TW201942231A - Curable resin composition, dry film, cured object, layered structure, and electronic component - Google Patents

Abstract

Provided are: a curable resin composition capable of giving a cured object which has excellent adhesion to roughening-free substrates or low-profile substrates, while retaining physical properties including low CTE; 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; a layered structure including a cured resin layer comprising the cured object; and an electronic component including the cured object. The curable resin composition is characterized by comprising a curable resin and surface-treated silica particles having a positive zeta potential.

Description

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

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

Generally speaking, in electronic components such as printed wiring boards, from the viewpoint of heat resistance or electrical insulation, it is widely used as an interlayer insulating material, a solder resist material, or a sealing material. A resin composition containing a curable resin such as an oxygen resin as a main component and further an additive component such as a filler.
In addition, the surface of the substrate on which the resin insulating layer of the solder resist material is formed is generally roughened by the formation step of the conductor layer (coarse transfer of copper foil or chemical treatment before copper plating) to improve the solder resist material alignment. Adhesiveness of the substrate.
The hardened body composed of the conventional resin composition used as the insulating material of the roughened substrate as described above has a problem of delay or loss of electric signals when communicating in a high frequency region.
In recent years, due to such a problem of transmission loss, the substrate surface tends to have no roughening or low-roughening surface (so-called low-profile substrate). As the substrate material, a low-polarity insulating material containing an active ester is used. Low dielectric loss material.

On the other hand, in response to the increase in density of printed wiring boards accompanying the thinner, lighter and shorter electronic components, the miniaturization or multi-pin semiconductor packaging systems have been put into practical use, and mass production has progressed. Recently, they have been widely adopted. BGA (ball grid array package), CSP (wafer-scale package), WLP (wafer-level package), etc. are used to replace the semiconductor package called QFP (Quad Flat Package) or SOP (Small Outline Package).
In addition, with the expansion of the smartphone market, in the field of digital cameras that require high-definition and high-sensitivity as a camera function, the requirements for high-speed / high-sensitivity require the use of CMOS image sensors, which are used in this system. Silicon wafers or glass substrates that cannot be roughened, not printed wiring boards.
In general, an insulating coating is formed on such a package substrate or glass substrate, and higher reliability is required for the insulating coating system (HAST resistance, PCT resistance, heat resistance, low warpage resistance, thermal dimensional stability, etc.) .
As a method for imparting high reliability, for example, it is generally performed to improve the thermophysical properties by filling an inorganic filler into the composition. Among these inorganic fillers, silicon dioxide is particularly used, and since it can be easily given a surface treatment and has a low coefficient of thermal expansion (CTE), it is widely used to improve the characteristics of insulating materials (see Patent Document 1).
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2012-83467 (Scope of Patent Application)

[Problems to be Solved by the Invention]

However, when the inorganic filler is filled, the proportion of the resin component is reduced, and therefore it is difficult to obtain adhesion. Here, the surface of the inorganic filler is treated with a silane coupling agent or the like to improve the dispersibility in the hardening resin to improve the adhesion. However, the surface-treated inorganic filler has a large shrinkage due to hardening. Therefore, it is difficult to obtain adhesion particularly to a substrate without roughening or a low-profile substrate. In recent years, since the physical properties of the resin insulating layer have been improved, it tends to be filled with an inorganic filler, and it has become difficult to obtain adhesion to a substrate without roughening or a low-profile substrate.
Therefore, an object of the present invention is to provide a hardenable resin composition which can obtain a hardened product having excellent adhesion to a substrate without roughening or a low-profile substrate while maintaining physical properties such as low CTE, and the like. The obtained dry film of the resin layer, the composition or the hardened material of the resin layer of the dry film, the laminated structure having the resin hardened layer composed of the hardened material, and the electronic component having the hardened material.

[Means to solve the problem]

In order to achieve the above object, the inventors of the present invention conducted in-depth studies focusing on the surface treatment of silicon dioxide used as an inorganic filler. As a result, the inventors have found that the problem of the decrease in adhesion to a substrate without roughening or a low-profile substrate as described above is caused by a charge, and the surface of the silicon dioxide particles is made to become positively charged. Processing can solve the above problems and complete the present invention.

That is, the curable resin composition of the present invention is characterized in that it contains surface-treated silica particles having a positive potential, and a curable resin.

In the curable resin composition of the present invention, the surface-treated silica particles are preferably at least any one of zirconium hydrated oxide, zinc hydrated oxide, titanium hydrated oxide, and aluminum hydrated oxide. Covered silica particles.

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

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

The laminated structure of the present invention is a structure comprising a resin hardened layer (A) and a resin hardened layer (B) or a substrate (C) adjacent to the resin hardened layer (A), wherein the resin is hardened. The layer (A) is a hardened product as claimed in claim 4, and the other potential of the resin hardened layer (B) or the substrate (C) is not positive.

The electronic component of the present invention is characterized by having the hardened material or the laminated structure.

[Effect of the invention]

According to the present invention, it is possible to provide a hardenable resin composition capable of obtaining a hardened product having excellent adhesion to a substrate without roughening or a low-profile substrate while maintaining physical properties such as low CTE, and having the obtained composition. A dry film of a resin layer, the composition or a hardened product of the resin layer of the dry film, a laminated structure having a hardened resin layer composed of the hardened material, and an electronic component having the hardened material.

The curable resin composition of the present invention is characterized in that it contains surface-treated silica particles having a positive potential, and a curable resin.

Generally speaking, as the constituent materials of the above-mentioned semiconductor packages (such as low-polar interlayer insulation materials or sealing materials) or the surface of silicon wafers or glass substrate wafers, the other potentials are often negative, and electrostatic repulsion can be considered. One reason for the decrease in adhesion. In the present invention, by performing surface treatment such that the silicon dioxide particles become positively charged, even if an adhesion promoter (AP: Adhesion Promoter) is not coated on these substrates, a low-polarity material (Low Df) can be obtained. Material) Good adhesion to low-profile substrates or substrates without roughening. In addition, the wettability of the surface-treated silica particles is presumed to be an effect due to the organic component in the curable resin composition being easily coated with the positively-charged silica particles and the dispersibility being improved. This is considered to be caused by Coulomb's force, but it is estimated that the curable resin composition is also effective when it contains a component that easily becomes alkaline, such as an amine-based curing catalyst or an alkaline additive.

In particular, when amine-based compounds are contained, the coulomb force of the surface-treated silicon dioxide particles with a positive sundial potential acts to improve the dispersibility of the surface-treated silicon dioxide particles to the hardening resin composition and the substrate without roughening. Or, the adhesion of the low-profile substrate is improved. Further, even when the constituent material to be adhered is composed of a material containing an amine compound, a hardened material having excellent adhesion to the adherend can be obtained.

The above-mentioned problem of adhesiveness is particularly significant when the filling amount is large, but according to the present invention, even when the filling amount of the silicon dioxide particles is large, for example, the total solid content of the composition is 30% by mass or more, and The adhesiveness of a chemically-formed substrate or a low-profile substrate is also excellent.
In addition, the curable resin composition of the present invention is not only excellent in adhesion between a hardened state and a substrate without roughening or a low-profile substrate, but also a dry film or liquid ink such as a resin layer of a dry film. This state is also excellent in adhesion to a substrate without roughening or a low-profile substrate.

Hereinafter, each component of the curable resin composition of this invention is demonstrated. In addition, in this specification, (meth) acrylic acid ester means the general term of an acrylic acid ester, a methacrylic acid ester, and these mixtures, and it is the same also about other similar expressions.

[Silicon dioxide particles]
The curable resin composition of the present invention contains surface-treated silicon dioxide particles having a positive potential. Sunda potentials are positive, zero, and negative. In this specification, the positive / negative of the sundat potential refers to the positive / negative when measured by ELSZ-2000ZS made by Otsuka Electronics. The other potential of the surface-treated silicon dioxide particles may be 0.1 mV or more, and preferably 1 mV or more. The upper limit value is not particularly limited, and is, for example, 60 mV.

The silicon dioxide particles to be surface-treated (that is, the silicon dioxide particles before the surface treatment) are not particularly limited, as long as the well-known and commonly used silicon dioxide particles that can be used as an inorganic filler are used. The shape of the silica particles to be surface-treated includes spherical silica, amorphous silica, crystalline silica, and the like, and spherical silica is preferred. Further, the silica particles to be surface-treated include fused silica and silica synthesized by a sol-gel method. The silicon dioxide particles are preferably synthetic silicon dioxide having a small amount of α-ray generation.

As long as the sundala potential becomes positive, various metal compounds can be used for the surface treatment, and there is no particular limitation. Preferable examples are zirconium hydrated oxide, zinc hydrated oxide, titanium hydrated oxide, and aluminum hydrated oxide. At least one kind of coated silica particles. In the case of a photosensitive resin composition, it is possible to increase the sensitivity by coating with a hydrated oxide of such a metal. It is presumed to act as a catalyst to promote photosensitivity.

The method of coating the silica particles with a hydrated oxide of zirconium can be performed by adding an aqueous solution of a water-soluble zirconium compound such as zirconium oxychloride to the aqueous slurry of the silica particles, and then neutralizing it with an alkali or acid. The surface of the silicon dioxide particles deposits a hydrated oxide of zirconium. The amount of silicon dioxide particles in the aqueous slurry is not particularly limited, and generally 30 to 300 g / l is appropriate. The alkali system uses sodium hydroxide, potassium hydroxide, ammonia, etc., and the added amount is the amount of the hydrated oxide that can form zirconium by the water-soluble zirconium compound, and the pH is preferably 7 ± 0.5.

A method for coating silica particles with a hydrated oxide of zinc, for example, by adding an aqueous solution of a water-soluble zinc compound such as zinc sulfate to an aqueous slurry of silica particles, and then neutralizing it with an alkali or an acid, The surface of the silicon particles deposits hydrated oxides of zinc. The amount of silicon dioxide particles in the aqueous slurry is not particularly limited, and generally 30 to 300 g / l is appropriate. Alkali-based sodium hydroxide, potassium hydroxide, and ammonia are added in an amount that is the amount of the hydrated oxide of zinc that the water-soluble zinc compound can form, and the pH is preferably 7 ± 0.5.

A method for coating silica particles with a hydrated oxide of titanium, for example, by adding an aqueous solution of a water-soluble titanium such as titanyl sulfate to an aqueous slurry of silica particles, and then neutralizing it with an alkali or an acid, The surface of the silicon particles deposits hydrated oxides of titanium. The amount of silicon dioxide particles in the aqueous slurry is not particularly limited, and generally 30 to 300 g / l is appropriate. For the acid system, hydrochloric acid, nitric acid, and the like are used, and the amount added is the amount of the hydrated oxide of titanium that can be formed by the water-soluble titanium compound, and the pH is preferably 7 ± 0.5.

The method of coating silica particles with a hydrated oxide of aluminum can be performed 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 the mixture with alkali or acid. The surface of the silicon oxide particles deposits a hydrated oxide of aluminum. The amount of silicon dioxide particles in the aqueous slurry is not particularly limited, and generally 30 to 300 g / l is appropriate. Sodium hydroxide, potassium hydroxide, ammonia is used as the alkali; hydrochloric acid, nitric acid, etc. are used as the acid; the added amount is the amount of the hydrated oxide of aluminum that the water-soluble aluminum compound can form, and the pH is preferably 7 ± 0.5.

Coating with the foregoing metal, that is, coating with at least any one of aluminum hydrated oxide, zirconium hydrated oxide, zinc hydrated oxide, and titanium hydrated oxide, with respect to 100 mass of silicon dioxide particles In terms of parts, the hydrated oxide of the metal is preferably coated with 1 to 40 parts by mass, more preferably 3 to 20 parts by mass. By coating with 1 part by mass or more, the dispersibility of the silica particles in the curable resin is excellent, and the adhesion is not easily reduced before and after the HAST treatment.

Since the adhesion after further HAST treatment is also excellent, the aforementioned surface-treated silica particles are preferably silica particles treated with a metal hydrated oxide coating. In addition, if it is a silica particle coated with a metal hydrated oxide, the affinity with the resin in the hardening resin is improved, the dispersibility becomes good, and coarse particles or agglomeration can be reduced, especially if a fine pattern is used. In the case of circuit boards, the insulation reliability is also excellent.

In addition, when the amount of silicon dioxide is large, the adhesion with a substrate having no roughening or low-roughening surface without anchoring effect (so-called low-profile substrate) or a substrate made of a low-polarity material is deteriorated, and further, There is a problem that the adhesiveness is easily reduced after HAST treatment. However, in the present invention, as the aforementioned surface-treated silicon dioxide particles, silicon dioxide particles coated with a hydrated oxide of silicon and a hydrated oxide of a metal are filled as the aforementioned surface-treated silicon dioxide particles. For the substrate as described above, a cured product having excellent adhesion after HAST treatment can also be obtained.

The surface-treated silica particles are preferably silica particles coated with at least a metal hydrated oxide. The surface-treated silicon dioxide particles preferably have a coating layer composed of a hydrated oxide of silicon and a coating layer composed of a hydrated oxide of a metal such as zirconium in this order. By coating in this manner, a hardened product having excellent dispersibility of the silica particles in the curable resin and having a hardly reduced adhesiveness after HAST treatment can be obtained.

A method of coating silicon dioxide particles with a hydrated oxide of silicon, for example, by adding an aqueous solution of a silicic acid alkali to an aqueous slurry of silicon dioxide to generate silicic acid on the surface of the silicon dioxide, and then adding an inorganic substance to the slurry Acid, which decomposes silicic acid into hydrated oxides of silicon, and deposits hydrated oxides of silicon on the surface of silicon dioxide particles. The amount of silica particles in the water slurry is not particularly limited, and generally 70 to 150 g / l is appropriate. Next, as described above, the alkali silicate added to the aqueous slurry is specifically sodium silicate, potassium silicate, etc., and its concentration is usually 10 to 200 g / l in terms of silicon dioxide conversion. Examples of the inorganic acid include hydrochloric acid, nitric acid, and sulfuric acid.

For coating with a hydrated oxide of silicon, it is preferable to cover the hydrated oxide of silicon with 60 to 99 parts by mass, more preferably 80 to 99 parts by mass, relative to 100 parts by mass of the silicon dioxide particles.

The surface-treated silicon dioxide particles having a metal hydrated oxide may have a hardening reactive group on the surface. When the filler has a hardening reactive group on the surface, the bond between the filler and the hardening resin can be strengthened, but when the filler is highly filled, the specific surface area of the filler particles is large, and on the other hand, the resin content is reduced, so it is easy A part having insufficient tightness with the resin is generated, and in particular, it becomes a cause of moisture absorption in a HAST (high temperature and high humidity) environment, and the part of the hardening reactive group is likely to be hydrolyzed. Therefore, the adhesion after HAST is poor, and peeling is likely to occur. Such a wettability is notable. When the particle diameter of the filler is small, the specific surface area of the filler is large, and the amount of resin to be coated must be large, which is particularly significant. However, in the present invention, even if the surface-treated silica particles have a hardenable reactive group on the surface, it is confirmed that the adhesion is not reduced by hydrolysis in a HAST environment. That is, the wettability with the curable resin can be maintained after the HAST treatment, so that an excellent effect that the adhesion is not easily reduced can be obtained, and further, the physical properties of the cured product obtained by the curable reactive group can be improved, such as low CTE.

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) incorporated in the curable resin composition, and may be a photocurable reactive group. It may be a thermosetting reactive group. Examples of the photocurable reactive group include methacrylfluorenyl, acrylfluorenyl, vinyl, and styryl groups. Examples of the thermosetting reactive group include epoxy groups, amino groups, hydroxyl groups, carboxyl groups, isocyanate groups, imine groups, and the like. Oxetane, mercapto, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, oxazoline and the like. The method for introducing a hardening reactive group on the surface of the aforementioned surface-treated silica particles is not particularly limited, and it may be introduced using a known and commonly used method, as long as a surface treating agent having a hardening reactive group, for example, a hardening reaction As the coupling agent or the like of the organic group, it is sufficient to treat the surface of the aforementioned surface-treated silica particles. 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, silane coupling agents are particularly preferred. By processing with a silane coupling agent, the shake property is reduced, so the fluidity is improved, and the embedding property to the fine-pitch circuit pattern is improved.

When the surface-treated silicon dioxide particles have a curable reactive group on the surface, when the curable resin composition of the present invention contains a photo-curable resin, a photo-curable reactive group is preferred, and when a thermo-curable resin is contained, it is preferred. It is a thermosetting reactive group.

The average particle diameter of the surface-treated silica particles is preferably, for example, 2 μm or less. The wavelength is preferably smaller than the exposure wavelength, and more preferably 0.4 μm or less. From the viewpoint of suppressing halation, it is preferably 0.25 μm or more. Here, in this specification, the average particle diameter of the silicon dioxide particles is not only the particle diameter of the primary particles, but also the average particle diameter (D50) of the particle diameter of the secondary particles (agglomerates), which is determined by lightning. D50 value measured by diffraction method. The maximum particle diameter of the surface-treated silica particles (D100 measured by the laser diffraction method) is preferably 5 μm or less, and more preferably 2 μm or less. As a measuring device for the laser diffraction method, Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. can be cited. When the thickness is 5 μm or less, the insulation reliability on a substrate having a fine-pitch circuit pattern, the formability (resolution) of a small-diameter pattern, and the embedding property on a substrate having a fine-pitch circuit pattern are excellent.

The average particle diameter of the surface-treated silica particles may also be adjusted. For example, a bead mill or a jet mill is preferably used for preliminary dispersion. In addition, the surface-treated silica particles are preferably blended in a slurry state. By blending in a slurry state, it is easy to highly disperse, prevent aggregation, and facilitate handling.

The surface-treated silica particles may be used singly or in combination of two or more kinds. The blending amount of the surface-treated silica particles is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more of the total solid content of the composition. As described above, in the present invention, even if the amount of silicon dioxide is large, the adhesiveness and dispersibility with low-polarity insulating materials or wafers are also excellent. Therefore, the physical properties of the hardened material can be improved, such as low CTE and resistance to warpage. For the purpose of flexibility and heat resistance, silicon dioxide is highly filled.

[Curable resin]
The curable resin composition of the present invention contains a curable resin. The curable resin used in the present invention is a thermosetting resin or a photocurable resin, and a mixture thereof may also be used. The blending amount of the curable resin is, for example, 1 to 50% by mass based on the total solid content of the composition.

(Thermosetting resin)
When the curable resin composition of the present invention contains a thermosetting resin, the heat resistance of the cured product is improved, and the adhesion to the substrate is improved. The thermosetting resin can be an isocyanate compound, a blocked isocyanate compound, an amine resin, a benzoxazine resin, a carbodiimide resin, a cyclic carbonate compound, an epoxy compound, a polyfunctional oxetane compound, a ring Known and commonly used thermosetting resins such as sulfur resins. Among these, epoxy compounds, polyfunctional oxetane compounds, and compounds having two or more thioether groups in the molecule, that is, episulfide resins are preferred; epoxy compounds are more preferred. The thermosetting resin can be used singly or in combination of two or more kinds.

The above-mentioned epoxy compound is a compound having an epoxy group, and any of conventionally known ones can be used. Examples thereof include polyfunctional epoxy compounds having a plurality of epoxy groups in a molecule. Furthermore, it may be a hydrogenated epoxy compound.

Multifunctional epoxy compounds include epoxidized vegetable oils; bisphenol A epoxy resin; hydroquinone epoxy resin; bisphenol epoxy resin; thioether epoxy resin; brominated epoxy resin; novolac type Epoxy resin; biphenol novolac epoxy resin; bisphenol F epoxy resin; hydrogenated bisphenol A epoxy resin; glycidylamine 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 novolac type epoxy resin; Tetraphenol-based ethane type epoxy resin; heterocyclic epoxy resin; diglycidyl phthalate resin; tetraglycidyl xylyl fluorenyl ethane resin; naphthyl-containing epoxy resin; bicyclic Epoxy resin with pentadiene skeleton; glycidyl methacrylate copolymerized epoxy resin; copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; epoxy modified polymer Butadiene rubber derivatives; CTBN modified epoxy resin, etc., but Limited to these. These epoxy resins can be used alone or in combination of two or more. Among these, novolac-type epoxy resin, bisphenol-type epoxy resin, bixylenol-type epoxy resin, biphenol-type epoxy resin, biphenol novolac-type epoxy resin, and naphthalene-type epoxy resin are particularly used. Resin or a mixture of these is preferred.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether and bis [(3-ethyl-3-oxetan Butylmethoxy) methyl] ether, 1,4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3- Ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) acrylate, methyl (3-ethyl-3-oxetan) Cyclobutane) methyl ester, (3-methyl-3-oxetanyl) methacrylate, (3-ethyl-3-oxetanyl) methacrylate, or Polyfunctional oxetanes such as these oligomers and copolymers include oxetanol and novolac resins, poly (p-hydroxystyrene), cardo-type bisphenols, and calixarene Type, resorcinol calixarene, or etherification of resins having hydroxyl groups such as silsesquioxane. Other examples include copolymers of unsaturated monomers having an oxetane ring and alkyl (meth) acrylates.

Examples of the compound having a plurality of cyclic sulfide groups in the molecule include a bisphenol A type episulfide resin. In addition, an episulfide resin or the like in which an oxygen atom of an epoxy group of a novolac epoxy resin is replaced with a sulfur atom by a similar synthetic method can also be used.

Examples of the amine-based resin such as a melamine derivative and a benzoguanamine derivative include a methylolmelamine compound, a methylolbenzoguanamine compound, a methylolacetylene urea compound, and a methylolurea compound.

A polyisocyanate compound may be blended as the isocyanate compound. Examples of the polyisocyanate compound include 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, o-xylene diisocyanate, Aromatic polyisocyanates such as m-xylene diisocyanate and 2,4-toluene isocyanate dimer; tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene Aliphatic polyisocyanates such as diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate; alicyclic polyisocyanates such as dicycloheptane triisocyanate; and the isocyanate compounds listed previously Adducts, biurets and isocyanurates.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. Examples of the isocyanate compound capable of reacting with the isocyanate blocking agent include the aforementioned polyisocyanate compounds. Examples of isocyanate blocking agents include phenol-based blocking agents; lactam-based blocking agents; active methylene-based blocking agents; alcohol-based blocking agents; oxime-based blocking agents; thiol-based blocking agents; Acid amine-based end-capping agent; fluorene imine-based end-capping agent; amine-based end-capping agent; imidazole-based end-capping agent; imine-based end-capping agent, etc.

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

As the photosensitive monomer, a photosensitive (meth) acrylate compound having one or more (meth) acrylfluorenyl groups in a molecule and which is liquid, solid, or semi-solid at room temperature can be used. The photosensitive (meth) acrylate compound is a liquid at room temperature for the purpose of improving the photoreactivity of the composition. In addition, it also plays a role in adjusting the composition to a viscosity suitable for various coating methods, or to help alkali The role of solubility in aqueous solutions.

Examples of the photopolymerizable oligomer include unsaturated polyester-based oligomers and (meth) acrylate-based oligomers. (Meth) acrylate-based oligomers include phenol novolak (meth) acrylate epoxy ester, cresol novolak (meth) acrylate epoxy ester, bisphenol type (meth) acrylate epoxy ester, and the like (Meth) acrylic epoxy esters; urethane (meth) acrylates, epoxy urethane (meth) acrylates, polyester (meth) acrylates, polyethers (methyl ether) Group) acrylate, polybutadiene modified (meth) acrylate, and the like.

Examples of the photopolymerizable vinyl monomer include styrene derivatives such as styrene, chlorostyrene, and α-methylstyrene; vinyl acetate, vinyl butyrate, and vinyl benzoate. Vinyl esters; vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-pentyl ether, vinyl isoamyl ether, vinyl-n- Octyl alkyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether and other vinyl ethers; acrylamide, methacrylamide, N -Hydroxymethacrylamide, N-Hydroxymethacrylamide, N-methoxymethacrylamide, N-ethoxymethacrylamine, N-butoxymethacrylamine (Meth) acrylamides such as amines; allyl compounds such as triallyl isocyanate, diallyl phthalate, diallyl isophthalate, and the like; (meth) 2-ethylhexyl acrylate, lauryl (meth) acrylate, tetrahydrofuran methyl (meth) acrylate, isoamyl (meth) acrylate, phenyl (meth) acrylate, phenoxy (meth) acrylate B (Meth) acrylic acid esters; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, etc .; Alkoxyalkanediol mono (meth) acrylates, such as methoxyethyl methacrylate, ethoxyethyl (meth) acrylate; ethylene glycol di (meth) acrylate, succinic acid Alcohol di (meth) acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and other alkylene polyols poly (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Polyoxyalkylene glycol poly (meth) acrylic acid such as di (meth) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri (meth) acrylate, etc. Esters; poly (meth) acrylates such as hydroxytrimethylacetate neopentyl glycol di (meth) acrylate, etc .; see [(meth) acrylic ethoxyethyl] isotricyanate Wait for Cyanurate poly (meth) acrylates.

(Alkali soluble resin)
The curable resin composition of the present invention may contain an alkali-soluble resin. Examples of the alkali-soluble resin include compounds having two or more phenolic hydroxyl groups, resins containing carboxyl groups, compounds having phenolic hydroxyl groups and carboxyl groups, and compounds having two or more thiol groups. Among them, if the alkali-soluble resin is a carboxyl group-containing resin or a phenol resin, the adhesion to the substrate is improved, so it is preferable. 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 resins can be used alone or in combination of two or more.

Specific examples of the carboxyl group-containing resin include the following compounds (both oligomers and polymers).

(1) Copolymerization sites of unsaturated carboxylic acids such as (meth) acrylic acid, and unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth) acrylates, and isobutylene The obtained carboxyl group-containing resin.

(2) By using diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and carboxyl-containing groups such as dimethylolpropionic acid and dimethylolbutanoic acid Glycol compounds and polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, and phenols Carboxyl group-containing urethane resin obtained by addition polymerization reaction of a diol compound such as a polar hydroxyl group and an alcoholic hydroxyl compound.

(3) For diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, etc., with polycarbonate-based polyols, polyether-based polyols, and polyester-based Polyol, polyolefin polyol, acrylic polyol, bisphenol A alkylene oxide adduct diol, diol compound obtained by addition polymerization reaction of phenolic hydroxyl group and alcoholic hydroxyl compound, etc. A urethane resin containing a carboxyl group at the end of a urethane resin by reacting an acid anhydride with the terminal.

(4) Diisocyanate with bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bixylenol epoxy resin (Meth) acrylates of bifunctional epoxy resins such as biphenol type epoxy resins or modified anhydrides thereof, carboxyl-containing compounds obtained by addition polymerization of carboxyl-containing glycol compounds and glycol compounds Urethane resin.

(5) adding a compound having one hydroxyl group and one or more (meth) acrylfluorenyl groups in a molecule such as hydroxyalkyl (meth) acrylate in the synthesis of the resin of (2) or (4) above, Carboxyl-containing urethane resins that are terminally (meth) acrylicated.

(6) In the synthesis of the resin of (2) or (4) above, molecules such as isophorone diisocyanate and pentaerythritol triacrylate are added to the molecule such as a mole reactant and have one isocyanate group and one or more (a (Meth) acrylic acid-based compound, a carboxyl group-containing urethane resin having terminal (meth) acrylic acid.

(7) Reaction of (meth) acrylic acid with a polyfunctional epoxy resin, and addition of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. to the hydroxyl groups present in the side chains Carboxyl-containing resin obtained from an acid anhydride.

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

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

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

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

(12) A compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule of p-hydroxyphenylethanol and the like, and an unsaturated monocarboxylic acid containing an unsaturated group such as (meth) acrylic acid and one molecule An epoxy compound having a plurality of epoxy groups is reacted, and maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic anhydride are made to the alcoholic hydroxyl group of the obtained reaction product. A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride such as polycarboxylic acid.

(13) To the carboxyl group-containing resin described in the above (1) to (12) and the like, (glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, etc.) are added in a molecule having 1 A carboxyl group-containing resin composed of a compound of one epoxy group and one or more (meth) acrylfluorenyl groups.

Further, an alkali-soluble resin having at least one of a sulfonium sulfonium imine structure and a sulfonium imine structure can also be suitably used.

An alkali-soluble resin can also be suitably used, which has the following formula (1) or (2)

Resin and imine resins having at least one of the structures and alkali-soluble functional groups shown. By containing a resin having a sulfonium imine bond directly bonded to a cyclohexane ring or a benzene ring, a hardened product having excellent toughness and heat resistance can be obtained. In particular, the amidamine and imine resin having a structure represented by (1) is excellent in light transmittance, so that the resolution can be improved. It is preferable that the amidamine imine resin has transparency. For example, the dry coating film of the amidamide imine resin is 25 μm, and the transmittance of light having a wavelength of 365 nm is preferably 70% or more.

The content of the structures of the formulas (1) and (2) in the amidamine and imine resin is preferably 10 to 70% by mass. By using this resin, a hardened product having excellent solvent solubility and excellent physical properties and dimensional stability such as heat resistance, tensile strength, and elongation can be obtained. It is preferably 10 to 60% by mass, and more preferably 20 to 50% by mass.

The amidoamine imine resin having a structure represented by the formula (1) is particularly one having the formula (3A) or (3B)

(In the formulae (3A) and (3B), R is a monovalent organic group, preferably H, CF ₃ or CH ₃ , and X is a direct bond or a divalent organic group, preferably a direct bond, Resins having a structure represented by an alkylene group such as CH ₂ or C (CH ₃ ) ₂ are preferred because of excellent physical properties and dimensional stability such as tensile strength and elongation. From the standpoint of solubility or mechanical properties, the aforementioned amidoamine imine resin can be suitably used as a resin having a structure of the formulae (3A) and (3B). More preferably, it is 20 to 80% by mass.

It is preferable that the amidamidine imine resin contains a structure having 5 to 100 mole% of the structures of the formulae (3A) and (3B) as the amidoimine resin. More preferably, it is 5 to 98 mole%, more preferably, it is 10 to 98 mole%, and particularly preferably, it is 20 to 80 mole%.

In addition, the amidamine and imine resin having a structure represented by the formula (2) is particularly preferably a compound having the formula (4A) or (4B)

(In the formulae (4A) and (4B), R is a monovalent organic group, preferably H, CF ₃ or CH ₃ , and X is a direct bond or a divalent organic group, preferably a direct bond, A resin having a structure represented by an alkylene group such as CH ₂ or C (CH ₃ ) ₂ is preferred because a hardened product having excellent mechanical properties such as tensile strength and elongation can be obtained. From the standpoint of solubility or mechanical properties, the aforementioned amidoamine imine resin can be suitably used as a resin having a structure of formulae (4A) and (4B) in an amount of 10 to 100% by mass. More preferably, it is 20 to 80% by mass.

For the reason that the amidamine imine resin exhibits good mechanical properties, it is also preferable to use amidamide imine resin having a structure of 2 to 95 mole% of formulae (4A) and (4B). More preferably, it is 10 to 80 mol%.

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

Examples of the diisocyanate compound having a biphenyl skeleton include 4,4'-diisocyanate-3,3'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-3,3'-di Ethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-di Ethyl-1,1'-biphenyl, 4,4'-diisocyanate-3,3'-di-trifluoromethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2 '-Di-trifluoromethyl-1,1'-biphenyl and the like. Alternatively, an aromatic polyisocyanate compound such as diphenylmethane diisocyanate can be used.

Examples of the cyclohexane polycarboxylic anhydride include cyclohexane tricarboxylic anhydride and cyclohexane tetracarboxylic anhydride.

Moreover, the fluorene amine imine resin which has a structure of (2) can be obtained using the said diisocyanate compound which has the biphenyl skeleton, and the polycarboxylic acid anhydride which has two acid anhydride groups, for example.

Polycarboxylic anhydrides having two acid anhydride groups include pyromellitic dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, and diphenyl ether-3,3', 4,4'-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, biphenyl-2 , 2 ', 3,3'-tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) Propane dianhydride, 2,3-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) fluorene dianhydride, bis (3,4-dicarboxyphenyl) ether Alkanediol dianhydride trimellitate, such as dianhydride, ethylene glycol dianhydrotrimellitate, and the like.

The amidoamine imine resin further has an alkali-soluble functional group in addition to the structures of the formulae (1) and (2). By having an alkali-soluble functional group, it becomes an alkali-developing resin composition. As the alkali-soluble functional group, those containing a carboxyl group, a phenolic hydroxyl group, a sulfo group, and the like are preferred, and those containing a carboxyl group are preferred.

In addition, specific examples of the amidamine imine resin include Unidic V-8000 series manufactured by DIC Corporation, and SOXR-U manufactured by NIPPON Advanced Paper Industries Co., Ltd.

Examples of the compound having a phenolic hydroxyl group include a compound having a biphenyl skeleton, an phenylene skeleton, or a skeleton of both of them, or a phenol, o-cresol, p-cresol, m-cresol, and 2,3-xylenol. , 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, Hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, gallophenol, resorcinol and other phenol resins with various skeletons.

Examples of the compound having a phenolic hydroxyl group include phenol novolac resin, alkylphenol novolac resin, bisphenol A novolac resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, and terpene modified phenol. Resins, polyvinyl phenols, bisphenol F, bisphenol S-type phenol resins, poly-p-hydroxystyrene, naphthol and aldehyde condensates, dihydroxynaphthalene and aldehydes, etc. Phenol resin.

Examples of commercially available phenol resins include HF1H60 (manufactured by Meiwa Chemical Co., Ltd.), Phenolite TD-2090, Phenolite TD-2131 (manufactured by Dainippon Printing Co., Ltd.), Besmol CZ-256-A (manufactured by DIC Corporation), Shonol BRG- 555, Shonol BRG-556 (manufactured by Showa Denko Corporation), CGR-951 (manufactured by Maruzen Oil Co., Ltd.), CST70, CST90, S-1P, S-2P (manufactured by Maruzen Oil Co., Ltd.) of polyvinyl phenol.

The acid value of the alkali-soluble resin is suitably in the range of 40 to 200 mgKOH / g, and more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the alkali-soluble resin is 40 mgKOH / g or more, alkali development becomes easy. On the other hand, when the acid value of the alkali-soluble resin is 200 mgKOH / g or less, the drawing of a normal hardened product pattern becomes easy, so it is preferable.

Although the weight-average molecular weight of the alkali-soluble resin varies depending on the resin skeleton, it is preferably in the range of 1,500 to 150,000, and further 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 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, 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 based on 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 that can harden the composition by light irradiation, and is preferably a photopolymerization initiator that generates radicals by light irradiation and a photobase that generates alkali by light irradiation. Any one of the generating agents. In addition, the photoreaction initiator may of course be a compound that generates both a radical and a base upon irradiation with light. Light irradiation means irradiation of ultraviolet rays in a wavelength range of 350 to 450 nm.

Examples of the photopolymerization initiator include bis- (2,6-dichlorobenzyl) phenylphosphine oxide and bis- (2,6-dichlorobenzyl) -2,5-dimethyl Phenylphenylphosphine oxide, bis- (2,6-dichlorobenzyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzyl) -1-naphthalene Phosphine oxide, bis- (2,6-dimethoxybenzyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzyl) -2,4,4- Trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethyl Dibenzylphosphine) -bisphosphonylphosphine oxides such as phenylphosphine oxide; 2,6-dimethoxybenzyldiphenylphosphine oxide, 2,6-dichlorobenzidine Diphenylphosphine oxide, methyl 2,4,6-trimethylbenzylidenephenyl hypophosphite, 2-methylbenzylidene diphenylphosphine oxide, trimethylacetamidobenzene Isopropyl hypophosphite, 2,4,6-trimethylbenzylidene diphenylphosphine oxide) and other monofluorenylphosphine oxides; 1-hydroxy-cyclohexylphenyl ketone, 1- [ 4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2 -Methyl-propanone ) -Benzyl] phenyl} -2-methyl-propane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and other hydroxyacetophenones; benzoin Benzene, diphenylethylenedione, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, etc. Marriage; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michelin, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenones and other benzophenones; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethyl Oxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholinyl-1-acetone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1, 2- (dimethylamino)- 2-[(4-methylphenyl) methyl) -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone, etc. Acetophenones; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2- Chlorothioxanthone, 2,4-diisopropylthioxanthone, etc. Thiothanone; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-pentylanthraquinone, 2- Anthraquinones such as amino anthraquinone; ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal; ethyl-4-dimethylamine benzoate, 2-benzoic acid 2- (Dimethylamino) ethyl esters, benzoates such as ethyl p-dimethylbenzoate; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O -Benzylidene oxime)], ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-ethyl Oxime esters such as fluorenyl oxime); bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl ) Titanocenes such as titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (1-pyrrole-1-yl) ethyl) phenyl] titanium; benzene Dinitrosulfide 2-nitroamidine, butyrin, anisyl ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide and the like. The photopolymerization initiator may be used singly or in combination of two or more kinds.

A photobase generator is a compound that changes one or more basic structures by irradiating light such as ultraviolet rays or visible light, or cracks the molecules to form one or more basic substances that can function as a catalyst for a thermosetting reaction. . Examples of the basic substance include a secondary amine and a tertiary amine.

Examples of the photobase generator include an α-aminoacetophenone compound, an oxime ester compound, or an oxoimino compound, an N-formylated aromatic amine compound, and an N-formated aromatic amine compound. , Nitrobenzyl aminoformate compounds, alkoxybenzylaminoformate compounds, and the like. Among them, oxime ester compounds and α-aminoacetophenone compounds are preferred; oxime ester compounds are more preferred; and ethyl ketone is even more preferred, 1- [9-ethyl-6- (2-methylbenzidine). ) -9H-carbazol-3-yl]-, 1- (O-acetamidooxime). The α-aminoacetophenone compound is particularly preferably one having two or more nitrogen atoms. The photobase generator may be used singly or in combination of two or more kinds. Examples of the photobase generator include quaternary ammonium salts and the like.

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) ethyl imidazole carboxylate), and the like.

Furthermore, a part of the photopolymerization initiator also functions as a photobase generator. The photopolymerization initiator that functions also as a photobase generator is preferably an oxime ester-based photopolymerization initiator and an α-aminoacetophenone-based photopolymerization initiator.

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

(Hardening accelerator)
The hardening accelerator of the present invention may contain a hardening accelerator. Examples of the hardening accelerator include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 1-cyanoethyl- Imidazole derivatives such as 2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamine, benzyldimethylamine, 4- (dimethylformamide) Amino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, 4 -Amine compounds such as dimethylaminopyridine; hydrazine compounds such as dihydrazine adipate, dihydrazine sebacate; phosphorus compounds such as triphenylphosphine. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, and 2-vinyl-2 can also be used. 2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isotricyanic acid adduct, 2,4-diamino-6-formaldehyde S-triazine derivatives such as propylene ethoxyethyl-S-triazine / isocyanuric acid adduct. A metal-based hardening accelerator may also be used, and examples thereof include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetoacetone, cobalt (III) acetoacetone, etc .; organic copper complexes of copper (II) acetoacetate, etc. Organic zinc complexes such as osmium zinc acetone (II), organic iron complexes such as ethyl acetone iron (III), organic nickel complexes such as ethyl acetonide nickel (II), and manganese (II) ) And the like. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. The hardening accelerator is preferably a compound that functions in combination with a hardening accelerator and also functions as such an adhesion-imparting agent. A hardening accelerator can be used individually by 1 type or in combination of 2 or more types.

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

(hardener)
The curable resin composition of the present invention may contain a curing agent. Examples of the curing agent include compounds having a phenolic hydroxyl group, polycarboxylic acids and their anhydrides, compounds having a cyanate group, compounds having an active ester group, compounds having a maleimide group, and alicyclic olefin polymers. . A hardening agent can be used individually by 1 type or in combination of 2 or more types.

As the compound having a phenolic hydroxyl group, phenol novolac resin, alkylphenol novolac resin, bisphenol A novolac resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, Cresol / naphthol resin, polyvinyl phenols, phenol / naphthol resin, phenol resin with α-naphthol skeleton, cresol novolac resin with triazine skeleton, biphenylaralkyl type phenol resin, Xylock A conventionally known phenol novolac resin and the like.
Among the compounds having a phenolic hydroxyl group, a hydroxyl equivalent of 100 g / eq. Or more is preferred. Examples of compounds having a phenolic hydroxyl group with a hydroxyl equivalent of 100 g / eq. Or more include, for example, dicyclopentadiene skeleton phenol novolac resin (GDP series, manufactured by Qunei Chemical Co., Ltd.), and Xylock type novolac resin (MEH-7800, (Made by Meiwa Kasei Co., Ltd.), biphenyl aralkyl type novolac resin (MEH-87851, manufactured by Meiwa Kasei Co., Ltd.), naphthol aralkyl type hardener (SN series, manufactured by Nippon Steel & Sumikin Co., Ltd.), triazine skeleton Cresol novolac resin (LA-3018-50P, manufactured by DIC Corporation), triazine skeleton-containing phenol novolac resin (LA-705N, manufactured by DIC Corporation), and the like.

The compound having a cyanate group is preferably a compound having two or more cyanate groups (-OCN) in one molecule. Any compound having a cyanate ester group can be used. Examples of the compound having a cyanate group include a phenol novolac type cyanate resin, an alkyl novolac type cyanate resin, a dicyclopentadiene type cyanate resin, and a bisphenol A type cyanate resin. , Bisphenol F-type cyanate resin, bisphenol S-type cyanate resin. In addition, it may be a triazinated prepolymer.

Commercially available compounds having a cyanate group include phenol novolac-type polyfunctional cyanate resin (Lonza Japan Co., PT30S), and some or all of the bisphenol A dicyanates are triazinated to form three Polymer prepolymer (Lonza Japan, BA230S75), dicyclopentadiene-containing cyanate resin (Lonza Japan, DT-4000, DT-7000) and the like.

The compound having an active ester group is preferably a compound having two or more active ester groups in one molecule. The compound having an active ester group is generally obtained by a condensation reaction between a carboxylic acid compound and a hydroxy compound. Among them, a compound having an active ester group obtained by using a phenol compound or a naphthol compound as a hydroxy compound is particularly preferable. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, and 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, resorcinol, pyroglycerol, dicyclopentadienyl diphenol, phenol novolac, etc. . The compound having an active ester group may be a naphthalene glycol alkyl / benzoic acid type.

Examples of commercially available compounds having an active ester group include cyclopentadiene-type diphenol compounds such as HPC8000-65T (manufactured by DIC), HPC8100-65T (manufactured by DIC), and HPC8150-65T (manufactured by DIC).

The compound having a maleimidine imine group is a compound having a maleimide imine skeleton, and any of the conventionally known ones can be used. A compound having a maleimidine imine group, preferably having two or more maleimide imine skeletons; more preferably 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 -Maleimide phenoxy) phenyl] propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4 -Methyl-1,3-phenylenebismaleimide, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, bisphenol A diphenyl ether bis At least one of maleimide, polyphenylmethanemaleimide, and oligomers thereof, and a diamine condensate having a maleimide skeleton. The oligomer is an oligomer obtained by condensing a compound having a maleimide group among monomers in the compound having a maleimide group.

Commercially available compounds having a maleimidine group include BMI-1000 (4,4'-diphenylmethanebismaleimide, manufactured by Daiwa Chemical Industry Co., Ltd.), and BMI-2300 (phenylmethanebisimide Maleimide, manufactured by Yamato Chemical Industry Co., Ltd.), BMI-3000 (m-phenylene bismaleimide, manufactured by Daiwa Chemical Industry Co., Ltd.), BMI-5100 (3,3'-dimethyl-5 , 5'-dimethyl-4,4'-diphenylmethane bismaleimide, manufactured by Daiwa Chemical Industry Co., Ltd.), BMI-7000 (4-methyl-1,3, -phenylene bismaline Laimide, manufactured by Daiwa Chemical Industry Co., Ltd., BMI-TMH ((1,6-bismaleimide-2,2,4-trimethyl) hexane, manufactured by Daiwa Chemical Industry Co., Ltd.), MIR- 3000 (biphenylaralkyl maleimide, manufactured by Nippon Kayaku Co., Ltd.) and the like.

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

(Thermoplastic resin)
In order to improve the mechanical strength of the obtained cured film, the curable resin composition of the present invention may further contain a thermoplastic resin. The thermoplastic resin is preferably soluble in a solvent. When soluble in a solvent, the softness of the film after drying is improved, and the occurrence of cracks or powder falling can be suppressed. Examples of the thermoplastic resin include thermoplastic polyhydroxy polyether resins, phenoxy resins which are condensates of epichlorohydrin and various bifunctional phenol compounds, or various acid anhydrides or acid chlorides for the hydroxyl groups of the hydroxy ether portion in the skeleton. Phenoxy resin, polyvinyl acetal resin, polyamide resin, polyamidamine resin, block copolymer, rubber particles, etc., obtained by esterification of a compound. The thermoplastic resin may be used singly or in combination of two or more kinds.

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.

(Colorant)
The curable resin composition of the present invention may contain a colorant. As the colorant, known colorants such as red, blue, green, yellow, black, white, and the like can be used, and any of pigments, dyes, and pigments can be used. However, from the viewpoint of reducing the environmental load and the influence on the human body, it is preferable not to contain halogen. The colorant can be used alone or in combination of two or more kinds.

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

(Organic solvents)
The curable resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition or adjusting the viscosity when coating the substrate or the carrier film. As the organic solvent, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cyperidine, methyl cyperidine, butyl cyperazole, and carbitur Alcohol, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether Glycol ethers such as ethyl ether; ethyl acetate, butyl acetate, butyl lactate, cyperidine acetate, butyl cyperidine acetate, carbitol acetate, butylcarbitol ethyl Esters of acetic acid, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate, etc .; aliphatic hydrocarbons such as octane, decane; petroleum ether, petroleum naphtha, solvents Well-known and commonly used organic solvents such as petroleum solvents such as petroleum naphtha. These organic solvents may 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 additives commonly used in the field of electronic materials. Other additives include thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antioxidants, antibacterial and antifungal agents, defoamers, leveling agents, and additives. Adhesives, adhesion-imparting agents, shake modifiers, light-starting aids, sensitizers, organic fillers, elastomers, mold release agents, surface treatment agents, dispersants, dispersion aids, surface modifiers , Stabilizers, phosphors, etc.

The curable resin composition of the present invention may contain a well-known and commonly used inorganic filler other than the surface-treated silica particles as long as the effect of the present invention is not impaired. Examples of such inorganic fillers include silicon dioxide other than the surface-treated silica particles, Neuburg silica, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, and hydrogen. Inorganic fillers such as alumina, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, zinc bloom, etc.

The curable resin composition of the present invention is not particularly limited, and may be any of a thermosetting resin composition, a photocurable resin composition, a photocurable thermosetting resin composition, and a photosensitive thermosetting resin composition. By. Moreover, it may be an alkali imaging type, a negative type, or a positive type. Specific examples include a thermosetting resin composition, a photocurable thermosetting resin composition, a photocurable thermosetting resin composition containing a photopolymerization initiator, and a photocurable thermosetting resin containing a photobase generator. Resin composition, negative photocurable thermosetting resin composition, positive photosensitive thermosetting resin composition, alkali developing photocurable thermosetting resin composition, solvent developing photocuring thermosetting A flexible resin composition, a swelling and peeling type thermosetting resin composition, a dissolution and peeling type thermosetting resin composition, and the like are not limited thereto.

The arbitrary components contained in the curable resin composition of the present invention may be selected from known and commonly used components in accordance with the curability and application.

For example, when the curable resin composition of the present invention is a thermosetting resin composition (without a photopolymerization initiator), it contains a thermosetting resin. Moreover, it is preferable to contain a hardening accelerator. It is preferable to contain a hardening | curing agent. The blending amount of the thermosetting resin is preferably 1 to 50% by mass of the total solid content of the composition. The blending amount of the hardening accelerator is preferably 0.01 to 30% by mass of the total solid content of the composition. The blending amount of the hardener is preferably 0.01 to 30% by mass of the total solid content of the composition.

Moreover, when the curable resin composition of this invention is a photocurable thermosetting resin composition, it contains a photocurable resin, a thermosetting resin, and a photoreaction initiator. In the case of an alkali developing type, the photocurable resin may be an alkali-soluble resin, or 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 of the total solid content of the composition. The blending amount of the thermosetting resin is preferably 1 to 50% by mass of the total solid content of the composition. The blending amount of the photocurable resin (except for the photocurable alkali-soluble resin) is preferably 1 to 50% by mass of the total solid content of the composition. The blending amount of the photoreaction initiator is preferably 0.01 to 30% by mass of the total solid content of the composition. The blending amount of the hardening accelerator is preferably 0.01 to 30% by mass of the total solid content of the composition.

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

The dry film of the present invention has a resin layer obtained by coating and curing the curable resin composition of the present invention on a carrier film. When forming a dry film, the curable resin composition of the present invention is first diluted with the above-mentioned organic solvent and adjusted to an appropriate viscosity, and then is cut off by a notch wheel applicator, a doctor blade applicator, a lip applicator, and a bar coater. A carrier, a squeeze coater, a reverse roll coater, a transfer roll coater, a gravure coater, a spray coater, etc. are applied to the carrier film to a uniform thickness. Thereafter, the coated composition is 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. Generally speaking, it is appropriately selected in a range of 3 to 150 μm, preferably 5 to 60 μm, based on the film thickness after drying.

As the carrier film, a plastic film can be used. For example, polyester film such as polyethylene terephthalate (PET), polyimide film, polyimide film, polypropylene film, polystyrene can be used. Film, etc. The thickness of the carrier film is not particularly limited, and is generally appropriately selected in a range of 10 to 150 μm. A more preferable range is 15 to 130 μm.

After forming a resin layer composed of the curable resin composition of the present invention on a carrier film, it is preferable to further laminate a peelable cover film on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. The peelable cover film can be, for example, a polyethylene film or a polytetrafluoroethylene film, a polypropylene film, or a surface-treated paper. As the cover film, as long as the cover film is peeled off, the adhesive force between the resin layer and the carrier film is smaller.

In addition, in the present invention, the hardening resin composition of the present invention is coated on the cover film and dried to form a resin layer, and a carrier film is laminated on the surface. That is, in the present invention, when the dry film is produced, the thin film, the carrier film, and the cover film that are applied to the curable resin composition of the present invention can be used.

As the method for producing a printed wiring board using the curable resin composition of the present invention, a conventionally known method may be used. When an alkali-developed photocurable thermosetting resin composition is used as an example, for example, the curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using the above-mentioned organic solvent, and is applied by dipping. Method, flow coating method, roll coating method, bar coating method, screen printing method, curtain coating method, etc. After coating on the substrate, the composition is applied at a temperature of 60 to 100 ° C. The contained organic solvent is evaporated and dried (temporarily dried) to form a non-sticky resin layer. In the case of a dry film, a resin layer is formed on the substrate after the carrier film is peeled off after being bonded to the substrate by a laminator or the like so that the resin layer is in contact with the substrate.

Examples of the substrate include a printed wiring board or a flexible printed wiring board in which a circuit is formed with copper or the like in advance. In addition, the use of paper phenol, paper epoxy resin, glass cloth epoxy resin, glass polyimide, and glass is used. Cloth / non-fiber cloth epoxy resin, glass cloth / paper epoxy resin, synthetic fiber epoxy resin, fluororesin / polyethylene / polyphenylene ether, polyphenylene ether / cyanate, etc. And other materials, and all grades (FR-4, etc.) copper-clad laminates, others include metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates , Ceramic substrate, wafer board, etc. Pre-processing can also be performed on the circuit. For example, GliCAP manufactured by Shikoku Kasei Corporation, New Organic AP (Adhesion promoter) manufactured by MEC Corporation, Nova Bond manufactured by Atotech Japan Corporation, etc. can be used to improve solder resist and curing Adhesiveness of the film, etc., or pretreatment with a rust inhibitor.

The volatilizing drying performed after the application of the curable resin composition of the present invention can be performed using a hot-air circulation type drying furnace, an IR furnace, a heating plate, a convection oven, etc. The method of contacting the hot air in the counter current and the method of blowing the support from the nozzle) is performed.

After the resin layer is formed on the printed wiring board, a mask with a specific pattern is formed to selectively expose it with active energy rays, and the unexposed portion is developed with a dilute aqueous alkali solution (for example, 0.3 to 3% by mass sodium carbonate aqueous solution). Form a pattern of hardened objects. Further, the hardened object is irradiated with active energy rays and then heat-cured (for example, 100 to 220 ° C.), or heat-cured and irradiated with active energy rays, or is subjected to final trimming and hardening (formal hardening) only by heating and hardening to form adhesion and hardness A cured film with excellent properties.

The exposure machine used for the above active energy ray irradiation may be a device equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short-arc lamp, and the like, and irradiates ultraviolet rays in the range of 350 to 450 nm. A projection exposure machine using a projection lens or a direct drawing device (for example, a laser direct imaging device that draws an image directly with a laser by using CAD data from a computer) without masking exposure without contacting the substrate. The light source or laser light source of the direct scan machine can be a maximum wavelength of 350 ~ 450nm. Although the exposure amount used to form an image varies depending on the film thickness and the like, it can generally be in the range of 10 to 1000 mJ / cm ² , preferably 20 to 800 mJ / cm ² .

The above-mentioned development method can be performed by a dipping method, a rinsing method, a spray method, a brush method, or the like, and the developing solution can be potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia , Amines and other alkaline aqueous solutions.

The curable resin composition of the present invention is suitable for forming a hardened film on an electronic part, especially a hardened film on a printed wiring board. It is more suitable for forming a permanent film, and is more suitable for forming a solder resist and an interlayer insulating layer. , Coating, sealing material. For example, the curable resin composition of the present invention may be an alkali developing type and used to form an interlayer insulating layer. Moreover, it is suitable for forming a printed wiring board which requires high reliability, such as a package substrate, especially a permanent film (especially a solder resist) for FC-BGA. The curable resin composition of the present invention can also be suitably used for a printed wiring board having a wiring pattern even if the thickness of the circuit surface is small, such as a high-frequency printed wiring board. 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 be used suitably also when forming a hardened film on a base material with low polarity, for example, a base material containing an active ester. Furthermore, it is also suitable for forming a cured film on a wafer or a glass substrate without roughening.

The laminated structure of the present invention is a structure comprising a resin hardened layer (A) and a resin hardened layer (B) or a substrate (C) adjacent to the resin hardened layer (A), which is characterized by the resin hardened layer (A) is the hardened resin composition of the present invention or the hardened resin layer of the dry film of the present invention, and the other potential of the resin hardened layer (B) or the substrate (C) is not positive.

As described above, in the present invention, by performing surface treatment such that the other potential of the silicon dioxide particles becomes positive, a decrease in adhesion can be suppressed, and thus a laminated structure having excellent adhesion between layers can be produced.

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

The thicknesses of the resin hardened layers (A), (B) and the substrate (C) in the laminated structure of the present invention are not particularly limited.

The combination of the resin hardened layer (A) and the resin hardened layer (B) is not particularly limited, and examples thereof include the solder resist 13 and the interlayer insulating material 11 and A combination of the flux 13 and the underfill 16, and the solder resist 13 and the sealing material 17. Any of the resin hardened layers (A) and (B) may be used in the above combination, but the resin hardened layer (A) is preferably a solder resist. Here, any one of the interlayer insulating material 11, the solder resist 13, the underfill material 16, and the sealing material 17 is filled with surface-treated silica particles having a positive potential, and a resin hardened layer adjacent thereto. The adhesion becomes good.

The combination of the resin hardened layer (A) and the substrate (C) is not particularly limited, and examples thereof include the solder resist (A) 13 and the interlayer insulation included in the laminated structure shown schematically in FIG. 1. Material (C) 11, solder resist (A) 13 and semiconductor wafer (C) 15, underfill (A) 16 and semiconductor wafer (C) 15, sealing material (A) 17 and semiconductor wafer (C) 15 combinations.

The surfaces of the resin hardened layer (B) and the substrate (C) need only be those in which the other potential is not positive, and 0 or negative.

[Example]

The following examples are used to explain the present invention in more detail, but the present invention is not limited to the following examples. In addition, the following are recorded as "part" and "%", unless otherwise specified, they are all based on quality.

[Synthesis of alkali-soluble resin]
(Synthesis of alkali-soluble resin A-1)
In a flask equipped with a cooling tube and a stirrer, 456 parts of bisphenol A, 228 parts of water, and 649 parts of 37% formalin were kept, and the temperature was kept below 40 ° C, and 228 parts of a 25% sodium hydroxide aqueous solution was added. After the addition was completed, the reaction was carried out at 50 ° C for 10 hours. After the completion of the reaction, it was cooled to 40 ° C, and neutralized to a pH of 4 with a 37.5% phosphoric acid aqueous solution while maintaining the temperature below 40 ° C. Then, it stood still and separated the water layer. After the separation, 300 parts of methyl isobutyl ketone was added to dissolve uniformly, and then washed three times with 500 parts of distilled water, and the water and the solvent were removed under a reduced pressure at a temperature of 50 ° C or lower. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1,230 parts of a polymethylol compound in methanol solution.
A part of the methanol solution of the obtained polymethylol compound was dried in a vacuum dryer at room temperature, and the solid content was 55.2%.
In a flask equipped with a cooling tube and a stirrer, 500 parts of the methanol solution of the obtained polymethylol compound and 440 parts of 2,6-xylenol were fed, and uniformly dissolved at 50 ° C. After homogeneous dissolution, at a temperature below 50 ° C, methanol was removed under reduced pressure. Then, 8 parts of oxalic acid was added, and it was made to react at 100 degreeC for 10 hours. After the reaction was completed, the distillate component was removed under a reduced pressure of 180 ° C. and 50 mmHg to obtain 550 parts of novolac resin A.
In a autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a stirring device, 130 parts of novolac resin A, 2.6 parts of 50% sodium hydroxide aqueous solution, and toluene / methyl isobutyl ketone (mass Ratio = 2/1) 100 parts, while replacing the inside of the system with nitrogen while stirring, and then heating up the temperature, 60 parts of propylene oxide was slowly introduced at 150 ° C and 8 kg / cm ² to react. The reaction system continued for about 4 hours until the gauge pressure became 0.0 kg / cm ² , and then cooled to room temperature. To this reaction solution, 3.3 parts of a 36% aqueous hydrochloric acid solution was added and mixed to neutralize sodium hydroxide. This neutralization reaction product was diluted with toluene, washed three times with water, and desolvated with an evaporator to obtain a propylene oxide adduct of novolak resin A having a hydroxyl value of 189 g / eq. This is an average addition of 1 mole of propylene oxide per phenolic hydroxyl group.
189 parts of propylene oxide adduct of the obtained novolak resin A, 36 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 parts of hydroquinone monomethyl ether, and 140 parts of toluene were fed to a mixer, a thermometer, and an air blower. The reactor that was introduced into the tube was stirred while blowing air, and heated to 115 ° C. The water and toluene produced by the reaction were distilled off as an azeotrope, and after reacting for 4 hours, it was cooled to room temperature. The obtained reaction solution was washed with a 5% NaCl aqueous solution and distilled off under reduced pressure to remove toluene, and then diethylene glycol monoethyl ether acetate was added to obtain an acrylic resin solution having a solid content of 67%.
Next, in a 4-neck flask equipped with a stirrer and a reflux cooler, 322 parts of the obtained acrylate resin solution, 0.1 part of hydroquinone monomethyl ether, and 0.3 part of triphenylphosphine were fed, and the mixture was heated to 110 ° C. Then, 60 parts of tetrahydrophthalic anhydride was added, the reaction was performed for 4 hours, and the mixture was taken out after cooling. The photosensitive carboxyl group-containing resin solution thus obtained had a solid content of 70% and a solid content acid value of 81 mgKOH / g. Hereinafter, this carboxyl group-containing photosensitive resin solution is referred to as a resin solution A-1.

[Surface treatment of silicon dioxide particles]
(Silica dioxide particles blended in Example 1: silica particles coated with aluminum hydrated oxide)
After 50 g of an aqueous slurry of spherical silica particles (SFP-20M manufactured by Denka Corporation, average particle size: 0.4 μm) was heated to 70 ° C., a 20% sodium aluminate (NaAlO ₂ ) aqueous solution was used for the silica particles. , Add 2 ~ 3% in the conversion of alumina (Al ₂ O ₃ ). Thereafter, a 20% sodium hydroxide aqueous solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. After that, the slurry was filtered and washed with a filter press, and dried under vacuum to obtain a solid substance of silica particles coated with aluminum hydrated oxide.

(Silica dioxide particles blended in Example 2: Silica particles coated with zirconium hydrated oxide)
After 50 g of an aqueous slurry of spherical silica particles (SFP-20M manufactured by Denka Corporation, average particle size: 0.4 μm) is heated to 70 ° C., an aqueous solution of a water-soluble zirconium compound such as zirconyl oxychloride is 100 g / 1 For silica particles, add 2 to 3% in terms of zirconia (ZrO ₂ ). Thereafter, a 20% sodium hydroxide aqueous solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. After that, the slurry was filtered and washed with a filter press, and dried under vacuum to obtain a solid substance of silica particles coated with hydrated oxide of zirconia.

(Silica dioxide particles blended in Example 3: silica particles treated with zinc oxide hydrated oxide coating)
After heating 50 g of spherical silica particles (SFP-20M manufactured by Denka Corporation, average particle size: 0.4 μm) to 70 ° C., an aqueous solution of zinc sulfate was added to the silica particles in ZnO conversion to 2 ~ 3%. Thereafter, a 20% sodium hydroxide aqueous solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. After that, the slurry was filtered and washed with a filter press, and dried under vacuum to obtain a solid substance of silica particles coated with zinc hydrated oxide.

(Silica dioxide particles blended in Example 4: silica particles coated with titanium hydrated oxide)
A 50 g aqueous slurry of spherical silica particles (SFP-20M manufactured by Denka, average particle size: 0.4 μm) was heated to 70 ° C., and then a 100 g / l titanyl sulfate aqueous solution was used for the silica particles by TiO ₂ conversions add 2 ~ 3%. Thereafter, a 20% sodium hydroxide aqueous solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. After that, the slurry was filtered and washed with a filter press, and dried under vacuum to obtain a solid substance of silica particles coated with titanium hydrated oxide.

(Silicon dioxide particles blended in Example 5: silicon dioxide particles treated with aluminum hydrated oxide coating treatment after silicon hydrated oxide coating treatment)
50 g of an aqueous slurry of spherical silica particles (SFP-20M manufactured by Denka, average particle size: 0.4 μm) was heated to 70 ° C., and then a 10% sodium silicate aqueous solution was used to dissolve the silica particles in the form of dioxide. Add 1% in silicon particle conversion. Hydrochloric acid was added to the slurry, the pH was adjusted to 4, and the mixture was aged for 30 minutes. The pH was further maintained at 5 ± 1 by hydrochloric acid, and a 20% sodium aluminate (NaAlO ₂ ) aqueous solution was used. (Al ₂ O ₃ ) converted and added 5%. Thereafter, a 20% sodium hydroxide aqueous solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. After that, the slurry was filtered and washed with a filter press, and vacuum dried to obtain a solid substance of silicon dioxide particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum.

(Silicon dioxide particles blended in Example 6: silicon dioxide particles treated with a hydrated oxide coating of zirconium after being coated with a hydrated oxide of silicon)
50 g of an aqueous slurry of spherical silica particles (SFP-20M manufactured by Denka, average particle size: 0.4 μm) was heated to 70 ° C., and then a 10% sodium silicate aqueous solution was used to dissolve the silica particles in the form of dioxide. Add 1% in silicon particle conversion. Hydrochloric acid was added to the slurry to adjust the pH to 4 and the mixture was aged for 30 minutes. The pH was further maintained at 5 ± 1 by hydrochloric acid, and the temperature was raised to 40 ° C. Then, a 100 g / l zirconyl oxychloride aqueous solution was added to the silica particles. Add 5% in ZrO ₂ conversion. Thereafter, a 20% sodium hydroxide aqueous solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. After that, the slurry was filtered and washed with a filter press, and vacuum dried to obtain a solid substance of silicon dioxide particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum.

(Silica dioxide particles blended in Example 7: silicon dioxide particles treated with zinc oxide coating after being treated with silicon hydrated oxide)
50 g of an aqueous slurry of spherical silica particles (SFP-20M manufactured by Denka, average particle size: 0.4 μm) was heated to 70 ° C., and then a 10% sodium silicate aqueous solution was used to dissolve the silica particles in the form of dioxide. Add 1% in silicon particle conversion. Hydrochloric acid was added to the slurry, the pH was adjusted to 4, and the mixture was aged for 30 minutes. The pH was further maintained at 5 ± 1 by hydrochloric acid, and the temperature was raised to 45 ° C. Then, an aqueous solution of zinc sulfate was converted to ZnO for silicon dioxide particles Add 5 mass%. Thereafter, a 20% sodium hydroxide aqueous solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. After that, the slurry was filtered and washed with a filter press, and vacuum dried to obtain a solid substance of silicon dioxide particles coated with a hydrated oxide of silicon and a hydrated oxide of zinc.

(Silicon dioxide particles blended in Example 8: Silicon dioxide particles treated with a hydrated oxide coating of silicon after being coated with a hydrated oxide of silicon)
50 g of an aqueous slurry of spherical silica particles (SFP-20M manufactured by Denka, average particle size: 0.4 μm) was heated to 70 ° C., and then a 10% sodium silicate aqueous solution was used for the silica particles, and Add 1% in silicon particle conversion. Hydrochloric acid was added to the slurry to bring the pH to 4, and the mixture was aged for 30 minutes. The pH was further maintained at 5 ± 1 by hydrochloric acid, and the temperature was raised to 40 ° C. Then, a 100 g / l titanyl sulfate aqueous solution was added to the silica particles. Add 5% in terms of TiO ₂ . Thereafter, a 20% sodium hydroxide aqueous solution was added to adjust the pH to 7, and the mixture was aged for 30 minutes. After that, the slurry was filtered and washed with a filter press, and vacuum dried to obtain a solid substance of silicon dioxide particles coated with a hydrated oxide of silicon and a hydrated oxide of titanium.

(Silica dioxide particles blended in Examples 9 and 11: silica particles coated with a hydrated oxide of aluminum and surface-treated with methacrylfluorenylsilane)
50 g of the aluminum oxide-coated silicon dioxide particles and 48 g of PMA as a solvent, and 1 g of a silane coupling agent (KBM-503 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) having a methacryl group were uniformly dispersed. Filtration, washing with water, and vacuum drying, to obtain a solid material of silica particles treated with methacrylfluorenylsilane.

(Silica dioxide particles blended in Example 12: silica particles coated with aluminum hydrated oxide and surface treated with amine silane)
50 g of the aluminum oxide-coated silica particles and 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 Industry Co., Ltd.) were uniformly dispersed, and filtered. , Washing with water, and drying under vacuum to obtain a solid substance of silica particles treated with phenylaminosilane surface.

(Silicon dioxide particles blended in Example 10: Silicon dioxide particles coated with a hydrated oxide of silicon and then coated with a hydrated oxide of aluminum and surface-treated with methacrylfluorenylsilane)
50 g of the silica particles coated with the hydrated oxide of silicon after being coated with the aluminum, and 48 g of PMA as a solvent, and a silane coupling agent having a methacryl group (Shin-Etsu Chemical Industry Co., Ltd.) KBM-503) (1 g) was uniformly dispersed, and filtered, washed with water, and dried under vacuum to obtain a solid material of silicon dioxide particles surface-treated with methacrylfluorenylsilane.

(Silicon dioxide particles blended in Comparative Example 5: silicon dioxide particles surface-treated with amine silane)
50 g of spherical silica particles (SFP-20M manufactured by Denka Corporation, average particle size: 0.4 μm), 48 g of PMA as a solvent, and a silane coupling agent having a phenylamino group (KBM-573 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 1 g was uniformly dispersed, and filtered, washed with water, and dried under vacuum to obtain a solid substance of silicon dioxide particles surface-treated with phenylaminosilane.

(Silica dioxide particles blended in Comparative Examples 2 and 4: Silica dioxide particles surface-treated with methacrylfluorenylsilane)
50 g of spherical silica particles (SFP-20M, manufactured by Denka Corporation, average particle size: 0.4 μm), 48 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and a silyl couple having a methacryl group 1 g of the mixture (KBM-503 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was uniformly dispersed, and filtered, washed with water, and dried under vacuum to obtain a solid material of silicon dioxide particles surface-treated with methacrylfluorenylsilane.

[Determination of Sunda Potential]
The ELSZ-2000ZS manufactured by Otsuka Electronics was used to measure silicon dioxide particles (SFP-20M manufactured by Denka Corporation, average particle diameter: 0.4 μm), and the other potential of the surface-treated silicon dioxide particles prepared as described above.
Specifically, each particle was adjusted with a PMA (propylene glycol monomethyl ether acetate) to a concentration of 0.1% by weight, and dispersed in an ultrasonic bath for 1 minute. For the measurement, a flow cell was used, an applied voltage of 300 V was applied, and the other potential at 20 ° C was measured. In addition, the potential was calculated by the calculation formula of Huckel.
(Huckel's formula)
ζ = 6πηU / ε
ζ: Sunda potential
U: electric mobility η: solvent viscosity

[Examples 1 to 12, Comparative Examples 1 to 5]
The various components shown in Tables 1 and 2 below were blended in the proportions (parts by mass) shown in Tables 1 and 2, and diluted with a bead mill with an organic solvent to a dispersible viscosity. The bead mill is kneaded to disperse the curable resin composition. The obtained dispersion was passed through a filter having a pore size of 10 μm to obtain a curable resin composition.

＜ Production of dry film ＞
To the curable resin composition obtained as described above, 300 g of methyl ethyl ketone was added and diluted, and the mixture was stirred for 15 minutes with a stirrer to obtain a coating solution. The coating solution was coated on a polyethylene terephthalate film (carrier film, Emblet PTH-25 manufactured by Unitika) with a surface roughness of Ra 150 nm and a thickness of 38 μm, usually at 80 to 100 ° C. (Example 1 ~ 11 and Comparative Examples 1 to 4 were dried at a temperature of 80 ° C for 15 minutes, and Example 12 and Comparative Example 5 were dried at a temperature of 100 ° C for 15 minutes) to form a resin layer having a thickness of 40 µm. Next, a polypropylene film (overlay film, OPP-FOA manufactured by Futamura Co., Ltd.) with a thickness of 18 μm was laminated on the resin layer to produce a dry film.

＜ Production of hardened film ＞
From the dry film release polypropylene film obtained as described above, the resin layer of the dry film was bonded to the glossy side of the copper foil of GTS-MP foil (manufactured by Furukawa Circuit Foil), and then a vacuum laminator (named MVLP-500 manufactured by Seisakusho Co., Ltd.) With a pressure of 0.8 MPa, 70 to 100 ° C (Examples 1 to 11 and Comparative Examples 1 to 4 are at 70 ° C, Example 12 and Comparative Example 5 are at 100 ° C), 1 minute, Vacuum degree: Under the condition of 133.3Pa, heat and overlap to make the copper foil and resin layer tightly adhere.
Next, Examples 1 to 11 and Comparative Examples 1 to 4 are self-drying films after exposure on a dry film using an exposure device equipped with a high-pressure mercury lamp (short arc lamp) (exposure amount: 400 to 600 mJ / cm ² ). The polyethylene terephthalate film was peeled to expose the resin layer. Thereafter, development was performed for 60 seconds using a 1% by weight Na ₂ CO ₃ aqueous solution at 30 ° C. and a spray pressure of 2 kg / cm ^{2 to} form a resin layer having a resist pattern having a width of 3 mm. Next, the resin layer was irradiated with a UV conveyor furnace equipped with a high-pressure mercury lamp at an exposure amount of 1 J / cm ² , and then heated at 160 ° C. for 60 minutes to completely harden the resin layer to produce a cured film. In Example 12 and Comparative Example 5, after the dry film was laminated, the PET film was peeled off and cured completely at 190 ° C for 60 minutes.

<Measurement of CTE (α1)>
The cured film obtained as described above was peeled from the copper foil to obtain a measurement size (size of 3 mm × 16 mm), and a sample was set on TMA-Q400EM manufactured by TA Instruments to measure CTE. The measurement conditions were a test load of 5 g, and the sample was heated twice from room temperature at a temperature increase rate of 10 ° C./minute to obtain a second linear expansion coefficient (CTE (α1)) of Tg or less. The lower CTE (α1) is more able to suppress the generation of stress, so it is preferably 40 ppm or less.

＜ Measurement of alpha ray quantity ＞
Based on the JEDEC89A standard specification (2006), the amount of alpha rays of each curable resin composition of Examples 1 to 12 and Comparative Examples 1 to 5 was measured.
〇: less than 0.02 c / h / cm ²
×: 0.02c / h / cm ² or more

＜ Evaluation of adhesion to wafer glass substrate ＞
A cured film was produced on AN100 glass (manufactured by Asahi Glass Co., Ltd., Sunda Potential: negative) as a glass substrate under the same conditions as in the above-mentioned "Production of cured film". Based on JIS K5400, a cross-cutting machine was used to make 100 square (1 × 10) square checkers of 1 mm square to the interlayer material. The celluloid bands were completely tightly sealed on it, and several of the 100 were confirmed after pulling away. adaptation.
〇: 100/100
△: Above 70/100 and less than 100/100
×: less than 70/100

＜ Evaluation of Adhesion of Low Polarity Insulating Materials ＞
A hardened film was produced on a low-transmission loss interlayer material (dielectric tangent of Ajinomoto ABF GL102 circuit board, solar potential: negative) of 10 GHz with a dielectric tangent of about 0.004, under the same conditions as in the above-mentioned "Production of hardened film" . Based on JIS K5400, a cross-cutting machine was used to make 100 square (1 × 10) square checkers of 1 mm square to the interlayer material. The celluloid bands were completely tightly sealed on it, and several of the 100 were confirmed after pulling away. adaptation.
〇: 100/100
△: Above 70/100 and less than 100/100
×: less than 70/100

＜ Evaluation of EMC adhesion (adhesion to mold material) ＞
A circular mold (2.523 mm in diameter and 3.00 mm in height) was compression-molded on a non-plasma-treated hardened film using a mold material (UV8710U manufactured by Panasonic), and the mold material was hardened by heating at 175 ° C for 4 hours. Thereafter, a shearing force was applied to the mold material provided on the surface of the cured film, and the peeling strength between the cured film and the mold material was measured.

<Peel strength measuring device>
Made by NIDEC-SHIMPO company, shear speed: 20mm / min

＜ Evaluation criteria ＞
〇: 150N or more △: 100N or more and less than 150N
×: Less than 100N

＜ Evaluation of sensitivity ＞
The polyethylene film was peeled from the dry film obtained as described above, and the resin layer of the dry film was bonded to the surface side of the copper-clad substrate roughened by CZ8101B. Then, Examples 1 to 11 and Comparative Examples 1 to 4 were vacuumed. The laminating machine (MVLP-500 manufactured by Meiki Seisakusho) was heated and laminated under the conditions of pressure: 0.8 MPa, 70 ° C, 1 minute, and vacuum: 133.3 Pa, so that the copper foil and the resin layer were closely adhered.
Next, after using a projection exposure machine to expose through a ladder plate (Stuffer 41 stage) (exposure amount: 100 mJ / cm ² ), the polyethylene terephthalate film was peeled from the dry film to expose the resin layer. Thereafter, development was performed for 60 seconds using a 1% by weight aqueous Na ₂ CO ₃ solution at 30 ° C. and a spray pressure of 2 kg / cm ^{2 to} confirm the residual sensitivity of the ladder plate.

* 1: Carboxyl-containing resin A-1 synthesized above
* 2: EMG-1015 manufactured by DIC Corporation: Carboxyl-containing resin A-2 with amidamine and imine structure
* 3: NC-6000 manufactured by Nippon Kayaku Co., Ltd.
* 4: DIC Corporation HP7200
* 5: ESN-475V (naphthol-type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.
* 6: jER828 (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation
* 7: Omnirad TPO (2,4,6-trimethylbenzyl-diphenyl-phosphine oxide) manufactured by IGM Resins
* 8: Irgacure OXE02 (ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl) -1- (o-ethyl Fluorenyl oxime)
* 9: A-DCP (tricyclodecane dimethanol diacrylate) manufactured by Shin Nakamura Chemical Industry Co., Ltd.
* 10: MIR-3000 manufactured by Nippon Kayaku Co., Ltd., a compound having a maleimidine group
* 11: Dicyandiamine
* 12: Melamine
* 13: Zinc (II) naphthenate refined by Wako Pure Chemical Industries, Ltd.
* 14: 13M-T (titanium black) manufactured by Mitsubishi Materials Electrochemical Corporation
* 15: Aluminium hydrated oxide-coated silica particles prepared as described above
* 16: Zirconium hydrated oxide-coated silica particles prepared as described above
* 17: The zinc oxide-coated silicon dioxide particles prepared as described above
* 18: Titanium oxide-coated silica particles prepared as described above
* 19: The silicon dioxide particles coated with the hydrated oxide of silicon and coated with the hydrated oxide of aluminum prepared as described above.
* 20: Silicon dioxide particles coated with hydrated oxide of silicon and coated with hydrated oxide of zirconium, prepared as described above.
* 21: The silicon dioxide particles coated with the hydrated oxide of silicon and coated with the hydrated oxide of zinc prepared as described above.
* 22: The silicon dioxide particles coated with the hydrated oxide of silicon and coated with the hydrated oxide of titanium prepared as described above.
* 23: Silicon dioxide particles coated with aluminum hydrated oxide and surface-treated with methacrylfluorenylsilane prepared as above.
* 24: Silica dioxide particles coated with aluminum hydrated oxide and surface treated with aminosilane
* 25: Silicon dioxide particles prepared by coating with the hydrated oxide of silicon and coated with the hydrated oxide of aluminum and surface-treated with methacryl fluorinated silane.
* 26: Aminosilane surface-treated silica particles prepared as described above
* 27: Silica dioxide particles prepared by methacrylfluorenylsilane surface treatment prepared as above
* 28: SFP-20M manufactured by Denka, average particle size: 400 nm (silicon dioxide)

From the results shown in the above table, it can be seen that the curable resin compositions of Examples 1 to 12 of the present invention can be formed in close contact with a substrate without roughening or a low-profile substrate while maintaining physical properties such as low CTE. Good hardened material.

10‧‧‧ laminated structure

11‧‧‧Interlayer insulation material (package substrate)

12a, 12b‧‧‧Conductor layer

13a, 13b ‧‧‧solder resist

14‧‧‧Solder

15‧‧‧Semiconductor wafer

16‧‧‧ Underfill

17‧‧‧sealing material

[Fig. 1] A schematic cross-sectional view schematically showing an embodiment of a laminated structure according to the present invention.

Claims (7)

A hardening resin composition, which is characterized by containing surface-treated silicon dioxide particles with a positive hypotene potential and a hardening resin. The curable resin composition according to claim 1, wherein the surface-treated silica particles are at least any one of zirconium hydrated oxide, zinc hydrated oxide, titanium hydrated oxide, and aluminum hydrated oxide. A coated silica particle. A dry film comprising a resin layer obtained by coating a film with a curable resin composition as claimed in claim 1 and drying the film. A cured product, which is obtained by curing a curable resin composition as claimed in claim 1 or 2 or a resin layer of a dried film as claimed in claim 3. A laminated structure comprising a resin hardened layer (A) and a resin hardened layer (B) or a substrate (C) adjacent to the resin hardened layer (A). The aforementioned resin hardened layer (A) is a hardened product as claimed in claim 4, The other potential of the resin hardened layer (B) or the substrate (C) is not positive. An electronic part characterized by having a hardened body as claimed in claim 4. An electronic part characterized by having a laminated structure as claimed in claim 5.