KR20200140289A - Curable resin composition, dry film, cured product, and electronic component - Google Patents

Abstract

A curable resin composition that has excellent adhesion after HAST treatment with the conductor layer and solder resist, and can obtain a cured product with low dielectric loss tangent, a dry film having a resin layer obtained from the composition, the composition or the resin layer of the dry film. It provides a cargo and an electronic component having the cured product. Silica particles coated with at least one of a hydration oxide of aluminum, a hydration oxide of zirconium, a hydration oxide of zinc, and a hydration oxide of titanium, an epoxy compound, a compound having an active ester group, and a cyanate ester group as a curing agent. It is a curable resin composition characterized by containing at least any 1 type of a compound and a compound which has a maleimide group.

Description

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

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

In general, in electronic components such as printed wiring boards, from the viewpoint of heat resistance and electrical insulation, as an interlayer insulating material or a solder resist material, a curable resin such as a carboxyl group-containing resin or an epoxy resin is used as a main component, and additional fillers are added. Resin compositions containing components are widely used.

In addition, the surface of the resin insulating layer, such as an interlayer insulating material, is usually roughened by a conductor layer formation process (copper surface rough transfer or chemical treatment before copper plating), thereby improving the adhesion to the solder resist material. .

In a cured product containing a conventional resin composition used as such an interlayer insulating material, there is a problem that a delay or loss of an electrical signal cannot be avoided when communicating in a high frequency region.

In recent years, from this problem of transmission loss, the interlayer insulating material surface tends to be roughening-free or low-roughening surface (so-called low-profile substrate), and as a material, an active ester is included. Low dielectric loss materials such as low polarity insulating materials have been used.

On the other hand, higher reliability (HAST resistance, PCT resistance, heat resistance, toughness, low warpage, thermal dimensional stability, etc.) has been required for permanent coatings such as solder resist used for semiconductor package substrates.

As a method of imparting high reliability to such a solder resist material or the like, it is generally practiced to improve thermal properties by, for example, high filling an inorganic filler in a composition. Among these inorganic fillers, silica, in particular, has excellent filling properties, has a low coefficient of thermal expansion (CTE), and allows easy introduction of a curable reactor, and has been widely used to improve the properties of solder resists (see Patent Document 1). However, in a solder resist material containing such a large amount of silica, since it becomes a low-polarity composition similar to the material of the low-profile substrate that solves the above-described problem of transmission loss, the adhesion is deteriorated, and in particular, the adhesion is liable to decrease after HAST treatment. Found a new problem to arise.

Japanese Patent Application Publication No. 2012-83467 (Patent Claims)

On the other hand, in the interlayer insulating material used as a material for a low profile substrate that has solved the problem of transmission loss, a component for reducing polarity such as an active ester is blended as described above in order to achieve a low dielectric loss tangent. It has been found that there is a problem in that the adhesion to the conductor layer or the solder resist is deteriorated when included or when the conductor layer is a roughened free or low roughened surface. In addition, as with the above solder resist material, from the viewpoint of CTE mismatch with the semiconductor chip, low dielectric loss tangent, etc., high filling of silica as an inorganic filler reduces the proportion of curable resin, so that the anchor effect due to desmear is reduced. In the case where it is not obtained, it has been found that it becomes a factor in which the adhesion to the solder resist or the conductor layer is further lowered. Therefore, when the above-described low-polarity material or high-filling material of silica is used, it is difficult to maintain excellent adhesion even after HAST treatment with a conductor layer and a solder resist, particularly a solder resist containing silica. In addition, since the solder resist imparting high-strength physical properties contains silica having a curable reactive group, curing shrinkage tends to increase along with the smaller diameter of the silica, and there is also a problem that adhesion is lowered.

From the above technical background, in the interlayer insulating material containing silica and a component aiming at lowering polarity such as active ester, which is used to solve the problem of transmission loss, even if the conductor layer is free or low roughened, the conductor Excellent adhesion after HAST treatment with layers, and excellent adhesion after HAST treatment with solder resists containing a large amount of silica particles, even if the interlayer insulating material and conductor layer surfaces are roughened-free or low-roughened. Is required to do.

Here, an object of the present invention is a curable resin composition having excellent adhesion after HAST treatment with a conductor layer and a solder resist, and capable of obtaining a cured product having a low dielectric loss tangent, a dry film having a resin layer obtained from the composition, the composition or It is to provide a cured product of the resin layer of the dry film and an electronic component having the cured product.

In order to achieve the above object, the inventors of the present invention focused on the surface treatment of silica used as an inorganic filler, and conducted intensive studies. As a result, the inventors use silica particles coated with any one of a hydrated oxide of aluminum, a hydrated oxide of zirconium, a hydrated oxide of zinc, and a hydrated oxide of titanium, and use a specific compound as a curing agent for the epoxy compound. It was found that can be solved, and came to complete the present invention.

That is, the curable resin composition of the present invention comprises silica particles coated with at least one of a hydration oxide of aluminum, a hydration oxide of zirconium, a hydration oxide of zinc, and a hydration oxide of titanium, an epoxy compound, and an active ester as a curing agent. It is characterized by containing at least any one of a compound having a group, a compound having a cyanate ester group, and a compound having a maleimide group.

In the curable resin composition of the present invention, it is preferable that the coated silica particles further have a curable reactive group on the surface.

The dry film of the present invention is characterized by having a resin layer obtained by applying and drying the curable resin composition to a film.

The cured product of the present invention is characterized in that it is obtained by curing the curable resin composition or the resin layer of the dry film.

The electronic component of the present invention is characterized by having the cured product.

According to the present invention, a curable resin composition having excellent adhesion after HAST treatment with a conductor layer and a solder resist and capable of obtaining a cured product having a low dielectric loss tangent, a dry film having a resin layer obtained from the composition, the composition or the dry A cured product of a resin layer of a film, and an electronic component having the cured product can be provided.

The curable resin composition of the present invention includes silica particles (hereinafter also referred to as ``coated silica particles'') coated with at least one of aluminum hydrated oxide, zirconium hydrated oxide, zinc hydrated oxide, and titanium hydrated oxide. , An epoxy compound, and as a curing agent, at least any one of a compound having an active ester group, a compound having a cyanate ester group, and a compound having a maleimide group is included.

In the present invention, as a curing agent, by including at least one of a compound having an active ester group, a compound having a cyanate ester group, and a compound having a maleimide group, and the coated silica particles, a conductor layer and a solder having a low dielectric loss tangent A cured product having excellent adhesion after HAST treatment with the resist can be obtained. If the coated silica further has a curable reactive group on its surface, it is preferable because it is effective in reducing CTE.

The problem of adhesion after the HAST treatment is particularly remarkable when the amount of filler is large.According to the present invention, when the amount of silica is large, for example, even if it is 30% by mass or more, it is difficult to obtain a curable resin composition in which adhesion is difficult to decrease even after HAST treatment of the cured product. It is possible.

In addition, it is preferable that the coated silica particles have a curable reactive group on the surface. In general, when a filler has a curable reactive group on its surface, it is possible to strengthen the bonding between the filler and the curable resin, but when the filler is high filled, the specific surface area of the filler particles is large and the resin content is reduced. It is easy to cause a portion with insufficient affinity, and in particular, under a HAST (high temperature, high humidity) environment, it becomes a factor of moisture absorption, thereby increasing the possibility of hydrolysis of the curable reactor portion. Therefore, the adhesion after HAST is poor, and peeling is liable to occur.

This poor wettability was particularly remarkable because, when the particle diameter of the filler is small, the specific surface area of the filler is large and a large amount of the covering resin is required. In addition, even if a curable reactive group is directly applied to the filler surface, the wettability with the curable resin is insufficient. In particular, in a strict environment such as HAST, the adhesion between the conductor layer and the solder resist decreased due to hydrolysis or the like.

However, in the present invention, even if the coated silica particles have a curable reactor on the surface, at least any of a hydrated oxide of aluminum, a hydrated oxide of zirconium, a hydrated oxide of zinc, and a hydrated oxide of titanium between the silica particles and the curable reactor Since one type is interposed, it has also been confirmed that there is no decrease in adhesion due to hydrolysis even in the HAST environment.

That is, even after the HAST treatment, since the wettability with the curable resin can be maintained, an excellent effect that the adhesion between the conductor layer and the solder resist is less likely to be reduced can be obtained. In addition, it is possible to improve the physical properties of the cured product by the curable reactor, for example, to reduce the CTE.

In addition, in the present invention, since the melt viscosity can be further reduced by increasing the number of hydroxyl groups based on the hydrated oxide on the surface of the silica particles and effectively providing a curable reactive group, it is preferable to have a curable reactive group on the surface. .

In addition, since the coated silica particles are coated with at least one of a hydrated oxide of aluminum, a hydrated oxide of zirconium, a hydrated oxide of zinc, and a hydrated oxide of titanium, granulation is difficult to occur in the curable resin, and is effectively curable. By providing a reactor, fluidity is improved, and workability such as flattening and thinning is excellent.

Hereinafter, each component of the curable resin composition of the present invention will be described. In addition, in this specification, (meth)acrylate is a term which collectively refers to an acrylate, a methacrylate, and a mixture thereof, and the same applies to other similar expressions.

[Silica particles]

The curable resin composition of the present invention contains silica particles coated with at least one of a hydrated oxide of aluminum, a hydrated oxide of zirconium, a hydrated oxide of zinc, and a hydrated oxide of titanium.

The silica particles to be coated (i.e., silica particles before coating) are not particularly limited, and known and commonly used silica particles that can be used as inorganic fillers may be used. Examples of the coated silica particles include fused silica, spherical silica, amorphous silica, and crystalline silica, but spherical silica is preferable.

As a method of coating silica particles with a hydrated oxide of aluminum, for example, adding an aqueous solution of a water-soluble aluminum compound such as sodium aluminate to a water slurry of the silica particles, and then neutralizing with an alkali or acid to produce aluminum on the surface of the silica particles. Hydrogenated oxides of can be deposited. The amount of silica particles in the water slurry is not particularly limited, but usually 30 to 300 g/l is suitable. As the alkali, sodium hydroxide, potassium hydroxide, ammonia, hydrochloric acid, nitric acid, etc. are used as the acid, and the amount added is an amount capable of forming the hydrated oxide of aluminum by the water-soluble aluminum compound, and the pH is preferably 7±0.5.

As a method of coating the silica particles with the hydrated oxide of zirconium, for example, zirconium on the surface of the silica particles by adding an aqueous solution of a water-soluble zirconium compound such as zirconium oxychloride to the water slurry of the silica particles, and neutralizing with alkali or acid. Hydrogenated oxides of can be deposited. The amount of silica particles in the water slurry is not particularly limited, but usually 30 to 300 g/l is suitable. As the alkali, sodium hydroxide, potassium hydroxide, ammonia, and the like are used, and the amount added is an amount capable of forming the hydrated oxide of zirconium by the water-soluble zirconium compound, and the pH is preferably 7±0.5.

As a method of coating silica particles with a hydrated oxide of zinc, for example, an aqueous solution of a water-soluble zinc compound such as zinc sulfate is added to a water slurry of the silica particles, and then neutralized with an alkali or acid to prevent zinc on the surface of the silica particles. Hydrated oxides can be deposited. The amount of silica particles in the water slurry is not particularly limited, but usually 30 to 300 g/l is suitable. As the alkali, sodium hydroxide, potassium hydroxide, and ammonia are added, and the amount to be added is an amount capable of forming a hydrated oxide of zinc, and the pH is preferably 7±0.5.

As a method of coating silica particles with a hydrated oxide of titanium, for example, an aqueous solution of water-soluble titanium such as titanyl sulfate is added to a water slurry of the silica particles, and then neutralized with an alkali or acid. Hydrated oxides can be deposited. The amount of silica particles in the water slurry is not particularly limited, but usually 30 to 300 g/l is suitable. Hydrochloric acid, nitric acid, and the like are used as the acid, and the amount added is an amount capable of forming the hydrated oxide of titanium by the water-soluble titanium compound, and the pH is preferably 7±0.5.

The coating with the hydration oxide of the metal, i.e., the hydration oxide of aluminum, the hydration oxide of zirconium, the hydration oxide of zinc, and the hydration oxide of titanium, the coating with at least one of the hydration oxide of titanium, hydrate the metal per 100 parts by mass of silica particles. The oxide is preferably coated with 1 to 40 parts by mass, more preferably 3 to 20 parts by mass. By coating in an amount of 1 part by mass or more, it is possible to obtain a cured product having excellent dispersibility of silica particles in the curable resin and less likely to decrease adhesion after HAST treatment.

As described above, in the present invention, even in the case of having a curable reactor on the surface, adhesion after HAST treatment is excellent, and a firm bond with the curable resin is obtained, so that the physical properties of the cured product by the curable reactor are improved, for example, low CTEization is also possible. Here, the curable reactor is not particularly limited as long as it is a group that reacts with a component (for example, a curable resin or an alkali-soluble resin) to be blended into the curable resin composition, and may be a photocurable reactor or a thermosetting reactor. Examples of curable reactive groups include epoxy group, amino group, hydroxyl group, carboxyl group, isocyanate group, imino group, oxetanyl group, mercapto group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group, oxazoline group, methacryl group, acrylic Group, vinyl group, styryl group, etc. are mentioned. The method of introducing the curable reactor to the surface of the coated silica particles is not particularly limited, and may be introduced using a known and conventional method, and a surface treatment agent having a curable reactive group, for example, a coupling agent having a curable reactive group as an organic group. The surface of the coated silica particles may be treated with or the like. 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. Among them, a silane coupling agent is preferable.

It is preferable that the curable reactor on the surface of the coated silica particles is a thermosetting reactor. When the curable resin composition of the present invention contains a photocurable resin, a photocurable reactor may be used.

It is preferable that the average particle diameter of the coated silica particles is preferably 1 μm or less. When the average particle diameter of the inorganic filler is small, aggregation is likely, but in the present invention, by coating the silica particles as described above, the dispersibility is excellent and aggregation is difficult. Moreover, it is preferable that it is smaller than an exposure wavelength, and it is more preferable that it is 0.4 micrometers or less. Further, from the viewpoint of suppressing halation, it is preferably 0.25 µm or more. Here, in the present specification, the average particle diameter of the silica particles is the 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 the D50 measured by laser diffraction method Value. Further, the maximum particle diameter (D100 measured by laser diffraction) of the coated silica particles is preferably 2 μm or less, more preferably 1 μm or less. As a measuring device by the laser diffraction method, the Nikkiso company Microtrac MT3300EXII is mentioned. By being 2 μm or less, a uniform and fine roughened surface is obtained.

The coated silica particles may have an average particle diameter adjusted and are preferably pre-dispersed in, for example, a bead mill or jet mill. In addition, the coated silica particles are preferably blended in a slurry state. By blending in a slurry state, highly dispersed oxidation is facilitated, aggregation is prevented, and handling becomes easy.

The coated silica particles may be used alone or in combination of two or more. The blending amount of the coated silica particles is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 45% by mass or more with respect to the total solid content of the composition. As described above, in the present invention, even if there is a large amount of silica, since the adhesion and dispersibility after HAST treatment are excellent, high silica filling is required for the purpose of improving the physical properties of the cured product, for example, low CTE, warpage resistance, and heat resistance. I can.

[Hardener]

The curable resin composition of the present invention contains, as a curing agent, at least any one of a compound having an active ester group, a compound having a cyanate ester group, and a compound having a maleimide group. By containing such a curing agent, it is possible to obtain a cured product of low dielectric constant. These curing agents may be used alone or in combination of two or more.

(Compound having an active ester group)

It is preferable that the compound having an active ester group is a compound having two or more active ester groups in one molecule. A compound having an active ester group can generally be obtained by condensation reaction of 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. As the phenol compound or naphthol compound, hydroquinone, resorcin, 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, trihydroxybenzo Phenone, tetrahydroxybenzophenone, fluoroglucine, benzenetriol, dicyclopentadienyldiphenol, phenol novolac, and the like. Moreover, as a compound which has an active ester group, naphthalenediol alkyl/benzoic acid type may be sufficient.

As a commercially available compound having an active ester group, a cyclopentadiene-type diphenol compound, such as HPC8000-65T (manufactured by DIC), HPC8100-65T (manufactured by DIC), HPC8150-65T (manufactured by DIC), EXB-8500-65T (Made by DIC Corporation) is mentioned.

(Compound having a cyanate ester group)

The compound having a cyanate ester group is preferably a compound having two or more cyanate ester groups (-OCN) in one molecule. As for the compound having a cyanate ester group, all conventionally known compounds can be used. As a compound having a cyanate ester group, for example, a phenol novolak type cyanate ester resin, an alkylphenol novolak type cyanate ester resin, a dicyclopentadiene type cyanate ester resin, a bisphenol A type cyanate ester resin, and bisphenol F Type cyanate ester resin and bisphenol S type cyanate ester resin. Further, a part of the prepolymer may be triazineated.

As a commercially available compound having a cyanate ester group, a phenol novolak type polyfunctional cyanate ester resin (manufactured by Lonza Japan, PT30S), a prepolymer in which part or all of the bisphenol A dicyanate is triazineized to form a trimer (Lonza Japan Co., Ltd. BA230S75), a dicyclopentadiene structure containing cyanate ester resin (the Lonza Japan company make, DT-4000, DT-7000), etc. are mentioned. Moreover, BA230 (manufactured by Ronza Japan) is also mentioned.

(Compound having a maleimide group)

The compound having a maleimide group is a compound having a maleimide skeleton, and all conventionally known compounds can be used. The compound having a maleimide group preferably has two or more maleimide skeletons, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N,N'- 4,4-diphenylmethane bismaleimide, 1,2-bis(maleimide)ethane, 1,6-bismaleimidehexane, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2,2'-bis-[4-(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4 -Methyl-1,3-phenylenebismaleimide, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bisphenol A diphenyletherbismaleimide, polyphenylmethanemaleimide and oligomers thereof, And it is more preferable that it is at least any 1 type of diamine condensates which have a maleimide skeleton. The oligomer is an oligomer obtained by condensing a compound having a maleimide group as a monomer among the compounds having a maleimide group described above.

As a commercially available compound having a maleimide group, BMI-1000 (4,4'-diphenylmethane bismaleimide, manufactured by Daiwa Kasei Kogyo Corporation), BMI-2300 (phenylmethane bismaleimide, manufactured by Daiwa Kasei Kogyo Corporation), 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 Corporation) ), BMI-7000 (4-methyl-1,3-phenylene bismaleimide, Daiwa Kasei Kogyo Co., Ltd.), BMI-TMH ((1,6-bismaleimide-2,2,4-trimethyl) hexane, Daiwa Kasei Kogyo Corporation), MIR-3000 (biphenyl aralkyl maleimide, Nippon Kayaku Corporation make), etc. are mentioned.

As the curing agent, a compound having an active ester group is preferable from the viewpoint of excellent low dielectric loss. In addition, cyanate esters are also preferred because of their excellent low dielectric loss. By using them in combination with maleimide, a three-dimensional structure including a triazine ring becomes possible, the water absorption characteristics are lowered, and migration resistance is improved, which is preferable.

The blending amount of the curing agent is preferably 1 to 30% by mass when the solid content in the curable resin composition is 100% by mass.

[Epoxy compound]

The curable resin composition of the present invention contains an epoxy compound. Epoxy compounds may be used alone or in combination of two or more.

The epoxy compound is a compound having an epoxy group, and all conventionally known compounds may be used. And polyfunctional epoxy compounds having a plurality of epoxy groups in the molecule. Further, it may be a hydrogenated epoxy compound.

Examples of the polyfunctional epoxy compound include epoxidized vegetable oil; Bisphenol A type epoxy resin; Hydroquinone type epoxy resin; Bisphenol type epoxy resin; Thioether type epoxy resin; Brominated epoxy resin; Novolak type epoxy resin; Biphenol novolak type epoxy resin; Bisphenol F 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 resins or mixtures thereof; Bisphenol S type epoxy resin; Bisphenol A novolak type epoxy resin; Tetraphenylolethane type epoxy resin; Heterocyclic epoxy resin; Diglycidylphthalate resin; Tetraglycidyl xylenoylethane resin; Naphthalene group-containing epoxy resin; Epoxy resins having a dicyclopentadiene skeleton; Glycidyl methacrylate copolymerized epoxy resin; Copolymerization epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives; CTBN-modified epoxy resins and the like may be mentioned, but the present invention is not limited thereto. These epoxy resins may 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 are particularly preferable.

The blending amount of the epoxy compound is preferably 5 to 60% by mass when the solid content in the curable resin composition is 100% by mass.

(Hardening accelerator)

The curable resin composition of the present invention may contain a curing accelerator. As a hardening accelerator, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1 -Imidazole derivatives such as cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, and adducts of imidazole and epoxy; Dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, 4- Amine compounds such as dimethylaminopyridine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid S-triazine derivatives such as adducts can also be used. Further, a metal-based curing accelerator may be used, and organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin may be mentioned. 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. Organic zinc complexes, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like. Among these, from the viewpoint of curability and solvent solubility, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, zinc (II) acetylacetonate, zinc naphthenate, and iron (III) acetylacetonate are preferred, and cobalt (II) Acetylacetonate and zinc naphthenate are more preferable. As the curing accelerator, preferably, a compound that also functions as an adhesive imparting agent is used in combination with the curing accelerator. The curing accelerator may be used alone or in combination of two or more.

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

(Thermoplastic resin)

The curable resin composition of the present invention may further contain a thermoplastic resin in order to improve the mechanical strength of the resulting cured film. It is preferable that the thermoplastic resin is soluble in a solvent. In the case of soluble in a solvent, flexibility is improved when dry film is formed, and generation of cracks and powder fall can be suppressed. As the thermoplastic resin, a thermoplastic polyhydroxypolyether resin, a phenoxy resin, which is a condensation product of epichlorohydrin and various difunctional phenol compounds, or the hydroxyl group of the hydroxyether moiety present in the skeleton, various acid anhydrides or acid chlorides are used. Esterified phenoxy resins, polyvinyl acetal resins, polyamide resins, polyamideimide resins, block copolymers, rubber particles, and the like. Thermoplastic resins may be used alone or in combination of two or more.

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 retardant)

The curable resin composition of the present invention may contain a flame retardant. As the flame retardant, a known and commonly used flame retardant can be used. Known and commonly used flame retardants include phosphoric acid esters and condensed phosphoric acid esters, phosphorus element-containing (meth)acrylates, phosphorus-containing compounds having phenolic hydroxyl groups, cyclic phosphazene compounds, phosphazene oligomers, phosphorus-containing compounds such as phosphinic acid metal salts, and antimony trioxide. , Antimony compounds such as antimony pentoxide, halides such as pentabromodiphenyl ether, octabromodiphenyl ether, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and layered plural oxides such as hydrotalcite and hydrotalcite-like compounds. I can. The flame retardant may be used alone or in combination of two or more.

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

(coloring agent)

The curable resin composition of the present invention may contain a colorant. As the colorant, a known colorant such as red, blue, green, yellow, black, and white can be used, and any of a pigment, a dye, and a dye may be used. However, it is preferable not to contain halogen from the viewpoint of reducing the environmental load and affecting the human body. Colorants may be used alone or in combination of two or more.

The blending amount of the colorant is, for example, 0.01 to 10% by mass of the total solid content of the composition.

(Organic solvent)

The curable resin composition of the present invention can contain an organic solvent for the purpose of preparing the composition or adjusting the viscosity when applied to a substrate or carrier film. 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, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether Glycol ethers such as acetate and tripropylene glycol monomethyl ether; Esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; Aliphatic hydrocarbons such as octane and decane; Known and common organic solvents, such as petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha, can be used. These organic solvents can be used alone or in combination of two or more.

(Other optional ingredients)

Further, the curable resin composition of the present invention may be blended with other known and commonly used additives in the field of electronic materials. Other additives include thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, antistatic agents, anti-aging agents, antioxidants, antibacterial/antifoaming agents, defoaming agents, leveling agents, thickeners, adhesion imparting agents, thixotropic agents, photoinitiation agents. Auxiliaries, sensitizers, organic fillers, elastomers, release agents, surface treatment agents, dispersants, dispersion aids, surface modifiers, stabilizers, phosphors, and the like are mentioned.

Further, the curable resin composition of the present invention may contain a well-known and commonly used inorganic filler other than the coated silica particles as long as the effects of the present invention are not impaired. Examples of such inorganic fillers include silica other than the coated silica particles, Neuburg silica, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, barium sulfate, titanium. Inorganic fillers such as barium oxide, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, and zinc.

Further, the curable resin composition of the present invention may contain a curing agent other than the curing agent described above as long as the effect of the present invention is not impaired. As such a curing agent, a compound having a phenolic hydroxyl group, a polycarboxylic acid and an acid anhydride thereof, an alicyclic olefin polymer, etc. are mentioned, for example.

Further, the curable resin composition of the present invention may contain a thermosetting resin other than the epoxy compound within a range not impairing the effects of the present invention. As such a thermosetting resin, an isocyanate compound, a block isocyanate compound, an amino resin, a benzoxazine resin, a carbodiimide resin, a cyclocarbonate compound, a polyfunctional oxetane compound, an episulfide resin, etc. are mentioned.

Examples of the polyfunctional oxetane compound include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, 1,4- Bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl )Methylacrylate, (3-ethyl-3-oxetanyl)methylacrylate, (3-methyl-3-oxetanyl)methylmethacrylate, (3-ethyl-3-oxetanyl)methylmethacryl In addition to polyfunctional oxetanes such as late or their oligomers or copolymers, oxetane alcohol and novolac resins, poly(p-hydroxystyrene), cardo-type bisphenols, calixarenes, calixresorcin arenes or yarns And etherified products with resins having a hydroxyl group such as sesquioxane. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate, etc. may be mentioned.

Examples of the episulfide resin, that is, a compound having a plurality of cyclic thioether groups in the molecule include bisphenol A episulfide resin. Further, an episulfide resin obtained by substituting a sulfur atom for an oxygen atom in the epoxy group of the novolak type epoxy resin can also be used using the same synthesis method.

Examples of amino resins such as melamine derivatives and benzoguanamine derivatives include methylolmelamine compounds, methylolbenzoguanamine compounds, methylolglycoluril compounds and methylolurea compounds.

As the isocyanate compound, a polyisocyanate compound can be blended. As a polyisocyanate compound, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Aromatic polyisocyanates such as xylylene diisocyanate and 2,4-tolylene isocyanate dimer; Aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate; Alicyclic polyisocyanates such as bicycloheptane triisocyanate; And the adduct body, biuret body, and isocyanurate body etc. of the isocyanate compound mentioned above are mentioned.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. As an isocyanate compound which can react with an isocyanate blocking agent, the polyisocyanate compound etc. mentioned above are mentioned, for example. As an isocyanate blocking agent, For example, a phenol type blocking agent; Lactam-based blocking agents; Active methylene-based blocking agents; Alcohol-based blocking agents; Oxime block agents; Mercaptan-based blocking agents; Acid amide block agents; Imide-based blocking agents; Amine block agents; Imidazole-based blocking agents; And immigration block systems.

(Photocurable resin)

The curable resin composition of the present invention may contain a photocurable resin. The photocurable resin may be a resin that exhibits electrical insulation by curing by irradiation with active energy rays, and a compound having at least one ethylenically unsaturated group in the molecule is preferably used. As the compound having an ethylenically unsaturated group, a photopolymerizable oligomer, a photopolymerizable vinyl monomer, etc. which are well-known and common photosensitive monomers 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 ethylenic unsaturated group as described later can be used. Photocurable resins may be used alone or in combination of two or more.

As the photosensitive monomer, a liquid, solid or semi-solid photosensitive (meth)acrylate compound at room temperature having one or more (meth)acryloyl groups in the molecule may be used. In addition to the purpose of increasing the photoreactivity of the composition, the photosensitive (meth)acrylate compound, which is liquid at room temperature, serves to adjust the composition to a viscosity suitable for various application methods, or to help the solubility in an aqueous alkali solution.

As a photopolymerizable oligomer, an unsaturated polyester type oligomer, a (meth)acrylate type oligomer, etc. are mentioned. Examples of (meth)acrylate oligomers include epoxy (meth)acrylates such as phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, bisphenol-type epoxy (meth)acrylate, and urethane (meth) Acrylate, epoxy urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polybutadiene-modified (meth)acrylate, and the like.

As a photopolymerizable vinyl monomer, it is a well-known thing, 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-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 Vinyl ethers such as ether and triethylene glycol monomethyl vinyl ether; Acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide, etc. Meth)acrylamides; Allyl compounds such as triallyl isocyanurate, diallyl phthalate, and diallyl isophthalate; 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isoboronyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth) ) Esters of (meth)acrylic acid such as acrylate; Hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and pentaerythritol tri (meth)acrylate; Alkoxyalkylene glycol mono(meth)acrylates such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; Ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, trimethylolpropanetri(meth)acrylate , Alkylene polyol poly(meth)acrylate such as pentaerythritol tetra(meth)acrylate and dipentaerythritol hexa(meth)acrylate; Polyoxyalkylene glycol poly(s) such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri(meth)acrylate, etc. Meth)acrylates; Poly(meth)acrylates such as hydroxypivalate neopentyl glycol ester di(meth)acrylate; Isocyanurate type poly(meth)acrylates, such as tris[(meth)acryloxyethyl]isocyanurate, etc. are mentioned.

(Alkaline Soluble Resin)

The curable resin composition of the present invention may contain an alkali-soluble resin. In particular, since it is excellent in developability, the alkali-soluble resin is more preferably a carboxyl group-containing resin. The carboxyl group-containing resin may be a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group or a carboxyl group-containing resin not having an ethylenically unsaturated group. Alkali-soluble resins can be used alone or in combination of two or more.

As a specific example of a carboxyl group-containing resin, the compound (all oligomer and polymer may be sufficient) enumerated below is mentioned.

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

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

(4) Bifunctional epoxy resins such as diisocyanate, 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 nonphenol type epoxy resin A carboxyl group-containing urethane resin obtained by polyaddition reaction of a (meth)acrylate or a partial acid anhydride modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

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

(6) Compounds having 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 during the synthesis of the resin of (2) or (4) above. A carboxyl group-containing urethane resin obtained by adding to the terminal (meth)acrylate.

(7) Carboxyl group-containing resin obtained by reacting a polyfunctional epoxy resin with (meth)acrylic acid, and adding dibasic acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride to the hydroxyl group present in the side chain.

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

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

(10) A monocarboxylic acid containing an unsaturated group is reacted with 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 and propylene oxide, and a polybasic acid anhydride is added to the reaction product. Carboxyl group-containing resin obtained by reaction.

(11) A monocarboxylic acid containing an unsaturated group is reacted with 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 and propylene carbonate, and a polybasic acid anhydride is added to the reaction product. Carboxyl group-containing resin obtained by reaction.

(12) In 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 unsaturation such as (meth)acrylic acid Obtained by reacting a group-containing monocarboxylic acid and reacting polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic anhydride with respect to the alcoholic hydroxyl group of the obtained reaction product. Carboxyl group-containing resin.

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

The acid value of the alkali-soluble resin is suitably in the range of 40 to 200 mgKOH/g, 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, whereas when the acid value of the alkali-soluble resin is 200 mgKOH/g or less, drawing of a normal cured product pattern becomes easy, which is preferable.

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, furthermore 1,500 to 100,000. When the weight average molecular weight is 1,500 or more, the dry-to-touch performance is good, the moisture resistance of the coating film after exposure is good, the film reduction during development can be suppressed, and the decrease in resolution can be suppressed. On the other hand, when the weight average molecular weight is 150,000 or less, developability is good and storage stability is also excellent.

The blending amount of the alkali-soluble resin is, for example, 5 to 50 mass% of the total solid content of the composition.

(Photoreaction initiator)

The curable resin composition of the present invention may contain a photoreaction initiator. The photoreaction initiator may be any one of a photopolymerization initiator that generates a radical by irradiation with light and a photobase generator that generates a base by irradiation with light. In addition, the photoreaction initiator may, of course, be a compound that generates both a radical and a base by irradiation with light. Light irradiation means irradiating ultraviolet rays in the range of 350 to 450 nm in wavelength.

As a photoinitiator, for example, 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, Bisacylphosphine oxides such as 6-trimethylbenzoyl)-phenylphosphine oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, blood Monoacylphosphine oxides such as isopropyl valeoylphenylphosphinate and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 1-hydroxy-cyclohexylphenylketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1 -{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropane- Hydroxyacetophenones such as 1-one; Benzoin, such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; Benzoin alkyl ethers; Benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2- Acetophenones such as (dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4-morpholinyl)phenyl]-1-butanone and N,N-dimethylaminoacetophenone; Thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 2,4-di Thioxanthones such as isopropyl thioxanthone; Anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione,1-[4-(phenylthio)-,2-(O-benzoyloxime)],ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-car Oxime esters such as bazol-3-yl]-,1-(O-acetyloxime); Bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)- Titanocenes such as bis[2,6-difluoro-3-(2-(1-pil-1-yl)ethyl)phenyl]titanium; Phenyl disulfide 2-nitrofluorene, butyloin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. are mentioned. A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more types.

The photobase generator is a compound that generates at least one basic substance capable of functioning as a catalyst for a thermosetting reaction by changing the molecular structure or cleaving the molecule by irradiation with light such as ultraviolet rays or visible light. As a basic substance, a secondary amine and a tertiary amine are mentioned, for example.

As a photobase generator, for example, α-aminoacetophenone compound, oxime ester compound, acyloxyimino compound, N-formylated aromatic amino compound, N-acylated aromatic amino compound, nitrobenzyl carbamate compound, alkoxy And benzyl carbamate compounds. Among them, an oxime ester compound and an α-aminoacetophenone compound are preferable, and an oxime ester compound is more preferable, and ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3 -Yl]-,1-(O-acetyloxime) is more preferable. As the α-aminoacetophenone compound, it is particularly preferable to have two or more nitrogen atoms. Photobase generators may be used individually by 1 type, and may be used in combination of 2 or more types. In addition, as a photobase generator, a quaternary ammonium salt etc. are mentioned.

As other photobase generators, WPBG-018 (trade name: 9-anthrylmethyl N,N'-diethylcarbamate (9-anthrylmethyl N,N'-diethylcarbamate)), WPBG-027 (trade name: (E)- 1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine ((E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine)), WPBG-082( Trade name: guanidinium 2-(3-benzoylphenyl)propionate (guanidinium2-(3-benzoylphenyl)propionate)), WPBG-140 (trade name: 1-(anthraquinone-2-yl)ethylimidazolecarboxyl Rate (1-(anthraquinon-2-yl)ethyl imidazolecarboxylate)) or the like may be used.

In addition, some substances of the photopolymerization initiator described above also function as a photobase generator. As the photopolymerization initiator which also functions as a photobase generator, an oxime ester photopolymerization initiator and an α-aminoacetophenone photopolymerization initiator are preferable.

The blending amount of the photoreaction initiator is, for example, 0.01 to 30 mass% of the total solid content of the composition.

The curable resin composition of the present invention is not particularly limited, and for example, any of a thermosetting resin composition, a photocurable thermosetting resin composition, and a photosensitive thermosetting resin composition may be used. Moreover, an alkali developing type may be sufficient, and a negative type or a positive type may be sufficient. Specific examples include a thermosetting resin composition, a photocurable thermosetting resin composition, a photocurable thermosetting resin composition containing a photoinitiator, a photocurable thermosetting resin composition containing a photobase generator, a negative photocurable thermosetting resin composition, and a positive photosensitive thermosetting resin. Composition, alkali developing type photocurable thermosetting resin composition, solvent developing type photocurable thermosetting resin composition, swelling release type thermosetting resin composition, dissolution release type thermosetting resin composition, and the like, but are not limited thereto.

As for the optional component contained in the curable resin composition of the present invention, a known and commonly used component may be selected according to the curability and use.

For example, when the curable resin composition of the present invention is a thermosetting resin composition (not including a photopolymerization initiator), a thermosetting resin is contained. Further, it is preferable to contain a curing accelerator. It is preferred to contain a curing agent. The blending amount of the thermosetting resin is preferably 1 to 50% by mass based on the total solid content of the composition. The blending amount of the curing accelerator is preferably 0.01 to 30% by mass based on the total solid content of the composition. The blending amount of the curing agent is preferably 0.01 to 30% by mass based on the total solid content of the composition.

Further, when the curable resin composition of the present invention is a photocurable thermosetting resin composition, it contains a photocurable resin, a thermosetting resin, and a photoreaction initiator. When setting it as an alkali developing type, the photocurable resin may be an alkali-soluble resin, and may contain an alkali-soluble resin further. Further, it is preferable to contain a curing accelerator. It is preferable that the blending amount of the alkali-soluble resin is 5 to 50 mass% of the total solid content of the composition. The blending amount of the thermosetting resin is preferably 1 to 50% by mass based on the total solid content of the composition. The blending 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 blending amount of the photoreaction initiator is preferably 0.01 to 30% by mass based on the total solid content of the composition. The blending amount of the curing accelerator is preferably 0.01 to 30% by mass based on the total solid content of the composition.

The curable resin composition of the present invention may be used after forming a dry film, or may be used as a liquid. In the case of using as a liquid, it may be one liquid or two or more liquids.

The dry film of the present invention has a resin layer obtained by applying and drying the curable resin composition of the present invention on a carrier film. When forming a dry film, first, after diluting the curable resin composition of the present invention with the organic solvent and adjusting it to an appropriate viscosity, a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, A gravure coater, a spray coater, or the like is applied to the carrier film with a uniform thickness. Thereafter, a resin layer can be formed by drying the applied composition for 1 to 30 minutes at a temperature of usually 40 to 130°C. There is no restriction|limiting in particular with respect to the coating film thickness, In general, the film thickness after drying is suitably selected in the range of 3 to 150 micrometers, Preferably it is 5 to 60 micrometers.

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. There is no particular limitation on the thickness of the carrier film, but it is generally appropriately selected in the range of 10 to 150 µm. It is more preferably in the range of 15 to 130 μm.

After forming the resin layer containing the curable resin composition of the present invention on the carrier film, for the purpose of preventing dust from adhering to the surface of the resin layer, a protective film (cover Film) is preferably laminated. As a peelable protective film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. can be used, for example. As a protective film, what is necessary is just what is smaller than the adhesive force of a resin layer and a carrier film when peeling a protective film.

Further, in the present invention, a resin layer may be formed by applying and drying the curable resin composition of the present invention on the protective film, and a carrier film may be laminated on the surface thereof. That is, when manufacturing a dry film in this invention, as a film to which the curable resin composition of this invention is applied, you may use either a carrier film and a protective film.

As a method for manufacturing an electronic component using the curable resin composition of the present invention, a conventionally known method may be used. For example, when the curable resin composition of the present invention is a thermosetting resin composition (not including a photopolymerization initiator), and a dry film having a three-layer structure in which a resin layer is sandwiched between a carrier film and a protective film, print by the following method. A wiring board can be manufactured. Either of the carrier film or the protective film is peeled off from the dry film, and heat-laminated on the circuit board on which the circuit pattern was formed, and then thermosetting. Thermal curing may be cured in an oven or by a hot plate press. When laminating or hot plate pressing the circuit board and the dry film of the present invention, a copper foil or a circuit board may be laminated at the same time. A substrate having an insulating layer can be manufactured by forming a pattern or a via hole by laser irradiation or a drill at a position corresponding to a predetermined position on the substrate on which the circuit pattern is formed, and exposing the circuit wiring. At this time, when a component (smear) that cannot be completely removed and remains on the circuit wiring in the pattern or via hole is present, a desmear treatment is performed. The remaining side of the carrier film or the protective film may be peeled off at any time after lamination, after thermosetting, after laser processing, or after desmear treatment.

Subsequently, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, known methods such as vapor deposition, sputtering, and ion plating can be used. In the case of wet plating, the surface of the first cured resin composition layer (insulation layer) is treated with an oxidizing agent such as permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide/sulfuric acid, and nitric acid. As the oxidizing agent, an aqueous sodium hydroxide solution (an alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. Next, a conductor layer is formed by a method combining electroless plating and electrolytic plating. In addition, a plating resist having an inverse pattern with the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. As a method of pattern formation after that, for example, a subtractive method, a semi-additive method, or the like known to those skilled in the art can be used. In addition, the connection method of the interlayer circuit may be a connection using a copper pillar.

Next, the surfaces of the conductor layer and the insulating layer are roughened. As the roughening treatment liquid, for example, a composition containing an aromatic compound having an amino group and an aromatic ring, a polybasic acid having two or more carboxyl groups, and a halide ion can be used. As a brand name, 01CZ etc. made by a Mack company are mentioned, for example.

In this way, the insulating layer and the conductor layer are alternately formed, and a solder resist may be formed on the circuit of the outermost layer. For example, a solder resist may be formed according to the method described in paragraphs 70 to 76 of Japanese Patent No. 5941180.

The curable resin composition of the present invention is suitably used to form a cured film on an electronic component, in particular, to form a cured film on a printed wiring board, and is more preferably used to form a permanent film. More suitably, the curable resin composition of the present invention is used to form an interlayer insulating layer from the viewpoint of excellent adhesion after HAST treatment with the conductor layer and the solder resist. Further, it is suitable for the formation of a permanent film (especially an interlayer insulating layer) for a printed wiring board requiring a high degree of reliability, for example a package substrate, particularly for FC-BGA. Further, the curable resin composition of the present invention can be suitably used also for a printed wiring board provided with a wiring pattern having a small circuit surface roughness, for example, a printed wiring board for high frequency use. For example, even if the surface roughness Ra is 0.05 µm or less, particularly 0.03 µm or less, it can be suitably used. In addition, it can be suitably used also when forming a cured film on a low-polarity substrate, for example, a substrate containing an active ester. The curable resin composition of the present invention contains an inorganic filler such as silica or barium sulfate, for example, 30% by mass or more, and further 40% by mass or more, from the viewpoint of excellent adhesion after HAST treatment with a solder resist containing a large amount of silica. It can be suitably used for forming a cured film that is in close contact with the cured product. In addition, the curable resin composition of the present invention can be used as one for forming a solder resist or a coverlay.

As an electronic component, applications other than a printed wiring board may be used, for example passive components, such as an inductor.

Example

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to the following examples. In addition, all of "parts" and "%" below are based on mass unless otherwise noted.

[Inorganic filler coating and surface treatment]

(Silica particles coated with hydrated oxide of aluminum)

Spherical silica particles (SFP-20M manufactured by Denka Corporation, average particle diameter: 0.4 µm) 50 g of a water slurry was heated to 70° C., and a 20% sodium aluminate (NaAlO ₂ ) aqueous solution was added to the silica particles with alumina (Al ₂ O). ₃ ) It added 2 to 3% in conversion. Thereafter, a 20% aqueous sodium hydroxide solution was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered with water by a filter press and dried under vacuum to obtain a solid substance of silica particles coated with a hydrated oxide of aluminum.

(Silica particles coated with hydrated oxide of zirconia)

After heating 50 g of a water slurry of spherical silica particles (SFP-20M manufactured by Denka Corporation, average particle diameter: 0.4 μm) to 70° C., an aqueous solution of a water-soluble zirconium compound such as 100 g/l zirconium oxychloride was added to the silica particles with zirconia ( ZrO ₂ ) 2 to 3% in conversion was added. Thereafter, a 20% aqueous sodium hydroxide solution was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered with water by a filter press and dried under vacuum to obtain a solid substance of silica particles coated with a hydrated oxide of zirconia.

(Silica particles coated with hydrated oxide of zinc)

After 50 g of a water slurry of spherical silica particles (SFP-20M manufactured by Denka Corporation, average particle diameter: 0.4 µm) was heated to 70° C., an aqueous solution of zinc sulfate was added 2 to 3% in terms of ZnO to the silica particles. Thereafter, a 20% aqueous sodium hydroxide solution was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered with water by a filter press and dried under vacuum to obtain a solid substance of silica particles coated with a hydrated oxide of zinc.

(Silica particles coated with hydrated oxide of titanium)

Spherical silica particles (SFP-20M manufactured by Denka Corporation, average particle diameter: 0.4 µm) 50 g of a water slurry was heated to 70° C., and then 100 g/l titanyl sulfate aqueous solution was added to the silica particles in terms of TiO ₂ 2 to 3% Added. Thereafter, a 20% aqueous sodium hydroxide solution was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered with water by a filter press and dried under vacuum to obtain a solid substance of silica particles coated with a hydrated oxide of titanium.

(Silica particles coated with hydrated oxide of aluminum and surface-treated with methacrylsilane)

50 g of silica particles coated with hydrated oxide of aluminum obtained above, 48 g of PMA as a solvent, and 1 g of a silane coupling agent having a methacrylic group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly dispersed, followed by filtration and washing with water. Solids of silica particles surface-treated with methacrylsilane were obtained by vacuum drying.

(Silica particles coated with hydrated oxide of aluminum and surface-treated with epoxysilane)

50 g of silica particles coated with hydrated oxide of aluminum obtained above, 48 g of PMA as a solvent, and 1 g of a silane coupling agent having an epoxy group (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly dispersed, followed by filtration, washing, and vacuum. A solid product of silica particles surface-treated with epoxysilane was obtained by drying.

(Silica particles coated with hydrated oxide of aluminum and surface-treated with phenylaminosilane)

50 g of silica particles coated with a hydrated oxide of aluminum obtained above, 48 g of PMA as a solvent, and 1 g of a silane coupling agent having a phenylamino group (KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly dispersed, followed by filtration and washing with water. A solid product of silica particles surface-treated with phenylaminosilane was obtained by vacuum drying.

(Silica particles surface-treated with phenylaminosilane)

Uniform dispersion of 50 g of spherical silica particles (SFP-20M manufactured by Denka Corporation, average particle diameter: 0.4 μm), 48 g of PMA as a solvent, and 1 g of a silane coupling agent having a phenylamino group (KBM-573 manufactured by Shin-Etsu Chemical Industries, Ltd.) And filtration, washing with water, and vacuum drying to obtain solids of silica particles surface-treated with phenylaminosilane.

(Silica particles surface-treated with methacrylsilane)

50 g of spherical silica particles (SFP-20M manufactured by Denka Corporation, average particle diameter: 0.4 μm), 48 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and a silane coupling agent having a methacrylic group (manufactured by Shin-Etsu Chemical Co., Ltd.) 1 g of KBM-503) was uniformly dispersed, followed by filtration, washing with water, and vacuum drying to obtain a solid substance of silica particles surface-treated with methacrylsilane.

(Talc coated with hydrated oxide of aluminum and surface-treated with phenylaminosilane)

Talc (SG2000 manufactured by Nippon Talc, average particle diameter: 1.0 μm) 50 g of water slurry was heated to 70° C., and then a 20% sodium aluminate (NaAlO ₂ ) aqueous solution was talc while maintaining the pH at 7±1 with hydrochloric acid. About 20% was added in terms of alumina (Al ₂ O ₃ ). Thereafter, a 20% aqueous sodium hydroxide solution was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered with water by a filter press and dried under vacuum to obtain a talc solid coated with a hydrated oxide of aluminum.

50 g of talc coated with a hydrated oxide of aluminum obtained above, 48 g of PMA as a solvent, and 1 g of a silane coupling agent having a phenylamino group (KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly dispersed, followed by filtration, washing, and vacuum. A solid product of talc surface-treated with phenylaminosilane was obtained by drying.

(Synthesis of alkali-soluble resin A-1)

In an autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device and a stirring device, a novolac cresol resin (trade name ``Shonol CRG951'', manufactured by Showa Kobunshi, OH equivalent: 119.4) 119.4 parts, potassium hydroxide 1.19 parts And 119.4 parts of toluene were introduced, and the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Then, 63.8 parts of propylene oxide was gradually added dropwise, and reacted at 125 to 132°C and 0 to 4.8 kg/cm ² for 16 hours. Then, it cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to this reaction solution, and potassium hydroxide was neutralized, and the novolac-type cresol of 62.1% nonvolatile matter and a hydroxyl value of 182.2 mgKOH/g (307.9 g/eq.) A propylene oxide reaction solution of resin was obtained. This was obtained by adding an average of 1.08 mol of propylene oxide per 1 equivalent of phenolic hydroxyl group.

293.0 parts of a propylene oxide reaction solution of the obtained novolak type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone and 252.9 parts of toluene were introduced into a reactor equipped with a stirrer, a thermometer and an air suction tube, and air was introduced into 10 ml. It was blown at a rate of /min, and reacted at 110°C for 12 hours while stirring. The water produced by the reaction was an azeotropic mixture with toluene, and 12.6 parts of water flowed out. Then, it cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 parts of 15% sodium hydroxide aqueous solution, and then washed with water. Thereafter, toluene was distilled off while replacing 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolac-type acrylate resin solution. Then, 332.5 parts of the obtained novolac-type acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air intake tube, air was blown at a rate of 10 ml/min, and tetrahydrophthalic acid while stirring. 60.8 parts of anhydrides were gradually added, reacted at 95 to 101°C for 6 hours, cooled, and then taken out. In this way, a solution of the carboxyl group-containing photosensitive resin A-1 having a nonvolatile content of 65% and an acid value of 80 mgKOH/g of a solid was obtained.

[Examples 1 to 13, Comparative Examples 1 to 5]

Various components shown in the following Tables 1 to 3 were blended in the proportions (parts by mass) shown in Tables 1 to 3, and after viscosity was adjusted with an organic solvent, premixed with a stirrer, and then kneaded with a bead mill to prepare a curable resin composition. . Similarly, after mixing the various components shown in Table 4 in the ratio (parts by mass) shown in Table 4, adjusting the viscosity with an organic solvent, premixing with a stirrer, kneading with a bead mill, <Solder Resist (SR) described later A curable resin composition for forming a solder resist (hereinafter, also referred to as a "solder resist composition") to be used in the evaluation of adhesion to> was prepared. These curable resin compositions were passed through a filter filter having an eye size of 15 μm to remove granulation, and then the following dry film was prepared.

<Production of dry film>

To the curable resin composition obtained as described above, 300 g of methyl ethyl ketone was added, diluted, and stirred for 15 minutes with a stirrer to obtain a coating solution. The coating solution was applied on a 38 μm-thick polyethylene terephthalate film (PET film, Unitika Corporation Envlet PTH-25) having an arithmetic surface roughness Ra 150 nm, and Examples 1 to 13 and Comparative Examples 1 to 5 were 100°C. At temperature, the solder resist composition was dried at 80° C. for 10 minutes to form a resin layer having a thickness of 20 μm. Next, a polypropylene film (protective film, OPP-FOA manufactured by Futamura) having a thickness of 18 µm was bonded to the resin layer to prepare a dry film having a thickness of the resin layer of 20 µm.

Further, in the same manner as above, a dry film having a thickness of the resin layer of 30 µm was produced.

<Lamination conditions of dry film>

After peeling off the protective film of the dry film, using a vacuum laminator (CVP-300: manufactured by Nikko Materials), Examples 1 to 13 and Comparative Examples 1 to 5 were vacuum 3 hPa in the first chamber, 100° C., and the solder resist composition was At 90°C, it is affixed under the conditions of a vacuum time of 30 seconds, laminated to the object, and presses are performed under the conditions of a press pressure of 0.5 MPa, 80°C, and a press time of 30 seconds.

<Evaluation of dispersibility>

The dispersion degree of each composition of Examples and Comparative Examples was confirmed by using a grind gauge having a width of 90 mm, a length of 240 mm, and a maximum depth of 25 μm in accordance with JIS K5101 and JIS K5600.

As a view of the degree of dispersion, the section confirmed 5 or more tablets was confirmed.

◎: No particles are found, or 5 μm or less

○: more than 5 μm and 12.5 μm or less

△: more than 12.5㎛ 20㎛ or less

×: more than 20 μm

<genetic tangent>

A dry film with a resin layer thickness of 30 µm prepared in Examples and Comparative Examples was laminated under the above conditions on a glossy surface of electrolytic copper foil GTS-MP-18 µm (manufactured by Furukawa Circuit Foil Co., Ltd.), and then flattened and PET on resin After peeling the film, the resin layer was completely cured (190°C, 60 minutes). After that, the cured film was peeled off from the copper foil to obtain a cured film having a thickness of 30 µm.

The cured film was cut into a length of 80 mm and a width of 2 mm, and a dielectric loss tangent at a measurement temperature of 22° C. and 5 GHz was measured with a perturbation method cavity resonator using 8510C, a network analyzer manufactured by Keysight, and CAMA-S, a complex relative permittivity calculation software manufactured by KEAD.

◎: less than 0.006 dielectric loss tangent

○: Dielectric loss tangent value 0.006 or more and less than 0.009

△: dielectric loss tangent value 0.009 or more and less than 0.012

×: dielectric loss tangent value 0.012 or more

<Measurement of thermal linear expansion coefficient CTE>

After peeling the cured film of 30 µm obtained by the same method as the dielectric tangent from the copper foil, cut it into a size of measurement size (3 mm x 16 mm), and measure CTE by tensile load measurement using TMA-Q400 (manufactured by TA Instruments). Measured. A test load of 5 g and a sample were heated from room temperature at a temperature rising rate of 10°C/min, and were continuously measured twice. The average coefficient of thermal linear expansion (?1) in the region of Tg or less in the second time was calculated.

◎: 30ppm or less

○: more than 30 ppm and less than 40 ppm

△: More than 40 ppm and less than 45 ppm

×: more than 45 ppm

<Adhesion with solder resist (SR)>

The composition of each Example and Comparative Example was coated on an ultrathin copper foil (manufactured by Mitsui Kinjoku Co., Ltd., MT18SD-EX, having a support made of 18 µm copper), and dried at 100° C. for 10 minutes to have a dry coating I got a sieve. Subsequently, it laminated|laminated under the conditions of 0.5 MPa, 120 degreeC, 1 minute, and 1 Torr so that the dry coating film of this laminated body might be bonded to the FR-4 (glass epoxy) substrate as a support body. Thereafter, the unreacted thermosetting component was completely cured by heating at 190° C. for 60 minutes.

Thereafter, the 18 µm copper support was peeled off, and the ultrathin copper foil was fully etched with an etching solution (McK bright QE-7300) to obtain a substrate having a cured film.

Thereafter, as a pretreatment for forming the solder resist layer, an acid treatment was performed on the substrate having the cured film to obtain a low profile cured film having Rz = 2 µm or less.

On the cured film, a 20 µm dry film having a resin layer containing the solder resist composition prepared above was laminated under the above conditions.

Thereafter, using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), the entire surface was exposed from the dry film (exposure amount: 400 to 600 mJ/cm ² ), and then the polyethylene terephthalate film was peeled from the dry film, and the resin layer Exposed. Then, development was performed for 60 seconds under the conditions of 30 degreeC and spray pressure 2 kg/cm ² using 1 weight% Na ₂ CO ₃ aqueous solution. Subsequently, after irradiating the resin layer at an exposure dose of 1 J/cm ² in a UV conveyor equipped with a high-pressure mercury lamp, the resin layer was completely cured by heating at 160° C. for 60 minutes to prepare an evaluation substrate having a cured solder resist film. A cross-section peeling test was performed on this cured film, and the adhesion between the cured film containing the compositions of Examples and Comparative Examples and the cured solder resist film was confirmed. Specifically, based on JIS K5400, 100 square grids (10×10) of 1 mm side were made by a cross cutter with a cutout reaching the cured film of Examples and Comparative Examples, and cellophane tape was completely adhered thereon. It was removed, and it was checked how many out of 100 are in close contact.

Similarly, the adhesion test was performed even after HAST conditions 130° C. 85% 100 hours.

◎: 96 or more/100

○: 61/100 to 95/100

△: 11/100 to 60/100

×: 10/100 or less

<Adhesion with copper>

As a pretreatment, the polished surface of the electrolytic copper foil GTS-MP-18 µm (manufactured by Furukawa Circuit Foil Corporation) was sprayed with 01CZ manufactured by McCormick Corporation to perform roughening treatment to obtain a low profile copper foil having a surface roughness Ra of 0.04 µm.

A dry film having a resin layer thickness of 20 µm produced in each of the Examples and Comparative Examples was laminated on the treated surface, and heat cured at 190°C for 60 minutes to obtain a sample in which an insulating layer was formed.

The insulating layer of this sample and the FR-4 (glass epoxy) substrate were adhered with an adhesive (AR-S 30 manufactured by Nichi Reflector). This adhesive body was treated for 100 hours in a high-temperature, high-humidity bath in an atmosphere of 130°C and 85% humidity. Then, the copper foil was peeled off using the tensile tester AG-X, and the strength at that time was evaluated.

After the initial value of this sample and the HAST test at 130° C. 85% RH for 100 hours, both samples were measured for peel strength based on JIS C6481 by Shimadzu Seisakusho Autograph AG-X.

The higher the peel strength, the better the adhesion, and the lower the adhesion strength decrease rate before and after the HAST test is better.

(Before HAST-After HAST)/Before HAST×100 (%)

HAST 130° C. 85% 100hrs A reduction rate of 40% or less is preferable.

*1: ESN-475V manufactured by Shinnittetsu Sumikin Chemical Co., Ltd., naphthol type (epoxy equivalent = 340g/eq)

*2: Nippon Kayaku Corporation NC-3000L, Biphenyl type (epoxy equivalent = 272g/eq)

*3: Showa Denko Corporation PETG (epoxy equivalent = 92g/eq)

*4: YX7200B35 manufactured by Mitsubishi Chemicals, epoxy compound

*5: EXB-8500-65T manufactured by DIC, a compound having an active ester group (active ester equivalent = 223 g/eq)

*6: HPC-9500 manufactured by DIC, a compound having a phenolic hydroxyl group (hydroxyl equivalent = 150 g/eq)

*7: BA230 manufactured by Ronza Japan, a compound having a cyanate ester group (cyanate equivalent = 232 g/eq)

*8: PT30 manufactured by Ronza Japan, a compound having a cyanate ester group (cyanate equivalent = 124 g/eq)

*9: Nippon Kayaku Corporation MIR-3000, a compound having a maleimide group

*10: Mitsubishi Chemical P200, an adduct body of imidazole and epoxy

*11: Wako Junyaku High School's Zinc Naphthenate (II) Mineral Spirit

*12: dimethylaminopyridine

*13: Clariant Chemical's OP-935

*14: Silica particles prepared above and coated with a hydrated oxide of aluminum

*15: Silica particles prepared above and coated with a hydrated oxide of zirconium

*16: silica particles prepared above and coated with hydrated oxide of zinc

*17: Silica particles coated with a hydrated oxide of titanium, adjusted above

*18: Silica particles prepared above, coated with a hydrated oxide of aluminum, and surface-treated with methacrylsilane

*19: Silica particles prepared above, coated with hydrated oxide of aluminum, and surface-treated with epoxysilane

*20: Silica particles prepared above, coated with a hydrated oxide of aluminum, and surface-treated with phenylaminosilane

*21: Silica particles prepared above and surface-treated with phenylaminosilane

*22: Silica particles prepared above and surface-treated with methacrylsilane

*23: SFP-20M manufactured by Denka Corporation, average particle diameter: 0.4 μm (silica)

*24: Talc prepared above, coated with hydrated oxide of aluminum, and surface-treated with phenylaminosilane

*25: phenol starting type photosensitive carboxyl group-containing resin synthesized in Synthesis Example 1

*26: Dicyandiamide

*27: melamine

*28: Irgacure TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by BASF Japan

*29: BASF Japan company Irgacure OXE02 (ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyloxime)

*30: DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Corporation

From the results shown in Tables 1 to 3, it can be seen that the curable resin compositions of Examples 1 to 13 of the present invention have excellent adhesion after HAST treatment with the conductor layer and the solder resist, and a cured product with low dielectric loss tangent can be obtained. .

Claims (5)

Silica particles coated with at least one of a hydrated oxide of aluminum, a hydrated oxide of zirconium, a hydrated oxide of zinc, and a hydrated oxide of titanium,
An epoxy compound,
As a curing agent, at least any one of a compound having an active ester group, a compound having a cyanate ester group, and a compound having a maleimide group
Curable resin composition comprising a. The curable resin composition according to claim 1, wherein the coated silica particles further have a curable reactive group on their surface. A dry film comprising a resin layer obtained by applying and drying the curable resin composition according to claim 1 to a film. A cured product obtained by curing the curable resin composition according to claim 1 or 2 or the resin layer of the dry film according to claim 3. An electronic component comprising the cured product according to claim 4.