JP2021044387A - Laminated cured product, curable resin composition, dry film, and manufacturing method of laminated cured product - Google Patents

Abstract

To provide a cured product layer that achieves both of embedding property and insulation reliability, a curable resin composition used for the cured product layer, a dry film made of the curable resin composition, and a manufacturing method of the cured product layer.SOLUTION: In a laminated cured product or the like in which a (A) first cured product layer composed of a first curable resin composition and a (B) second cured product layer composed of a second curable resin composition are sequentially laminated on a circuit board, the thickness of the (A) first cured product layer is thinner than the thickness of a connection circuit of the circuit board, the (B) second cured product layer includes an inorganic filler, and the (A) first cured product layer does not include an inorganic filler or includes a smaller amount of an inorganic filler than that of the (B) second cured product layer.SELECTED DRAWING: Figure 1

Description

The present invention relates to a laminated cured product, a curable resin composition, a dry film, and a method for producing a laminated cured product.

Generally, in electronic parts such as printed wiring boards, from the viewpoint of heat resistance and electrical insulation, curable resins such as carboxyl group-containing resins and epoxy resins are used as main components for interlayer insulation materials and solder resist materials. Further, a curable resin composition containing an additive component such as an inorganic filler is widely used.

On the other hand, in response to the increase in the density of printed wiring boards due to the miniaturization of electronic devices, the miniaturization and multi-pinization of semiconductor packages have been put into practical use and mass production has progressed. Recently, QFP (quad flat) Instead of semiconductor packages called packages) and SOPs (small outline packages), semiconductor packages such as BGA (ball grid array) and CSP (chip scale package) using package substrates will be adopted. It has become to. In such a package substrate, wiring patterns are formed at a higher density and in close proximity to each other. Therefore, a permanent coating such as a solder resist used for such a package substrate is required to have higher insulation reliability. It has become.

As a curable composition capable of obtaining a cured film having excellent electrical insulation, for example, Patent Document 1 describes light containing an acid-modified vinyl group-containing epoxy resin, an elastomer, a photopolymerization initiator, a diluent and a curing agent as essential components. Curable resin compositions are disclosed.

JP-A-2002-303974

When an inorganic filler is added to the curable resin composition, it is possible to suppress the occurrence of cracks due to CTE mismatch with the base material and wiring, and to suppress water absorption to improve HAST resistance. However, when the inorganic filler is highly filled, the melt viscosity increases, so that the gaps in the circuit, especially the gaps in the fine-pitch circuit, are not sufficiently embedded, resulting in voids and low electrical reliability. was there. For example, even the photosensitive resin composition disclosed in Patent Document 1 was not sufficient to form a cured product layer having both embedding property and insulation reliability.

Therefore, an object of the present invention is a cured product layer having both embedding property and insulation reliability, a curable resin composition used for the cured product layer, a dry film made of the curable resin composition, and the cured product layer. The purpose is to provide a manufacturing method.

As a result of diligent studies toward the realization of the above object, the present inventors have found that the above problems can be solved by forming a laminated cured product having a specific laminated structure, and have completed the present invention.

That is, the laminated cured product of the present invention has a (A) first cured product layer made of a first curable resin composition and a (B) second cured product made of a second curable resin composition on a circuit substrate. It is a laminated cured product in which layers are laminated in order, and the thickness of the (A) first cured product layer is thinner than the thickness of the connection circuit of the circuit board, and the (B) second cured product layer is inorganic. It contains a filler, and the (A) first cured product layer does not contain an inorganic filler or contains an inorganic filler in a smaller amount than the (B) second cured product layer. Is.

The first curable resin composition of the present invention is characterized in that it is used as the first curable resin composition in the laminated cured product.

The second curable resin composition of the present invention is characterized in that it is used as the second curable resin composition in the laminated cured product.

The first dry film of the present invention is characterized by having a resin layer made of the first curable resin composition.

The second dry film of the present invention is a dry film having a resin layer made of the second curable resin composition.

The laminated cured product of the present invention is preferably a semiconductor package substrate.

The method for producing a laminated cured product of the present invention comprises (A) a first cured product layer composed of a first curable resin composition and (B) a second cured product composed of a second curable resin composition on a circuit substrate. A method for producing a laminated cured product in which material layers are laminated in order, and the circuit substrate does not contain an inorganic filler or is inorganic in an amount smaller than that of the second curable resin composition in terms of solid content. A step of forming the (A) first cured product layer composed of the first curable resin composition containing a filler so as to be thinner than the thickness of the connection circuit of the circuit board, and the (A) first curing It is characterized by including (B) a step of forming a second cured product layer composed of the second curable resin composition containing an inorganic filler on the material layer.

According to the present invention, a laminated cured product having a cured product layer having both embedding property and insulation reliability, a curable resin composition used for the laminated cured product, a dry film composed of the curable resin composition, and the like. A method for producing a laminated cured product can be provided.

It is schematic cross-sectional view which shows typically one Embodiment of the laminated cured product of this invention and the manufacturing method thereof. It is schematic cross-sectional view which shows typically one Embodiment of the laminated cured product of this invention and the manufacturing method thereof. It is the schematic cross-sectional view which shows typically one Embodiment of the laminated hardened body of this invention.

In the laminated cured product of the present invention, a (A) first cured product layer made of a first curable resin composition and a (B) second cured product layer made of a second curable resin composition are formed on a circuit substrate. It is a laminated cured product that is laminated in order, and the thickness of the (A) first cured product layer is thinner than the thickness of the connection circuit of the circuit board, and the (B) second cured product layer contains an inorganic filler. It is characterized in that the (A) first cured product layer does not contain an inorganic filler or contains an inorganic filler in a smaller amount than the (B) second cured product layer. ..

In the present invention, the implantability is ensured by not containing the inorganic filler in the (A) first cured product layer on the circuit board side or by containing the inorganic filler in a smaller amount than the second curable resin composition. can do. On the other hand, the second cured product layer on the opposite side of the substrate, that is, the surface layer side, contains an inorganic filler, and the thickness of the first cured product layer is made thinner than that of the connection circuit. It is possible to form a laminated cured product having excellent insulation reliability. When (A) the thickness of the first cured product layer is the same as the thickness of the connection circuit, from the interface between (A) the first cured product layer and (B) the second cured product layer (also referred to as the connection circuit). Since cracks occur, good insulation reliability cannot be ensured.

The content of the inorganic filler in the (A) first cured product layer needs to be smaller than that in the (B) second cured product layer, and either does not contain the inorganic filler, or the upper limit is, for example, 30 mass. % Or less, 25% by mass or less, 20% by mass or less. When (A) the first cured product layer contains an inorganic filler, the content of the inorganic filler in the (A) first cured product layer is higher than the content of the inorganic filler in the (B) second cured product layer. It is preferably less than 5% by mass, and more preferably less than 10% by mass. The larger the difference between the content of the inorganic filler in the (A) first cured product layer and the content of the inorganic filler in the (B) second cured product layer, the easier it is to obtain a balance between embedding property and insulation reliability. it can.

Further, since the (A) first cured product layer does not contain an inorganic filler or contains a small amount of the inorganic filler, it has a low elastic modulus such as an elastomer or rubber particles as a stress relaxation agent from the viewpoint of crack resistance. It is preferable to contain a material having a high elongation rate.

The content of the inorganic filler in the second cured product layer (B) is not particularly limited, but a higher content is preferable because a cured product having insulation reliability, that is, a low water absorption rate can be obtained. (B) The content of the inorganic filler in the second cured product layer may be set according to the intended use, but HAST resistance by suppressing the water absorption rate and copper plating or the like in the opening of the second cured product layer, which will be described later, are used. From the viewpoint of adhesion when the conductive material is filled, the lower limit is, for example, 20% by mass or more, 25% by mass or more, 30% by mass or more, and 35% by mass or more. On the other hand, considering the resolution as the upper limit, for example, it is 85% by mass or less and 80% by mass or less.
The inorganic filler is preferably surface-treated as described later. Further, the inorganic filler is not particularly limited and may contain a heat-dissipating filler such as alumina, but the crack resistance can be improved by containing silica from the viewpoint of the heat ray expansion coefficient value of the cured product. Therefore, it is preferable.

Further, when the (B) second cured product layer contains a colorant, it is possible to prevent inspection defects during AOI (automated optical inspection equipment) inspection.

The second cured product layer preferably contains a curing accelerator in order to improve the adhesion with the underfill.

(A) The method for adjusting the thickness of the first cured product layer is not particularly limited, but as shown in FIG. 1 (1), for example, the curability for the first cured product layer is placed on the substrate 1 on which the circuit is formed. The resin composition (that is, the first curable resin composition) is applied and dried, or the resin layer is laminated in the form of a dry film to form the layer 3 composed of the first curable resin composition. Then, as shown in FIG. 1 (2), etching treatment is performed by a known method such as wet etching (alkaline aqueous solution) or dry etching (plasma) so as to be thinner than the thickness of the connection circuit 2a (A). 1 The thickness of the cured product layer can be adjusted.
Then, before or after curing the layer 3 composed of the first curable resin composition, the curable resin composition for the second curable resin composition (that is, that is, on the layer 3 composed of the first curable resin composition). The second curable resin composition) was applied, dried, or the resin layer was laminated in the form of a dry film, and then exposed and developed to form a fine pattern as shown in FIG. 1 (3). The layer 4 made of the curable resin composition may be formed. The layer 3 made of the first curable resin composition may be main-cured before the formation of the layer 4 made of the second curable resin composition, but at the same time as the layer 4 made of the second curable resin composition. This curing is more preferable from the viewpoint of insulation reliability because (A) the first cured product layer and (B) the second cured product layer can be brought into close contact with each other.

The laminated cured product of the present invention can be suitably used for electronic components. When the laminated cured product of the present invention is a package substrate, for example, a die 9 as shown in FIG. 1 (4) can be mounted as shown in FIG. 1 (5).

Further, in the present invention, the thickness is not limited to the (A) first cured product layer which is partially thinner than the connection circuit as shown in FIG. 1, and the whole is made thicker than the connection circuit as shown in FIG. It may be thinned. In FIG. 2, as shown in FIG. 2 (1), after forming the layer 3 made of the first curable resin composition, the first curable resin is formed by wet etching or the like as shown in FIG. 2 (2). The thickness of the layer 3 made of the composition is adjusted so as to be thinner than the connection circuit 2a as a whole. Further, as shown in FIG. 2 (3), a pattern may be formed on the layer 4 made of the second curable resin composition other than above the connection circuit 2a. For example, as shown in FIG. 2 (4). As described above, in the laminated cured product 12 on which the die is mounted, the dam 11 may be used to prevent the underfill from flowing.

Other layers may be further laminated on the laminated structure of the present invention. For example, as shown in FIG. 3, after laminating the conductor portion 13 on the connection circuit by a known and commonly used method using electroless plating, electrolytic plating, and conductive paste, a curable resin composition (not particularly limited, but for example, for example). The second curable resin composition) may be applied, dried, or the dry film thereof may be laminated, and then exposed and developed to form a layer 14 composed of a curable resin composition having a fine pattern formed. In the present invention, when the structure is formed by filling the opening of the second cured product layer with a conductive material such as copper plating, it is conductive when the second cured product layer is highly filled with the inorganic filler. CTE mismatch with the material is suppressed, and the adhesion with the conductive material is improved. The number of layers as described above is not particularly limited, and may be further laminated to the extent possible.

In the present invention, the thickness of the first cured product layer (A) may be thinner than that of the connection circuit. For example, when the thickness of the connection circuit is 100%, it may be 1 to 70% thinner. From the viewpoint of insulation reliability, the lower limit of the thinning treatment is preferably 2% or more, more preferably 3% or more, and most preferably 5% or more thinner. The upper limit is preferably 70% or less, more preferably 30% or less, from the viewpoint of (B) embedding property of the second cured product layer. That is, it is preferable that the thickness of the (A) first cured product layer remains 30% or more, and more preferably 70% or more of the thickness of the connection circuit.

In the present invention, the (A) first cured product layer and (B) second cured product layer are cured products of the first curable resin composition and the second curable resin composition, respectively. The first curable resin composition and the second curable resin composition (hereinafter, also abbreviated as "first and second curable resin compositions") are not particularly limited, and known and commonly used curable resin compositions are used. You may.

The first curable resin composition preferably has a melt viscosity of the composition at 90 ° C. of 50 to 1000 dPa · s in order to obtain embedding property (fluidity) and adhesion to a circuit board. In order to achieve the melt viscosity, it is preferable to contain an epoxy resin having a low softening point or a low epoxy equivalent, and the softening point is 60 ° C. or less or the epoxy equivalent is 200 g / eq. It is more preferable to contain the following epoxy resin.

Hereinafter, the components that can be contained in the first and second curable resin compositions will be described in more detail. In addition, in this specification, (meth) acrylate is a generic term for acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

(Inorganic filler)
The inorganic filler is not particularly limited, and known and commonly used inorganic fillers, for example, silica such as amorphous silica, crystalline silica, fused silica, and spherical silica, Neuburg silica soil, aluminum hydroxide, glass powder, talc, clay, and calcium carbonate. Use inorganic fillers such as magnesium, calcium carbonate, natural mica, synthetic mica, alumina, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, zinc flower, etc. Can be done. Among them, silica is preferable because it has a small specific gravity, can be highly filled in the cured product, and can be easily increased in strength, and from the viewpoint of insulation reliability of the laminated cured product.

The inorganic filler is preferably a surface-treated inorganic filler (also referred to as "surface-treated inorganic filler"), and more preferably the surface of the inorganic filler is subjected to a surface treatment capable of introducing a curable reactive group. .. Here, the curable reactive group is not particularly limited as long as it is a group that cures with a curable compound such as an alkali-soluble resin or a thermosetting resin, and may be a photocurable reactive group or a thermosetting reactive group. Examples of the photocurable reactive group include a methacryloyl group, an acryloyl group, a vinyl group, a styryl group and the like, and examples of the thermosetting reactive group include an epoxy group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, an imino group and an oxetanyl. Examples thereof include a group, a mercapto group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, an oxazoline group and the like. The method for introducing the curable reactive group onto the surface of the inorganic filler is not particularly limited, and it may be introduced by using a known and commonly used method, and a surface treatment agent having a curable reactive group, for example, a curable reactive group is introduced as an organic group. The surface of the inorganic filler may be treated with a coupling agent or the like. As the coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent and the like can be used. Examples of the surface-treated inorganic filler having no curable reactive group include silica-alumina surface treatment, titanate-based coupling agent treatment, aluminate-based coupling agent treatment, and organically treated inorganic filler. Can be mentioned.

Further, if the inorganic filler contained in the first cured product layer (A) contains a filler having a positive zeta potential, the adhesion to the circuit board can be improved.

The average particle size of the inorganic filler is preferably 1 μm or less. Further, it is preferably smaller than the exposure wavelength, and more preferably 0.3 μm or less. On the other hand, it is preferably 0.02 μm or more from the viewpoint of suppressing halation and aggregation during exposure. Here, in the present specification, the average particle size of the inorganic filler is the average particle size (D50) including not only the particle size of the primary particles but also the particle size of the secondary particles (aggregates), and is a laser diffraction method. It is a value of D50 measured by. Examples of the measuring device by the laser diffraction method include the Microtrac MT3300EXII manufactured by Microtrac Bell.

The average particle size of the inorganic filler may be adjusted, and it is preferable to pre-disperse the inorganic filler with, for example, a bead mill or a jet mill. Further, the inorganic filler is preferably blended in a slurry state, and by blending in a slurry state, high dispersion is facilitated, aggregation is prevented, and handling is facilitated.

The inorganic filler may be used alone or in combination of two or more.

The first curable resin composition does not contain an inorganic filler, or when it contains an inorganic filler, it is less than the amount of the inorganic filler compounded in the solid content of the second curable resin composition. When the inorganic filler is contained, the content is not particularly limited, but (A), as an upper limit, 30% by mass or less in the total solid content of the composition so as to be contained in the first cured product layer at the above-mentioned content. It is 25% by mass or less and 20% by mass or less. When the inorganic filler is contained, the content of the inorganic filler is preferably 5% by mass or more less than the content of the inorganic filler in the total solid content of the first curable resin composition, and is preferably 10% by mass. More preferably less than that.

The blending amount of the inorganic filler of the second curable resin composition is not particularly limited, but (B) as the lower limit is included in the total solid content of the composition so as to be contained in the second cured product layer at the above-mentioned content. For example, it is 20% by mass or more, 25% by mass or more, 30% by mass or more, and 35% by mass or more. On the other hand, considering the resolution as the upper limit, for example, it is 85% by mass or less and 80% by mass or less.

(Curable resin)
The curable resin is a thermosetting resin or a photocurable resin, and may be a mixture thereof. The blending amount of the curable resin of the first and second curable resin compositions is, for example, 1 to 80% by mass based on the total solid content of the composition, and depends on the blending amount of the inorganic filler in each composition. It may be adjusted as appropriate.

(Thermosetting resin)
When a thermosetting resin is contained, the heat resistance of the cured product is improved, and the adhesion to the substrate is improved. As the thermosetting resin, known and commonly used thermosetting resins such as isocyanate compounds, blocked isocyanate compounds, amino resins, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, epoxy compounds, polyfunctional oxetane compounds, and episulfide resins can be used. .. Among these, epoxy compounds, polyfunctional oxetane compounds, and compounds having two or more thioether groups in the molecule, that is, episulfide resins are preferable, and epoxy compounds are more preferable. As the thermosetting resin, one type may be used alone or two or more types may be used in combination.

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

Examples of the polyfunctional epoxy compound include epoxidized vegetable oil; bisphenol A type epoxy resin; hydroquinone type epoxy resin; bisphenol type epoxy resin; thioether type epoxy resin; brominated epoxy resin; novolac type epoxy resin; biphenol novolac type epoxy resin; bisphenol F. Type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; hydrantin type epoxy resin; alicyclic epoxy resin; trihydroxyphenylmethane type epoxy resin; bixyleneol type or biphenol type epoxy resin or a mixture thereof; Bisphenol S type epoxy resin; Bisphenol A novolac type epoxy resin; Tetraphenylol ethane type epoxy resin; Heterocyclic epoxy resin; Diglycidyl phthalate resin; Tetraglycidyl xylenoyl ethane resin; Naphthalene group-containing epoxy resin; Dicyclopentadiene skeleton Epoxy resin with glycidyl methacrylate copolymer; epoxy resin copolymerized with cyclohexyl maleimide and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivative; CTBN-modified epoxy resin and the like, but are not limited thereto. .. These epoxy resins may be used alone or in combination of two or more.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, and 1,4-bis [(3-3-oxythenylmethoxy) methyl] ether. Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-3- Oxetane) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and polyfunctional oxetane such as their oligomers or copolymers, as well as oxetane alcohols and novolak resins. , Poly (p-hydroxystyrene), cardo-type bisphenols, calix arrayes, calix resorcinarenes, etherified compounds with a resin having a hydroxyl group such as silsesquioxane, and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate can also be mentioned.

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

Examples of amino resins such as melamine derivatives and benzoguanamine derivatives include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycol uryl compounds and methylol urea compounds.

As the isocyanate compound, a polyisocyanate compound can be blended. Polyisocyanate compounds include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate and Aromatic polyisocyanates such as 2,4-tolyrene isocyanate dimer; aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexylisocyanate) and isophorone diisocyanate; Alicyclic polyisocyanates such as bicycloheptanetriisocyanate; and adducts, burettes, and isocyanurates of the isocyanate compounds mentioned above can be mentioned.

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

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

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

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

As the photopolymerizable vinyl monomer, known and commonly used ones, for example, styrene derivatives such as styrene, chlorostyrene, α-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl- Vinyl ethers such as n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, (Meta) acrylamides such as methacrylicamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylicamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide; triallyl isocyanurate, diallyl phthalate, Allyl compounds such as diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfreel (meth) acrylate, isobolonyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like. (Meta) acrylic acid esters; hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate; methoxyethyl (meth) acrylate, ethoxyethyl Alkoxyalkylene glycol mono (meth) acrylates such as (meth) acrylate; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di ( Alkylene polyol poly (meth) acrylates such as meta) acrylate, trimethylolpropantri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di. Polyoxyalkylene glycol poly (meth) acrylates such as (meth) acrylates, ethoxylated trimetylolpropan triacrylates, propoxylated trimethylol propantri (meth) acrylates; Poly (meth) acrylates such as neopentyl glycol ester di (meth) acrylate of hydroxybivariate; isocyanurate-type poly (meth) acrylates such as tris [(meth) acryloxyethyl] isocyanurate can be mentioned.

(Alkali-soluble resin)
Examples of the alkali-soluble resin include a compound having two or more phenolic hydroxyl groups, a carboxyl group-containing resin, a compound having a phenolic hydroxyl group and a carboxyl group, and a compound having two or more thiol groups. Above all, it is preferable that the alkali-soluble resin is a carboxyl group-containing resin or a phenol resin because the adhesion to the circuit board is improved. In particular, the alkali-soluble resin is more preferably a carboxyl group-containing resin because of its excellent developability. The carboxyl group-containing resin may be a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group or a carboxyl group-containing resin having no ethylenically unsaturated group. The alkali-soluble resin may be used alone or in combination of two or more.

Specific examples of the carboxyl group-containing resin include compounds (either oligomers and polymers) listed below.

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

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

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

(4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Meta) A carboxyl group-containing urethane resin obtained by a double addition reaction of an acrylate or a modified partial acid anhydride thereof, a carboxyl group-containing dialcohol compound and a diol compound.

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

(6) During the synthesis of the resin according to (2) or (4) above, one isocyanate group and one or more (meth) acryloyl groups are added to the molecule, such as an isophorone diisocyanate and pentaerythritol triacrylate equimolar reaction product. A carboxyl group-containing urethane resin that is terminal (meth) acrylicized by adding the compound to be possessed.

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

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

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

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

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

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

(13) A carboxyl group-containing resin having at least one of an amide structure and an imide structure.

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

Examples of the compound having a phenolic hydroxyl group include a compound having a biphenyl skeleton and / or a phenylene skeleton, or a phenol, orthocresol, paracresol, metacresol, 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, pyrogallol, fluoroglucolcinol, etc. Examples thereof include phenolic resins having various skeletons synthesized in the above.

Examples of the compound having a phenolic hydroxyl group include phenol novolac resin, alkylphenol volac resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene-modified phenol resin, polyvinylphenols, and bisphenol F. , Bisphenol S-type phenol resin, poly-p-hydroxystyrene, a condensate of naphthol and aldehydes, a condensate of dihydroxynaphthalene and aldehydes, and other known and commonly used phenol resins.

The acid value of the alkali-soluble resin is preferably in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the alkali-soluble resin is 40 mgKOH / g or more, alkaline development becomes easy, while drawing a normal cured product pattern of 200 mgKOH / g or less becomes easy, which is preferable.

The weight average molecular weight of the alkali-soluble resin varies depending on the resin skeleton, but is preferably in the range of 1,500 to 150,000, more preferably 1,500 to 100,000. When the weight average molecular weight is 1,500 or more, the tack-free performance is good, the moisture resistance of the coating film after exposure is good, film loss during development can be suppressed, and resolution deterioration 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 of the first and second curable resin compositions is, for example, 5 to 50% by mass based on the total solid content of the composition.

(Photoreaction initiator)
The first and second curable resin compositions can contain a photoreaction initiator. The photoreaction initiator may be any one of a photopolymerization initiator that generates radicals by light irradiation and a photobase generator that generates bases by light irradiation, as long as the composition can be cured by light irradiation. Is preferable. Of course, the photoreaction initiator may be a compound that generates both radicals and bases by irradiation with light. Light irradiation refers to irradiating active energy warfare in the wavelength range of 350 to 450 nm.

Examples of the photopolymerization initiator include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis- (2, 6-Dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Bisacylphosphine oxides such as trimethylbenzoyl) -phenylphosphine oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine Monoacylphosphine oxides such as acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 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-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one and other hydroxyacetophenones; benzoin, benzyl, benzoylmethyl Benzoyls such as ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, Benzoyls such as 4,4'-bisdiethylaminobenzophenone; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-diclo Loacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl) -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone, etc. Acetphenones; thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone , 2-Methyl anthraquinone, 2-Ethyl anthraquinone, 2-tert-butyl anthraquinone, 1-chloroanthraquinone, 2-amyl anthraquinone, 2-aminoanthraquinone and other anthraquinones; acetphenone dimethyl ketal, benzyl dimethyl ketal and other ketals; ethyl Orthoperic acid esters such as -4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate, p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1- [4- (phenylthio)-, 2-( O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) and other oxime esters; (Η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium, bis (cyclopentadienyl) -bis [2 6-Difluoro-3- (2- (1-pill-1-yl) ethyl) phenyl] Titanocenes such as titanium; phenyldisulfide 2-nitrofluorene, butyloin, anisoine ethyl ether, azobisisobutyronitrile, tetra Methylthiolam disulfide and the like can be mentioned. As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination.

The photobase generator produces one or more basic substances that can function as a catalyst for a thermal curing reaction by changing the molecular structure by irradiation with light such as ultraviolet rays or visible light or by cleaving the molecules. It is a compound. Examples of the basic substance include secondary amines and tertiary amines.

Examples of photobase generators include α-aminoacetophenone compounds, oxime ester compounds, acyloxyimino compounds, N-formylated aromatic amino compounds, N-acylated aromatic amino compounds, nitrobenzyl carbamate compounds, and alcoholic benzyl carbamate. Examples include compounds. Among them, an oxime ester compound and an α-aminoacetophenone compound are preferable, and an oxime ester compound is more preferable. Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) is more preferable. As the α-aminoacetophenone compound, those having two or more nitrogen atoms are particularly preferable. One type of photobase generator may be used alone, or two or more types may be used in combination. In addition, examples of the photobase generator include a quaternary ammonium salt and the like.

Other photobase generators include WPBG-018 (trade name: 9-anthrylmethyl N, N'-diethylcarbamate) and WPBG-027 (trade name: (E) -1- [3-] manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (2-hydroxyphenyl) -2-propenoyl] piperidine), WPBG-082 (trade name: guanidinium2- (3-benzoylphenyl) propionate), WPBG-140 (trade name: 1- (anthraquinone-2-yl) et al. Can also be used.

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

The blending amount of the photoreaction initiator of the first and second curable resin compositions is, for example, 0.01 to 30% by mass based on the total solid content of the composition.

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

The amount of the curing accelerator in the first and second curable resin compositions is, for example, 0.01 to 30% by mass based on the total solid content of the composition.

(Hardener)
The first and second curable resin compositions can contain a curing agent. Examples of the curing agent include a compound having a phenolic hydroxyl group, a polycarboxylic acid and its acid anhydride, a compound having a cyanate ester group, a compound having a maleimide group, an alicyclic olefin polymer and the like. As the curing agent, one type may be used alone or two or more types may be used in combination.

Examples of the compound having a phenolic hydroxyl group include phenol novolac resin, alkylphenol novolak resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene-modified phenol resin, cresol / naphthol resin, polyvinylphenols, and phenol. / Conventionally known substances such as naphthol resin, α-naphthol skeleton-containing phenol resin, triazine skeleton-containing cresol novolac resin, biphenyl aralkyl type phenol resin, and zylock type phenol novolac resin can be used.

The compound having a cyanate ester group is preferably a compound having two or more cyanate ester groups (-OCN) in one molecule. As the compound having a cyanate ester group, any conventionally known compound can be used. Examples of the compound having a cyanate ester group include phenol novolac type cyanate ester resin, alkylphenol novolac type cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, and bisphenol S type. Cyanate ester resin can be mentioned. Further, it may be a prepolymer in which a part is triazine-ized.

Commercially available compounds having a cyanate ester group include phenol novolac type polyfunctional cyanate ester resin (manufactured by Lonza Japan, PT30S), and a prepolymer in which part or all of bisphenol A disicianate is triazined to form a trimer. (Lonza Japan Co., Ltd., BA230S75), dicyclopentadiene structure-containing cyanate ester resin (Lonza Japan Co., Ltd., DT-4000, DT-7000) and the like can be mentioned.

The compound having a maleimide group is a compound having a maleimide skeleton, and any conventionally known compound can be used. The compound having a maleimide group preferably has two or more maleimide skeletons, N, N'-1,3-phenylenedi maleimide, N, N'-1,4-phenylenedi maleimide, 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-Maleimidephenoxy) phenyl] Propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, bis ( 3-Ethyl-5-methyl-4-maleimidephenyl) methane, bisphenol A diphenyl ether bismaleimide, polyphenylmethane maleimide, and oligomers thereof, and at least one of diamine condensates having a maleimide skeleton. Is more preferable. The oligomer is an oligomer obtained by condensing a compound having a maleimide group, which is a monomer among the above-mentioned compounds having a maleimide group.

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

The blending amount of the curing agent of the first and second curable resin compositions is, for example, 0.01 to 30% by mass based on the total solid content of the composition.

(Thermoplastic resin)
The first and second curable resin compositions can further contain a thermoplastic resin in order to improve the mechanical strength of the obtained cured film. The thermoplastic resin is preferably soluble in a solvent. When it is soluble in a solvent, its flexibility is improved when it is formed into a dry film, and the generation of cracks and powder falling can be suppressed. As the thermoplastic resin, various acid anhydrides or acid chlorides are used for the thermoplastic polyhydroxypolyether resin, the phenoxy resin which is a condensate of epichlorohydrin and various bifunctional phenol compounds, or the hydroxyl group of the hydroxyether portion existing in the skeleton thereof. Examples thereof include phenoxy resins, polyvinyl acetal resins, polyamide resins, polyamideimide resins, block copolymers, rubber particles and the like that have been esterified. The thermoplastic resin may be used alone or in combination of two or more.

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

(Stress relaxation agent)
The first and second curable resin compositions can contain stress relaxation agents such as elastomers and rubber particles. As the elastomer, a known elastomer can be used. As the elastomer, polyester-based elastomers, polyurethane-based elastomers, polyester-urethane-based elastomers, polyamide-based elastomers, polyesteramide-based elastomers, acrylic-based elastomers, olefin-based elastomers and the like can be used. Further, a resin obtained by modifying a part or all of the epoxy groups of the epoxy resin having various skeletons with both-terminal carboxylic acid-modified butadiene-acrylonitrile rubber can also be used. Further, epoxy-containing polybutadiene-based elastomers, acrylic-containing polybutadiene-based elastomers, hydroxyl group-containing polybutadiene-based elastomers, hydroxyl group-containing isoprene-based elastomers, block copolymers and the like can also be used. For example, the product names include R-45HT, Polybd HTP-9 (manufactured by Idemitsu Kosan Co., Ltd.), Epolide PB3600 (manufactured by Daicel Chemical Industry Co., Ltd.), Denarex R-45EPT (manufactured by Nagase ChemteX Co., Ltd.), and Tough Serene (Sumitomo Chemical Co., Ltd.). Made by), Ricon 130, Ricon 131, Ricon 134, Ricon 142, Ricon 150, Ricon 152, Ricon 153, Ricon 154, Ricon 156, Ricon 157, Ricon 100, Ricon 181, Ricon 184, Ricon 130MA8, Ricon 130MA8 , Ricon 131MA5, Ricon 131MA10, Ricon 131MA17, Ricon 131MA20, Ricon 184MA6, Ricon 156MA17 (all manufactured by Sartmer Co., Ltd.) and the like.

The rubber-like particles include polybutadiene rubber, polyisopropylene rubber, urethane-modified polybutadiene rubber, epoxy-modified polybutadiene rubber, acrylonitrile-modified polybutadiene rubber, carboxyl group-modified polybutadiene rubber, carboxyl group-modified or hydroxyl-modified acrylonitrile butadiene rubber, and cross-linking thereof. Examples include rubber particles and core-shell type rubber particles. These rubber-like particles are added to improve the flexibility of the obtained cured film, improve crack resistance, enable surface roughness treatment with an oxidizing agent, and improve the adhesion strength with copper foil and the like. Will be done.

As the stress relaxation agent, one type may be used alone, or two or more types may be used in combination. The blending amount of the stress relaxation agent of the first and second curable resin compositions is preferably 1 to 10% by mass based on the total solid content of the composition.

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

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

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

The blending amount of the colorant of the first and second curable resin compositions is, for example, 0.01 to 10% by mass based on the total solid content of the composition.

(Organic solvent)
The first and second curable resin compositions may contain an organic solvent for the purpose of preparing the composition, adjusting the viscosity when applied to a substrate or a carrier film, and the like. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethyl benzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol and propylene glycol monomethyl ether. , Dipropylene glycol monomethyl ether, Dipropylene glycol diethyl ether, Diethylene glycol monomethyl ether acetate, Tripropylene glycol monomethyl ether and other glycol ethers; Ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbi Esters such as tall acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha are known. Conventional organic solvents can be used. These organic solvents can be used alone or in combination of two or more.

(Other optional ingredients)
Further, the first and second curable resin compositions and the cured product layer may be blended with other additives known and commonly used in the field of electronic materials. Other additives include thermal polymerization inhibitors, UV absorbers, silane coupling agents, plasticizers, antistatic agents, antioxidants, antioxidants, antibacterial / antifungal agents, antifoaming agents, leveling agents, and more. Adhesives, Adhesive Agents, Tixo Properties, Photoinitiator Aids, Sensitizers, Organic Fillers, Release Agents, Surface Treatment Agents, Dispersants, Dispersion Aids, Surface Modifiers, Stabilizers, Phosphorants And so on.

The first and second curable resin compositions are not particularly limited, and may be any of, for example, a thermosetting resin composition, a photocurable thermosetting resin composition, and a photosensitive thermosetting resin composition. Good. Further, it may be an alkali-developed type, or may be a negative type or a positive type. Specific examples include a photocurable thermosetting resin composition containing a photopolymerization initiator, a photocurable thermosetting resin composition containing a photobase generator, and a negative photocurable thermosetting resin composition. And positive-type photosensitive thermosetting resin compositions, alkali-developed photocurable thermosetting resin compositions, solvent-developed photocurable thermosetting resin compositions, and the like, but are not limited thereto. Absent. The second curable resin composition is preferably an alkali-developed type as a composition for forming a fine pattern such as vias, but a thermosetting resin composition is used as the second curable resin composition. Fine patterns such as vias may be formed by laser processing.

As the optional components contained in the first and second curable resin compositions and the cured product layer, known and commonly used components may be selected according to the curability and application.

The first and second curable resin compositions may be used as a dry film or may be used as a liquid. When used as a liquid, it may be one-component or two-component or more. Further, the first and second curable resin compositions may be provided together as a kit. In that case, both may be in the form of a liquid, both may be in the form of a dry fill, or one may be in the form of a liquid and the other in the form of a dry film.

The dry film of the present invention has a resin layer obtained by applying a first curable resin composition or a second curable resin composition on a carrier film and drying it. When forming a dry film, first, the curable resin composition is diluted with the above organic solvent to adjust the viscosity to an appropriate level, and then a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, and a reverse coater. , Transfer coater, gravure coater, spray coater, etc., and apply to a uniform thickness on the carrier film. Then, the applied composition is usually dried at a temperature of 40 to 130 ° C. for 1 to 30 minutes to form a resin layer. The coating film thickness is not particularly limited, but is generally selected as appropriate in the range of 3 to 150 μm, preferably 5 to 60 μm after drying.

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

After forming a resin layer made of a curable resin composition on a carrier film, a peelable cover film is further laminated on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. It is preferable to do so. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, surface-treated paper, or the like can be used. The cover film may be smaller than the adhesive force between the resin layer and the carrier film when the cover film is peeled off.

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

The method for producing a laminated cured product of the present invention comprises (A) a first cured product layer composed of a first curable resin composition and (B) a second cured product composed of a second curable resin composition on a circuit substrate. A method for producing a laminated cured product in which material layers are laminated in order, and the circuit substrate does not contain an inorganic filler or is inorganic in an amount smaller than that of the second curable resin composition in terms of solid content. A step of forming the (A) first cured product layer composed of the first curable resin composition containing a filler so as to be thinner than the thickness of the connection circuit of the circuit board, and the (A) first curing It is characterized by including (B) a step of forming a second cured product layer composed of the second curable resin composition containing an inorganic filler on the material layer.

Conventionally known methods may be used in each step of the method for producing a laminated cured product of the present invention. Taking the case of manufacturing a printed wiring board as an example, in the step of forming the (A) first cured product layer, (A) the first cured product layer is an alkali-developed photocurable thermosetting first curable property. In the case of forming with a resin composition, for example, the first curable resin composition is adjusted to a viscosity suitable for the coating method using the above organic solvent, and a dip coating method or a flow coating method is applied on the circuit board. , Roll coating method, bar coater method, screen printing method, curtain coating method, spin coating method, etc., and then volatilize and dry (temporarily dry) the organic solvent contained in the composition at a temperature of 60 to 100 ° C. By letting it form a tack-free resin layer. Further, in the case of a dry film, the resin layer is formed on the substrate by sticking it on the circuit board with a laminator or the like so that the resin layer comes into contact with the substrate, and then peeling off the carrier film.

As the above-mentioned substrate, in addition to a printed wiring board and a flexible printed wiring board in which a circuit is formed in advance with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, etc. It is made of materials such as copper-clad laminates for high-frequency circuits using synthetic fiber epoxy, fluororesin / polyethylene / polyimideene ether, polyphenylene oxide / cyanate, etc., and all grades (FR-4, etc.) of copper-clad laminates. In addition, metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates and the like can be mentioned. The circuit may be pretreated, for example, pretreated with GliCAP manufactured by Shikoku Chemicals Corporation, New Organic AP (Adhesion promoter) manufactured by MEC, Nova Bond manufactured by Atotech Japan, etc., and soldered. Adhesion to a cured film such as a resist may be improved, or pretreatment may be performed with a rust preventive.

Volatile drying performed after applying the first curable resin composition is performed by hot air circulation type drying furnace, IR furnace, hot plate, convection oven, etc. (using a steam-based air heating type heat source, hot air in the dryer). It can be carried out by using a method of making a countercurrent contact and a method of spraying the support from a nozzle.

After forming the resin layer on the substrate, the first cured product (A) is made thinner than the thickness of the connection circuit of the circuit board by dry etching using oxygen plasma or the like or wet etching using an alkaline aqueous solution or the like. Form a layer. Wet etching with an alkaline aqueous solution is possible as long as the curable resin composition is alkali-soluble. For example, a non-alkali development type that does not contain a photocurable component, such as the composition of Example 1 described later. Even if it is a thermosetting resin composition, when it contains a compound having a phenolic hydroxyl group, which is also an alkali-soluble resin, as a curing agent, it can be thinned by wet etching.

After the etching treatment, the cured product layer made of the first curable resin composition is irradiated with active energy rays and then heat-cured (for example, 100 to 220 ° C.), or heat-cured and then irradiated with active energy rays, or only heat-cured. Although the final finish curing (main curing) may be performed in the above, it is preferable to perform the final curing at the same time as the layer made of the second curable resin composition as described above.

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

The developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and the developing solution includes potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, etc. Alkaline aqueous solutions such as ammonia and amines can be used.

Further, in the step of forming the (B) second cured product layer, when the (B) second cured product layer is formed of an alkali-developed photocurable thermosetting second curable resin composition, Similar to the first curable resin composition, for example, the viscosity is adjusted to be suitable for the coating method using the organic solvent, coated on the substrate, and then put into the composition at a temperature of 60 to 100 ° C. By volatilizing and drying (temporarily drying) the contained organic solvent, a tack-free resin layer is formed on the (A) first cured product layer. Further, in the case of a dry film, the resin layer is adhered onto the (A) first cured product layer so as to be in contact with the (A) first cured product layer by a laminator or the like, and then the carrier film is peeled off to (A). ) A resin layer is formed on the first cured product layer. Volatile drying after coating may be performed in the same manner as described above.

(A) After forming a resin layer on the first cured product layer, the resin layer is selectively exposed to active energy rays through a photomask having a predetermined pattern formed, and the unexposed portion is exposed to a dilute alkaline aqueous solution (for example, 0.3 to 3). It is developed with a mass% sodium carbonate aqueous solution) to form a pattern of the cured product. Further, the cured product is adhered by irradiating the cured product with active energy rays and then heat curing (for example, 100 to 220 ° C.), or by irradiating the cured product with active energy rays after heat curing or by performing final finish curing (main curing) only by heat curing. It forms a cured film with excellent properties such as properties and hardness. Exposure and development may be performed in the same manner as described above.

When the first curable resin composition is photocurable and thermosetting, the resin layer is irradiated with an exposure amount of ^{10 to 1000 mJ / cm 2 in a UV conveyor furnace before etching, and then at 100 to 220 ° C.} The first layer may be completely cured by heating for 5 to 60 minutes. When the first curable resin composition is thermosetting, the first layer may be heated at 100 to 220 ° C. for 5 to 60 minutes before etching. When the second layer is thermosetting, the second layer may be heated at 100 to 220 ° C. for 5 to 60 minutes to form a cured film.

The laminated cured product of the present invention is preferably used for electronic components, particularly printed wiring boards, more preferably for circuit boards having a permanent coating, and more preferably for solder resists, interlayer insulating layers, and covers. Used for circuit boards with a permanent insulating coating such as rays. Further, it is suitable for a printed wiring board that requires a high degree of reliability, for example, a package substrate, particularly a circuit board for FC-BGA.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. In the following, "part" and "%" are all based on mass unless otherwise specified. The numerical values shown in Table 1 are parts by mass of the solid content containing no solvent.

[Synthesis of alkali-soluble resin]
(Synthesis Example 1: Alkali-soluble resin A-1)
A flask equipped with a cooling tube and a stirrer was charged with 456 parts of bisphenol A, 228 parts of water, and 649 parts of 37% formalin, kept at a temperature of 40 ° C. or lower, and added 228 parts of a 25% sodium hydroxide aqueous solution. The reaction was carried out at ° C. for 10 hours. After completion of the reaction, the mixture was cooled to 40 ° C. and neutralized to pH 4 with a 37.5% aqueous phosphoric acid solution while maintaining 40 ° C. or lower. After that, it was allowed to stand and the aqueous layer was separated. After separation, 300 parts of methyl isobutyl ketone was added to uniformly dissolve the mixture, followed by washing with 500 parts of distilled water three times, and the water, solvent and the like were removed under reduced pressure at a temperature of 50 ° C. or lower. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1230 parts of a methanol solution of the polymethylol compound.
When a part of the obtained methanol solution of the polymethylol compound was dried in a vacuum dryer at room temperature, the solid content was 55.2%.
In a flask equipped with a cooling tube and a stirrer, 500 parts of a methanol solution of the obtained polymethylol compound and 440 parts of 2,6-xylenol were charged and dissolved uniformly at 50 ° C. After uniformly dissolving, methanol was removed under reduced pressure at a temperature of 50 ° C. or lower. Then, 8 parts of oxalic acid was added, and the reaction was carried out at 100 ° C. for 10 hours. After completion of the reaction, the distillate was removed at 180 ° C. under a reduced pressure of 50 mmHg to obtain 550 parts of novolak resin A.
In an autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device, and a stirring device, 130 parts of Novolak resin A, 2.6 parts of a 50% sodium hydroxide aqueous solution, and toluene / methyl isobutyl ketone (mass ratio = 2/1). 100 parts were charged, the inside of the system was replaced with nitrogen while stirring, then the temperature was raised by heating, and 60 parts of propylene oxide was gradually introduced at ^{150 ° C. and 8 kg / cm 2 to react.} The reaction was continued for about 4 hours until the gauge pressure reached 0.0 kg / cm ^{2, and then cooled to room temperature.} 3.3 parts of a 36% aqueous hydrochloric acid solution was added to and mixed with this reaction solution to neutralize sodium hydroxide. The neutralization reaction product was diluted with toluene, washed with water three times, and desolvated with an evaporator to obtain a hydroxyl value of 189 g / eq. A propylene oxide adduct of novolak resin A was obtained. This was an average addition of 1 mol of propylene oxide per equivalent of phenolic hydroxyl group.
189 parts of the obtained novolak resin A propylene oxide adduct, 36 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 part of hydroquinone monomethyl ether, and 140 parts of toluene were mixed with a stirrer, a thermometer, and an air blowing tube. The mixture was charged into a reactor equipped with the above, stirred while blowing air, heated to 115 ° C., and the water produced by the reaction was distilled off as an azeotropic mixture with toluene to react for another 4 hours, and then to room temperature. Cooled. The obtained reaction solution was washed with water using a 5% NaCl aqueous solution, toluene was removed by distillation under reduced pressure, and then diethylene glycol monoethyl ether acetate was added to obtain an acrylate resin solution having a solid content of 67%.
Next, 322 parts of the obtained acrylate resin solution, 0.1 part of hydroquinone monomethyl ether, and 0.3 part of triphenylphosphine were charged into a four-necked flask equipped with a stirrer and a reflux condenser, and the mixture was charged at 110 ° C. To, 60 parts of tetrahydrophthalic anhydride was added, the mixture was reacted for 4 hours, cooled, and then taken out. The solution of the photosensitive carboxyl group-containing resin A-1 thus obtained had a solid content of 70% and a solid content acid value of 81 mgKOH / g.

(Synthesis Example 2: Alkali Soluble Resin A-2)
119.4 parts of novolak type cresol resin (trade name "Shonol CRG951", manufactured by Showa High Polymer Co., Ltd., OH equivalent: 119.4) in an autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device, and a stirring device. , 1.19 parts of potassium hydroxide and 119.4 parts of toluene were introduced, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 parts of propylene oxide was gradually added dropwise, and the mixture was reacted at ^{125 to 132 ° C. and 0 to 4.8 kg / cm 2 for 16 hours.} Then, the mixture was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The non-volatile content was 62.1% and the hydroxyl value was 182.2 mgKOH / g (307. A propylene oxide reaction solution of a novolak-type cresol resin at 9 g / eq.) Was obtained. This was an average of 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
293.0 parts of the propylene oxide reaction solution of the obtained novolak type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone and 252.9 parts of toluene were mixed with a stirrer and temperature. It was introduced into a reactor equipped with a meter and an air blowing tube, and air was blown at a rate of 10 ml / min and reacted at 110 ° C. for 12 hours with stirring. As for the water produced by the reaction, 12.6 parts of water was distilled off as an azeotropic mixture with toluene. Then, the mixture was cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Then, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak type acrylate resin solution. Next, 332.5 parts of the obtained novolak type acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was introduced at a rate of 10 ml / min. With stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added, reacted at 95 to 101 ° C. for 6 hours, cooled, and then taken out. In this way, a solution of the carboxyl group-containing photosensitive resin A-2 having a non-volatile content of 65% and a solid acid value of 80 mgKOH / g was obtained.

[Preparation of filler]
(Adjustment Example 1: Solvent-dispersed product of surface-treated silica K-1)
Spherical silica (SFP-20M manufactured by Denka Co., Ltd., average particle size: 400 nm) 60 g, PMA (propylene glycol monomethyl ether acetate) 38 g as a solvent, and a silane coupling agent having a methacryloyl group (KBM-503 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 2 g and 2 g were uniformly dispersed to obtain a solvent-dispersed product K-1 of silica.

(Adjustment Example 2: Solvent-dispersed product of surface-treated silica K-2)
Spherical silica (SFP-20M manufactured by Denka Co., Ltd., average particle size: 400 nm) 60 g, PMA (propylene glycol monomethyl ether acetate) 38 g as a solvent, and a silane coupling agent having an amino group (KBM-573 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 2 g and 2 g were uniformly dispersed to obtain a solvent-dispersed product K-2 of silica.

(Adjustment Example 3: Solvent-dispersed product of surface-treated barium sulfate K-3)
60 g of barium sulfate (B-30 manufactured by Sakai Chemical Co., Ltd., average particle size: 300 nm), 35 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 5 g of a wet dispersant are uniformly dispersed to obtain a solvent-dispersed product of barium K. I got -3.

(Adjustment Example 4: Solvent-dispersed product of surface-treated alumina K-4)
Spherical alumina particles (ASFP-20 manufactured by Denka Co., Ltd., average particle size: 300 nm) 50 g, PMA (propylene glycol monomethyl ether acetate) 48 g as a solvent, and a silane coupling agent having an amino group (KBE-903 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) ) 2 g was uniformly dispersed to obtain a solvent-dispersed product K-4 of alumina.

[Making core-shell rubber I-1]
1300 g of rubber latex and 440 g of pure water were charged in a 3 liter glass reactor, and the mixture was heated to 70 ° C. with stirring under the introduction of nitrogen. This rubber latex contains 480 g of polybutadiene particles having an average particle size of 0.1 μm, and 1.5% by mass of sodium dodecylbenzenesulfonate, with the polybutadiene as 100% by mass. After adding 1.2 g of azoisobutyronitrile, a mixture of 36 g of styrene, 48 g of methyl methacrylate, and 24 g of acrylonitrile was added over 3 hours. Then, the mixture was further stirred for 2 hours to obtain core-shell rubber particles (latex (L)). The solid content of latex (L) was 32%. The gel fraction of the core-shell copolymer in latex (L) was 98%. The rubber particle size in the latex (L) was 0.5 μm.

[Composition of each layer of Examples 1 to 6 and Comparative Examples 1 to 4]
The various components in the table were mixed in the solid content ratio (parts by mass) shown in the table, premixed with a stirrer, kneaded with a bead mill, and cured for the first layer and the second layer, respectively. A sex resin composition was prepared.

<Making dry film>
300 g of methyl ethyl ketone was added to the curable resin composition for the first layer prepared as described above to dilute it, and the mixture was stirred with a stirrer for 15 minutes to obtain a coating liquid. The coating liquid is applied onto a polyethylene terephthalate film (carrier film: Unitika Ltd. Emblet PTH-25) having a thickness of 38 μm, dried at a temperature of 100 ° C. for 15 minutes, and has a thickness of 20 μm (however, Comparative Example 2). A resin layer having a thickness of 25 μm) was formed only in 3. Next, a biaxially stretched polypropylene film (cover film: OPP-FOA manufactured by Futamura Co., Ltd.) was laminated on the resin layer to prepare a dry film for the first layer. A dry film for the second layer was produced in the same manner as above except that the thickness of the resin layer was 10 μm.

<Manufacturing method of laminated cured product>
(Examples 1 to 6, Comparative Examples 1 and 4)
A circuit board was prepared by treating a BT board having a pattern of L / S = 20 μm / 15 μm, a conductor pad diameter of 70 μm as a connecting circuit, and a conductor thickness of 20 μm as a connecting circuit by CZ8101 treatment. On this circuit board, first, a vacuum laminator (CVP-600: manufactured by Nikko Material Co., Ltd.) was used to peel off the cover film of the first layer of the dry film of each Example and Comparative Example, and the temperature was 90 ° C. After laminating in one chamber under the conditions of a vacuum pressure of 3 hPa and a vacuum time of 30 seconds, pressing was performed under the conditions of a press pressure of 0.5 MPa and a press time of 30 seconds.
Then, the carrier film was peeled off, and the uncured resin layer was wet-etched so as to have the following etching amount.
Specifically, the first resin is thinned with a 10% by mass sodium metasilicate aqueous solution at 25 ° C. to a thickness equal to or less than the conductor thickness, and then washed with an aqueous solution having a pH of 5 to 10 containing an alkali metal carbonate and washing with water. The layer surface was made uniform.
Next, a second layer dry film having a thickness of 10 μm is laminated on the first layer under the same conditions as above, and an exposure that obtains 10 steps with a step tablet (41 steps) using a DI exposure machine. After pattern exposure so as to form a punched pattern of φ50 μm on the conductor pad by the amount, the carrier film is peeled off, and development (1 mass% Na ₂ CO ₃ , 30 ° C., 0.2 MPa) is performed in 60 seconds to form a resin layer. Formed a pattern. ^{Subsequently, the resin layer is irradiated with an exposure amount of 1 J / cm 2 in} a UV conveyor furnace equipped with a high-pressure mercury lamp, and then heated at 160 ° C. for 60 minutes to completely cure the resin layer to have an evaluation substrate having a pattern cured film. Was produced.

(Comparative Examples 2 and 3)
After laminating on the substrate under the above laminating conditions in the same manner as above, after pattern exposure so as to form a punched pattern of φ50 μm on the conductor pad with an exposure amount that can obtain 10 steps with a step tablet (41 steps) with a DI exposure machine. , PET film was peeled off, and development (1 mass% Na ₂ CO ₃ , 30 ° C., 0.2 MPa) was carried out in 60 seconds to form a pattern of a resin layer. ^{Subsequently, the resin layer is irradiated with an exposure amount of 1 J / cm 2 in} a UV conveyor furnace equipped with a high-pressure mercury lamp, and then heated at 160 ° C. for 60 minutes to completely cure the resin layer to have an evaluation substrate having a pattern cured film. Was produced.

(Etching amount)
The first resin layer was etched so as to have the following thickness with respect to the conductor thickness.
1. 1. 2. Thinner at a rate of more than 30% to 70% or less than the conductor thickness. 3. Thinner at a rate of more than 10% to 30% or less than the conductor thickness. 3. Thinner at a rate of 5% or more and 10% or less than the conductor thickness. Equivalent to conductor thickness (0%)

<Embedability>
A substrate having a conductor thickness of 15 μm and a circuit pattern of L / S = 12 μm / 12 μm is acid-treated with CZ8101, and then the first-layer dry films of each Example and Comparative Example are laminated according to the above-mentioned production method. Confirmation of embedding property was carried out by SEM observation of the cross section.
⊚: Embedded without voids.
X: Confirmed the presence of voids of about 1 to 2 μm.

<Insulation reliability>
Using the above laminated cured product, the HAST test was carried out under the conditions of 130 ° C., humidity 85%, and 5V.
⊚: Achieved insulation reliability for 300 hours or more.
Δ: Insulation reliability of 200 hours or more and less than 300 hours.
X: Insulation reliability of less than 200 hours.

A-1: Alkali-soluble resin A-1 synthesized in Synthesis Example 1 above
A-2: Alkali-soluble resin A-2 synthesized in Synthesis Example 2 above
B-1: Omnirad 907 manufactured by IGM Resins (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one)
B-2: Omnirad TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by IGM Resins.
C-1: DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd.
D-1: EPICLON N-770 manufactured by DIC (phenol novolac type epoxy resin, epoxy equivalent 188 g / eq., Softening point 70 ° C.)
D-2: NC-3000 manufactured by Nippon Kayaku Co., Ltd. (biphenyl type epoxy resin, epoxy equivalent 290 g / eq., Softening point 57 ° C.)
D-3: EPICLON N-695 manufactured by DIC (cresol novolac type epoxy resin, epoxy equivalent 215 g / eq., Softening point 95 ° C.)
D-4: glycidyl ether compound of NC-6000 (2- (4-hydroxyphenyl) -2- [4- [1,1-bis (4-hydroxyphenyl) ethyl] phenyl] propane manufactured by Nippon Kayaku Co., Ltd., epoxy. Equivalent 210 g / eq.)
D-5: NC-3000H manufactured by Nippon Kayaku Co., Ltd. (biphenol novolac type epoxy resin, epoxy equivalent 290 g / eq.)
E-1: FX-293 (phenoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.
F-1: HF-1M (phenol novolac resin) manufactured by Meiwa Kasei Co., Ltd.
F-2: LA-3018 manufactured by DIC (Novolak resin)
G-1: Phthalocyanine blue H-1: DICY (dicyandiamide)
H-2: DMAP
H-3: Melamine I-1: Core shell rubber I-1 prepared above
J-1: HCA-HQ manufactured by Sanko Co., Ltd. (10- (2,5-dihydroxyphenyl) -9,10-dihydro 9-oxa-10-phosphophenanthrene-10-oxide)
K-1: Solvent-dispersed product of silica surface-treated with a silane coupling agent having a methacryloyl group prepared above.
K-2: Solvent-dispersed product of silica surface-treated with a silane coupling agent having an amino group prepared above.
K-3: Barium sulfate (B-30 manufactured by Sakai Chemical Industry Co., Ltd., barium sulfate surface-treated with silica-alumina) solvent-dispersed product K-3 prepared above.
K-4: Solvent-dispersed product of alumina surface-treated with the silane coupling agent having an amino group prepared above K-4
K-5: MEK-AC-4130Y (methyl ethyl ketone dispersed silica sol) manufactured by Nissan Chemical Industries, Ltd.)

From the results shown in the above table, it can be seen that the laminated cured products of Examples 1 to 6 of the present invention can achieve both embedding property and insulation reliability.

1 Board 2a Connection circuit part (pad) of conductor circuit
2b Wiring part (line) of conductor circuit
3 Layer composed of first curable resin composition ((A) first cured product layer)
4 Layer composed of second curable resin composition ((B) second cured product layer)
5 Laminated hardened body 6 Solder bump 7 Conductor part 8 Semiconductor chip 9 Die 10 Laminated hardened body with die 11 Dam part 12 Laminated hardened body with die mounted 13 Laminated conductor part 14 Composed of curable resin composition Layer (cured product layer)
15 Laminated cured product with further laminated cured product layers

Claims (7)

A laminated cured product in which a (A) first cured product layer composed of a first curable resin composition and a (B) second cured product layer composed of a second curable resin composition are sequentially laminated on a circuit board. And
The thickness of the first cured product layer (A) is thinner than the thickness of the connection circuit of the circuit board.
The second cured product layer (B) contains an inorganic filler, and the second cured product layer contains an inorganic filler.
A laminated cured product, wherein the (A) first cured product layer does not contain an inorganic filler, or contains an inorganic filler in a smaller amount than the (B) second cured product layer. A curable resin composition according to claim 1, wherein the curable resin composition is used as the first curable resin composition in the laminated cured product. A curable resin composition according to claim 1, wherein the curable resin composition is used as the second curable resin composition in the laminated cured product. A dry film having a resin layer made of the curable resin composition according to claim 2. A dry film having a resin layer made of the curable resin composition according to claim 3. The laminated cured product according to claim 1, which is a semiconductor package substrate. On the circuit board
The (A) first cured product layer composed of the first curable resin composition and
A method for producing a laminated cured product in which (B) second cured product layers composed of a second curable resin composition are laminated in order.
(A) The first curable resin composition which does not contain an inorganic filler on a circuit board or contains an inorganic filler in a smaller amount than the second curable resin composition in terms of solid content. 1 A step of forming a cured product layer so as to be thinner than the thickness of the connection circuit of the circuit board.
Laminated curing comprising (B) a step of forming a second cured product layer composed of the second curable resin composition containing an inorganic filler on the (A) first cured product layer. How to make a body.

Images