WO2019187588A1

WO2019187588A1 - Curable resin composition, dry film, cured object, and electronic component

Info

Publication number: WO2019187588A1
Application number: PCT/JP2019/002809
Authority: WO
Inventors: 千穂植田; 岡田　和也; 沙和子嶋田; 知哉工藤
Original assignee: 太陽インキ製造株式会社
Priority date: 2018-03-30
Filing date: 2019-01-28
Publication date: 2019-10-03
Also published as: CN111936575A; KR20200140289A; JP2019178308A; CN111936575B; TW201941953A; JP7076263B2

Abstract

Provided are: a curable resin composition which is excellent in terms of conductor layer/solder resist adhesion after an HAST treatment and which can give cured objects having a low dielectric dissipation factor; a dry film including a resin layer obtained from the composition; a cured object obtained by curing a resin layer which is either the composition or the dry film; and an electronic component including the cured object. The curable resin composition is characterized by comprising: silica particles coated with at least any one of hydrated aluminum oxide, hydrated zirconium oxide, hydrated zinc oxide, and hydrated titanium oxide; an epoxy compound; and a hardener which is any one of active-ester-group-containing compounds, cyanate-ester-group-containing compounds, and maleimide-group-containing compounds.

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, the main component is a curable resin such as a carboxyl group-containing resin or an epoxy resin for an interlayer insulating material or a solder resist material. Furthermore, resin compositions containing additive components such as fillers are widely used.
In addition, the surface of the resin insulation layer such as an interlayer insulation material is usually roughened by a conductor layer formation process (copper foil rough surface transfer or chemical treatment before copper plating), and is in close contact with the solder resist material. Improves sex.
In the cured product made of the conventional resin composition used as such an interlayer insulating material, there is a problem that delay and loss of electric signals are unavoidable when communicating in a high frequency region.
In recent years, due to such a transmission loss problem, the surface of an interlayer insulating material tends to become a roughening-free or low-roughening surface (so-called low profile substrate), and the material includes a low-polarity insulating material containing an active ester, etc. The low dielectric loss material has come to be used.

On the other hand, higher reliability (HAST resistance, PCT resistance, heat resistance, toughness, low warpage, thermal dimensional stability, etc.) is required for permanent films such as solder resists used for semiconductor package substrates. It has become.
As a method for imparting high reliability to such a solder resist material or the like, it is generally performed to improve the thermophysical properties, for example, by highly filling the composition with an inorganic filler. Among these inorganic fillers, silica is particularly excellent in filling properties, has a low coefficient of thermal expansion (CTE), and can be easily introduced with a curable reactive group, and has been widely used to improve the properties of solder resists. (See Patent Document 1). However, in such a solder resist material containing a large amount of silica, as with the low-profile substrate material that solves the above-mentioned transmission loss problem, it becomes a low-polarity composition, resulting in poor adhesion, particularly HAST treatment. Later, it was found that a new problem arises that the adhesion tends to decrease.

JP 2012-83467 A (Claims)

On the other hand, an interlayer insulating material used as a material for a low profile substrate that solves the problem of transmission loss is blended with components for reducing polarity such as active esters as described above in order to reduce the dielectric loss tangent. However, it has been found that when such a low-polarity component is included, or when the conductor layer is roughening-free or has a low-roughening surface, the adhesion with the conductor layer or the solder resist decreases. Similarly to the solder resist material described above, when silica is highly filled as an inorganic filler from the viewpoint of CTE mismatch or low dielectric loss tangent with a semiconductor chip, the ratio of the curable resin is reduced, so that the anchor effect of desmear is reduced. When it was not obtained, it turned out that it becomes a cause that adhesiveness with a soldering resist or a conductor layer falls more. Therefore, when using a low-polarity material or a high-filling material such as silica as described above, excellent adhesion is maintained even after the HAST treatment with the conductor layer and the solder resist, particularly the solder resist containing silica. It was difficult. Furthermore, since the solder resist imparting high-strength physical properties contains silica having a curable reactive group, there is a problem in that the shrinkage of curing tends to increase as the diameter of the silica decreases, and the adhesion is further lowered.

From the technical background as described above, the conductive layer is free of roughening in the interlayer insulating material containing silica and a component aiming at low polarity such as active ester, which is used to solve the problem of transmission loss. Even if it is a low roughened surface, it has excellent adhesion after the HAST treatment with the conductor layer, and even if the surface of the interlayer insulating material and the conductor layer is a roughening free surface or a low roughened surface, as described above. It is required to have excellent adhesion after HAST treatment with a solder resist containing a large amount of silica particles.

Accordingly, an object of the present invention is to have a curable resin composition that has excellent adhesion after HAST treatment with a conductor layer and a solder resist, and that can obtain a cured product having a low dielectric loss tangent, and a resin layer obtained from the composition. A dry film, 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 diligently studied focusing on the surface treatment of silica used as an inorganic filler in order to achieve the above object. As a result, the inventors used silica particles coated with any one of aluminum hydrated oxide, zirconium hydrated oxide, zinc hydrated oxide, and titanium hydrated oxide, And it discovered that the said subject could be solved by using a specific compound as a hardening | curing agent of an epoxy compound, and came to complete this invention.

That is, the curable resin composition of the present invention is coated with at least one of aluminum hydrated oxide, zirconium hydrated oxide, zinc hydrated oxide, and titanium hydrated oxide. Silica particles, an epoxy compound, and 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 as a curing agent. It is.

In the curable resin composition of the present invention, the coated silica particles preferably 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 the curable resin composition to the film and drying it.

The cured product of the present invention 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.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in the adhesiveness after a HAST process with a conductor layer and a soldering resist, The curable resin composition which can obtain the hardened | cured material of a low dielectric loss tangent, Dry which has a resin layer obtained from this composition A cured product of the resin layer of the film, the composition or the dry film, and an electronic component having the cured product can be provided.

The curable resin composition of the present invention is a silica coated with at least one of aluminum hydrated oxide, zirconium hydrated oxide, zinc hydrated oxide, and titanium hydrated oxide. At least one of particles (hereinafter also referred to as “the coated silica particles”), an epoxy compound, a compound having an active ester group, a compound having a cyanate ester group, and a compound having a maleimide group as a curing agent It is characterized by including these.

In the present invention, 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 as a curing agent, and the coated silica particles, Although it is a low dielectric loss tangent, the hardened | cured material excellent in the adhesiveness after HAST processing with a conductor layer and a soldering resist can be obtained. It is preferable that the coated silica further has a curable reactive group on the surface because it is effective in reducing CTE.

The problem of adhesion after the HAST treatment is particularly noticeable when the amount of filler is large, but according to the present invention, when the amount of silica is large, for example, 30% by mass or more, the HAST of the cured product It is possible to obtain a curable resin composition in which the adhesiveness is not easily lowered after the treatment.

The coated silica particles preferably have 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. However, when the filler is highly filled, the resin has a large specific surface area while the filler particle has a large specific surface area. Since the content is reduced, it is easy to cause a part that is not sufficiently familiar with the curable resin. In particular, in a HAST (high temperature and high humidity) environment, it becomes a moisture absorption factor, and the possibility that the curable reactive group part is hydrolyzed increases. Therefore, the adhesiveness after HAST is inferior and peeling easily occurs.

Such poor paintability is particularly remarkable when the filler particle size is small because the filler has a large specific surface area and requires a large amount of resin to be covered. In addition, even if a curable reactive group is directly applied to the filler surface, the wettability with the curable resin is insufficient, so that adhesion with the conductor layer and the solder resist is caused by hydrolysis, etc., particularly in severe environments such as HAST. Sexual decline.
However, in the present invention, even if the coated silica particles have a curable reactive group on the surface, the hydrated oxide of aluminum and the hydrated zirconium are between the silica particles and the curable reactive group. Since at least one of oxides, hydrated oxides of zinc and hydrated oxides of titanium intervenes, it has been confirmed that there is no decrease in adhesion due to hydrolysis even in a HAST environment. Yes.
That is, since the wettability with the curable resin can be maintained even after the HAST treatment, it is possible to obtain an excellent effect that the adhesion between the conductor layer and the solder resist is not easily lowered. Furthermore, the physical properties of the cured product can be improved by the curable reactive group, for example, the CTE can be lowered.
Further, in the present invention, the surface of the silica particles has more hydroxyl groups based on the hydrated oxide, and can effectively impart a curable reactive group therein, so that the melt viscosity can be further reduced. It is preferable to have.

Furthermore, the coated silica particles are coated with at least one of aluminum hydrated oxide, zirconium hydrated oxide, zinc hydrated oxide, and titanium hydrated oxide, Coarse particles are unlikely to occur in the curable resin, and further, by imparting a curable reactive group effectively, the fluidity is improved and the processability 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 generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

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

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

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

As a method of coating silica particles with a hydrated oxide of zirconium, for example, by adding an aqueous solution of a water-soluble zirconium compound such as zirconium oxychloride to an aqueous slurry of silica particles, and then neutralizing with an alkali or acid, A zirconium hydrated oxide can be deposited on the surface of the silica particles. The amount of silica 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 an amount such that the water-soluble zirconium compound can form a hydrated oxide of zirconium, and preferably the pH is 7 ± 0.5. is there.

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 an aqueous slurry of silica particles, and then neutralized with an alkali or an acid. Zinc hydrated oxide can be deposited on the surface of the particles. The amount of silica 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, and ammonia are added in such an amount that the water-soluble zinc compound can form 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, after adding an aqueous solution of water-soluble titanium such as titanyl sulfate to an aqueous slurry of silica particles, the silica particles are neutralized with an alkali or an acid. Titanium hydrated oxide can be deposited on the surface of the substrate. The amount of silica 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 added is an amount such that the water-soluble titanium compound can form a hydrated oxide of titanium, and the pH is preferably 7 ± 0.5.

Coating with the metal hydrated oxide, that is, coating with at least one of aluminum hydrated oxide, zirconium hydrated oxide, zinc hydrated oxide and titanium hydrated oxide, The hydrated oxide of the metal is preferably coated with 1 to 40 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the silica particles. By covering with 1 part by mass or more, it is possible to obtain a cured product that is excellent in dispersibility of silica particles in the curable resin and whose adhesion is not easily lowered after the HAST treatment.

As described above, in the present invention, even when the surface has a curable reactive group, the adhesion after HAST treatment is excellent, and a strong bond with the curable resin can be obtained. The physical properties of the cured product can be improved by the group, for example, the CTE can be lowered. 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, and even a photocurable reactive group. It may be a thermosetting reactive group. Examples of curable reactive groups include epoxy groups, amino groups, hydroxyl groups, carboxyl groups, isocyanate groups, imino groups, oxetanyl groups, mercapto groups, methoxymethyl groups, methoxyethyl groups, ethoxymethyl groups, ethoxyethyl groups, oxazoline groups, methacrylic groups. Group, acrylic group, vinyl group, styryl group and the like. The method for introducing the curable reactive group to the surface of the coated silica 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 reaction. The surface of the coated silica particles may be treated with a coupling agent having a 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. Of these, a silane coupling agent is preferable.

The curable reactive group on the surface of the coated silica particle is preferably a thermosetting reactive group. When the curable resin composition of the present invention contains a photocurable resin, it may be a photocurable reactive group.

The average particle size of the coated silica particles is preferably 1 μm or less. When the average particle size of the inorganic filler is small, the particles tend to aggregate. However, in the present invention, the silica particles are coated as described above, so that the dispersibility is excellent and the aggregation is difficult. Further, it is preferably smaller than the exposure wavelength, and more preferably 0.4 μm or less. Moreover, it is preferable that it is 0.25 micrometer or more from a viewpoint of suppressing halation. Here, in this specification, the average particle diameter of the silica particles is an average particle diameter (D50) including not only the primary particle diameter but also the secondary particle (aggregate) particle diameter. Is the value of D50 measured by The maximum particle diameter of the coated silica particles (D100 measured by a laser diffraction method) is preferably 2 μm or less, and more preferably 1 μm or less. An example of a measuring apparatus using a laser diffraction method is Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. By being 2 μm or less, a uniform and fine roughened surface can be obtained.

The average particle diameter of the coated silica particles may be adjusted, for example, it is preferably predispersed with a bead mill or a jet mill. Further, the coated silica particles are preferably blended in a slurry state. By blending in the slurry state, high dispersion can be easily achieved, aggregation can be prevented, and handling can be facilitated.

The coated silica particles can be used singly or in combination of two or more. The blended amount of the coated silica particles is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 45% by mass or more in the total solid content of the composition. . As described above, in the present invention, even if the amount of silica is large, the adhesion and dispersibility after HAST treatment are excellent, so that the physical properties of the cured product can be improved, for example, low CTE, warpage resistance, and heat resistance. As described above, silica can be highly filled.

[Curing agent]
The curable resin composition of the present invention contains 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 as a curing agent. By containing such a curing agent, a low dielectric cured product can be obtained. These curing agents can be used alone or in combination of two or more.

(Compound having an active ester group)
The compound having an active ester group is preferably a compound having two or more active ester groups in one molecule. A compound having an active ester group can generally be obtained by a condensation reaction between a carboxylic acid compound and a hydroxy compound. Especially, the compound which has an active ester group obtained using a phenol compound or a naphthol compound as a hydroxy compound is preferable. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, 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 novolac and the like. Further, the compound having an active ester group may be naphthalenediol alkyl / benzoic acid type.

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), HPC8150-65T (manufactured by DIC), EXB-8500-65T (manufactured by DIC) may be 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 the compound having a cyanate ester group, any conventionally known compounds can be used. Examples of the compound having a cyanate ester group include 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, a bisphenol F type cyanate ester resin, and a bisphenol S type. Examples include cyanate ester resins. Further, it may be a prepolymer partially triazine.

Commercially available compounds having a cyanate ester group include a phenol novolak type polyfunctional cyanate ester resin (manufactured by Lonza Japan Co., Ltd., PT30S), and a prepolymer in which a part or all of bisphenol A dicyanate is triazine and becomes a trimer. (Lonza Japan, BA230S75), dicyclopentadiene structure-containing cyanate ester resin (Lonza Japan, DT-4000, DT-7000) and the like. Moreover, BA230 (made by Lonza Japan) is also mentioned.

(Compound having a maleimide group)
The compound having a maleimide group is a compound having a maleimide skeleton, and any conventionally known compound can be used. The compound having a maleimide group preferably has two or more maleimide skeletons. N, N′-1,3-phenylene dimaleimide, N, N′-1,4-phenylene dimaleimide, N, N′-4 , 4-diphenylmethane bismaleimide, 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′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, bis ( 3-ethyl-5-methyl-4-maleimidophenyl) methane, bisphenol A diphenyl ether bismaleimide, polyphenylmethanemaleimide, Beauty and more preferably at least any one of diamines condensates with these oligomers and maleimide skeleton. The said oligomer is an oligomer obtained by condensing the compound which has a maleimide group which is a monomer among the compounds which have the above-mentioned maleimide group.

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

As the curing agent, a compound having an active ester group is preferable because it is excellent in low dielectric loss. Cyanate esters are also preferable because they are excellent in low dielectric loss. However, when used in combination with maleimide, a three-dimensional structure containing a triazine ring can be formed, so that water absorption characteristics are lowered and migration resistance is improved.

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. An epoxy compound can be used individually by 1 type or in combination of 2 or more types.

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

Polyfunctional epoxy compounds include epoxidized vegetable oils; bisphenol A type epoxy resins; hydroquinone type epoxy resins; bisphenol type epoxy resins; thioether type epoxy resins; brominated epoxy resins; novolac type epoxy resins; biphenol novolac type epoxy resins; 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; Tetraphenylol ethane type epoxy resin; Heterocyclic epoxy resin; Phthalate resin; Tetraglycidylxylenoylethane resin; Naphthalene group-containing epoxy resin; Epoxy resin having dicyclopentadiene skeleton; Glycidyl methacrylate copolymer epoxy resin; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Polybutadiene rubber derivatives; CTBN-modified epoxy resins and the like can be mentioned, but are not limited thereto. These epoxy resins can be used alone or in combination of two or more. Among these, novolak type epoxy resins, bisphenol type epoxy resins, bixylenol type epoxy resins, biphenol type epoxy resins, biphenol novolac type epoxy resins, naphthalene type epoxy resins or mixtures thereof are particularly preferable.

The compounding 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.

(Curing accelerator)
The curing accelerator 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- (2-Cyanoethyl) -2-ethyl-4-methylimidazole, imidazole derivatives such as imidazole and epoxy adducts; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy -N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, amine compounds such as 4-dimethylaminopyridine, hydrazine compounds such as adipic acid dihydrazide, sebacic acid dihydrazide; triphenylphosphine, etc. Phosphorus compounds, and the like. 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. Moreover, you may use a metal type hardening accelerator and the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, and tin, is 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 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 organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. Among these, from the viewpoint of curability and solvent solubility, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, zinc (II) acetylacetonate, zinc naphthenate, iron (III) acetylacetonate are Cobalt (II) acetylacetonate and zinc naphthenate are more preferable. As the curing accelerator, a compound that also functions as an adhesion promoter is preferably used in combination with the curing accelerator. A hardening accelerator can be used individually by 1 type or in combination of 2 or more types.

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

(Thermoplastic resin)
The curable resin composition of the present invention can further contain a thermoplastic resin in order to improve the mechanical strength of the resulting cured film. The thermoplastic resin is preferably soluble in a solvent. When it is soluble in a solvent, the flexibility is improved when it is made into a dry film, and the generation of cracks and powder falling can be suppressed. As the thermoplastic resin, use is made of thermoplastic polyhydroxy polyether resin, phenoxy resin that is a condensate of epichlorohydrin and various bifunctional phenolic compounds, or hydroxyl group of hydroxy ether part present in the skeleton of various acid anhydrides and acid chlorides. And esterified phenoxy resins, polyvinyl acetal resins, polyamide resins, polyamideimide resins, block copolymers, rubber particles, and the like. A thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.

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

(Flame retardants)
The curable resin composition of the present invention may contain a colorant. As the flame retardant, a known and commonly used flame retardant can be used. Known and conventional 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, Layered layers of antimony compounds such as antimony trioxide and antimony pentoxide, halides such as pentabromodiphenyl ether and octabromodiphenyl ether, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, hydrotalcite and hydrotalcite-like compounds A double hydroxide is mentioned. A flame retardant can be used individually by 1 type or in combination of 2 or more types.

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

(Coloring agent)
The curable resin composition of the present invention may contain a colorant. As the colorant, known colorants 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 a halogen from the viewpoint of reducing the environmental burden and affecting the human body. A coloring agent can be used individually by 1 type or in combination of 2 or more types.

The blending amount of the colorant is, for example, 0.01 to 10% by mass in 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 and adjusting the viscosity when applied to a substrate or a carrier film. Examples of organic solvents 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, propylene glycol monomethyl ether , Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butylcarby Tall acetate, propylene glycol monomethyl ether acetate, dip 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 ingredients)
Furthermore, you may mix | blend the other well-known and usual additive in the field | area of an electronic material with the curable resin composition of this invention. Other additives include thermal polymerization inhibitors, UV absorbers, silane coupling agents, plasticizers, antistatic agents, anti-aging agents, antioxidants, antibacterial / antifungal agents, antifoaming agents, leveling agents, Sticky agent, adhesion promoter, thixotropic agent, photoinitiator, sensitizer, organic filler, elastomer, mold release agent, surface treatment agent, dispersant, dispersion aid, surface modifier, stabilizer, Examples thereof include phosphors.

Further, the curable resin composition of the present invention may contain a known and usual inorganic filler other than the coated silica particles as long as the effects of the present invention are not impaired. Examples of such inorganic filler include 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. Inorganic fillers such as barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate and zinc white.

Moreover, the curable resin composition of the present invention may contain a curing agent other than the above-mentioned curing agent as long as the effects of the present invention are not impaired. Examples of such a curing agent include compounds having a phenolic hydroxyl group, polycarboxylic acids and acid anhydrides thereof, and alicyclic olefin polymers.

Further, the curable resin composition of the present invention may contain a thermosetting resin other than the epoxy compound as long as the effects of the present invention are not impaired. Examples of such thermosetting resins include isocyanate compounds, blocked isocyanate compounds, amino resins, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional oxetane compounds, episulfide resins, and the like.

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) methyl acrylate, (3-ethyl-3- In addition to polyfunctional oxetanes such as oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin , 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. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

Examples of the episulfide resin, that is, a compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

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.

As the isocyanate compound, a polyisocyanate compound can be blended. Polyisocyanate compounds 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-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate; Alicyclic polyisocyanates such as bicycloheptane triisocyanate; and the isocyanate compounds listed above Adducts, biuret body and isocyanurate products thereof.

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 above-mentioned polyisocyanate compound etc. are mentioned, for example. As an isocyanate block agent, for example, phenol block agent; lactam block agent; active methylene block agent; alcohol block agent; oxime block agent; mercaptan block agent; acid amide block agent; imide block agent; Examples include amine-based blocking agents; imidazole-based blocking agents; imine-based blocking agents.

(Photo-curing resin)
The curable resin composition of the present invention may contain a photocurable resin. As a photocurable resin, what is necessary is just a resin which is hardened | cured by active energy ray irradiation and shows electrical insulation, and the compound which has a 1 or more ethylenically unsaturated group in a molecule | numerator is used preferably. As the compound having an ethylenically unsaturated group, a photopolymerizable oligomer, a photopolymerizable vinyl monomer or the like, which is a known and commonly used photosensitive monomer, can be used, and a radical polymerizable monomer or a cationic polymerizable monomer may be used. As the photocurable resin, a polymer such as a carboxyl group-containing resin having an ethylenically unsaturated group as described later can be used. A photocurable resin can be used individually by 1 type or in combination of 2 or more types.

As the photosensitive monomer, a liquid (solid) or semi-solid photosensitive (meth) acrylate compound having at least one (meth) acryloyl group in the molecule at room temperature can be used. The photosensitive (meth) acrylate compound that is liquid at room temperature is used for the purpose of increasing the photoreactivity of the composition, as well as adjusting the composition to a viscosity suitable for various coating methods and assisting in solubility in an aqueous alkali solution. Also fulfills.

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

As the photopolymerizable vinyl monomer, known and commonly used monomers, 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, triethylene glycol monomethyl vinyl ether; acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacryl (Meth) acrylamides such as amide, N-butoxymethylacrylamide; allyl compounds such as triallyl isocyanurate, diallyl phthalate, diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl Esters of (meth) acrylic acid such as (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 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, trimethylolpropane tri 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, ethoxylation 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 composition of the present invention may contain an alkali-soluble resin. In particular, since the developability is excellent, 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 having no ethylenically unsaturated group. Alkali-soluble resin can be used individually by 1 type or in combination of 2 or more types.

Specific examples of the carboxyl group-containing resin include the compounds listed below (any of oligomers and 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 diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems 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) Diisocyanate and 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, biphenol type epoxy resin ( Carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its partial acid anhydride modified product, carboxyl group-containing dialcohol compound and 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 the terminal ( (Meth) acrylic carboxyl group-containing urethane resin.

(6) During the synthesis of the resin of the above (2) or (4), one isocyanate group and one or more (meth) acryloyl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. The carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.

(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 the hydroxyl group present in the side chain Containing resin.

(8) A carboxyl group-containing resin in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added 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 resulting primary hydroxyl group.

(10) Reaction product obtained by reacting 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, with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride with a product.

(11) Obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a reaction product obtained by reacting a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with an unsaturated group-containing monocarboxylic acid. 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, and with respect to the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, anhydrous A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride such as adipic acid.

(13) In addition to the carboxyl group-containing resins described in the above (1) to (12) and the like, in the molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate, one epoxy group and one or more ( 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 is facilitated, and on the other hand, it is preferable to draw a normal cured product pattern of 200 mgKOH / g or less.

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, the tack-free performance is good, the moisture resistance of the coated film after exposure is good, the film loss during development can be suppressed, and the resolution can be suppressed from decreasing. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is good and the storage stability is also excellent.

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

(Photoinitiator)
The curable resin composition of the present invention can contain a photoinitiator. The photoreaction initiator may be any one that can cure the composition by light irradiation, and is any one of a photopolymerization initiator that generates radicals by light irradiation and a photobase generator that generates bases by light irradiation. Is preferred. The photoinitiator may of course be a compound that generates both radicals and bases upon light irradiation. Light irradiation means irradiation with ultraviolet rays having a wavelength in the range 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-cyclohexyl phenyl 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, hydroxyacetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoin, benzyl, benzoin methyl ether, benzoin ethyl Benzoins such as ether, benzoin n-propyl ether, benzoin isopropyl ether, 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-hydroxycyclohexyl phenyl 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. Thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone 2 Anthraquinones such as methyl anthraquinone, 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 p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O- Benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and other oxime esters; 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- ( Examples include titanocenes such as 1-pyr-1-yl) ethyl) phenyl] titanium; phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, and the like. A photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type.

The photobase generator generates one or more basic substances that can function as a catalyst for a thermosetting reaction by changing the molecular structure upon irradiation with light such as ultraviolet rays or visible light, or by cleaving the molecules. A compound. Examples of basic substances include secondary amines and tertiary amines.

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, alkoxybenzyl carbamates. Compounds and the like. Of these, oxime ester compounds and α-aminoacetophenone compounds are preferred, oxime ester compounds are more preferred, and ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) is more preferred. As the α-aminoacetophenone compound, those having two or more nitrogen atoms are particularly preferable. A photobase generator may be used individually by 1 type, and may be used in combination of 2 or more type. In addition, examples of the photobase generator include quaternary ammonium salts.

As other photobase generators, WPBG-018 (trade name: 9-anthrylmethyl N, N'-diethylcarbamate), WPBG-027 (trade name: (E) -1- [3- (2-hydroxyphenyl) -2- propenoyl] piperidine), WPBG-082 (trade name: guanidinium2- (3-benzoylphenyl) propionate), WPBG-140 (trade name: 1- (anthraquinon-2-yl) ethylidazole, etc. can also be used.

Furthermore, some of the aforementioned photopolymerization initiators also function as photobase generators. The photopolymerization initiator that also functions as a photobase generator is preferably an oxime ester photopolymerization initiator or an α-aminoacetophenone photopolymerization initiator.

The blending amount of the photoinitiator is, for example, 0.01 to 30% by mass in the total solid content of the composition.

The curable resin composition of the present invention is not particularly limited, and may be any of a thermosetting resin composition, a photocurable thermosetting resin composition, and a photosensitive thermosetting resin composition, for example. Moreover, an alkali development 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 photopolymerization initiator, and a photocurable heat containing a photobase generator. Curable resin composition, negative photocurable thermosetting resin composition and positive photosensitive thermosetting resin composition, alkali developing photocurable thermosetting resin composition, solvent developing photocurable thermosetting Examples include, but are not limited to, a curable resin composition, a swollen peelable thermosetting resin composition, and a melt peelable thermosetting resin composition.

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

For example, when the curable resin composition of the present invention is a thermosetting resin composition (not including a photopolymerization initiator), it contains a thermosetting resin. Moreover, it is preferable to contain a hardening accelerator. It is preferable to contain a curing agent. The compounding amount of the thermosetting resin is preferably 1 to 50% by mass in the total solid content of the composition. The blending amount of the curing accelerator is preferably 0.01 to 30% by mass in the total solid content of the composition. The blending amount of the curing agent is preferably 0.01 to 30% by mass in 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 photoinitiator. When the alkali developing type is used, the photocurable resin may be an alkali-soluble resin, and may further contain an alkali-soluble resin. Moreover, it is preferable to contain a hardening accelerator. The blending amount of the alkali-soluble resin is preferably 5 to 50% by mass in the total solid content of the composition. The compounding amount of the thermosetting resin is preferably 1 to 50% by mass in 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 in the total solid content of the composition. The blending amount of the photoinitiator is preferably 0.01 to 30% by mass in the total solid content of the composition. The blending amount of the curing accelerator is preferably 0.01 to 30% by mass in the total solid content of the composition.

The curable resin composition of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-component or two-component or more.

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, the curable resin composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and then a comma coater, a blade coater, a lip coater, a rod coater, and a squeeze coater. Apply a uniform thickness on the carrier film using a reverse coater, transfer roll coater, gravure coater, spray coater or the like. 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 coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 3 to 150 μm, preferably 5 to 60 μm.

As the carrier film, a plastic film is used. 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 within the range of 10 to 150 μm. More preferably, it is in the range of 15 to 130 μm.

After the resin layer made of the curable resin composition of the present invention is formed on the carrier film, the surface of the resin layer is further protected to be peelable for the purpose of preventing dust from adhering to the surface of the resin layer. It is preferable to laminate a film (cover film). As a peelable protective film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. As a protective film, what is necessary is just a thing smaller than the adhesive force of a resin layer and a carrier film, when peeling a protective film.

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. That is, as a film to which the curable resin composition of the present invention is applied when producing a dry film in the present invention, either a carrier film or a protective film may be used.

As a method for producing an electronic component using the curable resin composition of the present invention, a conventionally known method may be used. For example, the curable resin composition of the present invention is a thermosetting resin composition (not containing a photopolymerization initiator), and a three-layer dry film in which a resin layer is sandwiched between a carrier film and a protective film In this case, a printed wiring board can be manufactured by the following method. Either the carrier film or the protective film is peeled off from the dry film, heat laminated to the circuit board on which the circuit pattern is formed, and then thermally cured. The heat curing may be performed in an oven or by a hot plate press. When laminating or hot plate pressing the substrate on which the circuit is formed and the dry film of the present invention, the copper foil or the substrate on which the circuit is formed can be laminated simultaneously. A substrate having an insulating layer can be manufactured by forming a pattern or a via hole by laser irradiation or drilling 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, if there is a component (smear) that cannot be completely removed on the circuit wiring in the pattern or via hole, desmear processing is performed. The remaining carrier film or protective film may be peeled off after lamination, after heat curing, after laser processing, or after desmear treatment.

Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a known method such as vapor deposition, sputtering, or ion plating can be used. In the case of wet plating, first, the surface of the cured resin composition layer (insulating layer) is coated with permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / Treat with an oxidizing agent such as sulfuric acid or nitric acid. As the oxidizing agent, an aqueous sodium hydroxide solution (alkaline permanganate aqueous solution) such as potassium permanganate and sodium permanganate is particularly preferably used. Next, a conductor layer is formed by a method in which electroless plating and electrolytic plating are combined. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. As a subsequent pattern formation method, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used. Note that the connection method of the interlayer circuit may be a connection using a copper pillar.
Next, the surface of the conductor layer and the insulating layer is roughened. As the roughening treatment liquid, for example, an aromatic compound having an amino group and an aromatic ring, a polybasic acid having two or more carboxy groups, and a halide ion can be used. An example of the product name is 01CZ manufactured by MEC.
Insulating layers and conductor layers may be alternately formed as described above, and a solder resist may be formed on the outermost circuit. For example, a solder resist may be formed according to the method described in paragraphs 70 to 76 of Patent 5941180.

The curable resin composition 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 for forming a permanent film. Used for. More preferably, since the curable resin composition of the present invention is excellent in adhesion after HAST treatment with a conductor layer and a solder resist, it is used for forming an interlayer insulating layer. Further, it is suitable for forming a printed wiring board that requires high reliability, for example, a package substrate, particularly a permanent film (particularly an interlayer insulating layer) for FC-BGA. Moreover, the curable resin composition of this invention can be used suitably also for a printed wiring board provided with the wiring pattern with small roughness of a circuit surface, for example, the printed wiring board for high frequencies. 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. Moreover, it can use suitably also when forming a cured film on a low polarity base material, for example, the base material containing an active ester. Since the curable resin composition of the present invention is excellent in adhesion after HAST treatment with a solder resist containing a large amount of silica, an inorganic filler such as silica or barium sulfate is, for example, 30% by mass or more, and further 40% by mass. % Or more 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 this invention can be used as a thing for forming a soldering resist and a coverlay.
The electronic component may be an application other than the printed wiring board, for example, a passive component such as an inductor.

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 description, “parts” and “%” are all based on mass unless otherwise specified.

[Coating and surface treatment of inorganic filler]
(Silica particles coated with hydrated aluminum oxide)
A water slurry of 50 g of spherical silica particles (SFP-20M manufactured by Denka Co., Ltd., average particle size: 0.4 μm) was heated to 70 ° C., and then a 20% sodium aluminate (NaAlO ₂ ) aqueous solution was added to the silica particles with alumina (Al ₂ to 3% in terms of ₂ O ₃ ) was added. Thereafter, a 20% sodium hydroxide aqueous bath solution was added to adjust the pH to 7, followed by aging for 30 minutes. Thereafter, the slurry was washed with filtered water with a filter press and vacuum-dried to obtain a solid of silica particles coated with aluminum hydrated oxide.

(Silica particles coated with zirconia hydrated oxide)
After heating 50 g of water slurry of spherical silica particles (SFP-20M, Denka Corp., average particle size: 0.4 μm) to 70 ° C., an aqueous solution of a water-soluble zirconium compound such as 100 g / l zirconium oxychloride is added to the silica particles. 2 to 3% in terms of zirconia (ZrO ₂ ) was added. Thereafter, a 20% sodium hydroxide aqueous bath solution was added to adjust the pH to 7, followed by aging for 30 minutes. Thereafter, the slurry was washed with filtered water with a filter press and vacuum-dried to obtain a solid of silica particles coated with zirconia hydrated oxide.

(Silica particles coated with zinc hydrated oxide)
A water slurry of 50 g of spherical silica particles (SFP-20M, Denka Corp., average particle size: 0.4 μm) was heated to 70 ° C., and an aqueous solution of zinc sulfate was added in an amount of 2 to 3% in terms of ZnO with respect to the silica particles. . Thereafter, a 20% sodium hydroxide aqueous bath solution was added to adjust the pH to 7, followed by aging for 30 minutes. Thereafter, the slurry was washed with filtered water with a filter press and vacuum-dried to obtain a solid of silica particles coated with hydrated zinc oxide.

(Silica particles coated with hydrated titanium oxide)
After heating 50 g of water slurry of spherical silica particles (SFP-20M manufactured by Denka Co., Ltd., average particle size: 0.4 μm) to 70 ° C., 100 g / l titanyl sulfuric acid aqueous solution is 2 to 3 in terms of TiO _{2 with} respect to the silica particles. % Was added. Thereafter, a 20% sodium hydroxide aqueous bath solution was added to adjust the pH to 7, followed by aging for 30 minutes. Thereafter, the slurry was washed with filtered water with a filter press and vacuum-dried to obtain a solid of silica particles coated with titanium hydrated oxide.

(Silica particles coated with hydrated aluminum oxide and surface-treated with methacrylic silane)
50 g of silica particles coated with the hydrated oxide of aluminum obtained 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.) were dispersed uniformly. Filtration, washing with water, and vacuum drying gave a solid product of silica particles surface-treated with methacrylic silane.

(Silica particles coated with hydrated aluminum oxide and surface-treated with epoxy silane)
50 g of silica particles coated with the aluminum hydrated oxide 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 dispersed uniformly. Filtration, washing with water, and vacuum drying gave a solid product of silica particles surface-treated with epoxysilane.

(Silica particles coated with hydrated aluminum oxide and surface-treated with phenylaminosilane)
50 g of silica particles coated with the 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.) are uniformly dispersed. Then, a solid body of silica particles surface-treated with phenylaminosilane was obtained by filtration, washing with water, and vacuum drying.

(Silica particles surface-treated with phenylaminosilane)
50 g of spherical silica particles (SFP-20M manufactured by Denka Co., Ltd., average particle size: 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 Co., Ltd.) Dispersion was performed, and a solid of silica particles surface-treated with phenylaminosilane was obtained by filtration, washing with water, and vacuum drying.

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

(Talc coated with hydrated aluminum oxide and surface-treated with phenylaminosilane)
20% sodium aluminate (NaAlO ₂ ) aqueous solution while maintaining the pH at 7 ± 1 with hydrochloric acid after raising the temperature of a slurry of 50 g of talc (Nippon Talc SG2000, average particle size: 1.0 μm) to 70 ° C. Was added to talc in an amount of 20% in terms of alumina (Al ₂ O ₃ ). Thereafter, a 20% sodium hydroxide aqueous bath solution was added to adjust the pH to 7, followed by aging for 30 minutes. Thereafter, the slurry was washed with filtered water with a filter press and vacuum-dried to obtain a talc solid material coated with aluminum hydrated oxide.
50 g of talc coated with the 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 dispersed uniformly. Filtration, washing with water, and vacuum drying gave a talc solid that was surface treated with phenylaminosilane.

(Synthesis of alkali-soluble resin A-1)
119.4 parts of a novolac-type cresol resin (trade name “Shonol CRG951”, manufactured by Showa Polymer Co., Ltd., OH equivalent: 119.4) in an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device. Then, 1.19 parts of potassium hydroxide and 119.4 parts of toluene were introduced, the inside of the system was replaced with nitrogen while stirring, and the temperature was increased by heating. Next, 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. Thereafter, the reaction solution was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1%, and the hydroxyl value was 182.2 mgKOH / g (307. 9 g / eq.) Of a novolak-type cresol resin propylene oxide reaction solution. This was an average of 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
293.0 parts of a propylene oxide reaction solution of the obtained novolac-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 part of methylhydroquinone and 252.9 parts of toluene were mixed with a stirrer and a temperature. It was introduced into a reactor equipped with a meter and an air blowing tube, and air was blown at a rate of 10 ml / min and reacted at 110 ° C. for 12 hours while stirring. 12.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 parts of the obtained novolak acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was supplied at a rate of 10 ml / min. With stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added, reacted at 95 to 101 ° C. for 6 hours, cooled and taken out. Thus, a solution of a carboxyl group-containing photosensitive resin A-1 having a non-volatile content of 65% and a solid acid value of 80 mgKOH / g was obtained.

[Examples 1 to 13, Comparative Examples 1 to 5]
Various components shown in Tables 1 to 3 below are blended in proportions (parts by mass) shown in Tables 1 to 3, and after adjusting the viscosity with an organic solvent, premixed with a stirrer, kneaded with a bead mill, and cured. A resin composition was prepared. Similarly, various components shown in Table 4 below are blended in the proportions (parts by mass) shown in Table 4, after adjusting the viscosity with an organic solvent, premixed with a stirrer, kneaded with a bead mill, and described below < A curable resin composition for forming a solder resist (hereinafter, also referred to as “solder resist composition”) used for evaluation of the adhesion with the solder resist (SR)> was prepared. These curable resin compositions were passed through a filtration filter having an opening of 15 μm, and after removing coarse particles, the following dry film was produced.

<Production 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 solution. The coating solution was applied onto a 38 μm thick polyethylene terephthalate film (PET film, Emblet PTH-25 manufactured by Unitika Co., Ltd.) having an arithmetic surface roughness Ra of 150 nm. Examples 1 to 13 and Comparative Examples 1 to 5 were The solder resist composition was dried at 80 ° C. for 10 minutes at a temperature of 100 ° C. to form a resin layer having a thickness of 20 μm. Next, a 18 μm-thick polypropylene film (protective film, OPP-FOA manufactured by Futamura Co., Ltd.) was bonded onto the resin layer to produce a dry film having a resin layer thickness of 20 μm.
In the same manner as described above, a dry film having a resin layer thickness of 30 μm was produced.

<Dry film lamination conditions>
After peeling off the protective film of the dry film, Examples 1 to 13 and Comparative Examples 1 to 5 using a vacuum laminator (CVP-300: manufactured by Nikko Materials Co., Ltd.) were vacuum resisted at 3 hPa, 100 ° C., solder resist in the first chamber. The composition is laminated on the object to be attached at 90 ° C. under a vacuum time of 30 seconds, and pressed under conditions of a press pressure of 0.5 MPa, 80 ° C., and a press time of 30 seconds.

<Evaluation of dispersibility>
The dispersity of each of the compositions 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, a section in which 5 or more grains were confirmed was confirmed.
: Grain is not confirmed or 5 μm or less ○: Over 5 μm and 12.5 μm or less Δ: Over 12.5 μm and 20 μm or less ×: Over 20 μm

<Dielectric loss tangent>
The dry film having a resin layer thickness of 30 μm produced in the examples and comparative examples is laminated on the glossy surface of electrolytic copper foil GTS-MP-18 μm (Furukawa Circuit Foil) under the above conditions, and then flattened on the resin. After peeling off the PET film, the resin layer was completely cured (190 ° C., 60 minutes). Thereafter, the cured film was peeled 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 measurement temperature of 22 ° C. and 5 GHz was measured with a perturbation cavity resonator using a network analyzer, Keysight 8510C, and KEAD's complex dielectric constant calculation software CAMA-S. The dielectric loss tangent was measured.
A: Dielectric loss tangent value less than 0.006 O: Dielectric loss tangent value 0.006 or more and less than 0.009 Δ: 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>
A 30 μm cured film obtained by the same method as the dielectric loss tangent was peeled off from the copper foil, cut into a measurement size (3 mm × 16 mm), and measured for tensile load using TMA-Q400 (TA Instruments). CTE was measured. The test load was 5 g, and the sample was heated from room temperature at a temperature rising rate of 10 ° C./min, and continuously measured twice. The average thermal linear expansion coefficient (α1) in the region of Tg or less in the second time was calculated.
◎: 30 ppm or less ○: More than 30 ppm to 40 ppm or less △: More than 40 ppm to 45 ppm or less ×: More than 45 ppm

<Adhesion with solder resist (SR)>
The composition of each example and comparative example was applied onto the entire surface of an ultrathin copper foil (manufactured by Mitsui Kinzoku Co., Ltd., MT18SD-EX, having a 18 μm copper support), dried at 100 ° C. for 10 minutes and dried. A laminate having a film was obtained. Next, the laminate was laminated under the conditions of 0.5 Mpa, 120 ° C., 1 minute, 1 Torr so that the dried coating film of this laminate was bonded to an FR-4 (glass epoxy) substrate as a support. 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 (Meck Bright QE-7300, manufactured by MEC) to obtain a substrate having a cured film.
Thereafter, as a pretreatment for forming the solder resist layer, the substrate having the cured film was subjected to an acid treatment to obtain a low profile cured film with Rz = 2 μm or less.
A 20 μm dry film having a resin layer made of the solder resist composition prepared above was laminated on the cured film under the above conditions.
Then, using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), the entire surface of the dry film was exposed (exposure amount: 400 to 600 mJ / cm ² ), and then the polyethylene terephthalate film was peeled from the dry film, and the resin layer was removed. Exposed. Thereafter, development was performed for 60 seconds under the conditions of 30 ° C. and a spray pressure of 2 kg / cm ² using a 1 wt% Na ₂ CO ₃ aqueous solution. Subsequently, after 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, the resin layer was completely cured by heating at 160 ° C. for 60 minutes to have a cured solder resist film. A substrate was produced. A cross section peeling test was performed on the cured film, and the adhesion between the cured film made of the compositions of Examples and Comparative Examples and the cured solder resist film was confirmed. Specifically, based on JIS K5400, 100 crosses (10 × 10) of 1 mm square grids where the incision reaches the cured film of the example and the comparative example are made with a cross cutter, and the cellophane tape is completely adhered thereon. Then, it was pulled apart and it was confirmed how many out of 100 pieces were in close contact.
Similarly, the adhesion test was carried out after 100 hours at HAST conditions of 130 ° C. and 85%.
A: 96 or more / 100
○: 61/100 to 95/100
Δ: 11/100 to 60/100
X: 10/100 or less

<Adhesion with copper>
Electrolytic copper foil GTS-MP-18μm (Furukawa Circuit Foil Co., Ltd.) glossy surface is pre-processed by spraying MEC 01CZ to roughen the surface, and the surface roughness Ra is 0.04 μm. Got.
A dry film having a resin layer thickness of 20 μm prepared in each Example and Comparative Example was laminated on this 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 bonded with an adhesive (AR-S 30 manufactured by Nichiban). This bonded body was treated for 100 hours in a high-temperature and high-humidity tank in an atmosphere of 130 ° C. and 85% humidity. Thereafter, the copper foil was peeled off using a 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. and 85% RH for 100 hours, the peel strength of both samples was measured based on JIS C6481 by Autograph AG-X manufactured by Shimadzu Corporation.
The higher the peel strength, the better the adhesion, and the lower the strength reduction rate before and after the HAST test, the better.
(Before HAST-After HAST) / Before HAST x 100 (%)
HAST 130 ° C. 85% 100 hrs A reduction rate of 40% or less is desirable.

* 1: ESN-475V manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., naphthol type (epoxy equivalent = 340 g / eq)
* 2: Nippon Kayaku Co., Ltd. NC-3000L, biphenyl type (epoxy equivalent = 272 g / eq)
* 3: PETG manufactured by Showa Denko (Epoxy equivalent = 92 g / eq)
* 4: YX7200B35 manufactured by Mitsubishi Chemical Corporation, epoxy compound * 5: EXB-8500-65T manufactured by DIC Corporation, 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 Lonza Japan, a compound having a cyanate ester group (cyanate equivalent = 232 g / eq)
* 8: PT30 manufactured by Lonza Japan, compound having a cyanate ester group (cyanate equivalent = 124 g / eq)
* 9: MIR-3000 manufactured by Nippon Kayaku Co., Ltd., compound having maleimide group * 10: P200 manufactured by Mitsubishi Chemical Co., Ltd. Adduct of imidazole and epoxy * 11: Zinc (II) naphthenate mineral spirit manufactured by Wako Pure Chemical Industries, Ltd. * 12: Dimethylaminopyridine * 13: OP-935 manufactured by Clariant Chemicals
* 14: Silica particles coated with hydrated oxide of aluminum prepared above * 15: Silica particles coated with hydrated oxide of zirconium prepared above * 16: Zinc particles prepared above Silica particles coated with hydrated oxide * 17: Silica particles coated with hydrated titanium oxide prepared as described above * 18: Coated with hydrated oxide of aluminum prepared above, and Silica particles surface-treated with methacrylsilane * 19: Silica particles coated with aluminum hydrated oxide prepared above and surface-treated with epoxysilane * 20: Hydration of aluminum prepared above Silica particles coated with oxide and surface-treated with phenylaminosilane * 21: Silica particles surface-treated with phenylaminosilane prepared above * 2 : Prepared above, silica particles * 23 has been surface treated with methacrylsilane: Denka Co. SFP-20M, average particle size: 0.4 .mu.m (silica)
* 24: Talc coated with aluminum hydrated oxide and surface-treated with phenylaminosilane prepared above.

* 25: Phenol-starting 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: Irgacure OXE02 manufactured by BASF Japan (Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime)
* 30: Nippon Kayaku DPHA (dipentaerythritol hexaacrylate)

From the results shown in Tables 1 to 3, 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 having a low dielectric loss tangent is obtained. I understand that

Claims

Silica particles coated with at least one of aluminum hydrated oxide, zirconium hydrated oxide, zinc hydrated oxide, and titanium hydrated oxide;
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,
A curable resin composition comprising:
2. The curable resin composition according to claim 1, wherein the coated silica particles further have a curable reactive group on the surface.
A dry film comprising a resin layer obtained by applying the curable resin composition according to claim 1 to a film and drying the 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.