealing material (A) 17 and the semiconductor wafer (C) 15 in combination. Can be

Since the cured resin layer made of the curable resin composition of the second aspect of the present invention contains the coated titanium oxide particles, the zeta potential becomes positive, and the zeta potential of the other cured resin layers and the substrate is negative. It has excellent adhesion to other cured resin layers and substrates.

硬化 The cured product obtained by curing the curable resin composition of the second aspect of the present invention preferably has a dielectric constant of 5 or more, more preferably 10 or more. Further, the dielectric loss tangent is preferably 0.02 or less.

The curable resin composition of the third aspect of the present invention is preferably used for forming a cured film on an electronic component, particularly for forming a cured film on a printed wiring board, and more preferably, It is used for forming a permanent film, and more preferably, for forming a solder resist, an interlayer insulating layer, a coverlay, and a sealing material. In addition, since a cured product having high thermal conductivity can be formed, it can be suitably used in an environment exposed to high temperatures, for example, for forming a cured film of a printed wiring board for a vehicle. Further, it is suitable for forming a printed wiring board requiring a high degree of reliability, for example, a package substrate, particularly a permanent film (particularly a solder resist) for FC-BGA. Further, the curable resin composition of the third aspect of the present invention can be suitably used for a printed wiring board having a wiring pattern even if the surface roughness of the circuit is small, for example, a high-frequency printed wiring board. For example, even when the surface roughness Ra is 0.05 μm or less, particularly 0.03 μm or less, it can be suitably used. Further, it can also be suitably used when a cured film is formed on a low-polarity substrate, for example, a substrate containing active ester. Further, it is suitably used for forming a cured film on a wafer or a glass substrate without roughening. Further, the curable resin composition of the third aspect of the present invention is also suitably used for forming a cured film on a substrate having a small transmission loss, for example, a substrate having a dielectric loss tangent at a frequency of 10 GHz of 0.01 or less. You. Such a substrate having a low dielectric loss tangent can be manufactured using, for example, an interlayer insulating film (ABF) manufactured by Ajinomoto Co., Inc. The electronic component may be a use other than the printed wiring board, for example, a passive component such as an inductor.

硬化 A cured product obtained by curing the curable resin composition of the third aspect of the present invention preferably has a thermal conductivity of 1 W / (m · K) or more.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. In the following, “parts” and “%” are all based on mass unless otherwise specified.

[Synthesis of alkali-soluble resin A-1]
A flask equipped with a condenser and a stirrer was charged with 456 parts of bisphenol A, 228 parts of water and 649 parts of 37% formalin, kept at a temperature of 40 ° C. or lower, and added 228 parts of a 25% aqueous sodium hydroxide solution. Reaction was performed at 10 ° C. for 10 hours. After completion of the reaction, the mixture was cooled to 40 ° C., and neutralized to pH 4 with a 37.5% phosphoric acid aqueous solution while maintaining the temperature at 40 ° C. or lower. Thereafter, the mixture was allowed to stand, and the aqueous layer was separated. After the separation, 300 parts of methyl isobutyl ketone was added and uniformly dissolved, followed by washing three times with 500 parts of distilled water, and removing water, solvent and the like under a reduced pressure at a temperature of 50 ° C. or lower. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1230 parts of a methanol solution of the polymethylol compound.
A part of the obtained methanol solution of the polymethylol compound was dried in a vacuum dryer at room temperature, and the solid content was 55.2%.
In a flask equipped with a condenser and a stirrer, 500 parts of a methanol solution of the obtained polymethylol compound and 440 parts of 2,6-xylenol were charged and uniformly dissolved at 50 ° C. After uniform dissolution, methanol was removed under reduced pressure at a temperature of 50 ° C. or less. Thereafter, 8 parts of oxalic acid was added, and the mixture was reacted at 100 ° C. for 10 hours. After the reaction was completed, the distillate was removed at 180 ° C. under a reduced pressure of 50 mmHg to obtain 550 parts of novolak resin A.
In an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a stirring device, 130 parts of novolak resin A, 2.6 parts of a 50% aqueous sodium hydroxide solution, and toluene / methyl isobutyl ketone (mass ratio = 2/1) 100 parts were charged, the inside of the system was replaced with nitrogen while stirring, then the temperature was increased by heating, and 60 parts of propylene oxide was gradually introduced at 150 ° C. and 8 kg / cm ² to cause a reaction. The reaction was continued for about 4 hours until the gauge pressure became 0.0 kg / cm ^2, and then cooled to room temperature. To this reaction solution, 3.3 parts of a 36% hydrochloric acid aqueous solution was added and mixed to neutralize sodium hydroxide. The neutralized reaction product was diluted with toluene, washed three times with water, and the solvent was removed with an evaporator to give a hydroxyl value of 189 g / eq. Of novolak resin A was obtained. This was one in which propylene oxide was added on average to 1 mole per equivalent of phenolic hydroxyl group.
189 parts of the propylene oxide adduct of the obtained novolak resin A, 36 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 part of hydroquinone monomethyl ether, and 140 parts of toluene were stirred with a stirrer, a thermometer, and an air blowing tube. The mixture was stirred while blowing in air, heated to 115 ° C., and allowed to react for another 4 hours while distilling off water formed by the reaction as an azeotrope with toluene. Cool. The obtained reaction solution was washed with a 5% aqueous NaCl solution, and toluene was removed by distillation under reduced pressure. Diethylene glycol monoethyl ether acetate was added to obtain an acrylate resin solution having a solid content of 67%.
Next, 322 parts of the obtained acrylate resin solution, 0.1 part of hydroquinone monomethyl ether, and 0.3 part of triphenylphosphine were charged into a four-necked flask equipped with a stirrer and a reflux condenser. , 60 parts of tetrahydrophthalic anhydride was added, and the mixture was reacted for 4 hours. After cooling, the mixture was taken out. The photosensitive carboxyl group-containing resin solution thus obtained had a solid content of 70% and an acid value of the solid content of 81 mgKOH / g. Hereinafter, the solution of the carboxyl group-containing photosensitive resin is referred to as a resin solution A-1.

<First embodiment>
[Surface treatment of perovskite compound]
(Barium titanate coated with a hydrated oxide of silicon formulated in Example 1-1)
A 50 g water slurry of barium titanate (BT-03 manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter 0.3 μm, specific gravity 6.02) was heated to 70 ° C., and then a 10% aqueous sodium silicate solution was added to barium titanate. And 4% in terms of barium titanate. Hydrochloric acid was added to this slurry to adjust the pH to 4, aged for 30 minutes, and further adjusted to pH 7 ± 1 with hydrochloric acid. The slurry was filtered and washed with a filter press, and dried in vacuo to obtain a solid silica particle coated with a silicon hydrated oxide.

(Barium titanate coated with a hydrated aluminum oxide compounded in Example 1-2)
A 50 g aqueous slurry of barium titanate (BT-03, manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter 0.3 μm, specific gravity 6.02) was heated to 70 ° C., and then a 20% aqueous sodium aluminate (NaAlO ₂ ) solution was treated with titanic acid. 7-8% was added to barium in terms of alumina (Al ₂ O ₃ ). Thereafter, a 20% aqueous sodium hydroxide solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered and washed with a filter press, and dried under vacuum to obtain a solid of barium titanate coated with aluminum hydrated oxide.

(Barium titanate coated with hydrated oxide of aluminum and then coated with hydrated oxide of aluminum, blended in Example 1-3)
A 50 g water slurry of barium titanate (BT-03 manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter 0.3 μm, specific gravity 6.02) was heated to 70 ° C., and then a 10% aqueous sodium silicate solution was added to barium titanate. And 4% in terms of barium titanate. Hydrochloric acid was added to the slurry to adjust the pH to 4 and aged for 30 minutes. Further, while maintaining the pH at 5 ± 1 with hydrochloric acid, a 20% aqueous solution of sodium aluminate (NaAlO ₂ ) was added to barium titanate with alumina. 7-8% in terms of (Al ₂ O ₃ ). Thereafter, a 20% aqueous sodium hydroxide solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered and washed with a filter press, and dried under vacuum to obtain a barium titanate solid coated with a hydrated oxide of silicon and a hydrated oxide of aluminum.

(Barium titanate coated with aluminum hydrated oxide, coated with aluminum hydrated oxide, and surface-treated with methacrylsilane blended in Example 1-4)
50 g of barium titanate coated with a hydrated oxide of aluminum and then coated with a hydrated oxide of aluminum, 48 g of PMA as a solvent, and a silane coupling agent having a methacryl group (Shin-Etsu Chemical Co., Ltd.) And 2 g of KBM-503), which was filtered, washed with water, and dried under vacuum to obtain a barium titanate solid surface-treated with methacrylsilane.

(Barium titanate formulated in Examples 1-5 and 1-10, coated with a hydrated oxide of silicon, then coated with a hydrated oxide of aluminum, and surface-treated with phenylaminosilane)
50 g of barium titanate coated with a hydrated oxide of aluminum and then coated with a hydrated oxide of aluminum, PMA as a solvent, and a silane coupling agent having a phenylamino group (Shin-Etsu Chemical Co., Ltd.) And 2 g of KBM-573) (manufactured by K.K.), filtered, washed with water, and vacuum-dried to obtain a barium titanate surface-treated with phenylaminosilane.

(Calcium titanate formulated in Example 1-6, coated with a hydrated oxide of silicon, then coated with a hydrated oxide of aluminum, and surface-treated with methacrylsilane)
Surface-treated barium titanate blended in Example 1-4 except that barium titanate was changed to calcium titanate (CT-03, Sakai Chemical Industry Co., Ltd., average particle diameter 0.3 μm, specific gravity 3.98) It was manufactured by the same method as described above.

(Strontium titanate coated with hydrated oxide of silicon, then coated with hydrated oxide of aluminum, and surface-treated with methacrylsilane, formulated in Example 1-7)
Surface-treated barium titanate compounded in Example 1-4, except that barium titanate was changed to strontium titanate (ST-03, manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter 0.3 μm, specific gravity 5.13). It was manufactured by the same method as described above.

(Calculated in Examples 1-8, calcium zirconate coated with a hydrated oxide of silicon and then coated with a hydrated oxide of aluminum and surface-treated with methacrylsilane)
Surface-treated barium titanate compounded in Example 1-4, except that barium titanate was changed to calcium zirconate (CZ-03 manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter 0.3 μm, specific gravity 5.11). It was manufactured by the same method as described above.

(Strontium zirconate zirconate coated with hydrated oxide of aluminum, then coated with hydrated oxide of aluminum, and surface-treated with methacrylsilane blended in Example 1-9)
Surface-treated barium titanate compounded in Example 1-4 except that barium titanate was changed to strontium zirconate (SZ-03 manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter 0.3 μm, specific gravity 5.46) It was manufactured by the same method as described above.

(Barium titanate surface-treated with methacrylsilane blended in Comparative Example 1-2)
50 g of barium titanate (BT-03 manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter 0.3 μm, specific gravity 6.02), 48 g of PMA as a solvent, and a silane coupling agent having a methacryl group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) 2g) was uniformly dispersed, and filtered, washed with water, and vacuum-dried to obtain a solid barium titanate surface-treated with methacrylsilane.

[Examples 1-1 to 1-10, Comparative Examples 1-1 and 1-2]
Various components shown in the following Tables 1 to 3 are blended in the proportions (parts by mass) shown in Tables 1 to 3 and diluted with an organic solvent (propylene glycol monomethyl ether acetate (PMA)) to a viscosity that can be dispersed in a bead mill. After pre-mixing with a stirrer, the mixture was kneaded with a bead mill to disperse the curable resin composition. The obtained dispersion was passed through a filter having an opening of 10 μm to obtain a curable resin composition.

<Dispersibility>
For the curable resin compositions of the respective examples and comparative examples, the degree of dispersion was confirmed by using a grind gauge having a width of 90 mm, a length of 240 mm, and a maximum depth of 50 μm according to JIS K5101 and JIS K5600. As a viewpoint of the degree of dispersion, a section in which five or more grains were confirmed was confirmed.
：: 10 μm or less
Δ: More than 10 μm and 25 μm or less
×: Over 25 μm

<Preparation of dry film>
The curable resin composition obtained as described above was diluted by adding 300 g of methyl ethyl ketone and stirred for 15 minutes with a stirrer to obtain a coating liquid. The coating solution is applied on a 38 μm-thick polyethylene terephthalate film (PET film, Emblet PTH-25 manufactured by Unitika Ltd.) having an arithmetic surface roughness Ra of 150 nm, usually at 80 to 100 ° C. (Examples 1-1 to 100). 1-9 and Comparative Examples 1-1 and 1-2 were dried at a temperature of 80 ° C. for 15 minutes, and Example 1-10 was dried at a temperature of 100 ° C. for 15 minutes to form a resin layer having a thickness of 20 μm. Next, a 18 μm-thick polypropylene film (cover film, OPP-FOA manufactured by Futamura Co., Ltd.) was laminated on the resin layer to produce a dry film.

<Preparation of cured film>
The polyethylene film is peeled from the dry film obtained as described above on the glossy surface of the electrolytic copper foil GTS-MP-18 μm (made by Furukawa Electric Co., Ltd.), and the resin layer of the dry film is coated on the copper foil surface side. Lamination followed by Examples 1-1 to 1-9 and Comparative Examples 1-1 and 1-2 using a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho) with a degree of pressure of 0.8 MPa and 100 MPa. The laminate was heated and laminated at a temperature of 1 ° C. for 1 minute under a vacuum of 133.3 Pa, thereby bringing the copper foil and the resin layer into close contact with each other. In Example 1-10, heat lamination was performed under the conditions of 0.5 MPa, 100 ° C., 1 minute, and a degree of vacuum: 133.3 Pa, so that the copper foil and the resin layer were adhered to each other.
Next, in Examples 1-1 to 1-9 and Comparative Examples 1-1 and 1-2, exposure was performed from above the dry film (exposure amount: 400 to 400 mm) using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp). After 600 mJ / cm ² ), the polyethylene terephthalate film was peeled from the dry film to expose the resin layer. Thereafter, development was performed using a 1% by weight aqueous solution of Na ₂ CO _{3 at} 30 ° C. under a spray pressure of 0.2 MPa for 60 seconds to form a resin layer having a predetermined resist pattern. Subsequently, after irradiating the resin layer with an exposure amount of 1 J / cm ^{2 in} a UV conveyor furnace equipped with a high-pressure mercury lamp, the resin layer was completely cured by heating at 170 ° C. for 60 minutes to produce a cured film.
In Example 1-10, after laminating the dry film, the PET film was peeled off, and the resin layer was completely cured at 190 ° C. for 60 minutes.

<Dielectric constant>
A dry film prepared in the same manner as in the above <Preparation of dry film> except that the thickness of the resin layer was changed to other than 40 μm, was laminated on a glossy surface of electrolytic copper foil GTS-MP-18 μm (Furukawa Electric Co., Ltd.). Then, the resin layer was flattened and completely cured under the conditions described in the above <Preparation of cured film>. Thereafter, the cured product was peeled from the copper foil to obtain a cured product having a thickness of 30 μm.
The cured product was cut into a length of 80 mm and a width of 2 mm, and measured at a temperature of 22 ° C. and a frequency of 1 GHz by a perturbation method cavity resonator using a network analyzer 8510C manufactured by Keysight Corporation and software for calculating complex relative permittivity CAMA-S manufactured by KEAD Corporation. The dielectric constant was measured.
〇: relative permittivity 5 or more ×: relative permittivity less than 5 (dielectric tangent)
〇: dielectric loss tangent value 0.02 or less △: dielectric loss tangent value more than 0.02, 0.025 or less ×: dielectric loss tangent value more than 0.025

<Resolution>
The dry films of Examples 1-1 to 1-9 and Comparative Examples 1-1 and 1-2 obtained in the above <Preparation of dry film> were heat-laminated using a vacuum laminator to obtain a resin of a photosensitive resin composition. An evaluation substrate having a layer was obtained. The substrate was exposed to a pattern of L / S = 50 μm / 50 μm at an optimal exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and the PET film was peeled off. Thereafter, using a 1% by mass aqueous solution of sodium carbonate at 30 ° C., development was performed for 60 seconds under the condition of a spray thickness of 0.2 MPa to obtain a resist pattern.
〇: A good pattern was formed.
Δ: Chipping was confirmed.
X: Line formation was impossible.

<Adhesion with EMC (mold resin)>
A circular mold (2.523 mm in diameter, 3.00 mm in height) was molded on the cured film without plasma treatment obtained in the above <Preparation of cured film> using a mold material (UV8710U manufactured by Panasonic). The mold material was cured by heating at 175 ° C. for 4 hours. Then, a shear was given to the mold material provided on the surface of the cured film, and the peel strength between the cured film and the mold material was measured.
〇: 150 N or more △: 100 N or more and less than 150 N ×: less than 100 N

<Adhesion with Low Df material>
The curable resin compositions of Examples and Comparative Examples were coated on a low transmission loss interlayer material having a dielectric loss tangent of about 0.004 at 10 GHz and cured under the conditions described in the above <Preparation of cured film>. A sample was prepared. Based on JIS K5400, 100 crosscuts of 1 mm square (10 × 10) are made by a cross cutter to reach the interlayer material, and a cellophane tape is completely adhered to it, separated, and several hundred out of 100 are closely adhered. Was confirmed.
〇: 96 or more / 100
Δ: 51 to 95/100
×: 50 or less / 100

<Adhesion to copper after HAST>
As a pretreatment, CZ-8401 manufactured by MEC Co., Ltd. is sprayed as a pretreatment on the glossy surface of the electrolytic copper foil GTS-MP-18 μm (manufactured by Furukawa Electric Co., Ltd.), and then a roughening treatment is performed by AP-3004 to obtain a surface roughness Ra of 0. A low-profile copper foil of 0.04 μm was obtained.
A dry film having a resin layer thickness of 20 μm prepared in each of Examples and Comparative Examples was laminated on the treated surface, and cured under the above-described conditions for forming a cured film to obtain a sample in which an insulating layer was formed.
The insulating layer of this sample and an FR-4 (glass epoxy) substrate were bonded with an adhesive (AR-S30 manufactured by Nichiban). This bonded body was cut into 100 mm × 15 mm, and cut into copper foil at intervals of 10 mm.
After the initial value of this sample and the HAST test at 130 ° C. and 85% RH for 100 hours, the peel strength of both samples was measured by Autograph AG-X manufactured by Shimadzu Corporation based on JIS C6481.
The higher the peel strength, the better the adhesion, and the lower the rate of decrease in adhesion before and after the HAST test, the better.
(Before HAST-After HAST) / Before HAST × 100 (%)
●: Adhesion reduction rate less than 35% ◎: Adhesion reduction rate from 35% to less than 40% Δ: Adhesion reduction rate from 40% to less than 55% Δ: Adhesion reduction rate from 55% to less than 65% ×: Adhesion reduction Rate 65% or more

* 1-1: Carboxyl group-containing photosensitive resin A-1 synthesized above (carboxylic acid equivalent 654 g / eq)
* 1-2: Unidic EQG-1170 (alicyclic UV-curable amide imide resin) manufactured by DIC (carboxylic acid equivalent 962 g / eq)
* 1-3: Nippon Steel Chemical's ESN-475V (naphthalene type epoxy resin, epoxy equivalent: 340 g / eq)
* 1-4: Nippon Kayaku 830-S (bisphenol F type epoxy resin, epoxy equivalent: 170 g / eq)
* 1-5: PETG (polyfunctional aliphatic epoxy resin, epoxy equivalent: 92 g / eq) manufactured by Showa Denko KK
* 1-6: Primaset PT-30 manufactured by Lonza Japan (novolak type cyanate resin, cyanate equivalent: 124 g / eq)
* 1-7: YX7200B35 (phenoxy type) manufactured by Mitsubishi Chemical Corporation
* 1-8: DMAP (dimethylaminopyridine)
* 1-9: Dicyandiamide * 1-10: Melamine * 1-11: OP-935 manufactured by Clariant Chemicals (metal phosphinate)
* 1-12: Carbon black manufactured by Tokushiki * 1-13: Omnirad TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by IGM
* 1-14: A-DCP (tricyclodecane dimethanol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.
* 1-15: Barium titanate coated with hydrated oxide of silicon prepared above * 1-16: Barium titanate coated with hydrated oxide of aluminum prepared above * 1-17 : Silica particles prepared above, coated with hydrated oxide of silicon and then coated with hydrated oxide of aluminum * 1-18: After coated with hydrated oxide of silicon, prepared above Barium titanate coated with hydrated aluminum oxide and surface-treated with methacrylsilane * 1-19: Prepared above with hydrated oxide of aluminum after being coated with hydrated oxide of silicon Coated and surface treated with phenylaminosilane barium titanate * 1-20: coated with hydrated oxide of silicon, then coated with hydrated oxide of aluminum, prepared above And calcium titanate surface-treated with methacrylsilane * 1-21: coated with a hydrated oxide of silicon, coated with a hydrated oxide of aluminum, and surface-treated with methacrylsilane as prepared above Strontium titanate * 1-22: Calcium zirconate * 1 prepared above, coated with a hydrated oxide of silicon, then coated with a hydrated oxide of aluminum, and surface-treated with methacrylsilane -23: strontium zirconate * 1-24, prepared above, coated with a hydrated oxide of silicon, then coated with a hydrated oxide of aluminum, and surface-treated with methacrylsilane Barium acid (BT30 manufactured by Sakai Chemical Industry Co., Ltd.)
* 1-25: Barium titanate surface-treated with methacrylsilane prepared above

From the results shown in the above table, the curable resin compositions of Examples 1-1 to 1-10 of the present invention have improved dispersibility of the perovskite compound, excellent adhesion to the substrate, and high dielectric constant. It can be seen that a cured product that can achieve both a low dielectric loss tangent is obtained.

<Second embodiment>
[Surface treatment of titanium oxide particles]
(Titanium oxide particles that were coated with a hydrated oxide of silicon and then coated with a hydrated oxide of aluminum and surface-treated with methacrylsilane blended in Example 2-1)
After heating a water slurry of 50 g of titanium oxide particles (JA-C manufactured by Teica, average particle diameter 180 nm) to 70 ° C., a 10% aqueous solution of sodium silicate was added to the titanium oxide particles by 15% in terms of titanium oxide particles. did. Hydrochloric acid was added to the slurry to adjust the pH to 4 and aged for 30 minutes. Further, while maintaining the pH at 5 ± 1 with hydrochloric acid, a 20% aqueous solution of sodium aluminate (NaAlO ₂ ) was added to barium titanate with alumina. 20% in terms of (Al ₂ O ₃ ). Thereafter, a 20% aqueous sodium hydroxide solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered and washed with a filter press, and dried under vacuum to obtain a solid of titanium oxide particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum.
50 g of titanium oxide particles coated with the hydrated oxide of aluminum and then coated with the hydrated oxide of aluminum, 48 g of PMA as a solvent, and a silane coupling agent having a methacryl group (Shin-Etsu Chemical Co., Ltd.) And 3 g of KBM-503) were uniformly dispersed, filtered, washed with water, and vacuum-dried to obtain solid titanium oxide particles surface-treated with methacrylsilane.

(Titanium oxide particles blended in Examples 2-2 and 2-3, coated with hydrated oxide of silicon, coated with hydrated oxide of aluminum, and surface-treated with phenylaminosilane)
After heating a water slurry of 50 g of titanium oxide particles (JA-C manufactured by Teica, average particle diameter 180 nm) to 70 ° C., a 10% aqueous solution of sodium silicate was added to the titanium oxide particles by 15% in terms of titanium oxide particles. did. Hydrochloric acid was added to the slurry to adjust the pH to 4 and aged for 30 minutes. Further, while maintaining the pH at 5 ± 1 with hydrochloric acid, a 20% aqueous solution of sodium aluminate (NaAlO ₂ ) was added to barium titanate with alumina. 20% in terms of (Al ₂ O ₃ ). Thereafter, a 20% aqueous sodium hydroxide solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered and washed with a filter press, and dried under vacuum to obtain a solid of titanium oxide particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum.
50 g of titanium oxide particles coated with the hydrated oxide of aluminum and then coated with the hydrated oxide of aluminum, 48 g of PMA as a solvent, and a silane coupling agent having a phenylamino group (Shin-Etsu Chemical Co., Ltd.) And 3 g of KBM-573 (manufactured by Kuraray Co., Ltd.) were uniformly dispersed, filtered, washed with water, and dried under vacuum to obtain solid particles of titanium oxide particles surface-treated with phenylaminosilane.

(Titanium oxide particles surface-treated with methacrylsilane blended in Comparative Example 2-2)
50 g of titanium oxide particles (JA-C manufactured by Teica, average particle diameter 180 nm), 48 g of PMA as a solvent, and 3 g of a silane coupling agent having a methacryl group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly dispersed. Filtration, washing with water, and vacuum drying yielded solid particles of titanium oxide particles surface-treated with methacrylsilane.

<Measurement of zeta potential>
The zeta potential of titanium oxide particles (JA-C manufactured by Teica and R-780-2 manufactured by Ishihara Sangyo Co., Ltd.) and the surface-treated titanium oxide particles prepared above were measured using ELSZ-2000ZS manufactured by Otsuka Electronics. did.
Specifically, each particle was adjusted to a concentration of 0.1 wt% with PMA (propylene glycol monomethyl ether acetate), and dispersed in an ultrasonic bath for 1 minute. The measurement was performed by using a Flow Cell, applying an applied voltage of 300 V, and measuring the zeta potential at 20 ° C. The potential was calculated by the Huckel equation.
(Huckel formula)
ζ = 6πηU / ε
ζ: Zeta potential U: Electric mobility η: Viscosity of solvent

[Examples 2-1 to 2-3, Comparative Examples 2-1 to 2-3]
Various components shown in Table 4 below were blended in the ratio (parts by mass) shown in Table 4, diluted with an organic solvent PMA to a dispersible viscosity in a bead mill, preliminarily mixed with a stirrer, and kneaded in a bead mill. And the curable resin composition was dispersed. The obtained dispersion was passed through a filter having an opening of 10 μm to obtain a curable resin composition.

<Dispersibility>
For the curable resin compositions of the respective examples and comparative examples, the degree of dispersion was confirmed by using a grind gauge having a width of 90 mm, a length of 240 mm, and a maximum depth of 50 μm according to JIS K5101 and JIS K5600. As a viewpoint of the degree of dispersion, a section in which five or more grains were confirmed was confirmed.
○: 10 μm or less Δ: More than 10 μm 25 μm or less ×: More than 25 μm

<Preparation of dry film>
The curable resin composition obtained as described above was diluted by adding 300 g of methyl ethyl ketone and stirred for 15 minutes with a stirrer to obtain a coating liquid. The coating solution is applied on a 38 μm thick polyethylene terephthalate film (PET film, Emblet PTH-25 manufactured by Unitika Ltd.) having an arithmetic surface roughness Ra of 150 nm, and is usually dried at 80 ° C. for 15 minutes. A resin layer was formed. Next, a 18 μm-thick polypropylene film (cover film, OPP-FOA manufactured by Futamura Co., Ltd.) was laminated on the resin layer to produce a dry film.

<Preparation of cured film>
The polyethylene film is peeled from the dry film obtained as described above on the glossy surface of the electrolytic copper foil GTS-MP-18 μm (made by Furukawa Electric Co., Ltd.), and the resin layer of the dry film is coated on the copper foil surface side. Lamination, and subsequently, in Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-3, using a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho), the degree of pressurization: 0.8 MPa, 100 Heat lamination was performed at a temperature of 1 ° C. and a degree of vacuum of 133.3 Pa, and the copper foil and the resin layer were adhered to each other.
Next, in Examples 2-1 and 2-2 and Comparative Examples 2-1 to 2-3, exposure was performed from above the dry film (exposure amount: 400 to 400 mm) using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp). After 600 mJ / cm ² ), the polyethylene terephthalate film was peeled from the dry film to expose the resin layer. Thereafter, development was performed using a 1% by weight aqueous solution of Na ₂ CO _{3 at} 30 ° C. under a spray pressure of 0.2 MPa for 60 seconds to form a resin layer having a predetermined resist pattern. Subsequently, the resin layer was irradiated with an exposure amount of 1 J / cm ^{2 in} a UV conveyor furnace equipped with a high-pressure mercury lamp, and then heated at 160 ° C. for 60 minutes to completely cure the resin layer, thereby producing a cured film.
In Example 2-3, after laminating the dry film, the PET film was peeled off, and the resin layer was completely cured at 180 ° C. for 60 minutes.

<Dielectric constant and dielectric loss tangent>
A dry film prepared in the same manner as in the above <Preparation of dry film> except that the thickness of the resin layer was changed to other than 40 μm, was laminated on a glossy surface of electrolytic copper foil GTS-MP-18 μm (Furukawa Electric Co., Ltd.). Then, the resin layer was flattened and completely cured under the conditions described in the above <Preparation of cured film>. Thereafter, the cured product was peeled from the copper foil to obtain a cured product having a thickness of 30 μm.
The cured product was cut into a length of 80 mm and a width of 2 mm, and a network analyzer 8510C manufactured by Keysight and a complex relative permittivity calculation software CAMA-S manufactured by KEAD were used. The dielectric constant and the dielectric loss tangent at a measurement temperature of 22 ° C. and 10 GHz were measured using a perturbation cavity resonator.
(Dielectric constant)
〇: Dielectric constant value 5 or more ×: Dielectric constant value less than 5 (dielectric tangent)
〇: dielectric loss tangent value 0.02 or less △: dielectric loss tangent value more than 0.02, 0.025 or less ×: dielectric loss tangent value more than 0.025

<Red discoloration>
The compositions prepared in each of the examples and comparative examples were applied to a copper-clad laminate, photocured and heat-cured under the conditions described in the above <Preparation of cured film>, and then electroless gold plating was performed. The appearance after gold plating was visually checked for red discoloration due to adhesion of gold particles.
〇: No discoloration △: There is spot discoloration X: There is discoloration

<Adhesion to copper after HAST>
As a pretreatment, CZ-8401 manufactured by Mech Co., Ltd. is sprayed on the glossy surface of the electrolytic copper foil GTS-MP-18 μm (manufactured by Furukawa Electric Co., Ltd.), followed by AP-3002 treatment for roughening treatment, and surface roughness Ra of 0. A low-profile copper foil of 0.04 μm was obtained.
A dry film having a resin layer thickness of 20 μm prepared in each of Examples and Comparative Examples was laminated on the treated surface, and cured under the above-described conditions for forming a cured film to obtain a sample in which an insulating layer was formed.
The insulating layer of this sample and an FR-4 (glass epoxy) substrate were bonded with an adhesive (AR-S30 manufactured by Nichiban). This bonded body was cut into 100 mm × 15 mm, and cut into copper foil at intervals of 10 mm.
After the initial value of this sample and the HAST test at 130 ° C. and 85% RH for 100 hours, the peel strength of both samples was measured by Autograph AG-X manufactured by Shimadzu Corporation based on JIS C6481.
The higher the peel strength, the better the adhesion, and the lower the rate of decrease in adhesion before and after the HAST test, the better.
(Before HAST-After HAST) / Before HAST × 100 (%)
：: Adhesion decrease rate less than 40% 〇: Adhesion decrease rate 40% or more and less than 55% △: Adhesion decrease rate 55% or more and less than 65% ×: Adhesion decrease rate 65% or more

<Measurement of acid value of solid content of composition>
About 0.5 g of a composition sample was taken, completely dissolved in 50 ml of 2-butoxyethanol, and titrated with a 0.1N ethanolic potassium hydroxide solution, and the acid value was calculated from the following formula.
Acid value (mgKOH / g) = {N × f × 56100 × (V-BL) / (1000 × W)
W: sample amount (g), N: (concentration of potassium hydroxide solution (mol / l), f: titer, V: titer (ml), BL: blank titer

* 2-1: Carboxyl group-containing photosensitive resin A-1 synthesized above (carboxylic acid equivalent: 654 g / eq)
* 2-2: Unidic EQG-1170 manufactured by DIC (alicyclic UV curable amide imide resin, carboxylic acid equivalent: 962 g / eq)
* 2-3: Nippon Kayaku Co., Ltd. NC-6000 (bisphenol F type epoxy resin, epoxy equivalent: 210 g / eq)
* 2-4: TEPIC-VL (Nissan Chemical Industries, Ltd.) (polyfunctional epoxy resin, epoxy equivalent: 135 g / eq)
* 2-5: Dicyandiamide * 2-6: Melamine * 2-7: Omnirad TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by IGM
* 2-8: A-DCP (tricyclodecane dimethanol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.
* 2-9: Titanium oxide prepared above, coated with hydrated oxide of silicon, then coated with hydrated oxide of aluminum, and surface-treated with methacrylsilane * 2-10: Prepared above Titanium oxide coated with a hydrated oxide of silicon, then coated with a hydrated oxide of aluminum, and surface-treated with phenylaminosilane * 2-11: untreated titanium oxide (JA- C, average primary particle diameter: 180 nm)
* 2-12: Titanium oxide surface-treated with methacrylsilane prepared above * 2-13: Titanium oxide (R-780-2, manufactured by Ishihara Sangyo Co., average particle size: 0.24 μm, hydrated oxidation of silicon) Coated with hydrated oxide of aluminum and aluminum (approximately 20% treated)

From the results shown in the above table, the curable resin compositions of Examples 2-1 to 2-3 of the present invention have improved dispersibility of titanium oxide, excellent adhesion to a substrate, high dielectric constant and low dielectric constant. It can be seen that a cured product that can satisfy both the dielectric loss tangent is obtained.

<Third embodiment>
[Surface treatment of filler]
(Boron nitride particles coated with hydrated silicon oxide compounded in Example 3-1)
A 50 g water slurry of boron nitride particles (S1, manufactured by ESK Ceramics GmbH, average particle diameter 2 μm, specific gravity 3.65, thermal conductivity 200 W / m · k) is heated to 70 ° C., and then a 10% aqueous sodium silicate solution is nitrided. 1% was added to the boron particles in terms of boron nitride particles. Hydrochloric acid was added to this slurry to adjust the pH to 4, aged for 30 minutes, and further adjusted to pH 7 ± 1 with hydrochloric acid. The slurry was filtered and washed with a filter press, and dried under vacuum to obtain solid boron nitride particles coated with a silicon hydrated oxide.

(Boron nitride particles coated with a hydrated aluminum oxide compounded in Example 3-2)
50 g of a water slurry of boron nitride particles (S1, manufactured by ESK Ceramics GmbH, average particle diameter 2 μm, specific gravity 3.65, thermal conductivity 200 W / m · k) was heated to 70 ° C., and then 20% sodium aluminate (NaAlO _2). 1) The aqueous solution was added to the boron nitride particles at 1% in terms of alumina (Al ₂ O ₃ ). Thereafter, a 20% aqueous sodium hydroxide solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered and washed with a filter press, and dried under vacuum to obtain a solid of boron nitride particles coated with aluminum hydrated oxide.

(Boron nitride particles coated with hydrated zirconium oxide blended in Example 3-3)
50 g of a water slurry of boron nitride particles (S1, manufactured by ESK Ceramics GmbH, average particle size: 2 μm, specific gravity: 3.65, thermal conductivity: 200 W / m · k) was heated to 70 ° C., and then 100 g / l of zirconium oxychloride etc. An aqueous solution of a water-soluble zirconium compound was added to boron nitride particles at 1% in terms of zirconia (ZrO ₂ ). Thereafter, a 20% aqueous sodium hydroxide solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered and washed with a filter press and dried under vacuum to obtain a solid of boron nitride particles coated with a hydrated oxide of zirconia.

(Boron nitride particles coated with a hydrated oxide of zinc formulated in Example 3-4)
A 50 g water slurry of boron nitride particles (S1, manufactured by ESK Ceramics GmbH, average particle diameter 2 μm, specific gravity 3.65, thermal conductivity 200 W / m · k) was heated to 70 ° C., and an aqueous solution of zinc sulfate was subjected to boron nitride particles. 1% in terms of ZnO. Thereafter, a 20% aqueous sodium hydroxide solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered and washed with a filter press, and dried under vacuum to obtain a solid of boron nitride particles coated with a hydrated oxide of zinc.

(Boron nitride particles coated with a hydrated titanium oxide compounded in Example 3-5)
A 50 g water slurry of boron nitride particles (S1, manufactured by ESK Ceramics GmbH, average particle diameter 2 μm, specific gravity 3.65, thermal conductivity 200 W / m · k) was heated to 70 ° C., and then a 100 g / l aqueous solution of titanyl sulfate was nitrided. 1% was added to the boron particles in terms of TiO ₂ . Thereafter, a 20% aqueous sodium hydroxide solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered and washed with a filter press, and dried under vacuum to obtain a solid of boron nitride particles coated with a hydrated oxide of titanium.

(Boron nitride particles formulated in Example 3-6 and coated with hydrated oxide of silicon and then coated with hydrated oxide of aluminum)
A 50 g water slurry of boron nitride particles (S1, manufactured by ESK Ceramics GmbH, average particle diameter 2 μm, specific gravity 3.65, thermal conductivity 200 W / m · k) is heated to 70 ° C., and then a 10% aqueous sodium silicate solution is nitrided. 1% was added to the boron particles in terms of boron nitride particles. Hydrochloric acid was added to the slurry to adjust the pH to 4 and aged for 30 minutes. Further, while maintaining the pH at 5 ± 1 with hydrochloric acid, a 20% aqueous solution of sodium aluminate (NaAlO ₂ ) was added to the boron nitride particles to form an alumina. 1% in terms of (Al ₂ O ₃ ). Thereafter, a 20% aqueous sodium hydroxide solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered and washed with a filter press, and dried under vacuum to obtain a solid of boron nitride particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum.

(Boron nitride particles compounded in Example 3-7 and coated with hydrated oxide of silicon and then coated with hydrated oxide of zirconium)
After raising the temperature of a water slurry of 50 g of the same boron nitride particles as described above to 70 ° C., a 10% aqueous solution of sodium silicate was added to the boron nitride particles at 1% in terms of boron nitride particles. Hydrochloric acid was added to the slurry to adjust the pH to 4, and the mixture was aged for 30 minutes. The temperature was raised to 40 ° C. while maintaining the pH at 5 ± 1 with hydrochloric acid. Then, a 100 g / l aqueous zirconium oxychloride solution was added to the boron nitride particles. To 1% in terms of ZrO ₂ . Thereafter, a 20% aqueous sodium hydroxide solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered and washed with a filter press, and dried under vacuum to obtain a solid of boron nitride particles coated with a hydrated oxide of silicon and a hydrated oxide of zirconium.

(Boron nitride particles compounded in Examples 3-8, coated with hydrated oxide of silicon and then coated with hydrated oxide of zinc)
After raising the temperature of a water slurry of 50 g of the same boron nitride particles as described above to 70 ° C., a 10% aqueous solution of sodium silicate was added to the boron nitride particles at 1% in terms of boron nitride particles. Hydrochloric acid was added to the slurry to adjust the pH to 4, and the mixture was aged for 30 minutes. After the temperature was raised to 45 ° C. while maintaining the pH at 5 ± 1 with hydrochloric acid, an aqueous solution of zinc sulfate was added to the boron nitride particles. 1% by mass as ZnO was added. Thereafter, a 20% aqueous sodium hydroxide solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered and washed with a filter press, and dried under vacuum to obtain solid particles of boron nitride particles coated with a hydrated oxide of silicon and a hydrated oxide of zinc.

(Boron nitride particles formulated in Example 3-9 and coated with hydrated oxide of silicon and then coated with hydrated oxide of titanium)
After raising the temperature of a water slurry of 50 g of the same boron nitride particles as described above to 70 ° C., a 10% aqueous solution of sodium silicate was added to the boron nitride particles at 1% in terms of boron nitride particles. Hydrochloric acid was added to the slurry to adjust the pH to 4 and the mixture was aged for 30 minutes. After the temperature was raised to 40 ° C. while maintaining the pH at 5 ± 1 with hydrochloric acid, a 100 g / l aqueous solution of titanyl sulfate was added to the boron nitride particles. On the other hand, 1% was added in terms of TiO ₂ . Thereafter, a 20% aqueous sodium hydroxide solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered and washed with a filter press, and dried under vacuum to obtain solid particles of boron nitride particles coated with a hydrated oxide of silicon and a hydrated oxide of titanium.

(Boron nitride particles coated with a hydrated aluminum oxide and surface-treated with methacrylsilane blended in Example 3-10)
50 g of boron nitride particles coated with a hydrated aluminum oxide obtained in the same manner as above, 48 g of PMA as a solvent, and 1 g of a silane coupling agent having a methacryl group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) Was uniformly dispersed, filtered, washed with water, and dried under vacuum to obtain solid particles of boron nitride particles surface-treated with methacrylsilane.

(Boron nitride particles coated with hydrated aluminum oxide and surface-treated with phenylaminosilane, blended in Example 3-11)
50 g of boron nitride particles coated with a hydrated aluminum oxide obtained in the same manner as above, 48 g of PMA as a solvent, and a silane coupling agent having a phenylamino group (KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd.) And 0.5 g of the same, and the solid was filtered, washed with water, and dried under vacuum to obtain solid particles of boron nitride particles surface-treated with phenylaminosilane.

(Boron nitride particles formulated in Example 3-12, coated with hydrated oxide of silicon, then coated with hydrated oxide of aluminum, and surface-treated with methacrylsilane)
50 g of boron nitride particles coated with silicon and then coated with a hydrated oxide of aluminum, 48 g of PMA as a solvent, and a silane coupling agent having a methacryl group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) ) Was uniformly dispersed, and filtered, washed with water, and dried under vacuum to obtain solid particles of boron nitride particles surface-treated with methacrylsilane.

(Boron nitride particles surface-treated with methacrylsilane compounded in Comparative Example 3-1)
50 g of boron nitride particles (S1, manufactured by ESK Ceramics GmbH, average particle diameter 2 μm, specific gravity 3.65, thermal conductivity 200 W / m · k)), 48 g of PMA as a solvent, and a silane coupling agent having a methacryl group (Shin-Etsu Chemical) And 0.5 g of KBM-503 (manufactured by Kogyo Co., Ltd.), and the mixture was filtered, washed with water, and dried under vacuum to obtain solid particles of boron nitride particles surface-treated with methacrylsilane.

(Aluminum nitride particles coated with hydrated oxide of silicon, coated with hydrated oxide of zirconium, and surface-treated with methacrylsilane, blended in Example 3-13)
A 50 g water slurry of aluminum nitride particles (manufactured by Tokuyama Corporation, average particle diameter 1 μm, specific gravity 3.26, thermal conductivity 200 W / m · k) was heated to 70 ° C., and then a 10% aqueous sodium silicate solution was converted to aluminum nitride particles. On the other hand, 1% was added in terms of aluminum nitride particles. Hydrochloric acid was added to the slurry to adjust the pH to 4 and the mixture was aged for 30 minutes. After the temperature was raised to 40 ° C. while maintaining the pH at 5 ± 1 with hydrochloric acid, 100 g / l aqueous zirconium oxychloride solution was added to aluminum nitride particles. To 1% in terms of ZrO ₂ . Thereafter, a 20% aqueous sodium hydroxide solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered and washed with a filter press, and dried under vacuum to obtain a solid of aluminum nitride particles coated with a hydrated oxide of silicon and a hydrated oxide of zirconium.
50 g of the coated aluminum nitride particles, 48 g of PMA as a solvent, and 0.5 g of a silane coupling agent having a methacryl group (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) are uniformly dispersed, filtered, washed with water, and vacuum-dried. As a result, solids of boron nitride particles surface-treated with methacrylsilane were obtained.

(Magnesium oxide particles coated with zirconium hydrated oxide, coated with hydrated oxide of silicon, and surface-treated with methacrylsilane, blended in Example 3-14)
In the preparation of aluminum nitride particles in Example 3-13, the aluminum nitride particles were changed to magnesium oxide particles (SMO manufactured by Sakai Chemical Co., average particle diameter 0.4 μm, specific gravity 3.65, thermal conductivity 40 W / m · k). After raising the temperature of 50 g of the water slurry to 70 ° C., a 10% aqueous solution of sodium silicate was added to the magnesium oxide particles by 3% in terms of magnesium oxide particles. Hydrochloric acid was added to the slurry to adjust the pH to 4, and the mixture was aged for 30 minutes. After maintaining the pH at 5 ± 1 with hydrochloric acid, the temperature was raised to 40 ° C., and the aqueous solution of 100 g / l zirconium oxychloride was treated with magnesium oxide particles. Was added in an amount of 5 to 6% in terms of ZrO ₂ . Thereafter, a 20% aqueous sodium hydroxide solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered and washed with a filter press, and dried under vacuum to obtain a solid of magnesium oxide particles coated with a hydrated oxide of silicon and a hydrated oxide of zirconium.
50 g of the coated magnesium oxide particles, 48 g of PMA as a solvent, and 1 g of a silane coupling agent having a methacryl group (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) are uniformly dispersed, and the mixture is filtered, washed with water, and vacuum-dried to obtain methacryl. A solid of magnesium oxide particles surface-treated with silane was obtained.

(Aluminum oxide particles formulated in Example 3-15, coated with a hydrated oxide of silicon, then coated with a hydrated oxide of zirconium, and surface-treated with methacrylsilane)
In the preparation of the aluminum nitride particles in Example 3-13, the aluminum nitride particles were converted into aluminum oxide particles (ASFP-20 manufactured by Denka, average particle diameter 0.3 μm, specific gravity 4.0, thermal conductivity 28 W / mk). A solid of magnesium oxide particles surface-treated with methacrylsilane was obtained in the same manner as described above, except for the change.

(Spinel particles blended in Example 3-16, coated with a hydrated oxide of silicon and then coated with a hydrated oxide of zirconium and surface-treated with methacrylsilane)
In the preparation of the aluminum nitride particles in Example 3-13, the aluminum nitride particles were converted to spinel particles (MgAl ₂ O ₄ , SN-1 manufactured by Tateho Chemical Industry Co., Ltd., average particle diameter 0.4 μm, specific gravity 3.8, thermal conductivity 35 W / M · k) to obtain solids of spinel particles surface-treated with methacrylsilane in the same manner as described above.

(Silica particles surface-treated with methacrylsilane blended in Comparative Example 3-3)
50 g of silica particles (SFP-20M manufactured by Denka, average particle diameter 0.4 μm, specific gravity 2.2, thermal conductivity 1.3 W / m · k), 48 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and methacrylic acid 1 g of a silane coupling agent having a group (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was uniformly dispersed, filtered, washed with water, and vacuum-dried to obtain a solid of silica particles surface-treated with methacrylsilane.

[Examples 3-1 to 3-17, Comparative Examples 3-1 to 3-3]
Various components shown in the following Tables 5 to 7 are blended in the ratios (parts by mass) shown in Tables 5 to 7, and diluted with an organic solvent (propylene glycol monomethyl ether acetate (PMA)) to a viscosity that enables dispersion in a bead mill. After pre-mixing with a stirrer, the mixture was kneaded with a bead mill to disperse the curable resin composition. The obtained dispersion was passed through a filter having an opening of 10 μm to obtain a curable resin composition.

<Preparation of dry film>
The curable resin composition obtained as described above was diluted by adding 300 g of methyl ethyl ketone and stirred for 15 minutes with a stirrer to obtain a coating liquid. The coating liquid is applied on a 38 μm-thick polyethylene terephthalate film (PET film, Emblet PTH-25 manufactured by Unitika Ltd.) having an arithmetic surface roughness Ra of 150 nm, usually at 80 to 100 ° C. (Examples 3-1 to 3-1). 3-16 and Comparative Examples 3-1 to 3-3 were dried at a temperature of 80 ° C. for 15 minutes, and Example 3-17 was dried at a temperature of 100 ° C. for 15 minutes for 15 minutes to form a resin layer having a thickness of 20 μm. Next, a 18 μm-thick polypropylene film (cover film, OPP-FOA manufactured by Futamura Co., Ltd.) was laminated on the resin layer to produce a dry film.

<Preparation of cured film>
The polyethylene film is peeled from the dry film obtained as described above on the glossy surface of the electrolytic copper foil GTS-MP-18 μm (manufactured by Furukawa Electric Co., Ltd.), and the dry film The resin layers were laminated, and subsequently, in Examples 3-1 to 3-16 and Comparative Examples 3-1 to 3-3, the degree of pressurization was set to 0.degree. By using a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho). Heat lamination was carried out under the conditions of 8 MPa, 100 ° C., 1 minute, degree of vacuum: 133.3 Pa, and the copper foil and the resin layer were brought into close contact with each other. In Example 3-17, heat lamination was performed under the following conditions: 0.5 MPa, 100 ° C., 1 minute, degree of vacuum: 133.3 Pa, and the copper foil and the resin layer were adhered to each other.
Next, in Examples 3-1 to 3-16 and Comparative Examples 3-1 to 3-3, exposure was performed from above the dry film using a light exposure device equipped with a high-pressure mercury lamp (short arc lamp) (exposure amount: 400 to After 600 mJ / cm ² ), the polyethylene terephthalate film was peeled from the dry film to expose the resin layer. Thereafter, development was performed using a 1% by weight aqueous solution of Na ₂ CO _{3 at} 30 ° C. under a spray pressure of 0.2 MPa for 60 seconds to form a resin layer having a predetermined resist pattern. Subsequently, after irradiating the resin layer with an exposure amount of 1 J / cm ^{2 in} a UV conveyor furnace equipped with a high-pressure mercury lamp, the resin layer was completely cured by heating at 170 ° C. for 60 minutes to produce a cured film.
In Example 3-17, after laminating the dry film, the PET film was peeled off, and the resin layer was completely cured at 190 ° C. for 60 minutes.

<Thermal conductivity>
Under the same conditions as in the above <Preparation of dry film> and <Preparation of cured film>, the cured film of the resin layer prepared in each of the examples and comparative examples was replaced with electrolytic copper foil GTS-MP-18 μm (Furukawa Electric Co., Ltd. ) Was formed to a thickness of 400 μm on the glossy surface. Thereafter, the cured film was peeled off from the copper foil, a sample having a thickness of 400 μm and a diameter of 10 mm was prepared, and the thermal diffusivity was measured by a laser flash method thermophysical property measurement device LFA-502 manufactured by Kyoto Electronics Industry Co., Ltd. and analyzed by a curve fitting method. did. The density was measured by an underwater displacement method, and the specific heat was measured by a DSC method (PerkinElmer Oyris Diamond DSC), and the thermal conductivity was calculated by the following equation.
Thermal conductivity [W / (m · K)] = density (Kg / m ³ ) × specific heat [kJ / (kg · K)] × thermal diffusivity (m ² / s) × 1000
〇: Thermal conductivity 1 or more ×: Thermal conductivity less than 1

<Resolution>
The dry films of Examples 3-1 to 3-16 and Comparative Examples 3-1 to 3-3 obtained in the above <Preparation of dry film> were heat-laminated using a vacuum laminator to obtain a resin of a photosensitive resin composition. An evaluation substrate having a layer was obtained. The substrate was exposed to a pattern of L / S = 100 μm / 100 μm at an optimal exposure amount using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), and the PET film was peeled off. Thereafter, using a 1% by mass aqueous solution of sodium carbonate at 30 ° C., development was performed for 60 seconds under the condition of a spray thickness of 0.2 MPa to obtain a resist pattern.
〇: A good pattern was formed.
Δ: Chipping was confirmed.
X: Line formation was impossible.

<Adhesion with EMC (mold resin)>
Using a mold material (UV8710U manufactured by Panasonic Corporation), a circular mold (2.523 mm in diameter, 3.00 mm in height) was press-molded on the cured film without plasma treatment obtained in the above <Preparation of cured film>. Then, the mold material was cured by heating at 175 ° C. for 4 hours. Then, a shear was given to the mold material provided on the surface of the cured film, and the peel strength between the cured film and the mold material was measured.
〇: 150 N or more △: 100 N or more and less than 150 N ×: less than 100 N

<Adhesion with glass>
As a glass substrate, a cured film was produced on AN100 glass (manufactured by Asahi Glass Co., Ltd.) under the same conditions as the above <Preparation of cured film>. Based on JIS K5400, 100 crosscuts of 1 mm square (10 × 10) are made by a cross cutter to reach the interlayer material, and a cellophane tape is completely adhered to it, separated, and several hundred out of 100 are closely adhered. Was confirmed.
〇: 100/100
Δ: 70/100 or more and less than 100/100 x: less than 70/100

<Adhesion to copper after HAST>
As a pretreatment, a glossy surface of electrolytic copper foil GTS-MP-18 μm (made by Furukawa Electric Co., Ltd.) is sprayed with CZ-8401 manufactured by Mech Co., Ltd., and then subjected to AP-3002 treatment to roughen the surface. A low-profile copper foil having an Ra of 0.04 μm was obtained.
A dry film having a resin layer thickness of 20 μm prepared in each of Examples and Comparative Examples was laminated on the treated surface, and cured under the above-described conditions for forming a cured film to obtain a sample in which an insulating layer was formed.
The insulating layer of this sample and an FR-4 (glass epoxy) substrate were bonded with an adhesive (AR-S30 manufactured by Nichiban). This bonded body was cut into 100 mm × 15 mm, and cut into copper foil at intervals of 10 mm.
After the initial value of this sample and the HAST test at 130 ° C. and 85% RH for 100 hours, the peel strength of both samples was measured by Autograph AG-X manufactured by Shimadzu Corporation based on JIS C6481.
The higher the peel strength, the better the adhesion, and the lower the rate of decrease in adhesion before and after the HAST test, the better.
(Before HAST-After HAST) / Before HAST × 100 (%)
●: Adhesion reduction rate less than 35% ◎: Adhesion reduction rate from 35% to less than 40% Δ: Adhesion reduction rate from 40% to less than 55% Δ: Adhesion reduction rate from 55% to less than 65% ×: Adhesion reduction Rate 65% or more

* 3-1: Carboxyl group-containing photosensitive resin A-1 synthesized above (carboxylic acid equivalent: 701.25 g / eq)
* 3-2: ESN-475V manufactured by Nippon Steel Chemical Co., Ltd. (naphthalene type epoxy resin, epoxy equivalent: 340 g / eq)
* 3-3: NC-3000L manufactured by Nippon Kayaku (biphenyl type epoxy resin, epoxy equivalent: 275 g / eq)
* 3-4: Primaset PT30 (Novolak type polyfunctional cyanate resin) manufactured by Lonza Japan
* 3-5: NIR-3000 (a compound having a maleimide group) manufactured by Nippon Kayaku Co., Ltd.
* 3-6: Mitsubishi Chemical YX7200B35 (phenoxy type)
* 3-7: DMAP (dimethylaminopyridine)
* 3-8: Dicyandiamide * 3-9: Melamine * 3-10: OP-935 (Metal phosphinate) based on Clariant Chemicals
* 3-11: Phthalocyanine blue * 3-12: Carbon black manufactured by Tokushiki * 3-13: Omnirad TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by IGM
* 3-14: A-DCP (tricyclodecane dimethanol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd.
* 3-15: Boron nitride particles coated with hydrated oxide of silicon prepared above * 3-16: Boron nitride particles coated with hydrated oxide of aluminum prepared above * 3-17 : Boron nitride particles coated with hydrated oxide of zirconium prepared above * 3-18: Boron nitride particles coated with hydrated oxide of zinc prepared above * 3-19: Prepared above Boron nitride particles coated with hydrated oxide of titanium * 3-20: Boron nitride particles prepared above, coated with hydrated oxide of silicon and then coated with hydrated oxide of aluminum * 3-21: Boron nitride particles prepared above, coated with hydrated oxide of silicon and then coated with hydrated oxide of zirconium * 3-22: The hydrated oxide of silicon prepared above Hydration of zinc after being coated Boron nitride particles coated with halide * 3-23: Prepared above, boron nitride particles coated with hydrated oxide of silicon and then coated with hydrated oxide of titanium * 3-24: Prepared above Boron nitride particles coated with hydrated aluminum oxide and surface-treated with methacrylsilane * 3-25: Coated with hydrated aluminum oxide prepared above and surface-coated with phenylaminosilane Treated boron nitride particles * 3-26: The above-prepared boron nitride particles coated with a hydrated oxide of silicon and then coated with a hydrated oxide of aluminum and surface-treated with methacrylsilane * 3-27: Boron nitride particles surface-treated with methacrylsilane prepared above * 3-28: Untreated boron nitride particles (ESK Ceramics GmbH) S1, specific gravity: 3.65, average particle diameter: 2 μm, thermal conductivity: 200 W / m · k)
* 3-29: Aluminum nitride particles prepared above, coated with hydrated oxide of silicon, then coated with hydrated oxide of zirconium, and surface-treated with methacrylsilane * 3-30: Prepared magnesium oxide particles coated with hydrated oxide of silicon and then coated with hydrated oxide of zirconium and surface-treated with methacrylsilane * 3-31: hydrated silicon prepared as described above Aluminum oxide particles coated with oxide and then coated with hydrated oxide of zirconium and surface-treated with methacrylsilane * 3-32: after coated with hydrated oxide of silicon prepared above Spinel particles coated with a hydrated oxide of zirconium and surface-treated with methacrylsilane * 3-33: Surface prepared with methacrylsilane as prepared above Management silica particles

From the results shown in the above table, it can be seen that the curable resin compositions of Examples 3-1 to 3-17 of the present invention have improved filler dispersibility having high thermal conductivity, and have good adhesion to the substrate and high thermal conductivity. It can be seen that a cured product capable of satisfying both conditions can be obtained.

10 laminated structure 11 interlayer insulating material (package substrate)
12a,

12b Conductive layers

13a, 13b Solder resist 14 Solder 15 Semiconductor wafer 16 Underfill 17 Sealant

Claims

A perovskite compound coated with at least one of silicon hydrated oxide, aluminum hydrated oxide, zirconium hydrated oxide, zinc hydrated oxide and titanium hydrated oxide; And a curable resin.
The curable resin composition according to claim 1, wherein the coated perovskite compound accounts for 20% by volume or more based on the total solid content of the composition.
The curable resin composition according to claim 1, wherein the coated perovskite compound further has a curable reactive group on the surface.
A dry film having a resin layer obtained by applying and drying the curable resin composition according to claim 1 on a film.
(4) A cured product obtained by curing the curable resin composition according to any one of (1) to (3) or the resin layer of the dry film according to (4).
An electronic component comprising the cured product according to claim 5.
Titanium oxide particles coated with at least one of silicon hydrated oxide, aluminum hydrated oxide, zirconium hydrated oxide, zinc hydrated oxide and titanium hydrated oxide; , A curable resin, and a curable resin composition comprising:
A curable resin composition, wherein the coated titanium oxide particles have a curable reactive group on the surface.
The curable resin composition according to claim 7, wherein the coated titanium oxide particles account for 25% by volume or more of the total solid content of the composition.
8. The curable resin composition according to claim 7, wherein the coated titanium oxide particles have an absolute value of zeta potential of 15 mV or more.
The curable resin composition according to claim 7, wherein the solid content of the composition has an acid value of 25 mgKOH / g or less.
The curable resin composition according to claim 7, wherein the composition is applied to a substrate having a dielectric loss tangent of 0.01 or less at a frequency of 10 GHz.
A dry film comprising a resin layer obtained by applying and drying the curable resin composition according to claim 7 on a film.
硬化 A curable resin composition obtained by curing the curable resin composition according to any one of claims 7 to 11 or the resin layer of the dry film according to claim 12.
A structure comprising: a cured resin layer (A); and a cured resin layer (B) or a substrate (C) in contact with the cured resin layer (A),
The resin cured layer (A) has a positive zeta potential obtained by curing the curable resin composition according to any one of claims 7 to 11 or the resin layer of the dry film according to claim 12. Is a cured product of
A laminated structure, wherein the zeta potential of the cured resin layer (B) or the substrate (C) is negative.
An electronic component comprising the cured product according to claim 13.
An electronic component comprising the laminated structure according to claim 14.
Thermal conductivity coated with at least one of silicon hydrated oxide, aluminum hydrated oxide, zirconium hydrated oxide, zinc hydrated oxide and titanium hydrated oxide A filler of 15 W / mk or more,
A curable resin,
A curable resin composition comprising:
18. The curable resin composition according to claim 17, wherein the coated filler having a thermal conductivity of 15 W / mk is not less than 30% by volume based on the total solid content of the composition.
The curable resin composition according to claim 17, wherein the coated filler having a thermal conductivity of 15 W / mk or more further has a curable reactive group on its surface.
18. A dry film comprising a resin layer obtained by applying the curable resin composition according to claim 17 to a film and drying the film.
硬化 A cured product obtained by curing the curable resin composition according to any one of claims 17 to 19 or the resin layer of the dry film according to claim 20.
An electronic component comprising the cured product according to claim 21.